CN102876907B - Preparation method of tungsten carbide-cobalt or tungsten carbide-cobalt-chromium thermal spraying powder - Google Patents
Preparation method of tungsten carbide-cobalt or tungsten carbide-cobalt-chromium thermal spraying powder Download PDFInfo
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- CN102876907B CN102876907B CN201210370225.7A CN201210370225A CN102876907B CN 102876907 B CN102876907 B CN 102876907B CN 201210370225 A CN201210370225 A CN 201210370225A CN 102876907 B CN102876907 B CN 102876907B
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Abstract
The invention relates to a preparation method of tungsten carbide-cobalt or tungsten carbide-cobalt-chromium thermal spraying powder. The preparation method includes: proportionally mixing tungsten carbide powder with cobalt powder or tungsten carbide powder, cobalt powder and chromium powder, compounding slurry, performing spray granulation, screening and degreasing granulated powder prior to rapidly sintering the granulated powder in a vertical high-temperature sintering furnace, enabling the powder to continuously and uniformly pass through a heating area and a cooling area in a free-falling motion mode, completing sintering in the heating area for 0.1-5s at the sintering temperature of 1000-1700 DEG C in the nitrogen protective atmosphere, and performing classified screening for the sintered powder as required finally. The preparation method solves the problems of long production cycle, low production efficiency, high energy consumption and the like when tungsten carbide based composite spherical thermal spraying powder is prepared by a traditional method, is simple in technological process, capable of achieving continuous production, energy-saving and environment-friendly and can be widely applied to the fields of aerospace, machine manufacturing, petrochemical engineering and the like, and the obtained powder is uniform in component, high in sphericity degree and good in fluidity.
Description
Technical field
The invention discloses the preparation method of a kind of tungsten-cobalt carbide or tungsten-cobalt carbide-chromium hot spray powder; Relate to thermal spraying material technical field, mmaterial technical field and Wimet technical field.
Background technology
Wolfram varbide belongs to ceramic phase, there is the advantages such as fusing point is high, hardness is high, electrical and thermal conductivity is poor, stable chemical performance, it is the ideal material of preparing wear-and corrosion-resistant coating, but high-melting-point and high rigidity due to wolfram varbide, the tungsten carbide particle of spraying and the poor adhesive force of body material, and be easily oxidized during the temperature that raises in air, therefore pure WC powder is seldom used alone as hot spraying powder powder material, conventionally need to add the metal or alloy such as Co, Ni, Ni-Cr to make sintered type powder or cladded type powder for thermospray as Binder Phase.The tungsten-cobalt carbide of widespread use and tungsten-cobalt carbide-chromium series of heat dusty spray, because its prepared coating has high hardness, superior wear and corrosion behavior and good toughness, be widely used in the fields such as aerospace, automobile, metallurgy, electric power, papermaking, to improve the wear resisting property of component surface and to repair abrading section.
Tungsten-cobalt carbide and common the used preparation method of tungsten-cobalt carbide-chromium series of heat dusty spray comprise fusing method ﹑ sintering crushing method ﹑ plasma body nodularization method and traditional reunion sintering process etc., but these preparation technologies are more complicated, have that the production cycle is long, production efficiency is low and consume energy the difficult problem such as large.In addition, the dusty spray granule-morphology that fusing Fa ﹑ sintering crushing method is produced is irregular shape, sphericity is poor, poor mobile performance, powder deposition rate is lower, coating and substrate combinating strength are poor, and use procedure floating coat is prone to even peeling phenomenon and losing efficacy of crackle, brings dust and noise pollution in production process to surrounding environment simultaneously; For plasma body nodularization method, because whole nodularization process is carried out in high temperature and protective atmosphere environment, high to equipment requirements, production cost is high.For tradition reunion sintering process, although hot spray powder that also can excellent, powder soaking time in high-temperature sintering process is longer, power consumption is large, and the powder bonded after sintering is block, need carry out fragmentation, classification, extend manufacture cycle, improve production cost.
Summary of the invention
The object of the invention is to exist when adopting traditional method to prepare tungsten-cobalt carbide or tungsten-cobalt carbide-chromium hot spray powder that the production cycle is long, production efficiency is low and consume energy the difficult problem such as large, the preparation method of a kind of tungsten-cobalt carbide or tungsten-cobalt carbide-chromium hot spray powder is provided, the method technical process is simple, production efficiency is high, and made powder composition is even, sphericity is high and good fluidity.
The present invention relates to the preparation method of a kind of tungsten-cobalt carbide or tungsten-cobalt carbide-chromium hot spray powder, by the aimed quality proportioning of the tungsten-cobalt carbide of design or each component of tungsten-cobalt carbide-chromium powder end, get respectively tungsten carbide powder and cobalt powder or tungsten carbide powder, cobalt powder and chromium powder are through being mixed to get mixed powder, after wet-milling to mixed powder mean particle size is 0.1 micron ~ 10 microns, add the polyoxyethylene glycol that accounts for mixed powder massfraction 1% ~ 5% to make adhesive for granulating and dispersion agent, stir 1 ~ 3h, guarantee that polyoxyethylene glycol is uniformly dispersed, mist projection granulating, obtain prilling powder, prilling powder is crossed double-deck screen shale shaker, oversize powder and undersize powder all return to wet-milling again, granulation, get granularity and be powder in the sieve of 15～75 microns carries out after skimming treatment in tube type resistance furnace, high temperature Fast Sintering under protective atmosphere, air cooling, obtain sintered powder, described Fast Sintering temperature: 1000 ~ 1700 ℃, sintering time: 0.1 ~ 5s.
The present invention relates to the preparation method of a kind of tungsten-cobalt carbide or tungsten-cobalt carbide-chromium hot spray powder, each constituent mass per-cent of described tungsten-cobalt carbide powder is: tungsten carbide powder 1%-99%, cobalt powder 1%-99%; Described each constituent mass per-cent of tungsten-cobalt carbide-chromium hot spray powder is: tungsten carbide powder 1%-99%, cobalt powder 1%-99%, chromium powder 1%-20%.
The present invention relates to the preparation method of a kind of tungsten-cobalt carbide or tungsten-cobalt carbide-chromium hot spray powder, to adding in described mixed powder after deionized water or dehydrated alcohol are mixed with slip, carry out wet-milling; In slip, solid content is 50% ~ 80%.
The present invention relates to the preparation method of a kind of tungsten-cobalt carbide or tungsten-cobalt carbide-chromium hot spray powder, described mist projection granulating carries out in spray-drying tower, the inlet temperature of spray-drying tower is controlled at 200 ~ 300 ℃, temperature out is controlled at 100 ~ 150 ℃, and spray-drying tower tower internal gas pressure is controlled at 0 ~ – 1KPa.
The present invention relates to the preparation method of a kind of tungsten-cobalt carbide or tungsten-cobalt carbide-chromium hot spray powder, 600 ℃ ~ 1000 ℃ of described skimming treatment temperature, time 2h ~ 8h.
The preparation method who the present invention relates to a kind of tungsten-cobalt carbide or tungsten-cobalt carbide-chromium hot spray powder, described high temperature Fast Sintering is carried out in vertical high-temperature sintering oven, and the type of heating of described vertical high-temperature sintering oven is Frequency Induction Heating or resistive heating.
The present invention relates to the preparation method of a kind of tungsten-cobalt carbide or tungsten-cobalt carbide-chromium hot spray powder, powder after degreasing with the mode of motion continuous uniform of freely falling body complete liquid phase sintering in high-temperature zone by vertical high-temperature sintering oven and ，Qie Yu high-temperature zone, cooling zone.
The preparation method who the present invention relates to a kind of tungsten-cobalt carbide or tungsten-cobalt carbide-chromium hot spray powder, described protective atmosphere is nitrogen atmosphere.
The present invention relates to the preparation method of a kind of tungsten-cobalt carbide or tungsten-cobalt carbide-chromium hot spray powder, sintered powder adopts double-deck spin vibration sieve to sieve or air draught sorting, obtain tungsten-cobalt carbide or tungsten-cobalt carbide-chromium hot spray powder, its be shaped as spherical, class is spherical or aspherical particle.
Mechanism of the present invention and advantage sketch under: adopt the method for mist projection granulating that raw material powder is reunited for spherical or class spherical powder, after reunion powder degreasing in vertical high-temperature sintering oven with the mode of motion continuous uniform of freely falling body by completing liquid phase sintering in high-temperature zone and ，Qie Yu high-temperature zone, cooling zone.Because reunion powder is to pass through fast high-temperature zone by self gravitation with the movement of falling object, its sintering time extremely short (0.1 ~ 5s), each is to being heated evenly, can make fast the dusty spray of stable performance, and reunion powder is difficult for being bonded to piece in high temperature Fast Sintering process, after the classified screening of gained sintered powder, can be directly used in spraying, reduced production process, further energy-saving and emission-reduction, save production cost, and in sintering process, bringing dust and noise pollution hardly to surrounding environment, is a kind of novel green production process.
It is simple that the present invention has technical process, can produce continuously, energy-conserving and environment-protective, can be good at solving prior art exists that the production cycle is long, production efficiency is low and consumes energy the difficult problem such as large, and preparation tungsten-cobalt carbide and tungsten-cobalt carbide-chromium hot spray powder composition is even, sphericity is high and good fluidity, can meet thermospray requirement completely, be applicable to the high performance hard alloy coating of preparation, can be widely used in aerospace, machinofacture and field of petrochemical industry.
Accompanying drawing explanation:
Accompanying drawing 1 is 500 times of stereoscan photographs of tungsten-cobalt carbide hot spray powder of embodiment 1 preparation;
Accompanying drawing 2 is 500 times of stereoscan photographs of tungsten-cobalt carbide-chromium hot spray powder of embodiment 2 preparations.
From accompanying drawing 1,2, can see: the powder shape preparing be spherical, class is spherical and non-spherical, adopts counting statistics method to show that the percentage composition of non-spherical powder is less than 5%.
Embodiment:
Embodiment 1:WC-17Co hot spray powder
First the cobalt powder of the tungsten carbide powder of 83wt% and 17wt% is added in ball mill, add deionized water simultaneously, controlling solid content is 70%, wet-milling, wet-milling time 12h; After wet-milling, mixed powder mean particle size is 0.1 micron ~ 10 microns, adds the polyoxyethylene glycol that accounts for mixed powder massfraction 3%, stirs after 2h, carries out granulation in spray-drying tower, obtains prilling powder; Inlet temperature is controlled at 260 ℃, and temperature out is controlled at 110 ℃; Prilling powder is crossed to 200 orders and 900 order double-deck screen shale shakers, obtain the interior powder of sieve of 15～75 microns of granularities, 200 order oversize powders and 900 order undersize powders all return to wet-milling; Powder in gained sieve is carried out to skimming treatment in tube furnace, 800 ℃ of temperature, time 4h, fully removes the polyoxyethylene glycol in prilling powder; By the Fast Sintering in vertical high-temperature sintering oven of the powder after skimming treatment, powder with the mode of motion continuous uniform of freely falling body by completing sintering in heating zone and ，Qie Yu heating zone, cooling zone, obtain sintered powder; Feeding manner is vibration screen charging, and protective atmosphere is nitrogen, 1300 ℃ of sintering temperatures, and sintering time 0.4s, the type of cooling is air cooling; Adopt air draught to sub-elect the powder of size-grade distribution between 15 microns ~ 45 microns sintered powder, be WC-17Co hot spray powder.
Finally obtain particle shape comprise spherical, class is spherical and aspheric WC-17Co hot spray powder, this powder is pressed GB1482-1984 and is detected: mobility < 25s/50g, loose density < 4.0g/cm
3.
Embodiment 2:WC-10Co-4Cr hot spray powder
First the chromium powder of the cobalt powder of the tungsten carbide powder of 86wt% and 10wt% and 4wt% is added in ball mill, add deionized water simultaneously, controlling solid content is 75%, wet-milling, wet-milling time 12h; After wet-milling, mixed powder mean particle size is 0.1 micron ~ 10 microns, adds the polyoxyethylene glycol that accounts for mixed powder massfraction 2%, stirs after 2h, carries out granulation in spray-drying tower, obtains prilling powder; Inlet temperature is controlled at 260 ℃, and temperature out is controlled at 110 ℃; Prilling powder is crossed to 200 orders and 900 order double-deck screen shale shakers, obtain the interior powder of sieve of 15～75 microns of granularities, 200 order oversize powders and 900 order undersize powders all return to wet-milling; Powder in gained sieve is carried out to skimming treatment in tube furnace, 800 ℃ of temperature, time 4h, fully removes the polyoxyethylene glycol in prilling powder; By the Fast Sintering in vertical high-temperature sintering oven of the powder after skimming treatment, powder with the mode of motion continuous uniform of freely falling body by completing sintering in heating zone and ，Qie Yu heating zone, cooling zone, obtain sintered powder; Feeding manner is vibration screen charging, and protective atmosphere is nitrogen, 1250 ℃ of sintering temperatures, and sintering time 0.4s, the type of cooling is air cooling; Adopt air draught to sub-elect the powder of size-grade distribution between 15 microns ~ 45 microns sintered powder, be WC-10Co-4Cr hot spray powder.
Finally obtain particle shape comprise spherical, class is spherical and aspheric WC-10Co-4Cr hot spray powder, this powder is pressed GB1482-1984 and is detected: mobility < 25s/50g, loose density < 3.5g/cm
3.
Claims (7)
1. the preparation method of a tungsten-cobalt carbide or tungsten-cobalt carbide-chromium hot spray powder, it is characterized in that: by the aimed quality proportioning of the tungsten-cobalt carbide of design or each component of tungsten-cobalt carbide-chromium powder end, get respectively tungsten carbide powder and cobalt powder or tungsten carbide powder, cobalt powder and chromium powder are through being mixed to get mixed powder, after wet-milling to mixed powder mean particle size is 0.1 micron～10 microns, add the polyoxyethylene glycol that accounts for mixed powder massfraction 1%～5%, mist projection granulating, obtain prilling powder, prilling powder is through screening, get granularity and be the powder of 15～75 microns after skimming treatment, high temperature Fast Sintering under protective atmosphere, air cooling, obtain sintered powder, each constituent mass per-cent of described tungsten-cobalt carbide powder is: tungsten carbide powder 1%-99%, cobalt powder 1%-99%, each constituent mass per-cent of described tungsten-cobalt carbide-chromium powder end is: tungsten carbide powder 1%-99%, cobalt powder 1%-99%, chromium powder 1%-20%, described high temperature Fast Sintering is carried out in vertical high-temperature sintering oven, and the type of heating of described vertical high-temperature sintering oven is Frequency Induction Heating or resistive heating, described high temperature Fast Sintering temperature: 1000～1700 ℃, and sintering time: 0.1～5s.
2. the preparation method of tungsten-cobalt carbide according to claim 1 or tungsten-cobalt carbide-chromium hot spray powder, is characterized in that, to adding in described mixed powder after deionized water or dehydrated alcohol are mixed with slip, carries out wet-milling; In slip, solid content is 50%～80%.
3. the preparation method of tungsten-cobalt carbide according to claim 1 or tungsten-cobalt carbide-chromium hot spray powder, it is characterized in that, described mist projection granulating carries out in spray-drying tower, the inlet temperature of spray-drying tower is controlled at 200～300 ℃, temperature out is controlled at 100～150 ℃, and spray-drying tower tower internal gas pressure is controlled at 0～– 1KPa.
4. the preparation method of tungsten-cobalt carbide according to claim 1 or tungsten-cobalt carbide-chromium hot spray powder, is characterized in that, 600 ℃～1000 ℃ of described skimming treatment temperature, time 2h～8h.
5. the preparation method of tungsten-cobalt carbide according to claim 1 or tungsten-cobalt carbide-chromium hot spray powder, is characterized in that, described protective atmosphere is nitrogen atmosphere.
6. the preparation method of tungsten-cobalt carbide according to claim 1 or tungsten-cobalt carbide-chromium hot spray powder, it is characterized in that, sintered powder adopts double-deck spin vibration sieve to sieve or air draught sorting, obtain tungsten-cobalt carbide or tungsten-cobalt carbide-chromium hot spray powder, its be shaped as spherical, class is spherical or aspherical particle.
7. the preparation method of tungsten-cobalt carbide according to claim 1 or tungsten-cobalt carbide-chromium hot spray powder, it is characterized in that, powder after degreasing with the mode of motion continuous uniform of freely falling body complete liquid phase sintering in high-temperature zone by vertical high-temperature sintering oven and ，Qie Yu high-temperature zone, cooling zone.
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| WO2018169477A1 (en) * | 2017-03-14 | 2018-09-20 | Vbn Components Ab | High carbon content cobalt-based alloy |
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