多孔PVA水凝胶的组成、形貌及泊松比等力学性能研究

制备了不同含量的纯聚乙烯醇(PVA)水凝胶和不同表面活性剂含量的多孔PVA水凝胶,采用数字散斑测量其泊松比,并使用电镜和显微镜观察其微观结构,探讨了纯PVA水凝胶与多孔PVA水凝胶组成、微观结构、泊松比、压缩模量和体积模量的变化及相互关系.研究发现,采用表面活性剂成孔,反复冷冻成型制备的闭孔结构水凝胶,其泊松比随应力应变增加而减小;随PVA含量增加而泊松比值减小;随表面活性剂含量增加,孔径变大,泊松比值减小.PVA水凝胶泊松比值与压缩模量和体积模量的比值成正比.     

聚乙烯吡咯烷酮/黏土纳米复合水凝胶的制备及表征

通过原位聚合法, 以N-乙烯基吡咯烷酮(NVP)和黏土为原料制备了生物相容性有机-无机纳米复合水凝胶, 通过黏度、透明度、XRD及力学性能等研究了水凝胶体系的性质和微观结构. 结果显示, 单体NVP通过氢键作用吸附于黏土粒子周围, 从而有效阻止黏土颗粒的凝胶化; 通过对聚合过程透明度的变化、凝胶吸水性能以及拉伸力学性能分析发现, 其反应机理与丙烯酰胺类体系不同. 黏土颗粒间网链较短, 导致吸水率和断裂伸长率明显低于聚丙烯酰胺/黏土体系, 但模量和拉伸及压缩强度明显增加; XRD结果显示, 干凝胶中黏土颗粒呈有序排列, 随着黏土含量增加, 黏土粒子间距变小, 而在含水复合凝胶中, 黏土颗粒以剥离态均匀分散; 对于凝胶表面的细胞形态观察初步检验了此类纳米复合凝胶的细胞相容性, 未观察到显著不良影响.     

醇溶剂交换对聚合物/黏土纳米复合水凝胶的性能改进及结构表征

采用原位自由基聚合,制备了聚N,N-二甲基丙烯酰胺(PDMAA)/黏土(clay)纳米复合水凝胶(D-NCgel),黏土在体系结构中充当多官能团交联点的作用.考察了D-NC gel中溶剂水被交换为醇溶剂时,凝胶结构稳定性,溶胀特性,以及机械性能的变化.D-NC gel在醇溶剂中仍能保持完整的三维网络结构,体系没有瓦解.而且,D-NC gel在醇溶剂中表现出依赖于醇溶剂种类的溶剂交换和溶胀行为.在甲醇中,凝胶溶胀度呈现单调增长,但是在其它醇溶剂,如乙醇、1-丙醇或1-丁醇中,凝胶表现出先收缩后溶胀的特殊溶胀行为.通过在醇溶剂中先溶胀后干燥的方法,制备具有优异机械性能的醇溶剂纳米复合凝胶.与D-NC5 gel相比,D-NC5甲醇凝胶其拉伸力学强度提高了67%(从155 kPa增加到259 kPa),拉伸模量提高了49%(从7.5 kPa增加到11.2kPa).基于凝胶在醇水溶剂中结构可逆性讨论的基础上,探讨了醇溶剂对D-NC水凝胶的改性机理.     

溶胶-凝胶法原位复合PVA/HA水凝胶的结构表征与性能研究

采用溶胶-凝胶原位复合的方法制备了聚乙烯醇/羟基磷灰石生物活性复合水凝胶,探讨了HA含量对复合水凝胶结构性能的影响,用X射线衍射分析、红外光谱分析、DSC、扫描电镜等方法对HA在PVA水凝胶体系中的晶态结构及分散状态进行了表征,并与物理共混复合法进行了比较.研究发现,采用溶胶-凝胶法原位复合可在PVA水凝胶中形成具有生物活性的HA结晶结构,且分散良好,分布均匀.HA粉体作为异相成核剂,促进了PVA水凝胶基体的结晶,提高了复合水凝胶的力学性能.     

多孔纳米羟基磷灰石/聚乙烯醇复合水凝胶的表征

本文通过采用溶盐致孔法,制备了多孔纳米羟基磷灰石／聚乙烯醇复合水凝胶材料。用透射电子显微镜、红外光谱、扫描电子显微镜和图像分析对材料进行了表征。结果表明纳米羟基磷灰石与聚乙烯醇之间有一定键合,并且多孔纳米羟基磷灰石／聚乙烯醇复合水凝胶中大孔呈均匀分布且相互贯通,复合水凝胶的含水率在80％左右。该种多孔复合水凝胶是可用于人工角膜支架,是一种很有开发前景的生物医用材料。     

聚乳酸/羟基磷灰石多孔复合材料的制备及体外降解研究

采用溶剂浇铸-盐沥洗法制备了具有较高孔隙率的聚左旋乳酸/羟基磷灰石(PLLA/HA)多孔复合材料,用扫描电镜(SEM)和衰减全反射-傅立叶变换红外光谱(ATR-FTIR)研究了HA含量对制备样品的形貌以及体外降解行为的影响.结果表明,100/10、100/20、100/30、100/40和100/50的PLLA/HA复...     

PLA/MWNTs/HA复合材料的制备和性能研究

采用超声辅助原位湿法合成多壁碳纳米管／羟基磷灰石纳米复合材料(MWNTs／HA),并通过溶液浇铸法制备了PLA／MWNTs／HA复合材料薄膜。考察了MWNTs／HA纳米粒子含量对复合膜性能的影响,并通过力学性能、SEM、FTIR、以及DMTA对复合膜性能进行了表征,结果表明：随着纳米粒子质量分数的增加,复合膜的拉伸强度呈下降趋势;拉伸模量和储能模量呈现先下降后上升的趋势;玻璃化转变温度则呈现不断上升趋势。     

HA/Ag纳米复合材料的制备与性能

采用一锅热熔胶法制备出多孔花状羟基磷灰石/银(HA/Ag)纳米复合材料。通过检测罗丹明B揭示了HA/Ag作为SERS活性底物的独特拉曼增强效应,其检测极限为10~(-8) mol·L~(-1)。在检测中,改变拉曼激光强度,取点位置等手段能有效提高检测的灵敏度。此外,所制备的多孔纳米复合材料HA/Ag作为对硝基苯酚(4-NP)还原为对氨基苯酚(4-AP)反应的催化剂,可以大大缩短反应时间40 min。     

钛基多孔HA/SiO2复合涂层的制备及性能研究

为了制得表面多孔且与基材结合强度高的羟基磷灰石(HA)涂层,实验中以正丁醇为分散介质,以SiO2粉末为添加剂,纯钛片为基材,电泳沉积制备羟基磷灰石/二氧化硅/壳聚糖/(HA/SiO2/CS)复合涂层,经后续热处理得到多孔HA/SiO2复合涂层,采用扫描电镜(SEM)、傅立叶红外光谱仪(FT-IR)、X射线衍射仪(XRD)、万能材料试验机对涂层的表面形貌、组成、结构和结合强度进行测试和表征,并通过模拟体液(SBF)浸泡法对复合涂层的生物活性进行评价.结果表明:当悬浮液中的HA/SiO2/CS质量比为1∶1∶1时,制得的HA/SiO2/CS涂层经700℃热处理后获得的HA/SiO2复合涂层孔洞分布均匀,大孔孔径在10～15μm,小孔孔径在1～5μm;涂层与基材的结合强度达到25.5 MPa;多孔HA/SiO2复合涂层在SBF中浸泡7 d后,涂层表面碳磷灰石化;说明实验中添加SiO2所制得的多孔HA/SiO2复合涂层与钛基材结合强度高,且具有良好的生物活性.     

HA/GCPU复合多孔支架的可控制备及细胞相容性

以脂肪族异佛尔酮二异氰酸酯(IPDI)作为硬段、蓖麻油甘油酯(GCO)作为软段,通过原位聚合法制备了羟基磷灰石/蓖麻油甘油酯基聚氨酯(HA/GCPU)复合多孔支架.利用红外光谱和扫描电子显微镜对复合支架进行表征,并测试其力学性能及孔隙率.研究结果表明,HA/GCPU复合多孔支架的孔隙率和抗压强度依赖羟基磷灰石的含量,并具有明显的可控性.HA质量分数分别为0,20%和40%时,HA/GCPU复合多孔支架孔隙率分别为(61±3)%,(68±2)%和(57±3)%,抗压强度分别为(605±61),(2125±58)和(4588±260)k Pa,可见HA质量分数为20%时,HA/GCPU复合多孔支架具有与松质骨较为匹配的孔隙率和抗压强度.将MG63细胞与多孔支架共培养,通过倒置显微镜和扫描电子显微镜观察,用噻唑蓝(MTT)法表征HA/GCPU复合多孔支架的细胞相容性,结果表明,HA/GCPU复合多孔支架表面细胞黏附,生长良好,无细胞毒性,在骨组织工程领域具有一定的应用前景.     

In-situ Synthesis and Characterization of Poly(vinyl alcohol)/Hydroxyapatite Composite Hydrogel by Freezing-thawing Method

Poly(vinyl alcohol)/hydroxyapatite(PVA/HA) composite hydrogel was successfully in-situ synthesized via three cycles of freezing-thawing. The composition and structure of products were investigated by X-ray diffraction( XRD), Fourier transformed infrared spectroscopy(FTIR) and scanning electron microscopy(SEM). The influence of different preparation methods and contents of material on the mechanical properties of PVA/HA composite hydrogel was discussed through tensile and compressive tests. The template of PVA could avoid the agglomeration of HA particles, which improves the mechanical properties of the composite hydrogel effectively. The tensile strength, modulus and compressive performances of the PVA/HA composite hydrogel prepared by the in-situ synthesis method were better than those of hydrogel obtained by the simple blend metliod. In addition, the effect of the content of PVA, HA, and the pH value on tlie properties of tlie PVA/HA composite hydrogel has been discussed in detail.     

Amphiphilic urethane acrylate hydrogels having heterophasic gel structure: swelling behaviors and mechanical properties

 Amphiphilic urethane acrylate hydrogels containing ionic group (dimethylopropionic acid, DMPA) were prepared by varying the molecular weight of the soft segment (polyether type, PTMG) and type of diisocyanate, and their swelling behaviors and mechanical properties were examined. They showed amphiphilic property due to the hydrophilic ionic groups and hydrophobic polyethers comprising the urethane acrylate network. Heterophasic gel structure could be found for the hydrogels prepared in water, but not for the hydrogels in organic solvent (1,4-dioxane), through scanning electron microscopy. Because of this heterophasic gel structure, they were able to take in a large amount of water as well. The hydrophobic interaction generated by the polyether soft segments between urethane acrylate network chains decreased the degree of swelling, however, increased reversibly the tensile strengths at equilibrium swelling state. MDI-based hydrogel showed low swelling ratio and high tensile strength because of its ordered hard domain structure. These amphiphilic urethane acrylate hydrogels showed salt- and pH-dependent swelling behaviors. Received: 26 September 1997 Accepted: 24 December 1997     

Cellulose–halloysite nanotube composite hydrogels for curcumin delivery

Halloysite nanotubes (HNTs) were added to cellulose NaOH/urea solution to prepare composite hydrogels using epichlorhydrine crosslinking at an elevated temperature. The shear viscosity, mechanical properties, microstructure, swelling properties, cytocompatibility, and drug delivery behavior of the cellulose/HNT composite hydrogels were investigated. The viscosity of the composite solution increases with the addition of HNT. The compressive mechanical properties of composite hydrogels are significantly improved compared with pure cellulose hydrogel. The compressive strength of the composite hydrogels with 66.7% HNTs is 128 kPa, while that of pure cellulose hydrogel is only 29.8 kPa in compressive strength. Rheological measurement suggests the resistance to deformation is improved for composite hydrogels. X-ray diffraction and Fourier transform infrared spectroscopy show that the crystal structure and chemical structure of HNT are not changed in the composite hydrogels. Hydrogen bonding interactions between HNT and cellulose exist in the composites. A porous structure of the composite hydrogels with pore size of 200–400 μm was found by scanning electron microscopy. The addition of HNT leads to decreased swelling ratios in NaCl solution and pure water for the composite hydrogels. Cytotoxicity assays show that the cellulose/HNT composite hydrogels have a good biocompatibility with MC3T3-E1 cells and MCF-7 cells. Curcumin is further loaded into the composite hydrogel via physical adsorption. The curcumin-loaded composite hydrogels show a strong inhibition effect on the cancer cells. All the results illustrate that the cellulose/HNT composite hydrogels have promising applications such as anticancer drug delivery systems and anti-inflammatory wound dressings.     

Microstructured polyacrylamide hydrogels made with hydrophobic nanoparticles

Poly(methyl methacrylate) nanosize particles, made by microemulsion polymerization, were dispersed in an acrylamide aqueous solution, which was polymerized in the presence of a cross-linking agent to yield microstructured hydrogels. The kinetics of swelling and the mechanical properties of these hydrogels were investigated as a function of concentration of particles. The microstructured hydrogels exhibit higher equilibrium swelling and larger Young modulus than conventional (that is, without particles) polyacrylamide hydrogel. The morphology of the microstructured hydrogels was examined by transmission electron microscopy.     

基于Pickering乳液的磁性高强水凝胶的制备及性能表征

合成了一种磁性Fe3O4纳米颗粒稳定的水包油(O/W)Pickering乳液并以其作为交联剂,在适宜条件下引发单体丙烯酰胺聚合来制备了一种新型的磁性高强复合水凝胶.采用X射线衍射(XRD)及场发射扫描电子显微镜(SEM)分别对磁性Fe3O4纳米颗粒和复合水凝胶的结构进行了表征,结果表明Pickering乳胶粒子较均匀地分布在复合凝胶网络中.溶胀性能测试及溶胀动力学分析表明复合水凝胶具有良好的溶胀性能,能够吸收自身干重100倍左右的水,其溶胀过程不遵循Fickian扩散模型;拉伸测试表明该水凝胶具有优异的力学性能,其拉伸强度能够达到150 kPa左右,断裂伸长率能够达到300%左右,并且当其承受的应力释放后能快速地恢复到初始形态.磁性能测试的结果显示该水凝胶具有良好的磁性.     

RADIATION SYNTHESIS AND CHARACTERIZATION OF POLY(AA-co-NVP)/CLAY HYDROGELS

The pH-sensitive P(AA-co-NVP)/clay hydrogels were prepared with the monomers of acrylic acid(AA)and N-vinyl-2-pyrrolidone(NVP)based onγ-ray irradiation technique.The influence of pH values of buffer solutions and contents of clay and NVP on the equilibrium swelling ratio(SR)and compressive properties of the hydrogels was investigated in detail.The results of swelling property tests showed that,with the increase of clay content,the SR of hydrogels increases in the same buffer solution,and the SR of hydrog...     

TEMPERATURE AND pH RESPONSE, AND SWELLING BEHAVIOR OF POROUS ACRYLONITRILE-ACRYLIC ACID COPOLYMER HYDROGELS

Macroporous acrylonitrile-acrylic acid （AN-AA） copolymer hydrogels were synthesized by flee-radical solution polymerizations, using ammonium persulfate （APS）/N,N,N＇,N＇-tetramethylethylenediamine （TEMED） redox initiator system and alcohols porogens. The morphology, temperature and pH sensitive swelling behavior, and swelling kinetics of the resulting hydrogels were investigated. It was found that alcohol type and concentration had great influences on the pore structure and porosity of hydrogels. The pore size of hydrogel increases with the moderate increase of the length of alcohol alkyl chain. However, a further increase of alkyl length would result in the formation of cauliflower-like structure and the decrease of pore size. The porosity of hydrogels increases with the increase of porogen concentration in the polymerization medium. The hydrogels with macroporous structure swell or shrink much faster in response to the change of pH in comparison with the conventional hydrogel without macroporous structure. Furthermore, the response rate is closely related to the porosity of the hydrogels, which could be easily controlled by modulating the concentration of the porogen in the medium. The circular swelling behavior of hydrogels indicated the formation of a relaxing three-dimensional network.     

多孔聚乙烯醇缩甲醛凝胶力学行为对含水量变化的敏感性

通过成孔剂法制备具有连通孔结构的聚乙烯醇缩甲醛凝胶(PVFM) ,研究其在吸水膨胀脱水收缩过程中力学行为对含水量变化的响应性.实验表明多孔PVFM具有很快的吸水 脱水速度,吸水80s内就可达到最大的平衡膨胀应力,干燥4h内其膨胀应力可降低95 % ;同时还发现多孔PVFM在脱水干燥过程中出现明显的体积回弹和膨胀应力回复现象,而且压缩模量在一定范围内随含水量的减少反而降低,分析表明这些与PVFM的多孔结构、弹性网络的状态有密切关系.     

Structurally Enhanced Hydrogel Nanocomposites with Improved Swelling and Mechanical Properties

In this work, structurally enhanced hydrogel nanocomposites based on 2-acrylamido-2 methyl propane sulfonic acid (AMPS)-acrylamide (AAM) copolymer with high hydrophilic group content were prepared by in-situ copolymerization by using different types of clay (montmorillonite, mica and halloysite). Nanocomposite hydrogels were characterized by Fourier-Transform Infrared Spectroscopy (FTIR) and X-ray diffraction (XRD) analyses and determination of swelling degrees of the samples. Mechanical properties of the samples were also investigated by determination of the compressive elastic modulus. It was also found that exfoliated or highly expanded intercalated nanocomposite structure was obtained and clay incorporation into the AMPS-AAM hydrogel structure improved its swelling capacity. The highest swelling capacity (1030 g H₂O/g) was observed for the nanocomposite sample prepared with the montmorillonite amount of 5% (w). Furthermore, mechanical strength of the hydrogels against compression forces was significantly improved by the clay addition. It was found that the type of clay, in other word filler geometry, affected the compressive elastic modulus (E) of the samples. It was concluded that halloysite, which is considered to be a one dimensional (1D) nanotubular filler was less effective to enhance the compressive elastic modulus (E) of such materials compared with the montmorillonite and mica having two dimensional (2D) platelet or disk-like shapes at a particular amount of clay.     

Mussel-inspired chemistry in producing mechanically robust and bioactive hydrogels as skin dressings

The development of hydrogels as skin dressings demonstrates a great potential in real life applications. To achieve this, the hydrogel has to conquer its natural poor mechanical strength, and to prolong its lifetime, antifatigue and self-healing properties originating from dynamic interactions are also required. As skin dressings, the hydrogel needs to maintain its ductility while pursuing the above mentioned properties. In this work, poly(ethylene glycol) diacrylate is used to produce skin dressings by reinforcing poly(ethylene glycol) diacrylate/alginate double network hydrogels with a crosslinker from mussel-inspired chemistry, which is 3,4-dihydroxy-l-phenylalanine. This crosslinking methodology significantly improved mechanical strength of the hydrogel, with 11,200% increase in compressive failure strength; it endowed the hydrogel with outstanding antifatigue and training strengthening properties that makes its mechanical strength increasing in a 50 cycles compressive test; the hydrogel showed excellent self-healing properties that in rheological characterization; it also displayed enhanced storage modulus after withstanding a shear strain up to 1100%; meanwhile, the hydrogel exhibited extreme ductility with an elastic modulus of only 10.90–16.53 kPa. 3,4-dihydroxy-l-phenylalanine also renders the hydrogel its inherent antioxidant activity, conductivity, and bioadhesiveness. Together with the highly transparent appearance, the hydrogels possess a great potential and practibility in the fields of skin dressings.