一种完全、洁净气体发生剂配方基础与作用原理研究
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摘要
本文介绍了一种汽车安全气囊用气体发生剂的研制过程。此种气体发生剂是一种凝胶体，它以硝酸羟胺（HAN）作为主氧化剂，以硝酸铵(AN )作为辅助氧化剂，水作为溶剂，并选择一种高分子凝胶剂，通过凝胶化使氧化剂水溶液成为具有一定形状的胶体，要求选择的高分子凝胶剂具有一定数目的碳原子，同时作为可燃剂，本实验选择的高分子凝胶剂为聚乙烯醇（PVA）。在确定基础配方的前提下，通过实验探讨了制备凝胶的工艺条件（时间、温度）；通过控制体系的水含量来进一步优化配方；以零氧平衡为原则确定配方；用密闭爆发器实验评价了不同配方样品的燃烧性能，并通过密闭爆发器实验结果确定最佳配方；用60L压力舱试验去检验此种配方是否具有应用于汽车安全气囊的可行性。经过实验，结果表明此种气体发生剂具有较快的燃烧速度，较大的产气量，燃气的气相色谱也表明其燃气相对洁净，因此可以满足汽车安全气囊的基本要求。HAN气体发生剂以液态氧化剂为原料，是一种新型的气体发生剂，其各项性能优良，目前在国内气体发生剂的研制领域还属首创，它的研制为液态氧化剂应用于气体发生剂提供了一些思路，并为研究凝胶气体发生剂在气体发生器中的燃烧特性提供了一些有价值的基础数据。
The paper introduces a gas generating agent for automobile safety airbag. This gas generating material is a solid solution which comprises of a water soluble liquid and a hydrophilic gelling agent. It regards hydroxylammonium nitrate (HAN) as the main oxidant and ammonium nitrate(AN ) as the second oxidant . And water is regarded as the solvent. The preferred gelling agent is Polyvinyl acetate which comprises carbon atoms in an effective amount to function as a fuel with the liquid oxidizer .The preparation of the gel with fixed shape by means of gel test has been introduced and the influence factors of the technique process(time, temperature) of the gel preparation have been discussed. The prescription is choused and filled through controlling the content of water of the system; The prescription is determined and filled through zero- oxygen -balance; Based on the closed bomb test, the combustion characteristics of different samples are studied and the prescription bestly is defined; The feasibility analysis is carried on though 60L pressure tank. The results of above-mentioned experiments show that the higher burning rates and the larger volume product of this kind of gas generating agent can meet the requirements of automobile safety airbag. Gas chromatography shows the gas product is clean relatively. This is a new type of gas-generating agent, which the oxidizer is a kind of liquid oxidizer. This gas-generating gent has fine characteristic. And the research of this kind of gas generating gent is an innovation in domestic field. This study can offer some thought of the application of liquid oxidizer for gas generating agent，which may serve as a basis or reference for further study on calculation and design of gas generator .
The paper introduces a gas generating agent for automobile safety airbag. This gas generating material is a solid solution which comprises of a water soluble liquid and a hydrophilic gelling agent. It regards hydroxylammonium nitrate (HAN) as the main oxidant and ammonium nitrate(AN ) as the second oxidant . And water is regarded as the solvent. The preferred gelling agent is Polyvinyl acetate which comprises carbon atoms in an effective amount to function as a fuel with the liquid oxidizer .The preparation of the gel with fixed shape by means of gel test has been introduced and the influence factors of the technique process(time, temperature) of the gel preparation have been discussed. The prescription is choused and filled through controlling the content of water of the system; The prescription is determined and filled through zero- oxygen -balance; Based on the closed bomb test, the combustion characteristics of different samples are studied and the prescription bestly is defined; The feasibility analysis is carried on though 60L pressure tank. The results of above-mentioned experiments show that the higher burning rates and the larger volume product of this kind of gas generating agent can meet the requirements of automobile safety airbag. Gas chromatography shows the gas product is clean relatively. This is a new type of gas-generating agent, which the oxidizer is a kind of liquid oxidizer. This gas-generating gent has fine characteristic. And the research of this kind of gas generating gent is an innovation in domestic field. This study can offer some thought of the application of liquid oxidizer for gas generating agent，which may serve as a basis or reference for further study on calculation and design of gas generator .
引文
[1] 张盛榜，气体发生剂浅谈，火炸药，1980、5 ，43～46
[2] 邓康清，陶自成，国外气体发生剂研制动向，1996，19，3，34~40
[3] 汽车工程手册编写委员会，汽车工程手册?基础篇，北京，人民教育出版社，2001，866~874
[4] Donald R.Doole，Azide gas generating composition for inflatable devices， United States, 4931111,1990（4）
[5]陈守文，成一，叠氮化钠气体发生剂的研究，2001、4，3~739
[6] Tadao Yoshida,Air bag gas generating composition ,United States,5898126,1999(4)
[7] David D.Ryder, Gas generating material for vehicle occupant protection device, United States,6143103, 2000(11)
[8] Giovanetti, Air bag gas generating composition , United States ,5060973,1991(10)
[9] XingxiZhou, Gas generating composition for airbag , United States,6468369B1,
2002(10)
[10] Adriana Petronelle Martina Leenders, Gas generating preparation with iron and/or copper carbonate , United States ,6228191B1,2001(5)
[11] P·S·坎达迪尔,具有内在催化剂的非叠氮化物气体发生剂组合物,Chana, 1150794A, 1997(5)
[12] 成一，陈守文,PAK气体发生剂的燃气特性研究,固体火箭技术,2001、4，59～61
[13] 陈守文，成一，非叠氮化物气体发生剂的设计与研究，江苏化工，2002、12，38～41
[14] 陈守文，成一，汽车安全气囊用非叠氮化物气体发生剂的研究，汽车安全，2002、4，55～56，58
[15] 孙志刚，李朝阳，双基推进剂用于气囊充气的可行性探讨，火炸药学报，2003，26，1，62～64
[16] Giovanetti，Air bag gas generating composition ，United States,5060973，1991(10)
[17] Kerry L.Wagaman,Bryantown,MD，GAS-GENGRATING LIQUID COMPOSITIONS(PERHAN) ，United States， 6328831B1，2001(12)
[18] Harold R.Blomquist，Vehicle occupant protection device and solid solution gas generating composition therefore ，United States ，6228193B1，2001(5)
[19] Michael W.Barmes,Bradley D.Harris, L.Johnson，Hydroxylammonium nitrate/water/self -deflagrating fuels as gas generating pyrotechnics for use in automotive passive restraint systems，United States ，5684269，1997(11)
[20] 张豪侠，国外液体发射药生产技术的新进展，国外兵器动态，1991(34)
[21] 于恩江，黄怀安，周兴权等，硝酸羟胺在动力堆乏燃料后处理流程钚线第三循环中的应用，原子能科学技术，1993、27，5，451~456
[22] 张汉兴，沈建军，浆状炸药凝胶体系的研究，爆破，1992，2，57~60，49
[23] 张续柱，肖忠良，液体发射药，北京，中国科学技术出版社，1993，19~31
[24] 程永钢，羟胺及其盐，火炸药，1992、2，52~57
[25] 陈世武，凝胶推进剂的由来与发展，火炸药，1996、1，47～52
[26] 严瑞瑄，水溶性高分子，化学工业出版社，北京，1998，6
[27] 钱知勉等，塑料性能应用手册，上海，上海科学技术文献出版社，1981，106~107
[28] 王伯羲，冯增国，杨荣杰，火药燃烧理论，北京理工大学出版社，1994，1~17
[29] 徐文娟，张莺等，内弹道学（第三版），31~62
[30] 何天白，胡汉杰，功能高分子与新技术，化学工业出版社，2001，112~120
[31] 顾正秋，肖久梅，张湘虹，人工软骨材料-聚乙烯醇水凝胶的研制，生物医学杂志，1999，16，1，13~18
[32] B.沃尔默特（联邦德国）著，黄家贤译，高分子化学基础（中册），北京，化学工业出版社，1986，188～300
[33] 刘继华,火药物理化学性能,北京,北京理工大学出版社，1997,57～68
[34] 王泽山，韩盘铭，张续柱等,火药实验,北京,中国科学技术出版社，1992,78～80,136～140
[35] 成一等，PAK气体发生剂的燃气特性研究，固体火箭技术，2001，4 ，59～61
[36] 清华大学分析化学教研室编，现代仪器分析(下)，清华大学出版社，1983,10,400～416
[37] 白渝平，博士论文，聚丙烯酸(PAA)/聚乙烯醇(PVA)互穿聚合物网络(IPN)水凝胶的结构和性能研究 ，北京理工大学，北京理工大学，2001
[38] 徐燕莉, 表面活性剂的功能, 北京, 化学工业出版社,1997，148～151
[39] 柳明珠，程镕时，钱人元，聚乙烯醇水凝胶溶胀特性研究，高分子学报，1996、4，235～239
[40] 吴李国，章悦庭，蔡禄生，胡绍华，冷冻- 解冻法制聚乙烯醇水凝胶研究进展，化工新型材料，2001，29，11，19～20，25
[2] 邓康清，陶自成，国外气体发生剂研制动向，1996，19，3，34~40
[3] 汽车工程手册编写委员会，汽车工程手册?基础篇，北京，人民教育出版社，2001，866~874
[4] Donald R.Doole，Azide gas generating composition for inflatable devices， United States, 4931111,1990（4）
[5]陈守文，成一，叠氮化钠气体发生剂的研究，2001、4，3~739
[6] Tadao Yoshida,Air bag gas generating composition ,United States,5898126,1999(4)
[7] David D.Ryder, Gas generating material for vehicle occupant protection device, United States,6143103, 2000(11)
[8] Giovanetti, Air bag gas generating composition , United States ,5060973,1991(10)
[9] XingxiZhou, Gas generating composition for airbag , United States,6468369B1,
2002(10)
[10] Adriana Petronelle Martina Leenders, Gas generating preparation with iron and/or copper carbonate , United States ,6228191B1,2001(5)
[11] P·S·坎达迪尔,具有内在催化剂的非叠氮化物气体发生剂组合物,Chana, 1150794A, 1997(5)
[12] 成一，陈守文,PAK气体发生剂的燃气特性研究,固体火箭技术,2001、4，59～61
[13] 陈守文，成一，非叠氮化物气体发生剂的设计与研究，江苏化工，2002、12，38～41
[14] 陈守文，成一，汽车安全气囊用非叠氮化物气体发生剂的研究，汽车安全，2002、4，55～56，58
[15] 孙志刚，李朝阳，双基推进剂用于气囊充气的可行性探讨，火炸药学报，2003，26，1，62～64
[16] Giovanetti，Air bag gas generating composition ，United States,5060973，1991(10)
[17] Kerry L.Wagaman,Bryantown,MD，GAS-GENGRATING LIQUID COMPOSITIONS(PERHAN) ，United States， 6328831B1，2001(12)
[18] Harold R.Blomquist，Vehicle occupant protection device and solid solution gas generating composition therefore ，United States ，6228193B1，2001(5)
[19] Michael W.Barmes,Bradley D.Harris, L.Johnson，Hydroxylammonium nitrate/water/self -deflagrating fuels as gas generating pyrotechnics for use in automotive passive restraint systems，United States ，5684269，1997(11)
[20] 张豪侠，国外液体发射药生产技术的新进展，国外兵器动态，1991(34)
[21] 于恩江，黄怀安，周兴权等，硝酸羟胺在动力堆乏燃料后处理流程钚线第三循环中的应用，原子能科学技术，1993、27，5，451~456
[22] 张汉兴，沈建军，浆状炸药凝胶体系的研究，爆破，1992，2，57~60，49
[23] 张续柱，肖忠良，液体发射药，北京，中国科学技术出版社，1993，19~31
[24] 程永钢，羟胺及其盐，火炸药，1992、2，52~57
[25] 陈世武，凝胶推进剂的由来与发展，火炸药，1996、1，47～52
[26] 严瑞瑄，水溶性高分子，化学工业出版社，北京，1998，6
[27] 钱知勉等，塑料性能应用手册，上海，上海科学技术文献出版社，1981，106~107
[28] 王伯羲，冯增国，杨荣杰，火药燃烧理论，北京理工大学出版社，1994，1~17
[29] 徐文娟，张莺等，内弹道学（第三版），31~62
[30] 何天白，胡汉杰，功能高分子与新技术，化学工业出版社，2001，112~120
[31] 顾正秋，肖久梅，张湘虹，人工软骨材料-聚乙烯醇水凝胶的研制，生物医学杂志，1999，16，1，13~18
[32] B.沃尔默特（联邦德国）著，黄家贤译，高分子化学基础（中册），北京，化学工业出版社，1986，188～300
[33] 刘继华,火药物理化学性能,北京,北京理工大学出版社，1997,57～68
[34] 王泽山，韩盘铭，张续柱等,火药实验,北京,中国科学技术出版社，1992,78～80,136～140
[35] 成一等，PAK气体发生剂的燃气特性研究，固体火箭技术，2001，4 ，59～61
[36] 清华大学分析化学教研室编，现代仪器分析(下)，清华大学出版社，1983,10,400～416
[37] 白渝平，博士论文，聚丙烯酸(PAA)/聚乙烯醇(PVA)互穿聚合物网络(IPN)水凝胶的结构和性能研究 ，北京理工大学，北京理工大学，2001
[38] 徐燕莉, 表面活性剂的功能, 北京, 化学工业出版社,1997，148～151
[39] 柳明珠，程镕时，钱人元，聚乙烯醇水凝胶溶胀特性研究，高分子学报，1996、4，235～239
[40] 吴李国，章悦庭，蔡禄生，胡绍华，冷冻- 解冻法制聚乙烯醇水凝胶研究进展，化工新型材料，2001，29，11，19～20，25