United States
                   Environmental Protection
                   Agency
Water Engineering
Research Laboratory
Cincinnati OH 45268
                   Research and Development
EPA/600/S2-87/104 Jan. 1988
&EPA         Project Summary
                   Development  and
                   Assessment  of  Methods for
                   Estimating  Protective  Clothing
                   Performance
                   Rosemary Goydan, Arthur D. Schwope, Todd R. Carroll, Hsiao-Show Tseng,
                   andR. C. Reid
                     Methods were developed for estima-
                   ting the ability of protective clothing
                   polymers to act as a barrier to chemical
                   transport. The methods were devel-
                   oped for use by the U.S. Environmental
                   Protection Agency  (EPA),  Office of
                   Toxic Substances (OTS) to assess the
                   ability of protective clothing to reduce
                   chemical exposure risks as required in
                   Premanufacture Notification (PMN)
                   reviews.  Two methods  were focused
                   on:

                    1. Development of a mathematical
                       model based on Fickian diffusion
                       theory. The model emphasizes
                       prediction of cumulative permea-
                       tion and is based on refinements
                       of existing theoretical approaches
                       for  estimating   two  critical
                       parameters; the solubility, S, and
                       the diffusion coefficient, D. Per-
                       meation model predictions were
                       compared to well-documented
                       permeation data from the litera-
                       ture. The model's range of applic-
                       ability and its limitations  are
                       described.

                    2. Critical review of the applicability
                       and reliability of test methods for
                       measuring permeation resist-
                       ance, degradation resistance,
                       liquid immersion weight change,
                       and  chemical  sorption/desorp-
                       tion  of  protective  clothing
                       materials.

                     Efforts were initiated to develop an
                   integrated system  that will enable
                   accurate  and efficient  evaluation of
                   protective clothing requirements  and
                   recommendations.  Specific accomp-
lishments include: computerization of
the permeation estimation model,
development of a hierarchy that ranks
chemical resistance tests according to
their ability to generate data needed to
assess PMN clothing requirements,
and recommendations for improving
existing test methods.
  This Project Summary was devel-
oped by EPA's Water Engineering
Research Laboratory, Cincinnati, OH.
to announce key  findings of  the
research project that is fully docu-
mented in a separate report of the same
title (see  Project Report ordering
information at back).

Introduction
  Section 5  of  the  Toxic  Substances
Control Act (Public Law 94-469) requires
prospective manufacturers to  submit
PMN's, which are reviewed by OTS prior
to manufacture or import of new chem-
icals. OTS is  permitted only 90 days to
review each of the approximately 1,800
PMN's submitted annually. While many
substances are  not subjected to all
aspects of the review process, those that
are judged potentially toxic require
detailed assessments of the potential for
their environmental release and human
exposure during manufacture, process-
ing, and end use. If concerns are raised
to warrant  regulation; engineering con-
trols, work practice restrictions, or
protective clothing and equipment are
investigated  as  a  means to reduce
exposure risks.
  The submitter of the PMN often recom-
mends protective clothing as the means
to limit dermal exposures. Occasionally,
the  type of clothing  is specified; more
often it is not. In either case, OTS must

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have means of assessing the exposure
reduction provided by protective clothing.
Two options  are  available  to  OTS  for
estimating  the adequacy of protective
clothing: (1) OTS can request that PMN
submitters  test the clothing materials
and submit the resultant data, or (2) OTS
can estimate clothing performance using
available  information  and predictive
models. Because of the volume of PMN's
and the limited time permitted for each
review, the development of a  reliable
model  is desirable. If  a model is to be
used, it must estimate exposure protec-
tion  using only the  limited chemical
property data available for PMN substan-
ces. If testing is to be specified, OTS must
have  an awareness  of relevant test
methods and  the limitations of the data
that are produced.
  The  overall  assessment of protective
clothing requirements  must consider the
potential  health  effects of the PMN
substance,  the probable exposure con-
ditions, and the effectiveness of clothing
in limiting exposures. This study focused
on predicting the barrier effectiveness of
clothing materials. Figure 1 provides an
overview of the recommended system for
       judging clothing effectiveness. Clothing
       performance  depends  directly  on the
       exposure scenario, and the major factors
       that define the scenario are  highlighted.
       Three general methods  for assessing
       clothing performance were pursued—
       one  to develop  Pick's  law predictive
       models, a second  based on the analysis
       of existing performance test data, and a
       third  involving  the identification of
       appropriate  chemical  resistance  test
       methods.

       Predictive Models
         Permeation theory was used to esti-
       mate chemical  permeation  through
       clothing  materials  under  continuous
       exposure to pure substances. The model
       development effort focused on predicting
       the cumulative mass-permeated  as a
       function of time and not solely a break-
       through time.  OTS  needs more than a
       single breakthrough  time  to judge
       whether clothing performance  will be
       acceptable. OTS requires estimates of
       the time at which the cumulative amount
       permeated reaches  a limit of unaccep-
       table  human  risk. The  time when this
       toxicity limit  is reached may be  well
Exposure Scenario

• Physical state of chemical
  —Liquid, solid, gas
  —Neat
  —Mixture
• Temperature
• Duration
• Type of work
• Type of clothing
             (D

 Predictive Models

 • Permeation mechanisms
   —Pick's law
   —Solubility (S)
    —Equation of state
    —Group contributions
    —Statistical correlations

   —Diffusion Coefficient (D)
     —Empirical correlations
     —Concentration
      dependence

 • Paniculate penetration
   Protective
   Clothing
  Performance
Chemical Resistance
—Permeation
—Degradation
—Penetration
Physical Properties
—Abrasion
—Cut
—Torsional modulus
—Tear
—Tensile
— Thickness
—Puncture

Paniculate penetration
          (3)

      Data Bases

• Permeation
  —EPA "Guidelines"
  —NIOSH
  —CPCbase
  —GlovES

• S Values

• D Values

• Physical Properties
  —Must be developed
                       beyond the time when breakthrough i
                       detected.
                         Fickian  diffusion  behavior  wa
                       assumed and the classic mathematics
                       relationships were used for the estima
                       tion  of the rate, J, and  cumulativ
                       amount, Q, of  chemical that permeate
                       a polymer film  at any time following  th
                       initiation of the exposure. These relation
                       ships require two key parameters:  thi
                       diffusion coefficient, D, and the solubility
                       S.
                         Five  generic  polymers were  empha
                       sized:  butyl rubber, natural  rubber
                       Neoprene,*  nitrile rubber, and low
                       density polyethylene (LDPE). This repor
                       summarizes the progress to  date; refine
                       ments  to the   permeation estimatioi
                       model are continuing.
Solubility Estimation
  There  are  no well  tested, pureh
theoretical  approaches that  providi
accurate predictions of S for the system;
of interest. A theoretical equation of statt
(EOS) approach shows promise althougl
the technique  requires further refine
ment.  Three  group  contributior
approaches  were investigated and  th<
Oishi and Prausnitz approach was deter
mined the  most accurate and broadh
applicable.  Empirical  correlations with
the functional  groups of the  solutf
molecule were also explored.

Theoretical Approach—Kumar
Equation of State
  A statistical mechanics-based lattice
model EOS  was recently  used with
success by Kumar et al. to model  the
phase behavior of  supercritical  fluid;
containing polymer molecules. A simpli-
fied form of the Kumar EOS was usec
here  to  estimate  chemical/polymei
solubilities at  room  temperature  anc
pressure.  S  was predicted  using  thi;
approach for natural rubber, butyl rubber
and Neoprene. In general, the predictions
are accurate to an order of magnitude
but  tend to  underestimate values
reported in the literature. An importam
advantage is that this approach requires
only three pure component properties 01
the solute to estimate S: the moleculai
weight, vapor pressure, and liquid den-
sity at room temperature.
Figure 1.    Schematic representation of an integrated system for judging the suitability of
            protective clothing recommendations.
                                                "Mention of trade names or commercial product
                                                 does not constitute endorsement or recommenda
                                                 tion for use.

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 jroup Contribution Approaches

  Group contribution approaches require
only that  the  generic structure  of the
solute and  polymer be  known.  Most
methods proposed in the literature stem
from  an activity coefficient correlation
method called  UN1QUAC  (universal
quasi-chemical activity coefficients).  In
this approach,  x. the activity coefficient,
is expressed as a sum of y, and includes
terms for combinatorial,  residual, and
free volume contributions.
  Solubilities were predicted using three
group contribution approaches and
compared with measured values for butyl
rubber, LDPE, natural butyl rubber,
Neoprene,  and nitrile  rubber,  when
applicable. Table  1  presents results for
natural  rubber in which predictions by
the Oishi  and  Prausnitz, the  Holten-
Andersen,  and  the l!yas  and Doherty
techniques are compared with solubility
data. The UNIFAP (UNIQUAC  functional
group activity coefficients to polymer
systems) approach by Oishi and  Praus-
nitz and the Holten-Andersen approach
are both very accurate for a wide range
of chemicals; the predictions  are accu-
rate within an order of  magnitude and
many are within a factor of two (i.e., two
times higher or half the measured value).
Predictions are  less accurate  using the
llyas and Doherty method and can only
be  made for a  more  limited  set of
chemicals.  Results  for  butyl  rubber,
LDPE, Neoprene,  and nitrile rubber are
provided in the report.
Table 1.    Solubility Predictions for Natural Rubber/Solute Systems Using Group Contribution
           Approaches
Chemical Name
Acetic Acid
Acetic Anhydride
Acetone
Benzene
Benzyl Alcohol
Butylamine
Carbon Tetrachloride
Cyclohexane
Cyclohexanone
Dimethylaminopropylamine
Dimethylethanolamine
Dimethylformamide
Ethanol
Ethyl Acetate
2-Ethyl-1 -Butanol
Ethylene Dichloride
Eth yle nediamine
n-Heptane
n-Hexane
Isopropyl Alcohol
Methanol
Methyl Aery/ate
Methyl Chloroform
Methyl Ethyl Ketone
Methyl Isobutyl Ketone
Methyl Methacrylate
n-Pentanol
t-Pentanol
n-Propanol
n-Propyl Acetate
Tetrachloroethylene
Tetralin
Toluene
Trichloroethylene
o-Xylene
Average*
Experimental
S (g/cm)
0.078
0.039
0.095
3.2
0.15
1.4
8.3
2.8
2.4
1.1
0.17
0.039
0.007
0.43
0.42
2.1
0.087
1.6
1.3
0.040
O.OO2
0.52
4.5
0.46
1.2
1.1
0.12
0.39
0.088
1.3
7.0
4.4
3.5
7.5
3.8
Estimated S (g/cm)*'
UNIFAP
0.062
0.012
0.10
1.6
0.028
0.76
7.3
4.1
2.4
0.74
0.020
0.052
0.019
0.34
0.11
0.21
0.038
3.5
3.4
0.048
O.OO8
0.15
4.4
0.18
1.1
0.28
0.088
0.082
0.047
0.40
4.2
4.6
3.7
4.8
5.0
Holt-And%
na
0.009
0.13
1.7
0.019
na
2.4
0.93
0.62
na
na
na
0.019
0.75
0.068
2.9
na
2.0
1.8
0.035
OO08
0.14
5.0
0.24
0.55
0.37
0.085
0.085
0.036
0.22
na
1.6
1.2
na
0.79
Ily-Doh*
0.002
0.009
0.090
6.5
na
0.33
na
5.8
9.8
na
0010
na
6.2
0.52
0.007
na
6.5
4.5
45
0014
57
na
na
0.14
0.26
0.27
0.17
0028
0.015
1.4
na
38
1.4
na
1.5
 "Experimental solubility data are average values for that chemical in natural rubber in the
  temperature range from 20° to 30°C.
**(na) indicates that the required group interaction parameters are not available for this solute/
  polymer system.
 %Holten-Anderson approach.
 V/yas and Doherty approach.
  The Oishi and Prausnitz method is the
recommended approach. It can be used
to estimate  S for the five  polymers
emphasized  here.  In  some cases, the
Holten-Andersen approach is more
accurate but  its  applicability  is more
limited. At present, the Holten-Andersen
approach can treat natural rubber, butyl
rubber, LDPE, and solutes from chemical
classes including ketones,  alcohols,
esters, ethers, simple chlorinated com-
pounds, and  most hydrocarbons.  The
llyas  and Doherty approach  is more
limited and demonstrates only marginal
accuracy. For cases in which the UNIFAP
technique cannot be applied, the Kumar
EOS approach is recommended although
the approach is generally less accurate.
Chemical functional groups that cannot
be treated by the UNIFAP method include
nitriles,  tertiary  amines, phosphorous
containing compounds, and compounds
containing fluorine.

Diffusion Coefficient Estimation
  Models  to  estimate D for solute/
polymer matrix systems are much  less
advanced than  solubility  estimation
procedures. There  are no broadly appli-
cable  theoretical models to estimate D
in concentrated  polymer solutions. At
present, a useful approach is an empir-
ical correlation of experimental diffusion
coefficients with physical properties  of
the solute molecule.
  Theoretical Approach—Theoretical
approaches to diffusion coefficient  pre-
diction generally involved application of
free volume  theory.  Although  these
models provide a good qualitative repre-
sentation of variations in D with temper-
ature  and solute concentration, they are
difficult  to  apply  and require  physical
property data that are not  generally
available.  Consequently, these  ap-
proaches are not suitable for PMN review
evaluations where simplicity and broad
applicability are essential requirements.
  Empirical Approach—Because of the
limitations of theoretical approaches, the
project focused on correlating diffusion
coefficient data with  properties  of the
solute. The goal was  a simple, broadly
applicable technique that requires  only
the physical  property data typically
available in a  PMN. Published diffusion
coefficients were  obtained by literature
review.  Additional values were  calcu-
lated from permeation versus time  data
reported in the literature.
  Correlations of  measured  D  values
with properties representative of solute
size and shape were investigated. These

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properties  include  molecular weight,
molecular connectivity, surface/volume
ratios, and the acentric factor. The best
correlations were with molecular weight,
although,  for the  polymers with less
extensive data sets, the correlations are
not well defined.
  In Figure 2, D's are plotted for organic
liquids  and gases in  natural  rubber
versus  the  molecular weight  of  the
solute.  In general, the  data  show  a
consistent trend with molecular weight.
For the straight-chain hydrocarbons and
other approximately linear molecules,
the D  values decrease  approximately
linearly by two  orders of magnitude as
the molecular weight increases from 10
to 1,000 on the log-log scale.  However,
the values for branched or cyclic mole-
cules lie above the  general trend.
  The  development  of correlations
requires a sufficiently large  set of  D
values.  Few diffusion coefficient values
were found for  butyl rubber, Neoprene,
and nitrile rubber, (less than 10 in each
case), and the degree of confidence  in
the correlation equations is less for these
polymers. In general, the approach is not
accurate for cyclic molecules. Analysis
of additional permeation data sets con-
tinues and should enable  significant
improvements to the preliminary corre-
lations presented here.

Prediction  of Permeation
Behavior
  A permeation estimation model proto-
type was developed based on the above
estimation  techniques.  The model was
coded in FORTRAN and designed to run
on personal  computers  at OTS. The
permeation model  uses Pick's law with
the assumption of a  constant diffusion
coefficient. The overall accuracy of the
model is determined  by the accuracy to
which D and S can be predicted  and the
applicability of simple Fick's law equa-
tions  to  describe  the  permeation
behavior.
   Permeation  data from  the literature
were used to judge the accuracy of the
model in predicting the full permeation
curve. Four sources of good quality, well
documented data were used. In total, th
data set  for model  validation include
data for approximately 2 to 7 solutes fc
each of the five  polymers of interesi
Predictions were  generated using th
computer  model; two  approaches wer
used when  applicable—one using th<
molecular weight correlation for D am
UNIFAP for  S  and a second  using thi
molecular weight correlation for D am
Kumar EOS forS.
  The  permeation data and the mode
predictions are summarized in terms o
breakthrough  time and  steady-stati
permeation rate estimates; graphs com
paring  the model predictions with th<
data over the entire permeation curve an
provided in the report for each of the 2{
polymer/solute combinations evaluated
Values of the  breakthrough time wen
calculated at a given minimum detectei
flux or minimum detected amount per
mealed. The results for natural rubbe
are summarized in Table 2. Figure ;
compares the model  predictions
     10-'
I 1 1 1 1 1 1 1 I 1 1 1 ! 1 1 1 1
-
_




A


2
9
\ 9
T
\
\
%n
v
• te
— A
: o
-
_
i l i i i i ill 	 1 	 1 — 1 1 U 11
1 1 1 1 I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
( D ) Acetone
( A ) Benzene
( O ) Butane
( rj ) Cyclohexane
( A ) n-Decane
(A) n-Dotriacontane
\ ^v /
(3 ) Ethane
( ® ) n-Hexadecane
( B ) Hexane
( A ) Isobutane
( O) Isopentane
( • ) Methane
A ( • ) Pentane
( C ) Polybutadiene Oligomer
( + ) Propane
( v ) b-Propiolactone
( y ) Tolulene
\
x§ ^
O
c
1 i 1 1 1 1 1 1 1 1 1 1 1 1 U.J 	 1 	 J 	 U-i_L
1 L
-
_


_



—
-
I
-
-
_

-


~-
-


J_1_L
^ A
      70"
   u
   Q
      10'
      10'
                               10
           W2                  103

               Molecular Weight
 Figure 2.   Correlation of diffusion coefficients with solute molecular weight for solute/natural rubber systems.

                                    4

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Table 2.
Comparison of Permeation Data with Permeation Model Predictions for Natural
Rubber
                               Breakthrough Time
                                              Steady State Permeation
                                                Rate (ug/cm2-min)
              Thickness Measured    Basis*    Predicted"*
	(cm)	(min)    (ug/cm*-min)    (min)	Measured   Predicted

Natural Rubber
Acetone
Cvclohexane
Isopropanol
b-Propiolactone
Toluene
0.06
0.06
0.06
0.03
0.06
17
19
5340
25
10
0.76
1.8
1.0
19.7%
109.7
8
20
8
13
11
115
7
21
77
34
525
1.0
3.6
782
34
2
959
59
16
1
22
792
126
 *These values are the permeation rate detected at breakthrough and were used as the basis
  for predicting breakthrough times.
**AII predictions used the molecular weight correlation for D. Predictions using UNIFAP for S
  are reported on the first line followed by predictions using the Kumar EOS S on the second
  line. I—) indicates that predictions were not possible.
 §This value is the cumulative mass permeated, in units of fig/cm2, detected at breakthrough.
experimental data for natural  rubber/
acetone. In most cases, the permeation
predictions  using  a constant D  are
accurate within factors of 2 to 5 and are
often well within the range of experimen-
tal values reported in the literature.

Test Methods and Test Data
Interpretation
  For  instances when the  predictive
models do not apply or clothing perfor-
mance data for the chemical of interest
do not exist,  OTS may need  to request
protective clothing performance data to
facilitate a thorough review. This is often
the case for  mixtures. Thus, it is very
important  to have  well  defined test
methods  and data  reporting  require-
ments. Chemical resistance and physical
property test methods were reviewed
relative to OTS needs, with the emphasis
on chemical resistance testing.

Chemical Resistance
  Chemical  resistance test methods
were compared on the basis of the types
of results obtained,  their  approximate
cost, the relative skill level required to
perform them, and their inherent limita-
tions. Based on this comparison, a testing
hierarchy was developed, as discussed
below.
  Permeation Tests—In  a  permeation
test,  the chemical of interest is placed
on one side of the clothing material and
                              the other  side  is  monitored for the
                              appearance of the chemical. From the
                              results,  the total  amount (mass)  of
                              chemical permeating  a  known surface
                              area of the clothing at  any given time
                              can be calculated. The cumulative per-
                              meation (mass/area) or the correspond-
                              ing permeation  rate (mass/area/time)
                              can be  used along  with the estimated
                              frequency,  duration, and exposed body
                              surface area to  estimate dermal expo-
                              sures for specific workplace activities.
                                Although  the  test is  straightforward
                              and a  standard  method (ASTM  F739)
                              exists  for  its performance, variable
                              results can be obtained  under different
                              testing conditions for the same chemi-
                              cal/clothing material. Consequently,  in
                              describing or interpreting the results of
                              a permeation test,  there is a certain,
                              minimum   amount  of  information
                              required. This information includes the
                              breakthrough time, the steady  state
                              permeation  rate, the  clothing material
                              thickness and surface area, the analytical
                              sensitivity,  the collection medium flow
                              rate (open-loop  systems) or volume
                              (closed-loop systems), and temperature.
                                Immersion Tests—In  an  immersion
                              test, the clothing material is exposed on
                              one or  both sides  of the  chemical  of
                              interest for some period of time. The
                              change in  weight or  in other physical
                              characteristics is measured. In tests in
                              which the weight is accurately monitored
as a function  of time, D and  S of  the
chemical in the material can be calcu-
lated.  Such tests are  referred to as
sorption/desorption tests and  may be
performed  using either  liquid  or vapor
exposures.
  In  addition to weight,  other physical
characteristics of the clothing material
can  be used to assess the  overall
resistance to a chemical or  solution of
chemicals. These characteristics include
dimensions, puncture  resistance,  tear
resistance,  elongation resistance,
strength, and  so forth.  Such tests  are
referred to as degradation tests since
significant  detrimental changes in  the
clothing due  to the  chemical are of
interest.

Testing Hierarchy
  Both the chemical resistance and the
physical properties of the clothing mate-
rial must  be considered in  judging its
acceptability. While the physical property
requirements are specific to the partic-
ular  application,  chemical resistance is
a more general concept. Therefore, a test
hierarchy  was proposed for assessing
chemical resistance only (Table 3). The
testing hierarchy ranks chemical resist-
ance tests  according to their ability to
generate data  that can be used directly
to estimate the  effectiveness of  the
clothing material  in reducing exposure
risks.

Physical Characteristics
  In combination with chemical resist-
ance, protective  clothing must  possess
certain physical characteristics. These
characteristics can  be classified under
three headings: physical properties of the
base materials  and components of
construction, type and  quality of  con-
struction,  and human factors. Physical
property test  procedures to  measure
these  characteristics were  reviewed;
however, the applicability and limitations
of these  procedures  have  not been
established relative to clothing  require-
ments. The present state of the art is such
that  the ideal  set of physical character-
istics for any particular application may
be difficult to define and quantify. Efforts
in this  regard should be pursued.

Integrated System
Development
  The overall objective of this project is
to improve OTS's capability to rapidly and
effectively  assess the adequacy of  the
protective  clothing  recommendations

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                      Replicates of
                      Experimental data,
                      Bhown etal.. 1985
                                                                           O       (UNIFAP S/CORR D)
                        20
                                                                                                         740
Figure 3.   Comparison of model predictions for permeation flux as a function of time with experimental data for acetone/natural rubber.
 Table 3.    Test Data Priority for Estimating the Chemical Resistance of Protective Clothing
           Polymers

 Chemicals                                     Test Methods
Single- Component
 Liquid/Gases
Mult/component
 Solutions
1.  ASTM MethodF739 Permeation Test
2,  Permeation Cup (if chemical has sufficient vapor pressure)
3.  Weight change from liquid immersion.
4.  D and S from vapor or liquid sorption/desorption test.

1.  ASTM MethodF739 Permeation Test
provided in  PMN  submittals. This
involves assessing  the feasibility  of
developing a model,  test methods, and
test data interpretation guidelines  to
meet OTS needs for accuracy and effi-
ciency. This assessment will serve as the
basis for developing an integrated system
for reviewing PMN  protective clothing
requirements  based  on both predictive
model estimates and clothing perform-
ance data.
                The current PMN review process was
              analyzed in detail with  OTS. Based on
              this review,  a permeation  estimation
              computer  model  was  developed and
              evaluated by OTS for incorporation into
              the standard review process. The com-
              puter model was designed for use on IBM
              personal computers. The model requires
              input of basic physical  properties (i.e.,
              molecular weight, liquid density,  vapor
              pressure and/or the functional groups)
of the  PMN  substance.  Permeation
predictions are output  in either tabular
or graphic form. This  computer model
prototype  represents one component of
the overall system recommended for use
in reviewing clothing recommendations.
Existing databases  of  chemical  resist-
ance  information were also reviewed.
These were reviewed to  assess the
feasibility  of  using data  for existing
chemicals with structures and properties
similar to  those of a PMN substance to
estimate clothing performance for a PMN
substance.

Conclusions and
Recommendations
  A  system for  estimating clothing
performance should consider the cumu-
lative amount of chemicals that cross the
protective clothing boundary. A theoret-
ical model developed in this project was
successful in estimating the cumulative
permeation to within a factor of five. If

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'greater accuracy  is required in PMN
 review,  additional refinement  of the
 models is necessary. Alternatively, OTS
 can estimate protective clothing perform-
 ance on the basis of data for existing
 chemical analogues. Where there is no
 such chemical,  the PMN  chemical/
 clothing combination must be tested.
   The  recommended approaches to
 estimating  permeation  behavior as a
 function of time are those based on Pick's
 law. These require the estimation of the
 diffusion coefficient and the solubility of
 the chemical in the polymer. Techniques
 for estimating D and S were  developed
 and used in a permeation model proto-
 type based on Pick's law. In most cases,
 the permeation predictions were well
 within the range of experimental values
 reported for a specific permeant/polymer
 system. In other  cases, the predictions
 were less consistent with the experimen-
 tal data and this result may be because
 certain assumptions of the methodology
 were not valid. For example, the assump-
 tion of a constant diffusion coefficient is
 likely to be  invalid for polymers that are
 swollen  to a high degree by the
 permeant.
   For PMN substances that are mixtures
 and those with no chemical analogues
for  which there are permeation data,
testing is required. Permeation testing is
preferred and  should  be performed
according to ASTM  Method  F739 or  a
similar procedure under well controlled
and  documented experimental condi-
tions. Degradation and sorption/desorp-
tion test  methods provide either funda-
mental  parameters  for   use with
predictive models or general  indications
of clothing performance. However,  the
results of these  tests require interpre-
tation by persons with some  training in
polymer permeation  science.
  To achieve the goal of developing an
accurate and efficient method for judging
the suitability of PMN protective clothing
recommendations, OTS should continue
its  efforts to develop a three-part,
integrated system. The  system should
incorporate (1)  predictive models for
estimating chemical  resistance, (2)
existing chemical resistance  and phys-
ical  property databases,  and (3)  the
identification  and  specification  of
appropriate test methods.
  The full report was submitted in
fulfillment of  Contract No. 68-03-3293
by Arthur D. Little, Inc.,  under  the
sponsorship of the U.S. Environmental
Protection Agency.
   Rosemary Goydan. Arthur D. Schwope, Todd R. Carroll, and Hsiao-Show Tseng
     are with Arthur D. Little, Inc., Acorn Park, Cambridge, MA 02140; and Robert
     C. Reid is with Massachusetts Institute of Technology, Cambridge, MA 02139.
   Michael D. Royer is the EPA Project Officer (see below).
   The complete report, entitled  "Development and Assessment of Methods for
     Estimating Protective Clothing Performance." (Order No.  PB 88-133 657/
     AS; Cost: $25.95, subject to  change) will be available only from:
          National Technical Information Service
          5285 Port Royal Road
          Springfield.  VA 22161
           Telephone: 703-487-4650
   The EPA Project Officer can be contacted at:
           Water Engineering Research Laboratory
          U.S. Environmental Protection Agency
          Cincinnati, OH 45268

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United States
Environmental Protection
Agency
Center for Environmental Research
Information
Cincinnati OH 45268
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