超声波辅助纤维素酶水解制备纳米纤维素

以人纤浆为原料,利用超声波辅助纤维素酶水解制备纳米纤维素（NCC）,在单因素试验基础上,采用正交试验优化NCC的制备条件,并通过透射电镜（TEM）、X射线衍射（XRD）、红外光谱（FT-IR）、热重（TG）和Zeta电位测定对NCC的结构和性能进行了分析与表征。研究结果表明：NCC的最佳制备条件为酶用量为人纤浆质量的7%、50℃条件下酶解反应10 h,此时纳米纤维素的得率可达62.3%。TEM表征显示制备的纳米纤维素呈短棒状,纳米纤维素之间相互交织形成网络结构;XRD分析表明纳米纤维素的晶体结构并未发生改变,仍为纤维素Ⅰ型,结晶度由人纤浆的54.2%增大到73%;FT-IR分析显示纳米纤维素仍保持天然纤维素的化学结构;热重分析表明纳米纤维素的热稳定性较纤维素原料显著提高;Zeta电位测试结果表明纳米纤维素在水介质中具有良好的分散稳定性。     

不同晶型纳米TiO2的制备及其在水中分散性能的研究

采用凝胶-溶胶法制备了不同晶型纳米TiO2,通过X射线衍射(XRD)和扫描电子显微镜(SEM)表征制备出的纳米TiO2晶型为锐钛矿型和金红石型,粒径约为50 nm;考察了不同种类分散剂对不同晶型纳米TiO2在水中分散性能的影响,重力沉降评价、分光光度测试、粒径的测试结果表明:锐钛矿型纳米TiO2在含分散剂六偏磷酸钠(SHMP)的水溶液中分散较好;金红石型纳米TiO2在含分散剂羧甲基纤维素钠(CMC)的水溶液中分散性较好.     

纤维素纳米晶体制备工艺优化的研究

以微晶纤维素(MCC)为原料经硫酸水解制备纤维素纳米晶体(CNC)。采用单因素法结合正交试验系统地研究了硫酸质量分数、反应温度和反应时间对纤维素纳米晶体得率以及平均粒径的影响,并通过扫描电镜(SEM)、原子力显微镜(AFM)、X射线衍射仪(XRD)、纳米激光粒度仪对CNC的性能进行了表征,揭示了酸水解制备CNC的机理。结果表明：CNC制备的最佳工艺参数为硫酸质量分数64%、反应温度45 ℃、反应时间90 min,在此条件下CNC的得率为24.6%,粒径为204.8 nm。CNC水悬浮液呈一种稳定的淡蓝色胶体状态,其微观形貌比较规整,呈短棒状,直径约10~20 nm,长度在150~300 nm之间;XRD结果显示CNC的晶型为纤维素Ⅰ型,结晶度为80.2%。     

纤维素纳米晶/热塑性聚氨酯复合材料的性能研究

采用硫酸水解法制备了纤维素纳米晶,并用于增强热塑性聚氨酯弹性体。通过XRD、红外光谱、DMA和AFM等表征手段对纤维素纳米晶的表面基团以及溶液共混法制备的纤维素纳米晶/聚氨酯复合材料的微观结构和力学性能进行了研究。结果表明,质量分数2%的纤维素纳米晶能够在聚氨酯基体中均匀分散,复合材料的拉伸强度为纯聚氨酯薄膜的184%,且断裂伸长率没有损失。含有质量分数5%纤维素纳米晶的复合材料呈现特殊的相结构,此时复合材料的储能模量最大,玻璃化转变温度最高。     

纳米纤维素负载纳米金的制备及其催化性能研究

以高碘酸钠氧化纳米纤维素(NC)制备得到双醛基纳米纤维素(DNC),并以DNC为还原剂和负载体,制备得到NC负载纳米金催化剂。并通过UV、FT-IR、XRD、XPS及TEM对催化剂合成条件、化学结构、晶型结构、纳米金在纤维素载体表面的价态及大小分布等进行了表征。结果显示金离子90℃下9 h后基本被DNC完全还原为单质金;且纳米金粒子均匀分布在NC上,粒径在40 nm左右。以硼氢化钠还原4-硝基苯酚(4-NP)反应作为模型来研究纳米纤维素负载纳米金的催化性能,研究显示55 min后4-NP转化率可达94%,其催化速率常数为0.073 min~(-1)。     

溶剂热法可控合成纳米四氧化三锰

以高锰酸钾为锰源,以葡萄糖、果糖、纤维素、聚乙烯醇、丙酮为还原剂,通过溶剂热法成功制得纯相的纳米锰氧化物。采用X射线衍射(XRD)、透射电子显微镜(TEM)、X射线光电子能谱仪(XPS)等手段对制备产物进行表征。实验结果表明,以丙酮为还原剂,在反应温度为180℃、反应时间为4 h条件下,制备产物为棒状的纯相四氧化三锰纳米粒子,粒径为50~150 nm,粒径分布均匀,且可通过反应条件进行调控。     

酸解时间对纳米晶纤维素胆甾相液晶的影响

研究了酸解时间对纳米晶纤维素薄膜颜色和螺距的影响。以棉短绒为原料,采用硫酸酸解法,以酸解时间为影响因素,制备了三种纳米晶纤维素(CNC)悬浮液,再将三种悬浮液放入烘箱干燥,制成具有不同颜色的纳米晶纤维素薄膜。采用Zeta电位及纳米粒度分析仪对CNC悬浮液的Zeta电位和粒径进行表征。采用紫外可见近红外分光光度计(UV-vis-NIR)、全反射傅里叶红外光谱仪(FT-IR)、X-射线衍射仪(XRD)、扫描电子显微镜(SEM)以及偏光显微镜(POM)对薄膜进行表征进而研究了酸解时间对纳米晶纤维素胆甾相液晶螺距的影响。结果表明,随着酸解时间增长,CNC的粒径减小,引入的磺酸酯增多,表面负电荷增大,颗粒之间静电斥力增大,最终导致螺距增大,薄膜的反射波长红移,薄膜的颜色从蓝色逐渐转向红色。     

酸法制备纳米纤维素特性及其气凝胶的制备

以微晶纤维素(microcrystalline cellulose,MCC)为原料通过硫酸水解制得纳米纤维素(nanocrystalline cellulose,NCC),采用透射电子显微镜(TEM)、马尔文粒径仪、X-射线衍射仪(XRD)和傅利叶红外光谱仪(FI-TR)对所制备的NCC的微观形貌、谱学性能及晶型结构进行表征分析。结果表明:制备的NCC呈梭形短棒状,直径集中分布在20~40 nm之间,长度多分布200~300 nm之间;其傅立叶红外波普图与MCC谱图相似,NCC晶型仍然保持纤维素Ⅰ型结构,其相对结晶度略有提高,为90.57%。并以制得的NCC为原料,采用物理凝胶法成型,经乙醇置换后,通过超临界CO_2干燥法制备纳米纤维素气凝胶。通过描电子显微镜(SEM)、全自动比表面积与孔隙度分析和傅利叶红外光谱仪(FI-TR)对制备的纳米纤维素气凝胶微观形貌、比表面积、孔径分布以及普学性能进行表征分析。结果表明:制备的纳米纤维素气凝胶晶型结构不变,且具有丰富的三维网络结构,其孔隙以中孔为主,微孔与大孔兼而有之,比表面积可达308.422 9 m~2/g,平均孔径为8.21 nm。     

纳米二氧化钛薄膜的制备及其光催化性能

采用水热法制备了纳米二氧化钛溶胶,然后采用旋涂法制备了其纳米薄膜。通过X-射线衍射(XRD)和原子力显微镜(AFM)对样品进行了表征;XRD结果表明:通过控制反应条件可以制备不同晶型的纳米二氧化钛。AFM的表征结果表明:所制备的混晶型二氧化钛粒径在32 nm以下,锐钛矿型的二氧化钛粒径在4 nm以下,掺杂二氧化硅的二氧化钛粒径在160 nm以下,掺杂负离子粉的二氧化钛粒径在10 nm以下。对甲基橙的降解实验表明:掺杂负离子粉的二氧化钛的光催化性能最好。     

纳米活性炭/锌锰复合电极材料的制备及性能

使用溶胶-凝胶法合成锌掺杂二氧化锰的纳米晶电极材料,将其与干式振动滚压法制备的纳米活性炭混合制成超级电容器所需的片状电极。纳米活性炭材料为类球状颗粒,粒径约为50 nm,且为微孔和中孔并存的狭缝结构;制备的锌掺杂二氧化锰纳米晶材料为中孔占优的孔隙结构,含有纳米锌和氧化锌的成分,经XRD测试和比表面分析,得到此纳米晶材料的平均粒径小于30 nm。分析显示,经滚压振动研磨改性的纳米活性炭与10%纳米晶锌锰材料混合的电极材料具有较好的电容性能,比电容达到299 F.g-1。     

过硫酸铵氧化速生杨木残渣制备纤维素纳米晶体及其表征

以去除半纤维素的速生杨木残渣为原料,在70℃下按固液比1：100（g：mL）加入1.5 mol/L过硫酸铵溶液,处理16 h制备纤维素纳米晶体。所得样品为白色粉末状固体,得率（以原料中纤维素质量计）为57%,氧化度为0.156,表面电荷为-42.15 mV。采用透射电子显微镜、傅里叶变换红外光谱、X射线衍射、核磁共振等技术对得到的纳米纤维素进行表征。结果表明：过硫酸铵去除了原料中的木质素和残余的少量半纤维素,并有选择地将纤维素C6位置上的伯醇羟基氧化成羧基,纤维素纳米晶体保留了原纤维素的结构特征,结晶度为77%,晶体结构以I_β晶型为主,88.4%的纤维素纳米晶体宽度在10~24 nm之间。     

磷酸锆辅助催化水解菌糠制备纳米纤维素晶体的性能

以食用菌产业的副产品菌糠为原料,采用磷酸锆催化剂辅助稀硫酸水解制备纳米纤维素晶体(cellulose nanocrystals,CNCs).与传统酸水解方法相比,该方法简化了工艺流程,制备过程环境友好。考察了超声时间、超声温度以及稀硫酸浓度等因素对CNCs得率的影响。结果表明当超声时间为5h、超声温度为75℃及稀硫酸浓度为12.3%时,CNCs得率为42.80%.采用透射电子显微镜(TEM)、扫描电子显微镜(SEM)、傅里叶变换红外光谱(FTIR)以及X射线衍射仪(XRD)对样品的微观形貌、谱学性能和晶体结构进行了研究分析,结果表明所制得的CNCs呈棒状,直径介于10～30nm之间;CNCs属于纤维素I型,与原料菌糠相比,结晶度由63.79%增大到81.04%;且CNCs仍具有天然纤维素的基本化学结构。论文研究为菌糠的资源化高效利用开辟了新途径。     

离子液体与水混合溶剂应用于微晶纤维素溶剂液化研究

将离子液体氯化1-丁基-3-甲基咪唑（[BMIM]C1）、水、固体酸催化剂组成的混合溶剂应用于微晶纤维素的预处理过程中,并尝试把经过预处理的微晶纤维素应用于随后的溶剂液化的研究中,对经过混合溶剂处理后的微晶纤维素进行表征分析。通过测定纤维素的聚合度、官能团基变化、热重分析、结晶结构和表面结构等对微晶纤维素结构进行比较分析。通过对苯酚溶剂液化的基本表征、残渣物的结晶结构以及生成物相对分子质量的变化了解了混合溶剂对微晶纤维素的处理效果。结果表明,通过混合离子液体[BMIM]C1和水并且添加固体酸催化剂形成新的混合溶剂体系对微晶纤维素进行预处理,发现溶剂在保留纤维素主要葡萄糖单元的同时能够有效地降低聚合度。聚合度从未处理时的190降到样品[B]C1（10）的165和样品[B]C1（10）＋NR50的151。混合溶剂对非结晶或低结晶物质具有一定的溶解能力,并且对高结晶性纤维素部分的氢键结构起到破坏作用和造成整体结晶结构的歪曲。在随后的液化过程中,处理后的纤维素液化效率有所提高,在反应2min时,固体酸加混合溶剂处理的微晶纤维素液化残渣率为19％,而未处理的液化残渣率29％。表明使用了混合溶剂添加固体酸的溶剂体系对加速液化的效果更佳,预处理对最终液化生成物的性质影响不大。     

基于互穿网络技术构筑的氧化海藻酸钠/纤维素纳米晶/聚丙烯酰胺-明胶复合水凝胶与性能

为了提高海藻酸盐水凝胶的生物应用性,采用互穿网络技术、纤维素纳米晶(CNCs)补强和明胶表面覆积相结合的方法构建了氧化海藻酸盐/纤维素纳米晶/聚丙烯酰胺-明胶 (OSA/CNCs/PAM-GT) 复合水凝胶。通过FT-IR、TGA、 XRD、溶胀性和降解性实验以及细胞相容性测试考察了CNCs含量对OSA/CNCs/PAM-GT复合水凝胶结构和性能的影响。实验结果表明,CNCs能够与基体中的聚合物产生相互作用力。并且随着CNCs含量的增加,OSA/CNCs/PAM-GT 复合水凝胶的孔隙率下降,力学性能提高。而且它们的溶胀性和生物降解性虽然受CNCs含量增加而呈现下降的趋势,但是幅度较小,说明CNCs能够在一定程度上调控复合水凝胶的物化性能。同时,OSA/CNCs/PAM-GT 复合水凝胶展现出较好的细胞粘附、增殖和分化性能。当CNCs的含量在0.5%时,细胞增殖的效果最佳,而CNCs的含量为1.5%时,细胞分化效果最显著。因此,将CNCs掺杂到OSA/PAM互穿网络基体中能够有效地调控其生物性能,使其适用于生物医学领域。     

Extraction of cellulose nanocrystals and fabrication of high alumina refractory bricks using pencil chips as a waste biomass source

Extraction of “green” cellulose nanocrystals (CNCs) from waste biomass is a sustainable strategy for high valued valorization in the view of socio-economic and environmental issues. Herein, for the first time, waste pencil chips (PC) as a potential source of cellulose, were used for the extraction of CNCs. CNCs were successfully extracted from PC wastes using alkali and bleaching chemical treatments to remove hemicellulose and lignin followed by acid hydrolysis using concentrated sulfuric acid. The products after each step were characterized in terms of crystallinity, chemical structures, thermal properties, and morphologies. The XRD results showed that the crystalline index increased about 16% from PC (75%) to CNCs (91%). The FTIR analysis confirmed the removal of the hemicellulose and lignin from PC after alkali and bleaching treatments. The TGA analysis showed that the thermal stability of the CNCs is affected mainly by the dehydration reaction caused by sulfate groups. The SEM and FE-SEM images showed that after chemical treatments, defibrillation of fibers occurs and CNCs have a needle/rod like structure. Also, the specific surface aera was greatly increased from 0.495 for PC to 486.430 m²/g for CNCs. Herein, for the first time, lignin-containing cellulose extracted from PC was replaced with sawdust (SRB) in the production of alumina refractory bricks (RBs), as a pore former/binder. Interestingly, the prepared RBs (PC–NaOH/RB) had a greater amount of alumina (83%) and a lower density (0.75 g/cm³) than SRB. The classification temperature increased from 1650 for SRB to 1717 °C for PC-NaOH/RB.     

游离态和吸附态铁催化分解过氧化氢

通过制备差异态铁,研究了差异态铁对碱性过氧化氢的催化分解行为,考察了硫酸镁、硅酸钠及DTPA在差异态铁存在下的功能效果.研究发现,游离态铁以Fe₂O₃晶体颗粒形式存在,通过吸附在纤维表面或者填充在纤维“孔腔”内形成纤维素吸附态铁;游离态铁减弱了过氧化氢碱性分解,吸附态铁强化了过氧化氢碱性分解.DTPA、硫酸镁显著抑制游离态铁催化分解碱性过氧化氢,将过氧化氢分解率分别降至25%,50%.DTPA、硫酸镁对抑制纤维素吸附态铁的催化分解无效,1 h内碱性过氧化氢分解率达到80%以上.     

Compatibilization of poly(methyl methacrylate) and cellulose nanocrystals through co-continuous phase to enhance the thermomechanical properties

The present study focuses on enhancing the thermomechanical properties of poly(methyl methacrylate) (PMMA), a transparent and biocompatible polymer known for its high strength but limited toughness. The approach involves the development of PMMA/cellulose nanocrystals (CNCs) composites. To improve the interfacial compatibility between PMMA and CNCs, a two-step process is employed. Initially, the CNCs undergo oxidation using sodium periodate, followed by the introduction of amino groups through reductive amination. The aminated CNCs are then covalently bonded to PMMA via an amidation reaction using the “grafting onto” approach. Subsequently, the grafted CNCs are incorporated into the PMMA matrix using the solvent casting method. The resulting composites are extruded into filaments. Elemental composition analysis confirms CNC modification, revealing the presence of 1.6% nitrogen. The modified CNCs exhibit a higher degradation temperature than unmodified CNCs, showing a 50°C increase. The composites' dynamic mechanical analysis (DMA) reveals a 20% improvement in storage modulus (E′) upon incorporating 1.5% of the grafted CNCs into the PMMA matrix. This enhancement is attributed to the formation of co-continuous phases in the composite structure.     

Thermoplastic Starch Nanocomposites Reinforced with Cellulose Nanocrystal Suspensions Containing Residual Salt from Neutralization

Sulfuric acid-catalyzed hydrolysis of cellulose commonly isolates cellulose nanocrystals (CNCs). Neutralizing the reactant solution with sodium hydroxide facilitates efficient downstream processing, but residual salt remains in the product. This study examines the reinforcing effects of CNCs from suspensions that contain residual salt on the mechanical properties of thermoplastic starch nanocomposites. By reinforcing starch films with up to 5 wt% CNCs, stiffness and strength are improved by 118% and 79%, respectively, indicating a good dispersion of CNCs in the starch matrix. Compared to nanocomposites incorporating salt-free CNCs, the remaining salt has no significant impact on the material's mechanical performance. The results indicate great potential of CNCs containing residual salt as biobased, low-cost nanofiller in hydrophilic polymer matrices.     

Preparation and mechanism analysis of morphology-controlled cellulose nanocrystals via compound enzymatic hydrolysis of eucalyptus pulp

First, making from eucalyptus cellulose fiber, the influences of different compound enzymolysis conditions on the morphology of cellulose nanocrystals (CNCs) were studied. Under the actions of the compound enzyme composed of cellulase and xylanase with the concentration ratio of 9:1, total enzyme concentrations of 10 and 500 U mL⁻¹ and the hydrolysis time of 12 and 5 h, the rod-like CNCs (length 600 nm, width 30 nm) and the spherical CNCs (40 nm) were obtained, respectively. Subsequently, the crystallinities, chemical structures, and thermal stabilities of the rod-like and spherical CNCs revealed that, the CNCs structures were still similar to those of the eucalyptus cellulose fiber, the thermal decomposition temperatures of the rod-like and spherical CNCs (345, 343 °C) were a little lower than that of the eucalyptus cellulose fiber (364 °C). Lastly, the control mechanism of CNC morphology by the compound enzymatic hydrolysis was also discussed. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48407.     

Extraction and characterization of cellulose nanocrystals from cotton fiber by enzymatic hydrolysis-assisted high-pressure homogenization

Cellulose nanocrystals (CNCs) have attracted increasing attention in the field of nanomaterials because of its high aspect ratio, good structure, and high thermal stability. In this study, enzymatic hydrolysis-assisted high-pressure homogenization was applied as an environmentally friendly technique to extract CNCs from cotton-derived microcrystalline cellulose (MCC). The overall optimization of enzymatic pretreatment was conducted by response surface methodology, and the maximum CNCs yield was 40.09% under the optimized experimental conditions. The extracted CNCs under the optimal conditions showed needle-like shape with a length of 100–250 nm and a width of 5–10 nm and exhibited an overall particle size range of 3–80 nm. The basic chemical structure of cellulose was not changed after enzymatic hydrolysis and high-pressure homogenization. The CNCs exhibited slightly lower crystallinity and higher thermal stability than MCC. High aspect ratio CNCs extracted in this present study have great potential as a reinforcing agent in biodegradable packaging materials.