In situ scattering study of multiscale structural evolution during liquid–liquid phase transition in Mg-based metallic glasses

The glass-forming ability of Mg-Cu-Gd alloys could be significantly promoted with the addition of Ag.A calorimetric anomaly could be observed in the supercooled liquid region of the Mg-Cu-Ag-Gd metallic glass,indicating the occurrence of a liquid-state phase transition driven by entropy.However,the underlying mechanism of the polyamorphous phase transition remains unsettled.In the paper,in situ scattering techniques were employed to reveal multiscale structure evidence in a Mg65Cu15Ag10Gd10metallic glass with an anomalous exothermic peak upon heating.Resistivity measurements indicate a reentrant behavior for the Mg-Cu-Ag-Gd metallic glass in the anomalous exothermic peak temperature region during heating.In situ synchrotron diffraction results revealed that the local atomic structure tends to be ordered and loosely packed first,followed by reentering into the initial state upon heating.Moreover,time-resolved small-angle synchrotron X-ray scattering(SAXS) results show an increase in nanoscale heterogeneity first followed by a reentrant supercooled liquid behavior.A core-shell structure model has been used to fit the SAXS profiles when polyamorphous phase transition occurs.In contrast,there is no structure anomaly for the reference Mg-Cu-Gd alloy system.The detailed multiscale structural evidence suggests the occurrence of a liquid-liquid phase transition followed by a reentrant behavior in the MgCu-Ag-Gd metallic glass.Our results deepen the understanding of the structural origin of the glass-forming ability and shed light on the possibility of tuning the physical and mechanical properties by heat-treatment in the supercooled liquid region of Mg-based metallic glasses.

Mg-based bulk metallic glasses:A review of recent developments

Metallic biomaterials have been widely used in the field of medical implants for replacement purposes and/or for regeneration of tissue.Metals such as stainless steel(316 L),cobalt-chromium alloys and titanium alloys(Ti-6Al-4 V)are widely used as metallic implants today.However,they often exhibit unsatisfactory results such as stress shielding,the release of toxic ions and are often permanent and invasive–where a second surgery is required to remove the implant once the bone is fully healed.Magnesium as a biomaterial have attracted much attention recently due to its excellent biocompatibility,similar mechanical properties to bone and biodegradability.Unlike other metals and bio ceramics,the ability for magnesium alloys to undergo biodegradation eliminates the requirement for a second surgery to remove the implant.Additionally,the degradation of magnesium releases Mg2+ions,which stimulates metabolism as they are a cofactor in numerous numbers of enzymes.Despite the advantages of magnesium alloys,the rapid degradation of magnesium proved to be challenging as the implant is unable to retain its structural integrity sufficiently enough to act as an implant.To improve the corrosion resistance of magnesium alloys,researchers have been working on the synthesis and characterization of Mg-based bulk metallic glasses,which can significantly improve the corrosion resistance of Mg-based alloys.This paper is a comprehensive review that compiles,analyzes and critically discusses the recent literature on the latest understanding of the processing,mechanical and biological characteristics of Mg-based bulk metallic glasses.

Crystallization of Mg-based bulk metallic glass

Mg-based bulk metallic glass fabricated by conventional copper mould method was aged at different temperatures. X-ray diffractometry(XRD), scanning electron microscopy(SEM), atomic force microscopy(AFM) and focused ion beam(FIB) miller were employed to examine specimens obtained under different conditions. The crystallization of Mg-based bulk metallic glass depends upon both the aging temperature and the aging time. As temperature increases or the holding time increases, the microstructure of the aged specimen varies from glassy one to crystalline one plus glassy phase and then to absolutely multiphase crystalline one. From the FIB images, it is clear that Mg-based bulk metallic glass could not only crystallize completely but also display dendrite-like growth style. From the AFM images, there are not only significant variations of microstructures but also surface morphology of specimens obtained under different conditions. It is proposed that the surface morphology varies as the treating temperature increases. The Vickers hardness of different specimens increases as the fraction of crystalline phase (s) increases.

Corrosion and in vitro cytocompatibility investigation on the designed Mg-Zn-Ag metallic glasses for biomedical application

In the present work,seven Mg-Zn-Ag alloys with the nominal composition of Mg_(96-x)Zn_(x)Ag_(4)(x=17,20,23,26,29,32,35 in at.%)were prepared by induction melting and single-roller melt-spinning.The X-ray diffraction(XRD)analyses indicate the metallic glasses with three composition of Mg_(73)Zn_(23)Ag_(4),Mg_(70)Zn_(26)Ag_(4),and Mg_(67)Zn_(29)Ag_(4)were obtained successfully.The differential scanning calorimetry(DSC)measurement was used to obtain the characteristic temperature of Mg-Zn-Ag metallic glasses for the glass-forming ability analysis.The maximum glass transition temperature(Trg)was found to be 0.525 with a composition close to Mg_(67)Zn_(29)Ag_(4),which results in the best glass-forming ability.Moreover,the immersion test in simulated body fluid(SBF)demonstrate the relative homogeneous corrosion behavior of the Mg-Zn-Ag metallic glasses.The corrosion rate of Mg-Zn-Ag metallic glasses in SBF solution decreases with the increase of Zn content.The sample Mg_(67)Zn_(29)Ag_(4)has the lowest corrosion rate of 0.19mm/yr,which could meet the clinical application requirement well.The in vitro cell experiments show that the Madin-Darby canine kidney(MDCK)cells cultured in sample Mg_(67)Zn_(29)Ag_(4)and its extraction medium have higher activity.However,the Mg-Zn-Ag metallic glasses exhibit obvious inhibitory effect on human rhabdomyosarcoma(RD)tumor cells.The present investigations on the glass-forming ability,corrosion behavior,cytocompatibility and tumor inhibition function of the Mg-Zn-Ag based metallic glass could reveal their biomedical application possibility.

“Glass-quake”in elastically loaded bulk metallic glasses

Amorphous solids exhibit scale-free avalanches,even under small external loading,and thus can work as suitable systems to study critical behavior and universality classes.The abundance of scale-free avalanches in the entire elastic tension regime of bulk metallic glass(BMG)samples has been experimentally observed using acoustic emission(AE)measurements.In this work,we compare the statistics of avalanches with those of earthquakes,and find that they both follow the Gutenberg–Richter law in the statistics of energies and Omori’s law of aftershock rates,and share the same characteristics in the distribution of recurrence times.These resemblances encourage us to propose the term“glass-quake”to describe avalanches in elastically loaded BMGs.Furthermore,our work echoes the potential universality of critical behavior in disordered physical systems from atomic to planetary scales,and motivates the use of elastic loaded BMGs as valuable laboratory simulators of seismic dynamics.

Structural color of metallic glass through picosecond laser

The alteration in surface color of metallic glasses(MGs)holds great significance in the context of microstructuredesign and commercial utility.It is essential to accurately describe the structures that are formed during the laser and colorseparation processes in order to develop practical laser coloring applications.Due to the high oxidation sensitivity of Labasedmetallic glass,it can broaden the color range but make it more complex.Structure coloring by laser processing on thesurface of La-based metallic glass can be conducted after thermoplastic forming.It is particularly important to clarify therole of structure and composition in the surface coloring process.The aim is to study the relationship between amorphoussurface structural color,surface geometry,and oxide formation by laser processing in metallic glasses.The findings revealedthat the periodic structure primarily determines the surface color at laser energy densities below 1.0 J/mm^(2).In contrast,thesurface color predominantly depends on the proportion of oxides that are formed when energy densities exceed 1.0 J/mm^(2).Consequently,this study provides a novel concept for the fundamental investigation of laser coloring and establishes a newavenue for practical application.

Effect of overheating-induced minor addition on Zr-based metallic glasses

Melt treatment is well known to have an important influence on the properties of metallic glasses(MGs).However,for the MGs quenched from different melt temperatures with a quartz tube,the underlying physical origin responsible for the variation of properties remains poorly understood.In the present work,we systematically studied the influence of melt treatment on the thermal properties of a Zr50Cu36Al14 glass-forming alloy and unveiled the microscopic origins.Specifically,we quenched the melt at different temperatures ranging from 1.1Tl to 1.5Tl(Tl is the liquidus temperature)to obtain melt-spun MG ribbons and investigated the variation of thermal properties of the MGs upon heating.We found that glass transition temperature,Tg,increases by as much as 36 K,and the supercooled liquid region disappears in the curve of differential scanning calorimetry when the melt is quenched at a high temperature up to 1.5Tl.The careful chemical analyses indicate that the change in glass transition behavior originates from the incorporation of oxygen and silicon in the molten alloys.The incorporated oxygen and silicon can both enhance the interactions between atoms,which renders the cooperative rearrangements of atoms difficult,and thus enhances the kinetic stability of the MGs.

Unveiling the early stage evolution of local atomic structures in the crystallization process of a metallic glass

The early stage evolution of local atomic structures in a multicomponent metallic glass during its crystallization process has been investigated via molecular dynamics simulation.It is found that the initial thermal stability and earliest stage evolution of the local atomic clusters show no strong correlation with their initial short-range orders,and this leads to an observation of a novel symmetry convergence phenomenon,which can be understood as an atomic structure manifestation of the ergodicity.Furthermore,in our system we have quantitatively proved that the crucial factor for the thermal stability against crystallization exhibited by the metallic glass is not the total amount of icosahedral clusters,but the degree of global connectivity among them.

Design and characterization of biodegradable Mg-Zn-Ag metallic glasses

In order to develop the Mg-Zn-Ag metallic glasses(MGs)for biodegradable implant applications,the glass formation ability(GFA)and biocompatibility of Mg-Zn-Ag alloys were investigated using a combination of the calculation of phase diagrams(CALPHAD)and experimental measurements.High GFA potentiality of two alloy series,specifically Mg_(96-x)Zn_xAg_(4)and Mg_(94-x)Zn_xAg_6(x=17,20,23,26,29,32,35),was predicted theoretically and then substantiated through experimental testing.X-ray diffraction(XRD)and differential scanning calorimetry(DSC)techniques were used to evaluate the crystallinity,GFA,and crystallization characteristics of these alloys.The results showed that compositions between Mg_(73)Zn_(23)Ag_(4)and Mg_(64)Zn_(32)Ag_(4)for Mg_(96-x)Zn_xAg_4,Mg_(66)Zn_(28)Ag_(6)and Mg_(63)Zn_(31)Ag_(6for)Mg_(94-x)Zn_xAg_(6)displayed a superior GFA.Notably,the GFA of the Mg_(96-x)Zn_xAg_(4)series was better than that of the Mg_(94-x)Zn_xAg_(6)series.Furthermore,the Mg_(70)Zn_(26)Ag_4,Mg_(74)Zn_(20)Ag_6,and Mg_(71)Zn_(23)Ag_(6)alloys showed acceptable corrosion rates,good cytocompatibility,and positive effects on cell proliferation.These characteristics make them suitable for applications in medical settings,potentially materials as biodegradable implants.

Effect of high-energy Ne ions irradiation on mechanical properties difference between Zr_(63.5)Cu_(23)Al_(9)Fe_(4.5)metallic glass and crystalline W

In this paper,high-energy Ne ions were used to irradiate Zr_(63.5)Cu_(23)Al_(9)Fe_(4.5) metallic glass(MG)and crystalline W to investigate their difference in mechanical response after irradiation.The results showed that with the irradiation dose increased,the tensile micro-strain increased,nano-hardness increased from 7.11 GPa to 7.90 GPa and 8.62 GPa,Young’s modulus increased,and H3/E2 increased which indicating that the plastic deformability decreased in crystalline W.Under the same irradiation conditions,the Zr_(63.5)Cu_(23)Al_(9)Fe_(4.5) MG still maintained the amorphous structure and became more disordered despite the longer range and stronger displacement damage of Ne ions in Zr_(63.5)Cu_(23)Al_(9)Fe_(4.5) MG than in crystalline W.Unlike the irradiation hardening and embrittlement behavior of crystalline W,Zr_(63.5)Cu_(23)Al_(9)Fe_(4.5) MG showed the gradual decrease in hardness from 6.02 GPa to 5.89 GPa and 5.50 GPa,the decrease in modulus and the increase in plastic deformability with the increasing dose.Possibly,the irradiation softening and toughening phenomenon of Zr_(63.5)Cu_(23)Al_(9)Fe_(4.5) MG could provide new ideas for the design of nuclear materials.

Magnetic and magnetocaloric effect of Er_(20)Ho_(20)Dy_(20)Cu_(20)Ni_(20)high-entropy metallic glass

Er_(20)Ho_(20)Dy_(20)Cu_(20)Ni_(20)high-entropy metallic glass exhibited excellent magnetic refrigeration material with a wide temperature range and high refrigeration capacity(RC)was reported.Er_(20)Ho_(20)Dy_(20)Cu_(20)Ni_(20)high-entropy metallic glass was observed with typical spin glass behavior around 15.5 K.In addition,we find that the magnetic entropy change(-△S_(M))originates from the sample undergoing a ferromagnetic(FM)to paramagnetic(PM)transition around 20 K.Under a field change from 0 T to 7 T,the value of maximum magnetic entropy change(-△S_(M)^(max))reaches 12.5 J/kg·K,and the corresponding value of RC reaches 487.7 J/kg in the temperature range from 6 K to 60 K.The large RC and wide temperature range make the Er_(20)Ho_(20)Dy_(20)Cu_(20)Ni_(20)high-entropy metallic glass be a promising material for application in magnetic refrigerators.

Fabrication, tribological and corrosion behaviors of detonation gun sprayed Fe-based metallic glass coating

A metallic glass coating with the composition of Fe51.33Cr14.9Mo25.67Y3.4C3.44B1.26 （mole fraction, %） on the Q235 stainless steel was developed by the detonation gun （D-gun） spraying process. The microstructure and the phase aggregate were analyzed by scanning electron microscopy and X-ray diffractometry, respectively. Microhardness, wear resistance and corrosion behavior were assessed using a Vickers microhardness tester, a ball-on-disk wear testing machine and the electrochemical measurement method, respectively. Microstructural studies show that the coatings possess a densely layered structure with the porosity less than 2.1%. The tribological behavior of the coatings examined under dry conditions shows that their relative wear resistance is five times higher than that of the substrate material. Both adhesive wear and abrasive wear contribute to the friction, but the former is the dominant wear mechanism of the metallic glass coatings. The coatings exhibit low passive current density and extremely wide passive region in 3.5% NaCl solution, thus indicating excellent corrosion resistance.

Casting effect on compressive brittleness of bulk metallic glass

An interesting phenomenon of cooling-rate induced brittleness in Zr52.5Cu17.9Ni14.6Al10Ti5 bulk metallic glass （BMG） was reported. It was found that the as-cast BMG specimens exhibited a brittle-ductile transition when the larger specimens were machined into smaller specimens through removing the cast-softening surface layer by layer. After compression tests, the as-machined small specimens, owing to the absence of the cast-softening surface, displayed highly dense and intersecting shear bands, and extensive plastic deformation. This is in contrast to the catastrophic failure and low deformability in the as-cast large specimens. More free volume was detected in the smaller as-fractured specimens, by differential scanning calorimetry, which may be attributed to the occurrence of strain softening and increased plasticity. Compared with the relatively smooth fracture surface in the smaller specimens, the larger specimens showed more diverse features on the fracture surface due to their graded structures.

Effect of Ti on microstructure,mechanical and corrosion properties of (Zr_(0.55)Al_(0.1)Ni_(0.05)Cu_(0.3))_(100-x)Ti_x bulk metallic glasses

The（Zr_（0.55）Al_（0.1）Ni_（0.05）Cu_（0.3））_（100-x）Ti_x alloys were prepared using an in-situ suck-casting method in a copper mold. The effects of Ti addition on the microstructure, mechanical and corrosion properties of the（Zr_（0.55）Al_（0.1）Ni_（0.05）Cu_（0.3））_（100-x）Ti_x alloys were investigated by X-ray diffraction, scanning electron microscopy, compressive tests and corrosion tests. It has been found that the addition of Ti higher than 4%（mole fraction） causes the formation of many crystalline phases in the alloy. The alloys with 1%-3% Ti display an obvious yield stage on their compressive stress-strain curves. An appropriate addition of Ti can improve the strength and ductility of the alloys. All the alloys have high corrosion resistance in 1 mol/L Na OH solution, and are corroded in 1 mol/L HCl solution. However, the appropriate addition of Ti can significantly improve the corrosion resistance of the alloys in HCl solution.

Enhanced plasticity of Fe-based bulk metallic glass by tailoring microstructure

The room temperature compressive plasticity of Fe75MosP10Cs.3B1.7 bulk metallic glass （BMG） was improved from 0.5% to 1.8% by increasing the sample diameter from 1.5 mm to 2.0 mm. With increasing the sample diameter to 2.0 mm, a heterogeneous microstructure with in-situ formed a-Fe dendrite sparsely distributed in the amorphous matrix can be attained. This heterogeneous mierostructure is conceived to be highly responsible for the enhanced global plasticity in this marginal Fe-based BMG.

Effect of minor Fe addition on glass forming ability and mechanical properties of Zr_(55)Al_(10)Ni_5Cu_(30) bulk metallic glass

A series of rod samples with diameter of 3 mm（Zr0.55Al0.10Ni0.05Cu0.30）100-xFex（x=0,1,2,3,4） were prepared by magnetic suspend melting and copper mold suction casting method.The effects of a small amount of Fe on glass forming ability（GFA） and mechanical properties of Zr55Al10Ni5Cu30 bulk metallic glass（BMG） were investigated.The results show that the addition of an appropriate amount（less than 3%,mole fraction） of Fe enhances GFA,as indicated by the increase in the reduced glass transition temperature Trg（=Tg/Tl） and the parameter γ（=Tx/（Tg＋Tl）） with increasing Fe content,and GFA gets deteriorated by further Fe addition（4%）.The addition of Fe also effectively improves the compressive plasticity and increases the compressive fracture strength in these Zr-based BMGs.Compressive tests on BMG sample with 3 mm in diameter and 6 mm in length reveal work-hardening and a certain plastic strain in the alloy containing 2% Fe.The BMG composite containing 4% Fe also exhibits a high fracture strength along with significant plasticity.

Preparation and properties of novel Cu-based bulk metallic glasses Cu_(55-x)Zr_(37)Ti_8In_x

The glassy rods were successfully fabricated in the Cu-Zr-Ti-In alloy system by casting into a copper mold. The value of ATx reaches a maximum of 66 K for the BMG CusoZraTTi8In5 alloy. The reasons for enhancing glass forming ability of Cu-based BMGs with the addition of indium were discussed from atomic size and thermodynamics. Alternatively, the BMG Cu52Zra7Ti8In3 exhibits the highest compressive strength （1981 MPa） and the best plasticity among glassy Cu55-xZra7TisInx （x_〈5）. The total plastic deformation of Cu52Zr37TisIn3 before fracture approaches 1.2%.

Effects of Y addition on structural and mechanical properties of CuZrAl bulk metallic glass

The effects of Y addition on the structural and mechanical properties of CuZrAl bulk metallic glass（BMG） were studied.The results show that the glass forming ability of CuZrAl system is improved by the addition of Y and the fracture strength decreases with Y addition due to the reduction of binding energy induced by Y.The fracture surface is dominated by vein-like patterns in Cu45Zr48Al7 bulk metallic glass,and changes to smooth regions in Cu46Zr42Al7Y5 BMG.TEM observation shows that Cu45Zr48Al7 BMG has a composite microstructure of nanocrystalline phases dispersed in amorphous matrix.However,the Cu46Zr42Al7Y5 BMG shows a fully amorphous structure.

Electrochemical corrosion properties of Zr- and Ti-based bulk metallic glasses

The corrosion behaviors of Ti-based and Zr-based amorphous alloys and their corresponding crystallized alloys were studied by electrochemical methods. It is found that the corrosion potentials of Zr-based amorphous alloy and its corresponding crystalline counterpart are both lower than those of the Ti-based amorphous alloy in the 1 mol/L H2SO4 solution. In the 3.5% NaCl solution,Zr-based crystallized alloy exhibits the lowest corrosion potential among the experimental samples. No passivation is observed in the corrosion process for the Zr-based crystalline alloy. However, Zr- and Ti-based amorphous alloys both exhibit passivation characteristics. EIS measurements indicate the amorphous alloys exhibit better corrosion resistance than the crystallized one in the NaCl solution. Surface analysis shows that both amorphous alloys in the NaCl solution are eroded by pitting corrosion. In the H2SO4 solution, all the alloys display similar behaviors and their surfaces can mostly keep intact except for some cracks on the corroded surface at local region.

Thermal stability,crystallization behavior,Vickers hardness and magnetic properties of Fe-Co-Ni-Cr-Mo-C-B-Y bulk metallic glasses

Thermal stability,crystallization behavior,Vickers hardness and magnetic properties of the Fe41Co7-xNixCr15Mo14C15B6Y2（x=0,1,3,5） bulk metallic glasses were investigated.The Fe41Co7-xNixCr15Mo14C15B6Y2（x=0,1,3,5） metallic glasses were fabricated by copper mold casting method.The thermal stability and crystallization behavior of the metallic glass rods were investigated by differential scanning calorimetry and isothermal experiments.Hardness measurements for samples annealed at different temperatures for different time were carried out at room temperature by the Vickers hardness tester,and magnetic measurements were performed at different temperatures by the vibrating sample magnetometer.It is shown that the addition of Ni does not play a positive role for enlarging ΔTx and GFA from parameter γ（=Tx/（Tg＋Tl））,and it can,however,increase the activation energy in the initial stage of crystallization by changing the initial crystallization behavior.The minor addition of Ni can refine the crystal grain obtained from the full crystallization experiment.The primary crystallization causes the decrease of hardness in these alloys,and as the crystallization continues,the hardness in all samples increases instead due to the precipitation of carbide and boride.The annealing temperature has an obvious effect on magnetic properties of these alloys,and the minor addition of Ni can effectively prevent the alloy annealed at high temperature to transform from paramagnetic to ferromagnetic state.