Temperature influence on the physicochemical surface properties and adhesion behaviour of Enterococcus faecalis to glass and silicone

The interest in studies on the physicochemical surface properties of bacteria has increased because they are related to the causes of the initial adhesion of microorganisms to biomaterials and the subsequent biofilm formation on indwelling medical devices. The determination of physicochemical parameters such as hydrophobicity or surface tension is usually done at room temperature, not taking into account the real temperature at which bacteria cause infection inside the human body. In this work, the influence of the experimental temperature on the surface physicochemical characteristics and adhesion behaviour of Enterococcus faecalis ATCC29212 to glass and silicone has been studied. Water, formamide and diiodomethane contact angles on bacterial lawns changed when the experimental temperature was increased from 22°C to 37°C. Moreover, hydrophobicity, as determined by water contact angle, increases with temperature, in agreement with the higher and lower adhesion to silicone and glass, respectively, observed at 37°C, with respect to the results at 22°C. Also, when the formamide and diiodomethane contact angles are considered, the changes in the adhesion behaviour to glass and silicone are predicted by the sum of Lifshitz-van der Waals and acid-base interaction free energies if the measurement temperature is the same as the bacterial growth temperature, i.e. 37°C.     

Tissue adhesive using synthetic model adhesive proteins inspired by the marine mussel

The surface free energy and its dispersion and polar components of pigskin were determined by wettability measurements. The contact angles and work of adhesion of solutions of the synthetic model adhesive sequence poly(Gly-Tyr-Lys) inspired by marine adhesive proteins were measured on the epidermis and the dermis of pigskin. Also the surface free energy of pigskin was determined using contact angles of certain probe liquids. When a poly(Gly-Tyr-Lys) buffer solution containing tyrosinase as a bioadhesion formulation was used to close an incision of a living pig, a good incision adhesion and reduced immunological response after 1 week were observed from photographs using an optical microscope and the amount of macrophages by image analysis.     

Hydrophilic/electron-acceptor surface properties of metallic biomaterials and their effect on osteoblast cell activity

Mice osteoblast cells were cultured on samples of 316L stainless steel and titanium alloy (Ti-6Al-4V) with different surface treatments. The resulting cell differentiation was correlated with the solid surface tension and electron-acceptor surface tension parameter of the biomaterial samples. Both of these characteristics were determined through contact angle measurements, using the Lifshitz–van der Waals/Lewis acid–base interaction model. Before calculating the surface tension of the biomaterials, the experimental contact angles were corrected for the effect of roughness using the Wenzel equation. For this calculation, the roughness characteristics of the solid surfaces were determined using atomic force microscopy and interferometric profilometry at the nano-scale and micro-scale, respectively. It was found that osteoblast cell differentiation directly related to the implant surface tension and electron-acceptor properties. The alkaline phosphatase activity increased both with increasing surface tension and increasing electron-acceptor surface tension parameter of the implant materials. These results suggest that the formation of surface hydroxyl groups with acidic character gives rise to enhanced attachment of osteoblast cells.     

Surface characterization and adhesion of black-oxide-coated copper substrate: effect of surface hardening processes

The effects of surface-hardening processes on the changes in surface characteristics and adhesion of black copper oxide substrate with epoxy resins are studied. Various techniques, namely SEM, XPS, AFM, XRD, Auger electron spectroscopy, contact angle goniometry, D-SIMS and RBS, were used to identify the changes in surface characteristics. Dense, fibrillar cupric oxide crystals characterized the as-deposited oxide coating with high surface roughness. The surface-hardening process flattened and consolidated the fibrils without changing the compositional and thermodynamic characteristics of the coated surface. The surface-hardening process reduced the total thickness of copper oxide by approximately 50–150 nm. The reduction in oxide thickness was not a predominant factor for the reduced bond strength of the surface-hardened coating. The bond strengths of both the as-deposited and surface-hardened black oxide coatings increased with oxidation time, until saturation at about 120–150 s. For the as-deposited oxide coating, mechanical interlocking, high wettability and resistance to surface contamination are the three major sources for improved adhesion, amongst which the enhanced mechanical interlocking provided by the fibrillar cupric oxide is the most important. Surface hardening reduced the efficiency of mechanical interlocking mechanism. There was close functional dependence between the button-shear strength and surface characteristics, such as surface roughness, coating thickness and surface free energy.     

The interrelationships between electronically conductive adhesive formulations,substrate and filler surface properties,and joint performance. Part I: the effects of adhesive thickness

Electronically conductive adhesives (ECAs) have received a great deal of attention for interconnection applications in recent years. Even though ECAs have excellent potential for being efficient and less costly alternative to solder joining in electronic components, they still possess a number of problems with respect to durability and design to meet specific needs. One of the issues that requires understanding is regarding the optimum adhesive thickness (AT) to be used. This study addresses this issue in relation to the formulations of the conductive adhesives and their interactions with adherend surfaces. For this purpose, two different adherends varying in surface characteristics were utilized along with three different conductive adhesive formulations with varying particle loadings, and shapes and sizes of conductive nickel fillers. Joints were also prepared with two different AT values, to gain insight into the influence of AT on the joint strength, deformation and joint conductivity. As the AT was increased, only a small reduction in failure load and ultimate displacement values were observed with unetched adherends. With etched adherends, however, a small increase in joint stretchability was evident with higher adhesive thickness tested at a lower crosshead speed. When the AT was increased, we also noted a corresponding increase in the initial joint resistance.     

Effects of wood-surface roughness,adhesive viscosity and processing pressure on adhesion strength of protein adhesive

The objective of this research was to study the effects of wood-surface roughness, adhesive viscosity and processing pressure on adhesion strength between soybean protein adhesive and wood, and to seek the relative importance of the individual factors in determining adhesion strength. Processing pressure was found to be the most important factor in determining adhesion strength. An optimum pressure, which was about 4.55 MPa in this research, is needed for development of a strong bond. A higher pressure resulted in reduced adhesion strength, possibly due to damage to the wood surface; a lower pressure also resulted in decreased adhesion strength because of the lack of bond formation. Adhesive viscosity had greater effect on adhesion strength than surface roughness. Contact angle, which was found to be mainly determined by adhesive viscosity and surface roughness, was a major factor controlling adhesive penetration. A smaller contact angle, resulting from lower viscosity and rougher surface, produced deeper penetration, while a larger contact angle, resulting from higher viscosity and smoother surface, produced shallower penetration. An optimum penetration is needed to enhance adhesion strength by developing a three-dimensional interactive zone at the interface. Too deep or too much penetration would result in 'dry-out' at the interface; less penetration would limit the formation of the three-dimensional zone at the interface. Both cases resulted in reduced adhesion strength. Contact angles ranging from 35 to 47° provided the optimum penetration needed for good adhesion. The results of this research could be used as reference to determine optimum process parameters in plywood manufacturing when an aqueous based adhesive is used.     

The effects of urine and temperature on the physicochemical surface properties and adhesion behaviour of uropathogenic bacteria

Bacterial adhesion in relation to urinary-tract infections has gained importance in the last years because of the increasing catheterization in hospitals to assist post-surgery flow of urine. Since the initial adhesion of bacteria to biomaterials is governed by physicochemical forces emerging from the physicochemical properties of both interacting phases, we have investigated the physicochemical surface changes of uropathogen Enterococcus faecalis ATCC29212 bacteria due to the presence of urine in its growth medium and to the differences in the environmental temperature. Urine-grown cells were found to be less hydrophobic based on water contact angles at 22°C, while no changes were detected at 37°C. In addition, they exhibited higher acid-base surface energy component than urine-free cultured cells. These changes in surface properties were also reflected in thermodynamic predictions of the adhesion to glass and silicone, which were experimentally compared with the in vitro adhesion curves obtained in a parallel plate flow chamber. The shapes of the adhesion graphs indicated that interaction free energies should be used to describe only the initial adhesion stages. Adhesion to silicone was always enhanced by urine-grown cells, while the adhesion to glass did not seem to be affected by the urine constituents. Despite the fact that the interaction free energies were not able to explain the adhesion process in some cases, changes in the electron-donor and electron-acceptor parameters of their surface free energy due to urine addition seemed to have a relation with initial adhesion rates.     

Influence of chlorinated paraffin on properties of silica filled polychloroprene

Abstract

Roles of the two widely used chlorinated paraffins, namely Cereclor S45 and Cereclor 48, in properties of silica filled polychloroprene were investigated. The results reveal that chlorinated paraffin significantly improves the processability. The improvement is more pronounced for Cereclor S45 due to its lower viscosity. However, the addition of chlorinated paraffin has a negative effect on cure. Owing to the reduction of crosslink density and the plasticising effect of chlorinated paraffin, several mechanical properties are impaired, e.g. tensile strength, modulus, hardness, abrasion resistance as well as rebound resilience. However, the deterioration of both tensile strength and modulus is not pronounced at low loading of chlorinated paraffin (≤8·0 parts per hundred of rubber, phr). Although chlorinated paraffin has little influence on the relative tensile strength, the relative 100% modulus is affected to a greater extent due to the combination of post curing retardation and evaporation of chlorinated paraffin during thermal aging.     

Application of a new modified epoxy adhesive for bonding fluorine rubber to metal

Adhesion of fluorine rubber to metals is an important issue. The aim of this work was to develop a new kind of adhesive for bonding fluorine rubber to metals. A new modified epoxy adhesive containing a special tackifier resin obtained from polysulfones with a high heat deflection temperature (HDT) was prepared. Study on the curing behavior of the adhesive was carried out. Properties of the adhesive and the effects of several main factors were studied by gelation time test, differential scanning calorimetry (DSC) and Fourier transform infrared (FT-IR) spectroscopy. The optimum amount of the tackifier resin was found to be 50 phr; the average tensile lap shear strength could be achieved to a level of 8–10 MPa. Infrared attenuated total reflection (IRATR) spectroscopy indicated that the tackifier resin accelerated the establishment of epoxy resin adhesion to steel, and also promoted bonding and vulcanization of fluorine rubber. Easy diffusion of cyanamide (decomposition compound of dicyandiamide (DICY) in the curing process) into epoxy resin and fluorine rubber facilitated the dissolution and reaction of DICY, and also promoted formation of complex bond between fluorine rubber and adhesive, hence an enhanced adhesion of fluorine rubber to metal was achieved.     

Investigation of optimal surface treatments for carbon/epoxy composite adhesive joints

Although an adhesive joint can distribute the load over a larger area than a mechanical joint, requires no holes, adds very little weight to the structure and has superior fatigue resistance, but it not only requires a careful surface preparation of the adherends but also is affected by service environments. In this paper, suitable conditions for surface treatments such as plasma surface treatment, mechanical abrasion, and sandblast treatment were investigated to enhance the mechanical load capabilities of carbon/epoxy composite adhesive joints. A capacitively coupled radiofrequency plasma system was used for the plasma surface treatment of carbon/epoxy composites and suitable surface treatment conditions were experimentally investigated with respect to gas flow rate, chamber pressure, power intensity, and surface treatment time by measuring the surface free energies of treated specimens. The optimal mechanical abrasion conditions with sandpapers were investigated with respect to the mesh number of sandpaper, and optimal sandblast conditions were investigated with respect to sandblast pressure and particle size by observing geometric shape changes of adherends during sandblast process. Also the failure modes of composite adhesive joints were investigated with respect to surface treatment. From the peel tests on plasma treated composite adhesive joints, it was found that all composite adhesive joints failed cohesively in the adhesive layer when the surface free energy was higher than about 40 mJ/m², because of high adhesion strength between the plasma treated surface and the adhesive. From the peel tests on mechanically abraded composite adhesive joints, it was also found that the optimal surface roughness and adhesive thickness increased as the failure load increased.     

Effects of capillary force and surface deformation on particle removal in turbulent flows

A new rolling detachment model for particle removal in the presence of capillary forces based on the maximum adhesion resistance was developed. The new model uses an effective thermodynamic work of adhesion model that includes the effects of capillary forces generated by the formation of liquid meniscus at the interface. The JKR and DMT models for elastic particle and surface deformations and the Maugis and Pollock model for the plastic deformation were extended to include the effect of capillary forces. Under turbulent flow conditions, the criteria for incipient rolling detachments were evaluated. The turbulence burst model was used to evaluate the air velocity near the substrate. The critical shear velocities for resuspension of particles of different sizes were evaluated and the results were compared with those without capillary force. The model predictions were compared with the available experimental data and good agreement was found.     

The prediction of adhesion between polymer matrices and silane-treated glass surfaces in filled composites

Extending the database and the analysis of work reported earlier, the practical adhesion between a glass filler, modified by various silane coupling agents, and different polymeric matrices is measured and compared with predictions based on a generalized thermodynamic criterion. The criterion used is the magnitude of the (negative) molar Gibbs free energy of mixing, (-ΔGmix)_0.5, for a pseudo-solution consisting of equal molar amounts of the repeat units of the polymer matrix and the organo-functional group of the silane coupling agent. It is computed using the group contribution method of UNIFAC, in which molar volumes, molar areas, and molar interaction energies are constructed from contributions of the functional groups which make up the molecules of the solution. Measurements leading to the values of the adhesion strength are carried out using the singleparticle composite method, in which a rectangular polymer specimen containing a single silane-treated glass bead is subjected to increasing uni-axial tensile stress until interfacial failure, as observed using a microscope, occurs at one of the poles of the sphere. Earlier work reported a good correlation between the local stress at the pole computed from such measurements and the value of (-ΔG _mix)_0.5 computed using UNIFAC for ten different organo-silane-modified spheres imbedded in a poly(vinyl butyral) matrix. The present work extends the database to two additional matrices, viz. poly(methyl methacrylate) and poly(ethyl methacrylate). In addition, elastic fracture-mechanics theory is used to deduce specific adhesion energies in all cases. The relative values of the latter are all found to be in good correlation with the predictive thermodynamic criterion.     

On the work of adhesion and peel strength between pressure sensitive adhesives and the polymeric films used in LCD devices

Peel strength, a convenient measure of bond strength in adhesive/adherend systems, is known to be a function of various factors such as the thermodynamic work of adhesion, rate of measurement, thermal history, and temperature. Generally, it is believed that the work of adhesion is primarily involved in the first stage of adhesion through wetting phenomenon and beyond that its role diminishes in that the portion of thermodynamic contribution to actual bond strength is insignificant. In practice, however, we often observe that a suitable surface treatment increases the surface energy of the substrate, which further enhances the bond strength. One practical example is the surface treatment carried out in LCD industry to obtain sufficient bond strength between pressure sensitive adhesives and polymeric films. To further our understanding of the effect of surface treatment, we attempted to establish a possible correlation, if any, between the thermodynamic work of adhesion and peel strength. For this, we carefully measured the contact angles of water and diiodomethane against various polymeric films, and calculated the surface energy and the thermodynamic work of adhesion using the two widely used approaches: Young-Fowkes-Girifalco-Good, and Wu methods. Before establishing a correlation, some general aspects of the above two methods are discussed. The values of the work of adhesion obtained were compared with the measured peel strength. Indeed, we observed a clear correlation between the two quantities: the increase of the work of adhesion led to the increase of peel strength. As a reason for this correlation, we proposed that the increase of surface energy might be associated with the increase of various surface functional groups, which, in turn, contributed to the formation of chemical bonding with the PSA leading to the increase of peel strength.     

Thermoplastic film adhesives based on phenol-functional acrylic copolymers: synthesis,mechanical and adhesion properties

Acrylic polymers possessing varying proportions of pendant phenol groups were synthesized by the free radical copolymerization of N-(4-hydroxyphenyl) maleimide (HPM) with butyl acrylate (BuA) and acrylonitrile (AN) and characterized. These thermoplastics form excellent films and their mechanical and adhesion properties were evaluated as a function of the phenol content. Enhancing the HPM content increased both the tensile strength and the modulus but decreased the elongation. A nominal increase in the phenol content was found to be conducive for improving the adhesion properties of the films. At higher concentrations, the adhesion properties showed a decreasing trend due to the embrittlement caused by the rigid maleimide groups. The adhesion property at 50°C increased linearly with the HPM content due to an increased T _g, whereas a reverse trend was observed for the adhesion property measured at-196°C, due to the dominance of the embrittlement effect. The reduced flow characteristics of the high HPM-loaded systems led to a diminished honeycomb flat-wise tensile strength. Enhancing the HPM concentration in the chain promoted the adhesion properties for the vulcanization bonding of nitrile rubber to aluminium. Addition of silica filler marginally improved the lap shear strength (LSS) for the metal-metal system, but was detrimental for rubber-metal bonding; a reverse trend was observed for the carbon-filled system. The diminished performance for metal-metal bonding by carbon could be attributed to the weakening of the interphase, whereas the enhanced rubber-metal bonding could be due to possible reinforcement of the rubber phase by carbon. The fillers generally improved the high temperature adhesion. However, they impaired the flow properties of the resin and, thereby, adversely affected the flat-wise tensile strength in both cases.     

Improved adhesion of EVAs with different vinyl acetate contents treated with sulphuric acid

Four ethylene vinyl acetate copolymers (EVAs) containing 9, 12, 18 and 20 wt% vinyl acetate (VA) were treated with concentrated sulphuric acid to improve their adhesion to polychloroprene (PCP) adhesive. The tensile strength and Young's modulus of EVAs decreased as the VA content increased, due to the reduction in crystallinity of the polyethylene blocks in the copolymer. The modifications produced in the EVAs by treatment with sulphuric acid were followed using contact angle measurements (water, 25 °C), ATR-IR spectroscopy and scanning electron microscopy (SEM). Adhesive-bond strength was obtained by T-peel tests on treated EVA/polychloroprene adhesive joints. The vinyl acetate content in the EVA affected the extent, but not the nature, of the surface modification produced by treatment with sulphuric acid. The treatment produced both sulfonation and oxidation on the EVA surfaces. The higher the vinyl acetate content in the EVA, the more significant the modifications produced. Increased T-peel strengths of EVA/polychloroprene adhesive + 5 wt% polyisocyanate joints were obtained and a mixed failure (adhesion failure + cohesive failure in the adhesive) was produced. It was found that, to be effective, the treatment of EVAs must be carried out with 96 wt% sulphuric acid.     

Characterizing the mechanism of improved adhesion of modified wood plastic composite (WPC) surfaces

To have a better knowledge of the phenomena that affect the adhesion characteristics of wood plastic composites (WPCs) a series of surface treatments was performed. The treatments consisted of chemical, mechanical, energetic, physical, and a combination of energetic and physical WPC surface modifications. After each treatment, the composite boards were bonded using a commercial epoxy adhesive, and bond shear strength was determined according to ASTM D 905. All the surface treatments, except the mechanical one, were performed and presented in a previous paper (W. Gramlich et al., J. Adhesion Sci. Technol. 20, 1873–1887 (2006)). Mechanical treatment and surface characterization for all the treatments were performed in the present study. The surface characterization included application of thermodynamic and spectroscopic techniques. Most of the surface treatments improved the adhesive bondability of wood plastic composites and, particularly, the smoothest WPC surfaces increased the shear strength by 100% with respect to the control. Thermodynamic measurements indicate that the WPCs low surface energy of about 25 mJ/m², is likely due principally to the surface migration of a lubricant component used in the extrusion formulation. The surface energy increased over 45% with respect to the control samples after the chemical treatments. X-ray photoelectron spectroscopy analysis indicated that high oxidation levels of the WPC surfaces resulted in high surface energy and high bond shear strength.     

The role of interfacial interactions and loss function of model adhesives on their adhesion to glass

The measurement of adhesion and the evaluation of influencing factors are of great scientific and technological importance. There are two distinct viewpoints on adhesion: (i) surface chemistry, and (ii) fracture mechanics. For elucidation of the relative importance of mechanical properties in the bonding of adhesives, the strength of adhesion between model adhesives and glass plates was measured by the wedge cleavage (WC) test method. Copolymers of methyl methacrylate (MMA) with n-butyl acrylate (nBA) and methyl methacrylate with styrene (S) were prepared as model adhesives. The results show that in MMA-nBA copolymers, by increasing the amount of nBA, both the loss function and the adhesion energy of the adhesives increase. However, by increasing the amount of nBA above a certain level, the adhesion strength begins to decrease. In this situation, the cohesive strength of the adhesive dominates the failure mechanism. On the other hand, a decrease in adhesion was expected upon increasing the amount of styrene in the poly(styrene-co-methyl methacrylate) adhesive, because methyl methacrylate, an interactive monomer with glass, is replaced by a non-interacting styrene monomer, while the loss function of the adhesive is almost constant. But our practical adhesion measurement technique was not sensitive enough to detect this adhesion loss.     

The aging effects of repeated oxygen plasma treatment on the surface rearrangement and adhesion of LDPE to aluminum

The effects of aging temperature and time on the adhesion properties of oxygen plasmatreated low-density polyethylene (LDPE) were investigated. As the aging temperature and time increased, surface rearrangement and the migration of molecules containing polar functional groups into the bulk were accelerated to the surface to form a hydrophobic surface. The adhesion strength of oxygen plasma-treated LDPE/aluminum joints was measured using a 90° peel test by varying the plasma treatment time and aging temperature. The adhesion strength was constant, regardless of the plasma treatment time. As the aging temperature increased, the adhesion strength of the LDPE/aluminum joints decreased and the locus of failure changed from cohesive to interfacial failure. It was also found that the polar functional groups buried in the bulk could be reoriented to the surface in a polar environment. This study also investigated whether repeated oxygen plasma treatment would increase the concentration of polar functional groups at the surface and reduce the surface rearrangement and the migration of molecules containing polar functional groups during aging. Contact angle measurements and X-ray photoelectron spectroscopy (XPS) showed that repeated oxygen plasma treatments increased the concentration of polar functional groups at the surface. However, the aging time between plasma treatments had a negligible effect on the concentration of polar functional groups at the surface.     

Collagen immobilization onto the surface of artificial hair for improving the tissue adhesion

To improve the bonding ability of artificial hair towards soft tissue, type I atelocollagen was immobilized onto the hair surface. The artificial hair used was made of a poly(ethylene terephthalate) monofilament. Following photo-induced graft polymerization of a hydrophilic monomer onto the surface of artificial hair, collagen was complexed with the graft chains. Poly(acrylic acid) was selected as the polymer to be grafted onto the artificial hair because this synthetic polymer exhibited the greatest ability to form an interpolymer complex in solution with collagen among the three anionic polymers poly(acrylic acid), poly(2-acrylamido methylpropane sulfonic acid), and sodium poly(styrene sulfonic acid). When the surface of the poly(ethylene terephthalate) film used as a model substrate was grafted with poly(acrylic acid), the surface density of the collagen immobilized by interpolymer complexation was found to increase with increasing surface density of the graft chains. Immobilization of collagen onto the filament surface was confirmed by surface analysis with X-ray photoelectron spectroscopy and transmission electron microscopy. It was shown that in vitro degradation of the collagen immobilized onto poly(ethylene terephthalate) was suppressed by crosslinking the collagen molecules with glutaraldehyde. Cell culture tests revealed that L-cells were attached well to the surface of collagen-immobilized artificial hair. The surface-modified hairs were implanted percutaneously in the scalp of a human volunteer. Neither infection nor rejection of the hair filaments was observed after 1 year of implantation. It was found that the number of collagenimmobilized filaments remaining fixed in the scalp after 3 years of implantation was significantly larger than that of untreated filaments. These results indicate that surface-modified artificial hair is highly biosafe and shows excellent tissue adhesion.     

Surface reactivity of polyimide and its effect on adhesion to epoxy

Polyimides are commonly used as organic passivation layers for microelectronic devices due to their unique combination of properties such as low dielectric constant, high thermal stability, excellent mechanical properties and superior solvent resistance. Unfortunately, polyimides are well known to be difficult to bond to other materials, especially to epoxy resins. Many surface treatments have been developed to increase epoxy–polyimide adhesion. These treatments include exposure to ion beams, plasmas and chemical solutions. The goal of our research was to relate surface reactivity of epoxy and polyimide resins to the strength of epoxy–polyimide interfaces. The surface reactivity of four polyimides was studied and quantified using contact angle measurements, flow microcalorimetry (FMC), Fourier transform infrared (FT-IR) spectroscopy (using an attenuated total reflection (ATR) accessory) and X-ray photoelectron spectroscopy (XPS). Several ways of analyzing contact angles were tried and only a weak correlation between the polar component or the acid–base components of the surface free energy with the critical interfacial strain energy release rate (i.e., the interfacial fracture strength) was observed. FMC results suggest that the strength of epoxy–polyimide interfaces is related to the molecular interactions between the curing agent and polyimide. The molecular interactions between the curing agent and polyimide surfaces were found to be either greater than epoxy and polyimide interactions or more irreversible. Therefore, the curing agent (2,4-EMI) is thought to play a critical role in controlling adhesion strength.