Search results for: cu alloying
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 83

Search results for: cu alloying

23 Waste-Based Surface Modification to Enhance Corrosion Resistance of Aluminium Bronze Alloy

Authors: Wilson Handoko, Farshid Pahlevani, Isha Singla, Himanish Kumar, Veena Sahajwalla

Abstract:

Aluminium bronze alloys are well known for their superior abrasion, tensile strength and non-magnetic properties, due to the co-presence of iron (Fe) and aluminium (Al) as alloying elements and have been commonly used in many industrial applications. However, continuous exposure to the marine environment will accelerate the risk of a tendency to Al bronze alloys parts failures. Although a higher level of corrosion resistance properties can be achieved by modifying its elemental composition, it will come at a price through the complex manufacturing process and increases the risk of reducing the ductility of Al bronze alloy. In this research, the use of ironmaking slag and waste plastic as the input source for surface modification of Al bronze alloy was implemented. Microstructural analysis conducted using polarised light microscopy and scanning electron microscopy (SEM) that is equipped with energy dispersive spectroscopy (EDS). An electrochemical corrosion test was carried out through Tafel polarisation method and calculation of protection efficiency against the base-material was determined. Results have indicated that uniform modified surface which is as the result of selective diffusion process, has enhanced corrosion resistance properties up to 12.67%. This approach has opened a new opportunity to access various industrial utilisations in commercial scale through minimising the dependency on natural resources by transforming waste sources into the protective coating in environmentally friendly and cost-effective ways.

Keywords: aluminium bronze, waste-based surface modification, tafel polarisation, corrosion resistance

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22 Cold Spray High Entropy Alloy Coating Surface Microstructural Characterization and Mechanical Testing

Authors: Raffaella Sesana, Nazanin Sheibanian, Luca Corsaro, Sedat Özbilen, Rocco Lupoi, Francesco Artusio

Abstract:

High Entropy Alloy (HEA) coatings of Al0.1-0.5CoCrCuFeNi and MnCoCrCuFeNi on Mg substrates were prepared from mechanically alloyed HEA powder feedstocks and at three different Cold Spray (CS) process gas (N2) temperatures (650, 750 and 850°C). Mechanically alloyed and cold-sprayed HEA coatings were characterized by macro photography, OM, SEM+EDS study, micro-hardness testing, roughness, and porosity measurements. As a result of mechanical alloying (MA), harder particles are deformed and fractured. The particles in the Cu-rich region were coarser and more globular than those in the A1 phase, which is relatively soft and ductile. In addition to the A1 particles, there were some separate Cu-rich regions. Due to the brittle nature of the powder and the acicular shape, Mn-HEA powder exhibited a different trend with smaller particle sizes. It is observed that MA results in a loose structure characterized by many gaps, cracks, signs of plastic deformation, and small particles attached to the surface of the particle. Considering the experimental results obtained, it is not possible to conclude that the chemical composition of the high entropy alloy influences the roughness of the coating. It has been observed that the deposited volume increases with temperature only in the case of Al0.1 and Mg-based HEA, while for the rest of the Al-based HEA, there are no noticeable changes. There is a direct correlation between micro-hardness and the chemical composition of a coating: the micro-hardness of a coating increases as the percentage of aluminum increases in the sample. Compared to the substrate, the coating has a much higher hardness, and the hardness measured at the interface is intermediate.

Keywords: characterisation, cold spraying, HEA coatings, SEM+EDS

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21 Study on Hydrogen Isotope Permeability of High Entropy Alloy Coating

Authors: Long Wang, Yongjin Feng, Xiaofang Luo

Abstract:

Tritium permeation through structural materials is a significant issue for fusion demonstration (DEMO) reactor blankets in terms of fuel cycle efficiency and radiological safety. Reduced activation ferritic (RAFM) steel CLF-1 is a prime candidate for the China’s CFETR blanket structural material, facing high permeability of hydrogen isotopes at reactor operational temperature. To confine tritium as much as possible in the reactor, surface modification of the steels including fabrication of tritium permeation barrier (TPB) attracts much attention. As a new alloy system, high entropy alloy (HEA) contains at least five principal elements, each of which ranges from 5 at% to 35 at%. This high mixing effect entitles HEA extraordinary comprehensive performance. So it is attractive to lead HEA into surface alloying for protective use. At present, studies on the hydrogen isotope permeability of HEA coatings is still insufficient and corresponding mechanism isn’t clear. In our study, we prepared three kinds of HEA coatings, including AlCrTaTiZr, (AlCrTaTiZr)N and (AlCrTaTiZr)O. After comprehensive characterization of SEM, XPS, AFM, XRD and TEM, the structure and composition of the HEA coatings were obtained. Deuterium permeation tests were conducted to evaluate the hydrogen isotope permeability of AlCrTaTiZr, (AlCrTaTiZr)N and (AlCrTaTiZr)O HEA coatings. Results proved that the (AlCrTaTiZr)N and (AlCrTaTiZr)O HEA coatings had better hydrogen isotope permeation resistance. Through analyzing and characterizing the hydrogen isotope permeation results of the corroded samples, an internal link between hydrogen isotope permeation behavior and structure of HEA coatings was established. The results provide valuable reference in engineering design of structural and TPB materials for future fusion device.

Keywords: high entropy alloy, hydrogen isotope permeability, tritium permeation barrier, fusion demonstration reactor

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20 Microstructure, Mechanical, Electrical and Thermal Properties of the Al-Si-Ni Ternary Alloy

Authors: Aynur Aker, Hasan Kaya

Abstract:

In recent years, the use of the aluminum based alloys in the industry and technology are increasing. Alloying elements in aluminum have further been improving the strength and stiffness properties that provide superior compared to other metals. In this study, investigation of physical properties (microstructure, microhardness, tensile strength, electrical conductivity and thermal properties) in the Al-12.6wt.%Si-%2wt.Ni ternary alloy were investigated. Al-Si-Ni alloy was prepared in a graphite crucible under vacuum atmosphere. The samples were directionally solidified upwards with different growth rate (V) at constant temperature gradient G (7.73 K/mm). The microstructures (flake spacings, λ), microhardness (HV), ultimate tensile strength, electrical resistivity and thermal properties enthalpy of fusion and specific heat and melting temperature) of the samples were measured. Influence of the growth rate and flake spacings on microhardness, ultimate tensile strength and electrical resistivity were investigated and relationships between them were experimentally obtained by using regression analysis. According to results, λ values decrease with increasing V, but microhardness, ultimate tensile strength, electrical resistivity values increase with increasing V. Variations of electrical resistivity for cast samples with the temperature in the range of 300-1200 K were also measured by using a standard dc four-point probe technique. The enthalpy of fusion and specific heat for the same alloy was also determined by means of differential scanning calorimeter (DSC) from heating trace during the transformation from liquid to solid. The results obtained in this work were compared with the previous similar experimental results obtained for binary and ternary alloys.

Keywords: electrical resistivity, enthalpy, microhardness, solidification, tensile stress

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19 Forgeability Study of Medium Carbon Micro-Alloyed Forging Steel

Authors: M. I. Equbal, R. K. Ohdar, B. Singh, P. Talukdar

Abstract:

Micro-alloyed steel components are used in automotive industry for the necessity to make the manufacturing process cycles shorter when compared to conventional steel by eliminating heat treatment cycles, so an important saving of costs and energy can be reached by reducing the number of operations. Micro-alloying elements like vanadium, niobium or titanium have been added to medium carbon steels to achieve grain refinement with or without precipitation strengthening along with uniform microstructure throughout the matrix. Present study reports the applicability of medium carbon vanadium micro-alloyed steel in hot forging. Forgeability has been determined with respect to different cooling rates, after forging in a hydraulic press at 50% diameter reduction in temperature range of 900-11000C. Final microstructures, hardness, tensile strength, and impact strength have been evaluated. The friction coefficients of different lubricating conditions, viz., graphite in hydraulic oil, graphite in furnace oil, DF 150 (Graphite, Water-Based) die lubricant and dry or without any lubrication were obtained from the ring compression test for the above micro-alloyed steel. Results of ring compression tests indicate that graphite in hydraulic oil lubricant is preferred for free forging and dry lubricant is preferred for die forging operation. Exceptionally good forgeability and high resistance to fracture, especially for faster cooling rate has been observed for fine equiaxed ferrite-pearlite grains, some amount of bainite and fine precipitates of vanadium carbides and carbonitrides. The results indicated that the cooling rate has a remarkable effect on the microstructure and mechanical properties at room temperature.

Keywords: cooling rate, hot forging, micro-alloyed, ring compression

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18 Effect of Flux Salts on the Recovery Extent and Quality of Metal Values from Spent Rechargeable Lead Batteries

Authors: Mahmoud A Rabah, Sabah M. Abelbasir

Abstract:

Lead-calcium alloy containing up to 0.10% calcium was recovered from spent rechargeable sealed acid lead batteries. Two techniques were investigated to explore the effect of flux salts on the extent and quality of the recovered alloy, pyro-metallurgical and electrochemical methods. About 10 kg of the spent batteries were collected for testing. The sample was washed with hot water and dried. The plastic cases of the batteries were mechanically cut, and the contents were dismantled manually, the plastic containers were shredded for recycling. The electrode plates were freed from the loose powder and placed in SiC crucible and covered with alkali chloride salts. The loaded crucible was heated in an electronically controlled chamber furnace type Nabertherm C3 at temperatures up to 800 °C. The obtained metals were analyzed. The effect of temperature, rate of heating, atmospheric conditions, composition of the flux salts on the extent and quality of the recovered products were studied. Results revealed that the spent rechargeable batteries contain 6 blocks of 6 plates of Pb-Ca alloy each. Direct heating of these plates in a silicon carbide crucible under ambient conditions produces lead metal poor in calcium content ( < 0.07%) due to partial oxidation of the alloying calcium element. Rate of temperature increase has a considerable effect on the yield of the lead alloy extraction. Flux salts composition benefits the recovery process. Sodium salts are more powerful as compared to potassium salts. Lead calcium alloy meeting the standard specification was successfully recovered from the spent rechargeable acid lead batteries with a very competitive cost to the same alloy prepared from primary resources.

Keywords: rechargeable lead batteries, lead-calcium alloy, waste recovery, flux salts, thermal recovery

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17 Effect of Microstructure and Texture of Magnesium Alloy Due to Addition of Pb

Authors: Yebeen Ji, Jimin Yun, Kwonhoo Kim

Abstract:

Magnesium alloys were limited for industrial applications due to having a limited slip system and high plastic anisotropy. It has been known that specific textures were formed during processing (rolling, etc.), and These textures cause poor formability. To solve these problems, many researchers have studied controlling texture by adding rare-earth elements. However, the high cost limits their use; therefore, alternatives are needed to replace them. Although Pb addition doesn’t directly improve magnesium properties, it has been known to suppress the diffusion of other alloying elements and reduce grain boundary energy. These characteristics are similar to the additions of rare-earth elements, and a similar texture behavior is expected as well. However, there is insufficient research on this. Therefore, this study investigates the behavior of texture and microstructure development after adding Pb to magnesium. This study compared and analyzed AZ61 alloy and Mg-15wt%Pb alloy to determine the effect of adding solute elements. The alloy was hot rolled and annealed to form a single phase and initial texture. Afterward, the specimen was set to contraction and elongate parallel to the rolling surface and the rolling direction and then subjected to high-temperature plane strain compression under the conditions of 723K and 0.05/s. Microstructural analysis and texture measurements were performed by SEM-EBSD. The peak stress in the true strain-stress curve after compression was higher in AZ61, but the shape of the flow curve was similar for both alloys. For both alloys, continuous dynamic recrystallization was confirmed to occur during the compression process. The basal texture developed parallel to the compressed surface, and the pole density was lower in the Mg-15wt%Pb alloy. It is confirmed that this change in behavior is because the orientation distribution of recrystallized grains has a more random orientation compared to the parent grains when Pb is added.

Keywords: Mg, texture, Pb, DRX

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16 Processing and Characterization of Aluminum Matrix Composite Reinforced with Amorphous Zr₃₇.₅Cu₁₈.₆₇Al₄₃.₉₈ Phase

Authors: P. Abachi, S. Karami, K. Purazrang

Abstract:

The amorphous reinforcements (metallic glasses) can be considered as promising options for reinforcing light-weight aluminum and its alloys. By using the proper type of reinforcement, one can overcome to drawbacks such as interfacial de-cohesion and undesirable reactions which can be created at ceramic particle and metallic matrix interface. In this work, the Zr-based amorphous phase was produced via mechanical milling of elemental powders. Based on Miedema semi-empirical Model and diagrams for formation enthalpies and/or Gibbs free energies of Zr-Cu amorphous phase in comparison with the crystalline phase, the glass formability range was predicted. The composite was produced using the powder mixture of the aluminum and metallic glass and spark plasma sintering (SPS) at the temperature slightly above the glass transition Tg of the metallic glass particles. The selected temperature and rapid sintering route were suitable for consolidation of an aluminum matrix without crystallization of amorphous phase. To characterize amorphous phase formation, X-ray diffraction (XRD) phase analyses were performed on powder mixture after specified intervals of milling. The microstructure of the composite was studied by optical and scanning electron microscope (SEM). Uniaxial compression tests were carried out on composite specimens with the dimension of 4 mm long and a cross-section of 2 ˟ 2mm2. The micrographs indicated an appropriate reinforcement distribution in the metallic matrix. The comparison of stress–strain curves of the consolidated composite and the non-reinforced Al matrix alloy in compression showed that the enhancement of yield strength and mechanical strength are combined with an appreciable plastic strain at fracture. It can be concluded that metallic glasses (amorphous phases) are alternative reinforcement material for lightweight metal matrix composites capable of producing high strength and adequate ductility. However, this is in the expense of minor density increase.

Keywords: aluminum matrix composite, amorphous phase, mechanical alloying, spark plasma sintering

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15 Ni-W-P Alloy Coating as an Alternate to Electroplated Hard Cr Coating

Authors: S. K. Ghosh, C. Srivastava, P. K. Limaye, V. Kain

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Electroplated hard chromium is widely known in coatings and surface finishing, automobile and aerospace industries because of its excellent hardness, wear resistance and corrosion properties. However, its precursor, Cr+6 is highly carcinogenic in nature and a consensus has been adopted internationally to eradicate this coating technology with an alternative one. The search for alternate coatings to electroplated hard chrome is continuing worldwide. Various alloys and nanocomposites like Co-W alloys, Ni-Graphene, Ni-diamond nanocomposites etc. have already shown promising results in this regard. Basically, in this study, electroless Ni-P alloys with excellent corrosion resistance was taken as the base matrix and incorporation of tungsten as third alloying element was considered to improve the hardness and wear resistance of the resultant alloy coating. The present work is focused on the preparation of Ni–W–P coatings by electrodeposition with different content of phosphorous and its effect on the electrochemical, mechanical and tribological performances. The results were also compared with Ni-W alloys. Composition analysis by EDS showed deposition of Ni-32.85 wt% W-3.84 wt% P (designated as Ni-W-LP) and Ni-18.55 wt% W-8.73 wt% P (designated as Ni-W-HP) alloy coatings from electrolytes containing of 0.006 and 0.01M sodium hypophosphite respectively. Inhibition of tungsten deposition in the presence of phosphorous was noted. SEM investigation showed cauliflower like growth along with few microcracks. The as-deposited Ni-W-P alloy coating was amorphous in nature as confirmed by XRD investigation and step-wise crystallization was noticed upon annealing at higher temperatures. For all the coatings, the nanohardness was found to increase after heat-treatment and typical nanonahardness values obtained for 400°C annealed samples were 18.65±0.20 GPa, 20.03±0.25 GPa, and 19.17±0.25 for alloy coatings Ni-W, Ni-W-LP and Ni-W-HP respectively. Therefore, the nanohardness data show very promising results. Wear and coefficient of friction data were recorded by applying a different normal load in reciprocating motion using a ball on plate geometry. Post experiment, the wear mechanism was established by detail investigation of wear-scar morphology. Potentiodynamic measurements showed coating with a high content of phosphorous was most corrosion resistant in 3.5wt% NaCl solution.

Keywords: corrosion, electrodeposition, nanohardness, Ni-W-P alloy coating

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14 Properties of Magnesium-Based Hydrogen Storage Alloy Added with Palladium and Titanium Hydride

Authors: Jun Ying Lin, Tzu Hsiang Yen, Cha'o Kuang Chen

Abstract:

Nowadays, the great majority believe that there is great potentiality in hydrogen storage alloy storing hydrogen by physical and chemical absorption. However, the hydrogen storage alloy is limited by high operation temperature. Scientists find that adding transition elements can improve the properties of hydrogen storage alloy. In this research, outstanding improvements of kinetic and thermal properties are given by the addition of Palladium and Titanium hydride to Magnesium-based hydrogen storage alloy. Magnesium-based alloy is the main material, into which TiH2 / Pd are added separately. Following that, materials are milled by a Planetary Ball Miller at 650 rpm. TGA/DSC and PCT measure the capacity, spending time and temperature of abs/des-orption. Additionally, SEM and XRD analyze the structures and components of material. It is clearly shown that Pd is beneficial to kinetic properties. 2MgH2-0.1Pd has the highest capacity of all the alloys listed, approximately 5.5 wt%. Secondly, there are not any new Ti-related compounds found from XRD analysis. Thus, TiH2, considered as the catalyst, leads to the condition of 2MgH2-TiH2 and 2MgH2-TiH2-0.1Pd efficiently absorbing hydrogen in low temperature. 2MgH2-TiH2 can reach roughly 3.0 wt% in 82.4 minutes at 50°C and 8 minutes at 100°C, while2MgH2-TiH2-0.1Pd can reach 2.0 wt% in 400 minutes at 50°C and in 48 minutes at 100°C. The lowest temperature of 2MgH2-0.1Pd and 2MgH2-TiH2 is similar (320°C), otherwise the lowest temperature of 2MgH2-TiH2-0.1Pd decrease by 20°C. From XRD, it can be observed that PdTi2 and Pd3Ti are produced by mechanical alloying when adding Pd as well as TiH2 into MgH2. Due to the synergistic effects between Pd and TiH2, 2MgH2-TiH2-0.1Pd owns the lowest dehydrogenation temperature. Furthermore, the Pressure-Composition-Temperature (PCT) curve of 2MgH2-TiH2-0.1Pd is measured at different temperature, 370°C, 350°C, 320°C and 300°C separately. The plateau pressure is given form the PCT curves above. In accordance to different plateau pressures, enthalpy and entropy in the Van’t Hoff equation can be solved. In 2MgH2-TiH2-0.1Pd, the enthalpy is 74.9 KJ/mol and the entropy is 122.9 J/mol. Activation means that hydrogen storage alloy undergoes repeat abs/des-orpting processes. It plays an important role in the abs/des-orption. Activation shortens the abs/des-orption time because of the increase in surface area. From SEM, it is clear that the grain size and surface become smaller and rougher

Keywords: hydrogen storage materials, magnesium hydride, abs-/des-orption performance, Plateau pressure

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13 Study on Pd Catalyst Supported on Carbon Materials for C₂ Hydrogenation

Authors: Huanru Wang, Jianzhun Jiang

Abstract:

At present, the preparation of the catalyst by carbon carrier is one of the improvement directions of the C₂ pre-hydrogenation catalyst. Carbon materials can be prepared from coal direct liquefaction residues, coconut shells, biomass, etc., and the pore structure of carbon carrier materials can be adjusted through the preparation process; at high temperatures, the carbon carrier itself also shows certain catalytic activity. Therefore, this paper mainly selected typical activated carbon and coconut shell carbon as carbon carrier materials, studied their microstructure and surface properties, prepared a series of carbon-based catalysts loaded with Pd, and investigated the effects of the content of promoter Ag and the concentration of reductant on the structure and performance of the catalyst and its catalytic performance for the pre hydrogenation of C₂. In this paper, the carbon supports from two sources and the catalysts prepared by them were characterized in detail. The results showed that the morphology and structure of different supports and the performance of the catalysts prepared were also obviously different. The catalyst supported on coconut shell carbon has a small specific surface area and large pore diameter. The catalyst supported on activated carbon has a large specific surface area and rich pore structure. The active carbon support is mainly a mixture of amorphous graphite and microcrystalline graphite. For the catalyst prepared with coconut shell carbon as the carrier, the sample is very uneven, and its specific surface area and pore volume are irregular. Compared with coconut shell carbon, activated carbon is more suitable as the carrier of the C₂ hydrogenation catalyst. The conversion of acetylene, methyl acetylene, and butadiene decreased, and the ethylene selectivity increased after Ag was added to the supported Pd catalyst. When the amount of promoter Ag is 0.01-0.015%, the catalyst has relatively good catalytic performance. Ag and Pd form an alloying effect, thus reducing the effective demand for Ag. The Pd Ag ratio is the key factor affecting the catalytic performance. When the addition amount of Ag is 0.01-0.015%, the dispersion of Pd on the carbon support surface can be significantly improved, and the size of active particles can be reduced. The Pd Ag ratio is the main factor in improving the selectivity of the catalyst. When the additional amount of sodium formate is 1%, the catalyst prepared has both high acetylene conversion and high ethylene selectivity.

Keywords: C₂ hydrogenation, activated carbon, Ag promoter, Pd catalysts

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12 Direct Laser Fabrication and Characterization of Cu-Al-Ni Shape Memory Alloy for Seismic Damping Applications

Authors: Gonzalo Reyes, Magdalena Walczak, Esteban Ramos-Moore, Jorge Ramos-Grez

Abstract:

Metal additive manufacture technologies have gained strong support and acceptance as a promising and alternative method to manufacture high performance complex geometry products. The main purpose of the present work is to study the microstructure and phase transformation temperatures of Cu-Al-Ni shape memory alloys fabricated from a direct laser additive process using metallic powders as precursors. The potential application is to manufacture self-centering seismic dampers for earthquake protection of buildings out of a copper based alloy by an additive process. In this process, the Cu-Al-Ni alloy is melted, inside of a high temperature and vacuum chamber with the aid of a high power fiber laser under inert atmosphere. The laser provides the energy to melt the alloy powder layer. The process allows fabricating fully dense, oxygen-free Cu-Al-Ni specimens using different laser power levels, laser powder interaction times, furnace ambient temperatures, and cooling rates as well as modifying concentration of the alloying elements. Two sets of specimens were fabricated with a nominal composition of Cu-13Al-3Ni and Cu-13Al-4Ni in wt.%, however, semi-quantitative chemical analysis using EDX examination showed that the specimens’ resulting composition was closer to Cu-12Al-5Ni and Cu-11Al-8Ni, respectively. In spite of that fact, it is expected that the specimens should still possess shape memory behavior. To confirm this hypothesis, phase transformation temperatures will be measured using DSC technique, to look for martensitic and austenitic phase transformations at 150°C. So far, metallographic analysis of the specimens showed defined martensitic microstructures. Moreover, XRD technique revealed diffraction peaks corresponding to (0 0 18) and (1 2 8) planes, which are too associated with the presence of martensitic phase. We conclude that it would be possible to obtain fully dense Cu-Al-Ni alloys having shape memory effect behavior by direct laser fabrication process, and to advance into fabrication of self centering seismic dampers by a controllable metal additive manufacturing process.

Keywords: Cu-Al-Ni alloys, direct laser fabrication, shape memory alloy, self-centering seismic dampers

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11 Advanced Compound Coating for Delaying Corrosion of Fast-Dissolving Alloy in High Temperature and Corrosive Environment

Authors: Lei Zhao, Yi Song, Tim Dunne, Jiaxiang (Jason) Ren, Wenhan Yue, Lei Yang, Li Wen, Yu Liu

Abstract:

Fasting dissolving magnesium (DM) alloy technology has contributed significantly to the “Shale Revolution” in oil and gas industry. This application requires DM downhole tools dissolving initially at a slow rate, rapidly accelerating to a high rate after certain period of operation time (typically 8 h to 2 days), a contradicting requirement that can hardly be addressed by traditional Mg alloying or processing itself. Premature disintegration has been broadly reported in downhole DM tool from field trials. To address this issue, “temporary” thin polymers of various formulations are currently coated onto DM surface to delay its initial dissolving. Due to conveying parts, harsh downhole condition, and high dissolving rate of the base material, the current delay coatings relying on pure polymers are found to perform well only at low temperature (typical < 100 ℃) and parts without sharp edges or corners, as severe geometries prevent high quality thin film coatings from forming effectively. In this study, a coating technology combining Plasma Electrolytic Oxide (PEO) coatings with advanced thin film deposition has been developed, which can delay DM complex parts (with sharp corners) in corrosive fluid at 150 ℃ for over 2 days. Synergistic effects between porous hard PEO coating and chemical inert elastic-polymer sealing leads to its delaying dissolution improvement, and strong chemical/physical bonding between these two layers has been found to play essential role. Microstructure of this advanced coating and compatibility between PEO and various polymer selections has been thoroughly investigated and a model is also proposed to explain its delaying performance. This study could not only benefit oil and gas industry to unplug their High Temperature High Pressure (HTHP) unconventional resources inaccessible before, but also potentially provides a technical route for other industries (e.g., bio-medical, automobile, aerospace) where primer anti-corrosive protection on light Mg alloy is highly demanded.

Keywords: dissolvable magnesium, coating, plasma electrolytic oxide, sealer

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10 Corrosion Behavior of Organic-Inorganic Hybrid Coatings Fabricated by Electrostatic Method

Authors: Mohammed Ahmed, Ziba Nazarlou

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Mild steels have a limited alloying content which makes them vulnerable to excessive corrosion rates in the harsh medium. To overcome this issue, some protective coatings are used to prevent corrosion on the steel surface. The use of specialized coatings, mainly organic coatings (such as epoxies, polyurethanes, and acrylics) and inorganic coatings (such as Polysiloxanes) is the most common method of mitigating corrosion of carbon steel. Incorporating the benefits of organic and inorganic hybrid (OIH) compounds for the designing of hybrid protective coatings is still challenging for industrial applications. There are advantages of inorganic coatings have, but purely inorganic siloxane-based coatings are difficult to use on industrial applications unless they are used at extremely low thicknesses (< 1-2 microns). Hence, most industrial applications try to have a combination of Polysiloxanes with organic compounds.  A hybrid coating possesses an organic section, which transports flexibility and impact resistance, and an inorganic section, which usually helps in the decreasing of porosity and increasing thermal stability and hardness. A number of polymers including polyethylene glycol and polyvinyl pyrrolidone have been reported to inhibit the corrosion mild steel in acidic media. However, reports on the effect of polyethylene oxide (PEO) or its blends on corrosion inhibition of metals is very scarce. Different composition of OIH coatings was synthesized by using silica sol-gel, epoxy, and PEO. The effect of different coating types on the corrosion behavior of carbon steel in harsh solution has been studied by weight loss and electrochemical measurements using Gamry 1000 Interface Potentiostat. Coating structures were investigated by SEM. İt revealed a considerable reduction in corrosion rate for coated sample. Based on these results, OIH coating prepared by epoxy-silica sol gel-PEO and epoxy-silica sol-gel exhibit had a %99.5 and %98 reduction of (Corrosion rate) CR compares to baseline. Cathodic Tafel constant (βc) shows that coatings change both Tafel constants but had more effect on the cathodic process. The evolution of the Potentiostatic scan with time displays stability in potential, some of them in a high value while the other in a low value which can be attributed to the formation of an oxide film covering substrate surface. The coated samples with the group of epoxy coating have a lower potential along with the time test, while the silica group shows higher in potential with respect to time.

Keywords: electrostatic, hybrid coating, corrosion tests, silica sol gel

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9 Enhancement of Fracture Toughness for Low-Temperature Applications in Mild Steel Weldments

Authors: Manjinder Singh, Jasvinder Singh

Abstract:

Existing theories of Titanic/Liberty ship, Sydney bridge accidents and practical experience generated an interest in developing weldments those has high toughness under sub-zero temperature conditions. The purpose was to protect the joint from undergoing DBT (Ductile to brittle transition), when ambient temperature reach sub-zero levels. Metallurgical improvement such as low carbonization or addition of deoxidization elements like Mn and Si was effective to prevent fracture in weldments (crack) at low temperature. In the present research, an attempt has been made to investigate the reason behind ductile to brittle transition of mild steel weldments when subjected to sub-zero temperatures and method of its mitigation. Nickel is added to weldments using manual metal arc welding (MMAW) preventing the DBT, but progressive reduction in charpy impact values as temperature is lowered. The variation in toughness with respect to nickel content being added to the weld pool is analyzed quantitatively to evaluate the rise in toughness value with increasing nickel amount. The impact performance of welded specimens was evaluated by Charpy V-notch impact tests at various temperatures (20 °C, 0 °C, -20 °C, -40 °C, -60 °C). Notch is made in the weldments, as notch sensitive failure is particularly likely to occur at zones of high stress concentration caused by a notch. Then the effect of nickel to weldments is investigated at various temperatures was studied by mechanical and metallurgical tests. It was noted that a large gain in impact toughness could be achieved by adding nickel content. The highest yield strength (462J) in combination with good impact toughness (over 220J at – 60 °C) was achieved with an alloying content of 16 wt. %nickel. Based on metallurgical behavior it was concluded that the weld metals solidify as austenite with increase in nickel. The microstructure was characterized using optical and high resolution SEM (scanning electron microscopy). At inter-dendritic regions mainly martensite was found. In dendrite core regions of the low carbon weld metals a mixture of upper bainite, lower bainite and a novel constituent coalesced bainite formed. Coalesced bainite was characterized by large bainitic ferrite grains with cementite precipitates and is believed to form when the bainite and martensite start temperatures are close to each other. Mechanical properties could be rationalized in terms of micro structural constituents as a function of nickel content.

Keywords: MMAW, Toughness, DBT, Notch, SEM, Coalesced bainite

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8 Modeling of in 738 LC Alloy Mechanical Properties Based on Microstructural Evolution Simulations for Different Heat Treatment Conditions

Authors: M. Tarik Boyraz, M. Bilge Imer

Abstract:

Conventionally cast nickel-based super alloys, such as commercial alloy IN 738 LC, are widely used in manufacturing of industrial gas turbine blades. With carefully designed microstructure and the existence of alloying elements, the blades show improved mechanical properties at high operating temperatures and corrosive environment. The aim of this work is to model and estimate these mechanical properties of IN 738 LC alloy solely based on simulations for projected heat treatment conditions or service conditions. The microstructure (size, fraction and frequency of gamma prime- γ′ and carbide phases in gamma- γ matrix, and grain size) of IN 738 LC needs to be optimized to improve the high temperature mechanical properties by heat treatment process. This process can be performed at different soaking temperature, time and cooling rates. In this work, micro-structural evolution studies were performed experimentally at various heat treatment process conditions, and these findings were used as input for further simulation studies. The operation time, soaking temperature and cooling rate provided by experimental heat treatment procedures were used as micro-structural simulation input. The results of this simulation were compared with the size, fraction and frequency of γ′ and carbide phases, and grain size provided by SEM (EDS module and mapping), EPMA (WDS module) and optical microscope for before and after heat treatment. After iterative comparison of experimental findings and simulations, an offset was determined to fit the real time and theoretical findings. Thereby, it was possible to estimate the final micro-structure without any necessity to carry out the heat treatment experiment. The output of this microstructure simulation based on heat treatment was used as input to estimate yield stress and creep properties. Yield stress was calculated mainly as a function of precipitation, solid solution and grain boundary strengthening contributors in microstructure. Creep rate was calculated as a function of stress, temperature and microstructural factors such as dislocation density, precipitate size, inter-particle spacing of precipitates. The estimated yield stress values were compared with the corresponding experimental hardness and tensile test values. The ability to determine best heat treatment conditions that achieve the desired microstructural and mechanical properties were developed for IN 738 LC based completely on simulations.

Keywords: heat treatment, IN738LC, simulations, super-alloys

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7 Investigation Studies of WNbMoVTa and WNbMoVTaCr₀.₅Al Refractory High Entropy Alloys as Plasma-Facing Materials

Authors: Burçak Boztemur, Yue Xu, Laima Luo, M. Lütfi Öveçoğlu, Duygu Ağaoğulları

Abstract:

Tungsten (W) is used chiefly as plasma-facing material. However, it has some problems, such as brittleness after plasma exposure. High-entropy alloys (RHEAs) are a new opportunity for this deficiency. So, the neutron shielding behavior of WNbMoVTa and WNbMoVTaCr₀.₅Al compositions were examined against He⁺ irradiation in this study. The mechanical and irradiation properties of the WNbMoVTa base composition were investigated by adding the Al and Cr elements. The mechanical alloying (MA) for 6 hours was applied to obtain RHEA powders. According to the X-ray diffraction (XRD) method, the body-centered cubic (BCC) phase and NbTa phase with a small amount of WC impurity that comes from vials and balls were determined after 6 h MA. Also, RHEA powders were consolidated with the spark plasma sintering (SPS) method (1500 ºC, 30 MPa, and 10 min). After the SPS method, (Nb,Ta)C and W₂C₀.₈₅ phases were obtained with the decomposition of WC and stearic acid that is added during MA based on XRD results. Also, the BCC phase was obtained for both samples. While the Al₂O₃ phase with a small intensity was seen for the WNbMoVTaCr₀.₅Al sample, the Ta₂VO₆ phase was determined for the base sample. These phases were observed as three different regions according to scanning electron microscopy (SEM). All elements were distributed homogeneously on the white region by measuring an electron probe micro-analyzer (EPMA) coupled with a wavelength dispersive spectroscope (WDS). Also, the grey region of the WNbMoVTa sample was rich in Ta, V, and O elements. However, the amount of Al and O elements was higher for the grey region of the WNbMoVTaCr₀.₅Al sample. The high amount of Nb, Ta, and C elements were determined for both samples. Archimedes’ densities that were measured with alcohol media were closer to the theoretical densities of RHEAs. These values were important for the microhardness and irradiation resistance of compositions. While the Vickers microhardness value of the WNbMoVTa sample was measured as ~11 GPa, this value increased to nearly 13 GPa with the WNbMoVTaCr₀.₅Al sample. These values were compatible with the wear behavior. The wear volume loss was decreased to 0.16×10⁻⁴ from 1.25×10⁻⁴ mm³ by the addition of Al and Cr elements to the WNbMoVTa. The He⁺ irradiation was conducted on the samples to observe surface damage. After irradiation, the XRD patterns were shifted to the left because of defects and dislocations. He⁺ ions were infused under the surface, so they created the lattice expansion. The peak shifting of the WNbMoVTaCr₀.₅Al sample was less than the WNbMoVTa base sample, thanks to less impact. A small amount of fuzz was observed for the base sample. This structure was removed and transformed into a wavy structure with the addition of Cr and Al elements. Also, the deformation hardening was actualized after irradiation. A lower amount of hardening was obtained with the WNbMoVTaCr₀.₅Al sample based on the changing microhardness values. The surface deformation was decreased in the WNbMoVTaCr₀.₅Al sample.

Keywords: refractory high entropy alloy, microhardness, wear resistance, He⁺ irradiation

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6 Blister Formation Mechanisms in Hot Rolling

Authors: Rebecca Dewfall, Mark Coleman, Vladimir Basabe

Abstract:

Oxide scale growth is an inevitable byproduct of the high temperature processing of steel. Blister is a phenomenon that occurs due to oxide growth, where high temperatures result in the swelling of surface scale, producing a bubble-like feature. Blisters can subsequently become embedded in the steel substrate during hot rolling in the finishing mill. This rolled in scale defect causes havoc within industry, not only with wear on machinery but loss of customer satisfaction, poor surface finish, loss of material, and profit. Even though blister is a highly prevalent issue, there is still much that is not known or understood. The classic iron oxidation system is a complex multiphase system formed of wustite, magnetite, and hematite, producing multi-layered scales. Each phase will have independent properties such as thermal coefficients, growth rate, and mechanical properties, etc. Furthermore, each additional alloying element will have different affinities for oxygen and different mobilities in the oxide phases so that oxide morphologies are specific to alloy chemistry. Therefore, blister regimes can be unique to each steel grade resulting in a diverse range of formation mechanisms. Laboratory conditions were selected to simulate industrial hot rolling with temperature ranges approximate to the formation of secondary and tertiary scales in the finishing mills. Samples with composition: 0.15Wt% C, 0.1Wt% Si, 0.86Wt% Mn, 0.036Wt% Al, and 0.028Wt% Cr, were oxidised in a thermo-gravimetric analyser (TGA), with an air velocity of 10litresmin-1, at temperaturesof 800°C, 850°C, 900°C, 1000°C, 1100°C, and 1200°C respectively. Samples were held at temperature in an argon atmosphere for 10minutes, then oxidised in air for 600s, 60s, 30s, 15s, and 4s, respectively. Oxide morphology and Blisters were characterised using EBSD, WDX, nanoindentation, FIB, and FEG-SEM imaging. Blister was found to have both a nucleation and growth process. During nucleation, the scale detaches from the substrate and blisters after a very short period, roughly 10s. The steel substrate is then exposed inside of the blister and further oxidised in the reducing atmosphere of the blister, however, the atmosphere within the blister is highly dependent upon the porosity of the blister crown. The blister crown was found to be consistently between 35-40um for all heating regimes, which supports the theory that the blister inflates, and the oxide then subsequently grows underneath. Upon heating, two modes of blistering were identified. In Mode 1 it was ascertained that the stresses produced by oxide growth will increase with increasing oxide thickness. Therefore, in Mode 1 the incubation time for blister formation is shortened by increasing temperature. In Mode 2 increase in temperature will result in oxide with a high ductility and high oxide porosity. The high oxide ductility and/or porosity accommodates for the intrinsic stresses from oxide growth. Thus Mode 2 is the inverse of Mode 1, and incubation time is increased with temperature. A new phenomenon was reported whereby blister formed exclusively through cooling at elevated temperatures above mode 2.

Keywords: FEG-SEM, nucleation, oxide morphology, surface defect

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5 Understanding the Lithiation/Delithiation Mechanism of Si₁₋ₓGeₓ Alloys

Authors: Laura C. Loaiza, Elodie Salager, Nicolas Louvain, Athmane Boulaoued, Antonella Iadecola, Patrik Johansson, Lorenzo Stievano, Vincent Seznec, Laure Monconduit

Abstract:

Lithium-ion batteries (LIBs) have an important place among energy storage devices due to their high capacity and good cyclability. However, the advancements in portable and transportation applications have extended the research towards new horizons, and today the development is hampered, e.g., by the capacity of the electrodes employed. Silicon and germanium are among the considered modern anode materials as they can undergo alloying reactions with lithium while delivering high capacities. It has been demonstrated that silicon in its highest lithiated state can deliver up to ten times more capacity than graphite (372 mAh/g): 4200 mAh/g for Li₂₂Si₅ and 3579 mAh/g for Li₁₅Si₄, respectively. On the other hand, germanium presents a capacity of 1384 mAh/g for Li₁₅Ge₄, and a better electronic conductivity and Li ion diffusivity as compared to Si. Nonetheless, the commercialization potential of Ge is limited by its cost. The synergetic effect of Si₁₋ₓGeₓ alloys has been proven, the capacity is increased compared to Ge-rich electrodes and the capacity retention is increased compared to Si-rich electrodes, but the exact performance of this type of electrodes will depend on factors like specific capacity, C-rates, cost, etc. There are several reports on various formulations of Si₁₋ₓGeₓ alloys with promising LIB anode performance with most work performed on complex nanostructures resulting from synthesis efforts implying high cost. In the present work, we studied the electrochemical mechanism of the Si₀.₅Ge₀.₅ alloy as a realistic micron-sized electrode formulation using carboxymethyl cellulose (CMC) as the binder. A combination of a large set of in situ and operando techniques were employed to investigate the structural evolution of Si₀.₅Ge₀.₅ during lithiation and delithiation processes: powder X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), Raman spectroscopy, and 7Li solid state nuclear magnetic resonance spectroscopy (NMR). The results have presented a whole view of the structural modifications induced by the lithiation/delithiation processes. The Si₀.₅Ge₀.₅ amorphization was observed at the beginning of discharge. Further lithiation induces the formation of a-Liₓ(Si/Ge) intermediates and the crystallization of Li₁₅(Si₀.₅Ge₀.₅)₄ at the end of the discharge. At really low voltages a reversible process of overlithiation and formation of Li₁₅₊δ(Si₀.₅Ge₀.₅)₄ was identified and related with a structural evolution of Li₁₅(Si₀.₅Ge₀.₅)₄. Upon charge, the c-Li₁₅(Si₀.₅Ge₀.₅)₄ was transformed into a-Liₓ(Si/Ge) intermediates. At the end of the process an amorphous phase assigned to a-SiₓGey was recovered. Thereby, it was demonstrated that Si and Ge are collectively active along the cycling process, upon discharge with the formation of a ternary Li₁₅(Si₀.₅Ge₀.₅)₄ phase (with a step of overlithiation) and upon charge with the rebuilding of the a-Si-Ge phase. This process is undoubtedly behind the enhanced performance of Si₀.₅Ge₀.₅ compared to a physical mixture of Si and Ge.

Keywords: lithium ion battery, silicon germanium anode, in situ characterization, X-Ray diffraction

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4 Characterization of Alloyed Grey Cast Iron Quenched and Tempered for a Smooth Roll Application

Authors: Mohamed Habireche, Nacer E. Bacha, Mohamed Djeghdjough

Abstract:

In the brick industry, smooth double roll crusher is used for medium and fine crushing of soft to medium hard material. Due to opposite inward rotation of the rolls, the feed material is nipped between the rolls and crushed by compression. They are subject to intense wear, known as three-body abrasion, due to the action of abrasive products. The production downtime affecting productivity stems from two sources: the bi-monthly rectification of the roll crushers and their replacement when they are completely worn out. Choosing the right material for the roll crushers should result in longer machine cycles, and reduced repair and maintenance costs. All roll crushers are imported from outside Algeria. This results in sometimes very long delivery times which handicap the brickyards, in particular in respecting delivery times and honored the orders made by customers. The aim of this work is to investigate the effect of alloying additions on microstructure and wear behavior of grey lamellar cast iron for smooth roll crushers in brick industry. The base gray iron was melted in an induction furnace with low frequency at a temperature of 1500 °C, in which return cast iron scrap, new cast iron ingot, and steel scrap were added to the melt to generate the desired composition. The chemical analysis of the bar samples was carried out using Emission Spectrometer Systems PV 8050 Series (Philips) except for the carbon, for which a carbon/sulphur analyser Elementrac CS-i was used. Unetched microstructure was used to evaluate the graphite flake morphology using the image comparison measurement method. At least five different fields were selected for quantitative estimation of phase constituents. The samples were observed under X100 magnification with a Zeiss Axiover T40 MAT optical microscope equipped with a digital camera. SEM microscope equipped with EDS was used to characterize the phases present in the microstructure. The hardness (750 kg load, 5mm diameter ball) was measured with a Brinell testing machine for both treated and as-solidified condition test pieces. The test bars were used for tensile strength and metallographic evaluations. Mechanical properties were evaluated using tensile specimens made as per ASTM E8 standards. Two specimens were tested for each alloy. From each rod, a test piece was made for the tensile test. The results showed that the quenched and tempered alloys had best wear resistance at 400 °C for alloyed grey cast iron (containing 0.62%Mn, 0.68%Cr, and 1.09% Cu) due to fine carbides in the tempered matrix. In quenched and tempered condition, increasing Cu content in cast irons improved its wear resistance moderately. Combined addition of Cu and Cr increases hardness and wear resistance for a quenched and tempered hypoeutectic grey cast iron.

Keywords: casting, cast iron, microstructure, heat treating

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3 Investigation of Different Electrolyte Salts Effect on ZnO/MWCNT Anode Capacity in LIBs

Authors: Şeyma Dombaycıoğlu, Hilal Köse, Ali Osman Aydın, Hatem Akbulut

Abstract:

Rechargeable lithium ion batteries (LIBs) have been considered as one of the most attractive energy storage choices for laptop computers, electric vehicles and cellular phones owing to their high energy and power density. Compared with conventional carbonaceous materials, transition metal oxides (TMOs) have attracted great interests and stand out among versatile novel anode materials due to their high theoretical specific capacity, wide availability and good safety performance. ZnO, as an anode material for LIBs, has a high theoretical capacity of 978 mAh g-1, much higher than that of the conventional graphite anode (∼370 mAhg-1). However, several major problems such as poor cycleability, resulting from the severe volume expansion and contraction during the alloying-dealloying cycles with Li+ ions and the associated charge transfer process, the pulverization and the agglomeration of individual particles, which drastically reduces the total entrance/exit sites available for Li+ ions still hinder the practical use of ZnO powders as an anode material for LIBs. Therefore, a great deal of effort has been devoted to overcome these problems, and many methods have been developed. In most of these methods, it is claimed that carbon nanotubes (CNTs) will radically improve the performance of batteries, because their unique structure may especially enhance the kinetic properties of the electrodes and result in an extremely high specific charge compared with the theoretical limits of graphitic carbon. Due to outstanding properties of CNTs, MWCNT buckypaper substrate is considered a buffer material to prevent mechanical disintegration of anode material during the battery applications. As the bridge connecting the positive and negative electrodes, the electrolyte plays a critical role affecting the overall electrochemical performance of the cell including rate, capacity, durability and safety. Commercial electrolytes for Li-ion batteries normally consist of certain lithium salts and mixed organic linear and cyclic carbonate solvents. Most commonly, LiPF6 is attributed to its remarkable features including high solubility, good ionic conductivity, high dissociation constant and satisfactory electrochemical stability for commercial fabrication. Besides LiPF6, LiBF4 is well known as a conducting salt for LIBs. LiBF4 shows a better temperature stability in organic carbonate based solutions and less moisture sensitivity compared to LiPF6. In this work, free standing zinc oxide (ZnO) and multiwalled carbon nanotube (MWCNT) nanocomposite materials were prepared by a sol gel technique giving a high capacity anode material for lithium ion batteries. Electrolyte solutions (including 1 m Li+ ion) were prepared with different Li salts in glove box. For this purpose, LiPF6 and LiBF4 salts and also mixed of these salts were solved in EC:DMC solvents (1:1, w/w). CR2016 cells were assembled by using these prepared electrolyte solutions, the ZnO/MWCNT buckypaper nanocomposites as working electrodes, metallic lithium as cathode and polypropylene (PP) as separator. For investigating the effect of different Li salts on the electrochemical performance of ZnO/MWCNT nanocomposite anode material electrochemical tests were performed at room temperature.

Keywords: anode, electrolyte, Li-ion battery, ZnO/MWCNT

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2 Stabilizing Additively Manufactured Superalloys at High Temperatures

Authors: Keivan Davami, Michael Munther, Lloyd Hackel

Abstract:

The control of properties and material behavior by implementing thermal-mechanical processes is based on mechanical deformation and annealing according to a precise schedule that will produce a unique and stable combination of grain structure, dislocation substructure, texture, and dispersion of precipitated phases. The authors recently developed a thermal-mechanical technique to stabilize the microstructure of additively manufactured nickel-based superalloys even after exposure to high temperatures. However, the mechanism(s) that controls this stability is still under investigation. Laser peening (LP), also called laser shock peening (LSP), is a shock based (50 ns duration) post-processing technique used for extending performance levels and improving service life of critical components by developing deep levels of plastic deformation, thereby generating high density of dislocations and inducing compressive residual stresses in the surface and deep subsurface of components. These compressive residual stresses are usually accompanied with an increase in hardness and enhance the material’s resistance to surface-related failures such as creep, fatigue, contact damage, and stress corrosion cracking. While the LP process enhances the life span and durability of the material, the induced compressive residual stresses relax at high temperatures (>0.5Tm, where Tm is the absolute melting temperature), limiting the applicability of the technology. At temperatures above 0.5Tm, the compressive residual stresses relax, and yield strength begins to drop dramatically. The principal reason is the increasing rate of solid-state diffusion, which affects both the dislocations and the microstructural barriers. Dislocation configurations commonly recover by mechanisms such as climbing and recombining rapidly at high temperatures. Furthermore, precipitates coarsen, and grains grow; virtually all of the available microstructural barriers become ineffective.Our results indicate that by using “cyclic” treatments with sequential LP and annealing steps, the compressive stresses survive, and the microstructure is stable after exposure to temperatures exceeding 0.5Tm for a long period of time. When the laser peening process is combined with annealing, dislocations formed as a result of LPand precipitates formed during annealing have a complex interaction that provides further stability at high temperatures. From a scientific point of view, this research lays the groundwork for studying a variety of physical, materials science, and mechanical engineering concepts. This research could lead to metals operating at higher sustained temperatures enabling improved system efficiencies. The strengthening of metals by a variety of means (alloying, work hardening, and other processes) has been of interest for a wide range of applications. However, the mechanistic understanding of the often complex processes of interactionsbetween dislocations with solute atoms and with precipitates during plastic deformation have largely remained scattered in the literature. In this research, the elucidation of the actual mechanisms involved in the novel cyclic LP/annealing processes as a scientific pursuit is investigated through parallel studies of dislocation theory and the implementation of advanced experimental tools. The results of this research help with the validation of a novel laser processing technique for high temperature applications. This will greatly expand the applications of the laser peening technology originally devised only for temperatures lower than half of the melting temperature.

Keywords: laser shock peening, mechanical properties, indentation, high temperature stability

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1 Highly Robust Crosslinked BIAN-based Binder to Stabilize High-Performance Silicon Anode in Lithium-Ion Secondary Battery

Authors: Agman Gupta, Rajashekar Badam, Noriyoshi Matsumi

Abstract:

Introduction: Recently, silicon has been recognized as one of the potential alternatives as anode active material in Li-ion batteries (LIBs) to replace the conventionally used graphite anodes. Silicon is abundantly present in the nature, it can alloy with lithium metal, and has a higher theoretical capacity (~4200 mAhg-1) that is approximately 10 times higher than graphite. However, because of a large volume expansion (~400%) upon repeated de-/alloying, the pulverization of Si particles causes the exfoliation of electrode laminate leading to the loss of electrical contact and adversely affecting the formation of solid-electrolyte interface (SEI).1 Functional polymers as binders have emerged as a competitive strategy to mitigate these drawbacks and failure mechanism of silicon anodes.1 A variety of aqueous/non-aqueous polymer binders like sodium carboxy-methyl cellulose (CMC-Na), styrene butadiene rubber (SBR), poly(acrylic acid), and other variants like mussel inspired binders have been investigated to overcome these drawbacks.1 However, there are only a few reports that mention the attempt of addressing all the drawbacks associated with silicon anodes effectively using a single novel functional polymer system as a binder. In this regard, here, we report a novel highly robust n-type bisiminoacenaphthenequinone (BIAN)-paraphenylene-based crosslinked polymer as a binder for Si anodes in lithium-ion batteries (Fig. 1). On its application, crosslinked-BIAN binder was evaluated to provide mechanical robustness to the large volume expansion of Si particles, maintain electrical conductivity within the electrode laminate, and facilitate in the formation of a thin SEI by restricting the extent of electrolyte decomposition on the surface of anode. The fabricated anodic half-cells were evaluated electrochemically for their rate capability, cyclability, and discharge capacity. Experimental: The polymerized BIAN (P-BIAN) copolymer was synthesized as per the procedure reported by our group.2 The synthesis of crosslinked P-BIAN: a solution of P-BIAN copolymer (1.497 g, 10 mmol) in N-methylpyrrolidone (NMP) (150 ml) was set-up to stir under reflux in nitrogen atmosphere. To this, 1,6-dibromohexane (5 mmol, 0.77 ml) was added dropwise. The resultant reaction mixture was stirred and refluxed at 150 °C for 24 hours followed by refrigeration for 3 hours at 5 °C. The product was obtained by evaporating the NMP solvent under reduced pressure and drying under vacuum at 120 °C for 12 hours. The obtained product was a black colored sticky compound. It was characterized by 1H-NMR, XPS, and FT-IR techniques. Results and Discussion: The N 1s XPS spectrum of the crosslinked BIAN polymer showed two characteristic peaks corresponding to the sp2 hybridized nitrogen (-C=N-) at 399.6 eV of the diimine backbone in the BP and quaternary nitrogen at 400.7 eV corresponding to the crosslinking of BP via dibromohexane. The DFT evaluation of the crosslinked BIAN binder showed that it has a low lying lowest unoccupied molecular orbital (LUMO) that enables it to get doped in the reducing environment and influence the formation of a thin (SEI). Therefore, due to the mechanically robust crosslinked matrices as well as its influence on the formation of a thin SEI, the crosslinked BIAN binder stabilized the Si anode-based half-cell for over 1000 cycles with a reversible capacity of ~2500 mAhg-1 and ~99% capacity retention as shown in Fig. 2. The dynamic electrochemical impedance spectroscopy (DEIS) characterization of crosslinked BIAN-based anodic half-cell confirmed that the SEI formed was thin in comparison with the conventional binder-based anodes. Acknowledgement: We are thankful to the financial support provided by JST-Mirai Program, Grant Number: JP18077239

Keywords: self-healing binder, n-type binder, thin solid-electrolyte interphase (SEI), high-capacity silicon anodes, low-LUMO

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