WO2008028355A1

WO2008028355A1 - Method for making surface antibacterial products utilizing physical vapor deposition technology

Info

Publication number: WO2008028355A1
Application number: PCT/CN2006/003275
Authority: WO
Inventors: Peiqi Jiang
Original assignee: Peiqi Jiang
Priority date: 2006-08-28
Filing date: 2006-12-04
Publication date: 2008-03-13

Abstract

Disclosed is a method for making surface antibacterial products utilizing physical vapor deposition technology, the method involves using physical vapor deposition technology to coat antibacterial target materials or vaporization materials onto a substrate surface to form an antibacterial film layer, wherein the antibacterial target materials or vaporization materials are one or more selected form the group consisting of Ti, Zn, Ca, Si, Mg, Zr, Cd, As, Sb, Se, Ce, Re, Cu, Ag, Pb, Hg, Co, Ni, Al, Fe, and oxides, sulfides, nitrides, and carbides thereof, a reaction gas usedd in the physical vapor deposition technology is O2, N2, NH3, CH4, C2H6 or H2S. Holes (1) are drilled on the target (3) surface to feed a gas through gas passages (2), thereby preventing the target from poisoning efficiently to realize multi-arc coating and magnetron sputtering and improving coating efficiency and film layer quality.

Description

Method for manufacturing surface antibacterial products by physical vapor deposition technology

The present invention relates to a method for preparing a surface antibacterial article, and more particularly to a method for producing a surface antibacterial article by physical vapor deposition.

Background technique

The antibacterial ability of antibacterial products is mainly reflected on the surface of antibacterial products. Conventional antibacterial products are made by directly incorporating antibacterial materials into substrates such as metal materials, polymer materials, and glazes. 'This method causes a large amount of waste material to be wasted, and the manufacturing process is complicated and the processing cost is too high. In the prior art, some new technologies for manufacturing surface antibacterial products by physical vapor deposition technology have appeared, such as Chinese patent application "A surface antibacterial, wear-resistant stainless steel product and its preparation method" (application number: 200410027063. 2), The technology provides a method for preparing wear-resistant and antibacterial stainless steel products by magnetron sputtering. The method is purely used for the production of stainless steel products, and the use range is too small, and is not practical in many fields. Wear-resistant technology, such as disposable antibacterial catheter, medical wound suture surface, and ventilator tube inner wall; 2 the antibacterial material used is only silver and copper, which cannot meet the requirements in special technical fields, such as photocatalysis. Unachievable, the existing photocatalytic material Ti0 ₂ can only have an antibacterial effect under ultraviolet light of 387. 5 nm or less, and it is not antibacterial at 387. 5 nm or more; 3 This coating method has directionality and is not applicable. Plated parts on complex surfaces, such as the inner wall of a ventilator pipe.

There are four kinds of physical vapor deposition technologies: vacuum evaporation plating, magnetron sputtering, multi-arc plating and plasma plating. Among them, the above methods are applied by plasma plating, magnetron sputtering and multi-arc plating. Argon gas is added into the coating chamber, and argon gas becomes charged argon ions under the action of magnetic field and high-voltage current. The argon ions strike the target at high speed, thereby hitting the target against the workpiece to be plated. At the same time, in the reaction coating, A reaction gas such as oxygen, nitrogen, acetylene gas or hydrogen sulfide is added to cause the target material to become an oxide, a carbide, a nitride, a sulfide or the like. Ion plating refers to the application of a bias current to the forged workpiece, so that the deposited material has directionality and high-speed kinetic energy, so that the plating material and the substrate are more closely combined. There are mainly multi-arc ion plating, ion beam assisted deposition plating, Sediment plating and plasma plating of ionized clusters.

However, in the actual work, the above coating technologies have different technical defects, such as:

1. In actual work, it is found that the material utilization rate of the sputtering plane target is only 20%, and the material utilization rate of the sputtering cylinder target is 80%. The precious metal materials such as silver are mostly used for the cylindrical target, which will be made. The silver tube is placed over the copper target. During the use, the silver sleeve will undergo lateral expansion and longitudinal shrinkage, that is, the silver tube becomes thicker and shorter, which separates the silver tube from the copper core and affects the sputtering effect.

2. In the process of multi-arc coating, especially in the process of black coating, the reaction is not comprehensive, that is, the pure black product is not plated. This is because the multi-arc plating uses the arc method to evaporate the target and generate a large amount of ion gas flow. A large amount of ionic gas stream repels the reaction gas to the surface of the workpiece to be plated.

3. Target poisoning is prone to occur during magnetron sputtering black plating. This is because the molten carbon gas is filled into the furnace cavity for the plating of pure black products, which causes the concentration of argon ions to decrease, which affects the sputtering effect.

Summary of the invention

The object of the present invention is to overcome the above-mentioned drawbacks of the prior art, and to provide a method for manufacturing a surface antibacterial product by physical vapor deposition technology with low cost, wider use range and simple and convenient fabrication, and the method of the invention has 1 antibacterial method. The material is plated onto the surface of the complex surface to be plated; 2 to enhance the antibacterial effect of the photocatalytic antibacterial material; 3 to provide more antibacterial materials; 4 to solve the separation of the casing and the core of the cylindrical target; 5 with pure multi-arc plating Black film process; 6 magnetron sputtering is used to plate pure black film, and it also prevents target poisoning.

The technical solution of the present invention is:

A method for manufacturing a surface antibacterial article by using a physical vapor deposition technique, comprising: using a physical vapor deposition technique to plate an antibacterial target or an evaporant onto a surface of a substrate to form a film layer, wherein: the antibacterial material is Ti, Zn, Among Ca, Si, Mg, Zr, Cd, As, Sb, Se, Ce, Re, Cu, Ag, Pb, Hg, Co, Ni, Al, Fe and their oxides, sulfides, nitrides, carbides One or more of the reaction gases charged in the physical vapor deposition technique are 0 ₂ , N ₂ , M ₃ , CH ₄ , ( ₂ or 3.; The physical vapor deposition technique is evaporative plating, magnetron sputtering, multi-arc plating or plasma plating; the plasma plating is immersion plasma plating, magnetron sputtering, ion plating, radio frequency plasma plating, microwave plasma plating, and heat. Wire cathode assisted plasma plating or ionized cluster deposition plasma plating;

The ionized cluster deposition plasma plating apparatus is a heating source, an ionization device, an accelerating electrode and a substrate from bottom to top, and is installed inside the heating source, and is 3 to 5;

The ionization device is a microwave ionization device;

In the multi-arc plating process, it is required to drill a small pore on the antibacterial target, and use a gas pipe to introduce a reaction gas into the pore;

In the magnetron sputtering plating process, it is required to provide a ventilation line tube on the surface of the substrate;

The ratio of the antibacterial material in the film layer is 0.01% ~ 100%;

The cylindrical target is composed of an inner core made of a copper tube and a jacket made of an antibacterial material, and the antibacterial material is made into a metal strip and wound around the inner core;

The cylindrical target is composed of an inner core made of a copper tube and a jacket made of an antibacterial material, and the inner core and the outer sleeve are screwed;

The substrate is a dry solid material, which may be a metal material, a non-metal material, a fiber product, a polymer material, a dried plant material or a leather material;

The surface antibacterial product is a stainless steel cutter, and the manufacturing process is that the silver or copper-containing stainless steel plate is first welded or pasted on the blade edge of the cutter main body, and then the blade edge is ground, and then the physical vapor deposition coating is applied to the wear-resistant antibacterial surface layer. .

The technical solution of the present invention can produce the following technical effects:

1. The antimicrobial material can be plated onto the surface of a complex article, such as the inner wall of a ventilator tube. The present invention employs immersion plasma plating. In a magnetron sputtering glow discharge plasma, a pulse voltage is applied to a plated member at a voltage of several tens of kilovolts, and the plated member is immersed in the plasma, and ions in the plasma are applied to the surfaces of the workpiece. It can be plated in hooks and holes. In addition to magnetron sputtering plasma, there is RF plasma, Microwave plasma, hot wire cathode assisted plasma, can be used for antibacterial coating.

2. Enhance the antibacterial effect of photocatalytic antibacterial materials by using a combination of antibacterial materials: Photocatalytic antibacterial materials include: Ti0 ₂ , ZnO, CaO, Si0 ₂ , MgO, Zr0 ₂ , CdS , Se0 ₂ , SiC; These materials have low photocatalytic activity and show no antibacterial effect under natural light. When rare earth lanthanum, cerium or antibacterial materials such as Cu, Ag, Pb, etc. are added during the coating process, they have strong antibacterial effect under natural light. In the physical vapor deposition process, Ti, Zn, Ca, Si, Mg, Zr, Ca, Se, Si, the material is one or more of elemental materials or compounds, and is added to rare earth lanthanum, cerium or Cu, Ag, One or more materials in Pb are mixed and plated, and the corresponding gas ₀₂ is charged to deposit a specific photocatalytic composite antibacterial material.

3. Providing more antibacterial materials: The invention prepares surface antibacterial products by physical vapor deposition technology, the process is simple and convenient to manufacture, high in efficiency, low in cost, and the invention arranges and combines antibacterial materials having different characteristics according to requirements. Therefore, surface antibacterial products suitable for different technical fields are obtained, such as surface antibacterial products such as human implant materials and utensils prepared by using Ag, Cu, Zn, Ce, Ca which are safe and non-toxic to human body; safe Co, Ni, Al , Fe, S to prepare surface antibacterial products such as human contact materials; use antibacterial materials As, Sb, Se, Hg with strong bactericidal ability, but toxic to human body to prepare other surface antibacterial products; strong antibacterial such as Ag and antifungal For example, Cu mixed plating is used to prepare a broad-spectrum antibacterial product; Zn, Ce and Cr are added to the silver plating material to solve the defect that silver is easily oxidized and blackened, and a surface antibacterial product with beautiful appearance and stable properties is obtained. The charged reaction gas is 0 ₂ , N ₂ , NH ₃ , CH ₄ , C ₂ H ₆ , H ₂ S, and the above-mentioned antibacterial material and reaction gas can be combined with each other as needed, and the antibacterial materials can also be combined with each other, such as A _g S AgCeNi can also be combined with other metal non-metals such as AgW, CrAgN CuZnO, etc., and can be combined into thousands of new combined antibacterial materials. 01%〜100百分比。 The proportion of the inorganic material in the coating layer is 0. 01% ~ 100%.

4. The casing and the die phase separation defect of the cylindrical target are solved. The antibacterial target material of the invention is a cylindrical target, and the cylindrical target is an inner core made of a copper tube and a jacket made of an antibacterial material. The antibacterial material may be attached to the inner core by a metal strip or may be connected to the inner core by a screw connection. 5. The process of using a multi-arc plating pure black film is realized. The invention is applied to a small air hole around a multi-arc target, and directly passes CH ₄ and C ₂ H ₆ gas into the hole to form high carbon in the plating area. It can be plated with pure black film.

6. Realizing the disadvantages of magnetron sputtering plating which can both plate pure black film and prevent target poisoning. The present invention adopts a distribution line on the surface of the workpiece (substrate) to be plated, and gas CH ₄ and C _{2 are introduced} therein. The surface of the workpiece to be plated forms a high carbonized zone, which can effectively prevent target poisoning and can be plated with pure black film.

7. The invention also provides a combined ionizing cluster deposition technique. Ionized cluster deposition is the deposition of thin films using ionized radicals with a certain energy. The ionized atomic group may comprise hundreds or even thousands of atoms, which are deposited on the workpiece to be plated under the acceleration of the electric field. At the moment of contact with the working piece, the atomic group is broken, the atoms are dispersed and deposited on the lining. Bottom surface. This has a variety of materials deposited, the coating has good adhesion, low temperature and controllability. The technology of the present invention requires a plurality of evaporation enthalpy to meet the needs due to the need for composite material coating. Generally, the resistance heating method is used. For convenience of control, the present invention designs a carbon-embedded crucible, and a set of emblem-wave heating method. The method has a great advantage. The microwave can give the ionized group a charge, accelerate the ionization effect, and accelerate the sputtering rate of the ionized atomic group. The coating quality is better.

DRAWINGS

Figure 1 is a schematic diagram of a gas pipeline for distributing an arc source target, wherein 5 is an ion arc region;

Figure 2 is a cutaway view of the arc source target;

3 is a schematic structural view of a casing cylindrical target made by a metal strip winding method;

Figure 4 is a schematic view showing the structure of a casing cylindrical target made by screwing;

Figure 5 is a schematic view showing the principle of surface coating by immersion plasma plating;

6 is a schematic view showing the principle of surface coating by ionizing cluster deposition plasma plating;

Figure 7 is a schematic diagram showing the structure of an antibacterial stainless steel table knife;

Figure 8 is a view of the A - ή 图 of Figure 7.

1. Vent hole 2. Snorkel 3. Target or evaporant 4. Plated substrate · 5. Plasma furnace 6. Hot wire cathode 7. Gas input pipe 8. High pressure pulse 9. 坩埚 10. Heat source 11. Ionization source 12. Acceleration electrode 13. Substrate 14. Blade 15. Silver-containing stainless steel blade body 16. Antibacterial coating layer

detailed description

Example 1

The surface of the object is coated with an antibacterial layer by evaporation coating technology.

The coating technology is carried out in an existing activation reaction evaporation deposition apparatus: wherein the substrate is selected from a dry solid material such as a metal material, a non-metal material, a fiber product, a polymer material, a dried plant material or a leather material, and an antibacterial material. The evaporation material is selected from the group consisting of Ti, Zn, Ca, Si, Mg, Zr, Cd, As, Sb, Se, Ce, Re, Cu, Ag, Pb, Hg, Co, Ni, Al, Fe and their oxides, sulfides, One or more of a nitride or a carbide, the amount of which is 0.01% to 100% by weight of the entire film layer, and the reaction gas is 0 ₂ , N ₂ , NH ₃ , CH ₄ , C ₂ H ₆ i H ₂ S.

Example 2

The anti-bacterial layer is coated on the surface of the object by multi-arc plating technology.

The coating technology is carried out in an existing multi-arc ion coating machine: wherein the substrate is selected from dry solid materials such as metal materials, non-metal materials, fiber products, polymer materials, dried plant materials or leather materials, and antibacterial materials. The target is selected from the group consisting of Ti, Zn, Ca, Si, Mg, Zr, Cd, As, Sb, Se, Ce, Re, Cu, Ag, Pb, Hg, Co, Ni, Al, Fe and their oxides, sulfides, One or more of nitrides and carbides, in an amount of 0.01% - 100% by weight of the entire film layer, as shown in Fig. 1. Fig. 2, at which time it is required to be drilled on the antimicrobial target 3 The small pores 1 are opened, and the reaction gas is introduced into the pores 1 by the gas pipe 2. A magnetron sputtering antibacterial target is also disposed in the multi-arc coating furnace, and the antibacterial target 3 is a cylindrical target. As shown in FIG. 3, the cylindrical target is made of a copper tube inner core 3-1 and made of an antibacterial material. The formed jacket is composed of 3 - 2, and the above-mentioned antibacterial material is formed into a metal strip and wound around the inner core; the reaction gas is 0 ₂ , N ₂ , NH ₃ , CH ₄ , C ₂ H ₆ or H ₂ S. 磁Preparation of surface antibacterial products by magnetron sputtering coating technology.

The coating technology is carried out in an existing magnetron sputtering ion plating machine: wherein the substrate is selected from a dry solid material such as a metal material, a non-metal material, a fiber product, a polymer material, a dried plant material or a leather material. The antibacterial target is selected from the group consisting of Ti, Zn, Ca, Si, Mg, Zr, Cd, As, Sb, Se, Ce, Re, Cu, Ag, Pb, Hg, Co, Ni, Al, Fe and their oxides, and vulcanization. One or more of the substance, the nitride, and the carbide are used in an amount of 0.01% to 100% by weight of the entire film layer, and it is necessary to provide a ventilating tube on the surface of the substrate. And the antibacterial target 3 is a cylindrical target, and the cylindrical target shown in FIG. 4 is a cylindrical target composed of an inner core 3-1 made of a copper tube and a jacket 3 - 2 made of an antibacterial material, and the inner core and the outer sleeve are threaded. connection. The reaction gas is 0 ₂ , N ₂ , ₃ , CH ₄ , C ₂ H ₆ or H ₂ S.

Example 4

The preparation of surface antibacterial products is carried out by magnetron sputtering coating technology.

The coating technology is carried out in a ionization beam deposition plasma plating apparatus: wherein the substrate is selected from a dry solid material such as a metal material, a non-metal material, a fiber product, a polymer material, a dried plant material or a leather material, and an antibacterial material. The target is selected from Ti, Zn, Ca, Si, Mg Zr, Cd, As, Sb, Se, Ce, Re, 'Cu, Ag, Pb, Hg, Co, Ni, Al, Fe and their oxides, sulfides, One or more of nitrides and carbides, used in an amount of 0.01% to 100% by weight of the entire film layer, and the reaction gas is 0 ₂ , N ₂ , NH ₃ , CH ₄ , C ₂ H ₆ or H ₂ S.

The basic structure of the above-described ionized cluster deposition plasma plating apparatus is the same as that of the prior art. FIG. 6 shows the heating source 10, the ionization device 11, the accelerating electrode 12 and the substrate 13 in order from bottom to top, and the crucible 9 is mounted on the heating. Inside the source 10, the main difference is that there are a plurality of 坩埚9, generally 3 to 5, which can hold a variety of targets.

Example 5

浸 Preparation of surface antibacterial articles by immersion plasma plating.

The coating technology is carried out in a dip plasma plating apparatus, as shown in Figure 5: wherein the substrate is selected Dry solid materials, such as metal materials, non-metallic materials, fiber products, polymer materials, dry plant materials or leather materials, antibacterial. Targets use Ti, Zn, Ca, Si, Mg, Zr, Cd, As, Sb , Se, Ce, Re, Cu, Ag, Pb, Hg, Co, M, Al, Fe and one or more of its oxides, sulfides, nitrides, carbides, the amount of which is the entire film weight From 0.01% to 100%, it is necessary to provide a ventilation tube on the surface of the substrate. The reaction gas is 0 ₂ , N ₂ , NH ₃ , C , ( ₂ 11 ₆ or 3.

Example 6

Preparation of antibacterial stainless steel knife:

In the process of cutting, peeling and cutting, the knife is easy to passivate and the sharpness will decrease. It is necessary to grind the blade. In the process of grinding the blade, the antibacterial surface of the blade will be worn away, and the surface layer will be worn away. No antibacterial effect is achieved.

In order to solve this problem, use the following solution to solve, Figure 7. Figure 8: that is, before the coating, the stainless steel knife needs to be pre-treated, specifically to first weld or paste the silver or copper-containing stainless steel plate 15 in the tool body. The steel plate 14 is cut at the cutting edge, and then the blade is ground, and then the physical vapor deposition is applied to the wear-resistant antibacterial surface layer. The specific coating technique can adopt any one of the above embodiments 1 to 4.

The antibacterial stainless steel knife prepared by the above method has the following advantages: 1. The blade is still antibacterial after being ground. 2. Save on the use of silver-containing stainless steel.

Claims

要利要要

A method for fabricating a surface antibacterial article by using a physical vapor deposition technique, which comprises depositing an antibacterial target or an evaporating substance onto a surface of a substrate to be coated to form an antibacterial film layer by using a physical vapor deposition technique, wherein: the antibacterial target Or evaporating materials are Ti, Zn, Ca, Si, Mg, Zr, Cd, As, Sb, Se, Ce, Re, Cu, Ag, Pb, Hg, Co, κ Al, Fe and their oxides, sulfides One or more of a nitride, a carbide, and a reaction gas charged in the physical vapor deposition technique is 0 ₂ , N ₂ , NH ₃ , CH ₄ , C ₂ H ₆ or H ₂ S. '

2. A method for producing an antimicrobial substrate by physical vapor deposition according to the requirements of claim 1, wherein the physical vapor deposition technique is evaporation plating, magnetron sputtering, multi-arc plating or plasma plating.

3. The method for manufacturing a surface antibacterial article by physical vapor deposition according to claim 2, wherein: the plasma plating is immersion plasma plating, magnetron sputtering, ion plating, radio frequency plasma plating, microwave plasma. Plating, hot wire cathode assisted plasma plating or ionizing cluster deposition plasma plating.

4. A method for producing a surface antibacterial article by physical vapor deposition technique according to claim 3, characterized in that the ionized cluster deposition plasma plating device is a heating source U0) and an ionization device in order from bottom to top (11) ), the accelerating electrode (12) and the substrate (13), and the crucible (9) are installed inside the heating source (10), and are 3 to 5.

5. A method of producing a surface antibacterial article by physical vapor deposition as described in claim 4, characterized in that said ionization device (11) is a microwave ionization device.

6. A method of manufacturing a surface antibacterial article by physical vapor deposition according to claim 1 or 2, characterized in that: in said multi-arc plating process, said target is in said target (Fig. 3, Fig. 4) Shown)

(3) A small air hole (1) is drilled, and a reaction gas is introduced into the air hole (1) by using the air pipe (2).

1. The method for manufacturing a surface antibacterial article by physical vapor deposition technique according to claim 1 or 2. The method is characterized in that: in the magnetron sputtering plating process, a ventilation line tube is disposed on a surface of the substrate to be plated.

8. A method of producing a surface antibacterial article by physical vapor deposition as described in claim 1, wherein the antibacterial target accounts for 0.01% to 100% of the film layer.

9. The method of manufacturing a surface antibacterial article by physical vapor deposition technique according to claim 1, wherein: said antibacterial target is a cylindrical target or a planar target.

10. A method of manufacturing a surface antibacterial article by physical vapor deposition according to claim 9, characterized in that: the cylindrical target is made of an inner core (3-1) made of a copper tube and an antibacterial material. The outer casing (3-2) is composed of the above-mentioned antibacterial material which is formed into a metal strip and wound around the inner core.

11. The method of manufacturing a surface antibacterial article by physical vapor deposition technique according to claim 9, wherein: said cylindrical target is made of an inner core (3-1) made of a copper tube and an antibacterial material. Composed of a jacket (3- 2), the inner core and the outer casing are screwed.

12. The method of manufacturing a surface antibacterial article by physical vapor deposition according to claim 1, wherein said substrate to be plated is a metal material, a non-metal material, a fiber product, a polymer material, a dried plant. Material or leather material.

13. The method for manufacturing a surface antibacterial article by physical vapor deposition according to claim 1, wherein the surface antibacterial article is a stainless steel cutter, and the manufacturing process comprises first placing a silver-containing or copper-containing stainless steel plate (15). Solder or stick to the cutting edge of the tool body steel plate (14), then grind the blade edge, and then perform physical vapor deposition plating on the wear-resistant antibacterial surface layer (16).