Search Results (26)

It is widely recognized that fine surface structures found in nature contribute to surface functionality, and studies on the design of functional materials based on biomimetics have been actively conducted. In this study, polymer thin films with hierarchically ordered surface structure were prepared by combining both nanoimprinting using anodically oxidized porous alumina (AAO) as a template and surface-initiated atom transfer radical polymerization (SI-ATRP). To prepare such polymer films, we designed a new copolymer (poly{[2-(4-methyl-2-oxo-2H-chromen-7-yloxy)ethyl methacrylate]-co-[2-(2-bromo-2-methylpropionyloxy)ethyl methacrylate]}; poly(MCMA-co-HEMABr)) with coumarin moieties and α-haloester moieties in the pendants. The MCMA repeating units function to fix the pillar structure by photodimerization, and the HEMABr ones act as the polymerization initiation sites for SI-ATRP on the pillar surfaces. Surface structures consisting of vertically oriented multiple pillars were fabricated on the spin-coated poly(MCMA-co-HEMABr) thin films by nanoimprinting using an AAO template. Then, the coumarin moieties inside each pillar were crosslinked by UV light irradiation to fix the pillar structure. SEM observation confirmed that the internally crosslinked pillar structures were maintained even when immersed in organic solvents such as 1,2-dichloroethane and anisole, which are employed as solvents under SI-ATRP conditions. Finally, poly(2,2,2-trifluoroethyl methacrylate) and poly(N-isopropylacrylamide) chains were grafted onto the thin film by SI-ATRP, respectively, to prepare the hierarchically ordered surface structure. Furthermore, in this study, the surface properties as well as the thermoresponsive hydrophilic/hydrophobic switching of the obtained polymer films were investigated. The surface morphology and chemistry of the films with and without pillar structures were compared, especially the interfacial properties expressed as wettability. Grafting poly(TFEMA) increased the static contact angle for both flat and pillar films, and the con-tact angle of the pillar film surface increased from 104° for the flat film sample to 112°, suggesting the contribution of the pillar structure. Meanwhile, the pillar film surface grafted with poly(NIPAM) brought about a significant change in wettability when changing the temperature between 22 °C and 38 °C. Full article

The focus of this work was to perform a preliminary study on the suitability of commercially available nanofiltration (NF) and reverse osmosis (RO) membranes for the separation of 1,3-propanediol (1,3-PD) post-fermentation solutions. The experiments were conducted with the use of AFC30 and AFC99 (PCI Membrane System Inc., Milford, OH, USA) as well as BW30 membranes (Dow FilmTec Co., Midland, MI, USA) and various feed solutions: selected compounds of fermentation broths, and synthetic and real fermentation broths. Firstly, it was found that for pure water, the AFC30 membrane was characterized by the highest performance. It clearly indicated that the membrane is the most open membrane and is characterized by a more porous structure. In turn, the lowest flux was noted for the AFC99 membrane. Studies performed with the use of synthetic broth found that for the BW30 membrane, the order in which the rejection coefficient (R) was obtained was glycerol~lactic acid > 1,3-propanediol > acetic acid. It clearly confirmed that the R increased with the molecular weight (MW) of the solution compounds. With regard to ions, it was found that SO₄²⁻ and PO₄³⁻ is characterized by higher R than Cl⁻ and NO₃⁻ ions. Multivalent ions are characterized by higher charge density, hydrated radius, hydration energy and MW. Finally, experiments performed with the use of the AFC30 membrane and real broths showed that the membrane ensured almost complete separation of 1,3-PD. With regard to organic acid, the separation performance was as follows: succinic acid > lactic acid > butyric acid > acetic acid > formic acid. It has been documented that the AFC30 membrane can be successfully used to concentrate the following ions: SO₄²⁻, PO₄³⁻, NO₃⁻ and Na⁺. Hence, most of the medium used for the fermentation process was retained by the membrane and may be reused, which is crucial for the scaling up of the process and reducing the total technology cost. With regard to the obtained permeate, it can be subsequently purified by other methods, such as distillation or ion exchange. For further development of the tested process, determining the retention degree for 1,3-PD and other solutes during long-term separation of real broth is necessary. Full article

Anodic aluminum oxide (AAO) has been widely applied for the surface protection of electronic component packaging through a pore-sealing process, with the enhanced hardness value reaching around 400 Vickers hardness (HV). However, the traditional AAO fabrication at 0~10 °C for surface protection takes at least 3–6 h for the reaction or other complicated methods used for the pore-sealing process, including boiling-water sealing, oil sealing, or salt-compound sealing. With the increasing development of nanostructured AAO, there is a growing interest in improving hardness without pore sealing, in order to leverage the characteristics of porous AAO and surface protection properties simultaneously. Here, we investigate the effect of voltage on hardness under the same AAO thickness conditions in oxalic acid at room temperature from a normal level of 40 V to a high level of 100 V and found a positive correlation between surface hardness and voltage. The surface hardness values of AAO formed at 100 V reach about 423 HV without pore sealing in 30 min. By employing a hybrid pulse anodization (HPA) method, we are able to prevent the high-voltage burning effect and complete the anodization process at room temperature. The mechanism behind this can be explained by the porosity and photoluminescence (PL) intensity of AAO. For the same thickness of AAO from 40~100 V, increasing the anodizing voltage decreases both the porosity and PL intensity, indicating a reduction in pores, as well as anion and oxygen vacancy defects, due to rapid AAO growth. This reduction in defects in the AAO film leads to an increase in hardness, allowing us to significantly enhance AAO hardness without a pore-sealing process. This offers an effective hardness enhancement in AAO under economically feasible conditions for the application of hard coatings and protective films. Full article

In this study, we propose a new sub-diffusion two-temperature model and its accurate numerical method by introducing the Knudsen number ($K_n$) and two Caputo fractional derivatives ($0<\alpha ,\beta <1$) in time into the parabolic two-temperature model of the diffusive type. We prove that the obtained sub-diffusion two-temperature model is well posed. The numerical scheme is obtained based on the $L1$ approximation for the Caputo fractional derivatives and the second-order finite difference for the spatial derivatives. Using the discrete energy method, we prove the numerical scheme to be unconditionally stable and convergent with $O({\tau }^{min\{2-\alpha ,2-\beta \}}+h^2)$, where $\tau ,h$ are time and space steps, respectively. The accuracy and applicability of the present numerical scheme are tested in two examples. Results show that the numerical solutions are accurate, and the present model and its numerical scheme could be used as a tool by changing the values of the Knudsen number and fractional-order derivatives as well as the parameter in the boundary condition for analyzing the heat conduction in porous media, such as porous thin metal films exposed to ultrashort-pulsed lasers, where the energy transports in phonons and electrons may be ultraslow at different rates. Full article

In this work, thin film composite (TFC) membranes were fabricated with the selective layer based on a blend of polyimide Matrimid^®5218 and polymer of intrinsic microporosity (PIM) composed of Tröger’s base, TB, and dimethylethanoanthracene units, PIM-EA(Me₂)-TB. The TFCs were prepared with different ratios of the two polymers and the effect of the PIM content in the blend of the gas transport properties was studied for pure He, H₂, O₂, N₂, CH₄, and CO₂ using the well-known time lag method. The prepared TFC membranes were further characterized by IR spectroscopy and scanning electron microscopy (SEM). The role of the support properties for the TFC membrane preparation was analysed for four different commercial porous supports (Nanostone Water PV 350, Vladipor Fluoroplast 50, Synder PAN 30 kDa, and Sulzer PAN UF). The Sulzer PAN UF support with a relatively small pore size favoured the formation of a defect-free dense layer. All the TFC membranes supported on Sulzer PAN UF presented a synergistic enhancement in CO₂ permeance, and CO₂/CH₄ and CO₂/N₂ ideal selectivity. The permeance increased about two orders of magnitude with respect to neat Matrimid, up to ca. 100 GPU, the ideal CO₂/CH₄ selectivity increased from approximately 10 to 14, and the CO₂/N₂ selectivity from approximately 20 to 26 compared to the thick dense reference membrane of PIM-EA(Me₂)-TB. The TFC membranes exhibited lower CO₂ permeances than expected on the basis of their thickness—most likely due to enhanced aging of thin films and to the low surface porosity of the support membrane, but a higher selectivity for the gas pairs CO₂/N₂, CO₂/CH₄, O₂/N₂, and H₂/N₂. Full article

With the fast consumption of traditional fossil fuels and the urgent requirement for a low-carbon economy and sustainable development, supercapacitors are gaining more and more attention as a clean energy storage and conversion device. The research on electrode materials for supercapacitors has become a hot topic nowadays. An electrode material for a supercapacitor, comprising the ZIF-67 in-built carbon-based material, was prepared from a biomass pre-hydrolysate via a hydrothermal process. As a by-product of dissolving slurry, the pre-hydrolysate is rich in carbon, which is an excellent biomass resource. The utilization of pre-hydrolysate to prepare carbon energy materials could realize the high value utilization of pre-hydrolysate and the efficient energy conversion of biomass. Meanwhile, the cobalt-based MOF (such as ZIF-67), as a porous crystalline material, has the advantages of having a regular order, high specific surface area and controllable pore size, as well as good thermal and chemical stability. The addition of ZIF-67 modified the morphology and pore structure of the carbon, and the obtained samples showed outstanding electrochemical performance. One- and two-step synthetic processes generated specimens with a coral-like cross-linked structure and a new type of rough, hollow, dandelion-like structure, respectively, and the pore size was in the range of 2.0–5.0 nm, which is conducive to ion transport and charge transfer. In C2-ZIF-67, the hollow structures could effectively prevent the accumulation of the electrochemical active center, which could provide enough space for the shrinkage and expansion of particles to protect them from the interference of electrolytes and the formation of solid electrolyte interphase film layers. Additionally, the plush tentacle structure with low density and a large specific surface area could expose more active sites and a large electrolyte electrode contact area, and short electron and charge transport paths. Importantly, active, free electrons of small amounts of Co-MOF (1 wt%) could be stored and released through the redox reaction, further improving the electrical conductivity of Carbon-ZIF-67 materials in this work. Consequently, C2-ZIF-67 exhibited superior specific capacitance (400 F g⁻¹, at 0.5 A g⁻¹) and stability (90%, after 10,000 cycles). Full article

This study employed response surface methodology to optimize the preparation of biocomposites based on whey protein isolate, glycerol, and nanocrystalline cellulose from pineapple crown leaf. The effects of different concentrations of nanocrystalline cellulose as a filler and glycerol as a plasticizer on the thickness, the tensile strength, and the elongation at break on the resulting biocomposite films were investigated. The central composite design was used to determine the optimum preparation conditions for biocomposite films with optimum properties. The regression of a second-order polynomial model resulted in an optimum composition consisting of 4% glycerol and 3.5% nanocrystalline cellulose concentrations, which showed a desirability of 92.7%. The prediction of the regression model was validated by characterizing the biocomposite film prepared based on the optimum composition, at which the thickness, tensile strength, and elongation at break of the biocomposite film were 0.13 mm, 7.16 MPa, and 39.10%, respectively. This optimum composition can be obtained in range concentrations of glycerol (4–8%) and nanocrystalline cellulose (3–7%). Scanning electron microscope images showed that nanocrystalline cellulose dispersed well in the pure whey protein isolate, and the films had a relatively smooth surface. In comparison, a rough and uneven surface results in more porous biocomposite films. Fourier transform infrared spectroscopy revealed that nanocrystalline cellulose and glycerol showed good compatibility with WPI film by forming hydrogen bonds. The addition of nanocrystalline cellulose as a filler also decreased the transparency, solubility, and water vapor permeability and increased the crystallinity index of the resulting biocomposite film. Full article

Liquid-Infused Surfaces (LISs), particularly known for their liquid-repelling feature, have demonstrated plenty of applications in the medical, marine, and energy fields. To improve the durability and transparency highly demanded on glass-based vision devices such as an endoscope, this study proposed a novel self-assembly method to fabricate well-ordered porous Poly-Styrene (PS)/Styrene–Butadiene–Styrene (SBS) films by simply dripping the PS/SBS dichloromethane solutions onto the glass before spinning. The effects of the solutions’ concentrations and spin speeds on the porous structure were experimentally investigated. The results showed that a certain mass ratio of PS/SBS can make the structure of the ordered porous film more regular and denser under the optimal solution concentration and spin-coating speed. Superior transparency and durability were also realized by dripping silicone oil on the porous film to build a liquid-infused surface. Applications of the as-prepared surface on devices like endoscopes, viewfinders, and goggles have been explored respectively. Full article

Although the gas phase combustion of metallic magnesium (Mg) has been extensively studied, the vaporization and diffusive combustion behaviors of Mg have not been well characterized. This paper proposes an investigation of the vaporization, diffusion, and combustion characteristics of individual Mg microparticles in inert and oxidizing gases by a self-built experimental setup based on laser-induced heating and microscopic high-speed cinematography. Characteristic parameters like vaporization and diffusion coefficients, diffusion ratios, flame propagation rates, etc., were obtained at high spatiotemporal resolutions (μm and tens of μs), and their differences in inert gases (argon, nitrogen) and in oxidizing gases (air, pure oxygen) were comparatively analyzed. More importantly, for the core–shell structure, during vaporization, a shock wave effect on the cracking of the porous magnesium oxide thin film shell-covered Mg core was first experimentally revealed in inert gases. In air, the combustion flame stood over the Mg microparticles, and the heterogeneous combustion reaction was controlled by the diffusion rate of oxygen in air. While in pure O₂, the vapor-phase stand-off flame surrounded the Mg microparticles, and the reaction was dominated by the diffusion rate of Mg vapor. The diffusion coefficients of the Mg vapor in oxidizing gases are 1~2 orders of magnitude higher than those in inert gases. However, the diffusive ratios of condensed combustion residues in oxidizing gases are ~1/2 of those in inert gases. The morphology and the constituent contents analysis showed that argon would not dissolve into liquid Mg, while nitrogen would significantly dissolve into liquid Mg. In oxidizing gases of air or pure O₂, Mg microparticles in normal pressure completely burned due to laser-induced heating. Full article

The Langmuir-Blodgett (LB) method is a well-known deposition technique for the fabrication of ordered monolayer and multilayer thin films of nanomaterials onto different substrates that plays a critical role in the development of functional devices for various applications. This paper describes detailed studies about the best coating configuration for nanoparticles of a porous metal-organic framework (MOF) onto both insulating or conductive threads and nylon fiber. We design and fabricate customized polymethylmethacrylate sheets (PMMA) holders to deposit MOF layers onto the threads or fiber using the LB technique. Two different orientations, namely, horizontal and vertical, are used to deposit MIL-96(Al) monolayer films onto five different types of threads and nylon fiber. These studies show that LB film formation strongly depends on deposition orientation and the type of threads or fiber. Among all the samples tested, cotton thread and nylon fiber with vertical deposition show more homogenous monolayer coverage. In the case of conductive threads, the MOF particles tend to aggregate between the conductive thread’s fibers instead of forming a continuous monolayer coating. Our results show a significant contribution in terms of MOF monolayer deposition onto single fiber and threads that will contribute to the fabrication of single fiber or thread-based devices in the future. Full article

The treatment of organic dye contaminants in wastewaters has now becoming more imperative. Fenton-like degradation of methylene blue (MB) and methyl orange (MO) in aqueous solution was investigated by using a nanostructure that a layer of CuCl₂ nanoflake film grown on the top surface of nanoporus anodic alumina substrate (nano-PAA-CuCl₂) as catalyst. The new nano-PAA-CuCl₂ composite was fabricated with self-assembly approach, that is, a network porous structure film composed of CuCl₂ nanoflake grown on the upper surface of nanoporous anodic alumina substrate, and the physical and chemical properties are characterized systematically with the X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM), and high-resolution transmission electron microscopy (HRTEM), Energy Dispersive Spectrometer (EDS), X-ray photoelectron spectroscopy (XPS). The experimental results showed that the nano-PAA-CuCl₂ catalyst presented excellent properties for the degradation of two typical organic pollutants such as MB and MO, which were almost completely degraded with 8 × 10⁻⁴mol/L nano-PAA-CuCl₂ catalyst after 46 min and 60 min at reaction conditions of H₂O₂ 18 mM and 23 mM, respectively. The effects of different reaction parameters such as initial pH, H₂O₂ concentration, catalyst morphology and temperature were attentively studied. And more, the stability and reusability of nano-PAA-CuCl₂ were examined. Finally, the mechanism of MB and MO degradation by the nano-PAA-CuCl₂/H₂O₂ system was proposed, based on the experimental data of the BCA and the temperature-programmed reduction (H₂-TPR) and theoretical analysis, the reaction kinetics belonged to the pseudo-first-order equation. This new nanoporous composite material and preparation technology, as well as its application in Fenton-like reaction, provide an effective alternative method with practical application significance for wastewater treatment. Full article

Well-ordered porous films have been widely applied in various areas, such as chemical sensors, microreactors, and tissue engineering. In this article, we propose a novel air-liquid interface self-assembly method to fabricate well-ordered porous polystyrene (PS)/styrene–butadiene–styrene (SBS) films by simply dipping the PS/SBS chloroform solutions onto the surface of a mixed water/ethanol liquid phase. The proper volume ratio of water/ethanol is necessary for the formation of films with highly uniform pore size. The effect of weight ratio of PS/SBS, the volume ratio of water/ethanol and the concentration of the solutions were experimentally investigated. The pore size decreases with the concentration of polymer solution, and the structure becomes more regular with the decrease of water/ethanol volume ratio. Ordered structure can be formed under PS/SBS in a certain weight ratio. The self-assembled films also have the function of self-cleaning. Besides the analysis of structural characteristic, the self-assembly mechanism was also discussed. Full article

In this work, various NiAl-LDH thin films, exhibiting specific surface morphologies, were developed directly on aluminum AA 6082 substrate to understand the two main characteristics of layered double hydroxide (LDH), i.e., ion-exchange behavior and barrier properties, which are found to have a significant influence on the LDH corrosion resistance properties. The as-prepared NiAl-LDH films were analyzed through the scanning electronic microscope (SEM), X-ray diffraction (XRD), while the corrosion behavior of the synthesized films was investigated by the electrochemical impedance spectroscopy (EIS) and potentiodynamic curves. The results indicated that NiAl-LDH microcrystals grow in various fashions, from porous relatively flat domains to well-developed platelet structure, with the variation of nickel nitrate to ammonium nitrate salts molar ratios. The LDH structure is observed in all cases and is found to cover the aluminum surface uniformly in the lamellar order. All the developed NiAl-LDHs are found to enhance the corrosion resistance of the aluminum substrate, specifically, a well-developed platelet structure is found to be more effective in chloride adsorptive and entrapment capabilities, which caused higher corrosion resistance compared to other developed NiAl-LDHs. The comparison of the synthesized NiAl-LDH morphologies on their ion-exchange capabilities, barrier effect and their combined effect on corrosion resistance properties is reported. Full article

In this work, highly monodisperse porous alginate films from bubble bursting were formed on a glass substrate at ambient temperature, by a T-shaped microfluidic junction device method using polyethylene glycol (PEG) stearate and phospholipid as precursors in some cases. Various polymer solution concentrations and feeding liquid flow rates were applied for the generation of monodisperse microbubbles, followed by the conversion of the bubbles to porous film structures on glass substrates. In order to compare the physical properties of polymeric solutions, the effects of alginate, PEG stearate (surfactant), and phospholipid concentrations on the flowability of the liquid in a T-shaped microfluidic junction device were studied. To tailor microbubble diameter and size distribution, a method for controlling the thinning process of the bubbles’ shell was also explored. In order to control pore size, shape, and surface as well as internal structure morphologies in the scalable forming of alginate polymeric films, the effect of the feeding liquid’s flow rate and concentrations of PEG-stearate and phospholipid was also studied. Digital microscopy images revealed that the as-formed alginate films at the flow rate of 100 µL·min⁻¹ and the N₂ gas pressure of 0.8 bar have highly monodisperse microbubbles with a polydispersity index (PDI) of approximately 6.5%. SEM captures also revealed that the as-formed alginate films with high PDI value have similar monodisperse porous surface and internal structure morphologies, with the exception that the as-formed alginate films with the help of phospholipids were mainly formed under our experimental environment. From the Fourier-transform infrared spectroscopy (FTIR), Differential scanning calorimetry (DSC) and X-ray diffraction (XRD) measurements, we concluded that no chemical composition changes, thermal influence, and crystal structural modifications were observed due to the T-shaped microfluidic junction device technique. The method used in this work could expand and enhance the use of alginate porous films in a wide range of bioengineering applications, especially in tissue engineering and drug delivery, such as studying release behaviors to different internal and surface morphologies. Full article

Novel selective polymeric thin-film composite membranes (TFCMs) for applications at elevated temperatures were developed. Thin selective layers of the polyimides Matrimid 5218^® and 6FDA-6FpDA were cast on a developed polybenzimidazole (PBI) porous support prepared by a phase inversion process. The TFCM properties were investigated with different gases in a wide temperature range, including temperatures up to 270 °C. The membranes showed very high thermal stability and performed well at the elevated temperatures. The development of highly thermally resistant polymeric membranes such as these TFCMs opens opportunities for application in high-temperature integrated processes, such as catalytic membrane reactors for the water-gas shift reaction in order to maximize H₂ yield. Full article