。858· 北京科技大学学报 2006年第9期 证了反应以低温模式进行，促进了a-Si3N4的生 [3 Mukasyan A S.Borovinskaya I P.Stmucture formation in SHS 成 nitrides.Int J SHS 1992 1(1):55 [4 Merzhanov A G.Borovinskaya I P.Method of Preparing Sil- 3 结论 con Nitride with a High Alpha phase Content:US Patent 5032370.1991 (1)采用燃烧合成方法，以叠氯化钠作为固 [5 Zakorzhevski VV,Borovinskaya I P.Some regularities of 态氮化剂联合卤化铵制备了α相含量约94%的 synthesisaSigN in a commercial SHS reactor.Int J SHS 2000.9(2):171 氮化硅粉体. [6 Cano IG.Baelo S P.Rodriguez M A.et al.SeF-propagating (2)卤化铵在燃烧合成反应中起到了分解吸 high temperature-synthesis of SiN:role of ammonium salt 热，增加Si-N之间的有效接触面积，增加硅粉内 addtion.J Eur Ceram Soc 2001.21(3):291 部孔隙率和氨气渗透性以及降低Si一N反应的燃 [7]Holt J B.Kingman DD Bianchini G M.Synthesis of fine graineda-silicon Nitride by a Combustion Process:US Patent 烧温度的作用，有利于硅粉的氮化反应 4944930.1990 (3)叠氮化钠的加入主要是为SiN体系的 [8 Cao Y G.Chen H.Li J T.et al.Fomation of a-Sig N 燃烧合成反应提供了反应物内部氮源，同时也发 w hiskers with addition of NaN3 as catalyst.J Cryst Growth 2002.234(1):9 挥着SN反应的催化剂的作用. [9 Chen H.Cao YG.Xiang X W,et al.Fabricat ion ofB-SigN (4)叠氮化钠联合卤化铵的使用能够有效地 nano-fibers.J Alloy Compd 2001.325:LI 降低燃烧温度使燃烧反应以低温模式进行，有利 10]Gazzara C P.Messier D P.Determination of phase contents 于a一Si3N4的生成.在有叠氮化钠加入的条件 in SiN by X-ray diffraction analysis.Am Ceram Soc Bull, 1977,56(9):777 下，增加燃烧反应物中的卤化铵含量会导致燃烧 11]Lide D R.CRC handbook of chemistry and physics.83rd 产物中的aSi3N4含量增加.但过量的铵盐活性 Edition.CRC Press 2002 稀释剂加入会导致燃烧反应的自蔓延无法维持. [12]Piper L G.Krech RH.Taylor R L Generation of N3 in the theral decomposition of NaN J Chem Phys.1979 71 参考文献 (5):2099 13]Lidin R A.Molochko V A.Andreeva LL Reactivity of im [1]Hirao K.Miyamdo Y,Koizumi M.Synthesis of silicon ri- organic substances:handbook.revised and aumented ed- tride by a combustion reaction under high nit mogen presure.J tion.New York:Begell House Publishers 1996:478 Am Ceram Soc,1986.69(4):C6G-1 14]Chang A J Rhee S W,Baik S.Kinetics and mechanisms for 【2】李江海.气固体系自蔓延高温合成氮化物的研究学位论 nitridation of floating aluminum pow der.J Am Ceram Soc. 刘.北京：北京科技大学，1995：41 78(1),1995:33 Combustion sy nthesis of Si3N4 pow der using sodium azide and ammonium halide as additives WANG Fei2,SHEN Weiping,GE Changchun 1)Laboratory of Special Ceramics and Pow der Metallurgy.University of Science and Technology Beijng.Beijng 100083.China 2)Collge of Mining Ergineering Taiyuan University of Techndlogy,Taiyuan 030024 Chim ABSTRACT The effects of sodium azide used as solid nitrogen source and ammonium halide used as active diluent on the combustion synthesis of Si3N4 pow der were investigated through analyzing the combust ion temperature profiles and the phase composition of the combustion products.The research results show that the endothermic decomposition of these two kinds of additives can increase the porosity of the reactants and thus improve the nitrogen permeability.The additives can also provide interior nitrogen source and act as catalysts of Si-N reaction that facilitates the combust ion reaction of silicon in nitrogen atmosphere.The ad- dition of sodium azide and ammonium halide can effectively lower the combustion temperature and maintain the combustion reaction at a relatively low temperature w hich is in favor of the formation of Si3N4.Ap- propriate addition of sodium azide and ammonium halide can promote the nitridation of silicon and increase the a-content in the combustion products. KEY WORDS silicon nitride powder;combustion synthesis;sodium azide;ammonium halide证了反应以低温模式进行, 促进了 α-Si3N4 的生 成. 3 结论 (1)采用燃烧合成方法 ,以叠氮化钠作为固 态氮化剂联合卤化铵制备了 α相含量约 94 %的 氮化硅粉体. (2)卤化铵在燃烧合成反应中起到了分解吸 热,增加 Si-N 之间的有效接触面积 ,增加硅粉内 部孔隙率和氮气渗透性以及降低 Si -N 反应的燃 烧温度的作用, 有利于硅粉的氮化反应 . (3)叠氮化钠的加入主要是为 Si -N 体系的 燃烧合成反应提供了反应物内部氮源 , 同时也发 挥着 Si-N 反应的催化剂的作用. (4)叠氮化钠联合卤化铵的使用能够有效地 降低燃烧温度, 使燃烧反应以低温模式进行, 有利 于α-Si3N4 的生成 .在有叠氮化钠加入的条件 下,增加燃烧反应物中的卤化铵含量会导致燃烧 产物中的α-Si3N4 含量增加 .但过量的铵盐活性 稀释剂加入会导致燃烧反应的自蔓延无法维持. 参 考 文 献 [ 1] Hirao K , Miyamot o Y , Koizumi M .Synthesis of silicon ni￾tride by a combustion reaction under high nitrogen p ressure.J Am Ceram Soc , 1986 , 69(4):C60-1 [ 2] 李江涛.气-固体系自蔓延高温合成氮化物的研究[ 学位论 文] .北京:北京科技大学, 1995:41 [ 3] Mukasyan A S , Borovinskaya I P .Structure formation in SHS nitrides.Int J SHS, 1992 , 1(1):55 [ 4] Merzhanov A G , Borovinskaya I P.Method of Preparing Sili￾con Nitride w ith a High Alpha-phase Cont ent :US Pat ent 5032370 , 1991 [ 5] Zakorzhevskii V V , Borovinskaya I P .Some regularities of synthesisα-Si 3N4 in a commercial SHS reactor .Int J SHS, 2000 , 9(2):171 [ 6] Cano I G , Baelo S P, Rodriguez M A , et al.Self-propagating high temperature-synthesis of Si 3N4 :role of ammonium salt addition.J Eur Ceram Soc, 2001 , 21(3):291 [ 7] Holt J B , Kingman D D, Bianchini G M .Synthesis of fine￾grainedα-silicon Nitride by a Combustion Process:US Pat ent 4944930 , 1990 [ 8] Cao Y G , Chen H , Li J T , et al.Formation of α-Si 3N4 w hiskers with addition of NaN3 as cat alyst.J Cryst Growth, 2002 , 234(1):9 [ 9] Chen H , Cao Y G , Xiang X W, et al.Fabrication of β-Si3N4 nano-fibers.J Alloy Compd, 2001 , 325:L1 [ 10] Gazzara C P , Messier D P .Det ermination of phase cont ents in Si 3N4 by X-ray diffraction analysis.Am Ceram Soc Bull , 1977 , 56(9):777 [ 11] Lide D R.C RC handbook of chemistry and physics.83rd Edition.CRC Press, 2002 [ 12] Piper L G , Krech R H , Taylor R L.Generation of N3 in the thermal decompositi on of NaN3.J Chem Phys, 1979, 71 (5):2099 [ 13] Lidin R A , Molochko V A , Andreeva L L.Reactivity of in￾organic substances:handbook.revised and augmented edi￾tion.New York:Begell House Publishers, 1996:478 [ 14] Chang A J, Rhee S W, Baik S .Kinetics and mechanisms for nitridation of floating aluminum pow der .J Am Ceram Soc , 78(1), 1995:33 Combustion sy nthesis of Si3N4 pow der using sodium azide and ammonium halide as additives WANG Fei 1, 2), SHEN Weiping 1), GE Changchun 1) 1)Laborat ory of Special Ceramics and Pow der Metallurgy , Universit y of Science and Technology Beijing , Beijing 100083 , China 2)College of Mining Engineering, Taiyuan University of Technology , Taiyuan 030024 , C hina ABSTRACT The effects of sodium azide used as solid nitrogen source and ammonium halide used as active diluent on the combustio n synthesis of Si3N4 pow der were investigated through analyzing the combustion temperature profiles and the phase composition of the combustion products .The research results show that the endothermic decomposition of these tw o kinds of additives can increase the po rosity of the reactants and thus improve the nitrogen permeability .The additives can also provide interio r nitrogen source and act as catalysts of Si-N reaction that facilitates the combustion reaction of silicon in nitrogen atmosphere.The ad￾dition of sodium azide and ammonium halide can effectively lower the combustio n temperature and maintain the combustion reaction at a relatively low temperature w hich is in favo r of the formation of α-Si3N4 .Ap￾propriate addition of sodium azide and ammonium halide can promo te the nitridation of silicon and increase the α-content in the combustion products . KEY WORDS silicon nitride powder ;combustion synthesis ;sodium azide ;ammonium halide · 858 · 北 京 科 技 大 学 学 报 2006 年第 9 期