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

PRIMARY GOAL

TO INCREASE UNDERSTANDING OF

SAFE INSTALLATION PRACTICES REGARDING

USE, HANDLING AND DISPOSAL OF SPRAY

POLYURETHANE FOAM (SPF).
Industry-led Product Stewardship: ThreePronged 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 highpressure 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 InProgress

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 twocomponent, 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 InProgress

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 Site 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: Guidance 

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)

(Ethylhexanoic, 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. Collected 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

Concentration 

HFC-134a

- 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/min
Courtesy 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 

• Evaluated 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, m3 5.15E-05

Air Change Rate, h-1(N) 58.2

Loading, m2/m3(L) 62.5

Specific Air Flow Rate (N/L) 0.931

Initial Temperature 23 oC
Sampling from Micro Chamber

90mm Glass-Fiber Filters with PP Silica Gel with DNPH Tube

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 oC 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 semivolatile 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 

• Evaluated 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 microscale 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). 

NH2 NH2

+ R N C O

NH NH2

O

NH

R

HN NH

O

R NH2

+

1,8-DAN Perimidone
III Project 306

DAN Method Refinement 

OBJECTIVESDevelop 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 μL 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; source 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