CN102951849B - A kind of colorful glass microbead and preparation method thereof of interfering - Google Patents
A kind of colorful glass microbead and preparation method thereof of interfering Download PDFInfo
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- CN102951849B CN102951849B CN201210417897.9A CN201210417897A CN102951849B CN 102951849 B CN102951849 B CN 102951849B CN 201210417897 A CN201210417897 A CN 201210417897A CN 102951849 B CN102951849 B CN 102951849B
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Abstract
The present invention relates to a kind of colorful glass microbead and preparation method thereof of interfering. It is characterized in that: comprise spherical common flint glass matrix and be coated on successively the coating of metal oxides of its outer surface, described coating of metal oxides is one or more layers, the thickness of described each layer of coating of metal oxides meets following formula: 2nd+1/2 λ=k λ, the refractive index that wherein n is metal oxide; D is the thickness of coating; λ is for interfering long optical wavelength mutually, and value is 350～770nm; K value is except 0 natural number of thinking. The smooth densification of coating of metal oxides of this interference colorful glass microbead outer surface, reflecting properties is good, and color is various adjustable; Preparation technology is simple, easy to utilize.
Description
Technical field
The present invention relates to a kind of colorful glass microbead and preparation method thereof of interfering, belong to glass microballoon field.
Technical background
Glass microsphere is widely used in the fields such as road traffic label, billboard, screen, reflective heat-insulation paint. Two kinds of a reflecting glass microballon adularescent and silver gray at present, if need to have other color in actual application, maybe need to add versicolor film or pigment, and can greatly reduce like this its reflecting effect, or adopt coloured glass to prepare, and the bead reflecting effect that adopts the method to prepare is poor, and conventionally only for decoration field, less for reflection field.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of reflecting properties good for the deficiency of existing product, color-variable, adjustable interference colorful glass microbead and preparation method thereof.
A kind of colorful glass microbead of interfering, comprises spherical common flint glass matrix and is coated on successively the coating of metal oxides of its outer surface, described coating of metal oxides is one or more layers, and the thickness of described each layer of coating of metal oxides meets following formula:
2nd+1/2λ=kλ
The refractive index that wherein n is metal oxide;
D is the thickness of coating;
λ is for interfering long optical wavelength mutually, and value is 350～770nm;
K value is except 0 natural number of thinking.
What interfere that long optical wavelength reflects in visible-range mutually is exactly the color of light.
Press such scheme, the preferred value of described k is 1-3.
Press such scheme, the metal oxide in described coating of metal oxides is selected from titanium dioxide, iron oxide, zirconia, silica, cobalt oxide, chromium oxide, nickel oxide, aluminium oxide, vanadium oxide, molybdenum oxide, manganese oxide etc.
Press such scheme, the diameter of described interference colorful glass microbead is 1 μ m-5mm.
A preparation method who interferes colorful glass microbead, is characterized in that: comprise the following steps:
(a) common flint glass microballon is placed in water through pre-treatment, stirring makes its suspension, then pH requirement when basis is hydrolyzed with the corresponding slaine of metal oxide to be covered, the pH of regulation system is to setting range, under the state stirring, drip corresponding water-soluble metal salting liquid in 20-70 DEG C again, regulate and make system pH be stabilized in aforementioned pH setting range by respective acids basicity simultaneously, and make slaine constantly be hydrolyzed to metal oxide or metal hydroxides, and be coated on equably the surface of glass microballoon, finally reaching setting thickness when this clad, present after pre-color, stop being coated,
When described coating of metal oxides to be covered is multilayer, oxide or metal hydroxides until the first metal are coated on behind glass microballoon surface, then while dripping the corresponding water-soluble metal salting liquid of other each metal oxides corresponding regulation and control hydrolysis system pH value and be coated successively;
(b) filter, wash, dry;
(c) calcining, gets final product to obtain the surperficial interference colorful glass microbead that is coated with smooth compact metal oxide coating after naturally cooling.
Press such scheme, described pre-treatment comprises washing, alkali cleaning or acid pickling step.
Press such scheme, the concentration of described water-soluble metal salting liquid is 10-100g/L, and drop rate is 10-50mL/h.
Press such scheme, described metal oxide is selected from titanium dioxide, iron oxide, zirconia, silica, cobalt oxide, chromium oxide, nickel oxide, aluminium oxide, vanadium oxide, molybdenum oxide, manganese oxide etc.
Press such scheme, if coated metal oxide is titanium dioxide, water soluble salt used is titanium tetrachloride; If coated metal oxide is iron oxide, water soluble salt used is ferric trichloride; If coated metal oxide is zirconia, water soluble salt used is basic zirconium chloride; If coated metal oxide is silica, water soluble salt used is sodium metasilicate; If coated metal oxide is cobalt oxide, water soluble salt used is cobalt chloride; If coated metal oxide is chromium oxide, water soluble salt used is chromium chloride; If coated metal oxide is nickel oxide, water soluble salt used is nickel chloride or nickelous sulfate; If coated metal oxide is aluminium oxide, water soluble salt used is aluminium chloride or aluminum sulfate; If coated metal oxide is vanadium oxide, water soluble salt used is sodium metavanadate; If coated metal oxide is molybdenum oxide, water soluble salt used is sodium molybdate; If coated metal oxide is manganese oxide, water soluble salt used is manganese chloride or manganese sulfate.
Press such scheme, described metal oxide to be covered is TiO2Time, before its corresponding water-soluble metal salting liquid of dropping applies, according to SnCl4PH requirement when hydrolysis, the pH of regulation system, to setting range, drips SnCl under the state stirring4Solution is to be coated in advance one deck SnO outward at glass microballoon2Crystal type promoting reagent.
Press such scheme, described SnCl4With SnO2Metering, the water-soluble metal salt of described titanium is with TiO2Metering, SnCl4The 1%-10% of the addition water-soluble metal salt mole that is titanium.
Press such scheme, the baking temperature of described step (b) is 50-200 DEG C.
Press such scheme, described calcining heat is 200-800 DEG C, and calcination time is 20-100min. Oxide or hydroxide that described calcining heat and calcination time can be this metal according to the coated coating of stromal surface, and obtain in advance the metal oxide of which kind of crystal formation and select.
The present invention prepares metal oxide or metal hydroxides nano particle by hydrolysis, and make this nano particle be coated on equably the surface of glass microsphere, the colorful glass microbead of the surface clad oxide coating obtaining through post processing again, smooth surface densification, reflecting properties is good, not only do not reduce catoptrical brightness, increased on the contrary glass microballoon to reflection of light performance. In addition, by coated different coating of metal oxides, and control coating layer thickness, can prepare the adjustable colorful glass microbead of multiple color.
Principle of the present invention is described as follows:
Take coating of metal oxides as example as individual layer: as shown in Figure 1, in the time that incident illumination is mapped to glass microballoon surface, a part is by glass microballoon surface coating layer reflection (R1), and another part sees through clad, at glass microballoon surface reflection (R2). Because clad has the refractive index that is different from air, so this two-beam has certain phase difference, and be that the frequency that produces of same light beam is identical, thereby produced each other interference, finally show the color of interference colours. And by metal oxide or the coated different coating layer thickness of coated different refractivity, can reach the object of the colorful glass microbead of preparing multiple color. And while being multiple coating, the color difference that this glass microballoon also can be observed with the difference of viewing angle.
Beneficial effect of the present invention:
The smooth densification of coating of metal oxides of this interference colorful glass microbead outer surface, reflecting properties is good, and color is various adjustable;
Preparation technology is simple, easy to utilize.
Brief description of the drawings
Fig. 1 is silvery white glass microballoon and the simple glass microballon integrating sphere light diffuse reflection collection of illustrative plates that embodiment 1 makes.
Fig. 2 is the scanning electron microscope (SEM) photograph contrast of the silvery white glass microballoon that makes of embodiment 1 and simple glass bead surface;
Fig. 3 is colorful glass microbead colour developing schematic diagram of the present invention.
In figure: I is incident light; R1 is clad reverberation; R2 is glass microballoon surface reflection; D is the physical thickness of clad.
Detailed description of the invention
In order to further illustrate summary of the invention of the present invention, below in conjunction with embodiment, summary of the invention of the present invention is described further.
Embodiment 1
Take 10g glass microballoon in 250ml there-necked flask, add 200ml deionized water, stir washing 10 minutes, remove supernatant liquid standing a moment, repeat above-mentioned steps twice, wash complete. Then add 80ml deionized water, by NaOH adjusting pH value to 9, stir 10 minutes, remove supernatant liquid standing a moment, and alkali cleaning is complete. Add 80ml deionized water, with salt acid for adjusting pH value to 2.5, stir 10 minutes. Solution is heated to 60 DEG C, drips the TiCl of 100g/L with the speed of 0.3ml/min4Solution, drip mass percent simultaneously and be 10% NaOH solution with by system pH modification stability 2.5, in the time that products therefrom presents silvery white, stop dripping TiCl4Solution and NaOH aqueous slkali. Filter out solid product, use deionized water washes clean, with 150 DEG C of oven dry, then put into Muffle furnace, be heated to 650 DEG C, roasting 30 minutes, the naturally cooling glossy glass microballoon of silvery white that obtains in stove.
By the silvery white glass microballoon making and not coated TiO2The glass microballoon of interfering layer is analyzed it to reflection of light performance with ultraviolet/visible light spectrophotometer, sees Fig. 1, and silvery white glass microballoon will be better than simple glass microballon far away at the reflecting properties of visible ray and infrared light region as seen from Figure 1. This silvery white glass microballoon ultraviolet region reflecting properties declines, and is due to its TiO2Interfering layer makes the reflecting properties of ultraviolet light decline to some extent very by force to the absorption of ultraviolet light.
Fig. 2 is the scanning electron microscope (SEM) photograph contrast of silvery white glass microballoon and simple glass bead surface; As seen from Figure 2: be coated after interfering layer the surface of glass microballoon more smooth, smooth, and be more conducive to reflection of light.
Embodiment 2
Take 10g glass microballoon in 250ml there-necked flask, add 200ml deionized water, stir washing 10 minutes, remove supernatant liquid standing a moment, repeat above-mentioned steps twice, wash complete. In flask, add 80ml deionized water, by NaOH adjusting pH value, to 9 stirring 10 minutes, removed supernatant liquid standing a moment, and alkali cleaning is complete. Add 80ml deionized water, use salt acid for adjusting pH value to 2.5 stirring 10 minutes. Solution is heated to 60 DEG C, drips the TiCl of 100g/L with the speed of 0.3ml/min4Solution, drips mass percent simultaneously and is 10% NaOH solution so that system pH is stabilized in to 2.5, stops dripping TiCl in the time that products therefrom presents blueness4Solution and NaOH aqueous slkali. Filter out solid product, use deionized water washes clean, 150 DEG C of oven dry, put into Muffle furnace by the colorful glass microbead after drying, and are heated to 650 DEG C, roasting 30 minutes, naturally cooling in stove must blue glossy glass microballoon.
Embodiment 3
Take 10g glass microballoon in 250ml there-necked flask, add 200ml deionized water, mixing speed is per minute 300 to turn. Stir washing 10 minutes, remove supernatant liquid standing a moment, repeat above-mentioned steps twice, wash complete. In flask, add 80ml deionized water, by NaOH adjusting pH value, to 9 stirring 10 minutes, removed supernatant liquid standing a moment, and alkali cleaning is complete. Add 80ml deionized water, regulate pH value to 2 stirring 10 minutes with HCl. Solution is heated to 50 DEG C, drips the SnCl of 35g/L with the speed of 0.2ml/min4Solution 20ml drips 10% NaOH solution so that system pH is stablized to PH 2 simultaneously. Be added dropwise to complete rear stirring 10 minutes. The NaOH solution that dropping mass percent is 10% 2.5, then drips the TiCl of 100g/L with stabilising system pH value with the speed of 0.3ml/min4Solution stops dripping TiCl in the time that products therefrom presents redness4Solution and NaOH aqueous slkali. Filter out solid product, use deionized water washes clean, 100 DEG C of oven dry, by the 650 DEG C of roastings of colorful glass microbead 30 minutes after drying, naturally cooling in stove must red glossy glass microballoon.
By regulating TiCl4The addition of solution, adds crystal type promoting reagent if desired, to control thickness and the titanium dioxide crystal form of coating of titanium dioxide, can reach and control glass microsphere color as the object of the color such as silvery white, golden, yellow, red, purple, blue, green.
Embodiment 4
Take 10g glass microballoon in 250ml there-necked flask, add 200ml deionized water, stir washing 10 minutes, remove supernatant liquid standing a moment, repeat above-mentioned steps twice, wash complete. In flask, add 80ml deionized water, with NaOH adjusting pH value, to 9 stirring 10 minutes, removed supernatant liquid standing a moment, and alkali cleaning is complete. Add 80ml deionized water, with HCl adjusting pH value to 3, stir 10 minutes. Solution is heated to 30 DEG C, drips the FeCl of 30g/L3Solution, drip NaOH solution so that stable system pH value 3, stops dripping solution and NaOH aqueous slkali in the time that products therefrom presents yellow simultaneously. Filter out solid product, use deionized water washes clean, 150 DEG C of oven dry, put into Muffle furnace by the colorful glass microbead after drying, and 300 DEG C of roastings are naturally cooling in stove after 30 minutes obtains yellow glossy glass microballoon; 600 DEG C of roastings 30 minutes, after in stove naturally cooling the glossy glass microballoon of buff.
Regulate FeCl by adjusting3The amount of splashing into of solution, to control the thickness of coating oxidation iron, can control in conjunction with the setting of sintering temperature the crystal formation of iron oxide, and reach the object of controlling bead color simultaneously. Available color has gold, Huang, the multiple color such as red, purple, brown, black.
Embodiment 5
Take 10g glass microballoon in 250ml there-necked flask, add 200ml deionized water, stir washing, remove supernatant liquid standing a moment, repeat above-mentioned steps twice, wash complete. In flask, add 80ml deionized water, with NaOH adjusting pH value, to 9 stirring 10 minutes, removed supernatant liquid standing a moment, and alkali cleaning is complete. Add 80ml deionized water, with hydrochloric acid regulate pH value to 8 stirring 10 minutes. Solution is heated to 25 DEG C, drips the CrCl of 10g/L3Solution, drips mass percent simultaneously and is 3% NaOH solution to stablize pH value 8, stops dripping solution and NaOH aqueous slkali in the time that products therefrom presents green. Filter out solid product, use deionized water washes clean, with 80 DEG C of oven dry, the colorful glass microbead after drying is put into Muffle furnace, 300 DEG C of roastings are naturally cooling in stove after 30 minutes must green glossy glass microballoon; 600 DEG C of roastings after 30 minutes in stove naturally cooling the glossy glass microballoon of bottle green.
By regulating CrCl3The amount of splashing into of solution, to control the thickness of coating oxidation chromium, can control in conjunction with the setting of sintering temperature the crystal formation of chromium oxide, and reach the object of controlling bead color simultaneously. Available color has the multiple colors such as green, yellowish green, blue.
Embodiment 6
Take 10g glass microballoon in 250ml there-necked flask, add 200ml deionized water, stir washing, remove supernatant liquid standing a moment, repeat above-mentioned steps twice, wash complete. In flask, add 80ml deionized water, with NaOH adjusting pH value, to 9 stirring 10 minutes, removed supernatant liquid standing a moment, and alkali cleaning is complete. Add 80ml deionized water, solution is heated to 60 DEG C, drip the sodium silicate solution of 50g/L with the speed of 0.8ml/min, drip mass percent simultaneously and be 3% hydrochloric acid solution to stablize pH value 9, in the time that products therefrom presents golden yellow, stop dripping solution and aqueous slkali. Filter out solid product, use deionized water washes clean, with 120 DEG C of oven dry, the colorful glass microbead after drying is put into Muffle furnace, be heated to 600 DEG C, roasting 30 minutes, naturally cooling in stove must golden yellow glossy glass microballoon.
PH value required when above-mentioned coating also can, after alkali cleaning, with hydrochloric acid adjusting pH value to 2, then drip sodium silicate solution, so coated, in the time that products therefrom presents gold, stop being coated, after in 600 DEG C, roasting 30 minutes, naturally coolingly in stove obtains golden yellow glossy glass microballoon.
By regulating the amount of splashing into of sodium silicate solution, to control the thickness of coating silica, can reach the object of controlling bead color. Available color has silvery white, gold, Huang, the multiple color such as red, purple, blue, green.
Embodiment 7
Take 10g glass microballoon in 250ml there-necked flask, add 200ml deionized water, stir washing, remove supernatant liquid standing a moment, repeat above-mentioned steps twice, wash complete. In flask, add 80ml deionized water, with NaOH adjusting pH value, to 11 stirring 10 minutes, removed supernatant liquid standing a moment, and alkali cleaning is complete. Add 80ml deionized water, solution is heated to 60 DEG C, drip the cobalt chloride solution of 50g/L with the speed of 0.5ml/min, drip NaOH solution to stablize pH value 11 simultaneously, in the time that products therefrom presents blueness, stop dripping cobalt chloride solution and NaOH solution. Filter out solid product, use deionized water washes clean, with 150 DEG C of oven dry, the colorful glass microbead after drying is put into Muffle furnace, be heated to 600 DEG C, roasting 50 minutes, naturally cooling in stove must blue glossy glass microballoon.
By regulating the amount of splashing into of cobalt chloride solution, to control the thickness of coating cobalt dioxide, can reach the object of controlling bead color. Available color has indigo plant, the multiple color such as green, black.
Embodiment 8
Take 10g glass microballoon in 250ml there-necked flask, add 200ml deionized water, stir washing 10 minutes, remove supernatant liquid standing a moment, repeat above-mentioned steps twice, wash complete. In flask, add 80ml deionized water, with NaOH adjusting pH value, to 11 stirring 10 minutes, removed supernatant liquid standing a moment, and alkali cleaning is complete. Add 80ml deionized water, solution is heated to 60 DEG C, drip the zirconium oxychloride solution of 10g/L, drip NaOH solution to stablize pH value 11 simultaneously, in the time that products therefrom presents redness, stop dripping solution and aqueous slkali. Filter out solid product, use deionized water washes clean, with 150 DEG C of oven dry, the colorful glass microbead after drying is put into Muffle furnace, be heated to 600 DEG C, roasting 80 minutes, naturally cooling in stove must red glossy glass microballoon.
By regulating the amount of splashing into of zirconium oxychloride solution, to control the thickness of coating oxidation zirconium, can reach the object of controlling bead color. Available color has silvery white, gold, Huang, the multiple color such as red, purple, blue, green.
Embodiment 9
Take 10g glass microballoon in 250ml there-necked flask, add 200ml deionized water, washing is stirred 10 minutes, removes supernatant liquid standing a moment, repeats above-mentioned steps twice, washes complete. In flask, add 80ml deionized water, with NaOH adjusting pH value, to 8 stirring 10 minutes, removed supernatant liquid standing a moment, and alkali cleaning is complete. Add 80ml deionized water, solution is heated to 60 DEG C, drip the aluminum sulfate solution of 10g/L with the speed of 0.3ml/min, drip mass percent simultaneously and be 10% sodium hydroxide solution to stablize pH value 8, in the time that products therefrom presents redness, stop dripping solution and aqueous slkali. Filter out solid product, use deionized water washes clean, with 150 DEG C of oven dry, the colorful glass microbead after drying is put into Muffle furnace, be heated to 600 DEG C, roasting, naturally cooling in stove must red glossy glass microballoon.
By regulating the amount of splashing into of aluminum sulfate solution, to control the thickness of coating oxidation aluminium, can reach the object of controlling bead color. Available color has silvery white, gold, Huang, the multiple color such as red, purple, blue, green.
Embodiment 10
Take 10g glass microballoon in 250ml there-necked flask, add 200ml deionized water, stir washing 10 minutes, remove supernatant liquid standing a moment, repeat above-mentioned steps twice, wash complete. In flask, add 80ml deionized water, by NaOH adjusting pH value, to 9 stirring 10 minutes, removed supernatant liquid standing a moment, and alkali cleaning is complete. Add 80ml deionized water, use salt acid for adjusting pH value to 2.5 stirring 10 minutes. Solution is heated to 60 DEG C, drips the TiCl of 100g/L with the speed of 0.3ml/min4Solution, drips mass percent simultaneously and is 10% NaOH solution so that system pH is stabilized in to 2.5, stops dripping TiCl in the time that products therefrom presents blueness4Solution and NaOH aqueous slkali. Then regulate pH value to 3 with 10% NaOH solution, stir 10 minutes. Keep 60 DEG C of solution, drip the FeCl of 30g/L3Solution, drip NaOH solution so that stable system pH value 3, stops dripping solution and NaOH aqueous slkali in the time that products therefrom presents yellow simultaneously. Filter out solid product, use deionized water washes clean, 150 DEG C of oven dry, put into Muffle furnace by the colorful glass microbead after drying, and are heated to 600 DEG C, roasting 30 minutes, naturally cooling in stove must yellow slightly red gloss glass microballoon.
Embodiment 11
Take 10g glass microballoon in 250ml there-necked flask, add 200ml deionized water, stir washing 10 minutes, remove supernatant liquid standing a moment, repeat above-mentioned steps twice, wash complete. In flask, add 80ml deionized water, by NaOH adjusting pH value, to 9 stirring 10 minutes, removed supernatant liquid standing a moment, and alkali cleaning is complete. Add 80ml deionized water, use salt acid for adjusting pH value to 2.5 stirring 10 minutes. Solution is heated to 60 DEG C, drips the TiCl of 100g/L with the speed of 0.3ml/min4Solution, drips mass percent simultaneously and is 10% NaOH solution so that system pH is stabilized in to 2.5, stops dripping TiCl in the time that products therefrom presents blueness4Solution and NaOH aqueous slkali. Then regulate pH value to 11 stirring 10 minutes with NaOH, remove supernatant liquid standing a moment, and alkali cleaning is complete. Add 80ml deionized water, keep 60 DEG C of solution, drip the cobalt chloride solution of 50g/L with the speed of 0.3ml/min, drip NaOH solution to stablize pH value 11 simultaneously, in the time that products therefrom presents blueness, stop dripping cobalt chloride solution and NaOH solution. Filter out solid product, use deionized water washes clean, with 150 DEG C of oven dry, the colorful glass microbead after drying is put into Muffle furnace, be heated to 600 DEG C, roasting 30 minutes, the naturally cooling glass microballoon that obtains blue slightly red gloss in stove.
Claims (4)
1. the preparation method who interferes colorful glass microbead, is characterized in that:
The diameter of described interference colorful glass microbead is 1 μ m-5mm;
Described interference colorful glass microbead comprises spherical common flint glass matrix and is coated on successively the coating of metal oxides of its outer surface, and described coating of metal oxides is one or more layers, and the thickness of described each layer of coating of metal oxides meets following formula:
2nd+1/2λ=kλ
The refractive index that wherein n is metal oxide;
D is the thickness of coating;
λ is for interfering long optical wavelength mutually, and value is 350～770nm;
K value is the natural number except 0;
Metal oxide in described coating of metal oxides is selected from titanium dioxide, iron oxide, zirconia, silica, cobalt oxide, chromium oxide, nickel oxide, aluminium oxide, vanadium oxide, molybdenum oxide, manganese oxide;
Its preparation comprises the following steps:
(a) common flint glass matrix is placed in water through pre-treatment, stirring makes its suspension, then according to coating of metal oxides to be covered in the corresponding slaine hydrolysis of metal oxide time pH requirement, the pH of regulation system is to setting range, under the state stirring, drip corresponding water-soluble metal salting liquid in 20-60 DEG C again, regulate and make system pH be stabilized in aforementioned pH setting range by respective acids basicity simultaneously, and make slaine constantly be hydrolyzed to metal oxide or metal hydroxides, and be coated on equably the surface of glass matrix, finally reaching setting thickness when this clad, present after pre-color, stop being coated,
When described coating of metal oxides to be covered is multilayer, oxide or metal hydroxides until the first metal are coated on behind glass matrix surface, then while dripping the corresponding water-soluble metal salting liquid of other each metal oxides corresponding regulation and control hydrolysis system pH value and be coated successively; The concentration of the above-mentioned water-soluble metal salting liquid of mentioning is 10-100g/L, and drop rate is 10-18mL/h;
(b) filter, wash, dry;
(c) calcining, gets final product to obtain the interference colorful glass microbead of the smooth densification of face coat after naturally cooling;
The baking temperature of described step (b) is 80-150 DEG C; The calcining heat of described step (c) is 600-650 DEG C, and calcination time is 20-100min.
2. the preparation method of interference colorful glass microbead according to claim 1, is characterized in that: if metal oxide to be covered is titanium dioxide, water-soluble metal salt used is titanium tetrachloride; If metal oxide to be covered is iron oxide, water-soluble metal salt used is ferric trichloride; If metal oxide to be covered is zirconia, water-soluble metal salt used is basic zirconium chloride; If metal oxide to be covered is silica, water-soluble metal salt used is sodium metasilicate; If metal oxide to be covered is cobalt oxide, water-soluble metal salt used is cobalt chloride; If metal oxide to be covered is chromium oxide, water-soluble metal salt used is chromium chloride; If metal oxide to be covered is nickel oxide, water-soluble metal salt used is nickel chloride or nickelous sulfate; If metal oxide to be covered is aluminium oxide, water-soluble metal salt used is aluminium chloride or aluminum sulfate; If metal oxide to be covered is vanadium oxide, water-soluble metal salt used is sodium metavanadate; If metal oxide to be covered is molybdenum oxide, water-soluble metal salt used is sodium molybdate; If metal oxide to be covered is manganese oxide, water-soluble metal salt used is manganese chloride or manganese sulfate.
3. the preparation method of interference colorful glass microbead according to claim 2, is characterized in that, described metal oxide to be covered is TiO2Time, before its corresponding water-soluble metal salting liquid of dropping applies, according to SnCl4PH requirement when hydrolysis, the pH of regulation system, to setting range, drips SnCl under the state stirring4Solution is to be coated in advance one deck SnO on glass matrix surface2Crystal type promoting reagent.
4. the preparation method of interference colorful glass microbead according to claim 3, is characterized in that: described SnCl4With SnO2Metering, described TiO2Corresponding water-soluble metal salt is with TiO2Metering, SnCl4Addition be TiO2The 1%-10% of corresponding water-soluble metal salt mole.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1183741A (en) * | 1995-03-14 | 1998-06-03 | 日铁矿业株式会社 | Powder having multilayer film on its surface and process for preparing same |
| CN1597793A (en) * | 2004-08-10 | 2005-03-23 | 汕头市龙华珠光颜料有限公司 | Pigment of multi-gradition discolour at diffierent direction and production process thereof |
| CN101434759A (en) * | 2007-11-12 | 2009-05-20 | 温州大学 | Preparation of high glaze glass-based pearlescent pigment |
| CN102181177A (en) * | 2011-03-22 | 2011-09-14 | 华南理工大学 | Method for synthesizing rutile mica titanium pearlescent pigment without calcination |
-
2012
- 2012-10-26 CN CN201210417897.9A patent/CN102951849B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1183741A (en) * | 1995-03-14 | 1998-06-03 | 日铁矿业株式会社 | Powder having multilayer film on its surface and process for preparing same |
| CN1597793A (en) * | 2004-08-10 | 2005-03-23 | 汕头市龙华珠光颜料有限公司 | Pigment of multi-gradition discolour at diffierent direction and production process thereof |
| CN101434759A (en) * | 2007-11-12 | 2009-05-20 | 温州大学 | Preparation of high glaze glass-based pearlescent pigment |
| CN102181177A (en) * | 2011-03-22 | 2011-09-14 | 华南理工大学 | Method for synthesizing rutile mica titanium pearlescent pigment without calcination |
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