Fourier transform infrared imaging and microscopy studies of Pinus radiata pulps regarding the simultaneous saccharification and fermentation process

The distribution and chemical patterns of lignocellulosic components at microscopic scale and their effect on the simultaneous saccharification and fermentation process (SSF) in the production of bioethanol from Pinus radiata pulps were analyzed by the application of diverse microscopical techniques, including scanning electronic microscopy (SEM), confocal laser scanning microscopy (CLSM) and attenuated total reflectance (ATR) – Fourier transform infrared microspectroscopy. This last technique was accompanied with multivariate methods, including principal component analysis (PCA) and multivariate curve resolution with alternating least squares (MCR-ALS) to evaluate the distribution patterns and to generate pure spectra of the lignocellulosic components of fibers. The results indicate that the information obtained by the techniques is complementary (ultrastructure, confocality and chemical characterization) and that the distribution of components affects the SSF yield, identifying lignin coalescence droplets as a characteristic factor to increase the SSF yield. Therefore, multivariate analysis of the infrared spectra enabled the in situ identification of the cellulose, lignin and lignin-carbohydrates arrangements. These techniques could be used to investigate the lignocellulosic components distribution and consequently their recalcitrance in many applications where minimal sample manipulation and microscale chemical information is required.     

Improved surface properties of CTMP fibers with enzymatic pretreatment of wood chips prior to refining

Surface properties of chemithermomechanical pulp (CTMP) fibers produced from enzymatically pretreated eucalyptus wood chips prior to refining were investigated by Field Emission Scanning Electron Microscope (FE-SEM), Transmission Electron Microscope (TEM) and X-ray Photoelectron Spectroscopy (XPS). The results showed that in a traditional CTMP refining process most fiber disruptions occur in the middle lamella (ML) leaving behind a significant amount of hydrophobic materials on the resulting fiber surface. However, in a Bio-CTMP refining process, fiber fractures preferentially take place in the primary (P) and secondary 1 (S1) layers or the S1 and secondary 2 (S2) layers, which results in more fibrillation being generated in the subsequent refining thus improving inter-fiber bonding strength and paper strength. XPS chemical composition analysis together with pulp physical strength property showed that the surfaces of Bio-CTMP fibers become enriched with a greater proportion of carbohydrates in comparison with CTMP fiber surface, which supports FE-SEM and TEM observations.     

Single stage purification of flax,hemp, and milkweed stem and their physical and morphological properties

Agriculture biomass is an alternative possible solution for the extraction of cellulose, compared to the classical soft and hard wood. However, the valorization of cellulose is challenging for the researchers as it involves multiple steps. In the present study, the raw fibers of flax, hemp, and milkweed stem fibers were purified in single step using hydrogen peroxide in water. By this method authors successfully extracted the purified cellulose fibers without damaging the fiber length. The purified fibers were characterized to understand the thermal, functional, crystalline, and morphological properties by thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and scanning electron microscopy (SEM). The FTIR results showed the effective removal of lignin and significant improvement in thermal stability was observed by TGA. Evidently, the SEM results showed significant improvement in the morphology compared to that of the raw fibers. XRD results showed that the treatment does not affect the crystallinity of the fibers.     

The middle lamella remainders on the surface of various mechanical pulp fibres

The surfaces of various mechanical pulp fibres, including thermomechanical pulp (TMP), chemithermomechanical pulp (CTMP), and alkaline peroxide mechanical pulp (APMP) fibres, were characterized using scanning electron microscopy (SEM), atomic force microscopy (AFM), and X‐ray photoelectron spectroscopy (XPS). With SEM and AFM, the middle lamella material was observed to be non‐fibrillar and patch‐like, while the fibre secondary wall was observed to have a micro‐fibrillar structure. It was found that after the first‐stage refiner, lignin‐rich middle lamella remainders were present on the fibre surface of all three pulps, although most of the fibre surfaces exhibited a micro‐fibrillar structure. After the final‐stage refining, large amounts of granules were present on the TMP fibre surface. In contrast, most middle lamella remainders were still visible on the surface of CTMP fibres after the final‐stage refining and even after peroxide bleaching. XPS results have confirmed that the non‐fibrillar surface material is the lignin‐rich middle lamella remainder that contribute to the high surface lignin concentration. Copyright © 2006 John Wiley & Sons, Ltd.     

Preparation and characterization of cationic nanofibrillated cellulose from etherification and high-shear disintegration processes

Oat straw cellulose pulp was cationized in an etherification reaction with chlorocholine chloride. The cationized cellulose pulp was then mechanically disintegrated in two process steps to obtain trimethylammonium-modified nanofibrillated cellulose (TMA-NFC). The materials thus obtained were analyzed by elemental analysis, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), scanning electron microscopy (SEM) and other techniques. A higher nitrogen content of TMA-NFC samples was found by XPS analysis than by elemental analysis, which indicates that the modification occurred mainly on the surface of cellulose fibrils. XPS also confirmed the existence of ammonium groups in the samples. SEM provided images of very fine network structures of TMA-NFC, which affirmed the positive effect of ionic charge on mechanical disintegration process. According to XRD and SEM results, no severe degradation of the cellulose occurred, even at high reaction temperatures. Because of the different properties of the cationic NFC compared to negatively charged native cellulose fibers, TMA-NFC may find broad applications in technical areas, for instance in combination with anionic species, such as fillers or dyes. Indeed, TMA-NFC seems to improve the distribution of clay fillers in NFC matrix.     

Monitoring the polymerization process of polypyrrole films by thermogravimetric and X-ray analysis

Bio-composite fibers were developed from wood pulp and polypropylene (PP) by an extrusion process. The thermo-physical and mechanical properties of wood pulp-PP composite fibers, neat PP and wood pulp were studied using thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA). The thermal stability of bio-composite fibers was found to be significantly higher than pure wood pulp. An understanding into the melting behaviour of the composite system was obtained which would assist in selecting a suitable temperature profile for the extruder during processing. The visco-elastic properties of bio-composite fibers were also revealed from the study. The generated bio-composite fibers were also characterized using Fourier transform infrared spectroscopy (FTIR) to understand the nature of chemical interaction between wood pulp reinforcement and PP matrix. The use of maleated polypropylene (MAPP) as a compatibilizer was investigated in relation to the fiber microstructure. Changes in absorption peaks were observed in FTIR spectra of bio-composite fibers as compared to the pure wood pulp which indicated possible chemical linkages between the fiber and polymer matrix.     

Fourier transform Raman spectroscopic studies of a novel wood pulp bleaching system

The use of near-infrared (NIR) Fourier transform (FT) Raman spectroscopy for the study of lignocellulosic materials is discussed. An application utilizing NIR FT-Raman spectroscopy to study a novel chlorine-free process for the bleaching of wood pulps is presented in detail. The new process, still under development, entails the oxidation of residual lignin in wood pulps by vanadium-substituted polyoxometalates, and reoxidation of the reduced polyoxometalates by chlorine-free oxidants such as air, dioxygen, peroxides or ozone. Results from FT-Raman measurements of polyoxometalate-treated pulps are compared with those from chemical, spectroscopic and optical techniques commonly used in the pulp and paper industry.     

Sorption of spruce O-acetylated galactoglucomannans onto different pulp fibres

Sorption of spruce acetylated galactoglucomannans (GGM) onto different pulps, among which unbleached and peroxide-bleached mechanical pulps, and unbleached and bleached kraft (BK) pulps, was studied as a means of understanding the retention of acetylated GGMs in mechanical pulping and papermaking. The fibre surface coverage of lignin and carbohydrates was estimated by X-ray photoelectron spectroscopy (XPS) or electron spectroscopy for chemical analysis (ESCA). GGM sorption was clearly favoured on kraft pulps. Hardly any differences in sorption were, however, observed between unbleached and BK pulps, even if the surface coverage of lignin was lower on the bleached pulp. Neither thermomechanical pulp (TMP) nor chemithermomechanical pulp (CTMP) manufactured from spruce sorbed any acetylated GGMs. Peroxide bleaching of the pulp did not increase sorption. Only CTMP produced from aspen sorbed some GGMs. The anionic charge of neither chemical nor mechanical pulps influenced GGM sorption.     

Preparation and characterization of biodegradable sugarcane bagasse nano reinforcement for polymer composites using ball milling operation

The present work includes the processing and characterization of nano-based natural reinforcement for polymer composite materials. Sugarcane bagasse has been collected and the fibers were extracted using manual striping process. Undesirable materials present in the extracted fibers were removed by 1% NaOH-based chemical treatment. The macrofibers were reduced to nano scale by using high-energy ball milling process. Nanoparticles from bagasse fibers were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and thermogravimetric analysis (TGA). The degree of crystallinity of nano bagasse is 55.2% and it was reported by using XRD. A FTIR spectrum confirms the presence of cellulose functional groups in nano bagasse. The nano bagasse dimensions and morphology were investigated using SEM. The average length and diameter of the nano bagasse is 51.2 and 46.1 nm, respectively. Thermal stability of the nano bagasse was revealed by TGA analysis. The chemical composition of cellulose, lignin, and hemicellulose contents was also investigated.     

Influence of bath temperatures on the wettability of copper films surface prepared by electroless plating method on beech wood

Copper films were coated on beech wood substrates by electroless plating method. The influence of bath temperature on the copper films properties was studied by varying the bath temperatures 25, 35, 45 and 55 °C. Scanning electron microscopy (SEM) equipped with energy dispersive spectroscopy (EDS), X‐ray diffraction (XRD) pattern, X‐ray photoelectron spectroscopy (XPS), micro Raman spectroscopy and contact angle measurements were used to both characterize the physical and chemical copper films properties and understand the influence of bath temperature on the wettability of copper surface. In our studies, we have found that the gained copper mass significantly increased at 55 °C. The crystalline nature of the coated copper was confirmed by XRD. The presence of Cu₂O and CuO was observed by XPS and micro Raman techniques, which confirms the oxidization of the coated copper surface. Also these characterization techniques have shown the big influence of bath temperature on the morphology, grain size, chemical composition and the film thickness of the coated copper. The wettability was highly influenced by increasing CuO on the coated copper, which is increased by the bath temperature. The contact angle measurements have demonstrated the influence of C―O, O―C?O and CuO components of the surface on the wettability of the samples. Copyright © 2016 John Wiley & Sons, Ltd.     

Imaging Nanocarbon Materials: Soot Particles in Flames are Not Structurally Homogeneous

For the first time, nascent soot particles are probed by using helium‐ion microscopy (HIM). HIM is a technique that is similar to scanning electron microscopy (SEM) but it can achieve higher contrast and improved surface sensitivity, especially for carbonaceous materials. The HIM microscope yields images with a high contrast, which allows for the unambiguous recognition of smaller nascent soot particles than those observed in previous transmission electron microscopy studies. The results indicate that HIM is ideal for rapid and reliable probing of the morphology of nascent soot, with surface details visible down to approximately 5 nm, and particles as small as 2 nm are detectable. The results also show that nascent soot is structurally and chemically inhomogeneous, and even the smallest particles can have shapes that deviate from a perfect sphere.     

A new study on effect of various chemical treatments on Agave Americana fiber for composite reinforcement: Physico-chemical,thermal, mechanical and morphological properties

This research is focused to fundamentally understand the benefits of using Agave Americana C. plant as potential reinforcement in polymeric composites. The fibers were extracted from the external part of the bark of the plant, which grows worldwide in pastures, grasslands, open woodlands, coastal and riparian zones. In order to use the natural fiber as reinforcement it is paramount important to probe their chemical composition, microstructural behavior and mechanical properties. Hence, firstly the extracted fibers were chemically treated with NaOH, stearic acid, benzoyl peroxide and potassium permanganate. The chemical composition in terms of cellulose, hemicellulose, lignin and other waxy substances were determined using a standard TAPPI method. FT-IR technique was used to understand the character of molecular bonds, crystallinity and their correlations with various bonds in fiber structure. The thermal stability was investigated through thermogravimetric and differential scanning calorimetric analysis, and the mechanical characterization was performed by applying standard tensile test. The surface morphology of fibers was examined through scanning electron microscopy (SEM) and finally reliability scrutiny of all the analysis was carried out. The results of chemical modification techniques applied on the surfaces of natural fibers allows to produce superior fibers used to form the novel composite materials for light-weight application.     

Characterization of fossil Sequoioxylon wood using analytical instrumental techniques

In this study, fossil (Sequoioxylon) wood from the Oligocene–Miocene transition in İstanbul, Turkey was examined using non-destructive test methods to evaluate changes in anatomical and chemical structure. Molecular changes in the cell wall structure of the wood were determined using Fourier transform infrared (FTIR) and FT-Raman spectroscopy, along with the comparison to recent wood [Sequoiadendron giganteum (Lindl.)]. We found that the cell wall carbohydrates of the fossil wood were significantly more degraded compared with lignin; FT-Raman spectroscopy revealed the degradation in more detail compared with FTIR spectroscopy. FT-Raman spectra also demonstrated that hemicellulose and holocellulose were decreased in the fossil wood. Laser-induced breakdown spectroscopy (LIBS) analysis confirmed that the mass loss was due to the decreased H and O content of the fossil wood sample and was caused by decomposition. Light microscopy also showed that fossil and recent woods have similar anatomic structures, and that the micro-morphological structure of the fossil wood was well-preserved.     

Physico-chemical and anatomical characterization of residual lignocellulosic fibers

Anatomical and physico-chemical properties of residual natural fibers (sugarcane bagasse, coconut fibers and peanut hulls) were characterized in order to evaluate their potential for use in the production of particleboard. The bulk density was determined by helium pycnometer and the chemical characteristics by using an electronic pH meter (for pH determination) on fibers dissolved in acidic and neutral detergents (to determine the levels of cellulose, hemicellulose and lignin). The anatomical characteristics were established using scanning electron microscopy coupled with an X-ray detector system, as well as energy dispersive X-ray spectroscopy. Results indicated similarities and differences between physico-chemical and anatomical characteristics of the residual lignocellulosic fibers when compared with the Pinus sp. wood commercially employed in particleboard production. Bulk density and pH for residual lignocellulosic fibers and Pinus sp. wood presented analogous values. Similar amounts of cellulose and lignin were identified between waste fibers and Pinus sp. wood. The presence of silica was identified in coconut fiber, peanut hull and sugarcane bagasse waste fibers, and may affect the mechanical characteristics of panels. Coconut and sugarcane bagasse fibers show surface pores with diameters ranging from 1.2 to 2.1 μm, below the 5 μm identified for Pinus sp. wood. Both fibers present pores distributed over their entire surface, whereas peanut hull fibers have no pores on their surface. This characteristic contributes to resin dispersion among particles, reflecting positively on the physical–mechanical properties of the panels. Particleboards produced with residual lignocellulosic fibers present similar physical–mechanical properties to those of Pinus sp. wood panels.     

Structure and Properties of Electrochemically Synthesized Silver Nanoparticles in Aqueous Solution by High-Resolution Techniques

The aim of this work was to deeply investigate the structure and properties of electrochemically synthesized silver nanoparticles (AgNPs) through high-resolution techniques such as transmission electron microscopy (TEM), scanning electron microscopy (SEM), Zeta Potential measurements, and matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOF-MS). Strong brightness, tendency to generate nanoclusters containing an odd number of atoms, and absence of the free silver ions in solution were observed. The research also highlighted that the chemical and physical properties of the AgNPs seemed to be related to their peculiar oxidative state as suggested by X-ray photoelectron spectroscopy (XPS) and X-ray powder diffraction (XRPD) analyses. Finally, the MTT assay tested the low cytotoxicity of the investigated AgNPs.     

Precipitation of lignin and extractives on kraft pulp: effect on surface chemistry, surface morphology and paper strength

The effect of pH on the formation of precipitates (lignin, extractives and metals) on kraft pulp surfaces was examined by electron spectroscopy for chemical analysis, time-of-flight secondary ion mass spectrometry and atomic force microscopy (AFM). A softwood kraft pulp slurry from an oxygen delignification stage was diluted to 3% consistency with water or an acidic Z filtrate. After heating to 70 °C the pH was lowered from 11 to 2–5, using sulphuric acid. Lignin and extractives precipitated at pH values below 6, and their amounts increased with decreasing pH. Most of the precipitated lignin was found on the pulp surface after sheet forming, whereas the main part of the precipitated extractives could be easily washed away with water. The layer of precipitated lignin was apparently thicker than the layer of extractives. AFM showed the precipitated material as a granular phase. Neither surface morphology nor surface coverage depended on the addition of Z filtrate. The amount of metals ID the pulp and on the pulp surface decreased when pH was lowered to 2. More metals, such as Ca and Mg, were detected ID the pulps as well as on the sheet surfaces when the pulp was diluted with Z filtrate. Strength and bonding properties of the pulp sheets were slightly impaired by the precipitated material. Acidification appears to be the main reason for the precipitation of both lignin and extractives on the pulp surfaces. This should be taken into account when filtrates are recycled ID the bleaching or washing of pulps.     

Rapid Characterization of Wood Pulp Lignin by Fourier Transform Raman Spectroscopy

FT-Raman spectroscopy is used for the rapid measurement of wood pulp lignin. A total of 23 western softwood pulp samples with known kappa numbers (10–38) are used. Each sample is divided into three portions and scanned separately. The integrated area of the lignin band at approximately 1600 cm⁻¹is ratioed against the integrated area of the cellulose bands in the 1200–1010 cm⁻¹region and correlated to known kappa numbers. The measured ratios behave linearly with the kappa number (r= 0.99) and can be reproducibly determined with an error of approximately 2% or less. The data are presented and discussed in view of the potential for at-line analysis of lignin associated with chemical delignification of wood pulp.     

Castor oil-based biopolyurethane reinforced with wood microfibers derived from mechanical pulp

Wood fibers with high lignin content show promise to function in numerous applications with advantageous properties if the fiber features are appropriately exploited. The present study introduces a new approach to disintegrate and disperse wood fibers from groundwood pulp (GWP) directly to polyol without additional solvent exchanges or chemical modifications. In comparison bleached chemical pulp with low lignin content was ground in the polyol, but only low consistency (1 wt%) operation was possible, whereas up to 5 wt% consistency with GWP was carried out with ease. The micron sized fibers in polyol were reacted with polymeric diphenylmethane diisocyanate to produce fiber reinforced biopolyurethane (bioPU) composites. The mechanical properties of the composites improved compared to reference bioPU showing 14.6% increase in Young’s modulus, 54.5% in tensile strength and 26.1% in strain at break. The tan δ peaks shifted to higher temperature from 5.5 to 10.4 °C when fibers up to 5.1 wt% were incorporated to bioPU. Overall, the bulk microfibers from GWP with low degree of processing were cost-effective reinforcements for bioPUs, which improved the qualities of the fabricated composites and showed good compatibility with polyurethane.     

CP/MAS 13C-NMR技术对桉木浆纤维素微观结构的研究

利用交叉极化结合魔角旋转技术13C 核磁共振法(CP/MAS ¹³C NMR)对桉木浆纤维的微观结构进行研究, 为进一步研究木质纤维素材料开发过程中反应障碍特征奠定基础. 通过对NMR光谱C1区(δ 102～108)进行洛仑兹拟合, 得到桉木浆纤维中纤维素Iα的相对含量为26.92%, 纤维素Iβ的相对含量为52.04%, 主要以纤维素Iβ晶体形式为主. 通过计算纤维素C4结晶区(δ 86～92)和非结晶区(δ 80～86)的相对含量得到桉木浆的纤维素结晶度为47%. 通过洛仑兹和高斯函数的混合模型对NMR光谱C4区(δ 80～92)进行拟合得到基原纤尺寸和微原纤横向尺寸分别为4.0与17.9 nm, 并通过计算不同形态的结晶纤维素的相对含量得到纤维素结晶度为51%, 证实了在微原纤内部次晶纤维素的存在.     

Fragment analysis of different size-reduced lignocellulosic pulps by hydrodynamic fractionation

Micro- and nanocelluloses are typically produced using intensive mechanical treatments such as grinding, milling or refining followed by high-pressure homogenization to liberate individual nano- and microcellulose fragments. Even though chemical and enzymatic pretreatments can be used to promote fiber disintegration, the required mechanical treatments are still highly energy consuming and very costly. Therefore, it is important to understand the kinetics and factors affecting the disintegration tendency of cellulose. In this study, the disintegration tendency of three different wood cellulose pulps with varying chemical composition processed in a PFI mill was examined by analyzing the fractional composition of the microparticles formed. The fractional compositions of the microfibrils and microparticles formed were measured with novel analyzers, which fractionated particles using a continuous water flow in a long tube. The hydrodynamic fractionators used in this study gave valuable information about different size of particles. Results showed that the amount of lignin and hemicelluloses clearly affected the kinetics and the mechanics of cellulose degradation. The P and S1 layers were peeled off from the Kraft fibers, causing the S2 layer to be cropped out. The thermomechanical pulp (TMP) fibers were first degraded by comminution and delamination from the middle lamella and the primary wall. As the refining process progressed, the fibers and fiber fragments began to unravel. Surprisingly, the semi-chemical pulp (SCP) fibers degraded more like Kraft fibers than TMP fibers despite their high lignin and extractive content.