Influence of borate amount on the swelling and rheological properties of the Scleroglucan/borax system

Scleroglucan is a fungal polysaccharide that, when dispersed in water, assumes a very stable triple helix structure. It has numerous industrial applications in different fields, such as food industry, cosmetics, and pharmaceutics. In the presence of borate ions, this polymer forms weak gels that, after freeze‐drying and compaction, show an anisotropic swelling behavior, related to the borate/polymer ratio. By monitoring the evolution of the elastic and viscous moduli it was possible to follow the gel formation kinetics. The rheological properties of the network were studied as a function of crosslinking agent concentration and the corresponding flow curves and mechanical spectra were recorded. The kinetics of the crosslinking reaction was monitored by following the time evolution of the storage and loss moduli, after the addition of borate ions to the Scleroglucan system. Creep‐recovery experiments allowed acquiring recoverable strain values and those of the critical stress above which a very high compliance of the sample is reached. Obtained results are to be related to the specific type of bonds between the polysaccharide chains and the crosslinking agent. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42860.     

Effects of swelling on the viscoelastic properties of polyester films made from glycerol and glutaric acid

Viscoelastic properties have been determined for poly(glycerol‐co‐glutaric acid) films synthesized from Lewis acid‐catalyzed polyesterifications. The polymers were prepared by synthesizing polymer gels that were subsequently cured at 125°C to form polymer films. The polymers were evaluated for the extent of reaction before and after curing by Fourier transform infrared spectroscopy. They were subsequently immersed in dimethylsulfoxide, tetrahydrofuran, water, methanol, and hexane for 24 h. The amounts of solvent absorbed were monitored and recorded. Dependent up the solvent used, the polymers were able to absorb 9.5–261% of its weight. The effects of the solvent absorption on the viscoelastic properties of the polyester films were evaluated by determining their elastic modulus (G′), viscous modulus (G″), tan δG″/G′, and complex viscosity (η*) by performing oscillatory frequency sweep experiments. The elastic modulus (G′) and viscous modulus (G″) were both higher for the dry polymers than the solvent‐absorbed polymers. However, the polymer films were all higher in elastic (G′) character than viscous (G″) character. Therefore, tan δG″/G′ < 1 before and after immersion in solvents. Values for η* decreased with angular frequency for all of the polyesters tested in this study. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of emulsifier content on the rheological properties of asphalt emulsion residues

Rheological measurement was employed to study the effect of emulsifier content on the properties of asphalt emulsion. Three kinds of emulsifiers are employed, and both temperature and frequency sweep were carried out in this study. Through the analysis of the viscoelastic parameters, the emulsifier content has an obvious influence in the properties of asphalt emulsions. As the content is higher, both the viscosity and modulus increase at a given temperature and/or frequency. The rut factor also increases with the emulsifier content, which indicates an enhanced resistance of emulsified asphalt mixtures to deformation. Rheological results can guide the selection of optimal emulsifier concentration for a given method of preparation. Results of softening point, penetration, ductility and storage stability also show good agreement with the rheological measurements. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41806.     

Investigations on rheological properties and gelation of tasar regenerated silk fibroin solution

Tasar silk is a variety of non‐mulberry silk indigenous to the Indian subcontinent. We present the measured frequency‐dependent viscoelastic moduli of Tasar regenerated silk fibroin (RSF) solution using optical tweezers at two concentrations (0.16% and 0.25% w/v) and extend these measurements to the low frequency regime using a video microscopy technique. We extend the investigation on the rheological behavior of Tasar RSF for four more RSF concentrations, viz., 0.50%, 1.00%, 2.50% and 5.00% using video microscopy. In all the RSF samples, both storage and loss moduli are found to increase with frequency. At lower frequencies the loss modulus is more than the storage modulus and exhibit similar behavior until a crossover frequency beyond which the storage modulus exceeds the loss modulus at all frequencies. The relaxation time which is inversely related to the crossover frequency is found to rise sharply at 5% w/v, indicating the onset of gelation in the sample. These results are examined in relation to the viscoelastic parameters of mulberry silk, wherein the larger crossover frequencies at the same higher concentrations indicate relaxation times that are an order of magnitude smaller than those measured for Tasar RSF. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40104.     

Fundamental adsorption properties of chitosan gel particles prepared by suspension evaporation method

Chitosan gel particles were prepared by the suspension evaporation method, and their fundamental adsorption properties have been investigated. The chitosan gel particles were spherical in shape, 150 μm in diameter, and had large macropores, about 2 μm in diameter, formed by the polymer networks. The adsorption properties were evaluated from an interaction viewpoint using anionic surfactants having various numbers of carbon atoms, ethylbenzenesulfonate (EBS), octylbenzenesulfonate (OBS), and dodecylbenzenesulfonate (DBS). The pK_a values of the amino groups within the gel particles were remarkably small compared with those of chitosan polymer. EBS, with its short hydrophobic chain, was adsorbed mainly by an electrostatic interaction in the pH range 3.0 to 6.0, where the amino groups were dissociated. On the contrary, the adsorption of OBS and DBS, with their relatively long hydrophobic chains, took place via an electrostatic interaction in the pH range 3.0 to 5.0, and then by a hydrophobic interaction in the presence of an electrostatic interaction in the pH range 5.0 to 8.0. We conclude that an electrostatic interaction is essential, even for the adsorption of surfactants having strong hydrophobic interactions. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 901–906, 2002     

Fast‐swelling superabsorbent polymers with polymerizable macromolecular surfactant as crosslinker

Fast‐swelling superabsorbent polymers (SAPs) have been prepared by micellar cross‐linking copolymerization of acrylic acid and acrylamide using polymerizable macromolecular surfactants (PMSs) as multifunctional crosslinkers, with a foaming technique. Sodium bicarbonate (NaHCO₃)/acetone and Pluronic F127 were used as foam (or porosity) generators and stabilizer, respectively. It has been found that the PMSs with different polyethylene glycol (PEG) chain length have little effect on the swelling rate of the SAPs, while the foam generators are crucial. In addition, the monomer concentration and the concentration of the PMS are important to the fast swelling rate of the SAPs. For a balance of a relatively fast‐swelling rate, high water absorbency under load and low cost in drying, a monomer concentration of above 50%, 0.08% PMS, and 5% NaHCO₃ are preferable. The water absorbency of SAP prepared under optimal conditions could reach half of equilibrium water absorbency in 30 seconds and the saline water absorbency under load could reach 18.4 g/g. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44173.     

Effects of quasi‐nanogel particles on the rheological and mechanical properties of natural rubber: A new insight

The influence of sulfur‐crosslinked, quasi‐nanosized gels on the rheological and mechanical properties of raw natural rubber (NR) was investigated. Latex gels with different crosslink densities were prepared through the variation of the sulfur‐to‐accelerator ratio. These gels were characterized by dynamic light scattering, solvent swelling, and mechanical properties. The gels were mixed with raw NR latex at concentrations of 2, 4, 8, and 16 phr, and their effect on the rheological properties of NR was studied by Monsanto processability tester. The presence of gel in raw NR reduced the apparent shear viscosity and die swell considerably. Initially, the viscosity decreased up to a 8 phr gel loading and then increased with an increase in the gel loading. However, the change in the viscosity was related to the crosslink density of the gels. A new empirical equation relating the viscosity, volume fraction of the gels, and crosslink density was proposed. The die swell of gel‐filled raw NR was at least 10% lower than that of unfilled raw NR and decreased with an increase in the gel loading. The effect of the gels on the die swell properties was explained through the calculation of the principal normal stress difference of gel‐filled NR systems. Scanning electron photomicrographs of the extrudates revealed much better surface smoothness for the gel‐filled virgin rubber systems than for the unfilled rubber. The addition of the gels to raw NR increased the modulus and tensile strength, whereas the elongation at break decreased. The effect of the gels on the dynamic mechanical properties of NR was also investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and physical properties of hyaluronic acid‐based cryogels

Macroporous hydrogels based on hyaluronan (HA), a natural polysaccharide occurring in extracellular matrix, have attracted interest over many years owing to their numerous applications in the biomedical area. However, HA hydrogels produced so far suffer from low mechanical strength and slow rate of response against external stimuli, which limit their applications. Here, we prepared macroporous HA cryogels of high mechanical stability and fast responsivity from aqueous HA solutions at subzero temperatures using ethylene glycol diglycidyl ether as a crosslinking agent. HA cryogels are squeezable and no crack development was exhibited when compressed up to 80% strain. Depending on the synthesis parameters, the cryogels exhibit an elastic modulus between 0.2 and 2 kPa, and show fast swelling/deswelling behavior. The microstructure of the cryogels consists of large, interconnected pores on the order of 100 µm separated by thick pore walls, as observed by scanning electron microscopy and confocal scanning laser microscopy. © 2015 The Authors Journal of Applied Polymer Science Published by Wiley Periodicals, Inc. 2015 , 132, 42194.     

Influence of nonionic polymers on the rheological and electrical properties of Egyptian bentonite

The rheological properties of Egyptian bentonite suspensions in the presence of nonionic polymers were investigated. Two different types of nonionic polymers were studied: poly(ethylene glycol) (molecular weight = 6000 g/mol) and poly(vinyl pyrrolidone) (molecular weight = 40,000 g/mol). The rheological properties (plastic viscosity, apparent viscosity, and yield point) of concentrated clay suspensions (6–8% w/w) at different temperatures after 24 h were determined. As the nonionic polymer concentrations increased, the rheological properties of the bentonite suspensions showed a slight increase, especially at an 8% clay content. The electrical properties (electrophoretic mobility and ζ potential) of Egyptian bentonite in the presence of different nonionic polymers were measured with a ζ meter. The results showed that the ζ potential of this bentonite was higher with 200 mg/L poly (vinyl pyrrolidone) than with 1000 mg/L poly(ethylene glycol). Potential energy profiles for bentonite suspensions for these nonionic polymers were constructed to show that the net energy barrier for bentonite suspensions followed repulsion or attraction between particles. These profiles showed that the potential energy profile of a bentonite suspension with 200 mg/L poly(vinyl pyrrolidone) produced a high repulsion potential energy between clay surfaces; that is, the suspension stability improved. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects of clay concentration on the morphology and rheological properties of xanthan gum‐based hydrogels reinforced with montmorillonite particles

This work presents results of the morphology and rheological properties of xanthan gum (XG)‐based hydrogels reinforced by montmorillonite (MMT) particles. The results show that hydrogels exhibit self‐supporting characteristics when a critical MTT concentration of approximately 2.0% w/w is used. Wide‐angle, small‐angle X‐ray diffraction patterns and transmission electron microscopy reveal that for concentrations up to about 1.0% w/w the MTT particles are homogeneously distributed and exfoliated in the XG matrix. MTT particles aggregate at higher concentrations, contributing to the formation of junction points leading to hydrogels consolidation. Fourier transform infrared analysis indicates that the mechanism that enables the hydrogels formation might be attributed to hydrogen bonds crosslinking XG molecules with the surface of MTT particles. The storage modulus is higher as MTT concentration increases, but the loss modulus remains practically unchanged. Increasing temperature produces a drop in storage modulus, but the drop is minimized over a wider temperature range, as the MTT concentration is higher. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44517.     

Effects of microstructures on the viscoelastic and rheological properties of metallocene‐catalyzed cyclo‐olefin copolymers: A preliminary study

We characterized metallocene‐catalyzed cyclo‐olefin copolymers (mCOCs) with similar heat distortion temperatures but dramatic differences in melt‐flow indices to understand how the molecular conformation affected their rheological and viscoelastic properties. The mCOC conformations were identified with ¹³C‐NMR, whereas the viscoelastic and rheological properties were measured with cone‐and‐plate and high‐pressure capillary rheometers. Our preliminary results showed that the mCOC rheological and viscoelastic properties might depend strongly on the conformation rather than the norbornene content, molecular weight, and molecular weight distribution. mCOCs containing ‐NNN‐ locks (where N represents norbornene) exhibited stronger molecular entanglements than those having no ‐NNN‐ blocks, as reflected in lower crossover frequencies and higher crossover torque. Furthermore, the existence of larger rigid ‐NNN‐ blocks resulted in higher molten viscosities and flow activation energies. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3695–3701, 2002     

Synthesis and properties of a superabsorbent from an ultraviolet‐irradiated waste nameko mushroom substrate and poly(acrylic acid)

To better use the waste nameko mushroom substrate (WNMS) and prevent its pollution into the environment, a novel superabsorbent polymer was synthesized via the UV irradiation copolymerization of acrylic acid and WNMS in the presence of an initiator (dimethoxy‐2‐phenylacetophenone and ammonium persulfate) and crosslinker N,N′‐methylenebisacrylamide. The factors that had an influence on the water absorbency of the superabsorbent polymer were investigated and optimized. Under the optimized conditions, WNMS–poly(acrylic acid) was obtained. Its swelling behaviors, which followed the pseudo‐second‐order swelling kinetic model, were investigated in distilled water (1701 g/g) and a 0.9 wt % NaCl solution (388 g/g). The water absorbency was 1011 g/g in a 0.1 wt % urea solution and 80% amount of urea diffused into the gels. The urea diffusion followed a Fickian diffusion mechanism. Moreover, the product showed excellent water retention capabilities under the condition of high temperature or high pressure. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40471.     

Laboratory scale study on rheological behavior,morphological and structural properties of crosslinked polyacrylamide composite hydrogels embedded with date seed powder

Incorporation of biofillers in polymeric hydrogels has continued to receive great attention in recent times because of their excellent properties. In this study, polyacrylamide (PAM) and polyethyleneimine (PEI) were used to develop novel composite hydrogels filled with date seed powder (DSP) via chemical crosslinking technique. Pristine PAM/PEI hydrogel and PAM/PEI‐DSP hydrogels at various DSP loadings were fabricated and subjected to gelation at 40°C for 24 h. The impact of various DSP loadings on the hydrogel samples developed was investigated using hybrid rheometer, SEM, XRD, and FTIR instruments, respectively. Rheological measurements confirmed the viscoelastic responses of the neat PAM/PEI hydrogel and the PAM/PEI‐DSP hydrogels reinforced with various DSP contents (0.8, 2.4, and 4 wt %). The dynamic strain, dynamic frequency and time sweep tests demonstrated that PAM/PEI‐DSP hydrogels were slightly more elastic than the virgin PAM/PEI hydrogel. The SEM characterization revealed the surface micrographs of the neat PAM/PEI hydrogel and the PAM/PEI‐DSP hydrogels at different DSP loadings to be smooth, homogeneous, and dense. Besides, the SEM micrographs supported the incorporation of DSP in the PAM/PEI‐DSP hydrogel samples. XRD analysis showed that the structures of neat PAM/PEI hydrogel and PAM/PEI‐DSP hydrogels filled with various DSP contents were predominantly amorphous while FTIR results confirmed the functional groups and evidence of crosslinking in the neat PAM/PEI hydrogel and the PAM/PEI‐DSP hydrogels embedded with different DSP contents. It is believed that these new hydrogels have huge development potentials and promising future in wastewater treatment and removal of heavy metal ions in aqueous solutions. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42110.     

Effects of surfactants on the characteristics and biosensing properties of polyaniline

To investigate the effects of surfactants on the properties of polyaniline (PANI), a series of PANIs was synthesized in the presence of surfactants by chemical polymerization of aniline in an acidic medium, using (NH₄)₂S₂O₈ as oxidant. Three types of surfactant were used: (i) non‐ionic poly(ethylene oxide) (20) sorbitan monolaurate (Tween 20) and poly(ethylene oxide) (20) sorbitan monopalmitate (Tween 40); (ii) cationic (1‐tetradecyl)trimethylammonium bromide; and (iii) anionic sodium 1‐dodecanesulfonate and sodium 1‐pentanesulfonate. The structural, morphological and thermal properties of the various samples were characterized using Fourier transform infrared and UV‐visible spectroscopy, scanning electron microscopy and thermogravimetric analysis. Calorimetry was used to compare enthalpy changes during polymerization. The electrochemical and glucose biosensor properties of the PANIs were investigated using cyclic voltammetry and amperometric measurements. PANI‐Tween 20 and PANI‐Tween 40 were found to be good for immobilization of glucose oxidase enzymes and potential candidates for use in glucose biosensing. Copyright © 2010 Society of Chemical Industry     

Swelling and rheological study of calcium phosphate filled bacterial cellulose-based hydrogel scaffold

This work focuses mainly about swelling and rheological properties of calcium phosphate filled bacterial cellulose (BC)-based hydrogel scaffolds. Calcium phosphate is incorporated in the form of hydroxyapatite (HA) and β-tricalcium phosphate (β-TCP) in different ratios, that is, 00:00, 10:90, 20:80, 40:60, 50:50, and 60:40. These scaffolds are also comprised with polyvinylpyrrolidone (PVP), poly(ethylene glycol), agar, and glycerin; designated as “BC-PVP” and “BC-PVP-β-TCP/HA.” All the hydrogel scaffolds are showing the notable viscoelastic property at 28 and 37 °C temperatures. The degree of swelling is found significant in BC-PVP-β-TCP/HA_50:50 scaffold and it is notably elastic at 37 °C after 5 min of swelling. However, after 60 min of swelling and at equilibrium swelling state, the elastic property of BC-PVP-β-TCP/HA_20:80 is revealed the highest. Considering the degree of swelling and rheological properties, the BC-PVP-β-TCP/HA_50:50 and BC-PVP-β-TCP/HA_20:80 hydrogel scaffolds found suitable for their application in bone tissue engineering or bone tissue regeneration. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48522.     

Polymeric surfactants for enhanced oil recovery. IV—Thermodynamic properties of ethoxylated alkylphenol formaldehyde polymeric surfactants

The thermodynamic properties of some low molecular weight ethoxylated alkylphenol formaldehyde polymeric surfactants have been investigated. Surface tension as a function of concentration of the surfactants in aqueous solutions was measured at 28, 38, 48 and 58°C, using the spinning drop technique. From these measurements, the minimum area per molecule at the aqueous solution/air interface (A_min) was determined. The thermodynamic parameters of micellization (ΔG_mic, ΔH_mic, ΔS_mic) and of adsorption (ΔG_ad, ΔH_ad, ΔS_ad) for these polymeric nonionics were calculated. Micellization is more sensitive to ethylene oxide chain length while adsorption is more dependent on the length of the alkyl chain.     

Flow of viscoelastic surfactants through porous media

We compare the flow behavior of viscoelastic surfactant (VES) solutions and Newtonian fluids through two different model porous media having similar permeability: (a) a 3D random packed bed and (b) a microchannel with a periodically spaced pillars. The former provides much larger flow resistance at the same apparent shear rate compared to the latter. The flow profile in the 3D packed bed cannot be observed since it is a closed system. However, visualization of the flow profile in the microchannel shows strong spatial and temporal flow instabilities in VES fluids appear above a critical shear rate. The onset of such elastic instabilities correlates to the flow rate where increased flow resistance is observed. The elastic instabilities are attributed to the formation of transient shear induced structures. The experiments provide a detailed insight into the complex interplay between the pore scale geometry and rheology of VES in the creeping flow regime. © 2017 American Institute of Chemical Engineers AIChE J, 64: 773–781, 2018     

Effective removal of a cobalt‐tetrasulfonated phthalocyanine dye from an aqueous solution with a novel modified chitosan‐based superabsorbent hydrogel

Industrial wastewaters from the Merox process are heavily polluted by toxic cobalt‐tetrasulfonated phthalocyanine (CoTsPc) dye catalyst, and in this article, we describe the synthesis of novel chitosan hydrogels and their adsorption capabilities against CoTsPc as biosorbents. In this study, novel chitosan hydrogels were crosslinked by 3,3′,4,4′‐tetracarboxybenzophenone dianhydride and used for the first time. The adsorption capacities of the hydrogels were significantly improved, and they exhibited excellent sorption behavior with ammonium sulfate modification. The adsorption behavior was observed to be pH dependent, and the optimum pH was found to be 8. Moreover, the swelling studies indicated that the hydrogels are superabsorbent. The reusability of these dye‐adsorbent hydrogels was also evaluated. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46167.     

Adsorption of hexavalent chromium by chitosan‐based polymeric surfactants

Chitosan‐based polymeric surfactants (CBPSs) were prepared by the partial N‐acylation of amine groups on chitosan with acid anhydrides. To apply the CBPSs for the removal of Cr(VI) commonly found in wastewater, a batch test was conducted to evaluate the adsorption capacity. The removal efficiency of Cr(VI) by the CBPS depended on several factors, including the solution pH, CBPS dose, and ionic strength. Our results show that the CBPSs exhibited a greater adsorption capacity for Cr(VI) than have other modified chitosans reported in the literature. The maximum adsorption capacity of Cr(VI) was 180 mg/g of CBPS at a final pH of 5.3. From the results of dynamic light scattering, we propose that the removal mechanism of Cr(VI) by the CBPSs was mainly through the adsorption of negatively charged chromium ions by positively charged amine groups on the CBPSs followed by colloidal precipitation because of its lower solubility. Conclusively, we found that the CBPS was significantly effective for the removal of Cr(VI). © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 44–50, 2005     

Effect of the sodium dodecyl sulfate/monomer ratio on the network structure of hydrophobic association hydrogels with adjustable mechanical properties

The study of gel‐network structure is not as extensive as the study of the application of hydrogels. However, the distribution of the inner structure is crucial for designing hydrogels with tunable mechanical properties to meet certain kinds of demands. In this study, a series of hydrophobic association hydrogels (HA‐gels) were synthesized by free‐radical micellar copolymerization in a sodium dodecyl sulfate (SDS) surfactant solution. The hydrophobic monomer was palmityl alcohol poly(oxyethylene acrylate) (AEO–AC), which is an ecofriendly alternative to the traditional octyl phenol poly(oxyethylene acrylate). Interestingly, we found that the molar ratio [or ratio point (R)] of SDS to AEO–AC played a key role in tuning the mechanical properties. All series HA‐gels denominated a similar down–up–down tendency with increasing R, and the best R is 3. This result was consistent with the microscopic network structure number of the hydrophobic monomer (N_H = 21–24), and this indicated that each hydrophobic monomer associated three SDS monomers in its internal networks. The resulting AEO–AC–acrylamide gels exhibited the best mechanical strength (yield maximum broken stress = 218 kPa) and the maximum effective crosslink density. Moreover, the relationship between the network structure and the mechanical properties of the HA‐gels was investigated with various Rs. Two different interaction effects of distribution between SDS and AEO–AC are discussed in detail. The HA‐gels exhibited self‐healing properties and maintained their shape in water over 160 days. The results indicate that changing R is an effective method for tuning the mechanical properties of HA‐gels as a type of prospective biomedical material. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45196.