CN108587458A - ceramic surface material and surface coating - Google Patents
ceramic surface material and surface coating Download PDFInfo
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- CN108587458A CN108587458A CN201810399274.0A CN201810399274A CN108587458A CN 108587458 A CN108587458 A CN 108587458A CN 201810399274 A CN201810399274 A CN 201810399274A CN 108587458 A CN108587458 A CN 108587458A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/103—Anti-corrosive paints containing metal dust containing Al
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1687—Use of special additives
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- C09D5/18—Fireproof paints including high temperature resistant paints
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- C08K3/22—Oxides; Hydroxides of metals
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Abstract
The present invention provides a kind of ceramic surface materials comprising：The organosilicon of 20.0wt%~70.0wt%, the organic solvent of 20.0wt%~70.0wt%, the filler of 1.0wt%~50wt%, the auxiliary agent of 0.1wt%~3.0wt%, wherein organic solvent are one or more in butyl acetate, dimethylbenzene, n-butyl ether, butyl acetic acid esters, hexahydrotoluene, normal octane and butyl titanate；The filler is made of graphene, graphite, transition group metallic oxide, composition silicate, rare earth oxide, nonmetallic, nonmetallic compound, magnesium-yttrium-transition metal boride and metal.Component in the above-mentioned ceramic surface material of the application mutually acts synergistically, and has better comprehensive performance when making it as coating.
Description
Technical field
The present invention relates to surface material technology field more particularly to ceramic surface materials and surface coating.
Background technology
In Aeronautics and Astronautics device, station boiler, biomass boiler, garbage burning boiler, petrochemical heating furnace, middle unskilled labourer
In the production run of industry boiler, various engines and other heat power equipments, the high temperature corrosion of heating surface, erosive wear and it is stained with
Dirty slagging etc. causes above equipment the very big hidden danger of safe operation, at the same can also influence above equipment heat exchange efficiency and
Exchange capability of heat.High temperature corrosion and erosive wear cause the direct destruction of heating surface, heat exchange surface Slagging to directly result in heat exchange
Ability declines, heat power equipment therrmodynamic system is unbalance and the thermal efficiency reduces, and the fire box temperature raising also resulted in can also cause boiler tube
The problems such as overheating operation, excessively high NO_x formation and discharge aggravation and exhaust gas temperature；Slagging can also aggravate to change simultaneously
Hot surface corrodes.The above problem directly affects safety in production, energy-saving and emission-reduction, product quality and production capacity, and reduce equipment uses the longevity
Life, massive losses are brought to enterprise.
For above-mentioned high temperature corrosion, Slagging and erosive wear problem, traditional solution is optimization design, optimization
Operation, promoted heat-transfer surface basic material grade, using metal thermal spraying and built-up welding deposition silicates ceramic surface material with have
Machine silicon class ceramic surface material, but there is no fundamentally solve high temperature corrosion, erosive wear and Slagging for the above method
Problem, security risk still have.
Surfacing is a kind of important engineering material, is to be coated on body surface to form film under certain condition
And with protection, decoration, insulation, anti-corrosion, shockproof or the specific functions such as heat-resisting liquid or solid material.And composite organic is resistance to
High temperature corrosion self-healing ceramic surface material is a kind of novel environment-friendly function material, which has high temperature resistant, Applicable temperature
Range is wide, corrosion-resistant, high rigidity, high durable and it is not viscous many advantages, such as, be a kind of ideal surfacing.
In order to solve the problems, such as high temperature corrosion, erosive wear and the Slagging in the production runs such as boiler, researcher's research and development
The silicates ceramic material of a series of high temperature resistant resistive connection slag grinds to strengthen the stability of boiler in process of production
The person of studying carefully further enhances the performance of ceramic surface material simultaneously, is desirably to obtain the preferable ceramic surface material of comprehensive performance, from
And ensure that the heating equipments such as boiler being capable of stable operation in industry.Such as：Application No. is 201410687121.8 Chinese patents
Disclose a kind of high temperature resistant dirt-resistant slagging ceramic surface material comprising：Filler, binder and water, wherein filler include oxygen
Change zirconium, silicon nitride, silicon carbide, titanium dioxide, kaolin and rare earth oxide, the ceramic surface material which provides is resistant to
1050 DEG C of high temperature, but the surfacing comprehensive performance especially sulfur corrosion of reducing resistance atmosphere and chlorine corrosion ability is not still
It is very high.Application No. is 201510542509.3 Chinese patents to disclose a kind of high-temperature corrosion resistance dirt-resistant slagging ceramic watch plane materiel
Material comprising：Filler, binder and water, wherein filler include graphite, boron nitride and rare earth oxide, the pottery which provides
Porcelain surfacing is resistant to 850 DEG C of high temperature, but the surfacing comprehensive performance especially heat-resisting ability still cannot meet height
Warm environmental demand, and the patent of existing organosilicon high temperature corrosion resistance surfacing then generally existing organosilicon heat up pyrolytic process
Ceramic layer porosity is higher, there are through-wall crack, and used self-healing packing material is mostly alkali metal glass, metal oxide
And higher nonmetallic compound of melting temperature etc., so that self-healing ceramic surface material is most widely warm in commercial Application
It is relatively low to spend section (250~800 DEG C) self-healing capability, chlorine corrosion and reducible sulfur corrosion cannot be resisted very well, corrosion is caused to be situated between
Matter penetrates surfacing corrosion base material.
Invention content
Present invention solves the technical problem that being to provide a kind of preferable ceramic surface material of comprehensive performance, it is in particular in
The corrosion-resistant of ceramic surface material, high temperature resistant and self-healing capability are preferable.
In view of this, this application provides a kind of ceramic surface material, it is composed of the following components：
The organic solvent be selected from butyl acetate, dimethylbenzene, n-butyl ether, butyl acetic acid esters, hexahydrotoluene,
It is one or more in normal octane and butyl titanate；
The filler by graphene, graphite, transition group metallic oxide, composition silicate, rare earth oxide, it is nonmetallic,
Nonmetallic compound, magnesium-yttrium-transition metal boride and metal form.
Preferably, the organosilicon is selected from polysilazane, poly- silicon boron azane, polysiloxanes, silicones azane, poly- silicon-carbon
It is one or more in alkane, poly- silicon-carbon azane and polyborazine.
Preferably, the transition group metallic oxide is in zirconium oxide, chromium oxide, titanium oxide, molybdenum oxide and niobium oxide
It is one or more；The metal is one or more in chromium, nickel, titanium, aluminium and yttrium；The composition silicate is selected from copper chromium
It is one or more in spinelle, magnesium aluminate spinel, mullite, nepheline, kaolin, kyanite, alumina silicate and zirconium silicate；It is described
Rare earth oxide is one or more in cerium oxide, yttrium oxide and lanthana；It is described it is nonmetallic in silicon and boron one
Kind or two kinds；The nonmetallic compound in boron carbide, silicon boride, boron nitride, silicon nitride, silicon carbide and boron oxide one
Kind is a variety of；The magnesium-yttrium-transition metal boride is one or more in titanium boride, zirconium boride, chromium boride and nickel borides；
The auxiliary agent is one or more in silane coupling agent, wetting dispersing agent and catalytic curing agent.
Preferably, the granularity of the filler is 50~900nm.
Preferably, the organosilicon is selected from polysilazane, poly- silicon boron azane, polysiloxanes, silicones azane, poly- silicon-carbon
When one or more in alkane, poly- silicon-carbon azane and polyborazine, the polysilazane, poly- silicon boron azane, polysiloxanes, poly- silicon
The content of oxygen azane, poly- silicon-carbon alkane and poly- silicon-carbon azane independently is 0.5~70wt%.
Preferably, the organosilicon be polysilazane, poly- silicon boron azane, polysiloxanes, silicones azane, poly- silicon-carbon alkane,
When the mixture of poly- silicon-carbon azane and polyborazine, the polysilazane, polysiloxanes, silicones azane, gathers poly- silicon boron azane
The content of silicon-carbon alkane and poly- silicon-carbon azane independently is 0.5~67wt%.
Preferably, the organosilicon of stating is polysilazane, poly- silicon boron azane, polysiloxanes, silicones azane, poly- silicon-carbon
When the mixture of alkane, poly- silicon-carbon azane and polyborazine, the content of the organosilicon is 30wt%~60wt%, the poly- silicon nitrogen
The content of alkane is 10wt%~20wt%, and the content of the poly- silicon boron azane is 10wt%~20wt%, and the polysiloxanes gathers
Silica azane, poly- silicon-carbon alkane, poly- silicon-carbon azane and polyborazine content independently be 2wt%~5wt%.
Preferably, the organic solvent is butyl acetate, dimethylbenzene, n-butyl ether, butyl acetic acid esters, methyl ring
When one or more in hexane, normal octane and butyl titanate, the butyl acetate, dimethylbenzene, n-butyl ether, butyl
Acetic acid esters, hexahydrotoluene, normal octane and butyl titanate content independently be 0.5wt%~70wt%.
Preferably, the organic solvent is butyl acetate, dimethylbenzene, n-butyl ether, butyl acetic acid esters, methyl ring
When the mixture of hexane, normal octane and butyl titanate, the butyl acetate, dimethylbenzene, n-butyl ether, butyl acetic acid
Ester, hexahydrotoluene, normal octane and butyl titanate content independently be 0.5wt%~67wt%.
Preferably, when the rare earth oxide is cerium oxide, yttrium oxide and lanthana, the cerium oxide, yttrium oxide and oxygen
The content for changing lanthanum independently is 0.1wt%~2wt%；
The content of the graphite is 0.1wt%~3wt%；The content of the graphene is 0.1wt%~3wt%；
The metal is chromium, nickel, titanium, aluminium and when yttrium, the chromium, nickel, titanium, aluminium and yttrium content independently be 0.1wt%
~20wt%；
The composition silicate is copper picotite, magnesium aluminate spinel, mullite, nepheline, kaolin, kyanite, silicic acid
When aluminium and zirconium silicate, the copper picotite, magnesium aluminate spinel, mullite, nepheline, kaolin, kyanite, alumina silicate and silicic acid
The content of zirconium independently is 0.1wt%~20wt%；
It is described it is nonmetallic be silicon and boron when, the content of the silicon and boron independently is 0.1wt%~20wt%；
When the nonmetallic compound is boron carbide, silicon boride, boron nitride, silicon nitride, silicon carbide and boron oxide, the carbon
The content for changing boron, silicon boride, boron nitride, silicon nitride, silicon carbide and boron oxide independently is 0.1wt%~20wt%；
When the magnesium-yttrium-transition metal boride is titanium boride, zirconium boride, chromium boride and nickel borides, the titanium boride, boronation
The content of zirconium, chromium boride and nickel borides independently is 0.1wt%~20wt%；
When the transition metal oxide is zirconium oxide, chromium oxide, titanium oxide, molybdenum oxide and niobium oxide, the zirconium oxide,
Chromium oxide, titanium oxide, molybdenum oxide and niobium oxide content independently be 0.1wt%~20wt%.
Preferably, when the rare earth oxide is cerium oxide, yttrium oxide and lanthana, the cerium oxide, yttrium oxide and oxygen
The content for changing lanthanum independently is 0.3wt%~1.5wt%；
The content of the graphite is 0.2wt%~2wt%；The content of the graphene is 0.2wt%~2wt%；
The metal is chromium, nickel, titanium, aluminium and when yttrium, the chromium, nickel, titanium, aluminium and yttrium content independently be 0.2wt%
~3wt%；
It is described it is nonmetallic be silicon and boron when, the content of the silicon and boron independently is 0.2wt%~3wt%；
The composition silicate is copper picotite, magnesium aluminate spinel, mullite, nepheline, kaolin, kyanite, silicic acid
When aluminium and zirconium silicate, the copper picotite, magnesium aluminate spinel, mullite, nepheline, kaolin, kyanite, alumina silicate and silicic acid
The content of zirconium independently is 0.2wt%~3wt%；
When the nonmetallic compound is boron carbide, silicon boride, boron nitride, silicon nitride, silicon carbide and boron oxide, the carbon
The content for changing boron, silicon boride, boron nitride, silicon nitride, silicon carbide and boron oxide independently is 0.2wt%~3wt%；
When the magnesium-yttrium-transition metal boride is titanium boride, zirconium boride, chromium boride and nickel borides, the titanium boride, boronation
The content of zirconium, chromium boride and nickel borides independently is 0.2wt%~3wt%；
When the transition metal oxide is zirconium oxide, chromium oxide, titanium oxide, molybdenum oxide and niobium oxide, the zirconium oxide,
Chromium oxide, titanium oxide, molybdenum oxide and niobium oxide content independently be 0.2wt%~3wt%.
Present invention also provides a kind of surface coating, including investment precoat and priming paint, the investment precoat is said program
The ceramic surface material.
This application provides a kind of ceramic surface materials comprising：The organosilicon of 20.0wt%~70.0wt%,
The organic solvent of 20.0wt%~70.0wt%, the filler of 1.0wt%~50wt%, the auxiliary agent of 0.1wt%~3.0wt%,
Middle organic solvent is selected from butyl acetate, dimethylbenzene, n-butyl ether, butyl acetic acid esters, hexahydrotoluene, normal octane and titanium
It is one or more in acid butyl ester；The filler is by graphene, graphite, transition group metallic oxide, composition silicate, rare earth oxygen
Compound, nonmetallic, nonmetallic compound, magnesium-yttrium-transition metal boride and metal form.Ceramic surface material provided by the present application
In organosilicon pass through under first time heating and the condition of high temperature pyrolytic reaction discharge formed after carbon dioxide, the gases such as methane it is empty
Between netted nitrogen carbon borosilicate composite ceramic material structure, and react to form covalent bond and ceramic with other inorganic components, fill out simultaneously
Rare earth oxide in material is conducive to crystal grain refinement, and filling crystal grain gap forms network, and the fillers such as composition silicate and metal exist
Interaction forms melting softening or even flowable state composite ceramics constituent element under high temperature, can be filled in and be cracked by silicone thermal solution automatically
Gas generate hole and destroy generate crackle, to improve the high temperature of ceramic surface material and the toughness of room temperature, heat
Stability, high temperature corrosion and thermodynamic behaviour etc..To sum up, the said components synergistic effect in the application, makes ceramic watch
Plane materiel material has preferable performance, such as：High temperature resistant, high heat exchange property, corrosion-resistant, wear-resistant, high emissivity, dirt-resistant slagging
With self-healing capability.
Specific implementation mode
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are only the feature and advantage further illustrated the present invention, rather than to the claims in the present invention
Limitation.
For the bad problem of ceramic surface material comprehensive performance in the prior art, the embodiment of the invention discloses a kind of potteries
Porcelain surfacing, organic solvent, filler and auxiliary agent and organosilicon in the ceramic surface material form collaboration system, for difference
The specific requirement of use environment so that ceramic layer has anti-oxidant, corrosion-resistant, wear-resistant, automatically cleaning, high tenacity, some higher thermal conductivity
The high combination property of rate and emissivity, and there is excellent selfreparing self-healing capability.Specifically, this application provides a kind of potteries
Porcelain surfacing, it is composed of the following components：
The organic solvent be selected from butyl acetate, dimethylbenzene, n-butyl ether, butyl acetic acid esters, hexahydrotoluene,
It is one or more in normal octane and butyl titanate；
The filler by graphene, graphite, transition group metallic oxide, composition silicate, rare earth oxide, it is nonmetallic,
Nonmetallic compound, magnesium-yttrium-transition metal boride and metal form.
In this application, organosilicon is selected from polysilazane, poly- silicon boron azane, polysiloxanes, silicones azane, poly- silicon-carbon
It is one or more in alkane, poly- silicon-carbon azane and polyborazine；In a particular embodiment, the organosilicon is polysilazane, gathers
The mixture of silicon boron azane, polysiloxanes, silicones azane, poly- silicon-carbon alkane, poly- silicon-carbon azane and polyborazine.Institute in the application
Basic component of the organosilicon as surface ceramic coating is stated, as bridge and other component collective effects；Specifically, described have
After machine silicon discharges the gases such as carbon dioxide, methane under first time heating and the condition of high temperature by pyrolytic reaction, space networks are formed
Shape nitrogen carbon borosilicate composite ceramic material structure, and react to form covalent bond and ceramic with other inorganic components.
In this application, the organosilicon is selected from polysilazane, poly- silicon boron azane, polysiloxanes, silicones azane, poly- silicon
It is the polysilazane, poly- silicon boron azane, polysiloxanes, poly- when one or more in carbon alkane, poly- silicon-carbon azane and polyborazine
The content of silica azane, poly- silicon-carbon alkane and poly- silicon-carbon azane independently is 0.5~70wt%；The organosilicon be polysilazane,
Poly- silicon boron azane, polysiloxanes, silicones azane, poly- silicon-carbon alkane, poly- silicon-carbon azane and polyborazine mixture when, it is described poly-
Silazane, poly- silicon boron azane, polysiloxanes, silicones azane, poly- silicon-carbon alkane and poly- silicon-carbon azane content independently be 0.5~
67wt%.In a particular embodiment, the content of the organosilicon is 30wt%~60wt%, at this point, the polysilazane contains
Amount is 10wt%~20wt%, and the content of the poly- silicon boron azane is 10wt%~20wt%, the polysiloxanes, poly- silica nitrogen
Alkane, poly- silicon-carbon alkane, poly- silicon-carbon azane and polyborazine content independently be 2wt%~5wt%.If the content of organosilicon exceeds
Above range can not then effectively form space net structure, to the spatial stability of nitrogen carbon borosilicate composite ceramic material structure
Property can reduce, ceramic surface ceramic is insufficient or excessively fully, directly affects the self-healing capability of ceramic surface material and resistance to
Corrosive nature.
The solvent of the application ceramic surface material is organic solvent, and the organic solvent is selected from butyl acetate, dimethylbenzene, just
It is one or more in butyl ether, butyl acetic acid esters, hexahydrotoluene, normal octane and butyl titanate；It is being embodied
In example, the organic solvent is butyl acetate, dimethylbenzene, n-butyl ether, butyl acetic acid esters, hexahydrotoluene, just pungent
Alkane and butyl titanate.The content of the organic solvent is 20wt%~70wt%, in a particular embodiment, the organic solvent
Content is 30wt%~60wt%.Specifically, the organic solvent is butyl acetate, dimethylbenzene, n-butyl ether, butyl
When one or more in acetic acid esters, hexahydrotoluene, normal octane and butyl titanate, the butyl acetate, dimethylbenzene, positive fourth
Ether, butyl acetic acid esters, hexahydrotoluene, normal octane and butyl titanate content independently be 0.5wt%~
70wt%；The organic solvent is butyl acetate, dimethylbenzene, n-butyl ether, butyl acetic acid esters, hexahydrotoluene, just
When the mixture of octane and butyl titanate, the butyl acetate, dimethylbenzene, n-butyl ether, butyl acetic acid esters, methyl ring
The content of hexane, normal octane and butyl titanate independently is 0.5wt%~70wt%；In a particular embodiment, the acetic acid fourth
Ester, dimethylbenzene content independently be 10wt%~40wt%, the n-butyl ether, butyl acetic acid esters, methyl cyclohexane
The content of alkane, normal octane and butyl acetate independently is 2wt%~5wt%.If the content of organic solvent exceeds above range,
The film forming characteristics before the non-Cheng Tao of ceramic surface material and surface drying characteristic can be influenced, to influence the thermal cracking of ceramic surface material
Reaction, directly affect ceramic surface material at Tao Xingneng, the final self-cleaning property and toughness for influencing ceramic surface material.
In this application, the auxiliary agent is auxiliary agent well known to those skilled in the art, is not limited particularly this application
System, the auxiliary agent described in the specific embodiment of the application in silane coupling agent, wetting dispersing agent and catalytic curing agent one
Kind is a variety of.The content of the auxiliary agent is 0.1wt%~3.0wt%, and more specifically, the content of each auxiliary agent is only in the auxiliary agent
It is on the spot 0.05wt%~1.0wt%.If the independent content of auxiliary agent exceeds above range, ceramic surface material will have a direct impact on
Dispersibility, coupling performance and curing performance, cause ceramic surface material at Tao Xingneng, influence ceramic surface material and matrix knot
The self-healing capability of conjunction ability and ceramic surface material.
Heretofore described filler finally determines the performance of ceramic surface material as core component.In the application
The filler is made of graphene, graphite, transition group metallic oxide, composition silicate, rare earth oxide and metal.It is described to fill out
The granularity of material is 50~900nm.
In the filler, the graphite contributes to ceramic layer film formation and mask erosion type medium to ooze with graphene
Enter, improves the case hardness of base material under high temperature to metal base carburizing；Graphite forms carbon dioxide at high temperature with graphene, with
Silicone thermal cracking temperature matches, and is conducive to cracked gas and is discharged from ceramic layer；Meanwhile graphene also has at high temperature with graphite
Help other reactions inside promotion and catalytic ceramics layer, and carbide ceramics is generated with other materials.
The transition group metallic oxide can be selected from one kind in zirconium oxide, chromium oxide, titanium oxide, molybdenum oxide and niobium oxide
Or it is a variety of, the coefficient of thermal expansion of transition group metallic oxide is consistent with the coefficient of thermal expansion of metal base or swollen higher than the heat of base material
Swollen coefficient；And transition group metallic oxide and metal base binding ability are stronger, to contribute to ceramic surface material and gold
Belong to the binding ability and thermal shock resistance of base material.
The metal be chosen in particular from it is one or more in aluminium, nickel, titanium, chromium and yttrium, in a particular embodiment, the metal
Including aluminium, nickel, titanium, chromium and yttrium.The metal ceramic layer that adjustable ceramic surfacing is formed in ceramic surface material
Coefficient of thermal expansion is closer to metal base；Above-mentioned metal can form metal oxide under high temperature simultaneously.
The nonmetallic compound in boron carbide, silicon boride, boron nitride, silicon nitride, silicon carbide and boron oxide one
Kind is a variety of.In a particular embodiment, the nonmetallic compound is selected from boron carbide, silicon boride, boron nitride, silicon nitride, carbonization
The mixture of silicon and boron oxide.The boron carbide, silicon boride and boron nitride are in ceramic surface material in lower temperature and middle height
Has the characteristics that anti-oxidant, corrosion-resistant, wear-resistant and self-lubricating when warm；It is above-mentioned nonmetallic anti-with oxygen under high temperature degree simultaneously
Silica and boron oxide etc. should be generated, product interreaction re-forms boron glass, is filled with liquid phase more than after softening point temperature
The ceramic layer hole and crackle to be formed since silicone thermal cracks plays the role of selfreparing healing；Silicon nitride and silicon carbide are
With high temperature resistant, corrosion-resistant and anti abrasive filler；Silicate and decomposition in the boron oxide and ceramic surface material
Silica forms complex phase Pyrex, this kind of complex phase Pyrex are different with ratio different softening point temperature, so as to adjust
The selfreparing self-healing temperature of ceramic layer, with specific application environment matching criteria.
It is described it is nonmetallic be chosen in particular from one or both of boron and silicon, in a particular embodiment, it is described it is nonmetallic be boron
And silicon.The nonmetallic silicon and boron are in lower temperature and high temperature with anti-oxidant, corrosion-resistant, wear-resistant and self-lubricating spy
Point；Nonmetallic reacted with oxygen under high temperature degree above-mentioned simultaneously generates silica and boron oxide etc., and product interreaction is again
Boron glass is formed, the ceramic layer hole and crackle to be formed since silicone thermal cracks is filled with liquid phase more than after softening point temperature,
Play the role of selfreparing healing.
The magnesium-yttrium-transition metal boride is one or more in titanium boride, zirconium boride, chromium boride and nickel borides；
In specific embodiment, the magnesium-yttrium-transition metal boride is the mixture of titanium boride, zirconium boride, chromium boride and nickel borides.It is described
Magnesium-yttrium-transition metal boride has the advantages that high temperature resistant, corrosion-resistant, wear-resistant and higher thermal expansion coefficient, to be conducive to and gold
Belong to base material matched coefficients of thermal expansion；It also has better compatibility with metal base, metal packing and Pyrex simultaneously.
Further include composition silicate in above-mentioned filler, the composition silicate is chosen in particular from copper picotite, magnalium point
It is one or more in spar, mullite, nepheline, kaolin, kyanite, alumina silicate and zirconium silicate；Above-mentioned composition silicate exists
Silica can be introduced by reacting under high temperature, thus improve the corrosion-resistant of ceramic surface material, bond strength and mechanical property
Energy.
Rare earth oxide in filler specifically can be selected from cerium oxide, yttrium oxide and lanthana.The rare earth oxide due to
The lattice defect of itself can ceramic surface material formed coating in selective enrichment, fill up the seam generated in temperature-rise period
Gap can promote interpenetrating between component.
Using the ceramic surface material as base, the content of the filler is 1.0wt%~50wt%；In specific embodiment
In, the content of the filler is 1.5wt%~40wt%.Specifically, the rare earth oxide is cerium oxide, yttrium oxide and oxidation
When lanthanum, the content of the cerium oxide, yttrium oxide and lanthana independently is 0.1wt%~2wt%；The content of the graphite is
0.1wt%~3wt%；The content of the graphene is 0.1wt%~3wt%；The metal is chromium powder, nickel powder, titanium valve, aluminium powder
When with yttrium powder, the chromium powder, nickel powder, titanium valve, aluminium powder and yttrium powder content independently be 0.1wt%~20wt%；It is described compound
It is described when silicate is copper picotite, magnesium aluminate spinel, mullite, nepheline, kaolin, kyanite, alumina silicate and zirconium silicate
Copper picotite, magnesium aluminate spinel, mullite, nepheline, kaolin, kyanite, alumina silicate and zirconium silicate content independently be
0.1wt%~20wt%；When the transition metal oxide is zirconium oxide, chromium oxide, titanium oxide, molybdenum oxide and niobium oxide, institute
The content for stating zirconium oxide, chromium oxide, titanium oxide, molybdenum oxide and niobium oxide independently is 0.1wt%~20wt%.
In a particular embodiment, when the rare earth oxide is cerium oxide, yttrium oxide and lanthana, the cerium oxide, oxygen
The content for changing yttrium and lanthana independently is 0.3wt%~1.5wt%；The content of the graphite is 0.2wt%~2wt%；Institute
The content for stating graphene is 0.2wt%~2wt%；The metal is chromium, nickel, titanium, aluminium and when yttrium, the chromium, nickel, titanium, aluminium and
The content of yttrium independently is 0.2wt%~3wt%；The composition silicate be copper picotite, magnesium aluminate spinel, mullite,
When nepheline, kaolin, kyanite, alumina silicate and zirconium silicate, the copper picotite, magnesium aluminate spinel, mullite, nepheline, height
Ridge soil, kyanite, alumina silicate and zirconium silicate content independently be 0.2wt%~3wt%；The transition metal oxide is oxygen
Change zirconium, chromium oxide, titanium oxide, molybdenum oxide and when niobium oxide, the zirconium oxide, chromium oxide, titanium oxide, molybdenum oxide and niobium oxide
Content independently is 0.1wt%~3wt%.If the content of rare earth oxide is more than above range, ceramic surface material can be influenced
Dispersion performance and space net structure stability；The ceramic surface material if graphite and graphene content are beyond above range
Filming performance can have a certain impact, while its corrosion resistance can also be fluctuated and unstable, the ceramic surface of formation
The toughness of material and metal base can also have a certain impact；If the content of composition silicate exceeds above range, can be to ceramics
Self-healing capability, corrosion resistance and the toughness of surfacing have a certain impact；If metal and transition group metallic oxide
Content exceeds above range, can have a certain impact to the corrosion-resistant and thermal shock resistance of then ceramic surface material.
In a particular embodiment, it is described it is nonmetallic be silicon and boron, in the case, the content of the silicon and boron independently is
0.1wt%~20wt%；In a particular embodiment, the content of the silicon and boron independently is 0.2wt%~3wt%.If not golden
The content of category exceeds above range, can have an impact to the self-healing capability of ceramic surface material, to influence ceramic surface material
Corrosion resistance.
In a particular embodiment, the nonmetallic compound be boron carbide, silicon boride, boron nitride, silicon nitride, silicon carbide and
When boron oxide, the boron carbide, silicon boride, boron nitride, silicon nitride, silicon carbide and boron oxide content independently be 0.1wt%
~20wt%；In a particular embodiment, the content of the boron carbide, silicon boride, boron nitride, silicon nitride, silicon carbide and boron oxide
It independently is 0.2wt%~3wt%.If the content of nonmetallic compound exceeds above range, can to ceramic surface material from
Healing ability and self-healing controllability have an impact, while certain influence is generated to its wear-resisting property and toughness.
In a particular embodiment, when the magnesium-yttrium-transition metal boride is titanium boride, zirconium boride, chromium boride and nickel borides,
The titanium boride, zirconium boride, chromium boride and nickel borides content independently be 0.1wt%~20wt%；In a particular embodiment,
The titanium boride, zirconium boride, chromium boride and nickel borides content independently be 0.2wt%~3wt%.If magnesium-yttrium-transition metal boronation
When the content of object exceeds above range, can have to the thermal shock resistance of ceramic surface material, corrosion resistance and with base material binding ability
Certain influence.
Preferably, herein described ceramic surface material, including：
Using the ceramic surface material as base, the content of the organosilicon mixture is 35wt% (wherein, polysilazanes
Content is 10wt%, the content of poly- silicon boron azane is 10wt%, polysiloxanes, silicones azane, poly- silicon-carbon alkane, poly- silicon-carbon azane
Content with polyborazine is all 3wt%)；
The content of the organic solvent is that (wherein, the content of butyl acetate is 2wt% to 23wt%, the content of dimethylbenzene is
11wt%, n-butyl ether, butyl acetic acid esters, hexahydrotoluene, normal octane and butyl titanate content be all 2wt%)；
The content of the preferred auxiliary agent is 1.5wt% (wherein, silane coupling agent, wetting dispersing agent and catalytic curing agent
Content be all 0.5wt%)；
The total content of the filler mixture be 40.5wt% (wherein, the content of boron carbide be 1.5wt%, silicon boride
Content is 1.5wt%, the content of boron nitride is 1.5wt%, the content of silicon nitride is 1.5wt%, the content of silicon carbide is
1.5wt%, boron oxide content be 1.5wt%, the content of titanium boride is 2wt%, the content of zirconium boride is 2wt%, chromium boride
Content be 2wt%, the content of nickel borides is 2wt%, the content of zirconium oxide is 0.8wt%, the content of chromium oxide is
0.8wt%, titanium oxide content be 0.8wt%, the content of molybdenum oxide is 0.8wt%, the content of niobium oxide is 0.8wt%, copper
The content of picotite is 1wt%, the content of magnesium aluminate spinel is 1wt%, the content of mullite is 1wt%, the content of nepheline
For 1wt%, kaolinic content be 3wt%, the content of kyanite is 3wt%, the content of alumina silicate is 3wt% and zirconium silicate
Content is 3wt%, the content of graphite is 0.2wt%, the content of graphene is 0.2wt%, the content of cerium oxide be 0.4wt%,
The content of yttrium oxide is 0.4wt%, the content of lanthana is 0.2wt%, the content of silica flour is 0.55wt%, the content of boron powder is
0.55wt%, aluminium powder content be 0.2wt%, the content of nickel powder is 0.2wt%, the content of titanium valve is 0.2wt%, chromium powder contains
Amount is 0.2wt%, the content of yttrium powder is 0.2wt%).
" independently being " of content indicates that the content of each component can be selected in range intervals in said components in the application
It selects, the selection of content is unaffected between each component, but is the need to ensure that total content cannot exceed total size value.
Ceramic surface material each component provided by the present application and each component content make ceramic watch plane materiel by Optimized Matching
Material has higher comprehensive performance as coating material.
The preparation method of herein described ceramic surface material is prepared according to mode well known to those skilled in the art.
In order to keep the various components in surfacing more uniform, the preparation method of herein described ceramic surface material is preferably under
State step progress：
Organosilicon is mixed with organic solvent, obtains solvent-laden composite organic liquid；By the filler by refining
It is mixed with the solvent-laden composite organic liquid after processing, adds auxiliary agent uniform stirring, filtering encapsulation, obtain ceramic watch
Plane materiel material.
Present invention also provides application of the ceramic surface material in industrial furnace.The application ceramic surface material can
Coated on above-mentioned industrial furnace tube skin to form ceramic surface material, stabilization of the safeguard industries with stove in use
Property.Industrial furnace described above can be the industrial furnaces well known to those skilled in the art such as boiler, kiln and heating furnace.
For a further understanding of the present invention, ceramic surface material provided by the invention is carried out with reference to embodiment detailed
Illustrate, protection scope of the present invention is not limited by the following examples.
1~embodiment of embodiment 10
Organosilicon is mixed with organic solvent, obtains solvent-laden composite organic liquid；By the filler by refining
It is mixed with the solvent-laden composite organic liquid after processing, adds auxiliary agent uniform stirring, filtering encapsulation, obtain ceramic watch
Plane materiel material.The content for the ceramic surface material each component that embodiment 1 to embodiment 10 provides is as shown in table 1.
The ceramic surface material of Examples 1 to 10 is sprayed to the main combustion of water-cooling wall of Mr. Yu's 1000MW generating plant pulverized coal boilers respectively
Area's water-cooling wall, superheater and reheater surface, 600t/d bulky refuse furnace of power-plant boilers water coolings wall surface, the life of 130t/h large sizes
Substance boiler water wall and high temperature superheater surface, coating thickness are 30~100 μm.Using after 1 year according to country or industry
Interior general examination criteria carries out performance detection to product, and testing result is as shown in table 2.
1 1~embodiment of embodiment of table, 10 ceramic surface material each component content and specification data table (wt%)
The performance parameter tables of data for the ceramic surface material that 2 1~embodiment of embodiment 10 of table provides
The explanation of above example is only intended to facilitate the understanding of the method and its core concept of the invention.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvement and modification are also fallen within the protection scope of the claims of the present invention.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest range caused.
Claims (12)
1. a kind of ceramic surface material, composed of the following components：
The organic solvent is selected from butyl acetate, dimethylbenzene, n-butyl ether, butyl acetic acid esters, hexahydrotoluene, just pungent
It is one or more in alkane and butyl titanate；
The filler is by graphene, graphite, transition group metallic oxide, composition silicate, rare earth oxide, nonmetallic, non-gold
Belong to compound, magnesium-yttrium-transition metal boride and metal to form.
2. ceramic surface material according to claim 1, which is characterized in that the organosilicon is selected from polysilazane, poly- silicon
It is one or more in boron azane, polysiloxanes, silicones azane, poly- silicon-carbon alkane, poly- silicon-carbon azane and polyborazine.
3. ceramic surface material according to claim 1, which is characterized in that the transition group metallic oxide is selected from oxidation
It is one or more in zirconium, chromium oxide, titanium oxide, molybdenum oxide and niobium oxide；The metal is in chromium, nickel, titanium, aluminium and yttrium
It is one or more；The composition silicate be selected from copper picotite, magnesium aluminate spinel, mullite, nepheline, kaolin, kyanite,
It is one or more in alumina silicate and zirconium silicate；The one kind of the rare earth oxide in cerium oxide, yttrium oxide and lanthana
Or it is a variety of；It is described nonmetallic selected from one or both of silicon and boron；The nonmetallic compound be selected from boron carbide, silicon boride,
It is one or more in boron nitride, silicon nitride, silicon carbide and boron oxide；The magnesium-yttrium-transition metal boride is selected from titanium boride, boron
Change one or more in zirconium, chromium boride and nickel borides；The auxiliary agent is selected from silane coupling agent, wetting dispersing agent and catalytic curing
It is one or more in agent.
4. according to claims 1 to 3 any one of them ceramic surface material, which is characterized in that the granularity of the filler is 50
~900nm.
5. ceramic surface ceramics according to claim 1, which is characterized in that the organosilicon is selected from polysilazane, poly- silicon
It is described when one or more in boron azane, polysiloxanes, silicones azane, poly- silicon-carbon alkane, poly- silicon-carbon azane and polyborazine
Polysilazane, poly- silicon boron azane, polysiloxanes, silicones azane, poly- silicon-carbon alkane and poly- silicon-carbon azane content independently be 0.5
~70wt%.
6. ceramic surface material according to claim 2, which is characterized in that the organosilicon is polysilazane, poly- silicon boron
Azane, polysiloxanes, silicones azane, poly- silicon-carbon alkane, poly- silicon-carbon azane and polyborazine mixture when, the poly- silicon nitrogen
Alkane, poly- silicon boron azane, polysiloxanes, silicones azane, poly- silicon-carbon alkane and poly- silicon-carbon azane content independently be 0.5~
67wt%.
7. the ceramic surface material according to claim 2 or 6, which is characterized in that the organosilicon of stating is polysilazane, gathers
Silicon boron azane, polysiloxanes, silicones azane, poly- silicon-carbon alkane, poly- silicon-carbon azane and polyborazine mixture when, it is described organic
The content of silicon is 30wt%~60wt%, and the content of the polysilazane is 10wt%~20wt%, the poly- silicon boron azane
Content is 10wt%~20wt%, the polysiloxanes, silicones azane, poly- silicon-carbon alkane, poly- silicon-carbon azane and polyborazine
Content independently is 2wt%~5wt%.
8. ceramic surface material according to claim 1, which is characterized in that the organic solvent is butyl acetate, diformazan
It is described when one or more in benzene, n-butyl ether, butyl acetic acid esters, hexahydrotoluene, normal octane and butyl titanate
Butyl acetate, dimethylbenzene, n-butyl ether, butyl acetic acid esters, hexahydrotoluene, the content of normal octane and butyl titanate are only
It is on the spot 0.5wt%~70wt%.
9. ceramic surface material according to claim 1, which is characterized in that the organic solvent is butyl acetate, diformazan
Benzene, n-butyl ether, butyl acetic acid esters, hexahydrotoluene, normal octane and butyl titanate mixture when, the acetic acid fourth
Ester, dimethylbenzene, n-butyl ether, butyl acetic acid esters, hexahydrotoluene, normal octane and butyl titanate content independently be
0.5wt%~67wt%.
10. ceramic surface material according to claim 3, which is characterized in that the rare earth oxide is cerium oxide, oxidation
When yttrium and lanthana, the content of the cerium oxide, yttrium oxide and lanthana independently is 0.1wt%~2wt%；
The content of the graphite is 0.1wt%~3wt%；The content of the graphene is 0.1wt%~3wt%；
The metal is chromium, nickel, titanium, aluminium and when yttrium, the chromium, nickel, titanium, aluminium and yttrium content independently be 0.1wt%~
20wt%；
The composition silicate be copper picotite, magnesium aluminate spinel, mullite, nepheline, kaolin, kyanite, alumina silicate and
When zirconium silicate, the copper picotite, magnesium aluminate spinel, mullite, nepheline, kaolin, kyanite, alumina silicate and zirconium silicate
Content independently is 0.1wt%~20wt%；
It is described it is nonmetallic be silicon and boron when, the content of the silicon and boron independently is 0.1wt%~20wt%；
When the nonmetallic compound is boron carbide, silicon boride, boron nitride, silicon nitride, silicon carbide and boron oxide, the carbonization
Boron, silicon boride, boron nitride, silicon nitride, silicon carbide and boron oxide content independently be 0.1wt%~20wt%；
When the magnesium-yttrium-transition metal boride is titanium boride, zirconium boride, chromium boride and nickel borides, the titanium boride, zirconium boride, boron
The content for changing chromium and nickel borides independently is 0.1wt%~20wt%；
When the transition metal oxide is zirconium oxide, chromium oxide, titanium oxide, molybdenum oxide and niobium oxide, the zirconium oxide, oxidation
Chromium, titanium oxide, molybdenum oxide and niobium oxide content independently be 0.1wt%~20wt%.
11. ceramic surface material according to claim 1, which is characterized in that the rare earth oxide is cerium oxide, oxidation
When yttrium and lanthana, the content of the cerium oxide, yttrium oxide and lanthana independently is 0.3wt%~1.5wt%；
The content of the graphite is 0.2wt%~2wt%；The content of the graphene is 0.2wt%~2wt%；
The metal is chromium, nickel, titanium, aluminium and when yttrium, the chromium, nickel, titanium, aluminium and yttrium content independently be 0.2wt%~
3wt%；
It is described it is nonmetallic be silicon and boron when, the content of the silicon and boron independently is 0.2wt%~3wt%；
The composition silicate be copper picotite, magnesium aluminate spinel, mullite, nepheline, kaolin, kyanite, alumina silicate and
When zirconium silicate, the copper picotite, magnesium aluminate spinel, mullite, nepheline, kaolin, kyanite, alumina silicate and zirconium silicate
Content independently is 0.2wt%~3wt%；
When the nonmetallic compound is boron carbide, silicon boride, boron nitride, silicon nitride, silicon carbide and boron oxide, the carbonization
Boron, silicon boride, boron nitride, silicon nitride, silicon carbide and boron oxide content independently be 0.2wt%~3wt%；
When the magnesium-yttrium-transition metal boride is titanium boride, zirconium boride, chromium boride and nickel borides, the titanium boride, zirconium boride, boron
The content for changing chromium and nickel borides independently is 0.2wt%~3wt%；
When the transition metal oxide is zirconium oxide, chromium oxide, titanium oxide, molybdenum oxide and niobium oxide, the zirconium oxide, oxidation
Chromium, titanium oxide, molybdenum oxide and niobium oxide content independently be 0.2wt%~3wt%.
12. a kind of surface coating, including investment precoat and priming paint, which is characterized in that the investment precoat is claim 1~11
Any one of them ceramic surface material.
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