Raw material composition of brazing filler metal, brazing filler metal and preparation method and application of brazing filler metal
By optimizing the raw material composition of tin-zinc solder and adopting a specific preparation process, the problems of poor wettability and oxidation resistance of lead-free tin-zinc solder have been solved, and a high-performance solder suitable for electronic packaging has been prepared.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- JINLONG RARE EARTH INNOVATION TECHNOLOGY (XIAMEN) CO LTD
- Filing Date
- 2025-12-11
- Publication Date
- 2026-04-10
AI Technical Summary
Lead-free tin-zinc solders have poor wettability and weak oxidation resistance in circuit boards, which limits their large-scale application.
The raw material composition of tin-zinc brazing filler metal is optimized by adding one or more of copper, rare earth elements, and specific additives such as chromium, titanium, antimony, aluminum, nickel, bismuth, phosphorus, and silver. The preparation process includes smelting, solidification and molding, and possibly stirring, heat preservation, extrusion, rolling, and drawing to form filamentous brazing filler metal.
The prepared solder has excellent wetting and oxidation resistance properties, with a spreading area greater than 60 mm², a wetting angle less than 35°, and an oxidation rate less than 0.18*10⁻¹⁰, making it suitable for electronic packaging applications.
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Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to a raw material composition of a brazing filler metal, a brazing filler metal and a preparation method and application thereof. BACKGROUND
[0002] With the development of the field of electronic packaging, electronic components are gradually miniaturized and the packaging density is increasing, which leads to the continuous reduction of the interconnection point pitch, thus higher requirements are put forward for the wettability of the brazing filler metal in the electronic packaging process. Tin-based soft brazing filler metal is the most widely used brazing filler metal in the market due to its good wettability, strong plasticity and excellent corrosion resistance in the connection of circuit board components. Compared with other tin-based brazing filler metals such as tin-silver-copper and tin-copper, tin-zinc brazing filler metal has the advantages of low cost and rich resources. However, compared with other lead-free brazing filler metals, tin-zinc brazing filler metal has the disadvantages of poor solder joint wettability and weak oxidation resistance formed on the circuit board during use. Therefore, how to improve the wettability and oxidation resistance of lead-free tin-zinc brazing filler metal is the bottleneck for the large-scale application of tin-zinc brazing filler metal. SUMMARY
[0003] In order to solve the problem of poor wettability and oxidation resistance of lead-free tin-zinc brazing filler metal in the prior art, a raw material composition of a brazing filler metal, a brazing filler metal and a preparation method and application thereof are provided. The brazing filler metal prepared from the raw material composition of the brazing filler metal can have excellent wettability and oxidation resistance at the same time.
[0004] The present application solves the above technical problems by the following technical solutions.
[0005] The present application provides a raw material composition of a brazing filler metal, which comprises a main component, wherein the main component comprises tin (Sn) and zinc (Zn).
[0006] The raw material composition further comprises copper (Cu), rare earth elements and additive elements.
[0007] The additive elements comprise one or more of chromium (Cr), titanium (Ti), antimony (Sb), aluminum (Al), nickel (Ni), bismuth (Bi), indium (In), phosphorus (P) and silver (Ag).
[0008] The mass content of zinc is 5%-30%, the mass content of copper is less than 1%, and the mass content of rare earth elements is 0.01%-1%.
[0009] In the present application, the mass content refers to the mass percentage of the element in the raw material composition. For example, the mass content of zinc refers to the mass percentage of zinc in the raw material composition.
[0010] In the present application, preferably, the mass content of tin is 80-90%, more preferably 80-85%, for example 81.55% or 84.55%.
[0011] In the present application, preferably, the mass content of zinc is 10-25%, more preferably 12-25%, for example 15%, 16%, 17%, 18%, 19% or 20%.
[0012] In the present application, preferably, the mass content of copper is 0.3% or less, more preferably 0.25% or less, for example 0.05%, 0.1%, 0.2% or 0.25%.
[0013] In the present application, preferably, the mass content of rare earth elements is 0.05-1%, more preferably 0.1-0.5%, for example 0.2%, 0.3% or 0.4%.
[0014] In the present application, preferably, the mass content of the additive elements is 5% or less, more preferably 4% or less, for example 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 1%, 2%, 3% or 3.2%.
[0015] In the present application, preferably, the mass content of chromium is 0.01-1%, more preferably 0.05-0.5%, for example 0.1%, 0.2%, 0.3% or 0.4%.
[0016] In the present application, preferably, the mass content of titanium is 0.01-1%, more preferably 0.05-0.5%, for example 0.1%, 0.2%, 0.3% or 0.4%.
[0017] In the present application, preferably, the mass content of antimony is 1% or less, more preferably 0.05-0.5%, for example 0.1%, 0.2%, 0.3% or 0.4%.
[0018] In the present application, preferably, the mass content of aluminum is 0.01-1%, more preferably 0.05-0.5%, for example 0.1%, 0.2%, 0.3% or 0.4%.
[0019] In the present application, preferably, the mass content of nickel is 0.01-1%, more preferably 0.05-0.5%, for example 0.1%, 0.2%, 0.3% or 0.4%.
[0020] In the present application, preferably, the mass content of bismuth is 0.01-1%, more preferably 0.05-0.5%, for example 0.1%, 0.2%, 0.3% or 0.4%.
[0021] In this invention, preferably, the indium content is 0.01%-1%, more preferably 0.05%-0.5%, for example 0.1%, 0.2%, 0.3% or 0.4%.
[0022] Optionally, the rare earth elements in this invention include one or more of the lanthanides, scandium, and yttrium.
[0023] The lanthanide elements include one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.
[0024] In this invention, preferably, the rare earth element is lanthanum.
[0025] Preferably, the lanthanum content is 0.01%-1%, more preferably 0.05%-0.5%, for example 0.1% or 0.2%.
[0026] In this invention, preferably, the rare earth elements are lanthanum and cerium.
[0027] Preferably, the lanthanum content is 0.01%-1% by mass, and the cerium content is 0.01%-1% by mass; more preferably, the lanthanum content is 0.05%-0.5% by mass, and the cerium content is 0.05%-0.5% by mass.
[0028] The lanthanum content is, for example, 0.2% by mass, and the cerium content is, for example, 0.2% by mass.
[0029] In this invention, preferably, the rare earth elements are lanthanum and ytterbium.
[0030] Preferably, the lanthanum content is 0.01%-1% by mass, and the ytterbium content is 0.01%-1% by mass; more preferably, the lanthanum content is 0.05%-0.5% by mass, and the ytterbium content is 0.05%-0.5% by mass.
[0031] The lanthanum content is, for example, 0.2% by mass, and the ytterbium content is, for example, 0.2% by mass.
[0032] In this invention, preferably, the added element is phosphorus.
[0033] Preferably, the phosphorus content is less than 1%, preferably 0.05%-0.5%, for example 0.1%, 0.2%, 0.3% or 0.4%.
[0034] In this invention, preferably, the added element is silver.
[0035] Preferably, the silver content is 3% or less by mass, more preferably 1% to 3% or less, for example 3%.
[0036] In the present application, preferably, the additive element is silver and chromium.
[0037] Preferably, the mass content of silver is 3% or less, and the mass content of chromium is 0.01%-1%; preferably, the mass content of silver is 1%-3%, and the mass content of chromium is 0.05%-0.5%.
[0038] Preferably, the mass content of silver is 3%, and the mass content of chromium is 0.2%.
[0039] In the present application, preferably, the additive element is silver and titanium.
[0040] Preferably, the mass content of silver is 3% or less, and the mass content of titanium is 0.01%-1%; preferably, the mass content of silver is 1%-3%, and the mass content of titanium is 0.05%-0.5%.
[0041] Preferably, the mass content of silver is 3%, and the mass content of titanium is 0.2%.
[0042] In the present application, preferably, the additive element is silver and antimony.
[0043] Preferably, the mass content of silver is 3% or less, and the mass content of antimony is 0.01%-1%; preferably, the mass content of silver is 1%-3%, and the mass content of antimony is 0.05%-0.5%.
[0044] Preferably, the mass content of silver is 3%, and the mass content of antimony is 0.2%.
[0045] In the present application, preferably, the additive element is silver and nickel.
[0046] Preferably, the mass content of silver is 3% or less, and the mass content of nickel is 0.01%-1%; preferably, the mass content of silver is 1%-3%, and the mass content of nickel is 0.05%-0.5%.
[0047] Preferably, the mass content of silver is 3%, and the mass content of nickel is 0.2%.
[0048] In the present application, preferably, the additive element is silver and bismuth.
[0049] Preferably, the mass content of silver is 3% or less, and the mass content of bismuth is 0.01%-1%; preferably, the mass content of silver is 1%-3%, and the mass content of bismuth is 0.05%-0.5%.
[0050] wherein preferably the silver content is 3% by mass and the bismuth content is 0.2% by mass.
[0051] In the present application, the raw material composition can optionally further include an impurity element.
[0052] wherein the impurity element can be one or more of sulfur, iron, manganese, carbon, lead, cadmium, arsenic, and oxygen.
[0053] wherein the impurity element has a content of 0.1% by mass or less.
[0054] In one embodiment, the raw material composition consists of tin, zinc, copper, lanthanum, and phosphorus.
[0055] wherein, for example, the zinc content is 15% by mass, the copper content is 0.25% by mass, the lanthanum content is 0.1% by mass, the phosphorus content is 0.1% by mass, and the remainder is tin.
[0056] In one embodiment, the raw material composition consists of tin, zinc, copper, lanthanum, cerium, and silver.
[0057] wherein, for example, the zinc content is 15% by mass, the copper content is 0.05% by mass, the lanthanum content is 0.2% by mass, the cerium content is 0.2% by mass, the silver content is 3% by mass, and the remainder is tin.
[0058] In one embodiment, the raw material composition consists of tin, zinc, copper, lanthanum, ytterbium, and silver.
[0059] wherein, for example, the zinc content is 15% by mass, the copper content is 0.05% by mass, the lanthanum content is 0.2% by mass, the ytterbium content is 0.2% by mass, the silver content is 3% by mass, and the remainder is tin.
[0060] In one embodiment, the raw material composition consists of tin, zinc, copper, lanthanum, chromium, and silver.
[0061] wherein, for example, the zinc content is 15% by mass, the copper content is 0.05% by mass, the lanthanum content is 0.2% by mass, the chromium content is 0.2% by mass, the silver content is 3% by mass, and the remainder is tin.
[0062] In one embodiment, the raw material composition consists of tin, zinc, copper, lanthanum, titanium, and silver.
[0063] wherein, for example, the mass content of the zinc is 15%, the mass content of the copper is 0.05%, the mass content of the lanthanum is 0.2%, the mass content of the titanium is 0.2%, the mass content of the silver is 3%, and the balance is tin.
[0064] In a specific embodiment, the raw material composition consists of tin, zinc, copper, lanthanum, antimony, and silver.
[0065] wherein, for example, the mass content of the zinc is 15%, the mass content of the copper is 0.05%, the mass content of the lanthanum is 0.2%, the mass content of the antimony is 0.2%, the mass content of the silver is 3%, and the balance is tin.
[0066] In a specific embodiment, the raw material composition consists of tin, zinc, copper, lanthanum, nickel, and silver.
[0067] wherein, for example, the mass content of the zinc is 15%, the mass content of the copper is 0.05%, the mass content of the lanthanum is 0.2%, the mass content of the nickel is 0.2%, the mass content of the silver is 3%, and the balance is tin.
[0068] In a specific embodiment, the raw material composition consists of tin, zinc, copper, lanthanum, bismuth, and silver.
[0069] wherein, for example, the mass content of the zinc is 15%, the mass content of the copper is 0.05%, the mass content of the lanthanum is 0.2%, the mass content of the bismuth is 0.2%, the mass content of the silver is 3%, and the balance is tin.
[0070] The present application also provides a method for producing a brazing material, comprising the steps of:
[0071] The raw material composition of the brazing material as described above is subjected to melting and solidification molding in this order to obtain the brazing material.
[0072] In the present application, preferably, the pressure of the melting is 1 MPa or less, more preferably 0.5 MPa or less, for example, 0.1 MPa.
[0073] In the present application, preferably, the temperature of the melting is 500 to 800°C, more preferably 500 to 700°C, for example, 600°C.
[0074] In the present application, preferably, the time of the melting is 30 min to 90 min, more preferably 40 to 80 min, for example, 60 min.
[0075] In the present application, preferably, the melting is performed in a vacuum medium frequency furnace.
[0076] In the present application, preferably, the melting is performed in an argon atmosphere.
[0077] Optionally, the argon atmosphere is formed by the following steps: vacuumizing first, and then introducing argon to form the argon atmosphere.
[0078] Preferably, the method further comprises a stirring step after the melting and before the solidification forming.
[0079] Preferably, the stirring speed is 50-100 r / min, preferably 60-90 r / min, for example 70 r / min or 80 r / min.
[0080] Preferably, the stirring time is 5-10 min.
[0081] Preferably, the method further comprises a holding stage after the stirring, and the holding stage has a temperature of 500-800℃, for example 600℃.
[0082] In the present application, the solidification forming is naturally cooled at room temperature.
[0083] Preferably, the method further comprises the steps of extruding, rolling and drawing into wire after the solidification forming, to obtain the solder.
[0084] The present application also provides a solder prepared by the method for preparing the solder.
[0085] Preferably, the solder is in the form of wire.
[0086] Preferably, the diameter of the solder is 0.8-1.2 mm, for example 1 mm.
[0087] The present application also provides a solder, which comprises a main component, and the main component comprises tin (Sn), zinc (Zn);
[0088] The solder further comprises copper (Cu), rare earth elements and additive elements.
[0089] The additive elements comprise one or more of chromium (Cr), titanium (Ti), antimony (Sb), aluminum (Al), nickel (Ni), bismuth (Bi), indium (In), phosphorus (P) and silver (Ag).
[0090] Preferably, the mass content of zinc is 5%-30%, the mass content of copper is less than 1%, and the mass content of rare earth elements is 0.01%-1%.
[0091] In the present application, the mass content refers to the mass percentage of the element in the solder, for example, the mass content of zinc refers to the mass percentage of zinc in the solder.
[0092] In the present application, preferably, the mass content of tin is 80-90%, more preferably 80-85%, for example 81.55% or 84.55%.
[0093] In the present application, preferably, the mass content of zinc is 10-25%, more preferably 12-25%, for example 15%, 16%, 17%, 18%, 19% or 20%.
[0094] In the present application, preferably, the mass content of copper is 0.3% or less, more preferably 0.25% or less, for example 0.05%, 0.1%, 0.2% or 0.25%.
[0095] In the present application, preferably, the mass content of rare earth elements is 0.05-1%, more preferably 0.1-0.5%, for example 0.2%, 0.3% or 0.4%.
[0096] In the present application, preferably, the mass content of additive elements is 5% or less, more preferably 4% or less, for example 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 1%, 2%, 3% or 3.2%.
[0097] In the present application, preferably, the mass content of chromium is 0.01-1%, more preferably 0.05-0.5%, for example 0.1%, 0.2%, 0.3% or 0.4%.
[0098] In the present application, preferably, the mass content of titanium is 0.01-1%, more preferably 0.05-0.5%, for example 0.1%, 0.2%, 0.3% or 0.4%.
[0099] In the present application, preferably, the mass content of antimony is 1% or less, more preferably 0.05-0.5%, for example 0.1%, 0.2%, 0.3% or 0.4%.
[0100] In the present application, preferably, the mass content of aluminum is 0.01-1%, more preferably 0.05-0.5%, for example 0.1%, 0.2%, 0.3% or 0.4%.
[0101] In the present application, preferably, the mass content of nickel is 0.01-1%, more preferably 0.05-0.5%, for example 0.1%, 0.2%, 0.3% or 0.4%.
[0102] In the present application, preferably, the mass content of bismuth is 0.01-1%, more preferably 0.05-0.5%, for example 0.1%, 0.2%, 0.3% or 0.4%.
[0103] In this invention, preferably, the indium content is 0.01%-1%, more preferably 0.05%-0.5%, for example 0.1%, 0.2%, 0.3% or 0.4%.
[0104] Optionally, the rare earth elements in this invention include one or more of the lanthanides, scandium, and yttrium.
[0105] The lanthanide elements include one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.
[0106] In this invention, preferably, the rare earth element is lanthanum.
[0107] Preferably, the lanthanum content is 0.01%-1%, more preferably 0.05%-0.5%, for example 0.1% or 0.2%.
[0108] In this invention, preferably, the rare earth elements are lanthanum and cerium.
[0109] Preferably, the lanthanum content is 0.01%-1% by mass, and the cerium content is 0.01%-1% by mass; more preferably, the lanthanum content is 0.05%-0.5% by mass, and the cerium content is 0.05%-0.5% by mass.
[0110] The lanthanum content is, for example, 0.2% by mass, and the cerium content is, for example, 0.2% by mass.
[0111] In this invention, preferably, the rare earth elements are lanthanum and ytterbium.
[0112] Preferably, the lanthanum content is 0.01%-1% by mass, and the ytterbium content is 0.01%-1% by mass; more preferably, the lanthanum content is 0.05%-0.5% by mass, and the ytterbium content is 0.05%-0.5% by mass.
[0113] The lanthanum content is, for example, 0.2% by mass, and the ytterbium content is, for example, 0.2% by mass.
[0114] In this invention, preferably, the added element is phosphorus.
[0115] Preferably, the phosphorus content is less than 1%, preferably 0.05%-0.5%, for example 0.1%, 0.2%, 0.3% or 0.4%.
[0116] In this invention, preferably, the added element is silver.
[0117] Preferably, the silver content is 3% or less by mass, more preferably 1% to 3% or less, for example 3%.
[0118] In the present application, preferably, the additive element is silver and chromium.
[0119] Preferably, the mass content of silver is 3% or less, and the mass content of chromium is 0.01%-1%; preferably, the mass content of silver is 1%-3%, and the mass content of chromium is 0.05%-0.5%.
[0120] Preferably, the mass content of silver is 3%, and the mass content of chromium is 0.2%.
[0121] In the present application, preferably, the additive element is silver and titanium.
[0122] Preferably, the mass content of silver is 3% or less, and the mass content of titanium is 0.01%-1%; preferably, the mass content of silver is 1%-3%, and the mass content of titanium is 0.05%-0.5%.
[0123] Preferably, the mass content of silver is 3%, and the mass content of titanium is 0.2%.
[0124] In the present application, preferably, the additive element is silver and antimony.
[0125] Preferably, the mass content of silver is 3% or less, and the mass content of antimony is 0.01%-1%; preferably, the mass content of silver is 1%-3%, and the mass content of antimony is 0.05%-0.5%.
[0126] Preferably, the mass content of silver is 3%, and the mass content of antimony is 0.2%.
[0127] In the present application, preferably, the additive element is silver and nickel.
[0128] Preferably, the mass content of silver is 3% or less, and the mass content of nickel is 0.01%-1%; preferably, the mass content of silver is 1%-3%, and the mass content of nickel is 0.05%-0.5%.
[0129] Preferably, the mass content of silver is 3%, and the mass content of nickel is 0.2%.
[0130] In the present application, preferably, the additive element is silver and bismuth.
[0131] Preferably, the mass content of silver is 3% or less, and the mass content of bismuth is 0.01%-1%; preferably, the mass content of silver is 1%-3%, and the mass content of bismuth is 0.05%-0.5%.
[0132] wherein preferably the silver content is 3% by mass and the bismuth content is 0.2% by mass.
[0133] In the present application, the solder can optionally further comprise an impurity element.
[0134] wherein the impurity element can be one or more of sulfur, iron, manganese, carbon, lead, cadmium, arsenic, and oxygen.
[0135] wherein the impurity element has a content of 0.1% by mass or less.
[0136] In one embodiment, the solder consists of tin, zinc, copper, lanthanum, and phosphorus.
[0137] wherein, for example, the zinc content is 15% by mass, the copper content is 0.25% by mass, the lanthanum content is 0.1% by mass, the phosphorus content is 0.1% by mass, and the remainder is tin.
[0138] In one embodiment, the solder consists of tin, zinc, copper, lanthanum, cerium, and silver.
[0139] wherein, for example, the zinc content is 15% by mass, the copper content is 0.05% by mass, the lanthanum content is 0.2% by mass, the cerium content is 0.2% by mass, the silver content is 3% by mass, and the remainder is tin.
[0140] In one embodiment, the solder consists of tin, zinc, copper, lanthanum, ytterbium, and silver.
[0141] wherein, for example, the zinc content is 15% by mass, the copper content is 0.05% by mass, the lanthanum content is 0.2% by mass, the ytterbium content is 0.2% by mass, the silver content is 3% by mass, and the remainder is tin.
[0142] In one embodiment, the solder consists of tin, zinc, copper, lanthanum, chromium, and silver.
[0143] wherein, for example, the zinc content is 15% by mass, the copper content is 0.05% by mass, the lanthanum content is 0.2% by mass, the chromium content is 0.2% by mass, the silver content is 3% by mass, and the remainder is tin.
[0144] In one embodiment, the solder consists of tin, zinc, copper, lanthanum, titanium, and silver.
[0145] wherein, for example, the zinc content is 15% by mass, the copper content is 0.05% by mass, the lanthanum content is 0.2% by mass, the titanium content is 0.2% by mass, the silver content is 3% by mass, and the remainder is tin.
[0146] In one embodiment, the solder is composed of tin, zinc, copper, lanthanum, antimony and silver.
[0147] For example, the mass content of zinc is 15%, the mass content of copper is 0.05%, the mass content of lanthanum is 0.2%, the mass content of antimony is 0.2%, the mass content of silver is 3%, and the rest is tin.
[0148] In one embodiment, the solder is composed of tin, zinc, copper, lanthanum, nickel and silver.
[0149] For example, the mass content of zinc is 15%, the mass content of copper is 0.05%, the mass content of lanthanum is 0.2%, the mass content of nickel is 0.2%, the mass content of silver is 3%, and the rest is tin.
[0150] In one embodiment, the solder is composed of tin, zinc, copper, lanthanum, bismuth and silver.
[0151] For example, the mass content of zinc is 15%, the mass content of copper is 0.05%, the mass content of lanthanum is 0.2%, the mass content of bismuth is 0.2%, the mass content of silver is 3%, and the rest is tin.
[0152] The application also provides a use of the solder as described above in electronic packaging.
[0153] On the basis of common general knowledge in the art, the above-mentioned preferred conditions can be combined arbitrarily, thereby obtaining various preferred embodiments of the application.
[0154] The reagents and raw materials used in the application are commercially available.
[0155] The positive progress effect of the application is that:
[0156] The solder prepared from the raw material composition of the solder of the application has a spreading area of greater than 60 mm 2 , a wetting angle of less than 35°, indicating that it has excellent wetting performance; the solder prepared from the raw material composition of the solder of the application has an oxidation rate of 0.18*10 -10 , indicating that it has excellent oxidation resistance and is suitable for use in the field of electronic packaging and the like. It can be applied to the preparation of thin film capacitors or corrosion-resistant coatings and excellent effects are obtained.
[0157] In some preferred embodiments of the application, the solder prepared from the raw material composition of the solder of the application has a spreading area of further up to 70 mm 2 , a wetting angle of less than 26°, and an oxidation rate of 0.033*10 -10 or less. DETAILED DESCRIPTION
[0158] The present application will be further described in the following by way of examples without limiting the present application to the described examples. The experimental methods in the following examples, for which no specific conditions are indicated, are carried out according to conventional methods and conditions, or according to the instructions of the commercial suppliers.
[0159] Examples 1-8 and Comparative Examples 1-12
[0160] The compositions of the raw material compositions of the brazing filler metals of Examples 1-8 and Comparative Examples 1-12 are listed in Table 1:
[0161] Wherein, the total amount of each element is 100, and the data in the table is the mass percentage of each element in the raw material composition of the brazing filler metal, for example, the data of an element in the table is 15, which means that the mass percentage of the element in the raw material composition of the brazing filler metal of the example is 15%, that is, the mass content of the element is 15%. The raw material composition of the brazing filler metal of Examples 1-8 and Comparative Examples 1-12 does not contain impurity elements.
[0162] Table 1
[0163]
[0164] Note: " / " in the table means not containing the element.
[0165] Examples 1-8 and Comparative Examples 1-12 are the same except that the compositions of the raw material compositions of the brazing filler metals are different. The preparation method of the brazing filler metal of Examples 1-8 and Comparative Examples 1-12 includes the following steps:
[0166] The raw material composition of the brazing filler metal is sequentially subjected to melting, stirring, holding stage, solidification molding, extrusion, rolling, and drawing into wire to obtain a brazing filler metal with a diameter of 1 mm;
[0167] Wherein, the melting is carried out in a vacuum medium frequency furnace under an argon atmosphere, the melting pressure is 0.1 MPa, the melting temperature is 600°C, the melting time is 60 min, the stirring speed is 80 r / min, the stirring time is 10 min, the holding stage temperature is 600°C, and the solidification molding process adopts natural cooling at room temperature.
[0168] Wherein, the argon atmosphere can be formed by the following steps: first vacuumizing, and then introducing argon to form an argon atmosphere.
[0169] The loss of each element in the above preparation process can be ignored, and the composition of the brazing filler metal prepared by the preparation method is the same as that of the raw material composition of the brazing filler metal.
[0170] Example 1
[0171] 1. Spreading area test: The test was carried out according to the method for testing the wettability of brazing filler metal in GB / T 11364-2008, and a copper plate with a size of 40x40x1 mm was selected. 50 mg of each brazing filler metal was weighed, and the test temperature was 300-600℃. The spreading area after brazing was measured. The larger the spreading area, the better the wettability. 3
[0172] 2. Wettability angle test: The seat drop method was used. The molten brazing filler metal was dropped on the surface of the copper plate. After cooling and solidification, the contact angle between the brazing filler metal and the substrate was measured, that is, the wettability angle. The smaller the wettability angle, the better the wettability.
[0173] 3. Oxidation rate test: The weight method was used. The dried brazing filler metal sample with a mass of M0(mg) was placed in a crucible for cyclic oxidation experiment. Every 25 h, the sample was taken out, cooled to room temperature, and weighed. The mass was recorded as M1(mg), which was recorded as the first sampling. Every 25 h, the sample was taken out, cooled to room temperature, and weighed. The mass was recorded as M2, M3, M4, …, M N , which was recorded as the second sampling, the third sampling, the fourth sampling, …, the Nth sampling, respectively. The total oxidation time was 200 h, and the test temperature was 150-300℃. The first oxidation rate = (M1-M0) / M0, the second oxidation rate = (M2-M1) / M1, and so on. The average value of the oxidation rate calculated from the Nth sampling was taken as the oxidation rate of the example and the comparative example, that is, the oxidation rate = the sum of the Nth oxidation rate / N. The smaller the oxidation rate, the better the oxidation resistance.
[0174] The test results are shown in Table 2.
[0175] Table 2
[0176]
[0177] According to the above content, the spreading area of the brazing filler metal prepared from the raw material composition of examples 1-8 is greater than 60 mm 2 , and the wettability angle is less than 35°, indicating that it has excellent wettability performance. The oxidation rate of the brazing filler metal prepared from the raw material composition of examples 1-8 is 0.18*10 -10 , indicating that it has excellent oxidation resistance. The brazing filler metal of the present application is suitable for electronic packaging and other fields. When it is applied to the preparation of thin film capacitors or corrosion-resistant coatings, it can obtain excellent product performance.
[0178] According to the results of examples 2-3, if the rare earth elements are lanthanum and ytterbium, the oxidation rate can be reduced to 0.033*10 -10 , and the spreading area is greater than 70 mm 2 , the wetting angle is less than 26°; if the rare earth elements are lanthanum and cerium, the oxidation rate can be reduced to 0.058*10 -10 The spreading area is greater than 72 mm 2 , and the wetting angle is less than 26°.
[0179] According to the results of Example 4-Example 5, if the additive elements are silver and chromium or silver and titanium, the oxidation rate can be reduced to 0.1*10 -10 The spreading area is greater than 67 mm 2 , and the wetting angle is less than 28°.
[0180] Compared with the examples, Comparative Example 1 does not contain copper, rare earth elements and additive elements, resulting in a spreading area of the solder of only 39.4 mm 2 , a wetting angle of 57°, and an oxidation rate of 6.153*10 -10 , indicating that the wetting performance and oxidation resistance of Comparative Example 1 will significantly decrease.
[0181] Compared with the examples, Comparative Example 2 uses high-end tin-silver-copper lead-free solder, but its oxidation resistance decreases relative to the examples.
[0182] According to the results of Comparative Example 3 and Comparative Example 4 and the examples, the mass content of zinc in Comparative Example 3 and Comparative Example 4 is 1% and 31% respectively, resulting in a decrease in wetting performance and oxidation resistance.
[0183] The mass content of copper in Comparative Example 5 is too high, 2%, resulting in a decrease in wetting performance and oxidation resistance.
[0184] Comparative Example 6-Comparative Example 12 either do not contain copper or do not contain rare earth elements, resulting in a decrease in wetting performance and oxidation resistance.
Claims
1. A raw material composition of a brazing material, characterized by comprising: The raw material composition comprises a main component comprising tin, zinc; The raw material composition further comprises copper, rare earth elements and additive elements; The additive elements comprise one or more of chromium, titanium, antimony, aluminium, nickel, bismuth, indium, phosphorus and silver; The mass content of the zinc is 5-30%; the mass content of the copper is less than 1%; and the mass content of the rare earth elements is 0.01-1%.
2. The raw material composition of the brazing material according to claim 1, wherein It satisfies one or more of the following conditions: (a) the mass content of the tin is 80-90%, preferably 80-85%, for example 81.55% or 84.55%; (b) the mass content of the zinc is 10-25%, preferably 12-25%, for example 15%, 16%, 17%, 18%, 19% or 20%; (c) the mass content of the copper is 0.3% or less, preferably 0.25% or less, for example 0.05%, 0.1%, 0.2% or 0.25%; (d) the mass content of the rare earth elements is 0.05-1%, preferably 0.1-0.5%, for example 0.2%, 0.3% or 0.4%; (e) the mass content of the additive elements is 5% or less, preferably 4% or less, for example 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 1%, 2%, 3% or 3.2%; (f) the mass content of the chromium is 0.01-1%, preferably 0.05-0.5%, for example 0.1%, 0.2%, 0.3% or 0.4%; (g) the mass content of the titanium is 0.01-1%, preferably 0.05-0.5%, for example 0.1%, 0.2%, 0.3% or 0.4%; (h) the mass content of the antimony is 1% or less, preferably 0.05-0.5%, for example 0.1%, 0.2%, 0.3% or 0.4%; (i) the mass content of the aluminium is 0.01-1%, preferably 0.05-0.5%, for example 0.1%, 0.2%, 0.3% or 0.4%; (j) the mass content of the nickel is 0.01-1%, preferably 0.05-0.5%, for example 0.1%, 0.2%, 0.3% or 0.4%; (k) the mass content of the bismuth is 0.01-1%, preferably 0.05-0.5%, for example 0.1%, 0.2%, 0.3% or 0.4%; (l) the mass content of the indium is 0.01-1%, preferably 0.05-0.5%, for example 0.1%, 0.2%, 0.3% or 0.4%; (m) the rare earth elements comprise one or more of lanthanum series elements, scandium and yttrium; wherein the lanthanum series elements comprise one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
3. The raw material composition of the brazing material according to claim 1, wherein It satisfies any one of the following conditions: (a) the rare earth elements are lanthanum; wherein preferably the mass content of the lanthanum is 0.01-1%, preferably 0.05-0.5%, for example 0.1% or 0.2%. (b) the rare earth element is lanthanum and cerium; wherein, preferably, the mass content of the lanthanum is 0.01-1% and the mass content of the cerium is 0.01-1%; preferably, the mass content of the lanthanum is 0.05-0.5% and the mass content of the cerium is 0.05-0.5%; wherein, for example, the mass content of the lanthanum is 0.2% and the mass content of the cerium is 0.2%; (c) the rare earth element is lanthanum and ytterbium; wherein, preferably, the mass content of the lanthanum is 0.01-1% and the mass content of the ytterbium is 0.01-1%; preferably, the mass content of the lanthanum is 0.05-0.5% and the mass content of the ytterbium is 0.05-0.5%; wherein, for example, the mass content of the lanthanum is 0.2% and the mass content of the ytterbium is 0.2%.
4. The raw material composition of the brazing material according to claim 1, wherein which satisfies any one of the following conditions: (a) the additive element is phosphorus; wherein, preferably, the mass content of the phosphorus is 1% or less, preferably 0.05-0.5%, for example 0.1%, 0.2%, 0.3% or 0.4%; (b) the additive element is silver; wherein, preferably, the mass content of the silver is 3% or less, preferably 1-3% or less, for example 3%; (c) the additive element is silver and chromium; wherein, preferably, the mass content of the silver is 3% or less and the mass content of the chromium is 0.01-1%; preferably, the mass content of the silver is 1-3% and the mass content of the chromium is 0.05-0.5%; wherein, for example, the mass content of the silver is 3% and the mass content of the chromium is 0.2%; (d) the additive element is silver and titanium; wherein, preferably, the mass content of the silver is 3% or less and the mass content of the titanium is 0.01-1%; preferably, the mass content of the silver is 1-3% and the mass content of the titanium is 0.05-0.5%; wherein, preferably, the mass content of the silver is 3% and the mass content of the titanium is 0.2%; (e) the additive element is silver and antimony; wherein, preferably, the mass content of the silver is 3% or less and the mass content of the antimony is 0.01-1%; preferably, the mass content of the silver is 1-3% and the mass content of the antimony is 0.05-0.5%; wherein, preferably, the mass content of the silver is 3% and the mass content of the antimony is 0.2%; (f) the additive element is silver and nickel; wherein, preferably, the mass content of the silver is 3% or less and the mass content of the nickel is 0.01-1%; preferably, the mass content of the silver is 1-3% and the mass content of the nickel is 0.05-0.5%; wherein, preferably, the mass content of the silver is 3% and the mass content of the nickel is 0.2%; (g) the additive element is silver and bismuth; wherein, preferably, the mass content of the silver is 3% or less and the mass content of the bismuth is 0.01-1%; preferably, the mass content of the silver is 1-3% and the mass content of the bismuth is 0.05-0.5%; wherein, preferably, the silver content is 3% by mass and the bismuth content is 0.2% by mass.
5. The raw material composition of the brazing material according to claim 1, wherein It satisfies any one of the following conditions: (a) the raw material composition consists of tin, zinc, copper, lanthanum, and phosphorus; wherein, for example, the zinc content is 15% by mass, the copper content is 0.25% by mass, the lanthanum content is 0.1% by mass, the phosphorus content is 0.1% by mass, and the balance is tin; (b) the raw material composition consists of tin, zinc, copper, lanthanum, cerium, and silver; wherein, for example, the zinc content is 15% by mass, the copper content is 0.05% by mass, the lanthanum content is 0.2% by mass, the cerium content is 0.2% by mass, the silver content is 3% by mass, and the balance is tin; (c) the raw material composition consists of tin, zinc, copper, lanthanum, ytterbium, and silver; wherein, for example, the zinc content is 15% by mass, the copper content is 0.05% by mass, the lanthanum content is 0.2% by mass, the ytterbium content is 0.2% by mass, the silver content is 3% by mass, and the balance is tin; (d) the raw material composition consists of tin, zinc, copper, lanthanum, chromium, and silver; wherein, for example, the zinc content is 15% by mass, the copper content is 0.05% by mass, the lanthanum content is 0.2% by mass, the chromium content is 0.2% by mass, the silver content is 3% by mass, and the balance is tin; (e) the raw material composition consists of tin, zinc, copper, lanthanum, titanium, and silver; wherein, for example, the zinc content is 15% by mass, the copper content is 0.05% by mass, the lanthanum content is 0.2% by mass, the titanium content is 0.2% by mass, the silver content is 3% by mass, and the balance is tin; (f) the raw material composition consists of tin, zinc, copper, lanthanum, antimony, and silver; wherein, for example, the zinc content is 15% by mass, the copper content is 0.05% by mass, the lanthanum content is 0.2% by mass, the antimony content is 0.2% by mass, the silver content is 3% by mass, and the balance is tin; (g) the raw material composition consists of tin, zinc, copper, lanthanum, nickel, and silver; wherein, for example, the zinc content is 15% by mass, the copper content is 0.05% by mass, the lanthanum content is 0.2% by mass, the nickel content is 0.2% by mass, the silver content is 3% by mass, and the balance is tin; (h) the raw material composition consists of tin, zinc, copper, lanthanum, bismuth, and silver; wherein, for example, the zinc content is 15% by mass, the copper content is 0.05% by mass, the lanthanum content is 0.2% by mass, the bismuth content is 0.2% by mass, the silver content is 3% by mass, and the balance is tin.
6. A method for producing a brazing material, characterized by It includes the following steps: The raw material composition of the solder as claimed in any one of claims 1 to 5 is sequentially subjected to melting and solidification molding to obtain the solder.
7. The brazing material production method according to claim 6, wherein It satisfies one or more of the following conditions: (a) the pressure of the melting is 1 MPa or less, preferably 0.5 MPa or less, for example 0.1 MPa; (b) the temperature of the melting is 500-800℃, preferably 500-700℃, for example 600℃; (c) the time of the melting is 30-90 min, preferably 40-80 min, for example 60 min; (d) the melting is carried out in a vacuum frequency furnace; (e) the melting is carried out in an argon atmosphere; (f) the melting is followed by a stirring step before solidification molding; wherein, preferably, the stirring speed is 50-100 r / min, preferably 60-90 r / min, for example 70 r / min or 80 r / min; wherein, preferably, the stirring time is 5 min-10 min; wherein, preferably, the stirring is followed by a holding stage, and the temperature of the holding stage is preferably 500-800℃, for example 600℃.
8. A solder prepared by the method of claim 6 or 7.
9. A brazing material, characterized by The solder comprises a main component, and the main component comprises tin, zinc; The solder further comprises copper, rare earth elements and additive elements; The additive elements comprise one or more of chromium, titanium, antimony, aluminum, nickel, bismuth, indium, phosphorus and silver; wherein, the mass content of the zinc is 5%-30%; the mass content of the copper is less than 1%, and the mass content of the rare earth elements is 0.01%-1%.
10. Use of the solder of claim 8 or 9 in electronic packaging.