Wrinkles formed on a thin gold film deposited onto stretched elastic substrates

In this article the possibility of using various elastic polymer substrates for preparing wrinkled gold films was studied. The gold film was deposited on the substrate using an ion‐sputtering technique, while the substrate was stretched and fixed on a frame. The obtained gold film had wrinkles with a striped pattern. However, whether the pattern was well regulated or not depended on the substrate material. Polydimethylsiloxane (PDMS) was the preferable material when it did not contain fillers. Materials containing fillers are not suitable for this purpose. However, double layer substrates that consist of the PDMS without fillers (the upper layer) and the material containing fillers (the lower layer) could be used to obtain a relatively well‐ordered pattern. Copyright © 2005 John Wiley & Sons, Ltd.     

A model of melting of rare gases within bubbles of crystalline metal matrix

Abstract

On the basis of experimental results obtained in the present and some other works a model of melting of rare gas solids within bubbles formed in a crystalline metal matrix as a result of ion implantation is proposed. Rare gas solid is supposed to melt on heating at the expense of the bubble volume expansion by emission of a dislocation loop. On this basis the melting temperature can be estimated as one which is enough to provide for a pressure inside a bubble sufficient for the initiation of the dislocation loop punching. Values of melting temperatures obtained in this way are in good agreement with available experimental data.     

Radical copolymerization of vinylidene cyanide with 2,2,2‐trifluoroethyl methacrylate: Structure and characterization

A novel copolymer of vinylidene cyanide (VCN) and 2,2,2‐trifluoroethyl methacrylate (MATRIF) was synthesized by bulk free radical process in a 52% yield from an equimolar comonomer feed. The copolymer's composition and microstructure were analyzed by FTIR, ¹H‐ and ¹³C‐NMR spectroscopy, SEC, and elemental analysis. The reactivity ratios calculated from both the Q‐e Alfrey‐Price parameters and the Jenkins' Patterns Scheme indicate a tendency to alternation in the copolymerization, the latter method suggesting that MATRIF homopropagation be slightly favoured (r_V = r₁₂ = 0.1, r_M = r₂₁ = 0.3). The molar incorporation of VCN in the copolymer was only 42 mol % according to the 9.0 wt % nitrogen content determined by elemental analysis, in good agreement with the value obtained by ¹H‐NMR. High‐resolution ¹H and ¹³C‐NMR spectra were used to study the microstructure of the copolymer. As an example, the three well‐resolved carbonyl resonances in the ¹³C‐NMR spectrum were assigned to the MATRIF‐centered triads VMV, VMM, and MMM, respectively, (V and M stand for VCN and MATRIF, respectively). The presence of VCN dyads (e.g., in VVM and VVV sequences) was shown to be marginal or absent altogether. Thermogravimetric analysis of poly(VCN‐co‐MATRIF) copolymer showed good thermal stability, and its main pyrolytic degradation taking place only above 368 °C. A 4% weight loss at about 222 °C suggested the presence of a few VCN homodyads, possibly inducing thermal depolymerization. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Microstructural prototyping of ceramics by kinetic engineering: applications of spark plasma sintering

The significance of kinetics on the development of microstructures in connection with sintering of ceramics is well recognized. In practice, however, it still remains a challenge to prepare designed microstructures via engineering the sintering kinetics because of an insufficient understanding of the different operative mechanisms that are in many cases overlapping. In this article the kinetic issues involved in sintering are described and discussed with respect to their potential for prototyping microstructures that yield desired properties. By exploiting and mastering the differences present in the kinetics of grain sliding, densification, chemical reactions, and grain growth, respectively, we have established processing principles for producing bulk ceramics with microstructures consisting of nano-sized grains, aligned grains, and/or non-equilibrium-phase constitutions, and for achieving radically improved superplasticity in brittle ceramics. Although the studies quoted in this article were mainly carried out by spark plasma sintering, more general implications of them are expected, including efficient particle sliding, deformation-induced dynamic ripening, superplastic deformation-induced dynamic ripening, and non-equilibrium integration.     

Bridging the Length Scales: Micromechanics of Granular Media

Aristotle's statement that the whole is more than the sum of its parts aptly describes the essence of a granular material's rich and complex behaviour, which ultimately arises from internal mechanisms developed on many length scales. Recently, non-invasive experimental studies have given remarkable insight into the evolution of these mechanisms, thereby providing benchmarks and a unique opportunity for the theoretical modelling of these systems. This paper focuses on the challenges of capturing these multiscale mechanisms within the framework of continuum theory. In particular, a new approach toward developing a non-local micropolar constitutive model of granular media using micromechanics and internal variable theory is discussed. To demonstrate the predictive potential of these models, we present their application in the analysis of two fundamental problems to the mechanics of granular media: (i) formation and evolution of shear bands (the precursors of material failure), (ii) the classical Flamant problem. Finally, we briefly discuss the computational challenges in bridging the gap between micromechanical studies of granular media and the applications of continuum theory on the macro-scale via a finite element analysis of the flat punch problem. In practice, this problem is used to assess the load bearing capacity of a material and is fundamental to civil and structural engineering.     

Solid polymer electrolytes X: Preparation and characterizations of polyether–siloxane,organic–inorganic,hybrid nanocomposites complexed with lithium perchlorate

Organic–inorganic hybrid nanocomposites of poly(ethylene glycol)/siloxane were obtained via the sol–gel approach. In these composites, nanometric siloxane heterogeneity was embedded into a polymer matrix with a covalent bond at the interfaces. The ²⁹Si magic-angle spinning (MAS) spectrum exhibited a high degree of condensation through the relative abundance of T⁰ [RSi(OR)₃], T¹ [RSi(OR)₂(OSi)], T² [RSi(OR)(OSi)₂], and T³ [RSi(OSi)₃] silicone nuclei. The effect of lithium salt concentration on ionic interaction, conductivity, and thermal properties of these composite electrolytes were investigated by Fourier transform infrared spectroscopy, DSC, thermogravimetric analysis, alternating current impedance, and solid-state ⁷Li MAS NMR measurements. These observations indicated that the different types of complexes by the interactions of Li⁺ and ClO ions are formed within a hybrid host, and the formation of transient crosslinks between Li⁺ ions and the ether oxygens results in an increased glass-transition temperature of the polyether segment and decomposed rate of composite electrolyte. ⁷Li MAS NMR measurements revealed the changes in line shape of lithium resonances with different LiClO₄ contents, suggesting that a significant degree of ionic association is present in the polymer-salt complexes. The behavior of ion transport in these composite electrolytes was correlated with the interactions between ions and polymer host. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1928–1937, 2004     

High-affinity integration of hydroxyapatite nanoparticles with chemically modified silk fibroin

Hydroxyapatite (HA)-based nanocomposites were prepared by a co-precipitation method with silk fibroin (SF) serving as organic matrix. Silk fibroin was chemically modified with an alkali solution or an enzyme attempting to improve the interface between the mineral and the organic matrix. The influences of the alkali and enzyme pretreatments on microstructure and physicochemical properties of HA–SF composite were examined and compared. The results reveal that both the two kinds of pretreatments facilitate the formation of highly ordered three-dimensional porous network throughout the composites, increase the microhardness of the composite, and promote the preferential growth of HA crystallites along c-axis. Among all the as-prepared samples, the composite containing the enzyme pretreated SF shows desirable hierarchical microstructure with higher degree of organization and more uniform pore size distribution. Due to the enzyme pretreatment, HA crystallites undergo obvious changes in morphology from rod-like to␣whisker-like and in crystal growth towards more apparent epitaxy along c-axis. The alkali pretreatment induces the stronger chemical interactions between HA and SF and thus to strengthen the inorganic–organic interfacial adhesion. The newly developed HA–SF composites are expected to be attractive biomedical materials for bone repair and remodeling.     

Synthesis of repeating sequence copolymers of lactic,glycolic, and caprolactic acids

Repeating sequence copolymers of poly(lactic‐co‐caprolactic acid) (PLCA), poly(glycolic‐co‐caprolactic acid) (PGCA), and poly(lactic‐co‐glycolic‐co‐caprolactic acid) (PLGCA) have been synthesized by polymerizing segmers with a known sequence in yields of 50–85% with M_ns ranging from 18–49 kDa. The copolymers exhibited well‐resolved NMR resonances indicating that the sequence encoded in the segmers used in their preparation is retained and that transesterification is minimal. The exact sequences allowed for unambiguous assignment of the NMR spectra, and these standards were compared with the data previously reported for random copolymers. The glass transition temperatures (T_gs) of the PLCA and PGCA copolymers were found to depend primarily on monomer ratio rather than sequence. Sequence dependent T_gs were, however, noted for the PLGCA polymers with 1:1:1 L:G:C ratios; poly LGC and poly GLC exhibited T_gs that differed by nearly 8 °C. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Structure and mechanical properties controlling of elastomer modified polypropylene by compounded β/α nucleating agents

Previous work showed that there was a synergistic effect of nucleating agent (NA) and elastomer in improving the fracture resistance of isotactic polypropylene (PP), relating to the formation of large amounts of β‐PP (β‐NA nucleated system) or the decrease of the spherulites diameters of α‐PP (α‐NA nucleated system). To find the direct relation between the synergistic efficiency of NA/elastomer and the microstructures of the materials, in this work, the ethylene‐propylene‐diene terpolymer (EPDM) modified PP blends with compounded NAs (β/α) were adopted and the changes of the microstructure and mechanical properties were investigated comparatively. The results showed that, with the adjustment of the mass fraction of compounded NAs, the microstructures of PP matrix including supermolecular structure and the relative fraction of β‐PP (K_β) change accordingly. Specifically, the K_β of β‐PP was successfully adjusted in the wide range of 0–78.9%. Consequently, the stiffness and the fracture resistance of the PP/EPDM blends were easily controlled in different degrees. It is believed that this work could provide a guide map for the design and preparation of certain polymer blends satisfying certain requirement. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Relationships between strain,microstructure and oxide growth at the nano‐ and microscale

In the present article, the relationships between oxidation processes, surface strains and the microstructure of duplex stainless steels were investigated. Specimens were oxidized at 500 °C under secondary vacuum for 1 h to form a thin oxide film (thickness in the range of 20–50 nm). Such specimens were considered as the model system for developing novel methods of analysis in understanding the behavior of passive films. The interfacial strain field after oxidation was measured experimentally at the microscale using the point grid method. On the other hand, the chemical composition of the oxide film was determined at the submicroscopic scale by means of local scanning Auger spectroscopy (with a spot diameter of 50 nm). Local variations of the chemical composition of the oxide film were analyzed according to the specimen microstructure and the strain field. Copyright © 2008 John Wiley & Sons, Ltd.