硅藻土/重质碳酸钙复合调湿材料的制备及表征

调湿材料是一种重要的健康环保材料。本工作以硅藻土(DE)和重质碳酸钙(GCC)为原料, 用焙烧法制备了硅藻土/重质碳酸钙复合调湿材料(DE/GCC)。采用X射线衍射仪、傅里叶变换红外光谱仪、场发射扫描电子显微镜和低温氮吸附法对样品的物相、表面官能团、微观形貌、表面元素组成和孔结构特性进行了表征, 在恒温高湿度环境(RH=70%、80%、90%; 30℃)下测试了样品的吸湿性能, 并进行吸湿动力学和吸湿机理分析。结果表明, 焙烧法制备的DE/GCC中生成了硅酸钙和氢氧钙石, DE/GCC的介孔含量增多, 易于形成毛细管凝聚。在相对湿度为70%、80%和90%恒温高湿度环境下, DE/GCC的36 h吸湿量分别达到7.213%、11.159%和14.701%, 分别提高到DE的2.1、2.9和3.0倍。吸湿过程动力学符合准二级动力学模型。     

Preparation of nano-TiO2/activated carbon composite and its electrochemical characteristics in non-aqueous electrolyte

The composite of nano-TiO₂/activated carbon (ACT) was prepared by hydrolytic precipitation of TiO₂ from TiCl₄ in a mixed aqueous solution containing activated carbon and followed by calcination at 450 °C. The physical characteristics of the activated carbon and ACT composite have been studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectronic spectroscopy (XPS) and nitrogen adsorption–desorption measurements at 77 K. Three electrode systems with lithium metal as reference electrode were assembled to study the electrochemical performance of ACT composite and the activated carbon. It is found from galvanostatic charge–discharge tests that the mass specific capacitance and the area specific capacitance of ACT composite in the electrolyte of 1 M LiPF₆–ethylene carbonate (EC)/diethyl carbonate (DEC)/dimethyl carbonate (DMC) increase by 20% and 50%, respectively compared to the pure activated carbon on average. The a.c. impedance spectra show that the ACT composite electrode has higher interfacial electron transfer resistance (R_t) but lower equivalent series resistance (R_s) than the pure activated carbon electrode has. Therefore ACT composite is a promising electrode active material for electrochemical capacitors.     

Characterization of calcium phosphate powders originating from Phyllacanthus imperialis and Trochidae Infundibulum concavus marine shells

The study reports the preparation and characterization of powders consisting of the different phases of calcium phosphates that were obtained from the naturally derived raw materials of sea-shell origins reacted with H₃PO₄. Species of sea origin, such as corals and nacres, attracted a special interest in bone tissue engineering area. Nacre shells are built up of calcium carbonate in aragonite form crystallized in an organic matrix. In this work two natural marine origin materials (shells of echinoderm Sputnik sea urchin — Phyllacanthus imperialis and Trochidae Infundibulum concavus mollusk) were involved in the developing powders of calcium phosphate based biomaterials (as raw materials for bone-scaffolds) by hotplate and ultrasound methods. Thermal analyses of the as-prepared materials were made for an assessment of the thermal behavior and heat treatment temperatures. Samples from both sea shells each of them prepared by the above mentioned methods were subjected to thermal treatments at 450 °C and 850 °C in order to evaluate the crystalline transformations of the calcium phosphate structures in the heating process. By X-ray diffraction analyses various calcium phosphate phases were identified. In Sputnik sea urchins originated samples were found predominantly brushite and calcite as a small secondary phase, while in Trochidae I. concavus samples mainly monetite and HA phases were identified. Thermal treatment at 850 °C resulted flat-plate whitlockite crystals — β-MgTCP [(Ca, Mg)₃ (PO₄)₂] for both samples regardless the preparation method (ultrasound or hotplate) or the targeted Ca/P molar ratio according with XRD patterns. Scanning electron microscopy and Fourier transformed infrared spectroscopy were involved more in the characterization of these materials and the good correlations of the results of these methods were made.     

Growth of nacre in abalone: Seasonal and feeding effects

The processes of aggregation of mineral and organic materials to the growing surfaces in red abalone (Haliotis rufescens) are analyzed. The flat pearl implantation method is used to observe the transient stages of calcium carbonate deposition, the structure of the organic interlayer, and the steady-state growth of aragonite tiles. The morphology of the organic interlayer is characterized by scanning electron microscopy. These results enable a realistic depiction of the formation of the terraced cones that comprise the principal biomineralization mechanism in this gastropod. In all cases, the growth initiated through spherulites, followed by tile formation. The transient stage with spherulitic formation was shorter at higher temperature; this is indicative of a greater activity of the animal at 21 °C. The growth rate in a normally fed gastropod was found to be higher compared with one provided with limited food. The effect of water temperature (seasonal) was also established, with growth proceeding faster in the summer (T ~ 21 °C) than in winter (15 °C). The structures of the organic interlayer and of the epithelium are revealed by scanning electron microscopy.     

Reprint of: Growth of nacre in abalone: Seasonal and feeding effects

The processes of aggregation of mineral and organic materials to the growing surfaces in red abalone (Haliotis rufescens) are analyzed. The flat pearl implantation method is used to observe the transient stages of calcium carbonate deposition, the structure of the organic interlayer, and the steady-state growth of aragonite tiles. The morphology of the organic interlayer is characterized by scanning electron microscopy. These results enable a realistic depiction of the formation of the terraced cones that comprise the principal biomineralization mechanism in this gastropod. In all cases, the growth initiated through spherulites, followed by tile formation. The transient stage with spherulitic formation was shorter at higher temperature; this is indicative of a greater activity of the animal at 21 °C. The growth rate in a normally fed gastropod was found to be higher compared with one provided with limited food. The effect of water temperature (seasonal) was also established, with growth proceeding faster in the summer (T ~ 21 °C) than in winter (15 °C). The structures of the organic interlayer and of the epithelium are revealed by scanning electron microscopy.     

Multi-functional honeycomb ceramic materials produced from bauxite residues

Red mud is a hazardous waste produced by the Bayer process during commercial production of alumina. In this study, red mud is recycled to produce industrial honeycomb ceramic materials. The materials and processing parameters including the type and size the pore-forming agent, sintering temperature, and stripping methodology are studied. The optimal sintering temperature is determined to be 1075 °C. The bending strength, porosity, water absorption capacity, and bulk density are investigated by X-ray diffraction and scanning electron microscopy. The bending strength exceeds 32.66 MPa after addition of calcium carbonate but the porosity and water absorption capacity diminish to 28.6% and 12.6%, respectively. Incorporation of coal powders increases the porosity and water absorption capability to 36.0%, 20.24%, respectively, but the bending strength drops to 21.69 MPa.     

Natural diatomite particles: Size-, dose- and shape- dependent cytotoxicity and reinforcing effect on injectable bone cement

Natural diatomite(DT) is the ancient deposit of diatom skeleton with many regular pores of 50–200 nm and also an abundant source of biogenic silica. Although silica is considered biologically safe and there is an increasing interest of using natural diatomite for biomedical applications, the toxicity information about natural diatomite is still missing. Here, cytotoxicity of natural diatomite on osteoblasts and fibroblasts were compared to hydroxyapatite and the relationships between cytotoxicity and diatomite sizes, dose, geometry or impurity were systematically investigated. Cell adhesion and interaction with diatomite particles were also fluorescently observed. The results clearly suggested a size-, dose-and shape-dependent cytotoxicity of natural diatomite. Disk-shaped diatomite particles with average size of30 um in diameter revealed the least toxicity, while the diatomite particles with irregular shapes and sizes less than 10 um were remarkably toxic. Diatomite particles with proper sizes were then selected to investigate the reinforcing effect on injectable calcium phosphate bone cement. Results showed that diatomite significantly improved the compressive strength of bone cement but did not alter the injectability of the cement. This work provided important biocompatibility information of natural diatomite and demonstrated the feasibility of using selected diatomite as bone implant material.     

Effect of a ductility layer on the tensile strength of TiAl-based multilayer composite sheets prepared by EB-PVD

TiAl/Nb and TiAl/NiCoCrAl laminate composite sheets with a thickness of 0.4–0.6 mm and dimensions of 150 mm × 100 mm were successfully fabricated by electron beam physical vapor deposition. The microstructures of the sheets were examined, and their mechanical properties were compared with those of TiAl monolithic sheet produced by electron beam physical vapor deposition. Tensile testing was performed at room temperature and 750 °C, and the fracture surfaces were examined by scanning electron microscopy. Among the three microlaminate sheets, the TiAl/NiCoCrAl micro-laminate sheet had the best comprehensive properties at room temperature, and the TiAl/Nb micro-laminate sheet showed the ideal high-temperature strength and plasticity at 750 °C. The result was discussed in terms of metal strengthening mechanism.     

Carbonate binders: Reaction kinetics,strength and microstructure

This study focussed on the synthesis of calcium carbonate binders, in situ, from the reaction between hydrated lime and carbon dioxide (CO₂). The aim was to establish the characteristics of the calcium carbonate binders that are associated with its strength, which was considered as an indicator of binder performance. The role of the parameters that are known to play an important part in the kinetics of hydrated lime carbonation processes, in changing the strength of a binder was examined in detail.The parameters identified were CO₂ gas pressure, exposure time and the initial degree of compaction of raw material. All hydrated lime mixtures were prepared at a constant water/solid ratio of 0.25. The hydrated lime compacts made at a range of compaction water/solid ratio (W/S) of 0.25. The hydrated lime compacts made at a range of compaction pressures (0.65–6.0 MPa) were exposed to different CO₂ gas pressures (ambient to 2 MPa) for different periods of time. The resulting products were tested for the amount of Ca(OH)₂ that had converted to carbonate, and for compressive strength. A microstructural analysis of the products was carried out using scanning electron microscopy.The rate of Ca(OH)₂ conversion to carbonate seemed to be enhanced with increasing gas pressure, but it decreased with increasing compaction of the initial mixture. It was revealed that the crystalline state and the morphology of the carbonate formed, rather than the degree of conversion of calcium hydroxide into carbonate, is highly critical to the strength of the binder. The study concluded that in the development of calcium carbonate binder, it is important to meet the experimental conditions that favour the crystallisation of calcium carbonate.     

MOF-derived magnetic porous carbon-based sorbent: Synthesis,characterization, and adsorption behavior of organic micropollutants

Magnetic porous carbon-based sorbent (MPCS) with core-shell structure was prepared from the pyrolysis of Fe^III-modified MOF-5. The component, structure and surface properties of the as-obtained sorbent were investigated by Raman spectroscopy, X-ray diffraction, thermogravimetric analysis, scanning electron microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy. Sorption behaviors of five organic micropollutants (OMPs), such as atrazine, carbamazepine, bisphenol A, norfloxacin and 4-nitrophenol, onto the magnetic porous MPCS were studied in a batch system. The adsorption capacities of the five OMPs onto MPCS followed the order of 4-nitrophenol > norfloxacin > bisphenol A > carbamazepine > atrazine. All isotherms were fitted well by the Dubinin-Ashtakhov (DA) model, and the approximate site energy distributions were acquired. The possible adsorption mechanisms of the five OMPs onto as-prepared MPCS were discussed in detail. This study will aid in further understanding of interactions between the OMPs and MOF-derived carbon-based materials.     

Fabrication of ultrahigh hydrogen barrier polyethyleneimine/graphene oxide films by LBL assembly fine-tuned with electric field application

In this study, layer-by-layer self-assembly of polyethyleneimine (PEI)/graphene oxide (GO) was successfully controlled by an applied electric field. The influences of the applied electric field direction, voltage, and dipping time on the hydrogen barrier properties of PEI/GO self-assembled film were investigated. Ultraviolet–visible light absorption spectroscopy, ellipsometry, atomic force microscopy, and scanning electron microscopy were used to analyze the effects of the electric field on the growth, nanostructure, and micromorphology of the self-assembled film. Results indicated that an applied electric field accelerates the adsorption rate of assembly and increases the GO adsorption quantity. Additionally, such electric field modifies the composite structure of the self-assembled film and spreads out the GO sheets uniformly on the substrate, which results in the formation of a more compact and ordered gas barrier layer with significantly improved hydrogen barrier properties. Higher applied voltage results in a more noticeable field effect. Under 25 V, the hydrogen transmission rate of the PEI/GO self-assembled 10-layer film reached 81 cm³/m² 24 h 0.1 MPa, which was 65% lower than that of standard composite films prepared without using an electric field.     

Influence of mode ratio and hygrothermal condition on the delamination toughness of a thermoplastic particulate interlayered carbon/epoxy composite

Double cantilever beam, end-notched flexure and single leg bending tests were used to determine the effects of temperature and moisture on the toughness of a thermoplastic particulate-toughened carbon/epoxy composite. Tests were performed on both dry and moisture-saturated specimens at temperatures of ?43 °C, 21 °C and 98 °C, and on dry specimens only at 125 °C. In-situ observations and post-test scanning electron microscopy showed increasing matrix ductility with increasing temperature and moisture content. This correlated to an increase in the mode I and a decrease in the mode II toughness. The mixed-mode toughness data and fracture surface morphologies displayed a blend of the mode I and mode II behaviors.     

Accumulative press bonding; a novel manufacturing process of nanostructured metal matrix composites

A new manufacturing process for metal matrix composites has been invented, namely accumulative press bonding (APB). The APB process provided an effective method to produce bulk Al/10 vol.% WC_p composite using tungsten carbide (WC) powder and AA1050 aluminum sheets as the raw materials. The microstructural evolutions and mechanical properties of the monolithic aluminum and Al/WC_p composite during various APB cycles were examined by scanning electron microscopy, X-ray diffractometry, X’pert HighScore software, and tensile test equipment. The results revealed that by increasing the number of APB cycles (a) the uniformity of WC particles in aluminum matrix improved, (b) the porosity of the composite eliminated, (c) the particle free zones decreased and (d) the cluster characteristics improved. Hence, the final Al/WC_p composite processed by 14 APB cycles showed a uniform distribution of WC_p throughout the aluminum matrix, strong bonding between particles and matrix, and a microstructure without any porosity and undesirable phases. The X-ray diffraction results also showed that nanostructured Al/WC_p composite with the average crystallite size of 58.4 nm was successfully achieved by employing 14 cycles of APB technique. The tensile strength of the composites enhanced by increasing the number of APB cycles, and reached to a maximum value of 216 MPa at the end of 14th cycle, which is 2.45 and 1.2 times higher than obtained values for annealed (raw material, 88 MPa) and 14 cycles APBed monolithic aluminum (180 MPa), respectively. Though the elongation of Al/WC_p composite lessened during the initial cycles of APB process, it increased at the final cycles of the mentioned process by 78%. Role of WC particles, uniformity of reinforcement, porosity, bonding quality of the reinforcement and matrix, grain refinement, and strain hardening were considered as the strengthening mechanisms in the manufactured composites.     

Effect of particle size on the in vitro bioactivity,hydrophilicity and mechanical properties of bioactive glass-reinforced polycaprolactone composites

Polycaprolactone (PCL) composite films containing 5 wt.% bioactive glass (BG) particles of different sizes (6 μm, 250 nm, < 100 nm) were prepared by solvent casting methods. The ultra-fine BG particles were prepared by high-energy mechanical milling of commercial 45S5 Bioglass® particles. The characteristics of bioactive glass particles were studied by field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), dynamic light scattering (DLS), and X-ray diffraction (XRD) methods. In vitro bioactivity of the PCL/BG composite films was evaluated through immersion in the simulated body fluid (SBF). The films were analyzed by FE-SEM, energy dispersive spectrometry (EDS), XRD, and atomic force microscopy (AFM). The mechanical properties of highly-porous PCL/BG composites were examined on cylindrical specimens under quasi-static compression load. It was found that partial crystallization of amorphous BG particles during a prolonged mechanical milling occurred and calcium silicate (CaSiO₃) and sodium calcium silicate (Na₂CaSiO₄) phases were formed. The introduction of submicron BG particles (250 nm) was shown to improve the bioactivity of PCL films. In contrast to BG microparticles, the submicron BG particles were distributed on the film surfaces, providing a high surface exposure to SBF with an improved nanotopography. A notable increase in the stiffness and elastic modulus of the composite was also obtained. As compared to submicron BG particles, lower bioactivity and elastic modulus were acquired for PCL/BG nanoparticles. It was also shown that in spite of high specific surface area of the nanoparticles, partial crystallization during mechanical milling and agglomeration of the nanoparticles during processing decrease the bioactivity, hydrophilicity and mechanical response of the BG-reinforced PCL composites.     

Optimization and characterization of direct coating for ibuprofen particles using a composite fluidized bed

Ibuprofen particles (mean particle size, 27 μm and melting point, 76 °C) as core materials were directly coated with a water-soluble polymer. The primary particles were preserved using a composite fluidized bed with a dispersing mechanism at the bottom of the fluidized bed apparatus. Coated primary particles were obtained under the following 3 conditions: (1) Setting the spray air flow rate at 10 L/min from the initial to 2% coating, (2) adding the low-viscosity water-soluble polymer macrogol 6000 to the hypromellose coating solution, and (3) changing the spray air flow rate to 15 L/min from 2% coating. The particles obtained were confirmed to be coated primary particles by scanning electron microscopy of their cross sections prepared by the cryo-focused ion beam method. The dissolution test showed a marked improvement in the solubility of ibuprofen from the coated primary particles compared with that of a physical mixture. In conclusion, the optimization of the direct coating process made it possible to undertake primary particle coating of a raw material that has a low melting point and a particle size of not more than 50 μm. Primary particle coating contributes to improvements in the physicochemical properties of drugs.     

Biomimetic mineralization of calcium carbonate/carboxymethylcellulose microspheres for lysozyme immobilization

Porous calcium carbonate/carboxymethylcellulose (CaCO₃/CMC) microspheres were prepared by the biomimetic mineralization method for lysozyme immobilization via adsorption. The size and morphology of CaCO₃/CMC microspheres were characterized by transmitted electron microscopy (TEM) and zeta potential measurement. The lysozyme immobilization was verified by Fourier transform infrared (FTIR) spectroscopy. The effects of pHs and temperatures on lysozyme adsorption were investigated as well. It was revealed that CaCO₃/CMC microspheres could immobilize lysozyme efficiently via electrostatic interactions and a maximum adsorption capacity of 450 mg/g was achieved at pH 9.2 and 25 °C. Moreover, it was found that the adsorption process fitted well with the Langmuir isothermal model. In addition, UV, fluorescence, and circular dichroism (CD) spectroscopic studies showed that lysozyme maintained its original secondary structure during the adsorption/desorption process. Our study therefore demonstrated that CaCO₃/CMC microsphere can be used as a cost-effective and efficient support for lysozyme immobilization.     

Inclusion of cefalexin in SBA-15 mesoporus material and release property

SBA-15 (Santa Barbara Amorphous-15) is a high ordered mesoporous material. It has the advantages of a non-toxic property, good hydrothermal stability and thermal stability, etc. Inside inner surface a lot of silanols exist. Pore diameter size is uniform and pore size distribution is narrow. This structural feature makes SBA-15 have a higher loading drug amount and be able to effectively extend the drug release cycle. In this paper, polyethylene glycol-block-polypropylene glycol-block-polyethylene glycol was used as template and tetraethyl orthosilicate was used as silica source to prepare SBA-15 by hydrothermal synthesis method. Cefalexin was included in SBA-15 and the included cefalexin drug content was 158.72 mg/g. The composite materials were characterized by using chemical analysis, powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), infrared (IR) spectroscopy, and low temperature nitrogen adsorption–desorption. The results showed that cefalexin had been successfully included in host SBA-15 pore channels. Rational analyses of the release processes of cefalexin drug from the pores of SBA-15 to the simulated body fluid, simulated gastric juice and simulated intestinal fluid were made and sustained-release effects of the drug in complex system were studied. The results showed that in simulated body fluid within 1–5 h cefalexin was fast released and the cumulative release reached 50.00% at 5 h. In 15–20 h, the sustained release speed of cefalexin drug in the composite material decreased and the sustained-release cumulative amount reached 99.87% at 20 h. The release of cefalexin was basically complete. In simulated gastric fluid, composite material sustained-release ended at 4 h, the cumulative sustained release ratio reaching 26.10%. In simulated gastric fluid, the sustained-release was complete at 7 h, the cumulative sustained release ratio reaching 32.46%. The composite material of SBA-15 and cefalexin could improve efficiency of the sustained-release of drug and has a very great potential applicable value.     

Characterisation of the bioactive behaviour of sol–gel hydroxyapatite–CaO and hydroxyapatite–CaO–bioactive glass composites

The fabrication and characterization of sol–gel derived hydroxyapatite–calcium oxide (HAp–CaO) material is investigated focusing on the effect of the addition of a bioactive glass on the material bioactive behaviour through the fabrication of a novel HAp–CaO (70 wt.%)–bioactive glass (30 wt.%) composite material. The bioactive behaviour of the materials was assessed by immersion studies in Simulated Body Fluid (SBF) and the alterations of the materials surfaces after soaking periods in SBF were characterized by Scanning Electron Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FTIR). A brittle and weakly crystalline carbonate hydroxyapatite (HCAp) layer was found to develop on the surface of all samples, few hours after immersion in SBF, confirming the high bioactivity of the material. Alterations of the morphology of the developed HCAp layer, which led to a more compact structure, were observed on the surface of composite samples after 7 days of immersion in SBF. The presence of the CaO phase seems to accelerate the formation of HCAp, while the bioactive glass affects both the morphology and cohesion of the developed layer.     

As(V) removal from aqueous media using α-MnO2 nanorods-impregnated laterite composite adsorbents

We present a novel way of enhancing the utility of low cost readily available laterite by impregnating it with the α-MnO₂ nanorods, thus making a composite material suitable for the removal of As(V) from aqueous media. The composites were synthesized by two methods: (i) ball-milling of a physical blend of laterite with pre-synthesized MnO₂; and (ii) in situ formation of MnO₂ in the presence of laterite. The BET surface area of composites prepared by both methods was markedly higher compared to un-modified laterite, and the presence of MnO₂ in the composite was also confirmed by XRD analysis and TEM microscopy. The adsorption capacity for As(V) was found to be highly pH dependent and the adsorption kinetics followed a pseudo second-order kinetic model. The Langmuir adsorption isotherm was found to be the best model to describe the adsorption equilibrium of As(V) onto un-modified laterite as well both ball-milled and in situ formed composite. The adsorption capacities at room temperature and pH 7.0 were found to be 1.50 mg g^?1, 8.93 mg g^?1 and 9.70 mg g^?1, for un-modified laterite, ball-milled and in situ formed composite, respectively.     

A novel biodegradable nicotinic acid/calcium phosphate composite coating on Mg–3Zn alloy

A novel biodegradable composite coating is prepared to reduce the biodegradation rate of Mg–3Zn alloy. The Mg–3Zn substrate is first immersed into 0.02 mol L^? 1 nicotinic acid (NA) solution, named as vitamin B₃, to obtain a pretreatment film, and then the electrodeposition of calcium phosphate coating with ultrasonic agitation is carried out on the NA pretreatment film to obtain a NA/calcium phosphate composite coating. Surface morphology is observed by scanning electron microscopy (SEM). Chemical composition is determined by X-ray diffraction (XRD) and EDX. Protection property of the coatings is evaluated by electrochemical tests. The biodegradable behavior is investigated by immersion tests. The results indicate that a thin but compact bottom layer can be obtained by NA pretreatment. The electrodeposition calcium phosphate coating consists of many flake particles and ultrasonic agitation can greatly improve the compactness of the coating. The composite coating is biodegradable and can reduce the biodegradation rate of Mg alloys in stimulated body fluid (SBF) for twenty times. The biodegradation process of the composite coating can be attributed to the gradual dissolution of the flake particles into chippings.