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DRAFT FOR DISCUSSION
Chemical Warfare Agent (CWA) Simulant Program for Respirator Materials
Resistance Testing
CWA simulant agents for testing of respirators and respirator systems
are addressed separately for filtration and barrier materials. For filtration,
the technologies governing use of simulants, mass transfer and absorbent
capacity, are well understood. DMMP (dimethylmethylphosphate) is a good
filtration simulant since it is relatively non-toxic, is easily detectable
and has a volatility intermediate between GB and HD. Correlations between
DMMP and GB or HD are well understood. Reports will be identified and
made available to substantiate the use of DMMP as a filtration simulant
for GB and HD. Additionally, Carbon Tetrachloride and Cyclohexane can
be used as a GB and HD filtration simulant.
For barrier materials, the governing phenomenon relates to the chemical
as well as physical interaction of materials. Because of this interaction,
each barrier material needs to be considered individually to determine
precise agents to simulant correlations. The ever expanding and evolving
list of polymers and elastomers used as materials of construction for
respirators makes a one on one correlation a never-ending task.
In order to address the requirement to identify simulant agents for test,
manufacture and quality assurance uses with respirators, NIOSH has identified
the following program activities:
1. Filtration:
a. DMMP is identified as a test simulant for test and evaluation of
filter canisters and cartridges against GB and HD.
b. Correlation data for GB and HD testing with DMMP will be provided.
2. Barrier Materials:
a. A review of research and test information in Department of Defense
databases has identified eleven simulants from both current and past work
with GB and HD. As a result of the review and additional research, the
SBCCOM and NIOSH personnel are considering the following list of candidates
to be used as simulants for the GB and HD permeation study:
2-Chloroethyl phenyl sulfide
2-Chloroethyl cyclohexyl sulfide
Di-n-butyl sulfide
1,6-Dichlorohexane
Bis(4-chlorobutyl) ether
Diethyl methanephosphonate
Diethyl ethanephosphonate (DEEP)
Diisopropyl methylphosphonate (DIMP)
Dimethyl methanephosphonate (DMMP)
2,4-Dichlorophenol (DCP)
Triethly phosphate (TEP)
Additional simulants may be added or deleted from this list as information
evolves from the study. When using these or any other simulants, respirator
manufacturers must take into account the toxicity of the simulants.
b. A summary matrix derived from the military database has been developed
by the SBCCOM Agent Simulant Knowledge Advisory Office, dated February
20, 2002, identifying various barrier materials versus simulant breakthrough
information. The matrix can be used as a screening tool to determine
the overall protective characteristics of a barrier material. The matrix
is attached as an enclosure.
c. Accessible publications used in compiling the data matrix will be
identified for technical review. The publications combined with the matrix
will in some cases provide useful information in screening and evaluating
relative performance of barrier materials.
d. Specific CWA versus barrier material data, currently with restricted
access, will be reviewed with an objective to make the information obtainable
for general use. This will provide meaningful data concerning the protective
properties of specific barrier materials against GB and HD.
e. A project has been initiated by NIOSH and SBCCOM to identify chemical
compounds that can be used as simulants for GB and HD and a corresponding
laboratory procedure using simulants that can be used by manufacturers
for estimating GB and HD permeation through elastomeric materials. Investigations
with military scientists will be continued in an effort to develop additional
useable simulant information.
| |
A |
B |
C |
D |
E |
| 1 |
Reference 1. Permeation
Measurements of Chemical Agent Simulants Through Protective Clothing
Materials, Taransankar Pal, Guy D. Griffin, Gordon H. Miller,
Annetta P. Watson, Mary Lou Daugherty, and Tuan Vo-Dinh, Journal
of Hazardous Materials, 33, (1993) 123-141 * Unclassified - unlimited
distribution |
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| 2 |
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| 3 |
Material Composition* |
HD Simulant* |
HD Comments* |
GB Simulant* |
GB Comments* |
| 4 |
Teflon/fiberglass/Teflon
(10 mil) |
Dibutyl Sulfide (DBS) |
Ref 1: Breakthrough
Time > 24 hr |
Diisopropylmethyl phosphonate
(DIMP); Malathion (MAL) |
Ref 1: Breakthrough Time:
DIMP> 24 hr;
MAL > 24hr |
| 5 |
Teflon Kevlar Teflon(Force
Field) (17 mil) |
Dibutyl Sulfide (DBS) |
Ref 1: Breakthrough Time
> 100 hr |
Diisopropylmethyl phosphonate
(DIMP); Malathion (MAL) |
Ref 1: Breakthrough Time:
DIMP>100hr;
MAL > 100hr |
| 6 |
THf/Mws/Thf (First Team) |
Dibutyl Sulfide (DBS) |
Ref 1: Breakthrough
Time > 24 hr |
Diisopropylmethyl phosphonate
(DIMP); Malathion (MAL) |
Ref 1: Breakthrough Time:
DIMP> 24hr;
MAL > 24 hr |
| 7 |
Butyl/polyester/chloroprene(Chempruf
II) (19 mil) |
Dibutyl Sulfide (DBS) |
Ref 1: Breakthrough
Time > 24 hr |
Diisopropylmethyl phosphonate
(DIMP); Malathion (MAL) |
Ref 1: Breakthrough Time:
DIMP> 24hr;
MAL > 24hr |
| 8 |
Butyl/nylon/butyl (16
mil) (305 B/BA, 306 B/BA) |
Dibutyl Sulfide (DBS) |
Ref 1: Breakthrough
Time > 24 hr |
Diisopropylmethyl phosphonate
(DIMP); Malathion (MAL) |
Ref 1: Breakthrough Time:
DIMP> 24hr;
MAL >24hr |
| 9 |
Duct Tape (10 mil):
Special Type For Hazardous Materials |
Dibutyl Sulfide (DBS) |
Ref 1: Breakthrough
Time > 7 hr |
Diisopropylmethyl phosphonate
(DIMP); Malathion (MAL) |
Ref 1: Breakthrough Time:
DIMP 210 min;
MAL > 24hr |
| 10 |
Viton polyester/Viton
(9 mil) (305 B/BA, 306 B/BA) |
Dibutyl Sulfide (DBS) |
Ref 1: Breakthrough
Time > 100 hr |
Diisopropylmethyl phosphonate
(DIMP); Malathion (MAL) |
Ref 1: Breakthrough Time:
DIMP 140min;
MAL > 100hr |
| 11 |
Tyvek QC, Polyethylene-coated
(6 Mil) |
Dibutyl Sulfide (DBS) |
Ref 1: Breakthrough Time
30 min |
Diisopropylmethyl phosphonate
(DIMP); Malathion (MAL) |
Ref 1: Breakthrough Time:
DIMP 105min;
MAL 30min |
| 12 |
Barricade Chemical Barrier
Fabric (21 mil) |
Dibutyl Sulfide (DBS) |
Ref 1: Breakthrough Time
60min |
Diisopropylmethyl phosphonate
(DIMP); Malathion (MAL) |
Ref 1: Breakthrough Time:
DIMP 50 min;
MAL 90 min |
| 13 |
Butyl Nitrile glove (Pioneer
Gatorhide) |
Dibutyl Sulfide (DBS) |
Ref 1: Breakthrough Time
55min |
Diisopropylmethyl phosphonate
(DIMP); Malathion (MAL) |
Ref 1: Breakthrough Time:
DIMP 60min;
MAL 50 min |
| 14 |
Tyvek (Saranex-coated)
(8 mil) |
Dibutyl Sulfide (DBS) |
Ref 1: Breakthrough Time
90min |
Diisopropylmethyl phosphonate
(DIMP); Malathion (MAL) |
Ref 1: Breakthrough Time:
DIMP 30 min;
MAL 12 min |
| 15 |
Neoprene Plastic Glove |
Dibutyl Sulfide (DBS) |
Ref 1: Breakthrough Time
10min |
Diisopropylmethyl phosphonate
(DIMP); Malathion (MAL) |
Ref 1: Breakthrough Time:
DIMP 45min;
MAL 10 min |
| 16 |
PVC/nylon/PVC (305 PVC/BA)
(17 mil) |
Dibutyl Sulfide (DBS) |
Ref 1: Breakthrough Time
4min |
Diisopropylmethyl phosphonate
(DIMP); Malathion (MAL) |
Ref 1: Breakthrough Time:
DIMP 10min;
MAL 3min |
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A |
B |
C |
D |
E |
| 17 |
Reference 2. Chemical Agent Simulants for
Testing Transparent Materials,CRDEC-CR- 88069, Lewis, Randall,
Liebman, Shirley A., and Isaccson, Louis, Chemical Research, Development
and Engineering Center, Aberdeen Proving Ground, MD 21010-5423,
AD A197138 * Unclassified unlimited distribution |
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Ref 2: Possible problem: the simulant can
roll-off the transparent material or evaporate at a non- uniform
rate. |
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| 18 |
Material Composition* |
HD Simulant* |
HD Comments* |
GB Simulant* |
GB Comments* |
| 19 |
Polycarbonates |
2-chloroethyethyl sulfide (CEES), 2-chloroethylmethyl
sulfide (CEMS); 1,5dichloropentane |
Ref 2: All caused crazing |
Diisopropylmethyl phosphonate (DIMP); DiethylethylPhosphonate(DEEP);
DimethylHydrogen Phosphonate(DMHP) |
Ref 2: All caused crazing |
| 20 |
Cast PMMA |
2-chloroethyethyl sulfide (CEES), 2-chloroethylmethyl
sulfide (CEMS); 1,5dichloropentane |
Ref 2: All caused crazing |
Diisopropylmethyl phosphonate (DIMP); DiethylethylPhosphonate(DEEP);
DimethylHydrogen Phosphonate(DMHP) |
Ref 2: All caused crazing |
| 21 |
Stretched PMMA |
2-chloroethyethyl sulfide (CEES), 2-chloroethylmethyl
sulfide (CEMS); 1,5dichloropentane |
Ref 2: All caused crazing |
Diisopropylmethyl phosphonate (DIMP); DiethylethylPhosphonate(DEEP);
DimethylHydrogen Phosphonate(DMHP) |
Ref 2: All caused crazing |
| 22 |
Polyurethane |
2-chloroethyethyl sulfide (CEES), 2-chloroethylmethyl
sulfide (CEMS); 1,5dichloropentane |
Ref 2. CEES and CEMS caused crazing; 1,5 dichloropentane
had no crazing. |
Diisopropylmethyl phosphonate (DIMP); DiethylethylPhosphonate(DEEP);
DimethylHydrogen Phosphonate(DMHP) |
Ref 2: DIMP induced crazing: DEEP and DMHP did
not induce crazing. |
| 23 |
Reference 3. Determination of Permeation
Breakthrough Times by Droplet and Minicams Testing, Bodnar,
Stephen C., Sloan, James M., Gabriel, Karim M. Proceedings of the
1992 ERDEC Scientific Conference on Chemical Defense Research, 17-20
November 1992, AD 269-728, 799-803 * Unclassified- unlimited
distribution |
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| 24 |
Material Composition* |
HD Simulant* |
HD Comments* |
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| 25 |
Butyl Rubber |
2-chloroethyethyl sulfide (CEES), 2-chloroethylmethyl
sulfide (CEMS); 3-chloropropylthiolacetate(CPTA) |
Ref 3: Breakthrough Times of 2-chloroethylmethyl
(CEMS) more consistent to that of HD; 2-chloroethylethylsulfide
(CEES) slightly shorter than HD;
3-chloropropylthioacetate longer than HD |
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A |
B |
C |
D |
E |
| 26 |
Reference 4. Interpretations of Simulant
Breakthrough Time With Laminates of Rubber Materials, Anthony
F. Wilde and Stephen C. Bodner, Proceedings of the 1994 ERDEC Scientific
Conference on Chemical Defense Research, 15-18 November 1994, AD
313-080, 311-317. * Unclassified- unlimited distribution |
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| 27 |
Material Composition* |
HD Simulant* |
HD Comments* |
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| 28 |
Silicone/Silicone (45.6 mil avg) |
2-chloroethyethyl sulfide (CEES) |
Ref 4: Average Breakthrough times: 6.6 min |
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Butyl/Silicone (44.0 mil avg) |
2-chloroethyethyl sulfide (CEES) |
Ref 4: Average Breakthrough times: 34.1
min |
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| 30 |
Butyl/Butyl (33.4 mill avg) |
2-chloroethyethyl sulfide (CEES) |
Ref 4: Average Breakthrough times: 76.6 min |
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| 31 |
Nitrile/Butyl (43.1 mil avg) |
2-chloroethyethyl sulfide (CEES) |
Ref 4: Average Breakthrough times: 106.7 min
(3 tests) 88.8 min (7 tests) |
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| 32 |
Nitrile/Nitrile (41.9 mil avg) |
2-chloroethyethyl sulfide (CEES) |
Ref 4: Average Breakthrough times: 48.5 min |
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| 33 |
Reference 5. Prediction of Polymer-Liquid
Interaction Based on Polymer Phase Diagrams: Bis(2-Chloroethyl)Sulfide
Cohesion Parameter Predictions For Over One Hundred Materials,
ERDEC-TR-306, Wendel J. Shuely, Edgewood Research, Development and
Engineering Center, Aberdeen Proving Ground, MD 21010-5423, AD A310604*
Unclassified- unlimited distribution |
Ref 5. Very few commercial polymeric materials
are predicted to be HD resistant. |
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Material Composition* |
Predicted Solubility in HD* |
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| 35 |
Isobutylene Butyl Rubber |
insoluble |
Ref 5. Interaction of solubility/miscibility;
a familiar resistant/protective polymer for HD. |
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Teflon |
insoluble |
Ref 5. Interaction of solubility/miscibility;
a familiar resistant/protective polymer for HD. |
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Poly (vinylidene fluoride), TEDLAR |
insoluble |
Ref 5. Interaction of solubility/miscibility;
a familiar resistant/protective polymer for HD. |
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Polyvinyl Chloride( Vipla KR |
not soluble in all proportions |
Ref 5. Interaction of solubility/miscibility;
tested and prediction affirmed. |
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Nylon, Versamid 930 |
insoluble |
Ref 5. |
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Polyisoprene Cariflex IR305 |
not soluble in all proportions |
Ref 5. Interaction of solubility/miscibility;
tested and prediction affirmed. |
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Chlorosulfonated polyethylene ( Hypalon 20,30,40) |
insoluble |
Ref 5. |
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| 42 |
93 other materials |
soluble in all proportions |
Ref 5. |
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B |
C |
D |
E |
| 43 |
Reference 6. Currently Available Permeability
and Breakthrough data characterizing Chemical Warfare Agents and
Their simulants in Civilian Protective Clothing Materials, Mary
Lou Daugherty, Annetta P. Watson, and Tuan Vo-Dinh, Journal of Hazardous
Materials, 30 (1992) 2343-267 open literature |
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Ref 6. There is a paucity of simulant permeability
and breakthrough times data available. It is recommended to obtain
this report as a document that gives some agent versus manufacturer
trade name material data. |
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Material Composition* |
HD Simulant* |
HD Comments* |
GB Simulant* |
GB Comments* |
| 45 |
Chemrel |
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Malathion, 10% |
Ref 6. Breakthrough Time; >360 min |
| 46 |
Chemrel |
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Malthion, 60% |
Ref 6. Breakthrough Time; > 240 min |
| 47 |
Chemrel |
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Methyl Parathion,10 % |
Ref 6. Breakthrough Time; > 360 min |
| 48 |
Chemrel |
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Methyl Parathion,57 % |
Ref 6. Breakthrough Time; >120 min |
| 49 |
Teflon (ChemFAB Challenge 5100) |
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Naled |
Ref 6. Breakthrough Time; >288 min |
| 50 |
Teflon (ChemFAB Challenge 5100) |
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Ethion |
Ref 6. Breakthrough Time; >204 min |
| 51 |
Teflon (ChemFAB Challenge 5100) |
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Parathion |
Ref 6. Breakthrough Time; >180 min |
| 52 |
Natural Rubber (Edmont 36-124) (.51
mm) |
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Guthion |
Ref 6. Breakthrough Time; >190 min |
| 53 |
Neoprene (Edmont 29-865) (.51 mm) |
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Guthion |
Ref 6. Breakthrough Time; >510 min |
| 54 |
Nitrile (Edmont 37-175) (.46 mm) |
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Guthion |
Ref 6. Breakthrough Time; >510 min |
| 55 |
PVC (Edmont Canada) |
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Guthion |
Ref 6. Breakthrough Time; >250 min |
| 56 |
Reference 7. Sorption of Sulfur Mustard
and its Oxygen Analog in Black and Nonblack-Filled Butyl Rubber
Membranes, Vinita Dubey, N.B.S. Rao, S.N. Maiti, A.K. Gupta,
Journal of Applied Polymer Science, 69: 503-511, 1998 open literature |
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Butyl Rubber Membranes |
bis(2-chloroethyl) ether |
Ref 7. Gravimetric method for permeation studies. |
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Reference 8. Diffusion and Sorption of Sulfur
Mustard and Bis(2(chloroethyl)ether in Elastomers: A Comparative
Study,Vinita Dubey, A. K Gupta, Vinita Dubey,S.N. Maiti, N.B.S.
Rao, Journal of Applied Polymer Science, Vol 77, 2472-2479 (2000)
open literature |
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Various Elastomers |
bis(2-chloroethyl) ether |
Ref 8. Diffuses faster than sulfur mustard. |
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A |
B |
C |
D |
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| 61 |
GB Simulant* |
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HD / GB Simulant* |
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| 62 |
9. Diisopropylfluorophosphonate (DFP) has
been used as a vapor simulant for GB.* |
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10. Methyl Salicylate (MS, MES) has been used
as a vapor simulant for HD and GB.* |
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* Disclaimers and Comments |
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Comments |
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| 65 |
Disclaimer: While the Edgewood Chemical Biological
Center, Department of the Army believes that the data contained
herein are factual and the opinions expressed are those of qualified
experts regarding the results of the tests conducted, the data is
not to be taken as warranty or representation for which the Department
of Army or Edgewood Chemical Biological Center assumes legal responsibility.
they are offered solely for your consideration, investigation, and
verification. Any use of this data and information must be determined
by the user to be in accordance with applicable Federal, State,
and Local law regulations. The simulant information provided is
not to be used as a recommendation of any simulant. The data is
for informational use only. The findings are not to be construed
as an official Department of the Army position unless so designated
by other authorizing documents. We make no warranty of merchantability
or any other warranty, express or implied, with respect to such
information, and we assume no liability resulting from its use. |
Disclaimer: Users should make their own investigations
to determine the suitability of the information for their particular
purposes. In no way shall the Department of the Army or Edgewood
Chemical Biological Center be liable for any claims, losses, or
damages of any third party or for lost profits or any special, indirect,
incidental, consequential or exemplary damages, howsoever arising,
even if the Department of the Army or Edgewood Chemical Biological
Center has been advised of the possibility of such damages. |
Disclaimer: Reference herein to any specific
commercial product, process or service by trade name, trademark,
manufacturer, or otherwise, does not necessarily constitute or imply
its endorsement, recommendation, or favoring by the United States
Government or any agency thereof. The views and opinions of authors
expressed herein do not necessarily state or reflect those of the
United States Government or any agency thereof. |
a. There is no better simulant than the agent
itself.
b. There is very little (HD) (GB) simulant data versus materials
available. Because the US government had neat agent testing facilities,
there was no need to use simulants for materials testing. The agents
were tested directly against the materials; and data is available
on the effects of HD and GB versus materials. However, this information
has limited distribution.
c. The experimental testing procedures used in the above references
are different than those in the NIOSH SMARTMAN Test. |
d. CEES and CEMS evaporate more quickly than
HD. Therefore, if one used CEES or CEMS as
a HD liquid droplet simulant, a barrier may be needed to prevent
CEES and CEMS evaporation.
e. It may be necessary to use more than one simulant for an
agent: one simulant for the vapor challenge and another simulant
for the liquid challenge. |
| 66 |
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| 67 |
Simulant |
CAS Registry Number |
Simulant |
CAS Registry Number |
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| 68 |
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| 69 |
CEES |
693-07-2 |
DIMP |
1445-75-6 |
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| 70 |
DBS |
544-40-1 |
MAL |
121-75-5 |
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| 71 |
DEEP |
78-38-6 |
MS, MES |
119-36-8 |
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| 72 |
DFP |
55-91-4 |
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