Transcript
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ST/SG/AC.10/11/Rev.6
Recommendations on the
TRANSPORT OF DANGEROUS GOODS Manual of Tests and Criteria
Sixth revised edition
UNITED NATIONS New York and Geneva, 2015
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38.3
Lithium metal and lithium ion batteries
38.3.1
Purpose
This section presents the procedures to be followed for the classification of lithium metal and lithium ion cells and batteries (see UN Nos. 3090, 3091, 3480 and 3481, and the applicable special provisions of Chapter 3.3 of the Model Regulations). 38.3.2
Scope
38.3.2.1 All cell types shall be subjected to tests T.1 to T.6 and T.8. All non-rechargeable battery types, including those composed of previously tested cells, shall be subjected to tests T.1 to T.5. All rechargeable battery types, including those composed of previously tested cells, shall be subjected to tests T.1 to T.5 and T.7. In addition, rechargeable single cell batteries with overcharge protection shall be subjected to test T.7. A component cell that is not transported separately from the battery it is part of needs only to be tested according to tests T.6 and T.8. A component cell that is transported separately from the battery shall be subjected to tests T.1 to T.6 and T.8. 38.3.2.2 Lithium metal and lithium ion cells and batteries shall be subjected to the tests, as required by special provisions 188 and 230 of Chapter 3.3 of the Model Regulations prior to the transport of a particular cell or battery type. Cells or batteries which differ from a tested type by: (a)
For primary cells and batteries, a change of more than 0.1 g or 20% by mass, whichever is greater, to the cathode, to the anode, or to the electrolyte;
(b)
For rechargeable cells and batteries, a change in nominal energy in Watt-hours of more than 20% or an increase in nominal voltage of more than 20%; or
(c)
A change that would lead to failure of any of the tests,
shall be considered a new type and shall be subjected to the required tests. NOTE: The type of change that might be considered to differ from a tested type, such that it might lead to failure of any of the test results, may include, but is not limited to: (a)
A change in the material of the anode, the cathode, the separator or the electrolyte;
(b)
A change of protective devices, including hardware and software;
(c)
A change of safety design in cells or batteries, such as a venting valve;
(d)
A change in the number of component cells;
(e)
A change in connecting mode of component cells; and
(f)
For batteries which are to be tested according to T.4 with a peak acceleration less than 150 gn, a change in the mass which could adversely impact the result of the T.4 test and lead to a failure.
In the event that a cell or battery type does not meet one or more of the test requirements, steps shall be taken to correct the deficiency or deficiencies that caused the failure before such cell or battery type is retested.
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38.3.2.3
For the purposes of classification, the following definitions apply:
Aggregate lithium content means the sum of the grams of lithium content contained by the cells comprising a battery. Battery means two or more cells or batteries which are electrically connected together and fitted with devices necessary for use, for example, case, terminals, marking or protective devices. Units which have two or more cells that are commonly referred to as “battery packs”, “modules” or “battery assemblies” having the primary function of providing a source of power to another piece of equipment are for the purposes of the Model Regulations and this Manual treated as batteries. See definitions for "cell" and "single cell battery". Button cell or battery means a round small cell or battery when the overall height is less than the diameter. Cell means a single encased electrochemical unit (one positive and one negative electrode) which exhibits a voltage differential across its two terminals, and may contain protective devices. See definitions for battery and single cell battery. Component cell means a cell contained in a battery. A component cell is not to be considered a single cell battery. Cycle means one sequence of fully charging and fully discharging a rechargeable cell or battery. Disassembly means a vent or rupture where solid matter from any part of a cell or battery penetrates a wire mesh screen (annealed aluminium wire with a diameter of 0.25 mm and grid density of 6 to 7 wires per cm) placed 25 cm away from the cell or battery. Effluent means a liquid or gas released when a cell or battery vents or leaks. Fire means that flames are emitted from the test cell or battery. First cycle means the initial cycle following completion of all manufacturing processes. Fully charged means a rechargeable cell or battery which has been electrically charged to its design rated capacity. Fully discharged means either: a primary cell or battery which has been electrically discharged to remove 100% of its rated capacity; or a rechargeable cell or battery which has been electrically discharged to its endpoint voltage as specified by the manufacturer. Large battery means a lithium metal battery or lithium ion battery with a gross mass of more than 12 kg. Large cell means a cell with a gross mass of more than 500 g. Leakage means the visible escape of electrolyte or other material from a cell or battery or the loss of material (except battery casing, handling devices or labels) from a cell or battery such that the loss of mass exceeds the values in Table 38.3.1. Lithium content is applied to lithium metal and lithium alloy cells and batteries, and for a cell means the mass of lithium in the anode of a lithium metal or lithium alloy cell, which for a primary cell is measured when the cell is in an undischarged state and for a rechargeable cell is measured when the cell is fully charged. The lithium content of a battery equals the sum of the grams of lithium content contained in the component cells of the battery. - 425 -
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Lithium ion cell or battery means a rechargeable electrochemical cell or battery in which the positive and negative electrodes are both intercalation compounds (intercalated lithium exists in an ionic or quasi-atomic form with the lattice of the electrode material) constructed with no metallic lithium in either electrode. A lithium polymer cell or battery that uses lithium ion chemistries, as described herein, is regulated as a lithium ion cell or battery. Mass loss means a loss of mass that exceeds the values in Table 38.3.2.2 below. Table 38.3.1: Mass loss limit Mass M of cell or battery M<1g 1 g M 75 g M > 75 g NOTE:
Mass loss limit 0.5% 0.2% 0.1%
In order to quantify the mass loss, the following procedure is provided:
Mass loss (%)
M 1 M 2 M1
u 100
where M1 is the mass before the test and M2 is the mass after the test. When mass loss does not exceed the values in Table 38.3.1, it shall be considered as "no mass loss". Nominal energy or Watt-hour rating, expressed in watt-hours, means the energy value of a cell or battery determined under specified conditions and declared by the manufacturer. The nominal energy is calculated by multiplying nominal voltage by rated capacity expressed in ampere-hours. Nominal voltage means the approximate value of the voltage used to designate or identify a cell or battery. Open circuit voltage means the voltage across the terminals of a cell or battery when no external current is flowing. Primary cell or battery means a cell or battery which is not designed to be electrically charged or recharged. Prismatic cell or battery means a cell or battery whose ends are similar, equal and parallel rectilinear figures, and whose sides are parallelograms. Protective devices means devices such as fuses, diodes and current limiters which interrupt the current flow, block the current flow in one direction or limit the current flow in an electrical circuit. Rated capacity means the capacity, in ampere-hours or milliampere-hours, of a cell or battery as measured by subjecting it to a load, temperature and voltage cut-off point specified by the manufacturer. NOTE: capacity:
The following IEC standards provide guidance and methodology for determining the rated
(1) IEC 61960 (First Edition 2003-12) : Secondary cells and batteries containing alkaline or other non-acid electrolytes – Secondary lithium cells and batteries for portable applications; (2) IEC 62133 (First Edition 2002-10): Secondary cells and batteries containing alkaline or other non-acid electrolytes – Safety requirements for portable sealed secondary cells, and for batteries made from them, for use in portable applications; (3) IEC 62660-1 (First Edition 2011-01): Secondary lithium-ion cells for the propulsion of electric road vehicles – Part 1: Performance testing.
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Rechargeable cell or battery means a cell or battery which is designed to be electrically recharged. Rupture means the mechanical failure of a cell container or battery case induced by an internal or external cause, resulting in exposure or spillage but not ejection of solid materials. Short circuit means a direct connection between positive and negative terminals of a cell or battery that provides a virtual zero resistance path for current flow. Single cell battery means a cell externally fitted with devices necessary for use in equipment or another battery which it is designed to power, for example protective devices. See definitions for cell and battery. NOTE: A single cell battery is considered a “cell” and shall be tested according to the testing requirements for “cells” for the purposes of the Model Regulations and this Manual. Small battery means a lithium metal battery or lithium ion battery with a gross mass of not more than 12 kg. Small cell means a cell with a gross mass of not more than 500 g. Type means a particular electrochemical system and physical design of cells or batteries. Undischarged means a primary cell or battery that has not been wholly or partly discharged. Venting means the release of excessive internal pressure from a cell or battery in a manner intended by design to preclude rupture or disassembly. Watt-hour rating, see Nominal energy. 38.3.3 When a cell or battery type is to be tested under this sub-section, the number and condition of cells and batteries of each type to be tested are as follows: (a)
(b)
When testing primary cells and batteries under tests T.1 to T.5 the following shall be tested in the quantity indicated: (i)
ten cells in undischarged states;
(ii)
ten cells in fully discharged states;
(iii)
four small batteries in undischarged states;
(iv)
four small batteries in fully discharged states;
(v)
four large batteries in undischarged states; and
(vi)
four large batteries in fully discharged states.
When testing rechargeable cells and batteries under tests T.1 to T.5 the following shall be tested in the quantity indicated: (i)
ten cells at first cycle, in fully charged states;
(ii)
four small batteries at first cycle, in fully charged states;
(iii)
four small batteries after 50 cycles ending in fully charged states;
(iv)
two large batteries at first cycle, in fully charged states; and
(v)
two large batteries after 25 cycles ending in fully charged states.
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(c)
(d)
When testing primary and rechargeable cells under test T.6, the following shall be tested in the quantity indicated: (i)
for primary cells, five cells in undischarged states and five cells in fully discharged states;
(ii)
for component cells of primary batteries, five cells in undischarged states and five cells in fully discharged states;
(iii)
for rechargeable cells, five cells at first cycle at 50% of the design rated capacity; and
(iv)
for component cells of rechargeable batteries, five cells at first cycle at 50% of the design rated capacity.
When testing rechargeable batteries or rechargeable single cell batteries under test T.7, the following shall be tested in the quantity indicated: (i)
four small batteries at first cycle, in fully charged states;
(ii)
four small batteries after 50 cycles ending in fully charged states;
(iii)
two large batteries at first cycle, in fully charged states; and
(iv)
two large batteries after 25 cycles ending in fully charged states.
Batteries or single cell batteries not equipped with battery overcharge protection that are designed for use only as a component in another battery or in equipment, which affords such protection, are not subject to the requirements of this test. (e)
(f)
When testing primary and rechargeable cells and component cells under test T.8, the following shall be tested in the quantity indicated: (i)
ten primary cells in fully discharged states;
(ii)
ten primary component cells in fully discharged states;
(iii)
ten rechargeable cells, at first cycle in fully discharged states;
(iv)
ten rechargeable component cells, at first cycle in fully discharged states;
(v)
ten rechargeable cells after 50 cycles ending in fully discharged states; and
(vi)
ten rechargeable component cells after 50 cycles ending in fully discharged states.
When testing a battery assembly in which the aggregate lithium content of all anodes, when fully charged, is not more than 500 g, or in the case of a lithium ion battery, with a Watt-hour rating of not more than 6 200 Wh, that is assembled from batteries that have passed all applicable tests, one assembled battery in a fully charged state shall be tested under tests T.3, T.4 and T.5, and, in addition, test T.7 in the case of a rechargeable battery.
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(g)
38.3.4
When batteries that have passed all applicable tests are electrically connected to form a battery in which the aggregate lithium content of all anodes, when fully charged, is more than 500 g, or in the case of a lithium ion battery, with a Watt-hour rating of more than 6 200 Wh, the assembled battery does not need to be tested if the assembled battery is of a type that has been verified as preventing: (i)
Overcharge;
(ii)
Short circuits; and
(iii)
Over discharge between the batteries.
Procedure
Tests T.1 to T.5 shall be conducted in sequence on the same cell or battery. Tests T.6 and T.8 shall be conducted using not otherwise tested cells or batteries. Test T.7 may be conducted using undamaged batteries previously used in Tests T.1 to T.5 for purposes of testing on cycled batteries. 38.3.4.1
Test T.1: Altitude simulation
38.3.4.1.1
Purpose This test simulates air transport under low-pressure conditions.
38.3.4.1.2
Test procedure
Test cells and batteries shall be stored at a pressure of 11.6 kPa or less for at least six hours at ambient temperature (20 ± 5 °C). 38.3.4.1.3
Requirement
Cells and batteries meet this requirement if there is no leakage, no venting, no disassembly, no rupture and no fire and if the open circuit voltage of each test cell or battery after testing is not less than 90% of its voltage immediately prior to this procedure. The requirement relating to voltage is not applicable to test cells and batteries at fully discharged states. 38.3.4.2
Test T.2: Thermal test
38.3.4.2.1
Purpose
This test assesses cell and battery seal integrity and internal electrical connections. The test is conducted using rapid and extreme temperature changes. 38.3.4.2.2
Test procedure
Test cells and batteries are to be stored for at least six hours at a test temperature equal to 72 ± 2 °C, followed by storage for at least six hours at a test temperature equal to - 40 ± 2 °C. The maximum time interval between test temperature extremes is 30 minutes. This procedure is to be repeated until 10 total cycles are complete, after which all test cells and batteries are to be stored for 24 hours at ambient temperature (20 ± 5 °C). For large cells and batteries the duration of exposure to the test temperature extremes should be at least 12 hours.
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38.3.4.2.3
Requirement
Cells and batteries meet this requirement if there is no leakage, no venting, no disassembly, no rupture and no fire and if the open circuit voltage of each test cell or battery after testing is not less than 90% of its voltage immediately prior to this procedure. The requirement relating to voltage is not applicable to test cells and batteries at fully discharged states. 38.3.4.3
Test T.3: Vibration
38.3.4.3.1
Purpose This test simulates vibration during transport.
38.3.4.3.2
Test procedure
Cells and batteries are firmly secured to the platform of the vibration machine without distorting the cells in such a manner as to faithfully transmit the vibration. The vibration shall be a sinusoidal waveform with a logarithmic sweep between 7 Hz and 200 Hz and back to 7 Hz traversed in 15 minutes. This cycle shall be repeated 12 times for a total of 3 hours for each of three mutually perpendicular mounting positions of the cell. One of the directions of vibration must be perpendicular to the terminal face. The logarithmic frequency sweep shall differ for cells and batteries with a gross mass of not more than 12 kg (cells and small batteries), and for batteries with a gross mass of more than 12 kg (large batteries). For cells and small batteries: from 7 Hz a peak acceleration of 1 gn is maintained until 18 Hz is reached. The amplitude is then maintained at 0.8 mm (1.6 mm total excursion) and the frequency increased until a peak acceleration of 8 gn occurs (approximately 50 Hz). A peak acceleration of 8 gn is then maintained until the frequency is increased to 200 Hz. For large batteries: from 7 Hz to a peak acceleration of 1 gn is maintained until 18 Hz is reached. The amplitude is then maintained at 0.8 mm (1.6 mm total excursion) and the frequency increased until a peak acceleration of 2 gn occurs (approximately 25 Hz). A peak acceleration of 2 gn is then maintained until the frequency is increased to 200 Hz. 38.3.4.3.3
Requirement
Cells and batteries meet this requirement if there is no leakage, no venting, no disassembly, no rupture and no fire during the test and after the test and if the open circuit voltage of each test cell or battery directly after testing in its third perpendicular mounting position is not less than 90% of its voltage immediately prior to this procedure. The requirement relating to voltage is not applicable to test cells and batteries at fully discharged states. 38.3.4.4
Test T.4: Shock
38.3.4.4.1
Purpose This test assesses the robustness of cells and batteries against cumulative shocks.
38.3.4.4.2
Test procedure
Test cells and batteries shall be secured to the testing machine by means of a rigid mount which will support all mounting surfaces of each test battery.
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Each cell shall be subjected to a half-sine shock of peak acceleration of 150 gn and pulse duration of 6 milliseconds. Alternatively, large cells may be subjected to a half-sine shock of peak acceleration of 50 gn and pulse duration of 11 milliseconds. Each battery shall be subjected to a half-sine shock of peak acceleration depending on the mass of the battery. The pulse duration shall be 6 milliseconds for small batteries and 11 milliseconds for large batteries. The formulas below are provided to calculate the appropriate minimum peak accelerations. Battery
Minimum peak acceleration
Pulse duration
150 gn or result of formula Small batteries
Accelerati on( g n )
§ 100850 · ¨ ¸ © mass * ¹
6 ms
whichever is smaller 50 gn or result of formula Large batteries
Accelerati on ( g n )
§ 30000 · ¸ ¨ © mass * ¹
11 ms
whichever is smaller * Mass is expressed in kilograms. NOTE: IEC Standard 60068-2-27 (Fourth Edition 2008-02): Environmental testing-Part 2-27: Tests – Test Ea and guidance: Shock provides guidance on tolerance for acceleration and pulse duration.
The relationship between minimum peak acceleration and mass is illustrated in Figure 38.3.4.1 for small batteries and Figure 38.3.4.2 for large batteries.
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Figure 38.3.4.1: Relation between the Peak Acceleration and the Mass for small batteries (below 12.0 kg).
Figure 38.3.4.2: Relation between the Peak Acceleration and the Mass for large batteries (equal or above 12.0 kg). Each cell or battery shall be subjected to three shocks in the positive direction and to three shocks in the negative direction in each of three mutually perpendicular mounting positions of the cell or battery for a total of 18 shocks.
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38.3.4.4.3
Requirement
Cells and batteries meet this requirement if there is no leakage, no venting, no disassembly, no rupture and no fire and if the open circuit voltage of each test cell or battery after testing is not less than 90% of its voltage immediately prior to this procedure. The requirement relating to voltage is not applicable to test cells and batteries at fully discharged states. 38.3.4.5
Test T.5: External short circuit
38.3.4.5.1
Purpose This test simulates an external short circuit.
38.3.4.5.2
Test procedure
The cell or battery to be tested shall be shall be heated for a period of time necessary to reach a homogeneous stabilized temperature of 57 ± 4 °C, measured on the external case. This period of time depends on the size and design of the cell or battery and should be assessed and documented. If this assessment is not feasible, the exposure time shall be at least 6 hours for small cells and small batteries, and 12 hours for large cells and large batteries. Then the cell or battery at 57 ± 4 °C shall be subjected to one short circuit condition with a total external resistance of less than 0.1 ohm. This short circuit condition is continued for at least one hour after the cell or battery external case temperature has returned to 57 ± 4 °C, or in the case of the large batteries, has decreased by half of the maximum temperature increase observed during the test and remains below that value. The short circuit and cooling down phases shall be conducted at least at ambient temperature. 38.3.4.5.3
Requirement
Cells and batteries meet this requirement if their external temperature does not exceed 170 °C and there is no disassembly, no rupture and no fire during the test and within six hours after the test. 38.3.4.6
Test T.6: Impact/Crush
38.3.4.6.1
Purpose These tests simulate mechanical abuse from an impact or crush that may result in an internal
short circuit. 38.3.4.6.2
Test procedure – Impact (applicable to cylindrical cells not less than 18.0 mm in diameter)
NOTE: 18.0 mm).
Diameter here refers to the design parameter (for example the diameter of 18 650 cells is
The test sample cell or component cell is to be placed on a flat smooth surface. A 15.8 mm ± 0.1 mm diameter, at least 6 cm long, or the longest dimension of the cell, whichever is greater, Type 316 stainless steel bar is to be placed across the centre of the sample. A 9.1 kg ± 0.1kg mass is to be dropped from a height of 61 ± 2.5 cm at the intersection of the bar and sample in a controlled manner using a near frictionless, vertical sliding track or channel with minimal drag on the falling mass. The vertical track or channel used to guide the falling mass shall be oriented 90 degrees from the horizontal supporting surface. The test sample is to be impacted with its longitudinal axis parallel to the flat surface and perpendicular to the longitudinal axis of the 15.8 mm ± 0.1 mm diameter curved surface lying across the centre of the test sample. Each sample is to be subjected to only a single impact. - 433 -
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38.3.4.6.3 Test Procedure – Crush (applicable to prismatic, pouch, coin/button cells and cylindrical cells less than 18.0 mm in diameter) NOTE: Diameter here refers to the design parameter (for example the diameter of 18 650 cells is 18.0 mm).
A cell or component cell is to be crushed between two flat surfaces. The crushing is to be gradual with a speed of approximately 1.5 cm/s at the first point of contact. The crushing is to be continued until the first of the three options below is reached. (a)
The applied force reaches 13 kN ± 0.78 kN;
Example: The force shall be applied by a hydraulic ram with a 32 mm diameter piston until a pressure of 17 MPa is reached on the hydraulic ram. (b)
The voltage of the cell drops by at least 100 mV; or
(c)
The cell is deformed by 50% or more of its original thickness.
Once the maximum pressure has been obtained, the voltage drops by 100 mV or more, or the cell is deformed by at least 50% of its original thickness, the pressure shall be released. A prismatic or pouch cell shall be crushed by applying the force to the widest side. A button/coin cell shall be crushed by applying the force on its flat surfaces. For cylindrical cells, the crush force shall be applied perpendicular to the longitudinal axis. Each test cell or component cell is to be subjected to one crush only. The test sample shall be observed for a further 6 h. The test shall be conducted using test cells or component cells that have not previously been subjected to other tests. 38.3.4.6.4
Requirement
Cells and component cells meet this requirement if their external temperature does not exceed 170 °C and there is no disassembly and no fire during the test and within six hours after this test. 38.3.4.7
Test T.7: Overcharge
38.3.4.7.1
Purpose
This test evaluates the ability of a rechargeable battery or a single cell rechargeable battery to withstand an overcharge condition. 38.3.4.7.2
Test procedure
The charge current shall be twice the manufacturer's recommended maximum continuous charge current. The minimum voltage of the test shall be as follows: (a)
when the manufacturer's recommended charge voltage is not more than 18 V, the minimum voltage of the test shall be the lesser of two times the maximum charge voltage of the battery or 22 V.
(b)
when the manufacturer's recommended charge voltage is more than 18 V, the minimum voltage of the test shall be 1.2 times the maximum charge voltage.
Tests are to be conducted at ambient temperature. The duration of the test shall be 24 hours. - 434 -
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38.3.4.7.3
Requirement
Rechargeable batteries meet this requirement if there is no disassembly and no fire during the test and within seven days after the test. 38.3.4.8
Test T.8: Forced discharge
38.3.4.8.1
Purpose
This test evaluates the ability of a primary or a rechargeable cell to withstand a forced discharge condition. 38.3.4.8.2
Test procedure
Each cell shall be forced discharged at ambient temperature by connecting it in series with a 12V D.C. power supply at an initial current equal to the maximum discharge current specified by the manufacturer. The specified discharge current is to be obtained by connecting a resistive load of the appropriate size and rating in series with the test cell. Each cell shall be forced discharged for a time interval (in hours) equal to its rated capacity divided by the initial test current (in ampere). 38.3.4.8.3
Requirement
Primary or rechargeable cells meet this requirement if there is no disassembly and no fire during the test and within seven days after the test. 38.4
Substances evolving flammable vapour
38.4.1
Purpose
This section of the Manual presents the test procedure to determine whether during handling, transport and storage substances of Class 9 evolving flammable vapours (see UN No. 2211), are able to evolve a dangerous concentration of flammable vapours in closed containers resulting in the formation of a flammable atmosphere and, as a consequence, have to be classified or not. 38.4.2
Scope
The scope of the test method is to determine whether polymeric beads with encapsulated blowing agent, fulfilling the description of UN No. 2211, need not to be classified under these UN numbers. 38.4.3
Classification procedure for substances liable to evolve flammable vapours
Polymeric beads with encapsulated blowing agent shall be tested according to the procedures below to determine whether classification under UN No. 2211 is needed. 38.4.4
Test U 1: Test method for substances liable to evolve flammable vapours
38.4.4.1
Introduction
The ability to evolve flammable vapours is determined by placing the substance in a hermetically closed glass bottle, at a specified temperature for a prescribed period of time, and then, determine the identity and concentration of flammable vapours.
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38.4.4.2
Apparatus and materials
A serum flask equipped with polytetrafluoroethylene septa with a volume of 50 ml to allow for enough samples to be analysed. A heating cabinet for storage of samples at prescribed time and temperature. A gas chromatographic (GC) apparatus and accompanying equipment, for analysis of flammable vapour concentration in the gas-phase. 38.4.4.3
Procedure
The substance as offered for transport should be put in a serum flask of 50 ml, with a degree of filling of 50% volume ratio and sealed with polytetrafluoroethylene septa. The sealed flask is put into a heating cabinet at a minimum of 50 °C for 14 days. Under these conditions analyse the gas twice by gas chromatography and calculate the average concentration of the flammable vapour. The test shall be performed on three samples of the same substance. 38.4.4.4
Test criteria and method of assessing results
Substances need not be classified as Polymeric beads, expandable if the concentration of the flammable vapours is less than or equal to 20% of the Lower Explosive Limit (LEL) of the flammable vapour in all of the three samples.
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PART IV TEST METHODS CONCERNING TRANSPORT EQUIPMENT
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CONTENTS OF PART IV Section
Page
40. 40.1 40.2
INTRODUCTION TO PART IV ......................................................................................... PURPOSE ............................................................................................................................. SCOPE .............................................................................................................................
441 441 441
41.
DYNAMIC LONGITUDINAL IMPACT TEST FOR PORTABLE TANKS AND MULTIPLE-ELEMENT GAS CONTAINERS (MEGCs) .................................... GENERAL ............................................................................................................................. PERMITTED DESIGN VARIATIONS ................................................................................. TEST APPARATUS ...............................................................................................................
443 443 443 444
41.1 41.2 41.3
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SECTION 40 INTRODUCTION TO PART IV 40.1
Purpose
40.1.1 Part IV of the Manual presents the United Nations schemes for dynamic and longitudinal impact testing of portable tanks and MEGCs (see section 41 of this Manual and 6.7.2.19.1, 6.7.3.15.1, 6.7.4.14.1 and 6.7.5.12.1 of the Model Regulations). 40.2
Scope
40.2.1
The test methods of this Part should be applied when required by the Model Regulations.
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SECTION 41 DYNAMIC LONGITUDINAL IMPACT TEST FOR PORTABLE TANKS AND MULTIPLE-ELEMENT GAS CONTAINERS (MEGCs) 41.1
General
41.1.1 This test method is intended to prove the ability of portable tanks and MEGCs to withstand the effects of a longitudinal impact, as required by 6.7.2.19.1, 6.7.3.15.1, 6.7.4.14.1 and 6.7.5.12.1 of the Model Regulations. 41.1.2 A representative prototype of each design of portable tank and MEGC meeting the definition of "container" under the International Convention for Safe Containers, 1972, as amended (CSC), shall be subjected to and shall satisfy the requirements of the dynamic longitudinal impact test. Testing shall be conducted by facilities approved for this purpose by the competent authority. 41.2
Permitted design variations
The following variations in container design from an already tested prototype are permitted without additional testing: 41.2.1
41.2.2
Portable tanks
(a)
A reduction of no more than 10% or an increase of no more than 20% in capacity, resulting from variations in diameter and length;
(b)
A decrease in maximum permissible gross mass;
(c)
An increase in thickness, independent of design pressure and temperature;
(d)
A change to the grade of material of construction provided that the permitted yield strength meets or exceeds that of the tested portable tank;
(e)
A change in location of, or a modification to, nozzles and manholes.
MEGCs
(a)
A decrease in the maximum design temperature, not affecting thickness;
(b)
An increase in the minimum design temperature, not affecting thickness;
(c)
A decrease in the maximum permissible gross mass;
(d)
A decrease in the mass of each individual element and its lading or a decrease in the total mass of the elements and their lading;
(e)
An increase of no more than 10% or a decrease of no more than 40% in the diameter of the elements;
(f)
A change of no more than 10% in the length of the elements;
(g)
A decrease of no more than 3.1 metres (10 feet) in the length of the MEGC framework;
(h)
A decrease of no more than 50% in the height of the MEGC;
(i)
A change of no more than 50% in the number of elements;
(j)
An increase in the thickness of the materials of the framework provided the thickness stays within the range permitted by the welding procedure specifications; - 443 -
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(k)
A change to the service equipment and manifold such that the total mass of the service equipment and manifold changes no more than 10% of the maximum permissible gross mass (but not resulting in an increase in the maximum permissible gross mass as compared to that of the already-tested prototype);
(l)
The use of a different grade of the same type of material for the construction of the framework, provided that: (i)
The results of the design calculations for the different grade, using the most unfavourable specified values of mechanical properties for that grade, meet or exceed the results of the design calculation for the existing grade; and
(ii)
The alternate grade is permitted by the welding procedure specifications.
NOTE: For permitted MEGC design variations not requiring additional impact testing, the mounting apparatus attaching the elements to the framework must remain the same as that for the already-tested prototype MEGC design. 41.3
Test apparatus
41.3.1
Test platform
The test platform may be any suitable structure capable of sustaining without significant damage a shock of the prescribed severity with the container-under-test mounted securely in place. The test platform shall be: (a)
configured so as to allow the container-under-test to be mounted as close as possible to the impacting end;
(b)
equipped with four devices, in good condition, for securing the container-under-test in accordance with ISO 1161:1984 (Series 1 Freight containers – Corner fittings – Specification); and
(c)
equipped with a cushioning device to provide a suitable duration of impact.
41.3.2
Impact creation
41.3.2.1
The impact shall be created by: (a)
the test platform striking a stationary mass; or
(b)
the test platform being struck by a moving mass.
41.3.2.2 When the stationary mass consists of two or more railway vehicles connected together, each railway vehicle shall be equipped with cushioning devices. Free play between the vehicles shall be eliminated and the brakes on each of the railway vehicles shall be set. 41.3.3
Measuring and recording system
41.3.3.1 Unless otherwise specified, the measuring and recording system shall comply with ISO 6487:2002 (Road vehicles – Measurement techniques in impact tests – Instrumentation).
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41.3.3.2
41.3.4
The following equipment shall be available for the test: (a)
Two accelerometers with a minimum amplitude range of 200 g, a maximum lower frequency limit of 1 Hz and a minimum upper frequency limit of 3 000 Hz. Each accelerometer shall be rigidly attached to the container-under-test at the outer end or side face of the two adjacent bottom corner fittings closest to the impact source. The accelerometers shall be aligned so as to measure the acceleration in the longitudinal axis of the container. The preferred method is to attach each accelerometer to a flat mounting plate by means of bolting and to bond the mounting plates to the corner fittings;
(b)
A means of measuring the velocity of the moving test platform or the moving mass at the moment of impact;
(c)
An analogue-to-digital data acquisition system capable of recording the shock disturbance as an acceleration versus time history at a minimum sampling frequency of 1 000 Hz. The data acquisition system shall incorporate a low-pass anti-aliasing analogue filter with a corner frequency set to a minimum of 200 Hz and a maximum of 20% of the sampling rate, and a minimum roll off rate of 40 dB/octave; and
(d)
A means of storing the acceleration versus time histories in electronic format so that they can be subsequently retrieved and analysed.
Procedure
41.3.4.1 Filling the container-under-test may be undertaken before or after mounting on the test platform, as follows:
41.3.4.2
(a)
Portable tanks: The tank shall be filled with water or any other non-pressurized substance to approximately 97% of the tank volumetric capacity. The tank shall not be pressurized during the test. If for reasons of overload it is not desirable to fill to 97% of capacity, the tank shall be filled so that the mass of the container-under test(tare and product) is as close as practicable to its maximum rated mass (R);
(b)
MEGCs: Each element shall be filled with an equal quantity of water or any other non-pressurized substance. The MEGC shall be filled so that its mass is as close as practicable to its maximum rated mass (R) but in any event, to no more than 97% of its volumetric capacity. The MEGC shall not be pressurized during the test. Filling a MEGC is not required when its tare mass is equal to or higher than 90% of R.
The mass of the container, as tested, shall be measured and recorded.
41.3.4.3 The container-under-test shall be oriented in a manner that will result in the most severe test. The container shall be mounted on the test platform, as close as possible to the impacting end and secured using all four of its corner fittings so as to restrain its movement in all directions. Any clearance between the corner fittings of the container-under-test and the securing devices at the impacting end of the test platform shall be minimised. In particular, impacting masses shall be free to rebound after impact. 41.3.4.4 An impact shall be created (see 41.3.2) such that for a single impact the as tested Shock Response Spectrum (SRS, see 41.3.8.1) curve at both corner fittings at the impacting end equals or exceeds the minimum SRS curve shown in Figure 41.3.8.1 at all frequencies within the range from 3 Hz to 100 Hz. Repeated impacts may be required to achieve this result but the test results for each impact shall be considered individually; 41.3.4.5 Following an impact described in 41.3.4.4, the container-under-test shall be examined and the results recorded. To satisfy the test, the container shall show no leakage, permanent deformation or damage that would render it unsuitable for use, and shall be in conformity with the dimensional requirements regarding handling, securing and transfer from one means of transport to another. - 445 -
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41.3.5
Processing and analysis of data
41.3.5.1
Data reduction system
(a)
(b)
The acceleration versus time history data from each channel shall be reduced to the shock response spectrum, ensuring that the spectra are presented in the form of equivalent static acceleration plotted as a function of frequency. The maximum absolute value acceleration peak shall be recorded for each of the specified frequency break points. The data reduction shall follow the following criteria: (i)
If required, the corrected impact acceleration versus time history data shall be scaled using the procedure outlined in section 41.3.5.2;
(ii)
The acceleration versus time history data shall comprise the period commencing 0.05 seconds prior to the start of the impact event and the 2.0 seconds thereafter;
(iii)
The analysis shall span the frequency range of 2 to 100 Hz and calculation of the shock response curve points shall be performed at a minimum of 30 frequency break points per octave. Each break point in the range shall constitute a natural frequency; and
(iv)
A damping ratio of 5% shall be used in the analysis;
Calculation of the test shock response curve points shall be made as described below. For each frequency break point: (i)
A matrix of relative displacement values shall be calculated using all data points from the shock input acceleration versus time history using the following equation:
[L
ǻt
i
¦ X e Ȧ k 0
d
Y
ȗ
n
ǻt (i k)
k
sin
>Z
d
ǻt (i k )
@
where: 't = Zn =
time interval between acceleration values; undamped natural frequency (in radians);
Zd =
damped natural frequency =
Zn 1 ] 2
;
x k = kth value of acceleration input data; ]
i k (ii)
= damping ratio; = integer number, varies from 1 to the number of input acceleration data points; = parameter used in summation which varies from 0 to the current value of i.
A matrix of relative accelerations shall be calculated using the displacement values obtained in step i in the following equation: i
]Zn 't i k
[i 2]Zn 't ¦ xk e k 0
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cos > Zd 't i k @Zn2 2] 2 1 [i
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(iii)
The maximum absolute acceleration value from the matrix generated in step ii for the frequency break point under consideration shall be retained. This value becomes the SRS curve point for this particular frequency break point. Step i shall be repeated for each natural frequency until all natural frequency break points have been evaluated.
(iv)
The test shock response spectrum curve shall be generated.
Method for scaling measured acceleration versus time history values to compensate for 41.3.5.2 under or over mass containers
Where the sum of the as-tested payload mass plus tare mass of the container-under-test is not the maximum rated mass of the container-under-test, a scaling factor shall be applied to the measured acceleration versus time histories for the container-under-test as follows: The corrected acceleration-time values, Acc(t) (corrected), shall be calculated from the measured acceleration versus time values using following formula:
Acc ( t ) ( corrected ) Acc ( t ) ( measured ) u
1 'M 1 M 1 M 2
Where: Acc(t) (measured) = actual measured-time value; M1 =
mass of the test platform, without the container-under-test;
M2 =
actual test mass (including tare) of the container-under-test;
R
the maximum rated mass (including tare) of the container-under-test;
=
'M =
R - M2;
The test SRS values shall be generated from the Acc(t) (corrected) values. 41.3.6
Defective instrumentation
If the acquired signal from one accelerometer is faulty the test may be validated by the SRS from the functional accelerometer after three consecutive impacts provided that the SRS from each of the three impacts meets or exceeds the minimum SRS curve. 41.3.7
Alternate test severity validation method for portable tanks with frame length of 20 feet
41.3.7.1 If the design of a tank container-under-test is significantly different from other containers successfully subjected to this test and the SRS curves obtained have correct features but remain below the minimum SRS curve, the test severity may be considered acceptable if three successive impacts are performed as follows: (a)
First impact at a speed higher than 90% of the critical speed referred to in 41.3.7.2; and
(b)
Second and third impact at a speed higher than 95% of the critical speed referred to in 41.3.7.2.
41.3.7.2 The alternate validation method described in 41.3.7.1, shall be used only if the platform’s "critical speed" had been determined beforehand. The critical speed is the speed where the platform’s cushioning devices reach their maximum travel and energy absorption capacity beyond which the minimum SRS curve is normally obtained or exceeded. The critical speed shall have been determined from a minimum of five documented tests on five different tank containers. Each such test shall have been performed using the same equipment, measuring system and procedure. - 447 -
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41.3.8
Recording of data
At least the following data shall be recorded in the application of this procedure: (a)
Date, time, ambient temperature, and location of test;
(b)
Container tare mass, maximum rated mass, and as-tested payload mass;
(c)
Container manufacturer, type, registration number if applicable, certified design codes and approvals if applicable;
(d)
Test platform mass;
(e)
Impact velocity;
(f)
Direction of impact with respect to container; and
(g)
For each impact, an acceleration versus time history for each instrumented corner fitting. Figure 41.3.8.1: Minimum SRS Curve MINIMUM SRS (5% DAMPING)
ACCELERATION (g)
100
10
1 1
10
100
FREQUENCY (Hz)
Equation for generating the above Minimum SRS Curve: ACCEL = 1.95 FREQ 0.355 Table 41.3.8.1: Tabular representation of some data points for the minimum SRS curve above. FREQUENCY (Hz) 3 10 100
ACCELERATION (g) 2.88 4.42 10.0
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PART V CLASSIFICATION PROCEDURES, TEST METHODS AND CRITERIA RELATING TO SECTORS OTHER THAN TRANSPORT
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CONTENTS OF PART V Section
Page
50. 50.1 50.2
INTRODUCTION TO PART V .......................................................................................... PURPOSE ............................................................................................................................. SCOPE .............................................................................................................................
453 453 453
51.
CLASSIFICATION PROCEDURES, TEST METHODS AND CRITERIA RELATING TO THE HAZARD CLASS DESENSITIZED EXPLOSIVES .................. PURPOSE ............................................................................................................................. SCOPE ............................................................................................................................. CLASSIFICATION PROCEDURE ........................................................................................ BURNING RATE TEST (EXTERNAL FIRE) (D) ................................................................ Introduction ............................................................................................................................. Apparatus and materials .......................................................................................................... Procedure ............................................................................................................................. Test criteria and method of assessing results .......................................................................... Examples of results ................................................................................................................. Example of calculation ............................................................................................................
455 455 455 455 456 456 456 457 457 461 462
51.1 51.2 51.3 51.4 51.4.1 51.4.2 51.4.3 51.4.4 51.4.5 51.4.6
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SECTION 50 INTRODUCTION TO PART V
50.1
Purpose
Part V of the Manual presents the United Nations schemes for the classification of desensitized explosives for supply and use (including storage) according to the GHS. 50.2
Scope
The test methods of this Part should be applied when required by the GHS.
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SECTION 51 CLASSIFICATION PROCEDURES, TEST METHODS AND CRITERIA RELATING TO THE HAZARD CLASS DESENSITIZED EXPLOSIVES
51.1
Purpose
51.1.1 This section presents the United Nations scheme of the classification of liquid and solid desensitized explosives see Chapter 2.17 of the Globally Harmonized System of Classification and Labelling of Chemicals (GHS)). The text should be used in conjunction with the classification principles of Chapter 2.17 of the GHS and the test series given in sub-sections 16.4 and 16.5 of this Manual. For testing of liquid desensitized explosives for transport purposes, refer to section 32, subsection 32.3.2 of this Manual and to Chapter 2.3, sub-section 2.3.1.4 of the Model Regulations. Testing of solid desensitized explosives for transport purposes is addressed in section 33, sub-section 33.2.3 of this Manual and in Chapter 2.4, sub-section 2.4.2.4 of the Model Regulations. 51.2
Scope
51.2.1 Desensitized explosives are solid or liquid explosive substances or mixtures which are phlegmatized to suppress their explosive properties in such a manner that they may be excluded from the hazard class “Explosives” (Chapter 2.1 of GHS). Desensitized explosives, should be first tested according to the tests series 1 (type 1(a)), 2 and 6 (type (a) and (b), respectively) of this Manual1 . 51.2.2 The appropriate classification procedures for desensitized explosives should be undertaken before they are offered for supply and use unless: (a) They are manufactured with the view to producing a practical, explosive or pyrotechnic effect; (b) They have a mass explosion hazard according to Test Series 6(a) or 6(b) or their corrected burning rate according to the burning rate test 51.4 is more than 1 200 kg/min; (c) Their exothermic decomposition energy is less than 300 J/g2. 51.3
Classification procedure
51.3.1 Before packaged substances or mixtures are subjected to the burning rate test, the test series 6 types 6 (a) and 6 (b) shall be performed in alphabetical order. The substances or mixtures should be tested first with a standard detonator (Appendix 1 of the Manual) and, if no explosion occurs, with an igniter just
1
Unstable explosives as defined in Chapter 2.1 of GHS can also be stabilized by desensitization and consequently may be classified as desensitized explosive, provided all criteria of Chapter 2.17 of GHS are met. In this case the desensitized explosive should be tested according to test series 3 (Part I of this Manual) because information about its sensitiveness to mechanical stimuli is likely to be important for determining conditions for safe handling and use. The results should be communicated in the safety data sheet. 2
The exothermic decomposition energy should be determined using the explosive already desensitized (i.e.: the homogenous solid or liquids mixture formed by the explosive and the substance(s) used to suppress its explosive properties). The exothermic decomposition energy may be estimated using a suitable calorimetric technique (see Section 20, sub-section 20.3.3.3 in Part II of this Manual). - 455 -
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sufficient (but not more than 30 g of black powder) to ensure ignition of the substance or mixture in the packaging. The initiation system giving a positive result in the 6 (a) test should be used for the 6 (b) test. 51.3.2 However, it is not always necessary to conduct tests of all types. Test type 6 (b) may be waived if in each type 6 (a) test: (a) The exterior of the package is undamaged by internal detonation and/or ignition; or (b) The contents of the package fail to explode, or explode so feebly as would exclude propagation of the explosive effect from one package to another in test type 6(b). 51.3.3 If a substance or mixture gives a negative result (no propagation of detonation) in the Series 1 type 1(a) test, the 6(a) test with a detonator may be waived3). If a substance or mixture gives a negative result (no or slow deflagration) in a Series 2 type 2(c) test, the 6 (a) test with an igniter may be waived. 51.3.4 The test for determination of the burning rate by large-scale test need not be performed if, in a test type 6 (b), there is practically instantaneous explosion of virtually the total contents of the stack. In such cases the product is assigned to Division 1.1. 51.4
Burning rate test (external fire)
51.4.1
Introduction
51.4.1.1 The test method for determination of the burning rate (10 000 kg scale burning rate) is to be used to determine the behaviour of substances or mixtures as packaged for storage and use if involved in an external fire. This test is performed with several packages of the substances or mixtures to determine: (a) Whether there is a mass explosion hazard, a hazard from dangerous projection or a too violent burning, (b) A burning rate (10 000 kg scaled), which depends on the total mass. 51.4.1.2 The burning rate is defined as the extrapolated burning rate for a mass of 10 000 kg packaged material. In practice, this burning rate is determined using both a single package and stacks of packages, following by an extrapolation procedure. The tests are performed with the substances or mixtures in the packages as provided for storage and use. All types of packages are subjected to the tests unless: (a) A substance or mixture, as packed for supply and use, may be unambiguously assigned to a burning rate and category by a competent authority on the basis of results from other tests or of available information; or (b) The substance or mixture, as packed for supply and use, is assigned to the hazard class “Explosives”, Division 1.1. 51.4.1.3 The corrected burning rate (10 000 kg scaled) is to be used for classification into four different categories. 51.4.2
Apparatus and materials
51.4.2.1 The test should be applied to packages of substances or mixtures in the condition and form in which they are offered for supply and use (including storage). The following elements are needed: (a) A number of 1, 6 and 10 packages, with a net mass of desensitized explosive of 25 kg in each package; 3
If the type 1 (a) test is not carried out the Series 6 type 6(a) test cannot be waived. - 456 -
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(b) A number of 1, 3 and 6 packages, with a net mass of desensitized explosive between 25 kg and 50 kg in each package; (c) A number of 1 and up to six packages, with a net mass of desensitized explosive of more than 50 kg, the total net mass should not be greater than 500 kg; (d) One or two trays with an adequate size and height to contain the wooden pallets and the packages and to protect the ground; (e) Wooden pallets (e.g. according to DIN 15146), with wood-wool distributed between, under and above the packages; (f) A suitable ignition source guaranteeing the ignition of the wooden pallets/wood-wool and consequently the tested packages (a mixture of gasoline and light fuel oil 10/90 evenly distributed over the packages and the wood-wool is recommended); (g) Cine and/or video cameras and suitable equipment to measure the heat of radiation, e.g. infrared sensors and/or thermo cameras. 51.4.2.2 The number of tests and/or the total mass (whereas necessary) should be increased if the test results are ambiguous and the corresponding hazards cannot be clearly defined. 51.4.3
Procedure
51.4.3.1 The tests start with a single package and then the number of packages are successively increased as mentioned under 51.4.2.1 (a), (b) or (c). Normally the burning rate test should be performed once for each number of packages. The required numbers of packages, in the condition and way in which they are offered for supply and use (including storage), are arranged in such way, that the most severe results are anticipated, on wooden and leveled pallets. The pallets are placed in one (or two, if necessary) trays. A tray must comprise at least one complete pallet including 10 cm open space all around the pallet. Flammable material (wood-wool, paper, etc.) is placed under and around the packages in such a way that an optimum ignition is guaranteed (see 51.4.2.1 (f)). NOTE: A quantity of about 10 kg dry wood-wool is usually sufficient. The wooden pallets and the dry wood-wool shall be soaked with a liquid mixture of fuel (about 10 liter, see 51.4.2.1 (f)).
51.4.3.2 The heat of radiation is measured during the test by suitable equipment, at least at three locations with three different distances from the seat of fire (the distances depend on the sensitivity of the equipment (sensors, thermo camera, etc.) and should be calculated before the test. 51.4.3.3 The signals are continuously recorded. The starting-point of the fire outbreak is defined as the moment when a reaction of the substance is detected. The end of the fire is determined from registered radiation curves. 51.4.3.4 If a mass explosion or individual explosions or metallic projections (fragments) are observed this should be noted in the test report. 51.4.4
Test criteria and method of assessing results
51.4.4.1
The burning rates A and A10t are determined as follows: (a) The starting point of the fire is defined as the moment at which the substance or mixture reacts detectably. The end of the fire is characterized by a decrease in radiation level I (as caused by the fire) to less than 5% of the maximum level (Imax) (see Figure 51.4.1);
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(b) The effect of either remainder or burning materials, if present, shall be taken into account in the evaluation; (c) The burning time t is the time span between the starting point and the end of the fire; (d) The burning rate A [kg/min] can be calculated for each tested quantity m [kg] and its corresponding burning time t [min] from the equation: m t
A
(e) log A is plotted against log m, where A is the determined burning rate, and m is the mass of substance or mixture used for the test. The observed test results are extrapolated by means of this graph to an uncorrected burning rate A10t for a mass of 10 000 kg corresponding to the following function: 2
§ 10000 kg · 3 ¨ ¸ A m © ¹
A10 t
51.4.4.2
The corrected burning rate AC is determined as follows: (a) The internal amount of energy of the substance is partially converted into radiation. The percent average radiation efficiency ƾ at a distance from the fire is determined from the measured radiation level (dosemeasured) and the theoretical maximum energy (dosecalculated); K
dose measured dose calculated
(b) The theoretical maximum energy is calculated by multiplying the individual mass of tested substance m [kg] with the heat of combustion Hv [kJ/kg]4 dose calculated
Hv m
(c) The amount of energy that in practice appears to be transferred by radiation is determined by integrating the area below the measured radiation curve;
dose measured
f (t )
ª « «t ¬
end
¦
start
( I ( t 't ) I t 2
º 't » 4 S r 2 » ¼
The numerical integration of the radiation intensities It [W/m2] over the total burning time delivers dosemeasured [kJ] at the distance r [m]. (d) To this end a graph is made showing the radiation level I [kW/m2] as a function of time. The complete radiation dose is calculated by integration of the smoothed and corrected curve down to 1% to 5% of Imax;
4
Should be determined by a suitable technique e.g. combustion calorimeter. - 458 -
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(e) Irelevant is obtained from the maximum of the curve of heat radiation calculated as average value of the radiation by converting the integrated area in a rectangle of equal size during the same time span; (f) The form factor f that must be taken into account during the maximum fire intensity can be averaged from the formula: I relevant I calculated
f
(g) The corrected burning rate Ac is calculated as follows: Ac
A10r
Hv K f 33 500 0.25 2.78
Where Hv is the heat of combustion of the substance [kJ/kg] (i.e. reaction enthalpy of the burning reaction); ƾ is the radiation efficiency and f the form factor. AC is the corrected burning rate [kg/min] for a quantity of 10 000 kg. 51.4.4.3 If a mass explosion or individual explosions or metallic projections (fragments) occur the substance or mixture is classified in the hazard class “explosives”. 51.4.4.4 The test results are assessed on the basis of the corrected burning rate AC for a quantity of 10 000 kg of the packaged substance or mixture. 51.4.4.5
The test criteria for determining the burning behavior of substances or mixtures are:
Category 1: Any substance or mixture with a corrected burning rate AC equal to or greater than 300 kg/min but not more than 1200 kg/min; Category 2: Any substance or mixture with a corrected burning rate AC equal to or greater than 140 kg/min but less than 300 kg/min; Category 3: Any substance or mixture with a corrected burning rate AC equal to or greater than 60 kg/min but less than 140 kg/min; Category 4:
Any substance or mixture with a corrected burning rate AC less than 60 kg/min.
Any substance or mixture with a corrected burning rate greater than 1200 kg/min is classified as an explosive (See Chapter 2.1 of the GHS).
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Figure 51.4.1: Measurement of radiation as a function of time
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51.4.5
Examples of results
51.4.5.1 The nitrocellulose formulations are packed in fiber drums (1G) with a maximum mass of 140 kg and fiber board boxes (4G) with a maximum mass of 25 kg, assigned to categories as follows: (a) Ester soluble (E-grades) nitrocellulose formulations with different phlegmatizers and a nitrogen content of 11.8% to 12.3% NC-type IPA 35% 12E 3
IPA 30% 2
ETH 35% 4
ETH 30% 3
BUT 35% 2
22E
3
3
4
3
3
25E
3
3
4
3
3
BUT Water Chipsa) 30% 1 4 1 (330 kg/min) (1115 kg/min) 3 4 1 (1115 kg/min) 3 3 1 (1115 kg/min)
IPA (Isopropanol), ETH (Ethanol), BUT (Butanol), a) NC-Chips with 20% plasticizer
(b) Medium soluble (M-grades) nitrocellulose formulations with different phlegmatizers and a nitrogen content of 11.3% to 11.8% NC-type IPA 35% 15M 27M 3
34M
3
IPA 30% 3
ETH 35% 4
ETH 30% 4
BUT 35% 3 3
BUT 30% 2 3
Water
3
4
4
4
-
-
4
Chipsa)
1 (1115 kg/min) 1 (1115 kg/min)
IPA (Isopropanol), ETH (Ethanol), BUT (Butanol), a) NC-Chips with 20% plasticizer
(c) Alcohol soluble (A-grades) nitrocellulose formulations with different phlegmatizers and a nitrogen content of 10.7% to 11.3% NC-type IPA 35% 15A 4
IPA 30% 3
ETH 35% 4
ETH 30% 3
BUT 35% 3
BUT 30% 2
Water
Chipsa)
-
1 (1115 kg/min) 1 (1115 kg/min) -
30A
4
3
4
4
3
3
4
32 A
4
3
4
4
4
3
-
IPA (Isopropanol), ETH (Ethanol), BUT (Butanol), a) NC-Chips with 20% plasticizer
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51.4.6
Example of a calculation NC-formulation (nitrogen content 10.7% to 11.2%) wetted with 30% isopropanol: Mass of the tested NC formulation:
m = 285 kg
Burning time:
t = 9.7 min
Form factor:
f = 3.73
Radiation efficiency:
ƾ = 0.24
Enthalpy of combustion:
Hv = 15626 kJ/kg
Calculation of the burning rate A: m t
A
285 kg 9.7 min
29.4
kg min
Calculation of the burning rate A10t:
A10 t
§ 10 000 kg ¨ ¨¨ m ©
· ¸ ¸¸ ¹
2 3
A
§ 10 000 kg · ¨ ¸ ¨ ¸ ¨ 285 kg ¸ © ¹
2 3
29.4
kg min
315
kg min
Calculation of the corrected burning rate Ac:
At
Hv K f A10t 33 500 0.25 2.78
kJ 15 626 kg kg 0.24 3.73 315 min 33 500 kJ 0.25 2.78 kg
189
kg min
The desensitized explosive is classified in category 2.
References [1] German “Guideline for the assignment of substances which may show explosive properties to Storage Groups (SprengLR011)” [2] Thermal radiation hazards from organic peroxides, Roberts, T.A. and Merrifield, R., J. Loss. Prev. Process Ind. 1990, 3, 244. [3] Thermal radiation hazard and separation distances for industrial cellulose nitrate, Roberts, T.A. and Merrifield, R., J. Loss. Prev. Process Ind. 1992, 5,311. [4] Storage of Organic Peroxides, Publication Series on Dangerous Substances 8 (PGS 8), Ministries of Social Affairs and of the Interior, The State Secretary of Housing, Spatial Planning and Environment (VROM), The Netherlands 2006. [5] The storage and handling of organic peroxides, Guidance Note CS21, Health and Safety Executive, 1998, United Kingdom
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APPENDICES
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CONTENTS OF APPENDICES Appendix
Page
1
SPECIFICATIONS OF STANDARD DETONATORS ....................................................
467
2
BRUCETON AND SAMPLE COMPARISON METHODS .............................................
471
3
CAVITATION OF SAMPLES ..........................................................................................
475
4
NATIONAL CONTACTS FOR TEST DETAILS.............................................................
479
5
EXAMPLE OF A TEST METHOD FOR VENT SIZING ................................................
481
6
SCREENING PROCEDURES ...........................................................................................
487
7
HSL FLASH COMPOSITION TEST ................................................................................
493
8
RESPONSE DESCRIPTORS.............................................................................................
501
9
BALLISTIC PROJECTION ENERGY TEST FOR CARTRIDGES, SMALL ARMS (UN NO. 0012) ........................................................................................
504
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APPENDIX 1 SPECIFICATIONS OF STANDARD DETONATORS 1.
Description of the standard electric blasting cap 0.6 g PETN
Drawing No.
Part No.
I
A
Blasting cap
B
II
Part
Description
Remarks
Fusehead
It must not undergo compression. Recommended amount of the pyrotechnic substance forming the bead: 20 mg to 50 mg
Example: Electrical fusehead Fa. DNAG, Germany, T 10 - U - with aluminium coating
A
Tube
Hollow-drawn tube of pure copper, (5% zinc) or of other alloys whose compositions are in the range between that of the above alloy and pure copper. The dimensions of the tube are shown in the figure. If required, the tubes for making standard detonators should be selected by checking the exact dimensions of each tube to be used.
B
(a) Secondary charge
Base charge: 0.40 g (± 0.01 g) PETN; compressed at 440 bar;
The PETN may contain up to 0.5% of carbonaceous matter to prevent electrostatic charges during handling and to improve the flow properties.
Intermediate charge 0.20 g (± 0.01 g) PETN; compressed at 20 bar.
Total height of secondary charge 12.3 mm (± 0.6 mm)
C
III
D
Priming charge (initiation charge)
Free choice of the substance and of its quantity. However, at least twice the minimum quantity required for initiation should be used. The total oxygen balance of the priming charge plus the secondary charge should not be more negative than -9.5% O2
Example: 0.30 ± 0.01 g dextrinated lead azide with a purity of 88% compressed at 440 bar
E
Inner cup (pierced)
-
It is not required to use a pierced inner cup. Pressing the priming charge onto a highly compressed part of the secondary charge is excluded.
A
Fusehead
-
Example: Electrical fusehead Fa. DNAG, Germany T 10 - U - with aluminium coating
B
Closing plug
-
No special requirements. It should however provide an absolutely tight seal (to avoid the formation of cuprous azide and to ensure the desired initiating strength). The usual commercial design is satisfactory.
C
Wire
-
Free choice, providing the electrical risks (static electricity, stray currents) are taken into account. However, the use of an insulating sheath of plastic material inside the detonator tube is not allowed.
D
Short-circuiting tube
Plastic tube
E
Label
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I III V (A) (C) (E)
Electric blasting cap (standard detonator) Fusehead Inner cup Blasting cap Intermediate charge Inner cup
II IV
Blasting cap (standard detonator) Tube
(B) (D)
Fusehead Priming charge
Figure A1.1: STANDARD DETONATOR (EUROPEAN)
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(A) (B) (C) (D)
Aluminium shell (material - 5052 aluminium alloy; length 31.8 mm; outer diameter 7.06 mm; wall thickness 0.19 mm) Brigewire and ignition charge Primer charge (0.195 g dextrinated lead azide) Base charge (0.447 g PETN pressed at 28 MPa) Figure A1.2: No. 8 (USA) DETONATOR - 469 -
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APPENDIX 2 BRUCETON AND SAMPLE COMPARISON METHODS 1.
Bruceton method
Introduction: The Bruceton method is used to determine the level of stimulus at which there is a 50% probability of obtaining a positive result. Procedure: The method involves applying different levels of stimulus and determining whether or not a positive reaction occurs. Performance of the trials is concentrated around the critical region by decreasing the stimulus by one level in the next trial if a positive result is obtained and increasing the stimulus by one level if a negative result is obtained. Usually about 5 preliminary trials are performed to find a starting level in approximately the right region and then at least 25 trials are performed to provide the data for the calculations. Calculation of results: In determining the level at which the probability of obtaining a positive result is 50% (H50), only the positives (+) or only the negatives (-) are used, depending on which has the smaller total. If the numbers are equal, either may be used. The data are recorded in a table (e.g. as in Table A2.1) and summarised as shown in Table A2.2. Column 1 of Table A2.2 contains the drop heights, in ascending order, starting with the lowest level for which a test result is recorded. In column 2, 'i' is a number corresponding to the number of equal increments above the base or zero line. Column 3 contains the number of positives (n(+)) or negatives (n(-)) for each drop height. The fourth column tabulates the result of multiplying 'i' times 'n' and the fifth column tabulates the results of multiplying the square of 'i' times 'n'. A mean is calculated from the following equation: H 50
where N S
¦n
i
, A
· § A r 0.5 ¸¸ c d u ¨¨ ¹ © NS
¦ i u n , c = lowest drop height and d = height interval. i
If negative results are used, the sign inside the brackets is positive; it is negative if positive results are used. The standard deviation, s, may be estimated using: § N u B A2 · ¸ 0 . 029 s 1.62 u d u ¨ S 2 ¨ ¸ N S © ¹
where B
¦ i
2
u ni .
Example of results: Using the data from Table A2.2, lowest drop height 10 cm, height interval 5 cm, sum of i.n(-) 16, sum of i².n(-) 30 and sum of n(-) 12; the mean height is given as: H 50
· § 16 10 5 u ¨ 0.5 ¸ = 19.2 cm ¹ © 12
and the standard deviation as:
§ 12 u 30 16 2 · 0.029 ¸¸ = 6.1 s 1.62 u 5 u ¨¨ 2 12 © ¹ Reference: W.J. Dixon and F.V. Massey, Jr. "Introduction to Statistical Analysis, McGraw-Hill Book Co., Toronto, 1969. - 471 -
Table A2.1: RECORDING DATA Drop height (cm)
1
2
3
4
5
6
7
30 -
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
+ +
-
+
-
1 +
-
+ +
-
+
-
+
-
-
+ -
+
-
+ -
-
+
+
4
1
5
4
3
5
-
2 13
- 472 -
Table A2.2: SUMMARISING DATA
CALCULATIONS USING NEGATIVES Height (cm)
i(-)
n(-)
i(-).n(-)
i2(-).n(-)
25
3
1
3
9
20
2
4
8
16
15
1
5
5
5
10
0
2
0
0
Ns = 12
A = 16
B = 30
TOTALS
12
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20
10
8 +
25
15
FREQUENCY
DROP RESULT
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2.
Sample comparison method
Introduction: This technique can be applied to any test where the Bruceton method is used. The Sample Comparison Test (SCT) is a non-parametric procedure designed to afford a high degree of confidence in any difference in sensitiveness in situations where the mean values given by the Bruceton method are close to one another. Procedure: Samples of explosive A are tested following a normal Bruceton method, but are tested alternately with those of sample B. However, instead of following their own up-and-down programme, each sample of explosive B is subjected to the same level of stimulus as in the immediately preceding trial with sample A. Thus, at each level of stimulus as the test proceeds, one trial is performed with sample A and one with sample B. If both react or both do not react then the result is ignored for the appraisal. Only pairs of results which have afforded different responses are used for the appraisal. Calculation of results: If there are n pairs of results which have afforded different responses and x is the number of positive reactions of the least sensitive sample from these pairs, i.e. x < (n - x), then the confidence, K%, that this sample is really less sensitive is calculated using Bernoullian statistics. K can be estimated by:
§ § x · n! ¸ K 100 u ¨1 2 n u ¨¨ ¸ ¨ © i 0 i !u n i ! ¹ ©
¦
· ¸ ¸ ¹
Various illustrative values of K are given in the table below for a series of values of x and n.
n x
15
20
25
30
2
99
3
98
99
4
94
99
5
85
98
99
6
70
94
99
7
87
98
99
8
75
95
99
9
59
89
98
79
95
10
Where there is no real difference in two samples, the proportion of occasions where the pairs of results are the same increases and, at the same time, (n - 2x) does not show a general tendency to increase as the testing proceeds.
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Examples of results: HMX admixed with 0.01% of 45-63 Pm airborne grit, compared with unadulterated HMX, gave x = 3 at n = 13 indicating that the former was more sensitive at the confidence level of:
K
§ · § 3 13 ! ¸ 100 u ¨1 2 13 u ¨¨ ¸ ¨ © i 0 i! u 13 i ! ¹ ©
¦
· ¸ ¸ ¹
§ 1 13 78 286 · 100 u ¨1 ¸ 95.4% 8192 © ¹
Comparing a suspect sample of milled HMX with a normal sample gave x = 6 at n = 11 indicating that the former was more sensitive at the confidence level of:
K
§ · § 6 11! ¸ 100 u ¨1 2 11 u ¨¨ ¸ ¨ © i 0 i! u 11 i ! ¹ ©
¦
· ¸ ¸ ¹
§ 1 11 55 165 330 462 462 · 100 u ¨1 ¸ 27.4% 2048 ¹ ©
showing no evidence that the suspect sample was other than normal. NOTE: The simplest way to estimate K is to use K = 100 u {0.5 + G(z)} where G(z) is the Gaussian area between the centre ordinate and the ordinate at abscissa z where z = n0.5 - (2x+1)/n0.5. For example, where n = 13 and x = 3, z = 1.6641, G(z) = 0.452 and K = 95.2%. Reference: H J Scullion, Journal of Applied Chemistry and Biotechnology, 1975, 25, pp. 503 - 508.
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APPENDIX 3 CAVITATION OF SAMPLES 1.
German method
When a liquid is to be tested in the cavitated state, the cavitation may be achieved by passing a constant stream of gas bubbles through it. The test method is modified (see Figure A3.1) as follows: The bottom of the tube (extended by 100 mm) is closed with a screw cap and PTFE gasket instead of the normal welded plate. A short steel tube of approximately 5 mm inner diameter is welded into a central hole made in this cap. A porous glass filter is attached to the inner end of the tube by means of a flexible plastics tube so that it is positioned centrally and as close as possible to the bottom of the cap. The porous disc should have a diameter of at least 35 mm and have a pore size in the range 10 to 16 ȝm (porosity 4). The air, oxygen or nitrogen flow rate should be 28 ± 5 litres/hour. In order to prevent build-up of pressure the top cap should have four additional 10 mm diameter holes drilled through it. 2.
USA method
The apparatus for the detonation tests with cavitated liquids is the same as that for solids and uncavitated liquids except that a method of injecting bubbles into the liquid sample is provided. An example of the experimental set-up is given in Figure A3.2. The bubbles are injected by means of a 23.5 mm diameter loop of vinyl plastic tubing of the type used for medical catherisation with an outer diameter of 1.8 mm and a wall thickness of 0.4 mm located at the bottom of the sample. This loop is perforated with two rows of holes diametrically opposite to each other with the holes in each row spaced 3.2 mm apart. The holes are made by inserting a 1.3 mm diameter needle through the wall of the tubing. Because of the elastic nature of the tubing the holes contract almost completely when the needle is withdrawn, so the actual hole diameter is much smaller than 1 mm. The tubing is sealed at one end of the loop with epoxy cement and a length of the tubing from the other hand of the loop is led outside to the air supply through a hole in the steel tubing, which is sealed with epoxy cement. Air is supplied at a pressure of 30 to 100 kPa to obtain a flow rate of 1.2 litres/minute. 3.
French method
This method uses glass micro-balloons (hollow closed spheres) which are commonly used to sensitize emulsion explosives e.g. soda lime borosilicate glass bubbles, apparent density 0.15, mean diameter 50 ȝm, maximum diameter 200 ȝm and with 25% having a diameter less than 30 ȝm. It is applicable to liquids and pastes. Glass micro-balloons are added, if necessary with the aid of a small quantity of dispersant which is compatible with the test substance, in the ratio of 500 mg to one litre of test substance. The mixture is agitated until formed into a homogeneous, stable dispersion and is then loaded into the firing tube.
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(A) (C) (E) (G) (J) (L)
Lead wires Detonator Substance under test Steel tube to DIN 2441 specification material St 37 to DIN 1629 specification sheet 3 Flexible plastics tube PTFE gasket
(B) (D) (F) (H)
Electric igniter Screw cap of malleable cast iron Booster charge of RDX/wax (95/5) Porous glass filter
(K) Screw cap of steel St 35 (M) Small steel tube
Figure A3.1: GERMAN METHOD OF CAVITATION
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(A) (C) (E) (G) (J)
Spacers Steel tube Bubbler Detonator holder Air supply
(B) (D) (F) (H)
Witness plate Substance under test Pentolite pellet Detonator
Figure A3.2: USA METHOD OF CAVITATION
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APPENDIX 4 NATIONAL CONTACTS FOR TEST DETAILS
Country
Code
Address
CANADA
C
Canadian Explosives Research Laboratory Department of Natural Resources CANMET Complex, Bells Corners Ontario, Canada K1A 0G1
FRANCE
F
INERIS/LSE Parc Technologique ALATA B.P. 2 60550 Verneuil-en-Halatte France
GERMANY
D
Abteilung II Bundesanstalt für Materialforschung und -prüfung Unter den Eichen 87 D - Berlin 12205 Germany
NETHERLANDS
NL
TNO Prins Maurits Laboratory P.O. Box 45 2280 AA Rijswijk The Netherlands
JAPAN
J
Technology and Safety Division Transport Policy Bureau Ministry of Transport 2-1-3 Kasumigaseki Chiyoda-ku Tokyo 100, Japan
POLAND
PL
Institute of Industrial Organic Chemistry Laboratory of Dangerous Properties of Materials 6, Annopol Street 03 - 236 Warsaw Poland
RUSSIAN FEDERATION
RUS
The State Committee of the Russian Federation on Defensive Branches of Industry Central Scientific and Design Bureau 20 Goncharnaya Street Moscow, 109240 Russian Federation
SPAIN
E
Laboratorio Oficial Madariaga (LOM) Alenza, 1 Madrid 28002 Spain
SWEDEN
S
Saab Bofors Dynamics AB Research and Development Explosives S-691 80 Karlskoga Sweden
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NATIONAL CONTACTS FOR TEST DETAILS (continued)
Country
Code
Address
SWITZERLAND
CH
Eidg. Gefahrgutinspektorat Richtistrasse 15 CH-8304 Wallisellen Switzerland
UNITED KINGDOM
GB
HSE, Health and Safety Laboratory Harpur Hill, Buxton Derbyshire SK17 9JN United Kingdom
UNITED STATES OF AMERICA
USA
Associate Director for Hazardous Materials Safety RSPA/DOT Washington D.C. USA 20590
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APPENDIX 5 EXAMPLE OF A TEST METHOD FOR VENT SIZING 1.
Introduction
This example of a method for vent sizing is used to determine the required emergency vent capacity to be fitted to a specific IBC or tank for a particular organic peroxide Type F, or self-reactive substance Type F, or formulations thereof. The method is based on experimental data which indicates that, for organic peroxide or self-reactive substance formulations, the ratio of the minimum emergency vent area to the capacity of the IBC or tank is constant and can be determined using a reduced scale tank with a 10 litre capacity. In the tests, the reduced scale tank is heated at rates equivalent to that given by complete fire engulfment or, in the case of insulated IBC or tanks, the heat transfer through the insulation with the assumption that 1% of the insulation is missing (see 4.2.1.13.8 and 4.2.1.13.9 of the Model Regulations). Others methods may be used provided that they adequately size the emergency relief device(s) on an IBC or a tank to vent all the material evolved during self-accelerating decomposition or a period of not less than one hour of complete fire-engulfment. Warning: The method does not take into account the possibility of initiation of deflagration. If this is a possibility, particularly if initiation in the vapour phase can propagate to the liquid phase, then tests should be performed which take this into account. 2.
Apparatus and materials
The reduced scale tank consists of a stainless steel test vessel with a gross volume of 10 l. The top of the tank is provided with either a 1 mm opening which simulates the pressure relief valve (PRV) of the IBC or tank or a real PRV of a diameter which is scaled using the vent area to vessel volume ratio. A second opening simulates the emergency vent opening and is closed by a bursting disc. The diameter of this vent opening can be varied by using orifice plates with different apertures. The bursting pressure of the disc fixed to the 10 l vessel should be equal to the maximum rupture pressure of the bursting discs to be fitted to the IBC or tank. This pressure should be lower than the test pressure of the tank involved. Usually, the bursting pressure is set at a level that can cope with the pressures encountered during normal transport conditions such as hydrostatic pressure from the liquid due to turn over of the tank, slopping of the contents, etc. The 10 l vessel should be provided with a bursting disc with a set pressure in the range of the disc(s) fitted on the tank or IBC as to be used in transport. For safety, it is recommended to provide the test vessel with an extra bursting disc (bursting pressure approximately 80% of the design pressure of the 10 l test vessel) with a large opening for additional emergency venting of the test vessel in the event that the chosen orifice diameter is too small. The outer surface of the test vessel, below the liquid level, is provided with an electrical heating coil or cartridge heaters connected to a power supply. Vessel contents should be heated at a constant rate independent of the heat being generated by the organic peroxide or self-reactive substance. The resistance of the heating coil should be such that, with the power available, the calculated heating rate (see section 3) can be achieved. The whole vessel is insulated with rock wool, cellular glass or ceramic fibre. The temperature inside the tank is measured by means of three thermocouples, two located in the liquid phase (near the top and bottom) and one in the gas phase. Two thermocouples are used in the liquid phase to check the homogeneity of the heating. The pressure is recorded by a pressure transducer(s) capable of recording slow and fast (at least 1 000 points/sec.) changes of pressure. Examples of test vessels are illustrated in Figure A5.1. Additional information may be obtained if the tank is mounted in a tray designed to collect any solids or liquids ejected.
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The tests should be performed at a test site with suitable safety distances. Alternatively, the test can be performed in a bunker provided with sufficient ventilation and vent openings to prevent pressure build-up in it. Explosion-proof electrical equipment should be used in such a bunker to minimise the risk of ignition. However, the tests should be performed on the assumption that the decomposition products will ignite. 3.
Calculation of the heating rate to be used in the test
If an IBC or tank is non-insulated, a heat load of the shell as given in 4.2.1.13.8 of the Model Regulations is required. For an insulated IBC or tank, the Model Regulations require that the heat load to the shell be equivalent to the heat transfer through the insulation plus the heat load to the shell on the assumption that 1% of the insulation is missing. The following information on the IBC or tank and organic peroxide or self-reactive substance is needed for the heating rate calculation: Fr Mt K L U A Cp Tpo qi qd F
= = = = = = = = = = =
fraction of tank directly heated (1 if non-insulated, 0.01 if insulated) [ņ] total mass of organic peroxide or self-reactive substance and diluent [kg] heat conductivity of the insulation layer [W.m-1.K-1] thickness of insulation layer [m] K/L= heat transfer coefficient [W.m-2.K-1] wetted area of IBC or tank [m2] -1 specific heat of the organic peroxide or self-reactive substance formulation [J.kg .K-1] temperature of organic peroxide or self-reactive substance formulation at relieving conditions [K] [W] indirectly exposed heat directly exposed heat [W] insulation factor [ņ]
Heat input, qi (W), via indirectly exposed surface (insulated part) is calculated by equations (1) and (2):
qi where:
70961 u F u > 1 Fr u A @
0.82
(1)
F = insulation factor; F = 1 for non-insulated shells, or F 2u
U(923 TPO ) 47032
for insulated shells
(2)
In the calculation of F a multiplication factor of 2 is introduced to take into account a 50% loss in insulation efficiency in an incident. Heat input, qd (W), via the directly exposed surface (non-insulated part) is calculated by equation (3): qd where:
F
70961 u F u >Fr u A @
0.82
(3)
= insulation factor = 1 (non-insulated) The overall heating rate, dT/dt (K/min), due to fire engulfment is calculated by equation (4): dT / dt
(q i q d ) 60 M tCP
- 482 -
(4)
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Example 1: insulated tank
For a typical 20 m3 insulated tank: Fr Mt K L U A Cp Tpo
= fraction of tank directly heated = 0.01 = total mass of organic peroxide or self-reactive substance and diluent = 16 268 kg = heat conductivity of the insulation layer = 0.031 W.m-1.K-1 = thickness of the insulation layer = 0.075 m = heat transfer coefficient = 0.4 W.m-2.K-1 = wetted area of tank = 40 m2 = specific heat of the organic peroxide form = 2 000 J.kg-1.K-1 = temperature of peroxide at relieving conditions = 100 °C and 0.4 u 923 373 0.82 13558 W q i 70961 u 2 u u > 1 0.01 u 40@ 47032 qd
70961 u 1 u >0.01 u 40@
0.82
13558 33474 u 60
dT dt
16268 u 2000
33474 W
0,086 K min 1
Example 2: non-insulated IBC
For a typical 1.2 m3 non-insulated stainless steel IBC (only direct heat input, qd): Fr Mt A Cp
= = = =
fraction of rank directly heated total mass of organic peroxide and diluent wetted area of IBC specific heat of the organic peroxide form
and qd
= = = =
70961 u 1 u >1 u 5.04@
0.82
1 1 012 kg 5.04 m2 2 190 J.kg-1.K-1
267308 W
qi = 0 dT dt
4.
0 267308 u 60 1012 u 2190
7.2 K min 1
Procedure
Fill the test vessel shell with the amount of organic peroxide or self-reactive substance required to give the same degree of fill (by volume of the shell) as to be used in the tank (maximum degree of fill 90%, by volume) and then install the required orifice plate1 and bursting disc. For example, it is common practice to fit four 250 mm diameter bursting discs to a 20 ton tank. This corresponds to a test vessel orifice diameter of about 11 mm. The vessel is heated at the desired rate by applying power to the heating coil. A higher than calculated heating rate may be applied initially until a temperature 5 °C above the self-accelerating decomposition temperature (for a 50 kg package) of the organic peroxide or self-reactive substance is reached. The calculated heating rate should be applied once this temperature is reached. The temperature and 1
It is recommended that either small-scale vent experiments (100 - 200 ml scale) or experiments using a very strong vessel (>100 bar) be performed prior to the performance of the 10 l vent test in order to obtain information on the maximum pressure effect from the test substance and on the required orifice diameter to be used in the first 10 l scale vent test. - 483 -
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pressure in the test vessel are recorded during the entire experiment. After rupture of the bursting disc, the heating should be continued for approximately 30 minutes more to be sure that all dangerous effects are measured. Keep distance during the execution of the test and afterwards the vessel should not be approached until the contents have cooled. The diameter of the orifice should be varied (if necessary) until a suitable opening is determined at which the maximum recorded pressure does not exceed the pressure as specified in Section 5, Test criteria and method of assessing the results. The step size used should be related to the options available in practice for the tank, i.e. larger vent sizes or more vents. If necessary the concentration of the organic peroxide or self-reactive substances can be lowered. The test should be performed in duplicate at the level at which the total vent area has sufficient capacity. 5.
Test criteria and method of assessing the results
The minimum or suitable (if it is acceptable to use a vent size larger than the minimum vent size) IBC or tank vent area, AIBC or Atank (m2), can be calculated using the minimum or suitable orifice vent area as tested in the 10 litre test at which the maximum pressure during venting is: -
for tanks not more than test pressure of the tank (according to 4.2.1.13.4 of the Model Regulations, tank shall be designed for a test pressure of at least 0.4 MPa),
-
for IBC not more than 200 kPa gauge pressure, as tested according to 6.5.6.8.4 of the Model Regulations, or higher under an approval granted by the competent authority,
and the volumes of the test vessel and IBC or tank. The minimum total IBC or tank vent area is given by: For IBCs:
A IBC
A · VIBC u §¨ test vessel Vtest vessel ¸¹ ©
For tanks:
A tank
A · Vtan k u §¨ test vessel Vtest vessel ¸¹ ©
where: Atest vessel AIBC Atank Vtest vessel VIBC Vtank
= = = = = =
[m2] [m2] [m2] [m3] [m3] [m3]
Area of venting of 10 litre test vessel Area of venting of IBC Area of venting of tank Volume of 10 litre test vessel Volume of IBC Volume of tank
Example:
For a typical organic peroxide in a 20 m3 insulated tank: Atest vessel Vtank Vtest vessel
= = =
Minimum suitable orifice area found in test Volume of tank Volume of test vessel Atank
20 u
9.5 u 10 5 0.01
- 484 -
0.19 m 2
= = =
9.5 × 10-5 m2 20 m3 0.01 m3
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(A) (B) (C) (D) (E) (F) (G) (H) (J)
Thermocouples (two in liquid and one in vapour space) Heating coil/heating cartridge Drain line, optional Insulation Manometer, optional Pressure relief valve, optional Bursting disc Orifice plate Pressure transducer or pressure relief valve and transducer on tee
Figure A5.1: 10 LITRE VESSELS FOR VENTING TESTS
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APPENDIX 6 SCREENING PROCEDURES 1.
Purpose
1.1 Industry uses screening procedures to identify the hazard potential of raw materials, reactive mixtures and intermediates, products and by-products. The use of such procedures is essential to ensure safety during research and development and to ensure that new products and processes are as safe as possible. These procedures usually consist of a combination of a theoretical appraisal and small-scale tests and, in many cases, enable an adequate hazard evaluation to be carried out without the need for larger scale classification tests. This reduces the quantity of material required, lessens any detrimental effect on the environment and minimizes the amount of unnecessary testing. 1.2 The purpose of this Appendix is to present example screening procedures. It should be used in conjunction with any screening procedures given in the introductions to the relevant test series. With the specified safety margin, the results from the screening procedures adequately predict when it is not necessary to perform the classification test as a negative result would be obtained. They are presented for guidance and their use is not compulsory. Other screening procedures may be used provided that adequate correlation has been obtained with the classification tests on a representative range of substances and there is a suitable safety margin. 2.
Scope
2.1 A hazard evaluation for a new substance should be undertaken before it is offered for transport. Initially this evaluation can use the screening procedures given in this Appendix. If the screening procedure indicates that there is a hazard, the full classification procedure should be applied. 2.2 The screening procedures are only applicable to substances and stable, homogeneous mixtures of substances. If a mixture can separate out during transport, the screening procedure should also be performed on each reactive component of the mixture in addition to the mixture. 2.3 The remarks 1.1.2 from section 1 "General introduction" are emphasized that competence on the part of the testing authority is assumed and responsibility for classification is left with them. 3.
Screening procedures for substances which may have explosive properties
3.1 The screening procedure may be used for new substances which are suspected of having explosive properties. When considering the explosive properties of self-reactive substances of Division 4.1 or organic peroxides of Division 5.2, refer to Part II of this Manual and section 5.1 of this Appendix. It should not be used for substances manufactured with the intention of producing a practical explosive or pyrotechnic effect. 3.2 Explosive properties are associated with the presence of certain chemical groups in a molecule which can react to produce very rapid increases in temperature or pressure. The screening procedure is aimed at identifying the presence of such reactive groups and the potential for rapid energy release. If the screening procedure identifies the material to be a potential explosive, the Class 1 Acceptance Procedure (see 10.3) should be applied. NOTE: Neither a Series 1 type (a) propagation of detonation test nor a Series 2 type (a) test of sensitivity to detonative shock is required if the exothermic decomposition energy of organic materials is less than 800 J/g. For organic substances and mixtures of organic substances with a decomposition energy of 800 J/g or more, tests 1 (a) and 2 (a) need not be performed if the outcome of the ballistic mortar Mk.IIId test (F.1), or the ballistic mortar test (F.2) or the BAM Trauzl test (F.3) with initiation by a standard No. 8 detonator (see Appendix 1) is "No". In this case, the results of test 1 (a) and 2 (a) are deemed to be "-".
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3.3
The acceptance procedure for Class 1 explosives need not be applied: (a)
Table A6.1
When there are no chemical groups associated with explosive properties present in the molecule. Examples of groups which may indicate explosive properties are given in Table A6.1; or
EXAMPLES OF CHEMICAL GROUPS INDICATING EXPLOSIVE PROPERTIES IN ORGANIC MATERIALS
Structural feature
Examples
C-C unsaturation C-Metal, N-Metal Contiguous nitrogen atoms
Acetylenes, acetylides, 1,2-dienes Grignard reagents, organo-lithium compounds Azides, aliphatic azo compounds, diazonium salts, hydrazines, sulphonylhydrazides Peroxides, ozonides Hydroxylamines, nitrates, nitro compounds, nitroso compounds, N-oxides, 1,2-oxazoles Chloramines, fluoroamines Chlorates, perchlorates, iodosyl compounds
Contiguous oxygen atoms N-O N-halogen O-halogen
(b)
When the substance contains chemical groups associated with explosive properties which include oxygen and the calculated oxygen balance is less than -200. The oxygen balance is calculated for the chemical reaction: CxHyOz + [x + (y/4)-(z/2)] O2 ' x CO2 + (y/2) H2O using the formula: y · § ¨ 2x z ¸ 2 ¹ ; or oxygen balance = 1600 u © molecular weight
(c)
For the organic substance or a homogenous mixture of organic substances containing chemical group (or groups) associated with explosive properties: - when the exothermic decomposition energy is less than 500 J/g, or - when the onset of exothermic decomposition is 500 °C or above as indicated by Table A6.2.
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Table A6.2
DECISION TO APPLY THE ACCEPTANCE PROCEDURE FOR CLASS 1 FOR AN ORGANIC SUBSTANCE OR A HOMOGENOUS MIXTURE OF ORGANIC SUBSTANCES
Decomposition energy (J/g)
< 500 < 500 500 500
Decomposition onset temperature (°C)
< 500 500 < 500 500
Apply acceptance procedure for Class 1? (Yes/No) No No Yes No
The exothermic decomposition energy may be determined using a suitable calorimetric technique (see 20.3.3.3); or (d)
For mixtures of inorganic oxidizing substances of Division 5.1 with organic material(s), the concentration of the inorganic oxidizing substance is: -
less than 15%, by mass, if assigned to packing group I (high hazard) or II (medium hazard);
-
less than 30%, by mass, if assigned to packing group III (low hazard).
3.4 When the substance is a mixture containing any known explosives, the class 1 acceptance procedure should be applied. 4.
Screening procedures for mixtures which may be flammable liquids (Class 3)
4.1 The procedure only applies to possible flammable mixtures1 containing known flammable liquids in defined concentrations although they may contain non-volatile components e.g. polymers, additives etc. The flash point of these mixtures need not be determined experimentally if the calculated flash point of the mixture, using the method given in 4.2, is at least 5 °C2 greater than the relevant classification criterion (23 °C and 60 °C, respectively) and provided that: (a)
The composition of the mixture is accurately known (if the material has a specified range of composition the composition with the lowest calculated flash point should be selected for assessment);
(b)
The lower explosion limit of each component is known (an appropriate correlation has to be applied when these data are extrapolated to other temperatures than test conditions) as well as a method for calculating the lower explosion limit of the mixture;
(c)
The temperature dependence of the saturated vapour pressure and of the activity coefficient is known for each component as present in the mixture;
(d)
The liquid phase is homogeneous.
1
Up to now, the calculation method is validated for mixtures containing up to six volatile components. These components may be flammable liquids like hydrocarbons, ethers, alcohols, esters (except acrylates), and water. It is however not yet validated for mixtures containing halogenated, sulphurous, and/or phosphoric compounds as well as reactive acrylates. 2
If the calculated flash point is less than 5 °C greater than the relevant classification criterion, the calculation method may not be used and the flash point should be determined experimentally. - 489 -
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4.2 A suitable method is described by Gmehling and Rasmussen (Ind. Eng. Chem. Fundament, 21, 186, (1982)). For a mixture containing non-volatile components, e.g. polymers or additives, the flash point is calculated from the volatile components. It is considered that a non-volatile component only slightly decreases the partial pressure of the solvents and the calculated flash point is only slightly below the measured value. 5.
Screening procedures for substances which may be flammable solids (Class 4)
5.1
Substances which may be self-reactive substances (Division 4.1)
The classification procedures (see section 20.4) for self-reactive substances need not be applied if: (a)
Table A6.3:
There are no chemical groups present in the molecule associated with explosive or selfreactive properties; examples of such groups are given in Tables A6.1 and A6.3; or
EXAMPLES OF CHEMICAL GROUPS PROPERTIES IN ORGANIC MATERIALS
Structural feature Mutually reactive groups S=O P-O Strained rings Unsaturation
(b)
5.2
INDICATING
SELF-REACTIVE
Examples Aminonitriles, haloanilines, organic salts of oxidizing acids Sulphonyl halides, sulphonyl cyanides, sulphonyl hydrazides Phosphites Epoxides, aziridines Olefins, cyanates
For a single organic substance or a homogeneous mixture of organic substances, the estimated SADT is greater than 75 °C or the exothermic decomposition energy is less than 300 J/g. The onset temperature and decomposition energy may be estimated using a suitable calorimetric technique (see 20.3.3.3).
Substances which may be liable to spontaneous combustion (Division 4.2)
5.2.1 The classification procedure for pyrophoric solids and liquids need not be applied when experience, in production or handling, shows that the substance do not ignite spontaneously on coming into contact with air at normal temperatures (i.e. the substance is known to be stable at room temperature for prolonged periods of time (days)). 5.2.2 The classification procedure for self-heating substances need not be applied if the results of a screening test can be adequately correlated with the classification test and an appropriate safety margin is applied. Examples of screening tests are: (a)
The Grewer Oven test (VDI guideline 2263, part 1, 1990, Test methods for the Determination of the Safety Characteristics of Dusts) with an onset temperature 80 K above the reference temperature for a volume of 1 l (33.3.1.6);
(b)
The Bulk Powder Screening Test (Gibson, N. Harper, D. J. Rogers, R. Evaluation of the fire and explosion risks in drying powders, Plant Operations Progress, 4 (3), 181 - 189, 1985) with an onset temperature 60 K above the reference temperature for a volume of 1 l (33.3.1.6).
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5.3
Substances which in contact with water may react to emit flammable gases (Division 4.3)
The classification procedure for substances which may react with water to emit flammable gases need not be applied if: (a)
The chemical structure of the substance does not contain metals or metalloids; or
(b)
Experience in production or handling shows that the substance does not react with water, e.g. the substance is manufactured in water or washed with water; or
(c)
The substance is known to be soluble in water to form a stable mixture.
6. Screening procedures for substances which may be oxidizing substances and those which may be organic peroxides (Class 5) 6.1
Substances which may be oxidizing substances (Division 5.1)
6.1.1 For organic compounds, the classification procedure for oxidizing substances of Division 5.1 need not be applied if: (a)
The compound does not contain oxygen, fluorine or chlorine; or
(b)
The compound contains oxygen, fluorine or chlorine and these elements are chemically bonded only to carbon or hydrogen.
6.1.2 For inorganic substances, the test procedure in Section 34 need not be applied if the substance does not contain any oxygen or halogen atoms. 6.2
Substances which may be organic peroxides (Division 5.2)
6.2.1 Organic peroxides are classified by definition based on their chemical structure and on the available oxygen and hydrogen peroxide content of formulations (see 20.2.2).
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APPENDIX 7 HSL FLASH COMPOSITION TEST 1.
Introduction
This test is used to determine whether pyrotechnic substances in powder form or as pyrotechnic units as presented in the fireworks, that are used to produce an aural effect, or used as a bursting charge or lifting charge, are considered to be flash compositions for the purposes of determining the classification of fireworks using the UN default fireworks classification table in 2.1.3.5.5 of the Model Regulations. 2.
Apparatus and materials
2.1 The time/pressure apparatus (Figure A7.2) consists of a cylindrical steel pressure vessel 89 mm in length and 60 mm in external diameter. Two flats are machined on opposite sides (reducing the cross-section of the vessel to 50 mm) to facilitate holding whilst fitting the cone in firing plug and vent plug. The vessel, which has a bore of 20 mm diameter, is internally rebated at either end to a depth of 19 mm and threaded to accept 1" British Standard Pipe (BSP). A pressure take-off, in the form of a side-arm, is screwed into the curved face of the pressure vessel 35 mm from one end and at 90° to the machined flats. The socket for this is bored to a depth of 12 mm and threaded to accept the 1/2" BSP thread on the end of the side-arm. A washer is fitted to ensure a gastight seal. The side-arm extends 55 mm beyond the pressure vessel body and has a bore of 6 mm. The end of the side-arm is rebated and threaded to accept a diaphragm type pressure transducer. Any pressure-measuring device may be used provided that it is not affected by the hot gases or decomposition products and is capable of responding to rates of pressure rise of 690-2 070 kPa in not more than 1 ms. 2.2 The end of the pressure vessel furthest from the side-arm is closed with a cone in firing plug which is fitted with two electrodes, one insulated from, and the other earthed to, the plug body. The other end of the pressure vessel is closed by an aluminium bursting disc 0.2 mm thick (bursting pressure approximately 2 200 kPa) held in place with a retaining plug which has a 20 mm bore. A soft lead washer is used with both plugs to ensure a good seal. 2.3 A support stand (Figure A7.8) holds the assembly in the correct attitude during use. This comprises a mild steel base plate measuring 235 mm × 184 mm × 6 mm and a 185 mm length of square hollow section (S.H.S.) 70 × 70 × 4 mm. A section is cut from each of two opposite sides at one end of the length of S.H.S. so that a structure having two flat sided legs surmounted by an 86 mm length of intact box section results. The ends of these flat sides are cut to an angle of 60° to the horizontal and welded to the base plate. 2.4 A slot measuring 22 mm wide × 46 mm deep is machined in one side of the upper end of the base section such that when the pressure vessel assembly is lowered, firing plug end first, into the box section support, the side-arm is accommodated in this slot. A packing piece of steel 30 mm wide and 6 mm thick is welded to the lower internal face of the box section to act as a spacer. Two 7 mm thumb screws, tapped into the opposite face, serve to hold the pressure vessel firmly in place. Two 12 mm wide strips of 6 mm thick steel, welded to the side pieces abutting the base of the box section, support the pressure vessel from beneath. 2.5 The ignition system consists of a Vulcan electric fusehead, with lead wires, of the type commonly used for igniting pyrotechnic substances. Fuseheads with equivalent properties may be used. 2.6 The wires of the fusehead are cut to such a length that the fusehead sits 10 mm above the top of the cone of the firing plug (see Figure A7.1). The fusehead leads are held in position using the grub screws (see Figure A7.3). - 493 -
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3.
Procedure
3.1 The apparatus, assembled complete with pressure transducer but without the aluminium bursting disc in position, is supported firing plug end down. 0.5 g of the substance is introduced into the cone of the firing plug. Where the pyrotechnic substance is in consolidated form greater than 0.5 g it should be broken to produce a piece as close to 0.5 g as possible. Where the pyrotechnic substance is in consolidated form less than 0.5 g then whole and broken units should be chosen to give 0.5 g pyrotechnic substance. The lead washer and brass or aluminium bursting disc are placed in position and the retaining plug is screwed in tightly. The charged vessel is transferred to the firing support stand, bursting disc uppermost, which should be contained in a suitable, armoured fume cupboard or firing cell. An exploder dynamo is connected to the external terminals of the firing plug and the charge is fired. The signal produced by the pressure transducer is recorded on a suitable system which allows both evaluation and a permanent record of the time/pressure profile to be achieved (e.g. transient recorder coupled to a chart-recorder). 3.2 The test is carried out three times. The time taken for the pressure to rise from 690 kPa to 2 070 kPa above atmospheric is noted. The shortest interval of three firings should be used for classification. 4.
Test criteria and method of assessing results
The test results are interpreted in terms of whether a gauge pressure of 2 070 kPa is reached and, if so, the time taken for the pressure to rise from 690 kPa to 2 070 kPa gauge. The result is considered positive “+” and the pyrotechnic substances in powder form or as pyrotechnic units as presented in the fireworks, that are used in waterfalls, or used as a bursting charge or lifting charge, is to be considered as flash composition if the minimum time taken for the pressure rise is shown to be less than, or equal to, 6 ms for 0.5 g of pyrotechnic substance. Examples of results:
Substance
Maximum pressure rise (kPa)
Mean time for a pressure rise from 690 to 2 070 kPa (ms)
Result
1 2 4 5
> 2 070 > 2 070 > 2 070 > 2 070
0.70 4.98 1.51 0.84
Flash composition Flash composition Flash composition Flash composition
6
> 2 070
11.98
Not flash composition
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(A) (B) (C)
Fusehead 10 mm gap Substance under test Figure A7.1: SAMPLE SETUP
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Figure A7.2: APPARATUS
18.6 ½" BSP
18.5 5
18.6 6.4
½" BSP
17A/F
21
(A) (B) (C) (D) (E) (F) (G) (H) (J) (K) (L) (M) (N)
Pressure vessel body Bursting disc retaining plug Firing plug Lead washer Bursting disc Side arm Pressure transducer thread PTFE washer Insulated electrode Earthed electrode Insulator Insulator Shortened grub screw
48 A/F
20 1" BSP
30
20
30
60
Groove 20
1" BSP
20
1" BSP
20
30
6
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20
28
17.5 CTRS
33
40
1" BSP
Groove
Groove
NOTE Groove dia 25 mm Groove depth 0.8 mm
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MACHINING/ASSEMBLY SEQUENCE SCREW JN0003490:B2 INTO PRESSURE PLUG BODY SCREW JN0003490:A2 INTO JN0003490:B2 DRILL & TAP M3 0.5P 7 DEEP HOLE SCREWCUT 1" BSP PARALLEL THREAD ON PRESSURE PLUG BODY
HOLE 2.5 DIA 7.8 DEEP. TAP M3 0.5P 7 DEEP. REMOVE 1st THREAD. M3 SMALL CUP POINT HEXAGON SOCKET SET SCREW – 1 REQUD 1" BSP PARALLEL
Figure A7.3: ASSEMBLY
H OLE 1.2 DIA 25 DEEP. (2 POSN) 20
HO LE 2.5 DIA 7.8 DEEP. TAP M3 0.5P 7 DEEP. REMOVE 1st THREAD (1 POSN)
17.5 CTRS
CHAM 1.0 45 DEG
28 33
0.8 GROOVE DEPTH
40 INITIAL MACHINING
HOLE 3.3 DIA 10 DEEP. TAP M4 0.7P 8 DEEP. REMO VE 1st THREAD (1 POSN)
40 A/ F
1. 2. 3. 4.
6.55 HOLE 6.50 DIA 32 DEEP. C/DRILL 6.8 DIA 14 DEEP. TAP M8 0.7P 12 DEEP. REMOVE 1st THREAD (1 POSN)
Figure A7.4: PART B1
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CHAM 0.5 45 DEG
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1.2
M3 SMALL CUP POINT HEXAGON SOCKE T SE T S CRE W. END OF SET SCRE W T O B E M/CND FLAT
2.2 2.1
CHAM 0.5 0.5
44 NOM
O/A COMBINE D LENGT H O F SET SCREW AND SLUG NOT TO EXCEED 5.5 mm
2.85 2.80
INS UL AT ING SLUG TO BE M/CND FROM PEEK GF 30
CHAM 0.5 45 DEG
A3
A2
Figure A7.5: PARTS A3 AND A2
12 3.05 HOLE 3.00 DIA 32 DEEP. C/DRILL 3.3 DIA 12 DEEP. TAP M4 0.7P 10 DEEP. REMOVE 1st THREAD
34.3 NOM
6.5 DIA TO BOTTOM OF U/CUT
1.2
6.45 6.40
CHAM 0.5 45 DEG
Figure A7.6: PART B2
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CHAM 0.5 45 DEG BOTH ENDS SAME
Figure A7.7: PART A1
20
1" BSP
17.5 CTRS 28 33 40
Figure A7.8: ASSEMBLED CONE IN PLUG
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60°
Figure A7.9: SUPPORT STAND
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APPENDIX 8 RESPONSE DESCRIPTORS
These response descriptors are to be used for the purposes of Test Series 7 criteria and designed to be used by the competent authority to determine the response type of articles. For example, articles vary greatly in size, type, packaging and explosive substances; these differences need to be taken into account. For a reaction to be judged a particular type, the primary evidence (denoted P in the table below) for that type would need to be present. The entire (both primary and secondary) body of evidence must be weighed carefully and used in its entirety by the competent authority to assess the reaction. The secondary evidence provides other indicators that may be present.
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Observed or measured effects Response level Detonation
Explosive Substances (ES) Prompt consumption of all ES once the reaction starts
Partial detonation
Blast (P) Shock wave with magnitude & timescale = to a calculated value or measured value from a calibration test
Fragment or ES projection Perforation, fragmentation and/or plastic deformation of witness plates
Other Ground craters of a size corresponding to the amount of ES in the article
(P) Rapid plastic deformation of some, but not all, of the metal casing contacting the ES with extensive high shear rate fragmentation
(P) Shock wave with magnitude & timescale < that of a calculated value or measured value from a calibration test Damage to neighboring structures
Perforation, plastic deformation and/or fragmentation of adjacent witness plates. Scattered burned or unburned ES.
Ground craters of a size corresponding to the amount of ES that detonated.
(P) Rapid combustion of some or all of the ES once the article reaction starts
(P) Extensive fracture of metal casings with no evidence of high shear rate fragmentation resulting in larger and fewer fragments than observed from purposely detonated FDOLEUDWLRQWHVWV͞
Observation or measurement of a pressure wave throughout the test arena with peak magnitude << and significantly longer duration that of a measured value from a calibration test
Witness plate damage. Significant long distance scattering of burning or unburned ES.
Ground craters.
Deflagration
(P) Combustion of some or all of the ES
(P) Rupture of casings resulting in a few large pieces that might include enclosures or attachments. *
Some evidence of pressure in the test arena which may vary in time or space.
(P) At least one piece (casing, enclosure or attachment) travels beyond 15m with an energy level > 20J based on the distance/mass relationship of Figure 16.6.1.1. Significant scattered burning or unburned ES, generally beyond 15 m.
(P) There is no primary evidence of a more severe reaction and there is evidence of thrust capable of propelling the article beyond 15m. Longer reaction time than would be expected in an explosion reaction.
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Explosion
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Case (P) Rapid plastic deformation of the metal casing contacting the ES with extensive high shear rate fragmentation
Response level Burn
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(P) No reaction of the ES without a continued external stimulus. (P) Recovery of all or most of the unreacted ES with no indication of a sustained combustion.
Observed or measured effects Blast
Case (P) The casing may rupture resulting in a few large pieces that might include enclosures or attachments. *
Some evidence of insignificant pressure in the test arena.
(P) No fragmentation of the casing or packaging greater than that from a comparable inert test item. *
None
Other
Fragment or ES projection
(P) No item (casing, enclosure, attachment or ES) travels beyond 15m with an energy level > 20J based on the distance/mass relationship detailed at Figure 16.6.1.1. (P) A small amount of burning or unburned ES relative to the total amount in the article may be scattered, generally within 15m but no farther than 30m. None
(P) No evidence of thrust capable of propelling the article beyond 15m. For a rocket motor a significantly longer reaction time than if initiated in its design mode. None
* Note: Mechanical threats will directly induce damage causing disruption of the article or even a pneumatic response resulting in parts, particularly closures, being projected. This evidence can be misinterpreted as being driven by the reaction of the explosive substance contained in the article, which may result in a more severe response descriptor being assigned. Comparison of observed evidence with that of a corresponding inert article can be useful in helping to determine the article’s response.
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No Reaction
Explosive Substances(ES) (P) Low pressure burn of some or all of the ES
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APPENDIX 9 BALLISTIC PROJECTION ENERGY TEST FOR CARTRIDGES, SMALL ARMS (UN No. 0012)
1.
Introduction
This test is conducted with candidates for Cartridges, small arms (UN No. 0012) with individual cartridges and is used to determine the maximum possible energy of a projection that could be generated upon functioning in transport. The test takes worst-case conditions into account, since no packaging attenuates the energy of the projectile and the cartridge is supported by a fixed anvil block. It is not necessary to reverse the test set-up to a situation where the cartridge is propelled, because experimentation shows that energy transfer from the propellant to the bullet is equal or more than that to the case. 2.
Apparatus and materials
The following items are required:
3.
(a)
A suitable actuator to initiate ammunition and
(b)
A ballistic pendulum with an interception device for the projectile for determining the energy, or a high-speed camera and a background with a scale to determine the velocity of the projectile.
Procedure
The test is performed on single cartridges. The cartridge is actuated as designed by means of the primer cap and a firing pin. The cartridge, actuator and measuring device are arranged along the flight path in such a way that angle errors are minimized. The test is performed three times. 4.
Test criteria and method of assessing the results
The energy of the projectile is calculated either from the maximum displacement of the ballistic pendulum or from the velocity (v) determined by the high-speed camera taking the mass (m) of the projectile into account. The value of energy (E) can be calculated from the equation: E = ½mv2 If the energy of the projectile does not exceed 8 J in any of the test runs, the article, in the appropriate packaging in accordance with Chapter 3.2 of the Model Regulations, may be assigned to Cartridges, small arms (UN No. 0012).
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