Fabrications of hybrid Polyurethane-Pd doped ZrO2 smart carriers for self-healing high corrosion protective coatings.

The work demonstrates the effective utilization of hybrid Polyurethane - palladium doped zirconium oxide (Pd-ZrO2) as innovative carriers for corrosion protection coatings on steel materials. ZrO2 and Pd-ZrO2 nanoparticles were successfully synthesized using Photodeposition followed by the hydrothermal synthesis method. The synthesized nanoparticles were then incorporated into the polyurethane matrix and characterized using Fourier-transform infrared spectroscopy and scanning electron microscopy (SEM). The FTIR and SEM confirm the presence of ZrO2 and Pd-ZrO2 nanoparticles and their morphologies in polyurethane composites material. The thermogravimetric analysis (TGA) results indicated that the polyurethane matrix remained stable up to 250 °C. At 800 °C, >50% of residues are observed for Pd-ZrO2 - polyurethane in the TGA analysis, which confirms that the primer and nanoparticles addition enhances the thermal stability of the composite. The water contact angle measurement explains the hydrophobic behavior of nanocomposite modified coatings on a mild steel substrate. It indicates that Pd-ZrO2 and primer significantly increase the hydrophobicity of polyurethane. The major advantages of developing water-repellent or hydrophobic surfaces open up a world of possibilities for metals and alloys in terms of corrosion prevention. Electrochemical impedance spectroscopy (EIS) and a salt spray test were used to determine the anti-corrosion behavior of the prepared polymer nanocomposites. The polymer nanocomposite coatings have better anti-corrosive capabilities when compared to pure polyurethane. The corrosion protection efficiency increased from 76.63% to 97.57% upon incorporating 2 wt % of Pd-ZrO2 in the polyurethane matrix. The results confirmed that the modifications on the polyurethane enhanced the hydrophobicity and anti-corrosion properties of the polymer nanocomposite coatings.

Spatio-temporal variation and sensitivity analysis of aerosol particulate matter during the COVID-19 phase-wise lockdowns in Indian cities.

At the pandemic of COVID-19, the movement of business and other non-essential activities were majorly restricted at the end of March 2020 in India and continued in different lockdown phases until June 2020. By categorically, studying sensitivity towards anthropogenic factors with other environmental implications in urban Indian cities during phase-wise lockdown scenarios will pave the way for a refined Clean Air Programme (CAP). In this study, the aerosol particulate matter variations between the lockdown phases in both spatial and temporal scales have been explored along with cities exceeding national ambient air quality (NAAQ) standards covering different geographical regions of India for their air quality level. The results of the spatial pattern of Copernicus Atmosphere Monitoring System (CAMS) near-real-time data showed a negative change both in Aerosol Optical Depth (AOD) (-0.2 to 0.1) and black carbon AOD (bcAOD) (-0.9 to -0.75). The changes were evident in successive phases of lockdown with an overall AOD reduction of about 70-90%. Southern urban cities showed a significant impact of mobile sources from temporal analysis than other cities. Principal Component Analysis (PCA) for effects of pollutants by anthropogenic factors (mobile and point source) and meteorological factors (wind speed, wind direction, solar radiation, relative humidity) revealed the two significant driving factors. PM reduction was about 50-70%, predominantly due to anthropogenic factors. The factor analysis revealed the influence of meteorological factors between the major urban cities (Delhi, Kolkata, Mumbai, Chennai, Bengaluru, and Hyderabad). Cities that exceed NAAQ standard performed well during phase-wise lockdowns, exceptional to cities in Gangetic plain. This study helps to frame region-specific strategic action plans for the CAP.

Alkyl amine and vegetable oil mixture-a viable candidate for CO2 capture and utilization.

In this present work, the absorption of CO2 in alkyl amines and vegetable oil mixture has been evaluated. The results showed that the absorption is higher in alkyl amines and vegetable oil mixture compared with the aqueous alkyl amines. In addition to that, by employing the greener and non-toxic vegetable oil media, the CO2 gas has been captured as well as converted into value-added products, such as carbamates of ethylenediamine, diethylenetriamine, and triethylenetetramine. The carbamates have been isolated and characterized by Fourier transform infrared and 1H and 13C nuclear magnetic resonance spectroscopic techniques. The formation of these products in precipitate form has not been observed in the case of aqueous medium. Among the various alkyl amine and vegetable oil combinations, triethylenetetramine in coconut oil medium showed the maximum CO2 capture capacity of 72%. The coconut oil used for the process has been recovered, recycled, and reused for 3 cycles. Thus, this novel scheme seems to be a better alternative to conquer the drawback of aqueous amine-based CO2 capture as well as for the capture and utilization of the CO2 gas to gain the value-added products.

Direct mineral carbonation of steelmaking slag for CO2 sequestration at room temperature.

Rapid increase of CO2 concentration in the atmosphere has forced the international community towards adopting actions to restrain from the impacts of climate change. Moreover, in India, the dependence on fossil fuels is projected to increase in the future, implying the necessity of capturing CO2 in a safe manner. Alkaline solid wastes can be utilized for CO2 sequestration by which its disposal issues in the country could also be met. The present work focuses to study direct mineral carbonation of steelmaking slag (SS) at room temperature and low-pressure conditions (<10 bar). Direct mineral carbonation of SS was carried out in a batch reactor with pure CO2 gas. The process parameters that may influence the carbonation of SS, namely, CO2 gas pressure, liquid to solid ratio (L/S) and reaction time were also studied. The results showed that maximum sequestration of SS was attained in the aqueous route with a capacity of 82 g of CO2/kg (6 bar, L/S ratio of 10 and 3 h). In the gas-solid route, maximum sequestration capacity of about 11.1 g of CO2/kg of SS (3 bar and 3 h) was achieved indicating that aqueous route is the better one under the conditions studied. These findings demonstrate that SS is a promising resource and this approach could be further developed and used for CO2 sequestration in the country. The carbonation process was evidenced using FT-IR, XRD, SEM and TG analysis.

Conversion of carbon dioxide to resorcylic acid under ultrasonication by Kolbe-Schmitt reaction.

The present work focuses on a new approach for the synthesis of ß-resorcylic acid based on Kolbe-Schmitt reaction using carbon dioxide under ultrasonic and mild condition. The Kolbe-Schmitt reaction is a process for the synthesis of ß-resorcylic acid (2,4-dihydroxybenzoic acid) from resorcinol in aqueous potassium hydroxide solution with gaseous CO2. The influences of carbonation time, flow rate of CO2 and the molar ratio of resorcinol/potassium hydroxide on the yield percentage of resorcylic acid were investigated. The study was assessed with the conventional thermal method (non ultrasonic method) for Kolbe-Schmitt reaction and it was observed that applying ultrasound to save more than 95% and 38.6% energy as shown by energy consumption calculations in bath type and horn type sonicator respectively. ß-Resorcylic acid formed was characterized by (1)H NMR, (13)C NMR, DEPT NMR and FTIR spectroscopy. The amount of CO2 utilized in the reaction was evaluated from the yield percentage of ß-resorcylic acid yield. The maximum yield of resorcylic acid of 30% and 65% was obtained at the resorcinol/potassium hydroxide ratio of 1:3, carbonation time of 150 min and the CO2 flow rate of 2L/min in bath type and horn type ultrasonicator, respectively. The applicability of the research work was examined in two different positional isomers of resorcinol under optimum conditions.

Projected and Observed Aridity and Climate Change in the East Coast of South India under RCP 4.5.

In the purview of global warming, the present study attempts to project changes in climate and quantify the changes in aridity of two coastal districts in south India under the RCP 4.5 trajectory. Projected climate change output generated by RegCM 4.4 model, pertaining to 14 grid points located within the study area, was analyzed and processed for this purpose. The meteorological parameters temperature and precipitations were used to create De Martonne Aridity Index, to assess the spatial distribution of aridity. The original index values ranged from 13.7 to 16.4 mm/°C, characterizing this area as a semidry climate. The outcome from the changed scenario analysis under RCP 4.5 showed that, during the end of the 21st century, the aridity may be increased more as the index values tend to reduce. The increasing trend in the drying phenomenon may be attributed to the rising of mean annual temperatures.

Preconcentration and separation of copper, nickel and zinc in aqueous samples by flame atomic absorption spectrometry after column solid-phase extraction onto MWCNTs impregnated with D2EHPA-TOPO mixture.

A solid phase extraction method has been developed for the determination of copper, nickel and zinc ions in natural water samples. This method is based on the adsorption of copper, nickel and zinc on multiwalled carbon nanotubes (MWCNTs) impregnated with di-(2-ethyl hexyl phosphoric acid) (D2EHPA) and tri-n-octyl phosphine oxide (TOPO). The influence of parameters such as pH of the aqueous solution, amount of adsorbent, flow rates of the sample and eluent, matrix effects and D2EHPA-TOPO concentration have been investigated. Desorption studies have been carried out with 2 mol L(-1) HNO(3). The copper, nickel and zinc concentrations were determined by flame atomic absorption spectrometry. The results indicated that the maximum adsorption of copper, nickel and zinc is at pH 5.0 with 500 mg of MWCNTs. The detection limits by three sigma were 50 µg L(-1) for copper, 40 µg L(-1) for nickel and 60 µg L(-1) zinc. The highest enrichment factors were found to be 25. The adsorption capacity of MWCNTs-D2EHPA-TOPO was found to be 4.90 mg g(-1) for copper, 4.78 mg g(-1) for nickel and 4.82 mg g(-1) for zinc. The developed method was applied for the determination of copper, nickel and zinc in electroplating wastewater and real water sample with satisfactory results (R.S.D.'s <10%).

Photocatalytic degradation of procion blue dye in aqueous solution by a TiO2-carbon nano-composite.

A nano-composite consisting of TiO2-CNT was prepared via the sol-gel technique by using titanium n-butoxide along with carbon nano-tubes (CNTs) followed by calcination at 450 degrees C. Spectral analysis reveals that the TiO2 formed was present on the carbon in anatase form. The effect of adsorption was investigated in an aqueous solution of procion blue dye in a darkroom and the photochemical reaction in aqueous suspensions of titania composite under UV illumination. The reaction was studied by monitoring the discoloration of dye via employing a UV-Visible spectrophotometeric technique as a function of irradiation time. The composite catalyst was found to be efficient in the photodegradation of the dye.

Sonochemical degradation of textile dyes in aqueous solution using sulphate radicals activated by immobilized cobalt ions.

Decolorisation of dye solutions by cobalt activated persulphate and ultrasonication has been investigated. Rhodamine B, Methylene Blue dye (basic dyes) and Acid orange II, Acid scarlet red 3R (acid dyes) were used as model compounds in this study. Immobilized cobalt ions, activated the persulphate to form highly reactive sulphate radicals. The degradation studies were conducted with only persulphate (PS), cobalt activated persulphate (PS+Co), persulphate+ultrasonication (PS+US) and cobalt activated persulphate+ultrasonication (PS+US+Co). The decolorisation efficiency were in the order of PS

Textile anionic dyes recovery using tri-n-butyl phosphate as carrier through supported liquid membrane.

The recovery of anionic dyes Acid Red10 B (CI Acid Violet 54) and Acid Pink BE (CI Acid Red 183) in flat type supported liquid membrane (SLM) using tri-n-butyl phosphate as carrier was studied. The parameters studied were the effect of feed phase pH, stripping reagent concentration, string speed and initial dye concentration on permeability of dyes. The influence of salt concentration such as sodium chloride and sodium sulphate on the dye recovery was examined. The reusability of membrane and kinetics of transport were also studied. The optimum conditions of transport are feed phase pH 1 +/- 0.1, 0.1 M sodium hydroxide as stripping phase, stirring speed at 500 rpm. The maximum recovery under optimum conditions was observed as 94.2 % for Acid Red10 B and 85.7 % for Acid Pink BE. The maximum permeability was 11.0 x 10(-6) m/s for Acid Red10 B and 7.7 x 10(-6) m/s for Acid Pink BE.

Treatment of municipal landfill leachate by solar photocatalytic method using fixed titanium dioxide.

Treatment of municipal landfill leachate by fixed TiO2 photocatalytic method was investigated in the present study using sunlight as light source. Indigenous TiO2 was immobilized with white cement. The leachate used in the study was collected from Kodungaiyur dumpsite in Chennai. Optimization of pH, catalyst dose and exposure time were carried out. Chemical Oxygen Demand (COD) was used to determine the degradation efficiency. The degradation efficiency of leachate was found to be 85% with a batch flat reactor under optimum condition. Fixed catalyst was found to be reusable for 5 times without any reduction in the efficiency. The degradation process was found to follow pseudo first order kinetics.

Di(2-ethylhexyl)phosphoric acid-coconut oil supported liquid membrane for the separation of copper ions from copper plating wastewater.

Permeation of Cu(II) from its aqueous solution through a supported liquid membrane (SLM) containing di(2-ethylhexyl)phosphoric acid (D2EHPA) carrier dissolved in coconut oil has been studied. The effects of Cu(II), pH (in feed), H2SO4 (stripping) and D2EHPA (in membrane) concentrations have been investigated. The stability of the D2EHPA-coconut oil has also been evaluated. High Cu(II) concentration in the feed leads to an increase in flux from 4.1 x 10(-9) to 8.9 x 10(-9) mol/(m2 x s) within the Cu(II) concentration range 7.8 x 10(-4)-78.6 x 10(-4) mol/L at pH of 4.0 in the feed and 12.4 x 10-4 mol/L D2EHPA in the membrane phase. Increase in H2SO4 concentration in strip solution leads to an increase in copper ions flux up to 0.25 mol/L H2SO4, providing a maximum flux of 7.4 x 10(-9) mol/(m2 x s). The optimum conditions for Cu(II) transport are, pH of feed 4.0, 0.25 mol/L H2SO4 in strip phase and 12.4 x 10(-4) mol/L D2EHPA (membrane) in 0.5 microm pore size polytetrafluoroethylene (PTFE) membrane. It has been observed that Cu(II) flux across the membrane tends to increase with the concentration of copper ions. Application of the method developed to copper plating bath rinse solutions has been found to be successful in the recovery of Cu(II).

Adsorptive removal of chlorophenols from aqueous solution by low cost adsorbent--Kinetics and isotherm analysis.

Adsorptive removal of parachlorophenol (PCP) and 2,4,6-trichlorophenol (TCP) from aqueous solutions by activated carbon prepared from coconut shell was studied and compared with activated carbon of commercial grade (CAC). Various chemical agents in different concentrations were used (KOH, NaOH, CaCO(3), H(3)PO(4) and ZnCl(2)) for the preparation of coconut shell activated carbon. The coconut shell activated carbon (CSAC) prepared using KOH as chemical agent showed high surface area and best adsorption capacity and was chosen for further studies. Batch adsorption studies were conducted to evaluate the effect of various parameters such as pH, adsorbent dose, contact time and initial PCP and TCP concentration. Adsorption equilibrium reached earlier for CSAC than CAC for both PCP and TCP concentrations. Under optimized conditions the prepared activated carbon showed 99.9% and 99.8% removal efficiency for PCP and TCP, respectively, where as the commercially activated carbon had 97.7% and 95.5% removal for PCP and TCP, respectively, for a solution concentration of 50mg/L. Adsorption followed pseudo-second-order kinetics. The equilibrium adsorption data were analysed by Langmuir, Freundlich, Redlich-Peterson and Sips model using non-linear regression technique. Freundlich isotherms best fitted the data for adsorption equilibrium for both the compounds (PCP and TCP). Similarly, acidic pH was favorable for the adsorption of both PCP and TCP. Studies on pH effect and desorption revealed that chemisorption was involved in the adsorption process. The efficiency of the activated carbon prepared was also tested with real pulp and paper mill effluent. The removal efficiency using both the carbons were found highly satisfactory and was about 98.7% and 96.9% as phenol removal and 97.9% and 93.5% as AOX using CSAC and CAC, respectively.

Biosorption of copper(II) and cobalt(II) from aqueous solutions by crab shell particles.

Biosorption of each of the heavy metals, copper(II) and cobalt(II) by crab shell was investigated in this study. The biosorption capacities of crab shell for copper and cobalt were studied at different particle sizes (0.456-1.117 mm), biosorbent dosages (1-10 g/l), initial metal concentrations (500-2000 mg/l) and solution pH values (3.5-6) in batch mode. At optimum particle size (0.767 mm), biosorbent dosage (5 g/l) and initial solution pH (pH 6); crab shell recorded maximum copper and cobalt uptakes of 243.9 and 322.6 mg/g, respectively, according to Langmuir model. The kinetic data obtained at different initial metal concentrations indicated that biosorption rate was fast and most of the process was completed within 2h, followed by slow attainment of equilibrium. Pseudo-second order model fitted the data well with very high correlation coefficients (>0.998). The presence of light and heavy metal ions influenced the copper and cobalt uptake potential of crab shell. Among several eluting agents, EDTA (pH 3.5, in HCl) performed well and also caused low biosorbent damage. The biosorbent was successfully regenerated and reused for five cycles.

Recovery of phenol from aqueous solution by supported liquid membrane using vegetable oils as liquid membrane.

The transport of phenol through a flat sheet supported liquid membrane (SLM) containing vegetable oil as liquid membrane (LM) has been investigated. The permeation of phenol was investigated by varying the experimental conditions like, selection of LM, support material, feed phase pH, stripping solution concentration, stirring speed and different initial concentration of phenol. It has been found that, each LM investigated in the present study shows the effective removal of phenol using polytetrafluoroethylene (PTFE) membrane and PP supported membrane as a solid support. Among the various oils tested, palm oil has chosen to be the best LM with permeability of 8.5x10(-6) m/s in acidic feed of pH 2.0 with 0.2 M sodium hydroxide as effective stripping agent. After 6 h all the phenol from the feed side gets transported to strip solution with an initial concentration of 100 mg/L. A concentration factor of five has been achieved in the present investigation easily with 0.2 M sodium hydroxide as stripping reagent. After 10 transport studies with one impregnation of LM, the LM showed no significant loss in the transport rate with average permeability of 7.9x10(-6) m/s with initial concentration 100 mg/L. Further study has also been attempted with cresols to explore the possibility of applying this to industrial wastewater under the optimized conditions for phenol. After 14 h of the transport studies in the phenol-formaldehyde industry wastewater, phenolic concentration in the feed solution was found to be below detectable level (1x10(-2) mg/L). For wood processing industry wastewater the transport takes place at the initial permeability of 7.1x10(-5) m/s. Thus it has been demonstrated the use of renewable, cheap, non toxic, naturally occurring vegetable oils as a novel, green liquid membrane for the recovery of phenol from aqueous solution in SLM, which has never been employed before in liquid membrane techniques.

Biosorption of nickel(II) ions onto Sargassum wightii: application of two-parameter and three-parameter isotherm models.

Biosorption of nickel(II) ions from aqueous solution onto Sargassum wightii has been studied and the equilibrium isotherms were determined. The experimental data obtained at different pH conditions (pH 3.0-4.5) have been analyzed using five two-parameter models (Langmuir, Freundlich, Temkin, Dubinin-Radushkevich and Flory-Huggins) and five three-parameter models (Redlich-Peterson, Sips, Khan, Radke-Prausnitz and Toth). In order to determine the best fit isotherm, three error analysis methods were used to evaluate the data: correlation coefficient, residual root mean square error and chi-square test. The error analysis demonstrated that the three-parameter models better described the nickel biosorption data compared to two-parameter models. In particular, Toth equation provided the best model for nickel biosorption data at all pH conditions examined.

Destruction of cresols by Fenton oxidation process.

The present study was used to probe the treatment of simulated wastewater containing cresols by Fenton process. Experiments were conducted in a batch reactor to examine the effects of operating variables like pH, hydrogen peroxide concentration (H(2)O(2)) and ferrous ion concentration (Fe(2+)) on chemical oxygen demand (COD) removal. The progress of the degradation reaction was monitored by the decrease in COD content in the treated solution. The optimal reacting conditions were experimentally determined and it was found to be [H(2)O(2)]=31.64 mM, [Fe(2+)]=0.90 mM for o- and p-cresol while 0.72 mM for m-cresol at pH=3.0+/-0.2. The degradation efficiency for cresol isomers was as high as 82% within 120 min at optimum conditions. A pseudo-first-order kinetic model was adopted to represent the Fenton oxidation for cresols. The mineralization rate for cresols obeys the following sequence: m->p->o-. Maximum degradation occurred at 30 degrees C for the temperature range of 20-50 degrees C studied. The global activation energy for the first-order reaction was estimated to be in the range of 12.90-16.25 kJ/mol. Air/nitrogen did not play an active role in completely mineralizing the organic intermediates at the experimental conditions adopted. Irrespective of the position of methyl group in o-, m- or p-position, the maximum dissolved organic carbon (DOC) removal efficiency was 42%. Only 2/5th of cresol was mineralized to CO(2) by Fenton process. The results showed that the cresols were completely oxidized and degraded into lower molecular weight aliphatic acids. Among the acids, acetic and oxalic acids were identified as the major products formed during the degradation.

Biosorption of copper, cobalt and nickel by marine green alga Ulva reticulata in a packed column.

Biosorption of copper, cobalt and nickel by marine green alga Ulva reticulata were investigated in a packed bed up-flow column. The experiments were conducted to study the effect of important design parameters such as bed height and flow rate. At a bed height of 25 cm, the metal-uptake capacity of U. reticulata for copper, cobalt and nickel was found to be 56.3+/-0.24, 46.1+/-0.07 and 46.5+/-0.08 mgg(-1), respectively. The Bed Depth Service Time (BDST) model was used to analyze the experimental data. The computed sorption capacity per unit bed volume (N0) was 2580, 2245 and 1911 mgl(-1) for copper, cobalt and nickel, respectively. The rate constant (K(a)) was recorded as 0.063, 0.081 and 0.275 lmg(-1)h(-1) for copper, cobalt and nickel, respectively. In flow rate experiments, the results confirmed that the metal uptake capacity and the metal removal efficiency of U. reticulata decreased with increasing flow rate. The Thomas model was used to fit the column biosorption data at different flow rates and model constants were evaluated. The column regeneration studies were carried out for three sorption-desorption cycles. The elutant used for the regeneration of the biosorbent was 0.1 M CaCl2 at pH 3 adjusted using HCl. For all the metal ions, a decreased breakthrough time and an increased exhaustion time were observed as the regeneration cycles progressed, which also resulted in a broadened mass transfer zone. The pH variations during both sorption and desorption process have been reported.

Continuous sorption of copper and cobalt by crab shell particles in a packed column.

The ability of crab shell to remove copper and cobalt from aqueous solutions was examined in an up-flow packed column. The experiments were conducted to study the effect of important design parameters such as bed height and flow rate. At a bed height of 25 cm, metal uptake capacity of crab shell for copper and cobalt was 52.07 and 20.47 mg g(-1) respectively. In addition, the results obtained at different flow rates indicated that an increase in flow rate decreased the sorption performance of the crab shell. The Bed Depth Service Time model and the Thomas model were used to analyze the experimental data and the model parameters were evaluated for copper and cobalt sorption. The column regeneration studies were carried out for five sorption-desorption cycles. Loss of sorption performance was observed as the cycles progressed, indicated by a shortened breakthrough time and a broadened mass transfer zone. However, crab shell maintained a good metal sorption capacity for all the five cycles. The elutant used for the regeneration of the crab shell, 0.01 M EDTA at pH 3.5 adjusted using HCI, exhibited elution efficiencies greater than 98%.

Crab shell-based biosorption technology for the treatment of nickel-bearing electroplating industrial effluents.

This paper discusses the possible application of a biosorption system with acid-washed crab shells in a packed bed up-flow column for the removal of nickel from electroplating industrial effluents. Between two nickel-bearing effluents, effluent-1 is characterized by considerable amount of light metals along with trace amounts of lead and copper. Effluent-2 is characterized by relatively low conductivity, total dissolved solids and total hardness compared to effluent-1. Crab shells exhibited uptakes of 15.08 and 20.04 mg Ni/g from effluent-1 and effluent-2, respectively. The crab shell bed was regenerated using 0.01 M EDTA (pH 9.8, aq. NH3) and reused for seven sorption-desorption cycles. The EDTA elution provided elution efficiencies up to 99% in all the seven cycles. This, together with the data from regeneration efficiencies for seven cycles, provided evidence that the reusability of crab shell in the treatment of nickel-bearing electroplating industrial effluents is viable.