Poly (vinyl alcohol)/graphene oxide nanocomposite films and hydrogels prepared by gamma ray

ABSTRACT

Poly (vinyl alcohol)/graphene oxide (PVA/GO) gamma irradiated nanocomposite films and hydrogels were prepared. In composite films, GO was initially irradiated by gamma ray in order to improve interactions between GO and PVA. The film containing 1?wt-% GO was very strong where tensile modulus and tensile yield strength were 45 and 115% higher than those of pure PVA. In the second set of experiments PVA/GO hydrogels were made by irradiating PVA/GO suspensions by gamma ray at various doses. It was an interesting finding that GO increased the gel portion of hydrogels through contribution of H-bonds between PVA and GO. The hydrogels prepared at 20?kGy had remarkable water swelling ratio that reached as high as 20 at water temperature of 80°C. The hydrogel metal ion adsorption capability was tested on Cu²⁺ ions. It was shown that the GO contributed significantly to the adsorption capacity of PVA hydrogels.     

Functionalization of polyvinyl alcohol hydrogels with graphene oxide for potential dye removal

Because of highly frozen macromolecule chains, polyvinyl alcohol (PVA) hydrogels have never been used for dye removal. This work focuses on improving the adsorption capacity of the PVA hydrogel by using amphiphilic graphene oxide to improve its macromolecular chain mobility in crystal domain and introduce new functional groups. To evaluate its effectiveness, crystal structure, swelling kinetics, and model dye methylene blue (MB) adsorption of the as‐prepared PVA hybrid hydrogels were systematically investigated. The results indicate that the hybrid PVA hydrogels have lower crystallinity and less crystal stability, demonstrating the improved macromolecular chain mobility. Moreover, improved swelling ratios of PVA/GO hydrogels also illustrate the enhanced macromolecular chain mobility. MB adsorption experiment indicates that GO introduced can result in great improvement in MB adsorption. And the adsorption process follows the second‐order kinetic model and Morris–Weber model, which is determined by the intraparticle diffusion. Furthermore, MB adsorption isotherm follows Freundlich model and the adsorption is heterogeneous. Desorption studies indicate that the interaction between PVA hydrogels and MB consists of both physisorption and chemisorption. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39872.     

Comparative study of PEO and PVA hydrogels for removal of methylene blue dye from wastewater

In this study, poly(vinyl alcohol) (PVA) and poly(ethylene oxide) (PEO) hydrogels were synthesized and evaluated as adsorbent for dye removal from wastewater using methylene blue (MB) in aqueous solution as probe. PEO samples were photochemically prepared by varying irradiation time (1–16 h), while PVA samples were synthetized with different concentration of glutaraldehyde (GA) (0.03–0.48%). The obtained hydrogels were obtained through the analysis of a swelling test, scanning electron microscopy, and adsorption studies. PEO hydrogels adsorption capacity was dependent on the irradiation time, while the PVA hydrogel adsorption capacity reduces with GA concentration. Both hydrogels demonstrated a Langmuir isotherm adsorption model at the equilibrium and pseudo‐second order kinetic fits properly. pH studies showed that when pH reaches 12, the adsorbed MB amount is close to 8 and 2 times higher than pH = 2 both hydrogels. Photochemical preparation of hydrogels shows an easier way of tuning their properties in order to maximize dye removal. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45043.     

Superabsorbent,Breathable Graphene Oxide-Based Nanocomposite Hydrogel as a Dense Membrane for Use in Protective Clothing

This study examines the synthesis, fabrication and characterization of poly acrylamido methyl propane sulfonic acid (PAMPS)/graphene oxide (GO) nanocomposites. PAMPS-GO nanocomposite hydrogel was synthesized by radical initiated polymerization and its swelling properties, water vapor permeability (WVP), and stress-strain behavior were evaluated. The swelling behavior of hydrogel nanocomposites were improved at the presence of 0.2 wt% GO, as confirmed by water uptake experiments. It should be noted that as GO loading increased, so did the WVP of the hydrogel. The stress-strain test also revealed that the incorporation of just 0.1% of GO raised the tensile strength and young modulus of the hydrogels by 42% and 37% respectively. These fabricated dense membranes can have applications in protective clothing and wound dressing.     

Synergistic effect of graphene oxide and sodium carboxymethylcellulose on the properties of poly(vinyl alcohol) hydrogels

Hydrogels are a promising candidate for applications in biomedicine and bioengineering, but their mechanical properties often restrict their applications. To improve the mechanical performance of poly(vinyl alcohol) (PVA) hydrogels, we introduced sodium carboxymethylcellulose (CMC), and graphene oxide (GO) into them. We prepared a series of composite hydrogels composed of PVA, CMC, and GO with epichlorohydrin as a chemical crosslinker. We used Fourier transform infrared spectroscopy and X-ray diffraction to characterize the chemical structures of GO and the hydrogel. The dynamic mechanical analysis results show the synergistic enhancement effects of CMC and GO on the PVA hydrogel. The swelling process of the hydrogels also fit well with the second-order kinetic equation. Scanning electron microscopy results suggest that the neat mesh structure facilitated superior mechanical properties in the hydrogels. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47644.     

聚丙烯酸/氧化石墨烯复合水凝胶制备及对亚甲基蓝吸附

以丙烯酸(AA)为原料,二丙烯酸酯(Pul DA)分散的氧化石墨烯(GO)纳米胶粒(GO-Pul DA)为增强剂,N,N'-亚甲基双丙烯酰胺(BIS)为交联剂,通过自由基共聚合制备了一系列结构均一的聚丙烯酸/氧化石墨烯复合水凝胶(PAA/GO-Pul DA)。考察了BIS质量浓度、GO质量浓度以及溶液pH值对复合水凝胶力学性能、吸水性和亚甲基蓝(MB)吸附量的影响。结果表明,当GO质量浓度从0.1 g/L增加至1.0 g/L时,复合水凝胶拉伸强度从5.0 k Pa增加至10.4 k Pa,断裂伸长率高于100%,当GO的质量浓度为0.3 g/L时,复合水凝胶的断裂伸长率最高为151%;复合水凝胶表现出pH敏感的高吸湿性,pH从3.0增加至6.8时,平衡溶胀比(SRe)变化可达386 g/g,pH=6.8时最大SRe高达490 g/g。当溶液pH值从3.0增加至11.0时,PAA/GO-Pul D对MB的平衡吸附量(qe)可增加1 400~1 500 mg/g,pH=11.0时最大的qe高达1 789 mg/g。复合水凝胶对MB的吸附行为符合准一级动力学模型。5次吸附-解吸附循环后,相对于首次吸附,PAA/GO-Pul D对MB的吸附能力仍保持高达60%,解吸附效率高于90%。     

Poly(N,N-dimethylaminoethyl methacrylate)/graphene oxide hybrid hydrogels: pH and temperature sensitivities and Cr(VI) adsorption

Different amounts of graphene oxide (GO) were incorporated to N,N-dimethylaminoethyl methacrylate (DMAEMA), fabricating a series of pH and temperature dual sensitive PDMAEMA/GO hybrid hydrogels by in situ polymerization. Their microscopic network structures as well as swelling properties and Cr(VI) adsorption were characterized. The equilibrium swelling ratios (ESR) of hydrogels increased significantly with 0.5 wt% GO feeding of DMAEMA amount, and then decreased with further GO loading increasing. All hydrogels showed obvious deswelling when pH value of swelling mediums increased from 5 to 10 gradually. At pH 7, hydrogels revealed slight ESR increment with temperature up to 50 °C, above which obvious deswelling occurred. In pH 8 buffer, 0.5 wt% of GO loading triggered lower critical solution temperature (LCST) to decrease by 3 °C, and 2–7 °C increment was observed when 1–6 wt% of GO was loaded, as compared with that of GO-free PDMAEMA hydrogel. Cr(VI) adsorption of hydrogels was also improved by the introduction of GO to some extent, and the maximum Cr(VI) adsorption of 180 mg/g was realized, indicating that the obtained PDMAEMA/GO hybrid hydrogels possess excellent adsorption performance.     

In situ crosslinking of poly(vinyl alcohol)/graphene oxide Nano-composite hydrogel: intercalation structure and adsorption mechanism for advanced Pb(II) removal

Based on the industrialized graphene oxide (GO) product, poly(vinyl alcohol) (PVA)/GO nano-composite hydrogels were prepared through in situ crosslinking by incorporation of N-[(trimethoxysilyl)propyl] ethylenediamine-triacetic acid sodium (CSA) as a compatibilizer. Introduction of CSA led to more efficient grafting of PVA molecules onto GO surface with increasing average layer thickness through covalent and hydrogen bonding interaction, while GO was exfoliated and uniformly distributed in PVA matrix. Addition of appropriate content of GO can improve the storage modulus and the effective crosslinking density (υ_e) of the composite hydrogel, and the network structure with GO as crosslinking point formed, resulting in the remarkable increase of the hydraulic impact resistance, mechanical strength and toughness of the hydrogel. Pb²⁺ adsorption capacity of the hydrogel increased with GO content, while the adsorption belonged to the second-order kinetic model and fitted Langmuir adsorption isotherm model, indicating the homogeneous nature of monolayer chemical adsorption of Pb²⁺. A relatively good reusability of the composite hydrogel beads for Pb²⁺ removal can be achieved.     

Fabrication of 3D Polypyrrole/Graphene Oxide Composite Hydrogels with High Performance Swelling Properties

The polypyrrole (PPy)/graphene oxide (GO) composite hydrogels with hierarchical porous structures were fabricated by one-step self-assembly method. The static oxidation polymerization of pyrrole monomer in GO aqueous solution resulted in the formation of three-dimensional (3D) PPy/GO composite hydrogels, which consisted of one-dimensional PPy nanofibers and two-dimensional GO nanosheets. The as-prepared composite hydrogels exhibited shrinking–swelling behavior with cycles of suction and water-supplying. The effects of GO nanosheets content on the swelling properties were investigated. Results showed that the well-dispersed GO nanosheets in the hydrogel networks resulted in a significant improvement in water absorbencies of the hydrogels. PPy/GO composite hydrogels exhibited unobvious variation in the water absorbency even in saline solutions. Such excellent properties in water absorbencies endow the conducting 3D PPy/GO composite hydrogels with great potential applications in electrochemical sensors or controlled release.     

Preparation and adsorption mechanism of polyvinyl alcohol/graphene oxide-sodium alginate nanocomposite hydrogel with high Pb(II) adsorption capacity

A series of polyvinyl alcohol (PVA)/graphene oxide (GO)-sodium alginate (SA) nanocomposite hydrogel beads were prepared through in situ crosslinking for Pb²⁺ removal. It was found that PVA and SA molecules were intercalated into GO layers through hydrogen bonding interactions, leading to the destruction of orderly structure of GO, while GO uniformly distributed in PVA matrix. With increasing PVA solution concentration, the hydrogel beads became more regular, a large number of polygonal pores with thin walls and open pores formed, the average pore size decreased, and the dense network structure formed. Meanwhile, the permeability of the composite hydrogel decreased, leading to the decline of Pb²⁺ adsorption capacity of the composite hydrogel. With increasing GO content, the ballability of the hydrogel beads was weakened, the pore size increased, and relatively loose network structure formed, resulting in an increase in permeability and Pb²⁺ adsorption capacity of the hydrogel, reaching up to 279.43 mg g⁻¹. Moreover, the composite hydrogel presented relatively good reusability for Pb²⁺ removal. The adsorption mechanism was explored and showed that the adsorption system of the composite hydrogel belonged to the second-order kinetic model and fitted Langmuir adsorption isotherm model for Pb²⁺ removal, which might be mono-layer chemical adsorption. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47318.     

近红外光响应氧化石墨烯/微凝胶复合智能水凝胶

设计合成了一种包含氧化石墨烯（GO）片层、聚（N-异丙基丙烯酰胺）（PNIPAM）微凝胶球体和PNIPAM链段的复合结构水凝胶。通过控制聚合时间得到负载双键且粒径不同的PNIPAM微凝胶,将其作为交联点与N-异丙基丙烯酰胺（NIPAM）聚合,GO作为纳米填料掺入水凝胶体系,GO片层上的含氧基团与NIPAM上的胺基产生氢键物理交联。此方法制备的复合水凝胶同时具有温度敏感和近红外光敏感特性,通过改变GO浓度、微凝胶的合成时间、NIPAM浓度等条件,水凝胶的光敏感性和温度敏感性得到提升。相比于传统PNIPAM水凝胶,此种复合水凝胶能够对光响应,实现非接触式控制形变,且响应速率快、响应程度高,可应用于光控开关等领域。     

石墨烯水凝胶的制备及其吸附性能研究

通过改进的Hummers法制备氧化石墨烯(GO),利用乙二胺(EDA)作还原剂,制得三维网状结构石墨烯水凝胶.利用紫外分光光度计考察了其对Pb2+的吸附性能,结果表明:120 min左右达到吸附平衡,并且在吸附剂用量为18 m g、氯化铅溶液质量分数为80 m g/L时,吸附效果最好,并且其吸附行为更符合准二级吸附动力...     

Imidazole modified acrylate-containing photocured hydrogels for the efficient removal of malachite green dye from aqueous solutions

In this work, we aimed to prepare a simple and an efficient adsorbent for the removal of toxic, cationic dye; malachite green (MG). We reviewed many previous studies and designed our adsorbent based on the rationale that (1) acidic groups containing monomers which are capable of making hydrogen bonds (or electrostatic interactions) with MG are very effective in adsorption and (2) π-π stacking enhances the adsorption capacity. We first synthesized an imidazole-acrylate adduct and used it for the preparation of photocured hydrogels. The imidazole-acrylate adduct was characterized by H NMR and FTIR spectroscopy. The effect of experimental conditions on the MG adsorption properties of the hydrogels such as the effect of pH, time and MG concentration were also investigated. Under the optimum conditions (pH = 6 and 220 min contact time) at room temperature, the maximum adsorption capacity was found as high as 714.28 mg/g. The results showed that the adsorption process of the optimum hydrogel, which can be used 4 times without a significant loss in its adsorption capacity, fits the Langmuir isotherm model. The hydrogel adsorbent displayed good selectivity and reusability.     

Graphene oxide/poly(vinyl alcohol) hydrogels with good tensile properties and reusable adsorption properties

Graphene oxide (GO)/poly(vinyl alcohol) (PVA) hydrogel (PGOH), which possesses good tensile and reusable absorption properties, has been prepared by the freezing–thawing method. The presence of GO visibly decreases the swelling ratio of PGOH and significantly enhances the tensile properties of PGOH due to the formation of hydrogen bonds between the GO and PVA. The maximum tensile strength and the equilibrium adsorption capacity of methylene blue (MB) of PGOH with 0.5?wt-% GO (PGOH-0.5) is found to be 15, being 4.1 times higher than that of pure PVA hydrogel. The spontaneous adsorption obeys the intraparticle diffusion kinetic model. In addition, PGOH-0.5 exhibits a promising cycling absorption performance. The 1st and 5th cycle of dye removal for PGOH-0.5 reached to 92 and 70%, respectively. Such enhancement in adsorption can be attributed to π–π stacking and strong electrostatic attraction between GO and MB.     

Effect of graphene oxide on the pH-responsive drug release from supramolecular hydrogels

Polypseudorotaxane (PPR) hydrogels formed by inclusion complexes between poly(ethylene glycol) (PEG) and α-cyclodextrin (α-CD) are highlighted as promising biomaterial for drug delivery. Here, we report a novel injectable PPR hydrogel containing graphene oxide (GO) for pH-responsive controlled release of doxorubicin hydrochloride (DOX). Our results showed that the gelation rates of the PEG/α-CD supramolecular structures could be tailored depending on the reagent concentrations. The formation of PEG/α-CD inclusion complexes was confirmed by TEM and XRD, the latter further confirming that GO restricts their formation. The supramolecular hydrogels were easily loaded with DOX by simple addition into the PEG solution before the complex formation with the α-CD solution. Noteworthy, disruption of ionic interactions between DOX and GO in the nanocomposite at pH = 5.5 resulted in higher DOX release than under physiological conditions (pH = 7.4). This pH dependence was barely observed in pure PPR hydrogel. These findings introduce DOX-loaded supramolecular hydrogels nanocomposites as promising carriers for pH-responsive and therefore localized, drug delivery systems.     

Poly(acrylamide/laponite) nanocomposite hydrogels: Swelling and cationic dye adsorption properties

Super adsorbent polyacrylamide (PAAm)/nanoclay (laponite, Lap) hydrogels were prepared by in situ free radical polymerization of AAm in an aqueous solution with clay as a crosslinker. The swelling properties and water‐soluble cationic dye adsorption behaviors of the PAAm/laponite (PAAm/Lap) nanocomposite (NC) hydrogels were investigated. The parameters of swelling and diffusion of water in dye solutions were evaluated for the PAAm/Lap NC hydrogels. The adsorption behavior of the monovalent cationic dyes such as Basic Blue 12 (BB 12), Basic Blue 9 (BB 9), and Basic Violet 1 (BV 1), were studied on the NC hydrogels. The effects of the clay content of the hydrogel on its cationic dye uptake behavior were studied. The adsorption studies indicated that the rates of dye uptake by the NC hydrogels increased in the following order: BB 9 > BB 12 > BV 1. This order is similar to the swelling results of the PAAm/Lap NC hydrogel in the dye solutions. The equilibrium uptakes of the different dyes by the PAAm/Lap NC hydrogel were nearly the same. In the dye absorption studies, S‐type adsorption in the Giles classification system was found for the BB 12 and BV 1 dyes, whereas L ‐type was observed for the BB 9 dye. After the heat treatment of PAAm/Lap, the rate of dye uptake and equilibrium dye uptake were increased. The NC hydrogels may be considered as a good candidate for environmental applications to retain more water and to remove dyes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Application of graphene-based adsorbents in the treatment of dye-contaminated wastewater; kinetic and isotherm studies

The adsorption of methylene blue (MB) on graphene-based adsorbents was tested through the batch experimental method. Two types of graphene-based adsorbents as graphene oxide (GO) and reduced graphene oxide (RGO) were compared to investigate the best adsorbent for MB removal. So that optimizing the MB removal for the selected type of graphene-based adsorbent, the diverse experimental factors, as pH (2–10), contact time (0–1440 min), adsorbent dosage (0.5–2 g/L), and initial MB concentration (25–400 mg/L) were analyzed. The conclusions indicated that the MB removal rised with an increase in the initial concentration of the MB and so rises in the amount of adsorbent used and initial pH. Maximum dye removal was calculated as 99.11% at optimal conditions after 240 min. Adsorption data were compiled by the Langmuir isotherm (R²: 0.999) and pseudo-second-order kinetic models (R²: 0.999). The Langmuir isotherm model accepted that the homogeneous surface of the GO adsorbent covering with a single layer. And the adsorption energy was calculated as 9.38 kJ mol⁻¹ according to the D-R model indicating the chemical adsorption occurred. The results show that GO could be utilized for the treatment of dye-contaminated aqueous solutions effectively.     

Various carbon-based MgAl2O4 adsorbents and their removal efficiency of CR dye and antibiotics in aqueous media: High selective adsorption capacity,performance prediction and mechanism insight

Various carbon -based MgAl₂O₄ (MAO) adsorbents were synthesized by a simple ultrasound irradiation technology with the activated carbon (AC), carbon quantum dots (CQDs), C₃N₄ (CN) and graphene oxide (GO) as carbon sources. The optimum synthesis conditions for the carbon -based MAO adsorbents were determined by the study of the addition of different types of carbon and different mass ratios of m_{Various carbon}: m_MAO = 2.5%, 5.0%, 7.5% and 10%. The carbon -based MAO adsorbents were used for the adsorption of Congo red (CR) dye, tetracycline hydrochloride (TCH), oxytetracycline hydrochloride (OCH), ciprofloxacin (CIP), naproxen sodium (NPS) and tetrabromobisphenol A (TBBPA) and the seven factors affecting the adsorption behavior were discussed, including the type of carbon, AC content, initial dye concentration (C_CR), adsorbent dosage (C_{carbon -based MAO adsorbents}), adsorption time (A_t), pH value and reaction temperature (T). The corresponding adsorption isotherm models such as Langmuir, Tempkin, Koble-Corrigan, Toth and Freundlich models and thermodynamics of carbon -based MAO adsorbents for the adsorption of CR dye were also studied. When pH = 7.8, C_CR = 200 mg/L, A_t = 90 min, T = 287 K and C_{AC 5.0 wt%-MAO} = 1 g/L, the removal rate of CR dye reaches 89.7%. The back propagation (BP) neural network model was used to predict the adsorption percentage of carbon-based MAO adsorbents, which was consistent with the experimental results. The high adsorption capacity of AC 5.0 wt%-MAO adsorbents for the adsorption of CR dye can be assigned to the synergistic effects of electrostatic interaction, intermolecular force, n-π interaction and hydrogen bonding, while for the adsorption of TCH, OCH and CIP can be ascribed to the electrostatic interaction. This study demonstrated a huge potential of carbon -based MAO adsorbents as an eco-friendly adsorbent for the adsorption of dyes and drugs.     

Convenient method for preparation of a new absorbent based on biofunctionalized graphene oxide hydrogels using nitrene chemistry and click reaction

A new graphene oxide (GO)-based hydrogel was synthesized through cross-linking of biofunctionalized graphene oxide nanosheets by di-alkyne polyethylene glycol as cross-linking agent. In this respect, nitrene chemistry as a convenient and straightforward protocol was developed for biofunctionalization of GO using an azido-starch as an eco-friendly, biodegradable and cost-effective material. In the next step, 1,3-dipolar cycloaddition chemistry, a green and highly efficient approach was utilized in cross-linking of functionalized GO by PEG through click reaction between remaining azido groups of starch on the surface of GO sheets and terminal alkyne groups of polyethylene glycol. Formation of aziridine and triazole rings during functionalization and cross-linking in this method could evidently improve biological activities of the obtained hydrogel compared to the conventional methods. The antibacterial activity of the new compounds was explored. The synthesized hydrogel showed antibacterial properties against Gram-positive and Gram-negative bacteria due to the presence of triazole rings. Also, the resulting hydrogel exhibited high dye removal efficiency and it can be utilized in water treatment effectively. The adsorption kinetics was analyzed through the effects of adsorption time and the dye concentration on the adsorption capacity. Kinetic data were accurately described by a pseudo-second-order model.     

The effects of graphene oxide on the properties and drug delivery of konjac glucomannan hydrogel

Konjac glucomannan (KGM) hydrogel has good potential application in food and medical science, although to achieve this, the physical and mechanical properties need further improvement. In this study, graphene oxide (GO) was used to improve the functionality of KGM hydrogel. KGM/GO hydrogels were prepared by freezing the alkaline KGM/GO sols. Rotational rheometer was used to study the rheological properties of different alkaline KGM/GO sols. Fourier transform infrared, Raman, differential scanning calorimetry, thermogravimetric analyses, and scanning electron microscopy were used to evaluate the structure and properties of the hydrogels. In addition, different pH solutions and an in vitro assay were used to study the swelling property and the release behavior of KGM/GO hydrogels, respectively. The result revealed strong hydrogen‐bond interaction between KGM and GO. The incorporation of GO highly improved the gel properties of KGM/GO sol, higher thermal stability, and more compact structure of KGM/GO hydrogels. KGM/GO hydrogels showed better swelling properties in deionized‐distilled water and pH 7.2 PBS. The release of 5‐aminosalicylic acid (5‐ASA) from KGM/GO (KG4) hydrogel was different in various pH media, but the initial burst release effect was very severe. Therefore, incorporation of GO have a good potential in enhancing the properties of KGM hydrogel, but KGM/GO hydrogel is not an ideal carrier for 5‐ASA release. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45327.