Theoretical study on composition-dependent properties of ZnO·nAl2O3 spinels. Part II: Mechanical and thermophysical

Knowledge on the mechanical and thermophysical properties of ZnO·nAl₂O₃ is essential for practical applications. Based on the first-principles calculations and the bond valence method, the disordered spinel-type structure of ZnO·nAl₂O₃ (n = 1–4) was constructed to investigate the composition-dependent mechanical and thermophysical properties. The effects of cation substitution on the hardness, elastic modulus, thermal expansion, and thermal conductivity were revealed from the insights into the chemical bonds. At a higher n, the tetrahedral bond is stronger, manifested as its higher hardness and bulk modulus as well as smaller thermal expansion coefficient. Meanwhile, the octahedral bond is weaker, leading to the lower hardness and bulk modulus, along with the larger expansion coefficient. In consequence, the hardness and elastic moduli of ZnO·nAl₂O₃ are improved moderately while the expansion coefficient is decreased with the rise of n. Due to the different vibration characteristics of Zn^IV and Al^IV, the cation disorder in the 8a site provides the primary source of phonon scattering, resulting in the dramatic reduction of thermal conductivity as n increases. The understanding offers guidance on the application-oriented design of new oxide spinels.     

The effect of washing process on the cracking of ZrO2 microspheres by internal gelation

ZrO₂ microspheres are widely used as a simulant of UO₂ in the development of nuclear fuel. However, the cracking of ZrO₂ microspheres prepared by internal gelation is still a challenge during drying and sintering processes. To address this issue, we designed and optimized the washing process for obtaining crack-free ZrO₂ microspheres. Through thermogravimetric, infrared, Raman, BET, and SEM analysis, it is shown that the cracking of the microspheres is mainly related to the pores in microspheres. The washing solvent with low surface tension is used to reduce the effect of capillary force on pore shrinkage. Therefore, the optimal washing process was designed as trichloroethylene (TCE)—0.5 M NH₃.H₂O—Propylene glycol methyl ether (PM) and gel microspheres with a high specific surface area of 315.3 m²/g and pore volume of 0.4125 cm³/g were obtained. The characterizations also further showed that when the microspheres were dried and sintered, the water vapor and the decomposition gas of organic matter were completely released from the pores in the microspheres. Our new washing process could be directly extended for preparing crack-free ceramic microspheres by internal gelation.     

Cold Plasma Treatment of Soybean Oil with Hydrogen Gas

High-voltage atmospheric cold plasma (HVACP) treatment generates reactive gas species that induce inter- and intramolecular reactions in soybean oil. The goal of this study is to analyze the effect of HVACP treatment on the chemical structure of soybean oil in a hydrogen gas environment at atmospheric pressure. HVACP was used to treat soybean oil (15 g) for up to 6 hours by triplicate. Plasma-generated reactive gas species interact with the sample, producing three distinct fractions identified as a liquid, gel, and solid. Fatty acid profile, Fourier-transform infrared spectroscopy, proton and carbon nuclear magnetic resonance, size-exclusion chromatography, thermal properties, and peroxide value were used to characterize the chemical structure. Results indicated a lower content of polyunsaturated fatty acids, increased content of saturated fatty acids, and the presence of isomers. An insoluble portion was observed in the solid fraction and increased with treatment time up to 42% in the 6-h treated samples. Plasma species may cause two main reactions: polymerization and hydrogenation.     

Ti4+ modified MgZrNb2O8 microwave dielectric ceramics with an ultra-high quality factor

Ti⁴⁺-modified MgZrNb₂O₈ (MgZr_1-xTi_xNb₂O₈, x = 0, 0.1, 0.2, 0.3, 0.4) ceramics were synthesized using the traditional solid-state reaction method. Pure MgZr_1–xTi_xNb₂O₈ was detected without any secondary phase via the X-ray diffraction patterns. According to the sintering behavior and the surface morphology results, the introduction of Ti⁴⁺ reduced the sintering temperature and promoted the grain growth. The correlations between the dielectric properties and the crystal structure were analyzed through the Rietveld refinement and Raman spectroscopy. The slight shifts of the Raman peaks, corresponding to different vibration modes, were induced by the substitution of Ti⁴⁺ for Zr⁴⁺ and related to the improved quality factor. In general, the sample of MgZr_0.9Ti_0.1Nb₂O₈ sintered at 1320°C for 4 h exhibited promising microwave dielectric properties with an ultra-high Q × f value of 130 123 GHz (at 7.308 GHz, 20°C), which is potential for 5G communication applications.     

High extinction-ratio microstructure fiber based on chalcogenide glasses

Extinction ratio (ER) is one of the important parameters to characterize the polarization-maintaining (PM) performance of the fiber. In this paper, we report the preparation and properties of a novel chalcogenide microstructure fiber with a high ER. We fabricate a preform using a peeled-off extrusion method. The core and cladding material of the fiber are Ge₉As₂₃Se₆₈ and Ge₁₀As₂₂Se₆₈. The preform was drawn into a fiber with an average ER of −17.08 dB. The loss of the fiber is less than 2 dB over 5.20–8.55 μm, and the minimum loss of the fiber is 0.57 dB/m at 6.2 μm. Moreover, a flat mid-infrared supercontinuum spectrum spanning from 1.53 to 12.50 μm is generated by pumping an 18-cm-long PM fiber for the first time.     

Hot isostatic pressed pyrochlore glass-ceramics: Revealing structure insides at the reaction interface

As potential waste forms for immobilizing actinide-rich radioactive wastes, Eu₂Ti₂O₇ (Eu as a surrogate for minor actinides) pyrochlore glass-ceramics were fabricated via hot isostatic pressing (HIPing) at 1200°C. The structure and microstructure at the reaction interface between the glass-ceramic waste form and the stainless steel (SS) canister under HIPing conditions were carefully investigated with scanning electron microscopy (SEM), transmission electron microscopy (TEM), and synchrotron single crystal X-ray diffraction (SC-XRD). The interactions at the reaction interface led to the formations of a ~10-µm-thick Cr₂O₃ layer as the oxidation front of the SS and a layer of a mixed oxide phase (Eu_1.25SiCr_0.8Ti_1.2O_7.5) on the glass-ceramic side of the reaction interface. The crystal structure of such a unique mixed oxide phase was revealed indubitably with a combination of synchrotron SC-XRD and TEM assisted with a focused ion beam (FIB) SEM system. The improved structural understanding of the reaction interface will help to support the utilization of HIPing as a versatile hot consolidation process for the treatment of radioactive wastes.     

Reinforcing effect of nanocrystalline cellulose and office waste paper fibers on mechanical and thermal properties of poly (lactic acid) composites

Nanocrystalline cellulose (NCC) was prepared from office waste paper (OWP) by sulfuric acid hydrolysis method in this paper and it was used to prepare a series of poly (lactic acid) PLA/NCC composites by using a dissolution method in solvent N, N-dimethylformamide solution. The results indicated that with the addition of only 3 wt% NCC, the composites exhibited outstanding mechanical property. The tensile, bending and impact properties of the PLA/3NCC composite were improved by 8.2%, 13.1%, and 35.9% than those of pure PLA, respectively. On this basis, office waste paper fibers (OWF) were also used as a physical blended filler to enhance PLA/NCC composites to reduce the preparation cost of PLA composites and the perfect PLA/NCC/OWF sample was easily manufactured by melting–blending and injection molding. According to the crystallization and melting performance table, both NCC and OWF can act as nucleating agent to promote the crystallization properties on composites, while the blends did not have positive effect on thermal stability. Furthermore, the water absorption and degradation properties of PLA composites were also studied. This work not only provided a novel idea for the utilization of office waste paper but also successfully produced environment friendly composites with favorable mechanical properties and crystallization performance.     

A (4-fluorophenyl)(phenyl)phosphine oxide-modified epoxy resin with improved flame-retardancy,hydrophobicity, and dielectric properties

The compound (4-fluorophenyl)(phenyl) phosphine oxide (4-FPO) was designed, synthesized, and used in the modification of epoxy resin (EP). The 4-FPO-modified EP was prepared by curing the reaction mixture of diglycidyl ether of bisphenol A (DGEBA) and 4-FPO in the presence of 4,4′-diaminodiphenylsulfone (DDS). Compared with the unmodified EP, the limiting oxygen index value of the EP/4-FPO-0.6 (4-FPO-modified EP with 0.6 wt% of phosphorus) increased to 31.6%, and the sample achieved UL-94 V-0 rating. The peak of the heat release rate, average of the heat release rate, and total heat release of EP/4-FPO-0.6 were reduced by 39, 24, and 19%, respectively. Mechanism study showed that the quenching effect in the gas and barrier effect in the condensed phase were responsible for the enhanced flame-retardant properties of the 4-FPO-modified EP. The results showed that hydrophobicity and dielectric properties of the modified EP were clearly improved.     

Binary polymer blend of ArPTU/PI with advanced comprehensive dielectric properties and ultra-high thermally stability

Flexible high-temperature polymeric dielectrics with advanced dielectric properties are urgently demanded in various applications. In this work, series of polymer blend films were prepared from aromatic polythiourea (ArPTU) and polyimide (PI). The experimental results revealed that the blend films were properly engineered to achieve higher breakdown strength, greater dielectric constant, and larger energy density than pure PI film. For instance, the optimum property was obtained from the blend film with 10 wt% ArPTU, exhibiting prominent dielectric properties (K = 4.52, E_b = 443 MV/m), enhanced energy density (4.00 J/cm³) as well as excellent heat resistance (T_g = 419°C). In addition, stable dielectric properties at broad temperature range from −50 to 250°C were also acquired. It is deduced that the good compatibility from ArPTU and PI with similar polarity are responsible for the improved properties. The superior comprehensive properties which combine the advantages of ArPTU and PI suggest the potential applications of ArPTU/PI blend film in high-temperature dielectric areas.     

Synergistic improvement of mechanical and thermal properties in epoxy composites via polyimide microspheres

Achieving synergetic improvements of mechanical strength, toughness, and thermal stability of epoxy resin has been a crucial but very challenging issue. Herein, to explore a new solution for circumventing this issue, polyimide microspheres were successfully prepared through the inverse nonaqueous emulsion process, and the structure, size distribution and morphologies of polyimide (PI) microspheres were comprehensively investigated. Then the PI microspheres were incorporated in epoxy resin matrix to systematically investigate the mechanical and thermal properties of obtained epoxy/PI microspheres composites. It was found that the PI microspheres can not only enhance the mechanical strength of epoxy resin, but also significantly improve the toughness. Specially, the epoxy-based composites containing 3 wt% PI microspheres exhibit a 47% increase in tensile strength, while the G_IC and Charpy impact strength increase by 106% and 200%, respectively. The toughing mechanism of epoxy/PI microspheres composites was discussed. Moreover, the PI microspheres can also endow the epoxy resin with excellent thermal stability and heat resistance. Thus, this work may open a new opportunity to synergistically enhance the mechanical and thermal properties of epoxy-based composites and may also give some valuable inspiration for the rational design of other high-performance thermosetting composites.