Characterizing the hierarchical structures of bioactive sol-gel silicate glass and hybrid scaffolds for bone regeneration

Bone is the second most widely transplanted tissue after blood. Synthetic alternatives are needed that can reduce the need for transplants and regenerate bone by acting as active temporary templates for bone growth. Bioactive glasses are one of the most promising bone replacement/regeneration materials because they bond to existing bone, are degradable and stimulate new bone growth by the action of their dissolution products on cells. Sol-gel-derived bioactive glasses can be foamed to produce interconnected macropores suitable for tissue ingrowth, particularly cell migration and vascularization and cell penetration. The scaffolds fulfil many of the criteria of an ideal synthetic bone graft, but are not suitable for all bone defect sites because they are brittle. One strategy for improving toughness of the scaffolds without losing their other beneficial properties is to synthesize inorganic/organic hybrids. These hybrids have polymers introduced into the sol-gel process so that the organic and inorganic components interact at the molecular level, providing control over mechanical properties and degradation rates. However, a full understanding of how each feature or property of the glass and hybrid scaffolds affects cellular response is needed to optimize the materials and ensure long-term success and clinical products. This review focuses on the techniques that have been developed for characterizing the hierarchical structures of sol-gel glasses and hybrids, from atomicscale amorphous networks, through the covalent bonding between components in hybrids and nanoporosity, to quantifying open macroporous networks of the scaffolds. Methods for non-destructive in situ monitoring of degradation and bioactivity mechanisms of the materials are also included. © 2012 The Royal Society.

Supercritical carbonation of lime based sustainable structural ceramics

Abstract Structural ceramics were manufactured from industrial byproducts and lime by a compression moulding/vacuum dewatering technique. Treatment of these ceramics with supercritical carbon dioxide was found to both significantly increase their flexural strength and activate cementation in the industrial byproducts at least as efficiently as heat curing. Flexural strengths of up to 10 MPa were achieved. Strength improvements were associated with decreased porosity and conversion of calcium hydroxide to calcium carbonate. Life cycle assessment of proposed products made from such materials indicated that the total reduction in embodied carbon dioxide achieved, as a result of combining use of byproducts with recombination of carbon dioxide, was up to 70%. © 2010 Institute of Materials, Minerals and Mining.

Degradable poly(ethylene glycol)-based hydrogels:synthesis, physico-chemical properties and in vitro characterization

Designing degradable hydrogels is complicated by the structural and temporal complexities of the gel and evolving tissue. A major challenge is to create scaffolds with sufficient mechanical properties to restore initial function while simultaneously controlling temporal changes in the gel structure to facilitate tissue formation. Poly(ethylene glycol) was used in this work, to form biodegradable poly(ethylene glycol)-based hydrogels with hydrolyzable poly-l-lactide segments in the backbone. Non-degradable poly(ethylene glycol) was also introduced in the formulation to obtain control of the degradation profile that encompasses cell growth and new tissue formation. The dependence on polymer composition was observed by higher degradation profiles and decreased mechanical properties as the content of degradable segments was increased in the formulation. Based on in vitro tests, no toxicity of extracts or biomaterial in direct contact with human adipose tissue stem cells was observed, and the ultraviolet light treatment did not affect the proliferation capacity of the cells.

Bioactive glass sol-gel foam scaffolds:evolution of nanoporosity during processing and in situ monitoring of apatite layer formation using small- and wide-angle X-ray scattering

Recent work has highlighted the potential of sol-gel-derived calcium silicate glasses for the regeneration or replacement of damaged bone tissue. The work presented herein provides new insight into the processing of bioactive calcia-silica sol-gel foams, and the reaction mechanisms associated with them when immersed in vitro in a simulated body fluid (SBF). Small-angle X-ray scattering and wide-angle X-ray scattering (diffraction) have been used to study the stabilization of these foams via heat treatment, with analogous in situ time-resolved data being gathered for a foam immersed in SBF. During thermal processing, pore sizes have been identified in the range of 16.5-62.0 nm and are only present once foams have been heated to 400 degrees C and above. Calcium nitrate crystallites were present until foams were heated to 600 degrees C; the crystallite size varied from 75 to 145 nm and increased in size with heat treatment up to 300 degrees C, then decreased in size down to 95 rim at 400 degrees C. The in situ time-resolved data show that the average pore diameter decreases as a function of immersion time in SBF, as calcium phosphates grow on the glass surfaces. Over the same time, Bragg peaks indicative of tricalcium phosphate were evident after only 1-h immersion time, and later, hydroxycarbonate apatite was also seen. The hydroxycarbonate apatite appears to have preferred orientation in the (h,k,0) direction.

Effect of calcium source on structure and properties of sol-gel derived bioactive glasses

The aim was to determine the most effective calcium precursor for synthesis of sol-gel hybrids and for improving homogeneity of sol-gel bioactive glasses. Sol-gel derived bioactive calcium silicate glasses are one of the most promising materials for bone regeneration. Inorganic/organic hybrid materials, which are synthesized by incorporating a polymer into the sol-gel process, have also recently been produced to improve toughness. Calcium nitrate is conventionally used as the calcium source, but it has several disadvantages. Calcium nitrate causes inhomogeneity by forming calcium-rich regions, and it requires high temperature treatment (>400 C) for calcium to be incorporated into the silicate network. Nitrates are also toxic and need to be burnt off. Calcium nitrate therefore cannot be used in the synthesis of hybrids as the highest temperature used in the process is typically 40-60 C. Therefore, a different precursor is needed that can incorporate calcium into the silica network and enhance the homogeneity of the glasses at low (room) temperature. In this work, calcium methoxyethoxide (CME) was used to synthesize sol-gel bioactive glasses with a range of final processing temperatures from 60 to 800 C. Comparison is made between the use of CME and calcium chloride and calcium nitrate. Using advanced probe techniques, the temperature at which Ca is incorporated into the network was identified for 70S30C (70 mol % SiO, 30 mol % CaO) for each of the calcium precursors. When CaCl was used, the Ca did not seem to enter the network at any of the temperatures used. In contrast, Ca from CME entered the silica network at room temperature, as confirmed by X-ray diffraction, Si magic angle spinning nuclear magnetic resonance spectroscopy, and dissolution studies. CME should be used in preference to calcium salts for hybrid synthesis and may improve homogeneity of sol-gel glasses.

New negative temperature coefficient thermistor ceramics in Mn-doped CaCu3-xMnxTi4O12 (0≤x≤1) system

New negative temperature coefficient (NTC) ceramics based on CaCu 3-xMnxTi4O12 (0≤x≤1) compositions have been investigated. The grain size of the CaCu 3-xMnxTi4O12 samples decreases at first and then increases with increasing Mn content. The X-ray photoelectron spectroscopy analysis corroborates the presence of Mn3+ and Mn 4+ in Mn-doped samples, which results in a decrease in the activation energy. All the NTC thermistors prepared show a linear relationship between the natural logarithm of the resistivity and the reciprocal temperature, indicative of NTC characteristics. The Mn-doped CaCu3-xMnxTi 4O12 NTC thermistors provide various electrical properties, depending on Mn content. The values of ρ25, B constant and activation energy of the NTC thermistors are in the range of 2.22×106-3.22×108 Ω cm, 5488-8031 K, and 0.473-0.692 eV, respectively. © 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Novel organo-modifier for thermally-stable polymer-layered silicate nanocomposites

A new novel approach for the stabilisation of polymer-clay nanocomposites has been investigated based on reacting chemically an antioxidant function, a hindered phenol moiety, with an organic modifier based on a quaternary ammonium salt. The chemically linked antioxidant-containing organic modifier (AO-OM) was then introduced into natural montmorillonite (MMt) through a cation-exchange reaction resulting in antioxidant-containing organo-modified clay (AO-OM-MMt). The new antioxidant-containing modified clay, along with other organo-modified clays having a similar organo-modifier but without the reacted antioxidant, were characterised by spectroscopic, thermogravimetric and x-ray diffraction techniques and tested for their thermo-oxidative stability. PA11-based clay nanocomposites samples containing the AO-OM-MMt and the other organo-modified clays, both without and with an added (i.e. not chemically reacted) hindered phenol antioxidant (similar to the one used in the AO-OM) were prepared by melt processing and examined for their processing and long-term thermal-oxidative stability at high temperatures. It was shown that although the new organo-modifier, AO-OM, was also susceptible to the Hoffman elimination reaction, the nanocomposites containing this newly modified clay (PA11/AO-OM-MMt) showed higher melt processing and long-term thermo-oxidative stability, along with excellent clay dispersion and exfoliation, compared to the other PA11-nanocomposites examined here (with and without the conventionally added antioxidant). It is suggested here that the excellent overall performance observed for the PA11/AO-OM-MMt nanocomposites is due to an in-situ partial release of low molecular weight antioxidant species having stabilising functionalities that are capable of acting locally at the interface between the inorganic clay platelets and the polymeric matrix which is a critical area for the onset of degradation processes.