CN104404282A - Tungsten copper alloy with low tungsten content and preparation method of tungsten copper alloy - Google Patents
Tungsten copper alloy with low tungsten content and preparation method of tungsten copper alloy Download PDFInfo
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- CN104404282A CN104404282A CN201410717402.3A CN201410717402A CN104404282A CN 104404282 A CN104404282 A CN 104404282A CN 201410717402 A CN201410717402 A CN 201410717402A CN 104404282 A CN104404282 A CN 104404282A
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- SBYXRAKIOMOBFF-UHFFFAOYSA-N copper tungsten Chemical compound [Cu].[W] SBYXRAKIOMOBFF-UHFFFAOYSA-N 0.000 title claims abstract description 55
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 229910052721 tungsten Inorganic materials 0.000 title abstract description 6
- 239000010937 tungsten Substances 0.000 title abstract description 6
- 238000007731 hot pressing Methods 0.000 claims abstract description 62
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000010949 copper Substances 0.000 claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000011812 mixed powder Substances 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims description 32
- 239000001257 hydrogen Substances 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- 238000005245 sintering Methods 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 238000005096 rolling process Methods 0.000 claims description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- 238000004381 surface treatment Methods 0.000 claims description 16
- 238000005098 hot rolling Methods 0.000 claims description 14
- 238000000137 annealing Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 238000002203 pretreatment Methods 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 9
- 239000001307 helium Substances 0.000 claims description 9
- 229910052734 helium Inorganic materials 0.000 claims description 9
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 238000005097 cold rolling Methods 0.000 claims description 7
- 238000005056 compaction Methods 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- -1 carry out in vacuum Substances 0.000 claims description 4
- 238000000462 isostatic pressing Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 230000007547 defect Effects 0.000 description 10
- 239000000463 material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 4
- 238000000280 densification Methods 0.000 description 4
- 230000008595 infiltration Effects 0.000 description 4
- 238000001764 infiltration Methods 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 241001282153 Scopelogadus mizolepis Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 210000000867 larynx Anatomy 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Abstract
The invention provides a method for preparing a tungsten copper alloy. The preparation method comprises the steps of preparing tungsten and copper mixed powder into a briquet for presintering, and hot-pressing the briquet at a temperature lower than a melting point of copper. The tungsten copper alloy prepared by the preparation method is uniform in texture, high in density, excellent in performance and high in rate of finished products.
Description
Technical field
The invention belongs to alloy field, be specifically related to lower tungsten-copper alloy of a kind of W content and preparation method thereof.
Background technology
Tungsten-copper alloy is " pseudoalloy " that be made up of the copper of the tungsten of high-melting-point, high rigidity and high connductivity, thermal conductivity.It has the good advantage such as resistance to arc erosion, resistance fusion welding, high strength, high rigidity.In addition, its heat conduction, conductivity and thermal expansivity can be designed by adjustment tungsten, copper component concentration.Therefore, tungsten-copper alloy is widely used as the military project material (as rocket nozzle, aircraft larynx lining) etc. of electrical contact material, resistance welding, electrospark machining and plasma electrode material, electrical heating alloys and heavy metal, special purpose.In addition, tungsten-copper alloy is also used to the heat sink substrate of the electron device such as lead frame and solid state microwave pipe of computer central processing system, large-scale integrated circuit.
Along with the development of new and high technology, tungsten-copper alloy is applied in more field.Especially in military project, such as, as medicine cover, the nozzle of increasing journey big gun, the material etc. of magnetic artillery track of aerospacecraft, tank high explosive anti-tank cartridge.These fields for the requirement of tungsten-copper alloy performance considerably beyond the requirement as general contact material.Therefore, improve physicals and the processability of tungsten-copper composite material, produce high performance product, be the focus of Chinese scholars research always.
Prepare the method mainly infiltration method of tungsten-copper alloy at present, namely first prepare the POROUS TUNGSTEN skeleton of certain density, intensity, then ooze with molten copper liquid in W skeleton, utilize capillary action that copper liquid is packed in W skeleton thus form fine and close matrix material.Preparation even structure, W skeleton that is good to copper wettability, that have a certain amount of open pore are the keys that infiltration method prepares Tungsten-copper Composites.
For the tungsten-copper alloy (W content is less than 50 % by weight) that W content is lower, according to the infiltration method of routine, be difficult to obtain up-to-standard tungsten-copper alloy.Major cause is, when tungsten powder content is lower, is difficult to obtain high-quality W skeleton base.If mixed with copper powder by tungsten powder after suppressing and ooze copper, in the sintered blank obtained, still have the copper segregation district of unmanageable constriction zone and big scale.
Prior art also adopts high-temperature liquid-phase sintering process to prepare tungsten-copper alloy, because sintering temperature is very high, sintering time is very long, therefore sintering character is poor, sintered density lower (being only 90% ~ 95% of theoretical density), physics, the electrical and mechanical properties of material are still not ideal enough, can not meet service requirements.
Summary of the invention
An object of the present invention is to provide a kind of preparation method of tungsten-copper alloy.
Contriver finds, by carrying out hot pressing to the temperature of pressed compact below copper fusing point of tungsten powder and copper powder mixed powder, can obtain the tungsten-copper alloy of high-compactness, especially high-compactness, tungsten-copper alloy that W content is lower.Overcome the defect of traditional infiltration method and lqiuid phase sintering method.
The invention provides a kind of preparation method of tungsten-copper alloy, it comprises the following steps:
(1) pressed compact: tungsten powder and copper powder mixed rear pressed compact;
(2) presintering: presintering is carried out to the pressed compact that step (1) obtains, pre-sintering temperature is preferably 1000 ~ 1050 DEG C (such as 1010 DEG C, 1020 DEG C, 1030 DEG C or 1040 DEG C), and sintering time is preferably 30 ~ 120 minutes (such as 50 minutes, 60 minutes, 90 minutes, 100 minutes);
(3) hot pressing: hot pressing is carried out to the sintered blank that step (2) obtains, the temperature of hot pressing is preferably 850 ~ 1070 DEG C (such as 1000 ~ 1070 DEG C), pressure is preferably 2500 ~ 4000KN (more preferably 2800 ~ 3800KN or 3000 ~ 3500KN or 3000 ~ 3200KN, such as 3100KN, 3150KN or 3180KN), the dwell time is preferably 1-3 minute (such as 2 minutes);
(4) optionally, the heat-press step 2 ~ 3 times of repeating step (3).
In a preferred embodiment, the preparation method of tungsten-copper alloy of the present invention, wherein the hot pressing of step (3) first the sintered blank that step (2) obtains is heated to 850 ~ 1070 DEG C (such as 1000 ~ 1070 DEG C), be incubated and (be preferably incubated 15 ~ 40 minutes in 15 ~ 60 minutes, such as 20 minutes, 30 minutes, 40 minutes or 50 minutes) after, be placed on the upper pressurization of press (such as flatting mill or hydropress), the dwell time is preferably 1-3 minute.
In a preferred embodiment, the preparation method of tungsten-copper alloy of the present invention, in wherein said tungsten-copper alloy, W content is 5 ~ 50wt% (such as 50wt%, 40wt%, 30wt%, 20wt% or 10wt%).
In a preferred embodiment, the preparation method of tungsten-copper alloy of the present invention, wherein the pressed compact of step (1) is by isostatic pressing (such as cold isostatic compaction or hip moulding), and preferred isostatic pressed pressure is 100 ~ 300MPa (such as 150MPa, 200MPa, 250MPa or 280MPa).
In a preferred embodiment, the preparation method of tungsten-copper alloy of the present invention, purity >=99.95% of wherein said tungsten powder, is preferably the tungsten powder that average Fisher particle size is 3 ~ 8 microns;
Preferably, described copper powder is electrolytic copper powder, further purity >=99.95% of preferred copper powder, and more preferably the granularity of copper powder is-300 orders.
In a preferred embodiment, the preparation method of tungsten-copper alloy of the present invention, before the mixing of wherein tungsten powder and copper powder, also to carry out pre-treatment to tungsten powder, to break up the agglomerate of tungsten powder, air classification equipment (such as model is the air classification equipment of MQW10) is preferably adopted to carry out pre-treatment to tungsten powder.Carry out airflow crash stage treatment to tungsten powder to be conducive to putting forward heavy alloyed homogeneity and compactness.
In a preferred embodiment, the preparation method of tungsten-copper alloy of the present invention, wherein during step (3) hot pressing, mould pressed compact being put into monolateral 1 ~ 3mm (such as 2mm) gap pressurizes.
In a preferred embodiment, the preparation method of tungsten-copper alloy of the present invention, wherein the presintering of step (2) or the hot pressing of step (3) are at nonoxidizing atmosphere, such as, carry out in vacuum, nitrogen atmosphere, reducing atmosphere (such as hydrogen or cracked ammonium) or inert atmosphere (such as argon gas, helium), preferably in atmosphere of hydrogen, carry out presintering, in atmosphere of hydrogen, preferably carry out the heating steps in hot pressing.
In a preferred embodiment, the preparation method of tungsten-copper alloy of the present invention, the method also comprises the step of resintering knot, blank after the hot pressing obtain step (3) or step (4) carries out resintering knot, resintering knot is preferably at nonoxidizing atmosphere, such as vacuum, nitrogen atmosphere, reducing atmosphere (such as hydrogen or cracked ammonium) or inert atmosphere (such as argon gas, helium) in carry out, resintering junction temperature is preferably 1150 ~ 1180 DEG C, soaking time is preferably 15 ~ 30 minutes (such as 20 minutes, 22 minutes or 25 minutes), preferably by graphite cake lid pressure blank surface during resintering knot.Resintering knot is carried out to the blank after hot pressing, the defect occurred in hot pressing can be eliminated.In multiple sintering process, blank surface graphite cake covers, and can prevent hydrogen in stove from washing away and cause blank surface defect.
In a preferred embodiment, the preparation method of tungsten-copper alloy of the present invention, one or more during the method is further comprising the steps of:
(i) surface treatment, preferred surface treatment be selected from following process one or more: remove the tiny crack on surface, remove oxidation spot, rough place of polishing, the side bulge that produces when cutting hot pressing;
(ii) hot rolling, the temperature of hot rolling is preferably 400 ~ 600 DEG C (more preferably 450 DEG C, 480 DEG C, 500 DEG C or 550 DEG C), preferably roll lower amount is 0.5 ~ 1.5mm (such as 0.8mm, 1mm, 1.2mm) at every turn, selects suitable rolling number of times (preferred rolling 3 ~ 4 times) as required;
(iii) anneal, annealing temperature is preferably 800 ~ 1000 DEG C (being preferably 900 DEG C or 950 DEG C), and the soaking time of annealing is preferably 30 ~ 90 minutes (such as 40 ~ 60 minutes);
(iv) cold rolling, preferably roll lower amount is 0.01 ~ 0.5mm at every turn, selects suitable rolling number of times as required.
In the present invention, described surface-treated object removes the defect of blank surface, make any surface finish, solid colour, such as: polish off the tiny crack of blank surface, remove the oxidation spot of blank surface, the polishing rough place of blank surface, the side bulge that produces when cutting hot pressing.The side bulge produced when cutting hot pressing can prevent being out of shape inequality in the operation of rolling and cause edge cracks.
In a preferred embodiment, the preparation method of tungsten-copper alloy of the present invention, specifically comprises the following steps:
A () gets purity >=99.95%, average Fisher particle size is the tungsten powder of 3 microns, gets purity >=99.95%, and mean particle size is that-300 object electrolytic copper powders are stand-by;
B () carries out powder pre-treatment with airflow crash stage equipment to described tungsten powder, to break up the agglomerate of tungsten powder;
The c tungsten powder broken up that step (b) obtains by () mixes in powder mixer with electrolytic copper powder, obtains mixed powder;
D mixed powder isostatic pressing (such as cold isostatic compaction or hip moulding) that step (c) obtains by (), isostatic pressed pressure 100 ~ 300MPa, obtains pressed compact;
E pressed compact that step (d) obtains by () is at nonoxidizing atmosphere, such as, carry out presintering in vacuum, nitrogen atmosphere, reducing atmosphere (such as hydrogen or cracked ammonium) or inert atmosphere (such as argon gas, helium), pre-sintering temperature is 1000 ~ 1050 DEG C, sintering time is preferably 30 ~ 120 minutes, cool to room temperature with the furnace, obtain sintered blank;
F sintered blank that step (e) obtains by () is at nonoxidizing atmosphere, such as, be heated to 850 ~ 1070 DEG C in vacuum, nitrogen atmosphere, reducing atmosphere (such as hydrogen or cracked ammonium) or inert atmosphere (such as argon gas, helium), be incubated after 20 ~ 60 minutes, taking-up is placed directly in hot pressing on hydropress, pressure 2500 ~ 4000KN, pressurize 1 ~ 3 minute, the pressed compact of heating can be put into the mould in monolateral 2mm gap during hot pressing, split to reduce the limit produced in hot pressing;
(g) repeating step (f) 1 ~ 3 time (preferably 2 ~ 3 times);
Blank after h hot pressing that step (g) obtains by () is at nonoxidizing atmosphere, such as, carry out resintering knot in vacuum, nitrogen atmosphere, reducing atmosphere (such as hydrogen or cracked ammonium) or inert atmosphere (such as argon gas, helium), resintering junction temperature 1150 ~ 1180 DEG C, sintering time 15 ~ 30min, blank upper surface graphite cake is pushed down;
Blank after i resintering that step (h) obtains by () knot carries out surface treatment, preferred surface treatment be selected from following process one or more: remove the tiny crack on surface, remove oxidation spot, rough place of polishing, the side bulge that produces when cutting hot pressing;
The j blank after surface treatment that step (i) obtains by () is rolled, 500 DEG C of hot rollings, and roll lower amount is 0.5 ~ 1.5mm at every turn, Repeat-heating rolling 3 ~ 4 times;
Blank after k hot rolling that step (j) obtains by () carries out anneal, annealing temperature 800 DEG C;
L annealing blank that step (k) obtains by () carries out cold rolling, and roll lower amount is 0.01-0.5mm, repeatedly rolling at every turn, is rolled to desired thickness.
The present invention also provides a kind of tungsten-copper alloy, is prepared by the preparation method of tungsten-copper alloy of the present invention.The relative density of the tungsten-copper alloy prepared by the preparation method of tungsten-copper alloy of the present invention is greater than 98%.
Herein, "-" number before order number represents the screen cloth of " passing through " described order number.Such as, "-300 order " represents by 300 object screen clothes, for-300 object electrolytic copper powders, mean particle size represents that this electrolytic copper powder all can by 300 object screen clothes.
Beneficial effect of the present invention:
The invention provides a kind of method preparing tungsten-copper alloy, particularly a kind of W content is the preparation method of the low W content tungsten-copper alloy of 5wt% ~ 50wt%, this preparation method first carries out presintering to the briquet that tungsten powder and copper powder mixed powder are made, then the temperature lower than copper fusing point is adopted to carry out hot pressing to briquet, to ensure all even densification of its tissue.The tungsten-copper alloy homogeneous microstructure that the W content adopting preparation method of the present invention to prepare is lower, density are high, excellent property, yield rate are high.
Method of the present invention mixes rear pressed compact, directly according to product requirement preparation tungsten copper component content, without the need to oozing copper in down-stream directly by tungsten powder and copper powder.
In addition, the present invention, before the mixing of tungsten powder and copper powder, carries out pre-treatment to tungsten powder, to break up the agglomerate (preferably adopting air classification equipment to carry out pre-treatment to tungsten powder) of tungsten powder, thus obtains even-grained tungsten powder.After using this even-grained tungsten powder to mix with copper powder, the tungsten-copper alloy homogeneous microstructure, the compactness that obtain through sintering, hot pressing are high, and alloy is inner substantially containing the continuous accumulation area of W elements that size is greater than 100 μm.
Accompanying drawing explanation
Accompanying drawing described herein is used to provide a further understanding of the present invention, and form a application's part, schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 and Fig. 2 is respectively the metallograph of tungsten-copper alloy surface after polishing also corrosion prepared by embodiment 1, and in figure, particulate state region is tungsten, and back end region is copper.
Embodiment
Below by drawings and Examples, technical scheme of the present invention is described in further detail.
Embodiment 1: the preparation of the tungsten-copper alloy (W50Cu50) that W content is 50wt%, copper content is 50wt%
Preparation method comprises the steps:
(1) get purity >=99.95%, average Fisher particle size is the tungsten powder of 5 microns, gets purity >=99.95%, and mean particle size is that-300 object electrolytic copper powders are stand-by;
(2) with airflow crash stage equipment (unit type MQW10), powder pre-treatment is carried out to described tungsten powder, to break up the agglomerate of tungsten powder;
(3) tungsten powder broken up that step (2) obtains is mixed with electrolytic copper powder in powder mixer, obtain mixed powder;
(4) by the mixed powder cold isostatic compaction that step (3) obtains, isostatic pressed pressure 300MPa, obtains pressed compact, the thick 20mm of pressed compact;
(5) pressed compact that step (4) obtains is carried out presintering in logical hydrogen resistance furnace, pre-sintering temperature is 1050 DEG C, and sintering time is 120 minutes, is down to room temperature with stove, obtains sintered blank;
(6) sintered blank that step (5) obtains is heated in logical hydrogen resistance furnace, be heated to 1070 DEG C, be incubated after 30 minutes, take out and be placed directly in the upper hot pressing of hydropress (FS32-315), pressure 3150KN, pressurize 3 minutes.The pressed compact of heating can be put into the mould in monolateral 2mm gap during hot pressing, split to reduce the limit produced in hot pressing;
(7) pressed compact after hot pressing step (6) obtained, puts back in logical hydrogen resistance furnace, is heated to 1070 DEG C of insulations after 20 minutes, takes out and be again placed directly in hydropress hot pressing, pressure 3150KN, pressurize 3 minutes.The pressed compact of heating can be put into the mould in monolateral 2mm gap during hot pressing, make it densification, obtaining pressed compact thickness is 12mm;
(8) pressed compact after hot pressing step (7) obtained carries out resintering knot in logical hydrogen resistance furnace, to reduce the subsurface defect occurred in hot pressing, resintering junction temperature 1180 DEG C, sintering time 20min, pressed compact upper surface graphite cake is pushed down, and prevents hydrogen in stove from washing away and causes pressed compact surface imperfection;
(9) pressed compact after resintering knot step (8) obtained carries out surface treatment, the defect on pressed compact surface is ground off, such as polish off tiny crack, oxidation spot, rough place etc., make any surface finish, solid colour, and the side bulge produced during hot pressing is cut, to prevent, distortion in the operation of rolling is uneven forms edge cracks;
(10) be rolled by the pressed compact after surface treatment that step (9) obtains, 500 DEG C of hot rollings, every time to roll lower amount be 1mm, littlely rolls lower amount, multi-pass, and Repeat-heating rolling, is rolled to 5mm;
(11) pressed compact after hot rolling step (10) obtained carries out anneal, annealing temperature 900 DEG C, and soaking time is 60 minutes;
(12) undertaken cold rolling by the annealing pressed compact that step (11) obtains, every time rolls lower amount is 0.2-0.5mm, and light reduction multi-pass rolling, is rolled to 1.5mm, obtains the tungsten-copper alloy of the present embodiment.
Tungsten-copper alloy prepared by embodiment 1 is carried out to surface finish and corrodes, and in different positions sampling, respectively as depicted in figs. 1 and 2, wherein particulate state region is tungsten to metallograph, and back end region is copper.From Fig. 1 and Fig. 2, tungsten-copper alloy metallographic structure prepared by the present invention is even, and density is high, and product are on very good terms, substantially not containing the continuous accumulation area of W elements that size is greater than 100 μm.
Embodiment 2: the preparation of the tungsten-copper alloy (W30Cu70) that W content is 30wt%, copper content is 70wt%
Preparation method comprises the steps:
(1) get purity >=99.95%, average Fisher particle size is the tungsten powder of 8 microns, gets purity >=99.95%, and mean particle size is that-300 object electrolytic copper powders are stand-by;
(2) with airflow crash stage equipment (unit type MQW10), powder pre-treatment is carried out to described tungsten powder, to break up the agglomerate of tungsten powder;
(3) tungsten powder broken up that step (2) obtains is mixed with electrolytic copper powder in powder mixer, obtain mixed powder;
(4) by the mixed powder cold isostatic compaction that step (3) obtains, isostatic pressed pressure 200MPa, obtains pressed compact, the thick 20mm of pressed compact;
(5) pressed compact that step (4) obtains is carried out presintering in logical hydrogen resistance furnace, pre-sintering temperature is 1030 DEG C, and sintering time is 60 minutes, cools to room temperature with the furnace, obtains sintered blank;
(6) sintered blank that step (5) obtains is heated in logical hydrogen resistance furnace, be heated to 1000 DEG C, be incubated after 30 minutes, take out and be placed directly in the upper hot pressing of hydropress (FS32-315), pressure 3150KN, pressurize 2 minutes.The pressed compact of heating can be put into the mould in monolateral 2mm gap during hot pressing, split to reduce the limit produced in hot pressing;
(7) pressed compact after hot pressing step (6) obtained is put back in logical hydrogen resistance furnace, after 20 minutes 1000 DEG C of insulations, takes out and is again placed directly in hot pressing on hydropress, pressure 3150KN, pressurize 2 minutes.The pressed compact of heating can be put into the mould in monolateral 2mm gap during hot pressing, make it densification, obtaining pressed compact thickness is 12mm;
(8) pressed compact after hot pressing step (7) obtained carries out resintering knot in logical hydrogen resistance furnace, to reduce the subsurface defect occurred in hot pressing, resintering junction temperature 1160 DEG C, sintering time 20min, pressed compact upper surface graphite cake is pushed down, and prevents hydrogen in stove from washing away and causes pressed compact surface imperfection;
(9) pressed compact after resintering knot step (8) obtained carries out surface treatment, the defect on pressed compact surface is ground off, such as polish off tiny crack, oxidation spot, rough place etc., make any surface finish, solid colour, and the side bulge produced during hot pressing is cut, to prevent, distortion in the operation of rolling is uneven forms edge cracks;
(10) be rolled by the pressed compact after surface treatment that step (9) obtains, 500 DEG C of hot rollings, every time to roll lower amount be 1mm, littlely rolls lower amount, multi-pass, and Repeat-heating rolling, is rolled to 5mm;
(11) pressed compact after hot rolling step (10) obtained carries out anneal, annealing temperature 900 DEG C, soaking time 40 minutes;
(12) undertaken cold rolling by the annealing pressed compact that step (11) obtains, every time rolls lower amount is 0.05-0.5mm, and light reduction multi-pass rolling, is rolled to 0.5mm, obtains the tungsten-copper alloy of the present embodiment.
Embodiment 3: the preparation of the tungsten-copper alloy (W10Cu90) that W content is 10wt%, copper content is 90wt%
Preparation method comprises the steps:
(1) get purity >=99.95%, average Fisher particle size is the tungsten powder of 3 microns, gets purity >=99.95%, and mean particle size is that-300 object electrolytic copper powders are stand-by;
(2) with airflow crash stage equipment (unit type MQW10), powder pre-treatment is carried out to described tungsten powder, to break up the agglomerate of tungsten powder;
(3) tungsten powder broken up that step (2) obtains is mixed with electrolytic copper powder in powder mixer, obtain mixed powder;
(4) by the mixed powder cold isostatic compaction that step (3) obtains, isostatic pressed pressure 100MPa, obtains pressed compact, the thick 20mm of pressed compact;
(5) pressed compact that step (4) obtains is carried out presintering in logical hydrogen resistance furnace, pre-sintering temperature is 1000 DEG C, and sintering time is 30 minutes, cools to room temperature with the furnace, obtains sintered blank;
(6) sintered blank that step (5) obtains is heated in logical hydrogen resistance furnace, be heated to 850 DEG C, be incubated after 30 minutes, take out and be placed directly in the upper hot pressing of hydropress (FS32-315), pressure 3150KN, pressurize 3 minutes.The pressed compact of heating can be put into the mould in monolateral 2mm gap during hot pressing, split to reduce the limit produced in hot pressing;
(7) pressed compact after hot pressing step (6) obtained, puts back in logical hydrogen resistance furnace, 850 DEG C of insulations 20 minutes, then takes out and is again placed directly in hydropress hot pressing, pressure 3150KN, pressurize 2 minutes.During hot pressing, the pressed compact of heating is put into the mould in monolateral 2mm gap, make it densification, obtaining pressed compact thickness is 12mm;
(8) pressed compact after hot pressing step (7) obtained carries out resintering knot in logical hydrogen resistance furnace, to reduce the subsurface defect occurred in hot pressing, resintering junction temperature 1150 DEG C, sintering time 20min, pressed compact upper surface graphite cake is pushed down, and prevents hydrogen in stove from washing away and causes pressed compact surface imperfection;
(9) pressed compact after resintering knot step (8) obtained carries out surface treatment, the defect on pressed compact surface is ground off, such as polish off tiny crack, oxidation spot, rough place etc., make any surface finish, solid colour, and the side bulge produced during hot pressing is cut, to prevent, distortion in the operation of rolling is uneven forms edge cracks;
(10) be rolled by the pressed compact after surface treatment that step (9) obtains, 500 DEG C of hot rollings, every time to roll lower amount be 1mm, littlely rolls lower amount, multi-pass, and Repeat-heating rolling, is rolled to 5mm;
(11) pressed compact after hot rolling step (10) obtained carries out anneal, annealing temperature 800 DEG C, soaking time 30 minutes;
(12) undertaken cold rolling by the annealing pressed compact that step (11) obtains, every time rolls lower amount is 0.01-0.5mm, and light reduction multi-pass rolling, is rolled to 0.1mm, obtains the tungsten-copper alloy of the present embodiment.
Measure the density of tungsten-copper alloy prepared by embodiment 1 ~ 3 by standard GB/T/T 1423-1996, then calculate relative density (ratio of actual density and theoretical density), concrete numerical value is as shown in the table.
Finally should be noted that: above embodiment is only in order to illustrate that technical scheme of the present invention is not intended to limit; Although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the field are to be understood that: still can modify to the specific embodiment of the present invention or carry out equivalent replacement to portion of techniques feature; And not departing from the spirit of technical solution of the present invention, it all should be encompassed in the middle of the technical scheme scope of request of the present invention protection.
Claims (12)
1. a preparation method for tungsten-copper alloy, it comprises the following steps:
(1) pressed compact: tungsten powder and copper powder are mixed rear pressed compact;
(2) presintering: carry out presintering to the pressed compact that step (1) obtains, pre-sintering temperature is preferably 1000 ~ 1050 DEG C, and sintering time is preferably 30 ~ 120 minutes;
(3) hot pressing: hot pressing is carried out to the sintered blank that step (2) obtains, the temperature of hot pressing is preferably 850 ~ 1070 DEG C (such as 1000 ~ 1070 DEG C), pressure is preferably 2500 ~ 4000KN (more preferably 2800 ~ 3800KN or 3000 ~ 3500KN or 3000 ~ 3200KN), and the dwell time is preferably 1-3 minute (such as 2 minutes);
(4) optionally, the heat-press step 2 ~ 3 times of repeating step (3).
2. the preparation method of claim 1, wherein the hot pressing of step (3) first the sintered blank that step (2) obtains is heated to 850 ~ 1070 DEG C (such as 1000 ~ 1070 DEG C), be incubated and (be preferably incubated 15 ~ 40 minutes in 15 ~ 60 minutes, such as 20 minutes, 30 minutes, 40 minutes or 50 minutes) after, be placed on the upper pressurization of press (such as flatting mill or hydropress), the dwell time is preferably 1-3 minute.
3. the preparation method of claim 1 or 2, in wherein said tungsten-copper alloy, W content is 5 ~ 50wt% (such as 50wt%, 40wt%, 30wt%, 20wt% or 10wt%).
4. the preparation method of any one of claim 1-3, wherein the pressed compact of step (1) is by isostatic pressing (such as cold isostatic compaction or hip moulding), and preferred isostatic pressed pressure is 100 ~ 300MPa (such as 150MPa, 200MPa, 250MPa or 280MPa).
5. the preparation method of any one of claim 1-4, purity >=99.95% of wherein said tungsten powder, is preferably the tungsten powder that average Fisher particle size is 3 ~ 8 microns;
Preferably, described copper powder is electrolytic copper powder, further purity >=99.95% of preferred copper powder, and more preferably the granularity of copper powder is-300 orders.
6. the preparation method of any one of claim 1-5, before the mixing of wherein tungsten powder and copper powder, also will carry out pre-treatment to tungsten powder, to break up the agglomerate of tungsten powder, preferably adopts air classification equipment to carry out pre-treatment to tungsten powder.
7. the preparation method of any one of claim 1-6, wherein during step (3) hot pressing, mould pressed compact being put into monolateral 1 ~ 3mm (such as 2mm) gap pressurizes.
8. the preparation method of any one of claim 1-7, wherein the presintering of step (2) or the hot pressing of step (3) are at nonoxidizing atmosphere, such as, carry out in vacuum, nitrogen atmosphere, reducing atmosphere (such as hydrogen or cracked ammonium) or inert atmosphere (such as argon gas, helium), preferably in atmosphere of hydrogen, carry out presintering, in atmosphere of hydrogen, preferably carry out the heating steps in hot pressing.
9. the preparation method of any one of claim 1-8, the method also comprises the step of resintering knot, blank after the hot pressing obtain step (3) or step (4) carries out resintering knot, resintering knot is preferably at nonoxidizing atmosphere, such as, carry out in vacuum, nitrogen atmosphere, reducing atmosphere (such as hydrogen or cracked ammonium) or inert atmosphere (such as argon gas, helium), resintering junction temperature is preferably 1150 ~ 1180 DEG C, soaking time is preferably 15 ~ 30 minutes (such as 20 minutes, 22 minutes or 25 minutes), preferably by graphite cake lid pressure blank surface during resintering knot.
10. the preparation method of any one of claim 1-9, one or more during the method is further comprising the steps of:
(i) surface treatment, preferred surface treatment be selected from following process one or more: remove the tiny crack on surface, remove oxidation spot, polish rough place or cut hot pressing time the side bulge that produces;
(ii) hot rolling, the temperature of hot rolling is preferably 400 ~ 600 DEG C (more preferably 450 DEG C, 480 DEG C, 500 DEG C or 550 DEG C), preferably roll lower amount is 0.5 ~ 1.5mm (such as 0.8mm, 1mm, 1.2mm) at every turn, selects suitable rolling number of times (preferred rolling 3 ~ 4 times) as required;
(iii) anneal, annealing temperature is preferably 800 ~ 1000 DEG C (being preferably 900 DEG C or 950 DEG C), and soaking time is preferably 30 ~ 90 minutes (such as 40 minutes, 50 minutes or 60 minutes);
(iv) cold rolling, preferably roll lower amount is 0.01 ~ 0.5mm at every turn, selects suitable rolling number of times as required.
The preparation method of 11. any one of claim 1-10, the method comprises the following steps:
A () gets purity >=99.95%, average Fisher particle size is the tungsten powder of 3 microns, gets purity >=99.95%, and mean particle size is that-300 object electrolytic copper powders are stand-by;
B () carries out powder pre-treatment with airflow crash stage equipment to described tungsten powder, to break up the agglomerate of tungsten powder;
The c tungsten powder broken up that step (b) obtains by () mixes in powder mixer with electrolytic copper powder, obtains mixed powder;
D mixed powder isostatic pressing (such as cold isostatic compaction or hip moulding) that step (c) obtains by (), isostatic pressed pressure 100 ~ 300MPa, obtains pressed compact;
E pressed compact that step (d) obtains by () is at nonoxidizing atmosphere, such as, carry out presintering in vacuum, nitrogen atmosphere, reducing atmosphere (such as hydrogen or cracked ammonium) or inert atmosphere (such as argon gas, helium), pre-sintering temperature is 1000 ~ 1050 DEG C, sintering time is preferably 30 ~ 120 minutes, cool to room temperature with the furnace, obtain sintered blank;
F sintered blank that step (e) obtains by () is heated to 850 ~ 1070 DEG C in atmosphere of hydrogen, be incubated after 15 ~ 60 minutes, taking-up is placed directly in hot pressing on hydropress, pressure 2500 ~ 4000KN, pressurize 1 ~ 3 minute, can put into the mould in monolateral 2mm gap by the pressed compact of heating during hot pressing;
(g) repeating step (f) 1 ~ 3 time (preferably 2 ~ 3 times);
Blank after h hot pressing that step (g) obtains by () is at nonoxidizing atmosphere, such as, carry out resintering knot in vacuum, nitrogen atmosphere, reducing atmosphere (such as hydrogen or cracked ammonium) or inert atmosphere (such as argon gas, helium), resintering junction temperature 1150 ~ 1180 DEG C, sintering time 15 ~ 30min, blank upper surface graphite cake is pushed down;
Blank after i resintering that step (h) obtains by () knot carries out surface treatment, described surface treatment be selected from following process one or more: remove the tiny crack on surface, remove oxidation spot, polish rough place or cut hot pressing time the side bulge that produces;
The j blank after surface treatment that step (i) obtains by () is rolled, 500 DEG C of hot rollings, and roll lower amount is 0.5 ~ 1.5mm at every turn, Repeat-heating rolling 3 ~ 4 times;
Blank after k hot rolling that step (j) obtains by () carries out anneal, annealing temperature 800 DEG C;
L annealing blank that step (k) obtains by () carries out cold rolling, and roll lower amount is 0.01-0.5mm, repeatedly rolling at every turn, is rolled to desired thickness.
The tungsten-copper alloy that the preparation method of 12. any one of claim 1-11 prepares,
Preferably, the relative density of described tungsten-copper alloy is greater than 98%.
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