Christian Burger

Nanofabrication in polymer matrices

Abstract Polymeric systems have played important roles as templates for nanofabrication since they can offer nanotemplates with different morphologies and tunable sizes, can be easily removed after reactions, and can be further modified with different functional groups to enhance the interactions. This review covers recent advances in polymer-assisted fabrication of nanomaterials with emphasis on ordered polymeric nanostructures. Examples could include self-assembled amphiphilic block co-polymers/surfactants, cross-linkable polymers, dendrimers, microemulsions, latex particles, biomacromolecules, electric- or shear-induced structures as templates to fabricate inorganic, organic/inorganic composites and polymeric materials with nanoscale modifications. The phase behavior of block co-polymers in water and the use of templates to form ordered nanostructures are reviewed in detail. Modern physical techniques for nanoscale characterization are briefly discussed.

Ultrafine polysaccharide nanofibrous membranes for water purification.

Ultrafine polysaccharide nanofibers (i.e., cellulose and chitin) with 5-10 nm diameters were employed as barrier layers in a new class of thin-film nanofibrous composite (TFNC) membranes for water purification. In addition to concentration, the viscosity of the polysaccharide nanofiber coating suspension was also found to be affected by the pH value and ionic strength. When compared with two commercial UF membranes (PAN10 and PAN400), 10-fold higher permeation flux with above 99.5% rejection ratio were achieved by using ultrafine cellulose nanofibers-based TFNC membranes for ultrafiltration of oil/water emulsions. The very high surface-to-volume ratio and negatively charged surface of cellulose nanofibers, which lead to a high virus adsorption capacity as verified by MS2 bacteriophage testing, offer further opportunities in drinking water applications. The low cost of raw cellulose/chitin materials, the environmentally friendly fabrication process, and the impressive high-flux performance indicate that such ultrafine polysaccharide nanofibers-based TFNC membranes can surpass conventional membrane systems in many different water applications.

Ultra-fine cellulose nanofibers: new nano-scale materials for water purification

The major challenges in membrane technology for water filtration are the development of new materials (e.g. high durability, low cost and low environmental concerns) and new structures (e.g. directed water channels) that can produce high permeation flux (thus low energy input) while maintaining a high selectivity or rejection rate. This highlight discusses the utilization of ultra-fine cellulose nanofibers (UCN, diameter 5–10 nm), made by TEMPO/NaBr/NaClO oxidation of natural cellulose (e.g. wood pulp), in different nanofibrous composite formats that can meet this challenge for microfiltration (MF) and ultrafiltration (UF) applications. The unique features of ultra-fine cellulose nanofibers include small diameter, high surface-to-volume ratio, easy surface functionality, good mechanical properties and good chemical resistance. The electrospun nanofibrous scaffolds with fine pore size defined by the fiber diameter could be used to remove waterborne bacteria at two to three times higher flux when compared to that of commercial MF membranes (e.g., Millipore GS9035). When UCN were used as a functionalized adsorbent infused in the asymmetric two-layered non-woven fibrous format, the membranes exhibited a high ability to remove bacteria (by size exclusion) and viruses (by adsorption) simultaneously. When UCN were used as the barrier layer in an asymmetric three-layered non-woven fibrous format containing fibers of different diameters (from 5 nm to 20 µm), the membranes exhibited a two- to ten-fold increase in permeation flux over commercial membranes for ultrafiltration of oil and water emulsions (e.g., for purification of bilge water in ships or industrially produced water).

Time-resolved shear behavior of end-tethered Nylon 6–clay nanocomposites followed by non-isothermal crystallization

Abstract Simple shear of end-tethered Nylon 6–clay nanocomposites and the preservation of these effects into the crystalline state is reported. Typical conditions leading to mesoscopic (clays) and molecular (polymer chains) orientation of these systems at relatively low shear rates and at temperatures immediately above the nominal melting point showed a morphological change proportional to the shear time in the molten state. Gradual alignment of the through-view SAXS patterns indicated the rotation of the end-tethered clay along the shear direction. High temperature relaxation of clay after shear was substantially longer than the polymer. Thus, non-isothermal crystallization into the crystalline state could be used to preserve the orientation of the clay induced by shear. It was found that most of the clay planar alignment in Nylon 6–clay nanocomposites rendered the γ crystal habit, which is typically associated with the extended chain crystallization. Nylon 6, on the other hand, crystallized into the α habit commonly associated with quiescent crystals involving folded chains. The shear results were compared with quiescent crystallization, where the Nylon 6 nanocomposites exhibited the preferential γ habit and the Nylon 6 homopolymer exhibited mixed α/γ habits.

Nanofibrous Microfiltration Membrane Based on Cellulose Nanowhiskers

A multilayered nanofibrous microfiltration (MF) membrane system with high flux, low pressure drop, and high retention capability against both bacteria and bacteriophages (a virus model) was developed by impregnating ultrafine cellulose nanowhiskers (diameter about 5 nm) into an electrospun polyacrylonitrile (PAN) nanofibrous scaffold (fiber diameter about 150 nm) supported by a poly(ethylene terephthalate) (PET) nonwoven substrate (fiber diameter about 20 μm). The cellulose nanowhiskers were anchored on the PAN nanofiber surface, forming a cross-linked nanostructured mesh with very high surface-to-volume ratio and a negatively charged surface. The mean pore size and pore size distribution of this MF system could be adjusted by the loading of cellulose nanowhiskers, where the resulting membrane not only possessed good mechanical properties but also high surface charge density confirmed by the conductivity titration and zeta potential measurements. The results indicated that a test cellulose nanowhisker-based MF membrane exhibited 16 times higher adsorption capacity against a positively charged dye over a commercial nitrocellulose-based MF membrane. This experimental membrane also showed full retention capability against bacteria, for example, E. coli and B. diminuta (log reduction value (LRV) larger than 6) and decent retention against bacteriophage MS2 (LRV larger than 2).

Block Copolymers with a Twist

Chiral block copolymers (BCPs*) comprising chiral entities were designed to fabricate helical architectures (i.e., twisted morphologies) from self-assembly. A new helical phase (H*) with P622 symmetry was discovered in the self-assembly of poly(styrene)-b-poly(l-lactide) (PS-PLLA) BCPs*. Hexagonally packed, interdigitated PLLA helical microdomains in a PS matrix were directly visualized by electron tomography. The phase diagram of the PS-PLLA BCPs* was also established. Phase transitions from the H* phase to the stable cylinder and gyroid phases were found after long-time annealing, suggesting that the H* is a long-lived metastable phase. In contrast to racemic poly(styrene)-b-poly(d,l-lactide) BCPs, chiral interaction significantly enhances the incompatibility between achiral PS and chiral PLLA blocks in the PS-PLLA BCPs* and can be estimated through the determination of the interaction parameter.

Lateral Packing of Mineral Crystals in Bone Collagen Fibrils

Combined small-angle x-ray scattering and transmission electron microscopy studies of intramuscular fish bone (shad and herring) indicate that the lateral packing of nanoscale calcium-phosphate crystals in collagen fibrils can be represented by irregular stacks of platelet-shaped crystals, intercalated with organic layers of collagen molecules. The scattering intensity distribution in this system can be described by a modified Zernike-Prins model, taking preferred orientation effects into account. Using the model, the diffuse fan-shaped small-angle x-ray scattering intensity profile, dominating the equatorial region of the scattering pattern, could be quantitatively analyzed as a function of the degree of mineralization. The mineral platelets were found to be very thin (1.5 nm approximately 2.0 nm), having a narrow thickness distribution. The thickness of the organic layers between adjacent mineral platelets within a stack is more broadly distributed with the average value varying from 6 nm to 10 nm, depending on the extent of mineralization. The two-dimensional analytical scheme also leads to quantitative information about the preferred orientation of mineral stacks and the average height of crystals along the crystallographic c axis.

Chiral J‐Aggregates Formed by Achiral Cyanine Dyes

The self-assembly of helical supramolecular structures from chiral building units is a basic principle of biological materials. The mesoscopic structure of a chiral molecular aggregate, which formed spontaneously from a nonchiral J-aggregating cyanine dye in aqueous solution, is presented. In single crystals (as shown in the picture) a coexistance of planar molecules with left- and right-handed twisted conformers of the same dye are found; the latter may act as templates to build up the helical superstructures.

Preferred Orientation in Polymer Fiber Scattering

Fiber symmetry is one of the most important sample geometries encountered in both wide-angle x-ray scattering (WAXS) and small-angle x-ray scattering (SAXS) of polymers, applicable both to natural polymers like collagen or cellulose and to many synthetic polymers that come in fiber form or otherwise exhibit cylindrical rotational symmetry. The structural information to be determined in scattering experiments from such fiber systems includes both the structure of the individual structural unit and qualitative and quantitative information about the preferred orientation state of the ensemble. Existing approaches and new developments to analyze fiber scattering patterns are rigorously reviewed. Special emphasis is placed on the calculation of complete SAXS and WAXS fiber scattering patterns, and various practical examples including collagen and cellulose fibers as well as fibers based on copolymers of polyethylene and polypropylene are discussed.

Analysis of chord-length distributions

A closed-form analytical solution for the inversion of the integral equation relating small-angle scattering intensity distributions of two-phase systems to chord-length distributions is presented. The result is generalized to arbitrary derivatives of higher order of the autocorrelation function and to arbitrary projections of the scattering intensity (including slit collimation). This inverse transformation offers an elegant way to investigate the impact of certain features, e.g. singularities, in the chord-length distribution or its higher-order derivatives on the scattering curve, e.g. oscillatory components in the asymptotic behavior at a large scattering vector. Several examples are discussed.