Solvent Flammability Basics

The concept of flammability may seem elementary on the surface, when in actuality, flammability and flash point measurements must be performed using the correct standardized methods. You may be surprised when you do. by Ronald L. Shubkin and Barbara F. Kanegsberg There are a number of sources of confusion regarding flammability. One problem is the application of test methods conducted outside of the range of parameters for which the test is designed. Finally, the vapors of certain halogenated solvents can burn within a narrow concentration range in air even though they exhibit no flash point. They are self-extinguishing. All of these factors have led to incorrect flammability data. As with other physical and chemical parameters, it is crucial for manufacturers to have access to flash point data based on the appropriate consensus standard for the material in question and performed by independent test facilities. Flammability Definitions and Standards The Occupational Safety and Health Administration (OSHA) defines “Liquid, Flammable” as “any liquid having a flashpoint below 100 °F (37.8 °C), except any mixture having components with flashpoints of 100 °F (37.8 °C) or higher, the total of which make up 99 percent or more of the total volume of the mixture.”i The U.S. Department of Transportation (DOT) defines Class 3 Flammable Liquidsii for transportation purposes on essentially the same basisiii. Both regulatory agencies define “Flash Point” as the minimum temperature at which a liquid gives off a vapor in sufficient concentration to ignite when tested by specific methods as set forth in the regulationsiv. Both DOT and OSHA specify appropriate test methods from the American Society for Testing and Materials (ASTM), specifically ASTM D56, ASTM D93 and ASTM D3278. DOT also allows ASTM D3828. The National Fire Protection Agency (NFPA) Code 30 is a definitive consensus document for determining flammability. This document clarifies which flammability tests are considered valid for particular compounds or mixtures, referring to essentially the same ASTM test methods, as does OSHA. In Code 30, the characteristics of a flash point are defined in section as the minimum temperature of a liquid at which sufficient vapor is given off to form an ignitable mixture with the air, near the surface of the liquid or within the vessel used, as determined by the appropriate test procedure and apparatus specified in 1.7.4. Note that both the appropriate apparatus and the test procedure depend on the material being tested. The use of an inappropriate approach for the chemical under investigation, or the employment of an incorrect apparatus, may lead to an incorrect result. Choosing the Flash Point Test Method A variety of Flash Point test methods have been developed to determine the flammability of liquids. Certain of these have become industry standards and are correct in a technical sense. However, these various methodologies are valid only over specified temperature ranges and for liquids with viscosities within specified ranges. If an incorrect technique is used for the material in question, a result is obtained that is not valid. For example, nPB has a relatively low viscosity, and independent laboratories, using the accepted techniques for low viscosity materials, have determined that n-propyl bromide does not have a flash point.v,vi Contrarily, a method using the Pensky-Martens Closed Cup procedure (ISO 1523) a methodology designed for a viscous fluid and valid only at temperatures above +10°C obtained a flash point of –10°C for nPB.vii Following that report, an

Chilworth Technology Ltd. The results for nPB and for five widely accepted nonflammable liquids are given in Table I. The appropriate technique is ASTM D56. Flash Point Run Within Test Ranges ASTM D56 None None None None None None Flash Point.. A flash point test consists of passing a pilot light over the surface of the liquid being tested. The reason is that the flash point apparatus is designed to start fires under specific conditions. results obtained using ASTM D93 were compared to those obtained using ASTM D56 (Tag Closed Cup). In addition. The use of an apparatus and a method outside the range that it was designed for can give a flash point under conditions that are not relevant to real-world conditions.viii. Flash Points by Appropriate and Inappropriate Methods: The flash point method of choice depends on the compound to be measured.5 cSt at 104°F (40°C) or 9. For example. consensus document is NFPA Code 30. The lowest temperature at which this flame propagation happens is called the flash point. a consensus standard that employs the Pensky-Martens Closed Cup apparatus. more than an order of magnitude below the dividing line between the ASTM D56 technique (low viscosity) and the ASTM D93 technique (Pensky-Martens Closed Cup for high viscosity liquids).4.ix Tests were performed using ASTM D93. Observing a Flash Point Some of the confusion in reporting the results of flash point testing lies in understanding the definition of a flash point.4.4. °C Run Outside Test Ranges ASTM D93 -5 + 24 . is not more conservative or protective of workers. the same equipment specified in ISO 1523. “Standard Method of Test for Flash Point by the Tag Closed Cup Tester”.14 Compound n-propyl bromide Trichloroethylene Methylene chloride HFE-72DE HFE-71 DE HFE-71 DA Table 1.. even solvents accepted and used for decades as having no flash point can erroneously appear to be flammable. which is for liquids with a relatively low viscosity.16 .5 -9 .5.7. If the vapors of a liquid are flammable. Accepting the results of a seemingly more stringent flash point determination. is that described in section 1. determined if this methodology gave results that differed from what was reported for other wellestablished non-flammable liquids.7. ASTM D 3278 for small-scale testing is also permitted under certain conditions as indicated in Section 1. the viscosity of nPB is 0.1. ASTM D56 is specified to be used for low viscosity fluids and may be used at low temperatures. The NFPA gives a . Unlike ASTM D93.36 cSt at 25°C. capable of sustaining combustion. the flame front will propagate from the pilot light to the liquid surface.5 cSt at 77°F (25°C). in other words. which is not an industry standard. The relevant method for low viscosity liquids. a definitive. in other words. As indicated.independent testing laboratory. below 5. If an incorrect method for the compound being studied is employed.

e.8 vol.1-trichloroethane HCFC-141b HFE 7200b LELx 4. some hydrochlorofluorocarbons and nPB will burn when the vapor concentration in air is within narrow limits. the enhanced flame is above the pilot light and not near the surface of the liquid as required by the various NFPA definitions. the “flash” is readily apparent as it spreads almost explosively through the flash point cup and above it. methylene chloride. “The minimum temperature at which a liquid gives off vapor sufficient to form an ignitable mixture in air near the surface of the liquid. etc. Flammability limits are usually reported as the Lower Explosive Limit (LEL) and Upper Explosive Limit (UEL). erroneous identification of n-propyl bromide as a flammable liquid.1.. In this case. Table 2. can be combusted in an external source of ignition. Flammability Limits Most hydrochlorocarbons. Non-flammable liquids that will not burn at the temperature of the pilot light will not affect the pilot light flame. When such vapors begin to burn. halogenated liquids. The mistaken interpretation of pilot light enhancement for flashpoint led to early. Enhancement of the pilot light is typical of hydrochlorocarbons that are classified as non-flammable (i.). Specifically. The combustion rapidly self-extinguishes. nPropyl bromide does not exhibit this behavior under the conditions of the ASTM D56 or the Cleveland Open Cup methods.0 7. The units are commonly the volume percent of the vapor in air. The concentration in the vapor state is depleted by both consumption in the oxidation process and by expansion of the vapor caused by the exothermic combustion. several factors rapidly change the vapor concentration so that it is no longer within the flammable limits. trichloroethylene.7 A flash point test consists of moving a pilot light over an open cup of liquid (open cup tests) or opening the cover of a closed container when a pilot light is positioned over the cover (closed cup tests). The flammability limits of some well-known. the flame front must move from the pilot light to near the surface of the liquid. One source of erroneous reports of flash points consistent with inaccurate observations is that the vapors of certain halogenated compounds.” In lay terms. but they all include the phrase. some hydrofluoroethers.7 1070 g/m3 .number of definitions of flashpoint in its Glossary of Terms.5 13. Flammable liquids behave quite differently in flash point tests than do nonflammable. in contrast with halogenated solvents and other non-flammable liquids.0 10.0 7.% 13.6 210 g/m3 UEL12 7.% 23. “non-flammable” liquids are given in Table II.0 8.0 vol. The result of this characteristic in the performance of a flash point test is that the pilot light may be briefly enhanced before it is extinguished. Flammability Limits of Representative Non-Flammable Liquidsa Compound n-propyl bromide methylene chloride trichloroethylene 1.0 17.

a. Document No. an understanding of flammability characteristics is imperative. Morford. v Joe Miller. 15302 (5/10/2002). Kanegsberg.. submitted to the USEPA on 7/25/2003. Ltd. OAR-2002-0064-0040. For a discussion of this report see reference no. England). Some non-flammable liquids can burn within narrow concentration ranges. However. patents with ten dealing with formulations and applications for nPB-based solvents in critical cleaning. the combustion rapidly self-extinguishes. Morford. 49 CFR 173. The flammability range is approximately 2-10 vol. Inc. The bottom line is safety. 29 CFR 1910. Data from 3M Technical Data Sheet. OAR-2002-0064-0030 and –0031. She may be reached at Barbara@bfksolutions. About the Authors Ronald L. As with other issues concerning performance. pp. LLC. 49 CFR 173. and environment. an independent consulting company specializing in critical cleaning issues. iii Code of Federal Regulations.2. IBSA. She is a chemist with over eighteen years of experience in contamination control issues. 09802 (3/26/02) and No. He holds thirty U. including the flash point. 49 CFR 173. ix Stephen M. 111-131. 8. CRC Press.%. “normal-Propyl Bromide”. eds. He can be reached at shubkin@solvon. submitted to the USEPA on 8/4/003. a provider of nPB. Chapter 1.120(c)(1) and 29 CFR 1910. These may be viewed at reference 8. available consensus standards and methods are the ones to use. Kanegsberg and E.1200(c). Shubkin is Manager of Technical Services for Poly Systems USA. Rowe (Chilworth Technology. “Enviro Tech Comment re: Section IVD Flammability”. CRC Handbook for Critical Cleaning (B. Reports No. The use of any organic solvent. . Exhibit Enviro Tech International. document –0031. When an organic solvent is the appropriate selection. ________________________________________ i Code of Federal Regulations.S. vi Richard G. 2001. A number of additional considerations. b.7. or may be obtained from R. vii Report by the German National Flammables Laboratory to the European Chemicas Bureau (ECB). ii Code of Federal Regulations. “Albemarle Corporation – Flash Point Data for nPropyl Bromide”. Inc.120(a). or any blend containing volatile organic vapors. compatibility. viii Study done under contract to the International Brominated Solvents Association. Barbara Kanegsberg is President of BFK Solutions. Further. including process specifics and other processes performed in the vicinity must also be taken into account. Shubkin. must include an analysis of potential flammability. x Ronald L. Thanks to Battalion Chief Michael Bean of the Warminster Fire Department and Fire Marshal’s office for reviewing the NFPA sections of this article. document –0031. to be meaningful. Exhibit G. it is important to critically evaluate all flammability characteristics. iv Code of Federal Regulations. safety.1200(c). Document No.

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