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Ca,P-rich layer formed on high-strength bioactive glass-ceramic A-W.

Glass-ceramic A-W, containing crystalline apatite and wollastonite in a MgO-CaO-SiO2 glassy matrix shows high bioactivity as well as high mechanical strength, but other ceramics containing the same kinds of crystalline phases in different glassy matrices do not show the same bioactivity. In order to investigate the bone-bonding mechanism of this type of glass-ceramic, surface structural changes of the glass-ceramics after exposure to simulated body fluid were analyzed with various techniques. A solution with ion concentrations which are almost equal to those of the human blood plasma was used as the simulated body fluid, instead of Tris-buffer solution hitherto used. For analyzing the surface structural changes, thin-film x-ray diffraction was used in addition to conventional techniques. It was found that a bioactive glass-ceramic forms a Ca, P-rich layer on its surface in the fluid but nonbioactive ones do not, and that the Ca, P-rich layer consists of carbonate-containing hydroxyapatite of small crystallites and/or defective structure. These findings were common to those of Bioglass-type glasses. So, we conclude that the essential condition for glass and glass-ceramic to bond to bone is the formation of the surface apatite layer in the body environment but it is not essential to contain apatite within the material. Bioactivity of glass and glass-ceramic can be evaluated in vitro by examining the formation of the surface apatite layer in the simulated body fluid described above.

Apatites↗

Type I collagen production by osteoblast-like cells cultured in contact with different bioactive glasses.

Bioactive glasses are silica-based, surface-active bone substitutes that have shown good biocompatibility both in bone and in soft tissue and are used in oral and maxillofacial bone augmentation. Previous in vitro studies showing that bioactive glasses support the growth and maturation of rat osteoblast-like cells and promote the expression and maintenance of the osteoblastic phenotype have suggested that there is both a solution-mediated and a surface-controlled effect on cell activity. In this study, we investigated the behavior of human primary osteoblast-like cells cultured in contact with three different bioactive glasses and compared them with amorphous silica (SiO2) used in the form of granules. The specific activity of alkaline phosphatase determined biochemically was significantly higher at 2 and 4 days on the bioactive glass with 46.1 mol % silica content (45S5 Bioglass) cultures than in the control cultures and in the bioactive gel-glass cultures, which had 60 mol % (58S) and 80 mol % (77S) silica content. Osteoblasts synthesize collagen type I, which is subsequently mineralized. Immunoblot and biochemical studies showed increased collagen release from osteoblast-like cells cultured in contact with bioactive glasses over that of controls. Among the three bioactive glasses, 45S5 is the highest inducer of osteoblast-like cell collagen release; moreover, mRNA for type I collagen was stimulated approximately three- to fivefold after 45S5 treatment. 77S bioactive glass similarly increased type I collagen synthesis even though alkaline phosphatase was not higher. These results suggest that 45S5 Bioglass not only induces osteogenic differentiation of human primary osteoblast-like cells, but can also increase collagen synthesis and release. The newly formulated bioactive gel-glass 77S seems to have potential applications for tissue engineering, inducing increased collagen synthesis.

Adult↗

Biologic significance of surface microroughing in bone incorporation of porous bioactive glass implants.

A novel chemical etching method was recently developed to create a controlled microrough surface on porous bioactive glass implants. Our earlier in vitro studies showed enhanced attachment of osteoblast-like MG63 cells on a microrough bioactive glass surface. The purpose of our current study was to confirm the in vivo significance of surface microroughening for bone bonding of bioactive glass. Porous bioactive glass cones made of sintered microspheres were surgically implanted in the anterior cortex of rabbit femurs. Peripheral quantitative computed tomography (pQCT), biomechanical push-out testing, histomorphometry, and electron microscopy (BEI-SEM) were used to analyze bone ingrowth and osseointegration at 7, 10, 14, 28, 56, and 84 days after implantation. The results showed that microroughening of the bioactive glass surface significantly enhanced the bone-bonding response of the biomaterial. The positive response was seen in one of the three bioactive glass compositions studied. The affinity index of new bone on the glass surface was significantly (p = 0.02) increased with a trend (p = 0.10) toward improved mechanical incorporation. New bone formation was dependent on the glass composition, and it was found to occur not only through the mechanism of bone ingrowth but also based on in situ osteogenesis within implant interstices. Based on these results, the procedure of microroughening could enhance the osteopromotive properties of certain bioactive glass compositions.

Animals↗

Influence of physicochemical reactions of bioactive glass on the behavior and activity of human osteoblasts in vitro.

Bioactive glasses are characterized by a bond to bone with a hydroxyl carbonate apatite layer. They enhance bone tissue formation and for this purpose are used in orthopedic surgery and in dental implantology. In the current work, we studied the biological response of human osteoblasts with a bioactive glass. This bioactive glass is based on 50% Si0(2), 20% Na(2)O, 16% CaO, 6% P(2)O(5), 5% K(2)0, 2% Al(2)O(3) and 1% MgO and designated A9. Cracks and irregularities were observed on the material surface when it was immersed in the culture medium. In addition, energy dispersive X-ray analyses highlighted a selective release of the elements at the surface of the bioactive glass, such as Na(+) and K(+) ions, released from the first day, contrary to the Si, Al, Ca, P, and Mg elements, which were released more slowly. Cell proliferation kinetics, total protein synthesis, and DNA content of the osteoblasts in contact with bioactive glass were similar to control cells. The morphological studies by light and scanning electron microscopy revealed an increasing cellular density in culture with bioactive glass without contact inhibition. The immunohistochemical studies highlighted the expression of types I, III, and V collagens by osteoblasts cultured in the presence of bioactive glass. The pH measurement of the culture medium in the presence of bioactive glass demonstrated a slight alkalinization. We thus conclude that human osteoblasts preserve their properties in the presence of bioactive glass (A9).

Biocompatible Materials↗

In vitro studies of calcium phosphate glass ceramics with different solubility with the use of human bone marrow cells.

Two glass ceramics in the CaO--P2O5--MgO system with the incorporation of K2O or TiO2 oxides were prepared with the goal of using them as potential bone graft substitutes. The incorporation of TiO2 and K2O led to the preparation of specific crystalline phases in the structure of the glass ceramics, which show different degrees of biodegradation. In fact, the 45CaO--45P2O5--5MgO--5K2O has been previously demonstrated to be much more soluble in aqueous solutions than the 45CaO--37P2O5--5MgO--13TiO2 glass ceramic. The in vitro biological activity of the two calcium phosphate glass ceramics was studied with the use of human bone marrow osteoblast cell cultures maintained for 28 days, and seeded materials were assessed for cell proliferation and function. The Ti-containing glass ceramic showed a stable surface throughout the culture time, on macroscopic and SEM observation. Osteoblast cells proliferated gradually, especially during the third week, with a high alkaline phosphatase activity and formation of a mineralized matrix. On SEM observation, attached cells appeared with a spread-polygonal morphology typical of the osteoblast cells, with extensive cell-to-cell contact. Cell behavior on the seeded material was similar to that found on cultures performed on tissue-culture-grade polystyrene; except for the presence of lower cell numbers during the first 2 weeks. By contrast, the K-containing glass ceramic showed a highly instable surface with dissolution/precipitation processes occurring throughout the culture time. Few cells adhered to the material surface, and subsequent proliferation was also hindered, especially from the first week onwards. Cell numbers were significantly lower than those observed in the Ti-containing glass ceramic during most of the incubation time. Results suggest that the different in vitro biological behavior of these two glass ceramics is mainly due to the significant differences in the surface degradation rate, which is directly correlated to the chemical composition of the mother glass.

Alkaline Phosphatase↗

Intact surface of bioactive glass S53P4 is resistant to osteoclastic activity.

Bioactive glass reacts with body fluids and is gradually dissolved in tissues and in cell cultures. We investigated whether osteoclasts contribute to this process, by culturing newborn rat bone-marrow cells containing osteoclasts on polished bioactive glass plates (glass S53P4). The cultures were inspected at days 1-5 and stained for alkaline phosphatase (ALP) to demonstrate osteoblasts and for tartrate resistant acid phosphatase (TRAP) to visualize osteoclasts. Nonosteoclastic cells proliferated several-fold both on bioactive glass and on plastic, whereas osteoclasts and their precursors matured into multicellular giant cells and degenerated. Most cells on bioactive glass became ALP-positive, whereas on plastic the majority of cells remained ALP-negative. Osteoclasts survived on bioactive glass for 4-5 days, whereas on plastic they degenerated and disappeared after 3 days. Condensed nuclei indicating apoptosis were detected both in degenerating osteoclasts and osteoblasts. The surface of the bioactive glass reacted rapidly forming rounded pits, erosions, and cracks within 24 h in areas occupied by osteoblasts. Light microscopy and scanning electron micrographs demonstrated, however, a smooth surface below the cytoplasm of osteoclasts. This indicates that when applied on an intact bioactive glass surface, osteoclasts were unable to dissolve the glass material within this culture period.

Animals↗

Estimation of protein and drug adsorption onto silicone-coated glass surfaces.

Porous glass coated with silicone adsorbed proteins such as albumin, globulin, hemoglobin, lysozyme, and peroxidase in pH 7.2 phosphate-buffered saline in the amount of 33--53 mg of protein/g of glass (39.4 m2/g of glass). These proteins were not absorbed from distilled water (except peroxidase). The amounts of albumin adsorbed onto coated glass from several buffers at ionic strength greater than 0.05 mu were similar to amounts adsorbed from saline, despite the difference in salts and pH. The enzymes adsorbed onto coated glass were stable for at least 1 month. Drugs such as insulin, atropine sulfate, physostigmine salicylate, and epinephrine were adsorbed onto the coated glass in the amounts of 28, 0.32, 1.53, and 0.01 mg/g of glass, respectively. The adsorption of pharmaceutical biologicals composed proteins such as hormones and vaccines onto silicone-coated glass contains must be recognized and compensated for, particularly at low concentrations. Protein adsorption onto coated glass might be caused by hydrophobic interaction.

Adsorption↗

Release of chlorhexidine digluconate and flexural properties of glass fibre reinforced provisional fixed partial denture polymer.

The objective of this study was to determine the flexural properties and the release of chlorhexidine digluconate (CHX) of CHX laced unidirectional E-glass fibre reinforced provisional fixed partial denture polymer. Bar shaped test specimens (3.3 x 10.0 x 65.0 mm) were fabricated from provisional fixed partial denture polymer (mixture of poly[ethylmethacrylate] powder and n-poly[butyl methacrylate] monomer liquid) with E-glass fibre reinforcements. Poly(methyl methacrylate) preimpregnated continuous unidirectional glass fibre reinforcement was laced with CHX. The glass fibre reinforcements were incorporated into the polymer and the polymerised to the form of test specimens. In addition test specimens without CHX in glass fibre reinforcement were made for comparison. Control specimens did not contain glass fibres in the test specimens. Flexural strength and modulus of test specimens (n = 6) was tested with three-point bending test after storing the specimens dry or in water (two weeks). Released CHX was determined with high performance liquid chromatography during 180 days water immersion. In dry conditions, the flexural strength and the modulus of the polymer was 43 MPa and 1.7 GPa, and with glass fibre reinforcement 96 MPa and 3.5 GPa. With the reinforcement laced with CHX, the strength was 92 MPa and the modulus was 3.2 GPa. The water storage of test specimens did not weaken the reinforced polymer. The majority of the CHX released from the glass fibre reinforced polymer during the first days of storage in water. Flexural properties of provisional fixed partial denture polymer were increased using glass fibre reinforcement. The fibre reinforcement that was laced with CHX resulted in similar reinforcing effect.

Adhesives↗

An investigation into the structure and reactivity of calcium-zinc-silicate ionomer glasses using MAS-NMR spectroscopy.

The suitability of Glass Polyalkenoate Cements (GPCs) for orthopaedic applications is retarded by the presence in the glass phase of aluminium, a neurotoxin. Unfortunately, the aluminium ion plays an integral role in the setting process of GPCs and its absence is likely to hinder cement formation. However, the authors have previously shown that aluminium-free GPCs may be formulated based on calcium zinc silicate glasses and these novel materials exhibit significant potential as hard tissue biomaterials. However there is no data available on the structure of these glasses. (29)Si MAS-NMR, differential thermal analysis (DTA), X-ray diffraction (XRD), and network crosslink density (CLD) calculations were used to characterize the structure of five calcium zinc silicate glasses and relate glass structure to reactivity. The results indicate that glasses capable of forming Zn-GPCs are predominantly Q(2)/Q(3) in structure with corresponding network crosslink densities greater than 2. The correlation of CLD and MAS-NMR results indicate the primary role of zinc in these simple glass networks is as a network modifier and not an intermediate oxide; this fact will allow for more refined glass compositions, with less reactive structures, to be formulated in the future.

Aluminum↗

Glass-bead affinity chromatography of cell attachment and spreading-promoting factors of human serum.

The glass-binding properties of a number of purified glycoproteins capable of promoting attachment and spreading of a variety of types of animal cells in culture have been examined. Two such factors in human serum, fibronectin and serum spreading factor, exhibited strong affinities for glass beads and could be eluted from glass-bead columns under similar conditions. A number of other glycoproteins of human serum that do not promote cell adhesion did not bind to glass beads under conditions that resulted in binding of serum spreading factor or fibronectin. At a sufficiently low ratio of serum volume to glass-bead volume, human serum could be simultaneously depleted of serum spreading factor, fibronectin, and cell spreading-promoting activity by glass-bead affinity chromatography. Laminin, another cell spreading-promoting glycoprotein, possessed glass-binding properties similar to those of serum spreading factor and fibronectin while chondronectin, a fourth cell spreading-promoting factor of more limited specificity of biological activity and distribution in vivo, did not exhibit a strong interaction with glass beads under the same conditions. These observations suggest that glass-bead column affinity chromatography may prove useful as a general method for isolation and study of glycoprotein factors promoting attachment and spreading of cells in culture.

Animals↗

Influence of colorants on crystallization and mechanical properties of lithia-based glass-ceramics.

OBJECTIVES: The objective of the present study was to test the hypothesis that colorants such as AgNO3 and FeCl3 act as conucleating agents with P2O5 in the Li2O-Al2O3-CaO-SiO2 system and that the addition of either colorant and P2O5 produces a greater effect on crystallization and selected mechanical properties than the use of P2O5 alone. METHODS: Microstructural effects were observed by SEM and optical microscopy. Mechanical properties were determined to monitor the effects of structural changes after crystallization. These include controlled-flaw flexure strength, fracture toughness (KIC), and Vickers hardness (VHN). RESULTS: Based on a glass composition of 27.84 mol% Li2O, 2.45 mol% Al2O3, 5.88 mol% CaO, and 63.84 mol% SiO2 (LACS), the mechanical properties of LACS glass-ceramics were influenced by P2O5, the colorant type, and the colorant concentration. The mean strength of the glass-ceramic disks without P2O5 increased with AgNO3 concentration to a peak value of 188 MPa at a concentration of 0.78 mmol%. The maximum value of controlled-flaw flexure strength increased from 120 MPa for one of the FeCl3 groups to 188 MPa for one of the AgNO3 groups. The maximum fracture toughness of glass-ceramic disks without P2O5 (2.45 MPa.m1/2) was associated with a AgNO3 concentration of 0.58 mmol%. This value was significantly greater (p < 0.05) than that of the corresponding group (1.90 MPa.m1/2) which also contained P2O5. There was no significant change in KIC of glass-ceramic specimens containing P2O5 as the AgNO3 concentration increased. The increase in controlled-flaw flexure strength and fracture toughness of specimen groups containing 0.58 to 0.78 mmol% AgNO3 support its use as a colorant and as a nucleating agent in LACS glass-ceramics. SIGNIFICANCE: The development of tougher, higher strength glass-ceramics can be controlled by the use of colorants that are also effective as nucleating agents. Although certain colorants are believed to act synergistically when used in combination with known nucleating agents to enhance the fracture toughness of glass-ceramics, this effect was not observed in this study for the combined use of AgNO3 and the classical nucleating agent, P2O5. In fact, the colorant used in this study (AgNO3) was more effective than P2O5 as a nucleating agent for lithia-based glass-ceramics.

Ceramics↗

Curing shrinkage and volumetric changes of resin-modified glass ionomer restorative materials.

OBJECTIVES: The objective of the study was to evaluate initial curing shrinkage and volumetric change during water storage of six resin-modified glass ionomer cements (Dyract, DeTrey Dentsply; Fuji II LC, GC Dental Int.; Ionosit Fil, DMG; VariGlass VLC, DeTrey Dentsply; Vitremer, 3M Dental Products; Photac-Fil, ESPE), a hybrid composite (blend-a-lux, Blendax) and a chemical-cured glass ionomer cement (ChemFil Superior, DeTrey Dentsply). METHODS: The curing shrinkage was determined 5 min and 24 h after polymerization and mixing, respectively. Volumetric changes were examined after 14 d and 28 d water storage. Curing shrinkage and volumetric changes were evaluated using the hydrostatic principle. In addition, the total water content of the materials was measured after 28 d water storage. RESULTS: Curing shrinkage of most of the resin-modified glass ionomers was greater than the hybrid composite and the chemical-cured glass ionomer cement. After a 28 d water storage, the resin-modified glass ionomers showed volumetric expansion and the chemical-cured glass ionomer showed volumetric loss. All of the examined glass ionomer materials had a higher total water content than the composite. SIGNIFICANCE. The large curing shrinkage of the resin-modified glass ionomer materials measured in this in vitro study could affect the marginal integrity of glass ionomer restorations.

Acrylic Resins↗

Processing and properties of porous poly(L-lactide)/bioactive glass composites.

Porous poly(L-lactide)/bioactive glass (PLLA/BG) composites were prepared by phase separation of polymer solutions containing bioactive glass particles (average particle size: 1.5 microm). The composite microstructures consist of a porous PLLA matrix with glass particles distributed homogeneously throughout. Large pores (>100 microm) are present in a network of smaller (<10 microm) interconnected pores. The porous microstructure of the composites was not significantly influenced by glass content (9 or 29 vol%), but silane pretreatment of the glass resulted in better glass incorporation in the matrix. Mechanical tests showed that an increase in glass content increased the elastic modulus of the composites, but decreased their tensile strength and break strain. Silane pretreatment enhanced the increase in modulus and prevented the decrease in tensile strength with increasing glass content. Composites soaked in simulated body fluid (SBF) at body temperature formed bone-like apatite inside and on their surfaces. The silane pretreatment of glass particles delayed the in vitro apatite formation. This bone-like apatite formation demonstrates the composites' potential for integration with bone.

Biocompatible Materials↗

Release of angiogenic growth factors from cells encapsulated in alginate beads with bioactive glass.

Attempts to stimulate therapeutic angiogenesis using gene therapy or delivery of recombinant growth factors, such as vascular endothelial growth factor (VEGF), have failed to demonstrate unequivocal efficacy in human trials. Bioactive glass stimulates fibroblasts to secrete significantly increased amounts of angiogenic growth factors and therefore has a number of potential applications in therapeutic angiogenesis. The aim of this study was to assess whether it is possible to encapsulate specific quantities of bioactive glass and fibroblasts into alginate beads, which will secrete growth factors capable of stimulating angiogenesis. Human fibroblasts (CCD-18Co) were encapsulated in alginate beads with specific quantities of 45S5 bioactive glass and incubated in culture medium (0-17 days). The conditioned medium was collected and assayed for VEGF or used to assess its ability to stimulate angiogenesis by measuring the proliferation of human dermal microvascular endothelial cells. At 17 days the beads were lysed and the amount of VEGF retained by the beads measured. Fibroblasts encapsulated in alginate beads containing 0.01% and 0.1% (w/v) 45S5 bioactive glass particles secreted increased quantities of VEGF compared with cells encapsulated with 0% or 1% (w/v) 45S5 bioactive glass particles. Lysed alginate beads containing 0.01% and 0.1% (w/v) 45S5 bioactive glass contained significantly more VEGF (p<0.01) compared with beads containing no glass particles. Endothelial cell proliferation was significantly increased (p<0.01) by conditioned medium collected from alginate beads containing 0.1% (w/v) 45S5 bioactive glass particles. The results of this study demonstrate that bioactive glass and fibroblasts can be successfully incorporated into alginate beads for use in delivering angiogenic growth factors. With further optimization, this technique offers a novel delivery device for stimulating therapeutic angiogenesis.

Alginates↗

Accelerated degradation and improved bone-bonding ability of hydroxyapatite ceramics by the addition of glass.

Dense hydroxyapatite (HA) ceramics are useful bone substitutes, but they degrade minimally. One solution is to incorporate degradable materials in the HA. In this study, we manufactured glass-containing HA and investigated whether the degradability and bone-bonding ability of the HA were improved. The glass-containing HA was manufactured from a mixture of HA powder and 1.0 wt% glass powder. The control HA was manufactured from pure HA powder. In vitro degradability was evaluated by soaking in physiological saline, and a rabbit model was used to evaluate in vivo degradability and bone-bonding ability. Detaching tests were performed for all removed samples to quantify bone-bonding ability of each type of HA. The glass-containing HA showed higher degradability than the control HA, both in vitro and in vivo. The detaching failure load of the glass-containing HA was rapidly elevated after implantation and was higher than that of the control HA. Our results suggest that the dissolution of the added glass made the glass-containing HA degradable and that the detaching failure load of the glass-containing HA was elevated by reinforcement of the mechanical locking at the roughened interface. Incorporation of glass additives into HA can be concluded to be a good candidate for producing a bone substitute that can partially degrade and bond to bone firmly and rapidly.

Absorbable Implants↗

Glass formation in plant anhydrobiotes: survival in the dry state.

Anhydrobiotes can resist complete dehydration and survive the dry state for extended periods of time. During drying, cytoplasmic viscosity increases dramatically and in the dry state, the cytoplasm transforms into a glassy state. Plant anhydrobiotes possess large amounts of soluble non-reducing sugars and their state diagrams resemble those of simple sugar mixtures. However, more detailed in vivo measurements using techniques such as Fourier transform infrared spectroscopy and electron paramagnetic resonance spectroscopy reveal that these intracellular glasses are complex systems with properties quite different from those of simple sugar glasses. Intracellular glasses exhibit a high molecular packing and slow molecular mobility, resembling glasses made of mixtures of proteins and sugars, which potentially interact with additional cytoplasmic components such as salts, organic acids, and amino acids. Above the glass transition temperature, the cytoplasm of biological systems still exhibits a high stability and low molecular mobility, which could serve as an ecological advantage. All desiccation-tolerant organisms form glasses upon drying, but desiccation-sensitive organisms generally lose their viability during drying at water contents at which the glassy state has not yet been formed, suggesting that other factors are necessary for desiccation tolerance. Nevertheless, the formation of intracellular glasses is indispensable to survive the dry state. Storage stability of seeds and pollens is related to the molecular mobility and packing density of the intracellular glass, suggesting that the characteristic properties of intracellular glasses provide stability for long-term survival.

Acclimatization↗

The effect of calcium fluoride (CaF(2)) on the chemical solubility of an apatite-mullite glass-ceramic material.

OBJECTIVE: To assess the effect of varying CaF(2) on the chemical solubility of apatite-mullite glass-ceramic (G-C) materials in both the glassy and crystallized states. METHODS: Apatite-mullite forming glasses used in this study are ionomer cement derivatives based on the general formula (4.5SiO(2)-3Al(2)O(3)-1.5P(2)O(5)-3CaO-XCaF(2)). Six glass formulations were produced where X=0.5, 1, 1.5, 2, 2.5 and 3, and called HG1-6, respectively. Batches were melted in covered silliminite crucibles in a furnace overnight at 1050 degrees C, then at 1450 degrees C for 2h, before quenching in water. The six glass compositions were analyzed using differential thermal analysis (DTA), X-ray diffraction (XRD) and X-ray fluorescence spectrometry (XRF). Thirty discs (2mm thick and 12 mm diameter) were produced per glass using the lost wax casting technique. Ten were left as cast and 10 heat treated to either apatite or apatite-mullite. Solubility testing was carried out according to International Standard BS EN ISO 6872 1999 and the mass difference in solubility calculated as mug/cm(2). A lithium disilicate G-C system was used as a control material. RESULTS: All compositions formed glasses and on heat treatment could form apatite and apatite-mullite. The as-cast glass samples were the most soluble followed by the apatite samples. The apatite-mullite G-C was significantly less soluble than the other two phases (p<0.05) for all six compositions. The control material was significantly less soluble than all the HG glass-ceramic compositions for every phase (p<0.05). Decreasing the CaF(2) content (3-0.5 mol%) led to a decrease in solubility, without affecting the ability of the material to form apatite and apatite-mullite phases. SIGNIFICANCE: Increasing the CaF(2) content increases the chemical solubility for the glass, apatite G-C and apatite-mullite G-C phases. The solubility values obtained show that all the compositions, as cast and heat treated would be suitable for use as core ceramics.

Aluminum Silicates↗

Spectral analysis of Mn2+, Co2+ and Ni2+: B2O3-ZnO-PbO glasses.

This paper reports on the spectral properties of Mn2+, Co2+ and Ni2+ ions doped B2O3-ZnO-PbO glasses. XRD, FT-IR spectra and DSC profiles of these glasses have also been carried out, and the FT-IR profiles have shown the presence of both BO3 and BO4 units. It is interesting to notice that the FT-IR peak positions are slightly shifted towards higher energy with an increase in transition metal ion concentration change. From the measured DSC thermograms, glass transition (T(g)), crystallization (T(c)) and temperature of melting (T(m)) have been evaluated. From the UV absorption spectra of Mn2+, Co2+ and Ni2+ ions doped glasses, both direct and indirect optical band gaps have been calculated. The visible absorption spectra of Mn2+:glasses have shown a broad absorption band at 520 nm (6A1g(S) --> 4T1g(G)); with Co2+ ions one absorption band at 605 nm (4A2(4F) --> 4T1(4P)) and another at 1450 nm (4A2(4F) --> 4T1(4F)); and for Ni2+:glasses three absorption bands at 420 nm (3A2g(F) --> 3T1g(P)), 805 nm (3A2g(F) --> 1Eg(D)) and 880 nm (3A2g(F) --> 3T1g(F)) have been observed. For Mn2+:glasses, upon excitation with 262 nm, a green emission (539 nm) with a slight blue shift; and with 392 nm, a green emission (534 nm) with a slight red shift with Mn2+ ions concentration change (0.2-0.5 mol%) has been observed. This green emission has been assigned to (4T1(G) --> 6A1(S)) d-d transition of Mn2+ ions that are in tetrahedral co-ordination. For 0.5 mol% Co2+ ions doped glass, upon excitation with 580 nm, a red emission (625 nm) has been observed which originates from 2E(2G) --> 4A2(4F) transition of Co2+ ions in tetrahedral co-ordination. For Ni2+ ions doped glasses upon excitation with 420 nm, a green (577 nm) and red (670 nm) emissions are observed and are assigned to (1T2g(D) --> 3A2g(F)) and (1T2g(D) --> 3T2g(F)) d-d transitions of Ni2+ ions in octahedral co-ordination.

Borates↗