CN106077867B - One kind soldering polynary copper silver nickel niobium zirconium solder of tungsten base powder alloy - Google Patents
One kind soldering polynary copper silver nickel niobium zirconium solder of tungsten base powder alloy Download PDFInfo
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- CN106077867B CN106077867B CN201610564583.XA CN201610564583A CN106077867B CN 106077867 B CN106077867 B CN 106077867B CN 201610564583 A CN201610564583 A CN 201610564583A CN 106077867 B CN106077867 B CN 106077867B
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- base powder
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- tungsten base
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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
- B23K1/00—Soldering, e.g. brazing, or unsoldering
- B23K1/19—Soldering, e.g. brazing, or unsoldering taking account of the properties of the materials to be soldered
-
- 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
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/18—Dissimilar materials
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- Mechanical Engineering (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses one kind to be brazed the polynary copper silver nickel niobium zirconium solder of tungsten base powder alloy, and the purpose is to realize being reliably connected for tungsten base powder alloy and tungsten base powder alloy, tungsten base powder alloy and steel.Solder alloying component based on Cu, Ag, according to the mechanism of action of the alloy phase diagram of element and various addition element, addition Ni, Nb and Zr element comes from different backgrounds and possess different abilities copper silver nickel niobium zirconium solder, and brazing filler metal alloy component is by mass percentage (Wt/%)：Copper (Cu)：60 80, silver-colored (Ag)：10 30, nickel (Ni)：15, niobium (Nb)：15, zirconium (Zr) 0.1 0.5.
Description
Technical field
The present invention relates to one kind to be brazed the polynary copper silver nickel niobium zirconium solder of tungsten base powder alloy, applied to tungsten base powder alloy
Soldering and tungsten base powder alloy and other metals soldering, belong to welding and interconnection technique field.
Background technology
Tungsten base powder alloy is a kind of using tungsten as hard phase, is the composite wood that Binder Phase is formed with nickel, copper or nickel, iron etc.
Material, has high heat conduction, high intensity, high density, high-melting-point, low thermal coefficient of expansion, excellent corrosion stability, inoxidizability, shock resistance are tough
Property and the performance such as good ray absorption capacity, applied in numerous engineering fields, such as manufacture big mouth in military industry field
Footpath, rod-type kinetic energy penetrator bullet core material, machine gun armor piercing discarding sabot bullet core, counterweight and inertance element, bullet and warship canon bullet
High-explosive fragmentation in bullet material and some tactical missiles etc.；Field of machining manufacture drilling rod, connecting rod, cutter holder,
Knife bar, the pendulum of automatic watch, the compression mod of precision casting process and extrusion die etc..The development of any new material and application all from
Do not open secondary operation, only by secondary operation, material is converted to product, and this process must efficiently, low cost,
Meet the market demand in time.Tungsten base powder alloy has good ductility, can be rolled, be swaged, being forged, car, milling, plane,
Cutting thread and tapping etc. machine, and still, due to its special physical and chemical performance, there are certain difficulty for welding.This is because
Tungsten base powder alloy thermal conductivity is extremely strong, and when fusion welding, which be easy to cause, does not fuse phenomenon, when welding require using energy density it is high,
The efficient welding technology and technique that thermal weld stress amount is big, speed of welding is fast.Tungsten base powder alloy linear expansion coefficient is small, in connector
Residual stress can be produced, reduces the mechanical property and thermal shock resistance of connector.Chemism is strong under tungsten base powder alloy high temperature,
Surface staining at 300 DEG C, surface oxidation is serious at 500 DEG C, and welding process center tap is easily aoxidized, nitrogenized, inhaling hydrogen, weld seam
Metal grain is thick, requires during welding to take safeguard measure.Some researchers explore gas tungsten arc welding
(TIG), the technique such as welding (MIG) welding, laser welding, friction welding (FW), diffusion welding (DW) and soldering welding tungsten
Base powder alloy material.The power density of gas tungsten arc welding (TIG) and welding (MIG) compared with
Low, heat input is larger in welding process, and heat affected area is wide after welding, and weld grain is thick, causes joint performance to be deteriorated.Laser
Tungsten base powder alloy is directly welded, welding temperature is high, considerably beyond the recrystallization temperature (1100 ± 5 DEG C) of tungsten, what crystal grain was grown up
Quickly, the mechanical property of material substantially becomes fragile speed.Friction welding (FW) and diffusion welding (DW) are limited only be subject to equipment, technique and joint form
Small parts and component simple in structure can be welded.Using common silver-based and copper base solder soldering tungsten base powder alloy, due to tungsten
Alloy is not formed with silver, copper, soldering effect is unsatisfactory, and the intensity of brazed seam is affected, and result of the test shows, soldered fitting
Shear strength is less than 200MPa.Welding processing technology moves towards practical important processing method as exploitation new material, has
It is versatile and flexible, simple process；When manufacturing large-scale, complex components, mechanical processing, cast welding and forge welding method can be used, is changed
Greatly small, it is simple to change complexity, then gradually erection welding forms, and is one of net shaping optimum manufacturing process.Due to tungsten based powders
Alloy weldability is poor, can only manufacture component simple in structure by being machined, largely constrain it in large scale structure
Complicated parts development application.
The content of the invention
The object of the present invention is to provide one kind to be brazed the polynary copper silver nickel niobium zirconium solder of tungsten base powder alloy, realizes tungsten original washing powder
Last alloy is reliably connected with tungsten base powder alloy, tungsten base powder alloy and steel.A kind of polynary copper silver nickel niobium of the present invention
Zirconium solder, 800-900 DEG C of fusion temperature scope, has preferable wettability to tungsten base powder alloy.
What the above-mentioned purpose of the present invention was realized in：One kind soldering polynary copper silver nickel niobium zirconium pricker of tungsten base powder alloy
Material, the base alloy component of solder is used as using copper silver, adds Ni, niobium and zr element come from different backgrounds and possess different abilities copper silver nickel niobium zirconium solder, solder
Alloying component is by mass percentage (Wt/%)：Copper (Cu)：60-80, silver-colored (Ag)：10-30, nickel (Ni)：1-5, niobium (Nb)：1-
5, zirconium (Zr) 0.1-0.5.
Tungsten base powder alloy has the characteristics that high temperature resistant, anti-oxidant, anticorrosive, resistance to sudden heating, and especially excellent is anti-
High-temperature behavior, is usually all that therefore, tungsten base powder alloy is closed with tungsten based powders using its high-temperature behavior manufacture high temperature resistant parts
Gold, tungsten base powder alloy and steel are seldom attached using solder.Tungsten and copper, silver under liquid and solid-state interaction compared with
Weak, poor to the wetability of tungsten base powder alloy using common silver-based and copper base solder, soldering joint strength is relatively low.Test table
It is bright, the existing commercially available silver-base solder such as solder such as silver-bearing copper tin, Ag-Cu-Zn, silver-bearing copper indium, Ag-Cu-Zn cadmium and silver-bearing copper titanium, soldered fitting room temperature
Shearing strength is generally less than 150-200MPa, and high temperature shearing strength is generally less than 100-130MPa (400 DEG C of test temperature).In order to
Improve the processing performance (wetability, cross flow and joint filling etc.) of solder, improve its physics, chemistry and mechanical property, the present invention
A kind of soldering polynary copper silver nickel niobium zirconium solder of tungsten base powder alloy, it is polynary, trace alloying element to take addition
Method.The selection of alloying element is considered as following factor：(1) adjustment brazing filler metal alloy system fusion temperature scope should be able to control
Between 800-1000 DEG C.The recrystallization temperature of tungsten is 1100 ± 5 DEG C in tungsten base powder alloy, and the speed that crystal grain is grown up is very
It hurry up, brazing temperature is if it exceeds this temperature, material substantially become fragile.Therefore, in the case where brazing member operating temperature allows, soldering
Temperature is tried not more than 1100 DEG C, and this requires the liquidus curve of solder no more than 1000 DEG C.(2) craftsmanship of solder is improved
The mechanical property of soldered fitting and can be improved.Experimental study is found, if the alloying element of addition can be with being brazed material in liquid
Compound is mutually dissolved or formed under state or solid-state, then solder can soak mother metal in the liquid state, significantly improve soldered fitting
Mechanical property.(3) alloying element of addition should have the characteristics that fusing point is high, calorific intensity is high and corrosion resistance.
A kind of soldering tungsten base powder alloy of the present invention is the alloy based on Cu, Ag with polynary copper silver nickel niobium zirconium solder
Component, addition Ni, Nb and Zr element come from different backgrounds and possess different abilities copper silver nickel niobium zirconium solder.Ni, Nb and Zr fusing point are high, excellent corrosion resistance,
Compound can be mutually dissolved or formed under liquid and solid-state with W.According to the alloy phase diagram of Cu and Ag, amount containing Cu 28 (Wt/%),
Amount containing Ag 72 (Wt/%), Cu and Ag form binary eutectic, 780 DEG C of eutectic temperature.With in Cu, Ag bianry alloy, amount containing Cu increases
Add, aluminium alloy liquidus temperature improves.When amount containing Cu increases to 60 (Wt/%), aluminium alloy liquidus temperature reaches 905 DEG C；Amount containing Cu
When increasing to 80 (Wt/%), aluminium alloy liquidus temperature reaches 970 DEG C, if the amount containing Cu in solder is closed more than 80 (Wt/%)
Golden liquidus temperature is more than 1000 DEG C, and brazing temperature then will be more than 1100 DEG C, the result is that tungsten base powder alloy crystal grain is grown up, material
Material becomes fragile.Alloying component based on Cu, Ag, the amount containing Cu in solder should be controlled at 60-80 (Wt/%).According to the conjunction of W and Ni
Metallograph, W and Ni form limit solid solution, and at 1000 DEG C, W maxima solubilities in Ni are 12 (Wt/%), but at room temperature
Solubility of the W in Ni is smaller, and with the increase of ni content in solder, the plasticity and toughness of solder reduce.According to Cu's and Ni
Alloy phase diagram, Cu and Ni form unlimited solid solution, with the increase of ni content in solder, can also make solder solid, liquid liquidus temperature
Improve.According to the alloy phase diagram of W and Nb, W and Nb forms unlimited solid solution, and tungsten is the efficient hardening element of Nb, but with pricker
The increase of the amount containing Nb in material, plasticity/brittle transition temperature of tungsten base powder alloy soldered fitting will rise, and crystal grain is also significantly long
Greatly.Zr is active element, and solder liquid/gas surface tension and solder and tungsten base powder alloy solid-liquid can be reduced by adding Zr in solder
Interfacial tension, is conducive to improve the affinity of solder and tungsten base powder alloy, improves wetability of the solder to tungsten base powder alloy.
According to the alloy phase diagram of W and Zr, solubility of the W in Zr is relatively low at room temperature, forms β-Zr solid solution, amount containing W is more than 0.5
(Wt/%), then W is formed2Zr intermetallic compounds；In contrast, solubility of the Zr in W is extremely low at room temperature, with solder
The increase of the amount containing Zr, the plasticity and toughness of solder reduce, and soldered fitting becomes fragile.A kind of soldering tungsten base powder alloy of the present invention is used
Polynary copper silver nickel niobium zirconium solder, according to the mechanism of action of various addition element, is considering cost, the fusion temperature of solder
On the basis of scope, processing performance, physics, chemistry and mechanical property, make a service test the alloying element of addition research, control
The fusion temperature scope of polynary copper silver nickel niobium zirconium solder is made between 800-1000 DEG C, is had to tungsten base powder alloy preferable
Wettability, determines polynary copper silver nickel niobium zirconium brazing filler metal alloy component, and polynary copper silver nickel niobium zirconium brazing filler metal alloy component presses quality percentage
Than counting (Wt/%)：Copper (Cu)：60-80, silver-colored (Ag)：10-30, nickel (Ni)：1-5, niobium (Nb)：1-5, zirconium (Zr) 0.1-0.5.
Compared with prior art, the beneficial effects of the invention are as follows：
A kind of soldering tungsten base powder alloy of the present invention is existed with polynary copper silver nickel niobium zirconium solder, fusion temperature scope
Between 800-1000 DEG C, in the case where ensureing that brazing member operating temperature allows, fusion temperature and the soldering of solder are improved as far as possible
The re-melting temperature of connector, ensures the resistance to elevated temperatures of soldered fitting；The crystal grain of tungsten in tungsten base powder alloy is avoided to grow again at the same time
Greatly.A kind of soldering tungsten base powder alloy of the present invention is with polynary copper silver nickel niobium zirconium solder to tungsten base powder alloy wetability
Good, strong with the affinity of tungsten base powder alloy, soldered fitting shear strength is more than 200MPa.
Brief description of the drawings
Fig. 1 is polynary copper silver nickel niobium zirconium solder to tungsten base powder alloy wetability.
Fig. 2 is polynary copper silver nickel niobium zirconium solder brazing tungsten base powder alloy test specimen.
Note：Since attached drawing there cannot be color, illustrated with gray scale.
Embodiment
The embodiment that is given by the following simultaneously further is specifically described the method for the present invention with reference to attached drawing (Fig. 1 and 2).
Fig. 1 is polynary copper silver nickel niobium zirconium solder to tungsten base powder alloy wetability.
Fig. 2 is polynary copper silver nickel niobium zirconium solder brazing tungsten base powder alloy test specimen, as seen from the figure, polynary copper silver nickel niobium zirconium pricker
Material is fabulous to tungsten base powder alloy wetability, soaks any surface finish, forms good fillet.
A kind of soldering polynary copper silver nickel niobium zirconium solder of tungsten base powder alloy of the present invention, material therefor Cu, Ag,
Ni, Nb and Zr purity are 99.99%, and brazing filler metal alloy is determined by the result of study that makes a service test to the alloying element of addition
Component, brazing filler metal alloy component is by mass percentage (Wt/%)：Copper (Cu)：60-80, silver-colored (Ag)：10-30, nickel (Ni)：1-5,
Niobium (Nb)：1-5, zirconium (Zr) 0.1-0.5；Cu, Ag, Ni, Nb and Zr, which are weighed, by experimental design proportioning composition is put into ceramic crucible, then
Crucible is placed in vacuum melting furnace to heat and melt and is prepared into polynary copper silver nickel niobium zirconium solder.Smelting temperature should control
1150-1200 DEG C of scope, soaking time 10 minutes, and fully stir evenly alloying element.Solder is smelted in aforementioned manners,
Component is uniform, and the total scaling loss coefficient of solder is less than 0.1%.By national standard《GB/T 11364-2008 solder wettings experiment side
Method》With《GB/T 11363-2008 soldering joint strength test methods》Wettability and the connector for determining solder are anti-shearing strong
Degree.
A kind of soldering tungsten base powder alloy of the present invention is with polynary copper silver nickel niobium zirconium solder, the technical indicator reached：
(1) fusion temperature scope：812-978 DEG C；(2) wetability is good：130- is reached to the wetting areas of tungsten base powder alloy
150mm2；(3) it is 235-245Mpa to be brazed tungsten base powder alloy joint bending stiffness.
Following all embodiments use purity to pass through the conjunction to addition for 99.99% Cu, Ag, Ni, Nb and Zr metal
The gold element result of study that makes a service test determines brazing filler metal alloy component, forms following technical scheme, brazing filler metal alloy component presses matter
Measure percentages (Wt/%)：Copper (Cu)：60-80, silver-colored (Ag)：10-30, nickel (Ni)：1-5, niobium (Nb)：1-5, zirconium (Zr) 0.1-
0.5；Cu, Ag, Ni, Nb and Zr are weighed by experimental design proportioning composition and is put into ceramic crucible, then crucible is placed in vacuum melting furnace
It is middle to heat and melt and be prepared into polynary copper silver nickel niobium zirconium solder.Smelting temperature should be controlled in 1150-1200 DEG C of scope, insulation
Between 10 minutes, and fully alloying element is stirred evenly.
Embodiment see the table below 1：
More than 1 yuan of copper silver nickel niobium zirconium solder component of table and its performance for being brazed tungsten base powder alloy
Claims (8)
1. one kind soldering polynary copper silver nickel niobium zirconium solder of tungsten base powder alloy, it is characterised in that closed based on Cu, Ag
Golden component, addition Ni, Nb and Zr element come from different backgrounds and possess different abilities copper silver nickel niobium zirconium solder, and brazing filler metal alloy component is by mass percentage
（Wt/%）：Copper（Cu）：65-80, silver（Ag）：10-28, nickel（Ni）：1-4.9, niobium（Nb）：1-5, zirconium（Zr）0.1-0.5.
A kind of 2. soldering polynary copper silver nickel niobium zirconium solder of tungsten base powder alloy as claimed in claim 1, it is characterised in that pricker
Expect alloying component by mass percentage（Wt/%）：Cu：75, Ag：20, Ni：2.8, Nb：2, Zr：0.2.
A kind of 3. soldering polynary copper silver nickel niobium zirconium solder of tungsten base powder alloy as claimed in claim 1, it is characterised in that pricker
Expect alloying component by mass percentage（Wt/%）：Cu：70, Ag：24, Ni：1, Nb：4.5, Zr：0.5.
A kind of 4. soldering polynary copper silver nickel niobium zirconium solder of tungsten base powder alloy as claimed in claim 1, it is characterised in that
Brazing filler metal alloy component is by mass percentage（Wt/%）：Cu：65, Ag：28, Ni：4.9, Nb：2, Zr：0.1.
A kind of 5. soldering polynary copper silver nickel niobium zirconium solder of tungsten base powder alloy as claimed in claim 1, it is characterised in that pricker
Expect alloying component by mass percentage（Wt/%）：Cu：80, Ag：15, Ni：2, Nb：2.7, Zr：0.3.
A kind of 6. soldering polynary copper silver nickel niobium zirconium solder of tungsten base powder alloy as claimed in claim 1, it is characterised in that pricker
Expect alloying component by mass percentage（Wt/%）：Cu：75, Ag：15, Ni：4.9, Nb：4.9, Zr：0.2.
A kind of 7. soldering polynary copper silver nickel niobium zirconium solder of tungsten base powder alloy as claimed in claim 1, it is characterised in that
Brazing filler metal alloy component is by mass percentage（Wt/%）：Cu：70, Ag：24, Ni：2, Nb：3.5, Zr：0.5.
A kind of 8. soldering polynary copper silver nickel niobium zirconium solder of tungsten base powder alloy as claimed in claim 1, it is characterised in that pricker
Expect alloying component by mass percentage（Wt/%）：Cu：65, Ag：28, Ni：3, Nb：3.7, Zr：0.3.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610564583.XA CN106077867B (en) | 2016-07-18 | 2016-07-18 | One kind soldering polynary copper silver nickel niobium zirconium solder of tungsten base powder alloy |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610564583.XA CN106077867B (en) | 2016-07-18 | 2016-07-18 | One kind soldering polynary copper silver nickel niobium zirconium solder of tungsten base powder alloy |
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| CN106077867B true CN106077867B (en) | 2018-05-04 |
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| CN111151864B (en) * | 2020-01-16 | 2021-03-12 | 吉林大学 | Welding material and process for connecting tungsten-based powder alloy and low-expansion high-temperature alloy |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4009027A (en) * | 1974-11-21 | 1977-02-22 | Jury Vladimirovich Naidich | Alloy for metallization and brazing of abrasive materials |
| CN102448663A (en) * | 2009-05-27 | 2012-05-09 | 京瓷株式会社 | Solder material, heat dissipation base using same, and electronic device |
| CN105127534A (en) * | 2015-09-18 | 2015-12-09 | 吉林大学 | Brazing connecting method for tungsten-based powder alloy die |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0787996B2 (en) * | 1987-06-18 | 1995-09-27 | 田中貴金属工業株式会社 | Silver braze alloy |
| JPH0930870A (en) * | 1995-07-21 | 1997-02-04 | Toshiba Corp | Bonded material of ceramic metal and accelerating duct |
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2016
- 2016-07-18 CN CN201610564583.XA patent/CN106077867B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4009027A (en) * | 1974-11-21 | 1977-02-22 | Jury Vladimirovich Naidich | Alloy for metallization and brazing of abrasive materials |
| CN102448663A (en) * | 2009-05-27 | 2012-05-09 | 京瓷株式会社 | Solder material, heat dissipation base using same, and electronic device |
| CN105127534A (en) * | 2015-09-18 | 2015-12-09 | 吉林大学 | Brazing connecting method for tungsten-based powder alloy die |
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