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1.
Nucleation of isotactic polypropylene (iPP) crystallization by gold (Au) nanoparticles was studied. Regardless of their size, 4.3, 8.8, 28.3, and 84.5 nm, all particles were able to nucleate spherulites when deposited on the iPP surface. However, when added and melt‐mixed with iPP, only the smallest particles affected significantly the iPP bulk crystallization. Au nanoparticles larger than 4.3 nm, at the concentration of 0.001 wt %, did not influence the crystallization of iPP. Contrary to this, 0.001 and 0.005 wt % of Au nanoparticles having the size of 4.3 nm increased crystallization temperature of the iPP by 7–8 °C and decreased markedly the sizes of polycrystalline aggregates. Aggregation of Au nanoparticles in the polymer matrix was evidenced by electron microscopy and contributed to their decreased effectiveness in the nucleation of iPP crystallization. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 469–478, 2010  相似文献   

2.
Syndiotactic 1,2-polybutadiene/organoclay nanocomposites were prepared and characterized by thermogravimetry analysis (TGA), X-ray diffraction (XRD), polarized optical microscopy (POM), and differential scanning calorimetry (DSC), respectively. The XRD shows that exfoliated nanocomposites are formed dominantly at lower clay concentrations (less than 2%), at higher clay contents intercalated nanocomposites dominate. At the same time, the XRD indicates that the crystal structures of sPB formed in the sPB/organoclay nanocomposites do not vary, only the relative intensity of the peaks corresponding to (0 1 0) and (2 0 0)/(1 1 0) crystal planes, respectively, varies. The DSC and POM indicate that organoclay layers can improve cooling crystallization temperature, crystallization rate and reducing the spherulite sizes of sPB. TGA shows that under argon flow the nanocomposites exhibit slight decrease of thermal stability, while under oxygen flow the resistance of oxidation and thermal stability of sPB/organoclay nanocomposites were significantly improved relative to pristine sPB. The primary and secondary crystallization for pristine sPB and sPB/organoclay (2%) nanocomposites were analyzed and compared based on different approaches. The nanocomposites exhibit smaller Avrami exponent and larger crystallization rate constant, with respect to pristine sPB. Primary crystallization under isothermal conditions displays both athermal nucleation and three-dimensional spherulite growth and under nonisothermal processes the mechanism of primary crystallization becomes very complex. Secondary crystallization shows a lower-dimensional crystal growth geometry for both isothermal and nonisothermal conditions. The activation energy of crystallization of sPB and sPB/organoclay nanocomposites under isothermal and nonisothermal conditions were also calculated based on different approaches.  相似文献   

3.
The dependence of enantio-selective chromatographic performance on particle size, as measured by separation factor, was investigated for one-monomer molecularly imprinted polymers (OMNiMIPs) compared to traditionally formed EGDMA/MAA molecularly imprinted polymers (MIPs). Five particle size ranges were compared (<20 μm, 20-25 μm, 25-38 μm, 38-45 μm, and 45-63 μm), revealing that the particle sizes above 25 μm provided the highest separation factor, and thus the best enantiomer separation, for both imprinted polymers. Other chromatographic parameters such as the number of theoretical plates and resolution exhibited only minor changes for the OMNiMIPs as the particle size changed, except for particles 20 μm and below. However, the number of theoretical plates and resolution for EGDMA/MAA are higher for particles in the 20-25 μm range. Thus, chromatographic factors for the EGDMA/MAA polymers are better in this range, despite better enantioselectivity for particle sizes above 25 μm. In contrast, OMNiMIPs generally show the most favorable performance for particle sizes in the 38-45 μm range. It was also found that decreasing flow rate resulted in improved enantioselectivity for both MIPs for all particle sizes.  相似文献   

4.
Shear-induced isothermal crystallization in iPP based nanocomposites with organo-modified montmorillonite was followed by light depolarization technique. Prior to the crystallization, samples were sheared at 1 or 2 s−1 for 10 s in a plate-plate system at crystallization temperature of 136 °C. Structure of the solidified specimens was investigated by light microscopy and electron microscopy, X-ray techniques and IR spectroscopy. Strong enhancement of the nucleation and crystallization after shearing was observed in the compatibilized nanocomposites with the clay. Clay exfoliation was found to accelerate strongly the shear-induced nucleation and overall crystallization. However, the sheared samples exhibited only weak orientation of α crystals with (0 4 0) crystallographic planes parallel to shearing direction that resulted probably from a small population of oriented crystals that formed due to shear-induced orientation of iPP chains and served as nuclei for further nearly isotropic growth.  相似文献   

5.
Using an experimental setup with a three‐phase intersecting boundary of PTFE/PE/iPP, the nucleation power of PTFE compared to iPP on the PE was studied by TEM. It was found that the nucleation of the PE on the PTFE interface started at a higher temperature than epitaxial nucleation of the PE onto the iPP interface. During cooling of the melt, the growth direction of the PE crystalline lamellae changes in a continuous manner from the transcrystallization direction of the PTFE/PE interface into the heteroepitaxial “crosshatched” orientation of the iPP/PE interface. A (still highly speculative) self‐assembly of the PE macromolecules at the respective interface just in front of the actual crystallization edge is used to explain this observed phenomenon. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 80–83, 2000  相似文献   

6.
Although under normal conditions only the crystallization behavior of PE on oriented iPP substrates can be studied due to the higher melting point of iPP, the faster crystallization rate of a molten, oriented HDPE film compared to a nonoriented iPP layer was used to study the crystallization of iPP on the oriented HDPE film by means of transmission electron microscopy (TEM) and electron diffraction (ED). Besides the known epitaxial relationship of HDPE/iPP with their chains 50° apart, two new orientation relationships with (a) chains of both polymers parallel and (hk0)iPP in contact with the HDPE substrate, and (b) the a‐axis of iPP crystals parallel to the chain direction of HDPE but (001)iPP in contact with the HDPE substrate were observed. Both orientations are assumed as graphoepitaxy. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1893–1898, 1999  相似文献   

7.
Supermolecular structure and phase morphology of the ternary isotactic polypropylene/atactic polystyrene/poly(styrene-b-ethylene-co-propylene) (iPP/aPS/SEP) compression molded blends with 100/0, 90/10, 70/30, and 50/50 iPP/aPS weight ratios and with different amounts of added SEP compatibilizer were studied by optical microscopy (OM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD). SEP significantly reduced the size of dispersed aPS particles that enabled better spherulitization in the iPP matrix. Furthermore, iPP spherulites in ternary blends with 90/10 iPP/aPS weight ratio became larger in comparison with the pure iPP. TEM revealed that the SEP formed continuous interface layer around the dispersed aPS particles even when only 2.5 wt.% of SEP was added. Particle size distribution was distinctly bimodal. When the SEP content was increased to 10 wt.%, joining together smaller and bigger aPS and SEP particles formed dispersed aggregates. Additionally, both amorphous components (aPS and SEP) influenced crystallization process of iPP matrix and so modified, to some extent, its final supermolecular structure. SEP compatibilizer did not significantly affect crystallite orientation. The increase of crystallite sizes, which was more affected by the addition of aPS than by the addition of SEP, seemed to be influenced by the solidification effect rather than by the phase morphology of the blends.  相似文献   

8.
Spherulitic crystals of Poly(tetrafluoroethylene) (PTFE), for the first time, are observed in a kind of PTFE composite, and are verified by polarized optic microscopy (POM). Differential scanning calorimetry (DSC) is used to study the isothermal crystallization kinetics of PTFE matrix at different temperatures. The result shows that Avrami parameter is near 3, which may be elucidated that PTFE crystallizes three-dimensionally from preexisting nuclei. The result is in accordance with scanning electric microscopy (SEM) and POM observation of the crystalline morphology of PTFE. Compared with the rate of one-dimension crystallization, the rate of three-dimension crystallization is lower. So the three-dimension crystallization is easier to control than the one-dimension crystallization of PTFE.  相似文献   

9.
The morphology of crystals, isothermal and non-isothermal crystallization of poly(methylene terephthalate) (PMT) have been investigated by using polarized optical microscopy and differential scanning calorimeter (DSC). The POM photographs displayed only several Maltese cross at the beginning short time of crystallization indicating that some spherulites had been formed. The crystal cell belonged to the Triclinic crystal systems and the cell dimensions were calculated from the WAXD pattern. The commonly used Avrami equation and that modified by Jeziorny were used, respectively, to fit the primary stage of isothermal and non-isothermal crystallization. The Ozawa theory was also used to analyze the primary stage of non-isothermal crystallization. The Avrami exponents n were evaluated to be in the range of 2-3 for isothermal crystallization, and 3-4 for non-isothermal crystallization. The Ozawa exponents m were evaluated to be in the range of 1-3 for non-isothermal crystallization in the range of 135-155 °C. The crystallization activation energy was calculated to be −78.8 kJ/mol and −94.5 kJ/mol, respectively, for the isothermal and non-isothermal crystallization processes by the Arrhenius’ formula and the Kissinger’s methods.  相似文献   

10.
To investigate how the superfine particles disperse in the polymers, the paper presented the preparation of monodisperse silica particles by Stöber method, and then grafted by γ-methacrylic propyl trimethoxysilane (MPS) as a coupling agent. Using these modified particles, the more stable silica-PS superfine composite particles with higher monodispersity than these of previous reports are prepared and reported through dispersion polymerization (DP) method, whose morphology is investigated with transmission electron microscope (TEM). Their high stability is provided from the bonding of CC groups of MPS to the silanol groups on the surface of silica particles from FTIR.Using this DP process, the influence of different size grafted silica particles on the morphology, polystyrene (PS) encapsulation behavior and the distribution in these composite particles have been investigated. When the grafted silica size is in nanoscale or less than 54 nm, the spherical shape of neither silica particles nor their composite particles is regular, but they can homogeneously disperse in polystyrene. As the size (dn) of grafted silica particles increase to submicrometer (or 100 nm < dn < 1000 nm), their coefficient variance of size distribution (Cv) ranges from only 9.0% to 1.5%. These obtained particles are completely encapsulated by PS with more regular shape, and have their Cv below 7%. When the size of silica particles reaches 380 nm, their Cv obviously reduces to 2.5%, and specially, the number of grafted silica particles approaches to one in each of the composite particles. But, when the silica size reaches 602 nm, PS can hardly encapsulate grafted silica particles and free silica particles appear in reactive system.Furthermore, using the silica particles of 380 nm, a series of core-shell structured superfine composite particles of 640-1100 nm with Cv lower than 11% are obtained. Under the set conditions, the preparing factors on these composite particles using 380 nm grafted silica particles is discussed, and the best reaction condition for the well-dispersed and regular periphery silica-PS composite particles is optimized as, the additions amounts of PVP, styrene, AIBN, grafted SiO2 and H2O are 0.23 mmol L−1, 0.60 mol L−1, 6.10 mmol L−1, 0.10 mol L−1 and 5.50 mL, respectively. Under this case, the composite particles can be prepared with Cv below 8%.At last, these composite particles are mixed with poly(ethylene terephthalate) (PET) to investigate their nucleation effect. Results show that all different size particles can promote PET’s crystallization and enhance the crystallization rate, and PET’s crystallization temperature (Tmc) is obviously enhanced from 193 to 205 °C through differential scanning calorimetry (DSC). It is strongly suggested that different silica size level all play nucleation role in PET, and thus explain the nucleation effect of multiscale inorganic particles.  相似文献   

11.
Sodium benzoate (SB), a conventional nucleating agent of α‐phase isotactic polypropylene (iPP) was discovered to induce the creation of β‐phase iPP under certain crystalline conditions. Polarized optical microscopy (POM) and wide angle X‐ray diffraction (WAXD) were carried out to verify the versatile nucleating activity of SB and investigate the influences of SB's content, isothermal crystallization temperature, and crystallization time on the formation of β‐phase iPP. The current experimental results indicated that, under isothermal crystallization conditions, SB showed peculiar nucleating characteristics on inducing iPP crystallization which were different from those of the commercial β form nucleating agent (TMB‐5). The content of β crystal form of iPP nucleated with SB (PP/SB) increased initially with the increase of crystallization temperature, nucleating agent (SB) percentage or crystallization time, reached a maximum value, and then decreased as the crystallization temperature, nucleating agent percentage or crystallization time further increased. While the content of β crystal form of iPP nucleated with TMB‐5 (PP/TMB‐5) showed a completely different changing pattern with the crystallization conditions. The obvious difference of the two kinds of nucleating agents on inducing iPP crystallization can be explained by the versatile nucleating ability of SB. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1183–1192, 2008  相似文献   

12.
Aiming at further investigating the combination effect of concentration of β‐nucleating agent (β‐NA) and stereo‐defect distribution on the crystallization behavior of β‐nucleated isotactic polypropylene (β‐iPP), in this study, the crystallization behavior and polymorphic morphology of twoβ‐iPP resins with nearly same average isotacticity (PP‐A and PP‐B) but different uniformities of stereo‐defect distribution were investigated by differential scanning calorimetry (DSC), wide angle X‐ray diffraction (WAXD) and polarized optical microscopy (POM). The results of DSC and WAXD showed that the addition of TMB‐5 increases the crystallization temperature and decreases the spherulite sizes of both PP‐A and PP‐B, and reduces their crystallization energy barriers as well; however, the polymorphic behaviors of PP‐A and PP‐B exhibit different dependence on the TMB‐5 concentration. For PP‐A with less uniform distribution of stereo‐defects, β‐phase can be observed only when the TMB‐5 concentration is no less than 0.1 wt.%, while for PP‐B with more uniform stereo‐defect distribution, addition of 0.01 wt.% TMB‐5 can induce the formation of β‐phase. Moreover, the analysis of POM indicated that the crystalline morphologies of both PP‐A and PP‐B change greatly with the TMB‐5 concentration, and the variation features of PP‐A and PP‐B are quite different from each other. PP‐B with more uniform stereo‐defect distribution was more favorable for the formation of large amount of β‐phase in the presence of wide concentration range of TMB‐5. The different polymorphic behaviors and their different dependences on the β‐NA concentration were related to the different uniformities of stereo‐defect distribution of the samples, since the distribution of stereo‐defects could restrain the regular insertion of molecular chains during crystallization and thus determine the tendency the α‐phase crystallization of the sample. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

13.
Gamma-radiation induced degradation of polytetrafluoroethylene (PTFE) in 60 wt.% dispersion was studied in the dose range of 20-200 kGy and the change in property of PTFE was characterized by differential scanning calorimetry (DSC), photon cross correlation spectroscopy (PCCS), X-ray diffraction (XRD), scanning electron microscopy (SEM), FT-IR spectroscopy and X-ray photoelectron spectroscope (XPS). It was found that the mean particle size of PTFE reduces from 250 nm of the control to 170 nm at 100 kGy, as confirmed by dynamic laser scattering and SEM. The crystallinity degree of PTFE increased at 20 kGy but remained unvaried at higher dose level. G-value of scission, G(s), was determined to be 0.46 μmol/J.  相似文献   

14.
Linear low-density polyethylene (LLDPE) was grafted onto the backbone chains of isotactic polypropylene (iPP) during reactive melt-extrusion to produce a novel toughening modifier, propylene/ethylene graft copolymer (PEGC), to improve the properties of iPP random(-copolymerized with a small amount of ethylene) (PPR). The crystallization behavior as well as the non-isothermal crystallization kinetics of the PEGC modified PPRs were investigated via differential scanning calorimetry (DSC), polarized optical microscopy (POM) and wide-angle X-ray diffraction (WAXD). The fractured surface topography was characterized using scanning electron microscopy (SEM), and the mechanical properties through notched impact and tensile testing as well as dynamic mechanical thermal analysis (DMTA). The results show that, at a PEGC content of 8 wt%, notched impact strength of the PEGC modified PPR increased by 30.6% at low temperature (−25 °C). As regards crystalline morphology, the PEGC, as an effective heterogeneous nucleating agent, fostered nucleation of the PPR to elevate its crystallization temperature as well as rate of crystallization, thus refining the PPR (iPP) spherulites and improving the interfacial structure between iPP spherulites. The Jeziorny approach was unsatisfactory for simulation of the non-isothermal crystallization process of the PEGC modified PPRs; however, the Mo method described consistently the crystallization kinetics over the entire isothermal process.  相似文献   

15.
The non-isothermal crystallization kinetics of isotactic polypropylene (iPP) and nucleated iPP was investigated by DSC. The crystalline morphology of iPP was observed by polarized light microscopy. It was found that the crystallization rate increased with the addition of nanometer-scale calcium carbonate (nm-CaCO3) particles. The addition of dibenzylidene sorbitol (DBS) could greatly reduce the spherulite size of iPP. The crystallization temperature for the iPP with DBS was higher than for non-nucleated iPP. DBS was an effective nucleating agent for iPP. The results of measurements suggested that there was a coordinated action to the crystallization of iPP when the organic nucleating agents (DBS) and nm-CaCO3 were added to iPP together. Comparison to the modified Avrami equation and Ozawa equation, another method—Mo’s method can describe the non-isothermal crystallization behavior of iPP and nucleated iPP more satisfactorily.  相似文献   

16.
The crystalline structures of isotactic polypropylene (iPP) subjected to compression-molding were studied by means of differential scanning calorimeter (DSC), optical microscope (OM) and wide-angle X-ray diffraction (WAXD). β-crystal can be formed from nonisothermal crystallization of the sample compression-molded at the molten state and the β-phase content increased with increasing pressure of molding. Thermal treatment of the molten sample at 200 °C could eliminate the effect of compression-molding on crystalline structure. It was suggested that the compression-molding of iPP melt plays an important role in improving the nucleation ability of β-crystal.  相似文献   

17.
Crystallization, melting and structure of three different commercial types of isotactic polypropylene (iPP) grafted by maleic anhydride (PP-g-MAH) with different maleic anhydride content (AC) and their β-nucleated versions were studied by X-ray diffractometry (WAXS), differential scanning calorimetry (DSC), polarised light microscopy (PLM) and scanning electron microscopy (SEM). The presence of maleic anhydride units disturbs the chain regularity, hereby decreases the crystallization tendency of iPP in general and the β-crystallisation ability in particular. β-modification of iPP (β-iPP) forms only in β-nucleated PP-g-MAH polymers studied if the anhydride content is not larger than 0.5 mass%. The influence of AC of PP-g-MAH on the feature the spherulitic structure is demonstrated by PLM and SEM micrographs. The β-nucleated iPP/PP-g-MAH blends containing 10 mass% PP-g-MAH crystallise predominantly in β-form independently of AC of the latter. The β-nuceated blends of iPP and PP-g-MAH with lowest AC crystallise in β-form in whole concentration range. The interaction parameter between iPP and PP-g-MAH polymers calculated by Nishi-Wang equation indicate limited interaction between the components.  相似文献   

18.
A series of novel polyamide-imides (PAIs) with high glass transition temperature were prepared from diimide-dicarboxylic acid, 2,2′-bis(trifluoromethyl)-4,4′-bis(trimellitimidophenyl)biphenyl (BTFTB), by direct polycondensation with various diamines in N-methyl-2-pyrrolidinone using triphenyl phosphite and pyridine as condensing agents in the presence of dehydrating agent (CaCl2). The yield of the polymers was obtained was high with moderate to high inherent viscosities (0.80-1.03 dL g−1). Gel permeation chromatography (GPC) of the polymers showed number-average and weight-average molecular weights up to 8.6 × 104 and 22 × 104, respectively. The PAIs were amorphous in nature. Most of the polymers exhibited good solubility in various solvents such as N-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethylformamide (DMF), pyridine, cyclohexanone and tetrahydrofuran. The polymer films had tensile strength in the range of 79-103 MPa, an elongation at break in the range of 6-16%, and a tensile modulus in the range between 2.1 and 2.8 GPa. The glass transition temperatures of the polymers were determined by DMA method and they were in the range of 264-291 °C. The coefficients of thermal expansion (CTE) of PAIs were determined by TMA instrument and they were between 29 and 67 ppm °C−1. These polymers were fairly thermally stable up to or above 438 °C, and lose 10% weight in the range of 446-505 °C and 438-496 °C, respectively, in nitrogen and air. These polymers had exhibited 80% transmission wavelengths which were in the range of 484-516 nm and their cutoff wavelengths were in between 418 and 434 nm. The PAIs with trifluoromethyl group have higher bulk density resulting in higher free volume and then lowering the dielectric constant.  相似文献   

19.
PA6 composites with Cloisite® 30B (30B), prepared by different procedures, i.e., melt compounding, static annealing and solution blending, have been characterized by X-ray diffraction and microscopic analyses (TEM, SEM, POM) in order to shed more light on the mechanism of nanostructure development. It has been demonstrated that intercalation of the PA6 chains within the 30B galleries takes place very rapidly, in the absence of applied stresses, even when the size of the clay particles is relatively large (tens of microns) and the clay loading is very high (even 50 wt.%). It has also been shown that, if, conversely, the filler content is low (∼10 wt.% or less) and the particles are tiny (e.g., as for polymer/clay mixtures prepared by precipitation from a common solution), intercalation continues, under quiescent conditions, and leads in reasonable times to complete destruction of the silicate platelets stacking order. The composites with higher filler contents display a mixed exfoliated/intercalated morphology, with the intercalated silicate stacks characterized by an interlayer distance of about 3.7 nm. Contrary to statically annealed composites, the melt kneaded ones are characterized by a homogeneous dispersion of the filler particles and a local parallel orientation of the silicate platelets that induces, during polymer crystallization, an orientation of the polymer crystallites parallel to the faces of the compression molded specimens. Experiments carried out using 30B samples previously treated at 250 °C for 4 h under vacuum (30Bdegr) indicate that this treatment, probably due to the collapsed interlayer spaces, lowers the extent of PA6 chains intercalation. Thus, the relevant PA6/30Bdegr composites are characterized by the coexistence of unintercalated clay tactoids/agglomerates and individual silicate layers formed as result of intercalation on the edges of the filler particles.  相似文献   

20.
Core-shell type multiarm star copolymers with poly(ε-caprolactone) (PCL) as shells and hyperbranched polyethylenimine (PEI) as core have been successfully prepared by the Sn(Oct)2 catalyzed ring-opening polymerization of ε-caprolactone (CL) using high molecular weigh PEIs directly as macroinitiators. The initiation efficiency is in the range of 91-95% for PEI with Mn = 104 (PEI10K) and only around 60% for PEI with Mn = 2.5 × 104 (PEI25K), leading to star polymers with an average arm number in the range of 155-276. The thermal property of the obtained multiarm star polymers were also investigated by DSC. The melting and crystallization temperatures of the star polymers increase as the PCL arm length increases when the PEI core is fixed. The fusion enthalpy, crystalline enthalpy and degree of crystallinity values of the star polymers with PEI10K core are less than those with PEI1.8K core. Due to the polarity difference between PCL arm and PEI core, the resulting multiarm star polymers can act as inverted micellar nanocapsules capable of extracting and encapsulating water soluble guests. Increasing the size and polarity of the hydrophilic PEI core of the star nanocapsules are two effective ways to enhance their hydrophilic guest encapsulation capacity. Increasing the hydrophobic PCL arm length can increase the molar ratio, whereas reduce the weight ratio of the encapsulated hydrophilic guests to the star nanocapsules. Unexpectedly, the obtained nanocapsules can entrap the bigger size hydrophilic congo red guests more than the smaller size methyl orange.  相似文献   

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