WPCL( 2BJZCourier 3!L  i6X@`7 @HP LaserJet 4LHPLAS4L.PRS4i6X@`7\-R @ .,., USUK 3'3'Standard6&6&StandardrJet 4Lzư 2YC EIYzz 3!L  2> Z Ye HP LaserJet 4LHPLAS4L.PRS4XP\  P6Q\-RXP"4|Jx ^;C]ddCCCdCCCCddddddddddCCY~~vCN~sk~CCCddCYdYdYCdd88d8ddddJN8ddddYYdYdCdddddCddddddddd8YYYYYY~Y~Y~Y~YC8C8C8C8ddddddddddYdddddsdXYXXXYYx|X~Y~Y|XddddddddC8C8C8C8oNd|8|H~8<|8dtddddHHJlLlLlLkN|H|8~8dddddddXXXd~8dJkN~8ddxddCddCCCWxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxNdddCYQQddddddFddddFCChhd44ddzzdddvooChdF"dhddCCzCddoddCdYds]zUvdYYCCCCz~ozoY~NYdYC8YooYdYzsdzdd~YYzozzzzNd88YYYzYzzzzCCdddddddzzzzzzzzzzzzzzzzzzzNNNNNNNdddddddddddddddddddd888888888888YYYYYYYYYYYYYYYYYYYzzzzzzzzzzzzzzzzzzzzCs~CzdYC\   pxtll\tll@\@\`LCG TimesCourierCourier BoldCG Times BoldCG Times ItalicLetter GothicCourier Italic"4|Jx ^;C]ddCCCdCCCCddddddddddCCdxN`xoCCCddCdoYoYFdo8Co8odooYNCodddYddddCdddddCddddddddo8dddddYYYYYN8N8N8N8oddddooooddpddddxodddXXYYXYYXddddddooL8N8N8N8r`o8P8N8ppoddXXYpLoNpLoNPDCopoopodXYXo8oYoNCdddoCddCCCWxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxNdddCdUUddddddFddddFCCssd44ddzzddd~ooCsdF"dsddCCzCddoddCdYds`zUvdddCCCCzozoYNYYYN8YooYdYzzdzddYYzozzzzNY88YYYzYzzzzCCdddddddzzzzzzzzzzzzzzzzzzzNNNNNNNYYYYYYYYYYYYYYYYYYYY888888888888YYYYYYYYYYYYYYYYYYYzzzzzzzzzzzzzzzzzzzzCzNzdYC\   pxtll\tll@\@\`L2 pZ%FZJ("4|Jx ^;C`ddCCCdCCCCddddddddddCCdxxxsCYoxxdoxxooCCCddCddYdY8dd88Y8ddddLL8dYYYLYdYdCdddddCddddddddd8xdxdxdxdxdYxYxYxYxYC8C8C8C8dddddddddoYxddddoYdxdxdxdxdXXYYxxXxYxYxXddddddddD8C8C8C8dYYp8pHo8p8p8dxddddxLxLxLdLdLdLdLpHp8o8ddddddoYpLpLpLdo8dxLdLo8oYoYxddCddCCCWxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxxNdddCd]]ddddddFddddFCCddd88ddzzdddkddCddF"ddddCCzCdzdoddCdYds]zUvdYYCCCCzzzozoYzNoYdYC8YooYdYzzdzddoYoYzzozzzzNd88YYYzYzzzzCCdddddddzzzzzzzzzzzzzzzzzzzNNNNNNNdddddddddddddddddddd888888888888YYYYYYYYYYYYYYYYYYYzzzzzzzzzzzzzzzzzzzzCszzCozdYC\   pxtll\tll@\@\`L6_8wC;,WXw PE37XPlr5ddd,  d6X@`7@s4ddd,pd `7ti7zC;,(Xz_ pi7Xj6uC;,,PXu&_ x7XX\l#HHH,<{DH H@7@r5ddd,JPNd6Nhez7H 3'3'Standard6&6&StandardrJet 4Lzư  +  b  !3 3 )08;;@HPCCX`Distr.  !3 3 )08;;@HPCCX`RESTRICTED  !3 3 )08;;@HPCCX`ST/SG/AC.10/R.482  !3 3 )08;;@HPCCX`3 October 1994  !3 3 )08;;@HPCCX`Original: ENGLISH  COMMITTEE OF EXPERTS ON THE TRANSPORT OF DANGEROUS GOODS (Eighteenth session, Geneva, 28 November 7 December 1994, agenda item 3 (b))  Yb m, RATIONALIZATION OF THE MANUAL OF TEST AND CRITERIA 9AMENDMENT TO DIVISION 4.2  'Transmitted by the European Chemical Industry Council (CEFIC)  Introduction With respect to the decision of the subcommittee on document ST/SG/AC.10/C.3/R.385/Rev.1 amendments are necessary in the United Kingdom document ST/SG/AC.10/C.3/R.475, chapter 33.3 Division 4.2. In this document CEFIC proposes the revised Division 4.2 text for the Test Manual. Proposal The following revised Division 4.2 text (given in square brackets) should be added to the Test Manual:  Y 33.3 Division 4.2  Y! 33.3.1 Substances liable to spontaneous combustion  Y# 33.3.1.1 Purpose 33.3.1.1.1 This sub-section presents the United Nations scheme for the classification of substances liable to spontaneous combustion of Division 4.2 (see sub-section 14.3 of the GE.94 /a:\STR482E ()))bb 4 +#  bN ST/SG/AC.10/R.482 page 2  NN  Recommendations). The text should be used in conjunction with the classificafion principles given in paragraphs 14.3.2 and 14.3.3 of the Recommendations and the test prescriptions given here in 33.2.1.4 to 33.2.1.6, and in sub-sections 14.5.3 to 14.5.5 of the Recommendations. 33.3.1.1.2 The test procedures are intended to identify two types of substances with spontaneous combustion properties:  Y (a)$$Substances, including mixtures and solutions (liquid or solid) which, even in small quantities, ignite within five minutes of coming in contact with air. These substances are the most liable to spontaneous combustion and are called pyrophoric substances.  Y (b)$$Other substances which, in contact with air and without an energy supply, are liable to self-heating. These substances will ignite only when in large amounts (kilograms) and after long periods of time (hours or days) and are called self-heating substances. 33.3.1.1.3 The test procedures outlined here adequataly assess the relative hazard of substances liable to spontaneous combustion so that an appropriate classification for transport can be made.  Y@ 33.3.1.2 Scope 33.3.1.2.1 Products offered for transport should be subjected to the classification procedures as set out in paragraphs 14.3.2 and 14.3.3 of the Recommendations, unless it is impracticable (e.g. because of the physical properties) to perform the tests. The classification procedure should be undertaken before a product is offered for transport.  Y! 33.3.1.3 Classification procedure for substances liable to spontaneous combustion 33.3.1.3.1 Pyrophoric solids A test is performed to determine if a solid ignites within five minutes of coming in contact with air. The recommended test method is given here, in 33.2.1.4 and in section 14.5.3 of the Recommendations. Whether a substance is a pyrophoric solid of Division 4.2 is decided on the basis of the test result. Packing Group I is assigned to all pyrophoric solids. *+++Ԍ N $$| |  ',,/7?44GOWST/SG/AC.10/R.482 $$| |  ',,/7?44GOWpage 3 33.3.1.3.2 Pyrophoric liquids A test is performed to determine if a liquid ignites when added to an inert carrier and exposed to air for five minutes. If no ignition occurs then the second part of the test is performed to determine if it chars or ignites a filter paper. The recommended test method is given here in 33.2.1.5 and in section 14.5.4 of the Recommendations. Whether a substance is a pyrophoric liquid of Division 4.2 is decided on the basis of the test result. Packing Group I is assigned to all pyrophoric liquids. 33.3.1.3.3 Self-heating substances [33.3.1.3.3.1 Tests are performed to determine if substances in a 25 mm or 100 mm sample cube, at test temperatures of 100C, 120C or 140C, undergo spontaneous ignition or a 60$C rise in temperature over the oven temperature within 24 hours. The classification scheme is illustrated in figure 14.4 of the Recommendations. These criteria are based on the self-ignition temperature of charcoal, which is 50C for a sample cube of 27 m3. Substances with a temperature of spontaneous combustion higher than 50C for a volume of 27 m3 should not be assigned to Division 4.2. The recommended test method is given here in 33.2.1.6 and in section 14.5.5 of the Recommendations. 33.3.1.3.3.2 If self-heating does not occur with the substance in a 100 mm sample cube at 140C then the substance is not a self-heating substance of Division 4.2. 33.3.1.3.3.3 If self-heating occurs with the substance in a 100 mm sample cube at 140C then a test with the substance in a 25 mm sample cube should be performed at 140C to determine if it should be assigned to Packing Group II. 33.3.1.3.3.4 If self-heating occurs at 140C with the substance in a 100 mm sample cube, but not a 25 mm sample cube, then a test with the substance in a 100 mm sample cube should be performed: X$$at 120C if it is to be transported in packagings of not more than 3 m3 volume; or if selfheating occursƟ#$ X$$at 100C if the substance is to be transported in packagings of not more than 450 litres volume.Ɵ#$ Whether Packing Group III of Division 4.2 is assigned or the substance is not a self-heating substance of Division 4.2, in the packaging to be used, is decided on the basis of the test results. 33.3.1.3.3.5 Self-reactive substances type G which give a positive result with this test method may be classified in Division 4.2 (see 20.2.6).] 0F1F1F1Ԍ ę N ST/SG/AC.10/R.482 page 4  YH 33.3.1.4 Test N.2: Test method for pyrophoric solids  Yz 33.3.1.4.1 Introduction The ability of a solid to ignite on contact with air is tested by exposure to air and determining the time to ignition.  Y 33.3.1.4.2 Apparatus and materials No special laboratory equipment is required.  YV 33.3.1.4.3 Procedure One to two ml of the powdery substance to be tested should be poured from about 1 m height onto a non- combustible surface and it is observed whether the substance ignites during dropping or within 5 minutes of settling. This procedure should be performed six times unless a positive result is obtained earlier.  Y 33.3.1.4.4 Test criteria and method of assessing results If the sample ignites in one of the tests, the substance should be considered pyrophoric and should be classified in Division 4.2.  Yz 33.3.1.4.5 Examples of results   yq!dddy  Y  Substance| |  ',,/7?44GTime to ignition <<_g Result $$| |  ',,/7?44G (s)   y#dddjy  W" [Editorial note: Examples of results required]  2# y%dddy  YE# 33.3.1.5 Test N.3: Test method for pyrophoric liquids  Yw% 33.3.1.5.1 Introduction The ability of a liquid to ignite, when added to an inert carrier and exposed to air, or to char or ignite a filter paper on contact with air, is determined. )+++Ԍ N $$| |  ',,/7?44GOWST/SG/AC.10/R.482 $$| |  ',,/7?44GOWpage 5  YH 33.3.1.5.2 Apparatus and Materials A porcelain cup of about 100 mm diameter and some diatomaceous earth or silica gel is required for the first part of the test, and small pore size, filter paper for the second part.  Y 33.3.1.5.3 Procedure #Xw PE37WXP# 33.3.1.5.3.1 A porcelain cup of about 100 mm diameter should be filled with diatomaceous earth or silica gel at room temperature to a height of about 5 mm. Approximately 5 ml of the liquid to be tested should be poured into the prepared porcelain cup and it is observed if the substance ignites within 5 minutes. This procedure should be performed six times unless a positive result is obtained earlier. If a negative result is obtained then the procedure in 33.3.1.5.3.2 should be followed. 33.3.1.5.3.2 A 0.5 ml test sample should be delivered from a syringe to an indented dry filter paper. The test should be conducted at 25  2C and a relative humidity of 50  5%. Observations are made to see if ignition or charring occurs on the filter paper within five minutes of addition of the liquid. This procedure should be performed three times using fresh filter paper each time unless a positive result is obtained earlier.  Y, 33.3.1.5.4 Test criteria and method of assessing results If the liquid ignites in the first part of the test, or if it ignites or chars the filter paper, it should be considered to be pyrophoric and should be classified in Division 4.2.  Y 33.3.1.5.5 Examples of results   #wH|@E{D@#y"ddd>y  l#  Substance| |  ',,/7?44GEffect ofWEffect ongResult  l# $$| |  ',,/7?44Gexposure to airWfilter paper  +! y#dddy  l#>! Di-ethyl aluminium chloride/isopentane (10/90)?44GNo ignitionWNo charring gNot 4.2  l#! Di-ethyl aluminium chloride/isopentane (15/85)?44GNo ignition WCharringg4.2  l#" Di-ethyl aluminium chloride/isopentane (95/5)?44GNo ignitionWCharringg4.2  l#B# Tri-ethyl aluminium/heptane (10/90)7?44GNo ignition WNo charringgNot 4.2  l## Tri-ethyl aluminium/heptane (15/85)7?44GNo ignitionWCharring g4.2  l#$ Tri-ethyl aluminium/heptane (95/5)7?44GNo ignitionWCharringg4.2  % y(dddy#d  @E @#  Y& #Xw PE37WXP#33.3.1.6 Test N.4: Test method for self-heating substances  Y( 33.3.1.6.1 Introduction The ability of a substance to undergo oxidative self-heating is determined by exposure of it to air at temperatures of 100C, 120C or 140C in a 25 mm or 100 mm wire mesh cube. a-F1F1F1   4ST/SG/AC.10/R.482 page 6  Y #Xw PE37WXP#33.3.1.6.2 Apparatus and materials The following apparatus is required. X$$a hot-air circulating type of oven with an inner volume of more than 9 litres and a capable of controlling the internal temperature at 100C, 120 or 140C  2$C;Ɵ#$ X$$cubic sample containers of 25 mm and 100 mm side, made of stainless steel net with a mesh opening of 0.05 mm, with their top surface open; andƟ#$ X$$Chromel-Alumel thermocouples of 0.3 mm diameter; one placed in the centre of the sample and another between the sample container and the oven wall.Ɵ#$ Each sample container should be housed in a cubic container cover made from a stainless steel net with a mesh opening of 0.60 mm, and slightly larger than the sample container. In order to avoid the effect of air circulation, this cover is installed in a second stainless steel cage, made from a net with a mesh size of 0.595 mm and 150 x 150 x 250 mm in size.  Y 33.3.1.6.3 Procedure The sample, powder or granular, in its commercial form, should be filled to the brim of the sample container and the container tapped several times. If the sample settles, more is added. If the sample is heaped it should be levelled to the brim. The container is housed in the cover and hung at the centre of the oven. The oven temperature should be raised to 140$C and kept there for 24 hours. The temperature of the sample and of the oven should be recorded continiously. The first test */ should be conducted with a 100 mm cube sample. [A positive result is obtained if spontaneous ignition occurs or if the temperature of the sample exceeds the oven temperature by 60$C. If a negative result is obtained, no further test is necessary. If a positive result is obtained, a second test should be conducted at 140$C with a 25 mm cube sample to determine whether or not Packung Group II should be assigned. If a positive result is obtained at 140$C with the substance in a 100 mm sample cube, but not a 25 mm sample cube, then an additional test with the substance in a 100 mm sample cube should be performed: X$$at 120C if the substance is to be transported in packagings of not more than 3 m3 volume; orƟ#$ X$$at 100C if the substance is to be transported in packagings of not more than 450 litres volume.] Ɵ#$ */ If it is expected that a positive result will be obtained using a 25 mm cube sample then, for safety and environmental protection, the first test may be performed with a 25 mm cube sample. lf a positive result is obtained then a test with a 100 mm cube sample is not necessary. 33.3.1.6.4.3 Packing Group II should be assigned to self-heating substances which give a positive result in a test using a 25 mm sample cube at 140C. -F1F1F1   $$| |  ',,/7?44GOST/SG/AC.10/R.482 $$| |  ',,/7?44GOpage 7  Y 33.3.1.6.4 Test criteria and method of assessing results [33.3.1.6.4.1 A positive result is obtaibed if spontaneous ignition occurs or if the temperature of the sample exceeds the oven temperature by 60C during the 24 hour testing time. Otherwise, the result is considered negative. 33.3.1.6.4.2 A substance should not be classified in Division 4.2 if:  Y (a)X$$A negative result is obtained in a test using a 100 mm cube sample at 140C.Ɵ#$  Y (b)X$$A negative result is obtained in a test using a 25 mm cube sample at 140C, a negative result is obtained in a test using a 100 mm cube sample at 120C and the substance is to be transported in packaging with a volume not more than 3 m3.Ɵ#$  Y{ (c) X$$A negative result is obtained in a test using a 25 mm cube sample at 140C, a negative result is obtained in a test using a 100 mm cube sample at 100C and the substance is to be transported in packaging with a volume not more than 450 litres.Ɵ#$ 33.3.1.6.4.4 Packing Group III should be assigned to self-heating substances if.  Y (a)X$$A negative result is obtained in a test using a 25 mm cube sarnple at 140C and a positive result is obtained in a test using a 100 mm cube sample at 100C.Ɵ#$  Y  (b) X$$A negative result is obtained in a test using a 25 mm cube sample at 140C, a positive result is obtained in a test using a 100 mm cube sample at 120C and the substance is to be transported in packaging with a volume of more than 450 liters.Ɵ#$  Y9 (c)X$$A negative result is obtained in a test using a 25 mm cube sample at 140C, a positive result is obtained in a test using a 100 mm cube sample at 140C and the substance is to be transported in packaging with a volume of more than 3 m3.] Ɵ#$  Y  33.3.1.6.5 Examples of results   ! yv$dddy  Y"  Substance| |  ',,/7?44GCubeOMaximum temperature nResult  Y#  $$| |  ',,/7?44GsizeOreached  Y|$ $$| |  ',,/7?44G(mm)O( C)  e% y*(dddP y  W^& [Editorial note: Examples of results required.]  ) y +ddd y