Search

Plastics are an extremely important class of materials that are prevalent in all facets of society; however, their widespread use over time, combined with limited end-of-life strategies, has led to increasing levels of waste accumulation. Although currently considered a burden, plastics waste is potentially an untapped feedstock for numerous chemical and manufacturing processes. In this review, we discuss the state of the art of approaches for valorization of plastics waste from a materials research perspective, including previous efforts to utilize plastics waste and recent innovations that have opportunities to add significant value. Although additional progress is necessary, we present several diverse capabilities and strategies for valorization that, when brought together, address end-of-life challenges for plastics at every stage of design and product consumption. In short, a materials research–based framework offers a unique perspective to address the urgent issues posed by plastics, unlocking the potential of polymers and plastics waste.

Mobile-amorphous-free crystals of a semiconducting polymer, poly(3-hexyl thiophene) (P3HT), were made via a flow induced crystallization technique to yield crystals that were microns long while the...

Optical technologies in the midwave and long wave infrared spectrum (MWIR, LWIR) are important systems for high resolution thermal imaging in near, or complete darkness. While IR thermal imaging has been extensively utilized in the defense sector, application of this technology is being driven toward emerging consumer markets and transportation. In this viewpoint, we review the field of IR thermal imaging and discuss the emerging use of synthetic organic and hybrid polymers as novel IR transmissive materials for this application. In particular, we review the critical role of elemental sulfur as a novel feedstock to prepare high refractive index polymers via inverse vulcanization and discuss the fundamental chemical insights required to impart improved IR transparency into these polymeric materials.

Extensive efforts have been employed to improve the power conversion efficiency of organic solar cells. One of the most successful approaches is the morphological control of the solar cells’ active...

The morphology of poly (3-hexylthiophene) (P3HT) in its liquid phase and its manipulation via flow-induced solution crystallization and its crystallization kinetics was studied to determine its mechanism. Shear flow-induced ordering of semiconducting P3HT, which generates more perfect crystal structures than quiescent methods, is elucidated using in situ rheo-SANS and rheo-SALS measurements, and an Avrami analysis is performed. Characteristic lengths of P3HT crystals were measured as a function of time, and 3-D networks of percolated P3HT fibril crystals were determined by measuring the apparent fractal, ∼2.6, by fitting the rheo-SANS data with a power law function. Additionally, UV–vis and DSC results revealed a process of P3HT crystal perfection determined by following the evolution of absorption peak characteristics of pi–pi stacking at 600 nm and the melting peaks as they shifted and narrowed with respect to increasing shear time. The Avrami exponent, m, reached a maximum value of 2 indicating homogeneous nucleation of P3HT macromolecules that allowed one-dimensional fibril crystal growth and was limited by contact time between the P3HT molecules rather than the diffusion of P3HT chains and this is attributed to the highly directional pi–pi stacking attractions of electron pi in the thiophene rings.

We report on a new strategy for preparing polymer–nanoparticle composite Faraday rotators for use in magnetic sensing and optical isolation. While most applications of Faraday rotators make use of inorganic garnet crystals, these are generally limited by low magneto-optical activity (low Verdet constants), high cost, and/or limited processing options. This has led to an interest in new materials with improved activity and processing characteristics. We have developed a new type of magneto-optical material based on polymer–nanoparticle composites that can be completely prepared by solution processing methods with tunable Verdet constants and device sensitivity. By exchanging native surface ligands on magneto-optically active CoFe2O4 nanocrystals with polymer compatible ligands, enhanced nanoparticle dispersion in processible polymer matrices was observed at up to 15 wt% inorganic loading. Employing a multilayer polymer film construct, functional Faraday rotator devices were prepared by simple sequential spin-coating of active nanocomposite and protective, barrier cellulose acetate layers. For these assemblies, magneto-optic activity and sensitivity are easily tuned through variation of nanoparticle feed and control of polymer film layers, respectively. These multilayered Faraday rotators show up to a 10-fold enhancement in Verdet constant compared to reference terbium gallium garnets at 1310 nm, opening new possibilities for the fabrication of “plastic garnets” as low cost alternatives to existing inorganic materials for use in the near-IR.

Optical technologies in the long-wave infrared (LWIR) spectrum (7-14 μm) offer important advantages for high-resolution thermal imaging in near or complete darkness. The use of polymeric transmissive materials for IR imaging offers numerous cost and processing advantages but suffers from inferior optical properties in the LWIR spectrum. A major challenge in the design of LWIR-transparent organic materials is that nearly all organic molecules absorb in this spectral window which lies within the so-called IR-fingerprint region. We report on a new molecular-design approach to prepare high refractive index polymers with enhanced LWIR transparency. Computational methods were used to accelerate the design of novel molecules and polymers. Using this approach, we have prepared chalcogenide hybrid inorganic/organic polymers (CHIPs) with enhanced LWIR transparency and thermomechanical properties via inverse vulcanization of elemental sulfur with new organic co-monomers.

Many applications of 3D printing are enhanced by increased printing speed. In the hot end of a 3D printer, the polymer feed stock flows in a heated cylinder at a set temperature. Since the polymer must be hot enough to reach a pliant state before extrusion, this establishes a maximum velocity beyond which the polymer is too rigid to be extruded. A mathematical model is presented for this system, and both amorphous and crystalline polymer systems are examined. The former is a heat transfer problem; the latter is a Stefan problem. Several different conditions for establishing the maximum velocity are considered; using the average polymer temperature in the hot end matches well with experimental data.

Stresses result when polymer feed stock is extruded through the nozzle of a three-dimensional (3D) printer, causing undesirable surface roughness called “sharkskin,” which hinders effective bonding to the substrate. A promising method to remove the sharkskin is to reheat the polymer after extrusion. However, questions remain about the appropriate design parameters to guarantee success. A mathematical model is presented for this system, and both amorphous and crystalline polymers are examined. The former is a heat transfer problem; the latter a Stefan problem. Several effectiveness conditions are considered, including exit temperature and a duration condition related to the polymer relaxation time. Our results provide guidance on designing effective postextrusion heaters.

Material extrusion (ME), sometimes called Fused Deposition Modeling® or Fused Filament Fabrication, is an additive manufacturing technique that places order 300 μm diameter molten polymer filaments sequentially onto a moving substrate to build an object. The feed material is a solid fiber that acts like a continuous piston in a heated barrel, which plasticates itself to push molten material through a nozzle. The barrel pressure is substantial, of order 30 MPa ( ≈4000 psi), and similar to that developed in contemporary polymer processing. The similarity does not end here with all the non-Newtonian and viscoelastic effects and heat transfer limitations that challenge extrusion operations coming to bear in the ME. These will be discussed in this review with suggestions of areas of study.

The fused filament fabrication (FFF) process is similar to classic extrusion operations; solid polymer is melted, pressurized, and extruded to produce an object. At this level of investigation, it appears no new science or engineering is required. However, FFF has heat transfer limitations that are unique to it, due to its small throughput, not encountered in contemporary polymer processing, negating the use of present-day correlations or heuristics. Here, we quantify heat transfer by rheological modeling of the pressure drop data in the process to generate a general Nusselt number–Graetz number correlation. This is the first time the pressure has been measured in the die (nozzle) during normal printing that we accomplished by monitoring the power used to drive the hot end. Ultimately, we find that fouling within the region used to melt/soften the polymer significantly reduces the heat transfer rate.

Polymeric structures fabricated using Fused Filament Fabrication (FFF) suffer from poor inter-laminar fracture toughness. As a result, these materials exhibit only a fraction of the mechanical performance of those manufactured through more traditional means. Here we show that thermal annealing of confined structures manufactured using the FFF technique dramatically increases their inter-laminar toughness. Single Edge Notch Bend (SENB) fracture specimens made from acrylonitrile-butadiene-styrene (ABS) feedstock were isothermally heated in a supporting fixture, post-manufacture, across a range of times and temperatures. Fracture testing was then used to quantify the changes in inter-laminar toughness offered by annealing through measurements of the Mode I critical elastic-plastic strain energy release rate, JIc. Under the most aggressive annealing conditions, the inter-laminar toughness increased by more than 2700% over the non-annealed baseline material. Void migration and aggregation during the annealing process was analyzed using X-ray tomography and provides insight into the toughening mechanisms. Time-scales of reptation and polymer mobility at the interface during annealing are also modeled and agree with fracture experiments.

In this report, a new class of functional chalcogenide hybrid inorganic/organic polymers (CHIPs) bearing free aryl amine groups that are amenable to post-polymerization modifications were synthesized. These functional CHIPs were synthesized via the inverse vulcanization of elemental sulfur with 4-vinylaniline without the need for functional group protection of amines. This polymer is the first example of a polysulfide or CHIP material to carry a useful primary amine functional group which can be successfully post functionalized with acid chlorides and isocyanates to improve the mechanical properties.

We report on the preparation of ultrahigh refractive index polymers via the inverse vulcanization of elemental sulfur, selenium, and 1,3-diisopropenylbenzene for use as novel transmissive materials for mid-infrared (IR) imaging applications. Poly(sulfur-random-selenium-random-(1,3-diisopropenylbenzene)) (poly(S-r-Se-r-DIB) terpolymer materials from this process exhibit the highest refractive index of any synthetic polymer (n > 2.0) and excellent IR transparency, which can be directly tuned by terpolymer composition. Sulfur or selenium containing (co)polymers prepared via inverse vulcanization can be described as Chalcogenide Hybrid Inorganic/Organic Polymers (CHIPs) and are polymeric analogues to wholly inorganic Chalcogenide Glasses (ChGs), which are commonly used as transmissive materials in mid-IR imaging. Finally, we demonstrate that CHIPs composed of (poly(S-r-Se-r-DIB) can be melt processed into windows that enabled high quality mid-IR thermal imaging of human subjects and highly resolved imaging of...

We show that it is possible to assemble a sparse mono-layer of Fe3O4 nanoparticles (NPs) at cathode interface of a polymer solar cell based on poly(3-hexylthiophene): [6,6]-phenyl-C60-butyric acid methyl ester (P3HT: PCBM) through the synergic effect of strong convective outflow, surface energy, Fe3O4 NPs concentration and active layer thickness. When the distance between those Fe3O4 NPs is smaller than the size of P3HT, the P3HT is excluded from the inter-particle space, and fullerene molecules fill in the space to build electron transport pathways improving charge transport and collection near cathode interface proved by transmission electron microscopy and X-ray photoelectron spectroscopy. The power conversion efficiency of the devices is improved up to 20%. The bulk morphology of light absorbing layers is not affected by the addition of Fe3O4 NPs as demonstrated by neutron and X-ray scattering results.

The failure (maximum) feed velocity in a LulzBot Taz 4 3D printer at various temperatures is determined for three polymers: Acrylonitrile butadiene styrene, poly(lactic acid) (PLA), and a PLA polyhydroxybutyrate copolymer. Through an approximate solution of the energy balance, we develop a model to correlate the dimensionless fiber feed velocity (represented by a Peclet number) with a dimensionless temperature. Using these dimensionless parameters, all polymers fall onto the same curve. However, when molten polymer is forced through a small nozzle to enable 3D printing, this curve also depends on another parameter: Nozzle diameter. Our model does not account for this parameter because it does not consider hydrodynamics due to the complexity of the coupled energy and momentum balances. Thus, we modify the Peclet number to account for hydrodynamics and produce a satisfactory master curve for all diameters and polymers. Our dimensionless numbers require determining the polymer thermal and rheological propert...

Phenyl-C71-butyric acid methyl ester (PC71BM) could intercalate between the side-chains of poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene (pBTTT) creating a stable co-crystal structure, so optimal solar cell performance was obtained at high PC71BM concentrations promoting phase separated electron conductive pathways. Neutron reflectivity, with the application of magnetic contrast variation, was used to investigate the concentration profile of PC71BM within the active layer. And this profile was found to be homogeneous through the film thickness. Small angle neutron scattering was utilized to find there is amorphous PC71BM even at 50 wt% of fullerene while previously it was believed that all fullerene was consumed to form co-crystals when its concentration is below 75 wt%. These fullerene molecules evolve into approximately 15 nm sized agglomerates to improve the electron transport when their concentration is above 75 wt%. Thermal annealing gives these agglomerates mobility to form micrometer sized crystals causing a decrease of device performance. These findings can therefore correlate the morphology, especially in terms of fullerene agglomerates, vertical concentration profile and percolating structure they formed, with the device performance and provide valuable guidance for optimal morphology design of polymer: fullerene solar cells.

The synthesis of a novel high sulfur content material possessing improved thermomechanical properties is reported via the inverse vulcanization of elemental sulfur (S8) and 1,3,5-triisopropenylbenzene (TIB). A key feature of this system was the ability to afford highly cross-linked, thermosetting materials, where the use of TIB as a comonomer enabled facile control of the network structure and dramatically improved the glass transition temperature (relative to our earlier sulfur copolymers) of poly(sulfur-random-(1,3,5-triisopropenylbenzene)) (poly(S-r-TIB)) materials over a range from T = 68 to 130 °C. This approach allowed for the incorporation of a high content of sulfur–sulfur (S–S) units in the copolymer that enabled thermomechanical scission of these dynamic covalent bonds and thermal reprocessing of the material, which we confirmed via dynamic rheological characterization. Furthermore, the high sulfur content also imparted high refractive index (n > 1.75) and IR transparency to poly(S-r-TIB) copoly...

High sulfur content copolymers were prepared via the inverse vulcanization of elemental sulfur with styrene. This reaction was carried out at a relatively low temperature and invokes a new chain transfer mechanism of abstraction of benzylic protons to form stable copolymers. The use of styrene as a comonomer for inverse vulcanization was attractive due to the low cost and wide spread industrial use of styrenics in free radical processes. The copolymers were used as the active cathode material in Li-S batteries that exhibited outstanding device performance, maintaining 489 mAh/g capacity after 1000 cycles. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 107–116

Tapered block polymers are an emerging class of macromolecules with unique and diverse self-assembly behavior and properties. Herein, we directly examine the manipulation of self-assembled interfaces in poly(isoprene-b-styrene) (I-S)-based block polymers (BPs) by synthesizing non-tapered (I-S), normal tapered (I-IS-S), and inverse tapered (I-SI-S) BPs with controlled monomer segment distributions. We provide the first direct measurements of interfacial mixing for these tapered polymers through X-ray reflectivity (XRR). The density profiles from XRR are compared to results from fluids density functional theory (fDFT) with good agreement. We find that our normal tapered BPs (30 vol % tapering) have similar interfacial mixing to diblock polymers, while our inverse tapered BPs (30 vol % tapering) have much wider interfaces. Additionally, differential scanning calorimetry (DSC) studies elucidate the influence of tapering on the glass transition temperature (Tg) and change of heat capacity (ΔCP) for each BP pha...

Fused filament fabrication (FFF), sometimes called material extrusion (ME) offers an alternative option to traditional polymer manufacturing techniques to allow the fabrication of objects without the need of a mold or template. However, these parts are limited in the degree to which the welding interface is eliminated post deposition, resulting in a decrease in the interlaminar fracture toughness relative to the bulk material. Here reptation theory under nonisothermal conditions is utilized to predict the development of healing over time, from the rheological and thermal properties of Acrylonitrile-Butadiene-Styrene (ABS). ABS is rheologically complex and acts as a gel and as such considerations had to be made for the relaxation time of the matrix which is important in predicting the degree of interfacial healing. The nonsiothermal healing model developed is then successfully compared to experimental interlaminar fracture experiments at variable printing temperatures, allowing future optimization of the process to make stronger parts.

Numerical simulation is used to understand the melting and pressurization mechanism in fused filament fabrication (FFF). The results show the incoming fiber melts axisymmetrically, forming a cone of unmelted material in the center surrounded by melted polymer. Details of the simulation reveal that a recirculating vortex of melted polymer is formed at the fiber entrance to the hot end. The large viscosity within this vortex acts to effectively seal the system against back-pressures of order 1000 psi (10 MPa), which are typical under standard printing conditions. The Generalized Newtonian Fluid (GNF) model was appropriate for simulation within the region that melts the fiber, however, a viscoelastic model, the Phan-Thien-Tanner (PTT) model, was required to capture flow within the nozzle. This is due to the presence of an elongational flow as molten material transitions from the melting region (diameter of 3 mm) to the nozzle at the exit (diameter of 0.5 mm). Remarkably, almost half the pressure drop occurs over the short capillary (0.5 mm in length) attached to the end of the converging flow region. Increased manufacturing rates are limited by high pressures, necessitating more consideration in the nozzle design of future FFF printers.

Quantitative morphological analysis is essential to the fundamental understanding of semiconducting polymers. Temperature modulated differential scanning calorimetry is used to determine the amount of crystalline and noncrystalline phases within regioregular poly(3-hexylthiophene) (rrP3HT). Careful optimization of the experimental conditions shows that the glass transition of rrP3HT consists of three parts corresponding to the devitrification of the side chains, mobile amorphous fraction (MAF), and rigid amorphous fraction (RAF), consecutively. Measurements taken from this, as well as from the melting transition, allows the first calculation of the degree of crystallinity, MAF and RAF, to be achieved in a single experiment for rrP3HT. This technique thus enables the morphological phases to be determined and potentially related to the performance of electronic devices made from semiconducting polymers.

We report on dynamic covalent polymers derived from elemental sulfur that can be used as thermally healable optical polymers for mid-IR thermal imaging applications. By accessing dynamic S–S bonds in these sulfur copolymers, surface scratches and defects of free-standing films of poly(sulfur-random-1,3-diisopropenylbenzene) (poly(S-r-DIB) can be thermally healed, which enables damaged lenses and windows from these materials to be reprocessed to recover their IR imaging performance. Correlation of the mechanical properties of these sulfur copolymers with different curing methods provided insights to reprocess damaged samples of these materials. Mid-IR thermal imaging experiments with windows before and after healing of surface defects demonstrated successful application of these materials to create a new class of “scratch and heal” optical polymers. The use of dynamic covalent polymers as healable materials for IR applications offers a unique advantage over the current state of the art (e.g., germanium or ...

We detail the influence of tapered interfaces on the nanoscale morphologies of ion-doped poly(styrene-b-oligo-oxyethylene methacrylate) block polymers (BPs). Most significantly, the location of double-gyroid network phase window was found in ion-doped normal-tapered materials, and a similar window was not detectable in the corresponding non-tapered and inverse-tapered BPs. Additionally, the effective interaction parameters, χeff, were reduced substantially in the tapered materials in comparison with their non-tapered counterparts. Overall, this work demonstrates that tapering between polymer blocks provides unique control over BP morphologies and improves the material processability (due to lower χeff), potentially facilitating the development of future ion-conducting devices.

High molecular weight multiblock copolymers are synthesized as robust polymer fibers via interfacial bioorthogonal polymerization employing the rapid cycloaddition of s-tetrazines with strained trans-cyclooctenes. When cell-adhesive peptide was incorporated in the tetrazine monomer, the resulting protein-mimetic polymer fibers provide guidance cues for cell attachment and elongation.

High sulfur content copolymers were prepared via inverse vulcanization of sulfur with 1,4-diphenylbutadiyne (DiPhDY) for use as the active cathode material in lithium–sulfur batteries. These sulfur-rich polymers exhibited excellent capacity retention (800 mA h g−1 at 300 cycles) and extended battery lifetimes of over 850 cycles at C/5 rate.

Our previous study presented up to 20% power conversion efficiency (PCE) enhancement of poly(3-hexylthiophene):phenyl-C61-butyric acid methyl ester (P3HT:PCBM) solar cells under the Fe3O4 nanoparticles (NPs) self-assembly (SA) effect by spin coating. Fe3O4 NPs (about 11 nm hydrodynamic diameter) form a thin layer at the top interface of the light absorbing active layer, which results in the generation of PCBM rich region improving the charge transport (Zhang et al. Sol Energ Mat Sol C 160:126–133, 2017). In order to investigate the feasibility of this Fe3O4 NPs SA effect under large-scale production condition, a smooth rod was implemented to mimic roll-to-roll coating technique and yield active layers having about the same thickness as the spin-coated ones. Small angle neutron scattering and grazing incidence X-ray diffraction were employed finding out similar morphologies of the active layers by these two coating techniques. However, rod-coated solar cell’s PCE decreases with the addition of Fe3O4 NPs compared with the one without them. This is because PCBM rich region is not created at the top interface of the active layer due to the absence of Fe3O4 NPs, which is attributed to the weak convective flow and low diffusion rate. Moreover, in the rod-coated solar cells, the presence of Fe3O4 NPs causes decrease in P3HT crystallinity, thus the charge transport and the device performance. Our study confirms the role of spin coating in the Fe3O4 NPs SA effect and enables researchers to explore this finding in other polymer nanocomposite systems.

The synthesis of dynamic covalent polymers with controllable amounts of sulfur–sulfur (S–S) bonds in the polymer backbone via inverse vulcanization of elemental sulfur (S8) and 1,3-diisopropenylbenzene (DIB) is reported. An attractive feature of the inverse vulcanization process is the ability to control the number and dynamic nature of S–S bonds in poly(sulfur-random-(1,3-diisopropenylbenzene)) (poly(S-r-DIB) copolymers by simple variation of S8/DIB feed ratios in the copolymerization. S–S bonds in poly(S-r-DIB) copolymers of high sulfur content and sulfur rank were found to be more dynamic upon exposure to either heat, or mechanical stimuli. Interrogation of dynamic S–S bonds was conducted in the solid-state utilizing electron paramagnetic resonance spectroscopy and in situ rheological measurements. Time-dependent rheological property behavior demonstrated a compositional dependence of the healing behavior in the copolymers, with the highest sulfur (80 wt % sulfur) content affording the most rapid dynam...

The enthalpy of fusion for a perfect, infinite poly(3-hexylthiophene) (P3HT) crystal (ΔHm∞) must be known to evaluate the absolute crystallinity of P3HT. This value, however, is still ambiguous as different values have been reported using various experimental techniques. Here, we extrapolate the enthalpy of fusion for extended chain crystals of oligomeric P3HT to infinite molecular weight and obtain a value of ΔHm∞≈ 42.9 ± 2 J/g employing differential scanning calorimetry with a correction based on grazing incidence small angle X-ray scattering data. Also, we define the onset of chain folding within P3HT crystallites at a chain length of 5 Kuhn segments. Knowledge of ΔHm∞ allows calculation of P3HT percent crystallinity in thin films for applications such as organic field effect transistors and solar cells. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014, 52, 1469–1475

The rheological properties of poly(3-hexylthiophene) (P3HT) solutions were investigated in a nonvolatile solvent, 2-ethylnaphthalene, at various P3HT concentrations. A mild viscosity increase was noted during shear for lower concentration P3HT solutions over 24 h, yet the viscosity increase was greater than if the sample was not sheared at all over the same time period. In this case, crystalline fibrils with large aspect ratios were formed during shear. Crystallization was determined to be dictated by Brownian motion and mediated by shear, or in other words Brownian motion brought the molecules together while shear changed their conformation to allow crystallization. Higher concentration P3HT solutions produced a significant viscosity increase, up to 2 orders of magnitude, during shear. Again, if a similar solution was merely aged without shear, a much lower viscosity increase was noted. Simple calculations show that the fibril concentration was above the percolation threshold at the higher concentration ...

Polymers for IR imaging: The preparation of high refractive index polymers (n = 1.75 to 1.86) via the inverse vulcanization of elemental sulfur is reported. High quality imaging in the near (1.5 μm) and mid-IR (3-5 μm) regions using high refractive index polymeric lenses from these sulfur materials was demonstrated.

Polymers with the ability to heal themselves could provide access to materials with extended lifetimes in a wide range of applications such as surface coatings, automotive components and aerospace composites. Here we describe the synthesis and characterisation of two novel, stimuli-responsive, supramolecular polymer blends based on p-electron-rich pyrenyl residues and p-electron-deficient, chain-folding aromatic diimides that interact through complementary p–p stacking interactions. Different degrees of supramolecular “cross-linking” were achieved by use of divalent or trivalent poly(ethylene glycol)-based polymers featuring pyrenyl end-groups, blended with a known diimide–ether copolymer. The mechanical properties of the resulting polymer blends revealed that higher degrees of supramolecular “cross-link density” yield materials with enhanced mechanical properties, such as increased tensile modulus, modulus of toughness, elasticity and yield point. After a number of break/heal cycles, these materials were found to retain the characteristics of the pristine polymer blend, and this new approach thus offers a simple route to mechanically robust yet healable materials.

Adding metallic nanoparticles into bulk-heterojunction, polymer-based solar cells has been proven an effective strategy to enhance light absorption of the active layer and device performance. However, the high-energy surfaces on the nanoparticles may also affect the morphology of the active layer by influencing phase-separation, which has not been studied in detail. Here, we show that silica particles embedded in the active layer will affect the aggregation behavior of [6,6]-phenyl C61-butyric acid methyl ester (PCBM) in the bulk-heterojunction of poly(3-hexylthiophene) (P3HT):PCBM. Using a novel graphical technique to analyze the absolute scattering intensity of small angle neutron scattering data, we conclusively demonstrate that some PCBM will migrate away from the bulk solution to the surface of the silica upon annealing and improve the device performance. The overall effect is to decrease the device series resistance and improve the power conversion efficiency by 10 to 20% relative to the control group. In contrast to metallic nanoparticles that utilize the surface plasmon resonance, our results indicate that, even with optically inert particles, the induced phase separation of PCBM may also result in an improved device.

We present a dual length morphological model for the active layer of bulk-heterojunction, polymer-based solar cells using results from neutron and X-ray scattering techniques. Two critical characteristic lengths are found in the mixtures composed of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). A characteristic length at 15 nm is the local characteristic of the P3HT crystals and PCBM agglomerations, which is independent of the bulk composition upon relaxation by thermal annealing. Conversely, a larger bicontinuous structure described by Teubner–Strey model with phase distances between 23 and 35 nm forms only after thermal annealing, which is highly correlated to the bulk compositions. These results suggest phase separation between the polymer and fullerene can only be partially manipulated by simple processing techniques such as coating conditions and annealing, and a more rigorous design of the morphology should be implemented in the future. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym. Phys. 2014, 52, 387–396

The synthesis and thermomechanical properties of a novel class of self-healing perfluoropolyethers (PFPEs) is reported. By decoration of 2-ureido-4[1H]-pyrimidone end groups on the termini of low molar mass PFPE, the formation of supramolecular polymers and networks held together via hydrogen bonding associations was achieved. These novel supramolecular polymer materials exhibit a combination of enhanced modulus and elasticity, along with self-healing properties, where rapid self-healing time was demonstrated using dynamic rheological measurements. These types of supramolecular PFPEs are anticipated to be useful for a number of emerging areas in lubrication. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3598–3606

An excess of elemental sulfur is generated annually from hydrodesulfurization in petroleum refining processes; however, it has a limited number of uses, of which one example is the production of sulfuric acid. Despite this excess, the development of synthetic and processing methods to convert elemental sulfur into useful chemical substances has not been investigated widely. Here we report a facile method (termed ‘inverse vulcanization’) to prepare chemically stable and processable polymeric materials through the direct copolymerization of elemental sulfur with vinylic monomers. This methodology enabled the modification of sulfur into processable copolymer forms with tunable thermomechanical properties, which leads to well-defined sulfur-rich micropatterned films created by imprint lithography. We also demonstrate that these copolymers exhibit comparable electrochemical properties to elemental sulfur and could serve as the active material in Li–S batteries, exhibiting high specific capacity (823 mA h g−1 at 100 cycles) and enhanced capacity retention. A polymerization method for converting elemental sulfur into a chemically stable, processable and electrochemically active copolymer has been described. This methodology — termed inverse vulcanization — is conducted by a one-step process using liquid sulfur, as both reaction medium and reactant, and vinylic comonomers to form polymeric materials with a high content of sulfur (50–90 wt%).

A series of organic/inorganic hybrid block and random copolymers were prepared by reversible addition–fragmentation chain transfer (RAFT) polymerization using poly(ethylene glycol) methyl ether methacrylate (PEGMA) and 3-(3,5,7,9,11,13,15-heptaisobutylpentacyclo[9.5.1.13,9.15,15.17,13]octasiloxane-1-yl)propyl methacrylate (MA-POSS) as monomers in order to study the effect of polymer morphology and POSS content on the properties of polymer electrolytes. Flexible and dimensionally stable free-standing films were made from the hybrid block and random copolymers mixed with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) when the contents of MA-POSS unit were larger than 31 and 16 mol %, respectively. The ionic conductivity of the solid-state block copolymer (PBP) electrolyte was found to be 1 order of magnitude higher than that of the random copolymer (PRP) electrolyte when they had similar MA-POSS content, although their glass transition temperature values of their ion-conducting segments were quite clos...

β-hairpin peptide-based hydrogels are a class of injectable solid hydrogels that can deliver encapsulated cells or molecular therapies to a target site via syringe or catheter injection as a carrier material. These physical hydrogels can shear-thin and consequently flow as a low-viscosity material under a sufficient shear stress but immediately recover back into a solid upon removal of the stress, allowing them to be injected as preformed gel solids. Hydrogel behavior during flow was studied in a cylindrical capillary geometry that mimicked the actual situation of injection through a syringe needle in order to quantify effects of shear-thin injection delivery on hydrogel flow behavior and encapsulated cell payloads. It was observed that all β-hairpin peptide hydrogels investigated displayed a promising flow profile for injectable cell delivery: a central wide plug flow region where gel material and cell payloads experienced little or no shear rate and a narrow shear zone close to the capillary wall where gel and cells were subject to shear deformation. The width of the plug flow region was found to be weakly dependent on hydrogel rigidity and flow rate. Live-dead assays were performed on encapsulated MG63 cells three hours after injection flow and revealed that shear-thin delivery through the capillary had little impact on cell viability and the spatial distribution of encapsulated cell payloads. These observations help us to fundamentally understand how the gels flow during injection through a thin catheter and how they immediately restore mechanically and morphologically relative to pre-flow, static gels.

A supramolecular polymer blend, formed via π-π interactions between a π-electron rich pyrenyl end-capped oligomer and a chain-folding oligomer containing pairs of π-electron poor naphthalene-diimide (NDI) units, has been reinforced with cellulose nanocrystals (CNCs) to afford a healable nanocomposite material. Nanocomposites with varying weight percentage of CNCs (from 1.25 to 20.0 wt %) within the healable supramolecular polymeric matrix have been prepared via solvent casting followed by compression molding, and their mechanical properties and healing behavior have been evaluated. It is found that homogeneously dispersed films can be formed with CNCs at less than 10 wt %. Above 10 wt % CNC heterogeneous nanocomposites were obtained. All the nanocomposites formed could be rehealed upon exposure to elevated temperatures although, for the homogeneous films, it was found that the healing rate was reduced with increasing CNC content. The best combination of healing efficiency and mechanical properties was obtained with the 7.5 wt % CNC nanocomposite which exhibited a tensile modulus enhanced by as much as a factor of 20 over the matrix material alone and could be fully rehealed at 85 °C within 30 min. Thus it is demonstrated that supramolecular nanocomposites can afford greatly enhanced mechanical properties relative to the unreinforced polymer, while still allowing efficient thermal healing.

Previously we characterized the active layer in polymer-based solar cells containing Poly(3-hexylthiophene) with the electron acceptor Phenyl-C61-butyric acid methyl ester (PCBM) to find a thin, pure polymer layer at the air interface just after spin coating. In this study, we find that when the aluminum back electrode was thermally evaporated onto the active layer, at high enough rate, craters were found in the pure polymer layer. This was determined by dissolving the aluminum and characterizing the active layer with an atomic force microscope. Poor device performance was noted under this condition. However, if the aluminum was evaporated at a slower rate, resulting in a flat active layer surface and no crater formation, the efficiency more than doubled. A similar result is found if lithium fluoride (LiF) is deposited before aluminum evaporation and no craters were found even for the higher aluminum evaporation rate. So, it appears that LiF acts as a momentum shield to crater formation allowing superior device performance. If the active layer is annealed before deposition of the back electrode then, regardless of deposition rate, similar device performance is found. Again, in our previous study, it was found that annealing the active layer forced PCBM to the air interface which apparently also acts as a momentum shield. Annealing the device after aluminum deposition produces poorer performance than annealing before deposition. However, these devices have a better fill factor. Examining the active layer shows that it undergoes a buckling transition due to differences in the aluminum and active layers' thermal expansivities which reduces overall contact with the electrodes. However, whatever contact is made, is superior, accounting for the improved fill factor. If the buckling instability could be avoided then this processing procedure may be used in the future to manufacture even better devices than with any of the other annealing procedures. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011

An elastomeric, healable, supramolecular polymer blend comprising a chain-folding polyimide and a telechelic polyurethane with pyrenyl end groups is compatibilized by aromatic pi-pi stacking between the pi-electron-deficient diimide groups and the pi-electron-rich pyrenyl units. This interpolymer interaction is the key to forming a tough, healable, elastomeric material. Variable-temperature FTIR analysis of the bulk material also conclusively demonstrates the presence of hydrogen bonding, which complements the pi-pi stacking interactions. Variable-temperature SAXS analysis shows that the healable polymeric blend has a nanophase-separated morphology and that the X-ray contrast between the two types of domain increases with increasing temperature, a feature that is repeatable over several heating and cooling cycles. A fractured sample of this material reproducibly regains more than 95% of the tensile modulus, 91% of the elongation to break, and 77% of the modulus of toughness of the pristine material.

Diels−Alder (DA) chemistry is increasing popular due to its simplicity and efficiency; however, one concept that has yet to be thoroughly explored is incorporation of DA linkages within materials f...