聚乙二醇改性纳米纤维素/聚乙烯醇复合水凝胶的制备及性能

通过酸碱处理和机械研磨结合的方法制备纳米纤维素(CNFs),并利用冻融循环法分别制备了聚乙烯醇(PVA)和纳米纤维素/聚乙烯醇(CNFs/PVA)复合水凝胶,以及聚乙二醇(PEG)改性PVA和CNFs/PVA复合水凝胶。考察不同配方下复合水凝胶的微观形貌变化,并对复合水凝胶的溶胀性能、压缩强度及热稳定性能进行研究。结果表明,CNFs与PEG对PVA水凝胶的微观形貌均有改善作用,加入PEG后形成的PEG/PVA凝胶产生明显的三维网络结构。当PEG与CNFs同时加入到PVA凝胶后形成的CNFs-PEG/PVA凝胶具有均匀的互穿孔洞结构,此时复合水凝胶的孔隙率最高((67.5±4.3)%),溶胀度最好(980%),且压缩强度较PVA水凝胶也有所提升。PEG对复合凝胶的热稳定性无影响,而加入CNFs后,CNFs-PEG/PVA复合凝胶的初始热分解温度从235℃上升至300℃,显著提高了PVA凝胶的热稳定性。     

多孔PVA/CNFs复合水凝胶的制备与性能

目的研究聚乙二醇(PEG)的加入对复合凝胶微观结构、溶胀性能和热稳定性的影响,扩大复合凝胶在包装领域的应用。方法以PEG为致孔剂,纳米纤维素(CNFs)为增强相,利用物理交联法制备出多孔聚乙烯醇/纳米纤维素复合水凝胶。结果 PEG作为致孔剂时可制得网络互穿结构的多孔水凝胶,复合凝胶的溶胀度可达到1000,相比于纯PVA水凝胶有极大的提高,同时加入CNFs的聚乙烯醇凝胶与纯的聚乙烯醇凝胶相比具有更好的热稳定性。结论这种有着高溶胀性和良好热稳定性的多孔复合凝胶可用于包装产品的保鲜与物流防护。     

纳米细菌纤维素/聚乙烯醇复合水凝胶在模拟体液中的疲劳行为

聚乙烯醇(PVA)复合水凝胶作为半月板及软骨等长期承重植入体,在生理环境中的疲劳行为关系到植入体的持久性和稳定性。采用弥散增强的方法将纳米细菌纤维素(BC)均匀分散在PVA水凝胶基体中,制备了纳米BC/PVA复合水凝胶。在模拟体液(SBF)环境中,采用压缩疲劳过程分析、疲劳前后刚度变化分析及疲劳前后尺寸稳定性分析3种方法,测试和评价了复合水凝胶的抗疲劳性能和力学稳定性。结果表明:纳米BC/PVA复合水凝胶在模拟人体环境中具有良好的抗疲劳性能,能够满足体内植入物的抗疲劳性能需求;纳米BC的加入可以有效提升复合水凝胶的力学稳定性和抗疲劳性能,但随着纳米BC含量的进一步升高,复合水凝胶的抗疲劳性能有所减弱,当PVA与纳米BC质量比为30∶1时,纳米BC/PVA复合水凝胶疲劳前期与后期最大位移变化量最小(0.002mm),疲劳前后刚度变化最小(5.41%),且疲劳前后尺寸稳定性最强,变形量仅为0.427mm,抗疲劳性能达到最佳。     

聚对二氧环己酮/聚乙烯醇复合水凝胶的制备及性能

在聚乙烯醇(PVA)水凝胶的网络中引入完全生物降解的聚对二氧环己酮(PPDO),采用冻融法制备出生物降解周期可控的PPDO/PVA复合水凝胶。通过调整低分子量PPDO与高分子量PVA之间的比例,使PPDO柔性分子链与PVA分子链之间形成聚合物网络互穿结构,实现改善水凝胶力学性能和生物降解性能的目的。采用红外光谱、扫描电镜和万能试验机对水凝胶进行了结构表征和性能测试;并通过溶胀性能及失水性能测试、降解性能测试和抑菌性测试对水凝胶进行了研究。结果表明,PPDO/PVA复合水凝胶呈现出孔隙均匀的三维网络结构,拉伸强度和压缩强度与纯PVA水凝胶相比提高了1～3倍;在37℃的PBS缓冲溶液中降解,降解速率明显提升,35 d可以降解45%,且在伤口愈合的周期内保持优异的力学强度。平板细菌培养实验证明了复合水凝胶具有抑菌的特性。PPDO/PVA复合水凝胶在伤口敷料领域具有广泛的应用前景。     

纳米材料掺杂型聚乙烯醇双交联复合水凝胶的力-化学性质

以聚乙烯醇(PVA)为原料,氧化石墨烯(GO)和羟基磷灰石(HA)为共掺杂物,先以戊二醛作为交联剂,采用化学交联法制备了GO/HA/PVA单网络单交联复合水凝胶,再通过循环冷冻-解冻技术使PVA聚合物链间进一步发生氢键交联,制备得到GO/HA/PVA双网络双交联复合水凝胶。采用HRSEM、XRD表征了水凝胶的微观形貌和晶相结构,并研究了GO与PVA、HA与PVA在不同质量比及不同冷冻-解冻循环次数时制备所得GO/HA/PVA复合水凝胶的力学性能。结果表明:随着GO与PVA质量百分比的增加(0%～2.6%),该凝胶拉伸力学强度不断增强;随着HA与PVA质量比的增加(0.22～1.10),该凝胶的拉伸强度先增强后减弱;随着冷冻-解冻循环次数增加(0次、3次、7次)该凝胶的拉伸强度逐渐增强,弹性模量也逐渐提高。当GO与PVA质量百分比为1.9%、HA与PVA质量比为0.66、冷冻-解冻循环次数N=7次时,制备所得凝胶的拉伸力学性能最优(拉伸强度为695 kPa,断裂应变为286%,弹性模量为78 kPa)。此外,深入研究了不同冷冻-解冻循环次数对水凝胶含水率和溶胀率的影响规律。结果表明:不同冷冻-解冻循环次数(0次、3次、7次)的凝胶含水率为79.3%～81.7%,平衡溶胀率为50.1%～72%,且均在60 min后达到溶胀平衡。该水凝胶有望作为软骨替代材料应用于临床医学领域。     

聚乙烯醇/聚乙烯基吡咯烷酮复合水凝胶的结构与性能研究

用溶液共混法和冷冻解冻工艺制备聚乙烯醇(PVA)/聚乙烯基吡咯烷酮(PVP)二元复合水凝胶,通过红外、XRD、DSC、含水率与溶胀测试等对材料的结构与性能进行分析表征,并研究了材料的力学性能与细胞毒性.结果表明,PVP能与PVA通过化学键合形成分子级混合的PVA/PVP复合水凝胶.PVP含量可以影响PVA水凝胶的结构、结晶度、玻璃化转变温度、吸水率以及力学性能.该复合水凝胶具有高的吸水率和良好的细胞相容性,而且具有类似天然软骨的可渗透性.PVP/PVA复合水凝胶是一种有发展前景的人工软骨替代材料.     

PVA／HA复合水凝胶的结构和摩擦学性能

将聚乙烯醇(PVA)和纳米羟基磷灰石(HA)按一定比例共混,采用反复冷冻-融化法制备出PVA/HA复合水凝胶.观察了PVA/HA复合水凝胶的微观结构和晶态结构,并在小牛血清稀释液润滑条件下进行了PVA/HA复合水凝胶与牛膝关节软骨的摩擦磨损试验.结果表明:随着冷冻-融化循环数的增加,PVA/HA复合水凝胶结构中氢键的作用增强,缠结结构链上的交联点增多,复合水凝胶的结晶度也随之提高,微孔结构趋于完整,因而使其压缩刚度增大;PVA/HA复合水凝胶与牛膝关节软骨的摩擦系数、接触变形和磨损量都随着冷冻-融化循环数的增加而显著减小,使复合水凝胶的减摩性和耐磨性提高.     

聚乙烯醇/纤维素纳米纤热塑性复合材料的制备及表征

将聚乙烯醇(PVA)、纤维素纳米纤(CNFs)通过熔融共混成功制备出高性能PVA/CNFs热塑性复合材料。采用扫描电镜、红外光谱、X射线衍射、差示扫描量热分析、热重分析对PVA/CNFs复合材料的微观形态及结构进行表征,对复合材料的物理力学性能进行测试。结果表明,选用适当的增塑剂与PVA、CNFs组合可实现PVA/CNFs共混体系的热塑成型;CNFs与PVA间的氢键作用有助于提高CNFs与PVA基体之间的相容性,从而优化PVA/CNFs复合材料的力学性能,拉伸强度从19.5 MPa增加到34.3 MPa,弹性模量从114.4 MPa增加到287.5 MPa。     

Ag/PVA复合水凝胶的制备及其性能的研究

通过沉淀法制备Ag/PVA复合水凝胶,对复合水凝胶的微观结构进行了表征,并对其力学性能和抗菌性能进行了研究.结果表明,银微粒可以通过沉淀法均匀分散在水溶性的PVA中,形成Ag/PVA复合水凝胶,并且这种复合水凝胶具有抗菌性能,并改善了PVA水凝胶的力学性能.     

聚乙烯醇/乙二醇/氧化石墨烯/聚苯胺导电复合物水凝胶的制备及性能研究

通过共混和冻融循环法制备了聚乙烯醇(PVA)/乙二醇(EG)/氧化石墨烯(GO)/聚苯胺(PANl)复合水凝胶.并采用红外光谱(FTlR)、电子扫描显微镜(SEM)、X射线光电子能谱(XPS)、万能电子试验机和电化学工作站等手段对复合凝胶的微观结构、力学性能以及导电性能进行了研究.所获得的复合水凝胶的拉伸强度随着EG含量的增加而增强;复合水凝胶的电导率随着GO含量的增加呈先增大后减小的趋势.该复合凝胶在-20℃仍保持良好的柔韧性和电导率(5.93±0.55)S/m.同时,利用该水凝胶制作了一种简单的应变传感器,能够有效地检测人体的微小运动.     

微波原位合成2D Ni-Fe MOF/硅藻土复合材料及其改性聚乙烯醇水凝胶不锈钢筛网油水分离性能

如何高效处理含油污水的问题,是如今世界科研人员共同关注的问题。聚乙烯醇(PVA)水凝胶作为高含水量及具有三维亲水网络的软材料在油水分离领域引起了广泛的关注。但是,和大多数具有超润湿性质的水凝胶一样,PVA水凝胶类油水分离材料不仅力学性能差,同时也存在化学稳定性差的问题。基于此,通过微波法制备了2D Ni-Fe金属-有机框架材料(MOF)-硅藻土(Dia)纳米材料及其PVA复合水凝胶。同时,不锈钢网经过浸泡2D Ni-Fe MOF-Dia/PVA水凝胶溶液得到2D Ni-Fe MOF-Dia/PVA水凝胶不锈钢筛网,表现出超亲水-水下超疏油性质。利用SEM、XPS分析2D Ni-Fe MOF-Dia及其复合水凝胶的化学组成和表面形貌。研究了2D Ni-Fe MOF-Dia/PVA复合水凝胶的力学性能及2D Ni-Fe MOF-Dia/PVA复合水凝胶不锈钢筛网的油水分离与乳液分离的分离效率及水通量,并对其耐盐性、耐酸耐碱性油水分离性能进行了测试。结果表明:2D Ni-Fe MOF-Dia/PVA复合水凝胶具有优异的力学性能,拉伸与压缩强度分别达到1.49 MPa及0.58 MPa,同时表现出超亲水-水下超疏油性质,2D Ni-Fe MOF-Dia/PVA不锈钢筛网的油水分离与乳液分离效率与通量分别可达99.2%和742.7 L·m?2·h?1。在酸性、碱性、盐性环境下均保持优异的分离效率与通量,并且在5次循环后,依旧保持稳定的分离效率与通量。      

Properties of hydrogels synthesized by freezing and thawing aqueous polyvinyl alcohol solutions and their applications

The hydrogel synthesized by freezing a polyvinyl alcohol (PVA) aqueous solution and thawing it slowly has high water content, excellent mechanical properties of high tensile strength, elongation and good shape recovery by elasticity. The PVA used had a degree of polymerization of 2500 and a degree of saponification of 99.5 mol%. The solution was obtained by dissolving 7.5 g of PVA in 80 g of water, this was frozen at –50°C for 3 h and then warmed up to room temperature over 10h. This freezing–thawing process was repeated once again and a hydrogel was synthesized. The hydrogel had a water content of about 90 wt%. Its tensile strength was 0.6 MPa and the elongation at break was 130%. The shape of the hydrogel which was deformed by an external force recovered in a short time when it was released from the force. This recovery had good persistence and repeatability. Applying these properties a strain sensor and a gas pressure sensor were tested. Furthermore, a PVA hydrogel rod containing polyacrylic acid was used as a bending actuator. This hydrogel had the ability to deform when direct current was applied.     

基于离子交联复合水凝胶的易制备、高性能的可穿戴应变传感器

可响应多种机械激励模式且具有较高灵敏度的柔性传感器在电子皮肤、健康监测等领域具有重要意义.而模仿皮肤的多信号响应,如应变和温度,仍然是一个重要的挑战.因此,本文设计了具有韧性与导电性的多功能离子交联水凝胶.通过将丙烯酰胺与N,N’-亚甲基双丙烯酰胺、过硫酸铵交联,可制备出具有高力学强度特性的化学凝胶,交联时加入Ca^(...     

加工芳纶纳米纤维/聚乙烯醇水凝胶制备高强度复合薄膜

芳纶纳米纤维(ANF)具有大长径比、高比表面积、丰富的表面酰胺官能团和优异的力学性能,是制备高强度纳米复合材料的理想构筑单元。本文开发了一种新颖的水凝胶加工策略,用于制备ANF增强聚乙烯醇(PVA)复合薄膜,逐步优化了ANF的含量、水凝胶的预拉伸比和PVA组份的化学交联,表征分析了复合薄膜中ANF的分散、取向、PVA的交联形式及ANF与PVA之间的界面氢键作用,当ANF的质量分数为25wt%、水凝胶的预拉伸比为55%和采用氯化铜交联PVA基体时,复合薄膜的力学性能最优,其杨氏模量和拉伸强度分别高达(14.6±0.3) GPa 和(496.5±10.0) MPa,远远优于文献报道的ANF增强聚合物复合材料。此外,该高强度纳米复合薄膜同时具有良好的透明性和优异的紫外屏蔽性能,透明度大于72.1%,能够屏蔽大于99.98%紫外线,可用做先进包装材料。      

Facile preparation of low swelling,high strength,self-healing and pH-responsive hydrogels based on the triple-network structure

A polyacrylic acid(PAA)/gelatin(Gela)/polyvinyl alcohol(PVA)hydrogel was prepared by copolymerization,cooling,and freezing/thawing methods.This triplenetwork(TN)structure hydrogel displayed superior mechanical properties,low swelling ratio and self-healing properties,The superior mechanical properties are attributed to the triple helix association of Gela and PVA crystallites by reversible hydrogen bonding.The characterization results indicated that the fracture stress and the strain were 808 kPa and 370% respectively,while the compression strength could reach 4443 kPa and the compressive modulus was up to 39 MPa under the deformation of 90%.The hydrogen bonding in PVA contributed to maintain and improve the self-healing ability of hydrogels.Every type of hydrogels exhibited a higher swelling ratio under alkaline conditions,and the swelling ratios of PAA,PAA/PVA and PAA/Gela hydrogels were 27.71,12.30 and 9.09,respectively.The PAA/Gela/PVA TN hydrogel showed the lowest swelling ratio(6.57)among these hydrogels.These results indicate that the novel TN hydrogels possess good environmental adaptability and have potential applications in the biomedical engineering and sensor field.     

细菌纤维素/聚乙烯醇双网络复合水凝胶的制备与性能研究

利用冷冻-解冻法制备了细菌纤维素（BC）/聚乙烯醇（PVA）双网络复合水凝胶,研究不同BC含量及循环周期对BC/PVA复合水凝胶力学性能和溶胀特性的影响,结果表明,随着BC含量的增多,复合水凝胶的含水率、平衡溶胀比、拉伸强度和压缩强度与普通的PVA水凝胶相比均有一定程度的提高;综合考虑,当BC含量为4%时,各项性能均达到最佳值;随着循环次数的增多,水凝胶内部的物理交联点增多,导致水凝胶的含水率下降,拉伸强度和压缩强度则有明显的上升趋势。SEM观察的结果与之前的分析是一致的。     

牵伸倍率对PEDOT PSS/PVA复合导电纤维结构与性能的影响

将合成的导电聚(3,4-乙撑二氧噻吩)-聚对苯乙烯磺酸(PEDOT-PSS)与聚乙烯醇(PVA)共混, 通过湿法纺丝, 得到了电导率较高、力学性能良好、可进行机织的PEDOT-PSS/PVA复合导电纤维, 研究了牵伸倍率对纤维导电性能、结构、热性能和力学性能的影响。结果表明: 随着牵伸倍率的增加, PEDOT-PSS/PVA复合导电纤维表面的微纤数量增加, 结晶性能、热稳定性及力学性能均有所提高; 当PEDOT-PSS/PVA复合导电纤维的牵伸倍率为4.0时, 其断裂强度、伸长率和初始模量分别为6.74 cN/dtex、5.95%和42.43 cN/dtex, 电导率可达到34.5 S/cm, 具有良好的应用性能。     

纳米纤维素基泡沫材料在包装领域的研究进展

纳米纤维素作为天然可降解材料,具有优良的力学性能、高比表面积、大长径比等特性。为研究基于纳米纤维素开发的泡沫材料在包装领域的应用,对近年来纳米纤维素基泡沫材料的制备方法及其缓冲、隔热、阻燃、抗菌、疏水等性能进行总结,概括了纳米纤维素泡沫材料在纳米纤维素制备、湿泡沫发泡和泡沫成型干燥等领域的进展。但由于现阶段纳米纤维素制备工艺的复杂性,以及干燥过程中较高的能耗和较长的周期,作为包装材料的关键性能指标还有进一步提升的空间,实现规模化生产仍有一些问题有待解决。通过综述纳米纤维基泡沫材料在包装领域的研究进展,以期为可持续包装材料的发展提供理论支持。     

Strong,Tough, and Anti-Swelling Supramolecular Conductive Hydrogels for Amphibious Motion Sensors

Conductive polymer hydrogels (CPHs) are widely employed in emerging flexible electronic devices because they possess both the electrical conductivity of conductors and the mechanical properties of hydrogels. However, the poor compatibility between conductive polymers and the hydrogel matrix, as well as the swelling behavior in humid environments, greatly compromises the mechanical and electrical properties of CPHs, limiting their applications in wearable electronic devices. Herein, a supramolecular strategy to develop a strong and tough CPH with excellent anti-swelling properties by incorporating hydrogen, coordination bonds, and cation-π interactions between a rigid conducting polymer and a soft hydrogel matrix is reported. Benefiting from the effective interactions between the polymer networks, the obtained supramolecular hydrogel has homogeneous structural integrity, exhibiting remarkable tensile strength (1.63 MPa), superior elongation at break (453%), and remarkable toughness (5.5 MJ m⁻³). As a strain sensor, the hydrogel possesses high electrical conductivity (2.16 S m⁻¹), a wide strain linear detection range (0–400%), and excellent sensitivity (gauge factor = 4.1), sufficient to monitor human activities with different strain windows. Furthermore, this hydrogel with high swelling resistance has been successfully applied to underwater sensors for monitoring frog swimming and underwater communication. These results reveal new possibilities for amphibious applications of wearable sensors.     

Graphite/poly (vinyl alcohol) hydrogel composite as porous ringy skirt for artificial cornea

Graphite/poly (vinyl alcohol) (PVA) hydrogel composites, which were designed as the porous ringy skirt surrounding the transparent core of a novel artificial cornea, were prepared by using the freeze/thawing process and the particle-leaching technique. The properties of the composites, including the water content, the mechanical strength, the porous architecture and the interactions between the graphite and PVA, were investigated. The tissue responses to the composite and pure PVA hydrogel were studied by in vivo implantation in the dorsal muscles of mice. The results showed that chemical interactions were present between the graphite and PVA in the composite, which benefited the combination of the two phases and enhanced the uniform distribution of graphite particles in the PVA matrix. However, the present of graphites in the PVA hydrogels reduced the tensile strength, elongation at break and water content of the composite. Moreover, the porous graphite/PVA hydrogel composite had interconnective pore structure with high porosity and enough mechanical strength. According to the histological analysis of 1 week and 12 weeks post-implantation, the graphite/PVA hydrogel composites showed less inflammatory reactions than the PVA hydrogels at the 1 week post-implantation. Moreover, compared to pure PVA hydrogel, the graphite/PVA hydrogel composite exhibited enhanced migration and infiltration of cells, and more neovascularization and tissue ingrowth. These in vivo characteristics will be beneficial for the long-term biofixation of artificial cornea. Therefore, the porous graphite/PVA hydrogel composite has a potential to be used as novel artificial cornea skirt.