静电纺纤维素纳米晶体/壳聚糖-聚乙烯醇复合纳米纤维的制备与表征

通过探索纤维素纳米晶体（CNC）添加量对壳聚糖-聚乙烯醇（CS-PVA）基体性能的影响,为静电纺CNC/CS-PVA复合纳米纤维的制备提供理论支撑。以CNC、CS和PVA为原料,采用静电纺丝法成功制备不同CNC含量（质量分数）的静电纺CNC/CS-PVA复合纳米纤维,并通过SEM、TGA和FTIR等分析手段对CNC/CS-PVA复合纳米纤维的微观结构和性能进行了表征。结果表明：添加CNC后静电纺CNC/CS-PVA复合纳米纤维直径变大,表面变粗糙,力学性能和热学性能提高;随着CNC含量的增加,静电纺CNC/CS-PVA纤维的杨氏模量（E）和抗拉强度（σ）先增强后减弱,而外延起始温度继续上升。当CNC含量为3wt%时,静电纺CNC/CS-PVA复合纳米纤维力学性能最好,相比于CS-PVA复合纳米纤维,E和σ分别提高了43.9%和24.8%;当CNC含量为20wt%时,静电纺CNC/CS-PVA复合纳米纤维直径分布不均匀,可以观察到单根纤维表面存在少量的球状结构物质,同时外延起始温度达到328.83℃;FTIR分析得出,CNC与CS和PVA之间只存在分子间的相互作用而没有发生化学反应;随着溶液的酸性减弱,碱性增强,不同CNC含量的静电纺CNC/CS-PVA复合纳米纤维稳定性逐渐提高,而CNC含量对其稳定性影响不大。     

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。     

静电纺纳米粘土/亚麻复合纳米纤维的制备及表征

利用静电纺丝技术制备了纳米粘土/亚麻落麻复合纳米纤维,其中亚麻落麻纤维溶解在分散有纳米粘土的4-甲基吗啉-N-氧化物(NMMO)/水的混合体系中。探究了纳米粘土和亚麻落麻的浓度、纺丝条件对纺丝工艺的影响。采用光学显微镜、SEM、TEM、FTIR、XRD和TGA测试了复合纳米纤维的微观形貌、结构及热学行为。结果表明:亚麻纤维浓度为1%时,可纺制成丝,且纳米粘土的加入可有效地改善纤维的细度和均匀性;TEM测试结果表明:纳米粘土已成功附着在纳米纤维上,但分散性有待进一步提高;FTIR和XRD结果表明:纳米粘土成功附着在亚麻纤维中,且存在于亚麻纳米纤维和粘土/亚麻复合纳米纤维中的纤维素为纤维素II型结晶;TGA分析表明:纳米粘土的引入可显著提高亚麻纤维的热稳定性。     

静电纺壳聚糖/聚乙烯醇纳米纤维膜的制备及表征

通过静电纺丝技术首次将溶解在1%(体积分数)超低浓度乙酸溶液中的3%(wt,质量分数,下同)壳聚糖(CS)与溶解在去离子水中的11%聚乙烯醇(PVA)溶液进行混合,在20～22kV高压静电场下制备出直径在70～300nm之间、CS含量高达60%,具有均匀结构的CS/PVA纳米纤维膜。通过旋转流变仪、扫描电镜、X射线衍射仪、红外光谱、热重分析和万能试验机等手段对其混合溶液进行表征。结果表明:CS/PVA纳米纤维膜的形貌与CS和PVA的混合比例有关,当CS含量低于60%时,纤维形貌良好,当CS含量高于60%时,纤维中存在有液滴以及纺锤体。另外,CS与PVA之间存在强有力的氢键作用并具有很好的相容性,PVA可以降低壳聚糖的结晶性利于静电纺过程的进行;并且该CS/PVA纳米纤维膜具有较好的热稳定性和弹性,随着PVA比例的增加其最大拉伸强度可达到9.98MPa。     

静电纺缓释抗菌纳米纤维的制备及抗菌性能研究

目的 解决天然抗菌剂精油封装到聚合物中的受控释放问题。方法 选用聚乙烯醇和纳米纤维素为主体材料,采用百里香精油为活性物质,通过静电纺丝技术制备纳米纤维。结果 采用质量比为3∶4的纳米纤维素水凝胶(质量分数1%)和聚乙烯醇水溶液(质量分数6%),并加入质量分数为4%~10%的百里香精油制备纺丝液,在纺丝电压为16 kV、纺丝速率为0.8 mL/h、纺丝距离为11 cm、针头直径为0.7 mm的条件下制备了直径为100~150 nm的纳米纤维,并成功将百里香精油包埋在纳米纤维中。结论 所制备的纳米纤维可以达到百里香精油缓慢释放的效果,对大肠杆菌、金黄葡萄球菌、黑曲霉和橘青霉均有抑制作用。     

纳米纤维素增强聚乙烯醇/水性聚氨酯静电纺膜的研究

采用TEMPO(2,2,6,6-四甲基哌啶氧化物自由基)氧化纤维素纳米纤维(TOCNs)作为聚乙烯醇(PVA)/水性聚氨酯(WPU)静电纺膜的增强剂。研究中使用拉伸实验研究TOCNs的增强作用,此外还使用扫描电子显微镜、红外光谱仪、热重分析仪及差示扫描量热仪等对静电纺膜进行结构性能表征。扫描电镜观察发现当纳米纤维素加入量为5%(质量分数)时,其在聚合物基质中分散良好,所得静电纺纳米纤维保持了良好的形态。此外,加入5%(质量分数)的纳米纤维素能够将材料的抗张强度提高44%,且纳米纤维素的加入对材料的热稳定性也有一定的改善,纳米纤维素起到一种纳米填料的效果。鉴于PVA、WPU、TOCNs均为亲水性,无毒且具有生物相容性的物质,所得静电纺膜在组织支架及伤口护理材料等方面具有潜在应用。     

静电纺聚乙烯醇/纳米二氧化钛超细纤维的水稳定性

静电纺聚乙烯醇/纳米二氧化钛(PVA/TiO2)超细纤维的水稳定性较差,用于液体过滤时需进行预处理。文中对PVA/TiO2超细纤维分别采用热处理和甲醇处理进行交联,以提高其在水中的稳定性。通过对处理后的纤维进行差示扫描量热(DSC)测试,发现纤维最佳处理条件为140℃热处理10min,而甲醇处理最佳处理时间为8h。通过纤维形貌观察,发现热处理及甲醇处理后的纤维浸水24h后纤维仍然存在,只是发生了凝集和肿胀,且热处理比甲醇处理效果更好。     

静电纺丝法制备细菌纤维素纳米纤维

利用静电纺丝技术,以实验室自制的细菌纤维素(BC)为原材料,选择室温离子液体1-烯丙基-3-甲基咪唑氯化物(AMIMCL)为溶解体系,制备出细菌纤维素纳米纤维。实验中通过添加助溶剂N,N-二甲基甲酰胺(DMF)降低纺丝液的粘度,并设计了转动的滚筒收集器,考察了BC质量分数、DMF的添加量、电压、固化距离等因素对静电纺丝的影响,利用光学显微镜、扫描电子显微镜(SEM)以及X射线衍射(XRD)对纺丝进行分析。研究表明,在BC质量分数为5%、AMIMCL与DMF的质量比为1∶2.5、电压为23kV、固化距离为12cm、环境湿度为60%～80%的条件下能够制备出连续的、直径为500～800nm的细菌纤维素纳米纤维;BC的晶体结构为纤维素Ⅰ型,而BC经离子液体溶解并静电纺丝后其结构转化为纤维素Ⅱ型。     

空气过滤用静电纺聚苯乙烯/碳纳米管复合纤维膜的制备

采用静电纺丝技术制备聚苯乙烯(PS)超细纤维、PS/多壁碳纳米管(MWCNTs)复合纳米纤维,并对其纤维形态结构、直径大小及空气过滤性能进行了表征。通过PS纺丝溶液浓度变化调控制备纯PS纤维多孔膜,并通过在PS纺丝液中添加不同含量MWCNTs调控纤维形态结构。SEM分析结果表明PS/MWCNTs复合纤维表面形成"褶皱"型和"山峰"型纳米级突起,复合纤维表面的粗糙度明显增加,且纤维直径明显减小。空气过滤性能测试结果发现这种多级结构使复合膜的过滤效率相比光滑的纯PS纳米纤维膜大幅提高,过滤性能得到明显改善。在85L/min气流速度下,PS/MWCNTs复合膜过滤效率高达99.95%,空气阻力为374.6Pa。选择尺寸较粗的微米级PS纤维(~2μm)和相对较细的纳米级PS/MWCNTs复合纤维(~800nm)进行混纺,调节复合膜堆积密度可使得混纺膜空气阻力降低到235.4Pa,仍能保持高的过滤效率(99.68%)。     

纳米纤维素-碳纳米管/热塑性聚氨酯复合薄膜的制备及应变响应性能

采用2,2,6,6?四甲基哌啶?1?氧自由基(TEMPO)氧化法制备了不同羧基含量的纳米纤维素(CNF),并将其用作碳纳米管(CNTs)的分散剂,通过超声、离心处理制备出稳定均一的CNF?CNTs分散液,然后通过朗伯?比尔定律测定CNF?CNTs分散液中CNTs的浓度,研究了不同CNF羧基含量对CNTs的分散效果。此外,利用静电纺丝法制备出柔性、多孔的热塑性聚氨酯(TPU)薄膜作为基体,以CNF?CNTs分散液作为导电填料,通过真空抽滤法将CNF?CNTs负载于TPU多孔膜上,制备出CNF?CNTs/TPU复合薄膜,并探究了不同CNF羧基含量对CNF?CNTs/TPU复合薄膜应变响应性能的影响规律。结果表明,羧基含量对CNF的分散性能具有重要影响。随着CNF羧基含量的提高,CNF对CNTs分散效果越好,CNF?CNTs/TPU复合薄膜具有更大的应变响应范围。当CNF羧基含量为1.698 mmol/g时,CNF?CNTs/TPU复合薄膜的应变响应范围高达507%,灵敏度系数为335,表现出优异的应变响应性能。      

导电聚偏氟乙烯/碳纳米管复合膜的制备与性能研究

通过浸没沉淀相转化法制备了聚偏氟乙烯/多壁碳纳米管导电复合膜,研究了复合膜的亲水性、导电性、通量、表面形态以及机械性能。研究表明,碳纳米管的加入可以使复合膜中的β相增多,α相减少。扫描电镜表明通过超声分散处理可以使碳纳米管均匀地分散在聚偏氟乙烯基质中,同时由于碳纳米管的加入,复合膜的亲水性、通量、导电性、介电常数以及机械性能都得到了改善。     

细菌纤维素@聚吡咯-单壁碳纳米管导电膜的制备与表征

为了获得柔性高电导率导电材料,以细菌纤维素（BC）、吡咯（Py）和单壁碳纳米管（SWCNTs）为原料,在不添加任何黏合剂的情况下,通过简单的原位氧化聚合和真空过滤法制备了BC@聚Py-SWCNTs（BC@PPy-SWCNTs）新型导电膜。通过SEM、FTIR对BC@PPy-SWCNTs复合膜的表面形貌、化学成分进行表征。研究了BC@PPy-SWCNTs膜的电化学性能。结果表明,在SWCNTs添加量为4.7%（质量比）时,BC@PPy-SWCNTs复合膜的电导率可达到6.42 S·cm-1,相比BC@PPy有了很大提高,在充电电流为5 mA·cm-2时,其面积电容可达到0.53 F·cm-2,其能量密度达0.036 mWh·cm-2,功率密度达到1.75 mW·cm-2。BC@PPy-SWCNTs膜拓宽了电极材料的种类,有望应用于超级电容器、电池及传感器等领域。      

Preparation and properties of microfibrillated cellulose polyvinyl alcohol composite materials

This work reports the preparation of MFC–PVA composite films, and the thermal and mechanical properties of these films. Microfibrillated cellulose (MFC), which was separated from kraft pulp by a mechanical process, was used as the reinforcement in polyvinyl alcohol (PVA) matrix. This MFC reinforcement has an interconnected web-like structure with fibrils having a diameter in the range of 10–100 nm, as observed by TEM. MFC–PVA composite films were created by casting from a water suspension to produce a homogeneous dispersion of MFC in the polymer matrix. DMA shows an increase of the storage modulus in the glassy state with increasing MFC content, but a more significant increase in modulus is detectable above the glass transition temperature. There is a steady increase in both the modulus and strength of the composite films until a plateau is reached at 10 wt% MFC. The thermal stability of the PVA composite films is slightly increased with the addition of MFC.

As a result of this research, it has been shown that MFC is an excellent reinforcement comparable to cellulose nanowhiskers. Furthermore, by combining MFC with PVA in addition to good mechanical properties, this composite has good chemical resistance and biodegradability. The water soluble characteristics of PVA combined with a water dispersion of MFC are also easily processable.     

Preparation and characterization of composite fibers from organic-soluble chitosan and poly-vinylpyrrolidone by electrospinning

Ultrafine composite fibers were fabricated by electrospinning of chloroform solutions of organic-soluble chitosan (O-CS) and poly-vinylpyrrolidone (PVP). The composite fibers were subjected to detailed analysis by Fourier transformed infrared spectroscopy (FT-IR) and scanning electron microscopy (SEM). The FT-IR showed that the composite fibers contained the two polymers. The SEM image results confirmed that the morphology and diameter of the fibers were remarkably affected by the process and the parameters of the electrospinning. The governing parameters included the applied voltage, the viscosity of the electrospun solution and tip-to-collector distance, and were further investigated.     

多壁碳纳米管增强炭黑/聚丙烯导电复合材料导电行为

为了充分利用不同导电粒子的导电作用,在炭黑(CB)/聚丙烯(PP)导电复合体系中引入了多壁碳纳米管(CNTs)。研究发现：引入的CNTs分散在CB粒子间起到“桥梁”作用,使体系的导电性能得到明显改善,并且CB∶CNTs为19∶1时其协同导电效果最好,该复合体系出现逾渗现象,对应的导电填料体积分数明显降低。在导电填料总体积分数为4.76%时,少量CNTs的引入就可使复合体系的体积电阻率从109Ω·cm下降到105Ω·cm;同时少量的CNTs能明显抑制炭黑/聚丙烯导电复合材料的正温度效应(PTC),使PTC强度从6.10降低到1.48,PTC转变峰温度从166℃升高到174℃。少量的 CNTs可以使PP的结晶温度提高12℃,对PP结晶的成核作用比CB更加明显。复合体系力学性能随导电填料体积分数增加而明显降低,但因为体积电阻率一定时CB-CNTs/PP体系所需导电填料体积分数较CB/PP体系明显降低,因此少量CNTs的引入能够使复合体系的力学性能得到更大程度的保持。     

用定向冷冻干燥法制备具有一维取向微孔结构的炭黑/聚乙烯醇导电复合材料

通过定向冷冻干燥法,制得了具有一维取向微孔结构的导电炭黑(CB)/聚乙烯醇(PVA)复合材料。对CB/PVA复合材料的导电性测试结果表明,该复合材料的导电逾渗行为并不完全符合经典的逾渗理论。由于CB/PVA复合材料特殊的取向微孔结构和炭黑于PVA基体的非均匀分布,使得其电阻率临界指数t值高于经典的逾渗理论的取值范围。     

Preparation and characterization of polystyrene-multiwalled carbon nanotube composite fibers by electrospinning

Electrospinning is a simple technique to prepare polymer fibers in nanometer diameters using very high electrostatic fields. These nanofibers are useful in many applications since the surface area to volume ratio in these fibers is very high. Here we have prepared nanofibers of composites of Polystyrene (PS) with different concentrations (0.05% to 2% w/w) of multi-walled carbon nanotubes (MWCNT) by electrospinning. The fibers are characterized by SEM, TEM, Raman spectra, and TGA. The room temperature electrical conductivity of single fibers of these composites are measured and found to show dramatic improvement in the conductivity due to the addition of MWCNT to the polymer matrix compared to the pure PS.     

Highly strong and conductive carbon nanotube/cellulose composite paper

Carbon nanotube (CNT)/cellulose composite materials were fabricated in a paper making process optimized for a CNT network to form on the cellulose fibers. The measured electric conductivity was from 0.05 to 671 S/m for 0.5–16.7 wt.% CNT content, higher than that for other polymer composites. The real permittivities were the highest in the microwave region. The unique CNT network structure is thought to be the reason for these high conductivity and permittivity values. Compared to other carbon materials, our carbon CNT/cellulose composite material had improved parameters without decreased mechanical strength. The near-field electromagnetic shielding effectiveness (EMI SE) measured by a microstrip line method depended on the sheet conductivity and qualitatively matched the results of electromagnetic field simulations using a finite-difference time-domain simulator. A high near-field EMI SE of 50-dB was achieved in the 5–10 GHz frequency region with 4.8 wt.% composite paper. The far-field EMI SE was measured by a free space method. Fairly good agreement was obtained between the measured and calculated results. Approximately 10 wt.% CNT is required to achieve composite paper with 20-dB far-field EMI SE.     

纳米纤维素-聚吡咯/天然橡胶柔性导电弹性体的制备与性能

以纤维素纳米纤丝（Cellulose nanofibrils,CNFs）为生物模板,将聚吡咯（Polypyrrole,PPy）原位聚合在CNFs表面,再将CNF-PPy复合物均匀分散到天然橡胶（Natural rubber,NR）弹性基体中,制备了具有高柔韧性的纳米纤维素-聚吡咯/天然橡胶（CNF-PPy/NR）导电弹性体。结果表明：CNFs可协助PPy在NR基体中形成三维导电网络结构,并提高弹性体的力学性能和导电性能,有效降低其逾渗阈值。当添加质量比为5%（以橡胶质量为基准,下同）的CNF和20%的PPy时,CNF-PPy/NR的拉伸强度可达（8.97±0.92）MPa,分别约为PPy/NR及纯NR的1.56倍和9.54倍,电导率可达（0.134±0.063）S/m;在0.3 A/g的电流密度下,比电容可达96 F/g,并在1.0 A/g电流密度下循环充放电1 200次后,比电容仍可保持其初始值的72%。此导电弹性体具有良好的力学强度和电学性能,有望应用于柔性有机电子器件领域。