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1.
In this work, a novel PAA‐Fe3+‐Al3+ hydrogel with triple network structure (TN) was synthesized via bimetallic ions synergistic cross‐linking strategy. As‐synthesized samples were characterized by scanning electron microscope, Fourier transform infrared analysis, and X‐ray diffractometer. The relevant experiment results demonstrated that the hydrogel can rapidly self‐heal in ambient temperature without any external stimulus with 95% healing efficiency in 60 s. Simultaneously, the relatively rapid self‐healing of PAA‐Fe3+‐Al3+ polymer can be obtained through the coordination of metal ions with the ? COO? in PAA and the oxygen of agar in the TN hydrogel system. And the prepared hydrogels demonstrate excellent mechanical properties—high tensile strength (the tensile strain ≈ 1.011 mm/mm, tensile stress ≈ 0.34 MPa) and large elasticity (the elongation at break ≈ 74%). Especially, the antimicrobial activity of the novel hydrogel against Staphylococcus aureus and Escherichia coli bacteria was investigated using the inhibition zone method, showing remarkable antibacterial activity. POLYM. ENG. SCI., 59:919–927, 2019. © 2018 Society of Plastics Engineers  相似文献   

2.
A novel type of physical hydrogel based on dual‐crosslinked strategy is successfully synthesized by micellar copolymerization of stearyl methacrylate, acrylamide, and acrylic acid, and subsequent introduction of Fe3+. Strong hydrophobic associations among poly(stearyl methacrylate) blocks form the first crosslinking point and ionic coordination bonds between carboxyl groups and Fe3+ serve as the second crosslinking point. The mechanical properties of the hydrogel can be tuned in a wide range by controlling the densities of two crosslinks. The optimal hydrogel shows excellent mechanical properties (tensile strength of ≈6.8 MPa, elastic modulus of ≈8.0 MPa, elongation of ≈1000%, toughness of 53 MJ m?3) and good self‐recovery property. Furthermore, owing to stimuli responsiveness of physical interaction, this hydrogel also shows a triple shape memory effect. The combination of two different physical interactions in a single network provides a general strategy for designing of high‐strength hydrogels with functionalities.  相似文献   

3.
Hydrogels are increasingly investigated and applied in flexible electronic devices, but their practical applications are often restricted by the poor mechanical and limited anti‐fatigue properties. This works reports an approach to robust, anti‐fatigue, and strain‐sensitive hydrogels by introducing macromolecular microsphere and mediating their supramolecular cross‐linking points. A model network composed of sulfonated polystyrene (SPS) microspheres and poly(acrylamide‐co‐acrylic acid)/Fe3+ (poly(Am‐co‐AA)/Fe3+) is investigated. The resulting composite hydrogels have high tensile strength (4.29 MPa) and anti‐fatigue property. More interestingly, such composite hydrogels have strain‐dependent conductivity and can be applied in robust flexible strain sensors for monitoring various human motions. Overall, the hydrogels developed herein not only help to understand the enhancing mechanism of composite hydrogels, but also offer alternative materials for fabricating robust electronic devices.  相似文献   

4.
Strength, toughness and self‐recoverability are among the most important properties of hydrogels for tissue‐engineering applications. Yet, it remains a challenge to achieve these desired properties from the synthesis of a single‐polymer hydrogel. Here, we report our one‐pot, a monomer‐polymerization approach to addressing the challenge by creating dual physically crosslinked hybrid networks, in particular, synergistic “soft and hard” polyacrylic acid‐Fe3+ hydrogels (SHPAAc‐Fe3+). Favorable mechanical properties achieved from such SHPAAc‐Fe3+ hydrogels included high tensile strength (about 1.08 MPa), large elongation at break (about 38 times), excellent work of extension (about 19 MJ m?3), and full self‐recoverability (100% recovery of initial properties within 15 min at 50°C and within 60 min in ambient conditions, respectively). In addition, the hydrogels exhibited good self‐healing capabilities at ambient conditions (about 40% tensile strength recovery without any external stimuli). This work demonstrates that dual physical crosslinking combining hydrophobic interaction and ionic association can be achieved in single‐polymer hydrogels with significantly improved mechanical performance but without sacrificing favorable properties. POLYM. ENG. SCI., 59:145–154, 2019. © 2018 Society of Plastics Engineers  相似文献   

5.
Flexible sensors are becoming required in heath monitoring and human–machine interfaces, but it is still a challenge to develop flexible sensors with integrated high performances. Herein, high‐performance flexible sensors are fabricated that are self‐healing, reversibly adhesive, and utilizing stretchable hydrogels, which are composed of a pluronic F127 diacrylate (F127DA) cross‐linked poly(acrylic acid) (PAA) network and polydopamine (PDA), and further cross‐linked by Fe3+. The unique structure endows the resulting hydrogels (PAA‐PDA‐Fe3+ hydrogels) excellent self‐healing property, reversible adhesion property, mechanical stretchability, and electrical conductivity. On the basis of the excellent properties of PAA‐PDA‐Fe3+ hydrogels, flexible sensors with large sensing range (0–575%), high sensitivity (GF = 6.31), low response time (0.25 s), and excellent robustness (>500 cycles) are assembled and further applied in detecting both large and subtle strains induced by human motions and water ripple. Overall, this work not only provides an alternative clue to construct multi‐functional hydrogels, but also offers a new kind of high‐performance materials for flexible electronic devices, especially those for health monitoring and human–machine interface.  相似文献   

6.
Gelatin‐based hydrogels were synthesized and characterized for use as Cu2+‐ion sorbents. Gelatin was crosslinked in the presence of two different monomers, that is, acrylamide (AAm) and/or 2‐hydroxypropyl methacrylate, with N,N‐methylenebisacrylamide, ammonium persulfate, and sodium bicarbonate. The as‐prepared hydrogels were further characterized by scanning electron microscopy, Fourier transform spectroscopy, and the study of their swelling behavior as a function of temperature, time, and pH to evaluate their structure–property relationships. The hydrogels were observed to be good sorbents of Cu2+, and a maximum uptake of 84.8% was observed within 2 h at 37°C and with 10 ppm of the Cu2+‐ion solution for the gelatin and polyacrylamide hydrogel, which also exhibited the maximum retention capacity at 14.9 mg/g after four feeds. All of the experimental data exhibited good matches with the Langmuir isotherm and followed pseudo‐second‐order kinetics. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011  相似文献   

7.
The practical application of thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) hydrogels are severely limited by their poor mechanical properties. Herein, we reported a series of dual crosslinked (DC) PNIPAM hydrogels with superior mechanical properties prepared by simple copolymerization of N-isopropylacrylamide and sodium acrylate (SA) in the laponite RDS suspension, following by a soaking process in multivalent metal cations (e.g., Ca2+, Al3+, Fe3+) aqueous solutions to form ionic coordination interactions with  COO groups of copolymer side chains. The effect of laponite RDS, AANa (sodium acrylate), and metal cation (e.g., Fe3+) concentrations on the mechanical properties and deswelling properties of the DC hydrogels are evaluated. The DC hydrogel prepared with 10 w/v% laponite RDS, 0.25 mol/L AANa and 0.45 mol/L Fe3+ possesses the best mechanical properties (ca. 1.1 MPa of tensile strength, 9.1 MPa of compression strength at 80% of compression strain, 1.4 MPa of elastic modulus and 1.3 MJ/m3 of toughness). Moreover, we also discovered that the DC hydrogels crosslinked by Fe3+ showed better mechanical properties due to the larger charge and ion radius of Fe3+.  相似文献   

8.
A multiple shape memory and self‐healing poly(acrylic acid)‐graphene oxide‐Fe3+ (PAA‐GO‐Fe3+) hydrogel with supertough strength is synthesized containing dual physically cross‐linked PAA network by GO and Fe3+. The first GO cross‐linked hydrogel can be reversibly reinforced by immersing in FeCl3/HCl and pure water and softened by immersing in HCl. The tensile strength is 2.5 MPa with the break strain of 700%. Multiple shape memory capability is found depending on this unique feature, the hydrogel can be fixed in four temporary shapes by adjusting the immersing time in FeCl3/HCl and pure water, and recovered in sequence by immersing in HCl. This hydrogel also exhibits perfect self‐healing behavior, the cut as‐prepared hydrogel is almost completely healed by immersing in FeCl3/HCl. Besides, the hydrogel shows enhanced electrical conductivity with the presence of GO and Fe3+. This supertough hydrogel provides a new way to design soft actuators.

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9.
Ion exchange between H+ and Eu3+ and/or Tb3+ was studied in the material modified by in situ sorption and thermal polymerization of acrylic acid in low‐density polyethylene (LDPE–PAA) and in the composite system LDPE–Fe2O3–PAA. Fluorescence spectroscopy showed evidence of Eu3+ and/or Tb3+ ion exchanges in these materials. The matrix LDPE–PAA after Eu(III) ion exchange presented luminescence (excitation 265 nm). This was explained by an energy‐transfer process from the matrix LDPE–PAA to Eu3+ ions. The LDPE–PAA matrix after simultaneous Eu3+/Tb3+ ion exchange exhibited Eu3+ and Tb3+ ion luminescence (excitation 265 nm), confirming an energy‐transfer process from LDPE–PAA to Eu3+ ions in LDPE–PAA–Eu3+–Tb3+ matrix. Fe2O3 in LDPE–Fe2O3–PAA quenched the matrix for excitation at 265 nm and no emission at the region 400 nm was observed. The luminescence of Tb3+ ions in the matrix LDPE–Fe2O3–PAA–Tb3+ (excitation 265 nm) was partially quenched by Fe2O3. However, a weak emission of Eu3+ ions was observed (excitation 265 nm) in the matrix LDPE–Fe2O3–PAA after simultaneous Eu3+ and Tb3+ ion exchanges, suggesting an energy transfer from Tb3+ to Eu3+ ions. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 919–931, 2000  相似文献   

10.
The phosphorylated poly(vinyl alcohol) (P‐PVA) samples with various substitution degrees were prepared through the esterification reaction of PVA and phosphoric acid. By using chitosan (CTS), acrylic acid (AA) and P‐PVA as raw materials, ammonium persulphate (APS) as an initiator and N,N‐methylenebisacrylamide as a crosslinker, the CTS‐g‐PAA/P‐PVA semi‐interpenetrated polymer network (IPN) ssuperabsorbent hydrogel was prepared in aqueous solution by the graft copolymerization of CTS and AA and followed by an interpenetrating and crosslinking of P‐PVA chains. The hydrogel was characterized by Fourier transform infrared (FTIR), scanning electron microscopy (SEM), and differential scanning calorimetry (DSC) techniques, and the influence of reaction variables, such as the substitution degree and content of P‐PVA on water absorbency were also investigated. FTIR and DSC results confirmed that PAA had been grafted onto CTS backbone and revealed the existence of phase separation and the formation of semi‐IPN network structure. SEM observations indicate that the incorporation of P‐PVA induced highly porous structure, and P‐PVA was uniformly dispersed in the polymeric network. Swelling results showed that CTS‐g‐PAA/P‐PVA semi‐IPN superabsorbent hydrogel exhibited improved swelling capability (421 g·g?1 in distilled water and 55 g·g?1 in 0.9 wt % NaCl solution) and swelling rate compared with CTS‐g‐PAA/PVA hydrogel (301 g·g?1 in distilled water and 47 g·g?1 in 0.9 wt % NaCl solution) due to the phosphorylation of PVA. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

11.
To enhance the oxygen‐barrier and water‐resistance properties of poly(vinyl alcohol) (PVA) and expand its food packaging applicability, five crosslinked poly(vinyl alcohol)/poly(acrylic acid) (PVA/PAA) blend films were prepared via esterification reactions between hydroxyl groups in PVA and carboxylic acid groups in PAA. The physical characteristics of the blends, including the thermal, barrier, mechanical and optical properties, were investigated as a function of PAA ratio. With increasing PAA content, the crosslinking density was significantly increased, resulting in changes in the chemical structure, morphology and crystallinity of the films. The oxygen transmission rate of pure PVA decreased from 5.91 to 1.59 cc m?1 day?1 with increasing PAA ratio. The water resistance, too, increased remarkably. All the blend films showed good optical transparency. The physical properties of the blend films were strongly correlated with the chemical structure and morphology changes, which varied with the PAA content. © 2016 Society of Chemical Industry  相似文献   

12.
Interpenetrating polymer network (IPN) hydrogels based on poly(vinyl alcohol) (PVA) and poly(acrylamide‐co‐sodium methacrylate) poly(AAm‐co‐SMA) were prepared by the semi IPN method. These IPN hydrogels were prepared by polymerizing aqueous solution of acrylamide and sodium methacrylate, using ammonium persulphate/N,N,N1,N1‐tetramethylethylenediamine (APS/TMEDA) initiating system and N,N1‐methylene‐bisacrylamide (MBA) as a crosslinker in the presence of a host polymer, poly(vinyl alcohol). The influence of reaction conditions, such as the concentration of PVA, sodium methacrylate, crosslinker, initiator, and reaction temperature, on the swelling behavior of these IPNs was investigated in detail. The results showed that the IPN hydrogels exhibited different swelling behavior as the reaction conditions varied. To verify the structural difference in the IPN hydrogels, scanning electron microscopy (SEM) was used to identify the morphological changes in the IPN as the concentration of crosslinker varied. In addition to MBA, two other crosslinkers were also employed in the preparation of IPNs to illustrate the difference in their swelling phenomena. The swelling kinetics, equilibrium water content, and water transport mechanism of all the IPN hydrogels were investigated. IPN hydrogels being ionic in nature, the swelling behavior was significantly affected by environmental conditions, such as temperature, ionic strength, and pH of the swelling medium. Further, their swelling behavior was also examined in different physiological bio‐fluids. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 302–314, 2005  相似文献   

13.
Three series of novel semi‐interpenetrating polymer networks, based on crosslinked poly(N‐isopropylacrylamide), PNIPA, and different amounts of the linear poly(N‐vinylpyrrolidone), PVP, were synthesized to improve the mechanical properties and thermal response of PNIPA gels. The effect of the incorporation of the linear PVP into the temperature responsive networks on the temperature‐induced transition, swelling/deswelling behavior, and mechanical properties was studied. Polymer networks with four different crosslinking densities were prepared with varying molar ratios (25/1 to 100/1) of the monomer (N‐isopropylacrylamide) to the crosslinker (N,N′‐methylenebisacrylamide). The hydrogels were characterized by determination of the equilibrium degree of swelling, the dynamic shear modulus and the effective crosslinking density, as well as tensile strength and elongation at break. Furthermore, the deswelling kinetics of the hydrogels was studied by measuring their water retention capacity. The inclusion of the linear hydrophilic PVP in the PNIPA networks increased the equilibrium degree of swelling. The tensile strength of the semi‐interpenetrating networks (SIPNs) reinforced with linear PVP was higher than that of the PNIPA networks. The elongation at break of these SIPNs varied between 22% and 55%, which are 22 – 41% larger than those for pure PNIPA networks. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009  相似文献   

14.
In this work, the properties of novel ionic polymer blends of crosslinked and sulfonated poly(vinyl alcohol) (PVA) and sulfonated poly(ether ether ketone) (SPEEK) are investigated. Crosslinking and sulfonation of PVA were carried out using sulfosuccinic acid (SSA) in the presence of dispersed SPEEK to obtain semi‐interpenetrating network blends. PVA–SSA/SPEEK blend membranes of different compositions were studied for their ion‐exchange capacity, proton conductivity, water uptake, and thermal and mechanical properties. The hydrated blend membranes show good proton conductivities in the range of 10?3 to 10?2 S/cm. When compared with pure component membranes, the PVA–SSA/SPEEK blend membranes also exhibit improvement in tensile strength, tensile modulus, and delay in the onset of thermal and chemical degradation. Semi‐interpenetrating nature of the blends is established from morphology and dynamic mechanical analysis. Morphology of the membranes was studied using scanning electron microscopy after selective chemical treatment. The dynamic mechanical properties of the membranes are examined to understand the miscibility characteristics of the blends. The relative proportions of PVA and SPEEK and the degree of crosslinking of PVA–SSA are important factors in determining the optimum properties for the blend. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

15.
Poly(acrylic acid‐co‐acrylamide) (PAAAM) hydrogels have been prepared from partly neutralized acrylic acid (AA) and acrylamide (AM) by solution polymerization, and their absorbency and adsorption in both CuCl2 and FeCl3 solutions have been investigated. PAAAM hydrogels and their complexes with Cu2+ or Fe3+ have been characterized by FTIR. The absorbency of PAAAM in both CuCl2 and FeCl3 solutions increases initially and then decreases as the absorbing time increases. The adsorption of PAAAM in both CuCl2 and FeCl3 solutions can be described by the pseudo‐second order chemisorption kinetics proposed by Ho and McKay, and the equilibrium uptake of Cu2+ on PAAAM can well be fit with the Langmuir adsorption isotherm. However, the equilibrium uptake of Fe3+ on PAAAM increases as the initial Fe3+ concentration increases for Fe3+ concentration smaller than 5.625 × 10?3 mol/L, and then decreases with Fe3+ concentration. The largest uptakes for Cu2+ and Fe3+ are 247 and 173 mg/g, respectively. The results also show that the uptake of Cu2+ and Fe3+ on PAAAM increases remarkably when pH of the solution is changed from 2.3 to 4.2 and from 1.0 and 2.1, respectively. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007  相似文献   

16.
An easy and ecofriendly method for designing double‐network (DN) hydrogels based on chitosan and poly(vinyl alcohol) (PVA) with high mechanical performance is described. When covalent bonds in the networks are used as crosslinking agents in the achievement of a higher mechanical strength, the irreversible deformation of these hydrogels after a large force is applied is still one of the most important obstacles. To overcome this problem, we used physical crosslinking for both networks. The mechanical strength, surface morphology, and cytotoxicity of the films were studied by tensile testing, scanning electron microscopy analysis, and an MTT assay. The synthesized chitosan–PVA DN hydrogels showed a large improvement in the tensile strength to 11.52 MPa with an elongation of 265.6%. The surface morphologies of the films demonstrated the effective interactions between the two networks and a suitable porosity. Also, because of the use of a natural polymer and honey as a plasticizer, the cell culture indicated that the synthesized DN hydrogels had good biocompatibility (with 327.49 ± 11.22% viability) and could be used as capable biomaterials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45752.  相似文献   

17.
Graft copolymers and networks of gelatin were synthesized with three acrylamides (acrylamide, 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid, and N‐iso‐propylacrylamide) by using a redox initiator system consisting of ammonium peroxysulfate–ferrous ammonium sulfate in either the absence or the presence of a crosslinker (N,N‐methylene bisacrylamide) at two temperatures. Characterization of synthesized polymers was studied by FTIR and thermal studies to investigate evidence of grafting or interpenetrating network formation and to investigate the effect of reaction conditions and crosslinker concentration on the properties of synthesized polymers. Detailed investigation into water‐uptake properties of these hydrogels was carried out as a function of time, temperature, and pH. The inherent properties of the monomer incorporated onto gelatin collectively act as determinant of the water‐absorption behavior of the hydrogels. Sorption of Fe+2, Cr+6, and Cu+2 ions from their aqueous solutions was also studied on select hydrogels, where it was observed that metal ions are sorbed by effective partitioning between hydrogels and solution phase and apart from the nature of metal ions, and structural aspects of hydrogels also determine the quantum of metal ion uptake. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3856–3871, 2003  相似文献   

18.
A series of poly(acrylic acid) (PAA)–poly(vinyl alcoho) (PVA) semiinterpenetrating (SIPN) and interpenetrating (IPN) polymer network membranes were prepared by crosslinking PVA alone or by crosslinking both PVA and PAA. Glutaraldeyde and ethylene glycol were used as crosslinking agents for the PVA and PAA networks, respectively. The presence of PAA increases the permeability of the membranes while the presence of PVA improves their mechanical and film-forming properties. The mechanical properties of the membranes were investigated via tensile testing. These hydrophilic membranes are permselective to water from ethanol–water mixture and to ethanol from ethanol–benzene mixtures. The IPN membranes were employed for the former mixtures and the SPIN membranes for the latter, because the IPN ones provided too low permeation rates. The permeation rates and seperation factors were determined as functions of the IPN or SIPN composition, feed composition, and temperature. For the azeotropic ethanol–water mixture (95 wt % ethanol), the separation factor and permeation rate at 50°C of the PAA-PVA IPN membrane, containing 50 wt % PAA, were 50 and 260 g/m2h, respectively. For the ethanol–benzene mixture, the PAA–PVA SIPN membranes had separation factors between 1.4 and 1200 and permeation rates between 6 and 550 g/m2h, respectively, depending on the feed composition and temperature. © 1996 John Wiley & Sons, Inc.  相似文献   

19.
A simple, multiple‐hydrogen‐bond approach to fabricating physically crosslinked, Amylopectin reinforced polyacrylamide/poly(vinyl alcohol) (Amy/PAAm/PVA) double‐network (DN) hydrogels with super toughness in bulk and at solid interfaces is reported. The Amy/PAAm/PVA DN hydrogels exhibit high tensile strength (854.1 kPa), high extensibility (≈eight times), high bulk toughness (4094.8 kJ m?3), good self‐recovery property (≈92% of self‐recovery at room temperature), and strong adhesion to nonporous glass surfaces (≈158 kPa). Such tough and adhesive DN hydrogels have great potential for various applications in engineering artificial soft tissues, flexible electronics, and wearable devices.  相似文献   

20.
In this study, novel disulfide cross‐linked hydrogels were designed and synthesized. First, ethylenediaminetetraacetic dianhydride reacted with butanediamine and amino‐terminated polyethylene glycol via N‐acylation reaction to give biocompatible poly(amic acid) (PAA) with pendant carboxyl groups; then, the amino groups of cystamine reacted with carboxyl groups of PAA to generate disulfide cross‐linked network polymer (PAA‐SS). Fourier transform infrared spectroscopy, 1H nuclear magnetic resonance imaging, gel permeation chromatography with multiangle laser light scattering, potentiometric titration, rheology, hydrolytic degradation, morphology, porosity, and in vitro biocompatibility studies were used to qualitatively and quantitatively characterize the obtained polymers. The results indicated that the equilibrium swelling ratio of the PAA‐SS decreased with the increase in Rm. The PAA‐SS provided good mechanical strength to maintain their integrity, and the storage modules (G′) of the hydrogels can be adjusted by Rm. The PAA‐SS presented co‐continuum pores, and the pore size correlated with the cross‐linking degree. The degradation of PAA‐SS could be controlled by regulating the concentration of dithiothreitol. Particularly, the PAA‐SS possessed an excellent biocompatibility, as the average proliferating rate of osteoblasts on PAA‐SS was appreciably higher than that on PAA and glass coverslips. In conclusion, the above obtained results demonstrate that the performance of the PAA‐SS outbalance and facilitate the application in biomedical region, particularly in bone tissue regeneration. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40930.  相似文献   

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