Formation process of composite plasma electrolytic oxidation coating containing zirconium oxides on AM50 magnesium alloy

The formation processes of a composite ceramic coating on AM50 magnesium alloy prepared by plasma electrolytic oxidation （PEO） in a K 2 ZrF 6 electrolyte solution were studied by scanning electron microscope （SEM） and energy dispersive X-ray spectroscope （EDX）. Electrochemical impedance spectroscopy （EIS） tests were used to study the variation of the corrosion resistance of the coating during the PEO treatment. The results show that the coating formed on Mg alloy is mainly composed of MgO and MgF 2 when the applied voltage is lower than the sparking voltage, and zirconium oxides start to be deposited on Mg substrate after the potential exceeding the sparking voltage. The corrosion resistance of the coating increases with increasing the applied voltage.

Effects of co-precipitation temperature on structure and properties of La and Y doped cerium zirconium mixed oxides

Due to the oxygen storage and release properties,cerium zirconium mixed oxides are recognized as the key material in automotive three-way catalysts.To reveal the effects of co-precipitation temperature on structure,physical and chemical properties of multi-doped cerium zirconium mixed oxides,a series of La and Y doped cerium zirconium mixed oxides(CZLYs)were synthesized via a co-precipitation method,and the physical and chemical properties of CZLYs were systemically characterized by XRD,N_(2) adsorption−desorption,TEM,XPS,oxygen storage capacity(OSC)and hydrogen temperature programmed reduction(H_(2)-TPR).The results show that co-precipitation temperature is an important parameter to influence the crystal size,oxygen storage capacity and thermal stability of CZLYs.When the co-precipitation temperature was 60℃,the best redox properties and thermal stability of CZLYs were obtained.After thermal treatment at 1100℃for 10 h,the specific surface area and oxygen storage capacity of the corresponding aged sample were 15.42 m^(2)/g and 497.7μmol/g,respectively.In addition,a mechanism was proposed to reveal the effects of co-precipitation temperature on the structure and properties of CZLYs.

Experimental and Theoretical Study of Hydrogen Atom Abstraction from C2H6 and C4H10 by Zirconium Oxide Clusters Anions

The reactions of anionic zirconium oxide clusters ZrxOy- with C2H6 and C4H10 are investi-gated by a time of flight mass spectrometer coupled with a laser vaporization cluster source.Hydrogen containing products Zr2O5H- and Zr3O7H- are observed after the reaction. Den-sity functional theory calculations indicate that the hydrogen abstraction is favorable in the reaction of Zr2O5- with C2H6, which supports that the observed Zr2O5H- and Zr3O7H- are due to hydrogen atom abstraction from the alkane molecules. This work shows a newpossible pathway in the reaction of zirconium oxide cluster anions with alkane molecules.

Evaluation of nanometer-sized zirconium oxide incorporated Al-Mg-Ga-Sn alloy as anode for alkaline aluminum batteries

Zirconium oxide nanoparticles with 0.4 wt.%and 0.8 wt.%are incorporated into the Al-0.65 Mg-0.05 Ga-0.15 Sn(wt.%)alloy anode(base alloy)in order to improve the performance of the resulting anodes.Electrochemical characterization of the reinforced alloys was done by potentiodynamic polarization,electrochemical impedance spectroscopy and galvanostatic discharge and corrosion behavior was evaluated using self-corrosion rate and hydrogen evolution in 4 mol/L KOH solution.The surface morphology of the alloys was also studied using field emission scanning electron microscope(FESEM).The obtained results indicate that the base alloy shows high corrosion rate in 4 mol/L KOH solution by releasing 0.47 m L/(min·cm^2)hydrogen gas,whereas the alloy containing 0.8 wt.%Zr O2 provides the lowest hydrogen evolution rate by releasing 0.32 m L/(min·cm^2)hydrogen gas.Furthermore,by increasing zirconium oxide nanoparticles,the corrosion current density of the aluminum anodes is decreased and their corrosion resistance increases significantly compared to the base alloy in alkaline solution.In addition,nanometer-sized zirconium oxide incorporated anodes exhibit the improved galvanic discharge efficiencies,so that 0.8 wt.%nano-zirconium oxide incorporated base alloy displays the highest power density and anodic utilization compared with the others in 4 mol/L KOH solution.

Confocal Laser Scanning Microscope Evaluation of Early Bacterial Colonization on Zirconium Oxide and Titanium Surfaces:An in vivo Study

To investigate the bacterial colonization on zirconium oxide and titanium surfaces in vivo quantitatively using a confocal laser scanning microscope （CLSM）. Ten samples of zirconium oxide ceramic and commercially pure titanium were fabricated and polished using silicon carbide abrasive paper. One sample from each group was evaluated topographic pattern under a scanning electron microscope. One sample from each group was to evaluate roughness using a profilometer. Eight volunteers were selected. The samples were cemented at the buccal surfaces of upper first molars. All samples were removed after 48 hours, immersed in SYTO-9 and propidium iodide fluorescent to stain for adherent bacteria and obseIved with CLSM. Fewer bacteria were observed in zirconia group than titanium group. However, there was no statistical difference between two groups. The experimental results demonstrate that zirconium oxide may be considered as a promising material for dental implant abutments.

Experimental and Theoretical Study of Hydrogen Atom Abstraction from Ethylene by Stoichiometric Zirconium Oxide Clusters

The reactions of cationic zirconium oxide clusters （ZrxOy^＋） with ethylene （C2H4） were investigated by using a time-of-flight mass spectrometer coupled with a laser ablation/supersonic expansion cluster source. Some hydrogen containing products （ZrO2）xH^＋（x=-1-4） were observed after the reaction. The density functional theory calculations indicate that apart from the common oxygen transfer reaction channel, the hydrogen abstraction channel can also occur in （ZrO2）x^＋＋C2H4, which supports that the observed （ZrO2）xH^＋ may be due to （ZrO2）x^＋＋C2H4→（ZrO2）xH^＋＋C2H3. The rate constants of different reaction channels were also calculated by Rice-Rarnsberger-Kassel-Marcus theory.

Surface finish effect on dry sliding wear behavior of thermally oxidized commercially pure zirconium

The effect of surface polishing on the wear behavior of thermally oxidized commercial pure zirconium (CP-Zr) under dry sliding conditions was investigated. Surface ground CP-Zr with a roughness of 0.21 μm (Ra) was thermally oxidized (TO) at 650 °C for 6 h. After TO, some samples were polished to smoothen the surface with a finish of 0.04 μm (Ra). The response of the polished and unpolished TO samples to dry sliding wear was investigated under unidirectional sliding conditions. The results show that surface polishing after TO affects the dry sliding wear behavior of TO CP-Zr in several aspects, including coefficient of friction, wear rate, crack formation and oxide layer breakdown. In particular, it is found that smoothening the TO surface favors the formation of semi-circular cracks in the wear track and accelerates oxide layer breakdown during dry sliding. A slightly rough TO surface helps to reduce the tendency of the oxide layer towards cracking and to increase the wear resistance at high contact loads. The mechanisms involved are discussed in terms of asperity contacts, crack formation, propagation and final fracture.

Hydrothermal Preparation and Photocatalytic Water Splitting Properties of ZrW_2O_8

ZrW2O8 was prepared by adjusting Zr：W mole ratio and HCl concentration in hydrothermal reaction processes.The obtained sample was crystallized in α-ZrW2O8 phase （cubic,P213）,with band gap energy of 4.0 eV.The properties of photocatalytic water splitting were examined under UV light irradiation.The average rate of H2 evolution over 0.3wt% Pt/ZrW2O8 in the presence of CH3 OH as electron donor （ED） was 23.4 μmol/h,while the average rate of O2 evolution over ZrW2O8 in the presence of AgNO3 as electron scavenger （ES） was 9.8 μmol/h.Moreover,H2 was evolved over 0.3wt% Pt/ZrW2O8 from pure water splitting at a rate of 5.2 μmol/h.The study indicated that the band structure of ZrW2O8 was suitable for reducing H ＋ to H2 and oxidizing H2O to O2.The band structure and photocatalytic water splitting properties of ZrW2O8,different from either ZrO2 （5.0 eV） or WO3 （2.7 eV）,were attributed to the hybridization of W5d and Zr4d in conduction band （CB） as well as the change in crystal structure.

Optimization of ferroelectricity and endurance of hafnium zirconium oxide thin films by controlling element inhomogeneity

Ferroelectric thin films based on HfO_(2) have garnered increasing attention worldwide,primarily due to their remarkable compatibility with silicon and scalability,in contrast to traditional perovskite-structured ferroelectric materials.Nonetheless,significant challenges remain in their widespread commercial utilization,particularly concerning their notable wake-up effect and limited endurance.To address these challenges,we propose a novel strategy involving the inhomogeneous distribution of Hf/Zr elements within thin films and explore its effects on the ferroelectricity and endurance of Hf_(0.5)Zr_(0.5)O_(2) thin films.Through techniques such as grazing incidence X-ray diffraction,transmission electron microscopy,and piezoresponse force microscopy,we investigated the structural characteristics and domain switching behaviors of these materials.The experimental results indicate that the inhomogeneous distribution of Hf/Zr contributes to improving the frequency stability and endurance while maintaining a large remnant polarization in Hf_(0.5)Zr_(0.5)O_(2) ferroelectric thin films.By adjusting the distribution of Zr/Hf within the Hf_(0.5)Zr_(0.5)O_(2) thin films,significant enhancements in the remnant polarization(2P_(r)>35μC/cm2)and endurance(>109)along with a reduced coercive voltage can be achieved.Additionally,the fabricated ferroelectric thin films also exhibit high dielectric tunability(≥26%)under a low operating voltage of 2.5 V,whether in the wake-up state or not.This study offers a promising approach to optimize both the ferroelectricity and endurance of HfO_(2)-based thin films.

Nickel sulfate solution fluoride separation with hydrous zirconium oxide

Fluoride is an impurity in nickel sulfate production,which is required for electric vehicle batteries.Hydrous zirconium oxide(HZO)was evaluated for removing fl uoride from nickel sulfate solution.Maximum fluoride removal occurred at pH value 4 and optimal pH value is 4–5,considering Zr solubility.Fluoride availability decreases with pH due to hydrogen fluoride and zirconium fluoride aqueous species.Fluoride removal is initially rapid,with 50 wt.%removal in 7 min,followed by slow removal up to 68 wt.%after 72 h and follows second order rate kinetics.Fluoride removal was dominated by an ion exchange mechanism and resulting Zr–F bonds were observed using Fourier-transform infrared spectroscopy.The presence of nickel sulfate decreased loading capacity compared to a salt-free solution.HZO maintained adsorption capacity through five cycles of loading and regeneration.

Investigation of potential interferences on the measurement of dissolved reactive phosphate using zirconium oxide-based DGT technique

A diffusive gradients in thin films （DGT） technique based on hydrous zirconium oxide （Zr-oxide） has been recently developed for the measurement of dissolved reactive phosphate （DRP）. In this study, the detailed performance of the DGT technique is reported. Spiking experiments revealed that several orthophosphate monoester compounds contributed to the Zr-oxide DGT measurements of DRP. However, such a phenomenon is unlikely to occur during field conditions due to the low concentration of organic P in typical natural waters. The presence of Cl- （up to 106 g/L）, SO42- （up to 16 g/L）, HCO3- （up to 817 g/L）, and AsO2- and AsO 3 4 （both up to 1 mg As/L） in solutions had negligible effects on the measurement of DRP. The threshold concentrations of Cl-, SO42- and HCO3- have been increased from previous reports for the measurements of DRP using other adsorbent-based DGT techniques. The capacity for DGT measurements of DRP decreased with increasing solution pH （4.2-9.2）. The lowest capacity （95 μg P/m2 at pH 9.2） was still greater than that of other DGT techniques that are usually used for the measurement of DRP （2-12 μg P/cm2 ）. The Zr-oxide binding gel could be stored for up to 2 years without any aging effect. This period of validity was considerably longer than the ferrihydrite binding gel that is commonly used in present DGT devices （6 months）. The field application revealed that the concentrations of DRP measured in three fresh water samples using the Zr-oxide DGT technique were in agreement with those of the traditional colorimetric method.

Characterization of CeO_2-ZrO_2 mixed oxides prepared by two different co-precipitation methods

A series of cerium zirconium mixed oxides were prepared by two co-precipitation methods using magnesium hydrogen carbonate （MHC） and mixed ammonia-ammonia hydrogen carbonate （AAHC） as precipitant respectively. The crystal structure, BET surface area and morphology of the produced cerium zirconium mixed oxides were characterized by X-ray diffraction （XRD）, Bru- mauer-Emmett-Teller （BET） and scanning electron microscopy （SEM） techniques. The reduction-oxidation behavior and oxygen storage capacity （OSC） performance were also studied by temperature programmed reduction （TPR） and oxygen pulse chemical adsorption methods. The XRD results demonstrated that the cerium zirconium mixed oxides obtained by both methods possessed struc ture of cubic solid solution phase. The fresh surface area calcinated at 600 ℃, aged surface area after 1000 ℃and OSC at 500 ℃ of cerium zirconium mixed oxides were determined to be 89.337, 34.784 ma/g, and 567 pmol O2/g for MHC method and 122.010, 46.307 m2/g, and 665 pmol O2/g for AAHC method, respectively.

Structure and properties of cerium zirconium mixed oxide prepared under different precipitate aging processes

Oriented attachment and Ostwald ripening are two aging mechanisms of precipitation particles which may result in differ- ent crystallization mechanism of precipitates during the aging process. In this work, the effects of different aging process on the structure and properties of cerium zirconium mixed oxides were investigated. The results indicated that the mixed structure of 11.48% CeO2 phase and 88.52% Ce0.26Zr0.62（LaPr）0.1202 solid solution phase were obtained under oriented attachment aging process. The rod-like CeO2 phase coexisted with spherical Ce0.26Zr0.62（LaPr）0.1202 solid solution phase, which improved the surface area （64 m2/g） and pore volume （0.32 mL/g） of cerium zirconium mixed oxides after 1000 ℃ 4 h thermal treatment. However, through controlling the aging process, the Ce0.35Zr0.55（LaPr）0.1002 solid solution with homogenous phase structure was generated by Ostwald ripening ag- ing process, exhibiting higher oxygen storage capacity （501 μmol O2/g） and H2 consumption per gram （1378.3 μmol H2/g）.

The effect of hydrogen peroxide on properties of Ce0.35Zr0.55La0.055Pr0.045O2 oxides and the catalytic performance usedon Pd supported three-way catalyst

In this study,two series of cerium zirconium mixed oxides CeZrLaPrOwere prepared under traditional co-precipitation and oxidation co-precipitation methods respectively. The physicochemical properties of the samples were compared under these two methods and assessed by XRD,Raman,BET,TEM,HTPR,OSC,XPS and catalysts measurements. The formation of homogeneity phase structure can be facilitated by changing the precipitating properties of Ce3+ under oxidation coprecipitation method, which is helpful to enhance the homogeneity of Ce and Zr at atomic level.What’s more, it is conducive to remove impurities Na~+ and Cl~-by oxidation co-precipitation with hydrogen peroxide. The catalysts activities are related to both the redox properties and the textural properties of mixed oxides. The Pd-only TWCs supported on the CZLP-H-F exhibits better catalytic performance and thermal stability with wider air/fuel ratio operation window, lower light-off and full conversion temperatures of CHand NO. The homogeneity of phase structure for cerium zirconium mixed oxide can be predicted and deduced from detecting the atomic distribution uniformity of its precursor. So this work not only provides insights into the mechanisms for phase segregation of cerium zirconium mixed oxide, but also provides a guidance to improve homogeneity of cerium zirconium mixed oxide by adding additives.

Zirconium oxide ceramic foam: a promising supporting biomaterial for massive production of glial cell line-derived neurotrophic factor

This study investigated the potential application of a zirconium oxide （ZrO2） ceramic foam culturing system to the production of glial cell line-derived neurotrophic factor （GDNF）. Three sets of ZrO2 ceramic foams with different pore densities of 10, 20, and 30 pores per linear inch （PPI） were prepared to support a 3D culturing system. After primary astrocytes were cultured in these systems, production yields of GDNF were evaluated. The biomaterial bio- compatibility, cell proliferation and activation of cellular signaling pathways in GDNF synthesis and secretion in the culturing systems were also assessed and compared with a conventional culturing system. In this study, we found that the ZrO2 ceramic foam culturing system was biocompatible, using which the GDNF yields were elevated and sustained by stimulated cell proliferation and activation of signaling pathways in astrocytes cultured in the system. In conclusion, the ZrO2 ceramic foam is promising for the development of a GDNF mass production device for Parkinson＇s disease treatment.

The Analysis of Zirconium (Ⅳ) Oxide (ZrO_(2)) Nanoparticles for Peroxidase Activity

In this study,the peroxidase-like activity of zirconium(Ⅳ)oxide nanoparticles(nZr)is reported.Peroxidases catalyze the oxidation of their substrate in the presence of peroxide species.3,3′,5,5′-tetramethylbenzidine(TMB)is a peroxidase substrate,and we have demonstrated that nZr oxidizes the TMB in the presence of hydrogen peroxide resulting in a colored(TMBox)product.The reaction was tested in various buffers,and sodium acetate with pH 4 was observed to be an ideal buffer for the enzymatic reaction and the dispersity of the nZr in the solution.The nanozyme behavior was studied systematically at three different temperatures(25,35 and 45℃)and a wide range of H_(2)O_(2) concentrations.The dependence of the enzymatic reaction on temperature,nZr content and H_(2)O_(2) concentration was observed.The enzymatic reaction was tested in different protein solutions and no noticeable interference was observed with these proteins.Overall,we demonstrate that nZr,which is often used for industrial applications,mimics peroxidase enzyme and catalyzes oxidation of its substrate in the presence of peroxide species.

Corrosion resistance properties of colored zirconium conversion coating and powder coating on cold-rolled steel

Jiuhe Corporation developed a new surface pretreatment for producing a phosphate-free and colored zirconium conversion coating on cold-rolled steel(CRS).Scanning electron microscopy(SEM)and energy-dispersive spectroscopy(EDS)were applied to study the surface morphology and elemental composition of the golden yellow-colored conversion coating.Elec trochemic al impedance spectroscopy(EIS)was used to investigate the electrochemical performance of the conversion coatings with different colors.The corrosion resistance properties of the powder coatings were characterized using the neutral salt spray test(NSS)and the tape adhesion test.The EIS and NSS results demonstrate that the colored zirconium conversion coatings exhibit excellent corrosion resistance properties compared with the bare CRS.The golden yellow-colored conversion coating has a maximum EIS value(748Ω·cm^(2))and achieves 0 mm degree of corrosion,as stipulated by EN ISO 4628-8.This paper proposes a hypothesis concerning the ZrO_(2)-(β-FeOOH)-polymer conversion reaction to explain the color changes.

Performance improvements in complementary metal oxide semiconductor devices and circuits based on fin field-effect transistors using 3-nm ferroelectric Hf_(0.5)Zr_(0.5)O_(2)

In this work,a conventional HfO_(2) gate dielectric layer is replaced with a 3-nm ferroelectric(Fe) HZO layer in the gate stacks of advanced fin field-effect transistors(FinFETs).Fe-induced characteristics,e.g.,negative drain induced barrier lowering(N-DIBL) and negative differential resistance(NDR),are clearly observed for both p-and n-type HZO-based FinFETs.These characteristics are attributed to the enhanced ferroelectricity of the 3-nm hafnium zirconium oxide(HZO) film,caused by Al doping from the TiAlC capping layer.This mechanism is verified for capacitors with structures similar to the FinFETs.Owing to the enhanced ferroelectricity and N-DIBL phenomenon,the drain current(I_(DS))of the HZO-FinFETs is greater than that of HfO_(2)-FinFETs and obtained at a lower operating voltage.Accordingly,circuits based on HZO-FinFET achieve higher performance than those based on HfO_(2)-FinFET at a low voltage drain(V_(DD)),which indicates the application feasibility of the HZO-FinFETs in the ultralow power integrated circuits.

Preparation and properties of ZrO_(2)-strengthened porous mullite insulation materials using Y_(2)O_(3) additive

ZrO_(2)-strengthened porous mullite insulation materials were prepared by foaming technology utilizing ZrSiO_(4) and Al_(2)O_(3) as primary materials and Y_(2)O_(3) as an additive.The effects of Y_(2)O_(3) contents on the phase composition,microstructure,mechanical properties,and heat conductivity of the porous mullite insulation materials were investigated.A suitable Y_(2)O_(3) content could promote phase transition of monoclinic ZrO_(2)(m-ZrO_(2))to tetragonal ZrO_(2)(t-ZrO_(2)),reduce pore size,and improve the strengths of as-prepared specimens.The cold crushing strength and bending strength of as-prepared specimens with a 119µm spherical pore size using 6 wt.%Y_(2)O_(3) were 35.2 and 13.0 MPa,respectively,with a heat conductivity being only 0.248 W/(m K).

Tailoring thermal stability of ceria-zirconia mixed oxide by doping of rare earth elements:From theory to experiment

Ceria-zirconia mixed oxides(CZMO)are widely used in many important catalysis fields.However,pure CZMO is known to have poor thermal stability.In this paper,a strategy was proposed to design Ce_(0.475)Zr_(0.475)M_(0.05)O_(2)(M=La,Y,Pr,Nd,Pm,Sm,Eu,Gd,Tb,Er,Lu,and,Yb)oxide surface with high thermal stability by using first-principles molecular dynamics(FPMD)simulation and experiment method.Through the structure stability analysis at different temperatures,the surface energyγas a function of R_(ion)/D_(ave)is identified as a quantitative structure descriptor for analyzing the doping effect of rare earth(RE)elements on the thermal stability of Ce_(0.475)Zr_(0.475)M_(0.05)O_(2).By doping the suitable RE,γcan be adjusted to the optimal range to enhance the thermal stability of Ce_(0.475)Zr_(0.475)M_(0.05)O_(2).With this strategy,it can be predicted that the sequence of thermal stability improvement is Y>La>Gd>Nd>Pr>Pm>Sm>Eu>Tb>Er>Yb>Lu,which was further verified by our experiment results.After thermal treatment at 1100℃for 10 h,the specific surface area(SSA)of aged Y-CZ and La-CZ samples can reach 21.34 and 19.51 m~2/g,which is 63.02%and 49.04%higher than the CZMO sample without doping because the surface doping of Y and La is in favor of inhibiting the surface atoms thermal displacement.In a word,the strategy proposed in this work can be expected to provide a viable way for designing the highly efficient CZMO materials in extensive applications and promoting the usages of the high-abundance rare-earth elements Y and La.