硼复合粒子的制备及其热化学性能研究
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摘要
本文在大量实验的基础上,对硼粒子的包覆和不同粒径硼粉磨制工艺及其影响因素进行了深入系统的研究,对制得的复合粒子和不同粒径的硼粒子的表面性状和热化学性能进行了表征,并将复合粒子应用在推进剂中进行了测试。
本文研究结论如下:
1.采用不同的方法用高氯酸铵、纳米铝粉、LiF、HTPB对硼粉进行了包覆处理,并对包覆工艺进行了探索,研究了不同包覆方法和包覆比对复合粒子性能的影响。并通过SEM、EDS、DTA、TG各种测试手段对硼复合粒子进行了表征,研究结果表明:(a)对硼的包覆能大幅度的改善硼粒子的热化学性能;(b)采用纳米铝粉制备的硼复合粒子热化学性能最好;(c)机械化学法是一种比较好的包覆方法。
2.利用行星磨制得了不同粒径的硼粉,得到了较为成熟的工艺,研究了工艺中的影响因素。研究发现:在经历过球磨后,硼粉粒径分布较为均匀;粒径小的硼粉在热化学性能上有了明显的改善。
3.将制得的硼复合粒子应用在推进剂中,采用DTA表征了其性能,结果表明:采用复合粒子的推进剂的热化学性能比采用未包覆硼粉的推进剂有了明显的改善。
Coating technics of boron particles& milling technics of different diameter boron particles and its predominant factors were researched systemically and profoundly,on the base of a great deal of experiments. Surface character& thermal chemistry behavior are characterized of composite particles&particles of different diameter. Composite particles are applied in the propellant and characterized.The results are shown as follows:1.AP,nano aluminium powder,LiF,HTPB are separately coated on boron particles and its technics is explored. Composite particles are characterized by different testing methods ,such as SEM, EDS, DTA, TG..Conclusions are represented that: (a) Thermal chemistry behavior of boron particles is improved significantly by coating ; (b) Thermal chemistry behavior of boron particles which is coated with nano aluminium is best, (c) Mechanico-chemical Teatment is good for coating.2.Different diameter boron particles are made with planet milling-ball and its technics has been achieved.Conclusions are represented that:After milling, diameter of boron particles is became well-proportioned; Thermal chemistry behavior of boron particles of less diameter is improved observably.3.Composite particles are applied in the propellant and characterized by DTA, Conclusions are represented that: Thermal chemistry behavior of propellant which contains composite particles is better than the blank propellant which uses uncoated boron particles.
本文研究结论如下:
1.采用不同的方法用高氯酸铵、纳米铝粉、LiF、HTPB对硼粉进行了包覆处理,并对包覆工艺进行了探索,研究了不同包覆方法和包覆比对复合粒子性能的影响。并通过SEM、EDS、DTA、TG各种测试手段对硼复合粒子进行了表征,研究结果表明:(a)对硼的包覆能大幅度的改善硼粒子的热化学性能;(b)采用纳米铝粉制备的硼复合粒子热化学性能最好;(c)机械化学法是一种比较好的包覆方法。
2.利用行星磨制得了不同粒径的硼粉,得到了较为成熟的工艺,研究了工艺中的影响因素。研究发现:在经历过球磨后,硼粉粒径分布较为均匀;粒径小的硼粉在热化学性能上有了明显的改善。
3.将制得的硼复合粒子应用在推进剂中,采用DTA表征了其性能,结果表明:采用复合粒子的推进剂的热化学性能比采用未包覆硼粉的推进剂有了明显的改善。
Coating technics of boron particles& milling technics of different diameter boron particles and its predominant factors were researched systemically and profoundly,on the base of a great deal of experiments. Surface character& thermal chemistry behavior are characterized of composite particles&particles of different diameter. Composite particles are applied in the propellant and characterized.The results are shown as follows:1.AP,nano aluminium powder,LiF,HTPB are separately coated on boron particles and its technics is explored. Composite particles are characterized by different testing methods ,such as SEM, EDS, DTA, TG..Conclusions are represented that: (a) Thermal chemistry behavior of boron particles is improved significantly by coating ; (b) Thermal chemistry behavior of boron particles which is coated with nano aluminium is best, (c) Mechanico-chemical Teatment is good for coating.2.Different diameter boron particles are made with planet milling-ball and its technics has been achieved.Conclusions are represented that:After milling, diameter of boron particles is became well-proportioned; Thermal chemistry behavior of boron particles of less diameter is improved observably.3.Composite particles are applied in the propellant and characterized by DTA, Conclusions are represented that: Thermal chemistry behavior of propellant which contains composite particles is better than the blank propellant which uses uncoated boron particles.
引文
1.张炜,朱慧方,丁酉等.冲压发动机发展现状及其关键技术[J].固体火箭技术,1998,21(3):24～30
2.魏青.高含硼富燃固体推进剂工艺和燃烧性能研究.西北工业大学博士论文,2003,7
3.臧令千.硼用作推进剂燃料组分的选择[J].推进技术,1990(4):56～62
4.邰红勤.高含硼、高燃速固体推进剂研究.西北工业大学硕士论文,2004,2
5.张向宇等编.实用化学手册.北京:国防工业出版社,1990.8～9
6.北京师范大学无机化学教研室编.简明化学手册.北京:人民出版社,1980.27
7.王克秀等编.固体火箭推进剂及燃烧.北京:国防工业出版社,1983.17
8. CRC Handbook of Chemistry and Physics, 58th Edition, 1977～1978. 8～11
9.郑剑,李学军,庞爱民等.国内外含硼贫氧推进剂燃烧性能研究现状[J].推进技术,2003(4):50～57
10.戴耀松.固体火箭—冲压发动机的研究进展.推进技术,1987(5):40～45
11.李淑芬.含硼的固体燃料.含能材料,1995,3(2):1～8
12. M. K. King. Ignition and Combustion of Boron Particles and Clouds[J]. Spacecraft, 1982, 19: 294～306
13. T. Kuwahara and N. Kubota. Role of Boron in Burning Rate Augmentation of AP Composite Propellants. Propellants, Explosive, Pyrotechnics. 1989, 14: 43～46
14. Tai-Kang Liu, Song-Ping Luh, Huey-Cherng Perng. Effect of Boron Particle Surface Coating on Combustion of Solid Propellants for Ducted Rockets. Propellants, Explosives, Pyrotechnics, 1991, 16, 156～166
15. R. J. Markle, S. G. Stephenson. Optimum Zirconium and Boron Powder Characteristics for Solid Rocket Propellant Applications. The International Journal of Powder Metallurgy&Powder Technology 0361～3488 /820243～09S0075 vol. 18.No.3198216
16. Nobuo Tsujikado. An Experimental Study on Configuration of Secondary Combustion Chamber for Ram-Rocket.6thlnt.Symp.Air Breathing Engines.1983: 3～8
17. K. K. Kuo. Combustion of Borob-Based Solid Propellants and Solid Fuels.CRC. Press,1993
18. Glassman, I., Williams, F. A. and Antaki, P. A. Physical and Chemical Interpretation of Boron Particle Combustion. 20th Symp.(Int) on Combustion, 1984: 2057～2064
19. Mohan, G and Williams, F. A. Ignition and Combustion of Boron on OZ/Inert A tmosphere. AIAA, 1972, 10(6): 776～773
20. M. J. Spalding, Herman Krier and R. L. Burton. Chemical Kinetics of Boron Combustion in High Pressure Ar/F/OZ Mixture.AIAA 98～3823
21. T. K. Liu, I. M. Shyu and Y. S. Hsia. Effect of Fluorinated Graphite on Combustion of Boron and Boron-Based Fuel-Rich Rockets. Journal of Propulsion and Power,1 996, 12(1): 26～33
22. R. C. Brown, C. E. Kolb, R. A. Yetter, F.L.Dryer, and H.Rabitz.Kinetics Modeling and Sensitivity Analysis for B/H/O/C/F Combustion System. Combustion and Flame, 1995, 101(3): 22～238
23. W. Zhou, R. A. Yetter, F. L. Dryer, H. Rabitz, R. C. Brown, and C. E. Kolb. E ffect of Fluorine on Combustion of "Clean" Surface Boron Particles. Combustion and Flame, 1998, 112(4): 507～521
24. C. L. Yeh and K. K. Kuo. Ignition and Combustion of Boron Particles. Progress in Energy and Science, 1996, 22(6): 511～541
25. W. Lielunanm. Combustion of Boron-Based Slurries in a Ramburner. Propellants, E xplosives, Pyrotechnics, 1992, 17: 14～16
26. V. Rosenband, B. Natan and A. Gany. Ignition of Boron Particles Coated by a Thin Titanium Film. AIAA 93～2201
27. Yoshio Oyumi and Kiyokazu Nagayama. Combustion Behavior of Flourocarbon/ Boron/AP Propellant at High Pressure.Propellants,Explosives, Pyrotechnicals, 1995, 20: 79～82
28. J. S. Chong, E. B. Christiansen,and A.D.Baer.Rheology of concentrated suspensions. J. Appl. Poly. Sci. 1971,15:2007～2021
29.李疏芬.含硼推进剂燃烧性能的改善.固体火箭技术.1995,18(2):39～43
30.李疏芬等.提高含硼固体燃料燃烧性能的研究.推进技术.1997,18(5):100～105
31.李疏芬.含硼贫氧推进剂燃烧性能实验研究.固体火箭技术.1997,20(3):43～48
32.赵秀彬等.硼粒子包覆工艺及对硼的表面和燃烧特性的影响.固体火箭技术,1998,21(1):35～38
33.李辰芳.包覆硼粒子提高硼的燃烧效率.推进技术,1994;(2):53～57
34. Tsujikado N. Experimental Studies on Ram-Rocket Fuels. ISABE 85-7023
35.胡建新,夏智勋,罗振兵等.固体火箭冲压发动机补燃室内硼颗粒点火计算研究[J].含能材料,2004,12(6):342～345
36. Tsujikado N. ISABE 83-7000,1983
37. Tsujikado N. ISABE 85-7000, 1983
38. Besser H L. AGARD-CP-307,1981
39.桑原卓雄等.防卫技术,1992,1:2
40. Ing-Ming Shyn. Combustion of GAP-coated boron particles and the fuel-rich soli d peopellant.25th Int Annu Conf of I CT 23/1～23/4,1994
41. Liu Tai-kang et al. Effect of boron particle surface coating on combustion of solid propellants for ducted rockets. Propellants, Explosives, Pvrotechnics, 1991: (16): 156～166
42. Durrel D. et al. USP 397521
43. Yoshio Oyumi. Urethane reaction mechanism on the amarphous boron surface In GAP propellants. Propellants, Explosives, Pyrotechnics,1992:17:27～28
44.王英红,李葆萱,胡松启等.含AP包覆硼的富燃推进剂燃烧机理研究.火炸药学报[J],2004;17(2):44～47
45.王英红,李葆萱,胡松启等.AP粒度和AP包覆层对硼燃烧的影响[J].固体火箭技术,2003,27(1):50～53
46. Bogd D. Methods of coating boron particles with AP[P]. USP 3 976 521, 1977.
47. J C T row bridge, J D Breazewl. Coating of boron particles[P]. USP 4, 877～649,1989.
48.李疏芬,金荣超,郭敬为.硼粒子的表面包覆及其性能分析.含能材料[J];4(3):102～108
49 马振叶,李凤生,陈爱四等.纳米Fe_2O_3/高氯酸铵复合粒子的制备及其热分解性能研究.化学学报[J];62(13):1252～1255
50 李凤生.特种超细粉体制备技术及应用.国防工业出版社,北京,2002,PP:115～1-27
51 李凤生.纳米/微米复合技术及应用.国防工业出版社,北京,2002,PP:15～42
52 张付清.亚铬酸铜/高氯酸铵超细复合粒子的制备与性能研究.含能材料,1999,7(4):156～158
53 李凤生.纳米/微米复合技术及应用.国防工业出版社,北京,2002,PP:27～30
54 刘磊力.纳米金属及复合金属粉的制备及其催化性能的研究.南京理工大学博士论文,2004,10.
55 Ivanov V G, Leono S N, et al. Combustion of Mixtures of Ultradisperse Aluminum and Gel-like Water[J]. Combustion,Explosion and Shock Waves,1994,30(4):1 23-134
56 Tepper. Frederick,Ivonov G.V, Maret,etal.Energy Formulation from Nanosize Metal
2.魏青.高含硼富燃固体推进剂工艺和燃烧性能研究.西北工业大学博士论文,2003,7
3.臧令千.硼用作推进剂燃料组分的选择[J].推进技术,1990(4):56～62
4.邰红勤.高含硼、高燃速固体推进剂研究.西北工业大学硕士论文,2004,2
5.张向宇等编.实用化学手册.北京:国防工业出版社,1990.8～9
6.北京师范大学无机化学教研室编.简明化学手册.北京:人民出版社,1980.27
7.王克秀等编.固体火箭推进剂及燃烧.北京:国防工业出版社,1983.17
8. CRC Handbook of Chemistry and Physics, 58th Edition, 1977～1978. 8～11
9.郑剑,李学军,庞爱民等.国内外含硼贫氧推进剂燃烧性能研究现状[J].推进技术,2003(4):50～57
10.戴耀松.固体火箭—冲压发动机的研究进展.推进技术,1987(5):40～45
11.李淑芬.含硼的固体燃料.含能材料,1995,3(2):1～8
12. M. K. King. Ignition and Combustion of Boron Particles and Clouds[J]. Spacecraft, 1982, 19: 294～306
13. T. Kuwahara and N. Kubota. Role of Boron in Burning Rate Augmentation of AP Composite Propellants. Propellants, Explosive, Pyrotechnics. 1989, 14: 43～46
14. Tai-Kang Liu, Song-Ping Luh, Huey-Cherng Perng. Effect of Boron Particle Surface Coating on Combustion of Solid Propellants for Ducted Rockets. Propellants, Explosives, Pyrotechnics, 1991, 16, 156～166
15. R. J. Markle, S. G. Stephenson. Optimum Zirconium and Boron Powder Characteristics for Solid Rocket Propellant Applications. The International Journal of Powder Metallurgy&Powder Technology 0361～3488 /820243～09S0075 vol. 18.No.3198216
16. Nobuo Tsujikado. An Experimental Study on Configuration of Secondary Combustion Chamber for Ram-Rocket.6thlnt.Symp.Air Breathing Engines.1983: 3～8
17. K. K. Kuo. Combustion of Borob-Based Solid Propellants and Solid Fuels.CRC. Press,1993
18. Glassman, I., Williams, F. A. and Antaki, P. A. Physical and Chemical Interpretation of Boron Particle Combustion. 20th Symp.(Int) on Combustion, 1984: 2057～2064
19. Mohan, G and Williams, F. A. Ignition and Combustion of Boron on OZ/Inert A tmosphere. AIAA, 1972, 10(6): 776～773
20. M. J. Spalding, Herman Krier and R. L. Burton. Chemical Kinetics of Boron Combustion in High Pressure Ar/F/OZ Mixture.AIAA 98～3823
21. T. K. Liu, I. M. Shyu and Y. S. Hsia. Effect of Fluorinated Graphite on Combustion of Boron and Boron-Based Fuel-Rich Rockets. Journal of Propulsion and Power,1 996, 12(1): 26～33
22. R. C. Brown, C. E. Kolb, R. A. Yetter, F.L.Dryer, and H.Rabitz.Kinetics Modeling and Sensitivity Analysis for B/H/O/C/F Combustion System. Combustion and Flame, 1995, 101(3): 22～238
23. W. Zhou, R. A. Yetter, F. L. Dryer, H. Rabitz, R. C. Brown, and C. E. Kolb. E ffect of Fluorine on Combustion of "Clean" Surface Boron Particles. Combustion and Flame, 1998, 112(4): 507～521
24. C. L. Yeh and K. K. Kuo. Ignition and Combustion of Boron Particles. Progress in Energy and Science, 1996, 22(6): 511～541
25. W. Lielunanm. Combustion of Boron-Based Slurries in a Ramburner. Propellants, E xplosives, Pyrotechnics, 1992, 17: 14～16
26. V. Rosenband, B. Natan and A. Gany. Ignition of Boron Particles Coated by a Thin Titanium Film. AIAA 93～2201
27. Yoshio Oyumi and Kiyokazu Nagayama. Combustion Behavior of Flourocarbon/ Boron/AP Propellant at High Pressure.Propellants,Explosives, Pyrotechnicals, 1995, 20: 79～82
28. J. S. Chong, E. B. Christiansen,and A.D.Baer.Rheology of concentrated suspensions. J. Appl. Poly. Sci. 1971,15:2007～2021
29.李疏芬.含硼推进剂燃烧性能的改善.固体火箭技术.1995,18(2):39～43
30.李疏芬等.提高含硼固体燃料燃烧性能的研究.推进技术.1997,18(5):100～105
31.李疏芬.含硼贫氧推进剂燃烧性能实验研究.固体火箭技术.1997,20(3):43～48
32.赵秀彬等.硼粒子包覆工艺及对硼的表面和燃烧特性的影响.固体火箭技术,1998,21(1):35～38
33.李辰芳.包覆硼粒子提高硼的燃烧效率.推进技术,1994;(2):53～57
34. Tsujikado N. Experimental Studies on Ram-Rocket Fuels. ISABE 85-7023
35.胡建新,夏智勋,罗振兵等.固体火箭冲压发动机补燃室内硼颗粒点火计算研究[J].含能材料,2004,12(6):342～345
36. Tsujikado N. ISABE 83-7000,1983
37. Tsujikado N. ISABE 85-7000, 1983
38. Besser H L. AGARD-CP-307,1981
39.桑原卓雄等.防卫技术,1992,1:2
40. Ing-Ming Shyn. Combustion of GAP-coated boron particles and the fuel-rich soli d peopellant.25th Int Annu Conf of I CT 23/1～23/4,1994
41. Liu Tai-kang et al. Effect of boron particle surface coating on combustion of solid propellants for ducted rockets. Propellants, Explosives, Pvrotechnics, 1991: (16): 156～166
42. Durrel D. et al. USP 397521
43. Yoshio Oyumi. Urethane reaction mechanism on the amarphous boron surface In GAP propellants. Propellants, Explosives, Pyrotechnics,1992:17:27～28
44.王英红,李葆萱,胡松启等.含AP包覆硼的富燃推进剂燃烧机理研究.火炸药学报[J],2004;17(2):44～47
45.王英红,李葆萱,胡松启等.AP粒度和AP包覆层对硼燃烧的影响[J].固体火箭技术,2003,27(1):50～53
46. Bogd D. Methods of coating boron particles with AP[P]. USP 3 976 521, 1977.
47. J C T row bridge, J D Breazewl. Coating of boron particles[P]. USP 4, 877～649,1989.
48.李疏芬,金荣超,郭敬为.硼粒子的表面包覆及其性能分析.含能材料[J];4(3):102～108
49 马振叶,李凤生,陈爱四等.纳米Fe_2O_3/高氯酸铵复合粒子的制备及其热分解性能研究.化学学报[J];62(13):1252～1255
50 李凤生.特种超细粉体制备技术及应用.国防工业出版社,北京,2002,PP:115～1-27
51 李凤生.纳米/微米复合技术及应用.国防工业出版社,北京,2002,PP:15～42
52 张付清.亚铬酸铜/高氯酸铵超细复合粒子的制备与性能研究.含能材料,1999,7(4):156～158
53 李凤生.纳米/微米复合技术及应用.国防工业出版社,北京,2002,PP:27～30
54 刘磊力.纳米金属及复合金属粉的制备及其催化性能的研究.南京理工大学博士论文,2004,10.
55 Ivanov V G, Leono S N, et al. Combustion of Mixtures of Ultradisperse Aluminum and Gel-like Water[J]. Combustion,Explosion and Shock Waves,1994,30(4):1 23-134
56 Tepper. Frederick,Ivonov G.V, Maret,etal.Energy Formulation from Nanosize Metal