聚丙烯酰胺/改性纳米纤维素晶体纳米复合水凝胶的光聚合制备与表征

先用马来酸酐对纳米纤维素晶体(NCC)进行表面改性得表面含碳-碳双键的改性NCC(mNCC),然后将丙烯酰胺(AM)和mNCC一起光聚合得PAM/mNCC纳米复合水凝胶;通过红外光谱、扫描电镜、热重分析、差热分析、溶胀实验和拉伸实验研究了水凝胶的结构和性能。结果表明,PAM/mNCC纳米复合水凝胶是一种物理/化学共交联水凝胶;与用质量分数0.25%N,N-亚甲基双丙烯酰胺交联的PAM水凝胶相比,PAM/mNCC纳米复合水凝胶中的微孔尺寸分布更宽,PAM分子链的起始分解温度和玻璃化转变温度升高;当mNCC的用量占AM质量的5%~10%时,PAM/mNCC纳米复合水凝胶的饱和溶胀率、拉伸强度、断裂伸长率分别为PAM水凝胶的2.1~2.7倍、0.45~1.1倍、3.8~7.1倍。     

高力学强度羟乙基纤维素/聚丙烯酰胺复合水凝胶的制备EI北大核心CSCD

通过自由基聚合一步合成了羟乙基纤维素/聚丙烯酰胺(HEC/PAM)复合水凝胶,这种水凝胶具有优异的拉伸性能和压缩性能,可能源于PAM链与HEC链之间的氢键相互作用。经测试,HEC/PAM复合水凝胶可被拉伸至原尺寸的24倍,对应的拉伸断裂应力为113kPa;90%压缩形变对应的压缩强度达0.87 MPa;水凝胶的最大压缩形变达95%以上。同时,HEC/PAM水凝胶还表现出了优异的可恢复性能。因此,HEC/PAM复合水凝胶在生物医药领域有潜在的应用价值。     

高力学强度羟乙基纤维素/聚丙烯酰胺复合水凝胶的制备

通过自由基聚合一步合成了羟乙基纤维素/聚丙烯酰胺(HEC/PAM)复合水凝胶,这种水凝胶具有优异的拉伸性能和压缩性能,可能源于PAM链与HEC链之间的氢键相互作用。经测试,HEC/PAM复合水凝胶可被拉伸至原尺寸的24倍,对应的拉伸断裂应力为113kPa;90%压缩形变对应的压缩强度达0.87 MPa;水凝胶的最大压缩形变达95%以上。同时,HEC/PAM水凝胶还表现出了优异的可恢复性能。因此,HEC/PAM复合水凝胶在生物医药领域有潜在的应用价值。     

POSS杂化聚丙烯酰胺/PU复合水凝胶的制备及其对Pb~(2+)吸附性能研究

采用POSS杂化聚丙烯酰胺(PAM-co-OVPOSS)和聚丙烯酰胺(PAM)为交联剂,分别与PU作用形成交联网络结构,制备PAM/PU和PAM-co-OVPOSS/PU复合水凝胶。通过对比分析,详细探讨分子结构、溶液浓度等对凝胶性能的影响,使用扫描电镜(SEM)、红外光谱(FT-IR)、万能试验机对水凝胶的结构以及力学性能进行详细表征研究发现PAM/PU,PAM-co-OVPOSS/PU复合水凝胶对Pb2+的吸附主要是化学吸附为主结果表明两种凝胶均具有很好的吸附性能,PAM/PU [15%%(质量分数)PAM,40g/L PU]复合水凝胶最大吸附量为228mg/L,PAM-co-OVPOSS/PU [20%(质量分数)PAM-co-OVPOSS,60g/L PU]复合水凝胶最大吸附量为195mg/L。PAM-co-OVPOSS/PU比PAM/PU凝胶呈现更好的力学强度,通过实验研究、吸附动力学和吸附热力学理论模拟分析,详细讨论了凝胶对Pb2+的吸附机理和PAM-co-OVPOSS/PU凝胶力学性能的增强机理。     

PAM/AMPS/GO纳米复合水凝胶的制备及染料吸附性能研究

通过原位溶液聚合法制备聚丙烯酰胺/2-丙烯酰胺-2-甲基丙磺酸/氧化石墨烯(PAM/AMPS/GO)纳米复合水凝胶。采用X射线衍射和红外谱图对复合水凝胶的结构进行了表征,并研究pH对水凝胶的染料吸附性能的影响。结果表明:GO与聚合物基体间存在较强的相互作用,能够均匀的分散在基体中。另外,复合水凝胶在中性溶液中对亚甲基蓝染料的吸附效果最佳,且最快达到吸附平衡。     

氧化海藻酸钠/聚丙烯酰胺水凝胶的制备与表征

通过水-乙醇和水-正丙醇两种不同的溶剂体系制备高分子量和不同氧化度的氧化海藻酸钠(OSA),然后引入聚丙烯酰胺(PAM)交联网络结构,通过二步法获得OSA/PAM复合水凝胶。探讨了不同反应体系下,HCl体积分数对OSA分子量的影响以及氧化剂(高碘酸钠NaIO_4)添加量、反应时间对OSA氧化度的影响规律。结果表明:在水-正丙醇体系下,HCl体积分数为24vol%时,氧化海藻酸钠的分子量达到170 000;调节NaIO_4的添加量和反应时间可以控制OSA的氧化度在10%~85%范围内变化。在此基础上对OSA/PAM复合水凝胶的溶胀率和力学性能进行了探讨,发现氧化度10%的复合水凝胶48h后的溶胀率达1 777%,断裂强度为0.11MPa,随着OSA氧化度的增大,OSA/PAM复合水凝胶的溶胀率增大,而拉伸强度逐渐减小。     

氧化石墨烯/聚丙烯酰胺/聚甲基丙烯酸复合水凝胶

以N,N-亚甲基双丙烯酰胺(BIS)为交联剂,过硫酸铵(APS)为引发剂,采用自由基引发聚合,使丙烯酰胺(AM)和甲基丙烯酸(MAA)在氧化石墨烯(GO)水溶液中进行共聚,制备了GO/PAM/PMAA复合水凝胶。研究了GO、MAA和BIS含量对复合水凝胶性能的影响。结果表明,GO/PAM/PMAA复合水凝胶具有三维网络结构,表现出pH敏感性,具有较好的药物缓释性能;热稳定性、力学性能随GO、BIS含量的增加而增强;平衡溶胀比随GO、BIS含量的增加而降低,随MAA含量的增加先增大,后减小,当n(AM)∶n(MAA)=10∶1时达到最大值。     

聚丙烯酰胺/聚甲基丙烯酸(2-甲基氨基)乙酯高强度双网络水凝胶的制备及pH响应性

利用两步法合成了聚丙烯酰胺(PAM)/聚甲基丙烯酸(2-甲基氨基)乙酯(PDMAEMA)双网络水凝胶,第一网络为锂藻土(Laponite)物理交联的PAM纳米复合水凝胶,第二网络为化学交联剂N,N-亚甲基双丙烯酰胺(BIS)交联PDMAEMA。研究了2种网络相对含量、纳米黏土Laponite用量、化学交联剂BIS用量对水凝胶强度和pH响应性的影响。研究结果表明,PAM/PDMAEMA双网络水凝胶具有高强度,改变单体AM和DMAEMA的配比、交联剂的用量,其拉伸强度在36～91.9 kPa范围内可调。PAM/PDMAEMA双网络水凝胶还具有灵敏的pH刺激响应性,在pH=4时双网络水凝胶溶胀度急剧下降。     

SA/PAM/GO纳米复合水凝胶的制备和性能

用原位聚合法制备海藻酸钠(SA)/聚丙烯酰胺(PAM)/氧化石墨烯(GO)纳米复合水凝胶,用X射线衍射、原子力显微镜、红外光谱、热失重、扫描电镜等手段对GO及复合水凝胶的结构与性能进行表征,研究了GO含量对材料的结构、机械性能及溶胀性能的影响。结果表明:在聚合物体系中均匀分散的GO片层提高了分子之间的相互作用,并参与形成凝胶网络,显著提高了材料的强度与韧性。与纯SA/PAM凝胶相比,拉伸强度和断裂伸长率提高了近200%,压缩强度从2.95 MPa提高到4.3 MPa,而溶胀率随着GO量的增加呈先上升后下降的趋势,随着SA含量的增加呈上升趋势。     

丙烯酸纤维素纳米纤丝复合水凝胶颗粒的制备及其性能研究

以丙烯酸纤维素纳米纤丝（ACL-CNF）为聚合轴心，以过硫酸铵（NH₄）₂S₂O₈)为引发剂与丙烯酰胺（AM）、2-丙烯酰胺-2甲基丙磺酸（AMPS）通过反相悬浮聚合制备出复合水凝胶微球P（AAACC）。对P（AAACC）的聚合过程、微观形态、溶胀性、机械强度以及耐温耐盐性进行了研究。结果表明，在盐浓度为10%（质量分数）时平衡溶胀倍率为13.59 g/g,在120℃时平衡溶胀倍率为30.15 g/g,与普通水凝胶相比分别提高了2.63倍和3.15倍；复合水凝胶颗粒在压缩比为85%时恢复性为84.8%,而普通水凝胶已经出现破裂；利用TG-DTG分析可以看出ACL-CNF与单体之间发生了共聚反应，并且热稳定性得到了提升；在高温高盐下老化七天后复合水凝胶颗粒的保水率为92.1%与普通水凝胶相比提高了11%,机械强度在去离子水和盐水中分别提升了2.5倍和2.79倍。     

Effect of bentonite on the structure and mechanical properties of CE/CTBN system

Cyanate ester (CE) resins are among the most important engineering thermosetting polymers and have received attention because of their outstanding physical properties. However, their main drawback is brittleness. Toughening by rubbers is a notable way to improve the toughness but unfortunately it decreases the modulus and thermostability. The CE/carboxyl terminal butadiene-acrylonitrile (CTBN)/bentonite (BT, a kind of clay) composites were prepared by two-step melt blending of CE, CTBN and amino-modified bentonite. The nanostructure and mechanical properties of the CE/CTBN/BT composites were studied by X-ray diffraction (XRD), transmission electron microscopy (TEM) and dynamic mechanical analysis (DMA). Both of the intercalated and exfoliated structures of BT existed in CE/CTBN/BT composites while rubber particles also could be observed in CE/CTBN/BT composites by TEM. When an appropriate amount (about 0.5 wt.%) of BT added into CE/CTBN (100/10 by weight) system, both of the modulus and impact strength increased. A 30% increase of the modulus was obtained without greatly sacrificing the impact strength of the composite when the BT content was 1 wt.%.     

An amphoteric semi-IPN nanocomposite hydrogels based on intercalation of cationic polyacrylamide into bentonite

Amphoteric semi-interpenetrating polymer network nanocomposite (semi-IPN-NC) hydrogels were prepared by graft polymerization of acrylic acid onto starch in cationic polyacrylamide/bentonite nanocomposite aqueous dispersion. Cationic polyacrylamide (CPAM) was used as both an intercalating agent to enlarge interlayer space and a linear polymer chain to fabricate the semi-IPN structure. XRD and TEM confirmed a successful intercalation of CPAM into bentonite. Polymerization temperature was monitored in an attempt to explain the dependence of swelling on the polymerization conditions. The results showed that the hydrogel was of a high swelling and compressive strength even under water content of more than 99%.     

细菌纤维素/聚谷氨酸复合水凝胶的辐照制备及性能

采用Co~(60)-γ射线辐照交联法制备细菌纤维素/聚谷氨酸(BC/PGA)复合水凝胶。采用红外光谱和扫描电子显微镜等对复合水凝胶的结构进行表征,研究了BC引入对复合水凝胶的凝胶分数、热失重、溶胀性能、压缩性能和流变性能的影响,并利用CCK-8法对复合水凝胶进行了细胞毒性评价。研究结果表明,辐照作用下BC纳米纤维和PGA形成双交联复合凝胶网络,BC可有效增加复合水凝胶的压缩强度、储能模量(G')和凝胶分数,降低复合水凝胶的平衡溶胀度。50kGy辐照剂量下,相对于纯PGA水凝胶,复合水凝胶压缩强度增大5倍,G'增大10倍。同时复合水凝胶无细胞毒性,可安全应用于生物医学领域。     

原位插层聚合制备PVC/膨润土复合材料及性能初步研究

以新疆夏子街钠基膨润土为原矿制备的有机膨润土,通过原位插层聚合法制备了PVC/膨润土复合材料.通过对该复合材料的力学性能分析,复合材料的断裂伸长率为42%,比原PVC基体提高51.5%;复合材料的抗冲击强度为15.58 kJ/m2,比原PVC基体提高2.1倍;复合材料的拉伸强度为42.82 MPa,比原PVC基体提高14.6%.由此表明,复合材料的综合性能明显提高.SEM分析表明,PVC/膨润土复合材料具有明显的韧性特征;XRD分析表明,该复合材料是一种剥离型的复合材料.     

Polypropylene-clay composite prepared from Indian bentonite

In the present work, a set of experimental polypropylene (PP) clay composites containing pristine bentonite clay of Indian origin has been prepared and then characterized. The polymer clay composites are processed by solution mixing of polypropylene with bentonite clay using a solvent xylene and high speed electric stirrer at a temperature around 130°C and then by compression molding at 170°C. The mechanical properties of PP-clay composites like tensile strength, hardness and impact resistance have been investigated. Microstructural studies were carried out using scanning electron microscope and transmission electron microscope and the thermal properties were studied using differential scanning calorimeter. Mechanical properties of the prepared composites showed highest reinforcing and toughening effects of the clay filler at a loading of only 5 mass % in PP matrix. Tensile strength was observed to be highest in case of 5 mass % of clay loading and it was more than 14% of that of the neat PP, while toughness increased by more than 80%. Bentonite clay-PP composite (5 mass %) also showed 60% increase in impact energy value. However, no significant change was observed in case of hardness and tensile modulus. Higher percentages of bentonite clay did not further improve the properties with respect to pristine polypropylene. The study of the microstructure of the prepared polymer layered silicate clay composites showed a mixed morphology with multiple stacks of clay layers and tactoids of different thicknesses.     

七孔涤纶纤维对CPE-AO2246微观结构和性能的影响

利用氯化聚乙烯(CPE)、 2, 2-亚甲基-双( 4-甲基-6-叔丁基苯酚) (AO2246)和三维卷曲七孔中空涤纶纤维(SHPF)制备了一系列的SHPF/CPE-AO2246三元复合材料。通过DMA、 SEM、 SW230吸声仪以及HD026NE电子织物强力仪等对复合材料的微观结构和性能进行了测试及分析。结果表明, 加入的SHPF纤维充当了结晶诱导作用, 在复合材料中产生了大量AO2246的包覆式结晶, 从而加速了网络结构的形成; 含有20%质量比(以CPE和AO2246总质量为基)纤维的SHPF/CPE-AO2246复合材料的最大储能模量是未加纤维的3倍多, 由于复合材料的储能模量增幅较大而使其损耗因子下降较快, 但材料损耗模量-温度曲线下的面积(LA)随纤维含量增加而增大, 说明材料的阻尼耗能能力并未下降; SHPF纤维的加入使材料的力学性能获得了较大的改善, 中空网络结构的形成赋予三元复合材料吸声性能。     

Mechanical properties and in vitro behavior of nanofiber-hydrogel composites for tissue engineering applications

Hydrogel-based biomaterial systems have great potential for tissue reconstruction by serving as temporary scaffolds and cell delivery vehicles for tissue engineering (TE). Hydrogels have poor mechanical properties and their rapid degradation limits the development and application of hydrogels in TE. In this study, nanofiber reinforced composite hydrogels were fabricated by incorporating electrospun poly(ε-caprolactone) (PCL)/gelatin 'blend' or 'coaxial' nanofibers into gelatin hydrogels. The morphological, mechanical, swelling and biodegradation properties of the nanocomposite hydrogels were evaluated and the results indicated that the moduli and compressive strengths of the nanofiber reinforced hydrogels were remarkably higher than those of pure gelatin hydrogels. By increasing the amount of incorporated nanofibers into the hydrogel, the Young's modulus of the composite hydrogels increased from 3.29 ± 1.02 kPa to 20.30 ± 1.79 kPa, while the strain at break decreased from 66.0 ± 1.1% to 52.0 ± 3.0%. Compared to composite hydrogels with coaxial nanofibers, those with blend nanofibers showed higher compressive strength and strain at break, but with lower modulus and energy dissipation properties. Biocompatibility evaluations of the nanofiber reinforced hydrogels were carried out using bone marrow mesenchymal stem cells (BM-MSCs) by cell proliferation assay and immunostaining analysis. The nanocomposite hydrogel with 25 mg ml(-1) PCL/gelatin 'blend' nanofibers (PGB25) was found to enhance cell proliferation, indicating that the 'nanocomposite hydrogels' might provide the necessary mechanical support and could be promising cell delivery systems for tissue regeneration.     

Out‐of‐Plane 3D‐Printed Microfibers Improve the Shear Properties of Hydrogel Composites

One challenge in biofabrication is to fabricate a matrix that is soft enough to elicit optimal cell behavior while possessing the strength required to withstand the mechanical load that the matrix is subjected to once implanted in the body. Here, melt electrowriting (MEW) is used to direct‐write poly(ε‐caprolactone) fibers “out‐of‐plane” by design. These out‐of‐plane fibers are specifically intended to stabilize an existing structure and subsequently improve the shear modulus of hydrogel–fiber composites. The stabilizing fibers (diameter = 13.3 ± 0.3 µm) are sinusoidally direct‐written over an existing MEW wall‐like structure (330 µm height). The printed constructs are embedded in different hydrogels (5, 10, and 15 wt% polyacrylamide; 65% poly(2‐hydroxyethyl methacrylate) (pHEMA)) and a frequency sweep test (0.05–500 rad s^?1, 0.01% strain, n = 5) is performed to measure the complex shear modulus. For the rheological measurements, stabilizing fibers are deposited with a radial‐architecture prior to embedding to correspond to the direction of the stabilizing fibers with the loading of the rheometer. Stabilizing fibers increase the complex shear modulus irrespective of the percentage of gel or crosslinking density. The capacity of MEW to produce well‐defined out‐of‐plane fibers and the ability to increase the shear properties of fiber‐reinforced hydrogel composites are highlighted.     

D101大孔树脂颗粒/聚氨酯-环氧树脂弹性体复合材料水声吸声性能

用浇铸法制备了不同含量D101型聚苯乙烯大孔树脂颗粒改性的聚氨酯(PU)/环氧树脂(EP)(D101/PU-EP)弹性体复合材料声学试样, 并研究了该材料的水声吸声性能。基于等效夹杂原理的含涂层空心球复合泡沫材料的模量预测模型, 计算了D101/PU-EP弹性体复合材料的体积模量和剪切模量。根据计算模量和声学模型, 采用传递矩阵法对D101/PU-EP弹性体复合材料的水声性能进行了仿真, 得到了D101大孔树脂颗粒的添加量以及梯度结构对该复合材料水声性能的影响规律。运用水声材料声脉冲管系统测试了复合材料的水声声学性能(管中测试, 水背衬)。研究结果表明: D101大孔树脂颗粒能够有效改善PU-EP弹性体的水声吸声性能, 三层梯度结构的D101/PU-EP弹性体复合材料的吸声性能(D101树脂含量10%, 平均吸声系数0.53, 最大吸声系数0.64)优于同组成的单层复合材料(D101树脂含量10%, 平均吸声系数0.46, 最大吸声系数0.52)。算例验证表明, D101/PU-EP弹性体复合材料的水声性能测试结果与仿真结果基本吻合。     

纤维素纳米纤丝-碳纳米管/聚乙烯醇-硼酸盐复合导电水凝胶

利用纤维素纳米纤丝(Cellulose nanofibers,CNFs)搭载碳纳米管(Carbon nanotubes,CNTs),在水相中将CNF-CNT复合物均匀分散于聚乙烯醇-硼酸盐(PVA-B)基体中,制备具有立体网络结构的CNF-CNT/PVA-B复合导电水凝胶,旨在提高其动态黏弹性、力学强度和导电性能。结果表明:CNF-CNT/PVA-B内部呈现微米级蜂窝状多孔结构,CNFs与CNTs组成的立体网络在显著提高CNF-CNT/PVA-B力学强度和黏弹性的同时还赋予其导电功能。CNTs含量由0增至0.5wt%时,CNF-CNT/PVA-B的抗压强度和弹性模量分别达到24kPa和53kPa,最大和高频稳态剪切模量分别达到7 028Pa和6 945Pa,电导率达到0.8×10-1 S·cm-1。