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Atmospheric plasma surface treatment to change the surface energy of waterborne coatings for automotive industry

Atmospheric plasma surface treatment to change the surface energy of waterborne coatings for automotive industry

How does atmospheric plasma surface treatment ensure the adhesion of waterborne coatings in automobile industry?   When cleaning contaminated surfaces and activating non-polar plastics, it is not possible to obtain long-term stability and flawless adhesion of paint to the surface without a subtle degree of cleaning. There are a variety of cleaning and activation methods and the use of chemical solvents is widely used, but more than 50 per cent of volatile organic compound (VOC) emissions are due to the use of solvents and spraying operations account for the majority of these emissions.   Surface energy is the key factor to ensure wettability and adhesion. Whether the coating can have the adhesion force needed to combine with the substrate mainly depends on the surface energy of the coating. Good wettability means that the surface of the material is ultrafine and clean, and the surface of solid material can be higher than the surface tension of liquid. Chemical solvent-based pretreatment processes are harmful to the environment and are often health-damaging, energy-consuming and costly to dispose of. So it's no surprise that in an era of increasing environmental awareness, car manufacturers are looking for alternatives, and water-based paint systems are moving toward environmentally friendly surface treatment technologies. Atmospheric plasma surface treatment technology is an environmentally friendly, economical and efficient pretreatment process.   Plasma surface treatment technology is a dry pretreatment process without chemical solvent, which combines three effects of micro-cleaning, electrostatic dissipation and surface synchronous activation. Plasma is produced by a high-pressure discharge from a nozzle and is delivered to the surface in the form of an air stream. The surface is activated by chemical and physical interaction between plasma and matrix. When plasmas collide with the plastic surface, the groups containing oxygen and nitrogen combine with the non-polar polymer matrix, and the plasma activation increases the surface energy and makes it become polar. Plasma contains a lot of energy -- free radicals, ions, atoms and molecular fragments -- which release that energy onto the surface of the pretreated material, triggering a chemical reaction to produce an effect. The resulting functional hydroxyl, carbonyl, and carboxyl groups (as well as nitrous oxide) have a strong chemical bond with the coating and contribute to a significant increase in adhesion. During pretreatment, the surface temperature of the plastic generally does not exceed 30℃.   This plasma effect leads to uniform surface wettability, which not only produces good adhesion in a few seconds, but also ensures a high quality finish with waterborne coatings. This environmentally safe process requires only compressed air as the reaction gas and electricity.   The on-line spray gun system of atmospheric plasma surface processor controlled by computer can be monitored by screen and is fully compatible with the machine. At the same time, the process itself is powerful. Traditional pretreatment methods can be completely eliminated by plasma treatment in most cases. Unlike the chemical solvent pretreatment method, this method does not require drying and temporary storage, so it can be used to spray parts immediately after atmospheric plasma cleaning and activation, which not only eliminates some process steps, greatly reduces energy consumption and operating costs, and improves output and product quality.

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Application of low-temperature plasma in the field of polymer materials

Application of low-temperature plasma in the field of polymer materials

Conductive plastics is a very active research and development field nowadays. It has developed from pure laboratory research to applied research and become a new generation of electronic materials. According to the conductive mechanism, conductive polymer materials can be divided into two types: structural type and composite type.   At present, the synthesis process of structural conductive polymers is complex and the cost is high. Due to its simple processing technology and low cost, composite conductive polymer has been widely used in electronics, automobile, civil and other fields. Structural conductive plastic is a functional polymer material made by mixing resin with conductive material. It is mainly used in electronics, integrated circuit packaging, electromagnetic shielding and other fields.   Conductive plastics can generally be classified into the following two categories:   1, according to the electrical performance classification, can be divided into: insulator, antistatic body, conductive body, high conductor. Resistance is generally greater than 1010 Ω · cm called insulators; Resistance to Ω · cm diameter range of 104 ~ 109 is called semiconductor or antistatic body; Resistance value is less than 104 Ω · cm called conductive body, resistance under 100 Ω · cm called high conductor is even lower.   2. Manufacturing methods of electric plastics can be classified into two types: structural conductive plastics and composite conductive plastics. Structural conductive plastics, also known as intrinsic conductive plastics, refer to the conductivity of their own or their chemical modification.   Structural conductive polymer materials: (1) conjugated polymers: such as polyethylene, (Sr) N, linear polybenzene, layered high polymer, etc. (2) Metal chelates, such as polyketone phthalocyanine; (3) Charge mobile polymer complex: such as polycation, CQ complex. The production cost of polymer structural materials is high, and the technology is difficult, so it has not been produced on a large scale. Currently, conductive polymer materials are widely used as composite polymer materials, and their fillings mainly include: (a) Metal dispersion system; (b) Black carbon; (c) Organic complex dispersion system; (d) Carbon fiber.   3. According to different USES, low-temperature plasma can be divided into: Anti-static materials, conductive materials, electromagnetic shielding materials, tunnel theory explains the impact of conductive packing on conductivity. Conductive plastics conduct electricity because electrons can pass through the gaps between conductive fillers. At a certain concentration, as long as the distance between conductive fillers is reduced by a small part, electrons can conduct electricity through the pores between conductive fillers. At this time, the resistivity will be suddenly changed and the conductive plastic will change from the original insulator to conductor, which will produce leakage effect. The percolation concentration of carbon black filled LDPE compound is closely related to the structure of carbon black. The percolation concentration of the specially conductive carbon black filler compound is lower than that of the acetylene carbon black filler compound. In the production process, it is still difficult to reach the critical concentration, but the adoption of low temperature plasma treatment technology can make it easier to reach the critical concentration.

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Neutral ion beam etching technique for plasma surface processor

Neutral ion beam etching technique for plasma surface processor

When the characteristic dimensions of LsI are reduced to less than 7nm, the inherent defects of plasma etching in conventional PLASMA surface processors will limit their further development and applications, such as charge accumulation and deep ultraviolet photon (VUV) radiation. The accumulation of charge caused by electron masking effect will lead to the accumulation of too much positive charge at the bottom of the etching pattern, resulting in charge-induced damage and the reduction of etching accuracy caused by the distortion surface of positive ion orbit. Deep ultraviolet photonic radiation not only intensifies the accumulation of positive charge, but also forms defects on the surface of etched substrate, thus affecting the etching reaction process of the surface. Therefore, it will increase the surface roughness of the substrate and the amount of etching on the side wall, and reduce the precision of etching. In addition, in order to accurately control the surface reaction in the etching process of plasma surface processor, the reaction particles involved in the etching need to have low energy, so as to improve the controllability and precision of the whole etching process.   In order to eliminate the above problems in the traditional plasma etching and plasma etching process provides low energy particle surface processor, neutral particle beam etching technique has been developed and obtained a certain development, with the traditional pulse plasma etching and plasma etching and atomic layer etching system, plasma surface treatment machine neutral particle beam etching technology development suited to its own system. So far, the neutral particle beam etching system is mainly divided into three types: electron cyclotron resonance plasma, DC plasma and inductively coupled plasma plus parallel carbon plate. For the electron cyclotron resonance plasmas and dc plasmas, the neutral particle beam is formed by the charge transfer of positive ions, with low neutralization efficiency (about 60%), while the particle beam has high energy (>100eV). This low neutralization flux and high-energy particles, leading to the low, etching etching rate and selectivity, so it is not suitable for etching process is different from the former two ways, the plasma surface treatment machine parallel carbon plates with inductive coupling plasma way, neutral particle beam is formed by anion separation electronics.   In the power shutdown stage of plasma pulse technology, a large number of negative ions are generated and pass through parallel carbon plates to form neutral particle beams by separating electrons. Compared with the positive ions, when by parallel plate carbon anion is more likely to be neutral, mainly because of negative ion separation electron energy is much less than positive ion charge transfer, so the neutralization efficiency is much better than the cation, anion chlorine anion neutralization efficiency can be close to one hundred percent, for example, while the neutralization efficiency of chloride ions is only about 60%. In addition, for the inductively coupled plasmas with parallel carbon plates, the bias is applied to the bottom parallel carbon plates, so the negative ion beam energy can be accurately controlled to produce the neutral particle beam with low energy and high flux. Compared with the former two methods, the neutral particle beam etching technique of plasmas coupled by induction and parallel carbon plate has a better application prospect.   As the chip feature size is gradually reduced, the requirement of etching process will be higher and higher. When the feature size is reduced to less than 7nm, the need for accurately controlled anisotropic etching process becomes increasingly urgent. The neutral particle beam etching plasma surface treatment machine basic won't produce charge accumulation and ultraviolet photons (vacuum) radiation, and the resulting particle reaction energy is very low, so it is possible that plasma surface treatment machine will be very suitable for 7 nm below fins fet etching of silicon substrate, and under 5 nm carbon nanotubes or graphene devices accurate noninvasive etching.

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Influence of step height of plasma surface processor on polysilicon gate etching

Influence of step height of plasma surface processor on polysilicon gate etching

In addition to the effect of the surface etching of plasma surface processor on the size of polysilicon gate, the surface topography fluctuation caused by shallow groove isolation also has a significant effect on the size of polysilicon gate. The height of shallow grooved isolated steps characterizes the surface morphology of the wafer before polysilicon growth. Due to the flat growth of the furnace tube polysilicon, the positive step height (the upper surface of the shallow trench isolation silicon is higher than the bulk silicon active region) will lead to the thickening of the polysilicon near the shallow trench isolation region, thus affecting the side wall Angle of the polysilicon gate. At the positive step height, after the main etching step of the plasma surface processor polysilicon gate etching, the side wall of the polysilicon gate located in the isolation zone of the shallow groove is obviously more inclined than the active zone, and the characteristic size is also obviously larger than the active zone.   Even if the plasma surface treatment machine's main etching step USES gases that produce less polymerization byproducts, vertical gate wall cannot be formed in the shallow trench isolation zone, and this difference in side wall will remain until the etching is complete. The side wall Angle of the polysilicon gate near the shallow groove isolation is only 86°, while the side wall Angle of the polysilicon gate located in the center of the active region reaches 89°. Therefore, the difference of polysilicon film thickness leads to the difference of gate side wall Angle, while the difference of gate side wall Angle leads to the difference of feature size.   Under different characteristic sizes of active zones, the isolated step height of shallow trench will be different. The load caused by the difference of density in the source area during the chemical mechanical grinding after the shallow groove isolation will lead to the difference of step height, which will affect the difference of characteristic size and Angle of polycrystalline silicon etching. The relationship between the polysilicon height and the step height under different width of the fed region shows that the size of the fed region is closely related to the step height during gate etching. With different width of the source region, the characteristic dimensions of the optical polysilicon and the polysilicon with surface morphology before and after exposure and etching show that the width of the source region is different, and the etching deviation of the plasma surface processor will also be different.

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Plasma surface modification of polymer materials

Plasma surface modification of polymer materials

In the modification of polymer materials, the application of plasma surface treatment is mainly as follows:Surface hydrophilic or hydrophobic:The hydrophilic groups such as COOH, -C=O, -NH2 and -OH will be added to the surface of ordinary polymer materials after being treated by gas plasmas such as NH3, O2, CO, Ar, N2 and H2. The longer the treatment time is, the lower the contact Angle of the droplets will be, and the fluoropolymer surface will increase its hydrophobicity after being treated by fluoropolymer such as CF4 and CH2F2 plasma. The results showed that the contact Angle between the untreated PET film and water was 73.1°, and it was treated with Ar plasma for 5min. After being placed for a day, the contact Angle with water decreased to 33.7°. The contact Angle increased slowly with the extension of time, indicating that the treatment effect declined with time. The contact Angle measured after 10 days was 41.3°. After 20 days of treatment with N2 plasma, the surface polarity of LDPE disappeared. After plasma treatment of oxygen on the surface of 3-hydroxybutyl-3-hydroxypentanoic acid copolymer film, it was also found that the contact Angle of oxygen recovered from 20° to 70° after 60 days. It is believed that the polar groups introduced by plasma surface treatment are attenuated due to the movement of the polymer chain and thus transferred to the polymer material body. PET membrane is immersed in organic solvent with strong interaction before treatment. The rearrangement of molecular chains caused by solvent reduces chain activity and can stabilize the treatment effect.   The treatment effect decays not only with time but also with temperature. The surface of the polymer film was treated by O2 plasma and heat-treated at 80~140℃. The results showed that the surface tension and wettability of the film were increased after plasma treatment, and the plasma treatment effect was weakened after heat treatment. After heat treatment of PET, nylon and other surfaces, the surface energy and surface-COOH and -OH groups decreased significantly. The surface tension of polyimide and polyphenylene sulfide decreased obviously after heat treatment. This also indicates from one side that the difficulty degree of the polymer molecular chain itself in motion is also an important factor affecting the speed of reaction.   Improve bonding ability:   Plasma treatment can easily introduce polar groups or active points on the surface of polymer materials, form chemical bonds with the bonded materials and adhesives, and improve the bonding performance by increasing the van der Waals (intermolecular forces) between the bonded materials and adhesives. This process is not limited by the material quality and will not damage the overall mechanical properties of the material, which is far better than the common chemical process. Plasma treatment can obviously improve the adhesion between polymer films and improve the mechanical properties of composites. If the bonding property between the reinforced fiber and the base is not good, the stress cannot be transferred well, instead, the stress concentration source will be generated, leading to the deterioration of the mechanical properties of the composite. Ultrahigh molecular weight polyethylene (UHMWPE) fibres are plastically treated to enhance their binding strength with epoxy resins by more than four times. After treating polyethylene fiber with Ar, N2, CO2 and other gas plasma, the bonding between polyethylene fiber and PMMA(polymethyl methacrylate) was enhanced. Its toughness index and breaking strength, plasma treatment of high strength PE fiber can improve the fiber - epoxy resin composite bonding strength.   Improve printing and dyeing ability:   On the one hand, plasma surface treatment can increase the surface roughness of the treated material, destroy its amorphous region, make the surface structure of the treated material loose, and make the accessible area of dye/ink molecules increase due to the increase of the microgap; On the other hand, the introduction of polar groups on the surface can make the surface of the treated material easy to adsorb dye/ink molecules by intermolecular interaction force, hydrogen bond or chemical bond, thus improving the dyeing performance of the material. The adsorption of disperse dyes on PET fiber was enhanced by low temperature plasma treatment. After plasma treatment at low temperature, the linen fabric was washed with hot water. The dyeing properties of the fabric were good and the mechanical properties were not damaged. The dyeing properties of wool fabrics were improved by plasma treatment at low temperature. The use of toxic substances was reduced and the content of halogenated organic compounds was reduced before wool dyeing was treated by air plasma. Low temperature plasma method can improve dye fastness of polyester fiber.   The surface modification of plasma polymers is mainly aimed at the surface modification

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Microelectronic plasma cleaning machine equipment processing application

Microelectronic plasma cleaning machine equipment processing application

The development of microelectronics has fused information, communication and entertainment. The miniaturization of microelectronic devices is made possible by means of plasma technology. In the 1990s, plasma technology entered the field of microelectronic device manufacturing. The following will explore the plasma cleaning machine equipment in the core processing applications (examples of etching, deposition and doping).   In the late 1970s and early 1980s, plasma technology has become a key technology in IC manufacturing process. Today, 30% of the manufacturing process uses plasma. The global microelectronics industry bought $17.6 billion worth of plasma cleaning equipment in 1999, which produced $245 billion worth of chips. At present, plasma treatment technology has been widely used in the production of DRAMS, SRAIMS, MODFETS, thin insulated gate oxide layer and new photoelectric materials, such as silicon and germaniumalloy, high-temperature electronic materials (diamond or diamond-like carbon film), silicon carbide, cubic boron nitide and other materials and components.   The raw materials for semiconductor devices are crystalline silicon or amorphous thin films. The main process for producing A-SI :H is plasma chemical vapor deposition. Plasma chemical vapor deposition process is used to generate ionic components, and these ionic components participate in the reaction, so as to realize the deposition on the basement surface. Compared with traditional chemical vapor deposition (CVD) processes, plasma CVD processes can generate ionic components at temperatures far lower than those of conventional CVD processes, and can also modify films by ion bombardment. The precursor film of plasma chemical vapor deposition process is usually SH4 gas diluted by inert gas, and the reaction product is hydrogenated amorphous silicon film.   The application of plasma cleaning machine in deposition process can be divided into four steps. (1) The electron collision reaction between the electron and the reaction gas produces ions and free radicals; (2) The active ingredients are transmitted from the plasma to the base surface; (3) The active ingredients are deposited on the surface of the substrate by adsorption or physicochemical action; (4) The active ingredient or reaction product becomes the component of the deposition film. In the process of high density plasma chemical vapor deposition, deposition and etching are often carried out simultaneously. In this process, three main mechanisms are: plasma ion assisted deposition, argon ion sputtering and sputtering material redeposition. A high density plasma source (e.g., inductively coupled plasma (ICP), electron cyclotron resonance plasma (ECR), or helicon) was prepared by chemical vapor deposition (HDPCVD) to excite a mixture of gases containing silane, oxygen, and argon. With the base as the cathode, the high-energy positive ions in the plasma will be attracted to the crystal surface, and then the oxygen will react with silane to produce silane, and then the oxygen will be removed by argon ion sputtering.   There are two kinds of printing line platemaking techniques commonly used in semiconductor manufacturing, and they complement each other. One is to print the dielectric onto the metal surface, and the other is to insert the metal into the dielectric plate. The former is the ion etching (RIE) platemaking technique. The operation steps are as follows: (1) A metal layer with uniform thickness is deposited on the wafer surface; (2) Then evenly coat the surface with a layer of photosensitive polymer, namely photoresist; (3) The circuit pattern is transmitted to the photolithographic surface by optical means to change its solubility; (4) Remove the soluble part with a reactive etchant to form a mask layer; (5) Remove metal etching without mask layer protection; (6) The photoresist was removed by plasma removal; (7) Deposition passivation surface of silicon dioxide or silicon nitride.   The other is mosaicism, which is inspired by the ancient jewelry mosaicism, or Damascus mosaicism. The process requires that the grooves are etched in the dielectric plane, and then the grooves are filled with metal by metal deposition process, so as to embed the desired circuit in a plane. After being coated with an insulating layer, the next metal film can be reembedded.

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