Chemical Reaction and Bonding Mechanism at the Polymer-Metal Interface.

Polymer-metal hybrid structures have attracted significant attention recently due to their advantage of great weight reduction and excellent integrated physical/chemical properties. However, due to great physicochemical differences between polymers and metals, obtaining an interface with high bonding strength is a challenge, which makes it critically important to clarify the underlying bonding mechanisms. In the present research, we focused on revealing the underlying bonding mechanisms of a laminated Cr-coated steel-ethylene acrylic acid (EAA) strip prepared by hot roll bonding from the microscale to the molecular scale with experimental evidence. The microscale mechanical interlocking was analyzed and proven by scanning white light interferometry and scanning electron microscopy (SEM) by means of observing the surface and cross-sectional morphologies. Additionally, interfacial phases and chemical compositions were analyzed by transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDX). More directly and effectively, the interface was successfully exposed for X-ray photoelectron spectroscopy (XPS) analysis. Combined with time-of-flight secondary ion mass spectroscopy (ToF-SIMS) and depth profiling analysis, the formation of -(O═)C-O-Cr and -C-(O-Cr)2 covalent bonds through chemical reactions at the interface between -COOH and Cr2O3 was verified. Based on these characterization results, interfacial bonding mechanisms for the laminated Cr-coated steel-EAA strip were clearly identified to be chemical bonding and micromechanical interlocking, along with hydrogen bonding, which were all demonstrated with solid experimental evidence. In addition, 3D-render view and cross-section images of typical ion fragments at the interface were used to reveal the interfacial structure more comprehensively. The contributions of hydrogen bonds and covalent bonds to the interface were evaluated and compared for the first time. This study provides both methodological and theoretical guidance for investigating and understanding interfacial bonding formation in polymer-metal hybrid structures.

High-resolution insight into the competitive adsorption of heavy metals on natural sediment by site energy distribution.

Investigating competitive adsorption on river/lake sediments is valuable for understanding the fate and transport of heavy metals. Most studies have studied the adsorption isotherms of competitive heavy metals, which mainly comparing the adsorption information on the same concentration. However, intrinsically, the concentration of each heavy metal on competitive adsorption sites is different, while the adsorption energy is identical. Thus, this paper introduced the site energy distribution theory to increase insight into the competitive adsorption of heavy metals (Cu, Cd and Zn). The site energy distributions of each metal with and without other coexisting heavy metals were obtained. It illustrated that site energy distributions provide much more information than adsorption isotherms through screening of the full energy range. The results showed the superior heavy metal in each site energy area and the influence of competitive metals on the site energy distribution of target heavy metal. Site energy distributions can further help in determining the competitive sites and ratios of coexisting metals. In particular, in the high-energy area, which has great environmental significance, the ratios of heavy metals in the competitive adsorption sites obtained for various competitive systems were as follows: slightly more than 3:1 (Cu-Cd), slightly less than 3:1 (Cu-Zn), slightly more than 1:1 (Cd-Zn), and nearly 7:2:2 (Cu-Cd-Zn). The results from this study are helpful to deeply understand competitive adsorption of heavy metals (Cu, Cd, Zn) on sediment. Therefore, this study was effective in presenting a general pattern for future reference in competitive adsorption studies on sediments.

Quantification of the limitation of Langmuir model used in adsorption research on sediments via site energy heterogeneity.

The Langmuir model has been extensively introduced into the field of environmental adsorption, while some studies showed that it was difficult for the model to describe the adsorption of sediments. The purpose of this paper is to recognize the applicability of the Langmuir model used in the adsorption of contaminants onto sediments quantitatively through the relationship between the error of Langmuir (δ) and site energy heterogeneity (σ). The formula for calculating δ in sediments was developed based on the heterogeneity parameters (m, n). The data was extracted from papers discussing about the adsorption of pollutants on natural sediments. It was further used to investigate the error of Langmuir and the effect on the error from the site energy heterogeneity. The results indicate that the Langmuir model can be applied in sediments when each one of the conditions below is satisfied, (1) m and n lie in the area which signifies that the relative error is less than 10%, (2) the site energy heterogeneity of sediment is under 5.668. These findings are vital for the proper choice of models fitting the adsorption process of sediments.

Spatio-temporal variations of PM2.5 emission in China from 2005 to 2014.

With the rapid development of economy, air pollution has become increasingly serious nowadays in China, especially for the PM2.5. In this paper, the Spatio-temporal variations of PM2.5 emission over the past decade, from 2005 to 2014, were researched by cartograms. Meanwhile, a complex network technology was adopted to study the spatial auto-correlation of PM2.5 emission. The results showed that every province in China suffered a disparate increment in PM2.5 emission during the past ten years and also indicated that provinces in the same region had a huge influence on each other. There were three sectors including the thermal power, biomass burning and building materials that constituted the major sources of PM2.5 emission and they had different changing trends. There existed a dramatic difference in the east and west of China considering that the amount of PM2.5 was closely related to gross domestic product (GDP) and population. With higher GDP and population, eastern provinces emitted the most amount of PM2.5. Normalization results proposed that most of the provinces were PM2.5 exporting provinces in the southeast of China while most in the northwest were importing provinces. This study can help the policy-makers understand the distribution characteristics of PM2.5 emission and propose the effective strategy to mitigate the pollution of haze.

Spatial distribution, ecological risk assessment, and potential sources of heavy metal(loid)s in surface sediments from the Huai River within the Bengbu section, China.

The Huai River is one of the major drinking water resources in Bengbu City of China's eastern Anhui Province. The study focused on extracting information for spatial distributions of heavy metal(loid)s (As, Cd, Cr, Cu, Hg, Ni, Pb, and Zn) based on the contents of pollutants in 20 surface sediments. Geoaccumulation index and Hakanson potential ecological index were used to calculate the ecological risk of sediment environment in this paper. The I geo results indicated that the sediments were moderately contaminated by Hg and Pb. The potential ecological risk sequence of the metals was Hg > Cd > Pb > Cu > Ni > Cr > Zn > As. Among the metal(loid)s, Hg was the main source of pollution that contributed ∼76% towards the potential ecological risk, followed by Cd. Finally, multivariate statistical analysis methods were conducted to identify the potential causes of pollution and provide basis for environment treatment in Bengbu Reach. The results depicted that Pb may be mainly derived from the traffic emission and manufacturing industry, while Hg may be originated from agricultural emissions.

Morphology Evolution and Degradation of CsPbBr3 Nanocrystals under Blue Light-Emitting Diode Illumination.

Under illumination of light-emitting diode (LED) or sunlight, the green color of all-inorganic CsPbBr3 perovskite nanocrystals (CPB-NCs) often quickly changes to yellow, followed by large photoluminescence (PL) loss. To figure out what is happening on CPB-NCs during the color change process, the morphology, structure, and PL evolutions are systematically investigated by varying the influence factors of illumination, moisture, oxygen, and temperature. We find that the yellow color is mainly originated from the large CPB crystals formed in the illumination process. With maximized isolation of oxygen for the sandwiched film or the uncovered film stored in nitrogen, the color change can be dramatically slowed down whether there is water vapor or not. Under dark condition, the PL emissions are not significantly influenced by the varied relative humidity (RH) levels and temperatures up to 60 °C. Under the precondition of oxygen or air, color change and PL loss become more obvious when increasing the illumination power or RH level, and the large-sized cubic CPB crystals are further evolved into the oval-shaped crystals. We confirm that oxygen is the crucial factor to drive the color change, which has the strong synergistic effect with the illumination and moisture for the degradation of the CPB film. Meanwhile, the surface decomposition and the increased charge trap states occurred in the formed large CPB crystals play important roles for the PL loss.

Enhancing the Stability of CH3NH3PbBr3 Quantum Dots by Embedding in Silica Spheres Derived from Tetramethyl Orthosilicate in "Waterless" Toluene.

Methylammonium lead halide perovskites suffer from poor stability because of their high sensitivity to moisture. Inorganic material coatings of SiO2 are preferred for coupling with perovskites to improve their stability, whereas the conventional SiO2 formation method is unsuitable because it requires water. Here, a simple SiO2 generation method based on the high hydrolysis rate of tetramethyl orthosilicate in analytical-grade toluene was developed to avoid the addition of water and catalyst. As a result, SiO2-encapsulated CH3NH3PbBr3 quantum dots (MAPB-QDs/SiO2) were fabricated without decreasing the quantum yield. Photostability tests indicated that the MAPB-QDs/SiO2 samples were markedly more stable than the unencapsulated MAPB-QDs. The photoluminescence (PL) of the MAPB-QDs/SiO2 powders was maintained at 94.10% after 470 nm LED illumination for 7 h, which was much higher than the remnant PL (38.36%) of the pure MAPB-QD sample under a relative humidity of 60%. Similar test results were observed when the MAPB-QDs/SiO2 powders were incorporated into the poly(methyl methacrylate) films. The enhanced photostability is ascribed to the SiO2 barriers protecting the MAPB-QDs from degradation.

CaF2-Based Near-Infrared Photocatalyst Using the Multifunctional CaTiO3 Precursors as the Calcium Source.

Multistage formation of fluoride upconversion agents from the related-semiconductor precursors provides a promising route for the fabrication of near-infrared (NIR) photocatalysts with high photocatalytic activities. Herein, the cotton templated CaTiO3 "semiconduction" precursors (C-CaTiO3) were used to synthesize the NIR photocatalyst of Er3+/Tm3+/Yb3+-(CaTiO3/CaF2/TiO2) (C-ETYCCT), and the functions of the Ca2+ source for CaF2 and the heterostructure formations were displayed by C-CaTiO3. The generated CaF2 acted as the host material for the lanthanide ions, and the heterostructures were constructed among anatase, rutile, and the remaining CaTiO3. The induced oxygen vacancies and Ti3+ ions enabled the samples to utilize most of the upconversion luminescence for photocatalysis. The NIR driven degradation rate of methyl orange (MO) over C-ETYCCT reached 52.34%, which was 1.6 and 2.5 times higher than those of Er3+/Tm3+/Yb3+-(CaTiO3/TiO2) (C-ETYCT) and Er3+/Tm3+/Yb3+-(CaTiO3/CaF2) (C-ETYCC), respectively. The degradation rates of MO and salicylic acid over C-ETYCCT with UV-vis-NIR light irradiation were also much higher than those of other samples, which were mainly results of the contributions of its high upconversion luminescence and the efficient electron-hole pair separation.

Dosing time of ferric chloride to disinhibit the excessive volatile fatty acids in sludge thermophilic anaerobic digestion system.

An investigation into the effect of ferric chloride (FeCl3) on the disinhibition of excessive volatile fatty acids (VFAs) in sludge thermophilic anaerobic digestion (AD) system was performed. The optimum dosing time of FeCl3 was tested with the time interval of 0 h, 36 h, 72 h, 108 h and 144 h. The maximum biogas production was obtained in the case of 72nd hour dosing group, and the biogas production potential was 293.13 ± 11.38 mL/gVS based on modified Gompertz predicted model with the maximum rate of 8.55 ± 0.38 mL/(gVS day), which was triple as that in the control group. More biodegradable organic matters were generated from sludge with FeCl3 additive and then consumed efficiently according to excitation-emission matrix (EEM) fluorescence spectra analysis in the dissolved organic matter (DOM). Acetic acid was the main inhibitor and synthetic effects occurred for the disinhibition of excessive VFAs with the additive of FeCl3, except to direct removal of acetic acid in the system.

Comparison between solar utilization of a closed microalgae-based bio-loop and that of a stand-alone photovoltaic system.

This study compared the solar energy utilization of a closed microalgae-based bio-loop for energy efficient production of biogas with fertilizer recovery against that of a stand-alone photovoltaic (PV) system. The comparison was made from the perspective of broad life cycle assessment, simultaneously taking exergy to be the functional unit. The results indicated that the bio-loop was more environmentally competitive than an equivalent stand-alone PV system, but had higher economic cost due to high energy consumption during the operational phase. To fix the problem, a patented, interior pressurization scheduling method was used to operate the bio-loop, with microalgae and aerobic bacterial placed together in the same reactor. As a result, the overall environmental impact and total investment were respectively reduced by more than 75% and 84%, a vast improvement on the bio-loop.

Variations of organic matters and microbial community in thermophilic anaerobic digestion of waste activated sludge with the addition of ferric salts.

Ferric salts will influence the thermophilic anaerobic digestion of waste activated sludge (WAS). FeCl3 was found to contribute to the anaerobic digestion process with a cumulative biogas production of 357 mL/gVS, 79.6% higher than that in the control group, and Fe2(SO4)3 had no distinct impact, while Fe(NO3)3 inhibited the methanogenesis process. A favorable balance between the release of organic matters from WAS and consumption rate was established after dosing FeCl3 from the perspective of variations of soluble COD, volatile fatty acids (VFAs) and the dissolved organic matters (DOM) assessed by EEM fluorescence spectroscopy and fluorescence regional integration (FRI) technique. Conversely, the system with Fe(NO3)3 achieved an unsuitable substrates environment. Pyrosequencing revealed that the anaerobic digestion system with FeCl3 enriched Coprothermobacter for proteins fermentation and Methanosarcina for methanogenesis with the values of 18.7% and 63.2%, respectively, while that with the supplementation of Fe(NO3)3 obtained the lowest relative abundance.

Nanoindentation hardness and elastic modulus of nano-grained titanium produced by asymmetric and symmetric rolling.

To understand the nanomechanical properties of nano-grained (NG) Ti produced by combination of asymmetric and symmetric rolling, nanoindentation hardness (H(n)) and elastic modulus (E(n)) of different planes within the NG Ti specimens were measured using continuous stiffness measurement mode at room temperature. For comparison, the nanomechanical properties of the as-received hot-rolled coarse-grained (CG) Ti and ultrafine-grained (UFG) Ti with only asymmetric rolling process were also investigated. It was found that H(n) of the Ti samples increased significantly with the decrease of grain sizes, while E(n) exhibited a slight decrease as the grain sizes decreased from CG to NG regime. The increase of H(n) was expected to be caused by higher density of dislocations and finer grains attained by severer plastic deformation, while the slight decrease of E(n) was considered as a result of the increased density of lattice defects and volume fraction of the grain boundary atoms. Furthermore, the nanomechanical properties of different planes of the Ti specimen exhibited a little difference which can be expressed as H(n(RD-TD)) > H(n(N-RD)) > H(n(TD-ND)) and E(n(RD-TD)) > E(n(ND-RD)) > E(n(TD-ND)). These differences were ascribed to crystallographic textures formed by rolling deformation.

Near-infrared photocatalysts of BiVO4/CaF2:Er³âº, Tm³âº, Yb³âº with enhanced upconversion properties.

Upconversion photocatalysts have the potential to absorb the near-infrared (NIR) light in solar energy and improve the photocatalytic performance. A hierarchical upconversion photocatalyst of BiVO4 (BVO)/CaF2:Er(3+), Tm(3+), Yb(3+) (CF) combined with the narrow-band semiconductor of BVO and the luminescence agent of CF to enhance upconversion properties was synthesized via the hydrothermal method. The CF particles were deposited homogeneously on the surface of the BVO/CF composite with regular dendritic structure, which led to efficient upconversion emissions. The upconversion emission intensity of the BVO/CF composite was 8 times higher than that of pure CF, through tailoring the crystal symmetry of lanthanide ions by Bi(3+) ions. The upconverted ultraviolet (361 and 379 nm), violet (408 nm), and blue (485 nm) light was able to excite BVO for photocatalysis in BVO/CF under NIR irradiation, which improved the degradation rate of methyl orange (MO).