Whole Life Assessment of Nitrocellulose in

Double Base Propellants

Nathalie Mai
Michael Isherwood
Phil Gill
 Contents
• Introduction
• Aged DB rocket propellant analysis
– GPC
– HPLC

• Aged DB gun propellant analysis

– GPC
– microhardness

• Conclusion and future work

2
 The problem

Whole life assessment of NC in propellants

• Processing parameter during manufacture
– viscosity…
• Chemical ageing
– stabiliser depletion
– NC molar mass changes
• Mechanical ageing
– hardness…

3
 GPC method described in STANAG 4178

• Repeatable results once a month (5 months)

same batch of NC was analysed in 20 replicates

RSD (Mn) RSD (Mw)

5 measurements 2.8% 2.8%

• RSD 10-100% in the past
• Comparable to other analytical techniques

4
 Validation of the GPC method

• Broad distributed PS standard NBS 706a

• Certified by NIST (previously NBS)
• Injected in triplicate with every set of
propellant samples

5
Accuracy and precision of the GPC method

14 measurements of NBS 706a Mw in triplicate (5

month)
• Accuracy:
– Mw = 2.85 ± 0.23 105 g/mol (± 8%) certified by NIST
• Precision: RSD < 0.9%

6
 The aim

• To assess the life of DB propellants by:

– transferring the GPC method to formulated NC
product (aged DBP)
– measuring the kinetic parameters (k, Ea)

• To perform mechanical testing and correlate

results to average molar mass of NC

7
 Propellants used

• Generic DB rocket propellant

– NG, NC, p-NMA and 2-NDPA
– supplied by Roxel (UK Rocket Motors) Ltd

• DB gun propellant, 20 mm (Phalanx)

– NC, NG, DPA
– donated by DOSG MoD
– in addition naturally aged propellant (15 y old) was
supplied

8
 Ageing (AOP-48)
2g for DB rocket propellant / 5g for DB gun
propellant were
• pre-conditioned
– 60-70% RH level, 48h, 25oC
• heat sealed in polymer coated aluminium
bags
• aged at
– 30, 40, 50, 60oC (DB rocket propellant)
– 70, 80oC (DB gun propellant

9
 GPC sample preparation

• Simple, quick and easy with no pre-conditioning

• 24h in solution

• Automatic injection in 5 replicates

10
 Contents
• Introduction
• Aged DB rocket propellant analysis
– GPC
– HPLC

• Aged DB gun propellant analysis

– GPC
– Microhardness

• Conclusion and future work

11
 Mw changes for artificially aged DB rocket
propellant
Thousands
Mw (g/mol)

650

550

450

350

60 deg C 50 deg C 40 deg C 30 deg C

250
0 100 200 300 400 500 600
Ageing time (day)
• Mn follows the same trend
12
 Arrhenius plot for NC decomposition
10

8
LnKNC

Ea = 93.5 kJ/mol
6

4
0.0028 0.0029 0.003 0.0031 0.0032 0.0033 0.0034
1/T (K)

Decomposition of NC at T<60oC dominated by low Ea process.

13
 NC decomposition

NC decomposes following 2 pathways:

• Thermolysis of CO-NO2 group (producing 2
radicals) Ea = 160-170 kJ/mol
• Hydrolysis of CO-NO2 group (producing nitric
acid) Ea = 100 kJ/mol
Our result is consistent with hydrolysis
process

Ref: M. A. Bohn, J. of Thermal Analysis and Calorimetry, 2001, 65,103

14
 Depletion of stabilisers at 60oC

0.70
2-NDPA content, wt.%

0.60
2-NDPA p-NMA

0.50

0.40

0.30

0.20

0.10
0 20 40 60 80 100 120 140
Ageing time (day)

15
2-NDPA content, wt.%
2-NDPA depletion

0.40

0.30

0.20

60 deg C 50 deg C 40 deg C

0.10
0 50 100 150 200 250 300 350 400
Ageing time (day)

16
 Arrhenius plot for 2-NDPA depletion

-3

-5

-7 Ea = 175 kJ/mol
LnKstab

-9

-11

-13

-15
0.0028 0.003 0.0032 0.0034
1/T (K)

17
 P-NMA depletion
0.7
p-NMA content, wt.%

0.6

0.5

0.4

0.3

0.2

0.1 60 deg C 50 deg C 40 deg C 30 deg C

0.0
0 100 200 300 400 500
Ageing time (day)
18
 Arrhenius plot for p-NMA depletion

-3

-5
Ea = 103 kJ/mol
-7
LnKstab

-9

-11
p-NMA 2nd Mech.
Ea = 113 kJ/mol
-13 p-NMA 1st Mech.

-15
0.0028 0.003 0.0032 0.0034
1/T (K)

19
 Summary

• Mw and Mn decrease with ageing time

• Low Ea (Mw) consistent with hydrolysis
• p-NMA is consumed quicker than 2-NDPA with
lower Ea
• 2 mechanisms involved in depletion of p-NMA
• Material too soft to do mechanical tests

20
 Outline
• Introduction
• Aged DB rocket propellant analysis
– GPC
– HPLC

• Aged DB gun propellant analysis

– GPC
– microhardness

• Conclusion and future work

21
 Mw changes for artificially aged DB gun
propellant
Thousands
Mw (g/mol)

500

400 70 deg C 80 deg C

300

200

100
0 200 400 600 800
Ageing time (h)

22
 Mn changes for artificially aged DB gun
propellant
Thousands
70
Mn (g/mol)

70 deg C 80 deg C
60

50

40

30
0 100 200 300 400 500 600 700
Ageing time (h)

23
 Apparent number of chain scissions of NC
artificially aged at 70 and 80oC
Scissions per molecule

0.75
70 deg C 80 deg C

0.50
S = (Mno/Mnt) - 1

0.25

0.00
0 200 400 600 800
Ageing time (h)

24
 Vickers hardness test

• Easy and quick testing procedure

which consists of measuring the
diagonals of the impression left
by a load of various magnitudes

25
Grain hardness changes with ageing time

19
Hardness Vicker (Hv)

70 deg C 80 deg C

17

15

13

11
0 150 300 450 600 750 900
Ageing time (h)

26
Relationship between grain hardness and
NC Mw
Hardness Vickers (Hv)

19

70 deg C 80 deg C
17

15

13

11
140000 240000 340000
Mw (g/mol)

27
 Naturally aged propellant 15-16y
Hardness Vickers (Hv)

19

70 deg C 80 deg C

17 Naturally aged

15

13

11
140000 240000 340000
Mw (g/mol)

28
 Summary

• Mw and Mn decrease with ageing time

• Chain scission factor consistent with hydrolysis
• Grain hardness decreases with ageing time
• Good correlation between grain hardness and
Mw
• Naturally aged material fits with the curve

29
 Contents
• Introduction
• Aged DB rocket propellant analysis
– GPC
– HPLC

• Aged DB gun propellant analysis

– GPC
– microhardness

• Conclusion and future work

30
 Conclusion

• The GPC method successfully transferred to

formulated NC
• Ea (Mw) correlates well with published values
• Good correlation between the Mw and
mechanical properties.

31
 Ongoing experiments and future work

• Reducing sample preparation time (4h using

shaker)
• Comparison GPC analysis, mechanical
properties for aged propellants
– DMA, microhardness, nanoindentation

• Round Robin analysis of NC in propellants

planned for 2011/2012

32
 Acknowledgment

• AWE and DOSG for sponsoring the work

• Roxel (UK Rocket Motors) Ltd for providing the
DB rocket propellant
• Cranfield University staff and students

• Thank you for your attention

33
 Any question?

The Defence Academy Campus

34