Synthesis of silica microspheres on silicon-modified carbon foams under ablation

Silica microspheres (SMs) were in situ synthesized in silicon-modified porous carbon foams (SCFs) by an economic and efficient technique – high temperature oxyacetylene torch ablation. The microstructure and formation mechanism of SMs were analyzed in detail. Results showed that the resultant SMs generally were several microns in diameter, and mainly distributed in the ablation center zone. The formation mechanism was governed by the vapor–liquid–solid principle during the process of ablation and cooling. The influence of the ablative flame on the physicochemical property of SCFs was the leading cause of the bizarre SMs.     

Nano-scale hydroxyapatite formation on silica fiber by using carbon nanofibers as templates

Nano-scale hydroxyapatite particle network with uniform morphology and good crystallinity was fabricated on silica fiber by using carbon nanofibers as templates and with a methanol solution of Ca(NO3)2 x 4H2O-H3PO4. Field emission scanning electron microscopy, coupled with X-ray diffraction analysis confirmed the template effect and the existence of hydroxyapatite on silica fiber. It was clearly verified that by tuning the formation of carbon nanofibers on silica fiber, it was possible to control the properties of the resulting hydroxyapatite on silica fiber. In addition, the formation mechanism of hydroxyapatite on silica fiber via the template route was proposed.     

Processing of hydroxyapatite ceramic foams

A novel method of producing highly porous hydroxyapatite ceramics via the foaming of ceramic slips is discussed. Foams with densities 15% and an open cell structure have been produced.     

Mesoporous silica obtained by polycondensation of octahydridooctasilsesquioxane

Mesoporous silica, due to its porosity and morphological features, have been considered a fascinating material for many technological applications. In this report, we describe the preparation of a structurally stable mesoporous silica material using octahydridooctasilsesquioxane (T₈ ^H). The structure and properties of final samples were determined by XRD, FT-IR, and TEM methods. Structural analysis has shown that the siliceous material is amorphous but mesoporous. BET surface area, pore volumes, and pore size distribution were measured using nitrogen sorption methods—data were collected from the adsorption branch using BJH method for mesopores and t-plot method for micropores. It was found that the cage-type structure of T₈ ^H molecules and the process conditions determine the specific morphology of the cross-linked products. Completely inorganic, mesoporous silica of a narrow pore distribution was obtained. It was found that the materials have large surface area and pores in the meso range (2–5 nm). The amount of mesopores and the characteristic surface area of the prepared samples strongly depended on the reaction conditions.     

Novel method of preparing hydroxyapatite foams

Porous scaffolds are considered a key strategy in the concept of bone tissue engineering. Hydroxyapatite, which is a bioceramic has been used as a popular scaffold material due to its bioactive and osteoconductive properties. A combination of slurry-dipping and electrospraying has been used as a new foam fabrication method to produce porous and interconnected foam structures. The combined method has shown to overcome the shortcomings of the individual methods and it has produced open pores in the desired range of 100–350 μm. The porosity which was determined by calculation and microtomography was between 84% and 88%. Reduced cracks and thicker struts were observed in the microstructure, pointing to improved mechanical properties.     

Fabrication of hydroxyapatite with highly ordered macroporous frame by colloidal templating method

Three-dimensional, highly ordered macroporous frame of hydroxyapatite has been fabricated via a template-assisted colloidal processing technique. In the present method, colloidal template was first prepared with SiO₂ spheres by gravitational sedimentation, which was then infiltrated with hydroxyapatite precursor prepared by the sol-gel process. The resulting hydroxyapatite replicated the three-dimensionally ordered macroporous structure of SiO₂ template. Modified by H₂O₂, the SiO₂ spheres could be packed into better ordered templates. After removal of the template by immersing in NaOH solution, the well-ordered macroporous frame made from HA was obtained. The arrangement of the pore structure was hexagonal close-packed and pore sizes could be controlled by changing the sizes of SiO₂ spheres. The resulting highly ordered macroporous frame of hydroxyapatite could have potential applications in the biomedical field.     

可溶性酚醛树脂为碳源合成有序介孔炭及其电催化性能

利用介孔硅SBA-15与苯酚、甲醛混合,原位合成可溶性酚醛树脂,高温炭化得有序介孔炭(C1);同时将预聚的酚醛树脂与SBA-15 共混后再聚合,高温炭化得有序介孔炭(C2).微波多元醇还原法合成Pt/C1、Pt/C2、Pt/CMK-5(糠醇为碳源)电催化剂.使用X射线衍射仪(XRD),N2物理吸附,透射电镜(TEM)和循环伏安技术(CV)对介孔炭的结构和催化剂的性能进行了表征.结果表明:CI主要由规则的六方介孔孔道构成,比表面积为947m2/g,孔径分布集巾在4.5nm,Pt微粒在C1上具有良好的分散性,平均粒径约为3nm.C2的孔道较为模糊,负载的Pt微粒有一定程度的团聚.CV曲线显示,Pt/C1催化剂的电化学活性面积(EAS)为54.2m2/g,其催化甲醇氧化的性能优于Pt/C2及Pt/CMK-5而略筹于商用催化剂Pt/C(E-TEK).     

Controllable synthesis of silica hollow spheres by vesicle templating of silicone surfactants

Silica hollow spheres (SHSs) have been designed and prepared through three distinct synthetic routes based on the self-assembling of comb-like copolymer silicone surfactants. This process was based on the rule of similarities for hydrophobicity and hydrophilicity between the surfactant and a silica source. The directed silica wall formations were performed at different confined spaces of the vesicles, including the outer and inner surfaces, and the hydrophobic parts of the bi-layers. The resultant SHSs possess tailorable shell thicknesses (20–400 nm), particle sizes (200 nm–1.2 μm), and a high dispersibility in aqueous solutions.     

Evaluation of silica aerogel-reinforced polyurethane foams for footwear applications

In this work, a simple way to create a nanocellular structure within polyurethane (PU) foam was developed by the incorporation of silica aerogels, and the resultant foams were evaluated for footwear applications. To protect the brittle aerogels from breakage, the softness of PU foams was first tailored by changing the ratio of glycerol and polypropylene glycol. Different amounts of silica aerogels (0–15 wt%) were then loaded into a selected PU foam and analyzed in terms of compressive mechanical properties, shock attenuation performance, and thermal insulation. After incorporation of the aerogels, the compressive modulus, the compressive stress, and the deformation recovery of the foams improved, while the excellent flexibility was preserved. For simulated gait experiments, the shock attenuation capability of the foams was shown to increase with an increase in the aerogel content. These findings can probably be attributed to the improved elasticity of the solid phase and the changed morphology of the gaseous phase as observed from the SEM images. Moreover, the thermal insulation of the developed foams was also investigated, showing an increased trend with the aerogel content.     

Self-hardening calcium deficient hydroxyapatite/gelatine foams for bone regeneration

In this work gelatine was used as multifunctional additive to obtain injectable self-setting hydroxyapatite/gelatine composite foams for bone regeneration. The foaming and colloidal stabilization properties of gelatine are well known in food and pharmaceutical applications. Solid foams were obtained by foaming liquid gelatine solutions at 50°C, followed by mixing them with a cement powder consisting of alpha tricalcium phosphate. Gelatine addition improved the cohesion and injectability of the cement paste. After setting the foamed paste transformed into a calcium deficient hydroxyapatite. The final porosity, pore interconnectivity and pore size were modulated by modifying the gelatine content in the liquid phase.     

Mesoporous silica helical ribbon and nanotube-within-a-nanotube synthesized by sol-gel self-assembly

Using N-miristoyl-l-alanine sodium salt (C₁₄-l-AlaS) and 3-aminopropyltriethoxysilane (APES) as structure and co-structure-directing agents (CSDA), mesoporous silicas with the morphologies of helical ribbon and nanotube-within-a-nanotube have been fabricated just by increasing the APES/C₁₄-l-AlaS molar ratio from 1.0 to 1.15 and 1.25. The microstructures of the mesoporous silicas have been studied by electron microscopy and it was found that: 1) The mesostructure of the helical-ribbon silica materials was double-layer and the mesopores in the wall were disordered; 2) The nanotube-within-a-nanotube silica was multilayer and the mesopores in the wall were also disordered; 3) The silica materials obtained by increasing the APES/C₁₄-l-AlaS molar ratio to 1.25 maintained the nanotube-within-a-nanotube morphology, but with the existence of larger mesopores in the wall.     

Novel biopolymer-coated hydroxyapatite foams for removing heavy-metals from polluted water

3D-macroporous biopolymer-coated hydroxyapatite (HA) foams have been developed as potential devices for the treatment of lead, cadmium and copper contamination of consumable waters. These foams have exhibited a fast and effective ion metal immobilization into the HA structure after an in vitro treatment mimicking a serious water contamination case. To improve HA foam stability at contaminated aqueous solutions pH, as well as its handling and shape integrity the 3D-macroporous foams have been coated with biopolymers polycaprolactone (PCL) and gelatine cross-linked with glutaraldehyde (G/Glu). Metal ion immobilization tests have shown higher and fast heavy metals captured as function of hydrophilicity rate of biopolymer used. After an in vitro treatment, foam morphology integrity is guaranteed and the uptake of heavy metal ions rises up to 405 μmol/g in the case of Pb²⁺, 378 μmol/g of Cu²⁺ and 316 μmol/g of Cd²⁺. These novel materials promise a feasible advance in development of new, easy to handle and low cost water purifying methods.     

Processing and microstructure of particle stabilized silica foams

Silica foams containing ~ 85% porosity and with different shapes and sizes have been prepared by air entrainment in suspensions of hydrophobized silica + alumina (5 wt.%) powder mixture in aqueous solution of isopropanol and binders, followed by casting, drying and sintering. The silica powder with surfaces modified by presence of long chain amphiphilic molecules has been used successfully for stabilization of air bubbles in suspensions, so that their disproportionation and collapse could not be observed even after 4 weeks. Microstructural examination using optical and scanning electron microscopy as well as measurements by mercury porosimetry has shown trimodal pore size distribution with fine (4–10 μm), medium (50–100 μm) and coarse (~ 680 μm) pores.     

Blending effect of sucrose and surfactant templating agents on silica mesostructure

We report the blending effect of surfactant and sucrose as a nonsurfactant templating agent on the silica mesostructure. The CTAB/sucrose-templated mesoporous silica (SCS) was compared with CTAB-templated MCM-41. The MCM-41 showed spherical morphology with a particle diameter of 1.1–1.5 μm, and gave a bimodal size distribution, centered at 2.1 nm and 8.9 nm, which is assigned to hexagonally-arrayed cylindrical pores and interparticle-pores between small MCM-41 clusters, respectively. SCS gave unique and extraordinary morphology in which two different mesostructures have grown with both of them facing each other. The ordered MCM-41 pore structure clung to silica nanosphere-framed wormlike mesostructure, resulting in a bimodal pore size distribution centered at 2.1 nm and 7.0 nm. It was revealed that both of CTAB and sucrose act independently as a surfactant and a nonsurfactant template.     

Mesoporous silica templated biolabels with releasable fluorophores for immunoassays

A novel class of fluorescent immuno-biolabeling systems with extremely high F/P ratio (approximately 1000-6000) were prepared by combining the template method and layer-by-layer (LbL) technique. Labels were constructed by loading organic dye fluorescein diacetate (FDA) molecules onto hollow periodic mesoporous organosilica (H-PMO) particles followed by ployelectrolyte encapsulation and antibody attachment. The labeling systems were stimuli-responsive to the addition of concentrated NaOH with the loaded dye molecules being released and detected in a well-controlled manner. When applied in sandwich immunoassays, results indicated that the biolabels were immuno-active and generated an optimal signal that was approximately 50 times higher than the conventional dye labelled antibody system.     

Removal of lead ions in aqueous solution by hydroxyapatite/polyurethane composite foams

We have prepared hydroxyapatite/polyurehthane (HAp/PU) composite foams with two different HAp contents of 20 and 50 wt.% and investigated their removal capability of Pb2+ ions from aqueous solutions with various initial Pb2+ ion concentrations and pH values of 2-6. HAp/PU composite foams synthesized exhibited well-developed open pore structures which provide paths for the aqueous solution and adsorption sites for Pb2+ ions. With increasing the HAp content in the composites, the removal capability of Pb2+ ions by the composite foams increases owing to the higher adsorption capacity, whereas the removal rate is slower due to the less uniform dispersity of HAp in composite foams. The removal rate of Pb2+ ions is also slower with increasing the initial Pb2+ ion concentration in aqueous solutions. The removal mechanism of Pb2+ ion by the composites is varied, depending on the pH value of aqueous solution: the dissolution of HAp and precipitation of hydroypyromorphite is dominant at lower pH 2-3, the adsorption of Pb2+ ions on the HAp/PU composite surface and ion exchange reaction between Ca2+ of HAp and Pb2+ in aqueous solution is dominant at higher pH 5-6, and two removal mechanisms compete at pH 4. The equilibrium removal process of Pb2+ ions by the HAp/PU composite foam at pH 5 was described well with the Langmuir isotherm model, resulting in the maximum adsorption capacity of 150 mg/g for the composite foam with 50 wt.% HAp content.     

Mesoporous silica nanoparticles prepared by different methods for biomedical applications: Comparative study

In the current investigation, mesoporous silica nanoparticles were obtained by various techniques, namely sol–gel (S1), micro‐emulsion (S2) and hydrothermal synthesis (S3). The effect of those methods on the final features of the obtained mesoporous silica nanoparticles was studied. The obtained nanoparticles were investigated by TEM, BET surface area, Zetasizer, XRD and FTIR. The preparation method effect was evaluated on the drug release behaviour using doxycycline hyclate as a model drug. In addition, the degree of their compatibility against Saos‐2 cell line was also determined. The morphology and microstructure of silica nanoparticles were found to be dependent on the utilised method. Those techniques produced particles with particle sizes of 50, 30–20 and 15 nm and also surface areas of 111.04, 164 and 538.72 m²/g, respectively, for S1, S2 and S3. However, different preparation methods showed no remarkable changes for the physical and chemical integrities. The drug release test showed faster release from S2 compared with S1 and S3, which make them more applicable in cases require large doses for short periods. However, the release behaviour of S3 was satisfied for treatments which require long period with relatively highest release rate. The preparation method influenced the cell viability as S1 and S2 showed acceptable cell cytotoxicity compared with S3.     

The role of nanoscale architecture in supramolecular templating of biomimetic hydroxyapatite mineralization

Understanding and mimicking the hierarchical structure of mineralized tissue is a challenge in the field of biomineralization and is important for the development of scaffolds to guide bone regeneration. Bone is a remarkable tissue with an organic matrix comprised of aligned collagen bundles embedded with nanometer-sized inorganic hydroxyapatite (HAP) crystals that exhibit orientation on the macroscale. Hybrid organic-inorganic structures mimic the composition of mineralized tissue for functional bone scaffolds, but the relationship between morphology of the organic matrix and orientation of mineral is poorly understood. Herein the mineralization of supramolecular peptide amphiphile templates, that are designed to vary in nanoscale morphology by altering the amino acid sequence, is reported. It is found that 1D cylindrical nanostructures direct the growth of oriented HAP crystals, while flatter nanostructures fail to guide the orientation found in biological systems. The geometric constraints associated with the morphology of the nanostructures may effectively control HAP nucleation and growth. Additionally, the mineralization of macroscopically aligned bundles of the nanoscale assemblies to create hierarchically ordered scaffolds is explored. Again, it is found that only aligned gel templates of cylindrical nanostructures lead to hierarchical control over hydroxyapatite orientation across multiple length scales as found in bone.     

A novel anionic surfactant templating route for synthesizing mesoporous silica with unique structure

Anionic surfactants are used in greater volume than any other surfactants because of their highly potent detergency and low cost of manufacture. However, they have not been used as templates for synthesizing mesoporous silica. Here we show a templating route for preparing mesoporous silicas based on self-assembly of anionic surfactants and inorganic precursors. We use aminosilane or quaternized aminosilane as co-structure-directing agent (CSDA), which is different from previous pathways. The alkoxysilane site of CSDA is co-condensed with inorganic precursors; the ammonium site of CSDA, attached to silicon atoms incorporated into the wall, electrostatically interacts with the anionic surfactants to produce well-ordered anionic-surfactant-templated mesoporous silicas (AMS). These have new structures with periodic modulations as well as two-dimensional hexagonal and lamellar phases. The periodic modulations may be caused by the coexistence of micelles that differ in size or curvature, possibly owing to local chirality. These mesoporous silicas provide a new family of mesoporous materials as well as shedding light on the structural behaviour of anionic surfactants.