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Influence of glass composition on the properties of glass polyalkenoate cements. Part IV: influence of fluorine content.

The influence of fluorine content of the glass in a series of glasses based on: 4.5SiO2-3.0Al2O3-1.5P2O5-(5.0-X)CaO-XCaF2 was investigated on their cement formation with poly(acrylic acid). Increasing the fluorine content of the glass was found to reduce the glass transition temperature, as a result of fluorine replacing bridging oxygens by non-bridging fluorines. Working and setting times of the cement pastes reduced with increasing fluorine content of the glass. Compressive strength and Young's moduli increased with fluorine content initially and then remained approximately constant. Fracture toughness, toughness and un-notched fracture strength were not significantly influenced by fluorine content. The results are consistent with fluorine simultaneously disrupting the glass network and reducing the basicity of the glass.

Fluorine↗

Structure of bioactive glass and its application to glass ionomer cement.

We prepared a new glass ionomer cement using bioactive CaO-P2O5-SiO2(-MgO) glass and investigated its setting process using FT-IR and MAS NMR analyses. The compressive strengths of the cements depended on the glass composition and a maximum strength of 33.3 +/- 4.7 MPa was obtained using cement with the glass composition of MgO:4.6, CaO:44.9, SiO2:34.2 and P2O5:16.3% in weight. FT-IR analysis showed that the COOH group in the polyacrylic acid decreased and carboxylate ion (COO-Ca2+) increased after the setting reaction. A broad signal appeared around -82 ppm in 29Si MAS-NMR spectra of the glass and a new signal corresponding to hydrated silica gel formation appeared around -102 and -111 ppm after setting. This suggests that Ca2+ was released from the glass powder to form carboxylate salt and that a degree of polymerization in the silicate network increased. The setting mechanism of the cement was found to be essentially the same as in conventional glass ionomer cement.

Biocompatible Materials↗

Glass-reinforced hydroxyapatite: a comprehensive study of the effect of glass composition on the crystallography of the composite.

Glass-reinforced HA composites were produced using phosphate-based glasses, and a structure refinement was carried out to determine the effect of the glass on the structure of the residual HA. Quantitative phase analysis showed that the glass causes some of the HA to decompose to beta-TCP and, at higher temperatures, to alpha-TCP. It also was indicated that when three phases were present, the formation of the alpha-TCP arose from decomposition of the beta-TCP and not from further decomposition of HA to alpha-TCP. The unit cell dimensions showed a decrease in the a axis and an increase in the c axis, giving an overall unit cell decrease in volume. There also was a significant effect based on the amount of glass added. The changes found in the composite containing the 4 wt% glass were attributed to the loss of carbonate and loss of hydroxyl. This was expected to cause shrinkage in the unit cell; however this was not seen, and therefore the major changes in the unit cell were attributed to the ions from the glass taking an interstitial role in the HA structure, thus not allowing the unit cell to shrink as much as expected.

Ceramics↗

Role of the glass phase in bioactive glass-ceramics.

Glass-ceramics, or composites with a glass-ceramic matrix prepared by controlled crystallization, almost invariably contain a residual glass phase. A suitable composition for the residual glass phase of bioactive glass-ceramics can be found approximately and controlled on the basis of calculation of a structural parameter Y, which in the simplified concept of the glass structure corresponds to the mean number of bridging oxygens per polyhedron in the glass lattice.

Biocompatible Materials↗

Bioactive calcium pyrophosphate glasses and glass-ceramics.

Calcium phosphate glass-based materials in the pyrophosphate region are briefly reviewed. Calcium pyrophosphate glasses can be prepared by including a small amount of TiO(2) (<or=10mol%). Bonelike apatite forms on some of the glasses in simulated body fluid. By heating powder-compacts of the glasses, they are crystallized and subsequently are sintered, resulting in fabrication of high-strength glass-ceramics with machinability; they are easier to be machined using conventional tools in comparison with conventional calcium phosphate ceramics. beta-Ca(2)P(2)O(7) crystal formed in the glass-ceramics plays an important role in the machinability. Their apatite-forming ability in simulated body fluid is drastically enhanced after autoclaving in distilled water. The glass-ceramics can be easily coated on a new beta-type titanium alloy using a conventional glazing technique.

Alloys↗

Comparison of glass wool and glass powder methods for concentration of viruses from treated waste waters.

Enumeration of cultivable virus particle in sewage requires the samples to be concentrated. Two adsorption-elution methods, the glass wool cartridge method and the glass powder fluid layer method were compared. Firstly, it was demonstrated that virus could be readily recovered from the head, first 25 ml, of eluate of glass wool rather than from a reconcentration of the entire eluate, either by organic flocculation: 83% of positivity vs 44% respectively or double precipitation by PEG: 85% of positivity vs 61% respectively. Concentration on glass wool allowed the rescue of a greater number of positive samples (33/35) than on glass powder (16/35) as well as a higher mean titer of indigenous viruses, respectively 19 MPNCU/l vs 6 MPNCU/l (F1(34) = 36.02, P < 0.0001). Enteroviruses were the most frequently isolated viruses: found in 34/35 samples by either method, in 32/35 samples by glass wool, and in 14/35 samples by glass powder. Of the 12 enterovirus types identified by either method, a majority was Echovirus 6 (10 samples), Echovirus 11 (7 samples), Coxsackievirus B5 (4 samples) and also Coxsackievirus A7, A16, A21, B1, B6, Echovirus 1, 4, 12 and 19. Adenovirus types 1 and 5 were isolated from 4 samples by either method.

Adsorption↗

Mechanical and biological properties of two types of bioactive bone cements containing MgO-CaO-SiO2-P2O5-CaF2 glass and glass-ceramic powder.

In this study two types of bioactive bone cement containing either MgO-CaO-SiO2-P2O5-CaF2 glass (type A) or glass-ceramic powder (type B) were made to evaluate the effect of the crystalline phases on their mechanical and biological properties. Type A bone cement was produced from glass powder and bisphenol-a-glycidyl methacrylate (BIS-GMA) resin, and type B from glass-ceramic powder containing apatite and wollastonite crystals and BIS-GMA resin. Glass or glass-ceramic powder (30, 50, 70, and 80 by wt %) was added to the cement. The compressive strength of type A (153-180 MPa) and B (167-194 MPa) cement were more than twice that of conventional polymethylmethacrylate (PMMA) cement (68 MPa). Histological examination of rat tibiae showed that all the bioactive cements formed direct contact with the bone. A reactive layer was seen at the bone-cement interface. In specimens with type A cement the reactive layer consisted of two layers, a radiopaque outer layer (Ca-P-rich layer) and a relatively radiolucent inner layer (low-calcium-level layer). With type B cement, although the Ca-P-rich layer was seen, the radiolucent inner layer was absent. Up to 26 weeks there was progressive bone formation around each cement (70 wt %) and no evidence of biodegradation. The mechanical and biological properties of the cements were compared with those of a previously reported bone cement containing MgO-free CaO-SiO2-P2O5-CaF2 glass powder (designated type C).

Animals↗

Bone bonding behavior of MgO-CaO-SiO2-P2O5-CaF2 glass (mother glass of A.W-glass-ceramics).

In this study, it was found that a Ca-P layer and a Si layer were formed on the interface of the mother glass of apatite-wollastonite containing glass-ceramics (designated AW) and bone tissue. The dissolution of Si, Ca, and P from glass (MgO-CaO-SiO2-P2O5-CaF2) is necessary to form a chemical film (a Si layer and a Ca-P layer). The three kinds of glasses used were 1) a mirror surface of the mother glass (MgO 4.6, CaO 44.9, SiO2 34.2, P2O5 16.3, CaF 0.5 weight ratio) of AW (designated G-AW (mirror], 2) an abraded surface of G-AW (designated G-AW (#2000)), 3) a mirror surface SiO2 glass (designated G-Si, 100% SiO2). The glass plates (15 mm x 10 mm x 2 mm) were implanted into the metaphysis of tibia of mature male rabbits for 10 and 25 weeks. The failure load, when an implant detached from the bone or when the bone itself broke, was measured by a detaching test and the interface of glass/bone was observed by SEM-EPMA. Failure loads in G-Si, G-AW (mirror), and G-AW (#2000) 10 weeks after implantation were 0.18 +/- 0.24, 3.06 +/- 1.29, and 2.94 +/- 1.77 kg, respectively. Those in G-Si, G-AW (mirror), and G-AW (#2000) 25 weeks after implantation were 1.30 +/- 1.18, 3.88 +/- 1.06, and 3.55 +/- 1.51, respectively. The failure loads in G-Si vs. G-AW (mirror) and those in G-Si vs. G-AW (#2000) differed significantly (P less than 0.01). There were no significant differences in the failure load according to the surface roughness of G-AW. As shown by SEM-EPMA observation, a Si layer next to G was adjacent to a Ca-P layer next to the bone. The chemical film showed no increase in thickness as time passed. A Ca-P layer did not form on the interface of Si-G and bone.

Biocompatible Materials↗

The in vivo performance of a sol-gel glass and a glass-ceramic in the treatment of limited bone defects.

The in vivo evaluation, in New Zealand rabbits, of a SiO(2)-P(2)O(5)-CaO sol-gel glass and a SiO(2)-P(2)O(5)-CaO-MgO glass-ceramic, both bioactive in Kokubo's simulated body fluid (SBF), is presented. Bone defects, performed in the lateral aspect of distal right femoral epiphysis, 5mm in diameter and 4mm in depth, were filled with (i) sol-gel glass disks, (ii) glass-ceramic disks, or (iii) no material (control group). Each group included 8 mature and 8 immature rabbits. A 4-month radiographic study showed good implant stability without axial deviation of extremities in immature animals and periosteal growth and remodelling around and over the bone defect. After sacrifice, the macroscopic study showed healing of bone defects, with bone coating over the implants. The morphometric study showed a more generous bone formation in animals receiving sol-gel glass or glass-ceramic disks than in control group. Histomorphometric study showed an intimate union of the new-formed bone to the implants. This study allows considering both materials as eligible for bone substitution or repair. Their indications could include cavities filling and the coating of implant surfaces. The minimum degradation of glass-ceramic disks suggests its application in locations of load or transmission forces. As specific indication in growth plate surgery, both materials could be used as material of interposition after bony bridges resection.

Animals↗

How does the pre-massage and post-massage 2-glass test compare to the Meares-Stamey 4-glass test in men with chronic prostatitis/chronic pelvic pain syndrome?

PURPOSE: The Meares-Stamey 4-glass test is the standard method of assessing inflammation and the presence of bacteria in the lower urinary tract in men presenting with the chronic prostatitis syndrome. However, most urologists do not use it in daily practice because of the time and difficulty in performing it, as well as the additional expense. We evaluated a simpler test, the 2-glass pre-massage and post-massage test, and compared it with the Meares-Stamey 4-glass test to detect inflammation and bacteria in men with chronic prostatitis/chronic pelvic pain syndrome. MATERIALS AND METHODS: The study population included 353 men enrolled in the National Institutes of Health Chronic Prostatitis Cohort study with baseline leukocyte counts and 2-day bacterial cultures on specimens obtained from a standard 4-glass test (VB1, VB2, expressed prostatic secretions, VB3). The chi-square test was performed to assess associations of white blood cell counts in expressed prostatic secretions and VB3. A receiver operating characteristic curve was constructed to determine the optimal cut point of white blood cells in VB3 in predicting white blood cells in expressed prostatic secretions. Sensitivity and specificity of VB3 cultures predicting expressed prostatic secretions and positive Meares-Stamey results were calculated from 2 x 2 contingency tables. RESULTS: Analysis of binary leukocyte outcomes (no white blood cells vs any white blood cells) suggests that white blood cells tend to be present in expressed prostatic secretions when there are any white blood cells in VB3, p <0.0001, the optimal cut point being white blood cell counts of 3 in VB3 (best predictive ability with area under ROC 0.771) to predict 5+ in expressed prostatic secretions with a sensitivity of 76% and specificity of 70%. The optimal cut point of white blood cells in VB3 to predict 10 white blood cells in expressed prostatic secretions was 4 (62% sensitivity and 75% specificity). Uropathogens localizing to expressed prostatic secretions or VB3 confirms a positive 4-glass Meares-Stamey localization test. The sensitivity and specificity of a VB3 localizing culture only in predicting a positive Meares-Stamey 4-glass test result for any uropathogen were 44% to 54% (depending on definition) and 100%, respectively. The pre-massage and post-massage test predicted a correct diagnosis in more than 96% of subjects. CONCLUSIONS: The value of localizing leukocytes and uropathogens to prostate specific specimens remains controversial in chronic heavily pretreated patients, but these data may help direct therapy (anti-inflammatory or antimicrobial) when obtained at first presentation. The pre-massage and post-massage test has strong concordance with the 4-glass test and is a reasonable alternative when expressed prostatic secretions are not obtained.

Bacteria↗

Development of soluble glasses for biomedical use Part II: the biological response of human osteoblast cell lines to phosphate-based soluble glasses.

Soluble glasses are considered to be of potential clinical value in orthopaedic and dental surgery. However, the biological response to these materials is not well understood. To determine the effects of these glasses, two human osteoblast cell lines, MG63 and HOS (TE85), were incubated in vitro in the presence of increasing concentrations of extracts of the glasses. The effects of the extracts on cell growth was measured using the MTT assay and an ELISA assay was used to measure the expression of bone sialoprotein (BSP), osteonectin (ON) and fibronectin (FN), antigens which play a fundamental part in the integrity and function of hard connective tissue. The results showed that the proliferation of the cells was adversely affected only by the more soluble glasses, which also down-regulated the expression of the bone-associated proteins. In contrast, the extract of the glass with the lowest dissolution rate, which contains relatively elevated levels of Ca2+, was found to enhance bone cell growth and antigen expression. These findings suggest that the compositions of these glasses at least partly determine the response of cells and thus, that the glasses could be modified to elicit a more optimal biological response and clinical efficacy.

Journal Article↗

Glass structure and ion dynamics of lead-cadmium fluorgermanate glasses.

Glass structure and fluorine motion dynamics are investigated in lead-cadmium fluorgermanate glasses by means of differential scanning calorimetry, Raman scattering, x-ray absorption (EXAFS), electrical conductivity (EC), and (19)F nuclear magnetic resonance (NMR) techniques. Glasses with composition 60PbGeO(3)-xPbF(2)-yCdF(2) (in mol %), with x+y=40 and x=10, 20, 30, 40, are studied. Addition of metal fluorides to the base PbGeO(3) glass leads to a decrease of the glass transition temperature (T(g)) and to an enhancement of the ionic conductivity properties. Raman and EXAFS data analysis suggest that metagermanate chains form the basic structural feature of these glasses. The NMR study leads to the conclusion that the F-F distances are similar to those found in pure crystalline phases. Experimental results suggest the existence of a heterogeneous glass structure at the molecular scale, which can be described by fluorine rich regions permeating the metagermanate chains. The temperature dependence of the NMR line shapes and relaxation times exhibits the qualitative and quantitative features associated with the high fluorine mobility in these systems.

Journal Article↗

Chiral-glass transition and replica symmetry breaking of a three-dimensional heisenberg spin glass

Extensive equilibrium Monte Carlo simulations are performed for a three-dimensional Heisenberg spin glass with the nearest-neighbor Gaussian coupling to investigate its spin-glass and chiral-glass orderings. The occurrence of a finite-temperature chiral-glass transition without the conventional spin-glass order is established. Critical exponents characterizing the transition are different from those of the standard Ising spin glass. The calculated overlap distribution suggests the appearance of a peculiar type of replica-symmetry breaking in the chiral-glass ordered state.

Journal Article↗

Glass formation criterion for various glass-forming systems.

A conceptual approach to evaluate glass-forming ability for various glass-forming systems has been proposed from a physical metallurgy point of view. It was found that the glass-forming ability for noncrystalline materials was related mainly to two factors, i.e., 1/(T(g)+T(l)) and Tx (wherein Tx is the onset crystallization temperature, T ( g) the glass transition temperature, and T(l) the liquidus temperature), and could be predicated by a unified parameter gamma defined as T(x)/(T(g)+T(l)). This approach was confirmed and validated by experimental data in various glass-forming systems including oxide glasses, cryoprotectants, and metallic glasses.

Journal Article↗

Processing of an apatite-mullite glass-ceramic and an hydroxyapatite/phosphate glass composite by selective laser sintering.

The work presented details the results of an investigation into the feasibility of using Selective Laser Sintering (SLS) to directly produce customised bioceramic implants. The materials used were bioactive in nature and included a glass-ceramic and a combination of hydroxyapatite and phosphate glass. The glass-ceramic was selected from the range of apatite-mullite materials in the SiO2.Al2O3.CaO.CaF2.P2O5 series, due to their potentially suitable biological and mechanical properties. The hydroxyapatite and phosphate glass combination was chosen to allow an alternative production approach to be investigated. The viability of using both these materials with the SLS process was assessed and the process route and resulting material properties characterised using a variety of techniques including Differential Thermal Analysis (DTA), X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). The results obtained indicate that it was possible to produce multiple layer components from both materials using the SLS process. The glass-ceramic materials could only be processed at very low scan speeds and powers, yielding relatively brittle components. It was though possible to produce parts from the hydroxyapatite and phosphate glass combination across a much wider range of parameters, producing parts which had a greater potential for possible implant production.

Aluminum Silicates↗

The glass polyphosphonate cement: a novel glass-ionomer cement based on poly(vinyl phosphonic acid).

This paper outlines research which aimed to develop a new type of Glass-ionomer cement, the glass polyphosphonate cement. The glass polyalkenoate cement, a form of Glass-ionomer cement, is now widely used in dentistry and is based on the reaction between an ion-leachable aluminosilicate glass and an aqueous solution of poly(acrylic acid) or its copolymers. The new cements described in this paper employ a novel polymer, poly(vinyl phosphonic acid), PVPA, as the acidic component. This is a much stronger acid than those used in the glass polyalkenoate cement, and various means must be employed to moderate the reaction in order to obtain a viable cement. These cements show a number of important differences in performance in comparison with PAA-based systems and these differences are discussed in the paper.

Fluorocarbon Polymers↗

Self-reinforced composites of bioabsorbable polymer and bioactive glass with different bioactive glass contents. Part I: Initial mechanical properties and bioactivity.

Spherical bioactive glass 13-93 particles, with a particle size distribution of 50-125 microm, were combined with bioabsorbable poly-L,DL-lactide 70/30 using twin-screw extrusion. The composite rods containing 0, 20, 30, 40 and 50 wt% of bioactive glass were further self-reinforced by drawing to a diameter of approximately 3 mm. The bioactive glass spheres were well dispersed and the open pores were formed on the composite surface during drawing. The initial mechanical properties were studied. The addition of bioactive glass reduced the bending strength, bending modulus, shear strength, compression strength and torsion strength of poly-L,DL-lactide. However, the strain at maximum bending load increased in self-reinforced composites. Initially brittle composites became ductile in self-reinforcing. The bioactivity was studied in phosphate buffered saline for up to 12 days. The formation of calcium phosphate precipitation was followed using scanning electron microscopy and energy dispersive X-ray analysis. Results showed that the bioactive glass addition affected the initial mechanical properties and bioactivity of the composites. It was concluded that the optimal bioactive glass content depends on the applications of the composites.

Biocompatible Materials↗

Glass-ceramics obtained by the recycling of end of life cathode ray tubes glasses.

This work is concerned with open-loop recycling of end of life Cathode Ray Tubes glass (an unsolved problem when considering that in Europe almost 90% of EOL electronic goods is disposed of in landfills), focusing on the development of glass-ceramics from panel or funnel glass with dolomite and alumina, and the evaluation of the tendency towards crystallisation with particular attention on composition and thermal treatment. Glasses were melted at a temperature of about 1500 degrees C and transformed into glass-ceramics by different thermal treatments (900 degrees C to approximately 1100 degrees C temperature range and 0.5 to approximately 8h soaking time). By using the evaluation of thermal, mineralogical and microstructural data it has been pointed out that a good degree of crystallisation is reached at about 1000 degrees C and with a high proportion of waste glass (50-75%) if 40-45% of CaO and MgO bearer (dolomite) is introduced. In this way alkaline and alkaline-earth silicate and aluminosilicate mainly develop probably with a surface mechanism.

Ceramics↗