CN1228397C - Silver phosphate antibacterial modified titanium dioxide composite particle and its preparation method and use - Google Patents
Silver phosphate antibacterial modified titanium dioxide composite particle and its preparation method and use Download PDFInfo
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- CN1228397C CN1228397C CN 02117493 CN02117493A CN1228397C CN 1228397 C CN1228397 C CN 1228397C CN 02117493 CN02117493 CN 02117493 CN 02117493 A CN02117493 A CN 02117493A CN 1228397 C CN1228397 C CN 1228397C
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Abstract
The present invention belongs to a modified functional material of inorganic nanometer and an application area thereof, particularly to a preparation method of silver phosphate antibacterial modified titanium dioxide composite particles, and use. The silver phosphate antibacterial modified titanium dioxide composite particles of the present invention with an antibacterial function use nanometer titanium dioxide particles or submicron titanium dioxide particles as internal cores; after the surfaces of the titanium dioxide particles are coated with a silica and alumina layer, a silicon dioxide layer or an alumina layer; the titanium dioxide compound particles with porous properties are obtained; after a phosphoric acid silver layer is coated on the surfaces of the titanium dioxide compound particles, the sizes of the silver phosphate antibacterial modified titanium dioxide composite particles are between 52 nm and 2150 nm, and the respective thicknesses of the coating layers of the silicon dioxide, the aluminum oxide and the silver phosphate are from 1 to 50 nm. The composite particles are mixed into coating materials, ceramic materials, plastic materials or rubbery materials to be used as antibacterial materials. The composite particles have the advantages of high purity and high dispersibility, and the composite particles have antibacterial properties.
Description
Technical field
The invention belongs to inorganic nanometer modified functional materials and Application Areas thereof, particularly relate to silver phosphate antibacterial modified titanium dioxide composite particle and its production and use.
Background technology
Along with the high speed development of industry and the raising of people's living standard, the requirement that improves environment for human survival is urgent day by day, and anti-biotic material is the important component part of environment-friendly materials.Since the eighties in 20th century, developed countries such as U.S., day begin to use in a large number anti-biotic material at aspects such as hospital, dwelling house, public place, daily necessitiess.
Titanium dioxide is a kind of important Inorganic Chemicals, is widely used in numerous areas such as coating, printing ink, plastics, rubber, papermaking, chemical fibre, pottery, enamel, with people's lives and national economy close getting in touch is arranged.A.Fujishima is at Pure ﹠amp; Appl.Chem., Vol.70, NO.11, P.2177-2187Interfacial photochemistry:Fundamentals andapplication middle finger goes out nano-TiO
2Be a kind of photocatalyst, have good anti-microbial effect.Point out general TiO among " but Chinese first anti-biotic material industry development conference collection of thesis " P49-55 " the antibacterial and mouldproof application performance research of nano titanium oxide "
2Thick product powder is assembled serious, and the coacervate granularity reaches submicron and micron order, is difficult for producing active group, can not bring into play due anti-microbial property.While TiO
2Anatase titanium dioxide TiO particularly
2Be subjected to uviolizing, oxygen can break away from the following TiO of reduction, particularly 100nm
2Particle, because surface-area is big, the photocatalytic activity height, the easier degraded that causes other organic supplementary component, and cause the variation of self tone causes the efflorescence of filming, fades, variable color, becomes fragile, and sticking power, corrosion resistance nature descend.Therefore in the practical application, how not only suppress but also utilize TiO
2Photocatalytic activity, develop a kind of TiO with antibacterial
2Very extensive fields be can be applied to, huge social benefit and economic benefit created.
The anti-bacterial powder, the antibacterial matrices that have had some excellent performances on the current market.Common antimicrobial prod adds these anti-biotic materials in the antimicrobial prod to exactly according to a certain percentage.The consistency of anti-bacterial powder or master batch and antimicrobial prod main component just affects the dispersiveness of anti-biotic material like this.If both consistencies are poor, will cause anti-biotic material skewness in goods, even occur reuniting, make it be difficult to bring into play anti-microbial effect, and can influence the apparent state and the mechanical property of goods.Therefore to being entrained in the inorganic composition TiO in the materials such as coating, plastics, pottery, enamel
2Carry out antibacterial modified preparation antimicrobial prod, not only avoided adding the possible defective that antiseptic-germicide brings but also can reduce adjustment original production process.
Summary of the invention
One of purpose of the present invention provides a kind of silver phosphate antibacterial modified titanium dioxide composite particle, this composite particles purity height, and good dispersity, and have micropore; This particle is a characteristic of utilizing Trisilver phosphate, coats the Trisilver phosphate of desired thickness on the titanium dioxide granule surface, makes particle have antibacterial properties.
Two of purpose of the present invention provides a kind of preparation method of silver phosphate antibacterial modified titanium dioxide composite particle.
Three of purpose of the present invention provides a kind of purposes of silver phosphate antibacterial modified titanium dioxide composite particle.
Four of purpose of the present invention provides a kind of preparation method of antibacterial powder paint.
Purpose of the present invention will further be set forth by following detailed description.
Silver phosphate antibacterial modified titanium dioxide composite particle with antibacterial of the present invention is as kernel with nanometer or submicron titanium dioxide granule, be coated with silicon oxide and alumina layer, silicon dioxide layer or alumina layer on the titanium dioxide granule surface, obtain having the titanium dioxide composite particle of porous character, be coated with the phosphoric acid silver layer on the titanium dioxide composite particle surface;
Or the layer that is coated with silicon oxide on the titanium dioxide granule surface, the titanium dioxide composite particle that obtains having porous character is coated with the phosphoric acid silver layer on the titanium dioxide composite particle surface, is coated with alumina layer at the phosphoric acid silver layer then;
Or be coated with alumina layer on the titanium dioxide granule surface, and obtain having the titanium dioxide composite particle of porous character, coat the phosphoric acid silver layer on the titanium dioxide composite particle surface, be coated with silicon dioxide layer at the phosphoric acid silver layer then;
The size that obtains silver phosphate antibacterial modified titanium dioxide composite particle is between 52nm-2150nm;
The particle diameter of titanium dioxide granule is between 50nm-2000nm, and described silicon-dioxide, aluminum oxide, Trisilver phosphate coating thickness are respectively 1～50nm.
Preparation method with silver phosphate antibacterial modified titanium dioxide composite particle of antibacterial of the present invention is:
A. be A1 to the titanium dioxide antibiotic particle of titanium dioxide granule coated silica, aluminum oxide, Trisilver phosphate successively;
B. be A2 to the titanium dioxide antibiotic particle of titanium dioxide granule coated silica, Trisilver phosphate, aluminum oxide successively;
C. be A3 to the titanium dioxide antibiotic particle of titanium dioxide granule coated silica, Trisilver phosphate successively;
D. be A4 to the titanium dioxide antibiotic particle of titanium dioxide granule coated aluminum oxide, Trisilver phosphate successively;
E. be A5 to the titanium dioxide antibiotic particle of titanium dioxide granule coated aluminum oxide, Trisilver phosphate, silicon-dioxide successively;
F. be A6 to the titanium dioxide antibiotic particle of titanium dioxide granule coated aluminum oxide, silicon-dioxide, Trisilver phosphate successively;
This method steps is:
(1). in water, the weight percent concentration of gained titanium dioxide in water is 5～40%, is preferably 5～25% with the titanium dioxide granule dispersed with stirring.
(2). the aqueous solution of preparation water glass, its volumetric molar concentration is 0.01～1mol/L, is preferably 0.01～0.3mol/L; The thickness of the silicon-dioxide of the required coating of foundation is determined the volumetric molar concentration and the consumption thereof of water glass.
(3). the aqueous solution of preparation Tai-Ace S 150, its volumetric molar concentration is 0.01～1mol/L, is preferably 0.01～0.3mol/L; The thickness of the aluminum oxide of the required coating of foundation is determined the volumetric molar concentration and the consumption thereof of Tai-Ace S 150.
(4). the aqueous solution of preparation Sodium phosphate dibasic, its volumetric molar concentration is 0.01～1mol/L, is preferably 0.01～0.3mol/L.
(5). preparation silver complex solution, its volumetric molar concentration is 0.01～1mol/L, is preferably 0.01～0.3mol/L.
(6). the sodium silicate aqueous solution of step (2) preparation is slowly joined in the aqueous solution of titanium dioxide of step (1) preparation, preparation is used to prepare A1, A2 or A3 particulate solution;
Wherein, the consumption of sodium silicate aqueous solution is determined titanium dioxide in the mixed solution according to the thickness requirement of required coated with silica layer: the mol ratio of water glass is 1: 0.01～1: 0.4;
Or the aqueous solution of the Tai-Ace S 150 of step (3) preparation slowly joined in the titanium dioxide granule aqueous solution of step (1) preparation, preparation is used to prepare A4, A5 or A6 particulate solution;
Wherein, the consumption of aluminum sulfate aqueous solution is determined titanium dioxide in the mixed solution according to the size of titanium dioxide composite particle, the thickness requirement of required aluminum oxide coating layer: the mol ratio of Tai-Ace S 150 is 1: 0.01～1: 0.4.
(7). the water glass of continuous whipping step (6) preparation, the mixed solution of titanium dioxide, with acid the pH value of solution is adjusted to 9～10, in temperature is ageing 0.5～5 hour under 60～100 ℃, agitation as appropriate speed, separate mixed solution, to throw out washing, drying, prepare A1, A2 or A3 particulate coated with silica layer;
Or the Tai-Ace S 150 of constantly whipping step (6) preparation, the aqueous solution liquid of titanium dioxide, with alkali the pH value of solution is adjusted to 5～8, in temperature is 60～100 ℃, ageing is 2～8 hours under the agitation as appropriate speed, separate mixed solution, to throw out washing, drying, prepare A4, A5 or A6 particulate alumina-coated layer.
(8). with the particle that is used to prepare A1, A2, A3, A4, A5 or A6 that step (7) obtains, dispersed with stirring is in water, and weight percent concentration is 5～40%, is preferably 5～25%.
(9). for the particle that is used to prepare A1 in the step (8), the aqueous solution with the Tai-Ace S 150 of step (3) preparation, slowly join in step (8) aqueous solution, wherein, the consumption of alum liquor is determined titanium dioxide in the mixed solution according to the size of titanium dioxide composite particle, the thickness requirement of required aluminum oxide coating layer: the mol ratio of Tai-Ace S 150 is 1: 0.01～1: 0.4; Constantly mixing liquid, with alkali the pH value of solution is adjusted to 5～8, is 60～100 ℃ in temperature, and ageing is 2～8 hours under the agitation as appropriate speed, separates mixed solution, and to the throw out washing, drying is prepared A1 particulate alumina-coated layer.
Or for the particle that is used to prepare A2, A3, A4 or A5 in the step (8), disodium phosphate soln with step (4) preparation, slowly join in step (8) aqueous solution, wherein, the consumption of disodium phosphate soln is determined titanium dioxide in the mixed solution according to the thickness of required Trisilver phosphate coating layer: the mol ratio of Sodium phosphate dibasic is 1: 0.02～1: 0.5; And then slowly adding the silver complex solution that step (5) is prepared, the consumption of silver complex solution is determined according to the consumption of Sodium phosphate dibasic, Sodium phosphate dibasic in the mixed solution: the mol ratio of silver complex is 1: 1～1: 4; Stir ageing, separate mixed solution, to the throw out washing, drying is prepared A2, A3, A4 or A5 particulate Trisilver phosphate coating layer; Promptly obtain successively titanium dioxide antibiotic particle A3, or obtain successively titanium dioxide antibiotic particle A4 titanium dioxide granule coated aluminum oxide, Trisilver phosphate to titanium dioxide granule coated silica, Trisilver phosphate;
Or for the particle that is used to prepare A6 in the step (8), sodium silicate aqueous solution with step (2) preparation, slowly join in step (8) aqueous solution, the consumption of sodium silicate solution is determined titanium dioxide in the mixed solution according to the thickness requirement of required coated with silica layer: the mol ratio of water glass is 1: 0.01～1: 0.4.Constantly stirring, with acid the pH value of solution is adjusted to 9～10, is ageing 0.5～5 hour under 60～100 ℃, agitation as appropriate speed in temperature, and the separation mixed solution washs throw out, and drying is prepared A6 particulate coated with silica layer.
(10). to water, weight percent concentration is 5～40%, is preferably 5～25% with the particles dispersed that is used for preparing A1 or A6 of step (9).The disodium phosphate soln of step (4) preparation is slowly joined in the mixed solution.Wherein, the consumption of disodium phosphate soln is determined titanium dioxide in the mixed solution according to the thickness of required Trisilver phosphate coating layer: the mol ratio of Sodium phosphate dibasic is 1: 0.02～1: 0.5.Silver complex solution with step (5) preparation slowly joins in the mixed solution, and the consumption of silver complex solution is determined according to the consumption of Sodium phosphate dibasic, Sodium phosphate dibasic in the mixed solution: the mol ratio of silver complex is 1: 1～1: 4.Stir ageing, separate mixed solution, to the throw out washing, drying is prepared A1 or A6 particulate Trisilver phosphate coating layer, promptly obtains successively the titanium dioxide antibiotic particle A1 to titanium dioxide granule coated silica, aluminum oxide, Trisilver phosphate; Or obtain successively titanium dioxide antibiotic particle A6 to titanium dioxide granule coated aluminum oxide, silicon-dioxide, Trisilver phosphate.
(11). the particles dispersed that step (9) is used for preparing A2 is to water, and weight percent concentration is 5～40%, is preferably 5～25%.The aqueous solution of the Tai-Ace S 150 of step (3) preparation is slowly joined in the mixed solution.Wherein, the consumption of alum liquor is determined titanium dioxide in the mixed solution according to the size of titanium dioxide composite particle, the thickness requirement of required aluminum oxide coating layer: the mol ratio of Tai-Ace S 150 is 1: 0.01～1: 0.40.Constantly mix liquid, with alkali the pH value of solution is adjusted to 5～8, in temperature is 60～100 ℃, ageing is 2～8 hours under the agitation as appropriate speed, separate mixed solution, to throw out washing, drying, prepare A2 particulate alumina-coated layer, promptly obtain successively titanium dioxide antibiotic particle A2 titanium dioxide granule coated silica, Trisilver phosphate, aluminum oxide;
(12). in water, weight percent concentration is 5～40%, is preferably 5～25% with the A5 particles dispersed of step (9) preparation.The sodium silicate solution of step (2) preparation is slowly joined in the mixed solution.The consumption of sodium silicate solution is determined titanium dioxide in the mixed solution according to the thickness requirement of required coated with silica layer: the mol ratio of water glass is 1: 0.01～1: 0.4.Constantly stir, with acid the pH value of solution is adjusted to 9～10, in temperature is ageing 0.5～5 hour under 60～100 ℃, agitation as appropriate speed, separate mixed solution, throw out is washed, drying is prepared A5 particulate coated with silica layer, promptly obtains successively the titanium dioxide antibiotic particle A5 to titanium dioxide granule coated aluminum oxide, Trisilver phosphate, silicon-dioxide.
(13). A3 and A4 antibacterial granule that step (9) is obtained, A1 that step (10) obtains and A6 antibacterial granule, the A2 antibacterial granule that step (11) obtains, the A5 antibacterial granule that step (12) obtains, be 300 ℃ of-900 ℃ of roastings in temperature respectively, pulverize, finally obtain silver phosphate antibacterial modified titanium dioxide composite particle respectively.
Described silver complex can be silver-ammonia complex or silver thiosulfate complex etc., is preferably silver-ammonia complex.
The acid of described adjustment pH value is nitric acid, hydrochloric acid or sulfuric acid etc.; The alkali of described adjustment pH value is sodium hydroxide or ammoniacal liquor etc.
Described titanium dioxide is sharp attitude type titanium dioxide.
The titanium dioxide composite particle that this is antibacterial modified is entrained in coating, pottery, plastics or the elastomeric material and uses as anti-biotic material.
Silver phosphate antibacterial modified titanium dioxide composite particle of the present invention can also have multiple coating, as directly titanium dioxide granule being coated Trisilver phosphate etc.
Silver phosphate antibacterial modified titanium dioxide composite particle of the present invention is a kind of novel high functional inorganic materials, and the content of its antimicrobial component Trisilver phosphate can be entrained in the materials such as coating, pottery, plastics or rubber and use as anti-biotic material at 0.5-30%.
Antibacterial modified titanium dioxide composite particle is replaced titanium dioxide in the powder coating, mix, push, pulverize, sieve, spray, step such as baking just can prepare antibacterial powder paint.The anti-microbial property of the antibacterial powder coating of heat curing-type is tested with reference to GB15981-1995, Q/HDHKH002-2000 detection method and standard.Behind the testing sample sterilization and drying, 0.2ml bacterium bacterium to be measured liquid is evenly dripped on sample respectively, cover with film, put in the sterilising vessel, after placing 24 hours under 36 ℃ of temperature, the humidity 90%RH, add the 20ml elutriant respectively, wash-out fully vibrates, switching NA substratum carries out live bacterial count, with antibacterial powder paint sample and ordinary powder coating in the same old way recovery bacterium number is calculated its bacteriostasis rate.Test result shows that antibiotic paint all reaches more than 96% the antibiotic rate of intestinal bacteria and streptococcus aureus, has good antimicrobial property.
Silver phosphate antibacterial modified titanium dioxide composite particle of the present invention has:
1. prepare simplely, be easy to apply.
2. the white pigment TiO that is widely used of apparatus
2As antibiotic base material, the preparation anti-bacterial powder is not only utilized TiO
2Covering power, and be easy to the toning.
3. because TiO
2Be non-stripping property antiseptic-germicide, thereby be a kind of semi-permanent mould antiseptic-germicide, can effect descend gradually along with the stripping of antiseptic-germicide unlike other antiseptic-germicide.
4. with comparatively inexpensive anatase titanium dioxide TiO
2Make carrier compound phosphoric acid silver, can improve the dispersiveness of titanium dioxide, well keep the optically catalytic TiO 2 activity.
5. the TiO that is widely used of apparatus
2As antibiotic substrate preparation anti-bacterial powder, not only avoided the preparation antimicrobial prod to add the possible defective that antiseptic-germicide brings but also can reduce adjustment original production process.This method is a very economical and superior.
6. the TiO that is equipped with of porous silica of Bao Fuing and aluminum oxide and compound silvery
2Antibacterial granule just has very strong anti-microbial effect under more weak visible light effect.
7. coat TiO by adjusting
2Silicon-dioxide, alumina-coated layer, and coating thickness, be easy to make can with the compatible antimicrobial product of other composition of different sorts antimicrobial prod.
Embodiment
Embodiment 1
With TiO
2The particle dispersed with stirring is in the aqueous solution, and weight percent concentration is 10%.In this mixing solutions, slowly be added dropwise to sodium silicate aqueous solution after being warmed up to 85 ℃, make TiO
2The initial molar ratio of-water glass is 5: 1, and its dropping time is 20 minutes.Use sulfuric acid adjusts to 9.5 with the pH of mixed solution, stirs ageing down 2 hours, obtains white opacity solution, sedimentation, washing, separation, drying, the TiO that obtains having coated with silica
2Composite particles.Again with the TiO of this coated with silica
2The composite particles dispersed with stirring slowly adds the Sodium phosphate dibasic aqueous solution in the aqueous solution, make TiO
2The initial molar ratio of-Sodium phosphate dibasic is: 1: 0.05.Slowly be added dropwise to silver-ammonia complex solution then, the initial molar ratio that makes Sodium phosphate dibasic-silver ammonia complex is 1: 2.Stir ageing and obtain faint yellow turbid solution, sedimentation, washing, separation, drying, 500 ℃ of roastings obtain the titanium dioxide composite particle of coated silica, Trisilver phosphate successively, promptly obtain the antibacterial modified titanium dioxide particle.
Embodiment 2
With TiO
2The particle dispersed with stirring is in the aqueous solution, and weight percent concentration is 20%.In this mixing solutions, slowly be added dropwise to aluminum sulfate aqueous solution after being warmed up to 70 ℃, make TiO
2The initial molar ratio of-Tai-Ace S 150 is 5: 1.Use sodium hydroxide adjusts to 7.0 with the pH of mixed solution, stirs ageing down 4 hours, obtains white opacity solution, sedimentation, washing, separation, drying, the TiO that obtains having alumina-coated
2Composite particles.Again with the TiO of this alumina-coated
2The composite particles dispersed with stirring is in the aqueous solution, and weight percent concentration is 20%.Slowly add the Sodium phosphate dibasic aqueous solution, make TiO
2The initial molar ratio of-Sodium phosphate dibasic is 1: 0.06.Slowly be added dropwise to silver-ammonia complex solution then, the initial molar ratio that makes Sodium phosphate dibasic-silver ammonia complex is 1: 2.Stir ageing 1 hour, obtain faint yellow turbid solution, sedimentation, washing, separation, drying.550 ℃ of following roastings obtain the titanium dioxide composite particle of coated aluminum oxide, Trisilver phosphate successively, promptly obtain the antibacterial modified titanium dioxide particle.
Embodiment 3
With TiO
2The particle dispersed with stirring is in the aqueous solution, and weight percent concentration is 15%.In this mixing solutions, slowly be added dropwise to sodium silicate aqueous solution after being warmed up to 85 ℃, make TiO
2The initial molar ratio of-water glass is 6: 1, and its dropping time is 25 minutes.Use hydrochloric acid adjusts to 9.5 with the pH of mixed solution, stirs ageing down 2.5 hours, obtains white opacity solution, sedimentation, washing, separation, drying, the TiO that obtains having coated with silica
2Composite particles.In the aqueous solution, weight percent concentration is 25% with its dispersed with stirring.In this mixing solutions, slowly be added dropwise to aluminum sulfate aqueous solution after being warmed up to 70 ℃, make TiO
2The initial molar ratio of-Tai-Ace S 150 is 1: 0.04.Use sodium hydroxide that the pH of mixed solution is adjusted to 7, stir ageing down 4 hours, obtain white opacity solution, sedimentation, washing, separation, drying obtain having aluminum oxide, the TiO of coated with silica
2Composite particles.Again with this TiO
2The composite particles dispersed with stirring is in the aqueous solution, and weight percent concentration is 20%.Slowly add the Sodium phosphate dibasic aqueous solution, make TiO
2The initial molar ratio of-Sodium phosphate dibasic is 1: 0.08.Slowly be added dropwise to silver ammonia complex solution then, the initial molar ratio that makes Sodium phosphate dibasic-silver ammonia complex is 1: 1.Stir ageing and obtain faint yellow turbid solution, sedimentation, washing, separation, drying, 500 ℃ of following roastings obtain the titanium dioxide composite particle of coated silica, aluminum oxide and Trisilver phosphate successively, promptly obtain the antibacterial modified titanium dioxide particle.
Embodiment 4
With TiO
2The particle dispersed with stirring is in the aqueous solution, and weight percent concentration is 15%.In this mixing solutions, slowly be added dropwise to sodium silicate aqueous solution after being warmed up to 85 ℃, make TiO
2The initial molar ratio of-water glass is 4: 1, and its dropping time is 30 minutes.Use sulfuric acid adjusts to 9.5 with the pH of mixed solution, stirs ageing down 2.5 hours, obtains white opacity solution, sedimentation, washing, separation, drying, the TiO that obtains having coated with silica
2Composite particles.Again with this TiO
2The composite particles dispersed with stirring is in the aqueous solution, and weight percent concentration is 30%.Slowly add the Sodium phosphate dibasic aqueous solution, make TiO
2The initial molar ratio of-Sodium phosphate dibasic is 1: 0.1.Slowly be added dropwise to silver-ammonia complex solution then, the initial molar ratio that makes Sodium phosphate dibasic-silver ammonia complex is 1: 3.Stir ageing and obtain faint yellow turbid solution, sedimentation, washing, separation, drying obtain the titanium dioxide composite particle that silicon-dioxide and Trisilver phosphate coat.It is distributed in the water once more, and weight percent concentration is 18%.In this mixing solutions, slowly be added dropwise to aluminum sulfate aqueous solution after being warmed up to 70 ℃, make TiO
2The initial molar ratio of-Tai-Ace S 150 is 7: 1.Use sodium hydroxide adjusts to 7 with the pH of mixed solution, stir ageing down 4 hours, obtain turbid solution, sedimentation, washing, separation, drying, 650 ℃ of following roastings obtain the titanium dioxide composite particle of coated silica, Trisilver phosphate and aluminum oxide successively, promptly obtain the antibacterial modified titanium dioxide particle.
Embodiment 5
With TiO
2The particle dispersed with stirring is in the aqueous solution, and weight percent concentration is 30%.In this mixing solutions, slowly be added dropwise to aluminum sulfate aqueous solution after being warmed up to 70 ℃, make TiO
2The initial molar ratio of-Tai-Ace S 150 is 6: 1.Use sodium hydroxide adjusts to 7 with the pH of mixed solution, stirs ageing down 4 hours, obtains white opacity solution, and sedimentation, washing, separation, drying obtain having alumina-coated TiO
2Composite particles.Again with this TiO
2The composite particles dispersed with stirring is in water, and weight percent concentration is 35%.Slowly add the Sodium phosphate dibasic aqueous solution, make TiO
2The initial molar ratio of-Sodium phosphate dibasic is 1: 0.12.Slowly be added dropwise to silver ammonia complex solution then, the initial molar ratio that makes Sodium phosphate dibasic-silver ammonia complex is 1: 1.Stir ageing and obtain faint yellow turbid solution, sedimentation, washing, separation, drying obtain having the titanium dioxide composite particle of Tai-Ace S 150 and Trisilver phosphate coating layer.It is distributed in the water once more, and weight percent concentration is 15%.In this mixing solutions, slowly be added dropwise to sodium silicate aqueous solution after being warmed up to 85 ℃, make TiO
2The initial molar ratio of-water glass is 7: 1, and its dropping time is 25 minutes.Use sulfuric acid adjusts to 9.5 with the pH of mixed solution, stir ageing down 2 hours, obtain turbid solution, sedimentation, washing, separation, drying, 550 ℃ of following roastings obtain the titanium dioxide composite particle of coated aluminum oxide, Trisilver phosphate and silicon-dioxide successively, promptly obtain the antibacterial modified titanium dioxide particle.
Embodiment 6
In the aqueous solution, weight percent concentration is 20% with the titanium dioxide granule dispersed with stirring.Slowly be added dropwise to aluminum sulfate aqueous solution after being warmed up to 70 ℃ in this mixing solutions, the initial molar ratio that makes titanium dioxide and Tai-Ace S 150 is 5: 1.Use sodium hydroxide adjusts to 7 with the pH of mixed solution, stirs ageing down 3.5 hours, obtains white opacity solution, sedimentation, washing, separation, drying, the titanium dioxide composite particle that obtains having alumina-coated.In the aqueous solution, weight percent concentration is 25% with its dispersed with stirring.Slowly be added dropwise to sodium silicate aqueous solution after being warmed up to 80 ℃ in this mixing solutions, the initial molar ratio that makes titanium dioxide and water glass is 6: 1, and its dropping time is 25 minutes.Use sulfuric acid that the pH of mixed solution is adjusted to 9.5, stir ageing down 4 hours, obtain white opacity solution, sedimentation, washing, separation, drying obtain having aluminum oxide, the titanium dioxide composite particle of coated with silica.Again with this titanium dioxide composite particle dispersed with stirring in the aqueous solution, slowly add the Sodium phosphate dibasic aqueous solution, the initial molar ratio that makes titanium dioxide and Sodium phosphate dibasic is 1: 0.04.Slowly be added dropwise to silver complex solution then, the initial molar ratio that makes Sodium phosphate dibasic-silver complex is 1: 3.Stir ageing 1 hour, obtain faint yellow turbid solution, sedimentation, washing, separation, drying, 650 ℃ of following roastings obtain having the antibacterial modified titanium dioxide composite particle that coats Tai-Ace S 150, silicon-dioxide and Trisilver phosphate successively.
Embodiment 7
Modification TiO with embodiment 1-6 preparation
2Composite particles replaces the TiO in the powder coating respectively
2, mix, push, pulverize, sieve, step such as spraying, roasting just can prepare antibacterial powder paint.To the antibiotic rate of intestinal bacteria, streptococcus aureus all more than 96%.
Claims (11)
1. silver phosphate antibacterial modified titanium dioxide composite particle, it is characterized in that: this composite particles is as kernel with nanometer or submicron titanium dioxide granule, be coated with silicon oxide and alumina layer, silicon dioxide layer or alumina layer on the titanium dioxide granule surface, obtain having the titanium dioxide composite particle of porous character, be coated with the phosphoric acid silver layer on the titanium dioxide composite particle surface;
The particle diameter of titanium dioxide granule is between 50nm-2000nm, and described silicon-dioxide, aluminum oxide, Trisilver phosphate coating thickness are respectively 1～50nm.
2. particle as claimed in claim 1 is characterized in that: the described outer Trisilver phosphate laminar surface of silicon dioxide layer that is coated on further is coated with alumina layer.
3. particle as claimed in claim 1 is characterized in that: the described outer Trisilver phosphate laminar surface of the alumina layer layer that further is coated with silicon oxide that is coated on.
4. preparation method as any described silver phosphate antibacterial modified titanium dioxide composite particle of claim 1-3 is characterized in that:
A. be A1 to the titanium dioxide antibiotic particle of titanium dioxide granule coated silica, aluminum oxide, Trisilver phosphate successively;
B. be A2 to the titanium dioxide antibiotic particle of titanium dioxide granule coated silica, Trisilver phosphate, aluminum oxide successively;
C. be A3 to the titanium dioxide antibiotic particle of titanium dioxide granule coated silica, Trisilver phosphate successively;
D. be A4 to the titanium dioxide antibiotic particle of titanium dioxide granule coated aluminum oxide, Trisilver phosphate successively;
E. be A5 to the titanium dioxide antibiotic particle of titanium dioxide granule coated aluminum oxide, Trisilver phosphate, silicon-dioxide successively;
F. be A6 to the titanium dioxide antibiotic particle of titanium dioxide granule coated aluminum oxide, silicon-dioxide, Trisilver phosphate successively;
Steps of the method are:
(1). in water, the weight percent concentration of gained titanium dioxide in water is 5～40% with the titanium dioxide granule dispersed with stirring;
(2). the aqueous solution of preparation water glass;
(3). the aqueous solution of preparation Tai-Ace S 150;
(4). the aqueous solution of preparation Sodium phosphate dibasic;
(5). preparation silver complex solution;
(6). the sodium silicate aqueous solution of step (2) preparation is slowly joined in the aqueous solution of titanium dioxide of step (1) preparation, preparation is used to prepare A1, A2 or A3 particulate solution;
Wherein, titanium dioxide in the mixed solution: the mol ratio of water glass is 1: 0.01～1: 0.4;
Or the aqueous solution of the Tai-Ace S 150 of step (3) preparation slowly joined in the titanium dioxide granule aqueous solution of step (1) preparation, preparation is used to prepare A4, A5 or A6 particulate solution;
Wherein, titanium dioxide in the mixed solution: the mol ratio of Tai-Ace S 150 is 1: 0.01～1: 0.4;
(7). the water glass of whipping step (6) preparation, the mixed solution of titanium dioxide, with acid the pH value of solution being adjusted to 9～10, is 60～100 ℃ of following ageings in temperature, separates mixed solution, to throw out washing, drying, prepare A1, A2 or A3 particulate coated with silica layer;
Or the Tai-Ace S 150 of constantly whipping step (6) preparation, the aqueous solution liquid of titanium dioxide, with alkali the pH value of solution being adjusted to 5～8, is 60～100 ℃ of following ageings in temperature, separates mixed solution, to throw out washing, drying, prepare A4, A5 or A6 particulate alumina-coated layer;
(8). with the particle that is used to prepare A1, A2, A3, A4, A5 or A6 that step (7) obtains, dispersed with stirring is in water, and weight percent concentration is 5～40%;
(9). for the particle that is used to prepare A1 in the step (8), the aqueous solution with the Tai-Ace S 150 of step (3) preparation slowly joins in step (8) aqueous solution, and wherein, titanium dioxide in the mixed solution: the mol ratio of Tai-Ace S 150 is 1: 0.01～1: 0.4; Mixing liquid, with alkali the pH value of solution is adjusted to 5～8, is 60～100 ℃ of following ageings in temperature, separates mixed solution, and to the throw out washing, drying is prepared A1 particulate alumina-coated layer;
Or for the particle that is used to prepare A2, A3, A4 or A5 in the step (8), disodium phosphate soln with step (4) preparation, slowly join in step (8) aqueous solution, wherein, titanium dioxide in the mixed solution: the mol ratio of Sodium phosphate dibasic is 1: 0.02～1: 0.5; And then slowly adding the silver complex solution that step (5) is prepared, Sodium phosphate dibasic in the mixed solution: the mol ratio of silver complex is 1: 1～1: 4; Stir ageing, separate mixed solution, to the throw out washing, drying is prepared A2, A3, A4 or A5 particulate Trisilver phosphate coating layer; Promptly obtain successively titanium dioxide antibiotic particle A3, or obtain successively titanium dioxide antibiotic particle A4 titanium dioxide granule coated aluminum oxide, Trisilver phosphate to titanium dioxide granule coated silica, Trisilver phosphate;
Or for the particle that is used to prepare A6 in the step (8), the sodium silicate aqueous solution with step (2) preparation slowly joins in step (8) aqueous solution, and titanium dioxide in the mixed solution: the mol ratio of water glass is 1: 0.01～1: 0.4; Stirring, with acid the pH value of solution is adjusted to 9～10, is 60～100 ℃ of following ageings in temperature, separates mixed solution, and to the throw out washing, drying is prepared A6 particulate coated with silica layer;
(10). the particles dispersed that is used for preparing A1 or A6 of step (9) to water, is slowly joined the disodium phosphate soln of step (4) preparation in the mixed solution, and wherein, titanium dioxide in the mixed solution: the mol ratio of Sodium phosphate dibasic is 1: 0.02～1: 0.5; Silver complex solution with step (5) preparation, slowly join in the mixed solution, Sodium phosphate dibasic in the mixed solution: the mol ratio of silver complex is 1: 1～1: 4, stir ageing, separate mixed solution, to throw out washing, drying, prepare A1 or A6 particulate Trisilver phosphate coating layer, promptly obtain successively titanium dioxide antibiotic particle A1 titanium dioxide granule coated silica, aluminum oxide, Trisilver phosphate; Or obtain successively titanium dioxide antibiotic particle A6 to titanium dioxide granule coated aluminum oxide, silicon-dioxide, Trisilver phosphate;
(11). step (9) is used for preparing the particles dispersed of A2 to water, slowly join the aqueous solution of the Tai-Ace S 150 of step (3) preparation in the mixed solution, wherein, titanium dioxide in the mixed solution: the mol ratio of Tai-Ace S 150 is 1: 0.01～1: 0.40, mix liquid, with alkali the pH value of solution is adjusted to 5～8, in temperature is 60～100 ℃ of following ageings, separate mixed solution, throw out is washed, drying is prepared A2 particulate alumina-coated layer, promptly obtains successively the titanium dioxide antibiotic particle A2 to titanium dioxide granule coated silica, Trisilver phosphate, aluminum oxide;
(12). with step (9) be used for prepare the particles dispersed of A5 to water, slowly join the sodium silicate solution of step (2) preparation in the mixed solution, titanium dioxide in the mixed solution: the mol ratio of water glass is 1: 0.01～1: 0.4, stir, with acid the pH value of solution is adjusted to 9～10, in temperature is 60～100 ℃ of following ageings, separate mixed solution, throw out is washed, dry, prepare A5 particulate coated with silica layer, promptly obtain successively titanium dioxide antibiotic particle A5 titanium dioxide granule coated aluminum oxide, Trisilver phosphate, silicon-dioxide;
(13). A3 and A4 antibacterial granule that step (9) is obtained, A1 that step (10) obtains or A6 antibacterial granule, the A2 antibacterial granule that step (11) obtains, the A5 antibacterial granule that step (12) obtains, be 300 ℃ of-900 ℃ of roastings in temperature respectively, pulverize, finally obtain silver phosphate antibacterial modified titanium dioxide composite particle respectively.
5. method as claimed in claim 4 is characterized in that: described silver complex is silver-ammonia complex or silver thiosulfate complex.
6. method as claimed in claim 4 is characterized in that: the volumetric molar concentration of the aqueous solution of described step (2) water glass is 0.01～1mol/L.
7. method as claimed in claim 4 is characterized in that: the aqueous solution volumetric molar concentration of described step (3) Tai-Ace S 150 is 0.01～1mol/L.
8. method as claimed in claim 4 is characterized in that: the volumetric molar concentration of the aqueous solution of described step (4) phosphoric acid oxygen disodium is 0.01～1mol/L.
9. method as claimed in claim 4 is characterized in that: the volumetric molar concentration of described step (5) the silver complex aqueous solution is 0.01～1mol/L.
10. method as claimed in claim 4 is characterized in that: described acid is nitric acid, hydrochloric acid or sulfuric acid; Described alkali is sodium hydroxide or ammoniacal liquor.
11. the purposes as the described silver phosphate antibacterial modified titanium dioxide composite particle of claim 1-3 is characterized in that: described silver phosphate antibacterial modified titanium dioxide composite particle is entrained in coating, pottery, plastics or the elastomeric material and uses as anti-biotic material.
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