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Polarized optical microscopy (POM), scanning electron microscopy (SEM), and synchrotron microbeam wide-angle X-ray diffraction (WAXD) were used to investigate the mechanisms of periodic assemblies leading to ring-banded crystal aggregates with light-grating capacity for iridescence in poly (1,4-butylene adipate) (PBA) modulated with poly (ethylene oxide) (PEO). A critical finding is that the PBA crystal assembly on the top surface and in the interior constitutes a grating architecture, with a cross-bar pitch equaling the inter-band spacing. The inner lamellae are arranged perpendicularly to the substrate under the ridge region, where they scroll, bend, and twist 90° to branch out newly spawned lamellae to form the parallel lamellae under the valley region. The cross-hatch grating with a fixed inter-spacing in the PBA aggregated crystals is proved in this work to perfectly act as light-interference entities capable of performing iridescence functions, which can be compared to those widely seen in many of nature’s organic bio-species or inorganic minerals such as opals. This is a novel breakthrough finding for PBA or similar polymers, such as photonic crystals, especially when the crystalline morphology could be custom-made and modulated with a second constituent.

Extensive microscopic and thermal analyses and X-ray diffraction characterizations are conducted to investigate an unusual morphology and its evolution in extreme nonequimolar mixtures of poly(L-la...

Amorphous poly(p-vinyl phenol) (PVPh) was added into semicrystalline poly(p-dioxanone) (PPDO) to induce a uniquely novel dendritic/ringed morphology. Polarized-light optical, atomic-force and scanning electron microscopy (POM, AFM, and SEM) techniques were used to observe the crystal arrangement of a uniquely peculiar cactus-like dendritic PPDO spherulite, with periodic ring bands not continuingly circular such as those conventional types reported in the literature, but discrete and detached to self-assemble on each of the branches of the lobs. Correlations and responsible mechanisms for the formation of this peculiar banded-dendritic structure were analyzed. The periodic bands on the top surface and interior of each of the cactus-like lobs were discussed. The banded pattern was composed of feather-like lamellae in random fractals alternately varying their orientations from the radial direction to the tangential one. The tail ends of lamellae at the growth front spawned nucleation cites for new branches; in cycles, the feather-like lamellae self-divided into multiple branches following the Fibonacci sequence to fill the ever-expanding space with the increase of the radius. The branching fractals in the sequence and the periodic ring-banded assembly on each of the segregated lobs of cactus-like dendrites were the key characteristics leading to the formation of this unique dendritic/ringed PPDO spherulite.

Poly(butylene adipate) (PBA) self-aggregation into unique periodicity correlating to its interfacial photonic properties is probed in detail. Investigations on the unique periodic morphology and top-surface and interior architectures in specifically crystallized PBA are focused on its novel photonic patterns with periodic gratings. Detailed analysis of the interior lamellae from ringless to periodically ordered aggregates (crystallized at 33-35 °C vs. Tc = 30 °C) serves as ideal comparisons. Each interior arc-shape shell is composed of tangential and radial lamellae mutually intersecting at 90o angle. The interior layer thickness in SEM-revealed arc-shape shish-kebab shell is exactly equal to the optical inter-band spacing (≈6 µm). A 3D assembly mechanism of periodically banded PBA crystals is proposed, where the orderly arrays on top surfaces as well as the interior microstructures of strut-rib alternate-layered assembly resemble nature's photonic crystals and collectively account for the interfacial photonic properties in the ring-banded PBA crystal that is novel and has potential applications in future.

Star-shaped polylactide (SSPLA) nanoparticles (NPs) with dipyridamole (DIP) core conjugated with 5-fluorouracil (5FU) and 4-piperidinopiperidine (4PIP) were designed and synthesized to achieve apoptosis by synergistic dose-dependent delivery than using free drugs. In our current investigation, DIP was employed as the initiator in ring-opening polymerization reaction to make SSPLADIP. We then described the synthesis of tailor-made, self-assembled, carboxyl group-substituted fluorescent SSPLADIP conjugated with a secondary amine group of 5FU anticancer drug to form a dual prodrug complex (SSPLADIP5FU). To compare the efficacy of this combination, another anticancer drug 4PIP was also covalently conjugated with a hydroxyl-end terminal by nucleophilic substitution on SSPLADIP to form SSPLADIP4PIP. 4PIP inhibits the topoisomerase enzyme in DNA replication. Synthesized star-shaped drug constructs were characterized by atomic force microscopy, scanning electron microscopy, NMR, fluorescence spectroscopy, gel permeation chromatography, and MALDI-TOF. This is the first report on these drug combinations (DIP-5FU and DIP-4PIP) fabricated on the polylactic acid biopolymer to form NPs of size

Dendritic spherulites are one type of diversified ways of crystal aggregations into micrometer-size consortia by kinetics-driven assembly from nanometer-size crystal plates (i.e., lamellae or single crystals). Crystallized polymers can exist in states of different degrees of order, which lead to the resulting assembled morphologies are of non-equilibrium supramolecular hierarchical patterns of crystal structures. Diffusion-controlled growth patterns emerge, which change the details of dendritic morphology depending on Tc (degree of super-cooling), polymer-diluent interactions, confinement. Investigation to the diversified patterns of lamellar assembly into polymer dendritic spherulites has come to several key conclusions. This article reviews and summarizes the top-surface-relief morphology and interior dissections of polymer dendritic spherulites, where the dendrites may be composed of ringed stripes or fibrous cilia crystals. The results yield interesting consistency for constructing workable mechanisms to account for each type of morphologies with respect to their molecular weights and crystallization kinetics conditions (i.e., Tc, space confinements, film thickness, blend interaction, as well as blend composition).

Towards the development of high-performance green composites, the surface functionalized cellulose nanocrystals (CNC) have been widely used as reinforcement along with biopolymer. In our previous work, it has been demonstrated that CNC grafted with PDLA (CNC-g-PDLA) could improve the crystal nucleation density and heat distraction ability of PLLA matrix via the PLLA/PDLA stereocomplex interaction. Herein, to understand the role of CNC-g-PDLA on the deformation behavior of PLLA/CNC-g-PDLA nanocomposites, the melt-quenched PLLA/CNC-g-PDLA nanocomposite was uniaxially stretched at 160 °C with various draw ratios. The stretched PLLA/CNC-g-PDLA composites allow us to discriminate the crystal transformation and crystal orientation of three individual components in the composites, that is, (i) PLLA matrix, (ii) PLLA/PDLA stereocomplex existed as interfacial phase, and (iii) CNC reinforcement. The results indicate that PLLA α′ and PLLA/PDLA stereocomplex crystals (βC) appear at the initial stage of drawing process. The disordered α′ transforms to ordered α and β forms gradually with increasing in draw ratio, whereas βC-crystals keep almost unchanged during the whole drawing process. The calculation on orientation function of various crystals suggests that the lamellaes of α form have the largest orientation degree along the stretching axis. Meanwhile,CNC nanoparticles and the βC crystals form the nano-dimensional shish kebab structure during stretching and present relatively low orientation. This study provides the physical insight to guide the preparation of high performance PLLA nanocomposites with hierarchical crystal and orientation structure.

The self-assembly structures of lamellae in optical ring bands have a critical effect on their optical and physical arrangements. Two different types of dendritic banded spherulites (namely ring-banded and zigzag ring-banded) are formed in poly(ε-caprolactone)/poly (phenyl methacrylate) blend at crystallization temperatures of 42 and 46 °C, respectively. The difference in optical birefringence of ring bands in two types of spherulites is resolved by means of direct morphological comparison. Banded spherulites are fractured carefully to facilitate lamellar orientation analyses of both the top surface and the interior surface. The results have revealed the existence of tree-like dendritic fractal growth lamellar assemblies in both banded spherulites. The optical ring patterns of the banded spherulites are differentiated mainly by the fractal orientation of the edge-on crystal branches in the ridge region. On the basis of detailed morphological analysis, 3D-lamellar assembly mechanisms are proposed to explain the growth of dendritic ring-banded spherulites at 42 °C and dendritic zigzag ring-banded spherulites at 46 °C.

Poly(3-hydroxybutyric acid-co-3-hydroxyl-valeric acid) (PHBV) crystallized in the presence of a polymeric diluent impurity is analyzed at specific crystallization temperatures (Tc) from 60 °C to 80 °C. 3D-dissected interior analysis for ring-banded spherulites evidently reveals that the alternate bands exist in not only top surface but also 3D interiors composted of grating-assembled lamellae. Aggregation of the lamellae, initially from two ends of nucleus sheaf-bundles, packs via crystal-by-crystal mode into either Archimedean single-spirals or Fermat's double-spirals, which constitute the “ridge” bands. Then from the ridge-band lamellae, secondary lamellae then branch out at 60–80° oblique angles, with irregular bending, twisting, or scrolling to accommodate in the confined space, to form the “valley” bands. Each new growth cycle repeats the fractal patterns of previous one. The periodic cycles repeat themselves in a fractal fashion to form a cross-lamellar structure, with “crossbar pitch” equal to its optical band spacing. Periodicity of aggregation in top surface and interior is depicted in detailed 3D assembly, beyond and distinguished from conventional planar analytical approaches, for novel mechanisms.

3D morphology of poly(3-hydroxybutyrate) (PHB), crystallized in the presence of diluents of poly(1,3-trimethylene adipate) and poly(ethylene oxide), is probed using a novel approach coupled with selective etching. For interpreting the mechanisms of crystal periodic aggregation, various microscopic techniques and synchrotron microbeam X-ray analysis are used to observe the top surface in connection with the 3D crystal assemblies. Periodic grating architectures, with the cross-bar pitch exactly matching with the optical band spacing, are proved in banded PHB. The crystals under the ridge branch out to spawn finer crystals orienting/bending horizontally underneath the valley band, repeating till species drainage or impingement. The grating structure in the banded PHB resembles many nature's iridescence crystals and is further proved by photonic reflection results as a critical breakthrough novel finding.

The dipyridamole is emissive in the solution state; however, the emission is weakened in the solid state due to the aggregation-caused quenching. The aggregation of dipyridamole can be prevented by synthesizing star-shaped poly(l-lactide) (SSPLLA) using dipyridamole core. During crystallization of the polymer, chromophore molecules were expelled out of crystalline lamellae and reside at the interface of crystalline and amorphous phase. The helical chains of poly(l-lactide) (PLLA) can induce the helicity to chromophore moieties during the crystallization of PLLA. The photoluminescence (PL) quantum yield measured for the semicrystalline polymer is 46%. When the polymer is melt-quenched to amorphous, PLLA chains remain in the random conformation, and no induced circular dichroism of dipyridamole was found. In the amorphous polymer, the dipyridamole molecules are scattered and show higher PL quantum yield ∼55%. Transparency of the polymer and the disruption of π-stacking of chromophore resulted in the higher ...

A completely novel 3D dissection approach is taken to re-investigate high-density polyethylene (HDPE) crystallized into periodic architectures in a wide range of Tc . This work first discovers that ring bands present in HDPE are crystallized in a quite wide Tc range (90-120 °C) all within regime-III growth. With further detailed analyses of the top-surface-relief patterns and 3D architectures of HDPE spherulites, this work has fully clarified the periodic morphology packed with alternate ways of single-crystal aggregates in correlation with the optical banding patterns. The proposed assembly mechanism sheds light that the periodic bands are actually composed of a cross-hatch grating structure in that the alternately perpendicular orientations from the ridge to valley bands being related to the interior radial to tangential lamellae. Such grating architectures in the interiors of HDPE can be viewed as a mimicry resembling shish-kebab lamellae self-aligned by Archimedean spiral-spins from the nucleus center.

This work utilized an in-house synthesized aryl polyester, poly (decamethylene terephthalate) (PDT), to investigate the crystal assembly of unique camellia-flower-like extinction bands periodically assembled in spherulites formed at specific Tc's or driven by other kinetic factors. These extinction PDT bands at high Tc's (110–125 °C) and confined in thin films are packed by parallel flat plates of single-crystal-like dimensions in nanometer to micrometer scales (measuring 4 μm × 4 μm x 20 nm) self-assembled as terrace-like shingles that are bordered with an optically extinct boundary. The valley corresponds to where most amorphous ingredients accumulate and the growth precipitates suddenly from tip of ridge to near the substrate, resulting in an optical extinction border. All ridges (convex bands) are composed of discrete crystal plates aligned as roof-shingle stacks along the circumferential bands, and the crystals do not traverse across the bands. These lamellae on ridge bands are discrete and do not twist at all or rotate 360° angle continuously extending from nucleus to periphery. The circular-extinction bands of PDT of nanometer films (300–400 nm) are composed of parallel lamellae with the terrace alignment pointing along the circumferential direction; the epicycloid-extinction bands of thicker PDT specimens (2000–3000 nm) are assembled with single-crystal plates of lozenge shapes and aligned in growth-preferred directions to form petal-like tips.

Novel approaches and fractal-branching models are proposed to provide an evidence-supported mechanism of hierarchal lamellae assembly with regular periodicity in ring-banded poly(ϵ-caprolactone) (PCL) crystallized in bulk forms from PCL/poly(phenyl methacrylate) mixtures. Crystallized specimens are examined with two different film-thickness levels. For interior analysis, specimens are fractured in delicate ways to study correlations of the architectures on top-surface vs. interior lamellae, and how these crystal species self-assemble to display morphological repetitive fractals with optical-banding periodicity. 3D self-assembly of alternate horizontal and vertical lamellar bundles with fractal-branching leads to varieties of architectures of ring-banded aggregates packed with lamellar branches at periodic intervals.

Two triblock ABA copolymers poly( l -lactide- b -dimethylsiloxane- b - l -lactide) (PLLA- b -PDMS- b -PLLA) and poly( l -lactide- b -ethylene glycol- b - l -lactide) (PLLA- b -PEG- b -PLLA) containing poly( l -lactide) were synthesized by ring opening polymerization of l -lactide using bis(hydroxyalkyl) terminated PDMS and hydroxyl end-capped polyethylene glycol as macroinitiators, respectively. Both the triblock copolymers were melt-quenched to −40 °C to prepare the amorphous samples. The melt morphology of the triblock copolymers was preserved upon cooling the melt to −40 °C. PLLA and PDMS blocks are immiscible in the melt, and the amorphous triblock copolymer shows two distinct glass transition temperatures ( T g ) on heating. On the other hand, PLLA and PEG segments are miscible and the triblock copolymer shows the single T g . Structural evolution of PLLA during heating of the amorphous ABA triblock copolymers has been investigated by measuring the variable temperature small-angle and wide-angle X-ray scattering (SAXS and WAXS) and FTIR spectra. In the case of PLLA- b -PDMS- b -PLLA triblock copolymer (immiscible system), the mesophase of PLLA was found to appear just above the T g of PLLA block (∼45 °C), and on further heating the mesophase changed to the regular α form at around 90 °C. On the other hand, in PLLA- b -PEG- b -PLLA (miscible system), the mesophase of PLLA was found to appear at lower temperature i.e. −20 °C, because of the enhanced molecular mobility of PLLA chains in the presence of PEG. However, irrespective of the mesophase formation temperature, the ordered α form has appeared at around 90 °C. In this way, during heating of the amorphous triblock copolymers, the PLLA block was found to crystallize into the ordered α form always through the mesophase just above the T g of PLLA. These results are helpful in understanding the regularization process of semicrystalline polymers in different environments.

As a popular bioplastic, poly ( l -lactic acid) (PLLA) still faces some drawbacks mainly related to its low crystallization rate and heat distortion resistance. Herein, we demonstrate a facile and promising route to solve these problems by compositing PLLA with poly( d -lactide) grafted cellulose nanocrystal (CNC-g-PDLA) which can be synthesized via ring-opening polymerization of d -lactide on the CNC surface. The grafting density of PDLA on the CNC surface has been quantified by newly developed spectral method using FTIR technique. Moreover, the non-isothermal and isothermal crystallization behavior of PLLA/CNC-PDLA composites has been investigated by DSC, POM and WXRD. Our results show that the addition of small amount of CNC-g-PDLA could enhance the crystallization rate of PLLA significantly due to the heterogeneous nucleation effect of CNC and the presence of stereocomplex crystals. In addition, the specific stereocomplex interaction in the interphase of PLLA matrix and modified CNC particles results in great improvement of both storage modulus and the heat distortion resistance of the PLLA/CNC-g-PDLA nanocomposites. This study provides a way to design advanced PLLA-based nanocomposites with fast matrix crystallization ability and excellent heat distortion resistance.

The classical model of continuous helix-twist lamellae versus a novel corrugate-grating assembly in accounting for long-debated issues of periodic optical banding in poly(ethylene adipate) (PEA) polymer spherulites is critically assessed, by comparing and checking against a series of scientific evidence based on experimental data of scanning electron microscopy (SEM), ultrathin microbeam small-angle & wide-angle X-ray scattering (SAXS/WAXD), and optical microscopy. Analyses show that grating-structured model fits perfectly with all results. The novel proposition of grating-structured lamellae with a crossbar pitch fits perfectly with the experimental optical band spacing, and the interior morphology dissection is fully supported by the literature-reported microbeam X-ray data.

It is worthy to understand the reinforcement of nanoparticle in rubber blends in application prospect because of its dispersion and distribution. The dielectric and mechanical methods were used to study the reinforcement impact of the carbon black (CB) in NR/NBR blends, based on the percolation and reinforcement theories. Results indicated that the CB aggregates had dispersed in NBR phase and the reinforcement effect was dependent on both CB concentration and the rubber blend ratio. It has been observed that the CB particles diffused and filling in the NBR reinforcement network at 50:50 ratio of NR/NBR blend, CB particles assembled as supernanosphere at 70:30 ratio and CB particles wrapped/covered supernanosphere at 90:10 ratio. The highest elongation at break was observed in 90:10 ratio of NR/NBR. The new observations are conducive to providing guidelines for producing high mechanical performance and low conductivity percolation threshold elastomers via a maturely industrial method for a wide range of application.

In this study, lactic acid monomer or dimer is grafted onto CNC by a simple esterification reaction. The quantitative solid-state 13C NMR spectrum suggests that more than 87% of all the available OH groups on the surface of CNC are substituted by lactic acid. Such modified CNC (CNC-g-LA) exhibits excellent thermostability and nano-sized dispersion in chloroform. Benefit from this character, fully biobased PLLA/CNC-g-LA nanocomposite could be prepared simply by a solution-casting method. The crystallization behavior of obtained nanocomposites has been systematically investigated by differential scanning calorimetry (DSC). The results show that the crystallization rate of PLLA is distinctly enhanced. Moreover, the mechanical properties of nanocomposites are also improved remarkably by the addition of CNC-g-LA because of its excellent dispersion and compatibility with PLLA matrix. This study provides a green and facile way to modify CNC for fabricating bio-nanocomposites with fast crystallization rate and improved mechanical properties.

Poly(l-lactide-b-dimethylsiloxane-b-l-lactide) (PLLA-b-PDMS-b-PLLA) triblock copolymer was synthesized by ring-opening polymerization of l-lactide using bis(hydroxyalkyl)-terminated PDMS as a macroinitiator. The block copolymer was immiscible in the melt, and the melt morphology was preserved upon cooling the melt to −120 °C. It was also observed that at moderate cooling rates PDMS and PLLA blocks remain in the amorphous phase at temperatures below −120 °C. The breakout and preservation of the nanostructure morphology of the triblock copolymer have been investigated by variable temperature small-angle and wide-angle X-ray scattering (SAXS and WAXS) during heating. The crystallization and melting of PDMS block occurred within the confined space entrenched by the amorphous PLLA block in the temperature range from −120 to 40 °C by preserving the microphase-separated morphology. At around the glass transition temperature of PLLA (∼45 °C), chain stretching of PLLA and PDMS took place, resulting in the sudden i...

Poly(urethane–urea) (PUU) is prepared using dihydroxy functionalized polystyrene having Mw 2000 g/mol, 1,6 hexamethylene diisocyanate and three different diamines (1,2-ethylenediamine, 1,4-butanediamine and 1,6-hexamethylene diamine) by melt polymerization method. The synthesized copolymer is characterized by viscosity measurements, Fourier transform infrared (FT-IR) spectroscopy, wide angle 2D-X-ray scattering (WAXS) and differential scanning colorimetry (DSC). The inherent viscosity of the polymers is found to be in the range of 0.4–0.5 dl/g, suggesting that the polymers are of high molecular weight. FT-IR results conclude that the urea groups form both monodendate and bidendate assemblies. Temperature-dependent FT-IR and WAXS data confirm that the crystallinity of the copolymer is highly reversible and depends on the spacer length. DSC data also confirm that the crystallization pattern depends on the spacer length. The swelling behavior in water and the solubility of the polymer in chloroform are depending on the type of chain extender used in the PUU synthesis. Copyright © 2014 John Wiley & Sons, Ltd.

To reduce the complexity to monitor the bio-absorbable polymer in the implants, a new hyper branched star shaped polymer was developed with the synergetic combination of bio-absorbability and fluorescent characteristics. These hyper branched polymers were synthesized using arm fist method (AFM). This kind of advanced fluorescent specific bioabsorbable polymer (FBAP’s) is in high demand due to several advantages in replacing traditional materials for implants. Here, we have reported the molecular arrangement of the hyper branched polymer with respect to the fluorescent behavior.

The polymer nanocomposites were prepared by melt compounding from polypropylene/thermoplastic elastomer (PP-TPE) with sodium montmorillonite (Na-MMT) and cloisite 20A using maleic anhydride modified PP-grafted maleic anhydride (PP-g-MA) as a compatibilizer. Three different weight percentages (3, 5, and 7 wt%) of nanoclay (Na-MMT or C20A) were used to study the effect on the properties of nanocomposites. The optimized clay composition of 5% was tested by varying the wt% of compatibilizer (5, 10, 15, and 20) to obtain better performance properties of nanocomposites. The excellent improvements in mechanical properties were observed by the incorporation 5 wt% cloisite20A with 5% compatibilizer. TPO nanocomposites show higher melting point and thermal degradation temperature on heat loading. The good thermal stability was confirmed from DSC and TGA. The intercalated/exfoliated phenomenon was indicated by the increase in Tg and storage modulus using DMA. Wide angle X-ray scattering (XRD) was employed to study the size and changes in the morphology; it is also provided conclusive evidence for the formation of exfoliated structures.

The kinetics of ceric ion-poly(ethylene glycol) (PEG, mol. wt 6000) redox-coupled-initiated polymerization of acrylonitrile (M), yielding a block copolymer of PEG and poly(acrylonitrile) (PAN) in aqueous sulphuric acid medium, has been investigated. The polymerization experiments were conducted in the dark under a nitrogen atmosphere in the temperature range 35–60°. The polymerization was found to proceed without an induction period. The rate of monomer disappearance was found to be dependent on [M]2, [PEG] and independent of both [Ce(IV)] and [H+]. The rate of ceric ion disappearance was directly proportional to [Ce(IV)] and [H+] but independent of [M]. The FT-i.r. spectra of the block copolymer showed the presence of both PEG and PAN segments. The elemental analysis indicated the molar composition of PAN and PEG in the block copolymer to be 80:20.