Journal Pre-proof

Three-dimensional network structure nitramine gun propellant with nitrated bacterial

cellulose

Yingbo Wang, Limin Jiang, Jun Dong, Bin Li, Jinpeng Shen, Ling Chen, You Fu,
Weidong He

PII: S2238-7854(20)31956-6
DOI: https://doi.org/10.1016/j.jmrt.2020.10.097
Reference: JMRTEC 2380

To appear in: Journal of Materials Research and Technology

Received Date: 15 August 2020

Revised Date: 26 October 2020
Accepted Date: 29 October 2020

Please cite this article as: Wang Y, Jiang L, Dong J, Li B, Shen J, Chen L, Fu Y, He W, Three-
dimensional network structure nitramine gun propellant with nitrated bacterial cellulose, Journal of
Materials Research and Technology, https://doi.org/10.1016/j.jmrt.2020.10.097.

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© 2020 The Author(s). Published by Elsevier B.V.

 1 Three-dimensional network structure nitramine gun propellant with
2 nitrated bacterial cellulose

3 Yingbo Wanga,b#, Limin Jianga,b#, Jun Dongc, Bin Lic, Jinpeng Shena,b,d,
4 Ling Chena,b, You Fua,b, Weidong Hea,b*

a
5 School of Chemical Engineering, Nanjing University of Science and Technology,
6 Nanjing, Jiangsu, China; bKey Laboratory of Special Energy materials, Ministry of
7 Education, Nanjing, Jiangsu, China; cLuzhou North Chemical Industries Co., Ltd.,
8 Luzhou, Sichuan, China; dState Key Laboratory of Environment-friendly Energy

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9 Materials, Southwest University of Science and Technology, Mianyang, Sichuan, China.

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10 Highlights

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1. Nitrated bacterial cellulose was first applied to the propellant system to
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12 improve its mechanical properties.
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13 2. For the first time, nitramine propellant with nitrated bacterial cellulose
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14 formed a spatial 3D network structure that improved the performance of

15 the propellant system.
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16 3. The thermal behaviour of the nitrated bacterial cellulose nitramine

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17 propellant was studied, reflecting its good compatibility.

18 4. The performance stability of nitramine propellants with nitrated

19 bacterial cellulose with different plasticisers was discussed.

20 5. NBC can be directly applied in existing applications that could develop

21 the propellant industry.

*Corresponding Author: Weidong He (hwdchem331@163.com).

# Co-first authors: Yingbo Wang and Limin Jiang are co-first authors of the article.

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22 Abstract

23 The properties of gun propellants are important for the stability of weapon systems and

24 have been extensively studied in the field of weapon research. In this work, an applied

25 semi-solvent method was used to prepare a triple base gun propellant with nitrated

26 bacterial cellulose (NBC)/nitrocellulose (NC) as the binder system. For the first time,

27 the study found that the addition of NBC in the propellant system resulted in an distinct

28 spatial 3D network structure. The morphology, composition, mechanical properties,

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29 energy, thermal behaviour, and combustion performance of the network structure were

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30 characterised. The formation mechanism of the spatial network structure and effect of

31 -p
the NBC addition on the propellant performance were discussed. This work verified the
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32 application of NBC in different plasticisers and indicated the effective improvement of

33 the impact resistance and burning rate by the spatial network structure propellant with
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34 NBC, while retaining other properties.

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35 Keywords: nitrated bacterial cellulose; triple base gun propellant; combustion

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36 characterisation; spatial network structure

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*Corresponding Author: Weidong He (hwdchem331@163.com).

# Co-first authors: Yingbo Wang and Limin Jiang are co-first authors of the article.

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37 Graphical Abstract

38 With 5% nitrated bacterial cellulose, triple base gun propellants with different

39 plasticisers were prepared by a semi-solvent method. Notably, a 3D spatial network

40 structure was discovered. In addition, the impact resistance significantly improved with

41 a stable and safe thermal behaviour.

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42
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43 1 Introduction
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44 With the improvement in modern weapons, there is increased energy

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45 requirements from propellants. To satisfy this, high-energy additives are often added;
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46 however, this results in the decreased mechanical properties of propellants [1, 2], which

47 is an important parameter in evaluating their applicability to tank gun ammunition [3].

48 Therefore, in the design of a propellant formulation, not only should its energy be

49 improved but also its mechanical performance [4-6].

50 At present, nitrocellulose (NC) is the main binder in conventional propellant

51 systems [7]. Plant fibres are widely used for the production of NC owing to their wide

52 selection of materials and easy processing [8]. However, the propellant application of

53 NC derived from plant fibres faces two main problems: ① In addition to cellulose, plant

54 fibres contain lignin, hemicellulose, and pectin, which require further purification for its

55 suitability in practical applications [9]. The removal of lignin and hemicellulose is

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56 difficult, expensive, and detrimental to the environment [10]. ② The hair-like structure

57 of NC molecules leads to the relatively poor overall rigidity and mechanical properties

58 of the propellant system [11].

59 Currently, there are several studies carried out to solve the existing problems of

60 NC and satisfy the required mechanical properties for propellants. For a new adhesive

61 system, 0.5% neutral polymer binder (NPBA) is added to nitrate-plasticised polyether

62 (NEPE) propellant, thereby improving its mechanical properties [12]. However, as

63 NPBA does not contain nitrate ester groups, its addition reduces the energy of the NEPE

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64 propellant. The addition of new high-energy plasticisers, such as 1,5-diazido-3-

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65 nitrazapentane [13] and N-butyl-N-(2-nitroxy-ethyl) nitramine [14], can increase the

66
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energy of the propellant with minimal improvement in its mechanical properties.
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67 Studies have shown that the mechanical properties of nitramine propellants improved as
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68 the 1,3,5-trinitroperhydro-1,3,5-triazine (RDX) content increased. However, with

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69 further increase in the RDX content, its mechanical properties gradually deteriorates

70 [15]. Moreover, RDX does not significantly improve the mechanical properties of
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71 nitramine propellants. These existing methods still face limitations in terms of energy
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72 reduction, minimal improvement of the mechanical property, or inability to achieve

73 both improved energy and mechanical properties.

74 Bacterial cellulose (BC) is a type of bacterial secretion [16] with higher purity

75 [8], crystallinity [17], and mechanical properties [18] than plant fibres. It has a spatial

76 network structure and composition similar to NC [19]. Owing to its structure, BC

77 retains a spatial 3D network structure after nitration by mixed nitro-sulphur acid [20],

78 which is referred to as nitrated bacterial cellulose (NBC). The synthesis of NBC from

79 BC by nitrification method was studied at a nitrogen content of 12.1% [7]. A study of

80 the characteristics of NBC in acetone solution showed its increased viscosity with the

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 81 increase in its nitrogen content and molecular weight [21]. The rheology of NBC in

82 N,N-dimethylformamide solution has also been studied, noting a threshold

83 concentration of 5.0% NBC solution for Newtonian and non-Newtonian fluids. In

84 addition, NBC solution exhibits a shear thinning effect for non-Newtonian fluids [22].

85 This work studied the effect of NBC addition on the performance of triple base

86 propellants. A semi-solvent method was used to prepare the nitramine propellants with

87 NBC/NC as the binder (NBC content 5 wt.%) and nitroglycerine (NG) as the plasticiser.

88 The morphology, composition, mechanical properties, energy, thermal behaviour, and

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89 combustion performance of the samples were obtained. With the addition of NBC, a

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90 noticeable spatial 3D network structure was discovered for the first time. In addition,

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the application of NBC as different plasticisers for nitramine propellants has been
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92 verified. To date, the application of NBC in propellants is yet to be reported.
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93 2 Experiments
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94 2.1 Materials and Instruments

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95 NBC and NC with 12.6% nitrogen, respectively, RDX, NG/NC tablet (41/59

96 wt.%), diethyleneglycol dinitrate (DEGDN)/NC tablet (43/57 wt.%), trimethylolethane

97 trinitrate (TMETN)/NC tablet (43/57 wt.%), and N,N'-dimethyl-N,N'-diphenylurea were

98 supplied by Luzhou North Chemical Industry Co., Ltd. (Luzhou, China). Ethanol and

99 acetone were provided by Nanjing Chemical Reagent Co., Ltd. (Nanjing, China).

100 Scanning electron microscopy (SEM) images were obtained using Quanta FEG

101 250 (FEI, USA) with 5 kV accelerating voltage to characterise the surface morphology

102 of the nitramine gun propellants. X-ray diffraction (XRD) using D8 ADVANCE

103 instrument (Bruker, USA) characterised the crystal structure of NC, NBC, RDX, and

104 propellants. Fourier transform infrared spectrometer (FTIR, Nicolet 10, USA) obtained

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105 the changes in the functional groups. The spectra were recorded in transmission mode in

106 the range of 4500 to 500 cm−1 with a spectral resolution maintained at 4 cm−1. Thirty-

107 two scans were performed to achieve an acceptable signal-to-noise ratio. Mechanical

108 property experiments were carried out with the impact strength test equipment JJ-20

109 from Changchun Intelligent Instrument Equipment Co., Ltd. (Changchun, China) with a

110 hitting energy of 4 kJ for the pendulum. Before the impact strength tests, all specimens

111 were conditioned at −40, 20, and 50 °C for 12 h. The tensile and compression strength

112 tests were performed using a universal material experiment machine (WGD-1) from

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113 Shanghai Songdun Instrument Equipment Co., Ltd. (Shanghai, China) at across-head

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114 speed of 10 mm/min. All tests were conducted at −40, 20, and 50 °C, each sample was

115
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tested 10 times with the average results reported.
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116 The heat of explosion was measured using ZDHW-6W computer calorimeter
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117 from Hebi Auvai Dimension Electronic Technology Co., Ltd. (Hebi, China) under N2
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118 atmosphere with samples weighing 1.000±0.005 g. The detonation heat of each sample

119 was measured thrice with the average results reported. The thermal decomposition
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120 properties were investigated by thermogravimetric analysis (METTLER TOLEDO,

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121 SDTA851E Instruments, Switzerland) and differential scanning calorimetry (DSC,

122 METTLER TOLEDO, 823E Instruments, Switzerland). DSC experiments were carried

123 out under Ar atmosphere (20 mL/min) at a heating rate of 10 °C/min from 50 to 350 °C.

124 The closed vessel tests performed using a 100 cm3 vessel reflected a constant volume

125 combustion. A 1.0 g NC powder with 10.98 MPa ignition pressure was used as the

126 ignitor. The loading density of each sample was 0.2 g/cm3 at 20 °C. The burning

127 pressure (p), burning time (t), burning rate (u), dynamic vivacity (L), and relative

128 pressure (B) were used to characterise the stability of the combustion (p–t curves),

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129 change in burning rate (u–p curves), and combustion state of the burning surface (L–B

130 curves).

131 2.2 Preparation of BC, NBC, and composites

132 The preparation of BC and NBC is described in previous reports [7, 23].

133 Acetobacter xylinum was cultured by static incubation to obtain a BC gel. The BC film

134 was removed from the culture medium and treated with 4% (w/v) NaOH at 80 °C for

135 2 h to dissolve the impurities and cells and then washed thoroughly with tap water until

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136 the water achieved a neutral pH. The purified BC membrane was dried to a constant

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137 weight at 80 °C and crushed to obtain the BC powder. The mixed acid as added into the

138
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reaction kettle. The BC powder was then slowly added and after reacting within a
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139 certain temperature range (60 °C) for 60 min, the material was discharged and filtered.
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140 The obtained NBC was washed with water, alkali, and then water again. Subsequently,

141 it was dried to obtain the final NBC product.

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142 The composition of the NC and NBC/NC nitramine gun propellants are listed in
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143 Table 1. The raw materials were prepared according to the listed formula ratio and
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144 stirred at 2800 r/min for 3 h. The absorbed powder was then vacuum filtered, pressed

145 into a sheet using a calendar at a roller temperature of 80 °C for 15 min, and placed in

146 an oven at 50 °C for 5 days. The propellant material was then fully mixed with the

147 solvent. It was then plasticised for 2 h and then compressed into a tubular drug strip by

148 an extrusion moulding method (15~20kN). The samples were then cut into short tubes

149 40±1 and 60±1 mm long for the combustion characterisation and mechanical property

150 experiments, respectively. The samples were placed in a drying oven at 55 °C for 5 days

151 to completely remove the solvent. The NBC/NC nitramine gun propellants shown in

152 Figure 1 were obtained by a production method similar to existing engineering

153 application processes.

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154 3 Results and Discussion

155 3.1 Morphology

156 Figure 2(a) and 2(b) clearly show the difference in the morphology of

157 conventional and NBC/NC nitramine gun propellants. The NC-based propellant has

158 tiny, layered structures due to the rotation and twist forces during the extrusion process.

159 Meanwhile, the NBC/NC nitramine gun propellants have a 3D bone-like spatial

160 network structure with extremely high strength [5, 24-26] and noticeable grid layer

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161 structure. This network structure is helpful in the dispersion of forces. Holes sized

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162 approximately 5 μm caused by the stripping of RDX particles can also be noted. The

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cavities in this grid structure have diameters of 150–1000 nm, as shown in Figure 2(b)–
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164 2(g), which demonstrate the similar micromorphologies of the NBC nitramine
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165 propellants with different energetic plasticisers. A small amount of evenly dispersed

166 RDX particles can also be observed in the morphology of the samples, as shown in
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167 Figure 2(a) and 2(b), which is consistent with conventional propellants.
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168 3.2 Composition Analysis

169 XRD analysis was used to investigate the changes in the crystal structure of the

170 gunpowder nitramine propellant system. As shown in Figure 3, both NC and NBC

171 partly have crystal areas with the latter having a sharper diffraction peak. This

172 demonstrates the better crystallinity of NBC, which can be attributed to its smaller

173 molecular weight. The diffraction peak of NBC declined as plasticising disrupted its

174 crystal area. Different NBC/NC propellants have nearly similar spectra, indicating the

175 similar crystal structures in the NBC/NC matrix. Moreover, by XRD analysis, we can

176 confirm the aggregation of the binder, plasticiser, and nitramine components in the

177 propellants. For the triple base nitramine gun propellants, the sharp diffraction peaks of

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178 RDX represent (111), (210), and (321) among others. With the increase of 2θ from 10°

179 to 30°, crystal faces are noted in the diffraction peaks of the propellants, indicating the

180 compounding of RDX [27].

181 The molecular structures of the propellants were identified by FTIR analysis. From

182 Figure 4, similar stretching vibration peaks can be observed for all samples, which

183 explains the same functional groups for the NBC nitramine and conventional

184 propellants. The peaks at 1630.7 and 1267.6 cm−1 are related to the –NO2 asymmetric

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185 and –NO2 symmetric stretching vibrations, respectively. O–NO2 stretching vibration

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186 and twisting vibration absorption peaks are noted at 827.2, 748.9, and 681.1 cm–1,

187 -p
respectively. The FTIR absorption peaks of RDX at 910.0, 1267.6, 1630.7, and 3071.1

cm−1 correspond to the vibrations of CN, –NNO2, –NO2, and C–H, respectively [28].
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188

189 The small peak at 2918.7 cm–1 is attributed to the asymmetric stretching vibration of –
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190 CH2 in the NC molecular chain. Lastly, the small peak at 3071.1 cm−1 indicates the
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191 uneven distribution and random dispersion of RDX throughout the propellant. The
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192 results obtained through FTIR analysis agree with the SEM images.
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193 3.3 Mechanical Properties

194 Figure 5(a) shows the impact strength of the samples at −40, 20, and 50 °C. The

195 specific values are displayed in Table 2. At lower temperatures, NC-based propellants

196 are brittle and hard [29], thereby reducing its impact strength. There is an evident

197 improvement on the impact strength after incorporating 5% NBC to the NC nitramine

198 gun propellants. Particularly, the impact strength at −40, 20, and 50 °C increases by

199 41.73%, 103.80% and 76.08%, respectively, compared with NC nitramine gun

200 propellants. The improved impact performance is attributed to the significant

201 contribution of the spatial network structure in NBC that is conducive for force

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202 dispersion. The mechanical and chemical activities could also lead to enhanced

203 mechanical properties, similar to that of a carbon nanotube [30, 31]. Since NBC and NC

204 have the same structural unit, only the molecular weight and structure differed and

205 strong chemical similarities were noted [20]. Therefore, after swelling the two

206 celluloses with a solvent, their surfaces are easily dissolved and combined since

207 swelling is highly sensitive to parallel or antiparallel arrangements of cellulose

208 crystallite chains [32]. Moreover, even with the same total molecular weight, NBC has a

209 network structure with more chain ends; thus, it has a stronger nano-size effect than NC

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210 [22]. Nanomaterialisation is beneficial in reducing the internal cracks and crack

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211 branches in the composite structure [33].
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212 At −40 °C, the impact strength of NBC/NC–TMETN nitramine gun propellant is

213 higher than that of the NBC/NC–NG/DEGDN propellant. This can be attributed to the
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214 large molecular volume of TMETN that partially breaks the cross-linking of the NC
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215 molecular chain and influences the cross-link density and structure rigidity of the
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216 polymer. The glass transition temperature (Tg) is determined by the cross-link density
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217 and structural rigidity of the polymer [34, 35]. Different melting points were obtained

218 for the four different plasticisers used in this study. With a higher melting point, NG is

219 found to be the most brittle at low temperatures. The large molecular volume of

220 TMETN improved the molecular chain movements, thereby decreasing Tg [36] and

221 enhancing the mechanical properties at low temperatures. TMETN has a larger relative

222 molecular mass than NG with plasticisers accounting for 20 wt.% of the propellants;

223 thus, NG has more molecules. Similarly, due to its large number, NG molecules

224 damaged the cross-linked network, leading to NBC/NC–NG nitramine gun propellant

225 having a lower impact strength than NBC/NC–TMETN nitramine gun propellant.

226 Although TMETN has more molecules, DEGDN is a linear molecule, allowing it to

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227 enter the NC molecular chains and decreasing the rigidity of NC. Meanwhile, DEGDN

228 has less damage to the cross-link network than TMETN. Consequently, the impact

229 strength of NBC/NC–DEGDN, NBC/NC–TMETN, and NBC/NC–NG nitramine gun

230 propellant gradually decreased.

231 Figure 5(b) and 5(c) show the relatively high standard deviation of the tensile

232 strength values of the samples. The tensile strength of the NBC/NC samples at −40 °C

233 significantly improved, while those at 20 and 50 °C remained unchanged. On the other

234 hand, the compressive strength of NBC/NC at −40, 20, and 50 °C is significantly higher

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235 than those of the NC samples. Thus, NBC addition effectively improved the tensile and

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236 compressive strength of the propellant, especially in the low-temperature environment.

237
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The reason for this is similar to the mechanism of improved impact strength by NBC
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238 addition.
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239 3.4 Energy Performance

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240 After replacing NC with NBC, the energy of the propellant is nearly equal due to
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241 their similar composition even with the difference in their structures (Figure 6, Table 3).
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242 Among the three propellants, NBC/NC–NG propellant has the highest energy. As

243 expected, the detonation heat of NBC/NC–DEGDN and NBC/NC–TMETN propellants

244 has minimal disparity due to their equal heat of combustion. The uncertainty of the heat

245 of explosion can be attributed to the random dispersion of RDX in the propellant system

246 as the weight of RDX varies even with the same total weight.

247 3.5 Thermal Behaviours

248 As shown in Figure 7(a), a notable mass loss can be observed for all propellants at

249 100–170 °C due to the thermal decomposition [37] and volatilisation [38] of the

250 plasticisers. The decomposition temperature of TMETN is higher than that of DEGDN

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251 and NG; therefore, the mass loss in the curve is noted later at 200 °C due to the

252 decomposition of the nitrate ester composite.

253 In Figure 7(b), there are two decomposition peaks at 10 °C/min (heating rate)—

254 a main decomposition peak and weak peak (grey dashed box). The main exothermic

255 peaks are caused by the thermal decomposition of the composite propellants. The main

256 peak did not shift, indicating the nearly similar thermal decomposition performance of

257 NBC/NC and NC nitramine gun propellants. This similar decomposition peak indicates

258 the good compatibility between the NBC and plasticisers, thereby demonstrating the

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259 better storage performance and safety. The small peaks are attributed to the

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260 decomposition of RDX at 250 °C [39].

261
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The strength of the decomposition peak indicates the energy of the propellants.
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262 In Table 4, there is no significant difference between NBC/NC and NC nitramine gun
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263 propellants with respect to ΔH due to their similar chemical components. As shown in
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264 Figure 7(c), the trend of ΔH is similar to that of the detonation heat, thereby reaffirming

265 previous reports of detonation heat analysis [40-42]. The uncertainty in ΔH is attributed
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266 to the heterogeneous composition of the propellant, including RDX particles and NC
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267 fibres with wide size variations from nanometres to tens of micrometres [24].

268 3.6 Combustion Characteristics

269 Figure 8 shows the combustion characteristics curve of NC (1) and NBC/NC (2)

270 nitramine gun propellants at 20 °C. Both samples can be steadily burned; however, the

271 burning of NBC/NC–NG nitramine gun propellant slightly differs from that of the NC–

272 NG nitramine gun propellant due to the inevitable test bias. The maximum pressure of

273 the NC nitramine (Figure 8(a), line 1) and NBC/NC nitramine gun propellants (Figure

274 8(a), line 2) are 274.08 and 275.13 MPa, respectively. Without any significant

275 difference, NBC/NC nitramine propellants burned steadily and smoothly (Figure 8(a),

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276 lines 2–5).

277 The u–p curve in Figure 8(b) reflects the burning rate of the propellants. Under the

278 same environmental pressure, the burning rate of NBC/NC nitramine-gun propellant is

279 higher than that of the NC nitramine gun propellant. This phenomenon is aggravated as

280 the combustion pressure increases. The burning rate at 100 MPa is 9.70 and 10.10 m/s,

281 and 18.81 and 19.93 m/s at 200 MPa, which can be attributed to the promoted thermal

282 conduction, heat radiation, and combustion by the NBC network structure. As shown in

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283 Figure 8(c), at a B of 0.2–0.85, the L value of the five curves is constant at 0.72–1.07

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284 MPa/s. This proves the stable behaviour of the combustion surface during combustion,

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which conforms to the regulation of the surface combustion of NC nitramine gun and
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286 single-perforation grain propellants.
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287 4 Conclusion
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288 In this research, 5% NBC was added to a triple base gun propellant with evenly
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289 dispersed components. Owing to the spatial structure of NBC and size effect of
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290 nanomaterials, the gun propellant exhibited a spatial 3D network structure. This

291 structure played an important role in improving the impact resistance by 41.73%,

292 103.80%, and 76.08% from NC/NG nitramine gun propellants at −40, 20, and 50 °C,

293 respectively. This is mainly attributed to the stress dispersion caused by the network

294 structure in the NBC/NC nitramine gun propellant and compensation of the overall

295 propellant structure by the nano-NBC. The overall combustion of the NBC/NC

296 nitramine gun propellant is similar as that of the NC nitramine gun propellant with an

297 improved burning rate.

298 The energy and thermal behaviour of NBC/NC and NC–NG nitramine gun

299 propellants are nearly equal. It is worth noting that the NBC in the plasticiser system of

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300 the different triple base gun propellants has a highly consistent performance, which

301 confirms their stability. Different properties were noted for the plasticisers of the

302 NBC/NC nitramine gun propellants. Generally, the addition of NBC has a positive

303 effect on the impact resistance and burning speed of the triple base gun propellant with

304 minimal effect on its energy and thermal behaviour. With this work, NBC, which is a

305 more environmentally friendly, low-cost, better, and applicable alternative, is expected

306 to replace NC in future gun propellants.

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307 Acknowledgements

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308 Yingbo Wang and Limin Jiang are co-first authors of this article. This research

309
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did not receive any specific grant from funding agencies in the public, commercial, or
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310 not-for-profit sectors. Thanks to Dr. Chen Feiyun, Dr. Wang Binbin, Engineer Yu
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311 Yannian, Engineer Yin Shenglai and Master Wang Rutie for their experimental help and

312 technical support.

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313 I wish all countries and regions in the world get rid of the COVID-19 epidemic
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314 as soon as possible and return to normal life. I would like to thank all individuals who
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315 contributed during the COVID-19 epidemic, meanwhile, commemorate all the lives lost

316 due to the epidemic.

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432 -p
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433 Table 1. The composition of the NC and NBC/NC nitramine gun propellants.
Sample 1 2 3 4 5

NBC (wt%) - 5 5 5 5

RDX (wt%) 20 20 20 20 20

NC (wt%) 59 54 54 54 54

CT-2 (wt%) 1 1 1 1 1

NG (wt%) 20 20 10 - -

DEGDN (wt%) - - 10 20 -

TMETN (wt%) - - - - 20

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434 Table 2. The impact strength of the NC and NBC/NC nitramine gun propellants.

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No. Sample
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αk (kJ·m-2) σ αk (kJ·m-2) σ αk (kJ·m-2) σ

1 NC-NG 8.22 1.14 19.45 2.08 26.67 3.53

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2 NBC/NC-NG 11.65 3.48 39.64 5.17 46.96 8.71

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NBC/NC-
3 12.99 4.88 45.08 2.55 53.99 9.60
NG/DEGDN
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4 NBC/NCDEGDN 16.71 5.02 46.37 6.27 57.77 5.74

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5 NBC/NC-TMETN 16.44 2.62 42.92 3.93 53.42 8.05

435 Note: αk: impact strength of nitramine gun propellants, σ: standard deviation of impact
436 strength in 10 tests.

437 Table 3. Heat of detonation of the NC and NBC/NC nitramine gun propellants.

No. Sample Qe (J·g-1) σ

1 NC-NG 4873.67 19.35

2 NBC/NC-NG 4896.67 19.09

3 NBC/NC-NG/DEGDN 4833.47 30.35

4 NBC/NC-DEGDN 4476.33 180.93

5 NBC/NC-TMETN 4504.00 164.85

438 Note: Qe: Heat of detonation of the gun propellant samples, σ: standard deviation of
439 impact strength in 3 times.

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440 Table 4. Summarized results for DSC experiments of the NC and NBC/NC nitramine
441 gun propellants.

No. Name Tonset (°C) Texo (°C) ΔHdec (J/g)

1 NC-NG 192.71 207.39 1817.62

2 NBC/NC-NG 196.01 210.43 1819.12

3 NBC/NC-NG/DEGDN 197.21 211.75 1776.58

4 NBC/NC-DEGDN 199.09 211.06 1694.77

5 NBC/NC-TMETN 195.07 208.50 1689.59

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442 Note: Tonset: onset temperature of the exothermic peak, Texo: temperature of the
443 exothermic peak, ΔHdec: enthalpy of decomposition.

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444

445 Figure 1. Composite structure of NBC/NC nitramine gun propellants. The background

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446 picture is NBC raw materials structure (by Scanning Electron Microscope).

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447

448 Figure 2. SEM images of NC and NBC/NC nitramine gun propellants with different

449 plasticizers: (a) NC - NG propellants, (b) NBC/NC - NG propellants, (c) aperture size

450 of NBC/NC sample, (d) NBC/NC – NG/DEGDN propellants, (e) NBC/NC - DEGDN

451 propellants, (f) NBC/NC - TMETN propellants). The RDX particles and the cavities

452 formed after peeling are all marked in the samples.

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 of
453

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454 Figure 3. XRD spectra of NBC/NC nitramine gun propellants with different plasticizers

455 -p
(2: NBC/NC - NG propellants 3: NBC/NC – NG/DEGDN propellants, 4: NBC/NC -

456 DEGDN propellants, 5: NBC/NC - TMETN propellants).

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457

458 Figure 4. FTIR spectra of NC and NBC/NC nitramine gun propellants with different

459 plasticizers (1: NC - NG propellants, 2: NBC/NC - NG propellants 3: NBC/NC –

460 NG/DEGDN propellants, 4: NBC/NC - DEGDN propellants, 5: NBC/NC - TMETN

461 propellants).

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462

463 Figure 5. Mechanical properties of NC and NBC/NC nitramine gun propellants with

464 different plasticizers (1: NC - NG propellants, 2: NBC/NC - NG propellants 3: NBC/NC

465 – NG/DEGDN propellants, 4: NBC/NC - DEGDN propellants, 5: NBC/NC - TMETN

466 propellants): (a) impact strength of samples 1 to 5, (b) tensile strength of samples 1 and

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467 2, (c) compressive strength of sample 1 and 2.

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468

469 Figure 6. Detonation heat of NC and NBC/NC nitramine gun propellants with different

470 plasticizers (1: NC - NG propellants, 2: NBC/NC - NG propellants 3: NBC/NC –

471 NG/DEGDN propellants, 4: NBC/NC - DEGDN propellants, 5: NBC/NC - TMETN

472 propellants).

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473
474 Figure 7. The thermal decomposition properties (a), differential scanning calorimetry

475 (b), and Enthalpy of decomposition of the propellants (c) of NC and NBC/NC

476 nitramine gun propellants with different plasticizers (1: NC - NG propellants, 2:

477 NBC/NC - NG propellants 3: NBC/NC – NG/DEGDN propellants, 4: NBC/NC -

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478 DEGDN propellants, 5: NBC/NC - TMETN propellants).

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479

480 Figure 8. The stability of combustion (a), the change of burning rate (b) and the
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481 combustion state of burning surface (c) curves of NC and NBC/NC nitramine gun
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482 propellants with different plasticizers (1: NC - NG propellants, 2: NBC/NC - NG

483 propellants 3: NBC/NC – NG/DEGDN propellants, 4: NBC/NC - DEGDN propellants,

484 5: NBC/NC - TMETN propellants).

23
Declaration of interest statement

We declare that we have no financial and personal relationships with other people

or organizations that can inappropriately influence our work, there is no professional or

other personal interest of any nature or kind in any product, service and / or company

that could be construed as influencing the position presented in, or the review of the

of
manuscript entitled.

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