SC-CO2辅助挤出成型过程中双基发射药的流变特性

doi:10.12382/bgxb.2023.0023

摘要/Abstract

摘要：

为了部分替代在发射药挤出成型过程中使用的有机溶剂,将超临界二氧化碳(Supercritical Carbon dioxide,SC-CO₂)引入发射药的挤出成型过程中,借助其在临界点附近急剧变化的溶剂特性,实现增塑后可快速从产品中驱除,为最终实现SC-CO₂对有机溶剂的完全替代做铺垫。以剪切黏度为反映流变特性的参数,采用在线狭缝流变仪测量物料的剪切黏度并获得流变曲线,对物料在不同工艺条件下的流变特性进行研究。研究结果表明:SC-CO₂辅助双基药挤出成型过程中物料的流变行为可以用幂律模型描述,引入SC-CO₂后物料黏度显著降低,SC-CO₂在4.67 wt%含量下使得双基药的稠度系数降低17.10%,体现了SC-CO₂对于双基药的良好增塑作用;随着SC-CO₂含量、溶剂含量、温度等参数值持续升高,继续增大参数值所能提供的增塑效果将变得有限。

关键词: 双基发射药, 超临界二氧化碳, 挤出成型, 增塑, 流变特性

Abstract:

To partially substitute the organic solvents used in the extrusion process of propellant, supercritical carbon dioxide (SC-CO₂) was introduced into the extrusion process of propellant. Owing to its solvent properties that sharply changing near the critical point, SC-CO₂ is rapidly removed from the product after plasticization, paving the way for the complete replacement of organic solvents by SC-CO₂. Shear viscosity is adopted as a parameter to reflect the rheological property, and an in-line slit rheometer is used to measure the shear viscosity of material and obtain the rheological curves to investigate the rheological properties of material under various process conditions. The results indicate that the rheological behavior of material in the extrusion process of SC-CO₂ assisted double-base propellant can be described by power-law model. The viscosity of material decreases significantly due to the introduction of SC-CO₂. And the introduction of SC-CO₂ decreases the viscous coefficient of double-base propellant by 17.10% at the content of 4.67 wt%, reflecting the excellent plasticizing effect of SC-CO₂ on the double-base propellant. The plasticizing effect provided by increasing the parameter values is limited as the process parameters such as SC-CO₂ content, solvent content, and temperature increase.

Key words: double-base propellant, supercritical carbon dioxide, extrusion molding, plasticization, rheological property

中图分类号:

TQ562

胡启鹏, 杨昆, 张合, 李纯志, 应三九, 肖忠良. SC-CO₂辅助挤出成型过程中双基发射药的流变特性[J]. 兵工学报, 2024, 45(5): 1593-1601.

HU Qipeng, YANG Kun, ZHANG He, LI Chunzhi, YING Sanjiu, XIAO Zhongliang. Rheological Property of Double-base Propellant in SC-CO₂ Assisted Extrusion Process[J]. Acta Armamentarii, 2024, 45(5): 1593-1601.

图/表 15

表1 实验材料与设备

Table 1 Experimental materials and equipment

名称	规格	来源
混合酯吸收药片	NC content: 55wt%	泸州北方化学工业有限公司
丙酮	分析纯	国药集团化学试剂有限公司
乙醇	分析纯	国药集团化学试剂有限公司
CO₂	≥99.99%	南京文达特种气体有限公司
捏合机	2L	江苏国贸减速机有限公司
SC-CO₂辅助挤出成型设备	30 mm	无锡金凯盛机械制造有限公司

图1 SC-CO2辅助挤出成型设备示意图

Fig.1 Schematic diagram of SC-CO2 assisted extrusion equipment

图2 SC-CO2对于双基药流变特性的影响

Fig.2 Effect of SC-CO2 on the rheological property of double-base propellant

图3 不同SC-CO2含量下双基药的流变曲线

Fig.3 Rheological curves of double-base propellants with various SC-CO2 contents

表2 不同SC-CO2含量下双基药的幂律方程

Table 2 Power law equation of double-base propellants with various SC-CO2 contents

SC-CO₂/wt%	方程	n	R²
0.93	η=58.42· $γ · - 0.937$	0.063	0.99997
1.87	η=54.79· $γ · - 0.924$	0.076	0.99997
2.80	η=53.52· $γ · - 0.921$	0.079	0.99982
3.74	η=49.74· $γ · - 0.907$	0.093	0.99994
4.67	η=49.29· $γ · - 0.902$	0.098	0.99999

表2 不同SC-CO2含量下双基药的幂律方程

Table 2 Power law equation of double-base propellants with various SC-CO2 contents

SC-CO₂/wt%	方程	n	R²
0.93	η=58.42· $γ · - 0.937$	0.063	0.99997
1.87	η=54.79· $γ · - 0.924$	0.076	0.99997
2.80	η=53.52· $γ · - 0.921$	0.079	0.99982
3.74	η=49.74· $γ · - 0.907$	0.093	0.99994
4.67	η=49.29· $γ · - 0.902$	0.098	0.99999

图4 不同溶剂含量下双基药/SC-CO2的流变曲线

Fig.4 Rheological curves of double-base propellants/SC-CO2 with various solvent contents

表3 不同溶剂含量下双基药/SC-CO2的幂律方程

Table 3 Power law equation of double-base propellant/ SC-CO2 with various solvent contents

溶剂/wt%	方程	n	R²
25	η=58.48· $γ · - 0.909$	0.091	0.99994
28	η=52.55· $γ · - 0.905$	0.095	0.99989
31	η=49.29· $γ · - 0.902$	0.098	0.99999
34	η=49.20· $γ · - 0.911$	0.089	0.99999
37	η=47.20· $γ · - 0.902$	0.098	0.99974

表3 不同溶剂含量下双基药/SC-CO2的幂律方程

Table 3 Power law equation of double-base propellant/ SC-CO2 with various solvent contents

溶剂/wt%	方程	n	R²
25	η=58.48· $γ · - 0.909$	0.091	0.99994
28	η=52.55· $γ · - 0.905$	0.095	0.99989
31	η=49.29· $γ · - 0.902$	0.098	0.99999
34	η=49.20· $γ · - 0.911$	0.089	0.99999
37	η=47.20· $γ · - 0.902$	0.098	0.99974

图5 不同温度下双基药/SC-CO2的流变曲线

Fig.5 Rheological curves of double-base propellants/SC-CO2 with various temperature

表4 不同温度下双基药/SC-CO2的幂律方程

Table 4 Power law equation of double-base propellant/SC-CO2 at various temperatures

温度/℃	方程	n	R²
39	η=53.71· $γ · - 0.913$	0.087	0.99997
42	η=52.55· $γ · - 0.912$	0.088	0.99996
45	η=49.29· $γ · - 0.902$	0.098	0.99999
48	η=48.58· $γ · - 0.902$	0.098	0.99991
51	η=47.52· $γ · - 0.905$	0.095	0.99999

表4 不同温度下双基药/SC-CO2的幂律方程

Table 4 Power law equation of double-base propellant/SC-CO2 at various temperatures

温度/℃	方程	n	R²
39	η=53.71· $γ · - 0.913$	0.087	0.99997
42	η=52.55· $γ · - 0.912$	0.088	0.99996
45	η=49.29· $γ · - 0.902$	0.098	0.99999
48	η=48.58· $γ · - 0.902$	0.098	0.99991
51	η=47.52· $γ · - 0.905$	0.095	0.99999

表5 不同溶剂含量下双基药的幂律方程

Table 5 Power law equation of double-base propellant with various solvent contents

溶剂/wt%	方程	n	R²
28	η=62.46· $γ · - 0.922$	0.078	0.99994
31	η=59.46· $γ · - 0.915$	0.085	0.99997
34	η=53.55· $γ · - 0.894$	0.106	0.99996
37	η=53.72· $γ · - 0.905$	0.095	0.99985
40	η=49.33· $γ · - 0.899$	0.101	0.99999

表5 不同溶剂含量下双基药的幂律方程

Table 5 Power law equation of double-base propellant with various solvent contents

溶剂/wt%	方程	n	R²
28	η=62.46· $γ · - 0.922$	0.078	0.99994
31	η=59.46· $γ · - 0.915$	0.085	0.99997
34	η=53.55· $γ · - 0.894$	0.106	0.99996
37	η=53.72· $γ · - 0.905$	0.095	0.99985
40	η=49.33· $γ · - 0.899$	0.101	0.99999

图6 溶剂含量对双基药流变特性的影响

Fig.6 Effect of solvent content on the rheological property of double-base propellant

表6 双基药关于溶剂含量的指数方程

Table 6 Exponential equation of double-base propellant about solvent content

剪切速率/s^-1	方程	R²
10	η=11.37·e^-1^.⁴⁸^φ	0.96676
15	η=7.67·e^-1^.⁴⁰^φ	0.96488
20	η=5.80·e^-1^.³⁵^φ	0.95998
25	η=4.67·e^-1^.³⁰^φ	0.95364
30	η=3.91·e^-1^.²⁷^φ	0.94654
35	η=3.37·e^-1^.²⁴^φ	0.93902
40	η=2.96·e^-1^.²²^φ	0.93127

表7 双基药/SC-CO2关于SC-CO2含量的等效溶剂含量

Table 7 Exponential equation of double-base propellant/SC-CO2 about SC-CO2 content

剪切速率/ s^-1	SC-CO₂/wt%
剪切速率/ s^-1	0.93	1.87	2.80	3.74	4.67
10	35.2	37.5	38.6	40.3	41.2
15	36.2	38.3	39.4	40.8	41.6
20	36.8	38.7	39.8	40.9	41.7
25	37.7	39.4	40.4	41.4	42.1
30	38.0	39.6	40.6	41.4	42.0
35	38.6	40.0	41.1	41.7	42.3
40	38.9	40.2	41.2	41.7	42.2

表8 双基药/SC-CO2关于溶剂含量的等效溶剂含量

Table 8 Exponential equation of double-base propellant/SC-CO2 about solvent content

剪切速率/ s^-1	溶剂/wt%
剪切速率/ s^-1	25	28	31	34	37
10	30.8	37.4	41.2	42.8	44.2
15	30.7	37.6	41.6	43.5	44.7
20	30.5	37.6	41.7	43.8	44.9
25	30.6	37.9	42.1	44.4	45.4
30	30.4	37.8	42.0	44.6	45.4
35	30.5	38.0	42.3	45.0	45.8
40	30.3	37.9	42.2	45.1	45.8

表9 双基药/SC-CO2关于温度的等效溶剂含量

Table 9 Exponential equation of double-base propellant/SC-CO2 about temperature

剪切速率/ s^-1	温度/℃
剪切速率/ s^-1	39	42	45	48	51
10	37.1	38.5	41.2	42.2	44.2
15	37.6	38.9	41.6	42.6	44.8
20	37.7	39.1	41.7	42.7	45.0
25	38.2	39.6	42.1	43.2	45.6
30	38.2	39.7	42.0	43.2	45.7
35	38.5	40.0	42.3	43.4	46.1
40	38.5	40.0	42.2	43.4	46.1

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SC-CO₂辅助挤出成型过程中双基发射药的流变特性

Rheological Property of Double-base Propellant in SC-CO₂ Assisted Extrusion Process

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