CN106514039A - Copper-tin-titanium brazing filler metal and preparation method thereof - Google Patents
Copper-tin-titanium brazing filler metal and preparation method thereof Download PDFInfo
- Publication number
- CN106514039A CN106514039A CN201610955635.6A CN201610955635A CN106514039A CN 106514039 A CN106514039 A CN 106514039A CN 201610955635 A CN201610955635 A CN 201610955635A CN 106514039 A CN106514039 A CN 106514039A
- Authority
- CN
- China
- Prior art keywords
- titanium
- solder
- copper
- tin
- matrix
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B23K35/40—Making wire or rods for soldering or welding
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention discloses a copper-tin-titanium brazing filler metal. The copper-tin-titanium brazing filler metal comprises a CuSn-based matrix brazing filler metal and a metallic titanium electroplated layer coated outside the CuSn-based matrix brazing filler metal, wherein a transition layer formed through a diffusion reaction between a solid solution in the CuSn-based matrix brazing filler metal and the metallic titanium electroplated layer is arranged between the matrix brazing filler metal and the metallic titanium electroplated layer. According to the CuSnTi foil brazing filler metal and the preparation method thereof, which are provided by the invention, the operation is simple and convenient, the technical bottleneck of brazing filler metal preparation of a traditional method is broken through, and a new green manufacturing method is provided for a new-shape high-quality active brazing filler metal. The content of active element Ti in the CuSnTi brazing filler metal is increased with regard to the CuSnTi brazing filler metal, and the defect that a traditional CuSnTi brazing filler metal is difficult to form and the defects of titanium electroplating of a molten salt system are overcome. The method has the advantages of being easy to form, high in processing efficiency, low in cost and the like, and provides a new technical way for manufacturing and production for the copper-tin-titanium brazing filler metal.
Description
Technical field
The present invention relates to brazing material, more particularly, to a kind of copper and tin titanium solder, and the preparation method of the copper and tin titanium solder.
Background technology
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
It is many to exist with powder-form, it is difficult to shape, be a great problem for perplexing domestic and international soldering worker.
Titanium has the advantages that specific strength is high, corrosion resistance is strong, is usually used on submarine, aircraft as a kind of strategic light metal,
Play a great role in navigation, aviation field, in metal surface, electrodeposition of titanium can play the corrosion-resistant effect of protection, can be applicable 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 immature also imperfection of the electroplating technology of titanium.Mesh
Front conventional method is as follows：One be electric arc ionization electro-plating method, using Titanium ionize in vacuum or inert gas be titanium from
Son and then bombarding cathode implement plating；Two is second-level titanizing method, and last layer active metal is first plated mainly on matrix（Such as
Magnesium）, then cleaned with titanium tetrachloride solution, Titanium displaced by magnesium and be then plated on matrix；Three is fuse salt
Electro-plating method, with carbon oxygen titanium as anode, plating metal as negative electrode, fuse salt be electrolyte implement plating.But, electric arc ionization electricity
Electroplating method processing step is more, and energy resource consumption is high, and process is complicated, and operation difficulty is big；In second-level titanizing method, the electrode potential of magnesium is same
Sample is relatively low, and plating is difficult to；Fuse salt electro-plating method includes that titanium is smelted and titanium electroplates two processes, coating quality and stability
It is poor.
At present, 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
Little in arc light heated perimeter, the copper and tin titanium solder for preparing every time is less than 1000g, it is impossible to industrialization production, while prepared by the method
Copper and tin titanium solder due to arc light irradiation area it is narrow, easily there is tissue odds, Ti elements local segregation phenomenon so that copper and tin titanium
Solder performance deteriorates, it is difficult to normal to use.And vacuum smelting method when powdery copper and tin titanium solder is prepared with certain advantage,
But when copper and tin titanium foil band solder is prepared, due to there is CuSn brittlement phases so that solder plasticity is deteriorated and 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, it is impossible to meet engineering reality
Performance indications require.Therefore, electric arc melting and vacuum smelting method have certain in terms of copper and tin titanium foil is prepared with solder
Limitation.
The content of the invention
Present invention aims to the technology bottle of the deficiency and Titanium Electroplating technique of above-mentioned existing copper and tin titanium solder shaping
A kind of neck, there is provided the copper and tin titanium solder of excellent performance, and easily shaping, the preparation method of high in machining efficiency, low cost are provided.
The purpose of the present invention is realized in the following manner：
A kind of copper and tin titanium solder, including CuSn matrixes solder and the Titanium electrodeposited coating being coated on outside CuSn matrix solders, matrix
There is diffusion reaction for the solid solution in CuSn matrix solders and Titanium electrodeposited coating between solder and Titanium electrodeposited coating to be formed
Transition zone.
The CuSn matrixes solder, the percentage thickness between transition zone and titanium electrodeposited coating are respectively：Matrix solder 65.0 ~
92.0 %, 7.5 ~ 33.5 % of transition zone, 0.5 ~ 1.5 % of metal level.
The thickness of the copper and tin titanium solder is 15 ~ 85 μm.
Also containing the Ni elements that mass fraction is 0.4-1.2 % in the CuSn matrixes solder.
The preparation method of copper and tin titanium solder as above, comprises the following steps：
（1）Prefabricated CuSn matrixes solder；
（2）With CuSn matrix solders as negative electrode, simple substance titanium is anode, in CuSn matrix solder electroplating surface titanium coatings；
（3）After titanium technique to be electroplated is finished, 1 ~ 10 min, Ran Houyu will be permeated in its vacuum environment at 1650 ~ 1700 DEG C
After 2 ~ 30 h being spread in 1550 ~ 1650 DEG C of vacuum drying ovens, be obtained copper and tin titanium solder after cooling.
The step（2）Specially：With CuSn matrix solders as negative electrode, with simple substance titanium as anode, with every 1000mL water
Add 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 are formulated as electroplate liquid, implement Titanium Electroplating；
0.003 ~ 0.008 moL of sodium vanadate is additionally added in the electroplate liquid per 1000mL.
The surfactant is alkyl ether surfactant；Further, the alkyl ether surfactant is OP-
10th, any one of ethoxylated dodecyl alcohol, polyethylene glycol trimethyl nonyl ethers, NPE.
The Titanium Electroplating is carried out under vacuum environment or inert gas shielding environment, and technological parameter is：Current density 0.5 ~ 5
A/dm2, 35 ~ 50 DEG C of electroplating solution temperature, 2 ~ 15 min of plating time.
CuSnTi foil solders that the present invention is provided and preparation method thereof, it is simple, convenient, breach conventional method system
The technical bottleneck of standby solder, the high-quality active solder for neomorph provide a kind of new Method of Green Manufacture.To CuSnTi
The content of active element Ti in CuSnTi solders for solder, is improve, traditional CuSnTi solders is overcome and is difficult to shape and melts
Melt the shortcoming of salt system Titanium Electroplating, the method has easily shaping, high in machining efficiency, low cost and other advantages, is copper and tin titanium solder
Manufacture production provides a kind of new technological approaches.
Additionally, based on binary and above copper alloy, such as copper palladium, copper manganese, cupro-nickel manganese etc., using preparation method of the present invention
In its electroplating surface titanium, the copper alloy or spelter solder of titaniferous are prepared in the scope of the present invention.
Specific embodiment
Embodiment 1
A kind of copper and tin titanium solder, including CuSn matrixes solder and the Titanium electrodeposited coating being coated on outside CuSn matrix solders, matrix
There is diffusion reaction for the solid solution in CuSn matrix solders and Titanium electrodeposited coating between solder and Titanium electrodeposited coating to be formed
Transition zone；CuSn matrix solders, the percentage thickness between transition zone and titanium electrodeposited coating are respectively：Matrix solder 65.0 ~
92.0 %, 7.5 ~ 33.5 % of transition zone, 0.5 ~ 1.5 % of metal level；The thickness of copper and tin titanium solder is 15 ~ 85 μm；Further,
Except the Cu containing 55-65% in CuSn matrix solders, the Sn of 34-44.5%, also containing solder 0.4-1.2% based on quality
Ni, adds Ni that CuSn matrixes solder can be avoided to form CuSn frangible compounds, based on the shaping of solder lay the foundation.
The preparation method of copper and tin titanium solder as above, comprises the following steps：
（1）Prefabricated CuSn matrixes solder：First raw metal Cu, Sn and micro Ni are put in smelting furnace, Jing casting, annealing,
Extruding, roll forming, are made as CuSn matrix solders in advance；
（2）With CuSn matrix solders as negative electrode, simple substance titanium is anode, in CuSn matrix solder electroplating surface titanium coatings；
（3）After titanium technique to be electroplated is finished, 1 ~ 10 min of infiltration will be dried in its vacuum environment at 1650 ~ 1700 DEG C, so
After 1550 ~ 1650 DEG C of 2 ~ 30 h of diffusion in vacuum, to form transition zone, then along with the furnace cooling, is obtained thickness for 15 ~ 85 μm
Copper and tin titanium solder；The transition zone of formation contributes to matrix solder and titanium coating forms metallurgical binding, improves knot between the two
With joint efforts, while the mechanical property of CuSnTi solders can be improved, regulation and control combination interface is organized and thing phase composition, contributes to strengthening
The active function of CuSnTi solders；If no transition zone, titanium electrodeposited coating（1660 ℃）With matrix solder（970~990℃）It is molten
Change temperature difference larger, copper and tin titanium alloy is difficult to shape, easy embrittlement, does not have the effect of active solder.
Step（2）Specially：With CuSn matrix solders as negative electrode, with simple substance titanium as anode, to add 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, arranges electric current, voltage, under vacuum environment or inert gas shielding environment, implements electrodeposition of titanium；Electricity is heavy
Accumulating titanium technological parameter is：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 dispersant sodium vanadate, the surface-active are additionally added in every 1000mL electroplate liquids
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, NPE.
The invention has the advantages that：
1）Electrodeposition of titanium-infiltration-diffusion composite preparation process that the present invention is provided, overcomes traditional CuSnTi solders and is difficult to shape
And the deficiency of conventional electroplating method, it is a kind of new way of offer of neomorph CuSnTi solders shaping；2）Contain in matrix solder
Micro- Ni, it is to avoid CuSn frangible compounds are formed in CuSn matrix solders, based on the shaping of solder lay the foundation；3）Institute
The electrodeposition of titanium method of offer, not only can implement titanizing in monometallic, alloy surface, and in welding material ti coat on diamond,
Shaping for neomorph metal material especially titaniferous welding material provides a kind of new approaches；4）Applied in electrodeposition of titanium process
Bath temperature is low, the time is short, sedimentation rate is high, acts on energy-conservation, consumption reduction；5）Electrodeposition of titanium-infiltration-the diffusion is combined
Preparation method is in vacuum environment（Or inert gas shielding）Lower enforcement, the CuSnTi solders cleanliness factor of preparation are high, do not contain any
Impurity；6）Using current density, bath temperature, plating time, bath concentration multi-parameter Collaborative Control technology, by regulating and controlling titanium electricity
Coating, the thickness of transition zone improve the content of active element Ti in CuSnTi solders.
Embodiment 2
A kind of CuSnTi solders, by matrix solder BCu60Sn（Containing Ni 0.8%）With the gold being coated on outside BCu60Sn matrix solders
Category titanium electrodeposited coating composition, transition zone are that CuTi compound phases and SnTiNi compound phases are constituted.Matrix solder, transition zone, plating
The percentage thickness of layer is as follows, matrix solder：92.0 %, transition zone：7.5 %, electrodeposited coating：0.5 %.
The preparation method of copper and tin titanium solder as above, comprises the following steps：
600 g of metallic copper, 392 g of tin, 8 g of nickel are inserted into smelting furnace first, Jing casting, annealing, extruding, roll forming are prefabricated
It is 80 μm of ribbon base solder BCu60Sn for thickness；Then using Titanium Electroplating technique in BCu60Sn matrix solders positive and negative electricity
Titanizing（15 μm of one side thickness）；After technique to be electroplated is finished, 10 min in the vacuum drying chamber for putting it into 1650 DEG C, are permeated,
After 30 h are spread in being then placed in 1550 DEG C of vacuum drying oven, along with the furnace cooling, prepared thickness are 85 μm of CuSnTi solders.
Wherein：Plating titanium solution is by 50 g/L of titanium sulfate（0.208moL/L）, 25 g/L of sodium sulphate（0.176moL/L）, matter
Amount fraction is 98% concentrated sulfuric acid, 70 ml/L（1.288moL/L）, 25 g/L of OP-10,1000 ml of deionized water composition.Concrete 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 is carried out in vacuum environment.
CuSnTi solders prepared by said method, compared with matrix solder BCu60Sn, wetting areas improve 7.5 %.
Embodiment 3
A kind of CuSnTi solders, by matrix solder BCu55Sn（Containing 1.0 % of Ni）Be coated on outside BCu55Snu matrix solders
Titanium electrodeposited coating is constituted, and transition zone is that CuTi compound phases and SnTiNi compound phases are constituted.Matrix solder, transition zone, electricity
The percentage thickness of coating is as follows, matrix solder：85.0 %, transition zone：14.0 %, electrodeposited coating：1.0 %.
The preparation method of copper and tin titanium solder as above, comprises the following steps：
550 g of metallic copper, 440 g of tin, 10 g of nickel are inserted into smelting furnace first, Jing casting, annealing, extruding, roll forming are prefabricated
It is 30 μm of ribbon base solder BCu55Sn for thickness；Then using Titanium Electroplating technique in BCu55Sn matrix solders positive and negative electricity
Titanizing（10 μm of one side thickness）；After technique to be electroplated is finished, 5 min are permeated in the vacuum drying chamber for putting it into 1700 DEG C, so
After 2 h are spread in being put into 1650 DEG C of vacuum drying oven afterwards, along with the furnace cooling, prepared thickness are 35 μm of CuSnTi solders.
Wherein：Plating titanium solution is by 40 g/L of titanium sulfate（0.166moL/L）, 20 g/L of sodium sulphate（0.141moL/L）, matter
Amount fraction is 98% concentrated sulfuric acid, 40 ml/L（0.746moL/L）, 15 g/L of ethoxylated dodecyl alcohol, 1000 ml groups of deionized water
Into.Concrete 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 is carried out in helium environmental protection.
CuSnTi solders prepared by said method, compared with matrix solder BCu55Sn, wetting areas improve 9.6 %.
Embodiment 4
A kind of CuSnTi solders, by matrix solder BCu65Sn（Containing 0.5 % of Ni）With the gold being coated on outside BCu65Sn matrix solders
Category titanium electrodeposited coating composition, transition zone are that CuTi compound phases and SnTiNi compound phases are constituted.Matrix solder, transition zone, plating
The percentage thickness of layer is as follows, matrix solder：65.0 %, transition zone：33.5 %, electrodeposited coating：1.5 %.
The preparation method of copper and tin titanium solder as above, comprises the following steps：
650 g of metallic copper, 345 g of tin, 5 g of nickel are inserted into smelting furnace first, Jing casting, annealing, extruding, roll forming are prefabricated
It is 10 μm of ribbon base solder BCu65Sn for thickness；Then using Titanium Electroplating technique in Bcu65Sn matrix solders positive and negative electricity
Titanizing（6 μm of one side thickness）；After technique to be electroplated is finished, 1 min is permeated in the vacuum drying chamber for putting it into 1650 DEG C, so
After 12 h are spread in being put into 1550 DEG C of vacuum drying oven afterwards, along with the furnace cooling, prepared thickness are 15 μm of CuSnTi solders.
Wherein：Plating titanium solution is by 35 g/L of titanium sulfate（0.146moL/L）, 10 g/L of sodium sulphate（0.07moL/L）, matter
Amount fraction is 98% concentrated sulfuric acid, 50 ml/L（0.92moL/L）, 10 g/L of polyethylene glycol trimethyl nonyl ethers, deionized water 1000
Ml is constituted.Concrete 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 are carried out in vacuum environment.
CuSnTi solders prepared by said method, compared with matrix solder BCu65Sn, wetting areas improve 12.4 %.
Embodiment 5
A kind of CuSnTi solders, by matrix solder BCu55Sn（Containing 0.6 % of Ni）With the gold being coated on outside BCu55Sn matrix solders
Category titanium electrodeposited coating composition, transition zone are that CuTi compound phases and SnTiNi compound phases are constituted.Matrix solder, transition zone, plating
The percentage thickness of layer is as follows, matrix solder：78.8 %, transition zone：20.0 %, electrodeposited coating：1.2 %.
The preparation method of copper and tin titanium solder as above, comprises the following steps：
550 g of metallic copper, 444 g of tin, 6 g of nickel are inserted into smelting furnace first, Jing casting, annealing, extruding, roll forming are prefabricated
It is 25 μm of ribbon base solder BCu55Sn for thickness；Then using Titanium Electroplating technique in BCu55Sn matrix solders positive and negative electricity
Titanizing（10 μm of one side thickness）；After technique to be electroplated is finished, 3 min are permeated in the vacuum drying chamber for putting it into 1700 DEG C, so
After 20 h are spread in being put into 1650 DEG C of vacuum drying oven afterwards, along with the furnace cooling, prepared thickness are 30 μm of CuSnTi solders.
Wherein：Plating titanium solution is by 45 g/L of titanium sulfate（0.188moL/L）, 15 g/L of sodium sulphate（0.106moL/L）, matter
Amount fraction is 98% concentrated sulfuric acid, 55 ml/L（1.012moL/L）, 20 g/L of NPE, 1000 ml groups of deionized water
Into.Concrete 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 are carried out in argon gas protection environment.
CuSnTi solders prepared by said method, compared with matrix solder BCu55Sn, wetting areas improve 15.3 %.
Embodiment 6
A kind of CuSnTi solders, by matrix solder BCu60Sn（Containing 0.8 % of Ni）With the gold being coated on outside BCu60Sn matrix solders
Category titanium electrodeposited coating composition, transition zone are that CuTi compound phases and SnTiNi compound phases are constituted.Matrix solder, transition zone, plating
The percentage thickness of layer is as follows, matrix solder：81.0 %, transition zone：18.1 %, electrodeposited coating：0.9 %.
The preparation method of copper and tin titanium solder as above, comprises the following steps：
600 g of metallic copper, 392 g of tin, 8 g of nickel are inserted into smelting furnace first, Jing casting, annealing, extruding, roll forming are prefabricated
It is 50 μm of ribbon base solder BCu60Sn for thickness；Then using Titanium Electroplating technique in BCu60Sn matrix solders positive and negative electricity
Titanizing（15 μm of one side thickness）；After technique to be electroplated is finished, 10 min in the vacuum drying chamber for putting it into 1700 DEG C, are permeated,
After 25 h are spread in being then placed in 1650 DEG C of vacuum drying oven, along with the furnace cooling, prepared thickness are 60 μm of CuSnTi solders.
Wherein：Plating titanium solution is by 40 g/L of titanium sulfate（0.167moL/L）, 18 g/L of sodium sulphate（0.127moL/L）, matter
Amount fraction is 98% concentrated sulfuric acid, 60 ml/L（1.104moL/L）, 16 g/L of polyethylene glycol trimethyl nonyl ethers, deionized water 1000
Ml is constituted.Concrete 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, during plating
Between 5.5 min, the Titanium Electroplating technique carried out in vacuum environment.
CuSnTi solders prepared by said method, compared with matrix solder BCu60Sn, wetting areas improve 18.1 %.
Embodiment 7
A kind of CuSnTi solders, by matrix solder BCu62Sn（Containing 0.4 % of Ni）With the gold being coated on outside BCu62Sn matrix solders
Category titanium electrodeposited coating composition, transition zone are that CuTi compound phases and SnTiNi compound phases are constituted.Matrix solder, transition zone, plating
The percentage thickness of layer is as follows, matrix solder：75.0 %, transition zone：24.2%, electrodeposited coating：0.8 %.
The preparation method of copper and tin titanium solder as above, comprises the following steps：
620 g of metallic copper, 376 g of tin, 4 g of nickel are inserted into smelting furnace first, Jing casting, annealing, extruding, roll forming are prefabricated
It is 40 μm of ribbon base solder BCu62Sn for thickness；Then electroplated in BCu62Sn matrix solders positive and negative using Titanium Electroplating technique
Titanium（15 μm of one side thickness）；After technique to be electroplated is finished, 4min is permeated in the vacuum drying chamber for putting it into 1680 DEG C, then
After 15 h are spread in being put into 1600 DEG C of vacuum drying oven, along with the furnace cooling, prepared thickness are 50 μm of CuSnTi solders.
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 fraction is 98% concentrated sulfuric acid 0.9moL/L, and NPE 20g/L, 1000 ml of deionized water are constituted.It is concrete to electroplate
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
Carry out in argon gas protection environment.
CuSnTi solders prepared by said method, compared with matrix solder BCu62Sn, wetting areas improve 14.6 %.
Embodiment 8
A kind of CuSnTi solders, by matrix solder BCu55Sn（Containing Ni 1.2%）With the gold being coated on outside BCu55Sn matrix solders
Category titanium electrodeposited coating composition, transition zone are that CuTi compound phases and SnTiNi compound phases are constituted.Matrix solder, transition zone, plating
The percentage thickness of layer is as follows, matrix solder：70 %, transition zone：29.3%, electrodeposited coating：0.7%.
The preparation method of copper and tin titanium solder as above, comprises the following steps：
550 g of metallic copper, 438 g of tin, 12 g of nickel are inserted into smelting furnace first, Jing casts, anneals, extruding, roll forming, in advance
Thickness is made as 50 μm of ribbon base solder BCu55Sn；Then using Titanium Electroplating technique in BCu55Sn matrix solder positive and negatives
Titanium Electroplating（18 μm of one side thickness）；After technique to be electroplated is finished, in the vacuum drying chamber for putting it into 1670 DEG C, 8min is permeated,
After spreading 8h in being then placed in 1600 DEG C of vacuum drying oven, along with the furnace cooling, prepared thickness are 70 μm of CuSnTi solders.
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 fraction is 98% concentrated sulfuric acid 1.0moL/L, and polyethylene glycol trimethyl nonyl ethers 12g/L, 1000 ml of deionized water are constituted.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 is carried out in helium environmental protection.
CuSnTi solders prepared by said method, compared with matrix solder BCu55Sn, wetting areas improve 17.2 %.
Embodiment 9
A kind of CuSnTi solders, by matrix solder BCu65Sn（Containing Ni 1%）With the metal being coated on outside BCu65Sn matrix solders
Titanium electrodeposited coating is constituted, and transition zone is that CuTi compound phases and SnTiNi compound phases are constituted.Matrix solder, transition zone, electrodeposited coating
Percentage thickness it is as follows, matrix solder：90 %, transition zone：8.9%, electrodeposited coating：1.1%.
The preparation method of copper and tin titanium solder as above, comprises the following steps：
650 g of metallic copper, 440 g of tin, 10 g of nickel are inserted into smelting furnace first, Jing casts, anneals, extruding, roll forming, in advance
Thickness is made as 40 μm of ribbon base solder BCu65Sn；Then using Titanium Electroplating technique in BCu65Sn matrix solders positive and negative electricity
Titanizing（10 μm of one side thickness）；After technique to be electroplated is finished, 5min is permeated in the vacuum drying chamber for putting it into 1660 DEG C, so
After spreading 10h in being put into 1580 DEG C of vacuum drying oven afterwards, along with the furnace cooling, prepared thickness are 43 μm of CuSnTi solders.
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 fraction is 98% concentrated sulfuric acid 1.2moL/L, and ethoxylated dodecyl alcohol 18g/L, 1000 ml of deionized water are constituted.It is concrete to electroplate
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
Carry out in vacuum environment.
CuSnTi solders prepared by said method, compared with matrix solder BCu65Sn, wetting areas improve 13.5 %.
Above-described is only the preferred embodiment of the present invention, it is noted that for a person skilled in the art,
Under the premise of without departing from general idea of the present invention, some changes and improvements can also be made, these should also be considered as the present invention's
Protection domain.
Claims (10)
1. a kind of copper and tin titanium solder, it is characterised in that：Including CuSn matrixes solder and the metal being coated on outside CuSn matrix solders
Titanium electrodeposited coating, is occurred with Titanium electrodeposited coating for the solid solution in CuSn matrix solders between matrix solder and Titanium electrodeposited coating
The transition zone that diffusion reaction is formed.
2. copper and tin titanium solder as claimed in claim 1, it is characterised in that：The plating of the CuSn matrixes solder, transition zone and titanium
Percentage thickness between layer is respectively：65.0 ~ 92.0 % of matrix solder, 7.5 ~ 33.5 % of transition zone, metal level 0.5 ~ 1.5
%。
3. copper and tin titanium solder as claimed in claim 1, it is characterised in that：The thickness of the copper and tin titanium solder is 15 ~ 85 μm.
4. copper and tin titanium solder as claimed in claim 1, it is characterised in that：Also contain mass fraction in the CuSn matrixes solder
For the Ni elements of 0.4-1.2 %.
5. the preparation method of the copper and tin titanium solder according to any one of claim 1-4, it is characterised in that comprise the following steps：
（1）Prefabricated CuSn matrixes solder；
（2）With CuSn matrix solders as negative electrode, simple substance titanium is anode, in CuSn matrix solder electroplating surface titanium coatings；
（3）After titanium technique to be electroplated is finished, 1 ~ 10 min, Ran Houyu will be permeated in its vacuum environment at 1650 ~ 1700 DEG C
After 2 ~ 30 h being spread in 1550 ~ 1650 DEG C of vacuum drying ovens, be obtained copper and tin titanium solder after cooling.
6. the preparation method of copper and tin titanium solder according to claim 5, it is characterised in that：The step（2）Specially：With
CuSn matrixes solder is negative electrode, with simple substance titanium as anode, so that 0.146 ~ 0.208 moL of titanium sulfate, sulphur are added in every 1000mL water
0.07 ~ 0.176 moL of sour sodium, 0.736 ~ 1.288moL of sulfuric acid, 10 ~ 25 g of surfactant are formulated as electroplate liquid, implement plating
Titanium.
7. the preparation method of copper and tin titanium solder according to claim 6, it is characterised in that：In the electroplate liquid per 1000mL
It is additionally added 0.003 ~ 0.008 moL of sodium vanadate.
8. the preparation method of copper and tin titanium solder according to claim 6, it is characterised in that：The surfactant is alkyl
Ether surfactant.
9. the preparation method of copper and tin titanium solder according to claim 8, 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, NPE.
10. the preparation method of copper and tin titanium solder according to claim 6, it is characterised in that：The Titanium Electroplating is in vacuum ring
Carry out under border or inert gas shielding environment, technological parameter is：0.5 ~ 5 A/dm of current density2, electroplating solution temperature 35 ~ 50
DEG C, 2 ~ 15 min of plating time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610955635.6A CN106514039B (en) | 2016-11-03 | 2016-11-03 | A kind of copper and tin titanium solder and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610955635.6A CN106514039B (en) | 2016-11-03 | 2016-11-03 | A kind of copper and tin titanium solder and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106514039A true CN106514039A (en) | 2017-03-22 |
| CN106514039B CN106514039B (en) | 2019-03-08 |
Family
ID=58325418
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610955635.6A Active CN106514039B (en) | 2016-11-03 | 2016-11-03 | A kind of copper and tin titanium solder and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106514039B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107326364A (en) * | 2017-06-02 | 2017-11-07 | 泉州众志金刚石工具有限公司 | A kind of Cu Sn Ti diamond brazing coating and preparation method thereof |
| CN115989579A (en) * | 2020-10-07 | 2023-04-18 | 株式会社东芝 | Joined body, ceramic circuit board, and semiconductor device |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57209773A (en) * | 1981-06-18 | 1982-12-23 | Nippon Mining Co Ltd | Method for soldering copper or copper alloy fins to titanium tubes for finned heat exchanger |
| CN101987402A (en) * | 2010-11-30 | 2011-03-23 | 哈尔滨工业大学 | Cu-Sn-Ti solder and method for brazing Ti2AlC ceramics and Cu with same |
| CN103320822A (en) * | 2013-06-27 | 2013-09-25 | 中国铝业股份有限公司 | Method for electroplating titanium on surface of metal |
| CN105216120A (en) * | 2015-09-22 | 2016-01-06 | 河南科技大学 | A kind of diamond cutter and preparation method thereof, diamond compound tool |
| CN105345304A (en) * | 2015-12-02 | 2016-02-24 | 华北水利水电大学 | Supersaturated brazing filler metal and preparation method thereof |
| CN105862096A (en) * | 2016-06-02 | 2016-08-17 | 烟台工程职业技术学院 | Method for preparing FHA bioactive coating through electrical brush-plating-sintering method |
-
2016
- 2016-11-03 CN CN201610955635.6A patent/CN106514039B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57209773A (en) * | 1981-06-18 | 1982-12-23 | Nippon Mining Co Ltd | Method for soldering copper or copper alloy fins to titanium tubes for finned heat exchanger |
| CN101987402A (en) * | 2010-11-30 | 2011-03-23 | 哈尔滨工业大学 | Cu-Sn-Ti solder and method for brazing Ti2AlC ceramics and Cu with same |
| CN103320822A (en) * | 2013-06-27 | 2013-09-25 | 中国铝业股份有限公司 | Method for electroplating titanium on surface of metal |
| CN105216120A (en) * | 2015-09-22 | 2016-01-06 | 河南科技大学 | A kind of diamond cutter and preparation method thereof, diamond compound tool |
| CN105345304A (en) * | 2015-12-02 | 2016-02-24 | 华北水利水电大学 | Supersaturated brazing filler metal and preparation method thereof |
| CN105862096A (en) * | 2016-06-02 | 2016-08-17 | 烟台工程职业技术学院 | Method for preparing FHA bioactive coating through electrical brush-plating-sintering method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107326364A (en) * | 2017-06-02 | 2017-11-07 | 泉州众志金刚石工具有限公司 | A kind of Cu Sn Ti diamond brazing coating and preparation method thereof |
| CN107326364B (en) * | 2017-06-02 | 2023-08-11 | 泉州众志金刚石工具有限公司 | Cu-Sn-Ti diamond brazing coating and preparation method thereof |
| CN115989579A (en) * | 2020-10-07 | 2023-04-18 | 株式会社东芝 | Joined body, ceramic circuit board, and semiconductor device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106514039B (en) | 2019-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106825999A (en) | A kind of preparation method of foam metal Combined Welding tablet | |
| CN108039259A (en) | A kind of infiltration has the neodymium iron boron magnetic body of heavy rare earth and the method in neodymium iron boron magnetic body surface penetration heavy rare earth | |
| CN102011144A (en) | Nickel-based alloy material suitable for inert anode of metal molten salt electrolyzer | |
| CN110158121A (en) | Anti- tin must CP wire production technology | |
| KR101318545B1 (en) | Process for production of tin-plated steel sheets, tin-plated steel sheets and chemical conversion treatment fluid | |
| CN105345304B (en) | A kind of supersaturated solder and preparation method thereof | |
| CN106514039B (en) | A kind of copper and tin titanium solder and preparation method thereof | |
| CN114672755B (en) | Non-wetting coating suitable for resisting high-temperature aluminum permeation and preparation method thereof | |
| CN110205652A (en) | A kind of preparation method and application of copper bearing master alloy | |
| CN110158122A (en) | High temperature resistant high conductivity CP wire production method | |
| CN106334882B (en) | A kind of AgCuTi solder and preparation method thereof | |
| CN112222552B (en) | Gamma electrode wire and preparation method thereof | |
| CN107699735B (en) | Copper alloy hot dip tin alloy and preparation method thereof | |
| CN111304654B (en) | Method for plating platinum on surface of steel strip | |
| CN106757205B (en) | A kind of electrotyping process preparation method of high indium content silver solder | |
| CN103305870A (en) | Ferro-nickel anticorrosion alloy material for inert anode | |
| JP2529557B2 (en) | Lead alloy insoluble anode | |
| CN106498459B (en) | A kind of electrodeposition of titanium method | |
| CN108588507A (en) | The novel hot-dip plating aluminium alloy of resistance to hydrogen sulfide and chlorination sodium corrosion | |
| CN109778015A (en) | A kind of porous foam metal material and preparation method thereof | |
| CN107699736B (en) | One Albatra metal hot dip tin alloy and preparation method thereof | |
| CN107502782A (en) | Copper alloy hot dip rare earth tin-based alloy and preparation method thereof | |
| CN109834246A (en) | A method of composition metal porous material is prepared using hot dipping | |
| CN102031541B (en) | Production method of zinc-magnesium coated steel plate and zinc-magnesium coated steel plate | |
| US3007856A (en) | Insoluble anodes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |