Natural Rubber Composites Using Hydrothermally Carbonized Hardwood Waste Biomass as a Partial Reinforcing Filler-Part II: Mechanical, Thermal and Ageing (Chemical) Properties.

Natural rubber composites were reinforced by the co-fillers 'hydrochar' (HC), obtained by hydrothermal carbonization of hardwood sawdust and commercial carbon black (CB). The content of the combined fillers was kept constant while their ratio was varied. The aim was to test the suitability of HC as a partial filler in natural rubber. Due to its larger particle size and hence smaller specific surface area, large amounts of HC reduced the crosslinking density in the composites. On the other hand, due to its unsaturated organic character, HC was found to display interesting chemical effects: if it was used as the exclusive filler component, it displayed a very strong anti-oxidizing effect, which greatly stabilized the rubber composite against oxidative crosslinking (and hence embrittlement). HC also affected the vulcanization kinetics in different ways, depending on the HC/CB ratio. Composites with HC/CB ratios 20/30 and 10/40 displayed interesting chemical stabilization in combination with fairly good mechanical properties. The performed analyses included vulcanization kinetics, tensile properties, determination of density of permanent and reversible crosslinking in dry and swollen states, chemical stability tests including TGA, thermo-oxidative aging tests in air at 180 °C, simulated weathering in real use conditions ('Florida test'), and thermo-mechanical analyses of degraded samples. Generally, the results indicate that HC could be a promising filler material due to its specific reactivity.

A Novel Approach for Simulation and Optimization of Rubber Vulcanization.

The kinetic model, encompassing the curing and reversion phenomena of the NR/SBR rubber vulcanization process, was developed by means of the finite element method simultaneously with heat transfer equations, including heat generation due to curing reactions. The vulcanization simulation was conducted for three spheres of different diameters (1, 5 and 10 cm) and two rubber wheels, one of which was a commercial product of the rubber industry. The proposed advanced simulation model, based on products' two-dimensional axisymmetry, includes cooling after vulcanization, during which the crosslinking reactions continue to take place as a result of the products' heated interiors. As a criterion for removing the product from the mold, an average vulcanization degree of 0.9 was set, whereby, during cooling, the vulcanization degree increases, due to crosslinking reactions. Based on the minimal difference between the maximal and minimal vulcanization degrees, which did not exceed a value of 0.0142, the optimal process parameters for each product were determined, achieving homogeneity and obtaining high-quality rubber products, while simultaneously ensuring a more efficient vulcanization process and enhanced cost effectiveness for the rubber industry.

Natural Rubber Composites Using Hydrothermally Carbonized Hardwood Waste Biomass as a Partial Reinforcing Filler- Part I: Structure, Morphology, and Rheological Effects during Vulcanization.

A new generation biomass-based filler for natural rubber, 'hydrochar' (HC), was obtained by hydrothermal carbonization of hardwood waste (sawdust). It was intended as a potential partial replacement for the traditional carbon black (CB) filler. The HC particles were found (TEM) to be much larger (and less regular) than CB: 0.5-3 µm vs. 30-60 nm, but the specific surface areas were relatively close to each other (HC: 21.4 m2/g vs. CB: 77.8 m2/g), indicating a considerable porosity of HC. The carbon content of HC was 71%, up from 46% in sawdust feed. FTIR and 13C-NMR analyses indicated that HC preserved its organic character, but it strongly differs from both lignin and cellulose. Experimental rubber nanocomposites were prepared, in which the content of the combined fillers was set at 50 phr (31 wt.%), while the HC/CB ratios were varied between 40/10 and 0/50. Morphology investigations proved a fairly even distribution of HC and CB, as well as the disappearance of bubbles after vulcanization. Vulcanization rheology tests demonstrated that the HC filler does not hinder the process, but it significantly influences vulcanization chemistry, canceling scorch time on one hand and slowing down the reaction on the other. Generally, the results suggest that rubber composites in which 10-20 phr of CB are replaced by HC might be promising materials. The use of HC in the rubber industry would represent a high-tonnage application for hardwood waste.

Essential Oils from Apiaceae, Asteraceae, Cupressaceae and Lamiaceae Families Grown in Serbia: Comparative Chemical Profiling with In Vitro Antioxidant Activity.

The aim of the present study was to investigate the chemical profile and antioxidant activity of essential oils obtained from the most commonly grown plant species in Serbia. Aromatic and medicinal plants from Lamiaceae (Mentha x Piperita, Ocimum basilicum, Origanum majorana, Origanum vulgare, Salvia officinalis, Satureja hortensis, Satureja montana and Thymus vulgaris), Asteraceae (Ehinacea purpurea and Matricaria chamomilla), Apiaceae (Anethum graveolens, Carum carvi, Foeniculum vulgare, Petroselinum crispum and Pimpinella anisum) and Cupressaceae (Juniperus comunis) were selected as raw material for essential oils (EOs)' isolation. Hydrodistillation (HD) was used for the isolation of EOs while they were evaluated in terms of yield and terpenoid profiles by GC-MS. In vitro radical scavenging DPPH and ABTS+ radical activities were carried out for all EOs. Finally, a principal component analysis (PCA) was performed with the experimental results of the composition and antioxidant activity of the EOs, which showed a clear distinction between the selected plant species for the aforementioned responses. This work represents a screening tool for the selection of other EO candidates for further processing by emerging extraction techniques and the use of EOs as natural additives for meat products.

Dynamic Modeling Using Artificial Neural Network of Bacillus Velezensis Broth Cross-Flow Microfiltration Enhanced by Air-Sparging and Turbulence Promoter.

Cross-flow microfiltration is a broadly accepted technique for separation of microbial biomass after the cultivation process. However, membrane fouling emerges as the main problem affecting permeate flux decline and separation process efficiency. Hydrodynamic methods, such as turbulence promoters and air sparging, were tested to improve permeate flux during microfiltration. In this study, a non-recurrent feed-forward artificial neural network (ANN) with one hidden layer was examined as a tool for microfiltration modeling using Bacillus velezensis cultivation broth as the feed mixture, while the Kenics static mixer and two-phase flow, as well as their combination, were used to improve permeate flux in microfiltration experiments. The results of this study have confirmed successful application of the ANN model for prediction of permeate flux during microfiltration of Bacillus velezensis cultivation broth with a coefficient of determination of 99.23% and absolute relative error less than 20% for over 95% of the predicted data. The optimal ANN topology was 5-13-1, trained by the Levenberg-Marquardt training algorithm and with hyperbolic sigmoid transfer function between the input and the hidden layer.

Coriander essential oil as natural food additive improves quality and safety of cooked pork sausages with different nitrite levels.

The effect of coriander essential oil (CEO) at concentrations of 0.075-0.150 µL/g on pH, color, lipid oxidation (TBARS), residual nitrite concentration and microbial growth of cooked pork sausages produced with different levels of sodium nitrite (0, 50 and 100 mg/kg) was investigated. Artificial neural networks modeling and the multi-response optimization were used to determine the optimal combinations of process parameters and storage time. Reduced concentration of sodium nitrite (60 mg/kg) in combination with 0.12 µL/g of CEO resulted in satisfying redness (a* approx. 11.1) and improved oxidative (TBARS approx. 0.12 mg MDA/kg) and microbial stability (total plate count - TPC approx. 2.50 Log CFU/g) of cooked pork sausages during refrigerated storage. Therefore, the results of this paper revealed significant antioxidative and antimicrobial activity of CEO, and consequently its high potential of utilization in processing of cooked pork sausages with enhanced quality and shelf-life.

Kinetics of lactose fermentation in milk with kombucha starter.

The aim of this research was to investigate the effect of new, non-conventional starter culture on the kinetics of the lactose transformation during milk fermentation by kombucha, at pH 5.8; 5.4; 5.1; 4.8; and 4.6, at two different temperatures 37 °C and 42 °C. Milk fermentation at 42 °C lasted significantly shorter (about 5 h, 30 min) compared to the fermentation at 37 °C. Changes of lactose concentration at the both temperatures are consisting of two retaining stages and very steep decline in-between. The analysis of the rate curves showed that the reaction rate passes through the maximum after 9 h, 30 min at 37 °C and after 4 h at 42 °C. The sigmoidal saturation curve indicates a complex kinetics of lactose fermentation by kombucha starter.