CN107619981A - The carbonization tungsten-copper alloy and preparation method of a kind of boracic - Google Patents
The carbonization tungsten-copper alloy and preparation method of a kind of boracic Download PDFInfo
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- CN107619981A CN107619981A CN201710728339.7A CN201710728339A CN107619981A CN 107619981 A CN107619981 A CN 107619981A CN 201710728339 A CN201710728339 A CN 201710728339A CN 107619981 A CN107619981 A CN 107619981A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
Abstract
The invention discloses a kind of carbonization tungsten-copper alloy of boracic, and by weight percentage, the alloy is made up of following component：WC 49.97~80%, Cu 19.97~50%, B 0.01~0.03%；The invention also discloses the preparation method of the alloy, including batch mixing step, forming agent encapsulation steps, compressing step, sintering step, copper liquid infiltration step.Boracic carbonization Tungsten-copper Composites uniform texture provided by the invention, hardness is high, and wearability is good, and its density is 12.5~12.9g/cm3, hardness is 35~60HRC, and electrical conductivity is 16~35%.The production efficiency of the inventive method is high, and production cost is low.
Description
Technical field
The invention belongs to the production field for the tungsten-copper composite material that is carbonized, the carbonization tungsten-copper alloy of more particularly to a kind of boracic and
Its preparation method.
Background technology
Electrical contact is one of key element of device for switching, is responsible for conducting and the effect of breaking current, its quality are direct
Influence the service life and operational reliability of device for switching.Contact can produce electricity between conducting or the moment of disjunction circuit, contact
Arc discharge, cause the electrical arc erosion of contact, or even melting welding.When long-time is by big rated current or short circuit current, contact
Between contact resistance cause contact temperature rise, aoxidize, or even melting welding etc..So weigh a kind of quality of contact material not only
To be evaluated in terms of the physical and mechanical properties of material, it is necessary to consider its many electrical property, such as anti electric arc corrosion, pressure-resistant
Intensity, resistance fusion welding energy, Chopping Current, wearability etc..When device for switching is applied to different scope and environment, to contact material
Requirement be also not quite similar.Such as middle pressure vacuum circuit breaker, it is desirable to which material has high connecting-disconnecting function, but the requirement to value of damming can fit
When relaxing, and low-voltage vacuum contactor, it requires relatively low to connecting-disconnecting function, but require it is very low dam value and wearability it is good
Energy frequent operation, to improve its service life.Different application scenarios, from the contact material of different qualities, this has promoted to touch
The continuous development of head material.
Tungsten and carbonization tungsten-copper composite material are a kind of new function materials with excellent comprehensive performance, both with excellent
Electric conductivity, there is high intensity, hardness and excellent high-temperature behavior again, because of its good anti-galvanic corrosion, resistance fusion welding and low section
The characteristics such as flow valuve, it is widely used in high, medium and low voltage electrical equipment.The tungsten copper that is carbonized is applied compressing-high using high-quality tungsten carbide powder
Temperature sinter-ooze process for copper the manufacturing, the content of tungsten carbide from 50% to 80% (percentage by weight), its even tissue and cause
Close, performance is very excellent, have high temperature resistant, arc ablation resistance, intensity it is high, than it is great, conductive, thermal conductivity is good, be easy to cutting plus
The features such as work, compared to tungsten-copper alloy, carbonization tungsten-copper alloy has higher hardness, wearability and arc resistant corrosive nature, such as
WC70Cu30 hardness is 37HRC, and hardness reaches 47HRC after adding nickel, element silicon, and wearability is also more excellent.
Research of the Plansee companies of Austria to the tungsten-copper alloy that is carbonized is more deep, and its product already takes up both at home and abroad
Major market, the high hardness of carbonization tungsten copper, good anti-wear performance are more widely used it.China is from last century 80
Age proceeds by the research of carbonization tungsten-copper alloy, and wherein WC-Cu (40) alloys are as low pressure (below 6kV) vacuum switch tube
Contact material is developed rapidly, and the alloy material combines the good conductive thermal conductivity of copper and high-melting-point, the height of tungsten carbide
The good characteristic such as hardness, corrosion-resistant, having cost concurrently, also low advantage obtains the accreditation of Liao Ge vacuum switches manufacturer.The nineties
Just, Ministry of Machine-building and Electronics Industry discloses the standard SJ/T10168.4-91 of carbonization tungsten-copper alloy, it is specified that carbonization tungsten-copper alloy
Three kinds of trades mark, respectively F6000E, F6001E, F6002E, corresponding tungsten carbide content is 80,70,60%, afterwards not to tungsten carbide
Copper alloy carries out standard update, but with the popularization and use of product, it is external that new reform, mesh have been carried out to carbonization tungsten-copper alloy
Before be usually used in production carbonization tungsten-copper alloy mainly have tetra- trades mark of TC5, TC10, TC20, TC53, tungsten carbide content is respectively
50th, 56,70,70.12%, and excellent combination property, as shown in table 1.
The trade mark and performance of the carbonization tungsten-copper alloy of table 1
As can be seen from Table 1, nickel and element silicon are added in order to improve the hardness of carbonization tungsten-copper alloy, nickel and silicon plus
Enter so that tungsten carbide hardness of copper alloy improves, conductance declines.Therefore, in order to further improve it is existing carbonization tungsten-copper alloy it is hard
Degree, wearability and arc resistant ablation ability are, it is necessary to find more excellent carbonization tungsten-copper alloy of performance and preparation method thereof.
The content of the invention
The defects of for prior art, it is an object of the invention to provide a kind of carbonization tungsten-copper alloy of boracic and its preparation
Method, alloy product of the invention overcome the problem of existing alloy conductive rate is low, and cost is high, are prepared using present invention process
Be carbonized tungsten-copper alloy uniform texture, and hardness is high, and wearability is high, and conductance is good, its production technology efficiency high, and production cost is big
It is big to reduce.
To achieve these goals, present invention employs following technical scheme：
A kind of carbonization tungsten-copper alloy of boracic, by weight percentage, the alloy is made up of following component：WC 49.97~
80%, Cu 19.97~50%, B 0.01~0.03%.
In the carbonization tungsten-copper alloy of above-mentioned boracic, as a kind of preferred embodiment, in the alloy, B weight hundred
Divide than being 0.01~0.024%.
In the carbonization tungsten-copper alloy of above-mentioned boracic, as a kind of preferred embodiment, the carbonization tungsten copper of the boracic closes
Gold utensil has following performance parameter：Density is 12.5~12.9g/cm3, hardness is 40~60HRC, and conductance is 18~35%.
The present invention reduces cost to improve the hardness and wearability of carbonization tungsten-copper alloy, in existing tungsten carbide
Micro boron element is added in copper alloy to improve its performance, boron can be present in Copper substrate with gap form or displacement format, right
Alloy purification and crystal grain refinement contribution are more apparent, and addition trace B can be obviously improved its mechanical performance to being carbonized in tungsten-copper alloy,
Improve corrosion resistance.Specifically, the present invention makes to form boron copper Binder Phase, boron copper in carbonization tungsten-copper alloy using addition boron element
Dispersion-strengtherning causes carbonization tungsten copper tissue crystal grain substantially to refine, and adding micro boron element can make tungsten carbide hardness of copper alloy raise 10
~20HRC, its wearability and corrosion resistance also increase, but solubility of the boron in copper alloy is limited, when boron is in copper alloy
In solubility more than 0.02% when, will be separated out in the form of boride is mingled with, and deteriorate material plasticity, accelerated corrosion, therefore
B content elects 0.01~0.03wt% as in alloy of the present invention.
A kind of preparation method of the carbonization tungsten-copper alloy of above-mentioned boracic, includes successively：
Batch mixing step, matched according to the tungsten carbide copper alloy compositions of above-mentioned boracic, raw material tungsten carbide powder and boron powder are carried out
Mixing, obtains compound；
Forming agent encapsulation steps, forming agent is added in the compound and mixed, so that the forming agent is uniform
The outer surface of the compound powder is coated on, then drying, sieving obtains cladding material；
Compressing step, by the cladding material according to predetermined shape molding or isostatic pressing, obtain pressed compact；
Sintering step, the pressed compact is sintered, boracic carbonization W skeleton after being sintered；
Copper liquid infiltration step, boracic carbonization W skeleton is positioned over progress infiltration processing on the copper sheet of constant weight,
Obtain the carbonization tungsten-copper alloy of boracic.
Boracic carbonization W skeleton is placed on copper sheet by the method for the present invention, will not occur outside to ooze copper, interior prior to inside
Portion's gas can not be excluded, copper liquid can not be oozed, the internal phenomenon for losing copper, and infiltration effect is ideal.
In the preparation method of the carbonization tungsten-copper alloy of above-mentioned boracic, as a kind of preferred embodiment, the preparation side
Method also includes machining steps, and the carbonization tungsten-copper alloy for the boracic that the copper liquid infiltration step is obtained is machined to the carbon of boracic
Change tungsten-copper alloy finished product；It is highly preferred that described be machined as turning and/or grinding.
In the preparation method of the carbonization tungsten-copper alloy of above-mentioned boracic, as a kind of preferred embodiment, the tungsten carbide
The Fisher particle size of powder be 3.0~12.0 μm (such as：3.5μm、4.0μm、5μm、6μm、7μm、8μm、9μm、10μm、11μm)；Institute
State the Fisher particle size of boron powder for 1-5 μm (such as：1.5μm、2.0μm、3μm、4μm)；It is highly preferred that the purity of the tungsten carbide powder
For more than 99.8%, the purity of the boron powder is more than 96%；Further, the Fisher particle size of the boron powder is 3 μm.From upper
More suitably skeletal density can be obtained by stating the tungsten carbide powder of Fisher particle size, if undersized, skeletal density can be too high, such as fruit
Spend greatly, skeletal density can be too low；And in order to ensure uniformity that boron powder mixes with tungsten carbide powder, the Fisher particle size of boron powder is preferred
For 1-5 μm.
In the preparation method of the carbonization tungsten-copper alloy of above-mentioned boracic, as a kind of preferred embodiment, in the batch mixing
In step, the mixing is completed using V-type batch mixer；In order to ensure the uniformity of batch mixing and economy, it is highly preferred that
The mixing time is 10-16h (such as 11h, 12h, 13h, 14h, 15h), it is further preferred that the mixing time is 12h.
In the preparation method of the carbonization tungsten-copper alloy of above-mentioned boracic, as a kind of preferred embodiment, the forming agent
For the one or more in buna, polyethylene glycol, paraffin, methyl ethyl ketoxime, but from processability it is good, be easier to the angle of removing
To consider, preferably methyl ethyl ketoxime；It is highly preferred that the amount of the forming agent added in the compound is：Every kilogram of mixing
Added in material 40-60mL forming agents (40-60mL/kg, for example, 42mL/kg, 46mL/kg, 50mL/kg, 55mL/kg, 58mL/kg,
59ml/kg), it is further preferred that adding 50mL forming agents (50mL/kg) in every kilogram of compound.The dosage of forming agent is very few
Powder or graininess, processability are bad；Forming agent dosage can excessively cause green density and insufficient strength, blank during removing
Easily cracking.
In the preparation method of the carbonization tungsten-copper alloy of above-mentioned boracic, as a kind of preferred embodiment, in the shaping
In agent encapsulation steps, the mixing refers to：Forming agent and the compound described in shovel repeatedly rubbing and pressure；In order to ensure that powder mixes
Uniformity is closed, it is highly preferred that the number of the rubbing and pressure repeatedly is 8-15 times, more preferably 10 times.
In the preparation method of the carbonization tungsten-copper alloy of above-mentioned boracic, as a kind of preferred embodiment, the forming agent
Encapsulation steps are substituted by mist projection granulating step.Mist projection granulating can obtain more preferable effect.
In the preparation method of the carbonization tungsten-copper alloy of above-mentioned boracic, as a kind of preferred embodiment, in the shaping
In agent encapsulation steps, the temperature of the drying for 120-180 DEG C (such as 125 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, 170
DEG C, 178 DEG C), the time of the drying is 15-25min (such as 16h, 18h, 20h, 22h, 24h), it is highly preferred that the drying
Temperature be 150 DEG C, the time of the drying is 20min.
In the preparation method of the carbonization tungsten-copper alloy of above-mentioned boracic, as a kind of preferred embodiment, in the shaping
In agent encapsulation steps, the sieving referred to 55-65 mesh sieves, and took minus mesh as the cladding material；It is highly preferred that cross 60 mesh
Sieve.In order to ensure die mould effect, need to smash the powder of caking after drying, sieve.Further, if sieve mesh number mistake
Small, then tungsten carbide particle is excessively thick, easily causes green density uneven；Sieve mesh number is excessive, and particle is meticulous, causes compact strength
Deficiency.
In the preparation method of the carbonization tungsten-copper alloy of above-mentioned boracic, as a kind of preferred embodiment, the molding is
Refer to：The cladding material is placed in the mould corresponding with predetermined shape, and it is compressing on press；It is it is highly preferred that described
The pressure of compacting be 200~300MPa (such as 205MPa, 210MPa, 215MPa, 220MPa, 230MPa, 238MPa, 250MPa,
260MPa, 270MPa, 280MPa, 290MPa, 298MPa), time of compacting for 1~2min (such as 1min, 1.1min,
1.2min、1.4min、1.5min、1.7min、、1.8min、、1.9min)；Further, the density of the pressed compact contains for theory
Boron tungsten carbide skeletal density (i.e. the solid density of boracic tungsten carbide material) 85-95% (such as 86%, 88%, 90%,
91%th, 92%, 92%, 94%)；More preferably：The density of the pressed compact is the 90% of theoretical boracic tungsten carbide skeletal density.
In the preparation method of the carbonization tungsten-copper alloy of above-mentioned boracic, as a kind of preferred embodiment, the isostatic pressed
Shaping refers to：The cladding material is placed in isostatic pressed gum cover and carries out isostatic pressing；It is highly preferred that the isostatic pressing
Pressing pressure is 200~240MPa (such as 205MPa, 210MPa, 215MPa, 220MPa, 230MPa, 238MPa), the dwell time
For 5~10min (such as 6min, 7min, 8min, 9min)；Further, the density of the pressed compact is theoretical boracic tungsten carbide bone
The 85-95% (such as 86%, 88%, 90%, 91%, 92%, 92%, 94%) of frame density；Further, the pressed compact is close
Spend for the 90% of theoretical boracic tungsten carbide skeletal density.
In the preparation method of the carbonization tungsten-copper alloy of above-mentioned boracic, as a kind of preferred embodiment, at the sintering
The temperature of reason be 1400~1900 DEG C (such as 1410 DEG C, 1450 DEG C, 1500 DEG C, 1550 DEG C, 1600 DEG C, 1650 DEG C, 1700 DEG C,
1750 DEG C, 1800 DEG C, 1850 DEG C, 1890 DEG C), it is incubated as 2-5h (such as 2.5h, 3h, 3.5h, 4h, 4.5h), it is highly preferred that institute
The temperature for stating sintering processes is 1600~1700 DEG C, is incubated as 3h.For 70% or so tungsten carbide, sintering temperature mistake
Low, frame strength or density are inadequate；Sintering temperature is too high, and density can be caused too high, or decarburization has a strong impact on hardness.Sintering temperature
The too high or too low accuracy that can all influence composition.
In the preparation method of the carbonization tungsten-copper alloy of above-mentioned boracic, as a kind of preferred embodiment, at the sintering
The atmosphere of reason is reducing atmosphere；It is highly preferred that the reducing atmosphere is hydrogen atmosphere.
In the preparation method of the carbonization tungsten-copper alloy of above-mentioned boracic, as a kind of preferred embodiment, at the sintering
Reason is completed in intermediate frequency furnace.
In the preparation method of the carbonization tungsten-copper alloy of above-mentioned boracic, as a kind of preferred embodiment, in the copper liquid
In infiltration step, the copper sheet is electrolytic copper foil, and more preferably purity is more than 99.95%.
Above-mentioned boracic carbonization tungsten-copper alloy preparation method in, it is contemplated that during copper liquid infiltration the volatilization of copper and
In the residual of alloy surface, as a kind of preferred embodiment, in the copper liquid infiltration step, the copper sheet of the constant weight
Refer to amount of copper × (110-120) % calculated according to the tungsten carbide copper alloy compositions proportioning of above-mentioned boracic, be preferably：According to above-mentioned
Amount of copper × 115% that the tungsten carbide copper alloy compositions proportioning of boracic calculates.
In the preparation method of the carbonization tungsten-copper alloy of above-mentioned boracic, as a kind of preferred embodiment, in the copper liquid
In infiltration step, the temperature of infiltration processing for 1300-1500 DEG C (such as 1310 DEG C, 1350 DEG C, 1380 DEG C, 1400 DEG C,
1420 DEG C, 1450 DEG C, 1480 DEG C, 1490 DEG C), time of infiltration processing for 90~120min (such as 95min, 100min,
105min、110min、115min、119min)；It is highly preferred that the temperature of the infiltration processing is 1400 DEG C.Infiltrating temperature mistake
Height, melt evaporation seriously, excessive vapour pressure can be internally formed in infiltration blank, cause hole；Infiltrating temperature is too low, can cause to moisten
Moist deficiency, infiltration effect is bad, easily defective.
In the preparation method of the carbonization tungsten-copper alloy of above-mentioned boracic, as a kind of preferred embodiment, at the infiltration
Reason is carried out in boat stove is pushed away.
In the preparation method of the carbonization tungsten-copper alloy of above-mentioned boracic, as a kind of preferred embodiment, at the infiltration
The atmosphere of reason is reducing atmosphere；It is highly preferred that the reducing atmosphere is hydrogen atmosphere.
Compared with prior art, the present invention has the advantages that：
The present invention uses again on the basis of 85-95% of the green density for the density of theoretical boracic carbonization W skeleton is ensured
High temperature sintering improves the hardness of material, and sintered body shrinks during sintering, density and intensity increase, relative to directly will in compacting
The density of blank be pressed onto it is equal with theoretic skeleton density after directly ooze the technique of copper, its hardness is high, and uniformity is good, and porosity is low.
Sintering process changes traditional boat that pushes away and sintered in the present invention, but uses intermediate frequency furnace to sinter, and intermediate frequency furnace is sintering
During programming rate it is slow, uniform temperature fields, the tissue and performance of sintered article can be improved.
Present invention sintering and the protective gas oozed in process for copper are hydrogen, and one side hydrogen more often makes in the industrial production
With, it is even more important the reason for be, hydrogen is reducibility gas, can make tungsten carbide in tungsten carbide copper alloy at high operating temperatures
The oxidized part in surface reduces again, it is ensured that abundant infiltration of the liquid electrolyte copper to the W skeleton that is carbonized in process for copper is oozed.
Boracic carbonization Tungsten-copper Composites uniform texture provided by the invention, hardness is high, and wearability is good, and its density is 12.5
~12.9g/cm3, hardness is 35~60HRC, and electrical conductivity is 16~35%.The production efficiency of the inventive method is high, production cost
It is low.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of alloy material prepared by the embodiment of the present invention 1；
Fig. 2 is the scanning electron microscope (SEM) photograph of alloy material prepared by the embodiment of the present invention 2.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiment, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Involved raw material includes in following examples, tungsten carbide powder (purity >=99.8, Fisher particle size is 3.0~
12.0 μm), boron powder (purity >=96%, average Fisher particle size are 3 μm), electrolytic copper foil (purity >=99.95%).
Embodiment 1
Boracic carbonization tungsten-copper alloy manufactured in the present embodiment, is made up of, tungsten carbide 70% following components by weight percentage,
Copper 29.978%, boron 0.022%.Its preparation technology comprises the following steps：
(1) powder prepares
Purity >=99.8% is taken, the tungsten carbide powder that average Fisher particle size is 3.0 μm；Purity >=96% is taken, average Fei Shi grains
Spend stand-by for 3 μm of boron powder.
(2) batch mixing
By weight 3182:1 ratio mixes the tungsten carbide powder in step (1) and boron powder, is mixed in V-type batch mixer
12h is stand-by.
(3) forming agent is added
First and second are added in the compound that the amount of the compound obtained by 50ml forming agents/kg steps (2) obtains to step (2)
Ketoxime forming agent, with shovel, rubbing and pressure make methyl ethyl ketoxime equably be coated on powder particle surface 10 times repeatedly, then at 150 DEG C
20min is dried in baking material case, the powder after drying is crossed into 60 mesh sieves takes minus sieve stand-by.
(4) it is compressing
Cladding powder after step (3) processing is placed in mould corresponding with predetermined shape, and is pressed on press
Type, press pressure 200MPa, press time 1min, obtained green density are theoretical boracic tungsten carbide skeletal density
90%.
(5) high temperature sintering
The compressing boracic tungsten carbide green compact of step (4) are sintered in 1700 DEG C of logical hydrogen intermediate frequency furnaces, 3h is incubated, obtains
Boracic carbonization W skeleton after fine and close sintering, skeletal density is theoretic skeleton density, i.e. 8.88g/cm3。
(6) copper liquid infiltration
First, according to the proportioning of the present embodiment alloying component, the boracic carbonization W skeleton obtained according to step (5), which calculates, to be oozed
Copper dosage and the copper sheet for tailoring constant weight, wherein, the copper sheet for the constant weight tailored is the carbonization tungsten copper according to above-mentioned boracic
Amount of copper × 115% that alloy compositions proportioning calculates, then the electrolytic copper foil of purity >=99.95% is placed in below carbonization W skeleton
Ooze copper, put it into molybdenum boat, boat infiltration is pushed away using molybdenum boat when oozing copper, infiltrating temperature is 1400 DEG C, when be about 1.5 hours, ooze
The tungsten-copper alloy that is carbonized is obtained after the completion of copper.
(7) double-side grinding is processed
The carbonization tungsten-copper alloy obtained to step (6) carries out double-side grinding processing, feeds 0.02mm every time, obtains tungsten carbide
Copper alloy finished product.
Carbonization tungsten-copper alloy performance parameter is made from the present embodiment：Density 12.67g/cm3(relative density 98.5%),
Hardness 56HRC, electrical conductivity 20%, porosity 1.3%；Alloy material prepared by the present embodiment method has good uniform
Property, referring to Fig. 1.
The computational methods of mesopore rate of the present invention are：By weighing the weightening of the carbonization W skeleton of the boracic after oozing copper, calculate
The solid density of block, relative density is obtained with actual density/solid density, is then porosity with 1- relative densities.
Embodiment 2
Boracic carbonization tungsten-copper alloy manufactured in the present embodiment, is made up of following components by weight percentage：Tungsten carbide 70%,
Copper 29.976%, boron 0.024%.Its preparation technology comprises the following steps：
(1) powder prepares
Purity >=99.8 are taken, the tungsten carbide powder that average Fisher particle size is 5.8 μm；Purity >=96% is taken, average Fisher particle size
It is stand-by for 3 μm of boron powder.
(2) batch mixing
By weight 2917：1 ratio mixes the tungsten carbide powder in step (1) and boron powder, is mixed in V-type batch mixer
12h is stand-by.
(3) forming agent is added
First and second are added in the compound that the amount of the compound obtained by 50ml forming agents/kg steps (2) obtains to step (2)
Ketoxime forming agent, with shovel, rubbing and pressure make methyl ethyl ketoxime equably be coated on powder particle surface 12 times repeatedly, then at 150 DEG C
20min is dried in baking material case, the powder after drying is crossed into 60 mesh sieves takes minus sieve stand-by.
(4) it is compressing
Cladding powder after step (3) processing is placed in isostatic pressed gum cover mould corresponding with predetermined shape, and waited
Compressing on static pressure press, press pressure 240MPa, a length of 10min during pressurize, green density is theoretical boracic tungsten carbide
The 95% of skeletal density.
(5) high temperature sintering
The compressing boracic tungsten carbide green compact of step (4) are sintered in 1600 DEG C of logical hydrogen intermediate frequency furnaces, 3h is incubated, obtains
Boracic carbonization W skeleton after fine and close sintering, skeletal density is theoretic skeleton density, i.e. 8.88g/cm3。
(6) copper liquid infiltration
First, according to the proportioning of the present embodiment alloying component, the boracic carbonization W skeleton obtained according to step (5), which calculates, to be oozed
Copper dosage and the copper sheet for tailoring constant weight, wherein, the copper sheet for the constant weight tailored is the carbonization tungsten copper according to above-mentioned boracic
Amount of copper × 115% that alloy compositions proportioning calculates, then the electrolytic copper foil of purity >=99.95% is placed in below carbonization W skeleton
Ooze copper, boat infiltration pushed away using molybdenum boat when oozing copper, infiltrating temperature is 1400 DEG C, when be about 1.8 hours, ooze and be carbonized after the completion of copper
Tungsten-copper alloy.
(7) double-side grinding is processed
The carbonization tungsten-copper alloy obtained to step (6) carries out double-side grinding processing, feeds 0.02mm every time, obtains tungsten carbide
Copper alloy finished product.
Carbonization tungsten-copper alloy performance parameter is made from the present embodiment：Density 12.65g/cm3(relative density 98.4%),
Hardness 48HRC, electrical conductivity 22%, porosity 1.4%；Alloy material prepared by the present embodiment method has good uniform
Property, referring to Fig. 2.
Embodiment 3-10 and comparative example 1-3
Embodiment 3-10 and comparative example 1-3 is in addition to alloy compositions proportioning is different from embodiment 1, other preparation technologies step
It is rapid same as Example 1.Embodiment 3-10 and comparative example 1-3 alloy compositions are matched referring to table 2, the performance ginseng of obtained alloy
Number is referring to table 2.
The embodiment 3-10 of table 2 and comparative example 1-3 alloy compositions are with when alloy property
Embodiment 11-13 and comparative example 4,5
Embodiment 11-13 and comparative example 4,5 in addition to isostatic pressing in table 3 and sintering process are different from embodiment 1,
Target component and other step of preparation process are same as Example 1.The alloy that embodiment 11-13 and comparative example 4,5 obtain
Performance parameter is referring to table 3.
The embodiment 11-13 of table 3 and comparative example isostatic pressing and sintering process parameter and alloy property
Embodiment 14-18 and comparative example 6,7
Embodiment 14-18 and comparative example 6,7 in addition to infiltration process is different from embodiment 1 in table 4, target component and
Other step of preparation process are same as Example 1.The performance parameter for the alloy that embodiment 14-18 and comparative example 6,7 obtain referring to
Table 4.
The embodiment 14-18 of table 4 and comparative example infiltration process parameter and alloy property
Claims (10)
1. the carbonization tungsten-copper alloy of a kind of boracic, it is characterised in that by weight percentage, the alloy is made up of following component：
WC 49.97~80%, Cu 19.97~50%, B 0.01~0.03%.
2. the carbonization tungsten-copper alloy of boracic according to claim 1, it is characterised in that in the alloy, B weight percent
Than for 0.01~0.024%.
3. the carbonization tungsten-copper alloy of boracic according to claim 1, it is characterised in that the carbonization tungsten-copper alloy of the boracic
With following performance parameter：Density is 12.5~12.9g/cm3, hardness is 40~60HRC, and conductance is 18~35%.
4. the preparation method of the carbonization tungsten-copper alloy of the boracic described in claim any one of 1-3, it is characterised in that wrap successively
Include：
Batch mixing step, matched according to the tungsten carbide copper alloy compositions of the boracic described in claim any one of 1-3, raw material is carbonized
Tungsten powder and boron powder are mixed, and obtain compound；
Forming agent encapsulation steps, forming agent is added in the compound and mixed, so that the forming agent uniformly coats
In the outer surface of the compound powder, then drying, sieving obtains cladding material；
Compressing step, by the cladding material according to predetermined shape molding or isostatic pressing, obtain pressed compact；
Sintering step, the pressed compact is sintered, boracic carbonization W skeleton after being sintered；
Copper liquid infiltration step, boracic carbonization W skeleton is positioned over progress infiltration processing on the copper sheet of constant weight, obtained
The carbonization tungsten-copper alloy of boracic.
5. preparation method according to claim 4, it is characterised in that the preparation method also includes machining steps, will
The carbonization tungsten-copper alloy for the boracic that the copper liquid infiltration step obtains is machined to the carbonization tungsten-copper alloy finished product of boracic；It is preferred that
Ground, it is described to be machined as turning and/or grinding；
Preferably, the forming agent encapsulation steps are substituted by mist projection granulating step.
6. preparation method according to claim 4, it is characterised in that
The Fisher particle size of the tungsten carbide powder is 3.0~12.0 μm；The Fisher particle size of the boron powder is 1-5 μm；Preferably, it is described
The purity of tungsten carbide powder is more than 99.8%, and the purity of the boron powder is more than 96%；It is further preferred that the boron powder takes
Family name's granularity is 3 μm；
Preferably, in the batch mixing step, the mixing is completed using V-type batch mixer；Preferably, the mixing time
For 10-16h, it is further preferred that the mixing time is 12h.
7. preparation method according to claim 4, it is characterised in that the forming agent is buna, polyethylene glycol, stone
One or more in wax, methyl ethyl ketoxime, preferably methyl ethyl ketoxime；It is highly preferred that the shaping added in the compound
The amount of agent is：40-60mL forming agents are added in every kilogram of compound, it is further preferred that adding 50mL in every kilogram of compound
Forming agent；
Preferably, in the forming agent encapsulation steps, the mixing refers to：The forming agent and described described in shovel repeatedly rubbing and pressure
Compound；It is highly preferred that the number of the rubbing and pressure repeatedly is 8-15 times, more preferably 10 times；
Preferably, in the forming agent encapsulation steps, the temperature of the drying is 120-180 DEG C, and the time of the drying is
15-25min, it is highly preferred that the temperature of the drying is 150 DEG C, the time of the drying is 20min；
Preferably, in the forming agent encapsulation steps, the sieving referred to 55-65 mesh sieves, and took described in minus mesh conduct
Cladding material；Preferably, 60 mesh sieves are crossed.
8. preparation method according to claim 4, it is characterised in that
The molding refers to：The cladding material is placed in the mould corresponding with predetermined shape, and it is compressing on press；
Preferably, the pressure of the compacting is 200~300MPa, and the time of compacting is 1~2min；Further, the pressed compact is close
Spend for the 85-95% of theoretical boracic tungsten carbide skeletal density；More preferably：The density of the pressed compact is theoretical boracic tungsten carbide bone
The 90% of frame density；
The isostatic pressing refers to：The cladding material is placed in isostatic pressed gum cover and carries out isostatic pressing；Preferably, it is described
The pressing pressure of isostatic pressing is 200~240MPa, and the dwell time is 5~10min；It is further preferred that the pressed compact
Density is the 85-95% of theoretical boracic tungsten carbide skeletal density；It is further preferred that the density of the pressed compact is theoretical boracic carbon
Change the 90% of W skeleton density.
9. preparation method according to claim 4, it is characterised in that the temperature of the sintering processes is 1400~1900
DEG C, it is incubated as 2-5h, it is highly preferred that the temperature of the sintering processes is 1600~1700 DEG C, is incubated as 3h；
Preferably, the atmosphere of the sintering processes is reducing atmosphere；It is highly preferred that the reducing atmosphere is hydrogen atmosphere；
It is further preferred that the sintering processes are completed in intermediate frequency furnace.
10. preparation method according to claim 4, it is characterised in that in the copper liquid infiltration step,
The temperature of the infiltration processing is 1300-1500 DEG C, and the time of the infiltration processing is 90~120min；It is highly preferred that
The temperature of the infiltration processing is 1400 DEG C；
Preferably, the infiltration processing is carried out in boat stove is pushed away；
Preferably, the atmosphere of the infiltration processing is reducing atmosphere；It is highly preferred that the reducing atmosphere is hydrogen atmosphere；
Preferably, the copper sheet is electrolytic copper foil, and more preferably purity is more than 99.95%；
Preferably, in the copper liquid infiltration step, the copper sheet of the constant weight refers to according to any one of claim 1-3 institutes
Amount of copper × (110-120) % that the tungsten carbide copper alloy compositions proportioning for the boracic stated calculates, more preferably：According to claim 1-
Amount of copper × 115% that the tungsten carbide copper alloy compositions proportioning of boracic described in 3 any one calculates.
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| PCT/CN2018/100782 WO2019037651A1 (en) | 2017-08-23 | 2018-08-16 | Boron-containing tungsten carbide copper alloy and method for manufacturing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019037651A1 (en) * | 2017-08-23 | 2019-02-28 | 安泰天龙（宝鸡）钨钼科技有限公司 | Boron-containing tungsten carbide copper alloy and method for manufacturing same |
| CN110823656A (en) * | 2019-11-06 | 2020-02-21 | 株洲硬质合金集团有限公司 | Preparation method of tungsten carbide mosaic sample |
| CN111411280A (en) * | 2020-03-03 | 2020-07-14 | 福达合金材料股份有限公司 | Copper tungsten carbide diamond composite electrical contact material and preparation method thereof |
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| CN107619981B (en) * | 2017-08-23 | 2019-06-18 | 安泰天龙（宝鸡）钨钼科技有限公司 | A kind of the carbonization tungsten-copper alloy and preparation method of boracic |
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