High-temperature hedritic crystallization of the β-modification of isotactic polypropylene

 High-temperature crystallization of the β-modification of polypropylene (β-iPP), induced by an active β-nucleating agent, was studied by polarizing light and scanning electron microscopy (SEM). It was established that, in the early stage of crystallization of β-iPP, hedrites were formed as precursors of the spherulitic crystallization. Hedrites seen flat-on are characteristic hexagonal formations (hexagonites) with low birefringence. The central core of hedrites had positive birefringence. Hedrites seen edge-on were rod-like formations with strong negative birefringence which would transform into a radially symmetric spherulitic form through sheaf-like and then oval (ovalite) arrangements. According to the SEM micrographs, hedrites are clusters of multilayer lamellar crystallites. On the surfaces of lamellae hexagonal etch pits appear referring to screw dislocations. They are responsible for branching and proliferation of lamellae. Hedrites may reach considerable sizes (several hundred micrometres) presumably due to a coordinated cooperative growth of lamellae. There is an unequivocal correlation between the character of birefringence and the morphological structure shown by SEM of hexagonites, rods, ovalites and spherulites. It was demonstrated that, at temperatures of isothermal crystallization higher than the critical T(βα) , mixed polymorphic structures of α- and β-modifications were formed. Received: 15 August 1996 Accepted: 10 January 1997     

Thermal and structural studies of polypropylene blended with esterified industrial waste lignin

Microwave-assisted chemical modification of lignin was achieved through esterification using maleic anhydride. Modified lignin (ML) was blended in different proportions up to 25 mass% with polypropylene (PP) using Brabender electronic Plasticorder at 190 °C. The structural and thermal properties of blends were investigated by thermogravometric analysis (TG), differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD) and scanning electron microscopy (SEM). TG analysis showed increased thermal stability of blends due to antioxidant property of ML, which opposed oxidative degradation of PP. DSC analysis indicted slight depression in a glass transition temperature and melting temperature of blends due to partial miscible blend behavior between PP and ML. All blends showed higher crystallization temperatures and continuously reducing percentage crystallinity with increasing ML proportion in the blends. WAXD analysis indicated that PP crystallized in β polymeric form in addition to α-form in the presence of ML. However, proportion of β-form did not show linear relation with increase in ML proportion, thus ML acts as β nucleating agent in the PP matrix. SEM analysis showed good dispersion/miscibility in PP matrix indicating modification in lignin is useful.     

Study on melting and recrystallization of poly(butylene succinate) lamellar crystals <Emphasis Type="Italic">via</Emphasis> step heating differential scanning calorimetry

Differential scanning calorimetry (DSC) has been widely applied to study crystallization and melting of materials. However, for polymeric lamellar crystals, the melting thermogram during heating process usually exhibits a broad endothermic peak or even multiple endotherms, which may result from changes of metastability via recrystallization process. Sometimes, the recrystallization exotherm cannot be observed due to its overlapping with the melting endotherm. In this work, we employed a step heating procedure consisting of successive heating and temperature holding stages to measure the metastability of isothermally crystallized poly(butylene succinate) (PBS) crystals. With this approach we could gain the fraction of crystals melted at different temperature ranges and quantitatively detect the melting-recrystallization behavior. The melting-recrystallization behavior depends on the polymer chain structure and the crystallization temperature. For instance, PBS block copolymer hardly shows recrystallization behavior while PBS oligomer and high molecular weight PBS homopolymer demonstrate remarkable melting-recrystallization phenomenon. High molecular weight PBS isothermally crystallized in the low temperature range shows multiple melting-recrystallization while those isothermally crystallized at elevated temperatures do not exhibit observable recrystallization behavior. Furthermore, the melting endotherms were fitted via the melting kinetics equations. The original isothermally crystallized lamellae demonstrate quite different melting kinetics from the recrystallized lamellar crystals that melt at the highest temperature range, which is attributed to the different degrees of stabilization. Finally, the mechanism of melting-recrystallization is briefly discussed. We propose that apparent melt-recrystallization phenomenon be observed when melting of preformed lamellar crystals and recrystallization of thicker lamellae have similar free energy barrier.     

Thermodynamics of alternating copolymer of ethylene and carbon monoxide in the 0–600 K region

The temperature dependence of the heat capacity of the alternating copolymer (ACP) of carbon monoxide with ethylene was studied, and temperatures and enthalpies of its phase transformations were measured by adiabatic vacuum, dynamic, and isothermal calorimetry in the temperature range from 8 to 600 K. The energy of burning of ACP was measured at 298.15 K in a calorimeter with the static bomb and isothermal shell. The thermodynamic parameters of transformation of the α-form of ACP crystals into the β-form and fusion of the β-form were determined. The thermodynamic functions for the 0–507 K range and thermodynamic characteristics atT=298.15 K andp=101.325 kPa were calculated. The thermodynamic parameters of the alternating copolymerization of ethylene and CO at 0–507 K and standard pressure were calculated for the bulk reaction. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 284–288, February, 1998.     

An Unusual but Consistent View on Flow Induced Crystallization of Polymers

Summary.  There is a considerable difference of more than 40 degrees centigrade between the equilibrium melting point of the α-crystal modification of i-PP and the lower temperature, where the α-spherulites of this polymer melt. The equilibrium melting point represents the temperature, where ideal crystals melt. In these crystals the macromolecules are in a stretched conformation. In contrast, in the spherulites the molecules are contained in lamellae of finite thickness. As a consequence it seems that in the interval between these two characteristic temperatures the nucleation kinetics is very different from the kinetics observed at temperatures below the melting temperature of the spherulites. This observation is of importance because almost all measurements on flow induced crystallization have been carried out below the melting temperature of the spherulites. It can be shown that at these lower temperatures the kinetics of crystallization (including flow induced crystallization) has nothing to do with the classical ideas about sporadic nucleation.     

Study on Melting and Recrystallization of Poly(butylene succinate) Lamellar Crystals via Step Heating Differential Scanning Calorimetry

Differential scanning calorimetry (DSC) has been widely applied to study crystallization and melting of materials.However,for polymeric lamellar crystals,the melting thermogram during heating process usually exhibits a broad endothermic peak or even multiple endotherms,which may result from changes of metastability via recrystallization process.Sometimes,the recrystallization exotherm cannot be observed due to its overlapping with the melting endotherm.In this work,we employed a step heating procedure consisting of successive heating and temperature holding stages to measure the metastability of isothermally crystallized poly(butylene succinate) (PBS) crystals.With this approach we could gain the fraction of crystals melted at different temperature ranges and quantitatively detect the melting-recrystallization behavior.The melting-recrystallization behavior depends on the polymer chain structure and the crystallization temperature.For instance,PBS block copolymer hardly shows recrystallization behavior while PBS oligomer and high molecular weight PBS homopolymer demonstrate remarkable melting-recrystallization phenomenon.High molecular weight PBS isothermally crystallized in the low temperature range shows multiple melting-recrystallization while those isothermally crystallized at elevated temperatures do not exhibit observable recrystallization behavior.Furthermore,the melting endotherms were fitted via the melting kinetics equations.The original isothermally crystallized lamellae demonstrate quite different melting kinetics from the recrystallized lamellar crystals that melt at the highest temperature range,which is attributed to the different degrees of stabilization.Finally,the mechanism of melting-recrystallization is briefly discussed.We propose that apparent meltrecrystallization phenomenon be observed when melting of preformed lamellar crystals and recrystallization of thicker lamellae have similar free energy barrier.     

The mechanism of α-γ transition of poly- (vinylidene fluoride) in the miscible blends

The simultaneous DSC-FTIR was used for the observation of crystallization and melting of poly(vinylidene fluoride) (PVDF) and its blends with poly(methyl methacrylate) (PMMA) and poly(ethyl methacrylate) (PEMA). The isothermal crystallization was carried out under the condition of both α-form and γ-form crystallized competitively. The crystal growth rate of α -form and γ -form were evaluated from the absorbance changes at 795 cm^-1 (α -form, CH₂ rocking) and 810 cm^-1 (γ -form, CH₂ rocking) obtained by the DSC-FTIR. The crystal growth rate of γ -form decreased at the same crystallization temperature in the order of PVDF/syn-PMMA, PVDF/PEMA and PVDF/at-PMMA, which was corresponding to the order of interaction parameter. The mechanism of α -g transition of PVDF in the miscible blends with at-PMMA, syn-PMMA and PEMA was evaluated from the relationship between the decrease of α -form and the increase of γ -form. The critical crystallization temperature, at which the transformation from α -form to γ -form proceeded only in the solid state, shifted to higher temperature side in the order of interaction parameter. This revised version was published online in August 2006 with corrections to the Cover Date.     

New understanding on the memory effect of crystallized iPP

In this study, recovery processes of isotactic polypropylene(iPP) melted spherulites at 135 °C after melting at higher temperatures(170 °C–176 °C) were investigated with polarized optical microscopy and Fourier transform infrared spectroscopy. The recovery temperature was fixed to exclude the interference from heterogeneous nuclei. After melting at temperatures between 170 °C and 174 °C, the melted spherulite could recover back to the origin spherulite at low temperatures. Interestingly, a distinct infrared spectrum from iPP melt and crystal was observed in the early stage of recovery process after melting at low temperatures, where only IR bands resulting from short helices with 12 monomers or less can be seen, which indicates that the presence of crystal residues is not the necessary condition for the polymer memory effect. Avrami analysis further indicated that crystallization mainly took place in melted lamellae. After melting at higher temperatures, melted spherulite cannot recover. Based on above findings, it is proposed that the memory effect can be mainly ascribed to melted lamellae, during which crystalline order is lost but conformational order still exists. These conformational ordered segments formed aggregates, which can play as nucleation precursors at low temperatures.     

Melting behaviour and evolved gas analysis of xylose

Two enantiomeric forms of xylose were identified as α-D-xylopyranose and α-L-xylopyranose by powder diffraction. Their melting behaviour was studied with conventional DSC and StepScan DSC method, the decomposition was studied with TG and evolved gases were analyzed with combined TG-FTIR technique. The measurements were performed at different heating rates. The decomposition of xylose samples took place in four steps and the main evolved gases were H₂O, CO₂ and furans. The initial temperature of TG measurements and the onset and peak temperatures of DSC measurements were moved to higher temperatures as heating rates were increased. The decomposition of L-xylose started at slightly higher temperatures than that of D-xylose and L-xylose melted at higher temperatures than D-xylose. The differences were more obvious at low heating rates. There were also differences in the melting temperatures among different samples of the same sugar. The StepScan measurements showed that the kinetic part of melting was considerable. The melting of xylose was anomalous because, besides the melting, also partial thermal decomposition and mutarotation occurred. The melting points are affected by both the method of determination and the origin and quality of samples. Melting point analysis with a standardized method appears to be a good measure of the quality of crystalline xylose. However, the melting point alone cannot be used for the identification of xylose samples in all cases.     

Physico-chemical characterization of anhydrous <Emphasis Type="Italic">D</Emphasis>-mannitol

In this work the solid-state characterization of anhydrous D-mannitol has been performed: α and β modifications can be distinguished only by XRPD and FTIR as they show melting temperature and enthalpy that are the same within the standard deviation. The understanding of the thermal behaviour of the δ form (obtained by re-crystallization in acetone) has required XRPD experiments performed at variable temperature. This form during heating undergoes a solid phase transition to α modification. By cooling a melted sample, under a wide range of experimental conditions, a very fast crystallization occurs. Independently of the starting crystal form (β or δ form), the re-crystallization of D-mannitol from melt always leads to α form.     

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

The melting behavior of the -form of isotactic polypropylene (-iPP) was investigated as a function of crystallization time and temperature. Calcium suberate, a selective -nucleating agent was used to produce samples that consist entirely of -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 -iPP. The equilibrium melting point estimated through the non-linear Hoffman—Weeks analysis is about 30°C higher than that (T _m ⁰=177°C) obtained on the basis of the linear extrapolation. These results are consistent with earlier claims that a linear extrapolation of T _m–T _c data leads to an underestimation of the equilibrium melting point. The results obtained for -iPP exemplify the importance of accounting for both the isothermal lamellar thickening effects and the non-linearity in the T _m–T _c 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.This revised version was published online in November 2005 with corrections to the Cover Date.     

Crystallization and Melting of β-Nucleated Isotactic Polypropylene

Ca salts of suberic (Ca-Sub) and pimelic acid (Ca-Pim) were synthesized and used as β-nucleating agents in different grades of isotactic polypropylene (IPP). Propylene homo-, random- and block-copolymers containing these additives crystallize principally in pure β-modification as demonstrated in isothermal and non-isothermal crystallization experiments. Ca-Sub proved the most effective β-nucleating agent known, so far. It broadens the upper crystallization temperature range of pure β-IPP formation up to 140°C. The effect of the additives on the crystallization and melting characteristics of the polymers was studied. The degree of crystallinity of the β-modification was found to be markedly higher than that of α-IPP. High temperature melting peak broadening was first observed and discussed in literary results regarding the same phenomenon for α-IPP. This revised version was published online in August 2006 with corrections to the Cover Date.     

Solution crystallization of nylon 12

Electron microscopy and x-ray diffraction data have been obtained on nylon 12 crystallized from 1-hexanol, 1,6-hexanediol, and hexylene glycol. Ribbonlike lamellar crystals of the γ form are obtained by crystallization from all the solutions and elongated flat crystals of the α form by crystallization from the 1-hexanol and hexylene glycol solutions. The direction of the hydrogen bond in these crystals is almost parallel to that of maximum crystal elongation. α- and γ-form crystals both grow from 1-hexanol and hexylene glycol at appropriate crystallization temperatures. γ-form crystals alone are obtained from 1,6-hexanediol solution at every crystallization temperature. The long periods measured by small-angle x-ray diffraction for the solution-grown crystals are in the range 7.6–10.6 nm. The melting behavior of the solution-grown crystals is examined and discussed. The melting temperatures of the γ form may be lower than that of the α form. An equilibrium melting temperature of 208.4°C for γ-form crystals is obtained by using a relation between thickness of lamellar crystals and their melting temperatures observed by differential scanning calorimeter measurements. Solvents affect the growth of the two crystalline forms in solution crystallization.     

DSC and morphological studies on the crystallization behavior of β-nucleated isotactic polypropylene composites filled with Kevlar fibers

The crystallization behavior of β-nucleated isotactic polypropylene (PP) composites filled with Kevlar fibers (KFs), as well as that of non-nucleated PP/KF composites for comparison, was investigated using differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The morphological observations revealed that the KF addition could induce thick α-transcrystalline layer around their surfaces in PP/KF composites, while no obvious transcrystalline layer could be detected in β-nucleated PP/KF composites. Detailed DSC investigations suggested that for the PP/KF composites, the dominant modification was α-form, and the crystallization process of matrix was promoted by KF addition, as illustrated by faster isothermal crystallization rate, shorter induction time, and higher crystallization temperature. However, for β-nucleated PP/KF composites, the main modification was β-form, and their crystallization characteristics were independent of KF addition, indicating that the α-nucleating effect of KFs was absent in this system. The DSC results were confirmed by further rheological and wide angle X-ray diffraction (WAXD) studies. The mechanism of the formation of transcrystalline layer was also discussed.     

Real-time AFM study of lamellar growth of semi-crystalline polymers

Atomic force microscopy (AFM) has been used to study the lamellar development during the crystallization and melting processes of poly(bisphenol A-co-alkyl ether) (BA-Cn) films. High-resolution and real-time AFM phase imaging enables us to observe the detailed growth process of the lamellae. At the early stage of the lamellar growth, embryos appeared firstly and some disappeared on the film surface after a period of time. The stable embryo developed into a single lamella. Then the lamella developed into a lamellar sheaf through branching and splaying. Our results revealed that the branches of the lamellae were formed by induced nucleation and it was also dependent on the crystallization temperature. Real-time AFM study of the melting, recrystallization and remelting processes of lamellae indicated that the thermal stability of different segments of a single lamella is different and that the thermal stability of the different lamellae is also different even if they develop at the same annealing temperature. The orientation and the development of the lamellae at the characteristic eyes and boundaries of the spherulites are observed in details.     

The phase transformation of copper-oxinate crystals observed by electron microscopy

Summary The transformation of copper-oxinate dihydrates was studied by electron microscopy and electron diffraction method. The replica method was also applied. The mechanism by which the unstable α-form is transformed into the stable β-form is as follows. The deposition of unstable needle-like α-form crystal → internal transformation of the α-form and the formation of intermediate fine particles, (γ-form) → inter- and intra-particle condensation aggregation of the γ-form → formation of the plate like β-form crystal by internal transformation of the aggregates and by the cementation of dissolved part.

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Zusammenfassung Die Umwandlung von Kupferoxynat-Dihydraten wurde mit Elektronenmikroskop und Elektronenbeugung studiert. Es wurde die Abdruckmethode angewendet. Der Mechanismus, durch welchen die instabile Alphaform in die stabile Betaform übergeht, wird verfolgt. Der Abbau der instabilen nadelf?rmigen Alphaform-Kristalle zu interner Umwandlung der Alphaform und der Bildung von einer intermedi?ren aus feinen Partikeln bestehenden Gammaform in die inter- und intrapartikul?re Kondensationsaggregation der Gammaform und schlie?lich die Bildung der pl?ttchen?hnlichen Betaform-Kristalle durch interne Umwandlung der Aggregate und durch Verkittung der gel?sten Teile wird gezeigt.

     

β-Crystallisation tendency and structure of polypropylene grafted by maleic anhydride and its blends with isotactic polypropylene

Crystallization, melting and structure of three different commercial types of isotactic polypropylene (iPP) grafted by maleic anhydride (PP-g-MAH) with different maleic anhydride content (AC) and their β-nucleated versions were studied by X-ray diffractometry (WAXS), differential scanning calorimetry (DSC), polarised light microscopy (PLM) and scanning electron microscopy (SEM). The presence of maleic anhydride units disturbs the chain regularity, hereby decreases the crystallization tendency of iPP in general and the β-crystallisation ability in particular. β-modification of iPP (β-iPP) forms only in β-nucleated PP-g-MAH polymers studied if the anhydride content is not larger than 0.5 mass%. The influence of AC of PP-g-MAH on the feature the spherulitic structure is demonstrated by PLM and SEM micrographs. The β-nucleated iPP/PP-g-MAH blends containing 10 mass% PP-g-MAH crystallise predominantly in β-form independently of AC of the latter. The β-nuceated blends of iPP and PP-g-MAH with lowest AC crystallise in β-form in whole concentration range. The interaction parameter between iPP and PP-g-MAH polymers calculated by Nishi-Wang equation indicate limited interaction between the components.     

Kinetics of competitive crystallization of β- and α-modifications in β-nucleated iPP studied by isothermal stepwise crystallization technique

Crystallization kinetics of β-nucleated isotactic polypropylene (β-iPP) under isothermal conditions were investigated by differential scanning calorimetry. iPP was nucleated by a trisamide derivative, namely tris-2,3-dimethyl-hexylamide of trimesic acid (TATA). In the presence of TATA possessing dual nucleating ability, the formation of the α- and β-form occurs simultaneously. An isothermal stepwise crystallization method is suggested in this study, which can separate the crystallization process of β- and α-iPP and consequently their crystallization kinetics can be evaluated separately. The results indicated that the mechanism of crystallization changes in temperature especially in the vicinity of the upper critical temperature of the formation of the β-phase. In addition, it was found that the ratio of the growth rates of β- and α-modification determines the characteristics of crystallization and influences the apparent rate constant of crystallization of both polymorphs.     

Thermal analysis of the multiple melting behavior of poly(butylene succinate‐co‐adipate)

The melting behavior of poly(butylene succinate‐co‐adipate) (PBSA) isothermally crystallized from the melt was investigated by differential scanning calorimetry. Triple, double, or single melting endotherms were observed in subsequent heating scan for the samples isothermally crystallized at different temperatures. These endothermic peaks were labeled as I, II, and III for low‐, middle‐, and high‐temperature melting endotherms, respectively. The independence of endotherm III to the crystallization temperature, the existence of an exothermic crystallization peak just below the endotherm III, and the heating rate dependence of endotherm III indicated that endotherm III was due to the remelting of recrystallized lamellar during a heating scan. The influence of crystallization time on the melting behavior of PBSA showed that endotherms II and III developed prior to endotherm I; endotherm III developed rather simultaneously with endotherm II. Further investigation showed that the peak temperature of endotherm I increased linearly with the logarithm of the crystallization time. It suggested that endotherm II was attributed to the melting of the primary lamellae, while endotherm I was due to the melting of secondary lamellae. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3077–3082, 2005     

The Polymorphism of Glycine. Thermochemical and structural aspects

X-ray, DSC and solution calorimetric investigations were carried out for α-, β- and γ-modifications of glycine. Particular attention was paid to kinetic and thermochemical aspects of γ- → α-phase transition. The temperature of this phase transition turned out to be sensitive to a) conditions under which the crystals of the γ-modification were grown, b) tempering of crystals c) form (geometry) of crystals. Kinetics of this phase transition of single crystals of γ-phase in rhomboedric form can be described by the equation for two-dimension nuclei growth, whereas for crystals of triangle geometry the equation for three dimension growth is valid. On the basis of energy parameters describing growth of α-form in γ- →α-phase transition, the kind of structure defects, which are responsible for this phase transition, was estimated. Taking into account the Δ_sol H _m, the absolute values of the lattice energies of the investigated polymorphs indescending order are follows: γ->α->β-modification. The obtained results are discussed with respect to the peculiarity of the crystal lattice structures, particularly the network of hydrogen bonds. The β-modification of glycine is monotropically related to the other forms, whereas γ-and α-polymorphs are enantiotropically-related phases. This revised version was published online in July 2006 with corrections to the Cover Date.