Green Strategy Guided by Raman Spectroscopy for the Synthesis of Ammonium Carboxylated Nanocrystalline Cellulose and the Recovery of Byproducts
04 Feb 2013-ACS Sustainable Chemistry & Engineering (American Chemical Society)-Vol. 1, Iss: 2, pp 278-283
TL;DR: In this article, a one-pot green procedure for the treatment of cellulosic biomass with ammonium persulfate (APS) was developed for the synthesis of highly crystalline carboxylated nanocrystalline cellulose (NCC-COOH), an emerging nanomaterial with a plethora of diversified applications.
Abstract: A one-pot green procedure for the treatment of cellulosic biomass with ammonium persulfate (APS) was developed for the synthesis of highly crystalline carboxylated nanocrystalline cellulose (NCC–COOH), an emerging nanomaterial with a plethora of diversified applications. Raman spectroscopy proved applicable for monitoring the fate of APS and its two byproducts during the production of NCC–COOH from microcrystalline cellulose (MCC). The two main byproducts were then identified and quantified as ammonium sulfate (AS) and H2SO4 with the latter accounted for 60% of the total sulfate ions in solution. On the basis of such findings, one-step neutralization of H2SO4 and NCC with NH4OH immediately after reaction was implemented for the formation of additional AS, followed by its quantitative recovery by precipitation. This was a very effective and critical step in waste stream management and cost reduction for the large scale production of NCC. In addition, the process resulted in highly crystalline NCC with COO–...
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TL;DR: The dynamic batch adsorption of methylene blue (MB), a widely used and toxic dye, onto nanocrystalline cellulose (NCC) and crushed powder of carbon monolith (CM) was investigated using the pseudo-first- and -second-order kinetics, indicating the homogeneous surface of these two materials.
Abstract: The dynamic batch adsorption of methylene blue (MB), a widely used and toxic dye, onto nanocrystalline cellulose (NCC) and crushed powder of carbon monolith (CM) was investigated using the pseudo-first- and -second-order kinetics. CM outperformed NCC with a maximum capacity of 127 mg/g compared to 101 mg/g for NCC. The Langmuir isotherm model was applicable for describing the binding data for MB on CM and NCC, indicating the homogeneous surface of these two materials. The Gibbs free energy of −15.22 kJ/mol estimated for CM unravelled the spontaneous nature of this adsorbent for MB, appreciably faster than the use of NCC (−4.47 kJ/mol). Both pH and temperature exhibited only a modest effect on the adsorption of MB onto CM. The desorption of MB from CM using acetonitrile was very effective with more than 94 % of MB desorbed from CM within 10 min to allow the reusability of this porous carbon material. In contrast, acetonitrile was less effective than ethanol in desorbing MB from NCC. The two solvents were i...
290 citations
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TL;DR: With increase of oxidant content in the two methods, the carboxyl groups on the surfaces of TEMPO-oxidized CCNs and AO-CCNs were both improved and a remarkable decline of the DPv of cellulose sample also appeared in theTwo oxidative treatments.
177 citations
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TL;DR: In this paper, flame retardant cellulose aerogels were fabricated from waste cotton fabrics by in situ synthesis of magnesium hydroxide nanoparticles (MH NPs) in cellulose gel nanostructures, followed by freeze-drying.
Abstract: Cellulose aerogels with low density, high mechanical strength, and low thermal conductivity are promising candidates for environmentally friendly heat insulating materials. The application of cellulose aerogels as heat insulators in building and domestic appliances, however, is hampered by their highly flammable characteristics. In this work, flame retardant cellulose aerogels were fabricated from waste cotton fabrics by in situ synthesis of magnesium hydroxide nanoparticles (MH NPs) in cellulose gel nanostructures, followed by freeze-drying. Our results demonstrated that the three-dimensionally nanoporous cellulose gel prepared from the NaOH/urea solution could serve as scaffold/template for the nonagglomerated growth of MH NPs. The prepared hybridized cellulose aerogels showed excellent flame retardancy, which could extinguish within 40 s. Meanwhile, the thermal conductivity of the composite aerogel increased moderately from 0.056 to 0.081 W m–1 k–1 as the specific surface area decreased slightly from 3...
165 citations
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TL;DR: In this article, an efficient and low-cost approach to prepare spherical cellulose nanocrystals (SCNCs) is presented through chemical hydrolysis of lyocell fibers in an ammonium persulfate (APS) solution.
Abstract: An efficient and low-cost approach to prepare spherical cellulose nanocrystals (SCNCs) is presented through chemical hydrolysis of lyocell fibers in an ammonium persulfate (APS) solution. The as-prepared cellulose nanoparticles were characterized by scanning electron microscopy, atomic force microscopy, laser light scattering particle analysis, wide angle X-ray diffraction, Fourier transform infrared spectrometry and thermal gravimetric analysis. Effects of hydrolysis conditions, such as reaction time and temperature, and APS concentration on the morphology, microstructure, and thermal stability of cellulose nanoparticles are discussed. Moreover, it is found that under mild reaction conditions, cellulose nanoparticles are spherical particles with a narrow diameter distribution, and have a cellulose II polymorphic crystalline structure with surface carboxyl groups. The optimal hydrolysis time was found to be around 16 h for hydrolysis at 80 °C with a 1 M APS aqueous solution.
153 citations
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TL;DR: In this paper, the potentialities of cellulose nanocrystals (CNCs) as coatings for polyethylene terephthalate (PET) films were compared with two different processes: sulfuric acid hydrolysis and a less common treatment with ammonium persulfate (APS), able to provide also a cellulose oxidation.
Abstract: Cellulose nanocrystals (CNCs), extracted from trees, plants, or similar cellulose-containing materials, can be used in combination with other materials to improve their performance or introduce new applications. The main purpose of this study was to compare and understand the potentialities, as coatings for Poly(ethylene terephthalate) films, of CNCs obtained starting from the same cotton linters by two different processes: sulfuric acid hydrolysis and a less common treatment with ammonium persulfate (APS), able to provide also a cellulose oxidation. The results showed that CNCs produced through the APS treatment showed higher charge densities, due to the carboxylic groups formed during the process, higher crystallinity, higher clarity of the solution and, as a consequence, higher transparency of the coating. These characteristics provide a higher oxygen barrier with respect to the CNCs produced by the H2SO4 treatment, together with the availability of active sites for potential surface modification or chemical grafting. Both CNC coatings showed oxygen permeability coefficients that were lower than synthetic resins commonly used in flexible packaging. Furthermore, they did not significantly affect the optical properties of the substrate, while revealing good friction coefficients. Due though to the moisture sensitivity of the coating and its non-sealable nature, similar to EVOH or PVOH oxygen barrier synthetic resins, CNCs developed using APS will need to be laminated with another plastic layer such as a polyolefin. They could then be used to enhance the final properties of packaging solutions as an alternative to conventional food-packaging materials for perishable food products, while reducing their environmental impact with a thin layer of a bio-based polymer.
137 citations
Cites background from "Green Strategy Guided by Raman Spec..."
...Similarly, the COOH form of CNCs is reported as being more stable than the COONa? form (Lam et al. 2013)....
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...4 are referable, according to Lam (Lam et al. 2013), to C...
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References
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TL;DR: In this paper, an empirical method for determining the crystallinity of native cellulose was studied with an x-ray diffractometer using the focusing and transmission techniques, and the influence of fluctuations in the primary radiation and in counting and recording processes have been determined.
Abstract: An empirical method for determining the crystallinity of native cellulose was studied with an x-ray diffractometer using the focusing and transmission techniques. The influence of fluctuations in the primary radiation and in the counting and recording processes have been determined. The intensity of the 002 interference and the amor phous scatter at 2θ = 18° was measured. The percent crystalline material in the total cellulose was expressed by an x-ray "crystallinity index." This was done for cotton cellulose decrystallized with aqueous solutions containing from 70% to nominally 100% ethylamine. The x-ray "crystallinity index" was correlated with acid hydrolysis crys tallinity, moisture regain, density, leveling-off degree of polymerization values, and infrared absorbance values for each sample. The results indicate that the crystallinity index is a time-saving empirical measure of relative crystallinity. The precision of the crystallinity index in terms of the several crystallinity criteria is given. Bas...
6,189 citations
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TL;DR: This critical review provides a processing-structure-property perspective on recent advances in cellulose nanoparticles and composites produced from them, and summarizes cellulOSE nanoparticles in terms of particle morphology, crystal structure, and properties.
Abstract: This critical review provides a processing-structure-property perspective on recent advances in cellulose nanoparticles and composites produced from them. It summarizes cellulose nanoparticles in terms of particle morphology, crystal structure, and properties. Also described are the self-assembly and rheological properties of cellulose nanoparticle suspensions. The methodology of composite processing and resulting properties are fully covered, with an emphasis on neat and high fraction cellulose composites. Additionally, advances in predictive modeling from molecular dynamic simulations of crystalline cellulose to the continuum modeling of composites made with such particles are reviewed (392 references).
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TL;DR: Dr. Youssef Habibi’s research interests include the sustainable production of materials from biomass, development of high performance nanocomposites from lignocellulosic materials, biomass conversion technologies, and the application of novel analytical tools in biomass research.
Abstract: Cellulose constitutes the most abundant renewable polymer resource available today. As a chemical raw material, it is generally well-known that it has been used in the form of fibers or derivatives for nearly 150 years for a wide spectrum of products and materials in daily life. What has not been known until relatively recently is that when cellulose fibers are subjected to acid hydrolysis, the fibers yield defect-free, rod-like crystalline residues. Cellulose nanocrystals (CNs) have garnered in the materials community a tremendous level of attention that does not appear to be relenting. These biopolymeric assemblies warrant such attention not only because of their unsurpassed quintessential physical and chemical properties (as will become evident in the review) but also because of their inherent renewability and sustainability in addition to their abundance. They have been the subject of a wide array of research efforts as reinforcing agents in nanocomposites due to their low cost, availability, renewability, light weight, nanoscale dimension, and unique morphology. Indeed, CNs are the fundamental constitutive polymeric motifs of macroscopic cellulosic-based fibers whose sheer volume dwarfs any known natural or synthetic biomaterial. Biopolymers such as cellulose and lignin and † North Carolina State University. ‡ Helsinki University of Technology. Dr. Youssef Habibi is a research assistant professor at the Department of Forest Biomaterials at North Carolina State University. He received his Ph.D. in 2004 in organic chemistry from Joseph Fourier University (Grenoble, France) jointly with CERMAV (Centre de Recherche sur les Macromolecules Vegetales) and Cadi Ayyad University (Marrakesh, Morocco). During his Ph.D., he worked on the structural characterization of cell wall polysaccharides and also performed surface chemical modification, mainly TEMPO-mediated oxidation, of crystalline polysaccharides, as well as their nanocrystals. Prior to joining NCSU, he worked as assistant professor at the French Engineering School of Paper, Printing and Biomaterials (PAGORA, Grenoble Institute of Technology, France) on the development of biodegradable nanocomposites based on nanocrystalline polysaccharides. He also spent two years as postdoctoral fellow at the French Institute for Agricultural Research, INRA, where he developed new nanostructured thin films based on cellulose nanowiskers. Dr. Habibi’s research interests include the sustainable production of materials from biomass, development of high performance nanocomposites from lignocellulosic materials, biomass conversion technologies, and the application of novel analytical tools in biomass research. Chem. Rev. 2010, 110, 3479–3500 3479
4,664 citations
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TL;DR: This Review assembles the current knowledge on the isolation of microfibrillated cellulose from wood and its application in nanocomposites; the preparation of nanocrystalline cellulose and its use as a reinforcing agent; and the biofabrication of bacterial nanocellulose, as well as its evaluation as a biomaterial for medical implants.
Abstract: Cellulose fibrils with widths in the nanometer range are nature-based materials with unique and potentially useful features. Most importantly, these novel nanocelluloses open up the strongly expanding fields of sustainable materials and nanocomposites, as well as medical and life-science devices, to the natural polymer cellulose. The nanodimensions of the structural elements result in a high surface area and hence the powerful interaction of these celluloses with surrounding species, such as water, organic and polymeric compounds, nanoparticles, and living cells. This Review assembles the current knowledge on the isolation of microfibrillated cellulose from wood and its application in nanocomposites; the preparation of nanocrystalline cellulose and its use as a reinforcing agent; and the biofabrication of bacterial nanocellulose, as well as its evaluation as a biomaterial for medical implants.
3,452 citations
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TL;DR: Never-dried native celluloses (bleached sulfite wood pulp, cotton, tunicin, and bacterial cellulose) were disintegrated into individual microfibrils after oxidation mediated by the 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) radical followed by a homogenizing mechanical treatment.
1,540 citations