Achieving Narrowed Bandgaps and Blue-Light Excitability in Zero-Dimensional Hybrid Metal Halide Phosphors via Introducing Cation-Cation Bonding

Zero-dimensional(0D)hybrid metal halides,which consist of organic cations and isolated inorganic metal halide anions,have emerged as phosphors with efficient broadband emissions.However,these materials generally have too wide bandgaps and thus cannot be excited by blue light,which hinders their applications for efficient white light-emitting diodes(WLEDs).The key to achieving a blue-light-excitable 0D hybrid metal halide phosphor is to reduce the fundamental bandgap by rational chemical design.In this work,we report two designed hybrid copper(I)iodides,(Ph_(3)MeP)_(2)Cu_(4)I_(6)and(Cy_(3)MeP)_(2)Cu_(4)I_(6),as blue-light-excitable yellow phosphors with ultrabroadband emission.In these compounds,the[Cu_(4)I_(6)]^(2-)anion forms an I6 octahedron centered on a cationic Cu_(4)tetrahedron.The strong cation-cation bonding within the unique cationic Cu_(4)tetrahedra enables significantly lowered conduction band minimums and thus narrowed bandgaps,as compared to other reported hybrid copper(I)iodides.The ultrabroadband emission is attributed to the coexistence of free and self-trapped excitons.The WLED using the[Cu_(4)I_(6)]^(2-)anion-based single phosphor shows warm white light emission,with a high luminous efficiency of 65 Im W^(-1)and a high color rendering index of 88.This work provides strategies to design narrow-bandgap 0D hybrid metal halides and presents two first examples of blue-light-excitable 0D hybrid metal halide phosphors for efficient WLEDs.

Mechanical properties and interfacial characteristics of 6061 Al alloy plates fabricated by hot-roll bonding

This work aims to investigate the mechanical properties and interfacial characteristics of 6061 Al alloy plates fabricated by hotroll bonding(HRB)based on friction stir welding.The results showed that ultimate tensile strength and total elongation of the hot-rolled and aged joints increased with the packaging vacuum,and the tensile specimens fractured at the matrix after exceeding 1 Pa.Non-equilibrium grain boundaries were formed at the hot-rolled interface,and a large amount of Mg_(2)Si particles were linearly precipitated along the interfacial grain boundaries(IGBs).During subsequent heat treatment,Mg_(2)Si particles dissolved back into the matrix,and Al_(2)O_(3) film remaining at the interface eventually evolved into MgO.In addition,the local IGBs underwent staged elimination during HRB,which facilitated the interface healing due to the fusion of grains at the interface.This process was achieved by the dissociation,emission,and annihilation of dislocations on the IGBs.

Structure Regulation of Electric Double Layer via Hydrogen Bonding Effect to Realize High-Stability Lithium-Metal Batteries

The interfacial chemistry of solid electrolyte interphases(SEI)on lithium(Li)electrode is directly determined by the structural chemistry of the electric double layer(EDL)at the interface.Herein,a strategy for regulating the structural chemistry of EDL via the introduction of intermolecular hydrogen bonds has been proposed(p-hydroxybenzoic acid(pHA)is selected as proof-of-concept).According to the molecular dynamics(MD)simulation and density functional theory(DFT)calculation results,the existence of hydrogen bonds realizes the anion structural rearrangement in the EDL,reduces the lowest unoccupied molecular orbital(LUMO)energy level of anions in the EDL,and the number of free solvent molecules,which promotes the formation of inorganic species-enriched SEI and eventually achieves the dendrite-free Li deposition.Based on this strategy,Li‖Cu cells can stably run over 185 cycles with an accumulated active Li loss of only 2.27 mAh cm^(-2),and the long-term cycle stability of Li‖Li cells is increased to 1200 h.In addition,the full cell pairing with the commercial LiFePO_(4)(LFP)cathodes exhibits stable cycling performance at 1C,with a capacity retention close to 90%after 200 cycles.

Time-dependent effects in transient liquid phase bonding of 304L and Cp-Ti using an Ag-Cu interlayer

One of the challenges for bimetal manufacturing is the joining process.Hence,transient liquid phase(TLP)bonding was performed between 304L stainless steel and Cp-Ti using an Ag-Cu interlayer with a thickness of 75μm for bonding time of 20,40,60,and 90 min.The bonding temperature of 860℃ was considered,which is under the β transus temperature of Cp-Ti.During TLP bonding,various intermetallic compounds(IMCs),including Ti_(5)Cr_(7)Fe_(17),(Cr,Fe)_(2)Ti,Ti(Cu,Fe),Ti_(2)(Cu,Ag),and Ti_(2)Cu from 304L toward Cp-Ti formed in the joint.Also,on the one side,with the increase in time,further diffusion of elements decreases the blocky IMCs such as Ti_(5)Cr_(7)Fe_(17),(Cr,Fe)_(2)Ti,Ti(Cu,Fe)in the 304L diffusion-affected zone(DAZ)and reaction zone,and on the other side,Ti_(2)(Cu,Ag)IMC transformed into fine morphology toward Cp-Ti DAZ.The microhardness test also demonstrated that the(Cr,Fe)_(2)Ti+Ti_(5)Cr_(7)Fe_(17) IMCs in the DAZ on the side of 304L have a hardness value of HV 564,making it the hardest phase.The maximum and minimum shear strength values are equal to 78.84 and 29.0 MPa,respectively.The cleavage pattern dominated fracture surfaces due to the formation of brittle phases in dissimilar joints.

Bonding enhancement of cold rolling TA1 P-Ti/AA6061 composite plates via surface oxidation treatment

TA1 P-Ti/AA6061 composite plate was produced by oxidizing the surface of the titanium plate and adopting a cold roll bonding process.The results revealed that the oxide film(Ti6O)prepared on the surface of TA1 pure titanium was easy to crack during the cold roll bonding,thereby promoting the formation of an effective mechanical interlock at the interface,which can effectively reduce the minimum reduction rate of the composite plates produced by cold rolling of titanium and aluminium plates.Moreover,the composite plate subjected to oxidation treatment exhibited high shear strength,particularly at a 43%reduction rate,achieving a commendable value of 117 MPa.Based on oxidation treatment and different reduction rates,the annealed composite plates at temperatures of 400,450,and 500°C displayed favorable resistance to interface delamination,highlighting their remarkable strength-plasticity compatibility as evidenced by a maximum elongation of 31.845%.

Bonding interface characteristic and shear strength of diffusion bonded Ti-17 titanium alloy

The bonding interface characteristic and shear strength of diffusion bonded Ti-17 titanium alloy at different bonding time were investigated. The results show that the average size of voids decreases while the amount of voids decreases after increasing to the maximum value with the increasing bonding time. The irregular void with a scraggly edge tends to an ellipse void with smooth surface and then changes to a tiny void with round shape. The grains across bonding interface occur at bonding time of 60 min. The shear strength of bond increases with increasing bonding time, and the highest shear strength of bond is 887.4 MPa at 60 min. The contribution of plastic deformation on the void closure and the increase of shear strength is significant even though the action time of plastic deformation is short.

Effect of bonding parameters on microstructures and properties during TLP bonding of Ni-based super alloy

Ni-based alloy was transient liquid phase bonded using a BNi-2 interlayer. The effect of bonding parameters on the microstructures and mechanical properties of the joints was investigated. With the increase of bonding temperature or time, the number of Ni-rich and Cr-rich borides and the grain size of precipitation zone decrease. Higher bonding temperature or longer bonding time is beneficial to the diffusion of melting point depressant elements （B and Si） from the PZ to the base metal and atomic interdiffusion between the base metal and the joint. The chemical composition and microstructure of the joints bonded at 1170 ℃ for 24 h are comparable to the base metal. The shear test results show that both the room and elevated temperature shear-strengths of the joints increase with increasing bonding time. However, the effect of bonding time on elevated temperature tensile-shear strength is greater than on room temperature tensile-shear strength.

Effect of grain size of primary α phase on bonding interface characteristic and mechanical property of press bonded Ti-6Al-4V alloy

The effect of grain size of primary α phase on the bonding interface characteristic and shear strength of bond was investigated in the press bonding of Ti-6Al-4V alloy. The quantitative results show that the average size of voids increases from 0.8 to 2.6 μm and the bonding ratio decreases from 90.9% to 77.8% with an increase in grain size of primary α phase from 8.2 to 16.4 μm. The shape of voids changes from the tiny round to the irregular strip. The highest shear strength of bond can be obtained in the Ti-6Al-4V alloy with a grain size of 8.2 μm. This is contributed to the higher ability of plastic flow and more short-paths for diffusion in the alloy with smaller grain size of primary α phase, which promote the void closure process and the formation of α/β grains across bonding interface.

Effects of Fe-Al intermetallic compounds on interfacial bonding of clad materials

The growth of intermetallic compounds at the interface between solid Al and Fe and the effects of intermetallic compound layers on the interfacial bonding of clad materials were investigated. The results showed that the interface between the solid Fe and Al formed by heat-treatment consisted of Fe2Al5 and FeAl3 intermetallic compound layers, which deteriorated the interfacial bonding strength. Fractures occurred in the intermetallic compound layer during the shear testing. The location of the fracture depended on the defects of microcracks or voids in the intermetallic compound layers. The microcracks in the intermetallic compound layer were caused by the mismatch of thermal expansion coefficients of materials during cooling, and the voids were consistent with the Kirkendall effect. The work will lay an important foundation for welding and joining of aluminum and steel, especially for fabrication of Al-Fe clad materials.

Interface analysis of 7B52 Al alloy laminated composite fabricated by hot-roll bonding

The bonding interface of 7B52 Al alloy laminated composite （ALC） fabricated by hot rolling was investigated using optical microscopy （OM）, transmission electron microscopy （TEM）, scanning electron microscopy （SEM）, ultrasonic flaw detection （UFD）, and bonding strength tests. The results show that metallurgical bonding is achieved at the interface after composite rolling. The TEM analysis and tensile tests indicate that the 7B52 ALC plate combines high strength of the hard individual layer and good toughness of the soft individual layer. However, UFD technology and SEM analysis prove that the defects （thick oxide films, acid washed residues, air, oil and coarse particles） existing in the bonding interface are harmful to the bonding strength. To sum up, the composite roiling process is suitable for 7B52 ALC plate, and the content and size of the defects should be controlled strictly. Advanced surface treatment of each individual layer would be beneficial to further improve the bonding quality.

Tungsten/steel diffusion bonding using Cu/W-Ni/Ni multi-interlayer

Diffusion bonding between tungsten and 0Cr13Al stainless steel using a Cu/90W-10Ni powder mixtures/Ni multi-interlayer was carried out in vacuum at 1150 °C with a pressure of 5 MPa for 60 min. The microstructures, composition distribution and fracture characteristics of the joint were studied by SEM and EDS. Joint properties were evaluated by shear experiments and thermal shock tests. The results showed that the joints comprised tungsten/Cu-Ni sub-layer/W-Ni composites sub-layer/Ni sub-layer/0Cr13Al stainless steel. The W-Ni composites sub-layer with a homogeneous and dense microstructure was formed by solid phase sintering of 90W-10Ni powder mixtures. Sound bonding between tungsten base material and W-Ni composites sub-layer was realized based on transient liquid phase (TLP) diffusion bonding mechanism. Joints fractured at bonding zone of W-Ni composites sub-layer and Ni sub-layer during shear testing, and the average strength was 256 MPa. Thermal shock tests showed that joints could withstood 60 thermal cycles quenching from 700 °C to room temperature.

Preparation of ultra-fine grain Ni-Al-WC coating with interlocking bonding on austenitic stainless steel by laser clad and friction stir processing

The ultra-fine structured Ni?Al?WC layer with interlocking bonding was fabricated on austenitic stainless steel by combination of laser clad and friction stir processing (FSP). Laser was initially applied to Ni?Al elemental powder preplaced on the austenitic stainless steel substrate to produce a coating for further processing. The as-received coating was subjected to FSP treatment, processed by a rotary tool rod made of WC?Co alloy, to obtain sample for inspection. Microstructure, phase constitutions, hardness and wear property were investigated by methods of scanning electronic microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDX) microanalysis, and X-ray diffraction (XRD), hardness test alongside with dry sliding wear test. The results show that the severe deformation effect exerted on the specimen resulted in an ultra-fine grain layer of about 100μmin thickness and grain size of 1?2μm. Synergy between introduction of WC particles to the deformation layer and deformation strengthening contributes greatly to the increase in hardness and friction resistance. An interlocking bonding between the coating and matrix which significantly improves bonding strength was formed due to the severe deformation effect.

Microstructure and properties at bonding interface of AA4045/AA3003 aluminum alloy cladding billet prepared by semi-continuous casting

AA4045/AA3003 cladding billet was prepared by direct chill semi-continuous casting process. The macrostructures, microstructures, temperature distribution, compositions distribution and the mechanical properties at the bonding interface were investigated in detail. The results show that the cladding billet with few defects could be obtained by semi-continuous casting process. At the interface, diffusion layer of about 10μm on average formed between the two alloys due to the diffusion of alloy elements in the temperature range from 596 to 632 °C. From the side of AA4045 to the side of AA3003, the Si content has a trend to decrease, while the Mn content has a trend to increase gradually. Tensile strength of the cladding billet reaches 103.7 MPa, the fractured position is located on the AA3003 side, and the shearing strength is 91.1 MPa, revealing that the two alloys were combined metallurgically by mutual diffusion of alloy elements.

First principles calculation of electronic structure, chemical bonding and elastic properties of ultra-incompressible Re_2P

The electronic structures, chemical bonding and elastic properties of the Co2P-type structure phase ultra-incompressible Re2P （orthorhombic phase） were investigated by density-functional theory （DFT） within generalized gradient approximation （GGA）. The calculated energy band structures show that the orthorhombic structure phase Re2P is metallic material. The density of state （DOS） and the partial density of state （PDOS） calculations show that the DOS near the Fermi level is mainly from the Re-5d state. Population analysis suggests that the chemical bonding in Re2P has predominantly covalent character with mixed covalent-ionic character. Basic physical properties, such as lattice constant, bulk modulus, shear modulus, and elastic constants Cij, were calculated. The elastic modulus and Poisson ratio were also predicted. The results show that the Co2P-type structure phase Re2P is mechanically stable and behaves in a brittle manner.

Interfacial microstructure and chemical stability during diffusion bonding of single crystal Al_2O_3-fibres with Ni25.8Al9.6Ta8.3Cr matrix

BN coated A1203 fibre-reinforced NiAl-alloy composites were fabricated by hot pressing at 1 200-1 400 ℃, and the interracial microstructure and chemical stability of BN coated Al2O3 fibre-reinforced NiAl-alloy composites were investigated by scanning electron microscopy （SEM） and analytical transmission electron microscopy （TEM）. It was found that the complicated chemical reactions and diffusion processes happened in the interface area between BN-layer and Ni25.8A19.6Ta8.3 during the hot pressing at 1 200-1 400 ℃. A continuous AlN-layer was formed at the interface due to the reaction between NiAl and BN. At the same time, Cr diffused extensively into the BN-layer and reacted with boron to form Cr boride precipitates （CrsB3）. In addition, a few particles of Ta-rich phase were also precipitated in NiAl matrix near the interface.

Accelerating Oxygen Electrocatalysis Kinetics on Metal-Organic Frameworks via Bond Length Optimization

Metal-organic frameworks(MOFs)have been developed as an ideal platform for exploration of the relationship between intrinsic structure and catalytic activity,but the limited catalytic activity and stability has hampered their practical use in water splitting.Herein,we develop a bond length adjustment strategy for optimizing naphthalene-based MOFs that synthesized by acid etching Co-naphthalenedicarboxylic acid-based MOFs(donated as AE-CoNDA)to serve as efficient catalyst for water splitting.AE-CoNDA exhibits a low overpotential of 260 mV to reach 10 mA cm^(−2)and a small Tafel slope of 62 mV dec^(−1)with excellent stability over 100 h.After integrated AE-CoNDA onto BiVO_(4),photocurrent density of 4.3 mA cm^(−2)is achieved at 1.23 V.Experimental investigations demonstrate that the stretched Co-O bond length was found to optimize the orbitals hybridization of Co 3d and O 2p,which accounts for the fast kinetics and high activity.Theoretical calculations reveal that the stretched Co-O bond length strengthens the adsorption of oxygen-contained intermediates at the Co active sites for highly efficient water splitting.

The Role of Host-derived Dentinal Matrix Metalloproteinases in Reducing Dentin Bonding of Resin Adhesives

Dentin matrix metalloproteinases （MMPs） are a family of host-derived proteolytic enzymes trapped within mineralized dentin matrix, which have the ability to hydrolyze the organic matrix of demineralized dentin. After bonding with resins to dentin there are usually some exposed collagen fibrils at the bottom of the hybrid layer owing to imperfect resin impregnation of the demineralized dentin matrix. Exposed collagen fibrils might be affected by MMPs inducing hydrolytic degradation, which might result in reduced bond strength.Most MMPs are synthesized and released from odontoblasts in the form of proenzymes, requiring activation to degrade extracellular matrix components. Unfortunately, they can be activated by modem self-etch and etch-and-rinse adhe- sives. The aim of this review is to summarize the current knowledge of the role of dentinal host-derived MMPs in dentin matrix degradation. We also discuss various available MMP inhibitors, especially chlorhexidine, and suggest that they could provide a potential pathway for inhibiting collagen degradation in bonding interfaces thereby increasing dentin bonding durability.

法舒地尔缓解β-淀粉样蛋白1-42诱导的SH-SY5Y细胞凋亡

背景:法舒地尔对阿尔茨海默病小鼠脑内的线粒体动力学有调节作用,并且可以抑制神经炎症,但能否调节线粒体自噬和NLRP3炎症小体进而减轻β-淀粉样蛋白毒性尚不清楚。目的:探究法舒地尔对β-淀粉样蛋白1-42诱导的人源神经母细胞瘤细胞株SH-SY5Y凋亡和线粒体自噬以及NLRP3炎症小体的调节作用。方法:将SH-SY5Y细胞接种于孔板内,细胞贴壁后分3组干预:对照组不加入任何药物,模型组加入20μmol/L β-淀粉样蛋白1-42,法舒地尔组同时加入20μmol/L β-淀粉样蛋白1-42与15 mg/L法舒地尔,干预24 h后,采用MTT法检测细胞活性,TUNEL染色检测细胞凋亡,qRT-PCR和Western blot检测凋亡相关蛋白表达,免疫荧光染色和Western blot检测线粒体自噬相关蛋白表达,免疫荧光染色和Western blot检测NLRP3炎症小体相关蛋白表达。结果与结论:(1)与对照组比较,模型组细胞活性降低、凋亡率升高(P<0.05);与模型组比较,法舒地尔组细胞活性升高、凋亡率降低(P<0.05);(2)qRT-PCR和Western blot检测结果显示,与对照组比较,模型组细胞Bax mRNA与蛋白表达升高(P<0.05),Bcl-2 mRNA与蛋白表达降低(P<0.05);与模型组比较,法舒地尔组细胞Bax mRNA与蛋白表达降低(P<0.05),Bcl-2 mRNA与蛋白表达升高(P<0.05);(3)免疫荧光染色和Western blot检测结果显示,与对照组相比,模型组细胞PINK1、帕金森病蛋白和LC3蛋白表达降低(P<0.05),p62蛋白表达升高(P<0.05);与模型组相比,法舒地尔组细胞PINK1、帕金森病蛋白和LC3蛋白表达升高(P<0.05),p62蛋白表达降低(P<0.05);(4)免疫荧光染色和Western blot检测结果显示,与对照组相比,模型组细胞NLRP3、ASC、Caspase-1和白细胞介素1β蛋白表达升高(P<0.05);与模型组相比,法舒地尔组细胞NLRP3、ASC、Caspase-1和白细胞介素1β蛋白表达降低(P<0.05);(5)结果表明,法舒地尔可以减轻β-淀粉样蛋白1-42诱导的SH-SY5Y细胞凋亡,其机制可能与激活线粒体自噬且抑制NLRP3炎症小体激活有关。

Anti-proteolytic capacity and bonding durability of proanthocyanidin-biomodified demineralized dentin matrix

Our previous studies showed that biomodification of demineralized dentin collagen with proanthocyanidin（PA） for a clinically practical duration improves the mechanical properties of the dentin matrix and the immediate resin–dentin bond strength. The present study sought to evaluate the ability of PA biomodification to reduce collagenase-induced biodegradation of demineralized dentin matrix and dentin/adhesive interfaces in a clinically relevant manner. The effects of collagenolytic and gelatinolytic activity on PA-biomodified demineralized dentin matrix were analysed by hydroxyproline assay and gelatin zymography. Then, resin-/dentin-bonded specimens were prepared and challenged with bacterial collagenases. Dentin treated with 2% chlorhexidine and untreated dentin were used as a positive and negative control, respectively. Collagen biodegradation, the microtensile bond strengths of bonded specimens and the micromorphologies of the fractured interfaces were assessed. The results revealed that both collagenolytic and gelatinolytic activity on demineralized dentin were notably inhibited in the PA-biomodified groups, irrespective of PA concentration and biomodification duration. When challenged with exogenous collagenases, PA-biomodified bonded specimens exhibited significantly less biodegradation and maintained higher bond strengths than the untreated control. These results suggest that PA biomodification was effective at inhibiting proteolytic activity on demineralized dentin matrix and at stabilizing the adhesive/dentin interface against enzymatic degradation, is a new concept that has the potential to improve bonding durability.

Halogen Bonding or Hydrogen Bonding between 2,2,6,6-Tetramethyl- piperidine-noxyl Radical and Trihalomethanes CHX3 （X=CI, Br, I）

The halogen and hydrogen bonding complexes and trihalomethanes （CHX3, X=C1, Br, I） are between 2,2,6,6-tetramethylpiperidine-noxyl simulated by computational quantum chem- istry. The molecular electrostatic potentials, geometrical parameters and interaction energy of halogen and hydrogen bonding complexes combined with natural bond orbital analysis are obtained. The results indicate that both halogen and hydrogen bonding interactions obey the order CI〈Br〈I, and hydrogen bonding is stronger than the corresponding halogen bond- ing. So, hydrogen bonding complexes should be dominant in trihalomethanes. However, it is possible that halogen bonding complex is competitive, even preponderant, in triiodomethane due to the similar interaction energy. This work might provide useful information on specific solvent effects as well as for understanding the mechanism of nitroxide radicals as a bioprobe to interact with the halogenated compounds in biological and biochemical fields.