Supertwisted Chiral Gyroid Mesophase in Chiral Rod-Like Compounds.

Among the intriguing bicontinuous self-assembled structures, the gyroid cubic is the most ubiquitous. It is found in block and star polymers, surfactants with or without solvent, in thermotropic liquid crystals with end- or side-chains, and in biosystems providing structural color and modelling cell mitosis. It contains two interpenetrating networks of opposite chirality and is thus achiral if, as usual, the content of the two nets is the same. However, we now find that this is not the case for strongly chiral compounds. While achiral molecules follow the opposite twists of nets 1 and 2, molecules with a chiral center in their rod-like core fail to follow the 70° twist between junctions in net 2 and instead wind against it by -110° to still match the junction orientation. The metastable chiral gyroid is a high-entropy high-heat-capacity mesophase. The homochirality of its nets makes the CD signal of the thienofluorenone compounds close to that in the stable I23 phase with 3 isochiral nets.

Continuous Spectrum of Morphologies and Phase Behavior across the Contact Zone from Poly(l-lactide) to Poly(d-lactide): Stereocomplex, Homocrystal, and Between.

The enantiomeric ratio is a key factor affecting the crystallization behavior and morphology of poly-l-lactide/poly-d-lactide (PLLA/PDLA) blends. Despite a number of studies on crystallization of nonequimolar PLLA/PDLA blends, a full picture of the effect of the L/D ratio is still lacking. Here, we put the two enantiomers in contact and allow interdiffusion above the melting point of the stereocomplex crystal (SC) to prepare samples with a continuously changing L/D ratio from enantiopure PLLA (ratio 0/100) to enantiopure PDLA (100/0). Using polarized optical microscopy, atomic force microscopy, and microbeam X-ray diffraction, the continuous spectrum of morphologies and phase behaviors across the contact zone is investigated. The blend morphology shows clear evidence of "poisoning by purity" of SC crystallization at all blend compositions. The low birefringence of the 50/50 SC is found to be due to the meandering of broken edge-on lamellae. Its further decrease to near zero as L/D deviates further away from 50/50 is explained by transition from radial edge-on lamellae to fully random meandering lamellae, then to mixed flat-on lamellae, and finally to submicron-sized axialites. In comparison with the smooth and straight homocrystal (HC) lamellae of pure enantiomers, the lamellae in the blends often have serrated edges caused by pinning by rejected excess enantiomer acting as an impurity during lamellar growth. A feature of the binary phase diagram is pure enantiomers acting as an impurity to the SC and counter-enantiomer acting as an impurity to homocrystallization of the enantiomers. Crystallization was found to be most suppressed at 99% enantiomeric purity, where the amount of the counter-enantiomer is insufficient for creation of SC nuclei and HC growth is inhibited by the small amount of the enantio-impurity. These and other intriguing results are less likely to be noticed without the continuous composition gradient of the contact sample.

Enantiomers Self-Sort into Separate Counter-Twisted Ribbons of the Fddd Liquid Crystal─Antiferrochirality and Parachirality.

The recently discovered orthorhombic liquid crystal (LC) phase of symmetry Fddd is proving to be widespread. In this work, a chiral hydroxybutyrate linkage is inserted into the molecular core of hexacatenar rodlike compounds, containing a thienylfluorenone fluorophore. In addition to more usual tools, the methods used include grazing-incidence X-ray scattering, modulated differential scanning calorimetry (DSC), flash DSC with rates up to 6000 K/s, and chiro-optical spectroscopies using Mueller matrix method, plus conformational mapping. Although pure R and S enantiomers form only a strongly chiral hexagonal columnar LC phase (Colh*), the racemic mixture forms a highly ordered Fddd phase with 4 right- and 4 left-handed twisted ribbon-like columns traversing its large unit cell. In that structure, the two enantiomers locally deracemize and self-sort into the columns of their preferred chirality. The twisted ribbons in Fddd, with a 7.54 nm pitch, consist of stacked rafts, each containing ∼2 side-by-side molecules, the successive rafts rotated by 17°. In contrast, an analogous achiral compound forms only the columnar phase. The multiple methods used gave a comprehensive picture and helped in-depth understanding not only of the Fddd phase but also of the "parachiral" Colh* in pure enantiomers with irregular helicity, whose chirality is compared to the magnetization of a paramagnet in a field. Unusual short-range ordering effects are also described. An explanation of these phenomena is proposed based on conformational analysis. Surprisingly, the isotropic-columnar transition is extremely fast, completing within ∼20 ms. A clear effect of phase on UV-vis absorption and emission is observed.

3D Morphology of Different Crystal Forms in ß-Nucleated and Fiber-Sheared Polypropylene: α-Teardrops, α-Teeth, and ß-Fans.

Polymorphism of semicrystalline polymers has significant influence on their physical properties, with each form having its advantages and disadvantages. However, real-life polymer processing often results in different coexisting crystal polymorphs, and it remains a challenge to determine their shape, spatial distribution, and volume fraction. Here, i-polypropylene (i-PP) sheets containing both α- and ß-forms were prepared either by adding ß-nucleating agent or by fiber pulling-induced crystallization. By adding a compatible dye that is partially rejected from the growing crystalline aggregates (spherulites and cylindrites), we visualize the shape of these objects in 3D using two-photon fluorescence confocal microscopy. To distinguish between crystal forms, we take advantage of the difference in dye-retaining ability of the α- and ß-aggregates. Even in 2D, fluorescence microscopy (FM) distinguishes the two crystal forms better than polarized microscopy. In 3D imaging, the volume fraction and spatial distribution of α- and ß-forms in different morphological types could be determined quantitatively. Morphologies described as α-teeth, ß-fans, and α-teardrops were visualized for the first time in 3D. Furthermore, internal and surface microcracks were seen to be associated predominantly with the ß-form and around the fiber. Spatial distribution of α- and ß-forms was also determined by scanning with a synchrotron X-ray beam. Good agreement was obtained with 3D microscopy, but XRD could not match the detail obtainable by the tomography. The work demonstrates the ability of the 3D imaging method to distinguish different crystal forms and their specific morphologies.

Poisoning by Purity: What Stops Stereocomplex Crystallization in Polylactide Racemate?

Formation of stereocomplex crystals (SC) is an effective way to improve the heat resistance and mechanical performance of poly(lactic acid) products. However, at all but the slowest cooling rates, SC crystallization of a high-molecular-weight poly(l-lactic acid)/poly(d-lactic acid) (PLLA/PDLA) racemate stops at a high temperature or does not even start, leaving the remaining melt to crystallize into homochiral crystals (HC) or an SC-HC mixture on continuous cooling. To understand this intriguing phenomenon, we revisit the SC crystallization of both high- and low-molecular-weight PLLA/PDLA racemates. Based on differential scanning calorimetry (DSC), supplemented by optical microscopy and X-ray scattering, we concluded that what stops the growth of SC is the accumulation of the nearly pure enantiomer, either PDLA or PLLA, that is rejected from the SC ahead of its growth front. The excess enantiomer is a result of random compositional fluctuation present in the melt even if the average composition is 1:1. The situation is more favorable if the initial polymer is not fully molten or is brought up to just above the melting point where SC seeds remain, as proven by DSC and X-ray scattering. Moreover, we find that not only is SC growth poisoned by the locally pure enantiomer but also that at lower temperatures, the HC growth can be poisoned by the blend. This explains why SC growth, arrested at high temperatures, can resume at lower temperatures, along with the growth of HC. Furthermore, while some previous works attributed the incomplete SC crystallization to a problem of primary nucleation, we find that adding a specific SC-promoting nucleating agent does not help alleviate the problem of cessation of SC crystallization. This reinforces the conclusion that the main problem is in growth rather than in nucleation.

Morphology of Shear-Induced Polymer Cylindrites Revealed by 3D Optical Imaging.

Two-photon confocal laser microscopy was used to obtain three-dimensional (3D) images of the morphology of poly(lactic acid) after shear-induced crystallization. The necessary fluorescence contrast was achieved by doping the polymer with Nile Red. The dye gets partially rejected from the growing crystalline aggregates during their formation, thus creating a renderable high-low fluorescence boundary outlining the shape of the aggregates. Parallel-plate melt-shearing and pulling a glass fiber through the melt were used as the two methods to achieve shear-induced crystallization. This study focuses on the shape of the resulting cylindrites, i.e., large-diameter shish-kebabs. The first 3D images of polymer cylindrites show that, if far from boundaries, they are circular cylinders, highly regular after fiber pull, but less so after parallel-plate shear. In the latter case, the cylindrite reveals the trajectory of the foreign particle that had nucleated its growth. Interestingly, lateral growth of the cylindrites was found to accelerate toward the sample surface when approaching it, giving the cylindrite an elliptical cross section. Furthermore and surprisingly, in the case of fiber pull, a row of spherulites is nucleated at the polymer-substrate interface nearest to the fiber, aligned along the fiber axis and appearing ahead of the rest of the space-filling spherulites. Both the phenomena, elliptical cylindrites and row of spherulites, are attributed to negative pressure buildup peaking at the cylindrite growth front and at the nearby film surface caused by crystallization-induced volume contraction. The pressure and flow distribution in the system is confirmed by numerical simulation. The results illustrate the value of 3D imaging of crystalline morphology in polymer science and polymer processing industry.

Multicompartment Nanoparticles by Crystallization-Driven Self-Assembly of Star Polymers: Combining High Stability and Loading Capacity.

Herein novel multicompartment nanoparticles (MCNs) that combine high stability and cargo loading capacity are developed. The MCNs are fabricated by crystallization-driven self-assembly (CDSA) of a tailor-made 21 arm star polymer, poly(L-lactide)[poly(tert-butyl acrylate)-block-poly(ethylene glycol)]20 [PLLA(PtBA-b-PEG)20 ]. Platelet-like or spherical MCNs containing a crystalline PLLA core and hydrophobic PtBA subdomains are formed and stabilized by PEG. Hydrophobic cargos, such as Nile Red and chemotherapeutic drug doxorubicin, can be successfully encapsulated into the collapsed PtBA subdomains with loading capacity two orders of magnitude higher than traditional CDSA nanoparticles. Depolarized fluorescence measurements of the Nile Red loaded MCNs suggest that the free volume of the hydrophobic chains in the nanoparticles may be the key for regulating their drug loading capacity. In vitro study of the MCNs suggests excellent cytocompatibility of the blank nanoparticles as well as a dose-dependent cellular uptake and cytotoxicity of the drug-loaded MCNs.

Bowls, vases and goblets-the microcrockery of polymer and nanocomposite morphology revealed by two-photon optical tomography.

On the >1 µm scale the morphology of semicrystalline plastics like polyethylene or Nylon features spherulites, "shish-kebabs", cylinddrites and other crystalline aggregates which strongly affect mechanical and other material properties. Current imaging techniques give only a 2D picture of these objects. Here we show how they can be visualized in 3D using fluorescent labels and confocal microscopy. As a result, we see spherulites in 3D, both in neat polymers and their nanocomposites, and observe how unevenly nanoparticles and other additives are distributed in the material. Images of i-polypropylene and biodegradable poly(lactic acid) reveal previously unsuspected morphologies such as "vases" and "goblets", nonspherical "spherulites" and, unexpectedly, "shish-kebabs" grown from quiescent melt. Also surprisingly, in nanocomposite sheets spherulite nucleation is seen to be copied from one surface to another, mediated by crystallization-induced pressure drop and local melt-flow. These first results reveal unfamiliar modes of self-assembly in familiar plastics and open fresh perspectives on polymer microstructure.

Ultralight Cellulose Porous Composites with Manipulated Porous Structure and Carbon Nanotube Distribution for Promising Electromagnetic Interference Shielding.

Lightweight conductive polymer composites based on biomass could be a promising candidate for electromagnetic interference (EMI) shielding application. Herein, tailoring porous microstructure and regulating the distribution of carbon nanotubes (CNTs) in cellulose composites are attempts to achieve highly efficient EMI shielding properties accompanying desired mechanical property and low density. Specifically, aligned porous structure is fabricated by ice-template freeze-drying method; meanwhile, CNT is regulated to decorate inside the cellulose matrix (CNT-matrix/cellulose porous composites) or to directly bind over the cellulose cell walls (CNT-interface/cellulose porous composites). It is found that, owing to the preferential distribution of CNT on the cell walls, the CNT-interface/cellulose porous composites possess a very high electrical conductivity of 38.9 S m-1 with an extremely low percolation threshold of 0.0083 vol % with regard to CNT-matrix/cellulose porous composites. Therefore, a shielding effectiveness of 40 dB with merely 0.51 vol % CNT under a thickness of 2.5 mm is achieved in CNT-interface/cellulose porous composites, which is attributed to efficient multiple reflections and the accompanying absorption with promoted conductivity and better-defined porous structure. More laudably, the CNT-interface/cellulose porous composites reveal a superior mechanical property with a specific modulus of 279 MPa g-1 cm3. The value behind the current work is to pave an effective way to fabricate environmentally benign, high-performance EMI shielding materials to practically boost numerous advanced applications of cellulose.

A Criterion for Flow-Induced Oriented Crystals in Isotactic Polypropylene under Pressure.

Flow-induced oriented crystals have attracted considerable attention because they significantly increase stiffness and strength of polymer products. Naturally, understanding the necessary condition of forming oriented crystals is of importance for both industry and polymer physics. Following the concept of specific work of flow proposed by Mykhaylyk and co-workers, the expression of the specific work of flow, w (T,P) , was carefully summarized and verified that when w (T,P) is above a critical specific work of flow, w c(T,P) = (1.7 ± 0.7) × 107 J m-3 , oriented crystals in isotactic polypropylene can be induced by flow at pressures (50, 100, and 150 MPa) and at a undercooling of 65 K. The influences of pressure on w c(T,P) stem from two facets: one is the influence on the melt viscosity (the Barus law), and the other one is the influence on the equilibrium melting temperature (the Clapeyron equation). The current study can guide real processing to fabricate high-performance polymer products with oriented crystals.

Thicker Lamellae and Higher Crystallinity of Poly(lactic acid) via Applying Shear Flow and Pressure and Adding Poly(ethylene Glycol).

In this work, we explored the crystallization of poly(lactic acid) (PLA) blended with poly(ethylene glycol) (PEG) under two inevitable processing fields (i.e., flow and pressure) that coexist in almost all processing for the first time. Here, the PEG was incorporated into PLA as a molecular chain activity promoter to induce PLA crystallization. A homemade pressuring and shearing device was utilized to prepare samples and necessary characterization methods, such as differential scanning calorimetry, scanning electron microscopy, and synchrotron radiation, and were used to investigated the joint effects of PEG, pressure, and shear flow on the crystallization behaviors and morphologies of PLA/PEG samples. The results reveal that adding 3-5 wt % PEG into PLA can significantly increase the PLA crystallinity due to the efficient plasticization effect of PEG, while the PEG content reaches 10 wt %, the PLA crystallinity decreases drastically as the phase separation between PEG and PLA occurs. We also find that applying a higher pressure (∼100 MPa) can facilitate the formation of thicker lamellae with fewer defects as well as higher crystallinity under an equal degree of supercooling compared to normal pressure or a low pressure condition because the slip of molecular chains during crystallization makes the lamellae thicker under higher pressures. The PLA crystalline structure in the PLA/PEG sample is not influenced by the shear flow, yet the crystallinity is largely enhanced by applying a shear flow with an appropriate intensity (0-3.5 s-1). It is worth noting that pressure and shear flow show a synergetic effect to fabricate PLA/PEG samples with high crystallinity. These meaningful results could beyond doubt help comprehend the relationship between crystallization conditions and crystallization behaviors of PLA/PEG samples and thus provide guidance to obtain high-performance PLA/PEG products via controlling crystallization conditions.