Effects of formulation properties on sol–gel behavior of chitosan/glycerolphosphate hydrogel

Chitosan solution containing glycerolphosphate disodium salt (Gp) is an injectable thermosensitive in situ gel-forming system which undergoes sol–gel transition under certain physiological pH and temperature conditions. When a drug-incorporated chitosan/Gp solution is injected into the body, it forms a three-dimensional gel at 37 °C, which allows the drug to be released in a sustained manner. This hydrogel can be used as a drug delivery system for prolonged release of peptides and glycopeptides. The objective of this work was to investigate the effect of different excipients on the sol–gel behavior of this thermosensitive hydrogel. Chitosan polymeric solutions (2 % w/v) containing Gp and different excipients, such as hydroxypropyl methyl cellulose (HPMC), polyethylene glycol (PEG) with two different molecular weights (PEG200 and PEG1000), and poloxamer (F127) in various concentrations, were prepared, and the pH, sol–gel transition time, and syringeability of the final solutions were evaluated. The obtained results point to HPMC as the best additive for chitosan/Gp solutions in developing an in situ gel-forming drug delivery system with optimum gelling time. A significant decrease was noted in the sol-to-gel transition time (from 90 to 60 s) when HPMC was added to the system. This may have been due to the HPMC structure which acted as a viscosity-enhancing and gel-promoting agent. The in vitro release of vancomycin hydrochloride from chitosan/Gp/HPMC hydrogel was also studied. Vancomycin release studies showed a sustained release profile for over 20 days. It can be concluded that combining chitosan/Gp and HPMC is a promising strategy for preparing a thermally reversible in situ gel-forming delivery system with an optimized gelation time.     

The membrane properties of alumina-coated alumina support layers and alumina-coated diatomite–kaolin composite support layers

ABSTRACT

Porous ceramic membranes are a current research focus because of their outstanding thermal and chemical stability. Recent research has utilised inexpensive natural materials such as diatomite to reduce the expense of these porous ceramic membranes. However, insufficient data exist for microfiltration applications using the diatomite-based membranes. The measured membrane properties of alumina-coated alumina support layers and alumina-coated diatomite–kaolin composite support layers have been compared. These experiments have been used to determine whether the average pore size could be reduced effectively by controlling the thickness of the alumina coating layer, while maintaining acceptable water permeability. The membrane properties of the alumina-coated alumina support layers and the alumina-coated diatomite–kaolin composite support layers were examined using the scanning electron microscopy, mercury porosimetry, and a dead-end microfiltration system.     

Optimization of hybrid sol–gel coatings by combination of layers with complementary properties for corrosion protection of AA2024

The coating system usually employed for corrosion protection of metal substrates consists of different layers which can be constituted of a chemical conversion coating applied on the metal surface followed by a number of organic layers. Hybrid films prepared by the sol–gel method provide a good approach as protective layers on metallic surfaces, although it is necessary to combine the barrier functionality with an active protection mechanism to avoid corrosion when the coating is damaged. Previous works have shown that it is very difficult to reach this result in a mono-layer sol–gel because the amount of inhibitors incorporated tends to increase significantly the porosity of the coating and reduces drastically the barrier properties. This work presents the characterization of a multi-layer sol–gel hybrid inorganic–organic coating system with a structure composed of an intermediate cerium inhibited layer deposited between two un-doped layers on AA2024 alloy. The comparison between the inhibited system and a bi-layer non-inhibited one has allowed to assess the migration of the cerium ions into the hybrid coating towards the substrate corresponding to the improvement of the corrosion properties. The combination of the physical barrier and the active protection enables to obtain an effective protective system.     

Preparation of superparamagnetic β-cyclodextrin-functionalized composite nanoparticles with core–shell structures

In this article, we report an original and feasible protocol for the preparation of superparamagnetic β-cyclodextrin-functionalized composite nanoparticles with core–shell structures via cross linking reaction on the surface of carboxymethyl β-cyclodextrin-modified magnetite (Fe₃O₄) nanoparticles by using epichlorohydrin as a crosslinking agent. The structure and morphology of the prepared composite nanoparticles were studied by Fourier transform infrared spectrometry, X-ray diffraction measurement, transmission electron microscopy and the thermogravimetric analysis. The results show that the prepared roughly spherical composite nanoparticles (diameter about 10–20 nm) with core–shell structures turned out to be magnetite nanoparticles surface-surrounded by a layer of cross-linked CM-β-cyclodextrin polymer. Results of vibrating sample magnetometry testing and inclusive behaviour studying confirmed the superparamagnetism with saturation magnetization value of 52.0 emu/g in an external applied magnetic field of 20000 Oe and inclusion functionality of the composite nanoparticles consisting of magnetite cores and β-cyclodextrin moiety, which implies very important applications in targeting drug delivery technology and separation for specific substances.     

Study of molding structures and physicomechanical properties of carbon-ceramic composite materials of the SiC–C system

The microstructure of composite materials of the composition SiC–C is analyzed. It is established that they are a separate group of materials containing a ceramic matrix. The ceramic matrix experiences tensile stresses, as a result of which within the composite material a traditional internal stress field is distorted. The ceramic matrix increases strength at carbon phase boundaries of the composite material, and it reduces porosity. An excess of ceramic material reduces strength and thermal stress resistance. Requirements are provided for porosity of the structure that govern the optimum field of material composition.     

Preparation of bioactive TiO2–MgO composite ceramics with bone-promoting properties

In the field of hard tissue repair, titanium-based materials have excellent mechanical properties and magnesium-based materials have good bioactivity, but their shortcomings are that titanium-based materials do not have good bioactivity, while magnesium-based materials are limited in application due to their rapid degradation rate. In order to give full play to the advantages of these two materials, the TiO₂–MgO composite ceramic materials were prepared by combining the two elements and sintering at high temperature. By changing sintering temperature and MgO content, the structure composition and bioactivity of composite ceramic materials can be controlled. The surface morphology, mineralization ability in vitro, cytotoxicity and bone-promoting properties of composite ceramic materials were studied. The experimental results show that high MgO content composite ceramic materials will bring too strong alkalinity to the environment, which will accelerate the mineralization ability of materials, but is not conducive to the survival of cells. Composite ceramic materials with suitable sintering temperature and MgO content have good bioactivity and bone-promoting performance, while the porous structure produced by MgO degradation is beneficial to cell spreading and can form a good combination between the material and bone tissue at an early stage. Porous structure and Mg²⁺ can adjust the bone-promoting properties of materials together. Through the above experimental research, it is found that TiO₂–MgO composite ceramic material is a new type of material which is used in the field of hard tissue repair due to its good bioactivity.     

Behavior of alginate–gelatin blended gel with embedded macrovoids: Stress-induced changes and the solute release characteristics

Blending of gelatin to alginate promote cell–material interaction. However, the changes in diffusive and mechanical properties need to be ascertained. This study shows that the presence of two superposed polymer networks, where gelatin is not additionally crosslinked resulted in higher uptake and slower release of vitamin B₁₂. In the presence of gelatin, the stress is found higher for the same level of compressive deformation, and the permeability of the pore fluid during expulsion under compressive stress is found significantly lower. Also, a large residual strain at the end of each cycle in case of cyclic compression is observed, when gelatin is present. A microfluidic device is used to introduce voids uniformly across the blended gel with an objective to increase compressibility, permeability (for faster equilibration of pore pressure), and uptake of bioactive species. The results showing lower permeability and higher uptake in the presence of gelatin are discussed.     

Design and properties 1–3 multi-element piezoelectric composite with low crosstalk effects

Piezoelectric composites are gaining increasingly importance in ultrasonic fields due to their superior properties. Here novel 1–3 multi-element piezoelectric composites were developed by using piezoelectric ceramic as functional phase, epoxy resin as matrix phase, and silica gel and polyurethane as decoupling materials. The effects of decoupling materials and composite thickness on dielectric, piezoelectric and electromechanical coupling properties of the composites were investigated. The coupling response among various elements of the composites was discussed by setting up an ultrasonic testing platform. The results show that the multi-element piezoelectric composites have larger piezoelectric voltage factor than piezoelectric ceramic, however, less relative permittivity and piezoelectric strain factor. With decreasing the composite thickness, the thickness resonant peaks of the piezoelectric composite shift toward high frequency direction, and no obvious high-order and coupling resonant peaks appear. The multi-element piezoelectric composites have larger thickness electromechanical coupling coefficient k_t and less mechanical quality factor Q_m than piezoelectric ceramic. When composite thickness is 5 mm, the epoxy/silica piezoelectric composite has a maximum k_t value of 70.41%, and a minimum Q_m value of 11.29. The coupling response testing results show that epoxy/silica piezoelectric composite shows less crosstalk effect than epoxy/epoxy and epoxy/polyurethane piezoelectric composites.     

Fabrication and thermoelectric properties of SrTiO3–TiO2 composite ceramics

The paper presents the results of preparing biphase SrTiO₃–TiO₂ ceramics as a promising system for n-type thermoelectrics using the features of a two-dimensional electron gas. Ceramics was obtained by reactive spark plasma sintering of SrCO₃ and TiO₂. The dynamics of phase transformations are shown; it is clarified that phase transformations are not the driving force of sintering. The mutual stabilization of the SrTiO₃ and TiO₂ phases is shown. Unique data on the assessment of the temperature gradient in the system have been obtained. A comparison of the thermoelectric characteristics of biphasic ceramics and its constituent phases allows concluding that the role of the two-dimensional electron gas is reduced to modulating the properties of bulk phases. Clear signs of size quantization were detected by the X-ray luminescence method, which is expressed in the blueshift of the luminescence spectrum by 22.3 ± 0.8 meV.     

Mechanical properties of Si3N4–Al2O3 FGM joints with 15 layers for high-temperature applications

“Crack-free” alumina-silicon nitride joints, comprised of 15 layers of gradually differing compositions of Al₂O₃/Si₃N₄, have been fabricated using sialon polytypoids as functionally graded materials (FGM) bonding layers for high-temperature applications. Using flexural strength tests conducted both at room and at elevated temperatures, the average fracture strength at room temperature was found to be 437 MPa; significantly, this value was unchanged at temperatures up to 1000 °C. Scanning electron microscopy (SEM) observations of fracture surfaces indicated the absence of any glassy phase at the triple points. This result was quite contrary to the previously reported 20-layer Al₂O₃/Si₃N₄ FGM samples where three-point bend testing revealed a severe strength degradation at high temperatures. Consequently, we believe that the joining of alumina to silicon nitride using polytypoidally functional gradients can markedly improve the suitability of these joints for high-temperature applications.     

Comparison of solid state and sol–gel derived calcium aluminate coated graphite and characterization of prepared refractory composite

This paper entails an extended investigation on sol–gel thin film of calcium aluminate (CaAl₂O₄) over graphite flakes that improved their oxidation resistance and water wettability. The commercial preparation of calcium aluminate has been compared with the sol–gel synthesis by differential thermal analysis (DTA) and X-ray diffraction (XRD) to assess the feasibility of the latter for coating preparation. Poorly crystalline nanostructured Ca-doped γ-Al₂O₃ is considered to be an important intermediate for this preparation. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) of the calcined gel have been carried out to ascertain its composition. Quantitative chemical analysis of sol gel derived calcium aluminate was also estimated. Atomic force microscopy (AFM) has been conducted to ensure the evolution of hydrophilic nanosized cementitious phases on graphite. Zeta potential values of coated and uncoated graphites with increasing pH have also been determined to distinguish between their compatibility in a refractory castable matrix. Improved physical properties of that high alumina castable containing coated graphite, e.g. apparent porosity (AP), bulk density (BD), cold crushing strength (CCS) have been measured to evaluate the refractory quality. The reasons for its better performance are explored by taking further insight on the microstructural analyses of the fired castable (1500 °C) soaked for an extended period.     

Structural properties of 0.8CaZrO3–0.2CaFe2O4 composite

A composite with the 0.8CaZrO₃–0.2CaFe₂O₄ general formula was prepared by means of a double sintering process. Temperature of 1400 °C was found suitable to obtain the composite based on scanning electron microscopy and X-ray diffraction analysis. Phase composition, crystal structure, Mössbauer effect, microstructure and dielectric properties were studied. The influence of Fe ions on the CaZrO₃ structure has been reported. It was found that Fe substituted Zr in CaZrO₃ and vice versa in CaFe₂O₄ in the amount about 1.5 at% in both cases. The approximated formula of the obtained composite was 0.8Ca(Zr_0.9Fe_0.1)O₃–0.2Ca(Fe_0.8Zr_0.2)₂O₄. The SEM observations revealed that liquid CaFe₂O₄ occurred as a filling phase between CaZrO₃ grains which significantly enhanced densification of the material and influence on its properties. The dielectric constant reached the value of 170 at 1 MHz and the accompanying dissipation factor was very low – 0.005.     

Dielectric properties of Si3N4–SiCN composite ceramics in X-band

Si₃N₄–SiCN composite ceramics were successfully fabricated through precursor infiltration pyrolysis (PIP) method using polysilazane as precursor and porous Si₃N₄ as preform. After annealed at temperatures varying from 900 °C to 1400 °C, the phase composition of SiCN ceramics, electrical conductivity and dielectric properties of Si₃N₄–SiCN composite ceramics over the frequency range of 8.2–12.4 GHz (X-band) were investigated. With the increase of annealing temperature, the content of amorphous SiCN decreases and that of N-doped SiC nano-crystals increases, which leads to the increase of electrical conductivity. After annealed at 1400 °C, the average real and imaginary permittivities of Si₃N₄–SiCN composite ceramics are increased from 3.7 and 4.68 × 10^?3 to 8.9 and 1.8, respectively. The permittivities of Si₃N₄–SiCN composite ceramics show a typical ternary polarization relaxation, which are ascribed to the electric dipole and grain boundary relaxation of N-doped SiC nano-crystals, and dielectric polarization relaxation of the in situ formed graphite. The Si₃N₄–SiCN composite ceramics exhibit a promising prospect as microwave absorbing materials.     

High-strength functionalized pectin/fibroin hydrogel with tunable properties: A structure–property relationship study

Hydrogels possessing high mechanical strength and well-controlled properties are of utmost interest in bone tissue engineering. In the current study, a strong self-crosslinked hydrogel with variable properties has been developed from a combinatory composition of functionalized pectin and silk fibroin. Pectin chains underwent partial oxidation to be decorated with aldehyde functionalities. Later on, functionalized polysaccharide and protein were blended with different ratios, and corresponding variations in crystalline structure as well as in morphological, mechanical, and rheological properties have been monitored. Some theories have been used to better perceive the relation between blending ratio and hydrogel properties. Avrami equation based on time sweep rheological analysis elucidated that in sample with equivalent ratio of oxidized pectin and fibroin, the crystallization was highly delayed due to dominance of Schiff's base reaction. The Herschel–Bulkley model based on flow curve rheology test corroborated that aforesaid composition revealed the most noticeable shear thinning behavior and accordingly the strongest crosslinked network. Finally, rubber elastic theory based on dynamic mechanical analysis implied that said formulation possessed the highest crosslinking density due to higher availability of aldehyde to amine functionalities. Moreover, cell culture studies proved that P50 F50 sample prevailed over other compositions with respect to cell viability and function. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48859.     

Fabrication and properties of lateral p–i–p structures using single-crystalline CVD diamond layers for high electric field applications

Chemical-vapor-deposited diamond p–i–p structures have been fabricated on homoepitaxially grown single-crystalline layers using focused ion beam etching in order to investigate carrier transport properties of diamond in high electric fields more than 10⁶ V/cm. The examined structures included a 200-nm-thick intrinsic (undoped) diamond region laterally sandwiched between two p-type (B-doped) diamond regions. At high fields above ≈3×10⁷ V/cm, I–V characteristics of the lateral p–i–p structure revealed abnormal increases in current. The observed performances can be explained more reasonably in terms of impact ionization events from the valence band to the conduction band in the intrinsic diamond than in terms of direct Fowler–Nordheim tunneling events of electrons from the valence band of the negatively biased p diamond to the conduction band of the intrinsic diamond.     

Microstructure and properties of SiCf/SiC composite joints with CaO–Y2O3–Al2O3–SiO2 interlayer

Using CaO, Y₂O₃, Al₂O₃, and SiO₂ micron-powders as raw materials, CaO–Y₂O₃–Al₂O₃–SiO₂ (CYAS) glass was prepared using water cooling method. The coefficient of thermal expansion (CTE) of CYAS glass was found to be 4.3 × 10^?6/K, which was similar to that of SiC_f/SiC composites. The glass transition temperature of CYAS glass was determined to be 723.1 °C. With the increase of temperature, CYAS glass powder exhibited crystallization and sintering behaviors. Below 1300 °C, yttrium disilicate, mullite and cristobalite crystals gradually precipitated out. However, above 1300 °C, the crystals started diminishing, eventually disappearing after heat treatment at 1400 °C. CYAS glass powder was used to join SiC_f/SiC composites. The results showed that the joint gradually densified as brazing temperature increased, while the phase in the interlayer was consistent with that of glass powder heated at the same temperature. The holding time had little effect on phase composition of the joint, while longer holding time was more beneficial to the elimination of residual bubbles in the interlayer and promoted the infiltration of glass solder into SiC_f/SiC composites. The joint brazed at 1400 °C/30 min was dense and defect-free with the highest shear strength of about 57.1 MPa.     

Sol–gel synthesis of nano-sized silica in confined amorphous space of polypropylene: Impact of nano-level structures of silica on physical properties of resultant nanocomposites

Polypropylene (PP)/silica nanocomposites were prepared by the sol–gel reaction of silicon alkoxide that was impregnated in the confined amorphous nanospace of PP with the aid of supercritical carbon dioxide. This novel technique enabled us to prepare nanocomposites having a variety of silica morphology without altering the higher-order structures of PP, being ideal to study relationships between the silica morphology and mechanical properties of the nanocomposites. The synthesized silica particles were highly dispersed in PP with dimensions comparable to the amorphous thickness (<10 nm), while their mass fractal dimension acquired by small-angle X-ray scattering was dependent on the sol–gel conditions. We found that the Young's modulus as well as the storage modulus in melt viscoelastic measurements was negatively correlated with the mass fractal dimension of silica nanoparticles: A lower mass fractal dimension resulted in not only higher reinforcement but also percolation network formation at a lower silica loading.     

Improved electromagnetic absorbing properties of Si3N4–SiC/SiO2 composite ceramics with multi-shell microstructure

Porous Si₃N₄–SiC composite ceramic was fabricated by infiltrating SiC coating with nano-scale crystals into porous β-Si₃N₄ ceramic via chemical vapor infiltration (CVI). Silica (SiO₂) film was formed on the surface of rod-like Si₃N₄–SiC grains during oxidation at 1100 °C in air. The as-received Si₃N₄–SiC/SiO₂ composite ceramic attains a multi-shell microstructure, and exhibits reduced impedance mismatch, leading to excellent electromagnetic (EM) absorbing properties. The Si₃N₄–SiC/SiO₂ fabricated by oxidation of Si₃N₄–SiC for 10 h in air can achieve a reflection loss of ?30 dB (>99.9% absorption) at 8.7 GHz when the sample thickness is 3.8 mm. When the sample thickness is 3.5 mm, reflection loss of Si₃N₄–SiC/SiO₂ is lower than ?10 dB (>90% absorption) in the frequency range 8.3–12.4 GHz, the effective absorption bandwidth is 4.1 GHz.     

Compressive creep behavior of spark plasma sintered La2O3–YSZ composite

The present paper describes compressive creep behavior of cubic 8 mol% yttria stabilized zirconia+10 mol% La₂O₃ (fabricated by Spark Plasma Sintering) in the temperature range of 1300–1330 °C at a stress level of 45–78 MPa in vacuum. The pre- and post-creep microstructures, relative magnitudes of the stress exponent (n=1.7–2.1) and the activation energy (540–580 kJ/mol) suggest that grain boundary sliding aided by inter-diffusion of La and Zr leading to the formation of pyrochlore La_1.6Y_0.4Zr₂O₇ phase at the grain boundaries during creep is the active creep mechanism in this composite.     

Determination of the elastic properties of amorphous materials: Case study of alkali–silica reaction gel

The gel formed during alkali–silica reaction (ASR) can lead to cracking and deterioration of a concrete structure. The elastic properties of the ASR gel using X-ray absorption and Brillouin spectroscopy measurements are reported. X-ray absorption was used to determine the density of the gel as a function of pressure, and the result yields an isothermal bulk modulus of 33 ± 2 GPa. Brillouin spectroscopy was applied to measure isentropic bulk (24.9–34.0 GPa) and shear moduli (8.7–10.1 GPa) of the gel. The range of values obtained is attributed to the variable composition of samples that were collected under field conditions. Results suggested that amorphous silica becomes expanded and compressible as it absorbs water molecules and alkali ions. This could explain high gel migration rates through the complex pore structures in concrete.