Mechanism of adhesion promotion between aluminium sheet and polypropylene with maleic anhydride‐grafted polypropylene by γ‐aminopropyltriethoxy silane

The effect of concentration of γ‐aminopropyltriethoxy (γ‐APS) solution on shear strength of adhesive bonding between aluminium sheet and polypropylene (PP) with addition of a certain amount of maleic anhydride‐grafted polypropylene (PP‐g‐MAH) has been investigated. It is shown that the lap shear strength is promoted obviously with pre‐treatment of aluminium sheet by γ‐APS. The maximum strength is obtained at a concentration of 3% γ‐APS solution. With further high concentration of γ‐APS, the lap shear strength decreases. The examination of the separated surfaces by X‐ray photoelectron spectroscopy (XPS) shows that (C?O)₂? O? Al and C(?O)? O? Al are formed for adhesive bonding between PP with the addition of 20 wt% PP‐g‐MAH and aluminium sheet without pre‐treatment by γ‐APS, and that the area ratio of C related to oxygen on the separated aluminium side is 33.28%, which is obviously higher than 14% on the polymer side. As for adhesive bonding between PP with the addition of 20% PP‐g‐MAH and 3% γ‐APS pre‐treated aluminium sheet, C(?O)? N? C(?O) and C(?O)? NH are formed. The area ratio of C related to oxygen on the separated polymer side increases to 24.99%. It is proposed that γ‐APS pre‐treatment improves the distribution and shape of PP‐g‐MAH chains in the region adsorbed on the substrate and the region adjacent to this region. The chemical interactions at the interface are also proposed. Copyright © 2008 John Wiley & Sons, Ltd.     

A ToF‐SIMS investigation of a buried polymer/polymer interface exposed by ultra‐low‐angle microtomy

The interfacial region of a model multilayer coating system on an aluminium substrate has been investigated by high‐resolution time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS). Employing ultra‐low‐angle microtomy (ULAM), the interface between a poly(vinylidene difluoride) (PVdF)‐based topcoat and a poly(urethane) (PU)‐based primer ‘buried’ >20 µm below the PVdF topcoat's air/coating surface was exposed. Imaging ToF‐SIMS and subsequent post‐processing extraction of mass spectra of the ULAM‐exposed interface region and of the PVdF topcoat and PU primer bulks indicates that the material composition of the polymer/polymer interface region is substantially different to that of the bulk PVdF and PU coatings. Analysis of the negative ion mass spectra obtained from the PVdF/PU interface reveals the presence of a methacrylate‐based component or additive at the interface region. Reviewing the topcoat and primer coating formulations reveals that the PVdF topcoat formulation contains methyl methacrylate (MMA)–ethyl acrylate (EA) acrylic co‐polymer components. Negative ion ToF‐SIMS analysis of an acrylic co‐polymer confirms that it is these components that are observed at the PVdF/PU interface. Post‐processing extraction of ToF‐SIMS images based on the major ions of the MMA–EA co‐polymers reveals that these components are observed in high concentration at the extremities of the PVdF coating, i.e. at the polymer/polymer interface, but are also observed to be distributed evenly throughout the bulk of the PVdF topcoat. These findings confirm that a fraction of the MMA–EA acrylic co‐polymers in the formulation segregate to the topcoat/primer interface where they enhance the adhesive properties exhibited by the PVdF topcoat towards the underlying PU primer substrate. Copyright © 2004 John Wiley & Sons, Ltd.     

Interfacial chemistry of adhesives on hydrated aluminium and hydrated aluminium treated with an organosilane

The adsorption of a commercial adhesive and two of its major components—an amine curing agent [2,4‐toluene diisocyanate urone (TDI urone)] and an adhesive prepolymer resin [diglycidyl ether of bisphenol A (DGEBA)]—on a hydrated aluminium surface and the hydrated surface coated with γ‐glycidoxypropyltrimethoxysilane (GPS) has been investigated by x‐ray photoelectron spectroscopy (XPS) and time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS). The study of TDI urone adsorption indicated that adsorption was of the chemisorption type, and a specific interaction involving this molecule and the GPS immobilized on the hydrated aluminium surface was identified. From XPS and ToF‐SIMS data it was found that the types of interaction of the curing agent with the bare substrate were of the donor–acceptor type. Study of the DGEBA adsorption showed different‐shaped isotherms for the bare and the GPS‐coated substrates. It was found that the typical Langmuir isotherm type was obtained for the GPS‐coated substrate whereas no adsorption plateau was observed for the bare substrate within the concentration range studied. This resulted from a change in the conformation of the DGEBA molecule on the substrate when the concentration of DGEBA solution was increased. The bonding of DGEBA with both types of substrates was assumed to be via acid–base interactions (i.e. donor–acceptor interactions). Adsorption of the commercial adhesive on the hydrated surfaces was of BET Type IV form, rather than the simple monolayer adsorption isotherm (Langmuir type). This indicates multilayer adsorption, presumably in the pores of the hydrated substrate, as a result of a process analogous to adsorption condensation. Copyright © 2004 John Wiley & Sons, Ltd.     

High thermal conductivity EP adhesive based on the GO/EP interface optimized by TDI

Graphene oxide (GO) was used as the filler to modify the epoxy resin (EP) adhesive, and the GO/EP interface was optimized by toluene diisocyanate (TDI) in order to improve the thermal conductivity and T peel strength performance of the adhesive. Through the characterization of the GO product, which was modified by TDI, TDI was grafted onto the surface of GO, and there were NCO groups remaining; thus the chemical bonds were built onto the interface which was non‐wetting between GO and EP. The results of the properties characterization of the adhesive indicated that the bonding properties were significantly enhanced, especially the T peel strength, which was up to 9.62 N/mm, which was contributed by the optimized GO/EP interface. The thermal conductivity of the adhesive increased to 0.624 W m^?1 K^?1, as the interface thermal resistance was reduced after the interface between GO/EP was optimized by TDI. The insulation performance of the adhesive was also improved, since the well‐dispersed GO formed a micro‐capacitance model in EP, and the surface of GO was covered by the EP so that the electronic paths were blocked by the formed chemical bonds.     

ATR‐FTIR Kretschmann spectroscopy for interfacial studies of a hidden aluminum surface coated with a silane film and epoxy I. Characterization by IRRAS and ATR‐FTIR

Interfacial analysis is essential in many areas of interest, for instance within the ongoing research on environmentally friendly pretreatments of metal surfaces. While studies of the hidden interface between a metal and polymer top‐coat are of great importance, properties of a surface confined between two media are difficult to analyze in detail. Within the two parts of this study, ATR‐FTIR spectroscopy in the Kretschmann geometry is employed as the main analytical tool to study the interface between a thermo‐cured epoxy and aluminum pretreated with a silane film. The technique requires model systems based on thin metal films, but in contrast to most analytical techniques it permits the analysis of a hidden interface. Initial characterization of the silane film formed from a pH‐regulated γ‐APS and BTSE solution was conducted by both ATR‐FTIR Kretschmann and IRRAS spectroscopy. Absorption bands were obtained at 1250–900 cm^?1, assigned to Si? O functionalities, and at ～1570 and ～1410 cm^?1 assigned to acetate existing as a counter‐ion to γ‐APS. After application of the epoxy film, interfacial alterations were detected upon thermal curing including the densification of the epoxy film, the dehydration of aluminum and the formation of molecular epoxy reaction products. Few alterations could be assigned to the silane film. Calculated spectra derived from optical data can verify experimental results and aid data interpretation, and effects of metal oxidation of aluminum were confirmed by introducing gold as an additional substrate. The results showed that ATR‐FTIR Kretschmann spectroscopy is clearly a valuable tool for the study of hidden interfaces of stratified media. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis of Cyclic Carbonates Catalysed by Aluminium Heteroscorpionate Complexes

New aluminium scorpionate based complexes have been prepared and used for the synthesis of cyclic carbonates from epoxides and carbon dioxide. Bimetallic aluminium(heteroscorpionate) complexes 9 – 14 were synthesised in very high yields. The single‐crystal X‐ray structures of 12 and 13 confirm an asymmetric κ²‐NO‐μ‐O arrangement in a dinuclear molecular disposition. These bimetallic aluminium complexes were investigated as catalysts for the synthesis of cyclic carbonates from epoxides and carbon dioxide in the presence of ammonium salts. Under the optimal reaction conditions, complex 9 in combination with tetrabutylammonium bromide acts as a very efficient catalyst system for the conversion of both monosubstituted and internal epoxides into the corresponding cyclic carbonates showing broad substrate scope. Complex 9 and tetrabutylammonium bromide is the second most efficient aluminium‐based catalyst system for the reaction of internal epoxides with carbon dioxide. A kinetic study has been carried out and showed that the reactions were first order in complex 9 and tetrabutylammonium bromide concentrations. Based on the kinetic study, a catalytic cycle is proposed.     

Surface modification of aluminium with reactive microgels

The adsorption and organisation process of reactive microgels has been investigated on technical aluminium. The aim was to replace the present chromating procedure on reactive metals like aluminium because this process was been considered as an ecological problem. By means of a two‐step emulsion polymerization with phosphate substituted monomer we have obtained polymeric nano‐particles with phosphate groups on the surface. The core is synthesized by copolymerization from styrene (St) and butyl acrylate (BuA). The results of several analytical methods like contact angle SEM or TEM measurements showed, that these microgels were able to adsorb spontaneously onto the substrate surface and subsequently a structured molecular order was formed. The properties of the adsorbed microgel layers were confirmed by industrial linked adhesion and corrosion tests.     

Influence of aluminium on the oxidation of titanium between 550 and 750 °C

In order to study the influence of aluminium on the oxidation resistance of titanium at high temperature, a range of binary alloys containing 1.65, 3, 5 and 10 wt.% of aluminium was prepared. Their oxidation kinetics were studied at temperatures between 500 and 750 °C using either continuous thermogravimetry or daily weighing for periods of up to several thousand hours. The results obtained for oxidation in air confirm the beneficial role of aluminium which has been observed previously for oxidation in oxygen. With regard to morphology and structure, aluminium modifies the internal structure of the oxide layers and their growth laws. A general dispersion of aluminium in rutile is observed, although a concentration of this phase is noted near the external interface; there is also a reduction in the amount of oxygen dissolved in the metal substrate which is related to the aluminium content in the alloy. Moreover, the presence of aluminium also modifies the adhesion of the oxide layers to the substrate.     

Effect of surface hydroxyl concentration on the bonding and morphology of aminopropylsilane thin films on austenitic stainless steel

The adsorption of 3‐aminopropyltrimethoxysilane thin films on Fe? 18Cr? 7Mn? 3Ni (austenitic stainless steel) was investigated by X‐ray photoelectron spectroscopy (XPS) and inelastic electron background analysis. The bonding and morphology of the films were strongly dependent on the surface hydroxyl concentration, which was controlled by the oxidation pretreatment of the substrate. In particular, an aminopropylsilane (APS) monolayer with high degree of bonding to the substrate was obtained on an electrochemically passivated surface with very high hydroxyl concentration. On the other hand, the deposition of weakly bound APS clusters was observed on substrates having relatively low hydroxyl concentrations. The adsorption occurred initially via hydrogen bonding, whereas heating to 373 K resulted in the formation of covalent Si? O? M bonds at the silane/metal oxide interface. The results of this study provide insight into the interaction between silanes and stainless steels surfaces, and can be applied for functionalization of stainless steel materials in an extensive range of applications. Copyright © 2010 John Wiley & Sons, Ltd.     

Interactions at the interface between thermoplastic rubber and polychloroprene adhesive

The interface produced between a chlorinated thermoplastic styrene‐butadiene‐styrene rubber and a polychloroprene (PCP) adhesive has been studied and compared to the interface produced using a polyurethane (PU) adhesive. Chlorination of the rubber was produced by spin coating solutions of trichloroisocyanuric acid in methyl ethyl ketone. The adhesive solution was spin coated on to the chlorinated rubber and the interface between the chlorinated rubber and the adhesive was analyzed by infrared spectroscopy. Chlorination of the rubber produces cross‐linking of the outermost chlorinated and oxidized rubber surface, which becomes insoluble in toluene. The chlorinated rubber chains are able to migrate through the chlorinated rubber/adhesive interface and produce a cross‐linked interface. Similar interfaces are obtained with PU or PCP adhesive. However it is the addition of a thermoreactive phenolic tackifier resin to the PCP adhesive, which imparts appropriate rheological properties to the PCP adhesive, responsible for the increased adhesion properties. Copyright © 2008 John Wiley & Sons, Ltd.     

Gelation and adhesion behavior of mussel adhesive protein mimetic polymer

An acrylamide‐type copolymer containing catechol, amino, and hydroxyl groups was synthesized as a mimetic of the natural mussel adhesive protein (MAP). The obtained copolymer in a phosphate buffer solution (pH = 8.0) formed a hydrogel within 2 h under air, whereas gelation did not proceed under argon atmosphere. We confirmed that the cross‐linking reaction of the synthesized MAP mimetic copolymer was triggered by aerobic oxidation of catechol moieties to form an adhesive hydrogel. Two aluminum plates were adhered by the gelation of the MAP mimetic copolymer solution under humid air at room temperature. The interfacial region between the two aluminum plates failed at a lap shear strength of 0.46 MPa due to cohesive failure of the hydrogel. The adhesion strength was dominated by mechanical strength of the hydrogel as well as the interface interaction of catechol groups with substrate surface. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Analysis of thermal parameters and factors acting on thermal conduction of low‐k films

The thermal properties of a silicon oxide‐based low‐k film and a thermally oxidized silicon film were investigated using the 3‐omega and laser thermo‐reflectance (LTR) methods. Thermal conductivity and effusivity were successfully estimated by the 3‐omega and LTR methods, respectively. It was confirmed that the combination of thermal effusivity and conductivity can successfully provide the heat capacity and thermal diffusivity of the films. The thermal parameters thus obtained suggested that the lower thermal conductivity of the examined low‐k film comes mainly from the rather low level of thermal diffusivity. Based on an analysis of the X‐ray diffraction profiles of the films, it was found that the low thermal diffusivity of the low‐k film can be attributed to the discontinuity of the network structure of their clusters. The heat resistance at the interface between the film and Si substrate was also evaluated. We found that the low‐k film exhibited, interestingly, negative interfacial heat resistance, although interfacial heat resistance should have a positive value in general. In order to determine the origin of the negative interfacial heat resistance, the interface state of the films was analyzed in detail on the basis of X‐ray reflectivity (XRR) measurements. The XRR results showed clearly that a thin, high‐density layer was present at the interface of the low‐k films. This high‐density layer presumably promoted heat flow to the substrate, resulting in the apparent negative interfacial heat resistance. Copyright © 2008 John Wiley & Sons, Ltd.     

Interfacial toughness in polymer‐layered laminar composites

The investigation of the interfacial toughness of polymer layered laminar composites with two different approaches produced results differing by up to an order of magnitude and following opposite trends with respect to the strain rates. The flexural modulus and neutral axis of a constrained epoxy‐adhesive layer bound to a painted metal substrate varied with the thickness of the adhesive layer. The adhesion energy depended on the rate at which the force was transmitted to the adhesion bonds—not just on the strength of the adhesion bonds—and on the concomitant strain hardening at high strain rates. As the strain rate and thickness of the polymer layer increased, the transition from a cohesive mode to an adhesive–cohesive (polymer–polymer interface) mode of debonding led to the observed high adhesion energy. The high adhesion energy and increased strain hardening were attributed to the formation of organic–inorganic composites and nanocomposites within the polymer matrix, which evolved as a result of the interactions between the metal oxide pigments and fillers with the polymer matrix during curing. Scission of the polymer chains at the interface was proposed to be the predominant fracture mechanism; it was based on the high relaxation time (～10¹⁷ s) and the high activation energy (～175 kJ mol^?1). © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3822–3835, 2004     

Self‐assembly of stearic acid on aluminium: the importance of oxide surface chemistry

The influence of ambient atmospheric exposure on the chemistry of the magnetron‐sputtered aluminium surface has been characterized as hydroxyl incorporation to the oxide surface and concurrent adsorption of airborne carbonaceous contamination. Here, the consequence of these changes in oxide surface chemistry upon the adsorption of stearic acid from solution is investigated. Water contact angle and polarization modulation infrared refection–absorption spectroscopy (PM‐IRRAS) reveal a strong dependence of stearic acid monolayer order upon ambient exposure time prior to assembly. It is proposed that hydroxyl formation in the ambient atmosphere increases the stearic acid adsorption density and thus the self‐assembled monolayer (SAM) order, whereas airborne carbonaceous material blocks these adsorption sites and introduces disorder in the monolayers through a decrease in adsorption density. Monolayer adsorption has been correlated with the aluminium oxide surface chemistry. It is proposed that this phenomenon represents an explanation for the irreproducible results often reported for assembly on metal oxide substrates. Furthermore, it indicates that in this broad class of material surfaces assembly can be used as a means of estimating the reactivity of surfaces with respect to organic overlayers such as paints and adhesives. Removal of adsorbed carbonaceous material from the aluminium surface using an oxygen plasma resulted in a significantly increased order of the stearic acid monolayer, as assessed by water contact angle. This observation is rationalized as the removal of carbonaceous material blocking surface adsorption sites by the plasma, but retention of the underlying hydroxyl functionality. This is predicted to have important implications in the preparation of aluminium for painting and adhesive bonding. Copyright © 2004 John Wiley & Sons, Ltd.     

A NEXAFS orientation study of γ‐aminopropyltriethoxysilane on zinc oxide surfaces

Bifunctional silanes, such as γ‐aminopropyltriethoxysilane (γ‐APS), are able to adsorb to a substrate via both functional groups creating a number of possible orientations for an adsorbed molecule within an organosilane film. The orientation of dip coated γ‐APS films on native zinc oxide surfaces as a function of solution pH has been studied using near edge X‐ray absorption fine structure (NEXAFS) spectroscopy. The NEXAFS results shed further light on the changes in the orientation that take place during the oscillatory adsorption of these molecules and reveal new insights into the molecular reorganisations that occur with changing solution pH. The results are discussed in terms of an electrokinetic model that has been developed. Copyright © 2006 John Wiley & Sons, Ltd.     

Modification of poly(benzimidazole‐amide) nanocomposites by the incorporation of amine‐functionalized ZnO nanoparticles: Thermal and morphological characterization

Fabrication, characterization, and properties of novel poly(benzimidazole‐amide)/functionalized ZnO nanocomposites (PBIA/APS‐ZnO NCs) were investigated. At first, an aromatic PBA containing 3 imidazole units per repeat unit was synthesized by direct polycondensation of 1,3‐bis(5‐carboxylic acid‐2‐benzimidazole)benzene (BCAB) with 5‐(2‐benzimidazole)‐1,3‐phenylenediamine (DAMI) with good yield as a polymeric matrix. The periphery of zinc oxide nanoparticles (ZnO NPs) was modified with 3‐aminopropyltriethoxysilane (APS) to have a better dispersion NPs and enhancing interactions between nanoparticles and PBIA matrix. Different percentages of functionalized NPs (0, 4, 8, and 12 wt.%) were then embedded in PBA matrix through ultrasonic irradiation technique. Fourier transform infrared and thermo‐gravimetric analysis (TGA) confirmed that APS was successfully attached on the ZnO NP surface. The obtained NCs were characterized by means of Fourier transform infrared, X‐ray diffraction, scanning electron microscopy, and TGA. The TGA of the PBIA/APS‐ZnO NCs showed the enhancement in the thermal stability in comparison with the neat PBIA and that this increase is higher when the NP content increases. Scanning electron microscopy analyses of NCs revealed that the dispersion of APS‐ZnO NPs was uniformly done in the PBIA matrix.     

Ultra light tunable capacitor based on PZT thin film deposited onto aluminium foil

Lead zirconate titanate (PZT) thin films with a Zr/Ti ratio of 57/43, elaborated by a derived sol–gel process, have been deposited onto bare and RuO₂ coated aluminium substrate 16 μm thick. Commercial aluminium foil presents many advantages as ultra light weight (43 g m^?2), conformability, conduction, can be easily cut, and is one of the cheapest substrates used for PZT thin films deposition (<0.1$ m^-2). XRD measurements have shown a well crystallized PZT in the perovskite structure and ferroelectric behaviour has also been observed. By the use of a RuO₂ film 100 nm thick at the PZT/aluminium interface, the coercive field and tunability values have been strongly improved despite an increase of the dielectric losses. The lead excess introduced in the precursor solution has been increased up to 65 % in order to lower the crystallization temperature of the PZT around 560 °C and tunability has been studied as a function of annealing time and temperature.     

Quantitative Sputter Depth Profiling of Silicon- and Aluminium Oxynitride Films

 Silicon- and aluminium oxynitride films have gained attention because of their interesting properties in various fields of technology. The specific properties strongly depend on the concentration of oxygen and nitrogen in the films. For the quantitative analysis of homogeneous silicon- and aluminium oxynitride films, EPMA has been proven a very reliable and precise method of analysis. In order to characterise films with graded composition or interface effects between the film and the substrate it is necessary to use sputter depth profiling techniques such as SIMS, hf-SNMS, AES, or hf-GD-OES. Unfortunately, stoichiometric silicon- and aluminium oxynitride films are insulating and therefore charge compensation has to be applied. For the quantification it was necessary to prepare calibration samples which have been analysed by different bulk analytical techniques such as NRA, RBS and EPMA. With these calibration samples, sensitivity factors have been determined and the functional dependence of the sensitivity factors on the composition has been derived. The advantages and disadvantages of the different sputtering techniques and the applicability of the obtained sensitivity functions for the quantitative depth profiling of silicon- and aluminium oxynitride films are discussed.     

Compatibilizing effect of functionalized polystyrene blends: a study of morphology,thermal, and mechanical properties

Polystyrene (PS), being an amorphous polymer is immiscible with other polymers. To engender miscible blends, PS has been functionalized with an active amino‐functional group on the molecular chains of PS to yield amino‐substituted polystyrene (APS), which serves as a reactive compatibilizer. The compatibilization effect of amino functionalized polystyrene on the rubber toughening was explored and results were compared in terms of morphology, thermal, and mechanical properties of PS/SEBS‐g‐MA versus APS/SEBS‐g‐MA blends. In addition, the effect of rubber content on the blend morphology and mechanical properties were investigated. An appreciable change in the thermal stability of APS blends in comparison with PS blend has been probed. A marked correlation has been observed between phase morphology and thermal stability. Use of APS produced the compatibilized blends which render improved blend morphology, enhanced thermal and mechanical properties. Optimal thermal, morphological and mechanical profiles were depicted by 20‐wt% APS blend. Copyright © 2008 John Wiley & Sons, Ltd.     

Interface of ZnS single sheet and substrates: a first‐principles study

Two‐dimensional materials have aroused great interests because of their unique properties not seen in the bulk counterparts. The interface of the ZnS single sheet and substrates are studied in this paper. Different from isolated ZnS single sheet, here in this study, the ZnS single sheet has a remarkable corrugation feature because of the interaction between the ZnS single sheet and the substrate. The top‐site Zn means an attractive reaction with the substrate while the top‐site S means repulsive. For ZnS single sheet/Si(111) interface, the symmetry of the interface does not decrease after geometry optimization because the two layers have a good lattice matching. For ZnS single sheet/Ag(111) interface, an unbalanced interaction (attractive or repulsive) between the ZnS single sheet (Zn or S atom) and Ag surface leads to remarkable corrugation of the ZnS single sheet and the symmetry of the interface decreases. Copyright © 2017 John Wiley & Sons, Ltd.