Controlling thickener underflow rheology using a temperature responsive flocculant

Continuous solid–liquid separations with the temperature responsive flocculant poly (N‐isopropylacrylamide) (PNIPAM) were conducted in a pilot‐scale thickener for the first time, using fine quartz as the feed slurry. The performance in continuous operation was compared to batch sedimentation. The increase in sediment consolidation on cooling in batch sedimentation was less significant in the continuous operation due to kinetic limitations of the deeper sediment bed and shorter residence times in the pilot‐scale thickener. The reduction in underflow rheology which results when using the temperature responsive polymer as flocculant is significant. Paste‐like behavior results when underflow is discharged at 50°C, whereas low viscosity, near Newtonian behavior results when the underflow is discharged at 20°C. Compared to conventional polyacrylamide‐based flocculants, PNIPAM produces higher concentration underflow but lower clarity overflow and most importantly, significantly reduced underflow rheology (viscosity and yield stress). Temperature responsive flocculants have significant potential to reduce underflow pumping energy and cost for mineral tailings. © 2014 American Institute of Chemical Engineers AIChE J, 60: 2940–2948, 2014     

An investigation of the flocculation characteristics of polyacrylamide‐grafted chitosan

To investigate the flocculation characteristics of polyacrylamide (PAM)‐grafted chitosan, a series of PAM‐grafted chitosan copolymer (Chito‐g‐PAM1 to Chito‐g‐PAM4) have been synthesized by ceric ammonium nitrate‐induced solution polymerization technique in nitrogen atmosphere. The flocculation characteristics of the polymer samples (PAM, grafted and ungrafted chitosan) were studied by settling test and jar test methods in the colloidal suspensions of kaolin, iron ore, silica, and bentonite powder. It was found that the settling performance of Chito‐g‐PAM3 is best among the polymer samples. The jar test results indicate that the ungrafted chitosan has better water clarifying performance than both the PAM and grafted chitosan. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of molecular weight and charge density on the performance of polyacrylamide in low‐grade oil sand ore processing

The effect of charge density and molecular weight (MW) of partially hydrolyzed polyacrylamide (HPAM) polymers on their performance in processing low‐grade oil sand ores was investigated. Bitumen extraction and tailings settling tests were carried out and an atomic force microscope (AFM) was used to directly measure the bitumen‐solid and solid‐solid interaction forces. It was found that HPAM polymers with a low MW acted as dispersants in the bitumen extraction process, resulting in low bitumen recovery and slow tailings settling but improved froth quality. In contrast, the use of HPAM polymers with a high MW improved both bitumen recovery and tailings settling but deteriorated froth quality. To achieve high bitumen recovery and fast tailings settling, a HPAM polymer must have a low to medium charge density (～30%) and a high MW (17.5 million Daltons). A stronger clay‐bitumen adhesion force normally resulted in a lower bitumen recovery. Fast tailings settling was achieved in the presence of a strong solid‐solid adhesion force.     

α‐cyclodextrin assisted self‐assembly of poly(ethylene glycol)‐block‐poly(N‐isopropylacrylamide) in aqueous media

Poly(ethylene glycol)‐block‐poly(N‐isopropylacrylamide) (PEG‐b‐PNIPAM) block copolymers were synthesized by atom transfer radical polymerization, and the α‐cyclodextrin (α‐CD) induced self‐assembly characteristics of the system were elucidated. Below the lower critical solution temperature (LCST) of PNIPAM, CD threaded onto the PEG segments and induced micellization to form rod‐shaped nanostructures comprising of a PEG/α‐CD condensed phase and a PNIPAM shell. Increasing the temperature of system above the LCST caused the PNIPAM segments to collapse, which resulted in the dethreading of the CD. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Flocculation and sedimentation of cane sugar juice particles with cationic homo‐ and copolymers

Rapid flocculation and sedimentation of suspended particles in primary cane sugar juice is achieved using a high molecular weight anionic polymer flocculant. This work reports on efforts to enhance the performance of an anionic flocculant by the addition of cationic polymers. Homopolymers of poly(trimethylammonium ethyl methacrylate chloride) (TMAEMAC) and cationic copolymers of poly(trimethylammonium ethyl acrylate chloride) (TMAEAC) and acrylamide were synthesized and their performance, to enhance the flocculation and sedimentation of cane sugar juice particles, was evaluated by turbidity and settling rate measurements. The charge–patch mechanism best explains the performance of the homopolymers, whereas the action of the copolymers is attributed to the bridging mechanism. The results of this work indicate that the copolymers are more effective than the homopolymers to aid flocculation and sedimentation of the cane sugar juice particles, and that the best‐performing polymers are those that act by the bridging mechanism. Addition of increased amounts of anionic flocculant did not confer an improvement, suggesting that the cationic bridging flocculant targets a different population of particles that is largely responsible for the residual turbidity. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 316–325, 2003     

Thermoresponsive behaviour in aqueous solution of poly(maleic acid‐alt‐vinyl acetate) grafted with poly(N‐isopropylacrylamide)

The synthesis of a thermoresponsive graft copolymer consisting of a maleic acid/vinyl acetate alternating copolymer backbone (MAc‐alt‐VA) and poly(N‐isopropylacrylamide) (PNIPAM) side chains is reported. Turbidimetric measurements in dilute aqueous solutions showed that no macroscopic phase separation takes place when the temperature is raised above the lower critical solution temperature (LCST) of PNIPAM, even at pH = 2. Moreover, in semi‐dilute aqueous solutions, a pronounced thermally induced viscosity increase (thermothickening) was observed. This thermoresponsive behaviour has been attributed to the interconnection of the hydrophilic MAc‐alt‐VA graft copolymer backbones by means of the hydrophobic PNIPAM side chain aggregates formed as the temperature increases above the LCST of this polymer. Copyright © 2004 Society of Chemical Industry     

Polyacrylamides revisited: flocculation of kaolin suspensions and mature fine tailings

A series of acrylamide‐based water‐soluble (co)polymers was synthesized and they were investigated as flocculants of model kaolin suspensions and mature fine tailings of oil sands. The effects of molar mass, charge density, and polymer concentration on flocculation efficiency were studied by monitoring the initial settling rate during sedimentation. Hydrolyzed polyacrylamide (HPAM) with high molar mass and intermediate acrylic acid contents (0.14–0.41 mol/mol (14–41 mol%)) performed better in flocculation tests on kaolin suspensions requiring lower dose for maximum initial settling rate than native polyacrylamide (PAM). Surface force measurements showed that at low polymer concentrations (1 ppm), the partially‐adsorbed polymer induced a bridging attraction between the mica surfaces. Increasing the polymer concentration to 10 and 50 ppm caused purely repulsive forces. The presence of anionic groups in HPAM led to stronger repulsion, which was also demonstrated by the higher viscosity and larger hydrodynamic radius of the charged polymer. The charge‐induced increase in the viscosity of polymer solutions was suppressed by the screening effect of salts in a buffer solution and reducing the viscosity is desirable in the injection of flocculants in the industrial process.     

Self‐assembly and drug delivery behaviors of thermo‐sensitive poly(t‐butyl acrylate)‐b‐poly(N‐isopropylacrylamide) micelles

Self‐assembly of thermo‐sensitive poly (t‐butyl acrylate)‐b‐poly(N‐isopropylacrylamide) (PtBA‐ b‐PNIPAM) micelles in aqueous medium and its applications in controlled release of hydrophobic drugs were described. PtBA‐b‐PNIPAM was synthesized by atom transfer radical polymerization and aggregated into thermo‐sensitive core‐shell micelles with regular spheres in water, which was confirmed by ¹H‐NMR, fluorescence spectroscopy, transmission electron microscopic (TEM), and UV–vis spectroscopic techniques. The critical micelle concentration of micelles decreased with the increase of the hydrophobic components. The anti‐inflammation drug naproxen (NAP) was loaded as the model drug into polymeric micelles, which showed a dramatic thermo‐sensitive fast/slow switching behavior around the lower critical solution temperature (LCST). When the temperature was enhanced above LCST, release of NAP from core‐shell micelles was accelerated ascribed to the temperature‐induced deformation of micelles. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Flocculation characteristics of kaolin

The effect of metal cations on the flocculation behaviour of kaolin was investigated.The effects of pH, concentration of cations (Mg²⁺ and Al³⁺), and the presence of these cations in causticised cassava starch on the settling rate and percent reduction in sediment density were studied. Results show that the presence of high concentrations of divalent (Mg²⁺) and trivalent (Al³⁺) ions, and the presence of these cations in causticised cassava starch significantly contributed to the existence of low settling rates at high supernatant clarity often observed in some clay slurry treatment systems by flocculation and sedimentation method. It was also established that for efficient flocculation, the systems must be within the alkaline pH range (pH>10). The study further revealed that in some flocculation systems, fast settling corresponds to high sediment volume whereas in others, the opposite applies. It is therefore concluded that this phenomenon should be taken into consideration for proper design and operation of such treatment facilities.     

Synthesis and tunable thermoresponsive solution morphologies of 2,2‐bis‐methylolpropionic acid dendron–azobenzene–poly(N‐isopropyl acrylamide) copolymers

Amphiphilic temperature‐ and photoresponsive linear–dendritic block copolymers comprising second‐generation acetonide‐2,2‐bis‐methylolpropionic acid‐based polyester dendron and linear poly(N‐isopropyl acrylamide) (PNIPAM) linked by an azobenzene unit were synthesized using atom transfer radical polymerization (ATRP) followed by click chemistry. Linear PNIPAM precursor was prepared from an azide‐functionalized azobenzene containing ATRP initiator. Two polymers obtained by varying the chain length of the PNIPAM block showed different morphologies and lower critical solution temperature (LCST) values in aqueous solution. Complete change in morphology of the two polymers into large spherical aggregates and nanotubes, respectively, was observed upon heating the micellar solution above LCST. The azobenzene unit was found to undergo trans–cis photoisomerization in the assemblies and caused a change in the microenvironment of an encapsulated hydrophobic dye without any release. Acetonide groups on the dendron were deprotected to afford hydroxylated polymer that showed well‐defined morphologies above the LCST and after heating–cooling cycle while significant dye encapsulation was seen only above the LCST. © 2017 Society of Chemical Industry     

Pluronic‐based dual‐stimuli sensitive polymers capable of thermal gelation and pH‐dependent degradation for in situ biomedical application

Thermo‐sensitive hydrogels are considered ideal for applications in the biomedical fields for their biocompatibility, flexibility, tissue‐like water content, and reversible gelation property. By adjusting sufficient hydrophilic–hydrophobic balance in block copolymer structure, thermogel's critical gelation temperature (CGT) can be modified to be near the physiological temperature, which makes it an appealing candidate for in situ gel depot. In this study, we report successful syntheses of novel multiple block copolymer compounds, denoted as dual‐stimuli sensitive polymers (DSSPs), by copolymerizing Pluronic P104 (7100 Da) and 2,2‐bis(aminoethoxy)propane (BAP) using diisocyanate linkers, l ‐lysine ethyl ester diisocyanate (DSSP‐1), and 1,6‐hexamethylene diisocyanate (DSSP‐2). Through effective elongation of polymer chain lengths (DSSP‐1: 41,760 Da, DSSP‐2: 41,230 Da), Pluronic P104's reversible thermal gelation properties were enhanced, as demonstrated by lowered CGTs (DSSP‐1: 36 °C, DSSP‐2: 38.7 °C; 15 wt %) that is near the physiological temperature. Furthermore, integration of acid‐labile BAP allowed rapid pH‐dependent degradation of the polymer, which was displayed by gel permeation chromatography and release profiles of nile red and irinotecan from polymeric micelles and gels, respectively. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46552.     

Thermo‐responsive polymers for drag reduction in turbulent Taylor–Couette flow

The addition of a small amount of high molecular weight polymer to a solvent can substantially decrease friction losses by approximately 80%. This phenomenon known as drag reduction (DR) is used extensively in oil recovery during hydraulic fracturing and in many other applications to reduce the pumping costs. However, because of long chain length, these polymers get adsorbed on the surface of reservoir, diminishing the effectiveness of fracking. In the current study, a thermo‐responsive polymer, i.e., poly(N‐isopropylacrylamide) (PNIPAM) is investigated as a drag reducing agent (DRA), which collapses reversibly above 33 °C known as lower critical solution temperature (LCST), thereby preventing it from getting adsorbed beyond this temperature. Free radical polymerization was used to synthesize the PNIPAM and a Taylor–Couette (TC) setup with a rotating inner cylinder was utilized for measuring the DR. The effect of concentration, Reynolds number (Re), and temperature on DR were studied and a maximum of 50% DR was observed at 400 PPM concentration. PNIPAM demonstrated significant decrease in DR beyond LCST, validating its thermo‐responsive nature that could be beneficial for DR in oil recovery or in providing a control modality to DR technologies.DR versus temperature for PNIPAM solution (500 PPM) at Re = 100,000 demonstrating responsive behavior with temperature © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44191.     

Preparation and evaluation of radioiodinated thermoresponsive polymer based on poly(N‐isopropyl acrylamide) for radiotherapy

A thermoresponsive polymer based on poly N‐isopropylacrylamide (PNIPAM) was synthesized and radioiodinated to explore its potential use in localized radiotherapy. The synthesized PNIPAM polymer was functionalized with L ‐tyrosinamide to facilitate radioiodination. The content of tyrosinamide groups in the polymer was assayed spectrophotometrically (λ = 275nm). The functionalized polymer showed a cloud point temperature of 29–31°C and phase separation at 35°C, as revealed by Differential Scanning Calorimetry (DSC) and Dynamic Light Scattering (DLS). The phase transition temperature is conducive for preferential localization of the polymer at the site of injection due to changes in the polymer conformation at body temperature. For in vivo demonstration, the biodistribution studies of radioiodinated polymer were carried out in Swiss mice bearing fibrosarcoma tumor. Biodistribution studies showed a retention of 30% of the injected labeled polymer, PNIPAM‐¹²⁵I‐tyrosinamide, in the solid tumor tissues after 2 h of intratumoral injection. Although the activity decreased with time, 3–4% of the injected dose (i.d) was found to be retained in the tumor on 5 d post injection. The results suggest the potential use of thermosensitive polymer based on poly N‐isopropylacrylamide for locoregional radionuclide therapy. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 860‐868, 2013     

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.     

Synthesis,characterization and application of water‐soluble star polymers based on 2,4,6‐tris‐hydroxymethyl phenol and polyacrylamide

The synthesis of star polymers based on 2,4,6‐tris‐hydroxymethyl phenol (THP) and polyacrylamide (PAM) was carried out by free radical polymerization using potassium persulfate as an initiator. THP was prepared from phenol and formaldehyde by the Lederer?Manasse reaction. Varying the amount of acrylamide monomer, five different grades of star polymer were synthesized (THP‐PAM1 to THP‐PAM5). The star polymers were characterized by infrared spectroscopy, NMR spectroscopy, thermal analysis, viscosity measurements, scanning electron microscopy and X‐ray diffractometry. The flocculation performance of the star polymers was studied in kaolin suspension using the jar test and settling test methods. The flocculation efficiency of the star polymers was compared with commercially available flocculants and linear PAM. Several dye removal tests using methylene blue and various commercial textile acid dyes were performed. UV?visible spectra were employed to determine the reduced presence of dyes in the kaolin suspensions after treatment with star polymers. © 2014 Society of Chemical Industry     

Water‐soluble acrylamide copolymers. X. Flocculation efficiencies of poly[acrylamide‐co‐N,N‐dimethylacrylamide], poly[acrylamide‐co‐methacrylamide], poly[acrylamide‐co‐N‐t‐butylacrylamide], and their cationic derivatives

A hydrated, 1% by weight Na‐kaolinite suspension in deionized water was prepared, completely characterized, and reproducible measures of flocculation efficiency were validated. Flocculation tests of copolymers of acrylamide (AM) with dimethylacrylamide (DMA), methacrylamide (MeAM), or N‐t‐butylacrylamide (NTBAM) with 1% Na‐kaolinite suspensions gave average settling rate rates which decreased as the proportion of DMA, MeAM, or NTBAM in the copolymer increased. However, for a similar weight‐average molecular weight and slightly lower 〈r_g〉, the copolymer from DMA‐co‐AM‐3 gave settling rates and supernatant turbidities comparable to similar types of commercial polymers. This new copolymer was also more resistant to changes in pH or the presence of an electrolyte than were the tested commercial polymers. Cationic derivatives of the new copolymers gave lower average settling rates and higher supernatant turbidities than those of Percol 721 (cationic PAM), probably because of their lower charge densities. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2090–2108, 2002; DOI 10.1002/app.10562     

Dual‐stimuli‐responsive polymer‐coated mesoporous silica nanoparticles used for controlled drug delivery

In this article, a temperature‐ and pH‐responsive delivery system based on block‐copolymer‐capped mesoporous silica nanoparticles (MSNs) is presented. A poly[2‐(diethylamino)ethyl methacrylate)] (PDEAEMA)‐b‐poly(N‐isopropyl acrylamide) (PNIPAM) shell on MSNs was obtained through the surface‐initiated atom transfer radical polymerization. The block copolymer PDEAEMA‐b‐PNIPAM showed both temperature‐ and pH‐responsive properties. The release of the loaded model molecules from PDEAEMA‐b‐PNIPAM‐coated MSNs could be controlled by changes in the temperature or pH value of the medium. The as‐desired drug‐delivery carrier may be applied to biological systems in the future. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42395.     

Analysis of an electroforced sedimentation of highly concentrated clay slurry in consolidation region

A gravitational settling rate of highly concentrated slurry in which thickening proceeds due to consolidation mechanism is greatly enhanced by applying a D. C. electric field. Consolidation starts from the bottom of sediment and propagates upwards, but an abnormally strong consolidation also takes place in an upper portion of the sediment. The basic differential equation for such electroforced sedimentation is derived by use of Kobayashi’s equation which describes a flow in a porous material under an electric field. The relation among local hydraulic excess pressure, solid compressive pressure and gravitational force on solid particles is also obtained. Based on the theory, the larger the porosity of sediment, the greater the flow rate of electroosmosis; the electroosmotic flow at the settling surface is accordingly the largest among those at any layers in the sediment. An abnormal compaction of the layer near the settling surface is consequently due to the difference between flow rates at the surface and any layer under the surface. The theoretical change of porosity distribution and sediment height with time of Mitsukuri-Gairome clay compares favorably with experimental observations.     

Study of pH/temperature dual stimuli‐responsive nanogels with interpenetrating polymer network structure

Nanogels with interpenetrating polymer network (IPN) structure based on poly(N‐isopropylacrylamide) (PNIPAM) and poly(acrylic acid) (PAA) were synthesized by in situ polymerization of acrylic acid and N, N′‐methylenebisacrylamide within the PNIPAM nanogels. Their IPN structure was confirmed using transmission electron microscopy after staining by uranyl acetate. The temperature‐ or pH‐dependent hydrodynamic diameters measured using dynamic laser light scattering show that the IPN nanogels have pH and temperature dual stimuli‐responsive properties. As compared to previously reported pH/temperature dual stimuli‐responsive nanogels, these IPN nanogels have the advantage of less mutual interference between the temperature‐responsive and pH‐responsive components, which is beneficial for their applications in controlled drug release and sensors. The temperature‐ and pH‐triggered volume phase transition mechanisms of the IPN nanogels were tested by probing the microenvironment change of their PNIPAM and PAA chains upon phase transition using infrared (IR) absorption spectra measured at different pH values and IR difference spectra obtained by subtracting the IR spectrum obtained before temperature‐induced phase transition from that obtained after phase transition. Copyright © 2012 Society of Chemical Industry     

Gating Characteristics of Thermo‐Responsive Membranes with Grafted Linear and Crosslinked Poly(N‐isopropylacrylamide) Gates

Thermo‐responsive porous membranes with grafted linear and crosslinked poly(N‐isopropylacrylamide) (PNIPAM) gates are successfully prepared at temperatures above and below the lower critical solution temperature (LCST) of PNIPAM by using a plasma‐induced grafting polymerization method, and the effects of operation pressure and grafting temperature on the thermo‐responsive gating characteristics of the prepared membranes are investigated systematically. The fluxes of water through the grafted membranes increase simply with increasing the operation pressure no matter whether the environmental temperature is 40 °C or 25 °C. Under high operation pressure (e.g., higher than 0.14 MPa), the grafted linear PNIPAM gates deform to a certain extent, whereas the grafted crosslinked PNIPAM gates do not deform. For both membranes with grafted linear and crosslinked PNIPAM gates, the membranes prepared at 25 °C (below the LCST of PNIPAM) show larger thermo‐responsive gating coefficients than those prepared at 40 °C (above the LCST of PNIPAM), which results from different distributions of grafted PNIPAM gates in the membrane pores. When the PNIPAM gates are grafted at 25 °C, the grafted layer near the membrane surface is much thicker than that inside the membrane pores; on the other hand, when the PNIPAM gates are grafted at 40 °C, the grafted layer is homogeneously formed throughout the whole pore length. Both linear and crosslinked grafted PNIPAM gates in the membrane pores exhibit stable and repeatable thermo‐responsive “open‐close” switch performances under the operation pressure of 0.26 MPa. The results in this study provide valuable guidance for designing, fabricating, and operating thermo‐responsive gating membranes with desirable performances.