CN109467455A - A kind of cement matrix ceramic spraying method - Google Patents

A kind of cement matrix ceramic spraying method Download PDF

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CN109467455A
CN109467455A CN201811423115.6A CN201811423115A CN109467455A CN 109467455 A CN109467455 A CN 109467455A CN 201811423115 A CN201811423115 A CN 201811423115A CN 109467455 A CN109467455 A CN 109467455A
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powder
zirconia
cement matrix
alumina
oxide
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陈涛
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
    • C04B41/5031—Alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
    • C04B41/5042—Zirconium oxides or zirconates; Hafnium oxides or hafnates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61—Coating or impregnation
    • C04B41/65—Coating or impregnation with inorganic materials

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Coating By Spraying Or Casting (AREA)

Abstract

The invention belongs to building substrate coating treatment technical fields, and in particular to a kind of cement matrix ceramic spraying method in building.The present invention includes that (1.1) prepare cement matrix；(1.2) sandblasting is carried out to cement matrix or frosted pre-processes；(1.3) alumina raw material powder is prepared；(1.4) heated oxide aluminium sintering of nano-material powder is to molten condition；(1.5) spray aluminum oxide liquid nano material.Traditional spraying technology is that nano particle is directly placed into hot spraying in spray gun, since heating process is shorter, the melting process of particle has partial particulate and does not melt completely, is sprayed on matrix, can not meet enough strength demands and degree of adhesion demand in conjunction with effect.And sintering powder is melted into molten condition before spray gun feeds intake by the present invention, avoids this defect, and the comprehensive parameters such as the intensity, hardness, toughness of ceramic coating is made to be significantly better than the effect of usual spray techniques.

Description

A kind of cement matrix ceramic spraying method
Technical field
The invention belongs to building substrate coating treatment technical fields, and in particular to the cement matrix ceramics spray in a kind of building Coating method.
Background technique
Wall thermal insulating closes decorative energy-saving technology the 1940s originating from Europe, starts to answer in Germany and Sweden first With.Because Germany has large amount of building to be destroyed in World War II, one is pasted in order to repair out-wall crack people in exterior walls of buildings Strata styrene or rock wool board mend a split.In the near future it is found that this way can not only cover crack there are also it is many its His the advantages of: heat preservation, sound insulation, humidity resistance greatly improve, and residence comfort also greatly improves.The U.S. uses exterior-wall heat insulation The time of power-saving technology is shorter, is just begun to use in later period the 1960s.The power-saving technology of wall thermal insulating closing decoration Really being rapidly developed is due to energy shortage, while to have obtained European and American countries political affairs after world energy sources crisis in 1973 The market capacity of the promotion energetically at mansion, External Thermal Insulation Technology for External is increased rapidly with annual 15% speed.Due to American-European stringent Legislation demands, the energy-saving efficiency of the new building of America and Europe's same latitude is about 2 times~3 times of China at present.
The power-saving technology of China's wall thermal insulating closing decoration is started in the 1980s, being limited by prevailing condition, mainly Some applications have been done in terms of exterior wall internal insulation, have been mainly used in northern China cool region at the beginning, by practice, exterior wall Inside holding technology is increasingly appeared in northern cold and using the defect in heat supply heating area, due to the excessive easy formation of indoor/outdoor temperature-difference The problems such as condensed water.On the basis of study and Importing Foreign Advanced Technology, External Thermal Insulation Technology for External is gradually in China nearly ten years Ground grows up, and the development of external walls heating insulation is substantially synchronous with world's holding at present.
For national planning using energy-saving and emission-reduction as one of focus, the building energy conservation as wherein important component will Push more flourishing for wall thermal insulating closing decoration industry.But in recent years, closing decorative system is kept the temperature with construction wall Related fire frequently occurs, and makes hidden danger expression nothing left existing for the fire savety of construction wall heat preservation closing decorative system.
With the great-leap-forward development of the global manufacturing Second Revolution, the dress such as various productions, process equipment, assembly type components It sets higher and higher to surface abrasion resistance, skid-resistant, the resistance to performance requirement scratched.Obviously, if building it is whole according to wall it is whole Production cost can be not only greatly improved in the excellent material of equal service performance, Lai Tigao surface property, nor is conducive to save energy The environmental protection such as source and raw material sexual factor, this is clearly not scientific also without realistic meaning, therefore the superficiality of research material The research direction that important meaning is all had in terms of producing with scientific research can be become.
In the surface treatment processing engineering technology of huge number, thermal spraying, which is relatively common, and cost performance is higher changes Become one of material technological means of surface property itself, nowadays the technical method of thermal spraying plated film is in electronic device product, aviation Aerospace industry, derived energy chemical equipment, mechanical engineering processing, life products improvement, communications and transportation product manufacturing etc. are almost all of It is all widely used in national economy production industry, and obtains critical role in high-technology field.Thermal spraying is Refer to and use different hot spraying methods, plated film spray process is modified to material surface, so that the surface of material is with resistance to The processing method of mill, corrosion-resistant, resistance to oxidation or the performances such as conduction and insulation.Plasma spray technology can also be to damaged surfaces Material repaired and remanufactured, to obtain the attention of each industrial manufacturing sector.
Above-mentioned plasma spray technology according to technological means classification specifically include that electric arc spraying, flame-spraying, plasma spraying, The modes such as supersonic spray coating, detonation flame spraying all have wide application in this field with upper type.Wherein, plasma arc sprays Painting is using high-temperature plasma arc heat source, using powder as a kind of spraying method of sprayed on material.High-temperature plasma arc is mainly by straight Galvanic electricity arc and high-frequency induction electric arc generate, be mostly in the market using the high-temperature plasma arc that direct-current arc generates as heat source, with The working gas as spraying such as argon gas, hydrogen, the powdery metal or ceramic material of spraying are then will by gas or liquid In its plasma arc jet stream for being sent into high temperature and high speed, powder is heated and is accelerated in plasma arc heat source.Heating makes former material Material forms fusing or semi-molten state, and acceleration enables the very fast injection of material to workpiece surface, to sprawl rapidly, be set in base Material surface, a piece of coating for covering a piece of one layer of covering, one layer of formation lamellar packed structures, as shown in Figure 1.
The stability of plasma arc spraying method is fine, and can be by controlling spraying method during spray mo(u)lding Parameters, to obtain the spray-on coating of high quality.Particle during coating preparation, in plasma arc jet stream Flying speed is high, and after hitting with matrix, serious deformation can occur for the particle of fusing or semi-molten, at the same time base Body also will receive biggish impact force, and the particle after shock then can uniformly spread over and form coating on matrix.Coating and matrix Between bond strength depend on coating consistency, the intensity of coating with the increase of the binding force among coating and matrix and Enhancing.The coating of high quality is usually to pass through adjusting technological parameter, reduces the oxide inclusion content in coating and obtains.In addition The thickness of coating can be by adjusting spray time to efficiently control, and the surface of coating can also be flat and smooth after being ground. Compared to other spraying technologies, when being sprayed using plasma arc to part, the plasma arc jet stream of high temperature is to part The influence on surface is smaller, and the influence to the reheating of matrix is smaller, and matrix is notheated generation change.Plasma arc spray The heat source that painting technology uses is higher than the heat source temperature that other spraying technologies use for plasma arc jet stream, can make to spray material Material generates the state of fusing, part fusing, to prepare a greater variety of coatings, furthermore Plasma Arc Spraying Equipment is lightly clever It is living, it is readily produced operation, and in a large amount of continuous productions, the deposition efficiency of prepares coating is high, noise is small.
However, the granularity of the powder of spraying raw material be the coating level of plasma arc spraying a critically important influence because Element, when the partial size of powder particle is too small, powder is easy to block spraying pipeline in transmit process, so that spraying is difficult to carry out, when When the partial size of powder is excessive, powder in the jet be heated is not thorough, cannot dissolve completely, coating it is second-rate.And numerous Plasma arc ceramic spraying material in, due to the ABUNDANT NATUREAL RESOURSES of aluminium oxide ceramics raw material, low production cost, and it is hard Spend higher, coefficient of friction is less than normal, and chemical stability is more excellent compared with same type of material, has good wear-resistant and insulation performance, can Extend the service life of building substrate effectively, by the favor of domestic and international researcher.It is sprayed using atmospheric plasma arc Technology prepares alumina ceramic coating, and thickness can be from some tens of pm to several millimeters, because its is excellent wear-resisting, corrosion-resistant and insulation Performance can significantly improve the service life of product.
Summary of the invention
The purpose of the present invention is to provide a kind of at low cost, good, heat-insulated, moistureproof and mildewproof cement matrix ceramics of wear-resisting property Spraying method.
A kind of cement matrix ceramic spraying method, comprises the following steps that
(1.1) cement matrix is prepared:
Cement matrix is set up according to cement matrix model or design；
(1.2) sandblasting is carried out to cement matrix or frosted pre-processes；
(1.3) alumina raw material powder is prepared:
Alumina powder is passed through deionized water as dispersing agent by (1.3.1), and oxidation aluminium paste is made in alumina powder；
(1.3.2) is evenly spread out alumina powder using ultrasonic activation in deionized water；
Binder solution is added in oxidation aluminium paste in (1.3.3), and mixed slurry is put into ball milling 2 hours in ball mill, Mix aluminum oxide nanoparticle and binder uniformly；
Uniformly mixed oxidation aluminium paste is put into drying box and is dried by (1.3.4), makes to aoxidize aluminium paste solidification, then will Block-like alumina powder is crushed, is sieved, and the aluminum oxide nanoparticle of micron-scale is formed；
(1.3.5) carries out high temperature sintering to aluminum oxide nanoparticle, and sintering temperature is at 1100 degrees Celsius to 1200 degrees Celsius Between, grinding obtains aluminium oxide nano sintering powder after ten minutes for heat preservation；
(1.4) heated oxide aluminium sintering of nano-material powder is to molten condition；
Aluminium oxide nano sintering powder is heated to liquid melt state using electric heater unit；
(1.5) spray aluminum oxide liquid nano material:
The anode of power supply, cathode are connected to the anode of coating spray gun, on cathode by (1.5.1), make electric current by by Hydrogen, helium, argon and nitrogen composition mixed gas chamber and puncture and generate electric discharge generate plasma arc between a cathode and an anode Jet stream；
(1.5.2) makes high pressure draught blow over the aluminium oxide of plasma arc jet stream and the liquid melt state poured into according to flow Alumina material is blown out spray gun, sprayed to cement matrix by material；
(1.5.3) cooling coating makes aluminium oxide nano fluent material form aluminium oxide liquid ceramic coating.
The heated oxide aluminium sintering of nano-material powder refers to molten condition is burnt aluminium oxide nano using electric heater unit Knot powder is heated to liquid melt state.
The blasting treatment refers to: utilizing compressed air, sand grains is turned in sand-blasting machine to cement matrix surface, compression The pressure of air is 0.7MPa；When being surface-treated using sandblasting to cement matrix, Spray gun nozzle and cement matrix are formed 45 degree Angle, and at the uniform velocity moved from one end of cement matrix to the other end, using compressed air to cement matrix after blasting treatment Surface is cleared up, and cement matrix will carry out plasma arc spraying immediately after blasting treatment.
The jet stream is answered orthogonal with cement matrix surface.
Also mixed with zirconia material powder in alumina raw material powder in the step (1.3), zirconia material powder is adopted It is obtained with following steps:
It takes quantitative urea and zirconium nitrate to be dissolved in deionized water and is configured to zirconium nitrate mixed liquor；By 1 part of mass fraction Span-80 is added in the container for filling 10 parts of dimethylbenzene, with electric mixer to two in container during addition Span-80 Toluene mixture liquid is stirred, and when the dimethylbenzene mixed liquor in container becomes uniform, 1 part of prepared nitre is added into container Sour zirconium mixed liquor obtains white emulsion after emulsifying half an hour, emulsion is poured into reaction kettle, and after reaction kettle is sealed It is put into 120 degrees Celsius of baking oven and is reacted, taking-up reaction kettle is opened instead after it is cooled to room temperature after reacting 15 hours Kettle is answered to sample to obtain white crystal；White crystal obtains white powder after being filtered, washed, and reacts as follows:
CO(NH2)2+4H20→2NH3·H2O+H2CO3；
H2CO3→2H++CO3 2-；
NH3·H2O→NH4 ++OH-；
2OH-+CO3 2-+Zr4+→Zr(OH)2CO3↓；
White powder is put into drying in vacuum oven and for 24 hours, obtains the presoma of zirconia material powder；By what is obtained Precursor powder is put into Muffle furnace, obtains zirconia material powder after calcining 3 hours under 500 degrees Celsius.
Also mixed with zirconia material powder in alumina raw material powder in the step (1.3), the zirconium oxide is former Feed powder end is obtained using following steps:
Chlorine hydrate Zirconium oxide powder is weighed, chlorine hydrate Zirconium oxide powder is dissolved in deionized water, it is dense to obtain zirconium Degree is in the clarified solution of 0.1mol/L；The ammonium hydroxide that mass fraction is 26-27% is diluted to the NH that concentration is 1mol/L3·H2O is molten Liquid, the NH after dilution is slowly added dropwise in the clarified solution of Xiang Shangshu basic zirconium chloride3·H2Suspension is formed after O solution, determines suspension PH value be 8.5；Suspension is separated with centrifuge, is obtained Zr (OH)4Hydrate deposition then cleans precipitating with deionized water, Then it is centrifuged again, this process repeats 5-6 times, until chloride ion and ammonium ion are removed completely；By mass fraction The HNO that concentration is 2mol/L is diluted to for the nitric acid of 66-67%3Solution；HNO3 and quality point after dilution is added into precipitating The hydrogen peroxide that number is 30% forms the turbid solution of white；Finally white opacity solution is packed into container, is placed on magnetic agitation Uniform stirring on device waits and dispergation reaction occurs, clarifies after one day, measure the colloidal sol of clear；By the dioxy of clear Change zirconium colloidal sol heating evaporation moisture at 80 degrees celsius, obtain zirconium dioxide xerogel, then carries out calcining point in the lehr Solution, keeps the temperature 5min after being heated to set temperature with the heating rate of 10 centigrade per minutes, the cooled to room temperature in furnace；Most It is ground afterwards with agate mortar, 200 mesh screens fall impurity and large-size particles to get calcined white oxide zirconium raw material powder is arrived End.
It is described also mixed with yttria-stabilized zirconia superfine powder in alumina raw material powder in the step (1.3) Yttria-stabilized zirconia superfine powder using following steps obtain:
Weigh quantitative precipitating reagent NH4HCO3It is added in reactor with Surfactant PEG 4000, then slow from feed opening ZrOCl is added dropwise2·8H2O and stabilization agent Y (NO3)3·6H2After reaching the reaction time, reaction solution is taken out for the mixed solution of O, Through filtering, deionized water washing, decompression filter, secondary deionized water washing, decompression filter, dehydrated alcohol washing, decompression filter, Secondary dehydrated alcohol washing, decompression obtain the presoma of yttria-stabilized zirconia after filtering, then by presoma at 75 degrees Celsius Vacuum environment under dry 8 hours, it is finally certain in Muffle furnace then the agate mortar grinding distribution of the product after drying Yttria-stabilized zirconia superfine powder is received after temperature calcination.
A kind of cement matrix ceramic spraying method, includes the following steps:
(8.1) cement matrix is chosen；
(8.2) sandblasting pretreatment is carried out to cement matrix；
(8.3) alumina-zirconia composite ceramic material is prepared；
Aluminium oxide nano is sintered powder, zirconia nanopowder sintering powder and Al by (8.3.1)2O3-SiO2- CaO is complex sintered In the proportionally loading ball grinder of auxiliary agent；
(8.3.2) is added alcohol and abrading-ball and is placed on roller grinder, ball, material, alcohol ratio be 8:1:1, adjust Revolving speed ball milling 20-24h；
Suspension after ball milling is placed in pallet by (8.3.3), and 80 degrees Celsius are dried for standby；
(8.3.4) weighs mixed material powder, is placed in molding die, is forced into 200-300MPa pressure maintaining 15s, takes off Powder base is obtained after mould and is dried at 50 degrees Celsius；
(8.3.5) is normal pressure-sintered to obtain alumina-zirconia composite ceramic material；
(8.4) alumina-zirconia composite ceramic material powder is prepared respectively:
Then (8.4.1) passes through deionized water conduct respectively by alumina-zirconia composite ceramic material grind into powder Alumina-zirconia composite ceramic material slurries are made in alumina-zirconia composite ceramic material powder by dispersing agent；
(8.4.2) using ultrasonic activation respectively by alumina-zirconia composite ceramic material powder in deionized water It evenly spreads out；
Binder solution is added in alumina-zirconia composite ceramic material slurries in (8.4.3), and mixed slurry is put Enter ball milling 2 hours in ball mill, mixes the nano particle of alumina-zirconia composite ceramic material and binder uniformly；
Uniformly mixed alumina-zirconia composite ceramic material slurries are put into drying box and are dried by (8.4.4), Make alumina-zirconia composite ceramic material grout cures, then by block-like alumina-zirconia composite ceramic material powder It crushed, be sieved, form the alumina-zirconia composite ceramic material nano particle of micron-scale；
(8.4.5) carries out high temperature sintering to alumina-zirconia composite ceramic material nano particle, and sintering temperature is 1100 Degree Celsius between 1200 degrees Celsius, grinding obtains alumina-zirconia composite ceramic material sintering of nano-material after ten minutes for heat preservation Powder；
(8.5) heated oxide aluminium/zirconia composite ceramics material nano is sintered powder to molten condition；
Alumina-zirconia composite ceramic material sintering of nano-material powder is heated to liquid melt shape using electric heater unit State；
(8.6) spray aluminum oxide/zirconia composite ceramics liquid nano material:
The anode of power supply, cathode are connected to the anode of coating spray gun, on cathode by (8.6.1), make electric current by by Hydrogen, helium, argon and nitrogen composition mixed gas chamber and puncture and generate electric discharge generate plasma arc between a cathode and an anode Jet stream；
(8.6.2) makes high pressure draught blow over the oxidation of plasma arc jet stream and the liquid melt state poured into according to flow Alumina-zirconia composite ceramic material is blown out spray gun, injection to shape on cement matrix by aluminium/zirconia composite ceramics material At aluminium oxide liquid ceramic coating.
The zirconium oxide is 8% in the mass ratio of alumina-zirconia composite ceramic material.
A kind of cement matrix ceramic spraying method, includes the following steps:
(10.1) cement matrix is chosen:
(10.2) sandblasting is carried out to cement matrix or frosted pre-processes:
(10.3) zirconia material powder is prepared:
Zirconium oxide powder is passed through deionized water as dispersing agent by (10.3.1), and zircon oxide slurry is made in Zirconium oxide powder；
(10.3.2) is evenly spread out zirconia powder using ultrasonic activation in deionized water；
Binder solution is added in (10.3.3) in zircon oxide slurry, and mixed slurry is put into ball milling 2 hours in ball mill, Mix Zirconium oxide nano grain and binder uniformly；
Uniformly mixed zircon oxide slurry is put into drying box and is dried by (10.3.4), solidifies zircon oxide slurry, then Block-like Zirconium oxide powder is crushed, is sieved, the Zirconium oxide nano grain of micron-scale is formed；
(10.3.5) carries out high temperature sintering to Zirconium oxide nano grain, and sintering temperature is at 1600 degrees Celsius to 1900 degrees Celsius Between, grinding obtains zirconia nanopowder sintering powder after ten minutes for heat preservation；
(10.4) heated oxide zirconium sintering of nano-material powder is to molten condition:
(10.5) spraying zirconia nanopowder fluent material forms zirconium oxide liquid ceramic coating.
The beneficial effects of the present invention are: a kind of cement matrix ceramic spraying method provided by the invention, by ceramic coating Thermal jet is applied to cement matrix, instead of traditional ceramic integral forming technique, effectively reduces outer casing thickness, reduces cement base Body surface surface treatment cost, the method furthermore prepared through the invention is in order to coating material can preferably be combined with cement matrix Together, matrix, can biggish its surface roughness of raising after sandblasting post-processes.When carrying out plasma arc spraying, warp Arc Plasma Heating and the powder particle for melting or dissolving, rapid flight to coarse matrix surface, and between matrix mutually It is mutually engaged, therefore, the coating and matrix of plasma arc spraying technology preparation are mechanical bond.In addition blasting treatment is also to activation Matrix surface improves the residual stress on cement matrix surface.Core of the invention step is in spray aluminum oxide or zirconium oxide etc. Melting step before liquid nano material, traditional spraying technology are that nano particle is directly placed into hot spraying in spray gun, Since heating process is shorter, the melting process of particle has partial particulate and does not melt completely, is sprayed on matrix, in conjunction with effect Fruit can not meet enough strength demands and degree of adhesion demand.And sintering powder is melted by the present invention before spray gun feeds intake Molten condition avoids this defect, makes the comprehensive parameters such as the intensity, hardness, toughness of ceramic coating significantly better than usual spray The effect of technology.
Detailed description of the invention
Fig. 1 is plasma arc spraying schematic diagram；
Fig. 2 is the process flow diagram of alumina-zirconia composite ceramic material and complex sintering aids；
Fig. 3 is powder feeding (liquid oxidatively aluminium) rate VZ, liquid oxidatively zirconium powder sending quantity GZRelational graph；
Fig. 4 is liquid oxidatively aluminium powder sending quantity GZ, gas flow SZRelational graph；
Fig. 5 is the flow S of gasZ, spray power and spray distance DZRelational graph；
Fig. 6 is overall flow figure of the present invention.
Specific embodiment
The present invention is described further with reference to the accompanying drawing.
Embodiment 1
The invention proposes a kind of high rigidity, high-wearing feature, the cement matrix ceramic spraying method of high degree of safety, such as Fig. 6 Shown, steps are as follows for main body:
(1) cement matrix is prepared:
The selection of matrix should select the extensive cost-effective of material source, and cutting difficulty is low, the higher cement class material of intensity Material should also select still be able to maintain certain plasticity, wearability and tough after the processing of the high heat condition of high temperature when necessary The material of property.
(2) cement matrix is pre-processed: sandblasting or frosted processing:
In order to allow what ceramic coating raw material and matrix can be closer to be combined together, need to spray cement matrix Sand or frosted processing.The roughness of matrix surface can be greatly improved in the step.When carrying out plasma arc spraying, through plasma arc Heating and melt or the ceramic powder particle that dissolves, rapidly spray to coarse matrix surface, and with cement matrix it Between it is engaged, therefore, plasma arc spraying preparation ceramic coating and matrix be mechanical bond.In addition sandblasting or frosted Processing can also activated cement matrix surface, improve cement matrix surface residual stress.
(3) zirconium oxide (ZrO is prepared2) raw material powder:
By deionized water zircon oxide slurry is made as dispersing agent in Zirconium oxide powder by Zirconium oxide powder；
Zirconia powder is evenly spread out in deionized water using ultrasonic activation；
Binder (PVA) solution is added in zircon oxide slurry, and mixed slurry is put into ball milling 2 hours in ball mill, makes Zirconium oxide nano grain and binder uniformly mix；
Uniformly mixed zircon oxide slurry is put into drying box and is dried, zircon oxide slurry is solidified, it then will be block-like Zirconium oxide powder is crushed, is sieved, and the Zirconium oxide nano grain of micron-scale is formed；
High temperature sintering is carried out to Zirconium oxide nano grain, sintering temperature is protected between 1600 degrees Celsius to 1900 degrees Celsius Grinding obtains zirconia nanopowder sintering powder to temperature after ten minutes.
First zirconia powder is washed with deionized water before calcined zirconia nano particle, then for several times with ethanol washing, it can be with It avoids remaining in anion in zirconia powder to generate salt bridge effect and generate since the surface tension of deionized water is excessive Capillarity forms H-O-H to prevent to put up a bridge between HO- so as to cause generation reunion in nanometer powder.
(4) heated oxide zirconium sintering of nano-material powder is to molten condition；
Zirconia nanopowder sintering powder is heated to liquid melt state using electric heater unit；
Melting of the core of the invention step before spraying zirconia nanopowder fluent material, traditional zirconium oxide spray coating technology It is that Zirconium oxide nano grain is directly placed into hot spraying in spray gun, since heating process is shorter, the melting of zirconia particles Process has partial particulate and does not melt completely, is sprayed on cement matrix, can not meet in conjunction with effect enough strong Degree demand and degree of adhesion demand.And sintering powder is melted into molten condition before spray gun feeds intake by the present invention, avoids this lack It falls into, the comprehensive parameters such as the intensity, hardness, toughness of ceramic coating is made to be significantly better than the effect of usual spray techniques.
(5) zirconia nanopowder fluent material is sprayed:
The anode of power supply, cathode are connected to the anode of coating spray gun, on cathode, pass through electric current by hydrogen, helium, argon And nitrogen composition mixed gas chamber and puncture and generate electric discharge between a cathode and an anode generate plasma arc jet stream；Make height Pressure gas stream blows over the zirconia material of plasma arc jet stream and the liquid melt state poured into according to flow, and zirconia material is blown Spray gun out is sprayed to cement matrix.Jet stream is answered orthogonal with cement matrix surface.
When carrying out plasma arc spraying zirconia material, need to control powder feeding (liquid oxidatively zirconium) rate VZ, liquid oxygen Change zirconium powder sending quantity GZ, gas flow SZ, spray power and spray distance DZ, unit cm.When powder feeding rate is excessive, powder End is easy blocking powder feeding pipe, causes to spray, or cause spray efficiency low because powder feeding rate is too small, causes resource unrestrained Take.
Further, meet:
600m/s≥VZ≥200m/s；As shown in Figure 3；
As shown in Figure 4；
As shown in Figure 5；
It is further: 1000g/min >=GZ≥3500g/min；2000m3/d≥SZ≥19500m3/d。
As shown in Figure 3, the present invention simulates 10000 powder feedings (liquid oxidatively zirconium) rate V firstZ, liquid oxidatively zirconium Powder sending quantity GZDiscrete values point, discrete numerical point is fluctuation point, and the midpoint between continuous two o'clock is taken to carry out twice in succession Conic fitting obtains the scatter plot of Fig. 3 and obtains curve graph.Fig. 4 and Fig. 5 are similarly obtained.It can be with by above-mentioned formula The effectively parameter of control zirconia coating.
The present invention has been fitted every ginseng when plasma arc spraying zirconia material by data statistics and chemical simulation Number relationships, if sending point rate too fast or excessively slow, coating layer thickness is not easy to control, causes liquid to be subcooled or overheat, causes to apply Layer chemical property changes, and influences coating quality.And other parameters the problems such as also cost being caused to waste.
The working gas of equipment is mainly argon gas (main gas), hydrogen (secondary gas) and nitrogen (powder feeding gas).Main gas The performance of plasma arc is determined with the flow of secondary gas, hydrogen can improve the viscosity of the zirconia material of Arc Plasma Heating, Make zirconia material with more cohesiveness.The distance of spray gun should be moderate when spraying, if too close, the zirconia ceramics sprayed When powder is rapidly impinged upon on cement matrix, can generate and hit winged phenomenon, can not form uniform zirconia coating, and spray away from Too far away, the zirconia material sprayed may exhaust kinetic energy on the path of flight or because temperature reduces, and lead to not Form coating.In spray-on coating on cement matrix, prolonged spraying will lead to the raising of cement matrix temperature, due to formation The thermal expansion coefficient of coating and cement matrix is inconsistent, so when being cooled to room temperature, it may occur that the phenomenon that coating shedding, because This when spraying cement matrix needs that compressed air is used to cool down cement matrix as cooling gas.
The blasting treatment refers to:
Using compressed air, sand grains is turned in sand-blasting machine to cement matrix surface, the pressure of compressed air is about 0.7MPa.It when being surface-treated cement matrix using sandblasting, needs Spray gun nozzle and cement matrix forming 45 degree of angles, thus anti- The only surface of sand grains insertion cement matrix, and at the uniform velocity moved from one end of cement matrix to the other end, when cement matrix surface Completely it is coarse after, sandblasting complete.Cement matrix by blasting treatment firstly the need of use compressed air to cement matrix surface It is cleared up, prevents cement matrix remained on surface from having sand grains, next needs to carry out oil removing to cement matrix surface using acetone, prevents Sealing mud matrix surface greasy dirt impacts spraying result, in addition, in order to avoid the cement matrix surface after sandblasting is dirty again Dye, cement matrix need plasma arc spraying immediately after sandblasting.
Embodiment 2
A kind of cement matrix ceramic spraying method, includes the following steps:
(1) cement matrix is chosen:
Determine the cement matrix of zirconium oxide liquid ceramic spraying, the selection selection extensive cost of material source of cement matrix is suitable Preferably, and cutting difficulty is low, the higher cement material of intensity, should also select after the processing of the high heat condition of high temperature when necessary Still it is able to maintain the cement material of certain plasticity, wearability and toughness.
(2) cement matrix is pre-processed: sandblasting (frosted) processing.
The blasting treatment refers to:
Using compressed air, sand grains is turned in sand-blasting machine to cement matrix surface, the pressure of compressed air is about 0.7MPa.When being surface-treated using sandblasting to cement matrix, Spray gun nozzle and cement matrix are formed into 45 degree of angles, and from cement One end of matrix is at the uniform velocity moved to the other end, is cleared up using compressed air cement matrix surface after blasting treatment, Oil removing is carried out to cement matrix surface using acetone, cement matrix needs plasma arc spraying immediately after sandblasting.
(3) zirconium oxide/alumina composite ceramic material is prepared:
First by zirconia material powder, alumina raw material powder and Al2O3-SiO2- CaO complex sintering aids according to Ratio is fitted into ball grinder.Be added a certain amount of alcohol and abrading-ball (ball, material, alcohol ratio be 8:1:1) be placed in idler wheel and grind On grinding machine.Adjust revolving speed (1000r/min-1200r/min) ball milling 20-24h.Suspension after ball milling is placed in pallet, 80 take the photograph Family name's degree is dried for standby.Mixed material powder is weighed, is placed in molding die, 200-300MPa pressure maintaining 15s is forced into, is demoulded Powder base is obtained afterwards and is dried at 50 degrees Celsius.It is normal pressure-sintered.
0~200 degree Celsius of heating rate is 3 centigrade per minutes when being sintered in the early stage.Steam the Free water in powder base Hair；200~500 degrees Celsius, heating rate is 1.5 centigrade per minutes, allows binder sufficiently to decompose, powder base is slowly discharged. 500~1000 degrees Celsius, heating rate is 5 centigrade per minutes, can avoid growing up for crystal grain, saves sintering time.In temperature At 1000~1200 degrees Celsius, heating rate is 2 centigrade per minutes, and keeps the temperature 2 hours at 1200 degrees Celsius, and help improves m- ZrO2Also it can reduce the generation of internal stress while phase variable.Heating rate is after temperature is elevated above 1200 degrees Celsius 2.5 centigrade per minutes, Al2O3-SiO2- CaO complex sintering aids start to be changed into molten condition, help to create liquid phase and exist Diffusion in powder base.Zirconium oxide/alumina composite ceramic material is promoted to realize low temperature densification sintering.Keep the temperature the regular hour it After cool to room temperature with the furnace zirconium oxide/alumina composite ceramic material can be obtained.As shown in Figure 2.
(4) zirconium oxide/alumina composite ceramic material powder is prepared:
Respectively by zirconium oxide/alumina composite ceramic material grind into powder, then by deionized water as dispersing agent, Zirconium oxide/alumina composite ceramic material slurry is made in zirconium oxide/alumina composite ceramic material powder；
It is respectively that zirconium oxide/alumina composite ceramic material powder is evenly dispersed in deionized water using ultrasonic activation It opens；
Binder (PVA) solution is added in zirconium oxide/alumina composite ceramic material slurry, and mixed slurry is put into Ball milling 2 hours in ball mill mix zirconium oxide/alumina composite ceramic material nano particle and binder uniformly；
Uniformly mixed zirconium oxide/alumina composite ceramic material slurry is put into drying box and is dried, makes to aoxidize Zirconium/alumina composite ceramic material slurry solidification, then carries out powder for block-like zirconium oxide/alumina composite ceramic material powder Broken, sieving, forms zirconium oxide/alumina composite ceramic material nanoparticle of micron-scale；
High temperature sintering is carried out to zirconium oxide/alumina composite ceramic material nanoparticle, sintering temperature is at 1100 degrees Celsius To between 1200 degrees Celsius, grinding obtains zirconium oxide/alumina composite ceramic material nano sintering powder after ten minutes for heat preservation.
Aluminium oxide is 12% in the mass ratio of integral material.
(5) heated oxide zirconium/alumina composite ceramic material nano is sintered powder to molten condition:
Zirconium oxide/alumina composite ceramic material nano sintering powder is heated to liquid melt shape using electric heater unit State；
(6) zirconium oxide/alumina composite ceramic liquid nano material is sprayed:
The anode of power supply, cathode are connected to the anode of coating spray gun, on cathode, pass through electric current by hydrogen, helium, argon And nitrogen composition mixed gas chamber and puncture and generate electric discharge between a cathode and an anode generate plasma arc jet stream；Make height Pressure gas stream blows over zirconium oxide/alumina composite ceramic material of plasma arc jet stream and the liquid melt state poured into according to flow Zirconium oxide/alumina composite ceramic material is blown out spray gun, sprayed to cement matrix by material.Jet stream is answered with cement matrix surface It is orthogonal.
By experimental analysis, influence to relative density, three bending strength, Vickers hardness performance indicators, each factor Primary and secondary sequence is sintering temperature > ZrO2Content > sintering aid additive amount > soaking time.Optimal preparation process is, aoxidizes The additive amount of aluminium is 21% (mass fraction), and the additive amount of sintering aid is 5%, soaking time 3h.Zirconium oxide/aluminium oxide is multiple The mechanical property for closing ceramic coating is best.Zirconium oxide/the alumina composite ceramic prepared under this process condition is opposite Density is up to 94%, Vickers hardness 965MPa, bending strength 286MPa, fracture toughness 4.52MPa/m2。
Traditional ZrO2Ceramic material, toughness is strong but hardness is lower, and the present invention uses Al2O3-SiO2- CaO is complex sintered to be helped Agent is by single-phase Al2O3High-temperature phase-change humidification introduces ZrO2In ceramic material, zirconium oxide/alumina composite ceramic material is made to exist , there are aluminium oxide ceramics high rigidity, high intensity in the characteristics of mechanical property aspect, existing zirconia ceramics high tenacity again.
Embodiment 3
All steps are identical as embodiment 1 or embodiment 2, and difference is, the zirconia material powder is using as follows Step obtains:
It takes quantitative urea and zirconium nitrate to be dissolved in deionized water and is configured to zirconium nitrate mixed liquor；By 1 part of mass fraction Span-80 is added in the container for filling 10 parts of dimethylbenzene, with electric mixer to two in container during addition Span-80 Toluene mixture liquid is stirred, and when the dimethylbenzene mixed liquor in container becomes uniform, 1 part of prepared nitre is added into container Sour zirconium mixed liquor obtains white emulsion after emulsifying half an hour, emulsion is poured into reaction kettle, and after reaction kettle is sealed It is put into 120 degrees Celsius of baking oven and is reacted, taking-up reaction kettle is opened instead after it is cooled to room temperature after reacting 15 hours Kettle is answered to sample to obtain white crystal；White crystal obtains white powder after being filtered, washed, and reacts as follows:
CO(NH2)2+4H20→2NH3·H2O+H2CO3
H2CO3→2H++CO3 2-
NH3·H2O→NH4 ++OH-
2OH-+CO3 2-+Zr4+→Zr(OH)2CO3↓
White powder is put into drying in vacuum oven and for 24 hours, obtains the presoma of zirconia material powder.By what is obtained Precursor powder is put into Muffle furnace, obtains zirconia material powder after calcining 3 hours under 500 degrees Celsius.
Embodiment 4
All steps are identical as embodiment 1,2 or embodiment 3, and difference is, the zirconia material powder is using such as Lower step obtains:
Weigh chlorine hydrate zirconium oxide (ZrOCl2·8H2Chlorine hydrate Zirconium oxide powder is dissolved in deionization by O) powder In water, obtain in the clarified solution that zirconium concentration is 0.1mol/L；The ammonium hydroxide that mass fraction is 26-27%, which is diluted to concentration, is The NH of 1mol/L3·H2O solution, the NH after dilution is slowly added dropwise in the clarified solution of Xiang Shangshu basic zirconium chloride3·H2Shape after O solution At suspension, determine that the pH value of suspension is 8.5.Suspension is separated with centrifuge, is obtained Zr (OH)4Hydrate deposition, then Precipitating is cleaned with deionized water, is then centrifuged again, this process repeats 5-6 times, until chloride ion and ammonium ion are complete It is removed entirely.The nitric acid that mass fraction is 66-67% is diluted to the HNO that concentration is 2mol/L3Solution.It is added into precipitating dilute The hydrogen peroxide that HNO3 and mass fraction after releasing are 30%, forms the turbid solution of white.Finally white opacity solution is packed into In container, it is placed on uniform stirring on magnetic stirring apparatus, waits and dispergation reaction occurs, clarified after one day, measure the molten of clear Glue.By the zirconia sol of clear heating evaporation moisture at 80 degrees celsius, zirconium dioxide xerogel is obtained, is then existed Calcining and decomposing is carried out in annealing furnace, 5min is kept the temperature after being heated to set temperature with the heating rate of 10 centigrade per minutes, in furnace Interior cooled to room temperature.It is finally ground with agate mortar, 200 mesh screens fall impurity and large-size particles to get calcining is arrived White oxide zirconium raw material powder afterwards.
For the method for embodiment 3 and embodiment 4, used in low in raw material price, easy to operate and energy Guarantee the quality of oxide powder, and can control the pattern of zirconium oxide agglomerate powder, sphericity good oxidation zirconium can be prepared Powder.It is spherical powder by melted powder prepared by this method, there is good delivery efficiency.
Embodiment 5
All steps are identical as embodiment 1,2,3 or embodiment 4, and difference is, the phase of the zirconia material powder Parameter is closed to be set according to coating needs, specific as follows:
The anti-crack of coating expands power setting are as follows:
Wherein G is that the anti-crack of coating expands power；
α is the half of the coat side impression diagonal line given threshold of setting；
β is the average length of crystal of zirconium oxide surface void；
P is load threshold value；
The hardness of coating surface are as follows:
P=K (h-hd)t
AOC is projected contact area, and K and t are system fitting parameter, hdFor the displacement after unloading completely, hgIt is deep for contact Degree, h is compression distance,To be pressed into pressure head geometric shape parameters；Be S be contact stiffness.
The above method expands the hardness of power and surface by the anti-crack that the setting to each parameter can effectively control coating, The parameter that coating is controlled according to the property of different cement matrixes, is conducive to different product and adjusts different coating parameters.
Embodiment 6
A kind of cement matrix ceramic spraying method, includes the following steps:
(1) cement matrix is chosen:
Determine the cement matrix of zirconium oxide liquid ceramic spraying, the selection selection extensive cost of material source of cement matrix is suitable Preferably, and cutting difficulty is low, the higher material of intensity, should also select to remain to after the processing of the high heat condition of high temperature when necessary Keep the material of certain plasticity, wearability and toughness.
(2) cement matrix is pre-processed: sandblasting (frosted) processing
The blasting treatment refers to:
Using compressed air, sand grains is turned in sand-blasting machine to cement matrix surface, the pressure of compressed air is about 0.7MPa.When being surface-treated using sandblasting to cement matrix, Spray gun nozzle and cement matrix are formed into 45 degree of angles, and from cement One end of matrix is at the uniform velocity moved to the other end, is cleared up using compressed air cement matrix surface after blasting treatment, Oil removing is carried out to cement matrix surface using acetone, cement matrix needs plasma arc spraying immediately after sandblasting.
(3) yttria-stabilized zirconia superfine powder is prepared:
Weigh quantitative precipitating reagent NH4HCO3It is added in reactor with Surfactant PEG 4000, then slow from feed opening ZrOCl is added dropwise2·8H2O and stabilization agent Y (NO3)3·6H2After reaching the reaction time, reaction solution is taken out for the mixed solution of O, Through filtering, deionized water washing, decompression filter, secondary deionized water washing, decompression filter, dehydrated alcohol washing, decompression filter, Secondary dehydrated alcohol washing, decompression obtain the presoma of yttria-stabilized zirconia after filtering, then by presoma at 75 degrees Celsius Vacuum environment under dry 8 hours, it is finally certain in Muffle furnace then the agate mortar grinding distribution of the product after drying Yttria-stabilized zirconia superfine powder is received after temperature calcination.
(4) yttrium oxide stabilized zirconium oxide material powder is prepared:
By yttria-stabilized zirconia superfine powder grind into powder, then by deionized water as dispersing agent, by powder Yttrium oxide stabilized zirconium oxide material slurries are made in end；
Yttrium oxide stabilized zirconium oxide material powder is evenly spread out in deionized water respectively using ultrasonic activation；
Binder (PVA) solution is added in yttrium oxide stabilized zirconium oxide material slurries, and mixed slurry is put into ball milling Ball milling 2 hours in machine, mix the nano particle of yttrium oxide stabilized zirconium oxide material and binder uniformly；
Uniformly mixed yttrium oxide stabilized zirconium oxide material slurries are put into drying box and are dried, stabilized with yttrium oxide is made Then block-like yttrium oxide stabilized zirconium oxide material is crushed, is sieved by zirconia material grout cures, form micron-scale Yttrium oxide stabilized zirconium oxide material nano particle；
High temperature sintering is carried out to yttrium oxide stabilized zirconium oxide material nano particle, sintering temperature is at 1300 degrees Celsius to 1500 Between degree Celsius, grinding obtains yttrium oxide stabilized zirconium oxide material sintering of nano-material powder after ten minutes for heat preservation.
(5) heated oxide yttrium stable zirconium oxide material nano is sintered powder to molten condition；
Liquid melt state is heated to using yttrium oxide stabilized zirconium oxide material sintering of nano-material powder；
(6) yttrium oxide stabilized zirconium oxide material sintering of nano-material dusty material is sprayed:
The anode of power supply, cathode are connected to the anode of coating spray gun, on cathode, pass through electric current by hydrogen, helium, argon And nitrogen composition mixed gas chamber and puncture and generate electric discharge between a cathode and an anode generate plasma arc jet stream；Make height Pressure gas stream blows over the yttrium oxide stabilized zirconium oxide material of plasma arc jet stream and the liquid melt state poured into according to flow, by oxygen Change yttrium stable zirconium oxide material and blow out spray gun, sprays to cement matrix.Jet stream is answered orthogonal with cement matrix surface.
The step (3) further comprises:
Prepare reaction solution: the first zirconium oxychloride and quantitative yttrium nitrate of weighed amount is configured to reaction solution with deionized water, Add quantitative PEG4000.Then quantitative ammonium hydrogen carbonate is weighed, quantitative PEG4000 is added, is prepared with deionized water At precipitant solution.
Precipitation reaction process: 2.5L precipitant solution being added into submergence Circulative impinging stream reactor, and setting is corresponding to be turned Speed after reaching stable operation, the reaction solution of prepared oxygenated chlorinated zirconium and yttrium nitrate is slowly added dropwise from feed opening, anti- It answers and carries out hitting-precipitation reaction in device.
Still aging process: wait react after a certain period of time, instrument is closed, then moves the solution after reaction from reactor Out, still aging 2 hours.
Suction filtration, washing and drying: the solution after standing a few houres is filtered, filter cake successively uses deionized water and ethyl alcohol The solid particle for obtaining white several times is washed respectively, it is then drying over night at 75 DEG C in vacuum desiccator, it is steady to obtain yttrium oxide Determine zirconium oxide presoma zirconium carbonate yttrium.
Grinding and roasting: the yttria-stabilized zirconia presoma after 70 DEG C of vacuum drying is ground using agate mortar Mill, at a certain temperature in Muffle kiln roasting certain time, then natural furnace is cold, is ground again with agate mortar, obtains oxygen Change yttrium stable zirconium oxide superfine powder.
Since monoclinic zirconia has the surface energy bigger than tetragonal zircite, with growing up for zirconium oxide partial size, monocline Mutually the surface energy differential between tetragonal phase structure is gradually reduced, this method doping phase transiting stabilizer in zirconium oxide, stabilizer sun The incorporation of ion, makes Zr 4+Form the rock-steady structure of eight-coordinate.When foreign cation radius is greater than Zr 4+When radius, since displacement is made With increasing cube or the lattice constant of tetragonal zircite, and reduce the ratio of anion radius r- and cation radius r+, To reduce repulsive force between the oxygen oxygen of zirconium oxide part, increases the stability of zirconium oxide and adulterate the cation of lower valency Such as Y3+Substitute Zr 4+When, Lacking oxygen is introduced in dot matrix in order to keep the local electroneutrality of material, can also make high temperature phase zircite Retain to room temperature, improves the stability of coating.
Embodiment 7
A kind of cement matrix ceramic spraying method, includes the following steps:
(1) cement matrix is chosen:
(2) cement matrix is pre-processed: sandblasting (frosted) processing.
(3) nanoscale Fluorin doped Zirconium powder is prepared:
It is the zirconium salt solution of 0.5mol/L with chlorine hydrate zirconium oxide configuration concentration.By yttrium nitrate hexahydrate with 3% molar ratio It is added in zirconium salt solution, fluorine zirconic acid amine is added into the solution, the amount that fluorine is added is 7mol%, 1mol% and 27mol%.Stirring 45min is uniformly mixed fluorine zirconic acid amine with zirconium salt solution.Ammonium hydroxide is at the uniform velocity added dropwise in whipping process, adjusts pH value to 10, is formed Milky zirconium hydroxide presoma.Then zirconium hydroxide presoma is poured into polytetrafluoroethylene (PTFE), 100 DEG C hydro-thermal 6 hours.Hydro-thermal The water of solution afterwards and ethyl alcohol wash three times respectively, and last 90 DEG C of drying, 800 DEG C of sintering can obtain nanoscale Fluorin doped zirconia powder Body.
(4) nanoscale Fluorin doped Zirconium oxide powder is prepared
By nanoscale Fluorin doped Zirconium powder grind into powder, then by deionized water as dispersing agent, by powder Nanoscale Fluorin doped zirconia material slurries are made；
Nanoscale Fluorin doped zirconia material powder is evenly spread out in deionized water respectively using ultrasonic activation；
Binder (PVA) solution is added in nanoscale Fluorin doped zirconia material slurries, and mixed slurry is put into ball Ball milling 2 hours in grinding machine mix the nano particle of nanoscale Fluorin doped zirconia material and binder uniformly；
Uniformly mixed nanoscale Fluorin doped zirconia material slurries are put into drying box and are dried, nanoscale fluorine is made The solidification of doped zirconia material slurry, then block-like nanoscale Fluorin doped zirconia material is crushed, be sieved, and is formed micro- The nanoscale Fluorin doped zirconia material particle of meter ruler cun；
High temperature sintering is carried out to nanoscale Fluorin doped zirconia material particle, sintering temperature is taken the photograph at 1300 degrees Celsius to 1500 Between family name's degree, grinding obtains yttrium oxide stabilized zirconium oxide material sintering powder after ten minutes for heat preservation.
(5) heating nanoscale Fluorin doped zirconia material is sintered powder to molten condition；
(6) nanoscale Fluorin doped zirconia material sintering of nano-material dusty material is sprayed:
High pressure draught is set to blow over the nanoscale Fluorin doped of plasma arc jet stream and the liquid melt state poured into according to flow Nanoscale Fluorin doped zirconia material is blown out spray gun, sprayed to cement matrix by zirconia material.Jet stream and cement base body surface Answer orthogonal in face.
Embodiment 8
A kind of cement matrix ceramic spraying method, includes the following steps:
(1) cement matrix is chosen:
(2) cement matrix is pre-processed: sandblasting (frosted) processing.
(3) nanoscale zinc doping Zirconium powder is prepared:
Chlorine hydrate zirconium oxide is dissolved in the solution that 0.7mol/l is configured in distilled water, and the nitric acid of 5mol% yttrium content is added Yttrium adds the aqueous solution of six water and zinc nitrate that Zn content is 1wt%, 1.5wt% and 2wt%.Mixed solution has been stirred Entirely, ammonium hydroxide is at the uniform velocity added dropwise, adjusting solution to pH value is 10, obtains white zirconium hydroxide presoma, staticly settles 24 hours, will sink Shallow lake dehydrated alcohol and water clean completely, and 90 degrees Celsius of drying, 800 DEG C are calcined two hours, obtain zinc doping Zirconium powder.
(4) nanoscale zinc doping Zirconium oxide powder is prepared:
By nanoscale zinc doping Zirconium powder grind into powder, then by deionized water as dispersing agent, by powder Nanoscale zinc doping zirconia material slurries are made；
Nanoscale zinc doping zirconia material powder is evenly spread out in deionized water respectively using ultrasonic activation；
Binder (PVA) solution is added in nanoscale zinc doping zirconia material slurries, and mixed slurry is put into ball Ball milling 2 hours in grinding machine mix the nano particle of nanoscale zinc doping zirconia material and binder uniformly；
Uniformly mixed nanoscale zinc doping zirconia material slurries are put into drying box and are dried, nanoscale zinc is made The solidification of doped zirconia material slurry, then block-like nanoscale zinc doping zirconia material is crushed, be sieved, and is formed micro- The nanoscale zinc doping zirconia material particle of meter ruler cun；
High temperature sintering is carried out to nanoscale zinc doping zirconia material particle, sintering temperature is taken the photograph at 1300 degrees Celsius to 1500 Between family name's degree, grinding obtains nanoscale zinc doping zirconia material sintering powder after ten minutes for heat preservation.
(5) heating nanoscale zinc doping zirconia material is sintered powder to molten condition；
(6) spraying nanoscale zinc doping zirconia material is sintered dusty material:
High pressure draught is set to blow over the nanoscale zinc doping of plasma arc jet stream and the liquid melt state poured into according to flow Nanoscale zinc doping zirconia material is blown out spray gun, sprayed to cement matrix by zirconia material.Jet stream and cement base body surface Answer orthogonal in face.
The fluorine doped and mixing zinc zirconia material makes coating have antibacterial effect that embodiment 7 and embodiment 8 provide, overcome As simply antibacterial material and coating material are mixed or anti-biotic material is simply only sprayed on coating material surface, The defect of permanent effect is not had to the application of antibacterial.
Embodiment 9
Identical as embodiment in embodiment 1-8, difference is: when dusty spray material by further strength compression and Accelerate high pressure, high speed plasma gas to obtain the Extended-arc of high-energy density, lengthening, thus to obtain velocity of sound is several times as much as Supersonic speed plasma arc jet stream and sprayed, the high-energy density of supersonic speed plasma jet can instant melting high-melting-point, The sprayed on material of high rigidity.Sprayed particle speed is about 300-350m/s in Conventional plasma spraying process, and supersonic speed etc. from Sub- jet stream can accelerate rapidly the melt granules breakthrough velocity of sound to the level of 500-800m/s.
The technical solution breaks through traditional thought that supersonic jet is obtained by high-power, high gas flow, application Single anode Laval nozzle technology is designed using unique low-power, the structure of low gas flow, is obtained under lower energy consumption The supersonic speed plasma jet of high stability, high-energy density.Jet stream speeding scheme is based on mechanical compression, aerodynamic force boil down to It is auxiliary, reduce gas flow.Anode spot is forced by the pinch effect of enhancing electric arc initial segment using Laval nozzle technology In-migration elongating arc before point, to realize the acceleration to electric arc section；Breach traditional Double-positive-pole structure step by step elongating arc, only The method that the area Yan Liu is accelerated；The problem that anode and easily scaling loss are directly made in Laval nozzle type face has been captured, nozzle is improved Stability and service life.Using internal powder conveying structure, dusty spray can be directly sent to the high-temperature region of plasma flame flow.Relatively at present The deficiencies such as powder heating is uneven caused by general outer automatic powder feeding system both at home and abroad, deposition efficiency is low, significantly improve plasma arc Heat utilization rate improves the molten state of powder, improves coating deposition efficiency, and preferably overcomes common internal powder conveying spray Rifle easily gags somebody, the technical difficulty of viscous mouth.
Embodiment 10
Identical as embodiment 1-9, difference is:
When heated oxide zirconia material sintering powder to molten condition of the present invention, the widthization at the peak by calculating zirconia material It spends to statistically analyze the variation of coated grains size.
ω is the wavelength of homogeneous X-ray, and D is the diameter of average crystal grain,For Bragg angle,For merely because of crystal grain Spend widthization degree caused by effect.
The thermal diffusion coefficient of coating is σ
S is coating layer thickness, t1/2For the half for reaching coating maximum temperature threshold time.
The preset value ψ of the tensile strength of coating
ψ=4FI/πS2
FIDrawing force when for coating failure.
δ is average grain size, and g is abrasion constant, and Δ is microhardness, and ρ is internal stress,For micro- fracture occurs Critical grain size, ρmaxFor shearing stress outside maximum, TWFor the wear rate of coating.
For the wear intensity of complete dense oxide zirconia material, Q is the porosity of coating.
The above method controls stretching when coating thermal diffusion coefficient, coating failure by controlling the parameters of coating The properties such as the wear rate of power and coating.
Embodiment 11
A kind of cement matrix ceramic spraying method, includes the following steps:
(1) cement matrix is chosen:
(2) cement matrix is pre-processed: sandblasting (frosted) processing.
(3) preparation doping yttrium Zirconium powder:
With ZrOCl2·8H2O (contains 36%ZrO2, mass fraction), Y (NO3)3·6H2The O ((NO containing 62.7%Y3)3, quality point Number), stoichiometrically Zr1-xYxO2-0.5x(x=0.05) salting liquid of Zr and Y are taken respectively.It is stirred with constant temperature blender with magnetic force Mixing salt solution is uniformly mixed solution, after uniformly, concentrated ammonia liquor reaction is slowly added dropwise while stirring and generates white flock gel. It washs zirconium oxide gel repeatedly with deionized water, uses AgNO3There is no Cl in Filtrate solutions-1, then washed three times with dehydrated alcohol.It will Washed doped yttrium zirconium oxide gel deionized water dissolving continues to stir, and nitric acid is added dropwise and ammonium hydroxide adjusts hydro-thermal reaction forerunner The pH=10 of liquid, and continue stirring 45min and obtain the uniform precursor liquid of chemical composition.Precursor liquid is fitted into autoclave, In T=251-300 DEG C of hydro-thermal 12h.To reaction products therefrom filtering, washed repeatedly with deionized water, then in 80 DEG C of drying 15h Obtain doping yttrium Zirconium powder.
(4) preparation doping yttrium Zirconium oxide powder:
Yttrium Zirconium powder grind into powder will be adulterated, then powder is made and is mixed as dispersing agent by deionized water Miscellaneous yttrium zirconia material slurries；
Doping yttrium zirconia material powder is evenly spread out in deionized water respectively using ultrasonic activation；
Binder (PVA) solution is added in doping yttrium zirconia material slurries, and mixed slurry is put into ball mill Ball milling 2 hours, mix the nano particle for adulterating yttrium zirconia material and binder uniformly；
Uniformly mixed doping yttrium zirconia material slurries are put into drying box and are dried, make to adulterate yttrium zirconium oxide material Expect grout cures, then block-like doping yttrium zirconia material is crushed, is sieved, forms the doping yttrium oxidation of micron-scale Zirconia material particle；
To doping yttrium zirconia material particle carry out high temperature sintering, sintering temperature 1300 degrees Celsius to 1500 degrees Celsius it Between, grinding obtains doping yttrium zirconia material sintering powder after ten minutes for heat preservation.
(5) heating doping yttrium zirconia material is sintered powder to molten condition；
(6) spraying doping yttrium zirconia material is sintered dusty material:
High pressure draught is set to blow over the doping yttrium zirconium oxide of plasma arc jet stream and the liquid melt state poured into according to flow Doping yttrium zirconia material is blown out spray gun, sprayed to cement matrix by material.Jet stream should hang down mutually with cement matrix surface Directly.
Embodiment 12
The sintering temperature of the aluminium oxide is 600 DEG C -1280 DEG C, and the sintering temperature of zirconium oxide is 2700 DEG C, particle Partial size is at 20-100 μm, and the Doped with Titanium before spray gun is added in Zirconium oxide powder, Ti content is 6-18% mass fraction.Doped with Titanium can The further stability of stable aluminium oxide and zirconium oxide guarantees the hardness and toughness of coating.
Embodiment 13
A kind of cement matrix ceramic spraying method, includes the following steps:
(1) cement matrix is chosen
(2) cement matrix is pre-processed: sandblasting or frosted processing
(3) aluminium oxide (Al is prepared2O3) raw material powder
Pure alumina (Al2O3) it is white powder, density 4.0g/cm3, boiling point is 2980 degrees Celsius, and fusing point is taken the photograph for 2050 Family name's degree.The crystal structure of aluminium oxide has diversity, and there are many transitional faces, and there are mainly three types of isomers, respectively α- Al2O3、β-Al2O3、γ-Al2O3.Wherein α-Al2O3Performance is most stable, is hexagonal crystal system, has excellent comprehensive performance, is oxygen The main phase for changing aluminium ceramic coating, is phase the most stable at all temperatures in all isomers.α-Al2O3Structure is most close, Activity is minimum, and specific surface area is smaller.
Studies have shown that β-the Al when sintering temperature reaches 1200 degrees centigrade2O3、γ-Al2O3It can be fully converted to α-Al2O3, and when sintering temperature is at 1220 degrees Celsius or more, sintered alumina powder crystal grain increases extremely, many oxidations There is the phenomenon that merging growth in aluminum nanoparticles.Therefore the sintering temperature that the present invention selects is 1100 degrees Celsius to 1200 degrees Celsius Between.
(4) heated oxide aluminium sintering of nano-material powder is to molten condition；
(5) spray aluminum oxide liquid nano material.
In spraying liquid nano material after cement matrix forms coating, also to be handled by polishing process.
Here it must be noted that other unaccounted technologies that the present invention provides are because be all the known skill of this field Art, title or function according to the present invention, those skilled in the art can find the document of related record, therefore not do It further illustrates.The technical means disclosed in the embodiments of the present invention is not limited only to technological means disclosed in above embodiment, also Including technical solution consisting of any combination of the above technical features.

Claims (10)

1. a kind of cement matrix ceramic spraying method, which is characterized in that comprise the following steps that
(1.1) cement matrix is prepared:
Cement matrix is set up according to cement matrix model or design；
(1.2) sandblasting is carried out to cement matrix or frosted pre-processes；
(1.3) alumina raw material powder is prepared:
Alumina powder is passed through deionized water as dispersing agent by (1.3.1), and oxidation aluminium paste is made in alumina powder；
(1.3.2) is evenly spread out alumina powder using ultrasonic activation in deionized water；
Binder solution is added in oxidation aluminium paste in (1.3.3), and mixed slurry is put into ball mill ball milling 2 hours or more, Mix aluminum oxide nanoparticle and binder uniformly；
(1.3.4) uniformly mixed oxidation aluminium paste is dried using the mode of spray drying；Oxidation aluminium paste is set to be frozen into ball Shape particle, is then sieved, and forms the aluminum oxide nanoparticle of micron-scale；
(1.3.5) to aluminum oxide nanoparticle carry out high-temperature calcination, calcination temperature between 1100 degrees Celsius to 1200 degrees Celsius, Grinding obtains aluminium oxide nano calcined powder after ten minutes for heat preservation；
(1.4) heated oxide aluminium nanometer calcined powder to molten condition forms zirconia nanopowder fluent material；
By aluminium oxide nano powder and dispersant, it is made into slurry, injects electric heater, high-temperature fusion；
(1.5) plasma arc spraying or thermal spraying mode spray aluminum oxide liquid nano material, the plasma arc spray are used Painting mode are as follows:
The anode of power supply, cathode are connected to the anode of coating spray gun, on cathode by (1.5.1), make electric current by by hydrogen, Helium, argon and nitrogen composition mixed gas chamber and puncture and generate electric discharge between a cathode and an anode generate plasma arc penetrate Stream；
(1.5.2) makes high pressure draught blow over the oxidation aluminium of plasma arc jet stream and the liquid melt state poured into according to flow Alumina material is blown out spray gun, sprayed to cement matrix by material；
(1.5.3) cooling coating makes aluminium oxide nano fluent material form aluminium oxide liquid ceramic coating；
The thermal spraying mode are as follows: (1.5.4) preheats matrix；
(1.5.5) surface is preliminarily sprayed in aluminium oxide nano fluent material according to basic material, prevents basic material oxygen Change；Oxygen-acetylene torch of spraying uses neutral flame or weak carburizing flame；
(1.5.6) sets oxygen-acetylene pressure, confirms the angle of spray gun, distance and movement speed, conveys oxygen according to fixed amount Change aluminium liquid nano material, matrix is sprayed, aluminium oxide liquid ceramic coating is cooled into.
2. a kind of cement matrix ceramic spraying method according to claim 1, it is characterised in that: the heated oxide aluminium Nanometer calcined powder to molten condition, which refers to, is heated to liquid melt state for aluminium oxide nano calcined powder using electric heater unit.
3. a kind of cement matrix ceramic spraying method according to claim 1, it is characterised in that: the blasting treatment is Refer to: utilizing compressed air, the sand grains of unlike material is turned in sand-blasting machine to cement matrix surface, sand grains includes glass sand, steel Sand, aluminium oxide or zirconia ceramics sand, the pressure of compressed air are 0.7MPa-2.0MPa；In use sandblasting to cement base body surface When surface treatment, Spray gun nozzle and cement matrix surface are formed into 30-90 degree angle, and at the uniform velocity from one end of cement matrix to the other end It is mobile, cement matrix surface is cleared up using compressed air after blasting treatment, cement matrix is wanted after blasting treatment Plasma arc spraying is carried out immediately.
4. a kind of cement matrix ceramic spraying method according to claim 1, it is characterised in that: the jet stream and cement Matrix surface is answered orthogonal.
5. a kind of cement matrix ceramic spraying method according to claim 1, which is characterized in that in the step (1.3) Also mixed with zirconia material powder in alumina raw material powder, zirconia material powder is obtained using following steps:
It takes quantitative urea and zirconium nitrate to be dissolved in deionized water and is configured to zirconium nitrate mixed liquor；By 1 part of Span- of mass fraction 80 are added in the container for filling 10 parts of dimethylbenzene, with electric mixer to the dimethylbenzene in container during addition Span-80 Mixed liquor is stirred, and when the dimethylbenzene mixed liquor in container becomes uniform, 1 part of prepared zirconium nitrate is added into container Mixed liquor obtains white emulsion after emulsifying half an hour, emulsion is poured into reaction kettle, and is put into after reaction kettle is sealed It is reacted in 120 degrees Celsius of baking oven, taking-up reaction kettle opens reaction kettle after it is cooled to room temperature after reacting 15 hours Sampling obtains white crystal；White crystal obtains white powder after being filtered, washed, and reacts as follows:
CO(NH2)2+4H20→2NH3·H2O+H2CO3；
H2CO3→2H++CO3 2-；
NH3·H2O→NH4 ++OH-；
2OH-+CO3 2-+Zr4+→Zr(OH)2CO3↓；
White powder is put into drying in vacuum oven and for 24 hours, obtains the presoma of zirconia material powder；The forerunner that will be obtained Body powder is put into Muffle furnace, obtains zirconia material powder after calcining 3 hours under 500 degrees Celsius.
6. a kind of cement matrix ceramic spraying method according to claim 1, which is characterized in that the step (1.3) Also mixed with zirconia material powder in middle alumina raw material powder, the zirconia material powder is obtained using following steps:
Chlorine hydrate Zirconium oxide powder is weighed, chlorine hydrate Zirconium oxide powder is dissolved in deionized water, obtaining zirconium concentration is In the clarified solution of 0.1mol/L；The ammonium hydroxide that mass fraction is 26-27% is diluted to the NH that concentration is 1mol/L3·H2O solution, NH after dilution is slowly added dropwise into the clarified solution of above-mentioned basic zirconium chloride3·H2Suspension is formed after O solution, determines suspension PH value is 8.5；Suspension is separated with centrifuge, is obtained Zr (OH)4Hydrate deposition then cleans precipitating with deionized water, so It is centrifuged again afterwards, this process repeats 5-6 times, until chloride ion and ammonium ion are removed completely；It is by mass fraction The nitric acid of 66-67% is diluted to the HNO that concentration is 2mol/L3Solution；HNO3 and mass fraction after dilution are added into precipitating For 30% hydrogen peroxide, the turbid solution of white is formed；Finally white opacity solution is packed into container, is placed on magnetic stirring apparatus Upper uniform stirring waits and dispergation reaction occurs, clarifies after one day, measure the colloidal sol of clear；By the titanium dioxide of clear Zirconium colloidal sol heating evaporation moisture at 80 degrees celsius, obtains zirconium dioxide xerogel, then carries out calcining and decomposing in the lehr, 5min is kept the temperature after being heated to set temperature with the heating rate of 10 centigrade per minutes, the cooled to room temperature in furnace；Finally It is ground with agate mortar, 200 mesh screens fall impurity and large-size particles to get calcined white oxide zirconium raw material powder is arrived End.
7. a kind of cement matrix ceramic spraying method according to claim 1, which is characterized in that the step (1.3) Also mixed with yttria-stabilized zirconia superfine powder, the yttria-stabilized zirconia superfine powder in middle alumina raw material powder Body is obtained using following steps:
Weigh quantitative precipitating reagent NH4HCO3It is added in reactor with Surfactant PEG 4000, then be slowly added dropwise from feed opening ZrOCl2·8H2O and stabilization agent Y (NO3)3·6H2After reaching the reaction time, reaction solution is taken out for the mixed solution of O, is passed through Filter, deionized water washing, decompression suction filtration, secondary deionized water is washed, decompression filters, dehydrated alcohol washing, depressurizes suction filtration, is secondary Dehydrated alcohol washing, decompression obtain the presoma of yttria-stabilized zirconia after filtering, then presoma is true at 75 degrees Celsius Dry 8 hours under Altitude, then the agate mortar grinding distribution of the product after drying, the last certain temperature in Muffle furnace Yttria-stabilized zirconia superfine powder is received after roasting.
8. a kind of cement matrix ceramic spraying method, which comprises the steps of:
(8.1) cement matrix is chosen；
(8.2) sandblasting pretreatment is carried out to cement matrix；
(8.3) alumina-zirconia composite ceramic material is prepared；
Aluminium oxide nano is sintered powder, zirconia nanopowder sintering powder and Al by (8.3.1)2O3-SiO2- CaO complex sintering aids Proportionally loading ball grinder in；
(8.3.2) is added alcohol and abrading-ball and is placed on roller grinder, ball, material, alcohol ratio be 8:1:1, adjust revolving speed Ball milling 20-24h；
Suspension after ball milling is placed in pallet by (8.3.3), and 80 degrees Celsius are dried for standby；
(8.3.4) weighs mixed material powder, is placed in molding die, 200-300MPa pressure maintaining 15s is forced into, after demoulding It obtains powder base and is dried at 50 degrees Celsius；
(8.3.5) is normal pressure-sintered to obtain alumina-zirconia composite ceramic material；
(8.4) alumina-zirconia composite ceramic material powder is prepared respectively:
Then (8.4.1) is used as by deionized water and is dispersed respectively by alumina-zirconia composite ceramic material grind into powder Alumina-zirconia composite ceramic material slurries are made in alumina-zirconia composite ceramic material powder by agent；
(8.4.2) is uniform in deionized water by alumina-zirconia composite ceramic material powder respectively using ultrasonic activation It scatter；
Binder solution is added in alumina-zirconia composite ceramic material slurries in (8.4.3), and mixed slurry is put into ball Ball milling 2 hours in grinding machine, mix the nano particle of alumina-zirconia composite ceramic material and binder uniformly；
Uniformly mixed alumina-zirconia composite ceramic material slurries are put into drying box and are dried by (8.4.4), make oxygen Change aluminium/zirconia composite ceramics material slurry solidification, then carries out block-like alumina-zirconia composite ceramic material powder It crushes, sieving, forms the alumina-zirconia composite ceramic material nano particle of micron-scale；
(8.4.5) carries out high temperature sintering to alumina-zirconia composite ceramic material nano particle, and sintering temperature is Celsius 1100 It spends between 1200 degrees Celsius, grinding obtains alumina-zirconia composite ceramic material sintering of nano-material powder after ten minutes for heat preservation；
(8.5) heated oxide aluminium/zirconia composite ceramics material nano is sintered powder to molten condition；
Alumina-zirconia composite ceramic material sintering of nano-material powder is heated to liquid melt state using electric heater unit；
(8.6) spray aluminum oxide/zirconia composite ceramics liquid nano material:
The anode of power supply, cathode are connected to the anode of coating spray gun, on cathode by (8.6.1), make electric current by by hydrogen, Helium, argon and nitrogen composition mixed gas chamber and puncture and generate electric discharge between a cathode and an anode generate plasma arc penetrate Stream；
(8.6.2) makes high pressure draught blow over aluminium oxide/oxygen of plasma arc jet stream and the liquid melt state poured into according to flow Change zirconium composite ceramic material, alumina-zirconia composite ceramic material is blown out into spray gun, forms oxidation in injection to cement matrix Molten aluminum state ceramic coating.
9. a kind of cement matrix ceramic spraying method according to claim 8, it is characterised in that: the zirconium oxide is in oxygen Changing aluminium/zirconia composite ceramics material mass ratio is 8%.
10. a kind of cement matrix ceramic spraying method, which comprises the steps of:
(10.1) cement matrix is chosen:
(10.2) sandblasting is carried out to cement matrix or frosted pre-processes:
(10.3) zirconia material powder is prepared:
Zirconium oxide powder is passed through deionized water as dispersing agent by (10.3.1), and zircon oxide slurry is made in Zirconium oxide powder；
(10.3.2) is evenly spread out zirconia powder using ultrasonic activation in deionized water；
Binder solution is added in (10.3.3) in zircon oxide slurry, and mixed slurry is put into ball milling 2 hours in ball mill, makes oxygen Change zirconium nano particle and binder uniformly mixes；
Uniformly mixed zircon oxide slurry is put into drying box and is dried by (10.3.4), solidifies zircon oxide slurry, then by block The Zirconium oxide powder of shape is crushed, is sieved, and the Zirconium oxide nano grain of micron-scale is formed；
(10.3.5) to Zirconium oxide nano grain carry out high temperature sintering, sintering temperature 1600 degrees Celsius to 1900 degrees Celsius it Between, grinding obtains zirconia nanopowder sintering powder after ten minutes for heat preservation；
(10.4) heated oxide zirconium sintering of nano-material powder is to molten condition:
(10.5) spraying zirconia nanopowder fluent material forms zirconium oxide liquid ceramic coating.
CN201811423115.6A 2018-11-27 2018-11-27 A kind of cement matrix ceramic spraying method Withdrawn CN109467455A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111689730A (en) * 2020-05-21 2020-09-22 蚌埠明飞环保材料科技有限公司 Stone-like brick and coating construction method thereof
CN113529006A (en) * 2021-06-16 2021-10-22 洛阳理工学院 Wear-resistant nano ceramic coating and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111689730A (en) * 2020-05-21 2020-09-22 蚌埠明飞环保材料科技有限公司 Stone-like brick and coating construction method thereof
CN113529006A (en) * 2021-06-16 2021-10-22 洛阳理工学院 Wear-resistant nano ceramic coating and preparation method thereof

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