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 ------- 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. ------- 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 ------- 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 ------- 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 ------- 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 ------- '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 ------- United States Environmental Protection Agency Center for Environmental Research Information Cincinnati OH 45268 BULK RATE POSTAGE & FEES PAIC EPA PERMIT No G-35 Official Business Penalty for Private Use $300 EPA/600/S2-87/104 0000329 PS TKET ------- |