高浓度聚乙烯醇水凝胶性能研究

利用冷冻-解冻法制备了不同类型高浓度(30wt.%)聚乙烯醇(PVA)水凝胶,研究了PVA水凝胶的溶胀率、拉伸强度和流变特性。结果表明,高浓度PVA水凝胶的溶胀率受PVA的分子量和醇解度影响较大,PVA分子量越大,水凝胶的溶胀率越高;醇解度越高,溶胀率越低。随着冻融循环次数的增加,PVA水凝胶的强度增强;分子量越大,PVA水凝胶的强度反而越弱。在一定的频率范围内,PVA水凝胶的模量随着频率的增加而增加;随着冻融循环次数的增加,PVA水凝胶的储能模量增大。     

高强度多孔聚乙烯醇水凝胶的制备

为制备兼顾多孔性和高强度的水凝胶,本研究利用循环冷冻和冷冻干燥联用设计和制备了一系列聚乙烯醇水凝胶。从聚乙烯醇溶液的浓度、循环冷冻次数、单次冷冻时长三个方面对水凝胶的力学性能、内部微观形貌、含水量进行了研究。结果表明:以质量分数14%浓度的聚乙烯醇水溶液经过3次循环冷冻过程(16h冷冻,8h解冻)和液氮冷冻冰干后的支架,再经溶胀平衡后得到的PVA水凝胶具有最佳的力学性能,此时PVA水凝胶的拉伸强度为5.74MPa,断裂伸长率为347%;改变循环冷冻次数可有效地调节PVA水凝胶的含水量;水凝胶力学性能提高来源于体系结晶度的增大。     

PVA/Fe2O3磁敏感性水凝胶的制备及性能

采用循环冷冻-解冻方法制备了聚乙烯醇(PVA)/Fe2O3磁敏感性水凝胶. 考察了水凝胶的力学性能、溶胀性能和磁敏感性,并用扫描电镜观察了其表面形貌. 结果表明,当Fe2O3含量为1%(w)时,水凝胶的力学性能最好;水凝胶的溶胀度和脱水率随时间增加有相似的变化趋势,都随磁性粒子含量升高而降低;溶胀性能降低其交联程度增加;PVA和Fe2O3相容性较好;水凝胶在3000 Oe的磁场强度下达到饱和,呈现出很强的顺磁性,磁滞损耗较多,表明具有较好的磁敏感性.     

聚乙烯醇/粘土复合凝胶的制备及性能

文章采用冷冻-解冻法和硼酸法完成了聚乙烯醇包埋粘土微球复合材料的制备,进行了复合凝胶的力学性能和溶胀特性的测试,研究比较了不同的制备方法对复合凝胶的影响。结果表明冷冻-解冻法制备的PVA凝胶比硼酸法制备的PVA凝胶承受的拉升强度更大可以达到3.29MPa,添加粘土后的复合凝胶的溶胀性能减弱到原来的一半。     

聚乙烯醇水凝胶自修复性能

高浓度聚乙烯醇（PVA）水凝胶具有一定的修复功能,但其自修复机理及制备工艺参数对其修复性能的影响缺乏研究。本文采用冷冻-解冻法制备了高浓度自修复PVA水凝胶,通过调整PVA水凝胶制备工艺参数（PVA分子量、PVA浓度、冷冻时间、解冻时间、冷冻-解冻次数、修复时间、冷冻温度等）得到了最佳工艺条件,分析了水凝胶自修复机理,并研究了PVA水凝胶的多次自修复性能。研究结果表明：相对分子质量大的PVA制备的水凝胶自修复性能好;其中冷冻时间为2h,解冻时间为1h,一次冷冻-解冻循环制备得到的水凝胶自修复性能最好,最佳修复时间为12h,能较好地进行反复自修复。指出水凝胶自修复性能主要是由其内部可逆氢键的相互作用形成的,其主要影响源于冷冻-解冻处理后水凝胶内部羟基含量及PVA分子的流动性。     

天然纤维素/PVA复合水凝胶的形成机理及力学性能研究

为提高聚乙烯醇(PVA)水凝胶的力学性能,利用Na OH/尿素溶剂,通过物理交联循环冷冻-解冻法,制备了α-纤维素(α-CE)/PVA复合水凝胶。红外光谱,扫描电镜结果表明α-CE与PVA水凝胶基体形成互穿交联网状结构。研究发现α-CE与PVA分子链上的羟基间所形成的氢键使两者牢固结合。力学性能测试表明,复合水凝胶的力学性能得到了大幅度提高,当α-CE含量为4%(wt)时,复合水凝胶的拉伸强度以及在压缩型变量60%下的压缩应力分别由0.09和0.07 MPa提高到0.64和0.52 MPa,比纯PVA水凝胶提高了611%和643%。此外发现,α-CE能明显增强PVA水凝胶的弹性及压缩后的形变回复能力。     

聚丙烯酸钠/聚乙烯醇复合水凝胶的制备及其电响应行为

以过硫酸钾为引发剂,N, N′-二甲基双丙烯酰胺为交联剂结合冷冻-解冻交联,制备了一系列不同配比的聚丙烯酸钠(PAAS)/聚乙烯醇(PVA)互穿网络水凝胶,并用傅里叶红外光谱仪(FTIR)、场发射扫描电子显微镜(SEM)、热失重分析仪(TG)、万能试验机等对其进行表征。结果表明,PVA均匀分散于互穿网络水凝胶中,PVA的加入可以提高PAAS水凝胶的热性能;使PAAS水凝胶的溶胀速率和最大溶胀度减小,在PVA含量达到14%(质量分数,下同)时最低,随后又提高;PVA的加入可以显著提高其力学性能,断裂伸长率和拉伸强度均随PVA含量的增加而增大;PVA的加入提高了互穿网络的电响应灵敏度,且其最佳含量为21%。     

具有各向异性结构的聚乙烯醇水凝胶的制备及性能表征

首先对聚乙烯醇（PVA）水溶液进行定向冷冻-解冻制备出具有各向异性结构的PVA水凝胶,然后采用⁶⁰Co-γ射线对其进行辐射交联以提高其热稳定性和力学性能。扫描电子显微镜（SEM）结果显示PVA水凝胶保持了各向异性的微观结构,在平行冷冻方向上具有相对规整的取向结构,在垂直冷冻方向上呈现均匀孔洞结构。热稳定性测试结果表明：辐射剂量在30~70 kGy范围内、定向冷冻次数为1次的PVA水凝胶在60℃热水浴中保持凝胶状态长达10 h以上。对辐射交联PVA水凝胶进行拉伸力学性能测试,凝胶具有各向异性的拉伸性能,且拉伸强度和弹性模量均有提高,辐射剂量为10 kGy、定向冷冻次数为3次的PVA水凝胶（DFT-RC-3-10）在垂直定向冷冻方向上的拉伸强度和弹性模量分别为0.86和0.10 MPa。     

壳聚糖/碳酸钙杂化膜的研究

通过壳聚糖/钙盐复合膜浸泡在Na2CO3水溶液的方法制备出了壳聚糖/碳酸钙杂化膜。用X射线衍射仪和扫描电子显微镜表征了杂化膜内碳酸钙的晶体结构和形貌。研究了杂化膜的力学性能、溶胀率、吸光度及热稳定性。结果表明:杂化膜内碳酸钙为长3.0μm,宽1.0μm的棒状晶体,以及直径为1.0~5.0μm的多层球形晶体。随着碳酸钙的质量分数从2.69%增加到4.20%,杂化膜的溶胀率从231.6%下降到149.5%,膜的吸光度也逐渐增加。当w(CaCO3)=3.12%时,杂化膜的拉伸强度达到最大值52.12 MPa。杂化膜的分解温度为315℃,高于壳聚糖膜的分解温度290℃。这种生物相容性好的杂化膜有望用作骨细胞培养的支架材料。     

BES-Na磺酸型聚氨酯复合水凝胶的制备与性能研究

以N,N-双(2-羟乙基)-2-氨基乙磺酸钠(BES-Na)和二羟甲基丙酸(DMPA)为亲水扩链剂,原位聚合制备了一系列磺酸型水性聚氨酯(SWPU);再将丙烯酰胺(AM)引入SWPU中乳液聚合制备了一系列BES-Na磺酸型聚氨酯复合水凝胶(SWPUH)。采用傅里叶变换红外光谱(FTIR)表征了SWPUH的结构,研究了BES-Na含量对SWPUH水凝胶的溶胀性能、p H敏感性、离子强度敏感性以及力学性能的影响。结果表明,SWPUH6溶胀比最大,为33. 12,且较SWPUH1平衡溶胀比提升了50. 20%; SWPUH水凝胶还具有多重敏感性,BES-Na的加入能改善水凝胶的酸碱稳定性,且在不同离子强度溶液中,仍然具有较高的溶胀性能。另外,SWPUH水凝胶还具有优异的力学性能,其中SWPUH6水凝胶压缩强度达到最大3. 42 MPa,较SWPUH1压缩强度提升了约4. 5倍,拉伸强度最大值为0. 33 MPa,断裂伸长率最大达到了774%,相比SWPUH1分别提升了175%和59. 3%。     

Porous boron nitride nanofibers/PVA hydrogels with improved mechanical property and thermal stability

Polyvinyl alcohol (PVA) hydrogel is a promising material possessing good chemical stability, high water absorption, excellent biocompatibility and biological aging resistant. However, the poor mechanical performance of PVA hydrogel limits its applications. Here we report the utilization of one-dimensional (1D) BN nanofibers (BNNFs) as nanofillers into PVA matrix to prepare a novel kind of BNNFs/PVA composite hydrogel via a cyclic freezing and thawing method. For comparison, the composite hydrogels using spherical BN nanoparticles i.e. BN nanospheres (BNNSs) as fillers were also prepared. The mechanical properties, thermal stabilities and swelling behaviors of the composite hydrogels were investigated in detail. Our study indicates that the mechanical properties of the hydrogels can be improved by adding of BNNFs. After loading of BNNFs into PVA with content of 0.5?wt%, the compressive strength of the composite hydrogel increases by 252% compared with that of pure PVA hydrogel. The tensile performance of BNNFs/PVA composite hydrogels has also been improved. Impressive 87.8% increases in tensile strengths can be obtained with 1?wt% BNNFs added. In addition, with the increase of BNNFs content, the thermal stability and the swelling ratio of hydrogels are increased gradually. The swelling ratio of hydrogel increases by 56.3% with only 1?wt% BNNFs added. In comparison, the improvement effects of the BNNS fillers on the mechanical strengths and swelling ratios are much weaker. The enhanced effects of BNNFs can be ascribed to the strong hydrogen bond interaction between BNNFs and PVA. The high aspect ratios of the nanofibers should also be took into account.     

Hybrid Hydrogels Based on Poly(vinyl alcohol) (PVA)/Agar/Poly(ethylene glycol) (PEG) Prepared by High Energy Electron Beam Irradiation: Investigation of Physico‐Mechanical and Rheological Properties

A series of hybrid hydrogels based on poly(vinyl alcohol) (PVA)/agar/poly(ethylene glycol) (PEG) prepared by a solution casting method using e‐beam irradiation are investigated to determine the effect of agar and PEG content (1, 2, and 4 wt%) on their physicomechanical and rheological properties. The gel content of the hydrogels decreases with increasing agar and PEG contents. The equilibrium swelling of PVA hydrogel decreases on blending with agar while adding PEG to PVA/agar increases the swelling by about 400%. No obvious change in the dehydration behavior of the hybrid hydrogels is observed on changing agar and PEG contents. The solid‐like rheological behavior of the hydrogels is not significantly affected by agar content, while it approaches a liquid‐like behavior at high PEG loading. The tensile strength of the hybrid hydrogels is improved by increasing agar content, while its elongation‐at‐break is decreased. On the other hand, the opposite results are found regarding the influence of PEG and its content on the mechanical properties of the hybrid hydrogels.

     

Poly (vinyl alcohol)/graphene oxide nanocomposite films and hydrogels prepared by gamma ray

ABSTRACT

Poly (vinyl alcohol)/graphene oxide (PVA/GO) gamma irradiated nanocomposite films and hydrogels were prepared. In composite films, GO was initially irradiated by gamma ray in order to improve interactions between GO and PVA. The film containing 1?wt-% GO was very strong where tensile modulus and tensile yield strength were 45 and 115% higher than those of pure PVA. In the second set of experiments PVA/GO hydrogels were made by irradiating PVA/GO suspensions by gamma ray at various doses. It was an interesting finding that GO increased the gel portion of hydrogels through contribution of H-bonds between PVA and GO. The hydrogels prepared at 20?kGy had remarkable water swelling ratio that reached as high as 20 at water temperature of 80°C. The hydrogel metal ion adsorption capability was tested on Cu²⁺ ions. It was shown that the GO contributed significantly to the adsorption capacity of PVA hydrogels.     

基于动态共价键的pH响应自修复水凝胶制备与评价

以α-甲基丙烯酸、2-丙烯酰胺-2-甲基丙磺酸共聚产物和聚乙烯醇为单体，十水合四硼酸钠为交联剂合成P(MAA /AMPS)-PVA二重互穿网络的pH响应水凝胶；通过扫描电子显微镜(SEM)、红外光谱(FTIR)、凝胶渗透色谱（GPC）、热重分析(DSC-TG)和流变仪等表征了水凝胶的表面形貌和化学状态；测定了水凝胶的溶胀性﹑pH响应性﹑自修复性和流变性。结果表明，水凝胶形成稳定的IPN互穿网络结构且该水凝胶具pH敏感性、自修复性；PVA羟基与硼酸根离子形成的共价配位硼酸酯键决定水凝胶自修复性并受到介质酸碱控制；力学性能测定结果显示，自修复水凝胶拉伸强度668 kPa,断裂伸长率可达665%，修复效率可达81%。     

High strength and toughness of double physically cross-linked hydrogels composed of polyvinyl alcohol and calcium alginate

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.     

磺化β-环糊精/PVA凝胶电刺激响应行为的研究

首先将β-环糊精(β-CD)和聚乙烯醇(PVA)用戊二醛交联制成凝胶;然后以浓硫酸作为改性剂,将磺酸根引入凝胶中,制备出一种阴离子型磺化β-CD/PVA凝胶,并对该凝胶的平衡溶胀率、粘接性能和电刺激响应行为等进行了研究。结果表明:该凝胶在Na2SO4水溶液中的平衡溶胀率随离子强度增加而减小;其剪切强度随PVA含量增加呈先升后降态势,并且在w(PVA)=5%时相对最大(3.8 MPa)。在非接触性直流电场作用下,该凝胶在Na2SO4水溶液中弯向电场负极,其弯曲偏转速率和应变随外加电压增加而增大,并且在离子强度为0.15 mol/L时相对最大;在循环电场作用下,该凝胶的电刺激响应行为具有良好的重现性和可逆性。     

High performances of dual network PVA hydrogel modified by PVP using borax as the structure-forming accelerator

A dual network hydrogel made up of polyvinylalcohol (PVA) crosslinked by borax and polyvinylpyrrolidone (PVP) was prepared by means of freezing-thawing circles. Here PVP was incorporated by linking with PVA to form a network structure, while the introduction of borax played the role of crosslinking PVA chains to accelerate the formation of a dual network structure in PVA/PVP composite hydrogel, thus endowing the hydrogel with high mechanical properties. The effects of both PVP and borax on the hydrogels were evaluated by comparing the two systems of PVA/PVP/borax and PVA/borax hydrogels. In the former system, adding 4.0% PVP not only increased the water content and the storage modulus but also enhanced the mechanical strength of the final hydrogel. But an overdose of PVP just as more than 4.0% tended to undermine the structure of hydrogels, and thus deteriorated hydrogels’ properties because of the weakened secondary interaction between PVP and PVA. Likewise, increasing borax could promote the gel crosslinking degree, thus making gels show a decrease in water content and swelling ratio, meanwhile shrinking the pores inside the hydrogels and finally enhancing the mechanical strength of hydrogels prominently. The developed hydrogel with high performances holds great potential for applications in biomedical and industrial fields.     

Rheological investigation of poly(vinyl alcohol)/poly(N-vinyl pyrrolidone) mixtures in aqueous solution and hydrogel state

Rheological behavior of poly(vinyl alcohol) (PVA) and poly(N-vinyl pyrrolidone) (PVP) mixtures in aqueous solutions and hydrogel state was investigated. The complex dependence of the viscosity on PVA/PVP mixture composition could be attributed to cumulative effects of electrostatic interactions, hydrogen bonding or association phenomena. Physical hydrogels were prepared by freezing/thawing method and their viscoelastic properties were followed as a function of number of cryogenic cycles and aging time at 37 °C. From swelling experiments, it was observed that the diffusion of water molecules into the hydrogel pores is Fickian (for low number of cryogenic cycles) and it becomes pseudo-Fickian as the sample is submitted to more than 10 freezing/thawing cycles. PVA/PVP hydrogels obtained by physical interactions present a high degree of tailorability and they are suitable candidates for biomedical applications.     

Acid-treated Bentonite as filler in the development of novel composite PVA hydrogels

In this study, novel eco-friendly hydrogel adsorbents were synthesized based on poly(vinyl alcohol) (PVA) and different contents of an acid-treated bentonite (1–5 wt %). The hydrogels were prepared by freezing–thawing, which is a simple and nontoxic method. The materials were morphologically and thermally characterized by means of swelling assays, X-ray diffraction, scanning electron microscopy, dynamic scanning calorimetry, and thermogravimetric analysis in order to evaluate the effect of acid-treated bentonite loading. The composite hydrogels showed very distinct porous structure and thermal features in comparison to neat PVA as a consequence of the addition of the clay. Moreover, the performance of the obtained composite hydrogels was tested toward the adsorption of cationic (methylene blue) and anionic dyes (methyl red and methyl orange) from aqueous media. The presence of acid bentonite seems to be beneficial for improving the removal capacity of PVA-based hydrogels. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47663.     

聚丙烯酰胺/碳量子点/氧化石墨烯复合水凝胶制备及其性能分析

目前相比于只用一种物理交联剂,同时用两种物理交联剂提高复合水凝胶力学性能的研究少有报道。为了研究同时以碳量子点（CQDs）和氧化石墨烯（GO）作为多官能度物理交联剂对复合水凝胶力学性能的影响,本文首先分别用低温水热法和改进的Hummer法制备了50mg/mL 的CQDs水分散液和5mg/mL的GO水分散液。通过原位自由基聚合的方法,改变CQDs和GO用量,制备了一系列聚丙烯酰胺（PAM）类纳米复合水凝胶（PAM/CQDs/GO）。利用X射线衍射仪、拉力机和流变仪对所得的水凝胶进行表征和测试。得出当用1mL的CQDs水分散液和4mL的GO水分散液制备的PAM/CQDs/GO复合水凝胶力学综合性能最好,其断裂伸长率为3916.86%,拉伸强度为165.3kPa,杨氏模量为33.36kPa。结果表明：适量的CQDs和GO都能提高PAM/CQDs/GO复合水凝胶的多种力学性能,其中GO更有利于增大纳米复合水凝胶的拉伸强度、杨氏模量和耗散能,而CQDs更有利于增大断裂伸长率。与GO相反,CQDs的加入能提高纳米复合水凝胶的黏性、降低其刚性和再次被拉伸时的杨氏模量。通过对CQDs和GO的用量进行调节,可以制备出力学性能不同的纳米复合水凝胶,以满足不同领域的需要,拓宽水凝胶的应用范围。