New Standards for Nitrocellulose Testing –

STANAG 4178 Ed. 2 // MIL-DTL-244 B/ECP / C

Beat Vogelsanger, Ruth Sopranetti, Beate Pausch, Marc Müller and Dominik Werfl 1
Patrick Folly 2
Mario Paquet 3
Lucas R Lopez, Lydia Chang 4
1 NITROCHEMIE WIMMIS AG, Switzerland
2 FEDERAL DEPARTMENT OF DEFENCE, armasuisse, Thun, Switzerland
3 GENERAL DYNAMICS OTS, Valleyfield, Canada
4 US DoD, ARDEC, Picatinny NJ, USA

© Nitrochemie 2012
New Standards for NC Testing – STANAG 4178 Ed. 2 / MIL-DTL-244 B/ECP / C

Contents

Introduction
History of Standards for NC Testing
Differences between STANAG 4178 Ed. 2 and MIL-DTL-244 B/ECP / C
Status of Ratification / Implementation

Round Robin Test (RRT) on Nitrocellulose Analysis

Highlights of the new Standards

Drawbacks / not yet solved Problems

Summary and Outlook

2012 NC Symp Spiez _ Pres Vogelsanger et al 1 _ Standards for NC Testing.ppt Vob © Nitrochemie 2012 2
New Standards for NC Testing – STANAG 4178 Ed. 2 / MIL-DTL-244 B/ECP / C

Introduction – Recent History of Standards for NC Testing

MIL-N-244A UK M22 / M23 / M39 Other

(1962) (1987/89/88) Standards

MIL-DTL-244B STANAG 4178 Ed. 1

(1996) (1991)

2007 – 2009
NATO/PfP AC/326 SG/1 CNG + US Industrial
Product Team (IPT) + international NC Experts
55 Persons /// 36 MoD/DoD Agencies,
Institutes, Companies /// 17 Nations
3 Joint Meetings + many Sub-Team Meetings

MIL-DTL-244B/ECP Identical
STANAG 4178 Ed. 2
(2010) Test-
Procedures (2009)
MIL-DTL-244C (2012)
2012 NC Symp Spiez _ Pres Vogelsanger et al 1 _ Standards for NC Testing.ppt Vob © Nitrochemie 2012 3
New Standards for NC Testing – STANAG 4178 Ed. 2 / MIL-DTL-244 B/ECP / C

Differences between STANAG 4178 and MIL-DTL-244

Standard STANAG 4178 Ed. 2 MIL-DTL-244 B/ECP / C

Classification of NCs --- (Grades A–F; Types I-III)

Specification for NCs --- (only typical ranges)

Testing Procedures NC (all relevant tests) (only required tests)
Testing Quality Requirements ---
Alterations for chalked NC ---
Requirements Raw Material ---
Requirements Prod. Process ---

STANAG 4178 is a compendium of nitrocellulose test procedures

MIL-DTL-244 is a specification for nitrocellulose that also contains test
procedures (but only the ones that are needed for this specification)

2012 NC Symp Spiez _ Pres Vogelsanger et al 1 _ Standards for NC Testing.ppt Vob © Nitrochemie 2012 4
 New Standards for NC Testing – STANAG 4178 Ed. 2 / MIL-DTL-244 B/ECP / C

Test Methods of STANAG 4178 Ed. 2 and MIL-DTL-244 B/ECP / C

Basic Purity Polymeric Properties

Characterisation Viscosity
Visual Purity Test
Nitrogen Content Ash Molecular Mass Distribut.
- Ferrous Ion Titration Grit
- Nitrogen Analyzer
- Combustion Calorimetry
Ionic Impurities Water / Alcohol Cont.
- Ion Chromatography
- (Devarda's Alloy Method)
- (Schulze-Tiemann)
- Sulphate Content Total Volatile Content
- Residual Acidity - Oven Method
- (Nitrometer)
- Alkalinity - Moisture Analyzer
Ether-Alcohol Solubles - Calcium by Spectroscopy
- Filtration Method
Water Content
Oil and Grease Content - Karl-Fischer Titration
- Evaporation Method
(Abel-Type Heat Tests) - Karl-Fischer Oven
Acetone Insolubles
Alcohol and / or Water
- Gas Chromatography
Fibre Quality - NIR Spectroscopy
Stability
Fineness
132°°C Stability Test Fibre Length Distribution
- Bergmann-Junk
Other Properties
Water Retention Value
- Bergmann-Junk-Siebert Drainability Temperature of Ignition
134.5°°C Heat Test (MV) Agglomerates Heat of Explosion
2012 NC Symp Spiez _ Pres Vogelsanger et al 1 _ Standards for NC Testing.ppt Vob © Nitrochemie 2012 5
New Standards for NC Testing – STANAG 4178 Ed. 2 / MIL-DTL-244 B/ECP / C

STANAG 4178 Ed. 2 Ratification Status

Denmark
Nether-
lands

Latvia

UK
Canada Czech Rep.

Spain

USA

Switzerland is France Bulgaria

custodian nation
Slovenia

STANAG 4178 Ed. 2 is currently in NATO ratification

11 nations including US, UK and France have already ratified
a total of 14 nations (50% of the 28 NATO nations) need to ratify
many nations have already implemented the new testing procedures
2012 NC Symp Spiez _ Pres Vogelsanger et al 1 _ Standards for NC Testing.ppt Vob © Nitrochemie 2012 6
New Standards for NC Testing – STANAG 4178 Ed. 2 / MIL-DTL-244 B/ECP / C

MIL-DTL-244 B / C Status of Implementation

MIL-DTL-244 B with ECP # R10C3001 (2010)

ECP = Engineering Change Proposal
Officially implemented
Currently used by the US ARMY, NAVY and Air Force

MIL-DTL-244 C (2012)
Approved by the Nitrocellulose Configuration Manager (PM-CAS)
ARDEC standardization group is working on the document to ensure
spec language complies with DoD requirements
Not yet implemented !

Test procedures of MIL-DTL-244 B/ECP, MIL-DTL-244 C

and STANAG 4178 Ed. 2 are identical

2012 NC Symp Spiez _ Pres Vogelsanger et al 1 _ Standards for NC Testing.ppt Vob © Nitrochemie 2012 7
New Standards for NC Testing – STANAG 4178 Ed. 2 / MIL-DTL-244 B/ECP / C

Round Robin Test (RRT) on Nitrocellulose Analysis

Mandate: NATO/PfP AC/326 SG1 CNG

Organiser: US ARDEC, GD-OTS Valleyfield, Nitrochemie Wimmis
Goals:
Implementation of new methods (STANAG 4178 Ed.2 / MIL-DTL-244B/ECP)
To improve performance / get confidence in new testing methods
To obtain an idea about typical variations between labs
In the long term: To trigger communication within the NC community and
to further improve testing methods
Samples: 6 samples; each 2 samples Grade A, B, C
3 samples with known results (to adjust procedures / gain confidence)
3 samples with unknown results (for RRT).
Tests for RRT: N-Content, EA-Solubility, Acetone Insolubles, 134.5°°C Heat
Test, 132°°C Stability Test (Bergmann-Junk), Fineness, Viscosity

If you are interested to participate, please inform the organisers

2012 NC Symp Spiez _ Pres Vogelsanger et al 1 _ Standards for NC Testing.ppt Vob © Nitrochemie 2012 8
New Standards for NC Testing – STANAG 4178 Ed. 2 / MIL-DTL-244 B/ECP / C

Some Highlights of the new Standards

Ionic Impurities – Ion Chromatography Method:

Modern method to assess numerous different
ionic impurities simultaneously
Polymeric Properties – Gel Permeation Chromatography GPC:
Modern method to assess the distribution of degree of
polymerisation (conventional viscosity only results
indirect measure for average degree of polymerisation)
Tests for Fibre Quality:
Different test method to investigate the fibre properties
A new method to assess the fraction of the NC which is
present as agglomerates
Several indirect methods to estimate the amount of
cutting / grinding / refining the NC had undergone
A new direct method to determine the real fibre
length distribution of the NC

2012 NC Symp Spiez _ Pres Vogelsanger et al 1 _ Standards for NC Testing.ppt Vob © Nitrochemie 2012 9
New Standards for NC Testing – STANAG 4178 Ed. 2 / MIL-DTL-244 B/ECP / C

Highlight 1: Ion Chromatography Method

New method; procedure has been supplied by USA

Can be used to assess numerous different ionic impurities
Principle: Extraction of the ions from the NC with boiling
water, followed by analysis with ion chromatography
Recommended method in STANAG 4178 Ed. 2 !
Chromatograms
provided by

IC of Nitrocellulose A - Anions IC of Nitrocellulose A - Cations

NO3- = 109 ppm
NO2- = 44 ppm SO42- = 18 ppm Na+ = K+ =
195 ppm 18 ppm
Cl- = 15 ppm
Mg2+ = Ca2+ =
F- = 4 ppm 13 ppm 116 ppm

0 2 4 6 8 10 0 5 10 15 20 25
Retention Time [Min] Retention Time [Min]

2012 NC Symp Spiez _ Pres Vogelsanger et al 1 _ Standards for NC Testing.ppt Vob © Nitrochemie 2012 10
New Standards for NC Testing – STANAG 4178 Ed. 2 / MIL-DTL-244 B/ECP / C

Highlight 2: Gel Permeation Chromatography

CH2 ONO2 H ONO2 Degree of Polymerisation =

O Length of NC Polymer Chain
H H
O Typical Value: n = 500 – 1'400
H ONO2 H
ONO2 H H (= Molecular Mass of 300'000 – 800'000
O
H H O Daltons; may be lower or higher for
specific NC qualities)
H ONO2 CH2 ONO2
n

Viscosity → Average GPC → Distribution of Degree of

Degree of Polymerisation Polymerisation / Molecular Mass
2012 NC Symp Spiez _ Pres Vogelsanger et al 1 _ Standards for NC Testing.ppt Vob © Nitrochemie 2012 11
 New Standards for NC Testing – STANAG 4178 Ed. 2 / MIL-DTL-244 B/ECP / C

Highlight 3: New Methods for Fibre Length Determination

The Fibre Length of NC is a process relevant property as it reveals the amount
of cutting / grinding / refining the NC had undergone during manufacture

Indirect Methods Direct Method

Water Retention Fibre Length /
Fineness Drainability
Value WRV Shape Analyzer

NC
250 mL

10g dry NC wet pulp Light Ca-

250

+ water 230
NC Source mera
large
210

- shaking 190

170
centri- Ø small
- settling 1h 150
Ø
130 fuging SR

110

90
10
800

settling 70 30
600
L = 357 µm
50
50
volume 30 3000 g 400
mL

70
200
90

→ Water retention → NC average

→ NC settling value = water content → Drainability = rate
volume fibre length and
of centrifuged NC of dewatering of pulp
distribution
2012 NC Symp Spiez _ Pres Vogelsanger et al 1 _ Standards for NC Testing.ppt Vob © Nitrochemie 2012 12
New Standards for NC Testing – STANAG 4178 Ed. 2 / MIL-DTL-244 B/ECP / C

Highlight 3: Fibre Quality Analyzer – Principle of Operation

Sample
Dispersing
Unit
Example Picture

Pulsed
CCD
Light
Camera
Source

Cuvette - Instrument Control

- Data Acquisition
- Image Analysis
- Output of Result
Sample Flow

2012 NC Symp Spiez _ Pres Vogelsanger et al 1 _ Standards for NC Testing.ppt Vob © Nitrochemie 2012 13
New Standards for NC Testing – STANAG 4178 Ed. 2 / MIL-DTL-244 B/ECP / C

Highlight 3: Fibre Quality Analyzer – Image Analysis

Image analysis using the "Skeletonising Method":

Fibre length is determined as longest direct way
between two endpoints of the particle (fibre)

Agglomerates can be
eliminated from analysis
2012 NC Symp Spiez _ Pres Vogelsanger et al 1 _ Standards for NC Testing.ppt Vob © Nitrochemie 2012 14
 New Standards for NC Testing – STANAG 4178 Ed. 2 / MIL-DTL-244 B/ECP / C

Highlight 3: Fibre Quality Analyzer – Repeatability

100.0 Param. 1 Param. 2 x(10 %) x(50 %) x(90 %) opt. Konzentration Partikel in QICPIC-Ausw ertung Ausw .Mode 6.0
97.5 µm µm µm %
Sympatec
NirtoChemie GmbH
Faser Büro
M2 M2 d Augsburg
11,17 148,55 459,03 0,18 111138 LEFI 5.8
95.0
NirtoChemie Faser M2 M2 d 11,51 148,43 465,82 0,18 111934 LEFI
5.6
92.5 NirtoChemie Faser M2 M2 d 12,82 152,23 467,88 0,18 112159 LEFI
90.0 NirtoChemie Faser M2 M2 d 11,32 148,92 461,54 0,18 915304 LEFI 5.4
NirtoChemie Faser M2 M2 d 11,42 147,85 458,59 0,19 944728 LEFI
87.5
85.0
NirtoChemie Faser M2 M2 d 11,66 147,89 457,23 0,19 944292 LEFI 5.2 Excellent
NirtoChemie Faser M2 M2 d 12,90 150,43 465,92 0,19 952901 LEFI
82.5 NirtoChemie Faser M2
NirtoChemie Faser M2
M2 c
M2 c
12,24
11,72
151,99 469,29 0,11
152,95 467,48 0,11
67838
68684
LEFI
LEFI
5.0
Repeatability
80.0 4.8
77.5
NirtoChemie Faser M2
NirtoChemie Faser M2
M2 c
M2 c
12,49
11,30
150,72 455,08 0,11
148,50 454,53 0,11
70457
563775
LEFI
LEFI
4.6
(replicate
NirtoChemie Faser M2 M2 c 12,00 148,84 457,28 0,11 567366 LEFI
75.0
72.5
NirtoChemie Faser M2 M2 c 11,80 148,34 458,66 0,11 573572 LEFI 4.4 analysis)
NirtoChemie Faser M2 M2 c 12,51 150,54 457,00 0,12 571649 LEFI
70.0 NirtoChemie Faser M2 M2 c 12,67 153,97 471,94 0,12 587504 LEFI 4.2
NirtoChemie Faser M2 M2 b US 11,08 145,27 454,70 0,15 795358 LEFI
67.5
NirtoChemie Faser M2 M2 b 11,11 147,53 456,91 0,16 816595 LEFI 4.0
65.0
62.5
NirtoChemie Faser M2 M2 b 11,16 147,28 453,42 0,17 854051 LEFI Sample M2 3.8 Significant
60.0 - 4 replicates 3.6
difference
57.5
Verteilungssumme Q1 / %

- each replicate 3.4

between two

Verteilungsdichte q1*
55.0
Sample M6 3.2
52.5
50.0 - 2 replicates measured 3 to 8 times 3.0 different NC
47.5
45.0 - each measured - Number of fibres 2.8 samples
42.5
3 times measured: 2.6
found (as
40.0 2.4
37.5 >500’000 fibres 2.2
expected)
35.0
32.5
(= 30s with 400 frames/s) 2.0
Fibre Length:
30.0 or ≈ 70’000 fibres 1.8
27.5 (number of pixels) 1.6
25.0
1 2 3 4 (= 60s with 25 frames/s)
1.4
22.5
20.0 1.2
17.5
1.0
15.0
0.8
12.5
10.0 0.6
7.5
0.4
5.0
0.2
2.5
0.0 0.0
2 4 6 8 10 20 40 60 80 100 200 400 600 800 1000 2000 4000 6000
Faserlänge / µm

2012 NC Symp Spiez _ Pres Vogelsanger et al 1 _ Standards for NC Testing.ppt Vob © Nitrochemie 2012 15
New Standards for NC Testing – STANAG 4178 Ed. 2 / MIL-DTL-244 B/ECP / C

Highlight 3: Fibre Quality Analyzer – Refining Process

100
Cumulative Fibre Length Ll [%]

90
NC 01 I 196-10
80
Cut 1 _ 1 h
70 Cut 1_ 2 h
Cut 1_ 3 h
60 Cut 1 _ 3.7 h
50 Cut 2 _ 1h
Cut 2_2h
40 Progress of the refining Cut 2_3h
process can be tracked Cut 2 _ 3.7 h
30 almost in real-time Cut 3 _ 1h
20 Cut 3 _ 2 h
Cut 3 _ 2.8 h
10 Finished Lot
0
0 500 1000 1500 2000 2500 3000
Fibre Length [µm]
2012 NC Symp Spiez _ Pres Vogelsanger et al 1 _ Standards for NC Testing.ppt Vob © Nitrochemie 2012 16
New Standards for NC Testing – STANAG 4178 Ed. 2 / MIL-DTL-244 B/ECP / C

Highlight 3: Fibre Quality Analyzer – Different Instruments

Normalized Cumulative Lenght-Weighted Fiber Length Distribution for Sample M2

100
Instrument 2:
90
Fibres ≥ 12 µm
Ll = 218 ±7 µm
80 Instrument 1:
Fibres ≥ 5 µm
% Cumulative Fiber Length

70 Ll = 198 ±4 µm Downside of method:

60 Instrument 2: Result strongly depends
Fibres ≥ 36 µm on instrument type and
50 Ll = 273 ±4 µm chosen resolution
40 This because higher
optical resolution means
30 that also smaller fibres
Instrument 3:
("fines") are recognised
20 Fibres ≥ 42 µm
Ll = 268 ±4 µm and included in the data
10 analysis)

0
0 100 200 300 400 500 600 700 800
Fiber Length (µm)

2012 NC Symp Spiez _ Pres Vogelsanger et al 1 _ Standards for NC Testing.ppt Vob © Nitrochemie 2012 17
New Standards for NC Testing – STANAG 4178 Ed. 2 / MIL-DTL-244 B/ECP / C

Drawbacks / not yet solved Problems

General:
Many NC tests are still "old-fashioned" wet-chemistry methods
(time-consuming, difficult to automatise, yield little information)
No test for characterisation of NC processability available
Nitrogen Content of NC (Mean Value):
Existing test methods are complex and error-prone
Distribution of Nitrogen Content of NC:
No method for direct determination available
Is determined indirectly via solubility of NC in solvents
Polymeric Properties:
GPC method is not (yet) reproducible enough for routine testing
Falling sphere viscosity method is not suitable for low-viscosity NC
Fibre Quality – Agglomerate Content:
Actual method is not suitable for low agglomerate contents

2012 NC Symp Spiez _ Pres Vogelsanger et al 1 _ Standards for NC Testing.ppt Vob © Nitrochemie 2012 18
New Standards for NC Testing – STANAG 4178 Ed. 2 / MIL-DTL-244 B/ECP / C

Drawback 1: Assessment of Average Nitrogen Content of NC

All existing test methods for average N-content are complex + error-prone
Ferrous Ion Titration (FS/FAS) is reference method, but:
Many labs have reported problems with this method
Performance / results of FS/FAS depend strongly on
several experimental parameters → method is not robust
Not tolerable (and difficult to recognise) systematic
deviations may appear together with excellent precision
Exactly following the operating procedure as described in the
standards (MIL/ STANAG) does not guarantee correct results !
For example, STANAG 4178 Ed.2 / MIL-DTL-244B/ECP:
Allows to use from 50 mL to 125 mL of sulphuric acid
Does not specify the temperature of the acid (as long as below 25°°C)
Specifies titrant temperature to not exceed 25°°C for >30 s and to not
exceed 35°°C for >10 s and to not exceed 40°°C at all
However, changes within this range already markedly alter the result !!!
2012 NC Symp Spiez _ Pres Vogelsanger et al 1 _ Standards for NC Testing.ppt Vob © Nitrochemie 2012 19
 New Standards for NC Testing – STANAG 4178 Ed. 2 / MIL-DTL-244 B/ECP / C

Drawback 1: Average Nitrogen Content of NC – FAS Method

12.82 Adding cold
sulphuric acid to NC
n=2-3
12.80
12.79
→ no bubbles
12.78
12.79
12.78
→ no "loss of
12.78
12.78 12.78 12.78 12.78 nitrogen"
n=8
12.76
12.76 These effects seen
150 mL H2SO4 0°°C
Nitrogen Content [%]

for NC (bubbles
N = 12.79%
12.74 → strong sensitivity
75 mL H2SO4 0°°C on H2SO4 volume
12.72 N = 12.78%
12.71
and T as well as
n=2 on titration T) are
12.70 50 mL H2SO4 0°°C almost negligible for
max. titration T 20°°C
KNO3 calibration
12.68 N = 12.76%
standard !!!
50 mL H2SO4 0°°C
12.66 max. titration T 30°°C
Adding 22°°C warm
12.65 N = 12.71%
sulphuric acid to NC
12.64
50 mL H2SO4 22°°C → micro-bubbles of
n = 28 max. titration T 30°°C
12.62
NO → "loss of
N = 12.65%
nitrogen"
2012 NC Symp Spiez _ Pres Vogelsanger et al 1 _ Standards for NC Testing.ppt Vob © Nitrochemie 2012 20
New Standards for NC Testing – STANAG 4178 Ed. 2 / MIL-DTL-244 B/ECP / C

Drawback 2: No Method for Distribution of Nitrogen Content

No standardised method for direct determination of the distribution of
nitrogen content of NC (→
→ quality of nitration) is available
Solubility of the NC in Ether-Alcohol and Acetone gives only crude indi-
cation regarding N-content distribution but is the only available method

N-Content
N-Content < 9.5% > 13.0%
N-Content 10% – 12.8%
→ Insoluble in → Soluble in
both Acetone and → Soluble in both Acetone
and Ether-Alcohol Acetone
Ether-Alcohol but insoluble in
Ether-Alcohol

9 10 11 12 13 14
Nitrogen Content of NC [%]
2012 NC Symp Spiez _ Pres Vogelsanger et al 1 _ Standards for NC Testing.ppt Vob © Nitrochemie 2012 21
New Standards for NC Testing – STANAG 4178 Ed. 2 / MIL-DTL-244 B/ECP / C

Summary

The new standards STANAG 4178 Ed. 2 and MIL-DTL-244B/ECP /

MIL-DTL- 244C provide for the first time in history an internationally
accepted set of NC testing methods
STANAG 4178 Ed. 2 is currently in NATO ratification (11 nations including
US, UK and France have already ratified; a total of 14 is needed)
MIL-DTL-244B/ECP is currently used in US ARMY, NAVY and Air Force;
MIL-DTL-244C will be implemented by US when ARDEC Standardization
Group complete the review
The new test methods are already implemented in many nations
An international Round Robin Test will be organised to support further
implementation of the new methods
Test methods in these standards are
neither perfect nor complete; further
work is necessary to improve the
actual methods as well as to develop
new / better tests

2012 NC Symp Spiez _ Pres Vogelsanger et al 1 _ Standards for NC Testing.ppt Vob © Nitrochemie 2012 22
New Standards for NC Testing – STANAG 4178 Ed. 2 / MIL-DTL-244 B/ECP / C

Outlook

Ratification / approval / implementation

of STANAG 4178 Ed. 2 / MIL-DTL-244C
needs to be completed
Tests which are new in these standards or
known to produce problems should be carefully examined and, if
necessary, further improved (e.g. Nitrogen Content, Ion Chromatography,
Gel Permeation Chromatography* and Fibre Length Distribution)
New / improved test methods should be developed and included:
Test methods that better characterise the Processability of NC
Better test methods for Nitrogen Content Distribution* to replace
Ether-Alcohol / Acetone Solubility (e.g. chromatographic method)
New method suitable for low Agglomerate* contents
Modern spectroscopic methods such as IR / Near IR* / Raman
Spectroscopy with multivariate analysis to predict important properties
such as moisture content, nitrogen content, solubility, viscosity, etc.
* Presentations on these issues will be given in the 5th NC Symposium
2012 NC Symp Spiez _ Pres Vogelsanger et al 1 _ Standards for NC Testing.ppt Vob © Nitrochemie 2012 23
New Standards for NC Testing – STANAG 4178 Ed. 2 / MIL-DTL-244 B/ECP / C

Thanks very much for your attention !

2012 NC Symp Spiez _ Pres Vogelsanger et al 1 _ Standards for NC Testing.ppt Vob © Nitrochemie 2012 24