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Spiders silks have extraordinary strength and toughness simultaneously, thus has become dreamed materials by scientists and industries. Although there have been tremendous attempts to prepare fibers from genetically manufacture spider silk proteins, however, it has been still a huge challenge because of tedious procedure and high cost. Here, a facile spider-silk-mimicking strategy is reported for preparing highly scratchable polymers and supertough fibers from chemical synthesis route. Polymer films with high extensibility (>1200%) and supertough fibers (~387 MJ m-3) are achieved by introducing polypeptides with β-sheet and α-helical structure in polyureathane/urea polymers. Notabley,the toughness of the fiber is more than twice the reported value of a normal spider dragline silk, and comparable with the toughest spider silk, aciniform silk of Argiope trifasciata.

The success of a neutron or X-ray scattering experiment relies on sufficient signal from the system being studied. The intensity of scattered radiation depends on instrument resolution, the structu...

Summary Solution-processed colloidal quantum dots (CQDs) are promising optoelectronic materials; however, CQD solids have, to date, exhibited either excellent transport properties but fusion among CQDs or limited transport when QDs are strongly passivated. Here, we report the growth of monolayer perovskite bridges among quantum dots and show that this enables the union of surface passivation with improved charge transport. We grow the perovskite layer after forming the CQD solid rather than introducing perovskite precursors into the quantum dot solution: the monolayer of perovskite increases interdot coupling and decreases the distance over which carriers must tunnel. As a result, we double the diffusion length relative to reference CQD solids and report solar cells that achieve a stabilized power conversion efficiency (PCE) of 13.8%, a record among Pb chalcogenide CQD solar cells.

Two-dimensional (2D) nanosheets have attracted significant attention in photovoltaic devices in recent years owing to their outstanding photoelectric properties. Herein, 2D α-In2Se3 nanosheets with high conductivity and suitable work function are synthesized by liquid-phase exfoliation method. To ameliorate the low conductivity of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) (2.21 × 10-3 S cm-1), α-In2Se3 nanosheets are directly added into PEDOT:PSS to obtain the PEDOT:PSS:α-In2Se3 composite film. The composite film exhibits excellent optical transmittance, suitable work function, and enhanced conductivity (1.54 × 10-2 S cm-1). To profoundly investigate the mechanism of conductivity improvement, X-ray photoelectron spectroscopy, Raman spectroscopy, electron paramagnetic resonance, and atomic force microscopy are conducted. The results show that the synergistic effect of 2D α-In2Se3 nanosheets and isopropyl alcohol/deionized water cosolvent screens the Coulombic attraction among PEDOT and PSS. The screening effect results in the partial removal of PSS and the benzoid-quinoid transition of PEDOT. In addition, α-In2Se3 nanosheets may serve as physical linkers for PEDOT chains. Both these effects are beneficial to increase the interfacial contact area between PEDOT chains and form a larger conductive network of PEDOT, leading to an enhanced conductivity. The composite film is first employed as a hole transport layer (HTL) in polymer solar cells (PSCs). The power conversion efficiency (PCE) of the poly[2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene)-co-(1,3-di(5-thiophene-2-yl)-5,7-bis(2-ethylhexyl)benzo[1,2-c:4,5-c']dithiophene-4,8-dione)] (PBDB-T):3,9-bis(2-methylene(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)dithieno-[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene (ITIC)-based device with composite HTL is 10% higher than that of the unmodified PBDB-T:ITIC-based device, and the maximum PCE of 15.89% is achieved in the (poly[(2,6-(4,8-bis(5-(2-ethylhexyl)-4-fluorothiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene))-co-(1,3-di(5-thiophene-2-yl)-5,7-bis(2-ethylhexyl)-benzo[1,2-c:4,5-c']dithiophene-4,8-dione))] (PM6):(2,2'-((2Z,2Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2,″3″:4',50]thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile) (Y6) system. More interestingly, the stability of devices with composite HTL is improved owing to the partial removal of PSS. Thus, the PEDOT:PSS:α-In2Se3 composite can be a potential HTL material in PSCs.

Summary Living tissues are an integrated, multiscale architecture consisting of dense cellular ensembles and extracellular matrices (ECMs). The cells and ECMs cooperate to enable specialized mechanical properties and dynamic responsiveness. However, the mechanical properties of living tissues are difficult to replicate. A particular challenge is identification of a cell-like synthetic component, which is tightly integrated with its matrix and also responsive to external stimuli. Here, we demonstrate that cellular-scale hydrated starch granules, an underexplored component in materials science, can turn conventional hydrogels into tissue-like materials when composites are formed. By using several synchrotron-based X-ray techniques, we reveal the mechanically induced organization and training dynamics of the starch granules in the hydrogel matrix. These dynamic behaviors enable multiple tissue-like properties such as programmability, anisotropy, strain-stiffening, mechanochemistry, and self-healability.

Gas explosion has always been one of the leading disasters in chemical and mining industries, causing tremendous considerable casualties and property damage. It is very effective to control ignition parameters to prevent explosion accidents. To intensively investigate the impacts of C2H6/C2H4/CO/H2 mixtures on CH4 explosion, we added C2H6/C2H4/CO/H2 mixtures with different ratios (samples 1–4) and different volume fractions ([mixture] = 0–2.0 vol%) to CH4/air([CH4] = 7.0, 9.5 and 11.0 vol%) for measurement of the flammability limit and minimum oxygen concentration (MOC) for CH4 explosion in a 20-L spherical vessel. Changes of flammability limits of CH4 were obtained with the addition of C2H6/C2H4/CO/H2 mixtures at room temperature (18–22 °C) and pressure (1 atm). The experimental data about MOC of CH4 explosion were examined by principal component analysis (PCA). On the basis of experimental results, multiple regression models were established to determine the influences of principal components on MOC of CH4 explosion. The results clearly indicated that the impacts of organic and inorganic combustible gases on flammability limits of CH4 were significantly different. The involvement of sample 1 and sample 2 (main component is organic flammable gas) increased the explosive hazard degree (F value) of CH4 by 43.18% and 45.45%, respectively. However, it was increased by 15.91% and 4.55%, respectively after adding sample 3 or sample 4 (main component is inorganic flammable gas). Additionally, the required MOC for CH4 explosion was increased with the increase of C2H6/C2H4/CO/H2 mixtures, and they showed a quadratic parabola relationship. Moreover, the linear expressions between the concentrations of C2H6, C2H4, CO and H2 and the MOC of CH4 explosion were achieved by PCA. Based on these analyses, it is indicated that the effects of C2H6, C2H4 and CO were increasingly significant on MOC while H2 was just the opposite from the oxygen-rich state to the stoichiometric state and fuel-rich state for CH4/air mixture. The results presented in this paper can provide theoretical reference for the prevention and control of multiple flammable gas explosion.

We investigate directed self-assembly (DSA), with 3× density multiplication, of symmetric polystyrene-block-poly(methyl methacrylate) (L0 = 28 nm) with increasing film thicknesses and reveal a thic...

To investigate the effects of ethylene on methane-air explosions on a macro-to-micro level, the corresponding explosion and flame emission spectral behaviors were experimentally studied in a 20-L spherical chamber. The maximum explosion pressure, maximum pressure rising rate, and explosion duration were tested. The emission spectra of the key intermediates OH*, H* and CH2O* were obtained synchronously by using a photomultiplier-monochromator method. The detailed mechanism of GRI-Mech 3.0 was employed to analyze the kinetic reactions in the explosion process. A comprehensive analysis was performed by correlating the explosion parameters and emission spectral data. The results indicated that the added C2H4 would enhance the explosion of the fuel-lean methane-air mixture and attenuate the explosion of the fuel-rich mixture. It first promotes and then weakens the explosion of the stoichiometric methane-air mixture on the basis of the added volume fraction. The behavior of free radicals is well in accordance with the explosion parameters. The added C2H4 promotes the accumulation of the intermediates. Moreover, the variation in the production rate for the dominant reactions to generate the intermediates, caused by the addition of C2H4, directly results in a change in the average rising rate and maximum emission intensity of the intermediates.

The integration of metal-organic frameworks (MOFs) with semiconductors has attracted mounting attention for photocatalytic applications. However, more efforts are needed to unravel the interface structure in MOF/semiconductor composites and its role in charge transfer. Herein, a MIL-100(Fe)/TiO2 composite was synthesized as a prototypical photocatalyst and studied systematically to explore the interface structure and unravel the charge transfer pathways during the photocatalytic processes. The composite was fabricated by growing MIL-100(Fe) crystals on TiO2 using surface-coated FeOOH as the precursor. The as-prepared MIL-100(Fe)/TiO2 exhibited significantly improved photocatalytic performance over pristine TiO2, which was mainly because of the enhanced charge separation as confirmed by transient absorption spectroscopy analysis. This enhancement partially arose from the special chemical structure at the interface, where the Fe-O-Ti bond was formed. As verified by the density functional theory calculation, this distinct structure would create defect energy levels adjacent to the valence band maximum of TiO2. During the photocatalytic processes, the defect energy levels serve as sinks to capture excited charge carriers and retard the recombination, which subsequently leads to the increased charge density and promoted photocatalytic efficiency. Meanwhile, the intimate interactions between MIL-100(Fe) and TiO2 would also help to improve the charge separation by transferring photo-induced holes through the ligands to Fe-O clusters. These findings would advance the fundamental understanding of the interface structure and the charge transfer pathways in MOF/semiconductor composite photocatalysts.

This work aimed to experimentally evaluate the effects of a carbon monoxide-dominant gas mixture on the explosion characteristics of methane in air and report the results of an experimental study on explosion pressure measurement in closed vessel deflagration for a carbon monoxide-dominant gas mixture over its entire flammable range. Experiments were performed in a 20-L spherical explosion tank with a quartz glass window 110 mm in diameter using an electric spark (1 J) as the ignition source. All experiments were conducted at room temperature and at ambient pressure, with a relative humidity ranging from 52 to 73%. The peak explosion pressure (Pmax), maximum pressure rise rate ((dp/dt)max), and gas deflagration index (KG) were observed and analyzed. The flame propagation behavior in the initial stage was recorded using a high-speed camera. The spherical outward flame front was determined on the basis of a canny method, from which the maximum flame propagation speed (Sn) was calculated. The results indicated that the existence of the mixture had a significant effect on the flame propagation of CH4-air and increased its explosion risk. As the volume fraction of the mixed gas increases, the Pmax, (dp/dt)max, KG and Sn of the fuel-lean CH4-air mixture (7% CH4-air mixture) increase nonlinearly. In contrast, addition of the mixed gas negatively affected the fuel-rich mixture (11% CH4-air mixture), exhibiting a decreasing trend. Under stoichiometric conditions (9.5% CH4-air mixture), the mixed gas slightly lowered Pmax, (dp/dt)max, KG, and Sn. The Pmax of CH4-air mixtures at volume fractions of 7%, 9.5%, and 11% were 5.4, 6.9, and 6.8 bar, respectively. The Sn of CH4-air mixtures at volume fractions of 7%, 9.5%, and 11% were 1.2 m/s, 2.0 m/s, and 1.8 m/s, respectively. The outcome of the study is comprehensive data that quantify the dependency of explosion severity parameters on the gas concentration. In the storage and transportation of flammable gases, the information is required to quantify the potential severity of an explosion, design vessels able to withstand an explosion and design explosion safety measures for installations handling this gas.

How materials evolve at thermal equilibrium and under external excitations at small length and time scales is crucial to the understanding and control of material properties. X-ray photon correlation spectroscopy (XPCS) at X-ray free electron laser (XFEL) facilities can in principle capture dynamics of materials that are substantially faster than a millisecond. However, the analysis and interpretation of XPCS data is hindered by the strongly fluctuating X-ray intensity from XFELs. Here we examine the impact of pulse-to-pulse intensity fluctuations on sequential XPCS analysis. We show that the conventional XPCS analysis can still faithfully capture the characteristic time scales, but with substantial decrease in the signal-to-noise ratio of the g2 function and increase in the uncertainties of the extracted time constants. We also demonstrate protocols for improving the signal-to-noise ratio and reducing the uncertainties.

Controlled synthesis of nanostructure ultrathin films is critical for applications in nanoelectronics, photonics, and energy generation and storage. The paucity of structural probes that are sensitive to nanometer-thick films and also capable of in-operando conditions with high spatiotemporal resolutions limits the understanding of morphology and dynamics in ultrathin films. Similar to X-ray fluorescence holography for crystals, where holograms are formed through the interference between the reference and the object waves, we demonstrated that an ultrathin film, being an X-ray waveguide, can also generate fluorescence holograms as a result of the establishment of X-ray standing waves. Coupled with model-independent reconstruction algorithms based on rigorous dynamical scattering theories, the thin-film-based X-ray waveguide fluorescence holography becomes a unique in situ and time-resolved imaging probe capable of elucidating the real-time nanostructure kinetics with unprecedented resolutions. Combined with chemical sensitive spectroscopic analysis, the reconstruction can yield element-specific morphology of embedding nanostructures in ultrathin films., The authors introduce X-ray waveguide fluorescence holography based on the waveguiding properties of thin films. Combined with model-independent reconstruction algorithms, they show that the method can be used for real-time nanostructure kinetic studies.

A challenge of broad interest in both materials science and biology is the study of interfaces that are buried within a structure, particularly multilayer structures. Despite the enormous costs of corrosion and many decades of corrosion research, details of the mechanisms of various sorts of corrosion are still not clear, in part due to the difficulty in interrogating the interface between the corroding metal and an organic coating, which is typically used to mitigate corrosion. Generally, the performance of such coatings is evaluated by visual inspection after exposure or by modeling impedance data, which is a process not straightforwardly connected to physical interface structures. "Rocking-curve" X-ray scattering measurements provide a means of probing such interfaces due to the ability of X-rays to penetrate materials. Here, variations in the morphology of an interface between a protective coating and a metal substrate due to exposure to an electrolyte are derived from analysis of rocking-curve data in conjunction with atomic force microscopy imaging of the outer coating surface. The interfaces of cross-linked epoxy coatings with aluminum are irreversibly changed after 12 h of contact between the electrolyte solution and the face of the coating. The character of this change varies with the molecule used to cross-link the coating. Since X-ray off-specular scattering is sensitive to changes on the nanometer scale, it is also able to register interface degradation on time scales shorter than those probed by many other techniques, potentially expediting the evaluation of coatings for protection against degradation of the interface.

The search continues for means of making quick determinations of the efficacy of a coating for protecting a metal surface against corrosion. One means of reducing the time scale needed to differentiate the performance of different coatings is to draw from nanoscale measurements inferences about macroscopic behavior. Here we connect observations of the penetration of water into plasma polymerized (PP) protective coatings and the character of the interface between the coating and an oxide-coated aluminum substrate or model oxide-coated silicon substrate to the macroscopically observable corrosion for those systems. A plasma polymerized film from hexamethyldisiloxane (HMDSO) monomer is taken as illustrative of a hydrophobic coating, while a PP film from maleic anhydride (MA) is used as a characteristically hydrophilic coating. The neutron reflectivity (NR) of films on silicon oxide coated substrates shows that water moves more readily through the hydrophilic PP-MA film. Off-specular X-ray scattering indicates the PP-MA film on aluminum is less conformal with the substrate than is the PP-HMDSO film. Measurements with infrared-visible sum frequency generation spectroscopy (SFG), which probes the chemical nature of the interface, make clear that the chemical interactions between coating and aluminum oxide are disrupted by interfacial water. With this water penetration and interface disruption, macroscopic corrosion can occur much more rapidly. An Al panel coated with PP-MA corrodes after 1 day in salt spray, while a similarly thin (∼30 nm) PP-HMDSO coating protects an Al panel for a period on the order of one month.

Herein we report the finding that spectral reflectance (SR) can be used to identify thermal transitions in semi-crystalline polymer thin films. By studying film thickness as a function of temperature, we found that semi-crystalline polymers exhibit characteristic expansion and contraction profiles during the melting (Tm) and crystallization (Tc) transitions, respectively. Prior to this discovery, studies on the crystalline Tm in thin films have involved more expensive and complex techniques such as atomic force microscopy (AFM), ellipsometry, and grazing-incidence wide-angle X-ray scattering (GIWAXS). We correlate Tm and Tc as measured by SR with differential scanning calorimetry (DSC) in the bulk and temperature-controlled GIWAXS or AFM in thin films. We show that SR is accurate for measuring changes in films with thicknesses of 500 nm down to 21 nm and for detecting melting point depression due to thin film confinement. Thus, we demonstrate that SR is a powerful tool for measuring thermal transitions in semi-crystalline polymer films with single-degree resolution.

We report an in situ catalyst-free strategy to synthesize inorganic CsPbBr3 perovskite nanorods in a polymer matrix (NRs-PM) with good dimensional control, outstanding optical properties and ultrahigh environmental stability. Polarization photoluminescence (PL) imaging with high spatial resolution was carried out for the first time on single nanorod (NR) and shows a relatively high local polarization ratio (∼0.4) consistent with theoretical predictions based on a dielectric contrast model. We further demonstrate that macroscale alignment of the CsPbBr3 nanorods can be achieved through mechanically stretching the NRs-PM films at elevated temperature, without deteriorating the optical quality of the NRs. A polarization ratio of 0.23 is observed for these aligned NRs-PM films, suggesting their potential as polarized down-converters to increase the light efficiency in liquid crystal display (LCD) backlights.

The ineffective removal of antibiotics from the aquatic environment has raised serious problems, including chronic toxicity and antibiotic resistance. Among the numerous strategies, photocatalytic degradation appears to be one of the promising methods to remove antibiotics. Semiconductors are the most widely used photocatalysts, whereas, their efficiencies still suffer from limited light absorption and poor charge separation. Given their exceptional properties, including a superior surface area and massive active sites, MOFs are excellent candidates for the formation of hierarchical nanostructures with semiconductors to address the above issues. In this study, highly-oriented one-dimensional (1D) MIL-100(Fe)/TiO2 nanoarrays were developed as photocatalysts for the first time (MIL = Materials Institute Lavoisier). The 1D structured TiO2 nanoarrays not only enable the direct and enhanced charge transport, but also permit easy recycling. With the in situ growth of MIL-100(Fe) on the TiO2 nanoarrays, the composite exhibits enhanced light absorption, electron/hole separation, and accessibility of active sites. As a result, up to 90.79% photodegradation efficiency of tetracycline, a representative antibiotic, by the MIL-100(Fe)/TiO2 composite nanoarrays was achieved, which is much higher than that of pristine TiO2 nanoarrays (35.22%). It is also worth mentioning that the composite nanoarrays demonstrate high stability and still exhibit high efficiency twice that of the pristine TiO2 nanoarrays even in the 5th run. This study offers a new strategy for the degradation of antibiotics by using 1D MOF-based nanocomposite nanoarrays.

In this paper, we established the flow field and radiation intensity distribution models of water purification equipment based on computational fluid dynamics (CFD) technology and radiometric principles. From geometric shape to hydraulic state and radiation intensity distribution, we fully simulated the real scene of the Ultraviolet LED (UV-LED) water purification system, and provided the reliable data for the UV-LED in the water purification field. Compared with mercury lamp, UV-LEDs have a more flexible layout to produce a variety of radiation intensity distributions. UV dose (the product of radiation intensity over time) is an important indicator. We used a discrete phase model (DPM) to track the path of microbial particles, and found that the residence time of microorganisms in different parts of the model was different. By optimizing the UV-LED layout, the radiation intensity was increased in the sites where the microbes resided longer. The results show that we can improve the efficiency of the water purification equipment by simply adjusting the UV-LED layout without increasing the power, and make the UV dose achieves the national standard.

Generalized skew-symmetric probability density functions are proposed to model asymmetric interfacial density distributions for the parameterization of any arbitrary density profiles in the `effective-density model'. The penetration of the densities into adjacent layers can be selectively controlled and parameterized. A continuous density profile is generated and discretized into many independent slices of very thin thickness with constant density values and sharp interfaces. The discretized profile can be used to calculate reflectivities via Parratt's recursive formula, or small-angle scattering via the concentric onion model that is also developed in this work.

The quasi-static and dynamic deformation behavior of two Ta-W alloys (Ta-2.5W and Ta-10W, mass fraction) was investigated by the quasi-static and dynamic compression test and Split Hopkinson pressure bar (SHPB) and Taylor impact tests. The results show that the yield stress of Ta-W alloys exhibits sensitivity to strain rate and W content. Based on the quasi-static and high strain-rate experimental data, the material constants in Johnson-Cook (JC) model were obtained for the two Ta-W alloys. In addition, validation of the derived constitutive model was carried out through comparison of Taylor impact inhomogeneous deformations under high strain rate (103∼104 s−1), obtained from simulations with their experimental counterparts. It is shown that the simulation results agree well with post-test geometries in terms of side profiles and impact-interface footprints for Taylor impact tests. To bridge the different spatial scale involved in the process of tantalum-tungsten alloy deformation, a meso-scale research was proposed via optical microscope (OM) image analysis. The results presented in this paper, provide new insights into the mechanisms suitable for the constitutive relations determination process.

Controlling self-assembled nanostructures in thin films allows the bottom-up fabrication of ordered nanoscale patterns. Here we report the unique thickness-dependent phase behavior in thin films of a bolaform-like giant surfactant, which consists of butyl- and hydroxyl-functionalized polyhedral oligomeric silsesquioxane (BPOSS and DPOSS) cages telechelically located at the chain ends of a polystyrene (PS) chain with 28 repeating monomers on average. In the bulk, BPOSS-PS28-DPOSS forms a double gyroid (DG) phase. Both grazing incidence small-angle X-ray scattering and transmission electron microscopy techniques are combined to elucidate the thin film structures. Interestingly, films with thicknesses thinner than 200 nm exhibit an irreversible phase transition from hexagonal perforated layer (HPL) to compressed hexagonally packed cylinders (c-HEX) at 130 °C, while films with thickness larger than 200 nm show an irreversible transition from HPL to DG at 200 °C. The thickness-controlled transition pathway sug...

The cold-rolled bonding process of copper/aluminum bimetal plate was investigated by the velocity field of finite element method (FEM). At the same time, deformation characteristics of metal were analyzed in the bonding process. The study method was to combine theory calculation with field data. The circumferential velocity of rollers, rolling reduction rate, synchronous rolling of non-equal sized rollers and asymmetrical rolling of non-equal sized rollers were analyzed. Results show that the velocity field can explain the cold-rolled bonding process of copper/aluminum bimetal plate more effectively; the synchronicity of metal flow on bonding surface decreases with the increase of circumferential velocity about rollers near the exit of deformation area, and the bonding strength is reduced; in the process of synchronous rolling about non-equal sized rollers, diameter ratio of the rolls is 1.4∼1.6 with a great synchronicity of metal flow near the exit of deformation area and a high bonding strength; in the process of asymmetrical rolling about non-equal sized rollers, the circumferential velocity rate of rollers is 1.2 with a great synchronicity of metal flow near the exit of deformation area and a high bonding strength.

Two novel donor–acceptor π-conjugated polymers based on naphthodipyrrolidone (NDP) were synthesized and characterized. The polymers possess low band gaps and suitable molecular orbital levels as ambipolar semiconductors. The thin film organic field effect transistor of NDP polymers exhibited ambipolar transport properties with a high electron mobility up to 0.67 cm2 V−1 s−1. The grazing-incidence wide-angle X-ray scattering (GIWAXS) studies demonstrated that the polymer molecules pack into a long-range-ordered lamellar structure with isotropically oriented crystalline domains. Thermal annealing promoted edge-on lamellar stacking as evidenced by the increased diffraction intensity along the out-of-plane direction. The polymer with NDP and bithiophene units achieved the best edge-on lamellar stacking after thermal annealing, which yielded the best electron transport performance in this work.

In recent years, applications of different types of solid waste in fiber-reinforced soil are developed to improve the strength of soil. This study presents an experimental investigation of mechanical properties of polypropylene fiber-reinforced fly ash-soil mixtures. A series of direct shear tests and unconfined compression tests were carried out. The effects of fly ash content and fiber content on compaction characteristics, shear strength, strength parameters, and unconfined compressive strength of the reinforced soil are investigated and discussed. Results reveal that when the fly ash content of the specimen exceeds 20% and the curing period exceeds 14 days, specimens become more brittle in the unconfined compression tests. It can be deduced that 30% fly ash and 1% fiber provide the optimum content, and the inclusion of fiber reinforcement has positive benefits on the mechanical properties of the reinforced soil to a certain extent.

Based on the patient’s CT scanning data, a highly efficient and controllable porous element and a porous structure modeling method are studied, and the design structure and mechanical parameters are simulated and estimated. The porous titanium alloy implants are produced by laser selective melting, and the surface treatment is made by micro arc oxidation technique to prepare the precision. Less than 0.01 mm, the porous, controllable and active titanium alloy implanted with the thickness of the hydroxyl phosphor layer thickness >10 μm, the results of rational detection, comprehensive analysis and evaluation, forming the corresponding technical standards and technical standards, verifying the feasibility of the application of the technology in the application of titanium alloy materials in the Department of orthopedics, and the implantation of the porous titanium alloy. The application of body in the field of Department of orthopedics implantation provides material foundation and technical support.

Summary The irreversible phase transition by water incorporation, along with thermal decomposition, has long been thought to be the dominant degradation pathway to deteriorate electronic and optoelectronic properties of perovskite devices. However, comprehensive characterization and insightful understanding of beneficial effect of water incorporation remains scarce. Here, we capture the phase transformation of perovskite in situ from its precursor stage to the final film upon thermal annealing as a function of relative humidity (RH) by grazing-incident wide-angle X-ray scattering. Quantitative structural analyses show that a moderate water content (RH 40%) enhances the texture orientation of the perovskite. A consequence of the guided water-incorporated treatment is that the unencapsulated device, without any sophisticated instability-mitigation approaches, exhibits excellent tolerance to long-term, light soaking and high-temperature aging, retaining more than 80% of the peak power-conversion efficiency under constant 1-sun illumination or heating at 65°C for more than 1,000 h, respectively.

The coarse primary silicon structure will deteriorate the material properties of Al-Si alloy. It is necessary to optimize the morphology and size of primary silicon through modification, so as to improve the properties of Al-Si alloy. In this paper, four different phosphorus modifiers, AlP4, P-salt, P-Cu and Al-3P, were used to modify the Al-Si alloy. The microstructure and mechanical properties of the modified Al-Si alloy were compared and analyzed.

Swollen polymer brushes are found in various applications including biomedical coatings where the brush provides stability against harsh environmental conditions and mediates interactions with the surroundings. The surface height fluctuations of planar polystyrene brushes (0.04–0.61 chains/nm2) highly swollen in toluene vapor are so strongly slowed by the tethering of the chains that they are unobservable in the current experimental window of length and time. This is the case despite the fact that the segmental dynamics of the brush chains should be very fast due to the substantial plasticization by the solvent. With respect to thermally stimulated fluctuations, the surfaces of these swollen brushes are solidlike on time scales and length scales pertinent to many practical applications.

Grazing-incidence small-angle X-ray scattering (GISAXS) is increasingly used for the metrology of substrate-supported nanoscale features and nanostructured films. In the case of line gratings, where long objects are arranged with a nanoscale periodicity perpendicular to the beam, a series of characteristic spots of high-intensity (grating truncation rods, GTRs) are recorded on a two-dimensional detector. The intensity of the GTRs is modulated by the three-dimensional shape and arrangement of the lines. Previous studies aimed to extract an average cross-sectional profile of the gratings, attributing intensity loss at GTRs to sample imperfections. Such imperfections are just as important as the average shape when employing soft polymer gratings which display significant line-edge roughness. Herein are reported a series of GISAXS measurements of polymer line gratings over a range of incident angles. Both an average shape and fluctuations contributing to the intensity in between the GTRs are extracted. The results are critically compared with atomic force microscopy (AFM) measurements, and it is found that the two methods are in good agreement if appropriate corrections for scattering from the substrate (GISAXS) and contributions from the probe shape (AFM) are accounted for.

Lanthanide ions (Ln3+) doped upconversion materials have attracted great attention due to their potential applications in volumetric display, anti-counterfeiting, biodetection and biotherapy. However, red-emitting upconversion phosphors are scarcely reported especially basing on NaLnF4, which is the most efficient host matrix. Herein, we reported intensive red emissions observed in a low doping content NaLuF4:Yb/Er (20/1 mol%) microrod. The intensive red emission is considered to be obtained by the facilitated three-photon population routes of 4F9/2 energy levels of Er3+. Moreover, upon pulsed laser excitation its emission color can be rationally manipulated from red to yellow and to green. This is attributed to the temporal response deviation between 4S3/2 and 4F9/2 energy levels of Er3+, which impels green and red emission bands to reach different ratios under pulsed laser excitation. The color-manipulation method can also be applied to other red-emitting upconversion phosphors, enabling extended applications in volumetric colorful display, high-security-level anti-counterfeiting and deep-tissue bioimaging.

Revealing interfacial structure and dynamics has been one of the essential thematic topics in material science and condensed matter physics. Synchrotron-based x-ray scattering techniques can deliver unique and insightful probing of interfacial structures and dynamics, in particular, in reflection geometries with higher surface and interfacial sensitivity than transmission geometries. We demonstrate the design and implementation of an in situ shearing x-ray measurement system, equipped with both inline parallel-plate and cone-and-plate shearing setups and operated at the advanced photon source at Argonne National Laboratory, to investigate the structures and dynamics of end-tethered polymers at the solid-liquid interface. With a precise lifting motor, a micrometer-scale gap can be produced by aligning two surfaces of a rotating upper shaft and a lower sample substrate. A torsional shear flow forms in the gap and applies tangential shear forces on the sample surface. The technical combination with nanoscale rheology and the utilization of in situ x-ray scattering allow us to gain fundamental insights into the complex dynamics in soft interfaces under shearing. In this work, we demonstrate the technical scope and experimental capability of the in situ shearing x-ray system through the measurements of charged polymers at both flat and curved interfaces upon shearing. Through the in situ shearing x-ray scattering experiments integrated with theoretical simulations, we aim to develop a detailed understanding of the short-range molecular structure and mesoscale ionic aggregate morphology, as well as ion transport and dynamics in soft interfaces, thereby providing fundamental insight into a long-standing challenge in ionic polymer brushes with a significant technological impact.

The capability of transferring target materials especially functionality-reliable biomolecules, into specific locations and with arbitrarily designed patterns are of critical importance for high-throughput disease diagnosis, multiplexing, and drug screening. Herein, we report the simultaneous patterning of two types of biomolecules using the parallel dip-pen nanolithography technology where an array of the atomic force microscope (AFM) tips can be selectively and alternately coated with target biomolecules via a specially designed inkwell array. Moreover, mixing target biomolecules at a proper volumetric ratio with polyethylene glycol dissolved in PBS buffer solution that works as an ink carrier can not only facilitate the smooth transfer of ink materials from the AFM tip to the substrate, it can also help to adjust the ink diffusion constant of different biomolecules to be highly similar so that the multiplexed biofunctional dot and/or line arrays at similar sizes can be reliably generated.

We investigated the dynamics of polymer-grafted gold nanoparticles loaded into polymer melts using x-ray photon correlation spectroscopy. For low molecular weight host matrix polymer chains, normal isotropic diffusion of the gold nanoparticles is observed. For larger molecular weights, anomalous diffusion of the nanoparticles is observed that can be described by ballistic motion and generalized Levy walks, similar to those often used to discuss the dynamics of jammed systems. Under certain annealing conditions, the diffusion is one-dimensional and related to the direction of heat flow during annealing and is associated with an dynamic alignment of the host polymer chains. Molecular dynamics simulations of a single gold nanoparticle diffusing in a partially aligned polymer network semiquantitatively reproduce the experimental results to a remarkable degree. The results help to showcase how nanoparticles can under certain circumstances move rapidly in polymer networks.

We experimentally probed the stress relaxation of a monolayer of iron oxide nanoparticles at the water-air interface. Upon drop-casting onto a water surface, the nanoparticles self-assembled into islands of two-dimensional hexagonally close packed crystalline domains surrounded by large voids. When compressed laterally, the voids gradually disappeared as the surface pressure increased. After the compression was stopped, the surface pressure (as measured by a Wilhelmy plate) evolved as a function of the film aging time with three distinct timescales. These aging dynamics were intrinsic to the stressed state built up during the non-equilibrium compression of the film. Utilizing x-ray photon correlation spectroscopy, we measured the characteristic relaxation time (τ) of in-plane nanoparticle motion as a function of the aging time through both second-order and two-time autocorrelation analysis. Compressed and stretched exponential fitting of the intermediate scattering function yielded exponents (β) indicating different relaxation mechanisms of the films under different compression stresses. For a monolayer compressed to a lower surface pressure (between 20 mN/m and 30 mN/m), the relaxation time (τ) decreased continuously as a function of the aging time, as did the fitted exponent, which transitioned from being compressed (>1) to stretched (

Molecular engineering of intra- and interchain interactions transforms polymers into good heat conductors., Traditional polymers are both electrically and thermally insulating. The development of electrically conductive polymers has led to novel applications such as flexible displays, solar cells, and wearable biosensors. As in the case of electrically conductive polymers, the development of polymers with high thermal conductivity would open up a range of applications in next-generation electronic, optoelectronic, and energy devices. Current research has so far been limited to engineering polymers either by strong intramolecular interactions, which enable efficient phonon transport along the polymer chains, or by strong intermolecular interactions, which enable efficient phonon transport between the polymer chains. However, it has not been possible until now to engineer both interactions simultaneously. We report the first realization of high thermal conductivity in the thin film of a conjugated polymer, poly(3-hexylthiophene), via bottom-up oxidative chemical vapor deposition (oCVD), taking advantage of both strong C=C covalent bonding along the extended polymer chain and strong π-π stacking noncovalent interactions between chains. We confirm the presence of both types of interactions by systematic structural characterization, achieving a near–room temperature thermal conductivity of 2.2 W/m·K, which is 10 times higher than that of conventional polymers. With the solvent-free oCVD technique, it is now possible to grow polymer films conformally on a variety of substrates as lightweight, flexible heat conductors that are also electrically insulating and resistant to corrosion.

Using high-resolution in situ small angle x-ray scattering in conjunction with oscillatory shear on highly monodisperse silica suspensions, we demonstrate that an order-to-disorder transition leads to a dynamic shear thickening in a lower stress regime than the standard steady shear thickening. We show that the order-to-disorder transition is controlled by strain, which is distinguishably different from steady shear thickening, which is a stress-related phenomenon. The appearance of this two-step shear thinning and thickening transition is also influenced by the particle size, monodispersity, and measurement conditions (i.e., oscillatory shear versus steady shear). Our results show definitively that the order-to-disorder transition-induced thickening is completely unrelated to the mechanism that drives steady shear thickening.

The self-assembly behavior of specifically designed giant surfactants is systematically studied in thin films using grazing incidence X-ray scattering and transmission electron microscopy, focusing on the effects of molecular nanoparticle (MNP) functionalities and molecular architectures on nanostructure formation. Two MNPs with different surface functionalities, i.e., hydrophilic carboxylic acid functionalized [60]fullerene (AC60) and omniphobic fluorinated polyhedral oligomeric silsesquioxane (FPOSS), are utilized as the head portions of the giant surfactants. By covalently tethering these functional MNPs onto the end point or junction point of polystyrene-block-poly(ethylene oxide) (PS-b-PEO) diblock copolymer, linear and star-like giant surfactants with different molecular architectures are constructed. With fixed length of the PEO block, changing the molecular weight of the PS block leads to the formation of various ordered phases and phase transitions. Due to the distinct affinity, the AC60-based and FPOSS-based giant surfactants form two- or three-component morphologies, respectively. A stretching parameter for the PS block is introduced to characterize the PS chain conformation in the different morphologies. The highly diverse self-assembled nanostructures with high etch resistance between components in small dimensions obtained from the giant surfactant thin films suggest that these macromolecules could provide a promising and robust platform for nanolithography applications.

Self-assembly of nanoparticles at fluid interfaces has emerged as a simple yet efficient way to create two-dimensional membranes with tunable properties. In these membranes, inorganic nanoparticles are coated with a shell of organic ligands that interlock as spacers and provide tensile strength. Although curvature due to gradients in lipid-bilayer composition and protein scaffolding is a key feature of many biological membranes, creating gradients in nanoparticle membranes has been difficult. Here, we show by X-ray scattering that nanoparticle membranes formed at air/water interfaces exhibit a small but significant ∼6 Å difference in average ligand-shell thickness between their two sides. This affects surface-enhanced Raman scattering and can be used to fold detached free-standing membranes into tubes by exposure to electron beams. Molecular dynamics simulations elucidate the roles of ligand coverage and mobility in producing and maintaining this asymmetry. Understanding this Janus-like membrane asymmetry opens up new avenues for designing nanoparticle superstructures.

GIXSGUI is a MATLAB toolbox that offers both a graphical user interface and script-based access to visualize and process grazing-incidence X-ray scattering data from nanostructures on surfaces and in thin films. It provides routine surface scattering data reduction methods such as geometric correction, one-dimensional intensity linecut, two-dimensional intensity reshaping etc. Three-dimensional indexing is also implemented to determine the space group and lattice parameters of buried organized nanoscopic structures in supported thin films.

To meet the requirements of the energy storage materials for high energy density and high power density, porous silicon carbide/derived carbon-spherical natural graphite (SiC-CDCs@NG) composites were prepared. The composites were composed of tailored porous carbide-derived carbon and graphitized carbon with excellent conductivity and a high energy storage capacity. The composition, structure, morphology, pore structure, and specific surface area of the composites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, and N2 adsorption/ desorption analysis. The composites exhibited a high and adjustable specific surface area and micro-pore volume, with a micro-pore size of between 0.5 and 0.7 nm. Varying the molar ratio of NG and Si allowed optimization of the micro-pore volume, pore size distribution, specific surface area, and composition and content of the CDCs shell and NG core.

Although spin casting and chemical surface reactions are the most common methods used for fabricating functional polymer films onto substrates, they are limited with regard to producing films of certain morphological characteristics on different wetting and nonwetting substrates. The matrix-assisted pulsed laser evaporation (MAPLE) technique offers advantages with regard to producing films of different morphologies on different types of substrates. Here, we provide a quantitative characterization, using X-ray diffraction and optical methods, to elucidate the additive growth mechanism of MAPLE-deposited poly(3-hexylthiophene) (P3HT) films on substrates that have undergone different surface treatments, enabling them to possess different wettabilities. We show that MAPLE-deposited films are composed of crystalline phases, wherein the overall P3HT aggregate size and crystallite coherence length increase with deposition time. A complete pole figure constructed from X-ray diffraction measurements reveals that in these MAPLE-deposited films, there exist two distinct crystallite populations: (i) highly oriented crystals that grow from the flat dielectric substrate and (ii) misoriented crystals that preferentially grow on top of the existing polymer layers. The growth of the highly oriented crystals is highly sensitive to the chemistry of the substrate, whereas the effect of substrate chemistry on misoriented crystal growth is weaker. The use of a self-assembled monolayer to treat the substrate greatly enhances the population and crystallite coherence length at the buried interfaces, particularly during the early stage of deposition. The evolution of the in-plane carrier mobilities during the course of deposition is consistent with the development of highly oriented crystals at the buried interface, suggesting that this interface plays a key role toward determining carrier transport in organic thin-film transistors.

“Partially tethering” a thin film of a polymer melt by covalently attaching to the substrate a fraction of the chains in an unentangled melt dramatically increases the relaxation time of the surface height fluctuations. This phenomenon is observed even when the film thickness, h, is 20 times the unperturbed chain radius, Rg,tethered, of the tethered chains, indicating that partial tethering is more influential than any physical attraction with the substrate. Furthermore, a partially tethered layer of a low average molecular weight of 5k showed much slower surface fluctuations than did a reference layer of pure untethered chains of much greater molecular weight (48k), so the partial tethering effect is stronger than the effects of entanglement and increase in glass transition temperature, Tg, with molecular weight. Partial tethering offers a means of tailoring these fluctuations which influence wetting, adhesion, and tribology of the surface.

The commercialization of nonfullerene organic solar cells (OSCs) critically relies on the response under typical operating conditions (for instance, temperature and humidity) and the ability of scale-up. Despite the rapid increase in power conversion efficiency (PCE) of spin-coated devices fabricated in a protective atmosphere, the efficiencies of printed nonfullerene OSC devices by blade coating are still lower than 6%. This slow progress significantly limits the practical printing of high-performance nonfullerene OSCs. Here, a new and relatively stable nonfullerene combination is introduced by pairing the nonfluorinated acceptor IT-M with the polymeric donor FTAZ. Over 12% efficiency can be achieved in spin-coated FTAZ:IT-M devices using a single halogen-free solvent. More importantly, chlorine-free, blade coating of FTAZ:IT-M in air is able to yield a PCE of nearly 11% despite a humidity of ≈50%. X-ray scattering results reveal that large π–π coherence length, high degree of face-on orientation with respect to the substrate, and small domain spacing of ≈20 nm are closely correlated with such high device performance. The material system and approach yield the highest reported performance for nonfullerene OSC devices by a coating technique approximating scalable fabrication methods and hold great promise for the development of low-cost, low-toxicity, and high-efficiency OSCs by high-throughput production.

Due to their unique properties, polymers – typically thermal insulators – can open up opportunities for advanced thermal management when they are transformed into thermal conductors. Recent studies have shown polymers can achieve high thermal conductivity, but the transport mechanisms have yet to be elucidated. Here we report polyethylene films with a high thermal conductivity of 62 Wm−1 K−1, over two orders-of-magnitude greater than that of typical polymers (~0.1 Wm−1 K−1) and exceeding that of many metals and ceramics. Structural studies and thermal modeling reveal that the film consists of nanofibers with crystalline and amorphous regions, and the amorphous region has a remarkably high thermal conductivity, over ~16 Wm−1 K−1. This work lays the foundation for rational design and synthesis of thermally conductive polymers for thermal management, particularly when flexible, lightweight, chemically inert, and electrically insulating thermal conductors are required., Thermally conductive polymers can be used for advanced thermal management applications but the transport mechanisms have yet to be elucidated. Here the authors report the synthesis of polyethylene films with high thermal conductivity, which is attributed to the amorphous regions of the nanofibers.

The microporous nature of the porous organic polymer (POP) successfully limits the crystallization of sulfur and hence restrains the dissolution and diffusion of lithium polysulfides formed during the repeated charge and discharge process of lithium–sulfur batteries. In this study, we demonstrated for the first time that a POP–sulfur nanocomposite can lead to high coulombic efficiency and superior reversibility in lithium–sulfur batteries.

Bismuth oxysulfide (Bi2O2S) has been demonstrated as a potential candidate for photovoltaic material because of favorite band gap (1.5 eV), effective charge dissociation, high carrier mobility, and long carrier lifetime. In this work, we synthesis the Bi2O2S nanocrystals by hydrothermal method, and incorporate Bi2O2S nanocrystals as a third component into poly[[4,8-bis[(2-ethylhexyl)oxy]benzo [1,2-b:4,5-b'] dithiophene-2,6-diyl] [3-fluoro-2-(2-ethylhexy) carbonyl] thieno [3,4-b] thiophenediyl]] (PTB7):acceptor [6,6]-pheny C71-butyric acid methy ester (PC71BM) binary polymer solar cells (PSCs). The results show that the power conversion efficiency (PCE) of ternary PSCs is obviously improved by 21.8% in comparison with binary PSCs (from 8.79% to 10.71%) by adding 1 wt% Bi2O2S nanocrystals. Introduction of Bi2O2S nanocrystals into the PTB7:PC71BM system can expand absorption range of sunlight in the PSCs, effectively enhance the crystallinity of PTB7 and optimize the surface morphology of photoactive layer, which leads to more efficient photon harvesting, enhances exciton dissociation, accelerates charge carrier transport and reduces charge recombination. Moreover, the addition of appropriate amounts of Bi2O2S nanocrystals into PTB7:PC71BM can effectively improve the lifetime of PSCs due to the improvement of crystallinity of PTB7. This work demonstrates the great potential use of bismuth compounds for photovoltaic devices fields.