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Low-temperature plasma surface modification of metal biomaterials by graft polymerization of metal-polymers

Low-temperature plasma surface modification of metal biomaterials by graft polymerization of metal-polymers: The application of metal biomaterials in low temperature plasma surface modification mainly includes three aspects: improving biocompatibility, immobilizing bioactive macromolecules, and improving the physiological corrosion resistance of metal materials. Grafting is a commonly used plasma surface modification method. The grafting of appropriate monomers or polymers can improve the hydrophilicity, adhesion, corrosion resistance, electrical conductivity and biocompatibility of metal polymers. When a metal material is implanted into a living body, it must meet the requirements of biocompatibility. Biological compatibility is the degree to which a substance is compatible with blood and tissue. Surface modification of metal biomaterials with functional groups such as grafting, polymerization, and hydrophilicity is a surface modification method of metal biomaterials that is currently studied. It is mainly used to improve the biocompatibility of materials and induce the growth of living cells. biological activity of the material. Plasma surface modification of PEG was carried out by AgnesR, Denes, etc., so that PEG was grafted on the surface of stainless steel. The XPS results showed that the introduction of a large number of low-temperature plasma surface modification -CH2-CH2-O groups on the surface of stainless steel can significantly Improve the hydrophilicity of the material surface. Reduce roughness and greatly reduce the adsorption of bacteria on the surface of the material. Coronary angioplasty (PTCA) is often used in clinical treatment of coronary vascular disease. That is to say, a metal dilator is used to support the blood vessel inside the blood vessel, but the polymer metallized Stern fixation membrane used still has a high coagulation property, so the blood vessel will become more narrow. Lahann et al. used a CVD method to perform a chlorination reaction on the polymer metal surface, followed by SO2 microwave plasma treatment. The study found that after SO2 plasma treatment, the contact angle was reduced to 15 degrees, and the hydrophilicity of the material surface was improved. The grafting of organic organic grafts on the metal plasma surface or the metallization of the polymer surface involves the adhesion of the polymer to the metal. Zhang et al. investigated the adhesion of PTFE (PTFE) to metallic aluminum. First, PTFE was pretreated with argon plasma (frequency 40kHz, power 35W, argon pressure 80Pa). Then use acrylate glycerol, GMA, heat to evaporate aluminum, make it and GMA graft copolymerization reaction, generate hydrogen oxide and peroxide, and then use heat to evaporate aluminum, use GMA, the graft copolymer of PTFE and A's The adhesion is 22 times that of PTFE and Al and 3 times that of PTFE and Al pretreated with Ar plasma only. Calcium and phosphorus are the basic components of bone tissue. Depositing a layer of calcium phosphate or hydroxyapatite (HA) on the surface of metal implants can effectively improve its compatibility with bone tissue and enhance osteogenic induction. . The modification can be performed by plasma spraying (PSC). Polypropylene was treated by three methods (mechanical roughening method, low temperature plasma surface modification with oxygen, nitrogen and argon gas, and intermediate layer method), and the adhesion characteristics of metal polymer on the polymer were studied, The results show that the mechanical roughening method can effectively improve the adhesion between polypropylene and copper, but the effect of plasma treatment is better, especially Ar plasma, in the process of polypropylene polymerization, the intermediate layer contains C- 0 key, strong adhesion. Arc discharge (>10000°C) is generated through the high potential difference between the electrodes, ionizing the gas around the electrodes into plasma, and then hitting the modified powdery substance suspended on the surface at high speed, causing it to settle on the metal surface. Plasma spraying is a widely used deposition method. The coating can form a high bonding force between the substrate and the surface modification layer to obtain a fully covered coating (40~54m). Coatings formed by this process can rapidly nucleate and grow in body fluids. However, due to high temperature treatment, there are disadvantages such as uneven density, inconsistent structure, and large variation in bond strength, and hydroxyapatite is easily decomposed during the spraying process, and is prone to desolubilization under body fluid conditions. After spraying the HA coating, heat treatment or steam bath is also required to improve the composition and structure of the coating. If the vapor pressure is 0.15 MPa and the temperature is 125 ℃, and the steam bath is treated for 6 h, most of the amorphous HA phase will be transformed into crystals, and other decomposition products generated during spraying will

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Plasma surface modification equipment treatment to improve the corrosion resistance of biological scientific research metals

Plasma surface modification equipment treatment to improve the corrosion resistance of biological scientific research metals: Surface modification of metal materials by biomedical chemical methods is a new type of new technology developed in recent years. This method is based on the following assumptions: the biologically active substances are directly attached to the metal substrate, and the macromolecular protein or enzyme-like organic polymer materials are introduced to the surface of the substrate, so that they have better biological activity and are more direct and effective. Once the metal materials in the organic matter are corroded, the corrosion products produced by the dissolved metal ions will cause adverse effects on the human body, so it must be controlled. Studies have shown that metal materials themselves will not cause allergies to the human body. However, the dissolved metal ions or dissolved ions in the form of metal salts combine with biological molecules or form abrasive dust, which may cause harm to the human body. In addition, the fracture of human metal materials is mostly caused by fatigue and friction fatigue, and these two factors are not simple factors, but are actually caused by corrosion fatigue, which is closely related to corrosion. In order to prevent the toxicity of metals in the body, improve the safety of metal materials, and prolong their service life, it is of great significance to study the corrosion of metal materials with plasma surface modification equipment in the field of biological science research. Some researchers have treated metal surfaces with NH3 and N2 plasmas to enter amino groups, which are then quaternized by reaction with methyl iodide, and then use the negatively charged anticoagulant heparin to form the quaternized amino groups on the metal surface. complexes, thereby immobilizing heparin on metal surfaces. The nitrogen groups formed on the metal surface can also be used to immobilize proteins, and the surface of most metal materials is immobilized by attaching a layer of hydrophilic macromolecular film. Under certain conditions, it will interact with [H] or H- to form hydroxyl (-OH), which adheres to the surface of the substrate, in this case APS (An1inopropyltriethox-ysi-lane) plasma, and then passes through glutaryl The action of acid aldehyde (An1inopropyltriethox-ysi-lane) can chemically bond proteins or enzyme isolates such as trypsin to the substrate surface. The method can fix biomolecules on the surface of metal, inorganic, non-porous and non-loose biological materials, so that the surface activity of the materials is greatly improved. Most of the metal substrates, such as Ti, Ti6Al4V, Co-Cr-Mo, TiTa30, etc., can be modified by plasma grafting of organic matter plasma surface modification equipment, so that biomolecules can be directly adsorbed on the surface. Artificial biomaterials used for transplantation, tissue culture or other purposes must have good biocompatibility with the biological environment. Currently, when developing biocompatible surfaces to adhere cells, the main focus is on the surface immobilization of ECM proteins and metal substrates, while techniques for surface modification of materials that do not require adherent cells, such as blood cells, are the fabrication of high Inert surfaces, such as fluorohydrocarbons, or biologically active molecules prevent cell fixation, or generate highly hydrophilic groups, etc. Most of the medical stainless steels commonly used in clinical practice now contain nickel elements. For example, the nickel content in medical 316l stainless steel is 10~14. As a potential sensitizer, the toxic effects of nickel ions in the human body due to corrosion, abrasion, precipitation, and accumulation can cause cell destruction and inflammatory responses. Similarly, cobalt and nickel elements in medical cobalt-based alloys also have greater sensitization. However, V and Al in titanium alloys are harmful to organisms. This makes the application of metal biomaterials limited to a certain extent. In order to enable the implanted metal biomaterials to fully exert their functions, they can be surface-modified by plasma surface modification equipment, such as using low-temperature plasma to graft polymer films on the surface of stainless steel, or using cobalt-based alloys. The TiO2 film grafted on the surface of the titanium alloy and the surface of the titanium alloy by the bioscience plasma grafting plasma surface treatment equipment can effectively prevent the precipitation of nickel ions and improve the effect of the ion precipitation of the abrasive products on the surface of the nickel-based alloy and the titanium alloy on the surrounding tissue of the implant. adverse reactions, greatly improving the safety of long-term use of biological implant materials.

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Research status of biomedical metal material modification application by low temperature plasma technology

Research status of biomedical metal material modification application by low temperature plasma technology: Due to the development of basic industries and high-tech products, people's demand for high-quality, high-efficiency surface modification and coating technology is developing in depth. Breakthrough progress has been made in surface modification and coating process simulation and performance prediction. As an important part of the development of new metal biomaterials, low temperature plasma technology surface modification and coating technology has penetrated into traditional industries and high-tech industrial sectors, and further promotes the development of surface functionalized coating technology according to application needs. In the low temperature plasma surface modification technology, it is an important research direction to design the material surface according to the application requirements, tailor the material surface performance parameters to meet the special requirements, and further realize the prediction of the structure and properties of the surface covering layer. Different types of Plasma Chemical Vapor Deposition (PCVD) is a challenging research topic that is being carried out by research institutes and universities. Computer simulation studies on Plasma Chemical Vapor Deposition (PCVD) and other surface modification methods have been carried out abroad. , The PCVD process was simulated, and the macro and micro multi-level models were used to simulate and predict the various properties of the plasma process and coating and the bonding force of the substrate; Simulation allows for better control and optimization of the process. For half a century of the 20th century, the ideas and methods of physics dominated the discovery and preparation of new materials. Since the 1950s, the ideas and methods of molecular biology have been rapidly recognized as the guiding principles for the growth, discovery and crystallization of new materials. & Since most biological reactions occur at the interface and surface of materials, biologists introduce surface science into biology, which plays a decisive role in the development of biomedical materials, biomedical materials and devices have the ability to save human lives, huge The commercial value of it has strongly stimulated a lot of research. Since low-temperature plasma technology has unique advantages and potentials in the growth of biomedical materials and the fabrication of biomedical devices, if the two are organically combined, it is possible to realize the revolutionary development of biomedical technology in the 21st century. In the future, with the development of plasma surface modification technology at home and abroad, combined with the needs and status of biomedical engineering, we will focus on the development of a number of advanced and applicable key technologies for surface functionalization of metal materials, including low-temperature plasma vapor deposition technology and equipment. , Numerical simulation of surface coating process and quality, and research and development of optimal control. What we mean by biomedical materials refers to materials that are compatible with living organisms involved in biomedical research and medical practice, including materials for the manufacture of artificial organs, biosensing materials, external surface materials for in vivo implantation devices, and certain materials. The materials used in some medical devices, the surface reaction of these materials is mainly controlled by the surface chemistry and molecular structure of the materials, which requires biomedical materials not only to have certain physical properties such as strength and elasticity, but also to have a biocompatible surface. nature. It is quite difficult to design a new material with both the required physical properties and the required surface properties. Since the response of organisms to the material surface mainly depends on the chemical properties and molecular structure of the material surface, it is possible to choose existing materials. Surface modification of the material with the required body properties to make it have the required biocompatibility, so as to achieve the above purpose, for example, some macromolecular polymers have similar mechanical properties to human organs, but are not biocompatible Therefore, surface modification is required to fix specific functional groups on the surface to achieve the purpose of being compatible with living organisms. In conclusion, low-temperature plasma technology is being applied by many scientists in the research of surface modification and surface film synthesis of metal biomaterials due to its unique advantages, but most of these studies are still in the development or experimental stage. Low-temperature plasma surface modification technology, with the deepening of plasma theoretical research and the resolution of process problems, will definitely improve the biologi

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The use of plasma plasma surface treatment cleaning machine pretreatment technology on wafers

The use of plasma plasma surface treatment cleaning machine pretreatment technology on wafers: The connection quality of the chip leads is a key factor affecting the reliability of the device. The lead connection area should be guaranteed to be free of pollution and the connection effect should be good. The presence of contaminants such as oxides, organic residues, etc. will seriously impair the pull value of the lead connections. The traditional wet cleaning does not completely remove or cannot remove the contaminants in the bonding area, while plasma cleaning can effectively remove the surface dirt on the bonding area and activate the surface, which can significantly improve the bonding strength of the leads. Greatly improve the reliability of packaged devices. During the bonding process, there is often a certain adhesiveness between the chip and the package substrate. This bonding is usually hydrophobic and inert, and the bonding performance is poor. It can effectively improve the surface activity of the wafer, greatly improve the fluidity of the bonding epoxy resin on the surface of the wafer and the package substrate, and increase the efficiency of the wafer and the package. adhesion between substratesWetability, reduce the delamination of the chip and the substrate, increase the reliability and stability of the chip package, and prolong the service life of the product. The glow plasma produced by plasma surface treatment and cleaning machine can effectively remove the original contaminants and impurities on the surface of the treated material, and can produce etching to make the surface of the sample rough, form many tiny pits, and increase the contact area, improve the wettability of the surface (as the saying goes, enhance the adhesion of the surface, enhance the hydrophilicity). Plasma plasma surface treatment cleaning machine has a wide range of applications, which can solve technical problems such as bonding, printing, spraying, and destaticization, and achieve the goals pursued by modern manufacturing processes such as high quality, high reliability, high efficiency, low cost, and environmental protection. . Many factory operators, when using plasma surface treatment equipment, always consult the manufacturer, how dangerous is the plasma surface treatment equipment? Plasma plasma surface treatment cleaners produce trace amounts of ozone when they start up. Ozone gas is basically harmless to the human body. However, if the use environment is relatively closed and the ventilation conditions are poor, it will be too high, causing the surrounding people to smell irritating odors and causing slight dizziness and headache. Therefore, the production workshop of plasma equipment needs to keep unblocked with the outside air. If the use space is relatively closed and the ventilation conditions are poor, a special ventilation system needs to be installed. In flip-chip packaging, the use of plasma treatment technology to process the chip and the package carrier can not only achieve ultra-cleaning of the surface of the weld, but also significantly improve the activity of the weld, which can effectively prevent false welding and reduce voids. To improve the reliability of welding, it can also improve the edge height and tolerance of the welding seam, improve the mechanical strength of the package, reduce the internal shear force formed between the interfaces due to the thermal expansion coefficient of different materials, and improve the reliability of the product. life. The glow generated by the plasma surface treatment cleaning machine when it is in close contact can cause a burning sensation in the human body. Therefore, the material cannot be touched by hand when the plasma beam is processing the material. Generally, the distance between the direct injection plasma nozzle and the nozzle is 50 mm, and the distance between the rotating plasma nozzle and the nozzle is 30 mm (different distances for different types of equipment). In order to ensure the safe operation of the equipment, please use AC220V/380V power supply, and do a good job of grounding to ensure that the air supply source is dry and clean. The plastic packaging type of the lead frame still accounts for more than 80% of the microelectronic packaging field. The delamination of the copper lead frame leads to poor sealing performance after encapsulation, and leads to chronic outgassing. It also affects the bonding and wire bonding quality of the chip. To ensure the ultra-cleanness of the lead frame is to ensure the reliability of the package. And the key to the yield, the plasma treatment of the plasma surface treatment cleaning machine can realize the ultra-cleaning and activation of the surface of the lead frame. Compared with the traditional wet cleaning, the yield of the finished product is greatly improved, and there is no waste water discharge, reducing the chemical The purchase cost of the potion. Porcelain products are encapsulated, usuall

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Application explanation of low temperature plasma surface treatment technology characteristics of wide-width plasma cleaning machine:

Application explanation of low temperature plasma surface treatment technology characteristics of wide-width plasma cleaning machine: The surface treatment technology of the wide-width plasma cleaning machine can be matched with a variety of different post-processing processes, among which the typical post-processing includes printing, bonding, and painting. The low-temperature wide-width plasma cleaning machine is suitable for industrial applications in various fields. It can provide subsequent bonding, coating, and pre-printing treatment for different materials or composite materials, so that two different materials can be effectively and reliably combined together. The plasma surface treatment equipment for plasma cleaning, surface cleaning, activation and coating mainly provides pretreatment for bonding, painting, sputtering and other processes in the digital industry. The low-temperature plasma surface treatment technology is widely used in digital products for mobile phone casings, mobile phone keys, notebook computer casings, notebook keyboards, plastic products, etc. Widely used raw materials for printing, coating and bonding of polyethylene, polypropylene, polyvinyl chloride, polyester, polyoxymethylene, PTFE, vinyl, nylon, (silicon) rubber, plexiglass, ABS and other plastics Surface pretreatment of other processes. The shape, width, height, material type, process type, and need for online processing of these materials all directly affect and determine the solution of the entire surface treatment equipment. The main features of the low-temperature wide-width plasma cleaning machine: 1. High uniformity: atmospheric pressure plasma is a glow-type plasma curtain, which directly acts on the surface of the material. Experiments have shown that the processing uniformity of the same material at different positions is very high. This feature is useful for the next step in the industrial field. Coating, printing and other processes are very important. 2. Controllable effect: Atmospheric pressure plasma has three effect modes to choose from. One is to use argon/oxygen gas combination, which is mainly used for non-metallic materials and requires higher processing effect. The second is to use an argon/nitrogen combination, mainly for the metal area of ​​the product to be treated that cannot be treated. Due to the strong oxidation of oxygen, this problem can be controlled after replacing the nitrogen in this scheme. The third is the case where only argon is used. The surface modification can also be achieved by only using argon, but the effect is relatively low. This is a special case, and it is a solution adopted by a few industrial customers when a limited and uniform surface modification is required. 3. Safe and stable: atmospheric pressure plasma, also low temperature plasma, will not cause damage to the surface of the material. No arc, no vacuum chamber, and no harmful gas suction system, and it will not cause physical damage to the operator for a long time.

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Research on the reduction of bacterial adhesion and modification of aluminum sheets after plasma treatment

Research on the reduction of bacterial adhesion and modification of aluminum sheets after plasma treatment: During the production, packaging and transportation of medicines and food, bacteria in the environment can easily adhere to their surfaces to form a biofilm, causing contamination of medicines and reducing the shelf life of food production, thus affecting people's health. A step in biofilm formation is the adsorption of macromolecules such as bacteria and proteins. If the surface material can prevent bacteria from sticking, it can prevent the formation of biofilms. Polyethylene glycol (PEG) organic compounds are potential preservatives that can effectively prevent bacteria and proteins from adhering. Aluminum is a common packaging material widely used in the food and pharmaceutical industries. If polyethylene glycol is used to deposit a reinforcing film on the surface of the aluminum sheet, it can prevent bacteria from adhering. Surface modification methods include chemical and physical methods. The chemical method is a wet method, and its technological operation is relatively complicated, and chemical reagents that pollute the human body and the environment are required. Low-temperature plasma technology opens up a new avenue for surface modification of metal biomaterials. It is a dry process with the advantages of easy operation and control, no pollution to the environment, and has received more and more attention in the fields of food and biomedicine. The PEG-like structure was grafted on the surface of the aluminum sheet by low-temperature plasma to form a thin film, and a large number of -CH-CH-O bonds were mainly accumulated on the surface; Greatly reduces bacterial adhesion. Plasma-induced reactive species (such as free radicals, etc.) provide a mechanism for the recombination of surface di(ethylene glycol) methyl ether molecular fragments for reaction. The free radicals fall into the newly generated macromolecular network and can initiate a vigorous electronically excited in situ oxidation reaction. The ATR-FTIR analysis of the aluminum sheet macromolecular layer structure after plasma treatment shows that there is a strong absorption peak at 1583.07 cm, which is the characteristic absorption peak of the CO bond in the PEG structure, indicating that the deposited surface layer is PEG-like. structure. The absorption peak at 1780.21cm indicates that there is a C-O bond, which shows that a partial cross-linking reaction occurs while forming a PEG-like structure. Compared with before modification, the bacterial adhesion of aluminum sheet after plasma treatment is greatly reduced after plasma treatment. This is because PEG structure is produced by cross-linking on the surface, and the PEG molecular chain has high flexibility. It can reduce the configurational freedom of macromolecular chains such as bacteria, and thus have the ability to resist bacterial adhesion. The surface morphology of the bacteria biofilm adsorbed on the aluminum sheet before modification and the sample analysis of the surface adsorption on the aluminum sheet after modification can be known that the surface of the modified aluminum sheet can effectively resist bacterial adsorption after plasma modification. The elemental composition and chemical bond state on the surface of the aluminum sheet changed significantly after plasma treatment, and CO, OCO and O-CO-O bonds were formed on the surface layer. This indicates that plasma-induced reactive species (such as free radicals, etc.) provide a mechanism for the recombination of surface bis(ethylene glycol) methyl ether molecular fragments, which is different from non-oxidative reactions in which the formed free radicals fall into newly generated macromolecules. In the network, a vigorous electronically excited in-situ oxidation reaction can be initiated. The PEG-like structure deposited on the surface of the aluminum sheet can greatly reduce bacterial adhesion. Compared with before modification, bacterial adhesion is reduced by more than 80%, which has important application prospects in the food industry and medical transplantation.

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