CN100390321C - Gradient ceramic coating on steel substrate and its prepn process - Google Patents
Gradient ceramic coating on steel substrate and its prepn process Download PDFInfo
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- CN100390321C CN100390321C CNB2006100455021A CN200610045502A CN100390321C CN 100390321 C CN100390321 C CN 100390321C CN B2006100455021 A CNB2006100455021 A CN B2006100455021A CN 200610045502 A CN200610045502 A CN 200610045502A CN 100390321 C CN100390321 C CN 100390321C
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Abstract
The present invention relates to one kind of gradient Fe/Al2O3 material coating on steel substrate part and its preparation process. The coating consists of one inner layer, one middle layer and one outer layer, and has Al2O3 content gradually raised from 10-20 wt% in the inner layer to 100 wt% in the outer layer, Fe content gradually lowered from 65-85 wt% in the inner layer to 0 wt% in the outer layer, and Al content gradually lowered from 5-15 wt% in the inner layer to 0 wt% in the outer layer. The coating is prepared through spraying process to form the inner layer and the middle layer, and sol-gel process to form the outer layer with painted Al(OH)3 sol. The coating is wear resistant, corrosion resistant, high in high temperature oxidation resistance and high in high temperature heat stability, may be well matched physically and chemically with steel base in less macrostress and moderated interface combining strength.
Description
(1) technical field under
The present invention relates to a kind of gradient ceramic coating on steel substrate, particularly a kind of at base steel component surface coating Fe-Al/Al
2O
3Gradient material coating, and their preparation method.
(2) background technology
At present, iron and steel is to use one of maximum material on the engineering, but because the limitation of its performance such as high temperature resistant, corrosion-resistant, wear-resistant, be in for a long time at many steel component of industry such as metallurgy, chemical industry, machineries under the work condition environment of high temperature, wearing and tearing and seriously corroded and use, normal concentrated wear because of the surface, corrosion failure etc. cause whole component failure, the annual thus financial loss of bringing multi-billion dollar.Pottery has excellent properties such as hardness height, wear-resisting, stable chemical performance, but its toughness is low, it is contemplated that, will have broad application prospects with metal composite.In recent years, owing to the application potential at automobile, metallurgy and energy field, Fe-Al/Al
2O
3Composite study receives much concern.Scientists utilizes plasma spraying, laser melting coating plasma spraying, detonation flame spraying, sol-gel methods such as (Sol-gel) to prepare Al
2O
3The coated steel sill is in the hope of improving the performance such as high temperature resistant, corrosion-resistant, wear-resistant of base steel component.
Less to the research report of Fe-Al/Al2O3 gradient clad steel sill both at home and abroad.The method that obtains ceramic coating in the metallic surface is a lot, and the most frequently used is heat spraying method.Heat spraying method comprises plasma spraying, laser melting coating plasma spraying and detonation flame spraying etc.But plasma spraying, laser melting coating plasma spray coating process complexity are not suitable for scale operation, and detonation flame spraying costs an arm and a leg, and sedimentation velocity is low, so, be subjected to certain restriction in the application, and had unsettled γ-Al
2O
3Cracking often in the use takes place or phenomenon such as peels off in crystal formation and be difficult to shortcoming such as densification, and because the thermal expansivity and the Young's modulus of metal and pottery do not match, cause matrix and to be coated with the interlayer bonding strength low.Thereby fundamentally do not eliminate or relax the thermal stresses of pottery and intermetallic interface, the example of successful Application is not seen as yet on engineering report.
Wet processing is exactly that starting material to be coated are made solution, suspension or slip, sprays or brushes on the base material, makes it produce physical-chemical reaction or diffusional effect and the coating that forms through evaporation or heating.With fastest developing speed in the Wet technique, the most noticeable is sol-gel method (Sol-gel), and it comprises reactant hydrolysis (at first is complexing to polycomponent), polycondensation and steps such as drying, heat treated.The principal feature of this method is: (1) reactant is to mix reaction in the low viscous liquid of molecular level degree, can prepare the product of high purity, high homogeneous.(2) reaction can be carried out under lower temperature, so can prepare ceramic coating on the matrix widely.(3) can control the microtexture of gel.(4) required equipment is inexpensive, and is simple to operate.Therefore, the research of sol-gel becomes one of current glass, the most active problem of ceramic subject.The investigator of California, USA university with it as research topic for the aerospace pottery.This method is to making the coating particularly advantageous, and this is because will discharge water outlet or ethanol in polycondensation and exsiccant process, and coating is the easy defective such as bubble crackle that occurs unlike integral body.The eighties initial stage has been made the superconducting coating of fine and close aluminum oxide, zirconium white, titanium oxide, silicon oxide, cerium oxide, Thorotrast and sol-gel method preparation
(3) summary of the invention
The present invention is in order to overcome the deficiency of above technology, a kind of gradient ceramic coating on steel substrate is provided, can improve the work-ing life of steel component, improve performances such as its wear-resisting, corrosion-resistant and high-temperature oxidation resistant, make its performance that promptly has steel that the performance of alumina-ceramic be arranged again, hope is in some field energy instead of steel, so that can use the longer time in more field.
Another object of the present invention, be to provide the preparation method of above-mentioned base steel coating, the base steel coating of this preparation method's preparation has the gradient composite structure, macrostress between eliminating layer and interlayer and coating and steel matrix effectively, make interface bond strength moderate,, preparation method more superior with obtained performance is easy to realize suitability for industrialized production.
The objective of the invention is to realize by following measure:
Gradient ceramic coating on steel substrate of the present invention by internal layer, middle layer and outer the composition, contains Al successively
2O
3, Fe and Al, its special feature is: from inside to outside, its Al
2O
3Weight percent be increased to outer fieldly 100% gradually by 10～20% of internal layer, the weight percent of Fe is reduced to outer field 0% gradually by 65～85% of internal layer, the weight percent of Al is reduced to outer field 0% gradually by 5～15% of internal layer.All the components all is quasi-continuous variation.
Gradient ceramic coating on steel substrate of the present invention, the Al in described middle layer
2O
3Weight percent be 45～55%, the weight percent of Fe is 35～45%, the weight percent of Al is 3～12%.
Gradient ceramic coating on steel substrate of the present invention, described middle layer are divided into three layers, from inside to outside Al
2O
3Content raise gradually, the content of Fe reduces gradually, the content of Al reduces gradually.
The preparation method of above-mentioned gradient ceramic coating on steel substrate of the present invention, adopt following steps: described internal layer and middle layer are adopted spraying method to spray on steel matrix respectively and are made, and used spraying slip is by Fe powder, Al powder and α-Al
2O
3The Fe-Al/Al that powder is made into
2O
3Mixed slurry; The outer sol-gel method coating Al (OH) that adopts
3Colloidal sol is made; Carry out sintering, insulation then, cool off, come out of the stove.
The preparation method of the invention described above, described Al (OH)
3The raw material of colloidal sol is Tai-Ace S 150, ammoniacal liquor and dispersion agent trolamine.Al (OH)
3The main chemical reactions formula of colloidal sol preparation is as follows:
Al
2(SO
4)
3+6NH
3·H
2O＝2Al(OH)
3+3(NH
4)
2SO
4
The preparation method of the invention described above, the solvent of Fe-Al/Al2O3 mixed slurry is that weight percentage is the azeotropic solvent that 40～60% dehydrated alcohols and 60～40% tincture ketone are formed, wherein Fe-Al/Al
2O
3Fe-Al/Al in the mixed slurry
2O
3(described Fe-Al/Al
2O
3Represent Fe, Al
2O
3, three kinds of component sums of Al, down with) weight percent be 20～30%.
The preparation method of the invention described above, slip viscosity is 45～50cp during spraying, and the air pressure of spray gun is 0.25～0.4Mpa, and spray distance is 15～20cm.
The preparation method of the invention described above, the dispersion agent trolamine accounts for Al (OH)
3The colloidal sol weight percent is 0.5～1%, and applying viscosity during coating is 12～22cp, and wetting time is 10～15min, and pull rate is 0.2～2mm/s, more than the coating back seasoning 8h.
The preparation method of the invention described above, agglomerating plant is a non-pressure sintering furnace, and sintering temperature is 1100～1200 ℃, and soaking time is 0.5～1 hour.
The present invention is applied to metal matrix ceramic composite coating with the design philosophy of gradient material, adopts spraying method and spraying method and sol-gel method to combine and prepares gradient ceramic coating on steel substrate on steel matrix, Fe, Al and Al
2O
3Change α-Al in gradient
2O
3Weight percentage outside the steel matrix side direction, increase gradually, and the weight percentage of iron powder and aluminium powder reduces gradually, the three all is quasi-continuous variation.The content of iron is higher in the internal layer, and is bigger with the bonding force of base steel, Al in the skin
2O
3Content the highest, its work-ing life, wear resistance, corrosion-resistant and high-temperature oxidation resistance all improve a lot.In addition, because each components contents is quasi-continuous variation, the macrostress between eliminating layer and interlayer and coating and steel matrix effectively, bonding strength is better.
The composite material surface hardness of the present invention's preparation approximately is 8 times of steel matrix; Abrasion loss approximately is 1/10th of a steel matrix under the same terms; Corrosion resistance nature is obvious more superior than steel matrix.
The present invention is applied to metal matrix ceramic composite coating with the design philosophy of gradient material, adopts spraying method and spraying method and sol-gel method to combine and prepare multilayer Fe-Al/Al on steel matrix
2O
3Coating improves the bonding strength between top coat and steel matrix greatly.The bonding strength of common aluminum oxide coating layer and steel matrix is approximately 8.16Mpa, and the bonding strength of gradient cladding of the present invention and steel matrix on average reaches 17.62Mpa.
Measure the Vickers' hardness of material under the same conditions, gradient cladding hardness of the present invention on average reaches 4.1338GPa, and the average hardness of steel matrix is 0.5042GPa.
The same terms is measured the wear resistance of material, the abrasion loss average out to 4.119 * 10 of gradient cladding of the present invention down
-3G/min, and the abrasion loss average out to 38.744 * 10 of steel matrix
-3G/min.
Measure the erosion resistance of material under the same conditions, gradient cladding of the present invention is all superior than steel matrix.The steel matrix surface is by heavy corrosion, and composite material surface is slight being corroded.
Therefore, gradient ceramic coating on steel substrate of the present invention, have wear-resisting, corrosion-resistant, high-temperature oxidation resistance is good, the stable performance of high temperature calorifics, good with steel matrix physical chemistry matching, adopt the gradient compounding technology effectively the macrostress between eliminating layer and interlayer and coating and steel matrix make interface bond strength moderate.
Preparation method of the present invention, adopting process is simple, be easy to industrialized spraying method and sol-gel technique, can increase substantially steel component ground work-ing life, and have preparation technology, equipment simply, be convenient to characteristics such as scale operation.
(4) embodiment
Embodiment 1:
The gradient ceramic coating on steel substrate of present embodiment from inside to outside, is formed α-Al in each layer for three layers by internal layer, middle layer and skin successively
2O
3, Fe and Al weight percent see Table 1 respectively.
Table 1
| Internal layer | The middle layer | Outer | |
| α-Al 2O 3(wt％) | 15 | 45 | 100 |
| Fe(wt％) | 80 | 45 | 0 |
| Al(wt％) | 5 | 10 | 0 |
Concrete technology is as follows:
This test selects 45 for use
#Steel is a body material, sanding and polishing is carried out on its surface handle.Adopt spraying method and spraying method and the sol-gel method two kinds of methods that combine on steel matrix, to prepare three layers of Fe-Al/Al respectively
2O
3Coating, internal layer and middle layer adopt spraying method to spray Fe-Al/Al on steel matrix
2O
3Mixed slurry, outermost layer adopt sol-gel method to apply Al (OH) on base substrate
3Colloidal sol, dense sintering prepares base steel Fe-Al/Al2O3 gradient cladding matrix material under same temperature at last.
The present invention prepares Fe-Al/Al
2O
3The mixed slurry solvent for use is that weight percentage is the azeotropic solvent that 40～60% dehydrated alcohols and 60～40% tincture ketone are formed, best powder weight percentage 20～30% in the slip wherein, slip viscosity is during spraying: 45～50cp, the air pressure of spray gun: 0.25～0.4Mpa, spray distance: 15～20cm.
Al (OH)
3The raw material of colloidal sol is Tai-Ace S 150, ammoniacal liquor and dispersion agent trolamine.The dispersion agent trolamine accounts for 0.5～1% of total mass, applies viscosity: 12～22cp during coating, wetting time: 10～15min, and pull rate: 0.2～2mm/s, coating back base substrate must be more than the seasoning 8h.
Agglomerating plant of the present invention is traditional non-pressure sintering furnace, and final sintering temperature: 1100～1200 ℃, best soaking time is 0.5～1 hour, heat-up rate: 400 ℃ were difficult for too fast in the past, be 3～5 ℃/min, can suitably accelerate heat-up rate later for 400 ℃, for: 10～20 ℃/min.
Embodiment 2:
The gradient ceramic coating on steel substrate of present embodiment, from inside to outside, by internal layer, middle layer and outer the composition, the middle layer is divided into three layers again, totally five layers successively.Al in each layer
2O
3, Fe and Al weight percent see Table 2 respectively.
Table 2
Its preparation is substantially the same manner as Example 1.
Embodiment 3:
The gradient ceramic coating on steel substrate of present embodiment, from inside to outside, by internal layer, middle layer and outer the composition, the middle layer is divided into three layers again, totally five layers successively.Al in each layer
2O
3, Fe and Al weight percent see Table 3 respectively.
Table 3
Its preparation is substantially the same manner as Example 1.
Embodiment 4:
The gradient ceramic coating on steel substrate of present embodiment, from inside to outside, by internal layer, middle layer and outer the composition, the middle layer is divided into four layers again, totally six layers successively.Al in each layer
2O
3, Fe and Al weight percent see Table 4 respectively.
Table 4
Its preparation is substantially the same manner as Example 1.
Claims (9)
1. a gradient ceramic coating on steel substrate by internal layer, middle layer and outer the composition, contains Al successively
2O
3, Fe and Al, it is characterized in that: from inside to outside, its Al
2O
3Weight percent be increased to outer fieldly 100% gradually by 10～20% of internal layer, the weight percent of Fe is reduced to outer field 0% gradually by 65～85% of internal layer, the weight percent of Al is reduced to outer field 0% gradually by 5～15% of internal layer.
2. gradient ceramic coating on steel substrate according to claim 1 is characterized in that: the Al in described middle layer
2O
3Weight percent be 45～55%, the weight percent of Fe is 35～45%, Al weight percent be 3～12%.
3. gradient ceramic coating on steel substrate according to claim 1 and 2 is characterized in that: described middle layer is divided into three layers, from inside to outside Al
2O
3Content raise gradually, the content of Fe reduces gradually, the content of Al reduces gradually.
4. the preparation method of claim 1 or 2 described gradient ceramic coating on steel substrate, it is characterized in that: adopt following steps, described internal layer and middle layer are adopted spraying method to spray on steel matrix respectively and are made, and used spraying slip is by Fe powder, Al powder and α-Al
2O
3The Fe-Al/Al that powder is made into
2O
3Mixed slurry; The outer sol-gel method coating Al (OH) that adopts
3Colloidal sol is made; Carry out sintering, insulation then, cool off, come out of the stove.
5. preparation method according to claim 4 is characterized in that: described Al (OH)
3The raw material of colloidal sol is Tai-Ace S 150, ammoniacal liquor and dispersion agent trolamine.
6. preparation method according to claim 4 is characterized in that: Fe-Al/Al
2O
3The solvent of mixed slurry is that weight percentage is the azeotropic solvent that 40～60% dehydrated alcohols and 60～40% tincture ketone are formed, wherein Fe-Al/Al
2O
3Fe-Al/Al in the mixed slurry
2O
3Weight percent be 20～30%.
7. preparation method according to claim 6 is characterized in that: slip viscosity is 45～50cp during spraying, and the air pressure of spray gun is 0.25～0.4Mpa, and spray distance is 15～20cm.
8. preparation method according to claim 5 is characterized in that: the dispersion agent trolamine accounts for Al (OH)
3The colloidal sol weight percent is 0.5～1%, and applying viscosity during coating is 12～22cp, and wetting time is 10～15min, and pull rate is 0.2～2mm/s, more than the coating back seasoning 8h.
9. preparation method according to claim 4 is characterized in that: agglomerating plant is a non-pressure sintering furnace, and sintering temperature is 1100～1200 ℃, and soaking time is 0.5～1 hour.
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|---|---|---|---|
| CNB2006100455021A CN100390321C (en) | 2006-07-17 | 2006-07-17 | Gradient ceramic coating on steel substrate and its prepn process |
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|---|---|---|---|
| CNB2006100455021A CN100390321C (en) | 2006-07-17 | 2006-07-17 | Gradient ceramic coating on steel substrate and its prepn process |
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| CN100390321C true CN100390321C (en) | 2008-05-28 |
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| CN101775527B (en) * | 2010-03-11 | 2012-07-25 | 湖南大学 | Ceramic particle reinforced aluminum-based gradient composite material and preparation method thereof and jetting precipitation device for preparing material |
| CN102010167B (en) * | 2010-09-14 | 2012-09-05 | 浙江锦诚耐火材料有限公司 | Low-temperature wear-resisting plastic coating material |
| WO2013172911A1 (en) * | 2012-05-14 | 2013-11-21 | Arcanum Alloy Design Inc. | Sponge-iron alloying |
| DE102014104672A1 (en) * | 2014-04-02 | 2015-10-08 | Kennametal Inc. | Coated cutting tool and method for its manufacture |
| WO2017201418A1 (en) | 2016-05-20 | 2017-11-23 | Arcanum Alloys, Inc. | Methods and systems for coating a steel substrate |
| CN106119583B (en) * | 2016-06-30 | 2017-11-07 | 济南大学 | A kind of preparation method of pressureless sintering titanium/aluminum oxide gradient composites |
| CN106623945B (en) * | 2016-10-16 | 2019-01-08 | 浙江炊大王炊具有限公司 | A kind of metal matrix wear-resistant corrosion-resistant surface covering composite material and preparation method |
| CN109396447B (en) * | 2018-11-21 | 2021-01-19 | 武汉理工大学 | Hollow pipe forming method based on grain-size-graded titanium diboride and titanium gradient composite material |
| CN109550961B (en) * | 2018-12-20 | 2020-12-08 | 武汉理工大学 | Centrifugal sintering method of thin-wall pipe functional gradient material |
| CN111960823B (en) * | 2020-08-28 | 2021-11-02 | 昆明理工大学 | Alkaline earth metal ion doped rare earth tantalate or niobate thermal barrier coating and preparation method thereof |
| CN112876080B (en) * | 2021-02-04 | 2022-02-15 | 中国科学院合肥物质科学研究院 | Glass ceramic coating for lead-based reactor pump impeller and preparation method thereof |
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