DEPARTMENT OF HEALTH AND HUMAN SERVICES

Centers for Disease Control and Prevention

National Institute for Occupational Safety and Health

Estimating the Permeation 

Resistance of Nonporous Barrier 

Polymers to Sulfur Mustard (HD) 

and Sarin (GB) Chemical Warfare 

Agents Using Liquid Simulants
Estimating the Permeation 

Resistance of Nonporous 

Barrier Polymers to Sulfur 

Mustard (HD) and Sarin (GB) 

Chemical Warfare Agents 

Using Liquid Simulants 

Donald Rivin, Ph.D.

Wendel J. Shuely

Frank Palya, Jr. 

Robert S. Lindsay

Axel Rodriguez

Philip W. Bartram

DEPARTMENT OF HEALTH AND HUMAN SERVICES

Centers for Disease Control and Prevention

National Institute for Occupational Safety and Health
ii

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DHHS (NIOSH) Publication No. 2008–141 

July 2008 

Safer • Healthier • PeopleTM
iii

Foreword

In March 1999, the National Institute for Occupational Safety and Health (NIOSH) 

cosponsored a Chemical and Biological Respiratory Protection Workshop with 

the Occupational Safety and Health Administration (OSHA) and the Department 

of Defense, U.S. Army Research, Development and Engineering Command 

(RDECOM). The objectives of this meeting were to: (1) identify and understand 

the hazards associated with a terrorist chemical and biological incident, (2) 

identify the different civilian responders and their respiratory protections needs, 

(3) determine which respirators and selection criteria are currently being used for 

response to these incidents, and (4) determine public and medical community 

concerns that must be considered in developing standards for chemical and 

biological respiratory protective devices. NIOSH began collaborating with the 

National Institute of Standards and Technology (NIST), OSHA and RDECOM, 

which includes Edgewood Chemical Biological Center (ECBC) and Natick Soldier 

Center (NSC), to address the concerns identified at the workshop, and to discuss 

the development of standards for emergency first responder respiratory protection.

In April 2001, NIOSH held a public meeting on developing and implementing 

standards for chemical, biological, radiological and nuclear (CBRN) respiratory 

protective devices. At the meeting it was announced that actual military chemical 

warfare agents (CWA) would be used in future NIOSH certification testing of 

CBRN respiratory protective devices. Sarin (GB) and sulfur mustard (HD) had 

been chosen as representative CWA in their categories. Respirator and other 

personal protective equipment (PPE) manufacturers requested that NIOSH 

identify chemical compounds that could be used as test simulants in lieu of GB 

and HD. These manufacturers expressed an interest in using CWA simulants for 

in-house material and product development testing and to pretest their respirator 

systems for CWA agent permeation resistance. Manufacturers do not have access 

to CWA to perform testing and there are a limited number of certified laboratories 

able to perform CWA testing because of the high cost, toxicity, and the extensive 

regulatory controls. This makes any type of CWA testing very expensive and 

inconvenient as a result of the required lead-time. 

To address the needs of manufacturers, NIOSH initiated the Chemical Warfare 

Agent Simulant Project with ECBC and NSC. This yielded the development of a 

lower cost method to test the permeation resistance of candidate barrier materials 

for use in protective equipment and the identification of chemical compounds 

that can be used to simulate the permeation effects of GB and HD. I am pleased 

to release this document, which will assist manufacturers in providing CBRN 

protective devices to the first responders of a potential CBRN terrorist attack. In 

addition, I am also pleased to announce that NIOSH has released a NIOSH CBRN 
iv

standard for a self-contained breathing apparatus, an air-purifying respirator, 

an escape respirator, and a powered air-purifying respirator and that NIOSH 

is continuing its efforts to release CBRN standards for other respiratory 

protective devices. 

John Howard, M.D..

Director, National Institute for 

Occupational Safety and Health

Centers for Disease Control and Prevention
v

Contents

Foreword ......................................................................................................... iii

Tables............................................................................................................... vii

Figures............................................................................................................. vii

Acknowledgments.......................................................................................... viii

Executive Summary........................................................................................ ix

1.0 Introduction .............................................................................................. 3

1.1 Background .......................................................................................................... 3

1.2 Scope of Phase I................................................................................................... 5

1.2.1 Experimental Design...................................................................................... 5

1.2.2 Application of Test Method............................................................................ 6

1.2.3 Survey of the Applications of CWA Solvent Parameters 

 and Solubility Phase Diagrams...................................................................... 7

1.2.4 Limitations of the Current Investigation......................................................... 9

2.0 Procedures and Results .......................................................................... 13

2.1 Selection of Simulants .......................................................................................... 13

2.1.1 Kinetic Property Screen: Molecular Cross Section or Molecular Volume...... 14

2.1.2 Kinetic Property Screen: Vapor Pressure ...................................................... 14

2.1.3 Thermodynamic and Molecular Screen: Aprotic, Dipolar Structure.............. 14

2.1.4 Thermodynamic and Molecular Screen: Molecular Solvation Parameters.... 14

2.1.5 Toxicity........................................................................................................... 15

2.1.6 Experimental Screening: Sorption Measurements ........................................ 15

2.1.7 Experimental Screening: 

 Exploratory Permeation Testing of Thickness Effects ................................... 15

2.2 Polymeric Materials for Sorption and Permeation Studies................................... 17

2.2.1 Strategy for Material Selection ...................................................................... 17

2.2.2 Documentation on the Selected Elastomers ................................................. 21

2.2.3 Documentation of the Elastomer Compositions............................................ 22

2.2.4 Experimental Design for Elastomer Specimens ............................................ 26

2.3 Immersion Methods for Determination of 

 Solubility and Diffusion Coefficients ..................................................................... 27

2.4 Permeation Methodology ..................................................................................... 27

2.4.1 Equipment in Research and Development Studies 

 and Standardized Method............................................................................. 27

2.4.2 General Equipment........................................................................................ 27

2.4.3 Edgewood Chemical Biological Center (ECBC) Permeation Equipment ...... 28

2.4.4 Natick Soldier Center (NSC) Permeation Equipment .................................... 29

2.4.5 Permeation Conditions .................................................................................. 31
vi

2.5 Data Analysis of Solubility and Diffusion Properties............................................. 32

2.6 Immersion Results ................................................................................................ 33

2.7 Permeation Results............................................................................................... 36

2.7.1 Characteristic Parameters of the Permeation Curve..................................... 36

2.7.2 Data Analysis of Permeation Parameters ...................................................... 37

2.7.3 Normalized Permeation Parameters for 

 Comparisons Independent of Thickness....................................................... 37

2.7.4 Permeation Parameter Ratios Relative to DCH and DCH-Butyl Rubber....... 38

3.0 Discussion ................................................................................................ 47

3.1 Safe-Sided Simulants and Tests........................................................................... 47

3.2 Solubility Test as a One-Sided Candidate Material Screen .................................. 48

3.3 Relative Criteria for Selecting Candidate 

 Materials Based on Permeation Correlations ....................................................... 48

3.4 Absolute Criteria for Selecting Candidate 

 Materials Based on Permeation Correlations ....................................................... 48

3.5 Permeation Curve Comparisons........................................................................... 49

3.6 Infinite Versus Finite Source Permeation Geometry ............................................. 50

4.0 Summary................................................................................................... 53

References...................................................................................................... 57

Bibliography: Application of Solvent-Solute Parameters 

and Solubility Phase Diagrams to Chemical Defense, 

Unlimited Distribution Publications.............................................................. 61

Appendix A: Standard Test Method for Estimating 

Permeation Resistance of Nonporous Barrier Polymers 

to Liquid Chemical Warfare Agents (GB and HD) 

Using Liquid Simulants .................................................................................. 67

Appendix B: Liquid Permeation Cell Mechanical Drawings ....................... 85

Appendix C: CWA Permeation Tables........................................................... 95
vii

Tables

Table 1. Simulant selection criteria to match CWAs

 and simulants for sorption and permeation correlations ......................13

Table 2. Candidate simulants for exploratory sorption and 

 permeation testing with a spectrum of elastomer thickness values.....16

Table 3. Simulants selected based on kinetic, 

 thermodynamic, toxicity, and experimental screening factors .............17

Table 4. Selection criteria for selection of 

 materials in CWA simulant permeation studies ....................................18

Table 5. Commonly used materials in NIOSH-approved respirators..................20

Table 6. Elastomeric reference materials 

 based on chemical defense respirators................................................22

Table 7. Poly(dimethylsiloxane), silicone composition 

 based on molding formulation ..............................................................23

Table 8. Poly(ethylenepropylene), (EPDM) composition 

 based on molding formulation ..............................................................24

Table 9. Poly(isobutylene), (Butyl) composition 

 based on molding formulation ..............................................................25

Table 10. Experimental design matrix and specimen inventory 

 for flooded surface permeation for each material at 

 one temperature and thickness ............................................................26

Table 11. Solubility and diffusivity from immersion at 35oC .................................34

Table 12. Mean permeation parameters compensated 

 for specimen thickness .........................................................................41

Table A-1. Nominal Simulant Chemical Compounds .............................................75

Figures

Figure 1. Liquid Permeation Cell..........................................................................28

Figure 2. Flame ionization detector, SRI, Model 110 ...........................................29

Figure 3. Air heater controller, WPI, Model Air-ThermTM......................................30

Figure 4. Temperature control chamber, RDECOM, Natick Soldier Center .........31

Figure 5. Fractional weight gain (FWG)................................................................32

Figure 6. Permeation curve with characteristic parameters ................................36

Figure 7. Normalized breakthrough time relative to 

 DCH value for the same elastomer compound.....................................42

Figure 8a. Average permeability coefficient from the 

 mean of the replicates of the four polymers. ........................................42

Figure 8b. Average permeability coefficient from the 

 mean of replicates of Butyl, EPDM, and Nitrile.....................................43

Figure 9. Permeation rate of CWAs and simulants in 12-mil Butyl rubber...........49

Figure A-1a. Liquid Permeation Cell schematic: side view....................................74

Figure A-1b. Liquid Permeation Cell: top view.......................................................74

Figure A-2. Example Setup of Permeation Test System ......................................79

Figure A-3. Typical Permeation Curve, Electronic Signal in Voltage 

 Proportional to Permeation Rate.......................................................80
viii

Acknowledgments

This document was prepared by the National Institute for Occupational Safety 

and Health (NIOSH), National Personal Protective Technology Laboratory 

(NPPTL) in collaboration with the U.S. Army Research, Development and 

Engineering Command (RDECOM) including their staff from the Edgewood 

Chemical Biological Center (ECBC) and the Natick Soldier Center (NSC). 

Frank Palya, Jr. (NPPTL) was the project officer. Dr. Donald Rivin (NSC) was 

the principal investigator. Wendel J. Shuely, Science Applications International 

Corporation (SAIC) was the lead scientist under contract with ECBC. Robert 

S. Lindsay (ECBC) directed the chemical warfare agent (CWA) permeation 

resistance testing and assisted with the development of the test method. 

Axel Rodriguez (NSC) and Philip W. Bartram (ECBC) conducted laboratory 

experiments and provided technical expertise.

The following additional personnel from RDECOM are gratefully 

acknowledged for their contributions to the CWA Simulant Project:

 William P. Ashman of the ECBC, Agent Chemistry Team, performed the 

initial literature search in an attempt to find credible reports on chemical 

compounds that could be used as Sarin (GB) and sulfur mustard (HD) 

simulants. In addition, Mr. Ashman provided invaluable technical advice 

throughout the course of the CWA Simulant Project. 

 Susan Procell and Elaina Harrison of the ECBC, Applied Chemistry Test 

Team, performed the permeation resistance testing on the selected barrier 

materials using actual GB and HD chemical warfare agents.

Monica Hall, of ECBC, assisted with the GB and HD sorption experiments.

 Manuscript reviews were provided by Maryann D’Alessandro, Ph.D.; 

Pengfei Gao, Ph.D.; Paul Middendorf, Ph.D.; Leroy Mickelson, Ph.D.; 

Richard W. Niemeier, Ph.D.; and Capt. James S. Spahr (NIOSH); Lee 

Campbell (ECBC); Zane N. Frund (Mine Safety Appliances Company); 

and Larry A. Brey, Ph.D. (3M).

Acknowledgment is extended to NPPTL contracted personnel for their 

contribution in additional areas: Peter C. Bellina of EG&G Technical Services, 

Inc. (EG&G) for editorial support and for obtaining photographic releases 

from manufacturers for equipment depicted in this report and Candace A. 

Wolf (EG&G) for her technical support.
ix

Executive Summary

The purpose of this document is to report the results of tests to identify 

appropriate simulants for testing permeation and to specify the laboratory 

procedure for estimating chemical warfare agent (CWA) permeation of personal 

protective equipment (PPE). Advancements in this research can benefit the first 

responder community by providing PPE manufacturers with information and 

testing techniques that will reduce the time and resources needed to engineer 

products that weigh less, have better permeation resistance, are less cumbersome, 

and are potentially less expensive. 

The National Institute for Occupational Safety and Health (NIOSH) and the 

National Institute of Standards and Technology (NIST) signed an Interagency 

Agreement (IAA) in July 2000. Under this IAA, NIOSH initiated a collaborative 

effort with the Natick Soldier Center (NSC) and the Edgewood Chemical 

Biological Center (ECBC) of the U.S. Army Research, Development and 

Engineering Command (RDECOM) to develop standards for chemical, biological, 

radiological, and nuclear (CBRN) respiratory protective devices and to develop 

methods for certification testing of these devices, including evaluation of CWA 

permeation resistance. The NSC and ECBC are the primary organizations within 

the Department of Defense (DoD) that research, develop, engineer, and acquire 

equipment relating to nuclear, biological, and chemical (NBC) personal protection. 

During the April 2001 NIOSH public meeting on developing and implementing 

standards for CBRN respiratory protective devices, it was announced that actual 

military CWAs would be used in future NIOSH certification testing of CBRN 

respiratory protective devices. Sarin (GB) and sulfur mustard (HD) were the 

CWAs selected by NIOSH to be used as the representative CWAs for certification 

testing. Manufacturers of respirators and other PPE requested that NIOSH 

identify less toxic chemical compounds (simulants) that could be employed 

for testing at their laboratories. This testing would include in-house material 

and product development testing and respirator system pretesting for CWA 

permeation resistance. During a January 2002 meeting that was held in Pittsburgh, 

Pennsylvania to discuss CBRN respirator standards development, the International 

Safety Equipment Association (ISEA) expressed the need for the NIOSH National 

Personal Protective Technology Laboratory (NPPTL) to identify simulant test 

agents for GB and HD. In subsequent periodic meetings, the ISEA continually 

expressed the need for simulant test agents. Manufacturers do not have access to 

CWAs to perform testing, and only a limited number of certified laboratories are 

able to perform CWA testing because of the high test cost, toxicity of CWAs, and 

extensive regulatory controls. Overall, testing with CWAs would substantially slow 

the identification of PPE that would protect against CWAs.

As part of the collaboration between NIST, RDECOM, and NIOSH to develop 

CBRN respirator standards, a literature search was conducted by RDECOM 

employing the Agent Simulant Knowledge (ASK) database in February 2002. 
x

However, the search yielded few reports with data on CWAs and simulant 

permeation through barrier materials using consistent test methods and 

conditions. Thus simulants could not be identified from the literature. As a 

result, NIOSH determined that additional research was needed to address 

the requests of the PPE manufacturers and ISEA members to identify CWA 

simulants that can be used in testing. 

In May 2002, the Chemical Warfare Agent Simulant Project was initiated with 

the following goals:

1. Identify chemicals (simulants) that simulate the permeation of GB and 

HD through elastomeric barrier materials that are commonly used in 

respirators. 

2. Develop a convenient and reliable laboratory procedure (test method) that 

can be used by PPE manufacturers for estimating GB and HD permeation 

rates through barrier materials using the simulants. 

Research was initiated when the NSC developed an inexpensive permeation 

test method that uses a liquid permeation cell for testing both hard and soft 

barrier materials up to 0.7 cm thick. This permeation test method uses the 

flooded surface technique in which the test liquid covers one surface of the 

specimen material. 

A systematic methodology was employed to select three barrier materials 

to be used in the tests to identify the simulants with similar permeation 

characteristics to HD and GB. The three barrier materials selected are: 

polydimethylsiloxane [Silicone], poly(isobutylene) [Butyl], and poly(ethyleneco-propylene-co-diene) EP8A [EPDM]. 

Immersion experiments were used to identify simulants having a similar 

solubility to HD and GB in the three selected barrier materials. Nine liquids 

could be obtained commercially that had physicochemical properties similar 

to HD and GB and these were selected to test the permeability of barrier 

materials. From the nine liquids evaluated, the following four simulants were 

found to best replicate the permeation of GB and HD when challenging the 

three barrier materials: 1,6 dichlorohexane (DCH) and 2-chloroethyl phenyl 

sulfide (CEPS) are simulants for HD; diethyl methylphosphonate (DEMP) 

and diisopropyl methylphosphonate (DIMP) are simulants for GB.

Further testing is in progress to extend the CWA-simulant correlations to a 

wider range of barrier polymers. 

The test method developed at NSC can be used to test a variety of materials 

used in PPE. It can be used to perform permeation resistance testing with 

any nonreactive liquid, including toxic industrial chemicals (TICs), in which 

the polymer does not decompose or dissolve. This document will assist PPE 
xi

manufacturers by providing them with a method to assist in selecting the 

materials for use in PPE. This test method may reduce product development time 

and costs for manufacturers by reducing development/engineering fees, testing, 

and lead times.
Introduction

1.0
Introduction 3

1.0 Introduction

1.1 Background 

The National Institute for Occupational Safety and Health (NIOSH) held several 

public meetings to address the stakeholder need for NIOSH to develop and 

implement standards for chemical, biological, radiological, and nuclear (CBRN) 

respiratory protective devices. When NIOSH’s intent to use military chemical 

warfare agents (CWAs) was introduced to certify respiratory protective devices, 

some respirator and other personal protective equipment (PPE) manufacturers 

requested that NIOSH identify chemical compounds (simulants) that can be used 

to simulate the molecular permeation and defect penetration effects of CWAs 

on protective equipment. Similar concerns were expressed by the International 

Safety Equipment Association (ISEA) in a January 2002 meeting with NIOSH’s 

National Personal Protective Technology Laboratory (NPPTL). In subsequent 

meetings hosted by the ISEA, this need for NPPTL to identify simulant test 

agents was continually expressed. Manufacturers want to use CWA simulants 

for product development and quality control testing and to test their respirators 

prior to submitting an application for NIOSH CBRN certification. Manufacturers 

do not have access to military CWAs to perform in-house material and product 

development testing and a limited number of certified laboratories are able to 

perform CWA testing. This is due to high cost, toxicity and regulatory controls; 

thus making any type of CWA testing very expensive and inconvenient. 

In December 2001, while developing the NIOSH CBRN standard for an opencircuit, self-contained breathing apparatus (SCBA) [NIOSH 2001], NIOSH 

in collaboration with the U.S. Army Research, Development and Engineering 

Command (RDECOM), Edgewood Chemical Biological Center (ECBC), 

performed an evaluation of CWA and toxic industrial chemicals (TICs) listed 

in the USACHPPM Technical Guide 244 [U.S. Army 2000] and in the Draft 

National Fire Protection Association (NFPA) 1994 Standard [NFPA 1994]. NIOSH 

selected Sarin (GB) and sulfur mustard (HD) as the representative CWA test 

agents to be used in certification testing of respirators because they are among 

the most permeating through nonporous barrier materials and have the ability to 

penetrate through micro-pores resulting from material defects or poorly interfaced 

respirator components. In February 2002, a collaborative effort between NIOSH 

and ECBC was undertaken to identify viable GB and HD simulants to be used for 

permeation testing of elastomeric barrier materials. A literature search conducted 

by ECBC employed the Agent Simulant Knowledge (ASK) database in February 

2002 which revealed few reports providing both CWA agent permeation as well 

as simulant permeation data for barrier materials. In most cases, the data found 

in these reports were obtained using test methods and conditions that were not 

consistent with each other. Therefore, due to the lack of data and inconsistent test 
4 Introduction

methods, a relationship could not be determined between CWA and simulant 

permeation rates with adequate confidence. Note, the term correlation is used in 

the general sense in this report, rather than indicating a specific relationship of one 

dependent variable and one independent variable with a regression and correlation 

coefficient. Most often, correlation refers to a correlated ranking of solubility and 

permeation values that allows one to deselect materials with potentially poor GB 

and HD resistance, based on simulant measurements.

NIOSH determined that a research study was needed to identify chemical 

compounds that simulate the permeation effects of GB and HD through barrier 

materials, and to derive a correlation between CWAs and their simulants. NIOSH’s 

NPPTL collaborated with the Natick Soldier Center (NSC) and the ECBC both 

of the RDECOM in this research study by initiating the CWA Simulant Project in 

May 2002. 

The CWA Simulant Project was sectioned into two phases. This document reports 

the test methods and results of experiments conducted during Phase I of the CWA 

Simulant Project. Phase I was completed in October 2003 and encompasses the 

initial work that was completed to accomplish the following goals: 

1. Identify chemical compounds, with low toxicity relative to the CWAs, 

that simulate the permeation effects of GB and HD through elastomeric 

barrier materials. 

2. Develop a convenient and reliable laboratory procedure (test method) that 

can be used by manufacturers for estimating GB and HD permeation using 

the simulants. 

With continuing interest and support of the stakeholder community, the National 

Institute of Standards and Technology (NIST) funded the continuation of the 

project; hence, the continuing research effort designated as Phase II is being 

conducted by RDECOM in collaboration with NPPTL. The research will be 

conducted by RDECOM concurrently with publication of this Phase I report. 

The plan of Phase II includes selection of additional barrier materials, sorption/

desorption and permeation testing in 2005–2007, and use of these results to 

improve predictions of simulant to CWA permeation behavior in 2007. The test 

method established in Phase I provides a standardized permeation method for 

testing of additional materials in Phase II. Manufacturers can begin using this 

Phase I method immediately after publication of this report, before completion of 

Phase II.

Phase II is not within the scope of this document and, therefore, only a brief 

outline of the methodology of that phase is provided here. Phase II encompasses 

the following goals: 
Introduction 5

1. Improve the estimation reliability of the new permeation procedure by testing 

additional simulants and a wider range of polymeric barrier compounds. 

Also, determine the quantitative relationship between permeation behavior 

observed using a flooded surface and that of traditional low-loading (“finite”) 

liquid drop challenge (5–10 g/m2).

2. Compare CWA and simulant sorption and desorption characteristics for a 

wide range of representative barrier materials. 

3. Perform testing to elucidate trends in the barrier performance of polymer 

compounds based on readily available chemical and physical properties of the 

polymer and the permeating CWA molecules. Properties to be investigated 

include: permeant molecular volume and cross section, polymer free volume, 

crosslink density, molecular interaction factors such as solubility parameters, 

polymer cohesion phase diagrams, and viscoelastic parameters. Predictions 

will be validated using American Society for Testing and Materials (ASTM) 

standard methods and the test method described in the Procedures and 

Results section of this Phase I report.

4. Expand the solubility relationship of the more polar protective polymers, 

especially with respect to the solvent parameters of the chemical agents and 

simulants and the cohesion phase diagrams.

This document was written for technical experts on selecting materials for 

protective equipment; this test method report assumes a basic knowledge of the 

details of polymer chemistry, permeation testing, and sorption, solubility, and 

diffusion processes.

1.2 Scope of Phase I

This section describes the scope of Phase I of the CWA Simulant Project including 

experimental design, test methods, procedures, as well as the limitations of this 

phase of the project.

1.2.1 Experimental Design

This study was implemented using a small subset of possible barrier materials and 

CWAs. Only three barrier materials and two CWAs (GB and HD) were included 

in the experimental design. A full experimental design might include CWA 

compounds, simulants, material types, material compositions within each type, 

and experiment type. The CWA liquids studied could include several G-agents 

(GA, GB, GD, GF), vesicants, and V-agents. NIOSH selected GB and HD as the 

representative agents for CWAs when performing respirator certification testing 

[NIOSH 2001]; therefore, these two CWA compounds were selected for testing. 

This phase was limited to two simulants for each CWA that appeared to be 

representative of those reported in the literature, based on preliminary permeation 
6 Introduction

experiments with simulants (see Section 2.1) that differ in molecular cross section 

and solubility parameter.

In a full experimental design, the variables for materials could have included: 

physical state, such as elastomers or thermoplastics; structural type, such as 

acrylics or urethanes; chemical-material interaction type, such as dispersion, polar, 

or hydrogen bond donors; heterogeneity, unfilled or filled, such as composites or 

laminates. In this phase, the investigation was limited to three elastomers with 

primarily dispersion (London forces) interactions; the rationale is discussed in the 

Materials section. It was necessary to limit the field of materials to three elastomers 

because of the limited resources available. The three materials were selected 

based on past RDECOM experience with the materials where it was found that 

the materials provide an optimum combination of properties, as described in the 

section on materials selection. 

Previous experimental designs for testing protective materials have included: 

permeation to steady state, permeation to breakthrough, sorption at specific time 

intervals, sorption to equilibrium solubility values, desorption diffusion and/or 

a set of chemical resistance tests. In this phase, experimentation was limited to 

immersion sorption, equilibrium solubility, and permeation to steady state since 

these provided the most fundamental comparison of protective performance based 

on chemical interaction with the elastomers.

This study employs an infinite-source, flooded-surface technique rather than 

the traditional finite-source droplet technique in order to obtain fundamental 

chemical-material permeation properties that allow direct comparisons of material 

performance. Future work will include comparisons of the flooded-cell versus 

droplet permeation conditions.

Other variables were limited to a single, controlled value in this phase. 

Temperature was held constant at 35°C, near skin temperature. Thickness 

was varied for each polymer type with the thickness effect normalized for the 

permeation parameters.

1.2.2 Application of Test Method

A new test method was developed in Phase I of this program and is detailed in 

Appendix A. Data interpretation techniques are presented that use permeation 

and immersion test results to assist PPE manufacturers in selecting the appropriate 

barrier materials for their product to resist CWA permeation. This document 

describes the required test equipment, test procedures, and data analysis 

techniques in sufficient detail so that a qualified technician can perform the 

following tasks:

n Select and operate test equipment

n Select material specimens

n Perform the permeation test

n Analyze the test results
Introduction 7

Mechanical drawings of the permeation cell test fixture required for the test 

method are provided in Appendix B, enabling PPE manufacturers to reproduce 

the test fixture and obtain test results that can be compared with the permeation 

results contained in this document. The enclosed method is used to determine the 

barrier performance of flat nonporous films, membranes, and sheets up to 

0.7 cm thick when one surface of the material is entirely exposed (or “flooded”) 

to a test liquid.

The test method can be used to test permeation of any liquid that does not 

decompose or dissolve the test specimen, which could include most industrial 

solvents and many TICs. Simulant permeation is correlated with that of GB and 

HD in order to reduce the need for testing with highly toxic liquids, such as CWAs. 

Permeation test results of poly(dimethylsiloxane) [Silicone], poly(isobutyleneco-isoprene) [Butyl], and poly(ethylene-co-propylene-co-diene) EP8A [EPDM] 

during liquid contact with GB, HD, and simulants are included in this test report 

to assist in future test data analysis. In addition, poly(butadiene-co-acrylonitrile) 

[Nitrile] was tested with only simulants as part of the preliminary screening of 

candidate materials and is included in this report. 

The test method and data interpretation techniques were developed to provide 

PPE manufacturers with a lower cost, more rapid screening method, relative to 

CWA testing, for evaluating the performance of candidate barrier materials to 

be used in the development and production of PPE products such as respiratory 

protection devices and protective garments. This method was developed primarily 

so that PPE manufacturers could use accessible chemical compounds (simulants) 

that have lower toxicity while simulating the permeation effects of CWAs, 

specifically GB and HD. In conjunction with the development of this method, 

simulants were identified based on their physicochemical similarities to HD and 

GB [Rivin et al. 2005]. 

This publication describes a specific test method and test apparatus, and provides 

several simple, qualitative guidelines for applying the correlations between 

CWAs and simulants as given in the Discussion section. However, PPE material 

experts can apply other quantitative data reduction techniques to further rank 

their candidate materials, keeping in mind the caveats regarding overextending 

data analysis, given the multitude of nonlinear effects in solubility, diffusion, and 

permeation relationships.

1.2.3 Survey of the Applications of CWA Solvent Parameters and 

Solubility Phase Diagrams

Solvent-solute parameters are useful tools in screening materials for protective 

barrier performance. Given the time and resource constraints, a limited 

comparison of CWA and simulant solubility parameters was performed and 

a more thorough application was scheduled for future work. This area of 
8 Introduction

investigation was further limited because these values are generally not found in 

public documents, although the CWA solvent parameters from these diagrams had 

been measured and published at ECBC. Therefore, while performing this research, 

phase diagrams developed during the 1960s through the 1980s were used, but the 

specific values are not cited. 

There are several systems of solubility parameter sets and polymer phase diagrams 

in general use and some of these are covered in the earlier documents [Barton 

1983]. The values determined included the solubility parameter, hydrogen bond 

index, dielectric constant, and dipole moment. In addition, Hansen cohesion 

parameters, other cohesion parameters, linear solvation energy relationship 

(LSER) parameters, and molecular dimensions were estimated. The results of 

these estimates can be summarized by generalizing that the solubility parameters 

of the organophosphorus CWA (G and V series) were moderate, in the 

17.4–19.4 MPa1/2 range. 

The organophosphorus CWA dipole moments were high, in the 3.2–3.7 Debye 

range. The organophosphorus CWA hydrogen bond shifts or index values were 

moderately high. Coordinates of a dispersion, hydrogen bonding, and polarity 

parameter were plotted on the solubility phase diagram of polymers to estimate 

chemical resistance. The selection of simulants was based on both matching the 

coordinates with the target CWA and matching the vector distance from the liquid 

coordinates to the phase diagram center passing through the phase boundary for 

total miscibility. For more detailed information on this approach, see Bibliography 

in this document, Application of Solvent-Solute Parameters and Solubility Phase 

Diagrams to Chemical Defense, Unlimited Distribution Publications.

Given the CWA solubility parameter coordinates of the simulants employed, 

the solubility correlations obtained herein are likely limited to the evaluation of 

relatively nonpolar polymers containing predominantly dispersion forces. The 

3-D solvent parameters of GB are substantially different from those of diisopropyl 

methylphosphonate (DIMP) or diethyl methylphosphonate (DEMP). Likewise, 

the 3-D solvent parameters of HD are substantially different from those of 

2-chloroethyl phenyl sulfide (CEPS) or 1,6 dichlorohexane (DCH). However, for 

dispersion dominated polymers, the phase diagram boundary between solubility 

and insolubility has high vector distances from both the CWA and simulant liquid 

coordinates; therefore, a useful correlation can be obtained. For aprotic dipolar 

hydrogen bond acceptor or donor polymers, the phase diagram boundaries will be 

closer to the GB, HD, and simulant polymer solubility phase diagram coordinates 

and solubility differences will be magnified. Many of the protective materials 

are nonpolar polymers; therefore, the screening and further testing of nonpolar 

polymers is a productive starting point. Note that nonpolar polymers may not 

have the mechanical, thermal, or optical properties required for the spectrum of 

materials in a respirator ensemble; therefore, identification of candidate CWAresistant materials in a wider category of polymers is underway.
Introduction 9

1.2.4 Limitations of the Current Investigation

This phase of the work emphasizes fundamental comparisons of chemical-material 

interactions under one set of controlled conditions and does not address predicted 

performance due to the effects of high or low temperatures, moist elastomers, or 

other extreme environmental conditions. 

In Phase I, the permeation of single layers of polymeric materials was measured 

and the measurement of laminates or multiple layers was not included, although 

models of the military M40 series of protective masks employ a resistant elastomer 

over the silicone facepiece. In general, coatings and bonded laminates can be 

evaluated with the methodology described by Rivin [Rivin et al. 2005].
Procedures and Results

2.0
Procedures and Results 13

2.0 Procedures and Results

The four sections of this chapter primarily deal with procedures and include the 

following topics: simulant selection, elastomer material selection, immersion 

solubility procedures, and permeation procedures. 

2.1 Selection of Simulants

An overview of the criteria employed to screen candidate simulants can be 

obtained by reviewing Table 1. Permeation is a complex process that involves both 

kinetic (Table 1, items 1–2) and thermodynamic (Table 1, items 3–4) processes. 

The competitive kinetic processes are droplet evaporation versus diffusion into 

the protective material. The thermodynamic property is the equilibrium solubility 

of the test liquid in the barrier material. The candidate simulants for CWAs were 

evaluated with respect to both kinetics and thermodynamics; further details on 

these criteria are provided below. Relatively lower toxicity (Table 1, item 5) was 

also a criterion. Preliminary screening identified the most appropriate simulants 

and suitable specimen thicknesses that were targeted to provide breakthrough 

times greater than or equal to 1 hour and steady-state permeation in less than 24 

hours (Table 1, items 6 and 7). 

Table 1. Simulant selection criteria to match CWAs and simulants

for sorption and permeation correlations

Number Criterion

1 Kinetic property screen: molecular cross section or molecular volume

2 Kinetic property screen: vapor pressure

3 Thermodynamic and molecular screen: aprotic, dipolar structure

4 Thermodynamic and molecular screen: molecular solvation parameters

5 Relatively lower toxicity

6 Experimental screening: sorption measurements

7 Experimental screening: exploratory permeation testing of thickness effects
14 Procedures and Results

2.1.1 Kinetic property screen: molecular cross section or 

molecular volume

The selection of a kinetic simulant which has the same diffusion rate as a target 

CWA is dependent on the molecular cross section of the diffusing liquid. Matching 

the molecular cross section should allow similar jumps from one molecular-free 

volume site to another as chain motion provides access to adjacent free-volume 

sites. Matching only molecular volumes can cause an error since an identical 

molecular volume can be obtained from a long, narrow molecule and a more 

spherical molecule. Therefore, the minimum molecular cross section provided an 

appropriate correlation parameter. These values were surveyed and compared in 

the selection process.

2.1.2 Kinetic property screen: vapor pressure

Evaporation rate is another kinetic process that competes with diffusion into the 

barrier material; therefore, it was necessary to evaluate the vapor pressure property 

in order to screen candidates for evaporation. A close volatility match was not 

deemed as important for the flooded cell relative to the droplet geometry, since 

the surface of the specimen is always covered with liquid in this partially covered 

(not tightly sealed), low-evaporation cell design. However, vapor pressure was 

maintained as a screening property to maintain volatility in a reasonable range.

2.1.3 Thermodynamic and molecular screen: aprotic, dipolar structure

The G and H series chemical warfare agents are aprotic dipolar, hydrogen-bond 

acceptor liquids and the simulants selected were, therefore, aprotic dipolar, 

hydrogen-bond acceptor liquids, with the exception of DCH. 

2.1.4 Thermodynamic and molecular screen: 

molecular solvation parameters

The selection of a simulant based on only thermodynamic factors would provide 

a “thermodynamic simulant;” this would provide a similar sorption level to 

sorption of a target liquid, such as a CWA for a material. This thermodynamic 

sorption behavior is controlled by molecular interactions comprised of: dispersion, 

dipolar, resonance, hydrogen bond acceptor, and hydrogen bond donor forces. 

The first choice is to select a simulant with values that are as close as possible to 

this set of interaction parameters. Since few compounds will match closely to 

all of these parameters, it is convenient to match the coordinates formed by this 

set of solvation parameters with the relative position on the polymer solubility 

phase diagram. Since phase diagrams are asymmetric, this equivalent, relative 

position is determined by constructing a vector from the asymmetric center to the 

phase diagram boundary (of insolubility), passing through the simulant versus 

an analogous vector for the CWA. One then matches fractional vector lengths. 
Procedures and Results 15

This process is required for every polymer. The process is documented in detail in 

several DoD publications with limited access.

2.1.5 Toxicity

Simulants were screened for lower toxicity relative to the CWA using the ECBC 

ASK database employing all available toxicity data, but primarily oral-rat LD50. 

The toxicity of diisopropylfluorophosphate (DFP) was used as an upper limit 

because this compound is the closest analogue of G-agents that can be purchased 

by laboratories for use as a simulant. However, DFP, itself, was rejected as a 

simulant because it would be too difficult for some laboratories to handle, store, 

and use due to its toxicity constraints. The carcinogenic oxygen analog of HD, 

bis(2-dichloroethyl)ether, was also rejected for the same reason. 

After simulants were screened based on these structures and properties, samples 

were obtained of at least eight candidates (see Table 2) and screening experiments 

were performed. Although these simulants are safer than CWA, some lack 

critical toxicity data. Applicable manufacture safety data sheets (MSDS) should 

be consulted to inform workers of the dangers posed by handling these toxic 

substances. Appropriate safety procedures, adequate equipment and trained 

personnel should be in place prior to obtaining the recommended simulants. 

For more information relating to standard laboratory practice, safety and health 

precautions, refer to Appendix A, Section 7, Safety Precautions and Hazardous 

Waste Disposal, of this document. 

2.1.6 Experimental screening: sorption measurements

Semi-quantitative sorption screening results were compared to CWA values or 

estimates to rank or deselect simulants. 

2.1.7 Experimental screening: exploratory permeation testing of 

thickness effects

A limited number of thicknesses were available for each material. Therefore, 

simulants were screened to determine that the breakthrough times fell between 

about 0.5 and 24 hours. Breakthrough times of greater than 0.5 hours allow 

discrimination between the relatively rapid, defect penetration and slower 

permeation breakthrough (with the exception of rapid-permeating silicone). 

Breakthrough times of less than 24 hours are experimentally convenient and are 

less likely to require addition of liquid to prevent evaporation to dryness. 
16 Procedures and Results

Table 2. Candidate simulants for exploratory sorption and permeation testing 

with a spectrum of elastomer thickness values

Identification codes Chemical compounds

Simulants for bis-2-chloroethylsulfide

HD:

CEMS 2-Chloroethylmethylsulfide

CEiAS 2-Chloroethylisoamylsulfide

CECHS 2-Chloroethylcyclohexylsulfide

CEPS (CEPhS) 2-Chloroethylphenylsulfide

CnBE Chloro-n-butylether

BCEM bis(2-chloroethoxy)methane

BCEE 1,2-bis-(2-chloroethoxy)ethane

DCH 1,6-Dichlorohexane

Simulants for isopropyl methylphosphonofluoridate

GB:

DMMP Dimethylmethylphosphonate

DEEP Diethylethylphosphonate

DIMP Diisopropylmethylphosphonate

DEMP Diethylmethylphosphonate

TEPO Triethylphosphate

In general, the candidate simulants in Table 2 were ranked by the criteria in Table 

1 and the lower ranking simulants for each criterion were eliminated. Examples of 

additional pragmatic considerations included the inconsistent availability and/or 

purity of CEiAS and CECHS commercial samples. The final selection of simulants 

is shown in Table 3. These test chemicals were then used to obtain the permeation 

data for correlation with the chemical warfare agents bis (2-chloroethyl) sulfide 

(sulfur mustard, HD) and isopropyl methylphosphonofluoridate (Sarin, GB). All 

four candidates were evaluated as simulants for each CWA, regardless of structural 

types or their initial assignment as either a GB or HD simulant.
Procedures and Results 17

Table 3. Simulants selected based on kinetic, thermodynamic, 

toxicity, and experimental screening factors

ID Code Chemical compound CAS No.

Purity 

% Source

HD: CEPS 2-Chloroethylphenylsulfide 5535–49–9 98 Lancaster 

synthesis

HD: DCH 1,6-Dichlorohexane 2163–00–0 98 Aldrich 

chemical

GB: DIMP Diisopropylmethylphosphonate 1445–75–6 95 Alfa aesar

GB: DEMP Diethylmethylphosphonate 683–08–9 97 Aldrich 

chemical

2.2 Polymeric Materials for 

Sorption and Permeation Studies

The description of the polymeric materials studied is divided into four sections: 

a strategy for material selection, characteristics of the selected elastomer set, 

composition of each elastomer compound, and an outline of the experimental 

design for the elastomer specimens. 

2.2.1 Strategy for Material Selection

Several complementary strategies were devised for selecting a set of materials 

for the correlation of simulants with agents. The desired characteristics of the 

materials are summarized in terms of selection criteria in Table 4. Some of these 

criteria are operational characteristics; that is, the preferred materials would be 

chemically resistant (no. 1) or would be already in use in respirators (no. 2). 

Other criteria are geometry oriented, in terms of shape (no. 4) and thickness 

requirements (no. 5). Another pair of criteria refers to orthogonal molecular 

compositional characteristics (nos. 6 and 7). In addition, there was a requirement 

for availability of specimens in the quantities and thicknesses needed (no. 8). Each 

of these is outlined below. 
18 Procedures and Results

Table 4. Selection criteria for selection of materials 

in CWA-simulant permeation studies

Number Criterion

1 CWA chemical resistance. Chemical-agent-resistant 

elastomers to provide immediate assistance to NIOSH 

respirator manufacturers

2 Materials from NIOSH-approved respirators

3 Physical state: Material composition limited to elastomers 

4 Geometry: Available in sheet form in quantities required for 

full evaluation

5 Thickness: Available in a thickness providing breakthrough between 0.5 

and 24 hours for every agent-simulant combination.

6 Thermodynamic, orthogonal material interaction set 

7 Kinetic orthogonal polymer set

8 Specimen availability

CWA chemical resistance. The decision was made to not only provide the 

requested simulant selection but to also attempt to provide low sorption, resistant 

polymers to assist the PPE manufacturers in their immediate need to identify 

chemical agent-resistant polymers. A chemically resistant polymer screen was 

compiled from chemical warfare agent experimental sorption and permeation 

data available in various databases or derived from experience with materials from 

fielded chemical defense protective equipment.

Materials from NIOSH-approved respirators. A list of commonly used 

polymeric materials in NIOSH-approved respirators was compiled by evaluating 

the material content of several different systems from different manufacturers. 

These materials were identified on the mechanical drawings provided to NIOSH 

by respirator manufacturers. Selection of materials from this list has the advantage 

of evaluating materials already in use by manufacturers for respirator systems. 

Table 5 contains examples of materials found in current respirator systems; 

however, the list is not intended to be comprehensive or complete. Manufacturers 

also use other polymeric materials in the construction of respirator systems. 
Procedures and Results 19

Physical state. Thermoplastics, composites, laminates, and other more complex 

materials were considered; however, it was decided to begin with straightforward 

elastomeric materials. 

Specimen geometry. The first phase was limited to elastomers that were available 

in sheet form in quantities required to complete the initial phase and to extend the 

correlations to additional simulants if needed for follow-on work. 

Thickness. The sheets had to be available in a thickness that would provide 

permeation breakthrough times in a reasonable period. At the low end, a 

breakthrough time was desired that was longer than several gas chromatographic 

sampling cycle times in order to provide time resolution. At the longer periods, a 

breakthrough time was desired that did not allow the liquid to totally evaporate or 

did not extend the test cost. 

Thermodynamic, orthogonal material interaction set. A thermodynamic, 

orthogonal polymer interaction set consists of polymers differing in dispersion, 

dipolarity, resonance, hydrogen bond acceptor, and hydrogen bond donor polymer 

properties. The aprotic dipolar organophosphorus and chloroethylsulfide liquids 

should interact uniquely with each polymer to cover the broadest spectrum of 

sorption and permeation levels. The disadvantage is that high levels of sorption 

and fast permeation are likely for several of these structural classes and the data 

obtained would not apply to the chemically resistant polymers of interest to 

respirator manufacturers.

Kinetic orthogonal polymer set. A kinetic orthogonal polymer set consists of 

elastomers with a wide range of diffusion rates for organic liquids. The extremes 

of the elastomer diffusion rate range often cited are poly(dimethylsiloxane) at the 

rapid extreme and poly(isobutylene) at the slower extreme. 

Specimen availability and sources. A rigorous definition of the criteria for 

material selection was important; however, locating actual specimens that fulfilled 

even a small number of desired characteristics is always difficult. Several categories 

of specimen sources were surveyed: a variety of commercial sources, standards 

organizations such as ASTM and NIST, and ECBC’s internal research and 

development or quality assurance/quality control standards.
20 Procedures and Results

Table 5. Commonly used materials in NIOSH-approved respirators

Item number Material

1 Silicone rubber

2 Natural rubber

3 Butyl rubber

4 EPDM

5 Polycarbonate

6 Polyvinyl chloride

7 Neoprene

8 Fluorosilicone

9 Versamid (Nylon)

10 Polystyrene/polyphenylene oxide

11 Nylon 6/6

12 Polyphenyl sulfone

13 Nomex (fire-resistant material)

14 Synthetic rubber

15 Polyester

16 Fiberglass-filled polymer

17 Kevlar

18 Buna-N (Nitrile—sheet rubber gasket material)

19 Thermo plastic elastomer (TPE) 

Based on a conceptual Venn diagram of the elastomer candidates that met the 

criteria in Table 4, specimens were selected from the chemical defense reference 

and control materials that consist of five elastomers and four thermoplastic 

material compositions that had been standardized, procured, and archived for use 

in chemical-material compatibility studies. These chemical defense polymers are 

documented in the following sections. 
Procedures and Results 21

2.2.2 Documentation on the Selected Elastomers

In this section, the elastomers selected are documented from several viewpoints. 

The general compositional classes and several features are surveyed. Several 

thicknesses were available and the selection of one thickness that was used for 

evaluation is described here. 

Composition. The materials that met all selection requirements are from Set 1 

of the Chemical Defense Reference and Control Materials [Shuely 1999] and are 

shown as the first three elastomer compositions in Table 6. These specimens have 

physical and chemical properties that are the most appropriate for this phase of 

the study. The other two elastomer compositions have the potential to be used in 

future studies. In Table 6, the first column lists the chemical defense application 

of the elastomer. The second column lists the base elastomeric composition, 

often termed the gumstock composition. The final column lists the general recipe 

source for the formulation. Since many materials are produced to a performance 

specification, their compositions may vary with manufacturer and with time; 

however, these compositions have been standardized and held constant for this 

set of elastomers. 

Elastomer set features. Cutting multiple specimens from the same molded 

sheet allowed testing at the same cure and crosslink density and, therefore, 

controlled the composition across different tests. Sheet-to-sheet comparisons of 

solubility were measured and the values agreed within experimental error. The 

ASTM Standard Procedure D 3182 had been employed for sample preparation. 

All elastomer compounding and mold curing was carried out by Smithers 

Scientific, Akron, Ohio. The specimens were stored in sealed Mylar bags at 

room temperature until use. Examples of tests that could be performed with Set 

1 include permeation, sorption, and mechanical tests in accordance with the 

following test methods: ASTM F 739, D 471, D 543, D 2240, and D 1415.

Thickness. The nominal thickness ranged from 0.254–6.4 mm (10–250 mils), but 

the actual specimen thickness was measured before each test. The availability of a 

range of thickness values allowed the screening of thickness to obtain reasonable 

breakthrough times, between 0.5 and 24 hours. Sheet thickness was chosen as an 

experimental expedient to produce a completed permeation curve in a reasonable 

timeframe. The thickness selection can partially compensate for differences in 

barrier properties, which would facilitate comparison of permeation curves on 

a linear time scale. Initially, thickness can be selected to be near the end-use 

thickness and can then be decreased to produce breakthrough times within a 

reasonable period.
22 Procedures and Results

Table 6. Elastomeric reference materials based on 

chemical defense respirators

Chemical defense 

applications

Base elastomer 

composition

Source of formulation 

and elastomer 

compounding recipe

M40/42 Mask Faceblank Dimethyl siloxane, GE Mine Safety & Appliance

M40/42 Mask Drink Tube Ethylene propylene Generic Nordel 2744, 

DuPont EPDM

Protective gloves/suits Poly(isobutylene) 

derived from chlorobutyl 

gumstock Polysar Corp.

Generic formulation 

based on Army 

Research Lab prototype 

M43A1 Mask Faceblank Blend of natural and 

bromobutyl rubber 

Natural Rubber: SMR

5–CV60 DuPont

Bromobutyl: Miles Corp.

M17A2/M24/M25A1 

Mask Faceblank

Poly(isoprene), 

natural rubber

SMR–L–0836, DuPont

2.2.3 Documentation of the Elastomer Compositions

The compositions of the elastomers are documented in Tables 7 through 9. 

The rows contain a listing of each component. The second column contains 

the component identification. The third column indicates the function of 

each component. The fourth column contains the class, either estimated to be 

extractable (E) or nonextractable (NE). Only the lower molecular weight (MW), 

non-crosslinked compounds were assigned to the extractable class. The last 

column contains the proportional composition of each component in parts per 

hundred (pph). The convention in elastomer chemistry is to reference all other 

components to 100 pph of the elastomer gumstock. In the last two rows, the Total 

Extractables are summed and the Total Extractable Percent is reported. This is 

the maximum amount that can be extracted during a liquid sorption experiment 

[Shuely and Ince 2001] and provides a check on the experimental correction for 

extractables (see Table 11, column 4). This estimate of potential extractables is an 

important compositional variable since these additives can be extracted during 
Procedures and Results 23

the sorption experiments and confound the determination of sorbent weight gain 

in an elastomer. The sum of the fraction of these potential extractables is noted in 

the tables by adding the fraction of the additives that have the potential to migrate, 

based on the molecular weight and polarity of their structure. The components 

marked as “unknown” are assumed to be nonextractable in the calculations. 

(Note that Smithers, Inc. has modified the Butyl formulation to improve the 

reproducibility of the sheets as permeation standards for quality acceptance 

testing; therefore, the actual composition of current or future Butyl quality 

acceptance standards might be slightly different.) 

Table 7. Poly(dimethylsiloxane) silicone composition based on 

molding formulation 

Number Component Remarks Class*

Parts per 

hundred

1 Dow Corning TR55 Dimethylsiloxane 

Gumstock

NE 60

2 Dow Corning HS30 Dimethylsiloxane 

Gumstock

NE 40

3 HCC 11003 Green Pigment NE 1

4 Varox DBPH–50 Cure NE 1

Total 102

Total potential extractables %: E ~ 0/102 = ~ 0%

*Class: NE – nonextractable, E – extractable, UnK – unknown, assumed nonextractable

Cure, estimated, at 145oC for 0.75 hours; varied for different thickness levels
24 Procedures and Results

Table 8. Poly(ethylenepropylene) (EPDM) composition based on molding formulation 

Number Component Remarks Class*

Parts per 

hundred

1 Nordel 2744 Gumstock NE 100

2 Carbon black FEF Reinforcer NE 110

3 Carbon black MT Reinforcer NE 50

4 Circosol 4240 Hydrocarbon oil E 30

5 Stearic acid Cure activator UnK 1

6 Sulfur Crosslinker NE 2

7 ZnO Crosslinker at C-Cl NE 5

8 Agerite resin D 2,2,4-trimethyl-1,2 

hydroquinoline polymer

UnK 1

9 Captax 2-Mercapto 

benzothiazole

UnK 1.5

10 Tetramethylthiuramdisulfide Cure accelerator UnK 0.8

11 Tellurac 80% UnK 0.8

12 Tetrone A UnK 0.8

Total 302.9

Total potential extractables %: E ~30/302.9 = ~ 9.9%

*Class: NE – nonextractable, E – extractable, UnK – unknown, assumed nonextractable

Cure conditions: not available.
Procedures and Results 25

Table 9. Poly(isobutylene) (Butyl) composition based on molding formulation

Number Component Remarks Class*

Parts per 

hundred

1 Chlorobutyl gumstock NE 100

2 Carbon black N300 Reinforcer NE 60

3 Carbon black N550 Reinforcer NE 15

4 Stearic acid Cure activator Unk 1

5 Sulfur Crosslinker NE 1

6 MgO Crosslinker at C-CI NE 0.5

7 ZnO Crosslinker at C-CI NE 5

8 Altaz, Benzothiazyldisulfide Cure accelerator UnK 2

9 Tetramethylthiuramdisulfide Cure accelerator UnK 1

10 Polyethylene AC617 low MW Mold release E 4

11 Kenaflex A Plasticizer E 5

12 Drakeol 35 mineral oil Plasticizer E 5

13 Paracin #1 Plasticizer E 3

14 American cyanamid antioxidant E 1

Total 203.5

Total potential extractables %: E ~18/203.5 = ~ 8.8%

*Class: NE = nonextractable, E = extractable, Unk = unknown, assumed nonextractable.
26 Procedures and Results

2.2.4 Experimental Design for Elastomer Specimens

The number of permeation disk specimens available for each material is shown in 

Table 10. The large number of replicates, 22, was required to provide a low 95% 

confidence interval for a test with a relatively high variability, as often observed in 

CWA permeation tests. The simulant permeation had less variation (see Table 12) 

and, therefore, required fewer replicates, usually two to three. This specimen 

inventory relative to the experimental design size was necessary since the 

availability of specimens of identical material composition and thickness for all 

tests was a selection criterion. 

Table 10. Experimental design matrix and specimen inventory 

for flooded surface permeation for each material at 

one temperature and thickness

Liquid

Natick simulant 

tests inventory

Natick simulant 

tests replicates

Inventory 

and replicates, 

ECBC CWA tests

G simulant 1:

DEMP 6 2–3 0

G simulant 2:

DIMP 6 2–3 0

H simulant 1:

CEPS 6 2–3 0

H simulant 2:

DCH 6 2–3 0

GB 0 0 22

HD 0 0 22

Other candidate 

simulants

6 1–2 0
Procedures and Results 27

2.3 Immersion Methods for Determination 

of Solubility and Diffusion Coefficients

CWA solubility in the elastomer compounds was determined at 35°C by the ASTM 

D 471 method, modified for use with toxic chemicals [Shuely and Ince 2001]. A 

correction for extraction of components from the elastomer compound into the 

liquid was performed by desorbing the post-immersion specimens to a constant 

weight using mild vacuum at up to 110°C.

Simulant solubility was determined by the same general method used for CWAs. 

Diffusion rates were obtained for pre-dried elastomer compounds immersed in 

excess liquid simulant at 35°C ± 0.1°C by removing and weighing (surface dry) 

the swollen specimens at timed intervals until steady state was achieved. Simulant 

solubility was taken as the weight gain at steady state, corrected for extractables, 

and was reported in units of g/cm3.

2.4 Permeation Methodology

The procedure employed for testing liquid CWAs and simulants with Silicone, 

Butyl, Nitrile and EPDM rubber is described in Appendix A. The standard test 

method, in Appendix A, that was developed during this investigation, can be used 

to perform permeation resistance testing with any nonreactive liquid, including 

TIC, in which the polymer does not decompose, react, or dissolve. When using 

the data interpretation techniques and the permeation data provided in this 

document, it is required that the test method described in Appendix A is used in 

order to obtain meaningful test results. 

2.4.1 Equipment in Research and Development Studies and 

Standardized Method

There is a need to distinguish between the documentation of the specific 

equipment employed in this investigation and the generic equipment cited in 

the test method in Appendix A. This section documents the apparatus used in 

testing and provides an example of typical lab apparatus that are adequate for the 

measurements; any equipment with equivalent specifications can be substituted. 

The minimum specifications for the permeation system components are detailed 

in Appendix A.

2.4.2 General Equipment

Digital micrometer thickness gauge:

A digital micrometer thickness gauge (Mitutoyo, Inc. Model 293) that complied 

with Federal Specification GGG-C105C was used to obtain specimen thickness. A 

die set with approximately 3.8 cm diameter punch was employed to cut specimens 

from molded sheets. Other instrumentation and equipment are listed as part of the 

test method in Appendix A.
28 Procedures and Results

Permeation cell designs:

Several permeation cell designs were candidates for use in this study including 

the one- and two- inch ASTM F 739 cells, the U.S. Army Test and Evaluation 

Command (TECOM) Test Operation Procedure (TOP) 8–2–501 cell, the NSC 

Liquid Permeation Cell, and ECBC Quality Assurance permeation cell. The NSC 

Liquid Permeation Cell design was selected based on design simplicity, ease of 

sealing, minimization of permeant volume for a flooded surface geometry, and 

acceptance of hard and soft specimens up to 0.7 cm thick.

A photo of the liquid permeation cell (RDECOM, NSC design) is shown in 

Figure 1. (See the Liquid Permeation Cell Mechanical Drawings in Appendix B 

for design details). 

Figure 1. Liquid Permeation Cell

(Photo provided by Natick Soldier Center)

2.4.3 Edgewood Chemical Biological Center (ECBC) 

Permeation Equipment

The detection system used at ECBC is a MINIature Continuous Air Monitoring 

System (MINICAMS: OI Analytical), photo not included. The permeation 

equipment used at ECBC includes: a gas chromatograph equipped with a 

hydrogen flame emission detector and a pre-concentrator tube used for GB and 

HD detection. The detection system includes an internal data acquisition board 

and data acquisition system.
Procedures and Results 29

2.4.4 Natick Soldier Center (NSC) Permeation Equipment

This section describes all control and detection components used for permeation 

testing at NSC.

Flame ionization detector (FID) in a Gas Chromatograph (GC) system:

SRI, Model 110; used for simulant detection at NSC (Figure 2). 

Figure 2. Flame ionization detector, SRI, Model 110 (Photo courtesy of SRI).

 Data acquisition board—A/D converter:

Omega, PCI-DAS, 1001—a component of the simulant detection system 

at NSC (photo not provided).

Medium speed, PCI bus, 12 bit, analog input, digital IO

50-pin screw terminal board (Omega, CIO–MINI50)

100-pin ribbon cable (Omega, C100FF–2), 2’ length

 Personal computer—Dell, Optiplex model:

Integral to the simulant detection system at NSC (photo not provided).

Computer operating system: Microsoft Corporation, Windows 2000, integral 

to the simulant detection system at NSC;

Peripheral component interconnect (PCI) slot;

Portable high capacity storage medium with a minimum of 100 megabytes;

2.0 GHz with 400 MHz front-side bus.
30 Procedures and Results

Data acquisition software—National Instruments Corp., Omega, DASYLab 

Lite: A component of the simulant detection system at NSC (photo not provided).

Mass flow controller—MKS flow controller, Type 1179A:

General purpose mass flow controller; 1⁄4 inch tube Swagelok connections (photo 

not provided).

Air heater controller—WPI, Model Air ThermTM:

Used with the simulants at NSC (see Figure 3): 

Air or high heat capacity dry (unnecessary if ambient temperature can be 

maintained at 35oC ± 2oC).

Figure 3. Air heater controller, WPI, Model Air-ThermTM (Photo courtesy 

of WPI). 

Test liquid:

Test liquid (simulant chemical)—approximately 0.3 mL per test cell

Temperature control chamber:

Fabricated at RDECOM, NSC, no specific design requirements (Figure 4)

n Houses Liquid Permeation Cell

n Interfaces with the air heater controller to maintain constant temperature

n Contains ports for flame ionization detector sampling lines 

Carrier Gas:

Permeation tests were performed with dry nitrogen (UN 1977) from a 

compressed or liquefied source or dry air (UN 1002) containing < 10 parts per 

million (ppm) water.
Procedures and Results 31

2.4.5 Permeation Conditions

Temperature. Tests were performed at 35°C ± 0.1°C which is slightly below body 

temperature and near skin temperature. Higher or lower temperatures can be 

employed in order to control the duration of the test, however, it is usually difficult 

to accurately control temperature near ambient. 

Preconditioning Specimens. Specimens are often conditioned for hours to days 

before testing at a specified temperature and humidity; this is often critical for 

hydrophilic barrier materials. For the hydrophobic elastomers studied here, only 

temperature conditioning of less than 1 hour was required to raise the specimen 

temperature to the cell test temperature. 

Thickness. Thickness measurements were performed at four widely spaced sites 

within the middle 3 cm diameter circular area of the permeation specimens. 

Variations in thickness are quite small and the average value is reported. 

Flow Rate. The carrier (sweep) gas flow rate was 130 cm3

/min for GB, 

200 cm3/min for HD, and 33 cm3/min for the simulants. The flow rates were 

selected to optimize vapor concentration without incurring significant mass 

transfer limitations. Effluent vapor concentration was determined using a flame 

ionization detector (FID) for simulants and a MINICAMSTM-FID for CWAs. 

Repetitions. The number of replicates for simulants ranged from 2–3 for simulants 

and 22 for CWAs (see Table 10). Several test data sets for CWAs were discarded 

due to anomalous results or equipment failures.

Figure 4. Temperature control chamber, RDECOM, Natick Soldier 

Center (Photo provided by Natick Soldier Center)
32 Procedures and Results

2.5 Data Analysis of Solubility and Diffusion Properties

A brief explanation is provided here on the role of solubility and diffusion 

in permeation through a barrier material in order to provide the necessary 

background for the data reduction procedures employed.

For simple sorption (in the absence of relaxation and irreversible processes), 

the immersion of an elastomer specimen in the test liquid produces a diffusion 

flux that can be described by a unique diffusion coefficient or diffusivity (Di) at 

constant temperature. This diffusion process is described by Fick’s second law 

(equation 1) for diffusion at concentration c in the x dimension as a function 

of time.

δc/δt = Di δc2/δx2 (1)

Fick’s second law is plotted as fractional weight gain (FWG) versus square root of 

time (t1⁄2). FWG is defined as the incremental sorption at time (t) divided by the 

plateau value representing the final steady-state weight increase. This plateau value 

representing the final steady state weight increase also defines the equilibrium 

solubility (S) for the liquid in the elastomer specimen with a specific cross-link 

density, filler content, and other characteristic properties. In Table 11, S is reported 

in units of g/cm3 from a plot of absolute weight gain vs. square root of time, and 

diffusivity as cm2/s. A representative Fick’s law plot of fractional weight gain versus 

square root of time is shown in Figure 5 for dichlorohexane in Silicone.

Figure 5. Fractional weight gain (FWG). FWG by immersion versus square root of time 

(t1⁄2) for Silicone (0.323 cm thick) in dichlorohexane at 35oC ± 0.1oC. Points are 

experimental, line is Fickian curve when Di = 2.80E–06 cm2/s. [Rivin et al. 2005]

1.00

0.80

0.60

0.40

0.20

0.00

0 50 100 150 200 250 300

Square Root of Time (t1⁄2)

FWG
Procedures and Results 33

For some of the liquids with low solubility or high extraction in the polymer under 

investigation, the diffusivity cannot be readily determined under kinetic diffusion 

conditions due to the low solubility value with respect to the confidence interval of 

the measurement; that is, the small, absolute value of the weight gain is within the 

uncertainty of the measurement. In these cases, solubility values can be obtained 

using the steady state method for directly determining equilibrium solubility at 

long sorption time, as noted in the Experimental Section of a previous publication 

[Rivin et al. 2005]. This was the case for some phosphonate liquids sorbed into 

Butyl or EPDM (see Table 11. DMMP in Butyl).

In determining Di, it is assumed that specimen thickness is very small compared 

to face dimensions; this “edge effect” has been discussed in a previous publication 

[Barrer et al. 1962]. Note that this applies to diffusion coefficient determinations 

from sorption and not permeation experiments.

2.6 Immersion Results

Immersion results are presented in Table 11. The first column contains the 

polymer composition and the thickness for each specimen. Several different 

thickness levels were employed; equilibrium solubility does not depend on 

thickness; however, internal checks on the thickness effect on the diffusion 

coefficient were applied. The test liquid is listed in the second column. The 

weight gain in weight percent is listed under the “WG” heading in Column 3. The 

weight percent of extracted components is reported in the fourth column, and 

for polymer-liquid pairs showing a value under “Extract,” the solubility value in 

Column 5 has been corrected by addition of the measured extracted components 

to the raw weight gain data. All measured extract values are less than or equal to 

the maximum potential extractables that were calculated from the formulation 

content as a check on the measurement. In the fifth column, the weight gain, 

extractable correction, polymer density, and volume of the specimen are employed 

to calculate the solubility (S) in grams per cubic centimeter. The immersion 

diffusion coefficients, in cm2/sec, obtained from a plot of fractional weight gain 

verses square root of time, are listed in the last column. Note that GB and HD were 

not tested with Nitrile rubber. Sorption versus time are listed in the last column. 

Sorption versus time measurement of immersion diffusion coefficients was not 

included in the experimental design for GB and HD.

Due to solvent-solute parameter interaction differences, the relative solubility of the 

simulants and agents differed between polymers. In many cases, the solubility of 

the simulants was greater than that of the agent; therefore, the simulants were safesided with respect to the solubility-screening component in protective permeation 

performance. An exception was the Butyl and EPDM elastomers in which at least 

one of the two alkyl phosphonate solubility values is comparable to the GB value.
34 Procedures and Results

Table 11. Solubility and diffusivity from immersion at 35oC

Polymer and 

thickness (cm§) Liquid

WG

(wt%)

Extract*

(wt%)

S†

g/cm3

Di

10-7 cm2/s

Silicone:

0.074 HD 5.2 0.8 0.06 ND‡

0.074 GB 5.9 degraded 0.06 ND

0.318 DCH 21.6 ND 0.24 28.0

0.203 DCH 21.7 ND 0.24 21.0

0.318 CEPS 8.2 ND 0.09 30.0

0.318 DIMP 7.5 ND 0.08 23.0

0.318 DEMP 31.8 ND 0.35 10.0

Butyl:

0.030 HD 24.6 8.6 0.27 ND

0.030 GB 11.4 4.2 0.13 ND

0.030 DCH 44.6 ND 0.49 2.40

0.051 DCH 45.6 ND 0.50 2.40

0.030 CEPS 29.4 9.4 0.32 1.20

0.051 CEPS 29.4 9.4 0.32 1.20

0.030 DEEP 11.8 ND 0.13 ND††

0.030 DIMP 22.6 6.9 0.25 0.30

0.051 DIMP 22.6 6.9 0.25 0.30

0.030 DMMP 1.42 ND 0.16 ND††

0.030 DEMP 9.9 4.1 0.11 0.50

(continued)
Procedures and Results 35

Table 11 (continued). Solubility and diffusivity from immersion at 35oC

Polymer and 

thickness (cm§) Liquid

WG

(wt%)

Extract*

(wt%)

S†

g/cm3

Di

10-7 cm2/s

EPDM:

0.043 HD 9.0 2.4 0.10 ND

0.043 GB 2.5 0 0.03 ND

0.074 DCH 15.9 ND 0.18 3.30

0.048 DCH 13.4 ND 0.15 2.20

0.074 CEPS 10.0 2.2 0.11 2.95

0.048 CEPS 13.7 3.9 0.15 ND

0.048 DEEP 4.16 5.9 0.05 ND

0.048 DIMP 4.71 8.61 0.05 ND

0.048 DMMP 1.36 1.2 0.02 ND

0.048 DEMP 2.7 1.25 0.03 ND

Nitrile:

0.0279 DCP** 115.8 ND 1.27 2.20

0.0279 CEPS 130.9 ND 1.44 1.10

0.0279 DIMP 26.8 ND 0.30 0.50

0.0279 DEMP 50.2 ND 0.55 0.65

*Steady-state method. Corrected value within ±10% of kinetic method.

†Density of elastomer compounds taken as 1.1 g/cm3

 in order to convert from weight percent.

‡ND=not determined.

§Average thickness for individual specimens range from ± 0.005 cm for butyl and 

silicone to ± 0.003 for other polymers.

**Immersion data for dichloropentane.

††Low value with high standard deviation.
36 Procedures and Results

2.7 Permeation Results

In this section, the parameters that characterize a permeation curve are defined 

graphically and the equations that support the data analysis are described. Also 

presented in this section are the breakthrough time and permeability parameters, 

that were normalized for thickness (see section 2.7.3). Finally, several permeation 

parameters are presented as ratios, relative to reference values, so that the relative 

effects can be discerned. 

2.7.1 Characteristic Parameters of the Permeation Curve

Permeation of a liquid through a polymer membrane is dependent on the 

solubility and molecular diffusion coefficient of the test material in the polymer 

matrix. Parameters that characterize this process are shown on the representative 

permeation curve in Figure 6. Early time behavior is best described by the 

breakthrough time (Tb

) which is the intercept, extrapolated back to the baseline, 

of the initial linear rise of the permeation curve. The use of Tb is preferred to 

the time of first detection of test vapor because the latter is extremely 

instrument dependent.

Figure 6. Permeation curve with characteristic parameters [Rivin et al. 2005]

As permeation through the membrane continues, permeation rates are related 

to T1⁄2, the time at which permeation is half the steady-state value. Maximum 

permeation is given by the asymptotic steady-state permeation. The time at 

inception of steady state permeation (Ts

) is a measure of the minimum duration of 

a complete experiment but has no theoretical utility.
Procedures and Results 37

2.7.2 Data Analysis of Permeation Parameters

The permeability coefficient (P) at steady state [Wijmans and Baker 1995] is the 

product of a diffusion coefficient (Dp), solubility (S) and reciprocal thickness (L-1): 

P = D

p

 S L-1 (2)

D

p

 is primarily a function of the size and concentration of diffusing molecules in 

a specific polymer specimen; S is a function of the specific chemical interaction 

between these dissolved molecules and the polymer matrix, and is measured 

from the sorption isotherm. P is defined as the steady-state permeation flux for 

a 1 cm thick membrane over a 1 cm2 area. Therefore, if two liquids have identical 

solubility in a polymer compound, their permeability coefficient will be inversely 

proportional to their molecular cross-section or volume. However, to account for 

major polymer-solvent interaction effects, the solubility of a selected simulant 

should be similar to that of the CWA in the protective material under study. Based 

on this criterion, solubility and permeation experiments were performed with four 

simulants (DCH, CEPS, DIMP and DEMP) and two CWAs (GB and HD). 

Tb and T1⁄2 are fundamental values related to D at very low and intermediate 

dissolved concentrations, respectively. These D values differ if D exhibits nonlinear 

concentration dependence and are often different from Dp , calculated from the 

steady-state permeation flux (equation 2). There is a good correlation between Tb 

and T1⁄2 for each polymer-solvent pair [Rivin et al. 2005] but an exact solution of 

the permeation differential equation is obtained only for T1⁄2 [Crank and Park 1981 

and Meares 1965]. Equation 3 allows calculation of D in cm2/s from T1⁄2 in seconds, 

and L in cm. 

D1⁄2 = 0.139 (L2) / T1⁄2 (3)

Note: When D appears without subscripts, it refers to a generic diffusion 

coefficient with a magnitude dependent on the degree of swelling of the polymer. 

When subscripts are included, they refer to the method of determining D under 

different conditions and at different stages of the permeation process, each 

associated with a particular degree of swelling.

2.7.3 Normalized Permeation Parameters for 

Comparisons Independent of Thickness

Rationale and Definition. Normalized permeation parameters can be used to 

compare the permeation behavior of different materials independent of specimen 

thickness. Both Tb and T1⁄2 are kinetic permeation parameters, independent of 

thermodynamic solubility (S), and related to a diffusion coefficient (D) and 

the square of the thickness (L). The limiting permeation is a thermodynamic 

parameter equal to the product of D, S, and thickness. Therefore, the normalized 

parameters, Tb/L2, T1⁄2/L2 and P (permeability coefficient, permeation per cm 

thickness), can be used to compare the permeation behavior of different materials 
38 Procedures and Results

independent of specimen thickness. Normalization in the present context 

refers to dividing characteristic times by thickness squared in order to make 

comparisons at an identical unit thickness. As defined, P contains an inherent 

thickness correction. These normalized parameters should aid protective materials 

developers for CWAs in comparing results when materials of different thickness 

are employed for testing. 

Thickness Normalization of Breakthrough Time. To evaluate a different 

elastomer with the same set of simulants, it is necessary to determine whether 

the values of Tb/L2 and T1⁄2/L2 are equal to or larger than that of the CWAs or 

reference simulants in resistant materials such as Butyl and EPDM. If the new 

materials are similar to Butyl or EPDM, that indicates that the polymer is a 

candidate agent-resistant material. Most nonpolar and low polarity, nonhydrogen 

bonding polymers should fall between silicone, near the nonresistant extreme, 

and Butyl and EPDM near the resistant extreme. Next, the relative ratios of the 

four simulants should be examined to determine if similar rankings and ratios 

were observed, relative to the three polymers in Table 12 for which HD and GB 

results are available. These rankings are DCH< CEPS<<DIMP ~DEMP. If these 

relative ratios are repeated for the four simulants, there is a high probability that 

the relative rankings of the agents would be maintained for the new polymer. If, 

however, it is desired to determine if the barrier material at a specific thickness 

achieves a specified level of protection, the permeation curve should be applied 

without normalization in conjunction with either a predetermined Tb or a 

minimum permeation effluent concentration.

Thickness Normalized Permeability. Barrier performance increases with smaller 

values of P, the opposite of the Tb/L2 and T1⁄2/L2 values. Thus, P for a different 

elastomer can be compared directly with the values in the permeation column 

of Table 12. 

Overall, these normalized parameters provide several useful ratios of the 

experimental results that can be used to relate simulant to CWA behavior. 

Additional ratios of experimental measurements to expand the comparison of 

simulant to CWA are provided in the following sections.

2.7.4 Permeation Parameter Ratios 

Relative to DCH and DCH-Butyl Rubber

Rationale for Parameter Ratios. In order to rank the protective performance 

of the set of polymers against CWA and simulant, further data reduction is 

required in order to set one of the liquids and one of the polymers as a baseline 

for comparisons. Three ratios were calculated to highlight three effects: (1) a 

liquid effect, (2) a polymer effect, and (3) a combined polymer-liquid effect. As a 

reference liquid, it was most useful to select DCH because of its high permeation 

rate. An overall liquid effect could then be calculated to allow a ranking of the 
Procedures and Results 39

liquids for each polymer. One of the more permeation-resistant polymers, butyl, 

was selected as a reference polymer. An overall polymer effect could then be 

calculated and a polymer ranking identified. A combined overall baseline was then 

produced from the combined permeation parameters of DCH with butyl rubber; 

this is a combined polymer-liquid effect.

Ratio Results. The thickness normalized kinetic and thermodynamic parameters 

are summarized in Table 12 for GB, HD, and four liquid simulants in Silicone, 

Butyl, EPDM and Nitrile rubber compounds. Standard deviations for the three 

characteristic parameters (Tb/L2, T1⁄2/L2 and P) are shown in Table 12 for both 

CWAs, but are given only for simulant permeability due to limited replication 

(duplicate tests). In general, simulant results exhibited significantly less scatter 

than the corresponding data for the CWA (Appendix C). 

Breakthrough Time Ratios. Similar trends in Tb/L2 and T1⁄2/L2 are observed 

with all liquids, as represented for each parameter by the selectivity ratios 

RDP (relative to dichlorohexane with respect to the specific polymer) and 

RDB (relative to dichlorohexane with respect to Butyl). The coding employed 

defines R as the ratio, with the following subscripts: D for DCH, P for polymer, 

and B for Butyl. Thus, for example, the RDP (Column 3 in Table 12) is the ratio 

of [Tb/L2] (Challenge Chemical) divided by [Tb/L2](DCH) within the same polymer. The RDP

selectivity ratio provides a convenient “fingerprint” of the relative resistance of 

each polymer to CWAs and simulants, as shown in Figure 7. Bar graphs for HD 

and GB are not shown for Nitrile because CWA permeation was not determined 

for this polymer, however, as seen in Table 12, the simulant Tb profile for Nitrile is 

similar to that for EPDM. 

Permeability Ratios. To provide a comparison of the polymer effect, the RDB

selectivity ratio was calculated by dividing the permeation parameters by the value 

for DCH in Butyl for all polymers:

(Tb/L2 = 22,000 min/cm2).

Thus, RDB = [Tb/L2

]/ [Tb/L2] (DCH in Butyl) 

This allows a direct comparison of relative permeation across all polymer-liquid 

combinations. The remaining ratios (RDP and RDB) for T1⁄2 and P in Table 12 were 

derived using the same method as described for the Tb ratios of RDP and RDB. 

Rankings. Regarding the relative kinetic parameters, RDB shows a large decrease 

in barrier performance with all liquids in the order: Butyl > EPDM ~ Nitrile >> 

Silicone. There are smaller differences between the liquid permeants as shown 

by the maximum range in RDP, which varies from 2.9 for Silicone to 6 for Butyl, 

with EPDM and Nitrile having ratios near 4. Although, the permeation profile is 

different for each polymer, permeation parameters of simulants usually bracket the 

values for CWAs. 
40 Procedures and Results

The permeability coefficient provides a similar relationship between the polymers Butyl, 

EPDM, and Nitrile. The values in Table 12 are plotted in Figure 8a and 8b. Figure 8b plots 

the same data without Silicone, so that the y-axis scale can show the relative rankings for 

the other polymers. As shown in Figure 8, each polymer compound also has a unique 

permeation profile that differssignificantly from those obtained with kinetic parameters 

due to the effect of solubility.
Procedures and Results 41

Table 12. Mean permeation parameters compensated for specimen thickness 

P

ng • cm

cm2 • min

Tb/L2

103 min/cm2

T1⁄2/L2

103 min/cm2

Polymer:

liquid (replicates) RDP* RDB

† RDP RDB RDP RDB

Silicone:

HD(22) 0.62 (12)‡ 1.2 0.03 1.7 (6.7) 0.8 0.06 93.5 (14) 0.8 8.4

GB(22) 0.73 (11) 1.4 0.03 1.3 (3.4) 0.6 0.05 125 (20) 1.0 11.2

DCH(3) 0.51 1.0 0.02 2.2 1.0 0.08 120 (2.7) 1.0 10.7

CEPS(2) 0.93 1.8 0.04 3.6 1.6 0.13 76 (1.1) 0.6 0.8

DIMP(2) 1.5 2.9 0.07 3.7 1.7 0.13 115 (5.3) 1.0 10.3

DEMP(2) 1.4 2.7 0.06 2.8 1.3 0.10 93.5 (0.77) 0.8 8.4

Butyl:

HD(21) 33 (31) 1.5 1.5 81 (11) 2.9 2.9 7.3 (22) 0.7 0.7

GB(22) 60 (36) 2.7 2.8 175 (24) 6.3 6.3 1.3 (24) 0.1 0.1

DCH(2) 22 1.0 1.0 28 1.0 1.0 11.2 1.0 1.0

CEPS(3) 40 1.8 1.9 65 2.3 2.3 8.3 (16) 0.7 0.7

DIMP(2) 133 6.0 6.0 222 7.9 7.9 2.5 (7.2) 0.2 0.2

DEMP(2) 130 5.9 5.9 226 8.1 8.1 0.87 (26) 0.08 0.08

EPDM:

HD(22) 7.6 (24) 0.8 0.3 28 (6.2) 1.4 1.0 9.4 (14) 0.5 0.8

GB(17) 10 (36) 1.0 0.5 29 (42) 1.5 1.0 2.0 (15) 0.1 0.2

DCH(3) 10 1.0 0.5 20 1.0 0.7 18.4 (4.0) 1.0 1.6

CEPS(3) 15 1.5 0.7 31 1.6 1.1 16.9 (0) 0.9 1.5

DIMP(2) 35 3.5 1.6 88 4.4 3.1 2.51 (3.1) 0.1 0.2

DEMP(2) 39 3.9 1.8 84 4.2 3.0 1.24 (10) 0.1 0.1

Nitrile:

DCH(1) 8.2 1.0 0.4 14 1.0 0.5 10.9 1.0 1.0

CEPS(1) 12 1.5 0.6 31 2.2 1.1 5.9 0.5 0.5

DIMP(1) 28 3.4 1.3 40 2.9 1.4 18.4 0.2 1.6

DEMP(2) 31 3.8 1.4 50 3.6 1.8 18.4 (20) 0.2 1.6

*Relative to DCH for the same polymer.

†Relative to DCH for butyl.

‡Numbers in parenthese = % standard deviation.
42 Procedures and Results

Figure 7. Normalized breakthrough time relative to DCH value for the same elastomer 

compound

Figure 8a. Average permeability coefficient from the mean of the replicates of the 

four polymers

RDB (Tb)
Procedures and Results 43

Figure 8b. Average permeability coefficient from the mean of replicates of Butyl, EPDM, 

and Nitrile (without silicone to show detailed rankings of the other polymers).
Discussion

3.0
Discussion 47

3.0 Discussion

This discussion provides several approaches that can be applied by PPE 

manufacturers to screen and deselect candidate materials based on solubility 

and permeation with the simulants. These include: interpreting test results to 

make safe-sided selections of candidate materials, employing only solubility 

as a safe-sided screen, using the relative rankings and/or absolute values of 

permeation parameters, and finally, using direct graphical comparison of 

permeation curves as a tool for material evaluation. 

In general, the respective simulant solubility values in Table 11 (solubility 

and diffusivity values) are higher or equivalent to those for GB and HD. The 

thickness normalized permeation parameters of the two simulants bracket 

those of HD for all three polymers and GB for two of three polymers, except 

for Silicone. Based on these results and the absolute permeation curves, the 

data interpretation techniques described below can be employed to select 

candidate GB and HD resistant materials based on simulant testing. Although 

protective clothing developers can apply their own data interpretation 

strategies to the CWA-simulant data sets provided, the discussion that follows 

should provide a useful starting point for selecting candidate protective 

materials for further testing.

3.1 Safe-Sided Simulants and Tests 

Safe-sided simulants can be defined as simulants that bias the selection 

of candidate protective materials toward those with a high probability of 

providing equal or better protective performance against CWAs. The simulants 

selected from this study should provide a safe-sided screening tool for 

nonpolar protective polymers. The simulant solubility values and permeation 

results are generally higher than the CWA values. The flooded-cell permeation 

test is safe-sided relative to droplet permeation geometry. The disadvantage 

of safe-sided simulants is that potentially acceptable materials will rank low 

on a list of candidate materials for further testing. These materials might have 

a lower cost, have a greater durability, or have superior mechanical, thermal, 

optical or face-sealing properties. However, each PPE developer can apply 

their own judgment regarding an optimal testing strategy to screen candidate 

materials for CWA testing. Obviously, any highly soluble, rapidly diffusing 

liquid would not provide a useful safe-sided simulant. The best safe-sided 

simulants will have similar but slightly higher values of permeation when 

compared to the CWAs. 
48 Discussion

3.2 Solubility Test as a One-Sided Candidate Material 

Screen 

A material selection strategy can employ only the CWA and simulant solubility 

results to screen materials. For most chemical-material series, the simulants 

had greater or similar equilibrium solubility, after correction for extractables. 

Therefore, a new candidate elastomer tested with the simulants that results in 

equivalent or lower solubility values might be a good candidate protective material. 

However, when results of solubility are compared to permeation using GB and 

HD on silicone, the solubility values are quite low, 5%–6%, yet the permeation was 

extremely rapid due to the higher diffusion coefficient component in the silicone 

permeation. Therefore, the equilibrium solubility screen can only be used as a onesided test to eliminate materials with high solubility, but cannot be used to select 

candidate protective materials without a follow-on permeation or diffusion test.

3.3 Relative Criteria for Selecting Candidate Materials 

Based on Permeation Correlations 

Another possible evaluation method consists of comparing the relative values of 

a new PPE candidate material with those reported in Table 12. After performing 

the permeation experiments with the new material and simulants DEMP, DIMP, 

CEPS, and DCH, one would perform the data reduction to the variables listed 

in the column heading of Table 12 and produce an equivalent table for the new 

candidate material. For Tb/L2 and T1/2/L2,the higher the value, the longer the 

breakthrough time, and the slower the permeation. One would then determine if 

these favorable, high values were obtained for the new polymer by comparing with 

the simulant values in the table, relative to the CWA values. If the reduced data for 

the four simulants has a similar quantitative relationship to that shown in Table 12, 

then one can assume that the correlation with the agent permeation would be valid 

for the tested material; therefore, the material could remain a candidate for testing 

with the CWA. If the relative values are quite different and significantly lower than 

those in Table 12, then it is likely that the material is not a satisfactory barrier 

material to agent permeation.

3.4 Absolute Criteria for Selecting Candidate Materials 

Based on Permeation Correlations 

For GB and HD with the materials studied here, Butyl and EPDM provide an 

estimate of an upper level for elastomer permeation performance as demonstrated 

by relatively long breakthrough times and low permeation. Silicone permeation 

performance is poor because of the short breakthrough times and high 

permeation. After the relative correlation process above has been completed, 

one can go to the next step of evaluating the absolute permeation performance 

by comparing the values of the new candidate PPE polymer being tested by the 

manufacturer with the values in Table 12 for reduced times and permeation. 
Discussion 49

If values for the new polymer are comparable to or better than the values for 

Butyl and EPDM, this would indicate that the polymer is a good candidate. If 

the absolute breakthrough values for the new material approach the values for 

silicone, the polymer would be a poor candidate for further testing. Obviously, 

this assignment as a poor candidate would apply even if the new material met 

the relative criterion of having breakthrough parameters similar to those of DCH 

and less than those of CEPS, DIMP, and DEMP because the absolute permeation 

resistance was so poor.

3.5 Permeation Curve Comparisons

Another approach using simulants to assess whether a particular item or barrier 

material provides adequate protection against CWAs or other toxic chemicals is 

to compare the material’s permeation curve to that of a reference material under 

the same exposure conditions. For example, side-by-side comparison of the 

permeation flux curves (rather than thickness corrected permeability) obtained 

for HD, GB, and two simulants in 0.03 cm Butyl membranes (Figure 9) clearly 

shows the close correspondence between CEPS and GB, and the bracketing of 

HD between DCH and CEPS in this polymer. Flooded-surface permeation of HD 

Figure 9. Permeation rate of CWAs and simulants in 12-mil Butyl rubber 

In this figure, the permeation rate is the permeation flux at each of the times 

(expressed in minutes); whereas, the permeability coefficient is the steadystate permeation flux divided by the thickness.
50 Discussion

exceeds that of GB in good barrier membranes so that comparing permeation of 

DCH and CEPS in a new candidate material specimen to a Butyl reference curve 

affords a rapid estimate of the relative barrier performance of the test material. The 

available data is not sufficient to derive a quantitative correlation for all polymer 

compounds but it strongly supports the concept of this comparative method.

3.6 Infinite Versus Finite Source Permeation Geometry 

The infinite source (flooded surface) diffusion and permeation coefficients 

determined in this report provide a more systematic characterization for GB, 

HD, and related liquids with important barrier elastomers than the finite source 

droplet test geometries. The most common, current CWA permeation test method 

employs a liquid droplet challenge rather than a completely covered surface 

(i.e., flooded surface). Infinite source permeation represents an upper limit for 

each permeant-elastomer pair relative to the droplet tests. This is due to the 

following limitations in the latter: depletion of the drop mass via concurrent 

evaporation, lateral spreading toward adjacent unwetted areas, and insufficient 

applied liquid to attain the maximum concentration gradient in the membrane. 

Finite source droplet geometry is useful for determining the extent to which weartime can be extended by evaporative loss of the permeant. However, the infinite 

source experiment is required to characterize the polymer-liquid interaction with 

respect to solubility, diffusion, and the permeability coefficient, especially for 

structure-property relationships.
Summary

4.0
Summary 53

4.0 Summary

A new test cell with associated control and analytical components has been 

developed to facilitate flooded surface permeation testing of barrier materials. 

Flat sheet specimens (< 0.7 cm thick) of any hardness are evaluated under flooded 

surface conditions using toxic or nontoxic liquids to provide a rapid assessment 

of barrier effectiveness. The permeation of CWAs and other toxic liquids can be 

estimated using a less toxic test liquid by comparison to a reference material, either 

by a direct match of the permeation curve or by calculation of normalized kinetic 

and thermodynamic parameters. 
References
References 57

References

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mixed boundary conditions. Trans Faraday Soc 58:2473–2483.

Barton AFM [1983]. CRC handbook of solubility parameters and other cohesion 

parameters. 2nd ed. Boca Raton, FL: CRC Press, pp. 139–190.

Crank J, Park GS [1981]. Methods of measurement in J. Crank and G.S. Park 

(eds.), Diffusion in polymers. New York: Academic Press, pp. 1–39.

Meares P [1965]. Transient permeation of organic vapors through polymer 

membranes. J Appl Polymer Sci 9:917–932.

NIOSH [2001]. Chemical, biological, radiological, and nuclear (CBRN) standard 

for self-contained breathing apparatus statement of standard and supporting 

rationale. Pittsburgh, PA: U.S. Department of Health and Human Services, Centers 

for Disease Control and Prevention, National Institute for Occupational Safety 

and Health, National Personal Protective Technology Laboratory; Section 6; 

December 2001. 

NFPA [1994]. National fire protection association draft standard on protective 

ensembles for chemical/biological terrorism incidents, November 2000, Report 

of Proposal.

Rivin D, Lindsay RS, Shuely WJ, Rodriguez A [2005]. Liquid permeation through 

nonporous barrier materials. J Membr Sci 246:39–47.

Shuely WJ [1999]. Test methods and reference materials for selection of chemically 

resistant materials. Proc. 10th Annual Ground Systems Survivability Symposium, 

NDIA Conf., April 1999.

Shuely WJ, Ince BS [2001]. Evaluation of systematic and random error in the 

measurement of equilibrium solubility and diffusion coefficient for liquids in 

polymers. ECBC-TR-090 November 2001. Approved for public release.

U.S. Army Center for Health Promotion and Preventive Medicine 

(USACHPPM) [2000], Tech Guide 244, The Medical NBC Battlebook, May 2000.

Wijmans JG, Baker RW [1995]. The solution-diffusion model. 

J Membr Sci 107:1–21.
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Phase Diagrams to Chemical Defense, 

Unlimited Distribution Publications

Ince, Brian S., and Shuely, Wendel J., Comparison of Rheological Properties: 

Bis (2 chloroethyl) Sulfide Vs Model Liquids; in Material Interactions with Agents 

and Simulants, CRDEC SP 011, Proceedings of the Third International Simulant 

Workshop, CRDEC, 7–9 March 1989, Compiled by White, W.E., Ph.D., November 

1989, UNCLASSIFIED Report.

Ince, Brian S., and Shuely, Wendel J., Solubility, Sorption and Desorption in a 

Set of Standard Elastomers; in Material Interactions with Agents and Simulants, 

CRDEC SP 011, Proceedings of the Third International Simulant Workshop, 

CRDEC, 7–9 March 1989, Compiled by White, W.E., Ph.D., November 1989, 

UNCLASSIFIED Report.

Ince, Brian S., and Shuely, Wendel J., Comparison of Agent and Simulant 

Measurements of Equilibrium Solubility and Diffusion Coefficient; in Materials 

Research Contributions to the Evaluation of Test Liquids, CRDEC SP 025, 

Proceedings of the Fourth International Simulant Workshop, CRDEC, 6–8 March 

1990, Compiled by Famini, George R., July 1990, UNCLASSIFIED Report.

Ince, Brian S., and Shuely, Wendel J., Comparison of Equilibrium Sorption and 

Diffusion Coefficient Values for Agents and Simulants in Polymeric Materials; in 

Materials Research Contributions to the Evaluation of Simulants, CRDEC SP 034, 

Proceedings of the Fifth International Simulant Workshop, CRDEC, 5–7 March 

1991, April 1992, UNCLASSIFIED Report.

Ince, Brian S., and Shuely, Wendel J., Scaling and Normalization to Allow 

Simulant Agent Comparisons of Material Sorption; in Materials Research 

Contributions to the Evaluation of Simulants, CRDEC SP 042, Proceedings of 

the Fifth International Simulant Workshop, CRDEC, 5–7 March 1991, April 1992, 

UNCLASSIFIED Report.

McHugh, Vincent M., Ince, Brian S., and Shuely, Wendel J., Solubility Behavior 

of Model Liquids with a Polymeric Viscoelastic Thickener; in Material Interactions 

with Agents and Simulants, CRDEC SP 011, Proceedings of the Third International 

Simulant Workshop, CRDEC, 7–9 March 1989, Compiled by White, W.E., Ph.D., 

November 1989, UNCLASSIFIED Report.

Shuely, Wendel J, Simulant Use in Materials Testing, CRDEC SP 86016, 

Proceedings of the Workshop on Methodology for Testing of Materials with Agents 

and Decontaminants, 9–11 July 1985, Compiled by Shuely, W.J., Schneider, N. and 

Matthews, S.C., May 1986, UNCLASSIFIED Report, ADB105018L.
62 Bibliography

Shuely, Wendel J, Simulant Use in Fabric Testing, NATICK/TR 88/070L, 

Proceedings of the Workshop on Methodology for Testing Permeable CD 

Materials with Chemical Agents, 19–20 May 1987, Compiled by Angelini, Pio, 

and Shuely, Wendel J, September 1988, UNCLASSIFIED Report, ADB128725L, 

ADD442088L.

Shuely, Wendel J., Physical and Polymer Chemistry in Simulant Development, 

CRDEC SP 002, Proceedings of the Second International Simulant Workshop, 

CRDEC, 1–3 March 1988, Compiled by White, W.E., Ph.D., December 1988, 

UNCLASSIFIED Report.

Shuely, Wendel J., Materials Coordination Overview; in Material Interactions with 

Agents and Simulants, CRDEC SP 011, Proceedings of the Third International 

Simulant Workshop, CRDEC, 7–9 March 1989, Compiled by White, W.E., Ph.D., 

November 1989, UNCLASSIFIED Report.

Shuely, Wendel J., Overview of Progress and Trends in Materials Research and 

Development with Relevance to Simulants; in Materials Research Contributions 

to the Evaluation of Test Liquids, CRDEC SP 025, Proceedings of the Fourth 

International Simulant Workshop, CRDEC, 6–8 March 1990, Compiled by Famini, 

George R., July 1990, UNCLASSIFIED Report.

Shuely, Wendel J., Abraham, Michael H., Ince, Brian S., and McHugh, Vincent 

M., Volatilization from Material Surfaces; in Material Interactions with Agents 

and Simulants, CRDEC SP 011, Proceedings of the Third International Simulant 

Workshop, CRDEC, 7–9 March 1989, Compiled by White, W.E., Ph.D., 

UNCLASSIFIED Report.

Shuely, Wendel J., and Abraham, Michael H., Liquid Properties Influencing 

Transport and Interactions with Materials: Surface Free Energy and Refractive 

Index Comparisons of Model Liquids with GD and HD; in Materials Interactions 

with Agents and Simulants, CRDEC SP 011, Proceedings of the Third 

International Simulant Workshop, CRDEC, 7–9 March 1989, Compiled by White, 

W.E., Ph.D., November 1989, UNCLASSIFIED Report.

Shuely, W.J., Ince, B.S., and McHugh, V.M., Experimental Correlations Between 

Agent Simulant Transport Properties, CRDEC SP 002, Proceedings of the Second 

International Simulant Workshop, CRDEC, 1–3 March 1988, Compiled by White, 

W.E., Ph.D., December 1988, UNCLASSIFIED Report.

Shuely, Wendel J., and Ince, Brian S., Interactions with Optically Transparent 

Materials; in Material Interactions with Agents and Simulants, CRDEC SP 011, 

Proceedings of the Third International Simulant Workshop, CRDEC, 7–9 March 

1989, Compiled by White, W.E., Ph.D., November 1989, UNCLASSIFIED Report.
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Shuely, Wendel J., and Ince, Brian S., Normalization and Scaling of Material 

Liquid Interactions; in Materials Research Contributions to the Evaluation of 

Test Liquids, CRDEC SP 025, Proceedings of the Fourth International Simulant 

Workshop, CRDEC, 6–8 March 1990, Compiled by Famini, George R., July 1990, 

UNCLASSIFIED Report.

Shuely, Wendel J., and Ince, Brian S., Progress in the Development of Test 

Liquids for Acceptance of Butyl Coated Cloth, CRDEC SP 042, Proceedings of 

the Fifth International Simulant Workshop, CRDEC, 5–7 March 1991, April 1992, 

UNCLASSIFIED Report.

Shuely, Wendel J., and Ince, Brian S., Screening Strategies for Safety and Toxicity 

of Materials Simulants; in Materials Research Contributions to the Evaluation 

of Simulants, CRDEC SP 042, Proceedings of the Fifth International Simulant 

Workshop, CRDEC, 5–7 March 1991, April 1992, UNCLASSIFIED Report.
Appendix A
Appendix A 67

Appendix A: Standard Test Method for 

Estimating Permeation Resistance of 

Nonporous Barrier Polymers to Liquid 

Chemical Warfare Agents (GB and HD) 

Using Liquid Simulants

Introduction

The National Institute for Occupational Safety and Health (NIOSH) held several 

public meetings to address the concerns of the stakeholders on developing and 

implementing standards for CBRN respiratory protective devices. Sarin (GB), 

a nerve agent, and sulfur mustard (HD), a blistering agent, were chosen as 

representative chemical warfare agents (CWAs) to test for chemical permeation 

resistance of respiratory protective devices. When it was stated at these public 

meetings that NIOSH would use military CWAs to certify respiratory protective 

devices, some respirator and other personal protective equipment (PPE) 

manufacturers requested that NIOSH identify chemical compounds (simulants) 

that can be used to simulate the permeation and penetration effects of CWAs on 

protective equipment. Manufacturers do not have access to GB and HD CWAs to 

perform in-house material and product development testing. In addition, there are 

only a limited number of certified laboratories able to perform CWA testing due 

to the high cost, toxicity levels, required lead time, and regulatory controls. These 

factors make any type of CWA testing very expensive and inconvenient. 

This test method was developed to provide respirator and other PPE 

manufacturers with a lower cost, more rapid screening method, relative to 

CWA testing, for evaluating the performance of candidate barrier materials to 

be used in the production of their PPE products such as respiratory protection 

devices and protective garments. This method was developed primarily so that 

PPE manufacturers could use accessible chemical compounds (simulants) that 

have lower toxicity to simulate the permeation effects of CWAs, specifically GB 

and HD. However, this permeation test can be performed with any nonreactive 

liquid including toxic industrial chemicals (TIC) in which the polymer does not 

decompose or dissolve. The simulant testing does not replace CWA testing for 

NIOSH certification of respirators. 
68 Appendix A

1. Scope 

1.1 This test method measures the resistance of nonporous materials to a liquid 

chemical under the conditions where the upper exposed test surface of the 

material specimen is wet (flooded) by the test chemical. The materials are 

used to manufacture personal protective equipment such as respirators, 

gloves, boots, and other types of protective clothing. The procedures can 

be applied to two types of liquids: (1) CWA simulants, for comparison with 

previously generated data to estimate permeation of GB and HD and (2) 

liquid TIC, to obtain direct permeation times for a particular TIC.

1.2 CWA Simulant Procedure. This procedure estimates the permeation resistance 

of flat nonporous films, membranes, and sheets up to 0.7 cm thick to liquid 

Sarin (GB) and sulfur mustard (HD) CWAs by using four simulant chemical 

compounds. Permeation of GB or HD through a candidate material can be 

estimated by comparison to those barrier materials that have been previously 

tested with GB, HD, and the four simulants. The permeation test results of 

polydimethylsiloxane [Silicone], poly(isobutylene) [Butyl], poly(ethyleneco-propylene-co-diene) EP8A [EPDM] after being exposed to GB, HD, and 

simulants are included in this test report to assist in future test data analysis 

with the correlation techniques. The following four CWA simulants are 

recommended for use with this test method: 1, 6-dichlorohexane (DCH), 

2-chloroethyl phenyl sulfide (CEPS), diethyl methylphosphonate (DEMP) and 

diisopropyl methylphosphonate (DIMP). 

 Simulant/CWA permeation correlations have been developed and are 

discussed as an alternative to testing with GB and HD. In addition to 

permeation results with Silicone, Butyl, and EPDM, poly(butadieneco-acrylonitrile) [Nitrile] was tested with only simulants as part of the 

preliminary screening of candidate materials. For additional details on the 

correlation between CWAs and simulants, refer to: Liquid Permeation through 

Nonporous Barrier Materials, D. Rivin, R.S. Lindsay, W.J. Shuely and A. 

Rodriguez, Journal of Membrane Science, Volume 246, Issue 1, 1 January 2005, 

Pages 39–47.

1.3 The TIC Procedure measures the permeation resistance of flat nonporous 

films, membranes, and elastomers, either a single layer or a composite of 

multiple layers, to any available non-reactive, liquid TIC in which the material 

does not decompose or dissolve. Permeation resistance times can be obtained 

directly when using this procedure; no correlation techniques are needed.
Appendix A 69

2. Reference Documents

2.1 ASTM Standards:

D 471 Test Method For Rubber Property-Effect of Liquids

D 543 Standard Test Method for Resistance of Plastics to Chemical Reagents

D 1415 Indentation Standard Test Method for Rubber Property—

International Hardness

D 2240 Standard Test Method for Rubber Property—Durometer Hardness

D 3182 Standard Practice for Rubber—Materials, Equipment, and Procedures for 

Mixing Standard Compounds and Preparing Standard Vulcanized Sheets

E 17 Specification for Standard Atmospheres for Conditioning and Testing Flexible 

Barrier Materials 

F 739 Test Method for Resistance of Protective Clothing Materials to Permeation 

by Liquids or Gases Under Conditions of Continuous Contact

F 1194 Standard Guide for Documenting the Results of Chemical Permeation 

Testing of Materials Used in Protective Clothing

2.2 Military Standards

Evaluation of Systematic and Random Error in the Measurement of Equilibrium 

Solubility and Diffusion Coefficient for Liquids in Polymers. Shuely, Wendel J. and 

Ince, Brian S. ECBC-TR-090. November 2001. Approved for public release.

Liquid Permeation through Nonporous Barrier Materials, D. Rivin, R.S. Lindsay, 

W.J. Shuely and A. Rodriguez, Journal of Membrane Science, Volume 246, Issue 1, 1 

January 2005, Pages 39–47 [1].

U.S. Army Test and Evaluation Command, Test Operations Procedure (TOP) 

8–2–501, Permeation and Penetration of Air-permeable, Semipermeable, and 

Impermeable Materials with Chemical Agents or Simulants (Swatch Testing), 

1997.

MIL-STD-282, Methods 204–209 GB, VX, and Mustard: Resistance of 

Impermeable Materials (Static Diffusion); in “Filter Units, Protective Clothing, 

Gas-Mask Components and Related Products: Performance Test Methods” 

(revised 1992). 
70 Appendix A

2.3 Federal Standards 

Federal Standard No. 191, Method 5030.2–4.1.3.; Determination of Thickness of 

Textile Materials.

2.4 Other Standards

ISO 6529:2001, Protective clothing—Protection against chemicals—Determination 

of resistance of protective clothing materials to permeation by liquids and gases

2.5 Material Safety Data Sheets (MSDS)

For MSDS information for the liquid test chemicals, contact the supply source 

using the CAS numbers and purity level of the chemicals. 

3. Terminology

3.1 Definitions

3.1.1 analytical technique. A procedure to quantitatively determine the 

concentration of the liquid test chemical in a collection medium.

3.1.2 breakthrough time. The intercept on the baseline of the initial linear rise 

of the permeation curve.

3.1.3 chemical warfare agents. Chemicals that have been militarized for use in 

offensive operations in combat. 

3.1.4 diffusion. The process in which molecules are transported from 

one location in a material to another location due to random 

molecular motion. 

3.1.5 diffusion coefficient. The coefficient equating the rate of transport per 

unit area to the change in concentration of diffusing species per unit 

distance traveled by the species.

3.1.6 flooded cell. A permeation cell geometry in which the exposed portion 

of the top surface of the protective material specimen is totally covered 

with the liquid test chemical.

3.1.7 fractional weight gain. The incremental sorption at time (t) divided by 

the plateau value representing the final steady state weight increase.

3.1.8 extraction error. Weight loss due to extraction of chemical components 

of the protective equipment material specimen into the excess sorbing 

liquid during the immersion test. The chemical components are 

relatively low molecular weight, nonreactive additives to the material 
Appendix A 71

specimen that can migrate out of the specimen during contact with 

liquid. The weight loss of these extractables masks the additional weight 

gain from the sorbing liquid.

3.1.9 immersion test. a procedure to determine liquid uptake by the material 

specimen that includes complete immersion of the material specimen 

into the test chemical to determine fractional weight gain and sorption 

as a function of time.

3.1.10 permeation. the overall process by which a chemical moves through 

a protective equipment material on a molecular level resulting in an 

emergent vapor flux.

3.1.11 permeation curve. the permeation flux per exposed material specimen 

area plotted versus time.

3.1.12 simulant chemical. a chemical that simulates some aspect of the 

permeation of Sarin (GB), sulfur mustard (HD), or other chemical 

warfare agents.

3.1.13 solubility. the mass of solute that dissolves into a material after a 

specified time under immersion conditions; equilibrium solubility is 

the maximum mass of solute that dissolves into a material after a period 

long enough for the weight gain versus time plot to show a plateau 

indicating equilibrium has been reached.

3.1.14 steady-state permeation. the constant rate of permeation that occurs 

after breakthrough when the chemical contact is continuous and all 

forces affecting permeation have reached equilibrium.

3.1.15 sweep gas. dry air or dry nitrogen from a pressurized tank that flows 

beneath the material specimen and is used to carry the permeation 

effluent to the detector for analysis.

3.1.16 liquid test chemical. liquid that is used to challenge the protective 

equipment material specimen.

3.2 Symbols

3.2.1 A. Area of material specimen exposed to liquid inside the liquid 

permeation cell.

3.2.2 Di. The diffusion coefficient determined using Fick’s second law 

in an immersion experiment.

3.2.3 DP. The diffusion coefficient determined from the steady-state 

permeation and solubility.

3.2.4 F. Volumetric flow rate of the sweep gas flowing to the 

chemical detector.
72 Appendix A

3.2.5 L. Thickness of the protective equipment material specimen.

3.2.6 P ́. Permeation flux (at steady state) through the exposed area 

of a material specimen during a unit of time.

3.2.7 P. The permeability coefficient is defined as the permeation 

per cm of material specimen thickness. Note: This is a 

permeation parameter.

3.2.8 S. Solubility of liquid in a polymer under immersion conditions 

at steady-state sorption or the concentration of dissolved 

molecules during steady-state permeation, which decreases 

continuously in the direction of permeant transport.

3.2.9 T1⁄2. Time at which permeation is half the steady-state value.

3.2.10 Tb. Breakthrough time determined as the intercept on the baseline 

of the initial linear rise of the permeation curve.

3.2.11 TS. The time at inception of steady-state permeation.

3.2.12 RDB. The ratio of a permeation parameter for a given liquid and 

polymer relative to DCH in Butyl rubber.

3.2.13 RDP. The ratio of a permeation parameter for a given liquid and 

polymer relative to DCH.

3.2.14 T1⁄2 / L2. Normalized halftime independent of material specimen 

thickness.

Note: This is a permeation parameter.

3.2.15 TB / L2. Normalized breakthrough time independent of material 

specimen thickness. Note: This is a permeation parameter.

3.3 Liquid Permeation Parameters:

3.3.1 Units

3.3.1.1 A, cm2

3.3.1.2 D, cm2/min 

3.3.1.3 F, cm3/min

3.3.1.4 L, cm

3.3.1.5 P ́, ng/cm2•min 

3.3.1.6 P, ng•cm/cm2•min

3.3.1.7 S, ng/cm3

3.3.1.8 T1⁄2, min
Appendix A 73

3.3.1.9 Tb, min

3.3.1.10 T1⁄2 / L2, min/cm2

3.3.1.11 Tb / L2, min/cm2

4. Summary of Test Method

4.1 The permeation resistance of a protective equipment material to a 

chemical is measured by detecting initial breakthrough.

4.2 This permeation test can be performed with the identified simulant 

chemicals or with any liquid TIC in which the material specimen does not 

dissolve or decompose.

4.3 In the permeation test apparatus, the protective equipment material 

specimen partitions the challenging chemical from the collection media.

5. Significance and Use

5.1 This test method can be used to estimate the permeation resistance of GB 

and HD chemical warfare agents by using the four simulant chemicals 

identified in this Appendix in Section 6.4.1 and by using the data analysis 

techniques described in this Appendix in Sections 11 and 12. 

5.2 The breakthrough time (Tb), halftime (T1⁄2), and permeability coefficient 

(P) are key measures of the effectiveness of personal protective equipment 

material. Barrier effectiveness of a test material is most conveniently 

compared to that of a standard (e.g., Butyl rubber) using P or normalized 

time parameters (Tb / L2 or T1⁄2 / L2).

5.3 The sensitivity of the test method in detecting low permeation rates or 

amounts of the test chemical that permeates the material specimen is 

determined by the detection system selected. For this test, a minimum 

detection level of 1 μg/ L is recommended.
74 Appendix A

6. Apparatus

6.1 Thickness Gauge, suitable for measuring thickness to the nearest 0.0025 

mm (or the nearest 0.0001 inch) that meets the specifications of Federal 

Specification GGG-C-105C shall be used to measure the thickness of the 

material specimens. 

6.2 Analytical Balance, readable and reproducible to ± 0.5 mg, shall be used to 

determine weight per unit area of each material specimen.

6.3 Liquid Permeation Cell, as shown in Figures A-1a. and A-1b.; the test 

apparatus consists of a two-chambered test cell for contacting the material 

specimen with the test chemical on the specimen’s normally outside 

surface and with a collection medium on the specimen’s inside surface. 

Mechanical drawings of the U.S. Army Natick Soldier Center Liquid 

Permeation Cell are located in Appendix B. 

Agent

Cell top reservoir 1.905 cm

Teflon gasket

Sweep gas:

Air or N2

A A

Specimen

Detector

Liquid well

A

Note: Not a mechanical

drawing and not to scale

5.715 cm

7.620 cm

Figure A-1a. Liquid Permeation Cell schematic: side view (cross-section)

Figure A-1b. Liquid permeation cell: top view
Appendix A 75

 6.3.1 Mount material specimen by performing the following steps:

 6.3.1.1 Unscrew (counter-clockwise) the Cell Top Reservoir and 

remove the Gasket.

 6.3.1.2 Place the material specimen concentrically into the center of 

the Cell Base Assembly. 

Note: Ensure specimen’s outer surface is on top so it will be in contact with the 

liquid test chemical.

 6.3.1.3 Place gasket on the material specimen with the ridge facing 

down so the ridge will be in contact with the specimen. If 

the specimen is rigid, an additional flat, Butyl rubber Gasket 

having an inside diameter of 2 cm and an outside diameter of 

3 cm can be placed between the specimen and the gasket. The 

flat Butyl rubber gasket shall be 0.3 cm ± 0.1 cm in thickness.

 6.3.1.4 Replace the Cell Top Reservoir by screwing it clockwise until 

it is tight enough to prevent the test liquid from seeping 

between the Gasket and the top of the material specimen.

6.4 Liquid Test Chemical 

 6.4.1 Liquid simulant chemical, a liquid that is placed on the protective 

equipment material specimen in a permeation test to simulate the 

permeation effect of Sarin (GB) or sulfur mustard (HD) chemical 

warfare agents. The liquids indicated as “nominal” simulants for GB 

or HD are similar to each CWA in chemical structure and properties. 

However, the permeation data shows a less specific relationship, such 

that, permeation curves for GB and HD in each barrier material, are 

bracketed by those of the four listed simulants in Table A-1.

Table A-1. Nominal Simulant Chemical Compounds

ID Code Chemical compound CAS No. Purity Source

Nominal HD Simulants:

DIMP Diisopropylmethylphosphonate 1445–75–6 95% Alfa Aesar

DEMP Diethylmethylphosphonate 683–08–9 97% Aldrich Chemical

Nominal HD Simulants:

CEPS 2-Chloroethylphenylsulfide 5535–49–9 98% Alfa Aesar

DCH 1,6-Dichlorohexane 2163–00–0 98% Aldrich Chemical
76 Appendix A

 6.4.2 Liquid Toxic Industrial Chemical, placed on the protective equipment 

material specimen as the liquid test chemical to obtain direct 

permeation data for a particular TIC.

6.5 Detector, must be capable of a minimum detectable quantity of 1 μg /L.

6.6 CWA Simulant Procedure, a flame ionization detector (FID) in a gas 

chromatograph or a stand-alone detector can be used to determine the 

effluent concentration of the four simulant chemicals; however, other 

detectors may be used that employ different technologies as, for example, 

ultraviolet (UV) and infrared (IR) spectrophotometry, flame photometry, 

mass spectrometry, and radionuclide tagging/detection counting. 

6.7 TIC Procedure, the detector used depends on the liquid test chemical being 

used as the challenging chemical. A detector shall be used that employs a 

technology that is capable of detecting the selected liquid test chemical. 

The minimum detection level for the detector shall be 1 μg /L.

6.8 Personal Computer, used with a data acquisition software to obtain 

incremental chemical breakthrough time test data that has the following 

minimal requirements:

 n Microsoft operating system (NT, Windows 2000 or later)

 n Peripheral component interconnect (PCI) slot 

 n Portable high capacity storage medium with a minimum of 100 

megabytes

 n 2.0 GHz with 400 MHz front side bus

6.9 Carrier Gas, (sweep gas), dry nitrogen (UN 1977) from a compressed or 

liquefied source or dry air (UN 1002) containing less than 10 ppm water.

6.10 Thermostat, used to maintain air temperature in the temperature control 

chamber at 35°C ± 2°C during the duration of the test.

6.11 Temperature Control Chamber, an enclosure to house the Liquid 

Permeation Cell and maintain a consistent temperature. 

6.12 Flow Controller, regulates to ± 1% the sweep gas that passes underneath 

the material specimen mounted in the Liquid Permeation Cell used as the 

collection medium.

6.13 Charcoal Trap, removes the vapor of the challenging liquid test chemical 

from the sweep gas before it is released into a fume-hood or the 

atmosphere.
Appendix A 77

7. Safety Precautions and 

Hazardous Waste Disposal

7.1 Before carrying out this test method, safety precautions needed for 

handling potentially hazardous chemicals should be identified and 

reviewed to provide full protection to all personnel. 

 7.1.1 For carcinogenic, mutagenic, teratogenic, and other toxic chemicals, 

the work area should be isolated, well vented, and meticulously clean. 

Involved personnel should be outfitted with protective clothing and 

equipment.

 7.1.2 For corrosive or otherwise hazardous chemicals, involved personnel 

should, as a minimum, be outfitted with protective clothing and 

equipment.

 7.1.3 As is standard laboratory practice, safety and health precautions 

should be taken consistent with the properties of the simulants 

given in each corresponding MSDS. It is an actionable violation of 

the OSHA Hazard Communication Standard (29 CFR 1910) to use 

a laboratory chemical without an appropriate MSDS. This standard 

requires that manufacturers and importers of hazardous materials 

conduct a hazard evaluation of the products they manufacture or 

import. If the product is found to be hazardous under the terms 

of the standard, containers of the material must be appropriately 

labeled and the first shipment of the material to a new customer 

must be accompanied by a MSDS. Employers, using the MSDSs 

they receive, must train their employees to recognize and avoid the 

hazards the materials present.

7.2 Emergency equipment, such as a safety shower, eyewash, and NIOSHcertified escape respirators approved for the protection against the 

chemical(s) in use, should be readily accessible in the test area. Also, 

NIOSH-certified, self-contained breathing apparatuses and the appropriate 

protective clothing should be available for reentry into the contaminated 

test laboratory.

7.3 Appropriate procedures for the disposal of the chemicals should be 

followed. The procedures must comply with all laboratory safety and 

handling procedures and federal, state and local hazardous waste disposal 

rules and regulations.
78 Appendix A

8. Test Specimen

8.1 The test specimen is a nonporous material specimen used in this test 

method to determine the material’s permeation resistance to a liquid 

simulant chemical or a liquid toxic industrial chemical. 

8.2 Each flat, nonporous specimen of protective equipment material may 

consist of either a single layer or a composite of multiple layers, not to 

exceed 0.7 cm in thickness. If material is representative of an actual 

clothing construction, the specimen’s normally outer surface shall contact 

the liquid test chemical.

8.3 Each material specimen to be tested shall have a circular shape of 

4.2 cm ± 0.3 cm in diameter.

8.4 A minimum of six material specimens shall be tested.

9. Conditioning

9.1 Condition each protective equipment material specimen for a period of 

1–24 hours by exposure to a temperature of 35°C ± 2°C and a relative 

humidity of 30%–80% as described in Specification ASTM E 171. 

Hydrophobic materials should require only 1 hour of conditioning and 

hydrophilic materials might require up to 24 hours of conditioning.

10. Procedure 

10.1 Measure the thickness of each conditioned material specimen at four 

widely spaced sites within the middle 3 cm diameter circular area of the 

permeation specimens; report the average value.

10.2 Determine material specimen weight per unit area ± 10% and record.

10.3 Mount the material specimen in the Liquid Permeation Cell shown in 

Fig. A-1a. as described in section 6.3.1.

10.4 Equilibrate the Liquid Permeation Cell which contains the material 

specimen at a temperature of 35°C ± 2°C and a relative humidity of 

30%–80% for a period of 2 hours in the Temperature Control Chamber. 

This is accomplished by setting the Thermostat heat controller to 35°C 

indicated on Figure A–2. 
Appendix A 79

10.5 Start the sweep gas that is used for the collection medium. The sweep gas 

rate shall be set for the detector in accordance with the manufacturer’s 

recommendations. If a range is not provided by the detector’s 

manufacturer, set the sweep gas rate to 33cm3/min, which should be 

adequate for all detectors. 

10.6 Check all connections to ensure there are no leaks in the detection loop. 

See Figure A–2.

Temperature

control chamber

Compressed air

or nitrogen

source

Liquid Permeation Cell

Detector Analog digital

acquisition board

Personal

computer

Charcoal trap

Thermostat, air

heater

Heated air

Flow 

Controller

Exausted sample air

DETECTION SYSTEM

Note: Indicates detection

Circulating heated air

Figure A–2. Example setup of permeation test system

10.7 Check the seal between the Gasket and the material specimen by flowing sweep 

gas through the Liquid Permeation Cell and compare the outlet flow from the 

cell to the previously measured inlet flow reading at the delivered flow rate. If the 

readings are not the same (~10%) as the measured inlet flow, indicating a leak, 

tighten the Cell Top Reservoir. If tightening the Cell Top Reservoir fails to stop 

the leak, replace the specimen.
80 Appendix A

10.8 Initiate the data acquisition system on the personal computer and apply 

approximately 0.3 ml of liquid test chemical (one of the four identified 

simulant chemicals) to the material specimen in the center of the Cell Top 

Reservoir. Test time shall begin at the moment the liquid test chemical 

comes into contact with the material specimen. Confirm by visual 

inspection that sufficient liquid test chemical is present to cover the entire 

exposed surface of the specimen. Place the Cell Cap into the center of the 

Cell Top Reservoir to reduce evaporation. Caution must be taken not to 

overfill the reservoir with the liquid test chemical by not exceeding 1.2 ml 

because the Cell Cap will create pressure on the liquid and force it into the 

material specimen. Remove the Cell Cap and check if any dry spots appear 

on the specimen every 2 hours. If any dry spots appear, add additional 

liquid and replace Cell Cap.

10.9 Discontinue sampling and terminate the test after a steady state 

permeation rate is reached at T > TS (Figure A–3). See ASTM F 739, 

Figure 4, for a wide range of permeation curve shapes.

10.10 After test run is terminated, disconnect the sweep gas lines from the liquid 

permeation cell. Remove liquid permeation cell from the temperature 

control chamber, remove Cell Cap and remove excess liquid test chemical 

from top of the specimen by using a pipette or by absorbing the liquid in 

a disposable cloth. This procedure must comply with all laboratory safety 

and handling procedures and Federal, State and local hazardous waste 

disposal rules and regulations.

10.11 A minimum of six material specimens per liquid test chemical shall 

be tested. 

0

0.1

0.2

0.3

0 10000 20000 30000 40000 50000

Time (sec)

 Ts

T1/2

Tb

Liquid Permeation of EPDM w ith DEMP

Signal (V)

Figure A-3. Typical permeation curve, electronic signal in voltage proportional 

to permeation rate.
Appendix A 81

11. Calculations

11.1 Permeation Calculations

 11.1.1 P ́ = S F A-1, ng/cm2 • min

 11.1.2 P = P ́ L, ng • cm/cm2 • min

11.2 Data Reduction Techniques 

Perform data reduction and calculations in accordance with:

n ASTM F 739

n Liquid Permeation through Nonporous Barrier Materials, D. Rivin, R.S. 

Lindsay, W.J. Shuely and A. Rodriguez, Journal of Membrane Science, Volume 

246, Issue 1, 1 January 2005, Pages 39–47.

n Sections 2.6 and 2.7 of Estimating the Permeation Resistance Of Nonporous 

Barrier Polymers to Sulfur Mustard (HD) and Sarin (GB) Chemical Warfare 

Agents Using Liquid Simulants, D. Rivin, W.J. Shuely, F. Palya, R.S. Lindsay, A. 

Rodriquez, and P. Bartram; NIOSH Publication No. 2008-141, July 2008 

(body of this publication).

12. Report

Construct Tables and Plots as shown in: Liquid Permeation through Nonporous 

Barrier Materials, D. Rivin, R.S. Lindsay, W.J. Shuely and A. Rodriguez, Journal 

of Membrane Science, Volume 246, Issue 1, 1 January 2005, Pages 39–47. Report 

results to the extent applicable in accordance with ASTM F 1194–99, Standard 

Guide for Documenting the Results of Chemical Permeation Testing of Materials 

Used in Protective Clothing.
Appendix B
Appendix B 85

Appendix B: Liquid Permeation Cell 

Mechanical Drawings

Page Number Drawing Number Drawing Nomenclature

84 TC-001 Cell Top Reservoir

85 TC-002 Cell Cap

86 TC-003 Gasket

87 TC-004 Permeation Cell Base

88 TC-005 Cell Base Assembly

89 TC-006 Liquid Permeation Cell
86 Appendix B
Appendix B 87
88 Appendix B
Appendix B 89
90 Appendix B
Appendix B 91
Appendix C
Appendix C 95

Appendix C: CWA Permeation Tables 

Table C–1. Liquid HD permeation data at 35°C: Silicone

 Thickness BT* Tb T1⁄2 Ts Permeation rate Permeability coefficient D1⁄2 Dp

cm (min) (min) (min) (min) (μg/cm2 • min) (μg • cm/cm2 • min) (10-7 cm2/s) (10-7 cm2/s)

Sample: S†=5.2%:

0.328 0 80 150 900 19.5 6.39 16.5 18.6

0.323 0 70 170 800 16.7 5.39 14.1 15.7

0.318 0 70 160 800 16.7 5.30 14.6 15.4

0.323 0 60 180 700 16.7 5.39 13.4 15.7

0.312 0 50 160 800 22.9 7.15 14.1 20.8

0.318 0 50 160 700 16.3 5.18 14.6 15.1

0.320 0 60 180 800 18.6 5.95 13.1 17.3

0.330 0 70 170 800 18.6 6.14 14.8 17.9

0.323 1 50 150 800 21.8 7.03 16.0 20.5

0.318 <1 60 160 700 18.7 5.94 14.6 17.3

0.318 <1 70 170 800 18.7 5.94 13.7 17.3

0.312 <1 60 170 800 21.2 6.62 13.3 19.3

0.315 <2 60 150 800 18.7 5.89 15.3 17.2

0.318 <2 70 170 900 16.0 5.08 13.7 14.8

0.310 <2 60 180 800 19.1 5.92 12.3 17.2

0.323 <2 70 180 900 19.0 6.13 13.4 17.9

0.323 1 60 170 900 14.5 4.68 14.1 13.6

0.320 1 50 160 900 16.9 5.41 14.8 15.8

0.315 1 60 160 800 15.6 4.91 14.3 14.3

0.312 <1 60 150 900 16.1 5.03 15.0 14.7

0.320 10 70 160 800 12.9 4.13 14.8 12.0

0.318 10 60 160 800 13.9 4.41 14.6 12.9

*BT= Breaththrough: Sampling time immediately after initial detection of effluent vapor 

†S= Steady state solubility in wt% 
96 Appendix C

Table C–2. Liquid HD permeation data at 35°C: Butyl

 Thickness BT* Tb T1⁄2 Ts Permeation rate Permeability coefficient D1⁄2 Dp

cm (min) (min) (min) (min) (μg/cm2 • min) (μg • cm/cm2 • min) (10-7 cm2/s) (10-7 cm2/s)

Sample: S†=23.6%:

0.028 26 30 70 200 16.9 0.472 0.258 0.303

0.030 26 30 90 300 12.7 0.387 0.238 0.249

0.033 29 30 100 300 12.2 0.403 0.252 0.259

0.030 31 30 80 300 14.0 0.427 0.268 0.274

0.030 33 30 90 200 13.4 0.408 0.238 0.262

0.033 35 40 80 200 13.4 0.442 0.315 0.284

0.036 49 50 110 300 13.8 0.491 0.265 0.315

0.036 27 30 90 300 12.1 0.430 0.324 0.276

0.036 29 30 90 200 12.1 0.430 0.324 0.276

0.038 55 60 110 300 11.4 0.434 0.305 0.279

0.036 33 30 100 300 12.5 0.445 0.292 0.285

0.036 51 50 100 300 10.0 0.356 0.292 0.228

0.030 26 30 80 300 10.6 0.323 0.268 0.207

0.033 28 30 90 300 10.4 0.343 0.280 0.220

0.033 29 30 80 300 10.4 0.343 0.315 0.220

0.038 55 60 110 300 9.2 0.351 0.305 0.225

0.038 31 30 90 300 9.5 0.362 0.373 0.232

0.033 22 30 90 300 20.9 0.690 0.280 0.443

0.033 3 10 90 300 18.4 0.608 0.280 0.390

0.033 45 50 80 400 17.2 0.568 0.315 0.365

0.036 65 70 100 300 24.7 0.878 0.292 0.564

*BT=Breaththrough: Sampling time immediately after initial detection of effluent vapor

†S=Steady state solubility in wt%
Appendix C 97

Table C–3. Liquid HD permeation data at 35°C; EPDM

 Thickness BT* Tb T1⁄2 Ts Permeation rate Permeability coefficient D1⁄2 Dp

cm (min) (min) (min) (min) (μg/cm2 • min) (μg • cm/cm2 • min) (10-7 cm2/s) (10-7 cm2/s)

Sample: S†=9.0%:

0.074 49 50 150 500 7.60 0.560 0.835 0.942

0.084 75 80 200 700 6.10 0.511 0.811 0.861

0.086 53 50 220 700 6.40 0.553 0.783 0.930

0.086 78 80 210 600 6.00 0.518 0.820 0.872

0.066 31 30 130 600 7.10 0.469 0.775 0.789

0.079 57 60 170 600 5.50 0.433 0.842 0.729

0.071 26 30 130 600 9.20 0.654 0.899 1.10

0.071 26 30 150 700 7.20 0.512 0.779 0.862

0.074 27 30 160 600 7.10 0.523 0.783 0.880

0.071 28 30 160 700 7.70 0.548 0.730 0.922

0.076 29 30 170 600 6.30 0.480 0.789 0.808

0.069 6 40 120 400 8.30 0.569 0.905 0.958

0.069 26 30 120 500 8.50 0.583 0.905 0.981

0.071 26 30 150 400 7.20 0.512 0.779 0.862

0.069 28 30 130 700 7.60 0.521 0.836 0.877

0.074 55 60 150 600 7.20 0.530 0.835 0.893

0.069 33 30 130 700 7.40 0.507 0.836 0.854

0.074 35 40 140 600 8.80 0.648 0.895 1.09

0.069 34 40 120 800 11.1 0.761 0.905 1.28

0.084 51 50 180 600 8.00 0.671 0.901 1.13

0.076 52 50 160 700 8.10 0.617 0.838 1.04

0.071 38 40 140 700 8.20 0.583 0.834 0.982

*BT=Breakthrough: Sampling time immediately after initial detection of effluent vapor.

†S=Steady state solubility in wt%.
98 Appendix C

Table C–4. Liquid GB permeation at 35°C: Silicone

 Thickness BT* Tb T1⁄2 Ts Permeation rate Permeability coefficient D1⁄2 Dp

cm (min) (min) (min) (min) (μg/cm2 • min) (μg • cm/cm2 • min) (10-7 cm2/s) (10-7 cm2/s)

Sample: S†=5.9%:

0.312 72 70 130 500 28.5 8.90 17.3 22.9

0.310 72 70 130 500 27.2 8.43 17.1 21.6

0.318 73 70 140 500 26.1 8.29 16.6 21.3

0.320 74 80 140 500 26.0 8.32 16.9 21.4

0.312 73 70 130 500 17.5 5.47 17.3 14.0

0.320 76 80 140 500 16.6 5.31 16.9 13.6

0.310 63 80 130 500 17.4 5.39 17.1 13.8

0.312 61 80 130 400 19.0 5.94 17.3 15.2

0.318 76 80 140 500 17.9 5.68 16.6 14.6

0.325 77 80 140 500 17.1 5.56 17.4 14.3

0.318 78 80 140 500 18.9 6.00 16.6 15.4

0.318 64 80 130 500 19.0 6.03 17.9 15.5

0.318 61 60 130 400 27.4 8.70 17.9 22.3

0.320 63 60 130 500 28.7 9.19 18.2 23.6

0.315 64 60 130 500 26.8 8.44 17.6 21.7

0.323 66 70 130 500 27.6 8.90 18.5 22.9

0.310 66 70 130 500 29.0 8.99 17.1 23.1

0.312 62 60 120 500 25.2 7.87 18.8 20.2

0.315 68 70 130 500 28.4 8.94 17.6 23.0

0.320 68 70 130 500 28.1 8.99 18.2 23.1

0.196 9 10 50 300 38.7 7.57 17.7 19.4

0.196 10 10 50 300 38.6 7.55 17.7 19.4

*BT=Breaththrough: Sampling time immediately after initial detection of effluent vapor. 

†S=Steady state solubility in wt%. 
Appendix C 99

Table C–5. Liquid GB permeation at 35°C: Butyl

 Thickness BT* Tb T1⁄2 Ts Permeation rate Permeability coefficient D1⁄2 Dp

cm (min) (min) (min) (min) (μg/cm2 • min) (μg • cm/cm2 • min) (10-7 cm2/s) (10-7 cm2/s)

Sample: S†=11.4%:

0.028 29 30 130 500 2.90 0.0810 0.139 0.108

0.033 83 80 210 600 1.70 0.0561 0.120 0.0746

0.030 85 90 200 600 2.20 0.0671 0.107 0.0891

0.033 85 90 180 700 2.10 0.0693 0.140 0.0922

0.033 87 90 230 700 1.90 0.0627 0.109 0.0834

0.036 115 120 270 700 1.50 0.0533 0.108 0.0709

0.038 117 120 280 600 1.40 0.0533 0.120 0.0709

0.028 63 60 150 500 2.20 0.0615 0.120 0.0817

0.030 38 40 150 500 2.80 0.0853 0.143 0.113

0.030 56 60 160 500 3.10 0.0945 0.134 0.126

0.036 85 90 220 700 2.30 0.0818 0.133 0.109

0.038 114 110 290 700 2.00 0.0762 0.116 0.101

0.038 114 110 310 800 2.00 0.0762 0.108 0.101

0.036 60 60 190 400 2.30 0.0818 0.154 0.109

0.033 63 60 130 600 2.70 0.0892 0.194 0.118

0.038 65 70 300 800 1.80 0.0686 0.112 0.0911

0.036 40 40 170 500 4.00 0.142 0.172 0.189

0.028 30 40 120 500 2.80 0.0782 0.150 0.104

0.036 46 50 230 800 2.40 0.0853 0.127 0.113

0.033 48 50 230 700 2.40 0.0792 0.109 0.105

0.036 64 60 240 800 2.20 0.0782 0.122 0.104

0.038 21 20 40 600 2.30 0.0876 0.838 0.116

*BT=Breakthrough: Sampling time immediately after initial detection of effluent vapor.

†S=Steady state solubility in wt%.
100 Appendix C

Table C–6. Liquid GB permeation at 35°C: EPDM

 Thickness BT* Tb T1⁄2 Ts Permeation rate Permeability coefficient D1⁄2 Dp

cm (min) (min) (min) (min) (μg/cm2 • min) (μg • cm/cm2 • min) (10-7 cm2/s) (10-7 cm2/s)

Sample: S†=2.5%:

0.084 56 60 70 900 1.70 0.142 2.32 0.864

0.066 59 60 140 900 1.90 0.125 0.719 0.760

0.086 59 60 260 1000 1.40 0.121 0.662 0.733

0.084 62 60 100 700 1.10 0.0922 1.62 0.559

0.084 63 60 280 800 1.60 0.134 0.580 0.813

0.079 93 90 250 800 1.50 0.118 0.573 0.716

0.084 94 90 280 900 1.40 0.117 0.580 0.711

0.084 95 90 260 800 1.60 0.134 0.624 0.813

0.084 31 30 50 800 1.30 0.109 3.25 0.660

0.071 31 30 140 700 1.40 0.0996 0.834 0.603

0.084 34 30 200 800 1.00 0.0838 0.811 0.508

0.071 63 60 180 700 1.30 0.0925 0.649 0.560

0.076 92 90 230 800 1.40 0.107 0.583 0.647

0.084 93 90 260 800 1.20 0.101 0.624 0.610

0.084 68 70 80 600 1.30 0.109 2.03 0.660

0.066 1 1 90 700 2.00 0.132 1.12 0.800

0.076 6 10 30 600 1.70 0.130 4.47 0.785

*BT=Breakthrough: Sampling time immediately after initial detection of effluent vapor.

†S=Steady state solubility in wt%.
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