载Ag改性桑枝韧皮纤维素/聚乙烯醇复合膜的制备及表征

采用流延法制备了载Ag改性桑枝韧皮纤维素/聚乙烯醇（Ag-T-CMC/PVA）复合膜,并利用XRD、SEM、DSC等分析测试方法研究了该复合膜的结构和性能。结果表明:随着Ag-T-CMC含量增加,Ag-T-CMC/PVA复合膜的力学性能、耐水性及抗菌性能均有提高。当Ag-T-CMC与PVA质量比为2%时,力学性能达到最佳,拉伸强度提高了3.4%。SEM分析表明:Ag-T-CMC均匀分散于Ag-T-CMC/PVA复合膜中,表现出良好的相容性;随着Ag-T-CMC含量的增加,断层逐渐变得光滑平面,在Ag-T-CMC与PVA质量比为2%时,断层最光滑。吸水性能测试表明:Ag-T-CMC能明显降低Ag-T-CMC/PVA复合膜的吸水性。抑菌性能测试表明:Ag-T-CMC/PVA复合膜对大肠杆菌和金黄色葡萄球菌有一定的抑菌效果,且随着Ag-T-CMC含量的增大,抑菌圈直径变大,抑菌效果增强。      

PVA-壳聚糖/有机累托石复合膜的结构与性能

目的将聚乙烯醇(PVA)引入壳聚糖(CS)/有机累托石(OREC)复合体系制备插层效果、力学性能、抗紫外老化及阻隔性能良好的插层纳米复合膜。方法利用溶液流延法制备PVA-CS/OREC系列复合膜,以XRD及SEM研究复合膜的插层结构及OREC在基体中的分散性,研究复合膜的力学性能、抗紫外辐射性及水蒸气透过性。结果 OREC及PVA添加量较少时可与CS形成良好的插层结构。当OREC质量分数为2%,PVA质量分数为10%时的复合膜(标记为PVA10-CS/OREC2)插层结构最好,OREC在CS及PVA基体中分散性最好,与OREC质量分数为2%且不含PVA的复合膜(标记为CS/OREC2)相比,拉伸强度提高42.2%,断裂伸长率提高30%,水蒸气透过量降低10.2%,复合膜经紫外辐射后拉伸强度保持率、断裂伸长保持率仍达82.5%及68.2%。结论 PVA10-CS/OREC2膜可作为医用膜和药品、食品等的包装材料。     

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.     

淀粉/PVA复合膜的制备及血液相容性

在无化学处理的条件下制备出淀粉/聚乙烯醇(PVA)复合膜, 进行了力学性能、 溶胀度及红外光谱测试, 并通过溶血试验、 动态凝血试验、 血小板消耗试验对复合膜的血液相容性进行了表征。研究结果表明, 通过共混改性把淀粉引入到PVA中, 改善了力学性能和血液相容性。当PVA与淀粉的质量比为4∶1时, 复合膜的抗拉强度为13.73 MPa, 抗拉应变率为43.07%, 性能最佳。      

载银纳米纤维素/聚乙烯醇复合膜的制备及性能研究

目的制备一种具有良好力学性能和抑菌性能的新型抗菌聚乙烯醇复合膜。方法通过酸水解微晶纤维素制备纳米纤维素,经高碘酸钠氧化获得醛基纳米纤维素,加入银氨溶液原位合成载银纳米纤维素(Ag-DCNC)。以聚乙烯醇(PVA)为成膜基底,加入Ag-DCNC共混流延制备载银纳米纤维素/聚乙烯醇复合膜。结果 Ag-DCNC体积分数为3%时,复合膜的拉伸强度比纯PVA膜提高了8.8%。Ag-DCNC体积分数为5%的复合膜对大肠杆菌和金黄色葡萄球菌均具有较好的抑菌效果。结论载银纳米纤维素/聚乙烯醇复合膜具有较好的力学强度,对2种细菌均有良好的杀菌效果。该材料不但具有良好的性能,而且合成工艺简单,可以作为一种很有前途的抑菌膜用于包装行业。     

茶多酚对壳聚糖/聚乙烯醇复合膜性能的影响

目的以茶多酚为改性剂对壳聚糖/聚乙烯醇复合膜进行共混改性,制备一种综合性能良好的绿色包装材料。方法采用溶液共混法制备不同茶多酚质量分数的壳聚糖/聚乙烯醇复合膜,并对其进行红外光谱分析,以及力学性能、水溶性、气体阻隔性、抗氧化性能的测试。结果茶多酚与壳聚糖/聚乙烯醇基质间发生了分子间相互作用,当茶多酚的质量分数为2%时复合膜的综合性能最好,拉伸强度提高了4.99%,且可保持较高的断裂伸长率,水溶性、水蒸气透过率和氧气透过率分别降低了82.43%,51.40%和72.77%,抗氧化能力增强了58.54%。结论添加适量的茶多酚能够提高壳聚糖/聚乙烯醇复合膜的力学性能和耐水性,并改善其气体阻隔性和抗氧化性能。     

Structure and properties of nylon 6–clay nanocomposites: effect of temperature and reprocessing

Melt-compounding is a technique which has been commonly used for producing polymer–clay nanocomposites with enhanced mechanical, thermal, and physical properties. Twin-screw extruders have been found to effectively exfoliate the clay platelets due to their high shear intensity. However, concerns about polymer and organoclay degradation have been raised in some studies. In this investigation, a composite of nylon 6–Cloisite 30B with fully exfoliated and well-dispersed clay particles was produced using a single-screw extruder and hence with limited polymer degradation. We show that processing temperature plays an important role in enhancing dispersion and that reprocessing at a higher temperature can enhance both dispersion and exfoliation and thus can result in composites with superior properties. We attempt to elucidate how the change in melt viscosity—coupled with the change in processing temperature—affects clay exfoliation and dispersion.     

改性程度和质量比对QMS/PVA复合膜增韧作用的影响

为提高淀粉/聚乙烯醇(PVA)复合膜在纺织上浆等以薄膜为基础的应用领域中的使用效果,通过两步法合成了季铵盐醚化-顺丁烯二酸酯化淀粉(QMS),以QMS/PVA复合膜的断裂强度、断裂伸长率和耐挠曲疲劳性为量化指标,探索了QMS的改性程度(季铵盐醚化和顺丁烯二酸酯化改性程度之和)对QMS/PVA复合膜的增韧规律,考察了PVA与QMS的质量比对这种复合膜韧性的影响。研究发现:QMS/PVA复合膜的断裂强度由改性前的21.6 MPa逐渐降低到QMS改性程度为0.061的14.8 MPa,断裂伸长率和耐挠曲次数分别由26.6%和4 348次逐渐提高到29.5%和5 388次;QMS/PVA复合膜的断裂伸长率和耐挠曲次数由PVA与QMS的质量比为0的3.35%和2 128次逐渐增加到质量比为100%的43.9%和7 889次,而断裂强度由27.1 MPa逐渐下降为12.1 MPa。由此表明PVA与QMS的质量比是QMS/PVA复合膜韧性的主要影响因素,综合各指标PVA与QMS的质量比约为66.7%时为宜。     

纳米纤维素晶体增强补强聚乙烯醇薄膜性能研究现状

目的 综述近几年有关将纳米填料纳米纤维素晶体(CNC)作为增强补强剂,提高聚乙烯醇(PVA)薄膜的物理性能方面的研究,以期为PVA薄膜材料的进一步开发和应用提供参考。方法 通过对相关文献进行收集与整理,阐述PVA/CNC复合薄膜的应用现状,介绍CNC的形貌特性、化学改性及成膜方式对改善PVA/CNC薄膜物理性能的研究现状,综述CNC分散性、交联剂和成膜条件对提高PVA/CNC复合薄膜物理性能的影响。结论 通过增加CNC在PVA基体中的分散性,针对不同用途选择对应的成膜方式,这样可有效改善PVA薄膜的力学性能、阻隔性能和耐水性等,提高PVA薄膜的使用价值。     

Biodegradable amylose films reinforced by graphene oxide and polyvinyl alcohol

Graphene oxide/amylose (GO/amylose) composite films with different amounts of graphene oxide (GO), glycerol and polyvinyl alcohol (PVA) were prepared by a solution casting method. The structure, morphologies, and properties of the films were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, thermal gravimetric analysis, UV–vis spectroscopy and tensile tests. The results indicated good dispersion of the GO nanosheets in the GO/amylose composite films and consequently a significant improvement in their mechanical properties. The addition of GO increased the tensile strength of the GO/amylose films, significantly. When glycerol was used as a plasticizer, the elongation at break of the films increased. When PVA was also added to the composite films, the films were mechanically strong and flexible. The incorporation of GO also decreased the moisture absorbability and UV transmittance of the films. The stability of the GO/amylose films in acidic and alkaline solutions was also studied and the films had excellent stability in both acidic and alkaline aqueous mediums.     

Effects of carbon nanotube functionalization and annealing on crystallization and mechanical properties of melt-spun carbon nanotubes/poly(ethylene terephthalate) fibers

To generate poly(ethylene terephthalate) (PET) fibers with enhanced mechanical properties, we prepared melt-spun PET fibers that incorporated pristine, acid-treated, and functionalized multi-walled carbon nanotubes (MWNTs) with 2-phenylethyl alcohol and 4-phenyl-1-butanol. The incorporation of MWNTs into the melt-spun fibers resulted in increased crystallization of PET but lower breaking stress than that of pure PET fibers, even in those containing well-dispersed functionalized MWNTs. The breaking stress of drawn composite fibers was also lower than that of pure PET fibers prepared at the same draw ratio. However, the annealing of melt-spun fibers enhanced the mechanical properties and crystallization, and the annealing effect was more dominant for composite fibers with functionalized MWNTs. These findings indicate that the presence of well-dispersed MWNTs disturbs the crystallization and orientation of PET molecules in highly stressed fibers, which differs from MWNT-induced crystallization of PET molecules in relaxed fibers.     

纳米纤维素晶体和柠檬酸改性聚乙烯醇薄膜的制备及性能

以球形纳米纤维素晶体(NCC)作增强相、柠檬酸作交联剂对聚乙烯醇(PVA)进行改性,制备了PVA/NCC纳米复合薄膜和柠檬酸交联PVA/NCC纳米复合薄膜。通过热重分析、差热分析、吸水实验和拉伸实验考察了NCC的添加和柠檬酸的交联对薄膜热性能、耐水性和力学性能的影响。结果表明,与纯PVA薄膜相比,改性PVA薄膜的起始分解温度升高、熔融/结晶峰向高温方向移动、吸水率降低;只用NCC或柠檬酸对PVA改性时,所得PVA/NCC纳米复合薄膜、柠檬酸交联PVA薄膜的力学性能均对环境湿度敏感;同时用NCC(m(NCC)/m(PVA)=6/100)和柠檬酸(m(柠檬酸)/m(PVA)=3/100或m(柠檬酸)/m(PVA)=4.5/100)对PVA改性时,所得柠檬酸交联PVA/NCC纳米复合薄膜的力学性能不随环境湿度变化。     

Colorful and transparent poly(vinyl alcohol) composite films filled with layered zinc hydroxide salts,intercalated with anionic orange azo dyes (methyl orange and orange II)

Layered zinc hydroxide salts (zinc LHS) were intercalated with anionic orange azo dyes, namely methyl orange (MO) and orange II (OII), and co-intercalated with hydrated chloride anions. After characterization by X-ray diffraction (XRD), thermal analysis (TGA/DTA), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS), the materials were used as fillers for poly(vinyl alcohol) (PVA). Colorful transparent films were obtained by wet casting, revealing good dispersion of the material into the polymer. In the case of zinc LHS/OII, PVA was intercalated between the zinc LHS layers. Evaluation of the mechanical properties of the PVA composite films revealed that the layered colorful materials were able to increase the mechanical properties of the PVA films only when the films were stored under lower relative humidity. As expected, films with higher water content displayed reduced tensile strength and modulus because of the plasticizing effect of water. As for the films stored at 43% relative humidity, more pronounced improvement of modulus was observed for 1 and 4% zinc LHS/OII, and enhanced tensile strength was achieved for 0.5 and 1% zinc LHS/OII. This effect can be attributed to better dispersion of the layered filler and its better adhesion to the PVA matrix.     

Simultaneous Production and Functionalization of Boron Nitride Nanosheets by Sugar‐Assisted Mechanochemical Exfoliation

Due to their extraordinary properties, boron nitride nanosheets (BNNSs) have great promise for many applications. However, the difficulty of their efficient preparation and their poor dispersibility in liquids are the current factors that limit this. A simple yet efficient sugar‐assisted mechanochemical exfoliation (SAMCE) method is developed here to simultaneously achieve their exfoliation and functionalization. This method has a high actual exfoliation yield of 87.3%, and the resultant BNNSs are covalently grafted with sugar (sucrose) molecules, and are well dispersed in both water and organic liquids. A new mechanical force–induced exfoliation and chemical grafting mechanism is proposed based on experimental and density functional theory investigations. Thanks to the good dispersibility of the nanosheets, flexible and transparent BNNS/poly(vinyl alcohol) (PVA) composite films with multifunctionality is fabricated. Compared to pure PVA films, the composite films have a remarkably improved tensile strength and thermal dissipation capability. Noteworthy, they are flame retardant and can effectively block light from the deep blue to the UV region. This SAMCE production method has proven to be highly efficient, green, low cost, and scalable, and is extended to the exfoliation and functionalization of other two‐dimensional (2D) materials including MoS₂, WS₂, and graphite.     

淀粉/PVA膜在血浆模拟液及唾液模拟液中的体外降解行为及相关体外生物相容性评价

通过熔融浇注法制备出一系列厚度在0.05 mm～0.10 mm的淀粉/聚乙烯醇（PVA）（SP）薄膜。研究了薄膜在血浆（SBF）及唾液模拟液（SSF）中的降解行为,分析了降解过程中力学性能、失重率、溶胀度、热性能以及表面形态的变化。研究结果表明,膜在30天的降解过程中能够维持良好的尺寸稳定性和一定的力学强度。通过细胞毒性、细胞贴壁及溶血试验表征了膜的体外生物相容性。结果表明,SP膜具有良好的细胞和血液相容性。所有测试结果证明,SP薄膜是一种应用于诱导组织再生薄膜的潜在材料。      

埃洛石纳米管/聚乙烯醇-淀粉复合膜的结构与性能

采用溶液流延法制备了埃洛石纳米管(HNTs)/聚乙烯醇(PVA)-淀粉复合膜,并利用SEM、XRD、DMA、TGA等分析测试手段研究了该复合膜的结构与性能。结果表明:随着HNTs含量增加,HNTs/PVA-淀粉复合膜的力学性能、热稳定性、耐水性能和紫外屏蔽性能均有提高。当HNTs与PVA-淀粉质量比为10%时,力学性能达到最佳,拉伸强度提高了22%。扫描电镜分析表明:HNTs能够以纳米尺度均匀分散于HNTs/PVA-淀粉复合膜中,且以单管状分布,与PVA-淀粉基体界面结合较好。动态力学性能分析表明:HNTs的加入对HNTs/PVA-淀粉复合膜的玻璃化转变温度影响不大,复合膜的储能模量升高,力学损耗下降。透光率测试结果表明:HNTs对HNTs/PVA-淀粉复合膜的透明性影响不大,而在紫外光区域(200~400nm),透光率随HNTs量的增加而下降。     

聚乙烯醇/纳米零价铁复合膜的制备及性能

为了克服脱氧剂小袋包装与食品混装带来的工艺不足和安全问题,采用水热法制备了纳米零价铁（nZVI）,并将其与聚乙烯醇（PVA）进行溶液共混,制备了结构及阻氧性能更为优异的聚乙烯醇/纳米零价铁复合膜。利用傅里叶变换红外光谱（FTIR）、X射线衍射（XRD）、热重分析（TG）、差示扫描量热法（DSC）等对膜的结构和性能进行表征。结果表明：复合膜中PVA和nZVI实现了良好复合;加入nZVI后,复合膜的玻璃化温度（Tg）升高、热稳定性降低;随着nZVI含量的增加,复合膜的力学性能先增强后减弱,在nZVI质量分数为2%时,复合膜的抗拉强度和断后伸长率达到最大;复合膜的氧气透过系数随着nZVI含量的增加呈现先减小后增大的趋势,在nVZI质量分数为3%时,复合膜的氧气透过系数最小。在复合膜中,nZVI和PVA的羟基之间能形成一种强的相互作用,改善了复合材料的结构和性能,但nZVI及其表面部分氧化的变价铁催化加速了PVA的热降解。     

Morphological and mechanical properties of bile salt modified multi-walled carbon nanotube/poly(vinyl alcohol) nanocomposites

Non-covalently functionalized carbon nanotubes are more attractive for multifunction composites because they preserve nearly all the nanotubes’ intrinsic properties and enhance the electroconductivity of polymer composites. However, It is seldom reported that they make dramatic improvement in mechanical properties. In this paper we have successfully prepared a poly(vinyl alcohol) (PVA) nanocomposite with a non-covalently functionalized carbon nanotube (DOC-MWNTs) using a simple method, which achieve a significant enhancement in mechanical properties. The tensile modulus and tensile yield strength of the PVA composite film containing 5 wt% DOC-MWNTs increased by 140% and 65%, respectively, comparing to the pure PVA film. FT-IR, TEM, SEM, and DSC were used to investigate the MWNTs and PVA/MWNTs nanocomposites. The results show that the separately dispersed DOC-MWNTs filler throughout the PVA matrix and the strong adhesion between the DOC-MWNTs filler and the PVA matrix are responsible for the significant reinforcement of the mechanical properties of the composite prepared.     

防霉聚乙烯醇改性薄膜的制备及性能

目的研究以聚乙烯醇(PVA)为基材,通过柠檬酸(CA)改性制备出具有防霉效果的改性PVA薄膜。方法通过调整加热时间、加热温度及搅拌转速等参数,发现制备改性PVA母液规律性,并经溶液流延法加工制备出酸性防霉PVA改性薄膜,通过光学、力学性能研究其物理性能,通过半干鱼保鲜实验研究其防霉效果。结果得到的酸性防霉PVA改性薄膜均具有良好的光学及力学性能,在半干鱼实验中相对于对照组,实验组均体现了良好的防霉效果,其中含有质量分数为2%的柠檬酸的改性PVA薄膜防霉效果最佳。结论 PVA改性薄膜在其制备过程中具有一定规律性,得到的酸性PVA改性薄膜具有良好的防霉效果。     

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。