Crystallization behavior and mechanical properties of polypropylene/halloysite composites

In this work, halloysite nanotubes (HNTs), a new type of inexpensive filler, were used for the modification of polypropylene (PP). HNTs were first surface treated by methyl, tallow, bis-2-hydroxyethyl, quaternary ammonium, then melt mixed with PP. Scanning electron microscope (SEM) was used to examine the dispersion of HNTs in PP matrix. Differential scanning calorimetry (DSC), polarized light microscope (PLM), dynamic melt rheometry and wide angle X-ray diffraction (WAXD) were employed to investigate the crystallization behavior of the prepared PP/HNT composites. The mechanical properties were evaluated by Instron and impact tests. SEM results revealed that HNTs could be well-dispersed in PP matrix and had a good interfacial interaction with PP, even up to a high content of 10 wt%. DSC data indicated that HNTs could serve as a nucleation agent, resulting in an enhancement of the overall crystallization rate and the non-isothermal crystallization temperature of PP. PLM showed a constant spherulite growth rate and a decreased spherulite size at given isothermal crystallization temperature, suggesting that nucleation and growth of a spherulite are two independent processes. The result obtained by dynamic melt rheometry indicated that HNTs mainly promoted nucleation and had not much influence on the growth of PP crystallization. Nevertheless, by fast cooling the samples, almost constant spherulite size can be obtained for both pure PP and PP/HNT composites due to the limited nucleation effect of HNTs on PP crystallization. WAXD showed that HNTs mainly facilitated α-crystal form of PP. Though a good dispersion of HNTs in PP matrix was observed, out of our expectation, not much enhancement on mechanical properties of PP/HNT composites had been achieved, and this could be mainly ascribed to the constant crystallinity and spherulite size of PP as well as the small length/diameter ratio of HNTs.     

透辉石玻璃陶瓷的制备及其析晶特性研究

以废玻璃粉为原料,采用反应析晶烧结法制备了透辉石玻璃陶瓷。采用差热分析、X射线衍射分析、扫描电镜、能谱、高分辨透射电镜等方法研究了顽辉石-堇青石粉和废玻璃粉混合样品等温烧结过程中顽辉石-堇青石向透辉石转变的演变过程。结果表明:顽辉石-堇青石与玻璃粉在815°C下即可发生反应析晶;900°C保温2 h可获得透辉石为主晶相的玻璃陶瓷。在保温过程中,顽辉石的Mg~(2+)和O~(2-)向玻璃中扩散,玻璃中的Si~(4+)和Ca~(2+)向顽辉石中移动,使顽辉石晶体在b轴方向交替排列的两条链沿c轴方向断开,转变成单链,由Mg~(2+)和Ca~(2+)连接生成透辉石。保温0 h时,由于堇青石[MgO_6]八面体膨胀较小,玻璃中的Si~(4+)、Ca~(2+)、Na~+向堇青石中移动,反应析晶生成钠长石与透辉石;当保温时间延长至2 h时,堇青石[MgO_6]八面体骨架进一步扭曲,生成主晶相为透辉石的玻璃陶瓷。     

Effect of metastable phase on the crystallization and mechanical properties of MgO-Al2O3-SiO2 glass-ceramics without nucleating agents

Glass-ceramics without nucleating agents usually undergo surface crystallization, which deteriorates the overall performance of the products. In this paper, we evaluated the effects of the metastable MgAl₂Si₃O₁₀ crystalline phase on the crystallization behavior of a MgO–Al₂O₃–SiO₂ (MAS) glass without nucleating agents and mechanical properties of the glass-ceramics obtained. The results demonstrated that the precipitation of metastable MgAl₂Si₃O₁₀ crystallites promotes the crystallization mechanism transformed from surface crystallization into volume crystallization with two-dimensional crystal growth. Furthermore, the grain size of MgAl₂Si₃O₁₀ near the surface of the prepared glass-ceramics was larger than that of MgAl₂Si₃O₁₀ inside, which helps to generate compressive stress and improves its mechanical properties. The glass-ceramics containing metastable MgAl₂Si₃O₁₀ phase exhibited an enhanced hardness in the range of 7.6 GPa–9.5 GPa for indentation loads ranging from 2.94 N to 98 N, and indentation size effect behavior was observed in Vickers hardness tests of both MAS glass and glass-ceramics. The load-independent hardness values for MAS glass and glass-ceramics were reliably evaluated by the modified proportional specimen resistance (MPSR) model of 7.1 GPa and 7.6 GPa, respectively, with a high correlation coefficient of more than 0.9999. This work reveals the unexploited potential of the metastable phase in improving the crystallization ability and mechanical properties of glass-ceramics.     

A novel process of preparing glass-ceramics with pseudo-bioclastic texture

Water quenching-induced cracked-glass was used as parent glass to prepare glass-ceramics in this work. The cracked-glass panel was first heat-treated through two-step method, i.e. sintering for 1 h at 860 °C and subsequent crystallization for 1.5 h at 1080 °C, and then naturally cooled down to room temperature to be transformed into glass-ceramics. XRD and SEM observations confirm that the cracked-glass can be used as parent glass to deposit β-wollastonite crystals depending on crack crystallization mechanism. The volume densities, porosities and bending strengths of the glass-ceramics are respectively around 2.7 g/cm³, 0.5% and 40 MPa. As compared with glass-ceramics prepared by conventional glass grain sintering process, the new type of glass-ceramics produced by CGC process shows pseudo-bioclastic texture and has less gas pore flaws, and may therefore become an alternative for materials of architectural decoration.     

Thermo-magnetic properties of Fe2O3-doped lithium zinc silicate glass-ceramics for magnetic applications

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.     

Preparation of glass-ceramics from red mud in the aluminium industries

The feasibility of recycling red mud and fly ash in the aluminium industries by producing glasses and glass-ceramics has been investigated. The crystallization behavior of glass-ceramics mostly produced from red mud and fly ash was studied by DTA, XRD, optical microscopy techniques. According to DTA curve, nucleation experiments were carried out at various nucleation temperatures at the same crystallization temperature of 900 °C for 2 h, and crystallization experiments were performed at the same nucleation temperature of 697 °C for 2 h followed by crystallization at various temperatures. The nucleation results show that optimum nucleation temperature is near 697 °C, and the crystallization experiments show that the crystallization at a high temperature of over 900 °C results in denser grain size. The major crystallized phases were gehlenite (Ca₂Al₂SiO₇), and augite (Ca(Fe,Mg)Si₂O₆). The XRD results show that with the increase of crystallization temperature, the amount of gehlenite increases, and augite decreases, which is the result of augite transformation into gehlenite.     

Synergistic effect of glass fibre and Al powder on the mechanical properties of glass-ceramics

To explore the synergistic effect of glass fibre and Al powder on the mechanical properties of glass-ceramics, blast furnace slag was chosen as the main material, and glass fibre and Al powder as reinforcement materials. The phase compositions, microstructures, compressive properties, and apparent density of the glass-ceramics with varying quantities of glass fibre and Al powder were investigated. The experimental results indicated that Al powder could exist as a simple substance in glass-ceramics and form a dense net coating on the surface of blast furnace slag to improve the plasticity of the glass-ceramic. The glass fibre had better reinforcement effect than Al powder because of its extremely high mechanical strength. The plasticity of glass-ceramics, however, severely decreased; the glass-ceramics exhibited brittle failure during compression. A slight increase in the content of CaSi₂ and SiO₂ in the glass-ceramics was closely related to the addition of glass fibre. Considering safety and economy, glass-ceramics with 6% Al and 14% glass fibre (S4) have the best mechanical properties. The compressive strength, strain at maximum force, and apparent density were 40?MPa, 19% and 1.974?g/cm³, respectively.     

Nano-crystal glass-ceramics obtained from high alumina coal fly ash

Glass has been obtained by melting high alumina coal fly ash with fluxing additives. A thermal treatment was employed to convert the obtained glass into nano-crystal glass-ceramics. X-ray diffraction (XRD) patterns show that the main crystalline phases in both the glass-ceramics are anorthite (CaAl₂Si₂O₈) and wollastonite (CaSiO₃). The crystals are homogeneously dispersed within the parent glass. The average crystal size is below 200 nm. Physical and mechanical properties, such as density, thermal expansion coefficient, hardness, and bending strength, of the glass have been examined and the corresponding microstructures are discussed. The results demonstrate that the glass-ceramics have potential for a wide range of construction application.     

The effect of chromite ore addition on crystallization kinetics of basalt based machinable glass-ceramics

In this study, the properties of machinable glass-ceramic materials produced from basalt and chromite ore were investigated. Three different compositions by adding chromite ore in different ratios to the main composition produced from basalt and MgF₂ were prepared. In this way, the effects on the machinable glass-ceramic of chromium and iron oxides in the chromite ore were investigated. Thermal degradation of chromite ore and the effect of its compounds on the crystallization of machinable glass-ceramics were investigated. The samples were subjected to machinability testing. Scanning electron microscopy (SEM) and X-ray diffraction analysis (XRD) were used for characterization. The results show that chromite addition has positive effects on crystallization and machinability. Also, crystallization kinetic studies were realized. It was seen that the effect of iron oxide in chromite ore on crystallization is higher than that of chromium oxide for the crystallization conditions that used chromite ore as a nucleating agent.     

钙硅比对钙铁硅铁磁体微晶玻璃核化与晶化的影响

为了研制用作温热治疗癌症的铁磁体微晶玻璃热种子材料,制备了一组化学组成为40Fe2O3xCaO(60-x)SiO23B2O33P2O5玻璃(x=20、25、30、35质量分数),用XRD、DTA、VSM对其核化与晶化过程进行了研究.研究发现,钙铁硅微晶玻璃在还原气氛下热处理后,除了磁铁矿和硅灰石及少量赤铁矿晶相外,还会出现钙铁辉石、方石英晶相.钙硅比较小的玻璃,热处理温度-时间相图中钙铁辉石相区范围较大;钙硅比较大的,钙铁辉石相区范围较小.另外,钙硅比不同,玻璃的成核机理、开始析出磁铁矿的温度也不同.     

Phase evolution and microwave dielectric properties of MgO-B2O3-SiO2-based glass-ceramics

The densification and crystallization behaviors of MgO-B₂O₃-SiO₂ (MBS) glass with various amounts of TiO₂ additions (0-10 wt.%) were investigated by means of thermal analysis, X-ray powder diffraction and scanning electron microscopy. A microwave dielectric characterization was performed in order to evaluate the suitability of MBS glass-ceramics as a low-permittivity dielectric substrate. The densification of the MBS glass started below 700 °C. The main crystalline phases of Mg₂B₂O₅ and MgSiO₃ appeared at 800 and 950 °C, respectively. The Mg₃TiB₂O₈ and TiB_0.024O₂ phases additionally crystallized in TiO₂-added MBS glass-ceramics at 1000 °C. The permittivity increased from 6.1 in pure MBS glass to 6.9 in MBS glass with 10 wt.% of TiO₂. The addition of TiO₂ enhanced the crystallization and consequently increased the Qxf-values of the MBS glass (11 300 GHz) up to 16 500 GHz. The improvement of the Qxf-values became the most evident at 1050 °C. Dense MBS glass-ceramics sintered at 850 ≤ T ≤ 950 °C exhibited Qxf-values of 5000-8000 GHz (at ∼12 GHz), which are comparable with the values of CaO-B₂O₃-SiO₂-based glass-ceramics.     

Rheological and mechanical properties of blends of LDPE with high contents of UHMWPE wastes

The mixing of UHMWPE wastes with other polymers aims to reduce the environmental impact of waste materials. The dynamic rheological behavior of the blends, tensile and abrasion properties, Shore D hardness and impact resistance, and morphology are important in characterizing polymer blends. In this work, we have sought to obtain blends containing different proportions of UHMWPE wastes and LDPE with properties suitable for the manufacture of useful products. The blends exhibit an increase in complex viscosities, storage modulus, and Young's modulus with increasing content of UHMWPE wastes and a decrease in both the maximal elongation and Charpy impact resistance. Summarizing, the addition of up to 60 wt % of industrial fragments of UHMWPE is possible using conventional methods of processing to prepare blends with values of tensile strength, abrasion, and Shore D hardness similar to those of LDPE. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44996.     

Crystallization,microstructure and mechanical behavior of titanium doped barium fluormica glass-ceramics

Crystallization, microstructure and mechanical behavior of TiO₂ doped barium fluorphlogopite glass-ceramics were systematically studied. TiO₂ was used as a doper nucleant in the BaO·4MgO·Al₂O₃·6SiO₂·2MgF₂ glass system. Melting technique was adopted to prepare the glass samples which were analyzed by differential thermal analysis (DTA), X-ray diffraction, scanning electron microscopy, and micro hardness indenter. The DTA study demonstrated that the crystallization exotherm of fluorphlogopite mica appeared in the temperature window of 886-903°C. In this investigation, four glass samples were prepared using 2 (MA1), 4 (MA2), 6 (MA3), and 8 (MA4) wt% of TiO_2. Glass transition (T_g) and peak crystallization (T_p) temperatures escalated with an increase in the TiO₂ content from 2 (MA1) to 4 wt% (MA2). However, beyond this value, T_g and T_p decreased with a surge in TiO₂ content from 6 (MA3) to 8 wt% (MA4). Nevertheless, with a gradual rise in the TiO₂ content, the crystals of the glass-ceramics became enlarged and subsequently exhibited mechanical properties, such as hardness, fracture toughness, and machinability. Therefore, in solid oxide fuel cell applications, TiO₂ is a promising nucleating agent to generate fluorphlogopite mica-based glass-ceramics.     

Microstructural development and electrical behavior during crystalization of iron-rich glass-ceramics obtained from mill scale

Mill scale is one of the most hazardous waste generated from the steelmaking industry. In 2014, around 16.4–32.8 million t of mill scale was generated all over the world. In this paper, we present recent results about the effect of the structure and microstructure of iron-rich glass-ceramics obtained from mill scale on their electrical behavior. Five iron-rich glass compositions were investigated. The crystalline phases of the crystallized (glass-ceramic) materials were identified by X-ray diffractometry, and phase content quantifications were performed by the Rietveld method. The crystallinity and porosity were also related to the electrical behavior of the glass-ceramics, which was determined by impedance spectroscopy, and the hardness, measured by the Vickers indentation method. Albite, andradite, anorthite, clinopyroxene, franklinite, nepheline, and spinel were shown to be the main crystalline phases present in the investigated compositions. The conductivity showed an increasing trend with the degree of crystallinity. This behavior was attributed to a decrease in porosity, an increase in the concentration of charge carriers in the glass phase (iron, Li⁺, and Na⁺), and an increase in the number of conduction paths through the glassy phase/crystalline phase interfaces. The relationship between hardness and crystallinity could not be verified due to the structural complexity of the glass-ceramics studied. However, a nearly linear relationship was found between the effect of porosity and hardness. The G2Z composition exhibited a hardness of 6.1 ± 0.5 GPa at 850 °C, which is a value in very good agreement with other iron-rich glass-ceramics studied.     

Crystallization,structure and properties of MgO-Al2O3-SiO2 highly crystalline transparent glass-ceramics nucleated by multiple nucleating agents

Generally, highly crystalline transparent glass-ceramics possess excellent physical and chemical properties compared to organic and other inorganic optical materials. We have successfully prepared highly crystalline transparent glass-ceramics in the MgO-Al₂O₃-SiO₂ system by "extreme-time" nucleation & "finite-time" crystallization processes using P₂O₅, ZrO₂ and TiO₂ as multiple nucleating agents. The results revealed that the crystallization of glass is controlled by a three-dimensional interfacial crystal growth process. These glass-ceramics mainly consisted of cordierite crystals with a residual glassy phase, and crystallinity increased with crystallization time, but light transmittance decreased with crystallization time due to enlarged grain sizes. EDS mapping revealed a uniform distribution of elements within the glass-ceramic. In the optimal preparation condition (825?°C/96?h?+?990?°C/3?h), these glass-ceramics exhibited a high crystallinity (87.3?vol. %), high transmittance (78%), and excellent mechanical properties. This work provides a roadmap for preparing highly crystalline transparent glass-ceramics for applications in optical engineering.     

Sintering behavior,structure and dielectric properties of CuO-ZnO-MgO-B2O3 glass-ceramics for ULTCC applications

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.     

Addition of h-BN for enhanced machinability and high mechanical strength of AlN/Mo composites

Ceramic/metal composites, as high-temperature structural materials, have limited applications because of their poor machinability. AlN/Mo/Mo₂B machinable composites were fabricated by adding h-BN to AlN/Mo composites by plasma-activated sintering at various temperatures and at an axial pressure of 30 MPa under argon atmosphere. The sample sintered at 1500 °C exhibited excellent machinability for cemented carbide tools, with a bending strength of approximately 500 MPa and a Vickers hardness value of 9.34 GPa. The effects of sintering temperature on the microstructure, mechanical properties, and machinability were investigated, and the reactions introduced by adding h-BN were studied. These reactions reinforced the composite and newly introduced a Mo₂B phase, which showed better ability to deflect cracks and prevent them from moving deep inside the composite, thus improving its machinability. This research provides a possible solution for improving the machinability of ceramic/metal composites without sacrificing the strength.     

Influence of barium oxide on the crystallization, microstructure and mechanical properties of potassium fluorophlogopite glass-ceramics

The influence of barium oxide, heat treatment time and temperature on the crystallization, microstructure and mechanical behavior of the system Ba_x·K_1−2x·Mg₃·Al·Si₃O₁₀·F₂ (where x = 0.0, 0.3 and 0.5) was investigated in order to develop novel, high strength and machinable glass-ceramics. Three glasses were prepared and characterized by differential thermal analysis (DTA), X-ray diffraction (XRD), scanning electron microscope (SEM) techniques and some mechanical testing methods.The crystallization kinetics of glass-ceramics was also studied. Activation energy and Avrami exponent calculated for the crystallization peak temperature (T_p) of three different glass batches. The Vickers hardness decreased slightly on formation of the potassium fluorophlogopite and barium fluorophlogopite phases, but decreased significantly on formation of an interconnected ‘house of cards’ microstructure.     

Potential utilization of oil sludge incineration bottom ash for glass-ceramics: Crystallization kinetics,properties and toxicological evaluation

The bottom ash (OIBA) generated from the incineration of hazardous oil sludge is classified as a hazardous waste. In this work, the OIBA was applied as raw material to prepare SiO₂-Al₂O₃-CaO system glass-ceramics by melt-sintering with the addition of waste glass wool (GW). The effects of basicity (CaO/SiO₂ ratio, 0.52-1.05) and sintering temperature (900–1050 °C) on the crystallization kinetics, properties, microstructure, leaching concentrations of heavy metals and potential toxicity of glass-ceramics were investigated. The results showed that the crystallization pattern was two-dimensional crystallization, and with the decrease of basicity, the main crystalline phase evolved from gehlenite to diopside. And the glass-ceramics with basicity of 0.88 and sintering temperature of 950 °C exhibited the best comprehensive properties, including density (2.72 g/cm³), water absorption (0.06%), compressive strength (452.45 MPa) and chemical corrosion resistance. In addition, the reduction of heavy metal leaching concentration indicates that produced glass-ceramics showed excellent solidification effect on heavy metals, the low toxicity of glass-ceramics leaching solution to the wheat seeds and Artemia suggests the environmental protection characteristics of OIBA-based glass-ceramics. These findings proved that the glass-ceramics produced by OIBA and GW could be a promising method to dispose hazardous waste with preparing high value-added construction materials.     

Role of MgO in lowering glass transition temperature and increasing hardness of lithium silicate glass and glass-ceramics

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.