高能太根发射药中RDX迁移的研究
摘要
由硝化棉(NC)、硝化甘油(NG)、硝化三乙二醇(TENG)和黑索今(RDX)组成的高能太根发射药是一种正在积极开发的新型高能发射药，加入高能材料RDX后的太根发射药配方也已进入实验和应用研究阶段。
低分子固体物质RDX，在一定条件下会从火药内部迁移到表面。从而影响发射药的使用寿命。对加入RDX的太根发射药的组分迁移等性能，目前在国内外尚未开展系统的研究，特别是对RDX迁移的研究还未见资料报道。本文以高能太根发射药及其相关技术为研究对象，分析研究了迁移理论以及目前国内外测定RDX迁移性能的方法，对这些方法的优缺点进行了比较，并采用化学分析法、热失重法(TG)、差式扫描量热法(DSC)相结合的方法对各种不同储存时期高能太根发射药不同部位中RDX含量进行了测定，研究了使用两种不同粒度RDX制备的太根发射药的抗迁移性能。其中，首次成功地把热失重法(TG)和差式扫描量热法(DSC)应用于发射药迁移性能研究中。实验结果表明：高能太根发射药中RDX具有良好的抗迁移性能，在长储过程中没有发生明显的迁移现象，和化学分析法的结果比较表明：和其它方法相结合，热失重法(TG)和差式扫描量热法(DSC)可以应用于发射药中RDX迁移的研究中。
The high-energy TEGN gun propellant composed of NC, NG,TENG and RDX is one of the new pattern high-energy gun propellant which is in process of active exploitation now. The prescription of TEGN gun propellant filled with high-energy material-RDX has also been experimented and researched for using.
In some condition, low molecular solid substance RDX will migrate from the inside to the surface of the gunpowder. Consequently the migration will affect the using life of gun propellant. At the present time, the migration of TEGN gun propellant joined by RDX has not been studied systemically home or abroad, especially the research on the migration of RDX has not been reported. In this paper migration theory and techniques related to the high-energy TEGN gun propellant are presented, and some methods determining the migration of RDX are analyzed and compared. As a result, chemical and thermal analyses are employed associatively to test the content of RDX in different position of TEGN gun propellant stored different period. The antimigration capability of TEGN gun propellant making use of two different granularity of RDX is also been studied. In this work, Thermogravimetry (TG) and Differential Scanning Calorimetry (DSC) are used successfully to research the migration for the first time. Experimental results
show the antimigration capability of RDX is nice, and there isn't obvious migration in the long term of storing. By comparison to chemical analysis, TG and DSC can be used in detection of the migration of RDX when combined with other ways.
低分子固体物质RDX，在一定条件下会从火药内部迁移到表面。从而影响发射药的使用寿命。对加入RDX的太根发射药的组分迁移等性能，目前在国内外尚未开展系统的研究，特别是对RDX迁移的研究还未见资料报道。本文以高能太根发射药及其相关技术为研究对象，分析研究了迁移理论以及目前国内外测定RDX迁移性能的方法，对这些方法的优缺点进行了比较，并采用化学分析法、热失重法(TG)、差式扫描量热法(DSC)相结合的方法对各种不同储存时期高能太根发射药不同部位中RDX含量进行了测定，研究了使用两种不同粒度RDX制备的太根发射药的抗迁移性能。其中，首次成功地把热失重法(TG)和差式扫描量热法(DSC)应用于发射药迁移性能研究中。实验结果表明：高能太根发射药中RDX具有良好的抗迁移性能，在长储过程中没有发生明显的迁移现象，和化学分析法的结果比较表明：和其它方法相结合，热失重法(TG)和差式扫描量热法(DSC)可以应用于发射药中RDX迁移的研究中。
The high-energy TEGN gun propellant composed of NC, NG,TENG and RDX is one of the new pattern high-energy gun propellant which is in process of active exploitation now. The prescription of TEGN gun propellant filled with high-energy material-RDX has also been experimented and researched for using.
In some condition, low molecular solid substance RDX will migrate from the inside to the surface of the gunpowder. Consequently the migration will affect the using life of gun propellant. At the present time, the migration of TEGN gun propellant joined by RDX has not been studied systemically home or abroad, especially the research on the migration of RDX has not been reported. In this paper migration theory and techniques related to the high-energy TEGN gun propellant are presented, and some methods determining the migration of RDX are analyzed and compared. As a result, chemical and thermal analyses are employed associatively to test the content of RDX in different position of TEGN gun propellant stored different period. The antimigration capability of TEGN gun propellant making use of two different granularity of RDX is also been studied. In this work, Thermogravimetry (TG) and Differential Scanning Calorimetry (DSC) are used successfully to research the migration for the first time. Experimental results
show the antimigration capability of RDX is nice, and there isn't obvious migration in the long term of storing. By comparison to chemical analysis, TG and DSC can be used in detection of the migration of RDX when combined with other ways.
引文
1 张子青，陈素芬．包覆层—双基推进剂界面主要增塑剂的迁移．北京工业学院，1984
2 张子青，李伟生．双基推进剂中硝化甘油向阻燃包覆剂内迁移的温度效应．北京工业学院，1984
3 王新华．固体火箭发动机装药包覆层性能检测方法的讨论．西安近代化学研究所，1985
4 佟祥生．接触法测定包覆层对增塑剂的吸收．中国兵工学会弹箭用非金属材料第二届研究会论文，1984
5 武海顺，王泽山．钝感火药中增塑剂的迁移及其分布．南京理工大学学报4，43，1994
6 张来发等．国库发射药中增塑剂迁移研究．204所，1987
7 Agawal. J. P, and Pokharkan. J, Scientific and Industrial Research. 39.633, 1980
8 武海顺，王泽山．增塑剂迁移的温度效应．兵工学报(火化工分册)，No．2，1994
9 武海顺，王泽山．在老化过程中DNT的迁移及分布．南京理工大学学报(自然科学版)No．4．43，1994
10 武海顺，王泽山．DNT在包覆药中的迁移速率常数的测定研究．色谱，1994
11 武海顺，王泽山．包覆药的老化与DNT的迁移．南京理工大学学报(自然科学版)
12 武海顺，王泽山，刘玉海．钝感包覆药中阻燃剂二氧化钛迁移规律的研究．兵工学报(火化工分册)
13 武海顺，王泽山，刘玉海．钝感包覆药中增塑剂DNT迁移规律的研究．兵工学报(火化工分册)
14 武海顺，王泽山．钝感包覆药中阻燃剂二氧化钛的ICP—AES分析方法研究．光谱学与光谱分析，1994
15 刘子如．快速微量测定包覆层中硝化甘油的迁移量．西安近代化学研究所，1988
16 王新华．硝化甘油向包覆层迁移与贮存性能研究．西安近代化学研究所，1989
17 武海顺，王泽山．三基包覆药中阻燃剂二氧化钛迁移行为的研究．兵工学报(火化工分册)，No．2.1，1994(1)，1～5
18 胡荣祖，贾朝林，陆兴森．黑索今火药的热行为，兵工学报(火炸药专集)第一期，23-29，1991
19 Crank. J, and Park. G. S, Diffusion in Potymers, Academic Press New York, 1968
20 Cusslar. E. L, Multicomponent Diffusion, Amstordam Elsevier, 1976
21 Hirschfelder, J. O., Curtiss, C. F. and Bird, R. B., Molecular Theory of Gases and Liquids, Wiley, New York, 1964
22 Sherwood, T. K., Pigford, R. L., and Wilke, G. R., Mass Transfer, Mcgraw Hill, 1975
23 Gilland, E. R., Ind. Eng. Chem. Vol. 58. No. 5, 19, 1966
24 Schlihting, H., Boundary Layer Theory 7th ed. New York, Mcgraw Hill, 1979
25 范治新．工程传热原理．化学工业出版社，1982
26 丁培墉．物理化学．冶金工业出版社，1979
27 付献彩．物理化学．高等教育出版社，1988
28 Nakanishi, K., Infrared Absorption Spectroscopy—Practical, Tokyo, 1962
29 Potts, W. J., Chemical Infrared Absorption Spectroscopy, Volume 1, New York, 1963
30 Brugel, W., An Introduction To Infrared Spectroscopy, London, 1962
31 Bellamyml. J., The Infrared Spectra Of Complex Molecular, 2nd ed. London, 1958
32 Scholl, F., Arias Of Polymer And Plastics Analysis, Second, Completely Revised Edition, Vol. 3, Additives And Processing Aids, Carl Hanser Verlag Munich, Venna, 1981
33 Vanderberg, J. T., An Infrared Spectroscopy Atlas For The Coatings Industry, Philadelphia, Pennsylvania, U.S.A., 1980
34 Sadtler Research Laboratories, Inc, The Sadtle Standard Spectra, Commercial Spectra, IR Grating, Controlled Pyrolyzates Of Polymers
35 Oyum, y., Rhringdd, A. L., Thermal Decomposition Of Energetic Material 24: A Comparison Of The Cryslal Structures, IR Spectra, Thermalysis and Impact Sensiticities Of Nitro guanidine And Trinotroethyl nitro guanidine Propellants, Explosives, Pyrotechnics. 12 (2), 46 (1987)
36 董庆年．红外光谱法．石油工业出版社，1977
37 Littewood, A. B., Gas Chromatography, 2nded. New York, Academic Press, 1970
38 徐秋心．实用发射药光谱分析．四川科学技术出版社，1993
39 Thompson, M., And Walsh, J. N., A Handbook Of Inductively Coupled Plasma Spectrometry, Glasgow, Blackie & Son Limited, 1983
40 不破景一郎．ICP发光分析(化学领域增刊127号)，1980
41 中华人民共和国兵器部标准WJ33—75
42 傅若农，田林祥．兵工学报(1)，1984
43 王泽山．火药装药设计．国防工业出版社，1986
44 Oyum, y., Rhringdd, A. L., Propellants, Explosives, Pyrotechnics. 12 (2), 1984
45 Logd, J. B. F., Proc. Int. Syrup. Anal. Detect. Explos., 9 (1), 1983
46 Yinon, J., The Analysis of Explosives. New York, 1981
47 Dalton, R. W., Chandle, C. D., J. Chromatogr. Sci., B (1), 1975
48 Yinon, J., Critical Reviews Analytical Chemistry, 1977
49 吴宁生，顾光华．高效液相色谱．中国科学技术大学出版社，1989
50 钟长庚，曾石虞，单复，田德余．用DSC测量炸药和推进剂的近似爆热．兵工学报(火炸药专集)(2)65～72
51 王德才．火药学．南京理工大学出版，1988
52 张瑞庆．火药用原材料性能及制备．北京理工大学出版社出版，1993
53 Milmol, J. D.; Smith, F. L.; 和 and Kotlenslette, J. P.; PB Rep. of Teeh. Sets. (171) 256—535, 1959
54 Rogers, K. N.; Microchem, J., 5, 91—99, 1961
55 Krien, G. Explosivesto ffe, 13, 205—220, 1965
56 Abegg, M. T. Ficher, H. J.; and Weatherill, W. T.; Prept. Div. Fuel Chem., Am. Chem Soe., 7, 218—234, 1963
57 张国安．反相高效液相色谱法分离测定硝胺火药中的RDX，NG，C_2和DBP，色谱6(2)，1998
58 张瑞庆．火药用原材料性能与制备．第1版．北京：北京理工大学出版社，1995
59 任特生．硝胺及硝酸酯炸药化学与工艺学．北京：兵器工业出版，1994
60 叶刘鹏，曹欣茂，叶玲，庞晓萍．炸药结晶工艺学及其应用(第1版)．兵器工业出版社出版，1995
61 任玉力，陈少镇．火药化学与工艺学．国防工业出版社，1981
62 刘振海．热分析导论．北京：化学工业出版社，1991
63 刘雄，热分析技术基础．昆明：贵金属研究所出版社，1985
2 张子青，李伟生．双基推进剂中硝化甘油向阻燃包覆剂内迁移的温度效应．北京工业学院，1984
3 王新华．固体火箭发动机装药包覆层性能检测方法的讨论．西安近代化学研究所，1985
4 佟祥生．接触法测定包覆层对增塑剂的吸收．中国兵工学会弹箭用非金属材料第二届研究会论文，1984
5 武海顺，王泽山．钝感火药中增塑剂的迁移及其分布．南京理工大学学报4，43，1994
6 张来发等．国库发射药中增塑剂迁移研究．204所，1987
7 Agawal. J. P, and Pokharkan. J, Scientific and Industrial Research. 39.633, 1980
8 武海顺，王泽山．增塑剂迁移的温度效应．兵工学报(火化工分册)，No．2，1994
9 武海顺，王泽山．在老化过程中DNT的迁移及分布．南京理工大学学报(自然科学版)No．4．43，1994
10 武海顺，王泽山．DNT在包覆药中的迁移速率常数的测定研究．色谱，1994
11 武海顺，王泽山．包覆药的老化与DNT的迁移．南京理工大学学报(自然科学版)
12 武海顺，王泽山，刘玉海．钝感包覆药中阻燃剂二氧化钛迁移规律的研究．兵工学报(火化工分册)
13 武海顺，王泽山，刘玉海．钝感包覆药中增塑剂DNT迁移规律的研究．兵工学报(火化工分册)
14 武海顺，王泽山．钝感包覆药中阻燃剂二氧化钛的ICP—AES分析方法研究．光谱学与光谱分析，1994
15 刘子如．快速微量测定包覆层中硝化甘油的迁移量．西安近代化学研究所，1988
16 王新华．硝化甘油向包覆层迁移与贮存性能研究．西安近代化学研究所，1989
17 武海顺，王泽山．三基包覆药中阻燃剂二氧化钛迁移行为的研究．兵工学报(火化工分册)，No．2.1，1994(1)，1～5
18 胡荣祖，贾朝林，陆兴森．黑索今火药的热行为，兵工学报(火炸药专集)第一期，23-29，1991
19 Crank. J, and Park. G. S, Diffusion in Potymers, Academic Press New York, 1968
20 Cusslar. E. L, Multicomponent Diffusion, Amstordam Elsevier, 1976
21 Hirschfelder, J. O., Curtiss, C. F. and Bird, R. B., Molecular Theory of Gases and Liquids, Wiley, New York, 1964
22 Sherwood, T. K., Pigford, R. L., and Wilke, G. R., Mass Transfer, Mcgraw Hill, 1975
23 Gilland, E. R., Ind. Eng. Chem. Vol. 58. No. 5, 19, 1966
24 Schlihting, H., Boundary Layer Theory 7th ed. New York, Mcgraw Hill, 1979
25 范治新．工程传热原理．化学工业出版社，1982
26 丁培墉．物理化学．冶金工业出版社，1979
27 付献彩．物理化学．高等教育出版社，1988
28 Nakanishi, K., Infrared Absorption Spectroscopy—Practical, Tokyo, 1962
29 Potts, W. J., Chemical Infrared Absorption Spectroscopy, Volume 1, New York, 1963
30 Brugel, W., An Introduction To Infrared Spectroscopy, London, 1962
31 Bellamyml. J., The Infrared Spectra Of Complex Molecular, 2nd ed. London, 1958
32 Scholl, F., Arias Of Polymer And Plastics Analysis, Second, Completely Revised Edition, Vol. 3, Additives And Processing Aids, Carl Hanser Verlag Munich, Venna, 1981
33 Vanderberg, J. T., An Infrared Spectroscopy Atlas For The Coatings Industry, Philadelphia, Pennsylvania, U.S.A., 1980
34 Sadtler Research Laboratories, Inc, The Sadtle Standard Spectra, Commercial Spectra, IR Grating, Controlled Pyrolyzates Of Polymers
35 Oyum, y., Rhringdd, A. L., Thermal Decomposition Of Energetic Material 24: A Comparison Of The Cryslal Structures, IR Spectra, Thermalysis and Impact Sensiticities Of Nitro guanidine And Trinotroethyl nitro guanidine Propellants, Explosives, Pyrotechnics. 12 (2), 46 (1987)
36 董庆年．红外光谱法．石油工业出版社，1977
37 Littewood, A. B., Gas Chromatography, 2nded. New York, Academic Press, 1970
38 徐秋心．实用发射药光谱分析．四川科学技术出版社，1993
39 Thompson, M., And Walsh, J. N., A Handbook Of Inductively Coupled Plasma Spectrometry, Glasgow, Blackie & Son Limited, 1983
40 不破景一郎．ICP发光分析(化学领域增刊127号)，1980
41 中华人民共和国兵器部标准WJ33—75
42 傅若农，田林祥．兵工学报(1)，1984
43 王泽山．火药装药设计．国防工业出版社，1986
44 Oyum, y., Rhringdd, A. L., Propellants, Explosives, Pyrotechnics. 12 (2), 1984
45 Logd, J. B. F., Proc. Int. Syrup. Anal. Detect. Explos., 9 (1), 1983
46 Yinon, J., The Analysis of Explosives. New York, 1981
47 Dalton, R. W., Chandle, C. D., J. Chromatogr. Sci., B (1), 1975
48 Yinon, J., Critical Reviews Analytical Chemistry, 1977
49 吴宁生，顾光华．高效液相色谱．中国科学技术大学出版社，1989
50 钟长庚，曾石虞，单复，田德余．用DSC测量炸药和推进剂的近似爆热．兵工学报(火炸药专集)(2)65～72
51 王德才．火药学．南京理工大学出版，1988
52 张瑞庆．火药用原材料性能及制备．北京理工大学出版社出版，1993
53 Milmol, J. D.; Smith, F. L.; 和 and Kotlenslette, J. P.; PB Rep. of Teeh. Sets. (171) 256—535, 1959
54 Rogers, K. N.; Microchem, J., 5, 91—99, 1961
55 Krien, G. Explosivesto ffe, 13, 205—220, 1965
56 Abegg, M. T. Ficher, H. J.; and Weatherill, W. T.; Prept. Div. Fuel Chem., Am. Chem Soe., 7, 218—234, 1963
57 张国安．反相高效液相色谱法分离测定硝胺火药中的RDX，NG，C_2和DBP，色谱6(2)，1998
58 张瑞庆．火药用原材料性能与制备．第1版．北京：北京理工大学出版社，1995
59 任特生．硝胺及硝酸酯炸药化学与工艺学．北京：兵器工业出版，1994
60 叶刘鹏，曹欣茂，叶玲，庞晓萍．炸药结晶工艺学及其应用(第1版)．兵器工业出版社出版，1995
61 任玉力，陈少镇．火药化学与工艺学．国防工业出版社，1981
62 刘振海．热分析导论．北京：化学工业出版社，1991
63 刘雄，热分析技术基础．昆明：贵金属研究所出版社，1985