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At least 1,351 records · Page 75

Glutaraldehyde as Ambient Temperature Crosslinking Agent of Latex Films from Natural Rubber Grafted with Poly(diacetone acrylamide)

The concept of using glutaraldehyde (GTA) to crosslink natural rubber (NR) particles bearing diacetone acrylamide (DAAM) functional groups during film formation was investigated in the present work. The primary advantage of this curing system is that it is feasible under ambient conditions, which can lower operating costs of the curing process. Graft copolymers of NR and poly(diacetone acrylamide) prepared with 5 wt% of DAAM (NR–g–PDAAM5) were synthesized by seeded emulsion polymerization at 50 °C. Then, the tensile properties were measured for cast films formed from NR–g–PDAAM5 latex in the absence and presence of GTA. The results revealed increased tensile strength of the NR–g–PDAAM5 film, when GTA was added into the latex prior to film casting. The crosslinking of NR–g–PDAAM5 latex film by reaction with GTA, after film casting, was also investigated using attenuated total reflection Fourier transform infrared (ATR–FTIR) and dynamic mechanical thermal analysis (DMTA). ATR–FTIR analysis demonstrated that crosslinking reactions formed conjugated C=C double bonds between the active carbonyl groups of DAAM and GTA. The complementary use of DMTA also corroborated that crosslinking reactions took place involving the grafted PDAAM chains on the NR particles. This was evidenced by a clear shift towards higher temperatures of the tan δ peak, corresponding to the T{sub g} of NR–g–PDAAM phase, when GTA was incorporated into the NR–g–PDAAM5 latex before film formation. Additionally, a noticeable increase in thermal stability of the NR–g–PDAAM5 film was also observed with added GTA. Hence, it can be concluded that GTA is an efficient room-temperature crosslinker for NR particles functionalized with DAAM. This curing system can also be considered an alternative, simple, and inexpensive method for curing NR latex compounds, as only one component (GTA) is required in the curing process.

36 MATERIALS SCIENCE↗

A Review of Permanent Magnet Stirring During Metal Solidification

Rather than using conventional electromagnetic stirring (EMS) with three-phase alternating current, permanent magnet stirring (PMS), based on the use of sintered NdFeB material which has excellent magnetic characteristics, can be employed to generate a magnetic field for the stirring of liquid metal during solidification. Recent experience with steel casting indicates that PMS requires less than 20 pct of the total energy compared with EMS. Despite the excellent magnetic density properties and low power consumption, this relatively new technology has received comparatively little attention by the metal casting community. This paper reviews simulation modeling, experimental studies, and industrial trials of PMS conducted during recent years. With the development of magnetic simulation software, the magnetic field and associated flow patterns generated by PMS have been evaluated. Based on the results obtained from laboratory experiments, the effects of PMS on metal solidification structures and typical defects such as surface pinholes and center cavities are summarized. The significance of findings obtained from trials of PMS within the metals processing sector, including the continuous casting of steel, are discussed with the aim of providing an overview of the relevant parameters that are of importance for further development and industrial application of this innovative technology.

36 MATERIALS SCIENCE↗

Aluminothermic Reduction Process Under Nitrogen Gas Pressure for Preparing High Nitrogen Austenitic Steels

The aluminothermic reduction casting process under nitrogen gas pressure to make austenitic Cr-Mn-N (Ni-free) and Cr-N (Ni/Mn-free) high nitrogen stainless steels was investigated. Thermodynamic simulation of the redox reaction depending on process parameters was performed. As a result, the optimal ratio of aluminum to oxygen in the initial powder mixture to obtain the highest yield of metal product with minimal aluminum nitride contamination was predicted to be slightly greater than the stoichiometric ratio of 1.125. Microstructures of aluminothermic 26Cr1N and 23Cr9Mn1N steels, prepared taking into account the results of thermodynamic simulation, were investigated by X-ray diffraction, metallography, and transmission electron microscopy. The as-cast microstructure was a pseudo-pearlite (layered ferrite-nitride mixture) in 26Cr1N steel and a ferrite-austenite with signs of discontinuous austenite decomposition in 23Cr9Mn1N steel. After hot forging and subsequent water quenching from 1200 °C, the microstructure was fully austenitic in both steels. Tensile tests of quenched 23Cr9Mn1N steel showed a combination of high strength (ultimate strength of 1324 MPa) and ductility (elongation of 27 pct). The results illustrate that the aluminothermic casting process for producing high nitrogen steel is competitive with the commonly used methods, such as pressure electroslag remelting, both in terms of cost and mechanical properties of manufactured steel.

36 MATERIALS SCIENCE↗

Characteristics of Nozzle Clogging and Evolution of Oxide Inclusion for Al-Killed Ti-Stabilized 18Cr Stainless Steel

Characteristics of nozzle clogging and evolution of oxide inclusion were studied by sampling the deposits of submerged entry nozzle (SEN) and the molten steel in tundish during Al-killed Ti-stabilized 18Cr stainless steelmaking process. The deposits found in the clogging of SEN were mainly composed of frozen steel and inclusions. The inclusions in the deposits and tundish were both mainly (MgO-Al{sub 2}O{sub 3}){sub rich}-CaO-TiO{sub x}. The compositions of most inclusions were Liquid+Spinel or Liquid+TiSp phase. The (MgO-Al{sub 2}O{sub 3}){sub rich}-CaO inclusions that were not effectively modified by calcium treatment could be a source of clogging. By combining both the experimental results and thermodynamic calculation, (MgO-Al{sub 2}O{sub 3}){sub rich}-TiO{sub x} inclusions (TiSp inclusions) would be formed with the decreasing temperature in steel during continuous casting, which could be transported and accumulated on the inner wall of the SEN. Increasing the calcium content in the molten steel could decrease the formation of TiSp inclusions. During continuous casting, these inclusions accumulated on the inner wall of the SEN and gradually formed porous network of clog. Molten steel would gradually solidify in the porous space of the clog due to the increased residence time of the molten steel when flowing through it. The clogging gradually increased and caused the shutdown of continuous casting.

36 MATERIALS SCIENCE↗

Influence of Melt-Pouring Temperature and Composition of Primary Coating of Shell Mold on Tensile Strength and Creep Resistance of Ni-Based Superalloy

Eight investment castings of Inconel 713C superalloy were fabricated, varying in the melt-pouring temperature, from 1400 to 1520 °C, and CoAl{sub 2}O{sub 4} inoculant content, 0 or 5 wt.%, in the primary coat. Their influence on grain size on tensile and creep properties was investigated. The best combination of yield stress (815 MPa) and elongation (A{sub 4} = 7.65%) at ambient temperature was obtained in surface-modified castings poured from 1520 °C. The longest time to rupture was for the unmodified castings (76.8 h) poured from 1520 °C, while for the modified variant, the time to rupture was lower around, 7.4 h, which was still a satisfactory value. During tensile testing, microcracks were formed in large eutectic γ′, carbides and borides, due to the accumulation of stress at interfaces with the matrix. During creep, N-type rafting of γ′ precipitates and phase transformation MC + γ → γ′ + M{sub 23}C{sub 6} took place.

36 MATERIALS SCIENCE↗

Effects of Fine Particle Shot Peening Treatment on Fatigue Properties of Al-7Si-0.3Mg Alloy

In this study, two different fine particle shot peening (FPSP) treatments were performed on Al-7Si-0.3Mg alloy specimens to evaluate their effects on fatigue properties. After the treatment, the microstructure morphology of the specimens was observed, and the surface roughness and residual stress distribution were measured. Rotating bending fatigue tests were conducted, and the fatigue fracture surfaces were observed using scanning electron microscopy (SEM). The crack initiation and propagation behavior were investigated using the replica method. The results indicate that FPSP can introduce residual stress on the surface layer of the material and refine the surface microstructure, and also change the surface roughness. At low stress amplitude levels, FPSP can improve fatigue life significantly. At 5 × 10{sup 7} cycles, the fatigue strength of shot-peened specimens increased by 33% compared to unpeened specimens. In unpeened and steel shot-peened (SSP) specimens, both crystal slip and casting defects can induce fatigue failure, while only casting defects can cause failure in the case of ceramic shot-peened (CSP) specimens. Moreover, FPSP can move the crack initiation site to the subsurface from the surface. The range of threshold stress intensity factor of the material can be improved significantly by this treatment. Casting defects have a significant influence on fatigue strength; the effect on fatigue strength can be well evaluated by the modified Murakami equation.

36 MATERIALS SCIENCE↗

Microstructure and Mechanical Properties of Ni-based Superalloy K418 Produced by the Continuous Unidirectional Solidification Process

Adopting effective strategies to control the solidification structure of Ni-based superalloys is a very interesting subject for metallurgists. Despite the achievement of developing and applying the continuous unidirectional solidification process in simple alloys, the utilization of this process for K418 alloys has been ignored. The microstructure and mechanical properties of a K418 alloy ingot produced by the continuous unidirectional solidification process were investigated. We found that the γ dendrites were typically cross-shaped in the transverse section. The orientation of surviving grains along the casting direction was <001> during competitive growth. The secondary dendrite arm spacing was 32.3 ± 2.5 μm at a cooling rate of 1.75 ± 0.35 °C/s from the surface to the center of the K418 alloy ingot. Due to the higher cooling rate than that of the conventional casting process, a more uniform microstructure and finer γ′ precipitation were obtained in the ingot. Thus, compared with the conventional casting, the tensile strength and the elongation are increased by 8.4 and 21.3%, respectively, at 25 °C. The tensile strength and elongation increased by 15.2 and 49.3%, respectively, at 800 °C. In addition, the fracture surfaces exhibited numerous typical dimples and dendritic fracture characteristics.

36 MATERIALS SCIENCE↗

Friction surfaced Stellite6 coatings

Solid state Stellite6 coatings were deposited on steel substrate by friction surfacing and compared with Stellite6 cast rod and coatings deposited by gas tungsten arc and plasma transferred arc welding processes. Friction surfaced coatings exhibited finer and uniformly distributed carbides and were characterized by the absence of solidification structure and compositional homogeneity compared to cast rod, gas tungsten arc and plasma transferred coatings. Friction surfaced coating showed relatively higher hardness. X-ray diffraction of samples showed only face centered cubic Co peaks while cold worked coating showed hexagonally close packed Co also. - Highlights: Black-Right-Pointing-Pointer Stellite6 used as coating material for friction surfacing. Black-Right-Pointing-Pointer Friction surfaced (FS) coatings compared with casting, GTA and PTA processes. Black-Right-Pointing-Pointer Finer and uniformly distributed carbides in friction surfaced coatings. Black-Right-Pointing-Pointer Absence of melting results compositional homogeneity in FS Stellite6 coatings.

36 MATERIALS SCIENCE↗

Cryogenic EBSD reveals structure of directionally solidified ice–polymer composite

Despite considerable research efforts on directionally solidified or freeze-cast materials in recent years, little fundamental knowledge has been gained that links model with experiment. In this contribution, the cryogenic characterization of directionally solidified polymer solutions illustrates, how powerful cryo-scanning electron microscopy combined with electron backscatter diffraction is for the structural characterization of ice–polymer composite materials. Under controlled sublimation, the freeze-cast polymer scaffold structure is revealed and imaged with secondary electrons. Electron backscatter diffraction fabric analysis shows that the ice crystals, which template the polymer scaffold and create the lamellar structure, have a-axes oriented parallel to the direction of solidification and the c-axes perpendicular to it. These results indicate the great potential of both cryo-scanning electron microscopy and cryo-electron backscatter diffraction in gaining fundamental knowledge of structure–property–processing correlations. - Highlights: • Cryo-SEM of freeze-cast polymer solution reveals an ice-templated structure. • Cryo-EBSD reveals the ice crystal a-axis to parallel the solidification direction. • The honeycomb-like polymer phase favors columnar ridges only on one side. • Combining cryo-SEM with EBSD links solidification theory with experiment.

36 MATERIALS SCIENCE↗

Influence of surface morphology and UFG on damping and mechanical properties of composite reinforced with spinel MgAl{sub 2}O{sub 4}-SiC core-shell microcomposites

Interface between ceramic particulate and matrix is known to control the response of the materials and functionality of the composite. Among numerous physical properties, grain structure of the materials has also played a significant role in defining the behaviour of metal matrix composites. Usually, silicon carbide (SiC) particles show poor interfacial wettability in aluminium melt. Herein, we were successfully synthesized magnesium oxide (MgO) and nanocrystalline magnesium aluminate (MgAl{sub 2}O{sub 4}) spinel coated silicon carbide (SiC) core-shell micro-composites through sol-gel technique to improve the wettability of dispersoids. Core-shell structures of submicron size were thoroughly investigated by various characterization techniques. Further, aluminium matrix composites incorporated with pristine SiC, MgO grafted SiC and MgAl{sub 2}O{sub 4} grafted SiC particles were fabricated by stir casting technique, respectively. Additionally, as-cast composites were processed via friction stir processing (FSP) technique to observe the influence of grain refinement on mechanical and damping properties. Electron back scattered diffraction (EBSD), Field emission scanning electron microscopy (FE-SEM) and X-ray energy dispersion spectroscopy (EDX) analysis were conducted for investigating grain size refinement, adequate dispersion, stability and de-agglomeration of encapsulated SiC particles in aluminium matrix. The mechanical as well as thermal cyclic (from − 100 to 400 °C) damping performance of the as-cast and friction stir processed composites were studied, respectively. Finally, the enhanced properties were attributable to reduced agglomeration, stabilization and proper dispersion of the tailored SiC particles Al matrix. - Highlights: •Synthesizing a novel coating layer of MgO and MgAl{sub 2}O{sub 4} spinel onto SiC particles •Significant improvement in UTS and hardness by reinforcing tailored SiC in Al •Significant grain refinements were obtained through FSP •SiC/MgAl{sub 2}O{sub 4}/Al exhibits ~ 61% higher storage modulus as compare to pure Al after FSP.

36 MATERIALS SCIENCE↗

Effect of copper content on the tensile elongation of Al–Cu–Mn–Zr alloys: Experiments and finite element simulations

Microstructures of cast aluminum alloys used in automotive engine applications often consist of intermetallic particles that can impact the tensile elongation of these alloys. Here in this paper, we investigate the effect of intermetallic grain boundary particles on tensile elongation by fabricating a series of alloys with Cu content varying between 6.0 - 9.0 wt% in cast Al–Cu–Mn–Zr (ACMZ) type compositions. The tensile elongation of as-aged ACMZ alloys decreases monotonically with increase in Cu content. While the microstructure within the grains and yield stress of the alloy remains invariant with Cu content, the decrease in tensile elongation correlates well with increase in the size and volume fraction of grain boundary particles. Microstructural observations are combined with finite element simulations to explain the trend in tensile elongation with changing Cu content. Crack initiation is found to occur by brittle fracture of the grain boundary particles. Increase in particle size promotes crack initiation by reduction in size dependent particle fracture strength. Lower inter-particle spacing at higher particle volume fraction further facilitates crack initiation by increasing stress within the particles caused by the interaction between stress fields of neighboring particles. Increase in particle volume fraction also accelerates crack propagation through the formation of macro shear zones in the microstructure. The increase in Cu content of cast ACMZ alloys, therefore, decreases tensile elongation by promoting both crack initiation and crack propagation.

36 MATERIALS SCIENCE↗

Impact of carbonation on leaching of constituents from a cementitious waste form for treatment of low activity waste at the DOE Hanford site

Carbonation can be a major aging process during disposal of alkaline cementitious waste forms and can impact constituent leaching by changes in material alkalinity, pore structure, and controlling mineral phases. The effect of carbonation on the leaching of major and trace constituents from Cast Stone, a cementitious waste form developed to treat high salt content low activity waste, was studied through a combination of leaching experiments and reactive transport simulations. Diffusive transport of constituents in the waste form was evaluated using reactive transport modeling of diffusion-controlled leaching test results and a geochemical speciation model derived from pH-dependent leaching. Comparisons between Cast Stone materials aged under nitrogen, air, and 2% carbon dioxide in nitrogen showed that carbonation impacts solubility, physical retention and observed diffusivity of major and trace constituents. Carbonation under 2% CO 2 decreased the diffusion-controlled leaching of chromium by two orders of magnitude. Finally, modeling results suggest that carbonation may also decrease solubility of technetium while changes to microstructure by carbonation increases effective diffusivity of constituents in Cast Stone.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Development of a Castable High Strength Secondary Aluminum Alloy from Recycled Wrought Aluminum Scrap

A new process for recycling scrap AA7075 aerospace alloys directly into a high strength castable secondary alloy is demonstrated. The process involves enhancing the castability of the utilized primary wrought aluminum scrap feedstock by scrap alloy chemistry optimization and zirconium additions in order to mitigate the inherent hot tearing tendency of 7075 alloys. By utilizing the new process, the hot tearing index of scrap AA7075 was reduced from 26 to 4. Defect-free castings were obtained in pilot-scale castings trials. The developed secondary 7075 alloy also satisfied preset target mechanical properties with strength levels exceeding 250 MPa and elongation levels higher than 3%. The validity of the new approach and its readiness for transition to commercial practice was demonstrated by casting cylinder heads directly from the modified 7075 scrap.

36 MATERIALS SCIENCE↗

Novel Fuel Form Fabrication

Novel fuel form fabrication efforts have focused on casting of smaller diameter fuels in order to show the feasibility of the FAST test and the incorporation of a FCCI barrier either integral to the fuel or within the cladding tube. Casting of small diameter fuel slugs proved to be feasible at least one pin at a time using vacuum assisted arc casting. Integration of an integral FCCI barrier is also feasible although additional refinement will be necessary. If a sodium bonded fuel is employed, a more simple FCCI barrier may be to incorporate a thin barrier of material in the cladding before the sodium and fuel are loaded. Experiments have shown that sodium bonding of the barrier material and fuel is feasible.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Scalable Dry Printing Manufacturing to Enable Long-Life and High Energy Lithium-Ion Batteries

Slurry casting method dominates the electrode manufacture of lithium-ion batteries. The entire procedure is similar to the newspaper printing that includes premixing of cast materials into solvents homogeneously, and continuously transferring and drying the slurry mixture onto the current collector. As a market approaching US $80 billion by 2024, the optimization of manufacture process is crucial and attractive. However, the organic solvent remains irreplaceable in the wet method for making slurries, even though it is capital-intensive and toxic. In this paper, an advanced powder printing technique is demonstrated that is completely solvent-free and dry. Through removing the solvent and related procedures, this method is anticipated to statistically save 20% of the cost at a remarkably shortened production cycle (from hours to minutes). The dry printed electrodes outperform commercial slurry cast ones in 650 cycles (80% capacity retention in 500 cycles), and thick electrodes are successfully fabricated to increase the energy density. Furthermore, microscopy techniques are utilized to characterize the difference of electrode microstructure between dry and wet methods, and distinguish dry printing's advantages on controlling the microstructure. Finally, this study proves a practical fabrication method for lithium-ion electrodes with lowered cost and favorable performance, and allows more advanced electrode designs potentially.

25 ENERGY STORAGE↗

Sequential Processing for Organic Photovoltaics: Design Rules for Morphology Control by Tailored Semi-Orthogonal Solvent Blends

Design rules are presented for significantly expanding sequential processing (SqP) into previously inaccessible polymer:fullerene systems by tailoring binary solvent blends for fullerene deposition. Starting with a base solvent that has high fullerene solubility, 2-chlorophenol (2-CP), ellipsometry-based swelling experiments are used to investigate different co-solvents for the fullerene-casting solution. By tuning the Flory-Huggins χ parameter of the 2-CP/co-solvent blend, it is possible to optimally swell the polymer of interest for fullerene interdiffusion without dissolution of the polymer underlayer. In this way solar cell power conversion efficiencies are obtained for the PTB7 (poly[(4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl)(3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl)]) and PC61BM (phenyl-C61-butyric acid methyl ester) materials combination that match those of blend-cast films. Both semicrystalline (e.g., P3HT (poly(3-hexylthiophene-2,5-diyl)) and entirely amorphous (e.g., PSDTTT (poly[(4,8-di(2-butyloxy)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl)-alt-(2,5-bis(4,4'-bis(2-octyl)dithieno[3,2-b:2'3'-d]silole-2,6-diyl)thiazolo[5,4-d]thiazole)]) conjugated polymers can be processed into highly efficient photovoltaic devices using the solvent-blend SqP design rules. Grazing-incidence wide-angle x-ray diffraction experiments confirm that proper choice of the fullerene casting co-solvent yields well-ordered interdispersed bulk heterojunction (BHJ) morphologies without the need for subsequent thermal annealing or the use of trace solvent additives (e.g., diiodooctane). The results open SqP to polymer/fullerene systems that are currently incompatible with traditional methods of device fabrication, and make BHJ morphology control a more tractable problem.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of Precursor Solution Aging on the Crystallinity and Photovoltaic Performance of Perovskite Solar Cells

Perovskite materials due to their exceptional photophysical properties are beginning to dominate the field of thin‐film optoelectronic devices. However, one of the primary challenges is the processing‐dependent variability in the properties, thus making it imperative to understand the origin of such variations. Here, it is discovered that the precursor solution aging time before it is cast into a thin film, is a subtle but a very important factor that dramatically affects the overall thin‐film formation and crystallinity and therein factors such as grain growth, phase purity, surface uniformity, trap state density, and overall solar cell performance. It is shown that progressive aging of the precursor promotes efficient formation of larger seeds after the fast nucleation of a large density of small seeds. The hot‐casting method then leads to the growth of large grains in uniform thin‐films with excellent crystallinity validated using scanning microscopy images and X‐ray diffraction patterns. The high‐quality films cast from aged solution is ideal for thin‐film photovoltaic device fabrication with reduced shunt current and good charge transport. This observation is a significant step toward achieving highly crystalline thin‐films with reliability in device performance and establishes the subtle but dramatic effect of solution aging before fabricating perovskite thin‐films.

Tsai, Hsinhan↗

Mechanical and microstructural characterization of sulfonated pentablock copolymer membranes

ABSTRACT Creep experiments utilizing a membrane inflation geometry were used to characterize the mechanical properties of pentablock copolymer membranes designed for water purification applications. Membranes were formed by casting from micellar solutions, and structure development during the casting process was followed in real time with grazing incidence small angle X‐ray scattering. The thin film morphologies were consistent with previously published results obtained for much thicker solvent cast films. The biaxial creep compliance of the films for applied stresses in the megapascal range increased substantially as the degree of sulfonation and consequent hydration of the middle block was increased. The sulfonation level was much more important than the overall degree of ordering in determining the creep compliance of the hydrated membranes. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53 , 39–47

Laprade, Evan J.↗