Recent Advances in Transition Metal-Based Catalysts for Ethylene Copolymerization with Polar Comonomer.

The synthesis of polar functionalized polyolefin (PFP) offers improvement in mixing properties, polymer surface, and rheological properties with the potential of upgraded polyolefins for modern and ingenious applications. The synthesis of PFP from metal-based catalyzed olefin (non-polar in nature) copolymerization with polar comonomers embodies energy-efficient, atom-efficient, and apparently an upfront methodology. Despite their outstanding success during conventional polymerization of olefin, 3rd and 4th group (early transition metal)-based catalysts, owing to their electrophilic nature, face challenges mainly due to Lewis basic sites of the polar monomers. On the contrary, late transition metal-based catalysts have also made progress, in recent years, for PFP synthesis. The recent past has also witnessed several advancements in the development of dominating palladium-based catalysts while their lower resistance towards ligand functional groups has limited the practical application of abundant and cheaper nickel-based catalysts. However, the relentless efforts of the scientific community, during the past half-decade, have indicated rigorous progress in the development of nickel-based catalysts for PFP synthesis. In this review, we have abridged the recent research trends in both early as well as late transition metal-based catalyst development. Furthermore, we have highlighted the role of transition metal-based catalysts in influencing the polymer properties.

Enhanced removal of Eriochrome Black T from water using biochar/layered double hydroxide/chitosan hybrid composite: Performance evaluation and optimization using BBD-RSM approach.

In this research work, a novel hybrid composite consisting of biochar (B), layered double hydroxide (CuFe) and chitosan (CS) (B-CuFe-CS) was produced using an ultrasonication-assisted co-precipitation method. The resultant composite was employed for adsorptive removal of Eriochrome black T (EBT) from water. Physicochemical characterization indicated that the B-CuFe-CS containing 10 wt % CS exhibited a heterogeneous structure with better crystallographic and textural characteristics. The B-CuFe-CS with abundant surface functionalities (-CO, -C-O, -OH, -NO3, and MMO), facilitates faster and enhanced removal of the EBT. The kinetic results showed better fitting to the pseudo-second order model, and equilibrium was achieved within 30 min. Equilibrium data was well explained by Langmuir and Redlich Peterson isotherm models (R2 > 0.98), indicating the EBT removal onto B-CuFe-CS followed monolayer adsorption. The maximum adsorption capacity was 806.4 mg/g, which was higher than pristine B-CuFe (476.19 mg/g) and many other adsorbents. The spectroscopic analysis (FTIR and XPS) and experimental results suggested that EBT adsorption is mainly governed by electrostatic, chemical and anion-exchange interactions. It is evident from these results that coupling B-CuFe composite with bio-filler (chitosan) resulted in an efficient bio-adsorbent to effectively purify dye-contaminated water streams.

Sewage Sludge ZnCl2-Activated Carbon Intercalated MgFe-LDH Nanocomposites: Insight of the Sorption Mechanism of Improved Removal of Phenol from Water.

Keywords: sludge-activated carbon; MgFe layered double hydroxide; nanocomposite materials; phenol aqueous uptake; mechanistic studies; reusability performance.

Demulsification of asphaltene stabilized crude oil emulsions by biodegradable ethylcellulose polymers with varying viscosities.

Efficient demulsifiers for fast demulsification of asphaltene stabilized crude oil emulsions are currently in high demand. In this work, we evaluated the demulsification potential of ethyl cellulose (EC) demulsifiers with varying viscosities-4 cp, 22 cp, and 100 cp, designated as EC-4, EC-22, and EC-100. Demulsifcation efficiency (DE) of these demulsifiers to remove water from emulsions produced from distilled water, seawater, and different salts (NaCl, MgCl2, and CaCl2) solution were assessed using the bottle test technique at ambient and elevated temperatures (25 °C and 90 °C). The bottle test outcomes showed that EC-4 and EC-22 had better performance at the ambient conditions to demulsify the emulsions formed from distilled water with %DE of 85.71% and 28.57%, respectively, while EC-100 achieved 3.9% water removal owing to its high viscosity which inhibited its adsorption at the oil-water interface. At demulsification temperature (90 °C) under the emulsions from distilled water, the %DE of EC-4, EC-22, and EC-100 was 99.23%, 58.57%, and 42.85%, respectively. Seawater hastened the demulsification activities of these demulsifiers. Also, these demulsifiers demonstrated excellent demulsification in emulsions from various salts. The demulsification performance of the EC-4 demulsifier in the presence of any of these salts was approximately 98% while MgCl2 and CaCl2 accelerated the water/oil separation performance of EC-22 and EC-100 by promoting their diffusion and adsorption at the interface. Viscosity and shear stress measurements corroborated the results obtained from the bottle tests. Injection of EC demulsifiers led to a reduction in the viscosity and shear stress of the formed emulsion. Reduction in the shear stress and viscosity were highest in EC-4 and lowest in EC-100. Optical microscopic images of emulsion injected with EC-4 demulsifier were analyzed at various periods during viscosity measurements. Based on the optical images obtained at different durations, a demulsification mechanism describing the activity of the EC demulsifier was proposed.

Effect of the Surface Functionalization of Graphene and MWCNT on the Thermodynamic, Mechanical and Electrical Properties of the Graphene/MWCNT-PVDF Nanocomposites.

The nanocomposites of poly(vinylidene fluoride) (PVDF) with pristine graphene nanoflakes (GNF) and a multi-wall carbon nanotube (MWCNT) were prepared by the solution casting method. Additionally, the GNF and MWCNT were functionalized by acid treatment, and nanocomposites of the acid-treated MWCNT/GNF and PVDF were prepared in the same method. The effect of the acid treatment of MWCNT and GNF on the mechanical, thermal and thermo-oxidative stability and the thermal conductivity of the MWCNT/GNF-PVDF nanocomposites was evaluated, and the results were compared with the untreated MWCNT/GNF-PVDF nanocomposites. In both cases, the amount of GNF and MWCNT was varied to observe and compare their thermal and mechanical properties. The functionalization of the GNF or MWCNT resulted in the change in the crystallization and melting behavior of the nanocomposites, as confirmed by the differential scanning calorimetry analysis. The addition of the functionalized GNF/MWCNT led to the improved thermal stability of the PVDF nanocomposites compared to that of the non-functionalized GNF/MWCNT-PVDF nanocomposites. The thermal and electrical conductivity of the functionalized and non-functionalized GNF/MWCNT-PVDF composites were also measured and compared. The functional groups, crystal structure, microstructure and morphology of the nanocomposites were characterized by Fourier transformed infrared spectroscopy (FTIR), X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively.

Effect of Fabrication Method on the Thermo Mechanical and Electrical Properties of Graphene Doped PVDF Nanocomposites.

Nanocomposites of poly (vinylidene fluoride) PVDF with graphene nanoflakes (GNF) were prepared using two different routes. Initially, a mix-melting method was used to prepare composites, and their thermal and mechanical properties were evaluated to choose the better method for future experiment and properties investigation. Then, nanocomposite films were prepared by a simple solution-casting technique using a PVDF/graphene solution. In both cases, the amount of graphene was varied to observe and to compare their thermal and mechanical properties. The addition of graphene to the PVDF matrix resulted in changes in the crystallization and melting behaviors as confirmed by DSC analyses. Increasing the graphene content led to improved thermal stability of the PVDF nanocomposites prepared using both methods. Improvements in mechanical properties by the addition of graphene were also observed. Better performance was observed by the nanocomposites prepared by a mix-melting technique suggesting better dispersion and strong interface bonding between PVDF and graphene particles. Thermal and electrical conductivity were measured and compared. Microstructure and morphology were characterized using FTIR, XRD, and SEM analyses.

Thermal Degradation Kinetics Analysis of Ethylene-Propylene Copolymer and EP-1-Hexene Terpolymer.

LLDPE is a less crystalline polymer with vast industrial and domestic applications. It is imperative to understand the synthesis, processing conditions, and thermal degradation mechanism of the co- as well as terpolymers. This paper reports the in-situ synthesis and thermal degradation studies of the ethylene-propylene copolymer and ethylene-propylene-1-hexene terpolymer and its nanocomposite with ZnAL LDH sheets. The 1-hexene dosing during the in-situ process influenced the product yield and immensely affected the thermal stability of the resultant polymer. One milliliter 1-hexene in-situ addition increased the product yield by 170 percent, while the temperature at 10 percent weight loss in TGA was dropped by about 60 °C. While only 0.3 weight percent ZnAL LDH addition in the terpolymer improved the thermal stability by 10 °C. A master plot technique and combined kinetics analysis (CKA) were deployed to access the thermal degradation mechanism of the synthesized polymers.

Engineered biochar supported layered double hydroxide-cellulose nanocrystals composite-: Synthesis, characterization and azo dye removal performance.

In this work, engineered biochar decorated layered double hydroxides and cellulose nanocrystals (B-CuFe-CNC) biocomposites were synthesized by the facile ultrasonicated-co-precipitation technique. The biocomposite was investigated for purification of Eriochrome Black T (EBT) dye from water. The characterization results showed that the presence of CNC in biochar-layered double hydroxides resulted in a two-dimensional rod-like structure with excellent crystallinity, improved surface functionalities, and provides an attractive platform for the enhanced adsorption of azo anionic dye molecules. The adsorption system was appropriately demonstrated by the BBD-RSM (R2 > 0.994). The biocomposite exhibited higher EBT adsorption in the acidic pH range (2-5) due to strong electrostatic and chemical interactions. The kinetic and isotherm results were well demonstrated by pseudo-second order, Freundlich, and Redlich Peterson models. The maximum adsorption capacity of biocomposite was 876.2 mg/g achieved within 45 min. The spectroscopic analyses imply that the high removal of EBT by biocomposite is mainly governed by electrostatic attraction, hydrogen bonding, and chemical/metal complexation mechanisms. The biocomposite maintained high EBT removal after six successive adsorption cycles and excellent dye adsorption in the different water matrices. The results suggest that tailoring biochar properties with layered double hydroxide and CNC is a promising way for the enhanced removal of dye contaminants from wastewater.

Degree of conversion of two self-adhesive resin luting cements through different lengths of fiber post.

PURPOSE: To evaluate the degree of conversion (DoC) of self-adhesive resin luting cements when irradiated through different fiber post lengths. METHODS: A total of 60 teeth were sectioned to achieve lengths of 4 mm, 7 mm, and 10 mm, while 60 fiber posts were trimmed to give 3 mm, 6 mm, and 9 mm lengths. Post space was created to accommodate the fiber post and 1 mm of luting cement apically. Two self-adhesive resin luting cements (Multilink Speed and RelyX U200) were used. A total of four cycles of 20 s irradiation was done with an attenuated total reflectance Fourier transform infrared spectroscopy reading between each cycle. RESULTS: The mean ± standard deviation DoC achieved with a light-emitting diode and quartz tungsten halogen for Multilink Speed was 67.4 ± 2.7% and 72.4 ± 4.0%, respectively, while for RelyX U200, the corresponding values were 56.5 ± 2.7% and 62.0 ± 3.8%, respectively. For Multilink Speed, there was no significant difference between the control and the 3 mm group, while for RelyX U200, no significant difference was found between the 6 mm and 9 mm groups. All the other groups showed significant differences. CONCLUSION: The DoC reduced as the post length increased.

Sustainable wastewater treatment by biochar/layered double hydroxide composites: Progress, challenges, and outlook.

Biochar/layered double hydroxide (LDH) composites have gained considerable attention in recent times as low-cost sustainable materials for applications in water treatment. This paper critically evaluates the latest development in applications of biochar/LDH composites in water treatment with an emphasis on adsorption and catalytic degradation of various pollutants. The adsorption of various noxious contaminants, i.e., heavy metals, dyes, anions, and pharmaceuticals onto biochar/LDH composites are described in detail by elaborating the adsorption mechanism and regeneration ability. The synergistic effect of LDH with biochar exhibited significant improvement in specific surface area, surface functional groups, structure heterogeneity, stability, and adsorption characteristics of the resulting biochar/LDH composites. The major hurdles and challenges associated with the synthesis and applications of biochar/LDH composites in water remediation are emphasized. Finally, a roadmap is suggested for future research to assure the effective applications of biochar/LDH composites in water purification.

Date palm ash-MgAl-layered double hydroxide composite: sustainable adsorbent for effective removal of methyl orange and eriochrome black-T from aqueous phase.

Date palm ash (DPA) and MgAl-layered double hydroxide (LDH) composites were synthesized by the co-precipitation method and characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), X-ray diffraction (XRD), and Brunauer-Emmett-Teller (BET). The DPA-MgAl-LDH (DPA/MgAl) composites were employed for the removal of methyl orange (MO) and eriochrome black-T (EBT) from aqueous phase. Incorporation of 33.33% (w/w) DPA into the layers of MgAl increased the surface area from 44.46 to 140.65 m2/g, which leads to the improved adsorption performance. The maximum adsorption capacity of DPA/MgAl (1:2) at 298 K was 242.98 and 425.16 (mg/g) for MO and EBT, respectively. The adsorption data of dyes were adequately fitted by a pseudo-second-order and Langmuir isotherm model. The composite showed excellent reusability performance up to three cycles. Addition of DPA into MgAl-LDH resulted in an effective low-cost adsorbent for decontamination of dyes from wastewater. Graphical abstract ᅟ.