Al、Ag对Zn-Al钎料性能的影响及相关机理研究
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摘要
纯铝及3003铝合金钎焊通常采用Al-Si钎料，此类钎料润湿性好、强度高，缺点是熔点高，容易导致母材过烧甚至熔化，研发熔点较低的中温铝钎料是目前铝及铝合金钎焊的发展趋势。另外，由于铜的资源性短缺及铜价的居高不下，使以铝代铜成为当前研究的热点之一，研制性能优良的铜-铝钎焊用钎料亦是目前亟待解决的问题。本文以Zn-Al钎料为研究对象，旨在研究开发新型性能优良的铝-铝钎焊及铜-铝钎焊材料。
Zn-Al钎料由于其独特的熔化温度范围（381℃~500℃），在铝-铝钎焊、铜-铝钎焊领域将具有广阔的应用前景。本文研究了Al元素和Ag元素对Zn-Al钎料性能的影响，综合考虑钎料的熔化温度、铺展性能以及钎焊接头力学性能，研究了Zn-Al钎料在纯铝、3003铝合金、紫铜表面的铺展性能以及纯铝钎焊接头、3003铝合金钎焊接头、紫铜-纯铝钎焊接头的力学性能。在此基础上对钎料合金成分进行了优化，并分析了Al元素和Ag元素影响Zn-Al钎料性能的作用机理。
本文首先研究了Al元素对Zn-Al钎料钎焊纯铝性能的影响，分析了Al元素对Zn-Al钎料显微组织、在纯铝表面铺展性能以及纯铝钎焊接头力学性能的影响。研究表明，随着钎料中Al含量的增加，钎料在纯铝表面的铺展面积增大，当Al含量为15wt.%时，铺展面积达到最大，继续增加Al元素含量，铺展性面积减小。纯铝钎焊接头力学性能试验研究结果表明，搭接钎焊接头均断裂于母材，对接钎焊接头部分试件断裂于钎缝。随着钎料中Al含量的增加，对接接头的抗拉强度增大，当Al含量为15wt.%时抗拉强度达到最高，继续增加Al含量，钎缝显微组织变得粗大，钎焊接头抗拉强度降低。由此得出结论，85Zn-15Al钎料钎焊纯铝时，综合性能最好。
采用不同Al含量的Zn-Al钎料钎焊3003铝合金，铺展性能试验结果表明，随着钎料中Al含量的增加，钎料在3003铝合金表面的铺展性能提高，当Al含量为15wt.%时，铺展性能最佳，继续增加Al含量，铺展性能下降。3003铝合金钎焊接头力学性能试验研究结果表明，搭接钎焊接头均断裂于母材，对接钎焊接头部分试件断裂于钎缝。Al含量低于等于15wt.%时，对接钎焊接头均断裂于母材处。当Al含量超过15wt.%后，钎缝显微组织变得粗大，钎焊接头抗拉强度降低，部分试件断裂于钎缝处。综合考虑钎料铺展性能及钎焊接头力学性能，85Zn-15Al钎料钎焊3003铝合金性能最佳。
Al元素对Zn-Al钎料铜-铝钎焊过程中的铺展性能、钎焊接头力学性能及钎缝显微组织影响显著。研究结果表明，随着钎料中Al含量的增加，钎料在紫铜表面的铺展性能提高，但Zn-Al钎料在紫铜表面的铺展性能显著低于其在纯铝表面的铺展性能。因此，在铜-铝异种材料钎焊过程中，Zn-Al钎料在钎缝中的流动主要依赖于钎料在纯铝表面的润湿、铺展。钎焊接头力学性能试验结果表明对接与搭接钎焊接头均断裂于钎缝。随着钎料中Al含量的增加，铜-铝钎焊接头强度提高，当Al含量为15wt.%时钎焊接头力学性能最佳，继续增加Al含量，钎缝内的CuAl2化合物数量显著增加且变得粗大，粗大的CuAl2化合物与其周围组织之间容易产生应力集中而萌生裂纹，导致钎焊接头强度降低。综合考虑钎料铺展性能及钎焊接头力学性能，在不添加其他合金元素的情况下，钎焊铜-铝异种材料时，85Zn-15Al钎料较好。
然而，85Zn-15Al钎料在铜-铝钎焊中仍然存在一些缺点，特别是钎焊接头力学性能有待于进一步提高。本文以85Zn-15Al作为基体钎料，着重研究了Ag元素对Zn-Al钎料显微组织、熔化温度、铺展性能、铜-铝异种材料钎焊接头力学性能以及钎缝显微组织的影响。研究结果表明，随着钎料中Ag含量的增加，钎料的熔化温度显著提高，钎料在纯铝及紫铜表面的铺展面积均呈上升趋势。铜-铝钎焊接头力学性能试验结果表明，搭接与对接钎焊接头均断裂于钎缝处。随着Ag含量的增加，钎缝内部块状CuAl2相尺寸变得细小，产生应力集中的倾向减小，对应的钎焊接头力学性能显著提高。当Ag的添加量为3.3wt.%时，钎焊接头的力学性能最佳，继续增加Ag含量，钎焊接头强度变化不大。铜-铝异种材料钎焊用Zn-Al钎料的最佳Ag含量为3.3wt.%。上述研究结果已经指导实际生产，新配方钎料已经在五金、电力、制冷等行业广泛应用，效果良好。
Pure aluminium and3003Al-alloy are usually brazed by Al-Si filler metal. The spreadability ofAl-Si filler metal is excellent, and the strength of the joint brazed by Al-Si filler metal is good.However, the melting point of Al-Si filler metal is too high to handle, for example, the base metalmight be overheated and even melt during the brazing process. Novel filler metals are in great needfor brazing pure aluminium and Al-alloy at the middle temperature. In addition, because the price ofCu soared in recent years, it also becomes a hotspot to substitute Al for Cu. More and moreproblems exist and need to be solved in Cu/Al brazing before new filler metals for brazing Cu/Al jointdeveloped. In order to solve the problems as mentioned above, the Zn-Al alloy is studied for brazingAl/Al joint and brazing Cu/Al joint in this thesis.
The range of the melting temperature of Zn-Al alloy may keep within381℃~500℃, which isvery suitable to braze Al/Al joint and to braze Cu/Al joint at the middle temperature. The effects of Aland Ag addition on Zn-Al filler metal were studied deeply and systematically in this thesis and thecomprehensive properties of the Zn-Al filler metal were invesigated including the meltingtemperature of the filler metal, the spreadability and the brazed joint mechanical properties. On thebasis of studing and analyzing the mechanism of Al and Ag effects on the joints including purealuminium brazed joint,3003Al-alloy brazed joint, Cu/Al brazed joint, the compositionof the Zn-Alfiller metal were optimized.
The effects of Al on the spreadability of Zn-Al filler metal on pure aluminium surface werestudied, moreover, the mechanical properties and microstructures of the brazed joints also have beenstudied by brazing pure aluminium joints. The results indicate that the spreadability on purealuminium surface enhances with the increase of Al content in the Zn-Al filler metal. The filler metalgets the best spreadability on pure aluminum surface when Al content in the Zn-Al filler metal is15wt.%. However, the spreadability decreases when Al content in the Zn-Al filler metal exceeds15wt.%.Furthermore, the mechanical property tests indicate that all pure aluminium lap joints fracture on thebase metal. But some of pure aluminium butt joints fracture on the brazing seam. The strength of thepure aluminium butt joint enhances with the increase of Al content in the Zn-Al filler metal. Thehighest strength of the pure aluminium butt joint is obtained when Al content is15wt.%. However,when Al content exceeds15wt.%, the microstructures of the brazed joint become coarse, thecorresponding strength of brazed joint decreases. For comprehensive consideration,85Zn-15Al filler metal possesses the best comprehensive properties.
3003Al-alloy were brazed by the different Al content Zn-Al filler metals. The effects of Al onthe spreadability of Zn-Al filler metal were investigated on3003Al-alloy surface, and the mechanicalproperties and microstructures of the brazed joints were also studied. Results indicate that thespreadability on3003Al-alloy surface enhances with the increase of Al content in the Zn-Al fillermetal. The filler metal presents the best spreadability on3003Al-alloy surface when Al content inZn-Al filler metal is about at15wt.%. However, the spreadability gradually deteriorates when Alcontent exceeds15wt.%. Furthermore, the mechanical property tests indicate that all3003Al-alloylap joints fracture on the base metal. But some of3003Al-alloy butt joints fracture on the brazingseam. When Al content in the Zn-Al filler metal are less than or equal to15wt.%, the3003Al-alloybutt joint fracture on the base metal. However, when the Al content exceeds15wt.%, themicrostructures of the brazed joint become coarse and the strength of the brazed joint decreases. Thensome butt joints fracture on the brazing seam. According to the spreadability and the brazed jointstrength,85Zn-15Al filler metal possesses the best comprehensive properties for brazing3003Al-alloy.
Effects of Al on the spreadability of Zn-Al filler metal on pure copper surface were alsoinvestigated, moreover, the mechanical properties and microstructures of the brazed joints have beenstudied by brazing Cu/Al joints. Results indicate the spreadability on pure copper surface is improvedwith the increase of Al content in Zn-Al filler metal. It also has been found that the spreadability onpure copper surface is much lower than that on pure aluminum surface, so the filler metal flow in thebrazing seam depends mainly on its spreadability on the pure aluminium surface in the courese ofbrazing Cu/Al joints. Furthermore, the mechanical property tests indicate that all the Cu/Al brazedjoints fracture on the brazing seam including lap joints and butt joints. The strength of the Cu/Al jointsincluing lap joints and butt joints enhances with the increase of Al content in Zn-Al filler metal. Thepeak strength of the brazed joints presents when Al content is15wt.%. However, when Al contentexceeds15wt.%in Zn-Al filler metal, the CuAl2phase becomes coarse in the brazing seam. Stressconcenstration is easy to occur on the boundary of the coare CuAl2phase, which leads thecorresponding strength of the brazed joint to decrease, so far as we know,85Zn-15Al filler metal isthe better metal for brazing Cu/Al joint.
Some shortcomings of85Zn-15Al filler metal brazing Cu/Al joint have been found, especially,the mechanical properties of the Cu/Al brazed joints are not very high, so on the basis of85Zn-15Alfiller metal, the effects of Ag on the melting temperature of Zn-Al filler metal, spreadability, andmechanical property of the Cu/Al brazed joint as well as the brazing seam microstructure were studied respectively. Results show that the melting temperature rises with the addition of Ag, meanwhile, theaddition of Ag improves the spreadablity on the pure aluminium surface and on pure copper surface.Furthermore, the mechanical property tests indicate that all the Cu/Al brazed joints fracture on thebrazing seam including lap joints and butt joints. The microstructures of the brazed joints areimproved significantly with the addition of Ag. The addition of Ag can refine the CuAl2brittle phasein the brazing seam, which decreases the stress concentration and enhances the brazed joint strength.And the strength of the Cu/Al joints incluing lap joints and butt joints enhances with the increase ofAg content in Zn-Al filler metal. The Zn-Al filler metal with3.3.wt.%Ag shows the best mechanicalproperty when applied in the Cu/Al brazed joint. When the content of Ag exceeds3.3wt.%, themechanical properties of the brazed joints remain stable, the Zn-Al filler metal with3.3wt.%Agpossesses the best comprehensive properties, and the optimal composition of the Zn-Al filler metalhas been successfully applied in the hardware industry, electricity industry, refrigeration industry, andso on.
Zn-Al钎料由于其独特的熔化温度范围（381℃~500℃），在铝-铝钎焊、铜-铝钎焊领域将具有广阔的应用前景。本文研究了Al元素和Ag元素对Zn-Al钎料性能的影响，综合考虑钎料的熔化温度、铺展性能以及钎焊接头力学性能，研究了Zn-Al钎料在纯铝、3003铝合金、紫铜表面的铺展性能以及纯铝钎焊接头、3003铝合金钎焊接头、紫铜-纯铝钎焊接头的力学性能。在此基础上对钎料合金成分进行了优化，并分析了Al元素和Ag元素影响Zn-Al钎料性能的作用机理。
本文首先研究了Al元素对Zn-Al钎料钎焊纯铝性能的影响，分析了Al元素对Zn-Al钎料显微组织、在纯铝表面铺展性能以及纯铝钎焊接头力学性能的影响。研究表明，随着钎料中Al含量的增加，钎料在纯铝表面的铺展面积增大，当Al含量为15wt.%时，铺展面积达到最大，继续增加Al元素含量，铺展性面积减小。纯铝钎焊接头力学性能试验研究结果表明，搭接钎焊接头均断裂于母材，对接钎焊接头部分试件断裂于钎缝。随着钎料中Al含量的增加，对接接头的抗拉强度增大，当Al含量为15wt.%时抗拉强度达到最高，继续增加Al含量，钎缝显微组织变得粗大，钎焊接头抗拉强度降低。由此得出结论，85Zn-15Al钎料钎焊纯铝时，综合性能最好。
采用不同Al含量的Zn-Al钎料钎焊3003铝合金，铺展性能试验结果表明，随着钎料中Al含量的增加，钎料在3003铝合金表面的铺展性能提高，当Al含量为15wt.%时，铺展性能最佳，继续增加Al含量，铺展性能下降。3003铝合金钎焊接头力学性能试验研究结果表明，搭接钎焊接头均断裂于母材，对接钎焊接头部分试件断裂于钎缝。Al含量低于等于15wt.%时，对接钎焊接头均断裂于母材处。当Al含量超过15wt.%后，钎缝显微组织变得粗大，钎焊接头抗拉强度降低，部分试件断裂于钎缝处。综合考虑钎料铺展性能及钎焊接头力学性能，85Zn-15Al钎料钎焊3003铝合金性能最佳。
Al元素对Zn-Al钎料铜-铝钎焊过程中的铺展性能、钎焊接头力学性能及钎缝显微组织影响显著。研究结果表明，随着钎料中Al含量的增加，钎料在紫铜表面的铺展性能提高，但Zn-Al钎料在紫铜表面的铺展性能显著低于其在纯铝表面的铺展性能。因此，在铜-铝异种材料钎焊过程中，Zn-Al钎料在钎缝中的流动主要依赖于钎料在纯铝表面的润湿、铺展。钎焊接头力学性能试验结果表明对接与搭接钎焊接头均断裂于钎缝。随着钎料中Al含量的增加，铜-铝钎焊接头强度提高，当Al含量为15wt.%时钎焊接头力学性能最佳，继续增加Al含量，钎缝内的CuAl2化合物数量显著增加且变得粗大，粗大的CuAl2化合物与其周围组织之间容易产生应力集中而萌生裂纹，导致钎焊接头强度降低。综合考虑钎料铺展性能及钎焊接头力学性能，在不添加其他合金元素的情况下，钎焊铜-铝异种材料时，85Zn-15Al钎料较好。
然而，85Zn-15Al钎料在铜-铝钎焊中仍然存在一些缺点，特别是钎焊接头力学性能有待于进一步提高。本文以85Zn-15Al作为基体钎料，着重研究了Ag元素对Zn-Al钎料显微组织、熔化温度、铺展性能、铜-铝异种材料钎焊接头力学性能以及钎缝显微组织的影响。研究结果表明，随着钎料中Ag含量的增加，钎料的熔化温度显著提高，钎料在纯铝及紫铜表面的铺展面积均呈上升趋势。铜-铝钎焊接头力学性能试验结果表明，搭接与对接钎焊接头均断裂于钎缝处。随着Ag含量的增加，钎缝内部块状CuAl2相尺寸变得细小，产生应力集中的倾向减小，对应的钎焊接头力学性能显著提高。当Ag的添加量为3.3wt.%时，钎焊接头的力学性能最佳，继续增加Ag含量，钎焊接头强度变化不大。铜-铝异种材料钎焊用Zn-Al钎料的最佳Ag含量为3.3wt.%。上述研究结果已经指导实际生产，新配方钎料已经在五金、电力、制冷等行业广泛应用，效果良好。
Pure aluminium and3003Al-alloy are usually brazed by Al-Si filler metal. The spreadability ofAl-Si filler metal is excellent, and the strength of the joint brazed by Al-Si filler metal is good.However, the melting point of Al-Si filler metal is too high to handle, for example, the base metalmight be overheated and even melt during the brazing process. Novel filler metals are in great needfor brazing pure aluminium and Al-alloy at the middle temperature. In addition, because the price ofCu soared in recent years, it also becomes a hotspot to substitute Al for Cu. More and moreproblems exist and need to be solved in Cu/Al brazing before new filler metals for brazing Cu/Al jointdeveloped. In order to solve the problems as mentioned above, the Zn-Al alloy is studied for brazingAl/Al joint and brazing Cu/Al joint in this thesis.
The range of the melting temperature of Zn-Al alloy may keep within381℃~500℃, which isvery suitable to braze Al/Al joint and to braze Cu/Al joint at the middle temperature. The effects of Aland Ag addition on Zn-Al filler metal were studied deeply and systematically in this thesis and thecomprehensive properties of the Zn-Al filler metal were invesigated including the meltingtemperature of the filler metal, the spreadability and the brazed joint mechanical properties. On thebasis of studing and analyzing the mechanism of Al and Ag effects on the joints including purealuminium brazed joint,3003Al-alloy brazed joint, Cu/Al brazed joint, the compositionof the Zn-Alfiller metal were optimized.
The effects of Al on the spreadability of Zn-Al filler metal on pure aluminium surface werestudied, moreover, the mechanical properties and microstructures of the brazed joints also have beenstudied by brazing pure aluminium joints. The results indicate that the spreadability on purealuminium surface enhances with the increase of Al content in the Zn-Al filler metal. The filler metalgets the best spreadability on pure aluminum surface when Al content in the Zn-Al filler metal is15wt.%. However, the spreadability decreases when Al content in the Zn-Al filler metal exceeds15wt.%.Furthermore, the mechanical property tests indicate that all pure aluminium lap joints fracture on thebase metal. But some of pure aluminium butt joints fracture on the brazing seam. The strength of thepure aluminium butt joint enhances with the increase of Al content in the Zn-Al filler metal. Thehighest strength of the pure aluminium butt joint is obtained when Al content is15wt.%. However,when Al content exceeds15wt.%, the microstructures of the brazed joint become coarse, thecorresponding strength of brazed joint decreases. For comprehensive consideration,85Zn-15Al filler metal possesses the best comprehensive properties.
3003Al-alloy were brazed by the different Al content Zn-Al filler metals. The effects of Al onthe spreadability of Zn-Al filler metal were investigated on3003Al-alloy surface, and the mechanicalproperties and microstructures of the brazed joints were also studied. Results indicate that thespreadability on3003Al-alloy surface enhances with the increase of Al content in the Zn-Al fillermetal. The filler metal presents the best spreadability on3003Al-alloy surface when Al content inZn-Al filler metal is about at15wt.%. However, the spreadability gradually deteriorates when Alcontent exceeds15wt.%. Furthermore, the mechanical property tests indicate that all3003Al-alloylap joints fracture on the base metal. But some of3003Al-alloy butt joints fracture on the brazingseam. When Al content in the Zn-Al filler metal are less than or equal to15wt.%, the3003Al-alloybutt joint fracture on the base metal. However, when the Al content exceeds15wt.%, themicrostructures of the brazed joint become coarse and the strength of the brazed joint decreases. Thensome butt joints fracture on the brazing seam. According to the spreadability and the brazed jointstrength,85Zn-15Al filler metal possesses the best comprehensive properties for brazing3003Al-alloy.
Effects of Al on the spreadability of Zn-Al filler metal on pure copper surface were alsoinvestigated, moreover, the mechanical properties and microstructures of the brazed joints have beenstudied by brazing Cu/Al joints. Results indicate the spreadability on pure copper surface is improvedwith the increase of Al content in Zn-Al filler metal. It also has been found that the spreadability onpure copper surface is much lower than that on pure aluminum surface, so the filler metal flow in thebrazing seam depends mainly on its spreadability on the pure aluminium surface in the courese ofbrazing Cu/Al joints. Furthermore, the mechanical property tests indicate that all the Cu/Al brazedjoints fracture on the brazing seam including lap joints and butt joints. The strength of the Cu/Al jointsincluing lap joints and butt joints enhances with the increase of Al content in Zn-Al filler metal. Thepeak strength of the brazed joints presents when Al content is15wt.%. However, when Al contentexceeds15wt.%in Zn-Al filler metal, the CuAl2phase becomes coarse in the brazing seam. Stressconcenstration is easy to occur on the boundary of the coare CuAl2phase, which leads thecorresponding strength of the brazed joint to decrease, so far as we know,85Zn-15Al filler metal isthe better metal for brazing Cu/Al joint.
Some shortcomings of85Zn-15Al filler metal brazing Cu/Al joint have been found, especially,the mechanical properties of the Cu/Al brazed joints are not very high, so on the basis of85Zn-15Alfiller metal, the effects of Ag on the melting temperature of Zn-Al filler metal, spreadability, andmechanical property of the Cu/Al brazed joint as well as the brazing seam microstructure were studied respectively. Results show that the melting temperature rises with the addition of Ag, meanwhile, theaddition of Ag improves the spreadablity on the pure aluminium surface and on pure copper surface.Furthermore, the mechanical property tests indicate that all the Cu/Al brazed joints fracture on thebrazing seam including lap joints and butt joints. The microstructures of the brazed joints areimproved significantly with the addition of Ag. The addition of Ag can refine the CuAl2brittle phasein the brazing seam, which decreases the stress concentration and enhances the brazed joint strength.And the strength of the Cu/Al joints incluing lap joints and butt joints enhances with the increase ofAg content in Zn-Al filler metal. The Zn-Al filler metal with3.3.wt.%Ag shows the best mechanicalproperty when applied in the Cu/Al brazed joint. When the content of Ag exceeds3.3wt.%, themechanical properties of the brazed joints remain stable, the Zn-Al filler metal with3.3wt.%Agpossesses the best comprehensive properties, and the optimal composition of the Zn-Al filler metalhas been successfully applied in the hardware industry, electricity industry, refrigeration industry, andso on.
引文
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