Kinetic Control of Graphene Localization in Co-continuous Polymer Blends via Melt Compounding.

Selective localization of graphene in co-continuous polymer blends is an attractive method for preparing conductive polymer composites. Localization of graphene at the interface between the two polymer phases produces good conductivity at ultra-low concentrations. Although graphene localization is ultimately dependent on thermodynamic factors such as the surface energy of graphene and the two polymer components, kinetics also strongly affects the migration and localization of graphene in polymer blends during melt compounding. However, few studies have systemically investigated the important role of kinetics on graphene localization. Here, we introduced graphene nanoplatelets (GNPs) in polylactic acid (PLA)/polystyrene (PS) co-continuous polymer blends. Although GNPs in thermal equilibrium prefer the PS phase, we were able to kinetically trap GNPs at the interface of polymer blends via control of melt-compounding sequences, mixing times and shear rates. Utilizing morphological, rheological, and electrical measurements, we verified graphene localization and the suppression of coarsening in co-continuous polymer blends during annealing. When GNPs were premixed with the thermodynamically less-favorable PLA phase before mixing with the PS phase, GNPs can be kinetically trapped at the interface during melt compounding. Moreover, we show that a shorter melt-compounding time gives rise to a higher GNP interfacial coverage and a more effective morphology stabilization effect. Blends with as low as 0.5 wt % GNPs with only 30 s of melt compounding have a room-temperature conductivity of ∼10-6 S/cm, which is larger than blends with longer melt-compounding times and potentially useful for antistatic materials. The in-depth study on the kinetics of graphene localization in our work provides a general guideline for the kinetic control of the localization of platelike nanofillers in polymer blends. Our study also demonstrates a facile method for manufacturing conductive polymer blends with low percolation thresholds.

Capillary Coatings: Flow and Drying Dynamics in Open Microchannels.

Capillary flow and drying of polymer solutions in open microchannels are explored over time scales spanning seven orders of magnitude: from capillary filling (10-3-10 s) to the formation of a dry thin film (a "capillary coating"; 102-103 s). During capillary filling, drying-induced changes (increased solids content and viscosity) generate microscale pinning events that impede contact line motion. Three unique types of pinning are identified and characterized, each defined by the specific location(s) along the contact line at which pinning is induced. Drying is shown to ultimately pin the contact line permanently, and the associated total flow distances and times are revealed to be strong functions of channel width and drying rate. In general, lower drying rates coupled with intermediate channel widths are found to be most conducive to longer flow distances and times. After the advancing contact line permanently pins, internal flows driven by uneven evaporation rates continue to drive polymer to the contact line. This phenomenon promotes a local accumulation of solids and persists until all motion is arrested by drying. The effects of channel width and drying rate are investigated at each stage of this capillary coating process. These results are then applied to case studies of two functional inks commonly used in printed electronics fabrication: a PEDOT:PSS (poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate)) ink and a graphene ink. Although drying is shown to permanently arrest flow in both inks, both systems exhibit an increased resistance to pinning unexplained by mechanisms identified in aqueous polymer systems. Instead, arguments based on chemistry, particle size, and rheology are used to explain their novel behavior. These case studies provide insight into how functional inks can be better designed to optimize flow distances and maximize overall dry film uniformity in capillary coatings.

Dynamics of Capillary-Driven Flow in 3D Printed Open Microchannels.

Microchannels have applications in microfluidic devices, patterns for micromolding, and even flexible electronic devices. Three-dimensional (3D) printing presents a promising alternative manufacturing route for these microchannels due to the technology's relative speed and the design freedom it affords its users. However, the roughness of 3D printed surfaces can significantly influence flow dynamics inside of a microchannel. In this work, open microchannels are fabricated using four different 3D printing techniques: fused deposition modeling (FDM), stereolithography (SLA), selective laser sintering, and multi jet modeling. Microchannels printed with each technology are evaluated with respect to their surface roughness, morphology, and how conducive they are to spontaneous capillary filling. Based on this initial assessment, microchannels printed with FDM and SLA are chosen as models to study spontaneous, capillary-driven flow dynamics in 3D printed microchannels. Flow dynamics are investigated over short (∼10-3 s), intermediate (∼1 s), and long (∼102 s) time scales. Surface roughness causes a start-stop motion down the channel due to contact line pinning, while the cross-sectional shape imparted onto the channels during the printing process is shown to reduce the expected filling velocity. A significant delay in the onset of Lucas-Washburn dynamics (a long-time equilibrium state where meniscus position advances proportionally to the square root of time) is also observed. Flow dynamics are assessed as a function of printing technology, print orientation, channel dimensions, and liquid properties. This study provides the first in-depth investigation of the effect of 3D printing on microchannel flow dynamics as well as a set of rules on how to account for these effects in practice. The extension of these effects to closed microchannels and microchannels fabricated with other 3D printing technologies is also discussed.

Open-Pore Two-Dimensional MFI Zeolite Nanosheets for the Fabrication of Hydrocarbon-Isomer-Selective Membranes on Porous Polymer Supports.

Two-dimensional zeolite nanosheets that do not contain any organic structure-directing agents were prepared from a multilamellar MFI (ML-MFI) zeolite. ML-MFI was first exfoliated by melt compounding and then detemplated by treatment with a mixture of H2 SO4 and H2 O2 (piranha solution). The obtained OSDA-free MFI nanosheets disperse well in water and can be used for coating applications. Deposits made on porous polybenzimidazole (PBI) supports by simple filtration of these suspensions exhibit an n-butane/isobutane selectivity of 5.4, with an n-butane permeance of 3.5×10(-7)  mol m(-2) s(-1) Pa(-1) (ca. 1000 GPU).

Nanoparticles Containing High Loads of Paclitaxel-Silicate Prodrugs: Formulation, Drug Release, and Anticancer Efficacy.

We have investigated particle size, interior structure, drug release kinetics, and anticancer efficacy of PEG-b-PLGA-based nanoparticles loaded with a series of paclitaxel (PTX)-silicate prodrugs [PTX-Si(OR)3]. Silicate derivatization enabled us to adjust the hydrophobicity and hydrolytic lability of the prodrugs by the choice of the alkyl group (R) in the silicate derivatives. The greater hydrophobicity of these prodrugs allows for the preparation of nanoparticles that are stable in aqueous dispersion even when loaded with up to ca. 75 wt % of the prodrug. The hydrolytic lability of silicates allows for facile conversion of prodrugs back to the parent drug, PTX. A suite of eight PTX-silicate prodrugs was investigated; nanoparticles were made by flash nanoprecipitation (FNP) using a confined impingement jet mixer with a dilution step (CIJ-D). The resulting nanoparticles were 80-150 nm in size with a loading level of 47-74 wt % (wt %) of a PTX-silicate, which corresponds to 36-59 effective wt % of free PTX. Cryogenic transmission electron microscopy images show that particles are typically spherical with a core-shell structure. Prodrug/drug release profiles were measured. Release tended to be slower for prodrugs having greater hydrophobicity and slower hydrolysis rate. Nanoparticles loaded with PTX-silicate prodrugs that hydrolyze most rapidly showed in vitro cytotoxicity similar to that of the parent PTX. Nanoparticles loaded with more labile silicates also tended to show greater in vivo efficacy.

Dynamics and rheology of nonpolar bijels.

Bicontinuous, interfacially jammed, emulsion gels (bijels) are a novel class of materials composed of two immiscible phases with interpenetrating domains that are stabilized by a monolayer of colloidal particles at the interface. However, existing bijel systems so far all consist of at least one polar fluid, which is believed to be essential to induce electrostatic repulsion for stabilizing interfacial particles. It is not known whether two nonpolar fluids can form a bijel. Here, we experimentally achieve a bijel using styrene trimer and low molecular weight polybutene-two nonpolar fluids that are similar to polymer blends, which are important in technical applications. By combining laser scanning confocal microscopy, cryo-SEM and rheology measurement, we systematically investigate the dynamics and rheology of this nonpolar bijel. In contrast to previous studies on polar bijels, we observe the formation of localized regions of high particle concentration or "particle patches" on the interface which assemble during coarsening. We also provide the first quantitative relation between the morphology of a bijel, the interfacial particle coverage and the shear modulus during bijel coarsening. Moreover, we reveal a previously unnoticed increase in the elastic modulus of bijels that can be attributed to the rearrangement of interfacial particles at long time scales. In addition, we also found a hydrophobic particle framework that survives after the direct remixing of the nonpolar bijel. Our study provides important insights into the formation of bijels and is the first step to explore the missing link between polar bijels and particle-stabilized bicontinuous polymer blends.

2D Zeolite Coatings: Langmuir-Schaefer Deposition of 3†nm Thick MFI Zeolite Nanosheets.

Stable suspensions of zeolite nanosheets (3 nm thick MFI layers) were prepared in ethanol following acid treatment, which partially removed the associated organic structure-directing agent. Nanosheets from these suspensions could then be dispersed at the air-water interface and transferred to silicon wafers using Langmuir-Schaefer deposition. Using layer-by-layer deposition, control on coating thickness was demonstrated. In-plane X-ray diffraction (XRD) revealed that the deposited nanosheets contract upon calcination similar to bulk MFI crystals. Different methods for secondary growth resulted in preferentially oriented thin films of MFI, which had sub-12-nm thickness in certain cases. Upon calcination, there was no contraction detectable by in-plane XRD, indicating well-intergrown MFI films that are strongly attached to the substrate.

AFM probing of polymer/nanofiller interfacial adhesion and its correlation with bulk mechanical properties in a poly(ethylene terephthalate) nanocomposite.

The interfacial adhesion between polymer and nanofiller plays an important role in affecting the properties of nanocomposites. The detailed relationship between interfacial adhesion and bulk properties, however, is unclear. In this work, we developed an atomic force microscopy (AFM)-based abrasive scanning methodology, as applied to model laminate systems, to probe the strength of interfacial adhesion relevant to poly(ethylene terephthalate) (PET)/graphene or clay nanocomposites. Graphite and mica substrates covered with ∼2 nm thick PET films were abrasively sheared by an AFM tip as a model measurement of interfacial strength between matrix PET and dispersed graphene and clay, respectively. During several abrasive raster-scan cycles, PET was shear-displaced from the scanned region. At temperatures below the PET glass transition, PET on graphite exhibited abrupt delamination (i.e., full adhesive failure), whereas PET on mica did not; rather, it exhibited a degree of cohesive failure within the shear-displaced layer. Moreover, 100-fold higher force scanning procedures were required to abrade through an ultimate "precursor" layer of PET only ∼0.2-0.5 nm thick, which must be largely disentangled from the matrix polymer. Thus, the adhesive interface of relevance to the strength of clay-filler nanocomposites is between matrix polymer and strongly bound polymer. At 90 °C, above the bulk PET glass transition temperature, the PET film exhibited cohesive failure on both graphite and mica. Our results suggest that there is little difference in the strength of the relevant interfacial adhesion in the two nanocomposites within the rubbery dynamic regime. Further, the bulk mechanical properties of melt mixed PET/graphene and PET/clay nanocomposites were evaluated by dynamic mechanical analysis. The glassy dynamic storage modulus of the PET/clay nanocomposite was higher than that of PET/graphene, correlating with the differences in interfacial adhesion probed by AFM.

Flash nanoprecipitation: particle structure and stability.

Flash nanoprecipitation (FNP) is a process that, through rapid mixing, stabilizes an insoluble low molecular weight compound in a nanosized, polymer-stabilized delivery vehicle. The polymeric components are typically amphiphilic diblock copolymers (BCPs). In order to fully exploit the potential of FNP, factors affecting particle structure, size, and stability must be understood. Here we show that polymer type, hydrophobicity and crystallinity of the small molecule, and small molecule loading levels all affect particle size and stability. Of the four block copolymers (BCP) that we have studied here, poly(ethylene glycol)-b-poly(lactic-co-glycolic acid) (PEG-b-PLGA) was most suitable for potential drug delivery applications due to its ability to give rise to stable nanoparticles, its biocompatibility, and its degradability. We found little difference in particle size when using PLGA block sizes over the range of 5 to 15 kDa. The choice of hydrophobic small molecule was important, as molecules with a calculated water-octanol partition coefficient (clogP) below 6 gave rise to particles that were unstable and underwent rapid Ostwald ripening. Studies probing the internal structure of nanoparticles were also performed. Analysis of differential scanning calorimetry (DSC), cryogenic transmission electron microscopy (cryo-TEM), and (1)H NMR experiments support a three-layer core-shell-corona nanoparticle structure.

Interfacial rheology and structure of tiled graphene oxide sheets.

The hydrophilic nature of graphene oxide sheets can be tailored by varying the carbon to oxygen ratio. Depending on this ratio, the particles can be deposited at either a water-air or a water-oil interface. Upon compression of thus-created Langmuir monolayers, the sheets cover the entire interface, assembling into a strong, compact layer of tiled graphene oxide sheets. With further compression, the particle layer forms wrinkles that are reversible upon expansion, resembling the behavior of an elastic membrane. In the present work, we investigate under which conditions the structure and properties of the interfacial layer are such that free-standing films can be obtained. The interfacial rheological properties of these films are investigated using both compressional experiments and shear rheometry. The role of surface rheology in potential applications of such tiled films is explored. The rheological properties are shown to be responsible for the efficiency of such layers in stabilizing water-oil emulsions. Moreover, because of the mechanical integrity, large-area monolayers can be deposited by, for example, Langmuir-Blodgett techniques using aqueous subphases. These films can be turned into transparent conductive films upon subsequent chemical reduction.

Improved Polypropylene Thermoformability through Polyethylene Layering.

Due to its low cost, stiffness, and recyclability, isotactic polypropylene (iPP) is an excellent candidate for packaging applications. However, iPP is notoriously difficult to thermoform due to its low melt strength. The addition of just 10 thin layers of high-molecular-weight, linear low-density polyethylene (LLDPE) into iPP sheets by coextrusion significantly increased extensional viscosity and reduced sag. Both LLDPE and iPP were metallocene-catalyzed with excellent adhesion as measured in our previous work. We performed a series of hot tensile tests and sheet sag measurements to determine the properties of the iPP sheet and the multilayer sheet between 130 and 180 °C. To evaluate the thermoformability of these multilayer sheets, truncated conical cups were positive vacuum formed at different temperatures and heating times, and the crush strength was measured. Cups that released easily from the mold with good shape retention and a crush strength within 80% of the maximum value were used to define a temperature-time thermoformability window. We estimated the maximum stress that occurred during the thermoforming process to be 5 MPa. Layer thicknesses before and after thermoforming were used to estimate an average strain of 0.78. The thin LLDPE layers decreased the yield stress below 5 MPa. This enabled thermoforming at sheet temperatures as low as 150 °C. The immiscible LLDPE interfaces increased extensional viscosity, which decreased sag in the multilayer sheets compared to iPP. This broadened the thermoforming range to temperatures as high as 180 °C and allowed longer heating times. These highly thermoformable, layered sheets may be recycled as iPP since they contain only 8% of LLDPE.

Linear, Graft, and Beyond: Multiblock Copolymers as Next-Generation Compatibilizers.

Properly addressing the global issue of unsustainable plastic waste generation and accumulation will require a confluence of technological breakthroughs on various fronts. Mechanical recycling of plastic waste into polymer blends is one method expected to contribute to a solution. Due to phase separation of individual components, mechanical recycling of mixed polymer waste streams generally results in an unsuitable material with substantially reduced performance. However, when an appropriately designed compatibilizer is used, the recycled blend can have competitive properties to virgin materials. In its current state, polymer blend compatibilization is usually not cost-effective compared to traditional waste management, but further technical development and optimization will be essential for driving future cost competitiveness. Historically, effective compatibilizers have been diblock copolymers or in situ generated graft copolymers, but recent progress shows there is great potential for multiblock copolymer compatibilizers. In this perspective, we lay out recent advances in synthesis and understanding for two types of multiblock copolymers currently being developed as blend compatibilizers: linear and graft. Importantly, studies of appropriately designed copolymers have shown them to efficiently compatibilize model binary blends at concentrations as low as ∼0.2 wt %. These investigations pave the way for studies on more complex (ternary or higher) mixed waste streams that will require novel compatibilizer architectures. Given the progress outlined here, we believe that multiblock copolymers offer a practical and promising solution to help close the loop on plastic waste. While a complete discussion of the implementation of this technology would entail infrastructural, policy, and social developments, they are outside the scope of this perspective which instead focuses on material design considerations and the technical advancements of block copolymer compatibilizers.

Measurement of geometrical parameters in cocontinuous polymer blends: 3D versus 2D image analysis.

Formulae of stereology are used to estimate 3D geometrical parameters of cocontinuous structures measured from 2D micrographs of polymer blends. 3D images of symmetric and nonsymmetric polymer blends made of fluorescently labelled polystyrene and styrene-ran-acrylonitrile copolymer were obtained with laser scanning confocal microscopy. Geometrical parameters of the blend interface, specifically volume fraction, surface area per unit volume (S (V) ) and average of local mean curvature were measured directly from the 3D images and compared to the values estimated from analysis of a number of 2D slices combined with stereological relations. When the total length of phase boundary considered in the analysis of the 2D slices (L(Tot) ) was at least 6000 times bigger than the characteristic length of the microstructure (S(-1) (V) ), the standard deviation for all the parameters measured became negligible. However, considerable discrepancies between the average values computed from 3D and 2D images were observed for any value of L(Tot) . The mean curvature distribution was also measured from both the 3D images and the 2D slices. The distribution was estimated from the 2D slices but with a width about 2.4 times that of the true value obtained from the 3D images.

Direct measurement of interface anisotropy of bicontinuous structures via 3D image analysis.

A very important morphological parameter in two-phase fluids is the interface anisotropy, which can be quantified using the interface tensor, q(ij). However, the computation of this tensor for complex interfaces is not straightforward. A novel method (the local cross product method, LCPM) to compute the interface tensor of two-phase fluids using 3D imaging coupled with differential geometry is presented here. The method was used to evaluate the degree of anisotropy of phase separated systems with bicontinuous morphologies subjected to uniaxial and shear deformation fields. A model bicontinuous structure (i.e., the gyroid surface) was used to assess the accuracy and precision of the method. The method was then used to track the anisotropy changes of an immiscible polymer blend with cocontinuous morphology, during uniaxial deformation and subsequent retraction. It was found that the dependence of the anisotropy on the Hencky strain of both the gyroid surface and the cocontinuous blend follow the same trend. The retraction of the blend after uniaxial extension is accompanied by an exponential decay of the second invariant of q(ij), which obeys the relation: |II(q)|/Q(2) approximately e(-0.129t).

PET/Graphene Compatibilization for Different Aspect Ratio Graphenes via Trimellitic Anhydride Functionalization.

Two trimellitic anhydride-functionalized, thermally reduced graphenes with different aspect ratios, A f, and the same C/O ratio (8:1) were prepared and melt-mixed into poly(ethylene terephthalate) (PET), and the mechanical properties of the resulting nanocomposites were studied with a focus on plastic deformation behavior. A slight increase in the G' of the melt was observed for the surface-modified low-A f graphene composites (A f = 20) below the percolation threshold, whereas a significant enhancement in G' was observed for higher-A f graphene composites (A f = 80) at all graphene loadings, both below and above the percolation concentration. Furthermore, the use of modified low-A f graphene caused an improvement both in Young's modulus and elongation at break of the resulting PET nanocomposites because of enhancement of interfacial adhesion between filler and matrix which resulted in the formation of a coupled network via covalent bonding and the suppression both of strain-induced orientation and strain-induced crystallization. By contrast, the use of modified higher-A f surface graphene in nanocomposites caused a drastic improvement in Young's modulus but lower elongation-at-break than with the unmodified counterpart; the former effect is due to the formation of denser coupled networks and stronger interfacial adhesion as a result of graphene surface modification and the latter is due to the added geometrical restriction in unentangling chains from the PET matrix in the presence of higher-A f graphene. The preceding observations demonstrate the potential impacts of tuning both surface chemistry and aspect ratio of graphene in the fabrication of PET/graphene composites.

Higher-Order Structure in Amorphous Poly(ethylene terephthalate)/Graphene Nanocomposites and Its Correlation with Bulk Mechanical Properties.

Graphene of two different aspect ratios, A f, was melt mixed with poly(ethylene terephthalate) (PET) to form amorphous PET/graphene composites with less than 5% crystallinity. The higher-order structure and mechanical properties of poly(ethylene terephthalate) (PET) in these composites were investigated using techniques such as differential scanning calorimetry and dynamic mechanical analysis, whereas transmission electron microscopy, melt rheology, and electrical conductivity were used to study the graphene dispersion. A decrease in heat capacity changes, ΔC p, of PET in nanocomposites at the glass transition temperature, T g, without T g change suggests that a rigid amorphous fraction (RAF) of PET was formed at the PET/graphene interface. The stiffening effect of graphene below 1 wt % loading is quite small in the glassy state region and independent of the A f of graphene. Above 2 wt %, graphene forms a mechanical percolation network with the RAF of PET and the PET chains are geometrically restricted by the incorporation of graphene with a high A f, resulting in an unexpectedly higher modulus of nanocomposites both below and above T g.

Diamino Telechelic Polybutadienes for Solventless Styrene-butadiene-styrene (SBS) Triblock Copolymer Formation.

High molecular weight, high functionality diamino telechelic polybutadienes (TPBs) were synthesized by ring-opening metathesis polymerization (ROMP) of 1,5-cyclooctadiene (COD) in the presence of a chain transfer agent, 1,8-dicyano-4-octene, followed by lithium aluminum hydride reduction. Melt coupling of diamino TPB with anhydride-terminated polystyrene (PS-anh) resulted in the formation of styrene-butadiene-styrene (SBS) triblock copolymers; ca. 80% maximum conversion of PS-anh was achieved within 30 seconds. The results from SAXS, TEM, and rheological measurements of the coupling products confirmed the formation of SBS triblock copolymers having lamellar morphology. A fluororesent-labeled PS-anh was used to study the coupling kinetics by diluting the reactants by the addition of non-functional PS.

Combining polyethylene and polypropylene: Enhanced performance with PE/iPP multiblock polymers.

Polyethylene (PE) and isotactic polypropylene (iPP) constitute nearly two-thirds of the world's plastic. Despite their similar hydrocarbon makeup, the polymers are immiscible with one another. Thus, common grades of PE and iPP do not adhere or blend, creating challenges for recycling these materials. We synthesized PE/iPP multiblock copolymers using an isoselective alkene polymerization initiator. These polymers can weld common grades of commercial PE and iPP together, depending on the molecular weights and architecture of the block copolymers. Interfacial compatibilization of phase-separated PE and iPP with tetrablock copolymers enables morphological control, transforming brittle materials into mechanically tough blends.

Fluorine-Enriched Melt-Blown Fibers from Polymer Blends of Poly(butylene terephthalate) and a Fluorinated Multiblock Copolyester.

Melt-blown fibers (dav ∼1 µm) were produced from blends of poly(butylene terephthalate) (PBT) and a partially fluorinated random multiblock copolyester (PFCE) leading to enhanced hydrophobicity and even superhydrophobicity (static water contact angle = 157 ± 3°) of the associated fiber mats. XPS measurements demonstrated quantitatively that the surface fluorine content increased systematically with the bulk loading of PFCE, rising to nearly 20 atom %, which corresponds to 41 wt % PFCE at a bulk loading of 10 wt %. The PBT/PFCE fibers exhibit greater fluorine surface segregation than either melt-blown PBT/poly(ethylene-co-chlorotrifluoroethylene) (PBT/PECTFE) fibers or electrospun fibers obtained from blends of poly(styrene) and fluoroalkyl end-capped polystyrene (PS/PSCF). Dynamic contact angle measurements further demonstrated decreased surface adhesion energy of the melt-blown PBT/PFCE fiber mats due to the blooming of PFCE to the surface.