Study of the Polymorphism of Saturated Monoacid Triglycerides II: Polymorphic Behaviour of a 50/50 Mixture of Tripalmitin and Tristearin

The polymorphic behaviour of a 50/50 blend of tripalmitin and tristearin has been investigated in detail using differential scanning calorimetry and X-ray diffraction. The blend is characterized by a greater tendency to β'-crystallization as compared to the pure triglycerides. Tripalmitin and tristearin, when mixed in a 1:1 ratio, are miscible in both the α-form and the β-form. In the β-form, however, demixing occurs, resulting in a 2-phase solid state. The characteristics of the α-form are considerably affected by the crystallization conditions, due to the formation of concentration gradients during crystallization. The β'-form can be obtained from the melt as well as via recrystallization of the α-form, and is characterized by a much higher stability as compared to the pure triglycerides. The X-ray diffraction data of the β'-form of the blend reveal a β₁-crystal structure. The β'-form of the pure triglycerides, however, is characterized by a β'₂-crystal structure. On the basis of the present data, however, no clear structural distinction can be made between β'₂ and β'₁.     

Anomalous molecular orientation of isotactic polypropylene sheet containing N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide

Small amount of N,N′-dicyclohexyl-2,6-naphthalenedicarboxamide as a β-form nucleating agent is dissolved beyond 280 °C in a molten isotactic polypropylene (iPP) and appears as needle crystals around at 240 °C during cooling procedure. Further, iPP molecules crystallize on the surface of the needle crystals, in which c-axis of the β-form iPP crystals grows perpendicular to the long axis of the needle crystals. Under flow field at extrusion processing, the needle crystals orient to the flow direction prior to the crystallization of iPP. As a result, c-axis of the β-form iPP crystals orients perpendicular to the applied flow direction with a small amount of α-form iPP. Moreover, the vertical molecular orientation of the extruded sheet sample is responsible for unique mechanical anisotropy; the fracture occurs along the transversal direction.     

Higher order structures and mechanical properties of bacterial homo poly(3-hydroxybutyrate) fibers prepared by cold-drawing and annealing processes

Pure bacterial homo poly(3-hydroxybutyrate) (PHB) fibers were prepared by melt spinning, followed by cold-drawing in an amorphous state at a temperature just above its glass transition temperature. Cold drawn fibers obtained were further drawn at higher temperatures, followed by annealing at various temperatures under tension. Relations among the processing conditions, higher order structures and mechanical properties were investigated using wide- and small-angle X-ray diffractions (WAXD and SAXD, respectively), birefringence, differential scanning calorimetry (DSC), and tensile measurements. PHB has two different crystalline forms, 2₁ helix conformation (α-form) and planar zigzag conformation (β-form). A single broad reflection of β-form was detected even in a PHB fiber drawn once at a temperature just above its T_g immediately after quenching and it tended to be stronger after 2nd drawing at higher temperatures. Annealing under low temperature and high tension facilitates the occurrence of β-form. It is suggested that the β-form crystal is formed not only from the tie chains between α-form lamella, but also from completely free amorphous chains. Changes in the amount of two types of crystals were analyzed using the WAXD integrated intensity. Birefringence of these fibers shows negative and positive values, depending on process conditions. Changes in higher order structure on the mechanical properties are also discussed.     

Polymorphie von zweisäurigen Triglyceriden der Stearinsäure- und Behensäure-Reihe

Polymorphism of Diacid Triglycerides of the Stearic Acid and Behenoic Acid Series Short- to medium-chain saturated diacyl derivatives of 1-monostearin and 1-monobehenin were synthesized in highly pure state and tested for their polymorphous behaviour. With the exception of the dicaprylo derivative the triglycerides of the behenoic acid series were strikingly stable in a wax-like plastic and stretchable α- resp. subα-modification which is obviously stable in the stearic acid series. The most stable modification of both series was the β-form, only the dibutyro-1-monobehenin by no manner could be transformed to a β′- or β-form. On heating the chilled samples or vice versa on cooling of the α-form two adjacent reversible phase transitions (subα₂ ? subα₁ ? α) could be observed with most of the triglycerides investigated here whereas in literature in case of the 1-monostearin derivatives the existence of only one subα-form has been described up to now.     

Crystallization Behavior of High-Oleic High-Stearic Sunflower Oil Stearins Under Dynamic and Static Conditions

Soft (SS) and hard (HS) stearins obtained from high-oleic high-stearic sunflower oil were isothermally crystallized under dynamic (with agitation) and static conditions at 16, 17, 18, 19, and 20 °C and 24, 25, 26, 27, and 28 °C, respectively. Both fractions crystallized under the α-form at early stages of crystallization for all temperatures (T _c) tested. Polymorphic behavior strongly changed with T _c and shear conditions for both fractions. SS fractions were characterized by α, β₂ and/or β₁ polymorphs at lower T _c and β₁ crystals at higher T _c when crystallized under dynamic conditions, while this same fat system was characterized by β₂′ crystals at lower T _c and β₂ at higher T _c under static conditions. HS samples were mainly characterized by α and β₂ crystals at lower T _c and α and β₁ crystals at higher T _c when crystallized under dynamic conditions; while the same fat was characterized by β₁′ crystals when crystallized at lower T _c and α when crystallized at higher T _c under static conditions after 90 min at T _c. These different polymorphic behaviors, in combination with the different processing and tempering temperatures are translated in specific textural behavior of the samples.     

High resolution 13C n.m.r. spectra of solid isotactic polypropylene

The high-resolution ¹³C n.m.r. spectra of three samples of solid isotactic polypropylene are reported. The spectra, obtained under conditions of proton dipolar-decoupling and fast magic-angle rotation and using cross-polarization, are of annealed and quenched samples of the α-crystalline form and of a sample of the β-crystalline form. Attention is drawn to the importance of knowing the proton relaxation characteristics in these experiments and some illustrative proton T_1? data are given. The ¹³C n.m.r. spectrum of the annealed sample of the α-crystalline form shows well-resolved splittings of the methyl and methylene resonances in a 2:1 intensity ratio. These splittings are interpreted in terms of the crystal structure of the α-form as suggested by X-ray diffraction. Quenching the α-form causes significant changes in the spectrum including a loss of resolution of the splittings obtained from the annealed sample. The β-form shows broad symmetrical resonances for the methyl and methylene carbons. The chemical shifts and other spectral features are discussed in the light of the proposed crystal structures and the effects likely to be produced by quenching.     

Effects of crystallization temperature on the polymorphic behavior of syndiotactic polystyrene

The influence of crystallization temperature on formation of the α- and β-form crystals of syndiotactic polystyrene (sPS) was investigated by X-ray diffraction and non-isothermal differential scanning calorimetry analysis. For sPS samples without any thermal history, the crystallization temperature must be the intrinsic factor controlling the formation the α and β-form crystals. Being crystallized at different cooling rate from the melt, sPS forms the β-form crystal until the temperature cooled down to about 230 °C, and α-form crystal can only be obtained when the temperature was below about 230 °C.     

Thermal, spectroscopy, and morphological studies on polymorphic crystals in poly(heptamethylene terephthalate)

Polymorphism and its influential factors in poly(heptamethylene terephthalate) (PHepT) were probed using differential scanning calorimetry (DSC), Fourier-transform infrared (FTIR) spectroscopy, and wide angle X-ray diffraction (WAXD). PHepT exhibits two crystal types (α and β) upon crystallization at various isothermal melt-crystallization temperatures (T_cs) by quenching from different T_maxs (maximum temperature above T_m for melting the original crystals). Melt-crystallized PHepT with either initial α- or β-crystal by quenching from T_max lower than 110 °C leads to higher fractions of α-crystal, but crystallization from T_max higher than 140 °C leads to higher fractions of β-crystal. In addition to T_max, polymorphism in PHepT is also influenced by crystallization temperature (T_c = 25-75 °C). When PHepT is melt-crystallized from a high T_max = 150 °C (completely isotropic melt), it shows solely β crystal for higher T_c, and solely the α-crystal for T_c < 25 °C; in-between T_c = 25 and 35 °C, mixed fractions of both α- and β-crystals. However, by contrast, when PHepT is melt-crystallized from a lower T_max = 110 °C, it shows α-crystal only at all T_cs, high or low.     

Crystallization behavior of nano-composite based on poly(vinylidene fluoride) and organically modified layered titanate

To understand the effect of the nano-filler particles on the crystallization kinetics and crystalline structure of poly(vinylidene fluoride) (PVDF) upon nano-composite formation, we have prepared PVDF/organically modified layered titanate nano-composite via melt intercalation technique. The layer titanate (HTO) is a new nano-filler having highly surface charge density compared with conventional layered silicates. The detailed crystallization behavior and its kinetics including the conformational changes of the PVDF chain segment during crystallization of neat PVDF and HTO-based nano-composite (PVDF/HTO) have been investigated by using differential scanning calorimetric, wide-angle X-ray diffraction, light scattering, and infrared spectroscopic analyses. The neat PVDF predominantly formed α-phase in the crystallization temperature range of 110-150 °C. On the other hand, PVDF/HTO exhibited mainly α-phase crystal coexisting with γ- and β-phases at low T_c range (110-135 °C). A major γ-phase crystal coexists with β- and α-phases appeared at high T_c (=140-150 °C), owing to the dispersed layer titanate particles as a nucleating agent. The overall crystallization rate and crystalline structure of pure PVDF were strongly influenced in the presence of layered titanate particles.     

The influence of stem conformation on the crystallization of isotactic polypropylene

The influence of stem conformation on the crystallization of i-PP is studied by growing α-form lamellae in melts of β-form lamellae at different temperatures. The melting of β-form lamellae and the crystallization of α-form lamellae is observed in situ at the interface of α- and β-form spherulites by AFM. The growth rate of α-form lamellae in the melt of β-form lamellae is much lower than that in the isotropic melt due to the stem conformation barrier, which originates from the difference in the α and β unit cell packing models.     

Effects of polyoxyethylene nonylphenol on dynamic mechanical properties and crystallization of polypropylene

Polypropylene (PP) was blended with polyoxyethylene nonylphenol (PN) in a twin-screw extruder and injection moulded. The dynamic mechanical properties of PP/PN blends were characterized by dynamic mechanical analyser (DMA). The glass transition temperature (T_g) of PP showed a slight decrease with incorporation of PN. Differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD) and polarized optical microscopy (POM) were employed to investigate the effects of PN on crystallization of PP. In a study of nonisothermal crystallization of PP and PP/PN blends, crystallization parameter analysis showed the addition of PN reduced the peak temperature of crystallization. β-form crystals of PP coexisted with α-form crystals in PP/PN blends, and oriented on the surface layer of injection moulded bar as revealed by WAXD. The degree of orientation was determined using Hermans orientation function. The thermal stability of β-form crystals was evaluated using high temperature WAXD and POM.     

X-ray studies of multiple melting behavior of poly(butylene-2,6-naphthalate)

Multiple melting behavior of poly(butylene-2,6-naphthalate) (PBN) was studied with X-ray analysis and differential scanning calorimetry (DSC). Double endothermic peaks L and H attributed to the α-form crystal modification, a small peak attributed to the β-form crystal modification, and a new shoulder peak S at a lower temperature of peak H appeared in the DSC melting curves. Wide-angle X-ray diffraction patterns of the samples isothermally crystallized at 200 and 220 °C were obtained at a heating rate of 1 K min⁻¹, successively. In this heating process, change of crystal structure and increase of quantity of the β-form crystallites could not be observed up to the final melting. With increasing temperature, the diffraction intensity decreased gradually and then increased distinctly before a steep decrease due to the final melting. The X-ray analysis clearly proved the melt-recrystallization during heating. The β-form crystal modification was formed during slow heating process in the high temperature region.     

Segmented copolymers of uniform tetra-amide units and poly(phenylene oxide): 2. Crystallisation behaviour

The crystallisation behaviour of copolymers of telechelic poly(2,6-dimethyl-1,4-phenylene ether) segments with terephthalic methyl ester endgroups (PPE-2T), 13 wt% crystallisable tetra-amide segments of uniform length units (two-and-a-half repeating unit of nylon-6,T) and dodecanediol (C12) was studied. The crystallisation rate of the T6T6T units was found to be very high despite the high T_g/T_m ratio. The supercooling (T_m−T_c) as measured by DSC is 18 °C at a cooling rate of 20 °C/min. WAXD has elucidated that the tetra-amide units remain organised in the melt.     

Study of the Polymorphism of Saturated Monoacid Triglycerides I: Melting and Crystallization Behaviour of Tristearin

The crystallization and melting behaviour of tristearin has been considered in detail. Both the thermal and structural characteristics of the β'- and β-crystal forms have been found to be largely dependent on the crystallization conditions. For the α-form, crystallization takes place very fast at low undercooling (T about 3°C). Upon melting, the α-form transforms directly to β, without any detectable appearance of a β'-form. The β'-form can only be obtained properly from the isotropic melt within a narrow temperature range (54 to 57°C). Above 57°C, β-crystallization becomes dominant. The main difference between the β'- and β-crystallization process is the induction time for crystallization. The decrease in β'-crystallization kinetics with increasing crystallization temperature is expressed in a longer induction time as well as in a slower rate of crystallization. In the case of the β-crystallization, the decrease in the overall crystallization rate mainly results from the sharp increase in induction time. The experimental data do not support the existence of distinct multiple subforms for the β'-form. The difference between β'₂ and β'₁ seems to be due to differences in the degree of ordering of the molecules in the β'-form. No significant differences have been observed between tristearin and tripalmitin with respect to their polymorphic behaviour. Both triglycerides only differ from each other in the kinetics of the crystallization and transformation.     

Optimization of poly(1,4-cyclohexylidene cyclohexane-1,4-dicarboxylate) (PCCD) preparation for increased crystallinity

A key factor, which affects the crystallization temperature on cooling (T_c) of PCCD is the cis/trans isomer ratio of the cyclohexyl diester in the polymer. Isomerization of pure dimethyl-trans-1,4-cyclohexanedicarboxylate can occur during the polymerization, and the T_c on cooling decreases along with the trans content. The isomerization reaction is enhanced with temperature, time and catalyst amount, and these variables should be minimized to prepare PCCD polymers with high T_c. However, these same variables also control the molecular weight growth of the polymer, and so a compromise between the best conditions for high T_c and those for high M_w must be made. A set of optimized conditions were obtained leading to PCCD polymers with M_w of 75,000-80,000 and T_c on cooling of 164-167 °C. Solid state polymerization was used to prepare high molecular weight PCCD with a high level of crystallinity (T_c on cooling ∼193 °C). It was also shown that adding small amounts of supplementary diols facilitates PCCD preparation by ensuring that high molecular weight PCCD polymers will be obtained even when the stoichiometry of monomer feed is off by >3%, i.e. conditions which would otherwise lead to low M_w. Finally, less crystalline PCCD's have been prepared via either incorporation of diethylene glycol or increasing the cis-diester amount in the polymer.     

Temperature dependence of polymorphism in electrospun nanofibres of PA6 and PA6/clay nanocomposite

Polymorphism found in nanofibres of polyamide 6 (PA6) and PA6/clay nanocomposite (PA6-NC), prepared by an electrospinning process, was studied by transmission electron microscopy (TEM) and variable-temperature wide angle X-ray scattering (WAXS), and compared with the polymorphic changes occurring in the pre-electrospun bulk materials. TEM results, concerning morphology and dispersion of the nanoclays, reveal that the produced electrospun nanofibres have an average diameter of 50 nm, and nanoclays are much more uniformly dispersed in the electrospun PA6-NC fibres than in the pristine PA6-NC. According to WAXS measurements, both types of electrospun nanofibres predominantly consist of γ-form crystals of PA6. Upon heating, from room temperature to the melting point, a number of successive transitions are observed for both systems, namely, crystalline γ to α′, α′ to α and α to the “amorphous” δ-form due to breakage of hydrogen bonds. On subsequent cooling, it has been observed, for the first time, that the development of crystalline forms for both systems is quite different from each other. The molten electrospun pure PA6 fibres first crystallize in the high temperature α′-form, and then they show the room temperature α-form. For these nanofibres, during a temperature cycle of heating and cooling, the initial γ-form crystals completely turn into the α-form crystals as in bulk PA6. In contrast, for the electrospun nanofibres of the PA6-NC, the γ-form crystals are preserved after completing a thermal cycle down to room temperature. The present findings on the evolution of polymorphism in the electrospun nanofibres of both systems provide useful information regarding their use as reinforcing elements in polymer composites.     

Crystallization behavior of poly(l-lactic acid)

The crystallization behavior of poly(l-lactic acid) was studied in the range of 80-160 °C. The peak crystallization time (τ_p) was defined and obtained from the crystallization isotherm measured with a differential scanning calorimeter (DSC). Isothermal crystallization temperature (T_c) dependence of log(τ_p) discretely changed at 113 °C (= T_b). The linear growth rate of spherulite, G, was measured with a polarizing microscope. The T_c dependence of G and the size of the spherulite also discretely changed at T_b. Crystal structures for samples isothermally crystallized at temperatures which were higher and lower than T_b were orthorhombic (α-form) and trigonal (β-form), respectively. The discrete change of the crystallization behavior was explained by the formation of different crystal.     

Polymorphism and β-form structure of poly(octamethylene 2,6-naphthalate)

It was revealed that poly(octamethylene 2,6-naphthalate) (PON) existed in two different crystal structures, α- and β-form, depending on crystallization process: The α-form crystal was dominantly developed from the cold-crystallization, whereas the β-form was from the melt-crystallization. The apparent melting temperatures of α- and β-form crystals were characterized to be 175 and 183 °C, respectively. On the basis of X-ray diffraction and molecular modeling studies, the crystal structure of β-form, developed dominantly from the melt-crystallization, was identified to be triclinic with dimensions of a = 0.601 nm, b = 1.069 nm, c = 2.068 nm, α = 155.68°, β = 123.25°, γ = 52.85°, and with the space group of . The calculated crystal density was 1.243 g/cm³, supporting that one repeating unit of PON exists in a unit cell. The octamethylene units in the PON backbone take largely all-trans conformation in the β-form unit cell.     

Structure, phase transition and electric properties of poly(vinylidene fluoride-trifluoroethylene) copolymer studied with density functional theory

The geometry, energy, internal rotation, vibrational spectra, dipole moments and molecular polarizabilities of poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)) of α- and β-chain models were studied with density functional theory at B3PW91/6-31G(d) level and compared with those of the poly(vinylidene fluoride) (PVDF) homopolymer. The chain length and the trifluoroethylene (TrFE) concentration were examined to discuss the copolymer chain stabilities, chain conformations and electric properties. The asymmetrical internal-rotation potential energy curve shows that the angles for the g and g′ conformations in the α-chain (tg and tg′) models are 53° and −70°, respectively, and the β-chain (ttt) conformation is a slightly distorted all-trans plane with dihedral angle at 177°. The energy differences, E_β − E_α(g) and E_β − E_α(g′), between the β- and the α-conformation are 2.1 and 7.8 kJ/mol, respectively. These values are smaller than that in PVDF (8.4 kJ/mol), suggesting that the β-conformation in the copolymer will be more stable than in PVDF. The energy barriers for β → α(g) and β → α(g′) transitions are 16.2 and 5.8 kJ/mol, respectively. The former is almost twice of the energy barrier in PVDF by 8.2 kJ/mol and the latter is slightly smaller (by 2.4 kJ/mol) than that in PVDF. The respective energy barriers for α(g) → β and α(g′) → β transitions are 18.3 and 13.6 kJ/mol compared with the value 16.3 kJ/mol in PVDF. The asymmetrical energy barriers may be one of the reasons for the copolymers with 0.5-0.6 (mole fraction) VDF exhibiting complicated phase transition behavior. The conformation of α-chain P(VDF-TrFE) exhibits from a helical (containing higher TrFE) to a nearly beeline (containing lower TrFE). This behavior is different from that in the PVDF and the nearly beeline conformation might be responsible for the increasing crystallizability. The helical might also be associated with the complicated phase transition behavior and the larger lattice strain in the P(VDF-TrFE)s with higher TrFE concentration. The energy difference per monomer unit between the β- and α-chain decreases with increasing TrFE content. The ideal β-chain is curved with a radius of about 30 Å, which is similar to that in PVDF. The chain curvature and the TrFE content will affect the dipole moment contribution per monomer. The chain length and TrFE content will not significantly affect the mean polarizability. The calculations indicated that there are some additional characteristic vibrational modes that may be used in identification of the α- or β-phase P(VDF-TrFE)s with different TrFE contents.     

Melting behavior of poly(l-lactic acid): X-ray and DSC analyses of the melting process

To clarify the melting behavior of poly(l-lactic acid) (PLLA), the wide-angle X-ray diffraction patterns of the isothermally crystallized PLLA samples (ICSs) were successively obtained during heating. We have already suggested the discrete change in the crystallization behavior of PLLA at a crystallization temperature (T_c) of 113 °C (= T_b) and formation of two crystal modifications for the ICSs obtained in the temperature range T_c ≤ T_b and T_c ≥ T_b. It was elucidated from the change in the X-ray diffraction pattern that the phase transition from the low-temperature crystal modification (α′-form) to the high-temperature one (α-form) occurred in a range 155-165 °C for the ICSs(T_c ≤ T_b), and that the crystal structure for the ICSs(T_c ≥ T_b) did not change. Recrystallization during heating, which is the origin of the multiple melting behavior, was proved by the increase in the diffraction intensity before steep decrease due to the final melting. A temperature derivative curve of the X-ray diffraction intensity almost coincided with the DSC melting curve.