首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 15 毫秒
1.
《Ceramics International》2016,42(13):14700-14709
Two bioactive glasses with different chemical compositions (mol%) 46.2SiO2–26.9CaO–24.3Na2O–2.6P2O5 (45S5) and 40SiO2–54CaO–6P2O5 (A2) were synthesized by the use of sol–gel and melt–quenching techniques. The effect of synthesis method on glass structure was investigated using X-ray diffraction, FTIR, Raman, XPS, 29Si and 31P MAS–NMR spectroscopic methods. The results show that the synthesis route has significant influence on the glass structure. Both melt–derived A2 and 45S5 glasses exhibit fully amorphous structure, while gel–derived ones, stabilised at 700 °C, reveal the presence of crystalline silicate and phosphate phases. Gel–derived glasses exhibit more polymerized structure compared to melt–quenched ones. Phosphorus is present in the orthophosphate type environment (Q0) together with some pyrophosphate (Q1) species and it does not take part in the formation of Si–O–P bonds. This indicates that phosphorus acts as a glass structure modifier and forms phosphate-rich phase separated from a silica-rich one. The theoretically predicted network connectivity is consistent with the experimental determination only for melt–derived glasses, assuming silicon as the only network former.  相似文献   

2.
Thermal behavior, structural properties, and phase equilibria of the (100−x)TeO2-xNa2O system were studied in the 5 ≤  50 mol% composition range. Investigation of glass formation behavior in the binary system was realized, and the glass formation range was determined as 7.5 ≤  40 mol%. Differential thermal analysis (DTA) and Fourier transform infrared (FTIR) spectroscopy techniques were used for thermal and structural characterization of the glasses. Influence of Na2O content on glass transition temperature (Tg), glass stability (∆T), density (ρ), molar volume (VM), oxygen molar volume (VO), and oxygen packing density (OPD) values of sodium tellurite glasses was evaluated considering the structural transformations in the glass network. For the phase equilibria studies, DTA, X-ray diffraction (XRD), and scanning electron microscopy/energy dispersive X-ray (SEM/EDS) techniques were utilized to characterize the heat-treated samples. According to the phase equilibria studies, three eutectic regions were detected in the 0 < < 50 mol% composition range of the (100−x)TeO2-xNa2O system. A new invariant endothermic reaction was detected for the compositions between 40 ≤  45 mol%. Na2O.8TeO2 (11.11 mol% Na2O) compound that was claimed to exist in the binary system in the literature was found to be the metastable δ-TeO2 phase.  相似文献   

3.
Germanate glasses have potential applications as optical fibers. Materials doped with rare earth ions are good candidates for optical, lasing, and magnetic applications. Based on the ternary system, CeO2–Na2O–GeO2 a series of six glasses were fabricated using powder fusion, and varying the Na2O content from 0 to 45 mol%, and a CeO2 content constant at 3 mol%. The glasses were analyzed by FT‐IR, Raman and X‐ray photoelectron (XPS) spectroscopies to obtain information about the glass structure, cerium oxidation's state and how it is introduced in the glass network. FT‐IR and Raman spectra revealed the presence of GeO6 and GeO4 groups as well as Q2 and Q3 units in the glasses with alkali low content. XPS spectra analysis revealed that the cerium ions were reduced from Ce4+ to Ce3+. The nonbonding to total oxygen ratio was estimated from the curve fitting of the O 1s core level spectra. Density and elastic parameters showed a nonlineal tendency in the change of the physical properties as a function of Na2O content. Finally, photoluminescence spectroscopy confirmed the presence of Ce3+ ions. The characteristic 4f → 5d electronic transitions at 360 nm were detected, when a 280 nm excitation line of pulsed laser was used as excitation source.  相似文献   

4.
《Ceramics International》2022,48(9):12699-12711
The effect of variation of MgO (1.5, 4.5 and 7.5 mol%) content on glass structure, crystallization behavior, microstructure and mechanical properties in a Li2O–K2O–Na2O–CaO–MgO–ZrO2–Al2O3–P2O5–SiO2 glass system has been reported here. Increased amount of MgO enhanced the participation of Al2O3 as a glass network former along with [SiO4] tetrahedra, reducing the amount of non-bridging oxygen (NBO) and increasing bridging oxygen (BO) amount in glass. The increased BO in glass resulted in a polymerized glass structure which suppressed the crystallization and subsequently increased the crystallization temperature, bulk density, nano hardness, elastic modulus in the glasses as well as the corresponding glass-ceramics. MgO addition caused phase separation in higher MgO (7.5 mol%) containing glass system which resulted in larger crystals. The nano hardness (~10 GPa) and elastic modulus (~127 GPa) values were found to be on a much higher side in 7.5 mol% MgO containing glass-ceramics as compared to lower MgO containing glass-ceramics.  相似文献   

5.
《Ceramics International》2023,49(7):10652-10662
Transparent glass-ceramics containing eucryptite and nepheline crystalline phases were prepared from alkali (Li, Na) aluminosilicate glasses with various mole substitutions of Al2O3 for SiO2. The relationships between glass network structure and crystallization behavior of Li2O–Na2O–Al2O3–SiO2 (LNAS) glasses were investigated. It was found that the crystallization of the eucryptite and nepheline in LNAS glasses significantly depended on the concentration of Al2O3. LNAS glasses with the addition of Al2O3 from 16 to 18 mol% exhibited increasing Q4 (mAl) structural units confirmed by NMR and Raman spectroscopy, which promoted the formation of eucryptite and nepheline crystalline phases. With the Al2O3 content increasing to 19–20 mol%, the formation of highly disordered (Li, Na)3PO4 phase which can serve as nucleation sites was inhibited and the crystallization mechanism of glass became surface crystallization. Glass-ceramics containing 18 mol% Al2O3 showed high transparency ~84% at 550 nm. Moreover, the microhardness, elastic modulus and fracture toughness are 8.56 GPa, 95.7 GPa and 0.78 MPa m1/2 respectively. The transparent glass-ceramics with good mechanical properties show high potential in the applications of protective cover of displays.  相似文献   

6.
The structure of glasses with composition x TiO2·(65 ? x) P2O5·35 CaO (x = 0–30 mol%) has been studied and their glass transition temperature, Raman and NMR spectra have been analysed.For TiO2-free glass two phosphate species have been identified as Q2 and Q3. Increasing TiO2 content in glass compositions results in the disappearance of the Q3 and Q2 species and in the formation of, mainly, pyrophosphate structure, Q1.In calcium titanophosphate glass with higher TiO2 content the structure consists of a distorted Ti octahedral linked to pyrophosphate unit through P–O–Ti bonds. In these glass series the structural cohesion increases with TiO2, although a depolymerization in the original P–O–P network occurs.The study of these glasses and the understanding of their structural characteristics can give a valuable contribution for the clarification of their degradation behaviour namely in biological environments.  相似文献   

7.
This study reports on the sintering behavior, crystallization process, and mechanical properties of novel glass-ceramics (CGs) produced by the glass powder compact consolidation method. Substitution of K2O for Na2O and MgO for CaO was attempted in the parent glasses belonging to Na2O-CaO-MgO-SiO2-P2O5-CaF2 system. Glass powder compacts were heat treated at various temperatures between 700°C and 900°C, taking under consideration the glass transition (Tg) and the crystallization peak (Tp) temperatures, which were experimentally determined for each investigated glass by thermal analysis (dilatometry and differential scanning calorimetry). The experimental results showed that sintering always preceded crystallization, regardless of the type of substitution. In the case of MgO substitution for CaO, crystallization was advanced in the range of 800°C-850°C, resulting in the formation of an assembly of crystalline phases, such as diopside, fluorapatite, and wollastonite. The substitution of K2O for Na2O increased the activation energy for crystallization, shifting crystallization process to a high temperature region, with the formation of alpha-potassium magnesium silicate, instead of wollastonite. The GCs produced had values of 22-31 GPa regarding the modulus of elasticity, 5.0-6.1 GPa concerning the microhardness, and 1.4-1.9 MPa⋅m0.5 as regard the fracture toughness, which are similar to those of the human jawbone.  相似文献   

8.
Alkaline earth oxynitride glasses of (Ca, Mg)–Si–Al–O–N with different CaO/(CaO + MgO) molar ratios (0, 0.25, 0.5, 0.75, and 1) were successfully prepared using the sol-gel method, and their structural compositions were characterised by Raman and FT-IR techniques. The glass dynamic properties of thermal expansion coefficient, glass transition temperature (Tg), and static properties of density, molar volume, Vickers hardness and compressive strength were systematically measured and analysed. The results showed that the static properties exhibited an overall regular change as the CaO/(CaO + MgO) ratio gradually increased, while the dynamic properties had an obvious mixed alkaline earth effect, which represented the appearance of an extreme value point in CaO/(CaO + MgO) mole ratios of 0.25 and 0.75, respectively. The typical thermal expansion coefficient and Tg of mixed alkaline earth oxynitride glasses deviated far from the linear connection between single alkaline earth oxynitride glasses. Raman spectra and infrared spectra revealed that the ratio value of the Q3/(Q2+Q4) decreased (Qn: n = no. of bridging anions joining SiO4 tetrahedra) in the mixed alkaline earth oxynitride glasses with increasing the amount of Ca, confirming that Ca decreased the crosslinking between individual tetrahedra via the transformation of Q3 species into Q2 and Q4 species.  相似文献   

9.
Glass for pharmaceutical packaging requires high chemical durability for the safe storage and distribution of newly developed medicines. In borosilicate pharmaceutical glasses which typically contain a mixture of different modifier ions (alkali or alkaline earth), the dependence of the chemical durability on alkaline earth oxide concentrations is not well understood. Here, we have designed a series of borosilicate glasses with systematic substitutions of CaO with MgO while keeping their total concentrations at 13 mol% and a fixed Na2O concentration of 12.7 mol%. We used these glasses to investigate the influence of R = [MgO]/([MgO] + [CaO]) on the resistance to aqueous corrosion at 80°C for 40 days. It was found that this type of borosilicate glass undergoes both leaching of modifier ions through an ion exchange process and etching of the glass network, leading to dissolution of the glass surface. Based on the concentration analysis of the Si and B species dissolved into the solution phase, the dissolved layer thickness was found to increase from ~100 to ~170 nm as R increases from 0 to 1. The depth profiling analysis of the glasses retrieved from the solution showed that the concentration of modifier ions (Na+, Ca2+, and Mg2+) at the interface between the solution and the corroded glass surface decreased to around 40%–60% of the corresponding bulk concentrations, regardless of R and the leaching of modifier cations resulted in a silica-rich layer in the surface. The leaching of Ca2+ and Mg2+ ions occurred within ~50 and <25 nm, respectively, from the glass surface and this thickness was not a strong function of R. The leaching of Na+ ions varied monotonically; the thickness of the Na+ depletion layer increased from ~100 nm at R = 0 to ~200 nm at R = 1. Vibrational spectroscopy analysis suggested that the partial depletion of the ions may have caused some degree of the network re-arrangement or re-polymerization in the corroded layer. Overall, these results suggested that for the borosilicate glass, replacing [CaO] with [MgO] deteriorates the chemical durability in aqueous solution.  相似文献   

10.
The effect of the average ionic potential ξ = Ze/r of the network modifier cations on crack initiation resistance (CR) and Young's modulus E has been measured for a series of alkaline-earth aluminoborosilicate glasses with the compositions 60SiO2–10Al2O3–10B2O3–(20−x)M(2)O–xM’O (0 ≤ x ≤ 20; M, M’ = Mg, Ca, Sr, Ba, Na). Systematic trends indicating an increase of CR with increasing ionic potential, ξ, have been correlated with structural properties deduced from the NMR interaction parameters in 29Si, 27Al, 23Na, and 11B solid state NMR. 27Al NMR spectra indicate that the aluminum atoms in these glasses are essentially all four-coordinated, however, the average quadrupolar coupling constant <CQ> extracted from lineshape analysis increases linearly with increasing average ion potential computed from the cation composition. A similar linear correlation is observed for the average 29Si chemical shift, whereas the fraction of four-coordinate boron decreases linearly with increasing ξ. Altogether the results indicate that in pure alkaline-earth boroaluminosilicate glasses the crack resistance/E-modulus trade-off can be tailored by the alkaline-earth oxide inventory. In contrast, the situation looks more complicated in glasses containing both Na2O and the alkaline-earth oxides MgO, CaO, SrO, and BaO. For 60SiO2–10Al2O3–10B2O3–10MgO–10Na2O glass, the NMR parameters, interpreted in the context of their correlations with ionic potentials, are consistent with a partial network former role of the MgO component, enhancing crack resistance. Altogether the presence of MgO in aluminoborosilicate glasses helps overcome the trade-off issue between high crack resistance and high elasticity modulus present in borosilicate glasses, thereby offering additional opportunities for the design of glasses that are both very rigid and very crack resistant.  相似文献   

11.
Glasses in the Na2O–CaO–SrO–ZnO–SiO2 system have previously been investigated for suitability as a reagent in Al‐free glass polyalkenoate cements (GPCs). These materials have many properties that offer potential in orthopedics. However, their applicability has been limited, to date, because of their poor strength. This study was undertaken with the aim of increasing the mechanical properties of a series of these Zn‐based GPC glasses by doping with nitrogen to give overall compositions of: 10Na2O–10CaO–20SrO–20ZnO–(40?3x)SiO2xSi3N4 (x is the no. of moles of Si3N4). The density, glass‐transition temperature, hardness, and elastic modulus of each glass were found to increase fairly linearly with nitrogen content. Indentation fracture resistance also increases with nitrogen content according to a power law relationship. These increases are consistent with the incorporation of N into the glass structure in threefold coordination with silicon resulting in extra cross‐linking of the glass network. This was confirmed using 29Si MAS‐NMR which showed that an increasing number of Q2 units and some Q3 units with extra bridging anions are formed as nitrogen content increases at the expense of Q1 units. A small proportion of Zn ions are found to be in tetrahedral coordination in the base oxide glass and the proportion of these increases with the presence of nitrogen.  相似文献   

12.
Phosphate-based glasses 45P2O5–30CaO–(25 ? x)Na2O–xMgO for different compositions of x = 0, 1, 2.5, 5 and 10 mol% were prepared using the normal melt quench technique. To study the influence of MgO on phosphate glasses, a series of experimental analyses such as ultrasonic velocities, differential thermal analysis, X-ray diffraction, energy-dispersive X-ray spectroscopy, pH measurements, Fourier transform infrared spectroscopy, scanning electron microscopy and in vitro studies were carried out in all the prepared glasses. A maxima in ultrasonic parameters at x = 2.5 mol% of MgO content and a further decrease in the same with the addition of MgO content were observed in all glasses. The observed results indicate that structural compactness of glass network took place up to 2.5 mol% of MgO (PCNM2.5), beyond which a loose packing of atoms led to structural softening in glass network. The results obtained from X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy analyses in all glasses before and after in vitro studies revealed the existence of higher HAp-forming ability in PCNM2.5 glass.  相似文献   

13.
The effect of SrO/CaO and K2O/Na2O replacements on the crystallization process of glasses based on Na2O-CaO-P2O5-SiO2 system was investigated. The glasses were thermally treated through controlled heat treatment regimes to obtain glass ceramic materials. Combeite Na2Ca2Si3O9, sodium calcium silicate Na2Ca3Si6O16, wollastonite solid solution, and whitlockite Ca3(PO4)2 were identified as major crystalline phases in the prepared thermally treated glasses. No potassium and strontium-containing phases could be detected in the glass-ceramics; potassium seems to be accommodated in the wollastonite structure, while strontium might be incorporated in the sodium calcium silicate structure.The surface reactivity of the prepared glass-ceramic specimens was also studied in vitro in Kokobo's simulated body fluid (SBF). EDAX, SEM, inductively coupled plasma ICP, and FTIR were used to examine the formation of apatite layer's surface and characterize the glass ceramic surface and SBF compositional changes. A decrease in the bioactivity of the glass ceramic was observed as Na2O was replaced by K2O. Strontium together with calcium ions in the apatite layer formed was detected with SrO/CaO replacement.The role played by the glass oxide constituents in determining the crystallization and bioactivity behaviour of the prepared thermally treated glasses was discussed.  相似文献   

14.
It is known that indentation using a diamond indenter induces permanent densification to result in plastic or inelastic deformation of glass. However, it is still unclear whether a high tensile stress causes such a structural change or not. In this study, fracture- and indentation-induced structural changes of glasses with the compositions of 20 Na2O − 40x B2O3 – (80−40x) SiO2 (in mol%, = 0, 0.5, 1, 1.5) are investigated. Two-point bending tests of the glass fibers are performed to apply a high tensile stress to the glasses, and Vickers indentation tests of the glasses are also carried out for comparison. The structural change of the glass is evaluated by using Raman spectroscopy. It is elucidated that a tensile side of the fractured fiber for every composition shows a permanent structural change, which is characterized by a lower wave number shift of Raman peak assigned to the Si-O-Si bending vibration mode. It is also found that the behaviors of Raman peaks of the fractured fiber are opposite to those of the indented glass under a high compressive stress.  相似文献   

15.
《Ceramics International》2023,49(16):27201-27213
A glass system based on the Na2O/B2O3-doped CrO3 borosilicate has been prepared by the melt quenching technique. The structure, color, optical absorbance and ligand field parameters were investigated for a wide range of Na2O additives (20–60 mol%). All X-ray photoelectron spectroscopy (XPS) profiles were used to study the chemical shift states of the glass-constituting elements. Fourier transform infrared (FTIR) analyses explored the internal structure and subnetwork units. Furthermore, from the FTIR results, we concluded the transformation of trigonal borate units (BO3) to tetrahedral borate units (BO4) and the possibility of transformation from B3-O-Si linkages to B4-O-Si linkages. Despite the fixed CrO3 content, the doped glasses showed a color transition from green to yellow with additional Na2O content. The increased intensity of the band at 451–427 nm and the decreased intensity of the band at 619–627 nm are the main reasons for this color transformation. The optical absorption spectra confirmed the existence of Cr3+ and Cr6+ states. A decreasing behavior for the crystal field splitting (10Dq) and an increasing behavior for Racah parameter (B) were obtained with further Na2O additives. The decreasing behavior of 10Dq was attributed to reduced oxygen concentrations with more Na2O/B2O3 substitutions. The increasing behavior of B reflects the tendency of the bond between the Cr cations and their oxygen ligands towards an ionic nature. Moreover, the Dq/B values indicated that Cr3+ cations are in high-field positions for the glass sample containing 20 mol% Na2O, and Cr3+ cations are in intermediate field positions for the glass sample containing 30 mol% Na2O. However, for the glass samples doped with 40, 50 and 60 mol% Na2O glass samples, Cr3+-cations are in weak field positions. These results of (Dq/B) recommend the glass sample doped with 20 mol% Na2O for tunable laser applications.  相似文献   

16.
《Ceramics International》2017,43(16):13800-13809
In this work we developed improved bioactive glasses and glass-ceramics for biomedical applications, investigating their in vitro bioactivity, biocompatibility and antibacterial properties against E-Coli. A melt-quenched bioactive glass of the SiO2-CaO-P2O5-MgO system was modified with the addition of 1 and 2 mol% Ag2O and the 1 mol% Ag2O-containing glasses were then heat treated to produce glass-ceramics. Surface modifications after soaking in SBF and ionic concentration changes showed that addition of silver and crystallization did not affect bioactivity although crystalline phases promoted a decrease in the degradation rate.Biocompatibility of all Ag-containing glasses and glass-ceramics was confirmed for certain samples concentrations. The antibacterial activity of the glasses against E-Coli was generally improved with decreasing particle size or increasing Ag2O. The Ag-containing glass-ceramics with higher content of crystalline phase appears as a promising biocompatible biocidal material with potential applications in bone-related diseases.  相似文献   

17.
Mona A. Ouis 《SILICON》2011,3(4):177-183
Some glasses based on Hench’s patented bioglass have been prepared with ZnO replacing Na2O or CaO in order to investigate their bioactivity in the glassy state or after conversion to their glass-ceramic derivatives. In-vitro investigations of bioactivity of the prepared glass and their glass-ceramics derivatives were carried out by Infrared absorption spectra (IR) of the samples before and after immersion in simulated body fluid (SBF) for different time periods at 37 °C. An X-ray Diffraction (XRD) analysis technique was performed on the glass-ceramic samples to identify the crystalline phases formed during the controlled thermal treatment. Chemical corrosion experiments were also performed to evaluate the chemical behaviour of both glassy and the glass-ceramic derivatives towards SBF. The IR results showed that the amount of the apatite layer formed on the surface of the sample containing ZnO depends on the wt% of ZnO content. The X-ray results indicate that there are two phases formed: sodium calcium silicate and kilchoanite. Weight loss data were observed to change depending on the percent of ZnO and the role of housing of Zn2+ in the glass structure. Corrosion behaviour of glass-ceramic derivatives indicates higher durability than in the corresponding parent glasses as expected.  相似文献   

18.
《Ceramics International》2016,42(5):5842-5857
The effect of SrO substitution for CaO in two sol–gel glasses with different chemical compositions (mol%) A2Sr: (54−x)CaO–xSrO–6P2O5–40SiO2 and S2Sr: (16−x)CaO–xSrO–4P2O5–80SiO2 (x=0, 1, 3 and 5) stabilized at 700 °C on their structure (XRD, FTIR) and bioactive properties (SBF test) was investigated. Preliminary in vitro tests using human articular chondrocytes of selected A2Sr glass were also conducted. Moreover, the subject of this study was to detect the changes on material properties after heat treatment at 1300 °C. The results show that the effect of strontium substitution on structure, bioactivity and crystallization after treatment at both the above temperatures strongly depends on CaO/SiO2 molar ratio. The presence of 3–5 mol% of strontium ions creates more expanded glass structure but does not markedly affect crystallization ability after low temperature treatment. Sintering at 1300 °C of A2 type glasses results in crystallization of pseudowollastonite, hydroxyapatite and also Sr-substituted hydroxyapatite for 3–5 mol% of SrO substitution. The increase of strontium concentration in silica-rich materials after sintering leads to appearance of calcium strontium phosphate instead of calcium phosphate. Bioactivity evaluation indicates that substitution of Sr for Ca delays calcium phosphate formation on the materials surface only in the case of silica-rich glasses treated at 700 °C. Calcium-rich glasses, after both temperature treatments, reveals high bioactivity, while crystal size of hydroxyapatite decreases with increasing Sr content. High temperature treatment of high-silica glasses inhibits their bioactivity. Preliminary in vitro tests shows Sr addition to have a positive effects on human articular chondrocytes proliferation and to inhibit cell matrix biomineralization.  相似文献   

19.
《Ceramics International》2022,48(6):7796-7805
In this work, phospho-silicate glasses with SiO2–P2O5–Na2O–F-MO (M = Ca, Sr, Zn) composition were prepared by using the conventional melt quenching technology. Structural, physical, and chemical property tests were used to analyze the effects of different SrO and ZnO content on the structure and properties of the glasses. The results showed that the glass stability varied nonlinearly as CaO was replaced by SrO, which was mainly related to the different positions of Sr2+ and Ca2+ ions breaking the network connection in the network structure, and the substitution of ZnO for CaO led to a continuous decrease in the stability of the glasses. The immersion experiment showed that SrO doping was more feasible than ZnO doping to improve the biological activity of the glasses, and the doping of ZnO promoted the dissolution of ions in the glasses. The obtained results indicated that the glass samples prepared in this paper have potential biological activity, which has potential applications in dental treatment.  相似文献   

20.
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号