The influence of recycled material on the crystallization kinetics of thermoplastic polymers

The injection moulding of semi-crystalline thermoplastic polymers requires an exact knowledge of the thermodynamic data and of the crystallization kinetics. The behaviour of the polymer melt during rapid cooling in the mould determines, to a great extent, the quality and usability of a final product. Technical raw materials are often equipped with nucleating agents in order to obtain crystallization within the desired temperature range and at the required rate. The use of recycled material (regranulate) shows an analogous effect such as the addition of nucleating agents, i.e. crystallization begins at a higher temperature and a higher crystallization rate is detected compared to materials without added regranulate. Heat flux DSC was used to study the crystallization of polyamides, polyolefins and polyoxymethylene during cooling at various cooling rates. Although the temperature gradients and pressures which occur in the proceesing machine cannot be realised in DSC tests, the DSC results reproduce the direction of influence of the regranulate additive very clearly.     

Generalized kinetics of overall phase transition explicit to crystallization

Modeling of process for reaction kinetics is a fashionable subject of publications. This paper tests various phenomenological models starting with the Verhulst logistic functions, Kolmogorov adaptation up to the renowned KJMA and SB variants. The meaning of both the mortality (α) and fertility (1 ? α) terms are mathematically analyzed in detail involving variation of their power exponents, their characteristic points, and shape examination of the rate curves. Kolmogorov derivation of nucleation-growth process is revised.     

Thermal cycling effect on the kinetics of glass transition and crystallization of a Zr-based bulk metallic glass

Journal of Thermal Analysis and Calorimetry - This work presents the convective heat transfer and friction loss characteristics of novel functionalized graphene-based and metal oxide nanofluids....     

Nonisothermal crystallization kinetics and microstructure evolution of calcium lanthanum metaborate glass

This paper reports results on the crystallization kinetics of 35.5CaO–7.25La₂O₃–57.25B₂O₃ glass under nonisothermal conditions based on the studies carried out from the differential thermal analysis upon using various well-established models. The crystalline phases formed during the optimized ceramization process have been confirmed from the X-ray diffraction. The activation energies of the first (formation of CaLaB₇O₁₃) and second (formation of LaBO₃) crystallization events have been estimated using the conventional methods of Kissinger, Augis–Bennett, Ozawa, and Matusita, and the results are found to be in good agreement with each other. The Avrami exponents that are determined by these models for the crystallization of CaLaB₇O₁₃ and LaBO₃ are found to be in the range of (1.81–2.35) and (4.03–4.65), respectively. This indicates that the formation of CaLaB₇O₁₃ is dominated by a surface crystallization, whereas LaBO₃ is formed by three-dimensional bulk crystallization with an increased rate of nucleation. This observation is further validated by microstructural investigation, which shows the formation of CaLaB₇O₁₃ phase as a surface layer and a bulk crystallization of LaBO₃ in optimally ceramized samples.     

Isothermal crystallization kinetics of the chalcogenide glass Bi10Se70In20

Results of DSC under isothermal conditions on the chalcogenide glass Bi₁₀Se₇₀In₂₀ are reported and discussed. The Johnson-Mehl-Avrami equation was used to evaluate the crystallization activation energy (E _a) and the crystallization mechanism was studied. The results indicate that the crystallization mechanism involves one dimensional and surface processes for Bi₁₀Se₇₀In₂₀. The average calculated value ofE _a for Bi₁₀Se₇₀In₂₀ is 34.38±1.46 kcal/mol.

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Zusammenfassung Die Ergebnisse von isothermen DSC-Untersuchungen an dem Chalkogenglas Bi₁₀Se₇₀In₂₀ wurden beschrieben und diskutiert. Die AktivierungsenergieE _a der Kristallisierung wurde mit Hilfe der Johnson-Mehl-Avrami-Gleichung ermittelt und der Kristallisierungsmechanismus untersucht. Die Ergebnisse zeigen, da\ der Kristallisierungsmechanismus von Bi₁₀Se₇₀In₂₀ eindimensionale und OberflÄchenvorgÄnge beinhaltet. Der errechnete mittlere Wert vonE _a betrÄgt für Bi₁₀Se₇₀In₂₀ 34.38±1.46 kcal/mol.

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The authors are grateful to Dr. N. Afify for many helpful discussions. This work was partly supported by a Grant-in-Aid for Scientific Research from the Deutsche Gesellschaft für Technische Zussammenarbeit (G.T.Z.) and D.A.A.D., Germany     

Study of formation of nano-quasicrystals and crystallization kinetics of Zr-Al-Ni-Cu metallic glass

The formation of nano-quasicrystals on isothermal annealing of melt-spun ribbons of Zr_69.5Al_7.5Ni₁₁Cu₁₂ metallic glass has been investigated using transmission electron microscopy (TEM). The crystallization study of this metallic glass has been carried out using differential scanning calorimetry (DSC) in non-isothermal (linear heating) mode. It exhibits two-stage crystallization where the first stage corresponds to the precipitation of icosohedral nano-quasicrystalline phase. This has been confirmed with the help of TEM investigations. The crystallization parameters like the activation energy (E _c) and frequency factor (k ₀) have been derived using the Kissinger peak shift analysis. The activation energies for the first and second crystallization peak are found to be 278 and 295 kJ mol^–1, respectively. The frequency factors obtained for the two peaks are respectively 7.16·10¹⁹ and 1.42·10²⁰ s^–1. E _c, k ₀ and the Avrami exponent (n) have also been derived by fitting the Johnson-Mehl-Avrami-Kolmogorov (JMAK) equation for the transformed volume fraction (x) to the crystallization data. JMAK results of E _c for the first and second crystallization peak turn out to be 270 and 290 kJ mol^–1 respectively. However, k ₀ and n are found to be heating rate dependent as reported in similar studies. The values of n for the first crystallization stage ranges between 1.66 and 2.57 indicating diffusion-controlled transformation in agreement with earlier reports.     

The crystallization kinetics of polyamide-12

The crystallization kinetics of polyamide-12 has been investigated using a combination of differential scanning calorimetry (DSC) and hot-stage optical microscopy. The DSC data for isothermal crystallization were consistent with a simple two-parameter Avrami model for isothermal crystallization and optical measurements of the spherulite growth rates and nucleation density. On the basis of semiempirical expressions for these quantities, it is shown that with small adjustments the model can also account for DSC data for nonisothermal crystallization, provided that corrections are made for the dynamic heat balance between the sample and the DSC oven. Received: 9 March 2000 Accepted: 28 September 2000     

Crystallization-induced aggregation of block copolymer micelles: influence of crystallization kinetics on morphology

We present a systematic investigation of the crystallization and aggregation behavior of a poly(1,2-butadiene)-block-poly(ethylene oxide) diblock copolymer (PB-b-PEO) in n-heptane. n-Heptane is a poor solvent for PEO and at 70°C the block copolymer self-assembles into spherical micelles composed of a liquid PEO core and a soluble PB corona. Time- and temperature-dependent light scattering experiments revealed that when crystallization of the PEO cores is induced by cooling, the crystal morphology depends on the crystallization temperature (T _c ): Below 30°C, the high nucleation rate of the PEO core dictates the growth of the crystals by a fast aggregation of the micelles into meander-like (branched) structures due to a depletion of the micelles at the growth front. Above 30°C the nucleation rate is diminished and a relatively small crystal growth rate leads to the formation of twisted lamellae as imaged by scanning force microscopy. All data demonstrate that the formation mechanism of the crystals through micellar aggregation is dictated by two competitive effects, namely, by the nucleation and growth of the PEO core.     

Influence of particle size on the crystallization process and the bioactive behavior of a bioactive glass system

Bioactive glasses have attracted considerable interest in recent years, due to their technological application, especially in biomaterials research. Differential scanning calorimetry (DSC) has been used in the study of the crystallization mechanism in the SiO₂–Na₂O–CaO–P₂O₅ glass system, as a function of particle size. The curve of the bulk glass presents a slightly asymmetric crystallization peak that could be deconvoluted into two separate peaks, their separation being followed in the form of powder glasses. Also, a shift of the crystallization peaks to lower temperatures was observed with the decrease of the particle size. FTIR studies – that are confirmed by XRD measurements – proved that the different peaks could be attributed to different crystallization mechanisms. Moreover, it is presented the bioactive behavior of the specific glass as a function of particle size. The study of bioactivity is performed through the process of its immersion in simulated human blood plasma (simulated body fluid, SBF) and the subsequent examination of the development of carbonate-containing hydroxyapatite layer on the surface of the particles. The bioactive response is improved with the increase of the particle size of powders up to 80 μm and remains almost unchanged for further increase, following the specific surface to volume ratio decrease.     

Effect of polydispersity on the crystallization kinetics of suspensions of colloidal hard spheres when approaching the glass transition

We present a comprehensive study of the solidification scenario in suspensions of colloidal hard spheres for three polydispersities between 4.8% and 5.8%, over a range of volume fractions from near freezing to near the glass transition. From these results, we identify four stages in the crystallization process: (i) an induction stage where large numbers of precursor structures are observed, (ii) a conversion stage as precursors are converted to close packed structures, (iii) a nucleation stage, and (iv) a ripening stage. It is found that the behavior is qualitatively different for volume fractions below or above the melting volume fraction. The main effect of increasing polydispersity is to increase the duration of the induction stage, due to the requirement for local fractionation of particles of larger or smaller than average size. Near the glass transition, the nucleation process is entirely frustrated, and the sample is locked into a compressed crystal precursor structure. Interestingly, neither polydispersity nor volume fraction significantly influences the precursor stage, suggesting that the crystal precursors are present in all solidifying samples. We speculate that these precursors are related to the dynamical heterogeneities observed in a number of dynamical studies.     

The effect of molecular weight on the crystallization kinetics of polycaprolactone

The crystallization kinetics and degree of crystallinity of polycaprolactone (PCL) were studied using the technique of differential scanning calorimetry (DSC). The crystallization exotherms measured using DSC were analyzed using a modified Avrami equation. The modification limited the analysis of the data to the primary crystallization process, where the Avrami equation is applicable. Both the degree of crystallinity and primary composite rate constant were found to decrease with increasing molecular weight. The observations have been explained in terms of the unified reptation‐nucleation theory. Copyright © 2006 John Wiley & Sons, Ltd.     

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.     

The kinetics of flow-induced crystallization from solution

In situ birefringence measurements of the seeded growth in a tubular flow geometry of 0.01 wt% solution of a polyethylene fraction in xylene have been used to determine the flowinduced crystallization kinetics as a function of temperature and flow rate. In contrast to earlier reports on higher molecular weight polyethylene and polypropylene systems, orientational properties of the crystallized fibers do not show a clear correlation with growth conditions (i.e., temperature and flow rate). The combined kinetic data from these experiments and our earlier studies of higher molecular weight polyethylene—xylene and polypropylene—tetralin systems are analyzed in terms of a modified from of the Avrami equation which provides a basis for separately correlating temperature and flow rate effects. The observed temperature dependency of the crystallization process can be interpreted in terms of nucleation and growth models while the flow rate dependency can be interpreted on the basis of entanglement formation arguments. Results showing liquid phase precursor formation in an atactic polystyrene system are also presented to further document the liquidphase separation which can be induced in polymers under flow.     

Study of non-isothermal crystallization kinetics of Ge20Se70Sn10 chalcogenide glass

Journal of Thermal Analysis and Calorimetry - The glass transition and non-isothermal crystallization behavior of Ge20Se70Sn10 glass prepared by the melt-quenching technique was investigated using...     

Non-isothermal crystallization kinetics of continuous glass fiber-reinforced poly(ether ether ketone) composites

Current studies on crystallization kinetics for glass fiber-reinforced poly(ether ether ketone) mainly focused on short glass fiber-reinforced composites and their isothermal crystallization. It is worth noting that continuous glass fiber-reinforced poly(ether ether ketone) composite (CGF/PEEK) possesses relatively higher mechanical performance than short fiber-reinforced PEEK under high temperature. Here, for the first time, we investigate the non-isothermal crystallization kinetics and melting behavior of CGF/PEEK by differential scanning calorimetry at four different cooling rates. By evaluating the crystallite size of CGF/PEEK using X-ray diffraction, it is found that with the decreasing cooling rate, the crystallite size distribution evolves more uniform, and the size of crystallites enlarges. Besides, by systematical analysis, we find the modified Avrami equation can well describe crystallization behavior of the CGF/PEEK. The higher Avrami value of CGF/PEEK than pure PEEK indicates that CGF could introduce a more complex geometry effect on the crystallization. The addition of CGF greatly reduces the absolute value of crystallization activation energy of PEEK, suggesting that CGF can reduce the nucleation energy barrier. The obtained results illustrate that CGF can accelerate the nucleation rate due to heterogeneous nucleation while reduce the growth rate due to retarded polymer chain mobility. And the cooling conditions can influence crystal growth and morphology.

     

Effects of filler size and heat treatment on the crystallization behavior of glass bead‐filled polypropylene

The effects of glass bead (GB) size and annealing temperature on the formation of β‐crystals of glass bead‐filled polypropylene (PP) are studied in this articles. Differential scanning calorimetry (DSC) measurements indicated that the amount of β‐form in PP crystals was a function of the glass bead content and size. For a fixed glass bead content, it was found that the smaller the diameter of the glass bead, the higher was the content of β‐crystals formed in the PP. On the other hand, wide‐angle X‐ray diffraction (WAXD) measurements revealed that the annealing temperature was also a major factor that affected the crystallization behavior of glass bead‐filled PP. It seemed that the blends with different glass bead contents had their own optimal annealing temperatures for β‐crystal formation. As an example, when the glass bead content was 48 wt %, the optimal annealing temperature for β‐crystal formation was about 108 °C, whereas it shifted to 100 °C for 14 wt % glass bead‐filled polypropylene. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 306–313, 2005     

The effect of TiO2 on the kinetics of polyamide 6 crystallization

Colloid and Polymer Science - The kinetics of isothermal and nonisothermal crystallization of polyamide-6 (PA6) containing titania was studied by means of DSC. It was found thatTiO 2 causes an...     

Crosslinking kinetics of polyethylene with small amount of peroxide and its influence on the subsequent crystallization behaviors

Crosslinking reactions of high density polyethylene with low peroxide concentrations ranging from 0.1 wt% to 1.0 wt% at temperatures of 170, 180 and 190 ° C were monitored by rheological measurements. A critical gel forms at the peroxide concentration of 0.2 wt%, where the transition from long chain branching generation to crosslinking network formation could occur. Rheokinetics of crosslinking can be fitted well by Ding-Leonov's model. The curing rate k_2 at the earlier stage exhibits about 3 times acceleration per 10 °C with increasing temperature, while the equilibrium modulus G′ at the fully cured stage is almost independent of temperature. Influences of crosslinking on the subsequent crystallization behaviors were detected by DSC measurements. Above the critical gel concentration, crystallization is largely retarded as evidenced by the lower crystallization temperature Tc and crystallinity X_c due to the network formation. The secondary crystallization valley located at the temperature near 80 °C can be observed above the critical concentration, which becomes more evident with the increasing peroxide concentration and curing temperature. This phenomenon provides another evidence of crystallization retardation by the crosslinking network.