scholarly journals New Insights into Crystallization of Heterophasic Isotactic Polypropylene by Fast Scanning Chip Calorimetry

Polymers ◽  
2020 ◽  
Vol 12 (8) ◽  
pp. 1683
Author(s):  
Daniela Mileva ◽  
Jingbo Wang ◽  
Markus Gahleitner ◽  
Katalee Jariyavidyanont ◽  
René Androsch
Keyword(s):  
Crystallization Kinetics ◽  
Isotactic Polypropylene ◽  
Crystallization Rate ◽  
Crystal Nucleation ◽  
Crystallization Time ◽  
Chip Calorimetry ◽  
The Matrix ◽  
Homogeneous Crystal ◽  
Kinetics Of ◽  
Fast Scanning Chip Calorimetry

The crystallization kinetics of metallocene-catalyzed heterophasic isotactic polypropylene composed of a matrix of isotactic polypropylene (iPP) and rubbery particles made of random ethylene–propylene copolymers (EPC), often denoted as heterophasic iPP copolymers, was analyzed as a function of the cooling rate and supercooling in nonisothermal and isothermal crystallization experiments, respectively. Fast scanning chip calorimetry (FSC) allowed assessing crystallization at processing-relevant conditions, and variation of the content (0–39 wt %) and composition (0–35 wt % propylene counits) of the EPC particles revealed qualitatively new insight about mechanisms of heterogeneous crystal nucleation. For neat iPP homopolymer, the characteristic bimodal temperature dependence of the crystallization rate due to predominance of heterogeneous and homogeneous crystal nucleation at high and low temperatures, respectively, is reconfirmed. At high temperatures, in heterophasic iPP, the here studied ethylene-(C2)-rich EPC particles accelerate crystallization of the iPP-matrix, with the acceleration or nucleation efficacy correlating with the EPC-particle content. The crystallization time reduces by more than half in presence of 39 wt % EPC particles. An additional nucleating effect of the EPC particles on iPP-matrix crystallization is detected after their crystallization, suggesting that liquid/rubbery particles are less effective than solid/semicrystalline particles in affecting crystallization of the surrounding iPP-matrix. At low temperature, homogeneous crystal nucleation in the iPP-matrix outpaces all heterogeneous nucleation effects, and the matrix-crystallization rate is independent of the sample composition. The obtained results lead to the conclusion that the crystallization kinetics of iPP can be affected significantly by the content and composition of EPC particles, even towards superfast crystallizing iPP grades.

scholarly journals Fast-Scanning Chip-Calorimetry Measurement of Crystallization Kinetics of Poly(Glycolic Acid)

Polymers ◽  
2021 ◽  
Vol 13 (6) ◽  
pp. 891
Author(s):  
Yongxuan Chen ◽  
Kefeng Xie ◽  
Yucheng He ◽  
Wenbing Hu
Keyword(s):  
Crystallization Kinetics ◽  
Temperature Region ◽  
Glycolic Acid ◽  
Crystal Nucleation ◽  
Side Group ◽  
Half Time ◽  
Temperature Range ◽  
Chip Calorimetry ◽  
Kinetics Of ◽  
Fast Scanning Chip Calorimetry

We report fast-scanning chip-calorimetry measurement of isothermal crystallization kinetics of poly(glycolic acid) (PGA) in a broad temperature range. We observed that PGA crystallization could be suppressed by cooling rates beyond -100 K s−1 and, after fast cooling, by heating rates beyond 50 K s-1. In addition, the parabolic curve of crystallization half-time versus crystallization temperature shows that PGA crystallizes the fastest at 130 °C with the minimum crystallization half-time of 4.28 s. We compared our results to those of poly(L-lactic acid) (PLLA) with nearby molecular weights previously reported by Androsch et al. We found that PGA crystallizes generally more quickly than PLLA. In comparison to PLLA, PGA has a much smaller hydrogen side group than the methyl side group in PLLA; therefore, crystal nucleation is favored by the higher molecular mobility of PGA in the low temperature region as well as by the denser molecular packing of PGA in the high temperature region, and the two factors together decide the higher crystallization rates of PGA in the whole temperature range.

Effect of Hyperbranched Polymer on Crystallization Kinetics of Isotactic Polypropylene

2012 ◽  
Vol 535-537 ◽  
pp. 1142-1145
Author(s):  
Guang Tian Liu ◽  
Jing Lei
Keyword(s):  
Activation Energy ◽  
Crystallization Kinetics ◽  
Isotactic Polypropylene ◽  
Isothermal Crystallization ◽  
Hyperbranched Polymer ◽  
Crystallization Rate ◽  
Crystallization Activation Energy ◽  
Scanning Calorimetry ◽  
Isothermal Crystallization Kinetics ◽  
Kinetics Of

In this paper, the isothermal crystallization kinetics of isotactic polypropylene (iPP) and iPP with 5% hyperbranched polymer (HBP) added had been investigated by differential scanning calorimetry (DSC). The results show that a small addition of HBP affects the crystallization behavior of iPP. During isothermal crystallization, the crystallization rate of the blend is higher than those of iPP remarkably. An increase in the Avrami exponent may be attributed to the fractal structure of hyperbranched polymer. The crystallization activation energy is estimated by the Friedman equation, the results show that the activation energy decreases remarkably by addition of HBP and the crystallization rate of the blend is more sensitive to temperature than that of iPP.

Isothermal Crystallization Kinetics of Polypropylene and Hyperbranched Polyester Blends

2011 ◽  
Vol 396-398 ◽  
pp. 1688-1691
Author(s):  
Qing Chun Fan ◽  
Fei Hong Duan ◽  
Huai Bing Guo ◽  
Tian Wu
Keyword(s):  
Crystallization Kinetics ◽  
Isothermal Crystallization ◽  
Crystallization Rate ◽  
Nucleating Agent ◽  
Interfacial Free Energy ◽  
Crystallization Time ◽  
Hyperbranched Polyester ◽  
Isothermal Crystallization Kinetics ◽  
Half Crystallization Time ◽  
Kinetics Of

The isothermal crystallization kinetics of PP with different contents of AB2 hyperbranched polyester(HBP) added has been investigated. The results show that HBP acts as a nucleating agent for PP, and the hyperbranched polyester can decrease the half crystallization time (t1/2) and increase the crystallization rate of PP greatly. The Avrami exponents of PP and nucleated PP are all close to 2.5. Hoffman theory was adopted to calculate the interfacial free energy per unit area perpendicular to PP chains σe of PP and PP/HBP blends.

scholarly journals Nonisothermal Crystallization Kinetics of Acetylated Bamboo Fiber-Reinforced Polypropylene Composites

Polymers ◽  
2019 ◽  
Vol 11 (6) ◽  
pp. 1078 ◽  
Author(s):  
Yu-Shan Jhu ◽  
Teng-Chun Yang ◽  
Ke-Chang Hung ◽  
Jin-Wei Xu ◽  
Tung-Lin Wu ◽  
...  
Keyword(s):  
Crystal Growth ◽  
Crystallization Kinetics ◽  
Crystallization Rate ◽  
Bamboo Fiber ◽  
Crystallization Time ◽  
Nucleation Agent ◽  
Relative Crystallinity ◽  
Crystallinity Degree ◽  
Friedman Method ◽  
Kinetics Of

The crystallization behavior of bamboo fiber (BF) reinforced polypropylene (PP) composites (BPCs) was investigated using a differential scanning calorimeter (DSC). The results showed that unmodified BF as a nucleation agent accelerated the crystallization rate of the PP matrix during cooling whereas there is no significant effect on the improved crystallization rate in BPCs with acetylated BFs. Based on the Avrami method, Avrami–Ozawa method, and Friedman method, the corresponding crystallization kinetics of PP reinforced with different acetylation levels of BFs were further analyzed. The results demonstrated that the crystal growth mechanism of the PP matrix for BPCs with unmodified and various acetylated BFs exhibited tabular crystal growth with heterogeneous nucleation. A higher cooling rate is required to achieve a certain relative crystallinity degree at the unit crystallization time for BPCs with a higher weight percent gain (WPG) of acetylated BFs (WPG >13%). Furthermore, based on the Friedman method, the lowest crystallization activation energy was observed for the BPCs with 19% WPG of acetylated BFs.

scholarly journals Crystallization of Long-Spaced Precision Polyacetals III: Polymorphism and Crystallization Kinetics of Even Polyacetals Spaced by 6 to 26 Methylenes

Polymers ◽  
2021 ◽  
Vol 13 (10) ◽  
pp. 1560
Author(s):  
Stephanie F. Marxsen ◽  
Manuel Häußler ◽  
Stefan Mecking ◽  
Rufina G. Alamo
Keyword(s):  
Crystallization Kinetics ◽  
Crystallization Rate ◽  
Polymorphic Transition ◽  
Heat Of Fusion ◽  
Sequence Length ◽  
Crystallization Time ◽  
Scanning Calorimetry ◽  
Disordered Structures ◽  
Methylene Groups ◽  
Kinetics Of

In this paper we extend the study of polymorphism and crystallization kinetics of aliphatic polyacetals to include shorter (PA-6) and longer (PA-26) methylene lengths in a series of even long-spaced systems. On a deep quenching to 0 °C, the longest even polyacetals, PA-18 and PA-26, develop mesomorphic-like disordered structures which, on heating, transform progressively to hexagonal, Form I, and Form II crystallites. Shorter polyacetals, such as PA-6 and PA-12 cannot bypass the formation of Form I. In these systems a mixture of this form and disordered structures develops even under fast deep quenching. A prediction from melting points that Form II will not develop in polyacetals with eight or fewer methylene groups between consecutive acetals was further corroborated with data for PA-6. The temperature coefficient of the overall crystallization rate of the two highest temperature polymorphs, Form I and Form II, was analyzed from the differential scanning calorimetry (DSC) peak crystallization times. The crystallization rate of Form II shows a deep inversion at temperatures approaching the polymorphic transition region from above. The new data on PA-26 confirm that at the minimum rate the heat of fusion is so low that crystallization becomes basically extinguished. The rate inversion and dramatic drop in the heat of fusion irrespective of crystallization time are associated with a competition in nucleation between Forms I and II. The latter is due to large differences in nucleation barriers between these two phases. As PA-6 does not develop Form II, the rate data of this polyacetal display a continuous temperature gradient. The data of the extended polyacetal series demonstrate the important role of methylene sequence length on polymorphism and crystallization kinetics.

Crystallization Kinetics in Isotactic Polypropylene Films with Carbon Nanotubes

2011 ◽  
Vol 1312 ◽  
Author(s):  
Georgi Georgiev ◽  
Scott Schoen ◽  
Devin Ivy ◽  
Lauren Wielgus ◽  
Yaniel Cabrera ◽  
...  
Keyword(s):  
Carbon Nanotubes ◽  
Crystallization Kinetics ◽  
Isotactic Polypropylene ◽  
Crystallization Rate ◽  
Crystal Nucleation ◽  
Commercial Application ◽  
Peak Time ◽  
Slight Variation ◽  
Scanning Calorimetry ◽  
Avrami Analysis

ABSTRACTPolymer nanocomposites are the largest commercial application for carbon nanotubes (CNTs) which determines the interest in their effect on crystallization processes of polymers. We chose Isotactic Polypropylene (iPP) as one of the most widely used polymers. Nanocomposites with multiwall carbon nanotubes (MWCNTs) 0-5% by weight were studied, using differential scanning Calorimetry to measure the crystal nucleation and kinetics effects of MWCNTs. Isothermal crystallization at 138°C was performed and the data were analyzed using Avrami analysis. We obtained results for the effect of MWCNTs on the crystallization kinetics. The Avrami analysis showed a dramatic increase in the crystallization rate constant and constancy of the Avrami exponent with increase of the CNTs concentration. The full width at half maximum (FWHM) of the heat flow exotherm and the peak time for crystallization (tp) change dramatically. The crystallinity shows a slight variation with the CNTs concentration dipping at 2% CNTs which can be explored further at higher concentrations.

scholarly journals Isothermal Crystallization Kinetics of Poly(ethylene oxide)/Poly(ethylene glycol)-g-silica Nanocomposites

Polymers ◽  
2021 ◽  
Vol 13 (4) ◽  
pp. 648
Author(s):  
Xiangning Wen ◽  
Yunlan Su ◽  
Shaofan Li ◽  
Weilong Ju ◽  
Dujin Wang
Keyword(s):  
Molecular Weight ◽  
Ethylene Oxide ◽  
Crystallization Kinetics ◽  
Isothermal Crystallization ◽  
Crystallization Rate ◽  
Poly Ethylene Glycol ◽  
Isothermal Crystallization Kinetics ◽  
Poly Ethylene Oxide ◽  
Poly Ethylene ◽  
Kinetics Of

In this work, the crystallization kinetics of poly(ethylene oxide) (PEO) matrix included with poly(ethylene glycol) (PEG) grafted silica (PEG-g-SiO2) nanoparticles and bare SiO2 were systematically investigated by differential scanning calorimetry (DSC) and polarized light optical microscopy (PLOM) method. PEG-g-SiO2 can significantly increase the crystallinity and crystallization temperature of PEO matrix under the non-isothermal crystallization process. Pronounced effects of PEG-g-SiO2 on the crystalline morphology and crystallization rate of PEO were further characterized by employing spherulitic morphological observation and isothermal crystallization kinetics analysis. In contrast to the bare SiO2, PEG-g-SiO2 can be well dispersed in PEO matrix at low P/N (P: Molecular weight of matrix chains, N: Molecular weight of grafted chains), which is a key factor to enhance the primary nucleation rate. In particular, we found that the addition of PEG-g-SiO2 slows the spherulitic growth fronts compared to the neat PEO. It is speculated that the interfacial structure of the grafted PEG plays a key role in the formation of nuclei sites, thus ultimately determines the crystallization behavior of PEO PNCs and enhances the overall crystallization rate of the PEO nanocomposites.

Non-Isothermal Crystallization Kinetics of Graphene Oxide-Carbon Nanotubes Hybrids / Polyamide 6 Composites

2019 ◽  
Vol 41 (3) ◽  
pp. 394-394
Author(s):  
Zhi Qiang Wang Zhi Qiang Wang ◽  
Yong Ke Zhao and Xiang Feng Wu Yong Ke Zhao and Xiang Feng Wu
Keyword(s):  
Carbon Nanotubes ◽  
Graphene Oxide ◽  
Cooling Rate ◽  
Crystallization Kinetics ◽  
Isothermal Crystallization ◽  
Crystallization Rate ◽  
Polyamide 6 ◽  
Degree Of Crystallinity ◽  
Isothermal Crystallization Kinetics ◽  
Kinetics Of

The hybrids combined by nano-materials with different dimensions usually possess much better enhancement effects than single one. Graphene oxide-carbon nanotubes hybrids / polyamide 6 composites has been fabricated. The non-isothermal crystallization kinetics of the as-prepared samples was discussed. Research results showed that increasing the cooling rate was in favor of increasing the crystallization rate and the degree of crystallinity for the as-prepared samples. Moreover, the crystallization rate was first decreased and then increased with increasing the hybrids loading. Furthermore, the crystallization mechanism was changed with increasing the crystallization temperature and the cooling rate. The nucleation and growth modes of the non-isothermal crystallization could be classified into three different types, according to the Ozawa’s theory. These complicated results could be attributed to the important role of crystallization rate as well as the simultaneous hindering and promoting effects of the as-prepared hybrids. This work has reference values for understanding the crystallization kinetics of the polyamide 6-based composites.

Kinetics of crystallization for polypropylene/polyethylene/halloysite nanotube nanocomposites

2018 ◽  
Vol 33 (4) ◽  
pp. 451-463 ◽  
Author(s):  
MY Ong ◽  
WS Chow
Keyword(s):  
Crystallization Rate ◽  
Avrami Equation ◽  
Crystallization Time ◽  
Halloysite Nanotube ◽  
Kissinger Equation ◽  
Polyethylene Blends ◽  
Instantaneous Nucleation ◽  
Half Crystallization Time ◽  
T Values ◽  
Kinetics Of

The aim of this study is to investigate the kinetics of non-isothermal crystallization of polypropylene/high-density polyethylene/halloysite nanotube (PP/HDPE/HNT) nanocomposites using three methods, that is, Avrami equation, combined Ozawa–Avrami method (hereafter called Mo model), and Kissinger equation. The Avrami exponent ( n) is in the range of 1–2 for all the PP/HDPE/HNT nanocomposites indicating instantaneous nucleation while the crystallization rate constant ( Zt) values of PP/HDPE increased with the addition of HNT. This proved that addition of HNT increases the crystallization rate. The reduction of half crystallization time ( t 1/2) for PP/HDPE as the increasing HNT loading indicates faster crystallization rate. In the Mo model, the cooling rate chosen at unit crystallization time F( T) values for PP/HDPE decreases with the addition of HNT. Kissinger equation showed that the activation energy ( E a) of crystallization for the PP/HDPE decreases with the addition of HNT. All the results demonstrated that HNT can accelerate the crystallization rate for the PP/polyethylene blends.

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