La2Zr2O7 Nanoparticle-Mediated Synthesis of Porous Al-Doped Li7La3Zr2O12 Garnet.

In this work, we modified the reaction pathway to quickly (minutes) incorporate lithium and stabilize the ionic conducting garnet phase by decoupling the formation of a La-Zr-O network from the addition of lithium. To do this, we synthesized La2Zr2O7 (LZO) nanoparticles to which LiNO3 was added. This method is a departure from typical solid-state synthesis methods that require high-energy milling to promote mixing and intimate particle-particle contact and from sol-gel syntheses as a unique porous microstructure is obtained. We show that the reaction time is limited by the rate of nitrate decomposition and that this method produces a porous high-Li-ion-conducting cubic phase, within an hour, that may be used as a starting structure for a composite electrolyte.

Swelling of individual nanodomains in hydrated block copolymer electrolyte membranes.

In this work, we examine the swelling of nanostructured block copolymer electrolytes immersed in liquid water. A series of sulfonated polystyrene-b-polyethylene-b-polystyrene (S-SES) membranes having the same nominal chemical composition but two different morphologies are prepared by systematic changes in processing. We start with a membrane comprising a mixture of homopolymer polystyrene (hPS) and a polystyrene-b-polyethylene-b-polystyrene (SES) copolymer. hPS is subsequently selectively removed from the membrane and the polystyrene domains are sulfonated to give S-SES membranes. The morphology of the membranes is controlled by controlling ϕ v, the volume fraction of hPS in the blended membrane. The morphology of the membranes was studied by small angle X-ray scattering (SAXS), cryogenic scanning transmission electron microscopy (cryo-STEM), and cryogenic electron tomography. The overall domain swelling measured by SAXS decreases slightly at ϕ v = 0.29; a crossover from lamellar to bicontinuous morphology is obtained at the same value of ϕ v. The bicontinuous morphologies absorb more water than the lamellar morphologies. By contrast, the nanodomain swelling of the bicontinuous membrane (120%) is slightly less than that of the lamellar membrane (150%). Quantitative analysis of the STEM images and electron tomography was used to determine the swelling on the hydrophilic and hydrophobic domains due to exposure to water. The hydrophilic sulfonated polystyrene-rich domain spacing increases while the hydrophobic polyethylene domain spacing decreases when the membranes are hydrated. The extent of increase and decrease is not a strong function of ϕ v.

Effect of morphology of nanoscale hydrated channels on proton conductivity in block copolymer electrolyte membranes.

Hydrated membranes with cocontinuous hydrophilic and hydrophobic phases are needed to transport protons in hydrogen fuel cells. Herein we study the water uptake and proton conductivity of a model fuel cell membrane comprising a triblock copolymer, polystyrenesulfonate-block-polyethylene-block-polystyrenesulfonate (S-SES), as a function of water activity in both humid air and liquid water. We demonstrate that the water uptake and proton conductivity of S-SES membranes equilibrated in liquid water are fundamentally different from values obtained when they were equilibrated in humid air. The morphological underpinnings of our observations were determined by synchrotron small-angle X-ray scattering and cryogenic scanning transmission electron microscopy. A discontinuous increase in conductivity when nearly saturated humid air is replaced with liquid water coincides with the emergence of heterogeneity in the hydrated channels: a water-rich layer is sandwiched between two polymer-rich brushes. While the possibility of obtaining heterogeneous hydrated channels in polymer electrolyte membranes has been discussed extensively, to our knowledge, this is the first time that direct evidence for the formation of water-rich subdomains is presented.

Ionic Conductivity Enhancement of Polymer Electrolytes by Directed Crystallization.

We report that hot stretching of poly(ethylene oxide) (PEO)-based solid polymer electrolytes (SPEs) can lead to a preferred orientation of PEO crystalline lamellae, thereby reducing the tortuosity of the ion-conduction pathway along the thickness direction of the SPE film, causing improved ionic conductivity. The hot stretching method is implemented by stretching SPE films above the melting point of PEO in an inert environment followed by crystallization at room temperature while maintaining the applied strain. The effect of hot stretching on the crystalline orientation, crystallinity, morphology, and ion transport in PEO with two types of salts, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) and lithium triflate (LiCF3SO3), is investigated in detail. Wide-angle X-ray scattering (WAXS) and small-angle X-ray scattering (SAXS) show that the orientation of PEO crystalline lamellae induces the formation of a short ion-conduction pathway along the through-plane direction of the SPE films, leading to 1.4- to 3.5-fold enhancement in the through-plane ionic conductivity.

Upcycling of semicrystalline polymers by compatibilization: mechanism and location of compatibilizers.

With the continuous increase of global plastics production, there is a demand to develop energy efficient processes to transform mixed plastic wastes into new products with enhanced utility - a concept that is often referred to as upcycling. Compatibilization is one of the most promising strategies to upcycle communal waste plastics. In this work, poly(ethylene terephthalate) (PET) and high-density polyethylene (HDPE), both widely used semicrystalline packaging polymers, are used as the target polymer blend. We systematically evaluate and compare three commercial ethylene copolymer based compatibilizers, ELVALOY™ AC 2016 Acrylate Copolymer (EAA), ELVALOY™ PTW Copolymer (PTW), and SURLYN™ 1802 Ionomer (Surlyn). They represent different compatibilization mechanisms. Furthermore, this work tackles a challenging question: where the compatibilizers are located in the blend. We discover that the location of the compatibilizer molecules can be predicted by comparing the crystallinity change of PET and HDPE in binary and ternary systems. Gaining this knowledge will facilitate root cause analysis of an ineffective compatibilizer and guide the design strategy to upcycle commingled waste plastics.

Design of tough adhesive from commodity thermoplastics through dynamic crosslinking.

Tough adhesives provide resistance against high debonding forces, and these adhesives are difficult to design because of the simultaneous requirement of strength and ductility. Here, we report a design of tough reversible/recyclable adhesive materials enabled by incorporating dynamic covalent bonds of boronic ester into commodity triblock thermoplastic elastomers that reversibly bind with various fillers and substrates. The spectroscopic measurements and density functional theory calculations unveil versatile dynamic covalent binding of boronic ester with various hydroxy-terminated surfaces such as silica nanoparticles, aluminum, steel, and glass. The designed multiphase material exhibits exceptionally high adhesion strength and work of debonding with a rebonding capability, as well as outstanding mechanical, thermal, and chemical resistance properties. Bonding and debonding at the interfaces dictate hybrid material properties, and this revelation of tailored dynamic interactions with multiple interfaces will open up a new design of adhesives and hybrid materials.

Control of morphology and its effects on the optical properties of polymer nanocomposites.

Chain-grafted Au nanoparticles were synthesized and incorporated into a fluorescent polymer, poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV), host. We show that control of the Au nanoparticle distribution within MEH-PPV is achieved by manipulating the enthalpic and entropic interactions between the grafted brush layers and the host chains. Further, we show that the fluorescence of these Au/MEH-PPV nanocomposite thin films may be "tailored" by as much as an order of magnitude through changes in the nanoparticle distribution, brush length, and nanoparticle size. The ideas presented herein represent reliable strategies for materials design for devices.

Block Copolymer Membranes for Efficient Capture of a Chemotherapy Drug.

We introduce the use of block copolymer membranes for an emerging application, "drug capture". The polymer is incorporated in a new class of biomedical devices, referred to as ChemoFilter, which is an image-guided temporarily deployable endovascular device designed to increase the efficacy of chemotherapy-based cancer treatment. We show that block copolymer membranes consisting of functional sulfonated polystyrene end blocks and a structural polyethylene middle block (S-SES) are capable of capturing doxorubicin, a chemotherapy drug. We focus on the relationship between morphology of the membrane in the ChemoFilter device and efficacy of doxorubicin capture measured in vitro. Using small-angle X-ray scattering and cryogenic scanning transmission electron microscopy, we discovered that rapid doxorubicin capture is associated with the presence of water-rich channels in the lamellar-forming S-SES membranes in aqueous environment.

Orientation mapping of semicrystalline polymers using scanning electron nanobeam diffraction.

We demonstrate a scanning electron nanobeam diffraction technique that can be used for mapping the size and distribution of nanoscale crystalline regions in a polymer blend. In addition, it can map the relative orientation of crystallites and the degree of crystallinity of the material. The model polymer blend is a 50:50w/w mixture of semicrystalline poly(3-hexylthiophene-2,5-diyl) (P3HT) and amorphous polystyrene (PS). The technique uses a scanning electron beam to raster across the sample and acquires a diffraction image at each probe position. Through image alignment and filtering, the diffraction image dataset enables mapping of the crystalline regions within the scanned area and construction of an orientation map.

Membranes with artificial free-volume for biofuel production.

Free-volume of polymers governs transport of penetrants through polymeric films. Control over free-volume is thus important for the development of better membranes for a wide variety of applications such as gas separations, pharmaceutical purifications and energy storage. To date, methodologies used to create materials with different amounts of free-volume are based primarily on chemical synthesis of new polymers. Here we report a simple methodology for generating free-volume based on the self-assembly of polyethylene-b-polydimethylsiloxane-b-polyethylene triblock copolymers. We have used this method to fabricate a series of membranes with identical compositions but with different amounts of free-volume. We use the term artificial free-volume to refer to the additional free-volume created by self-assembly. The effect of artificial free-volume on selective transport through the membranes was tested using butanol/water and ethanol/water mixtures due to their importance in biofuel production. We found that the introduction of artificial free-volume improves both alcohol permeability and selectivity.

Morphology-Conductivity Relationship of Single-Ion-Conducting Block Copolymer Electrolytes for Lithium Batteries.

A significant limitation of rechargeable lithium-ion batteries arises because most of the ionic current is carried by the anion, the ion that does not participate in energy-producing reactions. Single-ion-conducting block copolymer electrolytes, wherein all of the current is carried by the lithium cations, have the potential to dramatically improve battery performance. The relationship between ionic conductivity and morphology of single-ion-conducting poly(ethylene oxide)-b-polystyrenesulfonyllithium(trifluoromethylsulfonyl)imide (PEO-PSLiTFSI) diblock copolymers was studied by small-angle X-ray scattering and ac impedance spectroscopy. At low temperatures, an ordered lamellar phase is obtained, and the "mobile" lithium ions are trapped in the form of ionic clusters in the glassy polystyrene-rich microphase. An increase in temperature results in a thermodynamic transition to a disordered phase. Above this transition temperature, the lithium ions are released from the clusters, and ionic conductivity increases by several orders of magnitude. This morphology-conductivity relationship is very different from all previously published data on published electrolytes. The ability to design electrolytes wherein most of the current is carried by the lithium ions, to sequester them in nonconducting domains and release them when necessary, has the potential to enable new strategies for controlling the charge-discharge characteristics of rechargeable lithium batteries.

Design of a humidity controlled sample stage for simultaneous conductivity and synchrotron X-ray scattering measurements.

We report on the design and operation of a novel sample stage, used to simultaneously measure X-ray scattering profiles and conductivity of a polymer electrolyte membrane (PEM) surrounded by humid air as a function of temperature and relative humidity. We present data obtained at the Advanced Light Source and Stanford Synchrotron Radiation Laboratory. We demonstrate precise humidity control and accurate determination of morphology and conductivity over a wide range of temperatures. The sample stage is used to study structure-property relationships of a semi-crystalline block copolymer PEM, sulfonated polystyrene-block-polyethylene.