Staff

Abstract:
In this research, electrophoretic deposition (EPD) was employed to prepare a porous composite film (ACF electrode) consisting of 90 wt% activated carbon particles, 10 wt% iron oxide nanoparticles, and a chitosan as binder in a facile, fast, and sustainable manner. This micro-mesoporous composite film, with a thickness of ∼45 µm and a surface area of ∼208.1 m2g−1, was coated on a stainless steel substrate. The SEM and TEM investigations proved the homogeneous distribution of carbon microparticles and iron oxide nanoparticles in the deposit, while the EDX, XRD, Raman spectroscopy, and XPS confirmed the chemical composition. ACF electrodes were also used in a symmetric two-electrode cell configuration with a sandwiched gel polymer electrolyte - PVdF(HFP)-PC-Mg(ClO4)2 and revealed a specific capacitance of ∼54.4 F g−1, along with satisfactory energy and power density of ∼4.7 Wh kg−1 and 1.2 kW kg−1, respectively, and excellent electrochemical stability up to ∼10,000 cycles (with merely 8.5% decay by the 5000th cycle). Obtained results confirmed the stability of the used system and its possible application in the field of energy storage and conversion.

Abstract:
New Surfactant PolyIon Complex (SPIC) micelles were assembled by electrostatic complexation of an antibacterial cationic surfactant, cetylpyridinium chloride (CPC), and a double hydrophilic block copolymer (DHBC) containing a neutral comb block of poly(oligo(ethylene glycol)) methyl ether acrylate (PEOGA) and a weak polyacid block of poly(acrylic acid) (PAA). The corresponding SPIC micelles, with a CPC/PAA core and a PEOGA corona, were successfully used as structure directing and functionalizing agents in a soft and sustainable sol-gel strategy, yielding hybrid mesoporous silica (MS) materials with a monomodal pore size distribution centred at 2.8 nm. The influence of synthesis parameters, including the pH, concentrations and ratios of components, was systematically investigated. The obtained hybrid MS materials were intrinsically functional, with PEOGA blocks anchored in silica walls via H-bonding, while weak polyacid blocks, complexed with CPC, were confined within the mesopores. The response of the materials to pH changes (pH 7.4, 4.2 and 3) indicated remarkable stability of the anchored DHBC, while CPC was selectively released under the acidic conditions typical of orodental biofilm microenvironments. This result is noteworthy, since the release of encapsulated amphiphilic drugs into water is less favorable than that of hydrophilic drugs. Owing to the control of their pore and functionality properties, ordered hybrid silica materials templated and functionalized with SPIC systems will be materials of choice for developing pH-responsive biomedical devices using wet processing techniques

Keywords:
Double hydrophilic block copolymer, Cooperative self-assembly, Surfactant-polyion complex micelle, Stimuli-responsive nanomaterials, Sustainable, Sol-gel synthesis

Abstract:
Mg-based materials are good candidates for biodegradable bone regeneration implants due to their favorable mechanical properties and an excellent compatibility with human bone. However, too high corrosion/degradation rate in body fluids still limits their applicability. Coatings based on chitosan (CS) and bioactive glass (BG) particles fabricated by electrophoretic deposition (EPD) on Dulbecco's Modified Eagle Medium (DMEM) pre- treated magnesium alloys have promising potential to suppress the substrate corrosion and additionally to incorporate bioactivity. However, the impact of processing parameters or type of coating components on the long-term substrate corrosion behavior and cell response have not been investigated previously. In this study, two types of composite coatings based on a high molecular weight CS (Mw 340–360 kDa, DDA ≥95%) and embedded particles: solid BG (2 μm) and a mixture of BG and mesoporous bioactive glass nanoparticles (MBGN, 100–300 nm with mesopores 2.3–5.6 nm) were fabricated by EPD on DMEM pre-treated WE43 magnesium alloy. It was found that partial replacement of BG particles with MBGN (ratio 3:1) in the composite coating increases the water contact angle, surface roughness and induces a positive cell response. Although the acidic CS-based solutions and applied EPD conditions may decrease the stability of the temporary barrier formed during the DMEM pre-treatment on WE43 substrate therewith slightly increasing its corrosion sensitivity, the composite coating with a mixture of different sizes of particles (BG, MBGN) is a promising candidate for bone regeneration applications.

Keywords:
WE43, magnesium alloy, chitosan, bioactive glass, mesoporous nano bioactive glass, electrophoretic deposition

Abstract:
Developing saloplastics composed of Compacted Polyelectrolyte Complexes (COPECs) represents a promising strategy for assembling multifunctional and processable polymer matrices in a simple manner. Here, a comprehensive investigation of the potential application of saloplastics as ion reactors for designing catalysts has been performed. First the propensity of saloplastics to exchange and concentrate ions has been elucidated through investigating the influence of Na+ to Cu2+ cation exchange within COPECs assembled from poly(methacrylic acid) (PMAA) and poly(allylamine hydrochloride) (PAH). The multi-scale responses of PMAA/PAH COPECs upon incubation with CuCl2 solutions at pH 3 and 4.5 were investigated chemically by ATR-FTIR, ICP, XPS, DSC and TGA, morphologically by SEM, and mechanically by strain-to-break measurements. Both the amplitude and the kinetics of the COPEC response were driven by the deprotonation rate of PMAA chains, enabling the formation of bridge complexes with Cu2+ and impacting the saloplastic's composition (water content and polyelectrolytes), structure (emergence of macropores) and mechanical properties. Kinetic-based tuning of the molality of copper ions trapped in PMAA/PAH COPECs was demonstrated, enabling the usage of saloplastics as reactors. This ability allowed controlling the growth of Cu(0) nanoparticles in saloplastics by thermal annealing, ultimately adjusting their catalytic activity toward carbon monoxide (CO) oxidation. This work highlights how the ionic reservoir properties of saloplastics must be accounted for when designing the applications of COPEC-based materials.

Abstract:
So far, it has been proven that the magnetic-field-induced (MFI) synthesis is a process which mainly leads to the formation of magnetic metallic one-dimensional nanostructures. Taking advantage of this method, the new procedures which allow manufacture of the magnetic bimetallic iron–cobalt wire-like nanochains with Fe0.75 Co0.25, Fe0.50 Co0.50, and Fe0.25 Co0.75 compositions are demonstrated in this work. They were produced through a simple one-step magnetic-field-induced (MFI) chemical co-reduction of three different mixtures containing a proper amount of Fe2+ and Co2+ ions with aqueous sodium borohydride solution as the reducing agent. The synthesis process was carried out at room temperature without the use of templates, surfactants, complexing agents, and organic solvents. The morphological and structural studies indicated that all as-prepared materials were amorphous, and they were composed of nanoparticles aligned in almost straight chains. Moreover, they revealed the core–shell structures with bimetallic alloy cores containing desired iron-to-cobalt ratios and very thin oxide shells. Furthermore, the obtained nanostructures behaved as ferromagnetic materials. Their magnetic properties were correlated with their structural properties and chemical compositions. It was observed that their saturation magnetization decreased significantly with increasing content of cobalt in the chains, whereas the variation of their coercivity was less pronounced.

Abstract:
The magnetically-assisted growth of the amorphous bimetallic iron–nickel wire-like nanostructures is presented in this work. The applied process is based on a simple reduction reaction of aqueous solutions containing Fe2+ and Ni2+ ions with NaBH4 in the presence of an external magnetic field of about 0.05 T. The morphology, chemical composition, and magnetic properties of as-prepared Fe–Ni nanostructures have been determined by means of scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffractometry, and vibrating sample magnetometry. The obtained experimental data indicate that the as-prepared samples exhibit quite complex architectures i.e., they comprise of nanoparticles aligned in almost straight lines. In addition, they reveal the typical core-shell structures where the amorphous bimetallic alloy cores are covered by thin amorphous oxide shells. In turn, the magnetic measurements show that the Fe–Ni wire-like nanostructures behave as typical ferromagnetic nanomaterials and their magnetic parameters like saturation magnetizations and coercivities are strictly dependent on their sizes and chemical compositions.

Keywords:
amorphous materials, bimetallic nanostructures, magnetic-field-induced synthesis, magneticmaterials, wire-like nanostructures

Abstract:
Compact polyelectrolyte complexes (COPECs), also named saloplastics, represent a new class of material with high fracture strain and self-healing properties. Here, COPECs based on poly(methacrylic acid) (PMAA) and poly(allylamine hydrochloride) (PAH) were prepared by centrifugation at pH 7. The influence of postassembly pH changes was monitored chemically by ATR-FTIR, ICP, DSC, and TGA, morphologically by SEM, and mechanically by strain to break measurements. Postassembly pH stimuli misbalanced the charge ratio in COPECs, impacting their concentration in counterions, cross-link density, and polymer chain mobility. At the material level, changes were observed in the porosity, composition, water content, and mechanical properties of COPECs. The cross-link density was a prominent factor governing the saloplastic's composition and water content. However, the porosity and mechanical properties were driven by several factors including salt-induced plasticization and conformational changes of polyelectrolytes. This work illustrates how multiple-scale consequences arise from a single change in the environment of COPECs, providing insights for future design of stimuli-responsive materials.

Abstract:
In this study, composites of aluminum alloy 6063 reinforced with 10 wt% boron carbide microparticles were successfully fabricated by a combination of spark plasma sintering and stir casting methods, followed by hot extrusion. A systematic study on the relationship between extrusion process variables (i.e. extrusion ratio, temperature, and punch speed) and porosity, particle refinement, particle distribution and consequently tensile properties and fracture behavior of the composites was performed. Extensive electron microscopy analysis and tensile testing of the composites revealed a multifactoral interdependency of microstructural evolution and mechanical properties on the extrusion process variables. For example, while increasing the extrusion ratio at higher temperatures led to moderate particle refinement, better densification of the composites, and improvement in mechanical properties, concurrent particle fragmentation and microvoid formation around the particles at lower temperatures had opposing effects on the mechanical behavior. We show that the dependency of mechanical properties on all such microstructural factors makes it difficult to predict optimum extrusion conditions in aluminum matrix composites. That is, unlike the common approach, extruding the composites at higher temperatures and achieving more reduction in area may not necessarily lead to the most favorable mechanical properties.

Keywords:
Aluminum matrix composite, Hot extrusion, Mechanical behavior, Microstructure, Spark plasma sintering, Stir casting

Abstract:
There have been many investigations on metal matrix microcomposites produced by conventional casting routes; however, in the past decade, the focus has shifted more toward nanocomposites produced via solid state routes. To have a realistic view of performance prediction and optimum design of such composites, in this work Al matrix composites (AMCs) reinforced with WC microparticles, nanoparticles, and bimodal micro-/nano-particles were prepared by spark plasma sintering. The effects of particle size and concentration, and process variables (i.e. sintering temperature, duration, and pressure) on the evolution of microstructure, density and hardness of the composites were studied comprehensively. Full densification of AMCs with high particle concentration was problematic because of ceramic cluster formations in the microstructure. This effect was more emphasized in AMCs containing nanoparticles. AMCs with microparticles were more easily densified, but their hardness benefits were inferior. On the other hand, the mixture of micro- and nano-particles in Al-WC bimodal composites led to better matrix reinforcement integrity and an overall improvement in the microstructural properties. Finally, increasing the sintering temperature improved the microstructural features and hardness of the composites (more enhanced in high wt.% samples), but sintering duration and pressure did not have a big impact on the composite properties.

Keywords:
composite, nanoparticle, microparticle, powder metallurgy, SPS, microstructure

Abstract:
In this research, the effect of the presence of living cells (SaOS-2) on in vitro degradation of Mg-2.0Zn-0.98Mn (ZM21) magnesium alloy was examined by two methods simple immersion/cell culture tests and electrochemical measurements (electrochemical impedance spectroscopy and potentiodynamic polarization) under cell culture conditions. In immersion/cell culture tests, when SaOS-2 cells were cultured on ZM21 samples, pH of cell culture medium decreased, therefore weight loss and Mg2+ ion release from the samples increased. Electrochemical measurements revealed the presence of living cells increased corrosion rate (Icorr) and decreased polarization resistance (Rp) after 48 h of incubation. This acceleration of ZM21 corrosion can mainly be attributed to the decrease of medium pH due to cellular metabolic activities.

Keywords:
biodegradable metals, biomaterials, electrochemical impedance spectroscopy, immersion, cell culture condition

Abstract:
Four kinds of biodegradable polymers were employed to prepare bioresorbable coatings on Mg-2.0Zn-0.98Mn (ZM21) alloy to understand the relationship between polymer characteristics, protective effects on substrate corrosion, cytocompatibility and cell functionality. Poly-l-lactide (PLLA), poly(3-hydroxybutyrate) (PHB), poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) or poly(lactic-co-glycolic) acid (PLGA) was spin-coated on ZM21, obtaining a smooth, non-porous coating less than 0.5 μm in thickness. Polymer coating characterization, a degradation study, and biocompatibility evaluations were performed. After 4 w of immersion into cell culture medium, degradation of PLGA and PLLA coatings were confirmed by ATR-FTIR observation. The coatings of PLLA, PHB and PHBV, which have lower water permeability and slower degradation than PLGA, provide better suppression of initial ZM21 degradation and faster promotion of human osteosarcoma cell growth and differentiation.

Keywords:
Biodegradable metal, Magnesium alloy, Biodegradable polymer, SaOS-2 differentiation, Calcification

Abstract:
In vitro degradation behavior of squeeze cast (CAST) and equal channel angular pressed (ECAP) ZM21 magnesium alloy (2.0 wt% Zn-0.98 wt% Mn) was studied using immersion tests up to 4 w in three different biological environments. Hanks' Balanced Salt Solution (Hanks), Earle's Balanced Salt Solution (Earle) and Eagle minimum essential medium supplemented with 10% (v/v) fetal bovine serum (E-MEM + 10% FBS) were used to investigate the effect of carbonate buffer system, organic compounds and material processing on the degradation behavior of the ZM21 alloy samples. Corrosion rate of the samples was evaluated by their Mg2 + ion release, weight loss and volume loss. In the first 24 h, the corrosion rate sequence of the CAST samples was as following: Hanks > E-MEM + 10% FBS > Earle. However, in longer immersion periods, the corrosion rate sequence was Earle > E-MEM + 10% FBS ≥ Hanks. Strong buffering effect provided by carbonate buffer system helped to maintain the pH avoiding drastic increase of the corrosion rate of ZM21 in the initial stage of immersion. Organic compounds also contributed to maintain the pH of the fluid. Moreover, they adsorbed on the sample surface and formed an additional barrier on the insoluble salt layer, which was effective to retard the corrosion of CAST samples. In case of ECAP, however, this effect was overcome by the occurrence of strong localized corrosion due to the lower pH of the medium. Corrosion of ECAP samples was much greater than that of CAST, especially in Hanks, due to higher sensitivity of ECAP to localized corrosion and the presence of Cl−.

The present work demonstrates the importance of using an appropriate solution for a reliable estimation of the degradation rate of Mg-base degradable implants in biological environments, and concludes that the most appropriate solution for this purpose is E-MEM + 10% FBS, which has the closest chemical composition to human blood plasma.

Keywords:
ZM21 magnesium alloy, ECAP, Simulated body fluids, In vitro degradationBicomponent nanofibers, Biodegradation, Biopolymer

Keywords:
magnetic-field-induced process, magnetic material, nanoalloy, wire-like nanostructure

Abstract:
Application of a biodegradable polymer coating is one of the methods to improve the initial corrosion resistance and cytocompatibility of magnesium (Mg) alloys. However, bulging of the coating film during long term immersion has been reported. Therefore, improvement of interface strength between the coating and the substrate surface is a key for the success of this method. Combination of surface modification [silanization with 3- (glycidyloxypropyl) triethoxysilane (GPTES)] and biodegradable polymer coating [poly-L-lactide (PLLA)] were applied to a Mg- 2.0Zn-0.98Mn (ZM21) cast alloy. Results of a cell proliferation assay show that PLLA and GPTES+PLLA coating successfully improved cell growth during 7 days of incubation and suppressed Mg2+ release after 4 days of incubation. The silanization process had no impact on suppression of corrosion. Calcification was observed on all samples after 1 week of incubation with calcification medium, but the calcified area was much larger on the GPTES+PLLA coated sample than on the uncoated sample.

Keywords:
biodegradable metal, ZM21, cytocompatibility, silane-coupling, PLLA