Control of structure and tack properties of acrylic pressure‐sensitive adhesives designed by a polymerization process

Free radical emulsion polymerization of methyl methacrylate (MMA) and 2‐ethylhexyl acrylate (EHA) results in the synthesis of pressure‐sensitive adhesives (PSAs) with good tack properties. Management of both the copolymer composition and the polymerization process allows one to control the behavior of the PSA. Semicontinuous (SC) processes create polymer particles whose instantaneous composition is close to that of the feed particle The SC Mixture process (continuous feeding with comonomer blends) affords nearly homogeneous latex particles and PSA films. The SC Gradient process (separate feedings at inversely varying rates) affords heterogeneous particles and films. The Batch process leads to somewhat heterogeneous films, but the hard (MMA‐rich) microdomains are made compatible with their soft (EHA‐rich) matrix because of the assumed formation of tapered‐type copolymers. Tack measurements indicate the importance of the particle and film structures. Too much hardness or softness leads to unacceptable lacks of adhesion and cohesion, respectively. Homogeneous structures prove adequate, but their tack properties collapse with rising temperature. Heterogeneous structures, with extensive phase segregation, prove unsatisfactory because they lack adhesion and cohesion. Finally, the association of well‐balanced composition and compatible heterogeneity is the criterion for suitable PSA behavior. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2749–2756, 2003     

Examination of the role of oxygen in the photografting of methacrylic acid on a polyethylene film with a mixed solvent consisting of water and organic solvents

The photografting of methacrylic acid (MAA) on a linear low‐density polyethylene film (thickness = 30 μm) under air and nitrogen atmospheres was investigated at 60°C in mixed solvents consisting of water and an organic solvent, with xanthone as a photoinitiator. The organic solvents used were acetone, methanol, tetrahydrofuran, and dioxane. A maximum percentage of grafting occurred at a certain concentration of the organic solvent in the mixed solvent. This was observed for the systems under both air and nitrogen. The grafting reaction under air exhibited an induction period, but the rate of grafting after the period was greater than that under nitrogen. The formation of poly(ethylene peroxide)s by photoirradiation seemed to be a factor for the accelerated photografting under air. On the basis of attenuated total reflection infrared spectroscopy and scanning electron microscopy of the grafted film, the MAA‐grafted chains of the sample prepared under air tended to penetrate more deeply inside the film than those of the sample prepared under nitrogen. The resulting grafted films exhibited a pH‐responsive character: the grafted films shrank in an acidic medium but swelled in alkaline medium. This was evaluated from measurements of dimensional changes in the grafted films. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 992–998, 2003     

Low surface energy films based on partially fluorinated isocyanates: the effects of curing temperature

Self-stratification strategy can be used to prepare films in which both bulk and surface properties can be optimized. By using this approach, only a very small quantity of fluorinated species is needed to generate a surface with low surface energy. When cross-linking is involved during film formation, we are dealing with a competition behavior between the diffusion of fluorinated species and the formation of cross-linked network. In this study low surface energy polymeric films were prepared on the basis of partially fluorinated polyisocyanates, in combination with hydroxyl-end-capped three-armed solventless liquid oligoesters and modified hyperbranched polyesters. At a fluorine concentration of only 0.5 wt.%, contact angles of water and hexadecane can reach 120° and 80°, respectively. A surface energy as low as 10–15 mN/m can be obtained upon the addition of less than 1 wt.% of fluorine in the films. It was shown, from real time ATR-FTIR and contact angle measurements, that the curing temperatures demonstrated significant effects on the cross-linking rate as well as on the wettability of the films.     

Block Copolymer Surface Reconstuction: A Reversible Route to Nanoporous Films

Thin films of block copolymers have been used as templates and scaffolds for the fabrication of arrays of nanostructured materials. In general, a chemical modification of the film or the removal of one of the components by photodegradative methods is required to produce a nanoporous film that serves as a template or scaffold. Here, however, the preferential interaction of one of the components with a solvent is shown to produce a reconstruction of the block copolymer film that, upon drying, leads to the generation of a nanoporous template. The area density of the pores is identical to that of the original copolymer thin film. Since no chemical reactions occurr, the process is fully reversible. Upon heating the copolymer film above its glass‐transition temperature, mobility is imparted to the copolymer and the original copolymer film with oriented domains is recovered. The film reconstruction significantly simplifies the generation of nanoporous templates.     

High temperature transport kinetics in heteroepitaxial LaFeO3 thin films

Heteroepitaxial LaFeO₃(1 1 0) thin films with a thickness of 150 nm were grown on LaAlO₃(0 0 1) by reactive sputtering in an inverted cylindrical magnetron geometry. Equilibrium conductivity was measured as a function of partial pressure of oxygen at T=1000 °C, and logσ plotted vs. logP(O₂) showed a minimum in conductivity for P(O₂)=10⁻¹¹ atm and a linear response between 10⁻¹⁰ and 1 atm. This linear response makes thin films of LaFeO₃ a promising material for oxygen sensor applications. We have also measured the time response of the film conductivity upon an abrupt change in the partial pressure of ambient oxygen from 10⁻² to 10⁻³ atm, which was determined at 60 s for T=700 °C and <3.5 s at T=1000 °C.     

Thickness-dependence of stoichiometry and microstructure characteristics in correlation with conductivity type of CdTe films

CdTe films were prepared by physical vapour deposition on a substrate at room temperature (RT) as well as on a cold (LT) one using low deposition rate. The thickness-dependence of stoichiometry revealed an abrupt decrease in the Cd/Te ratio as the thickness increases. Change of thickness did not affect the type of observed (111) crystallographic texture, only the degree of preferred orientation is enhanced as the film grows. The internal strain was negligible while the crystallite size increased rapidly at small thickness (up to 400 nm), and less thickness dependence was observed with further film growth. However, thickness dependence of lattice parameters showed a minimum and a maximum at approximately 300 nm in the case of RT and LT, respectively. The observed change in conductivity from n- to p-type and its vital correlation with the stoichiometry and structural characteristics were presented. Based on thickness dependence of stoichiometry and lattice parameters as well as the conductivity type, formation and annihilation of lattice defects were considered.     

Thermally stimulated discharge current studies in pure and fe-doped polystyrene films

Studies were made on the thermally stimulated discharge currents (TSDCs) in pure (undoped) and Fe-doped polystyrene films as a function of polarizing field, polarizing temperature and dopant concentration. While undoped films exhibited a single peak, doped films showed two peaks one at low temperatures and another at high temperatures. The low temperature peak, which exhibits a shift towards lower temperatures with increasing dopant concentration, is attributed to the relaxation of the main chain, while the high temperature peak, which shows a tendency to shift towards higher temperatures with dopant concentration, is due to space charge polarization. The TSDCs were higher for low dopant concentrations than their undoped counterparts, while for high concentrations of the dopant, the TSDCs decreased. Formation of charge transfer complexes at low dopant concentrations and molecular aggregates at higher dopant concentrations are suggested as the possible reasons for this behaviour.     

Oxygen Tracer Diffusion in Vitreous Silica

Oxygen diffusion in vitreous silica glass is studied using the gas exchange technique. The tracer concentration profiles are consistent with a model based on two mechanisms, one network and the other interstitial. These processes are coupled through limited network–interstitial exchange. Nuclear reaction analysis and secondary ion mass spectrometry techniques are performed and compared. These results are compared to experiments on transport in thin silica films grown on single-crystal silicon.     

Surface tailoring of an ethylene propylene diene elastomeric terpolymer via plasma‐polymerized coating of tetramethyldisiloxane

In the research presented here, we explore the use of a low‐energy plasma to deposit thin silicone polymer films using tetramethyldisiloxane (TMDSO) (H(CH₃)₂? Si? O? Si? (CH₃)₂H) on the surface of an ethylene propylene diene elastomeric terpolymer (EPDM) in order to enhance the surface hydrophobicity, lower the surface energy and improve the degradation/wear characteristics. The processing conditions were varied over a wide range of treatment times and discharge powers to control the physical characteristics, thickness, morphology and chemical structure of the plasma polymer films. Scanning electron microscopy (SEM) shows that pore‐free homogeneous plasma polymer thin films of granular microstructure composed of small grains are formed and that the morphology of the granular structure depends on the plasma processing conditions, such as plasma power and time of deposition. The thicknesses of the coatings were determined using SEM, which confirmed that the thicknesses of the deposited plasma‐polymer films could be precisely controlled by the plasma parameters. The kinetics of plasma‐polymer film deposition were also evaluated. Contact angle measurements of different solvent droplets on the coatings were used to calculate the surface energies of the coatings. These coatings appeared to be hydrophobic and had low surface energies. X‐ray photoelectron spectroscopy (XPS) and photoacoustic Fourier‐transform infrared (PA‐FT‐IR) spectroscopy were used to investigate the detailed chemical structures of the deposited films. The optimum plasma processing conditions to achieve the desired thin plasma polymer coatings are discussed in the light of the chemistry that takes place at the interfaces. Copyright © 2004 Society of Chemical Industry