Stabilization Of Tetragonal Phase Research Articles

Competition of L21 and L10 ordering in Pd2MnSe, Pd2FeSe, Pd2MnTe and Pd2FeTe Heusler alloys

Abstract Based on first-principles method, for Pd2MnSe, Pd2FeSe, Pd2MnTe and Pd2FeTe, we investigated the competition between cubic L21-type and their tetragonal L10-type ordering. Firstly, low-energy tetragonal ground states are found in these alloys during the tetragonal deformation. By regulating the c/a ratio under the fixed volume of equilibrium cubic phase, we obtain two minimums in total energy-c/a curve: a shallow one in c/a 1. Meanwhile the uniform strain is also taken into consideration in this work, and we found that ΔEM and Vopt + X%Vopt are negatively correlated, that is, with the volume increases from Vopt − 3%Vopt to Vopt + 3%Vopt, the absolute value of ΔEM decreases accordingly. Secondly, the origin of the tetragonal ground states of Pd2 [Fe/Mn][Se/Te] are also be explained by the density of states (DOS) figures. From the valley-and-peak structure, we can find the DOS at or in the vicinity of the Fermi level is much broader and shallower in tetragonal L10 state than cubic L21 state, indicating the phase stability of tetragonal L10 phases of these Pd2-based alloys. Moreover, to further study the competition of L21 and L10 ordering in these alloys and verify the stability of the tetragonal L10 state, elastic constants were introduced in this work, C11, C12 and C44 for cubic state while C11, C12, C13, C33, C44, C66 for tetragonal L10-type structure. According to the judgment basis, all alloys exhibit L10-stable, satisfying our conclusions about the stability of tetragonal states. We hope our work can provide a guidance for researchers to further explore and study new magnetic functional tetragonal materials among the full-Heusler alloys.

Corrosion Behavior and Oxide Films of New Zirconium Cladding Corroded at Different Conditions

Zirconium alloys are mostly served as the cladding materials in water reactors. Corrosion is one of the concerning problems in zirconium utilization. Transition of corrosion occurs every 2~3 μm in thickness, but its mechanism is not confirmed. To study the influence of water chemistry and the mechanism behind transition, a new type of zirconium cladding was tested for three corrosion conditions: the pure water, LiOH solution, LiOH/H3BO3 solution at 360°C/18.6MPa. For all cases, Zr-0.5Sn-0.15Nb-0.5Fe-0.2V cladding had a lower corrosion rate and a longer transition time than N36 cladding. The corrosion results showed that the corrosion rate was the highest and the transition time was the shortest in LiOH solution. Oxide phase information on the oxidized surface was obtained by Raman study. Tetragonal zirconia, embedded in the surface, was found at the beginning of corrosion. As the corrosion time increased, tetragonal phase stress was almost released and the content of tetragonal phase was also decreased to zero at the transition point. Stable tetragonal phase was found on the samples corroded in pure water. However, in LiOH solution, it was eliminated the quickest. The acceleration of transition in LiOH solution is partly resulted from the fast transformation of tetragonal phase. The reason for the longer transition time in N2 cladding can be directly attributed to the smaller decrease of the tetragonal phase.

Synthesis and thermal stability of ZrO2@SiO2 core-shell submicron particles.

ZrO2@SiO2 core–shell submicron particles are promising candidates for the development of advanced optical materials. Here, submicron zirconia particles were synthesized using a modified sol–gel method and pre-calcined at 400 °C. Silica shells were grown on these particles (average size: ∼270 nm) with well-defined thicknesses (26 to 61 nm) using a seeded-growth Stöber approach. To study the thermal stability of bare ZrO2 cores and ZrO2@SiO2 core–shell particles they were calcined at 450 to 1200 °C. After heat treatments, the particles were characterized by SEM, TEM, STEM, cross-sectional EDX mapping, and XRD. The non-encapsulated, bare ZrO2 particles predominantly transitioned to the tetragonal phase after pre-calcination at 400 °C. Increasing the temperature to 600 °C transformed them to monoclinic. Finally, grain coarsening destroyed the spheroidal particle shape after heating to 800 °C. In striking contrast, SiO2-encapsulation significantly inhibited grain growth and the t → m transition progressed considerably only after heating to 1000 °C, whereupon the particle shape, with a smooth silica shell, remained stable. Particle disintegration was observed after heating to 1200 °C. Thus, ZrO2@SiO2 core–shell particles are suited for high-temperature applications up to ∼1000 °C. Different mechanisms are considered to explain the markedly enhanced stability of ZrO2@SiO2 core–shell particles.

Dielectric study of Ti-doped Bi2VO5.5 solid electrolyte

Synthesis and characterization of Bi2V1−xTixO5.5−(x/2)−δ (0 ≤ x ≤ 0.150) was done. For the present system, the lower limit of Ti required for near-complete tetragonal phase stabilization has been found to be x = 0.125. The optimum values of ionic conductivity were obtained for the compositions; Bi2V0.875Ti0.125O5.4375 and Bi2V0.9Ti0.1O5.45 at 300 °C and 600 °C, respectively. Interestingly, two peaks have been observed in frequency versus dielectric loss spectra for parent compound, which is in $$\alpha$$ -orthorhombic phase, as well as for tetragonal phase stabilized specimens with compositions x ≥ 0.125 at temperatures below 300 °C. No such peaks have been found in $$\beta$$ -orthorhombic (x = 0.085) as well as in mixed tetragonal and orthorhombic (x = 0.1 and 0.1125) phases. Thus, we propose that frequency-dependent dielectric loss spectra can be used to qualitatively distinguish $$\alpha$$ and $$\gamma$$ -phases from $$\beta$$ -phase in BITIVOX system and it is the central result of this work.

Full Tetragonal Phase Stabilization in ZrO₂ Nanoparticles Using Wet Impregnation: Interplay of Host Structure, Dopant Concentration and Sensitivity of Characterization Technique.

Here, we show that wet impregnation of ZrO2 nanoparticles with 10% and 20% Eu oxide followed by thermal anneal in air above 500 °C produces full stabilization of the tetragonal phase of ZrO2 without evidencing any phase separation. The bare ZrO2 nanoparticles were obtained using three synthetic methods: oil in water microemulsion, rapid hydrothermal, and citrate complexation methods. The homogeneity of the solid solutions was assessed using X-ray diffraction, Raman spectroscopy, high resolution transmission electron microscopy, and advanced luminescence spectroscopy. Our findings show that wet impregnation, which is a recognized method for obtaining surface doped oxides, can be successfully used for obtaining doped oxides in the bulk with good homogeneity at the atomic scale. The limits of characterization technique in detecting minor phases and the roles of dopant concentration and host structure in formation of phase stabilized solid solutions are also analyzed and discussed.

Fabrication and analysis of the structural phase transition of ZrO2 nanoparticles using modified facile sol–gel route

ABSTRACTThe synthesis of zirconia nanoparticles is achieved through a modified facile sol–gel route. The as-prepared gel is analyzed thermally using TGA and DTA techniques to spot the crystallization process of zirconia nanoparticles. The prepared gel is then annealed at different temperatures and the structure was found to change between tetragonal and monoclinic crystal systems. The first stable tetragonal phase is achieved after annealing for 2 h at 400°C. The annealed powders between 600°C and 800°C demonstrate mixed tetragonal/monoclinic phases. Annealing at 1000°C and higher temperatures up to 1200°C resulted in pure monoclinic phase. Cubic phase was not detected within the annealing temperature range in this study. The elemental analysis of the annealed powder confirmed the formation of zirconia nanoparticles with the chemical formula ZrO2. The FTIR spectra of the annealed samples introduced a variation in the vibrational bands especially around the phase transition temperature. HR-TEM images reported the formation of nano-zirconia crystals with apparently large particle sizes. The optical energy gap of zirconia nanoparticles is investigated and determined.

Phosphorus-doped SrCo0.5Mo0.5O3 perovskites with enhanced bifunctional oxygen catalytic activities

Perovskite oxide has attracted wild attentions as a promising bifunctional electrocatalyst family for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in fuel cells and metal-air batteries. Here, phosphorus-doped SrCo0.5Mo0.5O3 perovskites has been prepared and evaluated as bifunctional oxygen electrocatalyst. X–ray diffraction and X-ray photoelectron spectroscopy results show that P-doping benefits the formation of more stable tetragonal phase, and the generation of more surface adsorbed oxygen species. Compared with SrCo0.5Mo0.5O3 perovskites without doping, rotating disk electrode measurements indicates that P-doped SrCo0.5Mo0.5O3 exhibits a positively shifted half-wave potentional of 50 mV for ORR, and a reduced OER overpotential (∼58 mV) at 10 mA cm−2 in 0.1 M KOH solution. The enhanced catalytic activities and stabilities contribute to optimized surface characteristic and stable phase structure. The work not only provides a new strategy to develop efficient bifunctional oxygen catalysts, but also enriches knowledge of perovskite oxides.

The effect of silica content on microstructure and mechanical properties of calcia-stabilized tetragonal zirconia polycrystalline ceramic

The present study was aimed at investigating the effect of silica impurities on structure and mechanical properties of zirconia ceramics, stabilized in tetragonal phase by addition of 6.5 mol% calcia. The effect of silica was studied in 0–5 mol% silica concentration range. It was shown that notable increase in fracture toughness (from 7.5 MPa m0.5 to 12.5 MPa m0.5) as well as limited rise in hardness (from 12 GPa to 13 GPa) can be achieved by addition of ~ 2.5 mol% of SiO2. It was shown that further increase in SiO2 concentration above 3.75 mol% results in destabilization of tetragonal phase and degradation of mechanical properties. It is suggested that silica reacts with calcia resulting in formation of amorphous calcium silicate, decreasing calcia content in zirconia matrix, and facilitates sintering and grain growth, resulting in lower stability of tetragonal phase.

The effect of hydrostatic pressure on magnetostructural transition in ferromagnetic cobaltite: Pr0.6Sr0.4CoO3

The ambient pressure temperature dependence of the magnetization (M) in P1-xSrxCoO3 series (x = 0.4, 0.5, 0.55 and 0.6) indicates the onset of ferromagnetic ordering at high temperatures (TC = 214-226K) and a step-like anomaly at lower temperatures (TS = 69-120 K). In this report we present the pressure dependence of magnetization and zero-field thermal expansion studies for a representative sample x = 0.4. The step-like anomaly in M(T) around TS = 69 K is accompanied by a pronounced peak in thermal expansion coefficient. The application of hydrostatic pressure of P = 1.16 GPa increases TS by 15 K, which is much larger than the increase of the ferromagnetic Curie temperature (ΔTC = 4 K) under the same pressure. The anomalous increase of TS under pressure is attributed to the occurrence of magnetization rotation at a temperature higher than TS = 69 K triggered by the stabilization of low temperature tetragonal phase at the expense of high temperature orthorhombic phase.

The stability and physical properties of the tetragonal phase of bulk CuMnAs antiferromagnet

The effect of Cu substitution on the stability of the CuMnAs tetragonal phase was studied both experimentally and by ab initio calculations. Polycrystalline samples with various compositions Cu1+xMn1-xAs (x = 0–0.5) were synthetized. The tetragonal phase of CuMnAs is found to be stabilized by substituting Mn by Cu in the amount of x ∼0.1 or higher. This observation is supported by ab initio calculations of the total energy of the tetragonal and orthorhombic phases; with increasing Cu content the tetragonal phase is favoured. Small variations of composition thus allow to grow selectively one of these two phases with distinct and unique features for antiferromagnetic spintronics.Measurements of magnetic susceptibility and differential scanning calorimetry have shown that the tetragonal Cu1+xMn1-xAs has an antiferromagnetic behaviour with the maximum Néel temperature TN = 507 K for the highest Mn content samples, decreasing with the decreasing Mn content.

The Effect of Pore Connectivity on Li Dendrite Propagation within Llzo Electrolytes Observed with Synchrotron X-Ray Tomography

Li7La3Zr2O12 (LLZO) is a garnet type material that demonstrates promising characteristics for all solid-state battery applications due to its high Li-ion conductivity and its compatibility with Li metal1,2. The primary limitation of LLZO is the propensity for short-circuiting at low current densities3. Microstructure features such as grain boundaries, pore character, and density all contribute to this shorting phenomenon. Toward the goal of understanding structure-processing relationships for practical design of solid electrolytes, the present study tracks structural transformations in solid electrolytes processed at three different temperatures (1000, 1050 and 1150 °C) using synchrotron x-ray tomography4. A sub volume of 300 μm3 captures the heterogeneity of the solid electrolyte microstructure while minimizing the computational intensity associated with 3D reconstructions. While the porosity decreases with increasing temperature, the underlying connectivity of the pore region increases. Solid electrolytes with interconnected pores short circuit at lower critical current densities than samples with less connected pores. [1]Thompson, Travis, et al. "Tetragonal vs. cubic phase stability in Al–free Ta doped Li 7 La 3 Zr 2 O 12 (LLZO)." Journal of Materials Chemistry A 2.33 (2014): 13431-13436. [2] Sharafi, Asma, et al. "Characterizing the Li–Li 7 La 3 Zr 2 O 12 interface stability and kinetics as a function of temperature and current density." Journal of Power Sources 302 (2016): 135-139. [3] Cheng, Eric Jianfeng, Asma Sharafi, and Jeff Sakamoto. "Intergranular Li metal propagation through polycrystalline Li 6.25 Al 0.25 La 3 Zr 2 O 12 ceramic electrolyte." Electrochimica Acta 223 (2017): 85-91. [4] Hatzell, Kelsey B., et al. "Direct observation of active material interactions in flowable electrodes using X-ray tomography." Faraday discussions 199 (2017): 511-524. Figure 1

Designer defect stabilization of the super tetragonal phase in >70-nm-thick BiFeO3 films on LaAlO3 substrates

The stability of the “T-like” (T′) phase in BiFeO3 films grown on LaAlO3(001) is investigated. We show that the T′ phase can be stabilized for thicknesses >70 nm under ultralow incident flux conditions in pulsed laser ablation growth. This low flux results in a low growth rate; thus, the sample is held at high temperatures (>600 °C) for much longer than is typical. Transmission electron microscopy and X-ray diffraction analysis suggest that such growth conditions favor the formation of nanoscale “defect pockets”, which apply a local compressive strain of ∼1.8%. We propose that the cumulative effect of local stresses induced by such “designer defects” maintains macroscale strain coherence mechanical boundary conditions, which then preserves the T′ phase to thicknesses beyond conventional wisdom. Finally, by intentionally introducing an amorphous phase at the film-substrate interface, it is shown that the mixed-phase proportion can be tuned for a given thickness.

Deposition rate dependent phase/mechanical property evolution in zirconia and ceria-zirconia thin film by EB-PVD technique

Pure zirconia (ZrO2) and ceria (16 mol%) stabilized zirconia (CeSZr) thin films were prepared by electron beam physical vapor deposition with varying deposition rates (1, 4 and 8 Å/s) in order to correlate the phase changes to the mechanical property. X-ray diffraction and Raman spectra results indicate the presence of mixed monoclinic and tetragonal phases in ZrO2 film, but tetragonal phase dominated at lower deposition rate. However, irrespective of the deposition rate, cerium addition to ZrO2 resulted in complete stabilization of tetragonal phase. Depending on the presence of dual (ZrO2) or single (CeSZr) phase, either surface cracks or well-connected grain structure was observed in SEM, respectively. Thus, CeSZr film showed a four-fold increase in hardness in comparison to ZrO2, which can be attributed to the complete stabilization of tetragonal phase that hinders the crack propagation along the grain. Plastic deformation of CeSZr film was found to be 1.80 × 10−2 GPa, which is about ∼55% higher as compared to pure ZrO2 film (8.04 × 10−3 GPa). Thus, the development of CeSZr coating may lead to better surface protection of many components.

Mechanism of Reduced Sintering Temperature of Al₂O₃⁻ZrO₂ Nanocomposites Obtained by Microwave Hydrothermal Synthesis.

A novel method to obtain Al2O3–ZrO2 nanocomposites is presented. It consists of the co-precipitation step of boehmite (AlO(OH)) and ZrO2, followed by microwave hydrothermal treatment at 270 °C and 60 MPa, and by calcination at 600 °C. Using this method, we obtained two nanocomposites: Al2O3–20 wt % ZrO2 and Al2O3–40 wt % ZrO2. Nanocomposites were characterized by Fourier transformed infrared spectroscopy, Raman spectroscopy, X-ray diffraction, and transmission electron microscopy. Sintering behavior and thermal expansion coefficients were investigated during dilatometric tests. The sintering temperatures of the nanocomposites were 1209 °C and 1231 °C, respectively—approximately 100 °C lower than reported for such composites. We attribute the decrease of the sintering temperature to the specific nanostructure obtained using microwave hydrothermal treatment instead of conventional calcination. Microwave hydrothermal treatment resulted in a fine distribution of intermixed highly crystalline nanoparticles of boehmite and zirconia. Such intermixing prevented particle growth, which is a factor reducing sintering temperature. Further, due to reduced grain growth, stability of the θ-Al2O3 phase was extended up to 1200 °C, which enhances the sintering process as well. For the Al2O3–20 wt % ZrO2 composition, we observed stability of the zirconia tetragonal phase up to 1400 °C. We associate this stability with the mutual separation of zirconia nanoparticles in the alumina matrix.

Fabrication of dense and porous Li2ZrO3 nanofibers with electrospinning method

Lithium zirconate (Li2ZrO3) has been extensively studied as CO2 capture material, electrolyte material and coating material. Most of the previous studies were focused on the powder structure, while seldom taking a consideration of fiber structure. In the present work, dense and porous Li2ZrO3 nanofibers with surface area of 16 m2 g−1 were prepared by electrospinning method. IR spectral results showed that lithium carbonate was the intermediate for the formation of Li2ZrO3. The phase transformation of Li2ZrO3 underwent the pathway of amorphous precursor fibers, tetragonal zirconia and Li2CO3, tetragonal Li2ZrO3, and monoclinic Li2ZrO3. XRD and XPS results further suggested that Li2O diffusion from the fiber body to surface occurred for Li2ZrO3 nanofibers when heat-treated above 900 °C, and the tetragonal Li2ZrO3 with high surface area could be obtained at 800 °C. Bamboo structure appeared both for the dense and porous nanofibers heat-treated at 1000 °C. The high surface area and high thermal stability of tetragonal phase of Li2ZrO3 make it a promising candidate in CO2 absorption, electrolyte and coating material.

Al-, Y-, and La-doping effects favoring intrinsic and field induced ferroelectricity in HfO2: A first principles study

III-valent dopants have shown to be most effective in stabilizing the ferroelectric, crystalline phase in atomic layer deposited, polycrystalline HfO2 thin films. On the other hand, such dopants are commonly used for tetragonal and cubic phase stabilization in ceramic HfO2. This difference in the impact has not been elucidated so far. The prospect is a suitable doping to produce ferroelectric HfO2 ceramics with a technological impact. In this paper, we investigate the impact of Al, Y, and La doping, which have experimentally proven to stabilize the ferroelectric Pca21 phase in HfO2, in a comprehensive first-principles study. Density functional theory calculations reveal the structure, formation energy, and total energy of various defects in HfO2. Most relevant are substitutional electronically compensated defects without oxygen vacancy, substitutional mixed compensated defects paired with a vacancy, and ionically compensated defect complexes containing two substitutional dopants paired with a vacancy. The ferroelectric phase is strongly favored with La and Y in the substitutional defect. The mixed compensated defect favors the ferroelectric phase as well, but the strongly favored cubic phase limits the concentration range for ferroelectricity. We conclude that a reduction of oxygen vacancies should significantly enhance this range in Y doped HfO2 thin films. With Al, the substitutional defect hardly favors the ferroelectric phase before the tetragonal phase becomes strongly favored with the increasing concentration. This could explain the observed field induced ferroelectricity in Al-doped HfO2. Further Al defects are investigated, but do not favor the f-phase such that the current explanation remains incomplete for Al doping. According to the simulation, doping alone shows clear trends, but is insufficient to replace the monoclinic phase as the ground state. To explain this fact, some other mechanism is needed.

Tetragonal zirconia quantum dots in silica matrix prepared by a modified sol–gel protocol

Tetragonal zirconia quantum dots (t-ZrO2 QDs) in silica matrix with different compositions (x)ZrO2–(100 − x)SiO2 were fabricated by a modified sol–gel protocol. Acetylacetone was added as a chelating agent to zirconium propoxide to avoid precipitation. The powders as well as thin films were given thermal treatment at 650, 875 and 1100 °C for 4 h. The silica matrix remained amorphous after thermal treatment and acted as an inert support for zirconia quantum dots. The tetragonal zirconia embedded in silica matrix transformed into monoclinic form due to thermal treatment ≥ 1100 °C. The stability of tetragonal phase of zirconia is found to enhance with increase in silica content. A homogenous dispersion of t-ZrO2 QDs in silica matrix was indicated by the mapping of Zr, Si and O elements obtained from scanning electron microscope with energy dispersive X-ray analyser. The transmission electron images confirmed the formation of tetragonal zirconia quantum dots embedded in silica. The optical band gap of zirconia QDs (3.65–5.58 eV) was found to increase with increase in zirconia content in silica. The red shift of PL emission has been exhibited with increase in zirconia content in silica.

Dominating role of crystal structure over defect chemistry in black and white zirconia on visible light photocatalytic activity

Nanometric powder particles of white zirconia were synthesized through precursor route by the pyrolysis of zirconium (IV) butoxide at varied temperatures in air ranging from 900–1400 °C and were predominantly monoclinic in nature. To control the defect chemistry, the precursor was also pyrolyzed in a reduced atmosphere at 900 °C, eventually resulting in black zirconia. The stabilization of tetragonal phase and observed color change from white to black in samples pyrolyzed under reduced atmosphere was attributed to the creation of oxygen vacancies and disorder. The black and white zirconia produced delineated the influence of crystal structure and oxygen vacancies on the photocatalytic performance. Furthermore, zirconia synthesized at lower temperatures (600 and 800 °C) in air confirmed the detrimental role of tetragonal phase on the degradation behavior of methylene blue dye. High photocatalytic degradation rate for white zirconia was attributed to the presence of increased density of nano-sized pores and low recombination rate of electron-hole pairs as confirmed by PL measurements. Interestingly, black zirconia exemplified relatively limited activity albeit presence of oxygen vacancies. This negative effect was attributed to the presence of tetragonal phase and possibly, the insufficient creation of new energy states near valence and conduction band towards Fermi energy level.

Microstructure and magnetic properties of core-shell Nd-La-Fe-B sintered magnets

To balance the utilization of rare earth (RE) resource, abundant La has been incorporated into the Nd-Fe-B sintered magnets via the binary main phase (BMP) approach. Microstructure and magnetic properties of the Nd-La-Fe-B BMP magnets with increasing La substitution from 0 to 45 wt% were investigated. The results show that RE-rich intergranular phase with high oxygen content forms easily in the triple junction region for the La-substituted magnets. Those hcp-RE2O3 precipitates exhibit poor wettability with the matrix phase, leading to the direct exchange coupling of adjacent grains. As a result, the coercivity of Nd-La-Fe-B BMP magnets is dramatically reduced. Fortunately, the remanence can be maintained at a high level, ascribing to the inhomogeneous RE distributions among the grains (core-shell morphology), and the stable tetragonal phase after high-temperature sintering. With 27 wt% La substitution for Nd in the BMP magnet, the remanence decreases from 13.15 to 13.01 kGs by merely 1.06%. This work suggests that if one can optimize the microstructure by constructing magnetically isolated grains, low-cost Nd-La-Fe-B BMP magnets can be promising candidates for mass production.

Effect of formation of micro reaction locations (MRLs) on properties of polyvinylidene fluoride (PVDF) membranes

Micro reaction locations (MRLs) formed in membrane impact the integrated properties of membrane. In this paper, in order to form effective MRLs in PVDF membrane which performs attractive properties, YxFeyZr1-x-yO2 solid superacid coated TiO2 nanotubes (MSYFZr-TiNs) modified by sodium dodecylbenzene sulfonate (SDBS) are embedded into PVDF to prepare MSYFZr-TiNs/PVDF composite membranes with effective MRLs inside channels and on the surface of membranes. MSYFZr-TiNs and MSYFZr-TiNs/PVDF composite membranes are characterized and tested. The results show that YxFeyZr1-x-yO2 solid superacid with stable tetragonal phase reaches a hammett acidity of − 16.468, decomposing inorganic pollutants or restraining their formation inside channels and surface. The MSYFZr-TiNs/PVDF composite membranes with MRLs perform attractive anti-compaction and anti-fouling properties through MRLs. The water contact angle, stable degradation ratios for oil and Fe2O3 are 36.5°, 13.2% and 12.1%, respectively. Furthermore, when treating oily wastewater, the membrane permeate flux and oil retention ratio are 354 L m−2 h−1 and 93.48%, respectively. Therefore, MSYFZr-TiNs/PVDF composite membranes will possess desirable application in water cleaning.