Unmodified Polymer Research Articles

Three-Dimensional Printing of Polymer Composites: Manufacturing and Mechanics

Polymers have been heavily used in manufacturing for decades, and with their use, improvements in the desired materials via composite materials utilizing a polymer matrix have been commonplace. Naturally, the increase in polymer additive manufacturing has come with an increase in interest in additively manufacturing polymer composites. This paper primarily covers the fused deposition modeling (FDM) method, ultraviolet (UV)-cured resin methods, multiple resin printing, and embedded sensors associated with additive manufacturing. In particular, the manufacturing and subsequent effect on material properties compared to unreinforced and unmodified 3D-printed polymers, the tradeoffs required in doing so, and the mechanisms behind these effects are discussed. The manufacturing methodology used or developed and the mechanisms behind these selections are discussed along with insights that could be gathered from material property effects seen across different studies. The mechanisms discussed also focus on the mechanisms between the different materials comprising the composite produced.

Optimization of sustainable polymer composites for surface metamorphosis in FDM processes

The demand for the development of sustainable manufacturing processes is enhanced by the necessity to optimize polymer composites, particularly in the context of fused deposition modeling (FDM). This research aims to enhance sustainable polymer composites to improve the surface metamorphosis during FDM processes. Various eco-friendly polymer matrices were integrated with novel composite reinforcements to evaluate their impact on surface quality, structural integrity, and the performance of FDM-printed components. Key surface features, including roughness (Ra), texture, and function, were quantified through both experimental and computational methods. The optimized composites led to a significant reduction in surface roughness, with Ra values improving by up to 45% compared to standard filaments. In addition, tensile strength was increased by 30% and flexural strength by 20% relative to unmodified polymer composites. Optimization strategies, guided by green chemistry principles and materials science, successfully enhanced surface finishes and functional properties, aligning with sustainability goals. The results demonstrate that optimized sustainable polymer composites can significantly improve the quality and performance of FDM prints, supporting more efficient and environmentally friendly manufacturing practices. This study contributes to advancing materials and processes in line with sustainability principles and surface engineering.

Zwitterionic Polymers for Biomedical Applications: Antimicrobial and Antifouling Strategies toward Implantable Medical Devices and Drug Delivery.

Poly(ethylene glycol) (PEG) is extensively utilized in biomedical applications due to its biocompatibility; however, its thermal instability and susceptibility to oxidative degradation significantly constrain its long-term effectiveness. Zwitterionic polymers, characterized by their distinctive structure, enhanced stability, and superior biocompatibility, offer a more advantageous alternative. These polymers exhibit super hydrophilicity, resist nonspecific protein adsorption, and maintain stability in biological environments due to their charge-neutral ionic nature. Zwitterionic polymers enhance anticancer drug delivery by precisely targeting tumor cells and facilitating an efficient drug release. Their inherent antifouling properties and prolonged circulation within the bloodstream render them highly suitable for redox-sensitive drug carriers, thereby augmenting the antitumor efficacy. Moreover, zwitterionic polymers markedly mitigate biofouling in implants, biosensors, and wound dressings, thereby improving both their functionality and their therapeutic outcomes. These advantages arise from the formation of robust hydration layers, which significantly enhance the hemocompatibility and inhibit the adhesion of proteins, platelets, and bacteria. Zwitterionic polymers, including sulfobetaine (SB), phosphorylcholine (PC), and carboxybetaine (CB), are increasingly employed in blood-contacting devices and as effective coating materials for implantable devices. This mini-review paper aims to explore the recent diverse biomedical applications of zwitterionic polymers and highlight their advantageous properties compared with unmodified polymers. We will cover their use in drug delivery systems, tumor targeting nanocarriers, antibiofouling and antibacterial activities in implantable devices, tissue engineering, and diagnostic devices, demonstrating how their unique properties can translate into different applications. Through this exploration, this Perspective will display the potential of zwitterionic polymers as innovative polymer materials in the field of biomedical engineering and beyond.

Impact of Surface Modification on the Oxidation of Linear Aliphatic Alcohols by Vanadium Complexes Supported on Merrifield Resin with Mixed Functionality Ligands

AbstractTwo oxidovanadium(IV) complexes [VO(xbp‐sc)] (1) and [VO(xbp‐tc)] (2) were prepared using hydrazine‐ether mixed functionality ligands Hxbp‐sc (I) and Hxbp‐tc (II), respectively. Complexes 1 and 2 were carefully grafted separately into imidazole‐modified chloromethylated polystyrene (Ps−Im) and unmodified chloromethylated polystyrene (PS−Cl) beads. Successfully anchored vanadium complexes Ps−Im‐[VO(xbp‐sc)] (3), Ps−Im‐[VO(xbp‐tc)] (4), Ps‐[VO(xbp‐sc)] (5), and Ps‐[VO(xbp‐tc)] (6) were tested for their catalytic potential towards the oxidation of aliphatic alcohols in the presence of hydrogen peroxide. Polymer‐grafted catalysts display excellent substrate conversion compared to most recent reports and good recyclability up to three cycles without losing much reactivity. High TOF values in the range of 183–591 h−1 are observed for the supported catalysts 3–6. The highest substrate conversion is observed for ethanol (63–97 %) under the optimized reaction conditions. Mainly, better substrate conversion is obtained with imidazole‐modified polymer beads grafted catalysts 3 and 4 than those grafted on unmodified polymer beads (5 and 6). Moreover, catalysts with the semicarbazide group in their ligand framework (3 and 5) show better reactivity towards alcohol with fewer carbon atoms. On the contrary, alcohols with longer carbon chains oxidize more easily in the presence of the catalyst with thiosemicarbazide frameworks (4 and 6).

Atomic oxygen erosion mechanism of polyimide via reactive molecular dynamics simulation and density functional theory calculation

Atomic oxygen (AO) causes serious oxidative degradation on polymeric materials in the space environment, yet understanding its reaction mechanism is a challenging task. Herein, we primarily investigate the reaction sites and reaction paths of pure polyimide material to AO erosion and propose a modification strategy involving electron-withdrawing groups to enhance the material's resistance to AO with density functional theory (DFT) and reactive force field molecular dynamics (ReaxFF MD). DFT calculations reveal that AO erosion is an electrophilic reaction, which preferentially interacts on the benzene ring with pronounced electron density distribution on the third part of the polyimide molecule. ReaxFF MD simulations validate this finding and provide additional reaction pathways that are divided into the early-stage reactions and later secondary reactions. In the early stage, only small number of AOs take part in the reactions that include the formation of CO bonds and ring opening processes. These reactions are relatively slow and majorly determine the AO resistance of the material. In the subsequent stage, AO predominantly reacts with reactive species and radicals generated from earlier reactions, leading to fast degradation. With these findings, we propose a strategy to enhance the AO resistance by introducing electron-withdrawing functional groups in the polyimides. As exemplified, the polyimide with -CF3 group shows 21.1% lower erosion yield than unmodified polymer. The present study gives a deep insight for the mechanism of AO erosion on polyimide by exploring its reaction sites and provides valuable theoretical guidance for improving the material's resistance to erosion.

Biopolymers and their Nanocomposites: Current Status and Future Prospects

Abstract: For many years, petroleum-based polymers have been successfully enhanced by the addition of nanoparticles as additives. Carbon nanotubes, graphene, nanoclays, 2-D layered materials, and cellulose nano whiskers are a few of the several nanoreinforcements that are currently being researched. In comparison to unmodified polymer resin, the use of these nanofillers with bio-based polymers could improve a wide range of physical properties, including barrier, flame resistance, thermal stability, solvent uptake, and rate of biodegradability. This nano-reinforcement is a very appealing method to create new functional biomaterials for a variety of applications because these enhancements are typically achieved at minimal filler content.

In English

Biopolymer matrices has been synthesized on the basis of ED-20 epoxy resin and soybean oil (SbO) bearing cyclocarbonate and epoxy groups. Mono(cyanoethyl)diethylenetriamine (UP) and tris(2-hydroxyethyl)amine (TEA) were used as hardeners. Chemical structure, mechanical properties, thermo-oxidative resistance of the samples and their changes after contact with distilled water, alkaline or acidic environment were studied. By means of ATR-FTIR the possible formation of H-NIPU (hybrid non-isocyanate polyurethane) fragments between cyclocarbonate groups of SbO and amino groups of the hardener was demonstrated. Influence of the curing mode and the type of hardener on water absorption, chemical and thermal oxidation resistance of the developed biopolymer matrices was thoroughly investigated. UP-based biopolymer matrices showed water and alkali resistance similar to the ones of neat epoxy polymers, while TEA-based biopolymer matrices showed better resistance to the acidic medium. The thermo-oxidative stability of the chosen samples was revealed by the TGA method in an air atmosphere. It was demonstrated that epoxy polymer cured with TEA hardener were more stable than the one cured with UP hardener. The similar dependence is observed for biopolymer matrices based on TEA hardener. At the same time, the curing mode has almost no effect on ultimate tensile strength value of the samples with ED-20/UP composition. However, the addition of functionalized SbO to the epoxy matrix cured with both TEA and UP hardeners increases the ultimate tensile strength values regardless of the type of oil functionalization. As expected, all biopolymer matrices exhibited higher ultimate tensile strength compared with unmodified epoxy polymers, which provides the possibility of their further application to obtain multi-layered bioplastics.

Preparation of xyloglucan-grafted poly(N-hydroxyethyl acrylamide) copolymer by free-radical polymerization for in vitro evaluation of human dermal fibroblasts

Xyloglucan is a rigid polysaccharide that belongs to the carbohydrate family. This hemicellulose compound has been widely used in biomedical research because of its pseudoplastic, mucoadhesive, mucomimetic, and biocompatibility properties. Xyloglucan is a polyose with no amino groups in its structure, which also limits its range of applications. It is still unknown whether grafting hydrophilic monomers onto xyloglucan can produce derivatives that overcome these shortcomings. This work aimed to prepare the first copolymers in which N-hydroxyethyl acrylamide is grafted onto tamarind xyloglucan by free-radical polymerization. The biocompatibility of these structures in vitro was evaluated using human dermal fibroblasts. Gamma radiation-induced graft polymerization was employed as an initiator by varying the radiation dose from 5–25 kGy. The structure of the graft copolymer, Xy-g-poly(N-hydroxyethyl acrylamide), was verified by thermal analysis, Fourier transform infrared spectroscopy, and nuclear magnetic resonance spectroscopy. The findings indicate that the degree of grafting and the cytotoxicity/viability of the xyloglucan-based copolymer were independent of dose. Notably, the grafted galactoxyloglucan exhibited efficient support for human dermal fibroblasts, showing heightened proliferative capacity and superior migration capabilities compared to the unmodified polymer. This copolymer might have the potential to be used in skin tissue engineering.

Influence of Low-Molecular-Weight Esters on Melt Spinning and Structure of Poly(lactic acid) Fibers.

Poly(lactic acid) has great potential in sectors where degradability is an important advantage due to its polymer nature. The medical, pharmaceutical, and packaging industries have shown interest in using PLA. To overcome the limitations of stiffness and brittleness in the polymer, researchers have conducted numerous modifications to develop fibers with improved properties. One such modification involves using plasticizing modifiers that can provide additional and desired properties. The scientific reports indicate that low-molecular-weight esters (LME) (triethyl citrate and bis (2-ethylhexyl) adipate) affect the plasticization of PLA. However, the research is limited to flat structures, such as films, casts, and extruded shapes. A study was conducted to investigate the impact of esters on the process of forming, the properties, and the morphology of fibers formed through the melt-spinning method. It was found that the modified PLA required different spinning and drawing conditions compared to the unmodified polymer. DSC, FTIR, WAXD, and GPC/SEC analyses were performed for the modified fibers. Mechanical tests and morphology evaluations using SEM microscopy were also conducted. The applied plasticizers lowered the temperature of the spinning process by 40 °C, and allowed us to obtain a higher degree of crystallinity and a better tenacity at a lower draw ratio. GPC/SEC analysis confirmed that the polymer-plasticizer interaction is physical because the booth plasticizer peaks were separated in the chromatographic columns. The use of LME in fibers significantly reduces the temperature of the spinning process, which reduces production costs. Additives significantly change the production process and the structure of the fiber depending on their rate, which may affect the properties, e.g., the rate of degradation. We can master the degree of crystallinity through the variable amount of LME. The degree of crystallization of the polymers has a significant influence on polymer application.

Eudragit® L100 Post-Modification via Ugi Multicomponent Reaction

This work investigated the post-modification of commercial poly(methyl mechacrylate-coacrylic acid) using the versatile multicomponent Ugi reaction. This reaction introduces diverse functionalities to tailor the polymer properties effectively. The commercial copolymer which is known for biocompatibility and drug delivery application was subjected to the Ugi reaction, altering its chemical structure. The structure of the modified polymer was checked by Fourier transform infrared spectroscopic and nuclear magnetic resonance and thermal characterizations, confirming successful Ugi component integration. Additionally, gel permeation chromatography assessed molecular weight changes. Results revealed enhanced thermal stability of the modified polymers compared to unmodified polymer, potentially advantageous in high-temperature applications. In summary, the study demonstrates efficient poly(methyl mechacrylate-co-acrylic acid) post-modification through a multicomponent Ugi reaction, yielding tailored polymers. Comprehensive spectroscopic, thermal, and gel permeation analyses shed light on structural changes and improved stability, pivotal for innovative applications like drug delivery.

Pendant Modification of Poly(methyl methacrylate) to Enhance Its Stability against Photoirradiation.

Photostabilization of functional polymeric materials is important for protection against aging and ultraviolet (UV) irradiation. There is, therefore, the impetus to modify polymers to increase their resistance to photodegradation and photooxidation on extended exposure to UV light in harsh conditions. Various polymeric additives have been designed and synthesized in recent years, and their potential as photostabilizers has been explored. Reported here is the effect of pendant functionalization of poly(methyl methacrylate) (PMMA) through organometallic moiety incorporation into the polymer's backbone. The reaction of PMMA with ethylenediamine leads to the formation of an amino residue that can react with salicylaldehyde to produce the corresponding Schiff base. Adding metal chlorides (zinc, copper, nickel, and cobalt) led to the formation of organometallic residues on the polymeric chains. Thin films of modified and unmodified PMMA were produced and irradiated with UV light to determine the effect of pendant modification on photostability. The photostabilization of PMMA was assessed using a range of methods, including infrared spectroscopy, weight loss, decomposition rate constant, and surface morphology. The modified PMMA incorporating organic Schiff base metal complexes showed less photodecomposition than the unmodified polymer or one containing the Schiff base only. Thus, the metals significantly reduced the photodegradation of polymeric materials. The polymer containing the Schiff base-cobalt unit showed the least damage in the PMMA surface due to photoirradiation, followed by those containing nickel, zinc, and copper, in that order.

Boosting the performances of lithium metal batteries through in-situ construction of dual-network self-healing gel polymer electrolytes

As an alternative to conventional liquid electrolytes, self-healing gel polymer electrolytes (SHGPEs) can effectively increase the safety performance and lifetime of lithium metal batteries (LMBs). However, the poor mechanical properties and unfavorable ionic conductivity limit its further use. Herein, based on a simple in situ polymerization strategy, a novel dual-network structure self-healing gel polymer electrolyte (DN-SHGPE) with mechanical strength and self-healing properties is designed and prepared. The brush copolymer PEG-UPy contains a large amount of dynamic urethane-pyrimidine (UPy) dimer, acting as the first network, which gives GPE great self-healing ability and increases the safety and cycle lifetime of lithium batteries. The second network is cross-linked polyethylene glycol diacrylate (PEGDA), which ensures the dimensional stability and mechanical qualities of GPE. In comparison to the unmodified polymer electrolyte PEG-UPy, DN-SHGPE exhibits better ionic conductivity, excellent mechanical property, and good thermal stability, as well as good interaction stability with Li metal anode. When assembled with LiFePO4 and lithium metal electrodes, the resultant cells show a high reversible specific capacity and good rate capability.

SYNTHESIS AND CHARACTERIZATION OF SOME MODIFIED EPOXY RESINS WITH FATTY ACIDS

Some modified epoxy resins were prepared from the reaction of epoxy resin with some fatty acids (palmitic acid, stearic acid, oleic acid)in the presence of paratoluene Sulfonic acid at low temperature ranging between 70,90C◦ and at high temperature ranging between 280,300C◦. All the epoxy modifiers were characterized by IR and acid value AV. The mechanical properties (Hardness, Impact strength, Elongation, Tensile strength) and thermal stability (TGA) were studied. The mechanical properties of modified are lower than unmodified polymers, but Oleic acid was the best of all. The thermal stability was decreased according to below (Stearic acid> Palmatic acid>Oleic. acid). 

DEAE/Catechol-Chitosan Conjugates as Bioactive Polymers: Synthesis, Characterization, and Potential Applications.

This work provides the first description of the synthesis and characterization of water-soluble chitosan (Cs) derivatives based on the conjugation of both diethylaminoethyl (DEAE) and catechol groups onto the Cs backbone (Cs-DC) in order to obtain a Cs derivative with antioxidant and antimicrobial properties. The degree of substitution [DS (%)] was 35.46% for DEAE and 2.53% for catechol, determined by spectroscopy. Changes in the molecular packing due to the incorporation of both pendant groups were described by X-ray diffraction and thermogravimetric analysis. For Cs, the crystallinity index was 59.46% and the maximum decomposition rate appeared at 309.3 °C, while for Cs-DC, the values corresponded to 16.98% and 236.4 °C, respectively. The incorporation of DEAE and catechol groups also increases the solubility of the polymer at pH > 7 without harming the antimicrobial activity displayed by the unmodified polymer. The catecholic derivatives increase the radical scavenging activity in terms of the half-maximum effective concentration (EC50). An EC50 of 1.20 μg/mL was found for neat hydrocaffeic acid (HCA) solution, while for chitosan-catechol (Cs-Ca) and Cs-DC solutions, concentrations equivalent to free HCA of 0.33 and 0.41 μg/mL were required, respectively. Cell culture results show that all Cs derivatives have low cytotoxicity, and Cs-DC showed the ability to reduce the activity of reactive oxygen species by 40% at concentrations as low as 4 μg/mL. Polymeric nanoparticles of Cs derivatives with a hydrodynamic diameter (Dh) of around 200 nm, unimodal size distributions, and a negative ζ-potential were obtained by ionotropic gelation and coated with hyaluronic acid in aqueous suspension, providing the multifunctional nanoparticles with higher stability and a narrower size distribution.

Structuring of Modified Epoxy Composite Materials by Infrared Spectroscopy

A comparative evaluation of the structuring processes of the epoxy polymer system with epoxy polymers modified with polyvinyl chloride solution and epoxy composites filled with finely dispersed titanium oxide powder was carried out. Analysis of the infrared (IR) absorption spectra of the studied epoxy polymer and epoxy composite materials showed the presence of deformation and valence vibrations of certain groups of atoms. The oscillations of groups of atoms with double bonds and regions of existence of triple bonds were also revealed. In the region of high frequencies, absorption bands correspond to valence vibrations of groups containing a hydrogen atom. The presence of triple bonds in the epoxy polymer system was determined, indicating unreacted functional groups. This fact corresponds to the low content of the gel fraction of unmodified epoxy polymers after heat treatment and indicates the formation of a system with insufficient chemical bonds. The absorption bands of the epoxy composite material filled with titanium oxide powder are characterized by a lower optical density and a larger peak area compared to the bands of the unmodified epoxy polymer, which indicates the formation of a higher number of crosslinking nodes of the epoxy composite material. The introduction of polyvinyl chloride into the composition of the epoxy polymer system increases the degree of structuring of epoxy polymers. However, a smaller number of formed chemical bonds of the modified epoxy polymer was recorded compared to epoxy composites containing titanium oxide particles. The highest degree of structuring is provided in polyvinyl chloride-modified epoxy composites containing titanium oxide powder due to intensive structuring and formation of double and triple bonds.

Transport properties of polymer blends and composite membranes for selective permeation of hydrogen

Graphene Oxide (GO) dispersed in a polymer blend of Polystyrene (PS)/Poly (methyl methacrylate) (PMMA) nanocomposite membranes have been prepared by the solution cast method for hydrogen gas permeation application. This paper reports a study of blends of PMMA and PS that were prepared in different ratios of weight percentage for PMMA: PS (80:20, 50:50 and 60:40) composite with 1 wt% of GO and 2 wt% of GO. The structural and morphological properties of these prepared composite membranes have been characterized using gas permeation, Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS). UV Spectroscopy and FT-IR have carried out the optical absorbance measurement of the composite membranes. The permeability measurements indicate that the GO nanofillers in blends of PS/PMMA have shown higher permeability for hydrogen gas than that of pure polymers. The gases used for the permeation measurements were H2, CO2, N2 and CH4. Selectivity has been calculated for H2/CO2, H2/N2 and H2/CH4 gas pairs and plotted to show Robeson's 2008 upper bound and compared with reported data. The transport properties of these gases have been compared with that of a neat membrane. The permeability of all gases has increased to that of the unmodified polymer membrane. The selectivity measurements show that GO composite with PS/PMMA blend membranes is highly selective for hydrogen gas from different gas pairs, therefore, these composite membranes can be used for hydrogen purification. There is a trade-off between permeability and selectivity parameters; GO nanofillers keep selectivity constant as permeability increases, which the nanogap theory could explain.

Synthesis, characterization and evaluation of hyaluronic acid-based polymers for nasal delivery

Epidemiological research has found that between 5 and 12 percent of the population suffers from chronic rhinosinusitis. Patients are dealing with local side effects such as nasal dryness, sporadic sneezing, and nasal pain in addition to the inflammation. The aim of this study was to synthesize a polymer based on hyaluronic acid in order to provide lubrication combined with a ligand leading to a covalent binding on the nasal mucosa. Hyaluronic acid (HA) was modified with L-cysteine ethyl ester hydrochloride (CYS) via amid bond formation. Ellman's assay, together with spectroscopic techniques like IR and 1H NMR, confirmed that HACys had been successfully synthesized. It was demonstrated that HACys is safe for administration on the nasal mucosa. The mucoadhesive potential was determined by 3.26-fold with the rotating cylinder assay and 1.4-fold in terms of bioadhesive examination, respectively. Further, the stability of the modified polymer was improved by 7.6-fold compared to the unmodified polymer. Spraying the formulation on the nasal mucosa, the residence time of a model drug was 1.74-fold prolonged at the site of action compared to unmodified polymer. In light of these findings, modified hyaluronic acid (HACys) displayed compelling properties such as lubricity, targeted application, long-lasting effect, and safety and therefore could be an excellent candidate for nasal application.

Entirely S-protected thiolated hydroxyethylcellulose: Design of a dual cross-linking approach for hydrogels

AimThe aim of this study was the synthesis and evaluation of entirely S-protected thiolated hydroxyethylcellulose (HEC) with low and high viscosity, as well as thiolated poly-L-lysine (poly-L-Lys) used as dual-acting ionic as well as thiol-disulfide exchange mediated cross-linking hydrogel. MethodsBis(mercaptosuccinic acid) was covalently attached to low and high viscous HECs via Fisher esterification, obtaining S-protected polymers. Poly-L-Lys-cysteine was synthesized via amidation of poly-L-Lys-HBr with cysteine (Cys). Thiolated polymers were examined in terms of cytotoxicity and rheological behavior of hydrogels containing these thiomers was evaluated with a cone-plate rheometer. ResultsThiomers showed less cytotoxicity compared to the corresponding unmodified polymers. Rheological studies showed that cross-linking occurred between the two polymers via thiol-disulfide exchange reactions facilitated by the complementary charges. Employing poly-L-Lys-Cys in a concentration of either 0.5 or 5% (m/v) resulted in a 34.5-fold or 17.3-fold as well as a 53.6-fold or 29.6-fold improvement in dynamic viscosity within 5 min at 37 °C on S-protected thiolated low and high viscous HEC, compared to the corresponding unmodified HECs, respectively. ConclusionBy the combination of anionic S-protected thiolated polymers with a cationic thiolated polymer, dual-acting hydrogels exhibiting a time dependent increase in viscosity can be designed.

Aniline-Naphthylamine Copolymer as Sorbent for Needle Trap Device

In current work, aniline-naphthylamine copolymers were prepared using electrochemical technique and then applied as a new sorbent for needle trap extraction of some volatile organic compounds from aqueous solution in headspace mode. The scanning electron microscopy and infrared spectrometry techniques were used to characterization of synthesized anilinenaphthylamine copolymers of aniline and naphthylamine. The results showed that aniline-naphthylamine copolymer compared to unmodified polymer, has higher porosity and non-uniform structures. The significant parameters of the sorbent preparation and extraction process such as the type and concentration of polymer, time and voltage of electrochemical deposition, the extraction time and temperatures and salt content were studied and optimized. The modified device is sensitive and fast providing good analytical parameters so that the detection limit of 0.9-2 ng L-1 and the quantification limit of 3-7 ng L-1 along with equilibrium time of 20 minutes were obtained. The linearity of method was obtained in the range of 15-1500 ng L-1 with R2 > 0.9996. The method repeatability was considered at 50 ng L-1 and relative standard deviations of 3-5% were obtained. To finish, the performance of proposed device was studied via the extraction of selected analytes in real water samples and the relative recovery values were found to be in the range of 94-102%, showing no matrix effect.

Synthesis and Optimization of Superhydrophilic-Superoleophobic Chitosan-Silica/HNT Nanocomposite Coating for Oil-Water Separation Using Response Surface Methodology.

In this current study, facile, one-pot synthesis of functionalised nanocomposite coating with simultaneous hydrophilic and oleophobic properties was successfully achieved via the sol–gel technique. The synthesis of this nanocomposite coating aims to develop a highly efficient, simultaneously oleophobic-hydrophilic coating intended for polymer membranes to spontaneously separate oil-in-water emulsions, therefore, mitigating the fouling issue posed by an unmodified polymer membrane. The simultaneous hydrophilicity-oleophobicity of the nanocoating can be applied onto an existing membrane to improve their capability to spontaneously separate oil-in-water substances in the treatment of oily wastewater using little to no energy and being environmentally friendly. The synthesis of hybrid chitosan–silica (CTS-Si)/halloysite nanotube (HNT) nanocomposite coating using the sol–gel method was presented, and the resultant coating was characterised using FTIR, XPS, XRD, NMR, BET, Zeta Potential, and TGA. The wettability of the nanocomposite coating was evaluated in terms of water and oil contact angle, in which it was coated onto a polymer substrate. The coating was optimised in terms of oil and water contact angle using Response Surface Modification (RSM) with Central Composite Design (CCD) theory. The XPS results revealed the successful grafting of organosilanes groups of HNT onto the CTS-Si denoted by a wide band between 102.6–103.7 eV at Si2p. FTIR spectrum presented significant peaks at 3621 cm−1; 1013 cm−1 was attributed to chitosan, and 787 cm−1 signified the stretching of Si-O-Si on HNT. 29Si, 27Al, and 13H NMR spectroscopy confirmed the extensive modification of the particle’s shells with chitosan–silica hybrid covalently linked to the halloysite nanotube domains. The morphological analysis via FESEM resulted in the surface morphology that indicates improved wettability of the nanocomposite. The resultant colloids have a high colloid stability of 19.3 mV and electrophoretic mobility of 0.1904 µmcm/Vs. The coating recorded high hydrophilicity with amplified oleophobic properties depicted by a low water contact angle (WCA) of 11° and high oil contact angle (OCA) of 171.3°. The optimisation results via RSM suggested that the optimised sol pH and nanoparticle loadings were pH 7.0 and 1.05 wt%, respectively, yielding 95% desirability for high oil contact angle and low water contact angle.