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1.
Polymer gel, as a water plugging treatment agent, has been successfully used in enhanced oil recovery (EOR) of mature oil fields. A new thermal‐resistance and salt‐tolerance polymer gel was developed based on HPAM and HQ/HMTA under the condition of high‐temperature (100.8 °C) and high‐salinity (up to 19.8 × 104 mg/L and Ca2+&Mg2+ 0.8 × 104 mg/L). The influence factors of gelling performance and coreflood performances were studied, the microstructure of the gel was observed with the environmental scanning electron microscopy, and gelation mechanism was proposed to illuminate the detailed gelation process. The gelation time decreases and the gel strength increases with the increase of polymer concentration, crosslinker concentration, or temperature. Although shearing had a negative effect on the viscosity of gelling solution, the gel strength, and the stability of gel have not been affected. The gelling solution has a good ability of injection and could selectively flow into high permeable zone. Additionally, the plugging rate increases and stays above 85% with the increase of the permeability or the gel strength. The microstructure of the gel confirms that the gel formed a three‐dimensional network structure. Based on the microstructure and the reaction process of the gel, a possible gelation mechanism is proposed. This study suggests that the gel system can be used in harsh reservoir conditions and the gelation time and gel strength can be controlled with adjusting the formation rate and the concentration of crosslinking agents. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44359.  相似文献   

2.
The gelation characteristics of acrylic‐acid‐based polymers in the presence of a range of cationic species, namely Ca2+, Mg2+ and Al3+, were investigated using in situ rheological measurements during photo‐polymerisation. Fourier transform mechanical spectroscopy was used to identify the gel point, using the Winter–Chambon criteria which allow the gel point to be pinpointed by establishing the sample spanning network and quantitatively determining stiffness, relaxation exponent, gel stiffness and fractal dimensions. The results showed that the gelation processes were greatly influenced by the type of cationic species that was used in the syntheses. At the gel point, more open network clusters were formed when Al3+ cations were used instead of Ca2+ cations or Mg2+ cations, all relating to chloride salts. Although the concentrations of the chelating/crosslinking aluminium species affected the kinetics of the gelation, the critical gel characteristics were hardly affected. Also the solubility of the chosen aluminium salt was shown to dictate the crosslinking rates and the properties of the critical gels. The extents of the reactions and the types of network formed at the gel point and beyond indicated that reactions between the Al3+ ions and COOH sites, from growing poly(acrylic acid) molecular chains, differ from those exhibited by Mg2+ and Ca2+ ions. All of the chelation/crosslinking reactions met the criteria of low mutation number (Nmu), such that in all cases Nmu ? 1. © 2019 Society of Chemical Industry  相似文献   

3.
The weak mechanical properties of hydrogels, especially physically cross-linked hydrogels are usually a major factor to hinder their application. To solve this problem, in this work, we prepared a high strength and toughness of double physically cross-linked (PDN) hydrogels composed of crystalline domain cross-linked polyvinyl alcohol (PVA) and Ca2+-cross-linked alginate (Alg). With a further annealing treatment, the noncovalent cross-linked network via the formed crystalline promote the as-prepared PDN PVA/Alg hydrogel to exhibit well mechanical properties with the tensile strength of ~1.94 MPa, elongation at break of ~607% and Young's modulus of ~0.45 MPa (above 70 wt% of water content). By analyzing the mechanism of improving the hydrogel mechanical properties, it is found that annealing can effectively improve the crystallinity of PVA in the hydrogel, and then greatly improve the mechanical properties of the hydrogel. This provides a general method for improving the mechanical properties of PVA PDN hydrogels. In addition, the PDN PVA/Alg hydrogel was also proved to have good ionic conductivity of 1.70 S m−1. These desirable properties make the prepared physically cross-linked hydrogels promising materials for medical and biosensing fields.  相似文献   

4.
Polyvinyl alcohol (PVA) microgels were prepared using electron beam irradiation. To improve the PVA microgel functionality and gel fraction, chains of polyacrylic acid (PAA) were incorporated into PVA microgel by radiation grafting technique. The increase in the acrylic acid (AA) content as well as PVA Mwt is accompanied by a mutual increase in the gel fraction and a decrease in the swelling%. Immobilization of different TiO2 concentrations on the surface of the prepared PVA–AA microgel was carried out. The structural changes in the prepared PVA–AA microgel immobilized with TiO2/were investigated using FTIR, EDX and XRD. Photodegradation efficiency of TiO2/PVA–AA microgel against metnil yellow dyes was studied. TiO2/PVA–AA microgel activity increases with the increase of the amount of TiO2 and results in an increase in the rate of the photodegradation reaction. Easily recovery and reusability made TiO2/PVA/AA of great important in practice use as a photocatalytic degradation composite, for dye removal from wastewater.  相似文献   

5.
The formation kinetics of chitosan–alginate polyelectrolyte complex (CAPEC) was investigated in the presence of various ionic crosslinkers. The effects of binary mixtures of some anions with Ca2+ cations were also studied as a novel application. CAPEC gelation was enhanced in cases where Ca2+ ions coexisted with anionic crosslinkers compared to their conventional individual use, and this resulted in dispersions with higher stability. We demonstrated that the effects of some anions on CAPEC gelation could be reversed in the presence of Ca2+ ions, such that the inhibitory anions became enhancers. The results also revealed that Ca2+ ions, the most widely used ionic crosslinkers in CAPEC synthesis, exerted inhibitory effect on CAPEC gelation at low concentrations; in addition, the use of Ca2+ ions alone resulted in decreased dispersion stability. The effects of the binary crosslinker on the structure and properties of CAPEC were studied by scanning electron microscopy, Fourier transform infrared spectroscopy, particle size analysis, and ζ‐potential analyses. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40019.  相似文献   

6.
Here, zinc-neutralized ethylene propylene diene monomer (EPDM) ionomers with different neutralization levels are prepared through melt blending, and are then incorporated with polyamide 1012 (PA1012) to fabricate PA1012/EPDM ionomer blends. Interestingly, complex crosslinking networks are formed in the blends due to the construction of sacrificial bonds (Zn2+-carboxyl, Zn2+-amide). The as-formed network structure and sacrificial bond endow the PA/EPDM blends with largely enhanced toughness (16 times higher than that of neat PA), as well as balanced strength and stiffness. Meanwhile, the rheological behaviors of PA1012/EPDM ionomer blends indicate their relative low melting viscosity, which can avoid the processing shortcomings of plastics toughened with rubber. Moreover, PA1012/EPDM ionomer blends show obvious gelation behavior, and a maximum notched Izod impact strength exhibited at the gel point, in which unique double network structure can be observed obviously, indicating that there is a corresponding correlation between the rheological and mechanical parameters. Furthermore, the supper-toughening mechanism of PA1012/EPDM ionomer blends at gel point is explored, which origins from the large deformation and cavitation of rubber particles and the destruction of special double network morphologies. This study provides a novel and effective strategy to fabricate PA materials with outstanding toughness and excellent strength simultaneously.  相似文献   

7.
A novel chicken feather protein‐g‐poly (potassium acrylate)/polyvinyl alcohol (CFP‐g‐PKA/PVA) semi‐IPNs superabsorbent resin (SAR) based on feather protein, acrylic acid (AA), and polyvinyl alcohol (PVA) was synthesized by graft copolymerization and semi‐interpenetrating technology. The results from FTIR, SEM, and TGA analysis showed that both CFP and PVA reacted with PKA during the polymerization process. The effects of AA, PVA, initiator and crosslinker content on water absorbency of semi‐IPNs SAR were studied. The swelling behavior in various pHs and saline solutions were also investigated. The water absorbency of SAR reached the maximum at pH = 6. The effect of the five cations on swelling had the following order: Al3+ > Ca2+ > Mg2+ > K+ > Na+. The highest water absorbency in distilled water and 0.9 wt % NaCl solutions were 714.22 and 70.08 g g?1, respectively. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39748.  相似文献   

8.
The composition and setting reaction of cements formed from aluminosilicates and poly(acrylic acid), the ASPA cements, are described. Setting and hardening results from interactions between specially-formulated, complex, fluorine-containing calcium aluminosilicate glasses and aqueous solution of poly(acrylic acid) or similar poly(alkenyl carboxylic acids). Protons from the polyacid penetrate the surface of the glass decomposing the negatively charged aluminosilicate network to a siliceous hydrogel and releasing Al3+, Ca2+ and F- ions. These ions migrate, probably as complexes, such as AlF2+, AlF2+ and CaF+, into the polyelectrolyte phase where they cross-link polyanionic chains, by ionic and possibly chelate binding, causing the cement to gel and set. Overall the reaction may be seen as one where flexible hydrogen bonds, in the liquid, are progressively replaced by more rigid ionic ones, leading to gelation. The set cement is a composite of glass particles sheathed by a silica gel bound by a metal poly anionic matrix. ASPA cements can attain a compressive strength of 200 N/mm2 in 24 h and are adhesive under oral conditions to tooth materials. They find a number of applications in conservative and preventive dentistry. Certain naturally-occurring aluminosilicate minerals react with poly(acrylic acid) to form cement but these are much weaker (not exceeding a compressive strength of 30 N/mm2) and are weakened by water.  相似文献   

9.
《Ceramics International》2023,49(10):15680-15688
Polyvinylalcohol/chitosan (PVA/CS) is an excellent dual-network hydrogel material, but some significant challenges remain in fabricating composites with specific structures. In this study, 3D gel printing (3DGP) combined with a water-level controlled crosslinker bath was proposed for the rapid in-situ prototyping of PVA/CS/Fe3O4 magnetic hydrogel scaffolds. Specifically, the PVA/CS/Fe3O4 hydrogels were extruded into the crosslinker water to achieve rapid in-situ gelation, improving the printability of hydrogel scaffolds. The effect of the PVA/CS ratio on the rheological and mechanical properties of dual-network magnetic hydrogels was evaluated. The printing parameters were systematically optimized to facilitate the coordination between the crosslinking water bath and printer. The different crosslinking water baths were investigated to improve the printability of PVA/CS/Fe3O4 hydrogels. The results showed that the printability of the sodium hydroxide (NaOH) crosslinker was significantly better than that of sodium tripolyphosphate (TPP). The magnetic hydrogels (PVA: CS= 1: 1) crosslinked by NaOH had better compressive strength, swelling rate, and saturation magnetization of 1.17 MPa, 92.43%, and 22.19 emu/g, respectively. The MC3T3-E1 cell culture results showed that the PVA/CS/Fe3O4 scaffolds promoted cell adhesion and proliferation, and the scaffolds crosslinked by NaOH had superior cytocompatibility. 3DGP combined with a water-level controlled crosslinker bath offers a promising approach to preparing magnetic hydrogel materials.  相似文献   

10.
Maleic anhydride (MA) was grafted onto both partially and fully hydrolyzed poly(vinyl alcohol) (PVA) in the presence of an initiator. Strong polyelectrolyte polymers were prepared by sulfonation of PVA–MA grafts. The sulfonation was completed by reaction of hydroxyl groups of PVA–MA grafts with two different sulfonating reagents (chlorosulfonic acid and pyridine sulfonic acid). The sulfonation degree was evaluated by acid–base titration and 1H NMR analysis. The solution behaviour of the prepared grafts was evaluated from viscosity measurements. Four kinds of water‐insoluble PVA–MA and PVA–MA‐SO3H hydrogels were prepared by heat treatment, physical gelation and chemical crosslinking with different weight ratios of N,N‐methylene bisacrylamide (MBA) crosslinker. The swelling parameters were measured for all prepared gels in deionized water and aqueous solutions at different pH values from 2 to 12 having constant ionic strength (I = 0.1). All gels exhibit a different swelling behaviour upon environmental pH changes. Copyright © 2004 Society of Chemical Industry  相似文献   

11.
The gelation characteristics of acrylic acid (AA)‐based hydrogels were investigated using real time in situ photocrosslinking and rheological measurements. The gel point and gelation times were established using Winter–Chambon criteria. Frequency independence of tan δ was observed in all cases, such that G′ and G″ scaled as ~ωn. The Flory–Stockmayer theory was used alongside other indices in order to probe the gelation and the post‐gelation characteristics of the critical gels and the fully formed hydrogels. Network relaxation exponents (n) were influenced by the concentrations of AA and methylene bis‐acrylamide. The gel stiffness (S) decreased with an increase in the concentration of the monomer and of the concentration of the crosslinker, while network branching decreased (lower fractal dimensions) at the gel point. The conversion at the gel point was found to be iso‐conversion with respect to the intensity of the UV irradiance used in the photocrosslinking reactions (1–20 mW/cm2). Thus, network clusters and the crosslinking reaction mechanism were the same irrespective of radiation intensity, although the rates of the reactions were affected. Having sufficient amounts of reactive species at the time of cure drive the crosslinking reactions beyond the gel point to greater crosslink density and smaller mesh sizes. The effects of auto‐acceleration and free‐volume were observed and shown to have key effects on the gelation mechanisms and the branching topographies of the network, when the concentration of the known polyacrylamide medium were not controlled. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46691.  相似文献   

12.
Chitosan and poly(vinyl alcohol) (PVA) were used to form a semi‐interpenetrating polymeric network with glutaraldehyde as the cross‐linker. The molecular weight and degree of deacetylation of the chitosan were 612 kDa and 72 %, respectively. The chemical bonds formed by the cross‐linking reaction and transition of these bonds in different pH media were investigated. The gelation property of the chitosan–PVA pregel solution and mechanical properties of the hydrogel were studied. The FTIR spectra of the hydrogel before and after swelling at pH 3 and pH 7 indicated formation of Schiff's base (C?N) and ? NH3+. They also showed pH‐induced transition of C?N to C? N, and ? NH3+ to ? NH2, as well as the instability of the Schiff's base. The chitosan is essential for hydrogel formation through Schiff's base reaction between the amino groups of the chitosan and the aldehyde groups of the glutaraldehyde. The addition of PVA improved the mechanical properties of the hydrogel. However, PVA tends to leach out at longer swelling times in the acidic medium due to hydrolysis of the gel networks, Schiff's base. Copyright © 2004 Society of Chemical Industry  相似文献   

13.
A 13C-labeled crosslinker (trimethylolpropane triacrylate, TMPTA) was synthesized and copolymerized with acrylic acid while monitoring the relative rates of reaction of the crosslinker and acrylic acid by 13C-NMR. This allowed easy quantification of the concentration of the minor component (crosslinker) in the polymer and monomer mixture to levels as low as 0.02%. Polymerizations were conducted in 5 mm NMR tubes under varied temperature, percent neutralization (pH), and percent solids. Reactivity ratios were determined from the rates of incorporation of the components into the gel by use of the integrated form of the copolymerization equation, and their sensitivity to the above variables was quantified. The relative rate of incorporation of the crosslinker into the gel was exceedingly fast. The reactivity ratio, r1 for acrylic acid, varied from 0.31 (65% neutralization) to 0.77 (unneutralized). The reactivity ratio was affected by the percent solids (solvent effect), but was insensitive to temperature over the range of 55–80°C. It was observed that all of the double bonds of TMPTA were incorporated into gel network as opposed to prior models predicting only two bonds reacting. The reported inefficiency of TMPTA is postulated to be caused by a solubility problem in the monomer mixture. Very low levels of extractables were found in the products even though the crosslinker was consumed by 70% conversion. Based on these data, we propose that a major component of the gel network is graft polymer that forms late in the polymerization onto the crosslinked gel formed earlier. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 439–451, 1997  相似文献   

14.
A rigid assembly of alginates is formed in aqueous media primarily via hydrogen bonding between guluronic units. A flow of aqueous alginate solution in a co‐flow capillary can form alginate gel fibers by contact with Ca2+ ions in sheath flow. Mixing with polyols [e.g., polyethylene glycol (PEG)] facilitates the shaping of the alginate assembly because PEG disrupts the assembly of the extended alginate chains to instead form alginate–PEG complexes that exhibit shear‐thinning behavior. The shear‐induced fibrous domains of the globular alginate–PEG complexes can be partitioned by a PEG‐rich phase, resulting in multiple parallel alginate gel filaments when the strong ionic‐field‐induced PEG‐rich phase is adjusted and an alginate–PEG complex phase is used as the aqueous two‐phase separation system.  相似文献   

15.
This paper provides a new method to fabricate an integrated Janus fabric that has excellent unidirectional water-penetration property. Based on commercial polyester fabric that is pretreated with CaCl2 solution, polyvinyl alcohol/sodium alginate (PVA/SA) solution is deposited directly on the fabric via electrospinning and in situ chelated with Ca2+ contained in the fabric. The in situ formed PVA/SA gel coating not only transfers the surface of polyester fabric from hydrophobic to hydrophilic but also retains original porous structure of polyester fabric. As the water droplet contacts with unelectrospun side of modified polyester fabric (M-PET) pretreated with 10 wt% CaCl2, it penetrates through the M-PET within 1 s from unelectrospun side to electrospun side after application, and disappears on unelectrospun side within 2 s, and in turn, droplet spreads out on electrospun side of M-PET within 2 s after application and no penetration occurs. The M-PET pretreated with CaCl2 solution has outstanding antistatic property, vapor, and air permeability. The impact of ratio (v/v) of the PVA and SA solution and the concentration of CaCl2 pretreating solution on properties of the M-PET are investigated.  相似文献   

16.
Human wild type (wt) cardiac α-actin and its mutants p.A295S or p.R312H and p.E361G correlated with hypertrophic or dilated cardiomyopathy, respectively, were expressed by using the baculovirus/Sf21 insect cell system. The c-actin variants inhibited DNase I, indicating maintenance of their native state. Electron microscopy showed the formation of normal appearing actin filaments though they showed mutant specific differences in length and straightness correlating with their polymerization rates. TRITC-phalloidin staining showed that p.A295S and p.R312H exhibited reduced and the p.E361G mutant increased lengths of their formed filaments. Decoration of c-actins with cardiac tropomyosin (cTm) and troponin (cTn) conveyed Ca2+-sensitivity of the myosin-S1 ATPase stimulation, which was higher for the HCM p.A295S mutant and lower for the DCM p.R312H and p.E361G mutants than for wt c-actin. The lower Ca2+-sensitivity of myosin-S1 stimulation by both DCM actin mutants was corrected by the addition of levosimendan. Ca2+-dependency of the movement of pyrene-labeled cTm along polymerized c-actin variants decorated with cTn corresponded to the relations observed for the myosin-S1 ATPase stimulation though shifted to lower Ca2+-concentrations. The N-terminal C0C2 domain of cardiac myosin-binding protein-C increased the Ca2+-sensitivity of the pyrene-cTM movement of bovine, recombinant wt, p.A295S, and p.E361G c-actins, but not of the p.R312H mutant, suggesting decreased affinity to cTm.  相似文献   

17.
Summary Gelation of poly(vinyl alcohol) (PVA) in dimethyl sulfoxide (DMSO)/water was observed at 23°C with viscometry, spectrophotometry, wide angle X-ray scattering and light scattering. Here transparent gel formation was found to take place prior to being turbid in some cases, whereas the solution became turbid prior to gelation in other cases. Whether transparent gel is formed at first or solution becomes turbid, depends on DMSO composition. PVA solution forms gel in the DMSO composition range from 20 to 80 wt.%. Below the boundary DMSO composition of 60–70 wt.%, gelation takes place at first (i.e. transparent gel is formed) and then becomes turbid eventually, while beyond this DMSO composition the solution becomes turbid and then opaque gel is formed.  相似文献   

18.
Poly(vinyl alcohol) (PVA) cryogels, which are formed as a result of freeze–thaw treatment of concentrated solutions of the polymer, were studied in respect to the amount of gel and sol fractions in these heterogeneous macroporous gel materials depending on the conditions of the thawing step of similar cryotropic gelation. It was shown that the yield of gel fraction (the efficiency of the gelation process) was not quantitative; this was controlled by the initial PVA concentration in the solution to be frozen, and to a higher extent, by the thawing rate, when the yield increased with slowing of the defrostation process. The sol fraction could be extracted from the PVA cryogels by their rinsing with water at room temperature; the extraction of the sol was accompanied with the variations of the swelling parameters of the gels (initial slight upswelling and subsequent gradual deswelling), as well as with analogous, in their character, variations of the gel strength. It was also demonstrated that at the evaluation of the fusion enthalpies of PVA cryogels with the aid of the Eldridge–Ferry equation a consideration of the values of gel‐fraction yield gave rise to the significantly higher ΔH values than in traditional cases commonly used for the thermoreversible gels, where such an yield was not taken into account. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1822–1831, 2000  相似文献   

19.
The mechanical strength of alginate gel layers containing varying amounts of yeast cells was assessed by static uniaxial compression tests and compared to that of gel structures filled with equivalent quantities of inert mineral microparticles. Suitable gelation conditions were first determined by compression experiments on neat gel structures: alginate concentration, 2% w/v; Ca2+ ion concentration of the cross-linking solution, 100 mM; gelation time, 2 h. The presence of yeast cells in alginate disks led to the weakening of the gel structures, this effect increasing with the immobilized-cell content. By contrast, calcium chloride microparticles showing granulometric characteristics similar to those of yeast cells induced gel strengthening. The storage for 3 weeks at 4 °C in phosphate-free buffer induced noticeable weakening of alginate structures, whether filled with yeasts or not. These results are discussed in light of literature data on composite materials, in particular matrix–filler interactions.  相似文献   

20.
Submicron‐sized thermoresponsive poly(N ‐isopropylacrylamide‐co ‐acrylic acid) microgels were synthesized by soap‐free emulsion polymerization. The physical state of the microgel suspensions, in a wide range of polymer concentrations (1.1–7.1 wt %), transformed from fluid to gel when the temperature was elevated across their volume phase transition temperature at pH = 3.0. Such thermoinduced gelation behavior was studied in detail by small‐deformation oscillatory rheological measurements within the linear viscoelastic region. It was found that the gelation temperature was strongly affected by the polymer concentration, decreasing as the polymer concentration increased. The gelation kinetics showed that the suspension gelled more quickly at either larger polymer concentration or higher isothermal heating temperature. In an isothermal frequency sweep for the as‐formed gels, both storage and loss moduli, G′ and G″ , exhibited a power‐law behavior, that is, G′ (ω) ~ ω0.2–0.4 and G″ (ω) ~ ω0.46?0.50 within the frequency range where G′ dominates G″ . In addition, the elasticity of the gels, which results from the attractive particle bonds, increased markedly with increasing polymer concentration. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45259.  相似文献   

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