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.

Kinetics of Microwave-Assisted Extraction Process Applied on Recovery of Peppermint Polyphenols: Experiments and Modeling.

The aim of this work was to investigate the microwave-assisted extraction (MAE) kinetics of polyphenolic compounds from organic peppermint leaves. The phytochemicals of peppermint (Mentha piperita L.) are increasingly used in food technology due to their numerous biological activities. The processing of various plant materials by MAE and the production of high-quality extracts is becoming increasingly important. Therefore, the influence of microwave irradiation power (90, 180, 360, 600, and 800 W) on total extraction yield (Y), total polyphenols yield (TP), and flavonoid yield (TF) were investigated. Common empirical models (first-order, Peleg's hyperbolic, Elovich's logarithmic, and power-law model) were applied to the extraction process. The first-order kinetics model provided the best agreement with the experimental results in terms of statistical parameters (SSer, R2, and AARD). Therefore, the influences of irradiation power on the adjustable model parameters (k and Ceq) were investigated. It was found that irradiation power exerted a significant influence on k, while its influence on the asymptotic value of the response was negligible. The highest experimentally determined k (2.28 min-1) was obtained at an irradiation power of 600 W, while the optimal irradiation power determined by the maximum fitting curve determination predicted the highest k (2.36 min-1) at 665 W.

Extraction of Peppermint Essential Oils and Lipophilic Compounds: Assessment of Process Kinetics and Environmental Impacts with Multiple Techniques.

Consumers are becoming more mindful of their well-being. Increasing awareness of the many beneficial properties of peppermint essential oil (EO) has significantly increased product sales in recent years. Hydrodistillation (HD), a proven conventional method, and a possible alternative in the form of microwave-assisted hydrodistillation (MWHD) have been used to isolate peppermint EO. Standard Soxhlet and alternatively supercritical fluid (SFE), microwave-assisted, and ultrasound-assisted extraction separated the lipid extracts. The distillations employed various power settings, and the EO yield varied from 0.15 to 0.80%. The estimated environmental impact in terms of electricity consumption and CO2 emissions suggested that MWHD is an energy efficient way to reduce CO2 emissions. Different extraction methods and solvent properties affected the lipid extract yield, which ranged from 2.55 to 5.36%. According to the corresponding values of statistical parameters, empiric mathematical models were successfully applied to model the kinetics of MWHD and SFE processes.

Modelling and efficiency evaluation of the continuous biosorption of Cu(II) and Cr(VI) from water by agricultural waste materials.

As a result of intensive anthropogenic activities, population growth and unplanned urbanization, enormous quantities of organic and inorganic pollutants are discharged into the environment every year. The primary hazardous substances of concern regarding their environmental load and health effects are heavy metals. Heavy metal pollution of aquatic ecosystems, including resources of drinking water and water intended for food processing, has been of increasing interest. Biosorption technology is a promising strategy, as it utilizes industrial or agricultural wastes to remove metals from aqueous media passively, and they represent efficient, cost-effective and environmentally friendly alternatives to traditional adsorbents such as activated carbon. In this paper, the efficiency of biosorption of copper and chromium ions was examined using different agricultural waste biomass - sugar beet shreds, poplar sawdust and wheat straw. The possibility of applying a parallel sigmoidal (PS) model to describe the biosorption process was investigated to confirm its applicability to different types of biomass and various kinds of heavy metal ions. The results showed that the biosorption of copper ions using poplar sawdust and wheat straw consist of two steps. The moiety of one step in the overall process, defined by the parameter p, was determined to be 0.85 for poplar sawdust and 0.86 for wheat straw. These values, being less than 1, clearly indicate that the process consists of two simultaneous, kinetically different steps that shift in their dominance over the process and thus could be successfully modelled by the PS model. These studies also deal with the phenomenological examination of an unusual breakthrough curve obtained for the chromium ions biosorption by sugar beet shreds, by the comparative view of the process flow and changing the pH of the effluent. The clarification of the appearance of a double curve with a negative trend in one part allows adjusting the biosorption conditions to avoid the initial blockage of chromium ion binding to the adsorbent and thus increase the adsorption process efficiency.

A new approach for modelling and optimization of Cu(II) biosorption from aqueous solutions using sugar beet shreds in a fixed-bed column.

The potential use of sugar beet shreds for copper ions removal from aqueous solution in a fixed-bed column was investigated. Experiments were performed using Box-Behnken experimental design on three levels and three variables: concentration of the inlet solution (50-150 mg L-1), adsorbent dosage (8-12 g) and pH of the inlet solution (4.0-5.0). The obtained breakthrough curves were fitted with two common empirical models, Bohart-Adams and dose-response. Observing the asymmetric shape of the breakthrough curves, the new mathematical model was proposed. The new model proposes the breakthrough curve composed of two parts, sum of which gives the asymmetrical S-shaped curve, accurately matching experimental data. Regarding the lowest SSer (7.8·10-4) and highest R2 (0.9998), new model exhibited the best fit comparing to the commonly used models. RSM and ANN modelling were employed for process variables evaluation and optimization. The most influential parameter exhibiting negative influence on target response (critical time) was concentration of the inlet solution, while the adsorbent dosage exhibited positive influence. Optimization procedure revealed that the highest critical time (341.4 min) was achieved at following conditions: C0 = 50 mg·L-1, ma = 12 g and pH 4.53 by ANN, while RSM considered pH as insignificant factor and obtained 314.8 min as the highest response.

Antifungal efficiency assessment of the TiO2 coating on façade paints.

The work studies the photocatalytic activity and the antifungal efficiency of the TiO2/Zn-Al coatings placed on the target commercial façade paints. The photocatalytic active nanocomposite based on TiO2 and Zn-Al-layered double hydroxides (ZnAl-LDHs) was synthesized by a wet impregnation technique with 3 % w/w TiO2. The freshly prepared suspension was applied by spray technique on the surfaces of the white façade paints. The goal of the work was to develop a method that quickly quantifies the antifungal activity of the commercial façade paints with and without biocidal components covered with a photocatalytic coating. The essence of the proposed method is the monitoring of the fungal growth (artificial ageing conditions) and the quantification of its development (UV-A 0.13 mWcm(-2)) on the façade paint surfaces. A special fungus nutrient (potato dextrose agar (PDA)) was inoculated with the spores of the Aspergillus niger ATCC 6275, and the test samples (façade paints with and without photocatalytic coating) were placed on the inoculated nutrient in the petri dishes. The images of the fungal growth on the samples of the facade paints, during a period of 5 days, were imported into Matlab R2012a where they were converted to binary images (BW), based on the adequate threshold. The percentage of the surface coverage was calculated by applying the specifically written program code which determines the ratio of the black and white pixels. The black pixels correspond to the surface covered with hyphae and mycelia of the fungus.