Sulfonation Process Research Articles

Synthesis of ion exchange film based on chemical grafting of styrene onto polyethylene/EPDM rubber blend for thorium removal.

Chemical grafting of low-density polyethylene film blended with ethylene propylene diene monomer rubber (PE/EPDM) using styrene monomer followed by a sulfonation process was investigated. Different factors affecting the grafting process, such as monomer and initiator concentrations, time of reaction, and grafting temperature, were studied. Sulfonation of the grafted films was carried out using chlorosulfonic acid in dichloromethane. Characterization of the grafted and sulfonated films was performed using ATR-FTIR, SEM, TGA, and XRD instruments. The grafting was successfully performed in aqueous media using sodium bisulfite as initiator, reaching a grafting yield of 130% and an ion exchange capacity of 1.2 meq/g. The removal of thorium ions from aqueous solution was studied using the obtained ion exchange films. The results showed that the maximum adsorption capacity of Th(IV) was 177.5 mg. g-1 (pH = 3, 298 K and 60 min). Removal isotherm and Kinetics were investigated, and the results revealed that the adsorption process was chemisorption homogeneous monolayer adsorption, exothermic, and spontaneous.

Correlation of proton conductivity and free volume in sulfonated polyether ether ketone electrolytes: A positron annihilation lifetime spectroscopy study

Proton-conducting polymers play a pivotal role in clean energy technologies and various industrial applications, with a significant emphasis on enhancing energy efficiency and minimizing environmental impact. Sulfonated polyether ether ketone (SPEEK), which is renowned for its proton conductivity, has emerged as a key material in electrochemical processes, notably in proton exchange membrane (PEM) fuel cells. This study investigated the proton conductivity and dielectric behavior of SPEEK electrolytes at varying degree of sulfonation (DS) of 65% and 80%, correlating these properties with free volume profiles determined by positron annihilation lifetime spectroscopy (PALS). The SPEEK-65 and SPEEK-80 electrolytes were prepared via a controlled sulfonation process and characterized by FTIR, TGA, and SEM analyses. Proton conductivity and dielectric measurements were conducted at temperatures ranging from 300-370 K and frequencies ranging from 20 Hz to 1 MHz. The results revealed that SPEEK-80 exhibited a maximum proton conductivity of 3.4×10-2 S/m at 300 K and 1 MHz, which was significantly greater than the 4.38×10-3 S/m observed for SPEEK-65 under the same conditions. PALS analysis demonstrated a notable increase in free volume with increasing DS, with SPEEK-80 showing a higher o-Ps lifetime and intensity, indicating larger free volume sizes and fractions. These findings underscore the critical interplay between DS, free volume, and proton conductivity, offering insights into optimizing SPEEK-based electrolytes for advanced electrochemical applications.

Myelin Sheath-Inspired Hydrogel Electrode for Artificial Skin and Physiological Monitoring.

Significant advancements in hydrogel-based epidermal electrodes have been made in recent years. However, inherent limitations, such as adaptability, adhesion, and conductivity, have presented challenges, thereby limiting the sensitivity, signal-to-noise ratio (SNR), and stability of the physiological-electrode interface. In this study, we propose the concept of myelin sheath-inspired hydrogel epidermal electronics by incorporating numerous interpenetrating core-sheath-structured conductive nanofibers within a physically cross-linked polyelectrolyte network. Poly(3,4-ethylenedioxythiophene)-coated sulfonated cellulose nanofibers (PEDOT:SCNFs) are synthesized through a simple solvent-catalyzed sulfonation process, followed by oxidative self-polymerization and ionic liquid (IL) shielding steps, achieving a low electrochemical impedance of 42 Ω. The physical associations within the composite hydrogel network include complexation, electrostatic forces, hydrogen bonding, π-π stacking, hydrophobic interaction, and weak entanglements. These properties confer the hydrogel with high stretchability (770%), superconformability, self-adhesion (28 kPa on pigskin), and self-healing capabilities. By simulating the saltatory propagation effect of the nodes of Ranvier in the nervous system, the biomimetic hydrogel establishes high-fidelity epidermal electronic interfaces, offering benefits such as low interfacial contact impedance, significantly increased SNR (30 dB), as well as large-scale sensor array integration. The advanced biomimetic hydrogel holds tremendous potential for applications in electronic skin (e-skin), human-machine interfaces (HMIs), and healthcare assessment devices.

Rapid surface modification of PEEK by ambient temperature sulfonation for high shelf-life biomedical applications

The aim of this study is to develop a rapid, simple, and economical surface treatment process for Poly (ether-ether-ketone) (PEEK) using concentrated sulfuric acid. PEEK is a biocompatible material, with a bonelike elastic modulus and is mechanically superior to other implant materials like titanium, stainless steel etc. This property brings PEEK to limelight as a promising alternative for bone implants. However, a strong challenge is observed of osseointegration mainly due to its inert surface behavior and poor hydrophilicity. Chemical surface modification is considered as one of the best ways to bioactivate the PEEK surface. In this work, two different sulfonation treatment methodologies have been designed and the effect of reaction time is systematically studied over its changing surface properties and favorable cellular growth. In one treatment, only rapid sulfonation is implemented while in other treatment processes, scaffolds are treated with NaOH solution to terminate the sulfonation process. The modified PEEK surface is next evaluated using Fourier transform infra-red spectroscopy (FTIR), contact angle, optical profilometer and scanning electron microscopy to ascertain its behavior. The modified surface is observed to possess higher hydrophilicity, higher surface roughness and high porosity. No significant difference in hydrophilicity is observed for over a month once treated, showing permanency in modification. A 90 second treatment is observed to have the highest hydrophilicity and thus selected for cellular integration studies. No sign of cell toxicity was observed in the modified surfaces, which also showed improved protein adsorption, cell viability, cell adhesion, and proliferation compared to untreated PEEK.The proposed chemical modifications are promising techniques for a rapid, easy, and economical bioactivation of PEEK polymer for improved cellular activity.

Study on gas–liquid sulfonation reaction under annular flow pattern in micro-reactor: Mechanism, model and process optimization

Micro-sulfonation is a new sulfonation method with great development potential. The gas–liquid micro-sulfonation are safe, efficient and low-cost, however, limited by the research progress and application scope of micro-reactors, the development of gas–liquid micro-sulfonation technique is far from enough. The gas–liquid sulfonation reaction process under annular flow pattern in micro-reactor is experimentally studied in this paper. The maximum MESA (fatty acid methyl ester sulfonic acid) yield under the experimental conditions in this study achieves 89.771 %, which is obviously higher than that (64.1 % for gas–liquid sulfonation and 76.82 % for liquid–liquid sulfonation) in conventional reactors and should be higher if the micro-reactor structure or operating conditions being further optimized. Based on the analyses of experimental results, the effect mechanisms of mass transfer and reaction on the gas–liquid micro-sulfonation efficiency are explored, and the sulfonation efficiency models and pressure drop model of four micro-reactors are established by dimensional analysis method. On account of both the mass transfer characteristics of gas–liquid two-phase flow and the high-viscosity of sulfonation products, enhancing the local disturbance of liquid phase can significantly improve the reaction efficiency. Finally, the operating conditions of two-phase flow rates and reaction time are optimized to ensure the high sulfonation product yield meanwhile reduce the fluid pressure drop or energy consumption of sulfonation process using the improved NSGA-II algorithm.

Emulsion graft polymerization of glycidyl methacrylate onto bamboo fiber composites for efficient removal of lead ions from aqueous solutions

The emulsion graft polymerization process was used to synthesize a novel polyglycidyl methacrylate grafted silanized bamboo fiber composites. The grafting percentage was assessed by varying surfactant, initiator and monomer concentrations. The surface morphologies and thermal behavior of the biocomposites were analyzed using FTIR, SEM, XRD and TGA techniques. In batch adsorption studies, the effect of adsorption parameters like pH, adsorption time, adsorbent dose and solution temperature were examined on the adsorption efficiency of lead ions. The adsorption capacity of biosorbent composites was enhanced through conversion of epoxy group of Poly glycidyl methacrylate (PGMA) into sulfonic acid groups via sulfonation process. The sulfonic acid groups were incorporated into VMBF-g-PGMA by stirring the grafted sample in H2SO4 (98 %) for 2 h at 90 °C to obtain sulfonated grafted polymer (VMBF-g-PGMA-S). By increasing the concentration of monomers up to 5 %, the maximum grafting percentage (289 %) was achieved. The grafting % increases rapidly from 0.5 to 0.20 g initiator and at 0.20 g of initiator, the highest grafting yield was 512 %. The maximum Pb+2 adsorption capacity of adsorbent was 200 mg/g. The thermodynamic parameters for pb+2 adsorption revealed an exothermic and spontaneous nature of sorption process, and the entropy change showed that there are no substantial structural changes occurred in biosorbent material. The experimental results confirmed that sulfonated biosorbent composites are effective, economical, and promising adsorbent which could be used for removal of lead and other ions from aqueous solution.

Effect of acid soak treatment of the precursor on the structure and properties of polypropylene-based carbon fibers

Polyolefin fibers have received wide attention as the precursor for low-cost carbon fiber, and cross-linking of linear polyolefin by strong acid has been proven to be an effective way to stabilize the precursor fiber prior to carbonization. However, the conventional temperature used in sulfonation process is too high and could result in severe decomposition of the linear chain of the polymer, which further deteriorated the mechanical properties of the as-prepared carbon fiber. Thus, reducing the duration of sulfonation process operated at high temperature may alleviate the degradation behavior, conferring the polyolefin-based carbon fibers with better performance. In this paper, polypropylene (PP) fibers were soaked in sulfuric acid at 50 °C–90 °C, before the conventional preparation protocol of PP-based carbon fiber. The structural evolution from PP to carbon fiber were characterized by Differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and Raman spectroscopy. The mechanical and conductive properties of carbonized fibers where further measured. The results showed that the soak in sulfuric acid resulted in swelling of PP fibers in diameter direction, as well as reducing the crystallinity of the fibers, both of which were physical transformation, and could be easily controlled by soak temperature. The subsequent sulfonation at conventional temperature was fastened for the soaked PP fibers, and the duration of sufficient sulfonation were almost reduced by half. The obtained carbon fibers exhibited better thermal conductivity and mechanical properties, which were enhanced by 25 % and 40 %, respectively, compared with that without soak pretreatment.

Hardness Reduction using Waste Plastic

This study focused on the utilisation of waste plastic as an ion exchanger to reduce water hardness. The three identical glass columns R1, R2, and R3 were used, each containing different types of waste plastic resin, such as styrofoam resin (SR), air bubble plastic resin (AR), or a mixture of both resins (MR), respectively. The plastics underwent a sulfonation process after crushing and sieving; their sulfonation was confirmed using FTIR analysis. For lab-scale experiments, each glass column was filled with sand, gravel, and coconut fiber as supporting media and equipped with a pump and flow-control valves. Groundwater collected from an urban area was passed through the columns at different flow rates and contact times. The process takes place by exchanging the Na+ ions of resins with polluting ions present in hard water. The treatment parameters involved are total hardness, calcium hardness, magnesium hardness, chloride, TDS, and pH. During the treatment process, pH was maintained between 7 and 8.5. All the parameters were tested twice, and the average of the observations was noted. The results showed that the maximum total hardness reduction achieved in reactors R1, R2, and R3 was 63%, 52%, and 58.6%, respectively, at a contact time of 24 h.

(Invited) Carbon Sulfonation Using Plasma: Trial to Enlarge Treatment Capacity

Heterogeneous catalysis is a promising technology in conversion of biomass to biofuels because of its high reactivity, easy post-separation, and great recyclability compared to homogeneous catalysis. Various functionalized catalytic materials have emerged as promising alternatives to the homogeneous liquid acid catalyst, such as carbon materials, metal–organic frameworks, and metal nanoparticles. Among them, carbon materials such as carbon nanotube, graphene oxide, carbon black, and so on have been investigated as catalysts for cellulose hydrolysis to produce glucose.Carbon materials show considerable catalytic activity by functionalization with active acidic groups including hydroxyl groups (-OH), carboxyl groups (-COOH), and sulfonic groups (-SO3H). Hydroxyl and carboxyl groups on the carbon catalysts act as connection center to access cellulose, where sulfonic group serves as the active site to cut off the linkage between glucose units in cellulose. So, the surface modification of carbon materials with these functional groups, namely, carbon sulfonation process, becomes the determining step to producing efficient carbon acid catalysts. Conventional methods for the carbon sulfonation are the hydrothermal and reflux method, in which hazardous chemicals are necessary, such as concentrated sulfuric acid (95–98%), chlorosulfonic acid, fuming sulfuric acid, or 4-benzenediazoniumsulfonate under elevated temperature for dozens of hours.As a green and effective carbon sulfonation process, we have utilized plasma generated in contact with dilute sulfuric acid. Recently, we have investigated the mechanism of carbon sulfonation in GLIP processes. Active species produced near the gas–liquid interface such as •OH, SO3, and HOSO2• probably play important roles in carbon sulfonation. We are currently trying to enlarge the treatment capacity of carbon sulfonation by two methods, namely parallel plasma generation with ballast capacitors and large-area plasma generation by a dielectric barrier discharge. Also, effects of gases used for plasma generation such as air and Ar on the carbon sulfonation are investigated.This work was partially supported by the Environment Research and Technology Development Fund (JPMEERF20223R01) of the Environmental Restoration and Conservation Agency of Japan.

Mesoporous carbon particles by biomass waste based on sulfonation and copper oxide functionalization as efficient and stable electrode material for supercapacitor.

Here, the hierarchical mesoporous-activated carbon particles obtained by KOH activation from pistachio shell wastes are modified by both the sulfonation process and CuO doping by hydrothermal heating (CuO@S-doped PSAC) for use as a supercapacitor. It is predicted that the electrochemical performance of the porous carbon electrode material obtained by such CuO doping and sulfonation process will be significantly increased with increased Faradaic capacitance. The electrochemical performance of CuO@S doped PSAC composite is systematically investigated by electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and galvanostatic charge/discharge (GCD) in the presence of 1M H2SO4, 1M Na2SO4, and 1M NaOH as electrolytes. The CuO@S doped PSAC-based electrode shows excellent stability with high specific capacitance up to 397.16 F/g at 0.1 A/g and 92.64% retention. Furthermore, FTIR, SEM, XRD, EDS, and nitrogen adsorption/desorption analyses are used for the characterisation of the obtained composites. Based on a significant supercapacitor performance, the synthesis strategy of carbon-based electrode material containing sulfonation and CuO modifications derived from agricultural biomass waste material is predicted to be a valuable example.

Enhancing the thermal and mechanical properties of sulfonated peek fiber composites with reduced smoke density and toxicity

AbstractPolyether ether ketone (PEEK) sulfonation process is a reasonably easy but time‐consuming to manufacture composites. This study focuses on altering PEEK powder in a sulfuric acid solution via a sulfonation process to develop sulfonated PEEK (SPEEK) resin for the fiber‐reinforced thermoplastic composite manufacturing and characterization steps. In this study, about 5 wt% PEEK powder was sulfonated in 98% sulfuric acid solution for 12 h at 65°C. The water bath technique was used for the precipitation process to obtain the SPEEK polymer. After proper washing and drying, the SPEEK matrix (resin) was obtained by dissolving it in dimethylformamide in a ratio of 1:2. This resin solution was then used to manufacture thermoplastic Kevlar and glass fiber‐reinforced composites employing wet layup process and cured at an elevated temperature under pressure. These SPEEK composites passed the flame retardancy UL94 test with a V0 rating. The average water contact angle of the glass fiber‐ and Kevlar‐SPEEK composites is 93.67° and 102.24°, respectively. The average tensile strength values of these composites were found 222.22 and 284.35 MPa, correspondingly. The smoke density and toxicity tests of the glass fiber‐SPEEK composite confirmed lower smoke generation with the modifications. These SPEEK‐fiber composites can be considered for various industrial applications, including aviation, energy, drone, defense, and automotive.

Alcohol formaldehyde resin solid acid catalytic conversion of biomass into furan compounds

The conversion of waste lignocellulosic biomass into biomass platform chemicals is very promising. In this work, a novel resin-based solid acid catalyst was obtained by condensation of furfuryl alcohol with furfural, and mild calcination and sulfonation process. Then it was used to convert sugars and biomass to obtain furan compounds. Results showed that the solid acid with a furfural to furfuryl alcohol molar ratio of 3:1 is an irregular mesoporous material, with a specific surface area of 134.18 m2/g and an acid content of 2.723 mmol/g, which is extremely stable below 200 °C. 82.2 % (from fructose), 15.8 % (from glucose), 10.0 % (from cellobiose) yields of 5-HMF and 35.5 % (from xylose) yield of furfural could be obtained at 160 °C for 2 h. It can be reused more than 5 times and can restore the best catalytic effect after re-sulfonation. Notably, in the catalytic conversion of rice husk, rice straw, camphor tree branch and leaves under typical reaction conditions, 5-HMF and furfural was in yields of 9.4–24.5 % and 20.3–47.9 %, respectively. Moreover, a 10 % water dropwise to solvent can effectively promote the catalytic conversion of biomass, while there is a significant inhibitory effect after it exceeds 20 %.

Fatliquor for fungus resistant leather-a sustainable ecofriendly approach

Surface-active softening agents, such as Fatliquors, have a significant impact on the leather industry as they enhance the physicochemical properties of leather. This study focuses on analyzing the synthesis, properties, characterization, and sulfonation of Swietenia mahagoni seed oil to determine its potential as a fatliquoring agent for leather. An investigation was conducted to verify the alteration of Swietenia mahagoni oil through the analysis of its properties before and after the sulfonation process. A scientific analysis was carried on the oil using GC-FID, revealing the presence of various unsaturated fatty acids such as linoleic, linolenic, oleic, palmitic, and arachidic acids. This demonstrates the sulfonating capability of this sky fruit seed oil. A fatliquor was created by sulfonating the oil, and the sulfonation was verified through Fourier Transform Infrared Spectroscopy (FTIR) and 1H Nuclear Magnetic Resonance (NMR) spectra. The prominent peak observed at 1209 cm-1 in the FTIR spectra indicated the stretching of S=O in both sulfate and sulfonate groups. The newly formed protons (H–C–S or H–C–O) showed signals between δ 4.09 and 4.29 ppm in the 1H NMR spectra, confirming the sulfonation of the fatliquor that was prepared. Moreover, the change in the melting point of sulfonated Mahogany oil from 40.8 °C to 48.1 °C suggests increased saturation levels. The fatliquor's emulsion stability was found to be at a satisfactory level. After conducting tests on the treated leather, the physical strength and morphological structure was analyzed using Field Emission Scanning Electron Microscopy (FE-SEM), the fatliquor improved the lubrication and strengthened the fibrous network structure of the leather, composed of thin and tight collagen fibers. The BOD5/COD ratio of the effluent from the experimental trial was determined to be 0.52, suggesting that the fatliquor developed is a biodegradable product. Finally, the antifungal capabilities of the fatliquor-treated leather were tested against four different fungus species: Aspergillus niger, Aspergillus flavus, Penicillium notatum, and Candida albicans, and the treated leather sample shown favorable antifungal activity.

Production of biosurfactant sodium lignosulfonate (NaLS) using elephant grass based lignin (Pennisetum purpureum) and NaHSO3

Elephant grass (Pennisetum purpureum) is an animal feed ingredient, especially ruminants with a lignocellulose content of 40.85% and lignin of 21.5% and can be used as a raw material for making biosurfactant sodium lignosulfonate. Biosurfactant is an amphiphilic molecule and has biodegradability. This study aims to obtain data on the effect of NaHSO3 concentration, reaction time, and the ratio of elephant grass: NaHSO3 on the sodium lignosulfonate content, yield, degree of sulfonation, and physico-chemical properties of sodium lignosulfonate obtained. This study consists of 3 treatment factors, namely NaHSO3 concentration, reaction time, and mass ratio of elephant grass : NaHSO3. The results showed that sodium lignosulfonate can be produced from elephant grass using direct sulfonation process. The best treatment combination was 80% concentration and 155 minutes reaction time which produced sodium lignosulfonate content of 20.619 mg/L and 65.83% yield. The physicochemical properties are: density 1.4061 g/mL, degree of sulfonation 57.73%, completely soluble in water, smells a little sulfur, has a brownish yellow color, pH 5, and the results of functional group analysis showed a change in functional groups.

In Vitro Evaluation of Optimized PEEK Surfaces for Enhanced Osseointegration

The materials traditionally used for implant applications, such as titanium alloys, cobalt chromium, and zirconium, often require surface modifications to achieve the desired osseointegration. These materials still have the problematic stress-shielding effect. To limit stress shielding, PEEK is the superior alternative to fulfill implant needs. However, the traditional methods of modifying and functionalizing the surface of PEEK are often expensive, time consuming, and are not easily translated into commercialization. Sulfonation is a process, which is dependent on controllable factors. Thus far, no research has been performed to optimize the sulfonation process. Our data suggest that the process factors can be controlled and optimized. Cellular activity was examined on the optimized PEEK surfaces through testing with pre-osteoblast MC3T3-E1 cells through cell viability (MTT assay), cell proliferation (DNA assay), cell differentiation (ALP assay), and cell mineralization (Alizarin red assay). Overall, sulfonated and heat-treated PEEK exhibited a statistically significant increase in DNA content over the course of 21 days, indicating more cell proliferation and viability for that surface. In vitro testing results showed that the optimized sulfonated and heat-treated PEEK exhibited superior cell proliferation and mineralization performance over smooth PEEK and sulfonated-only PEEK.

Exploring the weak visible-near-infrared and NO2 detection capabilities of PbS/Sb2O5 heterostructures with DFT interpretations

The need for photosensors and gas sensors arises from their pivotal roles in various technological applications, ensuring enhanced efficiency, safety, and functionality in diverse fields. In this paper, interlinked PbS/Sb2O5 thin film has been synthesized by a magnetron sputtering method. We control the temperature to form the nanocomposite by using their different nucleation temperature during the sulfonation process. A nanostructured PbS/Sb2O5 with cross-linked morphology was synthesized by using this fast and efficient method. This method has also been used to grow a uniform thin film of nanocomposite. The photo-sensing and gas-sensing properties related to the PbS/Sb2O5 compared with those of other nanomaterials have also been investigated. The experimental and theoretical calculations reveal that the PbS/Sb2O5 exhibits extraordinarily superior photo-sensing and gas-sensing properties in terms of providing a pathway for electron transport to the electrode. The attractive highly sensitive photo and gas sensing properties of PbS/Sb2O5 make them applicable for many different kinds of applications. The responsivity and detectivity of PbS/Sb2O5 are 0.28 S/mWcm−2 and 1.68 × 1011 Jones respectively. The sensor response towards NO2 gas was found to be 0.98 at 10 ppb with an limit of detection (LOD) of 0.083 ppb. The PbS/Sb2O5 exhibits high selectivity towards the NO2 gas. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) were used to analyze the geometries, electronic structure, and electronic absorption spectra of a light sensor fabricated by PbS/Sb2O5. The results are very analogous to the experimental results. Both photosensors and gas sensors are indispensable tools that contribute significantly to the evolution of technology and the improvement of various aspects of modern life.

Sugarcane bagasse valorization through integrated process for single cell oil, sulfonated carbon-based catalyst and biodiesel co-production

This study demonstrates the conversion of sugarcane bagasse (SB) into single cell oil (SCO), sulfonated carbon-based catalyst and biodiesel; this process aligns with waste-to-energy and circular bioeconomy concepts. SB was treated with dilute sulfuric acid to achieve SB hydrolysate (SBH) and SB solid residue (SBS). Candida tropicalis KKU-NP1, a newly isolated yeast, accumulated SCO content of 26.5 % from undetoxified SBH medium. A novel sulfonated carbon-based catalyst (SBS@SC) was generated from SBS by a one-step hydrothermal sulfonation process. It showed significant catalytic activity for the conversion of SCO-rich KKU-NP1 wet cell into biodiesel (FAME) under direct transesterification optimal conditions, with a FAME conversion yield of 90.1 %. Based on FAME profile, most of the estimated physicochemical and fuel properties of FAME were within the limits of ASTMD6751 and EN 14214 for biodiesel standards. For integrated process the final production of about 12.0 g SCO, 606.3 g SBS@SC catalyst and 10.8 g biodiesel from 1000 g raw SB were achieved.This study highlights the utilization of SB as a low-cost feedstock for producing multiple value-added products, emphasizing the advantages of waste utilization by integrated biorefinery concept, yielding practically no waste by-products over the whole production process.

The Formation Process and Mechanism of the 3D Porous Network on the Sulfonated PEEK Surface.

A three-dimensional (3D) porous network can be prepared on the PEEK surface by sulfonation with enhanced osseointegration and antibacterial properties. However, few studies have been conducted on the formation mechanism of a 3D porous network. In this work, the surface and cross-sectional morphologies, chemical compositions, functional groups, surface wettability, and crystalline states of sulfonated PEEK were investigated at different sulfonation times and coagulant concentrations. The results show that the number of nodular structures and broken fibers on the sulfonated PEEK surface as well as the size of macrovoids in the cross sections increase with increasing sulfonation times when water is used as a coagulant. In contrast, dilute sulfuric acid as a coagulant can inhibit the formation of surface porous structures and macrovoids in the cross sections. Moreover, all of the sulfonated PEEK samples have the same chemical compositions but exhibit better hydrophilicity as the number of microsized pores decreases. It is proposed that non-solvent-induced phase separation (NIPS) occurs during the sulfonation process, and the formation mechanism of surface and cross-sectional morphologies is discussed. Furthermore, it is assumed that the air is trapped in the microsized pores, leaving the surface of the 3D porous network in the Cassie-wetting state. All of these preliminary results throw light on the nature of the sulfonation process and may guide further modification of the structures of sulfonated PEEK.

Ultra high density carbon fiber derived from isotactic polypropylene fiber without skin‐core structure

AbstractPolypropylene (PP)‐based carbon fibers were prepared by sulfonation process of isotactic PP fibers with concentrated sulfuric acid, followed by stress‐less carbonization under nitrogen atmosphere. The stabilization behaviors of PP fiber under different sulfonation temperatures and time were discussed. The carbonization behavior of the stabilized PP fibers under different carbonization temperatures, as well as the mechanical performance of the obtained carbon fibers were investigated. The results indicated that linear PP molecule were effectively converted into thermally stable structure at higher temperature (≥130°C) in short time (2 h) through sulfonation‐desulfonation reaction, among which ordered graphite structure has been formed prior to the carbonization process. Meanwhile, the carbon fibers were considerably densified by increasing the sulfonation temperature and carbonization temperature, and a bulk density of 1.96 g/cm3 was achieved. Moreover, the temperature and time of the sulfonation process as well as the temperature of the carbonization process were regulated, and carbon fibers with tensile strength of 262.3 MPa was obtained, which was superior to that of 208.1 MPa for the linear low density polyethylene‐based carbon fibers reported previously. Isotactic PP was proved to be a promising candidate to develop carbon fibers with tunable graphite structure and mechanical performance.

Synthesis, characterization and optimization of sulfonated poly-ether-ether-ketone (sPEEK)/functionalized carbon nanotubes (c-CNTs) nanocomposite membranes for fuel cell application

Poly-ether ketone (PEEK) was modified to sulfonated poly-ether ketone (sPEEK) by sulfonation process with a degree of sulfonation 49.5%. Carbon nanotubes were acid-treated with sulfuric acid and nitric acid solution (3:1, v/v) for functionalization. sPEEK and sPEEK/c-CNT membranes were prepared by solvent casting method using dimethyl sulfoxide (DMSO) as solvent. The experimental part was conducted as per design of experiment employing response surface methodology consisting of three factors, namely (A) c-CNT (wt.%), (B) mixing temperature (°C), and (C) sPEEK concentration (mg/mL). The ion exchange capacity was found to increase with c-CNT (wt.%). Fourier-transform infrared spectroscopy confirms the sulfonation of PEEK. X-Ray diffraction investigates the influence of the sulfonation in the crystal structure of the sPEEK and sPEEK/c-CNT. Scanning electron microscopy images show that c-CNTs are dispersed well in the sPEEK matrix. The results showed slightly increasing water uptake and swelling ratio of the composites membranes. The analysis of variance (ANOVA) revealed that c-CNT (wt.%) is highly affecting the responses. Proton conductivity of sPEEK specimen is about 23.9 mS/cm, which is significantly increased to 57.0 mS/cm for sPEEK/0.12 c-CNT (wt.%) membrane suggesting its application for fuel cell.