The Structure of the Irreversibly Bound Adhesion Promoter-Substrate Interfacial Layer of γ-Aminopropylsilanetriol on Crystalline Si,as Measured by XPS and FTIR

The irreversibly bound interfacial layer deposited by the γ-aminopropysilanetriol adhesion promoter onto a crystalline silicon substrate, which remains even after profuse washing, was found by XPS to have resulted from the fragmentation and rearrangement of the original γ-aminopropylsilanetriol molecule. A mechanism is proposed, involving the homolytic scission of the terminal N-C bond. One of the subsequent reactions is believed to involve hydrogen loss by abstraction and the formation of a terminal vinyl group, which bonds to the substrate. Support for this mechanism is found in IR spectroscopy of this layer.     

Adhesion Mechanisms of Polyurethanes to Glass Surfaces. III. Investigation of Possible Physico-Chemical Interactions at the Interphase

Surface free energies of polyurethanes made from toluene diisocyanate and 1, 4 butanediol-based hard segments and caprolactone polyol-based soft segments were calculated using additive functions. Good agreement was found between the calculated values based on additive functions and the calculated values based on contact angle measurements. The phase-separated polyurethanes were found to have a higher polar surface free energy component (γ^P). This was linked to the preferential segregation of butanediol/butanediol-derived moieties to the polyurethane surfaces due to phase separation. The adhesion values of these polyurethanes to soda-lime glass were correlated with their respective γ^P values and a linear relationship was found. It was also shown that the adhesion values of the low γ^P polyurethanes improved substantially when the glass surfaces were coated with a thin layer of butanediol prior to the bonding. The modulus of the interphase region rich in butanediol was evaluated. Although a modulus increase was found at the interface, this increase was found to play a secondary role in the adhesion. The chemical interactions at the polyurethane/glass interphase were investigated by pre-treating the glass surfaces with methyl-trimethoxysilane and trimethylchlorosilane prior to adhesion testing. The adhesion data showed no significant difference between the uncoated and the silane-treated glass substrates. Based on this experimental evidence, the possibility of any covalent or ionic bonding at the polyurethane/glass interphase was assumed negligible. It was determined that the mechanism of adhesion between the polyurethanes and the glass surface could be through the formation of an interphase region in which hydrogen bonding between the butanediol-rich interphase region and the hydroxylated glass surface plays a key role.     

Effect of Peel Angle Upon Peel Force

Measurements of peel force P per unit width are reported for samples of three adhesive tapes, adhering to two different substrates. In all cases, the work of detachment per unit area of bonded interface was found to depend upon the angle θ of detachment, increasing as θ increases. This effect is attributed to dissipation of energy in bending the tape away from the substrate at the line of detachment, to a greater degree as θ increases. Extrapolation to θ = 0 is suggested as a simple way of minimizing contributions to the observed work of detachment that arise from bending an imperfectly-elastic adhering layer as it is peeled away from a flat rigid substrate. But at small peel angles the tape tends to stretch appreciably. Peeling at 45° is recommended to minimize both effects.     

Water uptake of epoxy coatings modified with γ-APS silane monomer

Epoxy resin was modified by a silane monomer, γ-aminopropyltrimethoxy silane (γ-APS), and was used as the protective coatings for LY12 aluminum alloys. The aim of the modification is to reduce the water uptake of polymeric coatings. The water absorption of coatings was measured by coating capacitance method in 3.5 wt.% NaCl aqueous solution. The result indicates that water uptake of epoxy coatings modified with 1.0 wt.% γ-APS decreases compared with pure epoxy coatings, whereas larger amounts of sliane result in the deterioration in performance against water permeation, due to the excessive consumption of epoxide group in epoxy resin by amino-group in silane agent, thus reduce the cross-linking of epxoy coating as a result of presence of excessive curing agent (polyamide). T_g of silane-modified coatings increases slightly after immersion, extremely contrasting with that of pure epoxy coating, which was observed to decrease significantly after water permeation. The formation of Si–O–Si structure resulting from the hydrolysis and condensation of silane components during the immersion in aqueous media may be a reasonable explanation for the abnormal change in T_g of silane-modified coatings. In addition, all silane-modified coatings display better protection performance, which is characterized by higher charge transfer resistances (R_ct) and lower double layer capacitance (C_dl) at substrate/electrolyte interface.     

Nanosized γ-Al2O3 protective film for fluorescent lamps

Nanosized γ-Al₂O₃ particles were prepared by the sol–gel method with aluminum ion hydrolysis control performed by nitric acid. The as-prepared particles were mixed with deionized-water and stabilizer, and cycled in a high speed sand mill to form a stable γ-Al₂O₃ suspended slurry, which was then coated on the surface of the glass substrate to form a γ-Al₂O₃ protective film. Observations of SEM and visible transmission spectra show that a well-dispersed γ-Al₂O₃ slurry could be obtained after three-cycle grinding suitable to coat fluorescent lamp glass with a dense and uniform film of visible light transmission up to 95%.     

Influence of Substrate Properties on the Dewetting Dynamics of Viscoelastic Polymer Films

We studied the dewetting process of thin polystyrene (PS) films on silicon substrates, coated with a thin, irreversibly adsorbed polydimethylsiloxane (PDMS) layer, by optical microscopy and atomic force microscopy. Besides demonstrating the exceptional potential of dewetting for a sensitive characterization of rheological properties of PS thin films, characterized by a stress-relaxation time, τ₁, we focused on the influence of the frictional behaviour (energy dissipation mechanism) at the interface between the PDMS-coated silicon wafer and the PS film on the dewetting process. Our results show that the initial stages of dewetting depend sensitively on the thickness and the way the PDMS layer was adsorbed. The maximum width of the dewetting rim at τ₁ increased with increasing PDMS layer thickness, which can be interpreted as an increase of the effective, velocity-dependent slippage length. Interestingly, τ₁ was found to be almost independent of the substrate properties. Our results demonstrate that dewetting is a really powerful approach for rheological and frictional studies of thin polymer films.     

Stability of pigment and resin dispersions in waterborne paint

The stability of a colloidal dispersion in a waterborne paint system, which consists of dispersed pigment and polymeric particles (dispersion or emulsion) along with a water-soluble acrylic polymer, was investigated. It was found that adsorption of appropriate ultrafine particles to the relevant particles could stabilize these particles against flocculation, leading to lower viscosity and yield value. The gloss and smoothness of the resultant films are notably improved. As the stability of the colloidal particles in an aqueous system is strongly dependent on the electrostatic effect, the effect was evaluated by measuring the ζ-potentials of the relevant colloidal particles. The ζ-potential is the electric potential on the outside of the surface layer, which includes the counterions around the particle. The ζ-potentials of a series of pigments in a solution of a water-soluble polymer were determined. By arranging the pigments according to their ζ-potentials, an order of basicity-acidity was established for pigments in a waterborne system, and the order was found to be different from that of solventborne systems, thought to be due to adsorbed counterions. After dispersing the pigment sufficiently with an appropriate polymer dispersant, ultrafine particles (of size under 0.05 μm) of lower refractive indexes were adsorbed to the surface of the pigments and polymeric particles. The adsorption layer of ultrafine particles can modulate the ζ-potentials of various colloidal particles to bring them into a certain range, so that the co-flocculation tendency between different colloids is remarkably diminished providing quite stable paint compositions by both electrostatic and steric hindrance effects.     

Measurement of the Surface Free Energy of Amorphous Cellulose by Alkane Adsorption: A Critical Evaluation of Inverse Gas Chromatography (IGC)

Surface energies of amorphous cellulose “beads” were measured by IGC at different temperatures (50 to 100°C) using n-alkane probes (pentane to undecane). The equation of Schultz and Lavielle was applied which relates the specific retention volume of the gas probe to the dispersive component of the surface energy of the solid and liquid, γ^d_s and γ^d_l, respectively, and a parameter (“a”) which represents the surface area of the gas probe in contact with the solids. At 50°C, γ^d_s was determined to be 71.5 mJ/m², and its temperature dependence was 0.36 mJ m^-2 K^-1. Compared with measurements obtained by contact angle, IGC results were found to yield higher values, and especially a higher temperature dependence, d(γ^d_s)/dT. Various potential explanations for these elevated values were examined. The surface energy, as determined by the Schultz and Lavielle equation, was found to depend mostly on the parameter “a”. Two experimental conditions are known to affect the values of “a”: the solid surface and the temperature. While the surface effect of the parameter “a” was ignored in this study, the dependence of the surface energy upon temperature and probe phase was demonstrated to be significant. Several optional treatments of the parameter “a” were modeled. It was observed that both experimental imprecision, but mostly the fundamental difference between the liquid-solid vs the gas-solid system (and the associated theoretical weakness of the model used), could explain the differences between γ^d_s and d(γ^d_s)/dT measured by contact angle and IGC. It was concluded that the exaggerated temperature dependence of the IGC results is a consequence of limitations inherent in the definition of parameter “a”.     

The Rule of Interfacial Equilibrium

The detailed analysis of the well-known relation γ₁₂ = γ₁ -γ₂ has been done (γ₁₂, γ₁ and γ₂ are interfacial and surface tensions of phases 1 and 2). The analysis of equilibrium of a liquid drop at the interface with another liquid allowed us to prove that this relation should be modified by including in it the value γ₂* which is considered as the result of all interactions at the interface and is accepted depending on γ₁. The value γ₂* represents the surface tension of a phase in the ternary point solid-liquid-gas, i.e. in the zone of interfacial nonuniformity. The modified form of the relation, called the rule of interfacial equilibrium, allows us to show that thermodynamic work of adhesion is equal to the cohesion energy of the interphase formed by phase 2.     

Anomalous properties of poly(γ-benzyl L-glutamate) film composed of unusual 7/2 helices

Poly(γ-benzyl L-glutamate) film composed of unusual 7-residue 2-turn (7/2) helices was prepared by slow casting from chloroform solution. The 7/2 helical conformation was irreversibly transformed at 84°C to the normal 18/5 conformation. In d.s.c. thermograms the transformation appeared as an endothermic first order transition with an enthalpy change of 3.4 cal g⁻¹. The viscoelastic and dielectric measurements indicated that the loss peak due to the side chain motion in this film was reduced to a great extent compared to the film of 18/5 helices. The dielectric relaxation strength dictated that there was a motional restriction in three quarters of the side chains. By comparison to a racemic mixture of poly(γ-benzyl glutamate), these anomalous properties were attributed to the stack of terminal benzyl groups of side chains (ormed in an alternating manner between neighbouring chains). The first order transition arises from the cooperative fusion of the stack and the side chains with their benzyl groups which are restricted in thermal motion. Such stacks may be facilitated by the precise ‘knob (side chain) and hole (space between side chains)’ packing which can be attained between neighbouring 7/2 helices.     

The crystallographic relationship of heteroepitaxial diamond films on scratched silicon substrates

By using the straight hot filament chemical vapor deposition method with one falt horizonatal filament, diamond films were rapidly grown on a scratched silicon substrate. Observing two kinds of interface structures of the samples by cross-section high-resolution transmission electron microscopy, we found that diamond {111}-oriented films are epitaxially grown on β-SiC{111} planes with a tilt angle of about 7° around the common [110] axis. We also found that diamond771 planes are parallel to silicon111 planes on which diamonds are directly epitaxially grown on silicon substrate. The interface dislocations are of either 60°-type or Schockley partial dislocation in relation to our observations.     

Role of iron surface oxidation layers in decomposition of azo-dye water pollutants in weak acidic solutions

While decomposition of water pollutants in the presence of metallic iron can be strongly influenced by the nature and structure of the iron surface layer, the composition and structure of the layer produced and transformed in the decomposition process, have been meagerly investigated. The studies presented here establish strong relationships between the composition and structure of the iron oxidized surface layer and the kinetics and reaction pathways of orange II decomposition. The most striking observation is a dramatic difference between dye decomposition at pH 3 and 4. Orange decomposition at pH 2 and 3 is a very fast process with pseudo-first-order kinetics, with a surface normalized rate constant k_SA = 0.18 L/m² min at pH 3 and 30 °C. Whereas at pH 4 and 5 the rate is lower with pseudo-zero-order kinetics, with normalized rate constant k_SA = 1.4 × 10⁻⁵ mol/m² min at pH 5 and 30 °C. At pH 3 the iron surface is covered by a polymeric Fe(OH)₂ mixed with FeO very thin layer whose thickness remains almost constant with reaction time. There is a slow formation of an additional surface product with akaganeite-like structure. At pH 3 almost all oxidized iron is detected in solution, whereas at pH 5 almost total oxidized iron is cumulated on iron surface in the form of a lepidocrocite, γ-FeOOH, layer. The thickness of the layer increases continuously with time. The quantitative evaluation of the produced surface lepidocrocite and its surface distribution were performed by means of infrared reflection spectroscopy and spectral simulation methods. At higher temperature 40–50 °C, other surface products such as goethite, -FeOOH, and feroxyhite, β-FeOOH, are also observed. Decomposition of orange is a multi-step process, at pH 3 the orange molecule is at first adsorbed on the very thin iron oxidized layers through SO₃ group and then undergoes reduction. Discoloration of orange II in aerobic solution takes place by reduction of the NN bond at the iron surface. The major intermediate is 1-amino-2-naphtol, which undergoes further decomposition without forming any aromatic species. The previously suggested sulfanilic acid as intermediate was not detected in solution. At pH 3 orange reduction and reduction of intermediates are governed by the combination of an electron transfer reaction, with the thin oxide surface layer as a mediator, and the catalytic hydrogenation reaction. At pH 4 and 5 continuous growing of lepidocrocite surface layer demonstrates the importance of the layer as a mediator in the electron transfer reaction. The layer shows a good conductivity, which results from adsorption and absorption of iron ions in the surface structure. It is observed that the decomposition reaction becomes significant at open circuit potential (OCP) below −120 mV (SHE). At pH 3 this condition is fulfilled almost immediately after introduction of iron to aqueous solution, whereas at pH 4 and 5 the OCP of iron decreases very slowly. Iron surface layer composition and structure can be modified by an addition of Fe²⁺ to solution, which increases the dye decomposition rate. The performed observations make the treatment of waste water in the presence of metallic iron a promising environmental solution.     

Waveguides in KNbO3 by He implantation

In a KNbO₃ single domain substrate crystal a permanent multimode waveguide has been produced for the first time by implantation of 2 MeV He⁺ ions. Annealing is unnecessary since electronic damage is small. The irradiation flux was controlled such that no unwanted phase transitions or domain formation occured. The refractive index profile was investigated by dark line mode spectroscopy and reconstructed by a new inverse WKB procedure. The waveguiding layer has a thickness of about 3 μm, in the region directly below this layer the refractive index is decreased by more than 0.1.     

THE ENHANCEMENT OF GAS ABSORPTION BY A HETEROGENEOUSLY CATALYSED CHEMICAL REACTION IN A STAGNANT LIQUID: TEMPERATURE RISE AND EFFECTIVENESS OF THE CATALYST

In the present paper a model has been developed to calculate the enhancement efficiency e of the gas absorption and the effectiveness factor η of the catalyst for a chemically reacting system consisting of a sedimented catalyst particles-containing layer of thickness γ_k adhering to the surface of a gas bubble situated in a stagnant liquid. This model predicts that for a heterogeneously catalysed first-order chemical reaction an increase in the thickness γ_k of the catalyst particles-containing layer will result in an increase of ε and a decrease of η. It has been shown that the optimum value (γ_k)_opt of this layer can be obtained from the relation (γ_k) = (D_AB/k₁₃). Further, a model is derived to calculate the steady-state temperature profile in the catalyst particles-containing layer adhering to the gas bubble surface. Both models have been applied to experimental results published in some of our previous papers. These experimental results concern the enhancement of the gas-absorption rate from a single hydrogen-containing gas bubble to a stagnant aqueous hydroxylaminephosphate-containing solution when a layer of sedimented Pd/C catalyst particles was adhered to the surface of the gas bubble. The model and the experimental results mentioned may approximately be considered as representative of slurry reactors in which finely divided catalyst particles show considerable adhesion to rising gas bubbles.     

Physico-Chemical Criteria for Maximum Adhesion. Part II: A New Comprehensive Thermodynamic Analysis

In this paper, two parameters defined as the relative work of adhesion [W_A/γ_L] and the relative interfacial energy [γ_SL/γ_L] have been examined for their assumed usefulness in correlating the thermodynamic properties of the components of the system substrate/ adhesive with its practical performance (strength). It is shown that the minimum value of [γ_SL/γ_L] relevant to conditions for the maximum adhesion becomes zero only for those systems (relatively rare) for which interaction factor Φ₀ is equal to 1.0.

Several transition points were identified for boundary conditions acquired at θ = 0° and θ = 90° which can be used to predict the properties and performance of an adhesive joint. These transition points are: a_MIN—energy modulus of the system (E. M. S.), relevant to the minimum interfacial energy; a_S—E. M. S. where self-spreading of adhesive occurs; a_CRIT—E. M. S. relevant to conditions under which the thermodynamic work of adhesion becomes negative and the system exhibits a tendency for self-delaminating or has “zero-strength”; a_CF—E. M. S. beyond which the geometry of the interface at any interfacial void or boundary of the joint may be regarded as a crack tip.

It is shown that only in those systems for which Φ₀ = 1.0 can a minimum contact angle of 0° indicate a condition for the maximum strength. If Φ₀ is known, the optimum contact angle can be estimated and hence the optimum surface energy of the substrate (adjusted by surface treatment, etc.) for the maximum adhesion.     

Theory and Analysis of Peel Adhesion: Adhesive Thickness Effects

The existing assumptions concerning boundary stress concentrations in peel adhesion are extended to treat the effects of adhesive thickness. In adhesive bonds involving the all-angle peeling of a flexible elastic adherend from a rigid substrate the varying of adhesive thickness is shown theoretically to predict a proportional increase of peel force (P) with adhesive interlayer thickness (a) when the product (βCa) of the cleavage stress concentration β, cavitation scale factor C, and adhesive thickness a is less than unity. When the product (βCa) becomes greater than unity the new theory predicts that cleavage stresses concentrate within a fractional layer of the total adhesive thickness f(a) and the peel force P tends to achieve a constant value P_max. This new theory is verified by experimental studies and the experimental analysis suggests new optimizations in the design and measurement of the peel adhesive bond.     

Features of corrosion resistance of AlN–SiC ceramics in air up to 1600°C

The kinetics and mechanism of (80% AlN + 20% SiC) and (50% AlN + 50% SiC) powders and ceramics oxidation in air up to 1600°C were studied with the aid of TG, DTA, XRD, EPMA, SEM and metallographic analysis methods. The ceramics samples were obtained by hot pressing fine-dispersion AlN and SiC powders with an average particle size of 1 μm at 1800°C for 2 h. This ensures a fine-grain material structure with a uniform distribution of phase components. It was shown that in a nonisothermal regime, a three-stage oxidation mechanism takes place. It was established that the scale formed consists of three oxide layers. In the inner layer, Al₁₀N₈O₂ oxynitride and β-SiO₂ (cristobalite) phases were observed; in the intermediate layer, β-SiAlON was found for samples with a relatively low SiC content whereas -Al₂O₃ was present in samples with a greater SiC content. The outer layer contains 3Al₂O₃.2SiO₂ (mullite) as a main phase, the latter ensuring highly protective properties of the scale. The materials investigated can be considered as having extremely high resistance to corrosion up to 1550°C.     

Influence of a metal–polymer interfacial interaction on dielectric relaxation properties of polyurethane

The influence of metal–polymer interaction on dielectric relaxation properties of polyurethane (PU), prepared from poly(oxypropylene)diol and hexamethylendiisocyanate, was investigated by means of dielectric relaxation spectroscopy in the frequency domain on the dependence of the thickness of the PU layer and electrode material (gold and steel). Strong electrostatic part of an adhesion interaction between steel substrate and PU results in changes of the -, β-, γ- and Maxwell–Wagner–Sillars relaxation of the PU, as compared to a gold substrate. The effect of the metal–polymer double layer results in the complication of the cooperative and local motions in the polymer. The influence of metal–polymer interaction on the relaxation parameters becomes pronounced at a thickness of less than 60 μm for the steel substrate. For the gold substrate the relaxation characteristics hardly depend on the thickness.     

低成本大比表面积γ-Al2O3的制备

以廉价无机铝盐硫酸铝为原料,氨水为沉淀剂,十二烷基硫酸钠为添加剂,采用简单沉淀法制备得到较大比表面积γ-Al₂O₃。通过N₂低温物理吸附-脱附、X射线衍射、红外光谱、热重、元素分析、扫描及透射电镜等,研究制备过程中沉淀温度、溶液pH值和添加剂用量对产物γ-Al₂O₃及其前驱体的晶相结构、形貌织构等性质的影响。结果表明,在沉淀温度75 ℃、硫酸铝浓度0.25 mol·L^-1、溶液pH=9.0、老化时间12 h和n(十二烷基硫酸钠)∶n[Al₂(SO₄)₃]=0.375∶1条件下,所得前驱体(拟薄水铝石)经600 ℃焙烧后,可获得大比表面积(416.65 m²·g^-1)γ-Al₂O₃,并且样品中因十二烷基硫酸钠添加,引入的S及Na等杂质含量极少。     

Preparation and characterization of palladium-plated porous glass for hydrogen enrichment

In this study, cylindrical porous glass tablets were plated by palladium using electroless plating technique. Hypophosphite and Co(II) complexes were used as reducing agents in the prepared plating baths. Experiments were carried out in an especially designed glass vessel in which helium gas was continuously bubbled through the solution to create uniform concentration and to remove hydrogen gas from the surface for the case of hypophosphite-based procedure. XRF analysis of the upper layer of the composite membrane prepared by the hypophosphite-based bath showed a Pd/Si ratio of 4.6. SEM photographs indicated impregnation of Pd into the substrate upto 200 μm. However, the thickness of the dense Pd layer was only about 15 μm. SEM photographs and XRF results showed that hypophosphite-based bath was much more successful than the Co(II) complex-bath in Pd plating. Permeation experiments carried out at different temperatures showed that the contribution of surface diffusion to the permeation was significant at low temperatures and solution–diffusion mechanism was not important in the 40–200 °C temperature range for these membranes. The selectivity ratio for H₂/N₂ was found to be about 7 at 200 °C.