NATO NATO STANDARDIZATION OFFICE

OTAN BuREAU OTAN DE NORMALISATION

16 November 2016 NS0/1406(2016)SGA/4666

STANAG 4666 SGA (EDITION 1)- EXPLOSIVES, ASSESSMENT OF AGEING OF POLYMER

BONDED EXPLOSIVES (PBXS) CAST-CURED COMPOSITIONS USING INERT OR
ENERGETIC BINDERS

Reference:
NS0/0416(2015)CASG/4666, dated 30 March 2015 (Edition 1) (Ratification Draft 1)

1. The enclosed NATO Standardization Agreement, which has been ratified by nations as
reflected in the NATO Standardization Document Database (NSDD), is promulgated herewith.

2. The reference listed above is to be destroyed in accordance with local document destruction
procedures.

ACTION BY NATIONAL STAFFS

3. National staffs are requested to examine their ratification status of the STANAG and, if they
have not already done so, advise the NSO, through their national delegation as appropriate of their
intention regarding its ratification and implementation.

4. It should be noted that this standard entered development/ratification under AAP-03(1) and
therefore is promulgated in its current format.

Edvardas MAZEIKIS
Major General, LTUAF
Director, NATO Standardization Office
Enclosure:
STANAG 4666 (Edition 1)

NATO Standardization Office- Bureau OTAN de normalisation

B-1110 Brussels, Belgium Internet site: http://nso.nato.int
E-mail: nso@nso.nato.int- Tel32.2.707.5556- Fax 32.2.707.5718
 STANAG 4666
(Edition 1)

NORTH ATLANTIC TREATY ORGANIZATION

{NATO)

NATO STANDARDIZATION OFFICE

(NSO)

STANDARDIZATION AGREEMENT
{STANAG)

SUBJECT: EXPLOSIVES. ASSESSMENT OF AGEING OF POLYMER BONDED EXPLOSIVES

(PBXS) CAST-CURED COMPOSITIONS USING INERT OR ENERGETIC
BINDERS

Promulgated on 16 November 2016

Edvardas MAZEIKIS
Major General, LTUAF
Director, NATO Standardization Office
 RECORD OF AMENDMENTS

No. Reference/Date of Date entered Signature

amendment

EXPLANATORY NOTES
AGREEMENT

1. This STANAG is promulgated by the Director NATO Standardization Office

under the authority vested in him by the North Atlantic Council.

2. No departure may be made from the agreement without informing the tasking
authority in the form of a reservation. Nations may propose changes at any time to the
tasking authority where they will be processed in the same manner as the original
agreement.

3. Ratifying nations have agreed that national orders, manuals and instructions
implementing this STANAG will include a reference to the STANAG number for purposes
of identification.

RATIFICATION, IMPLEMENTATION AND RESERVATIONS

4. Ratification, implementation and reservation details are available on request or

through the NSO websites (internet http://nso.nato.int; NATO Secure WAN
http://nso.hq.nato.int).

RESTRICTION TO REPRODUCTION

5. No part of this publication may be reproduced, stored in a retrieval system, used

commercially, adapted, or transmitted in any form or by any means, electronic,
mechanical, photocopying, recording or otherwise, without the prior permission of the
publisher. With the exception of commercial sales, this does not apply to member and
partner nations, or NATO commands and bodies.

FEEDBACK

6. Any comments concerning this publication should be directed to NATO/NSO – Bvd

Leopold III - 1110 Brussels - Belgium.
 STANAG 4666
(Edition 1)

NATO STANDARDIZATION AGREEMENT

(STANAG)

EXPLOSIVES, ASSESSMENT OF AGEING OF POLYMER BONDED EXPLOSIVES (PBXS) CAST-

CURED COMPOSITIONS USING INERT OR ENERGETIC BINDERS
Annexes:
A. Scope of the agreement
B. Principles and methodology
C. Accelerated ageing procedure
D. Test procedures

Related documents:
1. STANAG 4170, Principles and methodology for the qualification of explosive materials
for military use.
2. STANAG 4487, Explosives, Friction Sensitivity Tests.
3. STANAG 4488, Explosives, Shock Sensitivity Tests.
4. STANAG 4489, Explosives, Impact Sensitivity Tests.
5. STANAG 4490, Explosives, Electrostatic Discharge Sensitivity Tests.
6. STANAG 4491, Explosives, Thermal Sensitiveness and Explosiveness Tests.
7. STANAG 4506, Explosive Materials, Physical/Mechanical Properties, Uniaxial Tensile
Test, Edition 1.
8. STANAG 4507, Explosive Materials, Physical/Mechanical Properties, Stress Relaxation
Test in Tension.
9. STANAG 4515, Explosives, Thermal Analysis Using Differential Thermal Analysis
(DTA), Differential Scanning Calorimetry (DSC), Heat Flow Calorimetry (HFC), and
Thermogravimetric Analysis (TGA).
10. STANAG 4525, Explosives, Physical/Mechanical Properties, Thermomechanical
Analysis for Determining Coefficient of Linear Thermal Expansion (TMA).
11. STANAG 4540, Explosives, Procedures for Dynamic Mechanical Analysis (DMA) and
Determination of Glass Transition Temperature.
12. STANAG 4556, Explosives, Vacuum Stability Test.
13. STANAG 4581, Explosives, Assessment of Ageing of Composite Propellants
Containing an Inert Binder.
14. STANAG 4582, Explosives, Nitrocellulose Based Propellants, Stability Test Procedures
and Requirements Using Heat Flow Calorimetry.
15. UN Orange Book Recommendations on the Transport of Dangerous Goods: Model
Regulations, 2000
16. MIL-B-131 G Class 1
17. ASTM D 2240 00, Standard Test Method for Rubber Property-Durometer Hardness.
Unknown.

1
 STANAG 4666
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AIM
1. The aim of this agreement is to standardize accelerated ageing and testing protocol by
which aged samples of PBXs, cast-cured compositions using inert or energetic binders
can be assessed and compared.
2. This agreement is intended for use by the NATO Participating Nations.

AGREEMENT
3. Participating Nations agree that the scope of the agreement set out in Annex A, the
principles and methodology set out in Annex B, the procedure set out in Annex C and the
test methods set out in Annex D constitute basic data for ageing behaviour assessment
of PBXs, cast-cured compositions using inert or energetic binders.

4. The approach described in this STANAG consists of performing accelerated ageing in

accordance with the procedure set out in Annex C and subsequently examining the PBX
using the methods described in Annex D.

5. The procedures described in this STANAG may also find application to other types of
PBX (pressed, extrudable or non-cured) with inert or energetic binder.

IMPLEMENTATION OF THE AGREEMENT

6. This STANAG is considered implemented by a nation when that nation has issued
instructions that determination of ageing characteristics of PBXs shall be performed by
the test procedures described in this STANAG.

WARNING
This STANAG calls for the use of substances and test procedures that may be injurious to
health if adequate precautions are not taken. It refers only to technical suitability and in no
way absolves the user from the statutory obligations relating to health and safety at any
stage during use.

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SCOPE OF THE AGREEMENT

1. This STANAG covers procedures for accelerated ageing and testing to allow
assessment and comparison of PBX compositions.

2. This STANAG does not cover the evaluation of the service life of PBXs but only the
characterization of ageing of PBXs.

3. Because PBXs have different compositions and properties, there is no single chemical
method that can be applied in all cases. The applicability of each of the methods given
in Annex D will have to be specified.

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PRINCIPLES AND METHODOLOGY

1. GENERAL

1.1 The approach proposed in this STANAG makes it possible to evaluate the
accelerated ageing behaviour and testing of cast-cured PBXs using inert or
energetic binders. A single-temperature ageing and testing protocol is described to
allow comparisons to be made between aged samples.

NOTE B1: It is recognized that multi-temperature conditioning and testing could

result in a more complete assessment of ageing behaviour. Therefore the
accelerated ageing procedure, as specified in Annex C, can be applied to additional
and/or other temperatures and durations, provided that the conditions of ageing are
clearly stated in the test results.

1.2 The ageing mechanisms are mainly defined by the properties of the binder
combined with the crystalline high explosive as filler. The binder could be of the type
‘inert’ or ‘energetic’.
Examples for inert: HTPB (hydroxyl terminated polybutadiene) and energetic: GAP
(glycidyl azide polymer)

1.3 Because some properties (particularly mechanical) can be highly altered by humidity
and the presence of oxygen, it is critical that the ageing conditions are well
controlled:
1.3.1 The moisture content of the PBX must be analyzed by a suitable method
(e.g. Karl Fischer) and recorded.
1.3.2 The PBX should be aged in an environment and configuration similar to
its ammunition application. If it is not known, then the volume of air
present around the aged PBX should be less than 5 %.

1.4 The presence of transition metals might catalyze the breakdown of polymeric binder
chain during ageing, resulting in cracking of the material. Therefore if transition
metals are present, an analysis of the materials is recommended. Inductively
coupled argon plasma atomic emission spectrometry is a suitable analytical method
for the determination of transition metals but other methods could be considered.

2. PROPERTIES ALTERED BY AGEING

Ageing can give rise to many phenomena, which may modify the ageing behaviour of
PBXs.

For example:

- Oxidation of the binder leading to hardening which is generally increased by the

presence of air and is therefore greater at the surface than at the centre.

- Degradation of the binder by the rupture of chains.

- Migration of species (plasticizer) towards free surfaces can lead to material hardening
and to a higher sensitivity.

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- Solid fillers can undergo various surface phenomena like absorption of moisture, partial
dissolution followed by recrystalisation or even temperature-based phase transitions.
Any of these phenomena could modify the ageing behaviour of the PBX as a whole.

- Dewetting effect of crystals / binder interface leading to higher sensitivity of PBX

material.

3. CONTROL METHODS

The chemical and mechanical methods described in Annex D make it possible to identify
the changes in the key parameters set out in paragraph 2.

3.1 The measurement of residual antioxidant levels enables a qualitative assessment of

the state of binder degradation. However, there is not always a direct relationship
between the residual antioxidant level and the PBX mechanical properties.
3.2 The measurement of soluble fraction or crosslink density enables an assessment of
how far the degradation reactions have proceeded either by rupture of chains or
increase in crosslink density. There is a direct relationship between these
parameters and the PBX mechanical properties.
3.3 The measurement of plasticizer content at different locations will indicate any
migration.
3.4 The measurement of tensile or compression mechanical properties enables failure
and response properties to be measured at specific temperatures and crosshead
rates.
3.5 The use of dynamic mechanical analysis (DMA) enables PBX viscoelastic behaviour
to be assessed.
3.6 The measurement of Shore A hardness allows the change in this property to be
determined.

With respect to mechanical properties, only the specific conditions and results sheets are
described. The assessment of the results is discussed in Annex D. Other tests may be
conducted:

 Evaluation of thermal properties by DSC or DTA (STANAG 4515) or other

methods (STANAG 4491).
 Sensitivity tests (impact, friction, electrostatic discharge, thermal sensitivity)
(STANAG 4489, 4487, 4490, 4491).
 Analysis for transition metals by atomic absorption spectrometry or any other
suitable method.
 Stability analysis by HFC (STANAG 4582) and Vacuum Stability Test (STANAG
4556).
 Sol-Gel analysis.
 FTIR spectroscopy to detect changes.
 Mechanical analysis by DMA (STANAG 4540), uniaxial tensile testing (STANAG
4506) and TMA (STANAG 4540, 4525).

Specific chemical methods for certain types of antioxidants and plasticizers are
described in Annex D.

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ACCELERATED AGEING PROCEDURE

1. PRINCIPLE

The PBX is placed in the form of a block in a sealed conditioning system and artificially
aged at the prescribed temperature and duration. For single-temperature assessments,
60°C for 4 and 8 months (minimum) is recommended. For example in HTPB binder
systems this is considered to be equivalent to 5-6 years or 10-12 years of ambient
temperature.

NOTE C-1: It is recognized that multi-temperature conditioning and testing could result
in a more complete assessment of ageing behaviour. Therefore the accelerated ageing
procedure, specified below, can be applied to additional and/or other temperatures and
durations for the purpose of multi-temperature assessments. In all cases, the conditions
of ageing should be clearly stated in the test results.

NOTE C-2: It is important to avoid ageing too small samples of the PBX and it is
recommended to perform the ageing in bulk.

Ageing in polymer-coated aluminum bags

For this ageing method, polymer-coated, heat-sealable aluminum bags are used (e.g. 30
x 30 cm bags according to specifications of MIL-B-131 G Class 1 "Barrier Materials,
Watervapor-Proof, Grease-Proof, Flexible, Heat-Sealable"). This method is also
applicable for larger PBX blocks as well as for sticks.
The bags are filled up to approximately 20 – 30 % of their volume with sample. Excess
air is removed by flattening the empty part of the bags before heat-sealing the bags
according to the manufacturer's specifications. The bags are then placed in the heating
oven for the specified duration.

NOTE C-3: The main advantage of this ageing method is, apart from the possibility to
also age block materials, that gas evolution during ageing does not cause excessive
pressure build-up followed by seal leakage as often appears with glass tubes or vials.
Here, evolved gases just inflate the bags. Furthermore, an air/sample ratio similar to real
ammunition can be adjusted. Therefore, this ageing method is recommended for
materials of larger size (e.g. blocks) which otherwise have to be ground prior to ageing.
Other ageing methods for PBX propellants
If ageing of blocks of PBX in polymer-coated aluminum bags turns out to be
inappropriate, other bag material can be used (if compatible with PBX), further ageing
methods are possible:
1. Close wrapping of the propellant blocks into aluminum foil, or
2. Cutting the PBX block in order to fit into conditioning boxes. The wrapped blocks
or condition boxes are then placed in the heating oven for the specified duration.

NOTE C-4: Surface effects due to ageing may be assessed.

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2. APPARATUS

Oven maintained at 60  2°C for the required duration.

3. AGEING CONDITIONS

PBXs, cast-cured compositions using inert or energetic binders samples should be aged
in block.
A typical example is given in Figure 1 and the note attached to this figure. Place them flat
in the conditioning box or pack or wrap in aluminum foil or an inert wrap and close tightly.
Upon completion of ageing, remove the enclosed samples from the oven and allow
cooling down to ambient temperature. The visual presence of cracks, voids and other
flaws should be noted.

The size or number of the blocks has to be defined by the tests to be performed after
ageing the PBX material.

Before starting machining the block it is recommended to perform an X-ray or other NDT
(non-destructive testing) flaw detection for identifying cracks or flaws. The size and
number of blocks required have to be defined by the tests to be performed after ageing
the PBX.

In order to avoid surface effect, a minimum depth of 20 mm should be removed from all
surfaces of the bulk sample. This removal is intended to avoid localized irregularities
influencing quality of bulk PBX ageing test specimens extracted from aged PBX blocks.
These 20 mm pieces can be used to perform ageing profile assessment due to surface
effects. Ageing sample PBX blocks should be large enough to readily extract:

- 5 JANNAF Class C tensile specimens

- 3 dynamic mechanical analysis (DMA) bars
- 4 Shore A hardness discs

The remainder can be utilized for various chemical tests and perhaps for plasticizer
and/or antioxidant migration analysis. Figure 1 illustrates an example of the PBX block
size and test specimen descriptions suitable for use in PBX ageing studies. More
compact ageing test blocks may be used as long as the appropriate test sample set can
be easily obtained from each block.

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FIGURE 1
Typical example of the PBX block to be used for cutting the various samples needed.

NOTE: The actual block used for artificial ageing will have, in comparison to the one illustrated
above, an increase of at least 40 mm for each dimension since after the ageing
period, a minimum depth of 20 mm should be removed from all surfaces. Larger
blocks and/or multiple blocks described above may be used in cases requiring
additional material.

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TEST PROCEDURES

LIST OF TESTS

1. CHEMICAL TESTS

1A Measurement of the soluble fraction

1B Measurement of crosslink density
1C Measurement of antioxidant content (HPLC)
1D Measurement of plasticizer content

2. MECHANICAL TESTS

2A Uniaxial tensile test – STANAG 4506

2B Dynamic Mechanical Analysis – STANAG 4540
2C Measurement of Shore A hardness
2D Thermal Mechanical Analysis – STANAG 4525

3. THERMAL TESTS

3A Differential Scanning Calorimetry – STANAG 4515

3B Thermogravimetry – STANAG 4515
3C Vacuum Stability Test - STANAG 4556
3D Heat Flow Calorimetry (HFC) – STANAG 4582

4. OTHER TESTS

4A Microscopy
4B Shock Sensitivity – STANAG 4488
4C Friability Test
4D FTIR spectroscopy
4E Impact Test – STANAG 4489
4F Friction Test – STANAG 4487
4G Electrostatic Discharge Test – STANAG 4490

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CHEMICAL TESTS

TEST 1A: MEASUREMENT OF THE SOLUBLE FRACTION

1. INTRODUCTION

The soluble (sol) content of a crosslinked polymer is a useful measurement of the extent
of crosslinking within the polymer network. The greater the fraction of uncrosslinked
polymer, the higher the sol content.
Previous work on composite propellants has shown that the mechanical strain at
maximum stress (max) is also a function of the sol content.
The sol fraction can be determined by extraction at ambient temperature or by refluxing
with solvent. It can be used in the modified Charlesby-Pinner equation to evaluate the
crosslink density.

NOTE D-1: The methods described in this section may lead to incorrect results if
applied to PBXs containing fillers which are soluble in the chosen solvent. In that case, it
is advisable to use test 1B to determine crosslink density.

2. EXTRACTION AT AMBIENT TEMPERATURE

2.1 Outline of the method

A known weight of the PBX is swollen in toluene or dichloromethane for several days
at ambient temperature until a stable state of swelling is achieved. After that, the gel
fraction and solvent phase are separated and the soluble fraction evaluated.

2.2 Apparatus and reagents

- Toluene or dichloromethane - Analytical grade

- Oven at 50°C ± 2 °C

2.3 Extraction

Into a tarred beaker (W 1), add 2.0  0.1 g of the sliced PBX (roughly 1 mm x 2 mm x
2 mm) and reweigh accurately (W 2). Add approximately 100 ml of toluene or
dichloromethane and change the solvent after 24, 48 and 72 hours at ambient
temperature. After 4 days, separate gel fraction and solvent phase, dry the gel
fraction in an oven at 50°C to remove the solvent until a constant weight is obtained
(W s).
It might be required to retain the soluble fraction for plasticizer content as described
in test 1D.

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2.4 Calculation of soluble fraction (S)

Calculate the soluble fraction (S) from the equation:

Wi  WS
S
Wi
where:
W i = weight of unswollen sample in g (W 2-W 1)
W S = weight of gel fraction after extraction in g

The soluble fraction is expressed as a fraction of 1.

3. SOXHLET EXTRACTION

3.1 Outline of method

A known weight of the polymer bonded explosive is added to a weighed Soxhlet

extraction thimble. The sample is extracted for at least 16 hours in a Soxhlet
extraction apparatus using dichloromethane as solvent. The thimble is dried and
reweighed. The sol fraction of the sample is equal to the loss in weight of the
thimble divided by the weight of the PBX taken initially.

3.2 Apparatus

- Soxhlet extraction apparatus

- Ceramic or alumina Soxhlet extraction thimbles

Extractions are conveniently heated using a thermostatically controlled

electrothermal unit.

3.3 Extraction

Carry out the extraction and measurement in triplicate. Dry an extraction thimble by
heating in a vacuum oven for 3 hours at 60°C. Leave it to cool for one hour in a
vacuum desiccator and then weigh accurately (W 1 g). Add 3.0  0.1 g of the sliced
PBX (roughly 1 mm x 2 mm x 2 mm) and reweigh accurately (W 2 g). Extract for at
least 16 hours with 200 ml of dichloromethane in a Soxhlet extraction apparatus.
Remove the extraction thimble and place in a fume cupboard. Allow the excess
solvent to evaporate off by air drying for two hours. Then place the sample in a
vacuum oven at a pressure of less than 1 mm of mercury at ambient temperature
and leave overnight to remove traces of dichloromethane. Transfer it to a vacuum
desiccator containing dry silica gel and leave it to cool for an hour. Reweigh the
thimble and sample (W 3 g). Retain the soluble fraction for the measurement of
plasticizer content (test 1D).

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3.4 Calculation of the soluble fraction (S)

Calculate the sol fraction from the equation:

(W 2  W 3)
S
(W 2  W 1)
where:
W 1 = Weight of dry thimble
W 2 = Weight of thimble + sample before extraction
W 3 = Weight of thimble + sample after extraction
The soluble fraction is expressed as a fraction of 1.

4 CROSS LINK DENSITY (XLD)

The relative cross link density of the binder system (XLD) can be calculated with the
following equation:

2 s s 
XLD  (1  s) 
 
 
 s s 

Another value, also indicated as cross-link-density is Cx, defined as the effective

cross-link-density of the binder network:

Cx 

 1  s   2  s  s  
2M 0  s s 


where:
M0 = the molecular weight of primary chain

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NATO STANAG 4666 DATA SHEET

TEST 1A: MEASUREMENT OF THE SOLUBLE FRACTION

Report Reference Number: Page 1 of 1 Page
(Unique Reference Number)
TEST SITE INFORMATION CONDITIONS OF AGEING

Laboratory: Temperature of ageing (°C):

(Name of laboratory)

Date: Test time (months):

(Date that form was completed)

Test Procedure: CONDITIONS OF ANALYSIS:

(Name of test procedure used)

Date Tested: Divergences from standard procedure:

(Date of test period)

POC:
(Point of contact)

SPECIMEN INFORMATION TESTS RESULTS

Identification of Test Material: Sol fraction before ageing:

(Trade name and/or Identify code)

Manufacturer: Sol fraction after 3 months ageing:

(Name of manufacturer)

Test Material, Specification: (state if specification

controls chemical composition of product) Sol fraction after 6 months ageing:
Lot, Batch or Consignment Number:

Date of Manufacture or Receipt:

Special Storage Conditions: Comments:

(If applicable)
Data Sent to:

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CHEMICAL TESTS

TEST 1B: MEASUREMENT OF CROSSLINK DENSITY

1. INTRODUCTION

The crosslink density is a useful parameter for the physical property of the PBX. It is
known that this parameter will be affected by the ageing of the material. Consequently it
may be used to evaluate the degradation state.

2. SCOPE AND PRINCIPLES OF METHOD

A sample of the polymer bonded explosive with a known volume is swollen in toluene for
several days at a stable and known temperature (ideally room temperature). The
compression measurements are only performed after a stable state of swelling is
reached (typically one week). The compression modulus of the swollen material is
determined graphically and used for the calculation of the crosslink density.

3. APPARATUS AND REAGENTS

 Balance accurate to 0.1 mg
 Glassware and standard laboratory equipment
 Beaker with a cover to avoid solvent evaporation
 Modulus apparatus (see Figure 2). It consists of a dial micrometer to measure
the displacement of the swollen sample compressed by known weights.
 Toluene - Analytical grade

4. ANALYTICAL PROCEDURE

4.1 Sample preparation

PBX samples are finely cut in disc forms. Their heights and diameters are precisely
measured with a micrometer device (typically a height of 1.5 cm and a diameter of
2.5 cm).

Each sample is put in a beaker and approximately 60-100 ml of toluene is added.

The sample must always be completely submerged in toluene during the
experiments to keep the swelling state undisturbed.

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The sample is kept in toluene until a steady state of equilibrium is reached. One
way to evaluate if a steady state has been reached is by weighing the sample at
every 30 s during 5 minutes. The time zero is the time at which the sample has
been removed from the solvent. A graph of time as a function of weight measured is
plotted. This will give a straight line and by extrapolation, the weight at time zero is
evaluated. The steady state is reached when this weight at time zero of the swollen
sample is constant (typically of the order of one week).

4.2 Measurement

Each swollen sample is put under the tray of the modulus apparatus to be
compressed.

NOTE D-2: The measurements are performed on the swollen sample immersed in
toluene.

The dial of the modulus apparatus is adjusted to zero.

Compression measurements are then performed by adding various incremented

known weights (from 40 up to 400 g). The displacement is recorded for each weight
added.

After each measurement of displacement, the weight is removed for 2-5 minutes to
relax the sample at the original equilibrium state in the solvent. It might be
necessary to adjust the zero especially for the higher weight near the end of the
experiment.

The measurements are stopped when an acceptable plot is obtained (typically after
10 measurements).

The graph of the weight (kg) as a function of the deflexion (m) is plotted and the
slope is determined.

4.3 Calculation of the crosslink density (C)

The crosslink density is calculated according to the following formula:

h0 S
C [mole/m3]
3 A0 RT
where:

ho : Height of the sample (m)

Ao : Area of the cross section (i.e. circular face) (m2)
R : Gas constant (8.315 J/moleK)
T : Temperature (K)
S : Slope x 9.807 m/s2 (N/m)
C : Crosslink density (mole/m3)

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Scale for weights

5 cm Dial indicator
(0.001 cm division)

Beaker filled
with toluene

Tray to compress
the sample

PBX sample

FIGURE 2
Modulus apparatus used for measurement of crosslink density.

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NATO STANAG 4666 DATA SHEET

TEST 1B: MEASUREMENT OF CROSSLINK DENSITY

Report Reference Number: Page 1 of 1 Page

(Unique Reference Number)
TEST SITE INFORMATION CONDITIONS OF AGEING

Laboratory: Temperature of ageing (°C):

Date: Test time (months):

Test Procedure:

Date Tested: TEST CONDITIONS

Temperature (°C):
POC:
Relative humidity (%):

Solvent used:
SPECIMEN INFORMATION TYPICAL RESULTS
Dimensions: Height (ho) in m:
One line for each ageing time (0, 3 and 6 months)
Diameter in m:
Area of the cross section (A0) in m2:
Weight (kg)

Form:
Preparation Method:
Manufacturing Method:
Source:
Lot or ID Number:
Conditioning Period:
Composition: 0
Component Percent
  Deflexion (m)
 
  Slope (kg/m) for each ageing time:

Calculation of the crosslink density: C = h0S/3A0RT

where:
ho : Height of the sample (m) Ao : Area of the sample (m2)
T : Temperature (K) R : Gas constant (8.315 J/moleK)
C : Crosslink density (mole/m3) S : Slope x 9.807 m/s2 (N/m)

Crosslink density result before ageing =

Crosslink density result after 3 months ageing =
Crosslink density result after 6 months ageing =

Data Sent to (check in all datasheets) Comments

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CHEMICAL TESTS

TEST 1C: MEASUREMENT OF ANTIOXIDANT CONTENT

1. INTRODUCTION

This type of measurement depends on the nature of the antioxidant used. The method
described
below is suitable for:

- 2,2’-methylene-bis-(4-methyl-6-tert-butylphenol) for which some the commercial names

are CALCO, AO-2246 or MBP5
- 2,6-di-tert-butyl-p-cresol for which the commercial name could be IONOL

However, it can be used for other types of antioxidants.

NOTE D-3: Some antioxidants may be very reactive toward all types of isocyanates. As
a consequence, such antioxidants are attached to the molecular chain end of the HTPB
network by a covalent bond and therefore are not extractable by any procedure.
Therefore the method described here will not be suitable for such antioxidants. An
example of such an antioxidant is N-phenyl-N’-cyclohexyl-p-phenylene diamine
(Flexzone 6H) for which an amino group attached to an aliphatic group is very reactive
toward isocyanates. A phenolic type antioxidant such as 2,5-di-tert-butyl-hydroquinone
(DTBHQ) has also shown some covalent bonding with the polymeric network depending
on the NCO/OH ratio used during the manufacturing process of the PBX.

2. SCOPE AND PRINCIPLES OF METHOD

The method utilizes solutions obtained after maceration of the PBX in any suitable
solvent according to the formulation. The determination of antioxidant content is made
by high performance liquid chromatography (HPLC) using an internal standard
procedure.

3. APPARATUS AND REAGENTS

 Balance accurate to 0.1 mg

 Glassware and standard laboratory equipment
 Centrifuge
 Sample filtration system
 Liquid chromatograph with UV detector, integrator and appropriate HPLC column
 Appropriate antioxidant standard - Analytical grade
 Appropriate internal standard (e.g. triphenylamine)
 Methanol or any suitable solvent - HPLC grade

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4. ANALYTICAL PROCEDURE

4.1 Preparation of standard solution

In a flask, dissolve in 50 ml of methanol, or any suitable solvent, the following masses

accurately weighed to 0.1 mg
- approximately 10 mg of antioxidant
- approximately 10 mg of internal standard
Dilution to a larger volume is acceptable as long as the mass to volume ratio is kept
constant.

NOTE D-4: The internal standard can be introduced by weighing or by pipetting of a

stock solution. The standard solution should be stored in cool dark conditions for no
more than two weeks.

4.2 Preparation of the solution to be measured

Extract in 50 ml of methanol, or any suitable solvent, under agitation, approximately 5

g of the polymer bonded explosive (cut into 2 to 3 mm pieces) and approximately 10
mg of internal standard. Agitate the mixture for at least 6 hours. Allow to settle for a
few minutes and take 10 ml to 15 ml of the supernatant solution.
Centrifuge to obtain a perfectly clear solution or filter (3 μm) before injecting.

4.3 Analysis of standards and samples

Inject 3 µl of the solution to be analysed into the HPLC. The injections of standard
solutions and solutions to be analyzed must be done under the same operating
conditions.

The determination is performed by calculating peak areas.

5. EXPRESSION OF RESULTS

Results shall be expressed as percentage of antioxidant present in the material using

internal standard procedure.

6. EXAMPLE OF CHROMATOGRAM

This example (figure 3) illustrates an HPLC method based on a methanol/water mobile

phase but any other equivalent method using a different mobile phase can be used.

6.1 Column: Lichrosorb RP 18 (5 µm) 25 cm x 4 mm

Instrument conditions

Eluent composition: methanol / water (80/20 by volume)

Eluent flow: 1.3 ml/min
Column head pressure: approximately 130 bars
Temperature: 35°C
Injection volume: 3 µl
UV detector, wavelength: 205 nm

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1 0 .0 2 :2 T R IP H E N Y L A M IN E
400
mA b s

3 50

8 .6 8 :1 IO N O L
300

1 3 .3 7 :3 M B P 5
2 50

200

15 0

10 0

50

m in
-2 0
0 .0 2 .5 5 .0 7 .5 10 .0 12 .5 15 .0 17 .5 2 0 .0

FIGURE 3
HPLC chromatogram with:
IONOL: 2,6-di-tert-butyl-p-cresol
Triphenylamine
MBP5: 2,2’-methylene-bis- (4-methyl-6-tert-
butylphenol)

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NATO STANAG 4666 DATA SHEET

TEST 1C: MEASUREMENT OF ANTIOXIDANT CONTENT

Report Reference Number: Page 1 of 1 Page

(Unique Reference Number)
TEST SITE INFORMATION CONDITIONS OF AGEING

Laboratory: Temperature of ageing (°C):

(Name of laboratory)

Date: Test time (months):

(Date that form was completed)

CONDITIONS OF ANALYSIS BY HPLC

Test Procedure:
(Name of test procedure used) Name of antioxidant:
Column:
Name and flow of eluent:
Date Tested: Name of internal standard:
(Date of test period)

Divergences from standard procedure:

POC:
(Point of contact)
SPECIMEN INFORMATION TEST RESULTS
Identification of Test Material: Antioxidant before ageing:
(Trade name and/or Identify code)
Antioxidant after 3 months ageing:
Manufacturer:
(Name of manufacturer) Antioxidant after 6 months ageing:

Test Material, Specification: (state if specification Difference:

controls chemical composition of product)
after 3 months:
Lot, Batch or Consignment Number: after 6 months:

Date of Manufacture or Receipt:

Special Storage Conditions: Comments:

(If applicable)
Data Sent to:

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CHEMICAL TESTS

TEST 1D: MEASUREMENT OF PLASTICIZER CONTENT

1. INTRODUCTION

The methods for the measurement of plasticizer content in the polymer bonded explosive
described in this section were specifically developed for nonanoic acid 8-methylnonyl
ester, better known as isodecyl pelargonate (IDP) and commercially sold under the name
Emery® 2911 synthetic lubricant basestock by Cognis Corporation (formerly Henkel
Corporation Chemicals Group). Similar methods could be developed for other
plasticizers, such as bis (2-ethyl hexyl) adipate (BEHA) and nonanedioic acid di-octyl
ester (better known as di-octyl azelate or DOZ).

2. SCOPE AND PRINCIPLES OF METHOD

The determination of the plasticizer content is performed by using the gas

chromatography (GC) technique. Two different detectors could be used: the flame
ionization detector (FID) or a mass spectrometer (MS).

The Soxhlet extractions in dichloromethane conducted to determine the sol fraction of

the polymer bonded explosive is outlined in Paragraph 3 of Method 1A. However,
various modifications can be made to this procedure. These modifications are reported
in Paragraph 5.1 of the present section.

3. APPARATUS AND REAGENTS

 Balance accurate to 0.1 mg

 Glassware and standard laboratory equipment
 Sample filtration system
 Syringe
 GC with FID or GC/MS
 Appropriate GC column and other relevant GC accessories
 Isodecyl pelargonate (IDP) from Cognis Corporation or appropriate plasticizer
standard
 Dichloromethane – analytical grade
 Acetonitrile – analytical grade
 Acetone – analytical grade

4. ANALYTICAL PROCEDURE

4.1 Extraction procedures

The sample solution can be taken directly from the dichloromethane extract of the
soluble fraction (test 1A). However, the sample solution can be prepared according
to one of these three Soxhlet extraction procedures:

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4.1.1 Standard Soxhlet extraction procedure I

Weight of sample: 3.0 g

Volume of dichloromethane solvent: 200 ml
Extraction time: at least 16 hours
Container: alumina or ceramic extraction thimble

4.1.2 Soxhlet extraction procedure II

Weight of sample: 0.3 g

Volume of dichloromethane solvent: 30 ml
Extraction time: 4 hours
Container: glass filter extraction tube (porosity 3)

4.1.3 Soxhlet extraction procedure III

Weight of sample: 10 g
Volume of dichloromethane solvent: 100 ml
Extraction time: 17 hours
Container: cellulose extraction thimble

4.2 Preparation of standard solutions

Four plasticizer standard solutions ranging from 1 to 4 mg/ml are prepared in an

80/20 v/v mixture of acetonitrile/acetone.

4.3 Preparation of sample solutions

The dichloromethane extract of the sol fraction mainly consists of the plasticizer, the
antioxidants and the free polymer chains that are not or that are no longer attached
to the crosslinked network. To prepare the sample solutions, the dichloromethane
extract of the sol fraction is evaporated in a beaker under a fume hood for at least 6
hours. The beaker is then put in a vacuum oven at 50˚C for about 2 hours. A
volume of 100 ml of an 80/20 v/v mixture of acetonitrile/acetone is added to the solid
residue. In the obtained solution, the polymer remains in the beaker as a solid
residue whereas the other ingredients are soluble in the solvent. The upper liquid,
which contains the plasticizer, is filtered through a 13 mm / 0.45 μm PTFE syringe
filter prior to analysis by GC. The removal of the polymer from the sol fraction is
carried out in order to prevent the plugging of both the GC liner and column.

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4.4 Analysis of standards and samples

To analyse the standards and samples, a volume of 1 μl is injected into the

chromatograph using FID or MS as detector. A calibration curve is built from the
standards. The injections of standards and samples must be done under the same
operating conditions. Since some plasticizers (e.g. IDP) consist of a mixture of
isomers, the total area of all the peaks corresponding to these isomers is integrated
for quantification purposes.

5. EXPRESSION OF RESULTS

The results shall be expressed in percentages of plasticizer present in the polymer

bonded explosive sample as output by the chromatography integration system. The
original weight of the polymer bonded explosive sample from the sol fraction extraction
and the volume of the diluted extract will be required as input data for the
chromatography integration system.

6. EXAMPLES OF CHROMATOGRAMS

6.1 Examples of conditions suitable for procedure using GC-FID (see figure 4)

6.1.1 Column: DB-5, 30 m length, 0.53 mm inner diameter

6.1.2 Instrument conditions:

Carrier gas and flow rate: helium 5 ml/min

Injected sample volume: 1 μl
Oven conditioning: 160˚C (5 min), 2˚C/min to 250˚C
Injector temperature: 220˚C
Detector temperature: 250˚C

6.2 Examples of conditions suitable for procedure using GC-MS (see figure 5)

6.2.1 Column: DB-5, 30-m length, 0.25-mm inner diameter

6.2.2 Instrument conditions:

Carrier gas and flow rate: helium 1 ml/min (split ratio 1:100)
Injected sample volume: 1 μl
Oven conditioning: 160˚C (5 min), 10˚C/min to 250˚C (7 min)
Injector temperature: 220˚C (transfer line at 250˚C)
Detector temperature: 185˚C

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FIGURE 4
A chromatogram with conditions as given in 6.1 (GC/FID)

7
1.2x10

7
1.0x10

6
8.0x10

6
6.0x10
RIC

6
4.0x10

6
2.0x10

0.0

0 5 6 7 8 9 10 11 12 13 14 15
Retention Time (minute)

FIGURE 5
A chromatogram with conditions as given in 6.2 (GC/MS)

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NATO STANAG 4666 DATA SHEET

TEST 1D: MEASUREMENT OF PLASTICIZER CONTENT

Report Reference Number:
Page 1 of 1 Page
(Unique Reference Number)

TEST SITE INFORMATION CONDITIONS OF AGEING

Laboratory: Temperature of ageing (°C):

(Name of laboratory)
Test time (months):

Date:
(Date that form was completed) CONDITIONS OF ANALYSIS BY GC

Test Procedure: Name of plasticizer:

(Name of test procedure used)
Detector type (FID or MS):
Column type and dimensions:
Date Tested:
(Date of test period) Carrier gas and flow rate:

Injected sample volume:

POC:
(Point of contact) Oven temperature programming:

Injector temperature:
Detector temperature:

Divergences from standard procedure:

SPECIMEN INFORMATION TEST RESULTS

Identification of Test Material: Plasticizer content before ageing:

(Trade name and/or Identify code)
Plasticizer content after 3 months ageing:
Manufacturer:
(Name of manufacturer) Plasticizer content after 6 months ageing:

Test Material Specification: Difference:

(State if specification controls chemical composition
of product) After 3 months ageing:

Lot, Batch or Consignment Number: After 6 months ageing:

Date of Manufacture or Receipt:

Special Storage Conditions:

(If applicable) Comments:

Data Sent to:

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MECHANICAL TESTS

TEST 2A: UNIAXIAL TENSILE TEST

1. INTRODUCTION

The accelerated ageing of PBX may lead generally to changes in the modulus of
elasticity (Eo), the maximum stress (m) and the deformation at maximum stress (εm).

2. TEST PROCEDURE

The test procedure is that described in STANAG 4506 with the following specific
conditions.

2.1 Sample preparation (see paragraph 4.1 of STANAG 4506)

The samples are collected at the centre of the aged block as described in Figure 1.

2.2 Preconditioning (see paragraph 5.1 of STANAG 4506)

The samples will be preconditioned at 12% RH and 23  5 ºC for 48 hours.

2.3 Test temperature (see paragraphs 3.2 B and 5.2 of STANAG 4506)

The test temperature shall be 20  1 ºC. Additional tests at higher or lower temperatures
between -46 ºC and +60 ºC may be required as part of an ageing program. In this case it
is necessary to age PBX samples of greater dimensions.

2.4 Crosshead speed (see paragraph 3.3 of STANAG 4506)

The test speed is generally 50 mm/min.

2.5 Test (see paragraph 5.6 of STANAG 4506)

Test 5 samples of unaged PBX and 5 samples of PBX aged under the same operating
conditions.

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NATO STANAG 4666 DATA SHEET (Side A)

TEST 2A: Uniaxial Tensile Test
Report Reference Number: Page 1 of 2 Pages
(Unique Reference Number)
TEST SITE INFORMATION CONDITIONS OF AGEING
Laboratory:
Date: Temperature of Ageing (ºC):
Test Procedure:
NATO Test Procedure Number: STANAG Ageing Time (months):
4666
Date Tested:
POC:
SPECIMEN INFORMATION TEST CONDITIONS

Dimensions: Length (Gage length): Temperature (°C):

(mm) Width: Extensometer: Yes  No 
Thickness: Relative Humidity (%):
Cross-Sectional Area (mm2): Cross-Head Speed (mm/sec):
Form: Machine Type:
Preparation Method: Grip Type:
Manufacturing Method: Machine Stiffness (kN/mm):
Source:
Lot or ID Number:
Conditioning Period:
Composition:

Component Percent
 
 
 

TYPICAL RESULTS

(Plot typical results of unaged sample and aged samples together in this graph)

Stress (MPa)

Strain (%)

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NATO STANAG 4666 DATA SHEET (Side B)

TEST 2A: Uniaxial Tensile Test
Report Reference Number: Page 2 of 2 Pages
(Unique Reference Number)
RESULTS BEFORE AGEING
Specimen  m m r r E0 m r E0
Test ID T A0 (direct) direct (direct)
(ºC) (mm2) s-1 MPa % MPa % (MPa) (%) (%) (MPa)

Average before ageing

(n-1)

RESULTS AFTER AGEING FOR 3 MONTHS

Specimen  m m r r E0 m r E0
Test ID T A0 (direct) (direct) (direct)
(°C) (mm2) (s-1) (MPa) (%) (MPa) (%) (MPa) (%) (%) (MPa)

Average after 3 months

(n-1)

RESULTS AFTER AGEING FOR 6 MONTHS

Specimen  m m r r E0 m r E0
Test ID T A0 (direct) (direct) (direct)
(°C) (mm2) (s-1) (MPa) (%) (MPa) (%) (MPa) (%) (%) (MPa)

Average after 6 months

(n-1)

Data Send To: Comments

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TEST 2B: DYNAMIC MECHANICAL ANALYSIS

Dynamic Mechanical Analysis (DMA) provides a measurement of viscoelastic mechanical

properties of a PBX in a wide range of temperatures and frequencies and gives the
temperature/frequency dependencies of the storage modulus (G’ or E’), the loss modulus
(G’’ or E’’) and the loss factor (tan δ).

In a DMA plot, the storage modulus values generally tend to be highest in the low
temperature region (at approximately -110 to - 750C). In this region, the specimens
resemble hard, low strain to failure materials. The modulus values then tend to decrease
as the temperature is increased. In a temperature sweep, the low temperature peak of
the loss modulus corresponds to the glass transition temperature of the PBX which
characterize the brittle-to-ductile transition.

Accelerated ageing of PBX may lead to changes in the storage modulus across the
entire temperature range. These changes tend to be more obvious at the higher
temperature end. The older or greater the deterioration of the propellant, the greater the
modulus difference. The glass transition temperature, Tg, may also be seen to shift in
temperature.
The apparatus and the test procedures are described in detail in STANAG 4540.

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TEST 2C: MEASUREMENT OF SHORE A HARDNESS

1. INTRODUCTION

Shore A hardness provides a measurement of the hardness of the PBX measured in

Shore A. Ageing may lead to changes in hardness of the PBX.

2. TEST PROCEDURE

The test procedure used is that described in ASTM D 2240 00 with the following
conditions:

2.1 Sample preparation

The sample shall have a diameter of at least 35 mm with a smooth and even surface.
The
thickness of the sample shall be at least 6 mm.

2.2 Preconditioning
Samples shall be preconditioned for at least 30 minutes at ambient temperature (18-
250C).

2.3 Apparatus
An apparatus as specified in ASTM D 2240 00 shall be used.

2.4 Test method

(1) The apparatus shall be carefully placed in close contact with the sample, avoiding
any
form of impact.
(2) At least three measurements on each sample shall be made with a distance of at
least
5 mm from each other and with a distance from the edges of at least 13 mm.
(3) The Shore A hardness is read on the apparatus after 3 s.

2.5 Performance of the test

The difference between two measurements performed by the same person with the
same
apparatus must not exceed 2 Shore A.
The difference between two measurements performed by two different persons with
different
apparatus must not exceed 3 Shore A.

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NATO STANAG 4666 DATA SHEET

TEST 2C: MEASUREMENT OF SHORE A HARDNESS

Report Reference Number: Pages 1 of 2

Pages
(Unique Reference Number)
CONDITIONS OF AGEING
Temperature of ageing (ºC):

TEST SITE INFORMATION

Test time (months):

TEST CONDITIONS
Laboratory: Test temperature (°C):

Date: Conditioning history:

Date tested: Apparatus manufacturer:

Test Procedure: Apparatus number:

POC:

SPECIMEN INFORMATION COMPOSITION

Dimensions (mm):
(Component and percentage)
(Mean specimen diameter and thickness)

Length:

Width:

Thickness:

Form:

Identification:

(Trade name and/or identification code)

Preparation Method:

Manufacturer Method:

Source:

Lot, Batch or consignment Number:

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NATO STANAG 4666 DATA SHEET

TEST 2C: MEASUREMENT OF SHORE A HARDNESS

Report Reference Number: Pages 2 of 2

Pages
(Unique Reference Number)
RESULTS
(in Shore A)

Before Ageing

Sample/measurem
1 2 3 Mean SD
ent

After 3 months ageing

Sample/measurem
1 2 3 Mean SD
ent

After 6 months ageing

Sample/measurem
1 2 3 Mean SD
ent

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TEST 2D: THERMAL MECHANICAL ANALYSIS

This method is the preferred method for determining the coefficient of linear thermal expansion
(α) of solid materials (including the transition temperature dependence of α). The glass
transition
temperature is defined as the temperature where main chain molecular motion ceases, which
is not measured in this test.

a. Linear thermal expansion

Linear thermal expansion is the change in length of a specimen due to a temperature

change.

b. Coefficient of linear thermal expansion

The coefficient of linear thermal expansion (α) is defined as the change in length per
degree of temperature change divided by the initial length L0.

α(T) = (dL/dT)/L0

The initial length (L0) is measured at a reference temperature (usually room

temperature i.e. 23 ± 5 °C). α is expressed in units of inverse temperature.

The apparatus and the test procedures are described in detail in STANAG 4525.

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THERMAL TESTS

TEST 3A: DIFFERENTIAL SCANNING CALORIMETRY

This technique measures the difference between the heat flow to a sample and the heat flow
to an inert reference while the temperature is controlled. Two general types of instrumentation
can be used for measuring heat flow by differential scanning calorimetry - power compensation
DSC and Heat flow DSC.
A power compensation DSC consists of individual sample and reference holders each fitted
with its own heater and platinum resistance thermometer. In normal operation, the sample pan
contains the explosive and the reference pan can be left empty or contain some inert material
such as alumina. The system is operated by two electronic control loops.
Hence a signal is produced which is directly proportional to the difference between the heat
input to the sample and that to the reference. The area beneath the curve is a direct measure
of the heat involved in bringing about the transition i.e. heat flow to/from the sample (dH/dt)
which is usually measured in milliwatts.
Heat flow DSC (heat flux DSC). An important difference, however, is that in heat flow DSC
instruments, there must be a well-defined thermal resistance between the wall of the furnace
and the sample position of the sensor. In ideal circumstances exactly the same thermal
resistance must be present between the wall of the furnace and the reference position of the
sensor. By measuring temperature differences between strategically chosen positions, a signal
is obtained which is directly proportional to the difference between the heat input to the sample
and that to the reference.

The apparatus and the test procedures are described in detail in STANAG 4515.

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TEST 3B: THERMOGRAVIMETRY

TGA measures changes in weight of a sample as a function of temperature/time. Measure-

ments can be carried out with a gas flow of air, nitrogen or another specified gas. The
technique is useful in distinguishing phase changes from weight changes caused by chemical
reactions. The technique becomes even more useful if connected directly to a FT IR or to a
MS for evolved gas analysis (EGA). Gaseous decomposition products and volatile species can
readily be identified making the task of characterising transitions in unknown compositions
much simpler. Samples are weighed directly into a sample pan assembly fitted to the TGA or
with an outer microbalance. The sample pan assembly is completely surrounded by a furnace
for control of the sample temperature. It is possible to purge the furnace volume with inert or
reactive atmospheres.

The apparatus and the test procedures are described in detail in STANAG 4515.

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TEST 3C: VACUUM STABILITY TEST

The vacuum stability test is used to assess the thermal stability of an explosive by measuring
the volume of gas evolved on heating the explosive under specified conditions. It is
undesirable to attempt the test on explosives which exhibit an appreciable vapour pressure.

A sample of the explosive compound is heated for a specified time in an evacuated tube in a
heating bath maintained at a constant specified temperature. The volume of gas evolved is
determined by using a pressure transducer. A minimum of two tests shall be conducted on
each material to be tested.

The mass of explosive, the temperature and duration of the test together with the allowable
upper limit of the volume (at standard temperature and pressure – STP) of gas evolved is
prescribed.

The most commonly used test conditions are given below;

Test duration 40 hours

Test temperature
Explosives 100 °C or 120 °C
Nitrate ester plasticized polyether propellants 90 °C
Composite propellants 100 °C
Pyrotechnics 100 °C
PBX 100 °C

The explosive specimen shall consist of 5 g of a representative portion of the explosive or such
mass as shall be prescribed in the relevant specification. For testing primary explosives the
mass should be decreased because of safety reasons.

Compatibility of energetic materials with other components, used in ammunition, is extremely

important in connection with the high demands made on the safety and functioning. The ideal
case of compatibility would be that the materials do not react with each other even after long
storage periods at various conditions. For practical reasons materials are judged as
compatible if during and after a specified storage period the functioning and safety of the
components are still acceptable.

The apparatus and the test procedures are described in detail in STANAG 4556 and STANAG
4147.

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TEST 3D: HEAT FLOW CALORIMETRY

Samples are measured at a constant temperature between 40°C and 160°C for a specified
time dictated by the temperature chosen and the heat flow is measured as function of time. A
maximum permissible heat flow limit, also dictated by the experimental temperature employed
is used, as a criterion for sufficient chemical stability.
Heat flow calorimeter with a measuring range corresponding to 10 to 500 µW/g. The error
must be less than 2% during the total measuring time. If necessary to reach this level the drift
of the baseline must be estimated and used for correction.
Sample vessels with a minimum volume of 2 cm³ that can be hermetically sealed. It must be
proven that the vessel material does not react with PBX and its decomposition products.
The apparatus and the test procedures are described in detail in STANAG 4582 and 4147.

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OTHER TESTS

TEST 4A: MICROSCOPY

1. SCOPE

This is an optical and scanning electron microscopy (SEM) procedure for analysis of PBX
samples by observing crystal morphology, internal and external defects.

2. SUMMARY OF METHOD

This procedure uses microscopy to characterize PBX particles.

 PBX particles are mounted in a contrasting refractive index fluid and examined with
an optical microscope with transmitted white light.
 PBX particles are mounted in a matching refractive index fluid and their internal
defects examined with an optical microscope with transmitted white light.
 PBX particles samples are prepared and the external defects are examined via
SEM (Scanning Electron Microscope)

3. BACKGROUND AND DISCUSSION (measurement before and after ageing / result

sheet)

This procedure is based on the observation that one can rapidly rank the defects observed in
side-by-side photomicrographs of PBX samples when the samples vary widely in the number
and/or size of the defects. The aim of the work to be conducted under this procedure is to
rank the relevant defect density of PBX samples through a semi-quantitative system.

This procedure can be performed using equipment commonly available in modern laboratories
that analyze energetic materials and can be performed in a reasonable time.

It is generally assumed that the larger the number and/or size of the defects, the greater the
sensitivity to shock. However, the percent contribution of each of the defect categories
(morphological, internal, and external) to the shock sensitivity is not fully understood. The
points-based system employed here includes:
 Points assigned to the morphology bins to show a gradation from sharp corners to a
smooth surface and spherical shape.
 Points assigned to internal defects with consideration given to both size and number.
Defects such as dislocations and grain boundaries cannot be observed using this
procedure, but a qualitative relationship does exist between the number of inclusions
(internal defects) and the presence of dislocations.
 Points assigned to surface defects and surface roughness.

4. EQUIPMENT & SUPPLIES NEEDED

4.1 Equipment
 Optical microscope equipped with a mechanical stage and digital camera, computer &
computer monitor
 Scanning Electron Microscope (SEM)
 Vacuum/argon sputter coater with either gold or gold/palladium cathode target
 Supplies
o Glass microscope slides (3” x 1”)

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o Glass microscope cover glasses, No. 1½

o Refractive index immersion fluids: n = 1.51 and n = 1.59.
o Glass micro-pipette
o Stainless steel tweezers
o Aluminum SEM stubs
o Conductive carbon tape

5. SAFETY

Follow all the safety regulations and operating procedures that are normal for working with
energetic materials. Wear required personal protective equipment – minimum: safety glasses
and laboratory coat.

6. PROCEDURE

6.1 Preparation of samples

1. Prepare a suspension of the dried PBX particles in a contrasting refractive index fluid
(n = 1.51). By means of a glass pipette, transfer a small droplet of the suspension to
a glass slide. Make sure that the particles are well dispersed. Cover the droplet with
a cover glass.

2. Mount a representative sample of the dried PBX on double-sided adhesive

conductive carbon tape on an SEM stub, taking care to disperse the particles well,
and sputter coat with Au (or Au/Pd) to make the particles conductive.

NOTE D-5: Note: Sputter coating may not be necessary if one has the capability to
produce resolved images of the PBX particle surface by using a low acceleration
voltage (~1kV, or lower).

6.2 Optical microscopy with contrasting optical fluid – morphology assessment

In the following section, selection of the fields of view to be recorded should be done in
such a way as to provide representative views of the sample. Views that have a
disproportionate number of large, small, flawed or perfect crystals should be avoided.

1. Use SLIDE 1 prepared in the previous section for this analysis. Bring the particles
into focus so the Becke line is not moving either in or out of the majority of particles in
the field of view. Adjust the microscope for Köhler illumination.

2. Adjust the initial magnification to include nominally 50 crystals within the field of view
of the camera. Record and save a digital image of this field of view – clearly record
file name/s in Excel results spreadsheet.

3. Increase the magnification further to provide viewing of 3-5 separated crystals with
the field of view of the camera. Record and save digital images of 5 different fields of
view at this magnification.

6.3 Scanning electron microscopy analysis of samples – surface defect assessment

1. Use the SEM stub prepared above. Randomly select a large particle (~400 μm
particle size) whose image can be seen in its entirety and which fills at least 50% of
the computer screen. The surface features of the particle need to be well resolved.

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2. The exact SEM conditions to be used are dependent upon the screen and
instrument resolution and the ability to clarify defects. Suitable conditions for SEM
analysis of PBX particles have been found to involve:
 5 – 10keV beam
 500x / 1000x magnification
 Au (or Au/Pd) splutter coating

3. Record and save a digital image of the selected crystal. Analyze the imperfections
of the crystal as directed in steps 4 through 6 below. Repeat the procedure for nine
additional crystals, giving results for a total of 10 crystals – clearly record the file
names for each of the ten SEM images into the Excel results spreadsheet.

4. Knobs, Holes, and Depressions: Knobs are surface features that are convex in
appearance; depressions are surface features that are concave in appearance.
Knobs can be due to smaller particles that are aggregated with the selected
particle; decide whether it appears firmly attached (aggregated) or whether it is
loosely held (agglomerated). Most little particles attached to PBX are
agglomerated. Count only those that appear to be aggregated. Holes most often
appear as black circular areas with sharply defined edges. Count these features
and enter the data into the Excel results spreadsheet.

5. Cracks: Count the number of surface cracks and enter into the Excel results
spreadsheet.

6. Surface Roughness: Assess the overall surface roughness of each selected particle
and categorize it as very rough, medium rough, or slightly rough. Best judgment is
used in deciding whether the surface roughness of the particle is very rough, rough,
or slightly rough (includes smooth).

7. REPORTING THE RESULTS

Fill in the tables for Morphology, Internal Defects, and External Defects for each sample
included in the Excel results spreadsheet. Be sure to clearly identify all microscope images
files sent with the results table.

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NATO STANAG 4666 DATA SHEET

TEST 4A: MICROSCOPY and SCANNING ELECTRON MICROSCOPY
Report Reference Number:
(Unique Reference Number)
TEST SITE INFORMATION CONDITIONS OF AGEING

Laboratory: Temperature of Ageing (ºC)

(name of Laboratory)

Date: Test Time (days)

(Date that form was completed)

SPECIMEN INFORMATION TEST RESULTS

Identification of test material: Morphology:

(trade name and/or identity code)

Manufacturer:
(Name of manufacturer)
Test material specification: External Defects:
(state if specification controls chemical composition of
product)

Lot, batch or consignment number:

Date of manufacture or Receipt: Internal Defects:

Special storage conditions:

(If applicable)

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TEST 4B: SHOCK SENSITIVITY / GAP TEST

A reference is made to STANAG 4488; the aim is to establish test procedures which provide
information on the shock sensitivity of explosive materials.

The appropriate test to be used is determined by the confined critical diameter of the test
explosive.

The critical diameter of the test explosive should be less than the diameter of the acceptor test
body. In cases where the approximate shock sensitivity characteristics of the acceptor are
unknown, the first sensitivity test should be performed at zero gap (i.e. no attenuator used). If
no detonation occurs, one of the larger size gap tests should be performed. The use of the test
apparatus and test procedures should facilitate the exchange and direct comparison of test
data in conjunction with qualification testing according to STANAG 4170.

The shock sensitivity of an explosive will be determined using one of the following apparatus:

A. Small scale gap test

B. Intermediate scale gap test
C. Expanded large scale gap test
D. Super large scale gap test

The apparatus and the test procedures are described in detail in STANAG 4488.

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TEST 4C: FRIABILITY TEST

MEASUREMENT OF CHANGE OF PROPERIES OF AGED PBXs

1. INTRODUCTION

PBXs are used to reduce the tendency of a munition to respond violently in the different
IM scenarios. The complex nature of this type of explosive does however give reason to
doubt whether its initial excellent properties will be retained over the whole service
lifetime of the munition. This procedure is intended to investigate possible changes
during the lifetime of the munition and determine whether or not dangerous reactions can
be expected from the explosive filling.

2. SCOPE AND PRINCIPLES OF METHOD

As described in the UN-manual on the transport of dangerous goods. The friability test is
used to determine the effect of impact on an EIDS (Extremely Insensitive Detonating
Substance) candidate. However, the likelihood of an explosive to undergo severe
reaction (DDT: Deflagration-to-Detonation Transition) can be investigated with this test.
Less sensitive explosives are intended not to undergo a DDT reaction whether they are
pristine or aged. The test is split into two phases. In the first phase, a test sample of 9.0 g
has to be projected against a steel plate at a velocity of 150 m/s. In the second phase,
this damaged sample is tested in a manometric bomb (a closed vessel) to determine the
average maximum pressure rise rate, (dp/dt)max, of three tests, which is not allowed to
be more than 15.2 MPa/ms.

Also a relative change in material properties can be determined by comparing the

friability results of the aged samples with the data of the pristine materials. With an
additional methodology even the surface area changes of the aged and pristine materials
can be compared.

3. APPARATUS

 Balance accurate to 0.01 g

 A (gas) gun to accelerate 9.0±0.1 g samples (18 mm diameter) to 150 m/s
 A velocity window (optical barriers) to measure the velocity of the sample before
impact
 A recovery box
 A Z30C 13 stainless steel plate, 20 mm thick with a front face roughness of 3.2
microns (AFNOR) NF E 05-015 and NF E 05-016 standards)
 A manometric bomb (closed vessel) with a pressure transducer and data acquisition
system; working with a loading density of 0.1 g/cm3
 A firing capsule containing a heating wire on 0.5 g of black powder with a mean
particle size of 0.75 mm. The composition of the black powder is 74% potassium
nitrate, 10.5% sulphur and 15.5% charcoal. The moisture content should be less than
1%
 A cylindrical sample of compact substance of diameter 18 ± 0.1 mm. The length is
adjusted so as to obtain a mass of 9.0 ± 0.1 g. The sample is brought to and
maintained at a temperature of 20 °C.

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4. PROCEDURE

4.1 The gas gun experiment

Before the test sample is brought into the muzzle of the launching tube, the temperature
of the tube and sample must be checked not to exceed the value of 22 °C. If both values
are checked, the 9.0 ± 0.1 g sample (using a special sabot (plastic wad) is preferred) is
brought into the muzzle to a prescribed distance with a stick. After the standard safety
precautions have been taken, the sample can be fired against the steel plate at the end
of the recovery box. The velocity is measured just before impact and should be 150 m/s.
The fragments are gathered to be burned in the closed vessel test.

4.2 The closed vessel experiment

The mass of the recovered sample fragments, after a gas gun experiment, should be at
least enough material for a closed vessel testing. The closed vessel should be clean
before firing. A pressure transducer (type Kistler 6211 or comparable) should be used to
be able to measure the pressure increase in the bomb and be connected to the data
acquisition system. The vessel is preconditioned to a temperature of 21 ± 2 °C. The
sample is also preconditioned to the same temperature. The sample is placed in the
vessel chamber.

After the chamber is closed, the ignition plug together with the igniter is mounted into the
vessel wall and the sample is ready to be fired. After all safety precautions have been
taken and the data acquisition system is on standby, the igniter is fired. The igniter will
ignite the test sample and the pressure is recorded as a function of time. Two minutes
after the experiment, the pressure can be released by opening the plug.

After smoothing the raw pressure data, the time-derivative of the pressure can be
calculated. From this, the maximum pressure rise can be obtained corresponding to a
impact velocity of 150 m/s. For each type of material, three tests are carried out.

5. EXPRESSION OF RESULTS
The results shall be expressed as the average pressure derivative of a minimum of 3
samples at an impact speed of 150 m/s and can be compared with the pristine material
values.

In case of maximum surface area increase, the maximum surface area of the aged
material is compared with the pristine material.

6. EXAMPLE OF SAMPLES AND CLOSED VESSEL DATA

An example of a picture of a sample before and after gas gun testing is shown in figure
6. An example of a pressure curve and its time-derivative as a function of time is given in
figure 7.

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FIGURE 6
A pristine 9 g PBX sample before and after testing in the gas gun.

FIGURE 7
An example of the pressure and pressure derivative of damaged samples in a
closed bomb test. The maximum pressure in a duplicate experiment was about
100 MPa and the pressure derivative around 1.1 MPa/ms.

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NATO STANAG 4666 DATA SHEET

TEST 4C: FRIABILITY TEST
MEASUREMENT OF CHANGE OF PROPERTIES OF AGED PBXs
Report Reference Number: Page 1 of 1 Page
(Unique Reference Number)
TEST SITE INFORMATION CONDITIONS OF AGEING

Laboratory: Temperature of ageing (°C):

(Name of laboratory)

Date: Test time (months):

(Date that form was completed)

CONDITIONS testing
Test Procedure:
(Name of test procedure used) Temperature gas gun during testing:
Temperature samples during testing:
Velocity of sample:
Temperature of closed bomb:
Date Tested: Name of internal standard:
(Date of test period)

Divergences from standard procedure:

POC:
(Point of contact)
SPECIMEN INFORMATION TEST RESULTS
Identification of Test Material: Max. Presssure before ageing:
(Trade name and/or Identify code) Max Pressure derivative before ageing:

Manufacturer: Max. Presssure after 3 months ageing:

(Name of manufacturer) Max Pressure derivative after 3 months ageing:

Test Material, Specification: (state if specification Max. Presssure after 6 months ageing:
controls chemical composition of product) Max Pressure derivative after 6 months ageing:

Lot, Batch or Consignment Number: Difference:

Date of Manufacture or Receipt: after 3 months:

after 6 months:
Special Storage Conditions: Comments:
(If applicable)
Data Sent to:

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TEST 4D: FTIR SPECTROSCOPY

1. INTRODUCTION

The measurements that are made with this method depend on the complexity of the
sample.
This technique can be used for identification as well as for quantification of compounds.
Due to the fact that sample pretreatment is not needed, the additives can be analyzed
without the need for extraction. The limitations of this technique lie in the possibility of
overlapping or interfering compounds present in the matrix of the material and/or too low
concentrations.

2. SCOPE AND PRINCIPLES OF METHOD

The method utilizes the polymer bonded explosive in original form. The determination of
different components is performed by comparing, identifying and integrated the specific
wave-bands of the different components (after calibration) to obtain information about the
ratios. It is also possible to only compare the un-aged and aged materials.

3. APPARATUS AND REAGENTS

 Tweezers
 Fourier transform infrared spectroscope with Attenuated Total Reflection (ATR)
accessory
 Appropriate reference material and/or spectra - Analytical grade
 Standards or spectra in the search library of the other compounds present in the
sample
 Cleaning solvent acetone or ethanol – analytical grade

4. ANALYTICAL PROCEDURE

4.1 Clean the ATR surface with acetone or ethanol and let it evaporate before
analysis
4.2 Scan a background spectrum
4.3 Scan the individual reference compounds present in the sample if materials are
known
and no reference spectra are present in the spectra library.
4.4. Scan the un-aged sample and the aged sample. Compare the two spectra and
detect
differences.

5. EXPRESSION OF RESULTS

The results can only be obtained when the IR-bands of the antioxidant (additive) are not
undergoing interference or being overlapped by other compounds present in the sample.
The results can be listed as the ratios of the different components.

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6. EXAMPLES OF ATR-FTIR SPECTRA

1.4

1.2

1.0
ATR-UNIT

0.8

0.6

0.4

0.2

0.0

4000 3500 3000 2500 2000 1500 1000 500

3.5

3.0
ATR-UNIT

2.5

2.0

1.5

1.0

0.5

0.0

3500 3000 2500 2000 1500 1000

1.4

1.2
ATR-UNIT

1.0

0.8

0.6

0.4

0.2

0.0

4000 3500 3000 2500 2000 1500 1000 500

1.4

1.2

1.0
ATR-UNIT

0.8

0.6

0.4

0.2

0.0

4000 3500 3000 2500 2000 1500 1000 500

-1
WAVELENGTH (cm )
FIGURE 8
Infrared spectra of (from top to down)
HTPB, HMX, dioctyl adipate and isophorone diisocyanate

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NATO STANAG 4666 DATA SHEET

TEST 4D: FTIR SPECTROSCOPY
Report Reference Number:
(Unique Reference Number)
TEST SITE INFORMATION CONDITIONS OF AGEING

Laboratory: Temperature of Ageing (ºC)

(name of Laboratory)

Date: Test Time (days)

(Date that form was completed)
Specific wave-bands for the PBX components

Component name / Frequency (cm -1)

bond / functional
group

SPECIMEN INFORMATION TEST RESULTS

Identification of test material Identification of components:

(trade name and/or identity code)

Manufacturer: Calibration curves of components:

(Name of manufacturer)

Test material specification: Composition or ratio of components:

(state if specification controls chemical composition of (Variation between un-aged and aged material)
product)

Lot, batch or consignment number Spectra of samples and reference material:

Date of manufacture or Receipt: Comments:

Special storage conditions: Data Sent to:

(If applicable)

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TEST 4E: IMPACT SENSITIVITY TEST

A reference is made to STANAG 4489; the aim of that agreement is to standardize test
apparatus and test procedures for the determination of the impact sensitivity of explosives.
The use of the test apparatus and test procedures should facilitate the exchange and direct
comparison of test data in conjunction with qualification testing according to STANAG 4170.

The impact sensitivity of an explosive will be determined using one of the following apparatus:

a. ERL/Bruceton machine with Type 12 Tools

b. Rotter-type impact machine
c. BAM impact machine

The apparatus and the test procedures are described in detail in STANAG 4489.

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TEST 4F: FRICTION SENSITIVITY TEST

A reference is made to STANAG 4487; the aim of that agreement is to standardize test
apparatus and
test procedures for the determination of the friction sensitivity of explosives. The use of the test
apparatus and test procedures should facilitate the exchange and direct comparison of test
data in conjunction with qualification testing according to STANAG 4170.

The friction sensitivity of an explosive will be determined using one of the following apparatus:

a. BAM friction machine

b. Rotary friction machine

The apparatus and the test procedures are described in detail in STANAG 4487.

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TEST 4G: ELECTROSTATIC DISCHARGE TEST

A reference is made to STANAG 4490; the aim is to establish test procedures which provide
information on the electrostatic discharge sensitivity of explosive materials.

Most of ESD (electrostatic discharge) tests used at this time are "spark tests" that use small
quantities of material and simulate the discharge through such material by charged humans or
metallic pieces. Such tests do not provide the information required to explain accidents such
as:

a. accidental ignition of missiles during their handling due for instance to electrostatic
sensitivity of the energetic material at low temperature,

b. accidental ignition of rocket motor loadings during the production process (handling,
mandrel extraction).

Such accidents are the result of charging of surfaces made from poorly conducting materials
(plastics) in contact with explosive substances. These explosive substances may then be
charged to a potential where breakdown occurs. This can lead to arcing and catastrophic
accidental ignition. This illustrates the fact that the "spark tests" performed with about 100 mg
samples are not useful regarding this issue, and the need to adopt a "large scale ESD test",
which must be standardized.

A – Explosives, Small scale electrostatic discharge sensitivity test

B – Explosives, Large scale electrostatic discharge sensitivity test

The apparatus and the test procedures are described in detail in STANAG 4490.

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