Temperature effect on the swelling of PAAm‐κ‐carrageenan composites

The steady‐state fluorescence (SSF) technique was used for studying swelling of disc‐shaped polyacrylamide (PAAm)‐κ‐carrageenan (κC) composites which were prepared by free‐radical crosslinking copolymerization at 80°C. Pyranine was introduced as a fluorescence probe during polymerization. Swelling experiments were performed in water at various temperatures by real‐time monitoring of the pyranine (Py) fluorescence intensity, I which decreased as swelling proceeded. Stern–Volmer equation is modified for low quenching efficiencies to interpret the behavior of Py intensity during the swelling of PAAm‐κC composites. The Li‐Tanaka equation was used to determine the swelling time constants, τ₁, and cooperative diffusion coefficients, D₀, from fluorescence intensity, weight, and volume variations of the composites at various temperatures. It was observed that τ₁ first decreased up to 40°C and then increased; naturally, D₀ increased up to 40°C and then decrease for all κC content gels. Swelling activation energies, ΔE, were measured for the swelling composites, which are found to be exothermic and endothermic in between 30–40 and 40–60°C, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Studies on drying and swelling of PAAm‐NIPA composites in various compositions

The steady‐state fluorescence technique was introduced for studying the drying and swelling of disc‐shaped PAAm‐NIPA composites. Disc‐shaped gels were formed with various acrylamides (AAm) and N‐isopropylacrylamides (NIPA) by free radical crosslinking copolymerization in water. Composites were prepared with pyranine (Py) doped as a fluorescence probe. Scattered light, I_sc, and fluorescence intensities, I, were monitored during drying of these gels. The fluorescence intensity of pyranine increased and decreased as drying and swelling time increased respectively for all samples. The Stern‐Volmer equation combined with moving boundary and Li‐Tanaka models were used to explain the behavior of I during drying and swelling, respectively. It was found that the desorption coefficient, D, increased as NIPA contents were increased for a given temperature during drying. However, the cooperative diffusion coefficient, D₀, increased as NIPA contents were decreased during swelling at a given temperature. Supporting gravimetrical and volumetric experiments were also carried out during drying and swelling of PAAm‐NIPA composites. It was observed that NIPA contents affect the drying and swelling process. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Swelling of acrylamide gels made at various onset temperatures: an optical transmission study

Optical transmission experiments were performed using a UV–visible spectrometer during the swelling of polyacrylamide (PAAm) gels. These gels were prepared from acrylamide with N,N′‐methylenebisacrylamide at various onset temperatures (T_on) by free radical crosslinking copolymerization in water and dried before use for swelling experiments. Transmitted light intensity (I_tr) from the gels increased during early stages when PAAm gels were immersed in water at room temperature and then decreased continuously as swelling time was increased. Decrease in I_tr was attributed to the increase in the scattered light intensity which may originate from the contrast between ‘frozen blob clusters’ and holes in the swelling gel. Decrease in I_tr was modelled using the Li–Tanaka equation from which time constants (τ₁) and collective diffusion coefficients (D₀) were determined for the PAAm gels prepared at different onset temperatures. τ₁ and D₀ were found to be dependent on T_on. The correlation between T_on and τ₁ and D₀ was explained in terms of the size of microgels formed during gelation. © 2003 Society of Chemical Industry     

Edge‐functionalized graphene nanoplatelets with polystyrene by atom transfer radical polymerization: grafting through carboxyl groups

The surface modifier 3‐((4‐hydroxybutoxy)dimethylsilyl)propyl methacrylate (CD), which contains a double bond and a hydroxyl group, was synthesized through a coupling reaction of 1,4‐butanediol and (3‐methacryloxypropyl)dimethylchlorosilane. Subsequently, graphene oxide (GO) was functionalized with different amounts of CD from its edge carboxyl groups. Then, grafting through atom transfer radical polymerization of styrene in the presence of various amounts of the edge‐functionalized GO was carried out to evaluate the effect of graphene loading along with graft density. A peak at 3.8 ppm in the ¹H NMR spectrum of CD associated with the methylene adjacent to the Si–O group indicated a successful coupling reaction. Attachment of CD on the edges of GO was evaluated using X‐ray photoelectron and Fourier transform infrared spectroscopies. Expansion of GO interlayer spacing by functionalization was evaluated using X‐ray diffraction. The ordered and disordered crystal structure of carbon was studied using Raman spectroscopy. The close I_D/I_G values for GO and various kinds of functionalized graphenes show the preserved graphitic crystallite size. Relaxation behaviour of polystyrene chains in the presence of graphene nanoplatelets and also the effect of graft content on chain confinement were studied using differential scanning calorimetry. High‐graft‐density nanocomposites show higher glass transition temperatures. Morphology of graphene nanoplatelets was studied using scanning electron and transmission electron microscopies. The flat and smooth morphology of graphene nanoplatelets is disturbed and also the transparency of the nanoplatelets decreases during the oxidation and functionalization processes. © 2014 Society of Chemical Industry     

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.     

Effect of LCST on the swelling of PAAm-NIPA copolymers: a fluorescence study

Temperature sensitive copolymers were prepared by free radical crosslinking copolymerization in aqueous solution with different molar percentage of N-isopropylacrylamide (NIPA) and acrylamide (AAm) monomers. N,N′-methylenebis (acrylamide) (BIS) and ammonium persulfate (APS) were used as a crosslinker and an initiator, respectively. The steady-state fluorescence (SSF) technique was used to determine the low critical phase transition temperature (LCST) for PAAm-NIPA copolymers. Swelling experiments were performed in water at various temperatures by real time monitoring of pyranine (Py) fluorescence intensity, I which decreased as swelling proceeded. The Stern–Volmer equation is modified for low quenching efficiencies to interpret the behavior of pyranine intensity during the swelling of PAAm-NIPA copolymers. The Li–Tanaka equation was used to determine the swelling time constants, τ ₁ and the cooperative diffusion coefficients, D ₀ from fluorescence intensity, weight and volume variations of the copolymers at various temperatures. It was observed that τ ₁ first increased up to LCST, and then decreased; naturally D ₀ decreased up to LCST and then increased upon increasing temperature. It was understood that (LCST) increases as PAAm contents increase in the PAAm-NIPA copolymers.     

Radiation synthesis of graphene oxide/composite hydrogels and their ability for potential dye adsorption from wastewater

A high yield of graphene oxide (GO) was chemically synthesized from graphite powder utilizing adjusted Hummer's method. The contents of acidic functional groups in GO were determined using potentiometric titration. Composite hydrogels dependent on graphene oxide/poly(2-acrylamido-2-methylpropanesulfonic acid)/polyvinyl alcohol (GO/PAMPS/PVA) were synthesized utilizing a ⁶⁰Co gamma irradiation source at different doses. The synthesized graphene oxide and composite hydrogels were portrayed via X-ray diffraction, thermogravimetric analysis, and Fourier transform infrared analysis. The morphology of composite hydrogels was characterized by scanning electron microscope. The gel % and swelling % for the prepared hydrogel demonstrated that the swelling % of hydrogel increased with raising AMPS content. Whereas the increment of GO and increasing the irradiation dose lead to a reduction in the swelling %. The influences of pH, GO percentage, initial dye concentration, the adsorbent dosage, contact time, and temperature on the adsorption of basic blue 3 dye were evaluated and the adsorption capacity was 194.6 mg/g at optimum conditions; pH = 6, GO/PAMPS/PVA composite hydrogels with 5 wt% of GO, initial dye concentration = 200 mg/L, adsorbent dose = 0.1 g, solution volume = 50 mL after 360 min at room temperature (25°C). The adsorption of dye onto the GO/PAMPS/PVA composite hydrogels follows Pseudo-second-order adsorption kinetics, fits the Freundlich adsorption isotherm model.     

Preparation and properties of dopamine reduced graphene oxide and its composites of epoxy

To improve the thermal and mechanical properties and further to expand its applications of epoxy in electronic packaging, reduced graphene oxide/epoxy composites have been successfully prepared, in which dopamine (DA) was used as reducing agent and modifier for graphene oxide (GO) to avoid the environmentally harmful reducing agents and address the problem of aggregation of graphene in composites. Further studies revealed that DA could effectively eliminate the labile oxygen functionality of GO and generate polydopamine functionalized graphene oxide (PDA‐GO) because DA would be oxidated and undergo the rearrangement and intermolecular cross‐linking reaction to produce polydopamine (PDA), which would improve the interfacial adhesion between GO and epoxy, and further be beneficial for the homogenous dispersion of GO in epoxy matrix. The effect of PDA‐GO on the thermal and mechanical properties of PDA‐GO/epoxy composites was also investigated, and the incorporation of PDA‐GO could increase the thermal conductivity, storage modulus, glass transition (T_g), and dielectric constant of epoxy. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39754.     

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.     

Study on a new polymer/graphene oxide/clay double network hydrogel with improved response rate and mechanical properties

pH‐ and temperature‐responsive double network hydrogels (DN hydrogels) were prepared by using poly (N‐isopropylacrylamide) (PNIPAM) as a tightly crosslinked network (1st network), polyacrylic acid (PAA) as a loosely crosslinked network (2nd network), with clay and graphene oxide as effective crosslinkers and reinforcing fillers. The structure and morphology of the hydrogels were characterized by SEM, FTIR, DSC, and TGA. The synergetic effects of clay, GO and DN structure on various physical properties were investigated. With the increasing of crosslinking densities, the swelling ratios of DN hydrogels gradually decreased by increasing the contents of graphene oxide and PAA. While the DN hydrogels had much better mechanical properties than that of the conventional chemically cross‐linked PNIPAM hydrogels. POLYM. ENG. SCI., 55:1361–1366, 2015. © 2015 Society of Plastics Engineers     

Preparation of cellulose–graphene oxide aerogels with N‐methyl morpholine‐N‐oxide as a solvent

Cellulose–graphene oxide (GO) aerogel composites were successfully prepared from cellulose and GO dispersed in N‐methyl morpholine‐N‐oxide monohydrate, a nontoxic and environmentally friendly solvent, after a freeze‐drying process. Because of the strong interactions between the numerous oxygen‐containing groups located on the surface of GO and the functional groups of the cellulose molecules, the GO monolayers were well dispersed in the three‐dimensional porous structure of the cellulose aerogels. With the addition of 10 wt % GO, the swelling ratios and water contents of the composite cellulose–GO aerogels increased from 468 to 706% and from 82.4% to 87.6%, respectively. The corresponding maximum decomposition temperatures also increased from 335 to 353 °C with increasing GO content from 0 to 10%; this indicated that the thermal stability of the cellulose–GO aerogels was enhanced. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46152.     

Photon transmission technique for monitoring formation and swelling of polyacrylamide gels

The in situ, real-time photon transmission technique was used to monitor the free radical crosslinking copolymerization of acrylamide and N,N′-methylenebisacrylamide (Bis). Gelation experiments were performed with various Bis contents at various wavelengths. It was observed that the transmitted photon intensity, I _tr, decreased dramatically at a certain reaction time, which is attributed to the increase in scattered light intensity, I _sc, during the formation of microgels in the system. The increase in I _scwas modeled using Rayleigh's equation where the reaction time was found to be proportional to the volume of the microgels. The disc-shaped polyacrylamide (PAAm) gels were dried before use during swelling experiments. Transmitted light intensity, I _tr, from the gel increased at initial stages when PAAm gels were immersed in water and then decreased exponentially as the swelling time increased. Decrease in I _trwas attributed to the lattice heterogeneities, which might have originated between microgels and holes in the swelling gel. Decrease in I _trwas modeled using the Li–Tanaka equation from which cooperative diffusion coefficients, D _c, were determined for gels of various Bis contents. It is observed that the D _cvalues increased with the Bis content.     

Removal of paraquat pesticide from aqueous solutions using a novel adsorbent material based on polyacrylamide and methylcellulose hydrogels

This research studied the characteristics of poly(acrylamide) and methylcellulose (PAAm‐MC) hydrogels as a novel adsorbent material for removal of pesticide paraquat, from aqueous solution, with potential applications in curbing environmental risk from such herbicides. PAAm‐MC hydrogels with different acrylamide (AAm) and MC concentrations were prepared by a free‐radical polymerization method. The capability of the hydrogels in removing paraquat dichloride from aqueous solution was determined using UV–Vis analysis. The scanning electron microscopy method was used to study the morphological properties of the hydrogels, and swelling degree (Q) of the hydrogels was also measured. The entrapped MC in PAAm chains provoked significant changes in morphological, hydrophilic, and adsorption properties of the PAAm‐MC hydrogels. The adsorption capacity of hydrogels was strongly influenced by AAm, MC, and paraquat concentrations with the highest adsorption capacity (q_eq = 14.3 mg g^?1) was observed for hydrogels synthesized with 6.0% AAm with 0.75% MC swollen in 45.7 mg L^?1 of paraquat solution. Freundlich model performed better than Langmuir model in describing the adsorption isotherm of PAAm‐MC/paraquat system, implying a heterogeneous surface. These results suggest that PAAm‐MC hydrogels are potentially viable absorbents for removal of paraquat pesticide from aqueous solution and cleaning water contaminated with dyes, heavy metals, and others pesticides. © 2009 Wiley Periodicals, Inc. Journal of Appl Polym Sci, 2009     

Preparation and rheological investigation of tough PAAm hydrogel by adding branched polyethyleneimine

In this article, tough hydrogels are prepared by introducing the polyethyleneimine (PEI) with branched structure and a large number of  NH₂ and  NH groups into permanently crosslinked polyacrylamide (PAAm) hydrogels matrix. To investigate the effects of B-PEI and chemical crosslinking agent (Bis) on the strength and toughness of hydrogels, a series of B-PEI/PAAm hydrogels with different mass percentage of Bis and B-PEI were manufactured and the rheological and swelling properties were compared. For all hydrogels, the storage modulus (G′) was much higher than the loss modulus (G″) in the linear viscoelastic region through the whole frequency range. The solid-like behavior and elastic nature (G′ > G″) are attributed to the permanent covalence crosslinking. Therefore, G′ increased when more Bis was added. For the nonlinear oscillatory shear measurement, hydrogels with B-PEI broke at larger γ than the pure PAAm hydrogels, indicating that the toughness of B-PEI/PAAm hydrogels has been improved by introducing B-PEI. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48541.     

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.     

Preparation of functional reduced graphene oxide and its influence on the properties of polyimide composites

Homogeneous dispersion and strong filler–matrix interfacial interactions were vital factors for graphene for enhancing the properties of polymer composites. To improve the dispersion of graphene in the polymer matrix and enhance the interfacial interactions, graphene oxide (GO), as an important precursor of graphene, was functionalized with amine‐terminated poly(ethylene glycol) (PEG–NH₂) to prepare GO–poly(ethylene glycol) (PEG). Then, GO–PEG was further reduced to prepare modified reduced graphene oxide (rGO)–PEG with N₂H₄·H₂O. The success of the modification was confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis, and Raman spectroscopy. Different loadings of rGO–PEG were introduced into polyimide (PI) to produce composites via in situ polymerization and a thermal reduction process. The modification of PEG–NH₂ on the surface of rGO inhibited its reaggregation and improved the filler–matrix interfacial interactions. The properties of the composites were enhanced by the incorporation of rGO–PEG. With the addition of 1.0 wt % rGO–PEG, the tensile strength of PI increased by 81.5%, and the electrical conductivity increased by eight orders of magnitude. This significant improvement was attributed to the homogeneous dispersion of rGO–PEG and its strong filler–matrix interfacial interactions. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45119.     

Visualization of defect densities in reduced graphene oxide

Efficiently reducible graphene oxide (GO) was obtained, even if a high degree of functionalization is present. Graphite with few defects was used as starting material and oxidized according to Hummer’s method. An extremely high I_D/I_G ratio for rGO of 2.8 (532 nm) was observed in the Raman spectrum as a consequence of the lower defect density in GO. It was also possible to demonstrate the impact of local defects on the structure in rGO by local laser exposure experiments on single graphene oxide flakes. Raman spectroscopy can visualize the laser impact by I_D/I_G ratio measurements.     

Thermal and mechanical properties of liquid silicone rubber composites filled with functionalized graphene oxide

To improve the thermal and mechanical properties of liquid silicone rubber (LSR) for application, the graphene oxide (GO) was proposed to reinforce the LSR. The GO was functionalized with triethoxyvinylsilane (TEVS) by dehydration reaction to improve the dispersion and compatibility in the matrix. The structure of the functionalized graphene oxide (TEVS‐GO) was evaluated by Thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectra, X‐ray diffraction (XRD), and energy dispersive X‐ray spectroscopy (EDX). It was found that the TEVS was successfully grafted on the surface of GO. The TEVS‐GO/LSR composites were prepared via in situ polymerization. The structure of the composites was verified by FTIR, XRD, and scanning electron microscopy (SEM). The thermal properties of the composites were characterized by TGA and thermal conductivity. The results showed that the 10% weight loss temperature (T₁₀) increased 16.0°C with only 0.3 wt % addition of TEVS‐GO and the thermal conductivity possessed a two‐fold increase, compared to the pure LSR. Furthermore, the mechanical properties were studied and results revealed that the TEVS‐GO/LSR composites with 0.3 wt % TEVS‐GO displayed a 2.3‐fold increase in tensile strength, a 2.79‐fold enhancement in tear strength, and a 1.97‐fold reinforcement in shear strength compared with the neat LSR. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42582.     

Functionalized graphene‐reinforced rubber composite: Mechanical and tribological behavior study

A functionalized graphene, fluorinated graphene nanosheets (FGS), and SiO₂ nanoparticles as reinforcing fillers were employed to improve the mechanical properties of the solution styrene butadiene and butadiene rubber composites (SSBR‐BR). The results showed that the mechanical properties of SSBR‐BR composite filled with FGS were substantially improved than those of the unfilled and equivalent filler loaded graphene oxide (GO) and reduced graphene oxide (rGO) filled SSBR‐BR composites. It can be ascribed to the fact that the hydrophobic surface of FGS can be endowed the good dispersion in rubber matrix and stronger interfacial interaction between rubber and fillers. The tribological properties of these composites are also investigated. The results reveal that incorporation of GO, rGO, and FGS in SSBR‐BR composites can decrease antiwear properties because the existence of layered graphene promotes to tear and peel off. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44970.     

Dual pH‐ and temperature‐responsive hydrogels with extraordinary swelling/deswelling behavior and enhanced mechanical performances

pH‐ and temperature‐responsive semi‐interpenetrating nanocomposite hydrogels (NC hydrogels) were prepared with surface‐functionalized graphene oxide (GO) as the crosslinker, N‐isopropylacrylamide (NIPAM) as the monomer, and chitosan (CS) as an additive. The effects of 3‐(trimethoxysilyl)propylmethacrylate‐modified GO sheets and CS content on various physical properties were investigated. Results show that PNIPAM/CS/GO hydrogels undergo a large volumetric change in response to temperature. Swelling ratios of PNIPAM/CS/GO hydrogels are much larger than those of the conventional organically crosslinked PNIPAM hydrogels. The deswelling test indicates that the deswelling rate was greatly enhanced by incorporating CS into the hydrogel network and using the surface‐functionalized GO as the crosslinker. The pH‐sensitivity of PNIPAM/CS/GO hydrogels is evident below their volume phase transition temperature. Moreover, the PNIPAM/CS/GO hydrogels have a much better mechanical property compared with traditional hydrogels even in a high water content of 90%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41530.