Yusuf Z. Menceloğlu

Dispersion Polymerizations in Supercritical Carbon Dioxide

Conventional heterogeneous dispersion polymerizations of unsaturated monomers are performed in either aqueous or organic dispersing media with the addition of interfacially active agents to stabilize the colloidal dispersion that forms. Successful stabilization of the polymer colloid during polymerization results in the formation of high molar mass polymers with high rates of polymerization. An environmentally responsible alternative to aqueous and organic dispersing media for heterogeneous dispersion polymerizations is described in which supercritical carbon dioxide (CO2) is used in conjunction with molecularly engineered free radical initiators and amphipathic molecules that are specifically designed to be interfacially active in CO2. Conventional lipophilic monomers, exemplified by methyl methacrylate, can be quantitatively (>90 percent) polymerized heterogeneously to very high degrees of polymerization (>3000) in supercritical CO2 in the presence of an added stabilizer to form kinetically stable dispersions that result in micrometer-sized particles with a narrow size distribution.

Engineering Chemistry of Electrospun Nanofibers and Interfaces in Nanocomposites for Superior Mechanical Properties

The novelty of this work is based on designing the chemistry of the electrospun nanofibers, so that the resultant composites substantially benefit from cross-linking between the nanofibers and the polymer matrix. Specifically, the solution of in-house synthesized copolymers polystyrene-co-glycidyl methacrylate P(St-co-GMA) is electrospun to produce mats of surface reactive nano-to-submicron scale fibers that are accompanied later by spraying over the ethylenediamine (EDA) as a supplementary cross-linking agent for epoxy. The P(St-co-GMA)/EDA fiber mats are then embedded into an epoxy resin. Analysis of the three-point-bending mode of the composites reveals that the storage modulus of P(St-co-GMA)/EDA nanofiber-reinforced epoxy are about 10 and 2.5 times higher than that of neat and P(St-co-GMA) nanofiber-reinforced epoxy, respectively, even though the weight fraction of the nanofibers was as low as 2 wt %. The significant increase in the mechanical response is attributed to the inherently cross-linked fiber structure and the surface modification/chemistry of the electrospun fibers, that results in cross-linked polymer matrix-nanofiber interfacial bonding.

MWCNTs/P(St-co-GMA) Composite Nanofibers of Engineered Interface Chemistry for Epoxy Matrix Nanocomposites

Strengthened nanofiber-reinforced epoxy matrix composites are demonstrated by engineering composite electrospun fibers of multi-walled carbon nanotubes (MWCNTs) and reactive P(St-co-GMA). MWCNTs are incorporated into surface-modified, reactive P(St-co-GMA) nanofibers by electrospinning; functionalization of these MWCNT/P(St-co-GMA) composite nanofibers with epoxide moieties facilitates bonding at the interface of the cross-linked fibers and the epoxy matrix, effectively reinforcing and toughening the epoxy resin. Rheological properties are determined and thermodynamic stabilization is demonstrated for MWCNTs in the P(St-co-GMA)-DMF polymer solution. Homogeneity and uniformity of the fiber formation within the electrospun mats are achieved at polymer concentration of 30 wt %. Results show that the MWCNT fraction decreases the polymer solution viscosity, yielding a narrower fiber diameter. The fiber diameter drops from an average of 630 nm to 460 nm, as the MWCNTs wt fraction (1, 1.5, and 2%) is increased. The electrospun nanofibers of the MWCNTs/P(St-co-GMA) composite are also embedded into an epoxy resin to investigate their reinforcing abilities. A significant increase in the mechanical response is observed, up to >20% in flexural modulus, when compared to neat epoxy, despite a very low composite fiber weight fraction (at about 0.2% by a single-layer fibrous mat). The increase is attributed to the combined effect of the two factors the inherent strength of the well-dispersed MWCNTs and the surface chemistry of the electrospun fibers that have been modified with epoxide to enable cross-linking between the polymer matrix and the nanofibers.

Comparison of the effectiveness of chlorine, ozone, and photocatalytic disinfection in reducing the risk of antibiotic resistance pollution

Abstract Effectiveness of conventional chlorine and ozone disinfection on reduction of antibiotic resistance was compared with less commonly applied heterogeneous photocatalytic process. For this purpose plasmid DNA isolated from a multi-resistant Escherichia coli (E. coli) HB101 was treated in two different concentrations with the three oxidation processes. Oxidative damage on the plasmid DNA was analyzed with gel electrophoresis by comparing the extent of conformational changes in the DNA structure. The effectiveness of the applied oxidant in reducing the risk of resistance transfer was also evaluated by comparing the ability of treated plasmid DNA to transform competent cells. Chlorine did not affect plasmid DNA structure at the studied doses, while ozone and photocatalytic treatment resulted in conformational changes and the damage increased with increasing oxidant doses. Transformation experiments confirmed a similar trend. Chlorine did not affect the transformability and the cell counts of competent cells transformed with chlorine treated plasmid DNA were similar to those transformed by non-treated plasmid DNA in the control experiments.

Nano-engineered design and manufacturing of high-performance epoxy matrix composites with carbon fiber/selectively integrated graphene as multi-scale reinforcements

Three different architectural designs are developed for manufacturing advanced multi-scale reinforced epoxy based composites in which graphene sheets and carbon fibers are utilized as nano- and micro-scale reinforcements, respectively. In the first design, electrospraying technique as an efficient and up-scaleable method is employed for the selective deposition of graphene sheets onto the surface of carbon fabric mats. Controlled and uniform dispersion of graphene sheets on the surface of carbon fabric mats enhances the interfacial strength between the epoxy matrix and carbon fibers and increases the efficiency of load transfer between matrix and reinforcing fibers. In the second design, graphene sheets are directly dispersed into the hardener-epoxy mixture to produce carbon fiber/epoxy composites with graphene reinforced matrix. In the third design, the combination of the first and the second arrangements is employed to obtain a multi-scale hybrid composite with superior mechanical properties. The effect of graphene sheets as an interface modifier and as a matrix reinforcement as well as the synergetic effect due to the combination of both arrangements are investigated in details by conducting various physical–chemical characterization techniques. Graphene/carbon fiber/epoxy composites in all three different arrangements of graphene sheets show enhancement in in-plane and out of plane mechanical performances. In the hybrid composite structure in which graphene sheets are used as both interface modifier and matrix reinforcing agent, remarkable improvements are observed in the work of fracture by about 55% and the flexural strength by about 51% as well as notable enhancement on other mechanical properties.

Effects of solvent on TEOS hydrolysis kinetics and silica particle size under basic conditions

In-situ liquid-state 29Si nuclear magnetic resonance was used to investigate the temporal concentration changes during ammonia-catalyzed initial hydrolysis of tetraethyl orthosilicate in different solvents (methanol, ethanol, n-propanol, iso-propanol and n-butanol). Dynamic light scattering was employed to monitor simultaneous changes in the average diameter of silica particles and atomic force microscopy was used to image the particles within this time frame. Solvent effects on initial hydrolysis kinetics, size and polydispersity of silica particles were discussed in terms of polarity and hydrogen-bonding characteristics of the solvents. Initial hydrolysis rate and average particle size increased with molecular weight of the primary alcohols. In comparison, lower hydrolysis rate and larger particle size were obtained in the secondary alcohol. Exceptionally, reactions in methanol exhibited the highest hydrolysis rate and the smallest particle size. Ultimately, our investigation elaborated, and hence confirmed, the influences of chemical structure and nature of the solvent on the formation and growth of the silica particles under applied conditions.

Design and fabrication of multi-walled hollow nanofibers by triaxial electrospinning as reinforcing agents in nanocomposites

Multi-walled triaxial hollow fibers with two different outer wall materials are fabricated by core-sheath electrospinning process and integrated into epoxy matrix with or without primary glass fiber reinforcement to produce composites with enhanced mechanical properties. The morphologies of multi-walled hollow fibers are tailored by controlling the materials and processing parameters such as polymer and solvent types. The triaxial hollow fiber fabrication is achieved through using a nozzle containing concentric tubes, which allows for the transport of different fluids to the tip of the nozzle under the applied high voltage. In comparison to uniaxial electrospun fibers, the hollowness of electrospun fibers enables one to manufacture new reinforcing agents that can improve the specific strength of composites. It is shown that the mechanical properties of epoxy matrix composite incorporated with electrospun fibers as primary fiber reinforcement can be significantly tailored by properly selecting the wall materials, diameters, and the amount of electrospun fibers. We have also presented that triaxial electrospun hollow fibers as co-reinforcement in the glass fiber-laminated epoxy matrix composites enhance the flexural modulus by 6.5%, flexural strength by 14%, the onset of first layer of glass fabric failure strain by 12.5%, and final failure strain by 20%.

Dual scale roughness driven perfectly hydrophobic surfaces prepared by electrospraying a polymer in good solvent-poor solvent systems

We demonstrated a facile method to produce perfectly hydrophobic surfaces (advancing and receding angles both 180°) via electrospraying. When a copolymer of styrene and a perfluoroacrylate monomer was electrosprayed in good solvents, surfaces composed of micrometer size beads were formed and fairly low threshold water sliding angles could be achieved. Addition of high boiling point poor solvents to the solutions resulted nanoscale roughness on the beads due to a possible phase separation that occurs in a predominantly poor solvent environment. However, sliding angles were not zero even on the nanoscale roughness dominated topographies achieved by this method. On the other hand, when the electrospraying process parameters were set such that micrometer size hills of nanoscopically rough beads were formed, 0° sliding angles were measured. Videos of droplets recorded and the adhesive forces measured during a contact and release experiment revealed that these dual scale rough surfaces were indeed perfectly hydrophobic. Application of the method with other binary good solvent-poor solvent systems also resulted in perfect hydrophobicity. Overall results showed how the differences in surface topology affected the wettability of surfaces within a very narrow range between perfect and extreme hydrophobicity (advancing and receding angles both close to 180°).

Halloysite Nanotubes/Polyethylene Nanocomposites for Active Food Packaging Materials with Ethylene Scavenging and Gas Barrier Properties

Novel polymeric active food packaging films comprising halloysite nanotubes (HNTs) as active agents were developed. HNTs which are hollow tubular clay nanoparticles were utilized as nanofillers absorbing the naturally produced ethylene gas that causes softening and aging of fruits and vegetables; at the same time, limiting the migration of spoilage-inducing gas molecules within the polymer matrix. HNT/polyethylene (HNT/PE) nanocomposite films demonstrated larger ethylene scavenging capacity and lower oxygen and water vapor transmission rates than neat PE films. Nanocomposite films were shown to slow down the ripening process of bananas and retain the firmness of tomatoes due to their ethylene scavenging properties. Furthermore, nanocomposite films also slowed down the weight loss of strawberries and aerobic bacterial growth on chicken surfaces due to their water vapor and oxygen barrier properties. HNT/PE nanocomposite films demonstrated here can greatly contribute to food safety as active food packaging materials that can improve the quality and shelf life of fresh food products.

Multifunctional 3D printing of heterogeneous hydrogel structures.

Multimaterial additive manufacturing or three-dimensional (3D) printing of hydrogel structures provides the opportunity to engineer geometrically dependent functionalities. However, current fabrication methods are mostly limited to one type of material or only provide one type of functionality. In this paper, we report a novel method of multimaterial deposition of hydrogel structures based on an aspiration-on-demand protocol, in which the constitutive multimaterial segments of extruded filaments were first assembled in liquid state by sequential aspiration of inks into a glass capillary, followed by in situ gel formation. We printed different patterned objects with varying chemical, electrical, mechanical, and biological properties by tuning process and material related parameters, to demonstrate the abilities of this method in producing heterogeneous and multi-functional hydrogel structures. Our results show the potential of proposed method in producing heterogeneous objects with spatially controlled functionalities while preserving structural integrity at the switching interface between different segments. We anticipate that this method would introduce new opportunities in multimaterial additive manufacturing of hydrogels for diverse applications such as biosensors, flexible electronics, tissue engineering and organ printing.