Molecular structure of interfaces between plasma-polymerized acetylene films and steel substrates

Plasma-polymerized films of acetylene were deposited onto steel substrates in an inductively coupled reactor by exciting the plasma in an argon carrier gas and then injecting the monomer into the afterglow region. The molecular structure of the film/substrate interface was determined using reflection–absorption infrared spectroscopy (RAIR) and X-ray photoelectron spectroscopy (XPS) to characterize the films as a function of thickness. RAIR showed that thick (∼ 900 Å) as-deposited plasma-polymerized acetylene films had a complicated molecular structure and contained methyl and methylene, mono- and disubstituted acetylene, vinyl, and cis- and trans-disubstituted olefin groups. Evidence of oxidation resulting from the reaction of trapped radicals with atmospheric oxygen and moisture to form O—H and C=O groups was also obtained. The molecular structure of thin films (∼ 60 Å) was similar although evidence was obtained to indicate that acetylide groups (H—C≡C⁻) were present at the film/substrate interface. Results obtained using angle-resolved XPS analysis showed that carbonaceous contamination was removed from the substrate and that oxides and hydroxides on the substrate surface, especially FeOOH, were chemically reduced during deposition of the films. XPS also confirmed that plasma-polymerized acetylene films deposited on steel substrates contained groups. Preliminary results also showed that films deposited in an inductively coupled reactor were good primers for rubber-to-metal bonding, whereas films deposited in a capacitively coupled reactor were not. The differences may be due to the wide variety of functional groups found in the former type of films but not in the latter. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 1283–1298, 1998     

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.     

Adhesion and Scratch Resistance of Polycarbonate Films on Ferroplate Substrates: Effect of γ-APS Primers

The influence of γ-aminopropyltriethoxysilane (γ-APS) primers on the adhesion and scratch resistance of polycarbonate (PC) films on ferroplate substrates was determined from the critical normal loads at which debonding of the films from the substrates occurred during scratch testing. The critical load was a strong function of the concentration of the aqueous solutions from which the γ-APS primers were adsorbed and of the thickness of the primer films. Thus, the critical normal load increased from 0.09 ± 0.02 N to 0.31 ± 0.07 N as the concentration of the γ-APS solutions increased from 0.05% to 0.2%, respectively. However, the critical load increased only slightly as the solution concentration increased beyond 0.2%. The increase in critical load as concentration of γ-APS solutions increased was related to the formation of an interphase involving chemical reaction and physical entanglement of PC and γ-APS molecules. The critical load for debonding of PC films from the substrates also depended strongly on the temperature at which the γ-APS films were dried before application of the PC films. Thus, the critical normal loads for debonding were 0.31 ± 0.07, 0.20 ± 0.02, and 0.05 ± 0.01 N for γ-APS films that were dried for 15 min at room temperature, 60°C, or 110°C, respectively. The decrease in critical load with increasing drying temperature was attributed to the greater cross-link density in γ-APS films that were dried at elevated temperatures, which limited interdiffusion and physical entanglement of PC and γ-APS molecules. High reaction temperature of γ-APS and PC induced a fragmentation of amine. However, it also increased the probability of amines to react with carbonate because of increasing mobility of PC chains. Optimization of these two factors was required to obtain the greatest adhesion and scratch resistance. Chemical reactions occurring between PC films and γ-APS primers were investigated by reflection-absorption infrared spectroscopy (RAIR) and X-ray photoelectron spectroscopy (XPS) using diphenyl carbonate (DPC) as a model compound. The carbonyl absorption band of neat DPC was observed at 1780 cm^-1. However, two carbonyl bands were observed at 1738 and 1652 cm^-1 in RAIR spectra of γ-APS films that were reacted with DPC and were assigned to urethane and urea groups, respectively. XPS results revealed that urethane was the main reaction product between DPC and γ-APS. It was concluded that urethane groups formed by the reaction of PC with γ-APS were responsible for adhesion and scratch resistance of PC to ferroplate substrates that were primed with γ-APS.     

Chemical Reactions Between Model Rubber Systems and Plasma Polymerized Acetylene Films. Part A: XPS, AES and SIMS Investigations

Chemical reactions between natural rubber (NR) and plasma-polymerized acetylene films were investigated using model systems in which natural rubber was replaced by the unsaturated compound squalene (C₃₀H₅₀) or its saturated analogue, squalane (C₃₀H₆₂). Analysis of plasma-polymerized acetylene films on steel substrates before and after reaction with model rubber systems was accomplished using X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS), and Auger electron spectroscopy (AES). The importance of unsaturation in the model rubber compound was demonstrated by comparing the results for the two model systems. For the squalene-based model rubber system, the results obtained were consistent with a model in which components of the curing system reacted with both squalene and the plasma-polymerized acetylene film to form a relatively large number of polysulfidic pendant groups. In the early stages of the reaction, pendant groups were probably terminated by cobalt ions since sulfides were detected by XPS and AES. Pendant groups were probably terminated by zinc ions in the later stages of the reaction. The pendant groups dispro-portionated to form a relatively large number of mono-, di-, and tri-sulfidic crosslinks between the model rubber compound and the plasma polymerized primer. In the squalane-based model rubber system, components of the curing system reacted with the plasma-polymerized acetylene film to a small extent to form a few relatively long polysulfidic pendant groups. However, there was little evidence for reaction of the curing system with squalane and for crosslinking between squalane and the plasma polymerized primer.     

Determination of the Molecular Structure of Interphases Between Epoxy/4,4'-Diaminodiphenylsulfone Adhesives and Silver Substrates Using SERS and XPS

The molecular structure of interphases formed by curing an epoxy/4,4'-diaminodiphenylsulfone (DADPS) adhesive against rough silver substrates was determined using surface-enhanced Raman scattering (SERS) and x-ray photoelectron spectroscopy (XPS). SERS spectra obtained from the adhesive deposited onto silver island films were very similar to SERS spectra obtained from the DADPS curing agent spun onto silver island films, indicating that DADPS in the adhesive system segregated to the interphase and was preferentially adsorbed onto the silver substrate. Differences in the relative intensity of several bands in the normal Raman and SERS spectra of DADPS were observed. For example, the band near 1603 cm^-1 was stronger in SERS spectra of DADPS than in normal Raman spectra. The band near 1150 cm^-1 was weaker in SERS spectra of DADPS than in normal Raman spectra. These results implied that DADPS was adsorbed through one of the NH groups with an end-on conformation. Consistent results were also obtained from XPS spectra. C(ls) spectra of the adhesive and silver fracture surfaces of specimens prepared by curing the adhesive against silver substrates were more similar to the C(ls) spectra of DADPS than to those of the bulk adhesive. These results confirmed the preferential adsorption of DADPS onto the silver substrate from the adhesive system. The similarity of the C(ls) spectra obtained from adhesive and silver fracture surfaces indicated that a thin DADPS-rich interphase was formed between the bulk adhesive and the silver substrate and that the locus of failure was partially within this layer. However, less nitrogen and sulfur were detected on the silver fracture surface than on the adhesive fracture surface. A large amount of silver was observed on the substrate fracture surface and a trace was found on the adhesive fracture surface. These results indicated that failure of the adhesive joints was within the interphase but near the silver substrate. No evidence of chemisorption of DADPS onto the substrate was observed.     

Surface modification of polyimide films via plasma polymerization and deposition of allylpentafluorobenzene

Plasma polymerization of allylpentafluorobenzene (APFB) on the plasma-pretreated polyimide (PI) films was carried out. The fluorinated aromatic groups of the plasma-polymerized APFB (pp-APFB) could be preserved, to a large extent, by controlling the glow discharge parameters. The effect of the glow discharge parameters, including the type of the carrier gas and the input RF power, on the surface composition and chemical structure of the pp-APFB films were studied by X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and time-of-flight secondary ion mass spectrometry. The surface topography of the APFB plasma-polymerized PI (pp-APFB-PI) films was studied by atomic force microscopy. For plasma polymerization carried out at a high RF power and using argon as the carrier gas, an ultra-hydrophobic pp-APFB-PI surface was also obtained. The ultra-hydrophobic surface exhibited advancing/receding water contact angles (θ_A/θ_R) of 174°/135°. The effectiveness of the carrier gas in defluorinating the pp-APFB films followed the order of O₂>N₂>H₂>Ar. Thus, the role of the carrier gas in improving the surface hydrophobicity of the resulting pp-APFB-PI films followed the order of O₂22® tape adhesion test.     

Surface-Enhanced Raman Scattering As an In-Situ Probe of Polyimide/Silver Interphases

The molecular structure of interphases formed by chemically curing the polyamic acid of pyromellitic dianhydride (PMDA) and oxydianiline (ODA) against meta-aminothiophenol (m-ATP)-primed silver substrates was determined using surface-enhanced Raman scattering (SERS) and reflection-absorption infrared spectroscopy (RAIR). It was found that m-ATP was adsorbed dissociatively onto silver substrates through the sulfur atoms. When polyamic acid was deposited onto silver substrates pretreated with m-ATP, acid groups of the polyamic acid combined with amino groups of m-ATP to form ammonium carboxylate salts near the interphase. SERS and RAIR results indicated that the structure of the interphase was significantly different from that of the bulk polymer. Chemical curing of the polyamic acids located in the interphase was suppressed because of the formation of ammonium carboxylate salts. However, the bulk of the polyamic acid films was highly cured to form polyimide. It was also found that more isoimide groups were formed when thin polyamic acid films were chemically cured in acetic anhydride/pyridine solutions than in acetic anhydride/triethylamine solutions.     

ELECTROLESS PLATING OF GLASS AND SILICON SUBSTRATES THROUGH SURFACE PRETREATMENTS INVOLVING PLASMA-POLYMERIZATION AND GRAFTING PROCESSES

Electroless plating of nickel (or copper) was carried out on glass (or silicon) substrates that were previously surface modified by using plasma-polymerization and grafting processes, and then activated by immersion in a simple acidic PdCl₂ solution. Three pretreatments based on the deposition of plasma-polymerized thin films (PACVD process) on O₂ plasma-cleaned substrates were investigated. They include film deposition of (1) amorphous hydrogenated carbon (a-C:H) grown from CH₄, whose surface is subsequently plasma-functionalized in NH₃ or N₂; (2) amorphous hydrogenated carbon nitride (a-CN_x:H) grown from CH₄/NH₃ or CH₄/N₂ mixtures; and (3) amorphous hydrogenated carbon nitride grown from volatile organic precursors (allylamine, acetonitrile).

In the three cases, X-ray photoelectron spectroscopy (XPS) results show that chemisorption of the catalyst occurs on the nitrogen-containing functionalities created by plasma polymerization and grafting and thus that the electroless deposition is possible. Differences were observed depending on the nature and thickness of the plasma-polymerized thin films, as well as on the nature and concentration of the nitrogen-containing functionalities present or grafted at the surface. Practical adhesion of Ni films was investigated using a Scotch® tape test. Ni films up to 3 or 4 μm in thickness were shown to pass this test successfully, i.e., without causing any metal detachment.     

Adhesion of Injection Molded PVC to Steel Substrates

Interactions occurring at the interface between injection-molded poly (vinyl chloride) (PVC) and steel substrates that were coated with thin films of aminosilanes were investigated by X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FTIR). The silane films were formed by adsorption of γ-aminopropyltriethoxysilane (γ-APS) or N-(2-aminoethyl-3-aminopropyl)trimethoxysilane (γ-AEAPS) from 2% aqueous solutions onto polished steel substrates. PVC was injection molded onto the silane-primed steel substrates and annealed at temperatures up to 170°C for times as long as 30 min. PVC was peeled off of the primed steel substrates using a 90° peel test and the substrate failure surfaces were thoroughly rinsed with tetrahydrofuran (THF) and distilled water to remove PVC and other compounds that were not strongly bonded to the substrates. The PVC failure surfaces were characterized by attenuated total reflection infrared spectroscopy (ATR) and PVC rinsed off of the substrate failure surfaces was characterized by transmission infrared spectroscopy. The resulting transmission and ATR spectra showed an absorption band near 1650 cm^-1 that was attributed to unsaturation in PVC. The substrate failure surfaces were characterized by XPS; curve-fitting of N(1s) and Cl(2p) high-resolution spectra showed the formation of amine hydrochloride complexes by protonation of amino groups of the silanes with HCl that was liberated from PVC during the onset of thermal dehydrochlorination. Furthermore, quaternization or nucleophilic substitution of labile pendent allylic chloride groups by amino groups on the silanes took place, thus grafting PVC onto the aminosilanes. It was determined that PVC that had β-chloroallyl groupings along its chains showed better adhesion with steel primed with aminosilanes and that generation of allylic chloride groups in PVC chains was the rate-limiting step in the reaction between PVC and aminosilane. Moreover, the effect of crosslinking of silane films on adhesion between PVC and aminosilane primed steel was investigated and it was concluded that interdiffusion of the polymer phase and the silane phase was also critical in obtaining good adhesion.     

Titania Coatings on Polyethylene Terephthalate: Adhesion and XPS Studies

Titania coatings have been deposited on polyethylene terephtalate (PET) by the r.f. magnetron sputtering method in an oxygen-argon plasma from a titanium target and in a pure argon plasma from a titania target.

The dependence of the structural properties and the composition of the deposited films on the sputtering pressure and the r.f. power have been studied. In order to improve the adhesion strength between the titanium oxide films and their substrate, various cold plasmas are used to treat the polymer surface. These treatments' influence on the adhesion is studied by using the fragmentation test. The best results are obtained with a carbon dioxide plasma. The adhesion of the titania coating on the PET film also depends strongly on the deposition conditions. The highest values are reached when the titanium oxide films are deposited by the reactive sputtering process and when the elaboration parameters combine a total pressure as low as 0.8 Pa and a power density of 2.54 W cm^-2. The titania/PET interface, investigated by XPS, suggests the formation of Ti-O-C bonds in the first stage of the deposition of the titania films obtained by the reactive magnetron sputtering process, while no chemical reaction seems to occur between the PET and the titanium oxide film sputtered under a pure argon plasma.     

Molecular Structure of Polymer/Metal Interphases

The molecular structure of interphases in aluminum/epoxy and steel/epoxy adhesive joints was characterized using infrared spectroscopy. In one series of experiments, adhesive joints were prepared by curing beams of epoxy against aluminum or steel substrates. When the joints were cooled to room temperature, the residual stresses were sufficient for crack propagation along the interface. The adhesive and substrate failure surfaces were then analyzed with reflection-absorption infrared spectroscopy (RAIR), attenuated total reflection infrared spectroscopy (ATR) and X-ray photo-electron spectroscopy (XPS). When an epoxy/anhydride adhesive was cured against aluminum substrates primed with an aminosilane coupling agent, amide and imide groups were formed in the interphase. Chemical reaction between the primary amine of the primer and the anhydride of the curing agent precluded chemical bridge formation between the primer and adhesive. Metal cations from the 2024 aluminum substrate reacted with the anhydride to form carboxylate salts on the surface. When an epoxy/tertiary amine adhesive was cured against steel substrates, evidence of oxidation of the primary amine to imine was observed in the interphase.     

Molecular Structure of Polymer/Metal Interphases

The molecular structure of interphases in aluminum/epoxy and steel/epoxy adhesive joints was characterized using infrared spectroscopy. In one series of experiments, adhesive joints were prepared by curing beams of epoxy against aluminum or steel substrates. When the joints were cooled to room temperature, the residual stresses were sufficient for crack propagation along the interface. The adhesive and substrate failure surfaces were then analyzed with reflection-absorption infrared spectroscopy (RAIR), attenuated total reflection infrared spectroscopy (ATR) and X-ray photo-electron spectroscopy (XPS). When an epoxy/anhydride adhesive was cured against aluminum substrates primed with an aminosilane coupling agent, amide and imide groups were formed in the interphase. Chemical reaction between the primary amine of the primer and the anhydride of the curing agent precluded chemical bridge formation between the primer and adhesive. Metal cations from the 2024 aluminum substrate reacted with the anhydride to form carboxylate salts on the surface. When an epoxy/tertiary amine adhesive was cured against steel substrates, evidence of oxidation of the primary amine to imine was observed in the interphase.     

Interaction of Epoxy/Dicyandiamide Adhesives with Metal Substrates

The molecular structure of the interphase formed by curing a model adhesive system consisting of the diglycidyl ether of bisphenol-A (DGEBA) and dicyandiamide (DDA) against mechanically polished aluminum and electrogalvanized steel (EGS) substrates was determined using reflection-absorption infrared spectroscopy (RAIR) and X-ray photoelectron spectroscopy (XPS). RAIR analysis suggested that DGEBA/DDA mixtures created an interphase with a different molecular structure from the bulk of the adhesive when cured in contact with aluminum. The formation of this unique interphase was mainly due to interactions between DDA and the Al surface. XPS analysis indicated that aluminum ions exposed by heating the substrate surface were necessary for this interaction. DDA was found to adsorb onto the aluminum surface via the lone pair of electrons on the nitrogen atoms of the nitrile groups. A slight decrease in the nitrile stretching frequency suggested an additional back-bonding interaction between aluminum ions and the nitrile groups. Slight back donation of electrons from the metal to DDA resulted in a reduction product that led to the formation of the carbodiimide form of DDA. This specific reaction caused a decrease in the concentration of nitrile groups in the interphase and changed the extent of the reaction between DDA and DGEBA by inhibiting the formation of oxazolidine structures. The interaction of DDA with EGS surfaces followed a similar trend. However, the effects were much more pronounced with EGS and the extent of the curing reaction and the cross-linking rate near the metal surface were strongly affected by EGS/DDA interactions.     

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.     

Interaction of Epoxy/Dicyandiamide Adhesives with Metal Substrates

The molecular structure of the interphase formed by curing a model adhesive system consisting of the diglycidyl ether of bisphenol-A (DGEBA) and dicyandiamide (DDA) against mechanically polished aluminum and electrogalvanized steel (EGS) substrates was determined using reflection–absorption infrared spectroscopy (RAIR) and X-ray photoelectron spectroscopy (XPS). RAIR analysis suggested that DGEBA/DDA mixtures created an interphase with a different molecular structure from the bulk of the adhesive when cured in contact with aluminum. The formation of this unique interphase was mainly due to interactions between DDA and the Al surface. XPS analysis indicated that aluminum ions exposed by heating the substrate surface were necessary for this interaction. DDA was found to adsorb onto the aluminum surface via the lone pair of electrons on the nitrogen atoms of the nitrile groups. A slight decrease in the nitrile stretching frequency suggested an additional back-bonding interaction between aluminum ions and the nitrile groups. Slight back donation of electrons from the metal to DDA resulted in a reduction product that led to the formation of the carbodiimide form of DDA. This specific reaction caused a decrease in the concentration of nitrile groups in the interphase and changed the extent of the reaction between DDA and DGEBA by inhibiting the formation of oxazolidine structures. The interaction of DDA with EGS surfaces followed a similar trend. However, the effects were much more pronounced with EGS and the extent of the curing reaction and the cross-linking rate near the metal surface were strongly affected by EGS/DDA interactions.     

Molecular Structure of Interphases Between DGEBA/BTDA Adhesives and Silver Substrates Using Surface-Enhanced Raman Scattering

Surface-enhanced Raman scattering (SERS) was used for the non-destructive characterization of interphases between epoxy/anhydride adhesive systems and silver substrates. The normal raman spectrum of benzophenone tetracarboxylic dianhydride (BTDA) was characterized by strong bands near 1785 and 1860 cm^-1 that were assigned to the anhydride groups, a strong band near 1690 cm^-1 that was assigned to the benzophenone C─O stretching mode, and by a strong band near 1620 cm^-1 that was attributed to vibration v(8b) of the benzene rings. The bands due to v(8b) and to the benzophenone C─O stretching mode were prominent in the SERS spectrum of BTDA but the bands related to the anhydride group were missing, indicating that the anhydride groups were hydrolyzed at the silver surface to form carboxylate groups. A band related to a CH out-of-plane bending mode which was absent from the normal Raman spectrum of BTDA was strong in the SERS spectrum, indicating that the molecules were adsorbed onto silver with a flat configuration. SERS spectra obtained from a diglycidyl ether of bisphenol-A (DGEBA) epoxy cured against a silver substrate using BTDA as the curing agent were identical to SERS spectra of BTDA and were independent of the epoxy/BTDA ratio, indicating that the spectra were characteristic of the interface rather than the bulk adhesive and that BTDA was preferentially adsorbed onto the silver substrate. SERS spectra obtained from thin films of BTDA adsorbed onto silver and then overcoated with thick films of epoxy were identical to the spectrum of BTDA and showed no evidence of bands related to DGEBA, supporting the conclusion that the SERS spectrum obtained from the DGEBA/BTDA adhesive was characteristic of the interfacial region.     

Modification of Si(100) surface by plasma-enhanced graft polymerization of allylpentafluorobenzene

Abstract - Hydrophobic fluoropolymer thin films were deposited on Si(100) substrates by plasma polymerization of allylpentafluorobenzene (APFB) under different glow discharge conditions, and in the presence and absence of Ar plasma pre-activation of the substrate surfaces. The FTIR and X-ray photoelectron spectroscopy (XPS) results suggested that the plasma polymerization proceeded mainly through the C=C bond of APFB, and the fluorinated aromatic structure in the deposited polymer films was preserved to different extents, depending on the radio-frequency (RF) power used for plasma polymerization. The use of a low RF power (~5 W) readily resulted in the deposition of thin films having nearly the same fluorinated aromatic structure as that of the APFB homopolymer. For the plasma-polymerized APFB (pp-APFB) films deposited on the Ar plasma-preactivated Si(100) surfaces, solvent extraction results suggested that the pp-APFB films became covalently tethered onto the silicon substrate surfaces. Thermogravimetric (TG) analysis results indicated that the thermal stability of the pp-APFB films had been enhanced substantially after annealing at 270°C in a vacuum oven.     

Oxidative graft polymerization of aniline on Si(100) surface modified by plasma polymerization of glycidyl methacrylate

Modification of argon plasma-pretreated Si(100) surfaces via plasma polymerization of glycidyl methacrylate(GMA), followed by reactive coupling of the epoxide groups of the plasma deposited GMA chains with aniline, and finally by oxidative graft polymerization of aniline was carried out. An alternative approach involved the modification of the argon plasma-pretreated Si(100) surfaces via plasma polymerization of glycidyl methacrylate(GMA), followed by direct oxidative graft polymerization of aniline and thermal curing. The compositions and chemical states of the modified Si surfaces were characterized by X-ray photoelectron spectroscopy (XPS). The two methods of surface modification of the Si(100) surfaces produced similar results. The protonation-deprotonation behavior, the interconvertible intrinsic redox states, and the metal reduction behavior (the electroless plating of Pd from the Pd(II) ion solution) of the grafted polyaniline (PANI) chains on the Si(100) surface were grossly similar to those of the PANI homopolymer. The coupling of PANI to the covalently tethered GMA chains on the Si(100) surface was suggested by the cohesive failure inside the epoxy adhesive that was applied to the modified Si surface in an attempt to peel off the PANI layer from the GMA plasma-polymerized Si (GMA-pp-Si) substrate.     

Infrared Spectroscopy of Interphases Between Model Rubber Compounds and Plasma Polymerized Acetylene Films

Thin (～ 750 Å) plasma polymerized films of acetylene deposited onto polished steel substrates are promising primers for rubber-to-metal bonding. The as-deposited films contained mono- and di-substituted acetylene groups, aromatic groups, and groups such as carbonyl which apparently resulted from reaction of residual free radicals with oxygen when the films were exposed to the atmosphere. There was some evidence for formation of acetylides in the interphase between the films and the substrates. Reactions occurring in the interphase between the plasma polymerized films and natural rubber were simulated using a model “rubber” consisting of a mixture of squalene, zinc oxide, carbon black, sulfur, stearic acid, diaryl-p-diphenyleneamine, and N, N-dicyclohexyl-benzothiazole sulfenamide (DCBS). It was found that zinc oxide reacted with stearic acid to form zinc stearate in the interphase between squalene and the plasma polymerized acetylene primer. Zinc stearate reacted with DCBS and sulfur to form an accelerator complex and zinc perthiomercaptides. The perthiomercaptides reacted with squalene and the plasma polymer to form pendant groups which eventually reacted to form crosslinks between squalene and the primer. In the absence of cobalt naphthenate, the formation of pendant groups and eventually crosslinks was relatively slow and the length of the sulfur chains in the crosslinks and the pendant groups was relatively long. When cobalt naphthenate was added to the model “rubber,” the reactions in the interphase between squalene and the plasma polymerized film occurred much faster and the length of the crosslinks and the pendant groups was much shorter.     

Plasma treatment of automotive steel for corrosion protection – a dry energetic process for coatings

In the thrust of pursuing new environmentally friendly technology for automotive application, a new corrosion protection coating system for automotive steel has been developed through interface engineering affected by an energetic plasma process. The plasma treated coating system outperformed the current phosphated galvanized steel system in scab corrosion tests. In the plasma process, the steel substrate was subjected to plasma cleaning and in situ plasma polymerization deposition. Plasma of a mixture of argon and hydrogen was created to remove the surface contaminants and the inherent oxide layer. A very thin film (50–100 nm) was then deposited by a plasma generated from alkylsilanes (e.g. trimethylsilane (TMS)). The interface can be so designed that strong corrosion-resistant interfacial bonds such as Fe–Si, Fe–C, and Si–C can be obtained. The interfacial chemistry involved in the plasma process and corrosion reaction are characterized by reflection absorption infrared spectroscopy (RAIR), X-ray photoelectron spectroscopy (XPS), and sputter neutral mass spectroscopy (SNMS).