Enhanced chlorine-resistant and low biofouling reverse osmosis polyimide-graphene oxide thin film nanocomposite membranes for water desalination

The effect of graphene oxide (GO) loading (0.03, 0.06, 0.09, 0.12, and 0.30 wt%) in the aqueous phase on the performance of reverse osmosis (RO) polyimide (PI) thin film composite (TFC) membrane was investigated. TFC and thin film nanocomposite (TFN) membranes were produced through interfacial polymerization and the imide linkage was confirmed by attenuated total reflection Fourier transform infrared spectroscopy. The spongy-like structure with vertical fingers of RO PI-GO TFN membranes was explored by top-surface and cross-sectional field emission scanning electron microscope (FE-SEM). The roughness of the membranes was determined. All PI-GO TFN membranes exhibited enhanced desalination performance in comparison with PI membranes. Samples with 0.06 wt% GO performed the best with a water flux of 31.80 L/m²/h, salt rejection of 98.8%, and very good antibiofouling properties. This hydrophilic membrane displayed significantly enhanced chlorine-resistance with water flux of 36.3 L/m²/h and salt rejection of 98.5%. This work provides a promising start for designing rapid water permeation PI-GO TFN membranes in water desalination.     

Characterization of reactive graphene oxide synthesized from ball – milled graphite: its enhanced reinforcing effects on cement nanocomposites

In this study, commercial graphite powder (GP) of particle size 100 micron was subjected to high energy ball-milling (HEBM) to produce ball-milled graphite powder (BMGP) of particle size 780 nm. Both GP and BMGP were converted to respective graphene oxides (GOs) (labeled as GO1 and GO2) using Hummer’s method, which were then characterized using techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X- ray diffraction (XRD). GO1 and GO2 were then investigated for their effects on compressive strength of cement mortar matrix at different curing times of 7, 14, and 28 days. Effect of variation of concentration (ranging between 0.125 and 1.00 wt% of cement) of GO1 and GO2 on the strength of matrix was examined. Microstructures of GO1-cement mortar nanocomposite and GO2-cement mortar nanocomposite were studied after 28 days of curing using SEM. Obtained results show that addition of 1.00 wt% GO1 and GO2 showed best performance by increasing the strength to 63 and 78%, respectively, in comparison to the unreinforced control sample. Improved performance of GO2 was attributed to more number of reactive sites of GO nanosheets induced by ball-milling treatment of graphite precursor.     

Nanocomposite hollow fiber nanofiltration membranes: Fabrication,characterization, and pilot-scale evaluation for surface water treatment

Thin-film nanocomposite (TFN) membranes were fabricated by interfacial polymerization of a polyamide (PA) layer on the shell side of hollow fiber membrane supports. TiO₂ nanoparticle loadings in the thin-film layer were 0.01, 0.05, and 0.20 wt %. Nanoparticle-free PA thin-film composite (TFC) membranes served as the comparative basis. The TFN membranes were characterized in terms of the chemical composition, structure, and surface properties of the separation layer. Incorporating nanoTiO₂ improved membrane permeability up to 12.6-fold. During preliminary laboratory-scale evaluation, TFN membranes showed lower salt rejection but higher TOC rejection in comparisons with the corresponding values for TFC controls. Based on the performance in lab-scale tests, TFN membranes with 0.01 wt % nanoTiO₂ loading were selected for an evaluation at the pilot scale with synthetic surface water as the feed. While the permeate flux during long-term pilot-scale operation gradually decreased for TFC membranes, TFN membranes had a higher initial permeate flux that gradually increased with time. The TOC rejection by TFN and TFC membranes was comparable. We conclude that TFN membranes show promise for full-scale surface water treatment applications. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48205.     

Polyamide-based membranes consisting of nanocomposite interlayers for high performance nanofiltration

It is still a task to synthesize polyamide-based membranes with selective layers down to 10–20 nm for high performance desalination. Herein, cellulose nanocrystals (CNC) were used as one-dimensional (1D) nanorods and graphene oxides (GO) as two-dimensional (2D) nanosheets, respectively, to construct nanocomposite interlayers for synthesizing polyamide layers thinner than 15 nm. The 2D nanosheets are homogeneously mixed with the 1D nanorods and effectively reduce the surface roughness of the nanocomposite interlayers with decreasing the mass ratio of CNC/GO. Polyamide layers with a thickness of 10–15 nm have been synthesized at an ultralow monomer concentration of 0.025 wt% on these CNC/GO nanocomposite interlayers. The polyamide-based membranes exhibit extremely high water permeation (45.9 L/m²·h·bar) without losing their salt rejection ability. The nanofiltration performances of these polyamide-based membranes are higher than most of the reported nanofiltration membranes in recent years.     

金属有机骨架/聚酰胺薄层纳米复合膜的研究进展

相较于传统聚酰胺薄层复合（TFC）膜,金属有机骨架/聚酰胺薄层纳米复合（TFN）膜得益于MOFs材料的高比表面积、有序可控的孔隙结构、良好的聚合物相容性和可定制的化学功能,展现出更高的渗透选择性,在工业应用中显示出巨大的分子和离子分离潜力。本文首先简述了MOFs聚酰胺复合膜的研究背景,然后从MOFs材料的特性和MOFs聚酰胺复合膜的制备策略两个方面出发,总结了MOFs聚酰胺膜研究的最新进展。讨论了MOFs的物化特征在TFN膜的微观结构和分离性能中起的作用;介绍了MOFs聚酰胺复合膜的制备策略,重点对MOFs负载方法及效率进行了分析。最后简述了MOFs聚酰胺复合膜在气、液体系分离中的应用;对MOFs聚酰胺膜在应用过程中的稳定性问题进行了分析,并对未来MOFs聚酰胺复合膜优化MOFs负载和功能性设计的研究进行了展望。     

Novel composite nanofibers based on polyamide 66/graphene oxide- grafted aliphatic- aromatic polyamide: preparation and characterization

New polyamide 66/graphene oxide (GO)-grafted aliphatic-aromatic polyamide (polyamide-imide) (PAI) (PA66/GOF) composites nanofibers were successfully prepared via electrospinning method for the first time. An polyamide imide (PAI) was synthesized using polycondensation reaction from a dicarboxylic acid and a diamine based on 4,4′-(4,4′-isopropylidenediphenyl-1,1′-diyldioxy) dianiline, and characterized by ¹HNMR and FTIR. Morphological, structural, thermal and mechanical characteristics of the nanocomposite fibers were investigated by means of SEM, TEM, WAXD, DMTA and TGA techniques. Composites nanofibers of PA66/GO, PA66/PAI and PA66/GOF with smooth surface, uniform structure as well as with diameter ranging from 195 to 784 nm were obtained. The GO incorporation caused a reduction in the nanofibers diameters. The TEM images showed that the GO was well dispersed in the PA66 nanofibers without significant aggregation. An approximately 10 °C temperature increase in the glass transition temperature of PA66 was achieved by addition of 0.5 wt% of PAI, resulting from aliphatic-aromatic structure of PAI. By the TGA results, an increase about 40 °C was observed in the thermal stability of PA66/PAI composite nanofibers in comparison with that of pure PA66 nanofibers.     

Improved separation performance of polyamide based reverse osmosis membrane incorporated with poly(dopamine) coated carbon nanotubes

A series of polyamide thin-film nanocomposite (PA TFN) membranes have been fabricated by incorporating hydrophilic poly(dopamine) (PDA) coated carbon nanotubes (CNTs@PDA) into the PA selective layer via interfacial polymerization. The effects of PDA coating thickness on surface characteristics and separation performances of membranes are studied in detail. The PDA coating makes the surface of PA TFN membrane more hydrophilic, smoother and less electronegative. The desalination performance is obviously influenced by the coating thickness of PDA and the loading concentration of PDA@CNTs. The water fluxes of PDA@CNTs incorporated PA TFN membranes have been improved without sacrificing NaCl rejections. When the loading concentration is 0.0010%, the maximum water flux is 48.1 L m⁻² h increasing by 45% compared with that of pristine PA membrane. Meanwhile, the NaCl rejection is up to 99.8%. The CNTs@PDA incorporated PA TFN membranes exhibit better anti-fouling property and separation performance durability. This work proves that CNTs@PDA has great potential application in PA TFN membranes.     

Fabrication of polyamide thin film nanocomposite reverse osmosis membrane incorporated with a novel graphite-based carbon material for desalination

The properties of polyamide (PA) thin film composite (TFC) membranes are affected by many variables, especially the additives in the process of interfacial polymerization that play an important role in the properties of membranes. In this study, a new type graphite carbon was added into organic phase containing trimesoyl chloride for interfacial polymerization with aqueous phase containing m-phenylenediamine to prepare modified polyamide thin film nanocomposite (TFN) membranes for reverse osmosis (RO) adhibition. Polysulfone ultrafiltration membranes were used as the carrier of the interfacial polymerization. The concentration of graphite carbon was selected from 0.002 to 0.01 wt%. The polyamide nanocomposite membrane prepared with the concentration of 0.004 wt% graphite carbon showed the best RO desalination performance, which the water flux of this TFN membrane is over 2.3 times as much as pristine TFC membrane, and the salt rejection is over 99%. This article provides a well-performing polyamide thin film nanocomposite membrane modified by a new-type carbon nanoparticles consequently.     

Studying the Potential Application of Electrospun Polyethylene Terephthalate/Graphene Oxide Nanofibers as Electroconductive Cardiac Patch

Nowadays, engineering‐based cardiac patches aim to accelerate cardiac regeneration in myocardial infarcted tissues. Considering the fundamental role of cardiac electrophysiology in myocardial function, this study aims to investigate graphene oxide (GO) incorporation in the polyethylene terephthalate (PET) nanofibrous scaffold, as a conductive cardiac patch. The PET/GO nanocomposites are prepared using the uniaxial nozzle and coaxial nozzle electrospinning processes and comprehensively evaluated. The morphological observation indicates a uniform beaded free morphology with an average diameter of 147 ± 38 and 253 ± 67 nm for solid and core–shell nanocomposite fibers, respectively. Addition of GO to the PET nanofibers in a concentration of 0.05 wt% remarkably increases the Young modulus of mats from 30 ± 0.03 to 60 ± 0.02 and 69 ± 0.08 MPa for solid and core–shell nanofibers, respectively. Also, the electroconductivity is improved from 0.7 × 10^?6 to 1.175 × 10^?6 and 1.3 × 10^?6 S cm^?1 for solid and core–shell nanofibers, which are in the range of cardiac electroactivity values. PET/GO substrate interestingly supports human umbilical vein endothelial cells’ spreading morphology and cardiomyocyte elongated morphology, mainly where the GO nanosheets are distributed near the surface of nanofibers. In conclusion, the core–shell electrospun PET/GO nanocomposite fibers are suggested as a potential electroactive cardiac patch to improve cardiac cell attachment and proliferation.     

Core-shell particles for design of high-performance polymeric materials with good transparency and toughness

The exfoliated graphene oxides (GOs) prepared via the Hummer’s method were well dispersed in water but re-stacked if drying to a powder form as observed by transmission electron microscope and x-ray diffraction pattern. Hence, they were directly mixed with poly(vinyl alchohol) (PVA) in water to fabricate the PVA/GO nanocomposite films by casting the resulting aqueous solutions and drying. As the nanocomposite films with no less than 5 wt% GO content were subjected to combustion, the char residue could preserve their original film profile acting like an inflammable scaffold. The glassy transition temperature of as-fabricated PVA/GO nanocomposite films barely changed with the content of GO but significantly decreased from ~70 to ~10 °C as environmental relative humidity (RH) was increased from 20 to 80 % due to more moisture adsorption. Therefore, the mechanical behavior of PVA/GO nanocomposite films not only depended on the GO content but also RH, exhibiting from rubbery to glassy status.     

Enhanced thermal conductivity and dimensional stability of flexible polyimide nanocomposite film by addition of functionalized graphene oxide

Polyimide (PI) nanocomposites with both enhanced thermal conductivity and dimensional stability were achieved by incorporating glycidyl methacrylate‐grafted graphene oxide (g‐GO) in the PI matrix. The PI/g‐GO nanocomposites exhibited linear enhancement in thermal conductivity when the amount of incorporated g‐GO was less than 10 wt%. With the addition of 10 wt% of g‐GO to PI (PI/g‐GO‐10), the thermal conductivity increased to 0.81 W m^?1 K^?1 compared to 0.13 W m^?1 K^?1 for pure PI. Moreover, the PI/g‐GO‐10 composite exhibited a low coefficient of thermal expansion (CTE) of 29 ppm °C^?1. The values of CTE and thermal conductivity continuously decreased and increased, respectively, as the g‐GO content increased to 20 wt%. Combined with excellent thermal stability and high mechanical strength, the highly thermally conducting PI/g‐GO‐10 nanocomposite is a potential substrate material for modern flexible printed circuits requiring efficient heat transfer capability.     

The rheological,mechanical and templating effects of graphene oxide nanosheets in filled gel spun polyacrylonitrile

Polyacrylonitrile (PAN) in dimethylformamide solution containing 0.25 or 1 wt% graphene oxide (GO) was gel spun to tapes. Scanning electron microscopy of tapes showed compact staircase cross-sections hallmarking the gel spun products. Low shear rate rheometry of the tape precursors revealed a viscosity increase, while the structural viscosity indexes of dispersions dropped to 40 and 70% at high shear rates by 0.25 and 1 wt% GO inclusion, respectively. Furthermore, the sol–gel transition temperature of PAN solution was enhanced by about 2.5 and 10 °C with 0.25 and 1 wt% GO inclusion, respectively. Strain sweep test implied a gel-to-sol transition from 9 to 28% by 1 wt% GO inclusion. The experimental reinforcement coefficient corresponded the aligned Halpin–Tsai model confirming the suitable dispersion preparation route namely master batch dilution implementing strong interphase formation among the PAN chains and GO platelets. Molecular evolution analysis during air stabilization through a combined second derivative of FTIR spectra, Gaussian peak fitting represented by I_sd index, indicated the initial cyclization at 290 °C followed by its enhanced rate. Final I_sd was noticed to be 48% higher for the tapes containing GO nanosheets. GO inclusion not only enhanced the tape heat of stabilizations but also differentiated its proportional I_sd and toughness dependency based on the heat of stabilization.     

High-Performance and Biobased Polyamide/Functionalized Graphene Oxide Nanocomposites through In Situ Polymerization for Engineering Applications

In this study, biobased polyamide/functionalized graphene oxide (PA-FGO) nanocomposite is developed using sustainable resources. Renewable PA is synthesized via polycondensation of hexamethylenediamine (HMDA) and biobased tetradecanedioic acid. Furthermore, GO is functionalized with HMDA to improve its compatibility with biobased PA and in situ polymerization is employed to obtain homogeneous PA-FGO nanocomposites. Compatibility improvement provides simultaneous increases in the tensile strength, storage modulus, and conductivity of PA by adding only 2 wt% FGO (PA-FGO2). The tensile strength and storage modulus of PA-FGO2 nanocomposite are enhanced dramatically by ≈50% and 30%, respectively, and the electrical conductivity reached 3.80 × 10^–3 S m⁻¹. In addition, rheology testing confirms a shear-thinning trend for all samples as well as a significant enhancement in the storage modulus upon increasing the FGO content due to a rigid network formation and strong polymer-filler interactions. All these improvements strongly support the excellent compatibility and enhanced interfacial interactions between organic–inorganic phases resulting from GO surface functionalization. It is expected that the biobased PA-FGO nanocomposites with remarkable thermomechanical properties developed here can be used to design high-performance structures for demanded engineering applications.     

沸石/聚酰胺反渗透复合膜的制备

为了提高反渗透膜的通量,通过在界面聚合反应过程中添加NaA型纳米沸石分子筛制备了沸石/聚酰胺反渗透复合膜,采用SEM及复合膜性能测试的方法比较了沸石分子筛添加在水相或者油相中时对膜结构及分离性能的影响.SEM图谱结果表明:沸石分子筛添加在油相中时,沸石在聚酰胺基质中分散均匀,膜结构比较均一;但当沸石分子筛添加在水相中时...     

Polydopamine functional reduced graphene oxide for enhanced mechanical and electrical properties of waterborne polyurethane nanocomposites

Waterborne polyurethane/polydopamine (PDA) functional reduced graphene oxide (WPU/PDRGO) nanocomposites were prepared by in situ emulsification method. The presence of a PDA layer and the partial reduction of GO by PDA were confirmed by FTIR, XRD, Raman spectra, and TGA. It was found that the interfacial PDA layers facilitated the dispersion of the PDRGO sheets in the WPU matrix and enhanced mechanical properties of the WPU matrix. The resulting WPU/PDRGO nanocomposite coatings show excellent electrical conductivity (9.9?×?10^?6–1.1?×?10^?4 S cm^?1) corresponding to a PDRGO content of 1–16 wt%. The obtained waterborne polyurethane/graphene nanocomposite dispersions are promising for anticorrosion, antistatic, conductive, and electromagnetic interference shielding coatings.     

Effect of incorporation of graphene oxide and graphene nanoplatelets on mechanical and gas permeability properties of poly(lactic acid) films

Nanocomposite thin films of poly(lactic acid) (PLA) were produced incorporating small amounts (0.2 to 1 wt%) of graphene oxide (GO) and graphene nanoplatelets (GNP). The films were prepared by solvent‐casting. Mechanical properties were evaluated for plasticized (by residual solvent) and unplasticized films. Plasticized nanocomposite films presented yield strength and Young's modulus about 100% higher than those of pristine PLA. For unplasticized films improvements in tensile strength and Young's modulus were about 15 and 85%, respectively. For both film types, a maximum in mechanical performance was identified for about 0.4 wt% loadings of the two filler materials tested. Permeabilities towards oxygen and nitrogen decreased, respectively, three‐ and fourfold in films loaded with both GO or GNP. The glass transition temperature showed maximum increases, in relation to unloaded PLA films, of 5 °C for 0.4 wt% GO and 7 °C for 0.4 wt% GNP, coinciding with the observed maxima in mechanical properties. Copyright © 2012 Society of Chemical Industry     

Strengthening mechanism of poly(acrylamide)/graphene oxide/laponite dual nanocomposite hydrogels

Laponite or graphene oxide (GO) is usually used as a multifunctional crosslinker or a nanofiller to improve the nanocomposite gel strength. To explore the strengthening mechanism of GO/Laponite‐based dual nanocomposite hydrogels, we synthesized a dual nanocomposite hydrogel through in situ polymerization of acrylamide (AM) in the dispersion of GO and Laponite. The interactions between GO and Laponite were confirmed by rheological test. GO and Laponite nanosheets were exfoliated well and dispersed uniformly in the hydrogels at low concentration of GO. Crosslinking network and thermal behaviors were investigated with respect to the concentration of GO and Laponite. The gel exhibited a high mechanical strength of 391 kPa with extensibility of 1420% and a high toughness of 2.58 MJ/m³, which was expected to be applied in biological engineering field. GO is not a much more effective agent than Laponite due to formation of GO aggregates in high concentration of GO. This work provides a guidance for the synthesis of tough dual nanocomposite hydrogels. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44963.     

Synthesis,characterization, and anti-fouling properties of cellulose acetate/polyethylene glycol-grafted nanodiamond nanocomposite membranes for humic acid removal from contaminated water

Polyethylene glycol-grafted nanodiamond (ND-PEG) was synthesized from pristine detonation NDs and utilized to prepare novel cellulose acetate/polyethylene glycol-grafted nanodiamond(CA/ND-PEG)nanocomposite membranes. Due to unique thermal, mechanical, and antibacterial properties and very easy cleaning of fouled ND-embedded CA nanocomposite membranes, we tried to investigate the performance of CA/ND-PEG membrane for humic acid (HA) removal from contaminated water. Surface functionalization was confirmed by Fourier transform infrared spectroscopy and thermogravimetry analysis. Pristine and functionalized ND with different concentration was added in the casting solution containing CA. The prepared membranes were characterized using contact angle, mechanical strength, scanning electron microscopy (SEM), transmission electron microscopy, and permeation tests. SEM micrographs of the surface of the membranes depicted the increase in the number of pores by the addition of ND and especially ND-PEG into polymer matrix. The results indicated that the nanocomposite membrane with 0.5 wt% ND-PEG exhibited excellent hydrophilicity, mechanical properties, permeability, high rejection, high abrasion resistance, and good anti-fouling performance. The HA adsorption on the membrane surface decreased from 2.85 to 2.15 mg cm^?2 when the ND-PEG content increased from 0 to 0.5 wt%. Most importantly, the HA filtration experiments revealed that the incorporation of ND and especially ND-PEG particles reduced membrane irreversible fouling, dramatically. Meanwhile, the analysis of the fouling mechanism based on Hermia’s model revealed that cake formation is a prevailing mechanism for all membranes.     

Fabrication of fullerenol-incorporated thin-film nanocomposite forward osmosis membranes for improved desalination performances

Development and use of novel membranes for forward osmosis (FO) applications have gained popularity throughout the world. To enhance FO membrane performance, a novel thin-film nanocomposite membrane was fabricated by interfacial polymerization incorporating Fullerenol (C₆₀(OH)_n) nanomaterial, having n in the range of 24–28 into the active layer. Different concentrations of fullerenol loading (100, 200, 400, and 800 ppm) were added to the top skin layer. The structural and surface properties of the pure thin-film composite membrane (TFC) and fullerenol-incorporated thin-film nanocomposite (FTFC) membranes, were characterized by ATR-FTIR, SEM, and AFM. FO performance and separation properties were evaluated in terms of water flux, reverse salt flux, antifouling propensity, water permeability and salt permeability for all TFC and FTFC membranes. Osmotic performance tests showed that FTFC membranes achieved higher water flux and reverse salt flux selectivity compared with those of TFC membranes. The FTFC membrane with a fullerenol loading of 400 ppm exhibited a water flux of 26.1 L m^?2 h^?1 (LMH), which is 83.03% higher than that of the TFC membrane with a specific reverse salt flux of 0.18 g/L using 1 M sodium chloride draw solution against deionized water in FO mode. The fullerenol incorporation in FTFC membranes also contributed to a decreased fouling propensity.     

Synthesis and characterization of poly(ethylene tetrasulfide)/graphene oxide nanocomposites by in situ polymerization method

Poly(ethylene tetrasulfide) (PSP) is synthesized via interfacial polycondensation of 1,2 dichloroethane and sodium tetrasulfide, in the presence of graphene oxide (GO). This process resulted in homogeneously dispersed PSP/GO nanocomposites. Nanocomposites of 0.3 and 0.5?wt% of GO are synthesized and their morphology, chemical characteristics behavior are studied employing field emission scanning electron microscopy, Fourier transform infrared spectroscopy and X-ray diffraction techniques. Thermal characterization of composites is performed by differential scanning calorimetry and thermogravimetry analysis. Results indicate that the addition of only small amounts (0.5?wt%) of well-dispersed GO can increase the melting point more than 16°C resulting in better thermal properties for the composite. The solubility of nanocomposite is also studied and results show that the solubility depends on solvent concentration in addition to reinforcement (GO) deals.