基于熵模型镀锡银钎料钎焊性能的定量表征

以BAg50CuZn钎料和BAg34CuZnSn钎料为基材，采用镀覆扩散组合工艺制备了两类镀锡银钎料，利用综合热分析仪、润湿试验炉、万能拉力试验机测定镀锡银钎料的熔化温度区间、润湿面积及钎焊接头抗拉强度，建立了钎料润湿熵和接头强度熵的数学模型，并与熔炼合金化制备的相同Sn含量的传统钎料进行对比. 结果表明，与相同Sn含量的传统钎料相比，镀锡银钎料的润湿熵值更小、强度熵值略高. 同等Sn含量条件下，镀锡银钎料和传统钎料润湿熵值的变化趋势，与对应钎料在316LN不锈钢表面的润湿面积随Sn含量的变化趋势基本一致，强度熵值的变化趋势与对应钎料钎焊316LN不锈钢接头的抗拉强度随Sn含量的变化趋势几乎吻合；润湿熵和强度熵的模型在一定程度上可定量预测镀锡银钎料的钎焊工艺性和接头力学性能.     

Sn改性Ti-Zr-Cu-Ni钎料的微观组织和力学性能

采用自制Ti-Zr-Cu-Ni-Sn钎料钎焊TA2钛合金,研究了不同Sn元素含量改性Ti-Zr-Cu-Ni钎料的熔化特性、微观组织及物相、润湿及熔蚀性、接头拉伸强度。研究表明,Sn含量增加,Ti-Zr-Cu-Ni-Sn钎料固、液相线温度基本升高,但温度差值基本变窄,可更好地抑制钎焊界面脆性化合物形成。Ti-Zr-Cu-Ni-5Sn钎料组织由Ti、Zr基体和晶体相构成,Sn倾向与Ti、Zr结合形成Ti₂Sn₃、Ti₆Sn₅、Zr₅Sn₃等低熔点共晶相。Sn≤1.5%时,随Sn含量增加,钎料对TA2钛合金的润湿性逐渐变差;继续增加Sn,钎料润湿性改善,添加5%Sn的钎料对基体润湿最佳。添加5%Sn并降低Cu、Ni总量的改性钎料对TA2钛合金熔蚀减弱。相同钎焊工艺下,添加5%Sn接头的强度和塑性均有提升。钎焊温度升高,Ti-Zr-Cu-Ni钎料产生更多强化物相,致接头强度大幅提升,而Ti-Zr-Cu-Ni-5Sn钎料产生的含Sn物相强化作用对接头强度提升有限;相...     

Development of Ag based brazing filler metal with low melting point

Abstract

This study was carried out to develop cadmium free silver based brazing filler metals that meet the following requirements. First, they have to have a melting point lower than that of BAg-1 brazing filler metal. Second, they have to have not only good wetting characteristics and the ability to produce a sound joint with excellent mechanical properties but also plastic formability. Using the calculated phase diagrams on Ag–Cu–Zn–Sn quaternary system alloys, the authors selected several alloys with a possibility of meeting the above requirements. The melting point and other properties, such as hardness and brazeability of the selected alloys, were evaluated. As a result, the authors successfully developed silver based brazing filler metals that have a low melting point below ～600°C and meet the above requirements by adding a small amount of indium as an alloying element into the Ag–Cu–Zn–Sn quaternary system alloy. The newly developed brazing filler metals are slightly inferior in wetting characteristics to BAg-1; however, the brazing filler metal containing ～3 mass-% indium element showed wetting characteristics comparable to those of BAg-1. Furthermore, the new brazing filler metals could produce joints with a high tensile strength equivalent to ～83% of that of a joint brazed using BAg-1.     

合金元素锡和磷对低银钎料钎焊性能的影响

针对Sn和P对低银钎料的钎焊性能的影响进行了研究,发现Sn和P的添加使低银钎料的熔点降低,Sn的添加同时使低银钎料的钎焊性能变好。     

低熔合金粉末对药芯银钎料钎焊过程的影响

为克服高锡含量的AgCuZnSn钎料因脆性大而难以加工成形的问题,借鉴药芯焊丝的理念,设计了添加CuSn合金粉粉芯的复合药芯银钎料,研究了粉芯中添加质量分数30%～70%Cu60Sn40合金粉对药芯银钎料的润湿性、紫铜/Q235钢钎焊接头组织、界面显微硬度及抗拉强度的影响。结果表明,钎焊过程中芯部CuSn合金粉和外层BAg30CuZnSn原位反应合成高锡含量的AgCuZnSn钎料,获得了成分均匀,结合良好的接头。随着药芯粉芯中合金粉含量的升高,复合药芯银钎料在紫铜板及Q235钢板上的润湿面积不断增大,Cu/Q235钢钎焊接头显微硬度不断升高,抗拉强度呈现先升高后降低的趋势。当药芯粉芯中CuSn合金粉的质量分数为30%时,Cu/Q235钢钎焊接头的抗拉强度取得最大值(198.91 MPa),提高了23.4%。     

含锆Cu-P基非晶钎料钎焊紫铜接头的连接强度及微观组织

采用CuP7.7Sn5.4Ni14Si0.2Zr0.04非晶和常规钎料钎焊紫铜,分析了钎料和接头的微观组织及钎焊工艺对接头强度的影响.结果表明,相对于非晶钎料,常规钎料对钎焊工艺的敏感性更大;在相同的试验条件下,采用非晶钎料钎焊的接头强度比常规钎料提高30%以上;非晶钎料看不到明显的相结构,而常规钎料主要由初生（Cu,...     

Ga和Ce复合添加对低银无镉钎料组织及性能的影响

通过向Ag17CuZnSn钎料中复合添加微量的Ga元素和稀土元素Ce,研究了Ga和Ce元素的复合添加对低银无镉钎料组织及焊接性能的影响。采用火焰钎焊方法得到黄铜与不锈钢异种金属钎焊接头。试验表明,随着Ga和Ce元素的添加低银钎料的固液相线温度不断下降。当Ga和Ce含量分别为2%和0.15%时,钎料在母材表面的铺展面达到最大值。Ga和Ce元素的复合添加对低银钎料中的CuZn化合物相有明显的细化作用,黄铜与不锈钢钎焊接头的抗剪强度最大值为378.6 MPa。在钎焊过程中,钎缝与不锈钢母材之间发生了明显的元素扩散,Ga元素的扩散率大于其他元素。同时当低银钎料中的Ce元素含量大于0.3%时,钎料组织中出现了新生成的块状的稀土相。     

SnAg1.0Cu0.5对Ag30CuZnSn药芯钎料润湿性能及钎焊接头力学性能的影响

向Ag30CuZnSn药芯钎料药粉中添加SnAg1.0Cu0.5(SAC105)粉末,研究了不同SAC105含量对Ag30CuZnSn药芯钎料钎缝组织及钎焊接头性能的影响. 结果表明,SAC105的加入可以显著提高Ag30CuZnSn药芯银钎料的润湿铺展性能,随着SAC105的添加量增加,Ag30CuZnSn药芯银钎料的润湿铺展面积增大. 这主要是因为Sn元素的增加能显著降低钎料的熔化温度,从而增大液态金属的过热度,降低液态金属的粘度,增强液态金属的流动性,最终提高Ag30CuZnSn钎料在304不锈钢表面的润湿铺展性能. SAC105添加量为20% (质量分数)时,钎缝组织最细,主要由交织状的银基固溶体构成,相应的钎焊接头抗剪强度最大为453 MPa,提高了29.9%.     

腐蚀对复合银钎料的影响

采用恒温浸泡腐蚀、电化学腐蚀、润湿铺展测试和扫描电子显微镜(SEM)、万能力学试验机等手段研究了复合银钎料中钎剂与钎料合金的腐蚀及钎料腐蚀对钎焊性能的影响。结果表明,银钎料处于含水钎剂环境中,会被钎剂腐蚀。在钎料中加入1.5%~2.5%的Sn,缩小了Ag-Cu-Zn合金中Ag-Zn相与Cu-Zn相之间的电位差,降低了两相之间的微电池效应,Sn细化Ag-Cu-Zn钎料中的共晶相,降低银钎料发生腐蚀的敏感性;用被腐蚀的银钎料钎焊钢,钎焊接头抗拉强度损失,在钎料中添加Sn可抑制损失程度。     

AgCuZn-X(Ga, Sn, In, Ni)钎料显微组织及钎焊接头研究

研究了不同合金元素Ga,Sn,In和Ni添加对Cd银基钎料及其钎焊接头的显微组织影响,同时对AgCuZn-X(Ga,Sn,In,Ni)钎料的对接和搭接实验做了对比实验分析。结果表明,添加Ga,Sn,In和Ni4种元素的银钎料具有"特有的镓结构",具有较低的固相线和液相线,其钎缝力学性能优异,由SEM观察钎缝显微组织可知,低银含镓钎料具有与高银高镓钎料相近的织网状致密组织,添加适当的元素可以显著提高低银钎料的性能。     

Cu-P基非晶钎料钎焊机理

采用CuP7．7Sn5．4Nil4Si0．2Zr0．04晶态与非晶钎料钎焊紫铜,通过微观手段对比分析了钎焊温度和保温时间对晶态与非晶态钎料钎焊接头成分和组织的影响．结果表明,CuP7．7Sn5．4Nil4Si0．2Zr0．04非晶钎料钎焊接头由界面区、扩散区以及钎缝中心区组成;随钎焊温度提高或保温时间增加,晶态钎料和非...     

Microstructural characterization of diamond/CBN grains steel braze joint interface using Cu–Sn–Ti active filler alloy

In order to develop the new generation superhard abrasive tools of diamond and cubic boron nitride (CBN), the brazing joint experiments of diamond/CBN crystals and AISI 1045 steel matrix using Cu–Sn–Ti active filler powder alloy were investigated in vacuum furnace. The brazing temperature was 930 °C and the dwelling time was 20 min. Interfacial characteristics of the brazing joint among the diamond/CBN grains, the active filler layer and the steel substrate were analyzed using scanning electron microscopy, energy dispersive spectroscopy and X-ray diffraction techniques. The results indicated that Ti element in the Cu–Sn–Ti alloys diffused preferentially to the surface of diamond/CBN grits to form a Ti-rich reaction layer in the brazed joints by microanalyses. Moreover, the TiC, TiN and TiB₂ phases in diamond/CBN interface and Cu–Ti phase in steel interface were confirmed by X-ray diffraction phase analysis. The wetting and bonding reactions on diamond/CBN by melting Cu–Sn–Ti alloy were realized through the interfacial reaction products like TiC, TiN and TiB₂ compounds during the brazing process. The adhesive strength experiments of the joint interfaces revealed that the grains were not pulled out from the bond interface. The reliable bonding strength of brazed diamond/CBN grains to the steel substrate can meet the application requirements of high efficiency machining in the industrial field.     

Ag-Cu-Zn-Sn-xGa-yIn钎料性能与显微组织

通过对Ag-Cu-Zn-Sn-xGa-yIn钎料的钎焊试验发现:单独添加Ga或In元素时,Ga,In元素的添加量分别控制在3%,1.5%(质量分数)左右最佳;复合添加Ga与In元素时,Ag-Cu-Zn-Sn-3Ga-2In的力学性能最佳.对钎焊接头拉伸断口进行分析结果表明,Ag-Cu-Zn-Sn-3Ga-2In接头断口具备明显韧性断裂特征.当In元素添加量超过2%时,对钎焊接头强度的影响趋于平缓,但是断口已具有明显的解理形貌.Ga,In元素在钎料基体中分布均匀,无明显偏析现象,但是Ag-Cu-Zn-Sn-xGa-yIn钎料基体组织呈现明显的"骨架"状特征.     

热扩散对镀锡银钎料界面组织及熔化特性的影响

对带锡镀覆层的银钎料进行热扩散处理,采用差示扫描量热仪(DSC)、扫描电镜(SEM)、X射线衍射仪(XRD)研究热扩散工艺对其熔化温度和扩散界面组织、物相的影响. 结果表明,在扩散时间一定条件下,随着扩散温度升高,扩散界面层厚度增加;随着扩散温度升高或扩散时间延长,钎料的固、液相线温度均降低,熔化温度区间缩小;扩散界面层物相主要由棒状Ag₃Sn相和块状Cu₃Sn相组成;最佳热扩散工艺为220 ℃,24 h. 经最佳工艺处理后,扩散界面层厚度为9.1 μm,钎料中Sn含量为7.2%,此时钎料熔化温度区间为642.34 ℃~676.37 ℃. 与传统熔炼合金化方法相比,钎料中Sn含量提高近31%.     

Effects of Ga and In on the properties of cadmium-free Ag-Cu-Zn filler metal

Melting temperature,spreadability,mechanical properties and the microstructures of joints brazed with silver-base filler metals including different amounts of Ga and/or In were studied respectively in this paper,and the results show that the melting temperature of the silver-base filler metals is decreased,spreadability of the silver-base filler metals is improved,and the microstructures of silver-base filler metals are refined obviously with the addition of Ga and/or In.Using copper and brass plates as base metal and brazing with flame method,the mechanical properties of the lap-joint and butt joint were also examined and analyzed respectively,and the results indicate that the fracture position of two kinds of brazed joints occurred on the base metal,except for the lap-joint of brass,which shows better mechanical properties of the joints brazed with the silver-based filler metals including Ga.For the lap-joint of brass,the tensile strength gradually increased with the increase of Ga content,while the addition of In has little effect on mechanical properties.It is also found that the best comprehensive properties of cadmium-free Ag-Cu-Zn filler metals are obtained when Ga content is about 3.0 wt.% and In content is between 1.5 wt.% and 2.0 wt.%.     

Effect of gallium addition on microstructure and properties of Ag-Cu-Zn-Sn alloys

The effects of Ga on microstructures and mechanical properties of the cadmium-free silver based brazing filler metals have been investigated. The results indicated that Ga additions had the noticeable effect on the microstructure, especially on the shape of the phases. With the increase of Ga addition, the amount of eutectic structure increased, and the acicular eutectic structure changed into the fine eutectic structure with micro-vermiform and rod-like shape. When the addition of Ga was 3.0 wt.%, none of defects exist in the microstructure of the brazed joint. The tensile strength increased from 382 MPa to 511 MPa with the content of Ga increasing from 0 to 3.0 wt.%.     

热解还原法制备镀镍ZrO2增强低银SnAgCu系复合钎料及其钎焊

本文采用热分解-还原法制备镀镍ZrO2增强相,粉末冶金法制备镀镍ZrO2增强Sn1.0Ag0.5Cu复合钎料,研究了ZrO2纳米颗粒表面金属化以及其对Sn1.0Ag0.5Cu复合钎料的微观结构、材料性能及钎焊接头的影响。结果表明:经机械预处理的ZrO2粒径减小、团聚降低;采用热分解-还原法成功地制备出了镀镍ZrO2增强相,Ni粒子以8-11 nm间距均匀附着于ZrO2表面,ZrO2(02)和Ni(11)界面呈半共格关系;添加适量镀镍ZrO2对Ni/ZrO2-Sn1.0Ag0.5Cu复合材料的熔点、电阻率影响不大,提高了润湿性和抗拉强度,在镀镍ZrO2增强相添加量为0.7 wt.%时Ni/ZrO2-Sn1.0Ag0.5Cu复合钎料抗拉强度、钎焊接头剪切强度均达峰值,较基体材料的相比提高了43.3%、40%。随着Ni-ZrO2增强相的添加,复合钎料钎焊接头的断裂位置由界面IMC层向过渡区的近钎缝侧移动,断裂机制由韧-脆混合断裂逐渐转为韧窝为主的韧性断裂。     

钎料对TiC陶瓷/铸铁钎缝处剪应力的影响

采用有限元数值模拟方法研究了采用不同钎料对冷却过程中TiC陶瓷／铸铁焊缝处剪应力的影响。结果表明，无论采用Ni基钎料、Ti基钎料还是他基钎料，剪应力均主要集中在TiC陶瓷／铸铁的钎缝端点上。当采用Ni基和Ag基钎料时，剪应力的最大值出现在钎料／TiC陶瓷界而；而采用Ti基钎料时，剪应力的最大值出现在铸铁／钎料界面。当采用Ni基和Ti基钉料时，冷却到室温的钎缝最大剪应力值较大，因此接头的连接强度较低；当采用Ag基钎料时，冷却到室温的钎缝最大剪应力值较小，因此接头的连接强度较高。     

非晶铜磷钎料升温过程中的组织演变

研究了钎焊温度对非晶钎料微观组织转变的的影响,利用EPMA、XRD等方法分析在升温过程中钎料的组织转变及元素扩散情况,并与普通晶态钎料进行对比研究.结果表明:由于凝固方式的不同,非晶钎料在晶化后为完全共晶组织,且晶粒细小均匀,这有利于提高钎焊接头的性能.     

Cu-Ag-Si-Ga系低蒸气压钎料合金研究

研究了Cu-Ag-Si-Ga系钎料合金的熔化特性、加工性能和在Cu、Ni和不锈钢母材上的铺展性、钎焊接头强度以及Ga对钎料合金微观组织的影响.推荐一种典型的钎料,其成分为40Ag-2Si-2Ga-余量Cu(质量分数%),熔化温度为786.1～823.0℃,在500℃的条件下的蒸气压低于5.51×10~(-8)Pa,该钎料适合用于850～870℃电真空器件分级钎焊.