Corrosion resistance of in-situ Mg-Al hydrotalcite conversion film on AZ31 magnesium alloy by one-step formation

In situ growth of nano-sized layered double hydroxides （LDH） conversion film on AZ31 alloy was synthesized by a urea hydrolysis method. The formation mechanism of the film was proposed. Firstly, the dissolved Mg2＋ ions deposited into a precursor film consisted of MgCO3 and Mgs（CO3）4（OH）2·4H2O; secondly, the precursor translated into the crystalline Mg（OH）2 in alkaline conditions; finally, the Mg2＋ ions in Mg（OH）z were replaced by A13＋ ions, Mg（OH）2 translated into the more stable LDH structure, simultaneously, the OH- ions in the interlayer were exchanged by CO32-, thus led to the formation of the LDH （Mg6Alz（OHh6CO3·4H2O） film. The results indicated that the LDH film characterized by interlocking plate-like nanostructures and ion-exchange ability significantly improved the corrosion resistance of the AZ31 Mg alloy.

Influence of the preparation method on the catalytic activity of Mg-Al hydrotalcites as solid base catalysts

Mg-Al hydrotalcites were synthesized using different preparation methods(a co-precipitation method, a urea method, and a simple one) to analyze their effect on the catalytic activity of these solid base catalysts. The method strongly affected the structure of their layers(e.g., the growth and stacking of the layers, and the type of intercalated anions) and, accordingly, their catalytic activity. The Mg-Al hydrotalcite prepared by co-precipitation showed the best catalytic performance in the isomerization of glucose into fructose, due to the small crystallite size and sand rose morphology enhancing the exposure of surface active sites to reactants.

Tuning the base properties of Mg–Al hydrotalcite catalysts using their memory effect

Herein,the relationship between the structure and base properties of Mg–Al hydrotalcite catalysts was comprehensively investigated in relation to heat treatment and rehydration processes,which are well known as memory effects of hydrotalcite.The structure of Mg–Al hydrotalcites changed from layered double hydroxide(LDH)to mixed metal oxide and subsequently to a spinel structure during heat treatment,and it was returned from mixed metal oxide to a LDH structure by rehydration.Based on various characterizations,we successfully proposed a detailed mechanism of memory effect.We also confirmed that the Mg–Al hydrotalcites had weak or strong base sites and that their base properties could be systematically tuned by heat treatment and rehydration.The prepared Mg–Al hydrotalcites were applied to a model reaction,isomerization of glucose to fructose,as base catalysts.Among the catalysts tested,the rehydrated Mg–Al hydrotalcite efficiently produced fructose due to its appropriate base and structure properties.We finally concluded that the base sites of Mg–Al hydrotalcites can be designed as desired by heat treatment and rehydration.Moreover,through systematic design of the base sites of Mg–Al hydrotalcites,these can be promising catalysts for various heterogeneous reactions over base catalysts,giving excellent catalytic performances.

The Adsorption of NO_X on Magnesium Aluminium Hydrotalcite

Magnesium aluminium hydrotalcite (Mg-Al-HT) with molar ratio of Mg-to-Al of 3 to l was prepared and characterized by X-ray diffraction (XRD) and infrared spectra (IR). The performances of Mg-Al-HT for the adsorption and desorption of NOx were studied. The results indicated that the adsorption capacity of the hydrotalcite for NOx was 1398.2 mg/g, and it was higher than the acticarbon's. The adsorption capacities depended on adsorption time and temperature. Mg-Al-HT could be regenerated by thermal decomposition, and the adsorption efficiency had not changed markedly after three cycles.

Comprehensive Utilization of Natural Magnesium-Containing Resources and the Development of MgO-Based Refractories

This paper presents the ways of comprehensive utilization of the natural magnesium containing resources and the trends of the MgO based refractories used in high temperature industries. In the first part, the uses and productions of metal Mg, sorel cement, Mg (OH) 2 fire retardant, light magnesium carbonate, light magnesia and magnesium sulphate are described. In the second part, the developments of MgO based refractories used in steelmaking process, nonferrous metallurgy, cement rotary kiln and waste melting furnace are described from some applied theories, including corrosion resistant and slaking resistant MgO CaO materials, chrome free bricks such as MgO CaO ZrO 2 , MgO MgO Al 2 O 3 , MgO MgO·Al 2 O 3 ZrO 2 , MgO MgO·Al 2 O 3 2MgO ·TiO 2 and MgO FeO·Al 2 O 3 , and MgO containing monolithic refractories etc.

Microstructure of Cu-based Amorphous Composite Coatings on AZ91D Magnesium Alloy by Laser Cladding

To improve the sliding wear resistance of AZ91D magnesium alloy, Cu-based amorphous composite coatings made of CuaTTi34Zr11Nis and Cu47Ti34Zr11Ni8＋20 wt pct SiC powders were fabricated on AZ91D magnesium alloy by laser cladding, respectively. SEM （scanning electron microscopy）, EDS （energy dispersive X-ray spectroscopy）, XRD （X-ray diffraction） and TEM （transmission electron microscopy） techniques were employed to study the phases of the coatings. The results show that the coatings mainly consist of amorphous phase and different intermetallic compounds. The reason of formation of amorphous phase and the function of SiC particles were explained in details.

Electrochemical co-deposition of magnesium based alloy from molten salts

Magnesium based alloys with aluminum and zinc were obtained through electrochemical co-deposition from LiCl-NaCl-MgCl2 melt. The possibility of electrochemical co-deposition was discussed in detail by electro-analytical methods including cyclic voltametry,square wave voltametry,and chronopotentiometry. The co-deposition happens when the concentration of aluminum and zinc ions is kept at low value and the current density is high enough. The components of alloy elements can be controlled by fixing the components of the feeding salts. A laboratory experiment of the preparation by step-current co-deposition was also performed and certain compositions of the Mg-Al,and Mg-Zn were obtained. The alloys obtained from the co-deposition show a typical as-cast microstructure. The best conditions of electrolysis such as temperature,amount of addition and mode of feeding were discussed in detail.

Attack of Limestone Cement-based Material Exposed to Magnesium Sulfate Solution at Low Temperature

Limestone in cement could be a source of CO3^2- needed for thaumasite formation which will result in thanmasite form of sulfate attack （TSA） probably. TSA has more deterioration than ettringite or gypsum form of sulfate attack because it targets the calcium silicate hydrates （C-S-H） which is the main binder phase in all Portland cement-based materials. By means of physical and mechanical property testing as well as erosion phases analysis, magnesium sulfate attack of cement-based material containing 35% limestone powder by mass at 5 ± 2 ℃ is investigated. The compressive strength and flexural strength of mortar specimen immersed in MgSO4 solution increase firstly, then decrease rapidly with the immersing age. Relative dynamic elastic modulus of mortar specimen changes in a phased process. After immersing in MgSO4 solution for 15 weeks, the main erosion phases in paste specimen change from four phases compounds, three phases compounds to two phases compounds from surface to inside. Deterioration course of limestone cement-based material exposed to magnesium sulfate aggressive environment appears progressive damage layer by layer, and every layer probably suffers four stages, which are property strengthening stage, initial degradation stage, thaumasite formation stage and cementation loss stage, respectively.

Statistical model for combustion of high-metal magnesium-based hydro-reactive fuel

We investigate experimentally and analytically the combustion behavior of a high-metal magnesium-based hydro- reactive fuel under high temperature gaseous atmosphere. The fuel studied in this paper contains 73% magnesium powders. An experimental system is designed and experiments are carried out in both argon and water vapor atmo- spheres. It is found that the burning surface temperature of the fuel is higher in water vapor than that in argon and both of them are higher than the melting point of magnesium, which indicates the molten state of magnesium particles in the burning surface of the fuel. Based on physical considerations and experimental results, a mathematical one-dimensional model is formulated to describe the combustion behavior of the high-metal magnesium-based hydro-reactive fuel. The model enables the evaluation of the burning surface temperature, the burning rate and the flame standoff distance each as a function of chamber pressure and water vapor concentration. The results predicted by the model show that the burning rate and the surface temperature increase when the chamber pressure and the water vapor concentration increase, which are in agreement with the observed experimental trends.

Adsorption removal of thiocyanate from aqueous solution by calcined hydrotalcite

A hydrotalcite with Mg/AI molar ratio 2 was prepared by co-precipitation method and was characterized by XRD, TG/DTA, Zeta potential and BET surface area. The hydrotalcite was calcined at 500℃, with the dehydration from interlayer, the dehydroxilation from the brucite-like layer and the decomposition of carbonate successively, transformed into the mixed oxide type. The removal of thiocyanate from aqueous solution by using the original hydrotalcite and calcined hydrotalcite （HTC-500） was investigated. The results showed that the thiocyanate adsorption capacity of calcined hydrotalcite was much higher than that of the original form. Calcined hydrotalcite was particularly effective at removing thiocyanate, and that the effective range of pH for the thiocyanate removal are between 5.5-10.0. The experimental data of thiocyanate removal fit nicely with Langmuir isotherm, and the saturated adsorption uptake was 96.2 mg SCN-/g HTC-500. The adsorption of thiocyanate by calcined hydrotalcite follows first-order kinetics. And the intercalation to the structure recovery for calcined hydrotalcite. But the presence of additional anions could affect the adsorption behavior of thiocyanate.

Combinatorial Supports for Ru-based Ammonia Synthesis Catalysts

The support materials of ruthenium-based catalysts for ammonia synthesis were preparedusing mixed solutions composed of magnesium nitrate, aluminum nitrate and calcium nitrate with acertain ratio. The catalysts supported on complex oxides were more active and the optimal activitytemperatures were lower than that supported on single oxide under the same conditions. Thecatalyst with Mg-Al complex oxide as support prepared by calcinating hydrotalcite-like compoundhad significantly higher activity, 38.42 mL NH3?h-1?g-1 at 673 K. The BET determination showedthat the Mg-Al complex oxide possessed large surface area, 140.95 m2?g-1, similar to γ-Al2O3.

Development and experimental validation of kinetic models for the hydrogenation/dehydrogenation of Mg/Al based metal waste for energy storage

With the increased use of renewable energy sources,the need to store large amounts of energy will become increasingly important in the near future.A cost efficient possibility is to use the reaction of recycled Mg waste with hydrogen as thermo-chemical energy storage.Owing to the high reaction enthalpy,the moderate pressure and appropriate temperature conditions,the broad abundance and the recyclability,the Mg/Al alloy is perfectly suitable for this purpose.As further development of a previous work,in which the performance of recycled Mg/Al waste was presented,a kinetic model for hydro-and dehydrogenation is derived in this study.Temperature and pressure dependencies are determined,as well as the rate limiting step of the reaction.First experiments are carried out in an autoclave with a scaled-up powder mass,which is also used to validate the model by simulating the geometry with the scaled-up experiments at different conditions.

Effect of Schiff base as corrosion inhibitor on AZ31 magnesium alloy in hydrochloric acid solution

Schiff base derived from the condensation reaction of analar grade 1-amino-2-naphthol 4-sulphonic acid with cinnamaldehyde was prepared under microwave condition.The Schiff base was analysed by infrared spectroscopy.This Schiff base as a corrosion inhibitor of AZ31 magnesium alloy in 0.05 mol/L HCl solution was studied.The inhibition effect of the Schifif base compound（4Z）-4-（3-phenyl allylidene amino）-3-hydroxy naphthalene-1-sulfonic acid（AC） on AZ31 magnesium alloy corrosion was studied using mass loss,potentiodynamic polarization technique,electrochemical impedance spectroscopy methods.The potentiodynamic polarization curve shows that Schiff base AC inhibits both anodic and cathodic reactions at all concentration,which indicates it is a mixed type inhibitor.EIS results indicate that as the additive concentration is increased,the polarization resistance increases whereas double-layer capacitance decreases.The adsorption of AC on the AZ31 magnesium alloy surface in 0.05 mol/L HCl obeys the Langmuir adsorption isotherm.

Bullet-like vanadium-based MOFs as a highly active catalyst for promoting the hydrogen storage property in MgH_(2)

The practical application of magnesium hydride(MgH_(2))was seriously limited by its high desorption temperature and slow desorp-tion kinetics.In this study,a bullet-like catalyst based on vanadium related MOFs(MOFs-V)was successfully synthesized and doped with MgH_(2) by ball milling to improve its hydrogen storage performance.Microstructure analysis demonstrated that the as-synthesized MOFs was consisted of V_(2)O_(3) with a bullet-like structure.After adding 7wt%MOFs-V,the initial desorption temperature of MgH_(2) was reduced from 340.0 to 190.6℃.Besides,the MgH_(2)+7wt%MOFs-V composite released 6.4wt%H_(2) within 5 min at 300℃.Hydrogen uptake was started at 60℃under 3200 kPa hydrogen pressure for the 7wt%MOFs-V containing sample.The desorption and absorption apparent activity energies of the MgH_(2)+7wt%MOFs-V composite were calculated to be(98.4±2.9)and(30.3±2.1)kJ·mol^(-1),much lower than(157.5±3.3)and(78.2±3.4)kJ·mol^(−1) for the as-prepared MgH_(2).The MgH_(2)+7wt%MOFs-V composite exhibited superior cyclic property.During the 20 cycles isothermal dehydrogenation and hydrogenation experiments,the hydrogen storage capacity stayed almost unchanged.X-ray diffraction(XRD)and X-ray photoelectron spectrometer(XPS)measurements confirmed the presence of metallic vanadium in the MgH_(2)+7wt%MOFs-V composite,which served as catalytic unit to markedly improve the hydrogen storage properties of Mg/MgH_(2) system.

In vitro degradation resistance of glucose and L-cysteine-bioinspired Schiff-base anodic Ca−P coating on AZ31 magnesium alloy

A Schiff base(a compound containing a C=N bond)induced anodic Ca−P coating was prepared on AZ31 Mg alloy in a mixed solution of CaCl_(2) and KH_(2)PO_(4) at 60℃ in the presence of glucose and L-cysteine.The microstructure and chemical composition of the coatings were characterized using FE-SEM,FT-IR,XRD,and XPS.The in vitro degradation resistance of the coated samples was evaluated via potentiodynamic polarization(PDP),electrochemical impedance spectroscopy(EIS),and hydrogen evolution test.The experimental results show that the Ca−PSchiff base coating is composed of CaHPO_(4)(DCPA)and hydroxyapatite(HA),whereas HA is not present in the Ca−P coating.The Ca−P_(Schiff base) coating thickness is about 2 times that of Ca−P coating(Ca−P coating:(9.13±4.20)μm and Ca−P_(Schiff base):(18.13±5.78)μm).The corrosion current density of the Ca−P_(Schiff base) coating is two orders of magnitude lower than that of the Ca−P coating.The formation mechanism of the Ca−P_(Schiff base) is proposed.

Progress in Research on Vanadate-Based Coatings on Corrosion Resistance

Vanadate, usually used as the corrosion resistant inhibitor for the paint systems, is one of the substances that have been proposed as alternative to toxic chromate for the corrosion protection. In this paper, the possibility of vanadate passivating from its chemical properties was introduced firstly. Then, the progress and examples in research on vanadate conversion coatings on the corrosion resistance were summarized. And the substrates discussed here contained aluminum alloys, magnesium alloys and so on. Finally, the research tendency of vanadate-based coatings was discussed.

An efficient Hauser-base electrolyte for rechargeable magnesium batteries

Rechargeable magnesium batteries(RMBs)are considered the promising candidates for post lithium-ion batteries due to the abundant storage,high capacity,and dendrite-rare characteristic of Mg anode.However,the lack of practical electrolytes impedes the development and application of RMBs.Here,through a one-step reaction of LiCl congenital-containing Knochel–Hauser base TMPL(2,2,6,6-tetrame thylpiperidinylmagnesium chloride lithium chloride complex)with Lewis acid AlCl_(3),we successfully synthesized an efficient amino-magnesium halide TMPLA electrolyte.Raman and mass spectroscopy identified that the electrolyte comprises the typical di-nuclear copolymer[Mg_(2)Cl_(3)·6THF]+cation group and[(TMP)2AlCl_(2)]-anion group,further supported by the results of density functional theory calculations(DFT)and the Molecular dynamics(MD)simulations.The TMPLA electrolyte exhibits promising electrochemical performance,including available anodic stability(>2.65 V vs.SS),high ionic conductivity(6.05mS cm^(-1)),and low overpotential(<0.1 V)as well as appropriate Coulombic efficiency(97.3%)for Mg plating/stripping.Both the insertion Mo6S8cathode and conversion Cu S cathode delivered a desirable electrochemical performance with high capacity and good cycling stability based on the TMPLA electrolyte.In particular,when compatible with low cost and easily synthesized Cu S,the Cu S||Mg cell displayed an extremely high discharge capacity of 458.8 mAh g^(-1)for the first cycle and stabilized at 170.2 mAh g^(-1)with high Coulombic efficiency(99.1%)after 50 cycles at 0.05 C.Our work proposes an efficient electrolyte with impressive compatibility with Mg anode and insertion/conversion cathode for practical RMBs and provides a more profound knowledge of the Lewis acid–base reaction mechanisms.

Role of Al(III) in Zn-Based Electrode Synthesis for Supercapacitor

Supercapacitor is considered as one of the most promising energy storage systems because of its high power density, long life and low production cost. Electrode materials play important roles in the performance of Supercapacitor (SC). In this study, Zn-based hydrotalcite structure materials are prepared by hydrothermal method. The influence of Zn/Al ratio in precursors on electrochemical properties of electrode materials is investigated. The results show that Al(III) promotes the formation of relatively ordered active substances and participates in redox reaction on electrode surface. Specific capacitance of Zn-based electrode reaches 2557 F·g-1 (1.0 A·g-1) at Zn/Al molar ratio of 1:1 in precursors. This method is simple and environmentally friendly. The electrode exhibits excellent electrochemical activity and stability, showing this material application prospect for supercapacitor.

Cerium-Based Sealing Treatment of Mg–Al Hydrotalcite Film on AZ91D Magnesium Alloy

An environment-friendly cerium-based sealing treatment was developed to improve the surface integrity and corrosion resistance of Mg–Al hydrotalcite film on AZ91D magnesium alloy. The cerium dioxide was generated through three stages namely nucleation, growth and dissolution, modifying the surface of AZ91D Mg alloy, and the hydrotalcite film became integral after being treated for 30 min. The results of polarization curves showed that the anti-corrosive performance of the hydrotalcite film was enhanced by the sealing treatment. Moreover, the immersion tests and electrochemical impedance spectrum measurements also demonstrated that the sealed hydrotalcite film provided a longer-term protection of magnesium alloy from corrosion as compared to the unsealed one.

Electric field assisted chemical conversion process of AZ91D magnesium alloy in HCO_3^-/CO_3^(2-) solution

A new method for synthesizing Mg-Al hydrotalcite conversion coating on AZ91D Mg alloy was developed by the application of electric field （EF）. By using EF technique, the formation time of the coating can be significantly reduced. The SEM results indicate that a continuous and compact Mg-Al hydrotalcite coating is formed on the surface of Mg alloy after short time EF treatment. However, a long time treatment would make the coating partially exfoliate. The corrosion current density （Jcor ） of the coated sample （EF1＋1 h） is approximately two orders of magnitude lower than that of Mg alloy substrate. The test of electrochemical impedance spectroscopy （EIS） and immersion corrosion also suggest that the coating can effectively protect Mg alloy against corrosion.