Plasma Treatment of Polymers

Abstract

Plasma treatment of polymers encompasses a variety of plasma technologies and polymeric materials for a wide range of applications and dates back to at least the 1960s. In this article we provide a brief review of the United States patent literature on plasma surface modification technologies and a brief review of the scientific literature on investigations of the effects of plasma treatment, the nature of the plasma environment, and the mechanisms that drive the plasma–surface interaction. We then discuss low‐radio‐frequency capacitively coupled nitrogen plasmas and their characteristics, suggesting that they provide significant plasma densities and populations of reactive species for effective plasma treatments on a variety of materials, particularly when placing the sample surface in the cathode sheath region. We further discuss surface chemical characterization of treated polymers, including some results on polyesters treated in capacitively coupled nitrogen plasmas driven at 40 kHz. Finally, we connect plasma characterization with surface chemical analysis by applying a surface sites model to nitrogen uptake of poly(ethylene terephthalate) (PET) and poly(ethylene naphthalate) (PEN) treated in a 40 kHz nitrogen plasma. This example serves to suggest an interesting practical approach to comparisons of plasma treatments. In addition, it suggests an approach to defining the investigations required to conclusively identify the underlying treatment mechanisms.     

Vacuum Ultraviolet Irradiation of Polymers

The interest in incoherent sources for wavelength-selective photochemistry has increased lately, but little is still known about the behavior of polymers when exposed to far UV and vacuum UV (VUV) radiation. The same dearth of information exists regarding UV (VUV) radiation emitted by low-pressure plasmas during polymer treatment. In order to study VUV-UV effects on several polymers (polyethylene - PE, polystyrene - PS, hexatriacontane - HTC, and poly(methyl methacrylate) - PMMA), we have used the well-characterized emissions from hydrogen (broad-band emission) and hydrogen/argon mixture (near-monochromatic radiation) plasmas as light sources. During irradiation, samples were kept under vacuum or in a flow of pure oxygen at low pressure; in both cases the radiation fluxes at the sample position have been precisely determined by careful spectroscopic calibration experiments. We have employed a quartz crystal microbalance (QCM) to measure in-situ any possible mass change of the various polymers. Following irradiation, samples were analysed by ellipsometry (for thickness and refractive index), X-ray photoelectron spectroscopy (XPS, to evaluate the near-surface composition and content of various functional groups), and atomic force microscopy (AFM, for surface topography and roughness measurements).     

Treatment of a Polyethylene Powder Using a Remote Nitrogen Plasma Reactor Coupled with a Fluidized Bed: Influence on Wettability and Flowability

A Far Cold Remote Nitrogen Plasma is used both to fluidize and to treat a polyethylene powder in order to increase its hydrophilic character. The evolution of the wettability of the powder as well as the one of its physical (density, particles size distribution, average diameter, shape factor, and BET surface area) and flow properties (angle of repose, angle of slide, and Hausner index) are determined versus various experimental conditions. It is shown that the plasma treatment efficiency is strongly dependant on the oxygen content of the nitrogen flow and on the velocity of fluidizing gas. Best wettability is obtained by the addition of 0.75% of O₂ in the nitrogen plasma gas and with a high gas velocity. It is also evidenced that the flowability of the powder is slightly altered by the plasma treatment.     

Plasma Treatment of Polymers to Generate Stable,Hydrophobic Surfaces

Tailoring of polymers for multifaceted applications is an increasing field, whereby most often the surface properties must be adjusted. Therefore, the coating of common polymers by plasma polymerization is a promising way to modify the surface and meet the demands. Beside the tuning of the required surface properties, good adhesion and stability of the films is essential. This work investigates the plasma deposition of pp-HMDSO films on PC and PC/ABS to generate stable, hydrophobic surfaces. By examining the plasma conditions—deposition rate, energy range, and surface topography—ultrathin, stable films with advancing contact angles up to 110° and receding angles exceeding 90° can be designed. Storage of the siloxane films for 1 year in air at ambient conditions exhibits almost no aging. Thus, these films are superior to fluorocarbon films deposited for comparison.     

A comparative study of the silent discharge treatment of saturated and unsaturated hydrocarbon polymers

Dielectric barrier air discharge treatment of polyethylene, polypropylene, polyisobutylene, polystyrene, and polyisoprene substrates has been characterized by x-ray photoelectron spectroscopy (XPS). The relative reactivities of these polymers towards silent discharge oxidation are rationalized in terms of ozone molecules interacting with an excited surface. © 1994 John Wiley & Sons, Inc.     

Atmospheric Pressure Plasma Surface Treatment of Polymers and Influence on Cell Cultivation

Atmospheric plasma treatment is an effective and economical surface treatment technique. The main advantage of this technique is that the bulk properties of the material remain unchanged while the surface properties and biocompatibility are enhanced. Polymers are used in many biomedical applications; such as implants, because of their variable bulk properties. On the other hand, their surface properties are inadequate which demands certain surface treatments including atmospheric pressure plasma treatment. In biomedical applications, surface treatment is important to promote good cell adhesion, proliferation, and growth. This article aim is to give an overview of different atmospheric pressure plasma treatments of polymer surface, and their influence on cell-material interaction with different cell lines.     

聚丙烯微孔膜表面的空气等离子体处理

采用空气等离子体对聚丙烯微孔膜进行了处理，膜表面带有了氧元素，表面亲水性增强。微孔膜外表面改性程度较高，而孔内愈往深处改性程度愈弱。空气等离子体处理过的微孔膜力学性能下降。     

增容聚苯乙烯共混物的研究进展

综述了增容聚苯乙烯与聚乙烯、聚丙烯、聚酰胺共混物的研究进展。不同共混物采用不同的增容剂,可使增容聚苯乙烯共混物改善分散相尺寸、界面相互作用与粘结,达到提高共混物的力学性能的目的。增容效果与增容剂的类型、用量和分子结构有关。     

高强聚乙烯纤维的冷等离子体改进

高强聚乙烯纤维的冷等离子体改进金士九，倪亦斌，张佐光（中国科学院化学研究所北京１０００８０）（北京航空航天大学北京）关键词　高强聚乙烯纤维，等离子体，表面改性，界面性能由高强聚乙烯纤维制成的复合材料抗高速撞击（抗弹）性能远远优于芳纶纤维，广泛用作各种...     

Transition and relaxation processes of polyethylene,polypropylene, and polystyrene studied by positron annihilation

Transition and relaxation processes of polyethylene (PE), polypropylene (PP), and polystyrene (PS) were studied by the positron annihilation technique. From measurements of lifetime spectra of positrons as a function of temperature, the lifetime of ortho-positronium, τ₃, and its intensity, I₃, were found to increase above 260 K for PP. This fact was attributed to a cooperative motion of large segments of molecules above the glass transition temperature, T_g. For PE, above T_g (140 K), the value of τ₃ increased, but the temperature coefficient of I₃ was negative below 230 K. From this fact, for PE, the molecular motions that cause the glass transition were associated with a rearrangement of molecules by local motions such as kink motions. The discrepancy between the results for PE and PP was attributed to the presence of methyl groups in PP and the resultant suppression of the local motions. For PS (T_g = 340 K), the molecular motions were found to start above 260 K, but those were suppressed by an interphenyl correlation. Detailed annihilation characteristics of positrons in polymers were also discussed. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1601–1609, 1997     

Plasma and Polymers: Recent Progress and Trends

Plasma-enhanced synthesis and modification of polymers is a field that continues to expand and become increasingly more sophisticated. The highly reactive processing environments afforded by the inherently dynamic nature of plasma media are often superior to ambient or thermal environments, offering substantial advantages over other processing methods. The fluxes of energy and matter toward the surface enable rapid and efficient processing, whereas the charged nature of plasma-generated particles provides a means for their control. The range of materials that can be treated by plasmas is incredibly broad, spanning pure polymers, polymer-metal, polymer-wood, polymer-nanocarbon composites, and others. In this review, we briefly outline some of the recent examples of the state-of-the-art in the plasma-based polymer treatment and functionalization techniques.     

Calytic Degradation of Mixed Plastics Using Natural Clinoptilolite Catalyst

Catalytic degradation of the mixture of polyethylene (PE), polypropylene (PP), and polystyrene (PS) was investigated in a semi-batch reactor. The main degradation product was liquid oil with gasoline range carbon number distributions. Clinoptilolite a natural zeolite (HNZ) showed as good a catalytic performance as silica-alumina (SA). The protonated catalysts (HNZ, HZSM-5) showed an increased production of ethylbenzene, but a decrease of styrene production. Increase of degradation temperature resulted in a decrease of ethylbenzene and propylbenzene, but an increase of styrene. Thermogravimetric analysis revealed that the increased degradation rate in the mixed plastics came from the intermolecular carbenium ion transfer between the degraded fragments of PE, PP, and PS.This revised version was published online in December 2005 with corrections to the Cover Date.     

Temperature Distribution in a Pilot Plasma Tundish: Comparison Between Plasma Torch and Graphite Electrode Systems

Arc, bath, and refractory wall temperatures are measured in a pilot transferred-arc plasma furnace by atomic emission spectroscopy (AES) and multiwavelength pyrometry. Argon plasma torch and graphite electrode with nitrogen as plasma gas are both examined and compared using the steel bath as anode. With argon, a two-slope characteristic curve is measured for arc temperature, which ranges from 9000 to 25,000 K. Another trend is observed with nitrogen for temperatures in the range 8000–12,000 K. In this latter case, the bath temperature is very sensitive to arc length: more than 100 K increase results in arc length rise from 50 to 150 mm. Experimental data shows the variation of heat transfer efficiency between the two configurations, which is supported by results about surface emissivity in the spectral domain 1–15 m.     

N-取代丙烯酰胺的等离子体引发聚合及聚合物性能研究

温敏树脂;N取代丙烯酰胺的等离子体引发聚合及聚合物性能研究     

Spatial Transition of the Electron Gas from the Active to the Remote Plasma State

Starting from the active region of a weakly ionized plasma the spatial transition of the electron gas through an adjacent field decay region into the field-free remote plasma is studied in neon on a rigorous basis by using two independent kinetic approaches. The main objective of the analysis concerns the complex features of the electron gas in its transition process from a field-driven active plasma to a purely diffusion-driven remote plasma. In addition to the energy resolved characterization of the velocity distribution, in particular, the spatial decay behavior of important, energy space averaged transport and dissipation properties of the electrons, as the density, the particle and energy fluxes and the power transfer rates to the gas particles in electron collisions, is elaborated and interpreted. Moreover, the influence of a variation of the active plasma conditions and of the spread of the field decay region on the resultant transition behavior of the electron gas is evaluated. A particular finding is that the spatial field decay is generally accompanied by a large density increase in order to allow the continuation of the electron flux by a pure diffusion process in the adjacent remote plasma. This finding could be completely confirmed by the almost perfect coincidence of corresponding results obtained by two independent kinetic approaches.     

原生态聚丙烯等离子体处理接枝甲基丙烯酸甲酯

将等离子体接枝技术，用于原生态聚丙烯接枝甲基丙烯酸甲酯共聚物的合成。ＦＴ－ＩＲ证明所得产物为接枝共聚物，研究了不同等离子体处理功率、时间，不同接枝聚合反应时间、温度对接枝的影响，以及稀释剂、聚丙烯粒度对接枝的影响。结果表明，接枝过程中有自动加速现象，稀释剂亦使接枝有加速效应。接枝过程为扩散控制过程。     

间接等离子体聚合制备聚吡咯薄膜

通过吡咯在氩辉光放电气流下游区域的间接等离子体聚合作用制备了聚吡咯薄膜。研究了聚合膜的沉积速率，用ＦＴＩＲ、ＸＰＳ、ＳＥＭ、ＸＲＤ、ＴＥＤ等手段表征了聚合膜的结构和形态。结果表明，聚合膜完整地保留了吡咯单体的共轭结构，显示出较高的导电性，化学掺杂碘以后膜的室温电导率为１０－７～１０－６Ｓ／ｃｍ。     

等离子体改性聚丙烯纤维表面的XPS研究

用等离子体技术处理了聚丙烯纤维表面．用Ｘ－射线光电子能谱（ＸＰＳ）研究了聚合物表面的元素组成、相对含量的变化、表面官能团的类型．采用曲线拟合分峰技术对谱图进行数学处理，结果表明：尽管处理气氛不同，聚丙烯纤维表面除含有Ｃ—Ｈ和Ｃ＝Ｃ键外，还引入了Ｏ、Ｎ元素．形成活性基团：－ＯＨ、＞Ｃ＝Ｏ、－ＣＯＯＨ、－ＮＨ２和－ＣＯＮＨ２等，提高了聚合物表面活性。