WO2017050284A1 - 一种锡基银石墨烯无铅复合钎料的制备方法 - Google Patents

一种锡基银石墨烯无铅复合钎料的制备方法 Download PDF

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WO2017050284A1
WO2017050284A1 PCT/CN2016/099945 CN2016099945W WO2017050284A1 WO 2017050284 A1 WO2017050284 A1 WO 2017050284A1 CN 2016099945 W CN2016099945 W CN 2016099945W WO 2017050284 A1 WO2017050284 A1 WO 2017050284A1
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silver
graphene
silver graphene
mixture
tin
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French (fr)
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徐连勇
韩永典
荆洪阳
赵雷
吕小青
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Tianjin University
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Tianjin University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/40—Making wire or rods for soldering or welding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering or brazing
    • B23K35/0227—Rods or wires
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering or brazing
    • B23K35/0244—Powders, particles or spheres; Preforms made therefrom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400°C
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400°C
    • B23K35/262—Sn as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/36—Selection of non-metallic compositions, e.g. coatings or fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • B23K35/3601—Selection of non-metallic compositions, e.g. coatings or fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest with inorganic compounds as principal constituents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C13/00—Alloys based on tin
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
    • C22C47/14—Making alloys containing metallic or non-metallic fibres or filaments by powder metallurgy, i.e. by processing mixtures of metal powder and fibres or filaments
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2201/00—Treatment under specific atmosphere
    • B22F2201/10—Inert gases
    • B22F2201/11—Argon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2201/00—Treatment under specific atmosphere
    • B22F2201/20—Use of vacuum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/30—Low melting point metals, i.e. Zn, Pb, Sn, Cd, In, Ga
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2304/00—Physical aspects of the powder
    • B22F2304/10—Micron size particles, i.e. above 1 micrometer up to 500 micrometer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the present invention relates to the preparation of a composite solder by adding a silver graphene nanosheet to a conventional 96.5Sn-3.0Ag-0.5Cu solder and using a ball milling process to prepare a composite solder.
  • Tin-lead alloy solders have long been widely used in the electronics industry, and their solder joints are an indispensable part of electronic devices. They serve as interconnect materials to provide mechanical support between circuit devices, circuit conduction and heat transfer channels. However, lead is potentially harmful to human health and the natural environment.
  • microelectronics technology the development of electronic products in the direction of miniaturization and portability has made the soldering joints of electronic packages more and more dense, and the heat generated per unit volume of electronic products is increasing. The service temperature of the brazed joint is getting higher and higher, and the traditional tin-lead alloy cannot meet the requirements of the modern electronics industry due to poor creep resistance. Therefore, it is necessary to develop new lead-free solders with better performance.
  • solders of the prior art mainly include: tin-copper, tin-silver-copper, tin-zinc and other series alloys, and in order to enhance the mechanical, thermal and electrical properties of the solder, the researchers use composite technology. Adding a strengthening phase to the conventional solder further enhances the performance of the solder. Graphene has good mechanical, electrical and thermal properties, and can be an excellent reinforcing phase of traditional solder. Its low density and good structural stability make it an attractive application prospect in the field of composite solder.
  • the present invention selects Ag-modified graphene as a reinforcing material to improve the nano-silver-modified graphene and Load transfer between the Sn substrates to achieve a better strengthening effect.
  • the purpose of the invention is to use the silver graphene nanosheet as the strengthening phase, and the composite solder is prepared by the ball milling process, the operation is simple, the mixing effect is excellent, and the mechanical properties, the wettability and the growth of the IMC layer are tested by testing the composite solder. It indicates that the silver graphene composite solder prepared by the preparation method has reliable performance, and the application prospect is worthy of expectation.
  • the present invention provides a method for preparing a tin-based silver graphene lead-free composite solder, comprising the following steps:
  • Step 1 According to the mass ratio of 3:1, weigh the graphene and sodium lauryl sulfate and mix it into a mixture A. The amount of dimethylformamide is measured, and the mixture A is added to dimethylformamide to obtain a mixed solution. The mass to volume ratio of the mixture A to dimethylformamide is 1:1, and the unit is mg/ml, which will be mixed. Liquid sonication for 2 hours;
  • Step 2 adding a silver nitrate solution having a molar concentration of 0.06 mol/ml to the mixed solution of the first step, wherein the volume ratio of the silver nitrate solution to the volume ratio of dimethylformamide is 1:2, sonicating for 30 minutes, heating at 70 ° C After 1 hour, the mixture was filtered, washed successively, and washed with alcohol to obtain silver graphene nanosheets;
  • Step 3 using 96.5Sn-3.0Ag-0.5Cu alloy powder as a matrix material, the matrix material has a particle size of 25-45 ⁇ m; and an appropriate amount of silver graphene nanosheet is mixed as a strengthening phase and a matrix material to form a mixture B, wherein The mass percentage of the silver graphene nanosheet is 0.03 to 0.1%;
  • Step 4 Pour the mixture B into a planetary ball mill tank, and add a certain amount of ethanol.
  • the amount of ethanol added is just the mixture B in the ball mill tank and the stainless steel ball as the ball milling medium; the seal is vacuumed and the argon gas is used as protection. Gas, running at 300r/min for 5h, to obtain a powder in which the matrix material is sufficiently mixed with the silver graphene nanosheet;
  • Step 5 After the powder mixed in step 4 is dried, it is placed in a stainless steel mold with a diameter of 20 mm, and placed under a hydraulic press with a single-axis cold press forming at a pressure of 500 MPa;
  • Step 6 The cylinder after cold pressing in step 5 is placed in a high vacuum tubular resistance furnace, vacuum sintered at 175 ° C for 2 h, and then taken out after cooling to room temperature;
  • Step 7 The cylindrical sample sintered in the sixth step is placed in a granule mold, and a cylindrical rod having a diameter of 6 mm is formed under a hydraulic machine, thereby obtaining a tin-based silver graphene lead-free composite solder.
  • the preferred range of the mass percentage of the silver graphene nanosheet is from 0.03 to 0.05%, preferably 0.05%.
  • the addition of fine nano silver particles can also improve the load transfer between the Sn-based and nano-silver-modified graphene, thereby further improving the reliability of the joint and achieving better strength; (2) using the ball milling method for composite brazing
  • the preparation of the material, the mechanical energy of the ball milling process can induce chemical reaction or induce changes in the structure, structure and properties of the material, and has the advantages of significantly reducing the activation energy of the reaction, refining the crystal grains, greatly improving the powder activity and improving the uniformity of particle distribution.
  • Ratio diagram 1 is a pair of wet angles of a conventional Sn-Ag-Cu lead-free solder and Example 1, Example 2, and Example 3. Ratio diagram
  • FIG. 2 is a schematic view showing the comparison of the tensile strength of the conventional Sn-Ag-Cu lead-free solder and the first embodiment, the second embodiment and the third embodiment;
  • Figure 3 (a) is a schematic view showing the thickness of the IMC layer after reflow soldering of a conventional Sn-Ag-Cu lead-free solder;
  • 3(b) is a schematic view showing the thickness of the IMC layer after reflow soldering of the tin-based silver graphene lead-free composite solder containing 0.03% silver graphene nano silver sheet (AG-GNSs);
  • 3(c) is a schematic view showing the thickness of the IMC layer after reflow soldering of the tin-based silver graphene lead-free composite solder containing 0.05% silver graphene nano silver sheets (AG-GNSs);
  • Fig. 3(d) is a schematic view showing the thickness of the IMC layer after reflow soldering of the tin-based silver graphene lead-free composite solder containing 0.1% silver graphene nano silver sheets (AG-GNSs).
  • the design idea of the invention is to select nano-silver particle modified graphene nanosheets (AG-GNSs) as the strengthening phase, and the nano silver particles are embedded on the graphene layer sheet, so as to alleviate the nano-silver-modified graphene when combined with the matrix material. Agglomeration, so that the composite material composition is more uniform, and the silver graphene nanosheet improves the performance of the lead-free solder.
  • the ultrafine material can be prepared by ball milling.
  • the mechanical energy of the ball milling process can induce chemical reaction or induce changes in the structure, structure and properties of the material, which can significantly reduce the activation energy of the reaction, refine the grains, greatly improve the powder activity and improve. Advantages such as uniformity of particle distribution.
  • Example 1 Preparation of tin-based silver graphene lead-free composite solder, the steps are as follows:
  • step (3) weigh a certain amount of 96.5Sn-3.0Ag-0.5Cu alloy powder and the silver graphene nano silver sheet (AG-GNSs) prepared in step (2) (96.5Sn-3.0Ag-0.5Cu alloy) a powder as a matrix material, the matrix material has a particle size of 25-45 ⁇ m), and the mass fraction of the silver graphene nanosheet is 0.03% in the mixed powder;
  • the powder mixed in the step (4) was dried and placed in a stainless steel mold having a diameter of 20 mm, and placed under a hydraulic press to be uniaxially pressed at a pressure of 500 MPa.
  • step (5) The cylinder after cold pressing in step (5) is placed in a high vacuum tubular resistance furnace, vacuum sintered at 175 ° C for 2 h, and then taken out after cooling to room temperature;
  • Example 2 Preparation of tin-based silver graphene lead-free composite solder, the steps are basically the same as those in Embodiment 1, except that in step 3: 96.5Sn-3.0Ag-0.5Cu alloy powder and silver graphene nano silver When the sheets (AG-GNSs) were mixed, the mass fraction of the silver graphene nanosheets in the mixed powder was 0.05%.
  • Example 3 Preparation of tin-based silver graphene lead-free composite solder, the steps are basically the same as those in Embodiment 1, except that in step 3: 96.5Sn-3.0Ag-0.5Cu alloy powder and silver graphene nano silver When the sheets (AG-GNSs) were mixed, the mass fraction of the silver graphene nanosheets in the mixed powder was 0.1%.
  • FIG. 1 is a schematic view showing the comparison of the wetting angle of the prior art Sn-Ag-Cu lead-free solder and the first, second, and third embodiments of the silver-graphene nanosheet-reinforced lead-free solder, which can be seen from FIG. As the mass fraction of silver graphene nanosheets increased, the wetting angle also decreased gradually, from 40° when not added to 22° of Example 3.
  • FIG. 2 is a schematic view showing the comparison of the tensile strength values of the prior art Sn-Ag-Cu lead-free solder and the first and second embodiments of the silver-graphene nanosheet-reinforced lead-free solder. It can be seen from Fig. 2 that the addition of silver graphene nanosheets increases the tensile strength of the composite solder. When the mass fraction of the added silver graphene nanosheets is 0.05%, the tensile strength ratio is not significantly increased. The increase can reach 14.8%.
  • FIG. 3 is a schematic view showing the comparison of the thickness of the IMC after the reflow soldering of the prior art Sn-Ag-Cu lead-free solder and the first, second, and third embodiments of the silver graphene nanosheet-reinforced lead-free solder. It can be seen from Fig. 3 that as the mass fraction of silver graphene nanosheets increases, the IMC layer gradually decreases, indicating that the silver graphene nanosheets have a good inhibitory effect on the formation of IMC.
  • the present invention suggests the use of silver graphene nanosheets.
  • the fraction is from 0.03 to 0.05%, preferably 0.05%.

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  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
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  • Metallurgy (AREA)
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Abstract

一种锡基银石墨烯无铅复合钎料的制备方法，包括将一定量的石墨烯与十二烷基硫酸钠混合，随后加入一定量的二甲基甲酰胺，超声处理2小时，再将一定量的硝酸银加入混合液，继续超声处理，最后得到自制的银石墨烯纳米片；按照不同银石墨烯质量分数称量所需的钎料基体粉末，倒入球磨罐球磨5h，将粉末烘干之后放入不锈钢模具中，置于液压机下以500Mpa的压力压制成型，随后将冷压的圆柱体放入高真空管式电阻炉中在175℃下真空烧结2小时，冷却至室温后在液压机下冲成圆柱体。选用Ag粒子修饰的石墨烯作为强化材料，以提高纳米银修饰的石墨烯与Sn基体之间的载荷传递，从而达到更好的强化效果。

Description

一种锡基银石墨烯无铅复合钎料的制备方法 技术领域
本发明是关于复合钎料的制备，通过向传统的96.5Sn-3.0Ag-0.5Cu钎料添加银石墨烯纳米片，并使用球磨工艺制备复合钎料的方法。
背景技术
长期以来，锡铅合金焊料被广泛应用于电子行业中，其钎焊焊点是电子器件中不可缺少的关键部分，它们作为互连材料在电路器件间提供机械支持，电路导通与热传递通道，但是铅对人体健康和自然环境有潜在危害。另外随着微电子技术的发展，电子产品向小型化，便携化方向发展，这就使得电子封装的钎焊接头越来越密集，而电子产品运行时的单位体积发热量却越来越大，钎焊接头服役温度越来越高，传统的锡-铅合金由于抗蠕变性差，已经不能满足现代电子工业的要求。因此，开发性能更为优良的新的无铅钎料就显得很有必要。
人们从上世纪80年代开始在研究和发展电子应用中有关替代铅方面做出了共同的努力。现有技术比较成熟的无铅钎料主要包括：锡-铜、锡-银-铜、锡-锌等系列合金，而为了增强焊料的力学、热学以及电学性能，研究人员又采用复合材料技术，向传统钎料添加强化相，进一步提升钎料的性能。石墨烯具有良好的力学、电学和热学性质，可以成为传统焊料优良的增强相，其低密度和良好的结构稳定性，使其在复合焊料领域具有诱人的应用前景。
发明内容
为了改善石墨烯增强Sn基钎料存在的在基体中难以均匀分布且与金属基体结合强度较差的问题，本发明选用Ag粒子修饰的石墨烯作为强化材料，以提高纳米银修饰的石墨烯与Sn基体之间的载荷传递，从而达到更好的强化效果。本发明的目的是使用银石墨烯纳米片作为强化相，利用球磨工艺制备复合钎料，操作简单，混粉效果优良，通过测试复合钎料的力学性能、润湿性以及IMC层的生长情况，表明该制备方法所制备的银石墨烯复合钎料具有可靠的性能，应用前景值得期待。
为了解决上述技术问题，本发明提出一种锡基银石墨烯无铅复合钎料的制备方法，包括以下步骤：
步骤一、按照质量比为3：1称取石墨烯和十二烷基硫酸钠混合后为混合物A，用容 器量取二甲基甲酰胺，将混合物A加入到二甲基甲酰胺中获得混合液，其中，混合物A与二甲基甲酰胺的质量体积比为1：1，单位为mg/ml，将混合液超声处理2小时；
步骤二、将摩尔浓度为0.06mol/ml的硝酸银溶液加入步骤一的混合液中，其中硝酸银溶液的体积与二甲基甲酰胺体积比为1:2，超声处理30分钟，70℃加热1小时后过滤，依次水洗，酒精清洗，获得银石墨烯纳米片；
步骤三、以96.5Sn-3.0Ag-0.5Cu合金粉末作为基体材料，该基体材料的粒径为25-45μm；取适量银石墨烯纳米片作为强化相与基体材料混合后为混合物B，其中，银石墨烯纳米片的质量百分比为0.03～0.1％；
步骤四、将混合物B倒入行星式球磨罐，并加入一定量的乙醇，乙醇的加入量为刚好没过球磨罐中的混合物B和作为球磨介质的不锈钢球；密封抽真空，氩气作为保护气，以300r/min的转速运行5h，得到基体材料与银石墨烯纳米片充分混合的粉末；
步骤五、将步骤四混好的粉末烘干之后放入直径为20mm的不锈钢模具中，置于液压机下以500Mpa的压力单轴冷压成型；
步骤六、将步骤五冷压后的圆柱体放入高真空管式电阻炉中，在175℃下真空烧结2h，待冷却至室温后取出；
步骤七、将步骤六烧结后的圆柱体试样放入冲剂模具中，在液压机下冲剂成直径为6mm的圆柱体棒材，至此得到锡基银石墨烯无铅复合钎料。
进一步讲，上述步骤三中，银石墨烯纳米片的质量百分比的优选数值范围为0.03～0.05％，优选数值为0.05％。
与现有技术相比，本发明的有益效果是：
(1)利用银石墨烯纳米片(AG-GNSs)优异的力学、热学和电学性能，使其作为复合钎料的强化相，而纳米银颗粒镶嵌在石墨烯层片上，使得在与基体材料复合时缓解纳米银修饰的石墨烯的团聚，从而使复合后的材料成分更加均匀。同时细小的纳米银颗粒的加入也可以提高Sn基和纳米银修饰的石墨烯之间的载荷传递，从而进一步提高接头的可靠性，达到更好的强效果；(2)利用球磨法进行复合钎料的制备，球磨过程的机械能可诱发化学反应或者诱导材料组织、结构和性能发生变化，具有明显降低反应活化能、细化晶粒、极大的提高粉末活性和改善颗粒分布均匀性等优点。
附图说明
图1为传统的Sn-Ag-Cu无铅钎料与实施例1、实施例2、实施例3润湿角大小的对 比示意图；
图2为传统的Sn-Ag-Cu无铅钎料与实施例1、实施例2、实施例3抗拉强度的对比示意图；
图3(a)为传统的Sn-Ag-Cu无铅钎料回流焊后IMC层厚度示意图；
图3(b)为实施例1，即含有0.03％银石墨烯纳米银片(AG-GNSs)的锡基银石墨烯无铅复合钎料回流焊后IMC层厚度示意图；
图3(c)为实施例1，即含有0.05％银石墨烯纳米银片(AG-GNSs)的锡基银石墨烯无铅复合钎料回流焊后IMC层厚度示意图；
图3(d)为实施例3，即含有0.1％银石墨烯纳米银片(AG-GNSs)的锡基银石墨烯无铅复合钎料回流焊后IMC层厚度示意图。
具体实施方式
本发明的设计思路是选取纳米银颗粒修饰的石墨烯纳米片(AG-GNSs)作为强化相，纳米银颗粒镶嵌在石墨烯层片上，使得在与基体材料复合时缓解纳米银修饰的石墨烯的团聚，从而使复合后的材料成分更加均匀，以银石墨烯纳米片改善无铅钎料的性能。其中，采用球磨法可以制备超细材料，球磨过程的机械能可诱发化学反应或者诱导材料组织、结构和性能发生变化，具有明显降低反应活化能、细化晶粒、极大的提高粉末活性和改善颗粒分布均匀性等优点。
下面结合附图和具体实施例对本发明技术方案作进一步详细描述，所描述的具体实施例仅对本发明进行解释说明，并不用以限制本发明。
实施例1、制备锡基银石墨烯无铅复合钎料，步骤如下：
(1)用电子天平称取30mg石墨烯，10mg十二烷基硫酸钠，然后将其混合，用量筒量取40ml的二甲基甲酰胺，将混合好的30mg石墨烯与10mg的SDS(十二烷基硫酸钠)加入到40ml的DMF(二甲基甲酰胺)中，超声处理2小时。
(2)再用量筒量取20ml摩尔浓度为0.06mol/ml的硝酸银溶液，向其加入步骤(1)制得的混合液，超声处理30分钟，使石墨烯得到更好的修饰，再于70℃加热1小时后过滤，先水洗，后用酒精清洗，获得银石墨烯纳米片(AG-GNSs)。
(3)随后称取一定量的96.5Sn-3.0Ag-0.5Cu合金粉末与步骤(2)制备好的银石墨烯纳米银片(AG-GNSs)混合(以96.5Sn-3.0Ag-0.5Cu合金粉末作为基体材料，该基体材料的粒径为25-45μm)，在该混合的粉末中银石墨烯纳米片的质量分数为0.03％；
(4)将上述混合的粉末一起倒入行星式球磨罐，并加入不锈钢球(球磨介质)与一定量的乙醇(乙醇的加入量是刚好没过球磨罐中的不锈钢球和粉末)，密封抽真空并添加一定的高纯氩气作为保护气，随后以300r/min的转速运行5h，充分混合基体材料与强化相，使银石墨烯纳米片均匀分布在无铅焊料基体材料中。
(5)将步骤(4)混好的粉末烘干之后放入直径为20mm的不锈钢模具中，置于液压机下以500Mpa的压力单轴压制成型。
(6)将步骤(5)冷压后的圆柱体放入高真空管式电阻炉中，在175℃下真空烧结2h，待冷却至室温后取出；
(7)将上述烧结得到的圆柱体试样放入冲剂模具中，在液压机下冲剂成直径为6mm的圆柱体棒材，从而得到锡基银石墨烯无铅复合钎料。
实施例2、制备锡基银石墨烯无铅复合钎料，步骤与实施例1基本相同，其不同仅在于：步骤三中：将96.5Sn-3.0Ag-0.5Cu合金粉末与银石墨烯纳米银片(AG-GNSs)混合时，混合的粉末中银石墨烯纳米片的质量分数为0.05％。
实施例3、制备锡基银石墨烯无铅复合钎料，步骤与实施例1基本相同，其不同仅在于：步骤三中：将96.5Sn-3.0Ag-0.5Cu合金粉末与银石墨烯纳米银片(AG-GNSs)混合时，混合的粉末中银石墨烯纳米片的质量分数为0.1％。
图1为现有技术的Sn-Ag-Cu无铅焊料与实施例1、实施例2、实施例3通过银石墨烯纳米片增强无铅焊料的润湿角的对比示意图，由图1可以看出，随着银石墨烯纳米片质量分数的增加，润湿角也逐渐减小，由未添加时的40°减小到实施例3的22°。
图2为现有技术的Sn-Ag-Cu无铅焊料与实施例1、实施例2通过银石墨烯纳米片增强无铅焊料的抗拉强度值的对比示意图。由图2可以看出，银石墨烯纳米片的添加，使得复合钎料的抗拉强度提升，当添加的银石墨烯纳米片质量分数为0.05％时，抗拉强度比不添加提高最为显著，提高幅度可达14.8％。
图3为现有技术的Sn-Ag-Cu无铅焊料与实施例1、实施例2、实施例3银石墨烯纳米片增强无铅焊料的回流焊后IMC厚度情况的对比示意图。由图3可以看出，随着银石墨烯纳米片质量分数的增加，IMC层逐渐减小，说明银石墨烯纳米片对IMC的形成起到了良好的抑制作用。
结合实施例1、实施例2及实施例3可以看出，当银石墨烯纳米片含量由0.03％增长到0.1％时，复合钎料的力学性能、润湿性能以及IMC生长情况与未添加相比都有改善， 但是当其含量增至0.1％后，相对于0.05％含量的银石墨烯纳米片并未有显著提高，甚至在拉伸性能方面略有下降，因此，本发明建议使用银石墨烯纳米片的质量分数为0.03～0.05％，优选为0.05％。
尽管上面结合附图对本发明进行了描述，但是本发明并不局限于上述的具体实施方式，上述的具体实施方式仅仅是示意性的，而不是限制性的，本领域的普通技术人员在本发明的启示下，在不脱离本发明宗旨的情况下，还可以做出很多变形，这些均属于本发明的保护之内。

Claims (4)

  1. 一种锡基银石墨烯无铅复合钎料的制备方法，其特征在于：包括以下步骤：
    步骤一、按照质量比为3：1称取石墨烯和十二烷基硫酸钠混合后为混合物A，用容器量取二甲基甲酰胺，将混合物A加入到二甲基甲酰胺中获得混合液，其中，混合物A与二甲基甲酰胺的质量体积比为1：1，单位为mg/ml，将混合液超声处理2小时；
    步骤二、将摩尔浓度为0.06mol/ml的硝酸银溶液加入步骤一的混合液中，其中硝酸银溶液的体积与二甲基甲酰胺体积比为1:2，超声处理30分钟，70℃加热1小时后过滤，依次水洗，酒精清洗，获得银石墨烯纳米片；
    步骤三、以96.5Sn-3.0Ag-0.5Cu合金粉末作为基体材料，该基体材料的粒径为25-45μm；取适量银石墨烯纳米片作为强化相与基体材料混合后为混合物B，其中，银石墨烯纳米片的质量百分比为0.03～0.1％；
    步骤四、将混合物B倒入行星式球磨罐，并加入一定量的乙醇，乙醇的加入量为刚好没过球磨罐中的混合物B和作为球磨介质的不锈钢球；密封抽真空，氩气作为保护气，以300r/min的转速运行5h，得到基体材料与银石墨烯纳米片充分混合的粉末；
    步骤五、将步骤四混好的粉末烘干之后放入直径为20mm的不锈钢模具中，置于液压机下以500Mpa的压力单轴冷压成型；
    步骤六、将步骤五冷压后的圆柱体放入高真空管式电阻炉中，在175℃下真空烧结2h，待冷却至室温后取出；
    步骤七、将步骤六烧结后的圆柱体试样放入冲剂模具中，在液压机下冲剂成直径为6mm的圆柱体棒材，至此得到锡基银石墨烯无铅复合钎料。
  2. 根据权利要求1所述锡基银石墨烯无铅复合钎料的制备方法，其特征在于：步骤三中，所述银石墨烯纳米片的质量百分比为0.03～0.05％。
  3. 根据权利要求2所述锡基银石墨烯无铅复合钎料的制备方法，其特征在于：步骤三中，所述银石墨烯纳米片的质量百分比为0.03％。
  4. 根据权利要求2所述锡基银石墨烯无铅复合钎料的制备方法，其特征在于：步骤三中，所述银石墨烯纳米片的质量百分比为0.05％。
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