Astm stp 1589 2017

Paul Duffy and Richard Wood Flame Retardant Emissions from Spray Polyurethane Foam Insulation 57 Dustin Poppendieck, Matthew Schlegel, Angelica Connor, and Adam Blickley Glass Chamber Me

Selected technical PaPerS

StP1589

Editors: John Sebroski and Mark Mason

Developing Consensus

Standards for Measuring

Chemical Emissions from Spray Polyurethane Foam (SPF)

Library of Congress Cataloging-in-Publication Data

Names: Sebroski, John, editor | Mason, Mark 1947-, editor

Title: Developing consensus standards for measuring chemical emissions from

spray polyurethane foam (SPF) insulation / editors: John Sebroski, Mark

Mason.

Description: West Conshohocken, PA : ASTM International, [2016] | Series:

Selected technical papers ; STP 1589 | “ASTM Stock #STP1589.” | Includes

bibliographical references.

Identifiers: LCCN 2016046094 (print) | LCCN 2016046208 (ebook) | ISBN

9780803176232 | ISBN 9780803176249 (ebook)

Subjects: LCSH: Insulating materials–Standards–United States | Insulation

(Heat) Standards United States | Polyurethanes–Environmental aspects

| Aerosols Environmental aspects.

Classification: LCC TH1715 D4115 2016 (print) | LCC TH1715 (ebook) | DDC

691/.95 dc23

LC record available at https://lccn.loc.gov/2016046094

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When citing papers from this publication, the appropriate citation includes the paper authors, “paper title,” STP title, STP number, book editor(s), ASTM International, West Conshohocken, PA, year, page range, paper doi, listed in the footnote of the paper A citation is provided on page one of each paper Printed in Bay Shore, NY

February, 2017

THIS COMPILATION OF Selected Technical Papers, STP1589, Developing

Con-sensus Standards for Measuring Chemical Emissions from Spray Polyurethane Foam (SPF) Insulation, contains peer-reviewed papers that were presented at a sympo-

sium held April 30–May 1, 2015, in Anaheim, California, USA The workshop was sponsored by ASTM International Committee D22 on Air Quality and Subcommit-tee D22.05 on Indoor Air

Symposium Chairpersons and STP Editors:

John Sebroski

Covestro LLC Pittsburgh, PA, USA

Mark Mason

US Environmental Protection Agency Research Triangle Park, NC, USA

Foreword

Evaluation of Micro-Scale Chambers for Measuring Chemical Emissions

John Sebroski, Jason W Miller, Carl P Thompson, and Elizabeth Roeske

Measurement of Chemical Emissions from Spray Polyurethane Foam Insulation

Using an Automated Micro-Scale Chamber System 27 Yunyun Nie, Eike Kleine-Benne, and Kurt Thaxton

VOC Analysis of Commercially Available Spray Foam Products 43

J Paul Duffy and Richard Wood

Flame Retardant Emissions from Spray Polyurethane Foam Insulation 57 Dustin Poppendieck, Matthew Schlegel, Angelica Connor, and Adam Blickley

Glass Chamber Method for Screening of 4,4'- MDI and TCPP Emissions from

Doyun Won, Angelika Zidek, Gang Nong, and Ewa Lusztyk

Prioritizing Chemical Emissions from Closed-Cell Spray Polyurethane Foam:

Utilizing Micro-Scale Chamber Emission Factors and Field Measurement Data 98 Scott Ecoff, Shen Tian, and John Sebroski

Computer Simulation of Peak Temperatures in Spray Polyurethane Foam

Used in Residential Insulation Applications 119 Richard S Duncan

Assessment and Remediation of Misapplied Spray Polyurethane Foam 138

Ed Light

Estimating Re-Entry Times for Trade Workers Following the Application of

Three Generic Spray Polyurethane Foam Formulations 148 Richard Wood

Contents

Predicting TCPP Emissions and Airborne Concentrations from Spray

Polyurethane Foam Using USEPA i-SVOC Software: Parameter

Shen Tian, John Sebroski, and Scott Ecoff

A Modeling Approach for Quantifying Exposures from Emissions of

Spray Polyurethane Foam Insulation in Indoor Environments 199 Charles Bevington, Zhishi Guo, Tao Hong, Heidi Hubbard, Eva Wong,

Katherine Sleasman, and Carol Hetfield

Investigating Sampling and Analytical Techniques to Understand Emission

Characteristics from Spray Polyurethane Foam Insulation and Data Needs 228 Katherine Sleasman, Carol Hetfield, and Melanie Biggs

VOC Emissions from Spray Foam Insulation Under Different Application Conditions 278 Doyun Won, Joan Wong, Gang Nong, and Wenping Yang

The Symposium on Developing Consensus Standards for Measuring Chemical sions from Spray Polyurethane Foam (SPF) Insulation was held on April 30–May 1,

Emis-2015 Sponsored by ASTM Committee D22 on Air Quality, the symposium was held

in Anaheim, CA, in conjunction with the standards development meetings of the Committee ASTM D22.05 is developing tools to assist decision makers in answering fundamental questions, such as: What is emitted from SPF, how long do the emis-sions persist, and how does ventilation impact concentrations and potential expo-sures? How can we model these processes to address the multiplicity of products, applications, and environmental conditions that may impact exposure to emissions over the life cycle of the material? These are complex and interrelated questions that have challenged the indoor environments research community for many years

ObjeCtives Of symPOsium

SPF insulation is manufactured on-site by mixing and spraying chemicals that react to form an effective insulating material Standardized methods are needed to assess the potential impacts of SPF insulation products on indoor air quality, establish re-entry times for trade workers or re-occupancy times for building occupants after product installation and to evaluate post-occupancy ventilation The objective of the sympo-sium was to provide a forum for SPF manufacturers, regulatory agencies, indoor air quality professionals, testing labs, air quality consultants, instrument vendors and other stakeholders to exchange information After a series of presentations on the current status of measuring emissions from SPF insulation, participants discussed paths forward for research, method development and development of standards.The chairs of the symposium distributed a broad call for papers on the following topics, designed to represent the scope of complex challenges that diverse stakehold-ers, including industry and government, must address regarding the application and use of SPF insulation products:

• Research and method development for measuring potential SPF emissions of semi-volatile and volatile organic compounds used in the formulation (e.g., isocyanates, blowing agents, amine catalysts and flame retardants) and from potential reaction or byproducts;

• Federal and other governmental agencies’ regulatory approaches and ing investigation, assessment and research needs;

support-• Modeling, scaling up from lab to large scale chambers or buildings; 

Overview

• International perspective on regulation and testing of SPF insulation emissions; 

• Industry perspective/needs and product stewardship activities; 

• Field investigations or large-scale chamber/spray booth studies to evaluate emissions or ventilation rates; and

• Applying the knowledge from product emissions data/research to practice (e.g., stewardship commitment, green building practices, codes for residential ventilation and global leadership)

The collaboration and exchange of information during the symposium and the responding research papers will support the development of standards at ASTM D22.05 on Indoor Air for measuring emissions from SPF New standards are being developed to estimate the emissions of volatile and semi-volatile organic compounds (e.g., blowing agents, catalysts, flame retardants, byproducts) with micro- and large-scale chambers Analytical methods must be developed to measure emissions from the chambers Specialized chambers must be evaluated for measuring isocyanate emissions such as methylene diphenyl diisocyanate (MDI) to avoid adhesion to the chamber’s surfaces The data generated from the new ASTM standards may be useful

cor-as input parameters in computer simulation modelling software to help ers and distributors, researchers, and government agencies assess exposure potential and control mechanisms for SPF products In the following paragraphs, the sym-posium co-chairs summarize key presentations, findings, and knowledge gaps and identify new standard development activities that have been introduced in ASTM D22.05 as outcomes of the symposium

manufactur-seLeCteD teChniCaL PaPeRs with exCeRPts fROm abstRaCts

Several topics are covered in the selected technical papers (STP) resulting from the symposium including: field investigation studies, emissions measured in various-sized test chambers, emissions from misapplied material, computer simulation mod-elling of emissions and peak SPF temperatures in residential homes According to the paper “Investigating Sampling and Analytical Techniques to Understand Emis-

sion Characteristics from Spray Polyurethane Foam Insulation and Data Needs,”

reliable and validated emission test methods and sampling, and analytical protocols are needed to understand the variables that affect emissions and curing in order to develop and assess residential exposure scenarios

The paper “Evaluation of Micro-Scale Chambers for Measuring Chemical sions from Spray Polyurethane Foam Insulation” evaluates the use of micro-scale chambers for measuring emissions and compares the results with conventional small-scale chambers The authors also investigated the effect of the chamber’s temperature and trimming samples prior to testing Automating the micro-scale chamber testing was demonstrated in the paper “Measurement of Chemical Emissions from Spray Polyurethane Foam Insulation Using an Automated Micro-Scale Chamber System.”

Emis-An automated dynamic headspace system was used for on-line, fully automated

micro-scale chamber measurements of SPF to evaluate sampling time, volume and temperature The paper “Prioritizing Chemical Emissions from Closed-Cell Spray Polyurethane Foam: Utilizing Micro-Scale Chamber Emission Factors and Field Measurement Data” compares emission factors from the micro-scale chambers in conjunction with a screening model to emissions measured in a residential home after application of SPF insulation

The paper “Flame Retardant Emissions from Spray Polyurethane Foam tion” evaluates emissions of a commonly used flame retardant in SPF, tris (1-chloro-2-propyl) phosphate (TCPP), with micro-scale chambers and a full scale Net Zero Energy Residential Test Facility The authors measured emissions in the test house without the installation of furniture, carpeting, or other household goods to deter-mine if SPF in the facility was the primary source of the airborne concentrations of TCPP This flame retardant was also investigated in the paper “Glass Chamber Meth-

Insula-od for Screening of MDI and TCPP Emissions from Foam Joint Sealant.” The goal of this study was to develop a glass chamber method to examine the emissions of MDI and TCPP, which were measured during a 24-hour chamber test in a 3-L chamber.There is a great need to determine when it is safe for trade workers to re-enter a work area where SPF was recently applied during retrofit or new construction Emis-sions from three generic SPF formulations were evaluated in a room-size chamber at ventilation rates ranging from 1 to 10 air changes per hour in the paper “Estimating Re-Entry Times for Trade Workers Following the Application of Three Generic Spray Polyurethane Foam Formulations.” Chemicals selected for evaluation were MDI, amine catalysts, blowing agent and flame retardant that were used in the formula-tions The room-size chamber test was also utilized to evaluate commercial products

in the paper “VOC Analysis of Commercially Available Spray Foam Products.” The study was aimed at determining if worker reentry times could be reduced from the industry practice of 24 hours if specific rates of workplace ventilation were employed According to the paper “Assessment and Remediation of Misapplied Spray Polyu-rethane Foam,” the misapplication of SPF may result in occupant complaints asso-ciated with persistent odor, and that SPF installed in homes may fail to cure and perform as anticipated when the contractor does not follow the distributors speci-fied pre-application and installation procedures This paper discusses strategies for resolving odor complaints and suggests an assessment and mitigation protocol for field use Emissions from misapplied SPF are also investigated in “VOC Emissions from Spray Foam Insulation under Different Application Conditions.” The research-ers compare chemical emissions from SPF insulation applied in four different ways in

an attempt to simulate normal and abnormal applications Application temperature and A to B-side ratios are investigated to determine the effect of emissions

To begin to understand exposure to emissions from SPF and to identify and characterize uncertainty in assessing chemical exposures, a proof-of-concept multi-zone indoor model to estimate indoor air concentrations of chemicals is described

in the paper “A Modeling Approach for Quantifying Exposures from Emissions of Spray Polyurethane Foam Insulation in Indoor Environments.” A recently developed model, i-SVOC, was applied to estimate TCPP emitted from SPF and its fate and transport in a modeled indoor environment in the paper “Predicting TCPP Emis-sions and Airborne Concentrations from Spray Polyurethane Foam Using USEPA i-SVOC software: Parameter Estimation and Result Interpretation.” In order to evaluate the temperature gradient of SPF in buildings, a one-dimensional transient dynamic numerical simulation was evaluated in the paper “Computer Simulation

of Peak Temperatures in Spray Polyurethane Foam Used in Residential Insulation

Applications.”

what we have LeaRneD anD what we neeD tO LeaRn

The research methods and results reported in this STP provide a reference point from which to evaluate progress towards development of reliable methods, data, and mod-els that inform our understanding of the relationships between use of on-site applied spray polyurethane foam insulation materials and potential exposures to chemicals emitted from the insulation material The following paragraphs attempt to capture some of the key observations and identify the research needs that will better inform development of tools and knowledge for managing emissions The summary is in-tended to stimulate the reader to probe the manuscripts and to contribute to the discussion of progress and research needs

Key observations and findings

What is emitted and how long do emissions persist? The chemicals identified in sions include those used to produce the insulation material, i.e., MDI and polymeric MDI, additives to the polyols such as amine catalysts, blowing agents, flame retard-ants, as well as chemicals that may be related to production of the primary ingredients, reaction products, or minor constituents The papers by Nie, Klein-Benne, and Thax-ton, Poppendieck et al., and Won et al provide insight into the range of compounds identified in emissions reported in the course of methods development experiments reported herein Most of the studies reported in the STP are of relatively short dura-tion and focus on post application emissions over periods of 2 to 336 hours Ecoff, Tian, and Sebroski quantified emissions of blowing agents in the attic and occupied areas of a residence for 16 months Poppendieck et al observed airborne concentra-tions of TCPP attributable to SPF that was applied in the crawl space of a research house two years prior to testing Ecoff, Tian, and Sebroski quantified MDI emissions during application in an attic, and did not detect post application emissions Won, Zidek, et al observed that MDI emissions in a small glass chamber peaked within about 11 minutes and fell below quantification levels within about an hour These observations are consistent with post application spray room results reported by Wood and with reports in the literature as summarized by Sleasman, Hetfield, and Biggs

What factors impact emissions?

Sebroski et al demonstrate that temperature strongly impacts emission rates for tile and semivolatile emissions Won, Wong, et al demonstrated that environmen-tal conditions (temperature and relative humidity) impact amount and duration of post application MDI emissions Poppendieck et al demonstrated that TCPP emis-sion rates are impacted by external mass transfer factors (gas phase concentration

vola-in the boundary layer, air speed and turbulence) whereas more volatile emissions may be controlled by diffusion rates within the material Duffy and Wood demon-strate that amine catalyst emissions vary across product types and formulations, and Won, Wong, et al demonstrate that application outside of recommended conditions results in increased emissions Sebroski et al demonstrate that trimming the skin affects emissions from open cell foam and that aldehyde emissions correlate better with mass than sample surface area

hoW mature are the test methods?

Sleasman, Hetfield, and Biggs provide an overview of the sampling and analysis methods that may be employed to characterize SPF emissions Although there are many methods that have been validated for specific compounds or classes of com-pounds for specific uses, e.g., occupational exposure assessment, the adaptability and reliability of these methods for characterization of SPF insulation emissions during and following application have not been well-demonstrated Two of the approxi-mately eight to ten isocyanate derivatization methods were employed in studies that determined MDI emissions (see papers by Won et al., Wood, and Ecoff, Tian, and Sebroski) Won, Zidek, et al demonstrated an emissions characterization approach that generated model inputs for post application MDI and TCPP emissions; how-ever, this approach has not been demonstrated for application phase MDI emissions VOC collection on single or multi-sorbent traps followed by thermal desorption with GC/MS quantification was employed by several researchers The methodology pro-vides adequate detection limits for many SPF VOC emissions where sample sizes are appropriate to the concentrations However, the TD-GC/MS approach does not provide adequate quantification levels for some of the amine catalysts, and sampling media and sample volumes may need to be carefully selected

Micro chambers, small glass and stainless steel chambers, room-sized spray booth–spray room chambers, and residential structures were employed in emissions tests Uncertainty regarding interactions between reactive and semivolatile emis-sions, MDI and TCPP, with chamber surfaces provide challenges to data interpreta-tion in all test systems Attempts to compare emissions across scales of test systems were characterized by uncertainty due to many factors, including sorption of semi-volatile compounds by surfaces, uncertainty of concentration measurements and mixing in full-scale chambers, lack of data to characterize interzonal flows and air exchange rates in buildings

interpretation of results

Two general approaches were employed to interpret test results Duffy and Wood compare concentrations of specific emissions in a defined test environment to occupational exposure values Won et al employ the more typical indoor envi-ronment approach where chamber emissions data are used to construct a source model that is used in a room or building simulation model to predict potential indoor exposure

model system development

Bevington presents a new modeling approach based upon two models developed

by EPA, iSVOC and IAQx, to quantify exposures due to application of SPF Based upon results of a sensitivity analysis, the authors concluded that experimental data are needed to calibrate the model, particularly in the first 24 hours following appli-cation, characterize longer term mass transfer, and characterize flow paths and air exchange rates Tian, Sebroski, and Escoff use literature-based parameters in the in-door simulation system, iSVOC, to calculate TCPP concentrations in a model room due to application of SPF insulation Tian, Sebroski, and Escoff compare model predictions with predictions based upon micro chamber results and conclude that the micro chamber results were close to the upper end of the iSVOC predictions Sensitivity analysis suggested that the material–air partition coefficent was the most important parameter for explaining differences between Tian’s iSVOC predictions and micro chamber based predictions

summaRy Of ReseaRCh neeDs

Research is needed to:

• Better characterize emission factors during the first 24 hours following cation of SPF to provide data to calibrate models and to improve ventilation guidance for a range of scenarios

appli-• Characterize interactions of flame retardants with surfaces, characterize zonal flows and air exchange rates in SPF insulated buildings

inter-• Improve sampling and analysis of reactive amines compounds that behave poorly in thermal desorption systems

• Improve parameter estimation techniques and conduct experiments to validate parameters and modeling results

• Develop a better understanding of how micro chamber derived emission factors can be used to predict concentrations and potential exposures in buildings

• Develop a better understanding of how off-ratio or application or application outside of specified conditions impacts emissions

• Better understand how automated and integrated chamber/sampling and analysis systems might improve sensitivity and reliability of test methods

• Develop an improved understanding of the impact of environmental factors

on MDI emissions, reactions and products to improve confidence in modeling potential exposures

• Better understand how well thermal energy models predict temperatures in applied foam and in attics and crawl spaces

• Develop full-scale test methods that provide emission factor inputs to models

• Improve quality assurance procedures to ensure characterization of uncertainty

of test systems and test protocols

astm aCtivities ReLateD tO symPOsium

Knowledge learned from the symposium has been applied towards the development

of standards at ASTM Subcommittee D22.05 on Indoor Air The subcommittee

has continued to develop work item, WK40293, New Test Method for Estimating

Chemical Emissions from Spray Polyurethane Foam (SPF) Insulation Using Micro-Scale Environmental Test Chambers Several of the papers included micro-scale chamber

evaluations that examined method parameters (e.g., temperature, area specific flow rate, etc.) and compared the emissions data to small-scale chambers or residential buildings Isocyanate emissions will require the use of specialized chambers to avoid significant bias from adhesion to the chamber walls; therefore, work item WK51589

was created, New Test Method for Estimating Emissions of Methylene diphenyl

diisocy-anate (MDI) from Spray Polyurethane Foam (SPF) Insulation using Emission Cells or Micro-Scale Environmental Test Chambers.

Two of the symposium papers discussed the use of a large-scale spray room at various ventilation rates as an approach to evaluate potential impacts on the use of protective equipment and controls and re-entry times for trade workers without the use of protective equipment after application of the material This approach may

be useful to provide a better understanding of the emissions that occur during and post application under controlled conditions As a result, a new work item has been

created, WK51588, New Test Method for Measuring Chemical Emissions from Spray

Polyurethane Foam (SPF) Insulation Samples in a Large-Scale Spray Room The

emis-sions data from the large-scale spray room may also be used in conjunction with computer simulation models as a means of calibration or verification Two of the papers from the symposium discussed estimating emissions in buildings using such models The input parameters and the use of models to estimate SPF emissions are

being addressed in a new work item, WK52052, New Practice for Application of

Indoor Emission and Fate Modeling for Spray Polyurethane Foam (SPF) Insulation In

the future, additional standards may be necessary to measure key input parameters for the simulation models

John Sebroski,1Jason W Miller,1Carl P Thompson,1and

Elizabeth Roeske1

Evaluation of Micro-Scale

Chambers for Measuring

Chemical Emissions from

Spray Polyurethane Foam

Insulation

Citation

Sebroski, J., Miller, J W., Thompson, C P., and Roeske, E., “Evaluation of Micro-Scale Chambers for Measuring Chemical Emissions from Spray Polyurethane Foam Insulation,” Developing Consensus Standards for Measuring Chemical Emissions from Spray Polyurethane Foam (SPF) Insulation, ASTM STP1589, J Sebroski and M Mason, Eds., ASTM International, West Conshohocken, PA, 2017, pp 1–26, http://dx.doi.org/10.1520/STP1589201500392

Manuscript received May 14, 2015; accepted for publication August 28, 2016.

1 Covestro LLC, 1 Covestro Circle, Pittsburgh, PA 15205

2 ASTM Symposium on Developing Consensus Standards for Measuring Chemical Emissions from Spray Polyurethane Foam (SPF) Insulation on April 30–May 1, 2015 in Anaheim, CA.

STP 1589, 2017 / available online at www.astm.org / doi: 10.1520/STP158920150039

liquid chromatography After the application of open-cell SPF, the outer skin layer

of the foam may be trimmed to align the surface with wall studs or other structuralelements In this case, it may be necessary to mimic this practice when preparingsamples for analyses to measure emissions In order to investigate the impact ofemissions on trimmed SPF samples, micro-scale chamber studies were conducted

on both trimmed and untrimmed generic open-cell SPF material for comparison.The data from this study demonstrate that micro-scale chambers can be used toidentify and quantitate potential emissions from SPF insulation The findings fromthis research will be used to support the development of consensus standards

in ASTM Committee D22 on Air Quality, Subcommittee D22.05 on Indoor Air

of volatility and reactivity of compounds that are used to produce SPF insulation(e.g., isocyanates, blowing agents, amine catalysts, flame retardants), and there arecurrently no standardized methods to measure the emissions of many of these com-pounds Methods are needed to measure chemical emissions from SPF insulation tohelp manufacturers evaluate their products and regulatory agencies to make risk assess-ments Micro-scale chambers were evaluated during this study at selected temperatures

to measure chemical emissions from SPF insulation, and results were compared withconventional small-scale chambers The effect of removing the surface skin of SPF wasalso examined The findings from this research will be used to support the develop-ment of consensus standards in ASTM Subcommittee D22.05 on Indoor Air

BACKGROUND AND OBJECTIVES

During the last few years, an ASTM task group created several work items to developstandards to measure chemical emissions from SPF insulation The AmericanChemistry Council, Center for the Polyurethanes Industry (CPI), supported researchfor the development of ASTM standards for measuring emissions from SPF insula-tion [1] Part of this research led to the development of ASTM D7859-13e1,Standard Practice for Spraying, Sampling, Packaging, and Test Specimen Preparation

of Spray Polyurethane Foam (SPF) Insulation for Testing of Emissions Using mental Chambers [2], to standardize the way samples are sprayed, sampled, packaged,

Environ-and prepared for environmental chamber testing The ASTM practice describes men preparation for both micro- and small-scale test chambers.

speci-Small-scale chambers, described in ASTMD5116-10, Standard Guide for Small-ScaleEnvironmental Chamber Determinations of Organic Emissions from Indoor Materials/Products [3], range in size from a few liters to a few cubic meters and can be used to deter-mine emissions of volatile organic compounds (VOCs) from various types of buildingmaterials and consumer products Micro-scale test chambers range in size from a fewmilliliters to 150 mL According to ASTMD7706-11, Standard Practice for Rapid Screen-ing of VOC Emissions from Products Using Micro-Scale Chambers [4], micro-scale cham-bers can be operated at moderately elevated temperatures to enhance analytical signals,reduce the test time, boost emission rates, and facilitate the screening of emissions fromsemivolatile organic compounds (SVOCs) Other chambers, such as the full-scalechambers described in ASTM D6670-13, Standard Practice for Full-Scale ChamberDetermination of Volatile Organic Emissions from Indoor Materials/Products [5], permitthe testing of complete assemblages or may be used to evaluate activities such as spraying.According to ASTMD7859-13e1 [2], the surface skin of the SPF should not beremoved for chamber testing unless it is specified by the sample submitter Whenopen-cell SPF is sprayed at a construction site, the material may be over-sprayedbeyond the wall studs or other structural elements When this occurs, the SPF insu-lation’s surface skin must be trimmed off of the material, exposing the open cells ofthe foam It is not clear how the emissions would be affected if the surface skin isremoved during chamber testing One possibility is that the sample’s skin helps toseal the surface of the SPF, reducing the emissions measured in the micro-scalechamber; however, there are no known data to support this hypothesis

To further investigate the use of micro-scale chambers for measuring chemicalemissions from SPF insulation, 20-day emissions studies were conducted with twoSPF formulations with the following objectives:

• To compare emissions measured with micro-scale chambers to small-scalechambers at ambient temperatures

• To evaluate how elevated temperatures affect the emissions of SPF insulation

in micro-scale chambers and the appropriate time(s) to collect emissions ples from the micro-scale chambers by observing the decay curves

sam-• To compare emissions of open-cell SPF with surface skin removed to thosewith the skin intact

Apparatus and Instrumentation

INSTRUMENTATION

The following instrumentation was used during the study:

• Markes International (Llantrisant, Wales, UK) TD-100 thermal desorber nected to Agilent Technologies (Santa Clara, CA) 7890A gas chromatography(GC) and 5975C Inert XL mass selective detector (MSD), and

con-• Agilent Technologies 1100 Series LC/MSD and diode array detector

ENVIRONMENTAL TEST CHAMBERS AND ACCESSORIES

The following environmental rest chambers and accessories were used during the study:

• Markes International (Llantrisant, Wales, UK) M-CTE250 micro-chamber/thermal extractor, 114-mL capacity, and

• Small-scale chamber, Eagle Stainless (Warminster, PA) CTH-36-316L-J, 36-Lcapacity, electropolished stainless steel with VitonV R

gasket

LAB EQUIPMENT, SAMPLING PUMPS, AND FLOW CONTROLLERS

The following lab equipment, sampling pumps and flow controllers were usedduring the study:

• Ultra zero grade air, compressed, air source for micro chambers

• Parker Filtration, Balston (Lancaster, NY) 75-83N zero-air generator, airsource for small-scale chambers

• Parker Porter (Hatfield, PA) VCD-ABF-110 low-flow controller with optionalflow element, 0-535 cc/min

• Markes International (Llantrisant, Wales, UK) TC-20 tube conditioner

• Markes International (Llantrisant, Wales, UK) calibration solution loading rig

• DryCal (Butler, NJ) BIOS Defender 510 volumetric primary flow standard, brator, and

cali-• Thermo Fisher Scientific (Waltham, MA) TraceableV R

long-stem thermometer,Cat No S40799-3

SORBENT TUBES AND MEDIA FOR SAMPLE COLLECTION

The following sorbent tubes and media for sample collection were used during thisstudy:

• Markes International (Llantrisant, Wales, UK) thermal desorption tubes,stainless steel, 5-mm quartz wool, TenaxV R

SAMPLE COLLECTION EQUIPMENT

The following sample collection equipment was used during the study:

• Sheets of high-density polyethylene, 0.95-cm thick, cut into 30.5 by 30.5-cm pieces

• Aluminum foil, heavy-gage roll, approximately 0.024 mm thick

• Electric knife and band saw to scarf and cut SPF samples

• Circular foam coring tool constructed of steel to cut SPF insulation samples to

fit tightly into micro-scale chambers

open-cell SPF, a bag size of approximately 51 by 76 cm was used (zipper seal notavailable in this size)

Sample Matrices and Target Compounds

GENERIC SPF FORMULATIONS

Two generic high-pressure SPF formulations were evaluated during this study: density open-cell SPF and medium-density closed-cell SPF (Table 1) The genericformulations were developed by the CPI for research purposes The formulations

low-do not reveal confidential information of formulations sold in the marketplacetoday; rather, they are meant to represent typical commercial systems in terms oftheir density, reactivity, and volume ratios Although not completely optimized orcode compliant, the formulations are meant to be representative of commercial for-mulations and are suitable for the purpose of method development The two genericSPF formulations represent the following sample types:

• Open-cell, low-density (8 kg/m3or 0.5 lb/ft3), high-pressure SPF

• Closed-cell, medium-density (32 kg/m3or 2 lb/ft3), high-pressure SPF

TABLE 1 Generic SPF formulations.

Low-Density, High-Pressure, Open-Cell SPF

Silicone surfactant (1.0 %) Silicone surfactant (1.0 %)

Catalyst BDMAEE (0.9 %)

TMIBPA (3.0 %)

TMAEEA (4.0 %)

BDMAEE (0.7 %) DAPA (2.59 %) TMAEEA (0.3 %)

Note: BDMAEE ¼ bis(2-dimethylaminoethyl) ether; DAPA ¼ bis(dimethylaminopropyl) methylamine; HFC-245fa ¼ 1,1,1,3,3-pentafluoropropane; NPE ¼ nonylphenol ethoxylate; PMDI ¼ polymeric methy- lene diphenyl diisocyanate; TCPP ¼ tris(1-chloro-2-propyl) phosphate; TMAEEA ¼ N,N,N-trimethyla- minoethylethanolamine; TMIBPA ¼ tetramethyliminobispropylamine.

TARGET COMPOUNDS

The blowing agent, amine catalysts, and flame retardants used in the generic tions described inTable 2were treated as the primary compounds to evaluate the cham-ber test methods during this study Although aldehydes were not used in either of theproduct formulations, emissions of aldehydes are usually monitored from buildingproducts; therefore, aldehydes observed during previous research with the generic for-mulations were included in this study [1] The isocyanate compounds (e.g., methylenediphenyl diisocyanate [MDI], polymeric MDI) were not monitored during this studybecause specialized chambers are necessary to monitor emissions in order to minimizethe adsorption of isocyanates to the chamber surfaces [6]

formula-EXPERIMENTAL DESIGN

SAMPLE PREPARATION

The generic SPF was sprayed in a spray room with a Graco Reactor H-XP2TMtioner at a 1:1 ratio, and samples were prepared for chamber testing as described in

for 1 h and then were wrapped in aluminum foil prior to placing each sample into vidual MylarV R

indi-bags, which were stored for approximately 24 h at room temperature(approximately 23C) prior to chamber testing Immediately after opening the bags,specimens of SPF were cored to fit tightly into the micro-chambers (6.4-cm diameter;approximately 3 cm thick) The bottom of the samples was trimmed so that there wasminimal headspace in the micro-scale chambers (approximately 5 mm) The open-cellsamples were also prepared with approximately 2 mm of the top surface (skin)removed but with the same thickness (3 cm) for comparison Three sets of samplesfrom separate MylarV R

bags were prepared to evaluate three test temperatures Duplicatespecimens from the same block of foam were prepared for every test sample

TABLE 2 List of target compounds.

Note: BDMAEE ¼ bis(2-dimethylaminoethyl) ether; DAPA ¼ bis(dimethylaminopropyl) amine; HFC-245fa ¼ 1,1,1,3,3-pentafluoropropane; TCPP ¼ tris(1-chloro-2-propyl) phosphate; TMAEEA ¼ N,N,N-trimethylaminoethylethanolamine; TMIBPA ¼ tetramethyliminobispropylamine.

methyl-The samples were also prepared for testing in 36-L electropolished stainlesssteel small-scale chambers Specimens of open-cell SPF were cut 13 by 13 by 9 cm.Specimens of closed-cell SPF were cut 13 by 13 by 6 cm Open-cell SPF wastrimmed at the top with the surface skin removed so that there would be a smoothexposed surface The cut specimens were tightly fitted into a steel box of the sameinner dimensions Duplicate specimens were prepared for each test sample.

CHAMBER TESTING

The loading factor (L), which is described in ASTMD5116-10 [3], was calculated to

be 200 m2/m3 in the micro-scale chambers and 0.490 m2/m3 in the small-scalechambers The air change rate (N) was 188 air exchanges per hour in the micro-scale chambers and 0.522 air exchanges per hour in the small-scale chambers The36-L small-scale chambers were constructed of electropolished stainless steel withthree 0.25-in (0.635-cm) stainless steel compression fitting ports (inlet, outlet, andsampling port) To ensure adequate mixing in the small-scale chambers, a polyte-trafluoroethylene drop tube from the air inlet port was placed near the sample sur-face; another drop tube was placed midway in the chambers to collect air samplesfrom the chambers The air velocity at the air inlet above the sample was calculated

to be approximately 15.8 cm/s in the small-scale chambers and 10.5 cm/s in themicro-scale chambers The higher loading factor and air change rate in the micro-scale chambers may improve the recovery of reactive compounds and SVOCs.However, the area-specific flow rate (N/L) for the micro- and small-scale chamberswas similar (0.938 and 1.07 m/h, respectively) For consistency during this study,dry air was used as the carrier gas for both chambers, and the relative humidity was

<1 % The chamber parameters are summarized inTable 3

TABLE 3 Chamber parameters.

Note: Micro-scale chamber headspace assumes a planar surface and approximately 5-mm space The sample mass varies and depends on the formulation and trimming The small-scale chambers were operated only at ambient temperature, which was 23 6 2  C during this study Three micro-chamber apparatuses, each containing four micro-scale chambers, were operated indepen- dently of one another at 23 (ambient), 40, and 65  C The elevated temperatures were controlled with the micro-scale chamber apparatus and verified to be accurate within 62  C with a National Institute of Standards and Technology traceable long-stem thermometer.

head-SAMPLING FOR EMISSIONS

Airborne concentrations of amine catalysts, blowing agents, and flame retardantswere collected from the outlet of chambers using thermal desorption (TD) tubes.The TD tubes used to collect VOCs and flame retardants were stainless steel tubescontaining quartz wool, TenaxV R

TA 35/60, and CarbographTM5TD 40/60 Highlyvolatile organic compounds (blowing agents) were captured with stainless steel TDtubes containing TenaxV R

TA 35/60, CarbographTM1TD 40/60, and Carboxen 100340/60 The TD tubes selected for this study were previously evaluated for measuringemissions from SPF [1,7] The carbonyl compounds (aldehydes) were sampledwith glass sorbent tubes containing silica gel coated with dinitrophenylhydrazine(DNPH) as described in ASTM D5197-09e1, Standard Test Method for Deter-mination of Formaldehyde and Other Carbonyl Compounds in Air (Active SamplerMethodology) [8] The sampling flow rate for the micro-scale chambers was 50 mL/min; the sampling flow rate for the small-scale chambers was 100 mL/min Thesampling time and volume to collect air samples from the chambers were based

on previous research at 23C [1,7] Sample volumes for sampling TD tubes frommicro-scale chambers at elevated temperatures were decreased to avoid possiblyoverloading the tubes

Samples were collected at various times after being loaded into the chamberswhen the chamber testing concluded The emissions from the closed-cell SPF werecollected at 2, 24, 48, 72, 168, 216, 336, and 480 h The emissions from the open-cellSPF were collected at 2, 24, 48, 120, 168, 336, and 480 h Maximum sampling vol-umes with TD tubes were established for target compounds during previousresearch [7] The detection limits were dependent on the duration of emissionsampling from the chambers with TD tubes, which ranged from 1 min to 2 hdepending on the time each sample resided in the chamber and the chamber’stemperature

Aldehydes were collected on DNPH tubes for 16 h to optimize detection its The sampling rate for micro- and small-scale chambers was 50 and 100 mL/min,respectively Sorbent tubes were placed directly on the outlet of the micro-scalechamber; small-scale chambers were sampled with a personal sampling pump Allflows were verified with a volumetric primary flow standard

lim-ANALYTICAL METHODS

A Markes International TD-100 thermal desorber coupled to an Agilent 7890/5975gas chromatograph-mass spectrometer was used to analyze the tubes with method-ology based on U.S EPA TO-17 and ISO 16000, Part 6 [9,10] Based on previousresearch, the base-deactivated transfer line, analytical column, and methodconditions were optimized for the recovery of target compounds [1] Formaldehyde,acetaldehyde, and propionaldehyde were analyzed with an Agilent 1100 series high-performance liquid chromatograph with the use of the methodology based on

Results and Discussion

REPORTING AND DUPLICATE SAMPLES

The emissions results are reported as emission factors, which were calculated by directcalculation from individual concentration data points as described in ASTMD5116-

10, Section 9.4.1.1 [3] According to ASTMD5116, calculating emission factors prior

to reaching steady-state conditions can increase error; however, this approach is sistent with the draft ASTM method being investigated Unless otherwise specified,the emission factors are reported as area-specific emission rates in lg/m2per hour

con-To be consistent with the draft ASTM method, all test results are reported as themean of duplicate chamber samples with a relative percent difference (RPD) <25 %

If the RPD exceeded 25 %, the higher of the two values were reported as a tive approach to reporting the emissions from the sample Reporting limits wereestablished with the analytical method detection limits from previous research [7].The reporting limits for emission factors are based on these detection limits and thesample collection times onto the sorbents that varied depending on the expectedemissions The reporting limits are reported inTable 4andTable 5 The decay of targetcompounds was monitored during a 20-day test period The reported emissions ratesare those measured at the time emissions were collected from the test chambers

conserva-TABLE 4 Generic open-cell SPF: micro- versus small-scale chambers.

Small-scale <3.00 1,125 1,189 1,466 821 625 646 551 TCPP Micro-scale <4.00 <48.5 <24.2 25.0 19.0 23.0 25.7 25.2

Small-scale <2.30 <55.4 <27.7 <27.7 <13.8 <13.8 11.2 14.7 Formaldehyde Micro-scale <2.26 3.28 3.03 <2.23 <2.30 1.96 <1.67 <2.11

Small-scale <1.18 8.75 8.04 7.29 8.09 6.53 6.82 7.43 Acetaldehyde Micro-scale <2.26 <2.73 <2.37 <2.23 <2.30 <1.88 <1.67 <2.11

Small-scale <1.18 5.88 3.00 2.19 2.31 1.38 1.28 1.40 Propionaldehyde Micro-scale <2.26 <2.73 <2.37 <2.23 <2.30 <1.88 <1.67 <2.11

Small-scale 13.0 21.3 B 7.69 B 2.96 B <1.31 <1.08 <0.952 <1.21

Note: BDMAEE ¼ bis(2-dimethylaminoethyl) ether; TCPP ¼ tris(1-chloro-2-propyl) phosphate; TMAEEA ¼ N,N,N-trimethylaminoethylethanolamine Emission factors are reported as lg/m 2 per hour Emission factor reporting limits were calculated with the detection limit on the sorbent tube/ cartridge, sampling time/volume, and surface area of samples The reporting limits shown with a

“less than” symbol vary depending on the sampling conditions Results qualified with a B indicate not significantly greater than the corresponding chamber blank.

QUALITY CONTROL

Prior to chamber testing, each chamber configuration was evaluated for contamination

by testing emissions from empty chambers and sample holders The emissions collectedfrom the blank chambers were analyzed for target compounds concurrently with theSPF samples Blank chamber data are reported along with the corresponding samples.Calibration check samples were analyzed during each analytical sequence A summary

of the performance of the calibration checks is reported inTable 6 The amine catalysttetramethyliminobispropylamine (TMIBPA) showed relatively poor precision (29.7 %RSD) and bias (36.7 %) compared to the other target compounds; although notdetected in any of the samples, this compound was not reported Additional methoddevelopment may be necessary for this compound and possibly other reactive aminecatalysts that may be challenging to measure with the TD-GC-MS method

MICRO-SCALE CHAMBERS COMPARED TO SMALL-SCALE CHAMBERS

The emissions measured from open- and closed-cell SPF at ambient temperature arereported as area-specific emission factors in micro- and small-scale chambers.Duplicate chamber results are reported as mean values in Table 4 and Table 5

TABLE 5 Generic closed-cell formulation: micro- versus small-scale chambers.

Small-scale <42.5 <170 <170 <170 <85.0 <85.0 <85.0 <85.0 <85.0 BDMAEE Micro-scale <4.97 <9.94 <9.94 <9.94 <9.94 <4.97 <4.97 <4.97 <9.94

Small-scale <2.84 <11.4 <11.4 <11.4 <5.68 <5.68 <5.68 <5.68 <5.68 DAPA Micro-scale <34.5 <68.9 <68.9 <68.9 <68.9 <34.5 <34.5 <34.5 <68.9

Small-scale <19.7 <78.8 <78.8 <78.8 <39.4 <39.4 <39.4 <39.4 <39.4 TCPP Micro-scale <4.04 13.1 36.0 17.2 8.94 4.19 <4.04 <4.04 <8.07

Small-scale <2.30 <9.23 12.0 <9.23 <4.62 <4.62 <4.62 <4.62 <4.62 Formaldehyde Micro-scale <2.10 <2.22 <1.90 <1.90 <1.85 <1.94 <1.90 <2.27 <1.67

Small-scale <1.18 4.92 6.44 3.18 3.17 3.82 3.35 2.96 3.58 Acetaldehyde Micro-scale <2.10 30.0 15.8 8.91 8.50 5.51 4.57 3.72 3.07

Small-scale <1.18 42.3 24.0 12.6 11.7 9.41 7.44 5.74 6.19 Propionaldehyde Micro-scale <2.10 <2.22 5.40 <1.90 <1.85 <1.94 <1.90 <2.27 <1.67

Small-scale 13.0 28.1 B 15.3 B 10.0 B 7.61 B 4.88 B 4.74 B 4.20 B 3.43 B

Note: BDMAEE ¼ bis(2-dimethylaminoethyl) ether; DAPA ¼ bis(dimethylaminopropyl) amine; HFC-245fa ¼ 1,1,1,3,3-pentafluoropropane; TCPP ¼ tris(1-chloro-2-propyl) phosphate; TMAEEA ¼ N,N,N-trimethylaminoethylethanolamine Emission factors are reported as lg/m 2 per hour Emission factor reporting limits were calculated with the detection limit on the sorbent tube/ cartridge, sampling time/volume, and surface area of samples The reporting limits shown with a

methyl-“less than” symbol vary depending on the sampling conditions Results qualified with a “B” indicate not significantly greater than corresponding chamber blank.

Bis(2-dimethylaminoethyl) ether (BDMAEE) was the primary compound to emitfrom the generic open-cell SPF decaying from 2,985 lg/m2per hour on the daythe chambers were loaded to 244 lg/m2per hour at the end of the 20-day study(reported values from micro-scale chambers); however, no emissions of this com-pound were detected from the closed-cell formulation This compound is a non-reactive amine catalyst Because it is not consumed during the foaming processand has a relatively low molecular weight, this compound is highly emissive [11].Conversely, no emissions of the reactive catalysts bis(dimethylaminopropyl)methylamine (DAPA) and N,N,N-trimethylaminoethylethanolamine (TMAEEA)were detected from the generic foams in either chamber during the entire study.Method detection limits (MDLs) for the reactive catalysts TMAEEA, TMIBPA,and DAPA were 479, 654, and 222 ng/sample, respectively, whereas the MDL forthe nonreactive catalyst BDMAEE was much lower (32.2 ng/sample).

Based on duplicate chamber testing data from this study, the BDMAEE sions in the open-cell SPF appeared to be higher in the micro-scale chambers for thefirst 2 days of monitoring than the small-scale chambers, and then the decay rate wassimilar throughout the duration of the study The best correlation of the dataoccurred during days 5 and 7, when the emissions factors were 12 % and 9.7 % RPD,respectively The decay curves for BDMAEE are shown inFig 1for comparison Thereduced initial concentration of BDMAEE in the small-scale chamber may have beenfrom the catalyst adsorbing to the surface of the chamber’s walls or an indication thatthe mass transfer conditions are not the same for the two systems Conversely, theadsorbed compound could have re-emitted at a later time, which may have contribut-

emis-ed to the higher results in the small-scale chambers at days 14 and 20

The blowing agent 1,1,1,3,3-pentafluoropropane (HFC-245fa) was observed

in both the small- and micro-scale chambers The decay curve is shown inFig 2

TABLE 6 Summary of calibration checks.

FIG 1 Comparison of BDMAEE emissions from open-cell SPF in micro- and small-scale chambers.

The HFC-245fa emissions decayed from 2,164 to 334 lg/m2per hour over the day test period (reported values from micro-scale chambers) The HFC-245fa emis-sion factors were consistently higher in the micro-scale chambers than the small-scale chambers, although their decay curves were similar The emissions data ap-pear to correlate best after 7 days (168 h) in the chambers.

20-The emission factors for TCPP reported inTable 4andTable 5appeared to behigher in the micro-scale chambers compared to the small-scale chambers Sorption

of TCPP by small-scale chamber interior surfaces may be the reason the emissionfactor appeared to increase from 13.1 lg/m2per hour at 2 h to 36.0 lg/m2per hour

at 24 h in the open-cell SPF in the micro-scale chamber In addition, because theemissions of TCPP may be externally controlled by diffusion through the boundarylayer at the sample surface, this difference may be due to the air velocity or higherair exchange rate used in the micro-scale chambers [12]

The aldehyde emissions appeared to be greater in the small-scale chambers,although the measured amounts in the micro-scale chambers were near the detec-tion limits, thus making comparisons difficult Propionaldehyde was detected in thesmall-scale chamber blank, although the source of the contamination is unknown;results are reported without background subtraction Results that are qualified with

a B indicate not significantly greater than the corresponding chamber blank Thedetection limits for aldehydes were a factor of 2 times higher with micro-scalechambers due to decreased sample volume collected and the smaller surface area inthe micro-scale chambers There was a greater height and mass of sample per unitsurface area in the small-scale chambers, which could contribute to increasedemissions of aldehydes if the compounds readily diffused through the material Toevaluate this possibility, the emissions factors were recalculated based on the mass

of the sample in the chamber rather than the exposed surface area The specific emissions are reported as lg/kg per hour for comparison in Table 7 and

TABLE 7 Mass-specific emissions for aldehydes in generic open-cell SPF.

Small-scale <1.70 8.19 4.25 3.10 3.31 1.94 1.80 1.97 Propionaldehyde Micro-scale <7.27 <11.8 <10.3 <9.61 <9.90 <8.12 <7.18 <9.09

aldehydes InFig 3, acetaldehyde decay curves from mass-specific emission factorsare compared in micro- and small-scale chambers These data indicate that mass-specific emission factors should be reported for aldehydes.

TEMPERATURE EVALUATION WITH OPEN-CELL SPF

Conventional small-scale chambers are normally maintained between approximately

23 to 25C; however, micro-scale chambers can also be operated at elevated

TABLE 8 Mass-specific emissions for aldehydes in generic closed-cell formulation.

Small-scale <0.665 23.5 13.3 7.75 6.47 5.22 4.13 3.03 3.26 Propionaldehyde Micro-scale <1.69 <1.81 4.81 <1.55 <1.51 <1.59 <1.55 <1.85 <1.36

Small-scale 7.34 15.6 B 8.47 B 5.55 B 4.22 B 2.71 B 2.63 B 2.33 B 1.90 B

Note: Emission factors are reported as lg/m 2 per hour Emission factor reporting limits were calculated with the detection limit on the sorbent tube/cartridge, sampling time/volume, and surface area of sam- ples The reporting limits shown with a “less than” symbol vary depending on the sampling conditions Results qualified with a B indicate not significantly greater than the corresponding chamber blank.

FIG 3 Comparison of acetaldehyde emissions from closed-cell SPF in micro- and small-scale chambers using mass-specific emission factors.

11 % RPD

9 % RPD

temperatures to simulate warm environments or to enhance the detection of cals There are no standardized methods to our knowledge to measure emissions ofVOCs and SVOCs, specifically for SPF; however, there are test methods that specifyelevated temperatures when measuring chemical emissions from polyurethanefoams For example, ULC-S774-09 directs users to test polyurethane foam samplesfor VOC emissions at 40C, and ISO 12219-2-2012 specifies 65C for screeningVOC emissions from vehicle interior parts and materials (which may contain poly-urethane foam) [13,14].

chemi-The emission factors are reported as lg/m2per hour for open-cell SPF at threetemperatures inTable 9andTable 10 The data from this study show that temperaturedoes have an effect on chemical emissions of SPF insulation; however, we observedunexpected fluctuations in the decay of emissions during the first few days of chambertesting As shown inFig 4, at 40 and 65C, BDMAEE emissions from generic open-cell SPF were greatest during the day the samples were loaded in the chambers (2 h)

TABLE 9 Generic open-cell SPF in micro-scale chambers: temperature and skin-trimming evaluations.

Skin Temp Chamber

no <1,785 <1,785 <1,785 <893 <893 <595 <298 yes 65 <74.4 <8,925 <8,925 <8,925 <4,463 <4,463 <1,785 <893

no <8,925 <8,925 <8,925 <4,463 <4,463 <1,785 <893 BDMAEE yes 23 <5.00 4,443 2,740 2,461 1,353 998 607 391

a “less than” symbol vary depending on the sampling conditions.

a The word “no” indicates that the top surface of the sample was trimmed; “yes” indicates that the skin was left intact.

There appeared to be a relation between the temperature and unexplained fluctuations

in emissions during this time (Fig 5) That is, greater fluctuations were observed athigher temperatures After a drop, surge, and another drop in emissions during days 2(48 h) to 5 (120 h) at an elevated temperature, the emissions decayed during days 5(120 h) to 20 (480 h), with no apparent up and down fluctuations in the decay pattern

of emissions The reason for the apparent fluctuations in BDMAEE emissions factorsmay be due to BDMAEE evaporating from the surface of the sample during the firstfew days at an elevated temperature or other factors

As shown in Fig 6, TCPP emissions in generic open-cell SPF at an elevatedtemperature increased during the first few days of testing followed by a sharpdecrease of emissions, and then a quasi-steady state appeared to be reached afterapproximately 5 days (120 h) The initial spike and drop of emissions at elevatedtemperatures may be due to the compound rapidly emitting from the surface of thesample followed by the recovery time to reach equilibrium in the chamber or otherfactors Upon reaching quasi-steady-state conditions, the TCPP emission factorswere approximately 10 times higher at 60C compared to 40C and at 40C

TABLE 10 Generic open-cell SPF in micro-scale chambers: temperature and skin-trimming evaluations.

Skin Temp Chamber

Hours in Chamber Compound Present a

Formaldehyde yes 23 <2.26 3.72 3.69 2.99 <2.30 <1.88 <1.67 <2.11

no 3.28 3.03 <2.23 <2.30 1.96 <1.67 <2.11 yes 40 <2.26 7.98 6.44 4.37 5.33 4.07 2.30 2.62

no 4.16 <2.37 <2.23 <2.30 1.96 2.40 2.83 yes 65 <2.26 21.4 30.5 30.5 30.1 27.7 12.9 10.7

Propionaldehyde yes 23 <2.26 <2.73 <2.37 <2.23 <2.30 <1.88 <1.67 <2.11

no <2.73 <2.37 <2.23 <2.30 <1.88 <1.67 <2.11 yes 40 <2.26 <2.73 <2.37 <2.23 3.12 3.32 8.53 8.19

no 3.72 <2.37 <2.23 <2.30 3.39 8.50 7.38 yes 65 <2.26 115 130 93.7 49.6 39.9 20.0 11.7

Note: Emission factors are reported as lg/m 2 per hour Emission factor reporting limits were calculated with the detection limit on the sorbent tube/cartridge, sampling time/volume, and surface area of sam- ples The reporting limits shown with a “less than” symbol vary depending on the sampling conditions.

a The word “no” indicates that the top surface of the sample was trimmed; “yes” indicates that the skin was left intact.

FIG 5 BDMAEE emissions from open-cell SPF after 2 h in micro-scale chambers.

y = 974.7e 0.0675x

R ² = 0.9986

1,000 10,000

compared to 23C This trend continued throughout the duration of the 20-daystudy The apparent relation between TCPP emissions from generic open-cell SPFversus temperature are plotted inFig 7.

FIG 6 TCPP emissions from open-cell SPF at three temperatures in micro-scale chambers.

0 1,000 2,000 3,000 4,000 5,000 6,000 7,000 8,000

FIG 7 TCPP emissions from open-cell SPF after 480 h in micro-scale chambers.

y = 4.1541e 0.1049x

R ² = 0.9816

1.0 10.0

Aldehyde emissions were higher at elevated temperatures; however, a ture relation was not established As shown inFig 8, formaldehyde emissions werehigher at 40 and 65C; however, there were no apparent differences in emissions atthese elevated temperatures In this case, formaldehyde emissions were notdetected, or the result was close to the detection limit at ambient temperature Test-ing at elevated temperatures could potentially be used to enhance the detection ofaldehydes, although a temperature relation was not established.

tempera-TEMPERATURE EVALUATION WITH CLOSED-CELL SPF

The emission factors for closed-cell SPF are reported inTable 11 As shown inFig 9, sions of the blowing agent HFC-245fa at elevated temperatures also showed a drop, surge,and another drop pattern in the decay curve during the first few days in the chamber.After the emissions stabilized, the compound continued to decay, approaching steady-state conditions at 9 days (216 h) at 23C; the compound continued to decay through

emis-20 days (480 h) at 40 and 65C The relation between temperature and HFC-245fa sions appeared to be linear rather than exponential (Fig 10) At 40 and 65C, TCPP emis-sions were above the reporting limit for closed-cell SPF at 2 h, and then the emissionfactor dropped below the reporting limit for the duration of the 20-day study

emis-No emissions of formaldehyde or propionaldehyde were detected at 23 and

40C; however, both of these compounds were observed at 65C As shown inFig 11,acetaldehyde was detected at 23, 40, and 65C, but after 72 h, there was no apparent

FIG 8 Formaldehyde emissions from open-cell SPF at three temperatures in

micro-scale chambers.

0.00 5.00 10.00 15.00 20.00 25.00

difference in the emissions at 40C compared to those measured at 23C At 65C,emissions of formaldehyde, propionaldehyde, and acetaldehyde were all observedabove the detection limits These data suggest that operating the chambers at 65Cmay enhance the detection of potential aldehyde emissions.

OPEN-CELL SKIN TRIMMING

After application in a building, open-cell SPF insulation may be trimmed to alignwith wall studs or other structural elements prior to installing wallboard To testthe effect of trimming the surface on emissions, the generic open-cell SPF sampleswere evaluated with and without the surface skin present at the same time the

TABLE 11 Generic closed-cell SPF in micro-scale chambers: temperature evaluations.

40 <74.4 <298 <298 <298 <149 <149 <149 <149 <149

65 <74.4 <893 <893 <595 <298 <298 <298 <298 <298 BDMAEE 23 <4.97 <9.94 <9.94 <9.94 <9.94 <4.97 <4.97 <4.97 <9.94

40 <4.97 <19.9 <19.9 <19.9 <9.94 <9.94 <9.94 <9.94 <9.94

65 <4.97 321 <59.6 46.2 36.4 <19.9 <19.9 <19.9 <19.9 DAPA 23 <34.5 <68.9 <68.9 <68.9 <68.9 <34.5 <34.5 <34.5 <68.9

40 <34.5 <138 <138 <138 <68.9 <68.9 <68.9 <68.9 <68.9

65 <34.5 <414 <414 <276 <138 <138 <139 <138 <138 TCPP 23 <4.04 13.1 36.0 17.2 8.94 4.19 <4.04 <4.04 <8.07

40 <4.04 143 <16.1 <16.1 <8.07 <8.07 <8.07 <8.07 <8.07

65 <4.04 188 <48.4 <32.3 <16.1 <16.1 <16.1 <16.1 <16.1 Formaldehyde 23 <2.10 <2.22 <1.90 <1.90 <1.85 <1.94 <1.90 <2.27 <1.67

40 <2.10 <2.22 <1.90 <1.90 <1.85 <1.94 <1.90 <2.27 <1.67

65 <2.10 10.6 11.6 8.98 9.76 2.87 5.71 4.81 4.67 Acetaldehyde 23 <2.10 30.0 15.8 8.91 8.50 5.51 4.57 3.72 3.07

40 <2.10 55.4 28.1 20.1 12.1 5.59 5.10 4.04 <1.67

65 <2.10 135 46.9 26.8 19.4 10.3 11.5 9.35 10.4 Propionaldehyde 23 <2.10 <2.22 5.40 <1.90 <1.85 <1.94 <1.90 <2.27 <1.67

40 <2.10 15.9 8.60 <1.90 <1.85 <1.94 <1.90 <2.27 <1.67

65 <2.10 74.0 25.4 12.7 12.5 4.43 3.96 <2.27 6.93

Note: BDMAEE ¼ bis(2-dimethylaminoethyl) ether; DAPA ¼ bis(dimethylaminopropyl) methylamine; HFC-245fa ¼ 1,1,1,3,3-pentafluoropropane; TCPP ¼ tris(1-chloro-2-propyl) phosphate; TMAEEA ¼ N,N,N-trimethylaminoethylethanolamine Emission factors are reported as lg/m 2 per hour Emission factor reporting limits were calculated with the detection limit on the sorbent tube/cartridge, sampling time/volume, and surface area of samples The reporting limits shown with a “less than” symbol vary depending on the sampling conditions.

FIG 9 HFC-245fa emissions in closed-cell SPF at three temperatures in micro-scale

chambers.

0 1,000 2,000 3,000 4,000 5,000 6,000

FIG 10 HFC-245fa emissions in closed-cell SPF versus temperature after 216 h in

FIG 11 Acetaldehyde emissions in closed-cell SPF at three temperatures in micro-scale chambers.

FIG 12 BDMAEE emissions at 23  C in generic open-cell SPF: skin-trimming comparison.

0 500

FIG 13 TCPP emissions in generic open-cell SPF at 40  C: skin-trimming comparison.

0 500 1,000

temperature evaluation study was performed at 23, 40, and 65C Emission resultsfor the open-cell SPF are reported inTable 9andTable 10 As shown inFig 12, theBDMAEE emissions were consistently higher with the skin intact and lowerwith the skin removed Similarly, as shown inFig 13, after the chambers reached

a quasi-steady state, TCPP emissions at elevated temperatures were also lowerwith the skins removed, although there was a smaller difference When cut tothe same dimensions, samples with the skin intact weighed more than sampleswith the skin removed Therefore, samples with skins or samples that weresprayed with more than one pass during application (internal skins) have agreater density This may explain why BDMAEE and TCPP emissions were low-

er with the skins removed It is also feasible that during the exothermic foamingprocess, these compounds may have coalesced at the skin that was removed withtrimming Conversely, the aldehyde emissions did not show any apparent differ-ence with the skins removed (Fig 14), possibly because of the higher vapor pres-sure of these compounds

Conclusions

Micro-scale chambers may be useful in evaluating SPF insulation for chemicalemissions of VOCs under controlled conditions The higher air exchange rate andloading factor of the micro-scale chambers produced higher emissions of TCPP, anSVOC In general, micro-chamber emissions tend to be within an order of magni-tude compared to small-scale chamber data Some emission factors were higher forsmall-scale chambers (acetaldehyde for closed-cell SPF), and some were lower insmall-scale chambers (TCPP) The aldehyde emissions may be dependent on themass of the sample; therefore, mass-specific emission factors should be reported inaddition to area-specific emission factors

The data from this study demonstrate that SPF samples can be tested in scale chambers at temperatures ranging from 23 to 65C; however, additional re-search is needed to evaluate the relation between sample collection times and thevariability of emission factors of some compounds during the first 5 to 7 days of thetests In order to show the decay pattern, several samples may need to be collectedfrom the chambers over various times; otherwise, careful attention to the time of airsample collection may be necessary to avoid significant spikes and drops of emis-sions of some compounds prior to reaching a quasi-steady-state condition in thechambers At the time of this research, the draft ASTM method specified collectingsamples from micro-scale chambers after 2 and 24 h; this time may need to be ex-tended to reach a quasi-steady state and to evaluate emissions from SVOCs such asTCPP VOC emissions may initially be emitted at a higher rate when tested atelevated temperatures; however, emission rates may decay faster because of thedepletion of the compound in the source Elevated temperatures may be useful inenhancing the detection of potential aldehyde or other emissions that are notdetected at ambient temperature

micro-BDMAEE emissions were reduced when the skin of open-cell SPF was removed tosimulate trimming of the insulation against wall studs or other structural elements in abuilding There was no apparent difference of aldehyde or flame-retardant emissionswhen the skin was removed When the surface skin was removed from the samples,the density of the samples decreased, which may have reduced the emissions of thecatalyst Furthermore, the catalyst may have coalesced at the skin during the foamingprocess that was removed with trimming The aldehydes may readily diffuse throughthe material regardless of the presence of the surface skin.

TMIBPA showed poor precision (29.7 % RSD) and a negative bias (36.7 %)compared to other compounds that were evaluated with the TD-GC-MS method.Although the amine catalyst was not detected in any of the samples, this compoundwas not reported during this study because of its poor analytical performance.Further method development may be necessary for challenging compounds such asreactive amine catalysts These reactive compounds can be used in the formulations

to reduce emissions; however, they can be difficult to quantitate with existingmethodology The ASTM D22.05 task groups that are developing standards to mea-sure emissions from SPF may need to develop additional analytical methods toquantify these challenging compounds

To improve the data capture rate (less nondetects), a longer sample durationmay be necessary when collecting emissions onto the TD tubes Pretesting samplescan be useful in establishing the scale for sampling times and volumes to improvethe quality of the data Sampling very volatile compounds onto separate TD tubescontaining stronger sorbents (e.g., Carboxen) helps to avoid breakthrough of theblowing agent and allows the less volatile compounds (e.g., amine catalysts andflame retardants) to be sampled longer without exceeding maximum samplingvolumes Future research should examine extending the maximum sampling timesand volumes to optimize the detection limits of target compounds

ACKNOWLEDGMENTS

The authors thank Ken Riddle, Tim Takah, Scott Ecoff, Shen Tian, Brian Karlovich,Richard Romero, and Eloy Martinez at Covestro LLC; Todd Wishneski at BASF Cor-poration; CPI SPF Emissions Task Force; and ASTM International SubcommitteeD22.05 on Indoor Air

References

[1] Sebroski, J R., “Research Report for Measuring Emissions from Spray Polyurethane Foam (SPF) Insulation,” http://polyurethane.americanchemistry.com/Resources-and- Document-Library/Research-Report-for-Measuring-Emissions-from-Spray-Polyurethane-