Oil spill cleanup by raw flax fiber: Modification effect,sorption isotherm,kinetics and thermodynamics

Modification of raw flax fiber by acetylating process and microwave energy was useful in the application of oil spill cleanup. The change in fibers was characterized by scientific analysis(FTIR, SEM, XRD and contact angle). The results indicate that the modified fibers by the acetylating process have extra hydrophobic properties than both microwave radiation and raw fibers. Oil/Artificial seawater(3.5% salinity by NaCl) system (O/W-S) was used as a liquid phase operation system. Fast oil sorption was reached at 6 min and attained(equilibrium) at 10 min. Acetylated fiber(ACF)has higher oil sorption capacity(24.54 g/g) than both raw(13.75 g/g) and microwave fiber(17.42 g/g) with exothermic effect. The sorption kinetics and isotherms indicate that the oil sorption onto ACF agreement with pseudo second-order kinetic model and Freundlich isotherm model. Also, the economic reusing of fiber was evaluated. The process of acetylation demonstrated the ability to improve the absorptive properties of the fibers, which makes them able to compete with synthetic fibers in the oil spill cleanup and industrial applications, as well as cheap and eco-friendly due to their biodegradation.     

Hydrophobic,superabsorbing materials from reduced graphene oxide/MoS2 polyurethane foam as a promising sorbent for oil and organic solvents

This study illustrates the preparation of robust superhydrophobic and superoleophilic reduced graphene oxide (rGO) and MoS₂ nanoparticles incorporated polyurethane (PU) foam by in-situ polymerization via the one-shot method. Spectroscopic analyses confirmed the successful formation of nanoparticles and also the development of the hybrid PU material. The sponges were evaluated based on hydrophobicity and oil absorbance capacities and the modified foam exhibits the water contact angle of 151°. The pore size of the foam analyzed using an optical microscope and the effect on the density and porosity were also analyzed. The oil absorption capacity of the foam was studied using standard sorption testing. The oil and organic solvent selectivity and recyclability of hybrid PU foam were performed to estimate whether the foams could be recycled and reused. The modified system shows very high selectivity (83–94%). The recyclability of the foam was about 35 cycles without much reduction in its own weight and after 55 cycles more than 80% of the oil absorption capacity was conserved. The resulting hybrid PU material is highly efficient, porous, ultralight, hydrophobic and reusable sorbent material and displays great potential for versatile environmental remediation.     

Preparation and characterization of polyurethane based self-cleaning and antibacterial coating containing silver ion exchanged montmorillonite/TiO<Subscript>2</Subscript> nanocomposite

In order to reach an antibacterial, photocatalytic, and hydrophilic coating, commercial grade polyurethane (CPU) resin was modified with silver ion exchanged montmorillonite/TiO₂ nanocomposite in various montmorillonite to TiO₂ nanoparticle ratios. To characterize the prepared nanocomposites and coatings, X-ray diffraction patterns, FTIR and UV–Vis spectroscopy and SEM images were used. The modified commercial grade polyurethane coatings containing nanocomposites show better properties, including hydrophilicity, degradation of organic pollutants, antibacterial activity and water resistivity, compared to unmodified commercial grade polyurethane coatings. The water droplet contact angle of unmodified CPU coating was 70°, however it decreased to lower than 10° in modified CPU coatings after 24 h LED lamp irradiation. Decolorization efficiency of malachite green dye solution by the use of modified CPU coatings achieved up to 70% after 5 h LED lamp illumination, compared to less than 5% for unmodified CPU coatings. Modified CPU coatings also showed significant water resistivity and antibacterial properties.     

Superhydrophilic and superoleophobic chitosan-based nanocomposite coatings for oil/water separation

To overcome easy oil fouling and poor efficiency of traditional oil/water separation materials, superhydrophilic and superoleophobic coatings were fabricated by spray casting chitosan (CTS)-based nanocomposites. The molecular rearrangement of hydrophilic and oleophobic constituents, combined with the hierarchical rough surface structures, enabled a coating with a water contact angle of 0° and a hexadecane contact angle of 157° ± 1°. Hexadecane droplets can easily slide off the dried and water-wetted coating without leaving any obvious oily trailing stains. When the superhydrophilic and superoleophobic CTS-based nanocomposite coatings were applied to oil/water separation, they exhibited excellent anti-fouling capacity, high separation efficiency and easy recyclability. The superhydrophilic and superoleophobic CTS-based coating would be a good candidate for the treatment of industrial oil-polluted water and the cleanup of oil spills.     

Surface hydrophobization of polyester fibers with poly(methylhydro-dimethyl)siloxane copolymers: Experimental design for testing of modified nonwoven materials as oil spill sorbents

This paper reports on the hydrophobization of polyester fibrous nonwoven with poly(methylhydro-dimethyl)siloxane copolymers in order to produce water-repellent sorbents for oil spill cleanup. Polysiloxane copolymers were first synthesized and characterized prior to be used as hydrophobization agents. The produced hydrophobic sorbents were characterized by scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM/EDX); infrared spectra (FTIR) and water-contact angle measurements (WCA). Nonwoven sorbents were evaluated for oil sorption in pure oil bath and in the presence of water (W-test). A statistical experiment design was employed for materials testing and the development of data-driven models. The optimal hydrophobic nonwoven yielded maximal sorption capacities equal to 5.52 g/g and 10.03 g/g for dodecane and motor oil uptake, respectively. The mechanism of oil attachment on polymeric fibers was investigated by optical microscopy revealing a key role of inter-fiber voids for oil retention. Centrifugation tests demonstrated a high recycling ability of spent nonwoven sorbents.     

Superhydrophobic and superoleophilic polyethylene aerogel coated natural rubber latex foam for oil-water separation application

The oil-water separation has made an attention due to over-increased production of oily water from the industrial process and everyday routine of humans. The current work reports on preparation and characterization of High-Density Polyethylene (HDPE) aerogel coated Natural Rubber Latex foam (NRLF) with superhydrophobic and superoleophilic character, good sorption capacity for oil-water separation application and were investigated. The HDPE aerogel and the coated NRLF material was prepared by a cooling process from a solution of HDPE in xylene solvent (HDPE sole, which resulted into thermally induced phase separation of the Polyethylene molecular network). The HDPE aerogel coated NRLF displayed a porous surface morphology with particle-like structural features. The HDPE aerogel coated NRLF showed superhydrophobicity with static water contact angle >150°. The effect and recyclability of the HDPE aerogel coated NRLF for oil-water separation was investigated using different model oil solvents to explore their repeatable application in oil spill clean-up process. Modified NRLF shows an excellent mechanical property (compressibility). The average modulus and average stiffness of the modified NRLF increased with the increase of the concentration of HDPE sol. The modified superhydrophobic sponge has good durability under acid and base conditions.     

Evaluation of Hydrophobic Polyurethane Foam as Sorbent Material for Oil Spill Recovery

In this work, hydrophobic polyurethane foam was prepared using hy-drosilicone oil-grafted polybutadiene as soft segment via foaming technology. It was found that the hydrophobic polyurethane foams exhibited good hydrophobic capability and were regenerated easily. Of great interest, the hydrophobic polyurethane foams expand in contact with the oils. This indicates that the process of sorption by the hydrophobic polyurethane foams involves both the filling of the pores with oils and the absorption of oils by the polymer regions (polyurethane elastomer skeleton), and the adsorption capacity of the hydrophobic polyurethane foams can be enhanced by the swelling of the polyurethane elastomer skeleton. We can use this finding to improve the adsorption capacity of the hydrophobic polyurethane foams without merely changing the porosity. The effect of the swelling property of the hydrophobic polyurethane foams on the sorption capacity was further investigated. The results suggest that the hydrophobic polyurethane foams are promising in the application of oil spill recovery.     

羧甲基纤维素钠修饰的聚氨酯泡沫制备磁性吸油材料

采用聚氨酯泡沫为模板,依次修饰羧甲基纤维素钠(CMC)、Fe~(3+),在惰性气氛中高温热处理反应,制备多孔结构的磁性吸油材料.用光学显微镜、扫描电子显微镜、红外吸收光谱、X-射线衍射、接触角等技术对材料进行表征.详细考察了加热反应温度、CMC浓度和Fe~(3+)浓度对材料吸油性能和磁性的影响规律.实验表明,当加热反应温度选择230°C,CMC浓度为0.3 wt%,FeCl_3浓度为0.1 mol/L时,材料吸油性能最佳,对正己烷、二甲苯、环己烷、甲苯、乙酸乙酯、氯仿、机油、原油等有机溶剂和油类分子的吸附容量为10倍左右.磁性多孔材料具有明显的亲油、疏水特性,水的接触角达115.9°,同时材料密度只有0.036g/cm~3,能够漂浮于水面,实现对水面有机溶剂的快速吸附.吸附后的材料在外界磁场控制下,能够通过磁分离方式从水面快速分离.该材料具有良好的循环利用性能,可重复使用20次以上,吸油性能仍然保持良好.     

Improvement in Adhesion between Ethylene–Propylene–Diene Terpolymer (EPDM)-based Elastomer and Polyurethane Coating Using Epoxy–Polysulfide Copolymer As Adhesion Promoter

Epoxy–polysulfide copolymer as an adhesion promoter was added to ethylene–propylene–diene terpolymer and the effect of maleation of terpolymer with maleic anhydride on its adhesion to polyurethane coating was studied. The results show that using epoxy-polysulfide copolymer as the adhesion promoter cause a significant improvement in adhesion of terpolymer to polyurethane coating. The contact angle of the water reduced from 88° for the unmodified terpolymer to 65° for the maleated terpolymer containing 10 phr of epoxy–polysulfide copolymer. Peel strength was also increased from 0.2 N/mm for the unmodified terpolymer to 1.12 N/mm for the above-mentioned modified elastomer. Effect of the composition of the polymer blends on the loss tangent and storage modulus was studied to evaluate phase separation and crosslink density. The improvement of adhesion to polyurethane occurred without phase separation, which was further confirmed by the results of the mechanical and morphological investigations.     

聚氧化丙烯醚对SiO2减反膜性质的影响

采用溶胶-凝胶制备的SiO2减反膜具有优良的光学特性和高损伤阈值,可以用做高反膜和减反膜的低折射率匹配层.在高功率激光领域具有十分诱人的应用前景.     

Sequestration of Aqueous Lead(II) Using Modified and Unmodified Red Onion Skin

The efficacy of onion skins, both unmodified and chemically modified with thioglycolic acid, was investigated as alternative low-cost adsorbents for the sequestration of aqueous lead(II) ions from aqueous solution. The adsorbents were characterised using Fourier transform infrared spectroscopy and scanning electron microscopy – energy dispersive X-ray spectroscopy. Adsorption experiments were performed using batch sorption processes. The effects of contact time, pH, initial Pb(II) concentration, adsorbent dose, and temperature were investigated. Optimum sorption conditions were found at pH 4 and a 150?min equilibrium time for the modified onion skin and unmodified onion skin. The Langmuir, Freundlich, Dubinin-Radushkevich and Temkin models were used to characterize the equilibrium experimental results. The equilibrium process was best described by the Freundlich isotherm. The maximum adsorption capacities of 4.878 and 6.173?mg/g were obtained for modified and unmodified adsorbents, respectively, using the Langmuir model. Kinetic studies indicated that the sorption of Pb(II) ions followed a pseudo-second-order model. Thermodynamic parameters such as standard enthalpy change (ΔH°), entropy change (ΔS°), and free energy change (ΔG°) were evaluated from the sorption experimental measurements. The results showed that the sorption process of Pb(II) ions on unmodified and modified onion skins was feasible and exothermic under the conditions used in this study. The sorption process followed the mechanism of physisorption.     

ATRP法合成弹性蛋白接枝共聚物及其性能研究

弹性蛋白经α-溴异丁酰溴化制备了大分子ATRP引发剂溴化弹性蛋白(E-Br), 再以E-Br作为引发剂, 在CuCl/2,2-联吡啶催化体系下, 用原子转移自由基聚合方法合成了弹性蛋白-g-聚甲基丙烯酸-β-羟乙酯接枝聚合物. 用红外光谱(FTIR)、X射线光电子能谱(XPS)、热重分析(TGA)、扫描电镜(SEM)、离子色谱和动态接触角对接枝聚合物进行了表征. 结果表明, PHEMA键接到了弹性蛋白表面; SEM显示接枝改性后弹性蛋白的表面比未改性前光滑, 但改性后样品的热性能均比未改性样品的低, 起始热分解温度由改性前的307 ℃变为265 ℃; 动态接触角实验结果表明, 接枝改性后的样品具有良好的亲水性, 反应72 h后, 其前进角由接枝前的130.45°下降到29.80°.     

Removal of Zn(II) Ions from Aqueous Solution Using BPHA‐Impregnated Polyurethane Foam

Zn(II) ions sorption onto N‐Benzoyl‐N‐Phenylhydroxylamine (BPHA) impregnated polyurethane foam (PUF) has been studied extensively using radiotracer and batch techniques. Maximum sorption (～98%) of Zn(II) ions (8.9 × 10^?6 M) onto sorbent surface is achieved from a buffer of pH 8 solution in 30 minutes using 7.5 mg/mL of BPHA‐impregnated polyurethane foam at 283 K. The sorption data follow Langmuir, Freundlich and Dubinin‐Radushkevich (D‐R) isotherms. The Langmuir constants Q = 18.01 ± 0.38 μ mole g^?1 and b = (5.39 ± 0.98) × 10³ L mole^?1 have been computed. Freundlich constants 1/n = 0.29 ± 0.01 and C_m = 111.22 ± 12.3 μ mole g^?1 have been estimated. Sorption capacity 31.42 ± 1.62 μ mole g^?1, β = ?0.00269 ± 0.00012 kJ² mole^?2 and energy 13.34 ± 0.03 kJ mole^?1 have been evaluated using D‐R isotherm. The variation of sorption with temperature yields ΔH = ?77.7 ± 2.8 k J mole^?1, ΔS = ?237.7 ± 9.3 J mole^?1 K^?1 and ΔG = ?661.8 ± 117.5 k J mol^?1 at 298 K reflecting the exothermic and spontaneous nature of sorption. Cations like Fe(III), Ce(III), Al(III), Pb(II) and Hg(II) and anions, i.e., oxalate, EDTA and tartrate, reduce the sorption significantly, while iodide and thiocyanate enhanced the sorption of Zn(II) ions onto BPHA‐impregnated polyurethane foam.     

Fabrication of AgNPs/Silane coated mechanical and washing durable hydrophobic cotton textile for self-cleaning and oil-water separation application

This study deals to develop a simple and facile two-step dip-coating method using silver nanoparticles (AgNPs) and fluorine-free silane monomer, 3-(Trimethoxysilyl) propyl methacrylate (TMSPM) for the fabrication of hydrophobic coating on cotton fabric. The anti-wetting properties, surface morphology, chemical composition, and functionality of the cotton fabric before and after modification were well characterized by contact angle measurement, scanning electron microscope (SEM), and energy-dispersive X-ray spectrum (EDX) and FT-IR respectively. The fabricated cotton fabric displays strong durability against different pH solutions, different soft/hard mechanical treatments including adhesive peeling test, abrasion with tissue paper and finger wiping, home laundering, without losing the hydrophobic property. The contact angle values (water contact angle of 148.3 ?± ?2° and oil contact angle of 0°) imply that the modified cotton has considerable hydrophobic/oleophilic properties. Additionally, the modified hydrophobic/oleophilic cotton fabric exhibits self-cleaning and oil-water separation behavior for both industrial and household importance.     

Development of hydrophobic polyurethane film from structurally modified castor oil and its anticorrosive performance

Hydrophobic polyurethane (PU) films are widely used for various commercial and industrial applications due to their excellent water repelling and self-cleaning property. Nevertheless, achieving appreciable hydrophobicity in PU film is quite a challenge. Herein, we report on the development of a novel hydrophobic PU (fluorinated polyurethane [FCO-PU]) film and comprehensively evaluate its anticorrosive property. The FCO-PU was prepared by structural modification of castor oil (CO) through attachment of long fluorocarbon chains as pendant groups onto the backbone of CO. A model PU film (CO-PU) was also prepared from unmodified CO to compare the properties of FCO-PU film. All intermediate compounds, FCO-PU and CO-PU films were characterized by various spectroscopic techniques. Morphological, thermal and mechanical properties of the PU films were analyzed by field emission scanning electron microscopy (FESEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and dynamic mechanical thermal analysis (DMTA) studies. Successful introduction of long fluorocarbon chains into the FCO-PU film is reflected by its high hydrophobicity with a water contact angle of 119.1°, compared to the model CO-PU film with a water contact angle of 84.4°. Anticorrosive properties of the PU films were evaluated by polarization technique and electrochemical impedance spectroscopy under corrosive environment and the obtained results reveal a significant corrosion resistance (corrosion rate: 6.72 × 10⁻⁶ mm/year) behavior by the FCO-PU film. This work represents an effective strategy for the backbone modification of CO to develop novel functional PU materials.     

硫代-iniferters法改性弹性蛋白的研究

弹性蛋白经对氯甲基苯甲酰氯氯化、二乙基二硫代氨基甲酸钠(NaSD)硫化制备了大分子iniferter剂(E-S), 再以E-S为引发剂, 在紫外光(UV)照射下引发甲基丙烯酸-β-羟乙酯(HEMA)聚合, 合成了聚甲基丙烯酸-β-羟乙酯(E-PHEMA)改性的弹性蛋白聚合物. 用红外(FTIR)和X射线光电子能谱(XPS)、热重分析(TGA)、扫描电镜(SEM)和动态接触角对改性弹性蛋白进行了表征. 结果表明: PHEMA键接到了弹性蛋白上; SEM显示改性后弹性蛋白的表面比未改性前变得光滑, 但改性后样品的热性能均低于未改性样品, 起始热分解温度由改性前的307.0 ℃变为260.2 ℃, 最大失重速率温度由347 ℃降到316.3 ℃; 动态接触角实验表明改性后样品具有良好的亲水性, 反应72 h后前进角由改性前的130.45°下降到35.40°, 接触角滞后由70.42°变为35.40°.     

Thermo‐Driven Controllable Emulsion Separation by a Polymer‐Decorated Membrane with Switchable Wettability

A thermoresponsive Poly(N‐isopropylacrylamide) (PNIPAAm)‐modified nylon membrane was fabricated via hydrothermal route. Combining rough structure, proper pore size, and thermoresponsive wettability, the membrane can separate at least 16 types of stabilized oil‐in‐water and water‐in‐oil emulsions at different temperatures. Below the LCST (ca. 25 °C), the material exhibits hydrophilicity and underwater superoleophobicity, which can be used for the separation of various kinds of oil‐in‐water emulsions. Above the LCST (ca. 45 °C), the membrane shows the opposite property with high hydrophobicity and superoleophilicity, and it can then separate stabilized water‐in‐oil emulsions. The material exhibits excellent recyclability and high separation efficiency for various kinds of emulsions and the hydrothermal method is facile and low‐cost. The membrane shows good potential in real situations such as on‐demand oil‐spill cleanup, industrial wastewater treatment, remote operation of oil/water emulsion separation units, and fuel purification.     

The effect of repetitive frying on physicochemical properties of refined,bleached and deodorized Malaysian tenera palm olein during deep-fat frying

Refined, bleached and deodorized tenera palm olein is widely used for domestic and commercial food frying. However, repeated heating and frying might lead to oil spoilage. This study focuses on the effect of deep-frying on physicochemical properties of repeatedly heated palm olein. Recycled palm olein was prepared by frying potato strips up to 5 cycles with potato-to-oil (g/ml) ratio of 3:20 prior to colour, density, viscosity, moisture content, contact angle, peroxide value and iodine value analyses. The fluctuation in the temperature of the oil was insignificant for every cycle (p > 0.05). The increase in red colour of the oil was significant (p < 0.05) after two cycles of frying from 3.6 to 5.0 Lovibond unit. After 5 frying cycles, there was no change in the density of RBDPO-2 and RBDPO-3. The viscosity of the oil after 5 frying cycles was higher as compared to after 5 heating cycles (67.7 ± 0.6 and 58.2 ± 0.9 cP respectively). Besides, the viscosity of RBDPO-3 was lower than RBDPO-2 only. The moisture content of the oil increased from 3.7 ± 0.1% to 30.4% (w/w) for RBDPO-2, whereas for RBDPO-3, the viscosity increased from 3.7 ± 0.1% to 30.4 ± 0.1% (w/w) due to the presence of the moisture from the potato. The change in the contact angle of the RBDPO-1 (control) was significant (p < 0.05) between the 1st cycle and the 5th cycle from 19.16 ± 0.45° to 12.03 ± 0.45° respectively. Besides, there was a significant change (p < 0.05) of contact angle for RBDPO-2 between the 1st cycle and the 5th cycle from 32.53 ± 0.5° to 18.06 ± 0.15° respectively. The peroxide value of the fresh oil was 2.8 ± 0.2 meq/kg and the value after the 1st cycle for all RBDPO(s) treatment increased, indicating that primary oxidation had occurred after the 1st cycle of heating and frying. A decreasing trend was observed from the 2nd until the 5th frying cycle because the instability of peroxide at a high temperature, causes rapid degradation and produced a dimer and volatile compound. Frying also decreased the unsaturated value of the oil as indicated by a decrease in the iodine value. Based on Pearson’s correlation test, there was a positive correlation between the colour, density and viscosity of the oil. The higher the peroxide value, the higher the density of the oil. There was also a positive correlation between the contact angle, moisture content and peroxide value of the oil. Whereas, a negative correlation was found between the iodine values, colour, density and viscosity of the oil. In conclusion, the potato repetitive deep-frying darkened the colour of the oil, increased its density, viscosity, contact angle, and peroxide value and decreased the degree of unsaturation of the oil as it shows a prominent sign of oxidative rancidity.     

Cleanup of Water Surface from Oil Spills Using Natural Sorbent Materials

The following indicators were used to compare sorption efficiency of the test objects: oil capacity (OC), buoyancy, solubility of hydrocarbons in water, and water absorption (WA). Hereby, it was determined that the peat moss carbonized at the temperature of 200-250°С and modified by acetic acid has high sorption capacity. The sorbents introduced can increase the efficiency of water surface cleaning up until the water is almost clean and the residual oil content in water is less than 0.03 g/l.     

Super-hydrophobic carrageenan cross-linked graphene sponge for recovery of oil and organic solvent from their water mixtures

A novel ultra-light, superhydrophobic graphene based carrageenan sponge (GCS) absorbent was synthesized by one pot hydrothermal method, for the use of selective adsorption of oils and organic solvents from their water mixtures. The GO nanosheets were reacted in the presence of formaldehyde by the insertion of carrageenan, forming hydrophobic cross-linked structure in between them. The structure and properties of this GCS are well characterized by Fourier transform infrared spectroscopy, X-ray diffraction, Thermal gravimetric analysis, Scanning electron microscopy, and Water contact angle. The as-prepared GCS has good thermal stability (400 °C), low density (20 mg/cm⁻³), excellent hydrophobicity (water contact angle of 136.24°), and selective absorption capacity (25.2–35.95 g/g) of oils and organic solvents from their water mixtures. GCS has excellent oil sorption capacity in the range of 25.2–50 g of oil per gram of adsorbent. GCS could be easily reused by simple solvent treatment. Therefore, the adsorption capacity still retained even after 10 cycles. The present work suggests that GCS using biobased resources has high potentials for many widespread applications in industry to control environmental pollution.