STUDIES ON THE KINETICS OF PHASE TRANSITIONS OF A MAIN CHAIN THERMOTROPIC POLYESTER

The kinetics of phase transitions including a transition between mesophases were studied for a main-chain thermotropic polyester by means of DSC and depolarizing transmittance techniques. The isothermal process of these transitions was found to be described by the Avrami equation to high conversions. The Avrami exponents n are about 2,4, 5.3 and 2.2 for liquid crystallization, transition between mesophases and crystallization from mesophase respectively. The liquid crystallization from isotropic liquid phase occurs at very low undercoolings with high transformation rate. This behavior is explained as the results of the smaller value of the surface free energy for mesophase than that for crystallites which is evidenced by the very weak temperature dependence of liquid crystallization rate.     

MELTING CRYSTALLIZATION BEHAVIOR OF NYLON 66

Analysis of isothermal and nonisothermal crystallization kinetics of nylon 66 was carried out using differentialscanning calorimetry (DSC). The commonly used Avrami equation and that modified by Jeziorny were used, respectively, tofit the primary stage of isothermal and nonisothermal crystallizations of nylon 66, In the isothermal crystallization process,mechanisms of spherulitic nucleation and growth were discussed. The lateral and folding surface free energies determinedfrom the Lauritzen-Hoffman treatment are σ= 9.77 erg/cm~2 and σ_e= 155.48 erg/cm~2, respectively; and the work of chainfolding is q = 33.14 kJ/mol. The nonisothermal crystallization kinetics of nylon 66 was analyzed by using the Mo methodcombined with the Avrami and Ozawa equations. The average Avrami exponent n was determined to be 3.45, Theactivation energies (ΔE) were determined to be -485.45 kJ/mol and -331.27 kJ/mol, respectively, for the isothermal andnonisothermal crystallization processes by the Arrhenius and the Kissinger methods.     

CRYSTALLIZATION OF NaY ZEOLITE IN THE PRESENCE OF “CRYSTAL DIRECTION AGENT”AND RECRYSTALLIZATION OF NaA INTO NaY IN THE REACTION MIXTURE

The process of nucleation and crystal growth of NaY zeolite over a temperature rangeof 55°--100℃ in the presence of "crystal direction agent " are studied. The apparent ac-tivation energy for nucleation and that for crystal growth are evaluated. The mechanism ofthe recrystallization of NaA into NaY is investigated by adding NaA zeolite to the reactionmixture in which the crystallization of NaY zeolite is proceeding. The recrystallization ofNaA zeolite does not occur until the NaY crystallization from the reaction mixture is com-pleted. Thus the process of recrystallization of NaA into NaY might be shown as follows: Amorphous aluminosilicate gel→NaY NaA→NaY NaA Scanning electron microscopic observations and the recrystallization curves show that therecrystallization of NaA into NaY is getting n with a degradation and dissolution of surfacecrystals on the NaA zeolite and that the nucleation and crystal growth of NaY take placeimmediately at the surface of NaA crystals.     

Enhanced Crystallization Rate of Biodegradable Poly(ε-caprolactone) by Cyanuric Acid as an Efficient Nucleating Agent

The influence of cyanuric acid(CA) as an efficient nucleating agent on the crystallization behavior and morphology of biodegradable poly(ε-caprolactone)(PCL) was extensively studied in this work with several techniques for the first time. The nonisothermal melt crystallization behavior and overall isothermal melt crystallization rate of PCL were significantly enhanced by only a small amount of CA. The addition of CA apparently improved the nonisothermal melt crystallization peak temperature, overall isothermal melt crystallization rate, and nucleation density of PCL spherulites, but did not modify the crystallization mechanism and crystal structure of PCL, indicating that CA was an efficient nucleating agent for the crystallization of PCL. The possible nucleation mechanism of CA on the crystallization of PCL was also discussed on the basis of their crystal structures.     

A STUDY ON THE CRYSTALLIZATION KINETICS OF NYLON 1010

The kinetic behavior of isohermal and nonisothermal crystallization of nylon-1010has been studied by means of dilatometry and differential scanning calorimetry, respec-tively. The isothermal and nonisothermal process can be descibed by Avrami equationand Ozawa equation, respectively. From the experimental results the kinetic paramters ofcrystallization and crystalline mechanism for isothermal and nonisothermal measurementsare discussed.     

Studies on Kinetics of Crystallization of PA6／UFAPR Composites

The influence of Ultrafine Full-Vulcanized Acrylate Powdered Rubber(UFAPR) on the isothermal crys-tallization kinetics and nonisothermal crystallization behavior of PA8 has been studied by means of DSC. The results show that with the introduction of a small amount of UFAPR, the crystallization rate of PA8 can be increased obviously, and the crystallization temperature range can be augmented and the crystallite size distri-bution of the crystal can be narrowed down. The change of free energy perpendicular to the crystal nucleus, which has been calculated according to the Hoffman theory, is consistent with the result of Avrami′s equa-tion. The unit surface free energy of the radial-developing crystal spherulite decreases while the crystalliza-tion rate of PA8 increases with the introduction of UFAPR. Meanwhile, it is shown by means of the polariz-ing microscope(PLM) that the crystal size drops down and the number of the crystal grains augments with the addition of UFAPR, which shows that UFAPR can function as a nucleating agent.     

Effects of Branches on the Crystallization Kinetics of Polypropylene-g- Polystyrene and Polypropylene-g-Poly（n-butyl acrylate） Graft Copolymers with Well-defined Molecular Structures

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.     

CRYSTALLIZATION KINETICS OF HOMOGENEOUS AND HETEROGENEOUS LLDPE

Based on thermal analysis, the isothermal and nonisothemal crystallization kinetics of Ziegler-Natta catalyzedlinear low density polyethylene (Z-N LLDPE) and metallocene catalyzed LLDPE (m-LLDPE) were studied. Treating theresults with the Avrami equation and the Ozawa equation, the crystallization constant lgk and the Avrami exponent n wereobtained. Some other crystallization parameters were also discussed. According to the different characteristics of the chainstructures of Z-N LLDPE and metallocene LLDPE, their crystallizaton behaviors were analyzed. It is indicated that thehomogeneity and heterogeneity of the two polymers act in different way during the crystallization process of polymers,including the nucleation and the growth of crystals under various conditions.     

Direct Comparison of Crystal Nucleation Activity of PCL on Patterned Substrates

A sample containing different regions with poly(ε-caprolactone)(PCL), oriented polyethylene (PE), and oriented isotactic polypropylene (iPP) films in contact with glass slide has been prepared to be observed in the same view field in an optical microscope and the crystallization of PCL in different regions during cooling from 80 °C down to room temperature at a rate of 1 °C·min^-1 was studied. The results showed that the crystallization of PCL started first at the PE surface and then at the iPP surface, while its bulk crystallization occured much later. This indicates that though both PE and iPP are active in nucleating PCL, the nucleation ability of PE is stronger than that of iPP. This was due to a better lattice matching between PCL and PE than that between PCL and iPP. Moreover, since lattice matching existed between every (hk0) lattice planes of both PCL and PE but only between the (100)PCL and (010)iPP lattice planes, the uniaxial orientation feature of the used PE and iPP films resulted in the existence of much more active nucleation sites of PCL on PE than on iPP. This led to the fact that the nucleation density of PCL at PE surface was so high that the crystallization of PCL at PE surface took place in a way like the film developing process with PCL microcrystallites happened everywhere with crystallization proceeding simultaneously. On the other hand, even though iPP also enhanced the nucleation density of PCL evidently, the crystallization of PCL at iPP surface included still a nucleation and crystal growth processes similar to that of its bulk crystallization.     

Non-isothermal crystalliztion kinetics of poly(phenylene sulfide) with low crosslinking levels

Poly(phenylene sulfide) (PPS) with different crosslinking levels was successfully fabricated by means of high- temperature isothermal treatment (IT). The crosslinking degree of PPS was increased with IT time as revealed by Fourier-transform infrared spectroscopy and dynamic viscosity measurements. Its influence on the non-isothermal crystallization behaviors of PPS was studied by differential scanning calorimeter (DSC). The crystallization peak temperature of PPS with 6 h IT was 15 K higher than that of the one with 2 h IT at 30 K/min cooling rate. The non-isothermal crystallization data were also analyzed based on the Ozawa model. The Ozawa exponent m decreased from 3.5 to 2.2 at 232℃ with the increase of the IT time, suggestive of intensive thermal oxidative crosslinking reducing the crystallite dimension as PPS crystal grew. The reduced cooling crystallization function K(T) was indicative of the larger activation energy of crosslinked PPS chain diffusion into crystal lattice, resulting in a slow crystal growth rate. Additionally, the overall crystallization rate of PPS was also accelerated with the increase of crosslinking degree from the observation of polarized optical micrograph. These results indicated that the chemical crosslinked points and network structures formed during the high-temperature isothermal treatment acted as the effective nucleating sites, which greatly promoted the crystallization process of PPS and changed the type of nucleation and the geometry of crystal growth accordingly.     

Isothermal crystallization of polypropylene/surface modified silica nanocomposites

In the present work, 3-methacryloxypropyltrimethoxy-silane silanized silica(SiO_2-WD70) and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide immobilized silica(SiO_2-WD70-DOPO) nanoparticles were prepared. Silica, SiO_2-WD70 and SiO_2-WD70-DOPO were incorporated into polypropylene(PP) by melt compounding. Differential scanning calorimetry(DSC), X-ray diffraction(XRD) and polarized optical microscopy(POM) were employed to investigate the isothermal crystallization behavior of PP and PP/silica composites. The kinetic constant(kn), and half crystallization time(t1/2) were calculated by Avrami equation,while the surface free energy of folding was calculated by Lauritzen-Hoffman theory. The increased kn, decreased t1/2 and the surface free energy(σe) in the order of PP, PP/SiO_2, PP/SiO_2-WD70 and PP/SiO_2-WD70-DOPO nanocomposites were attributed to the surface modification of silica. XRD indicated that SiO_2-WD70-DOPO addition had no effect on PP crystal structure but accelerated the crystallization rate. POM determined that SiO_2-WD70-DOPO addition promoted the nucleation of PP by inducing a higher nucleation density during isothermal conditions. The surface modified nanoparticle SiO_2-WD70-DOPO might find possible application as a new type of inorganic nano-sized nucleation agent for PP.     

Nonisothermal crystallization and morphology of poly(butylene succinate)/layered double hydroxide nanocomposites

Biodegradable poly(butylene succinate) (PBS) and layered double hydroxide (LDH) nanocomposites were prepared via melt blending in a twin-screw extruder. The morphology and dispersion of LDH nanoparticles within PBS matrix were characterized by transmission electron microscopy (TEM), which showed that LDH nanoparticles were found to be well distributed at the nanometer level. The nonisothermal crystallization behavior of nanocomposites was extensively studied using differential scanning calorimetry (DSC) technique at various cooling rates. The crystallization rate of PBS was accelerated by the addition of LDH due to its heterogeneous nucleation effect; however, the crystallization mechanism and crystal structure of PBS remained almost unchanged. In kinetics analysis of nonisothermal crystallization, the Ozawa approach failed to describe the crystallization behavior of PBS/LDH nanocomposites, whereas both the modified Avrami model and the Mo method well represented the crystallization behavior of nanocomposites. The effective activation energy was estimated as a function of the relative degree of crystallinity using the isoconversional analysis. The subsequent melting behavior of PBS and PBS/LDH nanocomposites was observed to be dependent on the cooling rate. The POM showed that the small and less perfect crystals were formed in nanocomposites.     

INFLUENCE OF SAMPLE THICKNESS ON ISOTHERMAL CRYSTALLIZATION KINETICS OF POLYMERS IN A CONFINED VOLUME

Isothermal crystallization process of polymers in a confined volume was simulated in the case of instantaneous nucleation by use of the Monte Carlo method. The influence of sample thickness on some kinetic parameters of crystallization was quantitatively evaluated. It was found that there was a critical thickness value. Influence of thickness on the crystallization behavior was only found for samples of thickness near and less than the critical value. For thick samples the Avrami plot showed straight lines with a turning point at the late stage of crystallization due to the secondary crystallization. When the thickness was near or less than the critical value a primary turning point appeared in the Avrami plot at the very beginning of the crystallization process. A model was proposed to explain the mechanism of this phenomenon. According to this model the critical thickness value is related to the nucleation density or the average distance between adjacent nuclei, and the primary turning point is an indication of a transformation of crystal growth geometry from a three-dimensional mode to a two-dimensional one. Analysis of experimental results of PEO isothermally crystallized at 53.5℃ was consistent with the proposed model.     

THE STRUCTURE OF AGGREGATION STATE AND ISOTHERMAL CRYSTALLIZATION KINETICS OF NYLON-1010

The structure of aggregation state and isothermal crystallization behavior of Nylon-1010 have been studied by WAXD, DSE, Variance-Range Function and density measurement. The results show that crystallization of Nylon-1010 has the most suitable annealing temperature, the crystals of the Nxlon-1010 are two-dimension heterogeneous nucleation. Both low treatment temperature and high crystallization te, temperature are disadvantageous for Nylon-1010 crystal growth.     

CHAIN ENTANGLEMENT AND CRYSTALLIZATION OF cis-1, 4-POLYBUTADIENE

The morphological structure and mechanism of nucleation and growth of Ln-PB and Ni-PBwith different molecular weight were investigated by transmission electron microscopy. The crys-tallization of low molecular weight fraction is primarily from predetermined nuclei, crystallizationfor the high molecular weight fraction is primarily from sporadic nuclei. Two types morphologyof spherulite with different lamellar entanglement have been observed. The entanglement of highermolecular weight fractions are found to be of significance in the morphology and rate of crystallizationof polymer.     

A STUDY OF LOW-TEMPERATURE CRYSTALLIZATION BEHAVIOR THE cis-1,4 POLYBUTADIENE PREPARED WITH RARE-EARTH CATALYST SYSTEM

The effects of molecular weight and temperature on crystallization processes at low tempera-ture for cis-1,4 polybutadiene prepared with rare-earth catalyst (Ln-PB) have been studied by WAXDmethod. In the range of molecular weight from     

Miscibility and isothermal crystallization of poly(L-lactide) and poly(trimethylene carbonate) blends

Miscibility, isothermal crystallization kinetics, and morphology of poly(L-lactide)/poly(trimethylene carbonate)(PLLA/PTMC) crystalline/amorphous blends were studied by differential scanning calorimetry(DSC) and optical microscopy(OM). The heterogeneity of OM images and an unchanged glass transition temperature showed that PLLA was immiscible with PTMC. During isothermal crystallization, the crystallization rate of PLLA improved when the PTMC content was low(≤ 20%). However, when the PTMC content was high(≥ 30%), the crystallization rate decreased significantly. The reason of these nonlinear changes in crystal kinetics was analyzed according to the nucleation and growth process by virtue of a microscope heating stage. The isothermal crystallization morphologies of the blends were also studied by polarized optical microscopy and the results confirmed the conclusions obtained from crystallization kinetics.     

CRYSTALLIZATION AND MELTING OF NYLON 610

Differential scanning calorimetry was used to study the crystallization andmelting of nylon 610. For nylon 610 crystallized from the melt state (260℃), the overall rateof bulk crystallization can be described by a simple Avrami equation with Avrami exponentn ≈ 2, independent of crystallization temperature. With the experimentally obtainedT_m~0 (235℃ ～ 255℃) of nylon 610, the fold surface free energy σ_e was determined to be35 ～38 erg/cm~2. The effects of annealing temperature and time on the melting of quenchednylon 610 were also investigated. For nylon 610 quenched at room temperature there isonly one DSC endotherm peak DSC scans on annealed samples exhibited an endothermpeak at approximately 10℃ above the annealing temperature. The size and position of theendothermic peak is strongly related to annealing temperature and time. An additionalthird melting was observed when quenched nylon 610 was annealed at high temperaturefor a sufficiently long residence time. The existence of the third melting peak suggests thatmore than one kind of distribution of lamella thickness may occur when quenched nylon610 is annealed. The implications of these results in terms of crystal thickening mechanismwere discussed.     

NUCLEATION AND GROWTH ACTIVATION ENERGIES DURING CRYSTALLIZATION OF AMORPHOUS ALLOYS (Ⅰ)——CALCULATION METHOD

A new method is developed for the determination of activation energies for nucleation(E_n) and for growth of nuclei (E_g) during crystallization of amorphous alloys. This methodis based on the crystallization kinetics theory and the experimental results of the variationrelationships of local activation energy E_c(x) and local Avrami exponent n(x) with the crys-tallized volume fraction (x) during crystallization of an amorphous Ni--P alloy. Calculationresults of E_n and E_g in tbe case of crystallization of the amorphous Ni--P alloy by thismethod show that this method is not only simple in the experimental procedures, but alsoaccurate in the quantitative results.     

Crystallization behavior of disproportionately high and low molecular weight PEO blends

The crystallization behavior of PEOs with molecular weight of 1 Ok and 200k as well as their blends was studied in details. The results show that the lower molecular weight PEO crystallizes with faster crystallization rate as judged from a shorter time for completing the crystallization. On the other hand, the higher molecular weight PEO crystallizes at relatively higher temperature, indicating an early start of crystallization compared with the lower molecular weight one. The blends of these two PEOs with different blend ratios always cocrystallize during the cooling processes. It is confirmed that mixing of the 10k PEO with the 200k one is in favor of the crystallization of the system. This is not only demonstrated by the early start of the crystallization at higher crystallization temperature, and also a faster crystal growth of the blend with respect to the 200k PEO. The crystallization of the blends at higher temperature is caused by an early start of nucleation and an increment of nucleus density. This may originate from the density fluctuation of the blend and a reduction in energy barrier for nucleation. Moreover, it is found that the crystallinity of the 1 Ok PEO rich blends increases with increasing concentration of the 10k PEO. This is caused by the solvent effect of the 10k PEO toward the 200k PEO. On the other hand, the crystallinity of the 30/70 （10k/200k） PEO blend is decreased a little bit. This may be a balanced result of the improved crystallization of the 200k PEO at the expense of the high crystallization ability of the 1 Ok PEO.