Preparation and nonisothermal crystallization behavior of polypropylene/layered double hydroxide nanocomposites

Polypropylene (PP)/layered double hydroxide (LDH) nanocomposites were prepared via melt intercalation using dodecyl sulfate anion modified LDH and maleated PP as compatibilizing agent. Evidently the interlayer anions in LDH galleries react with maleic anhydride groups of PP-g-MA and lead to a finer dispersion of individual LDH layers in the PP matrix. The nanostructure was characterized by XRD and TEM; the examinations confirmed the nanocomposite formation with exfoliated/intercalated layered double hydroxides well distributed in the PP matrix. The nonisothermal crystallization behavior of resulting nanocomposites was extensively studied using differential scanning calorimetry (DSC) technique at various cooling rates. In nonisothermal crystallization kinetics, the Ozawa approach failed to describe the crystallization behavior of nanocomposites, whereas the Avrami analysis and Jeziorny method well define the crystallization behavior of PP/LDH nanocomposite. Combined Avrami and Ozawa analysis (Liu model) also found useful. The results revealed that very small amounts of LDH (1%) could accelerate the crystallization process relative to the pure PP and increase in the crystallization rates was attributed to the nucleating effect of the nanoparticles. Polarized optical microscopy (POM) observations also support the DSC results. The effective crystallization activation energy was estimated as a function of the relative degree of crystallinity using the isoconversional analysis. Overall, results indicated that the LDH particles in nanometer size might act as nucleating agent and distinctly change the type of nucleation, growth and geometry of PP crystals.     

Nonisothermal crystallization kinetics of nucleated poly(ethylene terephthalate)

Studies of the nonisothermal crystallization kinetics of poly(ethylene terephthalate) nucleated with anhydrous sodium acetate were carried out. The chemical nucleating effect was investigated and confirmed with Fourier transform infrared and intrinsic viscosity measurements. The Avrami, Ozawa, and Liu models were used to describe the crystallization process. The rates of crystallization, which initially increased, decreased at higher loadings of the additive. The activation energy, calculated with Kissinger's method, was lower for nucleated samples. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of silica nucleants on the rates of crystallization of poly(ethylene terephthalate)

Studies of the crystallization of poly(ethylene terephthalate) (PET) by d.s.c., both isothermally and non-isothermally, show that the addition of silica causes marked increases in rate at loadings < 1 part filler in 100 parts polymer. At higher loadings the overall rate of crystallization decreases until it becomes less than that of un-nucleated PET. Modified silica, with an alkoxy-coated surface, causes similar but less pronounced changes in rate. The retardation in rate inspite of an increase in the number of spherulites is attributed to an increase in the viscosity of the polymer melt due to strong adsorption onto the silica particles.     

Structure and conductive properties of poly(ethylene oxide)/layered double hydroxide nanocomposite polymer electrolytes

The oligo(ethylene oxide) modified layered double hydroxide (LDH) prepared by template method was added as a nanoscale nucleating agent into poly(ethylene oxide) (PEO) to form PEO/OLDH nanocomposite electrolytes. The effects of OLDH addition on morphology and conductivities of nanocomposite electrolytes were studied using wide-angle X-ray diffractometer, polarized optical microscopy, differential scanning calorimetry and ionic conductivity measurement. The results show that the exfoliated morphology of nanocomposites is formed due to the surface modification of LDH layers with PEO matrix compatible oligo(ethylene oxide)s. The nanoscale dispersed OLDH layers inhibit the crystal growth of PEO crystallites and result in a plenty amount of intercrystalline grain boundary within PEO/OLDH nanocomposites. The ionic conductivities of nanocomposite electrolytes are enhanced by three orders of magnitude compared to the pure PEO polymer electrolytes at ambient temperature. It can be attributed to the ease transport of Li⁺ along intercrystalline amorphous phase. This novel nanocomposite electrolytes system with high conductivities will be benefited to fabricate the thin-film type of Li-polymer secondary battery.     

Preparation and properties of layered double hydroxide/poly(ethylene terephthalate) nanocomposites by direct melt compounding

Thermal, rheological and mechanical properties of layered double hydroxide (LDHs)/PET nanocomposites were investigated. To enhance the compatibility between PET matrix and LDHs, organic modification of parent LDH having carbonate anion was carried out using various anionic surfactants such as dodecylsulfate (DS), dodecylbenzenesulfonate (DBS), and octylsulfate(OS) by rehydration process. Then, PET nanocomposites with LDH content of 0, 1.0, and 2.0 wt% were prepared by direct melt-compounding. The dispersion morphologies were observed by transmission electron microscopy and X-ray diffraction, indicating that LDH-DS were exfoliated in PET matrix. From the rheology study, there are some network structures owing to filler-filler and/or filler-matrix interactions in nanocomposite systems. Consequently, DS intercalated LDH provided good compatibility with PET molecules, resulting in exfoliated LDH-DS/PET nanocomposites having enhanced thermal and mechanical properties as compared to other nanocomposites as well as homo PET.     

Recycled poly(ethylene terephthalate)/layered silicate nanocomposites: morphology and tensile mechanical properties

Various amounts (1, 3 and 5 wt%) of a non-modified natural montmorillonite clay (Cloisite^® Na⁺) or of an ion-exchanged clay modified with quaternary ammonium salt (Cloisite^® 25A) were dispersed in a recycled poly(ethylene terephthalate) matrix (rPET) by a melt intercalation process. Microphotographs of composite fracture surfaces bring evidence that particles of Cloisite^® 25A are much better dispersed in the rPET matrix than those of Cloisite^® Na⁺. Moreover, WAXS measurements indicate that the lamellar periodicity of Cloisite^® 25A is increased in the composites, which evidences intercalation of rPET between silicate layers (lamellae) of the clay. In the case of Cloisite^® Na⁺, a very small thickening of lamellae due to mixing with rPET indicates only minute intercalation.Uniaxial tensile tests show that both clays increase the modulus of the rPET composites; more effective Cloisite^® 25A accounts for a 30% increase at loading of 5 wt%. Yield strength remains practically unaffected by the used fractions of the clays while tensile strength slightly decreases with the clay content; in parallel, strain at break dramatically drops. Tensile compliance of the composites is virtually independent of applied stress up to 26 MPa. Essential part of the compliance corresponds to the elastic time-independent component, while the viscoelastic component is low corresponding only to a few percent of the compliance even at relatively high stresses. The compliance of the composites is only slightly lower than that of the neat rPET, the reinforcing effect of Cloisite^® 25A being somewhat stronger. Both clays have beneficial effect on the dimensional stability of the composites since—in contrast to the neat rPET—the creep rate does not rise at long creep periods.     

Effect of water molecules on crystallization during unixial drawing of poly(ethylene terephthalate) films

The role played by sorbed water molecules present within poly(ethylene terephthalate) film at the moment of uniaxial drawing on the appearance and the percentage of the strain‐induced crystalline (SIC) phase is investigated by birefringence, X‐ray diffraction, and differential scanning calorimetry measurements. We show that, for law draw ratio, water play its traditional plasticizer effects. The SIC phase appears for a draw ratio, which depends weakly on the relative humidity. The water does not modify the degree of crystallinity of drawn films but impedes the growth of a part of the crystallites and modify their crystalline size. For high draw ratio, water impedes the orientation of the amorphous phase. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1056–1066, 2000     

Finite strain behavior of poly(ethylene terephthalate) (PET) and poly(ethylene terephthalate)-glycol (PETG)

Uniaxial and plane strain compression experiments are conducted on amorphous poly(ethylene terephthalate) (PET) and poly(ethylene terephthalate)-glycol (PETG) over a wide range of temperatures (25-110 °C) and strain rates (.005-1.0 s⁻¹). The stress-strain behavior of each material is presented and the results for the two materials are found to be remarkably similar over the investigated range of rates, temperatures, and strain levels. Below the glass transition temperature (θ_g=80 °C), the materials exhibit a distinct yield stress, followed by strain softening then moderate strain hardening at moderate strain levels and dramatic strain hardening at large strains. Above the glass transition temperature, the stress-strain curves exhibit the classic trends of a rubbery material during loading, albeit with a strong temperature and time dependence. Instead of a distinct yield stress, the curve transitions gradually, or rolls over, to flow. As in the sub-θ_g range, this is followed by moderate strain hardening and stiffening, and subsequent dramatic hardening. The exhibition of dramatic hardening in PETG, a copolymer of PET which does not undergo strain-induced crystallization, indicates that crystallization may not be the source of the dramatic hardening and stiffening in PET and, instead molecular orientation is the primary hardening and stiffening mechanism in both PET and PETG. Indeed, it is only in cases of deformation which result in highly uniaxial network orientation that the stress-strain behavior of PET differs significantly from that of PETG, suggesting the influence of a meso-ordered structure or crystallization in these instances. During unloading, PETG exhibits extensive elastic recovery, whereas PET exhibits relatively little recovery, suggesting that crystallization occurs (or continues to develop) after active loading ceases and unloading has commenced, locking in much of the deformation in PET.     

Synthesis and nonisothermal crystallization kinetics of biodegradable poly(ethylene terephthalate-co-ethylene succinate)s

In the current work, a series of biodegradable poly(ethylene terephthalate-co-ethylene succinate)s (P[ET-co-ES]s) were prepared via a traditional melting polycondensation method. First of all, the structures of prepared copolymers were characterized by nuclear magnetic resonance and Fourier transform infrared measurements. Meanwhile, the thermal properties of prepared samples were analyzed by differential scanning calorimetry and thermogravimetric analysis measurements, respectively. Subsequently, the mechanical properties of the P(ET-co-ES)s were evaluated, the tensile strength of P(ET-co-ES)s decreased with increasing of PES content in copolymer, however, corresponding P(ET-co-ES)s exhibited better elongation at break. Next, the biodegradability of P(ET-co-ES)s was evaluated using lipase as degrading enzyme. The results presented that the biodegradability of P(ET-co-ES)s improved with PES content, the corresponding results were supported by scanning electron microscopy test. Finally, the Mo's modified Avrami equation was employed to analyze the nonisothermal crystallization kinetics of prepared copolymers. The results showed the addition of the PES component improved the crystallization properties of the prepared P(ET-co-ES)s. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48422.     

Isothermal crystallization kinetics of anhydrous sodium acetate nucleated poly(ethylene terephthalate)

Studies on the isothermal crystallization kinetics of poly(ethylene terephthalate) (PET) nucleated with anhydrous sodium acetate were carried out. The nucleated agent had succeeded in promoting greater rates of crystallization in PET. A study of the melting behavior of the samples revealed that the nucleating agents promoted formation of thinner lamellae. The equilibrium melting temperature (T) of samples was determined using linear and nonlinear Hoffman Weeks procedure. The nonlinear Hoffman Week's procedure was found to be inapplicable in the current study. The Lauritzen‐Hoffman secondary nucleation theory was applied to determine the nucleation parameter (K_g), fold surface energy (σ_e), and work of chain folding (q). σ_e and q decreased on addition of nucleating agent. The approximate and exact form of the Lauritzen Z‐test was used to determine the operating regime. The operating regime was found to be primarily regime II for the range of temperatures studied. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Influence of molar mass and catalysts on the kinetics of crystallization and on the orientation of poly(ethylene terephthalate)

Poly(ethylene terephthalate) with different molar masses and different catalysts and additives (calcium acetate, manganese acetate, triphenylphosphate) was synthesized. The influence of the molar mass distribution, and of the additives used, on the rate of crystallization was studied. Also the dependence of the orientation obtained during drawing at elevated temperatures on the drawing conditions, on the average molar mass, and on the additives was investigated. It is shown that, under the same drawing conditions, an increase in molar mass leads to greater orientation. Also, at very small draw rates the orientation in the samples containing calcium acetate is greater than in those containing manganese acetate.     

Kinetics of non-isothermal cold crystallization of uniaxially oriented poly(ethylene terephthalate)

The non-isothermal equation was extended to describe non-isothermal cold crystallization kinetics of oriented polymers. The validity of the equation was examined by using a DSC crystallization curve of oriented poly(ethylene terephthalate) (PET) fibers with a constant heating rate. The double cold crystallization peaks appeared in the DSC curve. The relative degrees of crystallinity at different temperatures were analyzed by using the equation. The results show that the value of the Avrami exponent near to 1 at lower temperatures implies the bundle-like crystal growth geometry and the value of the Avrami exponent near to, 2, at higher temperatures implies the higher dimension crystal growth geometry. The first crystallization process crystallizes at faster rate than that of the isotropic sample, while the second process crystallizes at slower rate than that of isotropic sample. If a simple single process model was used, the value of the Avrami exponent, 0.77, was obtained. The result shows the simple single process model cannot describe the processes of crystallization of oriented PET fibers satisfactorily.     

Application of nonisothermal cure kinetics to the interaction of poly(ethylene terephthalate) with alkyd resin varnish

Linear and nonlinear viscoelasticity of an adhesion material for integrated circuit chips were investigated to control the processability. The material consists of acrylic polymer (AP) and epoxy oligomer (EP). EP content in AP/EP blend is 70 vol %. From the linear viscoelasticity, it was found that the iso‐free volume state of AP/EP blend was 20°C lower than that of AP and the entanglement molecular weight M_e of AP/EP was three times higher than that of AP. Nonlinear stress relaxation modulus G(t,γ) showed that the time‐strain separability, G(t,γ) = G(t)h(γ), was applicable at long time above a characteristic time τ_k, where G(t) is linear relaxation modulus and h(γ) is the damping function. The τ_k value was estimated to be 10 s for AP/EP and below 0.1 s for AP at an iso‐free volume state. (h(γ) for AP and AP/EP behaved like a usual linear homopolymer.) The time evolution of the elongational viscosity η_E(t) of each sample showed that AP/EP system exhibited strong strain hardening at , although AP did not show strain hardening at strain rate measured, when the data were compared at an iso‐free volume state. These results strongly suggest that the strain hardening behavior of AP/EP is attributable to enhancement of the stretch of AP polymer chains by diluting EP oligomer chains. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Crystallization kinetics of poly(ethylene terephthalate) with thermotropic liquid crystalline polymer blends

The isothermal and dynamic crystallization behaviors of polyethylene terephthalate (PET) blended with three types of liquid crystal polymers, i.e., PHB60–PET40, HBA73–HNA27, [(PHB60–PET40)–(HBA73–HNA27) 50 : 50], have been studied using differential scanning calorimetry (DSC). The kinetics were calculated using the slope of the crystallization versus time plot, the time for 50% reduced crystallinity, the time to attain maximum rate of crystallization, and the Avrami equation. All the liquid crystalline polymer reinforcements with 10 wt % added accelerated the rate of crystallization of PET; however, the order of the acceleration effect among the liquid crystalline polymers could not be defined from the isothermal crystallization kinetics. The order of the effect for liquid crystalline polymer on the crystallization of PET is as follows: (PHB60–PET40)–(HBA73–HNA27) (50 : 50); HBA73–HNA27; PHB60–PET40: This order forms the dynamic scan of the DSC measurements. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1383–1392, 1998     

Crystallization characteristics of weakly branched poly(ethylene terephthalate)

A series of branched poly(ethylene terephthalate) (BPET) samples were prepared from melt polycondensation by incorporation of various amount (0.4-1.2 mol%) of glycerol as a branching agent. These polymers were characterized by means of H¹ NMR, intrinsic viscosity. The general crystalline and melting behavior was investigated via DSC. It was found that the crystalline temperature T_cc from the melt shifted to high temperature and the T_hc from the glass got low for BPETs while the melting temperatures of BPETs kept almost unchanged. The kinetics of isothermal crystallization was studied by means of DSC and POM. It was found that the present branching accelerated the entire process of crystallization of BPETs, although prolonged the induced time. In addition, branching reduced nucleation sites; hence the number of nucleates for BPET got smaller. Therefore, more perfect geometric growth of crystallization and greater radius of spherulites could develop in BPET due to less truncation of spherulites.     

Carbon nanotubes induced crystallization of poly(ethylene terephthalate)

We have investigated the crystallization characteristics of melt compounded nanocomposites of poly(ethylene terephthalate) (PET) and single walled carbon nanotubes (SWNTs). Differential scanning calorimetry studies showed that SWNTs at weight fractions as low as 0.03 wt% enhance the rate of crystallization in PET, as the cooling nanocomposite melt crystallizes at a temperature 10 °C higher as compared to neat PET. Isothermal crystallization studies also revealed that SWNTs significantly accelerate the crystallization process. WAXD showed oriented crystallization of PET induced by oriented SWNTs in a randomized PET melt, indicating the role of SWNTs as nucleating sites.     

Effect of shearing on crystallization behavior of poly(ethylene terephthalate)

The shear‐induced crystallization behavior of PET was investigated by measuring the time‐dependent storage modulus (G′) and dynamic viscosity (η′) with a parallel‐plate rheometer at different temperatures and shear rate. The morphology of shear‐induced crystallized PET was measured by DSC, X‐ray, and polarizing optical microscopy. When a constant shear rate was added to the molten polymer, the shear stress increased with the time as a result of the orientation of molecular chains. The induction time of crystallization is decreased with frequency. Moreover, the rate of isothermal crystallization of PET was notably decreased with increasing temperature. The shape of spherulites is changed to ellipsoid in the direction of shear. In addition, aggregation of spherulites is increased with increasing frequency. Particularly, the row nucleation morphology could be observed under polarized light for ω = 1. From the results of DSC, the melting point and enthalpy have a tendency to decrease slightly with increasing frequency. The crystallite size and perfectness decreased with frequency, which was confirmed with X‐ray data. The unit length of the crystallographic unit cell of the PET increased and the (1 0 3) plane peak increased with increasing frequency. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2640–2646, 2001     

The complicated influence of branching on crystallization behavior of poly(ethylene terephthalate)

The randomly branched poly(ethylene terephthalate) (BPET) was prepared by bulk polycondensation from dimethyl terephthalate (DMT) and ethylene glycol (EG), with 0.4–5.0 mol % (with respect to DMT) of glycerol (GL) as a branching agent. The glass transition and crystallization behavior was studied by differential scanning calorimetry (DSC). It was found that the glass transition temperature of BPET reduced with the increasing content of GL until 1.2 mol %, and then increases a little at high degrees of branching. When compared with a linear PET, the crystallization temperature of BPET from the melt shifted to higher temperature as GL content was smaller than 1.2 mol %, and then became lower while GL load was added. Nonisothermal crystallization kinetics was studied through the modified Avrami analysis. It was revealed that the overall crystallization rate parameter of BPET became larger when the GL content was less than 1.2 mol %, then turned to lower at higher branching degree. This indicated that low degree of branching could enhance the overall crystallization of poly(ethylene terephthalate) (PET), whereas high degree of branching in the range of 3.5–5.0 mol % would block the development of crystallization. On the basis of Hoffman's secondary crystallization theory, the product σσ_e of the free energy of formation per unit area of the lateral and folding surface was calculated. According to the change of the product σσ_e with the degree of branching, a possible explanation was presented to illuminate this diverse effect of different degrees of branching on crystallization. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Melting behaviors and isothermal crystallization kinetics of poly(ethylene terephthalate)/mesoporous molecular sieve composite

Isothermal crystallization and subsequent melting behavior of mesoporous molecular sieve (MMS) filled poly(ethylene terephthalate) (PET) composites have been investigated at the designated temperature by using differential scanning calorimeter (DSC). The commonly used Avrami equation was used to fit the primary stage of the isothermal crystallization. The Avrami exponents n were evaluated to be 2<n<3 for the neat PET and composites. MMS particles acting as nucleating agent in composite accelerated the crystallization rate with decreasing the half-time of crystallization. The crystallization activation energy calculated from the Arrhenius' formula was reduced as MMS content increased. It is shown that the MMS particles made the molecular chains of PET easier to crystallize during the isothermal crystallization process. Subsequent differential scanning calorimeter scans of the isothermally crystallized samples exhibited different melting endotherms. It is found that much smaller or less perfect crystals formed in composites due to the interaction between molecular chains and the MMS particles. The crystallinity of composites was enhanced by increasing MMS content.