Synthesis,properties and XPS analysis of Cu-,Ni-,Ti-based metallic glasses

Metallic glasses(MG)represent an interesting group of materials as they possess outstanding physical,chemical and mechanical properties compared to their crystalline counterparts.This paper reviews the synergistic influence of Ni and Nb elements on thermal stability of supercooled liquid and corrosion resistance of as-cast Cu-Zr(Hf)-Ti-Ni-Nb bulk metallic glasses(BMGs).Additionally,in-situ second phase reinforced Cu-based BMG composites with high corrosion resistance and excellent mechanical properties are investigated.On the other hand,this paper reports the development of ultra-high corrosion resistant Ni-based metallic glasses at high temperatures for their potential applications.Corrosion resistance and XPS analysis of the Nifree Ti-based BMG are also introduced.

Dynamic indentation response of porous SiC/Ti-based metallic glass composite

Porous SiC/Ti-based metallic glass composite (Ti-BMGC), a new kind of composite, has significant application prospectin the field of light armor. To evaluate the dynamic mechanical response of the composite, dynamic Vickers hardness andindentation-induced deformation behavior were investigated by comparison with that under static indentation. The dynamic hardnesswas measured by a modified split Hopkinson pressure bar (SHPB). The dynamic hardness is obviously greater than the statichardness. The brittleness parameter under dynamic indentation is also greater than that under static indentation. Although thedynamic indentation induced more severe deformation behavior than the static indentation, the deformation and fracturecharacteristics in the two loading cases are nearly the same, both exhibiting extensive cracks in the SiC phase and severe plasticdeformation in the metallic glass phase.

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.

A tantalum-containing zirconium-based metallic glass with superior endosseous implant relevant properties

Zirconium-based metallic glasses(Zr-MGs)are demonstrated to exhibit high mechanical strength,low elastic modulus and excellent biocompatibility,making them promising materials for endosseous implants.Meanwhile,tantalum(Ta)is also well known for its ideal corrosion resistance and biological effects.However,the metal has an elastic modulus as high as 186 GPa which is not comparable to the natural bone(10–30 GPa),and it also has a relative high cost.Here,to fully exploit the advantages of Ta as endosseous implants,a small amount of Ta(as low as 3 at.%)was successfully added into a Zr-MG to generate an advanced functional endosseous implant,Zr58Cu25Al14Ta3 MG,with superior comprehensive properties.Upon carefully dissecting the atomic structure and surface chemistry,the results show that amorphization of Ta enables the uniform distribution in material surface,leading to a significantly improved chemical stability and extensive material-cell contact regulation.Systematical analyses on the immunological,angiogenesis and osteogenesis capability of the material are carried out utilizing the next-generation sequencing,revealing that Zr_(58)Cu_(25)Al_(14)Ta_(3)MG can regulate angiogenesis through VEGF signaling pathway and osteogenesis via BMP signaling pathway.Animal experiment further confirms a sound osseointegration of Zr_(58)Cu_(25)Al_(14)Ta_(3)MG in achieving better bone-implant-contact and inducing faster periimplant bone formation.

“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.

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.

Role of yttrium in glass formation of Ti-based bulk metallic glasses

Starting with Zr of two different purities, Ti-based bulk metallic glasses （BMGs） with a nominal composition of Ti40Zr25Cu12Ni3Be20 were prepared. The effect of the addition of yttrium at levels of 0.2 at.%, 0.4 at.%, 0.5 at.%, 0.6 at.%, and 1 at.% on the glass forming ability （GFA） of the alloy has been investigated by means of metallography, X-ray diffraction, and differential scanning calorimetry. Experimental data in-dicates that high impurity content dramatically reduces the glass forming ability. Microalloying with 0.5 at.% Y is effective in suppressing the crystalline phase formation and alleviating the detrimental effect of oxygen in the low-purity alloy. On the contrary, in the alloy contain-ing high-purity element, the effective yttrium addition is less than 0.4 at.%. The results indicate that the beneficial effect of the optimum dopants is mainly due to scavenging the oxygen impurity via the formation of innocuous phase.

New ductile laminate structure of Ti-alloy/Ti-based metallic glass composite with high specific strength

Bulk laminate structure of Ti-alloy/Ti-based metallic glass composite （MGC） was prepared by melting a preform of alternate stack-up foils in the high vacuum atmosphere. The composite demonstrates a good combination of yield strength （-1618MPa）, plasticity （-4.3%） and specific fracture strength （384 × 10^3 N m kg^-1 ） in compression. The maintained yield strength results from the unique microstruc- ture composed of the Ti layer, the solution layer with gradient structure and the MGC layer. Such a multilayer structure effectively inhibits the propagation of shear band, leading to the enhanced plastic- ity. Those extraordinary properities suggest that combining ductile lamella with brittle metallic glass （MG） by such a lay-up method can be an effective way to improve mechanical properties of MG.

Effects of Nitrogen on the Glass Formation and Mechanical Properties of a Ti-Based Metallic Glass

Effects of nitrogen addition on glass formation and mechanical properties of the Ti42.5Cu40Zr10Ni5Sn2.5 metallic glass were systematically investigated. It was found that a small amount of nitrogen addition facilitated the glass formation by suppressing formation of the competing eutectic structure. Unlike large atomic size elements such as Hf and Pd which usually deteriorate specific strength, nitrogen can also increase the specific strength of the current Ti-based BMGs. The results are not only helpful for understanding glass-forming ability in general, but also useful in developing cost-effective, high-performance Ti-based bulk metallic glasses with enhanced glass-forming ability.

Tensile and compressive behavior of Ti-based bulk metallic glass composites

This article focuses on the tensile and compressive characteristics of a Ti-based bulk metallic glass composite （BMGC）. It is found that the yield stress, maximum strength, and fracture strain are 1380 MPa, 1516 MPa, and 4.3% for uniaxial tension, but 1580 MPa, 4010 MPa, and 29% for uniaxial compression, respectively. The composite displays a linear ＂work hardening＂ capacity under compression; however, the ＂work softening＂ behavior is observed in the true engineering stress-strain curve upon tensile loading. The fracture surfaces of specimens also exhibit dissimilar properties under the different loadings.

Achieving work hardening by forming boundaries on the nanoscale in a Ti-based metallic glass matrix composite

Achieving work hardening in metallic glass matrix composites(MGMCs) is the key to the extensive use of these attractive materials in structural and functional applications.In this study,we investigated the formation of nanoscale boundaries resulted from the interaction between matrix and dendrites,which favors the work-hardening deformation in an in-situ Ti41Zr32Ni6 Ta7 Be14 MGMC with β-Ti dendrites in a glassy matrix at room temperature.The microstructures of samples after tension were observed by highresolution transmission electron microscopy(HRTEM) and X-ray diffraction(XRD).The work-hardening mechanism of the present composites involves:(1) appearance of dense dislocation walls(DDWs),(2)proliferation of shear bands,(3) fo rmation of boundaries on the nanoscale,and(4) interactions between hard and soft phases.A theoretical model combined with experimental data reveals the deformation mechanisms in the present work,proving that the in-situ dendrites with outstanding hardening ability in the glass matrix can provide the homogeneous deformation under tensile loading at room temperature.

Effect of carbon addition on microstructure and mechanical properties of Ti-based bulk metallic glass forming alloys

A kind of novel Ti-based composites was developed by introducing different amounts of carbon element to the Ti50Cu23Ni20Sn7 bulk metallic glass forming alloys. The thermal stability and microstructural evolution of the composites were investigated. Room temperature compression tests reveal that the composite samples with 1% and 3%（mass fraction） carbon additions have higher fracture strength and obvious plastic strain of 2195MPa, 3.1% and 1913MPa, 1.3% respectively, compared with those of the corresponding carbon-free Ti50Ni20Cu23Sn7 alloys. The deformation mechanisms of the composites with improved mechanical properties were also discussed.

A group of ductile metallic glasses prepared by modifying local structure of icosahedral quasicrystals

Inspired by research into the association between icosahedral local orders and the plasticity of metallic glasses(MGs),beryllium(Be) is added to the icosahedral quasi-crystal forming alloy Zr40Ti40Ni20. In this way, bulk metallic glasses(BMGs) with favorable compressive plasticity are fabricated. Therein, the icosahedral quasi-crystalline phase is the main competing phase of amorphous phases and icosahedral local orders are the main local atomic motifs in amorphous phases.The alloys of(Zr40Ti40Ni20)76Be24and (Zr40Ti40Ni20)72Be28with their greater plastic strain capacity show similar characteristics to highly plastic amorphous systems: The serrated flow of compression curves always follows a near-exponential distribution. The primary and secondary shear bands intersect each other, bifurcate, and bend. Typical vein patterns are densely distributed on the fracture surfaces. The relaxation enthalpy of four MGs is linearly correlated with the plastic strain, that is, the greater the relaxation enthalpy, the larger the plastic strain.

Structural origin for composition-dependent nearest atomic distance in Cu–Zr metallic glass

We systematically investigate the structures of Cu–Zr metallic glass(MG) by varying the Cu concentration in classic molecular-dynamics simulation. From the pair distribution functions(PDFs), it is found that the nearest atomic distance between Zr atom and Zr atom increases significantly after adding Cu, which is related to the composition-dependent coordination behavior between Cu atom and Zr atom in the nearest neighbors. The portion of PDF related to the nearest connection is decomposed into the contributions from quadrilateral structure, pentagonal structure, hexagonal structure,and heptagonal bipyramid structure. Although the population of denser structures, i.e. 5-, 6-, and 7-number sharing ones,increases with Cu addition increasing, the connection distances between the central atoms in all these bipyramids increase for Zr–Zr pairs, leading to the expansion of Zr–Zr nearest atomic distance. These results unveil the effect of the interplay between chemical interaction and geometric packing on the atomic-level structure in Cu–Zr metallic glasses.