Dense nanocrystalline UO2+x fuel pellets synthesized by high pressure spark plasma sintering

Nanocrystalline UO_2+x powders are prepared by high‐energy ball milling and subsequently consolidated into dense fuel pellets (>95% of theoretical density) under high pressure (750 MPa) by spark plasma sintering at low sintering temperatures (600°C‐700°C). The grain size achieved in the dense nano‐ceramic pellets varies within 60‐160 nm as controlled by sintering temperature and duration. The sintered fuel pellets are single phase UO_2+x with hyper‐stoichiometric compositions as derived by X‐ray diffraction, and micro‐Raman measurements indicate that random oxygen interstitials and Willis clusters dominate the single phase nano‐sized oxide pellets of UO_2.03 and UO_2.11, respectively. The thermal conductivities of the densified nano‐sized oxide fuel pellets are measured by laser flash, and the fuel stoichiometry displays a dominant effect in controlling thermal transport properties. A reduction in thermal conductivity is also observed for the dense nano‐sized pellets as compared with micron‐sized counterparts reported in the literature. The correlation among the SPS sintering parameters—microstructure control—properties is established, and the nano‐sized UO_2+x pellets with controlled microstructure can serve as the model systems for fundamental understandings of fuel behaviors and obtaining critical experimental data for multi‐physics MARMOT model validation.     

Preparation of bulk‐nanostructured UO2 pellets using high‐pressure spark plasma sintering for LWR fuel safety assessment

Nuclear fuel undergoes a significant restructuration during its lifetime in the nuclear reactor. Especially at the rim of the pellet, large UO₂ grains disintegrate into a nanosized material. In this paper, we focus on the preparation of bulk UO₂ with grain sizes below 100 nm to investigate the physico‐chemical properties of this so‐called “high burn up structure” (HBS). Preparation of bulk nanocrystalline materials is a challenge that can be overcome using the high‐pressure spark plasma sintering (HP SPS) technique. In‐house developed HP SPS with 500 MPa applied pressure was used for compaction of 11 nm UO₂ powder obtained by oxalate conversion. The procedure yielded dense (>90%) compacts with grain size as low as 34 nm for samples sintered at 800°C.     

Investigation of deformation and pore formation in isotactic polypropylene containing active nano‐CaCO3

In order to improve the β‐lamellae distribution and properties of β‐isotactic polypropylene (β‐iPP) membranes, amounts of 5 and 10% active nano‐CaCO₃ were added into β‐iPP. Differential scanning calorimetry, X‐ray diffraction and scanning electron microscopy results show that nano‐CaCO₃ does not reduce the content of β‐crystals, but the thickness, lamellae thickness distribution and stability of β‐lamellae decrease apparently. Tensile testing was conducted at 25 and 90 °C. The results manifest that the second yield point, which has a strong negative correlation with lamellae thickness distribution, is delayed monotonically with addition of nano‐CaCO₃ when stretched at 25 °C, indicating that nano‐CaCO₃ could narrow effectively the lamellae thickness distribution of β‐iPP. Furthermore, when stretched at 90 °C, the subdued yield peak, retarded necking‐down phenomenon and enhanced strain‐hardening modulus demonstrate that the deformation stability improves gradually with introduction of nano‐CaCO₃, which is completely opposite to the trend for β‐lamellae stability. Through further detailed characterization of morphological evolutions during stretching, we found that interfacial debonding between nano‐CaCO₃ and β‐iPP is triggered and abundant microviods can be formed, which can retard the rotation and slip of β‐lamellae and make the β–α transformation slow down in the initial stage of stretching, consequently leading to better isotropic deformation. Moreover, nano‐CaCO₃ could efficiently restrain the formation of coarse fibrils, leading to more uniform pore size distribution within the biaxial stretching microporous membrane. However, excessive nano‐CaCO₃ (10%) would cause aggregation within the β‐iPP cast film and finally result in larger pores and poor pore distribution in the membrane. © 2017 Society of Chemical Industry     

Preparation and characterization of bipolar membranes modified using photocatalyst nano‐TiO2 and nano‐ZnO

The nano‐ZnO and nano‐TiO₂ were added into chitosan (CS) anion layer to prepare polyvinyl alcohol (PVA) ‐ sodium alginate (SA)/ TiO₂‐ZnO‐CS (here, PVA:polyvinyl alcohol; SA:sodium alginate) bipolar membrane (BPM), which was characterized using scanning electron microscopy, atomic force microscopy (AFM), thermogravimetric analysis (TG), electric universal testing machine, contact angle measurer, and so on. Experimental results showed that nano‐TiO₂‐ZnO exhibited better photocatalytic property for water splitting at the interlayer of BPM than nano‐TiO₂ or nano‐ZnO. The membrane impedance and voltage drop (IR drop) of the BPM were obviously decreased under the irradiation of high‐pressure mercury lamps. At a current density of 60 mA/cm², the cell voltage of PVA‐SA/TiO₂‐ZnO‐CS BPM‐equipped cell decreased by 1.0 V. And the cell voltages of PVA‐SA/TiO₂‐CS BPM‐equipped cell and PVA‐SA/ZnO‐CS BPM‐equipped cell were only reduced by 0.7 and 0.6 V, respectively. Furthermore, the hydrophilicity, thermal stability, and mechanical properties of the modified BPM were increased. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Grain Growth and Twin Formation in 0.74PMN·0.26PT

The mechanisms controlling normal and exaggerated grain growth in lead magnesium niobate–lead titanate (PMN–PT) ceramics have been investigated by varying the PbO-based liquid-phase volume fraction from 0.03 to 0.6 and sintering temperature from 900° to 1100°C. There is a transition in matrix grain growth rate and matrix grain shape with liquid fraction; samples with liquid volume fractions less than ∼0.15 show relatively small equiaxed grains resulting from grain-to-grain impingement. Samples with higher liquid fractions show significantly larger, facetted, cube-shaped grains, whose size is independent of liquid fraction, indicating that a surface nucleation rate mechanism controls growth in this regime. Exaggerated grains were found in the high liquid fraction samples. Electron backscatter diffraction showed that all of the exaggerated grains contained 60°〈111〉 twins but none of the normal matrix grains contained twins. The reentrant angles in the twinned grains give them a growth advantage over untwinned grains, resulting in a population of exaggerated grains.     

Microstructural evolution in infiltration‐growth processed MgB2 bulk superconductors

The study reports phase and microstructural evolution in MgB₂ bulk superconductors fabricated by an infiltration and growth (IG) process. Three distinct stages, (1) intermediate boride formation, (2) bulk liquid Mg infiltration, and (3) MgB₂ layer formation, were identified in IG process after detailed examination of series of samples prepared with varied heating conditions. The intermediate phase Mg₂B₂₅, isomorphous to β‐boron, was detected prior to MgB₂ phase formation in stage (1). Due to volume expansion involved in stage 1, cracks formed in the β‐boron particles and propagated radially inwards during stage 3. The growing MgB₂ particles sintered simultaneously with formation of grain boundaries during the process, as evidenced by the measured hardness and critical current density in these samples. From our observations, we estimate the total time needed for complete transformation to MgB₂.     

Grain growth inhibition by sluggish diffusion and Zener pinning in high-entropy diboride ceramics

This work reported the grain growth kinetics of high-entropy diboride (HEB) and HEB-SiC ceramics containing 10, 20, and 30 vol% SiC during heat treatment at 1800°C. The coarsening of HEB phase occurred in the four kinds of ceramics during heat treatment, especially in HEB ceramics. The kinetic analysis showed that the grain growth of HEB phase in HEB and HEB-SiC ceramics is controlled by interface-controlled kinetics and grain-boundary pinning, respectively. The growth rate constant of HEB grains is lower than ZrB₂, which is related to the low grain-boundary energy and the sluggish diffusion effect in dynamics of high-entropy materials. The growth rate of matrix phase in HEB-SiC ceramics is similar to that in ZrB₂–SiC ceramics, indicating that the pinning effect of the SiC second-phase played the dominant role in inhibiting the grain growth of the high-entropy matrix phase and disguised the sluggish diffusion effect. This study reveals that the grain growth inhibition through sluggish diffusion effect in a high-entropy ceramic system may be magnified by the possible existence of segregated second-phase particles located at the grain boundaries.     

Study on the Effect between Dynamics of MgO Grain Growth and Additive of Y2O3

1IntroductionAdditive agent plays a great role in changingphysical and chemical properties and microstructure ofmaterials,especially in CaO-riched MgO-CaO refracto-ry system.Rare earth elements[1~6]have high electronlevel and special electronic structure …     

Texture Development and Microstructure Evolution in Liquid-Phase-Sintered α-Alumina Ceramics Prepared by Templated Grain Growth

Texture development in alumina that contains calcia and silica and has been templated with platelet-shaped α-Al₂O₃ particles has been evaluated. The texture fraction is shown to be related directly to template growth. Texture quality is controlled by the template concentration, decreasing at template concentrations of >10%, as a result of template–template interactions during tape casting. Almost fully textured alumina has been obtained at template concentrations of ≥20%. The growth of template grains is much more rapid in the radial direction and is shown to be inversely related to the thickness of the grain-boundary liquid. The activation energy for growth (376 kJ/mol) and the inverse relation with the grain-boundary thickness indicate that template growth in the radial direction is controlled by Al³⁺ diffusion.     

Suppressed grain growth in highly porous barium titanate foams by two‐step sintering

Porous barium titanate has gained significant attention in recent years for their potential use in applications such as scaffolds for bone tissue engineering, stress sensors, gas sensors, and many others. However, there is very little control over the grain size of the material during the sintering processes specially to achieve little or no growth of the starting powders. Here, using the two‐step sintering method barium titanate foams were shown to be synthesized with controlled grain size of the struts without significant differences in the pore structure of the materials. In order to evaluate the applicability of two‐step sintering for a variety of processing methods, highly porous (>80% porosity) foams synthesized through the direct polyurethane foaming method were used to create conditions furthest from bulk where two‐step sintering has shown success. Two‐step sintering parameters were identified and the processing conditions were confirmed to not alter the mechanical properties of the samples due to expected residual stresses or thermal shock resulting from the rapid heating and cooling rates employed.     

Preparation and characterization of nano‐SiO2 reinforced alginate‐based nanocomposite films (II)

Crosslinked alginate‐based nanocomposites at different SiO₂ contents were prepared successfully by blending the nano‐SiO₂ solution into low concentration alginate solution (0.5 wt %), with the alginate concentration increased step by step to the resulted concentration, in this course glycerol was used as plasticizer and 5 wt % CaCl₂ as crosslinker. The combined effect of SiO₂ content (1.5–8 wt %) on the microstructural, physical, mechanical, and optical properties of the nanocomposite films were investigated. The results showed that tensile strength and elongation was improved by about 40.33% and 89%, respectively, upon increasing the SiO₂ content to 4.5 wt %. In addition, water vapor permeability and swelling degree decreased by 19% and 16% with increasing SiO₂ content up to 8 and 4.5 wt %, respectively with respect to pure crosslinked alginate film. Thermogravimetric analysis also revealed that nano‐SiO₂ can improve the thermal stability of sodium alginate films produced by this method. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45286.     

Control of pore generation and pore size in nanoparticles of poly(styrene‐methyl methacrylate‐acrylic acid)

Seeded emulsion polymerization of styrene‐methyl methacrylate‐acrylic acid onto seed latexes of monodisperse particles of poly(styrene‐methyl methacrylate) was conducted with or without divinyl benzene as a crosslinking agent. Experiments revealed that almost no new particles were formed during the second stage of polymerization, and that the seeded latex particles obtained were almost monodisperse. An alkali‐acid treatment was then applied to the seeded latex particles swollen in 2‐butanone. Experimental results indicated that: (1) for uncrosslinked particles, an optimum volume expansion of >50% is reached for a ratio of the swelling agent, 2‐butanone, to polymer (methyl‐ethyl‐ketone/polymer by weight) between 2.0 and 2.9; the volume expansion is much lower outside the above range. (2) For crosslinked particles, the particle volume expansion follows the same pattern, but with smaller values. (3) pH plays an important role in pore generation and volume expansion. Pore generation is optimized by decreasing pH to a value as low as 1.5 during acid treatment, and by keeping pH in the optimum range between 11.98 and 12.20 during alkali treatment. Based on the above observations, a discussion regarding the mechanism of pore generation and particle expansion is provided. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 419–426, 1999     

Mechanical properties of 1 mol% CeO2‐10 mol% Sc2O3 co‐doped and stabilized ZrO2 synthesized through hydro/solve‐thermal method

Ultra‐fine 1 mol% CeO₂‐10 mol% Sc₂O₃ co‐doped and stabilized ZrO₂ (1Ce10ScSZ) powders with average grain size less than 10 nm in diameter were prepared by hydro/solve‐thermal method using either deionized water, ethanol, or methanol as solvent. As‐synthesized powders were characterized in terms of phase structure, particle morphology, and chemical composition by X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), high‐resolution transmission electron microscopy (HRTEM), and inductively coupled plasma‐optical emission spectroscopy (ICP‐OES), respectively. Sintering studying was conducted on pellets of 15 mm in diameter and 3 mm in thickness under uniaxial compaction using 25 MPa at either 600, 800, 1000, 1100, 1200, 1400, or 1500°C for 1 hour. Phase transitions and grain morphologies of those sintered samples were characterized by XRD and field emission scanning electron microscopy (FESEM). Mechanical properties were characterized on dense pellets sintered at 1500°C by nanoindentation. Experimental results showed that ethanol was more effective to synthesize agglomerate‐free 1Ce10ScSZ powders as compared with deionized water and methanol. Choice of solvent affected the environment of hydro/solve‐thermal solution, which led to variation of chemical compositions of powders and porosities of sintered pellets, and therefore, influenced their mechanical performance. Our study showed that solvent was important to make dense, thin, and mechanically robust 1Ce10ScSZ electrolyte for potential applications in electrochemical devices. Absolute values of hardness (H) and Young's modulus (E) measured from our samples are much higher and more consistence than those results obtained from commercial vendors reported in literatures.     

Stability and electrical properties of MoSi2‐ and WSi2‐oxide electroconductive composites

MoSi₂‐ and WSi₂‐based electroconductive ceramic composites were fabricated using 40‐80 vol% fine‐ and coarse‐Al₂O₃, and ZrO₂ particles (refractory oxides) after sintering in argon. Their chemical and thermal stability was tested between 1400°C‐1600°C for up to 48 hours. X‐ray diffraction analysis showed the formation of secondary 5‐3 metal silicide (Mo₅Si₃, W₅Si₃) and silica phases on the grain boundaries and surface. The fraction of the W₅Si₃ (11.4‐38.8 vol%) was significantly higher than that of the Mo₅Si₃ (3.3‐7.3 vol%) in the composites after annealing at 1400°C for 48 hours. The rates of grain growth in the composites (0.013‐0.023 μm/h) were highly decreased by a grain‐boundary pinning effect. This effect was relatively better with the addition of the coarse‐grained oxides due to their more homogeneous distribution throughout the microstructure. The 20–80 vol% MoSi₂‐Al₂O₃ (fine‐grained) composite exhibited an electrical conductivity of 8.8 S/cm at 900°C. At the 60 vol% silicide content, MoSi₂–Al₂O₃ (coarse‐grained) and WSi₂–Al₂O₃ (fine‐grained) showed higher electrical conductivity (126‐128 S/cm) at 900°C. The density, porosity level, particle distribution, intrinsic conductivity of silicide phase, particle size, and fraction of the secondary 5‐3 silicide phase highly influenced their electrical properties.     

Preparation and performance of high‐impact polystyrene (HIPS)/nano‐TiO2 nanocomposites

High‐impact polystyrene (HIPS)/nano‐TiO₂ nanocomposites were prepared by surface pretreatment of nano‐TiO₂ with special structure dispersing agent (TAS) and master batch manufacturing technology. The results show that when the nano‐TiO₂ content is 2%, the notched impact strength, tensile strength, and elastic modulus of HIPS/nano‐TiO₂ nanocomposites increased to a maximum. This result indicates that nano‐TiO₂ has both toughening and reinforcing effects on HIPS. The heat‐deflection temperature and flame‐retardance of HIPS/nano‐TiO₂ nanocomposites are also obviously improved as the nano‐TiO₂ content is increased. The nanocomposites manufactured by the two‐step method have better mechanical properties than that made by a one‐step method. HIPS/nano‐TiO₂ nanocomposites are also non‐Newtonian and pseudoplastic fluids. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 381–385, 2003     

Pervaporation of methanol/dimethyl carbonate using SiO2 membranes with nano‐tuned pore sizes and surface chemistry

Porous silica membranes with different pore sizes (average pore size: 0.3–1.2 nm) and surface chemistry were prepared from SiO₂, steam‐treated SiO₂, SiO₂? ZrO₂, and SiO₂? TiO₂ by sol‐gel processing, and were applied to the pervaporation (PV) separation of methanol (MeOH) /dimethyl carbonate (DMC) mixtures at 50°C. Although SiO₂? ZrO₂ membranes demonstrated a separation factor of <10, the SiO₂ porous membranes had an increased separation factor from 10–160. Silica membranes with an average pore size of 0.3 nm showed the highest permselectivity of methanol with a separation factor of 140 and a methanol flux of 180 mol/(m²h) for MeOH 50 mol% at 50°C. To characterize the surface property of SiO₂ membranes, SiO₂ powdered samples were used for an adsorption experiment of vapor (MeOH, DMC) in single and mixed systems, revealing increased MeOH selective adsorption for SiO₂ powders with hydrophilic and small pores, which was consistent with PV performance. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Microstructure in Silicon Nitride Containing β-Phase Seeding: III, Grain Growth and Coalescence

The mechanical properties of Si₃N₄ materials depend mainly on the microstructure, which originates during the densification process. The microscopic evidence indicates that β-Si₃N₄ seeds incorporated in the starting powders play an important role in microstructural development, especially in the heterogeneous grain growth of β-Si₃N₄ grains during sintering. The growth of β-grains is initiated from the β-seeds, resulting in a core/shell microstructure. The presence of Moiré fringes and dislocations is attributed to misfit strain and compositional differences between the core and the shell. Coalescence can occur at the final stage of sintering.     

Grain boundary driven mechanical properties of ZrB2 and ZrC‐ZrB2 nanocomposite: A molecular simulation study

In this study, we report the grain boundary driven mechanical behavior of 2 polycrystalline ultra‐high‐temperature ceramics (UHTCs), zirconium diboride (ZrB₂) and zirconium carbide (ZrC) with zirconium diboride (ZrC‐ZrB₂). These nanocomposites were investigated using large‐scale molecular dynamics simulations. First, the atomistic models of the polycrystalline ZrB₂ and ZrC‐ZrB₂ nanocomposites were subjected to tensile loading to determine their elastic constants and tensile strengths. It was found that the presence of nanoparticles imparts an insignificant effect on the mechanical properties of ZrB₂. It has also been observed that the failure mechanisms of both the ZrB₂ and ZrC‐ZrB₂ nanocomposite are driven by grain boundary deformation. At any instant during the applied load transfer, local tensile stress distribution data indicate that atomic stress becomes much higher near the grain boundaries compared to other locations. The authors performed additional sets of simulations to obtain tensile and shear properties of grain boundary material. When these properties were compared with the adjacent single crystal and overall polycrystalline material properties, it was found that the shear strength and stiffness of the grain boundary materials are significantly lower than the single crystal or polycrystal ZrB₂. It is believed that the overall deformation and failure properties of ZrB₂ and its composite are controlled by the properties of grain boundary. Hence, the addition of nanoparticles played an insignificant role on the mechanical properties of ZrB₂.     

The influence of interphase on nylon‐6/nano‐SiO2 composite materials obtained from in situ polymerization

Three commercially available silane, titanate and aluminate based coupling agents were used to pretreat nano‐SiO₂ for the preparation of nylon‐6/nano–SiO₂ composites via in situ polymerization. The interphases formed in different composite systems and their influence on material properties were investigated. Results indicated that the interfacial interactions differed between composite systems, whereas rigidity and toughness of composites were all improved by addition of pretreated silicas at an optimal content of 4.3 wt%. The presence of pretreated silicas did not have a distinct influence in the non‐isothermal crystallization behaviour of the nylon matrix. The composites containing pretreated silicas had slightly higher dynamic viscosities and superior storage moduli at high frequency, compared with neat nylon‐6. Copyright © 2003 Society of Chemical Industry