Types Of Spherulites Research Articles

Correlation of crack patterns and ring bands in spherulites of low molecular weight poly(l-lactic acid)

Only a single type of circular circumferential crack is conventionally reported for poly(l-lactic acid) (PLLA). In this study, PLLA samples were found to exhibit as many as four crack types of different directions and patterns, which cannot be feasibly explained simply by the directional difference in coefficients of thermal expansion. Depending on crystallization temperature (T c), PLLA crystallizes into ringless or ring-banded spherulites, whereas the crack patterns are dramatically different in these two types of spherulites. In ring-banded spherulites of PLLA crystallized at intermediate T c, two uniquely different crack types are present: (1) twin circumferential cracks coinciding with the dark–bright and bright–dark boundary and (2) radial short-segmental voids coinciding on the bright bands in spherulites. The radial short-segmental cracks on the bright band of ring-banded spherulites may be caused by PLLA crystals of radial direction with various twisting that contract laterally upon cooling. Only circumferential cracks are present in PLLA crystallized into ringless spherulites, where concentric continuous circumferential cracks are present in the ringless spherulites at low T c with finer lamellae, but discontinuous and irregular circumferential cracks are present in the ringless spherulites at high T c with coarse lamellae. Although all cracks are triggered by cooling from T c, all evidences indicate that the crack patterns and types are highly associated with the lamellar orientation, patterns, and coarseness in spherulites.

Dynamically confined crystallization in a soft lamellar space constituted by alternating polymer co-brushes

Crystallization kinetics and behavior of PCL side chains in polymer co-brushes constituted with PCL and PEO side chains alternatively attached on poly(styrene-alt-maleimide) backbones have been determined using in-situ FT-IR and DSC methods. Avrami analysis shows the exponent n increasing from one at 10 °C to two at 30 °C, demonstrating confined crystallization of PCL side chains through homogeneous or heterogeneous nucleation. PLM morphological characterization displays typical spherulites of which size is dependent on the crystallization temperature and further AFM visualization shows typical PCL lamellae at 30 °C and broken lamellae at 10 °C embedded within PEO + backbone matrix inside of spherulites. Such lamellar structure explains the confined crystallization with Avrami exponent n ≤ 2. Formation of the broken lamellae can further clarify the reason why Avrami exponent decreases to n ≈ 1 at 10 °C, that is, homogeneous nucleation in the isolated crystals. Dynamically confined crystallization has been proposed based on their special molecular architecture. Comparing to statically confined crystallization, the construction of confined space and the crystallization process were almost synchronous. The formation of spherulites mesoscopically reveals the entire molecule motion and assembly through a pathway of conventional crystalline polymers and the crystallization of PCL side chains in a space constituted by stiff backbones of poly(styrene-alt-maleimide) plus soft PEO layer microscopically reflects a confined character which has been observed in some conventional block copolymers.

Spherulitic crystallization of holmium tartrates in silica gels

Spherulites of holmium tartrate trihydrate and holmium nitro-tartrate monohydrate have been grown in silica gel medium by making holmium nitrate to react with tartaric acid at high supersaturations. The mechanism of spherulitic growth of holmium tartrates is discussed. The spherulitic crystallization is shown to be due to heterogeneous nucleation. In the early stages of growth an amorphous spherical mass gets nucleated inside the gel. Crystal fibers diverge radially from the surface of the spherical mass giving rise to a spherical polycrystalline holmium tartrate. Thermal stability of the two types of spherulites grown in the silica gel shows that the holmium tartrate trihydrate is more stable than holmium nitro-tartrate monohydrate. The surface morphology and internal structure of the spherulites of holmium tartrates have been studied by using scanning electron microscopy. The results on growth kinetics are given by studying the variation of radius of spherulites as a function of time. A non-linear time–size relations under several conditions of growth have been observed, which suggests a non-uniform solute concentration at the crystal surface.

Effect of processing conditions on the development of morphological features of banded or nonbanded spherulites of poly(3‐hydroxybutyrate) (PHB) and polylactic acid (PLLA) blends

AbstractTwo semicrystalline poly(3‐hydroxybutyrate) (PHB) and polylactic acid (PLLA) blends with and without poly(vinyl acetate) (PVAc) were prepared by dissolving different ratios in hot chloroform at 50 °C to obtain promising alternative biodegradable materials for eliminating plastic waste. The miscibility, crystallization, melting behavior and vibration modes of the prepared samples were characterized by differential scanning calorimetry (DSC), polarized optical microscopy (POM), Fourier transform infrared spectroscopy (FTIR), and wide angle X‐ray diffraction (WAXD) techniques. DSC analysis showed that only one crystallization temperature for blends with PVAc (single homogeneous phase) and two crystallization temperatures for blends without PVAc (immiscible blends) were obtained. The POM results indicated that the morphological structures of B381, B551, and B831 samples consist of two types of spherulites (fibrils and banded) which created at different crystallization temperatures. The irrelevant interaction between PHB and PLLA structures was detected from FTIR spectra. The addition of PVAc caused an obvious decrease in the peak position of the carboxyl group CO from 1752 to 1724 cm−1 due to dipole‐dipole interactions. WAXD indicated that the lattice parameters are changed in blends with PVAc and unchanged without PVAc. Our results indicated that, the PVAc can be used as compatibilizer and improved the compatibility between PHB and PLLA. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers

Surface and interior views on origins of two types of banded spherulites in poly(nonamethylene terephthalate)

Top-surface and three-dimensional views of Type-1 and Type-2 of ring-banded spherulites in poly(nonamethylene terephthalate) (PNT) in thicker bulk crystallized on a nucleating potassium bromide (KBr) substrate were examined using various microscopy techniques: scanning electron microscopy (SEM), polarized-optical microscopy (POM), and atomic-force microscopy (AFM). In PNT crystallized at higher crystallization temperature (T(c)) with heterogeneous nucleating substrate, typically two types of ring-banded spherulites are present that differ significantly in patterns and ring spacings: Type-1 Type-2 (single- and double-ring-banded spherulites). Three-dimensional view on fractured spherulites in bulk PNT samples reveals that the single-ring-banded spherulite (Type-1) tends to be well-rounded spheres as they are nucleated homogeneously from bulk; the double-ring-banded spherulite (Type-2) is concentric hemisphere or truncated sphere shells owing to be nucleated from bottom. With confined thickness of films, the 3-D hemispheres in PNT may become truncated into multi-shell annular cones or arcs when thickness or growth is restricted. Based on the top-surface vs. interior views of banded lamellar assembly, origins and inner structures of dual types of ring bands in PNT were examined in greater details.

Six types of spherulite morphologies with polymorphic crystals in poly(heptamethylene terephthalate)

Six types of spherulite morphologies packed with polymorphic crystals and their growth kinetics in melt-crystallized poly(heptamethylene terephthalate) (PHepT) were characterized using polarized-light optical microscopy (POM), Fourier transformed infrared microspectrometry (micro-FTIR), differential scanning calorimetry (DSC) and atomic-force microscopy (AFM). Two maximum melting temperatures (Tmax), a higher 150 °C and a lower 110 °C, were used to melt the initially crystallized PHepT of either α- or β-crystal. The high Tmax was enough to melt all nuclei, but the lower Tmax was considered as near or slightly below the equilibrium melting temperatures of these two cells (if estimated by nonlinear methods). When crystallized at various Tc from these two Tmax’s, PHepT can exhibit as many as six types of spherulites (Ring Type-I, -II, -III, Maltese-cross Type-1, -2, and -3) owing to different nucleations. Ring Type-I, Maltese-cross Type-1 and -3 spherulites are packed of the sole β-crystal, while Ring Type-II, -III and Maltese-cross Type-2 spherulites are attributed to the sole α-crystal. However, as the PHepT polymorphic cells are related to Tc, such correlations between the crystal cells and spherulite types (ring or ringless) cannot be ruled out to be a coincidence.

Microscopic Fourier Transform Infrared Characterization on Two Types of Spherulite with Polymorphic Crystals in Poly(heptamethylene terephthalate)

FTIR microspectrometry with in situ temperature variation and IR-peak-mapping capability, and POM characterization were used to study the crystal distribution in dual spherulites in poly(heptamethylene terephthalate). By tracing the crystalline IR bands of the α-crystal and β-crystal to get the crystal distribution, the techniques resolve that the ringed and ringless spherulites comprise α- and β-crystals, respectively. In addition, temperature-dependent IR analyses on the spots related to the two crystals also reveal the α- and β-crystals melt at 98 and 104 °C, respectively. The ringed and ringless spherulites were proven to be correlated with the α- and β-crystal forms, respectively.

Macromol. Rapid Commun. 15/2010

Front Cover: The image presents dual spherulite types in polymorphic poly(heptamethylene terephthalate) (PHepT), melt-crystallized at 80°C. Correlations between the spherulite morphology and polymorphic crystals in melt-crystallized PHepT are analyzed using Fourier-transform infrared microspectroscopy to characterize the microdomains in individual spherulites at various temperatures. Further information can be found in the article by K. C. Yen, E. M. Woo,* and K. Tashiro* on page 1343.

Single- and double-ring spherulites in poly(nonamethylene terephthalate)

A new mechanism of formation of ring-banded spherulites was discovered, where three different types of spherulites were present in poly(nonamethylene terephthalate) (PNT) cast in thin film forms. The growth and morphological features in three ring-banded spherulites were compared and analyzed using polarized/non-polarized light microscopy, differential scanning calorimetry (DSC), and scanning electron microscopy (SEM) and element analysis by energy dispersive spectroscopy (EDS) on surfaces of spherulites. Three types of spherulites (labeled: Type-0, 1, and 2) are possible in PNT when crystallized at wide range of crystallization temperature (Tc); however, only two of the three types can co-exist in PNT at a given Tc. At lower Tc (<55 °C), within Regime-III, the spherulites in PNT are either of Type-0 (appearing ringless in POM) or Type-2 (double-band in POM). When crystallized at temperature of Tc = 55 °C or higher (Regime-II), the morphology is featured with Type-1 (single-ring-banded in POM) spherulites as the majority species that co-exist with Type-2 (double-ring-banded in POM) spherulites as imbedded minority. Origins and morphological differences of the single-band vs. double-band spherulites were compared. The double-band spherulites have much larger inter-ring spacing than do the single-band spherulites. By comparison, the rod-like lamellae in the double-banded spherulites (Type-2) are longer and thicker, and more ordered than those in the single-banded spherulites (Type-1).

Dual Types of Spherulites in Poly(octamethylene terephthalate) Confined in Thin-Film Growth

Spherulite morphology and growth kinetics of poly(octamethylene terephthalate) (POT), cast on single-side glass or confined between two slides in thin-film forms, were characterized using polarized versus nonpolarized optical microscopy, scanning electron microscopy (SEM), and wide-angle X-ray (WAXD) analysis. POT can simultaneously display solely one type of spherulite or dual types of spherulites (double-ring-banded and ringless ones), depending on T c or T max imposed. Fractions of these two types depend on T c when quenched from a fixed T max = 160 degrees C. At lower T c's, POT exhibits higher crystallization rates leading to higher fractions of ringless spherulites; at higher T c's, POT exhibits lower crystallization rates leading to ring-banded spherulites. At intermediate to high T c's where the growth kinetics of POT could be monitored, the ring-band type dominates and the fraction of ringless spherulites is insignificantly small. Both ringless and ring-banded spherulites can be seen in regime III ( T c = 70-110 degrees C), with fractions of ringless type of spherulites decreasing with temperature. Thus, growth kinetics for POT was mainly focused on the regime of ring-banded spherulites. In regime III, the ring-band pattern is more orderly concentric with smaller inter-ring spacing (1-2 mum) for lower T c's but intermediately larger spacing (3-5 mum) for higher T c's. The orderly lamellar orientation in the ring-bands in contrast with the inter-ring valley region is discussed. In regime II (115 degrees C and above), the ring-band pattern is first distorted to highly zigzag irregularity at higher T c's and then eventually disappears at extremely high T c, with the lamellar crystals eventually turning dendritic with no rings. Apparently, the types of spherulites in polymers are more influenced by the growth rates as determined by T c and slightly less by T max, but not by the substrate surface nucleation.

Effect of crystallization rate on the formation of the polymorphs of solution cast poly(vinylidene fluoride)

A systematic study was carried out to investigate the effect of solvent type and temperature on the formation of the α and β phases from solution cast PVDF. Three solvents with different boiling points were used: N,N, dimethylformamide (DMF), N-methyl-2-pyrrolidone (NMP) and hexamethylphosphoramide (HMPA). Infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) revealed that the type of phase formed depends on the crystallization rate of PVDF, which in turn is determined by the evaporation rate of the solvent. Low rates result predominantly in the trans-planar β phase, high rates predominantly in the trans-gauche α phase and intermediate rates in a mixture of these two phases, regardless of solvent and temperature used. Since evaporation rate of the solvent is intimately related to temperature, PVDF films can be obtained predominantly in either one of these phases, or a mixture of these, by an adequate choice of the evaporation temperature range for a given solvent. The possible solubility curves of the two polymorphs α and β of PVDF were sketched. The formation of different types of spherulites, associated with the two different PVDF polymorphs, could be verified by surface micrographs of the cast films.

Influence of the Crystallization Kinetics on the Microstructural Properties of γ-PVDF

The kinetics of the isothermal crystallization of the γ-phase Poly(vinylidene fluoride) has been investigated. Samples were prepared from the melt at different crystallisation temperatures and the variation of the microstructure of the samples was monitored with time by optical microscopy. Raman and Infrared transmission spectroscopies also show the appearance of the γ-phase for higher crystallisation temperatures. Two types of γ-phase spherulites have been identified. These spherulites represents different ways to obtain the γ-phase and show different thermal stability. The correlation between microstructure and kinetic parameters allows the tailoring of the microstructure by choosing the crystallisation conditions of the samples.

SPHERULITIC STRUCTURE AND MORPHOLOGY OF POLY(ETHYLENE SUCCINATE)/POLY(ETHYLENE OXIDE) (PES/PEO) BLENDS WITH ONE-STEP CRYSTALLIZATION

The spherulitic structure and morphology development of poly(ethylene succinate)/poly(ethylene oxide) (PES/PEO) blends with one-step crystallization behavior were observed by means of polarizing optical microscope. It was found that the pure PES spherulite in which the adequate quantity of PEO melt existed in the interlamellar regions, and the blending spherulite formed by both PES and PEO lamellae could form simultaneously. When the two types of spherulites contacted with each other the front of the blending spherulite could penetrate into the pure PES spherulite to grow continually. This penetration growth behavior was also observed when the mini-crystal particles of the PES component were formed at lower crystallization temperatures. The kinetics analysis showed that the penetration growth rate was faster than that in the original melt. It was evidenced that the increasing of growth rate and the formation of new growth site should be the typical characteristics of interpenetrated growth in binary crystalline polymer blends.

Preparation of spherulites from jet cooked mixtures of high amylose starch and fatty acids. Effect of preparative conditions on spherulite morphology and yield

When high amylose cornstarch (amylose content: 70%) was jet cooked with 5% palmitic acid, based on amylose, spherulite yields of approximately 60%, based on total starch, were obtained. Spherulites were characterized by SEM and X-ray diffraction. The types of spherulites formed depended on the method used to cool the hot, jet cooked dispersions. Slow cooling for 22 h with magnetic stirring produced mixtures of torus/disc and spherical/lobed spherulites along with trace amounts of micron and sub-micron sized particles. In the absence of stirring, higher yields of sub-micron particles were observed along with spherulite aggregates that were comprised primarily of large, torus/disc spherulites with only minor amounts of spherical/lobed material. When jet cooked dispersions were rapidly cooled in ice, sub-micron spherical particles were the only particles observed. When defatted high amylose cornstarch was used, it was necessary to add an additional amount of palmitic acid to replace the native lipid removed from the starch sample in order to maximize yields and to avoid gel formation. Amounts of complexed palmitic acid in these spherulites varied from 4.5% to 6.1%, by weight. High yields of spherulites were also obtained when oleic acid was used; and, as observed with palmitic acid, sub-micron spherical particles were the only particles observed when the dispersion was rapidly cooled. Factors that affect the formation and morphology of these spherulites were considered.

Thermal Behavior of Ring‐Band versus Maltese‐Cross Spherulites: Case of Monomorphic Poly(ethylene adipate)

AbstractSummary: Two types of spherulites, extinction‐ring and Maltese‐cross, in poly(ethylene adipate) (PEA) were identified, isolated, and separately characterized using DSC and polarized‐light optical microscopy (POM). Ring‐band spherulites in PEA occurred only in a very narrow temperature range roughly between 25 and 30 °C, while Maltese‐cross spherulites at 35 °C and above or at 20 °C and below. Thermal behavior of ring‐spherulites is interpreted, analyzed, and compared to that of Maltese‐cross spherulites. The thermal behavior, like the morphology, was found to be significantly different between these two types of spherulites. Among the three multiple melting peaks in PEA, the highest P3 is proven to be related to melting of lamellae in the ring‐band spherulites; P1 and P2, whose relative extent of overlapping is dependent on the temperature of crystallization, are related to melting of lamellae in the regular ringless spherulites. This study has provided urgent and timely evidence for one major step further in the interpretation of relationships between the thermal behavior, melting, and extinction‐ring versus Maltese‐cross spherulites in semi‐crystalline polymers.DSC curves (10 °C · min−1, scanned from where the trace begins) for: (a) ring‐spherulites in PEA crystallized at 30 °C for 90 min, (b) sample‐(a) heated to 50 °C for 1 min, and (c) sample‐(a) heated to 50 °C, then quenched to 20 °C.magnified imageDSC curves (10 °C · min−1, scanned from where the trace begins) for: (a) ring‐spherulites in PEA crystallized at 30 °C for 90 min, (b) sample‐(a) heated to 50 °C for 1 min, and (c) sample‐(a) heated to 50 °C, then quenched to 20 °C.

Temperature Dependence of Crystallization Behavior in a Phase-Separated Blend of Poly(ε-caprolactone) Homopolymer and Poly(ε-caprolactone)-block-Polybutadiene Copolymer

The crystallization behavior in a macroscopically phase-separated blend consisting of poly(ε-caprolactone) homopolymer (PCL) and PCL-block-polybutadiene copolymer (PCL-b-PB) is investigated both by synchrotron small-angle X-ray scattering (SR-SAXS) and polarized optical microscope (POM) as a function of crystallization temperature Tc. The characteristic size of the phase-separated structure ξ existing in this blend before crystallization can arbitrarily be controlled by changing the phase separation time. When the blend with ξ=2.5 μm is quenched into various Tc, two scattering peaks are observed in the SR-SAXS curve during crystallization, which arise from the crystallized PCL and PCL-b-PB regions. The growth rates of these scattering peaks are identical at lower Tc (≤35 °C), while they deviate gradually with increasing Tc. Only one type of spherulites is observed for the blend with ξ=10 μm crystallized at Tc=35 °C to give a single growth rate, while two different types of spherulites appear at higher Tc (≥40 °C) and their growth rates are significantly different. Therefore the Tc dependence of crystallization behavior observed by POM is qualitatively similar to that obtained by SR-SAXS, though ξ is moderately different between both cases.

Observation of banded spherulites in pure poly(l-lactide) and its miscible blends with amorphous polymers

Banded spherulites of pure poly(l-lactide) (PLLA) were observed via the ‘crystallization after annealing’ procedure, while only common spherulites were obtained via the ‘direct isothermal crystallization’ procedure. Wide angle X-ray diffraction revealed that the two types of spherulites had the same crystal lattice of α-modification. Atomic force microscopy demonstrated that the alternative negative and positive birefringent bands resulted from the alternative edge-on and flat-on lamellar orientations in the spherulites. Furthermore, the effect of thermal history on the spherulitic morphology was investigated in details. The PLLA samples melted for longer time or those with lower melting point were more likely to form banded spherulites. The possibility that the change of molecular weight was a determining factor of banding was excluded by the results on differently prepared samples with the same molecular weight. Therefore, we conclude that it was complete melting of the crystalline residues that favored formation of PLLA banded spherulites. Blending of PLLA with atactic poly(d,l-lactide) or poly[(R,S)-3-hydroxybutyrate], led to reduced band spacing. Effect of blending on the chain mobility, spherulite growth kinetics, supercooling and lamellar surface energy was quantitatively studied, which suggests that the blending-reduced band spacing cannot be attributed to the above factors. Therefore, there are other blending-relevant factors leading to the reduced band spacing.

Atomic force microscopy study of the lamellar growth of isotactic polypropylene

The growth behaviors of cross-hatched and lath-like lamellae of α-form spherulites and flat-on lamellae of β-form pherulites of isotactic polypropylene were studied with a high-temperature atomic force microscopy in situ and in real time. The growth rates of crystal lamellae in types I, II and mixed α-form spherulites and in β-form spherulites, as well as the spatial frequency of tangential branching, were measured. The frequency of tangential branching increases with decreasing crystallization temperature, while the growth rates of leading radial and tangential lamellae are approximately the same at a given temperature. Observations of as-crystallized materials demonstrated that the spacing and length of transverse lamellae is sufficient to differentiate among spherulite types. Height measurements in the melt near the growth surface indicate roles of molecular transport in the crystallization process.

Mechanical properties and structure of high‐density polyethylene samples prepared by injection molding with low‐frequency vibration

AbstractTo better understand the formation of different crystal structures and improve the mechanical properties of high‐density polyethylene samples, melt vibration technology, which generally includes shear vibration and hydrostatic pressure vibration, was used to prepare injection samples. Through melt vibration, the crystal structure changed from typical spherulites of the traditional injection sample to obviously orientated lamellae of vibration samples. Sizes and orientation degrees of lamellae were different according to different vibration conditions. Crystallinity degrees of vibration samples increased notably. Therefore, the tensile strength of vibration samples increased with increasing vibration frequency and vibration pressure, whereas elongation of vibration samples decreased during the first stage and then continued to increase as the vibration frequency increased. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 818–823, 2005

Formation mechanism and morphology in precipitation of vaterite—nano-aggregation or crystal growth?

Spherical and polycrystalline particles of vaterite precipitated from solution has been shown to grow by crystal growth of a spherulitic type, and not by aggregation of nano-sized precursor crystals as often claimed in the literature. The mixing of concentrated solutions of calcium nitrate and sodium carbonate resulted in the formation of amorphous calcium carbonate which transforms within minutes to produce crystalline vaterite. Vaterite spheres nucleate and grow at a moderate relative supersaturation ratio of σ ≅ 5, determined by the dissolution of the amorphous compound. The size of the resulting vaterite spherulites is accounted for by the crystal growth rate determined in absence of nucleation, which disproves the nano-aggregation mechanism. The inner structure of fractured vaterite spheres exhibit the radiating pattern characteristic for spherulitic crystal growth. The final numbers of vaterite spherulites are typical for heterogeneous nucleation processes. It would take supersaturation values, orders of magnitude higher, to obtain the particle numbers required for the proposed nano-aggregation process.