CN101268784A - Method for preparing three-component coprecipitation molybdate antimicrobial by using microwave heating - Google Patents
Method for preparing three-component coprecipitation molybdate antimicrobial by using microwave heating Download PDFInfo
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- CN101268784A CN101268784A CNA2008100937752A CN200810093775A CN101268784A CN 101268784 A CN101268784 A CN 101268784A CN A2008100937752 A CNA2008100937752 A CN A2008100937752A CN 200810093775 A CN200810093775 A CN 200810093775A CN 101268784 A CN101268784 A CN 101268784A
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- antibacterial agent
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Abstract
The invention relates to a method for preparing Ag2MoO4-ZnMoO4-CuMoO4 by microwave heating. A test proves that the chemical reaction of the antimicrobial can be promoted to finish under microwave heating condition, thereby greatly shortening the preparation time of the antimicrobial. And when three components of coprecipitation molybdate antimicrobial powder body solution are prepared, a coprecipitation way is adopted, so that the grain diameter of the antimicrobial is evener, and the antimicrobial effect is improved. Through analyzing and comparing the XRD of a baking sample which is not baked at 1260 DEG C, the three components of molybdate antimicrobial has fine stability at high temperature. And the compound of parts of CuMoO4 and ZnMoO4 substitutes the compound of Ag2MoO4, so that the cost of the antimicrobial is lowered. The prepared Ag2MoO4-ZnMoO4-CuMoO4 antimicrobial is added into sanitary porcelain according to the proportion that the dosage of the antimicrobial is 1 to 2wt percent of the gross weight of dried glaze, and is baked at about 1260 DEG C to obtain an antimicrobial ceramic sample. Through an antimicrobial performance test, the bacteriostatic ratios of antimicrobial ceramic to colon bacillus and staphylococcus aureus are both at over 90 percent which accords with the standard of the antimicrobial ceramic in the building material industry.
Description
Technical field:
The present invention relates to the technology of preparing of inorganic antiseptic and the method in the introducing sanitary ceramics thereof.
Background technology:
Along with the generally raising of human substance life horizontal and civilization degree, the enhancing day by day of sense of self-protection.More and more wish to build a good ecotope that reduces germ as far as possible.Antibiotic construction sanitary ceramic is the healthy and safe product that is applied to building, family and public place.In the toilet, mankind's activity such as hospital ward and swimming pool frequently, easily grows the place that spreads disease germs and generally uses antibiotic construction sanitary ceramic, the requirement of cross-infection that reduces excremental pollution and public place is also more and more stronger, and this provides wide prospect for the antiseptic sanitary development.
At present, because the sterilizing ability of silver is better, the antibacterial agent that contains silver ion uses more.But because patina character is active, easy to change, reduced its anti-microbial property after the variable color, and silver is that anti-bacteria ceramic the ceramic surface cross-color, low in glossiness, poor durability, the cost that also have carrier the adding of antibiotic Effect on Performance, antibacterial agent is caused are high and how to make a series of problem such as the effective stripping of antibacterial material.
The molybdate inorganic antiseptic that the present invention is prepared belongs to the compound type antibacterial agent.Its advantage one is to prepare complex carrier, by form the antibiotic purpose of slowly-releasing that indissoluble of resistant to elevated temperatures molybdate compound own or insoluble characteristic and the very low performance of saturation solubility reach silver ion etc. in glaze.The 2nd, adopt heating using microwave to prepare Ag
2MoO
4-ZnMoO
4-CuMoO
4Three-component coprecipitation molybdate antimicrobial makes it have evenly, prepare characteristics efficiently.The 3rd, owing to use portion C uMoO
4, ZnMoO
4Compound replaces Ag
2MoO
4Compound makes the antibacterial agent cost reduce.
Summary of the invention:
The objective of the invention is to by the quick little and uniform co-precipitation three component molybdate antimicrobials of the stable particle diameter of preparation of heating using microwave, and then be incorporated in the preparation of anti-bacteria ceramic.
The antibacterial agent preparation method is as follows;
(1) the synthetic Ag of heating using microwave co-precipitation
2MoO
4-ZnMoO
4-CuMoO
4Antibacterial agent:
To prepare the mole ratio of components n of three component molybdenum hydrochlorates
Ag2MoO4: n
ZnMoO4: n
CuMoO4=2: be example at 1: 1:
1). first compound concentration is 0.1mol/L sodium molybdate solution 50ml, again toward wherein drip the copper nitrate that 10ml concentration is 0.1mol/L simultaneously, zinc nitrate and the 40ml concentration that 10ml concentration is 0.1mol/L is the silver nitrate of 0.1mol/L, obtains mixed solution.Mix about solution 1h, it is mixed.Placing power then is the micro-wave oven of 500～900W, and heating 30～120s makes it promote finishing of chemical reaction under microwave condition, and taking-up then again about agitating solution 1h, treats that sediment separates out after it is cooled off in stirring.
2). above-mentioned sediment is spent deionised water, filtered several times, to guarantee to remove the Na in the sediment
+, NO
3 -And MO
4 2-, and adopt AgNO
3There is not MO in the solution check cleaning solution
4 2-Ion residues.
3). it is that the micro-wave oven of 500～900W heats 3～5min and makes its drying that the sediment after will washing places power, promptly gets required antibacterial agent.Involved key reaction in the course of reaction:
3Na
2MoO
4+ 2AgNO
3+ Cu (NO
3)
2+ Zn (NO
3)
2=Ag
2MoO
4↓+CuMoO
4↓+ZnMoO
4↓+6NaNO
3(the co-precipitation color is pale yellow)
The weather resistance of antibacterial agent directly influences the outward appearance of anti-biotic material and the quality of anti-microbial property, and table 1 is the width test data of the antibacterial agent that makes antibacterial agent color and inhibition zone under different condition.
Antibacterial agent color under table 1 different condition and inhibition zone width
This antibacterial agent colors before and after 1260 ℃ of roastings all are faint yellow as known from Table 1, do not have the generation of the silver oxide of grey black and simple substance silver, copper oxide.And along with variation of temperature, in inhibition zone when test,, inhibition zone wide variety difference is about 0.20mm, and along with the rising of temperature, changes little.
From accompanying drawing 1 as can be seen, three component antibacterial agents do not burn with 1260 ℃ of calcinings after, the XRD figure spectrum that obtains is basic identical.According to the peak value in the XRD figure spectrum, several main characteristic peaks all meet Ag
2MoO
4-ZnMoO
4-CuMoO
4Feature, and before and after the calcining just crystalline form change to some extent, but do not change other material into, have good high-temperature stability.
Accompanying drawing 2 is respectively Ag
2MoO
4-ZnMoO
4-CuMoO
4The antibiotic circle test of the different temperatures of antibacterial agent.
(2) preparation of anti-bacteria ceramic sample:
With prepared Ag
2MoO
4-ZnMoO
4-CuMoO
4The antibacterial agent consumption adds in the sanitary ceramic glaze with the ratio of 1～2wt% of dried glaze gross weight, stirs about 1h, and antibacterial agent is disperseed in glaze fully.Then antibiotic glaze slip is imposed on the greenwave surface, dry again back adopts oxidizing atmosphere to burn till, and maximum sintering temperature is 1260 ℃, finally makes the anti-bacteria ceramic sample.
Carry out the anti-bacteria ceramic sample of making antibiotic and the weather resistance test.Antibiotic ceramic surface is cleaned and flooded experiment with hydrochloric acid and clorox, clean 3h respectively at sample surfaces, perhaps direct impregnation is 3 months, carries out antibacterial experiment again.Result such as table 2.
Table 2 anti-bacteria ceramic durability antibacterial tests result
By table 2 as seen, with Ag
2MoO
4-ZnMoO
4-CuMoO
4Antibiotic pulvis joins the anti-bacteria ceramic of making in the ceramic glaze, behind certain density hydrochloric acid and clorox scouring or dipping, though antibiotic rate has descended 0.3～1.3%, the anti-bacteria ceramic sample still keeps higher antibiotic property, illustrates that the acid and alkali resistance of anti-bacteria ceramic sample is stronger.
Accompanying drawing 3 is the digital photograph the during test of molybdate anti-bacteria ceramic antibiotic rate before and after cleaning, by with the contrast of non-anti-bacteria ceramic, can find out intuitively that anti-bacteria ceramic has good bactericidal property.Characteristics of the present invention are: first heating using microwave, the synthetic method of co-precipitation are introduced Ag
2MoO
4-ZnMoO
4-CuMoO
4In the preparation of three component molybdenum silicate antibiosis powders.Test shows that the cycle needs 4～12h for preparing antibacterial agent with the magnetic agitation heating method compares, and the method manufacturing cycle of employing heating using microwave only just can obtain the antibacterial agent of better effects if about 2h, saved the time so greatly; Secondly the synthetic method of co-precipitation is introduced Ag
2MoO
4-ZnMoO
4-CuMoO
4The powder preparation of three component molybdenum hydrochlorates, the antibacterial agent that obtains is even, and particle diameter is little.The 3rd owing to use portion C uMoO
4, ZnMoO
4Compound replaces Ag
2MoO
4Compound makes the antibacterial agent cost reduce.
Table 3 illustrates the comparison that heating using microwave and magnetic agitation add hot preparation antibacterial agent color, particle diameter and anti-microbial property;
The comparison of table 3 heating using microwave and magnetic agitation heating synthetic antibacterial agents
As can be seen from Table 3, heating using microwave prepares the cycle of three-component coprecipitation molybdate antimicrobial much smaller than adopting magnetic agitation heating manufacturing cycle, and it is convenient and swift to use micro-wave oven to add the hot preparation antibacterial agent; For the reactant liquor with concentration, the antibacterial agent color that microwave heating method makes, particle diameter, antibacterial effect all are better than the magnetic agitation heating method.
Carry out the antibacterial effect test to making antibacterial agent and anti-bacteria ceramic, the antibiotic rate of Escherichia coli and staphylococcus aureus is tested all more than 90%, meet the standard of Chinese building material industry anti-bacteria ceramic.
Description of drawings:
Fig. 1 three component antibacterial agents are in the XRD figure spectrum of heat treatments at different
The inhibition zone of Fig. 2 different temperatures three component antibacterial agents
Antibiotic rate test digital photograph: a. of the different ceramics samples of Fig. 3 does not add the anti-bacteria ceramic of ceramic b. dipping scouring after three months of antibacterial agent
Embodiment:
Embodiment 1
With concentration be liquor argenti nitratis ophthalmicus 40ml that the copper nitrate solution 10ml of 0.1mol/L, zinc nitrate solution 10ml that concentration is 0.1mol/L and concentration are 0.1mol/L to be added drop-wise to 50ml concentration simultaneously be in the 0.1mol/L sodium molybdate solution, obtain mixed solution.Mix about solution 1h, it is mixed.Placing power then is the micro-wave oven of 500～900W, and heating 30～120s makes it finish chemical reaction under microwave condition, takes out then, again about agitating solution 1h, treats that sediment separates out after it is cooled off in stirring.The sediment that washing, filtration, drying are separated out promptly gets Ag
2MoO
4-ZnMoO
4-CuMoO
4Three component antibacterial agent powders.
Embodiment 2
With prepared Ag
2MoO
4-ZnMoO
4-CuMoO
4The antibacterial agent consumption adds in the sanitary ceramic glaze with the ratio of 1～2wt% of dried glaze gross weight, stirs about 1h, makes antibacterial agent in glaze
Claims (2)
1. one kind is adopted heating using microwave to prepare Ag
2MoO
4-ZnMoO
4-CuMoO
4The method of three-component coprecipitation molybdate antimicrobial is characterized in that this method may further comprise the steps:
(1) first compound concentration is 0.1mol/L sodium molybdate solution 50ml, again toward wherein drip the copper nitrate solution that 10ml concentration is 0.1mol/L simultaneously, zinc nitrate solution and the 40ml concentration that 10ml concentration is 0.1mol/L is the liquor argenti nitratis ophthalmicus of 0.1mol/L, obtain mixed solution, mix about solution 1h, it is mixed, placing power then is the micro-wave oven of 500～900W, heating 30～120s makes it finish chemical reaction under microwave condition, take out then, treat that sediment separates out after it is cooled off in stirring;
(2) above-mentioned sediment is spent deionised water, filtered several times, to guarantee to remove the Na in the precipitation
+, NO
3 -And MO
4 2-, and adopt AgNO
3There is not MO in the solution check cleaning solution
4 2-Ion residues;
(3) to place power be that the micro-wave oven of 500～900W heats 3～5min and makes its drying to the sediment after will washing, and promptly gets required antibacterial agent.
2. Ag with the preparation of the described method of claim 1
2MoO
4-ZnMoO
4-CuMoO
4Antibacterial agent is used for the method for pottery, it is characterized in that the ratio that the antibacterial agent consumption is accounted for 1～2wt% of dried glaze gross weight joins in the sanitary ceramic glaze, stirs about 1h, and antibacterial agent is disperseed in glaze fully; Then antibiotic glaze slip is imposed on the greenwave surface, dry back adopts oxidizing atmosphere to burn till, and 1260 ℃ of maximum sintering temperatures make the anti-bacteria ceramic sample at last; Antibacterial test meets the standard of Chinese building material industry anti-bacteria ceramic.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267723A (en) * | 2011-06-26 | 2011-12-07 | 河北联合大学 | Method for synthesizing zinc molybdate nanosheet by virtue of a structure-directing-agent-assisted microwave radiation method |
| CN102502842A (en) * | 2011-11-07 | 2012-06-20 | 河北联合大学 | Preparation method for radial copper molybdate microspheres assembled by nanowires |
| CN105218384A (en) * | 2015-08-11 | 2016-01-06 | 泉州理工职业学院 | A kind of molybdenum compound and its preparation method and application |
| JP2016190808A (en) * | 2015-03-31 | 2016-11-10 | 住化エンバイロメンタルサイエンス株式会社 | Antiviral composition |
| CN108439469A (en) * | 2018-02-13 | 2018-08-24 | 浙江大学 | A kind of preparation of silver molybdate nano-powder in subsphaeroidal structure and application process |
| EP3082415B1 (en) * | 2013-12-19 | 2019-05-08 | Amistec GmbH & Co. KG | Antimicrobial composite material and process for the preparation thereof |
| DE102013114573B4 (en) | 2013-12-19 | 2022-10-13 | Fritz Egger Gmbh & Co. Og | Process for the production of an antimicrobially effective furniture and/or interior component |
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| CN102161509B (en) * | 2011-02-12 | 2013-04-03 | 河北联合大学 | Method for synthesizing metal molybdate micron/nano materials by adopting microwave radiation method |
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2008
- 2008-04-21 CN CNB2008100937752A patent/CN100556287C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102267723A (en) * | 2011-06-26 | 2011-12-07 | 河北联合大学 | Method for synthesizing zinc molybdate nanosheet by virtue of a structure-directing-agent-assisted microwave radiation method |
| CN102502842A (en) * | 2011-11-07 | 2012-06-20 | 河北联合大学 | Preparation method for radial copper molybdate microspheres assembled by nanowires |
| EP3082415B1 (en) * | 2013-12-19 | 2019-05-08 | Amistec GmbH & Co. KG | Antimicrobial composite material and process for the preparation thereof |
| DE102013114573B4 (en) | 2013-12-19 | 2022-10-13 | Fritz Egger Gmbh & Co. Og | Process for the production of an antimicrobially effective furniture and/or interior component |
| JP2016190808A (en) * | 2015-03-31 | 2016-11-10 | 住化エンバイロメンタルサイエンス株式会社 | Antiviral composition |
| JP7008914B2 (en) | 2015-03-31 | 2022-01-25 | 住化エンバイロメンタルサイエンス株式会社 | Antiviral composition |
| JP7460211B2 (en) | 2015-03-31 | 2024-04-02 | 住化エンバイロメンタルサイエンス株式会社 | How to impart antiviral performance |
| CN105218384A (en) * | 2015-08-11 | 2016-01-06 | 泉州理工职业学院 | A kind of molybdenum compound and its preparation method and application |
| CN105218384B (en) * | 2015-08-11 | 2017-08-01 | 臧树良 | A kind of preparation method and application of molybdenum compound |
| CN108439469A (en) * | 2018-02-13 | 2018-08-24 | 浙江大学 | A kind of preparation of silver molybdate nano-powder in subsphaeroidal structure and application process |
| CN108439469B (en) * | 2018-02-13 | 2019-12-20 | 浙江大学 | Preparation and application method of silver molybdate nano powder with nearly spherical structure |
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| CN100556287C (en) | 2009-11-04 |
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