Comparative study of interphase evolution in polysiloxane resin-derived matrix containing carbon micro and nanofibers during thermal treatment

The work presents the results of research on composite materials made of silicon-containing polymer-derived ceramic matrix composites (PDC-Cs) and nanocomposites (PDC-NCs). Carbon micro and nanofibers (CFs and CNFs) were used as reinforcements. The interactions between carbon micro and nanofibers and polysiloxane matrix, as well as interphase evolution mechanism in composite samples during their heating to 1000 °C were studied. CF/resin and CNF/resin composites were prepared via liquid precursor infiltration process of unidirectionally aligned fibers. After heating to 700 °C–800 °C, decomposition of the resin in the presence of CNFs led to the formation of fiber/organic-inorganic composites with pseudo-plastic properties and improved oxidation resistance compared to as-prepared fiber/resin composites. The most favourable mechanical properties and oxidation resistance were obtained for composites and nanocomposites containing the maximum amount of carbon nanoparticles precipitated in the SiOC matrix during the heat treatment at 800 °C. The precipitated carbon phase improves fiber/matrix adhesion of composites.     

Thermomechanical characterisation of coal tar pitch- based carbon containing SiC nanoparticles

Coal tar pitch (CTP) modified with silicon carbide nanoparticles (nSiC) was used as a carbon binder precursor for the manufacture of carbon materials. Carbon samples were prepared in the form of a composition consisting of synthetic coke, graphite and nSiC- modified CTP prior to heat treatment at temperatures from 800 °C to 2800 °C. The effect of ceramic nanofiller in CTP on oxidation resistance of carbon samples obtained at various temperatures was studied. Physical and mechanical properties of carbon samples obtained at 2000 °C and 2800 °C were analysed. nSiC presence in CTP was found to change the elevated temperature properties of carbon samples. The oxidation tests conducted at 600 °C in air showed a significant improvement of the resistance of carbon samples modified with small amount of nSiC and annealed at 2000 °C. Properties investigated included characteristics important for application of carbon materials for carbon electrode manufacturing, i.e., electrical and thermal conductivities as well as mechanical properties. Due to microstructural changes of carbon samples in the presence of nSiC filler physical and mechanical properties improved after annealing the samples at high temperature in comparison to unmodified carbon samples.     

含Si–O–C界面层的C/Si–C–N复合材料的抗氧化性能(英文)

为了研究利用Si–O–C界面层来提高碳纤维增强陶瓷基复合材料的抗氧化性能,利用化学气相浸渗和聚合物浸渗裂解工艺制备了以Si–O–C为界面的碳纤维增强Si–C–N陶瓷基复合材料（C/Si–O–C/Si–C–N）和无界面层的碳纤维增强Si–C–N陶瓷基复合材料（C/Si–C–N）。研究了C/Si–O–C/Si–C–N和C/Si–C–N在600、900℃和1 200℃空气环境中的氧化行为。结果表明：采用Si–O–C界面层后可提高复合材料的抗氧化性能;Si–O–C界面层较高的氧化抗力是碳纤维增强Si–C–N复合材料抗氧化性能提高的主要原因。     

A microstructural study of carbon–carbon composites impregnated with SiC filaments

Porous multidirectional carbon/carbon composite obtained by pulse chemical vapour infiltration (PCVI) was impregnated with silicon carbide (SiC) derived from pyrolysis of polymethylsiloxane resin (PMS). The impregnation process was made to improve oxidation resistance and mechanical properties of MD C/C composite. The resin was used as a source of silicon carbide component of the composite forming after heat treatment above 1000 °C. During this process SiC thin filaments were formed inside the porous carbon phase. The aim of this work was to investigate the structure and microstructure of the constituents of carbon composite obtained after pyrolysis of SiC PMS precursor. Microscopic observations revealed that during careful heat treatment of crosslinked polymethylsiloxane resin up to 1700 °C, the filaments (diameter 200–400 nm) crystallized within porous carbon phase. The filaments were randomly oriented on the composite surface and inside the pores. FTIR spectra and XRD analysis of the modified C/C composite showed that filaments had silicon carbide structure with the crystallite size of silicon carbide phase of about 45 nm. The Raman spectra revealed that the composite contains two carbon components distinctly differing in their structural order, and SiC filaments present nanocrystalline structure.     

Oxidation behavior of carbon materials derived from a carborane- and silicon-incorporated polymer

The oxidation behavior and oxidation mechanism of carbon materials containing silicon and boron elements (C–Si–B materials) were investigated at different high temperatures in air. The carbon materials were prepared by oxidative pyrolysis of the polymer precursor, carborane-incorporated poly(dimethylsilylene-ethynylenephenyleneethynylene) (CB-PSEPE), at 800, 1000, or 1200 °C for 1 h under static air. Homogeneous dispersion of silicon and boron components in the carbon matrix could be achieved in the carbon materials after the pyrolysis. The oxidation behavior of the C–Si–B materials during the oxidation process was studied. The evolution of elemental composition and morphology of the surface layers of carbon materials was monitored by X-ray photoelectron spectroscopy and scanning electron microscopy, respectively. The results imply that the formation of protective borosilicate layer in the surface is the main mechanism to provide remarkable oxidation resistance of the carbon materials. The obtained borosilicate layer with a self-healing property can withstand oxidation at 1000 °C in air.     

Development of UHTCMCs via water based ZrB2 powder slurry infiltration and polymer infiltration and pyrolysis

C_f/ZrB₂-SiC ultra-high temperature composites were manufactured via aqueous slurry impregnation coupled with polymer infiltration and pyrolysis, using a allylhydrido polycarbosilane precursor. For the first time we used ultra-high modulus pitch-based carbon fibres for the PIP process, investigating three different architectures, 0/0°, 0/90°, and 2D. Microstructure, mechanical properties and oxidation resistance in air at 1650 °C were investigated. As expected, the mechanical properties showed the tendency to decrease with increase of the preforms complexity, due to the higher amount of flaws and residual stresses. For instance, the flexural strength was approaching 500 MPa for 0/0°, 370 MPa for 0/90° and 190 MPa for 2D. The materials showed an optimal resistance to oxidation at 1650 °C thanks to formation of a viscous borosilicate glass that guaranteed a self-healing functionality.     

Thermal conversion of coal-tar pitch in the presence of silicon compounds

The effect of SiO₂ and polycarbosilane (PCS) additives on the thermal degradation of coal-tar pitch at temperatures to 900°C was studied by thermogravimetric analysis, differential thermal analysis, mass-spectrometric analysis, IR spectroscopy, and electron microscopy. It was found that, in the presence of the test additives, the character of release and the quantitative composition of volatile degradation products changed, the degree of aromaticity of the carbon residue decreased, and the concentration of oxygen-containing groups in this residue increased. In the case of the PCS additive, the combined thermal conversion of both of the components occurred. In this case, the contribution of structurization processes increased to cause a nonadditive increase in the yield of solid residue. Silicon mainly occurred as organosilicon fragments with Si-C and Si-O-C bonds, an oxycarbide, and, probably, silicon carbide. In the case of the SiO₂ additive, oxidation processes were enhanced; the yield of carbon somewhat decreased, and siloxane groups were present in the solid residue.     

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

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

Boron-modified phenol formaldehyde resin-based self-healing matrix for Cf/SiBOC composites

C_f/SiBOC was fabricated from 2D carbon fabric as reinforcement and slurry-containing boron-modified phenol formaldehyde (BPF) resin with silicon as matrix resin using reaction-bonded silicon carbide method. The processing involves synthesis of (BPF) resin by reacting various amount of boric acid with phenol formaldehyde resin, polymer to ceramic transformation at 1450°C under argon atmosphere, with and without silicon, thermal transformation of the polymer matrix composite into a ceramic matrix composite and evaluation of isothermal oxidation for ceramics and its composites at 1000, 1250 and 1500°C. The ceramic studies, confirmed the formation of B₄C, SiC and SiB₄ (SiBOC) mixed phase and the role of boron as a catalyst for graphitisation of free carbon present in the ceramic. Oxidation of C_f/SiBOC composite at various temperatures leads to the formation of borosilicate glass which heals the cracks, hindering the inwards diffusion of oxygen.     

Preparation and properties of phosphorus‐ and silicon‐modified phenolic resin with high ablation resistance

In order to further improve the ablation resistance of common phenolic resins, a modified phenolic resin containing phosphorus and silicon (SPPR) was synthesized and the corresponding properties were evaluated. With phosphorus and silicon involved in the macromolecule, SPPR showed excellent flame retardancy and obviously enhanced value (44.8%) of the limiting oxygen index. The thermal stability and charring performance of SPPR were greatly improved, with maximum decomposition temperature of over 500 °C and carbon yield of 60.1% in nitrogen. Differential scanning calorimetry indicated that the curing temperature shifted from 157 °C for the conventional phenolic resin to 182 °C for SPPR. Moreover, an improvement of impact strength from 4.3 to 16.5 kJ m^?2 confirmed that incorporation of flexible Si? O chain had a noticeable effect on the mechanical properties of SPPR. Such a modified phenolic resin has promising application prospects serving as an ablation material with high performance. © 2019 Society of Chemical Industry     

Thermal conversion of carbon fibres/polysiloxane composites to carbon fibres/ceramic composites

The aim of this work is to investigate the thermal conversion of carbon fibres/polysiloxane composites to carbon fibres/ceramic composites. The conversion mechanism of four different resins to the ceramic phase in the presence of carbon fibres is investigated. The experiments were conducted in three temperature ranges, corresponding to composite manufacturing stages, namely up to 160 °C, 1000 °C and finally 1700 °C.The study reveals that the thermal conversion mechanism of pure resins in the presence of carbon fibres is similar to that without fibres up to 1000 °C. Above 1000 °C thermal decomposition occurs in both solid (composite matrix) and gas phases, and the presence of carbon fibres in resin matrix produces higher mass losses and higher porosity of the resulting composite samples in comparison to ceramic residue obtained from pure resin samples. XRD analysis shows that at temperature of 1700 °C composite matrices contain nanosized silicon carbide. SEM and EDS analyses indicate that due to the secondary decomposition of gaseous compounds released during pyrolysis a silicon carbide protective layer is created on the fibre surface and fibre–matrix interface. Moreover, nanosized silicon carbide filaments crystallize in composite pores.Owing to the presence of the protective silicon carbide layer created from the gas phase on the fibre–matrix interface, highly porous C/SiC composites show significantly high oxidation resistance.     

A Study on Composites from Casein Modified Melamine-Formaldehyde Resin

Amino resins are used for various applications such as decorative plastic plates, decorative wood boards, particle boards, leather tanning, foam, coating, and molding materials. In the present work, it was planned to prepare modified melamine-formaldehyde resin by incorporating casein. The intended melamine-formaldehyde-casein (MFC) resin samples were prepared under alkaline condition with an 1:3 melamine: formaldehyde ratio. Casein was incorporated in varying proportions (up to 25% w/w of melamine content) at 85–90°C. The samples were characterized by viscosity measurement and vapor pressure osmometry (VPO). The resin samples were cured isothermally at 60°C using ammonium chloride as well as hydroxylamine hydrochloride and at 120°C using hexamine as the curing agents. Jute fabric (JFRC) and glass fabric reinforced composites (GFRC) were produced by maintaining 60:40 and 40:60 proportion of resin to reinforcement materials, respectively. The laminates thus formed were characterized for their mechanical properties and chemical resistance.     

Effect of ZrC content on the properties of biomorphic C–ZrC–SiC composites prepared using hybrid precursors of novel organometallic zirconium polymer and polycarbosilane

A novel organometallic zirconium polymer was synthesized through the copolycondensation using n-butyllithium, 1,4-diethynylbenzene, phenylacetylene and zirconium tetrachloride as raw materials. Then biomorphic C–ZrC–SiC composites were fabricated from corn stover templates by precursor infiltration and pyrolysis process using hybrid polymeric precursors containing the organometallic zirconium polymer and polycarbosilane. The microstructure, mechanical properties and oxidation resistance of the composites were investigated. With ZrC content increasing, the mechanical properties of the composites were enhanced due to dispersion strengthening and grain fining of the homogeneously dispersed ZrC nanoparticles. The oxidation behavior of C–SiC–ZrC indicated that the oxidation resistance of the composite was reduced at 1000 °C but improved at 1500 °C with the increase of ZrC content. The improved oxidation resistance was mainly attributed to a proper ZrC content, the formation of ZrSiO₄ layer on the surface of the composite, and its matrix microstructure characterized by a nano-sized dispersion of ZrC–SiC phases.     

Spherical indentations on hafnium carbide- and silicon-carbide-coated carbon–carbon composites after thermal shock test in air

In this study, high-temperature oxidations and indentations on silicon carbide (SiC)- and hafnium carbide (HfC)-coated carbon–carbon (C/C) composites were investigated to prevent the oxidation of C/C composites in air. The SiC and HfC layers were coated to protect the composite from oxidizing in air at a high temperature. High-temperature oxidation tests were performed at 500 °C, 1,000 °C, 1,350 °C, and 1,500 °C for 1 h in air and then cooled to room temperature by thermal shock. This cycle was repeated until the coating layer was damaged. As a result of measuring the weight change according to the thermal cycle and observing the fiber damage in the C/C composites, the oxidation resistance of HfC was evaluated to be superior to that of SiC. The change of the mechanical behavior was investigated using an indentation test with a tungsten carbide ball with a radius of either 3.18 or 7.93 mm before and after the high-temperature oxidation test by thermal shock. The relative elastic modulus was predicted based on the slope of the indentation load–displacement curve during loading or that of the curve during unloading. The relative hardness was also analyzed based on residual displacement after indentation. The hardness and elastic modulus of the HfC and SiC coating were higher than those of C/C composites and the mechanical properties of the HfC-coated C/C composite were relatively good compared with those of the SiC-coated composites prior to the thermal shock test. In particular, in this study, it was found that the mechanical behaviors of HfC-coated C/C composites exposed to temperatures >1,000 °C in air were transferred from elastic to quasi-plastic. The quasi-plasticity of the HfC coating layer was evaluated to be excellent regarding its resistance to mechanical damage as the coating layer was not easily delaminated or damaged even by oxidation.     

Characterization of a rigid silicone resin

Silicone resins have been used as binders for ceramic frit coatings and can withstand temperatures of 650°C to 1260°C. Conceptually, silicone resins can potentially be used as matrices for high temperature fiber‐reinforced composites. The mechanical and thermal properties of a commercially available silicone resin, Dow Corning® 6‐2230, were characterized. Neat 6‐2230 resin was found to have inferior room temperature mechanical properties such as flexural, tensile and fracture properties when compared to epoxy. The room temperature flexural properties and short beam shear strength of the silicone/glass composites were also found to be lower than those of epoxy/glass composite with similar glass content. However, the silicone resin had better elevated temperature properties. At an elevated temperature of 316°C, the retentions of flexural modulus and strength were 80% and 40% respectively of room temperature values; these were superior to those of phenolic/glass. Unlike the carbon‐based resins, the drop in flexural properties of the silicon/glass laminates with temperature leveled off with increase in temperature beyond 250°C. The resin weight loss at 316°C in 100 cm³/min of flowing air was small compared to other carbon‐based resins such as PMR‐15 and LaRC TPI. Only Avimid‐N appeared comparable to Dow Corning® 6‐2230.     

Improvement of the mechanical properties of SiC reticulated porous ceramics with optimized three-layered struts for porous media combustion

Silicon carbide reticulated porous ceramics (SiC RPCs) with three-layered struts were fabricated by polymer replica method, followed by infiltrating alumina slurries containing silicon (slurry-Si) and andalusite (slurry-An), respectively. The effects of composition of infiltration slurries on the strut structure, mechanical properties and thermal shock resistance of SiC RPCs were investigated. The results showed that the SiC RPCs infiltrated with slurry-Si and slurry-An exhibited better mechanical properties and thermal shock resistance in comparison with those of alumina slurry infiltration, even obtained the considerable strength at 1300 °C. In slurry-Si, silicon was oxidized into SiO₂ in the temperature range from 1300 °C to 1400 °C and it reacted with Al₂O₃ into mullite phase at 1450 °C. Meantime, the addition of silicon in slurry-Si could reduce SiC oxidation of SiC RPCs during firing process in contrast with alumina slurry. With regard to slurry-An, andalusite started to transform into mullite phase at 1300 °C and the secondary mullitization occurred at 1450 °C. The enhanced mechanical properties and thermal shock resistance of SiC RPCs infiltrated alumina slurries containing silicon and andalusite were attributed to the optimized microstructure and the triangular zone (inner layer of strut) with mullite bonded corundum via reaction sintering. In addition, the generation of residual compressive stress together with better interlocked needle-like mullite led to the crack-deflection in SiC skeleton, thus improving the thermal shock resistance of obtained SiC RPCs.     

C/C–SiC composites derived from single-source poly(silylene–acetylene) precursors

Carbon-fiber-reinforced carbon–silicon carbide (C/C–SiC) composites were prepared by impregnating carbon fibers with ethynylphenyl-terminated poly(silylene–acetylene) (EPTSA) as a single-source precursor with subsequent hot pressing and pyrolysis. The structural evolution, crystallization behavior, and graphitization of bulk C–SiC ceramics, as well as their mechanical properties and ablation behavior, were investigated. The EPTSA precursor starts to transform into inorganic SiC ceramic materials at 800°C, which is characterized by an amorphous structure with weight loss, shrinkage, and densification between 800 and 1000°C. The formation of SiC crystals inhibited the growth of the graphitic structure between 1000 and 1200°C. As the temperature was raised, both graphite and SiC crystals continued to grow, and the crystalline forms became more complete. The carbon-fiber cloth (T300CF)-reinforced C–SiC composite (T300CF/C–SiC) prepared using polymer infiltration and pyrolysis (PIP) exhibited excellent mechanical properties. After five PIP cycles, the flexural strength, flexural modulus, and interlaminar shear strength of the T300CF/C–SiC composite reached 169 MPa, 32.5 GPa, and 9.38 MPa, respectively. In addition, the chopped-carbon-fiber-reinforced C–SiC composite fabricated using the PIP process demonstrated good oxyacetylene-torch ablation properties.     

Oxidation resistant ceramic foam from a silicone preceramic polymer/polyurethane blend

Silicon oxycarbide (SiOC) ceramic foams, produced by the pyrolysis of a foamed blend of a methylsilicone preceramic polymer and polyurethane (PU) in a 1/1 wt.% ratio, exhibit excellent physical and mechanical properties. The proposed process allows to easily modify the density and morphology of the foams, making them suitable for several engineering applications. However, it has been shown that, due to residual carbon present in the oxycarbide phase after pyrolysis, the foams are subjected to an oxidation process that reduces their strength after high temperature exposure to air (12 h 1200°C). A modified process, employing the same silicone resin preceramic polymer but a much lower PU content (silicone resin/PU=5.25/1 wt.% ratio), has been developed and is reported in this paper. Microstructural investigations showed that carbon rich regions deriving from the decomposition of the polyurethane template are still present in the SiOC foam, but have a much smaller dimension than those found in foams with a higher PU content. Thermal gravimetric studies performed in air or oxygen showed that the low-PU containing ceramic foams display an excellent oxidation resistance, because the carbon-rich areas are embedded inside the struts or cell walls and are thus protected by the dense silicon oxycarbide matrix surrounding them. SiOC foams obtained with the novel process are capable to maintain their mechanical strength after oxidation treatments at 800 and 1200°C (12 h), while SiOC foams obtained with a higher amount of PU show about a 30% strength decrease after oxidation at 1200°C (12 h).     

Synthesis and characterization of a novel silicon‐containing polytriazole resin

4,4′‐Diazidomethylbiphenyl (DAMBP) and poly(dimethylsilylene‐ethynylenephenyleneethynylene) (PDMSEPE) were thermally polymerized to form a novel silicon‐containing polytriazole resin (PDMSEPE‐DAMBP) by 1,3‐dipolar cycloaddition. Differential scanning calorimetry, FTIR, and ¹³C‐NMR were used to characterize the curing behaviors of PDMSEPE‐DAMBP resins. The results indicated that the resins could cure at temperatures as low as 80°C. Dynamic mechanical analysis showed that there was a glass transition at 302°C for the cured PDMSEPE‐DAMBP resin. The carbon fiber (T700) reinforced PDMSEPE‐DAMBP composites exhibited excellent mechanical properties at room temperature and high property retention at 250°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Low-temperature fast curable behavior and properties of bio-based carbon fiber composites based on resveratrol

Environmentally friendly materials are an integral part of sustainable chemistry, and bio-based polymer composites are an important class of materials. The manufacture of composites is expected to reduce or even eliminate the use of adjuvants, considering the importance of reducing energy consumption and avoiding health and environmental risks. In this study, a phenyl-containing, polyfunctional, bio-based epoxy resin (TGER) was synthesized, and carbon fiber-reinforced, bio-based epoxy resin composites were fabricated by vacuum-assisted resin infusion using two aromatic amine curing agents, 4,4′-diaminodiphenylmethane (DDM) and 3,3′-diethyl-4,4′-diaminodiphenylmethane (DEDDM). Curing reactions and rheological behavior studies showed that TGER had higher curing reactivity toward DDM and DEDDM than to diglycidyl ether of bisphenol A (DGEBA) and possessed good processability. The results indicated that the resveratrol-based epoxy resin displayed low-temperature fast curing properties. The evaluation of the mechanical properties of the carbon fiber composites showed that the flexural strengths of CF/TGER/DDM and CF/TGER/DEDDM were 520 and 628 MPa, respectively. The initial decomposition temperature of CF/TGER composites is above 200°C. Furthermore, the carbon fiber–reinforced biopolymers possess excellent heat resistance. Therefore, carbon fiber-reinforced, resveratrol-based epoxy resin composites are promising candidates as alternatives to petroleum-based high-performance carbon fiber composites.