CN107699735B - Copper alloy hot dip tin alloy and preparation method thereof - Google Patents

Copper alloy hot dip tin alloy and preparation method thereof Download PDF

Info

Publication number
CN107699735B
CN107699735B CN201711002540.3A CN201711002540A CN107699735B CN 107699735 B CN107699735 B CN 107699735B CN 201711002540 A CN201711002540 A CN 201711002540A CN 107699735 B CN107699735 B CN 107699735B
Authority
CN
China
Prior art keywords
alloy
pure
tin
sncu7
hot dip
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.)
Expired - Fee Related
Application number
CN201711002540.3A
Other languages
Chinese (zh)
Other versions
CN107699735A (en
Inventor
田保红
刘玉亮
张毅
殷婷
王冰洁
孙国强
田然
张晓辉
赵转
刘勇
贾淑果
宋克兴
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henan University of Science and Technology
Original Assignee
Henan University of Science and Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henan University of Science and Technology filed Critical Henan University of Science and Technology
Priority to CN201711002540.3A priority Critical patent/CN107699735B/en
Publication of CN107699735A publication Critical patent/CN107699735A/en
Application granted granted Critical
Publication of CN107699735B publication Critical patent/CN107699735B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C13/00Alloys based on tin
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making alloys
    • C22C1/02Making alloys by melting
    • C22C1/03Making alloys by melting using master alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C13/00Alloys based on tin
    • C22C13/02Alloys based on tin with antimony or bismuth as the next major constituent
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/08Tin or alloys based thereon

Abstract

The present invention relates to an Albatra metal hot dip tin alloys, are made of the element of following mass fraction: the Cu of the Cr of the Sb of the Bi of the Zn of 1.0-9.0%, 0.5-10.0%, 0.3-3.5%, 0.15-0.9%, 0.1-0.5%, and surplus is Sn and inevitable impurity element.The performance indicator of copper alloy hot dip tin alloy of the invention are as follows: standard electrode potential 0.0531-0.3017V, 203.3-219.5 DEG C of fusing point, tensile strength 50.1-98.6MPa, elongation percentage 18.3-35.7%;Tin alloy preparation cost of the invention is low, fusion temperature is lower than pure tin, and hot-dip coating IMC thickness is thin and the long main trend of thickness is small, and cavity and whisker are not likely to produce in use.

Description

Copper alloy hot dip tin alloy and preparation method thereof
Technical field
The present invention relates to metal coating material fields, and in particular to an Albatra metal hot dip tin alloy and its preparation side Method.
Background technique
Tin plating copper alloy plate strip is widely used in the high-end fields such as aerospace, military project, automobile, communication and electronics, to the greatest extent Pipe China copper plate/strip industry continues to develop, but copper alloy plate strip tin plating at present is not still able to satisfy the market demand.At present about The research of the institutional framework of copper alloy plate strip tin coating, performance and production technology is concentrated mainly on the research of electrotinning, electrotinning Major advantage is coated metal thickness uniformly and can arbitrarily control, but its complex production process, operation require stringent, electroplating device Price is high, electroplating bath components are complicated.
Hot-dip is that treated metal works are immersed to a kind of method that the coat of metal is obtained in molten metal, referred to as Hot dip.Compared with plating, the advantages of hot-dip be weldability is good, plated layer compact securely, production is simple, process is simple, delivery Phase is short, the simple price of equipment is low etc., the disadvantage is that scruff is more, tin thickness is uneven, tin liquor is oxidizable, resting period is short etc..Mesh Preceding China is concentrated mainly on the hot dipped tinning of steel surface, i.e., the matrix gold of most of hot dipped tinnings about the research of hot dipped tinning Belonging to is steel material, and then more rare as the hot dipped tinning of basis material using copper or copper alloy.
Pure tin should not be directly used in or immersion, main reason is that, the room temperature residence time is longer or hot operation holds So that hot tinning material surface is formed the whisker of electric conductivity, cause electric power connector or integrated circuit board short circuit, thus to copper and The research of the dedicated kamash alloy of Cu alloy material hot dip is of great significance.
Summary of the invention
The purpose of the present invention is to provide Albatra metal hot dip tin alloys and preparation method thereof.
In order to solve the above technical problems, the technical scheme adopted by the invention is that: copper alloy hot dip tin alloy, by following The element of mass fraction forms: the Cr of the Sb of the Bi of the Zn of 1.0-9.0%, 0.5-10.0%, 0.3-3.5%, 0.15-0.9%, 0.1- 0.5% Cu, surplus are Sn and inevitable impurity element.
Further, the tin alloy refers to the intermediate alloy by pure Sn, pure Sb, pure Bi, pure Zn, intermediate alloy SnCu7( The mass fraction that the mass fraction of middle Cu is 7%, Sn is the quality for 93%) referring to Cr in the intermediate alloy with intermediate alloy SnCr1.5( The mass fraction that score is 1.5%, Sn is 98.5%) to be made.
Further, at least a kind of purity of metal is based on mass fraction in the pure Sn, pure Sb, pure Bi and pure Zn It is 99.95% or more.
Further, the purity of the intermediate alloy SnCu7 is based on mass fraction are as follows: Cu >=6.9%, surplus Sn.
Further, the purity of the intermediate alloy SnCr1.5 is based on mass fraction are as follows: Cr >=1.49%, surplus are Sn。
The preparation method of one Albatra metal hot dip tin alloy, comprising the following steps: each in tin alloy as described above Element mass fraction weighs pure Sn, pure Sb, pure Bi, pure Zn, intermediate alloy SnCu7 and intermediate alloy SnCr1.5, and pure Sn is put into Melting is carried out in intermediate frequency vacuum melting furnace, being evacuated to pressure in furnace is 0.005-0.010Pa, is then charged with argon gas to 0.2- 0.3MPa is warming up to 550-650 DEG C, and heat preservation to pure Sn is completely melt;Pure Sb and pure Bi is added, keeps the temperature complete to pure Sb and pure Bi Fusing;Pure Zn is added, heat preservation to pure Zn is completely melt;Intermediate alloy SnCu7 is added, heat preservation to intermediate alloy SnCu7 is completely molten Change;Intermediate alloy SnCr1.5 is added, heat preservation to intermediate alloy SnCr1.5 is completely melt;400 DEG C of casting ingot-formings are cooled to, that is, are made Obtain copper alloy hot dip tin alloy.
Further, the furnace lining material in the intermediate frequency vacuum melting furnace is magnesia.
Further, the preparation method of the intermediate alloy SnCu7 includes the following steps: to weigh according to mass ratio 93:7 pure Sn and pure Cu is put into water cooling copper sleeve vacuum non-consumable smelting furnace, and being evacuated to pressure in furnace is 0.007Pa, is then charged with argon gas To 0.2-0.3MPa, electric arc melting to ingredient is completely melt, closing electric arc makes melt be cooled to complete solidification, by melt after solidification Turn-over, repeated melting, cooling, turn-over step 2-4 times, obtains intermediate alloy SnCu7.
Further, the preparation method of the intermediate alloy SnCr1.5 includes the following steps: according to mass ratio 98.5:1.5 Pure Sn and pure Cr are weighed, water cooling copper sleeve vacuum non-consumable smelting furnace is put into, being evacuated to pressure in furnace is 0.005-0.010Pa, Argon gas is then charged with to 0.2-0.3MPa, electric arc melting to ingredient is completely melt, closing electric arc makes melt be cooled to complete solidification, Melt turn-over after solidifying, repeated melting, cooling, turn-over step 2-4 times obtain intermediate alloy SnCr1.5.
In the present invention each alloys producing and the utility model has the advantages that
1, Cu main function: when hot dip, improving the wetability between tin alloy and Copper substrate, improves liquid alloy copper-based Spreading ability on body, especially using the copper alloy containing Ni as basis material when, help to be formed on copper alloy matrix surface Alloy intermediate compound (CuNi)6Sn5, and then the wetability between tin alloy and Copper substrate is improved, while there is solution strengthening to mention High alloy hardness, the effect for improving Wear Resistance;
2, the effect of Zn: the fusing point of tin alloy is mainly reduced;It, can be in the case where keeping alloy plasticity to be basically unchanged Improve the tensile strength and croop property of alloy;SnZn mixed oxidization film is formed in wet condition, and due to mixed oxidization Membrane volume expansion is easy to crack, so that the reliability of electric power connector hot dip tin layers can be improved;
3, acicular Cu the effect of Bi: can be made6Sn5Compound is changed into the compound of scallop shape, prevents penetrability The formation of Cu6Sn5 compound;The surface tension for reducing the melt of tin alloy, improves the spreading ability of aluminium alloy;Reduce tin alloy Fusing point;Improve the intensity and hardness of hot-dip Sn alloy-layer;The presence of a small amount of Bi particle, the electrical contact that alloy can be improved are special Property, promote the peeling of alloy surface oxidation film;
4, the effect of Sb: the main growth tendency for inhibiting intermetallic compound and reduction growth rate;Reduce tin alloy at This;The hardness for improving tin alloy, to improve the fretting wear drag of hot dip tin alloy;
5, the effect of Cr: combining addition with Zn, and the antioxygenic property of tin alloy can be improved;Addition is cooperateed with Bi, it can be with The wettability for improving tin alloy, inhibits the growth of surface film oxide;Refining alloy tissue improves the plasticity of alloy;Long-term In use process, timeliness can occur under the action of heating effect of current and form SnZnCr interphase, there is artificial aging to strengthen effect It answers;
6, the performance indicator of copper alloy hot dip tin alloy of the present invention are as follows: standard electrode potential 0.0531-0.3017V melts 203.3-219.5 DEG C of point, tensile strength 50.1-98.6MPa, elongation percentage 18.3-35.7%;Tin alloy preparation cost of the invention Low, fusion temperature is lower than pure tin, and hot-dip coating IMC thickness is thin and the long main trend of thickness is small, and cavity and whisker are not likely to produce in use The advantages that, it can be used for processing copper alloy plate strip and carry out hot-dip deep processing, the copper alloy of hot-dip is carried out through alloy of the invention Strip product is mainly used for all kinds of electric power connectors in fields and the electronics such as integrated circuit, electronic apparatus, intelligence equipment, auto industry The manufacture of connector etc..
Specific embodiment
The present invention will be further described in detail combined with specific embodiments below.
Embodiment 1
A kind of copper alloy plate strip hot dip tin alloy, is made of the element of following mass fraction: 7.0% Zn, 3.0% Bi, 0.5% Sb, 0.15% Cr, 0.2% Cu, surplus are Sn and inevitable impurity element;
The preparation method of the tin alloy the following steps are included:
(1) preparation of intermediate alloy:
Pure Sn and pure Cu are weighed according to the mass ratio of 93:7, water cooling copper sleeve vacuum non-consumable smelting furnace is put into, is evacuated to Pressure is 0.007Pa in furnace, is then charged with argon gas to 0.2-0.3MPa, and electric arc melting to ingredient is completely melt, closing electric arc makes Melt is cooled to complete solidification, and by melt turn-over after solidification, repeated melting, cooling, turn-over step 3 time obtain intermediate alloy SnCu7;The purity of the intermediate alloy SnCu7 is based on mass fraction are as follows: Cu >=6.9%, surplus Sn;
Pure Sn and pure Cr are weighed according to the mass ratio of 98.5:1.5, is put into water cooling copper sleeve vacuum non-consumable smelting furnace, is taken out true Pressure is 0.007Pa in sky to furnace, is then charged with argon gas to 0.2-0.3MPa, and electric arc melting to ingredient is completely melt, closes electricity Arc makes melt be cooled to complete solidification, and by melt turn-over after solidification, repeated melting, cooling, turn-over step 3 time obtain centre Alloy SnCr1.5;The purity of the intermediate alloy SnCr1.5 is based on mass fraction are as follows: Cr >=1.49%, surplus Sn;
(2) pure Sn, pure Sb, pure Bi, pure Zn, intermediate alloy SnCu7 and centre are weighed according to each element mass fraction Purity in alloy SnCr1.5, the pure Sn, pure Sb, pure Bi and pure Zn is 99.95% or more based on mass fraction;It will be pure Sn, which is put into intermediate frequency vacuum melting furnace, carries out melting, and furnace lining material is magnesia, and being evacuated to pressure in furnace is 0.008Pa, then Argon gas is filled with to 0.2-0.3MPa, is warming up to 600 DEG C, heat preservation to pure Sn is completely melt (about 30-60min);Pure Sb and pure is added Bi, 600 DEG C of heat preservations to pure Sb and pure Bi are completely melt (about 30-60min);Pure Zn is added, 600 DEG C of heat preservations to pure Zn are completely melt (about 30-60min);Intermediate alloy SnCu7 is added, 600 DEG C of heat preservations are extremely completely melt (about 30- to intermediate alloy SnCu7 60min);Intermediate alloy SnCr1.5 is added, 600 DEG C of heat preservations to intermediate alloy SnCr1.5 are completely melt (about 30-60min);Drop Temperature selects punching block as die casting ingot, obtains copper alloy plate strip hot dip tin alloy to 400 DEG C;
The performance indicator of tin alloy obtained are as follows: standard electrode potential 0.1673V, 202.4 DEG C of fusing point, tensile strength 57.3MPa, elongation percentage 32.7%.
Embodiment 2
A kind of copper alloy plate strip hot dip tin alloy, is made of the element of following mass fraction: 8.0% Zn, 6.5% Bi, 2.0% Sb, 0.30% Cr, 0.25% Cu, surplus are Sn and inevitable impurity element;
The preparation method is the same as that of Example 1;The performance indicator of tin alloy obtained are as follows: standard electrode potential 0.0878V, fusing point 214.5 DEG C, tensile strength 81.73MPa, elongation percentage 25.9%.
Embodiment 3
A kind of copper alloy plate strip hot dip tin alloy, is made of the element of following mass fraction: 9.0% Zn, 10.0% Bi, 3.5% Sb, 0.5% Cr, 0.3% Cu, surplus are Sn and inevitable impurity element;
The preparation method is the same as that of Example 1;The performance indicator of tin alloy obtained are as follows: standard electrode potential 0.0775V, fusing point 227.4 DEG C, tensile strength 98.6MPa, elongation percentage 18.3%.
Embodiment 4
A kind of copper alloy plate strip hot dip tin alloy, is made of the element of following mass fraction: 1.0% Zn, 0.5% Bi, 0.3% Sb, 0.9% Cr, 0.4% Cu, surplus are Sn and inevitable impurity element;
The preparation method is the same as that of Example 1;The performance indicator of tin alloy obtained are as follows: standard electrode potential 0.3017V, fusing point 203.3 DEG C, tensile strength 50.1MPa, elongation percentage 35.7%.
Embodiment 5
A kind of copper alloy plate strip hot dip tin alloy, is made of the element of following mass fraction: 3.0% Zn, 4.5% Bi, 1.25% Sb, 0.65% Cr, 0.5% Cu, surplus are Sn and inevitable impurity element;
The preparation method is the same as that of Example 1;The performance indicator of tin alloy obtained are as follows: standard electrode potential 0.2138V, fusing point 209.2 DEG C, tensile strength 70.7MPa, elongation percentage 28.4%.
Embodiment 6
A kind of copper alloy plate strip hot dip tin alloy, is made of the element of following mass fraction: 5.0% Zn, 8.0% Bi, 2.8% Sb, 0.8% Cr, 0.1% Cu, surplus are Sn and inevitable impurity element;
The preparation method is the same as that of Example 1;The performance indicator of tin alloy obtained are as follows: standard electrode potential 0.1153V, fusing point 219.5 DEG C, tensile strength 74.6MPa, elongation percentage 26.9%.
Above embodiments are only some embodiments of the invention, in the case where not departing from basic idea of the present invention, Any replacement and improvement should all be included in protection scope of the present invention.

Claims (4)

1. the hot dip tin alloy of copper alloy containing Ni, which is characterized in that be made of the element of following mass fraction: 8.0-9.0%'s The Cu of the Cr of the Sb of the Bi of Zn, 6.5-10.0%, 0.3-3.5%, 0.15-0.9%, 0.1-0.5%, surplus is for Sn and inevitably Impurity element;
The tin alloy is made of pure Sn, pure Sb, pure Bi, pure Zn, intermediate alloy SnCu7 and intermediate alloy SnCr1.5;
The pure Sn, pure Sb, pure Bi and pure Zn purity be based on mass fraction 99.95% or more;
The purity of the intermediate alloy SnCu7 is based on mass fraction are as follows: Cu >=6.9%, surplus Sn;
The purity of the intermediate alloy SnCr1.5 is based on mass fraction are as follows: Cr >=1.49%, surplus Sn;
Tin alloy preparation method the following steps are included: weighing pure Sn, pure Sb, pure according to each element mass fraction Bi, pure Zn, intermediate alloy SnCu7 and intermediate alloy SnCr1.5, pure Sn is put into intermediate frequency vacuum melting furnace and carries out melting, is taken out Pressure is 0.005-0.010Pa in vacuum to furnace, is then charged with argon gas to 0.2-0.3MPa, is warming up to 550-650 DEG C, heat preservation is extremely Pure Sn is completely melt;Pure Sb and pure Bi is added, heat preservation to pure Sb and pure Bi is completely melt;Pure Zn is added, keeps the temperature complete to pure Zn Fusing;Intermediate alloy SnCu7 is added, heat preservation to intermediate alloy SnCu7 is completely melt;Intermediate alloy SnCr1.5 is added, heat preservation is extremely Intermediate alloy SnCr1.5 is completely melt;400 DEG C of casting ingot-formings are cooled to, a kind of hot dip tin alloy of copper alloy containing Ni is obtained.
2. the hot dip of copper alloy containing Ni tin alloy according to claim 1, it is characterised in that: the intermediate frequency vacuum melting furnace Interior furnace lining material is magnesia.
3. the hot dip of copper alloy containing Ni tin alloy according to claim 1, which is characterized in that the intermediate alloy SnCu7 Preparation method include the following steps: to weigh pure Sn and pure Cu according to mass ratio 93:7, it is molten to be put into water cooling copper sleeve vacuum non-consumable Furnace, being evacuated to pressure in furnace is 0.005-0.010Pa, is then charged with argon gas to 0.2-0.3MPa, electric arc melting to ingredient It is completely melt, closing electric arc makes melt be cooled to complete solidification, by melt turn-over after solidification, repeated melting, cooling, turn-over step 2-4 times, obtain intermediate alloy SnCu7.
4. the hot dip of copper alloy containing Ni tin alloy according to claim 1, which is characterized in that the intermediate alloy The preparation method of SnCr1.5 includes the following steps: to weigh pure Sn and pure Cr according to mass ratio 98.5:1.5, and it is true to be put into water cooling copper sleeve Empty non-consumable smelting furnace, being evacuated to pressure in furnace is 0.007Pa, is then charged with argon gas to 0.2-0.3MPa, electric arc melting is extremely Ingredient is completely melt that closing electric arc makes melt be cooled to complete solidification, by melt turn-over after solidification, repeated melting, cooling, turn-over Step 2-4 times obtains intermediate alloy SnCr1.5.
CN201711002540.3A 2017-10-24 2017-10-24 Copper alloy hot dip tin alloy and preparation method thereof Expired - Fee Related CN107699735B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711002540.3A CN107699735B (en) 2017-10-24 2017-10-24 Copper alloy hot dip tin alloy and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711002540.3A CN107699735B (en) 2017-10-24 2017-10-24 Copper alloy hot dip tin alloy and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107699735A CN107699735A (en) 2018-02-16
CN107699735B true CN107699735B (en) 2019-09-06

Family

ID=61181478

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711002540.3A Expired - Fee Related CN107699735B (en) 2017-10-24 2017-10-24 Copper alloy hot dip tin alloy and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107699735B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110724899A (en) * 2019-11-27 2020-01-24 云南电网有限责任公司电力科学研究院 Anti-corrosion method for electric power fitting

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101245427A (en) * 2008-03-26 2008-08-20 戴国水 Leadless metal spraying material adding alloy element
CN102581507A (en) * 2012-01-19 2012-07-18 广东中实金属有限公司 Tin, zinc and bismuth multi-element eutectic lead-free solder and preparation method

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006255784A (en) * 2004-11-24 2006-09-28 Nittetsu Micro Metal:Kk Unleaded solder alloy

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101245427A (en) * 2008-03-26 2008-08-20 戴国水 Leadless metal spraying material adding alloy element
CN102581507A (en) * 2012-01-19 2012-07-18 广东中实金属有限公司 Tin, zinc and bismuth multi-element eutectic lead-free solder and preparation method

Also Published As

Publication number Publication date
CN107699735A (en) 2018-02-16

Similar Documents

Publication Publication Date Title
CN105274545A (en) Electroplating or chemical-plating pretreatment method of aluminum alloy and application of electroplating or chemical-plating pretreatment method
CN107058796B (en) A kind of microalloying of rare earth acid bronze alloy, preparation method and the method for being squeezed into bar
WO2009010473A2 (en) Method of providing a metallic coating layer and substrate provided with said coating layer
CN104778997A (en) High-temperature and high-conductivity electrical wire and preparing method thereof
CN102242382A (en) Production method of silver-plated conductor for producing highly sophisticated products for aviation and aerospace
CN107699735B (en) Copper alloy hot dip tin alloy and preparation method thereof
CN107502782B (en) Copper alloy hot dip rare earth tin-based alloy and preparation method thereof
CN107699736B (en) One Albatra metal hot dip tin alloy and preparation method thereof
CN105543602A (en) Method for preparing magnesium alloy smart phone shell electroplating copper on surface
CN101805880A (en) Zinc-titanium-aluminum intermediate alloy for hot dipping and preparation method and application thereof
CN1152974C (en) Hot-dip technology for producing steel-in-copper wires by flux activating method and its apparatus
CN104195612A (en) Cyanide-free production process of silver-plated copper-clad steel wire
CN104762639B (en) Hydrometallurgy electro-deposition operation porous aluminum based composite anode and preparation method
CN107475563B (en) One Albatra metal hot dip rare earth tin-based alloy and preparation method thereof
CN110158121A (en) Anti- tin must CP wire production technology
CN109834246A (en) A method of composition metal porous material is prepared using hot dipping
CN102337422B (en) A kind of high temperature bends down the unleaded application warding off tin alloy of corrode
CN104294359A (en) Monocrystal copper gold-plated composite bonding wire and preparation method thereof
CN107460506A (en) A kind of electroplate liquid of nickel
CN106514039B (en) A kind of copper and tin titanium solder and preparation method thereof
CN112222552A (en) Gamma electrode wire and preparation method thereof
CN100464004C (en) Target pole for coating and its casting process for external sleeve
CN109837414A (en) A kind of preparation method haveing excellent performance multipurpose Engineering Foam metal material
CN111020294A (en) Zinc-nickel alloy and preparation method thereof
CN113174503A (en) Preparation method of high-strength magnesium-based three-dimensional graphene composite material

Legal Events

Date Code Title Description
PB01 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
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20190906

Termination date: 20201024

CF01 Termination of patent right due to non-payment of annual fee