Polyacrylonitrile-based Carbon Fibers Research Articles

Sizing-agent control of the high-focusing and spread-ability of a melt-spun polyacrylonitrile-based carbon fiber and its interfacial shear strength

Sizing-agent control of the high-focusing and spread-ability of a melt-spun polyacrylonitrile-based carbon fiber and its interfacial shear strength

Molecular Modeling of Stabilization during Processing of Polyacrylonitrile-Based Carbon Fibers

Molecular Modeling of Stabilization during Processing of Polyacrylonitrile-Based Carbon Fibers

Unravelling lithium distribution in carbon fibre electrodes for structural batteries with atom probe tomography

Carbon fibres in structural batteries are multifunctional by acting both as structural reinforcement and as lithium (Li)-ion battery electrode. The relationship between the microstructure and mechanical capabilities of carbon fibres are well established, but much remains unexplored regarding their electrochemical properties. Specifically needed is a nanoscale understanding of how Li atoms distribute and interact in the carbon fibres. Atom probe tomography (APT) is uniquely positioned to provide subnanometre resolution in three dimensions. However, it has previously been hampered by undesirable Li migration during analysis. Here, we show that APT is successfully used to analyse electrochemically cycled polyacrylonitrile-based carbon fibres, through electrostatic shielding by means of conductive coating. We measure ∼1.5 at% Li in the carbon fibres after full delithiation, and thus identify trapped Li to constitute a substantial part of the initial capacity fade. After lithiation, Li accounts for ∼9 at% and according to frequency distribution analysis tend to agglomerate on the atomic scale. With nearest neighbour analysis, Li agglomeration is shown independent of heteroatom dopants such as nitrogen. Thus, the agglomeration is more likely induced by differing accessibility for Li in the crystalline and amorphous domains in the carbon fibre. The method used in this study can inform APT experiments on other type of Li-containing carbon electrodes. The findings of the study can be used to guide design of novel carbon fibres for structural batteries with enhanced electrochemical properties.

Electro-activation of peroxymonosulfate using a carbon fiber membrane anode for high-efficient degradation of antibiotic wastewater: The dominant role of singlet oxygen

A flow-through peroxymonosulfate (PMS) electro-activation system with a polyacrylonitrile-based carbon fiber (PCF) membrane anode (denoted as E-PCF-PMS system) was developed. The introduction of the PCF membrane anode enabled the flow-through electrocatalytical system to achieve a remarkable tetracycline (TC) removal of 96.0 ± 0.2 % within 15 min, with a degradation rate of 0.273 min−1. Scavenging investigations revealed that singlet oxygen (1O2) was the dominant reactive oxygen species for TC degradation in the E-PCF-PMS system, and this finding was confirmed by electron paramagnetic resonance tests. Potential degradation pathways of TC were identified according to the detected intermediates and calculations of density functional theory, and a decreasing trend in the toxicity of TC intermediates was discovered. Thanks to the 1O2-dominated pathway, the constructed E-PCF-PMS system could achieve efficient TC degradation under different concentrations of several common anions (Cl−, NO3−, HPO42−, and HCO3−) and humic acid (HA). General applicability and reusability tests demonstrated the excellent practicability of the proposed system. The PMS electro-activation system offers a potential technique for high-efficient degradation of contaminants in water and wastewater.

One-step liquid-phase synthesis of platinum nanocatalysts supported on carbon fiber substrates and their electrochemical characterization

Highly dispersed Pt nanoparticles supported on polyacrylonitrile-based carbon fiber substrates were prepared using a one-step liquid-phase process. Nanoparticles were grown on the fiber surface via electric resistance heating of the substrate in ethanol solutions containing a platinum-based organometallic complex as the nanoparticle precursor. After the synthesis, Pt nanoparticles were formed on the surface in highly dispersed states. Electrochemical characterization of the Pt nanoparticles was conducted using the substrates directly after synthesis. The Pt nanoparticles were electrochemically active and exhibited superior methanol oxidation properties.

STRUCTURE PARAMETER OF INTERFACIAL INTERACTION IN Cf/C COMPOSITES AND ITS CHANGE DURING PORE FORMATION PROCESS

The C<sub>f</sub>/C composite oxidation of polyacrylonitrile-based carbon fibers with a combined carbon matrix at 600°C up to a weight loss of 80 wt% has been investigated. The changes in the open porosity, specific surface area, apparent and true densities of the composite, as well as the ultimate strength and elastic modulus during three-point transverse bending tests have been analyzed. An analytical model for obtaining qualitative and semi-quantitative estimates of the change in integral pore size during oxidation of heterophase materials has been developed. The change in pore size is estimated through the evolution of open porosity P and materials specific surface area S. The model has been validated in the C<sub>f</sub>/C composite oxidation study. The composite's mechanical properties dependences on the value of the integral pore size are obtained and analyzed. The structural parameter P/S characterizes the change in the interphase interaction during pores formation and development. It is established that the failure mechanism depends on the value of the parameter P/S and dynamically changes with the oxidation of C<sub>f</sub>/C composite. The use of P/S parameter as a criterion for estimation and control of composite materials structural integrity in open systems is proposed.

Reusable and Practical Biocomposite Based on Sphingopyxis sp. YF1 and Polyacrylonitrile-Based Carbon Fiber for the Efficient Bioremediation of Microcystin-LR-Contaminated Water.

Microbial degradation is a cost-effective and environmentally friendly method for removing microcystin-LR (MC-LR). However, the application of free bacteria has limitations due to low operational stability and difficulties in recovery. In a previous study, our group successfully isolated a highly efficient MC-LR-degrading bacterium, Sphingopyxis sp. YF1, from Taihu. To enhance its practical potential in addressing MC-LR-contaminated water pollution, a novel biological material named polyacrylonitrile-based carbon fiber @Sphingopyxis sp. YF1 (PAN-CF@YF1) was synthesized. The immobilization conditions of strain Sphingopyxis sp. YF1 on PAN-CF surfaces were optimized using Box-Behnken design and response surface methodology (RSM), which turned out to be an optimal pH of 7.6 for the culture medium, a ratio of 0.038 g of supporting materials per 100 mL of culture media, and an incubation time of 53.4 h. The resultant PAN-CF@YF1 showed a great degradation effect both for low and high concentrations of MC-LR and exhibited satisfactory cyclic stability (85.75% after six cycles). Moreover, the application of PAN-CF@YF1 in the bioreactors demonstrated effective and sustainable MC-LR removal, with a removal efficiency of 78.83% after three consecutive treatments. Therefore, PAN-CF@YF1 with high degradation activity, environmental compatibility, straightforward preparation, and recyclability shows significant application potential for the bioremediation of MC-LR-contaminated water bodies.

Tuning microstructures of polyacrylonitrile-based carbon fibers by catalytic influence of boron for enhancement of mechanical properties and oxidation resistance

Boron catalytic graphitization of carbon fibers (CFs) is an effective methodology for reducing energy costs with the enhancement of tensile and oxidation resistance properties by re-constructing the crystal structure of CFs. Herein, a microwave plasma graphitization system for boron catalytic graphitization was devised. The effect of boron on microstructure and properties of CFs during boron catalytic graphitization process was investigated and analyzed. The mechanism of boron doping in different graphitization times was proposed. Furthermore, the results show that the tensile properties and oxidation resistance of CFs are improved and directly related to the microstructure of CFs, which depends on the different boron catalytic graphitization stages. This work provides the effect of boron on microstructure and properties of CFs during microwave plasma catalytic graphitization in different graphitization times and has important implications for deeply understanding the boron catalytic graphitization process which is beneficial for the preparation of CFs with excellent performance.

Understanding the catalytic mechanism of calcium compounds for enhancing crystallinity in carbon fiber

Graphitized carbon fibers are attractive materials because of their high tensile modulus and thermal and electrical conductivities. These attributes derive from their crystalline structures that develop during heat treatments of up to 3000 °C. Despite the costly thermal processes, there is a structural limit for achieving these sought-after properties for polyacrylonitrile-based carbon fibers. Herein, the preparation of polyacrylonitrile-based carbon fibers with highly developed microstructures via calcium-assisted thermal treatments of up to 2700 °C is reported. Carbon fibers hydrothermally immersed in a solution of calcium carbonate were heat-treated and their chemical structures traced to investigate the calcium-assisted catalytic graphitization mechanism. Graphitic structures appeared at 1400 °C, accompanied by intermediate complexes of carbon and calcium on the carbon fibers surfaces. Further heat treatment of the calcium compounds at 1600 °C to incorporate carbon fibers resulted in an interlayer spacing of 0.3360 nm, which was unachievable solely through heat treatment at 2700 °C. In addition, the achieved tensile modulus and electrical conductivity of 480 GPa and 1.7 × 103 S/cm, respectively, were significantly higher than those of pure carbon fibers. The calcium ions penetrating the internal structure of the carbon fibers aligned the non-uniform graphene structure and developed the graphite structure of the carbon fibers by acting as catalysts, even at low temperatures.

A novel cost-effective flow-through electrode based on polyacrylonitrile carbon fiber for enhancing micropollutant degradation via electro-Fenton

Electrochemical filtration is an effective technology for treating the wastewater that containing low-concentration organic micropollutants. However, its practical application has been hindered by the lack of feasible flow-through electrodes. Herein, a physically assembled flow-through cathode, based on commercial polyacrylonitrile-based (PAN) carbon fiber (CF), was introduced in an electro-Fenton (EF) system. The conductive filtration element, created by coiling the FeOCl-functionalized CF onto a cylindrical support, exhibited effective and consistent degradation of diverse micropollutants (77.9–94.5 %, TOC: 32.4–50.5 %) after a single-pass filtration. The excellent two-electron (2 e−) oxygen reduction reaction (ORR) performance of PAN-CF, along with the enhanced mass transfer in the flow-through configuration, contributed to the pollutant degradation by generating considerable reactive oxygen species (ROSs, including H2O2 and •OH) and facilitating adequate contact between pollutants and ROSs. The integration of electrochemistry significantly improved the antifouling performance of the filter, making it promising for real wastewater treatment. Detailed calculations and comparisons further confirmed the cost advantages of the proposed flow-through electrodes. This study provides a unique solution for the design and fabrication of engineeringly and economically feasible flow-through electrodes in electrochemical filtration systems.

An open carbon–phenolic ablator for scientific exploration

Space exploration missions rely on ablative heat shields for the thermal protection of spacecraft during atmospheric entry flights. While dedicated research is needed for future missions, the scientific community has limited access to ablative materials typically used in aerospace. In this paper, we report the development of the HEFDiG Ablation-Research Laboratory Experiment Material (HARLEM), a carbon–phenolic ablator designed to supply the need for ablative materials in laboratory experiments. HARLEM is manufactured using polyacrylonitrile-based carbon fiber preforms and a simplified processing route for phenolic impregnation. We characterized the thermal protection performance of HARLEM in arcjet experiments conducted in the plasma wind tunnel PWK1 of the Institute of Space Systems at the University of Stuttgart. We assessed the performance of the new material by measuring surface recession rate and temperature using photogrammetry and thermography setups during the experiments, respectively. Our results show that HARLEM’s thermal protection performance is comparable to legacy carbon–phenolic ablators that have been validated in different arcjet facilities or in-flight, as demonstrated by calculations of the effective heat of ablation and scanning electron microscopy of as-produced samples. In-house manufacturing of carbon–phenolic ablators enables the addition of embedded diagnostics to ablators, allowing for the acquisition of data on internal pressure and more sophisticated pyrolysis analysis techniques.

Road use and electrothermal performance of graphene-conductive asphalt-recycled pervious concrete under severe cold environment

Conductive-asphalt-recycled pervious concrete alleviates the urban “heat island effect” and “rain island effect” to realize the resourceful and efficient use of waste concrete and also reduces the probability of urban snow and ice disasters to ensure the safety of winter operation of asphalt pavements in cold areas. This study presents a theoretical and technical basis for ensuring the winter operational safety of asphalt pavements in cold regions. First, we compound graphene and carbon fiber as conductive phase materials and prepare graphene-conductive asphalt-recycled permeable concrete using recycled coarse aggregates with straight top and bottom holes. Then, we analyzed the electrical conductivity, road performance, and electrothermal performance of the specimens prepared using different recycled coarse aggregate substitution rates under different snowfall levels to determine their snow melting efficiency and verify their application in cold regions. The results indicate that the quality of the recycled aggregates is high, the optimal conductive filler ratio is 0.3% polyacrylonitrile-based carbon fiber and 1.5% graphene by mass of asphalt, and the resistivity of the specimens is only 3.2 Ω·m. Moreover, the conductivity and road performance of the graphene-conductive asphalt-recycled concrete decreases with an increase in the replacement rate of the recycled coarse aggregate, and the artificially prefabricated upper and lower through holes affect the conductivity of the specimens to a certain extent. Further, the graphene-conductive asphalt-recycled pervious concrete shows excellent snow melting potential, and as the required snow melting thickness and snow melting time increase, the effect of pervious asphalt slabs for snow melting efficiency becomes more significant. Moreover, when the replacement rate of the recycled concrete aggregate is within the range of 0–50%, it can be completed in 2–3 h under different snowfall levels of snow melting requirements.

In situ biaxial loading and multi-scale deformation measurements of nanostructured materials at the CoSAXS beamline at MAX IV Laboratory.

Characterization of the mechanical response of polymers and composite materials relies heavily on the macroscopic stress-strain response in uniaxial tensile configurations. To provide representative information, the deformation process must be homogeneous within the gauge length, which is a condition that is rarely achieved due to stress concentration or inhomogeneities within the specimen. In this work, the development of a biaxial mechanical testing device at the CoSAXS beamline at MAX IV Laboratory is presented. The design facilitates simultaneous measurement of small- and wide-angle X-ray scattering (SAXS/WAXS), allowing assessment of the microstructural configuration before, after and during the continuous deformation process at multiple length scales. The construction also supports multiple deformation conditions, while guaranteeing stability even at high loads. Furthermore, the mechanical experiments can be complemented with spatially resolved mesoscopic surface deformation measurements using 3D-surface digital image correlation (DIC). Polycarbonate (PC) was used to demonstrate the varied material response to multi-axial deformation, as PC is isotropic with a high glass transition temperature (∼150°) and high strength. As a result, a clear correlation between full-field methods and the microstructural information determined from WAXS measurements is demonstrated. When a uniaxial load is applied, homogeneous strain regions could be observed extending perpendicular to the applied load. When a secondary axial load was added (biaxial mode), it was observed that high strain domains were created near the centre of the sample and at the boundaries after yield. With increased strain, the deformation in the main deformation direction also increases. Mechanical reliability was demonstrated by carrying out static loading of polyacrylonitrile-based carbon fibre (CF) bundles. As a result, the nonlinear stiffening behaviour typically observed in CFs was seen, while no evidence of the creation of new voids during loading was observed. The results support the reliability and broad applicability of the developed technique.

Investigation of the Tendency of Carbon Fibers to Disintegrate into Respirable Fiber-Shaped Fragments

Recent reports of the release of large numbers of respirable and critically long fiber-shaped fragments from mesophase pitch-based carbon fiber polymer composites during machining and tensile testing have raised inhalation toxicological concerns. As carbon fibers and their fragments are to be considered as inherently biodurable, the fiber pathogenicity paradigm motivated the development of a laboratory test method to assess the propensity of different types of carbon fibers to form such fragments. It uses spallation testing of carbon fibers by impact grinding in an oscillating ball mill. The resulting fragments were dispersed on track-etched membrane filters and morphologically analyzed by scanning electron microscopy. The method was applied to nine different carbon fiber types synthesized from polyacrylonitrile, mesophase or isotropic pitch, covering a broad range of material properties. Significant differences in the morphology of formed fragments were observed between the materials studied. These were statistically analyzed to relate disintegration characteristics to material properties and to rank the carbon fiber types according to their propensity to form respirable fiber fragments. This tendency was found to be lower for polyacrylonitrile-based and isotropic pitch-based carbon fibers than for mesophase pitch-based carbon fibers, but still significant. Although there are currently only few reports in the literature of increased respirable fiber dust concentrations during the machining of polyacrylonitrile-based carbon fiber composites, we conclude that such materials have the potential to form critical fiber morphologies of WHO dimensions. For safe-and-sustainable carbon fiber-reinforced composites, a better understanding of the material properties that control the carbon fiber fragmentation is imperative.

Lithiated carbon fibres for structural batteries characterised with Auger electron spectroscopy

Structural batteries are multifunctional devices that store energy and carry mechanical load, simultaneously. The pivotal constituent is the carbon fibre, which acts as not only structural reinforcement, but also as electrode by reversibly hosting Li ions. Still, little is known about how Li and carbon fibres interact. Here we map Li inserted in polyacrylonitrile based carbon fibres with Auger electron spectroscopy (AES). We show that with slow charge/discharge rates, Li distributes uniformly in the transverse and longitudinal direction of the fibre, and when fully discharged, all Li is virtually expelled. With fast rates, Li tends to be trapped in the core of the fibre. In some fibres, Li plating is found between the solid electrolyte interphase (SEI) and fibre surface. Our findings can guide AES analysis on other carbonaceous electrode materials for Li-ion batteries and be used to improve the performance of structural batteries.

Ion-Beam Surface Modification of Carbon Fibers

Carbon fibers are used in the production of automobiles, airplanes, sporting goods, energy, and biomedicine due to their unique properties such as high specific strength, high specific tensile strength, low coefficient of thermal expansion, and low density. The research and development of both the technology of carbon fibers production and their modification for a wide range of applications have been and remain relevant. The summary of the accumulated experience in the modification of carbon fibers shows that ion-beam treatment allows to obtain a variety of geometry of the developed surface topography, in particular, whisker-shaped and corrugated oriented across or along the fiber. Such processing compares favorably with ordinary fiber whiskering both by a variety of geometry of the composite interface, and by the absence of the problem of whisker-fiber adhesion. Ion-beam treatment also makes it possible to modify the surface layer structure from amorphized to ordered with different degrees of graphitization. Irradiation with chemically active ions leads to functionalization of carbon fiber due to formation, for example, of nitrides and carbon oxides. The choice of nitrogen ions for the technology of carbon-carbon and carbon-ceramic composites seems to be more preferable due to less stringent requirements for the temperature of the irradiated fiber. For ion-beam corrugation of polyacrylonitrile-based carbon fiber surface, only its heating above the temperature of dynamic annealing of radiation damage is required. The use of helium ions in technological plasma acceleration systems leads to a significant efficiency increase in ion-beam processing.

Innovative and efficient preparation of high-performance polyacrylonitrile-based carbon fiber paper by centrifugal spinning

Polyacrylonitrile (PAN) carbon fibers are often used to prepare high-performance paper-based materials owing to their high strength, good electrical and thermal conductivity, and superior comprehensive properties. In this study, a novel method for preparing PAN-based carbon fibers by centrifugal spinning was developed, and a stable and homogeneous PAN carbon fiber paper was successfully obtained. Subsequently, the formation process, microscopic morphology, electrical conductivity, electrochemical performance and hydrophobicity of the PAN carbon fiber paper were studied and evaluated. The results showed that the electrical conductivity of the PAN carbon fiber paper prepared via this method reached 43.250 s·cm−1, resistivity was as low as 0.023–0.033 Ω·cm, and contact angle exceeded 140°. This study adopted a new method to prepare PAN carbon fiber paper, which provided another method for the preparation of high-performance fiber paper.

Evolution of electrical properties and microstructure of polyacrylonitrile-based carbon fibers during carbonization

Evolution of electrical properties and microstructure of polyacrylonitrile-based carbon fibers during carbonization

The effect of heat treatment on temperature-dependent transport and magnetoresistance in polyacrylonitrile-based carbon fibers

The effects of heat treatment temperatures from 1000 to 2700 °C on the structural, chemical, and mechanical properties of polyacrylonitrile-based carbon fibers (CFs) were investigated. Structural changes affected mechanical properties, and in particular, a higher sp3 content induced a higher tensile strength below 1600 °C. For a comprehensive study on the heat treatment effect and the mechanism for developing high-strength CFs, electrical transport properties were measured for the CFs. The transport behaviors in temperature-dependent conductivity and magnetoresistance were also significantly modified, which led to crossover from strong localization to weak localization due to sp2 carbon ordering. Interestingly, in samples that were subjected to intermediate heat treatment temperatures ranging from 1100 to 1600 °C, anomalous metallic temperature-dependent behavior was observed at low temperatures of below 40 K. This unusual charge transport was analyzed further with a pertinent heterogeneous model employing three-dimensional variable range hopping, weak localization, and linear metallic transport. The results suggest that mixed noncrystalline and crystalline structures with sp2/sp3 carbons, oxygen, and quaternary N groups in CFs enabled the transition behavior at such low temperatures.

High electrical and thermal conductivities of a PAN-based carbon fiber via boron-assisted catalytic graphitization

The boron-assisted catalytic graphitization of carbonaceous materials is an attractive methodology for enhancing their electrical properties by modulating the chemical structures of pristine carbons. In this study, polyacrylonitrile-based carbon fibers (CFs) with highly developed microstructures were prepared by boron-assisted catalytic graphitization. Hydrothermally immersed CFs in boric acid were heat-treated up to 2700 °C, and their chemical structures were traced to investigate the boron-assisted catalytic graphitization mechanism. Boron from the gasified boron-related functional groups of CFs diffused into the CFs to form boron carbide, B4C. The boron-substituted CFs exhibited a highly developed crystalline structure that could not be achieved by heat treatment alone, indicating that boron accelerated the graphitic carbon structure. As a result, boron-assisted catalytic graphitization at 2700 °C simultaneously enhanced the electrical and thermal conductivities of CFs, with values of 3677.8 S/cm and 365.9 W/mK, respectively, which were 2.8 and 2.4 times higher than those of heat-treated CFs at 2700 °C. In addition, CFs were used to prepare CF papers using a wet-laid process, and their heat generation and thermal management capabilities were evaluated. Considering affordable CFs compared to nanomaterials, we believe that our study provides a feasible approach for fabricating heating elements and heat sinks.