CN115971491A - Tungsten-copper material and preparation method thereof - Google Patents
Tungsten-copper material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a tungsten copper material and a preparation method thereof, wherein the preparation method comprises the following steps: overlapping and placing a tungsten pressing blank and a copper material with an infiltration bridge, wherein the tungsten pressing blank and the copper material are arranged at intervals, and the infiltration bridge is overlapped with the tungsten pressing blank and the copper material respectively; the melting point of the infiltration bridge is higher than that of the copper material; the tungsten content of the tungsten compact is more than 50 wt%; carrying out infiltration treatment on the tungsten pressing blank, the copper material and the infiltration bridge which are arranged in an overlapped mode; and removing the infiltration bridge after cooling to obtain the tungsten-copper material. The preparation method provided by the invention overcomes the defect of insufficient copper infiltration rate in the tungsten framework, and the prepared tungsten-copper material has the advantages of uniformity and high density; the method is suitable for the requirements of the fields of aerospace, national defense and military industry, electronic information, metallurgy, machining and the like on tungsten-copper materials.
Description
Technical Field
The invention belongs to the technical field of metallurgy, relates to an alloy material, and particularly relates to a tungsten-copper material and a preparation method thereof.
Background
The tungsten-copper material consists of metal tungsten with high melting point and high hardness and metal copper with high plasticity, high electric conductivity and high thermal conductivity; because tungsten and copper are not compatible with each other, the tungsten and copper belong to pseudo alloys. This gives it both the characteristics of tungsten and copper, respectively, and the new properties that result from the combination of the two phases.
For example, tungsten copper materials have high strength and hardness at high temperature, high electrical and thermal conductivity, good electrical erosion resistance, good radiation absorption, low thermal expansion coefficient and certain plasticity; in an environment with high enough temperature, the copper phase of the tungsten copper material can evaporate to absorb heat, and the part can generate self-cooling effect. Therefore, the tungsten-copper material can be used in the fields of aerospace, national defense and military industry, electronic information, metallurgy, machining and the like.
CN107236876A discloses a preparation method of a high-compactness high-thermal conductivity tungsten copper material, which comprises: placing tungsten powder in a hydrogen furnace for reduction; (2) Performing magnetron sputtering on the reduced tungsten powder by taking a copper target as a sputtering target material to obtain a composite material; (3) Placing the composite material in a hot pressing furnace for hot pressing and sintering, and then naturally cooling to obtain a precursor; (4) And placing the precursor in a chemical vapor deposition furnace, and performing chemical vapor deposition on the precursor by taking a mixed gas of methane and water vapor as a reaction gas to obtain the high-compactness high-heat-conductivity tungsten-copper material. However, the preparation method has high process cost and is difficult to industrially popularize.
CN111250720A discloses a method for preparing a tungsten-copper composite material, which comprises the following steps: (1) Respectively taking a pure tungsten ingot and a pure copper ingot as two anodes, taking argon as a plasma gas source, heating and melting the tungsten ingot and the copper ingot by adopting different heating powers, and atomizing a melt by adopting different plasma gas pressures; (2) Carrying out hot pressing treatment on the tungsten-copper composite material billet obtained by atomization and deposition. The method comprises the steps of respectively heating and melting pure copper and pure tungsten through plasma, atomizing and depositing to obtain tungsten-copper composite materials with different W contents, and obtaining the tungsten-copper material with high density and uniform tissue. But it also has the problem of higher cost.
The preparation method of the tungsten-copper material also comprises a high-temperature liquid phase sintering method and an infiltration method. Because of the intrinsic incompatibility of two elements of tungsten (W) and copper (Cu), the tungsten-copper material prepared by adopting high-temperature liquid phase sintering has low density.
The traditional infiltration method is to prepare the tungsten framework first and then infiltrate Cu into the pores of the tungsten framework. For example, CN112355304A discloses a processing technology for preparing a CuW60-CuW90 metal profile part by injection molding: (1) Adding wax-based high-molecular binder into spherical tungsten powder of 1-10 μm, mixing, preparing injection molding feed on a feeder, and adding feed on an injection agent for injection molding to obtain a tungsten blank; sequentially degreasing and sintering the obtained tungsten blank at high temperature; (3) And then putting the tungsten blank and the copper blank into a high-temperature sintering furnace for infiltration.
However, the tungsten-copper material obtained by the traditional infiltration method has a great defect, if the infiltration temperature is too low, the viscosity of the copper melt is great, and at the moment, the capillary acting force in the tungsten skeleton is small, so that the efficiency of infiltration copper is low, and even more pores and low density exist in the skeleton after infiltration; if the temperature of the infiltration copper is too high, the viscosity of the copper melt is small, the acting force of a capillary tube in the tungsten framework is large, the speed of the copper entering the tungsten framework is too high, and the problem of local copper infiltration unevenness is caused.
Therefore, the preparation method of the uniform and high-compactness tungsten-copper material is provided, the defects of insufficient copper infiltration rate and nonuniform infiltration in a tungsten framework can be overcome, and the preparation method has important significance for reducing the preparation cost of the tungsten-copper material and carrying out industrial application on the tungsten-copper material.
Disclosure of Invention
The invention aims to provide a tungsten copper material and a preparation method thereof, wherein the preparation method is simple in process, and can overcome the defects of insufficient copper infiltration rate and non-uniform infiltration in a tungsten framework, so that the prepared tungsten copper material has the advantages of uniformity and high density.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a tungsten copper material, wherein the method comprises the following steps:
overlapping and placing a tungsten pressed blank and a copper material with an infiltration bridge, wherein the tungsten pressed blank and the copper material are arranged at intervals, the infiltration bridge is respectively overlapped with the tungsten pressed blank and the copper material, the melting point of the infiltration bridge is higher than that of the copper material, and the tungsten content of the tungsten pressed blank is more than 50 wt%;
carrying out infiltration treatment on the tungsten pressing blank, the copper material and the infiltration bridge which are arranged in an overlapped mode;
and removing the infiltration bridge after cooling to obtain the tungsten-copper material.
The preparation method provided by the invention has simple process, realizes indirect infiltration through the arrangement of the infiltration bridge, and overcomes the defect of low density of the obtained tungsten-copper material caused by insufficient copper infiltration rate. In the obtained tungsten-copper material, copper is uniformly distributed, and the tungsten-copper material has the advantages of uniformity and high density.
The tungsten content in the tungsten compact of the present invention is 50wt% or more, for example, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt%, 90wt%, or 95wt%, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the mass ratio of the copper material to the tungsten compact is 1 (2-10), and may be, for example, 1.
Preferably, the ratio of the area of the infiltration bridge to the tungsten compact to the area of the surface of the tungsten compact to be lapped is (0.01-0.5): 1, and may be, for example, 0.01.
Preferably, the ratio of the area of the infiltration bridge to the copper material to the area of the surface of the copper material to be lapped is (0.01-0.5): 1, which can be, for example, 0.01.
Preferably, the infiltration bridge is made of any one or a combination of at least two of tungsten, molybdenum, tungsten-copper alloy or molybdenum-copper alloy, and typical but non-limiting combinations include a combination of tungsten and molybdenum, a combination of molybdenum and tungsten-copper alloy, a combination of tungsten and molybdenum-copper alloy, or a combination of tungsten, molybdenum, tungsten-copper alloy and molybdenum-copper alloy.
Preferably, the copper material of the present invention has a purity of 99.999wt% or more, such as 99.9990wt%, 99.9991wt%, 99.9993wt%, 99.9995wt%, 99.9996wt%, 99.9998wt% or 99.9999wt%, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the composition of the tungsten copper material comprises 55-90wt% of tungsten and 10-45wt% of copper.
In a preferred embodiment of the present invention, the tungsten-copper material comprises 55-90wt% of tungsten, such as 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, 85wt% or 90wt%, but not limited to the recited values, and other values in the range of values are also applicable.
The tungsten copper material has a composition of 10 to 45wt% copper, which may be, for example, 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, or 45wt%, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the infiltration process is performed in a protective atmosphere.
Preferably, the gas used for the protective atmosphere comprises hydrogen.
Preferably, the infiltration treatment includes a first heat treatment and a second heat treatment which are sequentially performed.
Preferably, the temperature of the first heat treatment is 1000-1100 ℃ and the time is 100-140min.
The temperature of the first heat treatment according to the present invention is 1000 to 1100 deg.C, and may be, for example, 1000 deg.C, 1020 deg.C, 1050 deg.C, 1060 deg.C, 1080 deg.C or 1100 deg.C, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
The time of the first heat treatment of the present invention is 100 to 140min, and may be, for example, 100min, 105min, 110min, 115min, 120min, 125min, 130min, 135min or 140min, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the temperature of the second heat treatment is 1350-1450 ℃ and the time is 100-140min.
The temperature of the second heat treatment according to the present invention is 1350 to 1450 deg.C, and may be 1350 deg.C, 1380 deg.C, 1400 deg.C, 1420 deg.C or 1450 deg.C, but is not limited to the values listed, and other values not listed in the range of values are also applicable.
The time of the second heat treatment is 100-140min, for example, 100min, 105min, 110min, 115min, 120min, 125min, 130min, 135min or 140min, but is not limited to the values listed, and other values not listed in the range of values are also applicable.
Preferably, the method for preparing the tungsten compact comprises the following steps: and uniformly mixing raw material powder according to the component proportion of the tungsten pressed blank, and carrying out cold isostatic pressing treatment to obtain the tungsten pressed blank.
Illustratively, the intimate mixing is carried out in a V-blender.
Preferably, the composition of the tungsten compact comprises 80-95wt% tungsten and 5-20wt% copper.
The composition of the tungsten compact according to the invention comprises 80-95wt% of tungsten, which may be, for example, 80wt%, 81wt%, 82wt%, 84wt%, 85wt%, 86wt%, 88wt%, 90wt%, 95wt%, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
The composition of the tungsten compact according to the invention comprises 5-20wt% copper, which may be, for example, 5wt%, 10wt%, 12wt%, 14wt%, 15wt%, 16wt%, 18wt% or 20wt%, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the Fischer-Tropsch type particle size of the tungsten powder in the raw material powder is 2 to 10 μm, and may be, for example, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 8 μm, or 10 μm, but is not limited to the values recited, and other values not recited in the range of values are also applicable.
The Fisher size of the tungsten powder refers to the average Fisher size of the tungsten powder.
Preferably, the Fisher size of the copper powder in the starting powder is 50 μm or less, and may be, for example, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm or 50 μm, but is not limited to the values recited, and other values not recited in the range of values are equally applicable.
The Fisher size of the copper powder is less than or equal to 50 mu m, namely, the copper powder is sieved to ensure that the Fisher size of the copper powder is less than or equal to 50 mu m.
Preferably, the cold isostatic pressing has a pressure of 170-230MPa, which may be, for example, 170MPa, 180MPa, 185MPa, 190MPa, 195MPa, 200MPa, 205MPa, 210MPa, 220MPa or 230MPa, but is not limited to the values listed, and other values not listed within the range of values are equally applicable.
Preferably, the cold isostatic pressing has a dwell time of 60 to 120s, which may be, for example, 60s, 70s, 80s, 85s, 90s, 95s, 100s, 110s or 120s, but is not limited to the values listed, and other values not listed in the range of values are equally applicable.
Preferably, the method for preparing the infiltration tungsten bridge comprises the following steps: and (3) performing cold isostatic pressing on the tungsten powder and/or the molybdenum powder to obtain a pressed compact, and sintering in a protective atmosphere to obtain the infiltration bridge.
Preferably, the gas used for the protective atmosphere comprises hydrogen.
Preferably, the tungsten powder and/or molybdenum powder has a Fisher-Tropsch particle size of 2 to 10 μm, which may be, for example, 2 μm, 4 μm, 5 μm, 6 μm, 8 μm or 10 μm, but is not limited to the values recited, and other values not recited within the range of values are equally applicable.
The fern particle size refers to the average fern particle size.
Preferably, the pressure of the cold isostatic pressing is 170-230MPa, and the dwell time is 60-120s.
In the production of the infiltration tungsten bridge of the invention, the cold isostatic pressure is 170-230MPa, and may be, for example, 170MPa, 180MPa, 185MPa, 190MPa, 195MPa, 200MPa, 205MPa, 210MPa, 220MPa or 230MPa, but is not limited to the values listed, and other values not listed within the range of values are equally applicable.
In the production of the infiltration tungsten bridge according to the invention, the dwell time of the cold isostatic pressing is 60 to 120s, for example 60s, 70s, 80s, 85s, 90s, 95s, 100s, 110s or 120s, but is not limited to the values listed, and other values not listed in the range of values are equally suitable.
Preferably, the sintering temperature is 1000-1400 ℃, and the time is 60-240min.
In the preparation of the infiltration bridge of the present invention, the sintering temperature is 1000-1400 ℃, for example, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃, 1250 ℃, 1300 ℃, 1350 ℃ or 1400 ℃, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
When the infiltration bridge is prepared by the method, the sintering time is 60-240min, such as 60min, 80min, 100min, 120min, 150min, 160min, 180min, 200min, 210min or 240min, but the method is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the relative density of the infiltrated tungsten bridges is in the range of 40 to 80%, for example 40%, 50%, 60%, 70% or 80%, but not limited to the recited values, and other values not recited within the range of values are equally applicable.
As a preferable technical solution of the preparation method of the first aspect, the preparation method comprises the steps of:
carrying out infiltration treatment on the tungsten pressing blank, the copper material and the infiltration bridge which are arranged in an overlapped mode in a protective atmosphere, and removing the infiltration bridge after cooling to obtain the tungsten-copper material; the mass ratio of the copper material to the tungsten pressing blank is 1 (2-10);
the ratio of the overlapping area of the infiltration bridge and the tungsten pressing blank to the overlapped surface area of the tungsten pressing blank is (0.01-0.5): 1, and the ratio of the overlapping area of the infiltration bridge and the copper material to the overlapped surface area of the copper material is (0.01-0.5): 1;
the infiltration treatment comprises a first heat treatment and a second heat treatment which are sequentially carried out; the temperature of the first heat treatment is 1000-1100 ℃, and the time is 100-140min; the temperature of the second heat treatment is 1350-1450 ℃, and the time is 100-140min;
the method for preparing the tungsten compact comprises the following steps: uniformly mixing tungsten powder with the Fisher size of 2-10 mu m and copper powder with the Fisher size of less than or equal to 50 mu m, and carrying out cold isostatic pressing at 170-230MPa for 60-120s to obtain the tungsten pressed blank; the tungsten pressing blank comprises 80-95wt% of tungsten and 5-20wt% of copper;
the method for preparing the infiltration bridge comprises the following steps: treating tungsten powder with Fisher particle size of 2-10 μm with cold isostatic pressing at 170-230MPa for 60-120s; sintering the obtained blank in hydrogen atmosphere at 1000-1400 deg.C for 60-240min to obtain infiltration bridge with relative density of 40-85%.
In a second aspect, the invention provides a tungsten copper material prepared by the preparation method of the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method provided by the invention has simple process, realizes indirect infiltration through the arrangement of the infiltration bridge, and overcomes the defect of low density of the obtained tungsten-copper material caused by insufficient copper infiltration rate; in the obtained tungsten copper material, copper is uniformly distributed, and the density of the tungsten copper material is high.
Drawings
Fig. 1 is a schematic structural view of lap joint arrangement in embodiment 1, embodiment 2 and embodiment 3;
FIG. 2 is a metallographic micrograph of tungsten copper material obtained in example 1 wherein the dark grey areas 4 are tungsten and the light grey areas 5 are copper;
FIG. 3 is a metallographic micrograph of a tungsten copper material obtained in comparative example 1, in which the areas 4a are tungsten, the areas 5a are copper and the black areas 6a are pores.
Wherein: 1, copper material; 2, pressing a blank by tungsten; 3, infiltration of the bridge.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
In the specific implementation mode of the invention, the element content in the tungsten copper material is determined according to the standard of GJB 2299A-2005.
Example 1
The embodiment provides a preparation method of a tungsten copper material, which comprises the following steps:
preparing a tungsten pressed blank 2: weighing tungsten powder with the Fisher size of 3.5 mu m and copper powder with the particle size of 45 mu m according to the weight ratio of the tungsten powder to the copper powder of 85, then loading the tungsten powder and the copper powder into a small V-shaped mixer, and fully mixing for 24 hours to obtain tungsten-copper mixed powder; loading the tungsten-copper mixed powder into
In a polyurethane mold, into>
The stainless steel hard die is put into a cold isostatic press for cold isostatic pressing treatment, wherein the pressure is 195MPa, the pressure maintaining time is 90S, and the stainless steel hard die is obtained by demoulding after pressure relief
The tungsten compact 2.
Preparing copper material 1: putting the cathode copper with the purity of 99.95 percent into a high vacuum melting furnace, and controlling the vacuum degree to be 10 at 1300 DEG C -4 Vacuum melting is carried out for 1h under the condition of Pa, and then the casting is carried out in a mould with a water cooling sleeve to obtain a refined copper ingot; after cutting, the copper material is sequentially washed by acid and alkali, soaked and cleaned by deionized water and absolute ethyl alcohol, and then is placed in a 100 ℃ oven for drying, so that the copper material 1 with the purity of 99.995% is obtained.
Preparing an infiltration bridge 3: tungsten powder with the Fisher particle size of 3 mu m is filled into a polyurethane mold with the size of 50 multiplied by 15mm, then is put into a stainless steel hard mold with the size of 60 multiplied by 20mm, and is put into a cold isostatic press for cold isostatic pressing treatment, wherein the pressure is 195MPa, the pressure maintaining time is 90S, a billet is obtained after pressure relief and demolding, and then is put into a hydrogen furnace for sintering, so that infiltration bridges 3 with the size of 4 multiplied by 10mm are obtained, and the relative density of the infiltration bridges 3 is 70%.
And (3) infiltration treatment: weighing a copper material 1 and a tungsten pressing blank 2 according to a weight ratio of the copper material 1 to the tungsten pressing blank 2 being 30; placing the overlapped tungsten pressing blank 2, copper material 1 and infiltration bridge 3 into a container fully covered with No. 400 corundum sand, and putting the container into a hydrogen furnace for infiltration, wherein the infiltration process comprises the steps of firstly heating to 1050 ℃, preserving heat for 120min, then heating to 1400 ℃, and preserving heat for 120min.
And (3) machining treatment: taking out the whole body after cooling, cutting the lap joint of the infiltration bridge 3 and the tungsten copper material by using a cutting machine, and machining the surface of the tungsten copper material to obtain the tungsten copper alloy
The tungsten copper material of (1).
The tungsten copper material obtained in the embodiment adopts GJB2299A-2005 to measure the element content, and the tungsten copper material contains 60wt% of tungsten and 40wt% of copper.
The metallographic microscopic image of the tungsten-copper material obtained in the embodiment was measured by using a leica inverted metallographic microscope according to the standard of GB/T13298-2015, the metallographic fibrous image obtained in the embodiment is shown in fig. 2, the dark gray area 4 in fig. 2 is tungsten, and the light gray area 5 is copper, and as can be seen from fig. 2, the tungsten-copper material obtained in the embodiment has no pores (i.e., high copper infiltration rate) and is uniform in copper distribution.
Example 2
The embodiment provides a preparation method of a tungsten copper material, which comprises the following steps:
preparing a tungsten pressed blank 2: tungsten powder with a Fisher size of 2 mu m and copper powder with a particle size of 35 mu m are weighed according to the weight ratio of the tungsten powder to the copper powder of 80, then the weighed tungsten powder and copper powder are put into a small V-shaped mixer, and are fully mixed for 24 hours to obtain tungsten-copper mixed powder. Loading the tungsten-copper mixed powder into
Is placed in the polyurethane mold (4) and is placed in>
The stainless steel hard die is put into a cold isostatic press for cold isostatic pressing treatment, wherein the pressure is 170MPa, the pressure maintaining time is 120S, and the stainless steel hard die is obtained by demoulding after pressure relief
The tungsten compact 2.
Preparing copper material 1: putting the cathode copper with the purity of 99.95 percent into a high vacuum melting furnace, and heating the cathode copper at 1300 ℃ and the vacuum degree of 10 -4 And (3) vacuum melting is carried out for 1h under the Pa condition, and then the alloy is cast into a mould with a water cooling sleeve to obtain a refined copper ingot. After cutting, the copper material is washed by acid washing, alkali washing, deionized water and absolute ethyl alcohol, and then is dried in an oven at 100 ℃ to obtain the copper material 1 with the purity of 99.995%.
Preparing an infiltration bridge 3: tungsten powder with 2 mu m Fisher particle size is filled into a polyurethane mold with the size of 50 multiplied by 15mm, then the tungsten powder is put into a stainless steel hard mold with the size of 60 multiplied by 20mm, the stainless steel hard mold is put into a cold isostatic press for cold isostatic pressing treatment, wherein the pressure is 230MPa, the pressure maintaining time is 60S, the blank is obtained after pressure relief and demolding, then the blank is put into a hydrogen furnace for sintering, and infiltration bridges 3 with the size of 45 multiplied by 10mm are obtained, and the relative density of the infiltration bridges 3 is 85 percent.
And (3) infiltration treatment: weighing a copper material 1 and a tungsten pressing blank 2 according to a weight ratio of the copper material 1 to the tungsten pressing blank 2 being 1; placing the overlapped tungsten pressing blank 2, copper material 1 and infiltration bridge 3 into a container fully covered with No. 400 corundum sand, and putting the container into a hydrogen furnace for infiltration, wherein the infiltration process comprises the steps of firstly heating to 1000 ℃, preserving heat for 140min, then heating to 1350 ℃ and preserving heat for 140min.
And (3) machining treatment: taking out the whole body after cooling, cutting the lap joint of the infiltration bridge 3 and the tungsten copper material by a cutting machine, and machining the surface of the tungsten copper material to obtain the tungsten copper material
Tungsten copper material.
The tungsten copper material obtained in the embodiment adopts GJB2299A-2005 to measure the element content, and the tungsten copper material contains 60wt% of tungsten and 40wt% of copper.
Example 3
The embodiment provides a preparation method of a tungsten copper material, which comprises the following steps:
preparing a tungsten compact 2: tungsten powder with a Fisher size of 10 mu m and copper powder with a particle size of 50 mu m are weighed according to the weight ratio of the tungsten powder to the copper powder of 95 to be loaded into a small V-shaped mixer, and are fully mixed for 24 hours to obtain tungsten-copper mixed powder. Loading the tungsten-copper mixed powder into
Is placed in the polyurethane mold (4) and is placed in>
The stainless steel hard die is put into a cold isostatic press for cold isostatic pressing treatment, wherein the pressure is 230MPa, the pressure maintaining time is 60S, and the stainless steel hard die is obtained by demoulding after pressure relief
The tungsten compact 2.
Preparing copper material 1: putting the cathode copper with the purity of 99.95 percent into a high vacuum melting furnace, and heating the cathode copper at 1300 ℃ and the vacuum degree of 10 -4 Pa conditionAnd after vacuum melting for 1h, casting the copper ingot into a mold with a water cooling sleeve to obtain a refined copper ingot. After cutting, the copper material is washed by acid washing, alkali washing, deionized water and absolute ethyl alcohol, and then is dried in an oven at 100 ℃ to obtain the copper material 1 with the purity of 99.995%.
Preparing an infiltration bridge 3: tungsten powder with 10 mu m Fisher particle size is filled into a polyurethane mold with the size of 50 multiplied by 15mm, then the tungsten powder is put into a stainless steel hard mold with the size of 60 multiplied by 20mm, the stainless steel hard mold is put into a cold isostatic press for cold isostatic pressing treatment, wherein the pressure is 230MPa, the pressure maintaining time is 60S, the blank bar is obtained after pressure relief and demolding, then the blank bar is put into a hydrogen furnace for sintering, and the infiltration bridge 3 with the size of 45 multiplied by 10mm is obtained, and the relative density of the infiltration bridge 3 is 40%.
And (3) infiltration treatment: weighing a copper material 1 according to the weight ratio of the copper material 1 to a tungsten pressing blank 2 being 1; placing the overlapped tungsten pressing blank 2, copper material 1 and infiltration bridge 3 into a container fully covered with No. 400 corundum sand, and putting the container into a hydrogen furnace for infiltration, wherein the infiltration process comprises the steps of firstly heating to 1100 ℃, preserving heat for 100min, and then heating to 1450 ℃, and preserving heat for 100min.
And (3) machining treatment: taking out the whole body after cooling, cutting the lap joint of the infiltration bridge 3 and the tungsten copper material by a cutting machine, and machining the surface of the tungsten copper material to obtain the tungsten copper material
Tungsten copper material.
The tungsten copper material obtained in the embodiment adopts GJB2299A-2005 to measure the element content, and the tungsten copper material contains 85wt% of tungsten and 15wt% of copper.
Example 4
This example provides a method of manufacturing a tungsten copper material, which is the same as that of example 1, except that molybdenum powder was used instead of tungsten powder in manufacturing an infiltration bridge.
Example 5
This example provides a method for preparing a tungsten-copper material, which is the same as in example 1 except that the mass ratio of copper material to tungsten compact is 1.
The tungsten copper material obtained in the embodiment adopts GJB2299A-2005 to measure the element content, and the tungsten copper material contains 60wt% of tungsten and 40wt% of copper.
Example 6
This example provides a method for preparing a tungsten-copper material, which is the same as in example 3, except that the mass ratio of the copper material to the tungsten compact is 1.
The tungsten copper material obtained in the embodiment adopts GJB2299A-2005 to measure the element content, and the tungsten copper material contains 85wt% of tungsten and 15wt% of copper.
Example 7
This example provides a method for producing a tungsten-copper material, which is the same as in example 1, except that a tungsten compact is produced in a weight ratio of tungsten powder to copper powder of 90.
The tungsten copper material obtained in the embodiment adopts GJB2299A-2005 to determine the element content, and the tungsten copper material contains 70wt% of tungsten and 30wt% of copper.
Example 8
This example provides a method of producing a tungsten copper material, which is the same as that of example 1 except that the Fisher size of the tungsten powder used for producing the infiltration bridge is 0.5. Mu.m.
Example 9
This example provides a method of producing a tungsten copper material, which is the same as that of example 1 except that the Fisher size of the tungsten powder used for producing the infiltration bridge is 15 μm.
Example 10
This example provides a method of manufacturing a tungsten copper material, which is the same as that of example 1, except that the sintering temperature is lowered and the sintering time is shortened to make the relative density of the infiltration bridge 35%.
Example 11
This example provides a method of manufacturing a tungsten copper material, which is the same as that of example 1, except that the sintering temperature is increased and the sintering time is increased to make the relative density of the infiltration bridge 87%.
Example 12
This example provides a method for preparing a tungsten-copper material, which is similar to that of example 1 except that the infiltration process is performed only by the first heat treatment at 1050 ℃ for 240min.
Example 13
This example provides a method for preparing a tungsten-copper material, which is similar to that of example 1, except that the infiltration process is performed only by the second heat treatment at 1400 ℃ for 240min.
Comparative example 1
The method for preparing the tungsten-copper material of the comparative example is different from that of example 1 in the infiltration treatment step, which includes: weighing the copper material according to the weight ratio of the copper material to the tungsten pressed blank of 30, stacking the tungsten pressed blank and the copper material up and down, placing the tungsten pressed blank and the copper material into a container fully paved with No. 400 corundum sand, and putting the container into a hydrogen furnace for infiltration, wherein the infiltration process comprises the steps of firstly heating to 1050 ℃, preserving heat for 120min, then heating to 1400 ℃, and preserving heat for 120min.
The tungsten copper material obtained by the comparative example is subjected to element content measurement by adopting GJB2299A-2005, and the tungsten copper material contains 60wt% of tungsten and 40wt% of copper.
According to a metallographic microscopic picture of the tungsten copper material obtained by the comparative example, which is measured by a Leica inverted metallographic microscope according to the standard of GB/T13298-2015, the metallographic fibrous picture obtained by the comparative example is shown in FIG. 3, a region 4a in the FIG. 3 is tungsten, a region 5a is copper, and a black region 6a is a pore, and as can be seen from FIG. 3, the copper in the tungsten copper material prepared by the comparative example is unevenly distributed, copper does not permeate into a part of regions (regions 6a in FIG. 3), and the infiltration rate is low.
Performance testing
The tungsten copper materials provided in examples 1 to 13 and comparative example 1 were subjected to performance testing: measuring the density of the tungsten copper material by using a drainage method; randomly cutting a 5mm thin slice, inlaying, grinding and polishing the thin slice, and measuring the average hardness HV10 of the cross section; and manufacturing an arc contact, performing closing test under the condition of 1.2KA, and recording the closing times of closing the arc contact to damage as the service life.
The results obtained are shown in table 1.
TABLE 1
As can be seen from examples 1 to 7 in table 1, the preparation method provided by the present invention is suitable for tungsten copper materials with a wide copper content range, and when the copper content in the obtained tungsten copper material is in the range of 15 to 40wt%, arc contacts made of the tungsten copper material have closing times which can reach 2200 times or more.
From a comparison of examples 8, 9 and 1, it can be seen that when the Fisher size of the tungsten powder from which the infiltrated tungsten bridge is made is too low or too high, there is at least a 7.2% reduction in the density of the resulting tungsten-copper material, at least a 10.1% reduction in the average hardness (HV 10) and at least a 25% reduction in the service life of the finished arc contact. Therefore, the preparation method provided by the invention preferably controls the Fisher particle size to be 2-10 mu m when preparing the infiltration bridge.
From a comparison of examples 10, 11 and 1, it can be seen that when the relative density of the produced infiltration bridges is too low or too high, there is a reduction of at least 7.2% in the density of the obtained tungsten-copper material, at least 15.7% in the average hardness (HV 10) and at least 4.1% in the service life of the manufactured arcing contacts. Therefore, the preparation method provided by the invention preferably prepares the infiltration bridge with the relative density of 40-85%.
As can be seen from comparison between comparative example 1 and example 1, the tungsten copper material of the present invention prepared by the indirect infiltration method can improve the density and average hardness of the obtained tungsten copper material and the service life of the arc contact made of the tungsten copper material.
In conclusion, the preparation method provided by the invention has simple process, realizes indirect infiltration through the arrangement of the infiltration bridge, and improves the defect of low density of the obtained tungsten-copper material caused by insufficient copper infiltration rate; in the obtained tungsten copper material, copper is uniformly distributed, and the density of the tungsten copper material is high.
The above description is only for the specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.
Claims (10)
1. The preparation method of the tungsten copper material is characterized by comprising the following steps:
overlapping and placing a tungsten pressing blank and a copper material with an infiltration bridge, wherein the tungsten pressing blank and the copper material are arranged at intervals, and the infiltration bridge is overlapped with the tungsten pressing blank and the copper material respectively; the melting point of the infiltration bridge is higher than that of the copper material; the tungsten content of the tungsten compact is more than 50 wt%;
carrying out infiltration treatment on the tungsten pressing blank, the copper material and the infiltration bridge which are arranged in an overlapped mode;
and removing the infiltration bridge after cooling to obtain the tungsten-copper material.
2. The preparation method according to claim 1, characterized in that the mass ratio of the copper material to the tungsten compact is 1 (2-10);
preferably, the ratio of the overlapping area of the infiltration bridge and the tungsten pressing blank to the overlapped surface area of the tungsten pressing blank is (0.01-0.5): 1;
preferably, the ratio of the overlapping area of the infiltration bridge and the copper material to the area of the overlapped surface of the copper material is (0.01-0.5): 1.
3. The method of claim 1 or 2, wherein the material of the infiltration bridge comprises at least one of tungsten, molybdenum, tungsten-copper alloy or molybdenum-copper alloy;
preferably, the purity of the copper material is more than 99.999%;
preferably, the composition of the tungsten copper material comprises 55-90wt% of tungsten and 10-45wt% of copper.
4. The production method according to any one of claims 1 to 3, characterized in that the infiltration treatment is performed in a protective atmosphere;
preferably, the gas used for the protective atmosphere comprises hydrogen;
preferably, the infiltration treatment comprises a first heat treatment and a second heat treatment which are sequentially performed;
preferably, the temperature of the first heat treatment is 1000-1100 ℃, and the time is 100-140min;
preferably, the temperature of the second heat treatment is 1350-1450 ℃ and the time is 100-140min.
5. The production method according to any one of claims 1 to 3, characterized in that the method of producing the tungsten compact comprises the steps of: uniformly mixing raw material powder according to the component proportion of the tungsten pressing blank, and carrying out cold isostatic pressing treatment to obtain the tungsten pressing blank;
preferably, the composition of the tungsten compact comprises 80-95wt% of tungsten and 5-20wt% of copper.
6. The production method according to claim 5, wherein the Fisher size of the tungsten powder in the raw material powder is 2 to 10 μm;
preferably, the Fisher size of the copper powder in the raw material powder is less than or equal to 50 mu m.
7. The method of claim 5 or 6, wherein the cold isostatic pressing is at a pressure of 170-230MPa;
preferably, the cold isostatic pressing has a dwell time of 60 to 120s.
8. The method of any one of claims 1-7, wherein the method of making the infiltration bridge comprises the steps of: carrying out cold isostatic pressing on tungsten powder and/or molybdenum powder to obtain a pressed compact, and sintering in a protective atmosphere to obtain the infiltration bridge;
preferably, the gas used for the protective atmosphere comprises hydrogen;
preferably, the Fisher size of the tungsten powder and/or molybdenum powder is 2-10 mu m;
preferably, the pressure of the cold isostatic pressing is 170-230MPa, and the dwell time is 60-120s;
preferably, the sintering temperature is 1000-1400 ℃, and the time is 60-240min;
preferably, the relative density of the infiltration bridges is 40-85%.
9. The production method according to any one of claims 1 to 8, characterized by comprising the steps of:
carrying out infiltration treatment on the tungsten pressing blank, the copper material and the infiltration bridge which are overlapped in a protective atmosphere, and removing the infiltration bridge after cooling to obtain the tungsten-copper material; the mass ratio of the copper material to the tungsten pressing blank is 1 (2-10);
the ratio of the overlapping area of the infiltration bridge and the tungsten pressing blank to the area of the overlapped surface of the tungsten pressing blank is (0.01-0.5) to 1, and the ratio of the overlapping area of the infiltration bridge and the copper material to the area of the overlapped surface of the copper material is (0.01-0.5) to 1;
the infiltration treatment comprises a first heat treatment and a second heat treatment which are sequentially carried out; the temperature of the first heat treatment is 1000-1100 ℃, and the time is 100-140min; the temperature of the second heat treatment is 1350-1450 ℃, and the time is 100-140min;
the method for preparing the tungsten compact comprises the following steps: uniformly mixing tungsten powder with the Fisher size of 2-10 mu m and copper powder with the Fisher size of less than or equal to 50 mu m, and carrying out cold isostatic pressing at 170-230MPa for 60-120s to obtain the tungsten pressed blank; the tungsten pressing blank comprises 80-95wt% of tungsten and 5-20wt% of copper;
the method for preparing the infiltration bridge comprises the following steps: treating tungsten powder with Fisher particle size of 2-10 μm with cold isostatic pressing at 170-230MPa for 60-120s; sintering the obtained blank in hydrogen atmosphere at 1000-1400 deg.C for 60-240min to obtain infiltration bridge with relative density of 40-85%.
10. A tungsten-copper material produced by the production method according to any one of claims 1 to 9.
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