Progress and prospects of Mg-based amorphous alloys in azo dye wastewater treatment

Mg-based amorphous alloys exhibit efficient catalytic performance and excellent biocompatibility with a promising application probability,specifically in the field of azo dye wastewater degradation.However,the problems like difficulty in preparation and poor cycling stability need to be solved.At present,Mg-based amorphous alloys applied in wastewater degradation are available in powder and ribbon.The amorphous alloy powder fabricated by ball milling has a high specific surface area,and its reactivity is thousands of times better than that of gas atomized alloy powder.But the development is limited due to the high energy consumption,difficult and costly process of powder recycling.The single roller melt-spinning method is a new manufacturing process of amorphous alloy ribbon.Compared to amorphous powder,the specific surface area of amorphous ribbon is relatively lower,therefore,it is necessary to carry out surface modification to enhance it.Dealloying is a way that can form a pore structure on the surface of the amorphous alloys,increasing the specific surface area and providing more reactive sites,which all contribute to the catalytic performance.Exploring the optimal conditions for Mg-based amorphous alloys in wastewater degradation by adjusting amorphous alloy composition,choosing suitable method to preparation and surface modification,reducing cost,expanding the pH range will advance the steps to put Mg-based amorphous alloys in industrial environments into practice.

Crystallization microstructure of Mg_(65)Cu_(25)Y_(10) bulk amorphous alloy

Mg65Cu25Y10 bulk amorphous alloy specimens prepared by conventional copper mould method were heated at 200 °C for different time and the phase contents as well as microstructure were studied.The XRD results show that the crystallization of Mg65Cu25Y10 bulk amorphous alloy specimen becomes complete as the treating time increases and Mg2Cu,Mg24Y5 and HCP-Mg crystalline phases are found.Snowflake-like morphology is found in different specimens through SEM observation.The EDS patterns show that the composition of the snowflake-like structure is close to that of the as-cast alloy.Laminated structures are observed from the TEM images of the snowflake-like structure.From the electron diffraction patterns,it is seen that the snowflake-like structure is the combination of Mg24Y5 and amorphous matrix.The FCC-Mg phase in the matrix transforms into HCP-Mg during the heat-treating process.

Investigation of Micro Formability of Bulk Amorphous Alloy in the Supercooled Liquid State Based on Fluid Flow and Finite Element Analysis

Research results on the viscous flow deformation behavior of bulk amorphous alloy in different systems are reviewed. The material exhibits an ideal Newtonian fluid at a high temperature. Analytical solution of lamellar fluid flow behavior is used to discuss the viscous flow behavior of the bulk amorphous alloy in the supercooled liquid state. A material model, which describes such deformation behavior of Mg6oCusoYlo amorphous alloy, is introduced into the finite element method of microformin8 process. Surface feature size was investigated and found not sensitive to the micro formability. Bulk amorphous alloy may possibly be applied to microelectro-mechanical-systems （MEMS） fabrication.

Cyclic Fatigue Fracture of Zr_(55)Al_(10)Ni_5Cu_(30) Bulk Amorphous Alloy with Quenched-in Crystallites

The effects of quenched-in crystallites on the fracture of bulk amorphous alloys under cyclic loading condition wereinvestigated in this paper. For the fully amorphous alloy and specimen with fine crystallites the fatigue crack initiationoccurred on the surface. For the specimen with larger crystallites the crack originated from a big broken crystallitenear the surface. The average striation spacing on amorphous area is much larger than that on the crystallite.Crack initiation occurred at the crystallites is due to that the brittle crystallites broke easily under cyclic deformationcondition. The fine crystallites seemed to be protruded from the amorphous matrix and some bulges appeared onthe surface of specimen with fine crystallites under cyclic loading.

Crystalline Behavior and Magnetic Properties of Nd_(60) Fe_(30-x)Al_(10)Co_x (x=0,5,10) Bulk Amorphous Alloys

Crystalline behavior and magnetic properties of Nd 60 Fe 30- x Al 10 Co x (x =0,5,10) bulk amorphous alloys were investigated by differential scanning calorimeter (DSC), X ray diffraction (XRD) and the vibrating sample magnetometer (VSM). Neither glass transition nor supercooled liquid region before crystallization was observed for the as cast Nd 60 Fe 30- x Al 10 Co x (x =0,5,10) bulk amorphous alloys. The glass forming ability can be improved significantly by the addition of Co. The as cast Nd 60 Fe 30- x Al 10 Co x (x =0,5,10) alloys show hard magnetic behavior. With the addition of Co content, intrinsic coercivity ( i H c) increases while the saturation magnetization( σ s) and remanence ( σ r) decrease. The Curie temperature for the as cast Nd 60 Fe 30- x Al 10 Co x alloys increases from 451 K for x =0 to 468 K for x =10. Some precipitation of crystalline phases does not affect the hard magnetic properties of Nd 60 Fe 30- x Al 10 Co x (x =0,5,10) alloys, while the hard magnetic behavior disappears quickly after the alloys being completely crystallized.

Effect of Pd on GFA and Thermal Stability of Zr-based Bulk Amorphous Alloy

The effect of Pd addition on the glass-forming ability and thermal stability of the Zr55Al10Cu30Ni5-xPdx (x=0, 1, 3, 5 at. pct) alloys upon copper-mold casting has been investigated. The structure, thermal stability and microstructure were studied by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and transmission electron microscopy (TEM), respectively. It was identified that a new bulk amorphous alloy with the larger supercooled liquid region Tx of 100 K is obtained with substituting Ni by 1 at. pct Pd. Furthermore, the origins that thermal stability and GFA change with increasing of Pd have also beer discussed.

Deformation of Zr_(41)Ti_(14)Cu_(12.5)Ni_(10)Be_(22.5) bulk amorphous alloy under isobaric pressure in super-cooled liquid region

The curve of crystallization transition during continuous heating for the Zr41Ti14Cu12.5Ni10Be22.5 bulk amorphous alloy was measured by means of dilatation(Fully automatic transformation recording/measuring instrument) and X-ray diffraction(XRD) method. The deformation behavior of the alloy at various heating rates in the supercooled liquid region was studied. The results show that the glass transition temperature of the alloy increases slightly and the supercooled liquid region(SLR) increases significantly with increasing heating rate. The deformation amount under isobaric pressure of 1 N for the alloy in the SLR increases with increasing heating rate. As the heating rate of the alloy increases from 5 to 100 ℃/min, the amount of deformation of the alloy increases from 8.3% to 45%.

Preparation of Plate Fe_(60)Co_8Zr_(10)Mo_5W_2B_(15) Bulk Amorphous Alloy and Its Fracture Toughness

With processes of arc melting, inductive melting and copper mold suction casting, a plate Fe-based bulk amorphous alloy Fe_(60)Co_8Zr_(10)Mo_5W_2B_(15) with a thickness of 1mm was prepared. The surfaces and fractures of the cast bulk amorphous alloy were agleam and with typical metallic luster. The glass transition temperature(T_g), supercooled liquid region(△T_x)and reduced glass transition temperature(T_(rg))of the prepared Fe-based amorphous alloy are 884 K,63 K, and 0.611 respectively. The fracture toughness of the cast bulk amorphous alloy is at the level of 1.6 MPa·m^(1/2).

Investigation on Crystallization Kinetics of Zr-Al-Based Bulk Amorphous Alloys

Zr_~65 Al_~10 Ni_~10 Cu_~15 , Zr_~52.5 Al_~10 Ni_~10 Cu_~15 Be_~12.5 and Zr_~52.5 Al_~10 Ni_~14.6 Cu_~17.9 Ti_5 bulk amorphous alloys were prepared by copper mould casting. The crystallization kinetics was measured by differential scanning calorimeter(DSC) with different heating rates, and the activation energy was calculated using Kissinger equation. The relationship between thermal stability and rate constant of crystallization reaction is discussed on the view of crystallization kinetics, and the effect of small atom Beryllium on thermal stability of bulk amorphous alloys is also studied.

Correlation between Structures of Bulk Amorphous Zr-Ti-Ni-Cu-Be Alloy in Different States

The structures of the bulk amorphous Zr41Ti14Cu12.5Nil0.0Be22.5 alloy have been analyzed in solid, supercooled liquid and liquid with X-ray diffraction. The first coordination sphere radii and the first coordination numbers are 0.312 um, 11.2 in solid state.10.932 nm, 10.932 in supercooled liquid region and 0.305 urn, 11.296 in liquid state. The structures are the same in different states. But it shows some tendency to crystallizing that the first coordination sphere radius and the first coordination number drop in supercooled liquid region.

Thermal stability of Zr_(55)Al_(10)Ni_5Cu_(30)bulk amorphous alloy during continuous heating and isothermal annealing

The crystallization behavior of Zr 55 Al 10 Ni 5Cu 30 (mole fraction, %) bulk amorphous alloy during continuous heating and isothermal annealing was investigated. The results show that there exists a first order exponential decay relation between the characteristic temperatures and the heating rates during continuous heating process. The activation energy for glass transition E g and that for crystallization E p and E x during continuous heating were evaluated by Kissinger plots. In addition, there is a second order exponential decay relation between the annealing temperature and the corresponding crystallization time during isothermal annealing. The isothermal activation energy obtained by Arrhenius equation increases as crystallization proceeds, indicating the sufficient stability of the residual amorphous structure after initial crystallization.

Formation and crystallization of bulk Pd_(82)Si_(18) amorphous alloys

Bulk amorphous Pd 82 Si 18 alloy with the largest diameter of 8 mm was prepared by water quenching the molten alloy with flux medium in a quartz tube. The calculation result indicates that the bulk Pd 82 Si 18 amorphous alloys have a low critical cooling rate ( R c) of 4.589 K/s or less. The experimental results show that purifying melt may improve glass forming ability(GFA) of undercooled melt, while liquid phase separation (LPS) of undercooled melt will decrease its GFA. There are some differences in crystallization experiments between bulk metallic glass and amorphous ribbons of Pd 82 Si 18 alloys. These include the numbers of exothermic peak, glass transition temperature T g, crystallization temperature T x, region of undercooling liquid (Δ T=T x- T g) respectively. The links of cooling rates of melt and crystallization of Pd 82 Si 18 amorphous alloys are explored.

Amorphous phase formation rules in high-entropy alloys

There have been many interesting studies on high-entropy alloys（HEAs）, also known as multi-component（MC） alloys（MCAs）, in recent years. MC metallic-glasses（MGs） have shown the potential to express the advantages of MCAs and MGs in tandem. Amorphous phase formation rules are a crucial issue in the HEA and MCA field. For equal or near-equal atomic ratio alloys, mixed-entropy among the elements has a significant effect on the phase formation. This paper focuses on HEA amorphous phase formation rules. In the first two sections, the recent progress in amorphous phase formation in HEAs and MCAs is reviewed, including the effective factors and correlative parameters related to amorphous phase formation. In the third section, novel MCMGs including high-entropy（HE） bulk-metallic-glass（HE-BMG） and MCMG films developed in recent decades are summarized, and the giant-magnetic-impedance（GMI） effect of MC amorphous fibers is discussed.

Glass-forming ability and crystallization of Mg-Ni amorphous alloys with Y addition

Mg86.33Ni13.67-xYx(x=0, 1, 3, 6, 10) amorphous alloys were obtained by single-roller melt-spinning technique and the effect of Y addition on the glass forming ability(GFA), crystallization and micro-hardness of Mg-Ni alloys were studied. The results show that the GFA of Mg86.33Ni13.67-xYx(x=0, 1, 3, 6, 10) is improved successfully with the Y addition. The highest GFA appeares at x=6, while the reduced glass transition temperature (Trg) is 0.5225 and the supercooled liquid region(ΔTx) is 42.06 K; the position of the main diffraction halo is different for the alloys, and the maximum of the main diffraction halo of alloys with x=0, 1, 3 corresponds to the main peaks of a metastable fcc-Mg6Ni or fcc-Mg6Ni + Ni-Y intermetallic phases, and for the alloys with x=6, 10, it corresponds to Mg-Y and Ni-Y intermetallic phases; the micro-hardness of the alloys is improved with Y additions, and the highest micro-hardness is obtained at x=6 at.%, which is 960 MPa.

Effects of Ta addition on the microstructure and mechanical properties of Ti_(40)Zr_(25)Ni_8Cu_9Be_(18) amorphous alloy

The effects of Ta addition on the microstructure and mechanical properties of Ti40Zr25Ni8Cu9Be18 bulk amorphous alloy were investigated by using X-ray diffraction (XRD), transmission electron microscopy (TEM), scan electron microscopy (SEM) and compressive testing. As a result, the addition of Ta (0-8at%) prompted the successive precipitation of quasicrystalline phase, CuTi2 phase and bcc β-Ti solid solution. Additionally, the addition of less Ta content (3at%-5at%) led to the formation of amorphous ma- trix/nanoquasicrystal/CuTi2 complex phase structure; and nanoquasicrystals, as reinforcement precipitates, improved the fracture strength of Ti-Zr-Ni-Cu-Be-Ta alloys, which led to the high compressive fracture strength 1856 MPa of Ta5 alloy. With increasing Ta content (5at%-8at%), although the ductile dendritic β-Ti solid solution was precipitated, the strength and plasticity decreased to a great extent resulting from the growth of quasicrystalline phase and CuTi2 phase.

Eutectic reaction and cored dendritic morphology in yttrium doped Zr-based amorphous alloys

The microalloying effect of yttrium on the crystallization behaviors of （Zr0.525Al0.10Ti0.05Cu0.179Ni0.146）100-xYx, and （Zr0.55Al0.15- Ni0.10Cu0.20）100-xYx （x=0, 0.4, and 1, thus the two alloy systems were denoted as Zr52.5, Zr52.5Y0.4, Zr52.5Y1, and Zr55, Zr55Y0.4, Zr55Y1, respectively） was studied. Transmission electron microscopy （TEM） results suggested that the crystalline phases were different in the two Zr-based alloys and with different yttrium contents. ZrNi-phase and Al3Zr5 phase precipitations can be well explained by the mechanisms of nucleation and growth. Al3Zr5 phase is mainly formed by a peritectic-like reaction, while ZrNi-phase by a eutectic reaction. The contents of elements Y, A1, and Ti may dominate the reaction types. The orientation relationship between Y203 particles and A13Zr5 phase is also discussed.

Ductile Fe-based amorphous alloys with high iron content

Fe-based amorphous alloys with high iron content of 76at%-80at%were synthesized in the Fe-Mo-Si-P-C-B alloy system by the single roller melt-spinning technique.The amorphous ribbons exhibit high Vickers microhardness and good ductility,which can be indented and bent 180°without breaking.A number of shear bands could be observed around the indents and the bending traces.Studies on the magnetic properties of the amorphous alloys show that they possess high saturation magnetizations of 1.34-1.6 T,which increases with the increase of iron content.The core losses of these Fe-based amorphous alloys at various magnetic inductions were tested and found to be significantly dependent on their components.The Fe-Mo-Si-P-C-B amorphous alloys with excellent mechanical properties and soft magnetic properties have promising potential in functional applications.

Influence of niobium and yttrium on plastic deformation energy and plasticity of Ti-based amorphous alloys

Many amorphous alloys have been developed to date,but the low plasticity has limited their application.To achieve an amorphous alloy with high plasticity,a series of(Ti_(40)Zr_(25)Cu_(9)Ni_(8) Be_(18))_(100-x)TM_(x)(x=0,1,2,3,4 at.%,TM=Nb,Y)alloys were designed to study the influence of Nb and Y addition on the plasticity.The amorphous samples were prepared using the vacuum melting and copper mold casting process.The microstructures,glass forming ability and mechanical properties of the alloys were investigated by X-ray diffractometry(XRD),scanning electron microscopy(SEM),high-resolution transmission electron microscopy(HRTEM),depth-sensitive nanoindentation,and uniaxial compressive test.The plasticity of different bulk amorphous alloys was investigated by measuring the plastic deformation energy(PDE)during loading.The relationship between the PDE value and plasticity in bulk amorphous alloys was explored.Results show that Nb addition decreases the PDE value and promotes the generation of multiple shear bands,which significantly increases the fracture strength and plasticity,while the addition of Y element reduces the fracture strength and plastic strain of the alloy.

High-pressure sintering and magnetic properties of Fe_(86)Zr_(11-x)Nb_xB_3(x=5.5, 6) amorphous alloys

The thermal stability of milling Fe86Zr11-xNbxB3（x=5.5, 6） melt-spun strip powders and the influence of high-pressure sintering conditions on phase component and grain size of bulk alloys were investigated by X-ray diffractometry（XRD）, differential scanning calorimetry（DSC） and scanning electron microscopy（SEM）. The results show that milling melt-spun powder remains in the amorphous state, and the crystallization temperature of which is 480530℃, the apparent activation energy Ep of crystallization process is 294.1219.5kJ/mol. The increasing Nb content can increase crystallization temperature and decrease Ep. Under the sintering conditions of 5.5GPa/3min, when Pw is 1150W, single phase α-Fe nanocrystalline （20.626.7nm） bulk alloy with relative density higher than 99.0% can be obtained. Under the sintering conditions of 5.5GPa/1150W/3min, the magnetic properties of these nanocrystalline bulk alloys are Fe86Zr5.5Nb5.5B3 alloy, Bs=1.15T, Hc=5.08kA·m-1; Fe86Zr5Nb6B3 alloy, Bs=1.26T, Hc=4.27kA·m-1.

Decorating crystalline YFe_(2-x)Al_(x) on the Mg_(60)La_(10)Ni_(20)Cu_(10) amorphous alloy as “hydrogen pump” to realize fast de/hydrogenation

Mg-based amorphous alloys are one of the potential hydrogen storage materials but suffer from sluggish dehydrogenation/hydrogenation(de/hydrogenation)kinetics.In this work,as a new strategy,a hydrogen pump is built on the surface of amorphous alloys to solve this problem.By milling crystalline YFe_(2-x)Al_(x) hydrogen storage alloy with Mg_(60)La_(10)Ni_(20)Cu_(10) amorphous alloy,fine crystalline particles were seeded on amorphous alloy powder to form a“strawberry”structure.According to the TEM observation,a metallurgical bonding boundary formed between the Mg-based amorphous matrix and the Y-Fe-Al crystalline alloy.By microstructure and de/hydrogenation kinetics investigation,the“hydrogen pump”effect of the seeded crystalline alloy was confirmed,which makes it much easier for the hydrogen to dissociate on and diffuse through the surface of the Mg-based amorphous alloy.With such effect,the H absorption rate of Mg_(60)La_(10)Ni_(20)Cu_(10) amorphous alloy became almost eight times faster and it absorbs ~2.8 wt.% in 1 h at 130℃ under 4.5 MPa-H_(2).Further,fast hydrogenation can even achieve at 70℃ and the low-temperature dehydrogenation kinetics of the amorphous hydride can be also greatly promoted.The present work proves that surface modification is of great importance for obtaining Mg-based amorphous alloy with ideal hydrogen storage performance.