CN103651569A - Technology for preparing surface-coated modified Ag/ZnO nano composite antibacterial agent - Google Patents
Technology for preparing surface-coated modified Ag/ZnO nano composite antibacterial agent Download PDFInfo
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Abstract
The invention provides a technology for preparing a surface-coated modified Ag/ZnO nano composite antibacterial agent. The technology comprises the following steps: (1) adding sodium hexametaphoshpate serving as a dispersing agent into distilled water; (2) adding nano ZnO powder into the solution; (3) performing washing and filtering, and then drying the material in a constant-temperature drying oven at the temperature of 80-120 DEG C for 3-4 hours; (4) putting the material into a box type resistance furnace for roasting at the temperature of 600-800 DEG C for 2-4 hours; (5) taking out the material and grinding the material into raw powder of an Ag/ZnO nano composite antibacterial agent, adding the raw powder of the Ag/ZnO antibacterial agent into the distilled water, then adding a sodium laurate coating agent according to the mass ratio of the raw powder and the sodium laurate of 500 to 1, adjusting the pH value of the solution to 5-6, controlling the temperature of a water bath, and mechanically stirring the materials under the temperature range of 25-40 DEG C for 1-2 hours, filtering and drying the materials to obtain the surface-coated modified Ag/ZnO nano composite antibacterial agent. The surface-coated modified Ag/ZnO nano composite antibacterial agent disclosed by the invention is high in antibacterial performance and has a long-time antibacterial characteristic.
Description
Technical field
The present invention relates to anti-biotic material field, be specifically related to the technique that a kind of preparation table bread covers modified Nano complex antimicrobials.
Background technology
Anti-biotic material is the new function material with sterilization, bacteriostasis property, and the nucleus in anti-biotic material is antibacterial agent.Antibacterial agent is to make the microorganisms such as bacterium, fungi can not grow or suppress the material of their growths.Nano-ZnO not only have active high, photocatalysis antibacterial speed fast, Heat stability is good, the feature such as permanently effective and harmless, and has the functions such as purification, self-cleaning, deodorizing, thereby becomes a kind of photocatalyst-type inorganic antiseptic receiving much concern.But use separately photocatalysis antibacterial agent also to exist some problems, such as this class antibacterial agent must be under light conditions, particularly under UV-irradiation, just there is the ability of sterilization, degradation of organic substances and auto purification, therefore, using them as carrier, the metal ion with antibacterial functions is carried on this class antibacterial agent, improves the effect of photocatalysis antibacterial agent, widening its range of application just becomes the direction that a lot of researchers are studying.In metal ion, the sterilizing ability of silver is the strongest, and adding of silver can make the anti-microbial property of ZnO material improve, and expands its application in antibacterial product.The main method of the preparation Ag/ZnO nano composite material of report has high-molecular gel method, dipping light decomposition method, photo-reduction sedimentation, laser composite heating evaporation technique etc. at present.These method synthesis steps are various, and agglomeration easily occurs goods, also easy variable color.This technology be take nano-ZnO as carrier, add sodium hexametaphosphate dispersant, adopt ion set packing technique, by common solwution method (solution dipping method), nano-ZnO is carried out to the assembling of Ag ion, utilize sodium laurate to carry out surface coating modification to the antibacterial agent of preparation simultaneously, explored a kind of new technology of the Ag/ZnO of preparation composite nano germicide.This method technique is simple, and the product of preparation has excellent antibacterial and photocatalysis performance, is especially applied in macromolecular material antibacterial effect remarkable.The complex antimicrobials of preparation is added in high polymer and prepares antibiotic plastic, and result of study shows that the antibiotic plastic of preparation has strong antimicrobial effect, has again stable antimicrobial long-acting simultaneously.
Although nano-ZnO has photocatalysis antibacterial characteristic, and in antibacterial field, be applied gradually, due to its photo-catalysis capability a little less than, and need ultraviolet ray to irradiate just to embody photo-catalysis capability, its antibacterial ability is compared other anti-biotic materials as Ag/Ag
+also have larger gap, therefore in application, be restricted, the particularly application in thering are the plastics of stronger coating function, due to the strong coating function of plastics, the photocatalysis antibacterial ability of ZnO is almost not reflected.Therefore this research adopts ion set packing technique, nano-ZnO is carried out to the assembling of Ag ion, further promotes the broad-spectrum antiseptic ability of nano-ZnO.In addition, the reunion of nano-powder is the key issue of its extensive use of restriction always, this research has also been carried out further surface modified to prepared antimicrobial nano zinc oxide composite powder, to improve its dispersing characteristic, make it in plastics, there is good dispersing characteristic, given play to better its excellent specific property, and applied technical support is provided for the market of follow-up middle trial production and promotion nano zine oxide.
Nano-ZnO particle size is little, surface can be high, specific surface area is much larger than common material, and surface exists the atom of a large amount of coordination deficiencies simultaneously, can be used as carrier, utilize its surperficial high chemism and strong adsorptivity, the metal ion at its adsorption with antibacterial functions is prepared complex antimicrobials.
The difficult point of the research is:
1. in the assembling of the enterprising row metal Ag of nano-ZnO ion and the control of related process parameter thereof, be, key issue.Can adopt infusion process by adding the Zeta potential of the parameter regulator solutions such as surfactant, control pH value, make desired ion can be attached to ZnO particle surface, then by techniques such as roastings, make it anchor at powder surface, then inquire into technological parameter.
2., because the ion of institute's load is disperse state, distribute, for the sign of supported ionic existence, be also a large difficult point, so need to adopt multiple characterization method to combine and could analyze out.As observed the particle size of powder in conjunction with XRD in conjunction with the pattern of tem observation Ag/ZnO composite nano germicide, in conjunction with XPS, observe coated situation of split etc.
3., the agglomeration traits of nano-powder, the Ag/ZnO composite nano germicide of preparation is carried out surface modified, to improve its dispersibility in goods, it is disperseed more uniformly in plastics or coating, given play to better its excellent specific property.
Summary of the invention
Goal of the invention: the present invention, in order to solve the deficiencies in the prior art, provides a kind of technique of preparing surface coating modification Ag/ZnO composite nano germicide.
Technical scheme: a kind of technique of preparing the Ag/ZnO composite nano germicide of surface coating modification, comprises the steps:
1), in distilled water, add dispersant sodium hexametaphosphate, the mass ratio 500:1 of distilled water and dispersant, is stirred to completely and dissolves;
2), in step 1) solution in add nano ZnO powder, the mass ratio 60:1 of distilled water and nano ZnO powder, first disperses 30 minutes with ultrasonic afterwards, then adds AgNO
3, nano ZnO powder and AgNO
3mass ratio 20:1, the pH value of regulator solution is between 7-8, mechanical agitation 1-2h in 25-40 ℃ of water-bath;
3), washing, filtration, then 80-120 ℃ of dry 3-4h in thermostatic drying chamber;
4), put into chamber type electric resistance furnace roasting 2-4h at 600-800 ℃;
5), take out and grind the former powder of making Ag/ZnO composite nano germicide, in distilled water, add the former powder of Ag/ZnO antibacterial agent, add again sodium laurate covering, the mass ratio 500:1 of former powder and sodium laurate, regulator solution pH value is 5-6, controls bath temperature, at temperature range 25-40 ℃, mechanical agitation 1-2h, is dried after filtering, and obtains the Ag/ZnO composite nano germicide of surface coating modification.
Ag/ZnO composite nano germicide after the modification of preparation can add to makes antibiotic plastic, excellent anti-microbial property and long acting antibiotic characteristic in high polymer.
Beneficial effect: the present invention compared to the prior art, adopt solwution method (solution dipping method) altogether nano-ZnO to be carried out to the assembling of Ag ion, add dispersant sodium hexametaphosphate to play peptizaiton, utilize sodium laurate to carry out surface coating modification to the former powder of Ag/ZnO complex antimicrobials of preparation simultaneously.
After adopting this technique to Ag/ZnO complex antimicrobials surface coating modification, effectively improved silver-containing antibacterial agent and held allochroic problem.
Antibacterial agent variable color test: adopting the change color of sample after ultraviolet pre-irradiation is the variable color situation that value of chromatism is carried out assess sample.Under the high-pressure sodium lamp of 125W, irradiate one hour, with Minolta Co.Ltd.Japan color difference meter, measure its color value L1, a1, b1 and do not irradiate color value L0, a0, the b0 of sample.Then according to following formula, calculate corresponding value of chromatism △ E:
△E=[(L0-L1)2+(a0-a1)2+(b0-b1)2]0.5。
Note: L0, a0, b0 are respectively the brightness of pre-irradiation sample, red-green axle color value in space, the blue-yellow axle color value in space;
L1, a1, the brightness of sample after b1 is respectively and irradiates, red-green axle color value in space, the blue-yellow axle color value in space.
Result: irradiate under the uviol lamp of 125W after one hour, Ag/ZnO composite antibacterial sample becomes ash, and aberration is 9.65.; And Ag/ZnO sample after coated does not almost have metachromatism, its aberration is 0.88; The coated composite granule of this explanation sodium laurate has improved its discoloration problem really.
Accompanying drawing explanation: accompanying drawing 1 is soak time-silver ion active ingredient stripping quantity curve
Embodiment
Embodiment 1:
A technique of preparing the Ag/ZnO composite nano germicide of surface coating modification, comprises the steps:
1), in distilled water, add dispersant sodium hexametaphosphate, the mass ratio 500:1 of distilled water and dispersant, is stirred to completely and dissolves;
2), in step 1) solution in add nano ZnO powder, the mass ratio 60:1 of distilled water and nano ZnO powder, first disperses 30 minutes with ultrasonic afterwards, then adds AgNO
3, nano ZnO powder and AgNO
3mass ratio 20:1, between the pH value to 7 of regulator solution, mechanical agitation 1h in 25 ℃ of water-baths;
3), washing, filtration, then 80 ℃ of dry 3h in thermostatic drying chamber;
4), put into chamber type electric resistance furnace roasting 2h at 600 ℃;
5), take out and grind the former powder of making Ag/ZnO composite nano germicide, in distilled water, add the former powder of Ag/ZnO antibacterial agent, add again sodium laurate covering, the mass ratio 500:1 of former powder and sodium laurate, regulator solution pH value is 5, controls bath temperature, at 25 ℃ of temperature ranges, mechanical agitation 1h, is dried after filtering, and obtains the Ag/ZnO composite nano germicide of surface coating modification.
Embodiment 2:
A technique of preparing the Ag/ZnO composite nano germicide of surface coating modification: comprise the steps:
1), in distilled water, add dispersant sodium hexametaphosphate, the mass ratio 500:1 of distilled water and dispersant, is stirred to completely and dissolves;
2), in step 1) solution in add nano ZnO powder, the mass ratio 60:1 of distilled water and nano ZnO powder, first disperses 30 minutes with ultrasonic afterwards, then adds AgNO
3, nano ZnO powder and AgNO
3mass ratio 20:1, between the pH value to 8 of regulator solution, mechanical agitation 2h in 40 ℃ of water-baths;
3), washing, filtration, then 120 ℃ of dry 4h in thermostatic drying chamber;
4), put into chamber type electric resistance furnace roasting 4h at 800 ℃;
5), take out and grind the former powder of making Ag/ZnO composite nano germicide, in distilled water, add the former powder of Ag/ZnO antibacterial agent, add again sodium laurate covering, the mass ratio 500:1 of former powder and sodium laurate, regulator solution pH value is 6, controls bath temperature, at 40 ℃ of temperature ranges, mechanical agitation 2h, is dried after filtering, and obtains the Ag/ZnO composite nano germicide of surface coating modification.
Embodiment 3:
A technique of preparing the Ag/ZnO composite nano germicide of surface coating modification, comprises the steps:
1), in distilled water, add dispersant sodium hexametaphosphate, the mass ratio 500:1 of distilled water and dispersant, is stirred to completely and dissolves;
2), in step 1) solution in add nano ZnO powder, the mass ratio 60:1 of distilled water and nano ZnO powder, first disperses 30 minutes with ultrasonic afterwards, then adds AgNO
3, nano ZnO powder and AgNO
3mass ratio 20:1, between the pH value to 7.5 of regulator solution, mechanical agitation 1.5h in 35 ℃ of water-baths;
3), washing, filtration, then 100 ℃ of dry 3.5h in thermostatic drying chamber;
4), put into chamber type electric resistance furnace roasting 3h at 700 ℃;
5), take out and grind the former powder of making Ag/ZnO composite nano germicide, in distilled water, add the former powder of Ag/ZnO antibacterial agent, add again sodium laurate covering, the mass ratio 500:1 of former powder and sodium laurate, regulator solution pH value is 5.5, controls bath temperature, at 30 ℃ of temperature ranges, mechanical agitation 1.5h, is dried after filtering, and obtains the Ag/ZnO composite nano germicide of surface coating modification.
Embodiment 4:
In 600ml distilled water, add 1.2g sodium hexametaphosphate, be stirred to completely and dissolve; Add 10g nano ZnO powder, first with ultrasonic, disperse 30 minutes, then add 0.5g AgNO
3, regulate pH value between 7-8, mechanical agitation 2h in 40 ℃ of water-baths; Washing, filtration, then 120 ℃ of dry 4h in thermostatic drying chamber; Put into chamber type electric resistance furnace roasting 4h at 600 ℃; Take out and grind the former powder of making Ag/ZnO composite nano germicide.In 600ml distilled water, add the former powder 2g of Ag/ZnO antibacterial agent, then add 40m1 sodium laurate covering (0.1mol/L), regulator solution pH value is 5,40 ℃ of bath temperatures, mechanical agitation 1h; After filtration, be drying to obtain the Ag/ZnO composite nano germicide of surface coating modification.
Antibacterial antiplaque agent test: the MIC test result of Ag/ZnO composite antibacterial sample sees the following form.
The anti-microbial property test of the table former powder of 1Ag/ZnO complex antimicrobials and the surface coated antibacterial agent sample of Ag/ZnO
Test data from showing, its MIC of powder of preparation all meets the requirement of the antibacterial association of Japanese inorganic antibacterial, MIC is 200mg/L, being scaled concentration is 0.02%wt, it is containing meaning: when the interpolation concentration of this antibacterial agent is 0.02%wt, to the bacteriostasis rate of Escherichia coli and staphylococcus aureus, be 100%, under this concentration, the growth of Escherichia coli and staphylococcus aureus is suppressed completely.Meet the requirement that bacteriostasis rate is greater than 95%.
Test data in contrast table can be found in addition, and the antibacterial agent fungistatic effect after the coated processing in surface is better than coated, and its main cause is to make the dispersiveness of powder better after coated processing, can fully demonstrate the special performance of nano material.
The preparation of antibiotic plastic:
Adopt the method for adding antibacterial matrices to prepare antibiotic plastic, in the antibacterial product of preparing for fear of direct addition method, occur that macroscopic view is even, the poor problem of Micro-disperse State, can be first by antibacterial agent and substrate resin or have the resin of excellent compatibility to extrude the concentrated master batch that is prepared into antibacterial agent by double screw extruder with substrate resin, antibacterial matrices is that antibacterial agent is dispersed in to the concentrated master batch of the high concentration of being processed in vector resin, and it is mainly comprised of antibacterial agent, vector resin, a small amount of dispersant and some processing aids.
This technology adopts twin-screw extrusion legal system for antibacterial matrices.Use double screw extruder to carry out mixing granulator, can effectively improve the mixability of material, then antibacterial matrices is added in plastic raw materials and processed, be conducive to the dispersion of antibacterial agent, to give full play to its effect.General antibacterial agent is Powdered, and it is poor with the compatibility of resin, and a small amount of antibacterial agent powder is difficult for fine dispersion in resin, and this has just directly affected antibacterial effect.Before preparing antibacterial matrices, must first antibacterial agent be carried out to surface treatment, increase the compatibility of organic facies and inorganic phase, be so also more conducive to the dispersion of antibacterial agent in master batch.Extruding front antibacterial agent powder should be mixed evenly by a certain percentage with various auxiliary agents and vector resin in high mixer, then uses double screw extruder mixing extrusion, has made antibacterial matrices after pelleter granulation.The main component of auxiliary agent is coupling agent and dispersant.The former Main Function is to increase affinity between inorganic matter and polymer.It is between inorganic matter and polymer, and the winding by physics or carry out certain chemical reaction, forms firmly chemical bond, thereby the material that amphiprotic substance differs widely is combined closely.
This technology adopts PE-1F7B as the vector resin of the antibacterial PE plastics of preparation, and PP powder is as the vector resin of the antibacterial PP plastics of preparation, and the concentration of antibacterial matrices is 10%, and the composition of antibacterial matrices is as shown in table 2.In master batch making and research, adopt the double screw extruder of big L/D ratio to manufacture respectively the antibacterial agent master batch of high concentration, wherein in antibacterial agent master batch, contain appropriate dispersant and carry out low temperature and extrude, to prevent that antibacterial agent decomposes in manufacturing process.
The composition of table 2 antibacterial matrices
The preparation of antibiotic plastic: after antibacterial matrices prepares, antibacterial matrices being mixed by a certain percentage with matrix resin, is standard jig and batten through injection machine injection moulding, carries out performance test.This technology selects PE-5200B, PP-T30S as the matrix resin of antibacterial polymer, adds part LLDPE resin simultaneously and plays synergy.
For the impact on PE, PP antibiotic plastic anti-microbial property of the addition of investigating Ag/ZnO nano antibacterial agent, we add in different ratios the Ag/ZnO antibacterial matrices of making in matrix resin PE-5200B, PP-T30S to, make antibacterial PE, antibacterial PP plastics, the antibiotic rate of the Different adding amount of detection antibacterial agent to Gram-negative colon bacillus and Gram-positive staphylococcus aureus, testing result is as shown in table 3.
Antibacterial model prepared by the table 3 interpolation Ag/ZnO antibacterial agent anti-microbial property to colon bacillus and staphylococcus aureus
As can be seen from the above data, add antibacterial PE, antibacterial PP plastics prepared by homemade Ag/ZnO nano antibacterial agent and all there is high anti-microbial property.When the addition of Ag/ZnO nano antibacterial agent is matrix resin 1 ‰ time, antibiotic plastic is all greater than 90% to the antibiotic rate of colon bacillus and staphylococcus aureus, has shown very high antibiotic rate; When the addition of this antibacterial agent is matrix resin 3 ‰ time, antibiotic plastic has all been greater than 99% to the antibiotic rate of colon bacillus and staphylococcus aureus, has reached strong antimicrobial effect.
This test homemade Ag/ZnO composite nano germicide used is through surface modification treatment, fine with the compatibility of resin.Because its particle diameter is little, in antibacterial agent, the content of silver ion is high, so show very high anti-microbial property.
Antibiotic plastic long acting antibiotic test: in order to investigate the antimicrobial long-acting of antibacterial sample, the antibacterial model that we are 3 ‰ by interpolation Ag/ZnO nano-antibacterial agent content is further heated and washed away, and investigates the attenuation of its anti-microbial property.
Concrete grammar is:
Antibacterial sample is put into the beaker that 1000ml is housed, then beaker is put in the water-bath of 55 ℃, with agitator, ceaselessly stir, every 12 hours, change one time water, after certain hour, by the concentration of Antibacterial Constituents in the water of atomic absorption spectrophotometric determination immersion antibiotic plastic print, by sizing technique, measure print and soak the antibiotic rate after certain hour.According to the active ingredient stripping quantity of several time points of measuring, by extrapolation, release the active ingredient stripping tendency (seeing accompanying drawing 1) in whole use procedure.
From curve, can find out, in antibiotic plastic, the silver ion active ingredient amount of separating out is linear with dip time, after antibacterial agent active ingredient stripping quantity reaches certain value, its stripping does not stop but continuing carrying out slowly, according to the extrapolation of actual measurement stripping curve, antibiotic plastic use 10 years even after 20 years its silver ion active ingredient stripping quantity all well below the total content of silver ion active ingredient in antibiotic plastic, illustrate that the sample of preparing can keep antibacterial action for a long time.After sample being soaked to certain hour in order to upper method, measure its antibiotic rate, the results are shown in Table 4.
Table 4 immersion certain hour is heated and is washed away the anti-microbial property of the antibacterial model of rear PP
The test result of upper table shows, the antibacterial sample of preparation is after soaking certain hour and heating and wash away, it declines with original comparing slightly to some extent to the antibiotic rate of Gram-negative colon bacillus and Gram-positive staphylococcus aureus, but still remain near 99%, have extremely strong antibacterial effect, antibiotic plastic prepared by this explanation interpolation Ag/ZnO nano antibacterial agent has good antimicrobial long-acting.
Claims (1)
1. a technique of preparing the Ag/ZnO composite nano germicide of surface coating modification, is characterized in that: comprise the steps:
1), in distilled water, add dispersant sodium hexametaphosphate, the mass ratio 500:1 of distilled water and dispersant, is stirred to completely and dissolves;
2), in step 1) solution in add nano ZnO powder, the mass ratio 60:1 of distilled water and nano ZnO powder, first disperses 30 minutes with ultrasonic afterwards, then adds AgNO
3, nano ZnO powder and AgNO
3mass ratio 20:1, the pH value of regulator solution is between 7-8, mechanical agitation 1-2h in 25-40 ℃ of water-bath;
3), washing, filtration, then 80-120 ℃ of dry 3-4h in thermostatic drying chamber;
4), put into chamber type electric resistance furnace roasting 2-4h at 600-800 ℃;
5), take out and grind the former powder of making Ag/ZnO composite nano germicide, in distilled water, add the former powder of Ag/ZnO antibacterial agent, add again sodium laurate covering, the mass ratio 500:1 of former powder and sodium laurate, regulator solution pH value is 5-6, controls bath temperature, at temperature range 25-40 ℃, mechanical agitation 1-2h, is dried after filtering, and obtains the Ag/ZnO composite nano germicide of surface coating modification.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105199334A (en) * | 2015-09-17 | 2015-12-30 | 苏州新区佳合塑胶有限公司 | Antibacterial high-filled degradable plastic |
| CN106398316A (en) * | 2016-06-01 | 2017-02-15 | 沈阳理工大学 | Preparation method for metallic nickel ion-doped nanometer zinc oxide |
| CN109261957A (en) * | 2018-09-26 | 2019-01-25 | 云南大学 | A kind of silver coating zinc oxide composite powder material and its preparation method and application |
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| CN1821326A (en) * | 2006-03-30 | 2006-08-23 | 上海电力学院 | Process for preparing anti-wear, anti-corrosion nano composite epoxy zinc-enriched paint |
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| CN1796454A (en) * | 2004-12-22 | 2006-07-05 | 上海梅林正广和（集团）有限公司 | Method for manufacturing faucet of bacteria resistant watering trough apparatus |
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Non-Patent Citations (1)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199334A (en) * | 2015-09-17 | 2015-12-30 | 苏州新区佳合塑胶有限公司 | Antibacterial high-filled degradable plastic |
| CN106398316A (en) * | 2016-06-01 | 2017-02-15 | 沈阳理工大学 | Preparation method for metallic nickel ion-doped nanometer zinc oxide |
| CN106398316B (en) * | 2016-06-01 | 2018-08-10 | 沈阳理工大学 | A kind of preparation method of the nano zine oxide of doping metals nickel ion |
| CN109261957A (en) * | 2018-09-26 | 2019-01-25 | 云南大学 | A kind of silver coating zinc oxide composite powder material and its preparation method and application |
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Application publication date: 20140326 |