CN106514039B - A kind of copper and tin titanium solder and preparation method thereof - Google Patents
A kind of copper and tin titanium solder and preparation method thereof Download PDFInfo
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- CN106514039B CN106514039B CN201610955635.6A CN201610955635A CN106514039B CN 106514039 B CN106514039 B CN 106514039B CN 201610955635 A CN201610955635 A CN 201610955635A CN 106514039 B CN106514039 B CN 106514039B
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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
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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
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Abstract
一种铜锡钛钎料，包括CuSn基体钎料和包覆在CuSn基体钎料外的金属钛电镀层，基体钎料和金属钛电镀层之间为CuSn基体钎料中的固溶体与金属钛电镀层发生扩散反应形成的过渡层。本发明提供的CuSnTi箔带钎料及其制备方法，操作简单、方便，突破了传统方法制备钎料的技术瓶颈，为新形态的高品质活性钎料提供了一种新的绿色制造方法。对CuSnTi钎料来说，提高了CuSnTi钎料中活性元素Ti的含量，克服了传统CuSnTi钎料难以成形及熔融盐体系电镀钛的缺点，该方法具有易成形、加工效率高、成本低等优点，为铜锡钛钎料的制造生产提供一种新的技术途径。A copper-tin-titanium brazing filler metal, comprising a CuSn base brazing filler metal and a metal titanium electroplating layer coated on the CuSn base brazing filler metal, and between the base brazing filler metal and the metal titanium electroplating layer is a solid solution in the CuSn base brazing filler metal and metal titanium electroplating The transition layer formed by the diffusion reaction of the layer. The CuSnTi foil strip solder provided by the invention and the preparation method thereof are simple and convenient to operate, break through the technical bottleneck of preparing the solder by the traditional method, and provide a new green manufacturing method for a new form of high-quality active solder. For CuSnTi solder, the content of active element Ti in the CuSnTi solder is increased, which overcomes the shortcomings of the traditional CuSnTi solder that is difficult to form and the molten salt system electroplating titanium. This method has the advantages of easy forming, high processing efficiency and low cost. , to provide a new technical approach for the manufacture and production of copper-tin-titanium solder.
Description
Technical field
The present invention relates to brazing materials, more particularly, to the preparation method of a kind of copper and tin titanium solder and the copper and tin titanium solder.
Background technique
Copper and tin titanium solder is widely used in the soldering of graphite, diamond etc. as a kind of solder, but traditional copper and tin titanium solder
Mostly exist with powder-form, it is difficult to shape, be a great problem that puzzlement is brazed worker both at home and abroad.
Titanium has many advantages, such as that specific strength height, corrosion resistance are strong as a kind of strategic light metal, is usually used in submarine, on aircraft,
Play a great role in navigation, aviation field, in metal surface electrodeposition of titanium can play the role of protection it is corrosion-resistant, can be applied to as
Ocean, corrosive environment of sea water are medium.
The discharge potential of Titanium is low, realizes that the deposition of titanium is more difficult, while the electroplating technology of titanium is immature also not perfect.Mesh
Preceding common method is as follows: first is that electric arc ionize electro-plating method, ionize in vacuum or inert gas using Titanium be titanium from
Then bombarding cathode implements plating to son；Second is that second-level titanizing method, first plates one layer of active metal (such as mainly on matrix
Magnesium), it is then cleaned with titanium tetrachloride solution, Titanium is displaced by magnesium and is then plated on matrix；Third is that fuse salt
Electro-plating method, using carbon oxygen titanium as anode, plating metal be cathode, fuse salt is that electrolyte implements plating.But electric arc ionization electricity
Electroplating method processing step is more, and energy consumption is high, and process is complicated, and operation difficulty is big；The electrode potential of magnesium is same in second-level titanizing method
Sample is lower, and plating is difficult to realize；Fuse salt electro-plating method includes that titanium is smelted and titanium two processes of plating, coating quality and stability
It is poor.
Currently, the preparation method of copper and tin titanium solder mainly has two kinds of electric arc melting, vacuum melting.In electric arc melting method by
It is small in arc light heated perimeter, the copper and tin titanium solder prepared every time less than 1000g, can not industrialization production, while prepared by this method
Copper and tin titanium solder due to arc light irradiation area it is narrow, tissue odds, Ti element part segregation phenomenon are easy to appear, so that copper and tin titanium
Solder performance deteriorates, it is difficult to normal use.And vacuum smelting method when preparing powdery copper and tin titanium solder with certain advantage,
But when preparing copper and tin titanium foil band solder, since there are CuSn brittlement phases, so that solder plasticity variation is difficult to shape, while
Impurity Fe, C etc. are easily entrained in course of hot rolling, so that copper and tin titanium solder mechanical properties decrease, is unable to satisfy engineering reality
Performance indicator requirement.Therefore, electric arc melting and vacuum smelting method have centainly in terms of preparation copper and tin titanium foil is with solder
Limitation.
Summary of the invention
It is an object of the invention to the technology bottles of deficiency and Titanium Electroplating technique for above-mentioned existing copper and tin titanium solder forming
Neck provides a kind of copper and tin titanium solder haveing excellent performance, and provides easily forming, preparation method high in machining efficiency, at low cost.
The object of the present invention is achieved in the following manner:
A kind of copper and tin titanium solder, including CuSn matrix solder and the Titanium electroplated layer that is coated on outside CuSn matrix solder,
It is the solid solution and Titanium electroplated layer generation diffusion reaction in CuSn matrix solder between matrix solder and Titanium electroplated layer
The transition zone of formation.
Percentage thickness between the CuSn matrix solder, transition zone and titanium electroplated layer be respectively as follows: matrix solder 65.0 ~
92.0 %, 7.5 ~ 33.5 % of transition zone, 0.5 ~ 1.5 % of metal layer.
The copper and tin titanium solder with a thickness of 15 ~ 85 μm.
The Ni element for being also 0.4-1.2 % containing mass fraction in the CuSn matrix solder.
The preparation method of copper and tin titanium solder as described above, comprising the following steps:
(1) prefabricated CuSn matrix solder；
(2) using CuSn matrix solder as cathode, simple substance titanium is anode, in CuSn matrix solder electroplating surface titanium coating；
(3) after titanium technique to be electroplated, it is permeated into 1 ~ 10 min in the vacuum environment at 1650 ~ 1700 DEG C, so
After spreading 2 ~ 30 h in 1550 ~ 1650 DEG C of vacuum drying ovens afterwards, copper and tin titanium solder is made after cooling.
The step (2) specifically: using CuSn matrix solder as cathode, using simple substance titanium as anode, in every 1000mL water
0.146 ~ 0.208 moL of titanium sulfate, 0.07 ~ 0.176 moL of sodium sulphate, 0.736 ~ 1.288moL of sulfuric acid, surfactant is added
10 ~ 25 g are formulated as electroplate liquid, implement Titanium Electroplating；
0.003 ~ 0.008 moL of sodium vanadate is additionally added in every 1000mL electroplate liquid.
The surfactant is alkyl ether surfactant；Further, the alkyl ether surfactant is OP-
10, any one of ethoxylated dodecyl alcohol, polyethylene glycol trimethyl nonyl ethers, nonylphenol polyoxyethylene ether.
The Titanium Electroplating carries out under vacuum environment or inert gas shielding environment, technological parameter are as follows: current density 0.5 ~ 5
A/dm2, 35 ~ 50 DEG C of electroplating solution temperature, 2 ~ 15 min of plating time.
CuSnTi foil solder provided by the invention and preparation method thereof, it is simple, convenient, breach conventional method system
The technical bottleneck of standby solder provides a kind of new Method of Green Manufacture for the high-quality active solder of neomorph.To CuSnTi
For solder, the content of active element Ti in CuSnTi solder is improved, traditional CuSnTi solder is overcome and is difficult to shape and melt
The shortcomings that melting salt system Titanium Electroplating, this method have many advantages, such as easily to shape, are high in machining efficiency, at low cost, are copper and tin titanium solder
Manufacture production provides a kind of new technological approaches.
In addition, using binary and the above copper alloy as matrix, such as copper palladium, copper manganese, cupro-nickel manganese, using preparation method of the present invention
In its electroplating surface titanium, the copper alloy or spelter solder for preparing titaniferous all fall in the scope of protection of the present invention.
Specific embodiment
Embodiment 1
A kind of copper and tin titanium solder, including CuSn matrix solder and the Titanium electroplated layer that is coated on outside CuSn matrix solder,
It is the solid solution and Titanium electroplated layer generation diffusion reaction in CuSn matrix solder between matrix solder and Titanium electroplated layer
The transition zone of formation；Percentage thickness between CuSn matrix solder, transition zone and titanium electroplated layer is respectively as follows: matrix solder
65.0 ~ 92.0 %, 7.5 ~ 33.5 % of transition zone, 0.5 ~ 1.5 % of metal layer；Copper and tin titanium solder with a thickness of 15 ~ 85 μm；Into
One step is also matrix solder 0.4- containing quality in addition to the Cu containing 55-65%, the Sn of 34-44.5% in CuSn matrix solder
1.2% Ni, Ni, which is added, can avoid CuSn matrix solder formation CuSn frangible compounds, lay the foundation for the forming of matrix solder.
The preparation method of copper and tin titanium solder as described above, comprising the following steps:
(1) prefabricated CuSn matrix solder: raw metal Cu, Sn and micro Ni are put into smelting furnace first, cast, are moved back
Fire squeezes, roll forming, is made as CuSn matrix solder in advance；
(2) using CuSn matrix solder as cathode, simple substance titanium is anode, in CuSn matrix solder electroplating surface titanium coating；
(3) after titanium technique to be electroplated, dry infiltration 1 ~ 10 in the vacuum environment at 1650 ~ 1700 DEG C by it
Min, then after 1550 ~ 1650 DEG C of 2 ~ 30 h of diffusion in vacuum, to form transition zone, then furnace cooling is made with a thickness of 15
~ 85 μm of copper and tin titanium solder；The transition zone of formation facilitates matrix solder and titanium coating forms metallurgical bonding, improves between the two
Binding force, while the mechanical property of CuSnTi solder can be improved, regulates and controls combination interface tissue and object phase composition, help to enhance
The active function of CuSnTi solder；If titanium electroplated layer (1660 DEG C) and (970 ~ 990 DEG C) of matrix solder are molten without transition zone
It is larger to change temperature difference, copper and tin titanium alloy is difficult to shape, is easy embrittlement, does not have the effect of active solder.
Step (2) specifically: using CuSn matrix solder as cathode, using simple substance titanium as anode, to be added in every 1000mL water
0.146 ~ 0.208 moL of titanium sulfate, 0.07 ~ 0.176 moL of sodium sulphate, 0.736 ~ 1.288moL of sulfuric acid, surfactant 10 ~ 25
G is formulated as electroplate liquid, and electric current, voltage is arranged, and under vacuum environment or inert gas shielding environment, implements electrodeposition of titanium；Electricity is heavy
Product titanium technological parameter are as follows: 0.5 ~ 5 A/dm of current density2, 3 ~ 6 V of voltage, 35 ~ 50 DEG C of electroplating solution temperature, plating time 2 ~
15 min。
Preferably, 0.003 ~ 0.008 moL of dispersing agent sodium vanadate, the surface-active are additionally added in every 1000mL electroplate liquid
Agent is alkyl ether surfactant, and further alkyl ether surfactant is OP-10, ethoxylated dodecyl alcohol, poly- second
Any one in glycol trimethyl nonyl ethers, nonylphenol polyoxyethylene ether.
The invention has the following advantages:
1) electrodeposition of titanium-infiltration-diffusion composite preparation process provided by the invention overcomes traditional CuSnTi solder and is difficult to
The deficiency of forming and conventional electroplating method provides a kind of new way for the forming of neomorph CuSnTi solder；2) in matrix solder
Containing microelement Ni, avoids forming CuSn frangible compounds in CuSn matrix solder, lay the foundation for the forming of matrix solder；
3) electrodeposition of titanium method provided by not only can implement titanizing in monometallic, alloy surface, but also plate on welding material surface
Titanium, the forming for neomorph metal material especially titaniferous welding material provide a kind of new approaches；4) institute during electrodeposition of titanium
The bath temperature of application is low, the time is short, and deposition rate is high, has energy conservation, consumption reduction effect；5) electrodeposition of titanium-infiltration-diffusion
Composite preparation process is implemented under vacuum environment (or inert gas shielding), and the CuSnTi solder cleanliness of preparation is high, does not contain
Any impurity；6) current density, bath temperature, plating time, bath concentration multi-parameter Collaborative Control technology are used, regulation is passed through
Titanium electroplated layer, transition zone thickness improve CuSnTi solder in active element Ti content.
Embodiment 2
A kind of CuSnTi solder contains Ni 0.8% by matrix solder BCu60Sn() and be coated on outside BCu60Sn matrix solder
Titanium electroplated layer composition, transition zone be CuTi compound phase and SnTiNi compound phase composition.Matrix solder, transition zone,
The percentage thickness of electroplated layer is as follows, matrix solder: 92.0 %, transition zone: 7.5 %, electroplated layer: 0.5 %.
The preparation method of copper and tin titanium solder as described above, comprising the following steps:
600 g of metallic copper, 392 g of tin, 8 g of nickel are placed in smelting furnace first, through casting, annealing, extruding, roll forming,
It is made as in advance with a thickness of 80 μm of ribbon base solder BCu60Sn；Then positive and negative in BCu60Sn matrix solder using Titanium Electroplating technique
Face Titanium Electroplating (15 μm of single side thickness)；After technique to be electroplated, puts it into 1650 DEG C of vacuum oven and permeate 10
Min is then placed in after spreading 30 h in 1550 DEG C of vacuum drying oven, furnace cooling, and the CuSnTi solder with a thickness of 85 μm is made.
Wherein: plating titanium solution is by 50 g/L(0.208moL/L of titanium sulfate), 25 g/L(0.176moL/L of sodium sulphate), matter
Amount score is 98% concentrated sulfuric acid, 70 ml/L(1.288moL/L), 25 g/L of OP-10,1000 ml of deionized water composition.Specific electricity
Technology for plating titanium parameter is as follows: 1.5 A/dm of current density2, 3 V of voltage, 35 DEG C of solution temperature, 15 min of plating time, the electricity
Technology for plating titanium carries out in vacuum environment.
The CuSnTi solder of above method preparation, compared with matrix solder BCu60Sn, wetting areas improves 7.5 %.
Embodiment 3
A kind of CuSnTi solder, by matrix solder BCu55Sn(1.0 % containing Ni) and it is coated on BCu55Snu matrix solder
Outer Titanium electroplated layer composition, transition zone are CuTi compound phase and SnTiNi compound phase composition.Matrix solder, transition
Layer, the percentage thickness of electroplated layer are as follows, matrix solder: 85.0 %, transition zone: 14.0 %, electroplated layer: 1.0 %.
The preparation method of copper and tin titanium solder as described above, comprising the following steps:
550 g of metallic copper, 440 g of tin, 10 g of nickel are placed in smelting furnace first, through casting, annealing, extruding, roll forming,
It is made as in advance with a thickness of 30 μm of ribbon base solder BCu55Sn；Then positive and negative in BCu55Sn matrix solder using Titanium Electroplating technique
Face Titanium Electroplating (10 μm of single side thickness)；After technique to be electroplated, puts it into 1700 DEG C of vacuum oven and permeate 5
Min is then placed in after spreading 2 h in 1650 DEG C of vacuum drying oven, furnace cooling, and the CuSnTi solder with a thickness of 35 μm is made.
Wherein: plating titanium solution is by 40 g/L(0.166moL/L of titanium sulfate), 20 g/L(0.141moL/L of sodium sulphate), matter
Amount score is 98% concentrated sulfuric acid, 40 ml/L(0.746moL/L), 15 g/L of ethoxylated dodecyl alcohol, 1000 ml group of deionized water
At.Specific Titanium Electroplating technological parameter is as follows: 5 A/dm of current density2, 6 V of voltage, 50 DEG C of solution temperature, 4 min of plating time,
The Titanium Electroplating technique carries out in helium protection environment.
The CuSnTi solder of above method preparation, compared with matrix solder BCu55Sn, wetting areas improves 9.6 %.
Embodiment 4
A kind of CuSnTi solder, by matrix solder BCu65Sn(0.5 % containing Ni) and be coated on outside BCu65Sn matrix solder
Titanium electroplated layer composition, transition zone be CuTi compound phase and SnTiNi compound phase composition.Matrix solder, transition zone,
The percentage thickness of electroplated layer is as follows, matrix solder: 65.0 %, transition zone: 33.5 %, electroplated layer: 1.5 %.
The preparation method of copper and tin titanium solder as described above, comprising the following steps:
650 g of metallic copper, 345 g of tin, 5 g of nickel are placed in smelting furnace first, through casting, annealing, extruding, roll forming,
It is made as in advance with a thickness of 10 μm of ribbon base solder BCu65Sn；Then positive and negative in Bcu65Sn matrix solder using Titanium Electroplating technique
Face Titanium Electroplating (6 μm of single side thickness)；After technique to be electroplated, puts it into 1650 DEG C of vacuum oven and permeate 1
Min is then placed in after spreading 12 h in 1550 DEG C of vacuum drying oven, furnace cooling, and the CuSnTi solder with a thickness of 15 μm is made.
Wherein: plating titanium solution is by 35 g/L of titanium sulfate (0.146moL/L), 10 g/L(0.07moL/L of sodium sulphate), matter
Amount score is 98% concentrated sulfuric acid, 50 ml/L(0.92moL/L), 10 g/L of polyethylene glycol trimethyl nonyl ethers, deionized water 1000
Ml composition.Specific electroplating technological parameter is as follows: 3.5 A/dm of current density2, 4.5 V of voltage, 40 DEG C of solution temperature, plating time
2 min, the Titanium Electroplating technique carry out in vacuum environment.
The CuSnTi solder of above method preparation, compared with matrix solder BCu65Sn, wetting areas improves 12.4 %.
Embodiment 5
A kind of CuSnTi solder, by matrix solder BCu55Sn(0.6 % containing Ni) and be coated on outside BCu55Sn matrix solder
Titanium electroplated layer composition, transition zone be CuTi compound phase and SnTiNi compound phase composition.Matrix solder, transition zone,
The percentage thickness of electroplated layer is as follows, matrix solder: 78.8 %, transition zone: 20.0 %, electroplated layer: 1.2 %.
The preparation method of copper and tin titanium solder as described above, comprising the following steps:
550 g of metallic copper, 444 g of tin, 6 g of nickel are placed in smelting furnace first, through casting, annealing, extruding, roll forming,
It is made as in advance with a thickness of 25 μm of ribbon base solder BCu55Sn；Then positive and negative in BCu55Sn matrix solder using Titanium Electroplating technique
Face Titanium Electroplating (10 μm of single side thickness)；After technique to be electroplated, puts it into 1700 DEG C of vacuum oven and permeate 3
Min is then placed in after spreading 20 h in 1650 DEG C of vacuum drying oven, furnace cooling, and the CuSnTi solder with a thickness of 30 μm is made.
Wherein: plating titanium solution is by 45 g/L(0.188moL/L of titanium sulfate), 15 g/L(0.106moL/L of sodium sulphate), matter
Amount score is 98% concentrated sulfuric acid, 55 ml/L(1.012moL/L), 20 g/L of nonylphenol polyoxyethylene ether, 1000 ml group of deionized water
At.Specific Titanium Electroplating technological parameter is as follows: 3.0 A/dm of current density2, 3.5 V of voltage, 45 DEG C of solution temperature, plating time 6
Min, the Titanium Electroplating technique carry out in argon gas protection environment.
The CuSnTi solder of above method preparation, compared with matrix solder BCu55Sn, wetting areas improves 15.3 %.
Embodiment 6
A kind of CuSnTi solder, by matrix solder BCu60Sn(0.8 % containing Ni) and be coated on outside BCu60Sn matrix solder
Titanium electroplated layer composition, transition zone be CuTi compound phase and SnTiNi compound phase composition.Matrix solder, transition zone,
The percentage thickness of electroplated layer is as follows, matrix solder: 81.0 %, transition zone: 18.1 %, electroplated layer: 0.9 %.
The preparation method of copper and tin titanium solder as described above, comprising the following steps:
600 g of metallic copper, 392 g of tin, 8 g of nickel are placed in smelting furnace first, through casting, annealing, extruding, roll forming,
It is made as in advance with a thickness of 50 μm of ribbon base solder BCu60Sn；Then positive and negative in BCu60Sn matrix solder using Titanium Electroplating technique
Face Titanium Electroplating (15 μm of single side thickness)；After technique to be electroplated, puts it into 1700 DEG C of vacuum oven and permeate 10
Min is then placed in after spreading 25 h in 1650 DEG C of vacuum drying oven, furnace cooling, and the CuSnTi solder with a thickness of 60 μm is made.
Wherein: plating titanium solution is by 40 g/L(0.167moL/L of titanium sulfate), 18 g/L(0.127moL/L of sodium sulphate), matter
Amount score is 98% concentrated sulfuric acid, 60 ml/L(1.104moL/L), 16 g/L of polyethylene glycol trimethyl nonyl ethers, deionized water 1000
Ml composition.Specific Titanium Electroplating technological parameter is as follows: 4.0 A/dm of current density2, 4.2 V of voltage, 40 DEG C of solution temperature, when plating
Between 5.5 min, which carries out in vacuum environment.
The CuSnTi solder of above method preparation, compared with matrix solder BCu60Sn, wetting areas improves 18.1 %.
Embodiment 7
A kind of CuSnTi solder, by matrix solder BCu62Sn(0.4 % containing Ni) and be coated on outside BCu62Sn matrix solder
Titanium electroplated layer composition, transition zone be CuTi compound phase and SnTiNi compound phase composition.Matrix solder, transition zone,
The percentage thickness of electroplated layer is as follows, matrix solder: 75.0 %, transition zone: 24.2%, electroplated layer: 0.8 %.
The preparation method of copper and tin titanium solder as described above, comprising the following steps:
620 g of metallic copper, 376 g of tin, 4 g of nickel are placed in smelting furnace first, through casting, annealing, extruding, roll forming,
It is made as in advance with a thickness of 40 μm of ribbon base solder BCu62Sn；Then using Titanium Electroplating technique in BCu62Sn matrix solder front and back sides
Titanium Electroplating (15 μm of single side thickness)；After technique to be electroplated, puts it into 1680 DEG C of vacuum oven and permeates 4min,
It is then placed in after spreading 15 h in 1600 DEG C of vacuum drying oven, furnace cooling, the CuSnTi solder with a thickness of 50 μm is made.
Wherein: plating titanium solution is by titanium sulfate 0.18moL/L, sodium sulphate 0.07moL/L, 0.003 moL/L of sodium vanadate, matter
Amount score is 98% concentrated sulfuric acid 0.9moL/L, nonylphenol polyoxyethylene ether 20g/L, 1000 ml of deionized water composition.Specific plating
Titanium technological parameter is as follows: 1 A/dm of current density2, 3 V of voltage, 45 DEG C of solution temperature, plating time 8min, the Titanium Electroplating technique
It is carried out in argon gas protection environment.
The CuSnTi solder of above method preparation, compared with matrix solder BCu62Sn, wetting areas improves 14.6 %.
Embodiment 8
A kind of CuSnTi solder contains Ni 1.2% by matrix solder BCu55Sn() and be coated on outside BCu55Sn matrix solder
Titanium electroplated layer composition, transition zone be CuTi compound phase and SnTiNi compound phase composition.Matrix solder, transition zone,
The percentage thickness of electroplated layer is as follows, matrix solder: 70 %, transition zone: 29.3%, electroplated layer: 0.7%.
The preparation method of copper and tin titanium solder as described above, comprising the following steps:
550 g of metallic copper, 438 g of tin, 12 g of nickel are placed in smelting furnace first, through casting, annealing, squeezes, are rolled into
Shape is made as in advance with a thickness of 50 μm of ribbon base solder BCu55Sn；Then using Titanium Electroplating technique BCu55Sn matrix solder just
Reverse side Titanium Electroplating (18 μm of single side thickness)；After technique to be electroplated, puts it into 1670 DEG C of vacuum oven and permeate
8min is then placed in after spreading 8h in 1600 DEG C of vacuum drying oven, furnace cooling, and the CuSnTi solder with a thickness of 70 μm is made.
Wherein: plating titanium solution is by titanium sulfate 0.16moL/L, sodium sulphate 0.12moL/L, 0.008 moL/L of sodium vanadate, matter
Amount score is 98% concentrated sulfuric acid 1.0moL/L, polyethylene glycol trimethyl nonyl ethers 12g/L, 1000 ml of deionized water composition.Specifically
Titanium Electroplating technological parameter is as follows: current density 2.5A/dm2, 3.5 V of voltage, 40 DEG C of solution temperature, plating time 10min, the electricity
Technology for plating titanium carries out in helium protection environment.
The CuSnTi solder of above method preparation, compared with matrix solder BCu55Sn, wetting areas improves 17.2 %.
Embodiment 9
A kind of CuSnTi solder contains Ni 1% by matrix solder BCu65Sn() and be coated on outside BCu65Sn matrix solder
Titanium electroplated layer composition, transition zone are CuTi compound phase and SnTiNi compound phase composition.Matrix solder, transition zone, electricity
The percentage thickness of coating is as follows, matrix solder: 90 %, transition zone: 8.9%, electroplated layer: 1.1%.
The preparation method of copper and tin titanium solder as described above, comprising the following steps:
650 g of metallic copper, 440 g of tin, 10 g of nickel are placed in smelting furnace first, through casting, annealing, squeezes, are rolled into
Shape is made as in advance with a thickness of 40 μm of ribbon base solder BCu65Sn；Then using Titanium Electroplating technique BCu65Sn matrix solder just
Reverse side Titanium Electroplating (10 μm of single side thickness)；After technique to be electroplated, puts it into 1660 DEG C of vacuum oven and permeate
5min is then placed in after spreading 10h in 1580 DEG C of vacuum drying oven, furnace cooling, and the CuSnTi solder with a thickness of 43 μm is made.
Wherein: plating titanium solution is by titanium sulfate 0.2moL/L, sodium sulphate 0.15moL/L, 0.005 moL/L of sodium vanadate, matter
Amount score is 98% concentrated sulfuric acid 1.2moL/L, ethoxylated dodecyl alcohol 18g/L, 1000 ml of deionized water composition.Specific plating
Titanium technological parameter is as follows: current density 3A/dm2, 3 V of voltage, 35 DEG C of solution temperature, plating time 12min, the Titanium Electroplating technique
It is carried out in vacuum environment.
The CuSnTi solder of above method preparation, compared with matrix solder BCu65Sn, wetting areas improves 13.5 %.
What has been described above is only a preferred embodiment of the present invention, it is noted that for those skilled in the art,
Without depart from that overall concept of the invention, several changes and improvements can also be made, these also should be considered as of the invention
Protection scope.
Claims (8)
1. a kind of copper and tin titanium solder, it is characterised in that: including CuSn matrix solder and the metal being coated on outside CuSn matrix solder
Titanium electroplated layer occurs for the solid solution in CuSn matrix solder with Titanium electroplated layer between matrix solder and Titanium electroplated layer
The transition zone that diffusion reaction is formed, the percentage thickness point between the CuSn matrix solder, transition zone and Titanium electroplated layer
Not are as follows: 65.0 ~ 92.0 % of matrix solder, 7.5 ~ 33.5 % of transition zone, 0.5 ~ 1.5 % of Titanium electroplated layer, the copper and tin titanium
Solder with a thickness of 15 ~ 85 μm.
2. copper and tin titanium solder as described in claim 1, it is characterised in that: also contain mass fraction in the CuSn matrix solder
For the Ni element of 0.4-1.2 %.
3. the preparation method of copper and tin titanium solder according to claim 1 or 2, it is characterised in that the following steps are included:
(1) prefabricated CuSn matrix solder；
(2) using CuSn matrix solder as cathode, simple substance titanium is anode, in CuSn matrix solder electroplating surface titanium coating；
(3) after titanium technique to be electroplated, it is permeated into 1 ~ 10 min in the vacuum environment at 1650 ~ 1700 DEG C, then in
After spreading 2 ~ 30 h in 1550 ~ 1650 DEG C of vacuum drying ovens, copper and tin titanium solder is made after cooling.
4. the preparation method of copper and tin titanium solder according to claim 3, it is characterised in that: the step (2) specifically: with
CuSn matrix solder is cathode, using simple substance titanium as anode, 0.146 ~ 0.208 moL of titanium sulfate, sulphur to be added in every 1000mL water
Sour 0.07 ~ 0.176 moL of sodium, 0.736 ~ 1.288moL of sulfuric acid, 10 ~ 25 g of surfactant are formulated as electroplate liquid, implement plating
Titanium.
5. the preparation method of copper and tin titanium solder according to claim 4, it is characterised in that: in electroplate liquid described in every 1000mL
It is additionally added 0.003 ~ 0.008 moL of sodium vanadate.
6. the preparation method of copper and tin titanium solder according to claim 4, it is characterised in that: the surfactant is alkyl
Ether surfactant.
7. the preparation method of copper and tin titanium solder according to claim 6, it is characterised in that: the alkyl ether surface-active
Agent is any one of OP-10, ethoxylated dodecyl alcohol, polyethylene glycol trimethyl nonyl ethers, nonylphenol polyoxyethylene ether.
8. the preparation method of copper and tin titanium solder according to claim 4, it is characterised in that: the Titanium Electroplating is in vacuum environment
Or carried out under inert gas shielding environment, technological parameter are as follows: 0.5 ~ 5 A/dm of current density2, 35 ~ 50 DEG C of electroplating solution temperature,
2 ~ 15 min of plating time.
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