CN1286923C - Antibacterial nano supported materials capable of releasing anion and preparation method and use thereof - Google Patents
Antibacterial nano supported materials capable of releasing anion and preparation method and use thereof Download PDFInfo
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- CN1286923C CN1286923C CNB2004100069696A CN200410006969A CN1286923C CN 1286923 C CN1286923 C CN 1286923C CN B2004100069696 A CNB2004100069696 A CN B2004100069696A CN 200410006969 A CN200410006969 A CN 200410006969A CN 1286923 C CN1286923 C CN 1286923C
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Abstract
The present invention belongs to inorganic nanometer modifying functional material and an application area thereof and particularly relates to negative ion-releasing composite antibacterial material containing silver nitrate, titanium dioxide and tourmaline, a preparation method and purposes thereof. Nanometer or submicron tourmaline particles are used as a kernel for adsorbing the silver nitrate on the surface of tourmaline particles and are doped with titanium dioxide particles, and then, a silicon dioxide layer or an alumina layer is coated on the nanometer or submicron tourmaline particles to obtain porose negative ion-releasing antibacterial nanometer loading material which has the size from 52 to 4050 nm. The composite body has the functions of releasing negative ions, bacterium resistance, etc. The antibacterial material can be doped in textiles, paint, ceramics, plastics, rubber, paper or chemical fiber material as antibacterial health care material.
Description
Technical field
The invention belongs to inorganic nanometer modified functional materials and Application Areas thereof, particularly relate to discharge negative ion contain Silver Nitrate, titanium dioxide, tourmalinite composite antibacterial material and its production and use.
Background technology
" SARS " bears down menacingly, and wreaks havoc the whole world, and the existent environment of people that appears as of " SARS " virus has been beaten alarm bell once more.Public health consciousness and Personal hygiene custom difference is one of reason of breaking out in China of SARS epidemic situation.Take the measure of favourable public health and environment protection more and more urgent, set up health, healthy work, living environment, with the pool by later age, be benefited infinite.Anti-biotic material certainly will will use at aspects such as hospital, dwelling house, public place, daily necessitiess in a large number as a kind of important environment-friendly materials.
Inorganic antiseptic has advantages such as security is good, good heat resistance, long service life, no volatilization, so inorganic antiseptic becomes one of current antiseptic-germicide hot of research and development.According to the effective ingredient difference, inorganic antiseptic can be divided into silver system and (contain Ag
+, Cu
2+, Zn
2+Deng metal ion) and titanium system (having the titanium dioxide of photocatalysis etc.) antiseptic-germicide (Rong Hungren, Zhao Bin, Gu Hongchen, Gao Wei, inorganic antiseptic general introduction, chemistry world, 2000,7:339～342).Mostly commercial inorganic antiseptic is silver-series antibacterial agent.The nano titanium dioxide photocatalysis anti-biotic material has nontoxic, tasteless, nonirritant, thermostability and good heat resistance, and certainly as advantages such as whites, so application prospect is boundless.
Negative oxygen ion extensively is present in the Nature, and in the high place of content, as forest, river bank, waterfall etc., it makes the happiness of people's body and mind.As far back as 1902, the biological significance of air ion was just affirmed by scientific circles, and in 1980, German medical circle took the lead in proving that the many local people of positive ion suffer from various chronic diseases and get the ratio height; The local negative ion that " scenery with hills and waters " is good is many, and air is obviously pure and fresh, and sickness rate is low." negative ion " can make the seepage force of cell strengthen when entering lung by breathing.It will pass the lung endothelial cell wall, enter blood by capillary vessel, and the potential of hydrogen of blood is adjusted to weakly alkaline (pH=7.5).This weak surface activation effect of negative ion can be decomposed cholesterol, and the mitigation coagulation of blood brings high blood pressure down, and the accelerate blood circulation improves metabolism, promotes internal secretion, gets resistance against diseases thereby strengthen human body.The effect of negative aeroion is admitted by vast medical circle, except useful HUMAN HEALTH, also has sterilization, dedusting, deodorization (Lin Zhongning, the negative aeroion effect in health care, ecological science, 1999,18 (2): 87-90).
Tourmalinite is because of its pyroelectricity, piezoelectricity, and has a stronger ir radiation effect, discharge characteristics such as negative ion, can be developed as environmental protection and healthcare product (Wu Ruihua, Tang Yunhui, Zhang Xiaohui, the electrical effect of tourmalinite and the application prospect in environmental area thereof, 2001,21 (4): 474～477).With the tourmaline powder is carrier absorption Ag
+, titania-doped, and utilize nanotechnology that this release negative ion antibiotic material is carried out the surface to coat, can reach stable, long lasting purpose.
Summary of the invention
One of purpose of the present invention provides a kind of antimicrobial nano support materials that discharges negative ion, constitutes the composite particles purity height of this support materials, good dispersity; This particle is the pyroelectricity that utilizes tourmalinite, discharges negative ion, thereby improves metabolism, promotes internal secretion, strengthens the resistance against diseases of human body; Silver ions and titania nanoparticles make this material have excellent antibacterial properties simultaneously.
Two of purpose of the present invention provides a kind of preparation method who discharges the antimicrobial nano support materials of negative ion.
Three of purpose of the present invention provides a kind of purposes that discharges the antimicrobial nano support materials of negative ion.
Purpose of the present invention will further be set forth by following detailed description.
Antimicrobial nano support materials with negative ion-releasing function of the present invention is to have the nanometer of Silver Nitrate or submicron tourmaline particle to mix with titanium dioxide granule surface adsorption, coat layer of silicon dioxide or alumina layer then on the surface of this composite grain, obtain having the antimicrobial nano support materials of the release negative ion of porous character.Described titanium dioxide granule accounts for 2～50% of tourmaline particle and titanium dioxide granule gross weight, is preferably 10～30%.
Between 50nm～4000nm, described silicon-dioxide or alumina-coated layer thickness are respectively 2～50nm to the particle diameter of described tourmaline particle and titanium dioxide granule respectively.
Preparation method with antimicrobial nano support materials of negative ion-releasing function of the present invention is:
(1). the aqueous solution of preparation Silver Nitrate, its volumetric molar concentration is 0.01～1mol/L, is preferably 0.01～0.2mol/L.
(2). with the tourmaline particle dispersed with stirring in the aqueous solution of step (1) Silver Nitrate, the weight percent concentration of tourmaline particle in the aqueous solution of Silver Nitrate is 5～40%, be preferably 5～25%, 10～60 ℃ of constant temperature, be preferably 20～40 ℃, lucifuge, stirring about 5 hours, washing, drying obtain nanometer or submicron tourmaline particle that surface adsorption has Silver Nitrate.
(3). the particle that step (2) is prepared mixes with commercially available titanium dioxide granule, and wherein titanium dioxide granule accounts for 2～50% of composite grain gross weight, is preferably 10～30%.Add a certain amount of water, the weight percent concentration of composite grain in water is 5～40%, is preferably 5～25%.
Can carry out aluminum oxide or coated with silica respectively to the composite grain that step (3) prepare.
(4). 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.
Or
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.
(5). the aluminum sulfate aqueous solution of step (4) preparation is slowly joined in the composite grain solution of step (3) preparation, and preparation is used to prepare the solution of the negative ion antibiotic nano load material granule of coated aluminum oxide;
Wherein, the consumption of aluminum sulfate aqueous solution is determined composite particles in the mixed solution according to the size of step (3) preparation composite particles, the thickness requirement of required aluminum oxide coating layer: the mol ratio of Tai-Ace S 150 is 1: 0.01～1: 0.4;
Or
The aqueous solution of the water glass of step (4) preparation is slowly joined in the composite grain solution of step (3) preparation, and preparation is used to prepare the solution of the negative ion antibiotic nano load material granule of coated silica;
Wherein, the consumption of sodium silicate aqueous solution is determined composite particles 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.
(6). composite particles and Tai-Ace S 150 mixed solution that continuous whipping step (5) prepares, 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 the negative ion antibiotic nano load material of coated aluminum oxide;
Or the constantly composite particles for preparing of whipping step (5) and the mixed solution of water glass, 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 the negative ion antibiotic nano load material of coated silica.
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.
Antimicrobial nano support materials with negative ion-releasing function of the present invention is entrained in and can be used as the antimicrobial health-care material use in textiles, coating, pottery, plastics, rubber, paper or the fibers material.
Anti-microbial property with antimicrobial nano support materials of negative ion-releasing function of the present invention is tested with reference to GB15981-1995, and Q/HDHKH002-2000 detection method and standard are carried out.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 antimicrobial nano support materials sample and common material 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.
Antimicrobial nano support materials with negative ion-releasing function of the present invention has:
1. prepare simplely, be easy to apply.
2. the use tourmaline powder can produce negative ion, has the metabolism of improvement, promotes internal secretion, strengthens human body and gets resistance against diseases.
3. with comparatively inexpensive anatase titanium dioxide TiO
2And Silver Nitrate, having kept the optically catalytic TiO 2 activity, anti-microbial effect is remarkable.
4. negative ion antibiotic nano load material just has very strong anti-microbial effect under more weak visible light effect.
5. by adjusting silicon-dioxide, alumina-coated layer, and coating thickness, be easy to make can be compatible with other composition of different sorts antimicrobial prod the antibiotic health care product.
Embodiment
Embodiment 1
With particle diameter be the tourmaline particle dispersed with stirring of 200nm～1000nm in the aqueous solution of 0.1mol/L Silver Nitrate, the weight percent concentration of tourmaline particle is 25%.30 ℃ of constant temperature, lucifuge, stirring 5 hours, washing, drying obtain the tourmaline particle that surface adsorption has Silver Nitrate; Be that the titanium dioxide granule of 200～400nm mixes with particle diameter then, wherein titanium dioxide granule accounts for 20% of composite grain gross weight, adds certain water, and the weight percent concentration of composite grain in water is 10%.In this mixing solutions, slowly be added dropwise to sodium silicate aqueous solution, tourmalinite and TiO after being warmed up to 85 ℃
2The initial molar ratio of composite grain and water glass is 5: 1, and its dropping time is 20 minutes.Use sulfuric acid that the pH of mixed solution is adjusted to 9.5, stir ageing down 2 hours, obtain the grey turbid solution, sedimentation, washing, separation, drying obtain having the negative ion antibiotic nano load material of coated with silica layer.Coating thickness is about 20nm.This antimicrobial nano support materials can be used for powder coating, improves the quality of product.
Embodiment 2
With particle diameter be 200～1500nm tourmaline particle dispersed with stirring in the aqueous solution of 0.1mol/L Silver Nitrate, the weight percent concentration of tourmaline particle is 25%.40 ℃ of constant temperature, lucifuge, stirring 5 hours, washing, drying obtain the tourmaline particle that surface adsorption has Silver Nitrate.Be that the titanium dioxide granule of 100～400nm mixes with particle diameter then, wherein titanium dioxide granule accounts for 20% of composite grain gross weight, adds certain water, and the weight percent concentration of composite grain in water is 10%.In this mixing solutions, slowly be added dropwise to aluminum sulfate aqueous solution, tourmalinite and TiO after being warmed up to 70 ℃
2The initial molar ratio of composite grain and Tai-Ace S 150 is 5: 1.Use sodium hydroxide that the pH of mixed solution is adjusted to 7.0, stir ageing down 4 hours, obtain the grey turbid solution, sedimentation, washing, separation, drying obtain having the negative ion antibiotic nano load material of alumina-coated layer.Coating thickness is about 15nm.This antimicrobial nano support materials can be used as the filler of rubber, improves the quality of product.
Embodiment 3
With particle diameter be 100～1500nm tourmaline particle dispersed with stirring in the aqueous solution of 0.05mol/L Silver Nitrate, the weight percent concentration of tourmaline particle is 15%.60 ℃ of constant temperature, lucifuge, stirring are about 5 hours, and washing, drying obtain the tourmaline particle that surface adsorption has Silver Nitrate.Be that the titanium dioxide granule of 100～400nm mixes with particle diameter then, wherein titanium dioxide granule accounts for 10% of composite grain gross weight, adds certain water, and the weight percent concentration of composite grain in water is 15%.In this mixing solutions, slowly be added dropwise to sodium silicate aqueous solution, tourmalinite and TiO after being warmed up to 85 ℃
2The initial molar ratio of composite grain and water glass is 6: 1, and its dropping time is 25 minutes.Use hydrochloric acid that the pH of mixed solution is adjusted to 9.5, stir ageing down 2.5 hours, obtain the grey turbid solution, sedimentation, washing, separation, drying obtain having the negative ion antibiotic nano load material of silicon dioxide layer.Coating thickness is about 30nm.This antimicrobial nano support materials can be used as the filler of plastics, improves the quality of product.
Embodiment 4
With particle diameter be 50～2000nm tourmaline particle dispersed with stirring in the aqueous solution of 0.05mol/L Silver Nitrate, the weight percent concentration of tourmaline particle is 15%.40 ℃ of constant temperature, lucifuge, stirring 4.5～5 hours, washing, drying obtain the tourmaline particle that surface adsorption has Silver Nitrate.Be that the titanium dioxide granule of 50～500nm mixes with particle diameter then, wherein titanium dioxide granule accounts for 10% of composite grain gross weight.Add certain water, the weight percent concentration of composite grain in water is 15%.In this mixing solutions, slowly be added dropwise to sodium silicate aqueous solution, tourmalinite and TiO after being warmed up to 85 ℃
2The initial molar ratio of composite grain and water glass is 4: 1, and its dropping time is 30 minutes.Use sulfuric acid that the pH of mixed solution is adjusted to 9.5, stir ageing down 2.5 hours, obtain grey look turbid solution, sedimentation, washing, separation, drying obtain having the negative ion antibiotic nano load material of coated with silica layer.Coating thickness is about 2 nanometers.This antimicrobial nano support materials can be used as the filler of rubber, improves the quality of product.
Embodiment 5
With particle diameter be 50～4000nm tourmaline particle dispersed with stirring in the aqueous solution of 0.05mol/L Silver Nitrate, the weight percent concentration of tourmaline particle is 15%.10 ℃ of constant temperature, lucifuge, stirring 5 hours, washing, drying obtain the tourmaline particle that surface adsorption has Silver Nitrate.Be that the titanium dioxide granule of 100～300nm mixes with particle diameter then, wherein titanium dioxide granule accounts for 10% of composite grain gross weight, adds certain water, and the weight percent concentration of composite grain in water is 30%.In this mixing solutions, slowly be added dropwise to aluminum sulfate aqueous solution, tourmalinite and TiO after being warmed up to 70 ℃
2The initial molar ratio of composite grain and Tai-Ace S 150 is 6: 1.Use sodium hydroxide that the pH of mixed solution is adjusted to 7, stir ageing down 4 hours, obtain the grey turbid solution, sedimentation, washing, separation, drying obtain having the negative ion antibiotic nano load material of alumina-coated layer.Coating thickness is about 50nm.This antimicrobial nano support materials can be used as the filler of pottery, improves the quality of product.
Embodiment 6
With particle diameter be 50～4000nm tourmaline particle dispersed with stirring in the aqueous solution of 0.05mol/L Silver Nitrate, the weight percent concentration of tourmaline particle is 15%.40 ℃ of constant temperature, lucifuge, stirring 5～5.5 hours, washing, drying obtain the tourmaline particle that surface adsorption has Silver Nitrate.Then be that the titanium dioxide granule of 50～400nm mixes with particle diameter, wherein titanium dioxide granule accounts for 10% of composite grain gross weight, adds certain water, the weight percent concentration of composite grain in water is 20%.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 that the pH of mixed solution is adjusted to 7, stir ageing down 3.5 hours, obtain the grey turbid solution, sedimentation, washing, separation, drying obtain having the negative ion antibiotic nano load material of alumina-coated layer.Coating thickness is about 2nm.This antimicrobial nano support materials can be used as the filler of chemical fibre, improves the quality of product.
Embodiment 7
The negative ion antibiotic nano load material of embodiment 1～6 preparation is carried out antibiotic detection.The anti-microbial property experiment is with reference to GB15981-1995, and Q/HDHKH002-2000 detection method and standard are carried out.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 anti-biotic material sample and common material 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.
Claims (7)
1. antimicrobial nano support materials that discharges negative ion, it is characterized in that: described material is nanometer or submicron tourmaline particle and the titanium dioxide granule composition mixture that surface adsorption is had Silver Nitrate, coats layer of silicon dioxide or alumina layer on the surface of this mixture;
Titanium dioxide granule accounts for 2～50% of tourmaline particle and titanium dioxide granule gross weight in the described material;
The particle diameter of described tourmaline particle and titanium dioxide granule is respectively 50nm～4000nm;
Described silicon-dioxide or alumina-coated layer thickness are 2～50nm.
2. preparation methods as claimed in claim 1, it is characterized in that: described method may further comprise the steps:
(1). the aqueous solution of preparation Silver Nitrate;
(2). in the aqueous solution of the Silver Nitrate of step (1) preparation, wherein, the concentration of Silver Nitrate is 0.01～1mol/L in the aqueous solution with the tourmaline particle dispersed with stirring, and the weight percent concentration of tourmaline particle in silver nitrate aqueous solution is 5～40%; Constant temperature, lucifuge, stirring, washing, drying obtain nanometer or submicron tourmaline particle that surface adsorption has Silver Nitrate;
(3). the particle that step (2) is prepared mixes with titanium dioxide granule, and wherein titanium dioxide granule accounts for 2～50% of composite grain gross weight; Add entry, the weight percent concentration of composite grain in water is 5～40%;
(4). the aqueous solution of preparation Tai-Ace S 150, or the aqueous solution of preparation water glass;
(5). the aluminum sulfate aqueous solution of step (4) preparation is slowly joined in the composite grain solution of step (3) preparation, and wherein, composite particles in the mixed solution: the mol ratio of Tai-Ace S 150 is 1: 0.01～1: 0.4;
Or
The aqueous solution of the water glass of step (4) preparation is slowly joined in the composite grain solution of step (3) preparation, and wherein, composite particles in the mixed solution: the mol ratio of water glass is 1: 0.01～1: 0.4;
(6). composite particles that whipping step (5) prepares and Tai-Ace S 150 mixed solution, with alkali the pH value of solution is adjusted to 5～8, stirring, ageing separate mixed solution, to throw out washing, drying, prepare the negative ion antibiotic nano load material of coated aluminum oxide;
Or the composite particles for preparing of whipping step (5) and the mixed solution of water glass, with acid the pH value of solution is adjusted to 9～10, stirring, ageing separate mixed solution, to throw out washing, drying, prepare the negative ion antibiotic nano load material of coated silica.
3. method as claimed in claim 2 is characterized in that: described acid is nitric acid, hydrochloric acid or sulfuric acid.
4. method as claimed in claim 2 is characterized in that: described alkali is sodium hydroxide or ammoniacal liquor.
5. method as claimed in claim 2 is characterized in that: described titanium dioxide is sharp attitude type titanium dioxide.
6. method as claimed in claim 2 is characterized in that: the thermostat temperature in the described step (2) is 10～60 ℃.
7. the purposes of a material as claimed in claim 1 is characterized in that: described material dopedly use as antimicrobial health-care material in textiles, coating, pottery, plastics, rubber, paper or fibers material.
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|---|---|---|---|
| CNB2004100069696A CN1286923C (en) | 2004-03-03 | 2004-03-03 | Antibacterial nano supported materials capable of releasing anion and preparation method and use thereof |
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| CNB2004100069696A CN1286923C (en) | 2004-03-03 | 2004-03-03 | Antibacterial nano supported materials capable of releasing anion and preparation method and use thereof |
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| CN1286923C true CN1286923C (en) | 2006-11-29 |
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2004
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