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1.
《Ceramics International》2019,45(16):19689-19694
Li–Al–B–Si–O (LABS) glass-ceramics with a sintering temperature of 600 °C were studied for ultra-low temperature co-fired ceramics (ULTCC) applications. The crystal phase of LABS glass-ceramics is dendritic β-spodumene. The permittivity and dielectric loss of LABS glass-ceramics are εr = 5.8 and tgδ = 1.3 × 10−3 at 10 MHz, respectively. The coefficient of thermal expansion (CTE) of LABS glass-ceramics is 3.23 ppm/°C, which is close to that of silicon. The dielectric and thermal properties of LABS glass-ceramics are closely correlated to the degree of its crystallization. The permittivity decreases continually while the dielectric loss decreases first and slightly increases with the increasing of crystallization of β-spodumene. The CTE of LABS glass-ceramics decreases as β-spodumene crystallized from LABS glass. The crystallization kinetic and mechanism of LABS glass-ceramics indicate that the β-spodumene crystallizes in a two-dimensional interfacial growth mechanism due to the migration of Li-ions. The diffusion coefficients derived from energy-dispersive X-ray spectroscopy (EDS) results indicated that both Al and Ag electrodes have good compatibilities with ULTCC tapes, which could reduce the cost of multilayer electro-ceramic devices dramatically by using the ULTCC and base metallization.  相似文献   

2.
The dielectric and structural properties of the as-quenched melts of three CaO–B2O3–SiO2 compositions (denoted CBS-1, CBS-2, and CBS-3) were investigated to determine their suitability for use in millimeter-wave applications. The CBS-1 glass-ceramic exhibited the lowest coefficient of thermal expansion (CTE = 3.2 ppm/°C), lowest dielectric constant (εr = 4.04) at 60 GHz, and highest dielectric loss (tan δ = 0.0029) at 60 GHz, which were attributed to the presence of quartz (SiO2) as the major phase. In contrast, as the major phase constituent of the CBS-2 and CBS-3 glass-ceramics was β-CaSiO3, they presented relatively high CTEs (6.6 and 5.9 ppm/°C, respectively), relatively high dielectric constants at 60 GHz (6.29 and 7.61, respectively), and relatively low dielectric losses at 60 GHz (0.0020 and 0.0012, respectively). The CBS-1 glass-ceramic exhibited the highest dielectric loss because of the presence of SiO2 as the major phase constituent as well as lattice scattering induced by the high glassy phase content. The thermal conductivities (κ) of the CBS-1, CBS-2, and CBS-3 glass-ceramics were determined to be 2.43, 1.06, and 0.82 W/mK, respectively. Structural analysis using Raman and Fourier transform infrared spectroscopy revealed an absence of nonbridging oxygen in the CBS-1 glass-ceramic, while the high CaO content (>40 mol%) of the CBS-2 and CBS-3 glass-ceramics triggered the formation of nonbridging oxygen in the tetrahedral silicate units. The increase in CaO content of the glass-ceramics increased the number of nonbridging oxygen atoms, thereby resulting in the relaxation of the structure. Consequently, the CBS-2 and CBS-3 glass-ceramics exhibited low thermal conductivity. All the prepared glass-ceramics presented high electrical resistivities of greater than 5 × 1011 Ω cm. The CBS-1 glass-ceramic displayed the highest breakdown strength of 15.20 kV/mm. Overall, the excellent microwave dielectric properties and thermal properties of the CBS glass-ceramics will facilitate the utilization of these materials in millimeter-wave applications.  相似文献   

3.
《Ceramics International》2022,48(15):21355-21361
In this study, a transparent and environmentally friendly Li2O–Al2O3–SiO2 (LAS) glass-ceramic was prepared by melt-quenching and two-step heat treatment. The influence of the substitution amount of ZrO2 by SnO2 on the crystallization, microstructure, transparency, and mechanical properties of LAS glass and glass-ceramics was investigated by means of differential scanning calorimetry (DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Ultraviolet–visible Spectrophotometer, three-point bending strength test, and microhardness test. The results indicate that the main crystalline phase of LAS glass ceramics was a β-quartz solid solution when heat treated at 780 °C for 2 h and 870 °C for 1.5 h. When the substitution amount of ZrO2–SnO2 increased from 0.4 mol% to 2.5 mol%, the grain size and thermal expansion coefficient of LAS glass-ceramics first decreased and then increased, and the crystallinity first increased and then decreased. When the substitution amount of ZrO2–SnO2 was 0.8 mol%, the transparency of the LAS glass-ceramics was maximum, the bending strength was 96 MPa, and the Vickers hardness was 10.9 GPa.  相似文献   

4.
《Ceramics International》2022,48(7):9030-9037
In this study, sol–gel derived CaO–B2O3–SiO2 glass-ceramics with a set B2O3 content of 22.2 mol% and CaO/SiO2 ratios ranging between 0.15 and 0.27 were used for low-temperature cofired ceramic applications in the 5G millimeter-wave bands. X-ray diffraction analysis, scanning electron microscopy, Fourier-transform infrared spectroscopy, and Raman spectroscopy data indicated that, unlike the typical CaO–B2O3–SiO2 glass-ceramics prepared via melting resulted in the presence of calcium silicates, the CaO–B2O3–SiO2 glass-ceramics in this study comprised only an amorphous phase containing different amounts of CaB2O4 crystallites depending on the CaO/SiO2 ratio. Among the formulations evaluated, the 14.5CaO?22.2B2O3?63.3SiO2 glass-ceramic sintered at 950 °C exhibited a dielectric constant of 4.33 and a dielectric loss of 0.0012 at 60 GHz, which conferred its low signal propagation delay and low signal attenuation in applications. In addition, the electrical resistivity, breakdown strength, thermal conductivity, and coefficient of thermal expansion of the 14.5CaO?22.2B2O3?63.3SiO2 glass-ceramic were 1.72 × 1012 Ω cm, 15.49 kV/mm, 1.70 W/mK, and 4.1 ppm/°C, respectively. The 14.5CaO?22.2B2O3?63.3SiO2 glass-ceramic exhibited excellent insulating properties, facilitating its use as substrate material; moreover, its thermal properties matched those of Si and GaAs.  相似文献   

5.
《Ceramics International》2022,48(14):20053-20061
The composition governs the crystallization ability, the type and content of crystal phases of glass-ceramics. Glass-ceramic joining materials have generated more research interest in recent years. Here, we prepared a novel Li2O–MgO–Al2O3–SiO2 glass-ceramic for the application of joining Si3N4 ceramics. We investigated the influence of the MgO/Al2O3 composition ratio on microstructure and crystallization behaviour. The crystallization kinetics demonstrated that the glasses had excellent crystallization ability and high crystallinity. β-LiAlSi2O6 and Mg2SiO4 were precipitated from the glass-ceramics, and the increase of MgO concentration was conducive to the precipitation of Mg2SiO4. Among the glass-ceramic samples, the thermal expansion coefficient of LMAS2 glass-ceramic was 3.1 × 10?6/°C, which was very close to that of Si3N4 ceramics. The wetting test showed that the final contact angle of the glass droplet on the Si3N4 ceramic surface was 32° and the interface was well bonded.  相似文献   

6.
通过传统熔融法制备了具有低膨胀系数的Li2O-Al2O3-SiO2(LAS)微晶玻璃.利用扫描电镜、X射线衍射、差热分折及热膨胀系数测定等分 析手段,研究了玻璃组成中Li2O,Al2O3,SiO2的含量对微晶玻璃热膨胀系数的影响.结果表明:在标准样品的基础上,Li2O的含量对热膨胀系数影 响很大:Li2O的含量提高,由于形成β-锂辉石,微晶玻璃的结晶程度增加与晶粒尺寸增大,导致热膨胀系数增大.与此相比较,Al2O3和SiO2成分 的变化对膨胀系数的影响较小.当玻璃组成(质量分数,下同)为4%~6%Li2O,16%~18%Al203,66%~68%Si02时,Li2O-Al2Oy-SiO2玻璃的膨胀 系数为-1.5~1.5×10-7/℃(0~700℃)  相似文献   

7.
The price of lithium-containing minerals and other chemical materials continues to increase, resulting in an increase in the production cost of Li2O-Al2O3-SiO2 (LAS) system glass-ceramics. In the LAS glass-ceramics component, the reduction in the amount of Li2O used can reduce the cost of the product. It is worthwhile to study whether it is possible to prepare glass-ceramics with low expansion properties under low Li2O content. The effect of Li2O content on the glass-ceramics of LAS system was studied. In this paper, spodumene was used as the main raw material, and TiO2 and ZrO2 were added as crystal nucleating agents to prepare transparent glass-ceramics with low expansion coefficient. The effects of the change of Li2O content on the crystal phase and microstructure of glass-ceramics were investigated by XRD, DSC, FTIR and SEM. The results show that the main crystalline phase of the low expansion transparent glass-ceramics is β-quartz solid solution. When Li2O content is in the range of 2.99 wt% to 4.13 wt%, low expansion glass ceramics can be prepared by an appropriate method. With the increase of Li2O content, the average coefficient of thermal expansion (CTE) in the temperature range of 30 °C–300 °C shows a decreasing trend. When Li2O content is in the range of 3.51 wt% to 4.13 wt%, the thermal expansion coefficient of the glass ceramics is extremely small, and even a negative expansion coefficient occurs.  相似文献   

8.
Bioactivity of ferrimagnetic glass-ceramics is useful as thermo seeds for hyperthermia treatment of cancer. Ferrimagnetic glass-ceramics were prepared from the BaFe12O19(BF)–SiO2–CaO–Na2O–P2O5 system using the incorporation method. The mixture was then further sintered at 800 °C to form the glass-ceramic samples. The structure and microstructure of the samples were characterized by X-ray diffraction, energy dispersive X-ray analysis (EDXA) and scanning electron microscopy. Magnetic hysteresis loops of the glass-ceramic samples were obtained with maximum field of 10 kOe, in order to evaluate the potential of these samples for hyperthermia treatment of cancer. In vitro bioactivity was investigated in simulated body fluid (SBF) for 14 days. The results showed that Na2Ca2Si3O9 and BaFe12O19 were the main phases in the glass-ceramic samples. Apatite was formed on the surface layers of the glass-ceramics, confirming their biocompatibility. It was found that the bioactivity increased with an increase in BF contents.  相似文献   

9.
Various glass-ceramics were prepared based on the CaO-Al2O3-SiO2 system with the addition of Li2O in an attempt to develop a suitable sealant for SiC ceramic. The effects of Li2O content on crystallization behavior and thermal expansion properties were systematically investigated. The results revealed that the addition of Li2O significantly reduced the crystallization activation energy of glass. Besides, as the Li2O content increased, the precipitation of spodumene and wollastonite was promoted while the precipitation of anorthite was suppressed. By controlling the Li2O content and crystallization treatment, the coefficient of thermal expansion (CTE) of glass-ceramic could be adjusted in a certain range, from 8.5 × 10?6/°C to 2.8 × 10?6/°C. When the content of Li2O was 3 wt.%, the CTE of the formed glass-ceramic was well-matched with that of SiC ceramic. Furthermore, it was confirmed that this glass-ceramic possessed an excellent wettability and weldability to SiC ceramic.  相似文献   

10.
《Ceramics International》2021,47(18):25467-25474
The crystallization behaviour and thermo-magnetic characteristics of glass-ceramic based on the 15Li2O–20ZnO–10CaO–55SiO2 system doped with varied Fe2O3 additions (0.0125, 0.025, and 0.05 mol) are described in this work. In some cases, Al2O3 was also added to the iron-containing sample. Glasses were successfully prepared by melt-quenching technique and converted into glass-ceramics by controlled heat-treatment, using DTA, SEM, XRD, and VSM techniques. The density, thermal expansion coefficients (TCE), and magnetic characteristics of the glass-ceramic were examined. XRD results confirmed characteristic peaks for various phases like quartz, Li2ZnSiO4, wollastonite, Li2Si2O5, ZnFe2O4, and β-spodumene. By doping Fe2O3 and Al2O3 with lowering annealing temperature, the particle size was reduce, resulting in glass-ceramics with a more uniform and dense microstructure. The density of glass-ceramics rises from 2.74 g/cm3 to 3.45 g/cm3, whereas the TCE values in average 14–78 × 10−7/°C with temperature range of 25–500 °C. The doped glass-ceramics have superior magnetic properties with saturation magnetization (0.143–0.548 emu/g), the coercivity force (65.116–86.359 G), and remanence magnetization (0.074–0.436 emu/g). Under an alternating magnetic field, the presence of the Zn-ferrite phase in the glass-ceramics improves their magnetic properties and increases their heat-generating capability. Certain features of the doped glass-ceramics control the extensive variety of possibilities for their usage in various magnetic applications particularly for cancer hyperthermia treatment.  相似文献   

11.
《Ceramics International》2022,48(16):23145-23150
In this work, glass-ceramic materials are obtained from a precursor glass in which coffee husk ash is used as a K2O source. We demonstrate an analysis based on the structural, thermal and microstructural properties of the constituent materials. The final sintered bodies consist of diopside and nepheline crystals embedded into a glassy phase. These materials offer unique advantages as sealants for solid oxide cells (SOCs), with thermal expansion coefficients similar to those of other SOC components (9–10 × 10?6 °C?1) and Vicker's microhardness values of ~7 GPa. These results indicate the feasibility of obtaining glass-ceramics by an environment friendly route, using coffee husk ash instead of commercial potassium carbonate.  相似文献   

12.
Glass-ceramic materials were produced from fly ash samples obtained from the Seyitömer thermal power plant in Turkey. Glass samples were crystallized by suitable nucleation and crystal growth heat treatments on the basis of DTA results. The microstructural analysis of glass-ceramic samples were carried out using SEM and XRD techniques. SEM investigations clearly demonstrated the presence of a tiny crystallized phase dispersed in the microstructure. XRD results revealed that the main crystalline phase was diopside [Ca(Mg,Al)(Si,Al)2O6]. It was observed that the mechanical properties and the thermal expansion coefficient of the glass-ceramic samples depend only on the amount of the crystalline phase. Furthermore, chemical durability of the produced glass-ceramic samples were high.  相似文献   

13.
Two series (N-9 and N-18 series) of zirconia-doped Y–Si–Al–O–N oxynitride glasses and glass-ceramics were designed. Nominal compositions of the glass samples in equivalent percent (eq%) are xZr: (24–0.25x)Y: (15–0.25x)Al: (61–0.5x)Si: 91O: 9 N and xZr: (24–0.25x)Y: (15–0.25x)Al: (61–0.5x)Si: 82O: 18 N (x=0, 2, 4, 6), respectively. The obtained samples were characterized by differential thermal analysis (DTA), X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). Densities, Vickers hardness, fracture toughness, glass transition temperature, and thermal expansion coefficient data were established for each sample. Effect of Zr and N content on glass network structure, thermal and mechanical properties was investigated. It was found that the addition of zirconia is effective in preparing Y–Si–Al–O–N oxynitride glasses with lower glass transition temperature and higher hardness.  相似文献   

14.
Four different YAlSiO and YAlSiON compositions that produced either glass or glass-ceramic materials were designed. Densities, glass transition temperatures, coefficients of thermal expansion and hardness data were established for each material. The sintering behavior was determined from the hot stage microscopy (HSM) runs. For the YAlSiO glass compositions, the viscosity-temperature curves were estimated from five characteristic HSM points using Scholze's method. The YAlSiON glass-ceramics with higher Y content showed YAlO3 and SiAl6O2N6 crystals and the poorer Y composition had crystalline precipitates of Si3N4, Si4Al2O2N6 and Y2SiAlO5N. The effects of the Al/Si and Y/Si ratios, and the nitrogen content on the properties have been discussed. These glass-ceramics showed relatively high thermal expansion coefficient and hardness and, therefore, its application as protective coatings for metallic components against high temperatures and/or corrosive environments is envisaged.  相似文献   

15.
In this paper, we report an anodic bondable Li-Na-Al-B-Si-O (LNABS) glass-ceramic system with a low temperautre (150 °C) and voltage (200 V) for Si - ULTCC (Ultra-Low Temperature Co-fired Ceramics) heterougeneous integration. The ULTCC materials are predominantly composed of multicrystalline LiAlSi2O6 with a small amount of glass phase. The coefficient of thermal expansion (CTE) of LNABS is 3.27 ppm/°C (25–300 °C) leading to excellent theraml compatibility with silicon wafer over a wide temperature range from 60 °C to 300 °C. To demonstrate the utility of this system, a silicon micro-electro-mechanical (MEMS) systems pressure sensor is encapsulated between silicon and ULTCC substrates. This sensor exhibits high accuracy and good stability in the temperature range from ?40 °C to 120 °C. The bonding current, cross section and alkali ions concentration were investigated, and the anodic bonding mechanism at low temperature and voltage was revealed. The alkali ions migrate through the glass phase due to its lower activation energy, which also forms a high space-charge electric field at the bonding interface. The non-bridge oxygen (NBO) drifts towards silicon and oxidized silicon under high space-charge electric field. The calculated diffusion coefficient of NBO indicates that the elevated temperature and voltage both benefit the migration of NBO. These finding illustrate the great potential of LNABS glass-ceramic for high quality microelectronic and MEMS packaging technology with advantages of multilayer structure, low anodic bonding temperature and voltage, as well as the excellent theraml compatibility with Si wafers.  相似文献   

16.
Li2O-SiO2-ZrO2 (LZS) glass-ceramics have high mechanical strength, hardness, resistance to abrasion and chemical attack, but also a high coefficient of thermal expansion (CTE), which can be reduced adding alumina nanoparticles. The conventional glass-ceramic production is relatively complex and energy consuming, since it requires the melting of the raw materials to form a glass frit and a two-step milling process to obtain particle sizes adequate for compaction. This study describes the preparation of LZS glass-ceramics through a colloidal processing approach from mixtures of SiO2 and ZrO2 nanopowders and a Li precursor (lithium acetate obtained by reaction of the carbonate with acetic acid). Concentrated suspensions were freeze-dried to obtain homogeneous mixtures of powders that were pressed (100 MPa) and sintered conventionally and by spark plasma sintering. The effect of the alumina nanoparticles additions on suspensions rheology, sintering behavior and properties such as thermal expansion, thermal conductivity, hardness and Young’s modulus were evaluated.  相似文献   

17.

This work aims to study the thermal behavior of basic-geopolymers derived from metakaolin (clay). The geopolymers were characterized by different techniques: thermal analysis (DTA, TGA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and impedance spectroscopy. Some physicochemical properties of the products were also determined: the phases obtained after geopolymer heat treatment and their electrical properties. The results obtained after drying and heat treatment showed that the products kept their initial shapes, but revealed variable colors depending on the temperatures at which they were treated. The products obtained are amorphous between 300 up to 600 °C with peaks relating to the presence of nanocrystallites of muscovites and zeolite, thus at 900 °C it is quite amorphous but only contains nanocrystallites of muscovites. From the temperature of 950 °C, we notice that the geopolymer has been transformed into a crystalline compound predominated by the Nepheline (NaAlSiO4) with the presence of a crystalline phase by minor peaks of Muscovite, this crystalline character has been increased at 1100 °C to obtain a whole phase crystalline of a Nepheline. The treatment of this geopolymer for one hour at 1200 °C shows an amorphous phase again corresponding to corundum (α-Al2O3). This indicates that the dissolution of the grains by the liquid phase induces the conversion of the material structure from sialate [–Si–O–Al–O] to sialate siloxo [–Si–O–Al–O–Si–O–] and the formation of a new crystalline phase (α-Al2O3). This development of sialate to sialate-siloxo was confirmed by IR spectroscopy. As mentioned above, from 300 to 900 °C, Na-sialate geopolymer exhibits the same disorder structure of nepheline. The crystal structure of nepheline is characterized by layers of six-membered tetrahedral rings of exclusively oval conformation. The rings are built by Regularly alternating tetrahedral AlO4 and SiO4. Stacking the layer’s parallel to the c axis gives a three-dimensional network containing channels occupied by Na cations. This topology favors easy movement of Na+ ions throughout the structure. For this reason, ionic migration in nepheline is widely reported. The refinement of Na-Sialate geopolymer at room temperature gives bulk high ionic conductivity of about 5 × 10?5 S cm?1 and this is due to the probable joint contribution of H+ and Na+ ions. Above 200 °C, Na+ seems to remain the only charge carrier with a low activation energy of about Ea?=?0.26 eV. At higher temperatures, the characteristic frequencies become so close that it is impossible to distinguish the contributions. A total resistance comprising both grain and grain boundaries contribution is then determined.

  相似文献   

18.
High performance ultra-low temperature co-fired ceramic (ULTCC) materials were prepared from CuO- MgO- ZnO- Al2O3- B2O3- Li2O glass-ceramics. The sintering behaviors, crystalline phase evolution, microstructure and dielectric properties, as well as their compatibility with Ag and Al electrodes, were investigated. With the suitable substitution of MgO for ZnO, the dielectric properties of glass-ceramics were improved. It is mainly associated with the fine microstructure, highly crystallinity, and decrease in tetrahedral distortion in the crystal lattice. All the glasses completed the densification at 575–600 °C, and ZnB4O7 is the only crystalline phase precipitated from the glasses. Moreover, the glass-ceramic with 1 wt% MgO sintered at 575 °C for 5 h, exhibited low relative permittivity ~ 7.1 and low dielectric loss ~ 6.40 × 10?4. And the glass-ceramic with 4 wt% MgO sintered at 600 °C for 5 h, also displayed low relative permittivity ~ 7.1 and low dielectric loss ~ 5.77 × 10?4. Both two glasses have good sintering compatibility with silver and aluminum electrodes, which provided high potential for ULTCC application.  相似文献   

19.
Phosphate-based glasses of composition xNa2O−(45+(10−x))CaO−45P2O5 with different Na2O, CaO (= 1, 5, 10, 15, and 20 mol%), and invariable P2O5 (45 mol%) contents were prepared using the rapid melt quench technique. The obtained thermal data from differential thermal analysis revealed a decline in glass transition (Tg) and crystallization (Tc) temperatures of glasses against the compositional changes. The inclusion of Na2O at the cost of CaO in the glass network led to a reduction in its thermal stability. The thermal treatment carried out on glasses helped to derive their glass-ceramic counterparts. The amorphous and crystalline features of samples were characterized using X-ray diffraction patterns. The crystalline species that emerged out of the calcium phosphate phases confirmed the dominance of Q1 and Q2 structural distributions in the investigated glass-ceramics. The obtained scanning electron micrographs and atomic force microscopic images confirmed the surface crystallization and textural modification of the samples after thermal treatment. The N2-adsorption–desorption studies explored the reduction of porous structures due to thermal treatment on the melt-driven glass surface. The measured elastic moduli and Vicker's hardness values of the glasses showed an increase after thermal treatment, which were reduced against the inclusion of alkali content in both glass and glass-ceramics.  相似文献   

20.
The purpose of the current work was to research the effect of alkali metal oxide on the structure, thermal properties, viscosity and chemical stability in the glass system (R2O–CaO–B2O3–SiO2) systematically. Because the glass would emulsify when Li2O was added to the glass batch, this article did not discuss Li2O. The results showed that when the amount of Na2O was less than 4 mol.%, there was a higher interconnectivity of borate and silicate sub-networks in glass, as more mixed Si–O–B bonds were present in glass. The glass samples exhibited excellent thermal properties and chemical stabilities. As the amount of Na2O exceeded 4 mol.%, the interconnectivity of borate and silicate sub-networks was weakened. The thermal properties and chemical stabilities of the glass samples were reduced. The connectivity of the silicate sub-network was weakened slightly as the Na/K ratio varied, and the coefficient of thermal expansion (CTE) of the glass samples gradually increased, and the resistance to thermal shock (RTS) value gradually decreased. Moreover, the viscosity of the glass samples decreased with the ratio of Na/Si and Na/K increased.  相似文献   

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