Nanoscale composite materials in the system SiO2–TiO2

Nanoscale composite materials based on the SiO₂–TiO₂ system were prepared in the form of co-precipitated composites and core SiO₂–shell TiO₂ composites, with specific surface area 150–650 m²/g and sorption volumes 0.1–1.0 cm³/g. It is shown that variation of phase composition and morphology permits to change their structural-adsorption properties and nanocrystallites size after thermal treatment. It is discovered that co-precipitated composite materials differ from core SiO₂–shell TiO₂ composites by a component interaction degree. It determines the difference of the titan-containing component crystallization process and alteration of their structural-absorption properties after thermal treatment. The results of the tests of composites as photocatalysts for Rhodamine B decomposition reaction, as catalysts of Hantzsch and Biginelli reaction, and as fillers in electrorheological fluids are shown.     

CNT-based organic-inorganic composite materials with optoelectronic functionality

This paper focuses on the fabrication of organic-inorganic composite materials with optoelectronic functionality based on carbon nanotubes (CNTs) by chemical and physical modifications. The one-dimensionally (1D) ordered composites of rare earth phthalocyanine compounds (RePc₂) encapsulated by MWCNTs were obtained using a simple capillary filling method. The CNT-templated assembly of RePc₂ nanowires was performed by a phase-separation method. Two other kinds of organic-inorganic 1D-ordered optoelectronic composites were prepared using the template method: coating MWCNTs with a fluorescent poly(tripheny lamine) related co-polymer can be realized via a facile phase-separation strategy: 1D hy brid of bamboo-shaped CNTs covalently bound to RePc₂. The relationship between the microstructure of the obtained 1D-ordered composites and optoelectronic properties was studied, and it was found that these ordered composites exhibited enhanced photoconductivity due to the charge transfer between the composite components.     

Metal-ceramic composite materials from zeolite precursor

A straightforward technique of synthesis of metal-ceramic composite materials using a zeolite precursor is proposed. The first stage of this technique consists of the transition metal (Fe²⁺, Co²⁺, Ni²⁺ and Cu²⁺) cation exchange of commercial zeolites. The subsequent stages provide the reduction of these zeolites by thermal treatment under reducing atmosphere and the sintering of the ceramic matrix embedding the metallic particles. The stages of reduction and sintering may be performed according to two different modalities depending on the desired final product. If metal-ceramic composites for structural applications are desired, the stages of reduction and sintering are performed separately. If metal-ceramic composites for electromagnetic applications are desired, the stages of reduction and sintering are combined into a single firing step.     

Excess capacity on compound phases of Li2FeTiO4 composite cathode materials synthesized by hydrothermal reaction using optional titanium sources to boost battery performance

Li₂FeTiO₄ composites have been produced using commercial LiAC, FeCl₂ and different titanium sources by hydrothermal synthesis (HS) at 175 °C and subsequent annealing at 700 °C. Impure phase TiO₂, Fe₂O₃ and FeTiO₄ were detected out among the Li₂FeTiO₄ composites with different titanium sources. Micron and nano-sized particles of Li₂FeTiO₄ were prepared from various titanium raw materials, with nano-sized particles predominating when titanium raw materials were layered hydrogen titanate nanowire (H₂Ti₃O₇NW, HTO-NW) and titanium oxide nanotubes (TiO₂NB). The Li₂FeTiO₄ composites synthesized by HTO-NW shows a primary particle size of 50−200 nm of high crystallinity staggered with undissolved nanowire with a diameter size of about 100 nm. The samples using one-dimensional nanometer titanium oxide (TiO₂ NB) as the raw material can get a super high initial discharge capacity of 367.8 mAh/g at the rate of C/10 and excellent cycling stability. The selection of raw materials and adopting multi-phase modification can be considered as an effective strategy to improve the electro-chemical properties of Li₂FeTiO₄ composite cathode materials for the lithium secondary battery.     

High capacity silicon/carbon composite anode materials for lithium ion batteries

Silicon/carbon composite materials are prepared by pyrolysis of pitch embedded with graphite and silicon powders. As anode for lithium ion batteries, its initial reversible capacity is 800–900 mAh/g at 0.25 mA/cm² in a voltage range of 0.02/1.5 V vs. Li. The material modification by adding a small amount of CaCO₃ into precursor improves the initial reversibility (η₁=84%) and suppresses the capacity fade upon cycling. A little higher insertion voltage of the composites than commercial CMS anode material improves the cell safety in the high rate charging process.     

A combined Mössbauer spectroscopy and x-ray diffraction operando study of Sn-based composite anode materials for Li-ion accumulators

The reaction mechanisms of Li with Sn/BPO₄ composites to be used as negative electrode materials for Li-ion batteries were studied during electrochemical cycling by operando Mössbauer spectroscopy and X-ray diffraction using a specifically conceived in situ electrochemical cell. The starting composites consist of three main components: β-Sn particles as the electrochemically active species, an inactive matrix of BPO₄ and an amorphous Sn^II-borophosphate interfacial phase linking the two former components and improving the cohesion of the composite. During the first discharge, the latter Sn(II) species are first reduced to zerovalent tin forming Li-poor Li–Sn alloys. After its complete reduction, the reaction of Li continues with β-Sn leading to Li–Sn alloys increasingly rich in Li, with a final composition between those of Li₇Sn₂ and Li₁₃Sn₅. X-ray diffraction shows a progressive loss of long range order of the composites with the suppression of the diffraction peaks of the initial β-Sn and the formation of an ill-defined mixture of Li–Sn alloys. The evolution of this mechanism is investigated on going from a reference Sn/BPO₄ composite prepared by conventional ceramic methods with common micrometric BPO₄ to a new improved material prepared by carbothermal synthesis starting from nanometric BPO₄. With the new composite prepared by carbothermal synthesis, a significant improvement of the reversible capacity at the first cycle is obtained together with a slight improvement of the cycling behaviour. An additional improvement can be obtained by increasing the rate of the first discharge, and thus hampering the formation of the thermodynamically stable LiSn intermetallic.     

Latent heat nano composite building materials

Heat storage for heating and cooling of buildings reduces the conventional energy consumption with a direct impact on CO₂ emissions. The goal of this study was to find the physico-chemical fundamentals for tailoring phase change material (PCM)-epoxy composites as building materials depending on phase change temperature and latent heat using the optimal geometry for each application. Thus, some nano-composite materials were prepared by mixing a PCM with large latent heats with epoxy resin and Al powder. Some polyethylene glycols of different molecular weights (1000, 1500, and 2000) were used as PCMs. Subsequently these PCM-epoxy composites were thermo-physically characterized by DSC measurements and found to be suitable for building applications due to their large latent heat, appropriate phase change temperature and good performance stability. Moreover these cross-linked three dimensional structures are able to reduce the space and costs for encapsulation.     

LiVPO4F/Li3V2(PO4)3 nanostructured composite cathode materials prepared via mechanochemical way

Single-phase LiVPO₄F and LiVPO₄F/Li₃V₂(PO₄)₃ nanostructured composite cathode materials were prepared by heating of the VPO₄?+?LiF mechanochemically activated mixture to 700 °C and subsequent quick or slow cooling to room temperature, respectively. The formation of the composites was proved by a combination of different physico-chemical methods, including XRD, FTIR, ⁶Li and ³¹P NMR, SEM, TEM, and HRTEM. It has been shown that in the composites LiVPO₄F and Li₃V₂(PO₄)₃ nanocrystals well inset into each other resulting in the nanodomain composite formation. Charge–discharge curves of the composites have a sloping profile both in the high-voltage (3.0–4.5 V) and in the low-voltage (1.3–2.5 V) ranges, noticeably different from plateaus for a phase-pure LiVPO₄F, thus indicating a probable change of a two-phase regime of lithium intercalation for a single-phase one. Enhanced rate capability of the LiVPO₄F/Li₃V₂(PO₄)₃ composites is associated with their microstructure and high ionic conductivity of Li₃V₂(PO₄)₃.     

Electrochemical performance of LiVPO<Subscript>4</Subscript>F/C composite cathode prepared through amorphous vanadium phosphorus oxide intermediate

LiVPO₄F/C composites with better electrochemical performance were prepared by calcination of LiF and amorphous vanadium phosphorus oxide (VPO) intermediate synthesized by a sol–gel method using H₃PO₄, V₂O₅ and citric acid as raw materials. The properties of LiVPO₄F/C composites were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical tests. The analysis of XRD patterns and Fourier transform infrared spectra (FTIR) reveal that VPO intermediate prepared by sol–gel method is amorphous and VPO₄ may exist in VPO intermediate. The compositions of LiVPO₄F/C composites are related to the calcination temperature for preparation of amorphous VPO/C intermediate and LiVPO₄F/C composite prepared by VPO/C synthesized at 700°C consists of a single crystal phase of LiVPO₄F. The electrochemical tests show that LiVPO₄F/C composite prepared by VPO/C synthesized at 700°C exhibits higher discharge capacity and excellent cycle performance. This LiVPO₄F/C composite displays discharge capacity of 133 mAh g⁻¹ at 0.5 C (78 mA g⁻¹) and remains capacity retention of 96.8% after 30 cycles, even at a high rate of 5 C, the composite exhibits high discharge capacity of 115 mAh g⁻¹ and capacity retention of 97% after 100 cycles.     

Sol-gel synthesis and characterization of LiNO3-Al2O3 composite solid electrolyte

Composite solid electrolytes in the system (1 − x)LiNO₃-xAl₂O₃, with x = 0.0-0.5 were synthesized by sol-gel method. The synthesis carried out at low temperature resulted in voluminous and fluffy products. The obtained materials were characterized by X-ray diffraction, differential scanning calorimetry, scanning electron microscopy/energy dispersive X-ray, Fourier transform infrared spectroscopy and AC impedance spectroscopy. Structural analysis of the samples showed base centred cell type of point lattice of LiNO₃ for the composite samples with x = 0.1-0.2 and body centred cell for the sample with x = 0.3. A trace amount of α-LiAlO₂ crystal phase was also present in these composite samples. The thermal analysis showed that the samples were in a stable phase between 48 °C and 230-260 °C. Morphological analysis indicated the presence of amorphous phase and particles with sizes ranging from micro to nanometre scale for the composite sample with x = 0.1. The conductivities of the composites were in the order of 10⁻³ and 10⁻² S cm⁻¹ at room temperature and 150 °C, respectively.     

Lithium intercalation into disordered carbon/SiCN composite. Part 2: Raman spectroscopy and <Superscript>7</Superscript>Li MAS NMR investigation of lithium storage sites

Within this work, we analyze the lithium storage sites within carbon/silicon carbonitride (SiCN) composites. Commercial carbons, HD3 (hard carbon) and LD1N and LD2N (soft carbons), of varying porosity are impregnated with polysilazane (HTT 1800) and pyrolysed at 1100 °C. It is found in the first part of this study (Graczyk-Zajac et al. J Solid State Electrochem 19:2763–2769, 2015) that the initial porosity of the carbon phase plays an important role in determining the lithium insertion capacity and rate capability of the composite material. By applying Raman spectroscopy and solid-state ⁷Li MAS NMR on pristine, lithiated, and delithiated samples, we investigate the lithium storage sites within the composite materials. By means of Raman spectroscopy, it has been found that lithium storage in hard carbon-derived composites occurs in a significant extent via adsorption-like process within unorganized carbon, whereas for the soft carbon composites, storage in turbostratic carbon is identified. ⁷Li solid-state NMR confirms these findings revealing that more than 33 % of lithium stored in HD3/SiCN is adsorbed in ionic form at the surface and in pores of the composite, while around 38 % is stored between carbon layers. LD1N and LD2N composites store more than 50 % of lithium in the intercalation-type sites.     

Non-isothermal kinetics of degradation of ultra-high molecular mass polyethene composite materials

In the present work, the Coats-Redfern method was used to determine the kinetic parameters and the possible reaction mechanism of the thermal degradation of ultra-high molecular mass polyethene and its composites with fiber monocrystals in static air at three different heating rates − 6, 10 and 16 K min⁻¹. The analysis of the results obtained showed that the thermal degradation process of pure ultra-high molecular mass polyethene corresponded to a diffusion controlled reaction (three-dimentional diffusion, mechanism D₃), while its composites with fiber monocrystals degraded by two concurrent mechanisms (diffusion one D₃ and A₁,F₁ mechanism). The fiber monocrystals used increased the thermal stability of the composite materials obtained. The values of the activation energy, frequency factor, the changes of entropy, enthalpy and Gibbs energy for the active complex of the composites were calculated.     

Electrorheology and characterization of acrylic rubber and lead titanate composite materials

Oxide one‐pot synthesis was used to synthesize a polymer precursor to lead titanate, PbTiO₃. Perovskite lead titanate, PbTiO₃, was synthesized via the sol–gel process. The dielectric constant, electrical conductivity and loss tangent of our acrylic rubber (AR71)–lead titanate (PT) composite material (AR/PT_8) were 14.15, 2.62 × 10^?7/Ω m, and 0.093, respectively, measured at 27 °C and 1000 Hz. SEM micrographs of composites between the AR71 elastomer and PbTiO₃ showed that the particles were reinforced within the matrix. The electrorheological properties of the AR71/PT composites were investigated as functions of electric field strength from 0 to 2 kV/mm and PbTiO₃ particle volume fraction. The storage modulus increased linearly with particle volume fraction, with or without an electric field. Without an electric field, the particles merely acted as a filler to absorb or store additional stress. With the electric field on, particle‐induced dipole moments were generated, leading to interparticle interactions, and thus a substantial increase in storage modulus. With PbTiO₃ particle volume fractions as small as 10^?4 embedded in the elastomer matrix, the modulus increased by nearly a factor of 2 as the electric field strength varied from 0 to 2 kV/mm. Copyright © 2008 John Wiley & Sons, Ltd.     

Understanding the interfacial region in organic ionic plastic crystal composite electrolyte materials by solid-state NMR

Organic ionic plastic crystal composites exhibit properties that make them suitable for many applications including energy storage devices and CO₂ separation. In most cases, the mixing of organic ionic plastic crystals with a polymer, salt or a porous material leads to the formation of interfacial regions that can enhance the ion transport of desired ions like Li⁺ for battery applications. The study of these interfacial regions is challenging and requires the use of spectroscopic techniques like solid-state NMR to characterise the structure, interactions, and ion dynamics. This article summarises the advantages and challenges of organic ionic plastic crystals and their composites, and the common NMR methods used to study the interfacial regions between their components.     

Snx[BPO4]1−x composites as negative electrodes for lithium ion cells: Comparison with amorphous SnB0.6P0.4O2.9 and effect of composition

A comparative study of two Sn-based composite materials as negative electrode for Li-ion accumulators is presented. The former SnB_0.6P_0.4O_2.9 obtained by in-situ dispersion of SnO in an oxide matrix is shown to be an amorphous tin composite oxide (ATCO). The latter Sn_0.72[BPO₄]_0.28 obtained by ex-situ dispersion of Sn in a borophosphate matrix consists of Sn particles embedded in a crystalline BPO₄ matrix. The electrochemical responses of ATCO and Sn_0.72[BPO₄]_0.28 composite in galvanostatic mode show reversible capacities of about 450 and 530 mAh g⁻¹, respectively, with different irreversible capacities (60% and 29%). Analysis of these composite materials by ¹¹⁹Sn Mössbauer spectroscopy in transmission (TMS) and emission (CEMS) modes confirms that ATCO is an amorphous Sn^II composite oxide and shows that in the case of Sn_0.72[BPO₄]_0.28, the surface of the tin clusters is mainly formed by Sn^II in an amorphous interface whereas the bulk of the clusters is mainly formed by Sn⁰. The determination of the recoilless free fractions f (Lamb-Mössbauer factors) leads to the effective fraction of both Sn⁰ and Sn^II species in such composites. The influence of chemical composition and especially of the surface-to-bulk tin species ratio on the electrochemical behaviour has been analysed for several Sn_x[BPO₄]_1−x composite materials (0.17<x<0.91). The cell using the compound Sn_0.72[BPO₄]_0.28 as active material exhibits interesting electrochemical performances (reversible capacity of 500 mAh g⁻¹ at C/5 rate).     

Cathodic materials for intermediate-temperature solid oxide fuel cells based on praseodymium nickelates-cobaltites

A unique combination of methods (TPD of O₂, thermogravimetry, isotopic heteroexchange of oxygen in different modes) was used to carry out detailed studies of oxygen mobility and reactivity in mixed praseodymium nickelates-cobaltites (PrNi_{1 ? x} Co _x O_{3 + δ}) and their composites with doped cerium dioxide (Ce_0.9Y_0.1O_{2 ? δ}) as promising cathodic materials stable towards the effect of CO₂ in the intermediate-temperature region. It is shown that in the case of composites of PrNi_{1 ? x} Co _x O_3+δ-Ce_0.9Y_0.1O_{2 ? δ} synthesized using the Pechini method and ultrasonic treatment, stabilization of the disordered cubic perovskite phase due to redistribution of cations between the phases provides high oxygen mobility. Preliminary results on tests of cathodic materials of this type supported on planar NiO/YSZ anodes (H.C. Starck) with a thin layer of YSZ electrolyte and a buffer Ce_0.9Y_0.1O_{2 ? δ} layer showed that power density of up to 0.4 W/cm² was reached in the region of medium (600–700°C) temperatures, which was close to typical values for fuel cells of this type with cathodes based on strontium-doped perovskites and their composites with electrolytes.     

An experimental investigation of wear of glass fibre-epoxy resin and glass fibre-polyester resin composite materials

In this paper, the effects of resin content on the wear of woven roving glass fibre-epoxy resin and glass fibre-polyester resin composite materials have been examined. Furthermore, composite materials are experimentally investigated under different loads and speeds by using a block-on-shaft wear tester. The influences of two thermosetting resins epoxy and polyester on the wear of glass-woven roving reinforced composites under has been investigated dry conditions. The glass fibre-epoxy resin and the glass fibre-polyester resin composite materials specimens have been tested under different experiment conditions. Tests were conducted for 0.39 and 0.557 m/s speeds, at two different loads of 5 and 10 N. The weight losses were measured after measuring different sliding distances. Wear in the experiments was determined as weight loss. For each experiment, one specimen was used. The amount of wear was measured before the experiment and after the experiment with the apparatus of balance scales with the accuracy of 10⁻³ g. Glass fibre-epoxy resin composites generally showed higher strength and minimum wear when compared with glass fibre-polyester resin composites materials. In addition, Scanning electron microscopy (SEM) is used to study the worn surface to verify the results.     

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.     

Sol-gel synthesis of TeO<Subscript>2</Subscript>-based materials using citric acid as hydrolysis modifier

Sol-gel processing of tellurium oxide has been investigated in the tellurium isopropoxide/citric acid/isopropanol/water system. As evidenced by Fourier transformed infrared spectroscopy (FTIR), citric acid has been found to be a relevant chemical modifier to control hydrolysis-condensation reactions of highly reactive tellurium isopropoxide Te(OCH(CH₃)₂)₄. Thus, depending on the main synthesis chemical parameters such as alkoxide concentration, water and modifier ratios, colloidal sols and gels have been successfully synthesised. The thermal behaviour of the dried gels has been investigated by X-ray diffraction, differential scanning calorimetry coupled with thermogravimetry and also FTIR spectroscopy. On the one hand, the crystallisation of the non-centrosymmetric γ-TeO₂ polymorph as well as the α-TeO₂ phase which the crystallite size ranges from a few ten nanometers (∼50 nm) to a few microns as a function of heat treatment, and, on the other hand, the synthesis of homogeneous sols which can be handled in air and so particularly suitable for the elaboration of thin films provide new opportunities for making tellurite based materials and thin film devices for practical applications.     

Conductivity of composite materials based on Me2(WO4)3 and WO3 (Me = Sc,In)

Composites {Me₂(WO₄)₃ ? xWO₃} (Me = Sc, In) (x = 0.5–99%) are synthesized and characterized by XRD and electron microscopy methods and also by the density and specific surface measurements. Temperature dependences of the total conductivity of composites are measured. The contributions of σ_tot and σ_el are assessed by the $\sigma (a_{O_2 } )$ and EMF methods. The concentration dependences of conductivity and activation energy are plotted based on the σ_tot and σ_ion data. It is shown that (a) in the interval x = 0–30 vol % WO₃ (0–70 mol %), the conductivity is independent of composition and the ionic component prevails; (b) in the interval x = 60–94.5 vol % (90–99 mol %), the electron conductivity prevails and increases with the increase in x; (c) in the x interval of 30–60 vol % WO₃ (70–90 mol %), the conductivity is mixed, i.e., electron(n-type)-ionic; the latter region represents the transition interval from ionic to electron conductivity as x increases. These data are compared with the results obtained earlier for MeWO₄-WO₃ composites (Me = Ca, Sr, Ba). As regards the structural topology, the {Me₂(WO₄)₃ ? xWO₃} composites pertain to the randomly distributed type. It is shown that in contrast to {Me^IIWO₄ · xWO₃} composites, the composites under study do not form the nonautonomous interface phase with the high ionic conductivity. The possible reasons for the observed differences in the topology and the conduction type of composites based on MeWO₄ and Me₂(WO₄)₃ are analyzed.