Plasma etching and plasma polymerization coating of carbon fibers. Part 1. Interfacial adhesion study

Unsized AS-4 carbon fibers were etched by RF plasma and then coated via plasma polymerization in order to enhance their adhesion to vinyl ester resin. Gases utilized for plasma etching were Ar, N₂ and O₂, while monomers used in plasma polymerization coating were acetylene, butadiene and acrylonitrile. Plasma etchings were carried out as a function of plasma power (30–70 W), treatment time (1–10 min) and gas pressure (20–40 mtorr). Plasma polymerizations were performed by varying the treatment time (15–60 s), plasma power (10–30 W) and gas pressure (20-40 mtorr). The conditions for plasma etching and plasma polymerization were optimized by measuring interfacial adhesion with vinyl ester resin via micro-droplet tests. Plasma etched and plasma polymer coated carbon fibers were characterized by SEM, XPS, FT-IR and α-Step, dynamic contact angle analyzer (DCA) and tensile strength measurements. In Part 1, interfacial adhesion of plasma etched and plasma polymer coated carbon fibers to vinyl ester resin is reported, while characterization results including tensile strength of carbon fibers are reported in Part 2. Among the treatment conditions, a combination of Ar plasma etching and acetylene plasma polymer coating provided greatly improved interfacial shear strength (IFSS) of 69 MPa, compared to 43 MPa obtained from as-received carbon fiber. Based on the SEM analysis of failure surfaces and load-displacement curves, the failure was found to occur at the interface between plasma polymer coating and vinyl ester resin.     

Electrochemical properties of polypropylene membranes modified by the plasma polymerization coating of SO2/acetylene

Polypropylene membranes were modified by the plasma etching of SO₂, SO₂? O₂, or SO₂? H₂O, followed by the plasma polymerization coating of SO₂/acetylene. The conditions for SO₂ plasma etching were optimized by the measurement of the ion‐exchange capacity (IEC) as a function of the plasma‐etching power (10–30 W), gas pressure (40–60 mTorr), and treatment time (15–120 s). For the plasma etching of SO₂? O₂ and SO₂? H₂O, only the pressure ratio (SO₂/O₂ and SO₂/H₂O) was optimized under the optimized conditions determined from SO₂ plasma etching. Plasma etching was then combined with the plasma polymerization coating of SO₂/acetylene, for which the conditions were again optimized by the measurement of the IEC as a function of the plasma power (10–40 W), chamber pressure (50–200 mTorr), SO₂/acetylene ratio (15/135–60/90), and treatment time (0–10 min). Next, the electrical resistance and water uptake were evaluated. The modified membranes were also analyzed with scanning electron microscopy, whereas plasma polymer coatings were characterized with Fourier transform infrared/attenuated total reflection. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3692–3699, 2006     

Adhesion of Natural Rubber Compounds to Plasma-Polymerized Acetylene Films

Plasma-polymerized acetylene films were shown to be novel, highly effective primers for rubber-to-steel bonding. However, the performance of the primers depended strongly on processing variables such as the substrate pretreatment and the carrier gas. Miniature lap joints were prepared by using natural rubber as an “adhesive” to bond together pairs of pretreated steel adherends primed with plasma-polymerized acetylene films which were deposited using various carrier gases. The initial strength of joints prepared from substrates which were mechanically polished and then coated with plasma-polymerized acetylene films deposited using an argon or nitrogen carrier gas was 2000 N for a bonded area of 64 mm² and failure was 100% cohesive in the rubber. Similar results were obtained for joints prepared from mechanically-polished brass substrates. However, the initial strength of joints prepared from polished substrates which were coated with plasma-polymerized films deposited using oxygen as a carrier gas was lower by a factor of two and there was only 30% rubber coverage on the substrate failure surfaces. demonstrating the importance of the carrier gas.

The initial strength of joints prepared from substrates which were pretreated by alkaline cleaning, acid etching, or mechanical polishing and then coated with plasma polymers using argon as the carrier gas was also approximately 2000 N/64 mm² and failure was again 100% cohesive in the rubber. However, the strength of joints prepared from substrates which were pretreated by ultrasonic cleaning in acetone and then coated with plasma polymers using argon as the carrier gas was lower by a factor of almost two, demonstrating the significance of substrate pretreatment.

During exposure to steam at 121°C, the durability of miniature lap joints prepared from polished steel substrates primed with plasma-polymerized acetylene films using argon as a carrier gas was excellent. After exposure for 3 days, the breaking strength of the joints decreased slightly, from 1740 to 1410 N/64 mm², but the locus of failure remained cohesive in the rubber, implying that effect of steam was mostly to reduce the cohesive strength of the rubber. Similar results were obtained from joints prepared from polished brass substrates. However, the durability of joints prepared from polished brass substrates and from polished steel substrates primed with plasma-polymerized acetylene was poor during exposure to aqueous salt solutions for three days. Although all of the joints decreased significantly in breaking strength, the strength of the joints prepared from brass substrates was about 400 N/64 mm² higher than that of joints prepared from steel primed with plasma-polymers. Most of the joints prepared from steel primed with plasma-polymerized acetylene films failed near the interface between the primer and the steel substrate although some specimens had 20-40% rubber coverage on the failure surfaces.     

Plasma etching and plasma polymerization coating of carbon fibers. Part 2. Characterization of plasma polymer coated carbon fibers

Unsized AS-4 carbon fibers were subjected to RF plasma etching and/or plasma polymerization coating in order to enhance their adhesion to vinyl ester resin. Ar, N₂ and O₂ were utilized for plasma etching, and acetylene, butadiene and acrylonitrile were used for plasma polymerization coating. Etching and coating conditions were optimized in terms of plasma power, treatment time, and gas (or monomer) pressure by measuring the interfacial adhesion strength. Interfacial adhesion was evaluated using micro-droplet specimens prepared with vinyl ester resin and plasma etched and/or plasma polymer coated carbon fibers. Surface modified fibers were characterized by SEM, XPS, FT-IR, α-Step, dynamic contact angle analyzer (DCA) and tensile strength measurements. Interfacial adhesion between plasma etched and/or plasma polymer coated carbon fibers and vinyl ester resin was reported previously (Part 1), and characterization results are discussed is this paper (Part 2). Gas plasma etching resulted in preferential etching of the fiber surface along the draw direction and decreased the tensile strength, while plasma polymer coatings altered neither the surface topography of fibers nor the tensile strength. Water contact angle decreased with plasma etching, as well as with acrylonitrile and acetylene plasma polymer coatings, but did not change with butadiene plasma polymer coating. FT-IR and XPS analyses revealed the presence of functional groups in plasma polymer coatings.     

Improvement of adhesion of PET fibers to rubber by argon-oxygen plasma treatment

Polyethylene terephthalate fibers cords were modified with argon, oxygen, and successive argon/oxygen cold plasmas as a function of treatment time. Plasma treated cords were coated with resorcinol formaldehyde latex, then tested as rubber reinforcing materials. The peel strength was discussed with respect to the polar component of the surface energy and the etching of the fibers. An increased adhesion of ∼ 280% was obtained with 30 min argon plasma followed by 30 min oxygen plasma, at 75 W power and 40 Pa pressure without altering the traction strength of the fibers cords. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 2321–2330, 1998     

Comparison of a-C:H films deposited from methane–argon and acetylene–argon mixtures by electron cyclotron resonance–chemical vapor deposition discharges

Hydrogenated amorphous carbon (a-C:H) films are deposited from methane–argon and acetylene–argon gas mixtures in a microwave electron cyclotron resonance plasma reactor. The films deposited with the two different gas mixtures under similar input parameter conditions have substantially different properties, including deposition rate, mass density, optical absorption coefficient, refractive index, optical bandgap and hydrogen content. The deposition parameters varied include rf-induced dc substrate bias voltage (0 to −60 V), pressure (1–5 mTorr) and argon/hydrocarbon gas flow ratio (0–1.0). The discharge properties of the two different gas mixtures, including electron temperature, ion saturation current, and residual gas composition of the exit gas flow, are measured to help explain the different deposition results from the two different gas mixtures. The use of lower pressures is found to be critical for obtaining denser, lower hydrogen content films from acetylene. For the methane-deposited films the addition of argon to the discharge increased the film's mass density and lowered the hydrogen content. In both methane- and acetylene-based deposition processes the rf-induced bias is also a critical determining factor of film properties.     

Molecular Structure of the Interphase Formed by Plasma-Polymerized Acetylene Films and Steel Substrates

The molecular structure of the interphase between plasma-polymerized acetylene films and steel substrates was determined using in situ reflection-absorption infrared spectroscopy (RAIR) and X-ray photoelectron spectroscopy (XPS). Plasma-polymerized acetylene films were deposited onto polished steel substrates using argon as a carrier gas and inductively coupled, radio frequency (RF)-powered plasma reactors that were interfaced directly to the XPS and Fourier transform infrared (FTIR) spectrometers. RAIR showed that the plasma polymerized films contained large numbers of methyl and methylene groups but only a small number of mono substituted acetylene groups, indicating that there was substantial rearrangement of the monomer molecules during plasma polymerization. Bands were observed near 1020 and 855 cm^-1 in the RAIR spectra that were attributed to skeletal stretching vibrations in C-C-O-Fe groups, indicating that the plasma-polymerized films interacted with the substrate through formation of alkoxide bonds. Another band was observed near 1565 cm^-1 and attributed to carboxylate groups in the interphase between the films and the oxidized surface of the substrate. Results obtained from XPS showed that the surface of the iron substrate consisted mostly of a mixture of Fe₂O₃ and FeOOH and that iron was mostly present in the Fe(III) oxidation state. However, during plasma polymerization of acetylene, there was a tendency for the concentration of FeOOH groups to decrease and for the concentration of Fe(II) to increase, due to the reducing nature of argon/acetylene plasmas. Results from XPS also confirmed the formation of alkoxide and carboxylate groups in the interphase during plasma polymerization of acetylene.     

Evaluation of halogenated polyimide etching for optical waveguide fabrication by using inductively coupled plasma

Oxygen plasma etching of a series of halogenated polyimides was carried out for low‐loss waveguide fabrication by using inductively coupled plasma (ICP). The effects of etching parameters such as ICP power, rf power, and O₂ flow rate on the etching rate and etching profile of polymer films were investigated. The increase in the etch rate with the ICP power and the rf power was observed. Both the vertical profile and sidewall roughness were found to be related to the ion energy (dc bias). By optimizing these parameters, a vertical profile and a smooth sidewall were obtained by 500 W of ICP power, 150 W of rf power, 5 mTorr of chamber pressure, and 40 sccm of the O₂ flow rate. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 176–182, 2001     

Improvement of paint adhesion to a polypropylene bumper by plasma treatment

Improvement of the paint adhesion to a polypropylene (PP) bumper has been investigated without using a primer by treating the bumper surface with O₂, H₂O, and acetylene plasmas. All the plasma treatments resulted in an increase of the adhesion strength in dry conditions. The adhesion strength could be increased up to a value comparable to that obtained by applying a primer. The treated surfaces were quite stable for 7 days in air. After exposure to wet conditions, however, the adhesion strengths for both O₂ and H₂O plasma-treated samples decreased significantly, while the adhesion strength for the acetylene plasma-treated sample did not change much.     

Plasma surface modification of polyimide for improving adhesion to electroless copper coatings

The influences of oxygen plasma treatment of polyimide (PI) films on the adhesion of electroless copper coatings as well as on the chemical composition of the film surface and the PI surface morphology were investigated. The plasma operating parameters were 1800 W forward power with O₂ flowing at a rate of 300 cm³/min at a pressure of 200 mTorr. The peel strength increased with decreasing plasma treatment temperature. However, extension of the treatment time at higher temperatures had a positive effect on adhesion. A correlation between the enhancement in peel strength and the content of oxygen-containing groups at the PI surface (investigated using XPS) was observed. A change in the morphology as a result of plasma etching was also observed, in the formation of pits in the film surface. The pits ranged from 3 to 6 μm in depth and the diameter varied from 10 to 200 μm. Comparison of the data obtained after plasma treatment with the results of chemical etching in alkaline solutions of permanganate showed approximately the same adhesion increase (to 0.6 kN/m) in both cases. However, chemical etching did not affect the surface morphology and increased the oxygen content at the PI surface less than the plasma treatment.     

Effects of atmospheric pressure helium/air plasma treatment on adhesion and mechanical properties of aramid fibers

In order to investigate the effect of atmospheric pressure plasmas on adhesion between aramid fibers and epoxy, aramid fibers were treated with atmospheric pressure helium/air for 15, 30 and 60 s on a capacitively-coupled device at a frequency of 5.0 kHz and He outlet pressure of 3.43 kPa. SEM analysis at 10 000× magnification showed no significant surface morphological change resulted from the plasma treatments. XPS analysis showed a decrease in carbon content and an increase in oxygen content. Deconvolution analysis of C1s, N1s and O1s peaks showed an increase in surface hydroxyl groups that can interact with epoxy resin. The microbond test showed that the plasma treatment for 60 s increased interfacial shear strength by 109% over that of the control (untreated). The atmospheric pressure plasma increased single fiber tensile strength by 16-26%.     

Plasma polymerization of tetrafluoroethylene. III. Capacitive audio frequency (10 kHz) and AC discharge

The plasma polymerization of tetrafluoroethylene (TFE) is studied in a capacitively coupled system with internal electrodes using a 10 kHz (af) and a 60 Hz (ac) source. The emphasis is on identifying conditions that are compatible with continuous coating of plasma polymer on a substrate moving through the center of the interelectrode gap. Operation at a pressure below 100 mTorr is most favorable for deposition of a substantial portion of the plasma polymer on this substrate. Plasma polymer deposited in this way is characterized by ESCA and by deposition rate data and compared to that deposited using rf power in both capacitively and inductively coupled systems. The polymers found in all systems are broadly similar and completely different from conventional poly(TFE). The distribution of power density in the various systems has been identified and compared. This is accomplished by using the known susceptibility of fluorine-containing polymers (including plasma polymer) to a high-power plasma as a probe of plasma power density within the interelectrode gap in the capacitively coupled system. The most active zone of the af or ac plasma is close to the electrode at a plasma pressure of approximately 40 mTorr. The use of a magnetic field leads to an intense localized glow such that etching by active fluorine atoms occurs at a specific locus on the electrode. By contrast, the low-pressure rf capacitively coupled glow discharge is the mildest of those investigated, and its most active zone is further from the electrode and much more diffusely localized by a magnetic field.     

Effect of Glycerol Coating on the Atmospheric Pressure Plasma Treatment of UHMWPE Fibers

In order to investigate how coatings of glycerol affects atmospheric pressure plasma treatment, ultra high molecular weight polyethylene (UHMWPE) fibers were first pretreated with 0.2 and 0.6 mol/l glycerol solutions, respectively, and then were modified by an atmospheric pressure plasma jet (APPJ) using helium as the carrier gas with a flow rate of 20 l/min, discharge power of 30 W and a radio frequency of 13.56 MHz. After the plasma treatment, scanning electron microscopy (SEM) and atomic force microscopy (AFM) analysis revealed that the glycerol coated-APPJ treated samples possessed smoother surface than the APPJ directly treated samples. The X-ray photoelectron spectroscopy (XPS) analysis indicated that the changed content of oxygen containing groups on the surface of the glycerol coated groups compared with the non-glycerol coated group was mainly due to the remaining glycerol on the fiber surfaces. The water contact angle test revealed that the wettability of the glycerol coated-APPJ treated fibers decreased slightly in comparison with the APPJ directly treated fibers. Furthermore, the microbond pull-out test indicated that the interfacial bonding of the fiber to epoxy resin decreased when the fiber was pretreated with glycerol before plasma treatment. Therefore, it was concluded that the presence of glycerol on fiber surface weakened the effectiveness of APPJ treatment of UHMWPE fibers in improving the interfacial bonding to epoxy. This was mainly attributed to the consumption of plasma energy in etching the glycerol layer on the fiber surface and a weak interfacial layer due to the presence of residual glycerol.     

Enhanced adhesion of silica for epoxy molding compounds (EMCs) by plasma polymer coatings

Silica for epoxy molding compounds (EMCs) was coated via plasma polymerization using an RF plasma (13.56 MHz) as a function of the plasma power, gas pressure, and treatment time. The monomers utilized for the plasma polymer coatings were 1,3-diaminopropane, allylamine, pyrrole, 1,2-epoxy-5-hexene, allyl mercaptan, and allyl alcohol. The EMC samples were prepared from biphenyl epoxy resin, phenol novolac, triphenyl phosphine, and plasma polymer-coated silica, and the loading of silica was controlled to 60 wt%. The EMC samples were cured at 175°C for 4 h and subjected to T_g, CTE, and water absorption measurements. The adhesion of silica to epoxy resin was evaluated by measuring the flexural strength of EMC samples and the fracture surfaces were analyzed by SEM. Plasma polymer coatings were also characterized by FT-IR and coating thickness measurements. The plasma polymer coating of silica with 1,3-diaminopropane and allylamine enhanced the flexural strength of EMC samples (167 and 165 MPa), compared with the control sample (140 MPa), and exhibited a higher T_g, a lower CTE, and lower water absorption. The enhanced properties with 1,3-diaminopropane and allylamine plasma polymer coatings can be attributed to the amine functional groups in the plasma polymer coatings.     

Characteristics of nitrogen doped diamond-like carbon thin films grown by microwave surface-wave plasma CVD

Nitrogen doped diamond-like carbon (DLC:N) thin films were deposited on p-type silicon (p-Si) and quartz substrates by microwave (MW) surface-wave plasma (SWP) chemical vapor deposition (CVD) at low temperature (< 100 °C). For films deposition, argon (Ar: 200 sccm), acetylene (C₂H₂:10 sccm) and nitrogen (N: 5 sccm) were used as carrier, source and doping gases respectively. DLC:N thin films were deposited at 1000 W microwave power where as gas composition pressures were ranged from 110 Pa to 50 Pa. Analytical methods such as X-ray photoelectron spectroscopy (XPS), UV-visible spectroscopy, FTIR and Raman spectroscopy were employed to investigate the chemical, optical and structural properties of the DLC:N films respectively. The lowest optical gap of the film was found to be 1.6 eV at 50 Pa gas composition pressure.     

Effect of Plasma-Polymerized Primers on the Durability of Aluminum/Epoxy Adhesive Bonds

The durability of aluminum/epoxy adhesive joints prepared from substrates pretreated by plasma etching and then deposition of plasma-polymerized primers was determined using the wedge crack testing method. Plasma etching and polymerization were conducted using both direct current (DC) and microwave (2.45 GHz) driven plasma systems. Plasma-polymerized primers were deposited using trimethysilane (TMS) and hexa-methyldisiloxane (HMDSO) to form siloxane-like and silica-like films, respectively. Plasma etching with argon and argon/hydrogen plasmas was used as a substrate pre-treatment. In some cases etching with an oxygen plasma was used as a post-treatment to give a silica-like surface to siloxane-like films deposited from TMS. Adhesive joints were prepared using two different epoxy adhesives, Cytec FM-300 and FM-123-2. Differences in initial adhesion were observed for primer films with chemical differences. Siloxane-like primer films were not wetted by the adhesive and resulted in poor wedge test results. Silica-like primer films were not wetted by the adhesive and resulted in poor wedge test results. Silica-like primer films deposited onto aluminum substrates resulted in wedge specimens with good adhesion and durability. The initial crack was cohesive within the adhesive. However, crack growth occurred at the interface between the adhesive and silica-like primer. Durability of the wedge specimens was essentially invariant of the type of microwave plasma pretreatment for grit-blasted aluminum substrates that were coated with silica-like primers before bonding with FM-123-2.     

Thermal imidization of poly(amic acid) on Si(100) surface modified by plasma polymerization of glycidyl methacrylate

The plasma polymerization of glycidyl methacrylate (GMA) on pristine and Ar plasma-pretreated Si(100) surfaces was carried out. The epoxide functional groups of the plasma-polymerized GMA (pp-GMA) could be preserved, to a large extent, through the control of the glow discharge parameters, such as the radio-frequency (RF) power, carrier gas flow rate, system pressure, and monomer temperature. The pp-GMA film was used as an adhesion promotion layer for the Si substrate. The polyimide (PI)/pp-GMA-Si laminates, formed by thermal imidization of the poly(amic acid) (PAA) precursor poly(pyromellitic dianhydride-co-4,4′-oxydianiline) (PMDA-ODA) on the pp-GMA-deposited Si surface (the pp-GMA-Si surface), exhibited a 180°-peel adhesion strength as high as 9.0 N/cm. This value was much higher than the negligible adhesion strength for the PI/Si laminates obtained from thermal imidization of the PAA precursor on both the pristine and the argon plasma-pretreated Si(100) surfaces. The high adhesion strength of the PI/pp-GMA-Si laminates was attributed to the synergistic effect of coupling the curing of epoxide functional groups in the pp-GMA layer with the imidization process of the PAA, and the fact that the plasma-deposited GMA chains were covalently tethered onto the Si(100) surface. The chemical composition and structure of the deposited films were characterized, respectively, by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy, while the surface morphology of the deposited films was characterized by atomic force microscopy (AFM).     

Microwave plasma-assisted etching of diamond

Experimental results are presented for the microwave plasma-assisted dry etching of ultrananocrystalline (UNCD), polycrystalline and single crystal diamond materials. A high-rate and anisotropic etching process is developed using a 2.45 GHz microwave plasma reactor. The plasma discharge in this system measures 25 cm in diameter and is located inside a 30 cm diameter microwave cavity applicator. The system is an electron cyclotron resonance (ECR) plasma source operating at pressures of 1–100 mTorr. The process chemistries include mixtures of oxygen, sulphur hexafluoride, and argon. Anisotropic etching profiles have been demonstrated and the measured etching rates range from 4–26 μm/h.     

Surface modification of spectra™-900 polyethylene fibers using RF-plasma

RF-plasma polymerization and bonding of allylamine onto ultrahigh molecular weight polyethylene (UHMWPE) “Spectra™-900” is described using an inductively coupled plasma reactor. This process was found to enhance the interfacial strength between the fibers (Spectra-900) and room-temperature-cured epoxy matrix up to fivefold. Fibers covalently coated with allylamine plasma showed no loss in tensile strength, while argon gas plasma pretreatment of the same fibers caused up to 10% reduction in tensile strength depending on the energy and duration of the treatment. Optimum treatment was attained through a short argon plasma etching (15 s), followed by allylamine polymerization and coating for 3 min. The coating process was found to protect the fiber surface from etching by plasma ion bombardment. A loss of 19% of the original diameter was found during the 15 s precoating etching with argon plasma, indicating the sensitivity of the fiber structure to plasma etching.     

远程等离子体处理对聚四氟乙烯表面的功能化改性

采用远程氩等离子体对聚四氟乙烯(PTFE)膜进行了表面改性研究,通过接触角测定仪、扫描电子显微镜(SEM)和X射线光电子能谱仪(XPS)等手段,分析研究了改性后材料表面结构、性能的变化。结果表明:PTFE表面经远程氩等离子体处理后,表面微观形态和表面化学成分均发生了变化,且处理效果优于常规氩等离子体。远程氩等离子体可以在一定程度上抑制电子、离子的刻蚀作用,强化自由基反应,使材料表面获得更好的改性效果。经远程氩等离子体短时间(100s)处理后,PTFE表面的F/C比例从1.97降至1.44,O/C比例从0.015增至0.086;表面的水接触角从108°减小到53°;表面自由能从22.4×10-5N·cm-1增加至52.3×10-5N·cm-1。