CN100506702C - Titanium oxide sol, thin film, and processes for producing these - Google Patents
Titanium oxide sol, thin film, and processes for producing these Download PDFInfo
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- CN100506702C CN100506702C CNB2004100597964A CN200410059796A CN100506702C CN 100506702 C CN100506702 C CN 100506702C CN B2004100597964 A CNB2004100597964 A CN B2004100597964A CN 200410059796 A CN200410059796 A CN 200410059796A CN 100506702 C CN100506702 C CN 100506702C
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Abstract
An aqueous dispersion of titanium oxide particles comprising chloride ion, and a Bronsted base other than chloride ion, preferably at least one kind of ion selected from nitrate ion and phosphate ion. Preferably the titanium oxide particles are predominantly comprised of brookite titanium oxide particles. The aqueous titanium oxide dispersion is prepared by hydrolyzed titanium tetrachloride in the presence of at least one kind of a Bronsted acid. A thin film formed from this aqueous titanium oxide dispersion exhibits good photo-catalytic activity, transparency and adhesion to a base material.
Description
The application is dividing an application of the Chinese patent application 99808599.5 submitted on May 14th, 1999.
Technical field
The thin film of titanium oxide and the manufacture method of above-mentioned titanium oxide sol and the manufacture method for preparing Titanium particles by this colloidal sol that the present invention relates to titanium oxide sol, use this colloidal sol on substrate surfaces such as pottery, plastics, to form.
This thin film of titanium oxide is transparent, has good photocatalysis, and good with the binding property of base material.
Background technology
Titanium dioxide (hereinafter claiming " titanium oxide ") is known generally to be existed with Detitanium-ore-type, brookite type, three kinds of crystallization phasess of rutile-type.When making by vapor phase process under the situation of titanium oxide by making titanium tetrachloride and oxygen etc. carry out mixed firing, the stable titanium oxide that generates at minimum temperature section is the titanium oxide of Detitanium-ore-type.When the titanium oxide that is obtained being applied thermal treatment calcine, obtain the titanium oxide of brookite types at 816～1040 ℃ temperature sections, obtain the titanium oxide (physics and chemistry is learned dictionary the 3rd edition, P.514～515) of rutile-type structure at the temperature section that is higher than said temperature.
In addition, about make the method for titanium oxide with liquid phase method, for example, boat wood, good stone Wei Men etc. have at length reported the situation (technical chemistry of the relevant crystallization phases that titanium oxide had that generates when the titanium tetrachloride aqueous solution hydrolysis, the 59th volume, o.11, P1295 (1956)).According to their conclusion, when adopting this method, in the solution of high density, mainly generate the titanium oxide of rutile-type, in the solution of lower concentration, then mainly generate the titanium oxide of Detitanium-ore-type.According to its report, in liquid phase, can not generate brookite type and titanium oxide that be finely particulate.Because raw material is a titanium tetrachloride, therefore coexisting certainly in the titanium oxide that is obtained has chlorion.
Report according to these and to judge, up to now, use liquid phase method to be difficult to stably make the titanium oxide of brookite type.According to above-mentioned vapor phase process, though can make it be transformed into the brookite type titanium oxide by titanium oxide being carried out high-temperature heat treatment, in the method, owing to thermal treatment makes particle growth, therefore, always all be difficult to obtain the brookite type crystalline titanium oxide of minuteness particle shape.
On the other hand, titanium oxide sol generally can prepare as follows, promptly, crystal form or amorphous Titanium particles are scattered in the dispersion medium, perhaps the precursors of titanium oxide of titan-alkoxide, titanium sulfate, titanium tetrachloride etc. is sneaked in the dispersion medium, wait by neutralization, hydrolysis then to form colloidal sol.
Titanium oxide sol can be used for making titanium dioxide powder, perhaps forms thin film of titanium oxide by colloidal sol being coated on the surface that surfaces such as glass or plastics make these article.
Known titanium is a kind of photosemiconductor, as long as its particle diameter is enough little, just can makes it have the transparency and can improve its photo-catalysis function.For the photo-catalysis function of titanium oxide, research and develop just energetically in recent years.As the method for utilizing this photocatalyst, for example can reach antifouling, remove purposes such as foul gas, kill bacteria such as ammonia by removing objectionable impurities, the form of the titanium oxide that uses in order to reach these purposes can be various forms such as loose particles, film, colloidal sol.When requiring the said titanium oxide goods that utilize photo-catalysis function to have the transparency, in most cases all be to use the film of titanium oxide.For this reason, can use the titanium oxide of solation as the raw materials for production of producing film.
Photo-catalysis capability about titanium oxide, the ability of known anatase-type titanium oxide is better than Titanium Dioxide (Rutile) Top grade, this is by both bandwidth decisions, the bandwidth of rutile-type is 3.02eV, the bandwidth of Detitanium-ore-type is 3.23eV, the difference of the two be about 0.2eV (pottery (セ ラ ミ Star Network ス) 31 (1996), No.10, P.817).Consider that from this viewpoint that can differ from the anatase-type titanium oxide with high bandwidth is well suited for using as photosemiconductor.Yet, about the brookite type titanium oxide, still seldom report the example that it is obtained as monomeric substance up to now, wherein, because the manufacturing of brookite type titanium oxide is always all at high temperature carried out, therefore cause its particles sintering, thereby can not obtain to can be used as the micropartical that photosemiconductor (photocatalyst) uses, so still do not obtain the knowledge of relevant brookite type titanium oxide so far fully with photocatalyst with high-specific surface area.
Recently, utilize the lighting fixtures of mode as film, someone has proposed following scheme, for example on the Glass tubing of luminescent lamp or its guard shield the coating titanium oxide sol to form film, when organism such as oil smoke is arranged on above-mentioned Glass tubing or its guard shield adhere to, decompose owing to the photocatalysis of titanium oxide impels these organism, thereby prevented the pollution of Glass tubing or its guard shield.Yet, using the colloidal sol that obtains according to the method described above to come under the film forming situation, the unlikely high film of the transparency that obtains, the particularly relevant brookite type thin film of titanium oxide that uses still is not reported so far as the example of the photocatalyst of lighting fixtures etc.
When utilizing as photocatalyst, require this film to have very high catalytic activity when formation thin film of titanium oxide on glass, plastics and other base materials and with it.Because photocatalysis is the reaction on particle surface, therefore, has high reactivity in order to make particle, the preferred micropartical that uses with high-specific surface area.In addition, under surperficial film forming situations such as lighting fixtures, it must be transparent requiring this film.In order to enhance the transparency, when using titanium oxide, wish to use micropartical too and preferably with form dispersed microparticles of primary particle as catalyzer.As countermeasure, always be the method that adopts the titanium oxide miniaturization that makes Detitanium-ore-type so far at this problem.
In addition, when on base material, forming thin film of titanium oxide, require the binding property of film and base material enough good, so that guarantee that film is not easy to peel off.
For the method that made titanium tetrachloride hydrolysis in the past, it is very little and its crystallinity is good, the titanium oxide sol that the transparency when making film is high to be difficult to make a kind of atomic particle diameter.
For the method that makes the alkoxy titanium compound hydrolysis, though can make the titanium oxide in the colloidal sol become very little micropartical, thus good powder characteristics had, and the price of alkoxy titanium compound is more much higher than titanium tetrachloride.
Summary of the invention
Problem in view of above-mentioned prior art existence, the purpose of this invention is to provide titanium oxide sol, use the film of this colloidal sol formation and the method for making Titanium particles by this colloidal sol, thereby when said titanium oxide sol being coated on the various base materials when forming thin film of titanium oxide on the surface at this base material, this film has the good photo-catalysis function and the transparency, and the binding property of film and base material is good.
Present inventors have carried out all research at the thin film of titanium oxide that is formed by titanium oxide sol, found that, in titanium oxide sol except having chlorion, also there are other brnsted bases simultaneously, be preferably either party or both sides in nitrate ion and the phosphate anion, so just can improve the performances such as binding property of the transparency, film and the base material of film, also find in addition, titanium oxide based on the brookite type titanium oxide has the photocatalysis performance that is parity with or superiority over anatase-type titanium oxide, has so far just finished the present invention.
Therefore, according to the present invention, can provide a kind of titanium oxide sol that contains chlorion and chlorion other brnsted bases in addition simultaneously.Said herein " brnsted base " is meant the proton acceptor in the Bronsted acid theory.
In addition, according to the present invention, can provide a kind of thin film of titanium oxide that uses above-mentioned titanium oxide sol on substrate surface, to form.
In addition, according to the present invention, can provide a kind of and be coated on the substrate surface and the article that form by above-mentioned titanium oxide sol.
In addition, according to the present invention, a kind of manufacture method of titanium oxide sol can be provided, said colloidal sol contains the Bronsted soda acid beyond chlorion and at least a chlorion, it is characterized in that, make titanium tetrachloride hydrolysis in the presence of at least a in being selected from Bronsted acid; A kind of manufacture method of being disperseed the titanium oxide sol form by the Titanium particles that contains the brookite type titanium oxide particularly is provided; And the manufacture method that a kind of Titanium particles is provided, it is characterized in that, utilize the titanium oxide sol of making by above-mentioned manufacture method to obtain Titanium particles.
In addition, according to the present invention, a kind of manufacture method of titanium oxide sol can be provided, said colloidal sol be chlorion and be selected from nitrate ion and phosphate anion in the either party or both sides in the presence of make based on the Titanium particles of brookite type titanium oxide and disperse to form, it is characterized in that, in 75～100 ℃ hot water, add titanium tetrachloride, then either party in nitrate ion and phosphate anion or both sides in the presence of, in the temperature range of 75 ℃～solution boiling point, make titanium tetrachloride hydrolysis; In addition, also can provide a kind of manufacture method of Titanium particles, it is characterized in that, utilize the titanium oxide sol of making according to above-mentioned manufacture method to obtain to contain the Titanium particles of brookite type titanium oxide.
Description of drawings
Fig. 1 is the summary section of an example of the expression preferable reaction unit that is used to make titanium oxide sol of the present invention.
Embodiment
Titanium oxide sol of the present invention contains chlorion and is selected from least a in other brnsted bases beyond the chlorion, not only photo-catalysis function is good by film that this colloidal sol forms, and particularly the transparency of the binding property of film and base material and film itself is also very good.
As the brnsted base that in titanium oxide sol of the present invention, contains, preferably from nitrate ion, phosphate anion, pyrophosphate ion, metaphosphate ion, multi-phosphate ion, acetate ion and organic acid ion, select, especially preferably from nitrate ion and phosphate anion, select.These brnsted bases can contain independent one or more combination wherein.As the organic acid ion, the acid group of methylsulfonic acid, ethyl sulfonic acid, Witco 1298 Soft Acid, propanesulfonic acid etc. preferably.The amount of the above-mentioned brnsted base that contains in titanium oxide sol not only is included in the amount that exists evenly in the solution, and in fact it be meant the ionic absolute magnitude that exists in system.These ionic content are preferably 50～10 by its total amount, 000ppm, more preferably 100～4,000ppm.
The dispersion medium of titanium oxide sol is the mixture of water or water and organic solvent normally.By titanium tetrachloride hydrolysis is obtained in the method for titanium oxide sol, generate hydrogenchloride owing to reacting.In the colloidal sol that so obtains, hydrogenchloride almost all is dissociated into chlorion and hydrogen ion.In general, evaporate into outside the system in the hydrolysis reaction of the major part in this hydrogenchloride under heating.In addition, when containing hydrogenchloride in the colloidal sol, consider that hydrogenchloride can hinder from colloidal sol acquisition titanium dioxide powder or acquisition thin film of titanium oxide, therefore, when make hydrogenchloride in the colloidal sol residual when above to a certain degree by hydrolysis reaction, usually should carry out dechlorination as much as possible and handle, no longer contain hydrogenchloride in the colloidal sol so that make.Yet, do not consider chlorion in this colloidal sol to the thin film of titanium oxide Effect on Performance in the past, consider from this viewpoint, still there is not the technology that can control chlorion in the colloidal sol so far.
Present inventors find, when containing chlorion in the colloidal sol, the thin film of titanium oxide that is formed by this colloidal sol has very strong photocatalysis, and it is good with the binding property of base material, and find, if except chlorion, when also having at least a in other brnsted bases such as nitrate ion, phosphate anion, can improve the transparency and the binding property of film further, so far just finish the present invention.Though its reason does not still have final conclusion, can think, because the acid catalysis effect that the nitric acid, phosphoric acid of coexistence etc. are had causes carrying out condensation reaction on the Titanium particles surface, thereby improved the film-forming properties of filming and the binding property with substrate of filming.
In titanium oxide sol, though as long as exist chlorion and at least a above ion that is selected from chlorion other brnsted bases in addition (hereinafter to be referred to as chlorion and other brnsted bases simultaneously, sometimes be also referred to as " chlorion etc. ") get final product, but, in order to improve the thin film of titanium oxide that forms and the binding property of base material on base material, the total amount of contained chlorion etc. is preferably more than 50ppm.Particularly when film be under the situation about forming by sintering, the content that makes chlorion etc. can further improve the binding property of film more than 50ppm.On the other hand,, for example work as its content and surpass 10 if the content of the chlorion in the colloidal sol etc. is too much, during 000ppm, the transparent variation of film.In the above range, particularly preferred scope is 100～4,000ppm.
Other brnsted bases beyond the chlorion are not particularly limited with respect to the ratio of chlorion, and with respect to chlorion 1mol, the total amount of other brnsted bases can change in the wide like this scope of 0.1～200mol.
In addition, amazingly be, be controlled in the above-mentioned scope, can make it generate the brookite type titanium oxide by content with other brnsted bases beyond chlorion and the chlorion.Its reason does not still have final conclusion.Contain rutile-type crystallization or Detitanium-ore-type crystallization separately with those or contain the two titanium oxide sol of rutile-type crystallization and Detitanium-ore-type crystallization simultaneously and compare, contain brookite type crystalline titanium oxide sol and have better the film transparency and photocatalysis performance.Though brookite type crystalline content ratio does not have particular determination, preferably in 10～100 weight % scopes, when its content ratio is 50～100%, can improve its effect more significantly.
Effect about above-mentioned chlorion etc. does not still have final conclusion, but can infer, in titanium oxide sol, electric repulsive interaction often take place between the particle of titanium oxide and the particle, therefore make particle obtain good dispersiveness, the result makes film have the good transparency and stripping strength.
Titanium particles in the titanium oxide sol is thin more, and the photocatalysis of the thin film of titanium oxide that obtains is just high more, and its transparency is also good more.Yet meticulous Titanium particles is difficult to make, and therefore, the Titanium particles size in colloidal sol is preferred in the scope of 0.01～0.1 μ m by the median size of primary particle.
For the photo-catalysis function and the transparency that improves the film that is formed by above-mentioned titanium oxide sol, above-mentioned titanium oxide sol is 0.01～0.1 μ m by median size preferably, and specific surface area is 20m
2The above brookite type titanium oxide of/g is that the Titanium particles of main body is scattered in the colloidal sol that forms in the mixture of water or water and organic solvent.
Past, in order to obtain the brookite type titanium oxide, just resemble and take method that anatase-type titanium oxide is heat-treated above-mentioned, when the particle of the brookite type titanium oxide that obtains by thermal treatment is made film, increase owing to the nodulizing in heat treatment process makes the diameter of particle, therefore can not be used for forming film fully.
In titanium oxide sol of the present invention, if the excessive concentration of the Titanium particles in the colloidal sol, then particle condenses easily, thereby makes the colloidal sol instability.On the other hand, if the concentration of Titanium particles is low excessively, to need in the colloidal sol painting process when forming film for example then can to cause spending the problem of more time etc.Consider that from these aspects the Titanium particles concentration (content) in titanium oxide sol is preferably 0.05～10mol/L.
For titanium oxide sol of the present invention, can adopt ordinary methods such as filtration, washing, drying to handle to obtain Titanium particles.The median size of this particle is preferably 0.01～0.1 μ m by the particle diameter of primary particle.By the brookite type titanium oxide is that the median size of the particle that obtains of the titanium oxide sol of main body is preferably 0.01～0.1 μ m, and specific surface area is preferably at 20m
2More than/the g.
In addition, when using titanium oxide sol to form film,, for example can in colloidal sol, add on a small quantity 10～10, the water-soluble polymer about 000ppm in order to improve the film-forming properties of film.As water-soluble polymer, preferably use polyvinyl alcohol, methylcellulose gum, ethyl cellulose, CMC, starch etc.
When titanium oxide sol of the present invention being applied on the substrate surfaces such as various materials, molding, can on the surface of base material, form thin film of titanium oxide.As base material, can be pottery, glass, metal, plastics, timber, paper etc., almost without limits to this.These base materials also can be the prior article of application.As base material, also can use the support of the catalyst that forms by aluminum oxide, zirconium dioxide etc., the catalyzer of thin film of titanium oxide is carried to be held on these base materials use as catalyzer.In addition, if with the glass of the lighting fixtures of luminescent lamp etc. or its plastic lousing etc. as base material, form thin film of titanium oxide in the above, then require the film that obtains to be transparent and to have photocatalysis, therefore, it can shield lights, and organism such as oil smoke is decomposed, thereby can prevent the pollution of glass or cover effectively.In addition, if on glass for building purposes or wall material, form thin film of titanium oxide, then can prevent from equally to pollute, therefore, in the time of on the window material of using it for high-rise etc. or wall material, just there is no need it is carried out cleaning work, thereby can cut down the overhead charges in building.
For titanium oxide sol is coated on the base material, can adopt base material be impregnated in method in the colloidal sol, colloidal sol is sprayed on method on the base material, colloidal sol is coated on method on the base material etc. with hairbrush.The glue spread of colloidal sol reaches 0.01～0.2mm with the thickness that can make liquid film and is advisable.Be dried removing moisture wherein after coating, thereby obtained film, this film can be directly as uses such as catalyzer.
When base material is under the situation about being made of thermotolerance materials such as metal, pottery, glass, can carry out sintering after forming thin film of titanium oxide, and film is bonded on the base material more firmly, can also improve the hardness of film simultaneously.This sintering temperature is preferably more than 200 ℃.The upper limit to sintering temperature is not particularly limited, can be according to the decision of the thermotolerance of base material, still,, can not further increase the hardness of film or the binding property of film and base material, so this higher limit is advisable with 800 ℃ even temperature is raised to very high.In addition, under titanium oxide is situation based on brookite type, in order to keep its crystal habit, can be at the temperature sintering below 700 ℃.Particularly preferred situation be have phosphate anion in the presence of make titanium tetrachloride hydrolysis, obtain to contain the titanium oxide sol of chlorion and phosphate anion whereby, at this moment needn't be to wherein adding tackiness agent, as long as more than 200 ℃ less than 500 ℃ lower temperature range under sintering, just can be on the surface of the heat-resistant material of glass, stainless steel etc. the formation film that binding property is good and hardness is high.
Atmosphere gas during to sintering is not particularly limited, can be in atmosphere sintering.Sintering time is not particularly limited, for example can sintering 1～60 minute.The thickness of thin film of titanium oxide is the scope of 0.05～1.0 μ m under the situation of above-mentioned glue spread.
In addition, in order to make the transparent film that forms by titanium oxide sol of the present invention have higher intensity and base material to be had higher bounding force, can in titanium oxide sol, add suitable adhesive.As tackiness agent, for example preferably use silicoorganic compound such as alkyl silicate.Addition to tackiness agent is not particularly limited, but with respect to the titanium oxide content in the titanium oxide sol of the present invention, is converted into SiO by alkyl silicate
2The time addition be suitably about 1～50 weight %.If addition less than 1 weight %, the effect of then adding tackiness agent is very low.On the other hand, when addition is crossed 50 weight %, though very big to the bond strength of base material, owing to Titanium particles is covered by tackiness agent fully, thereby its photocatalysis is weakened.As the addition means of tackiness agent, can be chosen in according to the character of tackiness agent and be about to make before the film method of it being sneaked in the colloidal sol or, but no matter be that any method can both obtain effect of the present invention in the method for sneaking at the very start in the colloidal sol.For this film that contains tackiness agent, sintering not also can sintering.
The thin film of titanium oxide that uses titanium oxide sol of the present invention to make is crystalline, titanium oxide microparticle wherein is very fine particle, do not contain impurity, and this titanium oxide microparticle disperses with the state that is in close proximity to 1 particle, therefore, its photo-catalysis capability and the transparency are all higher, particularly when titanium oxide be that its catalytic capability is higher when being principal constituent (for example more than 50% weight) with the brookite type titanium oxide.
The following describes the manufacture method of titanium oxide sol of the present invention.
Titanium oxide sol of the present invention, chlorion that preferably contains the afore mentioned rules amount etc. gets final product, and its method for making is not had particular determination.For example, with the alkoxy compound hydrolysis of titanium, obtain a kind of titanium oxide sol that contains a small amount of alcohols, to wherein adding HC1 etc., and then be selected from least a in nitrate ion and the phosphate anion etc. to wherein adding, preferably the concentration of chlorion etc. is also in above-mentioned scope.Yet, preferably use the titanium tetrachloride that has generated hydrogenchloride by hydrolysis to make.The following describes the manufacture method of using titanium tetrachloride to make titanium oxide sol.
When titanium tetrachloride hydrolysis, the hydrogenchloride that preferably prevents from as much as possible to generate is by overflowing in the reactive tank and it being remained in the colloidal sol as far as possible.If allow the hydrogenchloride that produces overflow on one side,, then be difficult to make the titanium oxide in the colloidal sol to become the little particle of particle diameter, and its crystallinity be also bad Yi Bian carry out the hydrolysis reaction of titanium tetrachloride.
Overflow if can not prevent the hydrogenchloride that when hydrolysis, produces fully, also can take to suppress the method for its effusion.As said method, get final product so long as can suppress the hydrogenchloride effusion, this there is not particular determination, for example can adopt the method for pressurization, but method the easiest and that effective means is to use the reactive tank that is equipped with reflux exchanger to be hydrolyzed and to react.Fig. 1 shows an example of this device.Shown in the figure, in a reactive tank 1 that titanium tetrachloride aqueous solution 2 is housed, be provided with reflux exchanger 3, stirrer 4, thermometer 5, be used for the device 6 of reacting by heating groove.In hydrolysis reaction, can generate the steam of water and hydrogenchloride, but therefore their major part, there is not almost the chlorination Hydrogen Energy to escape into space outerpace from reactive tank 1 by reflux exchanger 3 condensations and return in the reactive tank 1.
If the titanium tetrachloride concentration at the titanium tetrachloride aqueous solution that is used for hydrolysis reaction is low excessively, then reaction yield is low, thereby make the efficient when forming film reduce by obtaining titanium oxide sol, on the other hand, if the excessive concentration of titanium tetrachloride, then reaction is too fierce, and the Titanium particles that is obtained is difficult to attenuate, and its bad dispersibility, therefore be unfavorable for using as the formation material of transparent film.Preferred titanium tetrachloride concentration is 0.05～10mol/L, if make its hydrolysis by the heating titanium tetrachloride aqueous solution, then can obtain a kind of titanium oxide (TiO
2) particle be scattered in the water and the colloidal sol that forms.If use the reflux exchanger reaction that is hydrolyzed, then the titanium oxide concentration in obtaining colloidal sol is greatly in the scope of 0.05～10mol/L, and therefore, institute's colloidal sol that obtains is the directly coating use of conduct with preferred titanium oxide concentration just.In addition, also water or colloidal sol is concentrated can be added in the colloidal sol that obtains by hydrolysis reaction as required, so that the concentration of titanium oxide is adjusted in the above-mentioned scope.
The temperature of hydrolysis reaction preferably more than 50 ℃ to the scope between the titanium tetrachloride aqueous solution boiling point.If 50 ℃ of temperature less thaies, then hydrolysis reaction needs the long period.Hydrolysis reaction can carry out about 10 minutes to 12 hours under the condition that keeps said temperature.Hydrolysis temperature is high more, keeps the time of this temperature can be short more.
The hydrolysis reaction of titanium tetrachloride aqueous solution is carried out in the temperature range of 75 ℃～this aqueous solution boiling point.At this moment, the mixing solutions of titanium tetrachloride and water can be placed reactive tank be heated to preset temperature, also can at first water be placed reactive tank to heat in advance, to wherein adding titanium tetrachloride, again it is adjusted to preset temperature then.By such hydrolysis reaction, generally can obtain a kind of is principal constituent with the brookite type, and wherein mixing has the mixed oxidization of Detitanium-ore-type and/or rutile-type titanium.Wherein, in order to improve the containing ratio of brookite type titanium oxide significantly, preferred adopt following method, that is, add water in the reactive tank and be heated to 75～100 ℃ in advance, preferred 85～95 ℃, then to wherein adding titanium tetrachloride, temperature is adjusted to the scope of 75 ℃～solution boiling point, if preheating temperature is 85～95 ℃, then temperature is adjusted to the scope of 85 ℃～solution boiling point, reaction with this understanding is hydrolyzed.According to this method, may account for more than the 70 weight % at the brookite type titanium oxide that is obtained in whole titanium oxide.About generating with the brookite type titanium oxide is that the reason of the mixture of principal constituent does not still have final conclusion, but can infer, the mixed solution of the brnsted base beyond employing contains chlorion and chlorion, and hydrolysis temperature is adjusted to more than 50 ℃ between the boiling point of titanium tetrachloride aqueous solution, being hydrolyzed with this understanding, just might to generate above-mentioned be the mixture of principal constituent with the brookite type titanium oxide, as Bronsted acid, preferably boiling point is higher than the nitric acid or the phosphoric acid of hydrochloric acid.
Be hydrolyzed when reaction, the heat-up rate of titanium tetrachloride aqueous solution is fast more, and the particle that is obtained is just thin more, therefore, heat-up rate preferably 0.2 ℃/more than the min, more preferably 0.5 ℃/more than the min.
According to the Titanium particles in the solution of this method acquisition, its median size preferably in the scope of 0.01～0.1 μ m, can become the good particle of crystallinity like this.
The manufacture method of titanium oxide sol of the present invention can be an intermittent type, can be continous way also, in continous way, for example reactive tank is made succeeding vats, on one side to wherein dropping into titanium tetrachloride and water continuously, from the opposition side-draw of input port go out reaction solution on one side, and carry out dechlorination continuously and handle.
The colloidal sol that generates is carried out dechlorination handle, perhaps in the scope that does not have influence, take to add processing such as water or dehydration chlorine ion concentration is adjusted to 10, below the 000ppm.
Dechlorination is handled and can be undertaken by general known method, for example can adopt methods such as electrodialysis, ion exchange resin, electrolysis.Less than 10, add either party or both sides in nitric acid and the phosphoric acid to chlorine ion concentration in the colloidal sol of 000ppm, these add the ionic total amount and are preferably 50～10,000ppm.Nitric acid and phosphoric acid also can add when carrying out the hydrolysis reaction of titanium tetrachloride.
As the dispersion medium of titanium oxide sol of the present invention, generally make the mixture of water or water and organic solvent.Organic solvent can join in the reacted colloidal sol of titanium tetrachloride hydrolysis, also can add in advance in the aqueous solution of titanium tetrachloride, and then make its reaction that is hydrolyzed.When containing organic solvent in the dispersion medium, the colloidal sol that is generated also can be used as titanium oxide coating and uses, and at this moment the preferred concentration of titanium oxide is 0.05～10mol/L.After colloidal sol generates, add again under the situation of organic solvent, can take as required with the concentration that colloidal sol concentrates, processing such as dehydration improves titanium oxide, perhaps to wherein adding organic solvent, so that the titanium oxide concentration in the colloidal sol is adjusted in the above-mentioned scope.
Organic solvent is preferably hydrophilic, for example can enumerate the monohydroxy-alcohol or the polyvalent alcohol of methyl alcohol, ethanol, ethylene glycol etc.; The ketone of acetone etc.; The ester class of ethyl acetate etc.; Cellosolve classes such as ethyl cellosolve etc.These solvents can be single solvent or their mixture.Organic solvent can mix by measuring arbitrarily with respect to colloidal sol, but organic solvent is with respect to 100 weight parts of the water in the colloidal sol, to be advisable below 2,000 weight parts.
When forming thin film of titanium oxide with titanium oxide sol of the present invention, preferably directly use the colloidal sol that in hydrolysis reaction, generates, also can earlier this colloidal sol be made titanium dioxide powder, again this powder is scattered in the water to make colloidal sol, use is provided then, but this is not a preferable methods, because the surfactivity of Titanium particles is very high, finer particles, its activity is high more, so be difficult to be scattered in the water, just become aggregate easily, with the film that such Titanium particles is made, its transparency is low, and photocatalysis is also poor.
Enumerate embodiment below and specifically describe the present invention, but the present invention is not subjected to the qualification of these embodiment.
In following embodiment, the evaluation of crystalline titanium dioxide structure and the containing ratio with titanium oxide of definite crystalline texture are measured by the following method.
The position at brookite (Brookite) type as the main crystallographic system of titanium oxide, anatase octahedrite (Anatase) type, three kinds of X ray peaks of rutile (Rutile) type has been shown in the table 1 (JCPDS card extracts), and as shown in table 1, the lap at these peaks is more.Particularly the d value of the main peak of brookite type and Detitanium-ore-type (strength ratio 100) is respectively 3.52 (crystal planes 120) and 3.51 (crystal planes 101), and at the Cu pipe ball that carries out using when X-ray diffraction method is measured, its 2 θ corner connection is bordering on 28.1 °.Below 0.1 °,, therefore can not recently obtain its containing ratio by the differential seat angle of 2 θ according to the main peak intensity of the two because main peak is overlapped.In addition, the brookite type titanium oxide locates also to have a peak in d value 3.47 (crystal plane 111).At above-mentioned three's place, peak, 2 θ all are near 28.1～28.5 °, overlap basically.
As mentioned above, the strength ratio of brookite type and the two main peak of Detitanium-ore-type can't be obtained, therefore use not peak in this article with 121 of the brookite types of the peak overlapping of Detitanium-ore-type, obtain strength ratio (peak intensities that brookite type is 121)/(intensity of three's overlapping peaks) of this peak and the overlapping peaks that forms by above-mentioned three peaks, obtain the titanium oxide containing ratio of brookite type and Detitanium-ore-type then according to this ratio.In addition, for Titanium Dioxide (Rutile) Top grade, can obtain its containing ratio according to its main peak (110 face) and the strength ratio (the main peak intensity of rutile-type)/(intensity of three's overlapping peaks) of above-mentioned three's overlapping peaks.Use X-ray diffraction device when practical measurement (electric (strain) of science system, the special floating Rake this (ロ--Off レ Star Network ス) of RAD-B labor) when carrying out X-ray diffraction mensuration, carries out the quantitative analysis of data processing.
Table 1 JCPDS card is taken passages (card numbering)
In the following embodiments, as the characteristic of titanium oxide sol of the present invention, carry out the evaluation of following film rerum natura.
The evaluation of film rerum natura
Coatings formulated liquid 2m1 in embodiment or the comparative example is coated on the soda-lime glass (substrate) of a 76 * 26mm, it is kept 10 minutes to remove the unnecessary feed liquid that is coated with under plumbness, so film.After filming, carry out drying or sintering according to the preset temperature of putting down in writing in embodiment or the comparative example (hereinafter referred to as " film-forming temperature ", the temperature of its expression heat-agglomerating), obtained thin film of titanium oxide (the about 0.2 μ m of thickness).Measure the transparency, photo-catalysis capability, binding property, tack and the pencil hardness of this film.
The turbidometer (according to JISK 6718) of the transparency-use (having) Tokyo electricity look technology セ Application -society's system is measured, and estimates by following three ranks.
◎ ... muddy rate is less than 2.0%
Zero ... muddy rate more than 2.0% less than 5.0%
* ... muddy rate is more than 5%
Photo-catalysis capability-several red ink are coated on the substrate, according to 2.1mW/cm
230 minutes ultraviolet ray (365nm) of uitraviolet intensity irradiation, judge the degree of fading of red ink by Three Estate with visual method
◎ ... fully fade
Zero ... have the part of not fading
* ... do not fade
With the binding property of substrate-wipe test, smear alcohol and wipe test and estimate according to smearing water.The eraser (キ system ワ イ プ) (Network レ シ ア society system) that water or alcohol is arranged with a libation at an ancient wedding ceremony reciprocal scrubbing brush 10 times on the soda-lime glass substrate is then reciprocally wiped 10 times with an exsiccant eraser, then the state of filming by following Three Estate evaluation with visual method.
◎ ... film and go up no scar
Zero ... filming upward, some part has scar
* ... have on filming to come off
The chessboard grid method that tack is tested-stipulated according to JIS K 5400 carries out.Cut the 1mm that is spaced apart of cut, test with 100 number of squares.
Pencil hardness-undertaken by pencil hardness test method (JIS K 5400).
Embodiment 1
Add entry in titanium tetrachloride (purity 99.9%), so being mixed with a kind of titanium tetrachloride concentration is the solution of 0.25mol/L (being 2 weight % when being converted into titanium oxide).At this moment use ice-cooledly, rise to more than 50 ℃ so that prevent the temperature of the aqueous solution.Then this aqueous solution 1L is packed in the reactive tank that has reflux exchanger as shown in Figure 1, be heated near boiling point (104 ℃) and under this temperature, keep 60 minutes with the reaction that is hydrolyzed.After the colloidal sol cooling that will be obtained, remove the residual chlorine that in reaction process, generates with electroosmose process, so be mixed with chloride ion-containing (C1 ion) 1, the colloidal sol of 000ppm.Use the electrodialysis unit G3 type of Asahi Chemical Industry's industry (strain) system during electrodialysis, under the condition of monitoring colloidal sol pH, carry out electrodialysis.In above-mentioned colloidal sol, add nitric acid then, contain 3 in the colloidal sol, the NO of 000ppm so that make
3Ion.
To the above-mentioned water-soluble polymer polyvinyl alcohol that adds in the titanium oxide sol that contains chlorion and nitrate ion as film coalescence aid for preparing, its add-on is 1 of a sol solutions weight, 000ppm.This colloidal sol is not through still observing the settled phenomenon of titanium oxide microparticle of generation more than one day.
Particle in the colloidal sol is taken out a part, use the infiltration type electron microscope observation, the median size that records these particles is 0.018 μ m.Measure the crystalline texture of this titanium oxide then with X-ray diffraction method.The strength ratio (intensity of the peak intensity that brookite type is 121/three's overlapping peaks) that the result records the X ray peak is 0.35, but does not observe the peak of rutile-type.This result shows that the titanium oxide that is obtained is crystalline, according to above-mentioned peak intensity ratio can in the hope of, this titanium oxide is made up of the Detitanium-ore-type of about 40 weight % and the brookite type of about 60 weight %.
Prepare then (to be converted into SiO as the methanol solution of the tetraethyl orthosilicate of tackiness agent
2Concentration be 0.25 weight %).
The above-mentioned colloidal sol aqueous solution is mixed by weight 1:1 with this binder solution, so made the coating of titanium oxide sol.The one-tenth of this coating is grouped into and is shown in Table 2.Estimate the rerum natura of above-mentioned coating solution according to above-mentioned evaluation method to film.But, the Heating temperature of filming is set at 100 ℃.Evaluation result to the film of acquisition like this is shown in Table 3.
Embodiment 2
According to similarly to Example 1 method preparation titanium oxide sol, and then with this colloidal sol formation film and estimate the rerum natura of this film.Used system component and manufacture method thereof are all identical with the foregoing description 1, but will heat (sintering) temperature change is 400 ℃.System component is shown in Table 2, and the evaluation result of film rerum natura is shown in Table 3.
Comparative example 1～4
Prepare titanium oxide sol similarly to Example 1, and then form film and estimate the rerum natura of this film with this colloidal sol.But do not add nitric acid and replace chlorion, the addition of chlorion is shown in Table 2.In comparative example 1 and 2, do not add tetraethyl orthosilicate (tackiness agent).The detailed composition of coating composition is shown in Table 2, and the evaluation result of film rerum natura is shown in Table 3.
Embodiment 3～12
Prepare titanium oxide sol similarly to Example 1, and then form film and estimate the rerum natura of this film with this colloidal sol.But changed the addition of phosphoric acid and nitrate ion.The detailed composition of coating composition is shown in Table 2, and the evaluation result of film rerum natura is shown in Table 3.
In addition, aspect the particle diameter and crystal habit of titanium oxide, comparative example 1,2 is also all almost identical with embodiment 1,2 with embodiment 3～12.
Embodiment 13
Distilled water 954ml packed into to be had in the reactive tank of reflux exchanger as shown in Figure 1, heats to 95 ℃.To wherein adding phosphoric acid, make PO
4Ion equals 200ppm.Keeping under the condition of about 200rpm stirring velocity, the aqueous solution 46ml of titanium tetrachloride (Ti content: 16.3 weight %, proportion 1.59, purity 99.9 weight %) is being splashed in the above-mentioned aqueous solution in the reactive tank according to the speed of about 5ml/min.At this moment note not allowing the temperature of reaction solution descend.As a result, the concentration of titanium tetrachloride is 0.25mol/L (being converted into titanium oxide is 2 weight %).
After reaction solution is dripped, in reactive tank, occur the white casse thing immediately, but at this moment continue to keep original temperature, drip finish after with the solution heating so that it is warming up to (104 ℃) near the boiling point, under this state, keep 60 minutes so that the end that reacts completely.After the cooling, remove the residual chlorine that in reaction, generates with electroosmose process, the pH value is adjusted to 1.9 (chlorion 600ppm, phosphate anion 200ppm), be equivalent to the water-soluble polymer polyvinyl alcohol of titanium oxide content 0.1 weight % to wherein adding then, thereby obtain titanium oxide sol (TiO as film coalescence aid
2About 0.25mol/L).This colloidal sol is stable, through still not observing the settled phenomenon of titanium oxide microparticle of generation more than 30 days.
The part of this colloidal sol is filtered, be dried under 60 ℃ with vacuum drier then, similarly it is carried out quantitative analysis with the powder taking-up of generation and with the foregoing description, the result shows, the ratio of (peak intensities that brookite type is 121)/(intensity of three's overlapping peaks) is 0.38, and the ratio of (the main peak intensity of rutile-type)/(intensity of three's overlapping peaks) is 0.05.The result who obtains according to these numerical value shows, the titanium oxide that is obtained is the crystalline titanium oxide that the Detitanium-ore-type of the rutile-type of a kind of brookite type by about 70.0 weight %, about 1.2 weight % and about 28.8 weight % is formed.In addition, find with this micropartical of infiltration type electron microscope observation the time that the median size of its primary particle is 0.015 μ m.In addition, the result who measures with the BET method shows that this atomic specific surface area is 140m
2/ g.
The one-tenth of coating is grouped into and the evaluation result of film rerum natura is shown in Table 3.
Embodiment 14
Make titanium tetrachloride hydrolysis according to similarly to Example 1 hydrolysising condition, obtained to contain the colloidal sol of 0.25mol/L titanium oxide.Before carrying out electrodialysis, earlier with this colloidal sol evaporation concentration so that titanium oxide concentration wherein becomes 2.5mol/L (being converted into titanium oxide is 20 weight %), remove residual chlorine with electroosmose process then, chlorion at this moment is about 1,200ppm.
In above-mentioned colloidal sol, add nitric acid and phosphoric acid then, make NO wherein
3Ion becomes 2,000ppm, PO
4Ion becomes 1,000ppm.In the titanium oxide sol of adjusting chlorion, nitrate ion and phosphate anion like this, add methyl alcohol, according to the amount shown in the table 2 it is mixed with polyvinyl alcohol as water-soluble polymer then, obtained titanium oxide sol (TiO as solvent
2About 0.5mol/L).
Use this colloidal sol and above-mentionedly similarly make film and the rerum natura of this film is estimated.Institute obtains and the results are shown in the table 3.Should illustrate that the median size of this Titanium particles, the ratio of each crystal type and specific surface area thereof are all almost identical with embodiment 1,2.
Industrial applicibility
Titanium oxide sol of the present invention except containing chlorion, also contain be selected from chlorion with More than at least a in other outer brnsted bases, preferably contain nitrate ion and/ Or phosphate anion, this colloidal sol is being coated on the various base materials when forming thin film of titanium oxide, This film is transparent and has good photocatalysis. Particularly working as titanium oxide is brockite During type, its photocatalysis is higher. In addition, the hardness height of the film that obtains, and with base material Cohesive is good.
Therefore, the film on the base material is durability, when film being used for ligthing paraphernalia for example In the time of above glass tube or its cover etc., it neither can interdict light, can keep in long-time again Photocatalysis.
Titanium oxide sol of the present invention can use with the aqueous systems manufacturing of titanium tetrachloride as raw material, Therefore its raw material is inexpensive, and can easily form film by this colloidal sol, thereby economically Also very favourable.
The film that is particularly formed by the titanium oxide sol that contains nitrate ion, its transparency more High. In addition, if contain phosphate anion in the colloidal sol, then work as this colloidal sol at the soda-lime glass substrate When carrying out sintering behind the upper formation film, phosphate anion have the reduction that prevents photo-catalysis capability and Keep the effect of high light catalytic capability.
Claims (14)
1, a kind of titanium oxide sol, it contains chlorion and at least a brnsted base that is selected from nitrate ion, phosphate anion, pyrophosphate ion, metaphosphate ion, multi-phosphate ion, methanesulfonate ion, ethyl sulfonic acid radical ion, Witco 1298 Soft Acid radical ion and the propanesulfonic acid radical ion, wherein, the content of chlorion and this brnsted base counts 50～10,000ppm (weight) by the negatively charged ion total amount of chlorion in the titanium oxide sol and this brnsted base.
2, by the described titanium oxide sol of claim 1, wherein, Titanium particles has the median size of 0.01～0.1 μ m.
3, by claim 1 or 2 described titanium oxide sols, wherein, the content of Titanium particles in titanium oxide sol is 0.05～10mol/L.
4, by claim 1 or 2 described titanium oxide sols, it also contains 10～10, the water-soluble polymer of 000ppm (weight).
5, by claim 1 or 2 described titanium oxide sols, it also contains tackiness agent.
6, by the described titanium oxide sol of claim 5, wherein, said tackiness agent comprises alkyl silicate.
7, a kind of thin film of titanium oxide, it is to use the described titanium oxide sol of claim 1 to form on substrate surface.
8, by the described thin film of titanium oxide of claim 7, wherein, said base material is to be made by at least a material that is selected from pottery, metal, glass, plastics, paper and the timber.
9, by the described thin film of titanium oxide of claim 7, wherein, said base material is to be made of at least a thermotolerance material that is selected from pottery, metal and the glass, and thin film of titanium oxide is through the incinerating film.
10, a kind of goods, it is made by the described titanium oxide sol of coating claim 1 on substrate surface.
11, by the described goods of claim 10, wherein, above-mentioned base material is to be made of at least a material that is selected from pottery, metal, glass, plastics, paper and the timber.
12, a kind of manufacture method of titanium oxide sol, said colloidal sol contains the brnsted base beyond chlorion and at least a chlorion, it is characterized in that, be selected from nitrate ion containing, phosphate anion, pyrophosphate ion, metaphosphate ion, the multi-phosphate ion, the methanesulfonate ion, the ethyl sulfonic acid radical ion, make titanium tetrachloride hydrolysis under the existence of the solution of at least a brnsted base in Witco 1298 Soft Acid radical ion and the propanesulfonic acid radical ion, wherein, the content of chlorion and brnsted base is mixed with by the negatively charged ion total amount of chlorion in the titanium oxide sol and this brnsted base counts 50～10,000ppm (weight).
13, by the manufacture method of the described titanium oxide sol of claim 12, wherein the hydrolysis reaction of titanium tetrachloride is to carry out in being equipped with the reactive tank of reflux exchanger.
14, by the manufacture method of the described titanium oxide sol of claim 12, wherein, brnsted base is at least a ion that is selected from nitrate ion and phosphate anion.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP132195/1998 | 1998-05-14 | ||
| JP13219598 | 1998-05-14 | ||
| JP132195/98 | 1998-05-14 | ||
| JP109171/99 | 1999-04-16 | ||
| JP109171/1999 | 1999-04-16 | ||
| JP10917199 | 1999-04-16 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99808599 Division CN1219703C (en) | 1998-05-14 | 1999-05-14 | Titanium oxide sol, thin film, and process for producing these |
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| Publication Number | Publication Date |
|---|---|
| CN1559914A CN1559914A (en) | 2005-01-05 |
| CN100506702C true CN100506702C (en) | 2009-07-01 |
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ID=34196314
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99808599 Expired - Fee Related CN1219703C (en) | 1998-05-14 | 1999-05-14 | Titanium oxide sol, thin film, and process for producing these |
| CNB2004100597964A Expired - Fee Related CN100506702C (en) | 1998-05-14 | 1999-05-14 | Titanium oxide sol, thin film, and processes for producing these |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 99808599 Expired - Fee Related CN1219703C (en) | 1998-05-14 | 1999-05-14 | Titanium oxide sol, thin film, and process for producing these |
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| TW (2) | TWI241278B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004161573A (en) * | 2002-11-15 | 2004-06-10 | Nippon Parkerizing Co Ltd | Titanium oxide sol, titanium oxide coating film, and its forming method |
| CN100366796C (en) * | 2005-04-22 | 2008-02-06 | 吉林大学 | Method for preparing film of inorganic phosphate in aqueous solution |
| CN100530516C (en) * | 2007-01-19 | 2009-08-19 | 上海和颐新材料有限公司 | Water paint containing brockite type TiO2 and its use |
| TWI421215B (en) * | 2009-09-30 | 2014-01-01 | Univ Nat Cheng Kung | Titanium dioxide gel and its application method |
| CN101830641B (en) * | 2010-04-01 | 2013-08-14 | 北京燕山润泽清洁能源技术开发有限公司 | Preparation method of self-assembly nano-crystalline titanium dioxide film |
| CN114272853B (en) * | 2021-12-24 | 2023-06-20 | 河北复朗施纳米科技有限公司 | Nanometer antibacterial coating manufacturing device |
-
1999
- 1999-05-14 TW TW93132721A patent/TWI241278B/en not_active IP Right Cessation
- 1999-05-14 CN CN 99808599 patent/CN1219703C/en not_active Expired - Fee Related
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| CN1559914A (en) | 2005-01-05 |
| TW200508154A (en) | 2005-03-01 |
| TWI241278B (en) | 2005-10-11 |
| TWI230688B (en) | 2005-04-11 |
| CN1219703C (en) | 2005-09-21 |
| CN1309621A (en) | 2001-08-22 |
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