Isothermal Crystallization Rate Research Articles

Isothermal Crystallization Kinetics, Morphology, and Mechanical Properties of Biocomposites Based on Poly(3-hydroxybutyrate-co-4-hydroxybutyrate) and Recycled Carbon Fiber

The biocomposites of poly(3-hydroxybutyrate-co-4-hydroxybutyrate) [P(3,4HB)] and recycled carbon fiber (RCF) were prepared via a melting extrusion. The crystallization behaviors and kinetics of the P(3,4HB) matrix in composites were exclusively studied under both nonisothermal and isothermal conditions. The corresponding results indicated that the P(3,4HB) either neat or compositing with RCF had a dual-peak cold crystallization behavior in the nonisothermal condition, and the isothermal crystallization rate of P(3,4HB) in composites was jointly determined by the rates of the nucleation and the crystal growth and integrity. However, it was reduced with the incorporation of RCF. Wide-angle X-ray scattering investigation demonstrated that the presence of RCF did not change the crystallization mechanism and crystalline structure of the P(3,4HB) matrix, but the crystallinity of the P(3,4HB) either neat or compositing with RCF was enhanced with an increase of crystallization temperature. Dynamic mechanical anal...

Effect of Uracil on the Isothermal Melt Crystallization Kinetics and Polymorphic Crystals Control of Biodegradable Poly(butylene adipate)

Biodegradable poly(butylene adipate) (PBA) and uracil composites were prepared via a solution and casting method at low uracil loadings in this work. The isothermal melt crystallization rate has been increased apparently in the composites by the addition of uracil, which acts as a nucleating agent for the crystallization of PBA. PBA may crystallize in the α- or β-form under different conditions. During the nonisothermal melt crystallization, the α-form crystals of neat PBA are formed at only relatively slow cooling rate; however, the formation of α-form crystals can be induced by uracil in the composites at relatively faster cooling rates. The formation of polymorphic crystals of PBA may be regulated by changing cooling rate and the uracil loading, which provides an efficient way of controlling the polymorphic crystals formation and biodegradation behaviors.

Effect of Low Thermally Reduced Graphene Loadings on the Crystallization Kinetics and Morphology of Biodegradable Poly(3-hydroxybutyrate)

Biodegradable poly(3-hydroxybutyrate) (PHB) and thermally reduced graphene (TRG) nanocomposites have been prepared successfully via a solution and coagulation method in this work at low TRG loadings. The effects of TRG on the crystal structure, spherulitic morphology, nonisothermal melt crystallization behavior, and isothermal melt crystallization kinetics of PHB in the PHB/TRG nanocomposites were investigated with various techniques. It was found that TRG does not change the crystal structure of PHB but apparently increases the nucleation density of PHB spherulites in the PHB/TRG nanocomposites. Moreover, both the nonisothermal and isothermal melt crystallizations of PHB are enhanced significantly in the nanocomposites because of the efficient nucleating agent effect of TRG. In addition, the isothermal melt crystallization kinetics of neat PHB and the PHB/TRG nanocomposites was analyzed by the Avrami equation. The overall isothermal melt crystallization rates of PHB are increased with deceasing crystallization temperature and increasing the TRG loadings in the nanocomposites; however, the crystallization mechanism remains unchanged in spite of the crystallization temperature and TRG loadings.

Influence of nanofiller dimensionality on the crystallization behavior of HDPE/carbon nanocomposites

AbstractThe isothermal and nonisothermal crystallization behavior of high density polyethylene (HDPE) containing various zero, one, and two dimensional (0‐D, 1‐D, and 2‐D) carbon nanofillers were investigated by means of differential scanning calorimetry. For a given temperature, the isothermal crystallization incubation time of HDPE became longer with the addition of lower dimensional carbon nanofillers, and the isothermal crystallization rate got slower. The values of Avrami and Tobin exponents indicated that the isothermal crystallization of HDPE followed two‐dimensional crystal growth in the presence of 2‐D and 1‐D carbon nanofillers, while exhibited three‐dimensional heterogeneous crystal growth in the presence of 0‐D carbon nanofillers. Contrary to the isothermal study, the nonisothermal crystallization of HDPE was accelerated in the presence of lower dimensional nanofillers. The nonisothermal crystallization data were finally analyzed using Ozawa and Mo methods. It was observed that only Mo approach could successfully describe the nonisothermal crystallization process of HDPE and HDPE/carbon nanocomposites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

Effect of polyhedral oligomeric silsesquioxane (POSS) reinforced polypropylene (PP) nanocomposite on the microstructure and isothermal crystallization kinetics of polyoxymethylene (POM)

In this study, effects of small amount of methyl-polyhedral oligomeric silsesquioxanes (methyl-POSS) on the microstructure and isothermal melt-crystallization behavior of polyoxymethylene (POM) were investigated, in detail. Introducing of methyl-POSS particles in POM phase was achieved via melt blending of methyl-POSS reinforced isotactic polypropylene (i-PP) nanocomposite as POSS carrier material with POM in a twin screw co-rotating extruder. Microstructural features of the POM/PP–POSS compounds were investigated with scanning electron microscopy (SEM) analysis. SEM analysis showed that the POM/PP–POSS compounds exhibited immiscible blend morphology. The POM, continuous matrix, phase includes a significant number of POSS particles due to interfacial interactions between the Si–O bonds of POSS and C–O bonds of POM, and resulted POSS migration from PP to POM phase during the melt processing. The kinetic parameters for the isothermal melt-crystallization process of the samples were determined with the Avrami and Lauritzen–Hoffman models. The crystallization activation energies were determined by the Arrhenius method. It was found that the PP–POSS nanocomposite significantly accelerated the isothermal crystallization rate of POM. Based on the results, it has been highlighted that POM compounds including a small amount of PP–POSS nanocomposite as POSS carrier material can be successfully used in the production of injection molded POM parts because the POM/PP–POSS compounds yield much faster molding cycle thus production rate than the POM.

Crystallization behavior of polypropylene/ethylene butene copolymer blends

AbstractOne polypropylene (PP) was mixed with two ethylene butene copolymers (EBM). EBM1 had 12.5 mol % of butene and was immiscible with the PP. EBM2 had 51.6 mol % of butene and was miscible with the PP. The dispersed PP in EBM1 showed fractionalized crystallization behavior with a crystallization temperature at around 45°C and a much slower isothermal crystallization rate comparing to the neat PP. The PP did not exhibit fractionalized crystallization behavior in EBM2. EBM1 did not decrease both the crystallization and melting temperatures of the continuous PP. However, EBM2 could decrease both the two temperatures. It was found that EBM2 could largely suppress the epitaxial lamellar branching of the PP. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Effect of Low Multi-Walled Carbon Nanotubes Loading on the Crystallization Behavior of Biodegradable Poly(Butylene Adipate)

The effect of low carboxyl-functionalized multi-walled carbon nanotubes (f-MWCNTs) loading on the crystallization behavior of biodegradable poly(butylene adipate) (PBA) was studied with various techniques in this work. For the nonisothermal melt crystallization, f-MWCNTs accelerate the crystallization process of PBA apparently due to the heterogeneous nucleation effect. The Ozawa method fails to describe the nonisothermal crystallization process of neat PBA and its nanocomposite. Isothermal melt crystallization kinetics of neat PBA and its nanocomposite was analyzed by the Avrami equation. The overall isothermal crystallization rate of neat PBA and its nanocomposite increases with increasing crystallization temperature. The addition of f-MWCNTs accelerates the isothermal crystallization of PBA as compared with that of neat PBA at a given crystallization temperature, indicative of the nucleating agent effect of f-MWCNTs; however, the crystallization mechanism does not change. The crystal structure of PBA remains unchanged in the PBA/f-MWCNTs nanocomposite despite the presence of f-MWCNTs.

Isothermal Crystallization Kinetics, Morphology, and Dynamic Mechanical Properties of Biodegradable Poly(ε-caprolactone) and Octavinyl–Polyhedral Oligomeric Silsesquioxanes Nanocomposites

Biodegradable poly(ε-caprolactone) (PCL) and octavinyl-polyhedral oligomeric silsesquioxanes (ovi-POSS) nanocomposites were prepared at low ovi-POSS loadings via a solution casting method in this work. Scanning electron microscopy observation reveals not only the fine dispersion but also the crystallization of ovi-POSS in the PCL matrix. The overall isothermal melt crystallization kinetics, spherulitic morphology, crystal structure, and dynamic mechanical properties of neat PCL and its nanocomposites were studied with various techniques. The presence of ovi-POSS has enhanced the overall isothermal melt crystallization rates of PCL in the nanocomposites; however, the crystallization mechanism and crystal structure of PCL remain unchanged despite the ovi-POSS loading. In addition, the storage modulus of the nanocomposites has been enhanced significantly relative to neat PCL, while the glass transition temperature varies slightly irrespective of the presence of ovi-POSS.

Isothermal Ice Crystallization Kinetics in the Gas-Diffusion Layer of a Proton-Exchange-Membrane Fuel Cell

Nucleation and growth of ice in the fibrous gas-diffusion layer (GDL) of a proton-exchange membrane fuel cell (PEMFC) are investigated using isothermal differential scanning calorimetry (DSC). Isothermal crystallization rates and pseudo-steady-state nucleation rates are obtained as a function of subcooling from heat-flow and induction-time measurements. Kinetics of ice nucleation and growth are studied at two polytetrafluoroethylene (PTFE) loadings (0 and 10 wt %) in a commercial GDL for temperatures between 240 and 273 K. A nonlinear ice-crystallization rate expression is developed using Johnson-Mehl-Avrami-Kolmogorov (JMAK) theory, in which the heat-transfer-limited growth rate is determined from the moving-boundary Stefan problem. Induction times follow a Poisson distribution and increase upon addition of PTFE, indicating that nucleation occurs more slowly on a hydrophobic fiber than on a hydrophilic fiber. The determined nucleation rates and induction times follow expected trends from classical nucleation theory. A validated rate expression is now available for predicting ice-crystallization kinetics in GDLs.

Isothermal crystallization kinetics of glass fiber and mineral-filled polyamide 6 composites

In this study, isothermal crystallization kinetics of polyamide 6 (PA6) composites reinforced with surface-treated glass fiber (GF) and natural, clay-type mineral (MN) were investigated by differential scanning calorimetry method in the presence and absence of a nucleating agent (NA). Microstructural features of the composites and interfacial interactions between filler and polyamide phases were also quantified by rheological measurements. The kinetic parameters for the isothermal melt-crystallization process of the samples were determined with the Avrami and Lauritzen–Hoffman models. The crystallization activation energies were determined by the Arrhenius method. It was found that the both fillers yielded a significant increase in the storage modulus of PA6. Kinetic calculations showed that the MN has a more pronounced acceleration effect on the crystallization rate of PA6 than the GF. Introduction of a small amount of NA significantly favored the isothermal crystallization rate of GF-reinforced PA6 but did not accelerate that of MN-reinforced one. Based on the results, it has been highlighted that PA6 composites reinforced with surface-treated GFs and including a small amount of clay-like mineral as a cheap and easy-accessible minor filler could yield the best performance for the injection-molded PA6 parts because the GF enhances the mechanical properties and the clay-like mineral accelerates the crystallization rate.

Crystallization behavior of random ethylene–butene copolymers modified with organic peroxide

The effect of molecular cross-linking on the crystallization of random ethylene–1-butene copolymers obtained from hydrogenation of model polybutadiene was studied by means of differential scanning calorimetry. The copolymers were modified with different concentrations of organic peroxide in the molten state to generate different crosslink levels. Under isothermal conditions, the crystallization rate of the modified polymers decreased with the average molecular weight likewise to that observed in the unmodified copolymers. Original and modified polymers show similar isothermal crystallization rates when compared to equivalent weight average molecular weights. Under no isothermal crystallization conditions, the temperature and the enthalpy of crystallization of the modified polymer decreased almost linearly with the concentration of peroxide. The activation energy for crystallization increased with the concentration of peroxide indicating that the increment in molecular crosslinking restricts the crystallization process.

Isothermal and Nonisothermal Cold Crystallization Behaviors of Biodegradable Poly(l-lactide)/Octavinyl-Polyhedral Oligomeric Silsesquioxanes Nanocomposites

Isothermal and nonisothermal cold crystallization behaviors of biodegradable poly(l-lactide) (PLLA)/octavinyl-polyhedral oligomeric silsesquioxanes (ovi-POSS) nanocomposites at low ovi-POSS loadings were investigated in this work. For both neat PLLA and its nanocomposites, the overall isothermal cold crystallization rates increase with increasing crystallization temperature; moreover, the overall isothermal cold crystallization rates of PLLA increase with increasing the ovi-POSS loading in the nanocomposites relative to neat PLLA, indicative of the nucleating agent effect of ovi-POSS. Crystallization mechanism and crystal structure of PLLA remain unchanged despite the ovi-POSS loading. For the nonisothermal cold crystallization, the crystallization process of PLLA is accelerated by increasing both heating rate and the ovi-POSS loading. The Ozawa equation failed to fit the crystallization process, while the Tobin equation could describe it well. The activation energies of nonisothermal cold crystallization were calculated by the Kissinger method, which increase with increasing the ovi-POSS loading in the nanocomposites relative to neat PLLA.

Crystallization kinetics and morphology of biodegradable poly( l-lactic acid)/graphene oxide nanocomposites: Influences of graphene oxide loading and crystallization temperature

Biodegradable poly( l-lactic acid) (PLLA)/graphene oxide (GO) nanocomposites have been prepared successfully at various GO loadings. Transmission electron microscopy and wide angle X-ray diffraction results indicate that a relatively fine dispersion of GO is achieved in the PLLA matrix. Nonisothermal melt crystallization peak temperatures are slightly higher in the nanocomposites than in neat PLLA. The overall isothermal melt crystallization rates are reduced for both neat PLLA and the PLLA/GO nanocomposites with increasing crystallization temperature; moreover, the overall isothermal melt crystallization rates are significantly greater in the nanocomposites than in neat PLLA although the crystallization mechanism remains unchanged. The crystal structure of PLLA is not modified in the PLLA/GO nanocomposites. Both the nonisothermal and isothermal melt crystallization of PLLA in the nanocomposites are influenced apparently by the GO loading.

Crystallization behaviors of biodegradable poly( l-lactic acid)/graphene oxide nanocomposites from the amorphous state

Crystallization behaviors of biodegradable poly( l-lactic acid) (PLLA)/graphene oxide (GO) nanocomposites at different GO loadings from the amorphous state were investigated in detail in this work. During the nonisothermal cold crystallization, the crystallization peak temperature of PLLA shifts to low temperature range in the nanocomposites with increasing the GO loading relative to neat PLLA despite heating rate; moreover, the overall nonisothermal cold crystallization has been accelerated with increasing heating rate for both neat PLLA and its nanocomposites. In addition, the variations of crystallization enthalpy of PLLA during isothermal and nonisothermal cold crystallization processes were also discussed. Relative to neat PLLA, the overall isothermal cold crystallization rate of PLLA is increased with increasing the GO loading in the nanocomposites despite crystallization temperature. The crystallization rate becomes faster with increasing crystallization temperature, while the crystallization mechanism and crystal structure remain unchanged for both neat PLLA and its nanocomposites.

Crystallization, Mechanical Properties, and Controlled Enzymatic Degradation of Biodegradable Poly(<I>ε</I>-caprolactone)/Multi-Walled Carbon Nanotubes Nanocomposites

Biodegradable poly(epsilon-caprolactone) (PCL)/multi-walled carbon nanotubes containing carboxylic groups (f-MWNTs) nanocomposites were prepared via simple melt compounding at low f-MWNTs loading in this work. Scanning and transmission electron microscopy observations indicate a homogeneous and fine distribution of f-MWNTs throughout the PCL matrix. The effect of low f-MWNTs loading on the crystallization, mechanical properties, and controlled enzymatic degradation of PCL in the nanocomposites were studied in detail with various techniques. The experimental results indicate that the incorporation of f-MWNTs enhances both the nonisothermal crystallization peak temperature and the overall isothermal crystallization rate of PCL in the PCL/f-MWNTs nanocomposites relative to neat PCL; moreover, the incorporation of a small quantity of f-MWNTs has improved apparently the mechanical properties of the PCL/MWNTs nanocomposites compared to neat PCL. The enzymatic degradation of neat PCL and the PCL/f-MWNTs nanocomposites at low f-MWNTs loading was studied in detail. The variation of weight loss with enzymatic degradation time, the surface morphology change, the reduced film thickness, the appearance of f-MWNTs on the surface of the films, and the almost unchanged molecular weight after enzymatic degradation suggest that the enzymatic degradation of neat PCL and the PCL/f-MWNTs nanocomposites may proceed via surface erosion mechanism. The presence of f-MWNTs reduces the enzymatic degradation rate of the PCL matrix in the nanocomposites compared with that of the pure PCL film.

Isothermal and non-isothermal crystallization behavior of PET nanocomposites

Polyethylene terephthalate (PET)/clay nanocomposites (PCNs) containing 1 wt% Cloisite 30B (C30B) were prepared via melt compounding. Modulated differential scanning calorimetry (MDSC) for isothermally crystallized samples revealed that the third endotherm at the highest temperature may be attributed to the recrystalization and melting of crystals, reorganized during heating. The first and second endotherms may be associated with melting of the secondary and primary crystals, respectively. The overall isothermal crystallization rate in PCNs was faster than in the neat resin. Growth kinetics revealed that the work required for chain folding and the equilibrium melting temperature in PCNs were somewhat higher than for neat PET. During isothermal crystallization, the steric hurdles introduced by clay layers lead to a reduction in the transport of the PET chains into crystallites. The effective non-isothermal activation energy for the PCNs was higher than for PET, possibly leading to less perfect crystals in the PCNs. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers

Novel miscible poly(ethylene sebacate)/poly(4-vinyl phenol) blends: Miscibility, melting behavior and crystallization study

High molecular weight samples of the novel biodegradable polyester poly(ethylene sebacate) (PESeb) were synthesized. Miscible poly(ethylene sebacate)/poly(4-vinyl phenol) semicrystalline/amorphous blends were prepared by applying the solvent casting method. Miscibility was proved by the single composition dependent glass transition temperature over the entire composition range observed in DSC traces of the quenched blend samples and also by the melting point depression. The Flory–Huggins interaction parameter was found to be x12 = −1.3. Also, FTIR spectra supported the hypothesis of intermolecular interactions due to hydrogen bonding. The crystallization of PESeb in blends was studied. As expected, isothermal crystallization rates decreased in the blends with increasing the PVPh content. The Lauritzen–Hoffman analysis was tested. The values of nucleation constant Kg did not show any substantial variation. The non-isothermal crystallization of the blends was also tested. It was found that the crystallization is retarded in the case of blends, compared to the neat PESeb.

Effect of compounding procedure on morphology and crystallization behavior of isotactic polypropylene/high‐density polyethylene/carbon black ternary composites

The effect of compounding procedure on morphology and crystallization behavior of isotactic polypropylene/high‐density polyethylene/carbon black (iPP/HDPE/CB) composite was investigated. iPP/HDPE/CB composites were prepared by four compounding procedures (A: iPP + HDPE + CB; B: iPP/HDPE + CB; C: HDPE/CB + iPP; D: iPP/CB + HDPE). Scanning electron microscopy observation showed that CB particles are mainly distributed in HDPE in all composites, and the phase morphology of composites was obviously affected by a compounding procedure. The size of the HDPE/CB domains in the composites prepared by procedures A and D decreased with the increase in CB content, whereas that of HDPE/CB in the composites prepared by procedures B and C rarely changed with the increase in CB content. The crystallization behaviors of the composites were significantly affected by their phase morphology, which resulted from the variation of compounding procedure. The isothermal crystallization rate of iPP in the composites prepared by procedures A and D was obviously increased, which may originate from the small HDPE/CB droplets dispersed in the iPP phase. The non‐isothermal crystallization curves of composites prepared by procedure D represented two peaks because the iPP component in these composites had the fastest crystallization rate, whereas the curves of composites prepared by other compounding sequences only exhibited one peak. Moreover, the crystallinity of HDPE almost increased by one time with the incorporation of only 1 phr CB because the CB particles selectively located in the HDPE phase, and the crystallinity of HDPE decreased with the further increase of CB content because of the strong restriction of CB on the HDPE chains. Copyright © 2011 John Wiley & Sons, Ltd.

Origin of enhanced cold crystallization rate for freeze‐dried poly(L‐lactide) from solutions

AbstractPoly(L‐lactide) (PLLA) freeze‐dried from dilute 1,4‐dioxane solutions exhibited very porous structure composed of thin membranes of which the mean thickness was estimated to be 104–135 nm. Heating measurements of differential scanning calorimetry (DSC) showed that the freeze‐dried PLLA (FDPLLA) exhibits an exothermic peak of cold crystallization at 78–81°C, which is at least 20 K lower than that for a quenched amorphous bulk PLLA. In accord with this, the overall rate of isothermal cold crystallization was revealed to be greater for the FDPLLA than that for the bulk. The origin of such high crystallizability of FDPLLA is attributed to its large surface area where the chain mobility is greater than in the bulk PLLA. The exothermic peak in the DSC trace shifted to a further lower temperature when the FDPLLA is immersed in ligroin (nonsolvent), which also suggests a major role of the free surface in enhancing the cold crystallization rate. On the other hand, the density and the chain conformational feature of the FDPLLA were revealed to be identical to the bulk PLLA. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers.

Preparation and Properties of Biodegradable Poly(l-lactide)/Octamethyl-Polyhedral Oligomeric Silsesquioxanes Nanocomposites with Enhanced Crystallization Rate via Simple Melt Compounding

Biodegradable poly(l-lactide) (PLLA)/octamethyl-polyhedral oligomeric silsesquioxanes (ome-POSS) nanocomposites were prepared via simple melt compounding at various ome-POSS loadings in this work. Scanning and transmission electron microscopy observations indicate that ome-POSS were homogeneously dispersed in the PLLA matrix. Effect of ome-POSS on the nonisothermal crystallization behavior, isothermal melt crystallization kinetics, spherulitic morphology, crystal structure, dynamic mechanical properties, and thermal stability of PLLA in the nanocomposites was investigated in detail. It is found that the presence of ome-POSS enhances both nonisothermal cold and melt crystallization of PLLA in the nanocomposites relative to neat PLLA. The overall isothermal melt crystallization rates are faster in the PLLA/ome-POSS nanocomposites than in neat PLLA and increase with increasing the ome-POSS loading; however, the crystallization mechanism of PLLA remains unchanged. The nucleation density of PLLA spherulites is enhanced, while the crystal structure of PLLA is not modified in the PLLA/ome-POSS nanocomposites. The storage modulus has been apparently improved in the PLLA/ome-POSS nanocomposites with respect to neat PLLA, whereas the glass-transition temperatures vary slightly between neat PLLA and the PLLA/ome-POSS nanocomposites. The thermal stability of PLLA matrix is reduced slightly in the PLLA/ome-POSS nanocomposites.