Thermal Conductivity and Sintering Mechanism of Aluminum/Diamond Composites Prepared by DC-Assisted Fast Hot-Pressing Sintering.

A novel DC-assisted fast hot-pressing (FHP) powder sintering technique was utilized to prepare Al/Diamond composites. Three series of orthogonal experiments were designed and conducted to explore the effects of sintering temperature, sintering pressure, and holding time on the thermal conductivity (TC) and sintering mechanism of an Al-50Diamond composite. Improper sintering temperatures dramatically degraded the TC, as relatively low temperatures (≤520 °C) led to the retention of a large number of pores, while higher temperatures (≥600 °C) caused unavoidable debonding cracks. Excessive pressure (≥100 MPa) induced lattice distortion and the accumulation of dislocations, whereas a prolonged holding time (≥20 min) would most likely cause the Al phase to aggregate into clusters due to surface tension. The optimal process parameters for the preparation of Al-50diamond composites by the FHP method were 560 °C-80 MPa-10 min, corresponding to a density and TC of 3.09 g cm-3 and 527.8 W m-1 K-1, respectively. Structural defects such as pores, dislocations, debonding cracks, and agglomerations within the composite strongly enhance the interfacial thermal resistance (ITR), thereby deteriorating TC performance. Considering the ITR of the binary solid-phase composite, the Hasselman-Johnson model can more accurately predict the TC of Al-50diamond composites for FHP technology under an optimal process with a 3.4% error rate (509.6 W m-1 K-1 to 527.8 W m-1 K-1). The theoretical thermal conductivity of the binary composites estimated by data modeling (Hasselman-Johnson Model, etc.) matches well with the actual thermal conductivity of the sintered samples using the FHP method.

Impact of different industrial activities on heavy metals in floodplain soil and ecological risk assessment based on bioavailability: A case study from the Middle Yellow River Basin, northern China.

Understanding the impact of different industrial activities on heavy metals and conducting scientific ecological risk assessments are critical to the management of heavy metal pollution. The present study compared soils affected by different industrial activities in three types of industrial cities (coal city, oil-gas city, and economic city) to control samples and examined the ecological risk based on bioavailability in the Middle Yellow River Basin. The findings revealed that the impact characteristics of different industrial activities on soil heavy metals in the research area were different. Both coal-based and oil-gas industry activities had a minor impact on soil heavy metals, whereas economic industry activities in the southern part had a major impact, as evidenced by significant enrichment of Cd, Hg, Cu, Pb, and Zn. In principal component analysis, the soil heavy metals affected by economic industry activities designated a distinct source from the control samples, particularly the anthropogenic sources represented by Hg and Cd. In the context of heavy metals in chemical form, three types of industrial activities all had an effect on bioavailability (0.72-24.27%) and could increase migratory activity in the environment. Furthermore, both traditional and improved assessments, based on total content and bioavailability, showed a low ecological risk near coal cities and oil-gas cities in the middle and northern parts, while there was a medium-high ecological risk near economically developed cities in the south, particularly Tianshui, Baoji, Qishan, Xianyang, Xi'an, and Tongchuan. In comparison, improved risk assessment based on bioavailability tends to not only compensate for an overestimation in traditional risk assessment from the perspective of total content, but additionally achieve a more reasonable, effective, and advanced assessment of heavy metal risks in scientific research. The outcome of this study has significance for the ecological conservation and high-quality development of the Yellow River Basin.

Distribution, source investigation, and risk assessment of topsoil heavy metals in areas with intensive anthropogenic activities using the positive matrix factorization (PMF) model coupled with self-organizing map (SOM).

Over the past decade, heavy metal (HMs) contamination in soil environments has become severe worldwide. However, their resulting ecological and health risks remained elusive across a variety of soil ecosystems due to the complicated distributions and sources. This study investigated the HMs (Cr, As, Cu, Pb, Zn, Ni, Cd, and Hg) in areas with multi-mineral resources and intensive agricultural activities to study their distribution and source apportionment using a positive matrix factorization (PMF) model coupled with self-organizing map (SOM). The potential ecological and health risks were assessed in terms of distinct sources of HMs. The results disclosed that the spatial distribution of HM contaminations in the topsoil was region-dependent, primarily located in areas with high population intensity. The geo­accumulation index (Igeo) and enrichment factor (EF) values collectively displayed that the topsoils were severely contaminated by Hg, Cu, and Pb, particularly in residential farmland areas. The comprehensive analysis combined with PMF and SOM identified both geogenic and anthropogenic sources of HMs including natural, agricultural, mining, and mixed sources (caused by multi-anthropogenic factors), accounting for 24.9%, 22.6%, 45.9%, and 6.6% contribution rates, respectively. The potential ecological risk was predominantly due to the enrichment of Hg, followed by Cd. The non-carcinogenic risks were mostly below the acceptable risk level, while the potential carcinogenic health risks caused by As and Cr should be paid prime attention to, particularly for children. In addition to the 40% geogenic sources, agricultural activities contributed to 30% of the non-carcinogenic risk, whereas mining activities contributed to nearly half of the carcinogenic health risks.

The enhanced ZrO2 produced by DLP via a reliable plasticizer and its dental application.

Digital light processing (DLP) is considered as one of the most promising additive manufacturing technologies to process ceramics. However, the potential defects produced in the debinding and sintering process extremely restrict ceramic application. In this work, a plasticizer which effectively inhibits defects of the green body in debinding process was investigated. The effects of plasticizer (Polyethylene glycol 200) on the rheological behavior and curing property of the slurry were discussed. In addition, the debinding process and the mechanical of zirconia parts with different PEG200 contents were studied. Adding 20 vol% PEG200 could efficiently suppress the defects in debinding process, and the flexural strength increased from 302 ± 15 to 1210 ± 25 MPa of the ZrO2 ceramic sintered at 1600 °C. The superior biocompatibility and mechanical property reveal that the DLP zirconia has a promising application prospect of biology dental ceramic prostheses.

Spatial-temporal variability and influence factors of Cd in soils of Guangxi, China.

In this study, the regional spatial-temporal variability of cadmium (Cd) in the topsoil of Guangxi, China from 2010 to 2016 was studied from data obtained from the China Geochemical Baseline Project (CGB Ⅰ and CGB Ⅱ). The driving forces of natural and anthropogenic variables were quantitatively analyzed using a geographically and temporally weighted regression model. The results showed that 1) soil Cd was highly enriched in 2010 and in soils of Hechi city in northwest Guangxi, a non-ferrous metal mining and metallurgy area, ~17% of the samples exceeded the soil contamination risk limit. In contrast, in 2016, the topsoil Cd content decreased significantly, with 7% of sites exceeding the soil risk limit. 2) Multiple factors jointly influenced the regional spatial variability of Cd. pH and organic carbon were found to be the main factors influencing Cd content and were strongly spatially correlated with Cd. Anthropogenic activities, including mining and industrial emissions, resulted in significant Cd enrichment in local areas, whereas agricultural and domestic pollutants were relatively weakly correlated with Cd. The weathering products of carbonates were significantly enriched in Cd; thus, the geological background played a significant role in the spatial variability of Cd. Soil-forming factors, including temperature, precipitation, and elevation influenced the spatial distribution of Cd, especially in the Cd background area. 3) Anthropogenic activities were the key factors influencing temporal changes in Cd. Mining caused significant enrichment of Cd in CGB Ⅰ, while industrial emissions were the primary factor for Cd enrichment in CGB Ⅱ. In addition, natural factors also played an important role; the increased Normalized Difference Vegetation Index suggested reduced desertification and reduction of soil erosion in the watershed and in pollutants transported from upstream.

Groundwater quality assessment and hydrogeochemical processes in typical watersheds in Zhangjiakou region, northern China.

It is of significance to elucidate the groundwater quality and hydrogeochemical processes for sustainable utilization of groundwater resources in water shortage regions. A total of 256 groundwater samples were collected in typical watersheds in Zhangjiakou, northern China. The hydrochemical parameters, conventional ions, and trace elements were measured, and δD and δ18O data were collected to delineate the groundwater quality and hydrogeochemical processes. The results showed that 32.91% of the groundwater could be directly used for drinking water sources in the Bashang Plateau, north of the study area. The F- and NO3--N were the main parameters above the standard threshold for drinking water. In contrast, the groundwater quality in the Baxia River Basins, south of the study area, was of a better scenario. Nonetheless, high concentrations of F-, total hardness, and SO42- were still observed. Most samples in the Bashang Plateau had relatively higher salinity than the Baxia River Basins. Both surface water and groundwater in the study area originated from local meteoric water with considerable hydraulic connections. The high-fluoride groundwater was primarily formed by dissolution of fluoride-rich minerals under conditions of high pH and Na+, low Ca2+, and rich in HCO3-. The dissolution of carbonate and silicate minerals accompanied by strong cation exchange and weak evaporation was the dominant water-rock interaction affecting the hydrochemical composition of groundwater, and anthropogenic NO3- input had an extra influence on hydrochemical process. This study provides a scientific guideline for the protection and allocation of local groundwater resources.

Spatial variations in soil organic carbon, nitrogen, phosphorus contents and controlling factors across the "Three Rivers" regions of southwest China.

Based on the data of China Geochemical Baselines project, geostatistical analysis was used to investigate the spatial variations in soil organic carbon (SOC), total nitrogen (TN) and total phosphorus (TP) contents across the "Three Rivers" regions of southwest China, and the factors affecting them were analyzed by the redundancy analysis (RDA) and Person's correlation. Results showed that, the average content of SOC, TN and TP in the study area were 7.20 g/kg, 0.84 g/kg and 0.55 g/kg, respectively. The SOC and TN contents showed an obvious enrichment characteristic with great spatial variability, while TP content was stable on regional scale. The SOC, TN and TP contents decreased with elevation increase in the northern frigid highland, but showed an opposite character in the southern tropical & subtropical, which actually reflected the control of temperature on them. Combined with that there were higher SOC, TN and TP contents in subalpine meadow soil and red earth-yellow earth of the middle latitude zone, these suggested that the suitable temperature was conducive to the accumulation of soil nutrients. The weak positive correlation between population density and soil nutrients, together with high level of soil nutrients in the vicinity of large cities, demonstrated that human activities had significantly increased the soil nutrients contents in the study area. The RDA results showed that soil nutrients in the northern frigid highland were mainly controlled by the environmental factors dominated by temperature and soil structural factors dominated by parent materials with the total explanatory power as high as 75.87%, while in the southern tropical & subtropical mainly by the environmental factors dominated by chemical and biological weathering and the biological factors dominated by vegetation with the total explanatory power as high as 88.53%. The above factors superimposing a certain degree of human activities converged to cause that the SOC and TP contents in the south were higher than that in the north while the TN content was lower than that in the north.

Bimetallic zeolite-imidazole framework-based heterostructure with enhanced photocatalytic hydrogen production activity.

Bimetallic zeolite-imidazole frameworks with controllable flat band position, band gap and hydrogen evolution reaction characteristics were adopted as a photocatalytic hydrogen production catalyst. Furthermore, the g-C3N4-MoS2 2D-2D surface heterostructure was introduced to the ZnM-ZIF to facilitate the separation as well as utilization efficiency of the photo-exited charge carriers in the ZnM-ZIFs. On the other hand, the ZnM-ZIFs not only inhibited the aggregation of the g-C3N4-MoS2 heterostructure, but also improved the separation and transport efficiency of charge carriers in g-C3N4-MoS2. Consequently, the optimal g-C3N4-MoS2-ZnNi-ZIF exhibited an extraordinary photocatalytic hydrogen evolution activity 214.4, 37.5, and 3.7 times larger than that of the pristine g-C3N4, g-C3N4-ZnNi-ZIF and g-C3N4-MoS2, respectively, and exhibited a H2-evolution performance of 77.8 µmol h-1 g-1 under UV-Vis light irradiation coupled with oxidation of H2O into H2O2. This work will furnish a new MOF candidate for photocatalysis and provide insight into better utilization of porous MOF-based heterostructures for hydrogen production from pure water.

Toward enhanced photocatalytic activity of graphite carbon nitride through rational design of noble metal-free dual cocatalysts.

The g-C3N4-MoS2-M(OH)x ternary heterostructures were designed and fabricated for the first time. The embedding of noble-metal-free MoS2-M(OH)x dual cocatalysts over g-C3N4 nanosheets led to obvious synergistic effect for improving the transport as well as utilization efficiency of photo-generated charge carriers. Consequently, the optimal ternary heterostructure (g-C3N4-MoS2-Ni(OH)2) exhibited photocatalytic hydrogen production activity 4.5 times larger than the sum of the photocatalytic HER activity of g-C3N4-MoS2 and g-C3N4-Ni(OH)2. More significantly, even in the absence of the sacrificial agent, the g-C3N4-MoS2-Ni(OH)2 ternary heterostructure exhibited a photocatalytic HER activity of 0.3 mmol h-1 g-1 with considerable H2O2 production under UV-visible light.

Versatile Functional Porous Cobalt-Nickel Phosphide-Carbon Cocatalyst Derived from a Metal-Organic Framework for Boosting the Photocatalytic Activity of Graphitic Carbon Nitride.

Metal-organic framework-templated g-C3N4-NiCoP2-porous carbon (PC) ternary hybrid nanomaterials were designed by taking full advantage of the metal-organic framework (MOF) derivative in the photocatalytic reaction for the first time. The MOF-templated porous structure could prevent the stacking of the carbon nitride nanosheet, and the carefully designed NiCoP2, possessing low electrocatalytic hydrogen evolution reaction (HER) overpotential and flat-band potential, could improve the separation as well as the utilization efficiency of photogenerated electron-hole pairs. Moreover, the ligand-templated porous carbon, acting as an interface mediator between g-C3N4 and the NiCoP2 cocatalyst, could boost the charge carrier transport. Consequently, the optimal ternary g-C3N4-NiCoP2-PC heterostructure exhibited enhanced photocatalytic HER performance and considerable H2 evolution performance of 5.8 µmol/h/g under UV-visible light with stoichiometric H2O2 production even in pure water. This work took full advantage of the MOF derivative for improving the photocatalytic reaction activity and provided a method that can hopefully help in designing a novel high-performance catalyst for solar conversion.

Enhanced photocatalytic hydrogen evolution over bimetallic zeolite imidazole framework-encapsulated CdS nanorods.

A hybrid of ZIF-8 with CdS nanorods could increase the transport efficiency of photo-generated charge carriers and the surface area. Notably, through doping Zn ions with a transition metal, in this work, we fabricated a bimetallic ZnM-ZIF (M = Ni, Cu, or Co)-encapsulated CdS nanorod heterostructure for the first time. Compared with ZIF-8, the bimetallic ZIF exhibited a modulated structure, flat band position, and lower overpotential for the hydrogen evolution reaction. ZnM-ZIF not only improved the transfer of water and light, but also boosted the separation of charge carriers. Consequently, the optimized CdS-ZnM-ZIF samples with Cu, Ni, and Co doping showed corresponding photocatalytic hydrogen activities 44, 92, and 59 times larger than that of pristine CdS nanorods. This work provides a new method for better utilization of porous MOF crystals for photocatalysts.

Co-Doped Zn1-xCdxS nanocrystals from metal-organic framework precursors: porous microstructure and efficient photocatalytic hydrogen evolution.

Nanoporous Co-doped Zn1-xCdxS were facilely fabricated via adopting ZIFs as templates, and Cd(NO3)2 and thiourea as precursors. The highly porous microstructure and uniform Co-doping of the photocatalyst afford a high H2-production rate (45.2 and 422.2 times larger than those of Zn0.5Cd0.5S and CdS), providing an effective way for the development of high performance nanoporous photocatalysts.

Design and construction of polymerized-chitosan coated Fe3O4 magnetic nanoparticles and its application for hydrophobic drug delivery.

In this study, a novel hydrogel, chitosan (CS) crosslinked carboxymethyl-ß-cyclodextrin (CM-ß-CD) polymer modified Fe3O4 magnetic nanoparticles was synthesized for delivering hydrophobic anticancer drug 5-fluorouracil (CS-CDpoly-MNPs). Carboxymethyl-ß-cyclodextrin being grafted on the Fe3O4 nanoparticles (CDpoly-MNPs) contributed to an enhancement of adsorption capacities because of the inclusion abilities of its hydrophobic cavity with insoluble anticancer drugs through host-guest interactions. Experimental results indicated that the amounts of crosslinking agent and bonding times played a crucial role in determining morphology features of the hybrid nanocarriers. The nanocarriers exhibited a high loading efficiency (44.7±1.8%) with a high saturation magnetization of 43.8emu/g. UV-Vis spectroscopy results showed that anticancer drug 5-fluorouracil (5-Fu) could be successfully included into the cavities of the covalently linked CDpoly-MNPs. Moreover, the free carboxymethyl groups could enhance the bonding interactions between the covalently linked CDpoly-MNPs and anticancer drugs. In vitro release studies revealed that the release behaviors of CS-CDpoly-MNPs carriers were pH dependent and demonstrated a swelling and diffusion controlled release. A lower pH value led to swelling effect and electrostatic repulsion contributing to the protonation amine impact of NH3(+), and thus resulted in a higher release rate of 5-Fu. The mechanism of 5-Fu encapsulated into the magnetic chitosan nanoparticles was tentatively proposed.

Detection of serum Alu element hypomethylation for the diagnosis and prognosis of glioma.

Global genomic hypomethylation is a hallmark of cancer in humans. In the present study, the feasibility of measuring hypomethylation of Alu elements (Alu) in serum and its clinical utility were investigated. Tumor tissues and matched serum specimens from 65 glioma patients and serum samples from 30 healthy controls were examined for Alu hypomethylation by bisulfite sequencing. The median serum Alu methylation level was 47.30 % in patients (interquartile range (IQR), 35.40-54.25 %) and 57.90 % in the controls (IQR, 55.25-61.45 %). The median Alu methylation level in tumor samples was 40.30 % (IQR, 36.80-54.20 %), which shows the correlation of Alu hypomethylation between tumor and serum samples (r = 0.882) in the study group. The methylation level was higher in the low-grade glioma group than in the high-grade group both in tumor and serum samples. A correlation between high methylation level and longer survival time was detected in tumor and serum samples. Receiver operating characteristic curve analysis showed that the area under the curve for diagnosis was 0.861 (95 % confidence interval, 0.789-0.933), suggesting that Alu hypomethylation in serum may be of diagnostic value. Our results indicate that the detection of Alu hypomethylation in serum may be clinically useful for the diagnosis and prognosis of glioma.

Highly luminescent quantum dots functionalized and their conjugation with IgG.

A sol-gel approach including partially removing capping agents, depositing SiO(2) monomers, and growing a SiO(2) shell was developed to generate a bio-compatible functionalization on CdTe quantum dots (QDs). The QDs retained their high photoluminescence (PL) efficiency after coating with a SiO(2) shell (22.5%) by controlling the surface state of the QDs to decrease PL degradation during a sol-gel preparation. Furthermore, the CdTe QDs with a SiO(2) shell were conjugated with IgG using 3-sulfo-N-hydroxysuccinimide or streptavidin-maleimide as linkers. The biotin-streptavidin linker resulted in a high PL efficiency retained (only ~23% lower than the initial value of the QDs), which is crucial for bio-applications.

Cadmium sulphide quantum dots in morphologically tunable triblock copolymer aggregates.

Cadmium sulfide (CdS) quantum dots (QDs) are formed within poly(ethylene oxide)-block-polystyrene-block-poly (acrylic acid) (PEO-b-PS-b-PAA) triblock copolymer aggregates of different architectures. These structures are obtained starting with the same ionically cross-linked primary micelles consisting of a cadmium acrylate core, a PS shell, and a PEO corona. One morphology is a worm-shaped micelle prepared in tetrahydrofuran (THF) in which the CdS QDs are surrounded by the PAA and aligned as a loose necklace in the PS matrix. The PEO serves as a corona around the PS rod. Another structure is a multicore spherical (ca. 50 nm) water soluble PS micelle, surrounded by PEO chains. The CdS particles within these two latter structures are formed by the reaction of cadmium ions present in the acrylate cores with hydrogen sulfide. In a third structure, the CdS QDs are located on the surface of PS micelles. A fourth spherical single-core micelle structure is postulated to exist in dilute THF solutions. The dimensions in all the aggregates can be controlled by the block length.

Preparation and pH triggered inversion of vesicles from poly(acrylic acid)-block-polystyrene-block-poly(4-vinyl pyridine).

The aggregate morphologies of the biamphiphilic triblock PAA(26)-b-PS(890)-b-P4VP(40) have been studied by TEM as a function of pH in DMF/THF/H(2)O mixtures. The outside surfaces of the aggregates were characterized by zeta potential measurements. Starting at the apparent pH (pH) of 1, and increasing gradually to pH14, the aggregate morphologies of this triblock change progressively from vesicles (pH1), to solid spherical or ellipsoidal aggregates (pH3 approximately 11), and finally back to vesicles (pH14). Vesicles prepared at pH1 contain P4VP chains on the outside and PAA chains on the inside, while those prepared from the same triblock at pH14 contain PAA outside and P4VP inside. The segregation is based on the difference in repulsive interactions within the PAA or P4VP corona under different pH conditions. At low pH, the curvature is stabilized through increased repulsive interactions between the P4VP chains on the outside relative to the less repulsive interactions between the PAA chains on the inside. At pH14, by contrast, the PAA is preferentially segregated to the outside and the P4VP to the inside because of the increased repulsive interaction between PAA chains and the decreased repulsive interaction between P4VP chains at high pH. Most importantly, vesicles with PAA on the outside can be inverted to P4VP on the outside by changing the pH while the vesicles have swollen cores and are under dynamic conditions. The conversion mechanism is suggested to involve a whole vesicle process because the CMC is far too low for single chain reassembly to be involved.