CN102584266A - Corundum hollow ball non-sticky to aluminum and preparation method of corundum hollow ball - Google Patents
Corundum hollow ball non-sticky to aluminum and preparation method of corundum hollow ball Download PDFInfo
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- CN102584266A CN102584266A CN2012100070471A CN201210007047A CN102584266A CN 102584266 A CN102584266 A CN 102584266A CN 2012100070471 A CN2012100070471 A CN 2012100070471A CN 201210007047 A CN201210007047 A CN 201210007047A CN 102584266 A CN102584266 A CN 102584266A
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- corundum bollow
- bollow ball
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Abstract
The invention discloses a corundum hollow ball non-sticky to aluminum and a preparation method of the corundum hollow ball. The preparation method of the corundum hollow ball comprises the steps of: preparing a fluorine-containing compound water solution, a calcium-containing compound water solution, a calcium fluoride sol and a calcium fluoride powder body slurry; preparing a sulfate radical-containing compound water solution, a barium-containing compound water solution, a barium sulfate sol and a barium sulfate powder body slurry; preparing a titanium-aluminum compound sol and an aluminum titanate powder body slurry; and respectively carrying out surface coating and heat treatment on the corundum hollow ball, and enabling the surface of the corundum hollow ball to be coated with a layer of calcium fluoride, barium sulfate or aluminum titanate or 2-3 layers of two or three of the calcium fluoride, the barium sulfate and the aluminum titanate. As the calcium fluoride, the barium sulfate and the aluminum titanate are non-infiltrative to the aluminum, the treated corundum hollow ball is non-infiltrative to the aluminum. While the calcium fluoride, the barium sulfate and the aluminum titanate enter in cracks and holes of the corundum hollow ball, and the cracks and the holes can be repaired after the calcium fluoride, the barium sulfate and the aluminum titanate are sintered at a high temperature, so that the compression strength of the corundum hollow ball is enhanced.
Description
Technical field
The present invention relates to a kind of fire resisting material particle and preparation method thereof, especially relate to a kind of aluminium corundum bollow ball and preparation method thereof of not being stained with.
Background technology
Along with the rapid growth of China to the non-ferrous metal demand; Coloured smelting factory is constantly adopted new technology and new technology; The maximization and the high efficiency that make non-ferrous metallurgical furnace are to adapt to requirements of the times, and this just makes that the working conditions of refractory materials is more and more harsh, and refractory materials has been proposed many new requirements; Selecting for use of refractory materials becomes one of key link in the production, and the molten metal contact site all adopts fine and close high quality refractory materials in the Non Ferrous Melting Furnace.
With the metallurgy of aluminium is example, and molten aluminium stove adopts starting material such as compact high-alumina alumina commonly used, fused alumina, sintered alumina, adds permeability-reducing admixtures such as silit, aluminium titanates, Calcium Fluoride (Fluorspan), permanent white, and is not only with high costs, and thermal conductivity is high, serious heat loss; If employing lightweight material and low-cost high silicon raw material then are prone to aluminising or react with aluminum melt, it is required that performance is difficult to satisfy production.If Calcium Fluoride (Fluorspan) such as anti-aluminum solutions infiltration of these raw material surface applied one decks or reaction, permanent white, aluminium titanates just can address these problems well.The light matter aggregate of introducing can reduce the goods thermal conductivity significantly as furnace charge in this external nonferrous metallurgy, reduces energy consumption; Help carrying out the great strategy of national energy-saving and emission-reduction; And can increase substantially the goods thermal shock performance, and increase the service life, reduce use cost.Aglite surface fluorination calcium, permanent white, the metatitanic acid calorize also can increase substantially its compressive strength.
Summary of the invention
The object of the present invention is to provide a kind of aluminium corundum bollow ball and preparation method thereof of not being stained with, utilize corundum bollow ball, surfacing is Calcium Fluoride (Fluorspan), permanent white, aluminium titanates or above the two or 2～3 layers of coating of above three, and makes it have the method for not being stained with the aluminium characteristic.
For realizing above-mentioned purpose, the technical scheme that the present invention adopts is following:
One, a kind of aluminium corundum bollow ball of not being stained with: in the corundum bollow ball surface coverage one deck Calcium Fluoride (Fluorspan), permanent white or aluminium titanates are arranged, more than the two or 2～3 layers of coating of above three.
Said when being coated with one deck, wherein Calcium Fluoride (Fluorspan), permanent white or aluminium titanates account for and are not stained with 0.05～50% of aluminium corundum bollow ball massfraction; Be coated with Calcium Fluoride (Fluorspan) and permanent white when two-layer, internal layer is a Calcium Fluoride (Fluorspan), and skin is a permanent white, and wherein Calcium Fluoride (Fluorspan) and permanent white account for and is not stained with 0.05～50% of aluminium corundum bollow ball massfraction; Be coated with permanent white and aluminium titanates when two-layer, internal layer is an aluminium titanates, and skin is a permanent white, and wherein permanent white and aluminium titanates account for and be not stained with 0.05～50% of aluminium corundum bollow ball massfraction; Be coated with Calcium Fluoride (Fluorspan) and aluminium titanates when two-layer, internal layer is an aluminium titanates, and skin is a Calcium Fluoride (Fluorspan), wherein Calcium Fluoride (Fluorspan) and aluminium titanates account for be not stained with aluminium corundum bollow ball massfraction 0.05～50%, aluminium titanates accounts for and is not stained with 0.05～50% of aluminium corundum bollow ball massfraction; When being coated with three layers, internal layer is that aluminium titanates, middle layer are that Calcium Fluoride (Fluorspan), skin are permanent white, and wherein Calcium Fluoride (Fluorspan), permanent white and aluminium titanates account for and be not stained with 0.05～50% of aluminium corundum bollow ball massfraction.
Two, plant the preparation method who is not stained with the aluminium corundum bollow ball, following seven kinds of methods specifically arranged:
1, following when not being stained with the step of aluminium corundum bollow ball surface coverage when the Calcium Fluoride (Fluorspan) layer is arranged:
(1) batching:
The preparation fluorochemicals aqueous solution, the calcium containing compound aqueous solution, Calcium Fluoride (Fluorspan) colloidal sol or Calcium Fluoride (Fluorspan) powdery pulp are subsequent use; Its concrete component target is: fluorochemicals aqueous solution massfraction is 2～48%; Calcium containing compound aqueous solution massfraction is 5～55%; Calcium Fluoride (Fluorspan) colloidal sol massfraction is 5～25% in the Calcium Fluoride (Fluorspan) colloidal sol; Calcium Fluoride (Fluorspan) massfraction content is 10～30% in the Calcium Fluoride (Fluorspan) powdery pulp;
(2) surface applied has following five kinds of methods:
2.1 corundum bollow ball is immersed in the fluorochemicals aqueous solution oven dry; And then the corundum bollow ball that will adopt the fluorochemicals aqueous solution to handle is immersed in generation Calcium Fluoride (Fluorspan) layer in the calcium containing compound aqueous solution, oven dry after cleaning again;
2.2 dry to moistening on the surface that the fluorochemicals aqueous solution is sprayed on corundum bollow ball; And then the calcium containing compound aqueous solution is sprayed on the surface of adopting the corundum bollow ball that the fluorochemicals aqueous solution handled generates Calcium Fluoride (Fluorspan), oven dry after cleaning;
2.3 dry to moistening fully on the surface that Calcium Fluoride (Fluorspan) colloidal sol is sprayed on corundum bollow ball;
2.4 corundum bollow ball is immersed in the Calcium Fluoride (Fluorspan) colloidal sol, constantly stir in the immersion process, soak time is 0.5～60min, takes out the back oven dry;
2.5 it is moistening until fully directly the Calcium Fluoride (Fluorspan) powdery pulp to be sprayed on the surface of corundum bollow ball, oven dry gets final product;
(3) thermal treatment:
The corundum bollow ball that the surface is scribbled one deck Calcium Fluoride (Fluorspan) places 800～1200 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation.
The described fluorine cpd aqueous solution is ammonium fluoride aqueous solution, sodium fluoride aqueous solution or potassium fluoride aqueous solution; The described calcium containing compound aqueous solution is calcium nitrate aqueous solution or calcium chloride water.
2, following when not being stained with the step of aluminium corundum bollow ball surface coverage when the permanent white layer is arranged:
(1) batching:
The preparation sulfur acid radical compound aqueous solution, the containing barium compound aqueous solution, barium sulfate sol or permanent white powdery pulp are subsequent use; Concrete component target is: sulfur acid radical compound aqueous solution massfraction is 5～42.9%; Containing barium compound aqueous solution massfraction is 3～26%; The permanent white massfraction is in the barium sulfate sol: 5～25%; The permanent white massfraction is 10～30% in the permanent white powdery pulp;
(2) surface applied has following five kinds of methods:
2.1 corundum bollow ball is immersed in the sulfur acid radical compound aqueous solution oven dry; And then the corundum bollow ball that will adopt the sulfur acid radical compound aqueous solution to handle is immersed in generation permanent white layer in the containing barium compound aqueous solution, oven dry after cleaning again;
2.2 dry to moistening on the surface that the sulfur acid radical compound aqueous solution is sprayed on corundum bollow ball; And then the containing barium compound aqueous solution is sprayed on the surface of adopting the corundum bollow ball that the sulfur acid radical compound aqueous solution handled generates permanent white, oven dry after cleaning;
2.3 dry to moistening fully on the surface that barium sulfate sol is sprayed on corundum bollow ball;
2.4 corundum bollow ball is immersed in the barium sulfate sol, constantly stir in the immersion process, soak time does
0.5～60min takes out the back oven dry;
2.5 it is moistening until fully directly the permanent white powdery pulp to be sprayed on the surface of corundum bollow ball, oven dry gets final product;
(3) thermal treatment
The corundum bollow ball that the surface is scribbled one deck permanent white places 600～900 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation.
The described sulfur acid radical compound aqueous solution is ammonium sulfate solution, potassium sulfate solution or aqueous sodium persulfate solution; The described containing barium compound aqueous solution is barium nitrate aqueous solution or barium chloride solution.
3, following when not being stained with the step of aluminium corundum bollow ball surface coverage when the metatitanic acid aluminium lamination is arranged:
(1) batching:
Purchase commercially available or preparation titanium aluminium complex sol, titanium colloidal sol and aluminium titanates powdery pulp subsequent use; Component target requires as follows:
A titanium aluminium complex sol: Ti
4+Concentration is 0.2～0.3mol/L, Al
3+Concentration is the titanium aluminium complex sol of 0.2～0.3mol/L; The adding x is 1.6～6% Mg in the colloidal sol
2+Be stablizer; Or the adding x is 3～5% Mg
2+With x be 0.4～0.8% Ce
4+Be stablizer; Or only to add x be 1.6～3.3% Fe
3+Be stablizer;
B titanium colloidal sol: Ti
4+Concentration is the colloidal sol of 0.2～0.3mol/L, and the adding x is 3.7～13% Mg in the colloidal sol
2+Be stablizer; Or the adding x is 7～10% Mg
2+With x be 0.9～1.7% Ce
4+Be stablizer; Or the adding x is 3.8～7% Fe
3+As stablizer;
C aluminium titanates powdery pulp: consist of massfraction and be 40～50% Al
2O
3With 50～60% TiO
2Wherein adding massfraction is that 1～4%MgO is a stablizer; Or to add massfraction be that 1～4% MgO and massfraction are 1～3% CeO
2Mixture is a stablizer; Or the adding massfraction is 3～8%Fe
2O
3Be stablizer; Or the adding massfraction is 0.5～2% ZrO
2Be stablizer;
(2) surface applied has following two kinds of methods:
2.1 corundum bollow ball is immersed in titanium aluminium complex sol or titanium colloidal sol or the aluminium titanates powdery pulp, constantly stir in the immersion process, soak time is 0.5～60min, takes out the back oven dry;
2.2 it is moistening until fully that titanium aluminium complex sol or titanium colloidal sol or aluminium titanates powdery pulp are sprayed on the corundum bollow ball surface, oven dry gets final product;
(3) thermal treatment
To soak or spray titanium aluminium complex sol, the corundum bollow ball of titanium colloidal sol and aluminium titanates powdery pulp places 1250～1450 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation.
4, when not being stained with aluminium corundum bollow ball surface coverage when Calcium Fluoride (Fluorspan) and permanent white two layers of coatings are arranged:
(1) earlier corundum bollow ball is carried out Calcium Fluoride (Fluorspan) and apply, its step is following:
(1) batching:
The preparation fluorochemicals aqueous solution, the calcium containing compound aqueous solution, Calcium Fluoride (Fluorspan) colloidal sol or Calcium Fluoride (Fluorspan) powdery pulp are subsequent use; Its concrete component target is: fluorochemicals aqueous solution massfraction is 2～48%; Calcium containing compound aqueous solution massfraction is 5～55%; Calcium Fluoride (Fluorspan) colloidal sol massfraction is 5～25% in the Calcium Fluoride (Fluorspan) colloidal sol; Calcium Fluoride (Fluorspan) massfraction content is 10～30% in the Calcium Fluoride (Fluorspan) powdery pulp;
(2) surface applied has following five kinds of methods:
2.1 corundum bollow ball is immersed in the fluorochemicals aqueous solution oven dry; And then the corundum bollow ball that will adopt the fluorochemicals aqueous solution to handle is immersed in generation Calcium Fluoride (Fluorspan) layer in the calcium containing compound aqueous solution, oven dry after cleaning again;
2.2 dry to moistening on the surface that the fluorochemicals aqueous solution is sprayed on corundum bollow ball; And then the calcium containing compound aqueous solution is sprayed on the surface of adopting the corundum bollow ball that the fluorochemicals aqueous solution handled generates Calcium Fluoride (Fluorspan), oven dry after cleaning;
2.3 dry to moistening fully on the surface that Calcium Fluoride (Fluorspan) colloidal sol is sprayed on corundum bollow ball;
2.4 corundum bollow ball is immersed in the Calcium Fluoride (Fluorspan) colloidal sol, constantly stir in the immersion process, soak time is 0.5～60min, takes out the back oven dry;
2.5 it is moistening until fully directly the Calcium Fluoride (Fluorspan) powdery pulp to be sprayed on the surface of corundum bollow ball, oven dry gets final product;
(3) thermal treatment:
The corundum bollow ball that the surface is scribbled one deck Calcium Fluoride (Fluorspan) places 800～1200 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation.
(2) again corundum bollow ball is carried out permanent white and apply, its step is following:
(1) batching:
The preparation sulfur acid radical compound aqueous solution, the containing barium compound aqueous solution, barium sulfate sol or permanent white powdery pulp are subsequent use; Concrete component target is: sulfur acid radical compound aqueous solution massfraction is 5～42.9%; Containing barium compound aqueous solution massfraction is 3～26%; The permanent white massfraction is in the barium sulfate sol: 5～25%; The permanent white massfraction is 10～30% in the permanent white powdery pulp;
(2) surface applied has following five kinds of methods:
2.1 corundum bollow ball is immersed in the sulfur acid radical compound aqueous solution oven dry; And then the corundum bollow ball that will adopt the sulfur acid radical compound aqueous solution to handle is immersed in generation permanent white layer in the containing barium compound aqueous solution, oven dry after cleaning again;
2.2 dry to moistening on the surface that the sulfur acid radical compound aqueous solution is sprayed on corundum bollow ball; And then the containing barium compound aqueous solution is sprayed on the surface of adopting the corundum bollow ball that the sulfur acid radical compound aqueous solution handled generates permanent white, oven dry after cleaning;
2.3 dry to moistening fully on the surface that barium sulfate sol is sprayed on corundum bollow ball;
2.4 corundum bollow ball is immersed in the barium sulfate sol, constantly stir in the immersion process, soak time does
0.5～60min takes out the back oven dry;
2.5 it is moistening until fully directly the permanent white powdery pulp to be sprayed on the surface of corundum bollow ball, oven dry gets final product;
(3) thermal treatment
The corundum bollow ball that the surface is scribbled one deck permanent white places 600～900 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation.
5, when not being stained with aluminium corundum bollow ball surface coverage when Calcium Fluoride (Fluorspan) and two layers of coating of aluminium titanates are arranged:
(1) earlier corundum bollow ball is carried out aluminium titanates and apply, its step is following:
(1) batching:
Purchase commercially available or preparation titanium aluminium complex sol, titanium colloidal sol and aluminium titanates powdery pulp subsequent use; Component target requires as follows:
A titanium aluminium complex sol: Ti
4+Concentration is 0.2～0.3mol/L, Al
3+Concentration is the titanium aluminium complex sol of 0.2～0.3mol/L; The adding x is 1.6～6% Mg in the colloidal sol
2+Be stablizer; Or the adding x is 3～5% Mg
2+With x be 0.4～0.8% Ce
4+Be stablizer; Or only to add x be 1.6～3.3% Fe
3+For being stablizer;
B titanium colloidal sol: Ti
4+Concentration is the colloidal sol of 0.2～0.3mol/L, and the adding x is 3.7～13% Mg in the colloidal sol
2+Be stablizer; Or the adding x is 7～10% Mg
2+With x be 0.9～1.7% Ce
4+Be stablizer; Or the adding x is 3.8～7% Fe
3+As stablizer;
C aluminium titanates powdery pulp: consist of massfraction and be 40～50% Al
2O
3With 50～60% TiO
2Wherein adding massfraction is that 1～4%MgO is a stablizer; Or to add massfraction be that 1～4% MgO and massfraction are 1～3% CeO
2Mixture is a stablizer; Or the adding massfraction is 3～8%Fe
2O
3Be stablizer; Or the adding massfraction is 0.5～2% ZrO
2Be stablizer;
(2) surface applied has following two kinds of methods:
2.1 corundum bollow ball is immersed in titanium aluminium complex sol or titanium colloidal sol or the aluminium titanates powdery pulp, constantly stir in the immersion process, soak time is 0.5～60min, takes out the back oven dry;
2.2 it is moistening until fully that titanium aluminium complex sol or titanium colloidal sol or aluminium titanates powdery pulp are sprayed on the corundum bollow ball surface, oven dry gets final product;
(3) thermal treatment
To soak or spray titanium aluminium complex sol, the corundum bollow ball of titanium colloidal sol and aluminium titanates powdery pulp places 1250～1450 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation.
(2) again corundum bollow ball is carried out Calcium Fluoride (Fluorspan) and apply, its step is following:
(1) batching:
The preparation fluorochemicals aqueous solution, the calcium containing compound aqueous solution, Calcium Fluoride (Fluorspan) colloidal sol or Calcium Fluoride (Fluorspan) powdery pulp are subsequent use; Its concrete component target is: fluorochemicals aqueous solution massfraction is 2～48%; Calcium containing compound aqueous solution massfraction is 5～55%; Calcium Fluoride (Fluorspan) colloidal sol massfraction is 5～25% in the Calcium Fluoride (Fluorspan) colloidal sol; Calcium Fluoride (Fluorspan) massfraction content is 10～30% in the Calcium Fluoride (Fluorspan) powdery pulp;
(2) surface applied has following five kinds of methods:
2.1 corundum bollow ball is immersed in the fluorochemicals aqueous solution oven dry; And then the corundum bollow ball that will adopt the fluorochemicals aqueous solution to handle is immersed in generation Calcium Fluoride (Fluorspan) layer in the calcium containing compound aqueous solution, oven dry after cleaning again;
2.2 dry to moistening on the surface that the fluorochemicals aqueous solution is sprayed on corundum bollow ball; And then the calcium containing compound aqueous solution is sprayed on the surface of adopting the corundum bollow ball that the fluorochemicals aqueous solution handled generates Calcium Fluoride (Fluorspan), oven dry after cleaning;
2.3 dry to moistening fully on the surface that Calcium Fluoride (Fluorspan) colloidal sol is sprayed on corundum bollow ball;
2.4 corundum bollow ball is immersed in the Calcium Fluoride (Fluorspan) colloidal sol, constantly stir in the immersion process, soak time is 0.5～60min, takes out the back oven dry;
2.5 it is moistening until fully directly the Calcium Fluoride (Fluorspan) powdery pulp to be sprayed on the surface of corundum bollow ball, oven dry gets final product;
(3) thermal treatment:
The corundum bollow ball that the surface is scribbled one deck Calcium Fluoride (Fluorspan) places 800～1200 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation.
6, when not being stained with aluminium corundum bollow ball surface coverage when aluminium titanates and two layers of coating of Calcium Fluoride (Fluorspan) are arranged:
(1) earlier corundum bollow ball is carried out aluminium titanates and apply, its step is following:
(1) batching:
Purchase commercially available or preparation titanium aluminium complex sol, titanium colloidal sol and aluminium titanates powdery pulp subsequent use; Component target requires as follows:
A titanium aluminium complex sol: Ti
4+Concentration is 0.2～0.3mol/L, Al
3+Concentration is the titanium aluminium complex sol of 0.2～0.3mol/L; The adding x is 1.6～6% Mg in the colloidal sol
2+Be stablizer; Or the adding x is 3～5% Mg
2+With x be 0.4～0.8% Ce
4+Be stablizer; Or only to add x be 1.6～3.3% Fe
3+For being stablizer;
B titanium colloidal sol: Ti
4+Concentration is the colloidal sol of 0.2～0.3mol/L, and the adding x is 3.7～13% Mg in the colloidal sol
2+Be stablizer; Or the adding x is 7～10% Mg
2+With x be 0.9～1.7% Ce
4+Be stablizer; Or the adding x is 3.8～7% Fe
3+As stablizer;
C aluminium titanates powdery pulp: consist of massfraction and be 40～50% Al
2O
3With 50～60% TiO
2Wherein adding massfraction is that 1～4%MgO is a stablizer; Or to add massfraction be that 1～4% MgO and massfraction are 1～3% CeO
2Mixture is a stablizer; Or the adding massfraction is 3～8%Fe
2O
3Be stablizer; Or the adding massfraction is 0.5～2% ZrO
2Be stablizer;
(2) surface applied has following two kinds of methods:
2.1 corundum bollow ball is immersed in titanium aluminium complex sol or titanium colloidal sol or the aluminium titanates powdery pulp, constantly stir in the immersion process, soak time is 0.5～60min, takes out the back oven dry;
2.2 it is moistening until fully that titanium aluminium complex sol or titanium colloidal sol or aluminium titanates powdery pulp are sprayed on the corundum bollow ball surface, oven dry gets final product;
(3) thermal treatment
To soak or spray titanium aluminium complex sol, the corundum bollow ball of titanium colloidal sol and aluminium titanates powdery pulp places 1250～1450 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation.
(2) again corundum bollow ball is carried out Calcium Fluoride (Fluorspan) and apply, its step is following:
(1) batching:
The preparation fluorochemicals aqueous solution, the calcium containing compound aqueous solution, Calcium Fluoride (Fluorspan) colloidal sol or Calcium Fluoride (Fluorspan) powdery pulp are subsequent use; Its concrete component target is: fluorochemicals aqueous solution massfraction is 2～48%; Calcium containing compound aqueous solution massfraction is 5～55%; Calcium Fluoride (Fluorspan) colloidal sol massfraction is 5～25% in the Calcium Fluoride (Fluorspan) colloidal sol; Calcium Fluoride (Fluorspan) massfraction content is 10～30% in the Calcium Fluoride (Fluorspan) powdery pulp;
(2) surface applied has following five kinds of methods:
2.1 corundum bollow ball is immersed in the fluorochemicals aqueous solution oven dry; And then the corundum bollow ball that will adopt the fluorochemicals aqueous solution to handle is immersed in generation Calcium Fluoride (Fluorspan) layer in the calcium containing compound aqueous solution, oven dry after cleaning again;
2.2 dry to moistening on the surface that the fluorochemicals aqueous solution is sprayed on corundum bollow ball; And then the calcium containing compound aqueous solution is sprayed on the surface of adopting the corundum bollow ball that the fluorochemicals aqueous solution handled generates Calcium Fluoride (Fluorspan), oven dry after cleaning;
2.3 dry to moistening fully on the surface that Calcium Fluoride (Fluorspan) colloidal sol is sprayed on corundum bollow ball;
2.4 corundum bollow ball is immersed in the Calcium Fluoride (Fluorspan) colloidal sol, constantly stir in the immersion process, soak time is 0.5～60min, takes out the back oven dry;
2.5 it is moistening until fully directly the Calcium Fluoride (Fluorspan) powdery pulp to be sprayed on the surface of corundum bollow ball, oven dry gets final product;
(3) thermal treatment:
The corundum bollow ball that the surface is scribbled one deck Calcium Fluoride (Fluorspan) places 800～1200 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation.
7, when not being stained with aluminium corundum bollow ball surface coverage when Calcium Fluoride (Fluorspan), permanent white, three layers of compound coating of aluminium titanates are arranged:
(1) earlier the aluminium titanates coating is carried out on the corundum bollow ball surface, its step is following:
(1) batching:
Purchase commercially available or preparation titanium aluminium complex sol, titanium colloidal sol and aluminium titanates powdery pulp subsequent use; Component target requires as follows:
A titanium aluminium complex sol: Ti
4+Concentration is 0.2～0.3mol/L, Al
3+Concentration is the titanium aluminium complex sol of 0.2～0.3mol/L; The adding x is 1.6～6% Mg in the colloidal sol
2+Be stablizer; Or the adding x is 3～5% Mg
2+With x be 0.4～0.8% Ce
4+Be stablizer; Or only to add x be 1.6～3.3% Fe
3+For being stablizer;
B titanium colloidal sol: Ti
4+Concentration is the colloidal sol of 0.2～0.3mol/L, and the adding x is 3.7～13% Mg in the colloidal sol
2+Be stablizer; Or the adding x is 7～10% Mg
2+With x be 0.9～1.7% Ce
4+Be stablizer; Or the adding x is 3.8～7% Fe
3+As stablizer;
C aluminium titanates powdery pulp: consist of massfraction and be 40～50% Al
2O
3With 50～60% TiO
2Wherein adding massfraction is that 1～4%MgO is a stablizer; Or to add massfraction be that 1～4% MgO and massfraction are 1～3% CeO
2Mixture is a stablizer; Or the adding massfraction is 3～8%Fe
2O
3Be stablizer; Or the adding massfraction is 0.5～2% ZrO
2Be stablizer;
(2) surface applied has following two kinds of methods:
2.1 corundum bollow ball is immersed in titanium aluminium complex sol or titanium colloidal sol or the aluminium titanates powdery pulp, constantly stir in the immersion process, soak time is 0.5～60min, takes out the back oven dry;
2.2 it is moistening until fully that titanium aluminium complex sol or titanium colloidal sol or aluminium titanates powdery pulp are sprayed on the corundum bollow ball surface, oven dry gets final product;
(3) thermal treatment
To soak or spray titanium aluminium complex sol, the corundum bollow ball of titanium colloidal sol and aluminium titanates powdery pulp places 1250～1450 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation.
(2) covered the aluminium titanates coating and formed calcium fluoride coating again, its step is following:
(1) batching:
The preparation fluorochemicals aqueous solution, the calcium containing compound aqueous solution, Calcium Fluoride (Fluorspan) colloidal sol or Calcium Fluoride (Fluorspan) powdery pulp are subsequent use; Its concrete component target is: fluorochemicals aqueous solution massfraction is 2～48%; Calcium containing compound aqueous solution massfraction is 5～55%; Calcium Fluoride (Fluorspan) colloidal sol massfraction is 5～25% in the Calcium Fluoride (Fluorspan) colloidal sol; Calcium Fluoride (Fluorspan) massfraction content is 10～30% in the Calcium Fluoride (Fluorspan) powdery pulp;
(2) surface applied has following five kinds of methods:
2.1 corundum bollow ball is immersed in the fluorochemicals aqueous solution oven dry; And then the corundum bollow ball that will adopt the fluorochemicals aqueous solution to handle is immersed in generation Calcium Fluoride (Fluorspan) layer in the calcium containing compound aqueous solution, oven dry after cleaning again;
2.2 dry to moistening on the surface that the fluorochemicals aqueous solution is sprayed on corundum bollow ball; And then the calcium containing compound aqueous solution is sprayed on the surface of adopting the corundum bollow ball that the fluorochemicals aqueous solution handled generates Calcium Fluoride (Fluorspan), oven dry after cleaning;
2.3 dry to moistening fully on the surface that Calcium Fluoride (Fluorspan) colloidal sol is sprayed on corundum bollow ball;
2.4 corundum bollow ball is immersed in the Calcium Fluoride (Fluorspan) colloidal sol, constantly stir in the immersion process, soak time is 0.5～60min, takes out the back oven dry;
2.5 it is moistening until fully directly the Calcium Fluoride (Fluorspan) powdery pulp to be sprayed on the surface of corundum bollow ball, oven dry gets final product;
(3) thermal treatment:
The corundum bollow ball that the surface is scribbled one deck Calcium Fluoride (Fluorspan) places 800～1200 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation.
(3) corundum bollow ball that has been coated with aluminium titanates and calcium fluoride coating forms the permanent white coating, and its step is following:
(1) batching:
The preparation sulfur acid radical compound aqueous solution, the containing barium compound aqueous solution, barium sulfate sol or permanent white powdery pulp are subsequent use; Concrete component target is: sulfur acid radical compound aqueous solution massfraction is 5～42.9%; Containing barium compound aqueous solution massfraction is 3～26%; The permanent white massfraction is in the barium sulfate sol: 5～25%; The permanent white massfraction is 10～30% in the permanent white powdery pulp;
(2) surface applied has following five kinds of methods:
2.1 corundum bollow ball is immersed in the sulfur acid radical compound aqueous solution oven dry; And then the corundum bollow ball that will adopt the sulfur acid radical compound aqueous solution to handle is immersed in generation permanent white layer in the containing barium compound aqueous solution, oven dry after cleaning again;
2.2 dry to moistening on the surface that the sulfur acid radical compound aqueous solution is sprayed on corundum bollow ball; And then the containing barium compound aqueous solution is sprayed on the surface of adopting the corundum bollow ball that the sulfur acid radical compound aqueous solution handled generates permanent white, oven dry after cleaning;
2.3 dry to moistening fully on the surface that barium sulfate sol is sprayed on corundum bollow ball;
2.4 corundum bollow ball is immersed in the barium sulfate sol, constantly stir in the immersion process, soak time is 0.5～60min, takes out the back oven dry;
2.5 it is moistening until fully directly the permanent white powdery pulp to be sprayed on the surface of corundum bollow ball, oven dry gets final product;
(3) thermal treatment
The corundum bollow ball that the surface is scribbled one deck permanent white places 600～900 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation.
The sulfur acid radical compound aqueous solution described in the method 1～7 is ammonium sulfate solution, potassium sulfate solution or aqueous sodium persulfate solution; The described containing barium compound aqueous solution is barium nitrate aqueous solution or barium chloride solution; The described fluorine cpd aqueous solution is ammonium fluoride aqueous solution, sodium fluoride aqueous solution or potassium fluoride aqueous solution; The described calcium containing compound aqueous solution is calcium nitrate aqueous solution or calcium chloride water.
The beneficial effect that the present invention has is:
Adopt surface applied Calcium Fluoride (Fluorspan), permanent white, the method for aluminium titanates is carried out surface-treated.Calcium Fluoride (Fluorspan), permanent white and aluminium titanates are attached to the surface of corundum bollow ball, and the entering slit, in crackle and the hole, and dry back Calcium Fluoride (Fluorspan), permanent white, aluminium titanates are distributed in the corundum bollow ball surface, slit and intergranule.Calcium Fluoride (Fluorspan) under the condition of being heated, permanent white, aluminium titanates corundum bollow ball sintering.Because Calcium Fluoride (Fluorspan), permanent white, aluminium titanates have not imbibition characteristic of pair aluminium, thereby treated corundum bollow ball does not soak into aluminium.And Calcium Fluoride (Fluorspan), permanent white, aluminium titanates get among corundum bollow ball crackle and the hole, ability mended crack and hole behind the high temperature sintering, thereby the compressive strength of raising corundum bollow ball.
Description of drawings
Fig. 1 is the corundum bollow ball sectional view with one deck coating.
Fig. 2 is the corundum bollow ball sectional view with two layers of coating.
Fig. 3 is the corundum bollow ball sectional view with three layers of coating.
Among the figure: 1, corundum bollow ball matrix; 2, Calcium Fluoride (Fluorspan), permanent white or aluminium titanates coating, 3 and 4 is respectively Calcium Fluoride (Fluorspan) and permanent white combination coating, aluminium titanates and Calcium Fluoride (Fluorspan) combination coating or aluminium titanates and permanent white combination coating, 5, the aluminium titanates coating; 6, calcium fluoride coating, 7, the permanent white coating.
Embodiment
Embodiment 1: (immersion)
Configure the fluorochemicals aqueous solution and the calcium containing compound aqueous solution earlier, corundum bollow ball is immersed in the fluorochemicals aqueous solution, will be immersed in the calcium containing compound aqueous solution through the corundum bollow ball that the fluorochemicals aqueous solution was handled again after the oven dry; The surface generates Calcium Fluoride (Fluorspan); Behind the washing and drying, put into High Temperature Furnaces Heating Apparatus thermal treatment, thermal treatment temp is 800～1200 ℃; Soaking time is 1～4 hour, obtains the corundum bollow ball surface at last and is covered with one deck Calcium Fluoride (Fluorspan).Specific embodiments is seen table 1.Adopt this method gained to have its sectional view of corundum bollow ball such as Fig. 1 of calcium fluoride coating, wherein 1 is the corundum bollow ball matrix, the 2nd, and calcium fluoride coating
It is 2% sodium fluoride aqueous solution that corundum bollow ball adopts massfraction and massfraction is 5% a calcium nitrite reactant aqueous solution when precipitating coating, Calcium Fluoride (Fluorspan) quality percentage composition 0.05%;
It is 3.8% sodium fluoride aqueous solution and massfraction when being 45% calcium nitrate aqueous solution reaction precipitation coating that corundum bollow ball adopts massfraction, Calcium Fluoride (Fluorspan) quality percentage composition 1.5%;
It is 2.5% sodium fluoride aqueous solution that corundum bollow ball adopts massfraction and massfraction is 20% a calcium nitrite reactant aqueous solution when precipitating coating, Calcium Fluoride (Fluorspan) quality percentage composition 0.08%;
It is 3.8% sodium fluoride aqueous solution and massfraction when being 42% calcium chloride water reaction precipitation coating that corundum bollow ball adopts massfraction, Calcium Fluoride (Fluorspan) quality percentage composition 1.2%;
It is 25% ammonium fluoride aqueous solution and massfraction when being 55% chlorine calcium nitrate aqueous solution reaction precipitation coating that corundum bollow ball adopts massfraction, Calcium Fluoride (Fluorspan) quality percentage composition 15%;
It is 20% ammonium fluoride aqueous solution that corundum bollow ball adopts massfraction and massfraction is 13% a Calcium hydrogen carbonate calcium reactant aqueous solution when precipitating coating, Calcium Fluoride (Fluorspan) quality percentage composition 8%;
It is 15% ammonium fluoride aqueous solution that corundum bollow ball adopts massfraction and massfraction is 13% a Calcium hydrogen carbonate reactant aqueous solution when precipitating coating, Calcium Fluoride (Fluorspan) quality percentage composition 7%;
It is 10% ammonium fluoride aqueous solution and massfraction when being 30% calcium chloride water reaction precipitation coating that corundum bollow ball adopts massfraction, Calcium Fluoride (Fluorspan) quality percentage composition 12%;
It is 48% potassium fluoride aqueous solution that corundum bollow ball adopts massfraction and massfraction is 5% a Calcium hydrogen carbonate reactant aqueous solution when precipitating coating, Calcium Fluoride (Fluorspan) quality percentage composition 6%;
It is 39% potassium fluoride aqueous solution that corundum bollow ball adopts massfraction and massfraction is 45% a calcium nitrite reactant aqueous solution when precipitating coating, Calcium Fluoride (Fluorspan) quality percentage composition 14%;
It is 30% potassium fluoride aqueous solution and massfraction when being 35% calcium nitrate aqueous solution reaction precipitation coating that corundum bollow ball adopts massfraction, Calcium Fluoride (Fluorspan) quality percentage composition 12%;
It is 20% potassium fluoride aqueous solution and massfraction when being 20% calcium chloride water reaction precipitation coating that corundum bollow ball adopts massfraction, Calcium Fluoride (Fluorspan) quality percentage composition 10%;
The modification of table 1 precipitator method is not stained with the aluminium corundum bollow ball and under differing temps, is handled
Embodiment 2 (spraying)
Configure the fluorochemicals aqueous solution and the calcium containing compound aqueous solution earlier, the fluorochemicals aqueous solution be sprayed on the corundum bollow ball skin drying, and then the calcium containing compound aqueous solution is sprayed on sprayed the fluorochemicals aqueous solution corundum bollow ball surface to moistening; Reaction generates the Calcium Fluoride (Fluorspan) deposition; High Temperature Furnaces Heating Apparatus thermal treatment is put in the washing oven dry, and thermal treatment temp is 800～1200 ℃; Soaking time is 1～4 hour, obtains the corundum bollow ball surface at last and is covered with one deck Calcium Fluoride (Fluorspan).Specific embodiments is seen table 2.Adopt this method gained to have its sectional view of corundum bollow ball such as Fig. 1 of calcium fluoride coating, wherein 1 is the corundum bollow ball matrix, the 2nd, and calcium fluoride coating
Corundum bollow ball adopts massfraction when be 2% sodium fluoride aqueous solution with massfraction being 5% calcium nitrite aqueous solution spraying reaction back generation coating, Calcium Fluoride (Fluorspan) quality percentage composition 0.08%;
Corundum bollow ball adopts massfraction when be 3.8% sodium fluoride aqueous solution with massfraction being 45% calcium nitrate aqueous solution spraying reaction back generation coating, Calcium Fluoride (Fluorspan) quality percentage composition 2.3%;
Corundum bollow ball adopts massfraction when be 2.5% sodium fluoride aqueous solution with massfraction being 20% calcium nitrite aqueous solution spraying reaction back generation coating, Calcium Fluoride (Fluorspan) quality percentage composition 0.78%;
Corundum bollow ball adopts massfraction when be 3.8% sodium fluoride aqueous solution with massfraction being 42% calcium chloride water spraying reaction back generation coating, Calcium Fluoride (Fluorspan) quality percentage composition 1.5%;
Corundum bollow ball adopts massfraction when be 25% ammonium fluoride aqueous solution with massfraction being 55% chlorine calcium nitrate aqueous solution spraying reaction back generation coating, Calcium Fluoride (Fluorspan) quality percentage composition 23%;
Corundum bollow ball adopts massfraction when be 20% ammonium fluoride aqueous solution with massfraction being 13% Calcium hydrogen carbonate calcium aqueous solution spraying reaction back generation coating, Calcium Fluoride (Fluorspan) quality percentage composition 10%;
Corundum bollow ball adopts massfraction when be 15% ammonium fluoride aqueous solution with massfraction being 13% Calcium hydrogen carbonate aqueous solution spraying reaction back generation coating, Calcium Fluoride (Fluorspan) quality percentage composition 9%;
Corundum bollow ball adopts massfraction when be 10% ammonium fluoride aqueous solution with massfraction being 30% calcium chloride water spraying reaction back generation coating, Calcium Fluoride (Fluorspan) quality percentage composition 15%;
Corundum bollow ball adopts massfraction when be 48% potassium fluoride aqueous solution with massfraction being 5% Calcium hydrogen carbonate aqueous solution spraying reaction back generation coating, Calcium Fluoride (Fluorspan) quality percentage composition 8%;
Corundum bollow ball adopts massfraction when be 39% potassium fluoride aqueous solution with massfraction being 45% calcium nitrite aqueous solution spraying reaction back generation coating, Calcium Fluoride (Fluorspan) quality percentage composition 120%;
Corundum bollow ball adopts massfraction when be 30% potassium fluoride aqueous solution with massfraction being 35% calcium nitrate aqueous solution spraying reaction back generation coating, Calcium Fluoride (Fluorspan) quality percentage composition 17%;
Corundum bollow ball adopts massfraction when be 20% potassium fluoride aqueous solution with massfraction being 20% calcium chloride water spraying reaction back generation coating, Calcium Fluoride (Fluorspan) quality percentage composition 13%;
The modification of table 2 precipitator method is not stained with the aluminium corundum bollow ball and under differing temps, is handled
Embodiment 3: (spraying)
With commercial or preparation calcium fluoride powder system form slurry, the Calcium Fluoride (Fluorspan) massfraction is 10%, 15%, 18% in the slurry; 22%, 26%, 30%, be sprayed on the corundum bollow ball surface to moistening fully; Oven dry was placed in the High Temperature Furnaces Heating Apparatus thermal treatment 1～4 hour, and thermal treatment temp is 800 ℃～1200 ℃.Specific embodiments is seen table 3.Adopt this method gained to have its sectional view of corundum bollow ball such as Fig. 1 of calcium fluoride coating, wherein 1 is the corundum bollow ball matrix, the 2nd, and calcium fluoride coating
The method that is employed in corundum bollow ball surface coating quality mark and is 10% Calcium Fluoride (Fluorspan) powdery pulp generates coating, Calcium Fluoride (Fluorspan) Calcium Fluoride (Fluorspan) quality percentage composition 13%;
The method that is employed in corundum bollow ball surface coating quality mark and is 15% Calcium Fluoride (Fluorspan) powdery pulp generates coating, Calcium Fluoride (Fluorspan) Calcium Fluoride (Fluorspan) quality percentage composition 18%;
The method that is employed in corundum bollow ball surface coating quality mark and is 18% Calcium Fluoride (Fluorspan) powdery pulp generates coating, Calcium Fluoride (Fluorspan) Calcium Fluoride (Fluorspan) quality percentage composition 27%;
The method that is employed in corundum bollow ball surface coating quality mark and is 22% Calcium Fluoride (Fluorspan) powdery pulp generates coating, Calcium Fluoride (Fluorspan) Calcium Fluoride (Fluorspan) quality percentage composition 35%;
The method that is employed in corundum bollow ball surface coating quality mark and is 26% Calcium Fluoride (Fluorspan) powdery pulp generates coating, Calcium Fluoride (Fluorspan) Calcium Fluoride (Fluorspan) quality percentage composition 41%;
The method that is employed in corundum bollow ball surface coating quality mark and is 30% Calcium Fluoride (Fluorspan) powdery pulp generates coating, Calcium Fluoride (Fluorspan) Calcium Fluoride (Fluorspan) quality percentage composition 50%;
Table 3 is not stained with the aluminium corundum bollow ball and under differing temps, is handled
Embodiment 4 Calcium Fluoride (Fluorspan) colloidal sols
Commercial Calcium Fluoride (Fluorspan) colloidal sol is configured to the Calcium Fluoride (Fluorspan) colloidal sol of various solubility; The Calcium Fluoride (Fluorspan) massfraction is 5%, 15%, 25% in the colloidal sol; Be sprayed on corundum bollow ball surface to moistening fully or corundum bollow ball is immersed in the Calcium Fluoride (Fluorspan) colloidal sol; Oven dry was placed in the High Temperature Furnaces Heating Apparatus thermal treatment 1～4 hour, and thermal treatment temp is 800 ℃～1200 ℃.Specific embodiments is seen table 4.Adopt this method gained to have its sectional view of corundum bollow ball such as Fig. 1 of calcium fluoride coating, wherein 1 is the corundum bollow ball matrix, the 2nd, and calcium fluoride coating
Table 4 Calcium Fluoride (Fluorspan) colloidal sol is handled corundum bollow ball
Embodiment 5: (immersion)
Configure the sulfur acid radical compound aqueous solution and the containing barium compound aqueous solution earlier, corundum bollow ball is immersed in the sulfur acid radical compound aqueous solution, will be immersed in through the corundum bollow ball that the sulfur acid radical compound aqueous solution was handled in the containing barium compound aqueous solution again after the oven dry; Make it the surface and generate permanent white; Behind the washing and drying, put into High Temperature Furnaces Heating Apparatus thermal treatment, thermal treatment temp is 600～900 ℃; Soaking time is 1～4 hour, obtains the corundum bollow ball surface at last and is covered with one deck permanent white.Specific embodiments is seen table 5.Its sectional view of corundum bollow ball such as Fig. 1 of adopting this method gained to have the permanent white coating, wherein 1 is the corundum bollow ball matrix, the 2nd, the permanent white coating
It is 42.9% ammonium sulfate solution and massfraction when being 5% barium nitrate aqueous solution reaction precipitation coating that corundum bollow ball adopts massfraction, permanent white quality percentage composition 8%;
It is 30% ammonium sulfate solution and massfraction when being 3% barium nitrate aqueous solution reaction precipitation coating that corundum bollow ball adopts massfraction, permanent white quality percentage composition 3%;
It is 20% ammonium sulfate solution and massfraction when being 7% barium nitrate aqueous solution reaction precipitation coating that corundum bollow ball adopts massfraction, permanent white quality percentage composition 5%;
It is 16% aqueous sodium persulfate solution and massfraction when being 26% barium chloride solution reaction precipitation coating that corundum bollow ball adopts massfraction, permanent white quality percentage composition 15%;
It is 12% aqueous sodium persulfate solution and massfraction when being 15% barium nitrate aqueous solution reaction precipitation coating that corundum bollow ball adopts massfraction, permanent white quality percentage composition 12%;
It is 10% aqueous sodium persulfate solution and massfraction when being 10% barium nitrate aqueous solution reaction precipitation coating that corundum bollow ball adopts massfraction, permanent white quality percentage composition 7%;
It is 10% potassium sulfate solution and massfraction when being 8% barium nitrate aqueous solution reaction precipitation coating that corundum bollow ball adopts massfraction, permanent white quality percentage composition 6%;
It is 8% ammonium sulfate solution and massfraction when being 6% barium nitrate aqueous solution reaction precipitation coating that corundum bollow ball adopts massfraction, permanent white quality percentage composition 1.6%;
It is 5% ammonium sulfate solution and massfraction when being 8% barium nitrate aqueous solution reaction precipitation coating that corundum bollow ball adopts massfraction, permanent white quality percentage composition 1.3%;
Corundum bollow ball adopts massfraction when be 42.9% ammonium sulfate solution with massfraction being 5% barium nitrate aqueous solution spraying reaction back generation coating, permanent white quality percentage composition 9%;
The modification of table 5 precipitator method is not stained with the aluminium corundum bollow ball and under differing temps, is handled
Embodiment 6 (spraying)
Configure the sulfur acid radical compound aqueous solution and the containing barium compound aqueous solution earlier; The sulfur acid radical compound aqueous solution is sprayed on the corundum bollow ball skin drying; And then the containing barium compound aqueous solution is sprayed on sprayed the sulfur acid radical compound aqueous solution corundum bollow ball surface to moistening, reaction generates barium sulfate precipitate, the washing oven dry; Put into High Temperature Furnaces Heating Apparatus thermal treatment; Thermal treatment temp is 600～900 ℃, and soaking time is 1～4 hour, and the surface that obtains corundum bollow ball at last is covered with one deck permanent white.Specific embodiments is seen table 6.With its sectional view of corundum bollow ball such as Fig. 1 that this method gained has the permanent white coating, wherein 1 is the corundum bollow ball matrix, the 2nd, and the permanent white coating
Corundum bollow ball adopts massfraction when be 30% ammonium sulfate solution with massfraction being 3% barium nitrate aqueous solution spraying reaction back generation coating, permanent white quality percentage composition 4%;
Corundum bollow ball adopts massfraction when be 20% ammonium sulfate solution with massfraction being 7% barium nitrate aqueous solution spraying reaction back generation coating, permanent white quality percentage composition 6%;
Corundum bollow ball adopts massfraction when be 16% aqueous sodium persulfate solution with massfraction being 26% barium chloride solution spraying reaction back generation coating, permanent white quality percentage composition 17%;
Corundum bollow ball adopts massfraction when be 12% aqueous sodium persulfate solution with massfraction being 15% barium nitrate aqueous solution spraying reaction back generation coating, permanent white quality percentage composition 14%;
Corundum bollow ball adopts massfraction when be 10% aqueous sodium persulfate solution with massfraction being 10% barium nitrate aqueous solution spraying reaction back generation coating, permanent white quality percentage composition 9%;
Corundum bollow ball adopts massfraction when be 10% potassium sulfate solution with massfraction being 8% barium nitrate aqueous solution spraying reaction back generation coating, permanent white quality percentage composition 8%;
Corundum bollow ball adopts massfraction when be 8% ammonium sulfate solution with massfraction being 6% barium nitrate aqueous solution spraying reaction back generation coating, permanent white quality percentage composition 2.7%;
Corundum bollow ball adopts massfraction when be 5% ammonium sulfate solution with massfraction being 8% barium nitrate aqueous solution spraying reaction back generation coating, permanent white quality percentage composition 2.3%;
The modification of table 6 precipitator method is not stained with the aluminium corundum bollow ball and under differing temps, is handled
Embodiment 7: (spraying)
With commercial or preparation blaue fixe system form slurry, the permanent white massfraction is 10%, 15%, 18% in the slurry; 22%, 26%, 30% is sprayed on the corundum bollow ball surface to moistening fully; Oven dry was placed in the High Temperature Furnaces Heating Apparatus thermal treatment 1～4 hour, and thermal treatment temp is 600 ℃～900 ℃.Specific embodiments is seen table 7.With its sectional view of corundum bollow ball such as Fig. 1 that this method gained has the permanent white coating, wherein 1 is the corundum bollow ball matrix, the 2nd, and the permanent white coating
The method that is employed in corundum bollow ball surface coating quality mark and is 10% permanent white powdery pulp generates coating, permanent white quality percentage composition 13%;
The method that is employed in corundum bollow ball surface coating quality mark and is 15% permanent white powdery pulp generates coating, permanent white quality percentage composition 18%;
The method that is employed in corundum bollow ball surface coating quality mark and is 18% permanent white powdery pulp generates coating, permanent white quality percentage composition 27%;
The method that is employed in corundum bollow ball surface coating quality mark and is 22% permanent white powdery pulp generates coating, permanent white quality percentage composition 35%;
The method that is employed in corundum bollow ball surface coating quality mark and is 26% permanent white powdery pulp generates coating, permanent white quality percentage composition 41%;
The method that is employed in corundum bollow ball surface coating quality mark and is 30% permanent white powdery pulp generates coating, permanent white quality percentage composition 50%;
Table 7 is not stained with the aluminium corundum bollow ball and under differing temps, is handled
Embodiment 8 barium sulfate sols
Commercial barium sulfate sol is configured to the barium sulfate sol of various solubility; The permanent white massfraction is 5%, 15%, 25% in the colloidal sol; Be sprayed on fire resisting material particle surface to moistening fully or fire resisting material particle is immersed in the barium sulfate sol; Oven dry was placed in the High Temperature Furnaces Heating Apparatus thermal treatment 1～4 hour, and thermal treatment temp is 600 ℃～900 ℃.Specific embodiments is seen table 8.With its sectional view of corundum bollow ball such as Fig. 1 that this method gained has the permanent white coating, wherein 1 is the corundum bollow ball matrix, the 2nd, and the permanent white coating
Table 8 barium sulfate sol is handled corundum bollow ball
Embodiment 9 (titanium aluminium complex sol),
Prepare titanium aluminium complex sol: Ti earlier
4+Concentration is 0.2～0.3mol/L, Al
3+Concentration is the titanium aluminium complex sol of 0.2～0.3mol/L; The adding x is 1.6～6% Mg in the colloidal sol
2+Be stablizer; Or the adding x is 3～5% Mg
2+With x be 0.4～0.8% Ce
4+Be stablizer; Or only to add x be 1.6～3.3% Fe
3+Be stablizer.Dry after corundum bollow ball put into that colloidal sol soaks 0.5～60min or colloidal sol is sprayed on corundum bollow ball surface to surface wettability; Put into High Temperature Furnaces Heating Apparatus thermal treatment then; Thermal treatment temp is 1250～1450 ℃; Soaking time 1～4 hour is not stained with the aluminium corundum bollow ball, and specific embodiments is seen table 9.With its sectional view of corundum bollow ball such as Fig. 1 that this method gained has the aluminium titanates coating, wherein 1 is the corundum bollow ball matrix, the 2nd, and the aluminium titanates coating.
Corundum bollow ball is immersed in contains Ti
4+Concentration is 0.2mol/L, Al
3+Concentration is 0.3mol/L, contains mass percent and be 1.6% Mg
2+Titanium aluminium colloidal sol generate coating, aluminium titanates quality percentage composition is 3.9%;
The corundum bollow ball immersion is contained Ti
4+Concentration is 0.25mol/L, Al
3+Concentration is 0.25mol/L, contains mass percent and be 3% Mg
2+, mass percent is 0.8%Ce
4+Titanium aluminium colloidal sol in generate coating, aluminium titanates quality percentage composition is 3.9%;
The corundum bollow ball immersion is contained Ti
4+Concentration is 0.3mol/L, Al
3+Concentration is 0.25mol/L, contains mass percent and be 1.6% Fe
3+Titanium aluminium colloidal sol generate coating, aluminium titanates quality percentage composition is 4.9%;
To contain Ti
4+Concentration is 0.2mol/L, Al
3+Concentration is 0.3mol/L, contains mass percent and be 1.6% Fe
3+Titanium aluminium colloidal sol be sprayed on corundum bollow ball and generate coating, aluminium titanates quality percentage composition is 4.5%;
To contain Ti
4+Concentration is 0.25mol/L, Al
3+Concentration is 0.25mol/L, contains mass percent and be 5% Mg
2+Titanium aluminium colloidal sol be sprayed on corundum bollow ball and generate coating, aluminium titanates quality percentage composition is 5.3%;
To contain Ti
4+Concentration is 0.3mol/L, Al
3+Concentration is 0.25mol/L, contains mass percent and be 3.3% Fe
3+Titanium aluminium colloidal sol be sprayed on corundum bollow ball and generate coating, aluminium titanates quality percentage composition is 5.9%;
The sol-gel modified aluminium corundum bollow ball of not being stained with of table 9 titanium aluminium is handled under differing temps
Embodiment 10 (titanium colloidal sol)
Prepare titanium colloidal sol: Ti earlier
4+Concentration is the colloidal sol of 0.2～0.3mol/L, and the adding x is 3.7～13% Mg in the colloidal sol
2+Be stablizer; Or the adding x is 7～10% Mg
2+With x be 0.9～1.7% Ce
4+Be stablizer; Or the adding x is 3.8～7% Fe
3+As stablizer.Put into that the colloidal sol for preparing soaks after 0.5～60 minute oven dry to corundum bollow ball then or colloidal sol is sprayed on the corundum bollow ball and to surface wettability, dry; Then corundum bollow ball is put into High Temperature Furnaces Heating Apparatus thermal treatment; Thermal treatment temp is 1250～1450 ℃; Soaking time 1～4 hour, what obtain that the surface contains aluminium titanates is not stained with the aluminium corundum bollow ball, and specific embodiments is seen table 10.With its sectional view of corundum bollow ball such as Fig. 1 that this method gained has the aluminium titanates coating, wherein 1 is the corundum bollow ball matrix, the 2nd, and the aluminium titanates coating
Corundum bollow ball is immersed in contains Ti
4+Concentration is 0.2mol/L, contains mass percent and be 13% Mg
2+Titanium colloidal sol in generate coating, aluminium titanates quality percentage composition is 1.2%;
Corundum bollow ball is immersed in contains Ti
4+Concentration is 0.25mol/L, contains mass percent and be 10% Mg
2+, mass percent is 0.9% Ce
4+Titanium colloidal sol in generate coating, aluminium titanates quality percentage composition is 2.0%;
Corundum bollow ball is immersed in contains Ti
4+Concentration is 0.3mol/L, contains mass percent and be 3.8% Fe
3+Titanium colloidal sol in generate coating, aluminium titanates quality percentage composition is 2.6%;
To contain titanium ion Ti
4+Concentration is 0.2mol/L, contains mass percent and be 3.7% Mg
2+Titanium colloidal sol in to generate coating aluminium titanates quality percentage composition be 3.1%;
To contain titanium ion Ti
4+Concentration is 0.25mol/L, contains mass percent and be 7% Mg
2+, mass percent is 1.7% Ce
4+Titanium colloidal sol be sprayed on and generate coating in the corundum bollow ball, aluminium titanates quality percentage composition is 3.4%;
To contain titanium ion Ti
4+Concentration is 0.3mol/L, contains mass percent and be 3.8% Fe
3+Titanium colloidal sol in to generate coating aluminium titanates quality percentage composition be 4.5%;
The sol-gel modified surface of table 10 titanium is not stained with the aluminium corundum bollow ball and under differing temps, is handled
Embodiment 11 (aluminium titanates powder),
Prepare the aluminium titanates powdery pulp: get the raw materials ready by the requirement of aluminium titanates quality mark, consist of massfraction and be 40～50% Al at present
2O
3With 50～60% TiO
2Wherein adding massfraction is that 1～4%MgO is a stablizer; Or to add massfraction be that 1～4% MgO and massfraction are 1～3% CeO
2Mixture is a stablizer; Or the adding massfraction is 3～8%Fe
2O
3Be stablizer; Or the adding massfraction is 0.5～2% ZrO
2Be stablizer.Corundum bollow ball is soaked 0.5～60min after drying in aluminium titanates powder slurry; Or the aluminium titanates powdery pulp is sprayed on the corundum bollow ball to the surface wettability after drying; Put into High Temperature Furnaces Heating Apparatus thermal treatment, thermal treatment temp is 1250～1450 ℃, soaking time 1～4 hour; What obtain that the surface contains aluminium titanates is not stained with the aluminium corundum bollow ball, and specific embodiments is seen table 11.With its sectional view of corundum bollow ball such as Fig. 1 that this method gained has the aluminium titanates coating, wherein 1 is the corundum bollow ball matrix, the 2nd, and the aluminium titanates coating
It is 40% Al that corundum bollow ball is immersed in mass percent
2O
3, mass percent is 60% TiO
2, molecular fraction is the aluminium titanates powdery pulp of 4% MgO, aluminium titanates quality percentage composition is 38%;
It is 42% Al that corundum bollow ball is immersed in mass percent
2O
3, mass percent is 58% TiO
2, molecular fraction is 8% Fe
2O
3The aluminium titanates powdery pulp process coating, aluminium titanates quality percentage composition is 40%
It is 43% Al that corundum bollow ball is immersed in mass percent
2O
3, mass percent is 57% TiO
2, molecular fraction is 0.5% ZrO
2The aluminium titanates powdery pulp process coating, aluminium titanates quality percentage composition is 45%
It is 45% Al that corundum bollow ball is soaked mass percent
2O
3, mass percent is 55% TiO
2, molecular fraction is 4% MgO, molecular fraction is 1% CeO
2The aluminium titanates powdery pulp process coating, aluminium titanates quality percentage composition is 47%;
With mass percent 42% Al
2O
3, mass percent is 58% TiO
2, molecular fraction is 3% Fe
2O
3The aluminium titanates powdery pulp be sprayed on the corundum bollow ball surface and process coating, aluminium titanates quality percentage composition is 50%;
With mass percent 45% Al
2O
3, mass percent is 55% TiO
2, molecular fraction is 2% ZrO
2The aluminium titanates powdery pulp be sprayed on the corundum bollow ball surface and process coating, aluminium titanates quality percentage composition is 49%;
With mass percent 43% Al
2O
3, mass percent is 57% TiO
2, molecular fraction is 1% MgO, molecular fraction is 2% CeO
2The aluminium titanates powdery pulp be sprayed on the corundum bollow ball surface and process coating, aluminium titanates quality percentage composition is 46%;
With mass percent 44% Al
2O
3, mass percent is 56% TiO
2, molecular fraction is 1% MgO, molecular fraction is 2% CeO
2The aluminium titanates powdery pulp be sprayed on the corundum bollow ball surface and process coating, aluminium titanates quality percentage composition is 43%;
Table 11 aluminium titanates powdery pulp modified surface is not stained with the aluminium corundum bollow ball and under differing temps, is handled
Embodiment 12. (forming Calcium Fluoride (Fluorspan) and permanent white two-layer compound coating successively) in the corundum bollow ball appearance
One of: carry out successively by embodiment 1 and embodiment 5,
Two: carry out successively by embodiment 1 and embodiment 6,
Three: carry out successively by embodiment 1 and embodiment 7,
Four: carry out successively by embodiment 1 and embodiment 8
Five: carry out successively by embodiment 2 and embodiment 5,
Six: carry out successively by embodiment 2 and embodiment 6,
Seven: carry out successively by embodiment 2 and embodiment 7,
Eight: carry out successively by embodiment 2 and embodiment 8
Nine: carry out successively by embodiment 3 and embodiment 5,
Ten: carry out successively by embodiment 3 and embodiment 6,
11: carry out successively by embodiment 3 and embodiment 7,
12: carry out successively by embodiment 3 and embodiment 8
13: carry out successively by embodiment 4 and embodiment 5,
14: carry out successively by embodiment 4 and embodiment 6,
15: carry out successively by embodiment 4 and embodiment 7,
16: carry out successively by embodiment 4 and embodiment 8
With its sectional view of corundum bollow ball such as Fig. 2 that this method gained has Calcium Fluoride (Fluorspan) and permanent white two-layer compound coating, wherein 1 is the corundum bollow ball matrix, the 3rd, and calcium fluoride coating, the 4th, permanent white coating
Embodiment 13. (forming aluminium titanates and Calcium Fluoride (Fluorspan) two-layer compound coating successively) in the corundum bollow ball appearance
One of: carry out successively by embodiment 9 and embodiment 1,
Two: carry out successively by embodiment 9 and embodiment 2,
Three: carry out successively by embodiment 9 and embodiment 3,
Four: carry out successively by embodiment 9 and embodiment 4
Five: carry out successively by embodiment 10 and embodiment 1,
Six: carry out successively by embodiment 10 and embodiment 2,
Seven: carry out successively by embodiment 10 and embodiment 3,
Eight: carry out successively by embodiment 10 and embodiment 4
Nine: carry out successively by embodiment 11 and embodiment 1,
Ten: carry out successively by embodiment 11 and embodiment 2,
11: carry out successively by embodiment 11 and embodiment 3,
12: carry out successively by embodiment 11 and embodiment 4
With its sectional view of corundum bollow ball such as Fig. 2 that this method gained has aluminium titanates and Calcium Fluoride (Fluorspan) two-layer compound coating, wherein 1 is the corundum bollow ball matrix, the 3rd, and aluminium titanates coating, the 4th, calcium fluoride coating
Embodiment 14. (forming aluminium titanates and permanent white two-layer compound coating successively) in the corundum bollow ball appearance
One of: carry out successively by embodiment 9 and embodiment 5,
Two: carry out successively by embodiment 9 and embodiment 6,
Three: carry out successively by embodiment 9 and embodiment 7,
Four: carry out successively by embodiment 9 and embodiment 8
Five: carry out successively by embodiment 10 and embodiment 5,
Six: carry out successively by embodiment 10 and embodiment 6,
Seven: carry out successively by embodiment 10 and embodiment 7,
Eight: carry out successively by embodiment 10 and embodiment 8
Nine: carry out successively by embodiment 11 and embodiment 5,
Ten: carry out successively by embodiment 11 and embodiment 6,
11: carry out successively by embodiment 11 and embodiment 7,
12: carry out successively by embodiment 11 and embodiment 8
With its sectional view of corundum bollow ball such as Fig. 2 that this method gained has aluminium titanates and permanent white two-layer compound coating, wherein 1 is the corundum bollow ball matrix, the 3rd, and aluminium titanates coating, the 4th, permanent white coating
Embodiment 15. (appearance forms aluminium titanates, Calcium Fluoride (Fluorspan) and three layers of compound coating of permanent white successively on the corundum bollow ball surface)
One of: by embodiment 9, embodiment 1 be, embodiment 5 carries out successively,
Two: by embodiment 9, embodiment 1 be, embodiment 6 carries out successively,
Three: by embodiment 9, embodiment 1 be, embodiment 7 carries out successively,
Four: by embodiment 9, embodiment 1 be, embodiment 8 carries out successively,
Five: by embodiment 9, embodiment 2 be, embodiment 5 carries out successively,
Six: by embodiment 9, embodiment 2 be, embodiment 6 carries out successively,
Seven: by embodiment 9, embodiment 2 be, embodiment 7 carries out successively,
Eight: by embodiment 9, embodiment 2 be, embodiment 8 carries out successively,
Nine: by embodiment 9, embodiment 3 be, embodiment 5 carries out successively,
Ten: by embodiment 9, embodiment 3 be, embodiment 6 carries out successively,
11: by embodiment 9, embodiment 3 be, embodiment 7 carries out successively,
12: by embodiment 9, embodiment 3 be, embodiment 8 carries out successively,
13: by embodiment 9, embodiment 4 be, embodiment 5 carries out successively,
14: by embodiment 9, embodiment 4 be, embodiment 6 carries out successively,
15: by embodiment 9, embodiment 4 be, embodiment 7 carries out successively,
16: by embodiment 9, embodiment 4 be, embodiment 8 carries out successively,
17: by embodiment 10, embodiment 1 be, embodiment 5 carries out successively,
18: by embodiment 10, embodiment 1 be, embodiment 6 carries out successively,
19: by embodiment 10, embodiment 1 be, embodiment 7 carries out successively,
20: by embodiment 10, embodiment 1 be, embodiment 8 carries out successively,
21: by embodiment 10, embodiment 2 be, embodiment 5 carries out successively,
22: by embodiment 10, embodiment 2 be, embodiment 6 carries out successively,
23: by embodiment 10, embodiment 2 be, embodiment 7 carries out successively,
24: by embodiment 10, embodiment 2 be, embodiment 8 carries out successively,
25: by embodiment 10, embodiment 3 be, embodiment 5 carries out successively,
26: by embodiment 10, embodiment 3 be, embodiment 6 carries out successively,
27: by embodiment 10, embodiment 3 be, embodiment 7 carries out successively,
28: by embodiment 10, embodiment 3 be, embodiment 8 carries out successively,
29: by embodiment 10, embodiment 4 be, embodiment 5 carries out successively,
30: by embodiment 10, embodiment 4 be, embodiment 6 carries out successively,
Hentriaconta-: by embodiment 10, embodiment 4 be, embodiment 7 carries out successively,
32: by embodiment 10, embodiment 4 be, embodiment 8 carries out successively,
33: by embodiment 11, embodiment 1 be, embodiment 5 carries out successively,
34: by embodiment 11, embodiment 1 be, embodiment 6 carries out successively,
35: by embodiment 11, embodiment 1 be, embodiment 7 carries out successively,
36: by embodiment 11, embodiment 1 be, embodiment 8 carries out successively,
37: by embodiment 11, embodiment 2 be, embodiment 5 carries out successively,
38: by embodiment 11, embodiment 2 be, embodiment 6 carries out successively,
39: by embodiment 11, embodiment 2 be, embodiment 7 carries out successively,
40: by embodiment 11, embodiment 2 be, embodiment 8 carries out successively,
41: by embodiment 11, embodiment 3 be, embodiment 5 carries out successively,
42: by embodiment 11, embodiment 3 be, embodiment 6 carries out successively,
43: by embodiment 11, embodiment 3 be, embodiment 7 carries out successively,
44: by embodiment 11, embodiment 3 be, embodiment 8 carries out successively,
45: by embodiment 11, embodiment 4 be, embodiment 5 carries out successively,
46: by embodiment 11, embodiment 4 be, embodiment 6 carries out successively,
47: by embodiment 11, embodiment 4 be, embodiment 7 carries out successively,
48: by embodiment 11, embodiment 4 be, embodiment 8 carries out successively,
Use this method gained to have its sectional view of corundum bollow ball such as Fig. 3 of aluminium titanates, Calcium Fluoride (Fluorspan) and three layers of compound coating of permanent white, wherein 1 is the corundum bollow ball matrix, the 5th, and aluminium titanates coating, the 6th, calcium fluoride coating, the 7th, permanent white coating.
Claims (10)
1. be not stained with the aluminium corundum bollow ball for one kind, it is characterized in that: in the corundum bollow ball surface coverage one deck Calcium Fluoride (Fluorspan), permanent white or aluminium titanates are arranged, more than the two or 2 ~ 3 layers of coating of above three.
2. a kind of aluminium corundum bollow ball of not being stained with according to claim 1 is characterized in that: said when being coated with one deck, wherein Calcium Fluoride (Fluorspan), permanent white or aluminium titanates account for and are not stained with 0.05～50% of aluminium corundum bollow ball massfraction; Be coated with Calcium Fluoride (Fluorspan) and permanent white when two-layer, internal layer is a Calcium Fluoride (Fluorspan), and skin is a permanent white, and wherein Calcium Fluoride (Fluorspan) and permanent white account for and is not stained with 0.05～50% of aluminium corundum bollow ball massfraction; Be coated with permanent white and aluminium titanates when two-layer, internal layer is an aluminium titanates, and skin is a permanent white, and wherein permanent white and aluminium titanates account for and be not stained with 0.05 ~ 50% of aluminium corundum bollow ball massfraction; Be coated with Calcium Fluoride (Fluorspan) and aluminium titanates when two-layer, internal layer is an aluminium titanates, and skin is a Calcium Fluoride (Fluorspan), wherein Calcium Fluoride (Fluorspan) and aluminium titanates account for be not stained with aluminium corundum bollow ball massfraction 0.05～50%, aluminium titanates accounts for and is not stained with 0.05～50% of aluminium corundum bollow ball massfraction; When being coated with three layers, internal layer is that aluminium titanates, middle layer are that Calcium Fluoride (Fluorspan), skin are permanent white, and wherein Calcium Fluoride (Fluorspan), permanent white and aluminium titanates account for and be not stained with 0.05～50% of aluminium corundum bollow ball massfraction.
3. a kind of preparation method who is not stained with the aluminium corundum bollow ball according to claim 1 is characterized in that, the step of aluminium corundum bollow ball surface coverage when the Calcium Fluoride (Fluorspan) layer is arranged is following when not being stained with:
(1) batching:
The preparation fluorochemicals aqueous solution, the calcium containing compound aqueous solution, Calcium Fluoride (Fluorspan) colloidal sol or Calcium Fluoride (Fluorspan) powdery pulp are subsequent use; Its concrete component target is: fluorochemicals aqueous solution massfraction is 2～48%; Calcium containing compound aqueous solution massfraction is 5～55%; Calcium Fluoride (Fluorspan) colloidal sol massfraction is 5～25% in the Calcium Fluoride (Fluorspan) colloidal sol; Calcium Fluoride (Fluorspan) massfraction content is 10～30% in the Calcium Fluoride (Fluorspan) powdery pulp;
(2) surface applied has following five kinds of methods:
2.1 corundum bollow ball is immersed in the fluorochemicals aqueous solution oven dry; And then the corundum bollow ball that will adopt the fluorochemicals aqueous solution to handle is immersed in generation Calcium Fluoride (Fluorspan) layer in the calcium containing compound aqueous solution, oven dry after cleaning again;
2.2 dry to moistening on the surface that the fluorochemicals aqueous solution is sprayed on corundum bollow ball; And then the calcium containing compound aqueous solution is sprayed on the surface of adopting the corundum bollow ball that the fluorochemicals aqueous solution handled generates Calcium Fluoride (Fluorspan), oven dry after cleaning;
2.3 dry to moistening fully on the surface that Calcium Fluoride (Fluorspan) colloidal sol is sprayed on corundum bollow ball;
2.4 corundum bollow ball is immersed in the Calcium Fluoride (Fluorspan) colloidal sol, constantly stir in the immersion process, soak time is 0.5 ~ 60min, takes out the back oven dry;
2.5 it is moistening until fully directly the Calcium Fluoride (Fluorspan) powdery pulp to be sprayed on the surface of corundum bollow ball, oven dry gets final product;
(3) thermal treatment:
The corundum bollow ball that the surface is scribbled one deck Calcium Fluoride (Fluorspan) places 800～1200 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation.
4. a kind of preparation method who is not stained with the aluminium corundum bollow ball according to claim 3 is characterized in that:
The described fluorine cpd aqueous solution is ammonium fluoride aqueous solution, sodium fluoride aqueous solution or potassium fluoride aqueous solution; The described calcium containing compound aqueous solution is calcium nitrate aqueous solution or calcium chloride water.
5. a kind of preparation method who is not stained with the aluminium corundum bollow ball according to claim 1 is characterized in that, the step of aluminium corundum bollow ball surface coverage when the permanent white layer is arranged is following when not being stained with:
(1) batching:
The preparation sulfur acid radical compound aqueous solution, the containing barium compound aqueous solution, barium sulfate sol or permanent white powdery pulp are subsequent use; Concrete component target is: sulfur acid radical compound aqueous solution massfraction is 5～42.9%; Containing barium compound aqueous solution massfraction is 3～26%; The permanent white massfraction is in the barium sulfate sol: 5～25%; The permanent white massfraction is 10～30% in the permanent white powdery pulp;
(2) surface applied has following five kinds of methods:
2.1 corundum bollow ball is immersed in the sulfur acid radical compound aqueous solution oven dry; And then the corundum bollow ball that will adopt the sulfur acid radical compound aqueous solution to handle is immersed in generation permanent white layer in the containing barium compound aqueous solution, oven dry after cleaning again;
2.2 dry to moistening on the surface that the sulfur acid radical compound aqueous solution is sprayed on corundum bollow ball; And then the containing barium compound aqueous solution is sprayed on the surface of adopting the corundum bollow ball that the sulfur acid radical compound aqueous solution handled generates permanent white, oven dry after cleaning;
2.3 dry to moistening fully on the surface that barium sulfate sol is sprayed on corundum bollow ball;
2.4 corundum bollow ball is immersed in the barium sulfate sol, constantly stir in the immersion process, soak time is 0.5 ~ 60min, takes out the back oven dry;
2.5 it is moistening until fully directly the permanent white powdery pulp to be sprayed on the surface of corundum bollow ball, oven dry gets final product;
(3) thermal treatment
The corundum bollow ball that the surface is scribbled one deck permanent white places 600～900 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation.
6. a kind of preparation method who is not stained with the aluminium corundum bollow ball according to claim 5 is characterized in that: the described sulfur acid radical compound aqueous solution is ammonium sulfate solution, potassium sulfate solution or aqueous sodium persulfate solution; The described containing barium compound aqueous solution is barium nitrate aqueous solution or barium chloride solution.
7. a kind of preparation method who is not stained with the aluminium corundum bollow ball according to claim 1 is characterized in that, the step of aluminium corundum bollow ball surface coverage when the metatitanic acid aluminium lamination is arranged is following when not being stained with:
(1) batching:
Purchase commercially available or preparation titanium aluminium complex sol, titanium colloidal sol and aluminium titanates powdery pulp subsequent use; Component target requires as follows:
A titanium aluminium complex sol: Ti
4+Concentration is 0.2 ~ 0.3mol/L, Al
3+Concentration is the titanium aluminium complex sol of 0.2～0.3mol/L; The adding x is 1.6～6% Mg in the colloidal sol
2+Be stablizer; Or the adding x is 3～5% Mg
2+With x be 0.4～0.8% Ce
4+Be stablizer; Or only to add x be 1.6～3.3% Fe
3+Be stablizer;
B titanium colloidal sol: Ti
4+Concentration is the colloidal sol of 0.2～0.3mol/L, and the adding x is 3.7～13% Mg in the colloidal sol
2+Be stablizer; Or the adding x is 7～10% Mg
2+With x be 0.9～1.7% Ce
4+Be stablizer; Or the adding x is 3.8～7% Fe
3+As stablizer;
C aluminium titanates powdery pulp: consist of massfraction and be 40～50% Al
2O
3With 50～60% TiO
2Wherein adding massfraction is that 1～4%MgO is a stablizer; Or to add massfraction be that 1～4% MgO and massfraction are 1～3% CeO
2Mixture is a stablizer; Or the adding massfraction is 3～8% Fe
2O
3Be stablizer; Or the adding massfraction is 0.5～2% ZrO
2Be stablizer;
(2) surface applied has following two kinds of methods:
2.1 corundum bollow ball is immersed in titanium aluminium complex sol or titanium colloidal sol or the aluminium titanates powdery pulp, constantly stir in the immersion process, soak time is 0.5 ~ 60min, takes out the back oven dry;
2.2 it is moistening until fully that titanium aluminium complex sol or titanium colloidal sol or aluminium titanates powdery pulp are sprayed on the corundum bollow ball surface, oven dry gets final product;
(3) thermal treatment
To soak or spray titanium aluminium complex sol, the corundum bollow ball of titanium colloidal sol and aluminium titanates powdery pulp places 1250～1450 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation.
8. a kind of preparation method who is not stained with the aluminium corundum bollow ball according to claim 1 is characterized in that, not being stained with aluminium corundum bollow ball surface coverage has Calcium Fluoride (Fluorspan), permanent white, when above the two two layers of coatings of aluminium titanates makes up, following three kinds of methods is arranged:
1. when not being stained with aluminium corundum bollow ball surface coverage when Calcium Fluoride (Fluorspan) and permanent white two layers of coatings are arranged:
(1) carries out Calcium Fluoride (Fluorspan) to corundum bollow ball earlier and applies, and its step is following:
(1) batching:
The preparation fluorochemicals aqueous solution, the calcium containing compound aqueous solution, Calcium Fluoride (Fluorspan) colloidal sol or Calcium Fluoride (Fluorspan) powdery pulp are subsequent use; Its concrete component target is: fluorochemicals aqueous solution massfraction is 2～48%; Calcium containing compound aqueous solution massfraction is 5～55%; Calcium Fluoride (Fluorspan) colloidal sol massfraction is 5～25% in the Calcium Fluoride (Fluorspan) colloidal sol; Calcium Fluoride (Fluorspan) massfraction content is 10～30% in the Calcium Fluoride (Fluorspan) powdery pulp;
(2) surface applied has following five kinds of methods:
2.1 corundum bollow ball is immersed in the fluorochemicals aqueous solution oven dry; And then the corundum bollow ball that will adopt the fluorochemicals aqueous solution to handle is immersed in generation Calcium Fluoride (Fluorspan) layer in the calcium containing compound aqueous solution, oven dry after cleaning again;
2.2 dry to moistening on the surface that the fluorochemicals aqueous solution is sprayed on corundum bollow ball; And then the calcium containing compound aqueous solution is sprayed on the surface of adopting the corundum bollow ball that the fluorochemicals aqueous solution handled generates Calcium Fluoride (Fluorspan), oven dry after cleaning;
2.3 dry to moistening fully on the surface that Calcium Fluoride (Fluorspan) colloidal sol is sprayed on corundum bollow ball;
2.4 corundum bollow ball is immersed in the Calcium Fluoride (Fluorspan) colloidal sol, constantly stir in the immersion process, soak time is 0.5 ~ 60min, takes out the back oven dry;
2.5 it is moistening until fully directly the Calcium Fluoride (Fluorspan) powdery pulp to be sprayed on the surface of corundum bollow ball, oven dry gets final product;
(3) thermal treatment:
The corundum bollow ball that the surface is scribbled one deck Calcium Fluoride (Fluorspan) places 800～1200 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation;
(2) carries out permanent white to corundum bollow ball again and applies, and its step is following:
(1) batching:
The preparation sulfur acid radical compound aqueous solution, the containing barium compound aqueous solution, barium sulfate sol or permanent white powdery pulp are subsequent use; Concrete component target is: sulfur acid radical compound aqueous solution massfraction is 5～42.9%; Containing barium compound aqueous solution massfraction is 3～26%; The permanent white massfraction is in the barium sulfate sol: 5～25%; The permanent white massfraction is 10～30% in the permanent white powdery pulp;
(2) surface applied has following five kinds of methods:
2.1 corundum bollow ball is immersed in the sulfur acid radical compound aqueous solution oven dry; And then the corundum bollow ball that will adopt the sulfur acid radical compound aqueous solution to handle is immersed in generation permanent white layer in the containing barium compound aqueous solution, oven dry after cleaning again;
2.2 dry to moistening on the surface that the sulfur acid radical compound aqueous solution is sprayed on corundum bollow ball; And then the containing barium compound aqueous solution is sprayed on the surface of adopting the corundum bollow ball that the sulfur acid radical compound aqueous solution handled generates permanent white, oven dry after cleaning;
2.3 dry to moistening fully on the surface that barium sulfate sol is sprayed on corundum bollow ball;
2.4 corundum bollow ball is immersed in the barium sulfate sol, constantly stir in the immersion process, soak time is 0.5 ~ 60min, takes out the back oven dry;
2.5 it is moistening until fully directly the permanent white powdery pulp to be sprayed on the surface of corundum bollow ball, oven dry gets final product;
(3) thermal treatment
The corundum bollow ball that the surface is scribbled one deck permanent white places 600～900 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation;
2. when not being stained with aluminium corundum bollow ball surface coverage when Calcium Fluoride (Fluorspan) and two layers of coating of aluminium titanates are arranged:
(1) carries out aluminium titanates to corundum bollow ball earlier and applies, and its step is following:
(1) batching:
Purchase commercially available or preparation titanium aluminium complex sol, titanium colloidal sol and aluminium titanates powdery pulp subsequent use; Component target requires as follows:
A titanium aluminium complex sol: Ti
4+Concentration is 0.2 ~ 0.3mol/L, Al
3+Concentration is the titanium aluminium complex sol of 0.2～0.3mol/L; The adding x is 1.6～6% Mg in the colloidal sol
2+Be stablizer; Or the adding x is 3～5% Mg
2+With x be 0.4～0.8% Ce
4+Be stablizer; Or only to add x be 1.6～3.3% Fe
3+For being stablizer;
B titanium colloidal sol: Ti
4+Concentration is the colloidal sol of 0.2～0.3mol/L, and the adding x is 3.7～13% Mg in the colloidal sol
2+Be stablizer; Or the adding x is 7～10% Mg
2+With x be 0.9～1.7% Ce
4+Be stablizer; Or the adding x is 3.8～7% Fe
3+As stablizer;
C aluminium titanates powdery pulp: consist of massfraction and be 40～50% Al
2O
3With 50～60% TiO
2Wherein adding massfraction is that 1～4%MgO is a stablizer; Or to add massfraction be that 1～4% MgO and massfraction are 1～3% CeO
2Mixture is a stablizer; Or the adding massfraction is 3～8% Fe
2O
3Be stablizer; Or the adding massfraction is 0.5～2% ZrO
2Be stablizer;
(2) surface applied has following two kinds of methods:
2.1 corundum bollow ball is immersed in titanium aluminium complex sol or titanium colloidal sol or the aluminium titanates powdery pulp, constantly stir in the immersion process, soak time is 0.5 ~ 60min, takes out the back oven dry;
2.2 it is moistening until fully that titanium aluminium complex sol or titanium colloidal sol or aluminium titanates powdery pulp are sprayed on the corundum bollow ball surface, oven dry gets final product;
(3) thermal treatment
To soak or spray titanium aluminium complex sol, the corundum bollow ball of titanium colloidal sol and aluminium titanates powdery pulp places 1250～1450 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation;
(2) carries out Calcium Fluoride (Fluorspan) to corundum bollow ball again and applies, and its step is following:
(1) batching:
The preparation fluorochemicals aqueous solution, the calcium containing compound aqueous solution, Calcium Fluoride (Fluorspan) colloidal sol or Calcium Fluoride (Fluorspan) powdery pulp are subsequent use; Its concrete component target is: fluorochemicals aqueous solution massfraction is 2～48%; Calcium containing compound aqueous solution massfraction is 5～55%; Calcium Fluoride (Fluorspan) colloidal sol massfraction is 5～25% in the Calcium Fluoride (Fluorspan) colloidal sol; Calcium Fluoride (Fluorspan) massfraction content is 10～30% in the Calcium Fluoride (Fluorspan) powdery pulp;
(2) surface applied has following five kinds of methods:
2.1 corundum bollow ball is immersed in the fluorochemicals aqueous solution oven dry; And then the corundum bollow ball that will adopt the fluorochemicals aqueous solution to handle is immersed in generation Calcium Fluoride (Fluorspan) layer in the calcium containing compound aqueous solution, oven dry after cleaning again;
2.2 dry to moistening on the surface that the fluorochemicals aqueous solution is sprayed on corundum bollow ball; And then the calcium containing compound aqueous solution is sprayed on the surface of adopting the corundum bollow ball that the fluorochemicals aqueous solution handled generates Calcium Fluoride (Fluorspan), oven dry after cleaning;
2.3 dry to moistening fully on the surface that Calcium Fluoride (Fluorspan) colloidal sol is sprayed on corundum bollow ball;
2.4 corundum bollow ball is immersed in the Calcium Fluoride (Fluorspan) colloidal sol, constantly stir in the immersion process, soak time is 0.5 ~ 60min, takes out the back oven dry;
2.5 it is moistening until fully directly the Calcium Fluoride (Fluorspan) powdery pulp to be sprayed on the surface of corundum bollow ball, oven dry gets final product;
(3) thermal treatment:
The corundum bollow ball that the surface is scribbled one deck Calcium Fluoride (Fluorspan) places 800～1200 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation;
3. when not being stained with aluminium corundum bollow ball surface coverage when aluminium titanates and two layers of coating of Calcium Fluoride (Fluorspan) are arranged:
(1) carries out aluminium titanates to corundum bollow ball earlier and applies, and its step is following:
(1) batching:
Purchase commercially available or preparation titanium aluminium complex sol, titanium colloidal sol and aluminium titanates powdery pulp subsequent use; Component target requires as follows:
A titanium aluminium complex sol: Ti
4+Concentration is 0.2 ~ 0.3mol/L, Al
3+Concentration is the titanium aluminium complex sol of 0.2～0.3mol/L; The adding x is 1.6～6% Mg in the colloidal sol
2+Be stablizer; Or the adding x is 3～5% Mg
2+With x be 0.4～0.8% Ce
4+Be stablizer; Or only to add x be 1.6～3.3% Fe
3+For being stablizer;
B titanium colloidal sol: Ti
4+Concentration is the colloidal sol of 0.2～0.3mol/L, and the adding x is 3.7～13% Mg in the colloidal sol
2+Be stablizer; Or the adding x is 7～10% Mg
2+With x be 0.9～1.7% Ce
4+Be stablizer; Or the adding x is 3.8～7% Fe
3+As stablizer;
C aluminium titanates powdery pulp: consist of massfraction and be 40～50% Al
2O
3With 50～60% TiO
2Wherein adding massfraction is that 1～4%MgO is a stablizer; Or to add massfraction be that 1～4% MgO and massfraction are 1～3% CeO
2Mixture is a stablizer; Or the adding massfraction is 3～8% Fe
2O
3Be stablizer; Or the adding massfraction is 0.5～2% ZrO
2Be stablizer;
(2) surface applied has following two kinds of methods:
2.1 corundum bollow ball is immersed in titanium aluminium complex sol or titanium colloidal sol or the aluminium titanates powdery pulp, constantly stir in the immersion process, soak time is 0.5 ~ 60min, takes out the back oven dry;
2.2 it is moistening until fully that titanium aluminium complex sol or titanium colloidal sol or aluminium titanates powdery pulp are sprayed on the corundum bollow ball surface, oven dry gets final product;
(3) thermal treatment
To soak or spray titanium aluminium complex sol, the corundum bollow ball of titanium colloidal sol and aluminium titanates powdery pulp places 1250～1450 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation;
(2) carries out Calcium Fluoride (Fluorspan) to corundum bollow ball again and applies, and its step is following:
(1) batching:
The preparation fluorochemicals aqueous solution, the calcium containing compound aqueous solution, Calcium Fluoride (Fluorspan) colloidal sol or Calcium Fluoride (Fluorspan) powdery pulp are subsequent use; Its concrete component target is: fluorochemicals aqueous solution massfraction is 2～48%; Calcium containing compound aqueous solution massfraction is 5～55%; Calcium Fluoride (Fluorspan) colloidal sol massfraction is 5～25% in the Calcium Fluoride (Fluorspan) colloidal sol; Calcium Fluoride (Fluorspan) massfraction content is 10～30% in the Calcium Fluoride (Fluorspan) powdery pulp;
(2) surface applied has following five kinds of methods:
2.1 corundum bollow ball is immersed in the fluorochemicals aqueous solution oven dry; And then the corundum bollow ball that will adopt the fluorochemicals aqueous solution to handle is immersed in generation Calcium Fluoride (Fluorspan) layer in the calcium containing compound aqueous solution, oven dry after cleaning again;
2.2 dry to moistening on the surface that the fluorochemicals aqueous solution is sprayed on corundum bollow ball; And then the calcium containing compound aqueous solution is sprayed on the surface of adopting the corundum bollow ball that the fluorochemicals aqueous solution handled generates Calcium Fluoride (Fluorspan), oven dry after cleaning;
2.3 dry to moistening fully on the surface that Calcium Fluoride (Fluorspan) colloidal sol is sprayed on corundum bollow ball;
2.4 corundum bollow ball is immersed in the Calcium Fluoride (Fluorspan) colloidal sol, constantly stir in the immersion process, soak time is 0.5 ~ 60min, takes out the back oven dry;
2.5 it is moistening until fully directly the Calcium Fluoride (Fluorspan) powdery pulp to be sprayed on the surface of corundum bollow ball, oven dry gets final product;
(3) thermal treatment:
The corundum bollow ball that the surface is scribbled one deck Calcium Fluoride (Fluorspan) places 800～1200 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation.
9. the sulfur acid radical compound aqueous solution according to claim 8 is ammonium sulfate solution, potassium sulfate solution or aqueous sodium persulfate solution; The described containing barium compound aqueous solution is barium nitrate aqueous solution or barium chloride solution; The described fluorine cpd aqueous solution is ammonium fluoride aqueous solution, sodium fluoride aqueous solution or potassium fluoride aqueous solution; The described calcium containing compound aqueous solution is calcium nitrate aqueous solution or calcium chloride water.
10. a kind of preparation method who is not stained with the aluminium corundum bollow ball according to claim 1 is characterized in that, when not being stained with aluminium corundum bollow ball surface coverage when Calcium Fluoride (Fluorspan), permanent white, three layers of compound coating of aluminium titanates are arranged:
(1) carries out the aluminium titanates coating to the corundum bollow ball surface earlier, and its step is following:
(1) batching:
Purchase commercially available or preparation titanium aluminium complex sol, titanium colloidal sol and aluminium titanates powdery pulp subsequent use; Component target requires as follows:
A titanium aluminium complex sol: Ti
4+Concentration is 0.2 ~ 0.3mol/L, Al
3+Concentration is the titanium aluminium complex sol of 0.2～0.3mol/L; The adding x is 1.6～6% Mg in the colloidal sol
2+Be stablizer; Or the adding x is 3～5% Mg
2+With x be 0.4～0.8% Ce
4+Be stablizer; Or only to add x be 1.6～3.3% Fe
3+For being stablizer;
B titanium colloidal sol: Ti
4+Concentration is the colloidal sol of 0.2～0.3mol/L, and the adding x is 3.7～13% Mg in the colloidal sol
2+Be stablizer; Or the adding x is 7～10% Mg
2+With x be 0.9～1.7% Ce
4+Be stablizer; Or the adding x is 3.8～7% Fe
3+As stablizer;
C aluminium titanates powdery pulp: consist of massfraction and be 40～50% Al
2O
3With 50～60% TiO
2Wherein adding massfraction is that 1～4%MgO is a stablizer; Or to add massfraction be that 1～4% MgO and massfraction are 1～3% CeO
2Mixture is a stablizer; Or the adding massfraction is 3～8% Fe
2O
3Be stablizer; Or the adding massfraction is 0.5～2% ZrO
2Be stablizer;
(2) surface applied has following two kinds of methods:
2.1 corundum bollow ball is immersed in titanium aluminium complex sol or titanium colloidal sol or the aluminium titanates powdery pulp, constantly stir in the immersion process, soak time is 0.5 ~ 60min, takes out the back oven dry;
2.2 it is moistening until fully that titanium aluminium complex sol or titanium colloidal sol or aluminium titanates powdery pulp are sprayed on the corundum bollow ball surface, oven dry gets final product;
(3) thermal treatment
To soak or spray titanium aluminium complex sol, the corundum bollow ball of titanium colloidal sol and aluminium titanates powdery pulp places 1250～1450 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation;
(2) has covered the aluminium titanates coating and has formed calcium fluoride coating again, and its step is following:
(1) batching:
The preparation fluorochemicals aqueous solution, the calcium containing compound aqueous solution, Calcium Fluoride (Fluorspan) colloidal sol or Calcium Fluoride (Fluorspan) powdery pulp are subsequent use; Its concrete component target is: fluorochemicals aqueous solution massfraction is 2～48%; Calcium containing compound aqueous solution massfraction is 5～55%; Calcium Fluoride (Fluorspan) colloidal sol massfraction is 5～25% in the Calcium Fluoride (Fluorspan) colloidal sol; Calcium Fluoride (Fluorspan) massfraction content is 10～30% in the Calcium Fluoride (Fluorspan) powdery pulp;
(2) surface applied has following five kinds of methods:
2.1 corundum bollow ball is immersed in the fluorochemicals aqueous solution oven dry; And then the corundum bollow ball that will adopt the fluorochemicals aqueous solution to handle is immersed in generation Calcium Fluoride (Fluorspan) layer in the calcium containing compound aqueous solution, oven dry after cleaning again;
2.2 dry to moistening on the surface that the fluorochemicals aqueous solution is sprayed on corundum bollow ball; And then the calcium containing compound aqueous solution is sprayed on the surface of adopting the corundum bollow ball that the fluorochemicals aqueous solution handled generates Calcium Fluoride (Fluorspan), oven dry after cleaning;
2.3 dry to moistening fully on the surface that Calcium Fluoride (Fluorspan) colloidal sol is sprayed on corundum bollow ball;
2.4 corundum bollow ball is immersed in the Calcium Fluoride (Fluorspan) colloidal sol, constantly stir in the immersion process, soak time is 0.5 ~ 60min, takes out the back oven dry;
2.5 it is moistening until fully directly the Calcium Fluoride (Fluorspan) powdery pulp to be sprayed on the surface of corundum bollow ball, oven dry gets final product;
(3) thermal treatment:
The corundum bollow ball that the surface is scribbled one deck Calcium Fluoride (Fluorspan) places 800～1200 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation;
The corundum bollow ball that (3) has been coated with aluminium titanates and calcium fluoride coating forms the permanent white coating, and its step is following:
(1) batching:
The preparation sulfur acid radical compound aqueous solution, the containing barium compound aqueous solution, barium sulfate sol or permanent white powdery pulp are subsequent use; Concrete component target is: sulfur acid radical compound aqueous solution massfraction is 5～42.9%; Containing barium compound aqueous solution massfraction is 3～26%; The permanent white massfraction is in the barium sulfate sol: 5～25%; The permanent white massfraction is 10～30% in the permanent white powdery pulp;
(2) surface applied has following five kinds of methods:
2.1 corundum bollow ball is immersed in the sulfur acid radical compound aqueous solution oven dry; And then the corundum bollow ball that will adopt the sulfur acid radical compound aqueous solution to handle is immersed in generation permanent white layer in the containing barium compound aqueous solution, oven dry after cleaning again;
2.2 dry to moistening on the surface that the sulfur acid radical compound aqueous solution is sprayed on corundum bollow ball; And then the containing barium compound aqueous solution is sprayed on the surface of adopting the corundum bollow ball that the sulfur acid radical compound aqueous solution handled generates permanent white, oven dry after cleaning;
2.3 dry to moistening fully on the surface that barium sulfate sol is sprayed on corundum bollow ball;
2.4 corundum bollow ball is immersed in the barium sulfate sol, constantly stir in the immersion process, soak time is 0.5 ~ 60min, takes out the back oven dry;
2.5 it is moistening until fully directly the permanent white powdery pulp to be sprayed on the surface of corundum bollow ball, oven dry gets final product;
(3) thermal treatment
The corundum bollow ball that the surface is scribbled one deck permanent white places 600～900 ℃ heat treatment furnace to be incubated 1～4 hour, with the stove cooling, accomplishes preparation;
The described sulfur acid radical compound aqueous solution is ammonium sulfate solution, potassium sulfate solution or aqueous sodium persulfate solution; The described containing barium compound aqueous solution is barium nitrate aqueous solution or barium chloride solution; The described fluorine cpd aqueous solution is ammonium fluoride aqueous solution, sodium fluoride aqueous solution or potassium fluoride aqueous solution; The described calcium containing compound aqueous solution is calcium nitrate aqueous solution or calcium chloride water.
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| CN2012100070471A CN102584266A (en) | 2012-01-11 | 2012-01-11 | Corundum hollow ball non-sticky to aluminum and preparation method of corundum hollow ball |
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| CN2012100070471A CN102584266A (en) | 2012-01-11 | 2012-01-11 | Corundum hollow ball non-sticky to aluminum and preparation method of corundum hollow ball |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105671337A (en) * | 2016-04-11 | 2016-06-15 | 河南金阳铝业有限公司 | Aluminum ball convenient to charge |
| CN111995417A (en) * | 2020-08-21 | 2020-11-27 | 浙江锦诚新材料股份有限公司 | Magnesium aluminate spinel castable for aluminum melting furnace |
| CN113124047A (en) * | 2021-05-24 | 2021-07-16 | 浙江大学 | Insulated rolling bearing with nano calcium fluoride coating and preparation method |
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| CN1215708A (en) * | 1997-10-27 | 1999-05-05 | 普拉塞尔技术有限公司 | Method for producing corrosion resistant refractories |
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| CN1215708A (en) * | 1997-10-27 | 1999-05-05 | 普拉塞尔技术有限公司 | Method for producing corrosion resistant refractories |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105671337A (en) * | 2016-04-11 | 2016-06-15 | 河南金阳铝业有限公司 | Aluminum ball convenient to charge |
| CN111995417A (en) * | 2020-08-21 | 2020-11-27 | 浙江锦诚新材料股份有限公司 | Magnesium aluminate spinel castable for aluminum melting furnace |
| CN113124047A (en) * | 2021-05-24 | 2021-07-16 | 浙江大学 | Insulated rolling bearing with nano calcium fluoride coating and preparation method |
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Application publication date: 20120718 |