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DFT calculations and kinetic analysis have been employed to comprehensively explore the possibility to prepare epoxides by one-step method using the in-situ generated peroxy radicals or hydroperoxides as epoxidizing agents. Computational studies demonstrated that the selectivities for the reaction systems of O2 /R2/R1, O2 /CuH/R1, O2 /CuH/styrene, O2 /AcH/R1 were 68.2%, 69.6%, 100% and 93.3%, respectively. The in-situ generated peroxide radicals, such as HOOË, CuOOË and AcOOË, could react with R1 or styrene by attacking the CC double bond to form a CO bond and subsequently undergoing a cleavage of OO bond to yield epoxides. Peroxide radicals could abstract a hydrogen atom from methyl group on R1, forming unwanted by-products. It should be noted that the hydrogen atoms of HOOË is easy to be abstracted by CC double bond and simultaneously the oxygen atom is connected to the CH moiety to form an alkyl peroxy radical (Rad11), greatly limiting the selectivity. The comprehensive mechanistic studies provide a deep understanding on preparing epoxides by one-step method.
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Microplastics are found in continental and oceanic waters worldwide, but their spatial distribution shows an intricate pattern. Their driving factors remain difficult to identify and widely discussed due to insufficient and unstandardized monitoring data. Here, based on in situ experiments and hundreds of river samples from the Qinghai-Tibet Plateau, we formulate a model to standardize aquatic microplastic measurements. The model was applied to existing data on a global scale. These data are standardized to a 20 µm mesh size, resulting in a new spatial distribution of aquatic microplastic densities, with average concentrations of 554.93 ± 1352.42 items/m3 in Europe, 2558.90 ± 4799.62 in North America and 1741.94 ± 3225.09 in Asia. Excessive contaminations (microplastic concentration > 104 items/m3) are in the Yangtze River, the Charleston Harbor Estuary, the Bodega Bay and the Winyah Bay. We show that, based on these standardized concentrations, new driving factors could be used to predict the global or regional microplastic distribution in continental waters, such as the Human Development Index with a correlation of 75.86% on a global scale, the nighttime lights with a correlation of 37.26 ± 0.30% in Europe and 39.02 ± 0.54% in Asia, and the Mismanagement Plastic Waste with a correlation of 61.21 ± 19.86% in North America. Mapping standardized concentrations of aquatic microplastics enables a better comparison of contamination levels between regions and reveals more accurate hotspots to better adapt remediation efforts and future plastic pollution scenarios.
Assuntos
Microplásticos , Poluentes Químicos da Água , Humanos , Plásticos , Poluentes Químicos da Água/análise , Monitoramento Ambiental , Padrões de ReferênciaRESUMO
Phosphorus imbalance for cropland can greatly influence environmental quality and productivity of agricultural systems. Resolving cropland phosphorus imbalance may be possible with more efficient multilateral crop trade within the involved trading countries; however, the driving mechanisms are unclear. This study calculates phosphorus budgets in China and five central Asian countries and proposes two optimal multilateral crop trade models to mitigate the phosphorus imbalance. Results show that the current trading pattern between China and Central Asia is causing a phosphorus imbalance intensification. Phosphorus surpluses in China and Uzbekistan are 41.7 and 8.9 kg/ha, while Kazakhstan, Kyrgyzstan, Tajikistan, and Turkmenistan exhibit phosphorus deficits with the negative value of -0.7, -1.2, -0.8, and -0.8 kg/ha, respectively. However, under the optimal multilateral crop trade patterns, phosphorus budget of China and Central Asia will become balanced. Phosphorus imbalance intensification for China is reduced to -2525 and -2472 kt under the single- and bilevel-objective-based crop trades. In Kyrgyzstan, it will drop 61.5 % and 50.0 % and change to 321 and 417 kt under the two optimal crop trades. Moreover, changes of phosphorus imbalance mitigations for other central Asian countries range from 11.9 % to 28.2 %. This provides a scientific basis when establishing policies for strengthening optimal multilateral crop trading across the world to promote global phosphorus management.
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Parylene C has been widely used in the fields of microelectromechanical systems (MEMS) and electronic device encapsulation because of its unique properties, such as biocompatibility and conformal coverage. However, its poor adhesion and low thermal stability limit its use in a wider range of applications. This study proposes a novel method for improving the thermal stability and enhancing the adhesion between Parylene and Si by copolymerizing Parylene C with Parylene F. The successful preparation of Parylene copolymer films containing different ratios of Parylene C and Parylene F was confirmed using Fourier-transform infrared spectroscopy and surface energy calculations. The proposed method resulted in the copolymer film having an adhesion 10.4 times stronger than that of the Parylene C homopolymer film. Furthermore, the friction coefficients and cell culture capability of the Parylene copolymer films were tested. The results indicated no degradation compared with the Parylene C homopolymer film. This copolymerization method significantly expands the applications of Parylene materials.
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Due to the high degree of design freedom and rapid prototyping, laser powder bed fusion (L-PBF) presents a great advantage in the super-hard cemented carbide compared with conventional methods. However, optimizing processing parameters to improve the relative density and surface roughness is still a challenge for cemented carbide fabricated by L-PBF. For this, the effect of the remelting strategy on the forming quality of the L-PBF processed cemented carbide was studied in this article, aiming to explore a suitable process window. The surface quality, relative density, microstructure, and microhardness of the cemented carbide parts fabricated under a single melting and remelting strategy were compared. The results showed that the remelting strategy could efficiently improve the specimens' surface quality and relative density. Besides, the cracks were not obviously aggravated, and the WC grains could distribute more homogeneously on the binder matrix under the remelting strategy. Therefore, the microhardness showed an improvement compared to the single melting strategy.
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In order to improve the wear resistance of offshore drilling equipment, CoCrFeNiMn high-entropy alloy coatings were prepared by cold spraying (CS) and high-speed oxygen fuel spraying (HVOF), and the coatings were subjected to vacuum heat treatment at different temperatures (500 °C, 700 °C and 900 °C). The friction and wear experiments of the coatings before and after vacuum heat treatment were carried out in simulated seawater drilling fluid. The results show that CoCrFeNiMn high-entropy alloy coatings prepared by CS and HVOF have dense structure and bond well with the substrate. After vacuum heat treatment, the main peaks of all oriented FCC phases are broadened and the peak strength is obviously enhanced. The two types of coatings achieve maximum hardness after vacuum heat treatment at 500 °C; the Vickers microhardness of CS-500 °C and HVOF-500 °C are 487.6 and 352.4 HV0.1, respectively. The wear rates of the two coatings at room temperature are very close. CS and HVOF coatings both have the lowest wear rate after vacuum heat treatment at 500 °C. The CS-500 °C coating has the lowest wear rate of 0.2152 mm3 m-1 N-1, about 4/5 (0.2651 mm3 m-1 N-1) of the HVOF-500 °C coating. The wear rates and wear amounts of the two coatings heat-treated at 700 °C and 900 °C decrease due to the decrease in microhardness. The wear mechanisms of the coatings before and after vacuum heat treatment are adhesive wear, abrasive wear, fatigue wear and oxidation wear.
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Cemented carbide materials are widely applied in cutting tools, drill tools, and mold fabrication due to their superior hardness and wear resistance. Producing cemented carbide parts via the laser powder bed fusion (L-PBF) method has the advantage of fabricating complex structures with a rapid manufacturing speed; however, they were underdeveloped due to their low density and crack formation on the blocks. This work studied the effect of different substrates including 316L substrates, Ni200 substrates, and YG15 substrates on the forming quality of WC-17Co parts fabricated by L-PBF, with the aim of finding the optimal substrate for fabrication. The results revealed that the Ni200 substrates had a better wettability for the single tracks formation than other substrates, and bonding between the built block and the Ni200 substrate was firm without separation during processing with a large range of laser energy inputs. This guaranteed the fabrication of a relatively dense block with fewer cracks. Although the high laser energy input that led to fine crack formation on the blocks formed on the Ni200 substrate, it was found to be better suited to restricting cracks than other substrates.
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The effects of titanium (Ti) ion-implanted doses on the chemical composition, surface roughness, mechanical properties, as well as tribological properties of 316L austenitic stainless steel are investigated in this paper. The Ti ion implantations were carried out at an energy of 40 kV and at 2 mA for different doses of 3.0 × 1016, 1.0 × 1017, 1.0 × 1018, and 1.7 × 1018 ions/cm2. The results showed that a new phase (Cr2Ti) was detected, and the concentrations of Ti and C increased obviously when the dose exceeded 1.0 × 1017 ions/cm2. The surface roughness can be significantly reduced after Ti ion implantation. The nano-hardness increased from 3.44 to 5.21 GPa at a Ti ion-implanted dose increase up to 1.0 × 1018 ions/cm2. The friction coefficient decreased from 0.78 for un-implanted samples to 0.68 for a sample at the dose of 1.7 × 1018 ions/cm2. The wear rate was slightly improved when the sample implanted Ti ion at a dose of 1.0 × 1018 ions/cm2. Adhesive wear and oxidation wear are the main wear mechanisms, and a slightly abrasive wear is observed during sliding. Oxidation wear was improved significantly as the implantation dose increased.
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This study experimentally investigated the effect of surface textures on the tribological mechanism of nitrided titanium alloy (Tiâ»6Alâ»4V). The titanium alloy samples were nitrided at various temperatures ranging from 750 to 950 °C for 10 h in a plasma nitriding furnace. Then, surface textures were fabricated on the polished titanium alloy and plasma nitrided samples by laser process system. The surface roughness, microhardness, and constitution of samples treated by single nitriding and samples treated by composite technology were characterized. The tribological properties of the samples were investigated on a CSM ball-on-disc tribometer. The results show that plasma nitriding effectively enhances the wear resistance of the substrate. The wear rate decreases first and then increases with the increase of nitriding temperature, and the wear rate reaches the minimum at 900 °C. However, the increase in roughness caused by nitriding treatment leads to an increase in the friction coefficient. It is found that surface textures can obviously reduce the friction coefficient of the nitrided titanium alloy. In addition, it can also reduce the wear rate of titanium alloys after nitriding at 900 and 950 °C. It can be concluded that the nitriding and surface texturing combined treatment can obviously reduce the friction coefficient and wear rate at the nitriding temperatures of 900 and 950 °C. This is attributed to the combined effect of high hardness of nitride layers and the function of micro-trap for wear debris of surface textures.
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The objective of the given work was to investigate abrasive wear behaviours of titanium (Ti) treated by ultrasonic surface rolling processing (USRP) pre-treatment and plasma nitriding (PN). Simulated lunar regolith particles (SLRPs) were employed as abrasive materials during characterization of tribological performances. The experimental results showed that SLRPs cause severe abrasive wear on Ti plasma-nitrided at 750 °C via the mechanism of micro-cutting. Due to the formation of a harder and thicker nitriding layer, the abrasive wear resistance of the Ti plasma-nitrided at 850 °C was enhanced, and its wear mechanism was mainly fatigue. USRP pre-treatment was effective at enhancing the abrasive wear resistance of plasma-nitrided Ti, due to the enhancement of the hardness and thickness of the nitride layer. Nevertheless, SLRPs significantly decreased the friction coefficient of Ti treated by USRP pre-treatment and PN, because the rolling of small granular abrasives impeded the adhesion of the worn surface. Furthermore, USRP pre-treatment also caused the formation of a dimpled surface with a large number of micropores which can hold wear debris during tribo-tests, and finally, polishing and rolling the wear debris resulted in a low friction coefficient (about 0.5).
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In this paper, the tribological behavior of 316L stainless steel with heterogeneous lamella structure (HLS), prepared through 85% cold rolling technology and subsequent annealing treatment (750 °C, 10 min), were conducted on a ball-on-disc tribometer under different normal loads in dry ambient air conditions. The morphologies, structures, and compositions of the raw and worn surfaces were analyzed by 3D surface profilometer, XRD, SEM, EDS and TEM. Based on this, the results showed that the HLS 316L stainless steel samples exhibited lower and more steady friction coefficients than coarse-grained samples, especially under higher loads, which can be attributed to the existence of numerous oxidative particles across sliding interfaces. However, the wear resistance of HLS 316L stainless steel sample was a little weakened compared to that of the coarse-grained sample under a normal load of 5 N. When the load increases up to 15 N, an obviously decreased wear resistance was found for the HLS of the 316L stainless steel sample, which was 50% lower than that of coarse-grained sample. This can be ascribed to the more severe oxidative and abrasive wear performance of HLS 316L stainless steel sample under dry sliding conditions.