Effect of pH on Crystallization of Nanocrystalline Zirconia in a Microwave-hydrothermal Process

Nanocrystalline zirconia（ZrO） was synthesized using a microwave-hydrothermal process.The effect of pH on the crystallization of the ZrO2 powders was investigated.The phase and microstructure of ZrO2 powders were examined using X-ray diffraction（XRD）,Raman spectroscopy,and transmission electron microscopy（TEM）.Results show that pure m-ZrO2 can be obtained at low pH（pH＆lt;2）.Pure t-ZrO2 is formed at pH = 7 and 14.The size of the ZrO2 crystals is in the range of 8-26 nm and decreases with increasing pH.The formation of m-ZrO2 results from the precipitation of ZrO2 from solution.The t-ZrO2 is formed through the in-situ structural rearrangement of amorphous Zr（OH）xOy.The stabilization of t-ZrO2 is attributed to the small crystal size and the adsorption of hydroxy ions on the surfaces of the crystals.

Influence of heat treatment on nanocrystalline zirconia powder and plasma-sprayed thermal barrier coatings

Nanostructured zirconia top coat was deposited by air plasma spray and NiCoCrAlTaY bond coat was deposited on Ni substrate by low pressure plasma spray.Nanostructured and conventional thermal barrier coatings were heat-treated at temperature varying from 1050 to 1 250oC for 2-20 h.The results show that obvious grain growth was found in both nanostructured and conventional thermal barrier coatings(TBCs)after high temperature heat treatment.Monoclinic/tetragonal phases were transformed into cubic phase in the agglomerated nano-powder after calcination.The cubic phase content increased with increasing calcination temperature.Calcination of the powder made the yttria distributed on the surface of the nanocrystalline particles dissolve in zirconia when grains grew.Different from the phase constituent of the as-sprayed conventional TBC which consisted of diffusionlesstransformed tetragonal,the as-sprayed nanostructured TBC consisted of cubic phase.

Preliminary Synthesis and Characterization of Mesoporous Nanocrystalline Zirconia

A novel method to prepare mesoporous nano-zirconia was developed. Thesynthesis was carried out in the presence of PEO surfactants via a solid-state reaction. Thematerials exhibit a strong diffraction peak at low 2θ angle and their nitrogenadsorption/desorption isotherms are typical of type IV with H1 hysteresis loops. The pore structureimaged by TEM can be described as wormhole domains. The tetragonal zirconia nanocrystals are uniformin size (around 1.5 nm) and their mesopores focus on around 4.6 nm. The zirconia nanocrystal growthis tentatively postulated to be the result of an aggregation mechanism. This study also revealsthat the PEO surfactants can interact with the Zr-O-Zr framework to reinforce the thermal stabilityof zirconia. The ratio of NaOH to ZrOCl_2, crystallization and calcination temperature play animportant role in the synthesis of mesoporous nano-zirconia.

Particle growth mechanism of nanocrystalline zirconia powder during high temperature heat treatment

Agglomerated nanocrystalline ZrO2-8%Y2O3 powder prepared by spray drying was heat-treated in air at temperatures from 1200 ℃ to 1400 ℃ for 2 h. Scanning electron microscopy was used to examine the changes of particle size and morphology, and X-ray diffraction was used to analyze the change of constituent phases before and after the high temperature heat treatment. Nano-particle growth behavior was also investigated. The results show that the major constituent phase of the agglomerated nanocrystalline powder is tetragonal, and non-uniform growth of the nano-particles occurs while the heat treatment temperature reaches 1 300 ℃. This non-uniform growth phenomenon is related with the inhomogeneous distribution of Y2O3 in ZrO2. Nano-particles grow into micron particles through the mechanisms of gradual merging of nano-particles in some areas and sudden merging of nano-particles in other areas.

Quasi-plastic deformation mechanisms and inverse Hall-Petch relationship in nanocrystalline boron carbide under compression

Grain boundaries(GBs)play a significant role in the deformation behaviors of nanocrystalline ceramics.Here,we investigate the compression behaviors of nanocrystalline boron carbide(nB_(4)C)with varying grain sizes using molecular dynamics simulations with a machine-learning force field.The results reveal quasi-plastic deformation mechanisms in nB_(4)C:GB sliding,intergranular amorphization and intragranular amorphization.GB sliding arises from the presence of soft GBs,leading to intergranular amorphization.Intragranular amorphization arises from the interaction between grains with unfavorable orientations and the softened amorphous GBs,and finally causes structural failure.Furthermore,nB_(4)C models with varying grain sizes from 4.07 nm to 10.86 nm display an inverse Hall-Petch relationship due to the GB sliding mechanism.A higher strain rate in nB_(4)C often leads to a higher yield strength,following a 2/3 power relationship.These deformation mechanisms are critical for the design of ceramics with superior mechanical properties.

Study on Acoustic Emission Characteristics of Deformation Damage Process of Zirconia Ceramics

Zirconia ceramics have become increasingly widely used in recent years and are favored by relevant enterprises. From the traditional dental field to aerospace, parts manufacturing has been used, but there is limited research on the deformation and damage process of zirconia ceramics. This article analyzes the acoustic emission characteristics of each stage of ceramic damage from the perspective of acoustic emission, and explores its deformation process characteristics from multiple perspectives such as time domain, frequency, and EWT modal analysis. It is concluded that zirconia ceramics exhibit higher brittleness and acoustic emission strength than alumina ceramics, and when approaching the fracture, it tends to generate lower frequency acoustic emission signals.

Optimizing the Preparation Parameters of Nanocrystalline Zirconia for Catalytic Applications

Nanocrystalline zirconia powder with high surface area and high tetragonal phase percentage is prepared by the precipitation method using ammonium hydroxide as a precipitating agent. The pH of precipitation, preparation temperature and calcinations＇ temperature are optimized.Crystallite size, specific surface area, tetragonal phase percentage and the thermal stability of the prepared samples are identified by diferent characterization tools such as X-ray difraction（XRD）, thermo gravimetric analysis（TGA）, diferential scanning calorimetry（DSC）, BET surface area, scanning electron microscopy（SEM） and transmission electron microscopy（TEM）. The optimum preparation parameters for obtaining nanocrystalline zirconia with high percentage of tetragonal phase and high surface area are pH 9, preparation temperature of 80℃ and calcinations＇ temperature of 400℃. The sample prepared under optimized conditions showed a high specific surface area of 179.2 m2/g, high tetragonal phase percentage of 81% and high catalytic activity（60%） for synthesis of butyl acetate ester.

Replacement of Unesthetic Posterior Metal Crowns with Monolithic Zirconia Crowns: A Case Report

Advances in metal-free materials and the popularization of Computer-Aided Design and Manufacturing (CAD/CAM) have led to the wide clinical use of all-ceramic crowns for esthetic restorations. A 72-year-old woman presented to our hospital with unesthetic restorations on the right upper and lower posterior teeth. Intraoral examination revealed poorly fitting metal crown margins. Defective prostheses were removed, and provisional restorations were provided to stabilize the mandibular position. Optical impressions and the maxillomandibular relationship were recorded using an intraoral scanner, and monolithic zirconia crowns were fabricated using CAD/CAM technology for complete veneer crown restorative treatment. Occlusal examination revealed an improvement in occlusal force distribution at initial examination (right side: 33.5%, left side: 66.5%) after placement of the zirconia crowns (right side: 54.9%, left side: 45.1%). Occlusal force and occlusal force distribution area also showed an increasing trend. The Oral Health Impact Profile short form (OHIP-14) score decreased from 7 points at initial examination to 0 points after prosthodontic treatment. Appropriate diagnosis and treatment planning contributed to the increased occlusal force and balanced occlusal force distribution. Therefore, the present case indicates the potential of monolithic zirconia crowns to achieve both esthetic and stable functional outcomes.

Formation of nanocrystalline AZ31B Mg alloys via cryogenic rotary swaging

A bulk nanocrystalline AZ31B Mg alloy with extraordinarily high strength was prepared via cryogenic rotary swaging in this study.The obtained alloy shows finer grains,higher strength,and a negligible tension-compression yield asymmetry,compared with that prepared via room-temperature rotary swaging.Transmission electron microscopy investigations showed that at the initial stage,multiple twins,mostly tension twins,were activated and intersected with each other,thereby refining the coarse grains into a fine lamellar structure.Then,two types of nanoscale subgrains were generated with increasing swaging strain.The first type of nanoscale subgrain contained twin boundaries and low-angle grain boundaries.This type of subgrain appeared at the twin-twin intersections and was mainly driven by high local stress.The second type of nanoscale subgrain was formed within the twin lamellae.The boundaries of this type of subgrain did not contain twin boundaries and were transformed from massive dislocation arrays.Finally,randomly oriented nanograins were obtained via dynamic recrystallization,under the combined function of deformation heat and increased stored energy.Compared with room-temperature rotary swaging,cryogenic rotary swaging exhibits a slower grain refinement process but a remarkably enhanced grain refinement effect after the same five-pass swaging.

Effect of Zirconia Corundum Addition on Properties of Chrome Corundum Castables

In order to investigate the effect of zirconia corundum on the preparation of chrome corundum castables,samples were prepared using tabular corundum,white fused corundum,active alumina micropowder,chromium oxide micropowder and fused ziconia corundum particles as the main raw materials,and pure calcium aluminate cement as the binder.The effects of the fused zirconia corundum particles addition(1-0.5 mm,0,4.5%,9%,and 18%,by mass)on the linear change rate,the apparent porosity,the cold modulus of rupture,and the thermal shock resistance of chrome corundum castables were studied,and the microstructure of the samples was analyzed.The results show that:(1)with the zirconia corundum addition increasing,the permanent linear change on heating of the samples gradually increases,the apparent porosity gradually increases,the cold modulus of rupture gradually decreases,and the thermal shock resistance gradually increases;(2)according to SEM,it can be found that the phase transformation of ZrO2 after heat treatment leads to a large number of microcracks in the material.On one hand,the cold modulus of rupture of the material is reduced;on the other hand,the thermal shock resistance of the material is improved.

Preparation and Mechanical Properties of Zirconia Ceramics Doped with Different Y_(2)O_(3)Contents

The sintering behavior and mechanical properties of zirconia doped with 2.0mol%-3.0mol%Y_(2)O_(3)were studied by pressure-less sintering.The experimental results show that the densification temperature of zirconia ceramics increases gradually with the decrease of Y_(2)O_(3)doping content by which decreases the sintering driving force due to the lower oxygen vacancy concentration of the systems.Furthermore,the bending strength and fracture toughness of the prepared zirconia ceramics increase with the decrease of Y_(2)O_(3)doping content.It can be attributed to the fact that the phase stability of tetragonal zirconia decreases with the decrease of Y_(2)O_(3)doping content,which is easier to induce"phase transformation toughening"and dissipate impact energy.The relative density,bending strength and fracture toughness of 2.0 mol%Y_(2)O_(3)doped zirconia ceramics(2.0Y-ZrO_(2))sintered at 1525℃are 99.00%,1256.65±20.82 MPa and 9.85±0.13 MPa·m^(1/2),respectively.

Light-stimulated adaptive artificial synapse based on nanocrystalline metal-oxide film

Artificial synapses utilizing spike signals are essential elements of new generation brain-inspired computers.In this paper,we realize light-stimulated adaptive artificial synapse based on nanocrystalline zinc oxide film.The artificial synapse photoconductivity shows spike-type signal response,long and short-term memory(LTM and STM),STM-to-LTM transition and paired-pulse facilitation.It is also retaining the memory of previous exposures and demonstrates spike-frequency adaptation properties.A way to implement neurons with synaptic depression,tonic excitation,and delayed accelerating types of response under the influence of repetitive light signals is discussed.The developed artificial synapse is able to become a key element of neuromorphic chips and neuromorphic sensorics systems.

Nacre-inspired Zirconia/Carbon Nanocomposites with High Strength and Toughness

Inspired by structures of natural shells,zirconia-carbon nanocomposites were obtained by using natural chitin from shrimp shells as templates via the sol-gel route in this study.Chitin was dispersed in the water and chelated with the zirconia precursors by amidogen.After a heat treatment for carbonization,nacre-like structures of carbon-zirconia nanocomposites were successfully synthesized.Due to the toughening mechanism of tetragonal zirconia,the mechanical properties of carbon-zirconia composites are further improved.The as-received zirconia/carbon nanocomposite with best mechanical property has a hardness of 5.88GPa and an elastic modulus of 80.6 GPa,which is even stronger than natural shells.This work might facilitate a versatile platform for developing green nanocomposites with reasonably good mechanical properties.

Machine learning potential for Ab Initio phase transitions of zirconia

Zirconia has been extensively used in aerospace,military,biomedical and industrial fields due to its unusual combination of high mechanical,electrical and thermal properties.However,the fundamental and critical phase transition process of zirconia has not been well studied because of its difficult first-order phase transition with formidable energy barrier.Here,we generated a machine learning interatomic potential with ab initio accuracy to discover the mechanism behind all kinds of phase transition of zirconia at ambient pressure.The machine learning potential precisely characterized atomic interactions among all zirconia allotropes and liquid zirconia in a wide temperature range.We realized the challenging reversible first-order monoclinic-tetragonal and cubicliquid phase transition processes with enhanced sampling techniques.From the thermodynamic information,we gave a better understanding of the thermal hysteresis phenomenon in martensitic monoclinic-tetragonal transition.The phase diagram of zirconia from our machine learning potential based molecular dynamics simulations corresponded well with experimental results.

Long-term corrosion behavior of HVOF sprayed FeCrSiBMn amorphous/nanocrystalline coating

A FeCrSiBMn amorphous/nanocrystalline coating with 700 μm in thickness and 0.65% in porosity, was prepared by high velocity oxygen fuel(HVOF) spraying process. The long-term corrosion behavior of the FeCrSiBMn coating was evaluated by potentiodynamic polarization and electrochemical impedance spectroscopy(EIS) tests in a 3.5% NaCl solution with a hard chromium coating as a reference. The FeCrSiBMn coating exhibited higher corrosion potential and lower corrosion current density than the hard chromium coating. The pore resistance(Rp) and charge transfer resistance(Rct) of FeCrSiBMn coating were higher than those of the hard chromium coating. In addition, after immersion in the Na Cl solution for 28 d, only small pores in the FeCrSiBMn coating were observed. All the results indicated that the FeCrSiBMn coating held superior corrosion resistance to the hard chromium coating. This could be attributed to the dense structure, low porosity and amorphous/nanocrystalline phases of the FeCrSiBMn coating.

Preparation of Ordered Mesoporous Nanocrystalline Ceria and Ceria-zirconia for Soot Oxidation

Ordered mesoporous ceria and ceria-zirconia with high specific surface area were prepared by nanocasting of a mesoporous silica KIT-6 template and used for soot oxidation.The as-synthesized ordered mesoporous ceria and ceria-zirconia were characterized by XRD,TEM,Nitrogen adsorption-desorption,Raman spectroscopy,and XRF.The results indicate that mesoporous ceria and ceria-zirconia possess highly ordered mesoporous structure,and exhibited excellent catalytic performance in soot oxidation.T_（50） of mesoporous ceria and ceria-zirconia are 475 and 470 ℃,respectively.The high catalytic activity of mesoporous materials can be attributed to the mesoporous structure and small crystallite size.Moreover,aged mesoporous materials exhibit high catalytic activity.

Phase evolution of plasma sprayed Al_2O_3-13%TiO_2 coatings derived from nanocrystalline powders

Commercial nanosized alumina and titania particles were selected as raw materials to prepare the blended slurry with composition of A1203-13%TiO2 （mass fraction）, which were reconstituted into micrometer-sized granules by spray drying, subsequently sintering at different temperatures to form nanostructured feedstock for thermal spraying, and then A1203-13%TiO2 nanocoatings were deposited by plasma spraying. The evolution of morphology, microstructure, and phase transformation of the agglomerated powder and as-sprayed coatings were characterized by X-ray diffraction （XRD） and scanning electron microscopy （SEM）. The results show that A1203 retains the same a phase as the raw material during sintering, while TiO2 changes from anatase to futile. During plasma spraying, some a-A1203 phases solidify to form metastable y-A1203, and the volume fraction of a-A1203 decreases as CPSP increases. However, peaks of the TiO2 phase are not observed from the as-sprayed coatings except for the coatings sprayed at the lower CPSP. As the CPSP increases, nanostructured TiO2 is dissolved easily in y-A1203 or z-A1203＇TiO2 phase. After heat treatment, y-A1203 in the coatings transforms to a-A1203, and rutile is precipitated.

Thermal stability of electrodeposited nanocrystalline nickel assisted by flexible friction

Nanocrystalline nickel coating was prepared by flexible friction assisted electrodeposition technology in an additive-free Watts bath.The coating consists of massive equiaxial crystals with an average grain size of about 24 nm and exhibits a（111） preferred orientation.The differential scanning calorimetry（DSC） analysis of nanocrystalline nickel demonstrates that the peak temperature of rapid grain growth is about 285.4 °C,and the peak temperature of grain growth towards equilibrium is around 431.5 °C.The isochronous annealing results reveal that abnormal grain growth behavior is not observed in nanocrystalline nickel without sulfur-containing.The thermal stability of the deposition was improved due to its initial microstructure of the as-deposited nickel and a certain amount of annealing nano-twins with low-energy,which reduces the driving force for grain growth.Consequently,the coating shows a low residual tensile stress of about 50 MPa and a high microhardness of HV 400 at the annealing temperature of 450 °C.

Fabrication and characterization of electrodeposited nanocrystalline Ni-Fe alloys for NiFe_2O_4 spinel coatings

Nanocrystalline Ni-Fe FCC alloy coatings with Fe content of 1.3%-39%（mass fraction） were fabricated on the nickel substrates using a DC electrodeposition technique. The crystal structure, lattice strain, grain size and lattice constant of the Ni-Fe alloy coatings were studied by X-ray diffraction technique. The chemical composition and surface morphology of the FCC Ni-Fe alloy coatings were investigated with the energy dispersive X-ray spectroscopy（EDS） and atomic force microscopy（AFM）. The results show that the Fe content of the Ni-Fe alloy coatings has a great influence on the preferred orientation, grain size, lattice constant and lattice strain. FCC Ni-Fe alloy coatings exhibit preferred orientations of（200） or（200）（111）. With an increase of Fe content, the preferred growth orientation of（200） plane is weakened gradually, while the preferred growth orientation of（111） increases. An increase of the Fe content in the range of 1.3%-25%（mass fraction） results in a significant grain refinement of the coatings. Increasing the Fe content beyond 25% does not decrease the grain size of FCC Ni-Fe alloys further. The lattice strain increases with increasing the Fe content in the FCC Ni-Fe alloys. Since the alloys with Fe content not less than 25% has similar grain size（~11 nm）, the increase in the lattice strain with the increase of Fe content cannot be attributed to the change in the grain size.

EFFECT OF GRID BIAS ON DEPOSITION OF NANOCRYSTALLINE DIAMOND FILMS

A positive grid bias and a negative substrate bias voltages are applied to the self-made hot filament chemical vapor deposited （HFCVD） system. The high quality nanocrystalline diamond （NCD） film is successfully deposited by double bias voltage nucleation and grid bias voltage growth. The Micro-Raman XRD SEM and AFM are used to investigate the diamond grain size, microstructure, surface morphology, and nucleation density. Results show that the obtained NCD has grain size of about 20 nm. The effect of grid bias voltage on the nucleation and the diamond growth is studied. Experimental results and theoretical analysis show that the positive grid bias increases the plasma density near the hot filaments, enhances the diamond nucleation, keeps the nanometer size of the diamond grains, and improves the quality of diamond film.