Creation of Polymerizable Species in Plasma Polymerization

Plasma polymerization of trimethylsilane (TMS) was carried out and investigated in a direct current (dc) glow discharge. The formation of TMS plasma glow was carefully examined with optical photography as compared with an Ar dc glow discharge. It was found that there exists a significant difference in the nature of glow and how the glow is created in TMS glow discharge, which polymerizes or causes deposition, and that of monatomic gas such as Ar, which does not polymerize or deposit. In dc Ar discharge, the negative glow, which is the most luminous zone in the discharge, develops in a distinctive distance away from the cathode surface, and the cathode remains in the dark space. In a strong contrast to this situation, in TMS dc discharge, the primary glow that is termed as cathode-glow in this paper appears at cathode surface, while a much weaker negative glow as a secondary glow was observed at the similar location to where the Ar negative glow appears. The deposition results of plasma polymers and gas phase composition data of TMS in a closed reactor acquired by ellipsometry and residual gas analyzer (RGA) measurements clearly indicated that the cathode-glow in TMS glow discharge is mainly associated with chemically reactive species that would polymerize or form deposition, but the negative glow is related to species from simple gases that would not polymerize or deposit. Based on the glow location with respect to the cathode, it was deduced that the cathode-glow is due to photon emitting species created by molecular dissociation of the monomer that is caused by low energy electrons emanating from the cathode surface. The negative glow is due to the ionization and the formation of excited neutrals of fragmented atoms caused by high-energy electrons. Polymerizable species that would cause deposition of material (plasma polymers) are created mainly by the fragmentation of monomer molecules by low energy electrons, but not by electron-impact ionization of the monomer.     

Surface Modification of Textile Fibers and Cords by Plasma Polymerization

In this paper we report on the treatment of industrial fibers and cords by means of plasma polymerization techniques. Coatings of plasma-polymerized pyrrole or acetylene were deposited on aramid fibers, aramid cords and polyester cords. The equipment was a custom-built semi-continuous reactor operated on a pulsed DC glow discharge. The fibers and cords were tested for adhesion to various polymers such as tire cord skim stock rubber compounds and epoxy adhesives. Standard industrial pull-out force adhesion measurement techniques were used. The deposition conditions of the plasma polymer films were varied within wide limits. It was found that, in general, films deposited under low-power and high-pressure conditions performed better than films prepared under high-power and low-pressure conditions. For some systems pulsing of the discharge power improved the performance further. For all systems studied, the optimized plasma polymer surface modification outperformed current industrial standards. The plasma-polymerized coatings were characterized by various techniques and the excellent performance results are explained in a tentative model based on the molecular structure of the films. This structure was found to be strongly dependent on the discharge conditions.     

Surface Modification of Ultra-high Molecular Weight Polyethylene Membranes Using Underwater Plasma Polymerization

Ultra-high molecular weight polyethylene membranes were modified and subsequently polymer coated using the underwater plasma produced by glow discharge electrolysis. This plasma pretreatment generated various O-functional groups among them OH groups have dominated. This modified inner (pore) surface of membranes showed complete wetting and strong adhesion to a hydrogel copolymerized by glow discharge electrolysis also. The deposited hydrogel consists of plasma polymerized acrylic acid crosslinked by copolymerization with the bifunctional N,N′-methylenebis(acrylamide). Tuning the hydrogel hydrophilicity and bio-compatibility poly(ethylene glycol) was chemically inserted into the copolymer. Such saturated polymer could only be inserted on a non-classic way by (partial) fragmentation and recombination thus demonstrating the exotic properties of the underwater plasma. The modification of membrane was achieved by squeezing the reactive plasma solution into the pores by plasma-induced shock waves and supported by intense stirring. The deposited copolymer hydrogel has filled all pores also in the inner of membrane as shown by scanning electron microscopy of cross-sections. The copolymer shows the characteristic units of acrylic acid and ethylene glycol as demonstrated by infrared spectroscopy. A minimum loss in carboxylic groups of acrylic acid during the plasma polymerization process was confirmed by X-ray photoelectron spectroscopy. Additional cell adhesion tests on copolymer coated polyethylene using IEC-6 cells demonstrated the bio-compatibility of the plasma-deposited hydrogel.     

Comparison Between Air Filamentary and Helium Glow Dielectric Barrier Discharges for the Polypropylene Surface Treatment

Recently, a glow like dielectric controlled barrier discharge (GDBD) working at atmospheric pressure has been observed. Such a discharge could replace a filamentary dielectric controlled barrier discharge (FDBD) used in corona treatment systems to improve the wettability or the adhesion of polymers. So it is of interest to compare these two types of discharges and their respective effect on a polymer surface. This is the aim of an extensive study we have undertaken. The first step presented here is the comparison of a filamentary discharge in air with a glow discharge in helium. Helium is the most appropriate gas to realize a glow discharge at atmospheric pressure. Air is the usual atmosphere for a corona treatment. The plasma was characterized by emission spectroscopy and current measurements. The surface transformations were indicated by the water contact angle, the leakage current measurement and the X-ray photoelectron spectroscopy. Results show that the helium GDBD is better than air FDBD to increase polypropylene wettability without decreasing the bulk electrical properties below a certain level. Contact angle scattering as well as leakage current measurements confirm that the GDBD clearly results in more reproducible and homogeneous treatment than the FDBD.     

Glow characterization in direct current plasma polymerization of trimethylsilane

Plasma polymerization of trimethylsilane (TMS) was carried out in a direct current (dc) glow discharge and was investigated by optical photography and plasma diagnostic techniques including optical emission spectroscopy and residual gas analysis. The nature of the glow formed in TMS discharge, which deposited plasma polymers, was significantly different from that of a simple gas such as Ar. In an Ar discharge, the dominant glow was the well known negative glow, which developed at a distinctive distance from the cathode, whereas the cathode surface remained in the dark space. In strong contrast to this situation, in TMS dc discharge the dominant or primary glow was the cathode glow, which appeared at the cathode surface. At a similar location where the Ar negative glow appeared, a very feeble glow as a secondary glow was also observed in TMS glow discharge. The deposition results and plasma diagnosis data evidently indicated that in TMS glow discharge, the cathode glow resulted from the low‐energy electron‐impact dissociation of TMS molecules that creates polymerizable species, but the negative glow was related to nonpolymerizable species such as hydrogen atoms and molecules. In this article, the cathode glow formed in glow discharges of organic compounds was designated as the dissociation glow according to its underlying plasma reactions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1042–1052, 2004     

Influence of Rubber Formulation on Surface Modifications Produced by RF Plasma

The effectiveness of nitrogen, oxygen and air Radio Frequency (RF) plasma treatments on two styrene-butadiene vulcanized rubbers with a different formulation has been studied. The presence of an antiadherent surface layer containing low-molecular weight ingredients (sulfur-rich vulcanization agents and wax) from SW (Sulfur-Wax) rubber formulation requires an extended plasma treatment capable of removing this surface layer. When the percentage of antiadherent moieties is reduced in ZS (Zinc Stearate) rubber formulation, shorter plasma treatment times are enough to modify rubber surface and increase its polarity by the creation of C–O and C=O polar groups that enhance adhesion towards a polyurethane adhesive. Air and oxygen plasma treatments are more aggressive than nitrogen plasma and therefore they are more effective in removing the antiadherent layer of the outermost rubber surface layer prior to oxidation of the rubber surface.     

甲醇溶液辉光放电等离子体电解

甲醇溶液辉光放电等离子体电解过程出现明显的非法拉第定律现象, 主要产物是氢气和甲醛, 还有少量一氧化碳、甲烷、乙烷、丙烷、1,3,5-三噁烷和水等, 产物和产量受放电极性和辅助电解质及放电电压等因素的影响. 在甲醇溶液电导率为11.40 mS·cm-1, 放电电压700 V 条件下, 阳极气体产量为55.90 mol/(mol electrons), 阴极气体产量为707.90 mol/(mol electrons), 阴极气体产量是阳极气体产量的12.66 倍, 气相产物中氢气含量在86%(molar fraction)以上. 在等离子体层中甲醇分解过程和其它类型的等离子体分解过程类似, 蒸汽鞘层中的加速电子是引发辉光放电过程非法拉第定律现象的决定因素. 阴极辉光放电过程中等离子体-溶液界面上的主要活性物种是中性粒子和电子,阳极辉光放电过程中等离子体鄄溶液界面上的主要活性物种是中性粒子和正离子. 辅助电解质对产物的影响主要是通过影响界面上发生的后续反应过程来表现.     

Plasma stencilling methods for cell patterning

In this paper we describe plasma stencilling techniques for patterning 10 mammalian cell lines on hydrophobic and cell repellent poly(dimethylsiloxane) (PDMS), methylated glass and bacterial grade polystyrene surfaces. An air plasma produced with a Tesla generator operating at atmospheric pressure was used with microengineered stencils for patterned surface oxidation, selectively transforming the surface to a hydrophilic state to enable cell adhesion and growth. Plasma stencilling obviates the need for directly patterning cell adhesion molecules. Instead, during cell culture, adhesion proteins from the media assemble in a bioactive form on the hydrophilic regions. Critically, the removal of protein patterning prior to cell culture provides the option to also use PDMS–PDMS plasma bonding to incorporate cell patterns within microfluidic systems. Linear patterns were generated using PDMS microchannel stencils, and polyimide stencils with through holes were used for the production of cellular arrays. For the production of smaller cellular arrays, a novel microcapillary-based dielectric barrier discharge system was developed. A numerical method to characterise the cell patterns is also introduced and was used to demonstrate that plasma stencilling is highly effective, with complete patterns confined during long term cell culture (>10 days). In summary, plasma stencilling is simple, rapid, inexpensive, reproducible and a potentially universal cell line patterning capability.

Cleaning Away the Oleic Acid Contaminant from Glass Surface by Negative Glow Plasma

Glass surfaces are contaminated by exposure to overheated oleic acid vapor and then cleaned by low-pressure plasma of a dc glow discharge in either air or argon. In this study, the oleic acid is used as model for hydrophobic organic contaminant and glass as a model for inorganic hydrophilic substrate. The processes of contamination and plasma cleaning are studied by atomic force microscopy (AFM), which revealed formation of oleic acid nanodroplets during contamination and, then, their removal during a few minutes of plasma cleaning. Water contact angle measurements show a much faster effect of plasma cleaning treatment, the contaminated surface changing from slightly hydrophobic to superhydrophilic in less than 30 s. This effect can be attributed to oxidation and hydroxylation of the oleic acid, as indicated by infrared absorption measurements. Also, the AFM indentation of the oleic acid nanodroplets after short plasma treatment indicates solidification of the remnant contaminant material.     

Plasma polymerization of phenyl isothiocyanate

Thin polymer films were obtained by plasma polymerization of phenyl isothiocyanate. Polymerizations were carried out in rf (13.56 MHz) glow discharge generated in an electrodeless flow system. It was found that this monomer produces uniform films with a wide range of thicknesses, from hundreds of nanometers to tens of micrometers. The deposition rate appeared to be dependent on the substrate distance from the monomer inlet. The chemical structure of plasma polymer was characterized by using elemental analysis, IR spectroscopy, gas chromatography, and mass spectrometry. Elemental analysis showed that the composition of polymer depends on the substrate position in the reactor. It was observed that sulphur content decreased with increasing the substrate distance from the monomer inlet, whereas nitrogen content appeared to increase. The IR data revealed significant decrease in —NCS groups content in the polymer as compared with the monomer spectrum and indicated for the appearance of new absorption bands corresponding to the ? CN and C? H aliphatic, groups. The results account for a strong fragmentation of monomer in plasma involved in decomposition of isothiocyanate group and phenyl ring. The soluble fraction of polymeric material was examined by gas chromatography and then the separated products were analyzed by mass spectrometry. The soluble fraction was found to be composed of numerous low molecular-weight compounds. Identification of their structure revealed the presence of residual monomer, thiophenol, cyanobenzene, diphenyl, diphenyl sulphide, diphenyl disulphide, phenyl thiocyanate, dicyanobenzene, phenatroline, and some other oligomeric products. Formation of these compounds proves high susceptibility of ? NCS group in the monomer towards different fragmentation reactions. The surface free energy and electrical conductivity of polymer films were evaluated. The surface free energy value was very close to those estimated for plasma polymers deposited from other benzene derivatives. The low electrical conductivity manifested by the investigated polymeric material indicated for its dielectric character. The photoelectrical measurements revealed some photoconductivity effect in this material.     

Anode Magnetron Enhanced DC Glow Discharge Processes for Plasma Surface Cleaning and Polymerization

The objective of this study was to examine some fundamental factors involved in the design and construction of the anode magnetron dc glow discharge processes as well as its performance in plasma cleaning and polymerization. Those advantages of anode magnetron include the capability of the magnetron to operate at low pressure, as well as decreasing the thickness of cathode dark space, i.e., the negative glow which contains a higher concentration of ions and active species was more closely to the cathode surface, which makes the plasma surface cleaning and polymerization an effective and uniform processes. The deposition rate at a given discharge power is increased by the presence of anode magnetrons, and is also much higher relative to rf and af. The refractive index of dc plasma film at a given polymer thickness (such as TMS, 70 nm, RI: 2.4) is higher than rf, af, and cascade arc plasma (RI: 1.6–1.7).     

Plasma polymerization and deposition of glycidyl methacrylate on Si(100) surface for adhesion improvement with polyimide

Thin polymer films were deposited on Si(100) surfaces by plasma polymerization of glycidyl methacrylate (GMA) under different glow discharge conditions. The FT‐IR, X‐ray photoelectron spectroscopy (XPS), and amine treatment results suggested that the epoxide functional groups of the deposited films had been preserved to various extents, depending on the plasma deposition conditions. The use of a low radio frequency power (～ 5 W) and a relatively high system pressure (100–400 Pa) readily resulted in the deposition of thin films having nearly the same composition of the epoxide functional groups as that of the GMA homopolymer. The plasma‐polymerized GMA (PP‐GMA) thin films deposited on the Ar plasma‐pretreated Si(100) surfaces were retained to a large extent after acetone extraction, suggesting the presence of covalent bonding between the PP‐GMA layer and the Si surface. Thermal imidization of the poly(amic acid) precursor of polyimide on the GMA plasma‐polymerized Si(100) surface resulted in a strongly adhered polyimide film. The adhesion results further suggested that the GMA polymer had been grafted on the Si(100) surface and the epoxide functional groups had undergone reactive interaction (curing) with the carboxylic and amine groups of the poly(amic acid) during thermal imidization. Copyright © 2001 John Wiley & Sons, Ltd.     

Structural Transformations in the Bulk of Polypropylene upon Plasma Treatment

Substantial changes not only on the surface but in the bulk of a polypropylene film can be induced by its treatment in a low-frequency glow discharge, direct-current discharge, and high-frequency discharge. Changes in the phase composition, an increase in crystallinity, melting point elevation, growth of the molecular mass, broadening of the molecular mass distribution, and lowering of the polymer solubility are possible. It was assumed that short-wavelength ultraviolet plasma radiation is responsible for the observed changes in the structure and molecular mass of polypropylene.     

Controllable Modification of Polymer Membranes by Long-Distance and Dynamic Low-Temperature Plasma Flow: Long-Distance and Dynamic Characteristics

The long-distance and dynamic characteristics of low-temperature plasma in a state of flow were studied by observing the glow distance of plasma and detecting the peroxide content formed on the polymer membrane after irradiation. The field emission scanning electron microscopy and accurate weight loss analysis were respectively employed to observe the decreased etching effect of long-distance plasma on uniaxially stretched poly(tetrafluoroethylene) membranes. The effects of plasma excitation time, plasma power, gas flowrate and chamber pressure on the peroxide contents were investigated using polypropylene fiber membranes. The dynamic characteristic of plasma was furthermore discussed by exploring the penetration of plasma flow through membrane pores. The dynamic plasma flow not only exhibited a longer glow distance than static plasma, but also can obtain greater peroxide contents, and even still can penetrate the first membrane and further treat the second membrane layer. The etching and degradation effects of membrane can be significantly reduced in a long-distance and dynamic low-temperature plasma (LDDLTP) flow. The safe distance to minimize the plasma damage to the membrane depends greatly on the plasma conditions. The long-distance acts and complete penetration performances of LDDLTP we have achieved could provide valuable references for membrane modifications in more flexible forms.     

Reactions of polyethylene surfaces with the downstream products of an air plasma: Gas phase and surface spectroscopic studies

The gas phase downstream products of an air glow discharge have been measured, using absorption and emission spectroscopies, as a function of plasma power, air flow rate, and distance from the plasma. In addition, the reaction of these products with a linear low density polyethylene (LLDPE) polymer surface has been followed using x-ray photoelectron spectroscopy (XPS). At higher air flow rates (>300 sccm), the primary reactive species is confirmed to be O(³P) atomic oxygen. Some O(³P) is generated in the plasma itself, but more appears to be formed in the downstream region, because of dissociation of molecules in their excited states. At low flow rates, the concentration of O(³P) is strongly depleted at the sample position, but other atomic oxygen states become more prominent. O(⁵S) and O(³S) are two states which are identified. XPS studies of the polyethylene surface reacted at high flow rates shows oxygen functionalities that are likely the result of an initiation by hydrogen abstraction. At low flow rates, the products suggest initiation by oxygen insertion. Thus, changes in flow rate can result in major changes to the polymer surface chemistry. © 1996 John Wiley & Sons, Inc.     

醛类的等离子体聚合Ⅰ.丁醛等离子体聚合及聚合物结构与性能

应用外部电容耦合式等离子体聚合方法,首次得到了丁醛聚合物,研究了其聚合规律,找到了较好的聚合条件。通过元素分析和红外光谱分析,证实丁醛等离子体聚合物为交联结构;电子衍射分析和X-射线衍射分析发现聚合物中存在部分结晶,而且部分以单晶形式存在;表面能测定表明丁醛等离子体聚合物为疏水性。并初步探讨了反应机理。     

Coupled Sliding Discharges: A Scalable Nonthermal Plasma System Utilizing Positive and Negative Streamers on Opposite Sides of a Dielectric Layer

A nonthermal plasma system based on simultaneously formed positive and negative streamers on either side of a dielectric layer is described. The coupled sliding discharge (CSD) reactor based on this concept was found to be scalable by stacking and operating multiple electrode assemblies in parallel, similarly to the shielded sliding discharge (SSD) reactor reported earlier. A comparison of the two systems showed that although the energy density in the CSD reactor was lower, the efficiency for NO conversion and ozone synthesis from dry air were significantly higher. The energy cost for 50 % NO removal was ~30 eV/molecule compared to ~60 eV/molecule in the case of the SSD under the same conditions of 330 ppm initial NO concentration in air. The energy cost decreased to ~12 eV/molecule in both cases when NO was mixed with plasma-activated air at the outlet of the reactor to utilize ozone for NO conversion i.e., indirect plasma treatment. The energy yield for ozone generation from dry air was at ~70 g/kWh, comparable in both systems. The results show that the concept of a CSD, as that of SSDs, allows the construction of compact, efficient plasma reactors.     

Experimental Investigation of Plasma Oxidization of Diesel Particulate Matter

Particulate matter (PM) from diesel vehicles is harmful to humans and should be removed from the exhaust gases before its emission into the atmosphere. Plasma PM oxidation is an advanced method to be used for oxidative PM removal. Factors influencing plasma PM oxidation include gas temperature, gas composition, PM amount, the geometry of plasma reactors. The PM oxidation in atmospheric air discharges was carried out using a pulsed dielectric barrier discharge reactor at temperatures of 100, 150, and 200 °C. It was found that PM is oxidized to CO and CO₂. CO₂/CO concentration ratio is a function of PM amount in the discharge space. PM removal efficiency (PM amount oxidized per kWh energy injection) increased with increasing air temperature and PM amount in the discharge space. Water promotes PM oxidation, which suggested that oxygen atoms produced in the discharge space react with water to yield hydroxyl free radicals that are of more reactivity than oxygen atoms. The activation energy of plasma PM oxidation was kinetically calculated to be 15.4 kJ/mol.     

Mechanism of antioxidant interaction on polymer oxidation by thermal and radiation ageing

The mechanism of polymer oxidation by radiation and thermal ageing was investigated for the life evaluation of cables installed in radiation environments. The antioxidant as a stabilizer was very effective for thermal oxidation with a small content in polymers, but was not effective for radiation oxidation. The ionizing radiation induced the oxidation to result in chain scission even at low temperature, because the free radicals were produced and the antioxidant could not stop the oxidation of radicals with the chain scission. A new mechanism of antioxidant effect for polymer oxidation was proposed. The effect of antioxidant was not the termination of free radicals in polymer chains such as peroxy radicals, but was the depression of initial radical formation in polymer chains by thermal activation. The antioxidant molecule was assumed to delocalize the activated energy in polymer chains by the Boltzmann statics (distribution) to result in decrease in the probability of radical formation at a given temperature. The interaction distance (delocalization volume) by one antioxidant molecule was estimated to be 5–10 nm by the radius of sphere in polymer matrix, though the value would depend on the chemical structure of antioxidant.     

Wachstum dünner Fluorkohlenstoffschichten auf der Anode einer Glühkathodenentladung

The polymerization of tetrafluorethylene on the anode of a hot glow discharge has been investigated. Rates of polymer deposition have been measured as a function of monomer pressure, discharge current density, and electrode surface temperature. A mechanism of polymer formation is suggested. The results are different from those obtained by polymerization of the same monomer in a glow discharge. It is concluded that negative ions have a great influence on mechanism of polymer formation. Additionally, monomer molecules adsorbed at the electrode are polymerized by electron bombardment.