纤维素、木质素对生物质与煤混烧特性的影响

利用热重红外分析仪着重分析了生物质中纤维素和木质素含量对混合热解及混烧特性的影响.生物质与煤的混合热解相比于纯煤的单一热解失重明显较大较快,并且纤维素含量越高,混合燃料失重越大;木质素含量较高,则混合燃料失重较慢.当燃烧温度为300～400℃之间时,混合燃料中纤维素含量越高,质量下降幅度越大;当燃烧温度为500～700℃之间时,混合燃料中则是木质素含量越高,质量下降幅度越大.     

近红外漫反射光谱法判别分析天然纤维素浆粕反应性能

提出一种采用近红外光谱测定天然纤维素浆粕反应性能的方法。采用国家标准方法(FZ/T50010.13-2011)测定天然纤维素浆粕样品的反应性能,采集了其漫反射近红外光谱。分别采用PCA和簇类独立软模式(SIMCA)方法,建立了浆粕样品反应性能是否合格的分类模型,其识别率达到100%。     

热处理柚木的红外光谱和二维相关红外光谱分析

利用红外光谱(FTIR)和二维相关红外光谱(2D-IR),对蒸汽热处理前后柚木的主要化学成分结构变化进行分析研究。结果显示,热处理后,半纤维素和木质素特征峰强度有不同程度的降低,证明热处理过程中半纤维素和木质素发生热降解。而纤维素热稳定性较好。二维光谱显示,半纤维素具有较高的热敏感性。当热处理温度提高至220℃时,半纤维素降解殆尽,木质素热敏感性高于半纤维素。     

静电纺丝技术制备Gd_2O_3:Eu~(3+)发光纳米纤维与表征

采用静电纺丝技术制备了PVA/[Gd(NO3)3+Eu(NO3)3]复合纳米纤维,并将其进行热处理,得到Gd2O3:Eu3+发光纳米纤维。X射线衍射分析表明,复合纤维为无定型,Gd2O3:Eu3+发光纳米纤维属于体心立方晶系,空间群为Ia 3。扫描电子显微镜(SEM)分析表明,复合纳米纤维的平均直径约为200 nm,经过800℃焙烧后,获得了直径约50 nm的Gd2O3:Eu3+发光纳米纤维。差热-热重分析表明,温度高于600℃时,复合纳米纤维中水份、有机物和硝酸盐分解挥发完毕,样品不再失重,总失重率为71.9%。傅里叶转换红外光谱(FTIR)分析表明,复合纳米纤维的红外光谱与纯聚乙烯醇的红外光谱基本一致,600℃以上生成了Gd2O3:Eu3+发光纳米纤维。荧光光谱分析表明,在251 nm紫外光激发下,Gd2O3:Eu3+发光纳米纤维发射出Eu3+离子特征的609 nm明亮红光。讨论了Gd2O3:Eu3+发光纳米纤维的形成机理,该技术可以推广用于制备其他稀土氧化物发光纳米纤维。     

近红外漫反射光谱法测定天然纤维素浆粕聚合度

提出一种采用近红外光谱测定天然纤维素(棉、木)浆粕聚合度的方法。实验收集了195个天然纤维素浆粕样品,采用GB/T 9107-1999方法测定了其聚合度,对样品进行粉碎预处理后,放入旋转杯中采集相应的近红外漫反射光谱。通过化学计量学偏最小二乘方法(PLS)将聚合度数据与近红外光谱关联,分别建立了棉木浆粕混合样品、棉浆粕样品和木浆粕样品的聚合度定量模型。最优模型相关系数分别为0.980,0.993,和0.886,预测均方根误差(RMSEP)分别为147,143和53。研究了近红外方法精密度和准确性。结果表明棉浆粕和木浆粕分类模型预测准确性优于混合模型,且其预测精密度符合国标(GB)方法要求。另外,采用主成分分析方法建立了棉浆粕和木浆粕的识别模型,结果表明该模型可以有效识别棉浆粕和木浆粕。该方法操作简单、分析速度快,能够满足天然纤维素浆粕聚合度在线检测要求,为实现清洁制浆新工艺聚合度在线监控目标提供了理论和技术依据。     

片层硅酸盐用于热固性PU/PLS复合可能性探讨

高岭土(Kaolinite)和蒙脱土(Montromollite)等粘土,被广泛用作添加剂来改善聚合物的耐热性能。文章用各种先进技术对高岭土与蒙脱土的形态、组成和结构进行表征比较。电子透射电镜及电子探针(TEM/EDX)结果显示高岭土较蒙脱土有较大的粒径和较小的硅铝比,TEM还显示出这些粘土是由片层粒子堆积而成。热重分析(TGA)的结果表明蒙脱土由于失去吸附水从60 ℃升温至90 ℃失重明显(约7%),而高岭土在此温度下几乎不失水。高岭土脱除结构羟基官能团脱水失重的温度大约在510 ℃,低于蒙脱土的670 ℃。室温下光声傅里叶变换(PAS-FTIR)红外光谱显示蒙脱土在羟基吸收区有较强的吸附水的吸收,1 650 cm-1处孤立的弱吸收谱带可给予左证。变温红外和TGA的结果显示,片层硅酸盐表面的结构羟基从100～500 ℃非常稳定,它可以和异氰酸酯基团(NCO)封端的预聚物反应形成热固性PU/PLS复合聚合物。     

棒状纳米纤维素仿生矿化及光谱分析

以棒状纳米纤维素为模板,采用仿生矿化的方法制备纳米纤维素/纳米羟基磷灰石复合材料。并利用X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电镜能谱分析(SEM-EDAX)对仿生矿化前后纳米纤维素中碳、氧、钙、磷元素的变化情况及分布状态进行了表征,并探讨了纳米羟基磷灰石的生长机理。结果表明纳米纤维素表面形成了纳米羟基磷灰石;纳米纤维素的碳氧比为1.81,仿生矿化后下降为1.54;仿生矿化后纳米纤维素的钙磷比nCa/nP=1.70;纳米羟基磷灰石成核是在纳米纤维素的羟基上,并且纳米纤维素表面羟基和纳米羟基磷灰石的钙离子之间发生了配位作用。纳米羟基磷灰石较为均一的形成在纳米纤维素的基体中。通过原子力显微镜(AFM)图片可以看出,直径为20nm左右的羟基磷灰石生长在纳米纤维素的表面。     

近红外漫反射光谱法快速测定天然纤维素清洁浆料α-纤维素含量

针对天然纤维素清洁制浆新型连续生产工艺,提出了采用近红外漫反射光谱测定天然纤维素(棉、木浆粕)清洁浆料中α-纤维素含量。收集了142个天然纤维素清洁浆料样品,采用GB/T 9107—1999方法(化学分析方法)测定其α-纤维素含量。通过粉碎预处理提高样品的均匀性,继而压入旋转杯采集光谱。采用簇类独立软模式(SIMCA)方法建立了有效的棉浆粕和木浆粕的分类模型,模型识别率达到100%。基于偏最小二乘(PLS)法分别建立的全部样品以及分类棉、木浆粕的α-纤维素含量定量校正模型相关系数分别为0.954,0.911和0.839,SEP分别为2.4%,1.2%和1.6%,模型预测精密度与GB方法的允差接近,表明该方法是可行的,且操作简单,分析速度快,对提高天然纤维素清洁浆料α-纤维素含量分析效率和指导其连续生产具有积极意义。     

阳离子香豆胶热裂解红外光谱研究

研究了香豆胶原粉、阳离子香豆胶的红外光谱归属,并测定了它们的热失重及相应热效应峰值的红外光谱(TG-IR)。根据不同温度下阳离子香豆胶光谱基团的吸收峰变化和热失重-红外光谱的分析,推断该样品可能的热解过程。     

TiO_2掺杂粒度对纤维素强度和热稳定性影响的分子模拟研究

变压器绝缘纸的主要成分为纤维素,为了提升绝缘纸的强度和热稳定性,利用纳米TiO_2掺杂纤维素,通过分子模拟方法研究不同纳米TiO_2粒度掺杂纤维素的强度和热稳定性.研究表明,纳米TiO_2使得纤维素强度提高,拉伸模量增大,抗形变能力增强,体积模量与剪切模量比值(K/G)增大,纤维素韧性增强;纳米TiO_2表面羟基与纤维素形成新的氢键网络使得径向分布函数峰值增大,复合体系更加稳定,其热稳定性增强.掺杂比例相同时,随着纳米TiO_2粒度减小,拉伸模量和柯西压增大,泊松比减小,纤维素的抗形变能力增强;纳米TiO_2表面羟基占有率越高,纳米TiO_2与纤维素越易形成氢键抑制纤维素链运动,纳米TiO_2也减小复合体系的自由体积,使得复合体系结构更加稳定,热稳定性更强.因此,掺杂小纳米TiO_2粒度是提升纤维素强度和热稳定性有效的方法.     

MORPHOLOGY OF POLYURETHANES REVISITED BY COMPLEMENTARY AFM AND TEM

Cast, segmented polyetherurethanes with 30 and 50% hard-segment content (HSC), respectively, were studied by transmission electron microscopy (TEM) and atomic force microscopy (AFM). Multi-phase segregation was observed in both samples on two levels (micro and nano) of structural organization. Spherulites with a prominent radial structure, built of branched fibrils and globules, were captured on the micrometer level. The use of AFM enabled us to investigate the nanostructure in the polyurethanes studied here. In the sample with low (30%) HSC, nano-scale phase separation was observed by AFM in areas outside the crystalline aggregates. The morphology in these domains exhibited short, rodlike hard domains embedded in the matrix of the soft segments. The other sample (50% HSC) contained four identifiable morphological features. These included spherulites, globules, bundles of lamellae, and nanophase-separated, rodlike hard domains, embedded in the soft-segment matrix.

The globules did not have any internal structure visible by AFM down to the nanometer scale. We speculate that the globules form as a result of macro-phase segregation, due to incompatibility of the reactants, during synthesis and may thus be identified as pockets of free hard segments. The AFM phase imaging has been very useful to observe the bundles of lamellae and the nanoscale phase-separated structures, which were not captured by TEM, due to large differences in AFM phase signal contrast between the hard and the soft domains.     

Characterization of adsorbed arsenate on amorphous and nano crystalline MgFe-layered double hydroxides

This article investigated sorption of toxic and carcinogenic arsenate (AsO₄ ³⁻) ions on positively charged surface of amorphous and nano crystalline MgFe-layered double hydroxides (LDHs). Based on Brunauer–Emmett–Teller (BET) and Transmission Electron Microscopy (TEM), average size, and specific surface area of nano crystalline MgFe-LDHs, which was about range of about 50–200 nm and 90.2 m²/g, was lower and higher when compared to them of amorphous MgFe-LDHs, respectively. In addition, X-ray diffraction (XRD) peak and point of zero charge (PZC) of crystalline MgFe-LDHs was higher intensity and same, respectively, when compared to that of nano crystalline FeMg-LDHs. Adsorption rate of arsenate on amorphous MgFe-LDHs was a little faster when compared to that of nano crystalline MgFe-LDHs. In addition, as pH decreased, adsorption amount of arsenate on amorphous MgFe-LDHs increased significantly when compared to that of nano crystalline MgFe-LDHs. These results indicate that mechanism of arsenate in two materials was significantly different. We investigate sorption characteristic at pH 5, based on XRD and Fourier-transformed infrared (FTIR). In amorphous MgFe-LDHs, ferric arsenate precipitate was formed on surface of amorphous MgFe-LDHs and constituted the predominant surface arsenate. However, in nano crystalline MgFe-LDHs, arsenate was dominantly sorbed as a “non-surface-complexed” As–O bond on surface and anion exchange in interlayer.     

纳米ZnO的表面化学修饰及其分析表征

采用水溶性羟丙基甲基纤维素HPMC对无机纳米ZnO粒子进行物理吸附处理 ,获得了核为无机纳米ZnO ,外壳为水溶性高分子HPMC的粒子。然后在其上进行了甲基丙烯酸甲酯的接枝聚合。采用红外光谱、差热分析的方法对复合粒子进行了表征 ,并采用透射电镜观察了粒子的形貌。红外光谱表明在纳米ZnO的表面吸附了HPMC并接枝了PMMA ,差热分析表明HPMC ,HPMC g PMMA和ZnO/HPMC g PMMA的热稳定性逐渐提高 ,透射电镜观察表明 ,在纳米ZnO的表面粘附了一层聚合物 ,成功地实现了纳米粒子的表面修饰。     

纳米纤维素碱法制备及光谱性质

在纳米尺寸范围操控纤维素分子,由此创制出具有优异功能的新纳米材料是纤维素科学的前沿领域。纳米纤维素作为一种可再生生物材料已成为国内外研究热点,研究开发新型的简单、绿色、低能耗、快速、高效的纳米纤维素制备方法显得尤为重要。该研究采用简易可行的碱性水解法制备得到粒径较小且分散性较好的纳米纤维素。同时采用了电子显微镜、X射线粉末衍射仪和傅里叶红外光谱仪对所制备纳米纤维素进行了表征,研究了其结构与谱学性质。所制备样品为准球形纳米纤维素,颗粒尺寸约为20～40 nm,样品仍属于纤维素Ⅰ型,结晶度为79.71%,晶粒平均尺寸为3～6 nm。结果表明,碱水解法制备纳米纤维素方法具有简易可行、得率高的优点,研究可为纳米纤维素的高效制备提供一条新途径。     

Surface modifications by swift heavy-ion irradiation of indium phosphide

InP (001) samples were irradiated with 200 MeV Au ions at different fluences. The surface nanotopographical changes due to increasing fluence of swift heavy ions were observed by Atomic Force Microscopy (AFM), where the onset of a large increase in surface roughness for fluences sufficient to cause complete surface amorphization was observed. Transmission Electron Microscopy (TEM) was used to observe bulk-ion tracks that formed in InP, and high resolution TEM (HRTEM) revealed that single-ion tracks might not be amorphous in nature. Surface-ion tracks were observed by AFM in the form of ill-defined pits (hollows) of ~12 nm in diameter (width). In addition, Rutherford backscattering was utilized to follow the formation of disorder to amorphization in the irradiated material. The interpretation of the large increase in surface roughness with the onset of amorphization can be attributed to the plastic phenomena induced by the change of states from crystalline to amorphous by ion irradiation. The text was submitted by the authors in English.     

Microstructure of hydrogenated silicon thin films prepared from silane diluted with hydrogen

We report results obtained from FTIR and TEM measurements carried out on silicon thin films deposited by plasma-enhanced chemical vapor deposition (PECVD) from silane diluted with hydrogen. The hydrogen content, the microstructure factor, the mass density and the volume per Si-H vibrating dipoles were determined as a function of the hydrogen dilution. Hydrogen dilution of silane results in an inhomogeneous growth during which the material evolves from amorphous hydrogenated silicon (a-Si:H) to microcrystalline hydrogenated silicon (μc-Si:H). With increasing dilution the transition from amorphous to microcrystalline phase appears faster and the average mass density of the films decreases. The μc-Si:H films are mixed-phase void-rich materials with changing triphasic volume fractions of crystalline and amorphous phases and voids. Different bonding configurations of vibrating Si-H dipoles were observed in the a-Si:H and μc-Si:H. The bonding of hydrogen to silicon in the void- and vacancy-dominated mechanisms of network formation is discussed.     

Characterization of nanosized partly crystalline photocatalysts

A thorough analysis of nanosized partly crystalline photocatalysts has been carried out. X-ray diffraction (XRD), Small angle X-ray Scattering (SAXS), Scanning electron microscope (SEM), and BET measurements have been applied to study the particle properties of different photocatalysts. The study permitted the determination of absolute crystallinity of partly and fully crystalline photocatalysts by XRD. The absolute crystallinity was determined with CaF₂ as a reference. SAXS measurements were used to study the morphology and to determine the primary particle size of the investigated photocatalysts. The study showed that the commercially available photocatalyst Hombikat UV100 consisted of a great fraction of amorphous material whereas Degussa P25 was found to be almost crystalline. A homemade sample was found to be 63% crystalline anatase and 37% amorphous. The study also revealed that there was a deviation between the primary particle size and the crystal size for the partly crystalline samples caused by the amorphous fraction; however, the fully crystalline Degussa P25 had agreement between the primary particle size and the crystal size.     

On the morphology of cellulose nanofibrils obtained by TEMPO-mediated oxidation and mechanical treatment

The morphological properties of cellulose nanofibrils obtained from eucalyptus pulp fibres were assessed. Two samples were produced with the same chemical treatment (NaClO/NaBr/TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical) oxidation), but distinct mechanical treatment intensities during homogenization. It was shown that the nanofibrils production yield increases with the mechanical energy. The effect of mechanical treatment on the yield was confirmed by laser profilometry of air-dried nanocellulose films. However, no significant differences were detected regarding the nanofibrils width as measured by atomic force microscopy (AFM) of air-dried films. On the other hand, differences in size were found either by laser diffraction spectroscopy or by dynamic light scattering (DLS) of the cellulose nanofibrils suspensions as a consequence of the differences in the length distribution of both samples. The nanofibrils length of the more nanofibrillated sample was calculated based on the width measured by AFM and the hydrodynamic diameter obtained by DLS. A length value of ca. 600 nm was estimated. The DLS hydrodynamic diameter, as an equivalent spherical diameter, was used to estimate the nanofibrils length assuming a cylinder with the same volume and with the diameter (width) assessed by AFM. A simple method is thus proposed to evaluate the cellulose nanofibrils length combining microscopy and light scattering methods.     

Sono-assisted TEMPO oxidation of oil palm lignocellulosic biomass for isolation of nanocrystalline cellulose

Highly stable and dispersible nanocrystalline cellulose (NCC) was successfully isolated from oil palm empty fruit bunch microcrystalline cellulose (OPEFB-MCC), with yields of 93% via a sono-assisted TEMPO-oxidation and a subsequent sonication process. The sono-assisted treatment has a remarkable effect, resulting in an increase of more than 100% in the carboxylate content and a significant increase of approximately 39% in yield compared with the non-assisted process. TEM images reveal the OPEFB-NCC to have rod-like crystalline morphology with an average length and width of 122 and 6 nm, respectively. FTIR and solid-state ¹³C-NMR analyses suggest that oxidation of cellulose chain hydroxyl groups occurs at C6. XRD analysis shows that OPEFB-NCC consists primarily of a crystalline cellulose I structure. Both XRD and ¹³C-NMR indicate that the OPEFB-NCC has a lower crystallinity than the OPEFB-MCC starting material. Thermogravimetric analysis illustrates that OPEFB-NCC is less thermally stable than OPEFB-MCC but has a char content of 46% compared with 7% for the latter, which signifies that the carboxylate functionality acts as a flame retardant.     

A novel application for oil palm empty fruit bunch: extraction and modification of cellulose for solid polymer electrolyte

Biopolymer-based materials from renewable sources are the core target of the researchers in modern time. Following this motivation, we have developed solid polymer electrolytes (SPEs) from empty fruit branch (EFB) of oil palm. The cellulose was extracted from EFB and modified to carboxymethyl cellulose (CMC) by its reaction with monochloroacetic acid in a strongly alkaline medium. The samples were characterized by FTIR, ¹³C NMR, and XRD to confirm the presence of different functional groups, new connectivity, and crystalline/amorphous nature of the materials, respectively. The CMC-based SPEs were fabricated by blending it with different quantities of lithium iodide (LiI) as dopant. The existence of polymer-salt interactions was revealed by FTIR analysis. The maximum ionic conductivity of 5.58?×?10^?3 S cm^?1 was observed on sample containing 65 wt% LiI with the lowest activation energy of 0.249 eV.