Lithiated Nafion-garnet ceramic composite electrolyte membrane for solid-state lithium metal battery

Single-ion conducting solid polymer electrolytes are expected to play a vital role in the realization of solid-state Li metal batteries.In this work,a lithiated Nafion(Li-Nafion)-garnet ceramic Li6.25La3 Zr2 Al0.25O12(LLZAO)composite solid electrolyte(CSE)membrane with 30μm thickness was prepared for the first time.By employing X-ray photoelectron spectroscopy and transmission electron microscope,the interaction between LLZAO and Li-Nafion was investigated.It is found that the LLZAO interacts with the Li-Nafion to form a space charge layer at the interface between LLZAO and Li-Nafion.The space charge layer reduces the migration barrier of Li-ions and improves the ionic conductivity of the CSE membrane.The CSE membrane containing 10 wt%LLZAO exhibits the highest ionic conductivity of2.26×10-4 S cm-1 at 30℃among the pristine Li-Nafion membrane,the membrane containing 5 wt%,20 wt%,and 30 wt%LLZAO,respectively.It also exhibits a high Li-ion transference number of 0.92,and a broader electrochemical window of 0-+4.8 V vs.Li+/Li than that of 0-+4.0 V vs.Li+/Li for the pristine Li-Nafion membrane.It is observed that the CSE membrane not only inhibits the growth of Li dendrites but also keeps excellent electrochemical stability with the Li electrode.Benefitting from the above merits,the solid-state LiFePO4/Li cell fabricated with the CSE membrane was practically charged and discharged at 30℃.The cell exhibits an initial reversible discharge specific capacity of 160 mAh g-1 with 97%capacity retention after 100 cycles at 0.2 C,and maintains discharge specific capacity of 126 mAh g-1 after500 cycles at 1 C.The CSE membrane prepared with Li-Nafion and LLZAO is proved to be a promising solid electrolyte for advanced solid-state Li metal batteries.

Vacuum brazing of Si/SiC ceramic composite and Invar alloy using TiSOCu-W filler metals

Si/SiC ceramic composite and lnvar alloy were successfidly joined by vacuum brazing using Ti5OCu-W filler metals into which W was added to release the thermal stress of the brazed joint. Microstructures of the brazed joints were irwestigated by scanning electron micrascope （SEM） and energy dispersive spectrometer （EDS）. The mechanical properties of the brazed joints were measured by shearing tests. The results showed that the brazed joints were composed of Ti-Cu phase, W phase and Ti-Si phase. W had no effect on the wettability and mobility of the .filler metals. The growth of Ti2 Cu phase was restrained, and the reaction between ceramic composite and filler metals was weakened. The specimen, brazed at 970°C for 5 rain, had the maximum shear strength of 108 MPa at room temperature.

Bonding of Silicon Nitride Ceramic Composite with RE_2O_3Al_2O_3SiO_2 Glass Solders

Liquid bonding of Si 3N 4 ceramic composite was carried out with RE 2O 3 Al 2O 3 SiO 2 glass solders. The effect of bonding conditions and interfacial reaction on the joint strength was studied. The joint strength under different bonding conditions was measured by four point bending tests. The interfacial microstructures were observed and analyzed by SEM, EPMA and XRD. It is shown that the liquid glass solders react with Si 3N 4 at interface, forming the Si 3N 4/Si 2N 2O/Y(La) sialon glass/Y(La) sialon glass gradient interface. With the increase of bonding temperature and holding time, the joint strength first increased reaching a peak, and then decreased. According to microanalyses, LaYO 3 precipitated from joint glass improves joint strength at room and high temperature.

Effect of Interfacial Bonding on the Toughening of Al_2O_3/Ni Ceramic Matrix Composites

The main Iimitation to the toughening of the α-Al2O3/Ni composite is the poor bonding atthe interface. which causes the nickel particles to be pulled-out during crack propagation with-out obvious plastic deformation. A proper control of oxygen content at the Al2O3-Ni interfacecan promote wetting at the intedece, and produce a mechanically interlocked and chemically strengthened intedece, causing most of the nickel particles to be stretched to failure and to expe-rience severe plastic deformation during crack propagation in the composite. Fracture toughnesstesting using a modified double cantilever beam method with in situ observation of crack prop-agation in a scanning electron microscope shows that the composite with the strengthenedinterface has a more desirable R-curve behaviour and a higher fracture toughness value than thenormal composite.

Coarse WC Particles Ceramic-Metal Composite Coating by Laser Cladding

The coarse WC particles ceramic-metal com- posite coatings with WC density of 67 wt-% and thickness of 1.0-1.2 mm have been cladded on 20Ni4Mo steel surface by a 2 kW CO_2 laser.The sintered WC particles with the size of 600-1000 μm are chosen as the main strengthening phase, Ni-base self-flux alloy as the binder in the compo- site coatings.The microstructure and microhardness of both WC particles and binder are analysed.The rigid ball indention with acoustic emission technique is used to evaluate the brittleness of the coating.Finally,the abrasive wear resistance of the coating is tested.Besides,the coatings with the same ratio and size of WC parti- cles in low carbon steel tube rod were cladded on 20Ni4Mo steel by atomic hydrogen welding tech- nique and analysed by the same way,their results are compared.

Identification of Growth Promoter to Fabrication SiCp/Al₂O₃Ceramic Matrix Composites Prepared by Directed Metal Oxidation of An Al Alloy

SiC particulates reinforced alumina matrix composites were fabricated using Directed Metal Oxidation (DIMOX) process. Continuous oxidation of an Al-Si-Mg-Zn alloy with different interlayers (dopents) as growth promoters, will encompasses the early heating of the alloy ingot, melting and continued heating to temperature in the narrow range of 950°C to 980°C in an atmosphere of oxygen. Varying interlayers (dopents) are incorporated to examine the growth conditions of the composite materials and to identification of suitable growth promoter. The process is extremely difficult because molten aluminum does not oxidize after prolonged duration at high temperatures due to the formation of a passivating oxide layer. It is known that the Lanxide Corporation had used a combination of dopents to cause the growth of alumina from molten metal. This growth was directed, i.e. the growth is allowed only in the required direction and restricted in the other directions. The react nature of the dopants was a trade secret. Though it is roughly known that Mg and Si in the Al melt can aid growth, additional dopents used, the temperatures at which the process was carried out, the experimental configurations that aided directed growth were not precisely known. In this paper we have evaluated the conditions in which composites can be grown in large enough sizes for evaluation application and have arrived at a procedure that enables the fabrication of large composite samples by determining the suitable growth promoter (dopant). Scanning electron microscopic, EDS analysis of the composite was found to contain a continuous network of Al2O3, which was predominantly free of grain-boundary phases, a continuous network of Al alloy. Fabrication of large enough samples was done only by the inventor company and the property measurements by the company were confirmed to those needed to enable immediate applications. Since there are a large number of variable affecting robust growth of the composite, fabrication large sized samples for measurements is a difficult task. In the present work, to identify a suitable window of parameters that enables robust growth of the composite has been attempted.

Metal-Ceramic Smart Composite in Ti(C,N)-Ni-Mo-W System

Goal: Low wolfram-containing cutting composite was obtained by fusion of titanium carbonitride and high melting temperature binding metallic phase. Method: The composite was obtained via compaction and further sintering in vacuum furnace at 1600°C under 10-3 Pa pressure. Phase analysis was performed on X-ray apparatus “DRON-3”;microstructure was determined by electron microscope NANOLAB-7, microhardness by MUCKE-mark microhardness meter;relative resistance of cutters was evaluated at similar modes of cutting according to distances they passed;experiments were carried out on turning lathe. Results: Physical-mechanical characteristics of the obtained composite are: σbend, = 1000 - 1150 MPa, σbend1000°C = 600 MPa, HV = 14 GPa;HV1000°C = 6.5 GPa. High speeds of cutting and high temperatures resistance of cutters made by the obtained composites exceeds 1.5 - 2-folds that of cutters made of the known BK8 and KNT20 hard alloys. Conclusion: Its application is recommended in hot steel treatment by cutting, for removal of the so-called burrs, as well as in steel treatment by cutting during pure and semi-pure operations. It can also be used in jet engines, chemical industry apparatuses, electric-vacuum devices, in industry of responsible details of rockets, nuclear reactors, flying apparatuses.

Processing of nanostructured metallic matrix composites by a modified accumulative roll bonding method with structural and mechanical considerations

Particulate reinforced metallic matrix composites have attracted considerable attention due to their lightweight, high strength, high specific modulus, and good wear resistance. A1/B4C composite strips were produced in this work by a modified accumulative roll bonding process where the strips were rotated 90° around the normal direction between successive passes. Transmission electron microscopy and X-ray diffraction analyses reveal the development of nanostructures in the Al matrix after seven passes. It is found that the B4C reinforcement distribution in the matrix is improved by progression of the process. Additionally, the tensile yield strength and elongation of the processed materials are increased with the increase of passes.

Features of microstructure and fracture in the transient liquid phase bonded aluminium-based metal matrix composite joints

Transient liquid phase (TLP) bonded aluminium based metal matrix composite (MMC) joints can be classified into three distinct regions, i.e. the particulate segregation region, the denuded particulate region and the base material region. The microstructure of the particulate segregation region consists of alumina particulate and Al alloy matrix with the Al 2Cu and MgAl 2O 4. It contains more and smaller alumina particulates compared with the base material region. The TLP bonded joints have the tensile strength of 150 MPa ～200 MPa and the shear strength of 70 MPa ～100 MPa . With increasing tensile stress, cracks initiate in the particulate segregation region, especially in the particulate/particulate interface and the particulate/matrix interface, and propagate along particulate/matrix interface, througth thin matrix metal and by linking up the close cracks. The particulate segregation region is the weakest during tensile testing and shear testing due to obviously increased proportion of weak bonds (particulate particulate bond and particulate matrix bond).

Transient liquid phase bonding of TiC particulate reinforced magnesium metal matrix composite (TiC_p/AZ91D)

Microstructures and mechanical properties of transient liquid phase （TLP） bonded magnesium metal matrix composite （ MMC） joints using copper interlayer have been investigated. With an increase of bonding times from 5 min to 50 min at bonding temperature of 510 ℃ , the average concentration of copper in the bonded zone decreased, the microstructure in the zone changed from Cu, α-Mg and CuMg2 to α-Mg, CuMg2 and TiC, and mechanical properties of the joint increased. The shear strength of the joint bonded at 510 ℃ for 50 min reached 64 MPa due to the metallurgical bonding of the joint and improving its homogeneity of composition and microstructure. It is favorable to increase the bonding time for improving mechanical properties of TLP bonded magnesium MMC joint.

FEM simulation on residual stress distribution during diffusion bonding between Ti （ C, N） metallic ceramic/interlayer/40Cr steel

Based on ANSYS FEM software, the distribution of residual stress in the diffusion bonding joints between Ti（ C,N） metallic ceramic/interlayer/4OCr steel was calculated and experimentally ver^ed. The results showed that the trend on the distribution of residual stress field in the joints was not changed with the use of interlayer. The maximum residual stress was always located in metallic ceramic with area ranging from 1 mm to 4 mm to the interlayer. The maximum residual stress in the joints was also affected by diffusion temperature. The satellite pulse current during the initial stage on diffusion bonding can promote the formation of liquid film at the interface, by which diffusion temperature and loading pressure can be greatly decreased. The crack initiation was easily produced at the corner of Ti （ C, N） metallic ceramic close to the interlayer. If a higher residual stress produced in the joints, the crack was propagated into the whole ceramic.

Metal-ceramic Bond Mechanism of the Co-Cr Alloy Denture with Original Rough Surface Produced by Selective Laser Melting

The porcelain fracture caused by low metal-ceramic bond strength is a critical issue in porcelain fused to metal（PFM） restorations. Surface roughening methods, such as sand blasting, acid etching and alkaline degreasing for the metal matrix are used to increase bond strength. However, the metal matrix of PFM processed by selective laser melting（SLM） has natural rough surface. To explore the effect of the original roughness on metal-ceramic bond strength, two groups of specimen are fabricated by SLM. One group of specimen surface is polished smooth while another group remains the original rough surface. The dental porcelain is fused to the specimens＇ surfaces according to the ISO 9693：1999 standard. To gain the bond strength, a three-point bending test is carried out and X ray energy spectrum analysis（EDS）, scanning electron microscope（SEM） are used to show fracture mode. The results show that the mean bond strength is 116.5 16 MPa of the group with rough surface（Ra= 17.2）, and the fracture mode is cohesive. However, when the surface is smooth （Ra =3.8）, the mean bond strength is 74.5 MPa _＋ 5 MPa and the fracture mode is mixed. The original surface with prominent structures formed by the partly melted powder particles, not only increases surface roughness but also significantly improves the bond strength by forming strong mechanical lock effect. Statistical analysis （Student＇s t-test） demonstrates a significant difference （p〈0.05） of the mean value of bond strength between the two groups. The experiments indicate the natural rough surface can enhance the metal-ceramic bond strength to over four times the minimum value （25 MPa） of the ISO 9693：1999 standard. It is found that the natural rough surface of SLM-made PFM can eliminate the porcelain collapse defect produced by traditional casting method in PFM restorations.

Formation process, microstructure and mechanical property of transient liquid phase bonded aluminium-based metal matrix composite joint

The formation process, microstructure and mechanical properties of transient liquid phase (TLP) bonded aluminium based metal matrix composite (MMC) joint with copper interlayer were investigated. The formation process of the TLP joint comprises a number of stages: plastic deformation and solid diffusion (stage 1), dissolution of interlayer and base metal (stage 2), isothermal solidification (stage 3) and homogenization (stage 4). The microstructure of the joint depends on the joint formation process (distinct stages). The plastic deformation and solid diffusion in stage 1 favoure the intimate contact at interfaces and liquid layer formation. The microstructure of joint consists of aluminium solid solution, alumina particle, Al 2Cu and MgAl 2O 4 compounds in stage 2. The most pronounced feature of joint microstructure in stage 3 is the alumina particle segregation in the center of the joint. The increase of joint shear strength with increasing bonding temperature is mainly attributed to improving the fluidity and wettability of liquid phase and decreasing the amount of Al 2Cu brittle phase in the joint. The principal reason of higher bonding temperature (>600 ℃) resulting in lowering obviously the joint shear strength is the widening of alumina particle segregation region that acts as a preferential site for failure. The increase of joint shear strength with increasing holding time is mainly associated with decreasing the amount of Al 2Cu brittle phase and promoting homogenization of joint.

Mechanical Behaviors of ZrO_2-Al_2O_3 Ceramic Composites with Y_2O_3 as Stabilizer

The ZrO2-Al2O3 ceramic composites were prepared by appropriate techniques with commercial ZrO2 and Al2O3 powders as raw materials and Y2O3 as stabilizer. The results indicate that with the introduction of Al2O3 into the ZrO2 matrix where the quantity of additive Y2O3 is 3.5% (mole fraction), the growth of ZrO2 grains is efficiently inhibited, which helps the ZrO2 grains exist in a metastable tetragonal manner; thus higher strength and toughness are acquired. When the content of alumina is 20% (mass fraction), the bending strength and fracture toughness of the composites are 676.7 MPa and 10 MPa·m1/2 respectively, the mechanical behaviors are close to those prepared with ZrO2 and Al2O3 powders synthesized through wet chemical approach. The mechanical behaviors of the composites are well improved owing to the dispersion toughening of alumina grains and phase transformation toughening of zirconia grains.

Joining mechanism of field-assisted diffusion bonding of solid electrolyte ceramic to metals

Field assisted diffusion bonding applied in the joining of solid electrolyte borosilicate glass, β ″ Al 2O 3, Y 2O ZrO 2 to monocrystal silicate and aluminum were proceeded with bonding machine in the assistance of static electric field. TEM, SEM, XRD and other means were applied to investigate and analyze microstructure of interface. It is supposed that the interfacial area is a model of metal oxides ceramic, and the joining mechanism is solid diffusion joining and static electric bonding. The process of ions migration and accumulation under electric field is the most essential factor for the anodic oxidation and interfacial joining. Temperature and voltage are the basic factors of the solid diffusion bonding of interfacial oxidation. And voltage, temperature, pressure and the condition of surface are the most important factors that govern the bonding process.

Development of Al-12Si-xTi system active ternary filler metals for Al metal matrix composites

To improve the wettability of Al metal matrix composites（Al-MMCs） by common filler metals,Al-12Si-xTi（x=0.1,0.5,1,3.0;mass fraction,%） system active ternary filler metals were prepared.It was demonstrated that although the added Ti existed within Ti（Al1-xSix）3（0≤x≤0.15） phase,the shear strength and shear fracture surface of the developed Al-12Si-xTi brazes were quite similar to those of traditional Al-12Si braze due to the presence of similar microstructure of Al-Si eutectic microstructure with large volume fraction.So,small Ti addition（～1%） did not make the active brazes brittle and hard compared with the conventional Al-12Si braze.The measured melting range of each Al-12Si-xTi foil was very similar,i.e.,580-590 ℃,because the composition was close to that of eutectic.For wettability improvement,with increasing Ti content,the interfacial gap between the Al2O3 reinforcement and filler metal（R/M） could be eliminated,and the amount of the remainder of the active fillers on the composite substrate decreased after sessile drop test at 610 ℃ for 30 min.So,the wettability improvement became easy to observe repeatedly with increasing Ti content.Additionally,the amount and size of Ti（AlSi）3 phase were sensitive to the Ti content（before brazing） and Si content（after brazing）.

3D core-shell nanofibers framework and functional ceramic nanoparticles synergistically reinforced composite polymer electrolytes for high-performance all-solid-state lithium metal battery

Satisfactory ionic conductivity,excellent mechanical stability,and high-temperature resistance are the prerequisites for the safe application of solid polymer electrolytes(SPEs)in all-solid-state lithium metal batteries(ASSLMBs).In this study,a novel poly(m-phenylene isophthalamide)(PMIA)-core/poly(ethylene oxide)(PEO)-shell nanofiber membrane and the functional Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZTO)ceramic nanopar-ticle are simultaneously introduced into the PEO-based SPEs to prepare composite polymer electrolytes(CPEs).The core PMIA layer of composite nanofibers can greatly improve the mechanical strength and thermal stability of the CPEs,while the shell PEO layer can provide the 3D continuous transport channels for lithium ions.In addition,the introduction of functional LLZTO nanoparticle not only reduces the crys-tallinity of PEO,but also promotes the dissociation of lithium salts and releases more Li^(+)ions through its interaction with the Lewis acid-base of anions,thereby overall improving the transport of lithium ions.Consequently,the optimized CPEs present high ionic conductivity of 1.38×10^(−4)S/cm at 30℃,signifi-cantly improved mechanical strength(8.5 MPa),remarkable thermal stability(without obvious shrinkage at 150℃),and conspicuous Li dendrites blocking ability(>1800 h).The CPEs also both have good com-patibility and cyclic stability with LiFePO_(4)(>2000 cycles)and high-voltage LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NMC811)(>500 cycles)cathodes.In addition,even at low temperature(40℃),the assembled LiFePO4/CPEs/Li bat-tery still can cycle stably.The novel design can provide an effective way to exploit high-performance solid-state electrolytes.

Selective interfacial bonding and thermal conductivity of diamond/Cu-alloy composites prepared by HPHT technique

Cu-based and Cu-alloy-based diamond composites were made by high-pressure-high-temperature （HPHT） sintering with the aim of maximizing the thermal conductivity of the composites. Improvements in interfacial bonding strength and thermo-physical properties of the composites were achieved using an atomized copper alloy with minor additions of Co, Cr, 13, and Ti. The thermal conductivity （TC） oh- mined exhibited as high as 688 W.m-1.K-1, but also as low as 325 W.m-1.K-l. A large variation in TC can be rationalized by the discrepancy of diamond-matrix interfacial bonding. It was found from fractography that preferential bonding between diamond and the Cu-alloy matrix occurred only on the diamond {100} faces. EDS analysis and Raman spectra suggested that selective interfacial bonding may be attributed to amorphous carbon increasing the wettability between diamond and the Cu-alloy matrix. Amorphous carbon was found to significantly affect the TC of the composite by interface modification.

Development of three kinds of active ternary filler metals of AI-Si-Ti, Zn-AI-Ti and Cu-AI-Ti systems for AI metal matrix composites

To improve the wettability of common fiUer metals on Al metal matrix composites （ AI-MMCs ） , three kinds of active ternary filler metals, Al-Si-Ti, Zn-Al-Ti and Cu-Al-Ti systems, were prepared by the addition of Ti. Excessive melting temperature made the gravity segregation of Ti remarkable in ingot. The effect of Ti content on the melting point for AI-Si-Ti ternary system was not as sensitive as that for Al-Ti binary system. The Al-12Si-1Ti filler metal showed good ability to form brazing foil during rapid cooling, ductile fracture surface and similar shear strength to conventional Al-12Si filler metal. Moreover, the Al2 03 reinforcements on initial surface could be covered by the Al-12Si-1Ti filler metal without interfacial gaps after sessile drop test. For Zn-9.5Al-0. 5 Ti braze alloy, severe vaporization of Zn and severe segregation of Ti Occurred. During wettability test for traditional Al-12Si and Zn-9.5Al-0. 5Ti, although some Si or Zn could penetrate into the composite, interfacial gap still remained. The prepared Cu-19Al-1 Ti interlayer consisted of primary phase of Al4Cu9 and network Cu-Al-Ti ternary intermetaUic compound, showing poor ability to form foil and very brittle nature. These results demonstrated that Al-Si-Ti system should be promising for Al-MMCs.

Properties of a reaction-bonded β-SiAlON ceramic doped with an FeMo alloy for application to molten aluminum environments

An FeMo-alloy-doped β-SiA1ON （FeMo/β-SiA1ON） composite was fabricated via a reaction-bonding method using raw materials of Si, Al2O3, A1N, FeMo, and Sm2O3. The effects of FeMo on the microstructure and mechanical properties of the composite were investi- gated. Some properties of the composite, including its bending strength at 700℃ and after oxidization at 700℃ for 24 h in air, thermal shock resistance and corrosion resistance to molten aluminum, were also evaluated. The results show that the density, toughness, bending strength, and thermal shock resistance of the composite are obviously improved with the addition of an FeMo alloy. In addition, other properties of the composite such as its high-temperature strength and oxidized strength are also improved by the addition of FeMo alloy, and its corrosion re- sistance to molten aluminum is maintained. These findings indicate that the developed FeMo/β-SiA1ON composite exhibits strong potential for application to molten aluminum environments.