Non-isothermal Crystallization Research Articles

Effect of the synergistic interaction of zinc adipate, hydrotalcite and ethylene propylene rubber on the performances of polypropylene

Polypropylene (PP) is widely used in a range of areas due to its excellent physical and chemical properties, but its low-temperature brittleness and low-impact resistance largely limits its application. Hence, this study investigated the changes in mechanical and thermal properties of isotactic polypropylene (iPP) modified by the addition of the β-nucleating agent zinc adipate (ZnAA), the inorganic rigid particle hydrotalcite (HT), and the rubber elastomer bipropylene rubber (EPR). The structure and properties of modified PP were investigated by Fourier transform infrared (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), electronic universal material testing machine, and simple-beam impact testing machine. At last, the non-isothermal crystallization kinetics of iPP was investigated by the Caze method. It was found that with the addition of EPR reached 30 wt%, the notched impact strength of iPP was 34.74 kJ/m2, which was 542.43 % higher than that of pure iPP, and more than twice as high as that of ZnAA and HT modification, and the relative crystallinity ( K β) value of the β-crystalline form reached 79.66 % when 10 wt% EPR was added to the iPP. The addition of ZnAA, HT and EPR could significantly increase the crystallisation peak temperature ( T c), shorten the half-crystallisation time ( t 1/2) and increase the crystallisation activation energy ( ΔE) of iPP.

Synergistic Effects of Polyethylene Glycol and Cellulose Nanofibers on the Isothermal and Non-isothermal Crystallization Behaviors of Polylactide

Synergistic Effects of Polyethylene Glycol and Cellulose Nanofibers on the Isothermal and Non-isothermal Crystallization Behaviors of Polylactide

An Improved Mampel Model of the Non-Isothermal Crystallization Kinetics of Fiber-Reinforced Thermoplastic Composites.

Fiber-reinforced thermoplastic composites (FRTPs) are gaining increasing attention and widespread use in engineering applications due to their high specific strength and stiffness, excellent toughness, and recyclability. The mechanical properties of these composites are closely tied to their crystallization process, making it crucial to accurately describe this phenomenon. Existing theoretical models for analyzing the non-isothermal crystallization of thermoplastic composites often face challenges relating to the complexity of obtaining multiple parameters and the difficulty of achieving a final relative crystallinity of 1. To address these issues, this paper introduces a novel functional form of the crystallization rate parameter K(T), tailored for engineering applications, and proposes an improved Mampel model. This model assumes K(T) to be zero before the onset of crystallization and also to be linearly dependent on temperature thereafter, ensuring that the final relative crystallinity reaches 1. The model requires only two easily accessible parameters: the initial crystallization temperature (Ts) and the linear slope (k). The simplicity of the model makes it particularly well suited to engineering applications. This provides a straightforward and effective tool for describing the non-isothermal crystallization kinetics of fiber-reinforced thermoplastic composites.

Liquid state properties and amorphous solidification kinetics of multicomponent Fe_{50-x}Co_{x}Cr_{14}Mo_{14}C_{9}B_{8}Tm_{5} alloys investigated under containerless processing conditions.

The liquid state thermophysical properties and amorphous solidification kinetics of Fe_{50-x}Co_{x}Cr_{14}Mo_{14}C_{9}B_{8}Tm_{5} (x=10, 15, 20, and 25) alloys were explored by electromagnetic and electrostatic levitation techniques. It was found that the surface tension of liquid alloys with Fe contents below 30 at.% had a strong temperature dependence. The high surface tension led to a sharp increase in the interfacial free-energy penalty. A high nucleation barrier was formed inside the melt, which greatly inhibited the nucleation rate. The liquid viscosity revealed the strong liquid feature of this alloy series, which became the dominant kinetic factor determining their solidification mechanisms. The high viscosity hindered atomic diffusion and delayed nucleation. The long crystallizing incubation time of Fe_{30}Co_{20}Cr_{14}Mo_{14}C_{9}B_{8}Tm_{5} ensured a strong glass-forming ability and a low critical cooling rate of 2.11×10^{3}Ks^{-1}. As a result, a bulk metallic glass rod with an 8-mm diameter was successfully prepared by a convenient casting procedure. This rod could remain in a glassy state at a higher temperature and over a wider temperature range due to its high glass-transition temperature and large undercooled liquid region. The apparent activation energy for nucleation was derived as 463.8 kJmol^{-1} according to the nonisothermal crystallization kinetics, indicating that the bulk metallic glass had to absorb a large amount of energy to overcome the potential barriers before nucleation and thus exhibited excellent thermal stability.

Non-isothermal crystallization kinetics and activation energy modeling of carbon nanotubes dispersed high-density polyethylene and polypropylene blends

The study presents the effect of the reinforcement of carbon nanotubes (CNT) into high-density polyethylene (HDPE) and polypropylene (PP) blends. The Avrami exponent of CNT blends ranges within the 1.3–1.6 range. It demonstrates the 3D growth of crystals and nucleation activity during crystallization. The change in the Ozawa exponent indicates a two-stage crystallization process. The values of the Mo exponent show that the nucleation activity is affected by changing temperatures during the cooling process and the formation of high-quality crystal growth. The activation energy of the HDPE/PP matrix is 420.5 kJ/mol and adding 1.5% CNT resulted in 369.9 kJ/mol for Run-3. The polymer chains encounter difficulties in transitioning during the cooling process and release a significant amount of energy. The composition of the nanofiller in the blend affects the nucleation activity of the crystals. The permeability of the pure HDPE/PP sample obtained from sorption studies is 1.05 × 10−5 m2/s and adding 1.5% CNT in Run-3 provides a permeability of 5.2 × 10−5 m2/s. The CNT has a homogeneous dispersion in the matrix to form a net-like morphology. The crystallinity index calculated using the Seagal method for HDPE/PP, Run-3, Run-4 and Run-5 is 75%, 75.8%, 77.34% and 78%, respectively.

Solid–liquid equilibria and non-isothermal crystallization kinetics of n-alkanes binary systems

Solid–liquid equilibria and non-isothermal crystallization kinetics of n-alkanes binary systems

Crystallization path and non-isothermal kinetics of the Zr59.5Cu14.4Ni11.6Al9.7Nb4.8 metallic glass under different heating rates

In this work, the crystallization path and non-isothermal kinetics upon heating of the Zr59.5Cu14.4Ni11.6Al9.7Nb4.8 metallic glass were investigated. The devitrification process consists the formation of phases in the sequence of icosahedral quasicrystal (IQ) phase, Ni-containing phases, and Cu-containing phases. Avrami exponents were calculated at various heating rates, providing insights into the non-isothermal crystallization kinetics. The IQ phase and Ni-containing phases are interface-controlled growth, while the Cu-containing phases are diffusion-controlled growth. In addition, a continuous heating transition (CHT) diagram with a heating rate range exceeding six orders of magnitude was constructed, and the crystallization mechanism under different heating rates was revealed. These findings enrich the understanding of crystallization path and kinetics of metallic glass.

Deciphering the role of FI catalyst’s C3 substituent on the non-isothermal crystallization kinetics of nascent disentangled UHMWPE

UH1 - UH4 were accessed using tetra-fluorinated phenoxy-imine catalysts (FI catalysts) with linear (allyl, n-propyl, 1-propenyl) or more steric demanding (isopropyl) C3 substituents ortho to the phenoxy-oxygen atom. To get a better understanding of the non-isothermal crystallization kinetics of these nascent ultra-high molecular weight polyethylenes (UHMWPEs), their thermo-rheological properties are investigated. Through the application of annealing-crystallization-melting thermal analysis and isoconversional method, it is verified that the samples are nascent disentangled UHMWPEs with higher crystallization rates compared to the commercial UHMWPE (CUH). The molar fraction of nascent entangled crystals and/or degree of supercooling have a significant influence on the non-isothermal crystallization kinetics of nascent disentangled UHMWPEs. Finally, under a lower supercooling, the electron-donating property and steric hindrance of C3 substituent strongly affect the synthesis and architecture of polyolefin which in turn has a specific non-isothermal crystallization kinetics.

Effects of molecular structure and temperature field on the crystallization behavior of poly(tetrafluoroethylene-co-perfluoroalkylvinyl ether)

Despite the wide industrial application of poly(tetrafluoroethylene-co-perfluoroalkylvinyl ether) (PFA) in semiconductor processing, its crystallization behavior has little been studied. In this work, three PFA resins with similar molecular weight but different comonomer content and distribution were synthetized. Then the non-isothermal crystallization kinetics and crystalline structures were studied by differential scanning calorimetry, polarizing optical microscopy, and X-ray diffraction systematically. It is found that the incorporation of comonomers destroys the chain regularity and reduces the crystallizability of PFA thermodynamically, while the comonomer insertion improves the chain flexibility to accelerate the crystal growth dynamically. When the comonomer content of PFA is low, both the nucleation and growth rates are quite fast, which is favorable for the formation of spherulite. As the comonomer content increases or distribute uniformly in the chain, the nucleation rate declines notably and the side groups distort the crystal cell to increase the spacing of [100] plane. Moreover, two-dimensional growth mode is dominant to form bundle-like structure when crystallizing at slow cooling, where nucleation is suppressed by growth. But three-dimensional symmetrical spherulite can be activated and perfected at high cooling rate due to the initiation of substantial nucleation sites. This unique crystallization behavior is opposite to that of conventional polymers, providing a guidance for the polymerization and processing of PFA.

An assessment of the mechanically alloyed equiatomic FeCoNiMnSi high entropy amorphous alloy for non-isothermal crystallization kinetics and magnetocaloric refrigeration application

We studied an equiatomic FeCoNiMnSi high entropy amorphous alloy successfully processed via mechanical alloying technique. The structural, magnetic, and magnetocaloric characteristics of the resulting materials were examined using X-ray diffraction, field emission scanning electron microscopy, high-resolution transmission electron microscopy, and a vibrating sample magnetometer. The structural analysis showed a prominent amorphous phase formation as the milling time increases from t = 0–35h of mechanical alloying. The differential scanning calorimetry was employed to investigate the non-isothermal crystallization kinetics of the 35-h milled sample. The results revealed that the milled powder consists of a single exothermic peak with its apparent activation energy (Eg, Ex, Ep) being determined using the Kissinger, Ozawa, and Augis-Bennett equations. The findings exhibit Ex > Ep > Eg, representing that nucleation is more complicated than the growth mechanism during the crystallization process. Meanwhile, under non-isothermal conditions, the Kissinger-Akahira-Sunose, Friedman, and Flynn-Wall-Ozawa models were calculated using the local activation energies that agree with the apparent activation energy. Furthermore, the Johson-Mehl-Avrami-Kolmogorov exponent (n) and Avrami-Ozawa combined [F(T)] models exhibit high-dimensional nucleation and growth with an increasing nucleation rate enabled by lowering the local activation energies as a function of degree of conversion with respect to temperature. In magnetic measurements, a feasible mathematical model was proposed as a novel strategy for predicting the value of saturation magnetization as a milling time function. The model has an exceptional predictive capability, confirmed by fitting other research outcomes. Finally, the proposed system also delivers the best magnetocaloric properties with a maximum magnetic entropy change of 3.70 Jkg−1 K−1 at 150 K curie temperature and a refrigeration capacity of 252.86 J/kg with 1000 Oe applied magnetic field.

Crystallization Kinetics and Melting Behavior of Novel Biobased Poly(butylene 2,5‐thiophenedicarboxylate)

AbstractPoly(butylene 2,5‐thiophenedicarboxylate) (PBTh) is a novel biobased semicrystalline polyester with superior thermal, mechanical, and gas barrier properties; however, the crystallization kinetics and melting behavior of PBTh have not been studied in detail so far. The crystallization kinetics of PBTh was first studied in this research. The Ozawa equation failed to describe the nonisothermal melt crystallization kinetics of PBTh due to the secondary crystallization. The crystallization activation energy value was calculated by the Friedman method, which was negative and exhibited the conversion dependence. The isothermal melt crystallization kinetics of PBTh was well described by the Avrami equation in a wide range of crystallization temperature from 84 to 120 °C. PBTh showed the fastest crystallization rate at 104 °C; moreover, the Avrami exponent value slightly varied between 2.2 and 2.7, suggesting the same crystallization mechanism within the investigated temperature range. PBTh displayed one or two melting endotherms depending on crystallization temperature, which was well explained by the melting, recrystallization, and remelting mechanism. In addition, the equilibrium melting point of PBTh was estimated to be 163.1 °C with the Hoffmann−Weeks equation.

Non-isothermal crystallization kinetics of biocomposites based on PLA/PHBV and spent coffee grounds

AbstractThis study deals with the modification of a predominantly amorphous poly(lactic acid) (PLA) by blending it with a semi-crystalline biopolymer, polyhydroxybutyrate-co-valerate (PHBV), which has a high crystallinity. The blends with different concentrations of PLA and PHBV were compounded with spent coffee grounds (SCGs) and processed by injection moulding. The structural, thermal and mechanical properties of the produced samples were investigated. Particular attention was paid to the effect of the presence of SCG and the concentration of PHBV in the blend on the crystallization kinetics and the heat deflection temperature (HDT). For equimolar blends, only a slight increase in HDT (about 5 °C) was observed, but the addition of PHBV suppressed the cold crystallization of PLA, which otherwise negatively affects the dimensional stability of injection moulded parts. A similar effect, but to a lesser extent, was achieved by adding SCG to the PLA matrix. Thus, it is clear that the material structures of PLA/PHBV blends and composites help to minimize additional shrinkage of the parts and increase their dimensional stability. Due to the co-continuous structure of the symmetric PLA/PHBV blends and the increase in the degree of crystallinity from 36 to 47% by annealing the produced samples, the heat deflection temperature increased from 65 up to 90 °C.

Synergistic effect of TiO2 nanoparticles and poly (ethylene-co-vinyl acetate) on the morphology and crystallization behavior of polylactic acid

The impact of adding ethylene vinyl acetate copolymer (EVA 80) and 1 wt% TiO2 nanoparticles on the morphology and crystallization behavior of poly(lactic acid) blends was investigated using DSC, SEM, and POM. Thermal analysis revealed the enhancement of crystallinity of PLA in the presence of TiO2 and higher EVA 80 content in the blend. The PLA and EVA 80 components showed compatibility, as evidenced by the shift of the glass transition temperatures of the PLA phase in the blend to lower values compared to neat PLA. The lower temperature shift of the cold crystallization of the PLA and the formation of the small spherulites of the PLA in the blends indicated that the EVA 80 and TiO2 act as a nucleating agent for crystallization. The non-isothermal crystallization parameters of the composites were evaluated using Avrami's modified model, the MO approach, and Friedman’s isoconversional method. The Avrami’s modified rate constant (K) and the effective activation energy values significantly increased with the incorporation of EVA 80 and TiO2 nanoparticles. Furthermore, the thermogravimetric analysis (TGA) showed improved thermal stability of PLA by adding EVA 80 and TiO2.

The Effect of Polyethylene Glycol on the Non-Isothermal Crystallization of Poly(L-lactide) and Poly(D-lactide) Blends.

The formation of polylactide stereocomplex (sc-PLA), involving the blending of poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA), enhances PLA materials by making them stronger and more heat-resistant. This study investigated the competitive crystallization behavior of homocrystals (HCs) and stereocomplex crystals (SCs) in a 50/50 PLLA/PDLA blend with added polyethylene glycol (PEG). PEG, with molecular weights of 400 g/mol and 35,000 g/mol, was incorporated at concentrations ranging from 5% to 20% by weight. Differential scanning calorimetry (DSC) analysis revealed that PEG increased the crystallization temperature, promoted SC formation, and inhibited HC formation. PEG also acted as a plasticizer, lowering both melting and crystallization temperatures. The second heating DSC curve showed that the pure PLLA/PDLA blend had a 57.1% fraction of SC while adding 5% PEG with a molecular weight of 400 g/mol resulted in complete SC formation. In contrast, PEG with a molecular weight of 35,000 g/mol was less effective, allowing some HC formation. Additionally, PEG consistently promoted SC formation across various cooling rates (2, 5, 10, or 20 °C/min), demonstrating a robust influence under different conditions.

Crystallinity and rheological behavior of polyetheretherketone during nonisothermal conditions

AbstractSolidification models are key during simulation of several industrial processes involving thermoplastics. For simplicity, crystallinity is often not considered within these models, despite it being responsible for the phase transition. Several advanced methods, which consider crystallinity as the onset of solidification have been proposed in literature however, these have primarily been applied to classical homopolymers such as polypropylene (PP). The focus of this study is to develop a model that can capture the rheological response observed during the transition from liquid‐like to solid‐like behavior in injection molding grade polyetheretherketone (PEEK) due to crystallinity. Isothermal rheological experiments are performed alongside dynamic scanning calorimetry (DSC) characterization to correlate relative crystallinity to the apparent increase in viscosity. The model is extended to nonisothermal processes through the incorporation of the Nakamura model. Nonisothermal crystallization rheology experiments are performed and compared with a simulation of the oscillating rheometer process for validation. The modeled viscosity response and crystallization half‐time reproduced the experimental data with sufficient accuracy at low cooling rates, with an error of less than 5% up to cooling rates of 20°C min−1. This shows that the method is an accurate means of obtaining the rheological response during crystallization in a numerical simulation.

Non-isothermal crystallization behavior of Cr50Fe6Co7Mo14C15B6Y2 metallic glass with super high content of Cr and integrated merits

In present work, non-isothermal crystallization behavior for novel Cr50Fe6Co7Mo14C15B6Y2 metallic glass (MG) with super high content of Cr and excellent merits was investigated by differential scanning calorimeter and X-ray diffraction. Both of the Kissinger and Ozawa methods show that the present glass transition is much harder than other transitions for a much larger apparent activation energy (E). While, the growth process of present second crystallization event is the easiest process, since it possesses the smallest E. Meanwhile, the local activation energy established by Kissinger-Akahira-Sunose and Ozawa-Flynn-Wall methods both exhibit a trend of increasing to the maximum value at first and then gradual decrease until the finish of the crystallization, indicating that the difficulty increases until to the maximum at first and then gradually decreases during crystallization. Moreover, all the local Avrami exponent n(x) possesses a value of about 0 <n(x) < 1.5, implying a crystallization with pre-existing nuclei for present non-isothermal crystallization. Furthermore, the glass formation melt of present MG is considered as an intermediate one with moderate thermal stability. Additionally, the alloy firstly changes from monolithic MG to a composite of amorphous matrix superimposed with the main crystalline phases ((Fe,Cr)23(C,B)6, (Cr2.5Fe4.3Mo0.1)C3, Fe3Mo3C, FeC and some unknown phases), and then the remained amorphous matrix thoroughly changes to these crystalline phases with enriched crystal planes and fraction during crystallization. The results can supply basic data for designing valid crystallization strategy to tune performances of metallic glasses with high content of Cr.

The impact of template effect at different temperatures on homocrystallization-to-stereocomplexation transformation in Poly(L-lactide)/Poly(d-lactide) racemic blends

Stereocomplexation, formed between enantiomeric poly(L-lactide) (PLLA) and poly(d-lactide) (PDLA), is 50 °C higher than the melting point of PLLA (or PDLA) homocrystallites (HCs). In a certain temperature range, stereocomplexation can induce homocrystallization-to-stereocomplexation (HC-to-SC) transformation through template effect. In this work, a series of temperature programs designed through differential scanning calorimetry (DSC) were used to study the impact of template effect at different temperatures (TH-S) on HC-to-SC transformation in PLLA/PDLA racemic blends. It was found that HCs can be efficiently converted to stereocomplex crystallites (SCs) through template effect when TH-S was 210 °C. When TH-S was 220 °C, SCs with large lamellar crystal thickness were obtained, which had a higher melting point, about 10 °C higher than the conventional SCs. At a TH-S of 230 °C, the melt-crystallization peaks of HCs and SCs were clearly observed during the DSC cooling process because PLLA/PDLA helical pairs were still retained in the PLLA/PDLA melt. The results demonstrated that the residual PLLA/PDLA helical pairs can accelerate remarkably the crystallization rate of SCs and generated new SCs due to template effect, and the new SCs significantly accelerated the crystallization rate of HCs resulted from the heterogeneous nucleation effect. Non-isothermal crystallization behavior of PLLA/PDLA racemic blends at different cooling rates was also studied. The results indicate that the lower cooling rate promotes SCs formation more strongly than the promotion effect on HCs.

Composition design and crystallization behavior of Zr–Cu–Ni–Al bulk metallic glasses

The Zr–Cu–Ni–Al system was explored in this study, and seven new compositions of Zr-based bulk metallic glasses (BMGs) were designed by combining different proportions of binary eutectic phases Zr38Cu62, Zr76Ni24 and Zr51Al49, and rod-like shape samples were prepared with different diameters using the copper mold casting method. Modifying the proportion coefficient of these eutectic units, the width of the supercooled liquid region was increased from 79 to 95 K, and the thermal stability of the prepared metallic glass was improved. Differential scanning calorimetry was used to investigate the non-isothermal and isothermal crystallization behavior of the prepared samples. Noticeably, there was a small low-temperature exothermic peak before the glass transition temperature Tg in the non-isothermal crystallization process, which was related to the structural relaxation. The crystallization transition activation energy fitted by the Kissinger equation had the same variation trend as that obtained by the Arrhenius equation. Among the four metallic glasses studied, the glassy phase of Zr55·5Cu23·25Ni9Al12.25 was more stable, showing higher glass transition activation energy and longer incubation time. In addition, the isothermal crystallization processes of four metallic glasses were studied according to the Johnson-Mehl-Avrami (JMA) model. The calculated average Avrami exponents were >2.5, indicating that the nucleation rate increased during the isothermal crystallization process.

Chain heterogeneity of poly(lactic acid) and its influence on crystallization kinetics

Temperature rising elution fractionation (TREF) approach was used to separate a biodegradable poly(lactic acid) (PLA) resin into ten fractions and completely establish the relationship between chain microstructure and properties. The main fractions were mainly eluted at 100, 110, 114, and 118 °C, and their mass percentages were 7.98 wt%, 44.83 wt%, 19.64 wt%, and 11.90 wt%, respectively. Through the use of successive self-nucleation/annealing (SSA) thermal fractionation, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and 13C-nuclear magnetic resonance spectroscopy (13C NMR), the intermolecular and intramolecular differences of PLA were further explored. Fractions eluted at 90, 110, 118, and 126 °C were also chosen to research the non-isothermal cold crystallization kinetics, and fractions eluted at 110, 118, and 126 °C were chosen to explore the non-isothermal crystallization kinetics in order to simulate the real process. The findings demonstrated that the Liu-Mo approach were more suited the non-isothermal crystallization and non-isothermal cold crystallization kinetics of PLA. As the elution temperature increased, so did the stereoregularity of the fractions, the crystallization rate, the crystallization capacity, and the lamellar thickness. These will lay a foundation for its basic research and industrial application.

Manipulation of non-isothermal crystallization kinetics of poly(lactic acid) composite film by a novel nucleating agent

As a type of renewable and biodegradable polymer, poly(lactic acid) (PLA) has been widely used in various fields. However, its weak crystallization ability deteriorates the properties of the final product. In this work, a novel nucleating agent (MWCNTs@CeO2), multi-walled carbon nanotubes (MWCNTs) decorated with ceria (CeO2), was synthesized using the hydrothermal method and subsequently used to manipulate the non-isothermal crystallization kinetics and nucleation behavior of PLA. The results show that MWCNTs@CeO2 can act as an effective nucleating agent to accelerate the crystallization rate of PLA by reducing the half-crystallization time. In non-isothermal crystallization kinetics, the Avrami equation modified by Jeziorny cannot accurately describe the non-isothermal crystallization behavior of PLA and PLA/MWCNTs@CeO2 composite films, whereas the Mo method can. Furthermore, it is found that the addition of MWCNTs@CeO2 does not change the crystal structure of PLA, but increases the nucleation and growth rate of PLA, thereby promoting its crystallization.