Effect of Na_(2)O Content on the Structure and Properties of LAS Glass-ceramics Prepared by Spodumene

The Li_(2)O-Al_(2)O_(3)-SiO_(2) (LAS) glass-ceramics with low lithium content were prepared from spodumene mineral by melting method.XRD,DSC,and FTIR were used to study the crystallization process and structure of the samples.The results showed that the addition of Na_(2)O promoted the precipitation of β-quartz solid solution and its transformation to β-spodumene solid solution.Mechanical performance tests and FESEM indicated that the larger grain size and inhomogeneous grain dispersion caused by the increase of Na_(2)O content led to lower mechanical properties.In addition,low expansion glass-ceramics were prepared by an appropriate heat treatment according to DSC result,and when Na_(2)O content was in the range of 1.22 wt% to 2.41 wt%,the average coefficient of thermal expansion (CTE) (30-300 ℃) increased from-5.810 ×10^(-7 )to 5.322×10^(-7)℃^(-1).

Properties of Ultra-low Thermal Expansion LAS Transparent Glass-ceramics Prepared by Spodumene

The glass-ceramics were prepared with the spodumene mineral as the main raw material,and the effects of ZrO_(2)replacing TiO_(2)on the samples were systematically investigated.The results show that the substitution of ZrO_(2)for TiO_(2)is not conductive to precipitate𝛽β-quartz solid solution phase,but can improve the transparency and flexural strength of glass-ceramics.And the glass-ceramic with the highest visible light transmittance(87%)and flexural strength(231.80 MPa)exhibits an ultra-low thermal expansion of-0.028×10^(-7)K^(-1)in the region of 30-700℃.

Preparation, Crystallization and Mechanical Properties of Potassium Aluminosilicate Glass-ceramics

In this study,transparent K_(2)O-Al_(2)O_(3)-SiO_(2)(KAS)glass-ceramics with leucite as the main crystalline phase were prepared by melting-quench method and two-step heat treatment.The effects of SiO_(2)/Al_(2)O_(3) ratio and heat treatment on crystallization and mechanical properties were studied.The crystallization kinetics and X-Ray Diffraction(XRD)results showed that SiO_(2)/Al_(2)O_(3) ratio and heat treatment system had a direct impact on the crystallization behavior of potassium aluminosilicate glass-ceramics.When heat-treated at 680℃/2 h and 780℃/1 h,cracks generated on the surface of the sample with the addition of SiO_(2)/Al_(2)O_(3)=4.8(in mol)due to the huge difference in the coefficient of thermal expansion between glass matrix and surface.When the addition of SiO_(2)/Al_(2)O_(3)(in mol)was 4,the sample with leucite as the main crystalline phase showed an excellent fracture toughness(1.46 MPa·m^(0.5))after the heat treatment of 680℃/2 h and 780℃/5 h.And there was a phase transformation from kaliophilite to leucite.The crystalline phases of the sample heat-treated at 680℃/8 h and 780℃/1 h were leucite and kaliophilite,which resulted in the visible light transmittance of 63%and the fracture toughness of 0.91 MPa·m^(0.5).Furthermore,after the heat treatment of 680℃/2 h and 780℃/5 h,the main crystalline phase of the sample with SiO_(2)/Al_(2)O_(3)=3.2(in mol)was still kaliophilite.Because leucite only grows on the surface of the sample and is hard to grow inward,it is hard to achieve the bulk crystallization of leucite in the sample with SiO_(2)/Al_(2)O_(3)=3.2(in mol).

Glass-Ceramics with High Strength and High Transmittance Obtained by Multi-Factor Controlling

The presence of Li_(2)Si_(2)O_(5) and LiAlSi_(4)O_(10) could effectively improve the elastic modulus and transmittance of lithium disilicate(LD)glass-ceramics.Through synergistically modulation of the crystal content and grain size,we obtained high strength and high transmittance of LD glass-ceramics.The optimal sample had a high transmittance of 90.3%,the hardness was 7.72 GPa,the fracture toughness was 1.07 MPa·m^(1/2),and the elastic modulus was 103.1 GPa.

Isotropic sintering shrinkage of 3D glass-ceramic nanolattices:backbone preforming and mechanical enhancement

There is a perpetual pursuit for free-form glasses and ceramics featuring outstanding mechanical properties as well as chemical and thermal resistance.It is a promising idea to shape inorganic materials in three-dimensional(3D)forms to reduce their weight while maintaining high mechanical properties.A popular strategy for the preparation of 3D inorganic materials is to mold the organic–inorganic hybrid photoresists into 3D micro-and nano-structures and remove the organic components by subsequent sintering.However,due to the discrete arrangement of inorganic components in the organic-inorganic hybrid photoresists,it remains a huge challenge to attain isotropic shrinkage during sintering.Herein,we demonstrate the isotropic sintering shrinkage by forming the consecutive–Si–O–Si–O–Zr–O–inorganic backbone in photoresists and fabricating 3D glass–ceramic nanolattices with enhanced mechanical properties.The femtosecond(fs)laser is used in two-photon polymerization(TPP)to fabricate 3D green body structures.After subsequent sintering at 1000℃,high-quality 3D glass–ceramic microstructures can be obtained with perfectly intact and smooth morphology.In-suit compression experiments and finite-element simulations reveal that octahedral-truss(oct-truss)lattices possess remarkable adeptness in bearing stress concentration and maintain the structural integrity to resist rod bending,indicating that this structure is a candidate for preparing lightweight and high stiffness glass–ceramic nanolattices.3D printing of such glasses and ceramics has significant implications in a number of industrial applications,including metamaterials,microelectromechanical systems,photonic crystals,and damage-tolerant lightweight materials.

Crystallization kinetics and temperature dependence of energy storage properties of niobate glass-ceramics

Glass-ceramic materials of strontium barium niobate system were prepared through a melt-quenching method. The effects of crystallization temperature on the mierostructure, dielectric property, breakdown strength and energy storage density of barium strontium niobate glass-ceramics were studied. The crystallization mechanism of the glass-ceramics was discussed and should be one-dimensional interfacial growth. The results indicate that the breakdown strength remarkably increases with the increase of crystallization temperature. The glass-ceramic heat treated at 900 ℃ was found to possess optimal properties with breakdown strength of 1300 kV/cm and energy storage density of 2.8 J/cm3, which is promising dielectric materials for high energy storage density dielectrics.

适用于LAS系统的全液体隔离液体系

固井施工过程中,在注入水泥浆前,需要先泵入一定量的隔离液,在海洋固井现场施工作业过程中,隔离液配制一般需要繁重的人工劳作,劳动强度大,作业效率低,加量不准确。为解决上述问题,用液体添加剂代替固体添加剂,通过LAS材料添加系统将材料混配作业,从传统的重体力劳动转化为智能化操作,降低作业强度,提高固井作业效率与降低人员成本。通过反相乳液聚合制备了一种液体隔离剂C-S70L,以它为主剂,构建了一套适用于液体加料系统(LAS)的隔离液体系。该体系推荐使用温度为20~120℃,适用密度为1.30~1.70 g/cm^(3);具有良好的悬浮稳定性(热滚后无沉降)、流变可调、失水可控以及相容性好的特点。

Influence of aluminium nitride as a foaming agent on the preparation of foam glass-ceramics from high-titanium blast furnace slag

To effectively reuse high-titanium blast furnace slag （TS）, foam glass-ceramics were successfully prepared by powder sintering at 1000℃. TS and waste glass were used as the main raw materials, aluminium nitride （AIN） as the foaming agent, and borax as the fluxing agent. The influence of the amount of A1N added （lwt%-5wt%） on the crystalline phases, microstructure, and properties of the produced foam glass-ceramics was studied. The results showed that the main crystal phases were perovskite, diopside, and augite. With increasing A1N content, a transformation from diopside to augite occurred and the crystallinity of the pyroxene phases slightly decreased. Initially, the aver- age pore size and porosity of the foam glass-ceramics increased and subsequently decreased; similarly, their bulk density and compressive strength decreased and subsequently increased. The optimal properties were obtained when the foam glass-ceramics were prepared by adding 4wt% AIN.

Luminescence of Er^(3+) in Oxyfluoride Transparent Glass-Ceramics

Erbium doped silicate, germanate, and tellurium-germanate oxyfluoride glasses were prepared in a bulk form. Through appropriate heat treatment of the as-prepared glasses, transparent glass-ceramics （TGCs） were obtained with the formation of β-PbF2：Er^3＋ nanocrystals in the glass matrix were confirmed by X-ray diffraction.Well-defined diffraction peaks were observed in the samples after heat-treatment. The average crystal diameter of these precipitated crystals from full-width at half-maximum （FWHM） of the diffraction peak was estimated to be between 8 and 13 nm. Optical absorption, photoluminescence, and upconversion luminescence were measured on as-prepared glass and glass-ceramics. Luminescence spectra in the TGC samples revealed well-resolved, sharp stark-splitting peaks, which indicates that a majority of Er^3＋ ions has been incorporated into the crystalline phase of the nanocrystals. The intensity of the visible and near infrared luminescence mostly increases in TSG compared to that in the as-prepared glass. In 1.53 μm absorption and emission bands, the maximum absorption peak is blue-shifted from 1531 to 1507 nm, whereas the maximum emission peak is redshifted from 1535 to 1543 nm in TGC, as compared with that in glass. The bandwidth at half-maximum （BWHM） of the emission band is significantly broader in TGC than in glass, which is beneficial to the erbium-doped fiber amplifier （EDFA）. Upconversion luminescence was measured using 800 nm near-infrared light excitation. Drastically increased upconversion 1 was observed from the TGC as compared to that from their corresponding as-prepared glasses. In addition to a strong green emission centered at 545 nm because of ^4S3/2→^4I15/2 transition and a weaker red emission centered at 662 nm because of ^4F9/2→^4I15/2 transition, generally seen from the Er^3＋ doped glasses, two violet emissions centered at 410 nm because of ^2H9/2→^4I15/2 transition and centered at 379 nm because of ^4G11/2→^4I15/2 transition were also observed from the was attributed to the decreased effective phonon energy and the increased energy transfer between the excited ions when Er^3＋ ions were incorporated into the precipitated β-PbF2 nanocrystals. The results indicated two attractive spectroscopic properties of the Er^3＋ doped TGC samples, compared to glass samples, namely a reduced multiphonon decay rate and a reduced inhomogeneous broadening. In addition, these oxyfluoride TGC materials were robust,easy and flexibile to process, and possible to be fabricated in the fiber form for device applications.

Nucleation and crystallization of tailing-based glass-ceramics by microwave heating

The effect of microwave radiation on the nucleation and crystallization of tailing-based glass-ceramics was investigated using a 2.45 GHz multimode microwave cavity. Tailing-based glass samples were prepared fi＇om Shandong gold tailings and Guyang iron tailings utilizing a conventional glass melting technique. For comparison, the tailing-based glass samples were crystallized using two different heat-treatment methods： conventional heating and hybrid microwave heating. The nucleation and crystallization temperatures were determined by performing a differential thermal analysis of the quenched tailing-based glass. The prepared glass-ceramic samples were further characterized by Fourier transform infrared spectroscopy, X-ray diffraction, Raman spectroscopy, thermal expansion coefficient measurements, and scanning electron microscopy. The results demonstrated that hybrid microwave heating could be successfully used to crystallize the tailing-based glass, reduce the processing time, and decrease the crystallization temperature. Furthermore, the results indicated that the nucleation and crystallization mechanism of the hybrid microwave heating process slightly differs fi＇om that of the conventional heating process.

基于氧化石墨烯/SiO_(2)的LAS玻璃薄膜涂层的制备及耐腐蚀性能研究

本文在研究不同质量氧化石墨烯(GO)在水和乙醇中的分散性,以及GO粉末和GO水分散液与正硅酸乙酯(TEOS)水解液的复合分散作用的基础上,以TEOS和GO为原料,采用溶胶-凝胶法制备了GO/TEOS溶液,并使用旋涂法在锂铝硅(LAS)玻璃表面镀膜,分析了GO/二氧化硅(SiO_(2))膜层的表面形貌和断面形貌、断面元素分布,研究了GO/SiO_(2)膜层对LAS玻璃耐腐蚀性能的影响。结果表明,当GO质量为0.05 g、去离子水为15 mL时,GO在水中具有良好的分散性,加入TEOS水解液后可形成均匀镀膜液。将旋涂法表面镀膜后的LAS玻璃在氮气气氛和600℃热处理2 h后获得致密GO/SiO_(2)薄膜,碳元素分析表明,GO在膜层中均匀分布。对比分析无镀膜、SiO_(2)薄膜以及GO/SiO_(2)复合薄膜对LAS玻璃在盐酸(HCl, 1 mol/L)溶液、氢氧化钠(NaOH,质量分数5%)溶液中的腐蚀性的影响,证明GO/SiO_(2)复合薄膜可以提高LAS玻璃的耐酸腐蚀性能。

Influence of CeO_2 addition on the preparation of foamed glass-ceramics from high-titanium blast furnace slag

Foamed glass-ceramics doped with cerium oxide（CeO_2）were successfully prepared from high-titanium blast furnace slag by one-step sintering.The influence of CeO_2 addition（1.5wt%–3.5wt%）on the crystalline phases,microstructure,and properties of foamed glass-ceramics was studied.Results show that CeO_2 improves the stability of the glass phase and changes the two-dimensional crystallization mechanism into three-dimensional one.XRD analysis indicates the presence of Ca（Mg,Fe）Si_2O_6 and Ca（Ti,Mg,Al）（Si,Al）_2O_（6 ）in all sintered samples.Added with CeO_2,Ti CeO_4 precipitates,and crystallinity increases,leading to increased thickness of pore walls and uniform pores.The comprehensive properties of foamed glass-ceramics are better than that of samples without CeO_2.In particular,the sample added with a suitable amount of CeO_2（2.5wt%）exhibits bulk density that is similar to and compressive strength（14.9 MPa）that is more than twice of foamed glass-ceramics without CeO_2.

Crystallization and dielectric properties of lead-free glass-ceramic composites with Gd_2O_3 addition

Lead-free glass-ceramic composites in barium sodium niobate silica system with Gd2O3 addition were synthesized through melt-casting fol-lowed by controlled crystallization technique. Crystallization and dielectric properties of the Gd2O3 adding glass-ceramic composites were investigated. With the increase in the concentration of Gd2O3, the glass transition temperature and the crystallization temperature of the pre-cursor glass shift towards the higher temperature. The crystallization behavior that occurred during the heat treatment procedure leads to the enhancement of dielectric constant. All the three compositions of glass-ceramic composites exhibit ferroelectricity when tested at room tem-perature. Both the values of the remanent polarization and coercive field are enhanced regularly with the gradual increase in the concentration of Gd2O3 additive under the same testing field.

Preparation,crystallization,and wetting of ZnO-Al_2O_3-B_2O_3-SiO_2 glass-ceramics for sealing to Kovar

A novel type of ZnO-Al2O3-B2O3-SiO2 glass-ceramics sealing to Kovar in electronic packaging was developed, whose thermal expansion coefficient and electrical resistance are 5.2× 10^-6/℃ and over 1×10^13 Ω·cm, respectively. The major crystalline phases in the glass-ceramic seals were ZnAl2O4, ZnB2O4, and NaSiAl2O4. The dielectric resistance of the glass-ceramic could be remarkably enhanced through the control of alkali metal ions into crystal lattices. It was found that crystallization happened first on the surface of the sample, leaving the amorphous phase in the inner, which made the glass suitable for sealing. The glass-ceramic showed better wetting on the Kovar surface, and sealing atmosphere and temperature had great effect on the wetting angle. Strong interracial bonding was obtained, which was mainly attributed to the interracial reaction between SiO2 and FeO or Fe3O4.

Effect of sintering temperature on the microstructure and properties of foamed glass-ceramics prepared from high-titanium blast furnace slag and waste glass

Foamed glass-ceramics were prepared via a single-step sintering method using high-titanium blast furnace slag and waste glass as the main raw materials The influence of sintering temperature(900–1060℃) on the microstructure and properties of foamed glass-ceramics was studied. The results show that the crystal shape changed from grainy to rod-shaped and finally turned to multiple shapes as the sintering temperature was increased from 900 to 1060℃. With increasing sintering temperature, the average pore size of the foamed glass-ceramics increased and subsequently decreased. By contrast, the compressive strength and the bulk density decreased and subsequently increased. An excessively high temperature, however, induced the coalescence of pores and decreased the compressive strength. The optimal properties, including the highest compressive strength(16.64 MPa) among the investigated samples and a relatively low bulk density(0.83 g/cm^3), were attained in the case of the foamed glass-ceramics sintered at 1000℃.

Effect of Water Washing Pre-treatment on the Properties of Glass-ceramics from Incinerator Fly Ash Using Electronic Arc Furnace

Production of glass-ceramics by sintering the molten slag obtained from electric arc furnace treatment of fly ash was investigated. The effect of washing pretreatment prior to melting the fly ash on the microstructure and properties of the glass-ceramics was examined. The results show that washing pretreatment of fly ash can decrease alkali metal chloride and increase network former in fly ash, which results in the increase of peak crystallization temperature of parent glass and strengthening of properties of bending strength and chemical stability of the glass-ceramics. The optimal heat treatment temperature for parent glass of washed fly ash is 1 173 K, at which the crystalline phase of glass-ceramics is composed of gelignite （Ca2A12SiO7） and akermanite （Ca2MgSi207）. Glass-ceramics produced at optimal heat treatment temperature are excellent in term of the physical and chemical properties and leaching characteristics, indicating attractive potential as substitute of nature materials.

Glass-ceramics made from arc-melting slag of waste incineration fly ash

Grate fly ash and fluidized bed fly ash mixed with glass cullet additive respectively were melted in the electronic arc-furnace. The product, arc-melting slag, was further treated by crushing, pressing and heat treatment in order to make the glass-ceramics. The crystallization behaviors of the produced glass-ceramics were examined by differential thermal analysis （DTA）, X-ray diffractometry （XRD） and scanning electron microscopy （SEM）. Results show that main crystalline phase of the glass-ceramics fi＇om grate fly ash is wollastonite （CaSiO3） with small amount of diopside （Ca（Mg,Al）（Si,Al）206）, and that from fluidized bed fly ash is diopside （Ca（Mg,Al）（Si,Al）206）. It is found that the glass-ceramics sintered at 850 ℃and 1 000℃ from grate fly ash and fluidized bed fly ash respectively have the optimal physical, mechanical and chemical characteristics. Glass-ceramics samples, produced from incinerator fly ash with desirable properties and the low leaching concentration of heavy metals, can be the substitute of nature materials such as marble, granite and porcelain tiles.

Effect of Nucleating Agents and Heat Treatments on the Crystallization of Magnesium Aluminosilicate Transparent Glass-ceramics

The crystallization behavior and transparent property of MgO-A1203-SiO2 （MAS） glasses with TiO2 and TiO2＋ZrO2 as nucleating agents were discussed by differential thermal analysis, X-ray diffraction, field emission-environment scanning electron microscope, energy dispersive spectrum and UV-VIS-NIR scanning spectrophotometer. It was found that the glass crystallized at 950 ℃ with ZrO2 less than 3% could obtain transparent glass ceramic, which presented purple to colorless. With the nucleating agent additives （5% TIO2＋3% ZrO2）, the colorless transparent glass-ceramics with spinel as the main crystal phase could be prepared, and the transmittance reached about 80%. As the crystallized temperature increase to 1 000 ℃, besides spinel（MgA1204）, sapphirine （Mg3.5A19Si1.5O20） and ZrTiO4 precipitated from matrix glass, and the transmitance of glass-ceramic decreased.

Crystallization Characteristic of Glass-ceramic Made from Electrolytic Manganese Residue

Electrolytic manganese residue （EMR） is a waste from electrolytic manganese industry that contains high concentration of toxic substances. Since the EMR disposal in landfill sites has a serious environmental impact, new ways of EMR utilization are being sought. Considering the melting of EMR to a glass at high temperature was a relatively less energy-intensive process, EMR was first made into a base glass and then the ground base glass was heat-treated in a certain procedure to make a glass-ceramic and the crystallization process was studied. It was determined by X-ray diffraction （XRD） that the primary crystalline phases of the EMR glass-ceramic were diopside and anorthite, which formed the surface crystallization mechanism with a crystallization activation energy of 429 kJ/mol. Scanning electron microscopy （SEM） observation showed that a layer of small spherical particles with an average size of about 0.5 ~tm were covered on the glass matrix surface, and among them there were some big particles. The low melting temperature and crystallization activation energy make it promising to reuse EMR for glass-ceramic production.

Structural characteristics and dielectric properties of glass-ceramic nanocomposites of(Pb,Sr)Nb_2O_6-NaNbO_3-SiO_2

The structure and dielectric properties of （Pb,Sr）Nb2O6-NaNbO3-SiO2 glass-ceramics with different Pb and Sr contents were investigated. The XRD pattern of glass-ceramics without Sr substitution is different from that with Sr substitution, which indicates the existence of orthorhombic phase in the latter ones. TEM bright field observation shows nanosized microstructures, while for samples with Sr, typical eutectic microstrncture with separated crystallized bands is found in the glass matrix. Dielectric properties measurement of the samples indicates an obvious improvement of dielectric constant, dielectric loss, DC field and temperature dependence of dielectric constant when the molar ratio of Sr to Pb is 4：6.