CN101190393A - Cu-Ag antimicrobial filtering metal material and preparing method and application thereof - Google Patents
Cu-Ag antimicrobial filtering metal material and preparing method and application thereof Download PDFInfo
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- CN101190393A CN101190393A CNA2006101343663A CN200610134366A CN101190393A CN 101190393 A CN101190393 A CN 101190393A CN A2006101343663 A CNA2006101343663 A CN A2006101343663A CN 200610134366 A CN200610134366 A CN 200610134366A CN 101190393 A CN101190393 A CN 101190393A
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- 229910017770 Cu—Ag Inorganic materials 0.000 title claims abstract description 35
- 239000007769 metal material Substances 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims description 16
- 230000000845 anti-microbial effect Effects 0.000 title description 12
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- 229910052802 copper Inorganic materials 0.000 claims abstract description 55
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- 239000000463 material Substances 0.000 claims abstract description 51
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- 238000007747 plating Methods 0.000 claims abstract description 12
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- 238000002360 preparation method Methods 0.000 claims abstract description 10
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- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
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- BRWIZMBXBAOCCF-UHFFFAOYSA-N hydrazinecarbothioamide Chemical compound NNC(N)=S BRWIZMBXBAOCCF-UHFFFAOYSA-N 0.000 description 1
- 206010022000 influenza Diseases 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
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- VZOPRCCTKLAGPN-ZFJVMAEJSA-L potassium;sodium;(2r,3r)-2,3-dihydroxybutanedioate;tetrahydrate Chemical compound O.O.O.O.[Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VZOPRCCTKLAGPN-ZFJVMAEJSA-L 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to an improved technology of filter screen material, in particular to a Cu-Ag composite net shaped antibacterial filtration metal material with excellent broad-spectrum antibacterial performance and the preparation method and application thereof. The invention solves the problems of insufficient copper intake of human body and propagation of bacilli, etc., and can be applied to the filter device of gas or liquid such as food, drinking, wine, etc. and the filter screens in air conditioners. The invention takes foam sponge or other net shaped fiber as basic material which is loaded with metal Cu-Ag to form high porosity net shaped broad-spectrum antibacterial filtration metal material. The preparation method is that electroplating Cu antibacterial cladding is carried out to the basic material which is disposed by conductance; when the copper plating reaches the required thickness, heat disposal is carried out in a vacuum furnace or a furnace which is protected by argon in order to form metal copper net; finally the surface of the metal copper net is plated with metal silver film, thus obtaining the finished Cu-Ag-loaded composite net shaped broad-spectrum antibacterial filtration metal material with the porosity ranging from 85% to 95% and the aperture can be adjusted between 100 micron and 500 micron according to practical requirement.
Description
Technical field:
The present invention relates to the improvement technology of screen pack material, be specially a kind of Cu-Ag composite mesh antiseptic filtering and its production and application, can be applicable to the screen pack in gases such as food, beverage, drinks or liquid production filter and the air-conditioning with good broad spectrum antibacterial performance.
Background technology:
In recent years, the global microorganism disaster incident that is caused by microorganism and mutation thereof repeatedly takes place, and antibiotic notion and product are more and more paid close attention to by everybody.
In the U.S., food processing enterprises must obtain ISO9000, ISO14000 or HACCP (HazardAnalysis and Critical Control Point) hazard analysis and CCP authentication.The HACCP authentication is NASA(The National Aeronautics and Space Administration) (the National Aeronautics and SpaceAdministration sixties in 20th century, NASA) the assurance inflight meal of Ti Chuing avoids standard [the document 1:I.T.Hong of germ contamination and other harm in process, C.H.Koo, Antibacterial properties, corrosion resistanceand mechanical properties of Cu-modified SUS 304 stainless steel, Materials Scienceand Engineering A 393 (2005): 213-222], developed into afterwards and a kind of food safety hazard was discerned, the systems approach of assessment and control also is one and guarantees that food production and supply chain avoid biological, the safety management instrument that chemistry and physical property harm are polluted.In food processing process, use compressed air, these compressed air can direct contact food.Therefore, compressed air will be through filtration treatment to remove solid particles such as dust wherein before being delivered into the workshop, if filter medium only has filter capacity merely, and do not possess the bactericidal function, some bacteriums will be multiplied in the long-term back of using on the surface of filter medium, it can become pollution sources on the contrary like this.
Need in the drinking water production process to guarantee that the clump count in the water body is lower than certain level.Therefore, the filtering material that uses in the production technology have antibacterial functions be necessary [document 2: Lu Shiying, Zhang Tingkai, Kang Xifan etc., special steel book series---stainless steel, [M]. Beijing: Atomic Energy Press, September nineteen ninety-five: P4].
Whenever hot summer is arrived, in family or public place, people need to use air-conditioning in order to work or to live in nice and cool space, and the bacterium place of multiplying easily often of the screen pack in the air-conditioning.Room air is when circulation process air-conditioning filter net, and just the bacterium that will multiply is thereon brought in the room air.People breathe this symptoms such as dizziness headache of will being felt behind the air of germ contamination, the air conditioner disease that Here it is it has often been said, and therefore, air-conditioning filter net also should have antibacterial functions.
As everyone knows, Cu is the antibacterial metal element.Cu can effectively kill bacteriums such as E.coli, S.aureus.
Copper, silver just are used as the material of making the daily life vessel since ancient times, adopt silver-bearing copper material processed recirculated water and drinking water on former Soviet Union's spaceship.
Copper also is [document 3:S.Saint, J.G.Elmore, S.D.Sullivan, S.S.Emerson, T.D.Koepsell, Am.J.Med, 1998,105 (3): 236 of indispensable trace element in the human body; Document 4:J.I.Greenfeld, L.Sampath, S.J.Popilskis, S.R.Brunnert, S.Stylianos, S.Modak, Crit, Care Med, 1995,23 (5): 894; Document 5:R.J.McLean, A.A.Hussain, M.Sayer, P.J.Vincent, D.J.Hughes, T.J.Smith, Can, J.Microbiol, 1993,39 (9): 895], particularly for the elderly, an amount of copper is to safeguarding the healthy important effect that has.Copper is the same with elements such as zinc, iron, all is to keep the requisite element of brain normal function [document 6:J.B.Bishop, L.G.Phillips, T.A.Mustoe, A.J.VanderZee, L.Wiersema, D.E.Roach, J.P.Heggers, D.P.Hill, E.L.Taylor, M.C.Robson, J.Vasc, Surg, 1992,16 (2): 251].Human body in hematopoiesis, the iron in the hemoglobin, the ferrous iron that needs origin to come from the food is converted into ferric iron, such conversion process must have the participation of copper just can finish.If lack copper in the body, will cause the conversion difficulty of iron and bring out anaemia [document 5].Copper prevents that in addition kovakorisan heart disease, protection cell are not subjected to infringement opposing aging, prevent and treat effect [document 7:T.N.Kim, Q.L.Feng, J.O.Kim such as influenza and cancer; et.al.; J.Mater.Sci.Mater.Med, 1998, (9): 129].
People's picked-up to copper in diet at present is generally not enough, differs about half with actual psychological need.This will ask for help to eat of the food of cupric at ordinary times more, as liver, oyster, shrimp, beans and the kernel etc. of animal.And, do not take vitamin C after the meal, because this vitamin can disturb the absorption of human body to copper.In addition, not eating overrefining cereal also is one of method that increases the copper intake.Certainly, intake is too much, also can bring side effect to healthy, and the copper of taking in 2 milligrams every day just is enough to satisfy physiological requirements.
By above narration as can be known, the copper of normal contents is nontoxic to human body, or even necessary, uses copper can not produce harm to human body and environment in anti-biotic material.
Summary of the invention:
The object of the present invention is to provide a kind of Cu-Ag composite mesh antiseptic filtering and preparation method thereof, solve bacterium and multiply and problem such as human body copper insufficiency of intake with good broad spectrum antibacterial performance.
Technical scheme of the present invention is:
A kind of Cu-Ag composite mesh antiseptic filtering, this metal material is for being the composite mesh structure of the metallic copper net surface plating silverskin that the plating copper film obtains on the base material at foam sponge or reticular fibre material, the thickness of copper film is 20 microns-100 microns, the thickness of silverskin is 100 nanometers-300 nanometers, the porosity of composite mesh structure is 85%-95%, and the aperture is adjustable in 150 microns-500 micrometer ranges.
The preparation method of described Cu-Ag composite mesh antiseptic filtering is a base material with foam sponge or reticular fibre, and carried metal Cu-Ag forms composite mesh antiseptic filtering, and concrete steps are as follows:
(1) the conduction processing of base material;
(2) plating copper film on base material;
(3) heat treatment, the material that plating is good are at 700-850 ℃ vacuum drying oven or have in the atmosphere of argon shield and heat-treated 1-4 hour, to remove organic foam or the fiber composition in the rack, form the metal copper mesh;
(4) the metallic copper net surface plating silverskin after heat treatment obtains the composite mesh broad-spectrum antiseptic filtering metal material of carried metal Cu-Ag, and the plated film of this composite mesh antiseptic filtering is made up of metallic copper and silver.
Described conduction processing can be with foam sponge material or reticular fibre material impregnation process in the solution of graphitiferous powder or conducting resinl solution, makes foam sponge material or reticular fibre material obtain electric conductivity and gets final product.
Described plated film can adopt conventional electro-plating method to carry out electro-coppering or silver, perhaps adopts electroless copper, silver-colored method to carry out plated film.
Composite mesh antiseptic filtering of the present invention can be applicable to the gas or the liquid production filter of food, beverage, drinks, perhaps is applied to the screen pack in the air-conditioning.
Advantage of the present invention and beneficial effect are:
1, the present invention utilizes metal Cu, Ag element unique biological inorganic chemistry performance (being anti-microbial property); it is carried on foam sponge or other reticular fibre material; form metal Cu-Ag mesh skeleton filtering material; at high-temperature vacuum or have under the hot conditions of protective atmosphere and make foam sponge or other reticular fibre material breakdown, has antimicrobial filtering material high temperature resistant and fire prevention character thereby become.
2, the present invention is through analysis of science and demonstration, courageously adopt Cu-Ag as filtering material, copper film and silverskin combine, composite mesh antiseptic filtering can be applied to filter in food, beverage, the drinks process units and the screen pack in the air-conditioning, not only can prevent multiplying of bacterium, can also increase the intake of human body, make human body copper content be tending towards normal index copper.
3, composite mesh antiseptic filtering preparation method of the present invention is simple, cost is lower.The present invention is the material of substrate with foam sponge or other reticular fibre (other reticular fibres can for: polyethylene, polypropylene etc.); the netted broad-spectrum antiseptic filtering metal material of carried metal Cu-Ag porous; base material through the conductionization processing; electroplate the antibiotic coating of Cu; when plated copper film reaches needed thickness; at vacuum drying oven or have in the stove of argon shield and heat-treat; form the metal copper mesh; at last at metallic copper net surface plating silverskin, the carried metal Cu-Ag composite mesh broad-spectrum antiseptic filtering metal material that can obtain making.The plated film of this composite mesh antiseptic filtering is made up of metallic copper and silver, and last composite mesh antiseptic filtering only has metallic framework to exist, and has made it fire prevention and resistance and high temperature resistance property.
4, adopt the composite mesh antiseptic filtering of the present invention's preparation, characteristics with porous, its porosity can reach 85-95%, the aperture can be adjusted in 150 microns-500 micrometer ranges as required, the advantage of this structure mainly contains: (1) specific area is big, can adsorb and kill various mushrooms dramatically like this; (2) aperture relatively evenly and mutually connects, and through hole is not easy to be stopped up by the field trash in air or the liquid; (3) light weight is given and being filtered and when killing the bacterium performance and the weight of equipment increase is very little; (4) after cleaning by proper method, excellent in durability, the Web materials after using after a while still can continue to use and keep the good bacterium effect of killing.
Description of drawings:
Fig. 1 is the ESEM photomacrograph of metal Cu-Ag composite mesh antiseptic filtering.
Fig. 2 is the stereoscan photograph of metal Cu-Ag composite mesh antiseptic filtering.
The specific embodiment:
Embodiment 1
Foam sponge material (aperture is about 550 microns) is flooded the back taking-up dry in containing the solution of graphite, make it obtain electric conductivity.Under composition proportion as shown in table 1 and technological parameter condition, foam sponge material after the conductive processing is carried out electroplating copper film, when the thickness of plated material is approximately 25 μ m, from electroplating solution, take out, dry after the washing, insert that (vacuum is about 10Pa) kept 2 hours in 800 ℃ the vacuum drying oven, take out the cooling back, remove the foam sponge in the rack, form the metal copper mesh;
Table 1 is electroplated Cu solution formula and technological parameter
Component and technological parameter | Content (g/L) or parameter | Component and parameter | Content (g/L) or parameter |
Cupric pyrophosphate (Cu 2P 2O 7) | 50-100 | PH value | 7.5-9.2 |
Potassium pyrophosphate (K 4P 2O 7.3H 2O) | 200-400 | Temperature/℃ | 25-60 |
Sodium potassium tartrate tetrahydrate (KNaC 4H 4O 6.4H 2O) | 10-30 | Voltage/V | 12-24 |
Nitrilotriacetic acid [N (CH 2COOH) 3] | 12-25 | Current density/A.dm -2 | 0.5-2.0 |
Potassium nitrate (KNO 3) | 10-30 |
At last, under composition proportion as shown in table 2 and technological parameter condition, the thick Ag film flash of 200nm is on the metallic copper net surface that has prepared;
Table 2 is electroplated Ag solution formula and technological parameter
Component and technological parameter | Content (g/L) or parameter | Component and parameter | Content (g/L) or parameter |
Silver nitrate [AgNO 3] | 45-50 | PH value | 5.0-6.0 |
ATS (Ammonium thiosulphate) [(NH 4)S 2O 3] | 230-260 | Temperature/℃ | 15-35 |
Ammonium acetate [NH 4C 2H 3O 2] | 20-30 | Voltage/V | 12-24 |
Anhydrous sodium sulfite [Na 2SO 3] | 80-100 | Current density/A.dm -2 | 0.1-0.3 |
Thiosemicarbazide [CH 5N 3S] | 0.5-0.8 |
Thereby, obtaining the composite mesh broad-spectrum antiseptic filtering metal material of carried metal Cu-Ag, the plated film of this composite mesh antiseptic filtering is made up of metallic copper and silver, and the porosity of present embodiment composite mesh structure is 95%, and the aperture is about 500 microns.
The present invention carries out the anti-microbial property test to the material for preparing, and concrete method of testing is as follows:
1 experimental strain is selected
Adopt ETEC (E.coli) ATCC 8099, staphylococcus aureus (S.aureus) ATCC6538, Candida albicans (C.albicans) ATCC 10231 and bacillus subtilis ATCC 9372 etc. have tested the anti-microbial property of material.
2 antibacterial experiments
(1) culture presevation
With bacterial classification inoculation on nutrient agar (NA) inclined-plane, after (37 ± 1) ℃ cultivate 24h down, at (0~5) ℃ following preservation (must not above 1 month), as the slant preservation bacterium.
(2) actication of culture
The slant preservation bacterium is transferred on the dull and stereotyped nutrient agar,, transfers every day 1 time, be no more than for 2 weeks at (37 ± 1) ℃ following 24h that cultivates.Should adopt fresh group of bacterium culture after the continuous switching 2 times (switching in the 24h) during test.
(3) bacteria suspension preparation
Get fresh bacterium with oese from (2) culture medium, add in the nutrient solution, and take turns doing 10 times and increase progressively dilution, select desired concn bacterium liquid to do experiment.
(4) laboratory sample
Laboratory sample is a: control sample: do not possess the sponge of antimicrobial component, size is 20 * 20mm
2The netted anti-biotic material sample of b:Cu-Ag: size is 20 * 20mm
2
Control sample adopts alcohol disinfecting, and sterilizes 30 minutes with ultraviolet disinfection lamp.Netted anti-biotic material sample is hot air sterilization 2h under 160 ℃ of conditions.
Draw the 5ml sterilized water and join in the sterile petri dish, pick up two aseptic slides with the sterilization tweezers, put into culture dish, the water surface is no more than top slide.Be put on the slide with tweezers folder sample, the test bacterium liquid of some 0.2ml suitable concn on sample makes bacterium liquid and sample even contact again.Culture dish seals with sealing film.Under (37 ± 1) ℃ condition, cultivate.By bacterium liquid being added on the control sample with quadrat method.Every kind of sample all do 3 parallel.
Treat that bacterium liquid and sample effect are after the regular hour, from incubator, take out culture dish, in each culture dish, add the 45ml eluent respectively, wash control sample, anti-biotic material sample repeatedly, after eluent fully shaken up, carry out gradient dilution, choosing the dilution of suitable concn coats in the nutrient agar plate medium (NA), a ℃ following cultivation was carried out count plate after 24 hours in (37 ± 1), pressed GB 4789.2 " microbiological test of food hygiene-total plate count method for measuring " and measured viable count.
More than test triplicate.
Antibacterial experiment the results are shown in Table 2,3,4.The computing formula of sterilizing rate is:
Viable count in the above-mentioned formula is the viable count behind the antibacterial experiment.
The anti-microbial property of table 3 metal Cu-Ag composite mesh antiseptic filtering
Escherichia coli | Staphylococcus aureus | Candida albicans | The eel grass bacillus | |
Concentration (cfu/ml) | 1.5×10 8 | 5.6×10 7 | 2×10 8 | 5×10 8 |
Time of contact (h) | 1 | 1 | 1 | 24 |
Antibiotic rate (%) | 100 | 100 | 100 | 97 |
Table 4 metal Cu-Ag composite mesh antiseptic filtering is to the antibiotic rate (%) of Escherichia coli ATCC 6099 different times, concentration: 3.5 * 10
6Cfu/ml
Table 5Cu-Ag composite mesh antiseptic filtering (old net, repeatedly experiment back) is to the antibiotic rate of variable concentrations Escherichia coli (44113), 24 hours time
Bacteria concentration (cfu/ml) | 10 10 | 10 9 | 10 8 |
Antibiotic rate (%) | 96.5 | 100 | 100 |
By table 3, table 4 and table 5 as can be seen, the Cu-Ag composite mesh antiseptic filtering all has good anti-microbial property for these four kinds of representative mushrooms of Escherichia coli, Staphylococcus aureus, candida albicans and eel grass bacillus, presents extremely superior broad spectrum antibacterial performance; The Cu-Ag composite mesh antiseptic filtering to kill bacterium effective and kill rate is very high, be 3.5 * 10 to concentration
6The Escherichia coli ATCC 6099 of cfu/ml, its antibiotic rate has just reached more than 99% in 20 minutes, has reached 100% after 30 minutes; The bacterium performance of killing of Cu-Ag composite mesh antiseptic filtering has long-acting, after using repeatedly to concentration up to 1 * 10
10The Escherichia coli ATCC44113 of cfu/ml still has the extremely strong bacterium ability of killing.
Embodiment 2
Difference from Example 1 is:
The netted fibrous material of polyethylene (aperture is about 450 microns) is flooded the back taking-up dry in containing the solution of graphite, make it obtain electric conductivity.Under composition proportion as shown in table 1 and technological parameter condition, foam sponge material after the conductive processing is carried out electroplating copper film, when the thickness of plated material is approximately 50 μ m, from electroplating solution, take out, dry after the washing, insert in 700 ℃ the argon gas atmosphere and kept 4 hours, take out the cooling back, remove the fiber composition in the rack, form the metal copper mesh; At last, under composition proportion as shown in table 2 and technological parameter condition, the thick Ag film flash of 100nm is on the metallic copper net surface that has prepared; Thereby, obtaining the composite mesh broad-spectrum antiseptic filtering metal material of carried metal Cu-Ag, the plated film of this composite mesh antiseptic filtering is made up of metallic copper and silver, and the porosity of present embodiment composite mesh structure is 90%, and the aperture is about 350 microns.
Present embodiment carries out the anti-microbial property test to the material for preparing, the Cu-Ag composite mesh antiseptic filtering all has good anti-microbial property for these four kinds of representative mushrooms of Escherichia coli, Staphylococcus aureus, candida albicans and eel grass bacillus, presents extremely superior broad spectrum antibacterial performance.
Embodiment 3
Difference from Example 1 is:
Polypropylene mesh fibrous material (aperture is about 350 microns) is flooded the back taking-up dry in containing the solution of graphite, make it obtain electric conductivity.Under composition proportion as shown in table 1 and technological parameter condition, foam sponge material after the conductive processing is carried out electroplating copper film, when the thickness of plated material is approximately 100 μ m, from electroplating solution, take out, dry after the washing, insert in 850 ℃ the argon gas atmosphere and kept 1 hour, take out the cooling back, remove the fiber composition in the rack, form the metal copper mesh; At last, under composition proportion as shown in table 2 and technological parameter condition, the thick Ag film flash of 300nm is on the metallic copper net surface that has prepared; Thereby, obtaining the composite mesh broad-spectrum antiseptic filtering metal material of carried metal Cu-Ag, the plated film of this composite mesh antiseptic filtering is made up of metallic copper and silver, and the porosity of present embodiment composite mesh structure is about 85%, and the aperture is about 150 microns.
Present embodiment carries out the anti-microbial property test to the material for preparing, the Cu-Ag composite mesh antiseptic filtering all has good anti-microbial property for these four kinds of representative mushrooms of Escherichia coli, Staphylococcus aureus, candida albicans and eel grass bacillus, presents extremely superior broad spectrum antibacterial performance.
Claims (5)
1. Cu-Ag composite mesh antiseptic filtering, it is characterized in that: this metal material is for being the composite mesh structure of the metallic copper net surface plating silverskin that the plating copper film obtains on the base material at foam sponge or reticular fibre material, the thickness of copper film is 20 microns-100 microns, the thickness of silverskin is 100 nanometers-300 nanometers, the porosity of composite mesh structure is 85%-95%, and the aperture is adjustable in 150 microns-500 micrometer ranges.
2. according to the preparation method of the described Cu-Ag composite mesh antiseptic filtering of claim 1, it is characterized in that: with foam sponge or reticular fibre is base material, carried metal Cu-Ag forms composite mesh antiseptic filtering, and concrete steps are as follows:
(1) the conduction processing of base material;
(2) plating copper film on base material;
(3) heat treatment, the material that plating is good are at 700-850 ℃ vacuum drying oven or have in the atmosphere of argon shield and heat-treated 1-4 hour, to remove organic foam or the fiber composition in the rack, form the metal copper mesh;
(4) the metallic copper net surface plating silverskin after heat treatment obtains the composite mesh broad-spectrum antiseptic filtering metal material of carried metal Cu-Ag, and the plated film of this composite mesh antiseptic filtering is made up of metallic copper and silver.
3. according to the preparation method of the described Cu-Ag composite mesh antiseptic filtering of claim 2, it is characterized in that: described conduction processing is with foam sponge material or reticular fibre material impregnation process in the solution of graphitiferous powder or conducting resinl solution, makes foam sponge material or reticular fibre material obtain electric conductivity and gets final product.
4. according to the preparation method of the described Cu-Ag composite mesh antiseptic filtering of claim 2, it is characterized in that: described plated film adopts conventional electro-plating method to carry out electro-coppering or silver, perhaps adopts electroless copper, silver-colored method to carry out plated film.
5. according to the application of the described Cu-Ag composite mesh antiseptic filtering of claim 1, it is characterized in that: this composite mesh antiseptic filtering is applied to the gas or the liquid production filter of food, beverage, drinks, perhaps is applied to the screen pack in the air-conditioning.
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