Water‐based freeze casting: Adjusting hydrophobic polymethylsiloxane for obtaining hierarchically ordered porous SiOC

The hydrophobic properties of methyl poly siloxane (MK) were pushed into the “hydrophilic” range by cross‐linking it with (3‐aminopropyl)triethoxysilane (APTES) and subsequent pyrolysis to enable water‐based freeze casting. Filler properties are investigated by varying the ratios of MK to APTES (1:1, 1:2, 1:3, 1:4, 1:5), and pyrolysis temperatures (400°C, 500°C, 600°C) for the purpose of determining an optimal set of characteristics for freeze casting. Additionally, filler selection for this purpose is facilitated by analysis of zeta potential values and vapor adsorption. It was found that water‐based freeze casting with hybrid fillers, followed by a pyrolysis step (600°C‐700°C), leads to a SiOC ceramic monolith with a lamellar pore morphology and a hierarchically ordered micro/meso/macropore structure. Samples pyrolyzed at 1000°C contain mesopores, having a SSA as high as 51.6 m²/g. The hierarchically porous structure is very promising for applications involving gas or liquid transportation.     

Structural Design of Polymer‐Derived SiOC Ceramic Aerogels for High‐Rate Li Ion Storage Applications

SiOC ceramic aerogels with different porosity, pore size, and specific surface area have been synthesized through the polymer‐derived ceramic route by modifying the synthesis parameters and the pyrolysis steps. Preceramic aerogels are prepared by cross‐linking a linear polysiloxane with divinylbenzene (DVB) via hydrosilylation reaction in the presence of a Pt catalyst under highly diluted conditions. Acetone and cyclohexane are used as solvent in our study. Wet gels are subsequently supercritically dried with CO₂ to get the final preceramic aerogels. The SiOC ceramic aerogels are obtained after a pyrolysis treatment at 900°C in two different atmospheres: pure Ar and H₂ (3%)/Ar mixtures. The nature of the solvent has a profound influence of the aerogel microstructure in terms of porosity, pore size, and specific surface area. Synthesized SiOC ceramic aerogels have similar chemical compositions irrespective of processing conditions with ~40 wt% of free carbon distributed within remaining mixed SiOC matrix. The BET surface areas range from 215 m²/g for acetone samples to 80 m²/g for samples derived from cyclohexane solvent. The electrochemical characterization reveals a high specific reversible capacity of more than 900 mAh/g at a charging rate of C (360 mA/g) along with a good cycling stability. Samples pyrolyzed in H₂/Ar atmosphere show a high reversible capacity of 200 mAh/g even at a high charging/discharging rate of 20 C. Initial capacities were recovered after whole cycling procedure indicating their structural stabilities resisting any kind of exfoliations.     

Preparation of Micro‐/Mesoporous SiOC Bulk Ceramics

Micro‐/mesoporous SiOC bulk ceramics with high surface area and bimodal pore size distribution were prepared by pyrolysis of polysiloxane in argon atmosphere at 1100°C–1400°C followed by etching in hydrofluoric acid solution. Their thermal behaviors, phase compositions, and microstructures at different nano‐SiO₂ filler contents and pyrolysis temperatures were investigated by XRD, SEM, DSC, and BET. The SiO₂ fillers and SiO₂‐rich clusters in the SiOC matrix act as pore‐forming sites and can be etched away by HF. At the same time, the SiO₂ filler promotes SiOC phase separation during the pyrolysis. The filler content and pyrolysis temperature have important effects on phase compositions and microstructures of porous SiOC ceramics. The resulting porous SiOC bulk ceramic has a maximum specific surface area of 822.7 m²/g and an average pore size of 2.61 nm, and consists of free carbon, silicon carbide, and silicon oxycarbide phases.     

Highly Porous SiOC Bulk Ceramics with Water Vapor Assisted Pyrolysis

Micro/mesoporous SiOC bulk ceramics with the highest surface area and the narrowest pore size distribution were prepared by water‐assisted pyrolysis of polysiloxane in argon atmosphere at controlled temperatures (1100°C–1400°C) followed by etching in hydrofluoric acid (HF) solution. Their pyrolysis behaviors, phase compositions, and microstructures were investigated by DSC, FTIR, XRD, and BET. The Si–O–Si bonds, SiO₂‐rich clusters, and SiO₂ nanocrystals in the pyrolyzed products act as pore‐forming species and could be etched away by HF. Water injection time and pyrolysis temperature have important effects on phase compositions and microstructures of the porous SiOC bulk ceramics, which have a maximum‐specific surface area of 2391.60 m²/g and an average pore size of 2.87 nm. The porous SiOC ceramics consist of free carbon phase, silicon carbide, and silicon oxycarbide.     

Investigation of membrane preparation condition effect on the PSD and porosity of the membranes using a novel image processing technique

A totally computerized image processing program package is developed to analyze the SEM images of membrane surface and cross‐section. Pore size distribution and porosity of the fabricated membranes are determined using the proposed image processing procedure. Furthermore, effect of coagulation bath temperature on the morphology and mechanical properties (such as tensile strength, strain break, tensile energy absorbent, and tensile stiffness) of Polysulfone (PSf) membranes are investigated. The results reveal that the mechanical properties are higher when N‐methyl‐2‐pyrrolidone (NMP) is used as solvent. Also, an increase in the coagulation bath temperature caused a monotonous increase in the mean pore size value of Dimethylformamide (DMF)‐based membranes. However, mean pore size curve has a maximum when NMP is used as solvent. Also, porosity of the fabricated membranes increased when coagulation bath temperature increased. For the NMP‐base membranes, pore's diameter was in the range of 0–5 μm. However, DMF‐based membranes have pore size value of smaller than 1 μm when the precipitation medium is kept at 8°C. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39899.     

Thermodynamic Control of Phase Composition and Crystallization of Metal‐Modified Silicon Oxycarbides

Silicon oxycarbides modified with main group or transition metals (SiMOC) are usually synthesized via pyrolysis of sol‐gel precursors from suitable metal‐modified orthosilicates or polysiloxanes. In this study, the phase composition of different SiMOC systems (M = Sn, Fe, Mn, V, and Lu) was investigated. Depending on the metal, different ceramic phases formed. For M = Mn and Lu, MO_x/SiOC ceramic nanocomposites were formed, whereas other compositions revealed the formation of M/SiOC (M = Sn), MSi_x/SiOC (M = Fe) or MC_x/SiOC (M = V) upon pyrolysis. The different phase compositions of the SiMOC materials are rationalized by a simple thermodynamic approach which generally correctly predicts which type of ceramic nanocomposite is expected upon ceramization of the metal‐modified precursors. Calculations show that the thermodynamic stability of the MO_x phase with respect to that of the C–O system is the most important factor to predict phase formation in polymer‐derived SiMOC ceramic systems. A secondary factor is the relative stability of metal oxides, silicates, carbides, and silicides.     

Template‐Free Synthesis of Porous Fe3O4/SiOC(H) Nanocomposites with Enhanced Catalytic Activity

We present a template‐free synthesis of Fe₃O₄/SiOC(H) nanocomposites with in situ formed Fe₃O₄ nanoparticles with a size of about 50 nm embedded in a nanoporous SiOC(H) matrix obtained via a polymer‐derived ceramic route. Firstly, a single‐source precursor (SSP) was synthesized by the reaction of allylhydridopolycarbosilane (AHPCS) with Fe‐acetylacetonate [Fe(acac)₃] at 140°C. The SSP was heat‐treated at 170°C to generate Fe₃O₄ nanocrystals in the cross‐linked polymeric matrix. Subsequently, the SSP was pyrolyzed at 600°C–700°C in argon atmosphere to yield porous Fe₃O₄/SiOC(H) nanocomposites with the high BET surface area up to 390 m²/g, a high micropore surface area of 301 m²/g, and a high micropore volume of 0.142 cm³/g. The Fe‐free SiOC(H) ceramic matrix derived from original AHPCS is nonporous. The in situ formation of Fe₃O₄ nanoparticles embedded homogeneously within a nanoporous SiOC(H) matrix shows significantly enhanced catalytic degradation of xylene orange in aqueous solution with H₂O₂ as oxidant as compared with pure commercial Fe₃O₄ nanoparticles.     

Structure and energetics of SiOC and SiOC‐modified carbon‐bonded carbon fiber composites

The incorporation of SiOC polymer‐derived ceramics into porous carbon materials could provide tailored shapeable, mechanical, electrical, and oxidation‐resistant properties for high‐temperature applications. Understanding the thermodynamic and kinetic stability of such materials is crucial for their practical application. We report here the dependence of structures and energetics of SiOC and SiOC‐modified carbon‐bonded carbon fiber composites (CBCFs) on the pyrolysis temperature using spectroscopic methods and high‐temperature oxide melt solution calorimetry. The results indicate that a SiOC ceramic pyrolyzed at 1200°C and 1600°C is energetically stable with respect to an isocompositional mixture of cristobalite, silicon carbide, and graphite by 4.9 and 10.3 kJ/mol, respectively, and more energetically stable than that pyrolyzed at 1450°C. Their thermodynamic stability is related to their structural evolution. SiOC‐modified CBCFs become energetically less stable with increasing preparation temperature and concomitant increase in excess carbon content.     

Optimization and investigation of the governing parameters in electrospinning the home‐made poly(l‐lactide‐co‐ε‐caprolactone‐diOH)

Poly(l ‐lactide‐co‐ε‐caprolactone‐diOH) (PCLA) with (ABA)_n type is synthesized using poly(lactic acid) (PLA) and poly(ε‐caprolactone) di‐OH (PCL‐diOH) via chain extending method. FT‐IR, ¹H‐NMR, and GPC data demonstrate that PLA and PCL‐diOH have reacted completely. The product is electrospun into ultrafine fibers subsequently. The optimum electrospinning parameters obtain from an orthogonal experiment are a solvent ratio (DMF/DCM) of 5/5, a polymer concentration of 28 wt %, a collector distance of 20 cm and a voltage of 18 kV. As a result, the average diameter of fibers is 0.77 µm and the uniformity is above 80%. Via range analysis, it is found that the order of the influence on diameter is solvent ratio, applied voltage, collector distance, and polymer concentration, successively. Single effect of the four governing factors on diameter and morphology is also experimentally investigated. This may provide clues for obtaining fibers with various structures by controlling the parameters. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3600–3610, 2013     

Effects of solvents on electrospun polymeric fibers: preliminary study on polystyrene

Six solvents [acetic acid, acetonitrile, m‐cresol, toluene, tetrahydrofuran (THF) and dimethylformamide (DMF)] with different properties (eg density, boiling point, solubility parameter, dipole moment and dielectric constant) were used to prepare electrospun polystyrene (PS) fibers. Fiber diameters were found to decrease with increasing density and boiling point of the solvents. A large difference between the solubility parameters of PS and the solvent was responsible for the bead‐on‐string morphology observed. Productivity of the fibers (the numbers of fiber webs per unit area per unit time) increased with increasing dielectric constant and dipole moment of the solvents. Among the solvents studied, DMF was the best solvent that provided PS fibers with highest productivity and optimal morphological characteristics. The beadless, well‐aligned PS fibers with a diameter of ca 0.7 µm were produced from the solution of 10 % (w/v) of PS in DMF at an applied electrostatic field of 15 kV/10 cm, a nitrogen flow rate of 101 ml min^?1 and a rotational speed of the collector of 1500 rev min^?1. Copyright © 2004 Society of Chemical Industry     

Production of hyaluronic‐acid‐based cell‐enclosing microparticles and microcapsules via enzymatic reaction using a microfluidic system

This article describes the preparation of cell‐enclosing hyaluronic acid (HA) microparticles with solid core and microcapsules with liquid core through cell‐friendly horseradish peroxidase (HRP)‐catalyzed hydrogelation. The spherical vehicles were made from HA derivative possessing phenolic hydroxyl moieties (HA‐Ph) cross‐linkable through the enzymatic reaction by extruding cell‐suspending HA‐Ph aqueous solution containing HRP from a needle of 180 μm in inner diameter into the ambient coaxial flow of liquid paraffin containing H₂O₂ in a microtubule of 600 μm in diameter. By altering the flow rate of liquid paraffin, the diameters of gelatin and HA‐Ph microparticles were varied in the range of 120–220 μm and 100–300 μm, respectively. The viability of the enclosed human hepatoma HepG2 cells in the HA‐Ph microparticles of 180 μm in diameter was 94.2 ± 2.3%. The growth of the enclosed HepG2 cells was enhanced by decreasing the HRP concentration. The microcapsules of 200 μm in diameter were obtained by extruding HA‐Ph aqueous solution containing thermally liquefiable cell‐enclosing gelatin microparticles of 150 μm in diameter using the same microfluidic system. The enclosed cells grew and filled the cavity within 10 days. Spherical tissues covered with a heterogeneous cell layer were obtained by degrading the microcapsule membrane using hyaluronidase after covering the surface with a heterogeneous cell layer. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43107.     

Effects of processing parameters on morphology of electrospun polystyrene nanofibers

This study focused on the preparation of electrospun polystyrene (PS) nanofibers. PS solutions were prepared in single (dimethylformamide; DMF, dimethylacetamide; DMAc or tetrahydrofuran; THF) and mixed solvent (DMF/THF and DMAc/THF) systems with and without tetrabutylammonium bromide (TBAB) salt. The effects of PS concentration, solvent system, the addition of salt, appearance and diameter of PS fibers were examined. The average diameter of the as-spun fibers increased upon increasing PS concentration. The morphology of the fibers significantly depended on the properties of the solvents. The obtained fibers were smooth without any beads and their diameters were affected by the amount of THF in the solvent and PS concentration. The beads in the fibers disappeared and the fiber diameter significantly decreased after the addition of TBAB. The smallest diameter and the narrowest diameter distribution of PS nanofibers (376±36 nm) were obtained from 15% PS solution in DMAc with 0.025% w/v TBAB.     

Flash pyrolysis of polymer-derived SiOC ceramics

For the first time, flash pyrolysis was carried out to fabricate polymer derived silicon oxycarbide (SiOC) ceramics. With the application of a DC electric field at a furnace temperature of only 780?°C, the SiOC ceramics exhibit characteristics that usually have to be pyrolyzed at ～1300?°C. Both electric field and current density accelerate the SiOC microstructure development, causing carbon and SiC phases to form at >520?°C lower pyrolysis temperatures than conventional within the SiOC matrix. With higher electric fields, the samples experience greater mass loss and linear shrinkage, while also forming more SiC and a more ordered carbon phase. The SiC formation inversely impacts the carbon content, causing a decrease in electrical conductivity. Further, reducing current density results in significant carbon precipitation without SiC formation. The fundamentals can be explained based on increased nucleation rate by the electrical field, accompanied by Joule heating and electromigration. This work is the first to demonstrate the great potential of flash pyrolysis on accelerated phase separation of polymer derived SiOC.     

Zr-doped SiOC ceramics fibers and the high-temperature thermal performance

Silicon-containing ceramics fibers are ideal candidates for thermal resistance due to their incomparable thermo-stability and chemical stability. Research into anti-oxidation behavior of silicon-containing ceramics through metal elements doping is important for the application in extreme high-temperature environment. Thus, uniform belts-like Zr-doped SiOC ceramics fibers were successfully prepared by electrospinning and polymer-derived ceramics routine with polycarbosilane (PCS) and zirconium butoxide as precursors. The morphology and dimension of the fibers were conveniently controlled by tuning PCS concentration, types of spinning additives and pyrolysis temperature. The ceramics fibers were composed of SiC, ZrO₂ and SiO₂ crystals, accompanied with amorphous Si_mZr_nC_xO_y. The structure and compositions realized the excellent thermal stability above 1300°C and the enhanced flexibility. The obtained fibers maintained ultra-low thermal conductivity of .038–.053 W/(m·K). Thus, the materials were anticipated to be ideal for the thermal insulation up to 1400°C or higher.     

Electrospinning of polycarbonate urethane biomaterials

Polycarbonate urethane (PCU) nano-fibers were fabricated via electrospinning using N,N- dimethylformamide (DMF) and tetrahydrofuran (THF) as the mixed solvent. The effect of volume ratios of DMF and THF in the mixed solvent on the fiber structures was investigated. The results show that nano-fibers with a narrow diameter distribution and a few defects were obtained when mixed solvent with the appropriate volume ratio of DMF and THF as 1∶1. When the proportion of DMF was more than 75% in the mixed solvent, it was easy to form many beaded fibers. The applied voltage in the electrospinning process has a significant influence on the morphology of fibers. When the electric voltage was set between 22 and 32 kV, the average diameters of the fibers were found between 420 and 570 nm. Scanning electron microscopy (SEM) images showed that fiber diameter and structural morphology of the electrospun PCU membranes are a function of the polymer solution concentration. When the concentration of PCU solution was 6.0 wt-%, a beaded-fiber microstructure was obtained. With increasing the concentration of PCU solutions above 6.0 wt-%, beaded fiber decreased and finally disappeared. However, when the PCU concentration was over 14.0 wt-%, the average diameter of fibers became large, closed to 2 μm, because of the high solution viscosity. The average diameter of nanofibers increased linearly with increasing the volume flow rate of the PCU solution (10.0 wt-%) when the applied voltage was 24 kV. The results show that the morphology of PCU fibers could be controlled by electrospinning parameters, such as solution concentration, electric voltage and flow rate.     

Polypropylene microfibers via solution electrospinning under ambient conditions

Uniform beadless fibers of chlorinated polypropylene (PP-Cl) are prepared by electrospinning of PP-Cl solutions in tetrahydrofuran at different concentrations, feed rates, applied voltages, and tip-to-collector distances (TCDs) under ambient conditions for the first time. Average fiber diameter and morphology of the electrospun PP-Cl fibers are determined by scanning electron microscopy. On the other hand, the wettability of the fibers is examined by water contact angle (WCA) measurements. Furthermore, thermal behavior of fibers is investigated by differential scanning calorimetry and thermogravimetric analyses, respectively. Obtained results show that the higher concentrations and feed rates of polymer solutions not only enhance the average diameter of the electrospun fibers ranging from 2.2 ± 0.5 to 2.8 ± 0.3 μm but improve the hydrophobicity of the fiber surfaces from 128° ± 1.1 to 141° ± 1.0 as well. On the other hand, when applied voltage is increased or TCD is decreased, diameters of achieved fibers are enhanced. It is suggested that PP-Cl is an useful material for solution electrospinning process at under ambient conditions, exhibiting great scientific merit and good industrial expectation in the potential PP applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48199.     

热解含铁聚硅氧烷原位生长硅氧碳纤维制备硅氧碳复合材料

将铁氯化物混入聚硅氧烷前驱体进行交联成型和热解,利用热解中在聚硅氧烷中形成的孔隙和在孔隙中形成的铁颗粒为催化剂,在硅氧碳陶瓷基体中原位生长出硅氧碳纳米纤维,制备出硅氧碳陶瓷和硅氧碳纤维复合材料。用扫描电子显微镜观察材料断面,结果显示：在硅氧碳陶瓷基体中生长出纳米纤维,部分纤维取向分布,纤维紧贴于硅氧碳陶瓷基体,二者呈良好结合;能谱分析显示纤维中含硅、氧和碳,证实其为硅氧碳。所制得的硅氧碳陶瓷和硅氧碳纤维的复合结构不同于通常热解纯聚硅氧烷形成的单相的硅氧碳结构,在硅氧碳基体中的硅氧碳纤维是在聚硅氧烷前驱体中引入的铁催化剂在热解过程中通过催化聚硅氧烷一维生长形成的,该过程可用于发展一步法原位制备纳米纤维前驱体陶瓷复合材料。     

Influence of free carbon on the Young's modulus and hardness of polymer-derived silicon oxycarbide glasses

Silicon oxycarbide (SiOC) glasses in the form of thin, dense, and crack-free samples were fabricated according to the polymer pyrolysis route starting from cross-linked polysiloxane. The amount of free carbon in the final SiOC materials was varied in the range 18-60 vol%. The mechanical properties of the SiOC glasses were measured by nanoindentaion technique and revealed that both the Young's modulus and the hardness decrease with increase in the free carbon content and follow a simple rule of mixtures model.     

A novel batch-scale fabrication method for hundred-micron YAG transparent ceramic fibers

YAG ceramic fiber is the preferred material for the gain medium of the new generation fiber laser. However, the fabrication of hundred-micron and defect-free YAG ceramic fibers is still the primary challenge. In this paper, YAG ceramic fibers with the diameter of 147 µm and length of 113 mm were successfully batch fabricated by the combination of gelcasting and mold design, and the diameter fluctuation rate was only 1.4%. The solid loading of the slurries (46–54 vol%) were systematically investigated to achieve high density and net-shape forming of green fibers. It was found that the YAG ceramic fiber was highly transparent with the optimized solid loading of 52 vol%, and the transmittance of the YAG ceramic (2 mm thick) at 800 nm was 82.6%. Its bending strength was as high as 1124 ± 86 MPa. The ideas and methods of this study will promote the development of gelcasting in the field of hundred-micron ceramic fibers.     

Enhanced mechanical and dielectric properties of SiCf/SiC composites with silicon oxycarbide interphase

SiC_f/SiC composites with silicon oxycarbide (SiOC) interphase were successfully prepared using silicone resin as interphase precursor for dip-coating process and polycarbosilane as matrix precursor for PIP process assisted with hot mold pressing. The effects of SiOC interphase on mechanical and dielectric properties were investigated. XRD and Raman spectrum results show that SiOC interphase is composed of silicon oxycarbide and free carbon with a relatively low crystalline degree. The surface morphology of SiC fibers with SiOC interphase is smooth and homogeneous observed by SEM. The flexural strength and failure displacement of SiC_f/SiC composites with SiOC interphase vary with the thickness of interphase and the maximum value of flexural strength is 289 MPa with a failure displacement of 0.39 mm when the thickness of SiOC interphase is 0.25 µm. The complex permittivity of the composites increases from 8.8-i5.7 to 9.8-i8.3 with the interphase thicker.