In Situ Optical Imaging of the Growth of Conjugated Polymer Aggregates

Understanding the mechanisms that contribute to conjugated polymer aggregate formation and growth may yield enhanced control of aggregate morphology and functional properties on the mesoscopic scale. In situ optical imaging of the growth of MEH‐PPV aggregates in real time in controlled swollen films shows that growth occurs through multiple mechanisms and is more complex than previously described. Direct evidence is provided for both Ostwald ripening and aggregate coalescence as operative modes of aggregate growth in solvent swollen films. These growth mechanisms have a distinct and strong impact on the evolution of morphological order of growing aggregates: while Ostwald ripening allows preservation of highly ordered morphology, aggregate coalescence occurs with no preferential orientation, leading to attenuation in degree of ordering.     

Effect of Substrate Temperature on the Epitaxial Growth of Oriented n-Alkane Thin Films on Graphite

A complex orientational morphology is observed when n-alkane thin films are vapor deposited on highly oriented pyrolytic graphite surfaces. Substrate temperature can be used to tune the orientation and morphology of n-alkane thin films. The molecular orientation changes from lateral to normal to the surface when the substrate temperature is raised sufficiently. Under specific substrate temperature conditions, the n-alkane molecules are aligned in the plane of the sample surface, in directions reflecting the 6-fold symmetry of the graphite substrate. A series of different morphologies, from uniform thin films to oriented bars, are observed as a function of chain length and substrate temperature. The systematic evolution of these oriented morphologies is mapped as a function of deposition conditions, and the kinetic and thermodynamic factors that govern the formation of different in-plane and normal domains are considered.     

Segmental orientation studies of polyether polyurethane block copolymers with different hard segment lengths and distributions

The orientation behavior of two series of segmented polyether polyurethanes containing different hard segment length distributions has been studied as a function of the average hard segment length which was varied from one to five methylene bis (p-phenyl isocyanate) (MDI) units. The orientation behavior of the soft segments, isolated hard segments, and of hard segments aggregated in hard domains was determined from the dichroic behavior of representative infrared bands. As the hard segment length increases, a transition in orientation behavior is observed which corresponds to a change in sample morphology.The effects of annealing and hard segment length distribution were also studied and were shown to affect the orientation response through their influence on sample morphology. Orientation hysteresis studies were performed to probe the mechanism of the transverse orientation and orientation inversion which occurred in polyurethanes with the longer, more crystallizable hard segment lengths.     

Enhancement of thermoelectric properties of D-A conjugated polymer through constructing random copolymers with more electronic donors

Developing new D-A conjugated polymer system for thermoelectric (TE) application is highly desirable. Herein, a series of random copolymers by incorporating 3,4-ethylenedioxythiophene (EDOT) electron rich units into a diketopyrrolopyrrole (DPP) D-A conjugated polymer were designed and synthesized. Compared to the alternating conjugated copolymer PDPP-3T, the HOMO level of the random copolymers are increased as part of the electron deficiency acceptor DPP units in the polymer chain were superseded by electron rich EDOT, which could contribute to effective p-doping. Moreover, through incorporating EDOT to construct random copolymers, it can also induce an orientation change from face-on dominated to edge-on dominated orientation as well as enhance the packing of copolymer chains, which is beneficial to the charge transport. Under same doping condition, the electrical conductivities of the doped polymers increase and the Seebeck coefficient decrease as the increasing of EDOT content, resulting in an optimized power factor of 6.4 μW m⁻¹ K⁻² for the random polymer with EDOT content of 40% which is four times higher than that of alternating conjugated copolymer PDPP-3T. These results demonstrated that constructing random copolymers by incorporating more electronic donors into D-A conjugated polymers may be a promising strategy for developing TE conjugated polymers.     

Molecular packing of high-mobility diketo pyrrolo-pyrrole polymer semiconductors with branched alkyl side chains

We describe a series of highly soluble diketo pyrrolo-pyrrole (DPP)-bithiophene copolymers exhibiting field effect hole mobilities up to 0.74 cm(2) V(-1) s(-1), with a common synthetic motif of bulky 2-octyldodecyl side groups on the conjugated backbone. Spectroscopy, diffraction, and microscopy measurements reveal a transition in molecular packing behavior from a preferentially edge-on orientation of the conjugated plane to a preferentially face-on orientation as the attachment density of the side chains increases. Thermal annealing generally reduces both the face-on population and the misoriented edge-on domains. The highest hole mobilities of this series were obtained from edge-on molecular packing and in-plane liquid-crystalline texture, but films with a bimodal orientation distribution and no discernible in-plane texture exhibited surprisingly comparable mobilities. The high hole mobility may therefore arise from the molecular packing feature common to the entire polymer series: backbones that are strictly oriented parallel to the substrate plane and coplanar with other backbones in the same layer.     

Liquid Crystal Ordering on Conjugated Polymers Film Morphology for High Performance

The electronic performance of conjugated polymers depends on the microstructure of the polymer films. A percolated network morphology with high crystallinity, ordered intermolecular packing and long‐range order is beneficial for charge transport. In recent reports, some conjugated polymers have been shown to exhibit liquid crystallinity. The appearance of liquid crystalline ordering provides a new solution to solve the difficulties in microstructure manipulation. In this review, we summarize how liquid crystallinity can assist molecular arrangement and guide long‐range orientation during film processing, leading to high charge mobility. We expect that this article could draw more attention to the liquid crystallinity of conjugated polymers. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1572–1591     

Morphological studies of blends of conjugated polymers and acceptor molecules using langevin dynamics simulations

We use coarse‐grained Langevin dynamics simulations of blends of generic conjugated polymers and acceptor molecules to show how architecture (e.g., side chains, backbone flexibility of oligomers) and the pair‐wise interactions between the constituents of the blend affect morphology and phase transition. Alkyl side chains on the conjugated oligomer backbones shift the liquid crystal (LC) transition temperature from that of bare conjugated backbones and the direction of the shift depends on backbone–backbone interactions. Rigid backbones and constrained side chains cause a layer‐by‐layer morphology of conjugated polymers and amorphous acceptors, whereas flexible backbones and unconstrained side chains facilitate highly ordered acceptor arrangement. Strong backbone–backbone attraction shifts LC transition to higher temperatures than weak backbone–backbone attraction, and strong acceptor–acceptor attraction increases acceptor aggregation. Pure macro‐phase separated domains form when all pair‐wise interactions in the blend are strongly attractive, whereas interconnected domains form at intermediate acceptor–acceptor attraction and strong polymer–polymer attractions. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Nanoarchitectonics on Electrosynthesis and Assembly of Conjugated Metallopolymers

In contrast to edge-on and face-on orientations, end-on uniaxial conjugated polymers have the theoretical possibility of providing a macroscopic crystalline film. However, their fabrication is insurmountable due to sluggishly thermodynamic equilibrium states. Herein, we report the programmatic pathway to fabricate nanoarchitectonics on end-on uniaxial conjugated metallopolymers by surface-initiated simultaneous electrosynthesis and assembly. Self-assembled monolayer (SAM) with bottom-up oriented electroactive molecules as a temple allows orientation, stacking, and reactive addition of monomers triggered by switching alternative redox reactions as well as crystallization of small molecules. Repeating the same reaction can repair the unreactive site on the SAM and dynamically and statistically ensure maximum iterative coverage with ideal linear coefficients between optical or electrical responses and iterative times. The resulting nanoarchitectonics on uniaxially assembled end-on polymers over centimeter-sized areas have a subnanometer-uniform morphology and exhibit ultrahigh modulus as well as an inorganic indium tin oxides and the highest conductance among conjugated molecular monolayers. Their memristive devices provide quantitative electrical and optical responses as a function of molecular length, bias, and iterative junctions. Precise processing of nanoarchitectonics as an electrically assisted assembly or printing technique can present sophisticated optoelectric functions and dimensional batch-to-batch consistency for micro-sized organic materials and electronics.     

Mesostructured silica containing conjugated polymers formed within the channels of anodic alumina membranes from tetrahydrofuran-based solution

The synthesis of mesostructured silica from a tetrahydrofuran (THF)-based sol gel was carried out in the channels of an anodic alumina membrane (AAM) using the evaporation-induced self-assembly (EISA) method. Two different nonionic surfactants were used as structure-directing agents, the triblock copolymer Pluronic P123 and the oligomer surfactant Brij56. The effect of the relative humidity and surfactant concentration on the type of mesophase and orientation of the in-channel mesostructures was studied using transmission electron microscopy (TEM) and grazing incidence small angel X-ray scattering (GISAXS). The in-channel structures obtained in this study were primarily of the 2D hexagonal phase with a circular orientation in which the hexagonally packed cylinders form a spiral-like shape from the channel wall inward. In addition, a columnar orientation of the hexagonal phase, in which the axes of the hexagonally packed cylinders are oriented parallel to the channel axes, was also observed. Finally, the use of the THF-based synthesis allowed the in situ incorporation of the highly hydrophobic yellow-emitting conjugated polymer poly[9,9-dioctylfluorene-co-benzothiadiazole] into the in-channel mesostructure upon its formation. The conjugated polymer was well distributed within the mesostructure and maintained its optical properties.     

Counterions Control Whether Self‐Assembly Leads to Formation of Stable and Well‐Defined Unilamellar Nanotubes or Nanoribbons and Nanorods

Self‐assembly of the amphiphilic π‐conjugated carbenium ion ATOTA‐1⁺ in aqueous solution selectively leads to discrete and highly stable nanotubes or nanoribbons and nanorods, depending on the nature of the counterion (Cl^? vs. PF₆^?, respectively). The nanotubes formed by the Cl^? salt illustrate an exceptional example of a structural well‐defined (29±2 nm in outer diameter) unilamellar tubular morphology featuring π‐conjugated functionality and high stability and flexibility, in aqueous solution.     

n-Type D-A Conjugated Polymers: Relationship Between Microstructure and Electrical/Mechanical Performance

Conjugated polymers are widely applied in optoelectronic devices due to their excellent optoelectronic properties, solution processibility, and intrinsic flexibility. High-performance films could be achieved with joint efforts from both molecular structure and film solid microstructure. Herein, research progress of the relationship between microstructure and electrical/mechanical performance of poly{[N,N'-bis(2-octyldodecyl)-representative of n-type donor-acceptor conjugated polymers, is reviewed. Its strong aggregation in solution is underlined and the methods to tune the degree of aggregation, such as solvent quality, molecular weight, and regioregularity, are compared. A liquid-crystalline behavior is evidenced in highly concentrated solutions during film drying, which favors the formation of highly anisotropic structures. Moreover, alignment techniques and thermal annealing are used to regulate molecular orientation and polymorphism in films. These structure characteristics offer great potential for researchers to handle film performances. Up to now, more attention has been paid to optimize the electrical performance of the devices. Achieving high-performance n-type conjugated polymer films with both superior mechanical and electrical properties is a newly emerging focus.     

规整链球型含C_(60)聚苯乙烯的亲水化修饰及其在水中的自组装

C60作为碳的第三种同素异型体,一经发现就为当今科学研究所关注.其独特的光学,电学性能吸引了许多化学工作者的不懈努力,以探索其在化学、材料科学等领域的应用.精确的化学修饰不仅是改善其较差的溶解和加工性能的主要途径之一,而且更能提供规整的结构,以利于对其性能的深入研究.     

Orientation of triplet and singlet transition dipole moments in polyfluorene, studied by polarised spectroscopies

The orientation of the transition dipole moments for four commonly studied optical transitions of the conjugated polymer polyfluorene have been deduced using polarised spectroscopies, including fluorescence, phosphorescence, and photoinduced absorption in oriented polymer films. The data show that all the transitions except from the phosphorescence are highly polarised parallel to the chain orientation. The phosphorescence in this polyfluorene homopolymer however, has its dominant component orthogonal to the chain orientation. The data are interpreted by regarding shape and electron distribution of the excited states. It has been deduced that the singlet states and higher triplet states are strongly delocalised along the chain whereas the T₁ excited state is more localised and has its electron distribution oriented orthogonal to the chain.     

聚丙烯熔体自干扰流动对其凝聚态取向效应的影响

通过一种由两个浇口小流道共享一个分流道的新型浇口 ,使两股熔体流入型腔 ,并在型腔内产生自干扰流动 (SIF) .在平行于注射方向熔体会产生迭加效应 ,而在垂直于注射方向熔体会产生挤压作用 ,并形成横向流动 .探讨了这种自干扰流动对注射PP试样的取向效应的影响 .采用热收缩和X 射线衍射法分别对分子链取向和晶体取向进行了检测 .热收缩试验结果显示SIF样比常规流动 (CFP)试样具有较小的链取向 .透射X 射线衍射的检测结果表明SIF样和CFP样在剪切层晶体具有大的取向效应 ,SIF样晶体的取向度为 65 % ,而CFP样则为 79% .     

Morphology changes in bulk donor–acceptor poly(benzodithiophene‐benzotriazole) after post‐treatment

The bulk order in donor–acceptor poly(benzodithiophene‐benzotriazole) was improved by two different post‐treatment procedures applied to the specimen. Two‐dimensional wide‐angle X‐ray scattering was used to investigate the structural changes after treatment. After post‐treatment the polymer turned into a highly crystalline morphology with well‐resolved and intensive π‐stacking reflections which were absent in the pristine sample. To understand the ordering mechanisms taking place during the two post‐treatment procedures, structural parameters like coherence length and paracrystallinity were extracted from the X‐ray data indicating the impact on crystallite size and cumulative lattice disorder. During temperature annealing the intralayer packing transforms from amorphous to highly ordered. On the other hand, solvent vapor annealing enhances in higher extent the interlayer organization due to interpenetration of solvent molecules between alkyl side chains. These results provide important insights for the morphology optimization of semicrystalline conjugated polymers. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2327–2334.     

Correlation of the minor-phase orientation to the flow-induced morphological transitions in thermotropic liquid crystalline polymer/PBT blends

Immiscible blends of thermotropic liquid crystalline polymers (TLCP) and a flexible polymer matrix show viscosity reductions and extensive fiber formation under certain flow conditions. Here we study these phenomena by directly examining the TLCP component's molecular orientation and the dispersed phase morphology. The rheology and morphology of blends of polybutylene terephthalate and a thermotropic copolyester (HX-8000 series, DuPont) at concentrations varying from 5 to 30 wt % of TLCP are characterized. It is found that the blends show viscosity reduction as well as stable fiber formation at shear rates dependent on the TLCP content. Wide-angle X-ray scattering is performed to measure the degree of molecular orientation of the TLCP phase. A deconvolution scheme isolates the scattering from the TLCP in the blends and a molecular model enables extracting an experimental orientation factor. It was found that a highly microfibrillated TLCP phase is coupled with an increase in the TLCP molecular orientation to values close to the pure TLCP at similar processing conditions. Further, the microfibrillated TLCP phase is found to be stable within the testing time. Current hypotheses about fiber formation in immiscible blends are tested against the experimental observations. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1769–1780, 1998     

THE EFFECT OF EC ON ORIENTATION AND RELAXATION OF PP OBTAINED VIA DYNAMIC PACKING INJECTION MOLDING

As a long term project aiming at engineering plastics based on polypropylene (PP), in this work, we report the effect of ethylene-cellulose (EC) on the orientation and relaxation of PP obtained via dynamic packing injection molding (DPIM). 2d-WAXD results showed that PP with a highly oriented structure and a shish-kebab structure were achieved by DIPM, leading to an increase of tensile strength from 35.0MPa to 48.6MPa. The degree of orientation of PP was increased by adding only 1% of EC, resulting in a further increase of tensile strength from 48.6MPa to 53.8MPa. Shish was found to exist not only in the oriented layer but also in the core of the sample after adding EC, as evidenced by DSC result.This was understood as due to the overall decrease of viscosity by the addition of EC, thus an increasing of shear rate. Higher shear rate can favor the orientation of molecules and continuous growth of shish structure, resulting in a change of shish distribution along the sample thickness. On the other hand, the relaxation mode of shish in the melt recrystallization of PP is also greatly affected by the presence of EC. A retarded relaxation of PP macromolecules was seen.Even more, SEM results showed that EC could form the short fibers in PP matrix along the shear flow direction. Compared with the morphology obtained by conventional injection molding, a much better dispersion and easy break-up of EC in PP matrix were observed for samples obtained by dynamic packing injection molding.     

MORPHOLOGY AND MECHANICAL PROPERTIES OF POLYPROPYLENE WITH in situ FORMED POLYAMIDE-6 FIBRILS

in situ Fibril formation of polyamide-6(PA6)in isotropic polypropylene(iPP)was first fabricated using a slit die extrusion and hot stretching process.Then the prepared materials were subjected to injection molding in the temperature range higher than the melting temperature of iPP but lower than that of PA6.The obtained injection-molded samples were characterized via scanning electron microscopy(SEM),differential scanning calorimetry(DSC)and two-dimensional wide- angle X-ray scattering(2D-WAXS).Mechanical properties were also investigated.The SEM result shows that the optimum fibril formation could be only achieved in the range of 20 wt% to 30 wt% of PA6 content for the studied system.The fibril morphology changes along the sample thickness in the injection-molded bars.The fibril morphology in the skin layer was better than that in the core layer.2D-WAXS results showed that the orientation of PP decreased with the increase of PA6 content,which indicated that the orientation of PP was confined by PA6 fibrils.Combined consideration of mechanical properties and morphology indicates that only PP/PA6 composites with 20 wt% of PA6 content show better properties because of the better fibril morphology and PP chain orientation.     

Mechanical relaxation in polypropylene as a function of polymorphism and degree of lamella orientation

Mechanical relaxation data as a function of temperature (ca. 1 Hz) have been obtained for several samples of isotactic polypropylene crystallized from the melt, which exhibit both α and β forms as well as varying degrees of lamella orientation. The samples ranged in morphology from an unoriented sample showing only the α form to one highly oriented having approximately 90 per cent the β form. Results for the logarithmic decrement Δ and loss modulus G″ are that the low temperature (ca. ?75°C) and glass temperature (ca. 0°C) relaxations show little or no sensitivity to orientation in the α form, but that the intensity of the two processes is different in the α form than in the β form for samples of nearly equal overall per cent crystallinity. In both Δ and G″, the low-temperature peak decreased and the glass temperature peak increased in intensity as the fraction of β form crystallinity present increased. Data for the high-temperature relaxation (ca. 80°C) indicate a dependence upon orientation and/or crystal form in addition to a dependence upon per cent crystallinity.     

Structural transitions of nanocrystalline domains in regioregular poly(3‐hexyl thiophene) thin films

The effects of solution processing and thermal annealing on thin film morphology and crystalline structures of regioregular poly(3‐hexyl thiophene) (RR P3HT) are studied in terms of molecular weight (M_w). Using grazing‐incidence X‐ray diffraction, π‐conjugated planes in drop‐cast films from chloroform solutions are found to be preferentially oriented parallel to the substrates regardless of M_w. However, the mesoscale nanocrystalline morphology of the drop‐cast films is significantly affected by M_w, exhibiting a distinctive morphological transition from short nanorods to long nanofibrils above a critical number‐averaged M_w (～ 3.6 kDa). This is probably due to the change in a conformation change from an extended‐chain to a folded‐chain, as M_w of RR P3HT increases. In contrast, spin‐casting of high M_w RR P3HT produces less ordered films with a lower crystallinity and mixed parallel/perpendicular orientations of π‐conjugated planes. The crystallinity and parallel π‐conjugated orientation of RR P3HT in spin‐cast films could be improved by thermal treatments at high‐temperatures either (1) above the glass transition temperature or (2) above the melting temperature of RR 3PHT followed by recrystallization upon cooling under vacuum. However, the charge mobility of the spin‐cast films for a field‐effect transistor application is still lower than that of the drop‐cast films. This would be attributed to the chain oxidation and the development of distinct grain boundaries between RR P3HT nanofibrils during the thermal treatments. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1303–1312, 2007