Volume 17 (2015): Issue 4 (December 2015)

β-cyclodextrin (β-CD) and its derivatives have been widely used to prepare inclusion complexes. However, systematic research on their thermal stabilities, pyrolysis characteristics and kinetics has rarely been reported. In this paper, thermogravimetric analysis was employed to investigate β-cyclodextrin and its two derivatives, 2-Hydroxypropyl-β-cyclodextrin (HP-β-CD) and monochlorotriazinyl-β-cyclodextrin (MCT-β-CD). The pyrolysis characteristics and kinetic parameters were obtained. The results show that three stages can be distinguished during the heating process of the above three samples. The temperature of initial decomposition of HP-β-CD (309.5°C is higher than that of β-CD (297.8°C), while the temperature of initial decomposition of MCT-β-CD (231.4°C) is lower than that of β-CD. For the three cyclodextrins, the thermal stability in descending order is HP-β-CD, β-CD and MCT-HP-β-CD. The activation energy values are 350.6, 303.3 and 113.9 KJ/mol, and the pre-exponential factor values are 1.11×10³¹, 1.37×10²⁶ and 1.39×10¹⁰ for β-CD, HP-β-CD and MCT-β-CD respectively.

Sewage sludge was dried in a rotary drum dryer under superheated steam. Particle size and moisture content were shown to have significant influences on sticking and agglomeration of the materials. Pouring partially dried sludge (70–80% moisture content, wet basis) directly into the screw feeder of the drum dryer resulted in a significant sticking to the surface of the drum and the final particle size of the product was greater than 100 mm in diameter. The moisture content of this product was slightly less than its initial value. To overcome this issue, the sludge was mixed with lignite at variety ratios and then chopped before being introduced to the feeding screw. It was found that mixing the sludge with lignite and then sieving the chopped materials through a four millimetre mesh sieve was the key to solve this issue. This technique significantly reduced both stickiness and agglomeration of the material. Also, this enabled for a significant reduction in moisture content of the final product.

Standards for highly toxic and carcinogenic pollutants impose strict guidelines, requiring values close to zero, regarding the degradation of such pollutants in industrial streams. In many cases, classic bioremoval processes fail. Therefore, we proposed a stream leaving the microbial membrane bioreactor (MBR) that is directed to an additional membrane separation mode (NF/RO). Under certain conditions, the integrated process not only benefits the environment but may also increase the profitability of the bioreactor operation. An appropriate model was developed and tested in which the bioremoval of benzene and toluene by Pseudomonas fluorescens was used as an example. This paper presents equations for selecting the operation parameters of the integrated system to achieve the expected degree of industrial wastewater purification.

This work presents the studies on the optimization the process of allyl alcohol epoxidation over the Ti-SBA-15 catalyst. The optimization was carried out in an aqueous medium, wherein water was introduced into the reaction medium with an oxidizing agent (30 wt% aqueous solution of hydrogen peroxide) and it was formed in the reaction medium during the processes. The main investigated technological parameters were: the temperature, the molar ratio of allyl alcohol/hydrogen peroxide, the catalyst content and the reaction time. The main functions the process were: the selectivity of transformation to glycidol in relation to allyl alcohol consumed, the selectivity of transformation to diglycidyl ether in relation to allyl alcohol consumed, the conversion of allyl alcohol and the selectivity of transformation to organic compounds in relation to hydrogen peroxide consumed. The analysis of the layer drawings showed that in water solution it is best to conduct allyl alcohol epoxidation in direction of glycidol (selectivity of glycidol 54 mol%) at: the temperature of 10–17°C, the molar ratio of reactants 0.5–1.9, the catalyst content 2.9–4.0 wt%, the reaction time 2.7–3.0 h and in direction of diglycidyl ether (selectivity of diglycidyl ether 16 mol%) at: the temperature of 18–33°C, the molar ratio of reactants 0.9–1.65, the catalyst content 2.0–3.4 wt%, the reaction time 1.7–2.6 h. The presented method allows to obtain two very valuable intermediates for the organic industry.

The aim of this study was to encapsulate, L-ascorbic acid, in biopolymers in order to obtain (i) enhancing its encapsulation efficiency (ii) increasing drug release ratio using different pH mediums. Microparticles based on polycaprolactone, polyethylene glycol and casein are prepared by spray drying technique. Microparticles are in vitro characterized in terms of yield of production, particle size, morphology, encapsulation efficiency, and drug release. In this manner, the importance of the study is producing of a stable and effective drug encapsulation system by PCL-PEG-CS polymer mixture by spray dryer. We achieved minimum 27.540±0.656 μm particle size with 0.512 m²/g surface area, 84.05% maximum drug loading, and 68.92% drug release ratio at pH 9.6. Release profiles are fitted to previously developed kinetic models to differentiate possible release mechanisms. The Korsmeyer–Peppas model is the best described each release scenario, and the drug release is governed by non-Fickian diffusion at pH 9.6. Our study proposed as an alternative or adjuvants for controlling release of L-ascorbic acid.

A carbon-based solid acid catalyst was prepared by the sulfonation of carbonized seed shells of Jatropha curcas (J. curcas L.). The structure of amorphous carbon consisting of polycyclic aromatic carbon sheets attached a high density of acidic SO₃H groups (2.0 mmol · g⁻¹) was identified with scanning electron microscopy (SEM), fourier transform infrared (FTIR) spectroscopy, powder X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The performance of the solid acid catalyst was evaluated for biodiesel production in the esterification of oleic acid with methanol. 95.7% yield of biodiesel was obtained after 2 h reaction and the conversions with reused catalyst varied in the range of 95.7% to 95.1%, showing better activity and stability than commercial catalyst amberlyst-46. It was also observed that the prepared catalyst showed enhanced activity in the transesterification of triolein with methanol when compared with other solid acid catalysts. A synergistic effect results from the high density of SO₃H groups and the good access of reactants to the acidic sites can be used to explain the excellent catalytic activity, as well as the strong affinity between the hydrophilic reactants and the neutral OH groups bonded to the polycyclic aromatic carbon rings.

The present case study is focused on performance evaluation of a Reverse Osmosis (RO) membrane based pilot plant to treat the ground/surface drinking water sources polluted by flood, rivers and/or canals. The RO plant was designed, fabricated and then operated with polluted water. Two feed water samples having a TDS of 2.000 mg · L⁻¹ and 10.000 mg · L⁻¹ respectively, were taken and analyzed for physical, chemical and microbiological contaminants. The RO plant was run once through over a span of 100 hrs at an operating pressure of 15 bar. TDS rejections were found to be more than 94% while permeate flux was measured to be 25.82 L · m⁻² · hr⁻¹ to 40.55 L · m⁻² · hr⁻¹. Results show that RO plant has a potential to remove physical, chemical and microbiological contaminants like Total Coliform and E. Coli in one step.

This research emphasizes eloquently on membrane technology for treatment of palm oil mill effluent (POME) as it is the Malaysia’s largest and most important agro based industry. Findings established significant quality improvement with an efficient recovery of water from palm oil mill via innovative membrane application. Conventional bio-methods, whilst adhering to the Department of Environment’s (DOE) discharge regulations, produces brownish liquid which pales in comparison to the crystal clear water obtained through membrane treatment. The pre-treatment process consists of coagulation-flocculation using green environmental coagulant bases such as Moringa oleifera (MO) seeds. The ultrafiltration polyvinylidene difluoride (PVDF) and thin film composite (TFC) reverse osmosis were vital for the membrane processes. The system gave 99% suspended solids reduction in suspended solid and 78% of water present was successfully recovered. This technology guarantees water recovery with drinking water quality; meeting the US Environmental Protection Agency (USEPA) standard or could be recycled into the plant with sludge utilization for palm oil estates, thus enabling the concept of zero discharge to be executed in the industries. In addition, green and healthy antioxidants such as oil and beta-carotene can be recovered from POME further demonstrate. Silica gel showed better performance in separation of carotenes from oil at temperature 40°C using adsorption chromatography with 1154.55 ppm. The attractiveness of this technology, enabling the utilization of reuse of agricultural waste into potentially value added products.

In this work a fouling study of polypropylene membranes used for microfiltration of glycerol solutions fermented by Citrobacter freundii bacteria was presented. The permeate free of C. freundii bacteria and having a turbidity in the range of 0.72–1.46 NTU was obtained. However, the initial permeate flux (100–110 L/m²h at 30 kPa of transmembrane pressure) was decreased 3–5 fold during 2–3 h of process duration. The performed scanning electron microscope observations confirmed that the filtered bacteria and suspensions present in the broth formed a cake layer on the membrane surface. A method of periodical module rinsing was used for restriction of the fouling influence on a flux decline. Rinsing with water removed most of the bacteria from the membrane surface, but did not permit to restore the initial permeate flux. It was confirmed that the irreversible fouling was dominated during broth filtration. The formed deposit was removed using a 1 wt% solution of sodium hydroxide as a rinsing solution.

Air dry potato starch (84.9% d.s.) was subjected to pressurizing under the pressure of 50, 100, 250, 500, 750, 1000 and 2000 MPa for 1 h. The physical properties of pressurized starch, such as morphology, surface and crystalline structure, gelatinization parameters, were studied by means of scanning and atomic force microscopy (SEM/AFM), X-ray diffraction (X-ray), differential scanning calorimetry (DSC). The susceptibility to the amylolytic enzyme (α-amylase) was also measured. Application of pressure in the range of 50–2000 MPa results in an increase in the compressed potato starch bulk density, change in the contours of the granules from oval to polyhedral, increase in the roughness of the granule surface, vanishing of the X-ray reflexes generated by the orthogonal structure and weakening of the reflexes generated by the hexagonal structure, lowering of the enthalpy of starch gelatinization, and the enhancement of hydrolytic susceptibility of starch granules to the amylolytic enzyme.

This paper presents a comparative study on which type of platelets nanofiller, organic or inorganic, will affect the properties of thermoplastic elastomer matrix in the stronger manner. Therefore, poly(trimethylene terephthalate-block-poly(tetramethylene oxide) copolymer (PTT-PTMO) based nanocomposites with 0.5 wt.% of clay (MMT), graphene nanoplatelets (GNP) and graphene oxide (GO) have been prepared by in situ polymerization. The structure of the nanocomposites was characterized by transmission electron microscopy (TEM) in order to present good dispersion without large aggregates. It was indicated that PTT-PTMO/GNP composite shows the highest crystallization temperature. Unlike the addition of GNP and GO, the introduction of MMT does not have great effect on the glass transition temperature of PTMO-rich soft phase. An addition of all three types of nanoplatelets in the nanocomposites caused the enhancement in tensile modulus and yield stress. Additionally, the cyclic tensile tests showed that prepared nanocomposites have values of permanent set slightly higher than neat PTT-PTMO.

This work presents the studies on the oxidation of limonene with hydrogen peroxide and tert-butyl hydroperoxide (TBHP) in the presence of : TS-2, Ti-Beta, Ti-MCM-41 and Ti-MWW catalysts, at the autogenic pressure and atmospheric pressure. The examination were performed at the following conditions: the temperature of 140°C (studies in the autoclave) and 80°C (studies in glass reactor), the molar ratio of limonene/oxidant (H₂O₂ or WNTB) = 1:1, the methanol concentration 80 wt%, the catalyst content 3 wt%, the reaction time 3 h and the intensity of stirring 500 rpm. The analysis of the results showed that in process not only 1,2-epoxylimonene was formed but also: 1,2-epoxylimonene diol, carveol, carvone and perillyl alcohol but for 1,2-epoxylimonene obtaining the better method was the method at the autogenic pressure and in the presence of TBHP.

In this study, thermally reduced graphene oxide (TRG)-containing polyurethane nanocomposites were obtained by the extrusion method. The content of TRG incorporated into polyurethane elastomer systems equaled 0.5, 1.0, 2.0 and 3.0 wt%. The morphology, static and dynamic mechanical properties, and thermal stability of the modified materials were investigated. The application of TRG resulted in a visible increase in material stiffness as confirmed by the measurements of complex compression modulus (E′) and glass transition temperature (T_g). The T_g increased with increasing content of nanofiller in the thermoplastic system. The addition of thermally reduced graphene oxide had a slight effect on thermal stability of the obtained materials. The incorporation of 0.5, 1.0, 2.0 and 3.0 wt% of TRG into a system resulted in increased char residues compared to unmodified PU elastomer. Also, this study demonstrated that after exceeding a specific amount of TRG, the physicomechanical properties of modified materials start to deteriorate.

Graphene – novel 2D material, which possesses variety of fascinating properties, can be considered as a convenient support material for the nanoparticles. In this work various methods of synthesis of reduced graphene oxide with metal or metal oxide nanoparticles will be presented. The hydrothermal approach for deposition of platinum, palladium and zirconium dioxide nanoparticles in ethylene glycol/water solution was applied. Here, platinum/reduced graphene oxide (Pt/RGO), palladium/reduced graphene oxide (Pd/RGO) and zirconium dioxide/reduced graphene oxide (ZrO₂/RGO) nanocomposites were prepared. Additionally, manganese dioxide/reduced graphene oxide nanocomposite (MnO₂/RGO) was synthesized in an oleic-water interface. The obtained nanocomposites were investigated by transmission electron microscopy (TEM), X-ray diffraction analysis (XRD), Raman spectroscopy and thermogravimetric analysis (TGA). The results shows that GO can be successfully used as a template for direct synthesis of metal or metal oxide nanoparticles on its surface with a homogenous distribution.

The aim of the work presented in the article was to clarify controversial comments about anti-corrosion and mechanical properties of graphene coatings, deposited on copper substrates. It was designed special experimental cycle comprising: preparation of graphene forms and copper, the observation of layers Cu / GO (rGO) after the thermal reduction processes and oxidative test in air at 150°C temperature and 350 h in time. The resulting coatings and graphene layers were subjected to tribological test for hardness. The observed differences in the continuity of the coverage copper surface by graphene forms, allowed to understand the macroscopic effect of increased hardness and wear resistance layers rGO/Cu.

The aim of the experimental research studies was to determine some electrical properties of graphite oxide and thermally exfoliated/reduced graphene oxide. The authors tried to interpret the obtained physicochemical results. For that purpose, both resistance measurements and investigation studies were carried out in order to characterize the samples. The resistance was measured at various temperatures in the course of composition changes of gas atmospheres (which surround the samples). The studies were also supported by such methods as: scanning electron microscopy (SEM), Raman spectroscopy (RS), atomic force microscopy (AFM) and thermogravimetry (TG). Moreover, during the experiments also the elemental analyses (EA) of the tested samples (graphite oxide and thermally exfoliated/reduced graphene oxide) were performed.

In this paper we report a study on influence of radio-frequency (RF) plasma induced with electron cyclotron resonance (ECR) on multiblock copolymer containing butylene terephthalate hard segments (PBT) and butylene dilinoleate (BDLA) soft segments. The changes in thermal properties were studied by DSC. The changes in wettability of PBT-BDLA surfaces were studied by water contact angle (WCA). We found that ECR-RF plasma surface treatment for 60 s led to decrease of WCA, while prolonged exposure of plasma led to increase of WCA after N₂ and N₂O₂ treatment up to 70°–80°. The O₂ reduced the WCA to 50°–56°. IR measurements confirmed that the N₂O₂ plasma led to formation of polar groups. SEM investigations showed that plasma treatment led to minor surfaces changes. Collectively, plasma treatment, especially O₂, induced surface hydrophilicity what could be beneficial for increased cell adhesion in future biomedical applications of these materials.

Two series of functionalised carbonaceous adsorbents were prepared by means of oxidation and nitrogenation of commercially available activated carbon and multi-walled carbon nanotubes. The effect of nitrogen and oxygen incorporation on the textural, surface, thermal and sorption properties of the adsorbents prepared was tested. The materials were characterized by elemental analysis, low-temperature nitrogen sorption, thermogravimetric study and determination of the surface oxygen groups content. Sorptive properties of the materials obtained were characterized by the adsorption of methylene and alkali blue 6B as well as copper(II) ions. The final products were nitrogen- and oxygen-enriched mesoporous adsorbents of medium-developed surface area, showing highly diverse N and O-heteroatom contents and acidic-basic character of the surface. The results obtained in our study have proved that through a suitable choice of the modification procedure of commercial adsorbents it is possible to produce materials with high sorption capacity towards organic dyes as well as copper(II) ions.

A new CaCO₃-SiO₂ composite with core-shell structure was successfully prepared by mechano-chemistry method (MCM). SEM and FTIR indicated that SiO₂ particles were homogeneously immobilized on the surface of CaCO₃. The well dispersion of this CaCO₃-SiO₂ composite into silicone rubber can not only reduce the usage amount of SiO₂, but also improve the mechanical properties of silicone rubber. By the calculation, the theoretical numbers of the SiO₂ particles is about 10 times as large as that of CaCO₃ particles in the CaCO₃-SiO₂ composite. Mixing CaCO₃-SiO₂ composite in silicone rubber can enhance the breaking strength of the silicone rubber about 18% as high as that when mixing the pure SiO₂. And the elongation at break is about 14% less than that of adding the pure SiO₂ sample.

New polyols were synthesized with 2-hydroxypropane-1.2.3-tricarboxylic acid and butane-1,4-diol (1.4-BD). The synthesis was performed using different catalysts in the amount of 0.1%. Used catalyst: Tyzor TPT, tin(II) acetate, sulfuric(IV) acid. The fourth reaction was conducted without the use of a catalyst. The polyols’ properties were evaluated with regards to the usefulness in rigid polyurethane-polyisocyanurate (PUR-PIR) foams (acid value, density, pH and solubility, FTIR spectra). Based on the research, it was evaluated that only the polyol synthesized using Tyzor TPT (E6) was useful in production of rigid PUR-PIR foams. Its hydroxyl number was 496 mgKOH/g and its viscosity was about 14 552 mPa · s. A series of five foams P6.1–P6.5 was produced with this polyol. Rigid foams test results indicated that the amount of this compound in the foam substantially affects its compressive strength, density and their retention. The foams have low brittleness values.