Tribological Properties of Magnesium Ion-exchanged α-Zirconium Phosphate as a Solid Lubricant Additive in Lithium Grease

Magnesium ion-exchanged a-zirconium phosphates(Mg-α-ZrP) with particle sizes of 600 and 80 nm were prepared through the sealed ion-exchange and one-step hydrothermal synthesis methods, respectively. It was found that larger particles of Mg-α-ZrP had a higher load-carrying capacity than that of smaller particles, whereas smaller Mg-α-ZrP particles had better anti-wear properties than that of larger Mg-α-ZrP particles under mild loads. The correlation between the particle size of the sample and the surface roughness of the friction pair thus seems to be a key factor influencing the performance.

Synthesis and Tribological Properties of Sodium-Ion-Exchangedα-Zirconium Phosphate

Sodium-ion-exchangedα-zirconium phosphate(Na-α-ZrP)was synthesized by using disodium hydrogen phosphate as the sodium source,which was an efficient ion exchange way.The tribological properties of Na-α-ZrP as an additive in lithium grease were investigated by a four-ball friction tester and a SRV tester,respectively.The synergistic effect of Na-α-ZrP with ZDDP was also studied.Results indicate that Na-α-ZrP can effectively improve the antiwear and friction-reducing properties of lithium grease.Combined with ZDDP,the grease demonstrated excellent anti-wear performance,especially under high loads.The possible wear mechanism was discussed by observing the worn surface using 3D optical profiler,scanning electron microscopy(SEM),energy-dispersive spectrometry(EDS),and X-ray photoelectron spectroscopy(XPS).The simple synthetic method and superior tribological performance make the Na-α-ZrP become a potential choice for lubricant additives.

Synthesis, characterization and antimicrobial activity of zinc and cerium co-doped α-zirconium phosphate

A series of zinc ions or/and cerium ions co-doped a-zirconium phosphate （Zn-Ce@ZrPs） were prepared. The novel Zn-Ce@ZrPs were characterized and the antibacterial activity on Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus were tested. The results showed that zinc ions （Zn2＋） or/and cerium ions （Ce3＋） were combined with ZrP, and the Ce3＋ was adsorbed on the surface of ZrP through hydrogen bonds, while Zn2＋ intercalated into the interlayer of ZrP. Zn-Ce@ZrPs showed excellent synergistic antibacterial activity. When Zn2＋/Ce3＋ atomic ratio was 0.6, the Zn-Ce@ZrP3 showed the highest synergistic antibacterial efficiency, suggesting great potential ap- plication as antibacterial agents in microbial control.

Dispersion–tribological property relationship in mineral oils containing 2D layered α-zirconium phosphate nanoplatelets

Inorganic nanomaterials exhibit superior friction-reduction and anti-wear properties in oils. In this study, 2D layered α-zirconium phosphate (α-ZrP) nanosheets intercalated with different amines have been synthesized to study their dispersion stabilities in lubricating oil and tribological applications. The intercalated amines should be sufficiently long and lipophilic to provide stabilization to α-ZrP nanosheets in mineral oil. The results of tribological tests illustrate that with the addition of well-dispersed nanosheets, the coefficient of friction (COF) and pin volume loss reduce by ~47% and 75%, respectively. The excellent dispersion stability enables the nanosheets to flow into the contact area at the beginning, and thereby protect the rubbing surface. A reduction in the van der Waals forces between the adjacent layers induced by the intercalated amines transforms the friction between adjacent layers from pin disk to sliding, leading to a decrease in the COF under hydrodynamic lubrication. The study provides a new method to enhance the tribological properties via tuning the dispersion stabilities of nanomaterials in oils.

Assembly of exfoliated α-zirconium phosphate nanosheets:Mechanisms and versatile applications

α-Zirconium phosphate(Zr(HPO_(4))_(2)⋅H_(2)O,α-ZrP)is an inorganic layered compound.Since the first report of crystallineα-ZrP in 1964,thanks to its simple synthesis and unique physiochemical properties,α-ZrP has found widespread application in many fields including mechanical reinforcing,barrier improvement,flame retardancy,anticorrosion,catalysis,environment,energy,and medicine.Because of the ease of exfoliation ofα-ZrP to obtain single-layer nanosheets,as well as its rich surface chemistry thanks to the high density of orderly arranged surface acidic hydroxyl groups,α-ZrP single-layer nanosheets are ideal building blocks for self-assembly or assembly with other chemicals.The assembly ofα-ZrP nanosheets could form a randomly dispersed structure(isotropic),roughly ordered structure(nematic),or highly ordered structure(smectic)within liquid colloids or solid hybrids(including hydrogels).Thanks to the combination of the unique structures and the novel functions of the components,the assembled materials have found a wide verity of applications due to their excellent properties.In this article,the methods to synthesizeα-ZrP,the approaches and mechanisms to exfoliateα-ZrP,and the strategies to assembleα-ZrP nanosheets to form various structures,as well as the applications of the assembled materials are reviewed.The emerging prospects ofα-ZrP nanosheets as a key material in next-generation functional applications are envisioned.

Novel interface engineering of LDH-based materials on Mg alloy for efficient photocatalytic systems considering the geometrical linearity of condensed phosphates

This study presents a facile and rapid method for synthesizing novel Layered Double Hydroxide(LDH)nanoflakes,exploring their application as a photocatalyst,and investigating the influence of condensed phosphates'geometric linearity on their photocatalytic properties.Herein,the Mg O film,obtained by plasma electrolysis of AZ31 Mg alloys,was modified by growing an LDH film,which was further functionalized using cyclic sodium hexametaphosphate(CP)and linear sodium tripolyphosphate(LP).CP acted as an enhancer for flake spacing within the LDH structure,while LP changed flake dispersion and orientation.Consequently,CP@LDH demonstrated exceptional efficiency in heterogeneous photocatalysis,effectively degrading organic dyes like Methylene blue(MB),Congo red(CR),and Methyl orange(MO).The unique cyclic structure of CP likely enhances surface reactions and improves the catalyst's interaction with dye molecules.Furthermore,the condensed phosphate structure contributes to a higher surface area and reactivity in CP@LDH,leading to its superior photocatalytic performance compared to LP@LDH.Specifically,LP@LDH demonstrated notable degradation efficiencies of 93.02%,92.89%,and 88.81%for MB,MO,and CR respectively,over a 40 min duration.The highest degradation efficiencies were observed in the case of the CP@LDH sample,reporting 99.99%for MB,98.88%for CR,and 99.70%for MO.This underscores the potential of CP@LDH as a highly effective photocatalyst for organic dye degradation,offering promising prospects for environmental remediation and water detoxification applications.

Effect of safety valve types on the gas venting behavior and thermal runaway hazard severity of large-format prismatic lithium iron phosphate batteries

The safety valve is an important component to ensure the safe operation of lithium-ion batteries(LIBs).However,the effect of safety valve type on the thermal runaway(TR)and gas venting behavior of LIBs,as well as the TR hazard severity of LIBs,are not known.In this paper,the TR and gas venting behavior of three 100 A h lithium iron phosphate(LFP)batteries with different safety valves are investigated under overheating.Compared to previous studies,the main contribution of this work is in studying and evaluating the effect of gas venting behavior and TR hazard severity of LFP batteries with three safety valve types.Two significant results are obtained:(Ⅰ)the safety valve type dominates over gas venting pressure of battery during safety venting,the maximum gas venting pressure of LFP batteries with a round safety valve is 3320 Pa,which is one order of magnitude higher than other batteries with oval or cavity safety valve;(Ⅱ)the LFP battery with oval safety valve has the lowest TR hazard as shown by the TR hazard assessment model based on gray-fuzzy analytic hierarchy process.This study reveals the effect of safety valve type on TR and gas venting,providing a clear direction for the safety valve design.

The synthesis and applications of α-zirconium phosphate

The synthesis of α-ZrP with a range of crystallinity is of high importance due to the different requirements in various applications.Nanosized crystalline α-ZrP is typically obtained by refluxing amorphous ZrP in concentrated H3PO4 solutions.Microcrystalline α-ZrP are obtained by direct precipitation in the presence of either HF or oxalic acid which are used as complexing agents for zirconium.These larger crystals are useful as ion-exchangers in column-type applications as the back pressure can be significantly reduced.A novel minimalistic synthesis that is green,simple and fast is highlighted in this review.Both nano-sized and micro-sized α-ZrP can be prepared via this protocol to meet many potential applications.Applications of α-ZrP in ion-exchange,catalysis,lubricants,intercalation hosts,polymer fillers and fire retardants are discussed.

Preintercalation of Layered γ-Zirconium Phosphate for Preparation of Immobilized Hemoglobin

Layeredγ-Zirconium phosphate (γ-ZrP) preintercalated with butylamine, tetra (n-butylammonium)hydroxide, dimethylamine respectively, or only ultrasonificated, for preparation of immobilized hemoglobin were investigated in this report.

Integrated Effects of Phosphate Rock and Chemical Fertilizers on the Dynamics of Soil Bacterial in Acidic Rice Paddy Soils of Man (Ivory Coast)

In agricultural soils, phosphorus is often limited, leading farmers to employ artificial supplementation through both inorganic and organic fertilization methods due to its restricted availability. Soil fertilization has the potential to augment both the abundance and diversity of bacterial communities. Our study aimed to assess the effects of phosphate amendments, derived from natural phosphate rock, and chemical fertilizers (TSP, NPK), on the density and diversity of bacterial communities within the study plots. We developed and applied eight phosphate amendments during the initial cultivation cycle. Soil samples were collected post 1st and 2nd cultivation cycles, and the quantification of both total and cultivable phosphate-solubilizing bacteria (PSB) was conducted. Additionally, we analyzed bacterial community structure, α-diversity (Shannon Diversity Index, Evenness Index, Chao1 Index). The combination of natural phosphate rock (PR) and chemical fertilizers (TSP, NPK) significantly increased (p 7 bacteria/g dry soil) and phosphate-solubilizing bacteria (0.01 to 6.8 × 107 PSB/g dry soil) in comparison to unamended control soils. The diversity of bacterial phyla (Firmicutes, Actinobacteria, Proteobacteria, Halobacterota, Chloroflexia) observed under each treatment remained consistent regardless of the nature of the phosphate amendment applied. However, changes in the abundance of the bacterial phyla populations were observed as a function of the nature of the phosphate amendment or chemical fertilizer. It appears that the addition of excessive natural phosphate rock does not alter the number and the diversity of soil microorganisms population despite successive cultivation cycles. However, the addition of excessive chemical fertilizer reduces soil microorganisms density and structure after the 2nd cultivation cycle.

Differential roles of C-3 and C-6 phosphate monoesters in affecting potato starch properties

The effects of starch phosphate monoester content(SPC),namely C-3(C3P)and C-6 phosphate monoesters(C6P),on the starch properties were investigated using four potato starches with varied SPC/C3P/C6P and two nonphosphorylated maize starches with a similar range of amylose content(AC)as controls.The starch property results showed that a higher SPC is associated with lower turbidity,storage and loss modulus after storage,and water solubility,but higher swelling power(SP)and pasting viscosities.These findings suggested that SPC inhibited molecular rearrangement during storage and starch leaching during heating,and enhanced swelling and viscosities due to increased hydration and water uptake caused by the repulsion effect of phosphate groups and a less ordered crystalline structure.Increased SPC also resulted in lower resistant starch(RS)content in a native granular state but higher RS after retrogradation.Pearson correlations further indicated that SPC/C3P/C6P were positively correlated with peak(r^(2)=0.925,0.873 and 0.930,respectively),trough(r^(2)=0.994,0.968 and 0.988,respectively),and final viscosities(r^(2)=0.981,0.968 and 0.971,respectively).Notably,SPC,mainly C3P,exhibited a significantly positive correlation with SP(r^(2)=0.859)and setback viscosity(r^(2)=0.867),whereas SPC,mainly C6P,showed a weak positive correlation with RS after retrogradation(r^(2)=0.746).However,SPC had no significant correlations with water solubility,turbidity and rheology properties,which were more correlated with AC.These findings are helpful for the food industry to select potato starches with desired properties based on their contents of SPC,C3P,or C6P.

Effect of Fluoride on the Ion-association of Calcium Phosphate and Crystallization of Hydroxyapatite

Using a titration setup to accurately control the reaction conditions and in situ monitor the reaction,we showed that fluoride exhibited negligible effects on the ion association process of calcium and phosphate and the formation of ACP nanospheres in a buffer solution with constant ionic strength.However,the stability of ACP increased with increasing fluoride concentration,which was ascribed to the inhibitory effect of fluoride on the aggregation of ACP nanospheres and the nucleation of nanocrystals on the surface of ACP nanospheres.Furthermore,fluoride could inhibit the lateral growth of HAP nanosheets and promote the formation of rod-like crystals.These results further improve our understanding of the crystallization pathway of HAP crystals and the regulatory effects of fluoride.

Preparation and interface state of phosphate tailing-based geopolymers

The long-term storage of phosphate tailings will occupy a large amount of land,pollute soil and groundwater,thus,it is crucial to achieve the harmless disposal of phosphate tailings.In this study,high-performance geopolymers with compressive strength of 38.8 MPa were prepared by using phosphate tailings as the main raw material,fly ash as the active silicon-aluminum material,and water glass as the alkaline activator.The solid content of phosphate tailings and fly ash was 60% and 40%,respectively,and the water-cement ratio was 0.22.The results of XRD,FTIR,SEM-EDS and XPS show that the reactivity of phosphate tailings with alkaline activator is weak,and the silicon-aluminum material can react with alkaline activator to form zeolite and gel,and encapsulate/cover the phosphate tailings to form a dense phosphate tailings-based geopolymer.During the formation of geopolymers,part of the aluminum-oxygen tetrahedron replaced the silicon-oxygen tetrahedron,causing the polycondensation reaction between geopolymers and increasing the strength of geopolymers.The leaching toxicity test results show that the geopolymer has a good solid sealing effect on heavy metal ions.The preparation of geopolymer from phosphate tailings is an important way to alleviate the storage pressure and realize the resource utilization of phosphate tailings.

Gadolinium-doped injectable magnesium-calcium phosphate bone cements for noninvasive visualization

Injectable bone cements are used in minimally invasive surgical techniques including vertebroplasty and kyphoplasty.This work is devoted to the development of magnesium-calcium phosphate cements(MCPCs)doped with gadolinium ions(Gd^(3+))for bone defect repair.Interaction between cement powders and a cement liquid resulted in the formation of newberyite and brushite phases,which gave mechanical strength up to 17 MPa without a thermal effect.The introduction of Gd3+into the lattice was confirmed by electron paramagnetic resonance spectroscopy;the doping increased injectivity while giving rise to antibacterial properties against Escherichia coli.Assays of the cement samples soaking in Kokubo’s simulated body fluid revealed the formation of calcium phosphate coatings on the cements’surface.The cements manifested biocompatibility with the MG-63 cell line and significantly enhanced contrast when Gd-MCPC was placed into a bone defect and examined by X-ray micro-computed tomography.For the first time,visualization of a Gd-doped cement material was achieved in a model of a bone defect analyzed by MRI.

Efficient Removal of Phosphate from Aqueous Solutions Using Corundum-hollow-spheres Supported Caclined Hydrotalcite Porous Thin Films

Phosphate was removed from aqueous environment by corundum-hollow-spheres supported caclined hydrotalcite (cHT) thin films. Mg-Al-CO3 hydrotalcite (HT) thin films were deposited on corundumhollow-sphere substrates by hydrothermal homogeneous precipitation at 120℃for 30-240 min and cHT thin films were obtained by annealing of the HT thin films at 500℃for 180 min. Their crystal phase, morphology and microstructure were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM).The results show that homogeneous, well-crystallized and hierarchical flower-like thin films were deposited firmly on the surface of the corundum. The mechanism of nucleation and growth of the HT thin films was fitted well with the anion coordination polyhedron growth unit model. To determine the absorption of phosphate by this adsorbent, different bed depth (10-30 cm) and flow rate (1.0-3.0 m L/min) were examined by column experiments. The highest removal efficiency of phosphate amounted to 98.5%under optimum condition (pH=7.2). The adsorption capacity increased as the bed depth increased and decreased as the flow rate increased.

Natural variation in ZmGRF10 regulates tolerance to phosphate deficiency in maize by modulating phosphorus remobilization

Phosphorus is a limiting factor in agriculture due to restricted availability in soil and low utilization efficiency of crops.The identification of superior haplotypes of key genes responsible for low-phosphate(Pi)tolerance and their natural variation is important for molecular breeding.In this study,we conducted genome-wide association studies on low-phosphate tolerance coefficients using 152 maize inbred lines,and identified a significant association between SNPs on chromosome 7 and a low-phosphate tolerance coefficient.ZmGRF10 was identified as a candidate gene involved in adaptation of maize to Pi starvation.Expression of ZmGRF10 is induced by Pi starvation.A mutation in ZmGRF10 alleviated Pi starvation stress.RNA-seq analyses revealed significant upregulation of genes encoding various phosphatases in the zmgrf10-1 mutant,suggesting that ZmGRF10 negatively regulates expression of these genes,thereby affecting low-Pi tolerance by suppressing phosphorus remobilization.A superior haplotype with variations in the promoter region exhibited lower transcription activity of ZmGRF10.Our study unveiled a novel gene contributing to tolerance to low-Pi availability with potential to benefit molecular breeding for high Pi utilization.

Surface-neutralization engineered NiCo-LDH/phosphate hetero-sheets toward robust oxygen evolution reaction

Developing highly active oxygen evolution reaction(OER)electrocatalysts with robust durability is essential in producing high-purity hydrogen through water electrolysis.Layered double hydroxide(LDH)based catalysts have demonstrated efficient catalytic performance toward the relatively sluggish OER.By considering the promotion effect of phosphate(Pi)on proton transfer,herein,a facile phosphate acid(PA)surface-neutralization strategy is developed to in-situ construct NiCo-LDH/NiCoPi hetero-sheets toward OER catalysis.OER activity of NiCoLDH is significantly boosted due to the proton promotion effect and the electronic modulation effect of NiCoPi.As a result,the facilely prepared NiCo-LDH/NiCoPi catalyst displays superior OER catalytic activity with a low overpotential of 300 mV to deliver 100 mA cm^(-2)OER and a Tafel slope of 73 mV dec^(-1).Furthermore,no visible activity decay is detected after a 200-h continuous OER operation.The present work,therefore,provides a promising strategy to exploit robust OER electrocatalysts for commercial water electrolysers.

In-situ construction of abundant active centers on hierarchically porous carbon electrode toward high-performance phosphate electrosorption: Synergistic effect of electric field and capture sites

Phosphate removal is crucial for eutrophication control and water quality improvement.Electro-assisted adsorption,an eco-friendly elec-trosorption process,exhibited a promising potential for wastewater treatment.However,there are few works focused on phosphate electro-sorption,and reported electrodes cannot attach satisfactory removal capacities and rates.Herein,electro-assisted adsorption of phosphate via in-situ construction of La active centers on hierarchically porous carbon(LaPC)has been originally demonstrated.The resulted LaPC composite not only possessed a hierarchically porous structure with uniformly dispersed La active sites,but also provided good conductivity for interfacial electron transfer.The LaPC electrode achieved an ultrahigh phosphate electrosorption capability of 462.01 mg g^(-1) at 1 V,outperforming most existing electrodes.The superior phosphate removal performance originates from abundant active centers formed by the coupling of electricfield and capture sites.Besides,the stability and selectivity toward phosphate capture were maintained well even under comprehensive conditions.Moreover,a series of kinetics and isotherms models were employed to validate the electrosorption process.This work demonstrates a deep understanding and promotes a new level of phosphate electrosorption.

Fluid-Related Performances and Compressive Strength of Clinker-Free Cementitious Backfill Material Based on Phosphate Tailings

Phosphate tailings are usually used as backfill material in order to recycle tailings resources.This study considers the effect of the mix proportions of clinker-free binders on the fluidity,compressive strength and other key performances of cementitious backfill materials based on phosphate tailings.In particular,three solid wastes,phosphogypsum(PG),semi-aqueous phosphogypsum(HPG)and calcium carbide slag(CS),were selected to activate wet ground granulated blast furnace slag(WGGBS)and three different phosphate tailings backfill materials were prepared.Fluidity,rheology,settling ratio,compressive strength,water resistance and ion leaching behavior of backfill materials were determined.According to the results,when either PG or HPG is used as the sole activator,the fluidity properties of the materials are enhanced.Phosphate tailings backfill material activated with PG present the largest fluidity and the lowest yield stress.Furthermore,the backfill material’s compressive strength is considerably increased to 2.9 MPa at 28 days after WGGBS activation using a mix of HPG and CS,all with a settling ratio of only 1.15 percent.Additionally,all the three ratios of binder have obvious solidification effects on heavy metal ions Cu and Zn,and P in phosphate tailings.

Enhancing sustainability in phosphate ore processing:Performance of frying oil as alternative flotation collector for carbonate removal

Recycling waste frying oils for the synthesis of flotation reagents presents a promising avenue for sustainable waste management.Moreover,it offers a cost-effective solution for crafting a specialized collector designed to efficiently remove carbonates and enhance phosphate enrichment in froth flotation processes.This study focuses on the synthesis of an anionic collector using the saponification reaction of a frying oil sample,subsequently applied to the flotation of calcite and dolomite.To elucidate the adsorption mechanisms of the frying oil collector(FrOC)and sodium oleate,a reference collector,on fluorapatite,calcite,dolomite,and quartz surfaces,comprehensive experiments were conducted,including zeta potential measurements and Fourier transform infrared spectroscopy.Results revealed diverse adsorption affinities of the molecules towards these minerals.To assess the practical performance of the collector,flotation tests were conducted using a natural phosphate ore mixture,employing a BoxBehnken experimental design.Notably,under optimized conditions(pH 9,1000 g/t of FrOC,3.5 min of conditioning,and 6 min of flotation),FrOC exhibited excellent performance,with calcite and dolomite recoveries exceeding 80%,while apatite recovery in the concentrate fraction remained below 10%.This work exemplifies both circular economy practices and the distinctive approach to sustainable mineral processing.