Study of thermal and mechanical properties of composites based on arc-grown carbon nanotubes and heat-resistant cyanoether binder

Multi-walled carbon nanotubes synthesized by means of arc evaporation of graphite were used to prepare composites with a heat-resistant binder based on cyanoether. To increase the homogeneity of distribution of nanotubes in the polymer matrix, the carbon material was cleaned of graphite particles and amorphous carbon with a potassium permanganate solution in concentrated sulfuric acid. By means of X-ray photoelectron spectroscopy, it was shown that the proposed purification procedure leads to the grafting of oxygen-containing groups to the surface of carbon nanotubes. By means of differential scanning calorimetry, it was revealed that the oxide overcoat on the nanotube surface exerts an influence on the character of binder polymerization. The mechanical properties of a carbon-reinforced plastic with different nanotubes contents were measured. It was shown that the admixture of 0.25–0.50% carbon nanotubes improves the mechanical characteristics of carbon-reinforced plastics by 10–20%.     

Variation of the capacity characteristics of a composite material consisting of acetylene black and polytetrafluoroethylene and of its wettability with an aqueous solution under the action of anodic current

The effect exerted by treatment with cyclic anodic current in 1 M H₂SO₄ in the interval 0.0–2.0 V on electrodes made of a porous (55 vol %) composite material consisting of A-437E acetylene black and polytetrafluoroethylene (60 wt %) was studied. The cyclic volt–ampere curves were recorded in 3 M KOH and 1 M H₂SO₄ to determine the double layer capacity. The anodic treatment leads to an increase in the volume of pores filled with the electrolyte and in the electrical capacity of the electrode due both to an increase in the area of the surface wetted with the electrolyte and to the pseudocapacity caused by oxidation of the carbon black surface.     

Influence of the synthesis conditions on the structure and composition of the titanium–magnesium nanocatalyst and on its activity in isoprene polymerization

Synthesis of titanium–magnesium nanocatalyst in a high-pressure reactor under the conditions modeling the industrial conditions was studied. A laboratory scale plant including the units for the product synthesis, washing, and filtration was developed. The effect of elevated pressure (10–90 atm) on the process course, on the properties of the catalyst formed, and on the isoprene polymerization was studied for the first time. An increase in pressure leads to an increase in titanium incorporation into the catalyst from 1.52 to 2–2.3 wt % and simultaneously to an increase in the trivalent titanium content to 81 wt %. The titanium–magnesium nanocatalyst with such properties exhibits enhanced performance in isoprene polymerization without deteriorating the polymer microstructure. The development of the catalyst synthesis procedure on the laboratory scale plant will allow pilot-scale modeling of this process in the future.     

Effect of organomodified layered silicates on the properties and structure of polytetrafluoroethylene

The physicomechanical and triboengineering properties and the structures of polymer composite materials based on polytetrafluoroethylene and layered silicates are studied. The triboengineering characteristics are substantially improved by the introduction of a small amount of layered silicates (2–5 wt %). It is found that the introduction of organomodified layered silicates leads to a considerable reduction in the friction coefficient, by an order of magnitude, and causes an increase in wear resistance (2000-fold). With the use of X-ray structural analysis and scanning electron microscopy, it is shown that, during friction loading, filler particles are localized on the friction surface, thereby hampering wear of the material.     

Influence of radiolysis on the yield of nanocellulose from plant biomass

Radiolysis of plant biomass with doses of 200–300 kGy prior to dispersing by chemimechanical methods increases the yield of nanocellulose from cellulosic feedstock by more than a factor of two. Another advantage of radiation pretreatment of initial samples is the effect of radiation sterilization of isolated nanocellulose hydrogels, whereas the hydrogel obtained without preliminary irradiation rapidly suffers from the attack of molds during storage in the laboratory. Photolysis of plant raw material at a wavelength of 253.7 nm has almost no effect on the yield of nanocellulose. The molecular and supramolecular structure of nanoparticles with a size of 200–300 nm remains unchanged on passing to the nanoscale and corresponds to the macromolecular structure of cellulose. Industrial testing of the hydrogel as an additive (2.5%) for an adhesive composite used in the manufacture of wood laminates (plywood) showed an enhancement of the strength characteristics of the products by 15–20%. The increase in strength is mainly due to an increase in the contact area of cohesive bonding through small coiled molecular entities composed of 10–16 Kuhn segments including up to 28 monomer units each.     

Phase composition and catalytic properties of ZrO2 and CeO2-ZrO2 in the ketonization of pentanoic acid to 5-nonanone

The phase composition, microstructure, and catalytic properties of the samples of ZrO₂ and CeO₂-ZrO₂ calcined in air at 450–500°C in the ketonization reaction of pentanoic acid were studied. It was found that ZrO₂ of tetragonal and monoclinic modifications is characterized by sufficiently high activity and selectivity for 5-nonanone; the yield of 5-nonanone was 66.3–64.9%. The modification of zirconium dioxide with cerium oxide leads to the formation of a substitutional solid solution based on tetragonal ZrO₂. Upon the addition of CeO₂ in an optimum amount of 10 wt % to zirconium dioxide, an increase in the conversion of pentanoic acid was observed with the retention of high selectivity for the target product, which led to an increase in the yield of 5-nonanone to 73.3%. Based on the results of physicochemical studies performed by high-resolution transmission electron microscopy, X-ray diffraction analysis, and X-ray photoelectron spectroscopy, the physicochemical and catalytic properties of the test catalysts were compared.     

Catalytic Etching of Platinoid Gauzes during the Oxidation of Ammonia by Air. Reconstruction of Surface of Platinoid Gauzes at 1133 K in Air,in Ammonia,and in an NH<Subscript>3</Subscript> + O<Subscript>2</Subscript> Reaction Medium

The structure, morphology, and chemical composition of the surface and near-surface layers of platinoid wires of polycrystalline gauzes, containing Pt (81 wt %), Pd (15 wt %), Rh (3.5 wt %), and Ru (0.5 wt %) after treatment at 1133 K in various media—in air, in ammonia, and after NH3 oxidation in air—are studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) spectroscopy, and X-ray photoelectron spectroscopy (XPS). A thin film is found on the surface of the initial gauze containing an oxide layer of Rh₂O₃ with a thickness of ~2 nm, on the surface of which an inhomogeneous graphite-like layer 10–50 nm thick is located. It is shown that the heat treatment of gauzes in air leads to the partial removal of the surface graphite-like film that forms the reticulated structure on the wire surface. The treatment of gauzes in an ammonia atmosphere leads to the complete removal of the graphite-like and oxide layers and to the growth of metal grains of ~10 μm. After the catalytic reaction of NH3 oxidation, a deep structural rearrangement of the surface layer of the wire takes place, as a result of which crystalline metal agglomerates of ~10 μm are formed. It is supposed that the reaction of NH3 molecules with oxygen atoms penetrated on the defects leads to the local increase of temperature, due to which the metal atoms emerge on the surface and form large crystalline agglomerates and pores in the region of the grain boundaries.     

Enzymatic Biosensor Based on the ISFET and Photopolymeric Membrane for the Determinaion of Urea

An ISFET based enzymatic biosensor was developed for the determination of urea. Immobilization of urease was accomplished by the use of liquid mixture which contained vinylpyrrolidone, oligouretane metacrylate and oligocarbonate metacrylate and which can form a polymer under the influence of ultraviolet. The biosensor has the following characteristics: the linear field of responses is in the range of 0.05–20 mM, curve slope – 38 mV/pC, and response time 5–10 min. The increase of the temperature from 28 to 41 °C leads to 15% increase in the intensity of the response of the biosensor. The maximum response is observed at pH 6.0–6.5. At the increase of the NaCl concentration in solution up to 300 mM the biosensor response drops off and achieves half of its initial level. NH₄Cl causes a stronger inhibition of enzyme activity comparing to NaCl. The results obtained with the developed biosensor correlate with the data of standard calorimetric methods. The intensity of the biosensor response decreases gradually during 40 days up to 80% of the initial level. The biosensors prepared with a fresh membrane or membrane preserved during 46 days at 2 °C gave similar responses in solution with an equal concentration of a substrate. It is concluded that the developed enzymatic biosensor is perspective for its clinical application for the determination of urea in blood and that the proposed method to prepare a selective biological membrane may be in a simple way included in integral technology of the semiconductor transducer manufacturing.     

Effect of surface modification of colloidal silica nanoparticles on the rigid amorphous fraction and mechanical properties of amorphous polyurethane–urea–silica nanocomposites

Colloidal silica nanoparticles (NPs) modified with eight different silane coupling agents were incorporated into an amorphous poly(tetramethylene oxide)‐based polyurethane–urea copolymer matrix at a concentration of 10 wt % (4.4 vol %) in order to investigate the effect of their surface chemistry on the structure–property behavior of the resulting nanocomposites. The rigid amorphous fraction (RAF) of the nanocomposite matrix as determined by differential scanning calorimetry and dynamic mechanical analysis was confirmed to vary significantly with the surface chemistry of the NPs and to be strongly correlated with the bulk mechanical properties in simple tension. Hence, nanocomposites with an RAF of about 30 wt % showed a 120% increase in Young's modulus, a 25% increase in tensile strength, a 15% decrease in elongation at break with respect to the neat matrix, which had no detectable RAF, whereas nanocomposites with an RAF of less than 5% showed a 60% increase in Young's modulus, a 10% increase in tensile strength and a 5% decrease in the elongation at break. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2543–2556     

Optimisation of the plasma electrolytic oxidation process efficiency on aluminium

Plasma electrolytic oxidation (PEO) is a surface treatment technology enabling fabrication of adherent thick (50–150 µm) coatings on light metal alloys with significantly enhanced hardness, wear and corrosion resistance compared with other conventional treatments. The technology has the potential to play a significant role in the transport sector for replacement of steel with light‐weight materials of improved durability. A main limitation of PEO lies in its relatively high cost, associated with high energy consumption and low coating efficiency. The present work explores possible routes to improve the process efficiency. It is shown that a combination of conventional pre‐anodising with sequential PEO treatment reduces specific energy consumption up to five times because of an increase of the coating growth rate, up to 10 µm/min, compared with existing PEO processes. A further approach to improved coating efficiency involves PEO in electrolytes with suspended fine or nanoparticles, which results in the formation of thicker coatings in reduced time as a result of the incorporation of the particles from the electrolyte into the coating. Additionally, melting of the coating material during the micro‐arc discharge process leads to formation of stabilised high‐temperature phases, such as tetragonal and cubic zirconia, which provide significantly improved microhardness of the coating material and give a potential for thermal barrier applications. Copyright © 2009 John Wiley & Sons, Ltd.     

Formation of a polyalkyl macromolecule from the hydrolysable component within sporopollenin during heating/pyrolysis experiments with Lycopodium spores

The most resistant component of Lycopodium spores is the macromolecule sporopollenin. The recent and fossil representatives of this material are structurally distinct and the transformations that bring about this chemical discord are poorly understood. To investigate the diagenesis of spores and their biopolymer, solvent extracted and saponified examples of Lycopodium clavatum underwent simulated diagenesis by heating (100–400 °C) under vacuum for 48 h. Following simulated maturation, spores were analysed by pyrolysis-gas chromatography–mass spectrometry (Py-GC–MS) and thermochemolysis-GC–MS. Py-GC–MS data clearly demonstrate that there is an increase in the polyalkyl hydrocarbon material in the pyrolysable component with increasing anhydrous maturation temperature. Hydrous pyrolysis of spores leads to similar changes but with an increased response from aliphatic relative to aromatic material. If the spores are hydrolysed prior to heating the generation of the polyalkyl portion of the macromolecule is markedly reduced. It appears, therefore, that the polyalkyl portion of fossil sporopollenin may be formed by maturation-induced polymerisation of the ‘labile’ hydrolysable component to form a recalcitrant polyalkyl network.     

炭化程度对核桃壳焦孔隙结构和燃烧特性的影响

利用傅里叶变换红外光谱仪(FT-IR)、扫描电子显微镜(SEM)和X射线衍射仪(XRD)研究了炭化程度对核桃壳焦孔隙及微晶结构的影响,并使用热重-差示扫描量热仪(TG-DSC)对核桃壳焦及其原料的燃烧特性进行了分析。结果表明,合适的炭化程度(焦炭挥发分含量为6%-15%)使焦炭内乱层石墨变得无序,碳质微晶结构中缺陷增多,导致焦炭内孔隙结构相对发达;热解温度为500℃时,核桃壳焦的比表面积最大,为374.60 m~2/g;热解温度为600℃时,核桃壳焦的燃烧特性最优,其燃烧特性指数为7.16×10~6;合适的炭化程度可使焦炭内的挥发分含量减少,从而使得核桃壳焦的高位热值升高,且由于相对发达的孔隙使焦炭在燃烧时与空气的接触面积增大,导致焦炭的燃烧速率加快。     

A short,highly efficient synthesis of coenzyme Q(10)

The most efficient synthesis reported to date of ubiquinone (CoQ10) is described. A sequence consisting of six operations is involved which leads to crystalline material in an overall yield of >64%.     

Determination of impurities in micro-amounts of silver alloys by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) after in-situ-digestion in the graphite furnace

Forgeries of antique silver objects can be identified by their fingerprints of impurities. The dissolution of the samples causes severe problems since Au and Ag have to be dissolved simultaneously. In order to overcome that difficulty and to minimize the amount of sample, an ETV-ICP-MS method is presented based on solid sampling and an in-situ-digestion with nitric acid in a graphite tube. Determinations of Au, Bi, Cd, Pb, Sb, Sn and Zn were performed in a range of 10 μg/g–1% and with an accuracy of 10%–50%. Less than 1 mg sample material is required.     

Effects of alkylation upon the proton affinities of nitrogen and oxygen bases

The protonation energies of alkylated derivatives of NH₃ and OH₂ are calculated at the Hartree–Fock level with the split-valence 4-31G basis set. The methyl, dimethyl, and ethyl amines are studied; oxygen bases include methanol, dimethylether, and ethanol. The geometries of each molecule and its protonated analog are fully optimized. It is found that protonation leads to significant changes in the molecular structures. In particular, the bonds to the N and O atoms are substantially elongated, especially when the other atom involved is C rather than H. The calculated absolute proton affinities are somewhat larger than the experimental values. However, the differences in protonation energies of the various molecules relative to one another agree quantitatively with experiment. Replacement of one H atom of the base by a methyl group induces an increase in proton affinity of some 10 kcal/mol. If a second methyl group is added to the N or O atom, a further increment of about 70% this amount is noted. On the other hand, placement of the second C atom on the first methyl group (to form an ethyl substituent) leads to a smaller increase (～30%). The magnitudes of these alkyl substituent effects are somewhat larger for the oxygen bases than for the amines.     

Influence of the Conditions for Preparing LaPO<Subscript>4</Subscript>-Based Materials with Inclusions of the LaP<Subscript>3</Subscript>O<Subscript>9</Subscript> Phase on Their Thermal and Mechanical Properties

A material based on lanthanum orthophosphate LaPO₄ with inclusion of particles of lanthanum metaphosphate LaP³O₉ was synthesized. The influence of the process parameters of the synthesis on the structure and properties of the material was determined. Heat treatment of the coprecipitated lanthanum phosphates at 700°C leads to the formation of a nanopowder with the LaPO₄crystallite size of approximately 17 nm. Heat treatment of the nanopowder at temperatures from 1100 to 1500°C yields compact materials based on the LaPO₄–LaP₃O₉ system. The heat treatment of the nanopowder at 1100°C leads to a sharp decrease in the porosity of the material (to ~5%) at insignificant grain growth (200–400 nm); under these conditions, the thermal conductivity [λ(25°C) = 3.2 W m–1 K^–1], microhardness [Hv(25°C) = 4.6 ± 0.4 GPa], Young’s modulus [E(25°C) = 132 ± 9 GPa], and cracking resistance [K_1c(25°C) = 1.6 ± 0.1 MPa m^1/2] pass through maxima. The thermal expansion coefficient of the material depends on the heat treatment conditions only slightly and amounts to (8.2 ± 0.2) × 10^–6 K^–1.     

Determination of the latex particle size in emulsion polymerization of methyl methacrylate with low emulsifier concentrations

The mean size of the latex particles formed in emulsion polymerization of methyl methacrylate under definite conditions (water: monomer volume ratio 15: 1, 80°C, potassium persulfate concentration 0.07 wt %) decreases from 200 to 9–10 nm as the concentration of an ionic surfactant (anionic Disponil AES 60, SDS, cationic C₁₉H₄₂BrN) is increased from 0.0 to 1.0 wt %. The nonionic surfactants studied influence the size of the latex particles formed differently: with ALM-10, the particle size decreases from 200 to 150–190 nm, whereas with ALM-7 and ALM-2 it increases from 200 to 320 nm as the surfactant concentration is increased from 0.0 to 1.0 wt %. An increase in the concentration of F127 amphiphilic ternary block copolymer from 0.0 to 1.0 wt % leads to a monotonic decrease in the size of the poly(methyl methacrylate) latex particles formed from 200 to 53 nm.     

Gas-transport properties of epoxidated metathesis polynorbornenes

The effect of postpolymerization epoxidation of metathesis polynorbornenes on their gas-transport behavior is studied. For two polymers, unsubstituted polynorbornene and poly(trimethylsilylnorbornene), postpolymerization modification via double bonds is implemented by epoxidation under the action of m-chloroperbenzoic acid to high conversions (95–100%). For initial polymers and their epoxidation products, the permeability and diffusion coefficients are measured and the solubility coefficients are estimated. It is shown that, for both initial polymers, functionalization leads to a marked reduction in permeability (by a factor of 2–10) and diffusion coefficients (by a factor of 3–10); simultaneously, the separation factors increase by a factor of 2–6. Although for all gases the solubility coefficients decrease as a result of epoxidation, the coefficients of CO₂ solubility in both epoxidated polymers increase. This effect may be explained by specific interactions of a СО₂ molecule possessing the quadrupole moment with С–О–С bonds appearing in a polymer.     

Nitric acid activation of graphite granules to increase the performance of the non-catalyzed oxygen reduction reaction (ORR) for MFC applications

Nitric acid and thermal activation of graphite granules were explored to increase the electrocatalytic performance of dissolved oxygen reduction at neutral pH for microbial fuel cell (MFC) applications. Electrochemical experiments showed an improvement of +400 mV in open circuit potential for graphite granules when they were activated. The improvement of ORR performance observed with activated granules was correlated to the increase of Brunauer–Emmett–Teller (BET) surface of the activated material and the emergence of nitrogen superficial groups revealed by X-ray photoelectron spectroscopy (XPS) analysis on its surface.The use of activated graphite granules in the cathodic compartment of a dual-chamber MFC led to a high open circuit voltage of 1050 mV, which is among one of the highest reported so far. The stable performance of this cathode material (current density of 96 A m^?3 at +200 mV/Ag–AgCl) over a period of 10 days demonstrated its applicability as a cathode material without any costly noble metal.