Lauritzen Hoffman Secondary Nucleation Research Articles

Biobased nucleation agents for poly-L-(lactic acid) — Effect on crystallization, rheological and mechanical properties

In the present work, the nucleating aptitude for poly-L-(lactic acid) (PLLA) of several biobased nanoparticles (NPs) with different morphologies and surface properties, including cellulose nanofibrils with and without lignin (LCNFs and CNFs) as well as cellulose, chitin and starch nanocrystals (CNCs, ChNCs and SNCs), was investigated. A single melt-processing step using a small amount of poly(ethylene glycol) (PEG) as carrier for the NPs was adopted to prepare films with the same nanofiller content of 1 wt%. The nucleation efficiency was investigated by differential scanning calorimetry using Avrami's and Lauritzen–Hoffman's secondary nucleation theory. The crystallization half-time was found to change considerably according to the morphology and surface properties of the NPs, with the lowest time observed for CNFs and CNCs, followed by ChNCs, SNCs and LCNFs. Comparing the surface energy components of the different nucleating agents, it was found that the nanofiller with the highest γp had the lowest t1/2 and demonstrated the most effective nucleating aptitude. The evolution of the melt rheological properties of the different compositions, and the mechanical and optical properties of the films with and without a short annealing treatment were also studied.

Lignin-coated cellulose nanocrystals as promising nucleating agent for poly(lactic acid)

We report the effect of lignin-coated cellulose nanocrystals (L-CNCs) on the crystallization behavior of poly(lactic acid) (PLA). PLA/L-CNC nanocomposites were prepared by melt mixing, and the crystallization behavior of PLA was investigated using differential scanning calorimetry. Isothermal crystallization data were analyzed using Avrami and Lauritzen–Hoffman secondary nucleation theory, while the equilibrium melting temperature was determined using the nonlinear Hoffman–Weeks method. The lignin-coated cellulose nanocrystals acted as a nucleating agent and significantly increased the rate of crystallization and degree of crystallinity of PLA in PLA/L-CNC nanocomposites. The Avrami exponent, n, increased in the presence of L-CNCs, displaying a conversion from lamellar morphology to two-dimensional crystal growth. PLA/L-CNC nanocomposites also gave lower values of the nucleation parameters, $$K_{\text{g}}$$ and σ e, due to a reduction in the activation energy for nucleation.

Evaluation of polyesters from renewable resources as alternatives to the current fossil-based polymers. Phase transitions of poly(butylene 2,5-furan-dicarboxylate)

Poly(butylene 2,5-furan dicarboxylate) (PBF) is an alipharomatic polyester that can be prepared using monomers derived from renewable resources such as 2,5-furan dicarboxylic acid and 1,4-butanediol. In the present work the thermal behavior of PBF was studied. Multiple melting was observed during heating traces of samples isothermally crystallized from the melt using differential scanning calorimetry (DSC). The wide angle X-ray diffraction (WAXD) patterns did not reveal the presence of a second crystal population, or a crystal transition upon heating. DSC study showed that the phenomena are closely related to recrystallization. Temperature modulated DSC (TMDSC) tests indeed evidenced enhanced recrystallization. The equilibrium melting point was estimated to be 184.5 °C using the linear Hoffman–Weeks extrapolation. The heat of fusion of the pure crystalline polymer was found equal to 129 J/g or (27.35 kJ/mol), a little lower than that of PBT. The Lauritzen–Hoffman secondary nucleation theory was used and the surface energy values and the work of chain folding were found to be comparable to those of PBT, but quite lower than those of poly(ethylene terephthalate) (PET). The non-isothermal crystallization on cooling and the cold-crystallization of quenched samples were also studied. Condensed spherulites were observed on isothermal crystallization under large supercoolings by using polarized optical microscopy (POM), while the spherulites turned to ring-banded morphology at higher temperatures. In every case the nucleation density was high.

Crystallization Regimes and Spherulitic Morphology of Poly(trimethylene terephthalate/isophthalate) Random Copolyesters

The crystallization regimes and spherulitic morphology of poly (trimethylene terephthalate/isophthalate) (TI) random copolyesters were studied in this work. A hot stage polarizing microscope was used to observe morphology and measure growth rate of the spherulite of TI copolyesters. Lauritzen-Hoffman secondary nucleation theory was applied to investigate crystallization kinetics and regimes of TI copolyesters. Results show that the spherulitic growth rate decreased with an increase in isophthalic acid content of the copolyesters. The analysis of Lauritzen-Hoffman secondary nucleation theory shows that regime I, II, and III were observed in TI11 and TI21. Regime III was observed in TI29. The spherulitic morphology of TI11, TI21, and TI29 changed from elliptical-shaped spherulite to irregular spherulite and then to normal spherulite at the regime transitions.

Temperature dependences of solid structure and properties of biodegradable poly(butylene succinate-co-terephthalate) (PBST) copolyester

In this paper, studies of the temperature dependence for spherulitic growth of PBST copolyester bearing 70 mol% butylene terephthalate units (named as PBST-70) ranged from 70 to 170 °C were first reported based on the Lauritzen–Hoffman secondary nucleation theory. The results showed that maximum spherulitic growth rate of PBST-70 was obtained under crystallization temperature of 90 °C, and more perfect spherulites were formed via increasing isothermal crystallization temperature by POM measurement. The classical regime I → II and regime II → III transitions occurred at the temperatures of 150 and 110 °C, respectively, using the empirical universal values of U* = 6300 J mol−1 and T∞ = Tg − 30 K. Moreover, the effects of isothermal crystallization temperature on crystal lamellar thickness, thermal and tensile properties of PBST-70 were systematically investigated by small angle X-ray scattering, differential scanning calorimeter, and strength tester. The results indicated that the crystal lamellar thickness increased by increasing isothermal crystallization temperature. The endothermic peak shifted to higher temperature and the tensile properties of PBST-70 were enhanced under higher isothermal crystallization temperature.

The impact of nanoclay on the crystal growth kinetics and morphology of biodegradable poly(ethylene succinate) composite

The impact of nanoclay on the isothermal crystal growth kinetics and morphology of biodegradable poly(ethylene succinate) (PES) is reported. A PES composite (PESNC) containing 5 wt% organically modified montmorillonite, was prepared via solvent casting method. The structural study of PESNC, using X-ray diffraction and optical microscope, showed the formation of micro-intercalated composite. The isothermal crystallization behavior of neat PES and PESNC was studied by differential scanning calorimetry, polarized optical and atomic force microscopes. Results show that the supercooling effect of neat PES reduces after composite formation. The Lauritzen–Hoffman secondary nucleation theory (the LH-model) was employed to understand the crystal growth mechanism of these systems. According to the LH-model, only one transition between regime II and regime III was found, but no transition from regime I to II was detected.

Impact of the nature and shape of cellulosic nanoparticles on the isothermal crystallization kinetics of poly(ε-caprolactone)

Polycaprolactone (PCL)/cellulose nanocomposites were prepared by mixing PCL with surface modified sisal nanowhiskers (CNW) and microfibrillated cellulose (MFC) extracted from sisal fibers. The influence of cellulosic nanoparticles on the crystallization behavior of PCL was investigated by differential scanning calorimetry. Isothermal crystallization data were modeled with Avrami’s kinetics, Lauritzen–Hoffman secondary nucleation theory and equilibrium melting points were determined with the Hoffman–Weeks method. The cellulose nanoparticles, acting as nucleating agents, drastically accelerate the crystallization of PCL while depressing its equilibrium melting by 9–10 °C. The crystallization of MFC-nanocomposites is slightly faster than that of CNW-nanocomposites, in agreement with the slightly lower bulk activation energy for crystallization and nucleation parameter in the former. The results are discussed based on the differences of specific surface area and surface chemistry of nanoparticles, as well as the confinement phenomenon.

Equilibrium melting temperature and spherulitic growth rate of poly(phenylene sulfide)

The equilibrium melting temperature ( T m ), through linear extrapolation method (HW) and nonlinear extrapolation method (MX) respectively, and the supercooling dependence of the spherulitic growth rate, in the context of the Lauritzen–Hoffman secondary nucleation theory, of poly(phenylene sulfide) (PPS) have been investigated by differential scanning calorimeter (DSC) and a polarized optical microscope (POM) equipped with a CSS450 shear hot stage. The results show that the T m value obtained by MX method is more suitable for analyzing the regime transition behavior of PPS than that by HW method. And the regime I/II and II/III transitions can be really observed at T X = 526 and T X = 516 K, respectively, while analyzing the secondary nucleation theory of PPS by use of the T m value obtained by MX method.

Thermal behavior of syndiotactic E-1,2-poly(3-methyl-1,3-pentadiene)

Syndiotactic E-1,2-poly(3-methyl-1,3-pentadiene) was synthesized with the catalyst system Fe(bipy) 2Cl 2-MAO. The thermal stability and kinetic parameters of degradation were determined by thermogravimetric analysis. The isothermal crystallization kinetics were described by means of the Avrami equation, which suggested a three-dimensional growth of crystalline units, developed by heterogeneous nucleation, followed by a secondary crystallization stage. Syndiotactic E-1,2-poly(3-methyl-1,3-pentadiene) isothermally crystallizes from the melt according to regime II of crystallization described by Lauritzen–Hoffman secondary nucleation theory. Non-isothermal crystallization kinetics were elaborated using different approaches. The equilibrium melting temperature was calculated. The kinetic and thermodynamic data were compared with those obtained from syndiotactic 1,2-poly(1,3-butadiene), which is the first example of 1,2 polydienes family.

Effects of metal ion-carbonyl interaction on miscibility and crystallization kinetic of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)/lightly ionized PBS

Poly(butylene succinate) (PBS) and PBS-based ionomers (PBSi) with 1.0 and 3.0mol% sodium sulfonate ionic group were synthesized and blended with poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHB-HHx) via direct melt compounding. FT-IR analysis demonstrated that the sodium metal ion–carbonyl interaction between PHB-HHx and PBS ionomer increased in strength with the ionic group concentration. Both non-isothermal and isothermal analyses showed the crystallization rates of PHB-HHx to decrease as the strength of the sodium metal ion–carbonyl interaction increased. However, the constant value obtained for the Avrami exponent indicated that the presence of PBS ionomer did not interfere in any way with the nucleation mechanism or the geometry of the crystal growth of PHB-HHx. DMTA analysis confirmed that PBS ionomer reduced the crystallinity of PHB-HHx, and this phenomenon increased in proportion to the ionic group content. As the ionic group concentration increased, the sodium metal–carbonyl interaction between PHB-HHx and PBS ionomer became much stronger, resulting in the improvement of the miscibility for the blend. The interaction parameter obtained by analyzing the equilibrium melting temperature was negative for all bend systems, with the ionomer having ionic group content, displaying a more negative value. Based on the Lauritzen–Hoffman secondary nucleation theory, the regime of the PHB-HHx/PBS ionomer blend remained unchanged throughout the crystallization process. In addition, both the nucleation constant and surface free energy were found to decrease as both ionomer content and ionic group concentration increased.

Crystallization and melting behavior of 1,2‐syndiotactic polybutadiene

Abstract1,2‐Syndiotactic polybutadiene was synthesized at −30°C using the catalyst system CrCl2(dmpe)2‐MAO. The syndiotactic index of the butadiene sequences, expressed as a percentage of syndiotactic pentads [rrrr], was evaluated by 13C‐NMR measurements. WAXD and SAXS techniques were employed to characterize the crystalline structure of the polymer. The thermal behavior of the polybutadiene was investigated by differential scanning calorimetry. The isothermal crystallization kinetics were described by means of the Avrami equation, which suggested a three‐dimensional growth of crystalline units, developed by heterogeneous nucleation, followed by a secondary crystallization stage. Polybutadiene isothermally crystallizes from the melt according to regime II of crystallization described by Lauritzen–Hoffman secondary nucleation theory. Nonisothermal crystallization kinetics were elaborated using the Ziabicki and Avrami methods modified by Jeziorny. The equilibrium melting temperature was calculated. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1680–1687, 2004

Determination of the equilibrium melting point of the β-form of polypropylene

The melting behavior of the β-form of isotactic polypropylene (β-iPP) was investigated as a function of crystallization time and temperature. Calcium suberate, a selective β-nucleating agent was used to produce samples that consist entirely of β-form i-PP. The experimental melting points were recorded at different crystallization times and were extrapolated to the start of the crystallization process in order to eliminate the effect of lamellar thickening. Using the non-linear Hoffman—Weeks approach to correlate these extrapolated experimental melting temperatures with the corresponding crystallization temperatures, an equilibrium melting point of 209°C was obtained for β-iPP. The equilibrium melting point estimated through the non-linear Hoffman—Weeks analysis is about 30°C higher than that (Tm0=177°C) obtained on the basis of the linear extrapolation. These results are consistent with earlier claims that a linear extrapolation of Tm−Tc data leads to an underestimation of the equilibrium melting point. The results obtained for β-iPP exemplify the importance of accounting for both the isothermal lamellar thickening effects and the non-linearity in the Tm−Tc correlation, when the determination of an equilibrium melting point is carried out using a procedure based on the predictions of the Lauritzen—Hoffman secondary nucleation theory.