Synthesis and characterization of pH- and thermoresponsive Poly(<Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide-co-itaconic acid) hydrogels crosslinked with <Emphasis Type="Italic">N</Emphasis>-maleyl chitosan

Biodegradable cross-linker N-maleyl chitosan (N-MACH) was synthesized with chitosan (CS) and maleic anhydride (MA) by acylation. With N-MACH cross-linker, a series of cross-linked poly(N-isopropylacrylamide-co-itaconic acid) [P(NIPAAm-co-IA)] hydrogels were prepared, and their pH-and temperature-responsive behaviors, water contents, swelling/deswelling kinetics were investigated. By alternating the NIPAAm/IA weight ratios, hydrogels had the volume phase transition temperature (VPTT) changed from 33 to 38 °C, whereas cross-linking density did not affect the VPTT apparently. The water content of hydrogels was controlled by the monomer weight ratios of NIPAAm/IA, swelling media, and the cross-linking density. The results of the influence of pH value on the swelling behaviors showed that the minimum swelling ratios of the hydrogels appeared in neutral buffer solution, which was attributed to chemical composition of the hydrogels and the swelling media. In the swelling/deswelling kinetics, all the dried hydrogels exhibited fast swelling within 480 min and fast deswelling within 20 min, which was independent of the content of IA and cross-linker.     

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

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

Preparation and Characterization of Porous Poly (N-isopropylacrylamide) /Clay Nanocomposite Hydrogels

Summary  A novel porous PNIPA/Clay nanocomposite hydrogel (NC hydrogel) was prepared by in situ free-radical polymerization using inorganic clay as a crosslinker and calcium carbonate (CaCO₃) particle as a pore-forming agent and subsequent extraction of CaCO₃ with acid. The structure and morphology of the hydrogels were characterized by means of FTIR, TEM and SEM. The temperature responsive behaviors, the deswelling behaviors and the mechanical properties of the NC hydrogels were investigated in detail. The results showed that the swelling ratios below VPTT and the deswelling rates of the NC hydrogels were significantly improved as compared with the hydrogels without introduction of CaCO₃. Moreover, the NC hydrogels thus prepared also exhibited good mechanical properties.     

Swelling behavior of sulfonated polyacrylamide nanocomposite hydrogels in electrolyte solutions: comparison of theoretical and experimental results

Nanocomposite hydrogels were prepared by cross-linking of aqueous solutions of sulfonated polyacrylamide/sodium montmorillonite with chromium triacetate as ionic cross-linker. The effect of montmorillonite content on equilibrium swelling in NaCl and CaCl₂ solutions, ultimate storage modulus and effective cross-link density was evaluated. The limiting storage modulus of the nanocomposite (NC) hydrogels dropped by increasing montmorillonite content up to 1,000?ppm, and then it increased by further montmorillonite loading. A mechanism is proposed for the formation of PAMPS/Na⁺-MMT/Cr³⁺ NC hydrogels. According to this mechanism, the drop in limiting storage modulus of the NC gels at low Na⁺-MMT concentration is due to ionic interactions between the negative layers of sodium montmorillonite and Cr³⁺, leading to decreased cross-link density. However, the increase of the limiting storage modulus of the NC gels at high clay concentration results from the strong interactions between the polyacrylamide chains and clay platelets. The equilibrium swelling ratio of the NC networks decreased with increase of montmorillonite content in both aqueous NaCl and CaCl₂ solutions. In addition, the experimental swelling data of these NC hydrogels were described by a modified Flory?CRehner theory. The modified model was sensitive to montmorillonite concentration and it described adequately the swelling data for NC gels in NaCl solutions. Nevertheless, theoretical predictions showed some deviations from experimental results for swelling of NC hydrogels in CaCl₂ solutions.     

A facile method for reinforcing poly(N‐isopropylacrylamide)‐hectorite clay nanocomposite hydrogels by heat treatment

A facile method was explored to reinforce the poly(N‐isopropylacrylamide) (PNIPAm)‐hectorite nanocomposite hydrogel (NC gel) by heat treatment at temperature above the volume phase transition temperature (VPTT), which enhanced mechanical strength and reduced swelling capacity with denser microporous structure as compared with the non‐treated NC gel. This reinforcement effect was increased by increasing treating temperature and/or treating time, which still remained even after swelling, indicating an irreversible structure change in the treated NC gels. Heat treatment became more effective when the NC gel contained higher clay content. The quartz crystal microbalance (QCM) data showed that the interaction between PNIPAm chains and clay platelets became stronger at temperatures higher than the VPTT, causing an increase in the crosslinking density of the treated NC gels. A strong hydrogel was obtained by heat treatment of the aqueous mixture of PNIPAm and hectorite clay for the first time. POLYM. COMPOS., 37:1557–1563, 2016. © 2014 Society of Plastics Engineers     

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 and properties of P(NIPAAm‐co‐AM)/SiO2 hybrid temperature‐sensitive hydrogels

Using N, N′‐methylene bisacrylamide as crosslinking agent and potassium peroxydisulfate as initiator, the temperature‐sensitive hydrogels were prepared with organic monomer N‐isopropylacrylamide (NIPAAm) and acrylic amide and inorganic material ethyl orthosilicate (TEOS). The structure of hybrid hydrogels was represented by scanning electron microscopy and Fourier transform infrared spectroscopy. The volume phase transition temperature (VPTT) of hybrid hydrogels was determined by differential scanning calorimetry thermograms of the swollen hydrogel. The results showed that the VPTT of the hydrogels increased with the increasing of TEOS dosage. When the temperature was lower than VPTT, the hydrogels exhibited excellent temperature sensitivity and kept at a swelling state, but when the temperature was higher than VPTT, the hydrogels deswelled significantly. In addition, the compressive strength of hydrogels was studied, the results showed that hybrid hydrogels had more ideal mechanical properties than organic hydrogels. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Microwave‐assisted preparation of temperature sensitive poly(N‐isopropylacrylamide) hydrogels in poly(ethylene oxide)‐600

In this article, a series of poly(N‐isopropylacrylamide) (PNIPAM)‐based hydrogels were prepared under microwave irradiation using poly(ethylene oxide)‐600 (PEO‐600) as reaction medium and microwave‐absorbing agent as well as pore‐forming agent. All of the temperature measurements, gel fractions, and FTIR analyses proved that the PNIPAM hydrogels were successfully synthesized. Within 1 min, the PNIPAM hydrogel with a 98% yield was obtained under microwave irradiation. The PNIPAM hydrogels thus prepared exhibited controllable properties such as pore size, equilibrium swelling ratios, and swelling/deswelling rates when changing the feed weight ratios of monomer (N‐isopropylacrylamide, NIPAM) to PEO‐600. These properties are well adapted to the different requirements for their potential application in many fields such as biomedicine. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:4177–4184, 2006     

Rheological properties of thermoresponsive nanocomposite hydrogels

Highly elastic and robust nanocomposite hydrogels based on N‐isopropylacrylamide (NIPAM) and cationic (3‐acrylamidopropyl) trimethylammonium chloride (AMPTMA) were synthesized by photopolymerization. Nanoscopic clay, laponite XLS, was added in the gels during the synthesis. The effect of a hydrophobic salt, lithium bis(trifluoromethane) sulfonimide (LiNTf₂), and clay content on the viscoelastic properties, swelling ratio, and stiffness of the nanocomposite hydrogels were investigated as a function of temperature. Synthetic clay served as a multifunctional cross‐linker, producing hydrogels with enhanced elastic properties. Anionic NTf₂ binds to the cationic comonomer units and significantly affected the viscoelasticity and thermal properties. DSC measurements showed that the volume phase transition temperature and its enthalpy changed with the clay content and with introducing the cationic comonomer (AMPTMA) in the PNIPAM network. With the addition of either laponite XLS or the comonomer and 5 mM solution of LiNTf₂, a fourfold and fivefold increase in elastic modulus was obtained, respectively, compared to that of the homopolymer PNIPAM hydrogel. With increasing the temperature from 20 to 45°C for the copolymer gel with 10% AMPTMA in 5 mM LiNTf₂, the elastic modulus grew 15 times larger. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43123.     

Preparation of antimicrobial polycarboxybetaine‐based hydrogels for studies of drug loading and release

A series of cationic poly(N‐isopropyl acrylamide) (PNIPAM)‐g‐poly(carboxybetaine ester) (PCBMAE) hydrogels were prepared by reversible addition–fragmentation chain‐transfer polymerization with PCBMAE precursors reacting with N‐isopropyl acrylamide in the presence of N,N′‐methylene bisacrylamide. These hydrogels exhibited excellent antimicrobial activities against Staphylococcus aureus and could switch to nontoxic zwitterionic hydrogels after hydrolysis. Nonionic tetracycline hydrochloride (TCHC) and anionic sodium salicylate (SA) were selected to evaluate the loading capacities and release kinetics of the cationic hydrogels. We found that the loading efficiencies of TCHC in the PNIPAM‐g‐PCBMAE hydrogels were approximately twice as high as those of SA. However, the cumulative release amount of TCHC was lower than that of SA from the corresponding cationic hydrogel at 37°C. In addition, the PNIPAM‐g‐PCBMAE hydrogels exhibited accelerated release rates of both TCHC and SA with increasing content of (2‐carboxymethyl)?3‐acryloxyethyldimethylammonium chloride methyl ester. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39839.     

Preparation and performance of nanocomposite hydrogels based on different clay

To look for economic substitute of Laponite, two kinds of clay minerals purchased in China were chosen to prepare nanocomposite hydrogels. Structure, morphology, temperature-sensitivity and swelling behavior were investigated by XRD, SEM, DSC and gravimetric method. In comparison with hydrogel cross-linked by Laponite XLG, the hydrogel with hectorite (Lvjie trademark) or montmorillonite (G-105) as cross-linker exhibited higher swelling ratios as well as faster response rate. In the case of temperature-sensitivity, the volume phase transition temperature (VPTT) of the hydrogels cross-linked by hectorite (Lvjie trademark) and montmorillonite (G-105) was 31–33 °C, slightly different from hydrogels with Laponite XLG. The hydrogel with montmorillonite (G-105) was brown and fragile. The hectorite (Lvjie trademark) appeared as optimal substitute of Laponite in hydrogels because the prepared hydrogel exhibited high swelling ratio, rapid response rate, excellent thermal responsibility, good dispersion in hydrogel matrix and high storage modulus.     

Preparation and characterization of pH‐ and temperature‐responsive semi–interpenetrating polymer network hydrogels based on linear sodium alginate and crosslinked poly(N‐isopropylacrylamide)

In this study, pH‐ and temperature‐responsive hydrogels based on linear sodium alginate (SA) and crosslinked poly(N‐isopropylacrylamide) (PNIPAAm) were prepared by semi‐interpenetrating network (semi‐IPN) technique. The dually responsive hydrogels were characterized by FTIR, DSC, and SEM, and their temperature‐ and pH‐responsive behaviors were investigated by measuring equilibrium swelling ratios and pulsatile swelling experiments. The results showed that these hydrogels underwent volume phase transition at around 33°C irrespective of the pH value of the medium, but their pH sensitivity was evident only below their volume phase transition temperature. Under basic conditions, the swelling ratios of SA/PNIPAAm semi‐IPN hydrogels were greater than that of pure PNIPAAm hydrogel and increased with increasing SA content incorporated into the hydrogels, but the case was inverse under acidic conditions. The pulsatile swelling experiments indicated that the higher the SA content in SA/PNIPAAm semi‐IPN hydrogels, the faster the response rate to both pH and temperature change. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1931–1940, 2005     

Fast swelling behaviors of thermosensitive poly(N‐isopropylacrylamide‐co‐methacryloxyethyltrimethyl ammonium chloride)/Na2WO4 cationic composite hydrogels

A facile method was explored to synthesize thermosensitive poly[N‐isopropylacrylamide (NIPAM)‐co‐methacryloxyethyltrimethyl ammonium chloride (DMC)]/Na₂WO₄ cationic hydrogels via copolymerization of NIPAM and DMC in the presence of Na₂WO₄. Na₂WO₄ acted as both a physical crosslinking agent and a porogen precursor. The hydrogels were characterized by Fourier transform infrared spectroscopy, energy dispersive X‐ray, thermogravimetry, environmental scanning electron microscopy, and transmission electron microscopy. Effects of various salt solutions, pH solutions on swelling were investigated. Thermosensitivity of the hydrogels were also investigated in various polar solvents at different temperatures. The resultant hydrogel showed a fast swelling rate and good salt tolerance. The hydrogels reached the swelling equilibrium within 10 min. Moreover, the swelling ratio of the hydrogels increased with the increase of the polarity of the solvent. In the water, the swelling ratio decreased with the increasing of temperature, but remained at a high level even at 80 °C since the pore structure weaken the lower critical solution temperature effect of PNIPAM. The swelling ratio increased instead in low polar solvent, while it became negligible in nonpolar solvent with the increasing of temperature. The whole swelling kinetics was fit for Schott's pseudo‐second order model. The hydrogels have a great potential as catalysts and smart materials. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46375.     

Swelling behaviour and paracetamol release from poly(<Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide-itaconic acid) hydrogels

Copolymer hydrogels of N-isopropylacrylamide and itaconic acid (IA), crosslinked with N,N′-methylenebisacrylamide, were prepared by radical copolymerization. These hydrogels were investigated with regard to their composition to find materials with satisfactory swelling and drug release properties. A paracetamol is used as a model drug to investigate drug release profile of the hydrogels. It was found that the investigated hydrogels exhibited pH- and temperature-dependent swelling behaviour with restricted swelling and lower equilibrium degree of swelling at lower pH values and temperatures above the LCST value of PNIPAM (around 34 °C). The diffusion exponent for paracetamol release indicate that the mechanism of paracetamol release are governed by Fickian diffusion, while in all release media initial diffusion coefficient was lower than late time diffusion coefficient. Furthermore, the paracetamol release rate depends on the hydrogel degree of swelling and it increased in the first stage of diffusion process, whereas was no significant difference thereafter. The presence of the IA moieties incorporated into the network weakened the shear resistance of the hydrogels. In order to calculate the pore size the characteristic ratio for PNIPAM, C _n  = 11.7, was calculated. Based on the pore size, the investigated hydrogels can be regarded as microporous. According to the obtained results swelling behaviour, mechanical properties, drug-loading capacity and the drug release rate could be controlled by hydrogel composition and crosslinking density, which is important for application of the investigated hydrogels as drug delivery systems.     

Synthesis and Characterization of Temperature-Sensitive Poly(N-isopropylacryamide) Hydrogel with Comonomer and Semi-IPN material

A series of temperature and pH sensitive hydrogels were synthesized using N-isopropylacrylamide (NIPAAm) as main monomer, sodium alginate (SA) as semi-IPN material, ethyl acrylate (EA) and acrylic acid (AA) as comonomer, and N-maleyl chitosan (N-MACH) as cross-linker. The temperature and pH sensitive behavior, swelling/deswelling kinetics of the hydrogels were investigated. And the mechanism of the phase transition was summed up. Sodium alginate/Poly(N-isopropylacryamide) semi-interpenetrating polymer network (SA/PNIPAAm semi-IPN) hydrogels exhibited a lower critical solution temperature (LCST) at about 32 °C with no significant deviation from the conventional PNIPAAm hydrogels. Poly(N-isopropylacryamide-co-ethyl acrylate) (P(NIPAAm-co-EA)) hydrogels exhibited LCST at 29–31°C, increasing the amount of EA in the hydrogel gradually decreased the LCST. Poly(N-isopropylacryamide-co-acrylic acid) [P(NIPAAm-co-AA)] hydrogels exhibited LCST at 34–39°C, with decreasing NIPAAm/AA from 96/4 to 92/8 and 90/10, the LCST increased from 34°C to 37°C and 39°C. In the swelling/deswelling kinetics, all the dried hydrogels exhibited fast swelling/deswelling behavior, which might be attributed to macroporous structures of the hydrogels.     

Preparation and Swelling Properties of Temperature‐Sensitive Semi‐Interpenetrating Polymer Networks Composed of Poly[(N‐tert‐butylacrylamide)‐co‐acrylamide] and Hydroxypropyl Cellulose

Summary: Temperature‐responsive hydrogels based on linear HPC and crosslinked P(NTBA‐co‐AAm) were prepared by the semi‐IPN technique. The structure of these semi‐IPN hydrogels was investigated by FT‐IR spectroscopy. An increase in normalized band ratios (A₂₉₈₀/A₁₆₆₅) was observed with increasing HPC content in the initial mixture. The swelling kinetics and water transport mechanism of these semi‐IPN hydrogels were examined and their temperature responsive behaviors were also investigated by measuring equilibrium swelling ratios and pulsatile swelling experiments. The results showed that these semi‐IPN hydrogels underwent a volume phase transition between 18 and 22 °C irrespective of the amounts of MBAAm and HPC. However, below the volume phase transition temperature, their equilibrium swelling ratios were affected by the amount of MBAAm and HPC. The pulsatile swelling experiments indicated that the lower the MBAAm and the higher HPC contents in semi‐IPN hydrogels the faster the response rate temperature change.

Equilibrium swelling ratios of the semi‐IPN P(NTBA‐co‐AAm)/HPC hydrogels in water shown as a function of temperature.     

Swelling characteristics of thermo‐ sensitive poly[(2‐diethylaminoethyl methacrylate)‐co‐(N,N‐dimethylacrylamide)] porous hydrogels

Temperature‐sensitive poly[(2‐diethylaminoethyl methacrylate)‐co‐(N,N‐dimethylacrylamide)] [P(DEAEMA‐co‐DMAAm)] hydrogels with five different DMAAm contents were synthesized with and without the addition of sodium carbonate as porosity generator. The synthesized hydrogels were characterized with dry gel density measurements, scanning electron microscopy observation and the determination of swelling ratio. The influence of the pore‐forming agent and content of DMAAm on swelling ratio and network parameters such as polymer–solvent interaction parameter (χ), average molecular mass between crosslinks (M?_c) and mesh size (ζ) of the cryogels are reported and discussed. The swelling and deswelling rates of the porous hydrogels are much faster than for the same type of hydrogels prepared via conventional methods. At a temperature below the volume phase transition temperature, the macroporous hydrogels also absorbed larger amounts water compared to that of conventional hydrogels and showed obviously higher equilibrated swelling ratios in aqueous medium. In particular, the unique macroporous structure provided numerous water channels for water diffusion in or out of the matrix and, therefore, an improved response rate to the external temperature changes during the deswelling and swelling processes. These properties are attributed to the macroporous and regularly arranged network of the porous hydrogels. Scanning electron micrographs reveal that the macroporous network structure of the hydrogels can be adjusted by applying porosity generation methods during the polymerization reaction. Copyright © 2007 Society of Chemical Industry     

pH–thermoreversible hydrogels. II. Synthesis and swelling behaviors of N-isopropylacrylamide-co-acrylic acid-co-sodium acrylate hydrogels

A series of pH–thermoreversible hydrogels are prepared from the three molar ratios of N-isopropylacrylamide (NIPAAm) and acrylic acid neutralized 50 mol % by sodium hydroxide (SA50) and N,N′-methylene bisacrylamide (NMBA). The influence of the environmental conditions, such as temperature and pH values, on the swelling behavior of these copolymeric gels is also investigated in this article. Results show that the hydrogels bearing negative charges exhibit different equilibrium swelling ratios under various pH media. The pH sensitivities of these gels also strongly depend on the molar ratio of SA50 in the copolymeric gels; thus, the more the SA50 content, the higher the gel pH sensitivity. These hydrogels exhibited thermosensitivity demonstrating a larger change of the equilibrium swelling ratio in aqueous media under temperature changes. An overshooting phenomenon is observed from the gel swelling kinetics under high-temperature conditions. The said hydrogels are also used to investigate the release of model drugs in this study. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1955–1967, 1999     

Synthesis,characterization, and drug release properties of poly(N-isopropylacrylamide) gels prepared in methanol–water cononsolvent medium

Poly(N-isopropylacrylamide) (PNIPAM) hydrogels were simply prepared by free radical polymerization in different methanol–water mixture. A scanning electron microscopy study revealed that the freeze-dried hydrogels were macroporous. The swelling ratios in water at 20°C of the resulting hydrogels followed the order: X_0.43>X_0.21>X_0.76 ≈ X_0.57>X_0.31>X_0.13>X_0.06>X₀, where X_m denotes a gel prepared in a methanol–water mixture with m mole fraction of methanol (x_m). Below the lower critical solution temperature, the swelling ratio values of all of the hydrogels gradually decreased with the increase in the temperature. The complete collapse of the PNIPAM chain of all the gels occurred at about 38°C, whereas the same was observed at about 35°C for the conventional gel prepared in water. The swelling ratio values of all the PNIPAM gels in the methanol–water mixtures with different x_m values at 20°C passed through a minimum in the cononsolvency zone. The deswelling rates of the hydrogels decreased in the following order: X_0.43> X_0.31> X_0.21> X_0.57> X_0.76 ≈ X_0.13> X_0.06> X₀. The reswelling rates of these hydrogels decreased in the following order: X₀> X_0.31> X_0.06 ≈ X_0.13 > X_0.76> X_0.57> X_0.21> X_0.43. The release rates of the Tramadol Hydrochloride drug at 37°C from the drug-loaded hydrogels were almost same for all of the hydrogels. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

聚（N-异丙基丙烯酰胺）／海藻酸钠／粘土复合水凝胶的制备及溶胀动力学研究

以无机粘土为交联剂制备了聚（N-异丙基丙烯酰胺）／海藻酸钠／粘土（PINPA／SA／Clay）复合水凝胶,通过红外光谱、X射线衍射对凝胶的结构进行了表征,结果表明：粘土的结晶结构已被破坏,粘土规整的片层被剥离并在凝胶中无序分布,起到交联剂的作用;随粘土含量的增加,凝胶网络交联密度增加,溶胀速度下降。在不同温度下对不同粘土含量的凝胶进行了溶胀动力学测试,表明在低于其相转变温度时,凝胶的扩散类型为non－Fickian扩散。