Polymer Surface Layer Research Articles

Control of Specific Attachment of Proteins by Adsorption of Polymer Layers

This study concerns the design of protein-resistant polymer adsorbed layers for the control of surface binding of biospecific recognition entities. Polymer surface layers were prepared using the adsorption of poly(allylamine hydrochloride) (PAH), poly(l-lysine) (PL), and branched and linear polyethyleneimine (PEI) and further modified by the covalent attachment of biotin for specific avidin attachment. The adsorption of PAH, PL, and PEI on silicon substrates was studied as a function of pH and ionic strength using ellipsometry. Average dry layer thicknesses of approximately 10, approximately 5, approximately 9, and approximately 3 A (+/-1 A) were obtained when polymer adsorption occurred from solutions at pH 9.5 that contained 0.5 M NaCl for PAH, PL, branched PEI, and linear PEI, respectively. These polymers showed significant differences in their efficiency to suppress nonspecific avidin adsorption. At low ionic strength, avidin adsorption occurred on all polymer-coated surfaces at basic pH values, despite the same positive electrostatic charge for protein globules and the surface. Though the net electrostatic repulsion between avidin molecules and branched PEI was efficiently screened in a protein solution of pH 7 and 0.15 M NaCl, branched-PEI coatings of high molecular weight were unique in their ability to provide avidin-resistant surfaces as a result of steric hindrance from the branched architecture of adsorbed polymer chains. All polymers studied were effective in suppressing avidin adsorption at pH 3 as a result of protonation of the avidin surface functional groups at this pH. Branched-PEI-coated surfaces were also effective for the suppression of smaller positively charged proteins such as lysozyme and ribonuclease A at pH 7 and 0.15 M NaCl. They were also resistant to the adsorption of negatively charged proteins such as BSA and fibrinogen at pH 7 and 0.75 M NaCl. Furthermore, by using PEI-modified protein-repellent surfaces, selective binding of avidin was achieved to surface-bound silver nanoparticles, which should provide a promising application for the label-free detection of biological species using surface-enhanced Raman scattering (SERS).

Morphology of the surface layer of polymers modified by gaseous fluorine

A change in the surface structure of low-density polyethylene films upon chemical modification by gaseous fluorine has been studied by scanning electron microcopy and X-ray spectral analysis. It has been demonstrated that this treatment leads to formation of the wavy surface; its characteristics depend on the method of polymer synthesis and the initial structure of the test sample. A possible mechanism for structural changes in the surface layer of the polymer during fluorination is considered. It is suggested that the molar volume and the configuration of polymer macromolecules change in the course of replacement of hydrogen atoms with fluorine atoms. Mathematical modeling has been performed for the formation of the fluorinated layer with due regard for chemical transformations of macromolecules and structural heterogeneity of the polymers. The isosurfaces of the polymer with various degrees of fluorination calculated within the framework of the above model indicate that the fluorinated layer being formed is characterized by unequal thickness due to different rates of fluorine diffusion in amorphous and crystalline regions. It has been shown that the degree of fluorination of the polymer is dependent on the duration of treatment. This relationship is in satisfactory agreement with the previous experimental data.

Evaluation of piezoelectric PVDF polymers for use in space environments. III. Comparison of the effects of vacuum UV and gamma radiation

AbstractFilms of piezoelectric PVDF and P(VDF‐TrFE) were exposed to vacuum UV (115–300 nm VUV) and γ‐radiation to investigate how these two forms of radiation affect the chemical, morphological, and piezoelectric properties of the polymers. The extent of crosslinking was almost identical in both polymers after γ‐irradiation, but surprisingly, was significantly higher for the TrFE copolymer after VUV‐irradiation. Changes in the melting behavior were also more significant in the TrFE copolymer after VUV‐irradiation due to both surface and bulk crosslinking, compared with only surface crosslinking for the PVDF films. The piezoelectric properties (measured using d33 piezoelectric coefficients and D‐E hysteresis loops) were unchanged in the PVDF homopolymer, while the TrFE copolymer exhibited more narrow D‐E loops after exposure to either γ‐ or VUV‐radiation. The more severe damage to the TrFE copolymer in comparison with the PVDF homopolymer after VUV‐irradiation is explained by different energy deposition characteristics. The short wavelength, highly energetic photons are undoubtedly absorbed in the surface layers of both polymers, and we propose that while the longer wavelength components of the VUV‐radiation are absorbed by the bulk of the TrFE copolymer causing crosslinking, they are transmitted harmlessly in the PVDF homopolymer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3253–3264, 2006

Relaxation Processes in Polymer Surface Layers

AbstractA recently built and patented device Nanoluminograph is used for the investigation of the relaxation processes in the surface layers of HDPE films, produced at various conditions. The work of the device is based on the phenomenon of radiothermoluminescence. The use of high‐frequency low‐power, low‐temperature plasma as an ionizing source, and a reduction of the consumed energy down to several orders of magnitude (as compared to that used in similar devices) provides excitation of a surface layer as thin as 100–200 nm. The high sensitivity of the device enables one to reduce the excitation time to 1–2 seconds for obtaining a sufficient intensity of glow curves even from ultrathin layers 20–30 nm thick. All of that minimizes the modifying plasma action on the samples under investigation and provides well reproducible and reliable data. It is found that the intensity, number and positions of peaks on the glow curves are strongly influenced by the preparation conditions of polymer films. The complicated profile of glow curve peaks allows one to assume the overlapping of multiple relaxation processes. Decomposing and fitting peak profiles with the help of a PEAKFIT computer program result in revealing at least 4 relaxation transitions in the temperature region from 109 to 213 K. The temperatures and activation energies of relaxation transitions in surface layers appeared to be lower than those inferred from the DSC data for the bulk polymer. The activation energies of trap depletion upon heating are calculated. The nature of traps is discussed in terms of molecular conformations, morphology and structural defects, as well as the attribution of the observed relaxation transitions to defreezing mobility of different kinetic units.

The structure and properties of polymer-metallic coating interphase

The structure of the surface layer in polymers (LDPE and PET) decorated with a thin metal (gold and platinum) layer was studied after their deformation under different conditions. It was found that relatively thick coatings debonded from the polymer substrate during tensile drawing. Debonding was observed at low tensile strains (below 20–30%). During the further drawing of a polymer, a regular microrelief typical of deformable “rigid coating on a soft substrate” systems appeared on its surface. This phenomenon is explained by the fact that the debonding metal coating uncovers not the surface of the pure polymer but a certain modified layer, which has a higher elastic modulus than the pure polymer. The formation of this layer is associated with the inclusion of metal atoms into the polymer during the metal decoration by plasma immersion ion deposition. As a result of this inclusion, a modified layer, which has a higher glass transition temperature, a higher elastic modulus, and other mechanical properties, is formed between the coating and the polymer.

Layer-by-Layer Nanocoating of Lignocellulose Fibers for Enhanced Paper Properties

The systematic modification of the surface charge of lignocellulose fibers was performed with a polyelectrolyte layer-by-layer (LbL) nanocoating process to produce negatively and positively charged fibers. The fibers were coated with 20-50 nm thick polymer surface layers which subsequently increased interaction between the fibers during paper formation. The modified fibers were added to standard fibers at varying proportions to produce paper with corresponding variation in properties such as strength and electrical conductivity. Paper strength was doubled by manipulating the surface charge and coating thickness of the LbL-treated pulp fibers. It is demonstrated that the LbL coating process increased the fiber interactions and that these interactions enhanced the paper properties. This process, when applied to a simulated sample of recycle grade of fibers, produce paper with an increase in tear strength as compared with untreated fiber paper. Nanocoating fibers with polythiophene/polyallylamine multilayers produced marginally conductive pulp and paper. Paper electrical conductivity was proportional to the number of the bilayers deposited.

Aspects of bond layer role in concrete repairs

The paper presents the role of a bond layer in the repair process of concrete and reinforced concrete elements as well as the place of its laying. For the purpose of a detailed analysis of the above problems two series of tests were carried out. In the first series of the tests, the influence of the state of the surface under repair (wet, oiled) on the adhesion of the bond layer is taken into account. In the second series, the influence of surface modification, grade of concrete and the placement of layers on the adhesion of bond layer to the surface was tested. It was shown that the use of a proposed polymer surface layer was possible both on wet and oil-contaminated surfaces. It was also proved that the adhesion of levelling layer (polymer–cement filler) to concrete is lower after sandblasting. The usage of the levelling layer under the polymer bond layer weakens their adhesion.

Modification of surface properties of high and low density polyethylene by Ar plasma discharge

Structural changes induced by Ar plasma discharge in low and high density polyethylene (LDPE and HDPE) were studied by different techniques. AFM and SEM methods were used to determine surface morphology, the changes in chemical structure were followed using FTIR and UV–vis spectroscopy. The content and the depth profile of incorporated oxygen was determined by RBS method. The degree of polymer ablation was determined gravimetrically. Standard goniometry was used to determine contact angle and to follow aging of plasma modified polymer. As a result of plasma treatment a lamellar structure or spherulites appear on the surface of HDPE and LDPE, respectively. Pronounced increase of the surface roughness is observed on HDPE contrary to LDPE. Plasma treatment for 400 s leads to the ablation of the surface layer of about 0.6 and 1 μm thick for LDPE and HDPE, respectively. Plasma treatment results in oxidation of the polymer surface layer which is more pronounced in HDPE. Concentration maximum of incorporated oxygen lies 25 nm beneath the sample surface in both polymer types. After exposure to plasma discharge carbonyl, carboxyl and amide groups were detected in the polymer surface layer together with C C bonds either in aromatic or in aliphatic structures. Immediately after the plasma treatment strong decline of the contact angle is observed, the decline being larger in HDPE. Later, in aged specimens the contact angle increases rapidly. The increase, which may be due to rearrangement of degraded structures, is stronger in the specimens exposed to plasma for longer times.

Tailoring of the PS surface with low energy ions: Relevance to growth and adhesion of noble metals

Ion–polymer interaction induces different phenomena in the near surface layer of polymers, and promotes its adhesion to metals. Using XPS, TEM and AFM, polystyrene surface was examined after 1keV ion-beam treatments with oxygen, nitrogen and argon ions in the ion fluence range from 1012 to 1016cm−2 to clarify the following points: chemical reaction after treatment in vacuum and after exposure to air, identification of adsorption-relevant species for metal atoms, formation of cross-links in the outermost polymer layer. The early stages of metal–polymer interface formation during metallization play a crucial role in the metal–polymer adhesion. Therefore, the influence of the ion fluence and ion chemistry on the condensation of noble metals, film growth and peel strength were measured. The peel strength showed a maximum at a certain fluence depending on ion chemistry. For example, the surface treatment with very low fluence of oxygen ions improved the adhesion between copper and polystyrene by two orders of magnitude without significantly increasing the surface roughness measured with AFM. The locus of failure changed at the same time from interfacial failure for untreated polymer surfaces to cohesive failure in the polymer for modified surfaces. A multilayer model of the metal–polymer interface after ion treatment is suggested.

Metal Nanoparticles on Polymer Surfaces: 5. Catalytic Activity of Colloidal Platinum Films Incorporated in Polystyrene Surface Layer

The fundamental possibility to enlarge Pt nanoparticles in monolayer ensembles formed on polystyrene surfaces by the adsorption from hydrosol in solution of isopropanol and K2PtCl4 is demonstrated for the first time. The enlargement of “seeding” nanoparticles is performed after their preliminary incorporation (partial embedding) into the polymer surface layer by the annealing of a system within the range between “surface” and “bulk” glass transition temperatures of polystyrene. It is shown that a colloidal film of metallic platinum with a thickness up to 200 nm is formed in the course of enlargement and it is mechanically fixed in the polymer surface layer. Such a system exhibits, over a long time, high catalytic activity in the model reaction of methyl viologen reduction with hydrogen.

Thermal and Fluctuation-Induced Deformations of Chemical Bonds in Surface and Boundary Layers of Polymers

The deformation of chemical bonds in polymer molecules of surface layers of samples, boundary layers between supramolecular aggregates, and boundary layers between polymers and solids in polymer composites is investigated using IR and Raman spectroscopy. It is found that the chemical bonds are elongated on a free surface and in boundary layers between supramolecular aggregates. By contrast, the chemical bonds are contracted in boundary layers between polymers and solids. The concentration and the strain of excited chemical bonds (strained to approximately a theoretical ultimate elongation) are increased on the free surface and in the boundary layers between supramolecular aggregates, whereas the concentration and the strain of excited chemical bonds in the boundary layers between polymers and solids are decreased. These effects are explained by the changes in the atomic vibrations in the surface and boundary layers.

Structure and composition of the surface layer in polymers modified by elemental fluorine

AbstractA model is proposed for the layered structure of a polymer surface modified by elemental fluorine mixed with helium. The composition of the modified surface layer has been determined, and the thermodynamic compatibility of the surface layer, transition layer, and unmodified bulk of the polymer has been studied. The thickness of the modified layers has been calculated as a function of the fluorination conditions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 897–902, 2005

Ultrathin Binary Grafted Polymer Layers with Switchable Morphology

Polymer surface layers comprised of mixed chains grafted to a functionalized silicon surface with a total layer thickness of only 1-3 nm are shown to exhibit reversible switching of their structure. Carboxylic acid-terminated polystyrene (PS) and poly (butyl acrylate) (PBA) were chemically attached to a silicon surface that was modified with an epoxysilane self-assembled monolayer by a "grafting to" routine. While one-step grafting resulted in large, submicron microstructures, a refined, two-step sequential grafting procedure allowed for extremely small spatial dimensions of PS and PBA domains. By adjusting the grafting parameters, such as concentration of each phase and molecular weight, very finely structured surfaces resulted with roughly 10-nm phase domains and less than 0.5-nm roughness. Combining the glassy PS and the rubbery PBA, we implemented a design approach to fabricate a mixed brush from two immiscible polymers so that switching of the surface nanomechanical properties is possible. Post-grafting hydrolysis converted PBA to poly(acrylic acid) to amplify this switching in surface wettability. Preliminary tribological studies showed a difference in wear behavior of glassy and rubbery surface layers. Such switchable coatings have practical applications as surface modifications of complex nanoscale electronic devices and sensors, which is why we restricted total thickness for potential nanoscale gaps.

Impact fracture toughness of polyethylene/polypropylene multilayers

AbstractIn a number of applications, a brittle polymeric surface layer is deliberately molded onto a tough substrate for decorative or protective purposes. This can increase the susceptibility of the tough polymer to premature failure. Similar problems arise when a surface layer becomes embrittled by environmental effects. Choosing a surface material that has good mechanical properties without having this effect can be difficult. In this work the fracture resistances of two polyethylenes and an ethylene/propylene copolymer, and of symmetrical two‐component multilayers of these polymers, were determined as a function of temperature, using instrumented impact tests. The law of mixtures accounts adequately for the fracture resistance of multilayer structures where there is no mechanical interaction between skin and core. However, it gave misleading results for a structure in which high skin modulus at low temperatures appeared to influence the fracture resistance of the core through a constraint effect. Polym. Eng. Sci. 44:1627–1635, 2004. © 2004 Society of Plastics Engineers.

The study of polystyrene surface layer glass transition by luminescent molecular probes

Producing of 2D ensembles of nanoparticles on polymer substrates is one of the key tasks in many fields of fundamental research and practical applications. A successful development of such nanocomposites is impossible without an intimate knowledge of polymer surface layer properties at a nanolevel. The glass transition process in a thin surface layer of polystyrene was studied in the present work by the method of luminescent molecular probes. A significant difference of polymer “surface” ( T g s) and “bulk” ( T b g) glass transition temperatures was proven. A strong dependence on the polymer molecular weight was found for the T g s value and probe dye molecules' mobility.

Vapor-Phase Polymerization of 3,4-Ethylenedioxythiophene: A Route to Highly Conducting Polymer Surface Layers

A new synthetic route to poly-3,4-ethylenedioxythiophene (PEDT) with a conductivity exceeding 1000 S/cm is described. The method is based on base-inhibited vapor-phase polymerization, where a surface covered with ferric p-toluenesulfonate as oxidant mixed with a volatile base (pyridine) is exposed to 3,4-ethylenedioxythiophene (EDT) vapors. The base is added to suppress an acid-initiated polymerization of EDT, leading to a product with little or no conjugation. The product of the base-inhibited vapor-phase polymerization is confirmed to be virtually identical to PEDT obtained by wet chemical oxidation by both spectroscopic and electrochemical methods. A possible reaction scheme for the acid-initiated polymerization is discussed.

Plasma protein adsorption to surfaces grafted with dense homopolymer and copolymer brushes containing poly(N-isopropylacrylamide)

Growing polymer chains from surface initiators in principle allows much more dense polymer surface layers to be created than can be produced by grafting of whole (self-excluding) chains. We have utilized aqueous atom transfer radical polymerization to graft a series of cleavable hydrophilic poly(N-isopropylacrylamide) (PNIPAM) homopolymers and block copolymers of substituted acrylamides from polystyrene latex to give brushes of controlled MW and surface density. Average chain separations much less than their free solution radii of gyration have been achieved. Exposure to radiolabeled single proteins or to whole plasma and subsequent analysis by SDS-PAGE shows that PNIPAM brushes decrease protein adsorption relative to the latex surface or other substituted polyacrylamides. The PNIPAM brushes exhibit a second-order phase transition around 30°C as reflected by a decrease in the hydrodynamic thickness of the brush at higher temperatures. Total plasma protein adsorption is increased at 40°C compared to 20°C but there is significant differential adsorption behavior among the proteins detected by gel-electrophoresis analysis.

Tailoring of the morphology and chemical composition of thin organosilane microwave plasma polymer layers on metal substrates

The growth of thin microwave organosilicon plasma polymers on model zinc surfaces was investigated as a function of the film thickness and the oxygen partial pressure during film deposition. The evolution of the topology of the film was studied by atomic force microscopy (AFM). The nano- and micro-roughness was investigated at the inner and the outer surfaces of the plasma polymers. A special etching procedure was developed to reveal the underside of the plasma polymer and thereby its inner surface. Rough films contained voids at the interface, which reduced the polymer/metal contact area. The increase in oxygen partial pressure led to a smoother film growth with a perfect imitation of the substrate topography at the interface. The chemical structure of the films was determined by infrared reflection absorption spectroscopy (IRRAS), X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectroscopy (ToF-SIMS). ToF-SIMS at the outer and the inner surface of the plasma polymers showed that the density of methylsilyl groups increases in the outer surface layer of the plasma polymer and depends on the oxygen partial pressure. The chemical composition of the films could be altered to pure SiO 2 without changing the morphology by using oxygen-plasma post-treatment. This was proved by means of IRRAS and AFM. Chemistry and topology of the films were correlated with the apparent water contact angle. It was found that a linear relationship exists between the nanoscopic roughness of the plasma polymer and the static contact angle of water. Superposition of a nanoscopic roughness of the metal surface and the nanoscopic roughness of methylsilyl-rich films led to ultra-hydrophobic films with water contact angles up to 160°.

Electrophoretic Mobility and Electric Conductivity in Dilute Suspensions of Charge-Regulating Composite Spheres

The electrophoresis and electric conduction in a dilute suspension of charged composite particles, each composed of a solid core and a surrounding porous shell, with an arbitrary thickness of the electric double layers are analytically studied. The porous shell of a particle is treated as a solvent-permeable, ion-penetrable, and charge-regulating surface polymer layer of finite thickness with uniformly distributed ionogenic functional groups and frictional segments. The electrokinetic equations that govern the electrostatic potential profile, the electrochemical potential distributions of ionic species, and the fluid flow field inside and outside the surface polymer layer of the particle migrating in an unbounded electrolyte solution are linearized assuming that the system is only slightly distorted from equilibrium. Through the use of a regular perturbation method, these linearized equations are solved for a composite sphere in a uniform applied electric field with the dimensionless fixed charge densities on the surface of the rigid core and of the surface polymer layer as the small perturbation parameters. Analytical expressions for the electrophoretic mobility of the charge-regulating composite sphere and for the effective electric conductivity of the suspension are derived as linear functions of these charge densities. The results demonstrate that the charge regulation phenomenon tends to thin down the electric double layer and to reduce the magnitudes of the electrophoretic mobility and the electric conductivity compared to the case that the fixed charge density in the surface polymer layer is a constant. The intensity of this effect depends on the regulation characteristics such as the association/dissociation equilibrium constants of the ionogenic functional groups in the surface polymer layer and the concentration of the potential-determining ions in the bulk solution.

Investigation on NIR, coating mechanism of PS-b-PAA coated calcium carbonate particulate

Particulate calcium carbonate is treated by polystyrene (PS)/polyacrylic acid (PAA) block copolymer with varied amount. Coating efficiency is obtained by measuring the dissolve curve. The results of near-infrared (NIR) analysis reveal the thickness and structural information of the surface polymer layer. The alignment of PS-b-PAA chain on and the interaction of carboxyl with the calcite surface are deduced on the basis of X-ray photoelectron spectroscopy (XPS) results.