# Industry Update: Spray 

# Polyurethane Foam Product Stewardship April 24, 2013

# Agenda

• Welcome

• CPI SPF Health and Safety Training Update

• CPI SPF Outreach Update

• CPI SPF Research Update

• International Isocyanate Institute Update

• SPFA Update on Professional Certification Program

• Federal Partner Updates

# Industry

- led Product Stewardship

P RIMARY 

## G OAL 

# T O INCREASE UNDERSTANDING OF
SAFE INSTALLATION PRACTICES REGARDING
USE 

# , HANDLING AND DISPOSAL OF SPRAY
POLYURETHANE FOAM 

# (SPF).

# Industry

- led Product Stewardship: Three



# Pronged Approach

Program focuses on practices and communications that can help to minimize potential for exposure of workers and building occupants to SPF chemicals.

• Worker Performance and Training

– develop and deploy health and safety training programs for professional SPF applicators.

• Outreach

- Educate DIY’ers , consumers and the building/construction sector about best practices on key issues including informing the selection of a contractor; different types of SPF products; health and safety considerations for DIY’ers and consumers during and after SPF product installation.

• Research

- Develop research and support testing programs to develop a better understanding of potential exposure to chemical components for workers applying SPF and potential consumer/occupant exposure to SPF emissions.

# CPI SPF Health and Safety



# Training Update Bill Robert, BASF

## High

- pressure product training launched in Dec. 2010.

The program provides free online health and safety information for SPF contractors, applicators or 

## helpers who work with two

- component high

pressure SPF systems.

More than 7,000 users have accessed the training 

## program either online or in an instructor

- led capacity.

This program was recently upgraded and translated 

## in to Spanish (Dec 2012). 

# CPI SPF Health and Safety Training Programs: 

# High

- Pressure

## ACC CPI High

- pressure Safety & Health Training Through 

## March 2013

Test Scores through February 2013 100% 90

- 99% 70

- 89%
Percent achieving test scores: English 43% 46% 11%
Percent achieving test scores: Spanish 0% 25% 75% February 2013 English February 2013

Spanish March 2013

English March 2013

Spanish Total Through March 2013

Job Description Fully Complete Fully Complete Fully Complete Fully Complete Fully Complete In Progress

Instructor Online Instructor Online Instructor Online Instructor Online Instructor Online Started, not finished

Applicator 0 112 0 4 11 121 0 4 234 1915 796

Helper 0 19 0 0 2 28 0 3 42 306 112

Other 0 60 0 1 2 45 0 0 218 1531 673

Supervisor 0 48 0 1 0 55 0 1 390 1021 598

Total 0 239 0 6 15 249 0 8 880 4773 2179

Total Students Fully Completed Through

March 2013 Total Students Started or Finished Through March 2013

5653 7832

# Low

- pressure product training launched in Dec. 2012 in English and Spanish.


# This training was supported by grant funding from OSHA.

The Low

- Pressure Training provides information for weatherization professionals, applicators or helpers, who work with one

- component SPF or two



# component, low

- pressure SPF kits for sealing and insulating. CPI SPF Health and Safety Training Programs: 

# Low

- Pressure

## ACC CPI Low

- pressure Safety & Health Training Through 

## March 2013

Test Scores through March 2013 100% 90

- 99% 70

- 89%
Percent achieving test scores: English 16% 59% 25%
Percent achieving test scores: Spanish 49% 51% 0% Total Students Fully Completed Through

March 2013 Total Students Started or Finished Through March 2013

320 533 February 2013 English February 2013

Spanish March 2013

English March 2013

Spanish Total Through March 2013

Job Description Fully Complete Fully Complete Fully Complete Fully Complete Fully Complete In Progress

Instructor Online Instructor Online Instructor Online Instructor Online Instructor Online Started, not finished

Applicator 0 33 0 3 0 32 1 5 1 102 64

Helper 0 11 0 0 0 9 0 0 0 27 11

Other 0 33 0 0 0 15 0 1 0 126 90

Supervisor 0 19 0 0 0 9 0 0 0 64 50

Total 0 96 0 3 0 65 1 6 1 319 215

## Trainees have the option of taking one or both of the training courses.



## Each training program takes between 1.5 to 2.5 hours to complete.



## Those who pass with a 70% or higher receive a “recognition of completion” form and wallet

- size card, which is valid for 2 years.



## Completion of the training programs is a prerequisite for any level of the certification in SPFA’s Professional Certification Program. 

# CPI SPF Health and Safety Training Programs

### For convenience, both programs are available online 24/7 or in a classroom setting when organized by a registered instructor.

Instructors must pass the course with a score of of 100% and sign an agreement to become an instructor.

The Instructor Guide, available online in English and Spanish, explains how to become a registered instructor.



### A dedicated landing page was developed so links from various organizations can drive traffic directly.

A searchable database is available to verify whether a user has 

### successfully completed the course (must renew every two years). 

# CPI SPF Health and Safety Training Programs 

# Instructor Training

### This video provides general guidance for professionals on how to apply low

- pressure spray polyurethane foam. It is intended as a 

### supplement to other job safety information already available such as specialized training, Safety Data Sheets (SDS ), product label information and other materials.

. 

# Working Safely with Low

- Pressure Spray Polyurethane Foam Insulation

Online DVD

The video is available to view or download at www.spraypolyurethane.org.

The video has over 2,400 downloads.

# Next Steps

• Continue to support the learning management system that hosts both training programs

• Provide user support to the training programs

• Work with members, allies and others to promote the training programs



### • Continue to look for ways to enhance the training program

# CPI SPF Outreach Update

Monica Karamagi, Huntsman

# CPI SPF

Outreach Outreach and education to the D

- I

- Y

market and directly to audiences using, specifying, requesting, or contracting for SPF and occupying buildings in which SPF has been installed.

Educate SPF contractors and weatherization professionals about 

### SPF EHS training available, health and safety practices, including occupant outreach.

# Website 

# www.spraypolyurethane.com

# Spray Polyurethane Foam: Posters 

# www.spraypolyurethane.com

# Spray Polyurethane Foam: Guidance Documents 

# www.spraypolyurethane.com

# SprayPolyurethane.com 

# Web Statistics

• Significant S ite Traffic Growth

EOY Results Should Exceed Even Further:

• organic campaign only ramping up

• PPC cost

- per
- click dropping

• PPC click

- through

- rate growing 

### Traffic Growth 2010

- 2012 Visitors: +168% Visits by Search: +1,131% 

### Pageviews: +81%

Site Performance 2012 Average Visit: 5.9 min Pages/Visit: 2.5 

### Bounce Rate: 56%

0 5,000 10,000 15,000 20,000 25,000 30,000 35,000 40,000

2010 2011 2012

Total Visitors 2010

- 2012

# SprayPolyurethane.com 

# Web Statistics

• Growing Visibility to Searchers using Google, Bing, Yahoo! etc.

EOY Results Should Exceed Even Further:

• organic campaign only ramping up

• PPC cost

- per
- click dropping

• PPC click

- through

- rate growing 

### Visits From Search 2010

- 12 Total Visits: +1,131% Organic Search: +1,264% 

### Paid Search: +694%

Visits By Source 2012 Search Activity: 46% Other Sites/Links: 30% 

### Direct/Typed: 24%

0 5,000 10,000 15,000 20,000 25,000

2010 2011 2012 Visits From Search Activity 2010

- 2012

Organic Search Paid Search

# SprayPolyurethane.com 

# Web Statistics

• High Interest in Site Content

EOY Results Should Exceed Even Further:

• organic campaign only ramping up

• PPC cost

- per
- click dropping

• PPC click

- through

- rate growing 

### Key Audience Segments Homeowner Building Professional 

### Weatherizing Professional Do

- It

- Yourself Installer

Content Types How

- to/Background Text Safety

- related Text/Video 

### Links to Trusted Resources

0 20,000 40,000 60,000 80,000 100,000 120,000

2010 2011 2012

Pages Viewed 2010

- 2012

# SprayPolyurethane.com 

# Web Statistics

• Most

- Viewed Pages Address Key Audience Segments

• Home Page

- 45 % of total page views (2012)

• I am an SPF Contractor or Homebuilder

- 11 %

• Spray Polyurethane Foam Chemical Health and Safety Training

- 11 %

• Insulating Foam Sealant for Do

- It

- Yourself (DIY) Projects

- 11 %

• I’m a Do

- It

- Yourselfer Installing Spray Polyurethane Foam (SPF )

- 7 %

• How Does Spray Polyurethane Foam (SPF) Insulation Work?

- 7%

# SprayPolyurethane.com 

# Web Statistics

• Site Enjoys Nationwide Reach

EOY Results Should Exceed Even Further:

• organic campaign only ramping up

• PPC cost

- per
- click dropping

• PPC click

- through

- rate growing 

### States Generating Highest Visitor Totals 2012 California 

### Texas New York Pennsylvania Florida 

### Illinois Ohio Michigan Massachusetts

# Website 

# www.spraypolyurethane.com

 Recently completed: G uidance for Selecting a Contractor for the Installation of SPF in School Buildings; Fire Safety 

### Guidance; Guidance for Videos or Images Showing SPF Application; and Guidance on Best Practices for the Insulation 

### of SPF

 Continue to promote available health and safety information 

### at industry events

# Worker Training

- Outreach

Outreach for new LP CPI SPF Worker 

### Training:

 December 2012, announcement to CPI, SPFA, agencies and other third parties about training launch and availability

 Email promotion to over 300 weatherization contacts and state officials (Dec. 2012)

 Press release on availability of on

- line training (Dec. 2012)

# Worker Training

- Outreach

Outreach for CPI SPF Worker Training 

### Programs:

 Launched new training landing page in English and Spanish (Dec. 2012)

 Fliers promoting training for events 

### e.g. SPFA Conference ( Feb. 2013)

 Spanish news release sent promoting the translated training programs (Feb. 2013)



###  Advertised in January/February 2013 SprayFoam Insulation and Roofing Magazine

 Training article published in SPFA’s 

### magazine (Feb. 2013)

# Path Forward Outreach

 Continue outreach and education on training program and information available on SPF website www.spraypolyurethane.org at 

# industry events.

 Continue to seek opportunities for 

# promotion.

 Continue on review and keeping content on www.spraypolyurethane.org up to date.

27

# SPF VENTILATION 

# RESEARCH UPDATE

RICHARD WOOD, CIH AIR PRODUCTS AND CHEMICALS

# Purpose

Objective

– Evaluate the impact of changes in ventilation rates on concentrations of SPF chemical vapor and particulate emitted during application.
Chemical ingredients of interest include:

• Methylene diphenyl diisocyanate (2,4

- MDI, 4,4

- MDI)

• Polymeric methylene diphenyl diisocyanate (pMDI)

• Amine Catalysts

– (BDMAEE, TMAEEA, DAPA, TMIBPA, and PMDETA)



### • Chemical Blowing Agents (HFC

- 245fa and HFC

- 134a)

• Flame Retardant (TCPP)

# Project Status

Phase 1

- Complete

• Develop and test generic high pressure low density, high pressure medium density, and low pressure kit formulations.

• Evaluate commercial spray equipment using the formulations.



### Phase 2

– In progress

• Conduct air sampling in a fabricated spray room and spray booth to measure chemical emissions during application of the generic 

### formulations under controlled environmental conditions.



### Phase 3

– Not started

• Conduct air sampling in the field, such as a medium

- sized residential building, to measure chemical emissions during SPF application.

# Phase 1

• Three generic formulations were developed:

• Low density open cell formulation

• Medium density closed cell formulation

• Low pressure 2

- component kit formulation



### • The formulations represent typical commercial systems; however, do not reveal confidential information of actual formulations on the market/in use.

• Generic formulations used for the CPI Ventilation and Emissions studies.Low density

- open cell Medium density

- closed cell Low pressure - Kit

A

- side

100% pMDI 100% pMDI 92.5% pMDI Blowing Agent HFC

- 134a (7.5% )

B

- side

Polyether polyol (Triol) 34% Aromatic Polyester Polyol (36.39%) Aromatic Amino Polyether Polyol (33.61%) Polyester Polyol (23%) Polyether Polyol (23%)

NPE Emulsifier (11.9%)

Blowing agent
Water 20% Blowing agent HFC

- 245a (6.97%) Water (2.53%) Blowing Agent
HFC

- 134a (17%)

Fire Retardant
Tris

- (1

- chloro

- 2

- propyl) phosphate (TCPP) (25.2%) Fire Retardant Tris

- (1

- chloro

- 2

- propyl) phosphate TCPP (15.91%) Fire Retardant
Tris

- (1

- chloro

- 2

- propyl) phosphate TCPP (30%)
Silicone Surfactant ( 1.0%) Silicone Surfactant ( 1.0%) Silicone Surfactant (2%)

Catalyst
Bis (2

- Dimethylaminoethyl) ether ( 0.9 %) (BDMAEE) Tetramethyliminobispropylamine (3.0 %) (TMIBPA) N,N,N

- Trimethylaminoethylethanolamine (4.0 %) (TMAEEA) Catalyst
Bis (2

- Dimethylaminoethyl) ether ( 0.7 %) (BDMAEE)
Bis ( dimethylaminopropyl ) methylamine (2.59 %) (DAPA)

N,N,N

- Trimethylaminoethylethanolamine (0.3 %) (TMAEEA) Catalyst (5%) Pentamethyldiethylene triamine (PMDETA) ( E thylhexanoic , 2

- , potassium salt/ Oxybisethanol , 2,2’)

# Phase 2 

# Test Protocol for Ventilated Spray Room

Three (3) generic formulations sprayed at four (4) ventilation rates

• proposed rates

- 0.3, 2, 5, and 10 Air Changes per Hour (ACH) 

### Testing has been completed for 10 ACH

• Four (4) sessions of personal and area sampling were completed for each formulation.

• Each session included post

- spray sampling beginning 30 min after the completion of the spray session. 

### Two (2) hour ventilation purge between sessions.

# Ventilated Spray Room

• Approximately 8 ft x 8ft x 8ft

• Adjustable air flow rates range between 0.3 ACH and 13 ACH

• Ventilation rate of 85 cfm or 10.4 ACH selected for first series of testing. Very low flow rate equivalent to 1 air change every 6 min.

• Make

- up air introduced on one side of the room and exhausted though a filter bank on the opposite wall of the room.

• Spray equipment and chemicals located outside the room.

# Work Process

• Applicator sprayed 2 inserts, removed the inserts, stacked them in the work area, placed new inserts in the substrate, and repeated the process.

• Twelve (12) inserts sprayed for low and medium density formulations. Six (6) inserts for the kit formulation. The amount of foam sprayed (lbs) and foam densities were recorded.

• Spray time limited to 15 minutes during SPF application.

• Post spray area samples collected 30 min after SPF application completed.

• Sprayed inserts remained in the room

• Ventilation continued to operate during the one hour test period

# Air Sampling

Area samples located behind the applicator. C ollected during SPF application and post

- spray session

Personal samples positioned on spray applicator

# Ventilated Spray Room

Courtesy of Air Products and Chemicals, Inc.

# Findings

- 10.4 ACH

• 2,4

- MDI, 4,4

- MDI and polymeric MDI detected in personal and area samples. No MDI detected in post

- spray samples.

• Amine catalysts detected in personal and area samples. Certain 

### amine catalysts also detected in post

- spray samples.

• TCPP fire retardant detected in personal and area samples. Trace quantities detected in post

- spray samples.

• Blowing agents HFC

- 245fa and HFC

- 134a detected in personal and area samples.

• No HFC

- 245fa in post

- spray samples

• HFC

- 134a detected in post

- spray samples

# 2,4

- MDI and 4,4

– MDI ( 

### Average of 4 sessions

- 15 min/session at 10.4 ACH)

0 0.005 0.01 0.015 0.02 0.025 0.03

2,4-MDI
4,4-MDI Concentration - ppm

Medium Density Low Density

Low Pressure Kit

# p - MDI (Average of 4 sessions

- 15 min/session at 10.4 ACH)

0 0.05 0.1 0.15 0.2 0.25 0.3

Applicator Area Post Spray Applicator Area Post Spray Applicator Area Post Spray p-MDI Concentration - mg/m3

Medium Density Low Density Low Pressure Kit

# Amine Catalysts (Average of 4 sessions

- 15 min/session at 10.4 ACH)

0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5

Applicator Area Post-Spray Applicator Area Post-Spray Applicator Area Post-Spray Concentration - ppm

BDMAEE

TMAEEA

DAPA

TMIBPA

PMDETA

Medium Density Low Density

Low Pressure Kit

# TCPP

– Fire Retardant (Average of 4 sessions

- 15 min/session at 10.4 ACH)

Medium Density Low Density

Low Pressure Kit Concentration - ppm

0 0.05 0.1 0.15 0.2 0.25 0.3 0.35

Applicator Area Post Spray Applicator Area Post Spray Applicator Area Post Spray TCPP

# Blowing Agents (Average of 4 sessions

- 15 min/session at 10.4 ACH)

1 10 100 1000 10000

Applicator Area Post Spray Applicator Area Post Spray HFC-245fa

HFC-134a Concentration - ppm

Medium Density Low Pressure Kit

# Summary

– 10.4 ACH Research

1. CPI Ventilation Research Task Force reviewed findings.

• Recommended future studies be conducted at higher air exchange rates.



### 2. Task Force recommended testing one formulation in an adjacent spray booth for the purpose of evaluating the impact of high ventilation rates on SPF emissions.

• Generic medium density formulation selected for testing.

# Ventilated Spray Room and Spray Booth

Courtesy of Air Products and Chemicals, Inc.

# Ventilated Spray Booth

• Spray booth dimensions 10 ft x 10.5 ft x 7 ft

• Booth operates at two ventilation rates

- full speed or reduced speed.

• Full speed ventilation rate 7,265 cfm or 598 ACH.

• Equivalent to approximately 10 air changes/minCourtesy of Air Products and Chemicals, Inc. Substrate X X Area Samples

Applicator Air Flow 10.4 ACH 598 ACH

10 ‘

10’ 6’’ Spray Booth Ventilated Spray Room and Spray Booth 10 air changes per hour vs. 10 air changes per min

# Work Process

• Applicator sprayed 2 inserts, removed the inserts, stacked them in the work area, placed new inserts in the substrate, and repeated the process.

• Twelve (12) inserts sprayed with generic medium density formulation. The amount of foam sprayed (lbs) and foam densities were recorded.

• Spray time limited to 15 minutes during SPF application.

• Post spray area samples collected 30 min after SPF application completed.

• Sprayed inserts remained in the room

• Ventilation continued to operate during the one hour test period.

# Findings

- 598 ACH

Concentrations of 2,4

- MDI, 4,4

- MDI and polymeric MDI detected in personal and area samples. No MDI detected in 

### post

- spray samples.
Amine catalyst, fire retardant, and blowing agent concentrations were at or below analytical detection limits.


### Higher ventilation rate did not obviate the need for use of PPE.

# 2,4

- MDI and 4,4

– MDI (Average of 4 sessions

- 15 min/session at 598 ACH)

0 0.002 0.004 0.006 0.008 0.01 0.012 0.014 0.016

Applicator Area Post Spray 2, 4-MDI
4,4-MDI Concentration - ppm

Medium Density Formulation

# 2,4

- MDI and 4,4

– MDI (Average of 4 sessions

- 15 min/session at 10.4 ACH and 598 ACH)

0 0.005 0.01 0.015 0.02 0.025 0.03

Applicator Area Post Spray 2,4-MDI - 10.4 ACH
4,4-MDI - 10.4 ACH
2,4-MDI - 598 ACH
4,4-MDI - 598 ACH Concentration - ppm

Medium Density Formulation

# p - MDI (Average of 4 sessions

- 15 min/session at 598 ACH)

0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2

Applicator Area Post Spray pMDI-598 ACH Concentration - mg/m3

Medium Density Formulation

# p - MDI (Average of 4 sessions

- 15 min/session at 10.4 ACH and 598 ACH)

0 0.05 0.1 0.15 0.2 0.25 0.3

Applicator Area Post Spray pMDI-10.4 ACH pMDI-598 ACH Concentration - mg/m3

Medium Density Formulation

# Path Forward

• CPI Ventilation Research Task Force reviewed all findings:

1. Recommended one additional air sampling session to be conducted as foam is sprayed in the spray booth at a reduced fan speed of 1/3 to 1/2 full speed rate to evaluate the effect of reduced ventilation on SPF emissions. 2. Generic medium density formulation selected for testing. 3. Testing to be conducted May 2013



### • CPI Ventilation Research Task Force will prepare an interim report summarizing combined monitoring results for generic medium density, low density, and kit formulations at specified air exchange rates.

• CPI Ventilation Research Task Force will continue to evaluate findings and consider additional Phase 2 or Phase 3 testing.

# QUESTIONS?

# SPF Emissions Update

John Sebroski, Bayer MaterialScience LLC

# CPI Emissions Task Force Objective

Develop methods for SPF standardization that can be used by manufactures to evaluate potential emissions released from SPF insulation samples.

Participate in research to support the development of SPF product emissions standards through ASTM Sub

- committee D22.05 on Indoor Air Quality.

# ASTM Subcommittee D22.05 on Indoor Air

SPF Emissions Task Group Members

• Industry/CPI



### • Regulatory (US EPA, CPSC, etc.)

• Instrument Vendors

• Consultants



### • Air Quality Testing Labs

• Certification Programs

• Other Stakeholders 

### SPF Emissions Task Group Chair

• John Sebroski, Bayer MaterialScience LLC

# Current ASTM Work Items

• ASTM WK30960
Standard Practice for Spraying, Sampling, Packaging, and Test Specimen Preparation of Spray Polyurethane Foam (SPF) Insulation Samples for Environmental Chamber Emissions Testing.



## • ASTM WK40292

New Test Method for Measuring Chemical Emissions from Spray Polyurethane Foam (SPF) Insulation Samples in Environmental Test 

### Chambers with Thermal Desorption and Gas Chromatography / Mass Spectroscopy (TD

- GC

- MS ).



## • ASTM WK40293

New Practice for Estimating Chemical Emissions from Spray Polyurethane Foam (SPF) Insulation using Micro

- Scale Environmental Test Chambers.

# Future ASTM Work Items

• Standard Practice for Development of Generic SPF Formulations

• Standard Test Method for Measuring MDI using LC 

## MS/MS During Chamber Testing/IAQ Studies

# Summary of CPI Emissions Research

• CPI developed generic SPF formulations for research

• Developed analytical method for SPF emissions

• Established micro

- scale chamber conditions for SPF

• Sample preparation, holding time and packaging study

• E valuated wall adhesion effects of SVOCs in chambers

# Generic SPF Formulations

Three generic SPF formulations were developed by CPI to evaluate the test methods for measuring emissions. The formulations represent the following sample types:

Spray Polyurethane Foam Closed

- cell 2 pound 

### High Pressure Spray Polyurethane Foam Open

- cell 1/2 pound 

### High Pressure

Spray Polyurethane Foam Kit Formulation 2 Component, Low Pressure

# Analytical Methodology

Developed thermal desorption GC/MS 

## analytical method for measuring potential SPF emissions

# Target Compounds by TD

- GC/MS

Peak Number Compound Name MS Quantitation Ion Retention Time, minutes Estimated

Quantitation Limit, ng

1 HFC

- 245a 51 1.48 20

2 TMAEEA 58 7.69 200

3 BDMAEE 58 7.72 20

4 PMDTA 72 8.26 50

5 DAPA 58 9.56 100

6 TMIBPA 58 9.65 200

7 TCPP 99 12.5 50

# TD

- GC/MS Precision and Recovery

Compound True Value, ng Mean, ng Recovery, % RSD, %

HFC

- 245a 706 634 89.7 10.9

TMAEEA 2179 1559 71.5 24.6

BDMAEE 1034 977 94.5 4.10

PMDTA 1114 1035 92.9 3.52

DAPA 1072 1031 96.2 3.38

TMIBPA 2397 1631 68.1 13.3

TCPP 996 922 92.6 2.94

# SPF Emissions with Micro Chamber

Established baseline conditions and sample preparation techniques for measuring SPF emissions with micro

- scale test chambers

# Specimen Preparation for Micro Chamber

Closed

- cell SPF specimen fits tightly into the micro chamber.

# Micro Chamber Test Conditions

Parameter Value

Sample Diameter, m 0.064

Volume, m 3 5.15E

- 05

Air Change Rate, h

- 1 (N) 58.2

Loading, m 2 /m 3 (L) 62.5

Specific Air Flow Rate (N/L) 0.931

Initial Temperature 23 o C

# Sampling from Micro Chamber

Silica Gel with DNPH Tube

90mm Glass

- Fiber Filters with PP 13mm Glass

- Fiber Filter with 1

- (2

- pyridyl) piperazine (PP) & diethyl phthalate Flow Calibrator

Thermal Desorption Tubes

# Holding Time and Packaging Study

Conducted SPF insulation holding time 

### and packaging study using generic SPF formulations
Data to support development of ASTM standard practice

# Holding Time Observations

Generic closed

- cell and open

- cell SPF samples can be stored for up to 48 hours at 23 o C in sealed PET bags. 

# During this time, the emission factor values for target compounds did not significantly change.

# SVOA Wall Effects Evaluation

There is a concern that semi

volatile organic compounds (SVOCs) may adhere to the walls of the environmental test chambers, which could bias emission results.

The SVOCs of interest (MDI, 

## selected amine catalysts and flame retardant) were spiked into micro chambers and small

- scale stainless chambers to evaluate recoveries.

# Spiking Study Observations

MDI spike recoveries were not consistent and a significant percentage of the spiked MDI adhered to the chamber walls, regardless of the material and size of the test chamber.



## Amine catalyst recoveries ranged from 4 to 45% with conventional chambers; improved to 81 to 99% with the micro chamber.


## The flame retardant recovery in conventional chambers ranged from 25 to 38%; however, complete recovery was observed in the micro chamber when using air as 

## the carrier gas.

# Summary of Emissions Research

• CPI developed generic SPF formulations for research

• Closed

- cell, Open

- cell and Kit Formulation



### • Developed analytical method for SPF emissions

• Thermal Desorption GC/MS can be used to measure blowing agent and other VOCs, amine catalysts and flame retardant



### • Established micro

- scale chamber conditions for SPF

• Flow rate, loading factor, carrier gas, sampling, etc.



### • Sample preparation, holding time and packaging study

• 48

- hr holding time in PET bag, supports ASTM draft practice



### • E valuated wall adhesion effects of SVOCs in chambers

• Improved amine catalyst and flame retardant recovery with micro chambers

# Current Activities

• ASTM D22 on Air Quality Ballot, January 2013

• Standard Practice for Spraying, Sampling, Packaging, and Test Specimen Preparation of Spray Polyurethane Foam (SPF) Insulation Samples for Environmental Chamber Emissions Testing



### • Collaboration with US EPA, Office of Research and Development

• Ongoing meetings and discussion to identify collaboration 

### opportunities

• 2013 Research Projects

• CPI to further develop analytical test methods; optimize recovery of flame retardant and amine catalysts using micro



### scale test chambers

• International Isocyanate Institute (III) to evaluate prototype of test chambers optimized for MDI emissions

# Next Steps

ASTM Committee D22 Ballot Item

• WK30960 Standard Practice for Spraying, Packaging and Test Specimen Preparation of SPF Insulation for Testing of Emissions Using Environmental Chambers 

## New Work Items at ASTM D22.05 on Indoor Air

• WK40292 Standard Test Method for Measuring SPF Chemical Emissions with Thermal Desorption Tubes and GC/MS

• WK40293 Standard Practice for using Micro Chamber to Measure SPF Emissions 

## Research to support development of ASTM standards

• Environmental Test Chamber Optimization of SVOCs (Amine Catalysts, Flame Retardant and MDI)

• Optimize Thermal Desorption GC/MS Method

• Planning Validation Study for Analytical Method

# QUESTIONS?

# III Project Proposal

Environmental Test Chamber Optimization for MDI


# John Sebroski, Bayer MaterialScience LLC

# Background and Objective

If MDI is emitted during product emission testing, it may adhere to the surface of conventional test chamber walls (e.g. micro chamber, small scale PTFE lined and stainless steel chambers). This objective will be to evaluate the suitability of modified FLEC cell and micro chamber prototype for 

## measuring MDI emissions during product emission testing.

# Modified FLEC Cell

A modified FLEC cell will be evaluated to optimize MDI recovery. The modified design will place the sampling filter inside the FLEC cell with rare earth magnet discs, 3mm diameter x 0.8mm thick to reduce 

## the exposed chamber walls.

The chamber will be fortified using 

## glass

- fiber filters that have been treated with PMDI or using a FLEC cell recovery kit.

# Micro Chamber Prototype

A modified micro chamber prototype, B

- PROD017, supplied by Markes International, will be evaluated to optimize MDI recovery.

The modified design places the sampling filter inside the chamber 

## near the top lid; the sample can be further elevated to reduce exposed chamber walls

.
The chamber will be fortified the same way as the FLEC cell.

# Analytical and Optimization

MDI emissions will be collected with glass

- fiber PP filters; the chamber walls will be sampled with glass

- fiber PP filters moistened with acetone. The emission and wipe samples will be tested for 2,4’

- MDI, 4,4’

- MDI, and p

- MDI with LC/MS/MS for optimal detection limits.



### Based on the results, the prototype and spiking protocol may be redesigned or optimized, and then the evaluation repeated. For example, spacers may need to be added to reduce the surface area of 

### the chamber walls; the flow rate of the carrier gas may need changed, etc. to optimize recovery.

# QUESTIONS?84



# Analyzing for Total NCO 

# Project 306 : DAN Method Refinement Principal Investigators: Bello (UMass), Streicher (NIOSH)
Presented By: Liz Hugel (BASF Corp; III

- AAG)

24

- April

- 2013

# Earlier DAN Method Work

III

- sponsored work by Streicher & Bello in the early 2000s:

• Conducted initial method development



### • Demonstrated potential utility of DAN for TRIG measurement



## Remaining method development issues:

• Spontaneous blank formation of perimidone

• High DAN concentration required for rapid reaction challenged analytical sensitivity

# DAN reaction sequence

Diaminonaphthalene (DAN) reacts with isocyanate to form a urea: a cyclization reaction forms perimidone. Each isocyanate group present forms a molecule of perimidone. 

### The Total Reactive Isocyanate Group (TRIG) can be quantified by the separation and quantification of only perimidone (PD).

# III Project 306 DAN Method Refinement

OBJECTIVES

Develop HPLC

- UV and LC

- MS/MS analytical methods for perimidone (PD).



### Optimize the sample clean

- up procedures to remove excess DAN reagent and other sample impurities with attention to the volumes needed for impinger samples.

Complete an investigation of the side reaction of PD blank formation from DAN reagent.

Conduct a field simulation study in which the developed DAN method 

### is compared to an existing TRIG method.

# Project 306 Results

Objective 1: Develop HPLC

- UV and LC

- MS/MS analytical methods for perimidone (PD).



## Sensitive and robust LC

- MS/MS method developed

• Minimal sample preparation

• High throughput (17 min injection

- to

- injection)

• Internal standard (deuterated PD) calibration linear over wide range (4 orders of magnitude)

# Project 306 Results

Objective 2: Optimize the sample clean

- up procedures to remove excess DAN reagent and other sample impurities with attention to the volumes needed for impinger samples.

2003 work: solid phase extraction technique needed in sample workup procedure to remove excess DAN With new MS/MS method no clean

- up needed

• DAN impinger solution levels ~ 10x lower

• High instrumental sensitivity permits sample dilution (10

- 40x) to stay in calibration range 

### Sample prep:

• Take 0.5 mL of sample impinger solution (5mM DAN in DMSO )



### • Add 0.5 mL formic acid

• After 30 min reaction time, add 10 μ L acetone (consumes unreacted DAN)

• Add internal standard to sample and analyze

# Project 306 Results

Objective 3: Complete an investigation of the side reaction of perimidone blank formation from DAN reagent. PD blank thought to come from two sources:

• Impurities in DAN (fast reaction, limited source)

• Side reaction with DAN itself (slower reaction, larger source) 

## Numerous investigations to clarify factors affecting PD blank formation; 

# s ource of carbonyl for blank PD still unknown Practical improvement: substitution of formic acid for acetic acid in step 2 (cyclization) lowers PD blank Conclusion: with current method improvements, PD blank levels now sufficiently controlled (low and consistent) to allow method

use.

# Project 306 Results

Objective 4: Conduct a field simulation study in which the developed DAN method is compared to an existing TRIG method.


## Field sampling conducted at an SPF training center during application of SPF insulation

• Purpose: To compare the DAN method to an existing TRIG 

### method; spray application method chosen to ensure the presence of airborne NCO

• Two area monitoring stations were established inside the spray room (no personal sampling)



### • Each spray period was approximately 15 minutes 

## Method comparison:

• DAN total NCO (from PD)

• MAP total NCO

o Modified NIOSH method 5525

o NCO calculated from sum of MDI monomers, 3

- , 4

- , 5

- ring peaks

# DAN simulated field study

“A” sampling round

• Only PMDI sprayed for a portion of the 15 min. spray period resulting in higher concentrations than in the other rounds

• DAN / MAP Total NCO ratio [ mean ( ± SD )] 

### :

o 

### 1.3 ( ± 0.5) [range of ratios: 0.9

- 2.0; n=4]  Based on preliminary analysis, data suggests a significant portion of the total NCO detected by the DAN method is accounted for by the monomeric MDI species 

## “B”

– “E” sampling rounds

• Normal SPF application

• DAN / MAP Total NCO ratio [mean ( ± SD )] 

### :

o 

### 7.9 ( ± 10) [ range of ratios: 1.5

- 44; n=16]  Based on preliminary analysis, data suggests that the majority of NCO detected by DAN is not accounted for by the monomeric MDI species, so it is likely from higher oligomeric species

# DAN Method

- Status

Data analysis from the field comparison is on

- going

Planning for DAN method’s application in research projects for total NCO determination

• Interpretation of which NCO

- containing species are present requires concurrent use of another method (e.g., MAP [NIOSH 5525], PP [OSHA 47])



### • UMass Lowell willing to serve as analytical lab for studies using the DAN method