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1.
The β‐cyclodextrin (β‐CD) and γ‐cyclodextrin (γ‐CD) inclusion complexes (ICs) with four kinds of polyolefin were prepared. The crystallization behavior of isotactic poly(1‐butene) (iPB‐1) blended with these CDs and ICs was investigated by differential scanning calorimetry, polarized optical microscopy, and wide‐angle X‐ray diffraction. The iPB‐1 blended with the ICs was found to exhibit higher crystallization temperature (TC), smaller spherulites, and faster crystallization rate than neat iPB‐1. These results indicate that the ICs can act as nucleating agent on the crystallization of iPB‐1 and induce the accelerated crystallization. The guest molecules of ICs play an important role in the nucleation effect of ICs on the crystallization of iPB‐1. ICs with polyolefin having higher TC as guest molecules have higher nucleation effect than the one with polyolefin having lower TC as guest molecules. And, the CDs and ICs induce different crystal form of iPB‐1. The crystal of iPB‐1 blended with CDs is defective, whereas the crystal of iPB‐1 blended with ICs is more perfect. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 389–395, 2010  相似文献   

2.
Crystallization of a polystyrene-b-poly(ethylene oxide)-b-polystyrene (S-EO-S) triblock copolymer, S40EO136S40, with lamellar morphology in the melt and low glass transition temperature (Tg=47 °C) of the S block was studied. The triblock copolymer was cooled from ordered melt and isothermal crystallization was conducted at crystallization temperatures (Tc) near the Tg of the S block. It is found that crystallization behavior of S40EO136S40 strongly depends on Tc. When Tc is far below Tg, an Avrami exponent n=0.5 is observed, which is attributed to diffusion-controlled confined crystallization. As Tc slightly increases, the Avrami exponent is 1.0, indicating that crystallization is confined and crystallization rate is determined by the rate of homogeneous nucleation. When Tc is just below the Tg of the S block, crystallization tends to become breakout and accordingly Avrami exponent changes from 1.0 to 3.2. Crystallinity and melting temperature of the EO block in breakout crystallization are slightly higher than those in confined crystallization. Time-resolved small and wide angle X-ray scattering (SAXS/WAXS) were used to monitor isothermal crystallization of S40EO136S40. It shows that the long period is constant in confined crystallization, but it gradually increases during breakout crystallization. WAXS result reveals that confined or breakout crystallization has no effect on the crystal structure of the EO block.  相似文献   

3.
The isothermal and non-isothermal crystallization kinetics of pure poly(ε−caprolactone) (PCL) and its blends with crosslinked tung oil were investigated as a function of composition, crystallization temperature, and heating rate using differential scanning calorimetric (DSC). The PCL/tung oil semi-interpenetrating polymer networks of different compositions were prepared via cationic polymerization of tung oil in the presence of homogenous solutions of PCL. This unique and relatively new in-situ polymerization and compatibilization blending technique created nano/micro-scale morphologies that cannot be obtained with the traditional melt-processing and/or solvent casting methods. Blends with different miscibility, phase behaviors, and morphologies (miscible, partially miscible, and immiscible) were observed as a function of composition with a constant concentration of boron trifluoride diethyl etherate (BFE) cationic initiator. The morphology of the semi-interpenetrating polymer networks was performed using scanning electron microscopy (SEM). Miscible blends with a single Tg for PCL ≤ 10 wt.%. were observed. While, on the other hand, partially miscible blends with two distinct Tgs and nanoscale morphologies and average particle sizes as small as 100 nm were observed for blends with 20 ≤ PCL wt.% ≤ 30. Immiscible blends with microscale highly interconnected, co-continuous two-phase morphology and two distinct Tgs were detected for 50 wt.% PCL. Both isothermal and non-isothermal crystallization kinetics were strongly influenced by the different miscibility and morphology of the blends. The isothermal and non-isothermal crystallization kinetics of PCL/tung oil blends were analyzed on the basis of Avrami and modified Avrami approaches, respectively. A substantial decrease in the isothermal (longer half time) and non-isothermal (Tm shifted to lower temperature) crystallization kinetics was observed as the concentration of PCL increased in the blends up to 30 wt.% due to the partially miscibility of the blends in this composition range. In a contrast, for 50 wt.% PCL blend, a considerable increase in the crystallization kinetics (isothermal and non-isothermal) was detected due to the highly interconnected, co-continuous two-phase morphology.  相似文献   

4.
This article discusses the influence of the oligomeric resin, hydrogenated oligo(cyclopentadiene) (HOCP), on the morphology, and thermal and tensile mechanical properties of its blends with isotactic poly(4-methylpentene-1) (P4MP1). The P4MP1 and HOCP are found not miscible in the melt state. P4MP1/HOCP blends after solidification contain three phases: the crystalline phase of P4MP1, an amorphous phase of P4MP1, and an amorphous phase of HOCP. From optical micrographs obtained at 150°C, it is found that the solidified blends show a morphology constituted by P4MP1 microspherulites and small HOCP domains homogeneously distributed in intraspherulitic regions. DSC and DMTA results show that the blends present two glass transition temperatures (Tg) equal to the Tgs of the pure components. The tensile mechanical properties have been investigated at 20, 60, and 120°C. At 20°C both the HOCP oligomer and the amorphous P4MP1 are glassy, and it is found that all the blends are brittle and the stress–strain curves have equal trends. At 60°C the HOCP oligomer is glassy, whereas the amorphous P4MP1 is rubbery. The tensile mechanical properties at 60°C are found to depend on blend composition. It is found that the Young's modulus, the stresses at yielding and break points slightly decrease with HOCP content in the blends and these results are related to the decrease of blend crystallinity. The decrease of the elongation at break is accounted for by the presence of glassy HOCP domains that act as defects in the P4MP1 matrix, hampering the drawing. At 120°C both the amorphous phases are rubbery. It is found decreases of Young's modulus, stresses at yielding and break points. These results have been related to the decrease of blend crystallinity and to the increase of the total rubbery amorphous phase. Moreover, it is found that the blends present elongations at break equal to that of pure P4MP1. This constancy is attributed to: (a) at 120°C the HOCP domains are rubbery and their presence seems not to disturb the drawing of the samples; (b) a sufficient number of the tie-molecules and entanglements of P4MP1 present in the blends. In fact, although the numbers of tie-molecules and entanglements decrease in the blends, increasing the HOCP oligomer, they seem to be enough to keep the material interlaced and avoid earlier rupture. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1269–1277, 1997  相似文献   

5.
A series of PB-g-SAN impact modifiers with different ratio of PB to SAN ranging from 20.6/79.4 to 91.9/8.1 were synthesized by seeded emulsion polymerization. ABS blends were prepared by blending these PB-g-SAN impact modifiers and SAN resin. The rubber concentration of these ABS blends was kept at a constant value of 15 wt%. The influences of different impact modifier on the mechanical behavior and morphology of ABS blends have been investigated. The dynamic mechanical analysis on ABS blends shows that Tg of the rubbery phase shifts to a lower temperature, (tan δ)max of the rubbery phase increases and then decreases with the increase of PB concentration in PB-g-SAN impact modifier. A uniform dispersion of rubber particles in the matrix can be observed when PB/SAN ratio in PB-g-SAN impact modifier is in the range from 20.6/79.4 to 71.7/28.3. When it exceeds 71.7/28.3, an agglomeration of rubber particles occurs. The mechanical tests indicate that the ABS blend, in which PB/SAN ratio in the impact modifier is 71.7/28.3, has the maximum impact strength and yield strength.  相似文献   

6.
Non-isothermal crystallization of polyethylene (PE) blends with bimodal molecular weight distribution (MWD) was investigated by differential scanning calorimetry (DSC) at various scanning rates. The bimodal PE blends were prepared by blending two unimodal polyethylenes with large difference in molecular weigh in different ratio in xylene solution. Different kinetic parameters such as the half-time of crystallization (t1/2), crystallization rate constant (Zc), F(T) and the effective activation energy were determined. Some complicated relationships between these parameters and the average molecular weight were found. The crystallization rate first increased and reached a maximum then decreased, and also correlated with the MWD. The Avrami index under non-isothermal conditions was analyzed with a method developed by Harnisch and Muschik; the results indicated that homogeneous nucleation and spherulitic growth regimes were present in all samples studied.  相似文献   

7.
Poly(butylene terephthalate) (PBT) was blended with nanoscale fully vulcanized acrylic rubber (FVAR) powders in a twin extruder, and the FVAR powders were dispersed well in PBT from scanning electron microscopy (SEM) and transmission electron microscope (TEM) investigation. The isothermal crystallization kinetics of PBT/FVAR blends were investigated by differential scanning calorimeter (DSC) and simulated by Avrami model. Equilibrium melting temperature was estimated by the nonlinear Hoffman-Weeks relation. The active energy (ΔE) and nucleation parameters (Kg) increased with the addition of FVAR, suggesting that FVAR particles hindered the crystallization; however more content FVAR had a lower ΔE and Kg because FVAR powders acted as heterogeneous nuclei in the nucleation of crystallization and facilitated the crystallization of PBT. The crystallization ability followed the order: PBT > PBT/FVAR6 > PBT/FVAR3 > PBT/FVAR1 when undercooling was considered.  相似文献   

8.
The glass-transition temperature and non-isothermal crystallization of poly(trimethylene terephthalate)/poly(ethylene 2,6-naphthalate) (PTT/PEN) blends were investigated by using differential scanning calorimeter (DSC). The results suggested that the binary blends showed different crystallization and melting behaviors due to their different component of PTT and PEN. All of the samples exhibited a single glass-transition temperature, indicating that the component PTT and PEN were miscible in amorphous phase. The value of Tg predicted well by Gordon-Taylor equation decreased gradually with increasing of PTT content. The commonly used Avrami equation modified by Jeziorny, Ozawa theory and the method developed by Mo were used, respectively, to fit the primary stage of non-isothermal crystallization. The kinetic parameters suggested that the PTT content improved the crystallization of PEN in the binary blend. The crystallization growth dimension, crystallization rate and the degree of crystallinity of the blends were increased with the increasing content of PTT. The effective activation energy calculated by the advanced iso-conversional method developed by Vyazovkin also concluded that the value of Ea depended not only on the system but also on temperature, that is, the binary blend with more PTT component had higher crystallization ability and the crystallization ability is increased with increasing temperature. The kinetic parameters U* and Kg were also determined, respectively, by the Hoffman-Lauritzen theory.  相似文献   

9.
In this paper, the isothermal crystallization kinetics of pure polypropylene (PP) and AB2 hyper-branched polymer (HBP)/PP blends have been investigated by differential scanning calorimetry (DSC). During isothermal crystallization, the crystallization rates of the blends are higher than those of PP. Furthermore, in the blends with different HBP contents, the value of t 1/2 became smaller with increasing HBP content; however, the crystallization rate of the blend decreased slightly when the content of HBP is 5 %. An increase in the Avrami exponent means the addition of HBP influences the mechanism of nucleation and the growth of PP crystallites. In addition, the crystallization activation energy of pure PP and HBP/PP blends were also discussed, and the result showed that the crystallization activation energy has decreased remarkably in HBP/PP blends.  相似文献   

10.
Crystallization behaviour of blends of poly(N-methyldodecano-12-lactam) (PMDL) with statistical copolymer poly(styrene-stat-acrylic acid) (PSAA) has been studied by the DSC and WAXD methods. The blend films prepared from dioxane solutions were crystallized at laboratory temperature for five days. Approximate crystallinities of as-prepared neat lower- PMDL 5 and higher-molecular weight PMDL 45 were 28% and 19%, respectively. With increasing PSAA content in the blends the crystallinities decreased sharply. The melting point of the primary crystalline structure of PMDL showed a decreasing dependence on PSAA content in the blends, confirming miscibility of the PMDL-PSAA pair. Recrystallization was strongly suppressed in the blends. The lower-melting endotherm appearing at about 10-15 °C above the crystallization temperature was attributed to melting to less perfect structures formed during secondary crystallization. In neat PMDL, the extent of secondary crystallization was approximately 5-10%. In the blends containing 20% PSAA approximate relative proportion of secondary crystallites on total crystallinity was 40% and 60% for the blends with PMDL 5 and PMDL 45, respectively. WAXD measurements did not reveal any change in crystal modification on blending. Increased Tg in blends of flexible PMDL cannot play a significant role in suppression of primary in favour of secondary crystallization. This was attributed to low mobility of PMDL chains due to dilution effect and specific interactions with the amorphous copolymer component, and, in case of the higher-molecular-weight PMDL, a greater involvement of entanglements. Higher Tg of blends was involved in retardation of non-isothermal crystallization on cooling and subsequent cold crystallization.  相似文献   

11.
Nonisothermal crystallization kinetics and melting behavior of bimodal-medium-density- polyethylene (BMDPE) and the blends of BMDPE/LDPE were studied using differential scanning calorimetry (DSC) at various scanning rates. The Avrami analysis modified by Jeziorny and a method developed by Mo were employed to describe the nonisothermal crystallization process of BMDPE. The BMDPE DSC data were analyzed by the theory of Ozawa. Kinetic parameters such as the Avrami exponent (n), the kinetic crystallization rate constant (Zc), the peak temperatures (Tp) and the half-time of crystallization (t1/2) etc. were determined at various scanning rates. The appearance of double melting peaks and the double crystallization peaks in the heating and cooling DSC curves of BMDPE/LDPE blends indicated that the BMDPE and LDPE could crystallize respectively.  相似文献   

12.
In this work, we prepared blends of bisphenol A polycarbonate (PC) and poly(ϵ‐caprolactone) (PCL) in a wide composition range by melt mixing and solution mixing. Two different molecular weights of PCL were used (nominally, 10.000 g/mol, PCL10, and 80.000 g/mol, PCL80). The thermal behavior of both systems was studied via differential scanning calorimetry under dynamic and isothermal conditions. The blends were miscible in the entire composition range in the liquid and amorphous states, as indicated by the single glass‐transition temperature (Tg) exhibited by both the PC/PCL10 and PC/PCL80 blends. The compositional variation of the Tg was accurately described by the Fox equation for the PC/PCL80 blends, whereas slight deviations from this equation were exhibited by the PC/PCL10 blends. For blend compositions containing 40% or more PCL, either one or both blend components crystallized. Crystallization occurred during cooling from the melt or during subsequent heating in the form of cold crystallization. Although PCL crystallization was reduced and its crystallization rate decreased with the addition of PC, PCL was a very effective macromolecular plasticizer for PC, to the extent that crystallization during the scan was detected for some blend compositions. Isothermal crystallization experiments allowed the determination of equilibrium melting points (T) by the Hoffman–Weeks extrapolation method. A T depression was found for both PCL and PC components as the content of the other blend component was increased. The Avrami equation was closely obeyed by both blend components during the isothermal overall crystallization kinetics up to crystalline conversion degrees of 60–70% and with values of Avrami indices ranging from 3 to 4, depending on the crystallization temperature employed. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 771–785, 2001  相似文献   

13.
We have established time–temperature transformation and continuous-heating transformation diagrams for poly(ether–ether–ketone) (PEEK) and PEEK/poly(ether–imide) (PEI) blends, in order to analyze the effects of relaxation control on crystallization. Similar diagrams are widely used in the field of thermosetting resins. Upon crystallization, the glass transition temperature (Tg) of PEEK and PEEK/PEI blends is found to increase significantly. In the case of PEEK, the shift of the α-relaxation is due to the progressive constraining of amorphous regions by nearby crystals. This phenomenon results in the isothermal vitrification of PEEK during its latest crystallization stages for crystallization temperatures near the initial Tg of PEEK. However, vitrification/devitrification effects are found to be of minor importance for anisothermal crystallization, above 0.1°C/min heating rate. In the case of PEEK/PEI blends, amorphous regions are progressively enriched in PEI upon PEEK crystallization. This promotes a shift of the α-relaxation of these regions to higher temperatures, with a consequent vitrification of the material when crystallized below the Tg of PEI. The data obtained for the blends in anisothermal regimes allow one to detect a region in the (temperature/heating rate) plane where crystallization proceeds in the continuously close proximity of the glass transition (dynamic vitrification). These experimental findings are in agreement with simple simulations based on a modified Avrami model coupled with the Fox equation. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 919–930, 1998  相似文献   

14.
Poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate) (PHB‐HHx) and methoxy poly(ethylene glycol) (MPEG) blends were prepared using melt blending. The single glass transition temperature, Tg, between the Tgs of the two components and the negative χ value indicated that PHB‐HHx and MPEG formed miscible blends over the range of compositions studied. The Gordon–Taylor equation proved that there was an interaction between PHB‐HHx and MPEG in their blends. FTIR supported the presence of hydrogen bonding between the hydroxyl group of MPEG and the carbonyl group of PHB‐HHx. The spherulitic morphology and isothermal crystallization behavior of the miscible PHB‐HHx/MPEG blends were investigated at two crystallization temperatures (70 and 40 °C). At 70 °C, melting MPEG acted as a noncrystalline diluent that reduced the crystallization rate of the blends, while insoluble MPEG particles acted as a nucleating agent at 40 °C, enhancing the crystallization rate of the blends. However, no interspherulitic phase separation was observed at the two crystallization temperatures. The constant value of the Avrami exponent demonstrated that MPEG did not affect the three‐dimensional spherulitic growth mechanism of PHB‐HHx crystals in the blends, although the MPEG phase, such as the melting state or insoluble state, influenced the crystallization rate of the blends. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2852–2863, 2006  相似文献   

15.
Crystallization behavior of synthetic cis-1,4 polyisoprene mixed with methyl linolate was investigated by differential scanning calorimetry and dilatometry. At isothermal crystallization temperature of ?25°C, a rate of crystallization decreased with the addition of 1 wt % methyl linolate, whereas it increased with a large amount of methyl linolate, about 30% by weight. Although Avrami constant of cis-1,4 polyisoprene was 2.82, that of mixtures containing 1 and 30 wt % methyl linolate was found to be approximately 4. This implies the same crystallization mechanism was in operation in the mixtures. Since glass transition temperature, Tg, of cis-1,4 polyisoprene decreased as the methyl linolate content of mixture increased, methyl linolate was found to be plasticizer for cis-1,4 polyisoprene. The increase in the rate of crystallization in the mixtures was corresponding to the decrease in Tg. © 1995 John Wiley & Sons, Inc.  相似文献   

16.
唐涛 《高分子科学》2014,32(3):333-349
Effects of branches on the crystallization kinetics of polypropylene-g-polystyrene(PP-g-PS) and polypropylene-gpoly(n-butyl acrylate)(PP-g-PnBA) graft copolymers with well-defined molecular structures were systematically investigated by DSC.The Avrami equation was used to analyze the isothermal crystallization process,while the analysis of nonisothermal crystallization process was based on the Jeziorny-modified Avrami model and Mo model.The kinetics results of isothermal and nonisothermal crystallization verified the peculiar effects of branches on the crystallization process of PP backbones in PP-g-PS and PP-g-PnBA graft copolymers:on one hand,the interaction between branches(π-π interaction between PS branches,or dipole-dipole interaction between PnBA branches) restrained the mobility and reptation ability of the PP backbones,which hindered the crystallization process;on the other hand,the heterogeneous nucleation effect resulting from the branched structure and fluctuation-assisted nucleation mechanism(caused by microphase separation between the PS or PnBA rich phase and the PP rich phase) became more pronounced with increasing branch length,which facilitated the crystallization process.  相似文献   

17.
The miscibility and the isothermal crystallization kinetics for PBT/Epoxy blends have been studied by using differential scanning calorimetry, and several kinetic analyses have been used to describe the crystallization process. The Avrami exponents n were obtained for PBT/Epoxy blends. An addition of small amount of epoxy resin (3%) leads to an increase in the number of effective nuclei, thus resulting in an increase in crystallization rate and a stronger trend of instantaneous three‐dimensional growth. For isothermal crystallization, crystallization parameter analysis showed that epoxy particles could act as effective nucleating agents, accelerating the crystallization of PBT component in the PBT/Epoxy blends. The Lauritzen–Hoffman equation for DSC isothermal crystallization data revealed that PBT/Epoxy 97/3 had lower nucleation constant Kg than 100/0, 93/7, and 90/10 PBT/Epoxy blends. Analysis of the crystallization data of PBT/Epoxy blends showed that crystallization occurs in regime II. The fold surface free energy, σe = 101.7–58.0 × 10?3 J/m2, and work of chain folding, q = 5.79–3.30 kcal/mol, were determined. The equilibrium melting point depressions of PBT/Epoxy blends were observed and the Flory–Huggins interaction parameters were obtained. It indicated that these blends were thermodynamically miscible in the melt. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1320–1330, 2006  相似文献   

18.
Effects of carbon nanotubes (CNT) on the isothermal crystallization kinetics of poly(L ‐lactic acid) (PLLA) were quantitatively investigated using the Avrami equation and the secondary nucleation theory of Lauritzen and Hoffman. CNT via grafting modification with PLLA could well disperse in the PLLA matrix and give significantly enhanced crystallization rate and crystallinity of PLLA as analyzed by differential scanning calorimetry and polarized optical microscopy. Analysis of isothermal crystallization kinetics using the Avrami equation demonstrated that CNT significantly enhanced the bulk crystallization of PLLA. Analysis of spherulite growth kinetics using the secondary nucleation theory of Lauritzen and Hoffman found that CNT could expand the temperature range of the crystallization regime III of PLLA. Values of the nucleation constant (Kg) in crystallization regimes III and II of PLLA both increased with increasing CNT contents. The Kg III/Kg II ratios were found to be close to the theoretical value 2 but were not clearly found to depend on the CNT contents. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 983–989, 2010  相似文献   

19.
Amorphous Mg61Cu24Y15 ribbons were manufactured by melt-spinning at wheel speeds in the range 5?C20?ms?1. The crystallization behavior of amorphous ribbons was investigated by a combination of differential scanning calorimetry (DSC) and X-ray diffractometry. DSC measurements showed that the amorphous ribbons exhibit distinct glass transition temperature and wide supercooled liquid region before crystallization. During continuous heating three exothermic peaks and two endothermic peaks were observed. The characteristic thermodynamic parameters such as T g, T x , ??T x , and T rg are around 432?C439, 478?C485, 46?C54?K, and 0.55?C0.56, respectively. Isothermal annealing DSC traces for this amorphous alloy, the first crystallization peak showed a clear incubation period and Avrami exponent was found to be 2.30?C2.74, which indicate that the transformation reaction involved nucleation and three-dimensional diffusion controlled growth. Mechanical properties of the as-quenched and subsequently annealed ribbons were examined by Vickers microhardness (HV) measurements. Results showed that microhardness of the as-quenched ribbons were about 309?HV. However, the results also showed that microhardness of the rapidly solidified ribbons increases with the increasing temperature.  相似文献   

20.
Polyethylene/montmorillonite (PE/MMT) nanocomposites, one intercalated sample with higher MMT content and one exfoliated sample with lower MMT content, were prepared by in situ polymerization using MMT-supported metallocene as catalyst. Non-isothermal crystallization behaviors of these two nanocomposites were investigated and compared. The exfoliated sample exhibits higher crystallization temperature (Tc) than the neat PE, showing nucleation effect of MMT. The intercalated sample has lower Tc than the neat PE due to the confinement of MMT. It is observed that the intercalated sample has longer induction period and faster overall crystallization rate, indicating co-existence of suppression and nucleation effects in this sample. The Avrami plots show that the crystal growth of PE in the intercalated sample is two-dimensional, while it is three-dimensional in the exfoliated sample. The crystallization activation energy of the intercalated sample is slightly smaller than that of the exfoliated sample.  相似文献   

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