Polyacrylonitrile Research Articles

First-Principles Study on Polymer Electrolyte Interface Engineering for Lithium Metal Anodes.

Modifying the interface between the lithium metal anode (LMA) and the electrolyte is crucial for achieving high-performance lithium metal batteries (LMBs). Recent research indicates that altering Li-metal interfaces with polymer coatings is an effective approach to extend LMBs' cycling lifespan. However, the physical properties of these polymer-Li interfaces have not yet been fully investigated. Therefore, the structural stability, electronic conductivity, and ionic conductivity of polymer-Li interfaces were examined based on first-principles calculations in this study. Several representative polymer compounds utilized in LMBs were assessed, including polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), and polyethylene oxide (PEO). Our research revealed that lithium fluoride is formed upon fluoropolymer degradation, explaining previously observed experimental results. Polymers containing nitrile groups exhibit strong adhesion to lithium metal, facilitating the formation of the stable interface layer. Regarding electronic conductivity, the fluoropolymers preserve a good insulating property, which diminished marginally in the presence of lithium, but that of PAN and PEO significantly reduces. Additionally, lithium diffusion on PTFE and PEO demonstrates low diffusion barriers and high coefficients, enabling easy transportation. Overall, our investigation reveals that the interfaces formed between various polymers and LMA have distinct characteristics, providing new fundamental insights for designing composites with tailored interface properties.

Mixed-mode cationic exchange paper combined with direct infusion mass spectrometry, a sustainable approach to determine opioids in biosamples

Direct infusion mass spectrometry (DI-MS/MS) allows the rapid analysis of samples and minimizes solvent usage by avoiding chromatographic separation. However, it is prone to ion suppression due to matrix effects, especially when biosamples are processed. In this context, sample preparation appears as the perfect complement to get proper analytical results. In this article, a novel and sustainable planar sorptive phase containing mixed-mode cationic exchange (MCX) particles is presented to overcome the limitations of DI-MS/MS in bioanalysis. The new phase uses cellulose paper as a natural substrate over which the particles can be retained using polyacrylonitrile (PAN) as the chemical binder. The high porosity of the cellulose substrate simplifies the synthesis since a straightforward dip-coating technique can be applied. For this purpose, MCX particles are initially dispersed in a PAN solution prepared in N,N-Dimethylformamide. A segment of paper is later introduced into the slurry, and the evaporation of the solvent leaves a film of PAN-MCX composite over the paper, where the particles are entrapped but accessible for the analyte's isolation. The resulting MCX-paper has been evaluated for the extraction of selected opioids (codeine, methadone, morphine, naloxone, oxycodone, and tramadol) from saliva and urine samples and their determination by direct infusion tandem mass spectrometry. Working at the optimized conditions, the limits of detection were in the low μg L−1 range. The precision, expressed as relative standard deviation, was better than 12 % under intra-day and inter-day conditions. The accuracy, expressed as relative recoveries, provides values in the ranges 89–113 % and 74–121% for saliva and urine, respectively. The method was finally applied to analyze saliva and urine samples collected from patients under codeine treatment.

Ferrocene-Modified Polyacrylonitrile-Containing Block Copolymers as Preceramic Materials.

In the pursuit of fabricating functional ceramic nanostructures, the design of preceramic functional polymers has garnered significant interest. With their easily adaptable chemical composition, molecular structure, and processing versatility, these polymers hold immense potential in this field. Our study succeeded in focusing on synthesizing ferrocene-containing block copolymers (BCPs) based on polyacrylonitrile (PAN). The synthesis is accomplished via different poly(acrylonitrile-block-methacrylate)s via atom transfer radical polymerization (ATRP) and activators regenerated by electron transfer ATRP (ARGET ATRP) for the PAN macroinitiators. The molecular weights of the BCPs range from 44 to 82 kDa with dispersities between 1.19 and 1.5 as determined by SEC measurements. The volume fraction of the PMMA block ranges from 0.16 to 0.75 as determined by NMR. The post-modification of the BCPs using 3-ferrocenyl propylamine has led to the creation of redox-responsive preceramic polymers. The thermal stabilization of the polymer film has resulted in stabilized morphologies based on the oxidative PAN chemistry. The final pyrolysis of the sacrificial block segment and conversion of the metallopolymer has led to the formation of a porous carbon network with an iron oxide functionalized surface, investigated by scanning electron microscopy (SEM), energy dispersive X-ray mapping (EDX), and powder X-ray diffraction (PXRD). These findings could have significant implications in various applications, demonstrating the practical value of our research in convenient ceramic material design.

Forward osmosis zwitterionic membranes for platelet concentration – Evaluation of the feasibility of the concept

This study focuses on the development of forward osmosis (FO) membranes tailored for platelet and growth factor enrichment applications while maintaining minimal activation throughout the process. The FO membrane structure comprises a polyacrylonitrile (PAN) layer, fabricated using vapor-induced phase separation (VIPS), atop a polyethylene terephthalate (PET) substrate. Then, a polyamide (PA) layer was formed through interfacial polymerization (IP) at the PAN layer interface. The PET side of the membrane was further enhanced with coatings of antifouling copolymers, based on poly(ethylene glycol) methyl ether methacrylate (PEGMA) alone or both PEGMA and zwitterionic sulfobetaine methacrylate (SBMA). In a first step, the formation of each layer was optimized. The structure of the PAN layer was adjusted through the polymer concentration (15 wt%) and the exposure time to vapors (15 min) during the VIPS step. The PA layer was optimized by adjusting the curing temperature to 70 °C. The antifouling copolymer was selected by conducting protein adsorption tests. Subsequently, these tailored FO membranes were employed in the enrichment of plasma proteins, growth factors, and platelets from platelet-rich plasma. It is shown that the membrane modified with a copolymer made of butyl methacrylate (BMA), PEGMA and SBMA, referred to as poly(BMA-r-PEGMA-r-SBMA), enabled to reach a Human Serum Albumin concentration factor of 1.32 and a platelet concentration using PRP of 2.4. Despite partial platelet activation (12 %) due to the high cell concentration, the platelet content is much higher than in PRP or whole blood, which could benefit platelet-based therapies. In addition, the system can be applied to the concentration of growth factors, with PDGF and VEGF concentration factors of 1.92 and 2.58, respectively, which could contribute to the advancement of regenerative medicine.

Enhanced anti-biochemical fouling properties of the polyacrylonitrile membranes assisted by the d-amino acid surface-modified halloysite nanotubes

Membrane fouling has always been one of the key problems to be solved in the liquid–liquid separation process of biomacromolecules, proteins, bacteria, etc. Here, halloysite nanotubes (HNTs) surface-modified with D-Amino acid (D-Aa) is synthesized in one step and introduced into the polyacrylonitrile (PAN) ultrafiltration membrane matrix to obtain a PAN mixed matrix membrane (MMM). D-Aas with three different R groups are selected to modify the HNTs. The results show that the carboxyl and amino groups of the D-Aa molecules interact with the surface of HNTs through hydrogen bonds, while the R groups are oriented towards the outside of the tube, thereby becoming the main factor affecting the surface chemical structure of the HNTs. Therefore, due to the low polarity of isobutyl and the good affinity with PAN and DMAc molecules, D-leucine-modified halloysite nanotubes (D-Leu@HNTs) can be evenly dispersed in the PAN membrane matrix and segregate to the membrane top-surface and pore wall during the non-solvent induced phase separation (NIPS) process with the solvent exchange between water and DMAc, thereby significantly improving the pore structure and hydrophilicity of the polyacrylonitrile membrane, and ultimately giving the PAN/D-Leu membrane ultra-high pure water permeability (PWP) of 1334 L·m−2·h−1·bar−1, rejection of 100 %, and excellent anti-biochemical fouling performances. The prepared PAN/D-Leu membrane maintains stable and efficient filtration performances in the 300-hour cross-flow experiment, and the membrane after testing still has excellent anti-biofilm fouling performance, showing a promising industrial application prospect.

Assessment of microplastic pollution and polymer risk in the sediment compartment of the Limfjord, Denmark

Estuarine sediments intercept and temporarily retain microplastics before they reach the marine seafloor, impacting various organisms, including key commercial species. This highlights the critical need for research on microplastic exposure in these transitional environments. This study provides a detailed assessment of microplastic pollution in the sediment compartment of the Limfjord, a 1500 km2 large Danish fjord, and introduces the Polymer Hazard Index (PHI) as a tool for evaluating polymer-specific risks. Thirteen sediment samples were collected, covering an anthropogenic gradient along the fjord. State-of-the-art methods were applied for extracting and identifying (FPA-μFT-IR imaging) microplastics (10–5000 μm). Our results indicate that microplastic contamination is pervasive across all sampled locations with concentrations ranging from 273 to 4288 particles kg−1, with a predominance of small microplastics (<100 μm). The estimated mass-based concentrations ranged between 2.60 × 104–1.11 × 106 ng kg−1. Overall, we estimated a microplastic stock of 3.8 × 103–1.65 × 105 kg in the surface sediments of the Limfjord, i.e., some 2.5–110 kg km−2. The application of the PHI revealed significant risks associated with specific polymers, such as polyacrylonitrile (PAN) and acrylonitrile butadiene styrene (ABS), underscoring the importance of considering polymer-specific hazards in environmental assessments.

Effect of surfactants on the permeation rate and selectivity of polyamide composite membranes for organic solvent nanofiltration

Solvent-resistant membranes are pivotal in industrial separations. This study aims to develop thin-film composite polyamide (TFC-PA) membranes with enhanced organic solvent nanofiltration (OSN) capabilities. Polyallylamine hydrochloride (PAAH) was used as the aqueous amine and isophthaloyl chloride (IPC) as the crosslinker to form the polyamide active layer by interfacial polymerization (IP) on a polyacrylonitrile (PAN) support. The impact of using anionic sodium dodecyl sulfate (SDS) and cationic cetyltrimethylammonium bromide (CTAB) to act as phase transfer agents during IP was investigated to understand their potential for facilitating the transfer of PAAH to the organic phase for reaction with IPC. The SDS and CTAB were separately dissolved into the PAAH solutions before IP to evaluate their effects on membrane properties. Extensive characterization including SEM, EDX, AFM, Water Contact Angle, ATR-FTIR, and Solid (CP-MAS) 13C NMR revealed various chemical and structural features of the membrane. The membrane M2 (PAAH-IPC) (exhibited >98% rejection for various anionic and cationic dyes. The inclusion of SDS during interfacial polymerization led to a substantial 3-fold increase in methanol permeate flux from 31 L m−2 h−1 to 119 L m−2 h−1, at a pressure of 15 bar. Conversely, the addition of CTAB resulted in membranes with higher permeate flux but insufficient dye rejection. Moreover, after three weeks of static aging of the membranes no significant changes were detected in either permeability or solute rejection, substantiating the stability of membranes.

A ternary composite nanofibrous photocatalyst: FcLR-gC3N4/polyisothianaphthene/polyacrylonitrile for degradation of organic dyes

BackgroundWater pollution by organic dyes is one of the important environmental issues. When substances such as organic dyes are discharged into water, they can severely pollute the water and harm the life of living organisms. MethodsA new ternary composite nanofibrous photocatalyst, FcLR-gC3N4/PITN/PAN, was produced through 1) synthesis of a graphitic carbon nitride (g-C3N4)-based ferrocenyl dithiophosphonic acid, FcLR-gC3N4, by the attachment of Ferrocenyl Lawesson's Reagent (FcLR) to g-C3N4 nanosheets, 2) incorporation of the FcLR-gC3N4 into the polymeric matrix of as-prepared polyisothianaphthene (PITN) blending with polyacrylonitrile (PAN), and 3) fabrication of electrospun nanofibers (NFs) through electrospinning. Significant findingsThe degradation of methyl orange (MO) and methylene blue (MB) was more efficient on FcLR-gC3N4 compared to g-C3N4 alone, and on FcLR-gC3N4/PITN/PAN compared to FcLR-gC3N4, confirming the effective role of both FcLR and PITN/PAN matrix in the degradation of the dyes. The ternary composite nanofiber degraded 92% of MB and 29% of MO. The MB mineralization percentages of 65% (TOC), 60% (COD), and 55% (BOD) were achieved after 2 h and 30 min. Radical trapping experiments consistent with the Tauc plots and Mott-Schottky plots distinguished O2•- as the primary species in the degradation mechanism of MB. The MB degradation pathway was determined through LC-MS-MS. The electrochemical impedance spectrum (EIS) and photocurrent measurements confirmed the higher photocatalytic activity of FcLR-gC3N4 compared to g-C3N4 alone by studying the charge carrier's separation and recombination. A high recyclability was found for FcLR-gC3N4. The recycling stability of FcLR-gC3N4 increased after its embedding into the nanofibrous matrix of PITN/PAN.

Polyacrylonitrile as a binder realizes high-rate activated-carbon-based supercapacitors

Highly polar CN functional groups on polyacrylonitrile (PAN) facilitate strong hydrogen bonding and dipole-dipole interactions with hydroxyl groups on the surfaces of active materials and current collectors. Here we report that the strong interaction between PAN and carbon black (CB) particles facilitates a uniform distribution of CB particles within the electrode and forms a well-connected conductive network on the surface of active material particles. This significantly enhances electron transport within the electrode, offering superior rate performance and cycling stability beyond traditional binders like polyvinylidene fluoride (PVDF). Activated carbon (AC) electrodes containing 7.70 wt.% PAN binder (AC-7.7PAN) deliver areal capacitances over 0.60 F cm⁻2 at a scan rate of 500 mV s⁻1, and exhibits a high gravimetric energy density (Eg) of 26.20 Wh kg⁻1 and high areal energy density (Ea) of 0.33 mWh cm⁻2 at a current density of 1 A g⁻1. An AC-7.7PAN coin-cell supercapacitor maintains up to 62 % of its initial capacitance at a scan rate of 200 mV s⁻1, while a controlled AC-7.7PVDF coin-cell keeps only 37 % under the same conditions. The AC-7.7PAN coin-cell retains 91 % of its capacity even after 50,000 charge/discharge cycles at a constant current of 5 A g⁻1. The ability of PAN to evenly distribute conductive agents might be attractive for other power-type electrochemical electrodes, for which effective electron transport are extremely required.

Enhancing Carbon Nanotube Yarns via Infiltration Filling with Polyacrylonitrile in Supercritical Carbon Dioxide.

Carbon nanotube (CNT) fibers are renowned for their exceptional axial tensile strength and modulus. However, in yarn form, they frequently encounter transverse loading in practical applications, which exposes their suboptimal mechanical attributes rooted in inadequate inter-tube interactions and yarn surface defects. Efforts to mitigate micro-slippage among CNTs have encompassed gap-filling methodologies with varied materials, yet the outcomes have fallen short of expectations. This work aimed to enhance the mechanical properties of CNT yarns via infiltration with polyacrylonitrile (PAN) under supercritical carbon dioxide (sc-CO2) conditions. PAN was strategically chosen for its capability to undergo pre-oxidation and subsequent carbonization, leading to robust graphitic reinforcement. Leveraging sc-CO2's swelling and high permeability properties, the infiltration process effectively plugged interstitial spaces, elevating the yarn's tensile strength to 277.50 MPa and Young's modulus to 5094.05 MPa. Additional enhancements were realized after pre-oxidation, conferring a dense, reinforced shell structure that augmented tensile strength by 96.93% and Young's modulus by 298.80%. Scanning electron microscopy (SEM) analyses revealed a homogeneous PAN distribution within the yarn matrix, corroborated by X-ray photoelectron spectroscopy (XPS) evidence of C-N bonding, indicative of a successfully interlaced network. Consequently, this investigation introduces a novel strategy to tackle micro-slippage in CNT yarns, thereby achieving substantial improvements in their mechanical resilience.

Simultaneous improvements in energy density and thermal conductivity of PAN polymer nanocomposites enabled by core-shell structure BZCT@BNNS nanofibers

If the heat generated by electronic devices in high-power applications cannot be dissipated in a timely manner, it will not only affect the use of the equipment but also reduce its service life. Therefore, there is an urgent need to develop thin films of dielectric nanocomposites with high thermal conductivity, high energy storage, and excellent flexibility and electrical insulation performance. In this study, we reported the successful preparation of BZCT nanofibers (BZCT NFs) and core-shell structures BZCT@BNNS nanofibers using electrospinning and coaxial electrospinning techniques, respectively, and there were used to composite with polyacrylonitrile (PAN) polymer matrix to prepare BZCT NFs/PAN and BZCT@BNNS/PAN dielectric nanocomposites thin film. Research has found that when the shell thickness of BNNS is 15 nm and BZCT@BNNS (15 nm) volume fraction is 20 vol%, the comprehensive performance of the dielectric nanocomposites is the best, with thermal conductivity and energy storage performance of 3.36 W m−1K−1 and 12.23 J/cm3, respectively. Therefore, the nanocomposites thin film can be used as a potential high-performance dielectric material for thermal management applications in high-power density electronic devices.

Effect of temperature gradient on the chemical structure and physical morphology of polyacrylonitrile fibers during thermal stabilization process

The thermal stabilization process is a crucial stage for microstructure transformation and quality of carbon fibers, which is determined by the stabilization temperature gradient. In this work, the effect of the temperature gradient on the evolution of both chemical structures and physical morphology of polyacrylonitrile (PAN) fibers at multistage of thermal stabilization process was investigated. Combined with functional groups, oxygen element content, and aromatization index, increasing temperature reasonably shifted oxidation and cyclization reaction into early stage and the corresponding samples possessed relatively large degree of cyclization. It was worth noting that high stabilization temperature gradient could accelerate the formation of the conjugated structures at early stage and facilitate the cyclization reaction in the stabilized fibers. As for morphologies, there were aligned microfibrils and transvers lamellae in stabilized fibers. Their radial structure difference increased firstly and then decreased in the later stage. The tensile strength and tensile modulus decreased during the thermal stabilization process. Moreover, increasing temperature resulted in reduction of tensile strength and tensile modulus, which was mainly resulted by the high degree of cyclization instead of structural defects. These results guide the design and optimization of temperature program and adjusting the processing parameters for all commercially PAN fibers without any additional conditions.

Synthesis of spiroindoline derivatives and biphenyl compounds in green solvent via a “capture–release” mechanism using modified polyacrylonitrile fiber as a catalyst

Green synthesis of critical bioactive molecules and fine chemicals is attracting increasing interest. This study investigates the use of two distinct functionalized polyacrylonitrile (PAN) fibers (PANEDBPF and PANEDBP-Pd0F) as effective catalysts in a green solvent comprising ethanol and water. Firstly, a PAN fiber was modified using 2-(diphenylphosphino) ethylamine, a strongly nucleophilic phosphine compound, to obtain PANEDBPF. Spiroindoline derivatives were obtained in 98 % yields when the reaction was conducted using 5 mol% of PANEDBPF as the catalyst at 70 °C for 30 min. Next, we loaded PdNPs onto PANEDBPF to obtain PANEDBP-Pd0F. When the Suzuki coupling reaction was conducted at room temperature (25 °C) using 0.5 mol% of PANEDBP-Pd0F, the products were obtained in an extremely high yield of 99 %. Additionally, the unique enrichment of the substrate by the functionalized fibers during the reaction and the subsequent release of the product from the microenvironment conform to the “capture–release” reaction mode of catalysis. Both PANEDBPF and PANEDBP-Pd0F demonstrated good gram-scale amplification, repeatability, catalytic activity, and stability. Hence, they are highly promising candidates for green chemistry applications.

Full‐Color and High‐Resolution Femtosecond Laser Patterning of Perovskite Quantum Dots in Polyacrylonitrile Matrix

AbstractLaser patterning of perovskite quantum dots (PQDs) in polymer matrix enables in situ synthesis, easy integration, and much improved long‐term stability, holding great promises for varieties of photonics, and optoelectronics applications. Although multi‐color PQD patterns have been demonstrated through tuning the halide stoichiometry, it remains significantly challenging to achieve full‐color patterns due to the slow and spontaneous crystallization of the chlorinated perovskite precursor at room temperature. Herein, polyacrylonitrile (PAN) is introduced to serve as the matrix material, the excess cyano groups of which would coordinate with dissociative cesium and lead cations in the precursor film, leading to the suppression of the unprompted crystallization process. Taking advantage of the nonthermal and contactless ultrafast femtosecond laser, full‐color PQDs are in situ fabricated by tuning the halide stoichiometry in the PAN matrix, with the emission wavelength in the range of 425–685 nm, spanning from deep blue to deep red color, and a sub‐diffraction feature size of ≈400 nm. The approach allows ultrafine and programmable fabrication of full‐color PQD arrays and arbitrary patterns with high resolution and stability. This facile, efficient, and reliable technique believed to offer a novel pathway for precise manufacturing of various photonic or optoelectronic devices based on patterned PQDs.

Synthesis and Characterization of Nanocellulose/Polyacrylonitrile‐based Carbon Nanofibers: An Approach toward Low Cost and Sustainable Agro Waste based Carbon Nanomaterials

AbstractThe cost of polymer precursors and high energy need in carbonization for the preparation of carbon materials are two limiting factors in the commercialization of carbon‐based materials. In this study, carbon nanofiber films were prepared by adding a very small concentration of polymer polyacrylonitrile in nanocellulose (extracted from agro waste i.e., rice straws) with an overall aim of producing carbon nanomaterials with cost effective, renewable and sustainable carbon source. Polyacrylonitrile (PAN) added nanocellulose solution was drop‐casted to prepare Nanocellulose/Polyacrylonitrile‐based nanofibers film (NC/PAN). It was further stabilized in air atmosphere at 280 °C followed by carbonized in nitrogen atmosphere at 700 °C. It was found that addition of NC/PAN have 18 % lower activation energies than PAN. Results of tunneling electron microscopy showed that polyacrylonitrile/nanocellulose films carbonized at 700 °C temperature exhibited amorphous carbon nanofibers structure similar to bare polyacrylonitrile based carbon film carbonized at higher temperature of 1000 °C‐1200 °C. Furthermore, polyacrylonitrile/nanocellulose based carbon nanofibers have showed high degree of carbonization ((ID)/(IG)=0.87) as compared to bare polyacrylonitrile based carbon nanofibers film ((ID)/(IG)=1.02). This may be attributed to chiral nature of nanocellulose which served as a template to orientation of graphene planes and showed efficient carbonization.

Morphology engineering of nanofibrous poly(acrylonitrile)-based strong anion exchange membranes for enhanced protein adsorption and recovery

The (bio)pharmaceutical and food industries are transitioning towards circular economy to minimise waste and foster sustainability in the supply chain of biomolecule-based drugs and supplements. Membrane chromatography is expected to play a crucial role in this transition, with the potential to maximize recovery and reduce operating costs. The development of chromatographical membranes is however impeded by the lack of understanding on the membrane structure – chemistry – performance relationship. Here a one-pot synthesis of anion exchange membranes with engineered nanofibrous morphology was studied by electrospinning the blend of polyacrylonitrile (PAN) and tailored quaternized poly(acrylonitrile)-co-poly(2-(dimethylamino)ethyl acrylate) copolymer containing 15 mol% of functional groups, namely PAN-pAQ membranes. Comprehensive evaluations were conducted on the influence of the electrospinning parameters on the nanofibre morphology, surface properties and binding capacity of model protein bovine serum albumin (BSA). The fibre alignment was shown to play a significant role, i.e., membrane with anisotropic fibres obtained by increasing the drum rotational speed to 2000 rpm allowed a high BSA binding capacity of 166 mg∙g−1, i.e., 45–66 % higher than other membranes with randomly-oriented nanofibres. This study is expected to contribute towards the design of future membranes for effective purification and recovery of biomolecules from natural and waste streams, promoting circular bio-economy.

Charge-patterned nanofiltration membranes with polystyrene sulfonate particles and polyethyleneimine in cross-linked polyvinyl alcohol

Removing salinity has always been a challenge for wastewater treatment. Utilizing nanofiltration (NF) membranes is a promising approach. However, currently available NF membranes are less effective in monovalent salt removal. In this study, work toward the initial aim of fabricating charge mosaic membranes led to charge-patterned NF-selective films on polyether sulfone (PES) or polyacrylonitrile (PAN) support membranes, with similar rejection for mono- and divalent salts. The membranes were fabricated by a two-step layer assembly of first negatively charged polystyrene sulfonate (PSS) particles immobilized in a polyvinyl alcohol (PVA) layer, followed by coating a positively charged polyethyleneimine (PEI) layer. Both PVA and PEI were crosslinked using glutaraldehyde that had initially been impregnated into the support membrane. The type of support membrane, nanoparticle, PVA, and PEI concentrations during fabrication, as well as feed pH and salt concentration, play significant roles in separation performance of obtained composite membranes. Charge-patterned NF membranes fabricated using 0.5 wt.% PVA and 0.05 wt.% PSS for assembly of the first layer followed by coating 0.5 wt.% PEI solution had even somewhat higher rejection for monovalent salt (NaCl; ∼82%) compared to multivalent salts (Na2SO4, MgSO4, and MgCl2; ∼74%), at a permeance of 5.5 LMH/bar on the PES and 3.1 LMH/bar on the PAN support membrane.

Deep-Learning Interatomic Potential Connects Molecular Structural Ordering to the Macroscale Properties of Polyacrylonitrile.

Polyacrylonitrile (PAN) is an important commercial polymer, bearing atactic stereochemistry resulting from nonselective radical polymerization. As such, an accurate, fundamental understanding of governing interactions among PAN molecular units is indispensable for advancing the design principles of final products at reduced processability costs. While ab initio molecular dynamics (AIMD) simulations can provide the necessary accuracy for treating key interactions in polar polymers, such as dipole-dipole interactions and hydrogen bonding, and analyzing their influence on the molecular orientation, their implementation is limited to small molecules only. Herein, we show that the neural network interatomic potentials (NNIPs) that are trained on the small-scale AIMD data (acquired for oligomers) can be efficiently employed to examine the structures and properties at large scales (polymers). NNIP provides critical insight into intra- and interchain hydrogen-bonding and dipolar correlations and accurately predicts the amorphous bulk PAN structure validated by modeling the experimental X-ray structure factor. Furthermore, the NNIP-predicted PAN properties, such as density and elastic modulus, are in good agreement with their experimental values. Overall, the trend in the elastic modulus is found to correlate strongly with the PAN structural orientations encoded in the Hermans orientation factor. This study enables the ability to predict the structure-property relations for PAN and analogues with sustainable ab initio accuracy across scales.

Centrifugally spun hydroxyapatite/carbon composite nanofiber scaffolds for bone tissue engineering

In recent years, advancements in tissue engineering have demonstrated the potential to expedite bone matrix formation, leading to shorter recovery times and decreased clinical challenges compared to conventional methods. Therefore, this study aims to develop composite carbon nanofibers (CNFs) integrated with nano-hydroxyapatite (nHA) particles as scaffolds for bone tissue engineering applications. A key strategy in achieving this objective involves harnessing nanofibrous structures, which offer a high surface area, coupled with nHA particles expected to accelerate bone regeneration and enhance biological activity. To realize this, polyacrylonitrile (PAN)/nHA nanofibers were fabricated using the centrifugal spinning (C-Spin) technique and subsequently carbonized to yield CNF/nHA composite structures. Scanning Electron Microscopy (SEM) confirmed C-Spin as a suitable method for PAN and CNF nanofiber production, with nHA particles uniformly dispersed throughout the nanofibrous structure. Carbonization resulted in reduced fiber diameter due to thermal decomposition and shrinkage of PAN molecules during the process. Furthermore, the incorporation of nHA particles into PAN lowered the stabilization temperature (by 5 °C–20 °C). Tensile tests revealed that PAN samples experienced an approximately 80% increase in ultimate tensile strength and a 187% increase in modulus with a 5 wt.% nHA loading. However, following carbonization, CNF samples exhibited a 50% decrease in strength compared to PAN samples. Additionally, the addition of nHA into CNF improved the graphitic structure. The incorporation of nHA particles into the spinning solution represents a viable strategy for enhancing CNF bioactivity.

Electrochemical degradation of small molecule dyes by TiO2-decorated polyacrylonitrile nanofiber membranes with superior properties

To optimize the uniform dispersion of nanoparticles and enhance their catalytic degradation effect on small molecule dyes in textile wastewater, titanium dioxide (TiO2) was deposited on polyacrylonitrile (PAN) fiber membranes using magnetron sputtering technology, and TiO2/PAN nanofiber membrane (NFM) with low content and high catalytic efficiency was successfully prepared. Through membrane separation coupling electrocatalysis, the composite membranes exhibited outstanding performance in removing Congo red (CR), Sunset yellow (SY), Methyl orange (MO), and Methylene blue (MB) dyes, with removal rates of 99.5%, 98.8%, 98.5%, and 87.2% respectively. Even after continuous catalysis for 10 h, the composite membranes maintained a high dye removal rate, demonstrating their remarkable stability and water treatment capabilities. Furthermore, TiO2/PAN NFMs displayed high pure water permeance, dye permeance, and mechanical strength. Specifically, M20 (magnetron sputtering time of 20 min) showed water permeance and dye (SY) permeance values of 1944 L·m−2·h−1·bar−1 and 816 L·m−2·h−1·bar−1, respectively, and indicate superior mechanical and electrochemical properties. During the electrocatalytic process, TiO2/PAN NFMs generated reactive oxygen species (ROS) on the surface, imparting a self-cleaning property that extended the service life of the membranes and offered an effective solution for textile wastewater treatment.