Effect of trifunctional cross-linker triallyl isocyanurate (TAIC) on the surface morphology and viscoelasticity of the acrylic emulsion pressure-sensitive adhesives

Acrylic pressure sensitive adhesive (PSA) latexes were synthesized via a starved monomer-seeded semi-continuous emulsion polymerization process with butyl acrylate (BA), methyl methacrylate, acrylic acid (AA), 2-hydroxyethyl acrylate and trifunctional cross-linker, triallyl isocyanurate (TAIC). Influences of TAIC on the resultant latex and PSA properties were comprehensively investigated. The results indicated that latex particle size was independent of the amount of TAIC in the pre-emulsion feed, while the viscosity of the latex increased remarkably with TAIC content increased. Thermal gravimetric analysis result showed that the thermal stability of the polymers was improved significantly with the addition of TAIC. Besides, with the increase in TAIC content, gel content of the polymer increased significantly, while molecular weight between cross link points (M_c) and sol molecular weight (M_w, M_n) of the polymer decreased remarkably. Moreover, for the cross-linked adhesive film, the shear strength was improved greatly while at the sacrifice of loop tack and peel strength, when compared with the uncrosslinked counterparts. Finally, dynamic mechanical analysis and atomic force microscopy were also used to evaluate the viscoelastic properties and surface morphology of the acrylic emulsion PSA film, respectively.     

Spin coating of thin and ultrathin polymer films

The spin coating of thin (> 200 nm thick) and ultrathin (< 200 nm thick) polymer films is examined in several solvents of varying volatility over a broad range of polymer solution concentrations and spin speeds. Experimentally measured film thicknesses are compared with a simple model proposed by Bornside, Macosko, and Scriven, which predicts film thickness based on the initial properties of the polymer solution, solvent, and spin speed. This model is found to predict film thickness values within 10% over the entire range of conditions explored, which gave film thicknesses from 10 nm to 33 μ:m. The model underpredicts film thickness for cases in which a very volatile solvent is used or the initial concentration of polymer is high, while overpredicting film thickness for cases in which a low volatility solvent is used or the initial polymer concentration is very low. These deviations are a consequence of how the model decouples fluid flow and solvent evaporation.     

Investigation of high-density polyethylene film surface treated with chromic acid mixture by use of 2,4-dinitrophenylhydrazine

High-density polyethylene films were treated with chromic acid mixture. 2,4-Dinitrophenylhydrazine was reacted on the treated films. The changes in amounts of 2,4-dinitrophenylhydrazones formed in the films were inferred by comparing the absorptions in the ultraviolet spectra. The changes in the film surfaces by chromic acid mixture treatment were investigated by comparing the changes in the amount of the hydrazones with changes in water wettability of the treated films. Scanning electron micrographs of the treated film surfaces were taken. Oxidation of the film surface zone, partial breakdown of polymer in the film surface zone, and oxidation of surface zone bared from the film inner zone seem to have occurred with increase in treatment time. When the treatment temperature was raised, the increase in carbonyl groups in the surface of the high-density polyethylene film with rise in treatment temperature seems to have been prevented by an increase in partial breakdown of polymer in the film surface.     

Adsorption of disulfide-modified polyacrylamides to gold and silver surfaces as cushions for polymer-supported lipid bilayers

Inclusion of a polymer cushion between a lipid bilayer membrane and solid surface has been suggested as a means to provide a soft, deformable layer that will allow for transmembrane protein insertion and mobility. In this study, we evaluate the properties of a disulfide- and lipid-modified polyacrylamide polymer cushion. High molecular weight random copolymers with various degrees of disulfide and lipid substitution were synthesized. X-ray photoelectron spectroscopy (XPS) was used to determine quantitatively the percentage of disulfide groups bound to gold and silver surfaces. A quartz crystal microbalance with dissipation (QCM-D) was used to study the adsorption process and resulting film properties in situ. The presence of backbone-surface interactions leads to a competition between physisorption of the acrylamide backbone and chemisorption of the disulfide side-chains. This competition limits the degree of chemisorption to gold and silver surfaces. For a polyacrylamide with 10 mol% disulfide side-chains, 78% of the side-chains covalently bind to silver and only 41% bind to gold. The undesired physisorption of the acrylamide backbone leads to adsorption of the homopolymer itself. In addition, film thicknesses, as indicated by both XPS and QCM-D, are limited to 15-30 Å. The QCM-D results for all films indicate the formation of relatively rigid films, rather than the soft, deformable films desired for a lipid membrane polymer cushion.     

Fluorination of epoxy surfaces by a physical method

To enhance the surface hydrophobicity of epoxy polymers, a simple physical method for the simultaneous surface fluorination during curing of epoxy resins was proposed and evaluated. Curing of epoxy resins against a polytetrafluoroethylene (PTFE) mold gave rise to fluorinated epoxy polymer surfaces due to the anchorage of PTFE molecules on the epoxy polymer surface. The modified epoxy surfaces were characterized using contact‐angle measurements and X‐ray photoelectron spectroscopy (XPS). The fluorinated epoxy resin surfaces are highly hydrophobic, exhibiting contact angles of similar magnitude to that of the pristine PTFE film surface. The PTFE mold can be used repeatedly to give fluorinated epoxy surfaces with large contact angles. Aging and solvent extraction tests indicated that the fluorinated epoxy surfaces were very stable. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 296–304, 2000     

Reactive processing of thermoset/thermoplastic blends: A potential for injection molding

Poly(2,6-dimethyl-1,4-phenylene ether) (PPE) is an engineering plastic with high heat distortion temperature. Melt processing of neat PPE is usually accompanied with thermal degradation. The degradation problem is solved by blending with polystyrene to reduce the processing temperature. We propose an alternative using triallylisocyanurate (TAIC). TAIC is a low viscosity liquid that can be cured by peroxide, e.g. α,α′-bis(t-butylperoxy-m-isopropyl)benzene (PBP), to provide a thermoset. The PPE/TAIC mixture was shown to have the upper critical solution temperature (UCST) type phase behavior. At the single-phase regime above UCST and below the cure temperature (∼180°C for PBP), the mixture had a low viscosity, less viscous than a conventional thermoplastic such as PC and PP. That is, a nice window for injection molding was available, e.g., at 100°C to 160°C for a 50/50 blend. After injecting into a hot mold set at cure temperature, the blend cured in a short time (∼80% conversion in 5 min). Then the molded and partly cured material kept its shape and dimensions during post-cure in a hot chamber at higher temperature (e.g. 250°C). Using transmission electron microscopy and dynamic mechanical analyses, it was shown that the cured blend had a bicontinuous two-phase structure with periodic spacings of ∼30 nm, suggesting a structure formation via a spinodal decomposition driven by the increase in molecular weight of TAIC during cure. The cured material showed excellent flexural strength and high chemical resistance.     

Moisture absorption into ultrathin hydrophilic polymer films on different substrate surfaces

Moisture absorption into ultrathin poly(vinyl pyrrolidone) (PVP) films with varying thickness was examined using X-ray reflectivity (XR) and quartz crystal microbalance (QCM) measurements. Two different surfaces were used for the substrate: a hydrophilic silicon oxide (SiO_x) and a hydrophobic hexamethyldisilazane (HMDS) treated silicon oxide surface. The total equilibrium moisture absorption (solubility) was insensitive to the surface treatment in the thickest films (≈150 nm). However, strong reductions in the equilibrium uptake with decreasing PVP film thickness were observed on the HMDS surfaces, while the SiO_x surface exhibited thickness independent equilibrium absorption. The decreased absorption with decreasing film thickness is attributed a depletion layer of water near the polymer/HMDS interface, arising from hydrophobic interactions between the surface and water. The diffusivity of water decreased when the film thickness was less than 60 nm, independent of the surface treatment. Changes in the properties of ultrathin polymer films occur even in plasticized films containing nearly 50% water.     

Migration of PVC plasticizers into alcohols

The use of labelled plasticizers and radioactivity measurements in conjunction with weight loss, can give quantitative information on the amount of migrated plasticizer, and on the amount of the liquid medium that diffuses into the polymer during the migration process. In the case of PVC plasticized with dibutyl phthalate and dioctyl phthalate and immersed in alcohols, the specimens soon become heterogeneous due to loss in compatibility between the polymer and the mixtures of plasticizer-alcohol high in alcohol. These mixtures are formed in the polymer as a result of continuous migration and diffusion processes. The following factors affecting the migration process were examined: nature of alcohol, nature of phthalate plasticizer, amount of plasticizer, molecular weight of polymer, thickness of specimens, presence of epoxy plasticizers, plasticization process, presence of stabilizers, temperature, and time.     

Relationship between particle size and photochromic characteristics of tungsten oxide films prepared by electric current heating method using tungsten wire

Tungsten oxide films were deposited on glass substrates placed above tungsten wires heated by electric current in air. The film thickness in a region just above the wire (region A) was thinner than that in other region (region B). The observation using scanning electron microscope revealed that the films consisted of particles. The shapes of the particles were sphere in the region A while smaller octahedron shape was found in the region B. The amount of the particles in the region B was greater than that in A. The ratio of the number of small particles with a diameter ≤500 nm to the total particle number in the region A increased with decreasing applied voltage during the electric current heating, whereas, in the region B, the size of particles was ≤500 nm and had no applied voltage dependence. The films exhibited photochromism; the reflectance in the near-infrared region was decreased by the ultraviolet irradiation. In region A, the photochromic effects increased with decreasing applied voltage to the wire. On the other hand, in region B, the photochromic effects did not show the applied voltage dependence. Consequently, it was found that the obtained films showed positive correlation between photochromic effect and the ratio of the number of small particles (≤500 nm) to the total particle number. The particles in region B are suitable for mass production of the photochromic material because the photochromic effect and the amount of particles in region B are greater than those in A.     

Preparation and characterization of thin organosilicon films deposited on SPR chip

The paper reports on the preparation and characterization of organosilicon thin polymer films deposited on glass slides coated with 5 nm adhesion layer of titanium and 50 nm of gold. The polymer was obtained by the decomposition of 1,1,3,3-tetramethyldisiloxane precursor (TMDSO) premixed with oxygen induced in a N₂ plasma afterglow using remote plasma-enhanced chemical vapor deposition (PECVD) technique. The film thickness was controlled by laser interferometry and was 9 nm. The chemical stability of the gold substrate coated with the organosilicon polymer film (p-TMDSO) was studied in different acidic and basic solutions (pH 1-14). While the gold/polymer interface showed a high stability in acidic media, the film was almost completely removed in basic solutions. The resulting surfaces were characterized using atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), water contact angle measurements, cyclic voltammetry, and surface plasmon resonance (SPR).     

Cyclophosphazene-containing Polymers as Imprint Lithography Resists

We present the evaluation of a cyclophosphazene-containing polymer as a patternable resist for imprint lithography. Hexamethacryloxybutoxycyclotriphosphazene layers containing small amounts of photoinitiator can be applied to silicon wafers substrates by spin coating techniques and cured photochemically to give tough, network polymer thin films. The films were characterized by FT-IR. Thin films approximately 200 nm in thickness were subjected to anisotropic O₂ and CF₄ plasmas and the etch rates were determined. The polymer films etch at a rate of 21 Å/s in CF₄ plasma, and as low as 1.6 Å/s in O₂ plasma, which is comparable or lower than the rates observed with commercially available silicon-containing photoresists. The surface chemical composition was surveyed by X-ray photoelectron spectroscopy, which gave results consistent with the formation of an etch resistant phosphorus-rich layer during reaction with O₂ plasma. The polymer was processed by nano-contact molding imprint lithography and replicated 200 nm period test patterns. This report is the first demonstration of a cyclophosphazene-containing polymer as a resist candidate for high-resolution lithography.     

Velocity and Temperature Gradient Boundary Layer Formation During a Continuum Drawing in a Polymer Melt Chamber

This paper presents a boundary layer model for the velocity and temperature gradient on the introduction of a continuum (wire, strip, tube, etc.) in a melt bath of polymer positioned before the plasto-hydrodynamic pressure unit prior to drawing or coating. Results are presented for the boundary layer thicknesses of velocity and temperature at different wire velocities. Also, the friction factor and Nusselt number have been given for polymer melt at different continuum velocities. The velocity and temperature gradient boundary layer thickness are also discussed in relation to the quality of hydrodynamic coating of wire.     

Multicomponent vapor deposition polymerization of poly(methyl methacrylate) in an axisymmetric vacuum reactor

An axisymmetric, multicomponent initiated chemical vapor deposition (i-CVD) apparatus was designed to study the vapor-phase growth of glassy poly(methyl methacrylate) (PMMA) films. Preheated monomer (methyl methacrylate) and initiator (t-butyl peroxide) vapors were metered into a pressure-controlled reaction chamber. Inside the chamber, gases pass through a high-temperature hot-zone where primary free radicals are formed. The gas mixture then condenses and polymerizes on a back-cooled target substrate. Key reactor operating parameters were systematically varied to understand film growth kinetics. These include the hot-zone temperature, reactor base-pressure, substrate temperature, and the monomer/initiator molar feed ratio. Polymer deposition requires good thermal contact between feed gases and the hot-zone. Packed with glass beads, the hot-zone reactor resulted in more efficient initiation and film growth. Experiments also show that polymer deposition rate is limited by thermal initiation of primary free radicals, transport of primary free radicals to the target substrate, and by monomer adsorption. Size exclusion chromatography of deposited polymers is used to relate molecular weight to the monomer-to-initiator feed ratio. The addition of a third vapor component, 1-butanol, was also found to affect polymer molecular weight.     

Graft polymerization of vinyl acetate onto starch. Saponification to starch–g–poly(vinyl alcohol)

Graft polymerizations of vinyl acetate onto granular corn starch were initiated by cobalt-60 irradiation of starch-monomer-water mixtures, and ungrafted poly(vinylacetate) was separated from the graft copolymer by benzene extraction. Conversions of monomer to polymer were quantitative at a radiation dose of 1.0 Mrad. However, over half of the polymer was present as ungrafted poly-(vinyl acetate) (grafting efficiency less than 50%), and the graft copolymer contained only 34% grafted synthetic polymer (34% add-on). Lower irradiation doses produced lower conversions of monomer to polymer and gave graft copolymers with lower % add-on. Addition of minor amounts of acrylamide, methyl acrylate, and methacrylic acid as comonomers produced only small increases in % add-on and grafting efficiency. However, grafting efficiency was increased to 70% when a monomer mixture containing about 10% methyl methacrylate was used. Grafting efficiency could be increased to over 90% if the graft polymerization of vinyl acetate-methyl methacrylate was carried out near 0°C, although conversion of monomers to polymer was low and grafted polymer contained 40-50% poly(methyl methacrylate). Selected graft copolymers were treated with methanolic sodium hydroxide to convert starch–g–poly(vinyl acetate) to starch–g–poly(vinyl alcohol). The molecular weight of the poly(vinyl alcohol) moiety was about 30,000. The solubility of starch–g–poly(vinyl alcohol) in hot water was less than 50%; however, solubility could be increased by substituting either acid-modified or hypochlorite-oxidized starch for unmodified starch in the graft polymerization reaction. Vinyl acetate was also graft polymerized onto acid-modified starch which had been dispersed and partially solubilized by heating in water. A total irradiation dose of either 1.0 or 0.5 Mrad gave starch–g–poly(vinyl acetate) with about 35% add-on, and a grafting efficiency of about 40% was obtained. A film cast from a starch–g–poly(vinyl alcohol) copolymer in which homopolymer was not removed exhibited a higher ultimate tensile strength than a comparable physical mixture of starch and poly(vinyl alcohol).     

Inhibition of thin polystyrene film dewetting via phase separation

By addition of a small amount of poly(methyl methacrylate) (PMMA) into polystyrene (PS), we present a novel approach to inhibit the dewetting process of thin PS film through phase separation of the off-critical polymer mixture (PS/PMMA). Owing to the preferential segregation of PMMA to the solid SiO_x substrate, a nanometer thick layer, rich in PMMA phase, is formed. It is this diffusive PMMA-rich phase layer near the substrate that alters the dewetting behavior of the PS film. The degree of inhibition of dewetting depends on the concentration and molecular weight of PMMA component. PMMA with low (15.9k) and intermediate (102.7k) molecular weight stabilizes the films more effectively than that with a higher molecular weight (387k).     

Polymerization of alkyl acrylates and alkyl methacrylates with starch

A series of C₄-C₁₂ alkyl acrylates and methacrylates was polymerized with starch by irradiating starch–monomer mixtures with ⁶⁰Co. Homopolymers were extracted with cyclohexane. The amounts of insoluble versus soluble synthetic polymer in polymerization run with alkyl acrylates varied less with the chain length of the alkyl substuent than in the polymerizations run with alkyl acrylates varied less with the chain length of the alkyl substituent than in the polymerizations run with alkyl methacrylates; and the poly(alkyl acrylate) contents of cyclohexane-insoluble fractions were all in the 38–45% range. Synthetic polymer contents of the products from butyl, hexyl, and decyl methacrylates were also close to this range. Octyl and lauryl methacrylate, however, gave high conversions to cyclohexane-soluble poly(alkyl methacrylate) along with little or no unextractable synthetic polymer in the starch-containing fractions. Poly(lauryl methacrylate) could be rendered insoluble by incorporating a small amount of tetramethylene glycol dimethacrylate in the polymerization mixture. In a series of polymerizations run with hexyl acrylate and hexyl methacrylate, lower irradiation doses led to more cyclohexane-soluble polymer and less synthetic polymer in the starch-containing fractions. Enzymatic digestion of starch-soluble polymer and less synthetic polymer in the starch-containing fractions. Enzymatic digestion of starch-containing polymers gave synthetic polymer fractions that were largely insoluble in cyclohexane. Crosslinking is, therefore, probably taking place during these polymerizations; however, we could not eliminate the possibility that reduced solubility was caused by small amounts of residual carbohydrate in these polymer fractions. Ceric ammonium nitrate-initiated polymerizations of butyl acrylate, hexyl acrylate, and butyl methacrylate with starch gave cyclohexane-insoluble polymers that contained 33–39% synthetic polymer. The higher alkyl acrylates and methacrylates produced little or no polymer under these conditions. Starch-containing fractions were tested as absorbents for hydrocarbons. Products prepared from decyl acrylate and lauryl acryle acrylate absorbed about 9 g of isooctane per 1 g of polymer, whereas the lowrer alkyl monomers gave polymers with lower absorbency.     

Synthesis of acrylate polymers by a novel emulsion polymerization for adhesive applications

Pressure‐sensitive adhesives (PSAs) are viscoelastic–elastomeric materials that can adhere strongly to solid surfaces with light contact pressure and a short contact time. Polyacrylates produced by solution polymerization are used widely because of their good adhesive properties. A novel emulsion polymerization was established to improve the low physical properties of PSA on the basis of conventional poly(n‐butyl acrylate) (PBA) by emulsion polymerization. PBA latex was synthesized by the emulsion polymerization of 50 wt % n‐butyl acrylate mixed with 15 wt % ethyl acetate (EA) with Emal‐10P and Emulgen‐920 as anionic and nonionic surfactants, respectively, at 70°C. Potassium persulfate (KPS) or a combination of KPS and dicumyl peroxide (DCP) was used as the initiator. The KPS/DCP system gave a very high‐molecular‐weight PBA of a narrow molecular weight distribution with a weight‐average molecular weight/number‐average molecular weight value of 1.01–1.03 in 15 min. The PSA tape was prepared by the casting of the PSA latex onto a corona poly(ethylene terephthalate) film as an adherent to obtain a 50‐μm‐dry‐thickness film. The PSA tape produced from PBA by the novel emulsion polymerization showed better adhesive properties, such as 180° peel adhesion, shear holding power, and rolling ball tack tests according to JIS and ASTM standards, than PSA tape produced from solution polymerization. The occlusion of a small amount of EA in emulsion particles before polymerization was found to give higher properties than those of PBA prepared by the addition of EA to the PBA latex after polymerization. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100:413–421, 2006     

Layer-by-Layer Self-Assembled Redox Polyelectrolytes on Passive Steel

Steel samples were passivated in 0.1 M NaOH solutions at 0.3 V vs. Ag/AgCl (3 M KCl) and then poly(allylamine) derivatized with osmium pyridine-bipyridine-chloride complex and poly-(vinylsulfonate) were sequentially self-assembled electrostatically layer-by-layer. The resulting electrodes were examined by cyclic voltammetry, ellipsometry, and X-ray Photoelectron Spectroscopy (XPS). These studies demonstrate the formation of a redox polyelectrolyte multilayer onto the passive film protecting the ferrous metal. As the number of deposited polyelectrolyte layers increases there is an increase in the measured thickness of the self-assembled film. The rate of thickness growth in osmium polymer film with the number of deposition cycles is slower for films thinner than ∼30 nm. Cyclic voltammetry shows that the electron transfer rate to the outer sphere osmium complex tethered to the polymer backbone is much slower for the multilayer on passive iron than on gold surfaces. This is in agreement with the well-known behavior of soluble redox couples on passive metals and with electrochemical tunelling spectroscopy.     

Thermogelling of highly branched poly(N‐isopropylacrylamide)

Highly branched poly(N‐isopropylacrylamide) (PNIPAM) has been synthesized by a reversible addition‐fragmentation chain transfer (RAFT) copolymerization of NIPAM and a vinyl contained trithiocarbonate RAFT agent. ¹H‐NMR measurements revealed that the degrees of branch (DB) are in the range of 0.032–0.105. Laser light scattering (LLS) measurements gave the hydrodynamic radii (R_h) of the polymers to be 3.6–5.7 nm with molecular weight in the range of 1.3 × 10⁴ g/mol–2.3 × 10^?4 g/mol. Highly branched PNIPAM with terminal thiol groups were obtained by aminolysis the polymers, and the product can be oxidized by air to form disulfide bonds (? S? S? ) among chains and resulting in the formation of nanoparticle in aqueous solution. Interestingly, the nanoparticle in size of R_h ? 80 nm showed a thermogelling behavior to form bulk hydrogel when the temperature was increased up to 25°C due to the thermo‐induced association of the PNIPAM chains among the nanoparticles. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Aspects of interactions in complex polymer coating formulations

Acid–base interaction parameters have been measured by inverse gas chromatography for mixed stationary phases of film‐forming polymers and pigments. The quantities of adsorbed polymer required fully to coat the pigment surfaces were established, and rheological measurements were used to evaluate the thickness of polymer barriers generated by the adsorption process. Both the barrier thickness and the critical amount of polymer needed to overcoat the pigments were found to be dependent on acid–base interactions. Acid–base considerations also determined the rate of material redistribution when a third component was added to premixtures of two‐component polymer/pigment combinations. Time‐dependent variations in the surface energies of polymer films were attributed to the component redistribution process. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1378–1386, 2000