CN1218878C - Normal temperature solidified titania sol - Google Patents
Normal temperature solidified titania sol Download PDFInfo
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- CN1218878C CN1218878C CN 03119113 CN03119113A CN1218878C CN 1218878 C CN1218878 C CN 1218878C CN 03119113 CN03119113 CN 03119113 CN 03119113 A CN03119113 A CN 03119113A CN 1218878 C CN1218878 C CN 1218878C
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Abstract
The present invention relates to titanium dioxide sol, particularly to titanium dioxide sol which is solidified at normal temperature. Self-generation crystal seeds are obtained by hydrolyzing inorganic titanium compound solution, white deposition is obtained by hydrolyzing the inorganic titanium compound at normal pressure under the action of the crystal seeds, and the white deposition is peptized in inorganic acid in order to obtain the titanium dioxide sol which is solidified at normal temperature. The titanium dioxide sol which is provided by the present invention and is solidified at normal temperature can form into titanium dioxide with an anatase crystal form without sintering at high temperature. The titanium dioxide sol can be extremely and conveniently used as a self-cleaning product at normal temperature, and is prepared by inorganic materials. In addition, the present invention has the advantages of low cost, low operating temperature, simple device, no pollution, easy popularization and easy industrial production.
Description
Technical field
The present invention relates to TiO 2 sol, relate in particular to a kind of preparation method of TiO 2 sol of ambient cure.
Background technology
Nano titanium oxide be meant particle diameter in 100 nanometers with interior titanium dioxide.In recent years, performances such as the automatically cleaning of nano titanium oxide, antibiotic, antifog and photocatalytic activity are subjected to people and pay close attention to widely, and particularly the development of self-cleaning nona titania coating has had a series of patent and bibliographical information with exploitation.As: in CN1224036A, disclosing a kind of sol-gel method that adopts prepares, mixed the TiO 2 sol of mineral compound nanoparticle, the titanium dioxide film materials that is coated by this TiO 2 sol can reach highly hydrophilic after UV-irradiation, therefore this TiO 2 sol can be used for glass, ceramic tile, antifog and the automatically cleaning of body surfaces such as mirror, but mineral compound nanoparticle wherein is directly to be added in the TiO 2 sol, because nanoparticle all has the characteristic of high surface energy and big specific surface area, therefore, the mineral compound nanoparticle very easily condenses or reunites, and then causes that the mineral compound nanoparticle disperses problems such as inhomogeneous and sedimentation in TiO 2 sol.
At application number is in the patent application of 00109176.X, disclose a kind of by titanic acid ester acid hydrolysis and synthetic TiO 2 sol, this TiO 2 sol has overcome the problem of condensing or reuniting, but the film with this colloidal sol coating must just have super parents' performance through high-temperature heat treatment, therefore this TiO 2 sol is used inconvenient, cost height, expensive big.
Though the TiO 2 sol of above mentioned sol-gel method preparation is fabulous in aspect performances such as antifog, automatically cleaning and transparences, but have following shortcoming simultaneously in this: (1) is the feedstock production TiO 2 sol with the organic titanium, the cost of material height, the industrial production cost height; (2) after prepared colloidal sol is coated with into film, this film must just may change into anatase titanium dioxide through high-temperature heat treatment, just has super parents' performance, need expend more thermal energy, and under a lot of practical occasions, be difficult to realize high-temperature heat treatment, industrialization poor practicability; (3) TiO 2 sol performance less stable, nanoparticle is easily reunited.
Summary of the invention
The objective of the invention is to,, provide a kind of TiO 2 sol of the ambient cure that obtains by the inorganic titanium compound hydrolysis in order to overcome above-mentioned organic titanium cost of material height, to need high-temperature heat treatment and nanoparticle that defectives such as reunion easily take place.
The preparation method's of the TiO 2 sol of ambient cure provided by the invention step is:
(1) preparation crystal seed
(a) with TiO
2The content meter, getting concentration is the inorganic titanium compound aqueous solution of 80～300g/l, and the inorganic titanium compound aqueous solution is heated to 28～85 ℃, with alkali lye the inorganic titanium compound pH value of water solution is adjusted into 1.5～4, stirs insulation down, obtains metatitanic acid crystal seed vitreosol;
(b) or with TiO
2The content meter, getting concentration is the meta-titanium acid solution of cleaning of 80～300g/l, and behind the hydro-oxidation sodium meta-titanium acid solution pH value is adjusted into 7.5～8.0, promptly has positive sodium titanate to form; Positive sodium titanate is contacted with cold water, hydrolysis generates positive metatitanic acid and sodium hydroxide again, and filtration, washing obtain titanic acid crystals kind;
(c) or with TiO
2The content meter, get the titanium sulfate solution that concentration is 80～300g/l, adding phosphoric acid accent pH is 3.0～3.5, generate white titanium phosphate precipitation, after filtration, the sodium hydroxide of washing back and liquid boils 1～5h altogether under 70～100 ℃, generate positive sodium titanate, more positive sodium titanate is contacted with cold water, just can hydrolysis generate positive metatitanic acid and sodium hydroxide, filtration, washing obtain titanic acid crystals kind.
(2) preparation white depositions
The metatitanic acid crystal seed vitreosol of step (1) preparation was boiled 0.5～6 hour under 50～140 ℃ of temperature, generate white depositions, after filtration, washing, obtain white depositions;
Under room temperature～100 ℃, can further in the metatitanic acid crystal seed vitreosol of step (1) preparation, add inorganic titanium compound solution, the amount that makes crystal seed in this vitreosol is TiO in the inorganic titanium compound solution
23～18% of total amount is with TiO
2Content meter, inorganic titanium compound strength of solution are 80～300g/l;
Perhaps adding concentration in the titanic acid crystals kind of above-mentioned steps (1) preparation is the inorganic titanium compound solution of 80～300g/l, and the inorganic titanium compound strength of solution is with TiO
2The content meter, titanic acid crystals kind amount is 5～13% of an inorganic titanium compound solution total amount; The inorganic titanium compound solution that contains crystal seed was reacted 0.5～6 hour under 50～140 ℃ of temperature, generate white depositions, after filtration, washing, obtain white depositions;
(3) peptization
The white depositions that above-mentioned steps (2) is obtained is distributed in the inorganic acid solution of 0.05～3M, under 25～90 ℃ temperature, dispergation 1～8 hour obtains the TiO 2 sol of transparent ambient cure, in content of titanium dioxide, collosol concentration is 60～240g/l.
The TiO 2 sol of ambient cure provided by the invention, in its preparation process, described inorganic titanium compound is metatitanic acid, titanium tetrachloride, titanium sulfate or titanyl sulfate etc., during use inorganic titanium compound is made into weight percent concentration (with TiO
2The content meter) is the solution of 80～300g/l.
In the process of step (1) preparation crystal seed, described alkali lye is NaOH or KOH solution, and concentration is 90～140g/l.The alkali lye for preparing preferably places encloses container, makes water vapor be unlikely like this and distributes, thereby kept the stability of concentration of lye.
It is to mix with the amount of 5～20ml sodium hydroxide solution by every gram titanium phosphate precipitation that the middle titanium phosphate precipitation of described step (1) is mixed with sodium hydroxide solution, and wherein, the concentration of sodium hydroxide solution is 1～3.5M.
In step (3) peptization, described inorganic acid solution is HCl, HNO
3Or H
3PO
4Solution.
In step (1) preparation seed crystal process, inorganic titanium compound solution generates crystal seed by adjusting the hydrolysis of pH value, this crystal seed carries out peptization and adds thermomaturation under mechanical agitation, soaking time is decided with crystal seed peptization degree, and purpose makes the colloidal particle micritization and generates the TiO with certain electric charge
2+And Ti
4+, make it have positive charge and be insoluble to diluted acid, and improve active.The metatitanic acid crystal seed vitreosol or the titanic acid crystals kind that are made by step (1) can be cooled to room temperature, give over to standby.
In the present invention, the preparation of crystal seed is most important, can not make the excessive hydrolysis of inorganic titanium compound, produces a large amount of white depositions, becomes muddy, loses efficacy and become the cur.
By the white depositions that step (2) obtains, after drying at room temperature forms white powder, carry out XRD determining and show that crystal formation is a Detitanium-ore-type; Through scanning electron microscope analysis titanium dioxide particle diameter is 20～60nm, narrow diameter distribution and very even.
The TiO 2 sol of ambient cure provided by the invention also can prepare by following method:
Under agitation, with TiO
2The content meter is that the inorganic titanium compound aqueous solution of 80～300g/l mixes with alkali lye with concentration, and the pH of mixing solutions is 1.5～4, obtains the metatitanic acid crystal seed; Inorganic titanium solution is joined in the metatitanic acid crystal seed, the add-on of metatitanic acid crystal seed is the 3-18% of inorganic titanium solution body product again; Again this mixture heating up to 50～140 ℃ are boiled, white precipitate, filter, washing, obtain white filter cake; White filter cake is distributed in the inorganic acid solution, and dispergation obtains the TiO 2 sol of transparent ambient cure.
The TiO 2 sol of ambient cure provided by the invention, in use, its dilution can be obtained the colloidal sol of different concns with industrial spirit, dehydrated alcohol or their mixture, the organosilicon that then adds suitable proportion, after mixing, can be on base materials such as interior exterior wall, glass, ceramic tile or plastics coating film forming, obtain that cementability is strong, the persistent coating of automatically cleaning effect.
The TiO 2 sol of ambient cure provided by the invention, by inorganic titanium compound hydrolysis automatic growing crystal species, inorganic titanium compound ordinary-pressure hydrolysis under the crystal seed effect and making, this method raw materials cost is low, and service temperature is low, and equipment is simple, pollution-free, be easy to expansion, suitability for industrialized production.
The TiO 2 sol of ambient cure provided by the invention, ambient cure need not the titanium dioxide that high temperature sintering can form anatase crystal type, and it is extremely convenient to use as normal temperature automatically cleaning product; And have TiO 2 sol concentration height, good stability and characteristics such as transparent; With industrial spirit, dehydrated alcohol or their mixture its dilution can be obtained the colloidal sol of different concns, obtain the titanium deoxid film of different thickness during coating; The titanium deoxid film that obtains of coating, performances such as antifog, automatically cleaning are fabulous.
Description of drawings
Fig. 1. the XRD figure of the embodiment of the invention 1.
Fig. 2. the embodiment of the invention 1 atomic force microscope figure.
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is further described:
Embodiment 1:
Concentration for the meta-titanium acid solution 5ml of (in content of titanium dioxide) 80g/l adds in the container, is heated to 55 ℃, is that the NaOH solution adjust pH of 90g/l is 3.0 with concentration, under agitation is incubated 0.5 hour then, obtains the crystal seed vitreosol; After resulting crystal seed vitreosol continued to be heated to 80 ℃, meta-titanium acid solution 20ml with 80g/l joins in the crystal seed vitreosol again, this reaction system is continued to be heated to 140 ℃ of down boilings 1 hour, white precipitate, after filtration, washing obtains white filter cake; The white filter cake of gained all is dispersed in the HCl solution of 20ml 3M,, obtains the TiO 2 sol of light blue transparent ambient cure in 25 ℃ of dispergation 8 hours.
The above-mentioned white filter cake that takes a morsel after the drying, is a Detitanium-ore-type through XRD test shows crystal formation at normal temperatures, and analyzing the titanium dioxide particle diameter through atomic force microscope is 8-60nm (seeing accompanying drawing 1,2)
Get the TiO 2 sol 1ml that present embodiment makes, it is dispersed in the 40ml industrial spirit dilutes, obtain the TiO 2 sol that concentration is 3g/l, the organosilicon that under well-beaten condition, in TiO 2 sol, adds 1 milliliter of 50g/l again, with the observation of filming after the mixed solution standing over night, bright, the no rainbow phenomena of the film that obtains, super parents' effect is obvious.The contact angle result of film and water measures and shows, complete drawout in the water droplet 1800ms of 2 μ l.
Embodiment 2:
Titanyl sulfate solution 3ml for (in content of titanium dioxide) 200g/l adds in the container with concentration, be heated to 28 ℃, with concentration is that the KOH solution adjust pH of 98g/l is 2.5, after above-mentioned mixed solution stirred 30 minutes, this reaction system is heated to 35 ℃, under agitation be incubated 180 minutes, promptly obtain the crystal seed vitreosol; Titanyl sulfate solution 30ml with 200g/l joins in the above-mentioned crystal seed vitreosol for preparing again, and this reaction system is continued to be heated to 100 ℃, reacted 5 hours, and resulting white precipitate, after filtration, 3% ammoniacal liquor and water washing obtain white filter cake; The gained filter cake is divided into two, is dispersed in 10 and the 1.5M HNO of 20ml respectively
3In the solution, dispergation is 4 hours under 60 ℃ of temperature, can obtain concentration and be respectively 200g/l and the light blue bright TiO 2 sol of 100g/l.
Press the measuring method of embodiment 1, the white filter cake titanium dioxide crystal form that present embodiment makes is a Detitanium-ore-type, and the titanium dioxide particle diameter is little, be evenly distributed; The TiO 2 sol photochemical catalysis that makes is effective, and it is long to keep the super hydrophilic time.
Embodiment 3:
With concentration (in content of titanium dioxide) is in the titanium tetrachloride solution 10ml adding container of 200g/l, be heated to 50 ℃, be that the NaOH solution adjust pH of 140g/l is 3.0 with concentration again, then this reaction system be heated to 85 ℃ and under agitation be incubated 40 minutes; Then this reaction system is continued to be heated to 105 ℃ and reacted 0.5 hour, the white precipitate that obtains after filtration, repetitive scrubbing, obtain 10 gram filter cakes.This 10 gram filter cake is joined the H that 30ml concentration is 0.05M
3PO
4In the solution,, obtain light blue transparent titanium dioxide colloidal sol in 85 ℃ of dispergation 5 hours.
Press the measuring method of embodiment 1, the white filter cake titanium dioxide crystal form that present embodiment makes is for being Detitanium-ore-type; Narrow diameter distribution, even, scope is at 30-80nm.
Embodiment 4:
Titanium sulfate solution 10ml for (in content of titanium dioxide) 300g/l adds in the container with concentration, be heated to 50 ℃, be that the NaOH solution adjust pH of 120g/l is 1.5 with concentration again, this reaction system continues to be heated to 68 ℃, and after being incubated 30 minutes under this temperature, prepare the crystal seed vitreosol, process adds the crystal seed vitreosol behind the thermomaturation, can use or keep standby through being cooled to room temperature.
Get the above-mentioned crystal seed vitreosol for preparing of 10ml, after being heated to 55 ℃, with 80ml concentration is that the titanium sulfate solution of 300g/l joins, stir after 40 minutes, this temperature of reaction system is heated to 125 ℃ of constant temperature boilings 4.5 hours with the speed of 5 ℃/min, resulting white depositions is filtered and is obtained filter cake, and the washing when white precipitate not occurring with barium chloride solution check filtrate of distilled water wash filter cake finishes; Then with the making beating of this filter cake adding distil water, the consumption of water without limits, stirring the back is 8 with the strong aqua adjust pH, again with this dope filtration, filters back distilled water wash filter cake 10 times; Filter cake after the washing is dissolved in the HCl solution that 50ml concentration is 2.5M,, just can obtains light blue transparent TiO 2 sol in 68 ℃ of dispergation 7.5 hours.
With the TiO 2 sol 1ml that present embodiment makes, be dispersed in the 20ml raw spirit back and stirred 30 minutes, the TiO 2 sol after the light blue dilution.
Embodiment 5:
Get the meta-titanium acid solution 5ml that concentration is cleaned for (in content of titanium dioxide) 130g/l, be heated to 38 ℃, adding concentration again is the KOH solution 9.6ml of 110g/l, and adjust pH is 3.5, above-mentioned mixed solution is continued to be heated to 70 ℃, stir insulation down after 35 minutes; Again reaction system is continued to be heated to 110 ℃ and boil 3 hours postcooling altogether, just have precipitation to generate; Filter back water repetitive scrubbing filter cake and remove foreign ion, can improve the activity of crystal seed like this, filter white filter cake; The gained filter cake all is dispersed in the HCl solution that 30ml concentration is 2M, and normal temperature dispergation 1 hour obtains glue-like or milky white shape mucilage, water or industrial spirit dilution visible blue opalescence.
Embodiment 6:
Under 30 ℃, be that slowly to add concentration in dilute hydrochloric acid (concentration of hydrochloric acid the is 3M) solution of 225g/l titanium tetrachloride be the 90g/l sodium hydroxide solution to 5ml concentration under the whipped state, regulating pH is 4.0, obtains a suspended substance; In the suspended substance that obtains, add the 3M hydrochloric acid soln again, the system acidity quotient of making is controlled at about 0.7, again this suspended substance is heated to 85 ℃ of insulations after 2 hours, the sodium hydroxide solution 10ml that adds concentration again and be 2M makes it to be condensed into white precipitate, filter, washing not till the chloride ion-containing, obtains white filter cake up to filtrate; At room temperature, this white filter cake is dispersed in the HNO that 40ml concentration is 2M
3In the solution, dispergation 10 hours just can get nattier blue TiO 2 sol.
Embodiment 7:
As method as described in the embodiment 6, different is: add the 3M hydrochloric acid soln in the suspended substance that obtains, the system acidity quotient of making is controlled at 0.3-0.5, again this suspended substance was heated to 85 ℃ gradually in 30 minutes, stir insulation down 15-30 minute, the potassium hydroxide solution 10ml that adds concentration again and be 1.96M makes it to be condensed into white precipitate, is cooled to room temperature after-filtration, washing and not till the chloride ion-containing, obtains white filter cake up to filtrate.Other is with embodiment 6.
Embodiment 8:
At normal temperatures, get 2M meta-titanium acid solution 10ml, its pH value is adjusted to 7.5, promptly have positive sodium titanate to generate, again it is contacted with 50ml cold water, just can hydrolysis generate positive metatitanic acid and sodium hydroxide with the sodium hydroxide solution of 2.5M.Sulfate ion and sodium ion are removed in the filtered water washing, can improve the activity of titanic acid crystals kind like this, obtain titanic acid crystals kind.In titanic acid crystals kind, add 2M meta-titanium acid solution 60ml again, this system be heated to 110 ℃ of boilings after 3 hours, this reaction system after filtration, washing, obtain white depositions.Is 2.1M hydrochloric acid with resulting white depositions with 40ml concentration, and the normal temperature peptization promptly obtained the TiO 2 sol of ambient cure in 1 hour.
The titanic acid crystals kind dispersiveness that this method of present embodiment makes is fabulous, and activity is very high.
Embodiment 9:
At normal temperatures, be that to add concentration in the 3M titanium sulfate solution be the phosphoric acid solution of 2.0M to 5ml concentration, adjust pH is 3.0, promptly the titanium phosphate of adularescent precipitation generates, after filtration, behind the distilled water wash 3 times, obtain the titanium phosphate precipitation; Adding 10ml concentration again in precipitation is the sodium hydroxide solution of 2.0M, boils altogether under 100 ℃ and generates positive sodium titanate in 1 hour, products therefrom is added in the 35ml cold water again, and hydrolysis generates positive metatitanic acid and sodium hydroxide; Filtration, distilled water wash are removed sulfate ion and sodium ion, can improve the activity of titanic acid crystals kind like this, obtain titanic acid crystals kind.Adding 20ml concentration in the titanic acid crystals kind again is the 3M titanium sulfate solution, and this system was heated to 115 ℃ of boilings after 5 hours, this reaction system after filtration, washing, obtain white depositions; Resulting white depositions was promptly obtained the TiO 2 sol of ambient cure in 2 hours with 60 ℃ of peptizations of 30ml 2.5M nitric acid.
Claims (7)
1. the preparation method of the TiO 2 sol of an ambient cure is characterized in that, described preparation method's step is:
(1) preparation crystal seed
(a) with TiO
2The content meter, getting concentration is the inorganic titanium compound aqueous solution of 80～300g/l, and the inorganic titanium compound aqueous solution is heated to 28～85 ℃, with NaOH or KOH solution the inorganic titanium compound pH value of water solution is adjusted into 1.5～4, stir insulation down, obtain metatitanic acid crystal seed vitreosol;
(b) or with TiO
2The content meter, getting concentration is the meta-titanium acid solution of cleaning of 80～300g/l, and behind the hydro-oxidation sodium meta-titanium acid solution pH value is adjusted into 7.5～8.0, promptly has positive sodium titanate to form; Positive sodium titanate is contacted with cold water, hydrolysis generates positive metatitanic acid and sodium hydroxide again, and filtration, washing obtain titanic acid crystals kind;
(c) or with TiO
2The content meter, get the titanium sulfate solution that concentration is 80～300g/l, adding phosphoric acid accent pH is 3.0～3.5, generate white titanium phosphate precipitation, after filtration, the sodium hydroxide of washing back and liquid boils under 70～100 ℃ altogether, generates positive sodium titanate, more positive sodium titanate is contacted with cold water, hydrolysis generates positive metatitanic acid and sodium hydroxide, and filtration, washing obtain titanic acid crystals kind;
(2) preparation white depositions
The metatitanic acid crystal seed vitreosol of preparation in the step (1) is boiled under 50～140 ℃ of temperature, generate white depositions, after filtration, washing, obtain white depositions; Wherein, the amount of crystal seed is TiO in the inorganic titanium compound solution in the vitreosol
23～18% of total amount;
Perhaps adding concentration in the titanic acid crystals kind of step (1) preparation is the inorganic titanium compound solution of 80～300g/l, and the inorganic titanium compound strength of solution is with TiO
2The content meter, titanic acid crystals kind amount is 5～13% of an inorganic titanium compound solution total amount; The inorganic titanium compound solution that contains crystal seed is reacted under 50～140 ℃ of temperature, generate white depositions, after filtration, washing, obtain white depositions;
(3) peptization
The white depositions that step (2) is obtained is distributed to HCl, HNO
3Or H
3PO
4In the inorganic acid solution, dispergation obtains the TiO 2 sol of transparent ambient cure.
2. the method for claim 1, it is characterized in that: before described step (2) the preparation white depositions, further add inorganic titanium compound solution in the metatitanic acid crystal seed vitreosol of step (1) preparation, the amount that makes crystal seed in this vitreosol is TiO in the inorganic titanium compound solution
23～18% of total amount is with TiO
2Content meter, inorganic titanium compound strength of solution are 80～300g/l.
3. method as claimed in claim 1 or 2 is characterized in that: described inorganic titanium compound is metatitanic acid, titanium tetrachloride, titanium sulfate or titanyl sulfate.
4. the method for claim 1 is characterized in that: described step (1) is 28～85 ℃ with the temperature of inorganic titanium compound solution heating.
5. the method for claim 1, it is characterized in that: it is to mix with the amount of 5～20ml sodium hydroxide solution by every gram titanium phosphate precipitation that the middle titanium phosphate precipitation of described step (1) is mixed with sodium hydroxide solution, wherein, the concentration of sodium hydroxide solution is 1～3.5M.
6. the preparation method of the TiO 2 sol of an ambient cure is characterized in that, described preparation method is:
Under agitation, with TiO
2The content meter is that the inorganic titanium compound aqueous solution of 80～300g/l mixes with NaOH or KOH alkali lye with concentration, and the pH of mixing solutions is 1.5～4, obtains the metatitanic acid crystal seed; Inorganic titanium solution is joined in the metatitanic acid crystal seed, the add-on of metatitanic acid crystal seed is the 3-18% of inorganic titanium solution body product again; Again this mixture heating up to 50～140 ℃ are boiled, white precipitate, filter, washing, obtain white filter cake; White filter cake is distributed to HCl, HNO
3Or H
3PO
4In the inorganic acid solution, dispergation obtains the TiO 2 sol of transparent ambient cure.
7. method as claimed in claim 6 is characterized in that: described inorganic titanium compound is metatitanic acid, titanium tetrachloride, titanium sulfate or titanyl sulfate.
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| CN100484880C (en) * | 2005-09-22 | 2009-05-06 | 中国科学院理化技术研究所 | Low-temperature crystallized nano titanium dioxide powder and synthesis method of sol |
| CN100347248C (en) * | 2006-01-06 | 2007-11-07 | 浙江大学 | Method for preparing broad-spectrum excitation responsible coating self-cleaning protector |
| CN103396634B (en) * | 2013-08-13 | 2016-01-13 | 武汉羿阳科技有限公司 | A kind of self-cleaning antibacterial anti-fog thin film |
| CN105664808B (en) * | 2016-01-13 | 2021-02-19 | 云南大学 | Method for preparing stable nano anatase titanium dioxide alcohol phase sol at low temperature |
| CN109250753A (en) * | 2018-12-10 | 2019-01-22 | 攀钢集团攀枝花钢铁研究院有限公司 | The method for preparing nano-anatase mine-titanium oxide |
| CN112845000A (en) * | 2020-12-31 | 2021-05-28 | 安徽百圣鑫金属科技有限公司 | Preparation method of heat-resistant coating for smelting high-purity aluminum ingot |
| CN114105193A (en) * | 2021-11-30 | 2022-03-01 | 重庆英诺维节能环保科技有限公司 | Preparation method of ultraviolet shielding nano titanium dioxide material |
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