Ultrathin Polydopamine-Graphene Oxide Hybrid Coatings on Polymer Filters with Improved Filtration Performance and Functionalities.

Thin polymer fiber mats, in particular those made of nonwoven polypropylene (PP) fibers, are extensively used for medical and industrial filtration. The recent pandemic has increased the demand for the fabrication of protective masks. The nonwoven PP filter has limitations in filtration efficiency and lacks advanced functionalities. Here, we propose a simple, effective, and low-cost method to functionalize PP filters and endow antimicrobial and photothermal properties. Our approach is based on the deposition of an ultrathin hybrid coating composed of graphene oxide (GO) and polydopamine on the surface of PP filters by spray-coating. The complementary properties and synergic effects of GO and polydopamine in the ultrathin coating improved the filtration efficiency of the PP filter by 20% with little change in pressure drop. Single component coatings did not result in similar improvements in performance. The ultrathin coating also makes the surface of the filter more hydrophilic with negative charges. The photothermal property of GO enables a rapid temperature increase of the surface-coated filter upon light irradiation for easy sterilization. Furthermore, cationic polymer brushes can be grafted to the ultrathin hybrid coating, which adds the highly desired antimicrobial property to the PP filters for their more effective protection against microorganisms.

Charge measurement of electrospun polyvinylidene fluoride fibers using a custom-made Faraday bucket.

Electrical charges on fabrics, films, and membrane materials are of scientific interest for material development and performance. In many applications, available instruments do not have sufficient sensitivity to detect variations in charge needed for scientific investigations. This paper discusses the design and construction of a custom-made Faraday bucket for measuring the charge of electrospun polyvinylidene fluoride fiber mats of sizes 3 × 3 cm2 and 4 × 4 cm2. An electrometer directly measured the change in the voltage potentials of the inner conductor of the Faraday bucket due to the insertion of fiber mat samples. The measured potentials were converted to electrical charge by modeling the Faraday bucket as a source-free resistance-capacitance circuit. The results show that the Faraday bucket was sufficiently sensitive and measured differences in the potential and charge of the fiber mats due to variations in sample size (or mass), and it detected differences in charge depending on whether the sample was taken from the center or the edges of the electrospun fiber mats.

Substantial Improvement of Oil Aerosol Filtration Performance Using In-Plane Asymmetric Wettability.

Oil aerosol usually causes air pollution, health issues, and corrosion to equipment. The removal of aerosol oil particles from the air is a crucial process in industrial production and daily life. Although fibrous filters have been a widely used material for the separation of oil aerosol from the air, it is still a challenge to separate submicrometer aerosol oil particles with both high filtration efficiency and low resistance. Herein, we report a novel approach to markedly reduce the pressure drop of a fibrous filter and simultaneously increase its aerosol filtration efficiency, only by surface treatment to make the filter have in-plane alternating superoleophilic and superoleophobic patterns. We used a spraying method to prepare superoleophobic and superoleophilic patterns on the filter. The best filtration results were achieved when two layers of the patterned filters that have superoleophobic and superoleophilic strips (both width, 5 mm) were stacked in a way that the opposite wetting surfaces contacted each other between the layers. The filter showed a much-reduced filtration resistance and the pressure drop (4.16 kPa) at the pseudo-steady state being at least 45% lower when compared to the two-layer controls with a homogeneous surface wettability (i.e., untreated surface, superoleophobicity, and superoleophilicity). It also showed higher filtration efficiency (98.37% for small oil mists and 99.99% for large oil mists) and over two times higher quality factor (0.99 kPa-1 for small oil mists and 2.27 kPa-1 for large oil mists). The asymmetric wettability leads to the formation of unobstructed channels for the air stream to penetrate through the filter matrix, leading to a low resistance with improved oil capture efficiency. The pattern strip width showed an effect on filtration performance. This unexpected finding may provide a novel approach to designing high-performance, low energy consumption, and long-life coalescence filters.

Polarized Catalytic Polymer Nanofibers.

Molecular scale modifications were achieved by spontaneous polarization which is favored in enhancements of ß-crystallization phase inside polyvinylidene fluoride (PVDF) nanofibers (NFs). These improvements were much more effective in nano and submicron fibers compared to fibers with relatively larger diameters. Metallic nanoparticles (NPs) supported by nanofibrous membranes opened new vistas in filtration, catalysis, and serving as most reliable resources in numerous other industrial applications. In this research, hydrogenation of phenol was studied as a model to test the effectiveness of polarized PVDF nanofiber support embedded with agglomerated palladium (Pd) metallic nanoparticle diameters ranging from 5-50 nm supported on polymeric PVDF NFs with ~200 nm in cross-sectional diameters. Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Atomic Force Microscopy (AFM), Energy Dispersive X-Ray Spectroscopy (EDX), Fourier Transform Infrared Spectroscopy (FTIR) and other analytical analysis revealed both molecular and surface morphological changes associated with polarization treatment. The results showed that the fibers mats heated to their curie temperature (150 °C) increased the catalytic activity and decreased the selectivity by yielding substantial amounts of undesired product (cyclohexanol) alongside with the desired product (cyclohexanone). Over 95% phenol conversion with excellent cyclohexanone selectivity was obtained less than nine hours of reaction using the polarized PVDF nanofibers as catalytic support structures.

A customized instrument with laser interferometry for measuring electrospun mat thickness.

Thickness is an important characteristic parameter of electrospun submicron of fiber mats and membranes. The thickness of the mats directly influences performance properties such as permeability and is necessary when determining volumetric parameters such as porosity. Typical electrospun mats are very thin (less than 1 mm) and highly compressive due to the small diameter fibers, both of which make accurate measurements difficult when using conventional methods. An accurate measure of the thickness is desired for characterizing and comparing membrane performances. In this work, a thickness measurement instrument using laser interferometry has been designed to measure electrospun fiber mat thickness. A small disk is used to apply a small (reproducible) force applied across a reasonably small area of the fiber mat. A traversing pin moves to contact the disk and completes an electrical circuit to stop movement and determine the location of the disk relative to a reference plane. The fiber mat thickness is determined by measuring the difference in locations of the disk with and without the fiber mat between the disk and the reference plane. The prototype is simple to operate and user-friendly. Precision and accuracy of the prototype are discussed.

Enhanced oxidation resistance of SiC/SiC minicomposites via slurry infiltration of oxide layers.

SiC based composite materials commonly have protective silica surface in air. Under humid environments at high temperatures, like occur in jet engines, the silica surface layer reacts with water molecules to form volatile silicon hydroxide (Si(OH)4) and the protection is reduced which cause jet engine degradation. An alternative approach to protect SiC based composites would be to infiltrate the SiC matrix via slurry with an oxide material that is resistant to the high-temperature and humid environment. As proof of concept, aqueous based mullite particle slurries were infiltrated by pressurized flow and by capillarity of the wetting slurry on the external surface of the porous SiC matrix of single-fiber-tow SiC/SiC minicomposites. Minicomposites were precracked at room temperature during tensile tests then tested in tensile creep in air at 1200 °C to study the degree of protection that the infiltrated mullite provided at high temperatures. Next, fracture surfaces were examined using SEM.

Separation of Water from Ultralow Sulfur Diesel Using Novel Polymer Nanofiber-Coated Glass Fiber Media.

Polymer nanofibers with interpenetrating network (IPN) morphology are used in this work for the development of composite, hydrophobic filter media in conjunction with glass fibers for removal of water droplets from ultralow sulfur diesel (ULSD). The nanofibers are produced from hydrophobic polyvinyl acetate (PVAc) and hydrophilic polyvinylpyrrolidone (PVP) by spinning the polymer solutions using gas jet fiber (GJF) method. The nanofibers coat the individual glass fibers due to polar-polar interactions during the spinning process and render the filter media highly hydrophobic with a water contact angle approaching 150°. The efficiency of the resultant filter media is evaluated in terms of separation of water droplets of average size 20 µm from the suspensions in ULSD.

Fabrication, Polarization of Electrospun Polyvinylidene Fluoride Electret Fibers and Effect on Capturing Nanoscale Solid Aerosols.

Electrospun polyvinylidene fluoride (PVDF) fiber mats with average fiber diameters (≈200 nm, ≈2000 nm) were fabricated by controlled electrospinning conditions. These fiber mats were polarized using a custom-made device to enhance the formation of the electret ß-phase ferroelectric property of the fibers by simultaneous uniaxial stretching of the fiber mat and heating the mat to the Curie temperature of the PVDF polymer in a strong electric field of 2.5 kV/cm. Scanning electron microscopy, Fourier transform infrared spectroscopy, thermal gravimetric analysis, differential scanning calorimetry and Brunauer-Emmett-Teller (BET) surface area analyses were performed to characterize both the internal and external morphologies of the fiber mat samples to study polarization-associated changes. MATLAB simulations revealed the changes in the paths of the electric fields and the magnetic flux inside the polarization field with inclusion of the ferroelectric fiber mats. Both polarized and unpolarized fiber mats were challenged as filters against NaCl particles with average particle diameters of about 150 nm using a TSI 8130 to study capture efficiencies and relative pressure drops. Twelve filter experiments were conducted on each sample at one month time intervals between experiments to evaluate the reduction of the polarization enhancement over time. The results showed negligible polarization loss for the 200-nm fiber sample. The polarized mats had the highest filter efficiencies and lowest pressure drops.

Polyvinylidene fluoride molecules in nanofibers, imaged at atomic scale by aberration corrected electron microscopy.

Atomic scale features of polyvinylidene fluoride molecules (PVDF) were observed with aberration corrected transmission electron microscopy. Thin, self-supporting PVDF nanofibers were used to create images that show conformations and relative locations of atoms in segments of polymer molecules, particularly segments near the surface of the nanofiber. Rows of CF2 atomic groups, at 0.25 nm intervals, which marked the paths of segments of the PVDF molecules, were seen. The fact that an electron microscope image of a segment of a PVDF molecule depended upon the particular azimuthal direction, along which the segment was viewed, enabled observation of twist around the molecular axis. The 0.2 nm side-by-side distance between the two fluorine atoms attached to the same carbon atom was clearly resolved. Morphological and chemical changes produced by energetic electrons, ranging from no change to fiber scission, over many orders of magnitude of electrons per unit area, promise quantitative new insights into radiation chemistry. Relative movements of segments of molecules were observed. Promising synergism between high resolution electron microscopy and molecular dynamic modeling was demonstrated. This paper is at the threshold of growing usefulness of electron microscopy to the science and engineering of polymer and other molecules.

Microscopy analysis and production rate data for needleless vertical rods electrospinning parameters.

A multiple vertical rod setup for needless electrospinning was used to fabricate submicron polymer fibers. The design with multiple vertical rods is a new concept for increased production of electrospun fibers. Different geometries and operating conditions are possible. The effects of varying the number of rods in the array have been studied and reported [1]. The goal of this work was a proof of concept of the threaded rod design by exploring the effects of variations in applied voltage and gap distance for a fixed array of rods. Effects on fiber diameter and production rate of fibers are reported. More extensive experiments are needed to quantify the interrelations between parameters and to guide the design and operation of the method. No attempt was made to optimize the operating parameters or the geometry in terms of production rates or fiber diameters.

A versatile microparticle-based immunoaggregation assay for macromolecular biomarker detection and quantification.

The rapid, sensitive and low-cost detection of macromolecular biomarkers is critical in clinical diagnostics, environmental monitoring, research, etc. Conventional assay methods usually require bulky, expensive and designated instruments and relative long assay time. For hospitals and laboratories that lack immediate access to analytical instruments, fast and low-cost assay methods for the detection of macromolecular biomarkers are urgently needed. In this work, we developed a versatile microparticle (MP)-based immunoaggregation method for the detection and quantification of macromolecular biomarkers. Antibodies (Abs) were firstly conjugated to MP through streptavidin-biotin interaction; the addition of macromolecular biomarkers caused the aggregation of Ab-MPs, which were subsequently detected by an optical microscope or optical particle sizer. The invisible nanometer-scale macromolecular biomarkers caused detectable change of micrometer-scale particle size distributions. Goat anti-rabbit immunoglobulin and human ferritin were used as model biomarkers to demonstrate MP-based immunoaggregation assay in PBS and 10% FBS to mimic real biomarker assay in the complex medium. It was found that both the number ratio and the volume ratio of Ab-MP aggregates caused by biomarker to all particles were directly correlated to the biomarker concentration. In addition, we found that the detection range could be tuned by adjusting the Ab-MP concentration. We envision that this novel MP-based immunoaggregation assay can be combined with multiple detection methods to detect and quantify macromolecular biomarkers at the nanogram per milliliter level.

Comparative dissolution of electrospun Al2O3 nanofibres in artificial human lung fluids.

Sub-micron sized alumina fibres were fabricated by electrospinning and calcination of a polymer template fibre. In the calcination step, different controlled temperature heating cycles were conducted to obtain fibres of different crystalline structures. Their biodurabilities were tested at pH 7.4 with lung airway epithelial lining fluid or serum ultrafiltrate (SUF) and at pH 4.5 with macrophage phagolysosomal simulant fluid (PSF). Potential to generate free radicals was tested in vitro. Through the variation in the soak temperature from 650 °C to 950 °C (experiments S650-S950), the heating protocol affected the morphological characteristics, crystal structure, surface area, and density of the alumina fibres while their dissolution half-times were not significantly affected in SUF or PSF. Fibre samples formed at different heating ramp rates (experiments R93-R600) showed significant variation in the dissolution rates with the highest ramp rate corresponding to the highest dissolution rate. Thus, by increasing the calcination temperature ramp rate the alumina fibres may be produced that have reduced biodurability and lower inflammogenic potential. The fibres with the highest dissolution rated had the least aluminium content. The solubility half-times of the alumina fibres were shortest for fibres calcined at the fastest temperature ramp rate (though soak temperature did not have an effect). The ramp rates also affected the aluminium content of the fibres suggesting that the content may affect the structural strength of the fibres and control the dissolution.

Contact angles of drops on curved superhydrophobic surfaces.

Superhydrophobic surfaces have contact angles that exceed 150 degrees and are known to reduce surface fouling, protect surfaces, and improve liquid-liquid separations. Electrospun sub-micron fiber mats can perform as superhydrophobic surfaces. Superhydrophobic behavior is typically measured on planar surfaces, whereas applications may require curved surfaces. This paper discuses the measurement of water contact angles of fiber mats formed on cylindrical surfaces to create superhydrophobic behavior on curved surfaces. Equations are derived that relate the radius of curvature of spherical and cylindrical surfaces and drop size to the observed contact angle on the curved surfaces. Calculations from the equations agree well with experimental observations on spherical surfaces reported in literature and on cylindrical surfaces created in our lab.