CN104404434B - A kind of ceramic coating of metal material surface and preparation method thereof - Google Patents
A kind of ceramic coating of metal material surface and preparation method thereof Download PDFInfo
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- CN104404434B CN104404434B CN201410614791.7A CN201410614791A CN104404434B CN 104404434 B CN104404434 B CN 104404434B CN 201410614791 A CN201410614791 A CN 201410614791A CN 104404434 B CN104404434 B CN 104404434B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
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- Coating By Spraying Or Casting (AREA)
Abstract
The present invention relates to ceramic coating of a kind of metal material surface and preparation method thereof, belong to ceramic coating preparing technical field.Use plasma spraying technology, toughener, compact agent, fining agent and viscosifier are added in ceramic matrix powder, once form that porosity is low by mechanical hand at material (metal or alloy etc.) parts surface, uniform texture and big the super thick (>=2mm of adhesion strength, more than 10mm can be reached) ceramic of compact coating, obtain plant equipment and the surface abrasion resistance of parts, corrosion-resistant, conduct electricity or insulate and high temperature oxidation resisting ultra high build coating.On the basis of playing matrix material performance, the characteristic of ceramic coating, elongate member life-span can be given full play to, save matrix material cost, expand the material selection range of mechanical part etc. simultaneously.
Description
Technical field
The present invention relates to ceramic coating of a kind of metal material surface and preparation method thereof, belong to ceramic coating technology of preparing
Field.
Background technology
Ceramic coating can meet different hardness, heat insulation, anticorrosion and antioxidation, conduct electricity and insulate, the difference portion such as high temperature resistance
The function of part, is widely used in such as Aero-Space (such as aero-engine high temperature blade), engineering machinery (various wear parts), building materials
Machinery (such as the auger of profiled part), hydroelectric facility (such as turbine blade) and pipeline (such as face abrasive wear
Pipeline valve), the field such as power generation gas turbine (such as high temperature blade surface).In special environment, thickness of ceramic coating is certainly
The important indicator of qualitative energy, such as ceramic layer have good insulating properties, and the thickness of ceramic coating can significantly improve and puncture
Voltage；The utilization of super thick abrasion-proof ceramic coat can improve component life further；Conductivity ceramics coating has good conduction
Performance, thicker coating can improve the application life in high-temperature corrosion environment greatly；Thermal barrier coating system is improving matrix
On the basis of antioxygenic property, thicker ceramic coating can reduce part temperatures etc. further.But metal and ceramic material
Physicochemical characteristics entirely different, especially because crystal structure, atomic bond structure, thermal coefficient of expansion and hardness etc., cause
It is difficult to prepare thicker (>=2mm) and the ceramic coating of height fine and close (>=96%) in metal alloy surface；Along with plasma thermal sprayed
The development of technology of preparing, the conventional ceramic coatings thickness utilizing the methods such as thermal spraying to be formed is essentially below 1mm, even with viscous
Knot layer improves the bond strength of coating, but in spraying process, the matrix such as pottery and alloy has bigger thermal expansion coefficient difference,
Repeatedly being easily caused ceramic coating after spraying and have bigger internal stress, crack and come off inefficacy；So, utilize traditional
Plasma spray technology technique and conventional material still large area can not prepare high fine and close (>=96%) ceramic coating of super thick (>=2mm).
Chinese patent 201010274694.X " restorative procedure of drill taper shank " is at alloy surface plasma spraying NiAl
Binder course, then utilizes flame-spraying CrNi-Cr3C2Coating, coating layer thickness is only 0.3-0.5mm.Chinese patent
201210533098.8 " preparation methoies of a kind of aluminium alloy wear-proof coating " utilize plasma spraying NiAl to tie in aluminum alloy surface
Close layer and oxide ceramic powder.Chinese patent 201310477478.9 " axial workpiece alumina powder plasma spraying reparation side
Method " by utilizing plasma or electric arc spraying to prepare aluminum oxide coating layer, thickness is about 20-30 μm.These potteries the most above-mentioned are coated with
Layer, all can not reach the thickness of 1mm-5mm, or relatively greatly and naturally come off due to internal stress when thicker, or due to bonding
Intensity is low and can not use by normal wear environment.And Chinese patent 200910242442.6 " a kind of large-area ceramic plate of preparing
Method " in, although the ceramic wafer of 6mm can be prepared, but owing to ceramic wafer is separated with graphite or plaster matrix, seriously limit
Make the application at parts such as machineries, can only use by single ceramic wafer.Chinese patent 201310272861.0 " a kind of target and
Manufacture method " in, utilization is plasma transferred arc spraying, and is only capable of preparing the alloy coat of 1-3mm in particular substrate.
Therefore for the applying working condition of alloy base, one is needed quickly and easily to prepare super thick (>=2mm) high fine and close
The heat spraying method of (>=96%) ceramic coating.
Summary of the invention
It is an object of the present invention to provide ceramic coating of a kind of metal material surface and preparation method thereof, described method uses heat
Spraying technology prepares surface thickness >=2mm, the abrasion-proof ceramic coat of consistency >=96%, and overcoming can not in conventional thermal spraying technology
The shortcoming preparing the ceramic of compact coating of thickness >=2mm at material surfaces such as structure members, expands thermal spraying and prepares answering of coating
By field and scope.
Described additive includes ceramic toughening agent, fine and close agent, fining agent, viscosifier, ceramic toughening agent in additive
Mass percent be 0.3～40%, the mass percent of fine and close agent is 0.5～35%, and the mass percent of fining agent is
0.8～35%, the mass percent of viscosifier is 0.5～30%；
Described ceramic material is oxide ceramic material, non-oxide ceramic material or cermet material；
Described ceramic toughening agent be the one in titanium boride, titanium carbide, aluminium oxide, rare earth oxide, titanium oxide and ferrum,
A kind of ratio (9:1 or 8:2) in molybdenum, copper, nickel and aluminum is mixed to get, and produces ductile layers and tough matrix between ceramic crystal；
Described compact agent is that one or more in kaolinite, montmorillonite, dickite are mixed to get, in any proportion at height
The lower particle surface of temperature produces the liquid of certain viscosity, improves ceramic body consistency, also rises when spraying non-oxide ceramics simultaneously
The effect of antioxidant.
Described grain refiner is that one or more in magnesium oxide, calcium oxide, Barium monoxide are mixed to get in any proportion,
Increase ceramic surface liquid high temperature viscosity, prevent ceramic crystal from excessively growing up, chromatographic analysis；
Described viscosifier powder is in cuprous oxide powder, ferrous oxide, iron suicide, ferromanganese powder, molybdenum-iron powder, brass powder
One or more are mixed to get in any proportion, improve the adhesion strength of ceramic coating and metallic matrix；
The granularity of ceramic powders of the present invention is 0.05-60 μm；Ceramic toughening agent, fine and close agent, fining agent, viscosifier
Granularity be 0.1-1 μm.
Another object of the present invention is to provide the preparation method of described metal material surface ceramic coating, its feature exists
In: specifically include following steps:
(1) weigh each raw material, use any one method of spray drying method, sintering crushing method or mechanical attrition method to carry out
Broken, make containing toughener, compact agent, grain refinement agent, the ceramic powders of viscosifier；
(2) metal base to be sprayed is carried out blasted rough process, then utilize dry air to the base material after sandblasting
Surface carries out clean process；
(3) dried powder step (1) obtained is sent in the powder feeder of thermal spray system, wherein, and powder feeder powder feeding gas
Body is Ar, and gas flow is 30-60L/min；Then the spray distance arranging manipulator control nozzle and metal base is 5-
11cm, the translational speed of nozzle is 0.001-0.05m/s.
(4) plasma spray coating process parameter is set, starts thermal spray system and mechanical hand, cover one at workpiece surface spraying
Ceramic coating is obtained after secondary.
Described in step of the present invention (2) in blasted rough processing procedure use grains of sand material be: white fused alumina, Brown Alundum or
Fused alumina zirconia, the granularity of the grains of sand is 18-25 μm.
Described plasma spray coating process parameter in step of the present invention (4) is: the throughput of argon is 90-130L/min,
The throughput of nitrogen is 5-30L/min, and operating current is 350-450A, and running voltage is 120-150V.
Plasma spray technology in step of the present invention (4), in addition to the steady plasma spraying technology of common gas, also includes Supersonic
Speed flame spray technique and the steady plasma spraying technology of water etc..
Compared with prior art, what the technical solution used in the present invention produced has the beneficial effect that:
(1) present invention uses plasma spraying technology direct spraying thickness to be on metal base >=the densification of 2mm
Ceramic coating, porosity≤0.1-4%；In spraying process of the present invention, the ceramic coating of thickness >=2mm is for once to have sprayed；
(2) strengthen toughness agent between ceramic crystal, produce ductile layers and tough matrix；Compact agent improves ceramic body consistency；
Fining agent is possible to prevent ceramic crystal excessively to grow up and chromatographic analysis；So relatively conventional multi-fold prepares the skill of thick coating
Art, thickness coatings internal stress of the present invention is little, thus has established mechanical foundation for thicker ceramic coating；
(3) suitable due to ceramic powders composition and ratio, the plasma spraying equipment current stabilization of employing, the oxygen formed
Changing the smooth densification of aluminized coating, good with metal base bond strength, hardness is HRC60-70, shows good functional characteristic, aobvious
Write service precision and the life-span that improve parts.
Accompanying drawing explanation
Fig. 1 is the process chart of the present invention.
Detailed description of the invention
It is below the specific embodiment of the present invention, technical scheme is described in further detail, but this
Bright protection domain is not limited to these embodiments, every change without departing substantially from present inventive concept or equivalent replacement and is included in this
Within the protection domain of invention.
Embodiment 1
(1) by non-oxide ceramics powder (carborundum and silicon nitride) and the additive of 10 weight portions, the institute of 90 weight portions
State additive include toughener (40wt%, 0.35 μm titanium oxide and 1.0 μm copper powders, ratio 9:1), fine and close agent (35wt%,
0.5 μm kaolinite), fining agent (0.8wt%, 0.5 μm magnesium oxide), viscosifier (24.2wt%, 1.0 μm molybdenum-iron powder) powder carry out
Sintering, then the broken powder size obtained is 45 μm, and dried powder is sent into plasma spraying equipment；
(2) potassium steel substrate surface to be sprayed is carried out 20 whitish eye corundum blasted rough and processes (the grains of sand material of use
For white fused alumina, the granularity of the grains of sand is 18 μm), then utilize dry air that the substrate surface after sandblasting carries out clean process；
(3) starting paint finishing and mechanical hand carries out plasma spraying, technological parameter is: main gas is Ar and N2, argon
Throughput is 90L/min, and the throughput of nitrogen is 15L/min；Operating current is 350A, and running voltage is 110V；Powder feeder send
Powder gas is Ar, and gas flow is 45L/min；Nozzle distance matrix distance is 9cm, and the translational speed of nozzle is 0.05m/s.?
To spray-on coating thickness be 2mm, consistency 99.5%.
Embodiment 2
(1) by metal ceramic powder (titanium boride and titanium carbide) and the additive of 20 weight portions of 80 weight portions, described in add
Add agent include toughener (0.3wt%, 0.35 μm titanium oxide and 1.0 μm nickel by powder, ratio 8:2), fine and close agent (34.7wt%,
0.5 μm montmorillonite), fining agent (35wt%, 0.5 μm Barium monoxide), viscosifier (30wt%, 1.0 μm iron suicide) powder burn
Knot, then the broken powder size obtained is 45 μm, and dried powder is sent into plasma spraying equipment；
(2) high-speed tool steel substrate surface to be sprayed is carried out 22 whitish eye corundum blasted rough and processes (the grains of sand of use
Material is Brown Alundum, and the granularity of the grains of sand is 25 μm), then utilize dry air that the substrate surface after sandblasting is carried out at cleaning
Reason；
(3) starting paint finishing and mechanical hand carries out plasma spraying, technological parameter is: main gas is Ar and N2, argon
Throughput is 100L/min, and the throughput of nitrogen is 20L/min；Operating current is 420A, and running voltage is 120V；Powder feeder send
Powder gas is Ar, and gas flow is 50L/min；Nozzle distance matrix distance is 10cm, and the translational speed of nozzle is 0.03m/s.
The spray-on coating thickness obtained is 3mm, consistency 98.0%.
Embodiment 3
(1) by oxide ceramic powder (aluminium oxide) powder and the additive of 35 weight portions, the described interpolation of 65 weight portions
Agent includes toughener (20wt%, 0.35 μm titanium dioxide powder), fine and close agent (32wt%, 0.5 μm dickite), fining agent
(18wt%, 0.5 μm calcium oxide), viscosifier (30wt%, 1.0 μm brass powders) powder are spray-dried, it is thus achieved that powder grain
Degree is 40 μm, and dried powder is sent into plasma spraying equipment；
(2) copper alloy substrate surface to be sprayed is carried out 24 whitish eye corundum blasted rough and processes (the grains of sand material of use
For fused alumina zirconia, the granularity of the grains of sand is 20 μm), then utilize dry air that the substrate surface after sandblasting carries out clean process；
(3) starting paint finishing and mechanical hand carries out plasma spraying, technological parameter is: main gas is Ar and N2, argon
Throughput is 120L/min, and the throughput of nitrogen is 25L/min；Operating current is 400A, and running voltage is 140V；Powder feeder send
Powder gas is Ar, and gas flow is 40L/min；Nozzle distance matrix distance is 11cm, and the translational speed of nozzle is 0.02m/s.
The spray-on coating thickness obtained is 5mm, consistency 97.5%.
Embodiment 4
(1) by ceramic powders (tungsten carbide) powder and the additive of 50 weight portions of 50 weight portions, described additive includes
Toughener (38wt%, 1.0 μm nickel by powder), fine and close agent (0.5wt%, 0.5 μm dickite), fining agent (30wt%, 0.5 μm
Barium monoxide), viscosifier (31.5wt%, 1.0 μm cuprous oxide powders) powder carry out mechanical ball milling, it is thus achieved that powder size is 40 μ
M, sends dried powder into plasma spraying equipment；
(2) high chrome substrate surface to be sprayed is carried out 24 whitish eye corundum blasted rough and processes (the grains of sand material of use
For white fused alumina, the granularity of the grains of sand is 22 μm), then utilize dry air that the substrate surface after sandblasting carries out clean process；
(3) starting paint finishing and mechanical hand carries out plasma spraying, technological parameter is: main gas is Ar and N2, argon
Throughput is 110L/min, and the throughput of nitrogen is 5L/min；Operating current is 380A, and running voltage is 130V；Powder feeder send
Powder gas is Ar, and gas flow is 30L/min；Nozzle distance matrix distance is 5cm, and the translational speed of nozzle is 0.001m/s.
The spray-on coating thickness obtained is 10mm, consistency 96.0%.
Embodiment 5
(1) by ceramic powders (tungsten carbide) powder and the additive of 50 weight portions of 50 weight portions, described additive includes
Toughener (35wt%, 1.0 μm nickel by powder), fine and close agent (30wt%, 0.5 μm dickite), fining agent (34.5wt%, 0.5 μ
M Barium monoxide), viscosifier (0.5wt%, 1.0 μm cuprous oxide powders) powder be sintered, the then broken powder size obtained
It is 40 μm, dried powder is sent into plasma spraying equipment；
(2) nickel cobalt base alloy base material surface to be sprayed is carried out 24 whitish eye corundum blasted rough and processes (the grains of sand of use
Material is Brown Alundum, and the granularity of the grains of sand is 24 μm), then utilize dry air that the substrate surface after sandblasting is carried out at cleaning
Reason；
(3) starting paint finishing and mechanical hand carries out plasma spraying, technological parameter is: main gas is Ar and N2, argon
Throughput is 130L/min, and the throughput of nitrogen is 30L/min；Operating current is 450A, and running voltage is 150V；Powder feeder send
Powder gas is Ar, and gas flow is 60L/min；Nozzle distance matrix distance is 7cm, and the translational speed of nozzle is 0.04m/s.?
To spray-on coating thickness be 10mm, consistency 96.0%.
Claims (5)
1. the ceramic coating of a metal material surface, it is characterised in that: described ceramic coating is by ceramic material and additive system
For obtaining, in ceramic coating, ceramic material is 50-90 weight portion, and additive is 10-50 weight portion；
Described additive includes ceramic toughening agent, fine and close agent, fining agent, viscosifier, the matter of ceramic toughening agent in additive
Amount percentage ratio is 0.3～40%, and the mass percent of fine and close agent is 0.5～35%, the mass percent of fining agent be 0.8～
35%, the mass percent of viscosifier is 0.5～30%；
Described ceramic material is oxide ceramic material, non-oxide ceramic material or cermet material；
Described ceramic toughening agent is the one in titanium boride, titanium carbide, aluminium oxide, rare earth oxide, titanium oxide and ferrum, molybdenum, copper
In one 9:1 or 8:2 in proportion be mixed to get；
Described compact agent is that one or more in kaolinite, montmorillonite, dickite are mixed to get in any proportion；
Described grain refiner is that one or more in magnesium oxide, calcium oxide, Barium monoxide are mixed to get in any proportion；
Described viscosifier powder is the one in cuprous oxide powder, ferrous oxide, iron suicide, ferromanganese powder, molybdenum-iron powder, brass powder
Or multiple be mixed to get in any proportion.
The ceramic coating of metal material surface the most according to claim 1, it is characterised in that: the granularity of described ceramic powders
For 0.05-60 μm；Ceramic toughening agent, fine and close agent, fining agent, the granularity of viscosifier are 0.1-1 μm.
3. the preparation method of metal material surface ceramic coating described in claim 1, it is characterised in that: specifically include following step
Rapid:
(1) weigh each raw material, use any one method of spray drying method, sintering crushing method or mechanical attrition method to break
Broken, make containing toughener, compact agent, grain refinement agent, the ceramic powders of viscosifier；
(2) metal base to be sprayed is carried out blasted rough process, then utilize dry air to the substrate surface after sandblasting
Carry out clean process；
(3) dried powder step (1) obtained is sent in the powder feeder of thermal spray system, and wherein, powder feeder powder feeding gas is
Ar, gas flow is 30-60L/min；Then the spray distance arranging manipulator control nozzle and metal base is 5-11cm, spray
The translational speed of mouth is 0.001-0.05m/s；
(4) plasma spray coating process parameter is set, starts thermal spray system and mechanical hand, after workpiece surface spraying covers once
Obtain ceramic coating.
The preparation method of metal material surface ceramic coating the most according to claim 3, it is characterised in that: institute in step (2)
Stating the grains of sand material used in blasted rough processing procedure is: white fused alumina, Brown Alundum or fused alumina zirconia, the granularity of the grains of sand is 18-25 μ
m。
The preparation method of metal material surface ceramic coating the most according to claim 3, it is characterised in that: in step (4)
Described plasma spray coating process parameter is: the throughput of argon is 90-130L/min, and the throughput of nitrogen is 5-30L/min, work
Being 350-450A as electric current, running voltage is 120-150V.
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