Combustion and Ball Milled Synthesis of Rare Earth Nano-Sized Ceria Powder

This paper reports a study on nanocrystalline ceria powder prepared by high energy ball-milling and combustion synthesis methods. The combustion synthesis was carried out using ceric ammonium nitrate as oxidizer and citric acid, glycine or citric acid plus glycine as fuel. The minimum crystallite size of ceria powder is obtained by combustion synthesis of ceric ammonium nitrate and citric acid. The ceria powder produced by combustion synthesis of ceric ammonium nitrate and citric acid and glycine has less agglomeration of particles than other techniques.

Synthesizing active and durable cubic ceria catalysts(<6 nm)for fast dehydrogenation of bio-polyols to carboxylic acids coproducing green H_(2)

Dehydrogenation is considered as one of the most important industrial applications for renewable energy.Cubic ceria-based catalysts are known to display promising dehydrogenation performances in this area.Large particle size(>20 nm)and less surface defects,however,hinder further application of ceria materials.Herein,an alternative strategy involving lactic acid(LA)assisted hydrothermal method was developed to synthesize active,selective and durable cubic ceria of<6 nm for dehydrogenation reactions.Detailed studies of growth mechanism revealed that,the carboxyl and hydroxyl groups in LA molecule synergistically manipulate the morphological evolution of ceria precursors.Carboxyl groups determine the cubic shape and particle size,while hydroxyl groups promote compositional transformation of ceria precursors into CeO_(2) phases.Moreover,enhanced oxygen vacancies(Vo)on the surface of CeO_(2) were obtained owing to continuous removal of O species under reductive atmosphere.Cubic CeO_(2) catalysts synthesized by the LA-assisted method,immobilized with bimetallic PtCo clusters,exhibit a record high activity(TOF:29,241 h^(-1))and Vo-dependent synergism for dehydrogenation of bio-derived polyols at 200℃.We also found that quenching Vo defects at air atmosphere causes activity loss of PtCo/CeO_(2) catalysts.To regenerate Vo defects,a simple strategy was developed by irradiating deactivated catalysts using hernia lamp.The outcome of this work will provide new insights into manufacturing durable catalyst materials for aqueous phase dehydrogenation applications.

Synthesis of Nano-sized Yttria via a Sol-Gel Process Based on Hydrated Yttrium Nitrate and Ethylene Glycol and Its Catalytic Performance for Thermal Decomposition of NH_4ClO_4

Nano-sized yttria particles were synthesized via a non-aqueous sol-gel process based on hydrated yttrium nitrate and ethylene glycol. The effects of the molar ratio of ethylene glycol to yttrium ion and calcination temperature on crystallite size of the products were studied. The catalytic performance of the as-prepared yttria for the ammonium perchlorate （AP） decomposition was investigated by differential scanning calorimetry （DSC）. The results indicate that the nano-sized cubic yttria particles with less than 20 nm in average crystallite size can be obtained after 2 h reflux at 70℃, dried at 90 ℃, forming xerogel, and followed by annealing of xerogel for 2 h, and that the addition of the nano-sized yttria to AP incorporates two small exothermic peaks of AP in the temperature ranges of 310 - 350 ℃ and 400 - 470 ℃ into a strong exothermic peak of AP and increases the apparent decomposition heat from 515 to over 1110 J·g^- 1. It is also clear that the temperature of AP decomposition exothermic peak decreases and the apparent decomposition heat of AP increases with the increase of the amount of nano-sized yttria. The fact that the addition of the 5 % nano-sized yttria to AP decreases the temperature of AP exothermic peak to 337.7℃ by reduction of 114.6℃ and increases the apparent decomposition heat from 515 to 1240 J·g^-1, reveals that nano-sized yttria shows strong catalytic property for AP thermal decomposition.

NiMo/Al_2O_3 catalyst containing nano-sized zeolite Y for deep hydrodesulfurization and hydrodenitrogenation of diesel

Two mixed-matrix NiMo/Al2O3 catalysts containing nano-and micro-sized zeolite Y have been prepared to explore the size effect of zeolite Y particle on the hydrodesulfurization（HDS）and hydrodenitrogenation（HDN）activities of fluid catalytic cracking（FCC）diesel.They were characterized by SEM,BET,XRD,H2-TPR,NH3-TPD and HRTEM.The results show that the catalyst containing nano-sized zeolite Y possesses larger average pore diameter,higher pore volume,weaker and lesser acid sites,more easily reducible metal phases,shorter MoS2 slabs and more slab layers than the catalyst containing micro-sized zeolite Y.The catalysts were also evaluated with a high-pressure fixed-bed reactor using real FCC diesel as feed.The results display that the catalyst containing nano-sized zeolite Y bears higher HDS and HDN activities and exhibits higher relative rate constant for the removal of total sulfur or nitrogen than the one containing micro-sized zeolite.

Synthesis and Characterization of Nano-sized Boron Powder Prepared by Plasma Torch

Hydrogen thermal plasma jet was employed to prepare nano-sized boron powder with hydrogen reduction of BCI3. The maximum yield of nano-sized boron powders was about 50% with the operational conditions of H2/BCl3 of 4.5：1, total feed of 4.9 m3/h, and plasma power of 25 kW. The samples were analyzed by X-ray diffraction （XRD）, field emission scanning electron microscopy （FE-SEM）, and inductively coupled plasma - mass spectrometry （ICP-MS）, inductively coupled plasma - atomic emission spectrometry （ICP-AES）, inductive combustion infrared absorption （ICIA） and infrared thermal conductivity of oxygen and nitrogen analyzer （ITCA）. The results show that the boron powders have different crystal structures with higher dispersion and purity. The average diameter is about 50 nm, and the purity is 90.29% or so. This new technology can use simple process to produce high quality boron powders, and is feasible for industrial production.

Kinetics and Mechanism of Decomposition of Nano-sized Calcium Carbonate under Non-isothermal Condition

Experiments on thermal decomposition of nano-sized calcium carbonate were carried out in a thermo-gravimetric analyzer under non-isothermal condition of different heating rates (5 to 20K·min-1). The Coats and Redfern's equation was used to determine the apparent activation energy and the pre-exponential factors. The mechanism of thermal decomposition was evaluated using the master plots, Coats and Redfern's equation and the kinetic compensation law. It was found that the thermal decomposition property of nano-sized calcium carbonate was different from that of bulk calcite. Nano-sized calcium carbonate began to decompose at 640℃, which was 180℃lower than the reported value for calcite. The experimental results of kinetics were compatible with the mechanism of one-dimensional phase boundary movement. The apparent activation energy of nano-sized calcium carbonate was estimated to be 151kJ·mol-1 while the literature value for normal calcite was approximately 200kJ·mol-1. The order of magnitude of pre-exponential factors was estimated to be 10~9 s-1.

Corrosion resistance of waterborne epoxy coating pigmented by nano-sized aluminium powder on steel

A novel kind of waterborne epoxy coating pigmented by nano-sized aluminium powders on high strength steel was formulated. Several coatings with different pigment volume content (PVC) were prepared. The coating morphology was observed using scanning electron microscopy (SEM), and the electrochemical properties were investigated by electrochemical impedance spectroscopy (EIS). Immersion test and neutral salt spray test were also conducted to investigate the corrosion resistance of the coating. It is demonstrated that the critical pigment volume content (CPVC) value is between 30% and 40%. The coating with PVC of 30% exhibits good corrosion resistance in 3.5% (mass fraction) NaCl solution.

Effects of nano-sized aluminum on detonation characteristics and metal acceleration for RDX-based aluminized explosive

Nano-sized aluminum(Nano-Al)powders hold promise in enhancing the total energy of explosives and the metal acceleration ability at the same time.However,the near-detonation zone effects of reaction between Nano-Al with detonation products remain unclear.In this study,the overall reaction process of 170 nm Al with RDX explosive and its effect on detonation characteristics,detonation reaction zone,and the metal acceleration ability were comprehensively investigated through a variety of experiments such as the detonation velocity test,detonation pressure test,explosive/window interface velocity test and confined plate push test using high-resolution laser interferometry.Lithium fluoride(LiF),which has an inert behavior during the explosion,was used as a control to compare the contribution of the reaction of aluminum.A thermochemical approach that took into account the reactivity of aluminum and ensuing detonation products was adopted to calculate the additional energy release by afterburn.Combining the numerical simulations based on the calculated afterburn energy and experimental results,the parameters in the detonation equation of state describing the Nano-Al reaction characteristics were calibrated.This study found that when the 170 nm Al content is from 0%to 15%,every 5%increase of aluminum resulted in about a 1.3%decrease in detonation velocity.Manganin pressure gauge measurement showed no significant enhancement in detonation pressure.The detonation reaction time and reaction zone length of RDX/Al/wax/80/15/5 explosive is 64 ns and 0.47 mm,which is respectively 14%and 8%higher than that of RDX/wax/95/5 explosive(57 ns and 0.39 mm).Explosive/window interface velocity curves show that 170 nm Al mainly reacted with the RDX detonation products after the detonation front.For the recording time of about 10 ms throughout the plate push test duration,the maximum plate velocity and plate acceleration time accelerated by RDX/Al/wax/80/15/5 explosive is 12%and 2.9 ms higher than that of RDX/LiF/wax/80/15/5,respectively,indicating that the aluminum reaction energy significantly increased the metal acceleration time and ability of the explosive.Numerical simulations with JWLM explosive equation of state show that when the detonation products expanded to 2 times the initial volume,over 80%of the aluminum had reacted,implying very high reactivity.These results are significant in attaining a clear understanding of the reaction mechanism of Nano-Al in the development of aluminized explosives.

Effect of deep cryogenic treatment on the formation of nano-sized carbides and the wear behavior of D2 tool steel

The effect of deep cryogenic treatment on the microstructure, hardness, and wear behavior of D2 tool steel was studied by scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, X-ray diffraction （XRD）, hardness test, pin-on-disk wear test, and the reciprocating pin-on-fiat wear test. The results show that deep cryogenic treatment eliminates retained austenite, makes a better carbide distribution, and increases the carbide content. Furthermore, some new nano-sized carbides form during the deep cryogenic treatment, thereby increasing the hardness and improving the wear behavior of the samples.

Deformation behavior of explosive detonation in electroformed nickel liner of shaped charge with nano-sized grains

Nickel liner of shaped charge with nano-sized grains was prepared by electroforming technique and the ultra-highstrain-rate deformation was performed by explosive detonation.The as-electroformed and post-deformed microstructures of electroformed nickel liner of shaped charge were observed by optical metallography(OM),scanning electron microscopy(SEM) and transmission electron microscopy(TEM) and the orientation distribution of the grains was analyzed by electron backscattering pattern(EBSP) technique.Both melting phenomenon in the jet fragment and recovery and recrystallization in the slug after ultra-high-strain-rate deformation were observed.The research evidence shows that dynamic recovery and recrystallization play an important role in ultra-high-strain-rate deformation for electroformed nickel liner of shaped charge with nano-sized grain.

Comparative study of the explosion pressure characteristics of micro- and nano-sized coal dust and methane–coal dust mixtures in a pipe

Coal dust explosion accidents often cause substantial property damage and casualties and frequently involve nano-sized coal dust.In order to study the impact of nano-sized coal on coal dust and methane–coal dust explosions,a pipe test apparatus was used to analyze the explosion pressure characteristics of five types of micro-nano particle dusts(800 nm,1200 nm,45μm,60μm,and 75μm)at five concentrations(100 g/m3,250 g/m3,500 g/m3,750 g/m3,and 1000 g/m3).The explosion pressure characteristics were closely related to the coal dust particle size and concentration.The maximum explosion pressure,maximum rate of pressure rise,and deflagration index for nano-sized coal dust were larger than for its micro-sized counterpart,indicating that a nano-sized coal dust explosion is more dangerous.The highest deflagration index Kst for coal dust was 13.97 MPa/(m·s),indicating weak explosibility.When 7%methane was added to the air,the maximum deflagration index Kst for methane–coal dust was 42.62 MPa/(m·s),indicating very strong explosibility.This indicates that adding methane to the coal dust mixture substantially increased the hazard grade.

Synthesis of Neodymium-Doped Yttrium Aluminum Garnet (Nd∶YAG) Nano-Sized Powders by Low Temperature Combustion

The homogeneously dispersed, less agglomerated (Nd0.01Y0.99)3Al5O12 nano-sized powders were synthesized by the low temperature combustion (LCS), using Nd2O3, Y2O3, Al(NO3)3·9H2O, ammonia water and citric acid as starting materials. This method effectively solves the problems caused by solid-state reaction at high temperature and hard agglomerates brought by the chemical precipitation method. The powders were characterized by TG-DTA, XRD, FT-IR, TEM respectively and the photoluminescence (PL) spectra of (Nd0.01Y0.99)3Al5O12 green and sintered ceramic disks were measured. The results show that the forming temperature of YAG crystal phase is 850 ℃ and YAP crystal phase appearing during the calcinations transforms to pure YAG at 1050 ℃. The particle size of the powders synthesized by the LCS is in a range of 20～50 nm depending on the thermal treatment temperatures. The effectively induced cross section (σin) with the value 4.03×10-19 cm2 of (Nd0.01Y0.99)3Al5O12 ceramics is about 44% higher than that of single crystal.

Seed-Assisted Synthesis and Catalytic Performance of Nano-sized ZSM-5 Aggregates in a One-Step Crystallization Process

Hierarchical nano-sized ZSM-5 aggregates were successfully synthesized via a seed-assisted method in the presence of cetyltrimethylammonium bromide(CTAB)through a facile one-step crystallization process.Commercial ZSM-5 zeolites with a SiO2/Al2O3 ratio comparable to that of ZSM-5 products were treated with alkali and used as the seed particles.The influences of crystallization conditions were investigated,and the possible synthesis mechanism was proposed.ZSM-5 zeolites with diff erent amounts of CTAB added were characterized using many techniques and evaluated in toluene alkylation with methanol.The results showed that a trace amount of CTAB signifi cantly promoted the crystallization of ZSM-5 zeolite,with the morphology changing from hexagonal-shape crystals to uniform spherical aggregates.CTAB may act as the structure-directing agent and assemble the primary crystallites to generate hierarchical ZSM-5 aggregates.The ZSM-5 zeolite with the smallest primary particles of 50-80 nm exhibited large specific surface area,abundant mesopores,and the greatest microporosity.The hierarchical nano-sized ZSM-5 aggregate showed higher toluene conversion and a longer lifetime without compromising the selectivity to xylene and p-xylene in toluene alkylation with methanol.

Fabrication of Fine-Grained Si_3N_4-Si_2N_2O Composites by Sintering Amorphous Nano-sized Silicon Nitride Powders

Si3N4-Si2N2O composites were fabricated with amorphous nano-sized silicon nitride powders by the liquid phase sintering （ LPS ）. The Si2 N2O phase was generated by an in-situ reaction 2 Si3 N4 （ s ） ＋ 1.5 02 （ g ） = 3 Si2 N2O （ s ） ＋ N2 （ g ） . The content of Si2 N2 O phase up to 60% in the volume was obtained at a sintering temperature of 1 650℃ and reduced when the sintering temperature increased or decreased, indicating the reaction is reversible. The mass loss, relative density and average grain size increased with increasing the sintering temperature. The average grain size was less than 500 nm when the sintering temperature was below 1 700 ℃. The sintering procedure contains a complex crystallization and a phase transition ： amorphous silicon nitride→equiaxial α- Si3 N4→ equiaxial β- Si3 N4→ rod- like Si2 N2O→ needle- like β- Si3N4 . Small round-shaped β→ Si3 N4 particles were entrapped in the Si2 N2O grains and a high density of staking faults was situated in the middle of Si2 N2O grains at a sintering temperature of 1 650 ℃. The toughness inereased from 3.5 MPa·m^1/2 at 1 600 ℃ to 7.2 MPa· m^1/2 at 1 800 ℃ . The hardness was as high as 21.5 GPa （Vickers） at 1 600 ℃ .

Effect of nano-sized Al2O3 reinforcing particles on uniaxial and high cycle fatigue behaviors of hot-forged AZ31B magnesium alloy

The effect of hot-forging process was investigated on microstructural and mechanical properties of AZ31 B alloy and AZ31 B/1.5 vol.%Al2 O3 nanocomposite under static and cycling loading. The as-cast alloy and composite were firstly subjected to a homogenization heat treatment at 450 ℃ and then an open-die forging at 450 ℃. The results indicated that the presence of reinforcing particles led to grain refinement and improvement of dynamic recrystallization. The forging process was more effective to eliminate the porosity in the cast alloy workpiece. Microhardness of the forged composite was increased by up to 80% and 16%, in comparison with those of the cast and forged alloy samples, respectively. Ultimate tensile strength and maximum tensile strain of the composite were improved by up to 45% and 23%, compared with those of the forged alloy in similar regions. These enhancements were respectively 50% and 37% in the compression test. The composite exhibited a fatigue life improvement in the region with low applied strain;however, a degradation was observed in the high applied strain region. Unlike AZ31 B samples, tensile, compressive and high cycle fatigue behaviors of the composite showed less sensitivity to the applied strain, which can be attributed to the amount of porosity in the samples before and after the hot-forging.

Fluoride-mediated nano-sized high-silica ZSM-5 as an ultrastable catalyst for methanol conversion to propylene

Fluoride mediated nano-sized ZSM-5 （ZSM-5-F） with a high Si/AI ratio of 181 was fabricated using a seed-induction method and evaluated the catalysis of the methanol to propylene （MTP） reaction. High propylene selectivity （45%） was similar to ZSM-5-OH synthesized via a hydroxide route. However, ZSM- 5-F showed much longer lifetime （305 h） compared with ZSM-5-OH （157 h） in spite of similar crystal size and aluminum content. Characterization by NH3-TPD. Py-IR, OH-IR, SEM, TG-DTA, XRD and 1H MAS NMR techniques indicated that the enhanced catalytic performance of ZSM-S-F is attributed to the fewer structural defects in the form of internal silanol groups and silanol nests.

Preparation and Mechanical Properties of Micro- and Nano-sized SiC/Fluoroelastomer Composites

Microand nano-sized SiC/fluoroelastomer （FKM） composites were prepared by a mechanical mixing method. These composites were first characterized by a rotorless rheometer. Then the effects of micro- and nano-sized SiC on hardness, static and dynamic mechanical properties of the composites were investigated. The increasing amount of the SiC filler increased the curing efficiency of the biphenyl curing system, which was evident from the rheometric properties of the resulting composites. The tensile properties of composite increased with the increasing of micro- and nano-sized SiC content. When the micro- and nano-sized SiC content was higher than 20 phr, the composites showed almost unchanged tensile properties. The increasing of the tensile property was mainly attributed to the well dispersed micro- and nano-sized SiC particles characterized by SEM images. Compared to pure FKM, the composites exhibited a higher glass transition temperature and lower tan peak value.

A Facile Route for Synthesis of LiFePO_4/C Cathode Material with Nano-sized Primary Particles

A facile and practical route was introduced to prepare LiFePO4/C cathode material with nano-sized primary particles and excellent electrochemical performance. LiH2PO4 was synthesized by using H3PO4 and LiOH as raw materials. Then, as-prepared LiH2PO4, reduced iron powder andα-D-glucose were ball-milled, dried and sin-tered to prepare LiFePO4/C. X-ray diffractometry was used to characterize LiH2PO4, ball-milled product and LiFePO4/C. Differential scanning calorimeter-thermo gravimetric analysis was applied to investigate possible reac-tions in sintering and find suitable temperature for LiFePO4 formation. Scanning electron microscopy was em-ployed for the morphology of LiFePO4/C. As-prepared LiH2PO4 is characterized to be in P21cn（33） space group, which reacts with reduced iron powder to form Li3PO4, Fe3（PO4）2 and H2 in ball-milling and sintering. The appro-priate temperature for LiFePO4/C synthesis is 541.3-976.7 ℃. LiFePO4/C prepared at 700 ℃ presents nano-sized primary particles forming aggregates. Charge-discharge examination indicates that as-prepared LiFePO4/C displays appreciable discharge capacities of 145 and 131 mA·h·g^-1 at 0.1 and 1 C respectively and excellent discharge ca-pacity retention.

Enhancing the Deactivation Durability of Nano-sized HZSM-5 for Aromatization by Adjusting its Ratio of Lewis/Brφnsted Acid Sites

Ratio of Lewis/Brfnsted acid sites (Cl/Cb) on the surface of nano-sized HZSM-5 was successfully manipulated by means of steaming and acid leaching. Significant enhancement of the deactivation durability of nano-sized HZSM-5 in the aromatization of fluid catalytic cracking (FCC) gasoline olefins seems to be closely related to the increase of Lewis/Brfnsted acid sites ratio.

Mechanism of expanding swept volume by nano-sized oil-displacement agent

The effect of expanding swept volume by iNanoW1.0 nanoparticles in ultra-low permeability core was studied by low-field nuclear magnetic resonance(LF-NMR)technology,and the mechanism of expanding swept volume was explained by oxygen spectrum nuclear magnetic resonance(17O-NMR)experiments and capillarity analysis.The results of the LF-NMR experiment show that the nano-sized oil-displacement agent iNanoW1.0 could increase the swept volume by 10%-20%on the basis of conventional water flooding,making water molecules get into the low permeable region with small pores that conventional water flooding could not reach.17O-NMR technique and capillary analysis proved that iNanoW1.0 nanoparticles could weaken the association of hydrogen bonds between water molecules,effectively change the structure of water molecular clusters,and thus increasing the swept volume in the low permeable region.The ability of weakening association of hydrogen bonds between water molecules of iNanoW1.0 nanoparticles increases with its mass fraction and tends to be stable after the mass fraction of 0.1%.