CN103469207A - High-temperature oxidation resistant and corrosion resistant glass ceramic composite coating and preparation technology thereof - Google Patents
High-temperature oxidation resistant and corrosion resistant glass ceramic composite coating and preparation technology thereof Download PDFInfo
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Abstract
The invention relates to an inorganic high temperature protection coating technology, particularly to a high-temperature oxidation resistant and corrosion resistant glass ceramic composite coating which can be used for components made of titanium alloy and other metallic materials and a preparation technology of the composite coating. The coating is formed through uniformly dispersing and distributing micron scale ceramic particle phase and nanoscale metal/oxide mixed powder into a glass matrix phase, the glass matrix phase is formed through performing high temperature conversion on sodium silicate water glass or potassium silicate water glass, the micron phase ceramic particle phase accounts for 15-60 wt% of the glass ceramic composite coating, and the nanoscale metal/oxide mixed powder accounts for 0.5-5 wt% of the glass ceramic composite coating. The coating preparation technology comprises the steps of coating material preparation, coating material spraying and high temperature processing. The glass ceramic composite coating, provided by the invention, is compact, has no holes, has higher strength and breaking tenacity, and has good binding force with a titanium alloy matrix and thermal expansion coefficient matched with the titanium alloy matrix, thereby having excellent anti-thermocycling thermal shock performance, high-temperature oxidation resistance and corrosion resistance.
Description
Technical field
The present invention relates to the inorganic high-temp protective coating technique, be specially a kind of corrosion resistant glass-ceramic compound coating of resistance to high temperature oxidation and preparation technology thereof who can be used for titanium alloy and other metallic substance parts.
Background technology
Titanium base alloy has higher specific tenacity because of it, and good high-temperature behavior, be widely used in space flight, aviation, navigation and war industry field.But, its resistance to high temperature oxidation, hot corrosion resistance deficiency and the crisp down phenomenon limits of oxygen its practical application in hot environment.For example: Ti-6Al-4V and Ti60 alloy, maximum operation (service) temperature is respectively 300 ℃ and 600 ℃, in higher temperature, there will be vigorous oxidation and the crisp phenomenon of oxygen, thereby causes the decline of alloy mechanical property.And take the TiAl intermetallic compound that Ti-47Al-2Cr-2Nb is representative, its hot strength can make its working temperature reach 800 ℃～900 ℃, but oxidation corrosion is serious in this temperature range, especially under the thermal etching environment, as: in the environment of sodium chloride salt and sodium sulfate salt or both mixing, the quick deterioration of serious thermal etching and mechanical property can occur in TiAl base alloy.
Traditional high-temperature protection coating comprises: simple calorized coating, modification calorized coating and NiCrAlY coating.These coatings are nickel base superalloy matrix development and design exploitation originally, problem occurred after being transplanted on titanium base alloy.Serious mutual diffusion occurs in NiCrAlY coating and TiAl base alloy, at interface formation fragility phase and a large amount of hole of coatings and substrate.Calorized coating is at the very high TiAl of titanium base alloy Surface Creation layer of brittle
3phase, easily germinate crackle.A kind of physical vacuum vapour deposition TiAlCr coating gone out for titanium base alloy is newly developed, have good oxidation susceptibility, but its hot corrosion resistance deficiency.In addition, NiCrAlY coating and TiAlCr coating all need to take vacuum technique, and preparation cost is higher.
The film forming matter of organic high-temperature coatings is prone to oxidative degradation and thermal destruction under hot environment, has limited its use temperature.Contain a large amount of zinc powders in waterborne zinc-rich coating, so its use temperature is generally lower than 300 ℃.The organic silica-based coating heatproof of nano modification can reach 700 ℃, but, because its nano particle cost is higher, is only limited to and is applied to a small amount of occasion, and coating mechanical properties decrease after the organic silicon high-temperature thermolysis, and coating is easily peeled off.Inorganic high-temp protective coating heatproof can reach 1000 ℃; and by adding the temperature tolerance of the ceramic particles raising coatings such as aluminum oxide, quartz; but the coating of adding separately aluminum oxide is often not fine and close because of the vigorous reaction porous of aluminum oxide and glass basis; easily in process of cooling, germinate crackle and add separately quartzy coating because of not mating of thermal expansivity and alloy substrate; or make coating peel off from matrix surface in the cold cycling process, therefore usually just as the temporary protective coat in the alloy hot procedure.As: the Chinese invention patent application that publication number is CN101314808A, high-temperature inoxidzable coating material can peel off from the steel substrate surface naturally in process of cooling, therefore can not use as the Long-term Anti oxide covering.
The glass-ceramic coating is the high-temperature protection coating technology of widespread use, by regulating glass ingredient and additive ceramics component and ratio, can control the matching of its thermal expansivity and matrix, has good heat resistanceheat resistant circulation spalling resistance.Its shortcoming is that the regulate process of glass ingredient needs the long period, the technological process of a smelting glass piece and mill glaze need to be arranged, and contradiction may occur between thermal expansivity optimization and oxidation and corrosion performance optimization.
Therefore, develop a kind of novel, preparation technology simple and the titanium base alloy matrix has high-performance high temperature resistance protective coating good matched coefficients of thermal expansion, that possess Long-term Anti oxidation corrosion resistance nature, there is important technology for the high temperature application of titanium base alloy and other metal workpieces and be worth and application prospect.
Summary of the invention
The object of the present invention is to provide the corrosion resistant glass-ceramic compound coating of a kind of resistance to high temperature oxidation and preparation technology thereof, only need to use market to make by firsthand raw material, raw material and preparation technology of coating process are nontoxic, pollution-free, the glass-ceramic compound coating possesses Long-term Anti high temperature oxidation corrosion resistance nature, and with the titanium base alloy matched coefficients of thermal expansion.
Technical scheme of the present invention is:
The corrosion resistant glass-ceramic compound coating of a kind of resistance to high temperature oxidation, this coating be micron order ceramic particle phase and nano level metal/oxide compound mixed powder even dispersion be distributed in glass basis mutually in, its composition comprises:
The glass basis phase, formed through pyrolytic conversion by sodium silicate water glass or potassium silicate water glass;
Micron order ceramic particle phase, particle size range is 1 μ m～20 μ m, total content accounts for the 15wt%～60wt% of glass-ceramic compound coating;
Nano level metal/oxide compound mixed powder, diameter range is 1nm～500nm, total content accounts for the 0.5wt%～5wt% of glass-ceramic compound coating; Wherein, nano level metal/oxide compound mixed powder is nano-titanium/titanium dioxide powder, titanium: the weight ratio of titanium oxide is 0.1～0.5.
The corrosion resistant glass-ceramic compound coating of described resistance to high temperature oxidation, the micron order ceramic particle is aluminum oxide and quartzy mixed powder mutually, aluminum oxide: quartzy weight ratio is 0.1～0.8.
The corrosion resistant glass-ceramic compound coating of described resistance to high temperature oxidation, alumina particle, partly or entirely replaced by the mineral that kaolin or other alumina content surpass 50wt%.
The corrosion resistant glass-ceramic compound coating of described resistance to high temperature oxidation, quartz particles, partly or entirely replaced by the mineral that quartzite or silicon carbide or other silica content surpass 50wt%.
The preparation technology of the corrosion resistant glass-ceramic compound coating of described resistance to high temperature oxidation comprises following three process step:
(1) coating preparation operation
Water glass, micron order ceramic particle and nano level metal/oxidate powder powder stock is mixed, adopt high-speed stirring dispersion machine or other mechanical means that solid particulate matter is dispersed in water glass, form coating; Wherein, water glass is sodium silicate water glass or potassium silicate water glass, and modulus is 3～3.9;
(2) paint spay-coating operation
The twice that the sprayed coating minimum thickness is micron order ceramic particle maximum diameter, and a coating thickness is no more than 100 μ m; Spraying method is the spraying of normal temperature atmosphere, and spray pressure is 0.3MPa～0.8MPa;
(3) pyroprocessing operation
Advanced person's prebake conditions of passing through is processed, and then carries out pyroprocessing.
The preparation technology of the corrosion resistant glass-ceramic compound coating of described resistance to high temperature oxidation, in step (1), the rotating speed of high-speed stirring dispersion machine is 1000～2000r/min, the time is 10～30min.
The preparation technology of the corrosion resistant glass-ceramic compound coating of described resistance to high temperature oxidation, in step (2), a spray-on coating thickness is at 10～100 μ m.
The preparation technology of the corrosion resistant glass-ceramic compound coating of described resistance to high temperature oxidation, in step (3), prebake conditions is processed and pyroprocessing all can be carried out in atmosphere, does not need vacuum or special protection atmosphere; The prebake conditions treatment temp is 70 ℃～300 ℃, and the treatment time is 24h～36h.
The preparation technology of the corrosion resistant glass-ceramic compound coating of described resistance to high temperature oxidation, in this prebake conditions treatment temp interval, carry out temperature-gradient method and insulation:
(1) at 70 ℃～80 ℃ baking 5～12h;
(2) at 110 ℃～130 ℃ baking 5～12h;
(3) at 230 ℃～260 ℃ baking 5～12h.
The preparation technology of the corrosion resistant glass-ceramic compound coating of described resistance to high temperature oxidation, in step (3), the pyroprocessing temperature is 700 ℃～950 ℃, the treatment time is 0.5h～2h.
Design philosophy of the present invention is:
Glass ceramic coating has good high-temperature stability and chemical stability, therefore can be as alloy protective coating at high temperature, but traditional glass ceramic coating adopts melting-fast cold method to prepare frit, and need follow-up high-temperature heat treatment to come optimized coatings mechanical property and thermal characteristics to separate out ceramic crystal from frit, coated component complexity and preparation technology's long flow path; If adopting potassium silicate water glass or sodium silicate water glass is base-material, by direct interpolation micron order ceramic particle phase and adopt the way of nano level metal/oxide compound mixed powder modification to prepare the glass-ceramic compound coating, technique is simple, and be base-material owing to adopting water glass, but coating direct spraying, thereby easy construction.
Water glass, potassium silicate water glass or sodium silicate water glass that the modulus of selecting can directly to buy on market is 3～3.9, be conducive to the large-scale application of glass ceramic coating of the present invention.
Micron order ceramic particle phase, selection can improve strength of coating and regulates the alumina ceramic grain of coating thermal expansivity and can improve coating failure toughness and control alumina particle and the quartz particles of glass basis phase interfacial reaction.Ratio by two kinds of ceramic particles of reasonable adjustment, make between glassy phase and ceramic particle phase wetting good, form fine and close bonding interface, reduce the coating internal void, suppress excessive surface reaction, improve strength of coating and fracture toughness property, and regulate the thermal expansivity of coating, optimize rear oxidation aluminium: quartzy weight ratio is 0.1～0.8, and the ceramic particle total content is controlled to 15wt%～60wt%.
Nano level metal/oxide compound mixed powder, select cubical expansivity after Pilling-Bedworth ratio(burning) be greater than 1.5, oxide compound evaporation rate oxygen rate of diffusion is low, can and SiO
2-Na
2o is glass and SiO
2-K
2o is the titanium/titanium dioxide powder of glass generation pyroreaction, wherein nano-titanium: the weight ratio of titanium oxide is 0.1～0.5.Nano level metal/oxide compound mixed powder can be filled up the space that may occur between glass basis phase and ceramic particle phase, further control surface reaction, improve intensity, and make the smooth flawless of coatingsurface, coating inside and coating/basal body interface dense non-porous hole, improve coated substrate interface binding power and thermal shock resistance, thereby make coating can bear cold cycling and long term high temperature working conditions; Selecting the diameter range of nanometer powder is 1nm～500nm, and content accounts for the 0.5wt%～5wt% of glass-ceramic compound coating.
This glass-ceramic compound coating preparation technology comprises the three process step: coating preparation, paint spay-coating and pyroprocessing; With common glass-ceramic compound coating, compare, its preparation section has reduced the glass frit refining and the glass glaze grinds operation.
In the coating preparation operation, adopt common high-speed stirring dispersion machine to get final product better dispersion paints, rotating speed is 1000～2000r/min, and the time is 10～30min.
In the paint spay-coating operation, adopt normal temperature atmosphere spraying method to get final product, spray pressure is 0.3MPa～0.8MPa.
In the pyroprocessing operation, take step-by-step processing, advanced person's prebake conditions of passing through is processed, and then carries out pyroprocessing, and prebake conditions is processed and pyroprocessing all can be carried out in atmospheric environment, does not need vacuum or special protection atmosphere; The prebake conditions treatment temp is 70 ℃～300 ℃, treatment time is 24h～36h, can in this prebake conditions treatment temp interval, carry out temperature-gradient method and insulation, process and can make the moisture of coating inside slowly volatilize by temperature-gradient method, thereby avoid the inner hole that forms of coating, be conducive to the fine and close compound coating of follow-up preparation.The pyroprocessing temperature is 700 ℃～950 ℃, and the treatment time is 0.5h～2h, by pyroprocessing, can make water glass be transformed into glassy phase,, increase strength of coating and improve coating and the bonding force of alloy substrate.
Advantage of the present invention and effect are:
1, the glass-ceramic compound coating that the present invention develops not with an organic solvent, does not therefore have the volatilization of organic solvent in the preparation process of coating, and preparation technology of coating is nontoxic, pollution-free.
2, the glass-ceramic compound coating that the present invention develops, adopt water glass as dispersion soln and utilize it can be transformed into glass basis these characteristics mutually in the later stage sintering procedure, make this coating can as traditional organic coating, adopt simple paint spay-coating technique, and compare with common glass-ceramic compound coating, its preparation section has reduced the glass frit refining and the glass glaze grinds operation, therefore greatly facilitates the construction of coating.
3, the coating of the present invention's development not only possesses good anti-constant temperature oxidation susceptibility, and, because coating and titanium alloy matched coefficients of thermal expansion are good, therefore has good anti-cyclic oxidation performance and thermal shock resistance.
4, coating of the present invention has good hot corrosion resistance, sodium-chlor and sodium sulfate mixing salt can effectively protect alloy substrate in severe environment.Because actual corrosive environment is not the pure zirconia environment, so the good hot corrosion resistance of coating is expanded the practical application of coating.
5, high temperature oxidation corrosion resistance glass-ceramic compound coating of the present invention, be particularly useful for running on the protection of the titanium base alloy product (as: common alpha+beta biphase titanium alloy, gamma-TiAl alloy etc.) of hot environment, adopt the mode of common spraying paint spay-coating can be arrived to the alloy surface through sandblasting, after pyroprocessing, coating can effectively reduce alloy substrate oxidation corrosion speed at high temperature.In addition, also can be applicable to the high temperature corrosion protection of the material (as: parts such as carbon steel, stainless steel) of other type.
The accompanying drawing explanation
Fig. 1 this glass-ceramic compound coating for preparing on the Ti-47Al-2Cr-2Nb alloy substrate.
Fig. 2 this glass-ceramic compound coating for preparing on the Ti-6Al-4V alloy substrate.
Fig. 3 for this glass-ceramic compound coating of preparing on the Ti-6Al-4V alloy substrate 900 ℃ of cross-section photograph after the 100h cyclic oxidation.
Fig. 4 for this glass-ceramic compound coating of preparing on the Ti-6Al-4V alloy substrate at 900 ℃ of surface topography photos after 50 thermal shocks are processed.
This glass-ceramic compound coating cross-section photograph 900 ℃ oxidation 100h after of Fig. 5 for preparing on the Ti60 alloy substrate.
Fig. 6 is not for having the photomacrograph of Ti-47Al-2Cr-2Nb alloy (b) after 850 ℃ of thermal etching 100h of cated Ti-47Al-2Cr-2Nb alloy (a) and this glass-ceramic compound coating of preparation.
This glass-ceramic compound coating cross-section photograph 1000 ℃ cyclic oxidation 120h after of Fig. 7 for preparing on the Ti-47Al-2Cr-2Nb alloy substrate.
Embodiment
The corrosion resistant glass-ceramic compound coating of resistance to high temperature oxidation of the present invention and preparation technology thereof, the glass-ceramic compound coating is that micron order ceramic particle phase and nano level metal/oxide compound mixed powder even dispersion are distributed in the glass basis parent phase, and glass basis is transformed through pyroprocessing by sodium silicate water glass or potassium silicate water glass; Micron order ceramic particle phase, total content accounts for the 15wt%～60wt% of glass-ceramic compound coating; Selection can improve strength of coating and regulates the alumina ceramic grain of coating thermal expansivity and can improve coating failure toughness and control alumina particle and the quartz particles of glass basis phase interfacial reaction.Nano level metal/oxide compound mixed powder, content accounts for the 0.5wt%～5wt% of glass-ceramic compound coating; Select nano-titanium/titanium dioxide powder, to fill up the space that may occur between glass basis phase and micron order ceramic particle phase, and improve the coated substrate interface binding power.The mineral that described alumina particle can be partly or entirely surpassed 50wt% by kaolin or other alumina content replace, and quartz particles can be partly or entirely surpassed 50% mineral by quartzite or silicon carbide or other silica content and replaces.Glass-ceramic compound coating of the present invention only need to use market can be firsthand raw material make and do not need previously prepared glass glaze, in the preparation process of coating not with an organic solvent, preparation process is nontoxic, pollution-free, meets energy-conservation and environmental protection development trend; Glass-ceramic compound coating dense non-porous of the present invention hole, there is bonding force that higher intensity, fracture toughness property and titanium alloy substrate are good and the thermal expansivity of coupling, therefore there is good cold-and-heat resistent cycling hot shock stability and resistance to high temperature oxidation corrosion resistance nature.The coating use temperature can reach 900 ℃ and even 1000 ℃, can be used for titanium alloy and other metal partss.
Embodiment 1
Take the potassium silicate water glass that the 200g modulus is 3.9, the aluminum oxide powder 20g that particle diameter is 1～10 μ m, the silica powder 60g that particle diameter is 1～10 μ m, in the nano-titanium that the peak value particle diameter is 50nm/titanium oxide mixed powder powder 8g(the present embodiment, titanium: the weight ratio of titanium oxide is 0.2), pre-mixing aluminum oxide, quartz, nano-titanium/titanium dioxide powder, then be added into the pre-mixing powder in water glass, and add 10g distilled water adjusting coating viscosity to make coating stir rear applicable spraying.In whipping process, add the pottery that particle diameter is 1mm to stir ball increase dispersed with stirring effect, after the rotating speed stirring 20min with 2000rpm in stirring dispersion machine, after 300 eye mesh screens filter, obtain coating.Adopt the mode of spraying that paint spay-coating is arrived to the Ti-47Al-2Cr-2Nb alloy component surface through sandblasting, the coating sprayed is after self-vulcanizing, at 70 ℃～80 ℃ baking 12h, 110 ℃～130 ℃ baking 10h, 230 ℃～260 ℃ baking 5h, then fire and process 90min taking-up air cooling through 900 ℃.
As shown in Figure 1, the glass-ceramic compound coating prepared on the Ti-47Al-2Cr-2Nb alloy substrate, this coat-thickness of preparation is about 25 μ m, and alumina particle and quartz particles well are dispersed in coating, and hole or crackle are not observed in coating inside.Coating and Ti-47Al-2Cr-2Nb alloy interface are in conjunction with intact.Coatingsurface is smooth, has vitreous luster, and the coating interior solid does not have hole or crackle.
Embodiment 2
Take the potassium silicate water glass that the 100g modulus is 3.9, the aluminum oxide powder 10g that particle diameter is 1～10 μ m, the silica powder 30g that particle diameter is 1～10 μ m, in the nano-titanium that the peak value particle diameter is 50nm/titanium oxide mixed powder powder 4g(the present embodiment, titanium: the weight ratio of titanium oxide is 0.2), pre-mixing aluminum oxide powder, silica powder, nano-titanium/titanium dioxide powder, then be added into the pre-mixing powder in water glass, and be applicable to spraying after adding 4g distilled water adjusting coating viscosity that coating is stirred.In whipping process, add the pottery that particle diameter is 1mm to stir ball increase dispersed with stirring effect, after the rotating speed stirring 20min with 1500rpm in stirring dispersion machine, after 300 eye mesh screens filter, obtain coating.Adopt the mode of spraying that paint spay-coating is arrived to the Ti-47Al-2Cr-2Nb alloy component surface through sandblasting, the coating sprayed is after self-vulcanizing, at 70 ℃～80 ℃ baking 12h, 110 ℃～130 ℃ baking 10h, 230 ℃～260 ℃ baking 5h, then fire and process 90min taking-up air cooling through 900 ℃.
In the present embodiment, the performance perameter of high temperature oxidation corrosion resistance glass-ceramic compound coating is as follows:
Application above-mentioned 25 μ m high temperature oxidation corrosion resistance glass-ceramic compound coating Ti-47Al-2Cr-2Nb alloys 800 ℃ and 900 ℃ through the 100h oxidation, coating is intact, the phenomenon such as occurs bubbling, peeling off.Execute the weightening finish after 800 ℃ and 900 ℃ of oxidations of cated sample and be respectively 0.19g/cm
2and 0.37g/cm
2, and the sample weightening finish that does not apply coating is respectively 1.06g/cm
2and 2.58g/cm
2.Coating is 800 ℃ and 900 ℃ through after 120 cyclic oxidations, and coating is complete, peeling phenomenon do not occur.
Embodiment 3
Take the potassium silicate water glass that the 150g modulus is 3, the aluminum oxide powder 15g that particle diameter is 1～10 μ m, the silica powder 45g that particle diameter is 1～10 μ m, in the nano-titanium that the peak value particle diameter is 70nm/titanium oxide mixed powder powder 4g(the present embodiment, titanium: the weight ratio of titanium oxide is 0.5), pre-mixing aluminum oxide powder, silica powder, nano-titanium/titanium dioxide powder, then be added into the pre-mixing powder in water glass, and be applicable to spraying after adding 5g distilled water adjusting coating viscosity that coating is stirred.In dispersed with stirring, add the zirconia ball that particle diameter is 1mm to increase dispersion effect, after the rotating speed stirring 20min with 1500rpm in stirring dispersion machine, after 200 eye mesh screens filter, obtain coating.Adopt the mode of spraying that paint spay-coating is arrived to the Ti-6Al-4V alloy component surface through sandblasting, the coating sprayed is after self-vulcanizing, and at 80 ℃ of baking 12h, 120 ℃ are toasted 10h, 260 ℃ of baking 5h, then fire and process 60min taking-up air cooling through 850 ℃.
As shown in Figure 2, the glass-ceramic compound coating prepared on the Ti-6Al-4V alloy substrate, this coat-thickness of preparation is about 40 μ m, and alumina particle and quartz particles well are dispersed in coating, and hole or crackle are not observed in coating inside.Coating and Ti-6Al-4V alloy interface are in conjunction with intact.Coatingsurface is smooth, has vitreous luster, and the coating interior solid does not have hole or crackle.
In the present embodiment, the performance perameter of high temperature oxidation corrosion resistance glass-ceramic compound coating is as follows:
Application the Ti-6Al-4V alloy of above-mentioned 40 μ m high temperature oxidation corrosion resistance glass-ceramic compound coatings (be incubated 1h at 900 ℃ in High Temperature Furnaces Heating Apparatus through the 100h cyclic oxidation, then taking out air cooling 10min is a loop cycle), coating is intact, the phenomenon such as occurs bubbling, peeling off; Execute cated sample only increases weight as 2.5g/cm after 900 ℃ of oxidations
2; Apply section structure after the coating sample oxidation as Fig. 3, the coatings and substrate interface is in conjunction with good, and hole, crackle do not appear in coating inside.
Embodiment 4
Take the Ti-6Al-4V alloy as matrix, and preparation technology parameter is with embodiment 3.
In the present embodiment, the thermal shock resistance of high temperature oxidation corrosion resistance glass-ceramic compound coating is as follows:
Application the Ti-6Al-4V alloy of above-mentioned 30 μ m high temperature oxidation corrosion resistance glass-ceramic compound coatings at 900 ℃, after 50 thermal shocks, (retort furnace that sample is placed in to 900 ℃ is incubated 10min, then taking out sample and putting it in room temperature distilled water is thermal shock experiment), the coatingsurface pattern is as Fig. 4, coating is intact, aluminum oxide or the quartz particles of rat for adding.The phenomenon such as coatingsurface do not observe foaming, peel off.
Embodiment 5
Take the sodium silicate water glass that the 300g modulus is 3, the aluminum oxide powder 30g that particle diameter is 1～10 μ m, the silica powder 90g that particle diameter is 1～10 μ m, in the nano-titanium that the peak value particle diameter is 70nm/titanium oxide mixed powder powder 8g(the present embodiment, titanium: the weight ratio of titanium oxide is 0.5), pre-mixing aluminum oxide powder, silica powder, nano-titanium/titanium dioxide powder, then be added into the pre-mixing powder in water glass, and be applicable to spraying after adding 15g distilled water adjusting coating viscosity that coating is stirred.In stirring, add the zirconia ball that the 150g particle diameter is 1mm to increase dispersion effect, after the rotating speed stirring 20min with 1500rpm in stirring dispersion machine, after 200 eye mesh screens filter, obtain coating.Adopt the mode of spraying that paint spay-coating is arrived to the Ti60 alloy component surface through sandblasting, the coating sprayed is after self-vulcanizing, at 70 ℃～80 ℃ baking 12h, 110 ℃～150 ℃ baking 10h, 230 ℃～280 ℃ baking 5h, then fire and process 60min taking-up air cooling through 850 ℃.
In the present embodiment, the performance perameter of high temperature oxidation corrosion resistance glass-ceramic compound coating is as follows:
Application the Ti60 alloy of above-mentioned 30 μ m high temperature oxidation corrosion resistance glass-ceramic compound coatings 800 ℃ and 900 ℃ through the 100h oxidation, coating is intact, the destruction such as occurs bubbling, peeling off.
Embodiment 6
Take the sodium silicate water glass that the 200g modulus is 3, the kaolin 20g that particle diameter is 0.5～3 μ m, the silica powder 40g that particle diameter is 1～10 μ m, in the nano-titanium that the peak value particle diameter is 100nm/titanium oxide mixed powder powder 5g(the present embodiment, titanium: the weight ratio of titanium oxide is 0.5), pre-mixing kaolin powder, silica powder, nano-titanium/titanium dioxide powder, then be added into the pre-mixing powder in water glass, and be applicable to spraying after adding 10g distilled water adjusting coating viscosity that coating is stirred.In stirring, add the zirconia ball that the 50g particle diameter is 1mm to increase dispersion effect, after the rotating speed stirring 15min with 2000rpm in stirring dispersion machine, after 200 eye mesh screens filter, obtain coating.Adopt the mode of spraying that paint spay-coating is arrived to the Ti60 alloy component surface through sandblasting, the coating sprayed is after self-vulcanizing, and at 70 ℃ of baking 12h, 110 ℃ are toasted 12h, 230 ℃ of baking 12h, then fire and process 60min taking-up air cooling through 850 ℃.
In the present embodiment, the performance perameter of high temperature oxidation corrosion resistance glass-ceramic compound coating is as follows:
Application the Ti60 alloy of above-mentioned 35 μ m high temperature oxidation corrosion resistance glass-ceramic compound coatings at 900 ℃ through the 100h oxidation, coating is intact, the destruction such as occurs bubbling, peeling off; After oxidation, cross-section photograph is as Fig. 5, and coating and Ti60 alloy substrate interface be in conjunction with good, coating interior solid, without hole or crackle.
Embodiment 7
Take the sodium silicate water glass that the 200g modulus is 3.3, the aluminum oxide powder 20g that particle diameter is 1～10 μ m, particle diameter is, the silica powder 60g that particle diameter is 1～10 μ m, in the nano-titanium that the peak value particle diameter is 50nm/titanium oxide mixed powder powder 8g(the present embodiment, titanium: the weight ratio of titanium oxide is 0.2), pre-mixing aluminum oxide powder, silica powder, nano-titanium/titanium dioxide powder, then the pre-mixing powder is added in water glass, and is applicable to spraying after adding 10g distilled water adjusting coating viscosity that coating is stirred.In the dispersed with stirring process, add the zirconia ball that the 100g particle diameter is 1mm to increase dispersion effect, after the rotating speed stirring 20min with 1500rpm in stirring dispersion machine, after 300 eye mesh screens filter, obtain coating.Adopt the mode of spraying that paint spay-coating is arrived to the Ti-47Al-2Cr-2Nb alloy component surface through sandblasting, the coating sprayed is after self-vulcanizing, and at 70 ℃ of baking 12h, 110 ℃ are toasted 10h, 260 ℃ of baking 5h, then fire and process 60min taking-up air cooling through 850 ℃.
At sample surfaces, by spraying one deck solute, be 25wt.%NaCl+75wt.%Na
2sO
4saturated aqueous solution, deposit thickness is 1.5～2.5mg/cm
2; Sample after painting salt is placed in the hot corrosion resistance of the retort furnace observation coating coating of 900 ℃; Do not prepare the Ti-47Al-2Cr-2Nb alloy of coating and application the Ti-47Al-2Cr-2Nb alloy of above-mentioned 35 μ m glass-ceramic compound coatings at 850 ℃ of macro morphologies after the 100h thermal etching as Fig. 6, the sample seriously corroded that does not prepare coating, corrosion product has foaming, peeling phenomenon; And application the alloy sample top coat of coating intact, destructions such as bubbling, peel off appears.
Embodiment 8
Take the potassium silicate water glass that the 200g modulus is 3.3, the aluminum oxide powder 20g that particle diameter is 1～10 μ m, the carborundum powder 40g that particle diameter is 1～5 μ m, in the nano-titanium that the peak value particle diameter is 50nm/titanium oxide mixed powder powder 6g(the present embodiment, titanium: the weight ratio of titanium oxide is 0.2), pre-mixing aluminum oxide powder, carborundum powder, nano-titanium/titanium dioxide powder, then be added into the pre-mixing powder in water glass, and be applicable to spraying after adding 8g distilled water adjusting coating viscosity that coating is stirred.Add the zirconia ball that the 100g particle diameter is 1mm to increase dispersion effect, after the rotating speed stirring 20min with 1800rpm in stirring dispersion machine, after 200 eye mesh screens filter, obtain coating.Adopt the mode of spraying that paint spay-coating is arrived to the Ti-47Al-2Cr-2Nb alloy component surface through sandblasting, the coating sprayed is after self-vulcanizing, and at 70 ℃ of baking 12h, 110 ℃ are toasted 10h, 230 ℃ of baking 5h, then fire and process 60min taking-up air cooling through 850 ℃.
In the present embodiment, the performance perameter of high temperature oxidation corrosion resistance glass-ceramic compound coating is as follows:
Application the Ti-47Al-2Cr-2Nb alloy of above-mentioned 25 μ m high temperature oxidation corrosion resistance glass-ceramic compound coatings (be incubated 1h at 900 ℃ and 1000 ℃ in High Temperature Furnaces Heating Apparatus after 120 loop cycle oxidations, then taking out air cooling 10min is a loop cycle), coating is intact, the destruction such as occurs bubbling, peeling off.Sample after 1000 ℃ of cyclic oxidations section structure as Fig. 7.
The embodiment result shows, the high temperature oxidation and corrosion glass-ceramic compound coating obtained by this technique has good corrosion-resistant and resistance to elevated temperatures, is easy to control, and is applicable to suitability for industrialized production, has nontoxic, free of contamination characteristic, is conducive to environment protection.
In addition, the above, be only the better feasible embodiment of the present invention, can not limit to this interest field of the present invention, and described high temperature resistant protective coating can, for the titanium base alloy product, also can be applicable to the protection of the material of other type as parts of stainless steel.Therefore, according to technical scheme of the present invention and technical thought, make other various corresponding changes and distortion, within still belonging to the protection domain that the present invention contains.
Claims (10)
1. the corrosion resistant glass-ceramic compound coating of resistance to high temperature oxidation, is characterized in that, this coating be micron order ceramic particle phase and nano level metal/oxide compound mixed powder even dispersion be distributed in glass basis mutually in, its composition comprises:
The glass basis phase, formed through pyrolytic conversion by sodium silicate water glass or potassium silicate water glass;
Micron order ceramic particle phase, particle size range is 1 μ m～20 μ m, total content accounts for the 15wt%～60wt% of glass-ceramic compound coating;
Nano level metal/oxide compound mixed powder, diameter range is 1nm～500nm, total content accounts for the 0.5wt%～5wt% of glass-ceramic compound coating; Wherein, nano level metal/oxide compound mixed powder is nano-titanium/titanium dioxide powder, titanium: the weight ratio of titanium oxide is 0.1～0.5.
2. according to the corrosion resistant glass-ceramic compound coating of resistance to high temperature oxidation claimed in claim 1, it is characterized in that: the micron order ceramic particle is aluminum oxide and quartzy mixed powder mutually, and aluminum oxide: quartzy weight ratio is 0.1～0.8.
3. according to the corrosion resistant glass-ceramic compound coating of resistance to high temperature oxidation claimed in claim 2, it is characterized in that: alumina particle is partly or entirely replaced by the mineral that kaolin or other alumina content surpass 50wt%.
4. according to the corrosion resistant glass-ceramic compound coating of resistance to high temperature oxidation claimed in claim 2, it is characterized in that: quartz particles is partly or entirely replaced by the mineral that quartzite or silicon carbide or other silica content surpass 50wt%.
5. the preparation technology of the corrosion resistant glass-ceramic compound coating of resistance to high temperature oxidation claimed in claim 1, is characterized in that, comprises following three process step:
(1) coating preparation operation
Water glass, micron order ceramic particle and nano level metal/oxidate powder powder stock is mixed, adopt high-speed stirring dispersion machine or other mechanical means that solid particulate matter is dispersed in water glass, form coating; Wherein, water glass is sodium silicate water glass or potassium silicate water glass, and modulus is 3～3.9;
(2) paint spay-coating operation
The twice that the sprayed coating minimum thickness is micron order ceramic particle maximum diameter, and a coating thickness is no more than 100 μ m; Spraying method is the spraying of normal temperature atmosphere, and spray pressure is 0.3MPa～0.8MPa;
(3) pyroprocessing operation
Advanced person's prebake conditions of passing through is processed, and then carries out pyroprocessing.
6. according to the preparation technology of the corrosion resistant glass-ceramic compound coating of resistance to high temperature oxidation claimed in claim 5, it is characterized in that: in step (1), the rotating speed of high-speed stirring dispersion machine is 1000～2000r/min, and the time is 10～30min.
7. according to the preparation technology of the corrosion resistant glass-ceramic compound coating of resistance to high temperature oxidation claimed in claim 5, it is characterized in that: in step (2), a spray-on coating thickness is at 10～100 μ m.
8. according to the preparation technology of the corrosion resistant glass-ceramic compound coating of resistance to high temperature oxidation claimed in claim 5, it is characterized in that: in step (3), prebake conditions is processed and pyroprocessing all can be carried out in atmosphere, does not need vacuum or special protection atmosphere; The prebake conditions treatment temp is 70 ℃～300 ℃, and the treatment time is 24h～36h.
9. according to the preparation technology of the corrosion resistant glass-ceramic compound coating of resistance to high temperature oxidation claimed in claim 8, it is characterized in that: in this prebake conditions treatment temp interval, carry out temperature-gradient method and insulation:
(1) at 70 ℃～80 ℃ baking 5～12h;
(2) at 110 ℃～130 ℃ baking 5～12h;
(3) at 230 ℃～260 ℃ baking 5～12h.
10. according to the preparation technology of the corrosion resistant glass-ceramic compound coating of resistance to high temperature oxidation claimed in claim 5, it is characterized in that: in step (3), the pyroprocessing temperature is 700 ℃～950 ℃, and the treatment time is 0.5h～2h.
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