Growth and inhibition of zinc anode dendrites in Zn-air batteries:Model and experiment

Zinc(Zn)-air batteries are widely used in secondary battery research owing to their high theoretical energy density,good electrochemical reversibility,stable discharge performance,and low cost of the anode active material Zn.However,the Zn anode also leads to many challenges,including dendrite growth,deformation,and hydrogen precipitation self-corrosion.In this context,Zn dendrite growth has a greater impact on the cycle lives.In this dissertation,a dendrite growth model for a Zn-air battery was established based on electrochemical phase field theory,and the effects of the charging time,anisotropy strength,and electrolyte temperature on the morphology and growth height of Zn dendrites were studied.A series of experiments was designed with different gradient influencing factors in subsequent experiments to verify the theoretical simulations,including elevated electrolyte temperatures,flowing electrolytes,and pulsed charging.The simulation results show that the growth of Zn dendrites is controlled mainly by diffusion and mass transfer processes,whereas the electrolyte temperature,flow rate,and interfacial energy anisotropy intensity are the main factors.The experimental results show that an optimal electrolyte temperature of 343.15 K,an optimal electrolyte flow rate of 40 ml·min^(-1),and an effective pulse charging mode.

Superplasticity of fine-grained Mg-10Li alloy prepared by severe plastic deformation and understanding its deformation mechanisms

The superplastic behavior and associated deformation mechanisms of a fine-grained Mg-10.1 Li-0.8Al-0.6Zn alloy(LAZ1011)with a grain size of 3.2μm,primarily composed of the BCCβphase and a small amount of the HCPαphase,were examined in a temperature range of 473 K to 623 K.The microstructural refinement of this alloy was achieved by employing high-ratio differential speed rolling.The best superplasticity was achieved at 523 K and at strain rates of 10^(-4)-5×10^(-4)s^(-1),where tensile elongations of 550±600%were obtained.During the heating and holding stage of the tensile samples prior to tensile loading,a significant increase in grain size was observed at temperatures above 573 K.Therefore,it was important to consider this effect when analyzing and understanding the superplastic deformation behavior and mechanisms.In the investigated strain rate range,the superplastic flow at low strain rates was governed by lattice diffusion-controlled grain boundary sliding,while at high strain rates,lattice diffusion-controlled dislocation climb creep was the rate-controlling deformation mechanism.It was concluded that solute drag creep is unlikely to occur.During the late stages of deformation at 523 K,it was observed that grain boundary sliding led to the agglomeration of theαphase,resulting in significant strain hardening.Deformation mechanism maps were constructed forβ-Mg-Li alloys in the form of 2D and 3D formats as a function of strain rate,stress,temperature,and grain size,using the constitutive equations for various deformation mechanisms derived based on the data of the current tests.

Effects of water and nitrogen rate on grain-filling characteristics under high-low seedbed cultivation in winter wheat

A high-efficiency mode of high-low seedbed cultivation(HLSC)has been listed as the main agricultural technology to increase land utilization ratio and grain yield in Shandong Province,China.However,limited information is available on the optimized water and nitrogen management for yield formation,especially the grain-filling process,under HLSC mode.A three-year field experiment with four nitrogen rates and three irrigation rates of HLSC was conducted to reveal the response of grain-filling parameters,grain weight percentage of spike weight(GPS),spike moisture content(SMC),and winter wheat yield to water and nitrogen rates.The four nitrogen rates were N1(360 kg ha^(-1) pure N),N2(300 kg ha^(-1) pure N),N3(240 kg ha^(-1) pure N),and N4(180 kg ha^(-1) pure N),respectively,and the three irrigation quotas were W1(120 mm),W2(90 mm),and W3(60 mm),respectively.Results showed that the determinate growth function generally performed well in simulating the temporal dynamics of grain weight(0.989<R^(2)<0.999,where R2 is the determination coefficient).The occurrence time of maximum filling rate(T_(max))and active grain-filling period(AGP)increased with the increase in the water or nitrogen rate,whereas the average grain-filling rate(G_(mean))had a decreasing trend.The final 1,000-grain weight(FTGW)increased and then decreased with the increase in the nitrogen rates and increased with the increase in the irrigation rates.The GPS and SMC had a highly significant quadratic polynomial relationship with grain weight and days after anthesis.Nitrogen,irrigation,and year significantly affected the T_(max),AGP,G_(mean),and FTGW.Particularly,the AGP and FTGW were insignificantly different between high seedbed(HLSC-H)and low seedbed(HLSC-L)across the water and nitrogen levels.Moreover,the moderate water and nitrogen supply was more beneficial for grain yield,as well as for spike number and grain number per hectare.The principal component analysis indicated that combining 240-300 kg N ha^(-1) and 90^(-1)20 mm irrigation quota could improve grain-filling efficiency and yield for the HLSC-cultivated winter wheat.

Microstructure evolution and grain growth behavior of Ti14 alloy during semi-solid isothermal process

Microstructure evolution of Ti14 （α＋Ti2Cu） alloy during semi-solid isothermal process at different temperatures was investigated. The results reveal that both the temperature and holding time have effect on the grain growth behavior. The grains grow obviously and the degree of globularity increases with the increase of holding time. According to the statistic analysis of experimental data, the grain growth indices are 0.88 and 0.97 at 1 000 ℃ and 1 050 ℃, respectively, which indicates that increasing isothermal temperature would accelerate microstructural evolution.

Microstructure,Properties,and Grain Growth Kinetics of Mo-5Ta Refractory Sputtering Targets Prepared by SPS

Mo-5Ta targets were prepared by the spark plasma sintering(SPS)technology under the sintering temperatures of 1400-1600℃,the holding times of 0-20 min,and the axial pressure of 30 MPa.The microstructure,performance,and grain growth kinetics of Mo-5Ta sputtering targets were studied.With the increase of sintering temperatures and times,Ta can more dissolve in Mo and form a Mo(Ta)solid solution.The grain sizes of Mo-5Ta targets remain unchanged at low temperatures(1400-1500℃)while increasing significantly at high temperature(1600℃)with the extension of the holding time.In addition,the densities and Vickers hardness(HV_(0.5))first ascend and then decrease with sintering proceeding.The thermal conductivity is positively correlated with the grain size and density,as a result of their joint action.Based on the comprehensive analysis,the grain growth is dominated by the combination of boundary diffusion and volume diffusion.When n=2,the activation energies of grain growth under holding times of 5,10,20 min are calculated as 762.70,617.86,and 616.52 kJ/mol,respectively.

GPU parallel computation of dendrite growth competition in forced convection using the multi-phase-field-lattice Boltzmann model

A graphics-processing-unit(GPU)-parallel-based computational scheme is developed to realize the competitive growth process of converging bi-crystal in two-dimensional states in the presence of forced convection conditions by coupling a multi-phase field model and a lattice Boltzmann model.The elimination mechanism in the evolution process is analyzed for the three conformational schemes constituting converging bi-crystals under pure diffusion and forced convection conditions,respectively,expanding the research of the competitive growth of columnar dendrites under melt convection conditions.The results show that the elimination mechanism for the competitive growth of converging bi-crystals of all three configurations under pure diffusion conditions follows the conventional Walton-Chalmers model.When there is forced convection with lateral flow in the liquid phase,the anomalous elimination phenomenon of unfavorable dendrites eliminating favorable dendrites occurs in the grain boundaries.In particular,the anomalous elimination phenomenon is relatively strong in conformation 1 and conformation 2 when the orientation angle of unfavorable dendrites is small,and relatively weak in conformation 3.Moreover,the presence of convection increases the tip growth rate of both favorable and unfavorable dendrites in the grain boundary.In addition,the parallelization of the multi-phase-field-lattice Boltzmann model is achieved by designing the parallel computation of the model on the GPU platform concerning the computerunified-device-architecture parallel technique,and the results show that the parallel computation of this model based on the GPU has absolute advantages,and the parallel acceleration is more obvious as the computation area increases.

In situ observation of austenite grain growth behavior in the simulated coarse-grained heat-affected zone of Ti-microalloyed steels

The austenite grain growth behavior in a simulated coarse-grained heat-affected zone during thermal cycling was investigated via in situ observation. Austenite grains nucleated at ferrite grain boundaries and then grew in different directions through movement of grain boundaries into the ferrite phase. Subsequently, the adjacent austenite grains impinged against each other during the α→γtransformation. After the α→γ transformation, austenite grains coarsened via the coalescence of small grains and via boundary migration between grains. The growth process of austenite grains was a continuous process during heating, isothermal holding, and cooling in simulated thermal cycling. Abundant finely dispersed nanoscale TiN particles in a steel specimen containing 0.012wt% Ti effectively retarded the grain boundary migration, which resulted in refined austenite grains. When the Ti concentration in the steel was increased, the number of TiN particles de- creased and their size coarsened. The big particles were not effective in pinning the austenite grain boundary movement and resulted in coarse austenite grains.

ON THE MONTE CARLO SIMULATION OF NORMAL GRAIN GROWTH

The microstructures and their kinetics of normal grain growth are simulated using different Monte Carlo （MC） algorithms. Compared with the relative figures and the theoretical normal grain growth exponents of n =0.5, the effects of some factors of MC algorithm, i.e. the lattice types, the methods of selecting lattice sites, and the neighbors selection for energy calculations, on the simulation results of grain growth are studied. Two methods of regression were compared, and the three-parameter nonlinear regression is much more suitable for fitting the grain growth kinetics. A better model with appropriate factors included triangular lattice, the attempted site randomly selected, and the first and second nearest neighbors for energy calculations is obtained.

Characterization of grain growth behaviors by BP-ANN and Sellars models for nickle-base superalloy and their comparisons

In order to deeply understand the grain growth behaviors of Ni80A superalloy,a series of grain growth experiments were conducted at holding temperatures ranging from 1223 to 1423 K and holding time ranging from 0 to 3600 s.A back-propagation artificial neural network(BP-ANN)model and a Sellars model were solved based on the experimental data.The prediction and generalization capabilities of these two models were evaluated and compared on the basis of four statistical indicators.The results show that the solved BP-ANN model has better performance as it has higher correlation coefficient(r),lower average absolute relative error(AARE),lower absolute values of mean value(μ)and standard deviation(ω).Eventually,a response surface of average grain size to holding temperature and holding time is constructed based on the data expanded by the solved BP-ANN model,and the grain growth behaviors are described.

Isothermal Growth Kinetics of Ultra-fine Austenite Grains in a Nb-V-Ti Microalloyed Steel

Ultra-fine austenite grains with size of i-3 μm were prepared in a Nb-V-Ti steel through repetitive treatment of rapid heating and quenching. A model for the growth kinetics of these ultra-fine austenite grains was successfully created through successive 2 processes, and the activation energy Q for growth was estimated to be about 693.2 kJ/mol, which directly shows the inhibition effect of microalloy elements on the growth of ultra-fine austenite grains.

Isothermal grain growth of reactive spray formed 7075 alloys in semi-solid state

The grain growth behavior in reactive spray formed 7075+2.91 vol percent TiCAl alloy was studied and compared with that of spray formed 7075 Al alloy at semi-solid state. Theeffects of in-situ TiC particles on the microstructure of spray formed 7075 Al alloy were alsoinvestigated. The specimens were heat-treated isothermally at various temperatures between thesolidus and liquidus of 7075 Al alloy for times in the range of 10-60 min, then quenched in water.The microstructure of reheated specimens was characterized using scanning electron microscopy andoptical microscopy. The grain size was measured using a mean linear intercept method. Results showthat the in-situ TiC particles can effectively retard grain growth and refine the grain at a limitedsize. The grain growth exponent in Arrhenius equation increases from 2 to 3, which indicates thatthe in-situ TiC particles have the significant pinning effect on grain coarsening in the semi-solidstate.

Doping Effect on the Grain Growth of Spinel LiMn_2O_4 Prepared by Sol-Gel Methods

The cathode-active materials, Li1＋yMxMn2-xO4 （M = Al, Co, Ni, Zn, y = 0.02, x = 0.02） powder, were synthesized by sol-gel method using LiOH, Mn（NO3）2 as the starting materials, citric acid as a carrier and Al（NO3）3·9H2O or Co（NO3）2·6H2O or Ni（NO3）2·6H2O or Zn（NO3）2·6H2O as dopants. The influence of different doping elements on the structural properties of the as-prepared samples was investigated by X-ray diffraction （XRD）, infrared （IR） spectroscopy and scanning electron microscopy （SEM）. X-ray diffraction patterns of the prepared samples were identified as the spinel structure with space group Fd3m. The grain size increases gradually as the sintering temperature rises and corresponding activation energies for the grain growth have been estimated using Arrhenius’ empirical relation.

Treatment of metastatic colorectal carcinomas by systemic inhibition of vascular endothelial growth factor signaling in mice

AIM： Tumor angiogenesis has been shown to be promoted by vascular endothelial growth factor （VEGF） via stimulating endothelial cell proliferation, migration, and survival. Blockade of VEGF signaling by different means has been demonstrated to result in reduced tumor growth and suppression of tumor angiogenesis in distinct tumor entities. Here, we tested a recombinant adenovirus, AdsFItl-3, that encodes an antagonistically acting fragment of the VEGF receptor 1 （Fit-l）, for systemic antitumor effects in pre-established subcutaneous CRC tumors in mice.METHODS： Murine colorectal carcinoma cells （CT26） were inoculated subcutaneously into Balb/c mice for in vivo studies. Tumor size and survival were determined. 293 cell line was used for propagation of the adenoviral vectors. Human lung cancer line A549 and human umbilical vein endothelial cells were transfected for in vitro experiments.RESULTS： Infection of tumor cells with AdsFlt1-3 resulted in protein secretion into cell supernatant, demonstrating correct vector function. As expected, the secreted sFlt1-3 protein had no direct effect on CT26 tumor cell proliferation in vitro, but endothelial cell function was inhibited by about 46% as compared to the AdLacZ control in a tube formation assay. When AdsFlt1-3 （5×10^9 PFU/animal） was applied to tumor bearing mice, we found a tumor inhibition by 72% at d 12 after treatment initiation, in spite of these antitumoral effects, the survival time was not improved. According to reduced intratumoral microvessel density in AdsFlt1-3-treated mice, the antitumor mechanism can be attributed to angiostatic vector effects. We did not detect increased systemic VEGF levels after AdsFlt1-3 treatment and liver toxicity was low as judged by serum alanine aminotransferase determination.CONCLUSION： In this study we confirmed the value of a systemic administration of AdsFItl-3 to block VEGF signaling as antitumor therapy in an experimental metastatic colorectal carcinoma model in mice.

The role of recrystallization and grain growth in optimizing the sheet texture of magnesium alloys with calcium addition during annealing

The contribution of recrystallization and grain growth to the texture evolution in AZ31 alloy and a modified version AZ31+0.5 wt.%Ca was investigated utilizing a multi-step annealing process.The results showed that the addition of Ca triggered a considerable texture modification by increasing the texture spread and decreasing the overall texture intensity.This effect was found to be temperature dependent.When the annealing temperature remained lower than 450℃,a weak double peak texture with large basal pole tilt towards the RD was formed.This is correlated to microstructure observations of a large number of Ca-containing nano-sized particles that seemed to suppress grain growth below 450℃,which stabilized the weak recrystallization texture.This favorable texture was lost upon annealing at higher temperatures.In AZ31,recrystallization nuclei were found to preserve the orientation of their deformed parents,which offered limited potential to optimize the texture via annealing treatments.Grain growth of recrystallized grains resulted in a distinct sheet texture transition from a double-peak to a single-peak basal texture.Aspects of grain boundary energy and grain topology are discussed to explain the growth advantage of the sharp basal component over other orientations.

The mechanisms of grain growth of Mg alloys:A review

Grain growth directly influences the plasticity and strength of Mg alloys.As the grain size decreases from the microscale to the nanoscale,the plasticity of Mg alloys continually increases,whereas the strength first increases and later decreases.These trends are observed because the plastic deformation mechanism changes from dislocation–twinning dominance to grain boundary dominance.In this study,the factors influencing grain growth,such as the temperature of plastic deformation/annealing,second-phase particles and solute atoms,are examined to aid effective control of the grain size.Additionally,the mechanisms of grain growth,typically induced by strain and thermal activation,are clarified.Strain-induced grain boundary migration is attributable to the difference in the strain energy stored in adjacent grains with high-density dislocations.Heat-induced grain boundary migration is driven by the difference in the energy of the grain boundary/subgrain boundary and boundary curvature.Abnormal grain growth can be induced by anisotropy of the strain energy,anisotropy of the grain boundary mobility,depinning of the second phase and high misorientation gradient.

Transactivation of the TIEG1 confers growth inhibition of transforming growth factor-β-susceptible hepatocellular carcinoma cells

AIM:To investigate the role of transforming growth factor(TGF)-β-inducible early gene 1(TIEG1) in TGF-β-induced growth inhibition in hepatocellular carcinoma(HCC) cells.METHODS:Human hepatocyte and HCC cell lines with varied susceptibilities to TGF-β1 were tested by methylthiazoletetrazolium(MTT) assay.The expression changes of Smad2,Smad3,Smad4,Smad7,TIEG1 and TIEG2 gene following treatment with TGF-β1 in a TGF-β-sensitive hepatocyte cell line(MIHA),a TGF-β-sensitive hepatoma cell line(Hep3B) and two TGF-β-insensitive hepatoma cell lines(HepG2 and Bel7404) were examined.SiRNA targeting TIEG1 was transfected into Hep3B cells and the sensitivity of cells to TGF-β1 was examined.Overexpression of TIEG1 was induced by lentiviral-mediated transduction in TGF-β1-resistant hepatoma cell lines(Bel7404 and HepG2).MTT assay and 4',6-Diamidino-2-phenylindole staining were used to identify cell viability and apoptosis,respectively.The expression level of stathmin was measured by reverse transcriptase polymerase chain reaction and Western-blotting analysis,and stathmin promoter activity by TIEG1 was monitored by a luciferase reporter gene system.RESULTS:TIEG1 was significantly upregulated by TGF-β1 in the TGF-β1-sensitive HCC cell line,Hep3B,but not in the resistant cell lines.The suppression of TIEG1 by siRNAs decreased the sensitivity of Hep3B cells to TGF-β1,whereas the overexpression of TIEG1 mediated growth inhibition and apoptosis in TGF-β1-resistant HCC cell lines,which resembled those of TGF-β1-sensitive HCC cells treated with TGF-β1.Our data further suggested that stathmin was a direct target of TIEG1,as stathmin was signif icantly downregulated by TIEG1 overexpression,and stathmin promoter activity was inhibited by TIEG1 in a dose-dependent manner.CONCLUSION:Our data suggest that transactivation of TIEG1 conferred growth inhibition of TGF-β-susceptible human HCC cells.

Grain growth simulation with the second phase particle pinning for heat-affected zone of microalloyed steel welds

The second phase particle dispersed in microalloyed steel has different effects on grain growth depending on their size and volume fiaction of the second phase particles which will change during welding thermal cycles. The particle coarsening and dissolution kinetics model was analyzed for continuous heating and cooling. In addition, based on experimental data, the coupled equation of grain growth was established by introducing limited size of grain growth with the consideration of the second phase particles pinning effects. Using Monte Carlo method based on experimental data model, the grain growth simulation for heat-affected zone of microalloyed steel welds was achieved. The calculating results were well in agreement with that of experiments.

Grain growth of Al-4Cu-Mg alloy during isothermal heat treatment

The microstructure of an Al-4Cu-Mg alloy during isothermal heat treatment in the Strain Induced Melt Activation （SIMA） process was investigated and the kinetics of grain growth was analyzed, The grain growth during isothermal heat treatment of the Al-4Cu-Mg alloy coincided with the Ostwald ripening theory. During isothermal heat treatment, both grain shape and the high volume fraction of solid phase have significant effects on grain growth. Therefore, a new grain growth model based on the Ostwald ripening theory was proposed taking into consideration the grain shape and the volume fraction of solid phase. By comparing the calculated results with the experimental results, it was confirmed that the present model could be applied to grain growth during isothermal heat treatment of the Al-4Cu-Mg alloy in the SIMA process.

Discussion on the Hillert Theory of Normal Grain Growthwith a Modified Monte Carlo Simulation

On the basis of analyzing some limitations in the existing algorithm, a modified Monte Carlo methodwas proposed to simulate two-dimensional normal grain growth. With the modified method. the simulated time exponent of grain growth attained n=0.49±0.01, which is very close to the theoretical value of the steady graingrowth n=0.5, indicating the possibility to investigate the total process of normal grain growth. The relationbetween the Hillert and the von Neumann equations were studied and identified, the Hillert's basic equation hasbeen found to hold during the normal grain growth. The grain size distribution was found to van continuouslyand slowly with the simulated time in the total growth process, the lognormal and the Hillert functions may betwo types of the expression forms during its transition, and the later seemingly corresponds at the distribution ofthe steady stage were n≈0.50.

Grain growth and thermal stability of nanocrystalline Ni-TiO_2 composites

The grain growth and thermal stability of nanocrystalline Ni-TiO2composites were systematically investigated.Thenanocrystalline Ni-TiO2composites with different contents of TiO2were prepared via electroplating method with the variation ofTiO2nano-particles concentration.The effect of TiO2content on the grain size,phase structure and microhardness was investigatedin detail.The corresponding grain growth and diffusion mechanisms during the heating process were also discussed.The optimalmicrohardness of HV50270was achieved for the composite with addition of20g/L TiO2nano-particles after annealing at400°C for90min.The calculation of the activation energy indicated that lattice diffusion dominated at high temperatures for thenanocrystalline Ni-TiO2composites.It was indicated that the increase of TiO2nano-particles content took effect on restricting thegrain growth at high temperatures by increasing the grain growth activation energy.