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.

Geochemistry of volcanic glass from Mahanadi offshore region,eastern continental margin of India:Constraints on the contribution of latest Toba super-eruption

The tephra layers in multiple sediment cores from the offshore region of the Mahanadi basin in the northern Bay of Bengal were investigated for possible volcanic sources. The glass shards from those tephra layers were studied for size distribution, texture, and elemental geochemistry to establish chronostratigraphic markers for regional and global Quaternary correlation. The textural features of fine-grained(silty) volcanic glasses suggest the distal source of these tephra deposits. Major element composition with elevated SiO_(2) contents ranging between75%–76% and dominance of K_(2)O(> 4.5%) over CaO(< 0.9%) suggest ashes have originated from siliceous rhyolitic melts, similar to the petrographic composition of tephra from the Toba volcano. The bulk trace element compositions of the same glass shards were comparable with those reported in the youngest Toba tephra reported elsewhere. Likewise, the LREE-dominated chondrite normalized REE profiles of tephra from the Mahanadi basin closely resemble the characteristic REE patterns in Toba ash from other parts of the Indian Ocean and thus confirmed the contribution of the youngest Toba super-eruption for this ash layers.

Mixed Alkali-zinc Effects on Thermo-mechanical Properties in Borosilicate Glasses

A series of mixed alkali-zinc borosilicate glasses with various r values(r=molar ratio of[ZnO]/([R^(2)O]+[ZnO]))from 0.00 to 1.00 were fabricated to probe the mixed alkali-zinc effects on thermo-mechanical properties.The nonlinear evolution of glass transition temperature(T_(g))with the addition of ZnO is ascribed to the competition of two converse factors,i e,the T_(g)depression as one of the colligative properties for a solution,on the one hand,and the enhancement of T_(g)due to the higher field strength of zinc cations compared to that of alkali ions.However,the nonlinear evolution of elastic moduli and coefficients of thermal expansion with r is attributed to the variance of intermediate-range clusters,which is confirmed by infrared and Raman scattering spectra.These findings are very helpful in tailoring the performance of borosilicate glasses.

Preparation and Characterization of ZnO-CuO-Bi_(2)O_(3)-B_(2)O_(3)-SiO_(2)System Low Melting Sealing Glasses

Lead-free low melting glasses,ZnO-CuO-Bi_(2)O_(3)-B_(2)O_(3)-SiO_(2)system,with fixed contents of 15 mol%CuO and 20 mol%Bi_(2)O_(3),were prepared by using melt cooling method.Structure and thermal properties of the glasses were studied by using X-ray diffractometer(XRD),infrared spectrometer(FIT-IR),thermal dilatometer and differential thermal analyzer(DTA).Chemical durability of the glasses was studied by using dissolution rate method.Wettability of glasses on substrate was tested by using button sintering experiment.It is found that alkaline resistance of the glass solders is lower than that of plate glass and the water resistance is comparable with that of plate glass.The sealing temperatures are Ts=445-490℃,while the average thermal expansion coefficient from room temperature to 300℃is in the range of(65-82)×10^(−7)℃^(−1).At sealing temperature,the glass solders have good wettability on plate glass or alumina substrate.They are not crystallized even sintered at the sealing temperature for 30 min.The solder glasses are suitable for sealing plate glass,alumina and other inorganic non-metallic materials.

Solid-state NMR reveals that oxygen tri-clusters make glass highly crackresistant

In a recent paper,advanced solid-state nuclear magnetic resonance(SSNMR)technology was employed to reveal the underlying mechanism contributing to the high hardness and exceptional resistance to fragmentation observed in certain special glasses[1].This study utilized SSNMR to analyze the atomic-scale internal structure of glass,enabling the quantification of the fraction of three-coordinated oxygen([^((3))O]).The research findings demonstrate a quantitative relationship between[^((3))O]and the resistance of glass to crack initiation.

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.

Influence of Al_(2)O_(3)/SiO_(2) Ratio on the Structure and Properties of Na^(+)/K^(+)Ion Exchange Na_(2)O-MgO-Al_(2)O_(3)-SiO_(2) Glasses

In this work,the structure,viscosity and ion-exchange process of Na_(2)O-MgO-Al_(2)O_(3)-SiO_(2) glasses with different Al_(2)O_(3)/SiO_(2) molar ratios were investigated.The results showed that,with increasing Al_(2)O_(3)/SiO_(2) ratio,the simple structural units Q_(1) and Q_(2) transformed into highly aggregated structural units Q_(3) and Q_(4),indicating the increase of polymerization degree of glass network.Meanwhile,the coefficient of thermal expansion decreased from 9.23×10^(-6)℃^(-1) to 8.88×10^(-6)℃^(-1).The characteristic temperatures such as melting,forming,softening and glass transition temperatures increased with the increase of Al_(2)O_(3)/SiO_(2) ratio,while the glasses working temperature range became narrow.The increasing Al_(2)O_(3)/SiO_(2) ratio and prolonging ion-exchange time enhanced the surface compressive stress(CS)and depth of stress layer(DOL).However,the increase of ion exchange temperature increased the DOL and decreased the CS affected by stress relaxation.There was a good linear relationship between stress relaxation and surface compressive stress.Chemical strengthening significantly improved the hardness of glasses,which reached the maximum value of(622.1±10)MPa for sample with Al_(2)O_(3)/SiO_(2) ratio of 0.27 after heat treated at 410℃for 2 h.

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 Fe_(2)O_(3)on the Structure,Physical Properties and Crystallization of CaO-Al_(2)O_(3)-SiO_(2)Glass

The calcium aluminosilicate-based glasses(CaO-Al_(2)O_(3)-SiO_(2),CAS)with different Fe_(2)O_(3)content(0.10wt%,0.50wt%,0.90wt%,and 1.30wt%)were prepared by traditional melt-quenching method.The glass network structure,thermal and mechanical properties,and crystallization behavior changes were investigated by nuclear magnetic resonance spectrometer,Fourier-transform infrared spectro-photometer,X-ray diffractometer,differential scanning calorimetry and field emission scanning electron microscope measurements.The change of Q^(n)in glass structures reveals the glass network connectivity decreases due to the increasing content of Fe_(2)O_(3)addition,resulting in the increasing of non-bridging number in glass structure.The glass densities slightly rise from 2.644 to 2.681 g/cm^(3),while Vickers’s hardness increases at first,from 6.469 to 6.901 GPa,then slightly drops to 6.745 GPa,with Fe_(2)O_(3)content increase.There is almost no thermal expansion coefficient change from different Fe_(2)O_(3)content.The glass transmittance in visible range gradually decreases with higher Fe_(2)O_(3)content,resulting from the strong absorption of Fe^(2+)and Fe^(3+)ions.The calculated activation energy from thermal analysis results first decreases from 282.70 to 231.18 kJ/mol,and then increases to 244.02 kJ/mol,with the Fe_(2)O_(3)content increasing from 0.10wt%to 1.30wt%.Meanwhile,the maximum Avrami constant of 2.33 means the CAS glasses exhibit two-dimensional crystallization.All of the CAS glass-ceramics samples contain main crystal phase of anorthite,the microstructure appears lamellar and columnar crystals.

Provenance of colorless and brown volcanic glass in late Pleistocene tephra layers in the Western Philippine Sea

Tephra layers in the western Philippine Sea,characterized by abundant volcanic glass shards,may provide crucial evidence on the eruption history of volcanoes and tectonic evolution of the western Pacific.A 220-ka sediment core from the Benham Rise in the western Philippine Sea offers new insights into the provenance of four intercalated tephra layers(T1–T4,in chronological order)containing either colorless or brown glass shards.Relative to primitive mantle,all glass shards are enriched in large-ion lithophile elements,such as Rb,Cs,and Pb,and depleted in high field-strength elements,such as Th,Nb,and Ta,indicating a subduction-related origin.The colorless glass shards are characterized by high SiO_(2)(>78%)and light rare earth element(LREE)contents as well as high La/Sm ratios(>9),low FeO and MgO contents(<1%),low Sr/Y(<15)and high Ba/Th ratios(>100),pointing to a rhyolitic composition and a medium-K calc-alkaline serial affinity.In contrast,the brown glass shards are characterized by lower SiO_(2)(<63%)and LREE contents,higher FeO,MgO,and CaO contents,lower La/Sm(<6)and Ba/Th(<75),and similar Sr/Y ratios(<15),indicating derivation from medium to high-K calc-alkaline andesite magma.Brown glass shards from layers T3(152 ka)and T4(172 ka)were correlated with volcanic deposits from the Taal and Laguna Caldera in the Maccolod Corridor,respectively,while the colorless glass shards from layers T1(36.5 ka)and T2(61.2 ka)were likely sourced from the Irosin Caldera in the Bicol Arc.Establishing the provenance of late Pleistocene tephra layers in the western Philippine Sea is helpful to complement a Philippine volcanic history and establish a regional tephrochronostratigraphy.

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.

The Effect of Na_(2)O/B_(2)O_(3)Composition Ratio on the Structure and Properties of Cu^(+)Doped Luminescent Glass

Cu^(+)-doped alkali borosilicate glasses with different Na_(2)O contents were prepared by the melting method,and the effects of different R values(R=Na_(2)O/B_(2)O_(3))on the structure,ion presence state and luminescence properties of Cu^(+)-doped alkali borosilicate glasses were investigated.The analysis by FT-IR and Raman spectroscopy shows that,with the increase of R value of the glass,the[BO_(3)]in the structure of Cu^(+)-doped alkali borosilicate glass transforms into[BO_(4)]and the number of non-bridging oxygen in the glass network appears to be slightly increased.The absorption spectra and EPR analysis reveal that the Cu^(+)content in the glass gradually decreases and the Cu^(2+)content gradually increases as the R value of the glass increases.XPS and PL tests further indicate that the transformation of the octahedral coordination structure of Cu^(+)to the octahedral coordination structure of Cu^(2+)and the cubic coordination structure of Cu^(+)occurs in the glass as the R value of the glass increases.This transformation can effectively reduce the concentration quenching phenomenon of Cu^(+)and improve the fluorescence luminescence intensity of the glass samples.Meanwhile,the samples were found to have luminescence tunability as well as good thermal stability.

Low-frequency hybridized excess vibrations of two-dimensional glasses

One hallmark of glasses is the existence of excess vibrational modes at low frequenciesωbeyond Debye’s prediction.Numerous studies suggest that understanding low-frequency excess vibrations could help gain insight into the anomalous mechanical and thermodynamic properties of glasses.However,there is still intensive debate as to the frequency dependence of the population of low-frequency excess vibrations.In particular,excess modes could hybridize with phonon-like modes and the density of hybridized excess modes has been reported to follow D_(exc)(ω)~ω^(2)in 2D glasses with an inverse power law potential.Yet,the universality of the quadratic scaling remains unknown,since recent work suggested that interaction potentials could influence the scaling of the vibrational spectrum.Here,we extend the universality of the quadratic scaling for hybridized excess modes in 2D to glasses with potentials ranging from the purely repulsive soft-core interaction to the hard-core one with both repulsion and attraction as well as to glasses with significant differences in density or interparticle repulsion.Moreover,we observe that the number of hybridized excess modes exhibits a decrease in glasses with higher density or steeper interparticle repulsion,which is accompanied by a suppression of the strength of the sound attenuation.Our results indicate that the density bears some resemblance to the repulsive steepness of the interaction in influencing low-frequency properties.

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.

Third-order nonlinear wavelength conversion in chalcogenide glass waveguides towards mid-infrared photonics

The increasing demand in spectroscopy and sensing calls for infrared(mid-IR)light sources.Here,we theoretically investigate nonlinear wavelength conversion of Ge_(28)Sb_(12)Se_(60)chalcogenide glass waveguide in the mid-IR spectral regime.With waveguide dispersion engineering,we predict generation of over an octave wavelength(2.8μm-5.9μm)tuning range Raman soliton self-frequency shift,over 2.5 octaves wavelength cover range supercontinuum(1.2μm-8.0μm),as well as single soliton Kerr comb generated in suspended Ge_(28)Sb_(12)Se_(60)waveguide.Our findings evidenced that Ge_(28)Sb_(12)Se_(60)chalcogenide glass waveguides can simultaneously satisfy the generation of Raman soliton self-frequency shift,supercontinuum spectrum,and Kerr frequency comb generation through dispersion engineering towards mid-IR on chip.

Coupling of quasi-localized and phonon modes in glasses at low frequency

Boson peak of glasses,a THz vibrational excess compared to Debye squared-frequency law,remains mysterious in condensed-matter physics and material science.It appears in many different kinds of glassy matters and is also argued to exist in damped crystals.A consensus is that boson peak originates from the coupling of the(quasi)-localized non-phonon modes and the plane-wave-like phonon modes,but the coupling behavior is still not fully understood.In this paper,by modulating the content of localized modes and the frequencies of phonon modes,the coupling is clearly reflected in the localization and anharmonicity of low-frequency vibrational modes.The coupling enhances with increasing cooling rate and sample size.For finite sample size,phonon modes do not fully intrude into the low frequency to form a dense spectrum and they are not sufficiently coupled to the localized modes,thus there is no Debye level and boson peak is ill-defined.This suggestion remains valid in the presence of thermal motions induced by temperature,even though the anharmonicity comes into play.Our results point to the coupling of quasi-localized and phonon modes and its relation to the boson peak.

Damping properties and mechanism of aluminum matrix composites reinforced with glass cenospheres

The damping properties were improved by preparing Al matrix composites reinforced with glass cenospheres through the pressure infiltration method.Transmission electron microscopy and scanning electron microscopy were employed to characterize the microstructure of the composites.The low-frequency damping properties were examined by using a dynamic mechanical thermal analyzer,aiming at exploring the changing trend of damping capacity with strain,temperature,and frequency.The findings demonstrated that the damping value rose as temperature and strain increased,with a maximum value of 0.15.Additionally,the damping value decreased when the frequency increased.Dislocation damping under strain and interfacial damping under temperature served as the two primary damping mechanisms.The increase in the density of dislocation strong pinning points following heat treatment reduced the damping value,which was attributed to the heat treatment enhancement of the interfacial bonding force of the composites.

Composition Analysis and Identification of Ancient Glass Products Based on L1 Regularization Logistic Regression

In view of the composition analysis and identification of ancient glass products, L1 regularization, K-Means cluster analysis, elbow rule and other methods were comprehensively used to build logical regression, cluster analysis, hyper-parameter test and other models, and SPSS, Python and other tools were used to obtain the classification rules of glass products under different fluxes, sub classification under different chemical compositions, hyper-parameter K value test and rationality analysis. Research can provide theoretical support for the protection and restoration of ancient glass relics.

基于Ameriflux通量观测数据的Hi-GLASS潜热通量产品验证

潜热通量产品的验证与分析对于研究气候变化及能量循环具有重要意义。全球陆表高分辨率蒸散产品(high resolution global lAnd surface evapotranspiration product,Hi-GLASS ET)融合了5种传统蒸散算法,能够生产出较高精度的陆表潜热通量产品,但目前没有针对此产品的验证研究。利用Ameriflux通量观测站点的潜热通量观测值与相应的Hi-GLASS陆表潜热通量产品估算值进行对比,获取多组有效验证数据。验证结果显示,所选站点实际观测值与产品估算值的决定系数(R 2)为0.6,均方根误差(RMSE)为34.4 W/m^(2),平均偏差(Bias)为-13.4 W/m^(2),克林-古普塔效率(Kling-Gupta efficiency,KGE)为0.49,Hi-GLASS潜热通量产品具有较高的精度,算法的拟合结果较好;此外,空间分布也表明Hi-GLASS陆表潜热通量产品符合正常的自然规律。由于数据获取的局限性,仅采用了美国地区18个站点数据对产品进行验证,在其他地区仍需进一步验证。

Density of excess modes below the first phonon mode in four-dimensional glasses

Glasses are known to possess low-frequency excess modes beyond the Debye prediction.For decades,it has been assumed that evolution of low-frequency density of excess modes D(ω) with frequency ω follows a power-law scaling:D(ω)~ω~γ.However,it remains debated on the value of γ at low frequencies below the first phonon-like mode in finitesize glasses.Early simulation studies reported γ=4 at low frequencies in two-(2D),three-(3D),and four-dimensional(4D)glasses,whereas recent observations in 2D and 3D glasses suggested γ=3.5 in a lower-frequency regime.It is uncertain whether the low-frequency scaling of D(ω)~ω^(3.5) could be generalized to 4D glasses.Here,we conduct numerical simulation studies of excess modes at frequencies below the first phonon-like mode in 4D model glasses.It is found that the system size dependence of D(ω) below the first phonon-like mode varies with spatial dimensions:D(ω) increases in2D glasses but decreases in 3D and 4D glasses as the system size increases.Furthermore,we demonstrate that the ω^(3.5)scaling,rather than the ω~4 scaling,works in the lowest-frequency regime accessed in 4D glasses,regardless of interaction potentials and system sizes examined.Therefore,our findings in 4D glasses,combined with previous results in 2D and 3D glasses,suggest a common low-frequency scaling of D(ω)~ ω^3.5) below the first phonon-like mode across different spatial dimensions,which would inspire further theoretical studies.