Preparation and Properties of Biodegradable Spent Tea Leaf Powder/Poly(Propylene Carbonate) Composite Films

The aim of the present work is to develop novel bio-based lightweight material with improved tensile and thermal properties. Spent tea leaf powder (STLP) was used as a filler to improve the tensile and thermal properties of polypropylene carbonate (PPC). Tea is an important material used in hotels and households, and spent tea leaf is a resulting solid waste. Composite films with STLP were obtained by the solution casting method. These films were characterized by optical and scanning electron microscopy, Fourier transform-infrared spectroscopy, thermogravimetric analysis, and tensile testing to examine the effect of filler content on the properties of the composites. The results showed that composite films have increased tensile strength due to enhanced interfacial adhesion between the filler and the matrix. In addition, the composite films also exhibited higher thermal degradation temperatures than pure polypropylene carbonate. The morphology results indicate that there is a good interface interaction between STLP and PPC. Results of the study reveal STLP to be a promising green filler for polymer plastics.     

纤维素/壳聚糖共混透明膜的制备及阻隔抗菌性能研究

利用壳聚糖溶液包覆法制备了具有高气体阻隔性及抗菌性的透明纤维素膜,其扫描电镜照片证明壳聚糖厚度在1.31 ～4.07 μm之间.通过红外光谱、紫外光谱、热重分析仪、电子万能试验机和接触角测试仪对纤维素/壳聚糖共混膜的结构和性能进行了详细研究,结果表明由于壳聚糖和纤维素之间具有一定的氢键相互作用,使得纤维素/壳聚糖共混膜较好地保持了纯纤维素膜的机械强度,其拉伸强度都大于110 MPa.此外,壳聚糖的包覆对纤维素膜的透明性没有影响,它在600 ～ 800 nm处的透光率仍维持在80％左右,并且提高了纤维素膜的疏水性,其水接触角从纤维素膜的70°提高到了100°.利用气体渗透仪进一步研究了纤维素/壳聚糖共混膜的氧气阻隔性,结果表明该膜具有很好的氧气阻隔性,其氧气渗透系数甚至低于市场上理想的氧气阻隔材料乙烯-乙烯醇共聚物(EVA).金黄色葡萄球菌抗菌测试表明,通过壳聚糖包覆法改性纤维素能够明显提高纤维素膜的抗菌性.     

纤维素/全硫化弹性纳米粒子复合膜的制备与性能

利用碱脲溶剂低温溶解纤维素,在该体系中掺杂一定比例的全硫化羧基丁苯弹性纳米粒子,制备了纤维素/全硫化弹性纳米粒子复合膜.通过透射电镜、扫描电镜、WAXD、固体核磁共振、热分析和力学性能测试等对该复合膜的结构和性能进行了表征.结果表明,全硫化羧基丁苯弹性纳米粒子(CSB ENP)均匀的分散在具有微纳孔洞结构的纤维素基体中.CSB ENP的引入对纤维素再生过程中的结晶性影响不大.纤维素/全硫化弹性纳米粒子复合膜具有良好的透光性,并且热稳定性也有所提高.加入少量的CSB ENP可以增韧纤维素膜,且能保持良好的力学性能.当CSB ENP的含量为5 wt%时复合膜的断裂拉伸强度和断裂伸长率同时得到了提高.     

纳米纤维素晶须的表面醋酸酯化改性及复合材料的力学性能

采用硫酸水解法制备纳米纤维素晶须, 再以冰醋酸为分散介质, 浓硫酸为催化剂, 醋酸酐为酯化剂对纳米纤维素晶须进行不同程度醋酸酯化改性, 得到醋酸酯化的纳米纤维素. 采用红外光谱(FTIR)、 X射线光衍射(XRD)、 透射电子显微镜(TEM)和X射线光电子能谱(XPS)等手段对改性产物进行分析和表征. 结果表明, 改性纳米纤维素晶须中醋酸酯基的平均取代度过小或过大时均不适宜用作复合材料的增强相. 当改性纳米纤维素晶须中醋酸酯基的平均取代度为0.05时, 醋酸酯化反应只发生在纳米纤维素晶须的表面. 此时, 晶须能在丙酮中稳定悬浮, 表现出流动双折射现象, 并保持了改性前纳米纤维素晶须的棒状形态和高结晶度. 将这种改性后的纳米纤维素晶须作为增强相与醋酸纤维素通过溶液浇铸法制成纳米复合膜, 结果显示, 与空白醋酸纤维素膜相比, 添加改性纳米纤维素晶须后, 纳米复合膜的拉伸强度、 杨氏模量和断裂伸长率都得到了提高. 在玻璃化转变区间纳米复合膜储能模量的降低幅度小于空白膜.     

Preparation,Characterization and Properties of Cellulose Acetate-Grafted-Poly(glycidyl methacrylate) Copolymers

The cellulose acetate-grafted-poly(glycidyl methacrylate) copolymers were synthesized successfully by free radical polymerization. The resulting copolymer was characterized by proton nuclear magnetic resonance (¹H-NMR), solid-state ¹³C-NMR, Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC). The crystallization behavior, thermal properties, specific particle surface area, moisture sorption behavior of the modified cellulose acetate were investigated by wide angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Brunauer-Emmett-Teller (BET) method and Dynamic Vapor Sorption (DVS) instrument. It was found that the poly(glycidyl methacrylate) (PGMA) grafting was effective in improving the water adsorption of cellulose acetate (CA) changing the specific surface area, and reducing the T_g of copolymers.     

聚乙烯醇/半纤维素/纤维素纳米晶复合膜的制备和性能

通过碱解醇沉法从玉米芯中提取半纤维素,进而采用溶液共混流延法制备出不同比例的聚乙烯醇(PVA)/半纤维素共混膜,在此基础上加入通过硫酸水解脱脂棉制备的纤维素纳米晶(NCC),制备了NCC增强的复合膜.DSC、TGA、FTIR、SEM和薄膜拉伸等研究表明,复合膜的各组分间形成了氢键作用,相容性良好.在PVA/半纤维素共混膜中,半纤维素的加入大幅度提高了复合膜的断裂伸长率:当PVA与半纤维素质量比为3∶1时,复合膜的断裂伸长率高达380%,比纯PVA的140%增加了1.7倍,而拉伸强度仍能保持在较高的水平;纤维素纳米晶的加入,还可改善复合膜的韧性;半纤维素对PVA组分的结晶性能产生了影响,而刚性结构的NCC则对PVA的结晶起抑制作用.此外半纤维素和NCC的引入也提高了复合膜的热性能,使第二阶段分解速率峰的温度提高了约50℃.     

Extraction and Characterization of Novel Lignocellulosic Fibers From Thespesia Lampas Plant

In this work, the lignocellulosic fibers from the plant Thespesia lampas were extracted and investigated in detail. The prime objective of this work was to study the effect of alkali treatment on the chemical composition, tensile properties, morphological and structural changes, and thermal degradation of Thespesia lampas fibers. Chemical analysis, FT-IR, and ¹³C CP-MAS NMR spectroscopic studies indicated lowering of amorphous hemicellulose content on alkali treatment. Wide-angle X-ray diffraction studies indicated increase in crystallinity of the fibers on alkali treatment. The tensile strength and modulus of the fibers and thermal stability increased on alkali treatment. Scanning electron micrographs revealed roughening of the surface of the fibers due to the removal of the hemicellulose layer on alkali treatment. Tensile properties of Thespesia fibers were compared to those of other important natural fibers, and it was indicated as an alternative suitable source for composite construction.     

蔗渣纳米纤维素的制备与表征

以甘蔗渣为原料,通过无废酸的一步法、两步法和三步法制备了蔗渣纳米纤维素(BNC),并与酸解法进行对比.采用傅里叶红外光谱(FTIR)、扫描电子显微镜(SEM)、X射线衍射(XRD)和热重分析(TGA)等手段表征了纳米纤维素的光谱性质、形貌结构、结晶性能及热稳定性能.结果表明,4种方法处理后纤维形貌尺寸均可达到纳米级别且在一定浓度的水溶液中均可形成类果冻状的胶体,其中酸解法和三步法所制备的纳米纤维素长径比较小,形貌多为短棒状,在水溶液中分散稳定性较好,可稳定悬浮超过30 d;一步法和两步法所制备的纳米纤维素长径比较大,为类纤维状结构,分散稳定性相对较差,但也可稳定悬浮至少5 d;一步法所制备的纳米纤维素晶型为纤维素Ⅰ型和纤维素Ⅱ型的混合物,两步法、三步法和酸解法处理后的纤维晶型没有改变,仍然保持纤维素Ⅰ型.与酸解法相比,无废酸法所制备的纳米纤维素热稳定性更优,无废酸法工艺简单,反应条件温和,而酸解法反应步骤繁复,会产生大量废酸增加后续处理成本.     

A Study on the Preparation,Structure, and Properties of Microcrystalline Cellulose

Abstract

The preparation, structure, and properties of microcrystalline cellulose (MCC) from rice straw were investigated by IR, x-ray, viscometry, polarizing microscope, SEM, etc. The results are as follows:

1. The leveling-off degree of polymerization (LODP) obtained from rice straw is about 80–150. The dimensions of MCC granules are 20–30 μm length, 0.5–0.8 μm thick, and the crystallinity is about 80%.

2. The aqueous suspension of a certain concentration of MCC can form a gel under the effect of shear force. The viscosity of MCC gel increased with an increasing content of MCC in water. A sharper increase of viscosity occurred in the 3–6% range.

3. The addition of one or two valence salts into the MCC gel increased the viscosity.

4. The viscosity of MCC gel has its maximum value at pH 8.

5. The MCC gel as an emulsifying agent can form a stable emulsion in the oil/water system when the ratio of oil/water is below 6/4.     

Physico-chemical,Tensile, and Thermal Characterization of Napier Grass (Native African) Fiber Strands

This article presents the extraction and effect of alkali treatment on the physical, chemical, tensile, and thermal characteristics of fiber strands obtained from Napier grass, a renewable biomass. In order to improve these properties, the Napier grass fiber strands were treated with sodium hydroxide. The alkali treatment was carried out using NaOH solution at three different concentrations (5, 10, and 15%) for 2 h. Characterization of untreated and alkali-treated Napier grass fiber strands was carried out by studying the chemical composition, surface morphology, functional group variation, crystallinity, and tensile and thermal behavior. It was found that untreated fiber strands have lower cellulose content, crystallinity, tensile properties, and thermal stability than alkali-treated fiber strands. Napier grass fiber strands treated with 10% NaOH showed optimum tensile strength, modulus, and percentage elongation with an improvement of 51.9, 47.3, and 12.1% respectively. Based on the properties determined for alkali-treated Napier grass fiber strands, we expect that these fibers will be suitable for use as a reinforcement in natural fiber composites.     

新创实验:废旧棉中纤维素的提取改性及水凝胶的制备

水凝胶作为一种有着广阔应用前景的高分子材料,是当今科学研究的热门领域,其制备方法相对简单,还将有机合成化学、高分子化学、无机配位化学和分析化学结合于一体,显示出进一步改编为教学实验的潜力。水凝胶自身环境友好的特点还十分贴合绿色化学的主题,便于在教学实验设计中引入相关内容。虽然绿色化学教育在当今的化学专业人才培养中的重要性与日俱增,但在实际推广中也遇到了一些困难,比如定性描述较多,概念模糊不清,很难激发学生兴趣;定量计算过于简单,只关注反应前后质量变化等。针对绿色化学的教学困境,我们在将水凝胶这一科研成果转化为教学实验外,还引入了最新的绿色化学半定量评价方法,引导学生在实验准备阶段运用新颖的半定量评价方法找寻绿色程度较高的水凝胶合成路线。最终以废旧棉为原料提取改性得到羧甲基纤维素钠,再以滴定法测定其取代度,然后采取金属离子交联方法制备出可视化水凝胶产品,并对其吸附性能进行了初步测试。     

纤维素丙酸酯-g-二乙二醇正十六烷基醚固-固相变材料的制备及性能

以二月桂酸二丁基锡(DBTDL)为催化剂,微晶纤维素为骨架材料,二乙二醇正十六烷基醚(E2C16)为相变材料,采用化学接枝法制备了系列纤维素丙酸酯-g-二乙二醇正十六烷基醚(CP-g-E2C16)固-固相变材料.利用傅里叶变换红外光谱(FTIR)、核磁共振氢谱(1H NMR)、差示扫描量热仪(DSC)、热重分析(TG)和X射线衍射(XRD)对CP-g-E2C16相变材料的结构和热性能进行了表征.结果表明,得到了E2C16的取代度和接枝含量分别为0.12~0.37和17.1%~33.4%的CP-g-E2C16固-固相变材料.CP-g-E2C16接枝共聚物的相变温度和相变焓分别为25~34℃和40~62 J/g,符合人的体感舒适温度范围.CP-g-E2C16固-固相变材料的耐热温度高于237℃,与E2C16相比提高21~40℃,有望应用于熔融纺丝法制备纤维素基储热调温纤维领域.     

Tensile and Thermal Properties of Poly(lactic acid)/Eggshell Powder Composite Films

Biodegradable composite films of poly(lactic acid) (PLA)/eggshell powder (ESP) were prepared by the composite film casting method using chloroform as the solvent. ESP was loaded in PLA in 1 to 5 wt.%. The films were subjected to tensile, FT-IR spectral, thermogravimetric, X-ray, and microscopic analyses. The tensile strength and modulus of the composite films were found to be higher than those of PLA and increased with ESP content up to 4 wt.% and then decreased. A reverse trend was observed in the case of percentage elongation at break. The X-ray diffractograms of the composite films indicated an increase in crystallinity with ESP content. The optical micrographs indicated uniform distribution of ESP particles in the composite films. However, the fractographs indicated agglomeration of ESP particles at 5 wt.% loading. The FT-IR spectra revealed no specific interactions between PLA and ESP. The thermal stability of the composite films increased with ESP content.     

稀土-天然皮革可穿戴X射线防护材料的合成及性能

X-rays are widely used in many fields, including medical imaging, chemical structure analysis, and nondestructive examinations. However, long-term X-ray exposure is harmful to human health. Hence, radiation protection materials, especially wearable materials with outstanding performances, are in need of development. Lead (Pb) plates are commonly used as traditional radiation protection materials but have the disadvantages of heavy mass, toxicity, and poor wearability. Cement and alloy also are used to shield the X-ray, whereas application is limited by its heavy mass. In recent years, the wearable polymer based radiation protection was developed but has the defect which is low interfacial compatibility, resulting in poor shielding properties of the material. The K or L absorption edge of an element plays a major role in the attenuation of X-ray photon energy, and has a significant attenuation effect on X-ray photons with similar energy. As an alternative, it has been reported that the K absorption edge of rare earth (RE) elements is located in the range of 40–80 keV, which corresponds to the energy range of X-rays and medical X-ray energy range. Additionally, natural leather (NL) is an abundant natural biomass that is composed of multi-layered collagen fibers and contains amino (―NH₂), carboxyl (―COOH), and hydroxyl (―OH) groups. We believe that RE nanoparticles can be uniformly immobilized and stabilized by NL. In this study, we developed a novel strategy to prepare X-ray radiation protective materials by combining RE nanoparticles with NL. NL-based protective materials have the advantages of being lightweight and wearable while providing excellent protection. NL-based RE oxide nanoparticle composites (RE-NL) were successfully prepared by a "retanning" method and verified by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrometer (EDS) and transmission electron microscopy (TEM). X-ray protection tests showed that La-NL had the best shielding performance compared to the other tested RE oxide-loaded NLs owing to the small difference between the K-edge energy of La and the incident energy. Moreover, La_7.80-NL (La₂O₃ content of 7.80 mmol·cm^-3, 0.7 mm) showed better protection performance than a Pb plate with a high-Z elemental content (54.7 mmol·cm^-3, 0.25 mm) at 40–80 keV, confirming that the uniform distribution of RE oxides in NL provides enhanced X-ray shielding performance. The RE-NL also displayed a much better tensile strength, tear strength, and softness compared with polymer-based RE oxide composites. Meanwhile, it has the foldability and character of tailor. Therefore, the reported NL-based RE protective materials show promising potential for various scenarios requiring radiation protection.     

Influence of Glycerol Content on Properties of Wheat Gluten/Hydroxyethyl Cellulose Biocomposites

Environmentally friendly biocomposites were prepared by blending wheat gluten（WG）as a matrix, hydroxyethyl cellulose（HEC）as a filler,and glycerol as a plasticizer,followed by thermo-molding of the mixture at 120°C for crosslinking the matrix.Moisture absorption,tensile properties,dynamic mechanical analysis,and dynamic rheology were evaluated in relation to the glycerol content.Tensile strength and modulus drop dramatically with increasing glycerol content,which is accompanied by significant depression in the glass transition temperature and improvement in the extensibility of the biocomposites.     

阳离子皮革加脂剂的研制及应用进展

本文综述了皮革化工材料中阳离子皮革加脂剂的研制及应用现状和最新进展,并预测了其今后的发展趋势。     

含咪唑离子聚乙烯离聚体的合成与性能

利用双(β-二酮单亚胺)钛催化乙烯和5-碘甲基降冰片烯(IMNB)的配位共聚,高效合成了高分子量、窄分子量分布和组分可控的烯烃共聚物.将该含有碘甲基侧基的共聚物与N-甲基咪唑进行亲核取代反应,然后再与有机金属盐进行离子交换,制备了一系列带有甲磺酸根(CH3SO3-)、三氟甲磺酸根(CF3SO3-)或双(三氟甲磺酰)亚胺负离子(Tf2N-)的聚乙烯离聚体.研究表明,离子基团的引入会破坏聚合物的结晶,熔融温度和结晶度均随着离子含量的增加而降低.但离聚体的玻璃化转变温度却高于乙烯/IMNB共聚物,表明离子基团之间的强相互作用抑制了链段运动.与共聚物前体相比,聚乙烯离聚体表现出更高的热稳定性、更好的亲水性和更高的抗拉强度.当离子含量相同时,聚乙烯离聚体的抗拉强度顺序为:CH3SO3->CF3SO3->Tf2N-,而断裂伸长率呈现相反的趋势.     

壳核型磁性纳米纤维素微球的超声制备及表征

A kind of cellulose magnetic nanoparticle with a core / shell structure has been prepared by ultrasonic irradiation. Cellulose acts as the shell while Fe3O4 magnetic nanoparticles take the role as the core. Magnetic force microscopy（MFM）with atomic force microscopy（AFM）measurement showed that the size of the magnetic nanoparticles is about 30-50 nm in diameter,while the Fe3O4 core is about 20-30 nm. FT-IR,XRD and MFM was used to provide the chemical and magnetic information of the nanoparticles. The MFM image showed that the nanoparticles separate very well with each other,indicating the cellulose shell produces a good prevention from the aggregation of the Fe3O4 particles. MFM studies also showed two magnetic nanoparticles can form particle-pairs,indicating a weak magneto-dipole interaction between magnetic nanoparticles. It is also found that the average sizes of magnetic nanoparticles have relation to the power of ultrasonic irradiation,and the possible mechanism is discussed.     

聚丙烯/锡氟磷酸盐玻璃复合材料的结构与性能

锡氟磷酸盐玻璃(Pglass)具有较低的玻璃化转变温度,在常规聚合物加工温度窗口内具有熔融流动性,是一种新型的无机类聚合物玻璃。本文采用双螺杆挤出机制备了聚丙烯(PP)/Pglass有机聚合物/无机玻璃复合材料,并对其相形貌、界面性能、流动性能、结晶性能、力学性能和热稳定性能进行了研究。结果表明:Pglass以微米级颗粒分散在PP基体中,且两相之间界面明显、相容性较差。Pglass的添加使复合材料的熔体剪切粘度降低。Pglass的存在促进了基体PP的结晶。复合材料的弹性模量随着Pglass含量的增加而增加。Pglass提高了复合材料的热稳定性。     

纺织品、皮革及其制品中五氯苯酚残留量的气相色谱-质谱法测定

介绍应用气相色谱-质谱法测定纺织品、皮革及其制品中防霉剂五氯苯酚的残留量,试样经硫酸溶液酸化后用正己烷提取,用气相色谱-质谱选择离子测定。方法简便、快速、灵敏,检出限20μg／kg,添加回收率86．7％～93．1％,变异系数4．1％～5．9％。