The role of the interface in a Ti‐based metallic glass matrix composite with in situ dendrite reinforcement

Many in situ metallic glass matrix (MGM) composites have been developed as promising engineering materials having distinguished properties because of sharing virtues of high strength of metallic glasses and large plasticity of crystal phase, for example, Ti₄₇Zr₁₉Be₁₅V₁₂Cu₇ MGM composites (the yield strength: 1600 MPa, the fracture strength: 3024 MPa and the total strain 32.6%). Although the toughening mechanisms in these materials have been investigated, the role of the interface bridging the ductile dendrite and the glass phase is still unclear. To this aim, specimens of the as‐received and after compression of this Ti‐based MGM composite were investigated to by using the transmission electron microscopy and the high‐resolution transmission electron microscopy. The results of the microstructure investigation indicated that the interface in the composite consists of a nanosized transform layer with an approximate width of 4 nm. During plastic deformation, the interface either suppresses plastic deformation caused by dislocations on the dendrite side or initiates nucleation of multiple shear bands throughout nanocrystallization on the glass phase side nearby the interface, which is favorable for the plastic deformation of the material. Copyright © 2014 John Wiley & Sons, Ltd.     

Formation and characteristics of starch‐based dual photo‐function composite hydrogel

Starch‐based dual photo‐functional hydrogel (SDPH) was obtained via incorporating the azo group onto the backbone of polymeric network and titanium dioxide within the gel at the same time. The structure and composition of SDPH were confirmed with Fourier transform infrared spectrometer, ultraviolet‐visible (UV‐Vis) spectroscopy, thermogravimetric analysis, and energy scattering X‐ray spectroscopy. Scanning electron microscopy observation revealed that titanium dioxide was well dispersed within SDPH. It was found that SDPH not only showed a reversible light‐sensitive behavior but also possessed photo‐catalytic activity. Moreover, the dual photo‐characteristics could be modulated by simply varying the initial amount of titanium dioxide.     

Fabrication of Al/AlN nano‐composite layers by friction stir processing of 6061 Al‐T6 substrate

Friction stir processing was employed for the production of Al/AlN nano‐composite layers on a 6061 Al‐T6 substrate. Nano‐sized AlN powder was inserted in a groove in the middle length of the substrate. Defect‐free layers were achieved using tool rotation and substrate advancing speeds in the range of 900–1400 rpm and 63–310 mm/s, respectively. Subsequent passes were conducted to break‐up AlN clusters that formed in a non‐uniform fashion after initial pass. The grain size of aluminum matrix was found to decrease by the introduction of AlN powder. A nano‐composite layer with near uniform dispersion of nano‐sized AlN reinforcements with a ~9.6% volume fraction was achieved in a matrix of fine dynamically restorated Al grains with a mean size of ~2.5 µm after three subsequent passes. This layer showed an average micro hardness value of ~164 HV (much greater than ~103 HV of the underlying substrate). In addition, the nano‐composite layer exhibited superior dry sliding wear performance against hardened steel compared to that of 6061‐T6 substrate. Increasing tool rotation and substrate advancing speeds were found to decrease the AlN content of the processed layer possibly due to increasing in powder scattering by the pin tool. This was associated with a decrease and increase in hardness values and wear‐loss data, respectively. Copyright © 2014 John Wiley & Sons, Ltd.     

Effect of nano‐modified SiO2/Al2O3 mixed‐matrix micro‐composite fillers on thermal,mechanical, and tribological properties of epoxy polymers

Thermo‐mechanically durable industrial polymer nanocomposites have great demand as structural components. In this work, highly competent filler design is processed via nano‐modified of micronic SiO₂/Al₂O₃ particulate ceramics and studied its influence on the rheology, glass transition temperature, composite microstructure, thermal conductivity, mechanical strength, micro hardness, and tribology properties. Composites were fabricated with different proportions of nano‐modified micro‐composite fillers in epoxy matrix at as much possible filler loadings. Results revealed that nano‐modified SiO₂/Al₂O₃ micro‐composite fillers enhanced inter‐particle network and offer benefits like homogeneous microstructures and increased thermal conductivity. Epoxy composites attained thermal conductivity of 0.8 W/mK at 46% filler loading. Mechanical strength and bulk hardness were reached to higher values on the incorporation of nano‐modified fillers. Tribology study revealed an increased specific wear rate and decreased friction coefficient in such fillers. The study is significant in a way that the design of nano‐modified mixed‐matrix micro‐composite fillers are effective where a high loading is much easier, which is critical for achieving desired thermal and mechanical properties for any engineering applications. Copyright © 2016 John Wiley & Sons, Ltd.     

Cobalt ferrite encapsulated in a zwitterionic chitosan derived shell: An efficient nano‐magnetic catalyst for three‐component syntheses of pyrano[3,2‐c]quinolines and spiro‐oxindoles

A nano‐magnetic core‐shell composite fabricated of a unique zwitterionic chitosan‐derived coating and cobalt ferrite core was found to be a green and reusable heterogeneous catalyst for efficient synthesis of pyrano[3,2‐c ]quinoline and spiro‐oxindole derivatives in high to excellent yields. Due to having negative charges at its outermost layer and a high magnetization, the catalyst is finely dispersed in ethanol and can be easily separated from reaction mixtures by using a simple external magnet. It is reasonably stable as can be reused several times without appreciable loss of catalytic activity.     

Improvement in gas separation properties of a polymeric membrane through the incorporation of inorganic nano‐particles

The present work tries to introduce a high‐performance nano‐composite membrane by using polydimethylsiloxane (PDMS) as its main polymer matrix to meet some specific requirements in industrial gas separations. Different nano‐composite membranes were synthesized by incorporating various amounts of nano‐sized silica particles into the PDMS matrix. A uniform dispersion of nano‐particles in the host membranes was obtained. The nano‐composite membranes were characterized morphologically by scanning electron microscopy and atomic force microscopy. Separation properties, permeability, and ideal selectivity of C₃H₈, CH₄, and H₂ through the synthesized nano‐composite membranes with different nano‐particle contents (0.5, 1, 1.5, 2, 2.5, and 3 wt%) were investigated at different pressures (2, 3, 4, 5, 6, and 7 atm) and constant temperature (35°C). It was found out that a 2 wt% loading of nano‐particles into the PDMS matrix is optimal to obtain the best separation performance. Afterwards, sorption experiments for the synthesized nano‐composite membranes were carried out, and diffusion coefficients of the gases were calculated based on solution‐diffusion mechanism. Gas permeation and sorption experiments showed an increase in sorption and a decrease in diffusion coefficients of the gases through the nano‐composite membranes by adding nano‐particles into the host polymer matrix. Copyright © 2011 John Wiley & Sons, Ltd.     

Hydrophobic poly(lauryl methacrylate)‐coated magnetic nano‐composite particles for removal of organic pollutants

This paper described a simple novel technique to prepare magnetic nano‐composite particles coated with highly crosslinked poly(lauryl methacrylate) (PLMA), a hydrophobic polymer because of its long chain alkyl group for application in waste water purification. Nano‐sized magnetite (Fe₃O₄) particles prepared by coprecipitation of Fe²⁺ and Fe³⁺ from their alkali aqueous solution were encapsulated with SiO₂ following treatment with tetraethylorthosilicate (TEOS). Finally precipitation copolymerization of LMA and divinyl benzene (DVB) in the presence of Fe₃O₄/SiO₂ particles was carried out within stable isolated droplets containing hexadecane–toluene mixture (4:1 mixture HD‐T). The produced PLMA‐coated magnetic composite particles named as Fe₃O₄/SiO₂/P(LMA‐DVB) were characterized by Fourier Transform IR (FTIR), transmission electron microscopy (TEM), thermogravimetry (TG) and X‐ray diffractometer (XRD) analyses. The performance of the composite particles was evaluated for the removal of organic pollutants from water. Copyright © 2015 John Wiley & Sons, Ltd.     

Interface characteristic of aramid fiber reinforced poly(phthalazinone ether sulfone ketone) composite

Interface is an important microstructure for advanced polymer‐matrix composite. The composite interface is the bridge and the link for stress transferring between the fiber and the matrix resin. In this work, oxygen plasma treatment was used for modification of aramid fiber surface. The effects of plasma treatment power on interlaminar shear strength of composite were evaluated by short‐beam shear test. The morphologies of both the aramid fiber surface and its composite interface fracture were observed by SEM. The chemical structure and surface chemical composition of the plasma‐treated and separated fibers were analyzed by Fourier transform infrared (FTIR) and XPS, respectively. The results showed that the interlaminar shear strength of composite was enhanced by 33% with plasma treatment power of 200 W. The FTIR and XPS results indicated that the active functional groups were introduced onto the aramid fiber surface by plasma treatment forming chemical bonds with the poly(phthalazinone ether sulfone ketone) resin. The SEM results proved that the aramid fiber surface was roughened by plasma treatment enhancing the mechanical bond with the poly(phthalazinone ether sulfone ketone) resin. The composite rupture occurred from the composite interface to the fiber or the matrix resin. Copyright © 2017 John Wiley & Sons, Ltd.     

Preparation of ZnO nanoparticle‐reinforced polyamide 6 composite by in situ‐coproduced method and their properties

Polyamide 6/ZnO nanocomposites (noted as PA6/ZnO) were prepared by an in situ co‐producing method, during which Zn₂(OH)₂CO₃ decomposed into nano‐ZnO in the process of the opening‐ring polymerization of caprolactam at high temperature. Transmission electron microscopy, X‐ray diffraction, thermogravimetric analysis, and differential scanning calorimetry were used to analyze the size and dispersive properties of nano‐ZnO, the crystallization and melting properties, the thermal properties, and crystal structure of PA6/ZnO composite, respectively. The results showed that the nano‐ZnO derived from Zn₂(OH)₂CO₃ via in situ polymerization of PA6‐ZnO was uniformly dispersed in PA6 matrix. However, the overall nano‐ZnO crystallization rate and crystal size in the PA6 matrix were hindered by the bulky PA6 molecular chains. The mechanical properties were evaluated using universal tensile and impact testing instruments. The results revealed that PA6/ZnO composite with 0.2% nano‐ZnO content possessed excellent tensile strength, enhanced by 75% in comparison with the pure PA6. The nano‐ZnO had little influence on the impact strength of PA6. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 165–170     

Interface characterization of a metal‐oxide‐semiconductor structure by biased X‐ray photoelectron spectroscopy

X‐ray photoelectron spectroscopy (XPS) measurements of a Pt/HfO₂(SiO₂)/Si metal‐oxide‐semiconductor (MOS) structure under a bias voltage applied between the gate metal and the silicon substrate were studied. The binding energy shifts of Pt 4f, Hf 4f, O 1s and Si 2p according to the applied voltage were investigated using the MOS structure. After the influence of measurements on the results was carefully examined under various conditions, the amount of the shifts was analyzed from a viewpoint of band alignment. Based on the experimental results, a new way of interpreting the deviation of the electric properties from the ideal ones in a band diagram was proposed. It was demonstrated that the biased XPS is a very powerful method to understand the origin of the electric properties of MOS. Copyright © 2010 John Wiley & Sons, Ltd.     

Intramolecular O‐arylation using nano‐magnetite supported N‐heterocyclic carbene‐copper complex with wingtip ferrocene

Nano‐magnetite supported N‐heterocyclic carbene‐copper complex with wingtip ferrocene has been prepared via multi‐step procedure. The complex has been characterized by various analytical techniques such as fourier transform infrared (FT‐IR), fourier transform Raman (FT‐Raman), X‐ray photoelectron spectroscopy (XPS), X‐ray diffraction (XRD), transmission electron microscopy (TEM) and vibrating sample magnetometer (VSM) analysis. The catalytic activity of the complex has been exploited in intramolecular O‐arylation of o‐iodoanilides under heterogeneous conditions. The complex could be successfully recycled up to twelve consecutive cycles.     

Nanoscale polyoxometalate‐based inorganic/organic hybrids

The latest advances in the area of polyoxometalate (POM)‐based inorganic/organic hybrid materials prepared by self‐assembly, covalent modification, and supramolecular interactions are presented. This Review is composed of five sections and documents the effect of organic cations on the formation of novel POMs, surfactant encapsulated POM‐based hybrids, polymeric POM/organic hybrid materials, POMs‐containing ionic crystals, and covalently functionalized POMs. In addition to their role in the charge‐balancing, of anionic POMs, the crucial role of organic cations in the formation and functionalization of POM‐based hybrid materials is discussed. DOI 10.1002/tcr.201100002     

Nano‐emulsion use for the synthesis of polyaniline nano‐grains or nano‐fibers

We report that nano‐emulsions can be creatively used as a morphology selective synthesis method to prepare not only nano‐grains but also nano‐fibers with high selectivity. Synthesis of the two different morphological materials was demonstrated using polyaniline synthesis as a model case. Polyaniline nano‐grains were synthesized from aniline molecules in nano‐size aqueous droplets as polymerization sites whose droplets were generated by inverse water‐in‐oil nano‐emulsion use, and polyaniline nano‐fibers were synthesized from aniline in aqueous nano‐dimensional channels as polymerization sites whose channels were generated by direct oil‐in‐water nano‐emulsion use containing high population of oil droplets. Using the approaches, we successfully synthesized nano‐fibers of 60 nm diameter with 0.5 µm length and also nano‐grains having diameter of 60–80 nm. The two different polymerization sites of nano‐scale dimension were made by changing the ratio among surfactant, aqueous aniline/HCl solution, and oil, i.e. organic solvent. We found the nano‐fibers synthesized from the channels formed by the direct oil‐in‐water nano‐emulsion have higher bulk electrical conductivity than the nano‐grains which were synthesized from the droplets formed by the inverse water‐in‐oil emulsion. We also found that the emulsion use allows us to use a room temperature synthesis unlike conventional synthesis methods which require to use ice bath temperature. Physical properties of both nano‐fibers and nano‐grains synthesized were characterized by Fourier transform infrared (FTIR), UV–Vis spectra, scanning electron microscopy (SEM), and four probes conductivity measurement. Copyright © 2009 John Wiley & Sons, Ltd.     

Antibacterial cellulose acetate films incorporated with N‐halamine‐modified nano‐crystalline cellulose particles

Cellulose acetate (CA) membranes have been widely used as food packaging materials as well as reverse osmosis systems. This study presents the manufacturing of composite CA film with antibacterial properties which is essential for CA film applications in the industry. N‐Halamine precursor of polymethacrylamide‐modified nano‐crystalline cellulose particles (NCC‐PMAMs) were prepared and incorporated into CA film. The composite films with intercalated structure were formed via a solvent‐casting technique. After chlorination, the composite film CA/NCC‐PMAM‐Cl‐1.0 with 1.82 × 10¹⁶ atoms/cm² covalently bonded chlorine showed excellent antibacterial properties by inactivating 6.04 logs of Staphylococcus aureus and 6.27 logs of Escherichia coli within 10 and 5 min, respectively. According to X‐ray diffraction spectra, NCC‐PMAMs behaved as a facilitator for film crystallization. The mechanical strength of the composite film also increased compared with that of pure CA film. However, the composite film became brittle and the maximum decomposition temperature decreased slightly. Preliminary data of in vitro cytocompatibility evaluation indicate that the film is not toxic and has potential use in food packaging. Copyright © 2016 John Wiley & Sons, Ltd.     

Surface/interface phenomena in nano‐multilayer coating under severing tribological conditions

An extensive study of surface/interface phenomena during wear of an adaptive TiAlCrSiYN/TiAlCrN nano‐multilayer coating deposited using physical vapor deposition was undertaken under increasingly severe tribological conditions associated with dry end milling of H13 hardened tool steel. The results of FEM modeling on the temperature/stress distribution at different cutting speeds outline actual cutting conditions on the both rake and flank frictional surfaces of the coated tool. Studies of the surface/interface phenomena were made by means of SEM/high‐resolution transmission electron microscopy/XPS analyses. Results demonstrate that intensifying tribological conditions facilitates improved wear performance of the adaptive coating layer. In extreme tribological conditions of ultra‐performance machining (cutting speed of 500 m/min), the self‐organization process establishes entirely through the formation of a nano‐scale layer of dynamically re‐generating tribo‐ceramic films. The formation of these surface nano‐films results in exceptionally efficient protection of the underlying coating layers. In response to the extreme external environment, the coating layer remained almost undamaged during a long run, demonstrating the capacity to efficiently replenish necessary tribo‐ceramic films. In this way, interconnection of various surface and undersurface processes is established in the hierarchically structured tribo‐films/coating layer. This integral performance is responsible for exceptional wear resistance under intensifying and extreme tribological conditions. Copyright © 2016 John Wiley & Sons, Ltd.     

Electrochemical Study of s‐Triazine Herbicides Transfer Across the Water/1,2‐Dichloroethane Interface

The transfer of three s‐triazine herbicides, atrazine (ATR), propazine (PRO) and prometrine (PROM), across the water/1,2‐dichloroethane interface was investigated using cyclic voltammetry. A facilitated proton transfer mechanism from the aqueous to organic phase is demonstrated by the analysis of positive peak potential and peak current as a function of pH. It is shown that the determination of 2.5×10^?5 M – 5×10^?4 M concentration of herbicides in aqueous phase may be possible under the experimental conditions employed.     

β‐cyclodextrin‐based polymeric nano‐receptor: the self‐assembly of cyclodextrin‐appended comb‐copolymer

Well‐defined β‐cyclodextrin (β‐CD)‐appended biocompatible comb‐copolymer ethyl cellulose‐graft‐poly (ε‐caprolactone) (EC‐g‐PCL) was synthesized via the combination of ring‐opening polymerization (ROP) and click chemistry. The resulting products were characterized by ¹H NMR, FT‐IR spectroscopy, and GPC. The synthesized comb‐copolymer could assemble to micelles, with the surface covered by β‐CD. The inclusion with ferrocene derivation was investigated by cyclic voltammetric (CV) experiments, which indicated the potential application of the micelles as nano‐receptors for molecule recognization and controlled drug release. Copyright © 2011 John Wiley & Sons, Ltd.     

Glass‐transition temperatures of nanostructured amorphous bulk polymers and their blends

Nanostructured amorphous bulk polymer samples were produced by processing them with small molecule hosts. Urea (U) and gamma‐cyclodextrin (γ‐CD) were utilized to form crystalline inclusion compounds (ICs) with low and high molecular weight as‐received (asr‐) poly(vinyl acetate) (PVAc), poly(methyl methacrylate) (PMMA), and their blends as included guests. Upon careful removal of the host crystalline U and γ‐CD lattices, nanostructured coalesced (c‐) bulk PVAc, PMMA, and PVAc/PMMA blend samples were obtained, and their glass‐transition temperatures, T_gs, measured. In addition, non‐stoichiometric (n‐s)‐IC samples of each were formed with γ‐CD as the host. The T_gs of the un‐threaded, un‐included portions of their chains were observed as a function of their degree of inclusion. In all the cases, these nanostructured PVAc and PMMA samples exhibited T_gs elevated above those of their as‐received and solution‐cast samples. Based on their comparison, several conclusions were reached concerning how their molecular weights, the organization of chains in their coalesced samples, and the degree of constraint experienced by un‐included portions of their chains in (n‐s)‐γ‐CD‐IC samples with different stoichiometries affect their chain mobilities and resultant T_gs. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1041–1050     

A two‐dimensional copper(II) coordination polymer based on 2‐propyl‐1H‐imidazole‐4,5‐dicarboxylic acid

Single‐crystal X‐ray diffraction analysis of poly[bis(μ₂‐5‐carboxy‐2‐propyl‐1H‐imidazole‐4‐carboxylato‐κ³N³,O⁴:O⁵)copper(II)], [Cu(C₈H₉N₂O₄)₂)]_n, indicates that one carboxylic acid group of the 2‐propyl‐1H‐imidazole‐4,5‐dicarboxylic acid (H₃PDI) ligand is deprotonated. The resulting H₂PDI⁻ anion, acting as a bridge, connects the Cu^II cations to form a two‐dimensional (4,4)‐connected layer. Adjacent layers are further linked through interlayer hydrogen‐bond interactions, resulting in a three‐dimensional supramolecular structure.     

Super‐Hydrophobic PDMS Surface with Ultra‐Low Adhesive Force

Summary: Rough polydimethylsiloxane (PDMS) surface containing micro‐, submicro‐ and nano‐composite structures was fabricated using a facile one‐step laser etching method. Such surface shows a super‐hydrophobic character with contact angle higher than 160° and sliding angle lower than 5°, i.e. self‐cleaning effect like lotus leaf. The wettabilities of the rough PDMS surfaces can be tunable by simply controlling the size of etched microstructures. The adhesive force between etched PDMS surface and water droplet is evaluated, and the structure effect is deduced by comparing it with those own a single nano‐ or micro‐scale structures. This super‐hydrophobic PDMS surface can be widely applied to many areas such as liquid transportation without loss, and micro‐pump (creating pushing‐force) needless micro‐fluidic devices.

Etched PDMS surface containing micro‐, submicro‐, and nano‐composite structures shows a self‐cleaning effect with water CA as high as 162° and SA lower than 5°.