Nanocrystal formation and structure in oxyfluoride glass ceramics

The up-conversion luminescent property of the oxyfluoride glass ceramics 30SiO2·15Al2O3· （50-x）PbF2·xCdF2 doped with 4ErF3·1YbF3 has been investigated. Up-conversion luminescent intensity of Er^3＋ ions increased obviously after heat-treatment due to co-doping with CdF2. The structure model of nanocrystals PbxCdl-xF2 was determined and the effect of CdF2 in oxyfluoride glass ceramics was explained by the analysis of x-ray diffraction data. Different nucleation temperatures of samples with different compositions were obtained by differential thermal analysis curves and the results showed the growth process of different nanocrystals in glass ceramics.

Oxy-Fluoride Borate Infrared Up-Conversion Glass Ceramics

The processing parameters and infrared up-conversion properties of fluoroborate glass ceramics in composition of BaB_2O_4+AlF_3+BaF_2+PbF_2∶YbF_3+HoF_3 were reported. The emission spectrum was measured by Hitachi F-4500 spectrometer. The results show that three emission peaks located at 470,545 and 655 nm respectively are observed,(among) which the peak at 545 nm is the strongest. Photon absorption theory and energy transmission theory are used to explain the emission spectrum.

Effects of ZnO,FeO and Fe_(2)O_(3)on the spinel formation,microstructure and physicochemical properties of augite-based glass ceramics

Augite-based glass ceramics were synthesised using ZnO,FeO,and Fe_(2)O_(3)as additives,and the spinel formation,matrix structure,crystallisation thermodynamics,and physicochemical properties were investigated.The results showed that oxides resulted in numerous preliminary spinels in the glass matrix.FeO,ZnO,and Fe_(2)O_(3)influenced the formation of spinel,while FeO simplified the glass network.FeO and ZnO promoted bulk crystallisation of the parent glass.After adding oxides,the grains of augite phase were refined,and the relative quantities of augite crystal planes were also influenced.All samples displayed good mechanical properties and chemical stability.The 2wt%ZnO-doping sample displayed the maximum flexural strength(170.3 MPa).Chromium leaching amount values of all the samples were less than the national standard(1.5 mg/L),confirming the safety of the materials.In conclusion,an appropriate amount of zinc-containing raw material is beneficial for the preparation of augite-based glass ceramics.

Optical temperature sensor based on up-conversion fluorescence emission in Yb^(3+):Er^(3+) co-doped ceramics glass

yb^3＋：Er^3＋ co-doped oxy-fluoride ceramics glass has been prepared. The mechanism of up-conversion emissions about Er^3＋ was discussed, and the temperature properties of green up-conversion fluorescence between 303 and 823 K were investigated. The results show that the sensitivity of this sample reaches its maximum value, about 0.0047 K^-1, when the temperature is 383 K, indicating that this kind of sample can be used as high temperature and high sensitivity optical temperature sensor.

Influence of Nucleation Agents Concentration on Crystallization Structure and Properties of Glass-ceramics

Deep color glass-ceramics is prepared by using gold tailings as the main raw material, and Cr2O3 is added as nucleation agent. Influence of different Cr2O3 additions on crystallization structure and properties of CaO-MgO-Al2O3-SiO2 glass-ceramics has been discussed so as to select optimum additions. DTA is employed to determine optimum crystallization and nucleation temperatures; XRD and SEM are used to characterize microstructure of each sample; and performance indexes, such as water absorption, bulk density, flexural strength and so on, are also determined. Experimental results show that when 3wt% Cr2O3 is introduced, fine glass-ceramics with diopside as the main crystal and Ca-Fe diopside as the second-crystal is obtained, and its corresponding performance indexes are as follows： water absorption 0.12%, bulk density 2.56 g/cm^3, and flexural strength 70.01 Mpa.

Up-conversion luminescence properties and energy transfer of Er^(3+)/Yb^(3+)co-doped oxyfluoride glass ceramic containing CaF_2 nano-crystals

The Er^3＋/yb^3＋ co-doped transparent oxyfluoride glass-ceramics containing CaF2 nano-crystals were successfully prepared. After heat treatments, transmission electron microscopy （TEM） images showed that CaF2 nano-crystals of 20-30 nm in diameter precipitated uniformly in the glass matrix. luminescence of Er^3＋ at 540 nm and 658 nm was observed in Comparing with the host glass, high efficiency upconversion the glass ceramics under the excitation of 980 nm. Moreover, the size of the precipitated nano-crystals can be controlled by heat-treatment temperature and time. With the increase of the nano-crystal size, the intensity of the red emission increased more rapidly than that of the green emission. The energy transfer process of Er^3＋ and Yb^3＋ was convinced and the possible mechanism of Er^3＋ up-conversion was discussed.

Enhancement of up-conversion luminescence properties in Yb^(3+)/Tm^(3+)/Er^(3+) tri-doped transparent oxyfluoride tellurite glass ceramics

Optically transparent Er3＋/Tm3＋/Yb3＋ tri-doped oxyfluoride tellurite based nano-crystallized glass ceramics with the batching composition of 73TeO2-15ZnO-7ZnF2-3YF3-1.5YbF3-0.3ErF3-0.2TmF3 （mol%） is prepared by a conventional melting quenching and the subsequent heat treatment processes. The sizes of grown nano-crystals in glass matrix appear to be smaller than 100 nm from the scanning electron mi- croscope measurement. Visible up-conversion luminescence of the as melted glass and glass ceramics is investigated. The three-color up-conversion luminescence intensities by 980-nm pumping are increased significantly due to the heat treatment, and the blue intensity increases with a higher magnitude than other wavelengths after heat treatment.

Evolution of Er^(3+) Distribution in the Oxyfluoride Glass Ceramics with Heating

The distribution characteristics of Er^3＋ ions doped in the oxyfluoride glass ceramics containing LaF3 nanocrystals heat-treated at 650 ℃ for different durations were investigated. The results of the integral absorption cross-section analysis demonstrated that the partition fraction of Er^3＋ in LaF3 nanocrystals increases with prolonging of heating time, The anomalous phenomena of Er^3＋ emissions in the up-and the down-conversion fluorescence spectra are well explained based on the calculated results.

Preparation and Luminescence of Er^(3+) Doped Oxyfluoride Glass Ceramics Containing LaF_3 Nanocrystals

Er^3＋ doped transparent oxyfluoride glass ceramics version and near infrared luminescence behavior of Er^3＋ in containing LaF3 nanocrystals were prepared and the up-conglasses heat-treating time and temperature, the size （varied from 0 to 19 and glass ceramics were investigated. With increasing nm） and crystallinity （varied from 0 to 47%） of LaF3 nanocrystals in the glass ceramics are increased. The up-conversion luminescence intensity of Er^3＋ ions in the glass ceramics is much stronger than that in the glasses The near infrared emission of Er^3＋ ions in and increased significantly with increasing heat-treating time and temperature the glass ceramics is found to be similar to that in the glasses.

Spectroscopic properties and mechanism of Tm^(3+)/Er^(3+)/Yb^(3+) co-doped oxyfluorogermanate glass ceramics containing BaF_2 nanocrystals

Transparent Tm^3＋/Er^3＋/yb^3＋ co-doped oxyfluorogermanate glass ceramics containing BaF2 nanocrystals are prepared. Under excitation of a 980-nm laser diode （LD）, compared with the glass before heat treatment, the Tm^3＋/Er^3＋/yb^3＋ co-doped oxyfluorogermanate glass ceramics can emit intense blue, green and red up-conversion luminescence and Stark- split peaks; X-ray diffraction （XRD） and transmission electron microscope （TEM） results show that BaF2 nanocrystals with an average diameter of 20 nm are precipitated from the glass matrix. Stark splitting of the up-conversion luminescence peaks in the glass ceramics indicates that Tm^3＋, Er^3＋ and （or） Yb^3＋ ions are incorporated into the BaF2 nanocrystals. The up-conversion luminescence intensities of Tm^3＋, Er^3＋ and the splitting degree of luminescence peaks in the glass ceramics increase significantly with the increase of heat treat temperature and heat treat time extension. In addition, the possible energy transfer process between rare earth ions and the up-conversion luminescence mechanism are also proposed.

Effect of SrO on the Structure of Apatite and Wollastonite Phases of Na₂O-CaO-SiO₂-P₂O₅Glass System

Glasses in the system 24.5Na2O·24.5CaO·6P2O5·xSrO·(45-x)SiO2 have been studied in the composition region of x = 0 - 15 mol%. The as prepared glasses are transparent and have an amorphous network structure. On the otherhand, heat treated glasses are transformed to opaque white glass ceramic characterized by their highly crystalline network structure. Crystalline apatite (calcium phosphate, Ca3(PO4)2, wollastonite (calcium silicate, CaSiO3), and strontium calcium phosphate Ca2Sr(PO4)2 are the main well-formed crystalline species played the major role in material bioactivity. Increasing SrO leads to enhancing material crystallite and enhances the hardness of the host glass matrix. The change of XRD spectra, 31P NMR chemical shift and hardness number upon increasing SrO are considered due to modification of the apatit Ca(PO3)2 to involve Sr ions inducing Ca2Sr (PO4)2 apatite one. Such species play the role in enhancing material properties and hardness.

Temperature sensing behavior of Tm^3+:1G4(a),1G4(b) in oxyfluoride glass ceramics containing BaYbxY1-xF5 nanocrystals

Tm3+-doped transparent oxyfluoride glass ceramics containing BaYbxY((1-x))F5 nanocrystals were prepared via high temperature solid phase melting method,of which up-conversion emission is achieved by the Yb3+-mediated energy transfer process.The required photon number of Tm3+ions emissions in BaYbxY(1-x)F5 nanocrystals was calculated through the luminescence spectra,revealing the strong dependence of energy transfer mechanism on Yb3+ions concentration.Meanwhile,based on the fluore scence intensity ratio technology,the effect of different energy transfer mechanism on the temperature sensitivity was investigated by the temperature-dependent luminescence intensity of thermally coupled energy levels of Tm3+:1G4(a),1G4(b).The obtained sensitivity decreases with the increase of Yb3+ions content,which is mainly attributed to the changes in photon absorption process of Tm^3+:1G4(b).

Structure and Properties of the Lithium Aluminosilicate Glasses with Yttria Addition

The structure and properties of lithium aluminosilicate glasses containing Y203 were investigated by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, differential thermal analysis （DTA） and Raman spectroscopy. Effects of yttria on the viscosity of LAS glasses were investigated, and found that the introduction of yttria effectively decreased the viscosity of LAS glasses. In Raman spectra of initial glasses it is shown the starting glasses are in almost complete disorder, since all bands are weak and broad. In the spectra of heat-treated specimens some new narrow bands appear and increase in intensity, and the frequency changes with varied yttria addition. The DTA and XRD results show that yttria controlled the crystallization of LAS glasses by increasing the crystallization peak temperature （T）, however, the main crystalline phase of glass-ceramics was β-spodumene.

Phase evolution and properties of glass ceramic foams prepared by bottom ash,fly ash and pickling sludge

Municipal solid waste incineration products of bottom ash(BA),fly ash(FA),and pickling sludge(PS),causing severe environ-mental pollution,were transformed into glass ceramic foams with the aid of CaCO3 as a pore-foaming agent during sintering.The effect of the BA/FA mass ratio on the phase composition,pore morphology,pore size distribution,physical properties,and glass structure was investigated,with results showing that with the increase in the BA/FA ratio,the content of the glass phase,Si-O-Si,and Q3Si units decrease gradually.The glass transmission temperature of the mixture was also reduced.When combined,the glass viscosity decreases,causing bubble coalescence and uneven pore distribution.Glass ceramic foams with uniform spherical pores are fabricated.When the content of BA,FA,and PS are 35wt%,45wt%,and 20wt%,respectively,contributing to high performance glass ceramic foams with a bulk density of 1.76 g/cm3,porosity of 56.01%,and compressive strength exceeding 16.23 MPa.This versatile and low-cost approach provides new insight into synergistically recycling solid wastes.

Silver Film Growth on Glass Ceramic by Radio Frequency Magnetron Sputtering

Thin silver films are deposited by radio frequency magnetron sputtering on glass ceramic at room temperature.Variations of sputtering power,bios voltage and power density are carried out for each deposition,then parts of as-deposited samples are subjected to annealing at 600 ℃ within a vacuum chamber.Structural properties are studied by X-ray diffraction(XRD),scanning electron microscope(SEM)and laser scanning confocal microscope(LSCM).It is shown that structural properties have a strong dependency on sputtering power and annealing temperature.Electrical contact resistance measured by a four point probe instrument is directly affected by the thickness of films.It is also found that the film conductivity,especially in thinner films,is improved by the increasing grain size.Finally,the film adhesion is observed by scratch tests.And the adhesive ability deposited by radio frequency magnetron sputtering shows a better performance than that produced by traditional methods.

Structural Changes by Thermal Treatment up to Glass Obtention of P₂O₅-Na₂O-CaO-SiO₂Compounds with Bioglass Composition Types

P2O5-Na2O-CaO-SiO2 compounds are the base of certain glass types. Glasses are solids obtained by fast cooling of melted mix of certain compounds. Different compositions give origin to many products with a variety of applications such as: bottles, coatings, windows, tools for chemical industry, laboratory equipment, optics, as bioceramics, etc. The aim of this work was to analyze structural changes of different composition in the P2O5-Na2O-CaO-SiO2 systems thermally treated up to 1250?C, that is to say, before glass formation, by X ray diffraction. Intermediate and final developed phases up to 1100?C thermal treatment in samples were generated as a function of Na2O/CaO (1 and 1.62) and P2O5/Na2O ratios (0, 0.2 and 0.245). High-and low-combeites, calcium and sodium-calcium silicate were found at the highest studied temperature.

Structural Characterization of Novel Cerium Phosphate Glass Ionomer Cements (GICs) Doped with GaCl (Phthalocyanine)

Cerium Pyrophosphate glass is prepared and investigated by different structural techniques. Resin modified glass ionomer cements (RGICs) of pyro cerium phosphate (40CeO2-60P2Os) composition doped with different concentrations from GaCl Phthalocyanine (C32H16ClGaN8) have been also prepared and studied for the first time. Different techniques have been applied to shed?light on the structural changes induced upon addition of GaCl-Phthalocyanine. The corresponding changes in material structure are widely approved by results of 31P magic angle spinning nuclear magnetic resonance (MAS-NMR), X-Ray diffraction and FTIR spectroscopy. The network structure of both base glass and GIC free from C32H16ClGaN8 is confirmed to be amorphous. Doping even with little concentration from GaCl-Phthalocyanine leads to changing the network structure from amorphous to a highly crystalline one. Formulation of GaCl-Phthalocyanine with water soluble acid leads to monocrystalline structure due to monoclinic lattice structure of Phthalocyanine. Carbonated hydroxyl cerium and gallium phosphate structural phases are evidenced to be formed upon GaCl-Phthalocyanine addition. Presence of such bioactive phases can support that the prepared GICs of considerable C32H16ClGaN8 concentration (1 and 1.5 mol%) can be applied as biocompatible materials used in biodental applications. The morphologies of some selected samples were characterized by SEM. The micrographs have revealed that formulating of cerium phosphate powder of the amorphous glass with polymeric acid successfully led to the formation of CePO4-H2O nanofibrous bundles. But formulation with GIC containing GaCl-Phthalocyanine can simply form co-aligned and elongated nanofibers (15 - 40 nm thick and up to ca. 1.2 m long). The formed nanofibers are mainly consisted of hydrated and carbonated CePO4 and GaPO4 nanocrystals. The hardness of the cemented material increases with increasing GaCl-Phthalocyanine concentrations.

铋酸盐封接玻璃的研究及其连接应用现状

无铅低温封接玻璃由于具有绿色安全、成本低、封接温度低等优势,被广泛应用于航空航天、电真空、集成电路等领域。在磷酸盐、钒酸盐、硼酸盐和铋酸盐等多种封接玻璃体系中,因铋与铅具有相似的性质特点,使得铋酸盐玻璃成为最有可能替代铅酸盐玻璃的绿色玻璃钎料。综述了铋酸盐玻璃的成分和性能调控、网络结构的研究现状,介绍了目前使用铋酸盐封接玻璃进行金属、陶瓷同质/异质材料连接的研究进展,最后对未来的发展趋势进行了展望。

Li_(2)O/Na_(2)O对YAS微晶玻璃结构、析晶与力学性能的影响

透明微晶玻璃由于优异的力学性能被广泛应用于电子领域。本文采用熔融法制备了不同质量分数Li_(2)O和Na_(2)O的Y_(2)O_(3)-Al_(2)O_(3)-SiO_(2)(YAS)微晶玻璃,通过Raman、DSC、XRD、FESEM、UV-VIS-NIR等测试方法研究了其结构特征、析晶与力学性能。结果表明:当碱金属氧化物R_(2)O(R=Li,Na)总量保持不变,随着Li_(2)O取代Na_(2)O含量的增加,YAS微晶玻璃的转变温度、软化温度和结晶峰温度逐渐降低,Q^(4)基团对应的含量逐渐减少,说明Li_(2)O作为网络外体使YAS微晶玻璃结构逐步解聚,玻璃的析晶能力逐渐增强。在同一热处理制度下,随着Li_(2)O取代量的增加,YAS微晶玻璃维氏硬度显著提升,而透过率明显下降。在680℃/10 h+750℃/1 h热处理制度下,可以制备出晶体大小一致且分布均匀的以钇稳定氧化锆为主晶相的透明YAS微晶玻璃,此时2%(质量分数,下同)Na_(2)O+4%Li_(2)O YAS微晶玻璃具有良好的综合性能,如维氏硬度为646 HV,断裂韧性为1.07 MPa·m^(1/2),透过率为85.7%,在诸多领域具有巨大的应用潜力。

两种方法制备微晶玻璃的介电与储能特性的影响

作为一种有潜质的电介质材料,微晶玻璃材料得以广泛研究。目前开展的相关研究都聚焦于材料体系与结构的优化,而有关制备工艺对性能的影响鲜有报导。本研究在之前工作基础上,系统性的研究了熔融法与烧结法两种不同的制备工艺对磷酸盐体系微晶玻璃的结构、介电与储能特性的影响。结果表明,采用熔融法所制备的微晶玻璃具有更有序的显微结构,同时获得了更高的介电常数和更低的介电损耗,兼具最佳的能量释放特性与能量效率的特性。