Polyols and Rigid Polyurethane Foams from Cashew Nut Shell Liquid

Cashew nut shell liquid (CNSL) is a natural aromatic oil consisting of a mixture of phenolic structures with a carboxyl group in ortho position and substituted in meta position with a hydrocarbon chain of 15 carbon atoms. The major component of CNSL is anacardic acid (90?%), which is easily decarboxylated to cardanol by distillation. The present work describes the synthesis of new biobased Mannich polyols for rigid polyurethane foams in two steps: synthesis of Mannich bases by reacting phenolic ring of cardanol with N-(2-hydroxyethyl)-1,3-oxazolidine followed by alkoxylation reactions. The polyols were characterized by wet methods (hydroxyl numbers, viscosity, acid value, density, water content, iodine value etc.), spectroscopic methods (FT-IR, ¹H NMR and ¹³C NMR) and by Gel Permeation Chromatography. The Mannich polyols from cardanol are excellent replacements for petrochemical derived Mannich polyols based on nonyl phenol. Cardanol-based polyols were used successfully for the preparation of rigid polyurethane foams of good physical?Cmechanical and fireproofing properties.     

Styrene/Lignin-Based Polymeric Composites Obtained Through a Sequential Mass-Suspension Polymerization Process

A modified sequential mass-suspension polymerization was employed to ensure adequate dispersion of lignin into the monomeric phase. Due to its complex macromolecular structure and low compatibility with styrene, eucalyptus wood-extracted lignin, via a modified Kraft method, was esterified with methacrylic anhydride to ensure organic phase homogeneity into the reaction medium. Infrared spectroscopy showed a decrease in the hydroxyl band, a characteristic of natural lignin (3200–3400 cm^?1) and an increase in the characteristic ester band (1720–1740 cm^?1) whereas nuclear magnetic resonance measurements exhibited intense peaks in the range from 1.7 to 2.05 ppm (–CH₃) and 5.4 to 6.2 ppm (=CH₂), related to methacrylic anhydride. Comparatively, the esterified lignin also displayed an increase of its glass transition temperature for 98?°C, related to natural lignin, whose T _g was determined to be equal to 91?°C. Styrene/lignin-based polymers exhibited higher average molar masses in comparison to the values observed for polystyrene synthesized with similar amounts of benzoyl peroxide, due to the ability of lignin to act as a free-radical scavenger. Composites obtained with styrene and natural or esterified lignin were successfully synthesized, presenting regular morphology and proper lignin dispersion. Based on a very simple polymerization system, it is possible to enhance the final properties of polystyrene through the incorporation of lignin, which represents an important platform for developing attractive polymeric materials from renewable resources.     

Preparation of Soybean Oil Polymers with High Molecular Weight

The cationic polymerization of soybean oils was initiated by boron trifluoride diethyl etherate in supercritical carbon dioxide medium. The resulting polymers had molecular weight ranging from 21,842 to 118,300 g/mol. Nuclear magnetic resonance spectroscopy and gel permeation chromatography analysis confirmed the polymerization had occurred. Parameters affecting the polymerization were studied, which included initiator amount and reaction time. Results show that the longer reaction time, up to 3 h, favored the higher molecular weight of polymers at conditions of 140 °C and initiator BF₃·OEt₂ (2.5 g, 0.018 mol). When reaction time was increased further, the molecular weight of polymers stayed the same or slightly decreased. Increased concentration of initiator gave the higher molecular weight of polymers. The high molecular weight polymers were possibly formed through two path ways: polymerization and intermolecular Diels-Alder reaction.     

Kinetic and Mechanistic Studies of NO X Selective Catalytic Reduction Over In/Al2O3 and N2O Decomposition Over Ru/Al2O3

Detailed kinetic studies are presented for two reactions: the nitric oxide (NO) selective catalytic reduction (SCR) by propene over indium/alumina (In/Al₂O₃) and the nitrous oxide (N₂O) reduction over ruthenium/alumina (Ru/Al₂O₃). Both reactions were studied in the presence of excess oxygen (O₂) to simulate the composition of flue gases. Apparent activation energies and apparent orders of reaction were calculated in experiments performed under differential reaction conditions. We used our experimental results to propose the reaction mechanism that leads to nitrogen formation over the two catalysts. The NO reduction proceeds through the initial formation of C _X H _Y O _Z N, a reaction intermediate that reacts with activated nitrogen oxides (NO _X ). Nitrous oxide is catalytically decomposed to nitrogen (N₂) over Ru/Al₂O₃.     

Formation and decomposition of tetrafluoroborate ions in the presence of aluminum

The formation and decomposition of tetrafluoroborate ions (BF₄⁻) in H₃BO₃-Al³⁺-F⁻ solutions were investigated via experiments and thermodynamic calculations. The concentration of the formed BF₄⁻ increased with decreasing pH, raising the total fluoride concentration and lowering the total aluminum ion concentration. Once formed, BF₄⁻ was stable under neutral and alkaline conditions. Fluoride in the form of BF₄⁻ was converted to fluoroaluminate ions by adding an aluminum compound under acidic conditions. A method for removing fluoride in the form of BF₄⁻ is proposed whereby fluoroaluminate ions formed by the reaction of BF₄⁻ with aluminum are decomposed with calcium ions. This process was applied to the treatment of wastewater from flue gas desulfurization plants, and resulted in a satisfying level of reduction in the range of the fluoride emission limit of 8 mg/l.     

Conjugation of Soybean Oil and It’s Free-Radical Copolymerization with Acrylonitrile

The conjugated soybean oil was synthesized through the isomerization reaction of soybean oil to transformed the structure of linoleic acid into conjugated linoleic acid structure, and Rhodium complexes (RhCl(Pph₃)₃) was used as catalyst. The efficiency on the conjugation of catalyst RhCl (Pph₃)₃, tin dichloride dehydrate (SnCl₂·2H₂O) and triphenylphosphine (Pph₃) were evaluated. The results showed when RhCl(Pph₃)₃, SnCl₂·2H₂O and Pph₃ are 9.25, 9.0 and 13.1 mg in 100 g soybean oil respectively, the highest conversion of conjugation achieved 96%. The free radical copolymerization of conjugated soybean oil with acrylonitrile (AN) and dicyclopentadiene (DCP) was studied. AIBN was used as the initiator. FT-IR and ¹H-NMR results indicates that the conjugated soybean oil with AN and DCP did occur free radical copolymerization with the initiator AIBN. The product is light yellow powder. The thermal properties of the soy-based copolymer were investigated by TG and DSC. The initial degradation temperature of polymers is higher then 250 °C.     

Assessing methane oxidation under landfill covers and its contribution to the above atmospheric CO₂ levels: the added value of the isotope (δ¹³C and δ¹⁸O CO₂; δ¹³C and δD CH₄) approach

We are presenting here a multi-isotope approach (δ¹³C and δ¹⁸O of CO₂; δ¹³C and δD of CH₄) to assess (i) the level(s) of methane oxidation during waste biodegradation and its migration through a landfill cover in Sonzay (France), and (ii) its contribution to the atmospheric CO₂ levels above the surface. The isotope approach is compared to the more conventional mass balance approach. Results from the two techniques are comparable and show that the CH₄ oxidation under the landfill cover is heterogenous, with low oxidation percentages in samples showing high biogas fluxes, which was expected in clay covers presenting fissures, through which CH₄ is rapidly transported. At shallow depth, more immobile biogas pockets show a higher level of CH₄ oxidation by the methanotrophic bacteria. δ¹³C of CO₂ samples taken at different heights (from below the cover up to 8 m above the ground level) were also used to identify and assess the relative contributions of its main sources both under the landfill cover and in the surrounding atmosphere.     

Influence of aeration on CH4, N2O and NH3 emissions during aerobic composting of a chicken manure and high C/N waste mixture

Co-composting of chicken manure, straw and dry grasses was investigated in a forced aeration system to estimate the effect of aeration rates on NH₃, CH₄ and N₂O emissions and compost quality. Continuous measurements of gas emissions were carried out and detailed gas emission patterns were obtained using an intermittent-aeration of 30 min on/30 min off at rates of 0.01 (A1), 0.1 (A2) and 0.2 (A3) m³ min⁻¹ m⁻³. Concentrations of CH₄ and N₂O at the low aeration rate (A1) were significantly greater than those at the other two rates, but there was no significant difference between the A2 and A3 treatments. CH₄ and N₂O emissions for this mixture could be controlled when the composting process was aerobic and ammonia emissions were reduced at a lower aeration rate. Comparison of CH₄, N₂O, NH₃ emissions and compost quality showed that the aeration rate of the A2 treatment was superior to the other two aeration rates.     

Spatial variability of nitrous oxide and methane emissions from an MBT landfill in operation: Strong N2O hotspots at the working face

Mechanical biological treatment (MBT) is an effective technique, which removes organic carbon from municipal solid waste (MSW) prior to deposition. Thereby, methane (CH₄) production in the landfill is strongly mitigated. However, direct measurements of greenhouse gas emissions from full-scale MBT landfills have not been conducted so far. Thus, CH₄ and nitrous oxide (N₂O) emissions from a German MBT landfill in operation as well as their concentrations in the landfill gas (LFG) were measured. High N₂O emissions of 20–200 g CO₂ eq. m^?2 h^?1 magnitude (up to 428 mg N m^?2 h^?1) were observed within 20 m of the working face. CH₄ emissions were highest at the landfill zone located at a distance of 30–40 m from the working face, where they reached about 10 g CO₂ eq. m^?2 h^?1. The MBT material in this area has been deposited several weeks earlier. Maximum LFG concentration for N₂O was 24.000 ppmv in material below the emission hotspot. At a depth of 50 cm from the landfill surface a strong negative correlation between N₂O and CH₄ concentrations was observed. From this and from the distribution pattern of extractable ammonium, nitrite, and nitrate it has been concluded that strong N₂O production is associated with nitrification activity and the occurrence of nitrite and nitrate, which is initiated by oxygen input during waste deposition. Therefore, CH₄ mitigation measures, which often employ aeration, could result in a net increase of GHG emissions due to increased N₂O emissions, especially at MBT landfills.     

Decomposition of dichloromethane and in situ alkali absorption of resulting halogenated products by a packed-bed non-thermal plasma reactor

For an effective decomposition and removal of organic halogenated compounds, a packed-bed non-thermal plasma reactor with in situ absorption of the resulting halogenated products by alkaline sorbent incorporated was proposed. In the plasma reactor, α-Al₂O₃ particles of 1 and 3 mm (mean particle diameter) were packed as solid dielectric medium to enhance the plasma power density in the reactor. Further, alkaline sorbent of Ca(OH)₂ was doped onto the surface of α-Al₂O₃ particles, in order to remove halogenated products by in situ absorption with Ca(OH)₂. A high-voltage and high-frequency pulsed power of −15 to 15 kV and 1 kHz was applied to the wire electrode of the plasma reactor by means of a DC power source. In the present study, as the sample of an organic halogenated compound that is most popularly used, we selected dichloromethane (CH₂Cl₂), and 500 ppm of the initial concentration of CH₂Cl₂ was fed into the reactor accompanied by air at a fixed flow rate of 500 × 10⁻⁶ m³ min⁻¹ at room temperature. As a result, it was recognized that the amount of CH₂Cl₂ decomposed by non-thermal plasma in an α-Al₂O₃ particle bed increased with an increase in plasma input power. The ratio of decomposition of CH₂Cl₂ was almost 100% at 13 kV of electric power and 1 kHz frequency, and CO₂, CH₃Cl, COCl₂, HCl, and Cl₂ were observed as the major reaction products. On the other hand, when CH₂Cl₂ was introduced into the plasma reactor where α-Al₂O₃ particles doped with Ca(OH)₂ were packed, the ratio of decomposition of CH₂Cl₂ became higher, compared to the case that α-Al₂O₃ particles were not doped with Ca(OH)₂. Moreover, there were no halogenated by-product gases detected in the outlet gas from the reactor. As the solid reaction products, CaClOH and Ca(ClO)₂·4H₂O were detected on Ca(OH)₂ by X-ray diffraction. From these findings, it was recognized that CH₂Cl₂ was decomposed more effectively without producing unwanted harmful halogenated by-products in the proposed non-thermal plasma reactor where α-Al₂O₃ particles doped with Ca(OH)₂ sorbent were packed.     

Gasification characteristics of sewage sludge combined with wood biomass

The gas products from gasification processes have been considered to have some limitations in gas composition and heating value from the previous studies. Gasification characteristics of sewage sludge and wood mixture were investigated using different mixing ratios with the purpose of better quality of gas product suitable for energy/power generation. The gasification experiment was performed by an indirectly heated fluidized bed reactor. As reaction temperature increased from 600 to 900 °C, the yield of gas product increased with higher generation of CO, H₂ and CH₄ by more activated gas conversion reactions. As the equivalence ratio increased from 0.2 to 0.4, composition ratio of CO₂ increased while CO, CH₄, H₂ decreased as expected. Several operating variables including mixing ratio of wood with dried sludge were also tested. From this initial stage of experiment, optimal operating conditions for the bubbling fluidized bed gasifier, could be considered 900 °C in temperature; 0.2 in equivalence ratio and 40 % in wood mixing ratio within test variables range. These results will be more thoroughly investigated for the application to the larger scale pilot system.     

Emissions of ammonia and greenhouse gases during combined pre-composting and vermicomposting of duck manure

Combined pre-composting and vermicomposting has shown potential for reclamation of solid wastes, which is a significant source of ammonia (NH₃), and greenhouse gases (GHG), including nitrous oxide (N₂O), methane (CH₄), and carbon dioxide (CO₂). Earthworms and amendments may both affect physico-chemical characteristics that control gas-producing processes, and thus affect NH₃ and GHG emissions. Here, we used two-way ANOVA to test the effects of addition of reed straw and combined addition of reed straw and zeolite on NH₃ and GHG emissions during pre-composting of duck manure, either with or without a follow-up phase of vermicomposting. Results showed that cumulative N₂O, CH₄, and CO₂ emissions during pre-composting and vermicomposting ranged from 92.8, 5.8, and 260.6 mg kg^?1 DM to 274.2, 30.4, and 314.0 mg kg^?1 DM, respectively. Earthworms and amendments significantly decreased N₂O and CH₄ emissions. Emission of CO₂ was not affected by earthworms, but increased in responses to addition of reed straw. Cumulative NH₃ emission ranged from 3.0 to 8.1 g kg^?1 DM, and was significantly decreased by reed straw and zeolite addition. In conclusion, combined pre-composting and vermicomposting with reed straw and zeolite addition would be strongly recommended in mitigating emissions of N₂O, CH₄, and NH₃ from duck manure. Moreover, this method also provides nutrient-rich products that can be used as a fertilizer.     

Gas production, composition and emission at a modern disposal site receiving waste with a low-organic content

AV Miljø is a modern waste disposal site receiving non-combustible waste with a low-organic content. The objective of the current project was to determine the gas generation, composition, emission, and oxidation in top covers on selected waste cells as well as the total methane (CH₄) emission from the disposal site. The investigations focused particularly on three waste disposal cells containing shredder waste (cell 1.5.1), mixed industrial waste (cell 2.2.2), and mixed combustible waste (cell 1.3). Laboratory waste incubation experiments as well as gas modeling showed that significant gas generation was occurring in all three cells. Field analysis showed that the gas generated in the cell with mixed combustible waste consisted of mainly CH₄ (70%) and carbon dioxide (CO₂) (29%) whereas the gas generated within the shredder waste, primarily consisted of CH₄ (27%) and nitrogen (N₂) (71%), containing no CO₂. The results indicated that the gas composition in the shredder waste was governed by chemical reactions as well as microbial reactions. CH₄ mass balances from three individual waste cells showed that a significant part (between 15% and 67%) of the CH₄ generated in cell 1.3 and 2.2.2 was emitted through leachate collection wells, as a result of the relatively impermeable covers in place at these two cells preventing vertical migration of the gas. At cell 1.5.1, which is un-covered, the CH₄ emission through the leachate system was low due to the high gas permeability of the shredder waste. Instead the gas was emitted through the waste resulting in some hotspot observations on the shredder surface with higher emission rates. The remaining gas that was not emitted through surfaces or the leachate collection system could potentially be oxidized as the measured oxidation capacity exceeded the potential emission rate. The whole CH₄ emission from the disposal site was found to be 820 ± 202 kg CH₄ d⁻¹. The total emission rate through the leachate collection system at AV Miljø was found to be 211 kg CH₄ d⁻¹. This showed that approximately ¼ of the emitted gas was emitted through the leachate collections system making the leachate collection system an important source controlling the overall gas migration from the site. The emission pathway for the remaining part of the gas was more uncertain, but emission from open cells where waste is being disposed of or being excavated for incineration, or from horizontal leachate drainage pipes placed in permeable gravel layers in the bottom of empty cells was likely.     

Effect of additives on dechlorination of PVC by mechanochemical treatment

Polyvinyl chloride (–CH₂–CHCl–) _n (PVC) was ground with a powdered inorganic material (CaO, CaCO₃, SiO₂, Al₂O₃, or slag) in a planetary ball mill under atmospheric conditions to investigate the effect of additions on its dechlorination. The grinding causes a dehydrochlorinating reaction, forming a mixture of partially dechlorinated PVC and inorganic chloride, depending on the grinding time. The dechlorination increases as the grinding progresses, and is improved with increasing amounts of additives. The most effective additive is a mixture of CaO, SiO₂, and Al₂O₃, which has the same constituent components as blast furnace slag. CaO, a mixture of CaO, SiO₂, and blast furnace slag, are also effective, but CaCO₃ is the least effective additive tired. Received: August 3, 2000 / Accepted: September 21, 2000     

Determination of nitrous oxide, methane, and ammonia emissions from a swine waste composting process

The amounts of harmful gas emissions from the process of composting swine waste were determined using an experimental composting apparatus. Forced aeration (19.2–96.1 l/m³/min) was carried out continuously, and exhaust gases were collected and analyzed periodically. With weekly turning and the addition of a bulking agent in order to decrease the moisture content and increase air permeability, the temperature of most of the contents rose to 70°C and composting was complete within 3–5 weeks. NH₃, CH₄, and N₂O emissions were high in the early stage of composting. About 10%–25% of the nitrogen in the raw material was lost as NH₃ gas during composting. The emission rate of NH₃ mainly depended on the aeration rate, so that as the aeration rate rose, the level of NH₃ emissions increased. The CH₄ and N₂O emissions could be kept lower with adequate treatment at more than 40 l/m³/min aeration. N₂O may be mainly the result of the denitrification of NO _x -N in the additional matured compost used as a composting accelerator. Received: September 11, 1998 / Accepted: November 8, 1999     

The Effect of Chain Extender on Poly(3-hydroxybutyrate-co-3-hydroxyvalerate): Thermal Degradation,Crystallization, and Rheological Behaviours

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), a semi-polycrystalline biopolymer from the polyhydroxyalkanonate family has in recent years become a commercial bioplastic with mechanical properties comparable to isotactic polypropylene and enhanced O₂, CO₂ and H₂O barrier properties. However, its brittleness and sensitivity to thermal and hydrolysis degradations restrict its applications. To overcome the problems associated with degradation during processing blending of PHBV and an epoxy-functionalized chain extender (Joncryl^® ADR-4368 S) was conducted in a twin screw extruder. The effect of concentration of the chain extender on thermal, crystallization and rheological behaviours of PHBV was investigated. Thermal gravimetric analysis results indicated improvement in the resistance to thermal decomposition of PHBV by introducing the chain extender. This was accompanied with calculation of thermal degradation activation energy (E_a) using the Flyn–Walls–Ozawa method which confirmed increase of E_a with the increase in content of the chain extender. The rheological behaviour and crystallization of modified PHBV was characterized by rotational rheometry and differential scanning calorimetry techniques, respectively. The results show that addition of chain extender enhanced viscosity of PHBV and also reduce the rate of crystallization.     

Quantification of multiple methane emission sources at landfills using a double tracer technique

A double tracer technique was used successfully to quantify whole-site methane (CH₄) emissions from Fakse Landfill. Emissions from different sections of the landfill were quantified by using two different tracers. A scaled-down version of the tracer technique measuring close-by to localized sources having limited areal extent was also used to quantify emissions from on-site sources at the landfill facility, including a composting area and a sewage sludge storage pit. Three field campaigns were performed. At all three field campaigns an overall leak search showed that the CH₄ emissions from the old landfill section were localized to the leachate collection wells and slope areas. The average CH₄ emissions from the old landfill section were quantified to be 32.6 ± 7.4 kg CH₄ h⁻¹, whereas the source at the new section was quantified to be 10.3 ± 5.3 kg CH₄ h⁻¹. The CH₄ emission from the compost area was 0.5 ± 0.25 kg CH₄ h⁻¹, whereas the carbon dioxide (CO₂) and nitrous oxide (N₂O) flux was quantified to be in the order of 332 ± 166 kg CO₂ h⁻¹ and 0.06 ± 0.03 kg N₂O h⁻¹, respectively. The sludge pit located west of the compost material was quantified to have an emission of 2.4 ± 0.63 kg h⁻¹ CH₄, and 0.03 ± 0.01 kg h⁻¹ N₂O.     

Extension of EU Emissions Trading Scheme to Other Sectors and Gases: Consequences for Uncertainty of Total Tradable Amount

Emissions trading in the European Union (EU), covering the least uncertain emission sources of greenhouse gas emission inventories (CO₂ from combustion and selected industrial processes in large installations), began in 2005. During the first commitment period of the Kyoto Protocol (2008–2012), the emissions trading between Parties to the Protocol will cover all greenhouse gases (CO₂, CH₄, N₂O, HFCs, PFCs, and SF₆) and sectors (energy, industry, agriculture, waste, and selected land-use activities) included in the Protocol. In this paper, we estimate the uncertainties in different emissions trading schemes based on uncertainties in corresponding inventories. According to the results, uncertainty in emissions from the EU15 and the EU25 included in the first phase of the EU emissions trading scheme (2005–2007) is ±3% (at 95% confidence interval relative to the mean value). If the trading were extended to CH₄ and N₂O, in addition to CO₂, but no new emissions sectors were included, the tradable amount of emissions would increase by only 2% and the uncertainty in the emissions would range from −4 to +8%. Finally, uncertainty in emissions included in emissions trading under the Kyoto Protocol was estimated to vary from −6 to +21%. Inclusion of removals from forest-related activities under the Kyoto Protocol did not notably affect uncertainty, as the volume of these removals is estimated to be small.     

Synthesis and Properties of Poly(d,l-lactide-co-p-dioxanone) Random and Segmented Copolymers

Two different polymerization routes, one-step and two-step bulk ring-opening polymerizations of d,l-lactide (LA) and p-dioxanone (PDO) monermers using stannous octoate [Sn(Oct)₂]/n-dodecanol as the initiating system, were employed to synthesize poly(d,l-lactide-co-p-dioxanone) P(LA-co-PDO) random and segmented copolymers with different compositions and chain microstructure. For the two-step copolymers, the average sequence lengths of the lactidyl (L_LA) and dioxanyl (L_PDO) units calculated from the ¹H-NMR spectra were much longer than those values for the one-step copolymers with the same LA/PDO feed ratio. Corresponding to this difference in microstructure, the two-step copolymers were semi-crystalline even when the PDO content was as low as 14.5 mol%, while the one-step copolymers were completely amorphous with PDO content below 60.6 mol%. However, irrespective of polymerization route, both types of copolymers displayed a single glass transition temperature that was in a linear relation with composition. The decrease of maximum decomposition temperature of the copolymers was in accordance with the decrease of L_PDO value. The mechanical and degradation properties of the copolymers were significantly affected by both the polymerization route and the chemical composition as well. In conclusion, the properties of P(LA-co-PDO) copolymers could be adjusted conveniently to meet specific applications by changing the composition and microstructure of the copolymers via different polymerization routes.     

Biosynthesis and Characterization of Poly-(3-hydroxybutyrate-co-3-hydroxyvalerate) from Bacillus cereus S10

The biodegradable and biocompatible copolymer poly-(3-hydroxybutyrate-co-5 mol% 3-hydroxyvalerate), poly-(3HB-co-5 mol% 3HV), was synthesized by Bacillus cereus S10 and the highest yield was determined as 69.91 % at pH 7 and 30 °C after 48 h of incubation using a glucose as the sole carbon source. Poly-(3HB-co-5 mol% 3HV) was purified from bacterial biomass using chloroform. FTIR analysis showed absorption bands at 1,723, 1,274, 1,373, 1,453, 2,932 cm^?1 corresponding to C=O, C–O stretching, CH₃, –CH₂ and –CH groups, respectively. ¹H-NMR and ¹³C-NMR analysis confirmed that the copolymer was composed of 95 mol% of 3-hydroxybutrate and 5 mol% of 3-HV monomeric units. Poly-(3-HB-co-5 mol% 3HV) was used for nanoparticles preparation. The diameter of nanoparticles was 202 nm.