CN102225650B - Graphene-LaTaO4/zinc-aluminum-nickel system corrosion resisting coating used for polysilicon ingot furnaces - Google Patents
Graphene-LaTaO4/zinc-aluminum-nickel system corrosion resisting coating used for polysilicon ingot furnaces Download PDFInfo
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Abstract
The invention provides a corrosion resisting coating used for polysilicon an ingot furnace. The coating is characterized in that: the coating comprises an alloy anticorrosive layer coated on a carbon fiber insulating layer, and an insulating anticorrosive layer coated on the alloy anticorrosive layer. The alloy anticorrosive layer comprises: 20wt% to 38wt% of aluminum powder, 30wt% to 45wt% of zinc powder, and 30wt% to 45wt% of nickel powder. The insulating anticorrosive layer comprises 55wt% to 72wt% of graphene powder, 25wt% to 40wt% of LaTaO4 powder, 1wt% to 5wt% of a film forming agent, and 1wt% to 5wt% of a mixture composed of a curing agent and a dispersant. The invention also provides a high-temperature resistant protective layer used for a polysilicon ingot furnace, and a preparation method thereof. The coating provided by the present invention has relatively high hardness and corrosion resistance, with which the service life of the carbon fiber insulating layer can be prolonged.
Description
Technical field
The present invention relates to field polysilicon, be specifically related to a kind of corrosion-resistant finishes that is used for polycrystalline silicon ingot or purifying furnace, the high temperature resistance protective layer that constitutes by this corrosion-resistant finishes and the preparation method of high temperature resistance protective layer.
Background technology
Solar energy is developed as a kind of reproducible green energy resource gradually in the world fast; Solar energy power generating is to utilize the photovoltaic effect of interface and directly change luminous energy a kind of technology of electric energy into, and solar cell carries out packaging protection after through series connection can form large-area photovoltaic module.Increasingly mature along with solar energy generation technology, photovoltaic module is obtained extensive use at numerous areas such as artificial satellite energy supplies.
Polycrystalline silicon ingot or purifying furnace is one of key equipment of photovoltaic industry chain (supply chain) front end; Polycrystalline silicon ingot or purifying furnace furnace wall innermost layer is a working lining, and temperature is up to 1560 ℃, in hot environment in the stove; Under the heating of the silicon material graphite heater in argon gas in the crucible; By the solid-state liquid state that becomes, through the conductive force of oriented growth piece, generate the fixedly polycrystal silicon ingot in crystal orientation then.Directly have influence on the electricity conversion of polycrystal silicon cell sheet by the quality of the polycrystal silicon ingot of polycrystalline silicon ingot or purifying furnace preparation.
Existing polycrystalline silicon ingot casting furnace main body adopts stainless steel, to reduce the pollution of equipment material to product.Under the hot environment of producing polysilicon, by roasting bad, on the inwall of working lining, lay the high temperature resistant heat insulation layer in order to prevent stainless steel casing.In numerous high temperature resistant heat insulation materials; The heat resisting temperature of carbon fiber reaches as high as 3000 ℃; Carbon fiber also has characteristics such as corrosion resistance, fatigue durability and intensity height preferably simultaneously; Therefore, in the production technology of existing polysilicon, adopt carbon fiber thermal insulating material usually as high temperature resistant heat insulation material.
As heat-barrier material, carbon fiber is under the situation of not mixing impurity, and carbon fiber can keep characteristic such as high temperature resistant, corrosion-resistant, that the coefficient of expansion is little.But when polycrystalline silicon ingot or purifying furnace was produced polysilicon, the raw material of making polysilicon contained impurity, the carbon fiber heat insulation layer usually; The thermal insulation layer at especially simple action position, along with use is easy to adsorb the minute impurities particle, carbon fiber can react with impurity and silicon then; Thereby changed the original character of carbon fiber heat insulation layer; Cause carbon fiber heat insulation layer density to diminish, wearing and tearing increase, and influence the effect of heat insulation of carbon fiber heat insulation layer.
In order to prevent that the sodium carbonate fibrous insulating layer is corroded; Application number is that 200910138449.3 Chinese patent document discloses a kind of corrosion-resistant finishes that is used for polycrystalline silicon ingot or purifying furnace and preparation method thereof; This patent discloses a kind of corrosion-resistant finishes that is used for polycrystalline silicon ingot or purifying furnace, and it comprises following component in percentage by weight: 85% ~ 93% the carbon fiber powder and the mixture of graphite powder, 1% ~ 4% film forming agent; 1% ~ 3% film forming agent; The heat-barrier material powder of 1% ~ 3% curing agent and the mixture of dispersant and 5% ~ 12%, the heat-barrier material that uses in this patent is Sr
3Ti
2O
7And Sr
4Ti
3O
10In one or both.Though above-mentioned corrosion-resistant finishes plays heat-insulation layer to the carbon fiber heat insulation layer and plays the certain protection effect, but its intensity and corrosion resistance still remain to be improved, and have longer service life to guarantee the carbon fiber heat insulation layer.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of corrosion-resistant finishes that is used for polycrystalline silicon ingot or purifying furnace; This coating has higher hardness and corrosion resistance; Thereby prolong the service life of carbon fiber heat insulation layer, the high temperature resistance protective layer that is made up of this corrosion-resistant finishes and the preparation method of high temperature resistance protective layer also are provided.
In order to solve the problems of the technologies described above, the present invention provides following technical scheme:
A kind of corrosion-resistant finishes that is used for polycrystalline silicon ingot or purifying furnace comprises: the alloy anticorrosive coat and the heat insulating and corrosion layer that is overlying on said alloy anticorrosive coat surface that are overlying on the carbon fiber heat insulation laminar surface.
Said alloy anticorrosive coat comprises: the nickel powder of the aluminium powder of 20wt% ~ 38wt%, the zinc powder of 30wt% ~ 45wt% and 30wt% ~ 45wt%;
Said heat insulating and corrosion layer comprises: the Graphene powder of 55wt% ~ 72wt%, the LaTaO of 25wt% ~ 40wt%
4The mixture of the film forming agent of powder, 1wt% ~ 5wt% and the curing agent of 1wt% ~ 5wt% and dispersant.
Preferably, be that the content of graphene powder is 62wt% ~ 68wt% in the said heat insulating and corrosion layer.
Preferably, the particle diameter of zinc powder, aluminium powder and nickel powder is 100 orders ~ 300 orders in the said alloy anticorrosive coat.
Preferably, said film forming agent is a waterglass.
Preferably, said curing agent is a fluosilicate.
Preferably, said dispersant is a tannic acid.
The weight ratio of preferred said fluosilicate and tannic acid is 1:1 ~ 2:1.
The present invention also provides a kind of high temperature resistance protective layer that is used for polycrystalline silicon ingot or purifying furnace, comprising: carbon fiber heat insulation layer and the above-mentioned corrosion-resistant finishes that is overlying on said carbon fiber heat insulation laminar surface.
Accordingly, the present invention also provides a kind of preparation method of above-mentioned high temperature resistance protective layer, may further comprise the steps:
1) after being mixed in proportion, aluminium powder, zinc powder and nickel powder obtain the diffusion medium powder; The carbon fiber heat insulation layer is embedded in is heated to 300 ℃ ~ 500 ℃ in the said diffusion medium powder; Be incubated 2 h ~ and take out after 5 hours, obtain the carbon fiber heat insulation layer that the surface is covered with the alloy anticorrosive coat;
2) mixture of curing agent and dispersant is applied to the surface of said alloy anticorrosive coat;
3) with Graphene powder, LaTaO
4After mixing in proportion, powder and film forming agent be applied to the surface of curing agent and dispersant;
4) will under vacuum state, be heated to 70 ℃ ~ 85 ℃ through the carbon fiber heat insulation layer that step 3) is handled, constant temperature 1.5 ~ 3 hours.
Preferably, step 2) in, 0 ℃～100 ℃ of environment temperatures, relative humidity <under 90% the condition is applied to curing agent and dispersant the surface of said alloy anticorrosive coat.
The present invention provides a kind of corrosion-resistant finishes that is used for polycrystalline silicon ingot or purifying furnace, and this corrosion-resistant finishes comprises alloy anticorrosive coat and heat insulating and corrosion layer successively.Wherein, The alloy anticorrosive coat comprises: the nickel powder of the aluminium powder of 20wt% ~ 38wt%, the zinc powder of 30wt% ~ 45wt% and 30wt% ~ 45wt%, and it directly is overlying on carbon fiber surface, has higher antiseptic property and hardness; Avoid impurity to contact, and improve the mechanical property of carbon fiber with carbon fiber.The heat insulating and corrosion layer comprises: the Graphene powder of 55wt% ~ 72wt%, the LaTaO of 25wt% ~ 40wt%
4The mixture of the film forming agent of powder, 1wt% ~ 5wt% and the curing agent of 1wt% ~ 5wt% and dispersant; It is with polycrystalline silicon ingot or purifying furnace in the nearest one deck of hot environment; The heat insulating and corrosion layer has heat-blocking action preferably on the one hand; Avoid alloy anticorrosive coat generation fusion, guarantee that the alloy anticorrosive coat plays best antisepsis; On the other hand, the heat insulating and corrosion layer has certain antiseptic effect and higher hardness, further the carbon fiber heat insulation layer is played a protective role, and prolongs the service life of carbon fiber heat insulation layer.
The specific embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiment of the invention is described, describe just to further specifying feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The embodiment of the invention discloses a kind of corrosion-resistant finishes that is used for polycrystalline silicon ingot or purifying furnace, this coating comprises alloy anticorrosive coat that is overlying on the carbon fiber heat insulation laminar surface and the heat insulating and corrosion layer that is overlying on alloy anticorrosive coat surface.Above-mentioned alloy anticorrosive coat comprises: the nickel powder of the aluminium powder of 20wt% ~ 38wt%, the zinc powder of 30wt% ~ 45wt% and 30wt% ~ 45wt%.Above-mentioned heat insulating and corrosion layer comprises: the Graphene powder of 5wt% ~ 72wt%, the LaTaO of 25wt% ~ 40wt%
4The mixture of the film forming agent of powder, 1wt% ~ 5wt% and the curing agent of 1wt% ~ 5wt% and dispersant.
Alloy anticorrosive coat in the above-mentioned corrosion-resistant finishes directly contacts with carbon fiber, is the coating that the carbon fiber heat insulation layer is played main antisepsis.Among the present invention in the alloy anticorrosive coat content of aluminium powder be 20wt% ~ 38wt%, be preferably 22wt% ~ 35wt%, 28wt% ~ 34wt% more preferably, preferred 100 orders of the particle diameter of aluminium powder ~ 300 orders, more preferably 200 orders ~ 300 orders.The content of zinc powder is 30wt% ~ 45wt% in the alloy anticorrosive coat of the present invention, is preferably 32wt% ~ 45wt%, 35wt% ~ 40wt% more preferably, preferred 100 orders of the particle diameter of aluminium powder ~ 300 orders, more preferably 200 orders ~ 300 orders.The adding of nickel powder helps to improve the intensity of alloy anticorrosive coat; The content of nickel powder is 30wt% ~ 45wt% in the above-mentioned alloy anticorrosive coat, is preferably 32wt% ~ 45wt%, more preferably 35wt% ~ 40wt%; Preferred 100 orders of the particle diameter of nickel powder ~ 300 orders, more preferably 200 orders ~ 300 orders.
As preferred version, alloy anticorrosive coat provided by the invention can also comprise the activator powder of 0.1wt ~ 2.0wt% and the filler of 0.1wt ~ 20wt%.The activator powder content is 0.5wt ~ 1.5wt% more preferably; The particle diameter of activator powder is preferably 50 orders ~ 200 orders; 100 orders ~ 200 orders more preferably, activator can be selected from one or more in ammonium chloride well known to those skilled in the art, sodium chloride, potassium chloride, aluminium chloride, zinc chloride, sodium fluoride, potassium fluoride, aluminum fluoride, the zinc fluoride.Filler is preferably quartz sand, and the particle diameter of filler powder is preferably 50 orders ~ 200 orders, more preferably 100 orders ~ 200 orders.
The process that the alloy anticorrosive coat forms is following: obtain the diffusion medium powder after aluminium powder, zinc powder and nickel powder are mixed in proportion; The carbon fiber heat insulation layer is embedded in is heated to 300 ℃ ~ 500 ℃ in the said diffusion medium powder; Be incubated 2 h ~ and take out after 5 hours, above-mentioned diffusion medium metal dust is oozing in the processing procedure altogether, under the infiltration expanding effect of metallic atom; Zinc, al and ni element infiltrate carbon fiber surface, form the alloy anticorrosive coat.
The alloy anticorrosive coat that forms according to the method described above not only can improve the corrosion resistance of carbon fiber surface, in addition, because hardness is high, has therefore also improved the anti-wear performance of carbon fiber heat insulation layer.
Though the alloy anticorrosive coat has excellent antiseptic property and higher hardness; But heat resistance is not good; Hot environment melts the alloy anticorrosive coat in the ingot furnace, and the present invention sets up the Graphene powder of the heat insulating and corrosion layer of following composition: 55wt% ~ 72wt%, the LaTaO of 25wt% ~ 40wt% on the alloy anticorrosive coat
4The mixture of the film forming agent of powder, 1wt% ~ 5wt% and the curing agent of 1wt% ~ 5wt% and dispersant.
In the above-mentioned heat insulating and corrosion layer, Graphene powder and LaTaO
4Powder is a basic substance, and Graphene is the hardest the thinnest material that has been found that in the world, and its good heat resistance, at high temperature still has excellent chemical stability; In addition, Graphene powder coefficient of friction is little, and greasy property is good, can make the corrosion-resistant finishes smooth surface that makes, and does not have burr.Therefore, the adding of graphene powder makes insulating have very excellent hardness, corrosion resistance and higher surface flatness preferably.The content of Graphene powder is 55wt% ~ 72wt% in the heat insulating and corrosion layer, is preferably 62wt% ~ 68wt%, more preferably 63wt% ~ 68wt%.Graphene powder is preferably according to following method preparation:
A), graphite is added in the mixture of strong oxidizing acid and nitrate, be cooled to 0 ℃ ~ 5 ℃, stirring slowly adds down and contains the potassium strong oxidizer, is warming up to 10 ℃ ~ 15 ℃; And continue to stir, subsequently mixed solution being imported temperature is in 30 ℃ ~ 40 ℃ the water-bath, slowly adds entry behind reaction 20min ~ 40min, is warming up to 90 ℃ ~ 100 ℃; Add hydrogen peroxide solution and water again, the back that stirs is alternately cleaned the back with hydrochloric acid and water and is filtered, and filter cake is dried; Grind, sieve, obtain oxidation graphite solid.
B), oxidation graphite solid that step a is obtained is dissolved in the solvent, earthquake power is to shake under the condition of 300w ~ 1200w then, obtains graphene oxide solution.
C), graphene oxide solution is placed in the supercritical reaction still; Under the inert gas shielding; In 20Mpa ~ 100Mpa, under the condition of the supercritical temperature that is higher than step b solvent for use, reaction 1 ~ 24h; Agitated reactor is cooled off or water is crisp emits gas in the agitated reactor after cold naturally, obtain graphene powder.
LaTaO in the heat insulating and corrosion layer
4Powder is as heat-barrier material, LaTaO
4Be that the patent of CN100376505C is disclosed by authorizing publication number.LaTaO
4Fusing point is high, and thermal conductivity is little, by LaTaO
4The corrosion-resistant finishes thermal conductivity that powder constitutes is lower, and good hear resistance is arranged, and is applicable to the parts that under thermal environment, use for a long time, and the alloy anticorrosive coat is played a protective role, and prevents that it from melting at high temperature.
In the corrosion-resistant finishes provided by the invention, the adding of film forming agent makes the heat insulating and corrosion layer can form the continuous film that can adhere to, and it is more firm on the alloy anticorrosive coat, to adhere, rub resistance.Film forming agent is preferably waterglass among the present invention.Waterglass is alkali silicate (M
2OnSiO
2) the aqueous solution, be comparatively general inorganic coating film forming agent.Water glass acid-proof property is good, and good heat resistance, the silica mesh skeleton that sclerosis back forms at high temperature intensity descend very for a short time, and the coating of formation has high temperature resistant, anti-solvent, heat insulation performance.Waterglass has many types according to the kind of metal M and modulus n value different, and M can be Na, K, Li; The size of modulus n can influence caking property and resistance to water.The amount of waterglass of the present invention is the 1wt%～5wt% of heat insulating and corrosion stratum total.
When utilizing waterglass to make heat-insulating anti-corrosive coating, in order to make the better film forming of waterglass, quicken the condensation cure speed and raising intensity of waterglass, and increase its resistance to water, add curing agent usually waterglass is carried out modification.
Curing agent is preferably fluosilicate among the present invention.If the fluosilicate incorporation very little, then the waterglass condensation cure is slow, and the intensity of the corrosion-resistant finishes of processing also can be influenced; If the fluosilicate incorporation is too many, then the waterglass setting and harden is too fast, and inconvenience is smeared the corrosion-resistant finishes material on thermal insulation layer; And after the sclerosis; Though the early strength of corrosion-resistant finishes is high, the later stage can descend to some extent, so the amount of curing agent and dispersant is the 1wt%～5wt% of heat insulating and corrosion stratum total.
Each composition keeps good dispersiveness in the heat insulating and corrosion coating material in order to make, and has also added dispersant in the heat insulating and corrosion coating material provided by the invention.Dispersant can reduce each composition completion needed time of dispersion process in the corrosion-resistant finishes material; Homogeneous disperses to be difficult to be dissolved in inorganic, the organic solid particle of liquid, stablizes each discrete particles, the surface nature of modification dispersed particle; The motility of adjustment particle prevents flocculation and deposition.
Dispersant among the present invention is preferably tannic acid.Tannic acid is claimed tannic acid again, is the compound of one type of complicacy, and is nontoxic and soluble in water, is present in many plants, and the structure of the tannic acid of separate sources is variant, but all has the polyphenol hydroxyl structure, has hydrophilic, oleophilic characteristics, and certain surface-active is arranged.
As preferably, curing agent potassium fluosilicate and dispersant tannic acid mixed proportion are 1:1～2:1, and be preferred, and the mixed proportion of potassium fluosilicate and tannic acid is 1:1.
Can know that by such scheme corrosion-resistant finishes provided by the invention comprises alloy anticorrosive coat and heat insulating and corrosion layer successively.Wherein, the alloy anticorrosive coat directly is overlying on carbon fiber surface, has higher antiseptic property and hardness, avoids impurity to contact with carbon fiber, and carbon fiber is had protective effect.The heat insulating and corrosion layer be with polycrystalline silicon ingot or purifying furnace in the nearest one deck of hot environment, it has heat-blocking action preferably on the one hand, avoids alloy anticorrosive coat generation fusion, guarantees that the alloy anticorrosive coat plays best antisepsis; On the other hand, the heat insulating and corrosion layer has certain antiseptic effect and higher hardness, further the carbon fiber heat insulation layer is played a protective role, and prolongs the service life of carbon fiber heat insulation layer.
The high temperature resistance protective layer that is used for polycrystalline silicon ingot or purifying furnace of the present invention comprises carbon fiber heat insulation layer and the corrosion-resistant finishes that is overlying on the carbon fiber heat insulation laminar surface, and corrosion-resistant finishes is processed by above material.This high temperature resistance protective layer prepares according to following method:
1) after being mixed in proportion, aluminium powder, zinc powder and nickel powder obtain the diffusion medium powder; The carbon fiber heat insulation layer is embedded in is heated to 300 ℃ ~ 500 ℃ in the said diffusion medium powder, be incubated 2 h ~ and take out the carbon fiber heat insulation layer that the surface is covered with the alloy anticorrosive coat after 5 hours;
2) mixture of curing agent and dispersant is applied to the surface of said alloy anticorrosive coat;
3) with Graphene powder, LaTaO
4After mixing in proportion, powder and film forming agent be applied to the surface of curing agent and dispersant;
4) will under vacuum state, be heated to 70 ℃～85 ℃ through the carbon fiber heat insulation layer that step 3) is handled, constant temperature 1.5～3 hours.
Step 1 is the process that forms the alloy anticorrosive coat at the carbon fiber heat insulation laminar surface; Step 2 ~ step 4 is the processes at alloy anticorrosive coat surface-coated heat insulating and corrosion layer; Preferably 10 ℃～100 ℃ of environment temperatures, relative humidity <under 90% the condition is applied to curing agent and dispersant the surface of said alloy anticorrosive coat in the step 2.
The high temperature resistance protective layer intensity of the present invention's preparation is high, and corrosion resistance is strong, avoids impurity to be deposited on carbon fiber surface, and service life is longer.
In order further to understand the present invention, below in conjunction with embodiment the high temperature resistance protective layer that is used for polycrystalline silicon ingot or purifying furnace provided by the invention to be described, protection scope of the present invention is not limited by the following examples.
Potassium fluosilicate in following examples is provided by Changshu Xinhua Chemical Factory, and tannic acid is provided by the magnificent forever fine chemicals in Jiangsu Co., Ltd, and KP1 is provided by the prosperous Sheng chemical industry of Shijiazhuang City Co., Ltd.
Embodiment 1 preparation Graphene powder
1,10g graphite is added in the mixed solution of the concentrated sulfuric acid and sodium nitrate, the mass ratio of the concentrated sulfuric acid and sodium nitrate is 0.5:1, and the mass ratio of the concentrated sulfuric acid and graphite is 10:1, and mixed solution is cooled to 0 ℃ ~ 5 ℃; Stir 30min, continue to stir and the slow potassium permanganate that adds, the mass ratio of potassium permanganate and graphite is 2:1, is warming up to 10 ℃ ~ 15 ℃; Continue to stir 12h, then mixed solution being imported temperature is in 30 ℃ ~ 40 ℃ the water-bath, slowly adds 200ml water behind the reaction 30min; Be warming up to 90 ℃ ~ 100 ℃ and keep 35min, add hydrogen peroxide solution and 100ml water again, the mass ratio of hydrogen peroxide solution and graphite is 0.5:1; Alternately clean 4 times with hydrochloric acid and water after stirring 2h, after with flushing with clean water, filter, filter cake is dried; Grind, sieve, obtain oxidation graphite solid.
2, the oxidation graphite solid that step 1 is obtained is dissolved in the ethanol, and earthquake power is to shake 10h under the condition of 700w then, obtains graphene oxide solution.
3, step 2 is obtained graphene oxide solution and place in the supercritical reaction still, under nitrogen protection,, under 260 ℃ the condition, react 1 ~ 24h, emit gas in the agitated reactor after agitated reactor is cooled off naturally, obtain graphene powder in 60Mpa.The graphene powder that uses in following examples prepares by present embodiment.
Embodiment 2
1, getting the 25wt% granularity is that the granularity of 100 purpose zinc powders, 40wt% is that 100 purpose aluminium powders, 40wt% granularity are 100 purpose nickel powders, evenly mixes obtaining the diffusion medium powder; Get the diffusion medium for preparing and carbon fiber heat insulation layer and put into vacuum and ooze stove altogether, and the carbon fiber heat insulation layer is embedded in the diffusion medium, the volume ratio of diffusion medium and workpiece is 1:1; Vacuum drying oven is evacuated to vacuum less than 0.5kPa, vacuum is oozed stove altogether be warming up to 350 ℃, vacuum flue per minute changes 3 circles; Be incubated after 8 hours; The carbon fiber heat insulation layer is taken out, clean up, dry.
Sampling is tested, and forms the about 80 microns alloy anticorrosive coat of thickness at the carbon fiber heat insulation laminar surface.The hardness of beta alloy anticorrosive coat and corrosion resistance, test result is listed in table 1.
2, potassium fluosilicate and tannic acid are mixed according to the weight ratio of 1:1; Put into dispersion machine after the mixing and stir, the amount of potassium fluosilicate and tannic acid is the 5wt% of heat insulating and corrosion coating, at 25 ℃; Under the condition of relative humidity 70%, the mixture that stirs is applied to the surface of carbon fiber heat insulation layer.
3, being that the amount of 60wt% takes by weighing graphene powder according to content in the heat insulating and corrosion layer, is that the amount of 30wt% takes by weighing LaTaO according to content in the heat insulating and corrosion layer
4Powder; According to content in the corrosion-resistant finishes is that the amount of 5wt% takes by weighing KP1.Above material is put into dispersion machine mix, be applied to the surface of the carbon fiber heat insulation layer that was coated with potassium fluosilicate and tannic acid, evenly smear, thickness is consistent, and coating layer thickness is 1.5mm.
4, the carbon fiber heat insulation layer of coating alloy anticorrosive coat and heat insulating and corrosion layer more than the general is put into vacuum furnace, under vacuum state, is heated to 80 ℃, and constant temperature 2 hours obtains high temperature resistance protective layer.The case hardness of test high temperature resistance protective layer, test result is listed in table 2.
Embodiment 3
1, getting the 35wt% granularity is that the granularity of 300 purpose zinc powders, 35wt% is that 300 purpose aluminium powders, 30wt% granularity are 300 purpose nickel powders, evenly mixes obtaining the diffusion medium powder; Get the diffusion medium for preparing and carbon fiber heat insulation layer and put into vacuum and ooze stove altogether, and the carbon fiber heat insulation layer is embedded in the diffusion medium, the volume ratio of diffusion medium and workpiece is 1:1; Vacuum drying oven is evacuated to vacuum less than 0.5kPa, vacuum is oozed stove altogether be warming up to 500 ℃, vacuum flue per minute changes 3 circles; Be incubated after 8 hours; The carbon fiber heat insulation layer is taken out, clean up, dry.
Sampling is tested, and forms the about 80 microns alloy anticorrosive coat of thickness at the carbon fiber heat insulation laminar surface.The hardness of beta alloy anticorrosive coat and corrosion resistance, test result is listed in table 1.
2, potassium fluosilicate and tannic acid are mixed according to the weight ratio of 2:1; Putting into dispersion machine after the mixing stirs; The amount of potassium fluosilicate and tannic acid is the 1.5wt% of heat insulating and corrosion coating; At 15 ℃, under the condition of relative humidity 70%, the mixture that stirs is applied to the surface of carbon fiber heat insulation layer.
3, being that the amount of 70wt% takes by weighing graphene powder according to content in the heat insulating and corrosion layer, is that the amount of 28wt% takes by weighing LaTaO according to content in the heat insulating and corrosion layer
4Powder; According to content in the corrosion-resistant finishes is that the amount of 1.5wt% takes by weighing KP1.Above material is put into dispersion machine mix, be applied to the surface of the carbon fiber heat insulation layer that was coated with potassium fluosilicate and tannic acid, evenly smear, thickness is consistent, and coating layer thickness is 1.6mm.
4, the carbon fiber heat insulation layer of coating alloy anticorrosive coat and heat insulating and corrosion layer more than the general is put into vacuum furnace, under vacuum state, is heated to 80 ℃, and constant temperature 2 hours obtains high temperature resistance protective layer.The case hardness of test high temperature resistance protective layer, test result is listed in table 2.
Embodiment 4
1, getting the 32wt% granularity is that the granularity of 200 purpose zinc powders, 36wt% is that 200 purpose aluminium powders, 32wt% granularity are 200 purpose nickel powders, evenly mixes obtaining the diffusion medium powder; Get the diffusion medium for preparing and carbon fiber heat insulation layer and put into vacuum and ooze stove altogether, and the carbon fiber heat insulation layer is embedded in the diffusion medium, the volume ratio of diffusion medium and workpiece is 1:1; Vacuum drying oven is evacuated to vacuum less than 0.5kPa, vacuum is oozed stove altogether be warming up to 400 ℃, vacuum flue per minute changes 3 circles; Be incubated after 8 hours; The carbon fiber heat insulation layer is taken out, clean up, dry.
Sampling is tested, and forms the about 75 microns alloy anticorrosive coat of thickness at the carbon fiber heat insulation laminar surface.The hardness of beta alloy anticorrosive coat and corrosion resistance, test result is listed in table 1.
2, potassium fluosilicate and tannic acid are mixed according to the weight ratio of 1.5:1; Putting into dispersion machine after the mixing stirs; The amount of potassium fluosilicate and tannic acid is the 1wt% of heat insulating and corrosion coating; At 15 ℃, under the condition of relative humidity 70%, the mixture that stirs is applied to the surface of carbon fiber heat insulation layer.
3, being that the amount of 63wt% takes by weighing graphene powder according to content in the heat insulating and corrosion layer, is that the amount of 35wt% takes by weighing LaTaO according to content in the heat insulating and corrosion layer
4Powder; According to content in the corrosion-resistant finishes is that the amount of 1wt% takes by weighing KP1.Above material is put into dispersion machine mix, be applied to the surface of the carbon fiber heat insulation layer that was coated with potassium fluosilicate and tannic acid, evenly smear, thickness is consistent, and coating layer thickness is 1.5mm.
4, the carbon fiber heat insulation layer of coating alloy anticorrosive coat and heat insulating and corrosion layer more than the general is put into vacuum furnace, under vacuum state, is heated to 80 ℃, and constant temperature 2 hours obtains high temperature resistance protective layer.The case hardness of test high temperature resistance protective layer, test result is listed in table 2.
The hardness of table 1 alloy anticorrosive coat and corrosion resistance test result
1.2g/L Ca (OH)
2Condition 1.2g/L Ca (OH)
2Condition 1.2g/L Ca (OH)
2Under the condition alkali resistance, under the nondiscolouring of 167h rete, under the nondiscolouring of 172h rete, the nondiscolouring of 193h rete
Can be known that by above result high temperature resistance protective layer provided by the invention has corrosion resistance and hardness preferably, and then guarantee that the carbon fiber heat insulation layer is difficult for being corroded, character is difficult for changing, and has prolonged the service life of carbon fiber heat insulation layer.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (10)
1. a corrosion-resistant finishes that is used for polycrystalline silicon ingot or purifying furnace is characterized in that, comprising: the alloy anticorrosive coat and the heat insulating and corrosion layer that is overlying on said alloy anticorrosive coat surface that are overlying on the carbon fiber heat insulation laminar surface;
Said alloy anticorrosive coat comprises: the nickel powder of the aluminium powder of 20wt% ~ 38wt%, the zinc powder of 30wt% ~ 45wt% and 30wt% ~ 45wt%;
Said heat insulating and corrosion layer comprises: the Graphene powder of 55wt% ~ 72wt%, the LaTaO of 25wt% ~ 40wt%
4The mixture of the film forming agent of powder, 1wt% ~ 5wt% and the curing agent of 1wt% ~ 5wt% and dispersant.
2. corrosion-resistant finishes according to claim 1 is characterized in that, the content of Graphene powder is 62wt% ~ 68wt% in the said heat insulating and corrosion layer.
3. corrosion-resistant finishes according to claim 1 is characterized in that, the particle diameter of zinc powder, aluminium powder and nickel powder is 100 orders ~ 300 orders in the said alloy anticorrosive coat.
4. corrosion-resistant finishes according to claim 1 is characterized in that, said film forming agent is a waterglass.
5. corrosion-resistant finishes according to claim 1 is characterized in that, said curing agent is a fluosilicate.
6. corrosion-resistant finishes according to claim 5 is characterized in that, said dispersant is a tannic acid.
7. corrosion-resistant finishes according to claim 6 is characterized in that, the weight ratio of said fluosilicate and tannic acid is 1:1～2:1.
8. a high temperature resistance protective layer that is used for polycrystalline silicon ingot or purifying furnace is characterized in that, comprises the carbon fiber heat insulation layer and is overlying on each described corrosion-resistant finishes in the claim 1 to 7 of said carbon fiber heat insulation laminar surface.
9. the preparation method of the described high temperature resistance protective layer of claim 8 is characterized in that, may further comprise the steps:
1) after being mixed in proportion, aluminium powder, zinc powder and nickel powder obtain the diffusion medium powder; The carbon fiber heat insulation layer is embedded in is heated to 300 ℃ ~ 500 ℃ in the said diffusion medium powder; Be incubated 2 h ~ and take out after 5 hours, obtain the carbon fiber heat insulation layer that the surface is covered with the alloy anticorrosive coat;
2) mixture of curing agent and dispersant is applied to the surface of said alloy anticorrosive coat;
3) with Graphene powder, LaTaO
4After mixing in proportion, powder and film forming agent be applied to the surface of curing agent and dispersant;
4) will under vacuum state, be heated to 70 ℃ ~ 85 ℃ through the carbon fiber heat insulation layer that step 3) is handled, constant temperature 1.5 ~ 3 hours.
10. the preparation method of high temperature resistance protective layer according to claim 9 is characterized in that, said step 2) in, 0 ℃～100 ℃ of environment temperatures, relative humidity <under 90% the condition is applied to curing agent and dispersant the surface of said alloy anticorrosive coat.
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| CN101638322A (en) * | 2009-05-15 | 2010-02-03 | 西安超码科技有限公司 | Method for preparing carbon/carbon heat shields used for polysilicon hydriding furnances |
| CN101643933A (en) * | 2009-08-19 | 2010-02-10 | 蒋建纯 | CZ method silicon single crystal growth furnace quartz crucible carbon protection crucible and manufacturing process thereof |
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| CN101638322A (en) * | 2009-05-15 | 2010-02-03 | 西安超码科技有限公司 | Method for preparing carbon/carbon heat shields used for polysilicon hydriding furnances |
| CN101643933A (en) * | 2009-08-19 | 2010-02-10 | 蒋建纯 | CZ method silicon single crystal growth furnace quartz crucible carbon protection crucible and manufacturing process thereof |
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