Thermal and mechanical properties of syndiotactic polystyrene/organoclay nanocomposites with different microstructures

The fabrication of syndiotactic polystyrene (sPS)/organoclay nanocomposite was conducted via a stepwise mixing process with poly(styrene‐co‐vinyloxazolin) (OPS), that is, melt intercalation of OPS into organoclay followed by blending with sPS. The microstructure of nanocomposite mainly depended on the arrangement type of the organic modifier in clay gallery. When organoclays that have a lateral bilayer arrangement were used, an exfoliated structure was obtained, whereas an intercalated structure was obtained when organoclay with a paraffinic monolayer arrangement were used. The thermal and mechanical properties of sPS nanocomposites were investigated in relation to their microstructures. From the thermograms of nonisothermal crystallization and melting, nanocomposites exhibited an enhanced overall crystallization rate but had less reduced crystallinity than a matrix polymer. Clay layers dispersed in a matrix polymer may serve as a nucleating agent and hinder the crystal growth of polymer chains. As a comparison of the two nanocomposites with different microstructures, because of the high degree of dispersion of its clay layer the exfoliated nanocomposite exhibited a faster crystallization rate and a lower degree of crystallinity than the intercalated one. Nanocomposites exhibited higher mechanical properties, such as strength and stiffness, than the matrix polymer as observed in the dynamic mechanical analysis and tensile tests. Exfoliated nanocomposites showed more enhanced mechanical properties than intercalated ones because of the uniformly dispersed clay layers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1685–1693, 2004     

Isothermal crystallization kinetics and spherulitic morphology of poly(4‐hydroxybutyric acid‐alt‐glycolic acid)

Isothermal crystallization behavior of a new regular polyester constituted by glycolic acid and 4‐hydroxybutyric acid units is studied by means of differential scanning calorimetry and hot‐stage optical microscopy. A wide range of crystallization conditions were experimentally accessible, allowing various morphological features to be observed and accurate estimates made of characteristic growth parameters, including radial growth and nucleation rates. Three‐dimensional spherulitic growth from heterogeneous nuclei is deduced from the Avrami analysis, whereas optical micrographs reveal two different spherulitic textures that agree with the existence of two crystallization regimes. These can be well distinguished from the breaks observed in the Lauritzen and Hoffman plots when the linear crystal growth rate or the overall crystallization rate is considered. Ringed and nonringed spherulites with negative and positive birefringence, respectively, can be obtained depending on crystallization conditions and regimes. The studied polyester shows rather complex melting behavior which is interpreted in terms of a recrystallization process involving the two different kinds of spherulites. This study allows polymorphism to be discounted. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2640–2653, 2007     

Study of clay nanocomposites of the biodegradable polyhexamethylene succinate. Application of isoconversional analysis to nonisothermal crystallization

Nanocomposites of organomodified montmorillonites and the biodegradable polyester derived from hexanediol and succinic acid were prepared by the solution‐casting method using chloroform as solvent. Samples were studied by means of X‐ray diffraction and transmission electron microscopy. Intercalated structures differentiated by the stacking mode between silicate layers were observed. The highest variability in interlayer spacing was found when C30B organoclay was added. In this case, hydroxyl groups of the modifier could interact with polar carbonyl groups of the polyester. Thermal stability and crystallization behavior under both isothermal and nonisothermal conditions were evaluated. The overall crystallization rate of the intercalated nanocomposites was higher than that of the neat polyester due to a significant increase in their nucleation density, which compensated for their lower crystal growth rate. Isoconversional analysis was used to determine effective activation energies and to estimate nucleation and transport energy parameters from nonisothermal hot crystallization experiments. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2234–2248, 2008     

A DSC study of the crystallization behaviour of polylactic acid and its nanocomposites

The isothermal crystallization behaviour of polylactic acid (PLA) and a clay nanocomposite of have been examined using differential scanning calorimetry. The data obtained clearly indicates that the presence of the nanocomposite particles in the composite material influences the crystallization kinetics of the PLA when crystallized both from the solid amorphous state as well as from the melt. When crystallized from the melt the presence of the clay nano-particles appears to be influencing the nucleation and crystal growth rate of the PLA such that the crystallization rate is enhanced by a factor of about 15 to 20. This result is of tremendous significance in identifying the processing window for the production of foamed nanocomposites from PLA. In addition the effect of thermal exposure at 200°C on the crystallization behaviour of these materials has been investigated, with the results suggesting that holding these materials at 200°C for periods of time up to 60 min in an inert atmosphere only has a marginal effect.     

Intercalated poly(vinylidene fluoride)/clay nanocomposites: Structure and properties

The preparation and characterization of melt‐intercalated poly(vinylidene fluoride) (PVDF)/clay nanocomposites are reported. Organophilic clay (clay treated with dimethyl dihydrogenated tallow quaternary ammonium chloride) was used for the nanocomposite preparation. The composites were characterized with X‐ray diffraction (XRD), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA). XRD results indicated the intercalation of the polymer in the interlayer spacing. The incorporation of clay in PVDF resulted in the β form of PVDF. DSC nonisothermal curves showed an increase in the melting and crystallization temperatures along with a decrease in crystallinity. Isothermal crystallization studies show an enhanced rate of crystallization with the addition of clay. DMA indicated significant improvements in the storage modulus over a temperature range of ?100 to 150 °C. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 31–38, 2003     

Effects of spacing between the exfoliated clay platelets on the crystallization behavior of polyamide‐6 in polyamide‐6/clay nanocomposites

Exfoliated polyamide‐6 (PA6)/organoclay nanocomposite films with planar‐oriented clay platelets were prepared by the simple hot pressing of melt‐extruded nanocomposite pellets. The average distance between the neighboring clay platelets was controlled by changes in the clay loading content in the nanocomposites. The effects of the clay platelet spacing on the crystallization behavior of PA6 were investigated with transmission electron microscopy and wide‐angle X‐ray diffraction. The crystal lamellae were found to be mainly perpendicular to the clay surface for the nanocomposites with large spacing between the clay sheets at low clay loading contents. This perpendicular orientation morphology was attributed to the strong interactions between the PA6 molecular chain and the clay surface. In contrast, the crystal lamellae were found to be parallel to the clay surface when the spacing between the neighboring clay platelets was less than 30 nm. It was concluded that the confinement crystallization of PA6 within the nanoscale channels formed by clay sheets resulted in this parallel orientation texture. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 284–290, 2006     

Investigation of the sub‐melting‐temperature exotherm in melt‐quenched polyamide‐6/clay nanocomposites

A sub‐melting‐temperature exotherm in a polyamide‐6/clay nanocomposite (containing 3 wt % montmorillonite) was investigated with differential scanning calorimetry. It existed only via air‐quenching from the melt; it did not exist at higher or lower heating rates. The exotherm could be ascribed to frozen‐in stresses in the interlamellar regions through hydrogen bonding. A combination of larger internal stresses and larger crystallinity was necessary to produce this exotherm. Its appearance was closely connected to the addition of montmorillonite. During the air‐quenching process, montmorillonite not only greatly accelerated the crystallization rate of polyamide‐6 but also further intensified the internal stresses produced during the quenching process. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 378–382, 2005     

Crystallization kinetics and crystallization behavior of syndiotactic polystyrene/clay nanocomposites

We investigated the effects of montmorillonite (clay) on the crystallization kinetics of syndiotactic polystyrene (sPS) with isothermal differential scanning calorimetry analyses. The clay was dispersed into the sPS matrix via melt blending on a scale of 1–2 nm or up to about 100 nm, depending on the surfactant treatment. For a crystallization temperature of 240 °C, the isothermal crystallization data were fitted well with the Avrami crystallization equation. Crystallization data on the kinetic parameters (i.e., the crystallization rate constant, Avrami exponent, clay content, and clay/surfactant cation‐exchange ratio) were also investigated. Experimental results indicated that the crystallization rate constant of the sPS nanocomposite increased with increasing clay content. The clay played a vital role in facilitating the formation on the thermodynamically more favorable all‐β‐form crystal when the sPS was melt‐crystallized. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2097–2107, 2001     

Polyethylene terephthalate–multiwall nanotubes nanocomposites: Effect of nanotubes on the conformations,crystallinity and crystallization behavior of PET

PET‐nanotube composite samples were manufactured by mixing neat PET with a PET‐multiwall carbon nanotube masterbatch. Fourier transform infrared (FTIR) spectroscopy was utilized to monitor the gauche and trans conformations of the polymeric chains with respect to the nanotube content. The crystallinity as well as the crystallization behavior of the polymer were studied via differential scanning calorimetry (DSC). An increase of the trans conformations and crystallinity was recorded at low NT contents followed by a sharp decrease at 1 wt % of nanotubes, further addition of nanotubes led once again to increase of the trans conformations and crystallinity. This behavior was attributed to the aggregations formation which as shown via transmission electron microscopy (TEM) was initiated at concentrations above 0.5 wt %. Discordance between the FTIR and DSC results in the case of the PET sample showed that the later bears relatively more trans non‐crystalline conformers than the nanocomposite samples. Thus it appears that the nanotubes incorporate the trans non‐crystalline segments into the crystalline phase. This work has shown that even a minor addition of carbon nanotubes (even 0.1 wt %) alters the crystallization behavior of the polymer dramatically, yielding a novel nanocomposite material rather than a simple mixture of two ingredients. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 668–676, 2008     

Structural effect of linear and star‐shaped poly(L‐lactic acid) on physical properties

The linear and star‐shaped poly(L‐lactic acid) (PLLA) with similar molecular weight were prepared and their physical properties such as thermal properties, rheological properties, and crystallization behavior in quiescent and dynamic states were compared. The differential scanning calorimetry showed that the linear PLLA gave higher glass transition, melting, and crystallization temperatures than the star‐shaped one. In dynamic crystallization, the linear PLLA gave longer induction time and longer overall crystallization time than the star‐shaped one, although the former gave higher rate of crystallization in quiescent crystallization. However, wide‐angle X‐ray diffractometer(WAXD) analysis revealed that the linear and star‐shaped PLLA developed the same crystal structure and application of shear had little effect on crystal structure. As predicted, the linear PLLA gave higher crystallinity than the star‐shaped PLLA. In the dilute solutions, the linear PLLA exhibited higher intrinsic viscosity than the star‐shaped one. In the concentrated solutions, the star‐shaped PLLA gave higher values of dynamic viscosity, storage, and loss moduli than the linear one. Further, the former exhibited more noticeable shear thinning behavior and greater dependence of rheological properties on temperature than the latter. For both PLLA melts, the modified Cole–Cole plot gave slope less than 2. Of two PLLA polymers the star‐shaped PLLA gave smaller slope than the linear one. In addition, the former showed greater change of the slope with temperature than the latter. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 939–946, 2004     

Degradable polyoctamethylene suberate/clay nanocomposites. Crystallization studies by DSC and simultaneous SAXS/WAXD synchrotron radiation

Several organo-modified montmorillonites were studied to prepare nanocomposites of polyoctamethylene suberate, a biodegradable polyester. Mixtures were analyzed by conventional powder X-ray diffraction and transmission electron microscopy techniques. C30B clay was effective in rendering an intercalated structure with rather variable silicate layer spacing. The hydroxyl groups of the organo-modifier may allow the establishment of good interactions with the polar carbonyl groups of the studied polyester. A slight decrease in thermal stability was detected when the modified clay was incorporated into the polymer matrix. Isothermal and nonisothermal crystallization kinetics were studied by DSC and results compared with those for the neat polyester. The overall crystallization rate determined by calorimetric methods depends on the nucleation density and the crystal growth rate, which were independently evaluated by means of optical microscopy. Crystallization and morphological features were also analyzed by simultaneous SAXS/WAXD measurements made at a selected crystallization temperature and cooling rate under both isothermal and nonisothermal conditions, respectively.     

Miktoarm star‐shaped poly(lactic acid) copolymer: Synthesis and stereocomplex crystallization behavior

The miktoarm star‐shaped poly(lactic acid) (PLA) copolymer, (PLLA)₂‐core‐(PDLA)₂, was synthesized via stepwise ring‐opening polymerization of lactide with dibromoneopentyl glycol as the starting material. ¹H NMR and FTIR spectroscopy proved the feasibility of synthetic route and the successful preparation of star‐shaped PLA copolymers. The results of FTIR spectroscopy and XRD showed that the stereocomplex structure of the copolymer could be more perfect after solvent dissolution treatment. Effect of chain architectures on crystallization was investigated by studying the nonisothermal and isothermal crystallization of the miktoarm star‐shaped PLA copolymer and other stereocomplexes. Nonisothermal differential scanning calorimetry and polarizing optical microscopy tests indicated that (PLLA)₂‐core‐(PDLA)₂ exhibited the fastest formation of a stereocomplex in a dynamic test due to its special structure. In isothermal crystallization tests, the copolymer exhibited the fast crystal growth rate and the most perfect crystal morphology. The results reveal that the unique molecular structure has an important influence on the crystallization of the miktoarm star‐shaped PLA copolymer. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 814–826     

Isothermal crystallization behavior of exfoliated‐PP/IMMT nanocomposites via in situ polymerization

Highly exfoliated isotactic‐polypropylene/alkyl‐imidazolium modified montmorillonite (PP/IMMT) nanocomposites have been prepared via in situ intercalative polymerization. TEM and XRD results indicated that the obtained composites were highly exfoliated PP/IMMT nanocomposites and the average thickness of IMMT in PP matrix was less than 10 nm, and the distance between adjacent IMMT particles was in the range of 20–200 nm. The isothermal crystallization kinetics of highly exfoliated PP/IMMT nanocomposites were investigated by using differential scanning calorimeter(DSC) and polarized optical microscope (POM). The crystallization half‐time t_1/2, crystallization peak time t_max, and the Avrami crystallization rate constant K_n showed that the nanosilicate layers accelerate the overall crystallization rate greatly due to the nucleation effect, and the crystallization rate was increased with the increase in MMT content. Meanwhile, the crystallinity of PP in nanocomposites decreased with the increase in clay content which indicated the PP chains were confined by the nanosilicate layers during the crystallization process. Although the well‐dispersed silicate layers did not have much influence on spherulites growth rate, the nucleation rate and the nuclei density increased significantly. Accordingly, the spherulite size decreased with the increase in MMT content. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2215–2225, 2009     

Poly(ethylene terephthalate) copolymers containing nitroterephthalic units. II. Crystallization and conformational studies

The effect of incorporating a nitro side group into the phenylene units of poly(ethylene terephthalate) (PET) on the conformation and crystallizability of this polyester was evaluated. Random poly(ethylene terephthalate‐co‐nitroterephthalate) (PETNT) copolymers containing 5, 10, and 15 mol % nitroterephthalic units were investigated with reference to PET. All the examined copolymers were semicrystalline and were found to adopt the triclinic crystal structure of PET, with the nitrated units being excluded from the crystallites. Both the crystallinity and crystallization rate of PETNT largely decreased with the content of nitrated units, and the O? CH₂? CH₂? O trans‐to‐gauche conformational ratio increased with crystallization, attaining comparable values for all the compositions. The conformation and crystallinity of isothermally crystallized PET and PETNT samples could be correlated with the size of the crystallites generated in each case. However, a different crystal perfecting mechanism seemed to operate for PET and for the PETNT copolymers when they were subjected to annealing. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2759–2771, 2002     

FTIR spectroscopic characterization of structural changes in polyamide‐6 fibers during annealing and drawing

First, we report the development of Fourier transform infrared (FTIR) spectroscopic methods to determine the α/γ‐crystalline phase ratio of polyamide‐6 fibers and, in combination with density measurements, the total crystallinity. Using density determinations of the crystallinity of pure α and pure γ samples, we found the absorption coefficient ratio for the 930 (α) and 973 cm⁻¹ (γ) bands to be 4.4, from which we could obtain the α/γ ratio for any polyamide‐6 sample. The application of this FTIR method to the quantitative analysis of phase changes during thermal treatment and the drawing of polyamide‐6 was then made. We confirmed that crystallization during thermal treatments involved increases in both phases and did not involve crystal‐to‐crystal transformation, whereas drawing involved both crystallization of the amorphous phase in the α form and γ→α transformation. Finally, we revisited the band assignments for the amorphous phase of polyamide‐6 and found that the band at 1170 cm⁻¹ was not an amorphous band but, because its absorbance was independent of crystallinity, could be used as an internal reference band. The band at 1124 cm⁻¹ was reliably attributed to the amorphous phase. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 536–547, 2001     

FTIR Spectroscopic Study of Crystallization of Uniaxial Drawn Syndiotactic Polystyrene/Carbon Nanotube Nanocomposite Films

The crystallization of uniaxial hot drawn syndiotactic polystyrene/multi-walled carbon nanotube (sPS/MWCNT) nanocomposite films was studied by FTIR spectroscopy. The effects of MWCNT content, draw ratio and drawing temperature on the sPS crystallinity were investigated. The sPS/MWCMT nanocomposite films show reduced crystallinities with the increase of MWCNT content. In addition, with the increase of draw ratio, both the pure sPS and the sPS/MWCNT nanocomposite drawn films exhibit increased crystallinity. The effect of drawing temperature on the sPS crystallization is complex. In a temperature range of 100―135 ℃, the crystallinity decreases with drawing temperature, whereas it increases at 140 ℃ for both pure sPS and its nanocomposite films.     

Crystallization kinetics of crosslinkable polymer complexes of novolac resin and poly(ethylene oxide)

Results of a study on the isothermal crystallization and thermal behavior of both uncured and hexamine-cured novolac/poly(ethylene oxide) (PEO) complexes are reported. The crystallization behavior of PEO in complexes is strongly influenced by factors such as composition, crystallization temperature, complexation, and crosslinking. The time dependence of the relative degree of crystallinity at high conversion deviated from the Avrami equation. The cured complexes exhibited an obvious two-stage crystallization (primary crystallization and crystal perfection), and this was more evident at higher crystallization temperature and high PEO-content. The addition of a noncrystallizable component into PEO caused a depression of both the overall crystallization rate and the melting temperature. In general, complexation and curing resulted in an increase in the overall crystallization rate. Complexation and curing are beneficial to the nucleation of PEO. Additionally, curing led to changes of the nucleation mechanism. Experimental data on the overall kinetic rate constant K_n were analyzed by means of the nucleation and crystal growth theory. For uncured complexes, the surface free energy of folding, σ_e, increased with increasing novolac content, whereas for cured complexes, σ_e displayed a maximum with the variation of composition. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2726–2736, 1999     

Montmorillonite reduces crystallinity of poly‐l‐lactic acid scaffolds to accelerate degradation

Poly‐l‐lactic acid (PLLA) is considered as a potential bone scaffold material because of good biocompatibility and bioabsorbability, whereas too slow degradation rate limits its application. In this study, montmorillonite (MMT) was introduced into PLLA scaffolds fabricated via selective laser sintering to accelerate degradation by reducing crystallinity. To be specific, MMT was a layered silicate with large surface area and aspect ratio, which provided nucleation site for the crystallization of PLLA molecular chain along their surface during the sintering process. As the surface of MMT plate was randomly oriented in the matrix, the growth direction of crystallite was also random, which interrupted the orderly crystallization, thus decreasing the overall crystallinity of PLLA. As a result, the crystallinity of PLLA scaffolds was decreased from 32.3% to 27.4% when introducing 4.5% MMT. Accordingly, weight loss was increased from 0.83% to 7.25% after immersing for 4 weeks. Besides, the tensile strength and modulus of the scaffolds increased by 44.1% and 66.9% because of the change of fracture mode from brittle fracture to ductile fracture. In addition, the scaffolds also demonstrated good hydrophilic property and cell compatibility.     

Poly(vinylidene fluoride)/clay nanocomposites prepared by melt intercalation: Crystallization and dynamic mechanical behavior studies

The preparation and properties of poly(vinylidene fluoride) (PVDF)/clay nanocomposites are reported for the first time. PVDF/clay nanocomposites were prepared by melt intercalation with organophilic clay. The composites were characterized with X‐ray diffraction, differential scanning calorimetry, and dynamic mechanical analysis. X‐ray diffraction results indicated intercalation of the polymer into the interlayer spacing. PVDF in the nanocomposites crystallized in the β form. Differential scanning calorimetry nonisothermal curves showed an increase in the melting and crystallization temperatures along with a decrease in crystallinity, as evidenced by the melting and crystallization peaks. Isothermal crystallization studies showed an enhanced rate of crystallization with the addition of clay, as evidenced by a reduction in the crystallization time. Dynamic mechanical analysis indicated significant improvements in the storage modulus over a temperature range of ?100 to 150 °C. The tan δ peak signifying the glass‐transition temperature of PVDF shifted to higher temperatures. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1682–1689, 2002     

Isothermal crystallization kinetics of polypropylene latex–based nanocomposites with organo‐modified clay

The effect of organo‐modified clay (Cloisite 93A) on the crystal structure and isothermal crystallization behavior of isotactic polypropylene (iPP) in iPP/clay nanocomposites prepared by latex technology was investigated by wide angle X‐ray diffraction, differential scanning calorimetry and polarized optical microscopy. The X‐ray diffraction results indicated that the higher clay loading promotes the formation of the β‐phase crystallites, as evidenced by the appearance of a new peak corresponding to the (300) reflection of β‐iPP. Analysis of the isothermal crystallization showed that the PP nanocomposite (1% C93A) exhibited higher crystallization rates than the neat PP. The unfilled iPP matrix and nanocomposites clearly shows double melting behavior; the shape of the melting transition progressively changes toward single melting with increasing crystallization temperature. The fold surface free energy (σ_e) of polymer chains in the nanocomposites was lower than that in the PP latex (PPL). It should be reasonable to treat C93A as a good nucleating agent for the crystallization of PPL, which plays a determinant effect on the reduction in σ_e during the isothermal crystallization of the nanocomposites. The activation energy, ΔE_a, decreased with the incorporation of clay nanoparticles into the matrix, which in turn indicates that the nucleation process is facilitated by the presence of clay. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1927–1938, 2010