Building Semipermeable Films One Monomer at a Time: Structural Advantages via Molecular Layer Deposition vs Interfacial Polymerization.

Molecular layer deposition (MLD) provides the opportunity to perform condensation polymerization one vaporized monomer at a time for the creation of precise, selective nanofilms for desalination membranes. Here, we compare the structure, chemistry, and morphology of two types of commercial interfacial polymerzation (IP) membranes with lab-made MLD films. M-phenylenediamine (MPD) and trimesoyl chloride (TMC) produced a cross-linked, aromatic polyamide often used in reverse osmosis membranes at MLD growth rates of 2.9 Å/cycle at 115 °C. Likewise, piperazine (PIP) and TMC formed polypiperazine amide, a common selective layer in nanofiltration membranes, with MLD growth rates of 1.5 Å/cycle at 115 °C. Ellipsometry and X-ray reflectivity results suggest that the surface of the MLD films is comprised of polymer segments roughly two monomers in length, which are connected at one end to the cross-linked bulk layer. As a result of this structure as well as the triple-functionality of TMC, MPD-TMC had a temperature window of stable growth rate from 115 to 150 °C, which is unlike any non-cross-linked MLD chemistries reported in the literature. Compared to IP films, corresponding MLD films were denser and morphologically conformal, which suggests a reduction in void volumes; this explains the high degree of salt rejection and reduced flux previously observed for exceptionally thin MPD-TMC MLD membranes. Using X-ray photoelectron spectroscopy and infrared spectroscopy, MLD PIP-TMC films evidenced a completely cross-linked internal structure, which lacked amine and carboxyl groups, pointing to a hydrophobic bulk structure, ideal for optimized water flux. Grazing-incidence wide-angle X-ray scattering showed broad features in each polyamide with d-spacings of 5.0 Å in PIP-TMC compared to that of 3.8 Å in MPD-TMC. While MLD and IP films were structurally identical to PIP-TMC, MPD-TMC IP films had a structure that may have been altered by post-treatment compared to MLD films. These results provide foundational insights into the MLD process, structure-performance relationships, and membrane fabrication.

Influence of support-layer deformation on the intrinsic resistance of thin film composite membranes.

It is commonly believed that the overall permeation resistance of thin film composite (TFC) membranes is dictated by the crosslinked, ultrathin polyamide barrier layer, while the porous support merely serves as the mechanical support. Although this assumption might be the case under low transmembrane pressure, it becomes questionable under high transmembrane pressure. A highly porous support normally yields under a pressure of a few MPa, which can result in a significant level of compressive strain that may significantly increase the resistance to permeation. However, quantifying the influence of porous support deformation on the overall resistance of the TFC membrane is challenging. In particular, it is difficult to determine the deformation/strain of the membrane during active separation. In this study, we use nanoimprint lithography (NIL) to achieve precise compressive deformation in commercial TFC membranes. By adjusting the NIL conditions, membranes were compressed to strain levels up to 60%. SEM and AFM measurements showed that the compression had minimal impact on the barrier-layer surface morphology and total surface area with most of the deformation occurring in the support layer. DI water permeation measurements revealed that the water flux reduction decreases with an increase of strain level. Most significantly, the intrinsic membrane resistance showed negligible changes at strain levels lower than 30%-40%, but increased exponentially at higher strain levels, reaching 250%-500% of pristine (unstrained) membrane values. Using a resistance-in-series model, the strain dependency of the TFC membrane resistance can be described.

Monitoring protein fouling on polymeric membranes using ultrasonic frequency-domain reflectometry.

Novel signal-processing protocols were used to extend the in situ sensitivity of ultrasonic frequency-domain reflectometry (UFDR) for real-time monitoring of microfiltration (MF) membrane fouling during protein purification. Different commercial membrane materials, with a nominal pore size of 0.2 µm, were challenged using bovine serum albumin (BSA) and amylase as model proteins. Fouling induced by these proteins was observed in flat-sheet membrane filtration cells operating in a laminar cross-flow regime. The detection of membrane-associated proteins using UFDR was determined by applying rigorous statistical methodology to reflection spectra of ultrasonic signals obtained during membrane fouling. Data suggest that the total power reflected from membrane surfaces changes in response to protein fouling at concentrations as low as 14 µg/cm2, and results indicate that ultrasonic spectra can be leveraged to detect and monitor protein fouling on commercial MF membranes.

In situ measurement of permeability.

Permeability of a porous material with a fluid interface is shown to be related to the propagation of the slow longitudinal wave. The propagation threshold of the slow longitudinal wave occurs when the wave number is higher than the critical wave number, k(cr). Measuring k(cr) can provide the intrinsic permeability of a porous interface. The ability to detect a change in k(cr) due to differences in pore size and fluid viscosity is demonstrated. This measurement is demonstrated in a model material with two pore sizes and two fluid viscosities. The results suggest opportunities to extend the method to a range of materials of scientific and technical importance.

The thermal properties of beeswaxes: unexpected findings.

Standard melting point analyses only partially describe the thermal properties of eusocial beeswaxes. Differential scanning calorimetry (DSC) revealed that thermal phase changes in wax are initiated at substantially lower temperatures than visually observed melting points. Instead of a sharp, single endothermic peak at the published melting point of 64 degrees C, DSC analysis of Apis mellifera Linnaeus wax yielded a broad melting curve that showed the initiation of melting at approximately 40 degrees C. Although Apis beeswax retained a solid appearance at these temperatures, heat absorption and initiation of melting could affect the structural characteristics of the wax. Additionally, a more complete characterization of the thermal properties indicated that the onset of melting, melting range and heat of fusion of beeswaxes varied significantly among tribes of social bees (Bombini, Meliponini, Apini). Compared with other waxes examined, the relatively malleable wax of bumblebees (Bombini) had the lowest onset of melting and lowest heat of fusion but an intermediate melting temperature range. Stingless bee (Meliponini) wax was intermediate between bumblebee and honeybee wax (Apini) in heat of fusion, but had the highest onset of melting and the narrowest melting temperature range. The broad melting temperature range and high heat of fusion in the Apini may be associated with the use of wax comb as a free-hanging structural material, while the Bombini and Meliponini support their wax structures with exogenous materials.

Extra-cellular polysaccharides, soluble microbial products, and natural organic matter impact on nanofiltration membranes flux decline.

Extra-cellular polysaccharides (EPS), soluble microbiological products (SMP), dispersed bacterial cells, and a well-characterized natural organic matter (NOM) isolate were observed to determine their influence on the flux decline of model nanofiltration membrane systems. Biofouling tests were conducted using bench-scale, flat-sheet membrane modules, fed with particle-free (laboratory) waters and natural waters, some of which were augmented with readily biodegradable organic carbon. The modules were operated 6.7 x 10(5) Pa, and 21+/- 2 degrees C. Membrane flux-decline was associated with increases in surface EPS mass: between 30 and 80% of normalized flux decline occurred when membrane-associated EPS content increased from 5to 50 microg/ cm2. As judged by standard culturing, heterotrophic cell densities recovered from membrane biofilm samples showed no significant correlations with the different carbon sources present in the feedwaters, or flux decline rates. Results suggested that, in the absence of microbiological activity, SMP and NOM have intrinsic membrane fouling properties at levels that are operationally significant to commercial-scale membrane treatment practices. Results also suggested that SMP may have a biofouling potential significantly greater than some types of NOM. Trends obtained relating these compounds with flux decline were successfully described by expanding existing resistance-in-series models.

Ultrasonic monitoring of early-stage biofilm growth on polymeric surfaces.

Biofilm growth on polymeric surfaces was monitored using ultrasonic frequency-domain reflectometry (UFDR). The materials utilized for this study included nonporous polycarbonate (PC) sheets, polyamide (PA) nanofiltration composite membranes and porous polyvinylidene fluoride (PVDF) microfiltration membranes (nominal pore size: 0.65 microm). Coupons of each material were placed in a biologically active annular reactor for up to 300 days, and subjected to a constant shear field (0.12 N m(-2)), which induced sessile microbial growth from acetate amended municipal tap water. Acoustic monitoring was non-destructively executed by traversing coupons in a constant temperature water bath using a spherically focused 20-MHz immersion transducer. This semi-automated system was configured to obtain reflections from 50 regions (c.a. 120x10(3) microm2) distributed evenly near the centerline of each coupon. The resulting reflected power distributions were compared with standard biochemical and microscopic assays that described surface associated biofilms. When compared to clean (virgin) conditions, biofilms growing on coupons induced consistent attenuations in reflection amplitude, which caused statistically significant shifts in reflected power (p<0.01). Using exocellular polysaccharides as a surrogate measure of total biofilm mass, UFDR was able to detect biofilms developing on any of the materials tested at surface-averaged masses < or = 150 microg cm(-2). Above these threshold levels, increasing amounts of exocellular polysaccharides correlated with significant decreases in total reflected power (TRP). The distribution of biomass on the coupon surfaces determined by acoustic spectra was consistent with that observed using environmental scanning electron microscopy (ESEM). These results suggest that UFDR may be used as a non-destructive tool to monitor biofouling in a wide variety of applications.

Interspecific variation in beeswax as a biological construction material.

Beeswax is a multicomponent material used by bees in the genus Apis to house larvae and store honey and pollen. We characterized the mechanical properties of waxes from four honeybee species: Apis mellifera L., Apis andreniformis L., Apis dorsata L. and two subspecies of Apis cerana L. In order to isolate the material effects from the architectural properties of nest comb, we formed raw wax in to right, circular cylindrical samples, and compressed them in an electromechanical tensometer. From the resulting stress-strain curves, values for yield stress, yield strain, stress and strain at the proportional limit, stiffness, and resilience were obtained. Apis dorsata wax was stiffer and had a higher yield stress and stress at the proportional limit than all of the other waxes. The waxes of A. cerana and A. mellifera had intermediate strength and stiffness, and A. andreniformis wax was the least strong, stiff and resilient. All of the waxes had similar strain values at the proportional limit and yield point. The observed differences in wax mechanical properties correlate with the nesting ecology of these species. A. mellifera and A. cerana nest in cavities that protect the nest from environmental stresses, whereas the species with the strongest and stiffest wax, A. dorsata, constructs relatively heavy nests attached to branches of tall trees, exposing them to substantially greater mechanical forces. The wax of A. andreniformis was the least strong, stiff and resilient, and their nests have low masses relative to other species in the genus and, although not built in cavities, are constructed on lower, often shielded branches that can absorb the forces of wind and rain.

Sliding-cavity fluid contactors in low-gravity fluids, materials, and biotechnology research.

The well-known method of sliding-cavity fluid contactors used by Gosting for diffusion measurements and by Tiselius in electrophoresis has found considerable use in low-gravity research. To date, sliding-cavity contactors have been used in liquid diffusion experiments, interfacial transport experiments, biomolecular crystal growth, biphasic extraction, multistage extraction, microencapsulation, seed germination, invertebrate development, and thin-film casting. Sliding-cavity technology has several advantages for spaceflight: it is simple, it accommodates small samples, samples can be fully enclosed, phases can be combined, multiple samples can be processed at high sample density, real-time observations can be made, and mixed and diffused samples can be compared. An analysis of the transport phenomena that govern the sliding-cavity method is offered. During sliding of one liquid over another flow rates between 0.001 and 0.1m/sec are developed, giving Reynolds numbers in the range 0.1-100. Assuming no slip at liquid-solid boundaries shear rates are of the order 1sec(-1). The measured consequence is the transfer of 2-5% of the content of a cavity to the opposite cavity. In the absence of gravity, buoyancy-driven transport is assumed absent. Transport processes are limited to (1) molecular diffusion, in which reactants diffuse toward one another at rates that depend on their diffusion coefficient and concentration gradient (Fick's second law), (2) solutocapillary (Marangoni) flow driven by surface-tension gradients, (3) capillary flow (drop spreading) at liquid-solid three-phase lines leading to immiscible phase demixing, and (4) vapor-phase diffusive mass transfer in evaporative processes. Quantitative treatment of these phenomena has been accomplished over the past few years in low-gravity research in space and on aircraft.