New insights into sodium alginate fouling of ceramic hollow fiber membranes by NMR imaging

Ceramic hollow fiber membranes are investigated with respect to the fouling behavior. Constant pressure dead‐end filtration experiments have been performed using alginate as model substance for extracellular polymeric substances. In addition to the evaluation of the filtration data using conventional cake filtration model, nuclear magnetic resonance imaging (MRI) was used to elucidate the influence of Ca²⁺ on the fouling layer structure for alginate filtration within ceramic hollow fiber membranes. To visualize the alginate layers inside the opaque ceramic hollow fiber membranes by means of MRI, specific contrast agents were applied. Supplementary to multi slice multi echo imaging, flow velocity measurements were performed to gain more insight into the hydrodynamics in the fouled membranes. MRI reveals the structure of the alginate layers with the finding that the addition of Ca²⁺ to the alginate feed solution promotes the formation of a dense alginate gel layer on the membrane's surface. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2459–2467, 2016     

Preparation of coatings on alumina ceramic for wettability

To improve the wetting ability between ceramic and metal, titanium and copper coatings on alumina ceramics were prepared by infiltration of molten salt and electroless plating, respectively. A Ti/Cu bi-layer was also obtained by combining the two methods. The preparation process was optimized. The phase composition of the coatings was analyzed by X-ray diffraction (XRD). And the wettability of the titanium coating was investigated. The results showed that the copper droplet was easily spread on the surface of titanium coated alumina. The titanium coated alumina was well composited with high chromium white cast iron and the interface between ceramic and metal was well combined.     

In‐situ characterization of deposits in ceramic hollow fiber membranes by compressed sensing RARE‐MRI

Ultrafiltration with ceramic hollow fiber membranes was investigated by compressed sensing rapid acquisition relaxation enhancement (CS‐RARE) magnetic resonance imaging (MRI) to characterize filtration mechanisms. Sodium alginate was used as a model substance for extracellular polymeric substances. Dependent on the concentration of divalent ions like Ca²⁺ in an aqueous alginate solution, the characteristics of the filtration change from concentration polarization to a gel layer. The fouling inside the membrane lumen could be measured by MRI with a CS‐RARE pulse sequence. Contrast agents have been used to get an appropriate contrast between deposit and feed. The lumen was analyzed quantitatively by exploring the membrane's radial symmetry, and the resulting intensity could be modeled. Thus, different fouling mechanisms could be distinguished. CS‐RARE‐MRI was proven to be an appropriate in situ tool to quantitatively characterize the deposit formation during in‐out filtration processes. The results were underlined by flux interruption experiments and length dependent studies, which make it possible to differentiate between gel layer or cake filtration and concentration polarization filtration processes. © 2018 American Institute of Chemical Engineers AIChE J, 64: 4039–4046, 2018     

Surface characterization of hollow fiber membranes used in artificial kidney

The internal and external curved surfaces of polysulfone hollow fiber membranes were characterized by atomic force microscopy (AFM), contact angle measurement (CAM), and scanning electron microscopy (SEM) with the aim of improving the membrane surface properties for blood compatibility. Novel approaches were applied to evaluate a number of properties, including the roughness, pore size, nodule size, and wettability of the surfaces of the hollow fibers. CAM studies were carried out by directly observing the liquid meniscus at the surfaces of hollow fibers. Observation of the meniscus and measurement of the contact angle became possible by using an imaging system developed in our laboratory. AFM and SEM studies were also conducted on the surfaces of the hollow fiber membranes by cutting them at an inclined angle. The effect of the molecular weight of poly(ethylene glycol) (PEG) in the polymer blend on the surface properties of the hollow fibers was studied. Increasing the PEG molecular weight increased the average pore size whereas it decreased the contact angle. The contact angle depended on the microscopic surface morphology, including nodule size and roughness parameters. The theoretical prediction along with the experimental data showed that the measured contact angle would be greater than the value intrinsic to the membrane material because of the formation of composite surface structures. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4386–4400, 2006     

A modified model for alumina membranes formed by gel-casting followed by dip-coating

α-Al₂O₃ membrane coating (top layer) was formed by dip-coating and investigated based on full factorial design of experiments. Statistical analysis showed that the effects of two variables; dipping time and withdrawal speed of the substrate, were highly significant in determining the thickness of the top layers (α<0.001). A modified model was developed to interpret quantitatively the formation process of the top layers onto the porous substrate during dip-coating. In this model, the effects of all variables affecting the top layer thickness were considered simultaneously. The experimental data corresponding to α-Al₂O₃ membranes obtained from suspensions with different volume fractions of ceramic powder showed good agreement with the model. The root mean square deviation was less than 0.02.     

新型温敏性中空纤维膜的制备与表征

采用自由基聚合方法对中空纤维膜（hollow fiber membranes,HFMs）进行了N-异丙基丙烯酰胺（NIPAAm）的接枝聚合,制备了一系列PNIPAAm-g-HFMs,同时考察了成纤维细胞在PNIPAAm-g-HFMs表面的培养与降温脱附情况。傅里叶红外光谱和元素分析结果表明PNIPAAm成功地在中空纤维膜上接枝聚合。动态接触角分析结果显示,当温度降至LCST以下,PNIPAAm-g-HFMs表面接触角明显降低;蛋白黏附测定结果进一步证实了当温度发生改变时,PNIPAAm-g-HFMs表面呈现亲疏水性质变化,即具有温敏性。37℃时,成纤维细胞在HFMs-0.005,HFMs-0.01和HFMs-0.05表面均能正常黏附、铺展与增殖;而HFMs-0.2不适宜细胞的黏附与生长。降温孵育后,黏附于PNIPAAm-g-HFMs表面的细胞发生明显的形态变化并从其表面发生脱附,细胞脱附率高达90%以上。以上实验结果表明,PNIPAAm-g-HFMs具有良好的温敏性,可实现细胞的降温脱附,可与生物反应器相结合用于贴壁型细胞的大规模扩增与降温收获。     

Preparation and characterization of polyvinylidene fluoride hollow fiber membranes for ultrafiltration

Polyvinylidene fluoride (PVDF) hollow fiber membranes were prepared using the solvent spinning method. N,N-dimethylacetamide was the solvent and ethylene glycol was employed as non-solvent additive. The effect of the concentration of ethylene glycol in the PVDF spinning solution as well as the effect of ethanol either in the internal or the external coagulant on the morphology of the hollow fibers was investigated. The prepared membranes were characterized in terms of the liquid entry pressure of water measurements, the gas permeation tests, the scanning electron microscopy, the atomic force microscopy, and the solute transport experiments. Ultrafiltration experiments were conducted using polyethylene glycol and polyethylene oxides of different molecular weights cut-off as solutes. A comparative analysis was made between the membrane characteristic parameters obtained from the different characterization techniques.     

Improved microstructure of asymmetric niobium pentoxide hollow fiber membranes

Asymmetric niobium pentoxide (Nb₂O₅) hollow fiber membranes were prepared by the phase inversion and sintering process at temperatures ranging from 1000 to 1350°C. The effects of extrusion parameters on the morphology and properties of the produced membranes were systematically explored. Asymmetric hollow fibers with regular inner contour were obtained at extrusion flow rates of 15 and 25 ml min⁻¹ of ceramic suspension and internal coagulant, respectively. Hollow fibers sintered at temperatures greater than 1200°C presented modifications in the morphology of Nb₂O₅ grains, which were also evidenced by X-ray diffraction and Raman analyses. Hollow fibers produced with an air gap of 50 mm presented a dense outer sponge-like layer and micro-voids formed from the inner surface. These hollow fibers sintered at 1200°C presented suitable bending resistance and water permeability (24.2 ± 0.60 MPa and 3.00 ± 0.01 L h^-1 m^-2 kPa^-1, respectively). The outer sponge like layer was mitigated when the fibers were produced without air-gap.     

Ultra-thin skin carbon hollow fiber membranes for sustainable molecular separations

A transformative platform is reported to derive ultra-thin carbon molecular sieve (CMS) hollow fiber membranes from dual-layer precursor hollow fibers with independently tuned skin layer and substrate properties. These ultra-thin CMS hollow fiber membranes show attractive CO₂/CH₄ separation factors and excellent CO₂ permeances up to ~1,400% higher than state-of-the-art asymmetric CMS hollow fiber membranes. They provide a unique combination of permeance and selectivity competitive with zeolite membranes, but with much higher membrane packing density and potentially much lower costs.     

Development and characterization of silica-based membranes for hydrogen separation

The method of chemical vapor deposition (CVD) in the counter current configuration was employed in the present study for the development of composite silica membranes. The experiments were carried out in a horizontal CVD reactor under controlled temperature conditions and at various reaction times and differential pressures across the substrate sides. Tetraethylorthosilicate (TEOS) and ozone were used as deposition precursors. Two types of substrates were employed: a porous Vycor tube and an alumina (γ-Al₂O₃) nanofiltration (NF) tube. Measurements with a novel mercury intrusion technique showed that significant reduction of the initial pore size of the γ-Al₂O₃ substrates was achieved, which reached 76% in the cases of extended silica deposition. Additionally, by appropriately interpreting the Knudsen type O₂ permeance results, acquired during the CVD treatment of Vycor tubes, a pore radius reduction even down to the 30% of the initial value was concluded. The permeance of Η₂ and other gases (Ηe, Ν₂, Αr, CO₂) on the developed membranes was measured in a home-made apparatus. The separation capability of the composite membranes was determined by calculating the selectivity of hydrogen over helium, nitrogen, argon and carbon dioxide.     

Preparation and performance of braid‐reinforced poly(vinyl chloride) hollow fiber membranes

A novel braid‐reinforced (BR) poly(vinyl chloride) (PVC) hollow fiber membrane was fabricated via dry‐wet spinning process. The mixtures of PVC polymer solutions were uniformly coated on the tubular braid which contained polyester (PET) and polyacrylonitrile (PAN) fibers. The influences of braid composition on structure and performance of BR PVC hollow fiber membranes were investigated. The results showed that the prepared BR PVC hollow fiber membranes were composed of two layers which contained separation layer and tubular braid supported layer when the PET and PET/PAN hybrid tubular braids were used as the reinforcement. But the sandwich structure appeared when the PAN tubular braid was used as the reinforcement, which revealed outer separation layer, tubular braid supported layer and the inner polymer layer. The BR PVC hollow fiber membranes that prepared by PET/PAN hybrid tubular braid had favorable interfacial bonding state compared with the membrane prepared by pure PET or PAN tubular braid. The pure water flux of the BR PVC hollow fiber membranes that prepared by the PET/PAN hybrid tubular braid were lower than that prepared by pure PET or PAN tubular braid, but the rejection of Bovine serum albumin was opposite. The tensile strength of prepared BR PVC hollow fiber membrane was higher than 50 MPa. Both of the tensile strength and elongation at break decreased with the increase of the PAN filaments in the PET/PAN hybrid tubular braid. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45068.     

Preparation and properties of polytetrafluoroethylene/CaCO3 hybrid hollow fiber membranes

A novel method of preparing polytetrafluoroethylene (PTFE) hollow fiber membrane was presented by utilizing poly (vinyl alcohol) (PVA) can form a gel of two dimensional complex compounds with Boric acid (H₃BO₃). Effects of H₃BO₃ on PTFE nascent hollow fiber were investigated, and the results showed that the introduction of H₃BO₃ effectively reduced the addition of PVA. The configuration named “fibril” formed between PVA and H₃BO₃ could be observed in nascent hollow fiber by SEM (Scanning electronic microscopy). Furthermore, Calcium carbonate (CaCO₃) particles (60 nm～ 90 nm) were introduced into PTFE matrix. The interfacial microvoids (IFMs) which were different from the PTFE sintering or node‐fibril network structure were obtained. The assumption of the IFMs formation was proposed in this study. Effects of CaCO₃ amount and draw ratios on structure and properties of hybrid hollow fiber membranes were analyzed, and the SEM results showed that the IFMs quantity and diameter improved with draw ratio increasing. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Improved spinnerette design for extrusion of polymeric large internal diameter hollow fiber membranes

Spinnerettes for extrusion of large (～ 1 mm) internal diameter (i.d.) hollow fiber membranes must possess certain features to extrude fibers with the proper tensile and geometrical properties. Spinnerette designs that properly extrude small i.d. (< 200 μm) hollow fibers will produce large i.d. hollow fibers with low burst strengths because of poor flow patterns and insufficient time in the spinnerette to knit a strong seam interface. In this report, an alternative design is offered that provides much better fiber properties without creating high pressure drops or shear stresses at the spinnerette wall that would normally result in melt fracture. The equations that guide the presented spinnerette design are provided and the suggested design is successfully guided by the results. The new spinnerette design also has the feature of allowing rapid change of hollow fiber wall thickness by making the core fluid pin replaceable. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2157–2163, 2002     

The effects of spinning temperature on morphologies and properties of polyethersulfone hollow fiber membranes

Polyethersulfone (PES) hollow fiber membranes were prepared by traditional dry‐wet spinning technique. Scanning electronic microscopy (SEM) was used to characterize membrane morphologies, and the membrane properties were evaluated via bubble point measurements and ultrafiltration experiments. The effects of spinning temperature on the morphologies and properties of PES fibers were investigated in detail. At a high spinning temperature, the obtained membrane structure consisting of a thin skin‐layer and loose sponge‐like sublayer endows PES membrane with not only good permeability, but also high solute rejection. Based on the determination of ternary phase diagrams and light transmittance curves, the relationship of membrane morphologies with thermodynamics and precipitation kinetics of membrane‐forming system was discussed. It was concluded that the morphologies and properties of PES hollow fiber membrane could be conveniently tuned by the adjustment of the spinning temperature and air gap. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of the volume ratio of zirconia and alumina on the mechanical properties of fibrous zirconia/alumina bi-phase composites prepared by co-extrusion

Fibrous zirconia/alumina composites with different composition were fabricated by piston co-extrusion. After a 3rd extrusion step and sintering at 1600 °C, crack-free composites with a fibre width of 50 μm were obtained for all compositions. The effect of the volume ratio of secondary phase on the mechanical properties was investigated. The Young's modulus of the composites decreased linearly with increasing the zirconia content. The fracture toughness of the composites was improved by introducing fine second phase filaments into the matrix. The maximum fracture toughness of 6.2 MPa m^1/2 was attained in the 3rd co-extruded 47/53 vol% zirconia/alumina composite. The improvement in toughness was attributed to both “stress-induced” transformation of zirconia and a crack deflection mechanism due to thermal expansion mismatch between the two phases. Bending strength of the composites was almost the same as that of the monolithic alumina regardless of the composition.     

Reactive alumina production for the refractory industry

In this study, fine reactive alumina powder production was investigated using Bayer gibbsite as a starting material. Experimental studies consist of three steps; in the first step, the soda content was reduced by means of boric acid and distilled water. In the second step, the effect of heating rate and calcinations temperature on crystal size, phase transformation and surface area were investigated and characterization of the powders was performed by means of XRD and SEM analyses. In the third step, the powders obtained optimum conditions were ground in an attritor mill and then particle size distribution and surface area were measured. The soda content of the gibbsite was reduced from 0.325 to 0.05% by H₃BO₃ treatment, calcination at 1200 °C and then washing in distilled water. The higher the heating rate, the smaller the crystal size is. Alumina ceramics with a density higher than 94.70% of theoretical density were obtained.     

Micro powder injection moulding of alumina micro-channel part

A feedstock consisting of submicron alumina powder and a formulated binder, was developed to fabricate alumina micro-channel part by micro powder injection moulding. During small scale-mixing, the mixing torques of feedstocks with four different powder loadings were used to establish a suitable powder loading. The thermal and rheological properties of the selected feedstock were examined and used to establish conditions for large scale mixing, debinding and injection moulding. The micro-channel parts were pressureless sintered at different temperatures. The results showed that the moulded, debound and sintered micro-channel parts had good shape retention. The dimensions of the micro-channel part changed with the different processing steps. High densification of the micro-channel parts was achieved at sintering temperatures of 1350 °C and above. Above 1350 °C, the grain grew significantly with increasing the sintering temperatures and thus it led to a decrease in the microhardness.     

Preparation of reusable glass hollow fiber membranes and methylene blue adsorption

In this work, the PVDF/glass as-prepared composite membrane was prepared through phase-inversion method and used to adsorb methylene blue dye. The results of SEM and BET showed that the membrane had an asymmetric nanoscale porous structure. The electronegativity on the surface of membrane was determined through zeta potential test. The adsorption properties of as-prepared composite membrane and glass membrane were studied through testing the removal ratio of methylene blue from aqueous solution. Then the effects of membranes dose, pH value, temperature and initial concentration on the removal ratio were systematically studied. The adsorption mechanism was also studied. The adsorption kinetics and adsorption isotherm fitted well with the pseudo-second-order model and Freundlich model, respectively. In addition, the adsorption efficiency of glass membrane basically remained 85% after eight repeated adsorption-calcination cycles. The obtained membranes could be reused for methylene blue removal with high efficiency for multiply times.     

Microstructural development of interface layers between co-sintered alumina and spinel compacts

Tests were performed to investigate the microstructure of the interface between alumina and spinel materials after high temperature thermal treatment (1500 °C). The first test involved co-sintering of co-pressed alumina and spinel compacts. Microstructures were investigated by SEM, EDS, WDS and EBSD. A microstructurally distinct layer with columnar grains of up to 40 μm length and 5 μm width was observed after 16 h at 1500 °C. Growth rate of the columnar spinel grains from parent spinel towards alumina follows parabolic kinetics, controlled by a mixed process of O²⁻ ion diffusion and interface reaction. Diffusion couples of spinel and alumina were investigated. Same columnar spinel grains were observed at the interface which grew into alumina during thermal treatment with the same kinetics as in co-sintering experiments. The shape of the phase boundaries between spinel and alumina can be a further indication of the direction of their growth.