p-benzoquinone dioxime

Explosiveness

Link to relevant study record(s)

Reference

Reference 1

Endpoint:

explosive properties of explosives

Type of information:

experimental study

Adequacy of study:

key study

Study period:

01-06-2019 to 07-05-2020

Reliability:

1 (reliable without restriction)

Rationale for reliability incl. deficiencies:

guideline study

Remarks:

Well documented guideline study performed, non-GLP. All relevant validity criteria were met. Testing conducted according to international transport and supply/use regulations and manual and criteria.

Reason / purpose for cross-reference:

reference to other study

Qualifier:

according to guideline

Guideline:

UN Manual of Tests and Criteria: Part I: Classification procedures, test methods and criteria relating to explosives of Class 1

Version / remarks:

UN Manual of Tests and Criteria: Part I (Seventh ed., 2019)
Testing consisted of:
1. DSC Screening
2. UN MTC Tests associated test UN Test Series as below:
(i) Gap test : UN Test 1 (a) and/or 2 (a)
(ii) Koenen tube test : UN Test 2 (b)
(iii) Time / pressure test : UN Test 1 (c) and/or 2 (c)(i)

(iv) BAM Fallhammer test : EU Method A.14 (mechanical sensitivity: shock) and/or equivalent or similar to UN Test 3 (a)(ii)
(v) BAM friction test : EU Method A.14 (mechanical sensitivity: friction) and/or equivalent or similar to UN Test 3 (b)(i)

(vi) Deflagration Test : UN Test C.2
(vii) Dutch Pressure Vessel Test: UN Test E.2
(viii) BAM Trauzl Test : UN Test F.3

(ix) Single Package Test: UN Test 6 (a) : (i) 34-gallon fibre drum (1G), net weight 45.4 kg
(xi) External fire (bonfire) test : UN Test 6 (c) : 34-gallon fibre drum (1G), net weight 45.4 kg

Deviations:

no

Qualifier:

according to guideline

Guideline:

EU Method A.14 (Explosive properties)

Version / remarks:

See above.

Deviations:

no

GLP compliance:

no

Remarks:

Well documented guideline study performed, non-GLP. All relevant validity criteria were met. Testing conducted according to international transport and supply/use regulations and manual and criteria.

Key result

Parameter:

other: DSC screening

Remarks on result:

other: DSC screening (heating rate +5 K/min): indicated > 800 J/g at onset temperature < 500 °C (actual: 229 – 237 °C and 1879 – 2153 J/g)

Key result

Test series:

UN Test series 2

Remarks:

and/or UN Test Series 1 (a)

Method:

UN Test 2 (a): UN gap test

Parameter:

fragmented length (cm)

Value:

31

Result:

negative, not sensitive to detonative shock

Remarks:

negative, no propagation of detonation

Key result

Test series:

UN Test series 2

Method:

UN Test 2 (b): Koenen test

Parameter:

limiting diameter (mm)

Value:

2

Result:

positive, violent effect on heating under confinement

Remarks:

Fragmentation type: 'F': Tube fragmented into three or more mainly large pieces (actual 'F3', i.e. three pieces)

Key result

Test series:

UN Test series 2

Method:

UN Test 2 (c) (i): Time/pressure test

Parameter:

other: time for a pressure rise (ms)

Value:

32

Result:

negative, no or slow deflagration

Remarks on result:

time for a pressure rise from 690 to 2070 kPa (ms)

Remarks:

Evaluation according to UN test 1 (c) (i) : "+" (positive), i.e. the test substance is capable of deflagration. Evaluation according to UN test 2 (c) (i) : “-“ (negative), i.e. the test substance is not capable of rapid deflagration.

Key result

Test series:

UN Test series 3

Method:

UN Test 3 (a) (ii): BAM Fallhammer

Parameter:

limiting impact energy (J)

Value:

7.5

Result:

result is considered "-" (negative)

Remarks on result:

other: The test item showed an explosion in five of six experiments with an impact energy of 40 J. The test item showed no explosion in six tests with an impact energy of 7.5 J.

Key result

Test series:

UN Test series 3

Method:

UN Test 3 (b) (i): BAM friction apparatus

Parameter:

limiting load (N)

Value:

360

Result:

result is considered "-" (negative)

Remarks on result:

limiting load > 360 N

Key result

Test series:

other: UN Test C.2 : Deflagration Test

Method:

other: Deflagration Test

Parameter:

other: No rupture of the disc with an orifice of 3.5 mm (sample mass 10 g), but rupture of disc with orifice of 1.0 mm or larger

Value:

1

Result:

positive, ability to deflagrate

Remarks:

In the first attempt the test item deflagration was so fast that the speed could not be determined. In the second attempt, a deflagration speed of 4.35 mm/s was measured, and the test came to an end. Evaluation according to UN test C.2 : "yes, rapidly"

Key result

Test series:

other: UN Test E.2 : Dutch Pressure Vessel Test

Method:

other: UN Test E.2 : Dutch Pressure Vessel Test

Parameter:

other: sensitiveness of substance to effect of intense heat under confinement

Value:

0

Result:

other: No rupture of the disc with an orifice of 3.5 mm (sample mass 10 g), but rupture of disc with orifice of 1.0 mm or larger Actual: rupture at 1.0 mm and 2.0 mm and 2.5mm Evaluation according to UN test E.2 : "low”

Remarks on result:

other: test method examines effect of heating under confinement

Key result

Test series:

other: UN Test F.3 : BAM Trauzl Test

Method:

other: UN Test F.3 : BAM Trauzl Test

Parameter:

other: Explosive Power

Value:

0

Result:

other: For 10 g test item an expansion of 24 cm3 was observed Evaluation according to UN test F.3 : "low”

Remarks on result:

other: test method examines explosive power

Key result

Test series:

UN Test series 6

Remarks:

34-gallon fibre drum (1G), net weight 45.4 kg

Method:

UN Test 6 (a): Single package test

Parameter:

other: Mass Explosion

Value:

0

Result:

negative, no explosion

Remarks on result:

mass explosion

Remarks:

Test item burned quickly with violent flames and smoke development. After the burn, the packaging showed that the clamping ring of the cardboard barrel opened and the test item burned off completely. The cardboard barrel was not destroyed, but it showed fire holes in some places. The detection/witness plate was not damaged.

Key result

Test series:

UN Test series 6

Remarks:

34-gallon fibre drum (1G), net weight 45.4 kg Total Net Weight: 136.2 kg (3 units)

Method:

other: External fire (bonfire) test : UN Test 6 (c)

Parameter:

other: Heat flux (5 m distance) (in kW/m^2)

Value:

4.9

Result:

Division 1.4

Remarks on result:

radiant heat

Remarks:

Burning time (in seconds): 130 s Heat flux (5 m distance) ( in kW/m2): 4.9 kW/m^2 Other: no evidence of explosion, no potentially hazardous projections

Table 1.0 : Screening tests, UN Test Series 6 (a) single package test and results of UN Test Series 6 (c) external bonfire testing

Test Name	Test Number	Test Result	Comments
UN Gap test	UN 2 (a)	Negative	The tube fragmentation length was 30 cm to 31 cm and the witness plate was curved/deformed ; no holes were punched through the witness plate.
Koenen Tube test	UN 2 (b)	Positive	The sample has been shown to have a limiting diameter of 2 mm (positive) Type: ‘F’ Tube fragmented into three or more mainly large pieces
Time / Pressure test	UN 2 (c)(i)	Negative	The shortest time for a pressure rise from 690 to 2070 kPa was 32 ms Actual: 43 ms, 32 ms and/or 34 ms (n=3 replicates) Evaluation according to UN test 1 (c) (i) : "+" (positive), i.e. the test item is capable of deflagration. Evaluation according to UN test 2 (c) (i) : “-“ (negative), i.e. the test item is not capable of rapid deflagration.
BAM Fallhammer test	UN 3 (a)(ii)	Negative	The sample was observed to have a limiting impact energy of > 7.5 J The test item showed an explosion in five of six experiments with an impact energy of 40 J. The test item showed no explosion in six tests with an impact energy of 7.5 J.
BAM friction test	UN 3 (b)(i)	Negative	The sample was observed to have a limiting load of > 360 N The test item was found not to be sensitive to friction with a friction load of 360 N.
Deflagration Test	UN Test C.2	Yes, rapidly (worst-case)	In the first attempt the test item deflagration was so fast that the speed could not be determined. In the second attempt, a deflagration speed of 4.35 mm/s was measured, and the test came to an end. Evaluation according to UN test C.2 : "yes, rapidly" (worst case).
Dutch Pressure Vessel Test	UN Test E.2	Low	No rupture of the disc with an orifice of 3.5 mm (sample mass 10 g), but rupture of disc with orifice of 1.0 mm or larger Actual: rupture at 1.0 mm and 2.0 mm and 2.5mm Evaluation according to UN test E.2 : "low”
BAM Trauzl Test	UN Test F.3	Low	For 10 g test item an expansion of 24 cm3 was observed Evaluation according to UN test F.3 : "low”
Single Package Test	UN 6 (a)	Negative (no mass explosion)	34-gallon fibre drum (1G), net weight 45.4 kg Test item burned quickly with violent flames and smoke development. After the burn, the packaging showed that the clamping ring of the cardboard barrel opened and the test item burned off completely. The cardboard barrel was not destroyed, but it showed fire holes in some places. The detection/witness plate was not damaged.   UN Test 6 (b), omitted based on the results of Test 6 (a)
External fire (bonfire) Test	UN 6 (c)	Negative	34-gallon fibre drum (1G), net weight 45.4 kg 136.2 kg (3 units) Burning time (in seconds) : 130 Heat flux (5 m distance) (in kW/m^2) : 4.9 Maximum height of flame (in meters) : ca. 15

 

Testing Facility comments:

(1) The criteria for thermal effects are the burning time and the heat flux in 15 m and 5 m distances. The heat flux is measured 5 s during the period of maximum heat generation. For an exemption from Class 1 "Explosives" of the UN Recommendations of the Transport of Dangerous Goods or the Hazard Class "Explosives" of the GHS the heat flux shall be determined at the distance of 5 m.

(2) The packaged test item showed no evidence of explosion and no potentially hazardous projections, but the measured burning time was less than 330 seconds for 100 kg net mass and the heat flux 5 m for 100 kg was higher than 4.0 kW/m^2 (comparable heat flux for 136 kg is 4.9 kW/m2).

Based on the test results the test item as packed shall be classified as GHS Explosive Division 1.4 Compatibility Group C.

Interpretation of results:

Division 1.4 (substances, mixtures and articles which present no significant hazard) based on GHS criteria

Remarks:

EU & GHS criteria utilised in assessment

Conclusions:

(i) Test item: unpackaged & repackaged in non-original container : EU Criteria: CLP Regulation (EC) 1272/2008 : has the potential to meet the GHS Criteria for Division 1.1 (substances, mixtures and articles which have a mass explosion hazard): - when heated under confinement. See CLP Regulation (EC) 1272/2008: Annex 1 – section 2.1.3 for more information.

(ii) Test item: when packaged as indicated in the current study: meets GHS Criteria for Division 1.4 (compatibility group C)

Executive summary:

The potential explosivity of the test item was assessed in accordance with the UN Transport of Dangerous Goods: Manual of Tests and Criteria (Seventh ed. 2019) using Test Series 1 & 2, 3 and 6. Further information was also obtained from the following additional tests: (i) UN Test C.2 : Deflagration Test ; (ii) UN Test E.2 : Dutch Pressure Vessel Test and/or (iii) UN Test F.3 : BAM Trauzl Test. The selection of testing was made by expert judgement and in accordance of the results observed in preceding tests. The test item was positive in the Koenen tube test : UN Test 2 (b) for heating under confinement but yielded otherwise negative UN Test Series 2(a) and (c) and negative UN Test Series 3 (a)(ii) and (b) tests. Further testing in the UN Test E.2 : Dutch Pressure Vessel Test and/or UN Test F.3 : BAM Trauzl Test, indicated low sensitiveness of the substance for heating under confinement and/or low explosive power, respectively. An external : Single Package Test to UN Test Series 6 (a), was conducted on a 34-gallon fibre drum (1G), net weight 45.4 kg. This indicated no mass explosion hazard. Subsequently, a UN Test Series 6 (c) external fire (bonfire) test of the test item was conducted in packaging which was: 34-gallon fibre drum (1G), net weight 45.4 kg with Total Net Weight: 136.2 kg (3 units). The wood crib was ignited using a mixture of liquid fuels and an igniter. The heat flux was measured using infrared sensors (bolometer). The criteria for thermal effects are the burning time and the heat flux in 15 m and 5 m distances. The heat flux is measured 5 s during the period of maximum heat generation. For an exemption from Class 1 "Explosives" of the UN Recommendations of the Transport of Dangerous Goods or the Hazard Class "Explosives" of the GHS the heat flux shall be determined at the distance of 5 m. Under the conditions of the study, the packaged test item showed no evidence of explosion and no potentially hazardous projections. The measured burning time was less than 330 seconds for 100 kg net mass and the heat flux in 5 m for 100 kg was higher than 4.0 kW/m^2 (comparable heat flux for 136 kg is 4.9 kW/m2). Based on the test results the test item as packed should be classified as GHS Explosive Division 1.4 Compatibility Group C.

Cross-reference to other study:

Anon., 2020 : UN Test 6 (c) : external fire (bonfire) test in multiple packaging types: The results of the current study external bonfire test (in 34-gallon fibre drum (1G), net weight 45.4 kg) are reported in conjunction with the remaining packaging type test results, for consistency purposes.

Reference 2

Endpoint:

explosive properties of explosives

Remarks:

UN MTC Tests E.6 : External fire (bonfire) test : UN Test 6 (c) in multiple packaging types.

Type of information:

experimental study

Adequacy of study:

key study

Study period:

04-09-2020 to 07-12-2020

Reliability:

1 (reliable without restriction)

Rationale for reliability incl. deficiencies:

guideline study

Remarks:

Well documented guideline study performed, non-GLP. All relevant validity criteria were met. Testing conducted according to international transport and supply/use regulations and manual and criteria.

Reason / purpose for cross-reference:

reference to other study

Reason / purpose for cross-reference:

reference to other study

Qualifier:

according to guideline

Guideline:

UN Manual of Tests and Criteria: Part I: Classification procedures, test methods and criteria relating to explosives of Class 1

Version / remarks:

UN Manual of Tests and Criteria: Part I (Seventh ed., 2019) - external bonfire test - in multiple packaging types.

Deviations:

no

GLP compliance:

no

Remarks:

Well documented guideline study performed, non-GLP. All relevant validity criteria were met. Testing conducted according to international transport and supply/use regulations and manual and criteria.

Key result

Test series:

UN Test series 6

Remarks:

34-gallon fibre drum (1G), net weight 45.4 kg Total Net Weight: 136.2 kg (3 units)

Method:

UN Test 6 (c): External fire (bonfire) test

Parameter:

other: Heat flux (5 m distance) ( in kW/m2)

Value:

4.9

Result:

Division 1.4

Remarks on result:

radiant heat

Remarks:

Burning time (in seconds): 130 s Heat flux (5 m distance) ( in kW/m2): 4.9 kW/m^2 Other: no evidence of explosion, no potentially hazardous projections

Key result

Test series:

UN Test series 6

Remarks:

10-gallon fiberboard drum (1G), net weight 15 kg Total net weight: 90 kg (6 units)

Method:

UN Test 6 (c): External fire (bonfire) test

Parameter:

other: Heat flux (5 m distance) ( in kW/m2)

Value:

4

Result:

Division 1.4

Remarks on result:

radiant heat

Remarks:

Burning time (in seconds): 80 s Heat flux (5 m distance) ( in kW/m2): > 4.0 kW/m^2 Other: no evidence of explosion, no potentially hazardous projections

Key result

Test series:

UN Test series 6

Remarks:

5-gallon fiberboard drum (1G), net weight 4 kg Total net weight: 43 kg (10 units)

Method:

UN Test 6 (c): External fire (bonfire) test

Parameter:

other: Heat flux (5 m distance) ( in kW/m2)

Value:

4

Result:

Division 1.4

Remarks on result:

radiant heat

Remarks:

Burning time (in seconds): 70 s Heat flux (5 m distance) ( in kW/m2): > 4.0 kW/m^2 Other: no evidence of explosion, no potentially hazardous projections

Key result

Test series:

UN Test series 6

Remarks:

5-gallon PE pails removable head (2H1) inserted in fibreboard box (4G), net weight of 5-gallon was about 8 kg Total net weight: 114 kg (14 units)

Method:

UN Test 6 (c): External fire (bonfire) test

Parameter:

other: Heat flux (5 m distance) ( in kW/m2)

Value:

4

Result:

Division 1.4

Remarks on result:

radiant heat

Remarks:

Burning time (in seconds): 100 s Heat flux (5 m distance) ( in kW/m2): > 4.0 kW/m^2 Other: no evidence of explosion, no potentially hazardous projections

Key result

Test series:

UN Test series 6

Remarks:

4 PE gallon jerricans (3H2) inserted in fibreboard box (4C), net weight of each gallon ranged between 1.4 - 1.7 kg Total net weight: 96 kg (15 units)

Method:

UN Test 6 (c): External fire (bonfire) test

Parameter:

other: Heat flux (5 m distance) ( in kW/m2)

Value:

4

Result:

Division 1.4

Remarks on result:

radiant heat

Remarks:

Burning time (in seconds): 20 s Heat flux (5 m distance) ( in kW/m2): > 4.0 kW/m^2 Other: no evidence of explosion, no potentially hazardous projections

Key result

Test series:

UN Test series 6

Remarks:

plastic jerricans (3H1) with removable head and a volume of 20 1/5 gallon (inner packaging). Each plastic jerrican was inserted in a fibreboard box (4G) (outer packaging), net weight was about 8 kg Total net weight: 112 kg (14 units)

Method:

UN Test 6 (c): External fire (bonfire) test

Parameter:

other: Heat flux (5 m distance) ( in kW/m2)

Value:

4

Result:

Division 1.4

Remarks on result:

radiant heat

Remarks:

Burning time (in seconds): 100 s Heat flux (5 m distance) ( in kW/m2): > 4.0 kW/m^2 Other: no evidence of explosion, no potentially hazardous projections

The test is performed on packages of the explosive substance to determine whether there is a mass explosion or a hazard from dangerous projection, radiant heat and/or violent burning when involved in a fire.

The test item was  evaluated in larger packages in accordance with test series 6 and classified in Division 1.4 (test facility reference provided in the full study report):

(i) 34-gallon fibre drum (1G), net weight 45.4 kg (see cross-referenced study)

(ii) 10-gallon fibreboard drum (1G), net weight 15 kg

(iii) 5-gallon fibreboard drum (1G), net weight 4 kg

(iv) 5-gallon PE pails removable head (2H1) inserted in fibreboard box (4G), net weight of 5-gallon was about 8 kg

(v) 4 PE gallon jerricans (3H2) inserted in fibreboard box (4C),  net weight of each gallon ranged between 1.4 - 1.7 kg

The (further) the UN-test 6 (c) should be used to examine whether the test substance in smaller packaging may be excluded from the Class "Explosives ": package type: (vi) plastic jerricans (3H1) with removable head and a volume of 20 1/5 gallon (inner packaging). Each plastic jerrican was inserted in a fibreboard box (4G) (outer packaging), net weight was about 8 kg

Within the UN-test 6 (c) observations are made on the following:

(a) Evidence of explosion;

(b) Potentially hazardous projections and

(c) Thermal effects.

For (vi) in the external fire test 14 packages each with 8 kg of the packaged test item were placed on the metal grid. The wood crib was ignited using a mixture of liquid fuels and an igniter. The heat flux was measured using infrared sensors (bolometer).

 

Table 1.0 : Packaging types and results of UN Test Series 6 (c) external bonfire tests

Test	Packaging unit	Total net weight	Burning time (in seconds)	Heat flux : 5 m distance (in kW/m^2)	Maximum height of flame (in meters)
(i)	34-gallon fibre drum (1G), net weight 45.4 kg	136.2 kg (3 units)	130	4.9	ca. 15
(ii)	10-gallon fiberboard drum (1G), net weight 15 kg	90 kg (6 units)	80	> 4	ca. 10
(iii)	5-gallon fiberboard drum (1G), net weight 4 kg	43 kg (10 units)	70	> 4	5.3
(iv)	5-gallon PE pails removable head (2H1) inserted in fibreboard box (4G), net weight of 5-gallon was about 8 kg	114 kg (14 units)	100	> 4	15
(v)	4 PE gallon jerricans (3H2) inserted in fibreboard box (4C),  net weight of each gallon ranged between 1.4 - 1.7 kg	96 kg (15 units)	20	> 4	9
(vI)	plastic jerricans (3H1) with removable head and a volume of 20 1/5 gallon (inner packaging). Each plastic jerrican was inserted in a fibreboard box (4G) (outer packaging), net weight was about 8 kg	112 kg (14 units)	100	> 4	ca. 15
	Criteria to pass test	100 kg net mass	> 330 s	< 4 kW/m^2 #1

Where:

#1: Irradiance measured over 5 s during period of max. output < 4 kW/m^2

Testing Facility comments:

(1) The criteria for thermal effects are the burning time and the heat flux in 15 m and 5 m distances. The heat flux is measured 5 s during the period of maximum heat generation. For an exemption from Class 1 "Explosives" of the UN Recommendations of the Transport of Dangerous Goods or the Hazard Class "Explosives" of the GHS the heat flux shall be determined at the distance of 5 m.

(2) The packaged test item showed no evidence of explosion and no potentially hazardous projections, but the measured burning time was less than 330 seconds for 100 kg net mass and the heat flux in 5 m for 100 kg was higher than 4.0 kW/m^2 (comparable heat flux for 112 kg is 4.3 kW/m2). Based on the test results the test item as packed shall be classified as GHS Explosive Division 1.4 Compatibility Group C.

Interpretation of results:

Division 1.4 (substances, mixtures and articles which present no significant hazard) based on GHS criteria

Conclusions:

For all packaging types : the packaged test item showed no evidence of explosion and no potentially hazardous projections. In all packaging types, the measured burning time was less than 330 seconds for 100 kg net mass and the heat flux in 5 m for 100 kg was higher than 4.0 kW/m^2 (comparable heat flux for 112 kg is 4.3 kW/m2). Based on the test results the test item as packed should be classified as GHS Explosive Division 1.4 Compatibility Group C.

Executive summary:

The potential explosivity of the test item was assessed in accordance with the UN Transport of Dangerous Goods: Manual of Tests and Criteria (Seventh ed. 2019) using Test Series 6 (c) : external fire (bonfire) test of the test item within multiple packaging types. The selection of testing was made by expert judgement of the testing facility and in accordance of the results observed in preceding tests. Testing was completed within the following packaging types: (i) 34-gallon fibre drum (1G), net weight 45.4 kg ; (ii) 10-gallon fibreboard drum (1G), net weight 15 kg ; (iii) 5-gallon fibreboard drum (1G), net weight 4 kg ; (iv) 5-gallon PE pails removable head (2H1) inserted in fibreboard box (4G), net weight of 5-gallon was about 8 kg ; (v) 4 PE gallon jerricans (3H2) inserted in fibreboard box (4C), net weight of each gallon ranged between 1.4 - 1.7 kg and/or (vi) plastic jerricans (3H1) with removable head and a volume of 20 1/5 gallon (inner packaging). Each plastic jerrican was inserted in a fibreboard box (4G) (outer packaging), net weight was about 8 kg. For (vi) in the external fire test 14 packages each with 8 kg of the packaged test item were placed on the metal grid. The wood crib was ignited using a mixture of liquid fuels and an igniter. The heat flux was measured using infrared sensors (bolometer). The criteria for thermal effects are the burning time and the heat flux in 15 m and 5 m distances. The heat flux is measured 5 s during the period of maximum heat generation. For an exemption from Class 1 "Explosives" of the UN Recommendations of the Transport of Dangerous Goods or the Hazard Class "Explosives" of the GHS the heat flux shall be determined at the distance of 5 m. Under the conditions of the study, for all packaging types : the packaged test item showed no evidence of explosion and no potentially hazardous projections. In all packaging types, the measured burning time was less than 330 seconds for 100 kg net mass and the heat flux in 5 m for 100 kg was higher than 4.0 kW/m^2 (comparable heat flux for 112 kg is 4.3 kW/m2). Based on the test results the test item as packed should be classified as GHS Explosive Division 1.4 Compatibility Group C.

Reference 3

Endpoint:

explosive properties of explosives

Type of information:

experimental study

Adequacy of study:

key study

Study period:

21-06-2017 to 30-01-2018

Reliability:

1 (reliable without restriction)

Rationale for reliability incl. deficiencies:

guideline study

Remarks:

Well documented guideline study performed, non-GLP. All relevant validity criteria were met. Testing conducted according to international transport and supply/use regulations and manual and criteria.

Reason / purpose for cross-reference:

reference to other study

Qualifier:

according to guideline

Guideline:

UN Manual of Tests and Criteria: Part I: Classification procedures, test methods and criteria relating to explosives of Class 1

Version / remarks:

UN MTC Tests E.2 and E.3 and E.6 and associated test UN Test Series as below:
(i) Gap test : UN Test 2 (a)
(ii) Koenen tube test : UN Test 2 (b)
(iii) Time / pressure test : UN Test 2 (c)(i)

(iv) BAM Fallhammer test : UN Test 3 (a)(ii)
(v) BAM friction test : UN Test 3 (b)(i)
(vi) Thermal stability test at 75°C : UN Test 3 (c)
(vii) Small scale burning test : UN Test 3 (d)

(viii) External fire (bonfire) test : UN Test 6 (c)

Deviations:

no

GLP compliance:

no

Remarks:

Well documented guideline study performed, non-GLP. All relevant validity criteria were met. Testing conducted according to international transport and supply/use regulations and manual and criteria.

Key result

Test series:

UN Test series 2

Method:

UN Test 2 (a): UN gap test

Parameter:

fragmented length (cm)

Value:

0

Result:

negative, not sensitive to detonative shock

Remarks:

negative, no propagation of detonation

Key result

Test series:

UN Test series 2

Method:

UN Test 2 (b): Koenen test

Parameter:

limiting diameter (mm)

Value:

2

Result:

positive, violent effect on heating under confinement

Remarks:

Fragmentation type: 'F': Tube fragmented into three or more mainly large pieces

Key result

Test series:

UN Test series 2

Method:

UN Test 2 (c) (i): Time/pressure test

Parameter:

other: time for a pressure rise (ms)

Value:

39

Result:

negative, no or slow deflagration

Remarks on result:

time for a pressure rise from 690 to 2070 kPa (ms)

Key result

Test series:

UN Test series 3

Method:

UN Test 3 (a) (ii): BAM Fallhammer

Parameter:

limiting impact energy (J)

Value:

15

Result:

result is considered "-" (negative)

Key result

Test series:

UN Test series 3

Method:

UN Test 3 (b) (i): BAM friction apparatus

Parameter:

limiting load (N)

Value:

360

Result:

result is considered "-" (negative)

Remarks on result:

limiting load > 360 N

Key result

Test series:

UN Test series 3

Method:

UN Test 3 (c) (i): Thermal stability test at 75°C

Parameter:

other: Thermal stability at 75 °C

Value:

0

Result:

result is considered "-" (negative)

Remarks:

No ignition / explosion / self-heating occurred during the test. The test result is therefore considered negative (-)

Key result

Test series:

UN Test series 3

Method:

UN Test 3 (d): Small-scale burning test

Parameter:

other: fails to ignite, burn and/or explode

Value:

0

Result:

result is considered "-" (negative)

Remarks on result:

other: observed to ignite and burn in all four tests

Test series:

UN Test series 6

Method:

other: External fire (bonfire) test : UN Test 6 (c)

Parameter:

other: basis of whether a mass explosion, potentially hazardous projections or damage to the witness screens occurs

Value:

0

Result:

result is considered "-" (negative)

Remarks on result:

other: See 'Remarks'

Remarks:

Package was quickly engulfed by the flames and ignited. The contents ignited and burned fiercely. Some burning material exited the drum and landed with 1 m of the fire, where it continued to burn. No metallic projections were seen and no impacts were recorded on the witness screens. No jetting of flames was seen.

Table1.0 : Test Results for the test item

Test Name	Test Number	Test Result	Comments
UN Gap test	UN 2 (a)	Negative	The tube remained intact during both tests and no holes were punched through the witness plate.
Koenen Tube test	UN 2 (b)	Positive	The sample has been shown to have a limiting diameter of 2 mm (positive) Type: ‘F’ Tube fragmented into three or more mainly large pieces
Time / Pressure test	UN 2 (c)(i)	Negative	The shortest time for a pressure rise from 690 to 2070 kPa was 39 ms
BAM Fallhammer test	UN 3 (a)(ii)	Negative	The sample was observed to have a limiting impact energy of 15 J
BAM friction test	UN 3 (b)(i)	Negative	The sample was observed to have a limiting load of > 360 N
Thermal stability test at 75°C	UN 3 (c)	Negative	No ignition / explosion / self-heating occurred during the test
Small scale burning test	UN 3 (d)	Negative	The sample was observed to ignite and burn in all four tests
External fire (bonfire) test	UN 6 (c)	Negative	The fibreboard drum was quickly engulfed by the flames and ignited. The contents of the drum then ignited and burned fiercely. Some burning material exited the drum and landed with 1 m of the fire, where it continued to burn. No metallic projections were seen and no impacts were recorded on the witness screens. No jetting of flames was seen.

 

 

Interpretation of results:

other: result for : Unpackaged substance. More information provided in 'Conclusions'.

Remarks:

EU & GHS criteria utilised in assessment

Conclusions:

Unpackaged Test Item: EU Criteria: CLP Regulation (EC) 1272/2008 : has the potential to meet the GHS Criteria for Division 1.1 (substances, mixtures and articles which have a mass explosion hazard): - when heated under confinement. See CLP Regulation (EC) 1272/2008: Annex 1 – section 2.1.3 for more information.

Executive summary:

The potential explosivity of the test item was assessed in accordance with the UN Transport of Dangerous Goods: Manual of Tests and Criteria (2015) using Test Series 2, 3 and 6. The selection of testing was made by expert judgement and in accordance of the results observed in preceding tests. The test item was positive in the Koenen tube test : UN Test 2 (b) for heating under confinement but yielded otherwise negative UN Test Series 2(a) and (b) and negative UN Test Series 3 (a)(ii), (b) and (d) tests. On the basis of preceding testing UN Test Series 6(a) and (b) were omitted. The test item packaged in a 34 gallon fibreboard drum used for transport, was tested in UN Test Series 6(c): bonfire test at an appropriately licenced facility.

Note: Within the present study (packaged substance) Test Series 6(c), result and conclusion is overridden by the later (anon., 2020) External fire (bonfire) test: UN Test 6 (c) in multiple packaging types. Refer to cross-referenced study.

Description of key information

Packaged substance - Explosivity: For all tested packaging types : the packaged test item showed no evidence of explosion and no potentially hazardous projections. The substance as packed should be classified as GHS Explosive Division 1.4 Compatibility Group C and H204: Fire or projection hazard ; UN MTC Test Series 6(c) - External fire (bonfire) test, 2020
Unpackaged substance or re-packaged substance (not in original packaging) - Explosivity: Explosive if heated under confinement, UN MTC Test Series 2(b) - Koenen Tube test, 2018 and/or MTC Test Series 2(b) - Koenen Tube test, 2020
For un-packaged or re-packaged substance (not in original packaging) the risk to users of the substance is explicitly communicated by the application of : CLP Regulation (EC) 1272/2008: Note 1 to Table 2.1.2 in Annex 1 – section 2.1.3 and due to associated communication of the ‘Risk of explosion if heated under confinement’.

Key value for chemical safety assessment

Explosiveness:

explosive

Additional information

Key study : UN MTC (2015), 2018: The potential explosivity of the test item was assessed in accordance with the UN Transport of Dangerous Goods: Manual of Tests and Criteria (2015) using Test Series 2, 3 and 6. The selection of testing was made by expert judgement and in accordance of the results observed in preceding tests. The test item was positive in the Koenen tube test : UN Test 2 (b) for heating under confinement but yielded otherwise negative UN Test Series 2(a) and (b) and negative UN Test Series 3 (a)(ii), (b) and (d) tests. On the basis of preceding testing UN Test Series 6(a) and (b) were omitted. The test item packaged in a 34 gallon fibreboard drum used for transport, was tested in UN Test Series 6(c): bonfire test at an appropriately licenced facility.
Note: Within the present study (packaged substance) Test Series 6(c), result and conclusion is overridden by the later (anon., 2020) External fire (bonfire) test: UN Test 6 (c) in multiple packaging types. Refer to cross-referenced study.

Table 1.0 : UN Transport MTC (2015) - results of test series

Test Name	Test Number	Test Result	Comments
UN Gap test	UN 2 (a)	Negative	The tube remained intact during both tests and no holes were punched through the witness plate.
Koenen Tube test	UN 2 (b)	Positive	The sample has been shown to have a limiting diameter of 2 mm (positive) Type: ‘F’ Tube fragmented into three or more mainly large pieces
Time / Pressure test	UN 2 (c)(i)	Negative	The shortest time for a pressure rise from 690 to 2070 kPa was 39 ms
BAM Fallhammer test	UN 3 (a)(ii)	Negative	The sample was observed to have a limiting impact energy of 15 J
BAM friction test	UN 3 (b)(i)	Negative	The sample was observed to have a limiting load of > 360 N
Thermal stability test at 75°C	UN 3 (c)	Negative	No ignition / explosion / self-heating occurred during the test
Small scale burning test	UN 3 (d)	Negative	The sample was observed to ignite and burn in all four tests
External fire (bonfire) test	UN 6 (c)	Negative	The fibreboard drum was quickly engulfed by the flames and ignited. The contents of the drum then ignited and burned fiercely. Some burning material exited the drum and landed with 1 m of the fire, where it continued to burn. No metallic projections were seen and no impacts were recorded on the witness screens. No jetting of flames was seen.

 

Key study : UN MTC (7th ed., 2019), screening tests, single package test and external bonfire test, 2020 : The potential explosivity of the test item was assessed in accordance with the UN Transport of Dangerous Goods: Manual of Tests and Criteria (Seventh ed. 2019) using Test Series 1 & 2, 3 and 6. Further information was also obtained from the following additional tests: (i) UN Test C.2 : Deflagration Test ; (ii) UN Test E.2 : Dutch Pressure Vessel Test and/or (iii) UN Test F.3 : BAM Trauzl Test. The selection of testing was made by expert judgement and in accordance of the results observed in preceding tests. The test item was positive in the Koenen tube test : UN Test 2 (b) for heating under confinement but yielded otherwise negative UN Test Series 2(a) and (c) and negative UN Test Series 3 (a)(ii) and (b) tests. Further testing in the UN Test E.2 : Dutch Pressure Vessel Test and/or UN Test F.3 : BAM Trauzl Test, indicated low sensitiveness of the substance for heating under confinement and/or low explosive power, respectively. An external : Single Package Test to UN Test Series 6 (a), was conducted on a 34-gallon fibre drum (1G), net weight 45.4 kg. This indicated no mass explosion hazard. Subsequently, a UN Test Series 6 (c) external fire (bonfire) test of the test item was conducted in packaging which was: 34-gallon fibre drum (1G), net weight 45.4 kg with Total Net Weight: 136.2 kg (3 units). The wood crib was ignited using a mixture of liquid fuels and an igniter. The heat flux was measured using infrared sensors (bolometer). The criteria for thermal effects are the burning time and the heat flux in 15 m and 5 m distances. The heat flux is measured 5 s during the period of maximum heat generation. For an exemption from Class 1 "Explosives" of the UN Recommendations of the Transport of Dangerous Goods or the Hazard Class "Explosives" of the GHS the heat flux shall be determined at the distance of 5 m. Under the conditions of the study, the packaged test item showed no evidence of explosion and no potentially hazardous projections. The measured burning time was less than 330 seconds for 100 kg net mass and the heat flux in 5 m for 100 kg was higher than 4.0 kW/m^2 (comparable heat flux for 136 kg is 4.9 kW/m2). Based on the test results the test item as packed should be classified as GHS Explosive Division 1.4 Compatibility Group C.

 

Table 1.1 : Screening tests, UN Test Series 6 (a) single package test

Test Name	Test Number	Test Result	Comments
UN Gap test	UN 2 (a)	Negative	The tube fragmentation length was 30 cm to 31 cm and the witness plate was curved/deformed ; no holes were punched through the witness plate.
Koenen Tube test	UN 2 (b)	Positive	The sample has been shown to have a limiting diameter of 2 mm (positive) Type: ‘F’ Tube fragmented into three or more mainly large pieces
Time / Pressure test	UN 2 (c)(i)	Negative	The shortest time for a pressure rise from 690 to 2070 kPa was 32 ms Actual: 43 ms, 32 ms and/or 34 ms (n=3 replicates)   Evaluation according to UN test 1 (c) (i) : "+" (positive), i.e. the test item is capable of deflagration. Evaluation according to UN test 2 (c) (i) : “-“ (negative), i.e. the test item is not capable of rapid deflagration.
BAM Fallhammer test	UN 3 (a)(ii)	Negative	The sample was observed to have a limiting impact energy of > 7.5 J   The test item showed an explosion in five of six experiments with an impact energy of 40 J. The test item showed no explosion in six tests with an impact energy of 7.5 J.
BAM friction test	UN 3 (b)(i)	Negative	The sample was observed to have a limiting load of > 360 N   The test item was found not to be sensitive to friction with a friction load of 360 N.
Deflagration Test	UN Test C.2	Yes, rapidly (worst-case)	In the first attempt the test item deflagration was so fast that the speed could not be determined. In the second attempt, a deflagration speed of 4.35 mm/s was measured, and the test came to an end. Evaluation according to UN test C.2 : "yes, rapidly" (worst case).
Dutch Pressure Vessel Test	UN Test E.2	Low	No rupture of the disc with an orifice of 3.5 mm (sample mass 10 g), but rupture of disc with orifice of 1.0 mm or larger Actual: rupture at 1.0 mm and 2.0 mm and 2.5mm Evaluation according to UN test E.2 : "low”
BAM Trauzl Test	UN Test F.3	Low	For 10 g test item an expansion of 24 cm3 was observed Evaluation according to UN test F.3 : "low”
Single Package Test	UN 6 (a)	Negative (no mass explosion)	34-gallon fibre drum (1G), net weight 45.4 kg Test item burned quickly with violent flames and smoke development. After the burn, the packaging showed that the clamping ring of the cardboard barrel opened and the test item burned off completely. The cardboard barrel was not destroyed, but it showed fire holes in some places. The detection/witness plate was not damaged.   UN Test 6 (b), omitted based on the results of Test 6 (a)

Note: The results of the current study external bonfire test (in 34-gallon fibre drum (1G), net weight 45.4 kg) are reported in conjunction with the remaining packaging type test results (below), for consistency purposes.

 

Key study : UN MTC (7th ed., 2019), external bonfire test - multiple packaging types, 2020 : The potential explosivity of the test item was assessed in accordance with the UN Transport of Dangerous Goods: Manual of Tests and Criteria (Seventh ed. 2019) using Test Series 6 (c) : external fire (bonfire) test of the test item within multiple packaging types. The selection of testing was made by expert judgement of the testing facility and in accordance of the results observed in preceding tests. Testing was completed within the following packaging types: (i) 34-gallon fibre drum (1G), net weight 45.4 kg ; (ii) 10-gallon fibreboard drum (1G), net weight 15 kg ; (iii) 5-gallon fibreboard drum (1G), net weight 4 kg ; (iv) 5-gallon PE pails removable head (2H1) inserted in fibreboard box (4G), net weight of 5-gallon was about 8 kg ; (v) 4 PE gallon jerricans (3H2) inserted in fibreboard box (4C), net weight of each gallon ranged between 1.4 - 1.7 kg and/or (vi) plastic jerricans (3H1) with removable head and a volume of 20 1/5 gallon (inner packaging). Each plastic jerrican was inserted in a fibreboard box (4G) (outer packaging), net weight was about 8 kg. For (vi) in the external fire test 14 packages each with 8 kg of the packaged test item were placed on the metal grid. The wood crib was ignited using a mixture of liquid fuels and an igniter. The heat flux was measured using infrared sensors (bolometer). The criteria for thermal effects are the burning time and the heat flux in 15 m and 5 m distances. The heat flux is measured 5 s during the period of maximum heat generation. For an exemption from Class 1 "Explosives" of the UN Recommendations of the Transport of Dangerous Goods or the Hazard Class "Explosives" of the GHS the heat flux shall be determined at the distance of 5 m. Under the conditions of the study, for all packaging types : the packaged test item showed no evidence of explosion and no potentially hazardous projections. In all packaging types, the measured burning time was less than 330 seconds for 100 kg net mass and the heat flux in 5 m for 100 kg was higher than 4.0 kW/m^2 (comparable heat flux for 112 kg is 4.3 kW/m2). Based on the test results the test item as packed should be classified as GHS Explosive Division 1.4 Compatibility Group C.

 

Table 1.2 : Packaging types and results of UN Test Series 6 (c) external bonfire tests

Test	Packaging unit	Total net weight	Burning time (in seconds)	Heat flux (5 m distance) ( in kW/m^2)	Maximum height of flame (in meters)
(i)	34-gallon fibre drum (1G), net weight 45.4 kg	136.2 kg (3 units)	130	4.9	ca. 15
(ii)	10-gallon fiberboard drum (1G), net weight 15 kg	90 kg (6 units)	80	> 4	ca. 10
(iii)	5-gallon fiberboard drum (1G), net weight 4 kg	43 kg (10 units)	70	> 4	5.3
(iv)	5-gallon PE pails removable head (2H1) inserted in fibreboard box (4G), net weight of 5-gallon was about 8 kg	114 kg (14 units)	100	> 4	15
(v)	4 PE gallon jerricans (3H2) inserted in fibreboard box (4C),  net weight of each gallon ranged between 1.4 - 1.7 kg	96 kg (15 units)	20	> 4	9
(vI)	plastic jerricans (3H1) with removable head and a volume of 20 1/5 gallon (inner packaging). Each plastic jerrican was inserted in a fibreboard box (4G) (outer packaging), net weight was about 8 kg	112 kg (14 units)	100	> 4	ca. 15
For information:	Criteria to pass test	100 kg net mass	> 330 s	< 4 kW/m^2 #1

Where:

#1: Irradiance measured over 5 s during period of max. output < 4 kW/m^2

Justification for classification or non-classification

The packaged substance meets the classification criteria under Regulation (EC) No 1272/2008 for explosives – Division 1.4 compatibility group C : H204: Fire or projection hazard.

The unpackaged substance & repackaged in non-original container has the potential to meet the classification criteria under Regulation (EC) No 1272/2008 for explosives – Division 1.1: H201: Explosive; mass explosion hazard ; if inappropriately packaged or when re-packaged (not in original packaging containers) due to ‘Risk of explosion if heated under confinement’. The risk to users of the substance when un-packaged or re-packaged substance (not in original packaging) is covered by the automatic application of : CLP Regulation (EC) 1272/2008: Note 1 to Table 2.1.2 in Annex 1 – section 2.1.3.

This is to ensure that substances which may technically be ‘inadequately covered’ by the classification criteria per se : due to ‘packaging dependence’ will remain covered and the risks of the substance which is unpackaged/re-packaged (non-original container) due to ‘Risk of explosion if heated under confinement’ are communicated. Refer to ECHA Guidance on the CLP criteria (2017) – pages 104-107 for further information.

References:
1. REACH Regulation (EC) 1907/2006, Annex VII, section 7.11
2. CLP Regulation (EC) 1272/2008, Annex I, section 1 and 2
3. UN Transport of Dangerous Goods Manual of Tests and Criteria, Seventh Edition (2019)
4. ECHA Guidance on Application on the CLP Criteria, section 2.1 (v5.0, July 2017)
5. ECHA Guidance on Information Requirements and Chemical Safety Assessment (Chapter R.7a: Endpoint Specific Guidance, July 2017)