The effect of template phase on the structures of As-synthesized silica nanoparticles with fragile didodecyldimethylammonium bromide vesicles as templates

The effect of template phase on the structures of as-synthesized silica nanoparticles with fragile DDAB vesicles as templates is reported. It is found that the template phase plays a critical role in the growth process of silica: the unstable DDAB vesicles in liquid-crystalline phase often lead to the formation of mesostructured solid spheres, and the rather stable DDAB vesicles in gel phase lead to the formation of hollow spheres with less mesostructures.

Growth of highly crystalline CaMoO4 : Tb3+ phosphor layers on spherical SiO2 particles via sol-gel process: Structural characterization and luminescent properties

Highly crystalline CaMoO4:Tb3+ phosphor layers were grown on monodisperse SiO2 particles through a simple sol-gel method, resulting in formation of core-shell structured SiO2@CaMoO4:Tb3+ submicrospheres. The resulting SiO2@CaMoO4: Tb3+ core-shell particles were fully characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectra (EDS), transmission electron microscopy (TEM), photoluminescence (PL), low-voltage cathodoluminescence (CL), and kinetic decays. The XRD results demonstrate that the CaMoO4:Tb3+ layers begin to crystallize on the SiO2 spheres after annealing at 400 degrees C and the crystallinity increases with raising the annealing temperature. SEM and TEM analysis indicates that the obtained submicrospheres have a uniform size distribution and obvious core-shell structure. SiO2@CaMoO4:Tb3+ submicrospheres show strong green emission under short ultraviolet (260 nm) and low-voltage electron beam (1-3 kV) excitation, and the emission spectra are dominated by a D-5(4) -F-7(5) transition of Tb3+(544 nm, green) from the CaMoO4:Tb3+ shells.

Silica-coated Y2O3 : Eu nanoparticles and their luminescence properties

Crystalline Y2O3:Eu is of paramount significance in rare earth materials and research on luminescence spectra. In this work, the nanocrystalline Y2O3:Eu was coated with silica by a facile solid state reaction method at room temperature. The transmission electron microscope (TEM) photographs showed that the prepared Y2O3:Eu particle is polycrystalline with the size of 20 nm, the size of silica-coated particle is about 25 nm. The XPS spectra indicated that the silica layer is likely to interact with Y2O3:Eu by a Si-O-Y chemical bond. The luminescence spectra showed that the intensity of ground samples is lower than that of unground ones, the intensity of silica-coated phosphors is higher than that of the ground samples, while almost the same as that of the unground ones. Therefore, the silica coating decreases the surface defects of nanoparticles of the nanocrystalline Y2O3:Eu, thus increasing their luminescent intensity.

Sol-Gel Preparation of Zn2 Si04：Mn Phosphor Layers on Silica Spheres and Their Luminescent Properties

The synthesis and luminescence properties of Zn2SiO4:Mn phosphor layers on spherical silica spheres,i.e.,a kind of core-shell complex phosphor,Zn2SiO4:Mn@SiO2 were described.Firstly,monodisperse silica spheres were obtained via the Stober method by the hydrolysis of tetraethoxysilane(TEOS)Si(OC2H5)4 under base condition (using NH4OH as the catalyst).Secondly,the silica spheres were coated with a Zn2SiO4:Mn phosphor layer by a Pechini sol-gel process.X-ray diffraction(XRD),scanning electron microscope(SEM),energy-dispersive X-ray spectrum(EDS) and photoluminescence(PL) were employed to characterize the resulting complex phosphor.The results comfirm that 1000℃ annealed sample consists of crystalline Zn2SiO4:Mn shells and amorphous SiO2 cores.The phosphor show the green emission of Mn2+ at 521nm corresponding 4T1(4G)-6A1(6S) transition,and the possible luminescence mechanism is proposed.

Confined crystallization behavior of PEO in silica networks

Poly(ethylene oxide) (PEO) and silica (SiO2) organic-inorganic hybrid materials have been synthesized by sol-gel approach. The crystallization behavior of PEO in silica networks has been investigated by differential scanning calorimeter (DSC) and scanning electron micrograph (SEM). The degree of PEO crystallinity in PEO/SiO2 hybrid networks reduces with the increase of SiO2. PEO is in amorphous state when the concentration of PEO is lower than 50 wt% in the hybrid materials. The melting points of PEO in the networks are lower than that of pure PEG, but the melting point of PEO in the networks almost has the same melting point. WAXD and SEM results show that the crystalline behavior of PEO in PEO/SiO2 hybrid system is sternly confined. (C) 1999 Elsevier Science Ltd. All rights reserved.

Application of mesoporous silica for the oral delivery of poorly water-soluble drugs

The objective of this thesis was to improve the dissolution rate of the poorly waters-soluble drug, fenofibrate by processing it with a high surface area carrier, mesoporous silica. The subsequent properties of the drug – silica composite were studied in terms of drug distribution within the silica matrix, solid state and release properties. Prior to commencing any experimental work, the properties of unprocessed mesoporous silica and fenofibrate were characterised (chapter 3), this allowed for comparison with the processed samples studied in later chapters. Fenofibrate was a highly stable, crystalline drug that did not adsorb moisture, even under long term accelerated storage conditions. It maintained its crystallinity even after SC-CO2 processing. Its dissolution rate was limited and dependent on the characteristics of the particular in vitro media studied. Mesoporous silica had a large surface area and mesopore volume and readily picked up moisture when stored under long term accelerated storage conditions (75% RH, 40 oC). It maintained its mesopore character after SC-CO2 processing. A variety of methods were employed to process fenofibrate with mesoporous silica including physical mixing, melt method, solvent impregnation and novel methods such as liquid and supercritical carbon dioxide (SC-CO2) (chapter 4). It was found that it was important to break down the fenofibrate particulate structure to a molecular state to enable drug molecules enter into the silica mesopores. While all processing methods led to some increase in fenofibrate release properties; the impregnation, liquid and SC-CO2 methods produced the most rapid release rates. SC-CO2 processing was further studied with a view to optimising the processing parameters to achieve the highest drug-loading efficiency possible (chapter 5). In this thesis, it was that SC-CO2 processing pressure had a bearing on drug-loading efficiency. Neither pressure, duration or depressurisation rate affected drug solid state or release properties. The amount of drug that could be loaded onto to the mesoporous silica successfully was also investigated at different ratios of drug mass to silica surface area under constant SC-CO2 conditions; as the drug – silica ratio increased, the drug-loading efficiency decreased, while there was no effect on drug solid state or release properties. The influence of the number of drug-loading steps was investigated (chapter 6) with a view to increasing the drug-loading efficiency. This multiple step approach did not yield an increase in drug-loading efficiency compared to the single step approach. It was also an objective in this chapter to understand how much drug could be loaded into silica mesopores; a method based on the known volume of the mesopores and true density of drug was investigated. However, this approach led to serious repercussions in terms of the subsequent solid state nature of the drug and its release performance; there was significant drug crystallinity and reduced release extent. The impact of in vitro release media on fenofibrate release was also studied (chapter 6). Here it was seen that media containing HCl led to reduced drug release over time compared to equivalent media not containing HCl. The key findings of this thesis are discussed in chapter 7 and included: 1. Drug – silica processing method strongly influenced drug distribution within the silica matrix, drug solid state and release. 2. The silica surface area and mesopore volume also influenced how much drug could be loaded. It was shown that SC-CO2 processing variables such as processing pressure (13.79 – 41.37 MPa), duration time (4 – 24 h) and depressurisation rate (rapid or controlled) did not influence the drug distribution within the SBA- 15 matrix, drug solid state form or release. Possible avenues of research to be considered going forward include the development and application of high resolution imaging techniques to visualise drug molecules within the silica mesopores. Also, the issues surrounding SBA-15 usage in a pharmaceutical manufacturing environment should be addressed.

Effect of Free-Fall Height in Water on Performance of Flowable Concrete

Concrete placed under water should be proportioned to flow readily into place with minimum materials separation. Unlike concrete cast for deep tremie seals, the use of concrete in repairs often necessitates some free fall of the mixture through water. Such placement conditions lead to greater risk of water erosion and segregation, and should be addressed in proportioning highly flowable underwater concrete. This paper evaluates the effect of free-fall height (FFH) of concrete through water on resulting in-place properties. Concrete was cast in blocks measuring 0.54 x 0.44 x 1 m with the initial FFH in water ranging between 0.25 and 0.60 m. In-place compressive and splitting tensile strengths, unit weight, and depth of washed-out and sedimentation materials were determined. In total, 24 highly flowable mixtures with slump flows greater than 500 mm were investigated. The evaluated mixtures were prepared with various hydraulic binders, including conventional Type 10 cement, a binary mixture with 10% of silica fume (SF), and a ternary binder incorporating 20% of fly ash (FA) and 6% of SF. The mixtures were proportioned with water-binder ratios (w/b) ranging between 0.41 and 0.47. Test results show that the increase of FFH of fresh concrete in water can greatly decrease the residual strength and significantly increase the thickness of washed out and sedimentation materials. The incorporation of 10% of SF, or 20% of FA and 6% of SF, and the reduction of the w/b from 0.47 to 0.41 can, however, lead to a significant increase in washout resistance and residual strength. A relationship between residual strength and the coupled factor of free-fall drop of concrete in water and washout resistance is established.

Cement-in-cement revision hip arthroplasty: an analysis of clinical and biomechanical literature

Introduction The number of revision hip arthroplasties is increasing but several aspects of this procedure could be improved. One method of reducing intra-operative complications is the cement-in-cement technique. This procedure entails cementing a smaller femoral prosthesis into the existing stable cement mantle. The aim of this systematic review is to provide a concise overview of the existing historical, operative, biomechanical and clinical literature on the cement-in-cement construct.

The Use of High Surface Area Silica and Supercritical Carbon Dioxide to Enhance Solubility of Poorly Water-Soluble Drugs

Purpose Poor water-solubility of BCS class II drugs can limit their commercialization because of reduced oral bioavailability. It has been reported that loading of drug by adsorption onto porous silica would enhance drug solubility due to the increased surface area available for solvent diffusion. In this work, solid dispersions are formed using supercritical carbon dioxide (scCO2). The aim of this research was to characterise the solid-state properties of scCO2 dispersion and to investigate the impact of altering scCO2 processing conditions on final amorphous product performance that could lead to enhancement of drug dissolution rate for BCS class II drugs. Methods Indomethacin (IND) was purchased from Sigma-Aldrich (Dorset, UK) and was used as a model drug with two grades of high surface area silica (average particle sizes 3&[micro] and 7&[micro]), which were obtained directly from Grace-Davison (Germany). Material crystallinity was evaluated using powder X-ray diffraction (PXRD, Rigaku™, miniflex II, Japan) and high-speed differential scanning calorimetry (Hyper-DSC 8000, Perkin Elmer, USA). Materials were placed in a high-pressure vessel consisting of a CO2 cylinder, a Thar™ Technologies P50 high-pressure pump and a 750 ml high-pressure vessel (Thar, USA). Physical mixtures were exposed to CO2 gas above its critical conditions. SEM imaging and elemental analysis were conducted using a Jeol 6500 FEGSEM (Advanced MicroBeam Inc., Austria). Drug release was examined using USP type II dissolution tester (Caleva™, UK). Results The two grades of silica were found to be amorphous using PXRD and Hyper-DSC. Using PXRD, it was shown that an increase in incubation time and pressure resulted in a decrease in the crystalline content. Drug release profiles from the two different silica formulations prepared under the same conditions are shown in Figure 1. It was found that there was a significant enhancement in drug release, which was influenced, by silica type and other experiment conditions such as temperature, pressure and exposure time. SEM imaging and elemental analysis showed drug deposited inside silica pores as well as on the outer surface. Conclusion This project has shown that silica carrier platforms may be used as an alternative approach to generating polymeric solid dispersions of amorphous drugs exhibiting enhanced solubility.

Biomass fly ash incorporation in cement based materials

In recent years, pressures on global environment and energy security have led to an increasing demand on renewable energy sources, and diversification of Europe’s energy supply. Among these resources the biomass could exert an important role, since it is considered a renewable and CO2 neutral energy resource once the consumption rate is lower than the growth rate, and can potentially provide energy for heat, power and transports from the same installation. Currently, most of the biomass ash produced in industrial plants is either disposed of in landfill or recycled on agricultural fields or forest, and most times this goes on without any form of control. However, considering that the disposal cost of biomass ashes are raising, and that biomass ash volumes are increasing worldwide, a sustainable ash management has to be established. The main objective of the present study is the effect of biomass fly ashes in cement mortars and concretes in order to be used as a supplementary cementitious material. The wastes analyzed in the study were collected from the fluidized bed boilers and grate boilers available in the thermal power plants and paper pulp plants situated in Portugal. The physical as well as chemical characterisations of the biomass fly ashes were investigated. The cement was replaced by the biomass fly ashes in 10, 20 and 30% (weight %) in order to investigate the fresh properties as well as the hardened properties of biomass fly ash incorporated cement mortar and concrete formulations. Expansion reactions such as alkali silica reaction (ASR), sulphate attack (external and internal) were conducted in order to check the durability of the biomass fly ash incorporated cement mortars and concretes. Alternative applications such as incorporation in lime mortars and alkali activation of the biomass fly ashes were also attempted. The biomass fly ash particles were irregular in shape and fine in nature. The chemical characterization revealed that the biomass fly ashes were similar to a class C fly ash. The mortar results showed a good scope for biomass fly ashes as supplementary cementitious materials in lower dosages (<20%). The poor workability, concerns about the organic content, alkalis, chlorides and sulphates stand as the reasons for preventing the use of biomass fly ash in high content in the cement mortars. The results obtained from the durability tests have shown a clear reduction in expansion for the biomass fly ash mortars/concretes and the binder blend made with biomass fly ash (20%) and metakaolin (10%) inhibited the ASR reaction effectively. The biomass fly ash incorporation in lime mortars did not improve the mortar properties significantly though the carbonation was enhanced in the 15-20% incorporation. The biomass fly ash metakaolin blend worked well in the alkali activated complex binder application also. Portland cement free binders (with 30-40 MPa compressive strength) were obtained on the alkali activation of biomass fly ashes (60-80%) blended with metakaolin (20-40%).

Surface reactivity enhancement of silica-based glass-ceramic scaffolds

A paradigm shift is taking place from using transplanting tissue and synthetic implants to a tissue engineering approach that aims to regenerate damaged tissues by combining cells from the body with highly porous scaffold biomaterials, which act as templates, guiding the growth of new tissue. The central focus of this thesis was to produce porous glass and glass-ceramic scaffolds that exhibits a bioactive and biocompatible behaviour with specific surface reactivity in synthetic physiological fluids and cell-scaffold interactions, enhanced by composition and thermal treatments applied. Understanding the sintering behaviour and the interaction between the densification and crystallization processes of glass powders was essential for assessing the ideal sintering conditions for obtaining a glass scaffolds for tissue engineering applications. Our main goal was to carry out a comprehensive study of the bioactive glass sintering, identifying the powder size and sintering variables effect, for future design of sintered glass scaffolds with competent microstructures. The developed scaffolds prepared by the salt sintering method using a 3CaO.P2O5 - SiO2 - MgO glass system, with additions of Na2O with a salt, NaCl, exhibit high porosity, interconnectivity, pore size distribution and mechanical strength suitable for bone repair applications. The replacement of 6 % MgO by Na2O in the glass network allowed to tailor the dissolution rate and bioactivity of the glass scaffolds. Regarding the biological assessment, the incorporation of sodium to the composition resulted in an inibition cell response for small periods. Nevertheless it was demonstrated that for 21 days the cells response recovered and are similar for both glass compositions. The in vitro behaviour of the glass scaffolds was tested by introducing scaffolds to simulated body fluid for 21 days. Energy-dispersive Xray spectroscopy and SEM analyses proved the existence of CaP crystals for both compositions. Crystallization forming whitlockite was observed to affect the dissolution behaviour in simulated body fluid. By performing different heat treatments, it was possible to control the bioactivity and biocompatability of the glass scaffolds by means of a controlled crystallization. To recover and tune the bioactivity of the glass-ceramic with 82 % crystalline phase, different methods have been applied including functionalization using 3- aminopropyl-triethoxysilane (APTES). The glass ceramic modified surface exhibited an accelerated crystalline hydroxyapatite layer formation upon immersion in SBF after 21 days while the as prepared glass-ceramic had no detected formation of calcium phosphate up to 5 months. A sufficient mechanical support for bone tissue regeneration that biodegrade later at a tailorable rate was achievable with the glass–ceramic scaffold. Considering the biological assessment, scaffolds demonstrated an inductive effect on the proliferation of cells. The cells showed a normal morphology and high growth rate when compared to standard culture plates. This study opens up new possibilities for using 3CaO.P2O5–SiO2–MgO glass to manufacture various structures, while tailoring their bioactivity by controlling the content of the crystalline phase. Additionally, the in vitro behaviour of these structures suggests the high potential of these materials to be used in the field of tissue regeneration.

Characteristics of silica-rich pedofeatures in a buried paleosol

Whitish and whitish-light brown milky-like textural pedofeatures and impregnations were found in the voids and the matrix of buried paleosols older than 2.7 million years in a site in Sardinia, Italy. The pedofeatures were described and analysed using micromorphology, X-ray diffraction and microprobe techniques, and their spatial distribution correlated with field evidence. The suite of analyses showed that the main components of the pedofeatures were more or less ordered silica phases. As well as forming a matrix cement, these pedofeatures also occurred as coatings and infillings in pores. Significant amounts of alumina and, less, Mg, Ca and Fe were also present in the pedofeatures, possibly in the form of silicate coatings and inclusions/impurities, or alumino-silicates of the adjacent soil matrix. A number of hypotheses are drawn on the possible mechanisms of formation of these silica-rich pedofeatures, including the possibility of prolonged weathering of volcanic materials and the resulting formation of colloids and more or less ordered silica phases, with successive dehydration and progressive ordering of phases during the at least 2.5 million years. (C) 2003 Elsevier B.V. All rights reserved.

Characteristics of silica-rich pedofeatures in a buried paleosol

Whitish and whitish-light brown milky-like textural pedofeatures and impregnations were found in the voids and the matrix of buried paleosols older than 2.7 million years in a site in Sardinia, Italy. The pedofeatures were described and analysed using micromorphology, X-ray diffraction and microprobe techniques, and their spatial distribution correlated with field evidence. The suite of analyses showed that the main components of the pedofeatures were more or less ordered silica phases. As well as forming a matrix cement, these pedofeatures also occurred as coatings and infillings in pores. Significant amounts of alumina and, less, Mg, Ca and Fe were also present in the pedofeatures, possibly in the form of silicate coatings and inclusions/impurities, or alumino-silicates of the adjacent soil matrix. A number of hypotheses are drawn on the possible mechanisms of formation of these silica-rich pedofeatures, including the possibility of prolonged weathering of volcanic materials and the resulting formation of colloids and more or less ordered silica phases, with successive dehydration and progressive ordering of phases during the at least 2.5 million years. (C) 2003 Elsevier B.V. All rights reserved.