This work aims at improving the interfacial bonding between polyamide‐12 and CNFs. CNFs were oxidized and dispersed in polyamide‐12 giving rise to polymer nanocomposites. The oxidation caused an increase in the specific surface area and structural defects of the fibers, as indicated by surface area and Fourier‐transform Raman spectroscopy. The nanocomposites exhibited improved thermal and thermo‐oxidative stabilities. The oxidized nanofibers had marginal effect on the crystallinity and crystallization of the polyamide‐12. An over‐proportional enhancement of stiffness due to the fibers could be achieved. In spite of these improvements the fiber/polymer adhesion should be further improved.
An amphiphilic LCBC PEO‐b‐PAz consisting of flexible PEO as a hydrophilic block and poly(methacrylic acid) containing an azobenzene moiety in side chain as a hydrophobic LC segment was synthesized and used to fabricated microporous films by spin‐coating method under a dry environment. With the help of a small amount of water, well‐arranged ellipsoidal micropores embedded in a LC matrix were obtained and the pore size is in the range of several tens µm of water. The influence of water content and rotational speed was studied in detail. It was found that regularly patterned microporous films can be prepared with certain water content, and the pore size can be easily tailored through changing the rotational speed. The obtained microporous structures showed good thermal and photo stability.
Nanostructuration of maleate and orthophthalic unsaturated polyester (UP) resins was achieved by the use of high molecular weight amphiphilic PBA‐b‐P(MMA‐co‐DMA)2 triblock copolymers. PBA is fully immiscible in cured UP resins, and the miscibility of P(MMA‐co‐DMA) random copolymers can be ensured with a minimum DMA content of 12 mol‐%. When using the triblock copolymers, fully transparent and nanostructured thermosets are obtained with a minimum DMA content in the outer blocks; the value of which is higher than 12 mol‐% and depends on the UP chemical structure. Finally, the fracture toughness of nanostructured thermoset was evaluated: for a triblock copolymer content as low as 5 wt.‐%, a 50% increase of KIc was obtained, as compared to the neat thermoset.
A new electrospinning set‐up is described for continuous aligning of poly(L ‐lactide) yarn. It comprises a slowly rotating grounded ‘funnel’ target and a winder placed right up to the funnel. A charged polymer jet is ejected from a nozzle. The electrospun fibers are first accumulated on the mouth plane of the funnel to form a web. The web is then pulled upward and guided to a winder on which twisted fibers are continuously wound as a bundle. Each filament of the bundle is slanted at about 45° relative to the collecting direction, and its average diameter is 6.0 ± 1.9 µm. The drawn fiber shows improved tensile properties as a result of the increased molecular orientation. The morphologies of the twisted fibers before and after drawing are compared.
MWCNT‐based composites have been successfully synthesized via layer‐by‐layer self‐assembly of crosslinked polyphosphazene nanoparticles on the surface of MWCNTs. The amino‐terminated CNTs were characterized by XPS, FT‐IR spectroscopy, EDS, XRD and TEM. The degree of functionalization could be controlled by simply changing the mass of hexachlorocyclotriphosphazene with 4,4′‐diaminodiphenyl ether. The activity of the surface amino groups was confirmed by the reaction of these groups with HAuCl4. In addition, the effects of the mass of HCCP and ODA ratios on the content of the surface amino groups was also investigated.
An ethylene‐octene copolymer (EOC) (45 wt% octene) is crosslinked using dicumyl peroxide (DCP). Differential scanning calorimetry (DSC) reveals a very low melting temperature (50 °C). The network density is evaluated by gel content. While 0.2–0.3 wt% of peroxide leads only to a molecular weight increase (samples completely dissolved in xylene), 0.4–0.6 wt% of peroxide caused network formation. High‐temperature creep was measured at 70, 120, and 200 °C at three stress levels. At 200 °C and above 0.6 wt% of peroxide, degradation due to chain scission is observed by rubber process analyzer (RPA) and is again supported by creep measurements. Residual strain at 70 °C is found to improve with increasing peroxide level. Dynamic mechanical analysis (DMA) reveals a strong influence of peroxide content on storage modulus and tan δ, in particular in the range 30–200 °C.
The first reported use of two‐dimensional mesh thermoplastic fibers in an epoxy matrix for mendable composites is presented, yielding 100% restoration of GIC, failure energy, and peak loads over repeated damage‐healing cycles. SEM imaging and EDS mapping showed different surface structures between CFRPp and CFRPf and confirmed strength recoveries were attained by delivery of EMAA to the fracture plane which enabled the fractured surfaces to rebind after heating to 150 °C for 30 min.
End‐grained wood/polyurethane composites were obtained by a water‐based one‐pot process free of diisocyanates. Wood was impregnated with both PEG and CBC‐functionalized PEG as a coupling agent. A thorough study of the CBC‐mediated end‐groups conversion of PEG was achieved. It came out that functionalization conditions strongly affected the polyurethane chain extension and its grafting onto the wood structure. Antiswelling efficiency measurements showed that the one‐pot procedure allowed to reach comparable dimensional stabilization than the diisocyanate‐based process previously described. Morphological analysis demonstrated that such an improvement was attributable to the formation of cell wall‐bulked WPCs.
Chemical and mechanical experiments are reported to elucidate the macroscopic effects of crosslinker length and composition on the thermomechanical response of acrylate‐based SMPs. To this end, EGA‐based formulations underwent a battery of basic tests which revealed that by increasing crosslinker chain length, polymer Tg can be decreased but there will be increases in compliance, step recoverability, and damping in a glassy state. Addition of methacrylate groups can cause increases in swelling, Tg, storage modulus in shorter chains, and greater damping at a rubbery state. All tested polymers exhibited mild hydrophilicity. PEGDA formulations exhibited good recoverability and could be an option for vascular applications.
A novel zirconia polyester nanocomposite is prepared using an in situ approach. Surface‐functionalized zirconia nanoparticles are obtained by attaching 3‐phosphonopropionic acid to the metal oxide. Neat and surface‐covered metal oxide particles are incorporated at the beginning of the polyesterification reaction of isophthalic acid and neopentyl glycol resulting in zirconia/poly(neopentyl isophthalate) (PNI) nanocomposites. TEM shows that the dispersibility of the inorganic filler is improved by covering the zirconia surface with carboxylic acid groups. These results are verified by SAXS. Rheological measurements reveal that the viscosities are increasing compared to pristine PNI at particle loads of 10 wt% (neat zirconia) and 5 wt% (phosphonic‐acid‐capped zirconia), respectively.
Iron‐oxide nanoparticles were functionalized with epoxy groups and were dispersed into a dicyclo‐aliphatic epoxy resin to obtain organic‐inorganic hybrid coatings via cationic ring‐opening photopolymerization. TEM investigations confirmed that the filler has a size‐distribution range between 5 to 20 nm, without the formation of aggregates. The influence of the presence of Fe2O3 on the rate of polymerization was investigated by real time FT‐IR spectroscopy. Increasing the iron‐oxide nanofiller in the photocurable resin induced an increase in the Tg values. By controlling the phase separation it was possible to obtain transparent iron‐oxide nanostructured coatings, characterized by improved hardness.
Multi‐wall CNT/poly[ethylene‐co‐(methacrylic acid)] composites were prepared by melt mixing. To improve dispersion and promote polymer/nanotube interactions, a novel non‐covalent compatibilizer is synthesized by reacting the polymer with 4‐(aminomethyl)pyridine. The composite based on the pristine polymer shows electrical and rheological percolation thresholds at nanotube loadings of 1.85 and 1.4 wt%, respectively. When 5 wt% of the pyridine‐modified compatibilizer is added, the corresponding values are reduced to 1.44 and 0.8 wt%, respectively. The electrical resistivity decreases even further as 10 wt% of the novel dispersing agent is used. Microscopy and Raman spectroscopy confirm the improved dispersion and π‐interactions established during melt mixing.
The influence of the functionalization of fully condensed POSS cages on the properties of POM‐based nanocomposites is studied. POSS with different organic substituents [glycidylethyl, aminopropylisobutyl, and poly(ethylene glycol)] are taken into account and melt mixed with POM. Good dispersion was achieved upon the addition of amino functionalized POSS, leading to an increase on the thermal decomposition temperature under nitrogen atmosphere up to 50 °C. However, µm‐size aggregates were observed for other nanocomposites. There is no significant change in other thermal properties of the nanocomposites. The relationships among these effects and the morphological characteristics of the systems were analyzed.
A method of manufacturing free‐standing, micrometer‐scale honeycomb polyetherimide films is reported for the first time. Films are manufactured with a dip‐coating technique under water‐assisted self‐assembly. It is shown that the addition of poly(organosilane/siloxane)s and poly(ethylene glycol) allows the formation of regular honeycomb patterns. The films demonstrated the high thermal stability inherent for polyetherimide. The wetting properties of films are reported. The presence of nanopores was revealed with SEM imaging of the films. The makeup of the films allows their use as asymmetric membranes for reverse osmosis and ultrafiltration.
Native and nucleated PHB has been melt‐spun and the properties of the resulting fibers have been investigated. Biocompatible nucleating agents such as HAP and THY were compared to BN as a reference material. DSC was used to investigate the non‐isothermal crystallization kinetics as a function of processing temperature and cooling rate. It was found that particularly the choice of process temperature can ensure sufficient primary crystallization of native PHB: heating not higher than 10–15 K above the melting temperature induced a favorable crystallization behavior of native PHB. Thus, melt spinning at low process temperatures without additives was demonstrated to be the key to the formation of well‐defined hollow PHB fibers.
We present a new strategy for fabricating thermally responsive adjustable stiffness materials. A microfabricated heater embedded within a composite film is used to modulate the temperature of a low melting point polymer. Currents ranging from 0 to 200 mA were applied to the microheater and modulated material stiffness ≈100‐fold between 1.03 GPa and 10.9 MPa. The outside temperature of the composite ranged from 23 to 45.5 °C over this range of currents, suggesting its possible use in biomedical applications. The softened composite was bent into arbitrary shapes and allowed to restiffen, highlighting the reconfigurable nature of the material.
CNT were dispersed in an epoxy matrix and cured by means of UV light. An increase on elastic modulus and Tg values was measured by DMTA analysis and attributed to the constraint effect of CNT on polymer chain mobility. Excellent scratch resistant coatings characterized by high critical load, small cracks and high recovery were obtained in the presence of a very low CNT content (0.025 wt.‐%). TEM analysis showed some isolated CNT and some cluster agglomerations of size of about 250 nm. It was shown that it was possible to decrease the surface resistivity of the cured samples by three orders of magnitude in the presence of 0.1 wt.‐% of SWCNT content.
The effects of MWNT content and aspect ratio on the properties of epoxy‐based nanocomposites are investigated using nanoindentation and nanoscratch methods. The Halpin‐Tsai model for predicting the elastic modulus and hardness is modified to include the effective aspect ratio factor. The modified model predicts the experimental results more accurately. The frictional behavior is investigated and a new equation is proposed that correlates the ploughing friction with the plasticity index. The dispersion state of MWNTs and the surface features of residual grooves are investigated using scanning electron micrographs and AFM profiles. The mechanisms of improvements in the properties are also discussed.
1,3,5‐Benzenetrisamide‐based supramolecular nucleating agents for poly(butylene terephthalate) (PBT) are reported. 1,3,5‐Benzenetrisamides combine excellent thermal stability with chemical resistance, basic requirements for the use in high‐melting thermoplastics. To establish structure–property relationships, the central core and peripheral substituents are varied systematically. Dissolution and crystallization behavior of the additives in the PBT melt and the crystallization temperature of PBT are investigated as a function of the additive concentration. Efficient nucleating agents can increase the crystallization temperature of PBT by 10.6 °C to 199.1 °C. A visualization of supramolecular nano‐objects formed in the polymer melt is provided.
The long‐term viscoelastic behavior of reinforced all‐poly(propylene) composites was studied by flexural creep tests. Both unidirectional and cross‐ply laminates were prepared from PURE® coextruded tapes by vacuum bag molding in an autoclave. The specimens were subjected to isothermal creep tests at different temperatures ranging from 20 to 80 °C under an applied load. The time‐temperature superposition principle was verified for the creep data. An Arrhenius type relationship was found to better describe the shift data obtained from the creep tests. The activation energies relating to the different reinforcement architecture and different relaxation process were calculated.
