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Advances in Cellulosic Materials 2014

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A special issue of Materials (ISSN 1996-1944).

Deadline for manuscript submissions: closed (30 July 2014) | Viewed by 87691

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Prof. Dr. Carlos Pascoal Neto

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Ciceco, Department of Chemistry, University of Aveiro, Aveiro, Portugal
Interests: wood chemistry; pulp and paper chemistry; pulping and bleaching; bio refineries; cellulose-based materials; composites from renewable resources
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Prof. Dr. Armando J. D. Silvestre

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CICECO–Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal
Interests: natural products; biorefinery; gc-ms; biobased polymers; HPLC-MS; extractives; biobased (nano)composites
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Prof. Dr. Carmen S. R. Freire

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CICECO—Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, 3810-193 Aveiro, Portugal
Interests: production and application of biogenic nanofibers (bacterial cellulose and protein fibrils); nanostructured biocomposites; bio-based materials for biomedical applications (wound healing, drug delivery and 3D-bioprinting); biocomposites and functional paper materials; chemical modification of (nano)cellulose fibers and other polysaccharides and their characterization and applications; chemistry of lignocellulosic materials (cellulose, wood, cork, etc.)
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Special Issue Information

Dear Colleagues,

Cellulose, due to its natural abundance and unique properties, is undoubtedly one of the most promising renewable raw materials for the large scale production of chemicals, fuels, and materials in a biobased economy. The unique features of cellulose fibers make them one of the most promising resources for the development of a wide range of sustainable and functional materials, with applications such as composites, transparent films, biomedical devices and products packaging, organic electronics, special papers, among many others. In this sense, this special issue is aimed at reporting the most recent developments on cellulose based materials; covering all forms of cellulose, namely plant cellulose, cellulose whiskers, nanofibrillated and bacterial cellulose, as well as the relevant processing techniques (including fiber modification) to produce new and innovative composite (nano)materials, characterization techniques, properties and applications. For this special issue we will invite authors to publish research articles or comprehensive reviews on the topics referred above.

Prof. Dr. Carlos Pascoal Neto
Prof. Dr. Armando J. D. Silvestre
Dr. Carmen S. R. Freire
Guest Editors

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Published Papers (9 papers)

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1065 KiB

Open AccessArticle

Phosphated Cellulose as an Efficient Biomaterial for Aqueous Drug Ranitidine Removal

by Roosevelt D. S. Bezerra, Márcia M. F. Silva, Alan I. S. Morais, Josy A. Osajima, Maria R. M. C. Santos, Claudio Airoldi and Edson C. Silva Filho

Materials 2014, 7(12), 7907-7924; https://doi.org/10.3390/ma7127907 - 9 Dec 2014

Cited by 35 | Viewed by 9025

Abstract

Crystalline cellulose chemically modified through a reaction with sodium trimetaphosphate (STMP) in an acidic or basic condition yielded Cel-P4 and Cel-P10. These phosphated solids were characterized by elemental analysis, X-ray diffraction (XRD), infrared (IR) spectroscopy, scanning electron microscopy (SEM), nuclear magnetic resonance (NMR) at the solid state for phosphorus nucleus and dispersive X-ray energy. The elemental results demonstrated that the phosphorylation reaction was more efficient in the basic medium, as supported by the amount of phosphorous content. The synthesized biomaterials decreased in crystallinity in comparison to the precursor cellulose, with an increase in roughness and present two distinct phosphorus environments in the formed structure. The phosphated cellulose in an alkaline condition was applied to sorb the drug ranitidine. This process was applied in varying pH, time, temperature and concentration. The best sorption kinetic model to fit the experimental data was the pseudo-second-order with a coefficient correlation of 0.8976, and the Langmuir isotherm model was the most adjusted to the variation in concentration. The efficient drug sorption has a low dependence on temperature, with maximum values of 85.0, 82.0 mg and 85.7 mg·g⁻¹ for Cel-P10 at 298, 308 and 318 K, respectively. The best sorption occurred at pH = 6 with a saturation time of 210 min. Full article

(This article belongs to the Special Issue Advances in Cellulosic Materials 2014)

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1564 KiB

Open AccessArticle

Study of Reactive Melt Processing Behavior of Externally Plasticized Cellulose Acetate in Presence of Isocyanate

by Rafael Erdmann, Stephan Kabasci, Joanna Kurek and Stefan Zepnik

Materials 2014, 7(12), 7752-7769; https://doi.org/10.3390/ma7127752 - 4 Dec 2014

Cited by 10 | Viewed by 8423

Abstract

Two types of externally plasticized cellulose acetate (CA) were chemically modified using 4,4'-methylene diphenyl diisocyanate (MDI) as crosslinking agent. Crosslinking was performed in the molten state by means of melt mixing in an internal mixer. The viscoelastic properties of the non-crosslinked, externally plasticized CA show typical temperature dependence, similar to conventional thermoplastics. A strong increase in storage modulus is observed with increasing crosslink density indicating that the crosslinked compounds exhibit predominately elastic response. The complex viscosity also increases considerably with increasing crosslink density and does not reach the typical Newtonian plateau at low radial frequencies any more. The viscoelastic properties correlate well with the data recorded online during reactive melt processing in the internal mixer. In comparison to the non-crosslinked CA, the crosslinked compounds show higher glass transition temperature, higher VICAT softening temperatures, improved thermal stability and lower plasticizer evaporation at evaluated temperatures. Full article

(This article belongs to the Special Issue Advances in Cellulosic Materials 2014)

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1334 KiB

Open AccessArticle

Mechanism for Tuning the Hydrophobicity of Microfibrillated Cellulose Films by Controlled Thermal Release of Encapsulated Wax

by Vibhore Kumar Rastogi, Dirk Stanssens and Pieter Samyn

Materials 2014, 7(11), 7196-7216; https://doi.org/10.3390/ma7117196 - 28 Oct 2014

Cited by 14 | Viewed by 9499

Abstract

Although films of microfibrillated cellulose (MFC) have good oxygen barrier properties due to its fine network structure, properties strongly deteriorate after absorption of water. In this work, a new approach has been followed for actively tuning the water resistance of a MFC fiber network by the inclusion of dispersed organic nanoparticles with encapsulated plant wax. The modified pulp suspensions have been casted into films and were subsequently cured at 40 to 220 °C. As such, static water contact angles can be specifically tuned from 120 to 150° by selection of the curing temperature in relation with the intrinsic transition temperatures of the modified pulp, as determined by thermal analysis. The appearance of encapsulated wax after curing was followed by a combination of morphological analysis, infrared spectroscopy and Raman mapping, showing balanced mechanisms of progressive release and migration of wax into the fiber network controlling the surface properties and water contact angles. Finally, the appearance of nanoparticles covered with a thin wax layer after complete thermal release provides highest hydrophobicity. Full article

(This article belongs to the Special Issue Advances in Cellulosic Materials 2014)

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953 KiB

Open AccessArticle

Mechanical and Thermal Properties of Polypropylene Composites Reinforced with Lignocellulose Nanofibers Dried in Melted Ethylene-Butene Copolymer

by Shinichiro Iwamoto, Shigehiro Yamamoto, Seung-Hwan Lee, Hirokazu Ito and Takashi Endo

Materials 2014, 7(10), 6919-6929; https://doi.org/10.3390/ma7106919 - 9 Oct 2014

Cited by 31 | Viewed by 7584

Abstract

Lignocellulose nanofibers were prepared by the wet disk milling of wood flour. First, an ethylene-butene copolymer was pre-compounded with wood flour or lignocellulose nanofibers to prepare master batches. This process involved evaporating the water of the lignocellulose nanofiber suspension during compounding with ethylene-butene copolymer by heating at 105 °C. These master batches were compounded again with polypropylene to obtain the final composites. Since ethylene-butene copolymer is an elastomer, its addition increased the impact strength of polypropylene but decreased the stiffness. In contrast, the wood flour- and lignocellulose nanofiber-reinforced composites showed significantly higher flexural moduli and slightly higher flexural yield stresses than did the ethylene-butene/polypropylene blends. Further, the wood flour composites exhibited brittle fractures during tensile tests and had lower impact strengths than those of the ethylene-butene/polypropylene blends. On the other hand, the addition of the lignocellulose nanofibers did not decrease the impact strength of the ethylene-butene/polypropylene blends. Finally, the addition of wood flour and the lignocellulose nanofibers increased the crystallization temperature and crystallization rate of polypropylene. The increases were more remarkable in the case of the lignocellulose nanofibers than for wood flour. Full article

(This article belongs to the Special Issue Advances in Cellulosic Materials 2014)

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517 KiB

Open AccessArticle

Drying of Pigment-Cellulose Nanofibril Substrates

by Oleg Timofeev, Katariina Torvinen, Jenni Sievänen, Timo Kaljunen, Jarmo Kouko and Jukka A. Ketoja

Materials 2014, 7(10), 6893-6907; https://doi.org/10.3390/ma7106893 - 1 Oct 2014

Cited by 9 | Viewed by 8793

Abstract

A new substrate containing cellulose nanofibrils and inorganic pigment particles has been developed for printed electronics applications. The studied composite structure contains 80% fillers and is mechanically stable and flexible. Before drying, the solids content can be as low as 20% due to the high water binding capacity of the cellulose nanofibrils. We have studied several drying methods and their effects on the substrate properties. The aim is to achieve a tight, smooth surface keeping the drying efficiency simultaneously at a high level. The methods studied include: (1) drying on a hot metal surface; (2) air impingement drying; and (3) hot pressing. Somewhat surprisingly, drying rates measured for the pigment-cellulose nanofibril substrates were quite similar to those for the reference board sheets. Very high dewatering rates were observed for the hot pressing at high moisture contents. The drying method had significant effects on the final substrate properties, especially on short-range surface smoothness. The best smoothness was obtained with a combination of impingement and contact drying. The mechanical properties of the sheets were also affected by the drying method and associated temperature. Full article

(This article belongs to the Special Issue Advances in Cellulosic Materials 2014)

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639 KiB

Open AccessArticle

Evaluation of Binding Effects in Wood Flour Board Containing Ligno-Cellulose Nanofibers

by Yoichi Kojima, Akiko Isa, Hikaru Kobori, Shigehiko Suzuki, Hirokazu Ito, Rie Makise and Masaki Okamoto

Materials 2014, 7(9), 6853-6864; https://doi.org/10.3390/ma7096853 - 22 Sep 2014

Cited by 29 | Viewed by 6933

Abstract

Wood-based materials are used extensively in residual construction worldwide. Most of the adhesives used in wood-based materials are derived from fossil resources, and some are not environmentally friendly. This study explores nanofiber technology as an alternative to such adhesives. Previous studies have shown that the three-dimensional binding effects of cellulose nanofiber (CNF), when mixed with wood flour, can significantly improve the physical and mechanical properties of wood flour board. In this study, ligno-cellulose nanofibers (LCNF) were fabricated by wet disk milling of wood flour. Composite boards of wood flour and LCNF were produced to investigate the binding effect(s) of LCNF. The fabrication of LCNF by disk milling was simple and effective, and its incorporation into wood flour board significantly enhanced the physical and mechanical properties of the board. Full article

(This article belongs to the Special Issue Advances in Cellulosic Materials 2014)

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1128 KiB

Open AccessArticle

Preparation and Characterization of Lignocellulosic Oil Sorbent by Hydrothermal Treatment of Populus Fiber

by Yue Zhang, Sheng Yang, Jian-Quan Wu, Tong-Qi Yuan and Run-Cang Sun

Materials 2014, 7(9), 6733-6747; https://doi.org/10.3390/ma7096733 - 18 Sep 2014

Cited by 33 | Viewed by 8659

Abstract

This study is aimed at achieving the optimum conditions of hydrothermal treatment and acetylation of Populus fiber to improve its oil sorption capacity (OSC) in an oil-water mixture. The characteristics of the hydrolyzed and acetylated fibers were comparatively investigated by FT-IR, CP-MAS ¹³C-NMR, SEM and TGA. The optimum conditions of the hydrothermal treatment and acetylation were obtained at170 °C for 1 h and 120 °C for 2 h, respectively. The maximum OSC of the hydrolyzed fiber (16.78 g/g) was slightly lower than that of the acetylated fiber (21.57 g/g), but they were both higher than the maximum OSC of the unmodified fiber (3.94 g/g). In addition, acetylation after hydrothermal treatment for the Populus fiber was unnecessary as the increment of the maximum OSC was only 3.53 g/g. The hydrolyzed and the acetylated Populus fibers both displayed a lumen orifice enabling a high oil entrapment. The thermal stability of the modified fibers was shown to be increased in comparison with that of the raw fiber. The hydrothermal treatment offers a new approach to prepare lignocellulosic oil sorbent. Full article

(This article belongs to the Special Issue Advances in Cellulosic Materials 2014)

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992 KiB

Open AccessArticle

Native Cellulose: Structure, Characterization and Thermal Properties

by Matheus Poletto, Heitor L. Ornaghi, Júnior and Ademir J. Zattera

Materials 2014, 7(9), 6105-6119; https://doi.org/10.3390/ma7096105 - 25 Aug 2014

Cited by 763 | Viewed by 19597

Abstract

In this work, the relationship between cellulose crystallinity, the influence of extractive content on lignocellulosic fiber degradation, the correlation between chemical composition and the physical properties of ten types of natural fibers were investigated by FTIR spectroscopy, X-ray diffraction and thermogravimetry techniques. The results showed that higher extractive contents associated with lower crystallinity and lower cellulose crystallite size can accelerate the degradation process and reduce the thermal stability of the lignocellulosic fibers studied. On the other hand, the thermal decomposition of natural fibers is shifted to higher temperatures with increasing the cellulose crystallinity and crystallite size. These results indicated that the cellulose crystallite size affects the thermal degradation temperature of natural fibers. This study showed that through the methods used, previous information about the structure and properties of lignocellulosic fibers can be obtained before use in composite formulations. Full article

(This article belongs to the Special Issue Advances in Cellulosic Materials 2014)

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1035 KiB

Open AccessArticle

SAXS Studies of the Endoglucanase Cel12A from Gloeophyllum trabeum Show Its Monomeric Structure and Reveal the Influence of Temperature on the Structural Stability of the Enzyme

by Lis S. Miotto, Caio V. Dos Reis, Mario De Oliveira Neto and Igor Polikarpov

Materials 2014, 7(7), 5202-5211; https://doi.org/10.3390/ma7075202 - 17 Jul 2014

Cited by 4 | Viewed by 8054

Abstract

Endoglucanases are key enzymes applied to the conversion of biomass aiming for second generation biofuel production. In the present study we obtained the small angle X-ray scattering (SAXS) structure of the G. trabeum endo-1,4-β-glucanase Cel12A and investigated the influence of an important parameter, temperature, on both secondary and tertiary structure of the enzyme and its activity. The CD analysis for GtCel12A revealed that changes in the CD spectra starts at 55 °C and the T_m calculated from the experimental CD sigmoid curve using the Boltzmann function was 60.2 ± 0.6 °C. SAXS data showed that GtCel12A forms monomers in solution and has an elongated form with a maximum diameter of 60 ± 5 Å and a gyration radius of 19.4 ± 0.1 Å as calculated from the distance distribution function. Kratky analysis revealed that 60 °C is the critical temperature above which we observed clear indications of denaturation. Our results showed the influence of temperature on the stability and activity of enzymes and revealed novel structural features of GtCel12A. Full article

(This article belongs to the Special Issue Advances in Cellulosic Materials 2014)

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