Alper Kiziltas

Preparation and characterization of transparent PMMA–cellulose-based nanocomposites

Nanocomposites of polymethylmethacrylate (PMMA) and cellulose were made by a solution casting method using acetone as the solvent. The nanofiber networks were prepared using three different types of cellulose nanofibers: (i) nanofibrillated cellulose (NFC), (ii) cellulose nanocrystals (CNC) and (iii) bacterial cellulose from nata de coca (NDC). The loading of cellulose nanofibrils in the PMMA varied between 0.25 and 0.5 wt%. The mechanical properties of the composites were evaluated using a dynamic mechanical thermal analyzer (DMTA). The flexural modulus of the nanocomposites reinforced with NDC at the 0.5 wt% loading level increased 23% compared to that of pure PMMA. The NFC composite also exhibited a slightly increased flexural strength around 60 MPa while PMMA had a flexural strength of 57 MPa. The addition of NDC increased the storage modulus (11%) compared to neat PMMA at room temperature while the storage modulus of PPMA/CNC nanocomposite containing 0.25 and 0.5 wt% cellulose increased about 46% and 260% to that of the pure PMMA at the glass transition temperature, respectively. Thermogravimetric analysis (TGA) indicated that there was no significant change in thermal stability of the composites. The UV-vis transmittance of the CNF nanocomposites decreased by 9% and 27% with the addition of 0.25 wt% CNC and NDC, respectively. This work is intended to spur research and development activity for application of CNF reinforced PMMA nanocomposites in applications such as: packaging, flexible screens, optically transparent films and light-weight transparent materials for ballistic protection.

Synthesis of bacterial cellulose using hot water extracted wood sugars

Bacterial cellulose (BC), a type of nanopolymer produced by Acetobacter xylinum is a nanostructured material with unique properties and wide applicability. However, a standard medium used for the cultivation of BC, the Hestrin-Schramm medium, is expensive and prevents wide scale extension of BC applications. In this research, a relatively low-cost culture media was successfully developed from wood hot water extracts for the Acetobacter xylinus 23769 strain. Hot water extract (HWE) is a residual material originating from pulp mills and lignocellulosic biorefineries and consists of mainly monomeric sugars, organic acids and organics. The effects of different pH (5, 6, 7 and 8) and temperatures (26, 28 and 30°C) were also examined in this research. There were no significant differences in the crystallinity and the recorded Iα fraction of cellulose produced between Hestrin-Schramm and the HWE medium. The maximum production of 0.15g/l of BC was obtained at a pH of 8 and temperature of 28°C. Glucose and xylose in the HWE were the main nutrient sources utilized in all BC cultivations based on high-pressure liquid chromatography (HPLC) results. HWE was shown to be a suitable carbon source for BC production, and a process was established for BC production from lignocellulosic feedstocks without using any modification of the HWE. HWE is an abundant and relatively inexpensive forest by-product. Using HWE for BC production could reduce burdens on the environment and also, achieve the goal of large scale BC production at low cost without using added culture nutrients.

Thermal analysis and crystallinity study of cellulose nanofibril-filled polypropylene composites

The isothermal and non-isothermal decompositions of cellulose nanofiber (CNF) and microfibrillated cellulose (MFC)-filled polypropylene (PP) composites were evaluated and compared with microcrystalline cellulose (MCC)-filled composites by means of thermogravimetric analysis (TG). X-ray diffraction was employed to evaluate crystallinity of the composites. The degree of maximum thermal degradation (ultimate DTG peak value) increased and thermal degradation onset temperature decreased as the cellulose content increased because the thermal stability of cellulose fillers is lower than that of neat PP, but the thermal degradation of the composite was hindered at higher temperature conditions because of the increased residual mass content of the cellulose nanofibril fillers compared to the matrix polymer. The isothermal residual mass of the cellulose nanofibril-filled PP composites under melt blending and injection molding temperatures was decreased marginally by incorporation of the cellulose reinforcement but still exhibited considerable isothermal stability. The raw materials and composites examined in this study were not affected by the manufacturing process temperatures utilized to produce the composites. The MCC decreased the composite crystallinity while the nano-sized cellulose (CNF and MFC) did not appear to have an effect on crystallinity.

Biosynthesis of bacterial cellulose in the presence of different nanoparticles to create novel hybrid materials.

The unique micro-nano porous three-dimensional network of bacterial cellulose (BC) can facilitate the incorporation of nanoparticles (NPs) into the BC matrix to create advanced BC-based functional nanomaterials for diverse applications. In this study, novel nanomaterials comprised of bacterial cellulose (BC) synthesized in the presence of different NPs (cellulose nanofibrils (CNF), exfoliated graphite nanoplatelets (xGnP), and nanoclay (NC)) were prepared using an in situ approach. NPs at 0.5 wt.% loading were added into the BC culture medium and their effect on the resulting nanocomposite structure was studied by field emission scanning electron microscopy (FE-SEM), X-Ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and thermogravimetric analysis (TGA). All BC-based nanomaterials produced, exhibited good dispersion of the NPs within the BC matrix and the NPs were found embedded among the voids and microfibrils. The thermal stability and residual mass of BC-xGnP and BC-NC nanomaterials was significantly increased compared with the neat BC. CNF incorporation into the BC matrix did not change the thermal stability and residual mass of the BC matrix. This study also provides novel insights into the properties of the hybrid materials, and shows the approach used to make these materials which results in increased performance for chosen applications.

Method to reinforce polylactic acid with cellulose nanofibers via a polyhydroxybutyrate carrier system.

The elastic moduli of PLA reinforced with 5 and 10wt.% CNF with the carrier, at a frequency (ω) of 0.07, were 67% and 415% higher, respectively, than that of neat PLA. The shear viscosity at a shear rate of 0.01 (η0.01) for PLA+10wt.% CNF was 32% higher than that of the neat PLA matrix. The η0.01 of PLA reinforced with 5wt.% CNF and the PHB carrier was similar to neat PLA. The tensile and flexural moduli of elasticity of the nanocomposites continuously increased with increased CNF loading. The results of the mechanical property measurements are in accordance with the rheological data. The CNF appeared to be better dispersed (less-aggregated nanofibers) in the PLA reinforced with 5wt.% CNF and the PHB carrier. Possible applications for the composites studied in this research are packaging materials, construction materials, and auto parts for interior applications.

Electrically conductive nano graphite-filled bacterial cellulose composites

A unique three dimensional (3D) porous structured bacterial cellulose (BC) can act as a supporting material to deposit the nanofillers in order to create advanced BC-based functional nanomaterials for various technological applications. In this study, novel nanocomposites comprised of BC with exfoliated graphite nanoplatelets (xGnP) incorporated into the BC matrix were prepared using a simple particle impregnation strategy to enhance the thermal properties and electrical conductivity of the BC. The flake-shaped xGnP particles were well dispersed and formed a continuous network throughout the BC matrix. The temperature at 10% weight loss, thermal stability and residual ash content of the nanocomposites increased at higher xGnP loadings. The electrical conductivity of the composites increased with increasing xGnP loading (attaining values 0.75 S/cm with the addition of 2 wt.% of xGnP). The enhanced conductive and thermal properties of the BC-xGnP nanocomposites will broaden applications (biosensors, tissue engineering, etc.) of BC and xGnP.

Thermal Analysis of Micro- and Nano-Lignocellulosic Reinforced Styrene Maleic Anhydride Composite Foams

The aim of this study was to measure the thermal properties of foamed nano/macro filler–reinforced styrene maleic anhydride (SMA) composites. SMA (66%) as a polymer matrix (10% maleic anhydride content) and various fillers including wood flour, starch, α-cellulose, microcrystalline cellulose and cellulose nanofibrils as reinforcing agents (30%) and lubricant (4%) were used to manufacture the composites in a twin-screw extruder. According to the thermogravimetric analysis (TGA) results, thermal degradation of all the foamed composites was found to be lower than that of SMA composites. The storage modulus values were negatively affected with a second time foaming (reprocessing [recycling] the initially processed composites a second time), as were loss modulus and Tg. As a result, second-time-foamed composite modulus values were lower than those of the foamed composites. According to the melt flow index (MFI) results, viscosity of the SMA was found to increase with the addition of fillers.

Understanding the Affinity between Components of Wood–Plastic Composites from a Surface Energy Perspective

To evaluate surface compatibility in wood-plastic composites (WPCs), the dispersion and acid–base components of surface energy of various thermoplastic resins (matrices) and several wood-based reinforcing materials were determined using inverse gas chromatography (IGC). Polypropylene (PP), nylon 6, poly(ethylene terephthalate) (PET), poly(trimethyl terephthalate) (PTT), high impact polystyrene (HIPS), and styrene maleic anhydride (SMA) were used as thermoplastic resins, while wood flour (hot water extracted and un-extracted), microcrystalline cellulose (MCC) (50 μm and 90 μm), α-cellulose (60 μm), and silicified microcrystalline cellulose (SMCC) (60 μm) were used as reinforcing materials. All matrices and reinforcing components were exposed to low vapor concentrations of apolar (decane, heptane, nonane, octane) and polar (chloroform, ethyl acetate, dichloromethane, acetone, and tetrahydrofuran) probes. Methane and helium were employed as reference and carrier gases, respectively. IGC retention times were used to determine the acid–base component of surface energy of the analyzed materials. The corresponding surface energy, work of adhesion, and work of cohesionwere calculated based on the van Oss–Chaudhury–Good approach (acid–base and Lifshitz–van der Waals interactions). Composite performance was analyzed by measuring tensile and flexural strengths according to ASTM standards. The results indicated that for the same type of filler (assuming similar shape and dimensions), the mechanical properties of the composites increased when the ratio of the work of adhesion to the work of cohesion increased. A similar trend was observed when the thermoplastic resin employed to create the composite possessed an acid–base component of surface energy greater than zero.

Glycerine Treated Nanofibrillated Cellulose Composites

Glycerine treated nanofibrillated cellulose GNFC was prepared by mixing aqueous nanofibrillated cellulose NFC suspensions with glycerine. Styrene maleic anhydride SMA copolymer composites with different loadings of GNFC were prepared by melt compounding followed by injection molding. The incorporation of GNFC increased tensile and flexural modulus of elasticity of the composites. Thermogravimetric analysis showed that as GNFC loading increased, the thermal stability of the composites decreased marginally. The incorporation of GNFC into the SMA copolymer matrix resulted in higher elastic modulus G′ and shear viscosities than the neat SMA copolymer, especially at low frequencies. The orientation of rigid GNFC particles in the composites induced a strong shear thinning behavior with an increase in GNFC loading. The decrease in the slope of elastic modulus with increasing GNFC loading suggested that the microstructural changes of the polymer matrix can be attributed to the incorporation of GNFC. Scanning electron microscopy SEM images of fracture surfaces show areas of GNFC agglomerates in the SMA matrix.

Influence of Micro- and Nanonatural Fillers on Mechanical and Physical Properties of Foamed SMA Composites

This study is to investigate the reinforcing effects of fillers on mechanical and physical properties of foamed styrene-maleic anhydride (SMA) composites. According to the results, the best foaming was determined for starch reinforced SMA composite. The best result of expansion ratio was found as 22.75% to SMA/starch composites. Stereo light microscopy results demonstrated that the foamed cell distribution is heterogeneous and composed of two sections. The minimum density was found as 0.64 g/cm3 for foamed SMA/starch composites. Mechanical properties of all foamed composites were found to be low as compared to neat SMA composite.