CN114871634A - 一种铜磷锡钎料丝及其制备方法 - Google Patents

一种铜磷锡钎料丝及其制备方法 Download PDF

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Publication number
CN114871634A
CN114871634A CN202210677638.3A CN202210677638A CN114871634A CN 114871634 A CN114871634 A CN 114871634A CN 202210677638 A CN202210677638 A CN 202210677638A CN 114871634 A CN114871634 A CN 114871634A
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China
Prior art keywords
copper
wire
solder wire
layer
phosphorus
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CN202210677638.3A
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CN114871634B (zh
Inventor
钟素娟
纠永涛
程亚芳
黄俊兰
丁天然
张冠星
路全彬
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Zhengzhou Research Institute of Mechanical Engineering Co Ltd
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Zhengzhou Research Institute of Mechanical Engineering Co Ltd
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Priority to CN202210677638.3A priority Critical patent/CN114871634B/zh
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Priority to US18/169,192 priority patent/US11931828B2/en
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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
    • B23K35/22—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
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/302—Cu 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
    • B23K35/02—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, brazing
    • B23K35/0227—Rods, 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
    • B23K35/0255—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in welding
    • B23K35/0261—Rods, electrodes, 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
    • B23K35/0255—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in welding
    • B23K35/0261—Rods, electrodes, wires
    • B23K35/0272—Rods, electrodes, wires with more than one layer of coating or sheathing material
    • 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
    • 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, fluxes; Selection of soldering or welding materials, conjoint with selection of non-metallic compositions, both selections being of interest
    • B23K35/365—Selection of non-metallic compositions of coating materials either alone or conjoint with selection of soldering or welding materials
    • 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
    • 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
    • B23K35/404—Coated rods; Coated electrodes
    • 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
    • B23K35/406—Filled tubular wire or rods
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
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    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/02—Layer formed of wires, e.g. mesh
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/043—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/02—Alloys based on copper with tin as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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Abstract

本发明提供了一种铜磷锡钎料丝及其制备方法，涉及钎焊材料技术领域。所述铜磷锡钎料丝为三层结构，内层为Cu，中间层为Cu‑14P合金，外层为Sn；其中Sn的质量百分比为7％以上。解决了现有技术中存在的铜磷银钎料焊接铜合金时易产生气孔、夹杂等缺欠，导致接头的力学性能下降的技术问题，同时提供了所述铜磷锡钎料丝的制备方法，解决了Sn含量较高情况下难以获得丝径在0.5mm以下的铜磷锡钎料丝的技术问题。

Description

一种铜磷锡钎料丝及其制备方法
技术领域
本发明涉及钎焊材料技术领域，尤其是涉及一种铜磷锡钎料丝及其制备方法。
背景技术
BCu89PAg和BCu91PAg是目前空调、制冷行业中钎焊黄铜或紫铜用量较大的两种铜磷银钎料。随着银的价格越来越高，这两种钎料消耗较多的贵金属银，导致空调、制冷、机械、电器、阀门管件等行业生产成本大幅提高。为降低成本，研制环保型的无银铜磷钎料是国内外钎焊领域研究热点。
目前，铜磷锡钎料是无银铜磷钎料的最新技术成果。为节约银，在铜磷钎料中加入Sn，可显著降低钎料的熔化温度。然而，铜磷钎料中Cu3P脆性相本就较多，随着Sn含量增加(大于4％)，钎料会进一步形成CuSn脆性相，进一步恶化钎料的加工性能，常规制备方法很难获得丝径在0.5mm以下的铜磷锡钎料丝。
另外，现有铜磷银钎料焊接铜合金时易产生气孔、夹杂等缺欠，导致接头的力学性能下降。
为了解决上述不足，需要开发一种用于铜及铜合金钎焊时缺欠少，钎焊质量好的铜磷锡钎料丝；同时需要开发一种铜磷锡钎料丝的制备技术以获得较细丝径的铜磷锡钎料丝。
鉴于此，特提出本发明。
发明内容
本发明的目的在于提供一种铜磷锡钎料丝及其制备方法，以解决现有技术中存在的铜磷银钎料焊接铜合金时易产生气孔、夹杂等缺欠，导致接头的力学性能下降的技术问题，同时解决Sn含量较高情况下难以获得丝径在0.5mm以下的铜磷锡钎料丝的技术问题。
本发明提供的技术方案如下：
在一个方面，本发明提供了一种铜磷锡钎料丝，所述钎料丝为三层结构，内层为Cu，中间层为Cu-14P合金，外层为Sn；其中Sn的质量百分比为7％以上。
本发明铜磷锡钎料丝的熔化温度低、流动性能好。
在一个实施方案中，所述钎料丝中各元素质量比为Cu：P：Sn＝86：7：7。所述Cu-14P合金中P的质量百分比为14％。
经本发明实验发现，当Cu：P：Sn为86：7：7的固定比例时，钎料的综合性能是最佳的。
在一个实施方案中，所述钎料丝中Cu：Cu14P：Sn各层的质量比为43：50：7。
在一个实施方案中，所述铜磷锡钎料丝的丝径为0.5mm以下，优选为0.1～0.5mm。
本发明铜磷锡钎料丝的丝径较细，为0.1～0.5mm，适于铜及铜合金的钎焊。
在另一个方面，本发明提供了一种铜磷锡钎料丝的制备方法，包括以下步骤：
(a)取Cu丝，根据Cu丝质量和以及钎料丝中Cu、P、Sn元素质量比，算出Cu、Cu-14P合金、Sn的质量以及所需Cu-14P层和Sn层厚度；
(b)取Cu-14P合金加热熔炼成Cu-14P合金液；
(c)取Sn加热熔炼成Sn金属液；
(d)将步骤(a)的所述Cu丝以第一速度穿过Cu-14P合金液，再以第二速度穿过Sn金属液；
(e)将从Sn金属液出来的钎料丝通过整形模，收卷得到铜磷锡钎料丝。
在一个实施方案中，Cu丝的直径、Cu-14P合金层厚度、Sn层厚度三者比值固定。在本发明中，取一定直径的Cu丝，根据铜丝的直径、长度和密度计算出Cu丝质量。根据Cu丝的质量，以及设定的以及钎料丝中Cu、P、Sn元素质量比(例如Cu：P：Sn＝86：7：7)算出Cu、Cu-14P合金、Sn的质量以及所需Cu-14P层和Sn层厚度。
在一个实施方案中，所述Cu、Cu-14P合金、Sn的质量比为43：50：根据采用的Cu丝的质量，算出Cu、Cu-14P合金、Sn的质量，然后算出所需Cu-14P层和Sn层厚度。
在一个实施方案中，取适量Cu-14P合金置于坩埚内部，加热到一定温度，熔炼成Cu-14P合金液备用；取适量Sn置于坩埚内部，加热到一定温度，熔炼成Sn金属液备用。将Cu丝以较低一定速度(第一速度)穿过Cu-14P合金液，再以一定速度(第二速度)穿过Sn金属液，最后通过整形模具，收卷得到铜磷锡钎料丝。
在一个实施方案中，取Cu-14P合金加热熔炼成Cu-14P合金液，在该步骤(b)中加热至温度为900℃～980℃，包括920℃～960℃，例如但不限于900℃、920℃、930℃、940℃、950℃、960℃和980℃。
在一个实施方案中，取Sn加热熔炼成Sn金属液，在该步骤中加热至温度为220℃～250℃，例如但不限于220℃、225℃、230℃、235℃、240℃、245℃和250℃。
在一个实施方案中，穿过Cu-14P合金液的速度小于穿过Sn金属液的速度，具体地，所述第一速度为10-20mm/s，所述第二速度为20-30mm/s。
在一个实施方案中，整形模材质为YG8。
在另一个方面，本发明还提供了所述铜磷锡钎料丝在铜及铜合金钎焊中的应用，如黄铜-紫铜分液器的钎焊中的应用。
有益效果：
本发明利用紫铜的高塑性，基于Cu14P对紫铜的自钎、润湿性能及Cu14P合金与Sn液间的浸润性能，将三者合金化成一体，形成丝径0.5mm以下的铜磷锡钎料丝，本发明的铜磷锡钎料丝的熔化温度较低(可达645-660℃)、流动性能好；
本发明的铜磷锡钎料丝用于铜及铜合金钎焊时，钎缝缺欠少、钎焊质量稳定；
本方明制备获得了Sn含量更高且丝径在0.5mm以下的铜磷锡钎料丝，克服了传统制备方法的技术局限。
附图说明
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本发明结构示意图；
图2为本发明制备工艺流程图(图中序号1、紫铜丝；2、感应线圈1；3、导轮1；4、导轮2；5、Cu14P液；6、导轮3；7、石墨坩埚；8、导轮4；9、导轮5；10、Sn液；11、导轮6；12、感应线圈2)；
图3为本发明实施例1钎料与传统钎料的铺展润湿试验的对比铺展形貌；
图4为BCu91PAg和实施例1的钎料的钎焊接头宏观形貌；
图5为BCu91PAg和实施例1的钎料的钎缝刨切形貌。
具体实施方式
下面将结合实施例对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
一种铜磷锡钎料丝，所述钎料丝由三层结构组成，内层为Cu，中间层为Cu-14P合金，外层为Sn。
所述钎料丝中各元素质量比Cu：P：Sn＝86：7：7。
所述钎料丝中各层质量比Cu：Cu14P：Sn为43：50：7。
如上所述铜磷锡钎料丝的制备方法，包括以下步骤：
步骤(1)：取一直径0.05mm的Cu丝4.3kg，根据铜丝质量和三者质量份数，分别算出Cu-14P、Sn的质量；根据密度，算出Cu丝所需Cu-14P层厚度为0.0475mm和Sn层厚度为0.0025mm；其中，步骤(1)所述Cu丝直径、Cu-14P层厚度、Sn层厚度三者比值一定；
步骤(2)：取适量Cu-14P合金置于坩埚内部，加热至一定温度(980℃)，熔炼成Cu-14P合金液备用；
步骤(3)：取适量Sn置于坩埚内部，加热至一定温度(250℃)，熔炼成Sn金属液备用；
步骤(4)：将步骤(1)的Cu丝以较低速度(20mm/s)穿过Cu-14P合金液，再以较高速度(30mm/s)穿过Sn金属液；
步骤(5)：从Sn液出来的钎料丝通过YG8整形模，收卷得到10Kg的直径约0.1mm的铜磷锡钎料丝。
图1为本发明千里奥斯的结构示意图；其中1为Sn层，10为Cu-14P层，5为Cu层。
图2为本发明的制备工艺流程图，其中图中序号表示：1、紫铜丝；2、感应线圈1；3、导轮1；4、导轮2；5、Cu14P液；6、导轮3；7、石墨坩埚；8、导轮4；9、导轮5；10、Sn液；11、导轮6；12、感应线圈2。本发明的制备方法中，Cu丝以较低速度穿过Cu-14P合金液(即Cu14P液)，再以较高速度穿过Sn金属液(即Sn液)，从Sn液出来的钎料丝通过YG8整形模，收卷得到铜磷锡钎料丝。
实施例2
本发明钎料成分、结构、制备方法均与实施例1相同。
与实施例1不同的是步骤(1)中所述Cu丝直径为0.1mm，Cu-14P层厚度为0.095mm，Sn层厚度为0.005mm。
步骤(2)所述的一定温度为960℃，步骤(3)所述的一定温度为240℃。
步骤(4)所述的较低速度为16mm/s，较高速度为28mm/s。
步骤(5)所述钎料丝直径约为0.2mm。
实施例3
本发明钎料成分、结构、制备方法均与实施例1相同。
与实施例1不同的是步骤(1)中所述Cu丝直径为0.15mm，Cu-14P层厚度为0.1425mm，Sn层厚度为0.0075mm。
步骤(2)所述的一定温度为940℃，步骤(3)所述的一定温度为230℃。
步骤(4)所述的较低速度为14mm/s，较高速度为26mm/s。
步骤(5)所述钎料丝直径约为0.3mm。
实施例4
本发明钎料成分、结构、制备方法均与实施例1相同。
与实施例1不同的是步骤(1)中所述Cu丝直径为0.2mm，Cu-14P层厚度为0.19mm，Sn层厚度为0.01mm。
步骤(2)所述的一定温度为920℃，步骤(3)所述的一定温度为235℃。
步骤(4)所述的较低速度为12mm/s，较高速度为22mm/s。
步骤(5)所述钎料丝直径约为0.4mm。
实施例5
本发明钎料成分、结构、制备方法均与实施例1相同。
与实施例1不同的是步骤(1)中所述Cu丝直径为0.25mm，Cu-14P层厚度为0.2375mm，Sn层厚度为0.0125mm。
步骤(2)所述的一定温度为900℃，步骤(3)所述的一定温度为220℃。
步骤(4)所述的较低速度为10mm/s，较高速度为20mm/s。
步骤(5)所述钎料丝直径约为0.5mm。
对比例1
为考察本发明铜磷锡钎料丝与传统铜磷银钎料的钎焊工艺性能，采用DTA热分析法对实施例钎料丝与传统BCu89PAg和BCu91PAg进行熔化温度测试，测试结果见下表，并按照GB/T11364的方法进行了实施例1钎料与传统钎料的铺展润湿试验，对比铺展形貌。
表1.钎料熔化温度测试结果
Figure BDA0003695367140000071
Figure BDA0003695367140000081
从表1可以看出，与传统铜磷银钎料相比，实施例中各钎料的熔化温度，特别是液相线温度，降低到660℃以下，降低了约150℃。
图3示出了不同钎料在黄铜上的铺展形貌(750℃)。从图3的铺展形貌对比可以看出，在同样的试验温度下(750℃)，实施例1的钎料的熔化温度低，铺展面积大，而传统钎料的熔化温度高，在该温度下钎料还没完全熔化，铺展面积较小。
其他实施例的钎焊工艺性能与实施例1类似，结果未一一示出。
对比例2
为考察实施例钎料与传统铜磷钎料的钎焊效果，采用实施例1的钎料与传统铜磷银钎料分别钎焊黄铜-紫铜分液器的钎焊，焊后锯开，观察焊缝的填缝情况，并估算钎缝钎着率(在刨切面上，有效填缝长度/名义填缝长度)。
图4示出了BCu91PAg和实施例1的钎料的宏观形貌；图5示出了BCu91PAg和实施例1的钎料的钎缝刨切形貌。表2使出了不同钎料填缝的情况。
表2.不同钎料填缝情况
Figure BDA0003695367140000082
Figure BDA0003695367140000091
从图5及表2可以看出，传统铜磷银钎料钎缝中有较多的气孔、夹杂等缺欠，实施例的钎料钎缝中的缺欠较少，整体钎焊质量较好，钎着率在89％以上。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。

Claims (10)

1.一种铜磷锡钎料丝，其特征在于，所述钎料丝为三层结构，内层为Cu，中间层为Cu-14P合金，外层为Sn；其中Sn的质量百分比为7％以上。
2.根据权利要求1所述的铜磷锡钎料丝，其特征在于，所述钎料丝中各元素质量比为Cu：P：Sn＝86：7：7。
3.根据权利要求1所述的铜磷锡钎料丝，其特征在于，所述钎料丝中Cu：Cu14P：Sn各层的质量比为43：50：7。
4.根据权利要求1-3中任一项所述的铜磷锡钎料丝，其特征在于，所述钎料丝的丝径为0.5mm以下，优选为0.1～0.5mm。
5.一种权利要求1所述铜磷锡钎料丝的制备方法，其特征在于，包括以下步骤：
(a)取Cu丝，根据Cu丝质量和以及钎料丝中Cu、P、Sn元素质量比，算出Cu、Cu-14P合金、Sn的质量以及所需Cu-14P层和Sn层厚度；
(b)取Cu-14P合金加热熔炼成Cu-14P合金液；
(c)取Sn加热熔炼成Sn金属液；
(d)将步骤(a)的所述Cu丝以第一速度穿过Cu-14P合金液，再以第二速度穿过Sn金属液；
(e)将从Sn金属液出来的钎料丝通过整形模，收卷得到铜磷锡钎料丝。
6.根据权利要求5所述的制备方法，其特征在于，Cu丝的直径、Cu-14合金层厚度、Sn层厚度三者比值固定。
7.根据权利要求5所述的制备方法，其特征在于，所述步骤(b)中加热至温度为900～980℃。
8.根据权利要求5所述的制备方法，其特征在于，所述步骤(c)中加热至温度为220～250℃。
9.根据权利要求5所述的制备方法，其特征在于，所述第一速度为10-20mm/s，所述第二速度为20-30mm/s。
10.根据权利要求5所述的制备方法，其特征在于，整形模材质为YG8。
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