CN101637680A - Antiseptic filtering metal material by plating Cu and CeO2 on surface of copper wire mesh, and preparation and application thereof - Google Patents

Abstract

The invention relates to the preparation technology of the filter material, specifically a (Cu+CeO ₂ )/Cu composite mesh antibacterial filter metal material with excellent antibacterial performance and its preparation method and application, which can solve the problem of bacteria breeding and insufficient copper intake of the human body, etc. It can be applied to food, beverage, wine and other gas or liquid production filter devices and filter screens in air conditioners. The invention uses the foam sponge as the base material, and supports metal (Cu+CeO ₂ )/Cu to form a high-porosity reticular antibacterial filtering metal material. Its preparation method: electroplating Cu antibacterial coating on the base material after conductive treatment, when the copper coating reaches the required thickness, heat treatment is carried out in a vacuum furnace or a furnace protected by argon gas to form a metal copper mesh, and finally on the metal Plating (Cu+CeO ₂ ) on the surface of the copper mesh can get the prepared loaded metal (Cu+CeO ₂ )/Cu composite mesh antibacterial filter metal material. Adjustable within the range of 350 microns - 500 microns.

Description

Antibacterial filter metal material with Cu and CeO2 plated on the surface of copper mesh and its preparation and application

Technical field:

The present invention relates to the preparation technology of filter screen material, specifically a kind of (Cu+CeO ₂ )/Cu composite mesh antibacterial filter metal material with excellent antibacterial performance and its preparation method and application, namely: copper mesh surface plating (Cu+CeO 2 ) CeO ₂ ) composite mesh antibacterial filter metal material and its preparation method and application can be applied to gas or liquid production filter devices such as food, beverages and wines, and filter screens in air conditioners.

Background technique:

The global theme of the 21st century is "health and the environment". Everyone's life and health, 60% are in their own hands. That is to say, apart from factors that cannot be changed such as genetics, the environment in which an individual lives plays an important role in life and health [Document 1: Jin Zongzhe, Inorganic Antibacterial Materials and Applications, Beijing: Chemical Industry Press, August 2004 ]. Sterilization and disinfection of air, clothing and furniture surfaces is a necessary means, but since the disinfectants used daily by people can only produce short-term effects, and contain chemical components harmful to human health, through surface contact and gasification of antibacterial agents, etc. way is harmful to health. Therefore, a new generation of antibacterial materials has appeared, which can antibacterial for a long time on the surface of the material, but is harmless and non-toxic inorganic antibacterial materials to the human body [Document 2: Xu Ying, Journal of Hebei Institute of Technology, 2001, 23 (4): 77 ; Literature 3: Sun Jian, Qiao Xueliang, Chen Jianguo, Materials Herald, 2007, 21(VIII): 344].

At present, Ag ⁺ , Cu ²⁺ and Zn ²⁺ are mostly used as antibacterial ions in commercialized inorganic antibacterial materials at home and abroad. Among them, Ag ⁺ has the best antibacterial effect, but the price is also the highest, and silver ions are easy to change color when exposed to light and heat. In addition, Ag ⁺ easily reacts with Cl ^- , HS ^- and S ^2- in the water medium to form water-insoluble precipitates, thus losing antibacterial activity [Document 4: Zhang Bin, Tang Xiaoning, Zhang Haodong, New Chemical Materials, 2007 , 35(2): 73; Literature 5: TNKim, QLFeng, JOKim, J.Wu, H.Wang, GCChen, FZCui, Journal of Materials Science: Materials in Medicine, 1998, 9: 129]. Rare earth elements have unique electronic structures and properties. People vividly call rare earth elements "MSG" of modern industry. They have been applied in more than 40 industries such as metallurgy, petrochemical industry, medicine and health. my country has abundant rare earth resources, and the development of rare earth products has unique conditions [Document 6: Mu Kangguo et al., Chinese Journal of Rare Earth, 2003, 21(1): 1].

At present, people's dietary intake of copper is generally insufficient, which is about half of the actual physiological needs. Of course, excessive intake will also have side effects on health, and a daily intake of 2 mg of copper is sufficient to meet physiological needs.

It can be seen from the above description that the normal content of copper is non-toxic to the human body, even necessary, and the use of copper in antibacterial materials will not cause harm to the human body and the environment. Similarly, a small amount of rare earth elements in antibacterial materials will not cause harm to the human body [Document 7: Gao Jinzhang, Long Quanjiang, Yang Tao, Journal of Northwest Normal University, 2002, 138(1): 108].

Invention content:

The object of the present invention is to provide a Cu+CeO ₂ /Cu composite mesh antibacterial filter metal material with excellent antibacterial performance and its preparation method and application, so as to solve the problems of bacteria breeding and insufficient copper intake of human body.

Technical scheme of the present invention is:

A kind of antibacterial filter metal material that copper net surface is plated Cu adds _CeO , this metal material is the metal copper net surface plated metal Cu that metal copper film obtains on the foam sponge base material adds _CeO Composite network structure, copper film The thickness of the Cu plus _CeO2 film is 20 microns-50 microns, the thickness of the Cu plus CeO2 film is 2 microns-3 microns, the porosity of the composite network structure is 85%-96%, and the pore size is adjustable in the range of 350 microns-500 microns.

The surface of the copper mesh is plated with Cu plus CeO ₂ The preparation method of the antibacterial filter metal material, with the foam sponge as the base material, the load metal (Cu+CeO ₂ )/Cu forms a composite mesh antibacterial filter metal material, the specific steps are as follows:

(1) conductive treatment of base material;

(2) plating metal copper film on base material;

(3) heat treatment, the plated material is heat-treated for 1-4 hours in an argon protective atmosphere at 700-850 ° C, to remove the organic foam components in the grid, and form a metal copper mesh;

(4) Metal Cu plus _CeO2 film is plated on the surface of the metal copper mesh after heat treatment, and the Cu plus _CeO2 coating is deposited in an electroplating copper solution that adds _CeO2 micropowder (8-10g/L) and is equipped with mechanical stirring, A metal-loaded (Cu+CeO ₂ )/Cu composite mesh antibacterial filter metal material is obtained, and the composite mesh antibacterial filter metal material is composed of metal copper mesh and metal Cu plus CeO ₂ coating.

The conductive treatment is to deposit a 2-3 micron copper film on the surface of the foam sponge material by ion sputtering coating method, so that the foam sponge material can obtain conductivity.

The composite mesh antibacterial filter metal material of the present invention can be applied to food, beverage, sprinkler gas or liquid production filter devices, or to filter screens in air conditioners.

Advantage of the present invention and beneficial effect are:

1. The present invention utilizes the unique bioinorganic chemical properties (i.e. antibacterial properties and non-toxicity) of metal Cu and Ce elements to deposit Cu on the foam sponge material, and decompose the foam sponge material under high temperature conditions protected by argon to form The metal Cu mesh skeleton material, and Cu plus CeO ₂ are deposited on the surface, so as to become a (Cu+CeO ₂ )/Cu antibacterial filter material with high temperature resistance and fireproof properties.

2. The preparation method of the composite mesh antibacterial filter metal material of the present invention is simple and easy, and the cost is low. The present invention uses foam sponge as the base material, loaded with metal (Cu+CeO ₂ )/Cu high-porosity mesh antibacterial filter metal material, and the composite mesh antibacterial filter metal material is composed of metal copper mesh and metal Cu plus CeO ₂ coating, The final composite mesh antibacterial filter metal material only has a metal skeleton, so that it can have the performance of fire prevention and high temperature resistance.

3. The composite mesh antibacterial filter metal material prepared by the present invention has the characteristics of high porosity, and its porosity can reach 85-96%, and the pore diameter can be adjusted as required within the range of 350 microns to 500 microns. This structure The main advantages are: (1) The specific surface area is large, which can greatly absorb and kill various fungi; (2) The holes are connected to each other, the pore diameter is relatively uniform, and the through holes are not easy to be included by smaller particles. (3) light specific gravity; (4) good durability, the mesh material after a period of use can continue to be used and maintain a good bactericidal effect after being cleaned by an appropriate method; (5) by adding _CeO2 micropowder It can improve the corrosion resistance of the material and properly slow down the release rate of Cu ²⁺ ions.

Description of drawings:

Fig. 1 is a macroscopic photo of the (Cu+CeO ₂ )/Cu composite mesh antibacterial filter metal material of the present invention.

Fig. 2 is the surface microscopic morphology of the (Cu+CeO ₂ )/Cu composite mesh antibacterial filter metal material of the present invention.

Fig. 3 results of the bacteriostatic zone test of the present invention. Among them, (a) Staphylococcus aureus; (b) Escherichia coli.

Detailed ways:

Example 1

A copper film of 3 micrometers is deposited on the surface of the foam sponge material (about 550 micrometers in pore size) by ion sputtering coating method, so that the foam sponge material obtains electrical conductivity. Under the conditions of composition ratio and process parameters shown in Table 1, electroplate copper film on the foam sponge material after conductive treatment. When the film thickness of the electroplating material is about 20 μm, take it out from the electroplating solution, wash it with water and dry it in the air. , heated to 800°C for 3 hours under the protection of argon, and took it out after cooling down to room temperature, and removed the foam sponge in the grid frame to form a metal copper grid;

Table 1 Cu electroplating solution formula and process parameters

Components and process parameters Content (g/L) or parameters Components and parameters Content (g/L) or parameters Copper pyrophosphate (Cu ₂ P ₂ O ₇ ) 50-100 pH value 7.5-9.2 Potassium pyrophosphate (K ₄ P ₂ O ₇ .3H ₂ O) 200-400 Temperature/℃ 25-60 Potassium sodium tartrate (KNaC ₄ H ₄ O ₆ .4H ₂ O) 10-30 Voltage/V 12-24 Nitrilotriacetic acid [N(CH ₂ COOH) ₃ ] 12-25 Current density/A·dm ^-2 0.5-2.0 Potassium nitrate (KNO ₃ ) 10-30

Finally, a 3-micron thick Cu plus CeO ₂ film was deposited on the surface of the prepared metal copper mesh to obtain a metal-loaded (Cu+CeO ₂ )/Cu composite mesh antibacterial filter metal material. Its bath composition and process parameter are identical with the copper plating solution shown in _table 1 basically, just added the CeO of 8-10g/L in this solution Micropowder and configure mechanical stirring; Among the present invention, the diameter of _CeO2 micropowder In the range of 0.8 microns to 3 microns. This composite mesh antibacterial filter metal material is made up of metal copper mesh and metal Cu plus _CeO coating, the porosity of the composite mesh structure of this embodiment is 96%, the aperture is about 500 microns, and the content of Ce in the surface film is 1.1 at % (see Table 2). Figure 1 shows the macroscopic photo of the (Cu+CeO ₂ )/Cu composite mesh antibacterial filter metal material. It can be seen from Figure 1 that the diameter of the micropores of the mesh material is relatively uniform in three directions and the holes are interconnected with each other. connected. Figure 2 shows the surface micro-morphology of (Cu+CeO ₂ )/Cu composite mesh antibacterial filter metal material. It can be observed from Figure 2 that in the Cu plus CeO ₂ film, the copper film is the base, and the CeO ₂ particles are in the The copper film is randomly distributed, and its surface shape is: a rectangle with a length of about 2 microns and a width of about 1 micron.

In the present invention, the meaning of (Cu+CeO ₂ )/Cu is: copper mesh is used as the substrate, and Cu plus CeO ₂ film is plated on the surface of the copper mesh.

Table 2 Composition of Cu plus CeO ₂ film on the surface of (Cu+CeO ₂ )/Cu composite mesh material

The present invention carries out antibacterial property test to prepared material, and concrete test method is as follows:

1 Selection of experimental strains

The antibacterial performance of the material was tested by Escherichia coli (E.coli) ATCC 8099, Staphylococcus aureus (S.aureus) ATCC6538 and Candida albicans (V.albicans) ATCC 10231. 2 Antibacterial experiment

(1) Activation of bacteria

The slant-preserved bacteria were transferred to the plate nutrient agar medium, cultured at (37±1)°C for 24 hours, and transferred once a day for no more than 2 weeks. Fresh bacterial cultures after three consecutive transfers were used in the experiment.

(2)) Experimental samples

The experimental samples are: a: control sample: sponge without antibacterial ingredients, with a size of Φ20mm; b: (Cu+CeO ₂ )/Cu mesh antibacterial material sample: two sizes: Φ20mm and Φ26.6mm.

The control sample was sterilized with alcohol and sterilized with an ultraviolet disinfection lamp for 30 minutes. The mesh antibacterial material samples were sterilized by dry heat at 160°C for 2 hours.

Draw 5ml of sterile water into a sterile petri dish, pick up two sterile glass slides with sterilized tweezers, and put them into the petri dish, with the water level not exceeding the upper glass slides. Hold the sample with tweezers and put it on the glass slide, and then put 0.2ml of the test bacteria solution with an appropriate concentration on the sample to make the bacteria solution evenly contact with the sample. The Petri dish was sealed with Parafilm. Cultivate at (37±1)°C. Add the bacterial solution to the control sample in the same way. Each sample was done in 3 parallels.

After the bacterial solution and the sample have interacted for a specified period of time, take out the petri dishes from the incubator, add 45ml of eluent to each petri dish, wash the control sample and the antibacterial material sample repeatedly, shake the eluent well, and carry out Gradient dilution, select the appropriate concentration of the diluent to spread on the nutrient agar plate medium (NA), and count the viable bacteria after culturing at (37±1)°C for 24 hours. Total Determination Method "Determination of the number of viable bacteria.

In order to ensure the reliability of the antibacterial test data, the above test was repeated three times.

The antibacterial test results are shown in Tables 3 and 4. The formula for calculating the sterilization rate is:

The number of viable bacteria in the above formula is the number of viable bacteria after the antibacterial experiment.

In addition, Staphylococcus aureus ATCC6538 with an initial viable count of 1.0×10 ⁶ cfu/ml was selected as the test strain, and the antibacterial properties of reticulated Cu and reticulated (Cu+CeO ₂ )/Cu materials were compared Test; the antibacterial properties of (Cu+CeO ₂ )/Cu composite mesh materials against Escherichia coli ATCC8099 and Staphylococcus aureus ATCC 6538 were also evaluated by the ring of inhibition test.

Table 3 Sterilization rate of mesh (Cu+CeO ₂ )/Cu antibacterial material

Table 4 Comparative test results of antibacterial properties of reticulated Cu and reticulated (Cu+CeO ₂ )/Cu

Test bacteria: Staphylococcus aureus, total number of initial viable bacteria: 1.0×10 ⁶ (cfu/ml)

It can be seen from Table 3 that the (Cu+CeO ₂ )/Cu composite mesh antibacterial filter metal material has excellent antibacterial properties against Escherichia coli, Staphylococcus aureus and Candida albicans, three representative fungi. Among them, the antibacterial effect on Escherichia coli was the best, and its antibacterial rate reached 98.2%, 99.1% and 100% after the action time of 20 minutes, 40 minutes and 60 minutes, but the antibacterial effect on Candida albicans was relatively poor, and the effect was 60%. Minutes later, there were still 14 cfu/ml colonies alive.

As can be seen from Table 4, the antibacterial rate of the two materials is 100% after acting on the bacterial solution for 60 minutes, and the number of colonies of the network (Cu+CeO ₂ )/Cu after acting on the bacterial solution for 20 minutes and 40 minutes is respectively 27.5cfu/ml and 13cfu/ml, respectively 20.5cfu/ml and 10cfu/ml higher than reticulated Cu. These data show that by adding CeO ₂ micropowder to the reticulated Cu material, its antibacterial performance does not change much, but only slightly slows down the dissolution rate of Cu ²⁺ ions, which is a good choice when the dissolution rate of Cu ²⁺ ions needs to be controlled. benefit.

Figure 3 shows the results of the inhibition zone test. As can be seen from Figure 3(a), no inhibition zone appears in the sponge control sample (white) in the test against Staphylococcus, while the high-porosity reticular (Cu+CeO ₂ )/Cu antibacterial material has an antibacterial ring with an inner diameter of 20mm and an outer diameter of 36.2mm; as shown in Figure 3(b), for E. mm antibacterial ring, showing good antibacterial properties.

Example 2

The difference from Example 1 is:

A 2-micron copper film is deposited on the surface of the foam sponge material (about 450 micrometers in pore size) by ion sputtering coating method, so that the foam sponge material obtains electrical conductivity. Under the conditions of composition ratio and process parameters shown in Table 1, electroplate copper film on the foam sponge material after conductive treatment. When the film thickness of the electroplating material is about 50 μm, take it out from the electroplating solution, wash it with water and dry it in the air. , heated to 850°C for 1 hour under the protection of argon, took it out after cooling down to room temperature, removed the foam sponge in the grid frame, and formed a metal copper mesh; finally, deposited 2.5 micron thick metal copper mesh on the surface of the prepared metal copper mesh Adding Cu to CeO ₂ film, so as to obtain metal-loaded (Cu+CeO ₂ )/Cu composite mesh antibacterial filter metal material. The composite mesh antibacterial filter metal material is composed of metal copper mesh and metal Cu plus CeO ₂ coating. The porosity of the composite mesh structure in this embodiment is 85%, and the pore diameter is about 350 microns.

In this embodiment, the antibacterial properties of the prepared materials are tested, and the (Cu+CeO ₂ )/Cu composite mesh antibacterial filter metal material is effective against Escherichia coli, Staphylococcus aureus and Candida albicans. Excellent antibacterial properties.

Example 3

The difference from Example 1 is:

A 2.5-micron copper film is deposited on the surface of the foam sponge material (with a pore size of about 450 micrometers) by ion sputtering coating method, so that the foam sponge material obtains electrical conductivity. Under the conditions of the composition ratio and process parameters shown in Table 1, electroplate copper film on the foam sponge material after conductive treatment. When the film thickness of the electroplating material is about 23 μm, take it out from the electroplating solution, wash it with water, and dry it in the air. , heated to 700°C for 4 hours under the protection of argon, took it out after cooling down to room temperature, removed the foam sponge in the grid frame, and formed a metal copper grid; finally, deposited a 2-micron-thick metal copper grid on the surface of the prepared metal copper grid. Adding Cu to CeO ₂ film, so as to obtain metal-loaded (Cu+CeO ₂ )/Cu composite mesh antibacterial filter metal material. The composite mesh antibacterial filter metal material is composed of metal copper mesh and metal Cu plus CeO ₂ coating. The porosity of the composite mesh structure in this embodiment is 90%, and the pore diameter is about 400 microns.

In this embodiment, the antibacterial properties of the prepared materials are tested, and the (Cu+CeO ₂ )/Cu composite mesh antibacterial filter metal material is effective against Escherichia coli, Staphylococcus aureus and Candida albicans. Excellent antibacterial properties.

Experimental results show that the composite mesh antibacterial filter metal material of the present invention is applied to gas or liquid production filter devices for food, beverages, and alcohol; or, it is applied to filter screens in air conditioners.

Claims (5)

1. a copper mesh surface plating Cu adds CeO ₂ antibacterial filter metal material, it is characterized in that: this metal material is the metal copper mesh surface plating Cu that obtains on the foam sponge substrate material and metal copper mesh surface plating Cu adds CeO ₂ composite network The thickness of the copper film is 20 microns-50 microns, the thickness of Cu plus _CeO2 is 2 microns-3 microns, the porosity of the composite network structure is 85%-96%, and the pore diameter is in the range of 350 microns-500 microns adjustable. 2. according to claim 1 copper mesh surface plating Cu adds CeO ₂ preparation methods of the antibacterial filter metal material, it is characterized in that, take foam sponge as base material, load metal (Cu+CeO ₂ )/Cu forms composite network shaped antibacterial filter metal material, the specific steps are as follows: (1) conductive treatment of base material; (2) plating metal copper film on base material; (3) heat treatment, the plated material is heat-treated for 1-4 hours in an argon protective atmosphere at 700-850° C., to remove the organic foam in the grid frame and form a metal copper mesh; (4) Cu plus CeO ₂ is plated on the surface of the metal copper mesh after heat treatment to obtain a composite mesh antibacterial filter metal material loaded with metal (Cu+CeO ₂ )/Cu. The composite mesh antibacterial filter metal material is composed of metal copper mesh and Metal Cu plus CeO ₂ coating composition. 3. according to the copper mesh surface plating Cu described in claim ₂ adds CeO The preparation method of the antibacterial filter metal material, it is characterized in that: described conductive treatment is to deposit 2 on the foam sponge material surface by ion sputtering coating method - 3 micron copper film to make the foam sponge material conductive. 4. according to the copper mesh surface plating Cu described in claim 2 adds CeO ₂ preparation methods of the antibacterial filter metal material, it is characterized in that: described coating adopts conventional electroplating method to carry out electroplating copper; Add CeO ₂ micropowder 8- 10g/L and equipped with mechanical stirring electroplating copper solution, deposit Cu plus CeO ₂ coating. 5. according to claim 1 copper net surface plated Cu adds CeO ₂ application of the antibacterial filter metal material, it is characterized in that: this composite mesh antibacterial filter metal material is applied to the gas or liquid production of food, beverage, wine A filter device; or, a filter used in an air conditioner.

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