Effects of Magnesia Fines Addition and Spinel with Different Compositions on Thermal Expansion Behavior of Alumina Magnesia Castables

Effects of magnesia fines addition ( 4% ,6% and 8% in mass) and spinel with different compositions ( alumina-rich,magnesia-rich and stoichiometric spinel) on thermal expansion behavior of alumina magnesia castables were researched using tabular corundum, magnesia fines,spinel fines,ρ-Al2O3,Secar-71 cement and SiO2 fume as main starting materials. The results show that: ( 1) thermal expansion coefficients of specimens with 4 mass% and 6 mass% magnesia fines have the similar change tendency,increasing slightly with temperature rising; when magnesia addition is 8 mass% ,the thermal expansion coefficient increases obviously at 1 050 ℃ and reaches the peak at 1 350 ℃ ; ( 2) when MgO content is the same,the specimen with magnesia-rich spinel has the lowest thermal expansion coefficient; ( 3) for the castables specimens with the same MgO content,the specimen with magnesia has higher thermal expansion coefficient than that with presynthesized spinel,which is related with the secondary spinelization during the heating process.     

Increasing Wet Green Strength of Alumina Body During Microfabrication by Colloidal Isopressing

Colloidal Isopressing involves formulating a slurry with a weakly attractive particle network that can be pre-consolidated to a high relative density by pressure filtration and still retain fluid-like characteristics. The pre-consolidated slurry is injected into an elastomeric mold and isopressed. Isopressing rapidly converts the slurry into an elastic body that can be removed from the mold without shape distortion. Not only is this process rapid, but since the water saturated compact produced by this method does not shrink during drying, it can also be converted into a green body without a long drying period. It is demonstrated that micron-size surface features, such as 5 μm wide channels with a depth/width ratio of 2, can be rapidly produced on the surface of alumina powder compacts. The fracturing of thin vertical portions of a micro-patterned surface during pressure release and demolding has been an obstacle to obtaining micron-sized features with high aspect ratios. A method is shown here that enables the fabrication of such features by strengthening the saturated isopressed body. It is shown that concentration controlled gelation of a poly(vinyl alcohol)–Tyzor^® Triethanolamine Tritanate (TE) additive effectively increases the strength of the elastic, isopressed body, saturated with water, while maintaining the low viscosity of the pre-consolidated slurry, which is required for transferring the pre-consolidated slurry into a rubber mold prior to isopressing.     

Size-Dependent Spontaneous Separation of Colloidal Particles in Sub-Microliter Suspension by Cations

Great efforts have been made to separate micro/nanoparticles in small-volume specimens, but it is a challenge to achieve the simple, maneuverable and low-cost separation of sub-microliter suspension with large separation distances. By simply adding trace amounts of cations (Mg²⁺/Ca²⁺/Na⁺), we experimentally achieved the size-dependent spontaneous separation of colloidal particles in an evaporating droplet with a volume down to 0.2 μL. The separation distance was at a millimeter level, benefiting the subsequent processing of the specimen. Within only three separating cycles, the mass ratio between particles with diameters of 1.0 μm and 0.1 μm can be effectively increased to 13 times of its initial value. A theoretical analysis indicates that this spontaneous separation is attributed to the size-dependent adsorption between the colloidal particles and the aromatic substrate due to the strong hydrated cation-π interactions.     

In situ Production of Polystyrene Magnetic Nanocomposites through a Batch Suspension Polymerization Process

This work presents the synthesis of micro‐sized polystyrene magnetic beads by in situ incorporation of oleic acid‐modified Fe₃O₄ magnetic nanoparticles via a suspension polymerization process. Fe₃O₄ nanoparticles with superparamagnetic characteristics were obtained through a coprecipitation technique. These particles present an average diameter equal to 7.4 ± 4.6 nm, as determined by AFM. This result is in agreement with the crystallite size of single domains calculated by using Scherrer's equation, which was equal to 7.7 nm, based on XRD measurements. The obtained materials were also studied using TGA. The weight loss behavior was independent of the Fe₃O₄ content and the stability to the thermal degradation was also not improved by magnetic nanoparticles present in the composite. Polystyrene/Fe₃O₄ magnetic nanocomposites exhibited the same diffraction peaks observed in the pure Fe₃O₄, which indicates that nanoparticles inside the composites preserved the structure and properties of pure Fe₃O₄. It was also shown that nanosized polystyrene particles, dispersed in the aqueous phase, are obtained due to the stabilization effect of the oleic acid on the styrene droplets. A cross‐section of polystyrene magnetic particles showed empty spherical regions, attributed to the encapsulation of water microdroplets during the polymerization reaction. The obtained polymeric materials also presented good magnetic behavior, indicating that the modified Fe₃O₄ nanoparticles were successfully dispersed in the polystyrene particles.

     

Direct Coagulation Casting of Alumina Suspension from Calcium Citrate Assisted by pH Shift

Direct coagulation casting of alumina suspension via controlled release of high valence counter ions (DCC–HVCI) using calcium citrate as coagulating agent was reported. Hydrolysis of glycerol diacetate shifts the pH of suspension to weakly acidic region which helps to decompose calcium citrate and release calcium ions. The effect of concentration of glycerol diacetate and calcium citrate on the pH and viscosity of alumina suspension was investigated at 25°C and 60°C, respectively. The pH of suspensions with glycerol diacetate and calcium citrate decreases to 8.6 and 7.5 treated at 25°C and 60°C, respectively. It is indicated that high viscosity is achieved by adding 2 vol% glycerol diacetate and 0.5 wt% calcium citrate which is enough to coagulate the suspension. Green body with compressive strength of 1.0 MPa is obtained by treating the alumina suspension with 2 vol% glycerol diacetate and 0.5 wt% calcium citrate at 60°C for 1 h. The alumina ceramics sintered at 1550°C have homogeneous microstructure with relative density above 99.0%.     

TiO2加入量对固相烧结合成镁铝尖晶石致密化行为的影响

以低品位菱镁矿和工业α氧化铝微粉为主要原料固相烧结合成镁铝尖晶石,探讨TiO2添加剂对合成镁铝尖晶石致密化行为的影响.用X射线衍射(XRD),扫描电镜(SEM)及相关分析软件对烧后试样的相组成和显微结构进行研究,以揭示镁铝尖晶石烧结致密化的过程机理.研究结果表明:添加剂TiO2与形成镁铝尖晶石的置换固溶作用是促进固相合成镁铝尖晶石烧结致密化的重要机理,阳离子空位的产生以及镁铝尖晶石的晶格缺陷,高温下有利于镁铝尖晶石的晶体发育和长大,在空间位阻效应的作用下,达到排除气孔使试样致密化的目的;随着TiO2加入量的增多,镁铝尖晶石的致密化程度也逐渐升高,能够有效的改善制品的烧结性能和显微结构.     

Elucidation of Viscosity Reduction Mechanism of Nano Alumina Suspensions with Fructose Addition by DSC

Control of the rheological properties of the nanoparticle suspensions is challenging. In this study influence of the solids content and the fructose addition on the viscosity of nano alumina suspensions have been investigated by low temperature differential scanning calorimetry (LT‐DSC), rheometry, and zeta potential measurements. Analysis of the water melting events in LT‐DSC revealed useful information for explaining the rheological behavior of the nanoparticle suspensions. It was shown that the bound water layer has a negligible effect on the viscosity of micrometer‐size particle suspension while it increases the effective solid content of alumina nanoparticle suspensions significantly leading to high viscosities. The presence of fructose modifies the bound water layer, decreases the effective solids content, hence resulting in viscosity reduction. Fructose addition lowers the pH of the suspension, but has a negligible effect on the zeta potential. The origin of the bound water, and electrostatic and steric effects of the fructose addition on the viscosity are discussed.     

Effect of Ultrasonication on the Microstructure and Tensile Elongation of Zirconia-Dispersed Alumina Ceramics Prepared by Colloidal Processing

To obtain dense, fine-grained ceramics, fine particles and advanced powder processing, such as colloidal processing, are needed. Al₂O₃ and ZrO₂ particles are dispersed in colloidal suspensions by electrosteric repulsion because of polyelectrolyte absorbed on their surfaces. However, additional redispersion treatment such as ultrasonication is required to obtain dispersed suspensions because fine particles tend to agglomerate. The results demonstrate that ultrasonication is effective in improving particle dispersion in suspensions and producing a homogeneous fine microstructure of sintered materials. Superplastic tensile ductility is improved by ultrasonication in preparing suspensions because of the dense and homogeneous fine microstructure.     

In situ chemically crosslinked chitosan membrane by adipic acid

Adipic acid, which is nontoxic, was used to dissolve chitosan. The chitosan/adipic acid solution was used to prepare chitosan membrane. After being heated at 80–100°C, the membrane was in situ chemically crosslinked by adipic acid, as verified by Fourier transform infrared and wide‐angle X‐ray diffractometer analysis. The crosslinked membrane did not collapse even without treatment in alkaline solution. In addition, the in situ crosslinking reaction was studied. The crosslinking degree (CLD) was quantitatively calculated based on the mass of water produced. The results showed that CLD was positively related to both heating temperature and time. Results of kinetic of crosslinking reaction suggested that the amidation was in agreement with the first‐order rate equation and that the temperature effect could be described with the Arrhenius equation. The results of weight loss of chitosan membrane in phosphate‐buffered solution (pH = 7.4) indicated that the best water resistance of chitosan membrane was obtained at 90°C. In brief, a straightforward, nontoxic, environment‐friendly, and economical chemically crosslinking approach has been developed for chitosan materials. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

In situ characterization of ceramic cold sintering by small-angle scattering

The first in situ characterization of the pore morphology evolution during the cold sintering process (CSP) is presented using small-angle X-ray scattering methods. For practical reasons, measurements have been made on a model system, KH₂PO₄ (KDP). The scattering signal revealed a striking behavior that could be modeled with nanoscale structural features associated with the dissolution and reprecipitation of KDP close to the grain/pore interface during CSP. The prospects for future more quantitative experiments under a range of temperature and pressure conditions, as well as for studies of more technologically important materials such as ZnO are considered.     

In situ fabrication of cross-linked protein membranes by using microfluidics

We report a novel technique for preparing cross-linked protein membranes within microchannels by using an interfacial cross-linking reaction. Glass microchannels with a Y input were assembled by using a simple adhesive bonding technique to achieve dual, parallel laminar flows. Membrane formation utilised an interfacial reaction at the liquid-liquid interface, which involved bovine serum albumin (aqueous solution with a flow rate of 300 microL min(-1)) and terephthaloyl chloride (xylene solution with a flow rate of 700 microL min(-1)), to form thin ( approximately 25 microm) cross-linked films along the length of the channel under the continuous pressure-driven laminar flow. Such microfabricated membranes could extend the separation potential of any microfluidic structure to provide a stable barrier layer. Furthermore, degradation of the membrane was possible by using an alkali sodium dodecyl sulfate solution, which led to the complete disappearance of the membrane. These membranes could facilitate additional modification to allow for different permeability properties by controlled degradation. The one-step in situ membrane-fabrication methodology reported here generated precisely localised membranes and avoided the complexities of subcomponent assembly, which require complicated alignment of small, preformed membranes. This methodology could become the basis for sophisticated microseparation systems, biosensors and several "lab-on-a-chip" devices.     

In situ study of photopolymerization by fourier transform infrared spectroscopy

The Fourier transform infrared (FTIR) in situ method was developed for the investigation of photopolymerization. Ultraviolet (UV) cure of a mixture of a cycloaliphatic epoxide, a 2-ethylhexyl acrylate, and photoinitiators, which forms simultaneous interpenetrating polymer network (IPN), was monitored while the sample was irradiated with UV light. Triphenylsulfonium salt and benzoin ether were used as photoinitiators. For the sake of comparison, similar experiments were performed for the epoxide with the triphenylsulfonium salt photoinitiator and the acrylate with the benzoin ether photoinitiator. The epoxy photopolymerization was monitored using an epoxy CH stretching band at 3005 cm^?1 and a ring vibration band at 790 cm^?1. The acrylic photopolymerization was monitored using a C?C stretching band at 1637 cm^?1. The epoxy conversion was less than 60% when the acrylic polymerization was completed in the IPN.     

Imaging Secondary-Ion Mass Spectroscopy Observation of the Scavenging of Siliceous Film from 8-mol%-Yttria-Stabilized Zirconia by the Addition of Alumina

The scavenging of a resistive siliceous phase via the addition of Al₂O₃ was studied, using imaging secondary-ion mass spectroscopy (SIMS), given the improved grain-boundary conductivity in 8-mol%-yttria-stabilized zirconia (8YSZ). The grain-boundary resistivity in 8YSZ decreased noticeably with the addition of 1 mol% of Al₂O₃. Strong SiO₂ segregation at the grain boundaries was observed in a SIMS map of pure 8YSZ that contained 120 ppm of SiO₂ (by weight). The addition of 1 mol% of Al₂O₃ caused the SiO₂ to gather around the Al₂O₃ particles. The present observations provided direct and visual evidence of SiO₂ segregation at the grain boundaries (which had a deleterious effect on grain-boundary conductivity) and the scavenging of SiO₂ via Al₂O₃ addition.     

In situ formation and compounding of polyamide 12 by reactive extrusion

The anionic polymerization of lauryllactam was initiated at 270°C using sodium hydride as an initiator and N,N′‐ethylene‐bisstearamide (EBS) as an activator (NaH:EBS molar ratio of 2). Polymerization occurred in less than 2 min and was successfully performed in an internal mixer and a twin‐screw extruder with corotating intermeshing screws (Werner & Pfleiderer ZSK 25). The content of residual monomer, as determined by thermogravimetric analysis, was lower than 0.5 wt %. Molecular weight, as measured by size exclusion chromatography, was governed by the lauryllactam:NaH molar ratio calculated on a M_n of 25 kg/mol at a constant NaH:EBS molar ratio of 2. Blends were prepared in situ by polymerization of lauryllactam solutions of various polymers. When poly(ethylene‐co‐butylacrylate) (Lotryl®; Atofina) was dissolved in lauryllactam, rubber‐toughened polyamide 12 blends were obtained. Mechanical properties of the injection‐molded polymers were examined by stress–strain as well as notched Charpy impact tests at different temperatures. Blend morphologies were imaged by scanning electron microscopy (SEM). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 344–351, 2003     

In situ compatibilization of PEN/LCP blends by ultrasonic extrusion

In situ compatibilization of immiscible blends of PEN and thermotropic LCP was achieved by the ultrasonically‐aided extrusion process. Ultrasonically‐treated PEN underwent degradation, leading to a decrease of its viscosity. Viscosity of LCP was unaffected by ultrasonic treatment. Because of reduced viscosity ratio of PEN to LCP at high amplitude of ultrasonic treatment, larger LCP domains were observed in molding of the blends. LCP acted as a nucleating agent, promoting higher crystallinity in PEN/LCP blends. Ultrasonically‐induced copolymer formation was detected by MALDI‐TOF mass spectrometry in the blends. Ultrasonic treatment of 90/10 PEN/LCP blends improved interfacial adhesion in fibers spun at intermediate draw down ratios (DDR), improving their ductility. The lack of improvement in the mechanical properties of fibers spun at high DDR after ultrasonic treatment was attributed to the disturbance of interfacial copolymer by high elongation stresses. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

In situ synthesis of orange rutile ceramic pigments by non-conventional methods

Different precursor-mixtures of orange Cr,Sb-TiO₂ ceramic pigment have been obtained by non-conventional methods (heterogeneous ammonia coprecipitation, urea homogeneous coprecipitation, PECHINI polyester method and an original aqueous–organic coprecipitation method in water–diethylenglycol medium) in order to produce in situ the pigment through the ceramic body firing. The pigmenting performances of powders were appraised in two cases: (a) as ceramic pigment for glazed porcelain stoneware and (b) as ceramic inks for screen printing of porcelain stoneware. Samples were characterised by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), UV–vis-NIR spectroscopy by diffuse reflectance method, CIE-L*a*b* colour parameters, BET specific surface area and crystallite size measured by the Scherrer method. The colouring performance of raw powders obtained by non-conventional methods in glazed porcelain stoneware improves that of the ceramic samples fired at 1100 °C used as reference. TEM observations indicate nanostructured powders with pigmenting performance depending on factors such as their specific surface area (BET), the crystalline phases detected by XRD (e.g. anatase–rutile presence) and their crystallite size (Scherrer measurements). Ammonia coprecipitated samples, both in water and in water–diethylenglycol medium without surfactant addition, or modified by the addition of sodium dodecyl sulphate as surfactant, stand out by their colouring performance.     

In situ TiC-reinforced austenitic steel composite by self-propagating high temperature synthesis

TiC-reinforced austenitic steel composites have been prepared by self-propagating high temperature synthesis (SHS). The in situ reinforcement of a Fe-Mn-based austenitic steel matrix with TiC was achieved upon aluminothermic reduction of iron oxide (Fe₂O₃), manganese dioxide (MnO₂) and titanium dioxide (TiO₂) powders in the presence of carbon (C). This highly exothermic thermite reaction was found to produce in situ the Fe-Mn-TiC austenitic steel composites. The reaction kinetics, recovery of Mn and TiC, yield of metal, and composite microstructure were found to strongly depend on the process parameters, such as green composition, blending sequence, and average particle size of Al powder used as a reducing agent. The text was submitted by the authors in English.     

Measurement of Microscopic Bridging Stresses in an Alumina/Molybdenum Composite by In Situ Fluorescence Spectroscopy

The R -curve behavior of an Al₂O₃ ceramic with 25 vol% of molybdenum-metal particles added was studied by using fracture-mechanics experiments and in situ piezospectroscopic measurements of microscopic bridging tractions. Cracks were propagated by using a crack stabilizer, which allowed stable crack growth in a bending geometry. Microscopic bridging stresses were measured in situ during fracture propagation by detecting the shift of the Cr³⁺ fluorescence lines of Al₂O₃. Laser spots ∼1 µm in diameter and ∼10 µm deep were focused at the ceramic/metal interface of the bridging sites, and the closure stresses that acted on the crack faces were recorded as a function of external load. The maximum stress that was experienced by the stretched metal particles prior to final failure was ∼0.4 GPa. The maximum stress magnitude was not markedly different in relatively small (i.e., <5 µm) metal particles, failing with large ductility, as compared with larger particles which, instead, fractured in semibrittle fashion. A map of bridging tractions along the crack wake was constructed under a constant stress intensity factor, almost equal to that which is critical for crack propagation. Using this map to theoretically predict the rising R -curve behavior of the composite led to results that were consistent with the fracture-mechanics experiments, thus enabling us to explain the observed toughening, primarily in terms of a crack-bridging mechanism.     

In situ nanostructured (TiCr)CN coating by reactive plasma spraying

In situ nanostructured (TiCr)CN composite coating was prepared by reactive plasma spraying Ti-Cr-graphite powder under air atmosphere. The phase composition, microstructure, mechanical properties and wear performance were investigated. The results show that the coating consists of a mixture of TiN, Ti(CN), (TiCr)N, Cr, Ti₃O, and amorphous graphite and CrN phases. The grain size is about 70 nm and the grains present equiaxed and columnar crystal morphologies. Moreover, 5 nm-sized nanocrystals are embedded in an amorphous phase. The (TiCr)CN composite coating possesses high hardness (1325 ± 120 HV) and toughness (4.35 ± 0.53 MPa m^1/2). The friction coefficient and wear rate of the coating are 0.46 and 3.01 ± 0.17 × 10^?6 mm³ N^?1 m^?1, respectively. The inclusion of metallic phase Cr could improve the toughness and wear resistance of the (TiCr)CN coating.     

In situ investigation by quasi-elastic light scattering of an irreversible sol-gel transition

We report a dynamic light scattering study of semi-dilute solutions of polydisperse branched polymers. The autocorrelation function of the intensity of scattered light exhibits two decay modes. Experiments performed in situ on the sol phase of a system undergoing irreversible gelation show that the slow relaxation time diverges at the sol-gel transition.