Fine Structures in the Spherulites of Regioregular Poly(3‐dodecylthiophene)

Summary: In this work, we employed various techniques to cooperatively characterize the crystalline structure and morphology of a regioregular poly(3‐dodecylthiophene). We observed the spherulites in casting films first by polarized light microscopy and then further studied the fine structures within the spherulites by scanning and transmission electron microscopy. These studies showed that the stripe‐like structures with a width of ≈20 nm and a length of 100–500 nm are the basic building blocks of the spherulites. The small‐angle X‐ray scattering and wide‐angle X‐ray diffraction studies further confirm the existence of such the structures. Considering the stiff and unfolding feature of the macromolecules, we believe that the stiff macromolecules may adopt a special way to form the fine structure: the orientation of stiff macromolecules parallel to the longitudinal direction of the stripes without any chain folding.

     

Structural Investigation of Poly(3‐hydroxybutyrate) Spherulites by Microfocus X‐Ray Diffraction

A banded spherulite of bacterial poly(3‐hydroxybutyrate) (band spacing 120 μm) was linearly scanned along the radial direction in 3 μm steps by means of microfocus X‐ray diffraction using a synchrotron source with a beam diameter of 3 μm. A large number of X‐ray patterns was collected inside each band. Those taken at the center of the bands represented the two limiting diffraction patterns from which the exact orientation of the unit cell was inferred. The intensity of the reflections (020) and (002), taken as indicators of parallelism to the X‐ray beam of the unit cell's c‐ or b‐axis, respectively, changed periodically along the spherulite radius, alternating maxima with zero‐intensity zones. When the reflection (020) showed a maximum, the reflection (002) was practically nil and vice versa. This behavior clearly shows that the unit cell's mean position smoothly rotates around the a‐axis with increasing distance from the spherulite center. The identity of the cell rotation period with the band spacing derived from optical microscopy observations provides structural evidence that the extinction bands originate from a regular twisting of the lamellar crystals during their growth.     

New Poly[(R)‐3‐hydroxybutyrate‐co‐4‐hydroxybutyrate] (P3HB4HB)‐Based Thermogels

Poly[(R )‐3‐hydroxybutyrate] (P3HB) is a potential candidate for biomaterials due to its biocompatibility and biodegradability. However, P3HB needs to have tunable hydrophobicity, modification through chemical functionalization and the right hydrolytic stability to increase their potential for water‐based biomedical applications such as using them as in situ forming gels for drug delivery. This work focuses on using a copolymer, poly[(R )‐3‐hydroxybutyrate‐co‐4‐hydroxybutyrate] (P3HB4HB) in a thermogelling multiblock system with polypropylene glycol and polyethylene glycol to study the effect of the hydrophobic P3HB4HB on gelation properties, degradation, and drug release rates with reference to P3HB. Thermogels containing P3HB4HB segments show lower critical micellization concentration values in a range from 3 × 10⁻⁴ to 1.08 × 10⁻³ g mL⁻¹ and lower critical gelation concentration values ranging from 2 to 6 wt% than that of gels containing P3HB. Furthermore, gels containing P3HB4HB degrade at a slower rate than the gels containing P3HB. Drug release studies of 5 µg mL⁻¹ of doxorubicin show that gels containing P3HB4HB exhibit sustained release although the release rates are faster than gels containing P3HB. However, this can be modified by varying the concentration of the gels used. Process optimization of purifying the starting material is one important factor before the synthesis of these biomaterials.

     

Crystallization and Ring‐Banded Spherulite Morphology of Poly(ethylene oxide)‐block‐Poly(ε‐caprolactone) Diblock Copolymer

Summary: The crystallization behavior of crystalline‐crystalline diblock copolymer containing poly(ethylene oxide) (PEO) and poly(ε‐caprolactone) (PCL), in which the weight fraction of PCL is 0.815, has been studied via differential scanning calorimeter (DSC), wide‐angle X‐ray diffraction (WAXD), and polarized optical microscopy (POM). DSC and WAXD indicated that both PEO and PCL blocks crystallize in the block copolymer. POM revealed a ring‐banded spherulite morphology for the PEO‐b‐PCL diblock copolymer.

DSC heating curve for the PEO‐b‐PCL block copolymer.     

Banded Spherulitic Morphology in Blends of Poly (propylene fumarate) and Poly(ϵ‐caprolactone) and Interaction with MC3T3‐E1 Cells

The thermal properties, morphological development, crystallization behavior, and miscibility of semicrystalline PCL and its 25, 50, and 75 wt% blends with amorphous PPF in spin‐coated thin films crystallized at various crystallization temperatures (T_c) from 25 to 52 °C are investigated. The surface roughness of PPF/PCL (?_PCL = 75%) films increases with increasing T_c and consequently the adsorption of serum proteins is also increased. No significant variance is found in surface hydrophilicity or in mouse MC3T3‐E1 cell attachment, spreading, and proliferation on PPF/PCL (?_PCL = 75%) films crystallized isothermally at 25, 37, and 45 °C, because of low ridge height, nonuniformity in structures, and PPF surface segregation.     

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

Summary: 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.     

Differences Between Stereocomplex Spherulites Obtained in Equimolar and Non‐Equimolar Poly(L‐lactide)/Poly(D‐lactide) Blends

PLLA/PDLA blends were crystallized between 120 and 195 °C. The stereocomplex spherulites acquired in equimolar and non‐equimolar blends were compared using POM, WAXD, DSC, and AFM. For equimolar blends, stereocomplex crystals show spherulites with positive birefringence, which is ascribed to the existence of domains made up of tangentially oriented lamellae. For PLLA‐rich (or PDLA‐rich) blends, the signs of the birefringence changed from a positive spherulite to a mixed spherulite and then to a negative spherulite. In negative spherulites, most lamellae orient radially. Radial and tangential cracks were observed in equimolar blends when crystallization took place above 175 °C whereas no cracks formed for non‐equimolar blends.

     

Thermoplastic Vulcanizates Based on Highly Compatible Blends of Isotactic Poly(propylene) and Copolymers of Atactic Poly(propylene) and 5‐Ethylidene‐2‐norbornene

Highly compatible thermoplastic/elastomer blends were used to prepare thermoplastic vulcanizates (TPVs) with refined morphologies and improved mechanical properties. Copolymers of atactic poly(propylene) (aPP) and 5‐ethylidene‐2‐norbornene (ENB) (aPP‐co‐ENB) were prepared via metallocene catalysis. Blends of isotactic poly(propylene) (iPP) and the aPP‐co‐ENB rubbers are immiscible in the melt, but the very high compatibility leads to a refinement of the morphology in comparison to blends based on iPP and ethylene‐propylene‐ diene (EPDM) rubber. The aPP‐co‐ENB‐based blends show improved tensile properties, while the relatively high T_g of the rubber phase retards the elastic recovery at room temperature. Dilution of the TPVs with oil broadens the temperature window for applications by a signification reduction of the T_g and improves the elasticity of the TPVs. This study demonstrates that the lower limit of the rubber particle size of TPVs that is attainable via dynamic vulcanization of immiscible blends is in the order of 300–500 nm.

     

Metallocenic Isotactic Poly(propylene) and its Copolymers with 1‐Hexene and Ethylene

A comprehensive study of the structure and properties has been performed for copolymers of propylene‐1‐hexene, CiPH, and propylene‐ethylene, CiPE, synthesized by an isotactic metallocene catalyst system. The comonomer content constitutes the most important factor affecting the structure and properties of these CiPH and CiPE copolymers, although the length of the comonomer is also very important. Thus, a considerable decrease in crystallinity is observed in the two kinds of copolymers as the comonomer content increases. The structure in the CiPH copolymers evolves, however, from the typical, monoclinic crystal lattice to mesomorphic‐like, ordered entities for the highest 1‐hexene molar fraction, whereas in the CiPE copolymers the structural evolution with molar fraction goes from a monoclinic lattice to an almost amorphous material. All of these variations in crystal structure significantly influence the viscoelastic and mechanical behavior of these CiPH and CiPE copolymers. Consequently, the location and intensity of the different relaxation mechanisms, as well as the rigidity parameters (storage and Young's moduli and microhardness) and deformation mechanism are strongly dependent upon composition.

     

Effects of Stereocomplex Nuclei or Spherulites on Crystalline Morphology and Crack Behavior of Poly(L‐lactic acid)

Introduction of sc‐PLA crystals as small nuclei or large sc‐PLA spherulites has great influence on patterning the inter‐phase boundaries and reducing the cracks in crystallized PLLA in mixtures with PDLA. Unmelted sc‐PLA crystals as nuclei induce cracks in later‐crystallized PLLA, whereas co‐crystallization of PLLA with PDLA to develop simultaneous PLLA and sc‐PLA spherulites is effective in altering the inter‐phases for minimizing the cracks. PLLA co‐crystallized with sc‐PLA spherulites tends to be more compact than PLLA spherulites crystallizing on sc‐PLA nuclei. In general, the sc‐PLA spherulites suppress the occurrence of a stressed interphase in PLLA spherulites and the depth of cooling‐induced cracks is also decreased.

     

Crystallization and Melting Behavior of Poly(3‐hydroxybutyrate)‐Based Blends

Summary: Blends of high molecular weight poly(R‐3‐hydroxybutyrate) (PHB) ( = 352 000 g · mol^?1), comprising of either low molecular weight poly(R‐3‐hydroxybutyrate) (D‐PHB) ( = 3 900 g · mol^?1) or poly[(R‐3‐hydroxybutyrate)‐co‐(R‐3‐hydroxyvalerate)] (PHBV) ( = 238 000 g · mol^?1) with 12 mol‐% hydroxyvalerate (HV) content as a second constituent, were investigated along with the thermal properties and morphologies. After isothermal crystallization, a lowering of the melting temperature of PHB can be observed with increasing content of the second component in the blends. This behavior points towards miscibility of the constituents both in the liquid and the solid state. Crystallization kinetics was studied under isothermal and non‐isothermal conditions. The overall kinetics of isothermal crystallization was analyzed in terms of the Avrami equation. Only one crystallization peak is observed in all cases for the PHB/D‐PHB and PHB/PHBV blends under the conditions studied. This demonstrates co‐crystallization of the constituents. The addition of D‐PHB or PHBV to PHB reduces the rate of crystallization of the blends compared to that of neat PHB. The corresponding activation energies of crystallization also decrease with an increasing concentration of the second constituent. Non‐isothermal crystallization, carried out with different cooling rates held constant, is discussed in terms of a quasi‐isothermal approach. The corresponding rate constants as functions of reciprocal undercooling show Arrhenius‐like behavior in a certain range of temperatures. At sufficiently high undercooling, the rate constants of crystallization for the isothermal process exceed those reflecting non‐isothermal conditions, whereas in the limit of low undercoolings, the rate constants become similar. Ring‐banded morphologies are observed when PHB is in excess. When the respective second component is the major component, fibrous textures of the spherulites develop.

Polarized micrograph of PHB/PHBV 90/10.     

In Situ FTIR Spectroscopy Study on the Melting Process of Isotactic Poly(propylene)

The melting process of isotactic poly(propylene) (iPP) sample isothermally crystallized at 130°C for half an hour is carefully studied by means of variable‐temperature FTIR spectroscopy and DSC. Based on the IR intensity changes of regularity and conformational bands vs. temperature, it is found that the helical structure of macromolecular chains can be retained in the iPP melt after the polymer crystals are melted. When temperature is somewhat higher than 170.5°C, the macromolecules get sufficient energy from surroundings to overcome the energy barrier of helical structure, so the quantity of helical structure in iPP melt reduces dramatically. This conclusion is also confirmed by DSC studies on crystallization behavior of different iPP melts. The activation energy to destroy the helical structure of iPP melt is 60.1 kcal/mol determined by the Snyder method. After the major transition, some level of order still persists in the melt and it is gradually lost at higher temperatures.     

Ring‐Banded Spherulitic Crystals of Poly(3‐butylthiophene) via Controlled Solvent Evaporation

The preparation of ring‐banded spherulites in poly(3‐butylthiophene) via controlled solvent evaporation of solution‐cast films is reported. The spherulites display unusual concentric ring‐banded structures under both polarized and unpolarized lights. The size of the ring‐banded spherulites is 300 ± 100 µm in diameter and the periodicity of the bands is 15 ± 2 µm. The periodic bands of the spherulite consist of alternating ridge and valley surface patterns and the crystalline lamellae in the bands are more or less parallel to the radial growth direction of the spherulites. Local lamellar bending and branching are observed analogous to that of classical non‐conjugated polymers. A possible diffusion‐induced rhythmic growth mechanism is proposed to interpret the formation of periodic banding of the spherulite.     

Non‐oxidative Thermal Degradation of Poly(glycidol), Poly(glycidol)‐g‐L‐lactide,and Poly(glycidol)‐g‐glycolide

Three polymers of pharmaceutical/medical relevance are synthesized: poly(glycidol) (PG), poly(glycidol)‐g‐L ‐lactide (PG‐g‐La), and poly(glycidol)‐g‐glycolide (PG‐g‐Gly). Because the thermal stability of these polymers is an essential factor of their processing and practical application, the study focuses on kinetic and mechanistic aspects of non‐oxidative thermal degradation. The study is conducted by combining thermogravimetry, Fourier transform infrared spectroscopy, and isoconversional kinetic analysis. It is found that PG degrades in a single mass loss step, whereas, PG‐g‐La and PG‐g‐Gly in two. It is demonstrated that the first step in degradation of PG‐g‐La and PG‐g‐Gly is associated with decomposition of the pendant groups and the second is due to degradation of the PG backbone.

     

Effect of β‐Cyclodextrins on the Morphological Change of Poly(3‐hydroxybutyrate)

Summary: The effects of β‐CD, partially methylated and per‐methylated β‐CDs on the crystallization behavior of P(3HB) have been investigated. All measurements, including FT‐IR spectra, WAXD, and DSC, showed that the details of interaction between P(3HB) and respective CDs were varied with the degree of methyl substitution of CDs. The crystallization of P(3HB) was enhanced by an addition of immiscible β‐CD, while it was restricted by the introduction of methylated CDs via the formation of miscible blend with di‐O‐methyl β‐CD and via the formation of an IC with tri‐O‐methyl β‐CD, respectively.

     

Effect of Methylated Cyclodextrins on the Crystallization of Poly(3‐hydroxybutyrate)

Summary: The effects of methylated CDs, α‐ and β‐DMCD and α‐ and β‐TMCD on the crystallization behavior of P(3HB) have been investigated by employing DSC and polarized optical microscopy (POM). The crystallization and nucleation of P(3HB) was improved by an addition of appropriate amount of each methylated CD, while negative effect of miscible blend was observed when the amount of addition exceeds the optimum value for the maximum nucleating effect. β‐TMCD was shown to be the most effective for the enhancement of the P(3HB) crystallization, thought to be due to the possibility of IC formation with P(3HB).

Plots of log{?ln [1 ? X(t)]} versus log (t) for mixtures of P(3HB) with different CDs or talc, respectively.     

Flow‐Induced Orientation in Miscible Crystalline Polymer Blends of Poly(vinylidene fluoride) and Poly[(3‐hydroxybutyrate)‐co‐(3‐hydroxyvalerate)]

Oriented films of miscible polymer blends of poly(vinylidene fluoride) and poly[(3‐hydroxybutyrate)‐co‐(3‐hydroxyvalerate)] were prepared using a flow‐orientation technique. The lamellar structure and crystal orientation depended upon composition and flow temperature (T_flow). An interlamellar exclusion structure was induced in the blend flow‐oriented below 150 °C, whereas an interlamellar inclusion structure was developed above 150 °C. The crystal orientation of PHBHV was affected by the lamellar structures because the PHBHV chains crystallized in the pre‐existing crystalline morphology of PVDF. Crystallization of PHBHV was markedly restricted at lower PHBHV contents.

     

Crystal Polymorphism and Spherulites in Poly(butylene adipate) Diluted with Strongly Versus Weakly Interacting Amorphous Polymers

Polymorphism and ring‐banded spherulites in poly(butylene adipate) (PBA) diluted with poly(vinyl acetate) (PVAc) or poly(hydroxyether of bisphenol A) (phenoxy) were studied. For neat PBA, polymorphism and ring‐banded spherulites occur at overlapped T_c = 28–31 °C (4 °C range). By comparison, ring bands of crystallized PBA/PVAc blend remain similar to neat PBA; while for PBA/phenoxy blend, ring bands are completely disrupted (revealed by surface AFM phase images), owing to strong interchain interactions between PBA and phenoxy. The results summarily demonstrate that the T_c range for polymorphism becomes much wider (T_c = 19–32 °C) with the addition of the amorphous polymers and reveals the phenomenon of ring bands in PBA is not correlated or attributed to its α+β polymorphism.     

Direct Observation of Poly(propylene)‐block‐Poly(ethylene‐co‐propylene) Molecules by Atomic Force Microscopy

Summary: Atomic force microscopy (AFM) has been applied to get molecular images of diblock poly(propylene)‐block‐poly(ethylene‐co‐propylene) copolymers deposited on mica from diluted solutions at elevated temperatures. Both isolated molecules and their small aggregates have been visualized as compact particles of various sizes with outspreading poly(ethylene‐co‐propylene) chains. On the base of the height, volume and morphological analysis AFM images were divided into three groups. In the first group the compact particles are suggested to be small regular‐shaped crystallites formed by a few poly(propylene) blocks. Some isolated particles of this group were connected with single copolymer chains. In the second group the compact particles have larger dimensions and irregular or round shapes implying unordered packing of constituents. The third group were represented by isolated poly(ethylene‐co‐propylene) coils. The two‐dimensional expansion of coils on mica both isolated and included in aggregates exceeds several times their dimensions in a solution. The probable mechanism of such an expansion is proposed relying on the existence of van‐der‐Waals surface force field of a sufficient strength in the vicinity of the crystal surface.

Enlarged AFM height images of block‐copolymer aggregates of group A with small compact particles of regular shapes (frames a, b, c) and group B (frame d) with a large globular compact particle.     

Molecular Motions in the Supramolecular Complexes between Poly(ε‐caprolactone)‐Poly(ethylene oxide)‐Poly(ε‐caprolactone) and α‐ and γ‐Cyclodextrins

The structure and molecular motions of the triblock copolymer PCL‐PEO‐PCL and its inclusion complexes with α‐ and γ‐cyclodextrins (α‐ and γ‐CDs) have been studied by solid‐state NMR. Different cross‐polarization dynamics have been observed for the guest polymer and host CDs. Guest–host magnetization exchange has been observed by proton spin lattice relaxation T₁, proton spin lattice frame relaxation T_1ρ and 2D heteronuclear correlation experiments. A homogeneous phase has been observed for these complexes. Conventional relaxation experiments and 2D wide‐line separation NMR with windowless isotropic mixing have been used to measure the chain dynamics. The results show that for localized molecular motion in the megahertz regime, the included PCL block chains are much more mobile than the crystalline PCL blocks in the bulk triblock copolymer. However, the mobility of the included PEO block chains is not very different from the amorphous PEO blocks of the bulk sample. The cooperative, long chain motions in the mid‐kilohertz regime for pairs of PCL‐PEO‐PCL chains in their γ‐CD channels seem more restricted than for the single PCL‐PEO‐PCL chains in the α‐CD channels, however, they are not influencing the more localized, higher frequency megahertz motions.