CN101117708A - Liquid deposition preparing method for germanium dioxide material - Google Patents
Liquid deposition preparing method for germanium dioxide material Download PDFInfo
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- CN101117708A CN101117708A CNA2006100481045A CN200610048104A CN101117708A CN 101117708 A CN101117708 A CN 101117708A CN A2006100481045 A CNA2006100481045 A CN A2006100481045A CN 200610048104 A CN200610048104 A CN 200610048104A CN 101117708 A CN101117708 A CN 101117708A
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Abstract
The present invention relates to a liquid-phase deposition process for preparing germanium oxide material and belongs to the technical field of material preparation. Promoted with heating and stirring, germanium oxide is dissolved with the water as the solvent and the ammonia water as the chelating agent; a good precursor of germanium oxide basal material is prepared by filtering the solution. Miscellaneous germanium oxide material or germanium oxide adulterated material can be obtained by mixing the precursor and other solution-state or sol-state substances according to a set proportion and then performing heat treatment on the mixture. With simple principle, the present invention can be implemented with common raw materials and common equipments without hidden dangers or toxicity. With mild and controllable reaction conditions, the present invention can not only synthesize germanium oxide material with low cost and high quality, but also cost-effectively synthesize other germanium oxide-based materials, e.g. SiO2-GeO2, TiO2-SiO2-GeO2, adulterated material of rare-earth elements and GeO2, adulterated material of GeO2 of other bases, etc.
Description
Technical field
The present invention relates to the liquid deposition preparation method of germanium dioxide material, belong to technical field of material.
Background technology
Germanium oxide is important Semiconductor Optoeletronic Materials, in optical-fibre communications and other field of optoelectronic devices extremely extensive and deep application is arranged all, so people have developed the method that much is used to prepare the germanium oxide material.The method that is used to prepare the germanium oxide material at present mainly contains chemical Vapor deposition process (CVD), magnetron sputtering method, scorification, ion implantation, flame decomposition method, chemical gas phase axle phase sedimentation and sol-gel processing.Chemical Vapor deposition process (CVD), magnetron sputtering method, ion implantation, flame decomposition method, chemical gas phase axle phase sedimentation all need expensive Special Equipment, severe reaction conditions, some can only use the gaseous compound of expensive germanium to make raw material.Scorification carries out under the high temperature more than 1150 ℃, not only has the high energy consumption characteristic, and because the high viscosity characteristic of high temperature oxidation germanium liquid makes it have the difficult and easy problem that produces air blister defect of moulding.Though sol-gel processing can realize that at a lower temperature (about 500-600 ℃) synthesizes germanium oxide, the precursor of germanium very expensive (300 yuan/mg) and hydrolysis wayward, be difficult to realize low-cost synthetic germanium oxide colloidal sol.Because colloidal sol-gelatinous material ubiquity is cracking and the bigger shortcoming of hole easily, be difficult to prepare high-quality germanium oxide thick film with sol-gel processing.In sum, there is the equipment requirements height in the germanium oxide material preparation technology at present, and raw material costliness, severe reaction conditions are difficult to control, the big deficiency that waits of the fault in material of making.
Summary of the invention
The objective of the invention is to overcome above-mentioned the deficiencies in the prior art, and provide a kind of principle simple, need not any Special Equipment, common, the no potentially dangerous of raw material and toxicity, the reaction conditions gentleness is controlled and can also be by controlling the liquid deposition preparation method that reaction conditions obtains having the germanium oxide class material of differing materials structure and performance.This method not only can realize that low-cost and high-quality ground synthesizes the germanium oxide material, and can realize synthetic at low cost other material of germanium oxide base, as SiO
2-GeO
2, TiO
2-SiO
2-GeO
2, rare earth doped GeO
2Material, GeO
2Other body material or the like mixes.
Purpose of the present invention can realize by following approach:
The liquid deposition preparation method of germanium oxide class material of the present invention comprises following preparation process:
(1) ammoniacal liquor dilution: ammoniacal liquor is mixed with water, and the volume ratio of control ammoniacal liquor and water is 1: 200-1: 10, obtain A liquid;
(2) adding under the gentle stirring condition, the germanium oxide powder is joined in the A liquid, control: the mass ratio of germanium oxide and water is 0-0.5, and churning time 0.5-24 hour, the Heating temperature scope was 25-100 ℃; With the liquid filtering that obtains, collecting filtrate is B liquid;
The ratio of water and germanium oxide need not heat less than 0.05 o'clock; When stirring more than 70 ℃, need add condensation reflux unit in container upper end.
(3) add high molecular weight water soluble polymer in B liquid, and stirred 0.5-4 hour, the add-on of high molecular weight water soluble polymer is to add the 0-20g polymkeric substance in the B liquid of every 40ml volume, obtains C liquid;
Described high molecular weight water soluble polymer is polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyacrylic acid, polyoxyethylene glycol, polyoxyethylene, polymaleic anhydride, Poly Dimethyl Diallyl Ammonium Chloride, polyvinylamine, poly-2-ethene tetrahydroglyoxaline, sodium polystyrene sulfonate, Sulfonated Copolymer of Styrene and Maleic Anhydride, open the mixture of pul resin or one of them.
(4) with C liquid as lotion, adopt dip-coating method plated film on the substrates such as glass, plastics, pottery or metallic substance of different shape, pull rate 0.01-25.00cm/min 30-1500 ℃ of scope thermal treatment, obtains the germanium oxide membrane material with the substrate of plated film.
Purpose of the present invention can also realize by following approach:
The liquid deposition preparation method of germanium oxide class material of the present invention also comprises following preparation process:
(1) add water-reducible acid solution in B liquid, the add-on scope of acid solution is that 0.001-98.000 determines by the quality ratio of acid and ammoniacal liquor, obtains D liquid;
Described acid solution is the mixing solutions of hydrochloric acid, sulfuric acid, acetate, phosphoric acid or one of them, and the massfraction of described acid solution is 0.001 to 98%.
(2) D liquid was left standstill 10 minutes to 90 days in room temperature, deposit the germanium oxide powder;
(3) add high molecular weight water soluble polymer in D liquid, the add-on of high molecular weight water soluble polymer is to add 0-50g in every 100mlD liquid, leaves standstill 10 minutes to 90 days in room temperature, deposits the germanium oxide powder of controllable appearance;
Described high molecular weight water soluble polymer is polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyacrylic acid, polyoxyethylene glycol, polyoxyethylene, polymaleic anhydride, Poly Dimethyl Diallyl Ammonium Chloride, polyvinylamine, poly-2-ethene tetrahydroglyoxaline, sodium polystyrene sulfonate, Sulfonated Copolymer of Styrene and Maleic Anhydride, open the mixture of pul resin or one of them.
(4) in D liquid, put into the solid support materials such as glass, pottery, plastics or metallic substance of different shape, left standstill 10 minutes to 90 days, on carrier, slowly grow uniform germanium oxide membrane material in room temperature;
Particularly, D liquid slowly is passed in the hollow pipe, caliber size is not less than 1 micron, the flow control that feeds is at 0-1000ml/min, circulation feeds, perhaps D liquid is filled hollow Guan Houyi end closure and left standstill, after 10 minutes to 90 days, can on inside pipe wall, deposit the uniform germanium oxide membrane material of thickness.This germanium oxide membrane material can be used as hollow core optical waveguide (optical fiber).
(5) the above-mentioned germanium oxide class material that deposits is heat-treated, can obtain the germanium oxide class material of voidage at 0-80%, thermal treatment temp is a 30-1500 ℃ of scope.
Purpose of the present invention can also realize by following approach:
The liquid deposition preparation method of germanium oxide class material of the present invention also comprises following preparation process:
Add soluble ree unit cellulose solution in B liquid, the molar ratio of germanium and rare earth element can obtain rare earth doped germanium oxide class material at 10-1000.
Add silicon dioxide gel and mix (E liquid) in B liquid, the quality percentage composition scope of silicon-dioxide is 0-99% in the silicon dioxide gel, and the molar ratio of silicon and element Ge can obtain silicon-dioxide-germanium oxide class material at 0-1000.
In E liquid, add soluble ree unit cellulose solution, can obtain rare earth doped silicon oxide-germanium oxide class material.
Add TiO 2 sol and mix (F liquid) in E liquid, the quality percentage composition scope of titanium dioxide is 0-90% in the TiO 2 sol, and the molar ratio of titanium and element Ge can obtain titanium oxide-silicon oxide-germanium oxide class material at 0-100.
In F liquid, add soluble ree unit cellulose solution, can obtain rare earth doped titanium oxide-silicon oxide-germanium oxide class material.
Described rare earth element solution is included as the mixed solution of soluble salt of yttrium, praseodymium, neodymium, palladium, erbium, ytterbium element or one of them.
Liquid-phase deposition technique has been successfully applied to TiO
2, Al
2O
3, ZnO, ZnS, the preparation of materials such as CdS.Generally be to utilize precipitin reaction that these metallic cations negatively charged ion corresponding with it carry out to realize the preparation of material.Thereby control nucleation and the process of growth of these products in solution medium, the material shape that obtains having project organization and performance thus by controlling these metallic cations or the negatively charged ion release rate in solution.Yet for GeO
2, be difficult to obtain with Ge
4+Therefore the solution medium of ionic species stable existence also is difficult to by the synthetic germanium oxide class material of common liquid deposition principle.
Generally germanium oxide is difficult to be dissolved in the multiple solvent.Solubleness in water only is the every 100ml water of 0.405g, but there is in fact running balance of existence between germanium oxide and the formed ammonia germanium chelation structure form in the form that germanium oxide can chelation structure in ammonia soln.In the present invention, as complexing agent, as solvent, impelled the dissolving of germanium oxide in water with ammoniacal liquor in the mode of heated and stirred with water.Can be used as the good precursor of preparation germanium oxide sill by the aqueous solution of the germanium oxide that obtains after the filtration treatment.The aqueous solution of this germanium oxide is mixed by preset proportion with other solution state or dissolved colloidal state material and just can obtain various forms of germanium oxide class materials or germanium oxide class dopant material through thermal treatment.
Add the appropriate amount of acid example hydrochloric acid in this germanium oxide solution, sulfuric acid, acetate, phosphoric acid etc. after a while, just begin slowly to separate out the germanium oxide crystal grain as precipitation agent in the solution.It separates out principle is that the acid that adds is reacted with ammoniacal liquor, has broken the balance between the germanium oxide and ammonia germanium chelation structure in the solution, and balance is moved to the direction of separating out germanium oxide.Concentration by adjusting germanium oxide solution and the amount that adds acid can obtain the germanium oxide micro crystal material of different shapes and performance, as cube, and taper etc.
If in this solution, add polymer morphology control agent such as polyvinyl alcohol, polyacrylamide, polyacrylic acid, polyoxyethylene glycol, polyoxyethylene, polymaleic anhydride, Poly Dimethyl Diallyl Ammonium Chloride, polyvinylamine, poly-2-ethene tetrahydroglyoxaline, sodium polystyrene sulfonate, Sulfonated Copolymer of Styrene and Maleic Anhydride, open the mixture of pul resin or one of them, can also obtain the sub-micro sphere, taper germanium oxide micro crystal material, these germanium oxide microcrystal grain materials with different structure and pattern are in catalysis, and aspects such as quantum optics effect device have important application.
In this solution, add template, the germanium oxide crystallite of separating out will be on template deposition growing, remove the germanium oxide sill that just can obtain having the special template shape after the template through Overheating Treatment at last.If the aqueous solution of this germanium oxide is mixed by preset proportion with other solution state or dissolved colloidal state material, can separate out equally and have different structure, the germanium oxide microcrystal grain material of pattern and characteristic, after Overheating Treatment, it is material modified to obtain the germanium oxide crystallite, because the quantum effect of these crystallites makes these materials have special optoelectronic applications.
In this germanium oxide solution, put into the solid support material of various materials and shape, just can on carrier, slowly grow uniform germanium oxide membrane material, the thin-film material that grows does not have cracking and has very high bounding force with carrier surface, thickness has adjustability and controllability in 1 nanometer between several millimeters, and this is that conventional sol-gel processing institute is inaccessiable.And with chemical Vapor deposition process (CVD), magnetron sputtering method, ion implantation, the flame decomposition method, scorification, it but is a high flow rate that chemical gas phase axle phase sedimentation will deposit several millimeters mould material, inefficient thing.The mould material of preparing can be a nano film material, can be the porous thick film material also, has important application at aspects such as opto-electronic device and membrane catalytic reaction-discrete devices.
In addition, the aqueous solution of this germanium oxide can also be mixed by the co-precipitation effect on carrier, depositing various germanium oxide class materials and Germania-doped material by preset proportion with other solution state or dissolved colloidal state material, enlarge its range of application.
Put into special-shaped carrier in this germanium oxide solution, tubular as hole shape, male and fomale(M﹠F) shape or the like can slowly grow uniform germanium oxide membrane material easily on these special-shaped carriers.And this is a magnetron sputtering method, ion implantation, flame decomposition method, what scorification was difficult to realize.
The germanium oxide sill of different voidages will can also be obtained after the germanium oxide membrane material heat treatment that deposit.
The present invention compared with prior art has the following advantages:
(1) presoma-germanium oxide aqueous solution (B liquid) of the present invention's preparation is highly stable, and room temperature is placed and still kept clear more than 1 year, and just can prepare this aqueous solution presoma under very common condition.Also much lower as presoma on cost than the metal alkoxide that uses germanium.Particularly can obtain the germanium oxide sill of high solids content at an easy rate.And the very easily hydrolysis of the metal alkoxide of germanium, and very expensive, this brings great difficulty to the material preparation operation, thereby causes cost of manufacture very high.
(2) thin-film material of the present invention's preparation does not have cracking and has very high bounding force with carrier surface, and thickness has adjustability and controllability between 1 nanometer is to several millimeters.
This is that conventional sol-gel processing institute is inaccessiable.And with chemical Vapor deposition process (CVD), magnetron sputtering method, ion implantation, the flame decomposition method, scorification, it but is a high flow rate that chemical gas phase axle phase sedimentation will deposit several millimeters mould material, inefficient thing.
The mould material of preparing can be a nano film material, can be the porous thick film material also, has important application at aspects such as opto-electronic device and membrane catalytic reaction-discrete devices.
(3) aqueous solution of presoma-germanium oxide of the present invention and other solution state or dissolved colloidal state material are mixed by preset proportion add acid and on carrier, deposit various germanium oxide sills and Germania-doped material, enlarge its range of application by the co-precipitation effect.
And, adding appropriate amount of acid (example hydrochloric acid, sulfuric acid, put into special-shaped carrier in the aqueous solution of presoma-germanium oxide of the present invention acetate, phosphoric acid), as hole shape, tubular, male and fomale(M﹠F) shape or the like can slowly grow uniform germanium oxide membrane material easily on these special-shaped carriers.And this is a magnetron sputtering method, ion implantation, flame decomposition method, what scorification was difficult to realize.
The germanium oxide sill of different voidages will can also be obtained after the germanium oxide membrane material heat treatment that deposit.
(4) the present invention adopts the simplest equipment, under common reaction conditions, finished the synthetic of germanium oxide sill by simple reaction principle, greatly overcome traditional method equipment requirements height, the raw material costliness, severe reaction conditions is difficult to control, the material of making easily produces deficiencies such as defective, has greatly reduced the cost of manufacture of germanium oxide sill.
(5) reaction involved in the present invention is carried out in solution, be very easy to realize that the germanium oxide component realizes mixing of molecular level in liquid phase medium with other material component, thereby have the potentiality of exploitation high quality germanium oxide base novel material and Germania-doped novel material.
Description of drawings
The pattern of the germanium oxide class material of the present invention's preparation is seen shown in the accompanying drawing 1-5.
Accompanying drawing 1 is cube shaped germanium oxide material;
Accompanying drawing 2 is taper germanium oxide material;
Accompanying drawing 3 is rosette silicon oxide-germanium oxide material;
Accompanying drawing 4 is a sedimentary germanium oxide class material in kapillary;
The dense film material that accompanying drawing 5 forms after through 1300 ℃ of processing for the thin-film material that deposits.
Embodiment
Embodiments of the invention are as follows:
Embodiment one:
The liquid deposition preparation method of germanium oxide class material of the present invention comprises following preparation process:
(1) ammoniacal liquor dilution: ammoniacal liquor is mixed with water, and the volume ratio of control ammoniacal liquor and water is 1: 20, obtains A liquid;
(2) adding under the gentle stirring condition, the germanium oxide powder is joined in the A liquid, control: the mass ratio of germanium oxide and water is 7: 100, and the Heating temperature scope is 65 ℃, churning time 3 hours; With the liquid filtering that obtains, collecting filtrate is B liquid;
(3) add polyvinyl alcohol in B liquid, and stirred 2 hours, the add-on of polyvinyl alcohol is to add 10mg in the B liquid of every 40ml volume, obtains C liquid;
(4) with C liquid as lotion, adopt dip-coating method plated film on various glass substrates, pull rate 10cm/min 500 ℃ of thermal treatments, obtains the germanium oxide membrane material with the substrate of plated film.
(5) add water-reducible hydrochloric acid soln in B liquid, the add-on of hydrochloric acid soln is: the quality ratio of hydrochloric acid and ammoniacal liquor is 1.5, and the massfraction of described hydrochloric acid soln is 30%, obtains D liquid;
(6) D liquid was left standstill 4 days in room temperature, deposit the germanium oxide powder;
(7) add polyvinyl alcohol in D liquid, add-on is to add 7g in every 100ml D liquid, leaves standstill 30 minutes to 90 days in room temperature, deposits the germanium oxide powder of controllable appearance;
(8) in D liquid, put into quartz glass plate, left standstill 10 days, on carrier, slowly grow uniform germanium oxide membrane material in room temperature;
(9) D liquid slowly is passed in the hollow pipe, 1000 microns of caliber sizes, the flow control of feeding is at 0.001ml/min, circulation feeds, perhaps D liquid is filled hollow Guan Houyi end closure, after 4 days, can on inside pipe wall, be deposited the uniform germanium oxide membrane material of thickness.
(10) the above-mentioned germanium oxide class material that deposits is heat-treated, can obtain voidage at 2% germanium oxide class material, thermal treatment temp is 1300 ℃.
(11) add praseodymium chloride solution in B liquid, the molar ratio of germanium and praseodymium can obtain the germanium oxide class material of praseodymium element doping at 300: 1.
(12) add silicon dioxide gel and mix (E liquid) in B liquid, the quality percentage composition scope of silicon-dioxide is 20% in the silicon dioxide gel, and the molar ratio of silicon and element Ge can obtain silicon-dioxide-germanium oxide class material at 3: 2.
(13) adding can add praseodymium chloride solution in E liquid, and the molar ratio of germanium and praseodymium can obtain the silicon oxide-germanium oxide class material of praseodymium element doping at 300: 1.
(14) add TiO 2 sol and mix (F liquid) in E liquid, the quality percentage composition scope of titanium dioxide is 5% in the TiO 2 sol, and the molar ratio of titanium and element Ge can obtain titanium oxide-silicon oxide-germanium oxide class material at 1: 5.
(15) add praseodymium chloride solution in F liquid, the molar ratio of germanium and praseodymium can obtain the titanium oxide-silicon oxide-germanium oxide class material of praseodymium element doping at 300: 1.
Embodiment two:
The liquid deposition preparation method of germanium oxide class material of the present invention comprises following preparation process:
(1) ammoniacal liquor dilution: ammoniacal liquor is mixed with water, and the volume ratio of control ammoniacal liquor and water is 1: 100, obtains A liquid;
(2) adding under the gentle stirring condition, the germanium oxide powder is joined in the A liquid, control: the mass ratio of germanium oxide and water is 2: 110, and the Heating temperature scope is 25 ℃, churning time 29 hours; With the liquid filtering that obtains, collecting filtrate is B liquid;
(3) add polypropylene acid in B liquid, and stirred 2.5 hours, the add-on of polypropylene acid is to add 5g in the B liquid of every 40ml volume, obtains C liquid;
(4) with C liquid as lotion, adopt dip-coating method plated film on ceramic substrate, pull rate 20cm/min 800 ℃ of thermal treatments, obtains the germanium oxide membrane material with the substrate of plated film.
(5) add water-reducible sulphuric acid soln in B liquid, the add-on of sulphuric acid soln is 5 definite by the quality ratio of sulfuric acid and ammoniacal liquor, obtains D liquid; The massfraction of described sulphuric acid soln is 98%.
(6) D liquid was left standstill 4 hours in room temperature, deposit the germanium oxide powder;
(7) add polypropylene acid in D liquid, add-on is to add 18g in every 100ml D liquid, leaves standstill 10 hours in room temperature, deposits the germanium oxide powder of controllable appearance;
(8) in D liquid, put into ceramic plate, left standstill 30 days, on carrier, slowly grow uniform germanium oxide membrane material in room temperature;
(9) D liquid slowly is passed in the hollow pipe, 1 centimetre of caliber size, the flow control of feeding is at 0.1ml/min, and circulation feeds, and perhaps D liquid is filled hollow Guan Houyi end closure, after 7 days, can deposit the uniform germanium oxide membrane material of thickness on inside pipe wall.
(10) the above-mentioned germanium oxide class material that deposits is heat-treated, can obtain voidage at 37% germanium oxide class material, thermal treatment temp is 100 ℃.
(11) add Erbium trichloride solution in B liquid, the molar ratio of germanium and erbium can obtain the adulterated germanium oxide class of er element material at 100: 1.
(12) add silicon dioxide gel and mix (E liquid) in B liquid, the quality percentage composition scope of silicon-dioxide is 30% in the silicon dioxide gel, and the molar ratio of silicon and element Ge can obtain silicon-dioxide-germanium oxide class material at 9: 1.
(13) adding can add Erbium trichloride solution in E liquid, and the molar ratio of germanium and erbium can obtain the adulterated silicon oxide of er element-germanium oxide class material at 100: 1.
(14) in E liquid, add TiO 2 sol and mix (F liquid), the quality percentage composition scope of titanium dioxide is 1% in the TiO 2 sol, the molar ratio of titanium and element Ge can obtain titanium oxide-silicon oxide-germanium oxide class material at 1: 20.
(15) add to add Erbium trichloride solution in F liquid, the molar ratio of germanium and erbium is at 100: 1,, can obtain the adulterated titanium oxide-silicon oxide of er element-germanium oxide class material.
Embodiment three:
The liquid deposition preparation method of germanium oxide class material of the present invention comprises following preparation process:
(1) ammoniacal liquor dilution: ammoniacal liquor is mixed with water, and the volume ratio of control ammoniacal liquor and water is 1: 12, obtains A liquid;
(2) adding under the gentle stirring condition, the germanium oxide powder is joined in the A liquid, control: the mass ratio of germanium oxide and water is 2: 3, and the Heating temperature scope is 95 ℃, churning time 7 hours; With the liquid filtering that obtains, collecting filtrate is B liquid;
(3) add sodium polystyrene sulfonate in B liquid, and stirred 1 hour, the add-on of sodium polystyrene sulfonate is to add 0.1mg in the B liquid of every 40ml volume, obtains C liquid;
(4) with C liquid as lotion, adopt dip-coating method plated film on ceramic substrate, pull rate 20cm/min 1200 ℃ of thermal treatments, obtains the germanium oxide membrane material with the substrate of plated film.
(5) add water-reducible acetic acid solution in B liquid, the add-on of acetic acid solution is 0.7 to determine by the quality ratio of acid and ammoniacal liquor, obtains D liquid; The massfraction of described acetic acid solution is 19%.
(6) D liquid was left standstill 3 days in room temperature, deposit the germanium oxide powder;
(7) add sodium polystyrene sulfonate in D liquid, add-on is to add 0.1mg in every 100ml D liquid, leaves standstill 3 days hours in room temperature, deposits the germanium oxide powder of controllable appearance;
(8) in D liquid, put into plastic substrate, left standstill 3 days, on carrier, slowly grow uniform germanium oxide membrane material in room temperature;
(9) D liquid slowly is passed in the hollow pipe, 3 millimeters of caliber sizes, the flow control of feeding is at 0.1ml/min, and circulation feeds, and perhaps D liquid is filled hollow Guan Houyi end closure, after 4 days, can deposit the uniform germanium oxide membrane material of thickness on inside pipe wall.
(10) the above-mentioned germanium oxide class material that deposits is heat-treated, can obtain voidage at 51% germanium oxide class material, thermal treatment temp is 100 ℃.
(11) add neodymium chloride solution in B liquid, the molar ratio of germanium and neodymium can obtain the adulterated germanium oxide class of neodymium element material at 100: 7.
(12) add silicon dioxide gel and mix (E liquid) in B liquid, the quality percentage composition scope of silicon-dioxide is 40% in the silicon dioxide gel, and the molar ratio of silicon and element Ge can obtain silicon-dioxide-germanium oxide class material at 6: 4.
(13) adding can add neodymium chloride solution in E liquid, and the molar ratio of germanium and neodymium can obtain the adulterated silicon oxide of neodymium element-germanium oxide class material at 100: 7.
(14) in E liquid, add TiO 2 sol and mix (F liquid), the quality percentage composition scope of titanium dioxide is 3% in the TiO 2 sol, the molar ratio of titanium and element Ge can obtain titanium oxide-silicon oxide-germanium oxide class material at 1: 15.
(15) add neodymium chloride solution in F liquid, the molar ratio of germanium and neodymium can obtain the adulterated titanium oxide-silicon oxide of neodymium element-germanium oxide class material at 100: 7.
Embodiment four:
The liquid deposition preparation method of germanium oxide class material of the present invention comprises following preparation process:
(1) ammoniacal liquor dilution: ammoniacal liquor is mixed with water, and the volume ratio of control ammoniacal liquor and water is 1: 187, obtains A liquid;
(2) adding under the gentle stirring condition, the germanium oxide powder is joined in the A liquid, control: the mass ratio of germanium oxide and water is 3: 5, and the Heating temperature scope is 100 ℃, churning time 1 hour; With the liquid filtering that obtains, collecting filtrate is B liquid;
(3) add polyoxyethylene glycol in B liquid, and stirred 1 hour, the add-on of polyoxyethylene glycol is to add 1g in the B liquid of every 40ml volume, obtains C liquid;
(4) with C liquid as lotion, adopt dip-coating method plated film on ceramic substrate, pull rate 15cm/min 1400 ℃ of thermal treatments, obtains the germanium oxide membrane material with the substrate of plated film.
(5) add water-reducible phosphoric acid solution in B liquid, the add-on of phosphoric acid solution is 79 to determine by the quality ratio of acid and ammoniacal liquor, obtains D liquid; The massfraction of described acid solution is 0.1%.
(6) D liquid was left standstill 3 days in room temperature, deposit the germanium oxide powder;
(7) add polyoxyethylene glycol in D liquid, the add-on of polyoxyethylene glycol is to add 5g in every 100ml D liquid, leaves standstill 87 days hours in room temperature, deposits the germanium oxide powder of controllable appearance;
(8) in D liquid, put into metal substrate, left standstill 57 days, on carrier, slowly grow uniform germanium oxide membrane material in room temperature;
(9) D liquid slowly is passed in the hollow pipe glass, 1 millimeter of pipe diameter, the flow control of feeding is at 0.001ml/min, circulation feeds, perhaps D liquid is filled hollow Guan Houyi end closure, after 30 days, can on inside pipe wall, be deposited the uniform germanium oxide membrane material of thickness.
(10) the above-mentioned germanium oxide class material that deposits is heat-treated, can obtain voidage at 40% germanium oxide class material, thermal treatment temp is 150 ℃.
(11) add yttrium chloride solution in B liquid, the molar ratio of germanium and yttrium can obtain the adulterated germanium oxide class of yttrium material at 1000: 1.
(12) add silicon dioxide gel and mix (E liquid) in B liquid, the quality percentage composition scope of silicon-dioxide is 20% in the silicon dioxide gel, and the molar ratio of silicon and element Ge can obtain silicon-dioxide-germanium oxide class material at 6: 4.
(13) adding can add yttrium chloride solution in E liquid, and the molar ratio of germanium and yttrium can obtain the adulterated silicon oxide of yttrium-germanium oxide class material at 1000: 1.
(14) in E liquid, add TiO 2 sol and mix (F liquid), the quality percentage composition scope of titanium dioxide is 3% in the TiO 2 sol, the molar ratio of titanium and element Ge can obtain titanium oxide-silicon oxide-germanium oxide class material at 1: 15.
(15) add yttrium chloride solution in F liquid, the molar ratio of germanium and yttrium can obtain the adulterated titanium oxide-silicon oxide of yttrium-germanium oxide class material 1000.
Claims (10)
1. the liquid deposition preparation method of germanium dioxide material, it is characterized in that: described preparation method comprises following preparation process:
(1) ammoniacal liquor dilution: ammoniacal liquor is mixed with water, and the volume ratio of control ammoniacal liquor and water is 1: 200-1: 10, obtain A liquid;
(2) adding under the gentle stirring condition, the germanium oxide powder is joined in the A liquid, control: the mass ratio of germanium oxide and water is 0-0.5, and churning time 0.5-24 hour, the Heating temperature scope was 25-100 ℃; With the liquid filtering that obtains, collecting filtrate is B liquid;
(3) add high molecular weight water soluble polymer in B liquid, and stirred 0.5-4 hour, the add-on of high molecular weight water soluble polymer is to add the 0-20mg polymkeric substance in the B liquid of every 40ml volume, obtains C liquid;
(4) with C liquid as lotion, adopt dip-coating method plated film on substrate, pull rate 0.01-25.00cm/min 30-1500 ℃ of scope thermal treatment, obtains the germanium oxide membrane material with the substrate of plated film.
2. the liquid deposition preparation method of germanium dioxide material as claimed in claim 1, it is characterized in that: described preparation method comprises following preparation process:
(1) add water-reducible acid solution in B liquid, the add-on of acid solution is that 0.001-98.000 determines by the mass ratio of acid and ammoniacal liquor, obtains D liquid;
(2) D liquid was left standstill 30 minutes to 90 days in room temperature, deposit the germanium oxide powder;
(3) add high molecular weight water soluble polymer in D liquid, the add-on of high molecular weight water soluble polymer is to add 0-50g in every 100ml D liquid, leaves standstill 30 minutes to 90 days in room temperature, deposits the germanium oxide powder of controllable appearance;
(4) in D liquid, put into the solid support material of different shape, left standstill 30 minutes to 90 days, on carrier, slowly grow uniform germanium oxide membrane material in room temperature;
(5) the above-mentioned germanium oxide class material that deposits is heat-treated, can obtain the germanium oxide class material of voidage at 0-80%, thermal treatment temp is a 30-1500 ℃ of scope.
3. as the liquid deposition preparation method of claim 1,2 described germanium dioxide materials, it is characterized in that: in B liquid, add soluble ree unit cellulose solution, the molar ratio of germanium and rare earth element can obtain rare earth doped germanium oxide class material at 0-500.
4. as the liquid deposition preparation method of claim 1,2 described germanium dioxide materials, it is characterized in that: in B liquid, add silicon dioxide gel and mix (E liquid), the quality percentage composition scope of silicon-dioxide is 0-99% in the silicon dioxide gel, the molar ratio of silicon and element Ge can obtain silicon-dioxide-germanium oxide class material at 0-1000.
5. the liquid deposition preparation method of germanium dioxide material as claimed in claim 4 is characterized in that: add soluble ree unit cellulose solution in E liquid, can obtain rare earth doped silicon oxide-germanium oxide class material.
6. the liquid deposition preparation method of germanium dioxide material as claimed in claim 4, it is characterized in that: in E liquid, add TiO 2 sol and mix (F liquid), the quality percentage composition scope of titanium dioxide is 0-90% in the TiO 2 sol, the molar ratio of titanium and element Ge can obtain titania-silica-germanium oxide class material at 0-100; In F liquid, add soluble ree unit cellulose solution, can obtain rare earth doped titania-silica-germanium oxide class material.
7. as the liquid deposition preparation method of claim 3,5,6 described germanium dioxide materials, it is characterized in that: described rare earth element solution is included as the mixed solution of soluble salt of yttrium, praseodymium, neodymium, palladium, erbium, ytterbium element or one of them.
8. as the liquid deposition preparation method of claim 1,2 described germanium dioxide materials, it is characterized in that: described high molecular weight water soluble polymer is polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyacrylic acid, polyoxyethylene glycol, polyoxyethylene, polymaleic anhydride, Poly Dimethyl Diallyl Ammonium Chloride, polyvinylamine, poly-2-ethene tetrahydroglyoxaline, sodium polystyrene sulfonate, Sulfonated Copolymer of Styrene and Maleic Anhydride, open the mixture of pul resin or one of them; Described substrate and solid support material are glass, plastics, pottery or the metallic substance of different shape.
9. the liquid deposition preparation method of germanium dioxide material as claimed in claim 2 is characterized in that: described acid solution is the mixing solutions of hydrochloric acid, sulfuric acid, acetate, phosphoric acid or one of them, and the massfraction of described acid solution is 0.001 to 98%.
10. the liquid deposition preparation method of germanium dioxide material as claimed in claim 2, it is characterized in that: D liquid slowly is passed in the hollow pipe, caliber size is not less than 1 micron, the flow control that feeds is at 0-1000ml/min, circulation feeds, after 30 minutes to 90 days, can on inside pipe wall, deposit the uniform germanium oxide membrane material of thickness; D liquid is filled hollow Guan Houyi end closure, leave standstill 30 minutes to 90 days after, also can on inside pipe wall, deposit the uniform germanium oxide membrane material of thickness.
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