Analysis of the isothermal crystallization of polypropylene/wood flour composites

Isothermal crystallization and melting of isotactic polypropylene in binary polypropylene-wood flour composites has been studied by DSC, and the influence of an ethylene-methacrylic acid copolymer interfacial agent analyzed. Wood flour induces a slight nucleating effect, reducing the basal interfacial free energy of nucleation and increasing the overall crystallization rate. The interfacial agent generates a compatibilization phenomenon and an increase in the basal interfacial free energies with respect to the binary composites. In both binary and ternary systems the melting behaviour is a function of undercooling and is unaltered by the presence of either wood flour or the interfacial agent.     

Interpretation of the nonisothermal crystallization kinetics of polypropylene using a power law nucleation rate function

A nucleation rate function is proposed for use in analyzing the overall crystallization kinetics of polymers. This function allows for the possibility that the nucleation rate varies substantially during the crystallization. This feature is particularly useful in analyzing nonisothermal crystallization, but it can be used to analyze isothermal crystallization as well. The nucleation rate function was used in the derivation of a modified transformation kinetics equation of the Avrami type. The modified Avrami equation was found to be suitable for kinetics analysis for the data obtained from nonisothermal crystallization at rapid cooling rates. Kinetics parameters used to describe nonisothermal crystallization under rapid cooling rates are presented and discussed. These include crystallization induction time, plateau (crystallization) temperature, crystallization half-time, crystallization rate constant, Avrami index, and newly defined quantities called nucleation index, geometric index, and nucleation rate constant. The procedure used to obtain the nucleation rate constant and nucleation index for the nucleation rate function is described and illustrated by application to the analysis of the crystallization kinetics of polypropylene. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1077–1093, 1997     

Effect of functionalization on non-isothermal crystallization behavior of polypropylene

The non-isothermal crystallization kinetics of three functionalized polypropylenes (PPs; polypropylenes-g-acrylic acid [PP-g-AA], polypropylenes-g-glycidyl methacrylate [PP-g-GMA], polypropylenes-g-maleic anhydride [PP-g-MAH]) at different cooling rates were investigated by differential scanning calorimetry, using the Jeziorny method, Ozawa method, and Mo method. The result showed that Mo method can adequately describe the non-isothermal crystallization kinetics of pure PP and functionalized PPs, and at a given relative crystallinity, the crystallization rate obtained using Mo method followed an order of PP-g-AA > PP-g-GMA > PP > PP-g-MAH. The crystallization activation energy for these samples was calculated using Kissinger's method, which indicated that the introduction of monomers had a confinement effect on the motion of PP chains.     

Experimental study of shear-induced crystallization of an impact polypropylene copolymer

The crystallization kinetics of polypropylene was observed during shear and after shear experiments under isothermal condition. The crystallizations were performed in a plate-plate and a fiber pull-out device. The nucleation density, the crystalline growth and the overall kinetics were measured and compared with data obtained in a similar way but during static experiments. The morphologies are spherulitic and formed from nuclei which seem to be randomly distributed. -phase spherulites are always observed but with a nucleation density and a growth rate which depend on shearrate. The nucleation density is strongly enhanced by shear and acts as the main factor on the overall kinetics. The overall kinetics can be analyzed with a two-step Avrami model, where an Avrami exponentn ₁ with a very high value is always observed first after shear and a more usual parametern ₂ for the subsequent crystallization period. This high value ofn ₁ seems to be related to the strong enhancement of nucleation density. The growth rate increases with the shear-rate, but the basic growth mechanisms do not seem to be modified. For crystallizations after shear the growth rate decreases with a long-time delay after shear but not down to the static value. The effect is characteristic of a partial relaxation of chain orientation after shear but with a very unusual time constant.     

The effect of nucleating agents on the crystallization kinetics of polypropylene

Compositions of neat polyproylene (PP), PP–PE (polyethylene) blend and PP–PE–DBS (dibenzylidene sorbitol) were studied with respect to their crystallization kinetics by means of differential scanning calorimetry in isothermal mode. A modified Avrami equation was applied to obtain the crystallization parameters of PP, PP–PE and PP–PE–DBS. Optical and hot-stage microscopy and dynamical analysis were used for structure determination. Experimental results have indicated that PE addition inhibits PP crystallization rate and acts as a plasticizer, while addition of DBS changes the crystallization kinetics. A detailed study of the DBS nucleation effects indicates that owing to the high surface energy, nuclei are formed during primary crystallization, leading to a fine PP crystalline structure and improved mechanical properties.     

Effect of fillers on fire retardancy of intumescent polypropylene blends

Addition of Ammonium Polyphosphate/Polyamide-6 system is known to provide flame retardancy in many polymers blends via an intumescent process. Particulate fillers (talc and calcium carbonate) are used in large quantities in PP. Combination of fillers in PP can modify the properties of the polymeric matrix. This study investigates the effect of fillers (talc and calcium carbonate) on the fire performance of the Polypropylene/Ammonium polyphosphate/Polyamide-6 blend. It is shown that the fire performance strongly depends on the nature of the filler used. Talc increases and calcium carbonate decreases in the fire performance of the blend.     

Fractionated crystallization of polypropylene droplets produced by nanolayer breakup

Layer‐multiplying coextrusion was used to fabricate assemblies of 257 layers, in which polypropylene (PP) nanolayers alternated with thicker polystyrene (PS) layers. The PP layer thickness was varied from 12 to 200 nm. When the assembly was heated into the melt, interfacial instability‐driven breakup of the thin PP layers produced a dispersion of PP particles in a PS matrix. Particle size analysis indicated that breakup of PP microlayers produced a bimodal particle size distribution. A population of submicron particles formed because of the Rayleigh instability, and a second population of large particles formed by relaxation. Breakup of 12‐nm layers resulted in primarily submicron particles. The fraction of PP as submicron particles dropped dramatically as the layer thickness increased to 40 nm. The particle dispersion was characterized by thermal analysis and wide angle X‐ray diffraction. Fractionated crystallization gave rise to four crystallization exotherms at 40, 60, 85, and 100 °C. The exotherm at 40 °C was identified with homogeneous nucleation of the submicron particles in the smectic form. Exotherms at higher temperatures represented fractionated crystallization of the large micron‐sized particles in the PP α‐form. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1138–1151, 2007     

The influence of thermoelastomers on the crystallization behavior of isotactic polypropylene under shear

The crystallization behaviors of isotactic polypropylene (iPP) and its blends with thermoelastomers have been investigated with in situ X‐ray scattering and optic microscopy. At quiescent condition, the crystallization kinetics of iPP is not affected by the presence of elastomers; while determined by the viscosity, the differences are observed on sheared samples. With a fixed shear strain, the crystallization rate increases with increasing the shear rate. The fraction of oriented lamellar crystals in blends is higher than that in pure iPP sample, while the percentage of β phase is reduced by the presence of the elastomers. On the basis of experimental results, no direct correlation among the fraction of oriented lamellae, the percentage of β phase, and growth rate can be deduced. The evolution of the fraction of oriented lamellae supports that shear field promotes nucleation rather than growth process. Shear flow induces the formation of nuclei not only with preferring orientation but also with random orientation. The total density of nuclei, which determines the crystallization kinetics, does not control the ratio between nuclei with and without preferring orientation, which determines the fraction of oriented lamellae. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1188–1198, 2006     

Isothermal crystallization kinetics of polypropylene/POSS composites

Polypropylene (PP)/octavinyl polyhedral oligomeric silsesquioxane (POSS) composites were prepared by two different processing methods: reactive blending and physical blending, and the crystallization behavior of PP and PP/POSS composites was studied by means of differential scanning calorimetry and polarized optical microscope. The results showed that the crystallization of PP in PP/POSS composites was strongly influenced by the different processing methods. POSS particles can act as effective nucleating agent, accelerating the crystallization of PP. The crystallization rate increased more dramatically for the reactive blending composite due to the stronger nucleating effect of PP grafted POSS. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1762–1772, 2008     

Nucleation of isotactic polypropylene crystallization by gold nanoparticles

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

Shear-induced crystallization of isotactic polypropylene based nanocomposites with montmorillonite

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

Attapulgite and ultrasonic oscillation induced crystallization behavior of polypropylene

In this article, the effect of ultrasonic oscillation on the dispersed morphology of attapulgite in polypropylene (PP) and crystallizing kinetics of PP/attapulgite composites prepared through extrusion in the presence and the absence of ultrasonic oscillation were studied. X‐ray diffraction analysis results showed that ultrasonic oscillation did not change attapulgite crystal structure during extrusion in PP/attapulgite composites. On the other hand, scanning electron microscopy and transmission electron microscope photographs indicated that ultrasonic oscillation promoted the dispersion of attapulgite particles in PP matrix. The dispersed morphology of attapulgite and ultrasound oscillation affected the crystalline form, nucleation rate, crystallization temperature, crystallinity, and spherulite size of PP crystals. PP transcrystals were formed on the attapulgite particle surface. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2300–2308, 2007     

Different influences of nucleating agents on crystallization behavior of polyethylene and polypropylene

The crystallization behavior of polyethylene (PE) and polypropylene (PP), including the neat ones and the ones nucleated with the same nucleating agent (NA), was studied by DSC. It was found that the nucleating agent decelerated the PE nonisothermal crystallization process. NA did enhance the nucleating rates for both PE and PP, but the linear growth rate dominated the volumetric growth rate for PE, and the volumetric growth rate dominated the overall crystallization rate. That is why PE nucleated with NA had a slower overall crystallization rate than the neat one.     

Effect of carbon nanotubes on the crystallization and properties of polypropylene

The effect of different concentrations of single‐walled carbon nanotubes (SWNTs) on the nonisothermal crystallization kinetics, morphology, and mechanical properties of polypropylene (PP) matrix composites obtained by melt compounding was investigated by means of X‐ray diffraction, differential scanning calorimetry, optical and scanning electron microscopy, and dynamic mechanical thermal analysis. Microscopy showed well‐dispersed nanotube ropes together with small and large aggregates. The modulus was found to increase by about 75% at a level of 0.5 wt % nanotubes. The SWNTs displayed a clear nucleating effect on the PP crystallization, favoring the α crystalline form rather than the β form. The crystallization kinetics analysis showed a significant increase in activation energy on incorporating nanotubes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2445–2453, 2005     

Nucleation and crystallization of polypropylene filled with BaSO4

The influence of high concentration of BaSO₄ as nucleating agent on crystallization of fiber-forming polypropylene was studied by DSC. The work presents experimental and calculated values of melting and crystallization enthalpies of filled polypropylene and the influence on the formation of interface interactions between filler and polymers. These results show minimal interactions of components (BaSO₄ and polypropylene) under experimental conditions.     

Nonisothermal crystallization kinetics of polypropylene/montmorillonite nanocomposites

The nonisothermal crystallization kinetics of poly(propylene) (PP) and poly(propylene)/organic‐montmorillonite (PP/Mont) nanocomposite were investigated by differential scanning calorimetry (DSC) with various cooling rates. The Avrami analysis modified by previous research was used to describe the nonisothermal crystallization process of PP and PP/Mont nanocomposite very well. The values of half‐time and Z_c showed that the crystallization rate increased with increasing cooling rates for both PP and PP/Mont nanocomposite, but the crystallization rate of PP/Mont nanocomposite was faster than that of PP at a given cooling rate. The activation energies were estimated by the Kissinger method, and the values were 189.4 and 155.7 kJ/mol for PP and PP/Mont nanocomposite, respectively. PP/Mont nanocomposite could be easily fabricated as original PP, although the addition of organomontmorillonite might accelerate the overall nonisothermal crystallization process. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 408–414, 2002; DOI 10.1002/polb.10101     

On the crystallization behavior of cold-drawn syndiotactic polypropylene

The influence of the chain conformation on the crystallization behavior of cold-drawn syndiotactic polypropylene (sPP) has been investigated. The conformational and structural changes depending on drawing conditions and thermal treatments has been observed by x-ray diffraction, infra-red spectroscopy and modulated differential scanning calorimetry. A nucleation and crystal growth model is introduced, which explains the low crystallinity of cold-drawn sPP.     

Nucleation effect of cyclodextrin inclusion compounds on the crystallization of polypropylene

The β‐cyclodextrin (β‐CD) and γ‐cyclodextrin (γ‐CD) inclusion compounds (ICs) with two different molecular weight isotactic polypropylene (iPP) were prepared. The ICs with high molecular weight iPP as guest molecule had lower inclusion rate. The crystallization behavior of iPP blended with the CDs and ICs was investigated by differential scanning calorimetry, polarized optical microscopy, and light scattering. The iPP blended with the ICs was found to exhibit higher crystallization temperature (T_C), smaller spherulites, and faster crystallization rate than those of neat iPP. These results indicate that the ICs play a role of nucleating agent on the crystallization of iPP and induce the accelerated crystallization. Both β‐CD‐iPP ICs and γ‐CD‐iPP ICs with longer iPP molecular chains had better nucleation effect than the ICs with shorter iPP molecular chains. This suggested that the nucleation effect of these ICs was affected by the inclusion rate of ICs. The lower inclusion rate could result in better nucleation effect, due to the interaction of extended iPP molecules inside the CD cavity and iPP molecules in the matrix. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 130–137, 2009     

Non-isothermal crystallization behavior of polypropylene with nucleating agents and nano-calcium carbonate

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

Compatibilization of polypropylene/poly (ethylene oxide) blends and crystallization behavior of the blends

The compatibilization of incompatible polypropylene (PP)/poly(ethylene oxide) (PEO) blends was studied. The experimental results showed that the graft copolymer [(PP-MA)-g-PEO] of maleated PP(PP-MA) and mono-hydroxyl PEO (PEO-OH) was a good compatibilizer for the PP/PEO blends in which PP-MA also had some compatibilization. The crystallization of the blends was affected by the compatibility between PP and PEO. The interfacial behavior of the compatibilizers had an important effect on crystallization behavior of the PP/PEO blends. PEO showed fractionated crystallization in the PP/PEO blends. This behavior was studied from the view point of the theory of fractionated crystallization. © 1994 John Wiley & Sons, Inc.