CN1296327C - Method for manufacturing ceramic light gathering cavity coated with highly reflective composite membrane - Google Patents

Method for manufacturing ceramic light gathering cavity coated with highly reflective composite membrane Download PDF

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CN1296327C
CN1296327C CNB2004100610653A CN200410061065A CN1296327C CN 1296327 C CN1296327 C CN 1296327C CN B2004100610653 A CNB2004100610653 A CN B2004100610653A CN 200410061065 A CN200410061065 A CN 200410061065A CN 1296327 C CN1296327 C CN 1296327C
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colloidal sol
tio
nitric acid
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sio
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CN1632993A (en
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徐晓虹
吴建锋
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Wuhan University of Technology WUT
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Abstract

The present invention relates to a production method for a ceramic light gathering cavity coated with a film, particularly to a production method for a ceramic light gathering cavity coated with a high reflection composite film. The present invention is characterized in that the present invention comprises the following steps: 1). a basal body of an Al2O3 ceramic light gathering cavity with multiple holes is produced, and is formed by preparing 70 to 80% of Al2O3, 10 to 20% of Suzhou soil and 2 to 10% of sintering aids (by weight percent), and hot pressure casting operation, blank finishing operation, wax removing operation and firing operation are used; 2). Al2O3-SiO2-TiO2-ZrO2 composite collosol is prepared, aluminium isopropoxide water solution is prepared, then, SiO2 collosol, TiO2 collosol and ZrO 2 collosol are added, nitric acid is dropped, and a ceramic light gathering cavity is obtained through back flow for 6 to 12h in a constant temperature bath of 85 to 95 DEG C; 3). a high reflection composite film is coated, and the basal body of the Al2O3 ceramic light gathering cavity is dipped in the collosol three to eight times for firing, namely that a ceramic lighting gathering cavity coated with a high reflection composite film is obtained. The ceramic lighting gathering cavity with a high reflection composite film, which is produced by the present invention, has the characteristics of good antifouling property and high reflectivity.

Description

A kind of manufacture method that scribbles the ceramic spotlight cavity of high reflection composite membrane
Technical field
The present invention relates to the manufacture method of the laser pump cavity that uses in a kind of solid statelaser, be specifically related to a kind of manufacture method of filming ceramic light gathering.
Background technology
Along with the widespread use of solid statelaser in industries such as mechanical workout, medical treatment, electronics, people have higher requirement to the optically focused performance and the emission efficiency of solid statelaser.The critical optical components that influences the optically focused performance is exactly laser pump cavity (claiming pump cavity again), and its effect is that the quantity of radiant energy with pump light source accumulates on the operation material to greatest extent.The closed geometry body that it is normally hollow, light source contains wherein, accumulates on the operation material by the reflection of laser pump cavity inwall.Laser pump cavity directly affects working effect and the service life of laser instrument.Because laser pump cavity is in the high temperature user mode for a long time, and need water quench, keep high optically focused reflecting properties again simultaneously, it is complex-shaped in addition, and the manufacturing dimension precision is higher, therefore is the focus material of Materials science worker research always.
Early stage pump cavity material as low power laser is metal (being generally aluminium, copper and stainless steel etc.), after the internal surface polishing, is coated with metallic membranes such as gold and silver again.Its shortcoming is not corrosion-resistant, and easily machinery scratches, and almost can not clean; Another kind of diffuse reflecting pump cavity is made with metal oxide powder (as magnesium oxide), and it is wrapped in the airtight cover of glass, and laser is sent in reflection by metal oxide.Its shortcoming is that thermal conductivity is low, can only be used for low power laser.Tetrafluoroethylene polyphosphazene polymer optical cavity is to use one of more laser pump cavity at present, its characteristic of processing easily makes the requirement of its easier satisfied high reflection, but resistance of aging is poor, and the dirt in the cooling fluid easily sticks on the polyphosphazene polymer optical cavity, so work-ing life is shorter.
Whiteware (mainly being aluminum oxide, zirconium white and barium sulfate etc.) becomes the main research object of laser pump cavity material gradually.United States Patent (USP) " a kind of preparation of ceramic spotlight cavity " (Pat4802186) adopts high purity aluminium oxide (99.7%) preparation laser pump cavity, obtains 96.8% reflectivity, but stains easily.Chinese patent " ceramic spotlight cavity material; ceramic spotlight cavity and manufacture method thereof " (publication number CN1419322A) adopts high purity aluminium oxide (92.6 ~ 93.7%), and mix with the activated material yttrium oxide and under 1560 ℃ of high temperature, obtained the sintered density height, the laser pump cavity that void content is low.The also unresolved problem that stains easily.
Chinese patent " height reflects, inhales the ultraviolet ceramic glaze and use this ceramic glaze to prepare the method for ceramic spotlight cavity " (publication number CN1475464A) adopts a kind of quartziferous parent glaze of admixture rare earth to improve the antifouling property of ceramic spotlight cavity, but may be to have covered too much Al 2O 3The high reflex of matrix, its reflectivity only can reach 93 ~ 98% (in 600 ~ 900nm scopes).
Summary of the invention
The object of the present invention is to provide the manufacture method of the ceramic spotlight cavity that scribbles high reflection composite membrane that a kind of antifouling property is good, reflectivity is high.
To achieve these goals, technical scheme of the present invention is: a kind of manufacture method that scribbles the ceramic spotlight cavity of high reflective composite membrane is characterized in that comprising the steps: 1). make porous Al 2O 3The ceramic spotlight cavity matrix the steps include: a). take percentage by weight as 70 ~ 80%Al 2O 3, 10 ~ 20% Suzhou soil and 2 ~ 10% sintering aids prepare burden, wherein sintering aid is TiO 2Or MgO, ball milling becomes compound in ball mill, crosses 250 sieves, dries in baking oven, and drying time is 24 ~ 30h, and bake out temperature is 100 ℃; B). add 35 ~ 45% paraffin and 8 ~ 10% oleic acid that account for compound weight in the material after oven dry again, add thermal agitation, heating-up temperature is 60-85 ℃; C). will add the material moulding in the hot-injection molding machine after the thermal agitation, demoulding repaired biscuit; D). base substrate 1100 ~ 1200 ℃ of de-waxings 60 ~ 80 hours in electric furnace behind the repaired biscuit are fed in 1400 ℃ ~ 1450 ℃ high temperature kiln roasting porous Al again 2O 3The ceramic spotlight cavity matrix;
2). preparation Al 2O 3-SiO 2-TiO 2-ZrO 2Complex sol: adopt the fractional hydrolysis method, a. prepares SiO 2Colloidal sol: be by volume: ethyl orthosilicate: C 2H 5OH: H 2O: HNO 3=1: 5: 3: 0.02～0.05, measure ethyl orthosilicate (TEOS), ethanol (C 2H 5OH), water and nitric acid, ethyl orthosilicate is dissolved in the ethanol, Yi Bian drip 1mol/l nitric acid and water, Yi Bian stir, should keep liquid in the whole process is transparent limpid shape always, stirs the SiO that 2～4h namely makes clarification again 2Colloidal sol; B. prepare TiO 2Colloidal sol: be by volume: Ti (OC 4H 9) 4: absolute ethyl alcohol: H 2O: HNO 3=1: 26.5: 1: 0.02～0.05, accurately take by weighing butyl titanate [Ti (OC 4H 9) 4], absolute ethyl alcohol, water and nitric acid, place a beaker to stir absolute ethyl alcohol, then butyl titanate is added in this beaker lentamente, Yi Bian drip 1mol/l nitric acid and water after 2～3h, stir on one side, should keep liquid in the whole process is transparent limpid shape always, stirs the TiO that obtains clarifying behind 0.5～1h again 2Colloidal sol; C. prepare ZrO 2Colloidal sol: be by volume: ZrOCl 28H 2O: C 2H 5OH: H 2O: HNO 3=1: 3.5: 1: 0.02～0.05, accurately take by weighing zirconium oxychloride (ZrOCl 28H 2O), ethanol, water and nitric acid, zirconium oxychloride is joined in the ethanolic solution, Yi Bian drip 1mol/l nitric acid and water, Yi Bian stir, should keep liquid in the whole process is transparent limpid shape always, stirs the ZrO that obtains clarifying behind 8～9h again 2Colloidal sol; D. distilled water is heated to 85 ~ 95 ℃ in there-necked flask, then aluminium isopropoxide is hydrolyzed in 85 ~ 95 ℃ of water, by volume H 2O/Al (OC 3H 7)=120 add aluminium isopropoxide and make the aluminium isopropoxide aqueous solution, stir on one side, add SiO on one side 2Colloidal sol, TiO 2Colloidal sol and ZrO 2Colloidal sol, above four volume ratio be: the aluminium isopropoxide aqueous solution: SiO 2Colloidal sol: TiO 2Colloidal sol: ZrO 2Colloidal sol=1 ~ 4: 1 ~ 4: 1 ~ 4: 1 (below be abbreviated as Al 2O 3: SiO 2: TiO 2: ZrO 2); The aluminium isopropoxide aqueous solution by volume again: nitric acid=1: 0.02～0.08, add 1mol/l nitric acid, control PH is 1.5 ~ 3, at 85 ~ 95 ℃ of waters bath with thermostatic control, the 6 ~ 12h that reflux, namely obtains colourless, transparent Al at last 2O 3-SiO 2-TiO 2-ZrO 2Complex sol;
3) porous Al 2O 3The ceramic spotlight cavity matrix applies high reflective composite membrane, uses the Ultrasonic Cleaning porous Al 2O 3The ceramic spotlight cavity matrix is with porous Al 2O 3The ceramic spotlight cavity matrix immerses Al 2O 3-SiO 2-TiO 2-ZrO 2In the complex sol, soaking the complex sol number of times is 3 ~ 8 times, behind air drying, places electric furnace with 850 ~ 950 ℃ of insulation 1.5 ~ 2h, after naturally cooling off in electric furnace, namely obtains scribbling the ceramic spotlight cavity of high reflective composite membrane.
The present invention adopts aforesaid method, the porous Al of preparation 2O 3The salient features of ceramic spotlight cavity matrix: water-intake rate 10 ~ 15%, void content 20 ~ 40%, volume density 2.0 ~ 2.5g/cm 3, aperture 0.2 ~ 0.4 μ m, folding strength 80 ~ 90MPa, whiteness 90.9, thermal expansivity 7.38 * 10 -6/ ℃ (Rt ~ 1000 ℃).
In this porous Al 2O 3Can apply in conjunction with good Al on the ceramic spotlight cavity matrix 2O 3-SiO 2-TiO 2-ZrO 2Complex sol forms composite membrane.This layer composite membrane evenly spreads over the inner surface of laser pump cavity matrix securely, can effectively protect matrix to avoid the pollution of the dirt in the cooling water, keeps for a long time the good reflection performance of laser pump cavity.Owing to be covered with numerous small grains and crystal boundary thereof in the composite membrane, so that good diffuse reflection takes place incident light in film.If the composition in the composite membrane and film-forming process adjusting is proper, just could be with (the fully reflection of wavelength 530 ~ 890nm) of Ear Mucosa Treated by He Ne Laser Irradiation light.In addition, because composite membrane thickness only is 5 ~ 10 microns, part is shone light also can be by porous Al 2O 3Crystal in the ceramic matrix, crystal boundary and small pore fully reflect.Like this, the synergic reflex effect of matrix and composite membrane can make irradiation light be gathered in to greatest extent on the laser bar and also bring into play enduringly usefulness, thus the reflectivity of Effective Raise laser pump cavity.
Al of the present invention 2O 3: SiO 2: TiO 2: ZrO 2=4: the reflectivity that 1: 1: 1 composite membrane obtains in 530 ~ 890nm wavelength reaches 94.3% ~ 99.5%.Be applicable to that all kinds of solid statelasers are (such as, YAG: xenon lamp laser apparatus etc.).
Description of drawings
Fig. 1 be the ceramic spotlight cavity that scribbles high reflection composite membrane made of the present invention partly cut open structural representation
Fig. 2 is the left view of Fig. 1
Among the figure, the 1-porous Al 2O 3The ceramic spotlight cavity matrix, the high reflective composite membrane of 2-.
Embodiment
Embodiment 1: be optimal way of the present invention:
A kind of manufacture method that scribbles the ceramic spotlight cavity of high reflective composite membrane comprises the steps: 1). make porous Al 2O 3The ceramic spotlight cavity matrix the steps include: a). take percentage by weight as 75%Al 2O 3, 20% Suzhou soil and 5% sintering aid batching, wherein sintering aid is TiO 2Or MgO, ball milling becomes compound in ball mill, and ball milling is 48 hours in ball mill, crosses 250 sieves, dries in baking oven, and drying time is 25h, and bake out temperature is 100 ℃; B). add 39% paraffin and 9% oleic acid that account for compound weight in the material after oven dry again, add thermal agitation, heating-up temperature is 60-85 ℃; C). will add the material moulding in the hot-injection molding machine after the thermal agitation, demoulding repaired biscuit; D). base substrate 1200 ℃ of de-waxings 80 hours in electric furnace behind the repaired biscuit are fed in 1450 ℃ high temperature kiln roasting porous Al again 2O 3The ceramic spotlight cavity matrix.The porous Al of making 2O 3The salient features of ceramic spotlight cavity matrix: water-intake rate 10 ~ 15%, void content 20 ~ 40%, volume density 2.0 ~ 2.5g/cm 3, aperture 0.2 ~ 0.4 μ m, folding strength 80 ~ 90MPa, whiteness 90.9, thermal expansivity 7.38 * 10 -6/ ℃ (Rt ~ 1000 ℃).
2). adopt the fractional hydrolysis legal system to be equipped with Al 2O 3-SiO 2-TiO 2-ZrO 2Complex sol.A. prepare SiO 2Colloidal sol: be by volume: TEOS: C 2H 5OH: H 2O: HNO 3=1: 5: 3: 0.03, measure ethyl orthosilicate (TEOS), ethanol (C 2H 5OH), water and nitric acid, ethyl orthosilicate (TEOS) is dissolved in ethanol (C 2H 5OH) in, Yi Bian drip 1mol/l nitric acid and water, Yi Bian stir, should keep liquid in the whole process is transparent limpid shape always, stirs the SiO that 2～4h namely makes clarification again 2Colloidal sol; B. prepare TiO 2Colloidal sol: be by volume: Ti (OC 4H 9) 4: absolute ethyl alcohol: H 2O: HNO 3=1: 26.5: 1: 0.03, accurately take by weighing butyl titanate [Ti (OC 4H 9) 4], absolute ethyl alcohol, water and nitric acid, with absolute ethyl alcohol C 2H 5OH stirs in a beaker, then butyl titanate is added in this beaker lentamente, Yi Bian drip 1mol/l nitric acid and water after the 2h, Yi Bian stir, should keep liquid in the whole process is transparent limpid shape always, stirs the TiO that obtains clarifying behind the 0.5h again 2Colloidal sol; C. prepare ZrO 2Colloidal sol: be by volume: ZrOCl 28H 2O: C 2H 5OH: H 2O: HNO 3=1: 3.5: 1: 0.04, accurately take by weighing zirconium oxychloride (ZrOCl 28H 2O), ethanol, water and nitric acid, zirconium oxychloride is joined in the ethanolic solution, Yi Bian drip 1mol/l nitric acid and water, Yi Bian stir, should keep liquid in the whole process is transparent limpid shape always, stirs the ZrO that obtains clarifying behind the 8h again 2Colloidal sol; D. distilled water is heated to 85 ~ 95 ℃ in there-necked flask, then aluminium isopropoxide is hydrolyzed in 85 ~ 95 ℃ of water, by volume H 2O/Al (OC 3H 7)=120 add aluminium isopropoxide and make the aluminium isopropoxide aqueous solution, stir on one side, add SiO on one side 2Colloidal sol, TiO 2Colloidal sol and ZrO 2Colloidal sol, above four volume ratio be: the aluminium isopropoxide aqueous solution: SiO 2Colloidal sol: TiO 2Colloidal sol: ZrO 2Colloidal sol=4: 1: 1: 1 (below be abbreviated as Al 2O 3: SiO 2: TiO 2: ZrO 2); The aluminium isopropoxide aqueous solution by volume again: nitric acid=1: 0.03, add 1mol/l nitric acid, control PH is 2, at 85 ~ 95 ℃ of water bath with thermostatic control backflow 10h, namely obtains colourless, transparent Al at last 2O 3-SiO 2-TiO 2-ZrO 2Complex sol;
3). porous Al 2O 3The ceramic spotlight cavity matrix applies high reflective composite membrane, uses the Ultrasonic Cleaning porous Al 2O 3The ceramic spotlight cavity matrix is with porous Al 2O 3The ceramic spotlight cavity matrix immerses Al 2O 3-SiO 2-TiO 2-ZrO 2In the complex sol, soaking the complex sol number of times is 6 times, behind air drying, places electric furnace with 950 ℃ of insulation 1.5h, after naturally cooling off in electric furnace, namely obtains scribbling the ceramic spotlight cavity of high reflective composite membrane.Scribble high reflective composite membrane ceramic spotlight cavity structure as shown in Figure 1 and Figure 2, among the figure, the 1-porous Al 2O 3The ceramic spotlight cavity matrix, the high reflective composite membrane of 2-.
Embodiment 2:
A kind of manufacture method that scribbles the ceramic spotlight cavity of high reflective composite membrane comprises the steps: 1). make porous Al 2O 3The ceramic spotlight cavity matrix the steps include: a). take percentage by weight as 70%Al 2O 3, 20% Suzhou soil and 10% sintering aid batching, wherein sintering aid is TiO 2, ball milling becomes compound in ball mill, and ball milling is 48 hours in ball mill, crosses 250 sieves, dries in baking oven, and drying time is 24h, and bake out temperature is 100 ℃; B). add 35% paraffin and 8% oleic acid that account for compound weight in the material after oven dry again, add thermal agitation, heating-up temperature is 60-85 ℃; C). will add the material moulding in the hot-injection molding machine after the thermal agitation, demoulding repaired biscuit; D). base substrate 1100 ℃ of de-waxings 60 hours in electric furnace behind the repaired biscuit are fed in 1400 ℃ high temperature kiln roasting porous Al again 2O 3The ceramic spotlight cavity matrix.
2). adopt the standby Al of fractional hydrolysis legal system 2O 3-SiO 2-TiO 2-ZrO 2Complex sol: a. prepares SiO 2Colloidal sol: be by volume: TEOS: C 2H 5OH: H 2O: HNO 3=1: 5: 3: 0.05, measure ethyl orthosilicate (TEOS), ethanol (C 2H 5OH), water and nitric acid, ethyl orthosilicate (TEOS) is dissolved in the ethanol, Yi Bian drip 1mol/l nitric acid and water, Yi Bian stir, should keep liquid in the whole process is transparent limpid shape always, stirs the SiO that 2～4h namely makes clarification again 2Colloidal sol; B. prepare TiO 2Colloidal sol: be by volume: Ti (OC 4H 9) 4: absolute ethyl alcohol: H 2O: HNO 3=1: 26.5: 1: 0.05, accurately take by weighing butyl titanate [Ti (OC 4H 9) 4], absolute ethyl alcohol, water and nitric acid, absolute ethyl alcohol is stirred in a beaker, then butyl titanate is added in this beaker lentamente, drip 1mol/l nitric acid and water after the 3h on one side, stir on one side, should keep liquid in the whole process is transparent limpid shape always, stirs the TiO that obtains clarifying behind the 1h again 2Colloidal sol; C. prepare ZrO 2Colloidal sol: be by volume: ZrOCl 28H 2O: C 2H 5OH: H 2O: HNO 3=1: 3.5: 1: 0.05, accurately take by weighing zirconium oxychloride (ZrOCl 28H 2O), ethanol, water and nitric acid, zirconium oxychloride is joined in the ethanolic solution, Yi Bian drip 1mol/l nitric acid and water, Yi Bian stir, should keep liquid in the whole process is transparent limpid shape always, stirs the ZrO that obtains clarifying behind 8～9h again 2Colloidal sol; D. distilled water is heated to 85 ~ 95 ℃ in there-necked flask, then aluminium isopropoxide is hydrolyzed in 85 ~ 95 ℃ of water, by volume H 2O/Al (OC 3H 7)=120 add aluminium isopropoxide and make the aluminium isopropoxide aqueous solution, stir on one side, add SiO on one side 2Colloidal sol, TiO 2Colloidal sol and ZrO 2Colloidal sol, above four volume ratio be: the aluminium isopropoxide aqueous solution: SiO 2Colloidal sol: TiO 2Colloidal sol: ZrO 2Colloidal sol=1: 4: 1: 1; The aluminium isopropoxide aqueous solution by volume again: nitric acid=1: 0.08, add 1mol/l nitric acid, control PH is 3, at 85 ~ 95 ℃ of waters bath with thermostatic control, the 6 ~ 12h that reflux, namely obtains colourless, transparent Al at last 2O 3-SiO 2-TiO 2-ZrO 2Complex sol;
3). porous Al 2O 3The ceramic spotlight cavity matrix applies high reflective composite membrane, uses the Ultrasonic Cleaning porous Al 2O 3The ceramic spotlight cavity matrix is with porous Al 2O 3The ceramic spotlight cavity matrix immerses Al 2O 3-SiO 2-TiO 2-ZrO 2In the complex sol, soaking the complex sol number of times is 3 times, behind air drying, places electric furnace with 850 ℃ of insulation 1.5h, after naturally cooling off in electric furnace, namely obtains scribbling the ceramic spotlight cavity of high reflective composite membrane.
Embodiment 3:
A kind of manufacture method that scribbles the ceramic spotlight cavity of high reflective composite membrane comprises the steps: 1). make porous Al 2O 3The ceramic spotlight cavity matrix the steps include: a). take percentage by weight as 80%Al 2O 3, 18% Suzhou soil and 2% sintering aid batching, wherein sintering aid is MgO, ball milling becomes compound in ball mill, ball milling is 48 hours in ball mill, crosses 250 sieves, dries in baking oven, drying time is 30h, bake out temperature is 100 ℃; B). add 45% paraffin and 10% oleic acid that account for compound weight in the material after oven dry again, add thermal agitation, heating-up temperature is 60-85 ℃; C). will add the material moulding in the hot-injection molding machine after the thermal agitation, demoulding repaired biscuit; D). base substrate 1200 ℃ of de-waxings 80 hours in electric furnace behind the repaired biscuit are fed in 1450 ℃ high temperature kiln roasting porous Al again 2O 3The ceramic spotlight cavity matrix.Porous Al 2O 3The salient features of ceramic spotlight cavity matrix: water-intake rate 10 ~ 15%, void content 20 ~ 40%, volume density 2.0 ~ 2.5g/cm 3, aperture 0.2 ~ 0.4 μ m, folding strength 80 ~ 90MPa, whiteness 90.9, thermal expansivity 7.38 * 10 -6/ ℃ (Rt ~ 1000 ℃).
2). adopt the standby Al of fractional hydrolysis legal system 2O 3-SiO 2-TiO 2-ZrO 2Complex sol: a. prepares SiO 2Colloidal sol: be by volume: TEOS: C 2H 5OH: H 2O: HNO 3=1: 5: 3: 0.04, measure ethyl orthosilicate (TEOS), ethanol (C 2H 5OH), water and nitric acid, ethyl orthosilicate is dissolved in the ethanol, Yi Bian drip 1mol/l nitric acid and water, Yi Bian stir, should keep liquid in the whole process is transparent limpid shape always, stirs the SiO that 2～4h namely makes clarification again 2Colloidal sol; B. prepare TiO 2Colloidal sol: be by volume: Ti (OC 4H 9) 4: absolute ethyl alcohol: H 2O: HNO 3=1: 26.5: 1: 0.04, accurately take by weighing butyl titanate [Ti (OC 4H 9) 4], absolute ethyl alcohol, water and nitric acid, absolute ethyl alcohol is stirred in a beaker, then with butyl titanate Ti (OC 4H 9) 4Add lentamente in this beaker, Yi Bian drip 1mol/l nitric acid and water after 2～3h, Yi Bian stir, should keep liquid in the whole process is transparent limpid shape always, stirs the TiO that obtains clarifying behind 0.5～1h again 2Colloidal sol; C. prepare ZrO 2Colloidal sol: be by volume: ZrOCl 28H 2O: C 2H 5OH: H 2O: HNO 3=1: 3.5: 1: 0.05, accurately take by weighing zirconium oxychloride (ZrOCl 28H 2O), ethanol, water and nitric acid, zirconium oxychloride is joined in the ethanolic solution, Yi Bian drip 1mol/l nitric acid and water, Yi Bian stir, should keep liquid in the whole process is transparent limpid shape always, stirs the ZrO that obtains clarifying behind 8～9h again 2Colloidal sol; D. distilled water is heated to 85 ~ 95 ℃ in there-necked flask, then aluminium isopropoxide is hydrolyzed in 85 ~ 95 ℃ of water, by volume H 2O/Al (OC 3H 7)=120 add aluminium isopropoxide and make the aluminium isopropoxide aqueous solution, stir on one side, add SiO on one side 2Colloidal sol, TiO 2Colloidal sol and ZrO 2Colloidal sol, above four volume ratio be: the aluminium isopropoxide aqueous solution: SiO 2Colloidal sol: TiO 2Colloidal sol: ZrO 2Colloidal sol=1: 1: 4: 1; The aluminium isopropoxide aqueous solution by volume again: nitric acid=1: 0.05, add 1mol/l nitric acid, control PH is 2.5, at 85 ~ 95 ℃ of waters bath with thermostatic control, the 6 ~ 12h that reflux, namely obtains colourless, transparent Al at last 2O 3-SiO 2-TiO 2-ZrO 2Complex sol;
3). porous Al 2O 3The ceramic spotlight cavity matrix applies high reflective composite membrane, uses the Ultrasonic Cleaning porous Al 2O 3The ceramic spotlight cavity matrix is with porous Al 2O 3The ceramic spotlight cavity matrix immerses Al 2O 3-SiO 2-TiO 2-ZrO 2In the complex sol, soaking the complex sol number of times is 8 times, behind air drying, places electric furnace with 950 ℃ of insulation 2h, after naturally cooling off in electric furnace, namely obtains scribbling the ceramic spotlight cavity of high reflective composite membrane.
Embodiment 4:
A kind of manufacture method that scribbles the ceramic spotlight cavity of high reflective composite membrane comprises the steps: 1). make porous Al 2O 3The ceramic spotlight cavity matrix the steps include: a). take percentage by weight as 80%Al 2O 3, 10% Suzhou soil and 10% sintering aid batching, wherein sintering aid is TiO 2, ball milling becomes compound in ball mill, crosses 250 sieves, dries in baking oven, and drying time is 26h, and bake out temperature is 100 ℃; B). add 40% paraffin and 9% oleic acid that account for compound weight in the material after oven dry again, add thermal agitation, heating-up temperature is 60-85 ℃; C). will add the material moulding in the hot-injection molding machine after the thermal agitation, demoulding repaired biscuit; D). base substrate 1200 ℃ of de-waxings 70 hours in electric furnace behind the repaired biscuit are fed in 1450 ℃ high temperature kiln roasting porous Al again 2O 3The ceramic spotlight cavity matrix;
2). adopt the standby Al of fractional hydrolysis legal system 2O 3-SiO 2-TiO 2-ZrO 2Complex sol: a. prepares SiO 2Colloidal sol: be by volume: TEOS: C 2H 5OH: H 2O: HNO 3=1: 5: 3: 0.04, measure ethyl orthosilicate (TEOS), ethanol (C 2H 5OH), water and nitric acid, ethyl orthosilicate is dissolved in the ethanol, Yi Bian drip 1mol/l nitric acid and water, Yi Bian stir, should keep liquid in the whole process is transparent limpid shape always, stirs the SiO that 2～4h namely makes clarification again 2Colloidal sol; B. prepare TiO 2Colloidal sol: be by volume: Ti (OC 4H 9) 4: absolute ethyl alcohol: H 2O: HNO 3=1: 26.5: 1: 0.04, accurately take by weighing butyl titanate [Ti (OC 4H 9) 4], absolute ethyl alcohol, water and nitric acid, place a beaker to stir absolute ethyl alcohol, then with butyl titanate Ti (OC 4H 9) 4Add lentamente in this beaker, Yi Bian drip 1mol/l nitric acid and water after the 2.4h, Yi Bian stir, should keep liquid in the whole process is transparent limpid shape always, stirs the TiO that obtains clarifying behind 0.5～1h again 2Colloidal sol; C. prepare ZrO 2Colloidal sol: be by volume: ZrOCl 28H 2O: C 2H 5OH: H 2O: HNO 3=1: 3.5: 1: 0.03, accurately take by weighing zirconium oxychloride (ZrOCl 28H 2O), ethanol, water and nitric acid, zirconium oxychloride is joined in the ethanolic solution, Yi Bian drip 1mol/l nitric acid and water, Yi Bian stir, should keep liquid in the whole process is transparent limpid shape always, stirs the ZrO that obtains clarifying behind 8～9h again 2Colloidal sol; D. distilled water is heated to 85 ~ 95 ℃ in there-necked flask, then aluminium isopropoxide is hydrolyzed in 85 ~ 95 ℃ of water, by volume H 2O/Al (OC 3H 7)=120 add aluminium isopropoxide and make the aluminium isopropoxide aqueous solution, stir on one side, add SiO on one side 2Colloidal sol, TiO 2Colloidal sol and ZrO 2Colloidal sol, above four volume ratio be: the aluminium isopropoxide aqueous solution: SiO 2Colloidal sol: TiO 2Colloidal sol: ZrO 2Colloidal sol=2: 1: 1: 1; The aluminium isopropoxide aqueous solution by volume again: nitric acid=1: 0.06, add 1mol/l nitric acid, control PH is 2.5, at 85 ~ 95 ℃ of waters bath with thermostatic control, the 6 ~ 12h that reflux, namely obtains colourless, transparent Al at last 2O 3-SiO 2-TiO 2-ZrO 2Complex sol;
3). porous Al 2O 3The ceramic spotlight cavity matrix applies high reflective composite membrane: use the Ultrasonic Cleaning porous Al 2O 3The ceramic spotlight cavity matrix is with porous Al 2O 3The ceramic spotlight cavity matrix immerses Al 2O 3-SiO 2-TiO 2-ZrO 2In the complex sol, soaking the complex sol number of times is 7 times, behind air drying, places electric furnace with 900 ℃ of insulation 2h, after naturally cooling off in electric furnace, namely obtains scribbling the ceramic spotlight cavity of high reflective composite membrane.
Adopt the high reflectivity that reflects the ceramic spotlight cavity of composite membrane that scribbles of four quasi-representatives of method manufacturing of the present invention to see the following form:
Embodiment 5:
A kind of manufacture method that scribbles the ceramic spotlight cavity of high reflective composite membrane comprises the steps: 1). make porous Al 2O 3The ceramic spotlight cavity matrix the steps include: a). take percentage by weight as 70%Al 2O 3, 20% Suzhou soil and 10% sintering aid batching, wherein sintering aid is TiO 2, ball milling becomes compound in ball mill, crosses 250 sieves, dries in baking oven, and drying time is 24h, and bake out temperature is 100 ℃; B). add 35% paraffin and 8% oleic acid that account for compound weight in the material after oven dry again, add thermal agitation, heating-up temperature is 60 ℃; C). will add the material moulding in the hot-injection molding machine after the thermal agitation, demoulding repaired biscuit; D). base substrate 1100 ℃ of de-waxings 60 hours in electric furnace behind the repaired biscuit are fed in 1400 ℃ high temperature kiln roasting porous Al again 2O 3The ceramic spotlight cavity matrix;
2). preparation Al 2O 3-SiO 2-TiO 2-ZrO 2Complex sol: adopt the fractional hydrolysis method, a. prepares SiO 2Colloidal sol: be by volume: ethyl orthosilicate: C 2H 5OH: H 2O: HNO 3=1: 5: 3: 0.02, measure ethyl orthosilicate (TEOS), ethanol (C 2H 5OH), water and nitric acid, ethyl orthosilicate is dissolved in the ethanol, Yi Bian drip 1mol/l nitric acid and water, Yi Bian stir, should keep liquid in the whole process is transparent limpid shape always, stirs the SiO that 2h namely makes clarification again 2Colloidal sol; B. prepare TiO 2Colloidal sol: be by volume: Ti (OC 4H 9) 4: absolute ethyl alcohol: H 2O: HNO 3=1: 26.5: 1: 0.02, accurately take by weighing butyl titanate [Ti (OC 4H 9) 4], absolute ethyl alcohol, water and nitric acid, place a beaker to stir absolute ethyl alcohol, then butyl titanate is added in this beaker lentamente, drip 1mol/l nitric acid and water after the 2h on one side, stir on one side, should keep liquid in the whole process is transparent limpid shape always, stirs the TiO that obtains clarifying behind the 0.5h again 2Colloidal sol; C. prepare ZrO 2Colloidal sol: be by volume: ZrOCl 28H 2O: C 2H 5OH: H 2O: HNO 3=1: 3.5: 1: 0.02, accurately take by weighing zirconium oxychloride (ZrOCl 28H 2O), ethanol, water and nitric acid, zirconium oxychloride is joined in the ethanolic solution, Yi Bian drip 1mol/l nitric acid and water, Yi Bian stir, should keep liquid in the whole process is transparent limpid shape always, stirs the ZrO that obtains clarifying behind the 8h again 2Colloidal sol; D. distilled water is heated to 85 ℃ in there-necked flask, then aluminium isopropoxide is hydrolyzed in 85 ℃ of water, by volume H 2O/Al (OC 3H 7)=120 add aluminium isopropoxide and make the aluminium isopropoxide aqueous solution, stir on one side, add SiO on one side 2Colloidal sol, TiO 2Colloidal sol and ZrO 2Colloidal sol, above four volume ratio be: the aluminium isopropoxide aqueous solution: SiO 2Colloidal sol: TiO 2Colloidal sol: ZrO 2Colloidal sol=1: 1: 1: 1; The aluminium isopropoxide aqueous solution by volume again: nitric acid=1: 0.02, add 1mol/l nitric acid, control PH is 1.5, at 85 ℃ of water bath with thermostatic control backflow 6h, namely obtains colourless, transparent Al at last 2O 3-SiO 2-TiO 2-ZrO 2Complex sol;
3) porous Al 2O 3The ceramic spotlight cavity matrix applies high reflective composite membrane, uses the Ultrasonic Cleaning porous Al 2O 3The ceramic spotlight cavity matrix is with porous Al 2O 3The ceramic spotlight cavity matrix immerses Al 2O 3-SiO 2-TiO 2-ZrO 2In the complex sol, soaking the complex sol number of times is 3 times, behind air drying, places electric furnace with 850 ℃ of insulation 1.5h, after naturally cooling off in electric furnace, namely obtains scribbling the ceramic spotlight cavity of high reflective composite membrane.
Example 6:
A kind of manufacture method that scribbles the ceramic spotlight cavity of high reflective composite membrane comprises the steps: 1). make porous Al 2O 3The ceramic spotlight cavity matrix the steps include: a). take percentage by weight as 80%Al 2O 3, 18% Suzhou soil and 2% sintering aid batching, wherein sintering aid is MgO, ball milling becomes compound in ball mill, crosses 250 sieves, dries in baking oven, drying time is 30h, bake out temperature is 100 ℃; B). add 45% paraffin and 10% oleic acid that account for compound weight in the material after oven dry again, add thermal agitation, heating-up temperature is 85 ℃; C). will add the material moulding in the hot-injection molding machine after the thermal agitation, demoulding repaired biscuit; D). base substrate 1200 ℃ of de-waxings 80 hours in electric furnace behind the repaired biscuit are fed in 1450 ℃ high temperature kiln roasting porous Al again 2O 3The ceramic spotlight cavity matrix;
2). preparation Al 2O 3-SiO 2-TiO 2-ZrO 2Complex sol: adopt the fractional hydrolysis method, a. prepares SiO 2Colloidal sol: be by volume: ethyl orthosilicate: C 2H 5OH: H 2O: HNO 3=1: 5: 3: 0.05, measure ethyl orthosilicate (TEOS), ethanol (C 2H 5OH), water and nitric acid, ethyl orthosilicate is dissolved in the ethanol, Yi Bian drip 1mol/l nitric acid and water, Yi Bian stir, should keep liquid in the whole process is transparent limpid shape always, stirs the SiO that 4h namely makes clarification again 2Colloidal sol; B. prepare TiO 2Colloidal sol: be by volume: Ti (OC 4H 9) 4: absolute ethyl alcohol: H 2O: HNO 3=1: 26.5: 1: 0.05, accurately take by weighing butyl titanate [Ti (OC 4H 9) 4], absolute ethyl alcohol, water and nitric acid, place a beaker to stir absolute ethyl alcohol, then butyl titanate is added in this beaker lentamente, drip 1mol/l nitric acid and water after the 3h on one side, stir on one side, should keep liquid in the whole process is transparent limpid shape always, stirs the TiO that obtains clarifying behind the 1h again 2Colloidal sol; C. prepare ZrO 2Colloidal sol: be by volume: ZrOCl 28H 2O: C 2H 5OH: H 2O: HNO 3=1: 3.5: 1: 0.05, accurately take by weighing zirconium oxychloride (ZrOCl 28H 2O), ethanol, water and nitric acid, zirconium oxychloride is joined in the ethanolic solution, Yi Bian drip 1mol/l nitric acid and water, Yi Bian stir, should keep liquid in the whole process is transparent limpid shape always, stirs the ZrO that obtains clarifying behind the 9h again 2Colloidal sol; D. distilled water is heated to 95 ℃ in there-necked flask, then aluminium isopropoxide is hydrolyzed in 95 ℃ of water, by volume H 2O/Al (OC 3H 7)=120 add aluminium isopropoxide and make the aluminium isopropoxide aqueous solution, stir on one side, add SiO on one side 2Colloidal sol, TiO 2Colloidal sol and ZrO 2Colloidal sol, above four volume ratio be: the aluminium isopropoxide aqueous solution: SiO 2Colloidal sol: TiO 2Colloidal sol: ZrO 2Colloidal sol=4: 4: 4: 1; The aluminium isopropoxide aqueous solution by volume again: nitric acid=1: 0.08, add 1mol/l nitric acid, control PH is 3, at 95 ℃ of water bath with thermostatic control backflow 12h, namely obtains colourless, transparent Al at last 2O 3-SiO 2-TiO 2-ZrO 2Complex sol;
3) porous Al 2O 3The ceramic spotlight cavity matrix applies high reflective composite membrane, uses the Ultrasonic Cleaning porous Al 2O 3The ceramic spotlight cavity matrix is with porous Al 2O 3The ceramic spotlight cavity matrix immerses Al 2O 3-SiO 2-TiO 2-ZrO 2In the complex sol, soaking the complex sol number of times is 8 times, behind air drying, places electric furnace with 950 ℃ of insulation 2h, after naturally cooling off in electric furnace, namely obtains scribbling the ceramic spotlight cavity of high reflective composite membrane.

Claims (2)

1. a manufacture method that scribbles the ceramic spotlight cavity of high reflective composite membrane is characterized in that comprising the steps: 1). make porous Al 2O 3The ceramic spotlight cavity matrix the steps include: a). take percentage by weight as 70 ~ 80%Al 2O 3, 10 ~ 20% Suzhou soil and 2 ~ 10% sintering aids prepare burden, wherein sintering aid is TiO 2Or MgO, ball milling becomes compound in ball mill, crosses 250 sieves, dries in baking oven, and drying time is 24 ~ 30h, and bake out temperature is 100 ℃; B). add 35 ~ 45% paraffin and 8 ~ 10% oleic acid that account for compound weight in the material after oven dry again, add thermal agitation, heating-up temperature is 60-85 ℃; C). will add the material moulding in the hot-injection molding machine after the thermal agitation, demoulding repaired biscuit; D). base substrate 1100 ~ 1200 ℃ of de-waxings 60 ~ 80 hours in electric furnace behind the repaired biscuit are fed in 1400 ℃ ~ 1450 ℃ high temperature kiln roasting porous Al again 2O 3The ceramic spotlight cavity matrix;
2). preparation Al 2O 3-SiO 2-TiO 2-ZrO 2Complex sol: adopt the fractional hydrolysis method, a. prepares SiO 2Colloidal sol: be by volume: tetraethoxy: C 2H 5OH: H 2O: HNO 3=1: 5: 3: 0.02～0.05, measure tetraethoxy, ethanol, water and nitric acid, tetraethoxy is dissolved in the ethanol, drip 1mol/l nitric acid and water on one side, stir on one side, should keep liquid in the whole process is transparent limpid shape always, and restir 2～4h promptly makes clarifying SiO 2Colloidal sol; B. prepare TiO 2Colloidal sol: be by volume: butyl (tetra) titanate: dehydrated alcohol: H 2O: HNO 3=1: 26.5: 1: 0.02～0.05, accurately take by weighing butyl (tetra) titanate, dehydrated alcohol, water and nitric acid, place a beaker to stir dehydrated alcohol, then butyl (tetra) titanate is added in this beaker lentamente, Yi Bian drip 1mol/l nitric acid and water after 2～3h, stir on one side, should keep liquid in the whole process is transparent limpid shape always, obtains clarifying TiO behind restir 0.5～1h 2Colloidal sol; C. prepare ZrO 2Colloidal sol: be by volume: ZrOCl 28H 2O: C 2H 5OH: H 2O: HNO 3=1: 3.5: 1: 0.02～0.05, accurately take by weighing zirconium oxychloride, ethanol, water and nitric acid, zirconium oxychloride is joined in the ethanolic soln, drip 1mol/l nitric acid and water on one side, stir on one side, should keep liquid in the whole process is transparent limpid shape always, obtains clarifying ZrO behind restir 8～9h 2Colloidal sol; D. distilled water is heated to 85 ~ 95 ℃ in there-necked flask, then with aluminum isopropylate hydrolysis, H by volume in 85 ~ 95 ℃ of water 2O/Al (OC 3H 7)=120 add aluminum isopropylate and make the aluminum isopropylate aqueous solution, stir on one side, add SiO on one side 2Colloidal sol, TiO 2Colloidal sol and ZrO 2Colloidal sol, above four volume ratio be: the aluminum isopropylate aqueous solution: SiO 2Colloidal sol: TiO 2Colloidal sol: ZrO 2Colloidal sol=1 ~ 4: 1 ~ 4: 1 ~ 4: 1; The aluminum isopropylate aqueous solution by volume again: nitric acid=1: 0.02～0.08, add 1mol/l nitric acid, control pH is 1.5 ~ 3, at 85 ~ 95 ℃ of waters bath with thermostatic control, the 6 ~ 12h that reflux, promptly obtains colourless, transparent Al at last 2O 3-SiO 2-TiO 2-ZrO 2Complex sol;
3). porous Al 2O 3The ceramic spotlight cavity matrix applies high reflective composite membrane: use the Ultrasonic Cleaning porous Al 2O 3The ceramic spotlight cavity matrix is with porous Al 2O 3The ceramic spotlight cavity matrix immerses Al 2O 3-SiO 2-TiO 2-ZrO 2In the complex sol, soaking the complex sol number of times is 3 ~ 8 times, behind air drying, places electric furnace with 850 ~ 950 ℃ of insulation 1.5 ~ 2h, after naturally cooling off in electric furnace, namely obtains scribbling the ceramic spotlight cavity of high reflective composite membrane.
2. a kind of manufacture method that scribbles the ceramic spotlight cavity of high reflective composite membrane according to claim 1 is characterized in that: described manufacturing porous A1 2O 3Al in the step of ceramic spotlight cavity matrix 2O 3, Suzhou soil and sintering aid percentage by weight be respectively: 75%, 20% and 5%.
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