Compressive behaviour of rigid rod polymer fibres and their adhesion to composite matrixes

Abstract

The deformation behaviour of the new high performance polymer fibres, poly(p-phenylene benzobisoxazole) (PBO) and polypyridobisimidazole (PIPD) and their adhesion to an epoxy composite matrix have been investigated. Both fibres give well defined Raman spectra, and the deformation micromechanics of PBO and PIPD single fibres and composites were studied from stress induced Raman band shifts. Single fibre stress-strain curves were determined in both tension and compression, thus providing an estimate of the compressive strength of these fibres. It was found that the PIPD fibre has a higher compressive strength (~1 GPa) than PBO (~0·3 GPa) and other high performance polymer fibres, because hydrogen bond formation is possible between PIPD molecules. It has been shown that when PBO and PIPD fibres are incorporated into an epoxy resin matrix, the resulting composites show very different interfacial failure mechanisms. The fibre strain distribution in the PBO-epoxy composites follows that predicted by the full bonding, shear lag model at low matrix strains, but deviations occur at higher matrix strains due to debonding at the fibre/matrix interface. For PIPD-epoxy composites, however, no debonding was observed before fibre fragmentation, indicating better adhesion than for PBO as a result of reactive groups on the PIPD fibre surface.     

A novel polyborosilazane for high-temperature amorphous Si–B–N–C ceramic fibres

Polyborosilazane synthesised from BCl₃, HMeSiCl₂, and Me₃SiNHSiMe₃ is easy to cross-link for dehydrogenation of Si–H and N–H, which limits its practical applications for Si–B–N–C fibres on an industrial scale. Therefore, in this context, MeSiCl₃ was used instead of HMeSiCl₂ to synthesise a novel polyborosilazane with limited cross-linking density to fabricate Si–B–N–C fibres. The polyborosilazane synthesised from BCl₃, MeSiCl₃, and Me₃SiNHSiMe₃ exhibits good melt-processability and 1 km long polyborosilazane fibre can be obtained by melt spinning. Prior to pyrolysis, chemical curing with vapour HSiCl₃ at 80 °C was utilised to make the λ green fibres infusible. The as-cured fibres were subsequently pyrolyzed at 1200 °C in nitrogen atmospheres to provide Si–B–N–C ceramic fibres with ca. 1.5 GPa in tensile strength, ca. 160 GPa in Young's modulus, ca. 12 μm in diameter and keeping amorphous up to 1700 °C, which makes them to be promising reinforcements in ceramic matrix composites for high temperature applications.     

Complete characterisation of BN fibres obtained from a new polyborylborazine

A new polymer was prepared at room temperature from a di-chloroborazine and a reactive aminoborane. It displays borazine rings unambiguously linked through three atoms N–B–N bridges. This connecting mode was evidence by ¹⁵N solid state NMR. This polyborazine was processed into a continuous polymer fibre of about 21 μm diameter, which was subsequently heat-treated under NH₃/N₂ up to 1800 °C for conversion into BN fibres. The achievement of hexagonal boron nitride was confirmed by X-ray diffraction and Raman spectroscopy. Tensile tests were carried out on the ceramic fibres. The average tensile strength is about 1000 MPa and the Young's modulus is close to 200 GPa. Structural characterisation of the BN fibres was undertaken by polarised light and transmission electronic microscopies.     

Study of SiC fiber axial compressive behavior using tensile recoil measurement

SiC fibers have been widely investigated as reinforcements for advanced ceramic matrix composites owing to their excellent high-temperature properties. However, the axial compressive strength of SiC fibers has not been thoroughly studied. In this study, the compressive behavior of two SiC fiber types containing different compositions and thermal degradation were characterized by tensile recoil measurements. Results illustrated that the SiC fiber compressive strength was 30%–50% of its tensile strength, after heat treatment at 1200℃–1800℃ for 0.5 h in argon. The fiber compressive failure mechanism was studied, and a “shear-bending-cleavage” model was proposed for the recoil compression fracture of pristine SiC fibers. The average compressive and tensile strengths of the pristine SiC-II fiber were 1.37 and 3.08 GPa, respectively. After treatment at 1800℃ for 0.5 h in argon, the SiC-II fiber compressive strength decreased to 0.42 GPa, whereas the tensile strength reduced to 1.47 GPa. The mechanical properties of the fibers degraded after high-temperature treatment. This could be attributed to SiC grain coarsening and SiC_xO_y phase decomposition.     

Evolution of the structure and mechanical performance of Cansas-II SiC fibres after thermal treatment

Herein, an in-depth analysis of the effect of heat treatment at temperatures between 900 and 1500 °C under an Ar atmosphere on the structure as well as strength of Cansas-II SiC fibres was presented. The untreated fibres are composed of β-SiC grains, free carbon layers, as well as a small amount of an amorphous SiC_xO_y phase. As the heat-treatment temperature was increased to 1400 °C, a significant growth of the β-SiC grains and free carbon layers occurred along with the decomposition of the SiC_xO_y phase. Moreover, owing to the decomposition of the SiC_xO_y phase, some nanopores formed on the fibre surface upon heating at 1500 °C. The mean strength of the Cansas-II fibres decreased progressively from 2.78 to 1.20 GPa with an increase in the heat-treatment temperature. The degradation of the fibre strength can be attributed to the growth of critical defects, β-SiC grains, as well as the residual tensile stress.     

Nanocomposite matrix for increased fibre composite strength

A new type of three-phase thermoplastic composite has been made, consisting of a main reinforcing phase of woven glass or carbon fibres and a PA6 nanocomposite matrix. Nanocomposites have the potential to improve the matrix dominated flexural and compressive strength by increasing the matrix modulus. Good quality fibre composites have been made with several types of PA6 nanocomposite and unfilled PA6 in combination with glass and carbon fibre reinforcement. Flexural tests on commercial PA6 fibre composites have shown the decrease of the flexural strength upon increasing temperature and this has been compared with the decrease of the matrix modulus. The nanocomposites used in this research have moduli that are much higher than unfilled PA6, also above T_g and in moisture conditioned samples. The strength of glass fibre composites can be increased by more than 40% at elevated temperatures and the temperature range at which a certain minimum strength is present can be increased by 40-50 °C. Carbon fibre composites also show significant improvements at elevated temperatures, although not at room temperature. The advantage of the use of nanocomposites instead of other polymers to improve the fibre composite properties is that the properties can be improved without any change in the processing conditions.     

Effect of high temperatures on high performance steel fibre reinforced concrete

After being subjected to different elevated heating temperatures, ranging between 105 °C and 1200 °C, the compressive strength, flexural strength, elastic modulus and porosity of concrete reinforced with 1% steel fibre (SFRC) and changes of colour to the heated concrete have been investigated.The results show a loss of concrete strength with increased maximum heating temperature and with increased initial saturation percentage before firing. For maximum exposure temperatures below 400 °C, the loss in compressive strength was relatively small. Significant further reductions in compressive strength are observed, as maximum temperature increases, for all concretes heated to temperatures exceeding 400 °C. High performance concretes (HPC) start to suffer a greater compressive strength loss than normal strength concrete (NSC) at maximum exposure temperatures of 600 °C. It is suggested that HPC suffers both chemical decomposition and pore-structure coarsening of the hardened cement paste when C-S-H starts to decompose at this high temperature. Strengths for all mixes reached minimum values at 1000 or 1100 °C. No evidence of spalling was encountered. When steel fibres are incorporated, at 1%, an improvement of fire resistance and crack [F.M. Lea, Cement research: retrospect and prospect. Proc. 4th Int. Symp. On the Chemistry of Cement, pp. 5-8 (Washington, DC, 1960).] resistance as characterized by the residual strengths were observed. Mechanical strength results indicated that SFRC performs better than non-SFRC for maximum exposure temperatures below 1000 °C, even though the residual strength was very low for all mixes at this high temperature. The variations with colour, which occured, are associated with maximum temperatures of exposure.     

Single and polycrystalline mullite fibres grown by laser floating zone technique

The laser floating zone technique was used to grow large 2Al₂O₃–SiO₂ mullite fibres (up to 1.6 mm in diameter and 40 mm in length). The fibres grown at 10 mm/h are single crystalline in nature, while those pulled at higher rates (40 and 100 mm/h) are polycrystalline with a cellular microstructure. The crystals are highly [0 0 1] textured with respect to the fibre axis, as determined by X-ray diffraction analysis. The Raman spectra taken at different orientations corroborate the strong anisotropy observed by X-ray and SEM on both single crystalline and textured polycrystalline samples.Four point bending tests and ultramicroindentation Vickers experiments were performed at room temperature in order to characterize the mechanical properties. The presence of lamellar inclusions in the single crystalline fibres decreases the flexural strength (431 MPa) and the fracture toughness (1.2 MPa.m^1/2) compared to the polycrystalline ones (631 MPa and 1.6 MPa.m^1/2). However, the absence of grain boundaries in the single crystals leads to higher ultramicrohardness (H_V = 15.6 GPa) and Young's modulus (E = 170 GPa) than those of the polycrystalline fibres (14.2 and 145 GPa), where a glassy intergranular phase exists.     

Compressive strength degradation in ZrB2-based ultra-high temperature ceramic composites

The high temperature compressive strength behavior of zirconium diboride (ZrB₂)-silicon carbide (SiC) particulate composites containing either carbon powder or SCS-9a silicon carbide fibers was evaluated in air. Constant strain rate compression tests have been performed on these materials at room temperature, 1400, and 1550 °C. The degradation of the mechanical properties as a result of atmospheric air exposure at high temperatures has also been studied as a function of exposure time. The ZrB₂-SiC material shows excellent strength of 3.1 ± 0.2 GPa at room temperature and 0.9 ± 0.1 GPa at 1400 °C when external defects are eliminated by surface finishing. The presence of C is detrimental to the compressive strength of the ZrB₂-SiC-C material, as carbon burns out at high temperatures in air. As-fabricated SCS-9a SiC fiber reinforced ZrB₂-SiC composites contain significant matrix microcracking due to residual thermal stresses, and show poor mechanical properties and oxidation resistance. After exposure to air at high temperatures an external SiO₂ layer is formed, beneath which ZrB₂ oxidizes to ZrO₂. A significant reduction in room temperature strength occurs after 16-24 h of exposure to air at 1400 °C for the ZrB₂-SiC material, while for the ZrB₂-SiC-C composition this reduction is observed after less than 16 h. The thickness of the oxide layer was measured as a function of exposure time and temperatures and the details of oxidation process has been discussed.     

Effect of short fibers on residual permeability and mechanical properties of hybrid fibre reinforced high strength concrete after heat exposition

Mechanical and permeability performance of fibre reinforced high strength concrete after heat exposition were evaluated in the experimental study. Cylindrical concrete specimens were exposed to heat with the rate of 10 °C/min of up to 400 °C. In order to study the effect of short fibres on residual performance of heated high strength concrete, polypropylene and steel fibres had been added into the concrete mix. The melting and vaporization of its fibre constituents were found to be responsible for the significant reduction in residual properties of polypropylene fibre reinforced high strength concrete. In terms of non-destructive measurement, UPV test was proposed as a promising initial inspection method for fire damaged concrete structure. Furthermore, the effect of hybrid fibre on the residual properties of heated fibre reinforced high strength concrete was also presented.     

Reactive infiltration processing (RIP) of ultra high temperature ceramics (UHTC) into porous C/C composite tubes

A novel reactive infiltration processing (RIP) technique was employed to infiltrate porous carbon fibre reinforced carbon (C/C) composite hollow tubes with ultra high temperature ceramic (UHTC) particles such as ZrB₂. The C/C composite tubes had initial porosity of ∼60% with a bimodal (10 μm and 100 μm) pore size distribution. A slurry with 40-50% ZrB₂ solid loading particles was used to infiltrate the C/C tubes. Our approach combines in situ ZrB₂ formation with coating of fine ZrB₂ particles on carbon fibre surfaces by a reactive processing method. A Zr and B containing diphasic gel was first prepared using inorganic-organic hybrid precursors of zirconium oxychloride (ZrOCl₂·8H₂O), boric acid, and phenolic resin as sources of zirconia, boron oxide, and carbon, respectively. Then commercially available ZrB₂ powder was added to this diphasic gel and milled for 6 h. The resultant hybrid slurry was vacuum infiltrated into the porous hollow C/C tubes. The infiltrated tubes were dried and fired for 3 h at 1400 °C in flowing Ar atmosphere to form and coat ZrB₂ on the carbon fibres in situ by carbothermal reaction. Microstructural observation of infiltrated porous C/C composites revealed carbon fibres coating with fine nanosized (∼100 nm) ZrB₂ particles infiltrated to a depth exceeding 2 mm. Ultra high temperature ablation testing for 60 s at 2190 °C suggested formation of ZrO₂ around the inner bore of the downstream surface.     

Effect of microstructure on the adhesion strength of TiBx coating on Ti6Al4V substrate

TiB_x coatings were deposited on Ti6Al4V and Si (100) wafer substrates by D.C. magnetron sputtering with various target-to-substrate distances (T.S. distances) from 50 mm to 200 mm. The influence of T.S. distance on the microstructure, hardness and adhesion strength of TiB_x coatings and Ti6Al4V substrate system was investigated. Results showed that the microstructure of TiB_x coatings transformed from dense to fibre columnar grain with the increase in T.S. distance, whilst the hardness decreased from 20.9 GPa to 9.4 GPa. The Rockwell-C indentation adhesion strength grade was also improved from HF6 to HF1. An adhesion evaluation factor G, which is related to the mechanical properties and the microstructure of TiB_x coating, is proposed based on the test results. The adhesion strength increased with G, which corresponded well with the results of indentation test. The high-speed rubbing test with a sliding speed of 300 m/s was performed to check the Al-adhesion resistance of the TiB_x coating against Al–hBN seal coating.     

Comparison of sintering and compressive strength tendencies of a model coal mineral mixture heat-treated in inert and oxidizing atmospheres

The chemical interactions responsible for sintering in a coal mineral mixture were investigated in air and in N₂. A mineral mixture was made up by mixing kaolin, pyrite, quartz, calcite, hydromagnesite, FeCO₃ and anatase in a fixed ratio. The mineral mixture was pelletized and heat-treated up to 1100 °C in order to evaluate sintering by recording the compressive strength values and visual assessment with scanning electron microscopy (SEM). Chemical interactions responsible for the trends in the compressive strength results were investigated with simultaneous thermogravimetric and differential thermal analysis (TG/DTA), as well as X-ray diffraction. The results indicated that the formation of anhydrite (CaSO₄) was responsible for increased mechanical strength in the mineral mixture pellets heated in air at temperatures higher that 400 °C. CaSO₄ formed from the reaction of the decomposition products of pyrite and calcite (SO_x and CaO). The TG/DTA results also indicated that the reaction with pyrite in air caused the decomposition of calcite in the mixture at a lower temperature than was observed for calcite only. The pellets heated in N₂ did not increase in mechanical strength during heat-treatment due to the lack of CaSO₄ formation in the inert atmosphere. However, SEM analysis indicated that sintering did occur at the higher temperatures in N₂. A decrease was observed in the compressive strength values obtained in air at temperatures from 900 °C to 1100 °C. Reasons for the decreased compressive strengths may include increased porosity, decomposition of CaSO₄, and changes in the characteristics of the aluminosilicate phases.     

Influence of substrate bias voltage on structure and properties of hard Si–B–C–N films prepared by reactive magnetron sputtering

We systematically investigated the effect of the rf induced negative substrate bias voltage, U_b, on characteristics of novel quaternary Si–B–C–N films. The films were deposited on Si(100) or glass substrates by reactive dc magnetron co-sputtering of silicon, boron and carbon from a single C–Si–B or B₄C–Si target in nitrogen–argon gas mixtures at substrate temperatures of 180–350 °C. Elemental compositions of the films, their surface bonding structure, and mechanical and electrical properties were primarily controlled by the U_b values, varied from a floating potential (being between − 30 and − 40 V) to U_b = − 700 V. The energy and flux of ions bombarding the target and the growing films were evaluated on the basis of the measured discharge characteristics. The films were found to be amorphous with thickness up to 5 μm and density around 2.4 g/cm³. They exhibited hardness up to 44 GPa, modified Young's modulus between 170 and 280 GPa, elastic recovery up to 82% and good adhesion to substrates at a low compressive stress (0.6–1.8 GPa). The results of stress measurements were compared with predictions of the model developed by Davis and a beneficial role of silicon in reducing the compressive stress in the films was proved. Electrical conductivity of the semiconductive Si–B–C–N films with a high (approximately 40 at.%) carbon content was controlled by the nitrogen–argon gas mixture composition and the U_b values.     

Aligned unidirectional PLA/bacterial cellulose nanocomposite fibre reinforced PDLLA composites

In an effort to enhance the properties of polylactide (PLA), we have developed melt-spinning techniques to produce both PLA/nanocellulose composite fibres, and a method akin to layered filament winding followed by compression moulding to produce self-reinforced PLA/nanocellulose composites. Poly(L-lactide) (PLLA) fibres were filled with 2 wt.% neat and modified bacterial cellulose (BC) in an effort to improve the tensile properties over neat PLA fibres. BC increased the viscosity of the polymer melt and reduced the draw-ratio of the fibres, resulting in increased fibre diameters. Nonetheless, strain induced chain orientation due to melt spinning led to PLLA fibres with enhanced tensile modulus (6 GPa) and strength (127 MPa), over monolithic PLLA, previously measured at 1.3 GPa and 61 MPa, respectively. The presence of BC also enhanced the nucleation and growth of crystals in PLA. We further produced PLA fibres with 7 wt.% cellulose nanocrystals (CNCs), which is higher than the percolation threshold (equivalent to 6 vol.%). These fibres were spun in multiple, alternating controlled layers onto spools, and subsequently compression moulded to produce unidirectional self-reinforced PLA composites consisting of 60 vol.% PLLA fibres reinforced with 7 wt.% CNC in a matrix of amorphous PDLLA, which itself contained 7 wt.% of CNC. We observed improvements in viscoelastic properties of up to 175% in terms of storage moduli in bending. Furthermore, strains to failure for PLLA fibre reinforced PDLLA were recorded at 17%.     

Effect of hydrogen bonding and moisture cycling on the compressive performance of poly-pyridobisimidazole (M5) fiber

A clear correlation between the degree of intermolecular hydrogen bonding (H-bonding) and axial compressive strength of pyridobisimidazole (M5) as-spun fiber specimens subjected to varying annealing conditions has been established by means of Fourier transform infrared microspectroscopy and single fiber elastica loop testing. As the water initially contained in the as-spun fiber is removed by heat treatment, improvements in polymer chain orientation promote the formation of intermolecular H-bonds, leading to enhanced fiber compressive strength values. M5 fiber specimens with the highest degree of intermolecular H-bonding of 96 ± 1% are found to have a compressive strength of 1.72 ± 0.09 GPa. Moisture cycling experiments of M5 annealed specimens have provided direct evidence of partial H-bond reversibility in this material, as saturation of M5 annealed fiber resulted in the reduction of the degree of intermolecular H-bonding from 93 to 64%. Upon drying the fiber at 120 °C in an inert atmosphere, the degree of H-bonding returned to the original value of 93%. However, repeated fiber moisture cycling resulted in a monotonic reduction in the degree of H-bonding in both the saturated condition (53%) and dry state (62%). The compressive strength of saturated and dried specimens after moisture cycling was found to be statistically equivalent at a reduced level of 1.29 GPa. The original degree of H-bonding and compressive strength could be recovered by re-annealing the fiber under tension.     

Polypropylene/cycloolefin copolymer blends: effects of fibrous phase structure on tensile mechanical properties

Tensile mechanical properties of polypropylene (PP)/cycloolefin copolymer (COC) blends were studied using an Instron tensile tester. As COC was expected to impart enhanced mechanical properties to the blends, their modulus, yield strength, tensile strength and tensile energy to break were measured as functions of blend composition. With regard to the reported sensitivity of the COC structure to thermal history, the influence of annealing at two different temperatures was also tested. The attention was primarily concentrated on blends with the volume fraction of COC in the interval 0<v₂<0.40, where COC formed (short) fibres almost uniaxially oriented in the direction of injection moulding. In the interval 0.40<v₂<0.75, the blends consisted of partially co-continuous components. Two different models were applied in the analysis of mechanical properties, namely (i) the rule of mixtures for fibre composites and (ii) the equivalent box model for isotropic blends (employing the data on the phase continuity of components obtained from modified equations of the percolation theory). Experimental data on the studied mechanical properties were better fitted by the models for fibre composites. Annealing of the samples (75 °C for 45 days; 120 °C for 3 h) did not markedly affect the tensile modulus, yield stress, and stress at break of the blends. On the other hand, the strain at break was markedly reduced by the annealing up to v₂=0.2; COC and the blend with 75% of COC ruptured in a brittle manner without yielding.     

Mechanical and microstructural characterisation of SiC- and SiBNC-fibre reinforced CMCs manufactured via PIP method before and after exposure to air

Non-oxide CMCs based on pyc-coated SiC-fibres (Tyranno SA3?) as well as novel amorphous ceramic fibres in the quaternary system Si–B–C–N (named SiBNC-fibres) were manufactured via polymer infiltration and pyrolysis process. Two different fibre architectures were applied: 0|90° unidirectional (UD) cross-ply and 0|90° plain weave fabric layer. UD cross-ply reinforced CMCs exhibit much more uniformly distributed filaments leading to better infiltration efficiency in resin transfer moulding process. Bending strength and fracture behaviour are strongly influenced by fibre architecture: UD cross-ply reinforced CMCs show higher bending strengths and less non-linear behaviour compared to plain weave fibre reinforcement. In tensile test there is no evidence of an influence of fibre architecture. Mechanical properties of unexposed SiC_pyc/SiCN and SiBNC_pyc/SiCN strongly correlate with fibre properties. After exposure to air (T = 1100 °C, 20 h), a significant decrease of mechanical properties could be observed, caused by complete oxidation of pyc-fibre coating interfered with silica formation.     

Reaction synthesis of SrTiO3 mineral-like ceramics for strontium-90 immobilization via additional in-situ synchrotron studies

The paper presents spark plasma sintering-reaction synthesis (SPS-RS) of SrTiO₃-based mineral-like ceramics with a perovskite structure, which is promising for immobilization of Sr-90 radionuclides. Detailed time-resolved study of phase transformations taking place in the reactive mixture (SrCO₃ and TiO₂) within 20–1000 °C temperature range was conducted using both in situ heating synchrotron XRD and TGA. Structure and composition dependence on consolidation temperature was revealed by the means of SEM and EDX. We determined optimal temperature conditions for rapid formation of SrTiO₃ ceramics with density – 4.49 g cm^?3, Vickers hardness – up to 6.2 GPa, compressive strength – 279 MPa, and strontium leaching rate of 10^?5–10^?6 g cm^?2·day. These results clearly show strong applied potential of the presented material for radioactive waste management and isotope production fields.     

Preparation and characterization of BaCe0.95Tb0.05O3−α hollow fibre membranes for hydrogen permeation

BaCe_0.95Tb_0.05O_3?α (BCTb) perovskite hollow fibre membranes were fabricated by spinning the slurry mixture containing 66.67 wt% BCTb powder, 6.67 wt% polyethersulphone (PESf) and 26.67 wt% N-methyl-2-pyrrolidone (NMP) followed by sintering at elevated temperatures. The influence of sintering temperature on the membrane properties was investigated in terms of crystal phase, morphology, porosity and mechanical strength. In order to obtain gas-tight hollow fibres with sufficient mechanical strength, the sintering temperature should be controlled between 1350 and 1450 °C. Hydrogen permeation through the BCTb hollow fibre membranes was carried out between 700 and 1000 °C using 50% H₂–He mixture as feed on the shell side and N₂ as sweep gas in the fibre lumen. The measured hydrogen permeation flux through the BCTb hollow fibre membranes reached up to 0.422 μmol cm^?2 s^?1 at 1000 °C when the flow rates of the H₂–He feed and the nitrogen sweep were 40 mL min^?1 and 30 mL min^?1, respectively.