p.1 

OAR Box 1392 

Prepped by Ollie Stewart 

Document Number: 

135) I l-A-10 

Docket Number: 

A-94-52 

Printed 7/7/2008 9:45:59 AM Sheet 135 of 136 
P.2 

vvEPA 

United States 

Environmental Protection 

Agency 

A-94-52 

EPA-600/R-97-0l8 b JT>A-/0 

March 1997 

Research and 

Development 

EVALUATION OF POLLUTION PREVENTION 

TECHNIQUES TO REDUCE STYRENE EMISSIONS 

FROM OPEN CONTACT MOLDING PROCESSES 

Volume II, Appendixes 

Prepared for 

Office of Air Quality Planning and Standards 

Prepared by 

National Risk Management 

Research Laboratory 

Research Triangle Park, NC 27711 
P.3 

FOREWORD 

The U. S. Environmental Protection Agency is charged by Congress with protecting the Nation's land, air, and water resources. Under a mandate of national 

environmental laws, the Agency strives to formulate and implement actions leading to a compatible balance between human activities and the ability of natural 

systems to support and nurture life. To meet this mandate, EPA's research 

program is providing data and technical support for solving environmental problems today and building a science knowledge base necessary to manage our ecological resources wisely, understand how pollutants affect our health, and prevent or reduce environmental risks in the future. 

The National Risk Management Research Laboratory is the Agency's center for 

investigation of technological and management approaches for reducing risks 

from threats to human health and the environment. The focus of the Laboratory's 

research program is on methods for the prevention and control of pollution to air, 

land, water, and subsurface resources; protection of water quality in public water 

systems; remediation of contaminated sites and groundwater; and prevention and 

control of indoor air pollution. The goal of this research effort is to catalyze 

development and implementation of innovative, cost-effective environmental 

technologies; develop scientific and engineering information needed by EPA to 

support regulatory and policy decisions; and provide technical support and .toifbrmation transfer to ensure effective implementation of environmental regulations 

and strategies. 

This publication has been produced as part of the Laboratory's strategic longterm research plan. It is published and made available by EPA's Office of Research and Development to assist the user community and to link researchers 

with their clients. 

E. Timothy Oppelt, Director 

National Risk Management Research Laboratory 

EPA REVIEW NOTICE 

This report has been peer and administratively reviewed by the U.S. Environmental 

Protection Agency, and approved for publication. Mention of trade names or 

commercial products does not constitute endorsement or recommendation for use. 

This document is available to the public through the National Technical Information 

Service, Springfield, Virginia 22161. 
P.4 

EPA-600/R-97-0l8b 

March 1997 

Evaluation of Pollution Prevention 

Techniques to Reduce Styrene Emissions 

from Open Contact Molding Processes 

Volume II, Appendixes 

By 

Emery J. Kong, Mark A. Bahner, Robert S. Wright, and C. Andrew Clayton 

Research Triangle Institute 

P.O. Box 12194 

Research Triangle Park, NC 27709 

EPA Cooperative Agreement CR 818419-03 

EPA Project Officer: Geddes Ramsey 

Air Pollution Prevention and Control Division 

National Risk Management Research Laboratory 

U.S. Environmental Protection Agency 

Research Triangle Park, NC 27711 

Prepared for 

U.S. Environmental Protection Agency 

Office of Research and Development 

Washington, DC 20460 
P.5 

Abstract 

Pollution prevention options to reduce styrene emissions, such as new materials and 

application equipment, are commercially available to the operators of open molding processes. 

However, information is needed about the percent reduction in emissions that is achievable 

with these options. 

To meet this need, several of these pollution prevention options were examined. 

Options examined were operator techniques, air flow velocities in the spraying area, gel coat 

and resin formulations, and application equipment. Styrene emission factors calculated from 

this test result were compared with the existing AP-42 emission factors for gel coat sprayup 

and resin applications. 

The study found that using controlled spraying (i.e., reducing overspray), low-styrene 

and styrene-suppressed materials, and nonatomizing application equipment can reduce styrene 

emissions from 11 to 52 percent. Facilities should investigate the applicability and feasibility 

of these pollution prevention options to reduce their styrene emissions. The calculated 

emission factors were from 1.6 to 2.5 times the mid-range AP-42 emission factors for the 

corresponding gel coat and resin application. These results indicate that facilities using 

existing .AP-42 emission factors to estimate emissions in open molding processes are likely to 

underestimate actual emissions. 

n 
P.6 

Contents 

Appendixes 

A. A Category III Quality Assurance Project Plan for the Evaluation of Pollution Prevention 

Techniques to Reduce Styrene Emissions from Open Contact Molding Processes 

B. Reichhold Standard Test Methods 

C. Verification and Intercomparison of Compressed Gas Calibration Standards 

D. Summary of Calibration Data, Calibration Error Tests, and Drift Checks 

E. A Summary of Emission Measurements, Gravimetric Measurements, and Calculated 

Emission Quantities and Emission Factors for the Test 

F. Statistical Analyses of Test Results 

G. THC Analyzer Evaluation: Sampling Line Loss and Pressure Effect 

H. An RTI Technical System Audit Report 

1. EPA Performance Evaluation of Total Hydrocarbon Analyzer 

in 
P.7 

Jit'--.' ' 

Appendix A 

A Category IE Quality Assurance Project Plan for the Evaluation of Pollution Prevention 

Techniques to Reduce Styrene Emissions from Open Contact Molding Processes (minus 

Appendixes) and RTFs Responses to EPA's Comments on the Category m Quality Assurance 

Project Plan 

A-i 
P.8 

POLLUTION PREVENTION TECHNOLOGY DEMONSTRATION 

EVALUATION OF POLLUTION PREVENTION TECHNIQUES 

TO REDUCE STYRENE EMISSIONS FROM OPEN CONTACT 

MOLDING PROCESSES 

CATEGORY III QUALITY ASSURANCE PROJECT PLAN 

EPA Cooperative Agreement CR 818419-03 

RTI Project No. 96U-5171-016 

Submitted to: 

EPA Project Officer - Carlos Nunez 

U.S. Environmental Protection Agency 

Office of Research and Development 

Air and Energy Engineering Research Laboratory 

Research Triangle Park, NC 27711 

Prepared by: 

Research Triangle Institute 

P.O. Box 12194 

Research Triangle Park, NC 27709 

April 28, 1995 

A-ii 
SIGNATURE PAGE 

P.9 

Project Officer r U.S. EPA, ORD 

Air & Energy Engineering Research Laboratory 

Quality Assurance Officer - U.S. EPA, ORD 

Air & Energy Engineering Research Laboratory 

fr rh if 

Carlos Nunez 

fancy /Vdams 

Date 

lam^tMk' A11A(K 

Date 

Project Manager 

Research Triangle Institute 

Project Leader 

Research Triangle Institute 

Quality Assurance Manager 

Research Triangle Institute 

Jesse Baskir Date 

Emery Kong Date' 

Cynthia Salmons Date 

A-iii 
P.10 

Recipients of official copies of this Quality Assurance Project Plan: 

Mr. Carlos Nunez 

Mr. Geddes Ramsey 

Dr. Nancy Adams 

Dr. Jesse Baskir 

Mr. Emery Kong 

Ms. Cynthia Salmons 

Mr. Mark Bahner 

Mr. Andrew Clayton 

Dr. R. K. M. Jayanty 

Mr. Mark Callicutt 

Mr. Federico Linares 

Mr. Lorenzo Esposito 

Mr. Mark Hollenbech 

Mr. Tom Hedger 

Mr. Charles Stard 

Mr. Casey Herbert 

Mr. Bob Lacovara 

Staff 

U.S. EPA, Air & Energy Engineering Research Laboratory 

Project Officer 

U.S. EPA, Air & Energy Engineering Research Laboratory 

Quality Assurance Officer 

Research Triangle Institute 

Pollution Prevention Program Acting Manager 

Research Triangle Institute 

Project Leader 

Research Triangle Institute 

Quality Assurance Manager 

Research Triangle Institute 

Testing Crew Chief 

Research Triangle Institute 

Experimental Design and Data Analysis 

Research Triangle Institute 

Emission Measurement Team 

Reichhold Chemicals, Inc. 

Technical Service Supervisor 

Reichhold Chemicals, Inc. 

Manager of Physical Testing and Application 

Reichhold Chemicals, Inc. 

Senior Technical Service Representative 

Cook Composites and Polymers 

Technical Manager for Gelcoat 

Magnum Industries 

Research and Development 

W.E.T. Inc. 

Composites Fabricators Association 

Director of Technical Service 

Research Triangle Institute 

Testing Crew Members 

A-iv 
P.11 

TABLE OF CONTENTS 

1.0 PROJECT DESCRIPTION A-1-1 

1.1 Background A-1-1 

1.2 Data Quality Objectives A-1-2 

1.3 Intended Use of Data A-1-2 

1.4 Scope of Work A-1-2 

1.4.1 Pilot Experiment A-1-3 

1.4.2 Gelcoat Experiment A-1-4 

1.4.3 Resin Experiment A-1 -5 

1.5 Schedule/Milestone Chart .. A-1-7 

1.6 Facility Description A-1 -9 

1.6.1 Total Enclosure System A-1 -9 

1.6.2 Resin Property Testing Laboratory A-1-11 

1.6.3 Open Contact Mold A-1-11 

1.7 Experimental/Test Matrix Design A-1 -11 

1.7.1 Critical and Noncritical Measurements A-1-11 

1.7.2. Experimental Design A-1-13 

1.7.2.1 Pilot Experiment A-1-13 

1.7.2.2 Gelcoat Experiment A-1-16 

1.7.2.3 Resin Experiment A-1-17 

1.7.2.4 Combining the Gelcoat and Resin Experiments A-1-18 

2.0 PROJECT ORGANIZATION AND RESPONSIBILITIES . . A-2-1 

3.0 DATA QUALITY INDICATOR GOALS FOR CRITICAL MEASUREMENTS A-3-1 

3.1 Objectives for Quantitative Data Quality Indicators ..-.'.' A-3-2 

3.1.1 Precision A-3-2 

3.1.2 Accuracy A-3-3 

3.1.3 Detection Limit A-3-3 

3.1.4 Completeness A-3-3 

3.2 Objectives for Qualitative Data Quality Indicators A-3-4 

3.2.1 Representativeness A-3-4 

3.2.2 Comparability A-3-4 

4.0 SAMPLING PROCEDURES A-4-1 

4.1 Total Enclosure and Capture Efficiency Test A-4-1 

4.2 Sampling Location and Duration of Test Run A-4-1 

4.3 Testing Procedures A-4-1 

4.4 Emission Measurement A-4-3 

4.5 Exhaust Air Flow Rate Measurement A-4-4 

4.6 Mass Balance Determination A-4-4 

4.7 Gelcoat and Resin Properties A-4-4 

A-v 
P.12 

4.8 Environmental Conditions A-4-5 

4.8.1 Linear Air Velocity in Spray Booth A-4-5 

4.8.2 Ambient Temperature A-4-6 

4.8.3 Relative Humidity A-4-6 

4.9 Equipment Type and Setup A-4-6 

4.9.1 Equipment Type A-4-6 

4.9.2 Equipment Setup A-4-6 

4.10 Operating Parameters for Parts A-4-7 

4.10.1 Catalyst Ratio A-4-7 

4.10.2 Gelcoat/Resin Thickness A-4-7 

4.10.3 Glass/Resin Ratio A-4-7 

5.0 ANALYTICAL PROCEDURES .'. A-5-1 

5.1 Types of Gelcoat and Resin Materials A-5-1 

5.2 Styrene Content A-5-1 

5.3 Gel time, Time to Peak, and Peak Exotherm Characteristics of 

Polyester Resins A-5-1 

6.0 DATA REDUCTION, VALIDATION, AND REPORTING A-6-1 

6.1 Data. Reduction A-6-1 

6.2 Data Validation A-6-3 

6.3 Data Reporting A-6-4 

7.0 INTERNAL PERFORMANCE AND SYSTEM AUDITS A-7-1 

7.1 Technical Systems Audits A-7-1 

7.2 Performance Evaluation Audits A-7-1 

7.3 Audits of Data Quality A-7-1 

8.0 CALCULATION OF DATA QUALITY INDICATORS A-8-1 

8.1 Precision A-8-1 

8.2 Accuracy A-8-1 

8.3 Method Detection Limit A-8-2 

8.4 Completeness A-8-2 

9.0 CORRECTIVE ACTION A-9-1 

A-vi 
P.13 

LIST OF FIGURES 

Figure 1-1. Proposed schedule and milestones A-1-8 

Figure 1 -2. Side view of the Reichhold Chemicals spray booth in a 

permanent total enclosure A-1-10 

Figure 1-3. Sketch of a male mold A-1-12 

Figure 2-1. Project organization chart A-2-3 

Figure 6-1. The data handling, reduction, validation, and reporting 

procedures A-6-2 

LIST OF TABLES 

Table 1-1. Anticipated Performance of Evaluation Test A-1-3 

Table 1-2. Test Runs for Pilot Experiment ; . A-1-4 

Table 1 -3. Test Runs for Each of the Gelcoat Formulations and 

Equipment Combinations A-1-5 

Table 1-4. Test Runs for the Resin Formulations and Equipment Types ..... . A-1-7 

Table 1-5. Summary of Critical and Noncritical Measurements A-1-14 

Table 1 -6. Randomly Ordered List of Trials for the Main Experiment . A-1 -20 

Table 3-1. Summary of Styrene Emission Data from a Previous RTI Testing .. A-3-1 

Table 3-2. Objectives for Quantitative Data Quality Indicators A-3-2 

Table 4-1. Summary of Measurement Location and Frequency A-4-2 

Table 4-2. Air Flow Pattern and Velocity in the Spray Booth A-4-5 

Table 4-3. Data Recording Sheet for the Pollution Prevention Technique Evaluation 

Test .; A-4-8 

Table 5-1. Data Recording Sheet for Gelcoat and Resin Properties A-5-2 

A-vii 
P.M 

Section No.: 

Revision: 0 

Date: 

Page: 

1.0 

April 

A-1-

28, 1995 

1 of 20 

1.0 PROJECT DESCRIPTION 

1.1 Background 

The Research Triangle Institute (RTI) is under a cooperative agreement with the 

U.S. Environmental Protection Agency (EPA), Air and Energy Engineering Research 

Laboratory (AEERL), to evaluate pollution prevention techniques to reduce styrene 

emissions from open contact molding processes. The open contact molding process is 

one of the most common production processes used by the reinforced plastics and 

composites (RP/C) industry. This process is used to manufacture boats, bathtubs, 

shower stalls, truck body parts, swimming pools, storage tanks, corrosion-resistant 

equipment, furniture and accessories, electrical and equipment housings and 

enclosures, duct and air handling equipment, etc. It is one of the RP/C processes that 

consumes the most polyester resins. It also has the greatest potential of emitting 

styrene due to the spraying equipment used and the openness of the process. 

Styrene is emitted during the application stage when a catalyzed gelcoat or resin 

is applied to the surface of an open contact mold. Styrene continues to emit from wet 

gelcoat or resin during gelation and curing. The open contact molding process usually 

is conducted in a facility with ample ventilation to maintain the ambient styrene 

concentrations under current Occupational Safety and Health Association (OSHA) 

standards of 100 ppm. Therefore, styrene emissions from open contact molding 

process are difficult to capture and control. 

The maximum achievable control technology <MACT) standards for the 

reinforced plastics and composites source category and boat building source category 

are scheduled to be promulgated by November 15,1997, and November 15, 2000, 

respectively. For some open contact molding processes, pollution prevention 

techniques could be used to reduce styrene emissions. These pollution prevention 

techniques include changing application equipment and environment and using 

different gelcoat or resin formulations. Existing information indicates that using 

nonspraying equipment or low-emitting/high-transfer efficiency spray guns, such as airassisted airless or high-volume low pressure spray guns, can reduce emissions from 

the application stage. Gelcoat and resin manufacturers also have developed different 

gelcoat and resin formulations to reduce emissions. However, the effects of these 

pollution prevention techniques have not been compared systematically. 

The purpose of this evaluation test is to use emission measurements and mass 

balance calculations to quantify and validate the effects of several pollution prevention 

techniques, specifically gelcoat/resin formulations and application equipment, on 

styrene emissions from the open contact molding process. The results of this study will 

be analyzed and presented to the RP/C industry so that individual facilities can identify 

A-1-1 
P.15 

Section No.: 1.0 

Revision: 0 

Date: April 28, 1995 

Page: A-1-2 of 20 

the most effective and practical pollution prevention techniques to reduce styrene 

emissions. 

This Quality Assurance Project Plan (QAPP) describes the scope of the 

proposed pollution prevention techniques evaluation test and the procedures that will be 

employed in the evaluation test to ensure that the data collected are of sufficient quality 

to achieve project objectives. 

1.2 Data Quality Objectives 

The objective of this testing is to determine the styrene emission reduction for 

several pollution prevention techniques from the baseline conditions. Pollution 

prevention techniques will be evaluated for gelcoat and resin applications on open 

contact molding processes. The baseline emissions will be determined for a regular 

gelcoat and a regular resin formulation using an air-assisted airless spray gun under a 

typical environmental condition. Comparison of emissions will be based on styrene 

emission factors expressed as weight percent of available styrene (% AS) and as mass 

per unit surface area (g/m2). The former unit is the unit used in the EPA Compilation of 

Air Pollutant Emission Factors, AP-42 Document. 

Table 1-1 summarizes the anticipated performance of the evaluation in terms of 

the widths of confidence intervals for differences in mean %AS associated with the 

primary comparisons of interest. The widths of the intervals depend on the magnitude 

of the measurement error standard deviation, which is denoted by o. Results are 

presented for a = 1, 3, and 5 percentage points. Thie prior test results (shown in Table 

3-1) suggest that standard deviations in this range should be achievable by mass 

balance calculation method. 

1.3 Intended Use of Data 

The test results will be analyzed, summarized, and presented to the RP/C 

industry in an EPA report. The report will provide quantitative emission reduction 

potentials for the pollution prevention techniques evaluated, so that a facility owner or 

operator can identify the most effective and practical pollution prevention techniques to 

reduce styrene emissions from its operation. 

1.4 Scope of Work 

This testing will include a pilot experiment and a main experiment. From the pilot 

experiment, the linear air flow velocity and the spraying technique will be determined for 

the main experiment. The main experiment will include a gelcoat experiment, which will 

examine two gelcoat formulations with three pieces of gelcoating equipment, and a 

resin experiment, which will examine six resin formulations and four pieces of resin 

A-1-2 
P.16 

Section No.: 

Revision: 0 

Date: 

Page: 

1.0 

April 28,1995 

A-1-3o»20 

application equipment. The formulations and equipment selected for the testing are 

representative of current and evolving technologies available to the RP/C industry. 

Each of the experiments is described in the following subsections. 

Table 1-1. Anticipated Performance of Evaluation Test 

Difference in mean 

%AS due to: 

Expected half width of 95% confidence interval on 

difference3 

0 = 1 o = 3 o = 5 

Alternative gelcoat formulation 

vs. baseline formulation 

(basedon12df)b 

±1.03 ±3.08 ±5.14 

Alternative gelcoat spray 

equipment vs. baseline 

equipment 

(basedon12df)b 

±1.26 ±3.77 ±6.29 

Alternative resin formulation vs. 

baseline formulation 

(based pn 15 df)c 

±1.51 ±4.52 ±7.54 

Alternative resin spray 

equipment vs. baseline 

equipment 

(based on 9 df)c 

±1.60 ±4.80 ±8.00 

Units for o and the half-widths are in percentage points. 

Construction of the interval is not meaningful if there is an interaction of the gelcoat formulations 

and equipment types. 

Half-widths are conservative in that larger numbers of degrees of freedom (df) may be available; 

this will lead to narrower confidence intervals. 

1.4.1 Pilot Experiment 

Before these formulations and equipment are examined, we will conduct a pilot 

experiment to determine the air flow velocity in the spray booth and the spraying 

method that will be used throughout the entire test. A low and a high air flow velocity in 

the spray area will be examined. A low air flow velocity in the spraying area will be 

established by diverting the makeup air away from the spraying area to the sides of the 

spray booth. A normal and a more careful spraying method will be examined for the 

application technique. The pilot experiment will be conducted using a low-profile resin 

or a regular gelcoat catalyzed with methyl ethyl ketone peroxide (MEKP) and by an airassisted airless (AAA) spray gun. Reichhold Chemicals or Cook Composites and 

A-1-3 

3 
P.17 

Section No.: 

Revision: 0 

Date: 

Page: " 

1.0 

April 28,1995 

A-1-4of20 

Polymers will provide the resin or gelcoat, respectively. Magnum Industries will provide 

the AAA spray gun and an operator to operate it. The results will be analyzed to 

determine whether there are any differences in styrene emissions resulting from 

different air flow velocities and spraying methods. Following the pilot experiment, one 

air flow velocity and one spraying method will be selected for the gelcoat and resin 

experiments in the evaluation test. 

The number of test runs for air flow velocity and spraying method are 

summarized as follows and presented in Table 1-2. 

A. Air flow velocity 

A1. Low air flow velocity (40 to 100 fpm) 

A2. High air flow velocity (100 to 200 fpm) 

B. Spraying method 

M1. Normal technique without conscious control of overspray from flanges 

M2. Alternative spraying technique with more conscious control of overspray 

Table 1 -2. Test Runs for Pilot Experiment 

M1-Normal technique 

M2-Alternative technique 

A1-Low air flow velocity 

3 

3 

A2-High air flow velocity 

3 

3 

1.4.2 Gelcoat Experiment 

The gelcoat formulations selected are one regular gelcoat with isophthalic 

acid/neopentyl glycol (ISO/NPG®)-based resin and a low volatile organic compound 

(VOC) gelcoat with the same base resin: Cook Composites and Polymers (CCP) will 

provide these two gelcoats. For the purpose of this testing, both gelcoats will contain 

straight styrene without any methyl methacrylate. MEKP catalyst will be used and the 

catalyst ratios will follow those suggested by CCP. 

The gelcoating equipment selected includes: one AAA external catalyst mixing 

spray gun, one high-volume low-pressure (HVLP) external catalyst mixing spray gun, 

and one HVLP internal catalyst mixing spray gun. The AAA external mixing spray gun 

is considered the baseline condition of the industry. The AAA spray gun will be 

compared with HVLP spray guns. The effects of internal and extemal catalyst mixing 

will be evaluated for the HVLP spray guns. Magnum will provide the AAA and the other 

two HVLP spray guns. A pump ratio of 20:1 will be selected for the gelcoat pump 

systems. The spray guns will be compared at similar gelcoat delivery rates. 

A-1-4 

H 
P.18 

Section No.: 

Revision: 0 

Date: 

Page: 

1.0 

April 28, 1995 

A-1-5of20 

The gelcoat formulations and application equipment are denoted as follows: 

a. Formulations 

GF1. a regular (ISO/NPG®) gelcoat containing only styrene monomer 

(baseline condition) 

GF2. a low VOC styrene-suppressed (ISO/NPG®) gelcoat containing only 

styrene monomer 

b. Equipment 

GE1. an AAA external catalyst mixing spray gun (baseline condition) 

GE2. an HVLP internal catalyst mixing spray gun 

GE3. an HVLP external catalyst mixing spray gun 

Table 1-3 shows the number of test runs for each of the gelcoat formulation and 

equipment combinations in the gelcoat experiment. 

Table 1-3. Test Runs for Each of the Gelcoat Formulations 

and Equipment Combinations 

Formulation 

GF1-Regular gelcoat 

GF2-Low VOC gelcoat 

Equipment type 

GEI-AAA(ext) 

3 

3 

GE2-HVLP(int) 

3 

3 

GE3-HVLP(ext) 

3 

3 

ext=External catalyst mixing. 

int=lnternal catalyst mixing. 

1.4.3 Resin Experiment 

The resin experiment will examine six resin formulations with an AAA spray gun 

and four application equipment with one standard resin. 

The resin formulations selected are one dicyclopentadiene (DCPD)-based lowprofile resin catalyzed with MEKP, one DCPD-based low-styrene resin, one 

orthophthalic(ORTHO)-based styrene suppressed resin, one DCPD-based low-profile 

resin catalyzed with benzoyl peroxide (BPO), a water-emulsified resin catalyzed with 

MEKP, and the same ORTHO-based styrene-suppressed resin at a higher suppressant 

concentration. All the resin formulations will be sprayed by an air-assisted airless spray 

gun. Reichhold Chemicals, Inc., will provide all resin formulations and catalyst, except 

the water-emulsified resin. The W.E.T., Inc. will provide the water emulsified resin. 

The catalyst ratios will follow those suggested by Reichhold and W.E.T., Inc. 

The resin application equipment selected are one AAA external catalyst mixing 

spray gun; an internal catalyst mixing flow coater; a pressure-fed roller; and an AAA 

A-1-5 

5 
P.19 

Section No.: 

Revision: 0 

Date: 

Page: 

1.0 

April 28, 1995 

A-1-6of20 

external catalyst mixing spray gun modified for the resin catalyzed with BPO. The AAA, 

external mixing spray gun is consider the baseline condition of the industry. The AAA 

spray gun is to be compared with other nonspraying equipment (i.e., the flow coater and 

the pressure-fed roller). Magnum will provide all the equipment for evaluation. A pump 

ratio of 11:1 will be selected for the resin pump systems. The equipment will be 

compared at similar resin delivery rates. 

Resin formulations and application equipment are denoted as follows: 

a. Formulations 

RF1. a DCPD-based low-profile resin catalyzed with MEKP (baseline 

condition) 

RF2. a DCPD-based low-styrene resin 

RF3. an ORTHO-based styrene-suppressed resin 

RF4. a DCPD-based low-profile resin catalyzed with BPO 

RF5. a water-emulsified resin 

RF6. the same ORTHO-based styrene suppressed resin at a higher 

suppressant concentration 

b. Equipment 

RE1. an AAA external catalyst mixing spray gun (baseline condition) 

RE2. an internal catalyst mixing flow coater 

RE3. an internal catalyst mixing pressure-fed roller 

RE4. a modified AAA, external catalyst mixing spray gun for the resin 

catalyzed with BPO 

Table 1-4 show the number of test runs for the resin formulation and equipment 

to be examined in the resin experiment. 

A-1-6 

I 
P.20 

Section No.: 

Revision: 0 

Date: 

Page: 

1.0 

April 28,1995 

A-1-7of20 

Table 1-4. Test Runs for the Resin Formulations 

and Equipment Types 

Formulation 

RF1 -DCPD-based lowprofile resin with MEKP 

RF2-DCPD-based lowstyrene resin 

RF3-ORTHO-based styrenesuppressed resin 

RF4-DCPD-based lowprofile resin with BPO 

RF5-water-emulsified resin 

RF6-the ORTHO-based 

styrene-suppressed resin at 

a higher suppressant 

concentration 

Equipment type 

REI-AAA(ext) 

6 

3 

3 

NA 

3 

3 

RE2-flow 

coater(int) 

3 

NA 

NA 

NA 

NA 

NA 

RE3-pressurefed roller(int) 

3 

NA 

NA 

NA 

NA 

NA 

RE4-modified 

AAA (ext) 

NA 

NA 

NA 

3 

NA 

NA 

ext=External catalyst mixing. 

Int=lntemal catalyst mixing. 

NA = Not included in the experiment. 

1.5 Schedule/Milestone Chart 

The schedule and milestones for this testing are shown in Figure 1 -1. The 

schedule and milestones are determined by the overall project completion date at the 

end of September. The evaluation test is scheduled to start in the first week of June 

1995 and will take 4 weeks to complete. The resin and gelcoat manufacturers and 

equipment vendors will need to provide the materials and equipment to the test site at 

Reichhold Chemicals Inc., c/o Mr. Mark Callicutt, 2400 Ellis Road, Durham, North 

Carolina 27703-5543 by May 26,1995. RTI will prepare a temporary total enclosure 

setup at Reichhold's spray booth in late May. RTI will conduct preliminary testing to 

.ensure that the enclosure and emission measurement instrument meet EPA 

requirements. The preliminary testing will also ensure that the emissions are within the 

proper concentration ranges of the total hydrocarbon (THC) analyzer prior to the actual 

testing. 

The proposed schedule shows that the testing will take place during the 

month of June. The testing schedule is based on the assumption that three test 

runs can be conducted in each working day and 19 working days will be needed to 

A-1-7 

7 
> 

03 

Major activities 

1. Prepare and submit a Category III QAPjP 

to EPA 

2. EPA reviews and approves the QAPjP 

3. RTI revises the QAPjP as needed 

4. Make arrangements to have materials 

and equipment delivered to Reichhold 

5. Set up the temporary total enclosure 

system and instrumentation at Reichhold, 

conduct preliminary testing to ensure that 

the setup, instrument, and equipment 

work properly 

6. Conduct the testing at Reichhold 

7. Analyze test results 

8. Prepare and submit a draft report to 

involved organizations for comments 

9. Technical review of the draft report 

by involved organizations 

10. Finalize the project report 

Project schedule and milestones 

March April May June July August Sept 

•V O 30 W 

m. 0 tt* a 

? ?. 5-1 

Figure 1-1. Proposed schedule and milestones. 

-» > o -» 

* a.

 b 

8.B 

u> 

to 

TJ 

ho 
P.22 

Section No.: 1.0 

Revision: 0 

Date: April 28, 1995 

Page: A-1-9of20 

complete the proposed 57 test runs. The final test period may be longer than the 

proposed duration, if Reichhold needs the spray booth for its own testing or the test 

team encounters technical difficulties that need to be resolved before the test can be 

resumed. 

1.6 Facility Description 

The evaluation test will be conducted in an isolated spray booth in the Reichhold 

Chemicals' physical testing laboratory, located in Research Triangle Park, North 

Carolina. This type of spray booth is commonly used in a gelcoating area of an RP/C 

facility. The Reichhold Chemicals' physical testing laboratory is used to conduct testing 

for their resin users. It is not a production facility; therefore, the background styrene 

concentration can be minimized. 

1.6.1 Total Enclosure System 

The spray booth is situated in an enclosed room with a double door leading to 

the physical testing laboratory. Figure 1-2 shows the side view of the spray booth. The 

room is 12 feet wide, 19 feet high, and 15 feet deep, which can be considered a 

permanent total enclosure. The double door measures 6 feet wide by 7 feet high, 

which can be consider the natural draft opening to the enclosure. 

The spray booth is 7 feet high, 11.5 feet wide, and 7.5 feet deep from the front 

edge to the filter bank. The filter bank is 6 feet high by 11 feet wide. The distance 

between the front edge of the spray booth to the double door is 4 feet 10 inches. The 

conditioned makeup air is provided through a duct (3 feet 9 inches by 4 feet) above the 

open space between the spray booth and the double door. This duct is considered a 

forced draft opening to the total enclosure system. The makeup air flows downward, 

then turns horizontally through the spray booth. The exhaust air flows through the filter 

bank at the end of the spray booth and is exhausted upward by a duct 34 inches in 

diameter. The exhaust flow rate from the spray booth is estimated to be 8,000 cfm 

when the double door is closed. The actual flow rate will be determined in preliminary 

testing. 

Emission measurements and exhaust air flow rate will be monitored from the 

exhaust duct. The sampling location is 8 diameters downstream of the last bend as 

shown in Figure 1-2. EPA Methods 1 and 2 will be used to determine the exhaust gas 

velocity and volumetric flow rate. EPA Method 25A will be used to determine total 

gaseous organic emissions. EPA Method 204 will be used to ensure that the enclosed 

room meets the criteria for a total enclosure. The sampling procedures are outlined in 

Section 4.0. 

A-1-9 

1 
P.23 

Section No.: 

Revision: 

Date: 

Page: 

1.0 

0 

April 28, 1995 

1-10 of 20 

o Emission and Air Row 

Rate Monitoring Location 

7'x6' (W) 

Double Door 

Ground Floor 

Application Equipment 

(Could be Placed Inside 

or Outside the Enclosure) 

Figure 1-2. Side view of the Reichhold Chemicals spray booth in 

a permanent total enclosure (19'H x 12'W x 15'L) 

A-1-10 

IO 
Section No.: 

Revision: 0 

Date: 

Page: 

1.0 

April 28,1995 

A-1-11 of 20 

1.6.2 Resin Property Testing Laboratory 

Reichhold Chemicals has a resin property testing laboratory located in the same 

building as the spray booth. The laboratory has all the instrument and equipment 

necessary to determine the styrene contents and curing characteristics for the gelcoat 

and resin formulations. Reichhold personnel will help the project team examine these 

properties for every gelcoat and resin formulation; Available instruments include an 

analytical balance, a forced-air oven, several Brookfield viscometers, a thermocouple, 

and a temperature recorder. 

1.6.3 Open Contact Mold 

A male mold will be used for this evaluation test. Figure 1-3 shows a drawing of 

this mold. The male mold will have five exposed smooth surfaces similar to a 

rectangular box. The mold will measure 2 feet high, 2,5 feet long, and 2 feet wide. A 2-

inch wide flange surrounds the bottom of the mold for ease of part removal. The total 

surface area, including flange, equals 24.5 ft2. The shape and surface area of this mold 

are selected to simulate real conditions in the open contact molding process. The mold 

is constructed of traditional reinforced plastics material to represent real molds used by 

the industry. The mold will be placed on a cart with wheels so that the operator can 

spray on all mold surfaces by turning the cart and without moving his position to the 

down-wind location. 

1.7 Experimental/Test Matrix Design 

1.7.1 Critical and Noncritical Measurements 

The critical and noncritical measurements, the frequency of measurement, the 

locations where these measurements are taken, and rhethods of measurements are 

shown in Table 1 -5. The emission measurements, exhaust air flow rate, and mass 

balance calculations are critical measurements for this study. The emission rates are to 

be determined from styrene emissions measured as total hydrocarbon concentration 

and the exhaust air flow rate monitored over the duration of the test run. Mass balance 

calculations will be used to determine transfer efficiency of the application equipment 

and to determine the weight losses from the mold and from the overspray. The styrene 

contents of the gelcoat and resin formulations are critical measurements; because the 

information will be used to express the styrene emission factors as the percent of 

available styrene in the materials. 

The linear air velocity over the mold and the ambient temperature are non-critical 

measurements, but they will be recorded to document actual test conditions. The type 

of gelcoat or resin materials and the equipment type will be noncritical parameters, but 

the emission quantities will be compared for different materials and equipment. 

A-1-11 
P.25 

Section No.: 

Revision: 

Date: 

Page: 

1.0 

0-

April 28, 1995 

1-12 of 20 

2" Flange surrounding 

the bottom of the mold 

to ease part removal 

Figure 1-3. Sketch of a male mold. 

A-1-12 
P.26 

Section No.: 

Revision: 0 

Date: 

Page: 

1.0 

April 28,1995 

A-1-13 of 20 

The equipment setup (such as pump and air pressure, spray tip size and angle, 

delivery rate, and catalyst ratio setting) are noncritical. The duration of application, 

gelcoat/laminate thickness, glass/resin ratio, gel time, total time to peak, and peak 

exotherm are noncritical measurements. However, these equipment conditions and 

gelcoat/resin parameters are important information that should be documented. 

1.7.2 Experimental Design 

1.7.2.1 Pilot Experiment 

Before executing the main experiment, several preliminary runs are proposed., 

The primary purpose is to help establish "standard" conditions under which the main 

experiment will be conducted. A secondary purpose is to gain insight into the 

magnitude of measurement error variability that might be anticipated in the main 

experiment. If the pilot experiment indicates major difficulties with the planned 

approach, this QAPP will be amended to indicate changes to the main experiment. -RTI 

will acquire verbal approval from the EPA Project Office for changes that occur during 

the test activities and submit a QAPP change as soon as possible. The proposed pilot 

consists of 12 trials -- namely, three replicates for each of the following conditions: 

a. Normal spraying method (M1), low air flow velocity (Al) 

b. Alternative spraying method (M2), low air flow velocity (A1) 

c. Normal spraying method (M1), high airflow velocity (A2) 

d. Alternative spraying method (M2), high airflow velocity (A2) 

Resin RF1 or gelcoat GF1 will be used in all cases, fhe following random 

ordering of the 12 trials will be used: b,c,d,c,b,a,d,a,d,b,c,a. Since one of the four 

conditions will be chosen as the standard method for the subsequent trials, it may be . 

possible to use those three pilot trials in the analysis of the.main resin experiment (e.g., 

to provide more degrees of freedom for error variability). 

The pilot will provide only a limited amount of information that can be used for 

statistical purposes. The data can be used, however, to give some idea of the impact 

of these two parameters on emissions. The analysis of variance for the experiment is 

as follows: 

A-1-13 

'•? > 
Section No.: 

Revision: 0 

Date: 

Page: 

1.0 

April 

A-1-

28, 1995 

4 of 20 

P.27_ 

Table 1-5. Summary of Critical and Noncritical Measurements 

Measurement 

THC concentration 

Exhaust air flow rate and velocity head^ApJ. 

Humidity 

Mass balance calculations 

1) gelcoat/resin materials used 

2) gelcoat/resin applied on mold 

3) cured material on mold 

4) cured material on other ground cover 

Types of gelcoat and resin materials 

Styrene content 

Gelcoat/resin properties 

1) gel time 

2) total time to peak 

3) peak exotherm 

Linear air velocity in the spray booth 

Ambient temperature 

Equipment type 

Equipment setup 

1) pump pressure 

2) air pressure 

3) spray tip size 

4) spray tip angle 

5) catalyst ratio setting 

6) equipment delivery rate 

Gelcoat/Resin data 

1) catalyst ratio 

2) gelcoat/laminate thickness 

3) gjass/resin ratio 

Classificatio 

n 

Critical 

Critical 

Noncritical 

Critical 

Noncritical 

Critical 

Noncritical 

Noncritical 

Noncritical 

Noncritical 

Noncritical 

Noncritical 

Method 

EPA Method 25A 

EPA Methods 1 and 2 

Sling psychrometer or relative 

humidity detector 

High precision scales with 150 kg 

capacity and 1 g readability 

Manufacturer data 

Reichhold standard test method 

No. 18-001 

Reichhold standard test method 

No. 18-050 and 18-051 

Hot wire anemometer 

Thermocouple 

Vendor information 

Vendor information and actual 

setting on equipment 

Mass calculation and mil gauges 

A-1-14 

if 
Source of 

variation 

M (spraying method) 

A (air flow velocity) 

M x A (interaction) 

Error 

Total 

Degrees of 

freedom 

1 

1 

1 

8 

11 

Section No.: 

Revision: 0 

Date: 

Page: 

1.0 

April 28, 1995 

A-1-15 0120 

P.28 

, 

The magnitude of differences in mean %AS that can be detected via the pilot 

experiment can be expressed in terms of the half-width of confidence intervals (Cl.) on 

the differences of interest: 

Difference in mean %AS Expected half-width of 95% Cl. 

M2 vs. M1 

A2 vs. A1 

For any two cells 

1.331o 

1.3310 

2.306O 

In this table, a denotes the standard deviation associated with measurement 

variability of emissions in %AS. The width of the confidence intervals is based on an 

assumption that the data for a given combination of M and A will be approximately 

normally distributed with a common measurement error.variability (similar assumptions 

apply to all other confidence intervals described herein). The 95 percent confidence 

interval half-width on the difference can be related to a pairwise hypothesis test 

(conducted at a significance level of 0.05) in two ways. First, if the estimated 

confidence interval does not include zero, then the corresponding test of no difference 

in mean %AS will be rejected. Second, if the true difference between the means (for 

A1 and A2, say) is equal to the expected half-width, then we will have a 50 percent 

chance of detecting a difference in the means. (Of course, if the true difference is 

larger than the half-width, then there will a higher likelihood that we will be able to 

detect a difference.) Thus if the underlying error variability of emissions in %AS is 5 

percentage points, then we should have about a 50 percent chance of finding a 

difference in the two flow rates if the true difference between them is about 6.7 (i.e., 

1.331x5). 

A similar statement can be made regarding the methods. Both of these 

statements assume that there is not a method by air flow interaction (in which case the 

overall comparisons would not generally be meaningful). It should be noted that the 

above analysis of variance (ANOVA) and confidence interval statements rely on an 

assumption of measurement-error variance homogeneity across the four combinations 

of factors M and A. 

A-1-15 

16 
P.29 

Section No.: 

Revision: 0 

Date: 

Page: 

1.0 

April 28,1995 

A-1-16of20 

1.7.2.2 Gelcoat Experiment 

The gelcoat experiment is one of the two major components in the main 

experiment. This experiment is aimed at evaluating how styrene emissions are affected 

by type of gelcoat formulation (factor GF) and type of equipment (factor GE). The 

factor combinations (two formulations and three equipment types) and proposed 

sample sizes are given in Table 1-3. The 18 trials are to be performed in random order 

(trials will be interspersed with the trials of the resin experiment, described below). 

The ANOVA associated with the design (a completely random design with three 

replications) has the following structure: 

Source of Degrees of 

variation freedom 

GF (gelcoats) 1 

GE (equipment) 2 

GF x GE (interaction) 2 

Error 12 

Total 17 

For the gelcoat experiment, the magnitude of differences that can be detected 

can be expressed in terms of the half-width of confidence intervals on the differences of 

interest: 

Difference in mean %AS Expected half-width of 95% Cl. 

GF2vs. GF1 

GE2vs. GE1,GE3vs. GE1, 

or GE3 vs. GE2 

For any two cells 

1.027O 

1.2580 

1.7790 

Again, o denotes the standard deviation associated with measurement error 

variability. The 95 percent confidence interval half-width on the difference can be 

related to a pairwise hypothesis test (conducted at a significance level of 0.05) in two 

ways. First, if the estimated confidence interval does not include zero, then the 

corresponding test of no difference will be rejected. Second, if the true difference 

between the means (for GF1 and GF2, say) is equal to the expected half-width, then we 

will have a 50 percent chance of detecting a difference in the means. Hence if the 

underlying error variability of emissions in percent available styrene is 5 percentage 

points, then we should have (1) about a 50 percent chance of finding a difference in the 

gelcoat formulations if the true difference between them is about 5.1, and (2) about a . 

50 percent chance of detecting a difference in two pieces of equipment if the true 

difference between them is about 6.3. Both of these statements assume that no 

A-1-16 

A 
P.30 

Section No.: 

Revision: 0 

Date: 

Page: 

1.0 

April 28, 1995 

A-1-17 of 20 

difference between them is about 6.3. Both of these statements assume that no 

interactions are present. It should be noted that the above ANOVA and confidence 

interval statements rely on an assumption of measurement error variance homogeneity 

across equipment, gelcoat formulations, and ieveis of percent available styrene. If the 

variability appears to change with level, then transformations such as logarithms will be 

considered (for the logarithmic transformation, the o can then be interpreted as the true 

underlying relative standard deviation). 

1.7.2.3 Resin Experiment 

The resin experiment is the other major component ofthe main experiment. This 

experiment is aimed at evaluating how styrene emissions are affected by type of resin 

formulation (factor RF) and type of equipment (factor RE). Table 1 -4 shows the 

proposed combinations and associated test runs. This design consists of 27 trials, 

which will be run in random order. Separate ANOVAs are used to test for different 

equipment (REs) and for the different resin formulations (RFs). 

The ANOVA for equipment comparisons is as follows: 

Source of Degrees of 

variation freedom 

RE (equipments) 2 

Error 9 or 12 or 19 or 22 

The various choices for the error degrees of freedom (df) result from which set of 

data is used for estimation of error variability: If just the 12 observations associated 

with the different equipment are employed, then 9 df result; if the 3 trials from the pilot 

are included, then 12 df result; if all trials in the resin experiment (Table 1-4) are used, 

19 df are available; and if the 3 pilot trials are added, 22 df are available. If variances 

across all cells in the experiment appear homogeneous and are also consistent with the 

variance of the pilot trials, then use of the larger degrees of freedom is warranted. 

The expected half-width of confidence intervals on the differences of equipment 

are as follows: 

Difference in mean %AS Expected half-width of 95% Cl. 

9 df 19 df 

RE2vs.RE1.RE3vs.RE1 1.599o 1.480o 

RE3vs. RE2 1.847o 1.709O 

A-1-17 

n 
P.31 

Section No.: 1.0 

Revision: 0 

Date: April 28, 1995 

Page: A-1-18of20 

The width of the confidence intervals will be slightly narrower if the same 

observations from the pilot experiment can be used for estimating measurement error 

variability (i.e., there will be more df for the error component ofthe ANOVA) If the 

underlying error variability of emissions in %AS is 5, then (assuming the 19 df situation) 

we should have about a 50 percent chance of finding a difference between the baseline 

spraying equipment and one of the alternatives if the true difference is 7.4 percentage 

points (i.e., 1.480x5). 

For resin formulation comparisons, the following ANOVA applies: 

Source of Degrees of 

variation freedom 

RF (resins) 5 

Error 15 or 18 or 19 or 22 

The various choices for the error df result from which set of data one uses, as 

previously discussed. 

The expected half-width of confidence intervals on the differences of resin 

formulations are as follows: 

Difference in mean %AS Expected half-width of 95% Cl. 

15 df 19 df 

RF2, RF3, RF4, RF5, 

orRF6vs. RF1 1.507o 1.480O 

All comparisons not 

involving RF1 1.740o 1.709o 

It should be noted that any comparison involving RF4 is a comparison not only of 

resin formulations but also of application methods. The width of the confidence 

intervals will be slightly narrower if some of the observations from the pilot experiment 

can be included in the data analysis. If the underlying error variability of emissions in 

%AS is 5, then (assuming the 19 df situation) we should have about a 50 percent 

chance of finding a difference between the RF1 and one of the alternative resin 

formulations if the true difference is 7.4 percentage points (i.e., 1.480 x 5). 

1.7.2.4 Combining the Gelcoat and Resin Experiments 

The gelcoat and resin experiments can be run effectively if trials of the two 

experiments are interspersed. In particular, it is desirable if each gelcoat trial is 

followed by at least one resin trial. To accomplish this and to randomize the ordering of 

A-1-18 

v. 
P.32 

Section No.: 1.0 

Revision: 0 

Date: April 28,1995 

Page: A-1-19of20 

trials within each separate experiment, a random ordering of the 27 trials in the resin 

experiment was first determined. Then a list of 27 "pseudo-trials" was created for the 

gelcoat experiment; the list contained the actual 18 gelcoat trials plus 9 dummy trials. 

These 27 "trials" were also independently randomly ordered and then the two randomly 

ordered lists were merged to produce the final composite set of trials, which is shown in 

Table 1-6. 

A-1-19 
P.33 

Section No.: 

Revision: 0 

Date: 

Page: 

1.0 

April 28,1995 

A-1-20of20 

Table 1 -6. Randomly Ordered List of Trials for the 

Main Experiment 

Trial 

No. 

1 

2 

3 

4 

5 

6 

7 

8 

9 

10 

11 

12 

13 

14 

15 

16 

17 

18 

19 

20 

21 

22 

23 

24 

25 

26 

27 

28 

29 

30 

31 

32 

33 

34 

35 

36 

37 

38 

39 

40 

41 

42 

43 

44 

45 

GF 

1 

1 

2 

1 

1 

1 

2 

2 

2 

2 

1 

2 

2 

2 

GE RF RE J 

3 

2 

1 

1 

1 

1 

3 

3 

2 

3 

2. 

2 

2 

1 

2 

1 

3 

3 

5 

, 

6 

5 

. 

1 

1 

1 

1 

3 

1 

, 

2 

4 

2 

6 

6 

2 

, 

1 

1 

1 

4 

1 

. 

3 

3 

5 

1 

. 

4 

1 

, 

1 

1 

1 

, 

1 

2 

3 

3 

1 

1 

1 

, 

1 

4 

1 

1 

1 

1 

1 

1 

3 

4 

2 

. 

1 

1 

1 

1 

, 

4 

1 

2 

Key: 

GF1 = a regular (ISO/NPG®) gelcoat containing only styrene 

monomer (baseline condition) 

GF2 = a low VOC styrene-suppressed (ISO/NPG®) gelcoat 

containing only styrene monomer 

GE1 = an AAA external catalyst mixing spray gun (baseline 

condition) 

GE2 = an HVLP internal catalyst mixing spray gun 

GE3 = an HVLP external catalyst mixing spray gun 

RF1 = a DCPD-based low-profile resin catalyzed with MEKP 

(baseline condition) 

RF2 = a DCPD-based low-styrene resin 

RF3 = an ORTHO-based styrene-suppressed resin 

RF4 = a DCPD-based low-profile resin catalyzed with BPO 

RF5 = • a water-emulsified resin 

RF6 = the same ORTHO-based styrene suppressed resin at a 

higher suppressant concentration 

RE1 = an AAA external catalyst mixing spray gun (baseline 

condition) 

RE2 = an internal catalyst mjxing flow coater 

RE3 = an internal catalyst mixing pressure-fed roller 

RE4 = a modified AAA, external catalyst mixing spray gun for the 

resin catalyzed with BPO 

A-1-20 

^ 0 
P.34 

Section No.: 

Revision: 0 

Date: 

Page: 

2.0 

• 

April 28, 1995 

A-2-1 of 3 

2.0 PROJECT ORGANIZATION AND RESPONSIBILITIES 

Figure 2-1 depicts the organizations and personnel involved in this pollution 

prevention technique evaluation test. Carlos Nunez is the EPA Project Officer for this 

research project. Nancy Adams is the EPA Quality Assurance Officer. 

Emery Kong, the RTI Project Leader, will coordinate the preparation and testing 

activities. Emery Kong will be responsible for developing the QAPP, all data generated 

under this study, all corrective action, and the overall technical quality of the evaluation 

test. Andrew Clayton will assist in the experimental design and data analysis. Mark 

Bahner is the RTI Testing Crew Chief. He and Keith Leese will conduct the actual 

testing. Craig Whitaker and Robert Wright will operate the THC analyzer and measure 

the exhaust air flow rate. Mark Bahner will also be responsible for the data reduction 

activities, analyzing the test results, and preparing the final report. Cynthia Salmons, the 

RTI QA Manager, William Yeager, and Shrikant Kulkarni will provide assistance in the 

QAPP preparation and ensure that the data collected adhere to the quality assurance 

requirements specified herein. They are independent of the technical activities on this 

project. 

Reichhold will provide technical assistance, resin materials, and catalysts for the 

testing. Mark Callicutt, Reichhold's Technical Service Supervisor, will be the primary 

contact at Reichhold. Federico Linares, Manager of Physical Testing and Application, 

will provide facility support, and Lorenzo Esposito, Reichhold's Senior Technical Service 

Representative, will provide technical support to the test. Reichhold's technical service 

personnel will analyze some specific properties of the gelcoat and resin formulations in 

their laboratory. 

Mark Hollenbech of Cook Composites and Polymers (CCP) will provide both the 

ISO/NPG®-based regular gelcoat and low VOC gelcoat for testing. Casey Herbert of 

W.E.T. Inc., will provide the water emulsified resin for testing. Tom Hedger of Magnum 

Industries will provide gelcoat and resin application equipment. Charles Stard from 

Magnum Industries will be onsite during the test period to operate the equipment. 

This testing will not have any off-site sample analysis. All measurements and 

process data will be collected onsite or analyzed in Reichhold Chemicals' laboratory 

during the test. Emery Kong will ensure that all testing procedures arid quality 

assurance requirements are correctly followed. Emery Kong will communicate with 

other contributing organizations that will provide materials, equipment, and support for 

the test. He will communicate with Reichhold personnel for necessary facility, 

laboratory, and technical support for the test. If Emery Kong is absent, Mark Bahner 

will assume all coordination responsibilities. 

A-2-1 
P.35 1 

Section No.: 2.0 

Revision: 0 

Date: April 28,1995 

Page: A-2-2 of 3 

As the Testing Crew Chief, Mark Bahner will coordinate all activities and on-site 

personnel during the testing and report to the Project Leader. He will communicate with 

the application equipment operator and the THC analyzer operator to address any 

concerns or problems that they might encounter. Decisions to stop or continue testing 

will be made by the Project Leader. 

A-2-2 

AA 
P.36 

Section No.: 

Revision: 

Date: 

Page: 

2.0 

0 

April 28, 1995 

2-3 of 3 

I I EPA Quality 1 

I I Assurance Officer 1 

Nancy Adams 

919-541-5510 

• I RTI Quality 

I I Assurance Officer I 

Cynthia Salmons 

919-541-6948 

William Yeager 

919-541-6287 

Shrikant Kulkarni 

919-541-5919 

Provide QA support 

and review QAPP 

• 1 RTI Experimental 

I I Design and 

| | Data Analysis 

Andrew Clayton 

919-541-6392 

1 Magnum Industries 

Charles Stard 

919-361-2095 

Operates application 

equipment on-site 

EPA/AEERL 

Project Officer 

Carlos Nunez 

919-541-1156 

1 RTI Project Leader 1 

Emery Kong 

919-541-5964 

Responsible for 

overall planning, 

coordination, and 

report preparation 

1 Testing Crew 1 

Mark Bahner (Chief) 

919-541-6016 

Keith Leese 

919-541-8020 

Responsible for data 

collection, analysis, 

and report preparation 

| RTI Emission I 

| Measurement Team I 

Craig Whitaker 

919-541-5988 

Robert Wright 

919-541-6263 

Operate the THC 

analyzer and measure 

air flow rate 

Composites Fabricators 1 

Association | 

Bob Lacovara 

215-721-9246 

Provides technical 

review and suggestions 

Reichhold 

Chemicals, Inc. 

Mark Callicutt 

919-990-8013 

Federico Linares 

919-990-8083 

Lorenzo Esposito 

919-990-8022 

Provide resins, catalysts, 

spray booth, and 

laboratory analysis 

1 Cook Composites I I 

1 and Polymers I I 

Mark Hollenbeck 

816-391-6000 

Provides gel coat 

formulations 

1 Magnum Industries l | 

Tom Heager 

813-573-2955 

Provides application 

equipment and operator 

1 W.E.T. Inc. II 

Casey Herbert 

803-556-2506 

Provides water emulsifier 

resin 

Figure 2-1. Project organization chart. 

A-2-3 

2 3 
P.37 

Section No.: 

Revision: 0 

Oate: 

Page: 

3.0 

April 28, 1995 

A-3-1 of 5 

3.0 DATA QUALITY INDICATOR GOALS FOR CRITICAL MEASUREMENTS 

This section presents the qualitative and quantitative descriptors that are used 

to interpret the degree of acceptability of the test data. The principal data quality 

indicators are precision, accuracy, detection limits, and completeness. 

The primary objectives for this testing are to quantify the emissions from 

selected pollution prevention techniques and to compare the emissions of these 

techniques with the baseline conditions. Styrene emissions for baseline conditions and 

each of the pollution prevention techniques will be expressed as percent of available 

styrene in the gelcoat and resin formulations. The data quality indicator (DQI) goals 

specified in this section are based on results obtained from previous tests. If these DQI 

goals are attained in this testing, sufficient valid data of known quality will be collected 

to evaluate different pollution prevention techniques. 

The results of a recent test conducted by RTI in early March 1995 are 

summarized in Table 3.1. This table presents the styrene emission data (expressed as 

%AS) and preliminary statistical analysis of the results measured by mass balance and 

THC emission measurement methods. In this table, a denotes the standard deviation 

associated with measurement variability of emissions in %AS. 

Table 3-1. Summary 

Formulation 

Gelcoat 

Resin 

Resin 

Equipment 

Spray-up 

Hand layup 

Chop and 

spray-up 

of Styrene 

Method 

MBa 

THC 

MB 

THC 

MBa 

THC 

Emission Data from a Previous RTI Testing 

No. of test 

runs 

3 

3 

3 

3 

4 

4 

Mean (% of 

AS) 

65.0 

66.7 

20.3 

19.7 

24.5 

20.8b 

O 

(standard 

deviation 

in %AS) 

2.6 

4.6 

1.2 

0.7 

1.3 

5.3b 

Relative 

standard 

deviation 

(%) 

4 

7 

6 

4 

5 

26b 

v1B=mass balance method. 

THC=THC emission measurement method. 

a

 Mass balance standard deviations for gelcoat and resin spray-up include corrected values. 

b

 Includes one chop spray test run that had a known large error. 

A-3-1 

Z Y 
P.38 

Section No.: 

Revision: 0 

Date: 

Page: 

3.0 

April 28,1995 

A-3-2 of 5 

3.1 Objectives for Quantitative Data Quality Indicators 

Quantitative DQIs are typically defined in terms of measurement precision, 

accuracy, detection limits, and completeness. The DQI objectives for the critical 

measurements are summarized in Table 3-2. These DQI objectives are based on the 

results of a recent RTI test and data in Table 3-1. Precision is typically determined from 

duplicate measurements and is usually expressed as percent difference or standard 

deviation in either absolute or relative terms. Accuracy is the degree of agreement 

between an observed value and an accepted reference value. For the THC analyzer 

and balance, the accuracy will be determined from standard reference styrene gases 

and weights, respectively. Detection limits are the lowest concentration or amount of 

weight that can be determined to be different from zero. Completeness is defined as • 

the ratio of the amount of valid data obtained compared to the planned amount. 

Procedures for determining these quantitative DQIs are discussed in more detail below. 

Table 3-2. Objectives for Quantitative Data 

Measurement 

(unit) 

THC conc. 

(ppm) 

Exhaust air 

flow rate 

(cfm) 

Mass balance 

(g) 

Styrene 

content (%) 

RPD = Relative p< 

Method 

EPA Method 

25A 

EPA Method 2 

Floor-type, highprecision 

balance 

Reichhold 

standard test 

method No. 18-

001 and a highprecision 

analytical 

balance 

jrcent difference as 

Precision 

(RPD or 

RSD) 

10% 

10% 

5% 

0.5 % 

calculated from 

Accuracy 

(%) 

+1-5 

+/-5 

+/-1 

+/-1 

duplicate meas 

Qualityjndicators 

Detection limit 

1 ppm 

NA 

i g 

0.0001 g 

jrements. 

Completeness 

(%) 

90 

90 

90 

90 

RSD = Relative standard deviation as calculated from three or more replicates 

3.1.1 Precision 

Precision objectives for all the listed measurements are presented as relative 

percent difference (RPD) of duplicate measurements or as relative standard deviation 

(RSD) of three or more replicates. The number of replicates for each test are shown in 

Tables 1-3 and 1-4. Precision for THC measurement, air flow rate measurement, and 

mass balance measurement is shown in Table 3-2. The styrene content for each 

A-3-2 

^5 
P.39 

Section No.: 

Revision: 0 

Date: . 

Page: 

3.0 

April 28.1995 

A-3-3 of 5 

gelcoat or resin formulation is determination by duplicate samples having an RPD of +/-

0.5 percent. If duplicate samples are not within +/- 0.5 percent, the entire test to 

determine styrene content will be repeated. 

3.1.2 Accuracy 

The accuracy of the THC analyzer will be determined following the calibration 

error test procedures in Section 6.4 of EPA Method 25A. Immediately prior to the test 

series, a zero gas and high-level calibration gas are introduced at the calibration valve 

assemble. Then the analyzer output is adjusted to the appropriate levels, if necessary. 

The predicted response for the low-level and mid-level gases based on a linear . 

response line between the zero and high-level responses is calculated. Then low-level 

and mid-level calibration gases are introduced successively to the measurement 

system. The analyzer responses for low-level and mid-level calibration gases are 

recorded and the differences between the predicted responses are determined. These 

differences must be less than 5 percent of the respective calibration gas values. If not, 

the measurement system is not acceptable and must be replaced or repaired prior to 

testing. 

The accuracy of the floor-type, high-precision balance (150,000 g capacity with 

1 g readability) will be determined usihg standard reference weights. The balance has 

an internal calibration weight that is used to calibrate the balance initially. Then the 

accuracy of the floor-type balance will be checked by placing reference standard 

weights from 1 g up to 1 kg with and without the cart and empty mold. The accuracy of 

the analytical balance will be checked using standard weights suitable for its capacity 

range. The accuracy of the floor-type balance and the analytical balance should be 

less than 1 percent of the respective standard weights. 

3.1.3 Detection Limit 

The detection limit is defined as the lowest concentration or amount of the target 

analyte that can be determined to be different from zero from a single measurement at 

a stated level of probability. The detection limits for the instruments used for critical 

measurements are presented in Table 3-2. These instruments include the THC 

analyzer for emission measurement, the floor-type high-precision balance for material 

balance determination, and the analytical balance for styrene content determination. 

The detection limits specified in Table 3-2 provide adequate quantification for the 

measurements of interest. 

3.1.4 Completeness 

Completeness is defined as the amount of valid data obtained compared to the 

planned amount. The completeness objective of 90 percent was selected based on the 

results of a recent RTI test that compared emission measurement and mass balance 

A-3-3 

Zk 
P.40 

Section No.: 3.0 

Revision: 0 

Date: April 28,1995 

Page: A-3-4 of 5 

methods to quantify styrene emissions from open contact molding processes. A 

completeness level of 90 percent ensures that sufficient valid data of known quality are 

collected to evaluate different pollution prevention techniques for styrene emission 

reduction. The results from emission measurements and mass balance methods will 

complement each other, because each method has good precision. In the event that 

both test methods failed for more than 10 percent of the planned test runs and the 

completeness level of 90 percent is not met, then those invalid test runs will be 

repeated. 

3.2 Objectives for Qualitative Data Quality Indicators 

Qualitative DQIs are typically defined in terms of representativeness and 

comparability. The representativeness is the degree to which the collected data 

accurately and precisely represent the population or the actual operations. The 

comparability is the degree or confidence to which one data set can be compared to 

another. These qualitative DQIs are described in more detail in the following sections. 

3.2.1 Representativeness 

The representativeness of this testing is best determined by the materials and 

equipment used, the environmental conditions of the testing, and the operator 

techniques. The gelcoat and resin materials, except the water-emulsified resin, and the 

application selected for testing are currently available to, and used by, the industry. 

Water-emulsified resin is currently used by the industry to a very limited extent; 

however, this testing will determine whetherfhis resin can significantly reduce styrene 

emissions. The environmental conditions (i.e., air flow velocity and ambient 

temperature) for the testing will be controlled so that they are representative of typical 

conditions in an operating facility. The person who will operate the equipment is an 

experienced technical support person from Magnum Industries. His experience will 

ensure that the operating procedures are consistent between test runs and 

representative of industry practice. 

The emissions in the spray booth will be representative of actual industry 

practice. As is discussed.in more detail in Section 4.1, EPA Method 204 for a total 

enclosure is to be followed to ensure that 100 percent of the emissions is captured. 

3.2.2 Comparability 

The baseline emissions of this testing will be compared to the results RTi 

collected from an early March testing at Dow Chemical that used similar spraying 

techniques and the same gelcoat and resin materials. Another styrene emission study 

is planned by Composites Fabricators Association (CFA) to be conducted at Dow 

Chemicals in a time frame similar to this testing. The same regular gelcoat and lowprofile resin materials will be applied by similar spraying techniques in the CFA testing. 

A-3-4 
P.41 

Section No.: 

Revision: 0 

Date: 

Page: 

3.0 

April 28,1995 

A-3-5 of 5 

The measurement procedures and methods will be similar for the CFA tests and this 

testing; therefore, results from both testings should be comparable. 

A-3-5 

Zr? 
P.42 

Section No.: 

Revision: 0 

Date: 

Page: 

4.0 

April 28, 1995 

A-4-1 of 9 

4.0 SAMPLING PROCEDURES 

4.1 Total Enclosure and Capture Efficiency Test 

The open contact molding process will be conducted at a spray booth in a total 

enclosure setup in Reichhold Chemicals' physical testing laboratory. The spray booth is 

described in Section 1.6.1. The enclosure will be tested prior to the pilot and main 

experiments to ensure that the enclosure meets EPA's total enclosure guidelines (EPA 

Method 204), so that the emissions from the test can be assumed 100 percent 

captured. The capture efficiency of the enclosure will be examined by (1) evaporating a 

known quantity of styrene (determined by a high- precision scale) and measuring the 

total styrene emissions at the exhaust stack and (2) making sure that all air flows at 

natural draft openings flow inward and the velocity is at least 200 fpm. 

4.2 Sampling Location and Duration of Test Run 

Emissions from the open contact molding processes will be measured at the 

exhaust stack of the enclosure. A test run will start when gelcoat or resin material is 

applied to a mold and finish when the gelcoat or resin material is cured (as determined 

by a negligible rate of emissions). An earlier RTI test at Dow Chemical Company 

indicated that a test run may last from 1 -1/2 to 2 hours. At the end of a test run, the 

mold will be removed from the enclosure and the enclosure will be flushed with fresh 

makeup air for the next test run. The THC analyzer will measure the background 

concentration before each test run. Any other VOC emission sources will be eliminated 

from the immediate area to minimize the background VOC concentration. 

Table 4-1 shows the locations and frequencies of the measurements for the 

test. 

4.3 Testing Procedures 

Procedures for individual test runs are outlined in this section. More detailed 

descriptions of the procedures are presented in the following sections. 

A Before the Test Run 

1. Measure and record the gelcoat/resin properties 

2. Calibrate the THC analyzer 

3. Measure the baseline concentration in the spray booth with the THC analyzer 

4. Measure and record initial air temperature, velocity head, and relative humidity 

A-4-1 

V\ 
P.43 

Section No.: 

Revision: 0 

Date: . 

Page: 

4.0 

April 28.1995 

A-4-2 of 9 

Table 4-1. Summary of Measurement Location and Frequency 

Measurement 

THC concentration 

Exhaust air flow rate and velocity head (Ap) 

Humidity 

Mass balance calculations 

1) gelcoat/resin materials used 

2) gelcoat/resin applied on mold 

3) cured material on mold 

4) cured material on other ground cover 

Types of gelcoat and resin materials 

Styrene content 

Gelcoat/resin properties 

1) gel time 

2) total time to peak 

3) peak exotherm 

Linear air velocity in the spray booth 

Ambient temperature 

Equipment type 

Equipment setup 

1) pump pressure 

2) air pressure 

3) spray tip size 

4) spray tip angle 

5) catalyst ratio setting 

6) equipment delivery rate 

Gelcoat/Resin data 

1) catalyst ratio 

2) gelcoat/laminate thickness 

3) glass/resin ratio 

Classification 

Critical 

Critical 

Noncritical 

Critical 

Noncritical 

Critical 

Noncritical 

Noncritical 

Noncritical 

Noncritical 

Noncritical 

Noncritical 

Location 

Exhaust stack 

Exhaust stack 

Spray booth 

Spray booth 

Manufacturer 

Laboratory 

Laboratory 

Spray booth 

Spray booth 

Equipment 

vendor 

Spray booth 

Spray booth 

Frequency 

Continuous 

Flow rate (weekly), 

Ap (every 15 

minutes) 

Before each test run 

Each test run 

Each gelcoat and 

resin formulation 

Each gelcoat and 

resin formulation 

Each gelcoat and 

resin formulation 

Every week 

Every test run 

Each equipment 

Each equipment 

Each test run 

A-4-2 

3° 
P.44 

Section No.: 4.0 

Revision: 0 

Date: April 28,1995 

Page: A-4-3 of 9 

5. Calibrate the balance(s) and check the accuracy with standard weights 

6. Prepare and adjust the application equipment 

7. Measure equipment delivery rate at the setup conditions in a remote location 

8. Record the equipment setup conditions 

9. Record the initial weights for mold, gelcoat/resin, catalyst, fiberglass 

reinforcement, protective skirt for cart, and ground cover 

B. During the Test Run 

1. Initiate the timer as soon as the application starts 

2. Record styrene emissions with the THC analyzer continuously 

3. Record velocity head (AP) and air temperature every 15 minutes 

4. Record the time and the weight of gelcoat/resin reading as soon as the 

application is completed (the application equipment can be removed for 

cleaning) 

5. Measure and record wet gelcoat/laminate thickness at the center of each mold 

surface 

6. Remove the protective skirt from the cart and record the weight of the wet mold 

at the end of application 

7. Reattach the protective skirt to the cart 

8. Stop the test run when the concentration returns to the baseline concentration or 

when incremental emissions are negligible 

9. Record the time at the end of the test run 

C. After the Test Run 

1. Record the final weights for mold, catalyst, fiberglass reinforcement, protective 

skirt for cart, and ground cover immediately 

2. Conduct the baseline drift determination for the THC analyzer 

3. Remove the moid from the enclosure and flush the enclosure with fresh makeup 

air until the baseline concentration stabilizes 

4.4 Emission Measurement 

Styrene emissions will be measured from the exhaust stack of the enclosure 

using a total hydrocarbon analyzer following the EPA Method 25A. The THC analyzer 

will provide real-time measurements of the emission concentrations. Any other VOC 

emission sources will be eliminated from the enclosure, so that the total VOC emissions 

measured can be assumed to be from styrene emissions. Two to three concentration 

ranges (0-11 ppm, 0-110 ppm, and 0-1,100 ppm) on the THC analyzer will be used for 

the emission measurement. If the highest concentration range (0-1,100 ppm) is used, 

the maximum concentration is not expected to exceed 300 ppm. The following styrene 

standard reference gases are available to establish the calibration curve for each of the 

concentration ranges; 5.1,10.7, 49.5, 81.5, and 237.1 ppm. Exceptions to EPA Method 

25A are that the calibration error check for lowest concentration range (0-11 ppm) will 

be done with one instead of two standard reference gases. 

A-4-3 

3^ 
P.45 

Section No.: 

Revision: 0 

Date: 

Page: 

4.0 

April 28,1995 

A-4-4 of 9 

4.5 Exhaust Air Flow Rate Measurement 

The exhaust flow rate will be measured using EPA Methods 1 and 2 at least 

once a week. EPA Method 2 specifies the use of either a standard or S-type pitot tube 

to traverse the duct. Because the particulate loading of the exhaust air stream is 

expected to be low for this test series, a standard pitot tube will be used. The exhaust 

flow rate will be measured at traverse points using a standard pitot tube with a 

differential pressure gauge that meets the specifications described in EPA Method 2, 

Section 2.2. The exhaust flow rate will be correlated to the velocity head measured at 

the center point. The center point velocity head (Ap) will be monitored periodically 

(every 15 minutes) to ensure that airflow rate is consistent during the test run. The 

relative humidity of the air in the spray booth will be measured by a sling psych rometer. 

4.6 Mass Balance Determination 

Weight losses due to styrene emissions will be determined using a floor-type, 

high-precision balance (Sartorius Corporation, Model F150S) that has a 150,000-g 

capacity and 1 g readability. The initial and final Weights of mold, gelcoat/resin 

materials, catalyst, fiberglass reinforcement, protective skirt for the cart, and ground 

cover will be measured by two balances. (A protective skirt will encircle the cart to 

prevent contamination during the application.) Total emission quantity will be 

determined from the difference of total materials used and the final weights after curing 

(see data reduction in Section 6.0). From the weights of materials used and materials 

applied on the mold, the transfer efficiency can be calculated for each test run. 

Weight loss due to emissions will be recorded for each test run and the results 

will be compared to the emission measurement to determine whether these two 

methods are comparable. 

4.7 Gelcoat and Resin Properties 

Roughly a liter of sample will be taken from each of the gelcoat and resin 

container for analysis. Before sampling, the content in the container will be thoroughly 

mixed by a hand-held mixer for 2 minutes. The content will be scooped out to a 

nonreactive container and delivered to the laboratory. The type of material, lot/batch 

number, and container number will be recorded on the sample container. This 

information will be recorded on the data sheet in Section 5.0. Analytical procedures 

used to determine gelcoat and resin properties are presented in Section 5.0. These 

gelcoat and resin properties will be documented in the report to show the reader what 

kind of gelcoat materials were examined in the testing. 

A-4-4 

^ 
P.46 

Section No.: 

Revision: 0 

Date: 

Page: 

4.0 

April 28,1995 

A-4-5 of 9 

4.8 Environmental Conditions 

Environmental conditions include linear air velocity and the ambient temperature 

in the spray booth. These conditions will be maintained at constant ieveis when 

feasible. The linear air velocity in the spray booth will be maintained at the level 

selected from the pilot testing. The temperature in the spray booth is affected by the 

temperature of the makeup air, which is heated or cooled according to the difference in 

indoor and outdoor temperatures. The actual temperature will be recorded for every 

test run on the data sheet shown at the end of Section 4. 

4.8.1 Linear Air Velocity in Spray Booth 

Linear air velocity in the spray booth will be measured with a hot wire 

anemometer at various traverse points in the spray booth. The spray booth will be 

divided into three sections (i.e., at front edge, in the middle, and at filter face), two 

layers (in the middle of top and bottom filter banks), and four divisions from left to right. 

These (3x2x4) volumetric traverse points will provide 24 readings to characterize the air 

flow pattern and velocities in the spray booth. Linear air velocities will be verified once 

every week or whenever the physical setup of the enclosure is changed. The air flow 

pattern and velocities will be recorded in Table 4-2. 

Table 4-2. Air Flow Pattern and Velocity in the Spray Booth 

Filter bank (top) 

Filter bank 

(bottom) 

Middle (top) 

Middle (bottom) 

Front edge (top) 

Front edge 

(bottom) 

1/5 width from left 

wall 

Dir. Vel. 

2/5 width from 

left wall 

Dir. Vel. 

3/5 width from 

left wall 

Dir. Vel. 

4/5 width from left 

wall 

Dir. Vel. 

Dir. = Air flow direction expressed by an arrow head. 

Vel.= air flow velocity in fpm. 

A-4-5 

33 
P.47 

Section No.: 

Revision: 0 

Date: 

Page: 

4.0 

April 28,1995 

A-4-6 of 9 

4.8.2 Ambient Temperature 

Ambient temperature in the exhaust air and in the spray booth will be monitored 

with thermocouples. The temperature will be recorded every 15 minutes during the test 

run. 

4.8.3 Relative Humidity 

Relative humidity in the spray booth will be measured before each test run by a 

sling psychrometer or a relative humidity detector. The relative humidity reading will be 

recorded on the data sheet shown later. 

4.9 Equipment Type and Setup 

The equipment type and setup will be documented in the report to show the 

reader what kinds of equipment are examined in the testing. 

4.9.1 Equipment Type 

The types of equipment to be examined are described in Section 1.4. 

4.9.2 Equipment Setup 

The equipment setup affects the operation of the equipment and the emission 

generated. These conditions include pump pressure, air pressure, spray tip size, spray 

tip angle, catalyst ratio, and equipment delivery rate. These set-up conditions will be 

adjusted according to the vendors' recommendations by an experienced operator so 

that the equipment will be operated under their optimum conditions. The setup will be 

recorded for each equipment in each test run. The same setup will be used for the 

same equipment and material in the replicate test runs. 

The equipment delivery rate will be determined during the standard calibration of 

the equipment under the same conditions of the testing. The standard calibration 

procedures consist of spraying the gelcoat or resin materials into a piastic bag for 30 

seconds and weighing the amount of output materials. The weight is then multiplied by 

2 to convert to a flow rate in pounds per minute. 

A-4-6 

3*f 
P.48 

Section No.: 

Revision: 0 

Date: 

Page: 

4.0 

April 28,1995 

A-4-7 of 9 

4.10 Operating Parameters for Parts 

The operating parameters for parts include catalyst ratio, gelcoat/laminate 

thickness, and glass/resin ratio. These parameters will be measured and documented 

in the report. 

4.10.1 Catalyst Ratio 

The actual catalyst ratio will follow the catalyst ratio suggested by the gelcoat 

and resin manufacturers. 

4.10.2 Gelcoat/Resin Thickness 

In the gelcoating and spray-up laminating tests, the operator will use a gelcoat 

and chop mil gauge during the application to determine the thickness. The operator will 

check and build the thickness of the gelcoat or laminate at various locations on the 

mold surface to the specified thickness. The wet gelcoat thickness is expected to be 18 

to 24 mils and is to be achieved by multiple passes of spraying. The spray-up laminate 

thickness is expected to be 80 to 100 mils and is to be achieved by two passes of 40- to 

50-mil thick laminate. Each pass of the spray-up laminate is equivalent to 1.5 oz/ft2 of 

glass. 

In the flow coating and pressure-fed rolling laminate tests, the primary thickness 

control will be the thickness of the chopped strand mat reinforcement. Two ply of 1.5-

oz/ft2 mat will be used to build the.laminate so that the thickness of the laminates 

fabricated by the flow coater and pressure-fed roller will be similar to that of the ' 

laminates fabricated by spraying equipment. 

4.10.3 Glass/Resin Ratio 

The glass/resin ratio will be determined from the weights of glass roving or 

chopped strand mat and the amount of resin used to build the laminate. The 

glass/resin ratio will be documented for resin laminate only. 

The data recording sheet for the measurements described in Section 4.0 is as 

follows: 

A-4-7 

35 
P.49 

Section No.: 4.0 

Revision: 0 

Date: April 28,1995 

Page: A-4-8of9 

Table 4-3. Data Recording Sheet for the Pollution Prevention Technique Evaluation 

Test 

Date/Time span: 

Test run No.: 

Formulation type (gelcoat/resin): 

Equipment type: 

Recorded by: 

1. Temporary Total Enclosure System 

a. Air flow velocities at natural draft openings (fprii) 

b. Air flow velocity over application area (fpm) 

2. Air Temperature, Exhaust Air Flow Rate, and Relative Humidity 

a. Ambient air temperature (°F) 

0' 15'(min) 30' 45' 60' 

75'. 90' 105' 120' . 135' 

b. Velocity head (Ap) on the pitot tube (inches) 

0' 15' 30' 45' 60' 

75' 90' 105' 120* 135' 

c. Exhaust air flow rate (cfm) 

d. Relative humidity (%) 

3. Emission Measurement 

a. Readings of THC analyzer calibration check 

Range 1 Low Med High 

Range 2 Low Med High 

Range 3 Low Med High 

b. Reading of zero gas before the test run 

c. Reading of zero gas after the test run 

d. Zero and span potentiometer setting before calibration 

e. Zero and span potentiometer setting after calibration 

4. Mass Balance Calculation 

Readings of balance accuracy check with standard weights 

1g 5g 10g 50g 100g 

200g 500g 1,000g 

a. Weight of empty mold, g 

b. Weight of empty ground cover, skirt for cart, gloves, and tapes, g 

(cont.) 

A-4-8 

> 
P.50 

Section No.: 

Revision: 0 

Date: 

Page: 

4.0 

April 28,1995 

A-4-9 of 9 

Table 4-3. Data Recording Sheet for the Pollution Prevention Technique Evaluation 

Test (continued) 

c. Initial weight of gelcoat/resin used, g (container No: ) 

Initial reading, g Final reading, g 

d. Weight of catalyst used, g 

Initial reading, g Final reading, g 

e. Weight of fiberglass reinforcement used, g 

Initial reading, g Final reading, g 

f. Weight of wet mold at the end of application, g 

g. Weight of mold with cured part, g 

h. Weight of ground cover, skirt for cart, gloves, and tapes with cured 

overspray, g 

5. Open Contact Molding Processes 

a. Type of spray gun 

b. Spray gun brand name/model No. 

c. Pump brand name/model No. 

d. Pump ratio 

e. Air supply pressure, psi 

f. Pressure at pump assembly, psi 

g. Spray tip number/size 

h. Catalyst ratio setting 

I. Delivery rate, gpm 

j . Gelcoat/laminate thickness, mil . 

top front . left right back 

k. Glass/resin ratio, % 

A-4-9 

39 
P.51 

Section No.: 

Revision: 0 

Date: 

Page: 

5.0 

April 28, 1995 

A-5-1 of 2 

5.0 ANALYTICAL PROCEDURES 

This section describes the analytical procedures that will be used to analyze the 

gelcoat and resin materials tested. Gelcoat and resin properties include types of 

materials, styrene contents, and curing characteristics of the materials. Laboratory 

procedures commonly used by the industry will be followed to measure these 

properties. The other measurements, such as emission and environmental 

measurements, are described in Section 4 in conjunction with sampling procedures. 

5.1 Types of Gelcoat and Resin Materials 

The types of gelcoat and resin materials to be examined are listed in Section 1.4. 

5.2 Styrene Content 

Styrene content for each of the gelcoat and resin materials will be measured 

using Reichhold Standard Test Method No. 18-001 {Appendix A) in the Reichhold 

laboratory. The gelcoat and resin manufacturers will be asked to provide materials that 

contain only styrene as the monomer. The Reichhold test method determines the 

nonvolatile content of the materials, and the remainder is considered the styrene 

content. The styrene content of the water-emulsified resin will be determined for the 

base resin material before water is added. 

5.3 Gel time, Time to Peak, and Peak Exotherm Characteristics of Polyester 

Resins 

The gel time, time to peak, and peak exotherm characteristics of polyester resins 

will be measured following the Reichhold Standard Test Method No. 18-050 (in 

Appendix A) for gelcoats and resins catalyzed with MEKP. The Reichhold. Standard 

Test Method No. 18-051 (in Appendix A) will be used for the resin catalyzed with BPO. 

The catalyst ratio suggested by the gelcoat and resin manufacturers will be used in the 

curing characteristics determination and in the actual testing. 

The data recording sheet for the measurements described in Section 5.0 is 

presented on the next page. 

A-5-1 

32 
P.52 

Section No.: 

Revision: 0 

Date: 

Page: 

5.0 

April 28,1995 

A-5-2 of 2 

Table 5-1. Data Recording Sheet for Gelcoat and Resin Properties 

Date/Time: 

Test run No.: 

Formulation type:(gelcoat/resin) 

Container No.: 

Recorded by: 

a. Gelcoat/Resin type 

b. Manufacturer, Lot/Batch No. 

c. Styrene content (%) 

d. Weight percent of water (water-emulsified resin only) 

e. Catalyst type 

f. Catalyst ratio (wt. %) 

g. Geltime (minute/second) 

h. Time to peak (minute/second) 

I. Peak exotherm (°F) 

A-5-2 
P.53 

Section No.: 

Revision: 0 

Date: 

Page: 

6.0 

April 28, 1995 

A-6-1 Of 4 

6.0 DATA REDUCTION, VALIDATION, AND REPORTING 

This section describes how data will be reduced, validated, and reported. The 

data handling, reduction, validation, and reporting procedures are shown in Figure 6-1. 

6.1 Data Reduction 

After daily sampling is completed, the recording sheets containing sampling and 

analytical results will be collected, verified, and analyzed by the Testing Crew Chief. If 

THC analyzer readings are not available on a recorder, they will be entered into a 

computer spreadsheet. The styrene concentrations will be calculated from the THC 

analyzer readings and the styrene standard calibration curve for each corresponding 

concentration range used. An average styrene emission concentration will be 

calculated for the duration of the test run. 

An average exhaust air flow rate will be calculated from the average velocity 

head monitored during the test run using the equations in EPA Method 2. Styrene 

emission quantity (Em) for each test run will be calculated by the following equation: 

Em, Ib = 2.6x109 x Q x MW x C x T 

Em, g = 1.18x10"6 x Q x MW x C x T 

where 

2.6x10'9, 1.18x10'6 = conversion factors to standard conditions (68 °F.and 29.92 

inches mercury) in English and metric units, respectively 

Q = average exhaust air flow rate (dry standard cubic feet per minute) 

MW = molecular weight of styrene (104) 

C = average styrene emission concentration (ppmv dry) 

T = duration of test run (minute). 

The weight loss due to emissions (Wloss) and the transfer efficiency (TReff) will 

be calculated by the following equations for each test run: 

Wloss, g = (Wa+Wb+Wc+Wd+We) - (Wg+Wh) 

TReff, % = (Wf-Wa) / (Wc+Wd+We) x 100% 

where 

Wa = Weight of empty mold (g) 

Wb = Weight of empty ground cover, skirt for the cart, gloves, tapes (g) 

A-6-1 

HO 
P.54 

Section No.: 

Revision: 

Date: 

Page: 

6.0 

0 

April 28, 1995 

6-2 of 4 

Testing Crew Chief collects 

data recording sheets from 

testing crew members and 

verifies raw data 

I 

Testing Crew Chief 

performs data reduction 

I 

Project Leader reviews 

raw and reduced data 

for correctness 

I 

Project Leader and Testing 

Crew Chief validate emission 

measurement and weight 

loss data for each test run 

if A > 30% 

If DQI for test 

completeness is not met. 

The test team repeats 

the flagged test run. 

Flag the test run. Project Leader 

and Testing Crew Chief identify 

and resolve the problem. 

if A < 30% 

Forward the reduced 

data to statistician 

for analysis 

I 

If DQI for test 

completeness is met. 

Project Leader and Testing 

Crew Chief summarize and 

interpret the data and prepare 

a final report which also includes 

a QA/QC evaluation section 

Note: A is the difference between the emission measurement and weight loss results for each test run. 

Figure 6-1. The data handling, reduction, validation, and reporting procedures. 

A-6-2 

H.v 
P.55 

Section No.: 6.0 

Revision: 0 

Date: April 28, 1995 

Page: A-6-3 of 4 

Wc = Weight of gelcoat/resin used (g) 

Wd = Weight of catalyst used (g) 

We = Weight of fiberglass reinforcement used (g) 

Wf = Weight of wet mold at the end of application (without the skirt on the 

cart)(g) 

Wg = Weight of cured part with mold (g) 

Wh = Weight of ground cover, skirt for the cart, gloves, and tapes with 

cured overspray (g). 

The emission quantity and weight loss data will be expressed as emission factor 

(Ef) in percent available styrene according to the following formula. 

Ef, %AS = (Em or Wloss, g) / (Wc, g x styrene content) x 100% 

where styrene content is the weight fraction of styrene in the gelcoat or resin 

formulation. 

The same emission quantity and weight loss data can also be expressed as 

emissions per unit mold area (Ea) in gram per square meter according to the following 

formula: 

Ea, g/m2 = (Em or Wloss, g) / (surface area of the mold, m2). 

The field data will be reduced by the Testing Crew Chief as they are generated. 

At the end of the pilot experiment, these field data and reduced data will be analyzed to 

establish "standard" conditions under which the main experiment will be conducted. 

The standard conditions will be selected that best represent the actual operating 

conditions in the industry. 

At the end of the main experiment, the field data and reduced data will be 

reviewed by the Project Leader for correctness. The reduced data are then passed to 

an RTI statistician for the analysis of variance as outlined in Section 1.7. The reduced 

data and the results of the statistical anaiysis will be included in the final report. 

6.2 Data Validation 

A key element in assessing data quality and validity is the comparison of 

emission measurement and the weight loss data for the pure styrene emissions test 

(described in Section 4.1) and for each test run. The Testing Crew Chief will perform 

the basic review and audit of the field data sheet for completeness and accuracy. The 

Testing Crew Chief will also compare the reduced emission measurement with the 

weight loss data to ensure that these two results are comparable within ± 30 percent. If 

these two results are not within ± 30 percent, the test run will be flagged. The test team 

will investigate the possible cause of the difference and correct the problem 

A-6-3 
P.56 

Section No.: 

Revision: 0 

Date: 

Page: 

6.0 

April 28, 1995 

A-6-4 of 4 

immediately. At the end of the main experiment, if the data quality indicator for 

completeness is not met for emission measurement and weight loss determination, 

then these flagged test runs will be repeated. 

6.3 Data Reporting 

An RTI statistician will analyze reduced data and prepare the results of the 

statistical analysis. The Project Leader and the Test Crew Chief will be responsible for 

data summary, interpretation, and final report preparation. The report will present the 

effects of air flow velocity, spraying methods, gelcoat formulations, gelcoat application 

equipment, resin formulations, and resin application equipment on styrene emissions. 

The emissions from different formulations or equipment will be compared with the 

emissions from the baseline conditions. The ability to differentiate any emission 

reduction potential will be determined by the variability of the measurement method and 

the actual difference between the two compared conditions. The final report will also 

contain a Quality Assurance/Quality Control (QA/QC) evaluation report to document the 

QA/QC activities and results. The final report will include a statement indicating 

whether the data quality objectives were met or not. If the QA objectives were not met, 

an explanation of the impact of not meeting the project's QA objectives will be included. 

A-6-4 

Ab 
P.57 

Section No.: 

Revision: 0 

Date: 

Page: 

7.0 

April 28.1995 

A-7-1 of 1 

7.0 INTERNAL PERFORMANCE AND SYSTEM AUDITS 

7.1 Technical Systems Audits 

A technical systems audit (TSA) is a qualitative on-site evaluation. A TSA 

evaluates compliance with the QAPP and any standard operating procedures (SOPs). 

One internal TSA is planned for this project. The TSA will be conducted by the project 

QA Manager, Ms. Salmons, or her designee and will cover sampling, analysis, and data 

handling steps. A written report will be prepared, summarizing the results of the audit 

and noting any deviations from the QAPP, within one month of completion of the audit. 

In addition, RTI will cooperate fully with any external audits performed by EPA. 

7.2 Performance Evaluation Audits 

A performance evaluation audit (PEA) is a quantitative evaluation of a 

measurement system. No internal performance audits are planned for this project. If 

EPA provides performance evaluation samples, RTI will analyze them. 

7.3 Audits of Data Quality 

Audits of data quality (ADQs) involve assessments of the methods used to 

collect, interpret, and report the information required to characterize data quality. While 

no formal ADQ is planned for the project, the project QA Manager or her designee will 

review the data at the end of the project, before the report is finalized. This review will 

check that reduction and validation, as described in Section 6, have been performed, 

and that data can be tracked from data forms and notebooks to the summary tables in 

the report. 

A-7-1 

^ 
P.58 

Section No.: 

Revision: 0 

Date: 

Page: 

8.0 

April 28, 1995 

A-8-1 of 2 

8.0 CALCULATION OF DATA QUALITY INDICATORS 

The exhaust air flow rate, the THC analyzer readings, and weight loss data are 

measured and recorded at the test site. These field data are immediately available for 

data quality review. The field data will be reduced during the testing to the extent 

possible to provide a means of immediately assessing the field data quality. If it is 

found during the testing that accuracy, precision, method detection limit, and 

completeness measurements deviate from the DQI goals indicated in Section 3, the 

source of error will be identified and the problem corrected as soon as possible. A pure 

styrene emission test as described in the capture efficiency test for the total enclosure 

may be used to identify the source of error. 

The following calculations will be used for this study. 

8.1 Precision 

For precision, relative standard deviation will be reported: 

RSD = (s/y)x100% 

where 

RSD = relative standard deviation 

s = standard deviation 

y = mean of replicate analyses. 

Standard deviation is defined as follows: 

s 

N M "-1 

where. 

y; = measured value of the with replicate 

n = number of replicates. 

8.2 Accuracy 

For accuracy, percent recovery will be reported. 

A-8-1 

H * 
P.59 

Section No.: 8.0 

Revision: 0 ' ~ 

Date: April 28,1995 

Page: A-8-2 of 2 

When a standard reference material (SRM) is used: 

%R = 100% x 

Cm 

srm 

where 

%R = percent recovery 

Cm = measured concentration of SRM 

Csm = actual concentration of SRM. 

8.3 Method Detection Limit 

MDL is defined as follows for all measurements: 

M D L

 = '(/>-1.1-a=0.99)*S 

where 

MDL = method detection limit 

s = standard deviation of the replicate analyses 

t(n-i,i-a=o.99) = students' t-value for a one-sided 99% confidence level and a 

standard deviation estimate for n-1 degrees of freedom. 

8.4 Completeness 

Completeness is defined as follows for all measurements: 

%C = 100% x 

where 

%C = percent completeness 

V = number of measurements judged valid 

n = total number of measurements planned 

A-8-2 
P.60 

Section No.: 

Revision: 0 

Date: 

Page: 

9.0 

April 28, 1995 

A-9-1 of 1 

9.0 CORRECTIVE ACTION 

The need for corrective action may be identified through internal performance 

and system audits (described in Section 7); whenever measurement precision, 

accuracy, detection limit, or completeness deviates from the objectives established in 

Section 3; or whenever the comparison of emission measurement and weight loss 

calculation for individual test runs differs by more than 10 percent. 

Corrective action begins with identifying the source of the problem. Potential 

sources of problems include failure to adhere to prescribed test procedures or methods, 

equipment malfunction, or error in data reduction. Pure styrene emission tests 

described in Section 4.1 may be used to identify problems related to the THC analyzer: 

If an instrument calibration check does not meet the specified acceptance criteria, 

recalibration will be required. 

The Testing Crew Chief has the primary responsibility for initiating and 

completing corrective action required to resolve measurement problems encountered 

during the testing. The Project Leader and the Testing Crew Chief will determine 

whether the corrective action has resolved the problem or not and when to resume the 

testing. The Quality Assurance Manager will be notified of all corrective actions 

undertaken at the test site. If necessary, the Project Leader will work with the Quality 

Assurance Manager to resolve major problems such as THC analyzer malfunction and 

to. obtain concurrence from the EPA Project Officer and QA Officer. All corrective 

actions and the nature of problem will be documented in the QA/QC evaluation in the 

final report. 

A-9-1 

yr\ 
P.61 

RESEARCH TRIANGLE INSTITUTE _RTJ 

Center for Environmental Analysis 

MEMORANDUM 

DATE: May 25, 1995 

TO: Carlos Nunez, EPA Project Officer 

FROM: Emery J. Kong ^\^-~ 

SUBJECT: Responses to EPA's Comments on the Category III Quality Assurance Project 

Plan (QAPP) 

RE: Evaluation of Pollution Prevention Techniques to Reduce Styrene Emissions 

from Open Contact Molding Processes 

EPA Cooperative Agreement No. CR 818419-03 

RTI Project No. 96U-5171-016 

Our responses to EPA's comments on the QAPP are presented in the attachment. As 

I have discussed with Dr. Nancy Adams on May 5, RTI will make the following changes to 

the QAPP: (1) RTI will calibrate the THC analyzer with propane standards and establish a 

response factor relationship between the propane and styrene standards, and this relationship 

will be used to determine the styrene concentrations monitored, and (2) RTI will use 

hydrogen gas as the fuel for the Ratfisch THC analyzer (as called for in the instrument 

manual) instead of a hydrogen/nitrogen mixture. 

In addition to the above changes, we will separate the gelcoat experiment from the 

resin experiment because we are able to resolve some technical problems in gelcoat and resin 

application. This change will not affect the validity of measurements for either gelcoat 

experiment or resin experiment because data analysis for each experiment is done separately. 

We will perform the pilot experiment first using the regular gelcoat, then the gelcoat 

experiment, and finally the resin experiment. 

Please fo.rward our responses to Dr. Nancy Adams. If you believe our responses 

have adequately addressed EPA's concerns in the QAPP, please sign and date the attached 

signature page and return it to me as soon as possible. Please call me at 541-5964 

immediately, if you think the responses are not adequate. Thank you very much. 

Attachments 

cc: Cynthia Salmons, RTI 

Mark Bahner, RTI 

.Bob Wright, RTI 

Andy Clayton, RTI 

Jesse B.askir, RTI 

3040 Cornwallis Road • Post Office Box 12194 . Research Triangle Park, North Carolina 27709-2194 USA 

Telephone 919 541-5816 • Fax 919 541-7155 

£ £ A-9-2 VXA 
Attachment 

Section Comment 

1. Table 1-4 TEST RUNS FOR THE RESIN FORMULATIONS AND EQUIPMENT 

TYPES 

How will RE-3 (pressure-fed rollers) and RE-4 (modified AAA) be 

compared when different resin formulations are being used in the testing of 

these two types of equipment? RE-1, RE-2, and RE-3 are all being tested 

with the same resin formulation, but RE-4 testing is proposed using a 

different formulation. A discussion of die way in which the four 

equipment types (REs) will be compared would add to the plan. 

Response: 

The resin catalyzed with benzoyl peroxide (BPO) catalyst requires the 

modification of the air-assisted airless (AAA) spray gun and pump system, 

so it is not possible to test the BPO system using the conventional AAA 

spray gun. This means that it will not be possible within the present test 

design to separate the effects of the BPO catalyst from the effects of the 

modified spray gun. Therefore, the test report will acknowledge tiiat no 

separation of these effects can be made. As noted on page 1-18, any 

comparison of RF-4 with other resin formulations will be confounded with 

the equipment difference. 

2. Table 1-5 SUMMARY OF CRITICAL AND NONCRITICAL MEASUREMENTS 

Reichhold Method No. 18-001 is proposed for the measurement of styrene 

content in the formulations tested. This method (Appendix A) involves 

weight loss with heating bf a small sample on foil. Method 18-001 seems 

to be a measurement of volatiles and not styrene. This matter is discussed 

in Section 5.2; the manufacturers will be asked to "provide materials that 

contain only styrene as the monomer." However, throughout the 

document, styrene measurement is listed as a critical measurement, and 

the proposed method is not measuring styrene. Is tliere any additional data 

that could be supplied to verify that the proposed method really is an 

accurate measure of styrene? 

Response: 

Reichhold Method No. 18-001 is commonly used by the industry to 

determine the non-volatile (NV) content of polyester resins. Section VI of 

1 

A-9-3 
P.63 

the method shows that the % monomer content is calculated using the 

following formula: 

% monomer = 100 - % NV. 

Since the materials used in the testing will contain only styrene monomer, 

we can use the method as an indirect measurement of styrene content. 

3. Section 3.1.2 ACCURACY 

These accuracy goals pertain to calibration error only. What about zero 

and calibration drift (post test checks)? 

There is a minor typo noted in the text. The word is "assembly". 

Response: 

The zero and mid-level calibration drift will be checked according to the 

procedures oudined in Method 25A section 7.2, at the end of each run (but 

not hourly during the run). The acceptable drift will be taken to be ±3 

percent of span value. If the drift exceeds tiie acceptable level, the THC 

response will be checked for all calibration gases within the range(s) used 

in the run. The test results will be reported using both sets of calibration 

data (before and after the run). The THC analyzer will then be 

recalibrated as described in Method 25A section 6.4, prior to the following 

run. 

4. Table 3-2 OBJECTIVES FOR QUPANTITATIVE DATA QUALITY INDICATORS 

The accuracy objectives should be clearly defined. Is % bias from full 

scale or from a known standard? Is the THC detection limit of 1 ppm 

realistic in the 0 - 1, 100 ppm range? How was the detection limit 

derived? Does the equation in Section 8.3 apply for non-discrete 

measurements such as those from CEMs? 

Response: 

RTI now plans to operate the total hydrocarbon analyzer on instrumental 

ranges that correspond to 0 to 20 ppm styrene (C8) and 0 to 200 ppm 

styrene (C8). These ranges are also equivalent to 0 to 53 ppm propane 

(C3) and 0 to 533 ppm propane (C3). The calibration gases will be 16, 

27, 45, 160, 267, and 453 ppm propane. These calibration gases will 

correspond to 30 percent, 50 percent, and 85 percent of the two full-scale 

ranges, as called for in EPA Method 25A. 

A-9-4 

J 
P.64 

The accuracy data quality objective is being changed from +/- 5 percent to 

+/- 3 ppm on the 0 to 53 ppm propane range and to +/- 31 ppm on the 0 

to 533 ppm propane range. The values are the root-sum-squares of the 

calibration gas accuracy, the calibration error, and the calibration drift. 

The following example is for the 0 to 53 ppm propane range: 

calibration gas accuracy = 5 % of 45 ppm =2.25 ppm 

calibration error = 5 % of 27 ppm =1.35 ppm 

calibration drift = 3 % of 53 ppm = 1.59 ppm 

root-sum-square = 3.07 ppm 

Please note that each of these accuracy components is measurable. The 

calibration gas accuracy will be detennined by comparing the specialty gas 

producer's certified value with RTI's verification value for the high-level 

calibration gases. The calibration error and calibration drift will be 

measured according to the procedures outlined in Method 25A section 7.2, 

at the end of each run. 

The THC detection limit of 1 ppm (as styrene) is quite realistic for the 0-

200 ppm (as styrene) range. As shown in the attached figure, the zero gas 

analysis in a March 1995 testing at Dow (using the same THC analyzer) 

showed that a detection limit of less than 1 ppm was achieved in a 0-350 

ppm (as styrene) range. The equation in Section 8.3 can be used if THC 

readings are taken at fixed intervals (such as every 15 seconds). 

5. Section 4.4 .EMISSION MEASUREMENT 

How many points will go into, the calibration? Based on the gases 

discussed in the QAPP, only the 1,100 ppm scale can be calibrated per 

Method 25A. What is the sample line made of? Is it heated? Are the 

other components of the sample delivery system heated? Are any system 

bias checks planned? Styrene is very reactive. What will be done to 

evaluate the bias of the sample delivery system? Where will the probe be 

located in the stack? Will an emissions profile be performed to assess 

stratification in the duct? A probe can be built to sample representatively 

across the duct (see 40 CFR Van 86.310-79). 

Response: 

In accordance with EPA Method 25, each of the two concentration ranges 

used in the total hydrocarbon analyzer will be calibrated with zero gas and 

low-level, mid-level, and high-level calibration gases. The concentrations 

of these calibration gases are shown in the response to Comment No. 4. 

A-9-5 

SV 
P.65 

RTI anticipates using PFA Teflon for the sample line. The sampling 

location will be 5 or 6 stack diameters downstream of the last bend. The 

sample line will be capped at its end and a number of holes will be drilled 

along its in-stack length to obtain a sample stream that is representative of 

the entire stack. In general, RTI will follow the specifications for the 

sample probe given in 40 CFR, Part 86.310.79 (b) except for the use of 

PFA Teflon rather than stainless steel. 

Method 25 states that the sample line should be heated, if necessary, to 

prevent condensation in the line. The total hydrocarbon analyzer will be 

sampling essentially room air at room.temperature. As such, there is no 

need to heat the sample line to prevent condensation. Further, heated 

sample line may cause styrene polymerization within the sample line. 

During a previous gas chromatographic verification study of styrene 

calibration gases, RTI checked for sample line losses using a calibration 

gas containing approximately 5 ppm styrene. No differences among 

unheated stainless steel, heated stainless steel, and unheated Teflon sample 

lines were found. Any sample line losses would likely be less at the much 

higher flow rate associated with the total hydrocarbon analyzer. 

The bias of the sample delivery system will be tested, before tiie actual 

testing, by comparing the instrumental responses to the styrene and 

propane calibration gases when they are delivered through the analyzer's 

calibration gas port and through the unheated sample line. If the responses 

for both styrene and propane gases are the same, the sample line will not 

be heated. If the response for styrene gas is different and the response for 

propane gas is the same, then the need for heating the sample line will be 

evaluated. If responses for both styrene and propane gases are different, 

then the THC analyzer will be checked and repaired. A THC analyzer 

rental unit can be arranged if the Ratfisch THC analyzer is not functional. 

In addition to the direct sample delivery system bias test, an indirect 

sample system bias check will be conducted in the preliminary testing using 

pure styrene evaporation. The pure styrene evaporation test will identify 

the bias in exhaust flow rate and THC measurements when the emission 

quantity is compared to the known quantity of styrene evaporated. The 

pure styrene evaporation test will release styrene at a constant rate; 

therefore, it can be used to determine the emissions profile and to assess 

stratification in the exhaust stack. The emission concentrations profile 

could not be performed during an actual test due to the changing styrene 

concentrations. Additionally, the multi-point sample probe described above 

should eliminate bias due to potential stratification. 

A-9-6 

<? 
P.66 

6. Section 4.5 .EXHAUST AIR FLOW MEASUREMENTS 

Is the exhaust flow rate stable enough to only measure flows weekly? Why 

was the center of the duct selected to monitor Ap? Wouldn't the average 

square root of Aps across the duct be more appropriate? Has an Annubar 

been considered to determine total flow with a single Ap? 

Response: 

Prior to the actual testing, several velocity traverse/centerline 

measurements will be made pn different days to determine whether the 

exhaust flow rate changes over time and whether the centerline Ap 

measurements accurately correlate with velocity traverse measurements. If 

the preliminary exhaust flow rate measurements indicate that centerline Ap 

measurements do no correlate to within ± 5 percent of the exhaust flow 

rate as determined by traverse measurements, an Annubar probe will be 

used for Ap monitoring in the actual testing. 

If the exhaust flow rate is relatively stable over time, a velocity traverse 

will be performed at the beginning of each week to determine the exhaust 

flow rate, and the Ap (either at centerline or by Annubar) will be 

monitored every 15 minutes during the test run. The exhaust flow rate 

during the test run will be calculated according to the following formula: 

Q run = [avg (Ap run)°-5/(Ap weekly)0,5] x Q weekly 

where 

Q run = exhaust flow rate during a test run (scfm) 

Q weekly = exhaust flow rate determined by the weekly velocity traverse 

(scfm) 

avg (Ap run)0-

3

 = average square root of the 15-minute Aps recorded 

during the test run, either at the centerline or by Annubar 

(Ap weekly)0-

3

 = square root of the Aps recorded during the weekly 

velocity traverse 

7. Section 4.7 GELCOAT AND RKIN PROPERTTES 

Is the hand-held mixer electric? If so, please be sure the motor is 

explosion proof since the flash point of styrene is 31°C. 

Response: 

The hand-held mixer will be powered by compressed air. 

5 

A-9-7 
P.67 

8. Section 8.3 METHOD DETECTION LIMIT 

Does the definition of s mean the (estimated) standard deviation of a single 

observation, or the average of the nl Presumably the "MDL" refers to a 

single observation but is based on a variance estimated from multiple 

observations. 

Response: 

The method detection limit will be calculated using the equation shown 

with s being determined from n measurements of zero gas taken at 15-

second intervals. RTI anticipates that n will equal 20. 

9. GENERAL COMMENTS FROM ROSS LEADBETTER 

Response: 

The entries in Table 1-1 are approximated half widths. 

The QAPP was arranged according to the format given in the QA manual; 

therefore, some of the texts may be disconnected to the reader. 

Nevertheless, the reader should be able to find the essential information by 

referring to the table of contents. 

A-9-8 

^ 
Sc\ri\o\:*\^ Arnb'.v*^ *•> 

Zero gas addition during 030795AC 

2.5 

2 

.5 

'•*•, • 

E 

o. 3. 

c o 

e 

o 

c 

o 

o 

0.5 

0 ) 0 

-0.5 

0.50 

^u/iicrl&L -ft> ^w> 4a> ^?y- banzUnx^ (JUUVM:nu-hjr^-

T 

• • • 

1.00 1.50 2.00 2.5ft" 3.00 

-1 

Elapsed time (minutes) 

030795AC.XLC 

0) 

00 
P.69 

Appendix B 

Reichhold Standard Test Methods 

B-i 
P.70 

Reichhold Standard Test Methods 

Test Method Page 

18-001. Detennination of non-volatile content of polyester resins B-1 

18-021. Determination of Brookfield viscosity and thixotropic index of polyester 

resins ; B-4 

18-050. Detennination of room temperature gel, time to peak and peak exotherm 

characteristics of polyester resins B-9 

18-152. Determination of static styrene emissions for compliance with SCAQMD 

Rule 1162 B-12 

B-ii 
REICHHOLD R.EACTIVE 

POLYMERS 

DIVISION 

P.71 

TEST PROCEDURE 

DETERMINATION OF NON-VOLATILE CONTENT 

OF POLYESTER RESINS 

METHOD 

ISSUED 

REVISED 

PAGE: 

18-001 

11/17/87 

02/27/89 

1 OF 3 

I. SCOPE 

This method describes a procedure for the rapid determination of the 

non-volatile content of polyester resin solutions. 

II. SAFETY 

Safety glasses are recommended for this procedure. 

III. EQUIPMENT 

1. Aluminum foil - 6" x 12", Thomas Scientific 1086-F27-F32 or 

equivalent. (Reynolds Wrap Heavy Duty) 

2. Paper clips, #1 gem clipsor equivalent. 

3. Cardboard sheet - 8" x 12" x 0.025". 

4. Analytical balance, capable of accurately weighing to +/- 0.0001 

grams. 

5. Disposable syringe, 3cc capacity, B-D #5586 or equivalent. 

6. Oven, forced air, of suitable capacity maintained at 120 +/- 2°C. 

7. Thermometer, (1.0°C divisions). 

8. Clean glass plates (2) approximately 8" x 8" x 1/4". 

9. Stopwatch or timer capable of measuring to one second intervals. 

The intormation herein is to assist customers in determining whether our products are suitable tor their applications. Our products are intended tor 

sale to industrial and commercial customers. Wa request that customers inspect and test our products before use and satisfy themselves as to contents 

and suitability. We warrant that our products will meet our written specifications. Nothing herein shall constitute any other warranty express or implied, 

including any warranty of merchantability or fitness, nor is protection from any law or patent to be inferred. AD patent rights are reserved. The exclusive 

remedy for all proven claims is replacement of our materials and in no event shal we be liable tor special, incidental or consequential damages. 

REICHHOLD CHEMICALS, INC. • REACTIVE POLYMERS DIVISION • JACKSONVILLE, FL 32245 • (904)739-2170 

B-1 5 
P.72 

METHOO: 18-001 

ISSUED: 11/17/87 

REVISED: 02/27/89 

PAGE: 2 OF 3 

IV. PROCEDURE 

1. Fill disposable syringe with polyester resin solution to be tested, 

cleaning away all excess resin from the exterior of the syringe and 

removing all excess air from the interior. Immediately replace 

syringe cap to insure minimal monomer loss due to evaporation. 

2. Fold a 6" x 12" aluminum foil sheet in half, shiny surface facing 

in, and measure its dry weight (without resin) to the nearest 0.0001 

gm. Record this weight as "A". 

3. Unfold the aluminum foil sheet and rest it shiny side up on one of 

the 8" x 8" x 1/4" glass plates. Place approximately 0.5 grams 

(0.5cc) of polyester resin solution in the center of either of the 

6" x 6" halves of the aluminum foil sheet. Replace the syringe cap. 

4. Carefully fold foil sheet halves together and gently place second 

glass plate oyer the folded foil sheet. Press carefully to ensure 

even distribution of the resin sample into a thin film without 

exuding from the edges of the aluminum foil. 

5. Quickly reweigh the aluminum foil containing the resin sample, to 

the nearest 0.0001 gram. Record this weight as "B". 

6. Unfold the foil sheet and place (resin side up) onto the cardboard 

sheet. Use the paper clips to carefully secure the foil to opposite 

corners of the cardboard. 

NOTE: Use care not to tear the aluminum foil sheet or allow the 

paper clips to come in contact with the resin. 

7. Place entire apparatus in 120 +/- 2°C oven, begin timer, and leave 

in oven for 10 minutes. 

8. Repeat steps two (2) through seven (7) for duplicate sample. 

9. After 10 minutes, remove the sample apparatus from the oven. 

Carefully remove the aluminum foil from the cardboard surface and 

fold several times to avoid the loss of dried resin sample. This 

will also help to minimize added moisture from condensation. 

Quickly reweigh the aluminum foil to the nearest 0.0001 gram. 

Record this weight as "C". 

B-2 

*A 
METHOD: 18-001 

ISSUED: 11/17/87 

REVISED: 02/27/89 

PAGE: 3 OF 3 

V. CALCULATIONS 

Percent non-volatile can then be calculated using the following formula: 

% NV =• Weight of Resin Solids X 100 

Weight of Resin Solution 

Where: Weight of resin solids = C - A 

Weight of resin solution = B - A 

Duplicate samples should agree to within +/- 0.5%. If duplicate samples 

are not within +/- 0.5%, rerun the entire test. 

NOTE: Occasionally, high boiling monomers are used in manufacturing 

polyester resins. Some may not evaporate as quickly as styrene. If 

samples don't agree on the second run, this may be the cause. 

VI. REPORT 

The percent non-volatile is reported as an average of the duplicate 

samples. Round the value to the nearest 0.1%. Once the % NV is known, % 

Monomer Content may be calculated using the following formula: 

% Monomer = 100 - %NV 

Author: 

Approved by: 

B-3 
REICHHOLD REACTIVE 

POLYMERS 

DIVISION 

P.74 

TEST PROCEDURE 

DETERMINATION OF BROOKFIELD VISCOSITY 

AND THIXOTROPIC INDEX OF POLYESTER RESINS 

METHOD: 18-021 

ISSUED: 02/17/84 

REVISED: 02/27/89 

PAGE 1 OF 5 

I. SCOPE 

This method describes a procedure for determining the Brookfield 

viscosity and/or thixotropy of polyester resins. 

II. SAFETY 

Safety glasses and protective gloves are recommended for this 

procedure. 

III. EQUIPMENT 

1. Brookfield Viscometer, Model LVF, (6,12,30 and 60 RPM) with 

spindles #1.through #4 and without guard. 

2. Brookfield Viscometer, Model RVF (2,4,10 and 20 RPM) with 

spindles #1 through #7 and without guard. 

3. Brookfield Viscometer, Model RVT (0.5,1,2.5,5,10,50 and 100 RPM) 

with spindles #1 through #7 and without guard. 

4. Brookfield Laboratory Stand. Model A. 

5. Circulating water bath controlled at 25°C +/- 0.2°C. 

6. Thermometer, ASTM-17C (19-27°C)< 

7. Stopwatch or timer capable of measuring to one second intervals. 

8. Quart can and lid. 

9. Brookfield factor finder or note page _5_ of 5 . 

The information herein is to assist customers in determining whether our products are suitable for their applications. Our products are intended tor 

sale to industrial and commercial customers. We request that customers inspect and test our products before use and satisfy themselves as to contents 

and suitability. We warrant that our products win meet our written specifications. Nothing herein shad constitute any other warranty express or implied, 

including any warranty of merchantability or fitness, nor is protection from any law or patent to be inferred. AD patent rights are reserved. The exclusive 

remedy for all proven claims is replacement of our materials and in no event shall we be liable for special, incidental or consequential damages. 

REICHHOLD CHEMICALS, INC. • REACTIVE POLYMERS DIVISION • JACKSONVILLE, FL 32245 • (904)739-2170 

B-4 ^V 
P.75 

METHOD: 18-021 

ISSUED: 02/17/84 

REVISED: 02/27/89 

PAGE 2 OF 5 

10. Laboratory monitored at 25+/-l°C or 77+/-2°F. 

IV. CALIBRATION 

1. Brookfield 500 cps and 2500 cps oil standards are to be used. Each 

viscometer calibration should be checked once per month using the . 

Brookfield Standardized oils. Select a spindle and RPM that will 

give a reading in the mid range of the viscometer scale; 40-60 on 

the dial. 

2. Mount the viscometer in air and level it. Deflect the needle 

lightly from its zero position and let it swing back under its own 

power. If the needle swings freely and returns to zero it is 

acceptable. 

V. PROCEDURE (N0N-THIX0TR0PIC RESINS) 

1. Pour approximately 800 ml of resin sample into a quart can and 

adjust to 25 +/- 0.2°C using a thermometer (avoid air entrapment). 

2. Place the resin sample into the constant temperature water bath at 

25 +/- 0.2°C. Allow sufficient time for the sample to deaerate 

completely since air bubbles will affect viscosity readings. 

3. Select the appropriate viscometer, spindle and spindle speed 

according to the Master Formula. If unspecified, select spindle and 

speed which will give a reading in the mid range of viscometer dial. 

4. Remove the lid and place the resin sample under the leveled 

viscometer. Lower the viscometer to a point where the spindle 

coupling is approximately two (2) inches from the resin surface. 

Insert the clean, dry spindle into the sample at an angle to avoid 

air entrapment under the spindle. Lift up on the spindle coupling 

and attach the spindle. (NOTE: left-hand thread). Avoid putting 

side or down thrust on the shaft when attaching spindle. 

5. Center the spindle, then raise or lower the viscometer housing until 

the upper surface of the sample is in the middle of the spindle 

shaft indentation. 

B-5 

U ^ 
P.76 

METHOD: 18-021 

ISSUED: 02/17/84 

REVISED: 02/27/89 

PAGE 3 OF 5 

6. After selecting the desired viscometer RPM, turn on viscometer motor 

and simultaneously start the stopwatch. 

7. After one (1) minute has elapsed, depress the viscometer clutch, 

stop the motor and take a dial reading. 

Va. CALCULATION 

1. Multiply the dial reading bv the factor obtained from the factor 

finder (see page _5__ of 5 ) to obtain a centipoise value. Report 

results in centipoises (CPS) showing temperature, Brookfield Model, 

spindle number and RPM. 

VI. PROCEDURE (THIXOTROPIC RESINS) 

1. Pour approximately 800 ml of resin sample into a quart can and 

adjust to 25 +/- 0.2°C using a thermometer (avoid air entrapment). 

2. Place the resin sample into the constant temperature water bath at 

25 +/- 0.2°C, undisturbed for exactly fifteen (15) minutes prior to 

viscosity determination. 

3. Select the appropriate viscometer, spindle and spindle speed. 

Unless specified, all thixotropic resins will be evaluated using the 

Brookfield Model LVF viscometer, #3 spindle at 6 RPM and 60 RPM. 

4. Follow steps (4) and (5) for non-thixotropic resins. Handle the 

sample with care to minimize disturbance of the resin. 

5. Set the speed to 6 rpm, then start the viscometer simultaneously 

with the timer. After 60 seconds, increase the speed to 60 rpm. 

After three (3) minutes depress the viscometer clutch and take a 

reading. Reduce the speed to 6 RPM and start the viscometer again. 

Take a final reading at third (3) minutes. 

Via. CALCULATIONS 

Multiply the dial reading taken at each speed by the respective factor 

obtained from the factor finder (see Page _5_ of 5 ) to obtain 

centipoise values. Report results in centipoises (CPS) showing 

temperature, Brookfield Model, spindle number and RPM. (NOTE: In most 

cases the viscosity is reported using the higher RPM value). 

B-6 

IA 
P.77 

METHOD: 18-021 

ISSUED: 2/17/84 

REVISED: 11/4/88 

PAGE 4 OF 5 

VII. THIXOTROPIC INDEX 

CALCULATIONS 

Divide the viscosity obtained at the slower spindle speed by the 

viscosity obtained at the higher spindle speed to obtain the 

thixotropic index. Thixotropic index has no units of measure and is 

reported to the nearest 0.1. 

T j = Viscosity @ 6rpm 

Viscosity @ 60rpm 

Author: 

Approved by: 

B-7 

LH 
BROOKFIELD FACTOR FINDER METHOD: 18-021 

ISSUED: 2/17/84 

REVISED: 2/27/89 

PAGE 5 OF 5 

w 

00 

frViscometer 

Model 

Spindle 

Number 

Speed 

RPM 

.5 

1 

2 

2.5 

4 

5 

10 

20 

50 

100 

RV 

1 

200 

100 

50 

40 

25 

20 

10 

5 

2 

1 

RV 

2 

800 

400 

200 

160 

100 

80 

40 

20 

8 

4 

RV 

3 

2M 

IM 

500 

400 

250 

200 

100 

50 

20 

10 

RV 

4 

4M 

2M 

IM 

800 

500 

400 

200 

100 

40 

20 

RV 

5 

8M 

4M 

2M 

1.6M 

IM 

800 

400 

200 

80 

40 

RV 

6 

20M 

10M 

5M 

4M 

26M 

2M 

IM 

500 

200 

100 

W 

7 

80M 

40M 

20M 

16M 

10M 

8M 

4M 

2M 

800 

400 

Speed 

RPM 

LV LV LV LV 

.3 

.6 

.5 

3 

6 

12 

30 

60 

200 

100 

40 

20 

10 

5 

2 

1 

• • 

IM 

500 

200 

100 

50 

25 

10 

5 

Factor 

4M 

2M 

800 

400 

200 

100 

40 

20 

20M 

10M 

4M 

2M 

IM 

500 

200 

100 

Factor 

To convert viscometer dial reading to centipoise, locate the column which identifies the viscometer 

model and spindle number used. Locate viscometer speed, RPM's. The number found at the intersection 

'of viscometer, spindle and speed is the factor. Multiply viscometer dial reading by the factor to 

determine viscosity in centipoise. M-1000 

oo 
P.79 

REICHHOLD REACTIVE 

POLYMERS 

DIVISION 

7IES7 PROCEDURE 

DETERMINATION OF ROOM TEMPERATURE GEL, METHOD: 18-050 

TIME TO PEAK AND PEAK EXOTHERM CHARACTERISTICS ISSUED: 2/17/84 

OF POLYESTER RESINS REVISED: 2/27/89 

PAGE 1 OF 3 

SCOPE 

This method describes a procedure for determining the gel, total-time to 

peak and peak exotherm of promoted or unpromoted resins when catalyzed 

with methyl ethyl ketone peroxide. 

II. SAFETY 

Safety glasses and protective gloves are recommended for this procedure. 

Use care when handling methyl ethyl ketone peroxide. Read and thoroughly 

understand the Material Safety Data Sheet provided with this material 

before its use. 

III. EQUIPMENT 

1. Temperature recorder with 0. to 500°F range. Type J thermocouple 

interface. Capable of speeds of 30"/nour and 60"/hour. 

2. Type J thermocouple, iron-constantan, 6" sheathed in stainless 

steel. 

3. Constant temperature water bath maintained at 25 +/- 0.2°C with 

suitable rack. 

4. Laboratory balance, 400 gm minimum capacity, capable of weighing to 

0.01 grams. 

5. ASTM-17C thermometer, (19-27°C). 

6. 6" wooden handle stainless steel spatula or wooden tongue depressor 

(6" X 3/4"). 

The intormation herein is to assist customers in determining whether our products are suitable tor their applications. Our products are intended tor 

sale to industrial and commercial customers. We request that customers inspect and test our products before use and satisfy themselves as to contents 

and suitability. We warrant that our products will meet our written specifications. Nothing herein shall constitute any other warranty express or implied, 

including any warranty of merchantability or fitness, nor is protection from any law or patent to be inferred. All patent rights are reserved. The exclusive 

remedy tor aD proven claims is replacement of our materials and in no event shall we be liable tor special, incidental or consequential damages. 

REICHHOLD CHEMICALS, INC. • REACTIVE POLYMERS DIVISION • JACKSONVILLE, FL 32245 • (904)739-2170 

B-9 U 
P.80 

METHOD: 18-050 

ISSUED: 2/17/84 

REVISED: 2/27/89 

PAGE: 2 of 3 

7. Disposable 150 ml polypropylene beaker (VWR Scientific Cat. no. 

13915-544 or equivalent). 

8. Stopwatch or timer capable of measuring to one second intervals. 

9. Laboratory - maintained @ 25 +/- 1°C or 77 +/- 2°F. 

10. Repipet dispenser. 5 ml capacity with 0.05 ml graduations (Fisher 

Scientific-Cat. no. 13-687-54 or equivalent) or Tuberculin Syringe, 

1.0 CC capacity with 1/100 graduations (Fisher Scientific-Cat. no 

14-820-15 or equivalent. 

IV. REAGENTS 

1. Methyl Ethyl Ketone Peroxide (Type specified by Master Formula). 

2. 12% (metal) cobalt octoate solution (optional). 

V. PROCEDURE 

1. Weigh 100 +/- 0.1 grams of resin into a 150 ml polypropylene beaker. 

2. Insert metal spatula, wooden tongue depressor, or thermometer into 

beaker. If the wooden tongue depressor is used, it must be coated 

1/2 inch above the resin level with previously weighed resin to 

prevent absorption.of cobalt solution, MEKP or any additional 

additives. 

3. Promote resin if necessary for room temperature cure. Unless 

specifically stated by Master Formula, unpromoted resins are 

promoted with 0.21 grams of 12% cobalt octoate. Any promoter must 

be thoroughly mixed into the resin before proceeding. 

4. Place the beaker containing resin into a constant temperature water 

bath at 25 +/- 0.2°C. Allow sufficient time for the resin sample to 

equilibrate to 25 +/- 0.2°C. If a thermometer is used to facilitate 

resin temperature adjustment it must remain in the sample until 

after the MEKP has been added and thoroughly dispersed. 

5. Add the type and amount of MEKP specifically stated in the Master 

Formula into the sample resin; simultaneously start the stopwatch 

and mix thoroughly for one minute in the water bath. Avoid air 

entrapment while mixing. Allow the stopwatch to run for the entire 

test. 

B-10 

W 
P.81 

METHOD: 18-050 

ISSUED: 2/17/84 

REVISED: 2/27/89 

PAGE: 3 of 3 

6. Check the sample periodically by lifting the spatula or tongue blade 

to. observe the resin flow rate watching for signs of gellation. Do 

not stir the sample when checking it, but simply lift the spatula or 

tongue blade straight up and replace it. The point at which the 

resin ceases to flow and "snaps" off the stick back into the beaker 

is called the gel point and the elapsed time from catalyst addition 

to the gel point is called "gel time". Record the gel time. Oo not 

stop the stopwatch. 

7. Upon reaching the gel time, immediately remove the beaker from the 

water bath, place on a non-heat-conductive surface (i.e., wood) and 

insert the thermoccuple. The tip pf the thermocouple is to be 

located 3/16 inch from the beaker's boc:om and within the center of 

the resin sample surface. 

8. Observe the recorder and stopwatch. Record the time elapsed from 

catalyst addition to the peak temperature. This is called, "Total 

Time to Peak". 

9. The maximum temperature reached is reported as the "Peak Exotherm". 

NOTE: Some customers require an interval time rather than "Total Time to 

Peak". The interval (also called Gel-to-Peak) is the Total Time to Peak 

minus the Gel Time. 

Example: 

GEL TIME: 13' 

TOTAL TIME TO PEAK: 28' 

PEAK EXOTHERM: 325°F 

Here, the interval (or Gel-to-Peak) is: 28' - 13' = 15' 

AUTHOR: 

APPROVED BY: 

B-11 

(oi 
P.82 

REICHHOLD REACTIVE 

POLYMERS 

DIVISION 

TEST PROCEDURE 

DETERMINATION OF STATIC STYRENE EMISSIONS 

FOR COMPLIANCE WITH SCAQMD RULE 1162 

METHOD 

ISSUED 

REVISED 

18-152 

06/07/88 

11/15/88 

PAGE: 1 OF 3 

I. SCOPE 

This method describes the procedure for determining the weight loss of 

styrene from a polyester resin during its gel and cure under static 

conditions. Results are reported in g/m for compliance with Rule 1162's 

limit-of 60 g/m maximum emissions. 

II. SAFETY 

Safety glasses and protective gloves are recommended for this procedure. 

Use care when handling methyl ethyl ketone peroxide. Read and thoroughly 

understand the Material Safety Data Sheet provided with this material 

before its use. 

III. EQUIPMENT 

1. Constant temperature water bath maintained at 25 +/- 0.2 deg C. • 

ASTM-17C Thermometer, (19-27 deg C). 

Laboratory balance, 400 gm minimum capacity, accurate to +/- 0.01 gm. 

Stopwatch or timer capable of one second intervals. 

Disposable 400 m-l polypropylene beaker. 

2. 

3. 

4. 

.5. 

6. 6" wooden handle stainless steel spatula or wooden tongue depressor 

(6" x 3/4"). 

7. Gallon can lid, 14.5 cm diameter, deep form to hold 100 gm resin. 

The intormation herein is to assist customers in determining whether our products are suitable tor their applications. Our products are intended tor 

sale to industrial and commercial customers. We request that customers inspect and test our products betore use and satisfy themselves as to contents 

and suitability. We warrant that our products win meet our written specifications. Nothing herein shall constitute any other warranty express or implied, 

including any warranty of merchantability or fitness, nor is protection from any law or patent to be inferred. All patent rights are reserved. The exclusive 

remedy tor all proven claims is replacement of our materials and in no event shall we be liable for special, incidental or consequential damages. 

REICHHOLD CHEMICALS, INC. REACTIVE POLYMERS DIVISION • JACKSONVILLE, FL 32245 

B-12 ^ 

(904) 739-2170 
P.83 

METHOD: 

ISSUED: 

REVISED: 

PAGE: 2 

18-152 

06/07/88 

11/15/88 

OF 3 

8. Paper clip; bent to 90 deg angle. 

9. Relative Humidity Meter, +/- 3% accuracy. 

10. Repipet dispenser 5 ml capacity with 0.05 ml graduations (Fisher 

Scientific Cat. No. 13-687-54 or equivalent). A Tuberculin syringe, 

1.0 cc capacity with 1/100 graduations (Fisher Scientific Cat. No. 

14-820-15 or equivalent) may also be used. 

IV. REAGENTS 

1. MEKP (Type specified on Master Formula). 

V. PROCEDURE 

1. Place bent paper clip on can lid. 

2. Weigh can lid.to +/- O.Olgm. Record weight. 

3. Record relative humidity and ambient temperature. 

4. Weigh 200 +/- O.lgm of resin into polypropylene beaker. 

5. Adjust temperature of resin to 25 +/- 0.2 deg C. 

6. Insert metal spatula, wooden tongue depressor or thermometer. If the 

wooden tongue is used the depressor much be coated 1/2 inch above the 

resin level with presiously weighed resin to prevent absorption of 

cobalt solution, MEKP or any additional additives. Add the type and 

amount of MEKP specified in the Master Formula, then start the 

stopwatch. Mix thoroughly for one (1) minute. 

7. Place the gallon lid on the balance then tare. Then pour 100 +/-

0.5gm of catalyzed resin into the lid. Record the weight of resin to 

+/- O.Olgm. 

8. Note the gel time of resin remaining in the beaker. Determine the gel 

time of the resin in the can lid by cautiously lifting paper clip. 

Record gel time of resin in the can lid. Avoid excessive movement of 

the paper clip as this will interfere with the results. 

B-13 

15 
P.84 . 

METHOD 

ISSUED 

REVISED 

18-152. 

06/07/88 

11/15/88 

PAGE: 3 OF 3 

9. Allow the resin to cure in the lid for one (1) hour, or until the 

resin has cooled to room temperature. 

NOTE I: If balance use is required, remove the can lid from the 

balance after gel and place the lid on a heat conductive surface until 

weight back is required. 

NOTE II: A draft-free area is required for the test. 

10. Record the final weight of resin in the can lid to +/- O.Olgm, or 

record the final weight of resin plus the can lid to +/- O.Olgm. 

VI. CALCULATION 

1. Styrene loss in g/m (E) 

a. Can lid left on balance for duration of test 

E = (W - W ) A . 

Where: W = initial weight of resin 

W = final weight of resin 

A = 60.56 for 14.5cm lid 

b. Can lid removed from balance during test for other balance use 

E = (W + W-W) A 

Where: W = initial weight of resin 

W * weight of can lid and paper clip 

W = final weight of resin plus can lid 

A = 60.56 for 14.5cm lid 

VII. REPORT 

Resin 

Batch Number 

Gel Time, Catalyst, and Catalyst Level 

Relative Humidity 

Ambient Temperature 

Styrene Loss in g/m 

Author: 

Approved by: 

B-14f 
P.85 

Appendix C 

Verification and Intercomparison of Compressed Gas Calibration Standards 

C-i 
P.86 

APPENDIX C. VERIFICATION AND INTERCOMPARISON OF COMPRESSED 

GAS CALIBRATION STANDARDS 

Styrene and propane compressed gas calibration standards used to calibrate the Ratfisch 

total hydrocarbon analyzer were purchased in 1994 and 1995 from Scott Specialty Gases in 

Durham, North Carolina. The styrene calibration standards could not be used directly for 

routine calibrations during styrene emission testing because of cylinder pressure limitations 

associated with styrene's dew point. Instead, propane calibration standards without such pressure 

limitations were used for the routine calibrations. Prior to the styrene emission testing at 

Reichhold Chemical, the certified concentrations ofthe styrene and propane calibration standards 

were verified at RTI. Additionally, the styrene and propane calibration standards were 

intercompared using the total hydrocarbon analyzer to obtain a propane-to-styrene correction 

factor for the styrene emission testing. This section discusses the verification and 

intercomparison ofthe calibration standards. 

The styrene in nitrogen calibration standards were verified using a Hewlett Packard 

Model 5890, Series II gas chromatograph with a flame ionization detector, a gas sampling valve, 

and a 10-foot long by 1/8-inch OD stainless steel column packed with 10-percent OV-101 on 

Chromasorb WHP, 80/100 mesh at an oven temperature of 150 degrees Celsius (oC) isothermal. 

The analytical reference standards were prepared by serial dilution ofa primary standard that was 

prepared by injection of liquid styrene and gaseous nitrogen into a canister. The analytical 

reference standard concentrations were 249, 25.1, and 2.49 parts per million by volume (ppmv). . 

Each analytical reference standard and calibration standard was analyzed three times in 

succession before the next standard was analyzed. Styrene concentrations were calculated by 

linear interpolation between the nearest two analytical reference standard measurements. 

The propane in air calibration standards were verified using a Hewlett Packard Model 

5890, Series II gas chromatograph with a flame ionization detector, a gas sampling valve, and a 

6-foot long by 1/8-inch OD stainless steel column packed with n-octane/Porasil Cj 80/100 mesh 

at an oven temperature of 40 oC isothermal. The analytical reference standards were National 

Institute of Standards and Technology (NIST) Standard Reference Materials (SRMs) containing 

propane in air at concentrations of 476, 94.8,48.6, and 0.99 parts ppmv. Each analytical 

reference standard and calibration standard was analyzed five times in succession before the next 

standard was analyzed. Propane concentrations were calculated from a least squares regression 

line determined from the analytical reference standard measurements. 

The results ofthe styrene and propane calibration standard verifications are given in the 

following table: 

C-1 

1? 
P.87 

Stamped Cylinder 

Number 

AAL17461 

BAL3703 

BAL1361 

ALM036826 

BAL4319 

1A009797 

ALM044162 

ALM019336 

AAL4968(1) 

A022617 

A12158 

A5406 

Scott- Certified 

Concentration 

237.1 ppm 

styrene(about 175 

ppm upon reanalysis) 

81.5 ppm styrene 

49.5 ppm styrene 

10.7 ppm styrene 

5.12 ppm styrene 

454 ppm propane 

275 ppm propane 

150.9 ppm propane 

95.4 ppm propane 

44.8 ppm propane 

26.9 ppm propane 

15.95 ppm propane 

RTI-Verified 

Concentration 

(year of RTI 

verification) 

184 ppm (95) 

85.0 ppm (94) 

87.9 ppm (95) 

53.4 ppm (94) 

53.9 ppm (95) 

9.83 ppm (95) 

5.42 ppm (94) 

5.33 ppm (95). 

453.6 ppm (95) 

278.0 ppm (95) 

153.4 ppm (95) 

95.77 ppm (93) 

96.9 ppm (95) 

45.03 ppm (95) 

27.02 ppm (95) 

15.99 ppm.(95) 

Percent Difference 

-22.4 

+4.3 

+7.9 

+7.9 

+8.9 

-8.1 

+5.9 

+4.1 

-0.1 

+1.1 

+1.7 

+0.4 

+1.6 

+0.5 

+0.4 

+0.3 

(1) This calibration standard was not used for routine calibrations during the styrene emission 

testing, but was used during the evaluation of the total hydrocarbon analyzer. 

In general, the Scott-certified concentrations and the RTI-verified concentrations for four 

of five styrene calibration standards agreed to within +/-10 percent. However, the agreement 

was -22.4 percent for AAL 17461. This calibration standard was returned to Scott Specialty 

Gases for reanalysis and its concentration was found to have shifted since its first analysis. It 

was judged to be unstable and was not used for routine calibrations. Three other styrene 

calibration standards (i.e., BAL1361, BAL3703, and BAL4319) had been verified by RTI in 

1994. The reasonably good agreement between RTFs 1994 and 1995 values for these three 

calibration standards supports the beliefs that all styrene calibration standards were measured 

accurately and that the styrene concentrations are stable over the time period between the 

verifications. 

C-2 

^ 
P.88 

The Scott-certified propane concentrations and the RTI-verified concentrations agreed to 

within +/- 2 percent for all seven propane calibration standards. One propane calibration 

standard (i.e. AAL4968) had been verified by RTI in 1993. The good agreement between RTI's 

1993 and 1995 values for this calibration standard supports the beliefs that all propane calibration 

standards were measured accurately and that the propane concentrations are stable over the time 

period between the verifications. The 1995 RTI-verified concentrations for the propane 

calibration standards were used in the routine calibrations during the styrene emissions testing. 

The styrene and propane calibration standards were intercompared using the Ratfisch 

total hydrocarbon analyzer to obtain a propane-to-styrene correction factor for the styrene 

emission testing. The calibration standards were delivered to the analyzer in a manner very 

similar to that employed during routine calibrations. The analyzer operating parameters were 

identical to those used during styrene emission testing. Two styrene calibration standards, four 

propane calibration standards, and zero air were measured twice on Range 2 (0 to 200 ppmv 

styrene). Two other styrene calibration standards, three other propane standards, and zero air 

were measured twice on Range 1 (0 to 20 ppmv styrene). Least squares regression analysis of 2-

minute mean voltages yielded the following slopes for the styrene and propane regression lines: 

Styrene Slope 

(Volts/ppmv) 

Propane Slope 

(Volts/ppmv) 

Slope Ratio 

Range 2 

0.04928 

0.01834 

2.686 

Range 1 

0.50550 

0.18305 

2.762 

A styrene molecule has 8 carbon atoms and a propane molecule has 3 carbon atoms. As a 

first approximation, one would expect the propane-to-styrene correction factor to equal the ratio 

ofthe carbon atoms (i.e., 8/3 = 2.667). The measured slope ratios are in good agreement with 

this theoretical value, particularly for Range 2. 

C-3 

15 
P.89 

Appendix D 

Summary of Calibration Data, Calibration Error Tests, and Drift Checks 

D-i 

~^G? 
P.90 

APPENDIX D. SUMMARY OF CALIBRATION DATA, CALIBRATION ERROR 

TESTS, AND DRIFT CHECKS 

The total hydrocarbon analyzer was calibrated prior to each test run and a calibration drift 

check was done at the end of each test run. This section presents a summary of the calibration 

data, including calibration error tests and drift checks. The calibration requirements of EPA 

Method 25A were met or exceeded for the styrene emission tests. The method specifies that the 

calibration error must be less than +/- 5 percent ofthe calibration standard's concentration. The 

mid-level calibration error was less than +/-1 percent for all test runs and the low-level 

calibration error was less than +/- 2 percent for all test runs. The method specifies that the zero 

and calibration drifts must be less than +/- 3 percent of scale. The zero and calibration drifts 

were less than or equal to +/-1 percent full scale (% FS) for all test runs. 

The propane calibration standards that RTI had verified and intercompared with styrene 

calibration standards were used for routine calibrations. The RTI-verified concentrations were 

used as the values for these calibration standards. For most test runs, the styrene measurements 

were made using Range 2 ofthe analyzer. These measurements were recorded by an Omega 

Engineering model OM-170 data logger and a Hewlett-Packard model 7132A strip chart 

recorder. The discussion of calibration error tests and drift checks in this section is based on 

those data recorded by the strip chart recorder. These data have an approximate resolution of 1/4 

%FS. 

The total hydrocarbon analyzer's response to the high-level calibration standard 

throughout the styrene emission testing is summarized in the following table. The analyzer was 

operated on Range 2 for all test runs, except for those Range 1 test runs marked by asterisks in 

the table. The analyzer's zero and span pots were not adjusted during the entire 5-week testing 

period. This table demonstrates that the analyzer's calibration remained very stable during the 

testing period. All 53 measurements ofthe high-level calibration standard on Range 2 fell 

between 87 and 90.5 % FS. 

Test Run 

PI 

P2 

P3 

P4 

P5 

High-Level 

Cal. Std. 

Response (% 

FS) 

89.75 

90.50 

90.00 

89.50 

89.75 

Test Run 

Gl 

G2 

G3 

G4 

G5 

High-Level 

Cal. Std.' 

Response (% 

FS) 

89.25 

88.75 

89.25 

89.25 

88.50 

Test Run 

Rl 

R2 

R3 

R4* . 

R5 

High-Level 

Cal. Std. 

Response (% 

FS) 

88.75 

89.00 

88.75 

89.50 

88.50 

D-1 
P.91 

Test Run 

P6 

P7 

P8 

P9 

P10 

Pll 

P12 

High-Level 

Cal. Std. 

Response (% 

FS) 

88.50 

89.00 

89.50 

88.50 

89.25 

89.00 

89.00 

Test Run 

G6 

G7 

G8 

G9 

G10 

Gil 

G12 

G13 

G14 

G15 

G16 

G17 

G18 

High-Level 

Cal. Std. 

Response (% 

FS) 

88.75 

90.00 

90.50 

90.00 

90.00 

90.25 

89.75 

89.50 

89.50 

88.50 

88.75 

88.50 

88.75 

Test Run 

R6 

R7 

R8 

R9 

RIO 

Rll 

R12 

R13 

R14 

R15 

R16* 

R17 

R18* 

R19 

R20 

R21 

R22 

R23 

R24 

R25 

High-Level 

Cal. Std. 

Response (% 

FS) 

87.75 

88.00 

88.25 

88.50 

88.00 

88.25 

88.00 

88.00 

88.50 

88.50 

89.00 

87.00 

88.00 

88.75 

89.00 

87.75 

87.50 

88.00 

88.25 

87.75 

* .Analyzer operated on Range 1 (0 to 20 ppm styrene). 

EPA Method 25A specifies that calibration error tests be conducted immediately prior to 

each test run. After the analyzer's calibration equation was determined by measurements ofthe 

high-level calibration standard and zero air, the linearity ofthe calibration curve was tested by 

measurements ofthe mid-level and low-level calibration standards. The calibration error is 

D-2 

< & 
P.92 

calculated as the difference between the analyzer's actual response to these calibration standards 

and the response that is predicted from the calibration equation. The method specifies that the 

calibration error must be less than +/- 5 percent ofthe calibration standard's concentration. The 

following table demonstrates that the mid-level calibration error was less than +/- 1 percent for 

all test runs and that the low-level calibration error was less than +/- 2 percent for all test runs. 

Other data not reported here supports the belief that the analyzer's calibration curve is a straight 

line. 

Test 

Run 

PI 

P2 

P3 

P4 

P5 

P6 

P7 

P8 

P9 

P10 

Pll 

P12 

Gl 

G2 

G3 

G4 

G5 

G6 

G7 

G8 

Mid-Level Cal. 

Error (percent) 

-1.30 

-0.35 

0.19 

-0.60 

0.02 

0.05 

-0.50 

-0.15 

0.05 

0.12 

-0.50 

-0.50 . 

-0.33 

-0.23 

-0.33 

-0.50 

0.05 

-0.23 

0.02 

0.18 

Low-Level Cal. 

Error (percent) 

-1.71 

-0.97 

0.28 

-0.71 

. -0.96 

0.31 

-0.20 

-0.71 

-0.45 

-0.46 

-1.72 

-0.96 

-0.46 

-0.71 

-1.21 

-1.70 

-0.45 

0.05 

-0.96 

0.03 

Test 

Run 

Rl 

R2 

R3 

• R4* 

R5 

R6 

R7 

R8 

R9 

R10 

Rll 

R12 

R13 

R14 

R15 

R16* 

R17 

R18* 

R19 

R20 

Mid-Level 

Cal. Error 

(percent) 

-0.40 

-0.23 

0.22 

0.08 

0.05 

-0.03 

0.15 

-0.13 

-0.40 

0.60 

-0.13 

-0.03 

-0.03 

-0.57 

-0.13 

0.71 

-0.27 

-0.74 

-0.23 

0.39 

Low-Level 

Cal. Error 

(percent) 

-1.20 

-0.70 

0.05 

. -0.73 

-0.45 

-0.44 

-0.70 

-0.96 

-1.21 

0.06 

-0.96 

-1.20 

-0.44 

-0.95 

-0.95 

-0.43 

-0.94 

-0.39 

0.05 

-0.20 

D-3 
P.93 

• Test 

Run 

G9 

G10 

Gil 

G12 

G13 

G14 

G15 

G16 

G17 

G18 

Mid-Level Cal. 

Error (percent) 

-0.42 

-0.42 

-0.52 

-0.59 

-0.60 

-0.60 

-0.40 

-0.23 

-0.40 

-0.23 

Low-Level Cal. 

Error (percent) 

-0.96 

-1.70 

-1.46 

-1.45 

-0.71 

-1.46 

-0.45 

-0.71 

-1.21 

-0.71 

Test 

Run 

R21 

R22 

R23 

R24 

R25 

Mid-Level 

Cal. Error 

(percent) 

-0.03 

0.53 

0.15 

-0.13 

-0.48 

Low-Level 

Cal. Error 

(percent) 

-1.21 

-0.69 

-0.70 

-0.96 

-1.21 

* Analyzer operated on Range 1 (0 to 20 ppm styrene). 

EPA Method 25A specifies that zero and calibration drift checks be conducted 

immediately following the completion of each test run. The same mid-level calibration standard 

and zero air that were measured during the calibration are to be remeasured at the end of the test 

run. The method specifies that the zero and calibration drifts must be less than +/- 3 percent of 

scale. The following table demonstrates that the zero and calibration drifts were less than or 

equal to +/- 1 % FS for all test runs. 

Test Run 

PI 

P2 

P3 

P4 

P5 

P6 

Zero Drift (% 

FS) 

0.00 

0.00 

0.00 

0.00 

0.00 

0.00 

Mid-Level 

Cal. Drift (% 

FS) 

0.50 

0.25 

0.50 

0.25 

0.00 

-0.50 

Test Run 

Rl 

R2 

R3 

R4* 

R5 

R6 

Zero Drift (% 

FS) 

0.00 

-0.25 

0.00 

0.00 

0.00 

0.00 

Mid-Level 

Cal. Drift (% 

FS) 

0.25 

0.00 

-0.25 

0.25 

-0.50 

0.50 

D-4 

gP 
P.94 

Test Run 

P7 

P8 

P9 

P10 

Pll 

P12 

Gl 

G2 

G3 

G4 

G5 

G6 

G7 

G8 

G9 

G10 

Gil 

G12 

G13 

G14 

G15 

G16 

G17 

G18 

Zero Drift (% 

FS) 

0.00 

0.00 

0.00 

0.00 

0.00 

0.00 

0.00 

0.00 

0.00 

-0.25 

0.00 

0.00 

0.00 

0.00 

-0.25 

-0.25 

0.25 

-0.25 

0.00 

0.00 

0.00 

0.00 

0.00 

0.00 

Mid-Level 

Cal. Drift (% 

FS) 

0.50 

-0.50 

0.25 

-0.50 

0.00 

0.50 

-0.25 

0.25 

0.25 

-0.25 

0.00 

0.25 

0.25 

-0.50 

0.50 

0.00 

-0.25 

0.00 

0.00 

-0.50 

-0.50 

-0.25 

0.25 

0.00 

Test Run 

R7 

R8 

R9 

RIO 

Rll 

R12 

R13 

R14 

R15 

R16* 

. R17 

R18* 

R19 

R20 

R21 

R22 

R23 

R24 

R25 

Zero Drift (% 

FS) 

0.00 

0.00 

0.00 

0.00 

0.25 

0.00 

0.00 

0.00 

0.00 

-0.25 

0.00 

-0.75 

0.00 

0.00 

0.00 

• -0.25 

0.00 

0.00 

0.00 

Mid-Level 

Cal. Drift (% 

FS) 

0.00 

0.00 

0.25 

-0.25 

0.00 

0.25 

0.00 

0.25 

-0.75 

-0.25 

0.25 

0.00 

0.50 

-1.00 

0.00 

0.00 

0.00 

0.25 

0.75 

* Analyzer operated on Range 1 (0 to 20 ppm styrene). 

D-5 
P.95 

Appendix E 

A Summary of Emission Measurements, Gravimetric Measurements, and Calculated Emission 

Quantities and Emission Factors for the Test 

E-i 

8z 
Emission Measurements, Gravimetric Measurements, and Calculated Emissions and Factors 

m 

u 

Date Time Test run # 

EXPERIMENTAL RUNS 

6/6/95 

6/6/95 

7/7/95 

7/7/95 

10:22 

14:55 

12:19 

14:12 

RF1-EXP 

GF1-EXP 

EXP1 

EXP2 

PILOT EXPERIMENT 

6/7/95 

6/8/95 

6/8/95 

678/95 

6/9/95 

6/9/95 

6/12/95 

6/12/95 

6/12/95 

6/13/95 

6/13/95 

6/13/95 

14:50 

10:01 

12:11 

14:40 

10:20 

14:45 

10:36 

13:47 

15:44 

10:37 

12:57 

15:21 

Average (12 runs) 

I 

P1 

P2 

P3 

P4 

P5 

P6 

P7 

P8 

P9 

P10 

P11 

P12 

M1-Normal spraying (6 runs) 

M2-Controlled spraying (6 runs 

I I 

A2-High air velocity (6 runs) 

A1 -Low air velocity (6 runs) 

I 

M1/A1 (3 runs) 

M2/A1 (3 runs) 

M1/A2 (3 runs) 

M2/A2 (3 runs) 

Material/ 

container # 

RF1 

GF1 

GF1 

GF1 

GF1 #10 

GF1#1 

GF1 #1 

GF1#1 

GF1#1 

GF1#1 

GF1 #1/#2 

GF1#2 

GF1#2 

GF1#2 

GF1#2 

GF1#2 

Equip. 

RE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

Application 

Method 

Normal 

Normal 

Enclosed 

Part. End. 

Controlled 

Normal 

Controlled 

Normal 

Controlled 

Normal 

Controlled 

Normal 

Controlled 

Controlled 

Normal 

Normal 

, 

Air Vel. 

High 

High 

Low 

Low 

Low 

High 

High 

High 

Low 

Low 

High 

Low 

High 

Low 

High 

Low 

Avg. sqrt 

. (delta P) 

0.3693 

0.3657 

0.3376 

0.3464 

0.3582 

0.3619 

0.3605 

0.3464 

0.3535 

0.3476 

0.3559 

0.3524 

0.3464 

0.3647 

0.3623 

0.3582 

0.3557 

0.3548 

0.3565 

0.3556 

0.3558 

0.3527 

0.3588 

0.3569 

0.3543 

Exhaust flow 

rate, cfm 

9124 

9054 

8510 

8681 

8909 

8980 

8953 

8681 

8818 

8704 

8864 

8796 

8681 

9034 

8987 

8909 

8860 

8843 

8876 

8858 

8862 

8803 

8920 

8883 

8833 

Avg. conc. 

ppm 

6.94 

7.54 

1.06 

4.90 

4.18 

7.60 

5.39 

7.75 

5.14 

6.62 

5.28 

7.85 

6.57 

5.64 

6.49 

6.61 

6.26 

7.15 

5.37 

6.51 

6.01 

7.03 

4.99 

7.28 

5.75 

Background 

conc, ppm 

0.59 

0.23 

0.48 

0.42 

0.32 

0.47 

0.33 

0.36 

0.42 

0.41 

0.29 

0.32 

0.65 

0.53 

0.45 

0.59 

0.43 

0.43 

0.42 

0.43 

0.43 

0.44 

0.43 

0.43 

0.42 

Avg. net 

conc, ppm 

6.35 

7.30 

0.58 

4.48 

3.85 

7.14 

5.05 

7.39 

4.72 

6.21 

4.99 

7.53 

5.92 

5.11 

6.04 

6.02 

5.83 

6.72 

4.94 

6.09 

5.57 

6.59 

4.56 

6.86 

5.32 

Test run 

duration, min 

88.8 

56.2 

102.2 

31.2 

76.3 

68.2 

68.8 

66.8 

77.8 

76.3 

78.7 

68.2 

66.9 

70.0 

71.9 

72.3 

71.8 

70.6 

73.1 

70.2 

73.5 

72.3 

74.7 

69.0 

71.5 

Total emissions 

by THC, g 

631 

456 

62 

149 

322 

536 

382 

526 

397 

506 

427 

554 

422 

396 

479 

476 

452 

513 

391 

462 

442 

512 

372 

514 

410 

SUMNEW.XLS 
Emission Measurements, Gravimetric Measurements, and Calculated Emissions and Factors 

m 

i 

IO ^ . r 

Date Time Test mn # 

EXPERIMENTAL RUNS 

6/6/95 

6/6/95 

7/7/95 

7/7/95 

10:22 

14:55 

12:19 

14:12 

RF1-EXP 

GF1-EXP 

EXP1 

EXP2 

PILOT EXPERIMENT 

6/7/95 

6/8/95 

6/8/95 

6/8/95 

6/9/95 

6/9/95 

6/12/95 

6/12/95 

6/12/95 

6/13/95 

6/13/95 

6/13/95 

14:50 

10:01 

12:11 

14:40 

10:20 

14:45 

10:36 

13:47 

15:44 

10:37 

12:57 

15:21 

Average (12 mns) 

I 

P1 

P2 

P3 

P4 

P5 

P6 

P7 

P8 

P9 

P10 

P11 

P12 

M1-Normal spraying (6 mns) 

Material/ 

container ft 

RF1 

GF1 

GF1 

GF1 

GF1 #10 

GF1#1 

GF1#1 

GF1 #1 

GF1#1 

GF1#1 

GF1 #1/#2 

GF1#2 

GF1#2 

GF1#2 

GF1#2 

GF1#2 

M2-Controlled spraying (6 mns) 

I I 

A2-High air velocity (6 mns) 

Al-Low air velocity (6 mns) 

1 

M1/A1 (3 runs) 

M2/A1(3runs) 

M1/A2 (3 mns) 

M2/A2 (3 runs) 

Equip. 

RE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

Avg. spraying 

conc, ppm 

65.74 

41.31 

1.05 

45.25 

29.73 

43.71 

42.14 

65.24 

39.44 

59.03 

48.30 

74.04 

52.82 

41.80 

64.60 

58.44 

51.61 

60.84 

42.37 

52.80 

50.41 

63.84 

36.99 

57.85 

47.75 

Avg. net 

spraying, ppm 

65.14 

41.08 

0.57 

44.83 

29.41 

43.24 

41.80 

64.87 

39.01 

58.62 

48.01 

73.71 

52.17 

41.27 

64.15 

57.85 

51.18 

60.41 

41.95 

52.37 

49.98 

63.39 

36.56 

57.42 

47.33 

Spraying 

time, min 

4.5 

5.0 

2.0 

2.2 

4.2 

6.5 

3.0 

3.7 

3.2 

3.5 

3.0 

3.4 

3.2 

3.2 

3.0 

3.2 

3.6 

3.9 

3.3 

3.7 

3.4 

3.4 

3.5 

4.4 

3.1 

Emissions 

during 

application 

(by THC) 

328 

228 

1 

103 

134 

310 

138 

253 

134 

219 

157 

271 

176 

145 

214 

204 

196 

245 

147 

208 

184 

231 

138 

259 

157 

Std. Dev. of 

application 

emissions 

(by THC) 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

57 

37 

15 

59 

51 

28 

5 

39 

16 

Wt. loss from 

part during 

curing stage 

(by MB) 

264 

193 

44 

50 

167 

190 

221 

203 

224 

242 

235 

217 

213 

221 

235 

218 

216 

218 

214 

216 

215 

226 

204 

209 

223 

Std. Dev. of 

curing loss 

from part 

(by MB) 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

20 

18 

22 

16 

23 

12 

26 

19 

9 

Wt. loss during 

application and from 

overspray, g 

(by MB) 

622 

285 

21 

102 

213 

417 

221 

212 

188 

264 

231 

282 

176 

236 

300 

224 

247 

283 

211 

260 

235 

257 

212 

310 

209 

SUMNEW.XLS 

^i 
(A) 

A' 

m 

i 

CO 

Emission Measurements, Gravimetric Measurements, and Calculated Emissions and Factors 

Date Time Test mn # 

EXPERIMENTAL RUNS 

6/6/95 

6/6/95 

7/7/95 

7/7/95 

10:22 

14:55 

12:19 

14:12 

RF1-EXP 

GF1-EXP 

EXP1 

EXP2 

PILOT EXPERIMENT 

6/7/95 

6/8/95 

6/8/95 

6/8/95 

6/9/95 

6/9/95 

6/12/95 

6/12/95 

6/12/95 

6/13/95 

6/13/95 

6/13/95 

14:50 

10.01 

12:11 

14:40 

10:20 

14:45 

10:36 

13:47 

15:44 

10:37 

12:57 

15:21 

Average (12 mns) 

I 

P1 

P2 

P3 

P4 

P5 

P6 

P7 

P8 

P9 

P10 

P11 

P12 

Ml-Normal spraying (6 mns) 

M2-Controlled spraying (6 mns 

1 1 A2-High air velocity (6 mns) 

A1-Low air velocity (6 mns) 

I 

M1/A1 (3 mns) 

M2/A1 (3 mns) 

M1/A2 (3 mns) 

M2/A2 (3 mns) 

Material/ 

container # 

RF1 

GF1 

GF1 

GF1 

GF1 #10 

GF1#1 

GF1#1 

GF1#1 

GF1#1 

GF1#1 

GF1 #1/#2 

GF1#2 

GF1#2 

GF1#2 

GF1#2 

GF1#2 

Equip. 

REI 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

Total emissions 

by MB, g 

886 

478 

65 

152 

380 

607 

442 

415 

412 

506 

466 

499 

389 

457 

535 

442 

463 

501 

424 

476 

449 

482 

416 

519 

432 

Ratio of two 

measurement 

methods 

(MB/THC) 

1.40 

1.05 

1.05 

1.02 

1.18 

1.13 

1.16 

o.7g 

1.04 

1.00 

1.09 

0.90 

0.92 

1.15 

1.12 

0.93 

1.03 

0.98 

1.09 

1.03 

1.03 

0.94 

1.12 

1.01 

1.06 

Material 

used, g 

9287 

1564 

1732 

1737 

1564 

2261 

1695 

2067 

1964 

2204 

1900 

2056 

2064 

2021 

2077 

2049 

1994 

2119 

1868 

2011 

1976 

2103 

1850 

2135 

1886 

Transfer 

eff. % 

90.1 

75.5 

99.9 

94.2 

79.8 

66.1 

80.0 

74.0 

85.1 

75.7 

81.2 

73.8 

85.0 

82.6 

74.5 

77.7 

78.0 

73.6 

82.3 

76.8 

79.1 

75.7 

82.5 

71.5 

82.1 

Styrene 

content, % 

38.33 

38.75 

38.75 

38.75 

38.75 

38.75 

38.75 

38.75 

38.75 

38.75 

38.75 

38.75 

38.75 

38.75 

38.75 

38.75 

38.75 

38.75 

38.75 

38.75 

38.75 

38.75 

38.75 

38.75 

38.75 

I 

EF, % available styrene 

by THC 

17.7 

75.2 

9.2 

22.2 

53.1 

61.2 

58.2 

65.7 

52.2 

59.2 

58.0 

69.6 

52.7 

50.6 

59.5 

60.0 

58.3 

62.5 

54.1 

59.2 

57.4 

62.9 

52.0 

62.1 

56.3 

by MB 

24.9 

78.9 

9.7 

22.6 

62.7 

69.3 

67.3 

51.8 

54.1 

59.2 

63.3 

62.6 

48.6 

58.4 

66.5 

55.7 

60.0 

60.9 

59.1 

61.1 

58.8 

59.2 

58.4 

62.5 

59.7 

1 Std. Dev.. % AS 

by THC 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

5.4 

3.8 

2.9 

3.9 

6.5 

4.7 

1.0 

2.6 

2.5 

by MB 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

6.2 

6.0 

6.2 

8.0 

3.2 

2.8 

3.5 

7.7 

8.0 

Total mold 

surface, m2 

2.28 

2.28 

0.32 

0.45 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

SUMNEW.XLS 

T l 

CO 

00 
Emission Measurements, Gravimetric Measurements, and Calculated Emissions and Factors 

Q> m 

i 

Date Time Test mn # 

EXPERIMENTAL RUNS 

6/6/95 

6/6/95 

7/7/95 

7/7/95 

10:22 

14:55 

12:19 

14:12 

RF1-EXP 

GF1-EXP 

EXP1 

EXP2 

PILOT EXPERIMENT 

6/7/95 

6/8/95 

6/8/95 

6/8/95 

6/9/95 

6/9/95 

6/12/95 

6/12/95 

6/12/95 

6/13/95 

6/13/95 

6/13/95 

14:50 

10:01 

12:11 

14:40 

10:20 

14:45 

10:36 

13:47 

15:44 

10:37 

12:57 

15:21 

Average (12 mns) 

I 

P1 

P2 

P3 

P4 

P5 

P6 

P7 

P8 

P9 

P10 

P l l 

P12 

Ml-Normal spraying (6 mns) 

M2-Controlled spraying (6 mns 

1 1 

A2-High air velocity (6 mns) 

A1-Low air velocity (6 mns) 

I M1/A1(3mns) 

M2/A1 (3 runs) 

M1/A2(3runs) 

M2/A2(3runs) 

Material/ 

container # 

RF1 

GF1 

GF1 

GF1 

GF1 #10 

GF1#1 

GF1#1 

GF1#1 

GF1#1 

GF1#1 

GF1 #1/#2 

GF1#2 

GF1#2 

GF1#2 

GF1#2 

GF1#2 

Equip. 

RE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

GE1 

1 

EF.j 

by THC 

277 

200 

194 

332 

141 

236 

168 

231 

175 

222 

188 

244 

185 

174 

210 

20g 

199 

225 

172 

203 

194 

225 

163 

226 

180 

i/m2 

by MB 

389 

210 

205 

339 

167 

267 

194 

182 

181 

222 

205 

219 

171 

201 

235 

194 

203 

220 

186 

209 

197 

212 

183 

228 

190 

I 

Std. Dev., g/m2 

by THC 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

30.2 

12.6 

15.2 

24.8 

34.2 

14.2 

15.6 

10.9 

8.8 

by MB 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

27.6 

27.4 

14.4 

32.7 

19.6 

12.6 

13.9 

34.8 

14.1 

1 

EF, g/g material 

by THC 

0.068 

0.291 

0.036 

0.086 

0.206 

0.237 

0.225 

0.254 

0.202 

0.230 

0.225 

0.270 

0.204 

0.196 

0.231 

0.232 

0.226 

0.242 

0.210 

0.229 

0.223 

0.244 

0.201 

0.241 

0.218 

by MB 

0.095 

0.306 

0.038 

0.088 

0.243 

0.268 

0.261 

0.201 

0.210 

0.230 

0.245 

0.243 

0.188 

0.226 

0.258 

0.216 

0.232 

0.236 

0.229 

0:237 

0.228 

0.229 

0.226 

0.242 

0.231 

1 

Std. Dev., g/g 

by THC 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

0.021 

0.015 

0.011 

0.015 

0.025 

0.018 

0.004 

0.010 

0.010 

by MB 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

0.024 

0.023 

0.024 

0.031 

0.012 

0.011 

0.014 

0.030 

0.031 

Catalyst 

Ratio, % 

1.33 

1.40 

NC 

NC 

1.66 

1.68 

1.65 

1.79 

1.63 

1.68 

1.74 

1.75 

1.74 

1.73 

1.69 

1.76 

1.71 

1.73 

1.69 

1.72 

1.70 

1.73 

1.67 

1.72 

1.71 

Glass/rtesin 

Ratio, % 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

SUMNEW.XLS 

T l 

CO 

CO 
Emission Measurements, Gravimetric Measurements, and Calculated Emissions and Factors 

QD m 

i 

cn 

Date Time Test mn # 

GELCOAT EXPERIMENT 

6/14/95 

6/14/95 

6/14/95 

6/15/95 

6/15/95 

6/15/95 

6/16/95 

6/16/95 

6/16/95 

6/19/95 

6/19/95 

6/19/95 

6/21/95 

6/21/95 

6/21/95 

6/22/95 

6/22/95 

6/22/95 

10:11 

13:46 

16:06 

11:38 

14:03 

15:59 

10:23 

12:49 

15:33 

10:36 

12:47 

15:23 

10:46 

13:18 

16:27 

11:14 

13:41 

15:55 

Average (18 mns) 

I 

G1 

G2 

G3 

G4 

G5 

G6 

G7 

G8 

G9 

G10 

G11 

G12 

G13 

G14 

G15 

G16 

G17 

G18 

GFl-Regular gel coat (9 mns) 

Material/ 

container # 

GFl #2 

GF1 #2/#3 

GF1 #2/#3 

GF2#1 

GFl #3 

GF1#3 

GF2#1 

GFl #3/#4 

GF1 #3/#4 

GFl #4 

GF2#1/#2 

GF2#1/#2 

GF2#2 

GF2#2 

GFl #4 

GF2#2/#3 

GF2#2/#3 

GF2#3 

GF2-Low VOC gel coat (9 mns) 

1 1 GE1-AAA ext mix gun (6 mns) 

GE2-HVLP int mix gun (6 mns) 

GE3-HVLP ext mix gun (6 mns 

1 GF1/GE1 (3 mns) 

GF1/GE2 (3 mns) 

GF1/GE3(3mns) 

GF2/GE1 (3 mns) 

GF2/GE2 (3 mns) 

GF2/GE3 (3 mns) 

) 

Equip. 

GE3 

GE2 

GE1 

GE1 

GE1 

GE1 

GE3 

GE3 

GE2 

GE3 

GE2 

GE2 

GE2 

GE1 

GE2 

GE1 

GE3 

GE3 

Application 

Method 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Air Vel. 

Low 

Low 

LowLow 

Low 

Low 

Low 

Low 

Low 

Low 

Low 

Low 

Low 

Low 

Low 

Low 

Low 

Low 

Avg. sqrt 

(delta P) 

0.3507 

0.3464 

0.3403 

0.3428 

0.3427 

0.3440 

0.3586 

0.3571 

0.3536 

0.3500 

0.3559 

0.3473 

0.3527 

0.3493 

0.3452 

0.3511 

0.3535 

0.3484 

0.3494 

0.3478 

0.3511 

0:3450 

0.3502 

0.3530 

0.3423 

0.3484 

0.3526 

0.3477 

0.3519 

0.3535 

Exhaust flow 

rate, cfm 

8764 

8680 

8563 

8610 

8609 

8633 

8916 

8887 

8819 

8752 

8866 

8700 

8804 

8739 

8660 

8775 

8820 

8722 

8740 

8707 

8772 

8655 

8755 

8810 

8602 

8720 

8801 

8708 

8790 

8819 

Avg. cone. 

ppm 

5.80 

5.89 

6.94 

3.80 

5.92 

5.80 

3.38 

5.60 

5.65 

5.60 

3.77 

3.47 

3.77 

3.36 

5.81 

3.47 

3.80 

3.80 

4.76 

5.89 

3.62 

4.88 

4.73 

4.66 

6.22 

5.79 

5.67 

3.54 

3.67 

3.66 

Background 

cone, ppm 

0.55 

0.59 

0.47 

0.39 

0.51 

0.68 

0.31 

0.63 

0.58 

0.46 

0.59 

0.72 

0.55 

0.51 

0.56 

0.47 

0.58 

0.60 

0.54 

0.56 

0.53 

0.50 

0.60 

0.52 

0.55 

0.58 

0.55 

046 

0.62 

0.50 

Avg. net 

cone, ppm 

5.25 

5.30 

6.46 

3.41 

5.41 

5.13 

3.07 

4.97 

5.07 

5.14 

3.18 

2.74 

3.22 

2.85 

5.25 

3.00 

3.21 

3.19 

4.21 

5.33 

3.10 

4.38 

4.13 

4.14 

5.67 

5.21 

5.12 

3.09 

3.05 

3.16 

Test mn 

duration, min 

70.0 

70.0 

60.3 

75.7 

70.4 

71.2 

80.7 

70.5 

70.2 

69.6 

85.1 

85.0 

83.7 

87.5 

60.7 

85.0 

85.7 

82.4 

75.8 

68.1 

83.4 

75.0 

75.8 

76.5 

67.3 

67.0 

70.0 

82.7 

84.6 

82.9 

Total emissions 

by THC, g 

395 

395 

409 

273 

403 

387 

271 

382 

386 

384 

294 

249 

291 

267 

339 

274 

298 

282 

332 

387 

278 

336 

326 

335 

400 

373 

387 

272 

278 

284 

SUMNEW.XLS 
Emission Measurements, Gravimetric Measurements, and Calculated Emissions and Factors 

m 

i 

CO 

Oate Time Test run # 

GELCOAT EXPERIMENT 

6/14/95 

6/14/95 

6/14/95 

6/15/95 

6/15/95 

6/15/95 

6/16/95 

6/16/95 

6/16/95 

6/19/95 

6/19/95 

6/19/95 

6/21/95 

6/21/95 

6/21/95 

6/22/95 

6/22/95 

6/22/95 

10:11 

13:46 

16:06 

11:38 

14:03 

15:59 

10:23 

12:49 

15:33 

10:36 

12:47 

15:23 

10:46 

13:18 

16:27 

11:14 

13:41 

15:55 

Average (18 runs) 

I 

G1 

G2 

G3 

G4 

G5 

G6 

G7 

G8 

G9 

G10 

G11 

G12 

G13 

G14 

G15 

G16 

G17 

G18 

GF1 -Regular gel coat (9 runs) 

GF2-Low VOC gel coat (9 mns 

I I 

GEI-AAA.ext mix gun (6 mns) 

Material/ 

container 9 

GFl #2 

GFl #2/#3 

GF1 #2/#3 

GF2#1 

GF1 #3 

GF1#3 

GF2#1 

GFl #3/#4 

GFl #3/#4 

GFl #4 

GF2#1/#2 

GF2 #1/#2 

GF2#2 

GF2#2 

GFl #4 

GF2 #2/#3 

GF2 #2/#3 

GF2#3 

) 

GE2-HVLP int mix gun (6 mns) 

GE3-HVLP ext mix gun (6 runs 

„• 1 

GF1/GE1 (3 runs) 

GF1/GE2 (3 mns) 

GF1/GE3(3mns) 

GF2/GE1 (3 mns) 

GF2/GE2 (3 runs) 

GF2/GE3<3mns) 

) 

Equip. 

GE3 

GE2 

GE1 

GE1 

GE1 

GE1 

GE3 

GE3 

GE2 

GE3 

GE2 

GE2 

GE2 

GE1 

GE2 

GE1 

GE3 

GE3 

Avg. spraying 

cone, ppm 

48.22 

44.48 

50.51 

21.88 

49.01 

45.34 

23.46 

44.31 

45.04 

43.40 

28.43 

29.10 

34.91 

30.12 

48.31 

26.75 

31.41 

29.39 

37.45 

46.51 

28.38 

37.27 

38.38 

36.70 

48.29 

45.94 

45.31 

26.25 

30.81 

28.09 

Avg. net 

spraying, ppm 

47.66 

43.89 

50.04 

21.50 

48.50 

44.66 

23.14 

43.68 

44.46 

42.94 

27.84 

28.37 

34.35 

29.61 

47.75 

26.28 

30.83 

28.79 

36.90 

45.95 

27.86 

36.76 

37.78 

36.17 

47.73 

45.37 

44.76 

25.80 

30.19 

27.59 

Spraying 

time, min 

3.0 

3.5 

3.0 

4.0 

3.0 

3.0 

3.2 

3.0 

3.2 

2.9 

3.1 

3.1 

3.0 

2.9 

3.2 

3.5 

3.0 

3.0 

3.1 

3.1 

3.2 

3.2 

3.2 

3.0 

3.0 

3.3 

3.0 

3.5 

3.1 

3.1 

Emissions 

during 

application 

(by THC) 

154 

164 

158 

91 

154 

142 

80 

143 

155 

134 

94 

94 

112 

92 

• 162 

99 

100 

93 

. , 

123 

152 

95 

123 

130 

"

7 

151 

160 

143 

94 

100 

91 

Std. Dev. of 

application 

• emissions 

(by THC) 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

30 

9 

8 

29 

31 

27 

7 

4 

8 

4 

9 

8 

Wt. loss from 

part during 

curing stage 

(by MB) 

220 

206 

204 

153 

212 

220 

161 

211 

205 

214 

159 

157 

163 

165 

201 

155 

157 

160 

185 

210 

159 

185 

182 

187 

212 

204 

215 

158 

160 

159 

Std. Dev. of 

curing loss 

frompart 

(by MB) 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

26 

6 

4 

28 

22 

28 

1 

2 

4 

5 

2 

2 

Wt. loss during 

application and from 

overspray, g 

(by MB) 

128 

200 

200 

74 

143 

190 

112 

261 

193 

146 

168 

189 

211 

167 

186 

147 

153 

126 

166 

183 

150 

154 

191 

154 

178 

193 

178 

129 

189 

130 

SUMNEW.XLS 

-o 

to 
Ofc, 

-Q 

m 

i 

Emission Measurements, Gravimetric Measurements, and Calculated Emissions and Factors 

Date Time Test mn # 

GELCOAT EXPERIMENT 

6/14/95 

6/14/95 

6/14/95 

6/15/95 

6/15/95 

6/15/95 

6/16/95 

6/16/95 

6/16/95 

6/19/95 

6/19/95 

6/19/95 

6/21/95 

6/21/95 

6/21/95 

6/22/95 

6/22/95 

6/22/95 

10:11 

13:46 

16:06 

11:38 

14:03 

15:59 

10.23 

12:49 

15:33 

10:36 

12:47 

15:23 

10:46 

13:18 

16:27 

11:14 

13:41 

15:55 

Average (18 mns) 

I 

G1 

G2 

G3 

G4 

G5 

G6 

G7 

G8 

G9 

G10 

G11 

G12 

G13 

G14 

G15 

G16 

G17 

G18 

GF1-Regular gel coat (9 mns) 

GF2-Low VOC gel coat (9 mns 

I I 

GE1-AAA ext mix gun (6 mns) 

Material/ 

container # 

GF1#2 

GFl #2/#3 

GF1 #2/#3 

GF2#1 

GF1#3 

GFl #3 

GF2#1 

GFl #3/#4 

GF1 #3/#4 

GF1#4 

GF2#1/#2 

GF2#1/#2 

GF2#2 

GF2#2 

GFl #4 

GF2#2/#3 

GF2#2/#3 

GF2#3 

) 

GE2-HVLP int mix gun (6 mns) 

GE3-HVLP ext mix gun (6 mns 

1 

GF1/GE1 (3 mns) 

GF1/GE2 (3 mns) 

GF1/GE3(3mns) 

GF2/GE1 (3 mns) 

GF2/GE2 (3 runs) 

GF2/GE3 (3 mns) 

) 

Equip. 

GE3 

GE2 

GE1 

GE1 

GE1 

GE1 

GE3 

GE3 

GE2 

GE3 

GE2 

GE2 

GE2 

GE1 

GE2 

GE1 

GE3 

GE3 

Total emissions 

by MB, g 

348 

406 

404 

227 

355 

410 

273 

472 

398 

360 

327 

346 

374 

332 

387 

302 

310 

286 

351 

393 

309 

338 

373 

342 

390 

397 

393 

287 

349 

290 

Ratio of two 

measurement 

methods 

(MB/THC) 

0.88 

1.03 

0.99 

0.83 

0.88 

1.06 

1.01 

1.24 

1.03 

0.94 

1.11 

1.39 

1.28 

124 

1.14 

1.10 

1.04 

1.01 

1.07 

1.02 

• 1.11 

1.02 

1.16 

1.02 

0.98 

1.07 

1.02 

1.06 

1.26 

1.02 

Material 

used, g 

1723 

1808 

1756 

1929 

1765 

1817 

1876 

1891 

1787 

1723 

1940 

1940 

2245 

1933 

1776 

2128 

2275 

1963 

1904 

1783 

2025 

1888 

1916 

1909 

1779 

1790 

1779 

1997 

2042 

2038 

Transfer 

eff. % 

84.6 

• 81.4 

79.0 

88.8 

84.3 

82.9 

87.3 

80.0 

82.4 

84.7 

83.3 

81.9 

81.1 

81.9 

82.0 

87.4 

85.7 

85.4 

83.6 

82.4 

84.8 

84.1 

82.0 

. 84.6 

82.1 

81.9 

83.1 

86.0 

82.1 

86.1 

Styrene 

content, % 

38.75 

38.75 

38.75 

25.35 

38.75 

38.75 

25.35 

38.75 

38.75 

38.75 

25.35 

25.35 

25.35 

25.35 

38.75 

25.35 

25.35 

25:35 

32.05 

38.75 

25.35 

32.05 

32.05 

32.05 

38.75 

38.75 

38.75 

25.35 

25.35 

25.35 

1 

EF, % available styrene 

by THC 

59.2 

56.4 

60.2 

55.8 

58.9 

54.9 

56.9 

52.1 

55.7 

57.6 

59.8 

50.6 

51.2 

54.6 

49.2 

50.9 

51.7 

56.6 

55.1 

56.0 

54.2 

55.9 

53,8 

55.7 

58.0 

53.8 

56.3 

53.7 

53.9 

55.1 

by MB 

52.1 

58.0 

59.4 

46.4 

51.9 

58.2 

57.4 

64.4 

57.5 

53.9 

66.5 

70.4 

65.7 

67.8 

56.2 

56.0 

53.8 

57.5 

58.5 

56.8 

60.2 

56.6 

62.4 

56.5 

56.5 

57.2 

56.8 

56.7 

67.5 

56.2 

I 

Std. Dev., % AS 

by THC 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

3.4 

3.3 

3.1 

3.0 

3.8 

2.8 

2.2 

3.2 

3.0 

2.1 

4.2 

2.4 

by MB 

NA 

NA 

NA 

. NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

6.1 

3.7 

7.4 

6.6 

5.4 

4.0 

3.3 

0.7 

5.4 

8.7 

2.0 

1.7 

Total mold 

surface, m2 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

228 

2.28 

2.28 

2.28 

SUMNEW.XLS 

CO 
Emission Measurements, Gravimetric Measurements, and Calculated Emissions and Factors 

.-8 m 

CO 

Date Time Test run tt 

GELCOAT EXPERIMENT 

6/14/95 

6/14/95 

6/14/95 

6/15/95 

6/15/95 

6/15/95 

6/16/95 

6/16/95 

6/16/95 

6/19/95 

6/19/95 

6/19/95 

6/21/95 

6/21/95 

6/21/95 

6/22/95 

6/22/95 

6/22/95 

10:11 

13:46 

16:06 

11:38 

14:03 

15:59 

10:23 

12:49 

15:33 

10:36 

12:47 

15:23 

10:46 

13:18 

16:27 

11:14 

13:41 

15:55 

Average (18 mns) 

I 

G1 

G2 

G3 

G4 

G5 

G6 

G7 

G8 

G9 

G10 

G11 

G12 

G13 

G14 

G15 . 

G16 

G17 

G18 

GF1 -Regular gel coat (9 mns) 

GF2-Low VOC gel coat (9 mns 

I I 

GE1-AAA ext mix gun (6 mns) 

Material/ 

container # 

, 

GF1#2 

GFl #2/#3 

GF1 #2/#3 

GF2#1 

GF1#3 

GF1 #3 

GF2#1 

GFl #3/#4 

GF1 #3/#4 

GFl #4 

GF2#1/#2 

GF2#1/#2 

GF2#2 

GF2#2 

GFl #4 

GF2#2/»3 

GF2#2/#3 

GF2#3 

) 

GE2-HVLP int mix gun (6 mns) 

GE3-HVLP ext mix gun (6 mns 

| 

GF1/GE1 (3 mns) 

GF1/GE2 (3 runs) 

GF1/GE3 (3 runs) 

GF2/GE1 (3 runs) 

GF2/GE2 (3 runs) 

GF2/GE3 (3 mns) 

) 

Equip. 

GE3 

GE2 

GE1 

GE1 

GE1 

GE1 

GE3 

GE3 

GE2 

GE3 

GE2 

GE2 

GE2 

GE1 

GE2 

GE1 

GE3 

GES 

1 

EF,£ 

by THC 

174 

174 

180 

120 

177 

170 

119 

168 

169 

169 

129 

109 

128 

117 

149 

120 

131 

124 

146 

170 

122 

147 

143 

147 

176 

164 

170 

119 

122 

124 

i/m2 

by MB 

153 

178 

177 

100 

156 

180 

120 

207 

175 

158 

144 

152 

164 

146 

170 

132 

136 

125 

154 

173 

135 

149 

164 

150 

171 

174 

173 

126 

153 

127 

I 

Std. Dev., g/m2 

by THC 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

25.1 

8.4 

6.4 

28.4 

23.2 

23.1 

4.2 

10.9 

2.5 

1.3 

9.1 

4.8 

by MB 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

25.1 

15.7 

17.9 

27.5 

12.4 

29.1 

10.8 

3.5 

24.5 

19.3 

8.4 

6.6 

I 

EF, g/g material 

by THC 

0.229 

0.218 

0.233 

0.141 

0.228 

0.213 

0.144 

0.202 

0.216 

0.223 

0.152 

0.128 

0.130 

0.138 

0.191 

0.129 

0.131 

0.144 

0.177 

0.217 

0.137 

0.180 

0.172 

0.179 

0.225 

0.208 

0.218 

0.136 

0.137 

0.140 

by MB 

0.202 

0.225 

0.230 

0.118 

0.201 

0.226 

0.146 

0.250 

0.223 

0.209 

0.169 

0.178 

0.167 

0.172 

0.218 

0.142 

0.136 

0.146 

0.186 

0.220 

0.152 

0.181 

0.196 

0.181 

0.219 

0.222 

0.220 

0.144 

0.171 

0.142 

I 

Std. Dev., g/g 

by THC 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

0.041 

0.013 

0.008 

0.045 

0.038 

0.040 

0.009 

0.012 

0,012 

0.005 

0.011 

0.006 

by MB 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

0.038 

0.014 

0.019 

0.042 

0.026 

0.042 

0.013 

0.003 

0.021 

0.022 

0.005 

0.004 

Catalyst 

Ratio, % 

1.86 

1.88 

1.82 

1.68 

1.92 

1.87 

1.65 

1.80 

1.82 

1.80 

1.86 

1.75 

1.87 

1.86 

1.89 

1.80 

1.71 

1.78 

1.81 

1.85 

1.77 

1.83 

1.85 

1.77 

1.87 

1.86 

1.82 

1.78 

1.83 

1.71 

Glass/Resin 

Ratio, % 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

SUMNEW.XLS 
Emission Measurements, Gravimetric Measurements, and Calculated Emissions and Factors 

m 

i 

to 

Date Time Test mn # 

RESIN EXPERIMENT 

6723/95 

6/23/95 

6/23/95 

6/26/95 

6/26/95 

6/26/95 

6/27/95 

6/27/95 

6/27/95 

6/28/95 

6/28/95 

6/28/95 

6/29/95 

6/29/95 

6/29/95 

6/30/95 

6/30/95 

6/30/95 

7/5/95 

• 7/5/95 

7/5/95 

7/6/95 

7/6/95 

7/6/95 

7/7/95 

11:06 

14:30 

16:35 

10:42 

13:27 

16:05 

10:46 

13:14 

15:51 

10.21 

12:45 

15:20 

10:22 

12:20 

14:36 

10:14 

13:13 

15:51 

11:53 

14:02 

16:19 

10:12 

14:34 

16:41 

10:10 

R1 

R2 

R3 

R4 

R5 

R6 

R7 

R8 

R9 

R10 

R11 

R12 

R13 

R14 

R15 

R16 

R17 

R18 

R19 

R20 

R21 

R22 

R23 

R24 

R25 

Material/ 

container # 

RF6#1 

RF1#3 

RF1#3 

RF1#4 

RF1#5 

RF3#1 

RF1 #5*6 

RF2#1 

RF4#1 

RF1#6 

RF6 #1/2 

RF6 #1/2/3 

RF2#2 

RF2#2 

RF1#6/7 

RF1#4/8 

RF4#2 

RF1 #4/8 

RF3#2 

RF3#2/3 

RF1#8/7 

RF1#8/#9 

RF4#3 

RF1#8/#9 

RF4#4 

Average (25 runs, w "Normal" run 1? 10) 

Average (24 mns, w/o "Normal" mn RIO) 

II. I- , 

Equip. 

REI 

RE2 

RE3 

RE3 

REI 

RE1 

REI 

RE1 

RE4 

RE1 

REI 

RE1 

RE1 

REI 

RE1 

RE3 

RE4 

RE2 

RE1 

REI 

REI 

RE1 

RE4 

RE2 

RE4 

RE1/RF1-AAA ext mix gun (6 runs, w/run R10) 

RE1/RF1-AAA ext mix gun (5 mns, w/o mn R10) 

RE2-Flow coater (3 mns) | 

RES-Pressure-fed roller (3 mns) .. . 

RE4-AAA ext mix gun for BPO system (see RF4) 

RF2-Low styrene Resin (3 mns) 

RF3-Styrene suppressed resin (3runs) 

RF4-BPO-Catalyzed Resin (4 mns) 

RF4-BPO-Catalyzed. Resin (2 mns, slow gel) 

RF4-BPO-Catalyzed Resin (2 mns, fast gel) 

RF5-Water emulsified resin (Not tested) 

RF6-Styrene suppressed resin plus wax (3 mns) 

Application 

Method 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Normal 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Controlled 

Air Vel. 

Low 

Low 

Low 

Low 

Low 

Low 

Low 

Low 

Low 

Low 

Low 

Low 

Low 

Low 

Low 

Low 

Low 

Low 

Low 

Low 

Low 

Low 

Low 

Low 

Low 

Avg. sqrt 

(delta P) 

0.3478 

0.3464 

0.3316 

0.3401 

0.3366 

0.3366 

0.3427 

0.3391 

0.3295 

0.3369 

0.3354 

0.3369 

0.3403 

0.3366 

0.3438 

0.3366 

0.3380 

0.3346 

0.3440 

0.3354 

0.3327 

0.3415 

0:3452 

0.3364 

0.3451 

0.3388 

0.3389 

0.3391 

0.3395 

0.3392 

0.3361 

0.3387 

0.3387 

0.3395 

0.3338 

0.3452 

NA 

0.3400 

Exhaust flow 

rate, cfm 

8710 

8683 

8399 

8563 

8495 

8495 

8613 

8543 

8358 

8501 

8471 

8501 

8566 

8495 

8633 

8495 

8521 

8457 

8637 

8471 

8419 

8589 

8661 

8492 

8658 

8537 

8539 

8542 

8550 

8544 

8486 

8535 

8534 

8550 

8440 

8659 

NA 

8561 

Avg. cone. 

ppm 

3.21 

3.97 

4.15 

3.63 

6.66 

4.08 

5.83 

5.59 

5.21 

7.95 

3.22 

2.55 

5.28 

5.43 

5.97 

4.51 

7.61 

4.52 

3.92 

3.91 

6.32 

6.15 

5.85 

4.38 

6.15 

5.04 

4.92 

6.48 

6.18 

4.29 

L 4.10 

5.44 

3.97 

6.20 

6.41 

6.00 

NA 

2.99 

Background 

cone, ppm 

0.35 

0.45 

0.46 

0.45 

0.39 

0.43 

0.77 

0.43 

0.46 

0.46 

0.42 

0.36 

0.27 

0.40 

0.37 

0.49 

0.51 

0.44 

0.29 

0.41 

0.45 

0.41 

0.30 

0.43 

0.62 

0.43 

0.43 

0.48 

0.48 

0.44 

0.46 

0.37 

0.38 

0.47 

0.48 

0.46 

NA 

0.38 

Avg. net 

cone, ppm 

2.86 

3.52 

3.70 

3.17 

6.27 

3.65 

5.05 

5.16 

4.76 

7.49 

2.81 

2.18 

5.01 

5.04 

5.59 

4.03 

7.10 

4.07 

3.63 

3.51 

5.87 

5.74 

5.55 

3.96 

5.53 

4.61 

4.49 

6.00 

5.71 

3.85 

3.63 

5.07 

3.59 

5.73 

5.93 

5.54 

NA 

2.62 

Test run 

duration, min 

103.1 

81.3 

75.0 

83.8 

67.3 

78.0 

75.7 

71.8 

152.4 

81.5 

91.3 

95.2 

76.5 

75.1 

76.5 

79.1 

102.6 

69.3 

75.6 

74.7 

77.2 

75.9 

88.9 

78.0 

85.1 

83.6 

83.7 

75.7 

74.5 

76.2 

79.3 

74.5 

76.1 

107.2 

127.5 

87.0 

NA 

96.5 

Total emissions 

by THC, g 

316 

305 

286 

279 

440 

296 

404 

389 

743 

636 

267 

217 

403 

394 

453 

332 

762 

293 

291 

272 

468 

459 

524 

322 

500 

402 

392 

477 

445 

306 

299 

395 

286 

632 

752 

512 

NA 

266 

SUMNEWJCLS 

Tl 

in 
Emission Measurements, Gravimetric Measurements, and Calculated Emissions and Factors 

m 

Date Time Test run # 

RESIN EXPERIMENT 

6/23/95 

6/23/95 

6/23/95 

6/26/95 

6/26/95 

6/26/95 

6/27/95 

6/27/95 

6/27/95 

6/28/95 

6/28/95 

6/28/95 

6/29/95 

6/29/95 

6/29/95 

6/30/95 

6/30/95 

6/30/95 

7/5/95 

" 7/5/95 

7/5/95 

7/6/95 

7/6/95 

7/6/95 

7/7/95 

11:06 

14:30 

16:35 

10:42 

13:27 

16:05 

10:46 

13:14 

15:51 

10:21 

12:45 

15:20 

10:22 

12:20 

14:36 

10:14 

13:13 

15:51 

11:53 

14:02 

16:19 

10:12 

14:34 

16:41 

10:10 

R1 

R2 

R3 

R4 

R5 

R6 

R7 

R8 

R9 

R10 

R11 

R12 

R13 

R14 

R15 

R16 

R17 

R18 

R19 

R20 

R21 

R22 

R23 

R24 

R25 

Material/ 

container # 

RF6#1 

RF1#3 

RF1#3 

RF1#4 

RF1#5 

RF3#1 

RF1 #5/#6 

RF2#1 

RF4#1 

RF1#6 

RF6#1/2 

RF6 #1/2/3 

RF2#2 

RF2#2 

RF1 #6/7 

RF1 #4/8 

RF4#2 

RF1 #4/8 

RF3#2 

RF3#2/3 

RF1 #8/7 

RF1 #8/#9 

RF4#3 

RF1 #8/#9 

RF4#4 

Average (25 runs* w "Normal" mn RIO) 

Average (24 runs, w/o "Normal" mn RIO) 

1 1 iv , 

Equip. 

REI 

RE2 

RE3 

RE3 

RE1 

RE1 

RE1 

REI 

RE4 

RE1 

REI 

RE1 

RE1 

RE1 

RE1 

RE3 

RE4 

RE2 

REI 

RE1 

RE1 

RE1 

RE4 

RE2 

RE4 

RE1/RF1-AAA ext mix gun (6 runs, w/ mn RIO) 

RE1/RF1-AAA ext mix gun (5 mns, w/o run R10) 

RE2-Flow coater (3 mns) | 

RE3-Pressure-fed roller (3 mns) 

RE4-AAA ext mix gun for BPO system (see Rl 

RF2^Low styrene Resin (3 mns) 

RF3-Styrene suppressed resin (3 runs) 

RF4-BPO-Catalyzed Resin (4 mns) 

RF4-BPO-Catalyzed Resin (2 mns, slow gel) 

RF4^BPO-Catalyzed Resin (2 mns, fast gel) 

RF5-Water emulsified resin (Not tested) 

=4) 

RF6-Styrene suppressed resin plus wax (3 runs) 

Avg. spraying 

cone, ppm 

40.88 

7.36 

7.31 

6.77 

58.52 

56.47 

65.93 

56.12 

73.79 

88.66 

44.67 

32.34 

52.43 

51.23 

60.23 

8.08 

56.67 

9.21 

53.18 

57.64 

57.03 

58.25 

50.51 

8.82 

58.01 

44.81 

42.98 

64.77 

59.99 

8.46 

7.39 

53.26 

55.77 

59.74 

65.23 

54.26 

NA 

39.30 

Avg. net 

spraying, ppm 

40.53 

6.91 

6.86 

6.32 

58.13 

56.04 

65.16 

55.69 

73.34 

88.20 

44.26 

31.98 

52.16 

50.83 

59.86 

7.60 

56.16 

8.77 

52.89 

57.24 

56.58 

57.83 

50:21 

8.39 

57.39 

44.37 

42.55 

64.29 

59.51 

8.02 

6.93 

52.90 

55.39 

59.27 

64.75 

53:80 

NA 

38.92 

Spraying 

time, min 

4.5 

23.0 

19.2 

21.4 

3.5 

3.3 

3.0 

3.3 

3.5 

3.4 

• 3.3 

2.9 

3.5 

3.6 

3.6 

27.9 

6!1 

13.9 

3.0 

3.0 

3.7 

3.4 

3.6 

15.3 

3.2 

7.5 

7.7 

3.4 

3.4 

17.4 

22.8 

3.5 

3.1 

4.1 

4.8 

3.4 

NA 

3.6 

Emissions 

during 

application 

(by THC) 

196 

169 

136 

142 

212 

193 

207 

195 

266 

310 

153 

97 

192 

191 

228 

221 

356 

126 

166 

180 

216 

207 

192 

134 

193 

195 

190 

230 

214 

143 

166 

192 

180 

252 

311 

193 

NA 

149 

Std. Dev. of 

application 

emissions 

(by THC) 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

55 

55 

36 

8 

19 

39 

2 

11 

67 

45 

0 

NA 

41 

Wt. loss from 

part during 

curing stage 

(by MB) 

71 

92 

135 

107 

193 

97 

187 

162 

451 

250 

85 

76 

175 

174 

204 

121 

314 

166 

78 

85 

210 

216 

262 

189 

262 

174 

171 

2.10 

202 

149 

121 

170 

87 

322 

383 

262 

NA 

77 

Std. Dev. of 

curing loss 

from part 

(by MB) 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

87 

87 

20 

11 

41 

11 

6 

8 

77 

69 

0 

NA 

6 

Wt. loss during 

application and from 

overspray, g 

(byMBl 

213 

243 

132 

173 

241 

205 

237 

199 

243 

357 

162 

127 

199 

192 

238 

215 

418 

99 

184 

188 

218 

215 

226 

100 

226 

210 

204 

2§1 

230 

147 

173 

197 

192 

278 

331 

226 

NA 

167 

SUMNEW.XLS 

Tl 

b> 
NP3 2 

OsEmission Measurements, Gravimetric Measurements, and Calculated Emissions and Factors 

Date Time Test run # 

RESIN EXPERIMENT 

6/23/95 

6/23/95 

6/23/95 

6726/95 

6/26/95 

6/26/95 

6/27/95 

6/27/95 

6/27/95 

6/28/95 

6/28/95 

6/28/95 

6/29/95 

6/29/95 

6/29/95 

6/30/95 

6/30/95 

6/30795 

7/5/95 

7/5/95 

7/5/95 

7/6/95 

7/6/95 

7/6/95 

7/7/95 

11:06 

14:30 

16:35 

• 10:42 

13:27 

16:05 

10:46 

13:14 

15:51 

10:21 

12:45 

15:20 

10:22 

12:20 

14:36 

10:14 

13:13 

15:51 

11:53 

14:02 

16:19 

10:12 

14:34 

16:41 

10:10 

Rl 

R2 

R3 

R4 

R5 

R6 

R7 

R8 

R9 

R10 

R11 

R12 

R13 

R14 

R15 

R16 

R17 

R18 

R19 

R20 

R21 

R22 

R23 

R24 

R25 

Material/ 

container # 

RF6#1 

RF1#3 

RF1 #3 

RF1#4 

RF1#5 

RF3#1 

RF1 #5/#6 

RF2#1 

RF4#1 

RF1#6 

RF6#1/2 

RF6 #1/2/3 

RF2#2 

RF2#2 

RF1 #6/7 

RF1#4/8 

RF4#2 

RF1 #4/8 

RF3#2 

RF3#2/3 

RF1#8/7 

RF1 #8/#9 

RF4#3 

RF1 #8/#9 

RF4#4 

Average (25 mns, w "Normal" mn RIO) 

Average (24 mns, w/o "Normal" run R10) 

•I I \ :. 

Equip. 

RE1 

RE2 

RE3 

RE3 

RE1 

REI 

REI 

RE1 

RE4 

REI 

RE1 

REI 

RE1 

RE1 

RE1 

RE3 

RE4 

RE2 

RE1 

REI 

REI 

RE1 

RE4 

RE2 

RE4 

RE1/RF1-AAA ext mix gun (6 runs, w/ mn R10) 

RE1/RF1-AAA ext mix gun (5 mns, w/o mn R10) 

RE2-Flow coater (3 mns) j 

RE3-Pressure-fed roller (3 mns) 

RE4nAAA ext mix gun for BPO system (see RF4) 

RF2-Low styrene Resin (3 mns) 

RF3-Styrene suppressed resin (3 mns) 

RF4-BPO-Catalyzed Resin (4 mns) 

RF4-BPO-Catalyzed Resin (2 mns, stow gel) 

RF4-BPO-Catalyzed Resin (2 runs, fast gel) 

RF5-Water emulsified resin (Not tested) 

RF6-Styrene suppressed resin plus wax (3 mns) 

Total emissions 

by MB, g 

284 

335 

267 

280 

434 

302 

424 

361 

694 

607 

247 

203 

374 

366 

442 

336 

732 

265 

262 

273 

428 

431 

488 

289 

488 

384 

375 

461 

432 

296 

294 

367 

279 

601 

713 

488 

NA 

•245 

Ratio of two 

measurement 

methods 

(MB/THC) 

0.90 

1.10 

0.93 

1.00 

0.99 

1.02 

1.05 

0.93 

0.93 

0.95 

0.93 

.0.94 

0.93 

0.93 

0.98 

1.01 

0.96 

0.90 

0.90 

1.00 

0.91 

0.94 

0.93 

0.90 

0.98 

0.96 

0.96 

0.97 

0.97 

0.97 

0.98 

0.93 

0.97 

0.95 

. 0.95 

0.95 

NA 

0.92 

Material 

used, g 

7712 

5445 

4919 

5041 

5978 

5663 

6160 

5979 

6116 

6133 

5152 

4872 

6566 

6870 

7000 

5328 

7467 

. 5371 

6689 

6423 

6958 

7256 

5606 

6040 

5698 

6098 

6096 

6581 

6670 

5619 

5096 

6472 

6258 

6222 

6792 

5652 

NA 

5912 

Transfer 

eff. % 

92.7 

96.2 

97.2 

97.3 

90.8 

91.7 

91.0 

91.4 

88.7 

80.5 

89.9 

92.7 

91.4 

93.2 

92.6 

• 96.7 

79.5 

97.7 

92.9 

92.9 

92.2 

93.5 

91.7 

97.9 

91.9 

92.2 

92.7 

90.1 

92.0 

97.3 

97.1 

92.0 

92.5 

88.0 

84.1 

91.8 

NA 

91.8 

Styrene 

content, % 

43.29 

36.33 

38.33 

38.33 

38.33 

43.45 

38.33 

35.34 

42.61 

38.33 

43.29 

43.29 

35.34 

35.34 

38.33 

38:33 

42.61 

38.33 

43.45 

43:45 

38:33 

38.33 

42.6f 

38.33 

42.61 

39.87 

39.93 

38.33 

38.33 

38.33 

38.33 

35.34 

43.45 

42.61 

42.61 

42.61 

NA 

43.29 

I 

EF, % available styrene 

by THC 

9.5 

14.6 

15.2 

14.5 

19.2 

12.0 

17.1 

18.4 

28.5 

27.1 

12.0 

10.3 

17.4 

16.2 

16.9 

16.3 

23.9 

14.2 

10.0 

9.8 

17.5 

16.5 

21.9 

13.9 

20.6 

16.5 

16.1 

19.1 

17.5 

14.2 

15.3 

17.3 

10.6 

23.7 

26.2 

21.3 

NA 

10.6 

by MB 

8.5 

16.1 

14.2 

14.5 

18.9 

12.3 

18.0 

17.1 

26.6 

25.8 

11.1 

9.6 

16.1 

15.1 

16.5 

16.5 

23.0 

12.9 

9.0 

. 9.8 

16.0 

15.5 

20.4 

12.5 

20.1 

15.8 

15.4 

18.5 

17.0 

13.8 

15.0 

16.1 

10.4 

22.5 

24.8 

20.3 

NA 

9.7 

1 Std. Dev., % AS 

by THC 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

4.9 

4.9 

3.7 

0.9 

0.3 

0.7 

0.9 

1.0 

3.0 

2.3 

0.7 

NA 

1.0 

by MB 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

4.7 

4.7 

3.5 

1.3 

1.6 

1.0 

0.8 

1.4 

2.6 

1.8 

0.2 

NA 

1.1 

Total mold 

surface, m2 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

2.28 

NA 

2.28 

SUMNEW.XLS 

Tl 
Emission Measurements, Gravimetric Measurements, and Calculated Emissions and Factors 

-g 11 

Date Time Test mn # 

RESIN EXPERIMENT 

6/23/95 

6/23/95 

6/23/95 

6/26/95 

6/26/95 

6/26/95 

6/27/95 

6/27/95 

6/27/95 

6/28/95 

6/28/95 

6/28/95 

6/29/95 

6/29/95 

6/29/95 

6/30/95 

6/30795 

6/30/95 

7/5/95 

7/5/95 

7/5/95 

7/6/95 

7/6/95 

7/6/95 

7/7/95 

11:06 

14:30 

16:35 

10:42 

13:27 

16:05 

10:46 

13:14 

15:51 

10:21 

12:45 

15:20 

10:22 

12:20 

14:36 

10:14 

13:13 

15:51 

11:53 

14:02 

16:19 

10:12 

14:34 

16:41 

10:10 

R1 

R2 

R3 

R4 

R5 

R6 

R7 

R8 

R9 

R10 

R11 

R12 

R13 

R14 

R15 

R16 

R17 

R18 

R19 

R20 

R21 

R22 

R23 

R24 

R25 

Material/ 

container # 

RF6#1 

RF1#3 

RF1#3 

RF1#4 

RF1#5 

RF3#1 

RF1 #5/#6 

RF2#1 

RF4#1 

RF1#6 

RF6#1/2 

RF6 #1/2/3 

RF2#2 

RF2#2 

RF1 #6/7 

RF1#4/8 

RF4#2 

RFl#4/8 

RF3#2 

RF3#2/3 

RFl#8/7 

RF1,#8/#9 

RF4#3 

RF1 #8/#9 

RF4#4 

; 

Average (25 run's,, w "Normal" run R10) 

Average (24 mns, w/o "Normal" mn R10) 

I \; . r .. 

Equip. 

RE1 

RE2 

RE3 

RE3 

RE1 

RE1 

REI 

REI 

RE4 

RE1 

RE1 

RE1 

RE1 

RE1 

RE1 

RE3 

RE4 

RE2 

RE1 

RE1 

REI 

RE1 

RE4 

RE2 

RE4 

RE1/RFT-AAA ext mix gun (6 mns, w/ run R10) 

RE1/RF1-AAA ext mix gun (5 runs, w/o mn R10) 

RE2-Flow coater (3 mns) | 

RE3-Pressure-fed roller (3 runs) 

RE4-AAA ext mix gun for BPO system (see RF4) 

RF2-Low styrene Resin (3 mns) 

RF3-Styrene suppressed resin (3 runs) 

RF4-BPO-Catalyzed Resin (4 mns) 

RF4-BPO-Catalyzed Resin (2 mns, slow gel) 

RF4-BPO-Catalyzed Resin (2 runs, fast gel) 

RF5-Water emulsified resin (Not tested) 

RF6-Styrene suppressed resin plus wax (3 runs) 

I 

EF, g/m2 

by THC 

138 

134 

125 

123 

193 

130 

177 

170 

326 

279 

117 

95 

177 

173 

199 

146 

334 

129 

127 

119 

205 

201 

230 

141 

219 

175 

172 

209 

195 

134 

131 

173 

126 

277 

330 

225 

NA 

117 

by MB 

125 

147 

117 

123 

190 

132 

186 

158 

304 

266 

108 

89 

164 

161 

194 

147 

321 

116 

115 

120 

188 

189 

214 

127 

214 

167 

165 

202 

189 

130 

129 

161 

122 

263 

313 

214 

NA 

107 

1 • 

Std. Dev., g/m2 

by THC 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

62.0 

62.0 

32.5 

9.8 

5.1 

10.3 

2:7 

4.5 

52.9 

4.0 

5.4 

NA 

17.7 

by MB 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

58.8 

58.8 

28.7 

2.7 

12.7 

13.1 

2.3 

7.4 

49.7 

8.3 

0.0 

NA 

14.5 

I 

EF, g/g material 

by THC 

0.041 

0.056 

0.058 

0.055 

0.074 

0.052 

0.066 

0.065 

0.122 

0.104 

0.052 

0.044 

0.061 

. 0.057 

0.065 

. 0.062 

0.102 

0.055 

0.043 

0.042 

0.067 

0.063 

0.094 

0.053 

0.088 

0.065 

0.064 

0.073 

0.067 

0.055 

0.059 

0.061 

0.046 

0.101 

0.112 

0.091 

NA 

0.046 

by MB 

0.037 

0.062 

0.054 

0.056 

0.073 

0.053 

0.069 

0.060 

0.113 

0.099 

0.048 

0.042 

0.057 

0.053 

0.063 

0.063 

0.098 

0.049 

0.039 

0.043 

0.062 

0.059 

0.087 

0.048 

0.086 

0.062 

0.061 

0.071 

0.065 

0.053 

0.058 

0.057 

0.045 

0.096 

0.106 

0.086 

NA 

6.042 

I 

Std. Dev., g/g 

by THC 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

. NA 

NA 

NA 

NA 

0.020 

0.020 

0.014 

0.004 

0.001 

0.003 

0.003 

0.004 

0.013 

0.010 

0.003 

NA 

0.004 

by MB 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

NA 

0.019 

0.019 

0.013 

0.005 

0.006 

0.004 

0.003 

0.006 

0.011 

0.008 

0.001 

NA 

0.005 

Catalyst 

Ratio, % 

1.50 

1.45 

1.65 

1.61 

1.46 

1.45 

1.46 

1.47 

1.67 

1.45 

1.44 

1.48 

1.42 

1.41 

1.47 

1.69 

2.50 

1.51 

1.44 

1.46 

1.45 

1.47 

3.12 

1.52 

3.09 

1.67 

1.67 

1,46 

1.46 

1.49 

1.65 

1.43 

1.45 

2.60 

2.09 

3.11 

NA 

1.47 

Glass/Resin 

Ratio, % 

29.2 

32.0 

33.6 

33.8 

33.0 

34.6 

32.4 

33.2 

34.3 

32.2 

33.4 

33.3 

34.8 

32.9 

32.6 

32.4 

35.4 

32.7 

30.0 

31.9 

32:7 

31.1 

37.5 

30.6 

38.1 

33.1 

33.1 

32.3 

32.4 

31.8 

33.3 

33.6 

32.2 

36.3 

34.9 

37.8 

NA 

32.0 

SUMNEW.XLS 

Tl 

00 
P.9 

Appendix F 

Statistical Analyses of Test Results 

Table of Contents 

Section Page No. 

F. 1 Pilot Experiment F-l 

F.2 Geicoat Experiment F-8 

F.3 Resin Experiment F-l5 

F.4 Summary F-23 

F-i 
P.10 

List of Tables 

Table No. Page No. 

1 Analysis of variance results for pilot study F-3 

2 Estimated mean differences and 95% confidence interval estimates 

for normal vs. controlled application methods in the pilot experiment F-4 

3 Confidence limits for pilot study: high vs. low air velocity F-5 

4 Within-cell standard deviations-pilot study data F-5 

5 Analysis of covariance results for pilot study F-7 

6 Analysis of variance results for geicoat experiment F-9 

7 Confidence limits for geicoat study: regular vs. low VOC gelcoats F-10 

8 Confidence limits for geicoat study: different spray guns F-l 1 

9 Within-cell standard deviations—geicoat experiment F-12 

10 Analysis of covariance results for geicoat experiment F-14 

11 Analysis of variance results for resin experiment F-17 

12 Estimated mean differences and confidence interval estimates for percent 

available styrene: resin experiment F-18 

13 Estimated mean differences and confidence interval estimates for emission 

factor (g/m2): resin experiment F-l9 

14 Estimated mean differences and confidence interval estimates for emission 

factor (g/g): resin experiment F-20 

15 Within-treatment standard deviations—resin experiment F-21 

16 Analysis of covariance results for resin experiment F-22 

17 Summary of results of specific hypothesis tests F-23 

F-ii 

qtp' 
P.11 

F.l Pilot Experiment. 

Before executing the main experiment, a pilot study was conducted to help establish 

"standard" conditions under which the subsequent experiments should be conducted. A 

secondary purpose was to gain insight into the magnitude of measurement error variability that 

might be anticipated in the main experiment. The pilot study was run as a factorial experiment 

involving two factors: M = spraying method, and A = air velocity. The experiment consisted of 

12 trials — namely, three replicates for each of the following conditions: 

(a) 

(b) 

(c) 

(d) 

Normal spraying method (Ml), low air velocity (Al) 

Controlled spraying method (M2), low air velocity (Al) 

Normal spraying method (Ml), high air velocity (A2) 

Controlled spraying method (M2), high air velocity (A2) 

A single geicoat formulation (GFl) and a single application equipment (GE1) were used 

throughout the pilot experiment. The 12 trials were run in a random order. 

Although it was recognized that the pilot study would provide only a limited amount of 

statistical information, the resultant data were subjected to statistical analysis in order to get some 

idea of the impact of the two factors on percent available styrene (%AS) and other related 

measures. The specific outcome measures that were analyzed are the following: 

Variable 

X 

Zl 

Z2 

Yl 

Y2 

Y3 

Y4 

Y5 

Y6 

Y7 

Y8 

Description 

Transfer Efficiency (%) (standardized to have mean 0) 

Total Emissions (g), by THC 

Total Emissions (g), by MB 

Emissions during the application stage (g), by THC 

Curing Loss from Part (g), by MB 

EF (% Available Styrene), by THC 

EF (% Available Styrene), by MB 

EF (g/m2), by THC 

EF (g/m2), by MB 

EF (g/g), by THC 

EF (g/g), by MB 

F'l 

QA 
P.12 

The x variable was considered a possible coovariate for the Zl and Z2 variables; as a result, the 

X variable was standardized to have a zero mean. 

For each variable, an initial analysis of variance (ANOVA) of the following form was performed: 

SOURCE OF DEGREES OF 

VARIATION FREEDOM 

M (methods) 1 

A (air flow) 1 

M x A (interaction) 1 

Error 8 

Total 11 

In each case, the interaction term appeared statistically nonsignificant; hence the interaction term 

was dropped to produce an ANOVA as follows: 

SOURCE OF DEGREES OF 

VARIATION FREEDOM 

M (methods) 1 

A (air flow) 1 

Error 9 

Total 11 

The results of the above analyses are summarized in Table 1 for the X variable and each 

of the Ys (the two Z variables are considered subsequently). The upper portion of the table gives 

means of the pertinent variables for each combination of the M and A factors. These rows are 

followed by rows giving the means separately for each level of each factor. The lower portion of 

the table provides information relating to the statistical tests. The first row gives the root mean 

squared error (RMSE); this is equivalent to the pooled within-cell variance. This is used to test 

whether, there is a METHOD by AIR VELOCITY interaction. The test results, summarized in 

the next row, show these interactions to be statistically nonsignificant (n.s.). Consequently, a 

new RMSE for testing the main effects of the factors is constructed (by pooling of the former 

RMSE and the interaction mean square); these RMSEs, based on 9 degrees of freedom (df), are 

displayed in the next row of Table 1. Results of the tests for main effects are given in the last 

two rows of the table. The effect of AIR VELOCITY is statistically nonsignificant, although the 

low velocity exhibited lower estimated values than the high velocity for each of the Y variables. 

For the METHOD effect, statistically signficant differences were found for several of the 

variables: the controlled spraying, as contrasted with the normal spraying, yielded a higher 

transfer efficiency (0.01 level), and lower average spraying emissions, percent available styrene, 

F-2 

<$> 
Tl 

i 

TABLE 1. Analysis of Variance Results for Pilot Study: Variables X, Yl, Y2,... , and Y8 

Means, by variable: 

n Xa Yl Y2 

Application Air 

method velocity 

Controlled High 

Controlled Low 

Normal High 

Normal Low 

Controlled 

Normal 

High 

Low 

Hypothesis Testing Results 

RMSE for testing 

interaction (8 df): 

Test for interaction: 

RMSE for testing main 

effects (9 df): 

Test for METHOD: 

Test for AIR VELOCITY: 

Y3 Y4 Y5 Y6 

3 

3 

3 

3 

6 

6 

6 

6 

4.1 

4.5 

-6.4 

-2.2 

4.3 

-4.3 

-1.2 

1.2 

3.16 

n.s. 

3.17 

n.s. 

n.s. n.s. n.s. n.s. n.s. n.s. 

n.s. n.s. 

*** 

Y7 Y8 

157.0 

137.7 

259.0 

231.3 

147.3 

245.2 

208.0 

184.5 

31.50 

223.0 

204.0 

209.3 

225.7 

213.5 

217.5 

216.2 

214.8 

21.74 

56.3 

52.0 

62.1 

62.9 

54.1 

62.5 

59.2 

57.5 

3.71 

59.7 

58.4 

•62.5 

59.2 

59.1 

60.9 

61.1 

58.8 

7.34 

180.3 

163.3 

225.7 

225.0 

171.8 

225.3 

203.0 

194.2 

15.76 

190.0 

183.0 

228.0 

211.7 

186.5 

219.8 

209.0 

197.3 

25.85 

0.218 

0.201 

0.241 

0.244 

0.210 

0.242 

0.229 

0.223 

0.014 

0.231 

0.226 

0.242 

0.229 

0.229 

0.236 

0.237 

0.228 

0.028 

n.s n.s 

29.79 22.89 3.80 6.95 15.59 24.52 0.015 0.027 

n.s. n.s. n.s. n.s. n.s. n.s. 

n.s 

n.s. n.s. 

* = statistically significant at the 0.05 level 

** = statistically significant at the 0.01 level 

*** = statistically significant at the 0.001 level 

'Overall mean for X prior to standardization was 79.96. 
P.14 

and emission factor (EF), as measured by THC. When measured via the mass balance (MB) 

approach, only the EF variable appeared statistically significant (at the 0.05 level). 

Point estimates and confidence interval estimates for the differences due to application 

methods and air velocities are shown in Tables 2 and 3, respectively. 

In Tables 2 and 3, the construction of the confidence intervals is based on an assumption 

that the data for a given combination of METHOD and AIR VELOCITY are approximately 

normally distributed with a common measurement error variability (the same assumption applies 

to the hypothesis tests previously described, and similar assumptions apply to all other 

confidence intervals described herein). Cell-specific estimates of the measurement error 

variablity (or standard deviations) are shown in Table 4. The 95 percent confidence interval on 

the difference is related to a pairwise hypothesis test (conducted at a significance level of 0.05) in 

that if the estimated confidence interval does not include zero, then the corresponding test of no 

difference in mean %AS will be rejected. 

TABLE 2. Estimated Mean Differences and 95% Confidence Interval Estmates for 

Normal Vs. Controlled Application Methods in the Pilot Experiment 

Variable and comparison 

X - Transfer efficiency (%) 

Zl - Total emissions by THC (g) 

Z2 - Total emissions by MB (g) 

Yl - Application emissions by THC 

(g) 

Y2 - Curing loss from part by MB (g) 

Y3 - EF as % AS by THC 

Y4 - EF as % AS by MB 

Y5 - EF as g/m2 by THC 

Y6 - EF as g/m2 by MB 

Y7 - EF (g/g) by THC 

Y8 - EF (g/g) by MB 

Lower 95% 

confidence 

limit 

-12.79 

76.40 

3.88 

58.92 

-25.90 

3.44 

-7.29 

33.14 

1.31 

0.0134 

-0.0282 

Esitmated 

mean 

difference 

-8.65 

121.83 

76.33 

97.83 

4.00 

8.40 

1.78 

53.50 

33.33 

0.0325 

0.0069 

Upper 95% 

confidence 

limit 

-4.51 

167.27 

148.79 

136.75 

33.90 

13.36 

10.86 

73.86 

65.35 

0.0516 

0.0420 

Significant 

** 

*** 

' * 

*** 

n.s 

** 

n.s 

*** 

* 

* 

n.s. 

* = Statistically significant at the 0.05 level. 

* * = Statistically significant at the 0.01 level. 

*** = Statistically significant at the 0.001 level, 

n.s. = Not statistically significant at the 0.05 level. 

F-4 

190 
P.15 

TABLE 3. Confidence Limits for Pilot Study: High Vs. Low Air Velocity 

Variable and comparison 

X - Transfer efficiency % 

Zl - Total emissions by THC (g) 

Z2 - Total emissions by MB (g) 

Yl - Application emissions by 

THC (g) 

Y2 - Curing loss from part by MB 

(g) 

Y3 - EF as % AS by THC 

Y4 -EFas%ASbyMB 

Y5 - EF as g/m2 by THC 

Y6 - EF as g/m2 by MB 

Y7 - EF (g/g) by THC 

Y8 -EF (g/g) by MB 

Lower 95% 

confidence 

limit 

-6.45 

-25.27 

-46.12 

-15.41 

-28.56 

-3.20 

-6.73 

-11.53 

-20.35 

-0.0122 

-0.0260 

Esitmated 

difference 

-2.32 

20.17 

26.33 

23.50 

1.33 

1.77 

2.35 

8.83 

11.67 

0.0069 

0.0091 

mean Upper 95% 

confidence 

limit 

1.82 

65.60 

98.79 

62.41 

31.23 

6.73 

11.43 

29.20. 

43.69 

0.0260 

0.0442 

Significant 

n.s. 

n.s. 

n.s. 

n.s. 

n.s. 

n.s. 

n.s 

n.s. 

n.s. 

n.s. 

n.s 

n.s = Not statistically significant at the 0.05 level. 

TABLE 4. Within-cell Standard Deviations - Pilot Study Data 

METHOD AIRVEL Zl Z2 Yl Y2 Y3 Y4 Y5 Y6 Y7 Y8 

Controlled 

Controlled 

Normal 

Normal 

High 

Low 

High 

Low 

2.6 24.7 

2.7 43.0 

4.7 30.4 

2.0 39.3 

39.4 

38.7 

97.0 

35.1 

19.0 

6.4 

48.3 

35.2 

11.1 

32.1 

23.2 

14.2 

3.1 

1.3 

3.2 

5.8 

9.8 

4.3 

9.4 

3.5 

10.8 

19.3 

13.8 

17.7 

17.3 

17.1 

42.9 

15.4 

0.012 

0.005 

0.012 

0.022 

0.038 

0.017 

0.036 

0.013 

F-5 

/bi 
P.16 

For the two total emission variables (Zl and Z2), an initial analysis of covariance 

(ANACOVA) of the following form was performed: 

SOURCE OF VARIATION DEGREES OF FREEDOM 

X (transfer efficiency) 1 

M (methods) 1 

A (air flow) 1 

M x A (interaction) 1 

Error 7 

Total 11 

Since in each case the interaction term appeared statistically nonsignificant, that term was 

dropped to produce the following: 

SOURCE OF VARIATION DEGREES OF FREEDOM 

X (transfer efficiency) 1 

M (methods) 1 

A (air flow) 1 

Error 8 

Total 11 

The results are summarized in Table 5. The format of the table is similar to that of Table 1 in 

that the upper portion shows means by cells and factor levels and the lower portion gives RMSEs 

and results of hypothesis tests. In this case, the hypothesis tests are performed on means of the Z 

variables after adjustment for the covariate X (assuming a linear relaionship between a Z and X). 

(The ANOVA results for the Z variables (i.e., ignoring adjustments for X) are shown in the lower 

left portion of the table while the ANACOVA results are given in the lower right portion.) The 

adjusted means are given in the upper righthand part of the table. Total emissions by THC 

(variable Zl) appear to be affected (0.05 significance level) by spraying method, while AIR 

VELOCITY and X appear to have nonsignificant effects on Zl. Neither factor A or M nor the 

covariate X appears to affect variable Z2. As noted previously (see Table 1), the METHOD 

factor appears to affect the covariate X and this situation can lead to problems with 

interpretation. For instance, it is not clear whether METHOD affects X only, which in turn 

induces differences in the Zl variate, or whether (at least part of) the effect of METHOD on Zl a 

direct effect (i.e., not related to the difference in X levels). 

F-6 

\o% J 
P.17 

TABLE 5. Analysis of Covariance Results for Pilot Study: Variables Zl and Z2 

MEANS MEANS ADJUSTED FOR X 

METHOD AmVEL N X Z l Z2 Zl Z2 

Controlled 

Controlled 

Normal 

Normal 

Controlled 

Normal 

High 

Low 

High 

Low 

High 

Low 

3 

3 

3 

3 

6 

6 

6 

6 

4.1 

4.5 

-6.4 

-2.2 

4.3 

-4.3 

-1.2 

1.2 

410.3 

371.7 

513.7 

512.0 

391.0 

512.8 

462.0 

441.8 

432.3 

416.3 

519.0 

482.3 

424.3 

500.7 

475.7 

449.3 

413.7 

375.4 

508.4 

510.2 

389.1 

514.7 

462.5 

441.3 

477.9 

466.8 

447.7 

457.6 

469.5 

455.5 

463.6 

461.4 

Hypothesis Testing Results: 

RMSE for testing 

interaction (8 df): 

(7df): 

35.1 58.5 

37.4 50.1 

Test for interaction: n.s. n.s. n.s. n.s. 

RMSE for testing main 

effects (9 df): 

(and covariate) (8 df): 

4.8 55.5 

36.9 47.2 

Test for METHOD: *** n.s. 

Test for AIR VELOCITY: n.s. n.s. n.s. n.s. 

Test for covariate X: n.s. n.s. 

* = statistically significant at the 0.05 level 

** = statistically significant at the 0.01 level 

*** = statistically significant at the 0.001 level 

F-7 

Yas 
F.2 Geicoat Experiment. 

This experiment is aimed at evaluating how styrene emissions are affected by geicoat 

formulation (factor GF) and type of equipment (factor GE). The factor combinations (two 

formulations and three equipment types) were each run in triplicate, with trials run in a random 

order (i.e., a 2x3 factorial experiment with three replications embedded in a completely random 

design). The analysis, which was conducted for the X variate and each of the previously defined 

Y variates, entailed conducting an analysis of variance (ANOVA) having the following structure: 

SOURCE OF VARIATION DEGREES OF FREEDOM 

GF (gelcoats) 1 

GE (equipments) 2 

GF x GE (interaction) 2 

Error 12 

Total 17 

In each case, the interaction term appeared statistically nonsignificant; hence the interaction term 

was dropped to produce an ANOVA as follows: 

SOURCE OF VARIATION DEGREES OF FREEDOM 

GF (gelcoats) 1 

GE. (equipments) 2 

Error 14 

Total 17 

The results are summarized in Table 6. The format of this table is similar to that described for 

Table 1: the upper portion gives means of the pertinent variables for each combination of the GF 

and GE factors, the middle portion shows the means separately for each level of each factor, and 

the lower portion gives the pertinent RMSEs and hypothesis testing results. With one exception 

(a difference in variable Yl for GE2 and GE3, at the 0.05 level of significance), the effect of 

EQUIPMENT is statistically nonsignificant. For the geicoat FORMULATIONS effect, 

statistically signficant differences were found for the X variable (0.05 level) and for several of 

the Y variables (Yl, Y2, Y5, and Y6, all highly significant). Statistically significant differences 

for the GF and GE factors were not found for the percent available styrene variables (Y3 and 

Y4). 

Point estimates and confidence interval estimates for the differences due to two gel coat 

formulations and three spray guns are shown in Tables 7 and 8, respectively. The with-in cell 

standard deviations for gel coat experiment are shown in Table 9. 

F-8 

/fA 
P.19 

Ov CN O rf — CN 

GO — Ol CN rt f- rt 

^, CN CN CN — — — 

d <5 CD d <6 o 

o 

CN 

CN 

CN 

UO 

*•"* 

— vo 

00 ON 

_ _«, 

_-

00 

~-

© o o o o 

r-

© 

© 

ro 

d 

* * * cf 

uooooovor^ o r-- r- o o\ CN 

r- CN O — ro ro rt — ro oor^r ~ 

^ , CN CN CN — — — CN — —. —. — 

d <z> d> d> d d> d o od d 

CM 

O 

d 

o 

d 

* 

v. 

Z 

w 

O ro r~; O ro O 

vo —• rt r i vd ro K 

>, r- t-- r- CN >o CN 

r-~ o ro o O r^ 

! 2 uo r t O ON CN rt 

?• r~ VO P- - N N 

r^ 

(N 

r— 

rt 

uo 

ro 

uo 

00 

rt 

00 

ro 

vo 

oo 

ON 

rt 

O ON 

d ~ 

r~- CN 

ro p uo 

r^ ro r^ 

rt rt rt 

ro 

ro 

rt 

ON 

r-' * 

uo * 

•— * * 00 

</5 

X 

Vi 

CU 

S 

« 

la 

CO 

> 

rr 

> 

ro 

uo CN oo r~ uo CN CN oo vo rt uo 

vo r- vo vo r— vo 

UO UO UO UO VO UO 

o VO 

vO 

UO 

VO CN vo 

uo vo IO 

o 

oo 

U0 

oo 

ro 

uo 

ro 

vO 

UO 

00 

ro 

UO 

ON 

ro 

uo 

— 

uo 

uo 

o 

VO 

uo 

CN 

rt 

UO 

ON 

uo 

uo 

oo 

CO 

uo 

r» 

uo 

>o 

00 

uo 

uo 

CN 

vq 

ro 

oo 

oo 

uo 

ro 

c/i 

c 

tn 

c 

C 

V S 

'E 

0) 

a 

es © 

u 

a 

3 

CA 

CU 

PS 

a> 

u 

C 

.2 'E 

> 

© 

.cw 

*55 

^ > 

Is 

C 

veW 

J 

ca 

o p p r-; r~; ro 

r? CN r t UO r~ ON ON 

>" — O — uo uo uo 

CN CN CN — — — 

ro ro r- © © © 

r* — O ro r t d —^ 

>< uo vo r t ON O ON 

« uo vq uo i o uo VD 

X — —I d CN —• CN 

Z ro ro ro ro ro ro 

5 . — o> ro — CN ro 

C U J UJ UJ UJ LU UJ 

W O O O O O O 

— — — CN CN CN 

fc. LL, U- U - LL, U- U . 

OOOOOO O 

ro 210 

00 

UO 

ON 158 

o 

uo 

ON 

00 184 

rCN 

CN 

oo 

00 

X 

CN 

o 

ro 

CN 187 

X 

ro 

r— 

CN CN 

ON ON 

— CN 

LL. LL, 

o o 

uo uo — 

d - r - -

vo vo vo 

uo 

ON 

ON 

CO 

NO 

CN 

rt 

uo 

Ov 

* * * 

* * * 

00 

CN 

CN 

— CN ro 

LU LU LU 

O O O 

<3 

"3 

cn 

cu 

POJS ) 

c 

cn cu H 

cn hesi ypot 

SC 

w j O 

C "O testi (12 for tion MSE terac 

DS .5 

B 

O 

CJ 

?3 

C3 

£ 

tn O 

.S2 

(Zl 

Z 

o 

p 

< 

D 

Oi 

O 

tti M <2 

W o ^ 

« fa U 

Cd ^ 3 H 

H 

Z 

w 

S 

S3 

a 

w 

cn 

H 

vO 

uo 

ro 

00 

> > — * 

cj CJ o * 

> c 

ui — u o 

o o — -x 

ddg S 

CJ CJ O • -

•S •£ <5? 

~ - 7.

 a 

o CJ _g •o 

e c Z B 

co 03 rt wj 

L> O w _ 

c c e 2 

'= '= S fe 

eo oo (2 .2 

•55 •« -E £_ 

•« "3 '* ^ 

•=• = = >£ 

« ui rt 

2 2 

wi to •S i 

" > C J 

ii 5 

* O 

F-9 /d? ^ 
TABLE 7. Confidence Limits for Geicoat Study: Regular Vs. Low Voc Gelcoats 

Variable and comparison 

X - Transfer efficiency % 

Zl - Total emissions by THC (g) 

Z2 - Total emissions by MB (g) 

Yl - Application emissions by THC 

(g) 

Y2 - Curing loss from part by MB (g) 

Y3 - EF as % AS by THC 

Y4 - EF as % AS by MB 

Y5 - EF as g/m2 by THC 

Y6 - EF as g/m2 by MB 

Y7 - EF (g/g) by THC 

Y8 -EF (g/g) by MB 

Lower 95% 

confidence limit 

-4.70 

90.44 

46.63 

48.72 

45.98 

-1.76 

-9.27 

39.87 

19.72 

0.0680 

0.0505 

Esitmated 

mean 

difference 

-2.39 

109.00 

86.78 

56.78 

51.44 

1.79 

-3.32 

48.11 

37.22 

0.0796 

0.0678 

Upper 95% 

confidence 

limit 

-0.08 

127.56 

126.93 

64.83 

56.91 

5.34 

2.62 

56.36 

54.73 

0.0912 

0.0851 

Significant 

* 

*** 

*** 

***' 

*** 

n.s. 

n.s. 

*** 

*** 

*** 

*** 

* = Statistically significant at the 0.05 level. 

** = Statistically significant at the 0.01 level. 

*** = Statistically significant at the 0.001 level. 

n.s. = Not statistically significant at the 0.05 level. 

F-10 

(0®: 
P.21 

TABLE 8. Confidence Limits for Geicoat Study: Different Spray Guns 

Variable and comparison 

Lower 95% 

confidence 

limit 

Comparison between AAA vs. HVLP (internal mix) 

X - Transfer efficiency % 

Zl - Total emissions by THC (g) 

Z2 - Total emissions by MB (g) 

Yl - Application emissions by THC (g) 

Y2 - Curing loss from part by MB (g) 

Y3 - EF as % AS by THC 

Y4 -EFas%ASbyMB 

Y5 - EF as g/m2 by THC 

Y6 - EF as g/m2 by MB 

Y7 - EF (g/g) by THC 

Y8 -EF (g/g) by MB 

Comparison between AAA vs. HVLP (extern* 

X - Transfer efficiency % 

Zl - Total emissions by THC (g) 

Z2 - Total emissions by MB (g) 

Yl - Application emissions by THC (g) 

Y2 - Curing loss from part by MB (g) 

Y3 -EFas%ASbyTHC 

Y4 - EF as % AS by MB 

Y5 - EF as g/m2 by THC 

-0.79 

-12.90 

-83.84 

-17.37 

-3.69 

-2.28 . 

-13.05 

-5.76 

-36.77 

:0.0063 

-0.0363 

il mix) 

-3.39 

-22.56 

-52.34 

-4.53 

-9.03 

-4.15 

-7.18 

-10.26 

Esitmated 

mean 

difference 

2.03 

9.83 

-34.67 

-7.50 

3.00 

2.07 

-5.77 

4.33 

-15.33 

0.0080 

-0.0151 

-0.57 

0.17 

-3.17 

5.33 

-2.33 

0.20 

0.10 

-0.17 

Upper 95% 

confidence 

limit 

4.86 

32.56 

14.50 

2.37 

9.69 

6.41 

1.51 

14.43 

6.11 

0.0222 

0.0062 

2.26 

22.90 

46.00 

15.20 

4.36 

4.55 

7.38 

9.93 

Significant 

n.s. 

n.s. 

n.s. . 

n.s. 

n.s. 

n.s. 

n.s. 

n.s. 

n.s. 

n.s. 

n.s. . 

n.s. 

n.s. 

n.s. 

n.s. 

n.s. 

n.s. 

n.s. 

n.s. 

n.s. 

F-l 1 

(cont.) 

/Ah 
P.22 

TABLE 8. Continued 

Variable and comparison 

Y6 - EF as g/m2 by MB 

Y7 - EF (g/g) by THC 

Y8 - EF (g/g) by MB 

Lower 95% Esitmated Upper 95% 

confidence mean confidence 

limit difference limit Significant 

-22.77 -1.33 20.11 n.s. 

-0.0127 0.0016 0.0158 n.s 

-0.0212 0.0000 0.0213 n.s. 

Comparison between HVLP (int) vs. HVLP (external mix) 

X - Transfer efficiency % 

Zl - Total emissions by THC (g) 

Z2 - Total emissions by MB (g) 

Yl - Application emissions by THC (g) 

Y2 - Curing loss from part by MB (g) 

Y3 - EF as % AS by THC 

Y4 - EF as % AS by MB 

Y5 - EF as g/m2 by THC 

Y6 - EF as g/m2 by MB 

Y7 - EF (g/g) by THC 

Y8 -EF (g/g) by MB 

-5.43 -2.60 0.23 n.s. 

-32.40 -9.67 13.06 n.s. 

-17.67 31.50 80.67 n.s. 

2.97 12.83 22.70 . * 

-12.03 -5.33 1.36 n.s. 

-6.21 -1.87 2.48 n.s. 

-1.41 5.87 13.15 n.s. 

-14.60 -4.50 5.60 n.s. 

-7.44 14.00 35.44 n.s. 

-0.0206 -0.0064 0.0078 n.s. 

-0.0061 0.0151 0.0363 n.s. 

* = Statistically significant at the 0.05 level. 

n.s. = Not statistically significant at the 0.05 level. 

TABLE 9. Within-cell Standard Deviations - Geicoat Experiment 

GF EQUIP X Zl Z2 Yl Y2 Y3 Y4 Y5 Y6 Y7 Y8 

GFl 

GFl 

GFl 

GF2 

GF2 

GF2 

GE1 

GE2 

GE3 

GE1 

GE2 

GE3 

2.7 

0.5 

2.7 

3.6 

1.1 

1.0 

11.4 

30.1 

7.0 

3.8 

25.2 

13.6 

30.2 

9.5 

68.4 

54.1 

23.6 

18.8 

8.3 

4.7 

10.0 

4.4 

10.4 

10.1 

8.0 

2.6 

4.6 

6.4 

3.1 

2.1 

2.8 

4.0 

3.7 

2.6 

5.1 

2.9 

4.0 

0.9 

6.6 • 

10.7 

2.5 

2.1 

5.1 

13.2 

3.2 

1.7 

11.3 

6.0 

13.1 

4.0 

29.8 

23.6 

10.1 

8.2 

0.010 

0.015 

0.014 

0.007 

0.013 

0.008 

0.016 

0.003 

0.026 

0.027 

0.006 

0.005 

F-12 

m 
P.23 

For the two Z variables, an initial analysis of covariance (ANACOVA) of the following 

form was performed: 

SOURCE OF VARIATION DEGREES OF FREEDOM 

X (transfer efficiency) 1 

GF (gelcoats) 1 

GE (equipments) 2 

GF x GE (interaction) 2 

Error 11 

Total 17 

Since in each case the interaction term appeared statistically nonsignificant, that term was 

dropped to produce the following: 

SOURCE OF VARIATION DEGREES OF FREEDOM 

X (transfer efficiency) 1 

GF (gelcoats) 1 

GE (equipments) 2 

Error 13 

Total 17 

Table 10 provides the ANOVA and ANACOVA results for the two Z variables. Type of 

geicoat FORMULATION appears to have a significant effect on both variables. Neither Zl nor 

Z2 exhibits differences attributable to types of EQUIPMENT. 

F-13 

/o9 
P.24 

TABLE 10. AnaFysis of Covariance Results for Geicoat Experiment: Variables Zl 

and Z2 

MEANS MEANS ADJUSTED FOR X 

GF 

GFl 

GFl 

GFl 

GF2 

GF2 

GF2 

GFl 

GF2 

. 

-

-

EQUIP 

GE1 

GE2 

GE3 

GE1 

GE2 

GE3 

. 

-

GE1 

GE2 

GE3 

N 

3 

3 

3 

3 

3 

3 

9 

9 

6 

6 

6 

X 

-1.5 

-1.6 

-0.5 

2.5 

-1.5 

2.6 

-1.2 

1.2 

0.5 

-1.5 

1.1 

Zl 

399.7 

373.3 

387.0 

271.3 

278.0 

283,7 

386.7 

277.7 

335.5 

325.7 

335.3 

Z2 

389.7 

397.0 

393.3 

287.0 

349.0 

289.7 

393.3 

308.6 

338.3 

373.0 

341.5 

Zl 

399.7 

373.4 

387.0 

271.3 

278.0 

283.6 

385.3 

279.0 

336.1 

323.9 

336.6 

Z2 

368.1 

373,5 

386.7 

322.7 

327.9 

326.8 

375.9 

326.0 

345.5 

350.4 

356.9 

Hypothesis testing results: 

RMSE for testing 

interaction (12 df): 

(11 df): 

Test for interaction: 

RMSE for testing main 

effects (14 df): 

(and covariate) (13 df): 

Test for FORMULATIONS: 

Test for EQUIPMENT: 

Test for covariate X: 

17.9 

n.s. 

18.4 

n.s. 

39.8 

n.s. 

39.7 

n.s. 

18.7 

n.s. 

18.9 

n.s. 

n.s. 

23.9 

n.s. 

22.4 

n.s. 

* = statistically significant at the 0.05 level. 

** = statistically significant at the 0.01 level. 

*** = statistically significant at the 0.001 level. 

F-14 

IO 
P.25 

F.3 Resin Experiment. 

This experiment was aimed at evaluating how styrene emissions are affected by type of 

resin formulation (factor RF) and type of equipment (factor RE). The factor combinations used 

in the experiment and the associated sample sizes were as follows: 

Treatment Level of RE Level of RF n 

1 

2 

3 

4 

5 

6 

7 

8 

REI 

REI 

REI 

REI 

RE2 

RE3 

RE4 

RE4 

RF1 

RF2 

RF3 

RF6 

RF1 

RF1 

RF4FG 

RF4SG 

5 

3 

3 

3 

3 

3 

2 

2 

This design deviates slightly from the orignally planned design. Resin RF4 was modified to 

shorten gel time after two test runs had shown that resin drains to the flange before it cures. 

These two RF4 test runs are noted with SG for slow gel. The modified RF4 resin has a faster gel 

time that allows resin to cure before it drains. RF 5 resin was not tested because the resin 

manufacturer decided to drop out from the testing. The actual runs yield 16 degrees of freedom 

for error. Separate analyses are used to test for equipment differences and for different resin 

formulations. 

The ANOVA for equipment comparisons among REI, RE2, and RE3 (for resin RF1) is 

as follows: 

SOURCE OF VARIATION DEGREES OF FREEDOM 

RE (equipments) 2 

Error 16 (assumes pooling of variances from within all treatments) 

For resin formulation comparisons (i.e., excluding treatments 5 and 6) the following 

ANOVA applies: 

SOURCE OF VARIATION DEGREES OF FREEDOM 

RF (resins) 5 

Error 16 (assumes pooling of variances from within all treatments) 

F-15 

/ / / 
P.26 

It should be noted that any comparison involving RF4SG or RF4FG versus one of the other 

treatments is not only a comparison of resin formulations but also of application method. 

Table 11 presents the ANOVA results for the X and all of the Y variables. The upper 

portion of the table gives means for each treatment (combination of equipment and formualtion) 

while the lower portion shows the results of testing hypotheses. Nonsignificant results were 

obtained for X and Yl with regard to differences due to resin formulations (while using a fixed 

type of equipment, REI); the remaining Y variables all exhibited highly significant effects due to 

these formulations. Type of equipment appeared to be a significant factor for all of seven of 

these variables. Point estimates of mean differences and 95 percent confidence interval estimates 

are given in Table 12 for EF in percent available styrene (% AS) as measured by THC and MB. 

Similar infonnation is presented in Table 13 for EF in g/m2 as measured by THC arid MB. 

Similar information is presented in Table 14 for EF in g/g as measured by THC and MB. The 

with-in cell standard deviations for resin experiment are shown in Table 15. 

For the two Z variables, an initial analyses of covariance were run by incorporating the 

transfer efficiency variable X into the ANOVA model. The results are given in Table 16. Both 

type of resin formulation and type of equipment appears to have a significant effect on both 

variables. 

F-16 
TABLE 11. Analysis of Variance Results for Resin Experiment: Variables X, Yl, Y2,..., Y8 

MEANS 

TREATMENT 

1 REI 

2 REI 

3 REI 

4 REI 

5RE2 

6RE3 

7RE4 

8RE4 

RF1 

RF2 

RF3 

RF6 

RF1 

RF1 

RF4FG 

RF4SG 

N 

5 

3 

3 

3 

3 

3 

2 

2 

X

a 

-0.6 

-0.7 

-0.2 

-0.9 

4.6 

4.4 

-0.9 

-8.6 

Yl 

214.0 

192.7 

179.7 

148.7 

143.0 

166.3 

192.5 

311.0 

Y2 

202.0 

170.3 

86.7 

77.3 

149.0 

121.0 

262.0 

382.5 

Y3 

17.4 

17.3 

10.6 

10.6 

14.2 

15.3 

21.3 

26.2 

Y4 

17.0 

16.1 

10.4 

9.7 

13.8 

15.1 

20.3 

24.8 

Y5 

195.0 

173.3 

125.3 

116.7 

134.7 

131.3 

224.5 

. 330.0 

Y6 

189.4 

161.0 

122.3 

107.3 

130.0 

129.0 

214.0 

312.5 

Y7 

0.067 

0.061 

0.046 

0.046 

0.055 

0.059 

0.091 

0.112 

Y8 

0.065 

0.057 

0.045 

0.042 

0.053 

0.058 

0.086 

0.106 

i 

-J 

Hypothesis Testing Results: 

RMSE for testing 

effects (16 df): 190 

Test for Treatments *** 

30.82 31.50 1.28 

*** 

1.52 11.14 11.17 

*** 

0.0053 

*** 

0.0061 

*** 

Test for Resin 

Formulations 

(Trt 1 vs. 2 

vs. 3 vs: 4): n.s. n.s. 

Test for Equipments 

(Trt 1 vs. 5 vs. 6): ** * 

* = statistically significant at the 0.05 level. 

** = statistically significant at the 0.01 level. 

*** = statistically significant at the 0.001 level. 

'Overall mean for X prior to standardization was 92.65. 

*** *** 

*** 

*** 

P 
P.28 

TABLE 12. Estimated Mean Differences and Confidence Interval Estimates for Percent 

Available Styrene (% AS): Resin Experiment 

Variable and comparison 

Y3 - EF, % AS (by THC) 

Equipment Comparisons 

RE1RF1 -RE2RF1 

RE1RF1 -RE3RF1 

RE2RF1 -RE3RF1 

Resin Formulation Comparisons 

RE1RF1 -RE1RF2 

RE1RF1 -RE1RF3 

RE1RF1 -REIRF6 

RE1RF2 -REIRF3 

RE1RF2 -RE1RF6 

RE1RF3 -RE1RF6 

Comparison of MEKP and BPO systems 

RE1RF1 -RE4RF4FG 

RE1RF1 -RE4RF4SG 

Y4 - EF, % AS (by MB) 

Equipment Comparisons 

RE1RF1 -RE2RF1 

RE1RF1 -RE3RF1 

RE2RF1 -RE3RF1 

Resin Formulation Comparisons 

RE1RF1 -RE1RF2 

RE1RF1 -RE1RF3 

RE1RF1 -RE1RF6 

RE1RF2 -RE1RF3 

RE1RF2 -RE1RF6 

RE1RF3 -REIRF6 

Comparison of MEKP and BPO systems 

RE1RF1 -RE4RF4FG 

RE1RF1 -RE4RF4SG 

Lower 95% Estimated 

confidence mean 

limit difference 

1.220 3.207 

0.120 2.107 

-3.322 -1.100 

-1.880 0.107 

4.853 6.840 

4.853 6.840 

4.512 6.733 

4.512 6.733 

-2.222 0.000 

-6.086 -3.810 

-11.036 -8.760 

0.796 3.147 

-0.437 1.913 

-3.322 -1.100 

-1.470 0.880 

4.263 6.613 

4.896 7.247 

3.105 5.733 

3.739 6.367 

-1.995 0.633 

-5.963 -3.270 

-10.513 -7.820 

Upper 95% 

confidence 

limit 

5.194 

4.094 

1.122 

2.094 

8.827 

8.827 

8.955 

8.955 

2.222 

-1.534 

-6.484 

5.497 

4.264 

1.122 

3.230 

8.964 

9.597 

8.361 

8.995 

3.261 

-0.577 

-5.127 

Significant 

** 

* 

*** 

*** 

*** 

*** 

** 

*** 

*• 

*** 

*** 

*** 

*** 

* 

*** 

Comparisons significant at the 0.05 level are indicated by '*' 

* = statistically significant at the 0.05 level. 

** = statistically significant at the 0.01 level. 

*** = statistically significant at the 0.001 level. 

F-18 

\\V 
P.29 

TABLE 13. Estimated Mean Differences and Confidence Interval Estimates for Emission 

Factor (g/m2): Resin Experiment 

Variable and comparison 

Y5 - EF, g/m2 (by THC) 

Equipment Comparisons 

RE1RF1 -RE2RF1 

RE1RF1 -RE3RF1 

RE2RF1 -RE3RF1 

Resin Formulation Comparisons 

RE1RF1 -RE1RF2 

RE1RF1 -RE1RF3 

RE1RF1 -RE1RF6 

RE1RF2 -RE1RF3 

RE1RF2 -RE1RF6 

RE1RF3 -RE1RF6 

Comparison of MEKP and BPO systems 

RE1RF1 -RE4RF4FG 

RE1RF1 -RE4RF4SG 

Y6 - EF, g/m2 (by MB) 

Equipment Comparisons 

RE1RF1 -RE2RF1 

RE1RF1 -RE3RF1 

RE2RF1 -RE3RF1 

Resin Formulation Comparisons 

RE1RF1 -RE1RF2 

RE1RF1 -RE1RF3 

RE1RF1 -RE1RF6 

RE1RF2 -RE1RF3 

RE1RF2 -RE1RF6 

RE1RF3 -RE1RF6 

Comparison of MEKP and BPO systems 

RE1RF1 -RE4RF4FG 

RE1RF1 -RE4RF4SG 

Lower 95% 

confidence 

limit 

43.094 

46.428 

-15.940 

4.428 

52.428 

61.094 

28.726 

37.393 

-10.607 

-49.250 

-154.750 

42.104 

43.104 

-18.338 

11.104 

49.771 

64.771 

19.329 

34.329 

-4.338 

-44.415 

-142.915 

Estimated 

mean 

difference 

60.333 

63.667 

3.333 

21.667 

69.667 

78.333 

48.000 

56.667 

8.667 

-29.500 

-135.000 

59.400 

60.400 

1.000 

28.400 

67.067 

82.067 

38.667 

53.667 

15.000 

-24.600 

-123.100 

Upper 95% 

confidence 

limit 

77.572 

80.906 

22.607 

38.906 

86.906 

95.572 

67.274 

75.940 

27.940 

-9.750 

115.250 

76.696 

77.696 

20.338 

45.696 

84.363 

99.363 

58.004 

73.004 

34.338 

-4.785 

-103.285 

Significant 

*** 

*** 

* 

* 

*** 

*** 

*** 

** 

*«* 

*** 

*** 

* * • 

* * • 

*** 

*** 

* * • 

* 

* • * 

Comparisons significant at the 0.05 level are indicated by '*'. 

* = Statistically significant at the 0.05 level. 

** = Statistically significant at the 0.01 level. 

*** = Statistically significant at the 0.001 level, 

n.s. = Not statistically significant at the 0.05 level. 

F-19 

AS 
P.30 

TABLE 14. Estimated Mean Differences and Confidence Interval Estimates for Emission 

Factor (g/g): Resin Experiment 

Variable and comparison 

Y7 - EF, g/g (by THC) 

Equipment Comparisons 

RE1RF1 -RE2RF1 

RE1RF1 -RE3RF1 

RE2RF1 -RE3RF1 

Resin Formulation Comparisons 

RE1RF1 -RE1RF2 

RE1RF1 -RE1RF3 

REIRF1 -RE.1RF6 

RE1RF2 -RE1RF3 

RE1RF2 -RE1RF6 

RE1RF3 -RE1RF6 

Comparison of MEKP and BPO 

systems 

RE1RF1 -RE4RF4FG 

RE1RF1 -RE4RF4SG 

Y8 - EF, g/g (by MB) 

Equipment Comparisons 

RE1RF1 -RE2RF1 

REIRF1 -RE3RF1 

Resin Formulation Comparisons 

RE1RF1 -RE1RF2 

RE1RF1 -RE1RF3 

RE1RF1 -RE1RF6 

RE1RF2 -RE1RF3 

RE1RF2 -RE1RF6 

RE1RF3 -RE1RF6 

Comparison of MEKP and BPO 

systems 

RE1RF1 -RE4RF4FG 

RE1RF1 -RE4RF4SG 

Lower 95% 

confidence 

limit 

0.004 

0.000 

-0.013 

-0.003 

0.013 

0.013 

0.006 

0.006 

-0.009 

-0.033 

-0.054 

0.003 

-0.002 

-0.015 

-0.001 

0.011 

0.014 

0.001 

0.004 

-0.008 

-0.032 

-0.051 

Esimtated 

mean 

difference 

0.012 

0.008 

-0.004 

0.006 

0.021 

0.021 

0.015 

0.015 

0.000 

-0.024 

-0.045 

0.012 

0.007 

-0.005 

0.008 

0.020 

0.023 

0.012 

0.015 

0.003 

-0.021 

-0.041 

Upper 95% 

confidence 

limit 

0.020 

0.016 

0.005 

0.014 

0.029 

0.029 

0.024 

0.025 

0.009 

-0.014 

-0.035 

0.022 

0.017 

0.006 

0.018 

0.030 

0.032 

0.022 

0.025 

0.013 

-0.010 

-0.030 

Significant 

** 

* 

*** 

*** 

** 

** 

*** 

*** 

* 

*** 

*** 

* 

** 

*** 

#** 

Comparisons significant at the 0.05 level are indicated by '*'. 

* = Statistically significant at the 0.05 level. 

** = Statistically significant at the 0.01 level. 

*** = Statistically significant at the 0.001 level, 

n.s. = Not statistically significant at the 0.05 level. 

F-20 

p(U 
P.31 

TABLE 15. Within-treatment Standard Deviations - Resin Experiment 

TRT N X Zl Z2 Yl Y2 Y3 Y4 Y5 Y6 Y7 Y8 

RE1RF1 

RE1RF2 

REIRF3 

RE1RF6 

RE2RF1 

RE3RF1 

RE4RF4FG 

RE4RF4SG 

5 

3 

3 

3 

3 

3 

2 

2 

1.1 

1.0 

0.7 

1.6 

0.9 

0.3 

0.1 

6.5 

25.0 

7.1 

12.7 

49.5 

14.6 

28.8 

17.0 

13.4 

6.8 

6.6 

20.7 

40.6 

35.6 

36.7 

0.0 

26.9 

8.7 

2.1 

13.5 

49.6 

22.9 

47.4 

0.7 

63.6 

11.9 

7.2 

9.6 

7.1 

50.7 

14.0 

0.0 

96.9 

1.0 

1.1 

1.2 

1.3 

0.4 

0.9 

0.9 

3.3 

1.4 

1.0 

1.7 

1.3 

2.0 

1.3 

0.2 

2.5 

11.0 

3.5 

5.7 

21.5 

6.0 

12.7 

7.8 

5.7 

3.0 

3.0 

8.7 

18.0 

15.7 

15.9 

0.0 

12.0 

0.004 

0.004 

0.005 

0.006 

0.001 

0.004 

0.004 

0.014 

0.005 

0.004 

0.007 

0.006 

0.008 

0.005 

0.001 

0.011 

F-21 

//A 
P.32 

TABLE 16. Analysis of Covariance Results for Resin Experiment: Variables Zl and Z2 

MEANS MEANS ADJUSTED FOR X 

TREATMENT N X" Zl Z2 Zl Z2 

1 REI 

2 REI 

3RE1 

4RE1 

5RE2 

6RE3 

7RE4 

8RE4 

RF1' 

RF2 

RF3 

RF6 

RF1 

RF1 

RF4FG 

RF4SG 

5 

3 

3 

3 

3 

3 

2 

2 

-0.6 

-0.7 

-0.2 

-0.9 

4.6 

4.4 

-0.9 

-8.6 

444.8 

395.3 

286.3 

266.7 

306.7 

299.0 

512.0 

752.5 

431.8 

367.0 

279.0 

244.7 

296.3 

294.3 

488.0 

713.0 

444.4 

394.9 

286.2 

266.0 

309.9 

302.1 

511.4 

746.5 

428.7 

363.8 

278.2 

240.3 

319.0 

316.0 

483.8 

671.0 

Hypothesis Testing Results: 

RMSE for testing 

effects (16 df): 

(and covariate) (15 df): 

Test for Treatments: 

25.46 

*** 

25.44 

*** 

26.26 24.45 

*** *** 

Test for Resin 

Formulations 

(Trt 1 vs. 2 

vs. 3 vs. 4): 

Test for Equipments 

(Trt 1 vs. 5 vs. 6): *** 

.*** 

*** 

*** *** 

*** *** 

* = statistically significant at the 0.05 level 

** = statistically significant at the 0.01 level 

*** = statistically significant at the 0.001 level 

"Overall mean for X prior to standardization was 79.96. 

F-22 

rl8 
P.33 

F.4 Summary 

Table 17 provides a summary of the hypothesis testing results. 

TABLE 17. Summary of Results of Specific Hypothesis Tests 

Comparison 

Ml vs.M2 

Al vs. A2 

GFl vs. GF2 

GEl vs.GE2 

GEl vs.GE3 

GE2 vs. GE3 

RFl vs. RF2 | REI 

RFl vs. RF3JRE1 

RFl vs. RF6 | REI 

RF2vs.RF3|REl 

RF2vs. RF6|RE1 

RF3 vs. RF6 | REI 

REI vs.RE2|RFl 

REl vs.RE3|RFl 

RE2 vs. RE3 | RFl 

REI RFl vs. RE4RF4FG 

RE1RFI vs.RE4RF4SG 

RE4RF4FG vs. RE4RF4SG 

X 

** 

# 

** 

** 

*** 

*** 

Zl 

*** 

*** 

*** 

*** 

*** 

* * • 

*** 

*** 

** 

*** 

*** 

Z2 

* 

*** 

** 

*** 

*** 

*** 

*** 

*** 

* 

*** 

*** 

Yl 

*** 

*** 

* 

* 

** 

*** 

*** 

Y2 

*** 

*** 

*** 

** 

** 

* 

** 

*** 

*** 

Y3 

** 

*** 

*** 

*** 

*** 

** 

* 

** 

*** 

*** 

Y4 

* • * 

*** 

*** 

*** 

* 

* 

*** 

Y5 

*** 

*** 

# 

*** 

*** 

*** 

»** 

*** 

* • * 

** 

*** 

* * • 

Y6 

* 

* # • 

** 

*** 

*** 

*** 

• * * 

*** 

* 

*** 

*** 

Y7 Y8 

* 

••* **• 

*** *** 

*** *** 

** * 

** ** 

** * 

* 

*** *»* 

*** *** 

** ** 

* = statistically significant at the 0.05 level. 

** = statistically significant at the 0.01 level. 

*** = statistically significant at the 0.001 level. 

F-23 

I fi 
P.34 

Appendix G 

THC Analyzer Evaluation: Sampling Line Loss and Pressure Effect 

Section 

Table of Contents 

G-i 

/ZO 

Page No. 

G. 1 Sampling Line Loss G-1 

G.2 Pressure Effect G-2 
P.35 

G.l Sampling Line Loss 

At the beginning of the project, questions were raised about whether styrene would be 

lost in the sampling line due to its reactive nature. RTI investigated potential sampling line 

losses prior to the styrene emission testing at Reichhold Chemical. Styrene and propane 

calibration standards were delivered through various sampling lines connected to the analyzer's 

calibration and sample ports in a manner very similar to that employed during routine 

calibrations. The analyzer operating parameters were identical to those used during styrene 

emission testing. The results of this study indicate that there are no significant pressure effects or 

styrene losses associated with the sampling line. 

In an initial test, two different lengths (4 feet versus 25 feet)of 1/8-inch ID PFA Teflon 

tubing were compared. In a second test, 4 feet of 1/8-inch ID PFA Teflon tubing was compared 

to 12 feet of 1/4-inch ED tetrafluoroethylene (TFE) Teflon tubing. 

In the initial test, two styrene calibration standards, four propane calibration standards, 

and zero air were measured on Range 2 (0 to 200 ppmv styrene) after being delivered through the 

4-foot and 25-foot lengths of 1/8-inch ID sampling lines. Two other styrene calibration 

standards, three other propane calibration standards, and zero air were measured on Range 1 (0 to 

20 ppmv styrene) after being delivered through the two sampling lines. Least squares regression 

analysis of 2-minute mean voltages yielded slopes for the 25-foot data regressed against the 4-

foof data. The results of this test are given in the following table: 

Styrene Slope 

(Volts/Volt) 

Propane Slope 

(Volts/Volt) 

Styrene-to-Propane Slope 

Ratio 

Range 2 

1.0697 

(+/- 0.0070) 

1.0485 

(+/-0.0150) 

1.0203 

Range 1 

1.1115 

(+/- 0.0266) 

1.0430 

(+/- 0.0032) 

1.0657 

A styrene or propane slope equal to 1.0000 would indicate equal or no losses for propane 

or styrene in the two different sampling lines. The measured slopes are greater than 1.0000, 

which could mean that the 25-foot sampling line had lower losses than the 4-foot sampling line. 

This possible conclusion is counterintuitive. Instead, it was hypothesized that the higher total 

hydrocarbon analyzer responses in the 25-foot sampling line were associated with some pressure 

effect in the analyzer. 

G-1 
P.36 

A styrene-to-propane slope ratio of 1.0000 would indicate that any styrene losses in the 

sampling lines were equal to any propane losses. No conclusions were drawn from these data 

concerning styrene losses due to questions about possible pressure effects. 

The sampling line loss measurements were repeated in a second test using a different 

sampling line. A 12-foot length of 3/16-inch ID TFE tubing, which more realistically simulates 

the actual sampling line, was compared to the 4-foot length of 1/8-inch ID PFA tubing. This test 

used the same calibration standards as was used in the previous test. The results of the least 

squares regression analysis of these test data are given in the following table: 

Styrene Slope 

(Volts/Volt) 

Propane Slope 

(Volts/Volt) 

Styrene-to-Propane Slope 

Ratio 

Range 2 

0.9972 

(+/-0.0186) 

1.0134 

(+/- 0.0020) 

0.9840 

Range 1 

1.0326 

(+/- 0.0072) 

1.0228 

(+/- 0.0064) 

1.0095 

These results indicate that there are no significant pressure effects associated with the two 

sampling lines that were tested and that there is no significant styrene losses in the longer 

sampling line. 

G.2 Pressure Effect 

During routine calibrations of the total hydrocarbon analyzer, RTI observed that the 

analyzer's response is very sensitive to changes in the sample pressure at the inlet of the FTD's 

capillary. The analyzer's operating manual states that it is very critical to maintain exactly the 

same sample pressure during calibrations as during analysis of actual samples, it may be 

necessary to adjust the back-pressure regulator to maintain the sample pressure. 

RTI carefully maintained the sample pressure at 3.0 psig during calibrations and routine 

sampling and noted that the sample pressure shifted by approximately 0.1 psig when the analyzer 

was switched between these two operating modes. The back-pressure regulator was adjusted as 

needed. RTI found that a +/- 0.1 psig sample pressure shift during a calibration produced an 

approximately +/- 6.5 percent shift in the analyzer's response. 

Some questions remained concerning possible residual pressure effects. The sample 

pressure gauge is connected to the inlet of the back-pressure regulator, which is about 9 inches 

downstream of the inlet of the FTD capillary. Differences in sampling line pressure drops 

upstream of the sampling pump may produce pressure differences at the FID inlet even though 

the sample pressure was maintained at 3.0 psig. 

G-2 

at-
P.37 

RTI investigated these questions by delivering three propane calibration standards and 

zero air through three different sampling lines to the analyzer in a manner similar to that used 

during routine calibrations. The analyzer was operated on Range 2. The three following sample 

lines were connected to the analyzer's three inlet ports: 

(A) 8-feet x 1/8-inch ID PFA Teflon tubing with gas pressure maintained at 5 psig by 

an in-line pressure regulator (normal calibration configuration); 

(B) 4-feet x 1/8-inch ED PFA Teflon tubing with gas pressure maintained at 0 psig by 

an atmospheric- pressure sampling manifold; and 

(C) 12-feet x 3/16-inch ED TFE Teflon tubing with gas pressure maintained at 0 psig 

by an atmospheric-pressure sampling manifold. 

Least squares regression analysis of 2-minute mean voltages yielded the following slopes 

:

or the regression lines associated with the three sampling lines: 

Sampling 

Line 

A 

B 

C 

Regression Slope 

(Volts/ppmv) 

0.01845 

0.01792 

0.01969 

Slope Ratio relative to Normal 

Calibration Configuration 

0.971 

1.067 

These results indicate that residual pressure effects exist even when the sample pressure 

is maintained at 3.0 psig. Although Sampling Lines B and C were operating at atmospheric 

pressure, the slopes differed by approximately 11 percent. It is hypothesized that the pressure 

drops across the sampling lines are the cause of the difference. The theoretical pressure drop 

across Sampling Line B is 0.47 psig at a flowrate of 7 liters per minute. The corresponding 

pressure drop across Sampling Line C is 0.20 psig. 

It is unclear how these results can be extrapolated to the 12-foot long by 1/4-inch ED PFA 

Teflon tubing used as the sampling line in the styrene emission tests. The theoretical pressure 

drop for this sampling line is 0.053 psig. 

Immediately following the EPA performance evaluation, RTI conducted an additional 

pressure effects test using the 153 ppm propane calibration standard and various sampling lines. 

The results of this test is given in the following table. 

GO 

/-2-s; 
P.38_ 

Sampling Line and 

Configuration 

8-feet x 1/8-inch ID PFA Teflon tubing with 

pressure maintained at 5 psig by an in-line 

pressure regulator (normal calibration 

configuration) 

12-feet x 3/16-inch ID TFE Teflon tubing with 

pressure maintained at G psig by an atmospheric 

pressure sampling manifold 

12-feet x 1/4-inch ID PFA Teflon tubing with 

pressure maintained at 0 psig by an atmospheric 

pressure sampling manifold (normal sampling 

line) 

Analyzer 

Response to 

153 ppm 

Propane (Volts) 

2.782 

2.809 

2.968 

Analyzer Response 

Ratio Relative to 

Normal Calibration 

Configuration 

1.010 

1.067 

These results are somewhat different from the previous set of results. The 3/16-inch 

tubing produced an analyzer response 1 percent greater than the normal calibration configuration 

whereas it was 6.7 percent greater in the previous set of results. This difference may be due to 

either a variation in the magnitude of the pressure effect during the two sets of measurements or 

to a variation in the concentration in the sampling lines. Nevertheless, the general trend of these 

results is the same (i.e., larger-bore sampling lines at atmospheric pressure produce greater 

responses than the normal pressurized calibration line). 

Based on these limited measurements and those obtained during the performance 

evaluation, the following conclusions may be drawn: 

• despite careful control of the analyzer's sample pressure, variations of the gas pressure in 

the sampling line and the calibration line produce changes in the analyzer's response; 

• the results of the pressure effects measurements are inconsistent and more measurements 

would be required to quantify definitively the magnitude of the pressure effect; and 

• the observed magnitude of the pressure effect ranged between 1 and 7 percent. 

The impact of the pressure effects on the total hydrocarbon measurements is not 

excessive relative to the +/- 5 percent accuracy objective that is given in the quality assurance 

project plan. Consequently, the total hydrocarbon measurements should not be corrected for 

pressure effects of unquantified magnitude. 

(Reference: F. Caplan, "Finding Air Pressure Drop Through Smooth Tubes", Plant Engineering. 

January 6, 1977, pp. 74-75.) 

G-4 

f l * 
P.39 

Appendix H 

An RTI Technical System Audit Report 

H-i 

/zs 
P.40 

RESEARCH TRIANGLE INSTITUTE 

/RTI 

MEMORANDUM 

TO: Emery Kong, RTI Project Leader 

FROM: Cynthia Salmons, RTI QA Officer (t& 

DATE: July 20, 1995 

SUBJECT: Technical Systems Audit of Evaluation of Pollution Prevention 

Techniques to Reduce Styrene Emissions From Open Contact Molding 

Processes 

On June 9, Dr. William Yeager and I conducted a technical systems audit 

(TSA) of the styrene emissions project. Pre-audit activities included preparation of 

an audit checklist based on the quality assurance project plan (QAPP, see 

attachment) and an informal walkthrough on June 2. This memorandum 

summarizes the audit findings. 

We generally found that the activities were conducted in accordance with 

the QAPP. The scales and total hydrocarbon analyzer (THA) were calibrated. The 

actual THA calibration procedure was more extensive than that described in the 

QAPP and Method 25A. Originally, use of two concentration ranges on the THA 

was planned so adequate cylinders to calibrate both were obtained. -Through June 

9, for all test runs involving spray guns, the higher concentration range (0-200 

ppm) was used, but all of the cylinders (seven all together) were used to calibrate 

and/or check the calibration of the one range before each run. In addition, the 

calibration drift test was performed after each run. When the flow coater or 

pressure-fed roller was used in the test run, the lower concentration range (0-20 

ppm) on the THA was used for better resolution. On days with three or four runs, 

this approach involved many checks with the same calibration gases. If a 

calibration is performed before each run, using two of the cylinders from the series 

of calibration gases for the calibration drift check immediately before, for nine 

analyses of the seven cylinders, is probably not necessary. While it seems 

reasonable to perform the seven point calibration at the start of the day, a four 

point calibration, as called for in the method, should be sufficient before the other 

runs of the day. While Method 25A is explicit about which concentrations should 

be used (80-90%, 45-55%, and 25-35% of the span value, and a zero) for the four 

point calibration, with this many calibrations taking place, it would seem 

reasonable to switch around the cylinders used for the four point calibration, 

appropriate for the high or low concentration range, in the course of the day. 

After June 9, when we discussed this issue, seven point calibrations were 

performed at the start of each day. Then, four point calibrations were performed 

before each test run. 

The scale calibrations consisted of adding 9 weights sequentially. This 

30-iO Comwaii.s Rcao • Pes: Office Box 12194 . Research Triangle Park, North Carolina 27709:2194 USA 

Telephone 919 541-6000 • Fax 919 541-5985 

H-l 726 
P.41 

procedure was then repeated with something heavy, such as the mold, on the 

scale. Both scales (i.e., inside the enclosure and outside the enclosure) were 

linear. 

The measurement point for the exhaust flow rate (i.e., where the pitot tube 

is placed) is approximately 5-6 diameters downstream from a bend. Thus, the 

measurement point satisfies the requirement that there not be a disturbance less 

than 2 diameters upstream of the measurement point, but is not consistent with 

the recommendation of not having a disturbance less than 8 diameters upstream 

of the measurement point. There is not a reasonable way of achieving the 

recommended 8 diameters. Method 1 requires at least 16 points for a velocity 

traverse; 24 points were used for this project. Mark Bahner checked for off-axis 

flow by rotating the pitot tube in the duct and making velocity head (A P) 

measurements. This check did not indicate a problem with off-axis flow. 

The demonstration that the spray booth meets the criteria for total

 ;" 

enclosure was not observed, but the notes from thisjwere reviewed.. A few of the -.., 

hot-wire anemometer readings at the natural draft openings were slightly less y 

than 200 fpm, and there was considerable fluctuation in the hot wire anemometer 

readings. Smoke tubes were used to check the natural draft at the door, and the " 

air was always observed to be flowing into the spray booth. Calculating the duct 

flowrate by dividing the duct flow rate, which averaged 8,674 cfm, by the open 

area (42 square feet) indicates a natural draft opening velocity of 206 fpm. The • *: 

results of the styrene evaporation experiments indicate that the styrene emissions 

were captured. ' - • •-"-•-- •••••-••••-••• -••••-••••••• •• ••..••—...-^-.-' i 

We did not observe the sampling and analysis of the geicoat and resin 

because this was not performed on the day of our visit. We understand that a 

Reichhold laboratory will perform the geicoat property measurements. We also 

did not observe the styrene evaporation experiment or the weekly traverse ' 

measurements, but we reviewed results from these activities. We also did riot see 

the measurement of the equipment delivery rate/ We understand that this was 

performed once per day, at the end of the day, during the early tests. Later, this 

was done after each test run, except for the pressure-fed roller, for which thisf ,. 

determination was difficult to make and inaccurate. ' ' ,!. "'' ' ,

wt

 " '' 

' •' 'The manufacturer's specifications for the geicoat and resin indicate that 

styrene is the only volatile component. The 55 gallon drum was mixed and then 

split into 5 gallon cans. One quart samples were taken for the laboratory 

measurements from the first 5 gallon cans when the material was used the first 

ytime.1' Small samples (approximately 30 grams) were taken when the material was 

last used for the analysis of non-volatile content. 

The baseline in the spray booth was measured with the THA for 

approximately 5 minutes before each run. For the purposes of ending a test, 

baseline was defined as a reading of less than 1 ppm styrene on the THA. 

Typically, the pre-test background was between 0.4 and 0.6 ppm, and tests were 

not ended until the readings reached this level. The data logger records every 2 

seconds. At the end of each run, the data were downloaded to a computer, but 

there was a computer software problem with this step during the period we 

observed. This computer software problem was resolved later, and all data were 

Go 

H-2 
P.42 

smoothly transferred to a computer. 

Bob Wright recorded the pitot tube measurements and temperature every 

15 minutes on data recording sheets and in his notebook. There is a NISTtraceable thermometer for checking these temperature measurements, but this 

had not been performed yet. 

We have reviewed the materials that Mark Bahner provided on June 20 in 

response to Bill Yeager's electronic mail request of June 12. This included results 

from the styrene evaporation experiment, the weekly traverse measurements, the 

checks for off-axis flow in the duct, and the tests that we observed during our 

audit. These results did not indicate any problems with the project activities. 

cc: Shri Kulkarni 

Bill Yeager 

Bob Wright 

Mark Bahner 

Keith Leese 

File: 5171-016 

H-3 

/ 
P.43 

TECHNICAL SYSTEMS AUDIT CHECKLIST 

Audit Subject: Styrene Emissions Date: June 9, 1995 

Auditee: RTI Auditors: Salmons, Yeager 

Location: Reichhold Chemical Auditor Affil.: RTI 

Personnel Present During Audit: Emery Kong, Mark Bahner, Bob Wright 

GENERAL 

1. Is a written and approved QA Project Plan (QAPP) available to .field personnel 

for this project? ,,.,, . 

Yes. 

2. Are all deviations from the QAPP and methods properly documented? 

The data logger is using a 2 second interval, which is more frequent than 

discussed in the QAPP. This still needs to be formally documented. 

3. How are corrective action procedures implemented? 

None needed so far. 

INITIAL AND PERIODIC PROCEDURES 

4. Are there records of the comparison between the propane and styrene 

standardizatons? When was the comparison performed? What were the results? 

Yes. May 26, 1995. Experimental and theoretical results are in good 

agreement. 

5. Are there records for the comparison of direct injection and unheated sample 

lines? When was this performed? What were the results? 

Yes. May 30, 1995? The agreement is good when the pressure is steady. 

When the pressure fluctuates, introducing gas through the sample line 

leads to higher, not lower, values. A larger diameter sample line was also 

used and seemed to improve agreement. 

6. Was EPA Method 204 used to demonstrate that the spray booth meets the 

criteria for a total enclosure? 

Yes. Some hot-wire anemometer measurements at the natural draft 

openings were less than 200 fpm (approx. 175). Considerable fluctuation in 

H-4 
P.44 

the hot-wire anemometer readings. 

7. Was the capture efficiency of the booth determined by evaporating a known 

amount of pure styrene? Was this test replicated? Within days? Among days? 

Yes. Five tests on 6/5; repeated on 6/7 and on 6/29. 

8. Is the measurement location for exhaust flowrate consistent with the EPA 

recommendation (8 diameters downstream of bend or disturbance and 2 diameters 

upstream)? Was the flow direction parallel to the axis of the duct at all points on 

the traverse? Was a 3D pitot tube used to check for turbulence? 

The measurement location is 5 or 6 diameters downstream of the bend so it 

meets the 2 diameter criteria but not the 8 diameter recommendation. A 

3D pitot tube was not used. At a later time, a check for off-axis flow was 

performed by rotating the pitot tube in the duct. Off-axis flow does not 

seem to be a problem. 

9. Does the flowrate derived from centerline A P accurately predict the flowrate 

determined by the traverse? How does the pitot tube A P at the center of the duct 

compare with the A Ps on the traverse? How much does this A P vary during a 

run? Are there any acceptance criteria for this variation? The precision goal for 

the exhaust flow rate is RPD less than or equal to 10%. 

Yes, within approximately 1 percent. Approx. 0.14 at center, approx. 0.10 

at side of the traverse. Velocity varies by approx. 18%. A P is slightly 

asymmetric across the duct. 

10. When was.the hot wire anemometer calibrated? Has it recently been checked 

against a pitot tube? 

Calibration on. April 14, 1995. Will check again after June. Not checked 

against a pitot tube. 

11. Were the linear air velocities in the spray booth consistent with the exhaust 

flow rate measurements? 

Approx. 7700 cfm versus 9000 in the duct. There were considerable 

fluctuations in the hot-wire anemometer used to measure flow rate at the 

filter face in the booth. 

12. Was the exhaust flow rate determined at least once per week? 

Yes. A traverse of both the spray booth and the stack was performed each 

week. The exhaust flowrate was calculated based on the center line A P 

measurements, which were taken every 15 minutes. 

H-5 
13. Were the air flow velocities determined and recorded for the natural draft 

openings and over the application area? 

Yes. 

14. Were the contents of the geicoat or resin container mixed for 2 minutes before 

sampling? 

.., „. Not observed, but discussed this with technical staff. 

,15. How was the 1 liter sample of geicoat or resin taken from the container to 

assure that it was representative? Was each container sampled? Were these ... ,,, 

determinations replicated? Within days? Among days? Does the manufacturer's^ 

invoice indicate that styrene is the only volatile component of the material? 

T.. A . Not observed. Manufacturer's specification indicates that styrene is the 7 ., 

''\"~ only volatile component. 55 gallon drums are broken down into 5 gallon 

^ ". i cans.' 1 quart samples will be taken from the first 5 gallon can and a 30 

-

 4 gram sample will be taken from the last 5 gallon can. The geicoat samples 

will be sent to a Reichhold laboratory for analysis. 

16. Were the material type, lot or batch number, and container number recorded 

oh'the geicoat or resin container delivered to the laboratory? '•".•" -Z-, • 

• . .. . i •• ..-J. Pi... . . . : .-..•••. - ,- .4.Z i . -' : , • . . • , PJ P i 

;%/$£:* lf^-/:, . "•""•.'':.:,'" ":::;x ;:'• ;i;-;;v:;;:'..'J." \~',.^'" 

17. Was styrene content for the geicoat an d resin materials determined with, 

Reichhold Standar d Test Method No. 18-001? .: *: 

.,'.»it;:v.f,;,u.'••Tj . , ,'>.. .-..-.. • . • . •::•-. P« ne* .:!•• .-." " ' '.''-".' 

'"^^•fiv;v, \ '\.v/V>' ' • , .•••,... , '• . • • • .,• • • • ; p .' . •" ,•.•-•,• ' •• ">;• ' P : * • i •"" < ; '•'- } 

"' Not observed. ' . '. / ,-•>" A ' '••'•; ; 

ppm. u.i. ..."••J .•'». . .' . P :P ." •'•• : •': ,-.': •"• Viy" v. ..«•:. : ...'•*.' p>r; rv^ . 18..Were the gel time, time to peak, and peak exotherm characteristics of.. . 

polyester resins measured following Reichhold Standar d Test Method No. 18-050 ' 

and,18-051?;.: . ; ', i'.'7,. .'"". " .... .' 7 ' •—•- • -

Not observed. ..,..' . , , , . k , ,, ,, 

. -.<ir*t p^ibru^*^ ' .-•.'•'-••' ' •• 1;; ;^ :-'--7>]i.-il} ~''-^Zd he i-yuFAtn:. h-?A7->. An Jher 

PROCEDURES FOR EACH RUN V ^ A a„Ji M ei . ^ 

•••-.I vte7-t >A\J-~JV--i-, 4;J .... . .. • . .:••-...:'. •-•• .":•:.•*."'. vk'ir.% and 3 ';erJ5: .. .A:. :...r,\r 

19. Was the THC ^calibrated before each run? \ A "i "'' , ' . : -7 7 „. 

spprct-y-^-tft fr»r th: AA> O" -'-; :.or1C:'ri,.r'/ti'ji.': rango, <:. fr.e course t>f tho day 

After J auk 9, when »vo d,;-',:'/;.c.i-.:^ this /SSJC, ?e-vyn point onKbrrtiur:: w'T« 

20..,Was the calibration error test procedure for the THC followed (i.e., 

introduction of the zero and high-level gases, adjustment, analysis of the low, and 

mid-level gases)? If so, were the results within 5% of expected? What were the 

H-6 

W 
P.46 

predicted and observed readings? 

During the project, the zero and span pots were not adjusted so that the 

instrument drift could be monitored. As is described in the memorandum to 

which this is attached, more standards were analyzed than are described in 

the method. The calculated calibration was based on the high span gas and 

the zero gas, which was assumed to be zero. The other standards 

functioned as linearity and calibration checks. The predicted and observed 

values were generally within 5%. Background, as determined from the 

instrument reading prior to the start of the test, was subtracted. 

21. Were the balances checked with standard reference weights? If so, how many 

and what size weights were used? 

Yes. Nine weights, ranging from 2 kg to 1 g. Also a box of fiberglass or a 

mold was added to the scale and the weights added again to check for 

linearity. 

22. Was the baseline in the spray booth measured with the THC before and after 

each run? For how long? 

Yes. The baseline is indicated by a THC reading of less than 1 ppm. 

Approx. 5 minutes. 

23. Were the initial air temperature, velocity head, and relative humidity 

measured and recorded? 

Yes. 

24. Was the equipment delivery rate measured in a remote location? 

Not observed, but told this was done at the end of the day during the early 

testing. Later, this was done after each test, except for the pressure-fed 

roller. 

25. Were the equipment setup conditions recorded? 

Not observed. 

26. Were the initial weights for the mold, gelcoat/resin, catalyst, fiberglass 

reinforcement, protective skirt for cart, and groundcover recorded? 

Yes. 

27. Was the time initiated as soon as application started? 

H-7 

.' :>7 

13Z-' 
P.47 

Yes. 

28. Were the velocity head and air temperature recorded every 15 minutes? 

Yes. Recorded on a data recording sheet and in Bob Wright's notebook 

except during lunch breaks. 

29. Were the time and weight of geicoat or resin recorded as soon as application 

was completed? 

Yes. 

30. Was the weight of the wet mold at the end of application without the 

protective skirt recorded? 

No. Recorded with the skirt on. The skirt was not removed until gel had 

cured and THC returned to baseline. 

31. Are the equipment delivery rates consistent with the before and after mass 

measurements for the mass balance calculations? 

Not observed. 

32. Was the run stopped when the THC indicated that the concentration returned 

to baseline? Was the time at which this happened recorded? 

Yes. 

. 33. Was the baseline drift for the THC determined at the end of the run? 

Yes. 

34. Was the enclosure flushed with fresh makeup air until the baseline stabilized? 

Yes. 

35. At the end of the day, were the recording sheets with sampling and analytical 

results collected, verified, and analyzed by the Testing Crew Chief? 

Not observed, but Mark Bahner had the results from the previous days and 

was able to show comparisons, etc. 

H-8 

6^ 
P.48 

Appendix I 

EPA Performance Evaluation of Total Hydrocarbon Analyzer 

I-i 

IM-
P.49 

APPENDIX I. EPA PERFORMANCE EVALUATION OF TOTAL 

HYDROCARBON ANALYZER 

EPA personnel conducted a performance evaluation of the total hydrocarbon analyzer on 

July 7, 1995. The purpose of the performance evaluation was to assess the accuracy of the 

analyzer and to compare this assessment with the accuracy data quality objective that was given 

in the quality assurance project plan. The assessment was accomplished by measurement of a 

styrene perforfance evaluation sample whose certified concentration was unknown to RTI. The 

measurements were performed on Range 2 of the analyzer. RTFs predicted concentration for this 

sample differed by 2 percent from its certified concentration. This result meets the data quality 

objective of +/- 5 percent for calibration gas accuracy that was given in the quality assurance 

project plan. Additional measurements showed that pressure effects did not exceed 3 percent 

during the performance evaluation. The styrene loss in the sampling line was found to be less 

than 2 percent. A more detailed discussion of the EPA performance evaluation is presented 

below. 

Discussions between RTI and EPA personnel resulted in agreement that three 

components of accuracy needed to be assessed during the performance evaluation: 

(1) the accuracy of RTI's calibration standards (especially in light of the use of 

propane to calibrate for styrene measurements); 

(2) pressure effects associated with calibration line/sampling line differences; and 

(3) styrene sampling line losses. 

EPA and RTI personnel agreed that these three accuracy components would be assessed 

by measurement of RTTs propane calibration standards and EPA's performance evaluation 

sample through RTFs calibration line from the cylinders directly and through RTI's sampling 

line from an EPA heated sampling manifold. 

The accuracy of RTI's propane calibration standards was determined from measurements 

in RTI's normal calibration configuration. RTI measured its propane calibration standards and 

the performance evaluation sample. RTI calculated a calibration equation from the propane 

measurements and predicted a concentration for the styrene sample based on this equation. This 

accuracy component was calculated as the percentage difference between the predicted and 

certified concentrations. 

Pressure effects were determined by comparing measurements of RTI's propane 

calibration standard through the normal calibration line and through the sampling line from an 

EPA heated sampling manifold. This accuracy component was calculated as the percentage 

difference between the two sets of analyzer responses. 

I-l 

/5S-
P.50 

Styrene sampling losses were determined from measurements of EPA's styrene 

performance evaluation sample in the normal calibration configuration and through the EPA 

heated sampling manifold/ RTI sampling line. This accuracy component was calculated as the 

percentage difference between the two predicted styrene concentrations. 

The EPA performance evaluation sample was a compressed gas calibration standard that 

was prepared in June 1995 by Scott Specialty Gases. Its certified styrene concentration is 31.0 

ppm as measured by Scott, but this value was not independently verified by EPA. RTI did not 

know the certified concentration until after the evaluation had been completed. 

EPA's sampling manifold was constructed from a 28-inch length of 2-inch OD stainless 

steel tube. Stainless steel tubing fittings were welded to the tube. RTI's sampling line was 

inserted into the manifold along the tube's long axis. The manifold was heated to approximately 

130 oC. The static pressure inside the manifold was measured by RTI's Magnehelic® 

differential pressure gauge and was maintained at 0.01 inches of water to ensure that it was at 

near-atmospheric conditions. 

The results of the evaluation are given in the following table: 

Parameter 

Equivalent Styrene 

Concentration 

THC Analyzer 

Response via Cal Port 

(Volts) 

THC Analyzer 

Response via EPA 

Manifold (Volts) 

Predicted Styrene 

Concentration (Cal 

Port) 

Predicted Styrene 

Concentration (EPA 

Manifold) 

RTI 45.03 ppm 

Propane 

Calibration 

Standard 

16.88 

0.844 

0.863 

— 

— 

RTI 153.37 ppm 

Propane 

Calibration 

Standard 

. 57.51 

2.848 

2.765 

— . 

— 

EPA Styrene 

Performance 

Evaluation 

Sample 

Unknown during 

analysis 

1.511 

1.469 

30.39 

29.82 

RTI 

Zero 

Air 

0.00 

0.008 

0.035 

-0.08 

-0.81 

1-2 

m 
P.51 

Parameter 

Response Change due 

to Pressure Effects 

(percent) 

Styrene Loss in 

Sampling Line 

(percent) 

RTI 45.03 ppm 

Propane 

Calibration 

Standard 

+2.23 

— 

RTI 153.37 ppm. 

Propane 

Calibration 

Standard 

-2.92 

— 

EPA Styrene 

Performance 

Evaluation 

Sample 

-2.76 

-1.87 

RTI 

Zero 

Air 

— 

— 

Using measurements in RTI's normal calibration configuration, the predicted 

concentration of the styrene performance evaluation sample is 30.39 ppm. This value differs by -

2.0 percent from the certified value of 31.0 ppm. 

The results of the pressure effects measurements are inconsistent. The analyzer's 

response for one propane calibration standard increased by 2.2 percent, but response decreased 

by 2.9 and 2.8 percent for the other propane calibration standard and for the styrene performance 

evaluation sample, respectively. It is hypothesized that stabilization problems or some unknown 

problem were biasing the EPA manifold results. In any case, pressure effects do not appear to 

exceed +/- 3 percent. 

The styrene loss in RTI's sampling line were less that 2 percent if one accepts all the 

propane and styrene measurements as being correct. 

1-3 

Ir 
TECHNICAL REPORT OATA 

(Please read Instructions on Ihe reverse before completing) 

1. REPORT NO. 

EPA-600/R-97-018b 

3. RECIPIENT'S ACCESSION NO. 

4. TITLE ANO SUBTITLE 

Evaluation of Pollution Prevention Techniques to 

Reduce Styrene Emission s from Open Contact 

Molding Processes; Volume II, Appendixes 

5. REPORT OATE 

March 1997 

6. PERFORMING ORGANIZATION CODE 

7. AUTHOR(S) 

Emer y Kong, Mark Bahner, Robert Wright, and 

Andrew Clayton 

8. PERFORMING ORGANIZATION REPORT NO. 

9. PERFORMING ORGANIZATION NAME ANO ADDRESS 10. PROGRAM ELEMENT NO. 

Researc h Triangl e Institute 

P . O. Box 12194 

Researc h Triangl e Park , North Carolina 27709 

11. CONTRACT/GRANT NO. 

CR 818419-03 

12. SPONSORING AGENCY NAME ANO AOORESS 

EPA , Office of Research and Development 

Air Pollution Prevention and Control Division 

Research Triangle Park, NC 27711 

13. TYPE OF REPORT AND PERIOD COVERED 

Final; 4/94-9/9 5 

14. SPONSORING AGENCY CODE 

EPA/600/13 

I8.SUPPLEMENTARYNOTESAPPCD p r o j e C t officer is GeddesH . Ramsey, Mail Drop 61. 919/ 

541-7963. Volume I is the final report. 

i«. ABSTRACT Tn e re p 0 r t give s results of a study to evaluate severa l pollution prevention 

techniques that could be used to reduc e styrene emissions from open molding pro -

cesse s in the fiberglass-reinforce d plastics/composite s (FRP/C) and fiberglass boat 

building industries. Styrene emission s using standard industry techniques, materials, and equipment wer e evaluated in a controlled environment and compared to a 

basline condition to determin e the effects of these pollution prevention techniques on 

styren e emissions. The study found that using controlled spraying (i.e. , reducing 

overspray), low-styren e and styrene-suppresse d materials, and nonatomizing application equipment can reduc e styren e emissions by from 11 to 52%. Facilitie s should 

investigat e the applicability and feasibility of these pollution prevention options to 

reduc e their styrene emissions. The calculated emission factors wer e from 1.6 tb 

2. 5 time s the mid-rang e AP-4 2 emission factors for the corresponding gel coat and 

resi n application. Thes e results indicate that facilities using AP-42 emission factors 

to estimat e emission s in open molding processe s ar e likely to underestimat e actual 

emissions. 

17. KEY WORDS AND DOCUMENT ANALYSIS 

DESCRIPTORS b.lOENTIFIERS/OPEN ENDED TERMS c. COSATI Field/Group 

Pollution 

Styrene Resin s 

Emissio n 

Molding Techniques 

Fiberglass-reinforce d Plastic s 

Boats 

Pollution Prevention 

Stationary Source s 

Boat Building 

13 B 

111, UJ 

14G 

13H 

11D 

13 J 

18. DISTRIBUTION STATEMENT 

Releas e to Publi c 

19. SECURITY CLASS (ThisReport) 

Unclassified 

2 1 . NO. OF PAGES 

148 

20. SECURITY CLASS (This page) 

Unclassified 

22. PRICE 

EPA Form 2220-1 (9-73) 1-4 

l€fe 
U.S. ENVIRONMENTAL PROTECTION AGENCY 

Office of Research and Development 

National Risk Management Research Laboratory 

Technology Transfer and Support Division 

Cincinnati, Ohio 45268 

OFFICIAL BUSINESS 

PENALTY FOR PRIVATE USE. S300 

AN EQUAL OPPORTUNITY EMPLOYER 

If your address is incorrect, please change on the above label 

tear off; and return to the above address. 

If you do not desire to continue receiving these technical 

reports. CHECK Wfflf • ; tear off label, and return it to the 

above address. 

Publication No. EPA- 600/R - 97-018b