CN105132727B - A kind of plasma agglomeration preparation method of the fine grain tungsten-copper alloy with tungsten copper-clad phenomenon - Google Patents

A kind of plasma agglomeration preparation method of the fine grain tungsten-copper alloy with tungsten copper-clad phenomenon Download PDF

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CN105132727B
CN105132727B CN201510630243.8A CN201510630243A CN105132727B CN 105132727 B CN105132727 B CN 105132727B CN 201510630243 A CN201510630243 A CN 201510630243A CN 105132727 B CN105132727 B CN 105132727B
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copper
tungsten
clad
phenomenon
plasma agglomeration
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CN105132727A (en
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李继文
张会杰
魏世忠
潘昆明
徐流杰
张国赏
马小冲
王展
李志勋
王长记
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Henan University of Science and Technology
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Henan University of Science and Technology
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Abstract

A kind of plasma agglomeration preparation method of the fine grain tungsten-copper alloy with tungsten copper-clad phenomenon, comprises the following steps:First, prepare the deionized water solution of sodium tungstate and copper nitrate respectively, and be 7 according to the atom mass rate of W and Cu:30 mixing, then in mixed liquor add ammoniacal liquor adjust solution ph after ultrasonic vibration, hydro-thermal process, filtering, drying again through calcining and and two step hydrogen reductions after obtain W-Cu composite powder, will prepare W-Cu composite powder it is sintered, cooling after, that is, be obtained product;Tungsten copper two-phase is evenly distributed in quick, workable and gained the alloy of present invention reaction.

Description

A kind of plasma agglomeration preparation method of the fine grain tungsten-copper alloy with tungsten copper-clad phenomenon
Technical field
The present invention relates to the preparation technology of tungsten-copper composite material, particularly relate to a kind of with the thin of tungsten copper-clad phenomenon The plasma agglomeration preparation method of brilliant tungsten-copper alloy.
Background technology
W-Cu composites are two phase structure " the vacation conjunctions being uniformly mixed to form by two kinds of tungsten of different nature, copper products Gold ", therefore it has many good characteristics of tungsten and copper concurrently, with conduction higher and heat conductivility, low contact resistance and The features such as low thermal coefficient of expansion, thus be widely used in contact material, the shielding material of microwave device, towards plasma In the function and structure devices such as the Divertor Materials of body, electrode and heat sink material.
For with particle re-arrangement as the W-Cu systems of sintering densification leading mechanism, the refinement of material powder and composition Homogenization can effectively improve its sintering character and density etc..Therefore, ultra-fine in recent years and nanograined W-Cu powder system It is standby to become study hotspot.Hydro-thermal method is carried out at high temperature under high pressure, reactive material can be made fully to dissolve, nucleation and crystallization, system Standby process is simple, and the grain size and pattern of powder can be controlled by adjusting the parameters such as temperature and time, preparing Have great advantage in terms of the nanometer crystal alloy powder of high-purity, uniform ultra-fine grain is prepared.
Because tungsten copper is immiscible or inappreciable dissolubility, W-Cu sample sintering characters are poor, traditional infiltration of copper, liquid phase Tungsten-copper alloy generally existing composition obtained in the activated sintering method of the activation constituent element such as sintering and addition Ni, Co, Fe, Cd is not , the low shortcoming of consistency.In recent years, discharge plasma sintering is developed rapidly, and is considered as preparing with Ultra-fine Grained A kind of more feasible method with nano structural material.Discharge plasma sintering has and rises that gentle cooling velocity is fast, sintering temperature Low, sintering temperature is short and the advantages of materials microstructure and controllable composition.In short-term, the characteristics of low temperature, energy-conservation, high-efficiency sintered, can Effectively suppress crystal grain to grow up, the advantage of uniqueness is shown in terms of ultra-fine grain even nano bulk material is prepared.
The content of the invention
The present invention is in order to solve the above-mentioned technical problem, there is provided a kind of quick, strong operability and be obtained in that with tungsten copper-clad The plasma agglomeration preparation method of the fine grain tungsten-copper alloy of phenomenon.
The technical solution adopted in the present invention is:A kind of plasma agglomeration of the fine grain tungsten-copper alloy with tungsten copper-clad phenomenon Preparation method, comprises the following steps:
Step one, the deionized water solution for preparing sodium tungstate and copper nitrate respectively, it is standby;
Step 2, sodium tungstate deionized water solution obtained in step one and copper nitrate deionized water solution are taken according to W and Cu Atom mass rate be 7:30 mixing, then to adding ammoniacal liquor to adjust solution ph to 5.0~5.6 in mixed liquor, then will be mixed Hydro-thermal reaction 15-20 h, gained hydrothermal product warp are carried out at a temperature of 150~170 DEG C after closing the h of liquid supersonic oscillations 0.5~1 It is standby after filtering, drying;
Step 3, will through the dried hydro-thermal reaction product of step 2 through calcining and and two step hydrogen reductions after obtain tungsten copper and answer Powder is closed, it is standby;
Step 4, W-Cu composite powder prepared by step 3 is put into plasma agglomeration stove, and to plasma agglomeration stove In be passed through Ar as protective atmosphere, be to be incubated 10 min under conditions of 30 MPa, sintering temperature are 950-1050 DEG C in pressure, Finally cool to room temperature with the furnace, that is, product is obtained.
The purity of a kind of sodium tungstate for using of the step and copper nitrate is pure to analyze.
In the step 3, calcination process is carried out in chamber type electric resistance furnace, and calcining heat is 520 DEG C, calcination time 2h.
In the step 3, the two steps During Hydrogen Reducing is carried out in four pipe sintering and reducing stoves, and reducing atmosphere is H2/N2, The two steps During Hydrogen Reducing includes following two stages:1)500-550 DEG C, insulation 0.5-1 h;2):750-780 DEG C, protect Warm 1.0-1.2 h, cool down water cooling afterwards.
Plasma agglomeration stove in the step 4 is SPS-30 discharge plasma sintering stoves.
Sintering process in the step 4 includes following two stages:1), be increased to 600 DEG C with 100 DEG C/min, protect 10 min of temperature;2)950-1050 DEG C, 10 min of insulation insulation are increased to 50 DEG C/min.
Beneficial effects of the present invention:This method use the composite powder in tungsten coated copper phenomenon that chemically prepares for Raw material, generates the tungsten-copper alloy that the tiny tungsten of crystal grain coats steel structure, Er Qiesuo in the plasma agglomeration of follow-up repid discharge Tungsten copper two-phase is evenly distributed in the alloy for obtaining.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of W-Cu composite powder prepared by hydro-thermal co-reducing process of the present invention;
Fig. 2 is the high-resolution transmission plot of W-Cu composite powder prepared by hydro-thermal co-reducing process of the present invention;
Fig. 3 is the scanning electron microscope (SEM) photograph of the tungsten-copper alloy prepared by spark plasma sintering of the present invention.
Specific embodiment
Further explaination is of the invention with reference to embodiments.
A kind of plasma agglomeration preparation method of the fine grain tungsten-copper alloy with tungsten copper-clad phenomenon, comprises the following steps:
Step one, the deionized water solution for preparing sodium tungstate and copper nitrate respectively, it is standby;
Step 2, sodium tungstate deionized water solution obtained in step one and copper nitrate deionized water solution are taken according to W and Cu Atom mass rate be 7:30 mixing, then to adding ammoniacal liquor to adjust solution ph to 5.0~5.6 in mixed liquor, then will be mixed Hydro-thermal reaction 15-20 h, gained hydrothermal product warp are carried out at a temperature of 150~170 DEG C after closing the h of liquid supersonic oscillations 0.5~1 It is standby after filtering, drying;
Step 3, will through the dried hydro-thermal reaction product of step 2 through calcining and and two step hydrogen reductions after obtain tungsten copper and answer Powder is closed, it is standby;
Step 4, W-Cu composite powder prepared by step 3 is put into plasma agglomeration stove, and to plasma agglomeration stove In be passed through Ar as protective atmosphere, be to be incubated 10 min under conditions of 30 MPa, sintering temperature are 950-1050 DEG C in pressure, Finally cool to room temperature with the furnace, that is, product is obtained.
The purity of a kind of sodium tungstate for using of the step and copper nitrate is pure to analyze.
In the step 3, calcination process is carried out in chamber type electric resistance furnace, and calcining heat is 520 DEG C, calcination time 2h.
In the step 3, the two steps During Hydrogen Reducing is carried out in four pipe sintering and reducing stoves, and reducing atmosphere is H2/N2, The two steps During Hydrogen Reducing includes following two stages:1)500-550 DEG C, insulation 0.5-1 h;2):750-780 DEG C, protect Warm 1.0-1.2 h, cool down water cooling afterwards.
Plasma agglomeration stove in the step 4 is SPS-30 discharge plasma sintering stoves.
Sintering process in the step 4 includes following two stages:1), be increased to 600 DEG C with 100 DEG C/min, protect 10 min of temperature;2)950-1050 DEG C is increased to 50 DEG C/min, 10 min are incubated.
Embodiment 1
A kind of plasma agglomeration preparation method of the fine grain tungsten-copper alloy with tungsten copper-clad phenomenon, comprises the following steps:
Step one, the deionized water solution that sodium tungstate and copper nitrate are prepared respectively, standby, the sodium tungstate and nitric acid for being used The purity of copper is pure for analysis;
Step 2, sodium tungstate deionized water solution obtained in step one and copper nitrate deionized water solution are taken according to W and Cu Atom mass rate be 7:30 mixing, then to adding ammoniacal liquor to adjust solution ph to 5.0 in mixed liquor, then surpass mixed liquor The h of hydro-thermal reaction 15 is carried out after the h of sonication 0.5 at a temperature of 150 DEG C, gained hydrothermal product is standby after filtering, drying;
Step 3, will through the dried hydro-thermal reaction product of step 2 through calcining and and two step hydrogen reductions after obtain tungsten copper and answer Powder is closed, the calcination process is carried out in chamber type electric resistance furnace, calcining heat is 520 DEG C, calcination time 2h, and the two steps hydrogen is also Former process is carried out in four pipe sintering and reducing stoves, and reducing atmosphere is H2/N2, the two steps During Hydrogen Reducing include following two ranks Section:1)500-550 DEG C, insulation 0.-1 h;2):750-780 DEG C, 1.0 h are incubated, water cooling is cooled down afterwards;
Step 4, by step 3 prepare W-Cu composite powder be put into SPS-30 discharge plasma sintering stoves, and to etc. Ar is passed through in ion sintering furnace as protective atmosphere, is to be incubated 10 under conditions of 30 MPa, sintering temperature are 950 DEG C in pressure Min, finally cools to room temperature with the furnace, that is, product is obtained.
Sintering process in the step 4 includes following two stages:1), be increased to 600 DEG C with 100 DEG C/min, protect 10 min of temperature;2)950-1050 DEG C, 10 min of insulation insulation are increased to 50 DEG C/min.
Embodiment 2
A kind of plasma agglomeration preparation method of the fine grain tungsten-copper alloy with tungsten copper-clad phenomenon, comprises the following steps:
Step one, the deionized water solution that sodium tungstate and copper nitrate are prepared respectively, standby, the sodium tungstate and nitric acid for being used The purity of copper is pure for analysis;
Step 2, sodium tungstate deionized water solution obtained in step one and copper nitrate deionized water solution are taken according to W and Cu Atom mass rate be 7:30 mixing, then to adding ammoniacal liquor to adjust solution ph to 5.6 in mixed liquor, then surpass mixed liquor The h of hydro-thermal reaction 20 is carried out after the h of sonication 0.5 at a temperature of 150 DEG C, gained hydrothermal product is standby after filtering, drying;
Step 3, will through the dried hydro-thermal reaction product of step 2 through calcining and and two step hydrogen reductions after obtain tungsten copper and answer Powder is closed, the calcination process is carried out in chamber type electric resistance furnace, calcining heat is 520 DEG C, calcination time 2h, and the two steps hydrogen is also Former process is carried out in four pipe sintering and reducing stoves, and reducing atmosphere is H2/N2, the two steps During Hydrogen Reducing include following two ranks Section:1)500-550 DEG C, it is incubated 1 h;2):750-780 DEG C, 1.2 h are incubated, water cooling is cooled down afterwards;
Step 4, by step 3 prepare W-Cu composite powder be put into SPS-30 discharge plasma sintering stoves, and to etc. Ar is passed through in ion sintering furnace as protective atmosphere, is to be incubated 10 under conditions of 30 MPa, sintering temperature are 1050 DEG C in pressure Min, finally cools to room temperature with the furnace, that is, product is obtained.
Temperature-rise period in the step 4 includes following two stages:1), be increased to 600 DEG C with 100 DEG C/min, protect 10 min of temperature;2)1050 DEG C, 10 min of insulation insulation are increased to 50 DEG C/min.
Embodiment 3
A kind of plasma agglomeration preparation method of the fine grain tungsten-copper alloy with tungsten copper-clad phenomenon, comprises the following steps:
Step one, the deionized water solution that sodium tungstate and copper nitrate are prepared respectively, standby, the sodium tungstate and nitric acid for being used The purity of copper is pure for analysis;
Step 2, sodium tungstate deionized water solution obtained in step one and copper nitrate deionized water solution are taken according to W and Cu Atom mass rate be 7:30 mixing, then to adding ammoniacal liquor to adjust solution ph to 5.3 in mixed liquor, then surpass mixed liquor The h of hydro-thermal reaction 17.5 is carried out after the h of sonication 0.5 at a temperature of 150 DEG C, gained hydrothermal product is through filtering, drying standby With;
Step 3, will through the dried hydro-thermal reaction product of step 2 through calcining and and two step hydrogen reductions after obtain tungsten copper and answer Powder is closed, the calcination process is carried out in chamber type electric resistance furnace, calcining heat is 520 DEG C, calcination time 2h, and the two steps hydrogen is also Former process is carried out in four pipe sintering and reducing stoves, and reducing atmosphere is H2/N2, the two steps During Hydrogen Reducing include following two ranks Section:1)500-550 DEG C, it is incubated 0.75 h;2):750-780 DEG C, 1.1h is incubated, water cooling is cooled down afterwards;
Step 4, by step 3 prepare W-Cu composite powder be put into SPS-30 discharge plasma sintering stoves, and to etc. Ar is passed through in ion sintering furnace as protective atmosphere, is to be incubated 10 under conditions of 30 MPa, sintering temperature are 1000 DEG C in pressure Min, finally cools to room temperature with the furnace, that is, product is obtained.
Temperature-rise period in the step 4 includes following two stages:1), be increased to 600 DEG C with 100 DEG C/min, protect 10 min of temperature;2)1000 DEG C, 10 min of insulation insulation are increased to 50 DEG C/min.

Claims (5)

1. a kind of plasma agglomeration preparation method of the fine grain tungsten-copper alloy with tungsten copper-clad phenomenon, it is characterised in that:Including with Lower step:
Step one, the deionized water solution for preparing sodium tungstate and copper nitrate respectively, it is standby;
Step 2, take the original of sodium tungstate deionized water solution obtained in step one and copper nitrate deionized water solution according to W and Cu Protonatomic mass ratio is 7:30 mixing, then to adding ammoniacal liquor to adjust solution ph to 5.0~5.6 in mixed liquor, then by mixed liquor Hydro-thermal reaction 15-20 h are carried out after the h of supersonic oscillations 0.5~1 at a temperature of 150~170 DEG C, gained hydrothermal product passes through It is standby after filter, drying;
Step 3, will through the dried hydro-thermal reaction product of step 2 through calcining and two step hydrogen reductions after obtain class composite W-Cu powder End, it is standby;
Step 4, by step 3 prepare W-Cu composite powder be put into plasma agglomeration stove, and in plasma agglomeration stove lead to Enter Ar as protective atmosphere, be to be incubated 10 min under conditions of 30 MPa, sintering temperature are 950-1050 DEG C in pressure, finally Cool to room temperature with the furnace, that is, product is obtained;Wherein, sintering process includes following two stages:1), be increased to 100 DEG C/min 600 DEG C, it is incubated 10 min;2)950-1050 DEG C is increased to 50 DEG C/min, 10 min are incubated.
2. a kind of plasma agglomeration preparation method of the fine grain tungsten-copper alloy with tungsten copper-clad phenomenon as claimed in claim 1, It is characterized in that:The sodium tungstate and the purity of copper nitrate used in the step one are pure to analyze.
3. a kind of plasma agglomeration preparation method of the fine grain tungsten-copper alloy with tungsten copper-clad phenomenon as claimed in claim 1, It is characterized in that:In the step 3, calcination process is carried out in chamber type electric resistance furnace, and calcining heat is 520 DEG C, calcination time 2h。
4. a kind of plasma agglomeration preparation method of the fine grain tungsten-copper alloy with tungsten copper-clad phenomenon as claimed in claim 1, It is characterized in that:In the step 3, the two steps During Hydrogen Reducing is carried out in four pipe sintering and reducing stoves, and reducing atmosphere is H2/N2, the two steps During Hydrogen Reducing include following two stages:1)500-550 DEG C, insulation 0.5-1 h;2):750-780 DEG C, 1.0-1.2 h are incubated, water cooling is cooled down afterwards.
5. a kind of plasma agglomeration preparation method of the fine grain tungsten-copper alloy with tungsten copper-clad phenomenon as claimed in claim 1, It is characterized in that:Plasma agglomeration stove in the step 4 is SPS-30 discharge plasma sintering stoves.
CN201510630243.8A 2015-09-29 2015-09-29 A kind of plasma agglomeration preparation method of the fine grain tungsten-copper alloy with tungsten copper-clad phenomenon Expired - Fee Related CN105132727B (en)

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