Deposition conditions influence the postdeposition oxidation of methyl methacrylate plasma polymer films

Plasma polymer films were deposited from methyl methacrylate (MMA) vapor under various plasma conditions and XPS and FTIR used to study the changes to the compositions of the films as they were stored in air for longer than 1 year. The plasma power input per monomer mass unit (W/FM) markedly affected the composition of the freshly deposited MMA plasma polymers. A low value of W/FM led to a high degree of retention of the original monomer structure, whereas a high value of W/FM resulted in substantial monomer fragmentation and the formation of a partially unsaturated material considerably different to conventional PMMA. As the MMA plasma coatings were stored in ambient air after fabrication, all showed spontaneous oxidative changes to their composition, but the extents and reaction products differed substantially. Deposition at low W/FM led to moderate oxidative changes, whereas high power led to a pronounced increase in the oxygen content over time and resulted in a wide range of carbon–oxygen functionalities in the aged material. As the initial compositions/plasma deposition conditions thus influenced the oxidative postdeposition reactions, MMA plasma polymers deposited under different conditions not only varied in their initial composition but then became even more diverse as they aged. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 985–1000, 1998     

Optical emission diagnostics in cascade arc plasma polymerization and surface modification processes

Optical Emission Spectroscopy (OES) was used to identify reactive species and their excitation states in low-temperature cascade arc plasmas of N₂, CF₄, C₂F₄, CH₄, and CH₃OH. In a cascade arc plasma, the plasma gas (argon or helium) was excited in the cascade arc generator and injected into a reactor in vacuum. A reactive gas was injected into the cascade arc torch (CAT) that was expanding in the reactor. What kind of species of a reactive gas, for example, nitrogen, are created in the reactor is dependent on the electronic energy levels of the plasma gas in the cascade arc plasma jet. OES revealed that no ion of nitrogen was found when argon was used as the plasma gas of which metastable species had energy less than the ionization energy of nitrogen. When helium was used, ions of nitrogen were found. While OES is a powerful tool to identify the products of the cascade arc generation (activation process), it is less useful to identify the reactive species that are responsible for surface modification of polymers and also for plasma polymerization. The plasma surface modification and plasma polymerization are deactivation processes that cannot be identified by photoemission, which is also a deactivation process. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1583–1592, 1998     

Surface modification of poly(tetrafluoroethylene) by a low-temperature cascade arc torch and radio-frequency plasmas

Poly(tetrafluoroethylene) (PTFE) films were treated with a low-temperature cascade arc torch (LTCAT) and radio-frequency (RF) plasmas of argon and hydrogen. The plasma-treatment effect on the PTFE surface was studied with contact-angle measurement and scanning electron spectroscopy (SEM). LTCAT argon plasma, which is recognized as a beam of excited argon neutrals, was very efficient at improving the surface hydrophilicity of PTFE. For both the LTCAT and RF operation, argon plasma was more effective at modifying the surface wettability of PTFE films than hydrogen plasma was. Furthermore, the sample positions (inside or beyond the glow region) had a strong impact on the efficiency of the plasma treatment. SEM surface images indicated that no significant morphology change was induced on the PTFE films exposed to a LTCAT and RF argon plasmas. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4432–4441, 1999     

An Optical Emission Study on Expanding Low-Temperature Cascade Arc Plasmas

The optical emission spectra from expanding low-temperature cascade arc plasmas were studied. The objective of this study was to examine the distinctive features of low-temperature cascade arc plasmas in comparison with a radio frequency (RF) plasma source. The principal results obtained in this study were: (1) in an expanding cascade arc plasma jet, active heavy particles (mainly excited argon or helium neutral species under our operating conditions), rather than electrons, are responsible for the excitation of reactive species when a reactive gas is injected into the plasma jet, (2) the excitation of reactive species was found to be controlled by the electronic energy levels of these excited argon or helium neutrals, (3) changing the operating parameters affected only the emission intensities of excited species, and no effect on the emission nature of plasmas was observed.     

Penetration of plasma surface modification. II. CF4 and C2F4 low-temperature cascade arc torch

The depth of surface modification by low-temperature cascade arc torch is investigated. A stack of 10 sheets of nonwoven fabrics of polyester fibers is exposed to a low-temperature cascade arc torch containing CF₄ or C₂F₄, and the fluorination effect is examined by ESCA. It is shown that interaction of chemically reactive species, created in a low-temperature cascade arc torch, with the surface is not limited to the surface contacted by the torch (flame). The results indicate that the fluorination effect is observed on surfaces which are shadowed from the torch by overlying fibers. The highest degree of fluorination is found on the second layer, rather than on the first layer which the torch contacts directly. No significant differences in the trends of penetration of CF₄ and C₂F₄ treatment through porous samples are observed. However, ESCA data show principal differences in chemical structures of the surfaces treated with CF₄ (nonpolymer-forming gas) and C₂F₄ (polymer-forming gas). These results indicate that chemically reactive species induced by the excited species of argon rather than primary species created by the ionization process seem to play predominant roles in the surface treatment as well as the low-temperature cascade arc torch polymerization of perfluorinated compounds. © 1994 John Wiley & Sons, Inc.     

Distribution of polymer deposition in plasma polymerization. III. Effect of discharge power

Distribution of polymer deposition in an inductively coupled rf discharge system is studied as a function of level of discharge power with acetylene and styrene as monomers. When a fixed flow rate is used, the discharge power has a relatively small effect on the pattern of distribution of polymer deposition as long as values of W/FM, where W is discharge wattage, F is flow rate, and M is molecular weight of monomer, are maintained above a critical level to maintain full glow in the reaction tube. It has been shown that plasma polymerization of two monomers which have different molecular weights can be compared in a fair manner by selecting conditions to yield similar value of W/FM.     

Plasma diagnostics of barrier-torch discharge in argon flow in a capillary by cross-correlation spectroscopy

The radiation kinetics of the plasma of barrier-torch disrcharge in argon flow in a capillary has been studied by cross-correlation spectroscopy. It was established that the discharge emission spectrum consists of peaks of electronically excited states of argon, bands of hydroxyl radicals, and a second positive system of nitrogen. An analysis of the spatio-temporal distributions of emission intensity for the selected spectral indicators showed that the causes of the torch are ionization waves that extend through the capillary from the electrode system with a speed of 10⁵ m/s and project up to 3–4 mm. It was established that the formation of electronically excited molecules of nitrogen N₂(C ³Π _u ) in the torch of discharge occurs mainly on the reaction between metastable electronically excited atoms of argon and molecules of nitrogen in the electronic ground state.     

Atomic and molecular emission spectroscopy on an expanding argon/methane plasma

A supersonically expanding cascaded arc plasma in argon is analyzed axperimentally by emission spectroscopy. The thermal cascaded arc plasma is allowed to expand through a conically shaped nozzle in the arc anode into the vacuum vessel. In the nozzle monomers (C _n H _v ) are injected. The monomers are dissociated and ionized by the argon carrier plasma, and transported toward a substrate by means of the expansion. Emission spectroscopy is used to obtain temperatures and particle densities. By varying external parameters (e.g., arc power, gas flow rates) plasma parameters can be linked with (e.g. parameters (e.g., refractive index).     

Penetration of plasma surface modification into porous media. III. Multiple samples exposed to CF4 and C2F4 low temperature cascade arc torch

The depth and possible mechanisms of the penetration of surface modification into porous media by a low temperature cascade are torch are investigated. Two different modes of such penetration (“flow controlled” and “diffusion controlled”) are evaluated. Three porous samples [stacks of 10 sheets of nonwoven fabrics of poly(ethylene terephthalate)each], placed at an axial distance of 24, 28, and 32 cm from the cascade are anode, are exposed to a low temperature cascade arc torch containing argon and CF₄ or C₂F₄, and surface properties of each of the sheets within treated porous samples are examined by ESCA. It is shown that interaction of chemically reactive species, created in the low temperature cascade arc torch, with the surface is not limited to the surface directly contacted by the torch. The flow controlled penetration is more pronounced for the outer layers, while diffusion controlled penetration is within the inner layers of the porous structure. Substantial differences in the fluorination effect of CF₄ (nonpolymer forming gas) and C₂F₄ (polymer forming gas) discharges for the second and third stacks are observed, that can be explained by the fact that the major effect of the CF₄ cascade arc torch treatment is based on the reaction of reactive species with the surface polymer molecules. The effect of C₂F₄ cascade arc torch treatment is based on the reactions of reactive species with polymers as well as reactions of reactive species themselves at the surface (plasma polymerization). Reactivity of the species created in C₂F₄ discharge is much higher compared to that created in CF₄ discharge, which is one of the major factors influencing penetration trends of low temperature cascade arc treatment into porous media. © 1995 John Wiley & Sons, Inc.     

Plasma homo- and copolymerizations of tetrafluoroethylene and chlorotrifluoroethylene

The plasma homo- and copolymerizations of tetrafluoroethylene (TFE) and chlorotrifluoroethylene (CTFE) in a capacitively coupled tubular reactor (TR) with external electrodes were studied by means of microgravimetry and FT-IR and XPS analyses. The deposition rates for CTFE/TFE plasma copolymers, as well as the ratios of IR absorbances at 1180 and 1225 cm⁻¹, and the XPS-derived Cl/C and F/C ratios, varied regularly with mol % CTFE in the feed, all of which results were dependent upon the rf power at which the plasma copolymerizations were conducted. The deposition rates for the plasma homopolymers of TFE (PPTFE) and CTFE (PPTCFE) depended markedly on rf power (W) and monomer molar flow rate (F). The F/C ratio for PPTFE was nearly independent of the composite parameter,W/FM (whereM is the monomer molecular weight), while for PPCTFE, the F/C ratio decreased significantly and the Cl/C ratio increased slightly with increase inW/FM. The percentage of carbon as CF₃ was 20–24% in PPTFE and 7–14% in PPCTFE. Plots of deposition rate versusW/FM for PPTFE and PPCTFE obtained in a TR differed considerably from corresponding plots in the literature for the same homopolymers prepared in a glass-cross or bell-jar reactor.     

Molecular adsorption and the chemistry of plasma-deposited thin organic films: Deposition of oligomers of ethylene glycol

Weakly ionized, radio-frequency, glow-discharge plasmas formed from methyl ether or the vapors of a series of dimethyl oligo(ethylene glycol) precursors (general formula: H-(CH₂OCH₂)_n-H;n=1 to 4) were used to deposit organic thin films on polytetrafluoroethylene. X-ray photoelecton spectroscopy (XPS) and static secondary ion mass spectrometry (SIMS) of the thin films were used to infer the importance of adsorption of molecular species from the plasma onto the surface of the growing, organic film during deposition. Films were prepared by plasma deposition of each precursor at similar deposition conditions (i.e., equal plasma power (W), precursor flow rate (F), and deposition duration), and at conditions such that the specific energy (energy/mass) of the discharge (assumed to be constrained byW/FM, whereM=molecular weight of the precursor) was constant. At constantW/FM conditions, two levels of plasma power (and, hence, twoFM levels) and three substrate temperatures were examined. By controlling the energy of the discharge (W/FM) and the substrate temperature, these experiments enabled the study of effects of the size and the vapor pressure of the precursor on the film chemistry. The atomic % of oxygen in the film surface, estimated by XPS, and the intensity of theC-O peak in the XPS C_ls spectra of the films, were used as indicators of the degree of incorporation of precursor moieties into the plasma-deposited films. Analysis of films by SIMS suggested that these two measures obtained from XPS were good indicators of the degree of retention in the deposited films of functional groups from the precursors. The XPS and SIMS data suggest that adsorption of intact precursor molecules or fragments of precursor molecules during deposition can have a significant effect on film chemistry. Plasma deposition of low vapor pressure precursors provides a convenient way of producing thin films with predictable chemistry and a high level of retention of functional groups from the precursor.     

Internal stress in plasma polymer films prepared by cascade arc torch polymerization

Thin plasma polymer films were deposited from several liquid monomers (mainly siloxane‐type monomers) in a low‐temperature cascade arc torch (CAT) reactor. The effects of monomer structures and plasma parameters on internal stress in the films were experimentally studied. By appropriately adjusting these factors, the internal stress in the film was reduced nearly two orders of magnitude from 10⁹ to 10⁷ dyn/cm². It was noted that the polymer films prepared from siloxane‐type monomers showed lower internal stress than their hydrocarbon counterpart. Fourier transform‐infrared spectroscopy (FTIR) studies indicated that a large amount of Si O Si structure from siloxane monomers, which are very flexible bonds, was preserved in the resultant plasma polymers. Ellipsometry results suggested that the internal stress can be qualitatively correlated with the refractive index of the plasma polymer film. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1577–1587, 1999     

Comparisons of glow-discharge polymerizations among tetramethylsilane,dimethyldimethoxysilane, and tetramethoxysilane

Glow-discharge polymerizations among tetramethylsilane, dimethyldimethoxysilane, and tetramethoxysilane were compared by elemental analyses and infrared spectroscopy. The elemental composition of the polymers prepared from the three monomers depended strongly on the operational conditions necessary to sustain a glow discharge, i.e., the W/FM parameter, where W is the rf power, F is the flow rate of the monomer, and M is the molecular weight of the monomer. Methoxy groups were more susceptible to glow discharge than methyl groups. Differences in chemical structure among these monomers appeared in the polymer structures formed when the glow-discharge polymerization was carried out at a low value of the W/FM parameter, while the differences disappeared at high values of the W/FM parameter, for analogous polymers. Substitution with methoxy groups was favorable for the formation of polymers of low carbon content only when the glow-discharge polymerization was performed at low values of W/FM.     

Intramolecular excited state complexes in trichromophoric model compounds for polyesters derived from 2,6‐naphthalenedicarboxylic acid and aliphatic glycols: experiment,rotational isomeric state model,and molecular dynamics

Steady‐state fluorescence was used to measure the ratio of emission intensities, denoted I_D/I_M, for excited state complexes and excited monomers of five trichromophoric compounds, 2‐naphthyl‐COO‐(CH₂)_m‐OOC‐2,6‐dinaphthyl‐COO‐(CH₂)_m‐OOC‐2‐naphthyl, m = 2–6. The linear aliphatic alcohols H(CH₂)_nOH, n = 1–7, as well as mixtures of ethylene glycol and methanol, were used to change the viscosity of the medium, η. The values of I_D/I_M depend on η and m. A Rotational Isomeric State model and Molecular Dynamics simulations were used for interpretation of the experimental results. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 253–266, 1999     

Some aspects of plasma polymerization of fluorine-containing organic compounds. II. Comparison of ethylene and tetrafluoroethylene

Plasma polymerizations of ethylene and tetrafluoroethylene are compared. In the plasma polymerization of ethylene and of tetrafluoroethylene, glow characteristics play an important role. Glow characteristic is dependent on a combined factor of W/F_m, where W is discharge power and F_m is monomer flow rate. At higher flow rates, higher wattages are required to maintain “full glow.” In the plasma polymerization of tetrafluoroethylene, simultaneous decomposition of the monomer competes with plasma polymerization. Above a certain value of W/F_m, decomposition becomes the predominant reaction, and the polymer deposition rate decreases with increasing discharge power. ESCA results indicate that the plasma polymer of tetrafluoroethylene that is formed in an incomplete glow region (low W/F_m) is a hybrid of polymers of plasma polymerization and of plasma-induced polymerization of the monomer. Polymers formed under conditions of high W/F_m to produce “full glow” are similar, regardless of the extent of decomposition of the monomer. They contain carbons with different numbers of F(CF₃, ? CF₂? , >CF? , >C<) and carbons bonded to other more electronegative substituents.     

Plasma polymerization investigated by the substrate temperature dependence

Plasma polymerization of tetra fluoroethylene (TFE), perfluoro-2-butyl-tetrahydrofuran (PFBTHF), ethylene, and styrene were investigated in various combinations of monomer flow rates and discharge wattages for the substrate temperature range of ?50 to 80°C. The polymer deposition rates can be generally expressed by k₀ = Ae^?bt, where k₀ is the specific deposition rate given by k₀ = (deposition rate)/(mass flow rate of monomer), A is the preexponential factor representing the extrapolated value of k₀ at zero absolute temperature, and b is the temperature-dependence coefficient. It was found that the value of b is not dependent on the condensibility of monomer but depends largely on the group of monomer; that is, perfluorocarbons versus hydrocarbons. The values of A are dependent on domains of plasma polymerization. In the energy deficient region A is given by A = α(W/FM)ⁿ, where α is the proportionality constant, W is discharge wattage, FM is the mass flow rate, and n is close to unity. In the monomer deficient region A becomes a constant. The kinetic equation is discussed in view of the bicyclic rapid step-growth polymerization mechanisms.     

An overall mechanism for the deposition of plasma polymers from methane in a low-pressure argon plasma jet

An overall mechanism for plasma polymer deposition from a methane-seeded argon plasma jet was established from experimental measurements and a simplified model of reaction kinetics within the plasma jet. Total mass deposition rates were obtained at various substrate positions and methane flow rates. Methane consumption was estimated from residual gas analysis. The influence of substrate coolant temperature on deposition rate was evaluated. The model was based on particle densities, jet temperature, and jet velocity data published previously, and reaction rate constants from the literature were used. No adjustable parameters were employed in this model. Experimental results for total deposition rate and methane consumption were in good agreement with model predictions. The overall deposition mechanism consists of three steps: Penning ionization of methane by excited argon neutrals, followed by dissociative recombination of CN _x ⁺ to yield CH, followed by incorporation of CH into the growing film upon impact. Contributions of species other than CH to the total deposition rate are minor, and adsorption is not a prerequisite for incorporation into the growing film.     

Rod-like polyelectrolyte adsorption onto charged surfaces in monovalent and divalent salt solutions

We analyze the adsorption of strongly charged polyelectrolytes onto weakly charged surfaces in divalent salt solutions. We include short-range attractions between the monomers and the surface and between condensed ions and monomers, as well correlations among the condensed ions. Our results are compared with the adsorption in monovalent salt solutions. Different surface charge densities (σ), and divalent (m) and monovalent (s) salt concentrations are considered. When the Wigner-Seitz cells diameter (2R) is larger than the length of the rod, the maximum amount of adsorption scales like n_max ∼ σ^4/3 in both monovalent and divalent solutions. For homogeneously charged surfaces, the maximum adsorption occurs at s* ∼ σ² when s* > ϕ, where ϕ is the monomer concentration, the counterpart for divalent salt solution, m* roughly scales as σ^2.2 when m* > ϕ. The effective surface charge density has a maximum absolute value at m′ < m*. A discrete surface charge distribution and short-range attractions between monomers and surface charge groups can greatly enhance surface charge inversion especially for high salt concentration. The critical salt concentration for adsorption in divalent salt solution roughly scales as m_c ∼ bσ^1.9, where b is the distance between two neighboring charged monomers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3642–3653, 2004     

Two-Temperature Chemical-Nonequilibrium Modelling of a High-Velocity Argon Plasma Flow in a Low-Power Arcjet Thruster

A numerical simulation has been performed of a high-velocity argon plasma arc flow in a low power arcjet including a finite-rate chemical kinetic model. Electrons, ions, molecular ions ( $ {\text{Ar}}_{2}^{ + } $ ), neutral atoms including the ground and excited argon atoms (Ar^*) are treated as separate species in the plasma mixture. The chemical reactions considered are excitation, de-excitation, ionization and recombination processes, in which reactions involving excited argon atoms (Ar^*) and molecular ions ( $ {\text{Ar}}_{2}^{ + } $ ) are taken into account. The relative importance of different production and loss processes in determining the densities of excited argon atoms and ions is calculated inside the constrictor and expansion portion of the nozzle. The roles of the excited argon atoms and molecular ions are investigated. It is found that excited argon atoms play an important role in the ionization of argon atoms in the core of plasma arc, while the molecular ions have a significant effect on the recombination process at the arc fringes inside the constrictor and in the arc attachment zone of the anode.     

Glow discharge polymerization of tetramethylsilane investigated by infrared spectroscopy and ESCA

The influence of operating conditions (W/FM parameter: W input energy of rf power; F flow rate of monomer; M molecular weight of monomer) on glow discharge polymerization of tetramethylsilane (TMS) was investigated by infrared spectroscopy and ESCA. Elemental analyses showed that the compositions of the polymers formed strongly depended on the level of the W/FM parameter, i.e., whether the W/FM value was more or less than 190 MJ/kg. The infrared spectra indicated that these polymers were composed of Si? H, Si? O, Si? C, Si? CH₃, and Si? CH₂ groups, and that there was no significant difference in structural features between polymers prepared at W/FM parameters of more or less than 190 MJ/kg. ESCA spectra (C_1s and Si_2p core-level spectra) showed that the polymers included carbonized carbon, aliphatic carbon Si? C, C? O, Si? O, and SiO₂ species, and that the sum of carbonized and aliphatic carbons reached more than 50%. Raising the W/FM value increased the formation of the carbonized carbon but did not influence the formation of Si units such as Si? C and Si? O groups. From this evidence the rupture of Si? CH₃ bonds in the polymer forming process is emphasized. The magnitude of the W/FM parameter may be related to the detachment of hydrogen from the aliphatic carbon units.