Layer-by-layer fabrication of montmorillonite coating immobilizing Cu_(2)O nanoparticles for continuously catalyzing glycerol to dihydroxyacetone

Microreactors are increasingly used for green and safe chemical processes owing to their benefits of superior mass and heat transfer,increased yield,safety,and simplicity of control.However,immobilizing catalysts in microreactors remains challenging.In this investigation,a technique for creating Cu_(2)O/montmorillonite catalyst coating,using electrostatic attraction for layer-by-layer self-assembly,was proposed.The montmorillonite film's morphology and thickness could be efficiently regulated by adjusting the degree of exfoliation and surface charge of montmorillonite,alongside layer-by-layer coating times.The Cu_(2)O nanoparticles were immobilized using the flow deposition approach.The resulting Cu_(2)O@montmorillonite-film-coated capillary microreactor successfully transformed glycerol into dihydroxyacetone.The conversion of glycerol and product selectivity could be controlled by adjusting the molar ratio of reactants,temperature,residence time,and Cu_(2)O loading.The maximum glycerol conversion observed was 47.6%,with a 27%selectivity toward dihydroxyacetone.The study presents a technique for immobilizing montmorillonite-based catalyst coatings in capillary tubing,which can serve as a foundation for the future application of microreactors in glycerol conversion.

Self-repairing Al_(2)O_(3)-TiO_(2)coatings fabricated through plasma electrolytic oxidation with various cathodic pulse parameters

The influence of cathodic pulse parameters was evaluated on plasma electrolytic oxidation(PEO)coatings grown on 7075 aluminum alloy in a silicate-based electrolyte containing potassium titanyl oxalate(PTO)using pulsed bipolar waveforms with various cathodic duty cycles and cathodic current densities.The coatings were characterized by SEM,EDS,and XRD.EIS was applied to investigate the electrochemical properties.It was observed that the increase of cathodic duty cycle and cathodic current density from 20%and 6 A/dm^(2) to 40%and 12 A/dm^(2) enhances the growth rate of the inner layer from 0.22 to 0.75μm/min.Adding PTO into the bath showed a fortifying effect on influence of the cathodic pulse and the mentioned change of cathodic pulse parameters,resulting in an increase of the inner layer growth rate from 0.25 to 1.10μm/min.Based on EDS analysis,Si and Ti were incorporated dominantly in the upper parts of the coatings.XRD technique merely detectedγ-Al_(2)O_(3),and there were no detectable peaks related to Ti and Si compounds.However,the EIS results confirmed that the incorporation of Ti^(4+)into alumina changed the electronic properties of the coating.The coatings obtained from the bath containing PTO using the bipolar waveforms with a cathodic duty cycle of 40%and current density values higher than 6 A/dm^(2) showed highly appropriate electrochemical behavior during 240 d of immersion due to an efficient repairing mechanism.Regarding the effects of studied parameters on the coating properties,the roles of cathodic pulse parameters and PTO in the PEO process were highlighted.

LPCS Ni-Zn-Al_(2)O_(3) Intermediate Layer Enhanced SPS NiCr-Cr_(3)C_(2) Coating with Higher Corrosion and Wear Resistances

The double-layer NiCr-Cr_(3)C_(2)/Ni-Zn-Al_(2)O_(3) coatings with sufficient corrosion and wear resistance were prepared on low carbon steel substrates.The intermediate layers Ni-Zn-Al_(2)O_(3) were fabricated by using low-pressure cold spray (LPCS) method to improve the salt fog corrosion resistance properties of the supersonic plasma spray (SPS) NiCr-Cr_(3)C_(2) coatings.The friction and wear performance for the double-layer and single-layer NiCr-Cr_(3)C_(2) coatings were carried out by line-contact reciprocating sliding,respectively.Combined with the coating surface analysis techniques,the effect of the salt fog corrosion on the tribological properties of the double-layer coatings was studied.The results showed that the double-layer coatings exhibited better wear resistance than that of the single-layer coatings,due to the better corrosion resistance of the intermediate layer;the wear mass losses of the double-layer coatings was reduced by 70%than that of the single layer coatings and the wear mechanism of coatings after salt fog corrosion conditions is mainly corrosion wear.

In-situ coating and surface partial protonation co-promoting performance of single-crystal nickel-rich cathode in all-solid-state batteries

The poor electrochemical performance of all-solid-state batteries(ASSBs),which is assemblied by Ni-rich cathode and poly(ethylene oxide)(PEO)-based electrolytes,can be attributed to unstable cathodic interface and poor crystal structure stability of Ni-rich cathode.Several coating strategies are previously employed to enhance the stability of the cathodic interface and crystal structure for Ni-rich cathode.However,these methods can hardly achieve simplicity and high efficiency simultaneously.In this work,polyacrylic acid(PAA)replaced traditional PVDF as a binder for cathode,which can achieve a uniform PAA-Li(LixPAA(0<x≤1))coating layer on the surface of single-crystal LiNi_(0.83)Co_(0.12)Mn_(0.05)O_(2)(SC-NCM83)due to H^(+)/Li^(+)exchange reaction during the initial charging-discharging process.The formation of PAA-Li coating layer on cathode can promote interfacial Li^(+)transport and enhance the stability of the cathodic interface.Furthermore,the partially-protonated surface of SC-NCM83 casued by H^(+)/Li^(+)exchange reaction can restrict Ni ions transport to enhance the crystal structure stability.The proposed SC-NCM83-PAA exhibits superior cycling performance with a retention of 92%compared with that(57.3%)of SC-NCM83-polyvinylidene difluoride(PVDF)after 200 cycles.This work provides a practical strategy to construct high-performance cathodes for ASSBs.

Mathematical modeling and simulations of stress mitigation by coating polycrystalline particles in lithium-ion batteries

A chemo-mechanical model is developed to investigate the effects on the stress development of the coating of polycrystalline Ni-rich LiNixMnyCo_(z)O_(2)(x≥0.8)(NMC)particles with poly(3,4-ethylenedioxythiophene)(PEDOT).The simulation results show that the coating of primary NMC particles significantly reduces the stress generation by efficiently accommodating the volume change associated with the lithium diffusion,and the coating layer plays roles both as a cushion against the volume change and a channel for the lithium transport,promoting the lithium distribution across the secondary particles more homogeneously.Besides,the lower stiffness,higher ionic conductivity,and larger thickness of the coating layer improve the stress mitigation.This paper provides a mathematical framework for calculating the chemo-mechanical responses of anisotropic electrode materials and fundamental insights into how the coating of NMC active particles mitigates stress levels.

Development of Superhydrophobic Nano-SiO_(2)and Its Field Application in Low-permeability,High-temperature,and High-salinity Oil Reservoirs

In this study,to meet the stringent requirements on the hydrophobicity of nano-SiO_(2)particles for use in depressurization and enhanced injection operations in high-temperature and high-salinity oil reservoirs,secondary chemical grafting modification of nano-SiO_(2)is performed using a silane coupling agent to prepare superhydrophobic nano-SiO_(2) particles.Using these superhydrophobic nano-SiO_(2)particles as the core agent,and liquid paraffin or diesel as the dispersion medium,a uniform dispersion of nano-SiO_(2)particles is achieved under high-speed stirring,and a chemically enhanced water injection system with colloidal stability that can be maintained for more than 60 d is successfully developed.Using this system,a field test of depressurization and enhanced injection is carried out on six wells in an oilfield,and the daily oil production level is increased by 11 t.The cumulative increased water injection is 58784 m^(3),the effective rate of the measures was 100%,and the average validity period is 661 d.

Preventing formation of intermetallic compounds in ultrasonic-assisted Sn soldering of Mg/Al alloys through pre-plating a Ni coating layer on the Mg substrate

Magnesium and aluminum alloys are widely used in various industries because of their excellent properties,and their reliable connection may increase application of materials.Intermetallic compounds(IMCs)affect the joint performance of Mg/Al.In this study,AZ31 Mg alloy with/without a nickel(Ni)coating layer and 6061 Al alloy were joined by ultrasonic-assisted soldering with Sn-3.0Ag-0.5Cu(SAC)filler.The effects of the Ni coating layer on the microstructure and mechanical properties of Mg/Al joints were systematically investigated.The Ni coating layer had a significant effect on formation of the Mg_(2)Sn IMC and the mechanical properties of Mg/Al joints.The blocky Mg_(2)Sn IMC formed in the Mg/SAC/Al joints without a Ni coating layer.The content of the Mg_(2)Sn IMC increased with increasing soldering temperature,but the joint strength decreased.The joint without a Ni coating layer fractured at the blocky Mg_(2)Sn IMC in the solder,and the maximum shear strength was 32.2 MPa.By pre-plating Ni on the Mg substrate,formation of the blocky Mg_(2)Sn IMC was inhibited in the soldering temperature range 240–280℃and the joint strength increased.However,when the soldering temperature increased to 310℃,the blocky Mg_(2)Sn IMC precipitated again in the solder.Transmission electron microscopy showed that some nano-sized Mg_(2)Sn IMC and the(Cu,Ni)_(6)Sn_(5)phase formed in the Mg(Ni)/SAC/Al joint soldered at 280℃,indicating that the Ni coating layer could no longer prevent diffusion of Mg into the solder when the soldering temperature was higher than 280℃.The maximum shear strength of the Mg(Ni)/SAC/Al joint was 58.2 MPa for a soldering temperature of 280℃,which was 80.7%higher than that of the Mg/SAC/Al joint,and the joint was broken at the Mg(Ni)/SAC interface.Pre-plating Ni is a feasible way to inhibit formation of IMCs when joining dissimilar metals.

Study on the effective elastic performance of composites containing decagonal symmetric two-dimensional quasicrystal coatings

On account of the Mori-Tanaka approach,the effective elastic performance of composites containing decagonal symmetric two-dimensional(2D)quasicrystal(QC)coatings is studied.Explicit expressions for the effective elastic constants of rare-earth QC reinforced magnesium-based composites are provided.Detailed discussion is presented on the effects of the volume fraction of the inclusions,the aspect ratio of the inclusions,the coating thickness,and the coating material parameters on the effective elastic constants of the composites.The results indicate that considering the coating increases the effective elastic constants of the composites to some extent.

Comparative investigation of microstructure and high-temperature oxidation resistance of high-velocity oxy-fuel sprayed CoNiCrAlY/nano-Al_(2)O_(3) composite coatings using satellited powders

Satellited CoNiCrAlY–Al_(2)O_(3)feedstocks with 2wt%, 4wt%, and 6wt% oxide nanoparticles and pure CoNiCrAlY powder were deposited by the high-velocity oxy fuel process on an Inconel738 superalloy substrate. The oxidation test was performed at 1050℃ for 5, 50, 100,150, 200, and 400 h. The microstructure and phase composition of powders and coatings were characterized by scanning electron microscopy and X-ray diffraction, respectively. The bonding strength of the coatings was also evaluated. The results proved that with the increase in the percentage of nanoparticles(from 2wt% to 6wt%), the amount of porosity(from 1vol% to 4.7vol%), unmelted particles, and roughness of the coatings(from 4.8 to 8.8 μm) increased, and the bonding strength decreased from 71 to 48 MPa. The thicknesses of the thermally grown oxide layer of pure and composite coatings(2wt%, 4wt%, and 6wt%) after 400 h oxidation were measured as 6.5, 5.5, 7.6, and 8.1 μm, respectively.The CoNiCrAlY–2wt% Al_(2)O_(3)coating showed the highest oxidation resistance due to the diffusion barrier effect of well-dispersed nanoparticles. The CoNiCrAlY–6wt% Al_(2)O_(3)coating had the lowest oxidation resistance due to its rough surface morphology and porous microstructure.

Effect of chromium on hot corrosion behavior of arc-sprayed NiCr coatings

In this article,NiCr coatings with chromium content of 13%,27%and 41%were prepared by arc spraying.They were exposed in molten salts(NaCl-Na_(2)SO_(4))at 800℃for 200 hours.The effect of chromium content on the hot corrosion behavior of the coatings was in-vestigated.X-ray diffraction(XRD)and scanning electron microscope with energy dispersion spectrum(SEM-EDS)were used to analyze the phase compositions,morphologies and chemical compositions of the coatings.The results show that NiCr13 coating exhibited the worst hot corrosion resistance due to the low chromium content,which resulted in NiO being the major reaction product.It should be noted that the hot corrosion resistance of NiCr27 coating was better than that of NiCr41 coating.The basic fluxing of Cr_(2)O_(3) lowered its protection during the hot corrosion process and led to the formation of porous Cr_(2)O_(3) on the NiCr41 coating.The molten salts accelerated the oxidation reac-tion resulting in thicker and porous oxide scales formed on the surfaces of coatings.

Critical current degradation in an epoxy-impregnated rare-earth Ba_(2)Cu_(3)O_(7-x)coated conductor caused by damage during a quench

High-temperature superconducting(HTS)rare-earth Ba_(2)Cu_(3)O_(7-x)(REBCO)coated conductors(CCs)have significant potential in high-current and high-field applications.However,owing to the weak interface strength of the laminated composite REBCO CCs,the damage induced by the thermal mismatch stress under a combination of epoxy impregnation,cooling,and quenching can cause premature degradation of the critical current.In this study,a three-dimensional(3D)electromagnetic-thermal-mechanical model based on the H-formulation and cohesive zone model(CZM)is developed to study the critical current degradation characteristics in an epoxy-impregnated REBCO CC caused by the damage during a quench.The temperature variation,critical current degradation of the REBCO CC,and its degradation onset temperature calculated by the numerical model are in agreement with the experimental data taken from the literature.The delamination of the REBCO CC predicted by the numerical model is consistent with the experimental result.The numerical results also indicate that the shear stress is the main contributor to the damage propagation inside the REBCO CC.The premature degradation of the critical current during a quench is closely related to the interface shear strength inside the REBCO CC.Finally,the effects of the coefficient of thermal expansion(CTE)of the epoxy resin,thickness of the substrate,and substrate material on the critical current degradation characteristics of the epoxy-impregnated REBCO CC during a quench are also discussed.These results help us understand the relationship between the current-carrying degradation and damage in the HTS applications.

Two-Dimensional Graphitic Carbon-Nitride(g-C_(3)N_(4))-Coated LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)Cathodes for High-Energy-Density and Long-Life Lithium Batteries

High-capacity nickel-rich layered oxides are promising cathode materials for high-energy-density lithium batteries.However,the poor structural stability and severe side reactions at the electrode/electrolyte interface result in unsatisfactory cycle performance.Herein,the thin layer of two-dimensional(2D)graphitic carbon-nitride(g-C_(3)N_(4))is uniformly coated on the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(denoted as NCM811@CN)using a facile chemical vaporization-assisted synthesis method.As an ideal protective layer,the g-C_(3)N_(4)layer effectively avoids direct contact between the NCM811 cathode and the electrolyte,preventing harmful side reactions and inhibiting secondary crystal cracking.Moreover,the unique nanopore structure and abundant nitrogen vacancy edges in g-C_(3)N_(4)facilitate the adsorption and diffusion of lithium ions,which enhances the lithium deintercalation/intercalation kinetics of the NCM811 cathode.As a result,the NCM811@CN-3wt%cathode exhibits 161.3 mAh g^(−1)and capacity retention of 84.6%at 0.5 C and 55°C after 400 cycles and 95.7 mAh g^(−1)at 10 C,which is greatly superior to the uncoated NCM811(i.e.129.3 mAh g^(−1)and capacity retention of 67.4%at 0.5 C and 55°C after 220 cycles and 28.8 mAh g^(−1)at 10 C).The improved cycle performance of the NCM811@CN-3wt%cathode is also applicable to solid–liquid-hybrid cells composed of PVDF:LLZTO electrolyte membranes,which show 163.8 mAh g^(−1)and the capacity retention of 88.1%at 0.1 C and 30°C after 200 cycles and 95.3 mAh g^(−1)at 1 C.

Assessment of Mg(OH)_(2)/TiO_(2) coating in the Mg-Ca-Zn alloy for improved corrosion resistance and antibacterial performance

The high activity of metallic magnesium and alloys limits its potential in biomedical applications;in recent years,extensive efforts have been devoted to modulating this reactivity.In this work,we present Mg(OH)_(2) and TiO_(2)barrier coatings to reduce the degradation of magnesium alloy(Mg-Ca-Zn)surfaces.These coatings were deposited by the anodization method and the spin-coating technique,respectively.The anodized layer was coated with TiO_(2)generated from the hydrolysis of 3%weight of TTIP(Ti[OCH(CH_(3))_(2)]_(4),Titanium(IV)isopropoxide)in 2-Propanol deposited by the spin-coating method.Studying the degradation in Ringer’s solution by electrochemical impedance spectroscopy and OCP revealed a 98%reduction in pittings in uncoated samples after 14 days of immersion.The p H measurements revealed that the TiO_(2)coating reduced the alkalization of the physiological environment,keeping the pH at 6.0 values.In vitro studies of two types of bacteria(E.coli and S.aureus)exhibited zones of inhibition in the agar and activity bactericidal(kill time test).The mechanisms behind the improved degradation resistance and enhanced antibacterial activity are presented and discussed here.Surface modification with Mg(OH)_(2)/TiO_(2)coatings is a promising strategy to control the biodegradation of magnesium implants for bone regeneration.

Two-Dimensional Co_(2)(OH)1,4-Benzenedicarboxylate-Halloysite Nanotube Nanocomposite-Epoxy Coating with High Corrosion Resistance

Introducing inorganic nanomaterials into a polymer matrix greatly improves the anticorrosion performance of epoxy coatings(EP);however,poor compatibility between the materials can limit the improvement in properties.In this work,based on the high interface compatibility of two-dimensional(2D)Co_(2)(OH)_(2)BDC(BDC=1,4-benzenedicarboxylate)in the epoxy coating that we reported in previous work,we fabricated a 2D Co_(2)(OH)_(2)BDC-halloysite nanotube(HNT)nanocomposite have a structure consisting of alternating of nanosheets and nanotube by in situ synthesis.The nanocomposite was characterized by Fourier transform infrared spectroscopy,X-ray diffraction,and scanning electron microscopy.The mechanical and anticorrosion performance of the 2D Co_(2)(OH)_(2)BDC-HNT/EP coating was evaluated by mechanical tests and electrochemical impedance spectroscopy spectra.Compared with a conventional unreinforced epoxy coating,the 2D Co_(2)(OH)_(2)BDC-HNT/EP coating had higher mechanical strength and toughness,and the low-frequency impedance modulus of 2D Co_(2)(OH)_(2)BDC-HNT/EP coating was increased by three orders of magnitude,demonstrating the high corrosion resistance of our reinforced coating.

Effect of N_(2) partial pressure on comprehensive properties of antibacterial TiN/Cu nanocomposite coating

Foreign body reactions to the wear debris and corrosion products from the implants,and bacterial infections are the main factors leading to the implant failures.In order to resolve these problems,the antibacterial TiN/Cu nanocomposite coatings with various N_(2) partial pressures were deposited on 304 stainless steels(SS)using an arc ion plating(AIP)system,named TiN/Cu-x(x=0.5,1.0,1.5 Pa).The results of X-ray diffraction analysis,energy-dispersive X-ray spectroscopy,and scanning electron microscopy showed that the N_(2) partial pressures determined the Cu contents,surface defects,and crystallite sizes of TiN/Cu nanocomposite coatings,which further influenced the comprehensive abilities.And the hardness and wear resistances of TiN/Cu coatings were enhanced with increase of the crystallite sizes.Under the co-actions of surface defects,crystallite sizes,and Cu content,TiN/Cu-1.0 and TiN/Cu-1.5 coatings possessed excellent corrosion resistance.Besides,the biological tests proved that all the TiN/Cu coatings showed no cytotoxicity with strong antibacterial ability.Among them,TiN/Cu-1.5 coating significantly promoted the cell proliferation,which is expected to be a novel antibacterial,corrosion-resistant,and wear-resistant coating on the surfaces of medical implants.

Preparation and oxidation property of ZrB_2-MoSi_2/SiC coating on carbon/carbon composites

To improve the oxidation resistance of carbon/carbon composites,ZrB2-MoSi2/SiC coating on the carbon/carbon substrate was prepared.The inner coating of SiC was prepared by pack cementation and the outer coating of ZrB2-MoSi2 was prepared by slurry painting.The phase compositions and microstructures of the coating were characterized by XRD and SEM,respectively.The preparation and the high temperature oxidation property of the coated composites were investigated.The results show that the outer coating of carbon/carbon composites is composed of ZrB2,MoSi2 and SiC phases.The mass losses of the ZrB2-MoSi2/SiC coated samples with SiC nano-whiskers after 30 h and 10 h of oxidation at 1 273 K and 1 773 K were,respectively,5.3% and 3.0%.The ZrB2-MoSi2/SiC coated samples exhibit self-sealing performance and good oxidation resistance at high temperature.

SiC-MoSi_2/ZrO_2-MoSi_2 coating to protect C/C composites against oxidation

To improve the oxidation resistance of carbon/carbon （C/C） composites in air at high temperatures, a SiC- MoSi2/ZrO2-MoSi2 coating was prepared on the surface of C/C composites by pack cementation and slurry method. The microstructures and phase compositions of the coated C/C composites were analyzed by scanning electron microscopy and X-ray diffraction, respectively. The result shows that the SiC-MoSi2/ZrO2-MoSi2 coating is dense and crack-free with a thickness of 250-300 μm. The preparation and the high temperature oxidation property of the coated composites were investigated. The as-received coating has excellent oxidation protection ability and can protect C/C composites from oxidation for 260 h at 1773 K in air. The excellent anti-oxidation performance of the coating is considered to come from the formation of ZrSiO4, which improves the stability of the coating at high temperatures.

Anti-oxidation properties of ZrB_2 modified silicon-based multilayer coating for carbon/carbon composites at high temperatures

To improve the anti-oxidation ability of silicon-based coating for carbon/carbon （C/C） composites at high temperatures, a ZrB2 modified silicon-based multilayer oxidation protective coating was prepared by pack cementation. The phase composition, microstructure and oxidation resistance at 1773, 1873 and 1953 K in air were investigated. The prepared coating exhibits dense structure and good oxidation protective ability. Due to the formation of stable ZrSiO4-SiO2 compound, the coating can effectively protect C/C composites from oxidation at 1773 K for more than 550 h. The anti-oxidation performance decreases with the increase of oxidation temperature. The mass loss of coated sample is 2.44% after oxidation at 1953 K for 50 h, which is attributed to the decomposition of ZrSiO4 and the volatilization of SiO2 protection layer.

Tribological properties of nanostructured Al_2O_3-40%TiO_2 multiphase ceramic particles reinforced Ni-based alloy composite coatings

The Ni-based alloy composite coatings reinforced by nanostructured Al2O3-40%TiO2 multiphase ceramic particles were prepared on the surface of 7005 aluminum alloy by plasma spray technology. The microstructure and tribological properties of the composite coatings were researched. The results show that the composite coatings mainly consist of γ-Ni, α-Al2O3, γ-Al2O3 and rutile-TiO2 etc, and exhibit lower friction coefficients and wear losses than the Ni-based alloy coatings at different loads and speeds. The composite coating bears low contact stress at 3 N and its wear mechanism is micro-cutting wear. As loads increase to 6-12 N, the contact stress is higher than the elastic limit stress of worn surface, and the wear mechanisms change into multi-plastic deformation wear, micro-brittle fracture wear and abrasive wear. With the increase of speeds, the contact temperature of worn surface increases. The composite coating experiences multi-plastic deformation wear, fatigue wear and adhesive wear.

Tribological behavior and mechanisms of graphite/CaF_2/TiC/Ni-base alloy composite coatings

In order to reduce the friction coefficients and improve the wear resistance of mechanical parts, which work in the severe friction and wear conditions at heavy loads, the graphite/CaFg/TiC/Ni-base alloy composite coatings were prepared by plasma spray and their tribological behavior and mechanisms were investigated. The results show that the friction coefficients of the composite coatings are in the range of 0.22-0.288, which are reduced by 25.9% to 53% compared with those of the pure Ni-base alloy coatings, and the wear rates of the former are 18.6%-70.1% less than those of the latter. When wear against GCr15 steel balls, a transferred layer mainly composed of ferric oxides, graphite and CaF2 may gradually develop on the worn surface of the composite coatings, which made the friction and wear between GCr15 steel ball and the composite coatings change into that between the former and the transferred layer. So the friction coefficients and the wear lubrication effect of the transferred layer. The main wear layer in friction process. rates of the composite coatings are greatly reduced because of the solid mechanism of the composite coatings is delamination of the transferred