Electron tomography reveals details of the internal microstructure of desalination membranes.

As water availability becomes a growing challenge in various regions throughout the world, desalination and wastewater reclamation through technologies such as reverse osmosis (RO) are becoming more important. Nevertheless, many open questions remain regarding the internal structure of thin-film composite RO membranes. In this work, fully aromatic polyamide films that serve as the active layer of state-of-the-art water filtration membranes were investigated using high-angle annular dark-field scanning transmission electron microscopy tomography. Reconstructions of the 3D morphology reveal intricate aspects of the complex microstructure not visible from 2D projections. We find that internal voids of the active layer of compressed commercial membranes account for less than 0.2% of the total polymer volume, contrary to previously reported values that are two orders of magnitude higher. Measurements of the local variation in polyamide density from electron tomography reveal that the polymer density is highest at the permeable surface for the two membranes tested and establish the significance of surface area on RO membrane transport properties. The same type of analyses could provide explanations for different flux variations with surface area for other types of membranes where the density is distributed differently. Thus, 3D reconstructions and quantitative analyses will be crucial to characterize the complex morphology of polymeric membranes used in next-generation water-purification membranes.

High-Modulus Low-Cost Carbon Fibers from Polyethylene Enabled by Boron Catalyzed Graphitization.

Currently, carbon fibers (CFs) from the solution spinning, air oxidation, and carbonization of polyacrylonitrile impose a lower price limit of ≈$10 per lb, limiting the growth in industrial and automotive markets. Polyethylene is a promising precursor to enable a high-volume industrial grade CF as it is low cost, melt spinnable and has high carbon content. However, sulfonated polyethylene (SPE)-derived CFs have thus far fallen short of the 200 GPa tensile modulus threshold for industrial applicability. Here, a graphitization process is presented catalyzed by the addition of boron that produces carbon fiber with >400 GPa tensile modulus at 2400 °C. Wide angle X-ray diffraction collected during carbonization reveals that the presence of boron reduces the onset of graphitization by nearly 400 °C, beginning around 1200 °C. The B-doped SPE-CFs herein attain 200 GPa tensile modulus and 2.4 GPa tensile strength at the practical carbonization temperature of 1800 °C.

Carbon diffusion from methane into walls of carbon nanotube through structurally and compositionally modified iron catalyst.

To understand diffusion processes occurring inside Fe catalysts during multiwall carbon nanotube (MWCNT) growth, catalysts were studied using atomic-resolution scanning transmission electron microscopy combined with electron energy-loss spectroscopy. Nanotube walls emanate from structurally modified and chemically complex catalysts that consist of cementite and a 5 nm amorphous FeOx cap separated by a 2-3 nm thick carbon-rich region that also contains Fe and O (a-C:FexOy). Nonuniform distribution of carbon atoms throughout the catalyst base reveals that carbon molecules from the gas phase decompose near the catalyst multisection junction, where the MWCNT walls terminate. Formation of the a-C:FexOy region provides the essential carbon source for MWCNT growth. Two different carbon diffusion mechanisms are responsible for the growth of the inner and outer walls of each MWCNT.

Probing the Internal Microstructure of Polyamide Thin-Film Composite Membranes Using Resonant Soft X-ray Scattering.

Characterization of the internal morphology of thin film composite membranes used in reverse osmosis (RO) is a prerequisite for understanding the connection between microstructure and water transport properties and is necessary for the design of membranes with improved performance. Here, we examine a series of fully aromatic polyamide active layers of RO membranes that vary in crosslinking using a combination of resonant soft X-ray scattering (RSoXS), transmission electron microscopy (TEM), and atomic force microscopy (AFM). Analysis of RSoXS profiles reveals a correlation between membrane structure and crosslinking density. Through a combination of scattering contrast calculations, TEM, and AFM micrographs, we assign the dominant contribution to RSoXS data as either surface roughness or chemical heterogeneity, depending on the X-ray energy used. Altogether, our results demonstrate the utility of soft X-ray scattering to examine the microstructure of water filtration membranes.

Orientation and morphological evolution of catalyst nanoparticles during carbon nanotube growth.

We examined the structure, morphology, and orientation of catalyst nanoparticles used for seeding and growing multiwall carbon nanotubes (MWCNTs) by plasma enhanced chemical vapor deposition in CH4/H2 gas mixtures. Iron catalyst nanocrystals are converted to Fe3C in CH4/H2 plasmas and the MWCNTs grow from Fe3C nanocrystals. Initially faceted and equiaxed catalyst nanocrystals are distorted and elongated significantly once a tubular CNT structure is formed around the catalyst particles. Eventually, catalysts deform into elongated tear-drop shapes. Once this morphology forms, CNT structures produced are straight and have uniform diameters. Surprisingly, the Fe3C nanocrystals located inside the base of well-graphitized nanotubes do not exhibit a preferred orientation relative to the nanotube axis. Catalyst nanocrystals in a variety of orientations relative to the nanotube axis still produce well-graphitized nanotubes with similar diameters and structures.