Zvonimir Katančić

Weathering of High-Density Polyethylene-Wood Plastic Composites

Abstract Due to the widespread use of wood-plastic composites (WPCs), high-density polyethylene-wood flour composites (HDPE/WF) were studied in order to determine their stability in different application conditions. UV degradation and periodic absorption/desorption of moisture cause damaging changes to material during WPCs’ exterior application, so it is necessary to ensure WPCs’ durability against atmospheric influences. Samples were characterized by FTIR spectroscopy and scanning electron microscopy (SEM) in order to study the degradation after simulated weathering. The degree of water absorption was also determined. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were used for the determination of composites’ thermal properties. Results show that the stability of the HDPE/WF composites to UV treatment highly depends on stabilizer content and its dispersion in the polymer matrix. Incompatibility of HDPE and wood particles is a major problem that should be solved to achieve good durability and satisfying properties in use.

Effect of modified nanofillers on fire retarded high-density polyethylene/wood composites

In this study fire retarded HDPE/WF composites based on high density polyethylene (HDPE) and wood flour (WF) were investigated. Polymer and WF ratio was kept at 70/30 while concentration of fire retardant was 20 mass %. Ammonium polyphosphate and aluminum hydroxide were used as fire retardants. To diminish the influence of high loadings of fire retardants on mechanical properties two different types of organically modified nanofillers (CaCO3 and SiO2) were used. Surface modification of HDPE polymer and nanofiller was done to enhance the compatibility in composite and improve the mechanical properties and fire performance. Mechanical properties were characterized by dynamic mechanical analysis while compatibility of components in composites was followed through morphology by scanning electron microscopy. Thermal and fire properties were characterized by thermogravimetric analysis, pyrolysis combustion flow calorimetry, and limiting oxygen index. The obtained results show that addition of surface modified nanofiller considerably affects the morphology resulting in the enhancement of mechanical and fire properties. Ammonium polyphosphate fire retardant in combination with SiO2 nanofiller showed the highest limiting oxygen index value, the lowest heat release rate, and total heat released in pyrolysis-combustion flow calorimetry test indicating best overall fire performance.

Effect of preparation on morphology-properties relationships in SAN/EPDM/PCC composites

Mechanical and morphological properties of composites containing styrene—acrylonitrile (SAN) copolymer, ethylene— propylene—diene (EPDM) polymer, and different types of precipitated calcium carbonate (PCC) were investigated and their properties were analyzed in regard to PCC surface properties and the way of sample preparation (with or without use of a masterbatch (MB)). Contact angles of test liquids on PCC samples were measured in order to determine surface free energies of filler and to predict strength of filler—polymer interactions. Filler—polymer interactions play a significant role in determining preferential localization of the filler in the composite. The tensile and impact strength results of the composites without the MB show much higher values than composites prepared with the MB. Significant decrease of tensile strength is observed for the samples prepared with the MB due to change in morphology, which is elongated dispersed EPDM particles in SAN matrix, compared to the samples prepared without the MB that have droplet morphology.

Thermal decomposition of fire-retarded high-impact polystyrene and high-impact polystyrene/ethylene–vinyl acetate blend nanocomposites followed by thermal analysis

Blend nanocomposites of high-impact polystyrene and ethylene–vinyl acetate at a ratio of 3:1, with the addition of aluminum hydroxide Al(OH)3 and diphenyl 2-ethylhexyl phosphate (DPO) as fire retardants (FRs) and silica (SiO2) nanofiller were prepared by extrusion. Thermal decomposition, mechanism and kinetics of degradation of the studied samples were characterized by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The fire-retarded samples were characterized by following the degradation kinetics obtained from TGA data by recording the samples at four different heating rates. That enables us to determine one of the kinetic parameters, activation energy (E a) of thermal decomposition. The effect of high concentration of FRs on morphology and properties of the studied samples were analyzed by scanning electron microscopy and mechanical properties. The obtained results show that the FRs delay thermal decomposition, particularly in combination with SiO2 nanofiller, which significantly contributes to slowing down the degradation process.

Characterization of Casein Fractions – Comparison of Commercial Casein and Casein Extracted from Cow’s Milk

Biopolymer casein was isolated from cow’s milk by acid coagulation, which was initiated by acetic acid and sodium acetate in the first, and hydrochloric acid in the second process. The casein isolated by acid coagulation, i.e. by first process, and commercial casein were separated on α-, β-, (α+κ)- and κ casein by urea fractionation. The aim of this study was to compare various properties of commercial casein fractions with casein fractions isolated from cow’s milk. The structure of casein and casein fraction samples were monitored by Fourier transform infrared spectroscopy (FTIR), and the obtained vibrational bands showed structural differences between isolated and commercial casein (presence of various amino acids), as well as their fractions. Differential scanning calorimetry (DSC) was used to determine glass transition temperature. The results showed that the glass transitions of the isolated and commercial casein were below room temperature (Tg = 2–30 °C) due to the destruction of the samples structure that provides molecules mobility and leads to a phase transition. Thermal degradation obtained by thermogravimetric analysis (TGA) of all samples occurred in multiple steps. From the results, it is evident that 5 mass % of the each sample degraded at significantly different temperatures (T95), and it can be concluded that isolated casein and its fractions showed better heat stability than commercial casein and its fraction.

Kinetic analysis of thermal and thermo-oxidative degradation of polyethylene (nano)composites

Thermal properties and degradation of polyethylene LDPE (nano)composites were investigated by isoconversional thermogravimetric analysis in air and nitrogen atmosphere by applying the Kissinger–Akahira–Sunose method. Low-density polyethylene (LDPE) composites containing 3 wt.% nanofiller Cloisite 20A and 4, 6, and 8 wt.% of natural zeolite were prepared using extrusion/injection moulding. The parameters of thermal stability of the samples were determined i.e. onset temperature of the degradation (T90), which exhibit initial mass loss (10 mass %) and maximum loss rate temperature (Tmax). Also, activation energy (Ea) of samples was calculated and interpreted in terms of thermal degradation mechanisms. Under nitrogen, the thermal degradation of LDPE (nano)composites follows a random scission pathway but it was retarded and slowed by the presence of the fillers. The results show that thermo-oxidative degradation of studied (nano)composites is induced at lower temperatures and appears as much more complex and multi-stage process.

Flammability and Thermal Properties of Zeolite-Filled High-Impact Polystyrene Composites

Effect of zeolite and organically modified montmorillonite (MMT) clay on flammability of high-impact polystyrene (HIPS) with ammonium polyphosphate (APP) flame retardant was investigated. Composites were prepared by melt blending in a twin-screw extruder, and it was found that zeolite and APP improve fire performance of HIPS with optimal concentration of 4 mass % of zeolite. Samples with MMT/APP and zeolite/APP have similar results of flammability, yet combination MMT/zeolite/APP had no additional improvement of thermal and fire properties. Mechanical properties were degraded with increasing concentration of zeolite, and improvement was visible when only MMT clay was used in combination with APP.

Synthesis of PEDOT/ZnO Photocatalyst: Validation of Photocatalytic Activity by Degradation of Azo RR45 Dye Under Solar and UV-A Irradiation

To study the photocatalytic efficiency of wastewater treatment processes, the nanocomposites of conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) and ZnO nanoparticles were prepared by in-situ synthesis. ZnO is an excellent photocatalyst under UV light, but due to high band gap, photons of visible light have insufficient energy to excite electrons from valence to conductive band, which limits its activity under visible light and therefore practical usage is limited. The PEDOT conductive polymer was used to increase the photocatalytic activity of ZnO since conductive polymers are known as efficient electron donor and good electron transporters upon visible-light excitation. Polymerization of pure PEDOT and PEDOT/ZnO nanocomposites was carried out at varying monomer:oxidant ratio (1:2; 1:3; 1:5) with the ammonium persulfate (APS) used as the oxidant. Samples were characterized by FTIR spectroscopy, XRD analysis, SEM microscopy, UV-Vis spectroscopy and TG analysis. Photocatalytic activity was assessed through removal of C.I. Reactive Red 45 (RR45) azo dye under simulated Solar and UV-A irradiation. Photocatalysis was monitored by measuring discoloration of RR45 using UV/Vis spectroscopy. The results indicate that very low concentration of PEDOT conductive polymer in PEDOT/ZnO nanocomposite can significantly contribute to the efficiency of the photocatalytic process during wastewater treatment.

Surface characteristics and enhancement of water vapour properties of paperboard coated with polycaprolactone nanocomposites

Abstract Offset printed paperboard coated with polycaprolactone (PCL) polymer and nanoparticles was studied to elucidate the interactions and adhesion in two-layered packaging material. SiO2, Al2O3 and ZnO nanoparticles were used due to their specific interactions with water vapour that results in inhibition of water permeability. The good dispersion of nanoparticles in PCL matrix is crucial for enhancement of the barrier properties of coated paperboard. To gain an insight into the interactions between the nanoparticles, paperboard and PCL matrix determination of surface parameters was performed. The samples were characterized for water vapour permeability, mechanical and thermal properties. Their morphology was analysed by SEM microscopy, FTIR and UV/Vis spectroscopy. UV stability of the PCL nanocomposites coatings was also studied. It can be concluded that the nanoparticles have a significant effect on the surface properties and they influenced adhesion between paperboard and PCL coating.