Class 4 Learning Tool T-990

1. Class 4 Learning Tool T-990 This work has been produced by DGL (Aust) Pty Ltd This Learner’s Tool is about the skills and knowledge required to store and warehouse Class 4 at DGL (Aust) facilities. This includes operational requirements for the safe and efficient control of all functions and effective management of hazardous situations.

2. Before you get started • It is important that you complete all sections in this learning tool as it has been designed so that • You can abide by the procedures of our organization. • You can apply what you have learnt in this package in your day to day activities • This Learning Tool is designed to be relevant only to DGL (Aust) Pty Ltd employees and only applied whilst employed with DGL (Aust) Pty Ltd • You may have already acquired knowledge in the area identified in this package as you may have completed some specialized training. Or you may have been working within the industry for some time. Should you identify any improvement opportunities in the information contained in this package or have difficulties completing the package please contact National Training and Compliance Manager DGL (Aust) Pty Ltd PO BOX 1594 EAGLE FARM QLD 4009 Ph 07 3868 1001 Fax 07 3868 1055

3. Definition of a Class 4 • Class 4 is divided into three divisions as follows: • Division 4.1 Flammable solids • Solids which, under conditions encountered in transport, are readily combustible or may cause or contribute to fire through friction; self-reactive substances which are liable to undergo a strongly exothermic reaction; solid desensitized explosives which may explode if not diluted sufficiently; • Division 4.2 Substances liable to spontaneous combustion • Substances which are liable to spontaneous heating under normal conditions encountered in transport, or to heating up in contact with air, and being then liable to catch fire; • Division 4.3 Substances which in contact with water emit flammable gases • Substances which, by interaction with water, are liable to become spontaneously flammable or to give off flammable gases in dangerous quantities. • (Note 1) • Note (1) Source the Australian Dangerous Goods Code 7th Edition page 61

4. Properties of Class 4 • Division 4.1 • Flammable Solids Solids which may cause fire through friction are classified in Division 4.1 by analogy with existing entries (e.g. matches) until definitive criteria are established. • Self Reactive Substances The decomposition of self-reactive substances can be initiated by heat, contact with catalytic impurities (e.g. acids, heavy-metal compounds, bases), friction or impact. The rate of decomposition increases with temperature and varies with the substance. Decomposition, particularly if no ignition occurs, may result in the evolution of toxic gases or vapours. For certain self-reactive substances, the temperature must be controlled. Some self-reactive substances may decompose explosively, particularly if confined. This characteristic may be modified by the addition of diluents or by the use of appropriate packagings. Some self-reactive substances burn vigorously. Self-reactive substances are, for example, some compounds of the types listed below: • (a) Aliphatic azo compounds (-C-N=N-C-); and • (b) Organic azides (-C-N3); and • (c) Diazonium salts (-CN2+Z-); and • (d) N-nitroso compounds (-N-N=O); and • (e) Aromatic sulphohydrazides (-SO2-NH-NH2). • Solid desensitized explosivesare explosive substances which are wetted with water or alcohols or are diluted with other substances, to form a homogeneous solid mixture to suppress their explosive properties. Entries in the Dangerous Goods List for solid desensitized explosives are: • UN 1310, UN 1320, UN 1321, UN 1322, UN 1336, UN 1337, UN 1344, UN 1347, UN 1348, UN 1349, UN 1354, UN 1355, UN 1356, UN 1357, UN 1517, UN 1571, UN 2555, UN 2556, UN 2557, UN 2852, UN 2907, UN 3317, UN 3319, UN 3344, UN 3364, UN 3365, UN 3366, UN 3367, UN 3368, UN 3369, UN 3370,UN 3376, UN 3380 and UN 3474. • (Note 2)

5. Properties of Class 4 continued • Division 4.2 • Pyrophoric substances, which are substances, including mixtures and solutions (liquid or solid), which even in small quantities ignite within five minutes of coming in contact with air. These are the Division 4.2 substances are the most liable to spontaneous combustion; and • Self-heating substances, which are substances, other than pyrophoric substances, which in contact with air without 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). • (Note 3) • Division 4.3 • Certain substances in contact with water may emit flammable gases that can form explosive mixtures with air. Such mixtures are easily ignited by all ordinary sources of ignition, for example naked lights, sparking handtools or unprotected light bulbs. The resulting blast wave and flames may endanger people and the environment. The test method referred below • (a) spontaneous ignition takes place in any step of the test procedure; or • (b) there is an evolution of a flammable gas at a rate greater than 1 litre per kilogram of the substance per hour is used to determine whether the reaction of a substance with water leads to the development of a dangerous amount of gases which may be flammable. This test method should not be applied to pyrophoric substances. • (Note 4) • Note (2) Source the Australian Dangerous Goods Code 7th Edition page 62, 63 & 71 • Note (3) Source the Australian Dangerous Goods Code 7th Edition page 71 • Note (4) Source the Australian Dangerous Goods Code 7th Edition page 73

6. Class 4 Labels Note 1 Note (1) Source the Australian Dangerous Goods Code 7th Edition page 426

7. Classification of Class 4 Products • Division 4.1 • Classification of flammable solids • For readily combustible solids (other than metal powders), packing group II must be assigned if the burning time is less than 45 s and the flame passes the wetted zone. Packing group II must be assigned to powders of metal or metal alloys if the zone of reaction spreads over the whole length of the sample in five minutes or less. • For readily combustible solids (other than metal powders), packing group III must be assigned if the burning time is less than 45 s and the wetted zone stops the flame propagation for at least four minutes. Packing group III must be assigned to metal powders if the reaction spreads over the whole length of the sample in more than five minutes but not more than ten minutes. • Classification of self-reactive substances • Self-reactive substances are classified into seven types according to the degree of danger they present. The types of self-reactive substance range from type A, which may not be accepted for transport in the packaging in which it is tested, to type G, which is not subject to the provisions for self-reactive substances of Division 4.1. The classification of types B to F is directly related to the maximum quantity allowed in one packaging. • Classification of Solid Desensitized Explosives • Substances that: • (a) have been provisionally accepted into Class 1 according to Test Series 1 and 2 but exempted from Class 1 by Test Series 6; and • (b) are not self-reactive substances of Division 4.1; and • (c) are not substances of Class 5; are also assigned to Division 4.1. Though not desensitized explosives, UN 2956, UN 3241, UN 3242 and UN 3251 are such entries that are assigned to Division 4.1. • (Note 1)

8. Classification of Class 4 continued • Division 4.2 • Packing group I must be assigned to all pyrophoric solids and liquids. • Packing group II must be assigned to self-heating substances which give a positive result in a test using a 25 mm sample cube at 140 °C. • Packing group III must be assigned to self-heating substances if: • (a) a positive result is obtained in a test using a 100 mm sample cube at 140 °C and a negative result is obtained in a test using a 25 mm cube sample at 140 °C and the substance is to be transported in packages with a volume of more than 3 m3; • (b) a positive result is obtained in a test using a 100 mm sample cube at 140 °C and a negative result is obtained in a test using a 25 mm cube sample at 140 °C, a positive result is obtained in a test using a 100 mm cube sample at 120 °C and the substance is to be transported in packages with a volume of more than 450 litres; • (c) a positive result is obtained in a test using a 100 mm sample cube at 140 °C and a negative result is obtained in a test using a 25 mm cube sample at 140 °C and a positive result is obtained in a test using a 100 mm cube sample at 100 °C. • (Note 2)

9. Classification of Class 4 continued • Division 4.3 • Packing group I must be assigned to any substance which reacts vigorously with water at ambient temperatures and demonstrates generally a tendency for the gas produced to ignite spontaneously, or which reacts readily with water at ambient temperatures such that the rate of evolution of flammable gas is equal to or greater than 10 litres per kilogram of substance over any one minute. • Packing group II must be assigned to any substance which reacts readily with water at ambient temperatures such that the maximum rate of evolution of flammable gas is equal to or greater than 20 litres per kilogram of substance per hour, and which does not meet the criteria for packing group I. • Packing group III must be assigned to any substance which reacts slowly with water at ambient temperatures such that the maximum rate of evolution of flammable gas is equal to or greater than 1 litre per kilogram of substance per hour, and which does not meet the criteria for packing groups I or II. • (Note 3) • Note (1) Source the Australian Dangerous Goods Code 7th Edition page 62, 64 & 71 • Note (2) Source the Australian Dangerous Goods Code 7th Edition page 72 • Note (3) Source the Australian Dangerous Goods Code 7th Edition page 73

10. Temperature Control Requirements • Division 4.1 • Self-reactive substances are subject to temperature control in transport if their self accelerating decomposition temperature (SADT) is less than or equal to 55 °C. Test methods for determining the SADT are given in the Manual of Tests and Criteria, Part II, section 28. The test selected must be conducted in a manner which is representative, both in size and material, of the package to be transported. • (Note 1) • Note (1) Source the Australian Dangerous Goods Code 7th Edition page 68

11. Storage • GENERAL REQUIREMENTS - PACKAGED • Except for storage cabinets, stores for packages of dangerous goods shall comply with the following requirements and recommendations, as appropriate. • (a) Packages shall be kept in a manner such that they cannot fall and cause spillage outside the compound. • Packages should be kept at least 600 mm from the inner edge of the bund wall, or restraints provided to prevent falls or spills outside the compound. • (b) Clear access shall be available to the store. • (c) One or more safety showers, eyewash facilities and water for the washing of hands shall be provided within 10 m of, but not nearer than 2 m to, any area where packages are opened and their contents transferred, the number, location and type of equipment being based on risk assessment. • Such eyewash facilities and safety showers shall comply with ANSI Z358. • (d) All relevant requirements of Operational & Personal Safety of the AS/NZS 3833:2007 shall apply • (e) Where the dangerous goods could generate combustible dusts or flammable vapours or gases, a Hazardous Zone, as described in AS/NZS 2430 series, might exist. In such a case, all equipment used in the Hazardous Zone shall be suitable for use in that Zone. • (f) Any forklift truck used in Hazardous Zone shall comply with the relevant requirements of AS 2359.12 for use in the relevant Zone. Any forklift trucks or similar vehicles that are not approved for use in Zone 2, or that do not comply with AS 2359.12, shall not be used unless both the store and the vehicle comply with all of the requirements of Appendix E of AS/NZS 3833:2007.

12. Storage Continued • GENERAL REQUIREMENTS – IBC’S • Intermediate bulk containers (IBCs) of up to 1.6 m3 capacity may be stored in a package store provided that— • (a) they are not connected to any piping or product delivery system; • (b) the ventilation and spillage control provisions are adequate to cater for the quantity of IBCs being stored; • (c) the IBCs are stored at least 1 m from the bund or edge of the store, unless splash shields or baffles constructed from compatible, non-combustible materials are used; • (d) they comply with the ADG Code; and • (e) the IBCs are not stacked more than two high unless purpose-built racking is provided. • All storage areas shall be appropriately secured against access by unauthorized persons. Any additional regulatory requirements, e.g. those for ‘security sensitive’ or ‘high consequence dangerous goods’, shall also apply. • (Note 1) • Note (1) Source the AS/NZS 3833:2007 - The storage and handling of mixed dangerous goods in packages and intermediate bulk containers page 35 & 36 • Note (1) Source the Australian AS 1940—2004 The storage and handling of Flammable and combustible liquids page 51

13. Management of Leaks • General • Every endeavour shall be made to prevent leaks or spills, and to control them if they do occur. Clean-up action shall be initiated immediately. Leaked or spilled dangerous goods shall be kept and disposed of in accordance with Local & State legislation. • Clean-up materials and equipment • In order to deal with leaks and spills, cleanup equipment, chemicals for neutralizing or decontaminating spills, and absorbent materials shall be maintained at every premises on which dangerous goods are kept or handled. Sufficient neutralizer should be available to treat the contents of the largest container stored. • The following is a typical list of such materials and equipment: • (a) Adequate quantities of absorbent material, e.g. sand, fuller’s earth or suitable proprietary substances. • (b) Calcium hydroxide (hydrated lime), for use on acidic spills. • (c) Sodium bisulfate, for use with alkaline spills. • (d) Sodium carbonate (soda ash), for use on acidic spills. • (e) Crushed calcium carbonate (limestone), for use on acidic spills. • (f) A sufficient number of resealable waste-recovery containers, e.g. drums, made of materials compatible with the substances being kept and appropriately marked as being for emergency use only. • NOTE: A means of labelling the recovery containers should also be provided. • (g) Portable pumps and decanting equipment. • NOTE: Petrol-powered pumps are unsuitable for use with flammable liquids. • (h) Shovel (non-sparking if flammable liquids are stored) • (i) Yard brooms.

14. Management of Leaks Continued • Actions for dealing with leaks and spills • At every occurrence of a leak or spill, the emergency plan shall be implemented and consideration shall be given to notifying the emergency services. • NOTE: Emergency services should be notified when— • (a) the dangerous goods have spread, or have the potential to spread, beyond the boundary of the installation; • (b) it is beyond the resources of the occupiers to clean up the spill or leak effectively and safely; • (c) the protective equipment is inadequate for dealing with the situation; • (d) staff are not experienced in dealing with the situation; or • (e) staff and the public are, or could potentially be, placed at risk. • Leaking packages shall be positioned in such a manner as to stop or minimize the leak and, if necessary, shall be moved to a safe location. The package should either be placed in a suitable container, e.g. a plastic bag or an oversize drum, or its contents should be transferred to a clean packaging. The exterior of such clean packaging shall be clearly labelled. • Small spills on the floor, or on the walls or structures of a building, should be collected, absorbed, or diluted, as appropriate. Where spills are absorbed, the used absorbent shall be placed in a suitable waste container for disposal in accordance with Local & State legislation as soon as is practicable. • Note (1) • Note (1) Source the AS/NZS 3833:2007 - The storage and handling of mixed dangerous goods in packages and intermediate bulk containers page 58

15. Personal Habits • The following directions shall be followed by all persons whose work involves handling packaged dangerous goods: • (a) Do not introduce, keep, prepare or consume any food or drink, or use tobacco, in any area where dangerous goods are kept or handled. • (b) After handling any dangerous goods, always wash your hands before eating, drinking, smoking or using the toilet, and after work. • (c) Immediately attend to injuries caused by contact, or suspected contact, with dangerous goods. • The above directions, or wording to the same effect, shall be prominently displayed in the work area. • Note (1) • Note (1) Source the AS/NZS 3833:2007 - The storage and handling of mixed dangerous goods in packages and intermediate bulk containers page 54

16. First Aid • A first aid station shall be provided in a clean area. It shall comprised of, as a minimum, an appropriate first aid kit and first aid instructions, e.g. MSDSs, for all dangerous goods being kept or handled on the premises. • It is recommended that— • (a) at least one person on the premises is trained in first aid; and • (b) a list of persons trained in and responsible for administering first aid should be shown on all notice boards on the premises. • Note (1) • Note (1) Source the AS/NZS 3833:2007 - The storage and handling of mixed dangerous goods in packages and intermediate bulk containers page 55

17. Test your knowledge • Through the following slides you will be asked an number of questions to show that you have understood the content of this learning tool • Please record your answer on the training form F-260. • You will be required to submit the answers to the DGL HSEQ unit

18. Question 1 • What are the 3 Divisions of Class 4? • a) Flammable solids, Self Reactive Substances & Solid desensitized explosives • b) Self-heating substances, Pyrophoric substances & Substances which in contact with water emit flammable gases • c) Flammable solids, Substances liable to spontaneous combustion & Substances which in contact with water emit flammable gases • d) Substances liable to spontaneous combustion, Substances which in contact with water emit flammable gases & Self Reactive Substances

19. Question 2 • In most cases of the Class 4 placard what is the most common colour of the writing? • a) White • b) Grey • c) Red • d) Black

20. Question 3 • What is the Division and what type of substance that can ignite within 5 minutes once it has come into contact with the air? • a) 4.3 - Substances which in contact with water emit flammable gases • b) 4.2 - Pyrophoric substances • c) 4.1 - Solid desensitized explosives • d) 4.2 - Self-heating substances

21. Question 4 • What is the main way for classifying Class 4? • a) Via Packing Group • b) Via the SADT • c) Via a UN code • d) Via Reactivity

22. Question 5 • At what SADT temperature are Self-reactive substances subject to controlled temperature for transport? • a) less than or equal to 75 °C • b) less than or equal to 65 °C • c) less than or equal to 55 °C • d) less than or equal to 85 °C

23. Question 6 • In what manner should packages be kept? • a) in a manner such that they cannot fall and cause spillage outside the compound • b) in a manner such that they can fall and cause spillage outside the compound • c) in a manner such that they are damaged and cause spillage outside the compound • d) in a manner such that they cannot not fall but have caused spillage outside the compound

24. Question 7 • What should be done with a small spill on the floor or walls of a building? • a) Should be collected, absorbed, or diluted, and dumped in the bin • b) Should be collected, absorbed, or diluted, placed in a suitable waste container for disposal • c) Should be collected, absorbed, or diluted, placed back in the drum it has leaked from ready for disposal • d) None of the Above

25. Question 8 • Neutralizer should be available to treat the contents a spill, how much should you have? • a) Not really compulsory to have neutralizer on site at any given time • b) Enough to treat 200 litres • c) Enough to treat a small spill as you have to contact emergency services for a large one • d) Enough to treat the largest container stored

26. Additional information • For more information on Class 4 products the following sources may be of assistance • Australian Dangerous Goods Code 7th Edition • Available to all DGL employees via the company’s intranet • AS/NZS 3833:2007 - The storage and handling of mixed dangerous goods in packages andintermediate bulk containers • Available to all DGL employees via the company’s intranet