一锅法合成氨基化纳米纤维素及其性能表征

为实现纳米纤维素衍生物的绿色高效制备,以过硫酸铵为氧化剂,基于机械力化学作用,在微波-水热条件下氧化降解竹浆粕得到羧基化纳米纤维素(CNC),然后与二乙烯三胺发生缩合反应,实现水相中氨基化纳米纤维素(ACNC)的一锅法合成,并对其性能进行研究。结果表明:ACNC呈棒状,直径为10~40 nm,长度为50~300 nm, 氨基的接枝率为6.29%;ACNC的晶型并未发生改变,仍为纤维素Ⅰ型,结晶度由竹浆粕的59%增加到79%;ACNC的热稳定性较竹浆粕并未显著下降,但较CNC显著提高,说明CNC表面接枝氨基后热稳定性能得到改善;该制备方法绿色高效,得到的纤维素衍生物有望在生物固化和物理性能增强方面发挥作用。     

纤维素的研究进展

纤维素是自然界最丰富的有机高分子,具有可再生、绿色和生物相容性,不仅在制浆造纸产品中得到大宗应用,也是化学化工的重要基础原材料。本文主要对纤维素的溶解、化学改性、纳米纤维素制备和纤维素/纳米纤维素新材料等方面的研究进展进行了综述。     

Industrialization Progress of Nanocellulose in China

Nanocellulose, a kind of cellulose with nanometer sizes, has drawn great interest in the pulp and paper industry due to its unique structure and excellent performance. It can be divided into five categories: nanocrystalline cellulose (NCC), nanofibrillated cellulose (NFC), bacterial cellulose (BC), electrospun cellulose nanofibers (ESC), and precipitation regenerated cellulose nanofibers (PRC). In this paper, we reviewed the industrialization progress of nanocellulose in China. Furthermore, we proposed that efficient and environmentally friendly preparation methods and high value utilization would be the focus of nanocellulose development.     

Simultaneous Extraction of Carboxylated Cellulose Nanocrystals and Nanofibrils via Citric Acid Hydrolysis—Sustainable Route

In this study, cellulose nanocrystals (CNC) with surface carboxylic groups were prepared from bleached softwood pulp by hydrolysis with concentrated citric acid at concentrations of 60 wt%~80 wt%. The solid residues from acid hydrolysis were collected for producing cellulose nanofibrils (CNF) via post high-pressure homogenization. Citric acid could be easily recovered after hydrolysis reactions through crystallization due to its low water solubility or through precipitation as a calcium salt followed by acidification. Several important properties of CNC and CNF, such as dimension, crystallinity, surface chemistry, thermal stability, were evaluated. Results showed that the obtained CNC and CNF surfaces contained carboxylic acid groups that facilitated functionalization and dispersion in aqueous processing. The recyclability of citric acid and the carboxylated CNC/CNF give the renewable cellulose nanomaterial huge potential for a wide range of industrial applications. Furthermore, the resultant CNC and CNF were used as reinforcing agents to make sodium carboxymethyl cellulose (CMC) films. Both CNC and CNF showed reinforcing effects in CMC composite films. The tensile strength of CMC films increased by 54.3% and 85.7% with 10 wt% inclusion of CNC and CNF, respectively. This study provides detailed information on carboxylated nanocellulose prepared by critic acid hydrolysis; a sustainable approach for the preparation of CNC/CNF is of significant importance for their various uses.     

超声辅助硫酸水解法制备银杏果壳纳米纤维素及其特性表征

为充分利用银杏的工业生产副产物,以银杏果壳为原料,采用超声辅助硫酸水解法制备银杏果壳纳米纤维素（nanocrystalline cellulose isolated from ginkgo nut shell,NCC-GNS）。通过单因素实验研究了硫酸质量分数、反应温度和反应时间3个因素对NCC-GNS得率的影响,并应用正交试验进行优化,获得NCC-GNS的最佳制备条件。以常规硫酸水解法（未加超声辅助）制备的纳米纤维素（nanocrystalline cellulose,NCC）为对照,通过扫描电镜（scanning electron microscopy,SEM）、透射电镜（transmission electron microscopy,TEM）、Zeta电位和动态光散射（dynamic light scattering,DLS）、X-射线衍射（x-ray diffraction,XRD）、傅里叶变换红外光谱（fourier transform infrared spectroscopy,FT-IR）、热重（thermogravimetric analysis,TGA）等分析超声辅助处理对NCC-GNS的影响。结果表明:超声功率120 W时,制备NCC-GNS的最佳条件为硫酸质量分数48%、反应温度60 ℃、反应时间25 min,最优条件下NCC-GNS得率为37.01%;超声辅助和常规硫酸水解法制备的NCC-GNS均为长棒型,尺寸无明显差异,超声辅助制备的NCC-GNS长度和直径的分布范围相对集中,长度80～180 nm、直径3.5～5.5 nm;超声辅助制备的NCC-GNS结晶度为88%,高于常规硫酸水解的75%;两种方法制备的NCC-GNS均具有较低的Zeta电位和有良好的热稳定性。综上,超声辅助硫酸水解法制备的NCC-GNS得率较高,获得的NCC-GNS结晶度高、热稳定性好,在生物质复合材料领域表现出良好的应用前景。     

纳米纤维素晶体的性能研究

竹子溶解浆经植物粉碎机预处理,再用硫酸水解制备纳米纤维素晶体(NCC)。利用马尔文激光粒度仪、扫描电镜(SEM)、透射电镜(TEM)、X射线衍射(XRD)、红外光谱(FTIR)、热重分析仪(TGA)对原料及纳米纤维素晶体的尺寸、形貌、晶体特性、结构和热性能进行表征。结果表明:NCC的Z均粒径为128.7nm;竹浆经机械粉碎部分纤维长链被切断;由TEM图观察可知NCC为棒状,直径5~10nm,长度100~200nm;竹浆及NCC属于纤维素Ⅰ型,结晶度由竹浆的64.27%提高到72.04%;FTIR图谱表明竹浆与NCC化学结构基本一致;TGA分析表明NCC的热稳定性低于竹浆,但NCC的降解速率较竹浆缓慢,并且NCC的热解残余率增大。     

Nanocellulose-based fibres derived from palm oil by-products and their in vitro biocompatibility analysis

Abstract

Fibres with nanocellulose isolated from oil palm empty fruit bunches (OPEFBs) were produced. Nanocellulose and PVA-nanocellulose fibres were prepared by wet spinning in an acetone coagulation bath without drawing. The addition of nanocellulose was varied from 10% to 30%, to reveal the beneficial effects of nanocellulose content on the properties of produced spun-fibres. Higher concentration of nanocellulose increased the stiffness of spun-fibres. PVA and PVA-bacterial cellulose fibres were also produced as a control and for comparison, respectively. The nanocellulose fibre formed a compact structure, while PVA fibres had hollow structures. The effect of the produced spun-fibres on the biocompatibility of calf pulmonary artery endothelial cells was assayed by an MTT test. Based on the MTT assay the addition of nanocellulose increased the percentage of cell viability of the obtained spun-fibres slightly. These results point towards the use of sustainable sources of nanocellulose as a beneficial and biocompatible fibre material.     

硅烷偶联剂改性纳米纤维素气凝胶的制备及其表征

为研究硅烷偶联剂含量对纳米纤维素气凝胶性能的影响,选用氨丙基三乙氧基硅烷(KH-550)和甲基三甲氧基硅烷(MTMS)2种硅烷偶联剂对纳米纤维素(CNF)气凝胶进行修饰。通过扫描电子显微镜、热重分析仪、万能强力机和热常数分析仪进行测试与表征。结果表明:硅烷偶联剂的添加使改性气凝胶红外光谱图上出现了含硅峰值,但并未改变气凝胶的组分;改性后气凝胶的孔洞明显增多;MTMS与CNF的质量比为1∶2时,改性气凝胶的压缩回弹性最好(7.25 kPa);MTMS的添加使改性气凝胶具有良好的疏水性,接触角为156°;随着KH-550的添加,气凝胶导热系数先降低后升高;随着MTMS的添加,气凝胶导热系数逐渐降低。     

纳米零价铁-微纤化纤维素复合材料的制备及在造纸废水深度处理中的应用

以微纤化纤维素作为天然高分子载体,通过原位液相化学还原反应负载零价铁制备得到了纳米零价铁-微纤化纤维素(NZVI-MFC)复合材料。通过红外光谱(FT-IR)、透射电镜(TEM)、X射线衍射(XRD)和热重分析仪(TGA)来表征NZVI-MFC复合材料并研究其耐热性能,同时,将NZVI-MFC复合材料应用于造纸废水深度处理,探讨了NZVI-MFC复合材料添加量和废水初始pH值对废水处理效果的影响。结果表明,NZVI通过原位化学反应均匀负载到MFC基材上,在废水深度处理最佳条件下,造纸废水的COD_Cr和色度总去除率分别达到78.4%和90.7%。     

利用甘蔗渣制备羟甲基纤维素的工艺研究

本文采用甘蔗渣为原料，经单一态氧漂白，在乙醇溶剂中与氢氧化钠、氯乙酸反应，制备了羟甲基纤维素。讨论了反应温度、时间及物料配比对产品性能的影响。确定了最佳反应条件。     

Nanocellulose preparation via a dissolution and regeneration process and application to wood‐plastic composites as toughness enhancement

In this work, nanocellulose (NC) was prepared by a new route consisting of dissolution of cellulose in phosphoric acid followed by regeneration in water. To facilitate the dissolution, the cellulose was pre-treated with aqueous solution of urea. Although the regenerated cellulose from water had been in nanoscale, its size could be further reduced through ball milling. The composition, structure, and morphology of the materials from different preparation stages were studied by infrared spectroscopy (FTIR), X-ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. NC was then incorporated into the HDPE based wood-plastic composites (WPCs) in a skillful way to guarantee its good dispersion. The influence of addition content of NC on the mechanical and thermal properties of WPCs was investigated comprehensively. WPCs incorporated with NC exhibited an obvious increase in impact strength compared with those without NC. In addition, the Rockwell hardness, Vicat softening temperature and thermal stability of WPCs incorporated with NC were also correspondingly improved. The effect of ball milling on the size of nanocellulose was also investigated. The application results showed that the NC prepared without ball milling was more efficient in enhancing the toughness of WPCs.

     

玉米秸秆纳米纤维素的制备及表征

利用超声辅助硫酸水解法制备玉米秸秆纳米纤维素（corn straw nanocellulose,NCSC）,研究超声辅助酸解条件对NCSC得率的影响,并通过响应面法优化得到最佳工艺条件为：硫酸体积分数64%、超声功率160?W、酸解温度48?℃、酸解时间78?min,在此条件下制备NCSC得率达38.29%。制备的NCSC较洁白、细腻,具有较好的吸水膨胀力。通过红外光谱分析、X射线衍射和热失重分析表明,NCSC仍保持着玉米秸秆纤维素（corn straw cellulose,CSC）的基本化学结构,其结晶度（70.53%）高于CSC,同时具有较高的热分解温度。     

Isolation of Nanocellulose from Pomelo Fruit Fibers by Chemical Treatments

This study aims to isolate cellulose nanofibers from locally abundant pomelo fruit. The peels were subjected to alkali treatment (NaOH) with different concentrations and soaking times. Acid hydrolysis was also carried out to obtain an aqueous suspension of nanocellulose. The treated cellulose fibers were characterized by various methods. Alkali treatment was able to remove noncellulosic constituents. Microscopy techniques yielded morphology of elementary fibers with a compact structure with both micro- and nano-scaled fibers. An improved onset of degradation was likely caused by an increase in crystallinity evidenced by X-ray diffractometry (XRD). Acid hydrolysis could successfully individualize cellulose nanofibers as observed by transmission electron microscopy (TEM).     

纤维素资源的开发及利用新进展

文章介绍了纤维素资源开发的一些最新进展,包括纳米纤维素、新型成网技术、绿色纤维素产品以及醋酯纤维的开发等。在此基础上探讨了新形势下我国再生纤维素纤维行业的发展路径。     

Transition characteristics of Brazilian vegetable fibers investigated by heating microscopy

ABSTRACT

Structural studies of three vegetable fibers plus eucalypt wood through heating microscopy, Fourier transform infrared spectroscopy, X-ray diffraction (XRD), and thermal analysis through Thermal Gravimetric Analysis/Differential Thermal Analysis are presented in this work. Morphological and dimensional changes obtained from heating microscopy were observed, showing shrinkage occurrences of vegetable fibers related to their diameter and length, respectively. The thickness decreased by 50% when heated at 450–500°C, this process starting at 300–400°C with an initial percentage length of ≈ 90%, that corresponds to a fast weight loss. These results were compared with simultaneous thermal analysis under the same conditions. Thus, for the first time, it was possible to quantify vegetable fiber dimensional changes and surface aspects under heating that cannot be seen by traditional thermal analysis. We also performed crystallinity calculations from XRD data, observing that cellulose/hemicellulose contents had major contribution in all samples.     

一种新型球形纤维素螯合吸附剂的制备

以硫酸盐马尾松浆纤维素为原料制备黏胶纤维,利用热溶胶转相法和反相悬浮技术制得球形纤维素珠体,然后对其进行接枝和微波催化改性制备球形纤维素螯合吸附剂SCCA,并应用现代分析测试方法对SCCA进行理化性能表征。研究表明,SCCA含咪唑基和羧基等特征官能团,改性的最佳条件为：单体与珠体质量比为5：1,引发剂硝酸铈铵与硝酸的浓度分别为9.12 mmol/L和0.1mol/L,反应温度50℃,反应时间60min;微波功率600 W,辐射时间60s,二乙烯三胺浓度4.85 mol/L,催化剂浓度0.39 mol/L。制备的SCCA对Cr3+的吸附容量为38.53 mg/g。     

桉木常规KP浆和RDH浆的氧脱木素研究(Ⅰ)--常规KP浆和RDH浆的氧脱木素效果

对桉木常规KP浆和RDH硫酸盐浆的氧脱木素进行了研究和对比，确定了氧脱木素的最佳条件。结果表明，常规KP浆和RDH硫酸盐浆在适宜的条件下经氧脱木素后，纸浆卡伯值分别降低58．2％和42．25％，纸浆白度分别增加了29．5％ISO和22．4％ISO，达到56．8％ISO和63．O％ISO，而纸浆的粘度变化不大。综合而言，氧脱木素对常规KP浆和RDH浆的卡伯值、白度和脱木素选择性的影响规律类似，但由于RDH浆的初始卡伯值和粘度较低，因而氧脱木素时可以采用相对温和的反应条件，且RDH氧漂浆的粘度也相对较低。     

Chilled orange juices stabilized by centrifugation and differential heat treatments applied to low pulp and pulpy fractions

Thermal treatments of citrus juices to inactivate microorganisms and pectinmethylesterase (PME) must be as soft as possible to preserve fresh taste. PME, a cell wall enzyme associated with pulp, is more heat resistant than spoilage microorganisms. This paper analyzes fresh taste and storage stability of orange juices in which the pulp receives a heat treatment more intense than the rest of the juice. The products compared where: A) low pulp juice treated at 60 °C–15 s; B) aseptic blend of A and the corresponding pulpy fraction treated at 85 °C–15 s; C) non aseptic blend of non-treated low pulp fraction and the corresponding pulpy fraction treated at 85 °C–15 s. Product C was finally treated at 60 °C–15 s and packed under aseptic conditions. PME activity in A, B and C was around 10% of that in the original juice (1.30 nkat/ml).After 12 months at 3 °C, juices B and C retained the original fresh taste with minimal losses of color and cloudiness. Juice A maintained fresh taste but its color and cloud were not satisfactory.

Industrial Relevance

The procedures proposed in this paper can be applied to produce chilled orange juices without losses in fresh taste having in addition, higher stability than commercial juices. Other advantages when compared to non thermal emergent technologies are that can be carried out by regular equipments used in citrus industries with an important energy saving. These procedures imply energy savings of 22% to 38% when compared to thermal requirements of juice pasteurization at 85 °C.     

Micron- and nano-cellulose fiber regenerated from ionic liquids

In this research, two types of ionic liquid, 1-butyl-3-methylimidazolium chloride (BMIMCl) and ionic liquid 1-ethyl-3-methylimidazolium acetate (EMIMAc), were used as recyclable solvents for dissolving raw cellulose in the spinning of micron- and nano-scale regenerated cellulose fiber. The approach for preparing the cellulose solution using these ionic liquids is described. A comparative study was also conducted on cellulose solubility, the spinning method, and cellulose fiber properties produced with each solvent. The experimental fibers are characterized in terms of fiber diameter, strength, thermal property, crystallinity, and content of solvent residual, using tensile test, thermogravimetric analysis, scanning electron microscopy, X-ray diffraction, and mass spectrometry. The study concluded that there was a significant difference in the tensile strength, but not in the elongation and modulus of the fibers regenerated from BMIMCl and EMIMAc. For crystal size, crystal orientation, and crystallinaty index, the BMIMCl-generated fiber had higher values than the EMIMAc-regenerated fiber. For the thermal property, EMIMAc fiber was more stable at higher temperatures than BMIMCl fiber. It was also revealed that the EMIMAc fiber had significantly less solvent residual content than the BMIMCl fiber.     

高温法棉浆二醋片与木浆二醋片可纺性之比较

本文比较了高温法木浆二醋片和棉浆二醋片丙酮纺丝原液的透明度、过滤性、可纺性及其纤维的结构和性能．认为木浆二醋片纺丝原液的透明度和最大纺丝速度较低，而过滤性能较好．由二者生产的二醋纤结构及性能相近．