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.

Two decades of continuous progresses and breakthroughs in the field of bioactive ceramics and glasses driven by CICECO-hub scientists

Over the past two decades, the CICECO-hub scientists have devoted substantial efforts to advancing bioactiveinorganic materials based on calcium phosphates and alkali-free bioactive glasses. A key focus has been thedeliberate incorporation of therapeutic ions like Mg, Sr, Zn, Mn, or Ga to enhance osteointegration and vascularization,confer antioxidant properties, and impart antimicrobial effects, marking significant contributions tothe field of biomaterials and bone tissue engineering. Such an approach is expected to circumvent the uncertaintiesposed by methods relying on growth factors, such as bone morphogenetic proteins, parathyroidhormone, and platelet-rich plasma, along with their associated high costs and potential adverse side effects. Thiscomprehensive overview of CICECO-hub’s significant contributions to the forefront inorganic biomaterials acrossall research aspects and dimensionalities (powders, granules, thin films, bulk materials, and porous structures),follows a unified approach rooted in a cohesive conceptual framework, including synthesis, characterization, andtesting protocols. Tangible outcomes [injectable cements, durable implant coatings, and bone graft substitutes(scaffolds) featuring customized porous architectures for implant fixation, osteointegration, accelerated boneregeneration in critical-sized bone defects] were achieved. The manuscript showcases specific biofunctionalexamples of successful biomedical applications and effective translations to the market of bone grafts foradvanced therapies.

基于阴极往复运动的TGV电铸铜实心填充工艺

玻璃通孔(TGV)转接板因其具有优良的高频电学特性,在先进封装领域受到广泛关注。然而随着TGV深宽比的不断增加,采用传统的阴极定轴旋转式电铸工艺,其填充难度与成本将随之提高。为实现高深宽比TGV的无缺陷填充,减少电铸耗时和成本,提出一种基于阴极往复运动的TGV无缺陷镀铜填充新工艺。在仿真和实验的基础上,系统研究了阴极运动方式对TGV孔内电铸液传质、离子浓度、填充速率的影响。仿真和实验结果均表明,采用阴极往复运动能有效地保证TGV孔内各处离子浓度分布的均匀一致性,减缓浓差极化,从而提高沉积速率及其上限值。在不含任何添加剂的体系中,同等沉积电位条件下平均填充速率从阴极定轴旋转式电铸工艺的6.1μm/h提高至9.2μm/h。当电位为0.5 V时,阴极往复运动方式下平均填充速率达到45.2μm/h,且电铸铜填充层中未发现孔隙缺陷。这为在无添加剂电铸铜体系中实现高深宽比TGV的无缺陷电铸铜填充提供了一种可行的低成本方案。

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.

Sodium Diffuses from Glass Substrates through P1 Lines and Passivates Defects in Perovskite Solar Modules

Most thin-film photovoltaic modules are constructed on soda-lime glass(SLG)substrates containing alkali oxides,such as Na_(2)O.Na may diffuse from SLG into a module's active layers through P1 lines,an area between a module's constituent cells where the substrate-side charge transport layer(CTL)is in direct contact with SLG.Na diffusion from SLG is known to cause several important effects inⅡ-Ⅵand chalcogenide solar modules,but it has not been studied in perovskite solar modules(PSMs).In this work,we use complementary microscopy and spectroscopy techniques to show that Na diffusion occurs in the fabrication process of PSMs.Na diffuses vertically inside P1 lines and then laterally from P1 lines into the active area for up to 360 pm.We propose that this process is driven by the high temperatures the devices are exposed to during CTL and perovskite annealing.The diffused Na preferentially binds with Br,forming Br-poor,l-rich perovskite and a species rich in Na and Br(Na-Br)close to P1 lines.Na-Br passivates defect sites,reducing non-radiative recombination in the perovskite and boosting its luminescence by up to 5×.Na-Br is observed to be stable after 12 weeks of device storage,suggesting long-lasting effects of Na diffusion.Our results not only point to a potential avenue to increase PSM performance but also highlight the possibility of unabated Na diffusion throughout a module's lifetime,especially if accelerated by the electric field and elevated temperatures achievable during device operation.

TGV互联技术的机遇与挑战

随着半导体电路集成度越来越高,进而对封装技术提出新的要求,TSV(Through-Silicon Via)技术已不能满足多器件、多芯片的高性能互联要求。TGV(Through-Glass Via)技术凭借其高频电学特性、制造生产流程简单、成本低、机械稳定性强等应用优势,开始在3D集成半导体封装等领域受到关注。本文主要综述了TGV技术的研究进展,介绍了TGV技术的背景及优势特性,梳理了TGV技术关键核心工艺和最新进展,尤其是TGV通孔成孔技术和填充工艺,最后讨论了TGV当前面临的技术问题与挑战,为后续研究TGV技术的研究提供了思路和参考。

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.

污水处理场TGV滤池施工质量控制

针对TGV滤池具有多池壁、多顶板、标高不一的结构特点,论文结合在燕山威立雅牛口峪污水处理场工程TGV滤池中的施工,通过合理设置施工缝、附加抗裂网片、分块拼装滤板、改进缝隙封堵工艺等方法,降低了池体裂缝的发生概率,提高了滤板安装精度,加快了施工进度,保证了施工质量。

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.

“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.

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.