Melting and crystallization behavior of poly(trimethylene 2,6-naphthalate)

The melting and crystallization behavior of poly(trimethylene 2,6-naphthalate) (PTN) are investigated by using the conventional DSC, the temperature-modulated DSC (TMDSC), wide angle X-ray diffraction (WAXD) and polarized light microscopy. It is observed that PTN has two polymorphs (α- and β-form) depending upon the crystallization temperature. The α-form crystals develop at the crystallization temperature below 140 °C while β-form crystals develop above 160 °C. Both α- and β-form crystals coexist in the samples crystallized isothermally at the temperature between 140 and 160 °C. When complex multiple melting peaks of PTN are analyzed using the conventional DSC, TMDSC and WAXD, it is found that those arise from the combined mechanism of the existence of different crystal structures, the dual lamellar population, and melting-recrystallization-remelting. The equilibrium melting temperatures of PTN α- and β-form crystals determined by the Hoffman-Weeks method are 197 and 223 °C, respectively. When the spherulitic growth kinetics is analyzed using the Lauritzen-Hoffmann theory of secondary crystallization, the transition temperature of melt crystallization between regime II and III for the β-form crystals is observed at 178 °C. Another transition is observed at 154 °C, where the crystal transformation from α- to β-form occurs.     

Crystal structure of poly(pentamethylene 2,6-naphthalate)

The crystal structure of poly(pentamethylene 2,6-naphthalate) (PPN) was determined by using X-ray diffraction and molecular modeling. The unit cell of PPN was found to be triclinic ( space group) with dimensions of a=0.457 nm, b=0.635 nm, c=2.916 nm, =121.6°, β=90.4°, γ=87.6°, and the calculated crystal density was 1.311 g cm⁻³. The unit cell contains one polymer chain with two repeating units. In the unit cell, the PPN backbone takes gauche/gauche conformation in the middle part of each pentamethylene unit, and two naphthalene rings are in face-to-face arrangement.     

Crystallization behavior and morphology of poly(ethylene 2,6-naphthalate)

The crystallization behavior and morphology of poly(ethylene 2,6-naphthalte) (PEN) were investigated by means of differential scanning calorimetry (DSC), polarized optical microscopy (POM) and transmission electron microscopy (TEM). POM results revealed that PEN crystallized at 240 °C shows the coexistence of α and β-form spherulite morphology with different growth rates. In particular, when PEN crystallized at 250 °C, the morphology of spherulites showed a squeezed peanut shape. The Avrami exponents decreased from 3 to 2.8 above the crystallization temperature of 220 °C, indicating a decrease in growth dimension. Analysis from the secondary nucleation theory suggests that PEN crystallized at 240 °C has crystals with both regime I and regime II. In TEM observation, the ultra-thin PEN film crystallized at 200 °C showed the spherulitic texture with characteristic diffractions of α-form, while PEN crystallized at 240 °C generated an axialite structure with only β-form diffraction patterns. In addition, despite a long crystallization time of 24 h, amorphous regions were also observed in the same specimen. It was inferred that the initiation of PEN at 240 °C generates only β-form crystals from axialite structures.     

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.     

Uniaxial orientation and tensile properties of poly(ethylene terephthalate)/poly(ethylene-2,6-naphthalate) blends

Amorphous films of poly(ethylene terephthalate)/poly(ethylene-2,6-naphthalate) (PET/PEN) blends with different blend ratios were uniaxially drawn by solid-state coextrusion and the structure development during solid state deformation was studied. As-prepared blends showed two T_gs. The lower T_g was ∼72 °C, independent of the blend ratio. In contrast, the higher T_g increased with increasing PEN content. Thus, the coextrusion was carried out around the higher T_g of the sample. At a given draw ratio of 5, which was close to the achievable maximum draw ratio, the tensile strength of the drawn samples from the initially amorphous state increased gradually with increasing PEN content. On the other hand, the tensile modulus was found to decrease initially, reaching a minimum at 40-60 wt% PEN, and then increased as the PEN content increased. The results indicate that we can get the drawn films with a moderate tensile modulus and a high tensile strength. The drawn samples from the blends containing 40-60 wt% of PEN showed a maximum elongation at break, and a maximum thermal shrinkage around 100 °C. Also, the degree of stress-induced crystallinity showed a broad minimum around the blend ratio of 50% of PEN. These morphological characteristics explained well the effects of blend ratio on the tensile modulus and strength of drawn PET/PEN blend films.     

Light scattering studies on the crystalline morphology of stretched poly(ethylene 2,6-naphthalate) film

The crystalline morphology of poly(ethylene 2,6-naphthalate) (PEN) film obtained by uniaxial stretching at 145 °C (T_g + 25 °C) was investigated by use of a light scattering photometer equipped with a CCD camera system. The Hv scattering showed a symmetric, circular pattern at a low stretch ratio of λ < 3. The intensity profile became sharper with an increase in λ, suggesting that anisotropic crystal rods are randomly assembled and that the length of the rods increases with λ. At a high stretch ratio of λ ≥ 3, a double-cross-type pattern consisting of a broad rod-like pattern and sharp cross streaks was observed. The rod-like pattern became smaller and the streaks became sharper with an increase in λ. By the model calculation of the scattering pattern, the double-cross-type pattern is explained by the stacking of anisotropic crystal rods oriented in the stretch direction. As λ increases, the thickness of the rods and the number per stack increase, and the stacks and rods are slightly oriented in the stretch direction. The change in the wide angle X-ray diffraction pattern suggested that the ordering of the molecular chain in the crystal rods increases with increasing λ.     

Nanostructure of atmospheric and high-pressure crystallized poly(ethylene-2,6-naphthalate). Part II: structure-microhardness correlations

The microhardness of poly(ethylene naphthalene-2,6-dicarboxylate) (PEN), with a detailed characterized nanostructure has been investigated. PEN samples were crystallized from the glassy state at atmospheric pressure and from the melt at high pressure and were characterized using small-angle X-ray scattering (SAXS), wide-angle X-ray scattering (WAXS) and differential scanning calorimetry (DSC). Results show that the degree of crystallinity derived from WAXS, for both atmospheric and high-pressure crystallized PEN, is smaller than that obtained by density and calorimetry. For high-pressure crystallized samples, both, crystallinity and microhardness values are larger than those found for the material crystallized under atmospheric pressure. In the latter case, the hardness values depend on the volume fraction of lamellar stacks within spherulites X_L that depends on the crystallization temperature T_c. For T_c<200 °C, X_L is found to be less than 50%. Thus, for T_c<200 °C a linear relationship between H and T_c is observed provided a sufficiently long crystallization time is used. Results are discussed in terms of the rigid amorphous fraction that appears as a consequence of the molecular mobility restrictions due to the crystal stacks.     

Mesomorphic phase in oriented poly(pentamethylene 2,6-naphthalate)

The mesomorphic structure of poly(pentamethylene 2,6-naphthalate) (PPN) was investigated using a synchrotron X-ray scattering. The PPN fibers cold-drawn from the super-cooled amorphous state showed a smectic mesomorphic structure and further a crystalline phase at high strain. Based on the experimental evidence showing the split of amorphous halo up and down the equator and the conformational constraint suggested by the crystal structure refinement and computation, we suggested the smectic phase as S_CA where the mesogens are tilted against the layer surface normal and the tile direction is opposite between the neighboring layers.     

Studies on the Crystallization and Melting Behavior of Poly(ethylene 2,6-naphthalate)

Abstract

Crystallization behaviour of low molecular weight (oligomeric) and high molecular weight poly(ethylene 2,6-naphthalate)s (PEN) was studied using wide angle X-ray diffraction (WAXS) and differential scanning calorimetry (DSC). It was found that the crystallization conditions determine the nature of crystalline modification. Crystallization from the glassy state gives a-modification, whereas, crystallizing from the melt above 220°C results in β-modification. In contrast, the oligomers gives both the modifications up on crystallizing from the melt. The equilibrium melting temperatures of PEN were determined from DSC experiments, based on conditions of crystallization of a and β-modifications.     

Synthesis and characterization of poly(propylene terephthalate/2,6-naphthalate) random copolyesters

Poly(propylene terephthalate/2,6-naphthalate) random copolyesters (PPT-PPN) were synthesized and characterized from the molecular and thermal point of view. All the polymers showed a good thermal stability. The main effect of copolymerization was a lowering in the crystallinity and a decrease of T_m respect to homopolymers. WAXD measurements indicated that PPT-PPN copolymers are characterized by isodimorphic cocrystallization. The defect free energies, calculated on the basis of the inclusion model proposed by Wendling and Suter, indicated that the amount of PT units incorporated in the poly(propylene 2,6-naphthalate) (PPN) β crystals is higher than the amount of PN units which cocrystallizes in the poly(propylene terephthalate) (PPT) crystalline phase, probably due to the larger molar volume of PN units compared to PT ones. Amorphous samples showed a monotonic increment of T_g as the content of PN units is increased, due to the stiffening effect of naphthalene rings in the chain. Finally, the Fox equation described well the T_g-composition data.     

Morphology and crystal structures of poly(2,6-naphthalene terephthalate) and poly(2,6-naphthalene naphthalate)

The morphology and crystal structures of poly(2,6-naphthalene terephthalate) (PNT) and poly(2,6-naphthalene naphthalate) (PNN), prepared by confined thin film melt/solution polymerization (CTFMP/CTFSP), were characterized by transmission electron microscopy, electron diffraction and molecular modeling. The unit cells of PNT and PNN are both monoclinic (P12₁/a1 space group) with parameters a=8.18 Å, b=5.80 Å, c=14.9 Å and β=101.9° for PNT, and a=7.85 Å, b=5.97 Å, c=17.1 Å and β=99.5 for PNN, respectively. Simulated ED patterns from the proposed unit cells agree well with the observed ED patterns. The crystal structures of PNT and PNN are also compared with those of poly (p-phenylene naphthalate) (PPN) and poly(2,6-oxynaphtalate) (PONA).     

Poly(ethylene 2,6-naphthalate)/layered silicate nanocomposites: fabrication, crystallization behavior and properties

In this study, poly(ethylene 2,6-naphthalate) (PEN)/layered silicate nanocomposites (PLSNs) were successfully prepared by the intercalation of PEN polymer into organically-modified layered montmorillonite through the melt blending process. Both X-ray diffraction data and transmission electron microscopy images of PEN/layered silicate nanocomposites indicate most of the swellable silicate layers were exfoliated and randomly dispersed into the PEN matrix. Mechanical and barrier properties of the fabricated nanocomposites performed by dynamic mechanical analysis and permeability analysis show significant improvements in the storage modulus and water permeability when compared to neat PEN. Differential scanning calorimeter (DSC) was used to investigate the isothermal crystallization behavior and melting behavior of PLSNs. DSC isothermal results revealed that the crystal growth process of PEN and PLSNs are a three-dimensional spherulitic growth. The activation energy of PEN increases with increasing content of layered silicates. The result indicates that the addition of layered silicate into PEN reduces the transportation ability of polymer chains during crystallization processes.     

Block copolyetheresters with poly(trimethylene 2,6-naphthalenedicarboxylate) segments: Effect of composition on thermal properties

Block copolyetheresters with hard segments of poly(trimethylene 2,6-naphthalenedicarboxylate) and soft segments of poly(tetramethylene oxide) were prepared by melt polycondensation of dimethyl 2,6-naphthalenedicarboxylate, 1,3-propanediol and poly(tetramethylene ether)glycol (PTMEG) of molecular weights of 650, 1000 and 2000. The block copolyetheresters were characterized by FTIR, ¹H NMR, DSC, X-ray diffraction, TSC (thermal stimulated current), DMA and TGA. It was found that the thermal transitions were dependent on the composition. As the charge molar ratio of PTMEG to dimethyl 2,6-naphthalenedicarboxylate, x, increased, the T_m and ΔH_m of the polyester segments decreased, which has been also confirmed by the X-ray diffraction data. The polyether segments of the block copolyetheresters derived from PTMEG2000 could crystallize after cooling, but those of the block copolyetheresters derived from PTMEG1000 and PTMEG650 could not crystallize. The DSC, TSC and DMA results show consistent T_g data of the polyether segments. Based on the shift in T_g of the polyether segments, the amorphous parts of the polyether segments and the amorphous parts of the polyester segments were immiscible for the block copolyetheresters derived from PTMEG2000, but became partially miscible for the block copolyetheresters derived from PTMEG1000 and PTMEG650. The TGA results indicated that composition had little effect on thermal degradation under nitrogen.     

The effect of flexible chain length on thermal and mechanical properties of poly(m-methylene 2,6-naphthalate)s

The effect of flexible chain length on the thermal and mechanical properties such as melting temperature, glass transition temperature, dynamic mechanical relaxation behavior, and uniaxial tensile deformation for melt-quenched poly(m-methylene 2,6-naphthalate) (PmN) films was investigated using differential scanning calorimeter (DSC), dynamic mechanical thermal analyzer, and universal tensile machine. It was found from DSC thermograms that PmNs with even number of methylene group have higher melting temperatures and faster crystallization rates than PmNs with odd number of methylene group, showing an odd-even fluctuation. The plots of versus temperature show that all PmN samples have three relaxation processes (β, β^∗, and α) regardless of the number of methylene group in their backbone. It was found that both β^∗- and α-relaxations are cooperative processes and that the activation energies of both relaxations as well as the glass transition temperature associated with the α-relaxation show odd-even fluctuations as a function of the number of methylene group. The initial tensile modulus at the low drawing rate of 0.15 cm/min also shows an odd-even fluctuation. In summary, the macroscopic thermal and mechanical properties of PmN such as melting temperature, glass transition temperature, crystallization rate, activation energies of α- and β^∗-relaxations, and initial modulus measured under a slow drawing rate exhibit odd-even fluctuations as the number of methylene group in PmN increases.     

Crystallization temperature dependence of interference color and morphology in poly(trimethylene terephthalate) spherulite

The relationship between retardation and morphology in highly birefringent poly(trimethylene terephthalate) spherulites was studied from the viewpoint of crystallization temperature dependence. Both the retardation and the morphology relate with the degree of orientation of the molecular chains. Therefore, the degree of orientation of the crystal lamellae was estimated by image processing of transmission electron microscope (TEM) images of the spherulite. It was found that the degree of orientation changed remarkably between the non-banded and the banded morphology and the temperature dependence of the degree of orientation correlated with that of the retardation. Based on the image-processed TEM images, it was recognized that the crystal lamellae formed bundles in the banded spherulite, while few bundled lamellae were observed in the non-banded ones. It is suggested that the formation of bundled lamellae played the significant role for both the magnitude of retardation and determination of the morphology; i.e. whether to form banded spherulites or non-banded ones.     

The crystal structure of poly(2,6-naphthalenebenzobisthiazole)

The crystal structure of poly(2,6-naphthalenebenzobisthiazole) (Naph-2,6-PBT) was studied using X-ray and molecular modeling methods. The X-ray pattern of the annealed Naph-2,6-PBT fiber showed several Bragg reflections as well as streaks along the layer lines indicating that the registry between adjacent chains exists in the crystal with a great deal of axial disorder. Disordered structure in the crystal was fitted into the triclinic unit cell with the unit cell parameters of a=6.78 Å, b=3.46 Å, c=14.61 Å, α=88.0°, β=114.7°, and γ=94.8° with space group. The calculated density, 1.68 g/cm³ was comparable with the observed density, 1.56 g/cm³. The Δc/c (staggering ratio) representing the registry between the adjacent chains in the ac plane was −0.19, which is in good agreement with the energy calculation although another local energy minimum was found at Δc/c=0.31. The disordered structure in Naph-2,6-PBT was probably due to the discrete axial shift between Δc/c=0.31 and −0.19 in the ac plane. The LALS refinement showed that the naphthalene group was rotated by 9 (±3)° from the ac plane on the projected structure along the chain axis with a torsion angle between the naphthalene and benzobisthiazole rings of 23°.     

Nanofibrous mats of poly(trimethylene terephthalate) via electrospinning

Nanofibrous mats were prepared by electrospinning of poly(trimethylene terephthalate) (PTT) with diameter ranging from 200 to 600 nm. Morphology of electrospun nanofiber obtained by changing processing parameters such as solution concentration and their deposition time, was investigated with scanning electron microscope (SEM). Especially, periodic feature of surface roughness, such as diamond-shaped structure, was exhibited as the deposition time increased. In this work, it was shown that this phenomenon might result from polymer chain mobility, which was induced by solvent properties, and point bonding structure. In addition, schematic diagram was introduced to identify the formation of diamond-shape structure in PTT electrospun nanofibrous mats.     

Crystallization kinetics and morphology of poly(trimethylene terephthalate)

In this work, the isothermal crystallization kinetics of polytrimethylene terephthalate (PTT) was first investigated from two temperature limits of melt and glass states. For the isothermal melt crystallization, the values of Avrami exponent varied between 2 and 3 with changing crystallization temperature, indicating the mixed growth and nucleation mechanisms. Meanwhile, the cold crystallization with an Avrami exponent of 5 indicated a character of three-dimensional solid sheaf growth with athermal nucleation. Through the analysis of secondary nucleation theory, the classical regime I→II and regime II→III transitions occurred at the temperatures of 488 and 468 K, respectively. The average work of chain folding for nucleation was ca. 6.5 kcal mol⁻¹, and the maximum crystallization rate was found to be located at ca. 415 K. The crystallite morphologies of PTT from melt and cold crystallization exhibited typical negative spherulite and sheaf-like crystallite, respectively. Moreover, the regime I→II→III transition was accompanied by a morphological transition from axialite-like or elliptical-shaped structure to banded spherulite and then non-banded spherulite, indicating that the formation of banded spherulite is very sensitive to regime behavior of nucleation.     

High birefringence of poly(trimethylene terephthalate) spherulite

Poly(trimethylene terephthalate) (PTT) spherulite shows interference color under polarized light microscope without a sensitive tint plate. The fact indicates that the retardation of PTT spherulite is high, while it was reported that the birefringence in PTT fiber is low. In this study, the reason why the high birefringence is observed in PTT spherulite was discussed. By small area X-ray diffraction measurement, it was confirmed that a-axis of unit cell of PTT crystal was parallel to the radial direction of the spherulite. Based on the result, we calculated the refractive indices of parallel to a-axis and the other orthogonal directions. It was clarified that the refractive index of a-axis is much lower than the others and the intrinsic birefringence for a-axis orientation is high. It is the reason why the PTT spherulite shows high and negative birefringence.