CN105478753A - Tungsten carbide and tungsten composite powder and preparation method thereof - Google Patents

Tungsten carbide and tungsten composite powder and preparation method thereof Download PDF

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Publication number
CN105478753A
CN105478753A CN201510937763.3A CN201510937763A CN105478753A CN 105478753 A CN105478753 A CN 105478753A CN 201510937763 A CN201510937763 A CN 201510937763A CN 105478753 A CN105478753 A CN 105478753A
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China
Prior art keywords
tungsten
carbide
tungsten carbide
composite powder
preparation
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CN201510937763.3A
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CN105478753B (en
Inventor
高峰
沈婕
胡宇
白智辉
李�杰
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Bgrimm Advanced Materials Science & Technology Co ltd
Beijing General Research Institute of Mining and Metallurgy
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Bgrimm Advanced Materials Science & Technology Co ltd
Beijing General Research Institute of Mining and Metallurgy
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/17Metallic particles coated with metal
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/16Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • B22F9/22Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors

Abstract

The invention discloses tungsten carbide and tungsten composite powder and a preparation method thereof, and the tungsten carbide powder is firstly placed in an inert gas environment; then introducing oxygen with the molar ratio of 1-5%, heating to 300-800 ℃, and preserving heat for 5-30 minutes to decarburize the surface of the tungsten carbide to form a mixture of tungsten and tungsten oxide; then introducing hydrogen as a reducing agent, wherein the introduction amount is 0.5-4 m3Heating to 600-800 ℃ for 1-2 hours; and then heating to 1100-1500 ℃, and preserving the heat for 10-30 minutes to obtain the tungsten carbide composite powder with the tungsten on the surface. The method can form a continuous and stable metal tungsten layer on the surface of the tungsten carbide, prevent the generation of eta phase in the spraying or spray welding process and effectively improve the toughness of the coating.

Description

Composite powder of a kind of tungsten carbide and tungsten and preparation method thereof
Technical field
The present invention relates to heat spray coating layer material technical field, particularly relate to composite powder of a kind of tungsten carbide and tungsten and preparation method thereof.
Background technology
At present, tungsten carbide or ditungsten carbide are conventional metal ceramic wear-resisting materials, in field of thermal spray, under the metal-cermic spraying material being hard, wear-resistant phase with tungsten carbide or ditungsten carbide is widely used in various wear-resisting working condition.
But in thermal spraying or spray process, because spraying temperature is higher, tungsten carbide easily decomposes generation ditungsten carbide, and then generates η phase (Co due to the existence of surrounding metal Binder Phase 3w 3c, Co 6w 6c etc.), the hardness that η phase not only reduces coating also seriously reduces the toughness of coating, and the generation of η phase is because carbon diffusion in a metal causes, and how to suppress the diffusion of carbon in spraying or surfacing to become the key improving coating toughness.
Summary of the invention
The object of this invention is to provide composite powder of a kind of tungsten carbide and tungsten and preparation method thereof, utilize the method can form the metal tungsten layer of one deck continous-stable in tungsten carbide surface, in spraying or spray process, prevent the generation of η phase, effectively improve the toughness of coating.
A composite powder for tungsten carbide and tungsten, described composite powder take tungsten carbide as core, and the surface that tungsten is distributed in described tungsten carbide forms complete clad;
And the thickness of tungsten layer is 1 ~ 5% of described tungsten carbide core granule diameter.
The diameter range of described tungsten carbide core granule is: 1 ~ 200 micron;
And the thickness range of tungsten layer is 0.05 ~ 5 micron.
Present invention also offers the preparation method of the composite powder of a kind of tungsten carbide and tungsten, described method comprises:
By tungsten-carbide powder as under inert gas environment;
Then pass into the oxygen that mol ratio is 1 ~ 5%, and be heated to 300 ~ 800 DEG C, be incubated 5 ~ 30 minutes, make tungsten carbide surface decarburization form the mixture of tungsten and tungsten oxide;
Pass into hydrogen again as reducing agent, intake is 0.5 ~ 4m 3/ h, and be heated to 600 ~ 800 DEG C, be incubated 1 ~ 2 hour;
And then be heated to 1100 ~ 1500 DEG C, be incubated 10 ~ 30 minutes, obtain the wolfram carbine composite powder that surface is tungsten.
Described inert gas is: not with gas and the combination of gases of tungsten carbide generation chemical reaction;
Specifically comprise: nitrogen or argon gas.
Described tungsten carbide is replaced with ditungsten carbide.
As seen from the above technical solution provided by the invention, utilize the method can form the metal tungsten layer of one deck continous-stable in tungsten carbide surface, in spraying or spray process, prevent the generation of η phase, effectively improve the toughness of coating.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme of the embodiment of the present invention, below the accompanying drawing used required in describing embodiment is briefly described, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 provides by the embodiment of the present invention preparation method's schematic flow sheet of the composite powder of tungsten carbide and tungsten.
Detailed description of the invention
Below in conjunction with the accompanying drawing in the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on embodiments of the invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to protection scope of the present invention.
Preparation method described in the embodiment of the present invention passes through at tungsten carbide (or ditungsten carbide) Surface Creation one deck tungsten layer, form the composite powder of tungsten carbide/tungsten, and as spraying, surfacing raw material, to solve the problem that tungsten carbide (or ditungsten carbide) easily generates η phase in thermal spraying, spray process.
The composite powder of the tungsten carbide that the embodiment of the present invention provides and tungsten take tungsten carbide as core, and the surface that tungsten is distributed in described tungsten carbide forms complete clad;
And the thickness of tungsten layer is 1 ~ 5% of described tungsten carbide core granule diameter.
In specific implementation, the diameter range of this tungsten carbide core granule is: 1 ~ 200 micron; And the thickness range of tungsten layer is 0.05 ~ 5 micron.
Be illustrated in figure 1 the embodiment of the present invention preparation method's schematic flow sheet of the composite powder of tungsten carbide and tungsten is provided, described method comprises:
Step 11: by tungsten-carbide powder as under inert gas environment;
Here, described inert gas is: not with gas and the combination of gases of tungsten carbide generation chemical reaction;
Specifically can comprise: nitrogen or argon gas.
Step 12: then pass into the oxygen that mol ratio is 1 ~ 5%, and be heated to 300 ~ 800 DEG C, is incubated 5 ~ 30 minutes, makes tungsten carbide surface decarburization form the mixture of tungsten and tungsten oxide;
Step 13: pass into hydrogen again as reducing agent, intake is 0.5 ~ 4m 3/ h, and be heated to 600 ~ 800 DEG C, be incubated 1 ~ 2 hour;
In this step, this hydrogen also can replace with other reducibility gas, as cracked ammonium, carbon monoxide etc.
Step 14: and then be heated to 1100 ~ 1500 DEG C, be incubated 10 ~ 30 minutes, obtain the wolfram carbine composite powder that surface is tungsten.
In specific implementation, above-mentioned tungsten carbide also can replace with ditungsten carbide.
Be described in detail with the technical process of concrete example to above-mentioned preparation method below:
Embodiment 1, first by grain graininess d 50the tungsten carbide of=10 microns is placed in nitrogen, oxygen mixed gas, and wherein oxygen accounts for 1.5% of gas gross, is heated to 350 DEG C, is incubated 10 minutes;
Then hydrogen is passed into, hydrogen flowing quantity: 0.5m 3/ h, is heated to 630 DEG C, is incubated 1 hour;
Be increased to 1100 DEG C again, be incubated 10 minutes, obtain the Surface coating tungsten-carbide powder of tungsten layer, tungsten layer thickness is about 0.3 micron.
Embodiment 2, first by grain graininess d 50tungsten carbide/ditungsten carbide the eutectic powder of=60 microns is placed in nitrogen, oxygen mixed gas, and wherein oxygen accounts for 5% of gas gross, is heated to 800 DEG C, is incubated 15 minutes;
Then hydrogen is passed into, hydrogen flowing quantity: 2m 3/ h, is heated to 780 DEG C, is incubated 1.5 hours;
Be increased to 1300 DEG C again, be incubated 30 minutes, obtain the Surface coating tungsten-carbide powder of tungsten layer, tungsten layer thickness is about 1.5 microns.
Embodiment 3, first by grain graininess d 50the tungsten-carbide powder of=2 microns is placed in nitrogen, oxygen mixed gas, and wherein oxygen accounts for 2% of gas gross, is heated to 300 DEG C, is incubated 10 minutes;
Then hydrogen is passed into, hydrogen flowing quantity: 4m 3/ h, is heated to 720 DEG C, is incubated 1 hour;
Be increased to 1150 DEG C again, be incubated 30 minutes, obtain the Surface coating tungsten-carbide powder of tungsten layer, tungsten layer thickness is about 0.1 micron.
In sum, the method utilizing the embodiment of the present invention to provide can form the metal tungsten layer of one deck continous-stable in tungsten carbide surface, prevents the generation of η phase in spraying or spray process, effectively improves the toughness of coating.
The above; be only the present invention's preferably detailed description of the invention, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.

Claims (5)

1. a composite powder for tungsten carbide and tungsten, is characterized in that, described composite powder take tungsten carbide as core, and the surface that tungsten is distributed in described tungsten carbide forms complete clad;
And the thickness of tungsten layer is 1 ~ 5% of described tungsten carbide core granule diameter.
2. the composite powder of tungsten carbide and tungsten as claimed in claim 1, is characterized in that,
The diameter range of described tungsten carbide core granule is: 1 ~ 200 micron;
And the thickness range of tungsten layer is 0.05 ~ 5 micron.
3. a preparation method for the composite powder of tungsten carbide and tungsten, is characterized in that, described method comprises:
By tungsten-carbide powder as under inert gas environment;
Then pass into the oxygen that mol ratio is 1 ~ 5%, and be heated to 300 ~ 800 DEG C, be incubated 5 ~ 30 minutes, make tungsten carbide surface decarburization form the mixture of tungsten and tungsten oxide;
Pass into hydrogen again as reducing agent, intake is 0.5 ~ 4m 3/ h, and be heated to 600 ~ 800 DEG C, be incubated 1 ~ 2 hour;
And then be heated to 1100 ~ 1500 DEG C, be incubated 10 ~ 30 minutes, obtain the wolfram carbine composite powder that surface is tungsten.
4. the preparation method of the composite powder of tungsten carbide and tungsten according to claim 3, is characterized in that,
Described inert gas is: not with gas and the combination of gases of tungsten carbide generation chemical reaction;
Specifically comprise: nitrogen or argon gas.
5. the preparation method of the composite powder of tungsten carbide and tungsten according to claim 3, is characterized in that,
Described tungsten carbide is replaced with ditungsten carbide.
CN201510937763.3A 2015-12-15 2015-12-15 Tungsten carbide and tungsten composite powder and preparation method thereof Active CN105478753B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106747449A (en) * 2016-12-26 2017-05-31 哈尔滨职业技术学院 New tungsten carbide composite and preparation method thereof
CN107716917A (en) * 2017-09-20 2018-02-23 西安理工大学 A kind of method that gas carburization method reaction in-situ prepares W/WC composite powders
CN109321803A (en) * 2018-11-30 2019-02-12 苏州艾默特材料技术有限公司 A kind of heating element with porous ceramics coating

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62192501A (en) * 1986-02-18 1987-08-24 Mitsubishi Metal Corp Co-w coated wc powder
US5912399A (en) * 1995-11-15 1999-06-15 Materials Modification Inc. Chemical synthesis of refractory metal based composite powders
CN1608983A (en) * 2004-09-16 2005-04-27 北京科技大学 Prepn process of nano level tungsten powder and WC powder

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62192501A (en) * 1986-02-18 1987-08-24 Mitsubishi Metal Corp Co-w coated wc powder
US5912399A (en) * 1995-11-15 1999-06-15 Materials Modification Inc. Chemical synthesis of refractory metal based composite powders
CN1608983A (en) * 2004-09-16 2005-04-27 北京科技大学 Prepn process of nano level tungsten powder and WC powder

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李玲玲: "碳化钨涂覆金刚石的新方法", 《中国钨业》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106747449A (en) * 2016-12-26 2017-05-31 哈尔滨职业技术学院 New tungsten carbide composite and preparation method thereof
CN107716917A (en) * 2017-09-20 2018-02-23 西安理工大学 A kind of method that gas carburization method reaction in-situ prepares W/WC composite powders
CN109321803A (en) * 2018-11-30 2019-02-12 苏州艾默特材料技术有限公司 A kind of heating element with porous ceramics coating

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