Polytetrafluoroethylene (PTFE) films have been irradiated by electron beam in vacuum at various temperatures ranging from room temperature up to temperatures far above the melting temperature. Changes of the chemical structure have been analyzed by 19F solid‐state NMR and IR spectroscopy. The concentration of several structures generated by irradiation increases with increasing irradiation temperature up to the beginning of the thermal degradation. The molar ratio of >CF? branching points to ? CF3 end groups changes with crossing of the melting temperature. The generation of >CF? branching points is accelerated if the PTFE is irradiated in the molten state, where branching reactions become more important.
Summary: Polycaprolactone (PCL) and starch/PCL blends (SPCL) are shown to have the potential to be used in a range of biomedical applications and can be processed with conventional melting‐based procedures. In this paper, the thermal and thermomechanical analyses of PCL and SPCL were performed, using DSC, optical microscopy and DMA. Starch effectively increased the non‐isothermal crystallisation rate of PCL. Non‐isothermal crystallisation kinetics was analyzed using Ozawa model, and a method, which combines the theories of Avrami and Ozawa. Starch effectively reinforced PCL and enhanced its damping properties, which indicated that SPCL could be more suitable than PCL in some biomedical applications, as it might help in the dissipation of the mechanical energy generated by the patient movements.
Dynamic mechanical behaviour of PCL and SPCL at 1 Hz. 相似文献
Poly(methyl methacrylate)‐poly(ε‐caprolactone) (PMMA/PCL) microparticles were synthesized by suspension polymerization of methyl methacrylate in the presence of PCL. The incorporation of a small amount of a macromonomer, methacryloyl‐terminated PCL (M‐PCL), into the reaction mixture, led to the formation of grafted systems, namely PMMA‐g‐PCL/PCL. The synthesis of the macromonomer and its characterization by nuclear magnetic spectroscopy (1H NMR) is described. The role of M‐PCL as an effective compatibilizing agent in the composite was investigated. PMMA/PCL and PMMA‐g‐PCL/PCL composites were fully characterized by 1H NMR, gel permeation chromatography (GPC) and thermal analysis, including thermogravimetric analysis (TGA), conventional differential scanning calorimetry (DSC), modulated DSC (MDSC) and dynamic mechanical thermal analysis (DMTA). Finally, the morphology of the prepared systems was investigated by scanning electron microscopy (SEM). The addition of compatibilizing agent led the formation of a more homogeneous microcomposite with improved mechanical properties.
SEM picture of PMMA‐g‐PCL/PCL composite surface. 相似文献
The properties of segmented‐copolymer‐based H‐bonding and non‐H‐bonding crystallisable segments and poly(tetramethylene oxide) segments were studied. The crystallisable segments were monodisperse in length and the non‐hydrogen‐bonding segments were made of tetraamidepiperazineterephthalamide (TPTPT). The polymers were characterised by DSC, FT‐IR, SAXS and DMTA. The mechanical properties were studied by tensile, compression set and tensile set measurements. The TPTPT segmented copolymers displayed low glass transition temperatures (Tg, ?70 °C), good low‐temperature properties, moderate moduli (G′ ≈ 10–33 MPa) and high melting temperatures (185–220 °C). However, as compared to H‐bonded segments, both the modulus and the yield stress were relatively low.
This study is related to the use of hydroxyl functional acrylic cross‐linked polymer microparticles (CPM, also named microgels) as a chain transfer agent in cationic photopolymerization of cycloaliphatic epoxy monomer. All CPM were based on butyl acrylate and were consequently rubbery at ambient temperature. The effect of the stabilizing acrylate monomer used during the CPM synthesis was evaluated with respect to the viscoelastic properties of the photopolymerized cationic‐type epoxy films. The viscoelastic properties were correlated to the photopolymerized film morphology observed by transmission electron microscopy. Two acrylate monomers used as stabilizing agents during CPM synthesis were compared: cardura acrylate (CA) and lauryl acrylate (LA). CA was a good stabilizer for CPM in epoxy monomer before photocure and the CPM were well dispersed into the network after reaction. In contrast, LA was a poor stabilizer resulting in large CPM aggregation. The blend of these two types of CPM led to intermediate morphology, probably because of the flocculation of the CPM stabilized with LA. Conversely, CPM synthesized with a blend of the two stabilizing acrylate monomers induced in epoxy matrix a specific bi‐continuous morphology and consequently unique viscoelastic properties.
TEM micrographs of a photopolymerized film with 15 wt.‐% CPM(BA + 20%HEA)‐20%CA + 15% CPM(BA + 18%HEA)‐27%LA used as chain transfer agents. 相似文献
Summary: Silica‐supported single‐site catalysts show limitations with respect to catalyst homogeneity and maximum metal content. A novel emulsion‐based catalyst heterogenization concept is described, which allows these limitations to be overcome. The method produces catalyst particles with an inherently perfect spherical shape and unique intra‐ and inter‐particle homogeneity. The catalyst particles are very compact and have a low surface area. Video microscopic studies confirm that the improved catalyst homogeneity leads to a more uniform polymerization behavior on a single particle level. The catalysts contain significantly more complex, compared to silica‐supported catalyst systems, which leads to correspondingly higher catalyst activities. No differences, in terms of the mass‐transfer kinetics of these low‐porosity catalysts, compared to porous catalyst systems have been observed.
Electron microscopy image of self‐supported single‐site catalyst prepared by the emulsion‐based method. 相似文献
Natural biomaterials were used to improve the biocompatibility of synthetic biopolymers. PCL was electrospun with natural biopolymers, silk fibroin, and small intestine submucosa. Due to increased electrical conductivity, the diameter of the composite fibers highly depended on the amount of SIS in the polymer solution. PCL/SF/SIS electrospun composites exhibited various synergistic effects, including enhanced mechanical properties and incredibly improved hydrophilicity compared to those of pure PCL and PCL/SF fibers. An initial cell attachment test demonstrated that the interactions between PC‐12 nerve cells and the PCL/SF/SIS composites were more favorable than those between PC‐12 cells and a PCL/SF composite.
The viscoelasticity of two thermally crosslinked polymer coatings was examined in terms of relaxation of the applied stress after a sudden strain. Two different transient methods were utilized: flat‐ended cylindrical indentation testing of a polymer film on a rigid substrate and tensile testing of a corresponding free‐standing polymer film. The correlation between tensile and indentation tests was studied. The mechanical response of a viscoelastic layer deposited on a rigid substrate was investigated as a function of indentation depth. There was good agreement between the results of the tensile and indentation tests for thick film layers at moderate indentation depths. The findings indicate that the substrate influences the coating performance by reducing the viscous contribution to the stress response and amplifying the magnitude of the equilibrium modulus for large indentation depths. The indentation method utilized here was shown to be a potentially suitable tool for the determination of Poisson's ratio of polymer films.
Summary: The preparation of poly(ε‐caprolactone)‐g‐TiNbO5 nanocomposites via in situ intercalative polymerization of ε‐caprolactone initiated by an aluminium complex is described. These nanocomposites were obtained in the presence of HTiNbO5 mineral pre‐treated by AlMe3, but non‐modified by tetraalkylammonium cations. These hybrid materials obtained have been characterized by Fourier transform infrared absorption spectroscopy, wide‐angle X‐ray scattering, scanning electron microscopy, and dynamic mechanical analysis. Layered structure delamination and homogeneous distribution of mineral lamellae in the poly(ε‐caprolactone) (PCL) is figured out and strong improvement of the mechanical properties achieved. The storage modulus of the nanocomposites is enhanced as compared to pure PCL and increases monotonously with the amount of the filler in the range 3 to 10 wt.‐%.
SEM image of the fractured surface of a PCL‐TiNbO5 nanocomposite film. 相似文献
The ternary Ziegler‐Natta‐type catalyst system based on neodymium versatate (NdV), diisobutylaluminium hydride (DIBAH) and ethylaluminium sesquichloride (EASC) was used for the in situ preparation of a compatibilized blend consisting of poly(cis‐1,4‐butadiene) (BR = butadiene rubber) and poly(ε‐caprolactone) (PCL). Poly(cis‐1,4‐butadiene)‐block‐poly(ε‐caprolactone) which acts as compatibilizer for the two immiscible polymers BR and PCL was obtained by a two step sequential polymerization with the preparation of a living cis‐1,4‐BR building block in the first stage and the subsequent polymerization of CL during the second stage. This preparation method resulted in a polymer blend comprising the homopolymers BR and PCL as well as the block copolymer BR‐block‐PCL. For detailed characterization the block copolymer was separated from the respective homopolymers BR and PCL by means of fractionation with the binary solvent mixture dimethylformamide/methylcyclohexane (DMF/MCH) which mixes well at elevated temperature and exhibits phase separation at ambient temperature. 1H NMR, IR, SEC and TEM were used for characterization of the block copolymer.
Pressure‐sensitive adhesives (PSA) were microencapsulated using simple and complex coacervation and aminoplaste. The microcapsules thus prepared were characterized by FTIR spectroscopy, particle size distribution, rheological behavior, and peeling tests. The microcapsules were isolated and found to be out of sticky indicating that the PSAs were indeed encapsulated. The prepared suspensions were deposited at the surface of a paper sheets and the dried labels were then pressed against each other. The ensuing complex was then characterized in terms of peeling forces and showed that the encapsulation using aminoplaste technique of a commercial PSA yielded peel energy of 170 J · m?2, which constitutes the recovering of about 68% of the adhesive power of the original nonencapsulated PSA.
Summary: Ethylene vinyl acetate (EVA) copolymer/dodecyl ammonium ion intercalated montmorillonite (12Me‐MMT) nanocomposites were swelled in xylene under atmospheric condition. Swelling index of these nanocomposites decreased with filler loading indicating that the solvent uptake of these nanocomposites was inversely related to the filler contents. The volume fractions of nanocomposites showed an increasing trend with filler concentration because of unswelling effect exerted by aluminosilicate layers. The cross‐link density was determined using the Flory‐Rehner equation and it was observed that the cross‐link density of these nanocomposites also showed an increasing trend with increasing filler loading. Free energy change (ΔGmix) and the change in entropy (ΔSmix) on swelling of EVA/12Me‐MMT nanocomposites in xylene were calculated and these values reaffirmed that the interaction between polymer chains and silicate layers was very strong which induced remarkable inhibiting ability on EVA matrix when swelled in xylene.
TEM photograph of EVA/12Me‐MMT nanocomposite containing 8 wt.‐% 12Me‐MMT. 相似文献
In the field of hot plate welding, experimental investigations show that the stress cracks are caused by inherent stresses in the component, which are induced in the part while it is being heated on the tool. For the better understanding of the process parameters and their effects on the phenomenon of stress cracking, a simple theoretical model for the calculation of the temperature and the stress field is to be developed. The application of the presented method shows the effects of the process parameters on the phenomenon of stress cracking and correlates with the experimental results of further investigations.
A microfluidic system was designed, fabricated and implemented to study the behavior of polyelectrolyte capsules flowing in microscale channels. The device contains microchannels that lead into constrictions intended to capture polyelectrolyte microcapsules which were fabricated with the well‐known layer‐by‐layer (LbL) assembly technique. The behavior of hollow capsules at the constrictions was visualized and the properties of the capsules were investigated before and after introduction into the device.
Time series of video frames showing capsules being compressed into a constriction. 相似文献
Electrically conducting films containing AgNws, hydrophilic and hydrophobic resins were prepared. FT‐IR reveals that the interface between the AgNws and epoxy could be successfully modified by APTES. XPS shows that the AgNws were attracted by hydrogen bonds of ? NH2 and ? NH? groups after APTES modification. SEM analysis shows that the AgNws were well dispersed in the resin. The AgNws were also blended with hydrophilic and acrylic resins, and the resulting blends were compared with AgNws/epoxy blends. Results show that AgNw/PVA‐resin films possess the lowest surface electrical resistance. The AgNw/PVA‐resin and silane‐modified AgNw/epoxy resin conductive films possess a similar electrical percolation threshold.
Summary: An organic‐inorganic hybrid material consisting of a 3‐(methacryloxy)propyl functionalized SiO2/MgO framework was synthesized. This hybrid was successfully reacted with styrene, butyl acrylate and butyl methacrylate via a free radical emulsion polymerization to form polymer composites. The polymer composites were investigated by means of FT‐IR spectroscopy, TGA, DSC and rheometry. It is shown that the polymer is linked covalently to the organic/inorganic hybrid. Although the polymer content is rather low, the composites exhibit a polymer‐like character and enhanced mechanical properties compared to the corresponding homopolymers.
Summary: It is well known that the weight‐average molecular weight ( ) is strictly dependent on conversion in step‐growth polymerizations performed in batch and that the is very sensitive to impurities and molar imbalance. This makes the work of controlling a non trivial job. In this paper a new methodology is introduced for in‐line monitoring and control of conversion and of polyurethanes produced in solution step‐growth polymerizations, based on near‐infrared spectroscopy (NIRS) and torquemetry. A calibration model based on the PLS method is obtained and validated for monomer conversion, while the weight‐average molecular weight is monitored indirectly with the relative shear signal provided by the agitator. Control procedures are then proposed and implemented experimentally to avoid gelation and allow for maximization of . The proposed monitoring and control procedures can also be applied to other step growth polymerizations.
Summary: Blends of different compositions were prepared from: a thermoplastic elastomer (EPDM), a low density polyethylene (PE), a polystyrene crosslinked with a small amount of divinylbenzene (PS‐co‐DVB) and an inorganic proton conductor: antimonic acid (HSb). The blends obtained were sulfonated heterogeneously with chlorosulfonic acid and were then structurally and electrically characterized by means of the following techniques: differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), crystallization kinetics under non‐isothermal conditions and complex impedance spectroscopy.
Dynamic mechanical analysis for EPDM and EP‐3 blends series. 相似文献
Summary: Hydroxyapatite, chitosan, and aliphatic polyester were compounded using a twin‐screw extruder. The polyesters include poly(ε‐caprolactone) (PCL), poly(lactic acid) , poly(butylene succinate) (PBS), and poly(butylene terephthalate adipate). The mass fraction of chitosan ranged from 17.5 to 45%, while that of HA ranged from 10 to 30%. These blends were injection molded and evaluated for thermal, morphological, and mechanical properties. The addition of hydroxyapatite decreased the crystallinity in chitosan/PBS blends, while in blends containing chitosan/PCL, the crystallinity increased. Addition of hydroxyapatite significantly decreased the tensile strength and elongation of polyester/hydroxyapatite composites as well as chitosan/polyester/hydroxyapatite composites with elongations undergoing decreases over an order of magnitude. The tensile strength of the composite was dictated by the adhesion of HA to the chitosan/polyester matrix. The tensile strength of composites containing hydroxyapatite could be predicted using the Nicolai and Narkis equation for weak filler adhesion (K ≈ 1.21). Tensile‐fractured and cryogenically‐fractured surface indicates extensive debonding of hydroxyapatite crystals from the matrix, indicating weak adhesion. The adhesion of hydroxyapatite was higher for pure polyester than those containing chitosan and polyester. The modulus of the composites registered modest increase. The two main diffraction peaks observed using WAXS are unaffected by the amount of chitosan or hydroxyapatite.
Hybrid organic‐inorganic materials based on the sol‐gel synthesis of an organically modified silicon alkoxide have demonstrated their great potential for optical applications. They offer a high versatility in terms of chemical, physical properties and macroscopic shape molding of the final component. Recently, a photolithographic process allowed the generation of relief optical elements without requiring a wet treatment to reveal the latent image. It enabled a low cost, simple and quick method for the fabrication of integrated optical components. The aim of the present paper is to give new insights into the mechanisms of surface self‐corrugation leading to gratings generation in hybrid sol‐gel films. A study of the relief formation was led by giving particular attention to the kinetic aspects of the polymerization of the organic component. The control of the C?C double bonds conversion of methacrylate functionalized alkoxides in case of photopolymerization is therefore an essential issue to tailor material properties. The study also focuses on the influence of physico‐chemical parameters that govern the relief generation and underlines the particular role of temperature. Kinetics of surface corrugation point out the importance of strain relaxation, mass‐transfer by flowing and organic network formation during the photolithographic process. Some illustrations of the generated diffraction gratings are given.
Interferogram of the diffraction grating obtained after 120 s exposure through a chromium mask. 相似文献