Impact of the Processing-Induced Orientation of Hexagonal Boron Nitride and Graphite on the Thermal Conductivity of Polyethylene Composites.

Emergent heat transfer and thermal management applications require polymer composites with enhanced thermal conductivity (κ). Composites filled with non-spherical fillers, such as hexagonal boron nitride (hBN) and Graphite (Gr), suffer from processing-induced filler orientations, resulting in anisotropic κ, commonly low in the through-plane direction. Here, the effects of extrusion and compression molding-induced orientations on κ of hBN- and Gr-filled polyethylene composites were investigated. The effect of extrusion on the hBN orientation was studied using dies of various shapes. The shaped extrudates exhibited hBN orientations parallel to the extrusion flow direction, which prompted additional hBN orientation during compression molding. κ of the composites produced with shaped extrudates varied from 0.95 to 1.67 W m-1 K-1. Pelletizing and crushing the extrudates improved κ, by exploiting and eliminating the effect of extrusion-induced hBN orientations. Gr-filled composites showed better κ than hBN composites due to the higher intrinsic conductivity and bigger particle sizes. A maximum κ of 5.1 and 11.8 W m-1 K-1 was achieved in composites with oriented hBN and Gr through a thin rectangular die and stacking the sheets to fabricate composites with highly oriented fillers.

Complex treatment of oily polluted waters by modified melamine foams: from colloidal emulsions to a free oil removal.

This study deals with the efficient, low-cost, and scalable treatment of oily polluted waters including colloidal emulsions, oil-in-water mixtures, and free oil removal using melamine foams (MFs) modified by ferric chloride (FeCl3). Modified foams have superhydrophobic character due to the coordination of Fe3+ with free electron pairs on nitrogen and oxygen atoms within the melamine structure. The water contact angles (WCA) were 146° ± 2°, 148° ± 4°, 153° ± 2°, and 150° ± 4° for foams modified by the solutions with concentrations of 0.001 M, 0.005 M, 0.01 M, and 0.02 M, respectively. This modification enables the efficient treatment of various oil/water systems, including oil/water colloidal emulsions (99 vol% of the droplets have dimensions below 500 nm), oil-in-water mixtures up to 40 weight % of the oil component, and "free" oil removal as it was demonstrated in this study for the first time. The emulsions containing 100 ppm diesel oil (DO) were separated with 91.4% efficiency, and the mixtures containing 20 and 40 weight % DO were separated with 99.9% efficiency. Modified foams also quickly remove free DO from the water surface, absorbing 95 g/g DO, whereas water sorption was negligible. The separation of colloidal oil in water emulsions represents the key finding of this study as it indicates the applicability of the treated MFs for the treatment of emulsified industrial wastewater. The demulsification mechanism is based on multiple diffusion processes running at different time scales, including diffusion of the emulsion into the foam and diffusion of oil droplets within the foam, combined with parallel adsorption of oil droplets onto the solid skeleton of the foam. A multiplied usage of these foams for all these niche operations was also proven. The application of our current study with previous studies on modified MFs and polyurethane for water oil separation utilization is summarized in Table S1 ESI.

Novel Slippery Liquid-Infused Porous Surfaces (SLIPS) Based on Electrospun Polydimethylsiloxane/Polystyrene Fibrous Structures Infused with Natural Blackseed Oil.

Hydrophobic fibrous slippery liquid-infused porous surfaces (SLIPS) were fabricated by electrospinning polydimethylsiloxane (PDMS) and polystyrene (PS) as a carrier polymer on plasma-treated polyethylene (PE) and polyurethane (PU) substrates. Subsequent infusion of blackseed oil (BSO) into the porous structures was applied for the preparation of the SLIPS. SLIPS with infused lubricants can act as a repellency layer and play an important role in the prevention of biofilm formation. The effect of polymer solutions used in the electrospinning process was investigated to obtain well-defined hydrophobic fibrous structures. The surface properties were analyzed through various optical, macroscopic and spectroscopic techniques. A comprehensive investigation of the surface chemistry, surface morphology/topography, and mechanical properties was carried out on selected samples at optimized conditions. The electrospun fibers prepared using a mixture of PDMS/PS in the ratio of 1:1:10 (g/g/mL) using tetrahydrofuran (THF) solvent showed the best results in terms of fiber uniformity. The subsequent infusion of BSO into the fabricated PDMS/PS fiber mats exhibited slippery behavior regarding water droplets. Moreover, prepared SLIPS exhibited antibacterial activity against Staphylococcus aureus and Escherichia coli bacterium strains.

Copolyamide-Clay Nanotube Polymer Composite Nanofiber Membranes: Preparation, Characterization and Its Asymmetric Wettability Driven Oil/Water Emulsion Separation towards Sewage Remediation.

To address the problem of ever-increasing oily wastewater management, due to its directional liquid transport property, membranes with asymmetric wettability can be effectively used for emulsion separation. This study reports the synthesis of electrospun polymer-clay nanocomposite nanofibers, using co-polyamide polymer (COPA) and halloysite nanotubes (HA) as filler. The influence of clay content on the morphological, thermal and dielectric properties of the polymer composite nanofiber was investigated comprehensively to address the material characteristics of the developed system. The surface structure analysis and contact angle measurements of the electrospun composite nanofibers confirms the change in surface roughness and wettability when the fillers are added to the polymer. The porosity of the composite electrospun nanofiber membrane was found to be 85% with an oil adsorption capacity of 97% and water permeability of 6265 L/m2 h. Furthermore, the asymmetric wettability-driven oil/water emulsion separation abilities of the as-synthesized membranes shows that the separation efficiency of the composite fiber membrane is 10% improved compared to that of the neat fiber membrane, with improved separation time.

Foamed Phase Change Materials Based on Recycled Polyethylene/Paraffin Wax Blends.

Foamed phase-change materials (FPCMs) were prepared using recycled linear low-density polyethylene (LLDPE) blended with 30 wt.% of paraffin wax (PW) and foamed by 1,1'-azobiscarbamide. The protection of pores' collapse during foaming process was insured through chemical cross-linking by organic peroxide prior foaming. This work represents one of very few attempts for a preparation of polymeric phase change foams without a use of micro-encapsulated phase change component leading to the enhancement of the real PCM component (PW) within a final product. The porous structure of fabricated foams was analyzed using micro-computed tomography, and direct observation, and reconstruction of the internal structure was investigated. The porosity of FPCMs was about 85-87 vol.% and resulting thermal conductivity 0.054-0.086 W/m·K. Differential Scanning Calorimetry was used to determine the specific enthalpies of melting (22.4-25.1 J/g) what is the latent heat of materials utilized during a heat absorption. A stability of samples during 10 heating/cooling cycles was demonstrated. The phase change changes were also investigated using the dynamic mechanical analysis from 0° to 65 °C during the 10 cycles, and the mechanical stability of the system and phase-change transition were clearly confirmed, as proved by DSC. Leaching test revealed a long-term release of PW (around 7% of its original content) from samples which were long term stored at temperatures over PW melting point. This is the usual problem concerning polymer/wax blends. The most common, industrially feasible solution is a lamination of products, for instance by aluminum foils. Finally, the measurement of the heat flow simulating the real conditions shows that samples containing PW decrease the energy passing through the sample from 68.56 to 34.88 kJ·m-2. In this respect, FPCMs provide very effective double functionality, firstly common thermal insulators, and second, as the heat absorbers acting through melting of the PW and absorbing the excessive thermal energy during melting. This improves the heat protection of buildings and reduces temperature fluctuations within indoor spaces.

The Separation of Emulsified Water/Oil Mixtures through Adsorption on Plasma-Treated Polyethylene Powder.

This paper addresses the preparation and characterization of efficient adsorbents for tertiary treatment (oil content below 100 ppm) of oil/water emulsions. Powdered low-density polyethylene (LDPE) was modified by radio-frequency plasma discharge and then used as a medium for the treatment of emulsified diesel oil/water mixtures in the concentration range from 75 ppm to 200 ppm. Plasma treatment significantly increased the wettability of the LDPE powder, which resulted in enhanced sorption capability of the oil component from emulsions in comparison to untreated powder. Emulsions formed from distilled water and commercial diesel oil (DO) with concentrations below 200 ppm were used as a model of oily polluted water. The emulsions were prepared using ultrasonication without surfactant. The droplet size was directly proportional to sonication time and ranged from 135 nm to 185 nm. A sonication time of 20 min was found to be sufficient to prepare stable emulsions with an average droplet size of approximately 150 nm. The sorption tests were realized in a batch system. The effect of contact time and initial oil concentrations were studied under standard atmospheric conditions at a stirring speed of 340 rpm with an adsorbent particle size of 500 microns. The efficiency of the plasma-treated LDPE powder in oil removal was found to be dependent on the initial oil concentration. It decreased from 96.7% to 79.5% as the initial oil concentration increased from 75 ppm to 200 ppm. The amount of adsorbed oil increased with increasing contact time. The fastest adsorption was observed during the first 30 min of treatment. The adsorption kinetics for emulsified oils onto sorbent followed a pseudo-second-order kinetic model.

Slippery Liquid-Infused Porous Polymeric Surfaces Based on Natural Oil with Antimicrobial Effect.

Many polymer materials have found a wide variety of applications in biomedical industries due to their excellent mechanical properties. However, the infections associated with the biofilm formation represent serious problems resulting from the initial bacterial attachment on the polymeric surface. The development of novel slippery liquid-infused porous surfaces (SLIPSs) represents promising method for the biofilm formation prevention. These surfaces are characterized by specific microstructural roughness able to hold lubricants inside. The lubricants create a slippery layer for the repellence of various liquids, such as water and blood. In this study, effective antimicrobial modifications of polyethylene (PE) and polyurethane (PU), as commonly used medical polymers, were investigated. For this purpose, low-temperature plasma treatment was used initially for activation of the polymeric surface, thereby enhancing surface and adhesion properties. Subsequently, preparation of porous microstructures was achieved by electrospinning technique using polydimethylsiloxane (PDMS) in combination with polyamide (PA). Finally, natural black seed oil (BSO) infiltrated the produced fiber mats acting as a lubricating layer. The optimized fiber mats' production was achieved using PDMS/PA mixture at ratio 1:1:20 (g/g/mL) using isopropyl alcohol as solvent. The surface properties of produced slippery surfaces were analyzed by various microscopic and optics techniques to obtain information about wettability, sliding behavior and surface morphology/topography. The modified PE and PU substrates demonstrated slippery behavior of an impinged water droplet at a small tilting angle. Moreover, the antimicrobial effects of the produced SLIPs using black seed oil were proven against Gram-positive Staphylococcus aureus (S. aureus) and Gram-negative Escherichia coli (E. coli).

Thermally Conductive Polyethylene/Expanded Graphite Composites as Heat Transfer Surface: Mechanical, Thermo-Physical and Surface Behavior.

Composites of high-density polyethylene (HDPE) and expanded graphite (EG) are prepared for heat exchangers in multi-effect distillation (MED) desalination. At 50 wt.% EG loading, the thermal conductivity of HDPE was increased by 372%. Moreover, the surface wettability of the HDPE/EG composite was enhanced by corona and RF plasma treatment as demonstrated by the increase in surface free energy from 28.5 mJ/m2 for untreated HDPE/EG to 55.5 and 54.5 mJ/m2 for HDPE/EG treated by corona and RF plasma, respectively. This enhanced surface wettability was retained over a long time with only a 9% and 18% decrease in RF and corona plasma-treated samples' surface energy after two months. The viscoelastic moduli and the complex viscosity profiles indicated that EG content dictates the optimum processing technique. At loading below 30 wt.%, the extrusion process is preferred, while above 30 wt.% loading, injection molding is preferred. The plasma treatment also improved the HDPE/EG composite overall heat transfer coefficient with an overall heat transfer coefficient of the composite reaching about 98% that of stainless steel. Moreover, the plasma-treated composite exhibited superior resistance to crystallization fouling in both CaSO4 solution and artificial seawater compared to untreated composites and stainless-steel surfaces.

Electrochemical Investigation of Interfacial Properties of Ti3C2T x MXene Modified by Aryldiazonium Betaine Derivatives.

For efficient and effective utilization of MXene such as biosensing or advanced applications, interfacial modification of MXene needs to be considered. To this end, we describe modification of Ti3C2Tx MXene by aryldiazonium-based grafting with derivatives bearing a sulfo- (SB) or carboxy- (CB) betaine pendant moiety. Since MXene contains free electrons, betaine derivatives could be grafted to MXene spontaneously. Kinetics of spontaneous grafting of SB and CB toward MXene was electrochemically examined in two different ways, and such experiments confirmed much quicker spontaneous SB grafting compared to spontaneous CB grafting. Moreover, a wide range of electrochemical methods investigating non-Faradaic and Faradaic redox behavior also in the presence of two redox probes together with contact-angle measurements and secondary ion mass spectrometry (SIMS) confirmed substantial differences in formation and interfacial presentation of betaine layers, when spontaneously grafted on MXene. Besides spontaneous grafting of CB and SB toward MXene, also electrochemical grafting by a redox trigger was performed. Results suggest that electrochemical grafting provides a denser layer of SB and CB on the MXene interface compared to spontaneous grafting of SB and CB. Moreover, an electrochemically grafted SB layer offers much lower interfacial resistance and an electrochemically active surface area compared to an electrochemically grafted CB layer. Thus, by adjusting the SB/CB ratio in the solution during electrochemical grafting, it is possible to effectively tune the redox behavior of an MXene-modified interface. Finally, electrochemically grafted CB and SB layers on MXene were evaluated against non-specific protein binding and compared to the anti-fouling behavior of an unmodified MXene interface.

Ti3C2Tx MXene-Based Light-Responsive Hydrogel Composite for Bendable Bilayer Photoactuator.

Soft actuators based on hydrogel materials, which can convert light energy directly into mechanical energy, are of the utmost importance, especially with enhancements in device development. However, the hunt for specific photothermal nanomaterials with distinct performance remains challenging. In this study, we successfully fabricated a bilayer hydrogel actuator consisting of an active photothermal layer from incorporated Ti3C2Tx MXene in poly(N-isopropylacrylamide) p(NIPAm)hydrogel structure and a passive layer from the N-(2-hydroxylethylpropyl)acrylamide (HEAA) hydrogel structure. The uniform and effective incorporation of MXene into the NIPAm hydrogel structures were characterized by a battery of techniques. The light responsive swelling properties of the MXene-embedded NIPAm-based hydrogel demonstrated fully reversible and repeatable behavior in the light on-off regime for up to ten consecutive cycles. The effect of MXene loading, the shape of the actuator, and the light source effects on the bilayer NIPAm-HEAA hydrogel structure were investigated. The bilayer hydrogel with MXene loading of 0.3% in the NIPAm hydrogel exhibited a 200% change of the bending angle in terms of its bidirectional shape/volume after 100 s exposure to white light at an intensity of 70 mW cm-2. Additionally, the bending behavior under real sunlight was evaluated, showing the material's potential applicability in practical environments.

Separation of Water/Oil Emulsions by an Electrospun Copolyamide Mat Covered with a 2D Ti3C2Tx MXene.

Purpose: Copolyamide 6,10 (coPA) electrospun mats were covered with multilayered (ML) and single-layered (SL) MXene (Ti3C2Tx) as a membrane for the separation of water/vegetable oil emulsions. Methods: Prepared membranes were characterized by atomic force microscopy (AFM), profilometry, the contact angle measurements of various liquids in air, and the underwater contact angle of vegetable oil. The separation efficiency was evaluated by measuring the UV transmittance of stock solutions compared to the UV transmittance of the filtrate. Results: The MXene coating onto coPA mats led to changes in the permeability, hydrophilicity, and roughness of the membranes and enhanced the separation efficiency of the water/vegetable oil emulsions containing 10, 100, and 1000 ppm of sunflower vegetable oil. It was found that membranes were highly oleophobic (>124°) under water, unlike in air, where the membranes showed high oleophobicity (<5°). The separation efficiency of water/oil emulsions for both types of covered membranes reached over 99%, with a surface coverage of 3.2 mg/cm2 Ti3C2Tx (for ML-Ti3C2Tx) and 2.9 mg/cm2 (for SL-Ti3C2Tx). Conclusions: The separation efficiency was greater than 98% for membranes covered with 2.65 mg/cm2 of ML-Ti3C2Tx, whereas the separation efficiency for membranes containing 1.89 and 0.77 mg/cm2 was less than 90% for all studied emulsion concentrations.

Piezoresistive Sensors Based on Electrospun Mats Modified by 2D Ti3C2Tx MXene.

The preparation methodology and properties of electroconductive, electrospun mats composed of copolyamide 6,10 and Ti3C2Tx are described in this paper. Mats of several compositions were prepared from a solution of n-propanol. The obtained electrospun mats were then tested as piezoresistive sensors. The relative resistance (AR) of the sensor increased with an increase in the Ti3C2Tx content, and materials with relatively higher electrical conductivity displayed noticeably higher sensitivity to applied pressure. The pressure-induced changes in resistivity increased with an increment in the applied force.

Electrically Conductive, Transparent Polymeric Nanocomposites Modified by 2D Ti3C2Tx (MXene).

The electrically conductive, transparent, and flexible self-standing thin nanocomposite films based on copolyamide matrix (coPA:Vestamelt X1010) modified with 2D Ti3C2Tx (MXene) nanosheets were prepared by casting and their electrical, mechanical and optical properties and then, were investigated. The percolation threshold of the MXene filler within the coPA matrix was found to be 0.05 vol. %, and the highest determined electrical conductivity was 1.4 × 10-2 S·cm-1 for the composite filled with 5 wt. % (1.8 vol. %) of MXene. The electrical conductivity of the as-prepared MXene was 9.1 S·cm-1, and the electrical conductivity of the MAX phase (the precursor for MXene preparation) was 172 S·cm-1. The transparency of the prepared composite films exceeded 75%, even for samples containing 5 wt. % of MXene, as confirmed by UV spectroscopy. The dynamic mechanical analysis confirmed the improved mechanical properties, such as the storage modulus, which improved with the increasing MXene content. Moreover, all the composite films were very flexible and did not break under repeated twisting. The combination of the relatively high electrical conductivity of the composites filled with low filler content, an appropriate transparency, and good mechanical properties make these materials promising for applications in flexible electronics.

Recycled Polyethylene/Paraffin Wax/Expanded Graphite Based Heat Absorbers for Thermal Energy Storage: An Artificial Aging Study.

An artificial aging study of novel heat absorbers based on phase change materials (PCMs) prepared from recycled high-density polyethylene (HDPE), paraffin wax (PW), and expanded graphite (EG) was investigated. The optimal composition of PCMs contained 40 wt% HDPE, whereas the paraffin wax content ranged from 40 to 60 wt% and the expanded graphite content ranged from 5 to 15 wt%. PCMs were artificially aged through exposure to UV irradiation, enhanced temperature, and humidity. It was clearly demonstrated that the addition of EG to PCMs led to the suppression of PW leakage and improved the photooxidation stability of the PCMs during the aging process. The best performance was achieved by adding 15 wt% of EG to the PCMs. The sample shows a leakage of paraffin wax below 10%, retaining a melting enthalpy of PW within PCMs of 54.8 J/g, a thermal conductivity of 1.64 W/mK and the lowest photooxidation, characterized by an increase in the concentration of carbonyl groups from all investigated materials after artificial aging. Furthermore, PCMs mixed with EG exhibited good mechanical properties, even after 100 days of exposure to artificial aging. Finally, this work demonstrates a justification for the use of recycled plastics in the formation of PCMs.

Smart Non-Woven Fiber Mats with Light-Induced Sensing Capability.

This article is focused on the facile procedure for 2D graphene oxide (GO) fabrication, utilizing reversible de-activation polymerization approach and therefore enhanced compatibility with surrounding polymer matrix. Such tunable improvement led to a controllable sensing response after irradiation with light. The neat GO as well as surface initiated atom transfer radical polymerization (SI-ATRP) grafted particles were investigated by atomic force microscopy, Fourier transform infrared spectroscopy and thermogravimetric analysis. To confirm the successful surface reduction, X-ray photoelectron spectroscopy and Raman spectroscopy was utilized. The composites in form of non-woven fiber mats containing ungrafted GO and controllably grafted GO with compact layer of polymer dispersed in poly(vinylidene-co-hexafluoropropylene) were prepared by electrospinning technique and characterized by scanning electron microscopy. Mechanical performance was characterized using dynamic mechanical analysis. Thermal conductivity was employed to confirm that the conducting filler was well-dispersed in the polymer matrix. The presented controllable coating with polymer layer and its impact on the overall performance, especially photo-actuation and subsequent contraction of the material aiming on the sensing applications, was discussed.

Piezoresponse, Mechanical, and Electrical Characteristics of Synthetic Spider Silk Nanofibers.

This work presents electrospun nanofibers from synthetic spider silk protein, and their application as both a mechanical vibration and humidity sensor. Spider silk solution was synthesized from minor ampullate silk protein (MaSp) and then electrospun into nanofibers with a mean diameter of less than 100 nm. Then, mechanical vibrations were detected through piezoelectric characteristics analysis using a piezo force microscope and a dynamic mechanical analyzer with a voltage probe. The piezoelectric coefficient (d33) was determined to be 3.62 pC/N. During humidity sensing, both mechanical and electric resistance properties of spider silk nanofibers were evaluated at varying high-level humidity, beyond a relative humidity of 70%. The mechanical characterizations of the nanofibers show promising results, with Young's modulus and maximum strain of up to 4.32 MPa and 40.90%, respectively. One more interesting feature is the electric resistivity of the spider silk nanofibers, which were observed to be decaying with humidity over time, showing a cyclic effect in both the absence and presence of humidity due to the cyclic shrinkage/expansion of the protein chains. The synthesized nanocomposite can be useful for further biomedical applications, such as nerve cell regrowth and drug delivery.

2D Ti3C2Tx (MXene)-reinforced polyvinyl alcohol (PVA) nanofibers with enhanced mechanical and electrical properties.

Novel 2D Ti3C2Tx (MXene)-reinforced polyvinyl alcohol (PVA) nanofibers have been successfully fabricated by an electrospinning technique. The high aspect ratio, hydrophilic surfaces, and metallic conductivity of delaminated MXene nanosheet render it promising nanofiller for high performance nanocomposites. Cellulose nanocrystals (CNC) were used to improve the mechanical properties of the nanofibers. The obtained electrospun nanofibers had diameter from 174 to 194 nm depending on ratio between PVA, CNC and MXene. Dynamic mechanical analysis demonstrated an increase in the elastic modulus from 392 MPa for neat PVA fibers to 855 MPa for fibers containing CNC and MXene at 25°C. Moreover, PVA nanofibers containing 0.14 wt. % Ti3C2Tx exhibited dc conductivity of 0.8 mS/cm conductivity which is superior compared to similar composites prepared using methods other than electrospinning. Improved mechanical and electrical characteristics of the Ti3C2Tx /CNC/PVA composites make them viable materials for high performance energy applications.

Photoimmobilization of zwitterionic polymers on surfaces to reduce cell adhesion.

Simple and robust methods for modifying hydrophobic polymer surfaces with zwitterionic polymers using UV irradiation were developed. Two random zwitterionic copolymers consisting of either carboxybetaine or sulfobetaine methacrylamide monomers and monomers bearing a photolabile azidophenyl group were directly photoimmobilized on polymeric surfaces (polyester, polyethylene and polystyrene) via covalent interactions in a spatially controlled manner. These copolymers were also electrospun to form self-standing mats. The modified surfaces were characterized by X-ray photoelectron spectroscopy, atomic force microscopy, infrared spectroscopy and contact angle measurements. The electrospinning method involved the use of a trifluoroethanol solution with a copolymer concentration in the range from 2 to 10wt.%. BHK 21 cell adhesion to both modified surfaces and mats was dramatically reduced compared to unmodified surfaces.

Light-switchable polymer from cationic to zwitterionic form: synthesis, characterization, and interactions with DNA and bacterial cells.

A novel cationic polymer poly(N,N-dimethyl-N-[3-(methacroylamino) propyl]-N-[2-[(2-nitrophenyl)methoxy]-2-oxo-ethyl]ammonium chloride) is synthesized by free-radical polymerization of N-[3-(dimethylamino)propyl] methacrylamide and subsequent quaternization with o-nitrobenzyl 2-chloroacetate. The photolabile o-nitrobenzyl carboxymethyl pendant moiety is transformed to the zwitterionic carboxybetaine form upon the irradiation at 365 nm. This feature is used to condense and, upon the light irradiation, to release double-strand DNA tested by gel electrophoresis and surface plasmon resonance experiments as well as to switch the antibacterial activity to non-toxic character demonstrated for Escherichia coli bacterial cells in solution and at the surface using the self-assembled monolayers.