Effects of HCl hydrolyzed cellulose nanocrystals from waste papers on the Hydroxypropyl methylcellulose/Cationic Starch biofilms

ABSTRACT The study reports on the preparation of nanocrystalline cellulose from waste papers (WPNCC), as an environmental friendly approach of source material and investigation of their effects on the morphological, mechanical and barrier properties of the Hydroxypropyl methylcellulose/Cationic starch (HPMC/CS) nanocomposites. HCl hydrolysis followed by alkali treatment and deinking of the fibers resulted in the production of WPNCC. The TEM results confirmed the rod like shape of WPNCC; the average diameter was 22± 7 nanometers and the length was 125± 25 nanometers. The hydrolysis yield was 65% with high crystallinity index of 79.6%. The results of X-ray diffraction confirmed the successfully production of WPNCC and their effective presence in the HPMC/CS matrix. The homogeneity of WPNCC dispersion in the polymer matrix was approved by FESEM analysis. The WPNCC also did not affect the nanocomposites optical clarity. The optimum amount of 9 wt% WPNCC, showed the highest barrier, mechanical and biodegradablility properties.

Effect of Chemical Treatment Sequence on Pineapple Peel Fiber: Chemical Composition, Thermal Stability and Thermal Degradation Kinetics

Millions of tons of fruit wastes are generated globally every year from residual agriculture, which makes essential to find alternative uses to increase their aggregate value and reduce the impact of environmental damage. The present study aimed to explore pineapple peel as an alternative source of cellulose by evaluating its composition and physical properties, which are essential to provide a clue to its application function diverse. Cellulose was extracted by a sequence of chlorine-free treatments to delignify the fresh pineapple peels, followed by characterization using chemical composition, XRD, FTIR, SEM and TGA to determine its crystallinity, structural properties, morphology thermal characteristics, and thermal degradation kinetic study. The result revealed that the pineapple peel amorphous segments containing hemicelluloses and lignin were extensively removed with increasing chemical treatments, leading to increased purity, crystallinity index and thermal stability of the extracted materials. The maximum degradation, and crystallinity index of the 2B isolated from the PPF are 150 °C and 80.91% respectively. The cellulose content increased from 24.05% (pineapple peel) to 80.91% (bleached cellulose). These results indicated that pretreatment via bleaching has suitable potential applications in nanocrystal production and suggests possible uses in the development of cellulose nanocrystal and application for packaging films.

Synthesis of Green Deep Eutectic Solvents for Pretreatment Wheat Straw: Enhance the Solubility of Typical Lignocellulose

Deep eutectic solvents (DESs), a novel and environmentally-friendly solvent, have high potential for biomass pretreatment due to its advantages of low cost, low toxicity, strong solubility, excellent selectivity and biocompatibility. Two types of DES (binary and ternary) were synthesized and characterized, and optimized ternary DES was selected to pretreat wheat straw for enhancement of the solubility of lignocellulose. Moreover, enzymatic hydrolysis was tested to verify the performance of pretreatment. In addition, the changes in surface morphology, structure and crystallinity of wheat straw pretreated by DES were analyzed to reveal the pretreatment mechanism. Experimental results indicated that viscosity exhibited little difference in different types of DESs, and a declining trend as the temperature increases in same DES. The ternary DES pretreatment efficiently enhanced the solubility of typical lignocellulose, with the optimal removal rate of lignin at approximately 69.46%. Furthermore, the total sugar concentration of the residue was about 5.1 times more than that of untreated wheat straw after the pretreated samples were hydrolyzed by the cellulase for 24 h, indicating that DES has the unique ability to selectively extract lignin and hemicellulose from wheat straw while retaining cellulose, and thus enhanced the solubility of lignocellulose. The scanning electron microscope (SEM) observation and X-ray diffraction (XRD) determination showed that the surface of wheat straw suffered from serious erosion and the crystallinity index of wheat straw increased after DES5 pretreatment. Therefore, DES cleaves the covalent bond between lignin and cellulose and hemicellulose, and reduces the intractability of lignin resulting in the lignin dissolution. It suggests that DES can be used as a promising and biocompatible pretreatment way for the cost-effective conversion of lignocellulose biomass into biofuels.

Ubim Fiber (Geonoma baculífera): A Less Known Brazilian Amazon Natural Fiber for Engineering Applications

The production of synthetic materials generally uses non-renewable forms of energy, which are highly polluting. This is driving the search for natural materials that offer properties similar to synthetic ones. In particular, the use of natural lignocellulosic fibers (NLFs) has been investigated since the end of 20th century, and is emerging strongly as an alternative to replace synthetic components and reinforce composite materials for engineering applications. NLFs stand out in general as they are biodegradable, non-polluting, have comparatively less CO2 emission and are more economically viable. Furthermore, they are lighter and cheaper than synthetic fibers, and are a possible replacement as composite reinforcement with similar mechanical properties. In the present work, a less known NLF from the Amazon region, the ubim fiber (Geonoma bacculifera), was for the first time physically characterized by X-ray diffraction (XRD). Fiber density was statistically analyzed by the Weibull method. Using both the geometric method and the Archimedes’ technique, it was found that ubim fiber has one of the lowest densities, 0.70–0.73 g/cm3, for NLFs already reported in the literature. Excluding the porosity, however, the absolute density measured by pycnometry was relatively higher. In addition, the crystallinity index, of 83%, microfibril angle, of 7.42–7.49°, and ubim fiber microstructure of lumen and channel pores were also characterized by scanning electron microscopy. These preliminary results indicate a promising application of ubim fiber as eco-friendly reinforcement of civil construction composite material.

Study on the Evaluation of Thermal Damage According to the Manufacturing Conditions of Korean Paper

In this study, we aimed to analyze the chemical changes that occur in Korean paper in an accelerated deterioration environment of 105℃. We selected the Korean paper produced with different types of cooking agents (plant lye, Na2CO3) and during different manufacturing seasons (winter, summer). The degree of deterioration of the Korean paper was confirmed by measuring the brightness, yellowness, and pH level, and the degree of change in each vibrational region of cellulose as deterioration progressed through infrared (FT-IR) spectroscopy. The FT-IR analysis showed that, as deterioration progressed, the absorbance of the amorphous region in cellulose decreased, whereas the absorbance of the crystalline region slightly increased. X-Ray diffraction (XRD) analysis and Raman spectroscopy were performed to verify the changes in the crystalline and amorphous regions in cellulose indicated by the FT-IR results. Furthermore, the crystallinity index (CI) was calculated; it showed a slight increase after deterioration; therefore, CI was confirmed to follow the same trend as that observed for absorbance in the FT-IR results. In addition, as a result of Raman spectroscopic analysis, the degree of decomposition of the amorphous region in the cellulose under the manufacturing conditions was confirmed by the fluorescence measured after the deterioration.

Extraction of Lignin from Empty Fruit Bunch Fiber via Microwave-Assisted Deep-Eutectic Solvent Heating

This work study about the extraction of lignin from Empty Fruit Bunch (EFB). It is a type of lignocellulosic waste produced during the palm oil extraction process. There are three main components of lignocellulosic, which is one of them is lignin. A deep eutectic solvent (DES) with microwave-assisted heating has been used as a process to extract the lignin from EFB and turn it into a value-product. This convenient method was started with the mixing of EFB and DES. After that, the mixture was heated via microwave synthesis reactor at different temperature and time parameters. The extracted lignin yield was dried and ground into a powder form. The highest lignin yield recovered is 30 % by the highest time and temperature. Interestingly, the purity of all lignin yields are above than 80 %. The highest yield of lignin was characterized. According to Fourier-Transform Infrared (FTIR) spectra, there was a significant functional group of phenolic and aliphatic hydroxyl in lignin. Besides, the methoxy group was also configured in lignin spectra. The presence of conjugated alkene also conveyed the characteristic of lignin. The FTIR spectra were intensified with 1H Nuclear Magnetic Resonance (NMR) spectra where there was a chemical shift in lignin and raw EFB which was designated to aliphatic and aromatic protons bonded to a carbon atom. Three regions of decomposition occur in the Thermogravimetric Analysis (TGA) spectra. The initial decompose temperature of lignin was lower compare to raw EFB. Next, second-stage lignin decomposed at 434.14 ℃ with weight loss of 36.21 %. Lastly, for the final stage, lignin decomposes at 552.54 ℃. Moreover, Differential Scanning Calorimetry (DSC) spectra demonstrate that the Tg value of lignin managed to be identified. However, the Tg value of raw EFB cannot be well defined. As for the characterization in residual fractions of EFB, the lowest crystallinity index (CrI) value of raw EFB has proven the presence of lignocellulosic in its structure. The residual fractions that reacted at higher temperatures have an inflated value of CrI as they contain abundant left out cellulose.

Infrared Spectroscopic Analysis of the Inorganic Components from Teeth Exposed to Psychotherapeutic Drugs

Teeth are unique and complex anatomical organs that can provide relevant data about a person's health, and play an important role in forensic medicine. Teeth are exposed to food, drinks, and the microbiota of the oral cavity; therefore, they have developed a high resistance to localized demineralization. Nevertheless, the continuous demineralization–remineralization cycle present in the oral environment can be influenced by stress, medication, mineralization agents, and other factors such as individual habits, especially diet. In this study, based on attenuated total reflectance Fourier-transform infrared spectroscopy (ATR-FTIR) spectra from tooth samples of 36 patients, several parameters were estimated: the crystallinity index (CI), the phosphate/amide I ratio, and the carbonate/phosphate ratio. In addition, in eight representative samples (six of the root of the tooth and two of the enamel area of the crown), additional characterization by X-ray powder diffraction (XRPD), scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) was conducted. From the FTIR data, it was observed that the highest CI values were found in patients who smoked. Further, in both root and crown samples, the intensity of the absorption band corresponding to PO43- increased in patients undergoing treatment with psychotherapeutic drugs. On the other hand, the intensity of the absorption band of the amide I group decreased with medical treatment and with the patient's biological age. Moreover, it was found that the remineralization process was more active in enamel than in the root due to direct contact with saliva. Regarding the results obtained from the X-ray powder diffractograms, exposure to psychotherapeutic drugs affected the definition of the peaks corresponding to hydroxyapatite, both in the crown and root samples. Concerning SEM results, qualitative differences in the stratification process in demineralized surfaces were observed, and EDS analyses showed some differences in the Ca/P ratio between pathological samples and control ones, but without clear patterns. The above techniques, in particular ATR-FTIR, showed promise for the investigation of the effect of changes produced in the hydroxyapatite structure in teeth and, consequently, to determine possible strategies in the diagnostic protocol.

Study on Combustion Characteristics and Thermodynamic Parameters of Thermal Degradation of Guinea Grass (Megathyrsus maximus) in N2-Pyrolytic and Oxidative Atmospheres

This study provides an extensive investigation on the kinetics, combustion characteristics, and thermodynamic parameters of the thermal degradation of guinea grass (Megathyrsus maximus) in N2-pyrolytic and oxidative atmospheres. A model-fitting technique and three different iso-conversional techniques were used to investigate the kinetics of the thermal process, after which an analysis of the combustion characteristics and thermodynamic parameters was undertaken. Prior to this, experiments on the physico-chemical characterization, thermogravimetric, and spectroscopic analyses were carried out to provide insight into the compositional structure of the guinea grass. The volatile matter, fixed carbon, and total lignin contents by mass were 73.0%, 16.1%, and 21.5%, respectively, while the higher heating value was 15.46 MJ/kg. The cellulose crystallinity index, determined by XRD, was 0.43. The conversion of the GG in air proceeded at a relatively much higher rate as the maximum mass-loss rate peak in a 20 K/min read was −23.1 and −12.3%/min for the oxidative and the pyrolytic, respectively. The kinetics investigation revealed three distinctive stages of decomposition with their corresponding values of activation energy. The average values of activation energy (FWO) at the latter stages of decomposition in the pyrolytic processes (165 kJ/mol) were higher than those in the oxidative processes (125 kJ/mol)—an indication of the distinctive phenomenon at this stage of the reaction. The Coats–Redfern kinetic model revealed that chemical reactions and diffusional models played a predominant role in the thermal decomposition process of the GG. This study showed that the thermodynamic parameters varied with the conversion ratio, and the combustion performance increased with the heating rates. The use of GG as an energy feedstock is recommended based on the findings from this work.

Impact of the Incorporation of Nano-Sized Cellulose Formate on the End Quality of Polylactic Acid Composite Film

Polylactic acid (PLA) films with good sustainable and biodegradable properties have been increasingly explored recently, while the poor mechanical property of PLA limits its further application. Herein, three kinds of nano-sized cellulose formate (NCF: cellulose nanofibril (CNF), cellulose nanocrystal (CNC), and regenerated cellulose formate (CF)) with different properties were fabricated via a one-step formic acid (FA) hydrolysis of tobacco stalk, and the influence of the properties of NCF with different morphologies, crystallinity index (CrI), and degree of substitution (DS) on the end quality of PLA composite film was systematically compared. Results showed that the PLA/CNC film showed the highest increase (106%) of tensile strength compared to the CNF- and CF-based films, which was induced by the rod-like CNC with higher CrI. PLA/CF film showed the largest increase (50%) of elongation at the break and more even surface, which was due to the stronger interfacial interaction between PLA and the CF with higher DS. Moreover, the degradation property of PLA/CNF film was better than that of other composite films. This fundamental study was very beneficial for the development of high-quality, sustainable packaging as an alternative to petroleum-based products.

Dragon Fruit Foliage: An Agricultural Cellulosic Source to Extract Cellulose Nanomaterials

In this report, we focus our effort to extract cellulose nanomaterials (CNs) from an agricultural cellulosic waste, Dragon Fruit foliage (DFF). DFF was first pretreated by several mechanical treatments and then bleached by chemical treatment to obtain bleached DFF. CNs were then produced from the hydrolysis of the bleached DFF catalyzed by sulfuric acid. We obtained CNs with a small diameter (50 to 130 nm) and length (100 to 500 nm) and a height of 3 to 10 nm. The CNs have a high crystallinity (crystallinity index 84.8%), high −COOH content (0.74 mmol. g−1), good thermal stability and a good Cu (II) adsorption capacity with an adsorption maximum of ~103 mg. g−1. These findings demonstrated the great potential of converting many agricultural cellulosic wastes into valuable cellulose nanomaterials.