CN104446397A - Submicron crystalline ceramic coating for hard alloy and preparation method - Google Patents
Submicron crystalline ceramic coating for hard alloy and preparation method Download PDFInfo
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Abstract
The invention provides a submicron crystalline ceramic coating for a hard alloy and a preparation method. The components of the submicron crystalline ceramic coating comprise Al2O3, ZrO2, TiO2, and SiO2. The preparation method comprises the following steps: respectively weighing powder materials, mixing the powder materials, heating to smelt the mixture, carrying out water quenching on the mixture to obtain non-crystalline ceramic, and ball-milling to obtain non-crystalline ceramic powder; adding Co powder into the non-crystalline ceramic powder, adding a solvent, and wet-milling to obtain coating slurry; coating the surface of the hard alloy with the coating slurry, drying the hard alloy, and sintering the hard alloy in a vacuum environment to obtain the submicron crystalline ceramic coating for the hard alloy. According to the invention, problems that the sintering temperature of SAZ ceramic coating is high, and the thermal expansion coefficient is not matched with the hard alloy are solved, the prepared coating has the advantages of high-temperature resistance and corrosion resistance, the preparation method is simple, the production cost of the hard alloy coating can be greatly reduced, such failure problems as oxidation, corrosion and attrition of hard alloy components under actual working conditions are solved to a certain extent, and the service lives of hard alloy materials and devices are prolonged.
Description
Technical field:
The present invention relates to a kind of coating and preparation method, particularly Wimet sub-micron crystal ceramic coating and preparation method, belongs to field of surface engineering technique.
Background technology:
In use often there is high temperature oxidation, wearing and tearing, etching problem in Wimet, have a strong impact on metal parts performance and used life, protective coating is applied at alloy surface, both Alloy Anti oxidation and corrosion resistance nature can have been improved, substantially can keep again the mechanical property of alloy, be used widely in engineering.On inserted tool matrix, such as apply the metal that one or more layers hardness is high, wear resistance is good or nonmetallic compound film (as TiC, TiAlN, Al
2o
3deng) coating, combine the advantage of matrix high strength, high tenacity and coating high rigidity, high-wearing feature, improve on the one hand alloy and reduce rubbing factor between cutter and workpiece, improve the wear resistance of alloy, anti-oxidant, corrosion resistance nature and do not reduce the toughness of matrix.
At present, what commonly use in hard alloy coating is TiCN, (Ti, Al) N coating.TiCN coating has excellent toughness and the hardness of TiC and TiN coating concurrently, it in coating procedure by continuously changing the composition of C and N to the character of control TiCN, and the gradient-structure of different components can be formed, reduce the internal stress of coating, improve toughness, increase coat-thickness, Anticrack, reduce tipping.In recent years, be that four metamember new coating material (as TiZrCN, TiAlCN, TiSiCN etc.) of base also occur one after another with TiCN.(Ti, Al) N coated material is one of current most widely used hard alloy coating, (Ti, Al) N has very high hot hardness and resistance of oxidation, maximum operating temperature 800 DEG C, oxidation onset temperature 700 DEG C, coating hardness HV3000, color is purplish grey.But alloy environment for use is often abrasion environment, high-temperature oxidation environment, corrosive environment etc., and often exists for several condition simultaneously.Be applied to the advantage that the coating system such as the TiCN of Wimet, (Ti, Al) N coating has excellent in abrasion resistance at present, but there is the problems such as antioxidant property is poor, heat-proof quality is poor, coating repairs difficulty, and production cost is high.
Many-sided over-all properties must be possessed: low thermal conductivity with the stupalith of making coatings; With the thermal expansivity of Matrix Match; Low sintering activity; High thermal stability; Good anti-thermal shock and hot corrosion resistance.
Compound oxidate ceramic coating, owing to having good heat-proof quality, wear resisting property, antioxidant property, corrosion resistance nature and cost is low, preparation technology is simple, in recent years, becomes one of alloy coat study hotspot gradually.As conventional ceramic coating material, oxide ceramics mainly contains alumina series, zirconium white system, titanium oxide, zirconium white, mullite, spinel ceramics etc.It is good that oxide ceramic coating material has stability at elevated temperature, corrosion resistance and good, and scour resistance and the feature such as thermal insulation is good, Application Areas is very extensive, comprises the chemistry such as petrochemical complex, metal metallurgy smelting and field of metallurgy that utilize its corrosion resisting property.The nearly all land of the current U.S. with and marine gas turbine engine all have employed oxide ceramic coating, in 10 years of future, oxide ceramic coating will reach the annual growth of 12%, annual growth wherein in engine parts will reach 25%, have wide application and development prospect.And alumina series has obtained extensive research and apply in Wimet, the steel product turning trade mark GC4225, GC4235 that such as Sweden Sandvik Coromant company releases, have employed the gradient hard alloy matrix of superfine crystal particle, be equipped with warm chemical coating (MT-CVD) and thin crystal column shape a-Al in TiCN
2o
3coating, carbide chip has good anti-micro-tipping performance, antistripping ability and good surface smoothness.GC4225 blade compares cutter life with general P25 blade can improve 60%, and production efficiency improves 33%, is the first-selected trade mark of steel part processing.But the thermal expansion matching aspect of this system coating and matrix is slightly not enough, and do not mate due to the hardness of base material and coated material, Young's modulus and thermal expansivity, lattice types is also different, cause between matrix and coating and produce unrelieved stress, bonding force is not strong, and at high temperature long-time application easily causes the problems such as coating shedding.
Along with Machining Technology progress, existing coating can not meet day by day harsh job requirement.
Summary of the invention:
The object of the invention is to overcome the deficiency of prior art and provides a kind of reasonable mixture ratio of components, high temperature resistant, corrosion resistance and good, preparation cost is low, and coating is good with mating of hard alloy substrate, the Wimet sub-micron crystal ceramic coating that bonding strength is high and preparation method.
A kind of Wimet sub-micron crystal ceramic coating of the present invention, comprises following component by percentage to the quality:
Al
2O
335～40％；
ZrO
210～20％；
TiO
21～8％；
Surplus is SiO
2with inevitable impurity.
A kind of Wimet sub-micron crystal ceramic coating of the present invention, described TiO
2nucleating Agent effect is played in component.
A kind of Wimet sub-micron crystal ceramic coating of the present invention, the purity of described titanium dioxide, silicon-dioxide is all >=99.9%; Purity >=98% of described aluminum oxide; The purity of described zirconium dioxide, cobalt powder all >=99%; Each component powders particle diameter is 0.1-1 micron.
The preparation method of a kind of Wimet sub-micron crystal of the present invention ceramic coating, comprises the steps:
Step one is prepared burden, mix
According to the coating ingredients quality proportioning of design, get SiO respectively
2, Al
2o
3, ZrO
2, TiO
2powder, adds in mixing tank, mechanically mixing 1-24h, obtains compound;
Step 2 prepares ceramic powder
After mixed material heating to the 1650 ~ 1700 DEG C fusing that step one is obtained, insulation 2 ~ 4h, shrend, obtains transparent noncrystal pottery, being 0.1-10 micron, obtaining amorphous ceramic powder by being milled to granularity after noncrystal ceramic fragmentation;
Step 3 configuration coating slip
Get amorphous ceramic powder obtained in step 2, add the Co powder accounting for amorphous ceramic powder quality 2%-10%, then, adding mass percentage concentration is in the PVB solution of 1-4wt%, configuration solid-liquid mass ratio is the mixed liquor of 1:1-1:5, by mixed liquor ball milling, mixing, obtains coating paste; Described PVB solution in PVB ethanolic soln, adds distilled water form, and PVB refers to polyvinyl butyral acetal, and PVB plays dispersion agent effect.
Step 4 coating, sintering
Coating slip obtained for step 3 five is coated on carbide surface, after drying; Under vacuum environment, carry out three step staircase method heat-agglomeratings with the temperature rise rate of 10-25 DEG C/min, obtain Wimet sub-micron crystal ceramic coating; Three step staircase method heating technique parameter are: first 400-500 DEG C of temperature, insulation 0.5-3h, the binding agent in decoating; Then 900-1000 DEG C is heated to, insulation 0.5 ~ 3.0h; Finally, be heated to 1200-1300 DEG C, after insulation 0.5 ~ 3.0h; Furnace cooling.
The preparation method of a kind of Wimet sub-micron crystal of the present invention ceramic coating, in the first step, described SiO
2, Al
2o
3, ZrO
2, TiO
2the granularity of powder is 0.1-1 micron; The purity of described titanium dioxide, silicon-dioxide all>=99.9%; Purity>=98% of described aluminum oxide; The purity of described zirconium dioxide, cobalt powder all>=99%.
The preparation method of a kind of Wimet sub-micron crystal of the present invention ceramic coating, in second step, compound is placed in corundum crucible, uses silicon molybdenum rod furnace heat fused.
The preparation method of a kind of Wimet sub-micron crystal of the present invention ceramic coating, in second step, carry out in the cold water of shrend in stainless steel vessel, quench cooling rate is 100-1000 DEG C/S.
The preparation method of a kind of Wimet sub-micron crystal of the present invention ceramic coating, in second step, ball milling 1-24h after noncrystal pottery is broken, ball material mass ratio is 15:1-5:1, drum's speed of rotation is 100-500 rev/min, obtains the amorphous ceramic powder that granularity is 0.1-10 micron.
The preparation method of a kind of Wimet sub-micron crystal of the present invention ceramic coating, in 3rd step, mixed liquor milling parameters is: ball material mass ratio is 15:1-5:1, drum's speed of rotation is 100-500 rev/min, Ball-milling Time 1-24h, in the coating paste obtained, amorphous ceramic powder size is 50-500 nanometer.
The preparation method of a kind of Wimet sub-micron crystal of the present invention ceramic coating, in the 4th step, coating slip adopts the method for spraying or dip-coating to be coated on carbide surface, ensures that coating uniform is fine and close, thickness is moderate, sends into the dry 1-24h of loft drier.
The preparation method of a kind of Wimet sub-micron crystal of the present invention ceramic coating, in the 4th step, sintering, carries out in vacuum sintering furnace or atmosphere sintering furnace, and in control stove, vacuum tightness is within the scope of 0.0001-10pa.
Principle and advantage
The present invention owing to adopting said components proportioning and preparation technology, provide Al-Si-Zr-O stupalith there is excellent thermostability and thermal shock resistance, having lower thermal conductivity, is a kind of extremely promising oxide ceramic coating material.
In preparation method, the spraying adopted or dip coating by the restriction of metallic matrix shape, be applicable to the matrix of different shape, and required equipment are not simple, cheap, cost is low, also has film forming area large, uniform film thickness simultaneously, fast and the thickness of rate of film build is easy to the advantages such as control, thus this method is to workpiece shapes strong adaptability, applied widely, is conducive to commercial scale production.
The present invention adopts the speed of cooling controlling melt quenching; prepare the ultra tiny complex phase Amorphous Crystallization pottery of Al-Si-Zr-O; after being processed into the slip of suitable fineness and viscosity, after coating and high-temperature melting, form the ceramic supercoat of uniformly continous on alloy base material surface.Amorphous Crystallization legal system is that a kind of non-crystalline state prepares the technology of nano ceramics through original position dominated crystallization for nano ceramics, it and traditional prepare ceramic technology with expensive nanometer powder through high-temperature sintering process and have fundamental difference, from operational path, thoroughly can avoid nanometer powder reunite, during high temperature sintering can not completely fine and close and grain growth speed be difficult to control etc. a series of when sintering process insoluble problem, be conducive to acquisition high uniformity, high-compactness, the nano level of high reliability, submicron order ceramic coating material.
The preparation method of Wimet sub-micron crystal ceramic coating provided by the invention, realize that cemented carbide base material is high temperature resistant, wear-resisting, anticorrosive, the General Promotion of heat-proof quality, the problem that under solution actual condition, cemented carbide member oxidation corrosion was lost efficacy, effectively extends material and equips work-ing life.Al-Si-Zr-O system Amorphous Crystallization ceramic coating slip spraying (or dip-coating)-gradient sintering technique is prepared novel multiple phase oxide ceramic coating by the present invention on cemented carbide base material, obtains high temperature resistant, corrosion resistant submicron complex phase ceramic coating.Coated material prepared by the present invention, superior performance, cost is low, stable preparation process, and yield rate is high, under the prerequisite of use properties not affecting base material, achieves the significantly lifting of metal parts resistance to elevated temperatures, corrosion resistance nature and heat dispersion.Its concrete reason is as follows:
Adopt Amorphous Crystallization method, realize non-crystalline state and prepare submicron or nanocrystalline ceramics powder through original position dominated crystallization, it and traditional prepare ceramic coating technology with expensive nanometer powder through high-temperature sintering process and have fundamental difference, from operational path, thoroughly can avoid nanometer powder reunite, during high temperature sintering can not completely fine and close and grain growth speed be difficult to control etc. a series of when sintering process insoluble problem, be conducive to acquisition high uniformity, high-compactness, the submicron of high reliability or nanometer scale ceramics coated material.
Amorphous ceramic powder and the addition of C o powder are made coating slip by the present invention, be coated on carbide surface, high temperature resistant, the corrosion-resistant sub-micron crystal ceramic coating finished product of Wimet is prepared by gradient sintering technique, its key point, be the setting of gradient sintering technique on the one hand, first sintering process is incubated 0.5-3h at 400-500 DEG C of temperature, and main purpose is the binding agent in decoating; And middle high temperature section 900-1000 DEG C and 1200-1300 DEG C of sintering temperature are just in time arranged near the temperature range of complex phase ceramic Amorphous Crystallization, by original position dominated crystallization technology, achieve the preparation of submicron complex phase ceramic coating, meanwhile, because amorphous ceramic has lower melt temperature mutually, when coating sinters, greatly can reduce the sintering temperature of coating, simplify preparation technology, save the energy, reach the object reduced costs; On the other hand, add the addition of C o powder, coating is more mated with carbide matrix isolator CTE, and coating possesses good bonding strength and thermal shock performance; Metal Co particle is as the connection phase of coating with matrix, Co element can be good at matching coating and intermetallic thermal expansivity, pass through adjusting component, micro-crystalline ceramic can be made to have wider use temperature scope and controlled thermal expansivity, make its hot physical performance and metallic matrix reach better matching.Compare with other structure coatings, this coating is owing to connecting the transitional function of phase, and the internal stress thus between ceramic layer and matrix is little, under high temperature, shock load Working environment, its thermal stresses of bearing, shock stress obtain certain mitigation, ensure that the matched well of coating and hard alloy substrate.
In coated material selection, many-sided over-all properties must be possessed with the diphase ceramic material of making coatings: low thermal conductivity; With the thermal expansivity of Matrix Match; Low sintering activity; High thermal stability; Good anti-thermal shock and hot corrosion resistance.The Al-Si-Zr-O stupalith that the present invention adopts has excellent thermostability and high temperature oxidation resistance, there is lower thermal conductivity and erosion rate, this is the heterogeneous composite structure due to Al-Si-Zr-O system complex phase Amorphous Crystallization stupalith, the tiny crack mechanism formed due to the difference of the thermal expansivity not between homophase and boundary stress and each mutually between stop lead crack expand or crack the effects such as deflection, fracture toughness property and the heat-shock resistance of stupalith can be improved.Moreover, due to transformation toughening, the high-temperature behavior of Al-Si-Zr-O series ceramic material also can be improved, when the material is heated, ZrO
2just there is phase in version in particle, and causes tiny crack in the base, thus absorb the energy of crack propagation, weakens or prevent the expansion of crackle, reaches toughness reinforcing effect.Thus improve the thermostability of pottery.In addition, Al-Si-Zr-O system pottery is made up of three kinds of oxide compound compounds, and matrix component is oxide compound inherently, can not be oxidized, and oxidisability is naturally good.And by adding the addition of C o powder in coating material, make coating more mate with carbide matrix isolator CTE, coating possesses good bonding strength and thermal shock performance, excellent combination property.
Embodiment
Embodiment 1
Ceramics component is: the aluminum oxide of 35wt%, the zirconium dioxide of 10wt%, the titanium dioxide of 3wt%, and surplus is that silicon-dioxide and total amount are not more than 0.05% inevitable impurity.
Above-mentioned ceramics component is added mechanically mixing 5h in mixing tank successively, afterwards the material mixed is added in corundum crucible, with silicon molybdenum rod furnace heating, at 1650 DEG C, be incubated 2h.Poured into by obtained high-temperature fusion liquid in the cold water in stainless steel vessel and obtain transparent noncrystal, by noncrystal pulverizing, high-energy ball milling 5h, detecting the amorphous ceramic powder particle mean particle size obtained is 5.2 microns.
Get amorphous ceramic powder 20g, add 1.5g cobalt powder, joining 100ml percent mass agriculture degree is in the PVB solution of 2wt%, is prepared into coating paste, and utilizes spray gun that the slurry of preparation is evenly coated on carbide surface by batch mixing, high-energy ball milling 5h.After spraying, Wimet is placed in loft drier dry 3 hours.
Dry complete hard alloy coating sample, be positioned in vacuum sintering furnace, heat with the temperature rise rate of 20 DEG C/min, vacuum tightness remains on about 5pa, first at 400 DEG C, is incubated 1h, after the binding agent in decoating, be heated to 950 DEG C, after insulation 1h, be warming up to 1300 DEG C, soaking time 0.5h; Last powered-down furnace cooling, obtains high temperature resistant, corrosion-resisting hard-alloy sub-micron crystal ceramic coating.
Coating sample prepared by the present embodiment carries out Performance Detection, and the data obtained are: oxidation resistance temperature reaches 1300K, static antioxidant defense time 80000s; Coating room temperature-1200K circulation thermal shock number of times reaches 1478 times; After applying coating, corrosion resistance nature improves 60%; After applying coating, wear resisting property improves 25%; 1000K coating normal direction whole radiation rate is 0.87.
Embodiment 2
Ceramics component is: the aluminum oxide of 40wt%, the zirconium dioxide of 20wt%, the titanium dioxide of 8wt%, and surplus is that silicon-dioxide and total amount are not more than 0.05% inevitable impurity.
Above-mentioned ceramics component is added mechanically mixing 15h in mixing tank successively, afterwards the material mixed is added in corundum crucible, with silicon molybdenum rod furnace heating, at 1700 DEG C, be incubated 4h.Poured into by obtained high-temperature fusion liquid in the cold water in stainless steel vessel and obtain transparent noncrystal, by noncrystal pulverizing, high-energy ball milling 10h, detecting the amorphous ceramic powder particle mean particle size obtained is 2.4 microns.
Get amorphous ceramic powder 50g, add 5g cobalt powder, joining 200ml percent mass agriculture degree is in the PVB solution of 1wt%, is prepared into coating paste, and utilizes spray gun that the slurry of preparation is evenly coated on carbide surface by batch mixing, high-energy ball milling 10h.After spraying, Wimet is placed in loft drier dry 4 hours.
Dry complete hard alloy coating sample, is positioned in vacuum sintering furnace or atmosphere sintering furnace, heats with the temperature rise rate of 15 DEG C/min, vacuum tightness remains on about 2pa, first at 400 DEG C, is incubated 1.5h, after the binding agent in decoating, be heated to 1000 DEG C, after insulation 2h; Be warming up to 1300 DEG C, insulation 1h; Last powered-down furnace cooling, obtains high temperature resistant, corrosion-resisting hard-alloy sub-micron crystal ceramic coating.
Coating sample prepared by the present embodiment carries out Performance Detection, and the data obtained are: oxidation resistance temperature 1300K, static antioxidant defense time 78000s; Coating room temperature-1200K circulation thermal shock number of times reaches 1556 times; After applying coating, corrosion resistance nature improves 55%; After applying coating, wear resisting property improves 45%; 1000K coating normal direction whole radiation rate is 0.86.
Embodiment 3
Ceramics component is: the aluminum oxide of 36wt%, the zirconium dioxide of 15wt%, the titanium dioxide of 4wt%, and surplus is that silicon-dioxide and total amount are not more than 0.05% inevitable impurity.
Above-mentioned ceramics component is added mechanically mixing 10h in mixing tank successively, afterwards the material mixed is added in corundum crucible, with silicon molybdenum rod furnace heating, at 1700 DEG C, be incubated 3h.Poured into by obtained high-temperature fusion liquid in the cold water in stainless steel vessel and obtain transparent noncrystal, by noncrystal pulverizing, high-energy ball milling 15h, detecting the amorphous ceramic powder particle mean particle size obtained is 1.9 microns.
Get amorphous ceramic powder 25g, add 2g cobalt powder, joining 130ml percent mass agriculture degree is in the PVB solution of 4wt%, is prepared into coating paste, and utilizes dip coating that the slurry of preparation is evenly coated on carbide surface by batch mixing, high-energy ball milling 15h.After dip-coating, Wimet is placed in loft drier dry 2 hours.
Dry complete hard alloy coating sample, is positioned in vacuum sintering furnace or atmosphere sintering furnace, heats with the temperature rise rate of 10 DEG C/min, vacuum tightness remains on about 6pa, first at 400 DEG C, is incubated 2h, after the binding agent in decoating, be heated to 900 DEG C, insulation 1.5h; Then 1250 DEG C are warming up to, insulation 1h; Last powered-down furnace cooling, obtains high temperature resistant, corrosion-resisting hard-alloy sub-micron crystal ceramic coating.
Coating sample prepared by the present embodiment carries out Performance Detection, and the data obtained are: oxidation resistance temperature 1300K, static antioxidant defense time 70000s; Coating room temperature-1200K circulation thermal shock number of times reaches 1398 times; After applying coating, corrosion resistance nature improves 53%; After applying coating, wear resisting property improves 35%; 1000K coating normal direction whole radiation rate is 0.87.
Embodiment 4
Ceramics component is: the aluminum oxide of 38wt%, the zirconium dioxide of 12wt%, the titanium dioxide of 5wt%, and surplus is that silicon-dioxide and total amount are not more than 0.05% inevitable impurity.
Above-mentioned ceramics component is added mechanically mixing 12h in mixing tank successively, afterwards the material mixed is added in corundum crucible, with silicon molybdenum rod furnace heating, at 1700 DEG C, be incubated 2h.Poured into by obtained high-temperature fusion liquid in the cold water in stainless steel vessel and obtain transparent noncrystal, by noncrystal pulverizing, high-energy ball milling 12h, detecting the amorphous ceramic powder particle mean particle size obtained is 2.1 microns.
Get amorphous ceramic powder 20g, add 1.8g cobalt powder, joining 100ml percent mass agriculture degree is in the PVB solution of 3wt%, is prepared into coating paste, and utilizes dip coating that the slurry of preparation is evenly coated on carbide surface by batch mixing, high-energy ball milling 12h.After dip-coating, Wimet is placed in loft drier dry 3 hours.
Dry complete hard alloy coating sample, is positioned in vacuum sintering furnace or atmosphere sintering furnace, heats with the temperature rise rate of 10 DEG C/min, vacuum tightness remains on about 0.1pa, first at 400 DEG C, is incubated 1.0h, after the binding agent in decoating, be heated to 1000 DEG C, insulation 1.5h; Then 1300 DEG C are warming up to, insulation 1h; Last powered-down furnace cooling, obtains high temperature resistant, corrosion-resisting hard-alloy sub-micron crystal ceramic coating.
Coating sample prepared by the present embodiment carries out Performance Detection, and the data obtained are: oxidation resistance temperature 1300K, static antioxidant defense time 94000s; Coating room temperature-1200K circulation thermal shock number of times reaches 1756 times; After applying coating, corrosion resistance nature improves 58%; After applying coating, wear resisting property improves 30%; 1000K coating normal direction whole radiation rate is 0.87.
Comparative example: (Ti, Al) N top coat, in coating, Ti, Al massfraction is respectively 50%.
Preparation technology of coating:
Matrix sample is cut into the fritter being of a size of 30mm × 10mm × 3mm; Then matrix is carried out pre-treatment, after mechanical grinding and polishing 5min, through alcohol ultrasonic cleaning 10min, be placed on after drying up in 4 arc source ions platings and hallow cathode deposition, HCD composite film coating press proof sample platform and prepare plating, target to be high-purity Ti target and massfraction ratio be respectively 50% Ti-Al alloys target.Sample chamber is evacuated to 3 × 10
-3pa, bombards 10min to obtain clean surface with the Ar (purity is higher than 99.9%) of ionization to specimen surface, then at matrix surface pre-deposition TiN bottom, closes pure Ti target after keeping 20min, start Ti-Al alloys target, regulate Ar and N
2ratio be 1:2, deposition (Ti, Al) N coating.Depositing time is 60min, and pulsed bias gets-200V, and deposition terminates rear sample furnace cooling and takes out to room temperature.Obtain (Ti, Al) N coating.
The coating sample that above-mentioned technique obtains carries out Performance Detection, and the data obtained are:
Oxidation resistance temperature 1100K, static antioxidant defense time 30000s; Coating room temperature-1100K circulation thermal shock number of times reaches 312 times; After applying coating, corrosion resistance nature improves 25%; After applying coating, wear resisting property improves 20%.
The coating performance index prepared by embodiment of the present invention 1-4 and comparative example compare known: the coating that after coating oxidation resistance temperature prepared by the present invention, static antioxidant defense time, coating room temperature-1200K circulation thermal shock number of times, applying coating, after corrosion resistance nature, applying coating, wear resisting property all hands over prior art to prepare exceeds a lot.
Above embodiment is further illustrating and explaining this patent, instead of limitation of the present invention, and at moral rights protection domain of the present invention, any amendment made, all falls into protection scope of the present invention.
Claims (10)
1. a Wimet sub-micron crystal ceramic coating, comprises following component by percentage to the quality:
Al
2O
335～40％；
ZrO
210～20％；
TiO
21～8％；
Surplus is SiO
2with inevitable impurity.
2. bright a kind of Wimet sub-micron crystal ceramic coating according to claim 1, is characterized in that: the purity of described titanium dioxide, silicon-dioxide all >=99.9%; Purity >=98% of described aluminum oxide; The purity of described zirconium dioxide, cobalt powder all >=99%; Each component powders particle diameter is 0.1-1 micron.
3. prepare the method for a kind of Wimet sub-micron crystal ceramic coating as claimed in claim 2, comprise the steps:
Step one is prepared burden, mix
According to the coating ingredients quality proportioning of design, get SiO respectively
2, Al
2o
3, ZrO
2, TiO
2powder, adds in mixing tank, mechanically mixing 1-24h, obtains compound;
Step 2 prepares ceramic powder
After mixed material heating to the 1650 ~ 1700 DEG C fusing that step one is obtained, insulation 2 ~ 4h, shrend,
Obtain transparent noncrystal pottery, being 0.1-10 micron by being milled to granularity after noncrystal ceramic fragmentation, obtaining amorphous ceramic powder;
Step 3 configuration coating slip
Get amorphous ceramic powder obtained in step 2, add the Co powder accounting for amorphous ceramic powder quality 2%-10%, then, add in PVB solution, configuration solid-liquid mass ratio is the mixed liquor of 1:1-1:5, by mixed liquor ball milling, mixing, obtains coating paste;
Step 4 coating, sintering
Coating slip obtained for step 3 five is coated on carbide surface, after drying; Under vacuum environment, carry out three step staircase method heat-agglomeratings with the temperature rise rate of 10-25 DEG C/min, obtain Wimet sub-micron crystal ceramic coating; Three step staircase method heating technique parameter are: first 400-500 DEG C of temperature, insulation 0.5-3h, the binding agent in decoating; Then 900-1000 DEG C is heated to, insulation 0.5 ~ 3.0h; Finally, be heated to 1200-1300 DEG C, after insulation 0.5 ~ 3.0h; Furnace cooling.
4. method according to claim 3, is characterized in that: in the first step, described SiO
2, Al
2o
3, ZrO
2, TiO
2the granularity of powder is 0.1-1 micron; The purity of described titanium dioxide, silicon-dioxide all>=99.9%; Purity>=98% of described aluminum oxide; The purity of described zirconium dioxide, cobalt powder all>=99%.
5. method according to claim 3, is characterized in that: in second step, compound is placed in corundum crucible, uses silicon molybdenum rod furnace heat fused.
6. method according to claim 3, is characterized in that: in second step, carries out in the cold water of shrend in stainless steel vessel, and quench cooling rate is 100-1000 DEG C/S.
7. method according to claim 3, is characterized in that: in second step, and ball milling 1-24h after noncrystal pottery is broken, ball material mass ratio is 15:1-5:1, and drum's speed of rotation is 100-500 rev/min, obtains the amorphous ceramic powder that granularity is 0.1-10 micron.
8. method according to claim 3, it is characterized in that: in the 3rd step, mixed liquor milling parameters is: ball material mass ratio is 15:1-5:1, drum's speed of rotation is 100-500 rev/min, Ball-milling Time 1-24h, in the coating paste obtained, amorphous ceramic powder size is 50-500 nanometer.
9. method according to claim 3, is characterized in that: in the 4th step, and coating slip adopts the method for spraying or dip-coating to be coated on carbide surface, ensures that coating uniform is fine and close, thickness is moderate, sends into the dry 1-24h of loft drier.
10. the method according to claim 3-9 any one, is characterized in that: in the 4th step, and sintering, carries out in vacuum sintering furnace or atmosphere sintering furnace, and in control stove, vacuum tightness is within the scope of 0.0001-10pa.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114959680A (en) * | 2021-11-16 | 2022-08-30 | 湖北理工学院 | Thermal barrier coating and preparation method thereof |
| CN115532569A (en) * | 2022-11-09 | 2022-12-30 | 深圳市拉普拉斯能源技术有限公司 | Preparation method of substrate surface coating |
| CN115821092A (en) * | 2022-11-22 | 2023-03-21 | 华中科技大学 | Preparation method of hard alloy composite material with gradient structure and performance |
| CN116060624A (en) * | 2022-12-21 | 2023-05-05 | 华侨大学 | High-temperature-resistant high-hardness composite powder, preparation method and application thereof in laser additive manufacturing |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114959680A (en) * | 2021-11-16 | 2022-08-30 | 湖北理工学院 | Thermal barrier coating and preparation method thereof |
| CN114959680B (en) * | 2021-11-16 | 2023-11-14 | 湖北理工学院 | Thermal barrier coating and preparation method thereof |
| CN115532569A (en) * | 2022-11-09 | 2022-12-30 | 深圳市拉普拉斯能源技术有限公司 | Preparation method of substrate surface coating |
| CN115821092A (en) * | 2022-11-22 | 2023-03-21 | 华中科技大学 | Preparation method of hard alloy composite material with gradient structure and performance |
| CN115821092B (en) * | 2022-11-22 | 2023-12-26 | 华中科技大学 | Preparation method of hard alloy composite material with gradient structure and performance |
| CN116060624A (en) * | 2022-12-21 | 2023-05-05 | 华侨大学 | High-temperature-resistant high-hardness composite powder, preparation method and application thereof in laser additive manufacturing |
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| CN104446397B (en) | 2016-08-24 |
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