Fabrication and morphology control of poly(methyl methacrylate) hollow structures via coaxial electrospinning

A modified electrospinning method known as coaxial electrospinning was used to fabricate poly(methyl methacrylate) (PMMA) hollow structures. In this study to understand morphology control, the effect of processing parameters such as concentration of polymer sheath solution, size of core/sheath capillaries, feed rate, and applied voltage had been evaluated. Morphological observations via scanning electron microscope (SEM) revealed that via the control of polymer concentration within the sheath solution, morphologies such as hollow particles and fibers could be obtained. With the use of fine core/sheath capillaries, micron hollow fibers with walls of less than 20 nm were obtained. This study has demonstrated how the investigated processing parameters have a direct influence on the structures and how these parameters have supported the notion that effective encapsulation process is the key to the dual layer bicomponent structures. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation of poly(L-lactic acid) honeycomb monolith structure by unidirectional freezing and freeze-drying

Honeycomb monolith structured porous poly(L-lactic acid) (PLLA) was successfully fabricated by combining pseudo steady state unidirectional freezing and freeze-drying techniques. Dehydrated 1,4-dioxane was used as a solvent for PLLA and the single-phase mixture was unidirectionally frozen by lowering the sample tube into liquid nitrogen at a constant rate. The 1,4-dioxane crystal was nucleated in the solution and grown in the freezing direction. Using the crystalline structure as a template, the PLLA was solidified and structured. Then, the crystal was allowed to sublimate by freeze-drying and the aligned porous structure, which has either smooth wall microtubes or ladder-like microtubes aligned along the freezing direction and a honeycomb structure in its vertical direction was prepared. The effects of polymer concentration, sample tube lowering rate and water contents on the aligned porous structure were thoroughly investigated. We found that the smoothness of the microtube wall and its interconnectivity could be controlled by the polymer concentration and water content in solution.     

Facile fabrication of polycarbonate monolith by non-solvent induced phase separation method

Polycarbonate (PC) monoliths with three-dimensional continuous interconnected porous structure in a single piece are fabricated via non-solvent induced phase separation (NIPS) for the first time. The morphology of fabricated monolith is observed through SEM, the surface area is determined by BET method and the thermal property is measured via DSC. The pore and skeleton sizes of the monolith are readily controlled by varying the fabrication parameters such as the polymer concentration and molecular weight, the standing temperature and the solvent composition. The PC monolith possesses relatively large surface area and sharp melting point at 232 °C. These monoliths with high thermal stability can offer various potential applications of functional materials.     

Simulations of photodegradation of toluene and formaldehyde in a monolith reactor using computational fluid dynamics

In this study, simulations were conducted on a monolith reactor for the photodegradation of toluene and formaldehyde. The monoliths in the reactor were treated as porous zones and the photocatalytic oxidation occurring on the monolith surfaces was modeled using Langmuir–Hinshelwood kinetics. A discrete ordinates model was used to simulate the light intensity with a novel approach, which involved an adjustable parameter—the absorption coefficient of the channel wall, for modeling the local light intensity across the porous media. The advantage of this approach was that despite its simplicity, it was able to capture and visualize the local light profile across the monolith channels and to integrate it into the reaction kinetics. Although it required a trial‐and‐error to determine the correct value of the channel wall absorption coefficient, the proposed model achieved a reasonable agreement between the simulation results and published experimental data. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Evaluation of poly(butyl acrylate-co-ethylene glycol dimethacrylate) sorbents for chromatographic separation of biomolecules

Copolymers of butyl acrylate (BA) crosslinked with ethylene glycol dimethacrylate (EGDMA) were evaluated as potential chromatographic packings. It was found that slightly crosslinked copolymers (up to 30 wt.-% EGDMA) did not provide porous material, while for matrices which exceeded 40 wt.-% of EGDMA the porous structure remained unchangeable. The increase of crosslinker content mostly affected the surface hydrophobicity. Two methods of measurement of this property were discussed: Sorption of alkyl alcohols and amino acids. Taking the latter for testing, a polymer matrix hydrophobicity index was calculated as the slope of dependence of column capacity vs. amino acid hydrophobicity parameter. The indices were verified against well-established interaction energies of ? CH₂? groups of alkyl alcohols and polymer surfaces. Some benefits of the use of the hydrophobicity index in evaluation of polymer sorbents were demonstrated.     

Facile fabrication of porous cross-linked monolith based on nature soybean oil by low temperature phase separation photopolymerization

Acrylate epoxy soybean oil based porous cross-linked monolith have been successfully prepared by low temperature phase separation photo initiated polymerization. Type and concentration of the photoinitiator and sample thickness on the polymerization behavior at low temperature were studied. The optimum conditions for the preparation of the sample were found out. The porous morphology was affected by monomer concentration, freezing rate and temperature of the solution. The average pore size increased with increasing solvent, decreasing freezing temperature and speed. Compress stress of porous materials was related to the pore size of porous monolith.     

Characterization of polymer adsorption in tube flow of drag reducing fluids

Elucidation of the polymer adsorption and flow characteristics at the tube wall is essential for an understanding of turbulent drag reduction. The polymer adsorbed onto the tube wall, in the flow of dilute solutions of linear random coiling macromolecules, also produces a concentrated fluid layer at the surface of the adsorption zone, as a result of the flow of the solvent micromolecules in the porous network comprising the adsorption zone.Velocity profiles are developed and used to determine the radial variation in the adsorption zone of porosity, as well as fractional surface coverages and mean separation or interpenetration distances between macromolecules in the various adsorption layers. The polymer concentration build-up in the concentrated fluid layer is also evaluated. Predictions of the latter for aqueous Polyox WSR-301 solutions are in qualitative agreement with experimental measurements and suggest that turbulent drag reduction is related to the level of polymer build-up in the concentrated fluid layer.     

Surface modification of coil coatings with thin plasma polymer films structure and stability

Plasma deposition of a thin top layer with tailored properties is an effective strategy of modification of the organic coating surface. Thin plasma polymer layers are candidates and can provide superior hardness, scratch resistance, modified surface hydrophobicity and easy to clean properties.The present work studies the stability of thin plasma polymer films deposited as top layer on polyurethane coil coating systems. Microwave, hollow cathode and radio frequency plasma polymerization reactors were employed in order to deposit a thin SiO_x based plasma polymer layer.The plasma film stability was studied using surface analysis techniques, ex situ and in situ atomic force microscopy and scanning electron microscopy. Energy dispersive spectroscopy, FTIR spectroscopy and optical measurements confirm the composition and plasma layer properties. The structure of the plasma layers was investigated by means of transmission electron microscopy.The surface morphology together with composition evolution allows the study of the stability of the different coatings. The structure examination of the formed plasma polymer film offers good clarification for coating failure. Decrease of the operating pressure during plasma polymerization and oxygen concentration in precursor mixture lead to formation of compacter layer with higher stability. Introduction of fluorine-containing precursor also increases the anti-weathering performance of the plasma polymer films.     

Conceptual design and CFD simulation of a novel metal-based monolith reactor with enhanced mass transfer

This paper introduces a novel structured metallic catalyst that improves mass transfer performance of a monolith reactor for highly exothermic gas–solid reactions. The monolith channels are designed to have metallic substrates that consist of two layers with one of the layers being the metallic support and another layer being a foam metal annular that is tightly deposited onto the support surface by some means. Parametrical studies based on a 2D monolith reactor model showed that the present design yields an enhanced mass transfer between the bulk fluid and the catalyst layer due to a decrease in external film resistance, and an enhanced mass transfer within the solid phase mainly due to the viscous flow effect within the porous catalyst layer.     

Porous polyurethane film fabricated via the breath figure approach for sustained drug release

The breath figure (BF) method is an effective process for fabricating porous polymeric films. In this study, we fabricated porous polymer films from thermoplastic polyurethane (PU) through static BF with CHCl₃ as a solvent under 55–80% relative humidity. The porous PU films were prepared within various pore structures and sizes, which were adjustable, depending on the fabrication conditions. The humidity and exposure time were examined as variable parameters affecting the surface morphology, wettability, and cytotoxicity. Atorvastatin calcium, a hyperlipidemic agent, was loaded into the porous films during the casting process, and the drug-loading and drug-releasing behaviors of the porous PU membranes were evaluated. Approximately 60–80% of the drug was released in 14 days. The films exhibited sustained drug-release performances because of the hydrophobicity and nonbiodegradable nature of PU for perivascular drug administration. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47658.     

Analysis on the apparent slip and depleted layer of polymer flow in narrow-bore capillaries

Polymer solutions flowing through small-diameter capillaries of which length scale is much larger than that of polymers were experimentally demonstrated to have the enhanced flow rate as compared to in bulk flow. Thisapparent slip phenomenon was analyzed by obtaining theslip velocity and concentrationdepleted layer thickness. Hydrolyzed polyacrylamide (HPAM) of highly flexible polymer and Xanthan of rigid rodlike polymer were made to flow through stainless steel capillaries having the diameter range of about 100 to 250 μm. The results showed that both slip velocity and depleted layer thickness decreased markedly with increasing polymer concentration. This behavior can be interpreted as being due to the reduction of diffusion coefficient and flexibility of polymer chains as the concentration is increased. The depleted layer thickness of HPAM was much larger than the polymeric length scale and was shown to increase with increasing wall shear stress. This is considered as an evidence of thestress-induced diffusion of polymer chains being a dominant factor for the apparent slip of flexible polymer solution. On the other hand, the depleted layer thickness of Xanthan solution was almost constant with the wall shear stress, which can not be explained by the stress-induced diffusion mechanism alone.     

Controlling the microstructure of lyophilized porous biocomposites by the addition of ZnO‐doped bioglass

The study presents the results of the study on porous composite biomaterials obtained using lyophilization method based on polymer solutions: chitosan solution, sodium alginate solution, or polylactide solution, and ZnO‐doped bioglass from CaO‐SiO₂‐P₂O₅ system. The properties of zinc ions were used, which have bactericidal, immune‐stimulating, and tissue‐regenerating functions in the organism. The effects of the polymer type, granulation, and bioglass amount, as well as the amount of solvent on composite microstructure, were studied. SEM‐EDS technique was used to visualize and describe the surface results occurring after incubation of composite in the Simulated Body Fluid (SBF). The selected method of preparation, used substrates, and the process conditions resulted in porous composites of the open, connected pore structure. It was proved that composite microstructure may be controlled by the appropriately selected amount of bioglass in relation to the polymer and its appropriate grain sizes. The morphology of the obtained composites is also affected by the amount of the solvent in lyophilizated dispersions. It was proved that bioactivity in composite material is induced by bioglass because after SBF incubation the surface layer is enriched with Ca and P, what may lead to a gradual formation of apatite layer. The obtained results enabled selection of the composites for further in vitro studies concerning cytotoxicity and antibacterial activity.     

Multi-Layer Electrospun Membrane Mimicking Tendon Sheath for Prevention of Tendon Adhesions

Defect of the tendon sheath after tendon injury is a main reason for tendon adhesions, but it is a daunting challenge for the biomimetic substitute of the tendon sheath after injury due to its multi-layer membrane-like structure and complex biologic functions. In this study, a multi-layer membrane with celecoxib-loaded poly(l-lactic acid)-polyethylene glycol (PELA) electrospun fibrous membrane as the outer layer, hyaluronic acid (HA) gel as middle layer, and PELA electrospun fibrous membrane as the inner layer was designed. The anti-adhesion efficacy of this multi-layer membrane was compared with a single-layer use in rabbit flexor digitorum profundus tendon model. The surface morphology showed that both PELA fibers and celecoxib-loaded PELA fibers in multi-layer membrane were uniform in size, randomly arrayed, very porous, and smooth without beads. Multi-layer membrane group had fewer peritendinous adhesions and better gliding than the PELA membrane group and control group in gross and histological observation. The similar mechanical characteristic and collagen expression of tendon repair site in the three groups indicated that the multi-layer membrane did not impair tendon healing. Taken together, our results demonstrated that such a biomimetic multi-layer sheath could be used as a potential strategy in clinics for promoting tendon gliding and preventing adhesion without poor tendon healing.     

Effect of Surface Modification on the Synthesis of Pore‐Filling Polymeric Monoliths in Microfiltration Membranes Made from Poly(propylene) and Poly(ethylene terephthalate)

The effect of pre‐modification on the interaction of macroporous substrates (membranes) with mainly micro‐ and mesoporous polymer monoliths has been studied. Bulk, porous polymer monoliths were synthesized to optimize the synthesis conditions and their pore morphology, and the data were used as benchmark for this study. Pre‐modification of the entire pore surface of PP microfiltration membranes and PET track‐etched membranes by UV‐initiated grafting with PEGMA was performed using well‐established methods, including coating with the photo‐initiator, benzophenone. Subsequently, these membranes were functionalized by filling the pores with porous polymer monoliths from MAA and EDMA and compared with membranes that had been functionalized without the pre‐modification step. The materials were characterized mainly by the degree of grafting, SEM and by the gas‐adsorption‐isotherm method. The DG values, after composite‐membrane preparation under identical conditions, were not influenced by the pre‐modification. However, it could be clearly seen from the SEM images that the pre‐modification step prevents the formation of voids at the monolith‐membrane pore interface. Larger specific surface area and pore volume values for composite membranes, prepared after pre‐modification, fully support the SEM results. Especially large differences in pore structure between the two different composite membranes were found in the mesopore range. The results of this study indicate that it is possible to prepare porous, composite membranes where the trans‐membrane transport is exclusively controlled by the pore and surface structure of a functional polymeric monolith, for example, made from a molecularly‐imprinted polymer.

     

Breath figure templated semifluorinated block copolymers with tunable surface properties and binding capabilities

Patterning of functionalized polymeric surfaces enables the adjustment of their characteristics and use in novel applications. We prepared breath figure (BF) films from three semifluorinated diblock copolymers, which all are composed of a polystyrene block and a semifluorinated one to compare their surface properties. “Click” chemistry was employed to one of the polymers, containing a poly(pentafluorostyrene) block to incorporate hydrophilic sugar or carboxylic acid moieties. The structure of the polymer alters the obtained porous morphology of the films. Contact angle (CA) analyses of the BF films reveals that the surface porosity increases water CAs compared with solvent cast films, and, in the case of hydrophobic polymers, leads to significant increase in the CAs of dodecane. The hydrophobicity of the BF films is further amplified by the removal of the topmost layer which leads in some cases to superhydrophobic surfaces. BF films containing glucose units are hydrophilic exhibiting water CAs below 90°. These glycosylated porous surfaces are shown to bind lectin Con A‐FITC or can be labelled with isothiocyanate marker. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41225.     

Facile fabrication of poly(methyl methacrylate) monolith via thermally induced phase separation by utilizing unique cosolvency

Poly(methyl methacrylate) (PMMA) monoliths with a three-dimensional continuous interconnected porous structure in a single piece were fabricated via thermally induced phase separation (TIPS) by utilizing unique cosolvency toward PMMA. We found that PMMA was soluble in a mixture of non-solvents (ethanol and water) at 60 °C. Cooling the solution resulted in formation of a monolith having interconnected pores. Cross-sectional analysis using scanning electron microscopy (SEM) showed a continuous porous network with submicron-sized skeleton. The pore size of the monolith was readily controlled by varying the fabrication parameters such as the polymer concentration and molecular weight, the cooling temperature and the solvent composition. The cross-section of the monolith showed high water repellency. The PMMA monolith was also obtained in a mixture of isopropanol and water with an appropriate solvent ratio.     

搅拌对高内相比乳液法制备多孔聚合物的影响

研究了不同的搅拌速率和搅拌时间下,采用高内相比乳液法制备的多孔聚合物密度、孔径和吸附性能,用扫描电镜和N2吸附仪对多孔聚合物的形态和结构进行了表征。结果表明:搅拌速率和搅拌时间主要影响高内相比乳液的形成和稳定性,对多孔聚合物的密度影响不大,增加搅拌时间,增加了多孔聚合物的比表面积和孔容,从而增加了对水和甲苯的吸附,由于多孔聚合物的亲油性,使之对甲苯的吸附率明显高于水的吸附率。     

A novel porous epoxy acrylate resin monolith prepared by the low-temperature phase separation photopolymerization

A novel porous epoxy acrylate resin monolith has been successfully prepared by low-temperature phase separation photoinitiated polymerization. The process parameters of low-temperature photopolymerization, including photoinitiators type, concentration, and sample thickness were studied. The optimum conditions for the preparation of the sample were also evaluated. The results showed that the porous morphology of the prepared monolith was affected by monomer concentration, freezing speed and temperature of the solution. The average pore size increased with increasing solvent amount, decreasing freezing temperature and speed.     

Fabrication and characterization of dual-layer hollow-fiber ultrafiltration membranes

In this study, poly(vinylidene fluoride) (PVDF) dual-layer hollow-fiber UF membranes were prepared via phase inversion in one step. Laboratory-synthesized amphiphilic poly(vinylidene fluoride)-g-poly(ethylene glycol) methyl ether methacrylate (PVDF-g-POEM) was incorporated as a hydrophilic modifier of the outer layer by blending. The effects of the dope formulation and membrane formation conditions on membrane structure and UF performance were investigated. The parameters investigated included the PVDF-g-POEM loading in the outer layer, the PEG additive content in the outer layer, the external coagulant composition, and the polymer concentration in the inner layer. The effects of adding PVDF-g-POEM and PEG were found to depend on the external coagulant composition; when a water/ethanol mixture was used as coagulant, the fibers formed in the presence of PEG exhibited larger pores, as confirmed by both SEM characterization and a solute rejection method. The porosity of the inner layer was observed to increase with decreasing inner-layer dope concentration and upon weakening the external coagulant. A more porous inner layer led to a higher transmembrane pure water flux. An antifouling test confirmed that both membrane hydrophobicity and surface pore size affected the membrane fouling pattern and the final FRR. The highest FRR of 83.3% was obtained with the hollow fiber M5A, which was characterized by a compact surface and contained PVDF-g-POEM in its polymer matrix.     

Characterization of unsteady flow in a 3D-printed Schwarz Diamond monolith using magnetic resonance velocimetry

Process engineering applications such as heat transfer, reactions, and separations involve passing fluid through a porous medium. Historically, random-channel porous media have been used for these operations. Such systems do not represent optimal configurations for process performance because of poor flow distribution and high-pressure drop. It is now possible to fabricate porous monoliths with tailored morphology and regular channel structure using 3D-printing. In this work, we use magnetic resonance imaging to study flow through a Schwarz Diamond triply periodic minimal surface (TPMS) monolith for Reynolds numbers up to 350. A transition to unsteady flow was observed experimentally for the first time. The channel structure diverts flow such that free shear layers form in the channel centers that contribute to flow instability. These measurements serve to inform the design of novel transport processes with enhanced performance.