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Due to the surface hydrophobicity, the absorbing effect of the tobacco extract droplets on the reconstituted tobacco paper is unsatisfactory. Therefore, the surface property regulation of the tobacco paper has gained increasing attention. This work reports a novel argon (Ar) plasma treatment technique for improving the surface hydrophilicity and bacteriostatic effect of the paper. Firstly, Ar plasma was selected as the treatment gas and its improving effect was demonstrated through studying the contact angle changes of water droplet on the A4 paper. Then, the capillary fibers on the paper were bombarded by Ar plasma jet. The extract droplet contact angle on the reconstituted tobacco paper-15 s surface is only 14.6° within 1 s. In comparison to the pristine paper (5.9°/s), the absorption dynamic of the droplet increased to as high as 62.5°/s, which indicated the hydrophilicity was greatly improved by the Ar plasma method. The mechanism for improving the surface hydrophilicity of the cellulose in the tobacco paper also contributed to the generation of holes by Ar plasma jet, which increased the surface permeability of cellulose. At last, Ar plasma treatment showed excellent bacteriostatic effect, which could effectively inhibit the propagation and growth of fungi, Escherichia coli, and Staphylococcus aureus on the tobacco paper. [ABSTRACT FROM AUTHOR]

The three cellulosic key chromophores, 2,5-dihydroxy-[1,4]-benzoquinone, 5,8-dihydroxy-[1,4]-naphthoquinone and 2,5-dihydroxy-acetophenone, are nearly ubiquitous in cellulosic materials because of their special structures and resonance stabilization with highly delocalized double bonds that renders them thermodynamically very stable and resistant towards bleaching. All of these compounds possess acidic hydroxyl groups. The current work explores the derivatization of these OH groups by a phosphitylation agent followed by 31P NMR analysis, an approach that is very frequently used for quantitative OH group analysis and differentiation in lignins and lignin derivatives. The chemical shifts are reported and structural peculiarities of the chromophore derivatives are discussed. The 31P NMR approach adds to the toolbox of methods applicable in cellulose chromophore analysis, bleaching and aging studies. [ABSTRACT FROM AUTHOR]

Pulp fibers are among the most abundant and cost effective cellulose source for the fabrication of polymer-cellulose composites. A straightforward method is to impregnate pulp fibers into thermoplastic films by hot press forming. As such, tissue materials made from hard or soft wood lignin-free Kraft fibers are attractive. In this work, we prepared cellulose fiber-polylactic acid (PLA) composite films by impregnating PLA films into a 40 g/m2 tissue paper texture. A PLA film was sandwiched between single and multiple layers of cellulose tissues by hot pressing, forming composite films. Up to 40 wt% cellulose could be incorporated into PLA in this way. The effect of cellulose fiber content on the composite thermomechanical properties has been studied and reported. A natural terpene, limonene, was infused into the cellulose fibers by immersion coating to produce antioxidant composites. Limonene-modified composites demonstrated long-term antioxidant release and activity for three days, verified by 2, 2-Diphenyl-1-picrylhydrazyl (DPPH), cupric ion reducing antioxidant capacity (CUPRAC) and free iron ions (Fe2+)/ferrozine chelating assays separately. The short-term (2 h) antioxidant activity of the biocomposites reached 50–70% levels depending on the cellulose fiber concentration for the DPPH and CUPRAC assays but remained lower at 20–55% levels in the metal chelating assay. Due to sustained release of limonene from the composites, at the end of the 5-day period, the iron chelating antioxidant activity of the composites improved reaching 75%, whereas for DPPH and CUPRAC assay, 90% activity was recorded. These biocomposite films can be used in active protective packaging of both food (fruit) and cosmetic products. [ABSTRACT FROM AUTHOR]

Cellulose-based materials represent a renewable, biodegradable, and environmentally friendly alternative to plastic from fossil resources. Nanopaper is a strong and lightweight material formed from cellulose nanofibrils (CNFs). Paper and nanopaper have been considered as excellent alternatives to plastics for use in agriculture and for packaging applications. However, common for both paper and nanopaper is their hydrophilic character, and consequently, poor water-resistance properties. ORMOCER®s are a class of inorganic–organic polymers with excellent barrier and protective properties used for a range of coating applications. Here we present ORMOCER®-coated paper and nanopaper. The coated papers and nanopapers are characterized, both in terms of their morphology, hydrophobicity, and mechanical properties. We demonstrate that the pressure used during the pressing and drying of paper and nanopaper influence their tear and tensile—properties, and that the morphology of the coated nanopaper differs significantly from that of the coated paper. While the ORMOCER® was impregnated within the porous network of the paper, a well-defined two-layered morphology was obtained with the coated nanopaper. Further, the biodegradability of the nanopaper with and without coating was assessed. The degradation study demonstrated that both the pressure used during the pressing and drying of the nanopaper, and the composition of the ORMOCER®, influenced the rate of degradation. Taken together, ORMOCER®-coated paper and nanopaper are promising for the preparation of materials that are both water-resistant, renewable, and biodegradable. [ABSTRACT FROM AUTHOR]

This publication presents the results of the fundamental research on the interaction of laser radiation and lignocellulosic fibres with respect to the melting of the fibre main components cellulose, hemicellulose and lignin. In the first part, hand sheets made of different lignocellulosic fibres were irradiated with laser radiation from a carbon monoxide laser. Fluence-dependent interaction regimes, the dynamics of flash pyrolysis and chemical changes due to irradiation are discussed. Using a high-speed camera, an intermediate liquid state could be observed as a result of the irradiation. This is decomposed into gaseous reaction products by a highly dynamic boiling process. In addition to the time-resolved investigations, extensive FTIR studies were carried out. The second part is intended to further investigate former work on melting of cellulose. The basic idea is to combine laser radiation and mechanical pressure by compressing the sample between two steel bolts and simultaneously irradiating the joint. The processed samples show some visual indications of intermediate melting, such as increased transparency or flow behaviour. However, these can be traced back to effects that do not require a melting state. [ABSTRACT FROM AUTHOR]

Direct fire, indirect heat, and extinguishing water cause great damage to cultural assets upon a fire disaster in a library or archive. Conservation and restoration of heat-damaged papers are particularly challenging due to the complexity and severity of the damage. Since valuable originals obviously cannot be used for the development of treatment methods and only to a limited extent for the analysis of the damage, it is necessary to produce model paper materials that have a high degree of similarity to fire-damaged papers, which was addressed in the present study. Three different heating methods were tested to produce model papers of different heating levels. Their altered optical, structural, and chemical properties were analyzed and compared with the results of original fire-damaged samples. The study points out pathways to enable the production of comparable sample materials. Heating between hot plates or in an oven produces papers that have properties quite similar to the originals in terms of surface area, paper structure, cellulose integrity, and interactions with water. Stack heating in the oven has proven to be a particularly effective manufacturing method for larger quantities of model papers. [ABSTRACT FROM AUTHOR]

Correctness and reliability of molar mass data by viscometry in organometallic solvents (cuen, cuoxam, cadoxen) are compromised by the alkalinity of these solvents which causes immediate depolymerization especially in the case of pulps with higher carbonyl content (oxidative damage). The viscosity values thus correspond to the molar mass after the beta-elimination reactions that underly these degradative processes, which is sometimes significantly smaller than the molar mass determined by gel permeation chromatography (GPC) in the non-degrading solvent system DMAc/LiCl. Despite this well-known drawback, viscosity measurements have become a standard approach for molar mass measurements due to their ease and fastness, especially in the pulp and paper industries. A potential way to reduce the inherent error of these molar mass determinations via viscosity measurements is a reductive treatment prior to dissolution of the pulp in the organometallic solvents, which converts the labile, alkali-sensitive carbonyl structures back to the respective alcohols. Using sodium borohydride (NaBH4) on different types of cellulosic pulps, we demonstrate the beneficial effects of such a reduction step on the determined degree of polymerization (DP) for all three common solvents: cuen, cuoxam and cadoxen. Molar mass distributions and profiles of carbonyl groups were determined by GPC and by carbonyl selective fluorescence labeling ("CCOA method"). Such a reductive treatment was especially valuable for hemicellulose-containing pulps. While the decreased measurement error according to the new protocol is beyond doubt, an immediate acceptance in the pulp and paper industries is at least questionable, because the new, more correct data would not agree with the old – wrong, but consistent – numbers accumulated over years and decades. In the long run, however, the new, improved protocol will prevail here as well due to its lower error rate. [ABSTRACT FROM AUTHOR]

As a green material, cellulose is widely used in friction triboelectric nanogenerators (TENGs). However, the weak polarity of the cellulose fibers surface leads to its weak contact electrification performance, which is not conducive to its utilization in TENGs. In this study, epoxy chloropropane and ethylenediamine were grafted onto cellulose fibers to form paper and were assembled with an Fluorinated ethylene propylene film. The output voltage, current, and surface charge density were 34.9%, 26.7%, and 16.7% higher than those of ordinary paper, respectively. When 20% nano TiO2 filler was added to the paper made from amino-modified cellulose fibers, the output voltage, current, and surface charge density of the TENG increased by 70.9%, 226.7%, and 122.2%, respectively, compared with ordinary paper. As the air humidity of the TENG increased from 60 to 90%, the output voltage, current, and surface charge density were maintained at 53.7%, 38.9%, and 61.0%, respectively. When a 5 × 107 Ω resistor was connected to the working circuit, its output power reached 13.78 μ W cm2. This showed that cellulose as a green material has wide application prospects in the field of TENG. [ABSTRACT FROM AUTHOR]

We combine biodegradable plastic (polyvinyl alcohol/glycerol polymer), and cellulose-based tissue paper in a very short time (5 s) by a facile way to form a new matrix, named plastic-paper, which has high optical transmittance (~ 89%) and high optical haze (~ 90%) in broadband. Results showed that the plastic-paper is durable in different solvents, with high folding strength (over 3500 folding times) and good mechanical strength (> 30 MPa tensile strength). Interestingly, the plastic-paper presents a two-sidedness of surface morphology. The smooth side shows high light transmittance and the rough side presents high optical haze. The smooth side of the plastic-paper is successfully applied to Organic Light-Emitting Diode (OLED). When the rough surface of plastic-paper is used in solar cells, the maximum output power increases by 2.6% compared with bare solar cells. The developed plastic-paper with high optical transmittance and high optical haze holds a great potential in flexible optoelectronic devices. [ABSTRACT FROM AUTHOR]

Cellulose-based materials are considered to be green and sustainable substitutes for plastics. However, their hydrophilicity and water instability limit further applications. Herein, ethyl cellulose (EC) and hydrophobic SiO2 nanoparticles (NPs) were employed to prepare hydrophobic SiO2@EC/P materials by dipping-spraying method. A series of cellulosic papers with various hydrophobicity (water contact angle (WCA) from about 90° to 166°, and contact angle hysteresis (CAH) less than 5°) were fabricated by varying the amount of SiO2 NPs. The dry and wet strength of the modified paper increased by 72.3% and 916.7%, respectively. Soaking test shows that the SiO2@EC/P straws remain intact after being placed in different beverages and water at the temperature of 0 to 90 °C for 2 h. Furthermore, these straws can be completely degraded after being buried into the soil for 200 days. Therefore, SiO2@EC/P materials are promising alternative materials for plastic straws. The potential application of SiO2@EC/P materials would effectively alleviate the 'white pollution' problem. [ABSTRACT FROM AUTHOR]

This contribution focuses on understanding of paper wet-strength properties, by taking a closer look at the spatial distribution of wet-strengthening polymers inside the cellulosic fiber network deposited under different treatment conditions using confocal laser scanning microscopy as in situ imaging tool. We compare the behavior of paper samples treated with a photochemically cross-linkable copolymer using an impregnation process employing three different solvents, namely water, 2-propanol (IPA) and 1-butanol (BuOH), respectively. As these solvents swell paper fibers to quite different extents, the deposition of the polymer, on, in or in-between the cellulosic fibers varies quite strongly, as is shown by in-depth analysis using confocal laser scanning microscopy. The difference in accessibility of distinct surface sites exclusively on or also in and between the fibers controls the macroscopic tensile strength under both dry and wet conditions. [ABSTRACT FROM AUTHOR]

To more accurately predict the permanence of paper during natural aging, we studied cellulose aging according to closed vial setup, which compared to alternative paper aging methods is closer to natural aging with regard to predictions of paper life expectancy. To improve kinetic evaluation, not only cellulose degradation by hydrolysis and oxidation, but also the moisture content in the closed vial were measured during the aging process. This allowed to eliminate the long-known errors of the method caused by vial leakage which falsely produce different aging rates for different aging periods. With the aim of predicting paper permanence more accurately, several ways of considering the moisture changes and the influences of paper moisture and vial leakage were considered and an improved protocol was elaborated that corrects the rate of cellulose chain scission based on the average moisture content in the paper. Based on this hydrolysis rate, the expected half-life DP becomes independent of the aging period and thus less error-prone and more reliable. We hope that this improvement of the very common closed-vial aging method will quickly be accepted and welcomed by the paper conservation community. [ABSTRACT FROM AUTHOR]

Moisture absorption in the cell wall structure of wood is well known to induce considerable swelling of the wood exerting high expansion forces. This swelling is mainly induced by the sorptive action of the hydroxyl groups of the carbohydrate wood polymers; cellulose and hemicelluloses. On the ultrastructural level, there are, however, still questions with regard to the detailed deformations induced by this moisture absorption. Here, FTIR spectroscopy and synchrotron-radiation-based X-ray diffraction were used on paper samples to study the deformation of the cellulose crystals as a consequence of moisture absorption and desorption. Both techniques revealed that the moisture absorption resulted in a transverse contraction of the cellulose crystals accompanied by a somewhat smaller elongation in the cellulose chain direction. The deformations were found to be a direct response to the increased moisture content and were also found to be reversible during moisture desorption. It is hypothesised that these deformations are a consequence of the swelling forces created by the combined longitudinal and lateral expansions of the non-crystalline cellulose molecules and the glucomannan hemicellulose aligned along the cellulose crystals. These forces will impose a lateral contraction of the cellulose crystals, as well as a longitudinal extension of it. [ABSTRACT FROM AUTHOR]

In paper containing multilayer composite structures and laminates, polarization is usually investigated under dry environmental conditions. The aim of this research is to determine polarization dependence of paper and paper-dielectric structures on environmental relative humidity (RH). The role of each component was identified. The obtained and recorded data are used for identification and clarification of the physical mechanism of polarization. The polarization was studied by applying a dosed charging and forced discharge method and was evaluated by a depolarization potential and its formation kinetics. The polarization level of investigated structures increases with RH and is determined mainly by the paper (cellulose) and moisture content in it. In composite structures of the paper between dielectric films and dielectric on paper the polarization dependence on RH correlates with moisture absorption isotherm. It was found that the surface electrical conductivity of paper distorts the results of the paper and structure paper on dielectric. Analysis of the formation kinetics of the depolarization potential together with the potential decay of the charged paper has determined the role of orientation polarization and space charges. The formation of space charges is faster than orientation polarization and dominates in polarization process at higher RH. The process modeling by superposition of two exponents confirms this polarization mechanism. [ABSTRACT FROM AUTHOR]

The use of nanocelluloses is being conducted for the most diverse applications. Their performance as coating agent has been mainly explored to improve barrier properties, as they emerge as perfect candidate for plastic substitution, but it is also important to explore their potential to improve printing quality. In the present work, the influence of different nanocelluloses, obtained through mechanical, enzymatic, TEMPO-mediated oxidation and carboxymethylation treatments, in the coating process and inkjet printability of office papers was assessed. The results revealed that the cellulose nanofibrils are better for printability than the microfibrils. But the size and charge of the former must be taken into account, since fibrils of very small size penetrate the paper structure, dragging the pigments from the surface, and very anionic nanofibrils can also have negative influence on the optical density. Besides, an interesting synergy between surface-sizing starch and the cellulose nanofibrils was found to occur as the latter closed the paper structure, which prevented starch from penetrating, while potentiating both of their positive effects on ink pigment entrapment. An additional study of characterization of inkjet pigments was also performed. [ABSTRACT FROM AUTHOR]

In this study, different methods for incorporating mixed or laminar copper microparticles (CuMPs) during papermaking were evaluated to determine the optimum paper-making process and correlate particle concentration and shape with antimicrobial activity. The addition of CuMPs during the disintegration of dry pulp stage was observed to produce a paper with uniformly distributed CuMPs, as determined through optical microscopy and UV–Vis spectroscopy analyses by measuring absorbance spectra in different areas of papers. Determination of two indices related to the concentration and distribution of copper will allow to predict the copper content in other papers. CuMP-paper samples were evaluated for structural, optical, and mechanical strength properties according to paper industry standards. Quantitative analyses by atomic absorption showed that between 24 and 39% of CuMPs were embedded in the paper fibre, independent of particle type. Finally, antibacterial activity analyses were performed according to ISO 20645 and ISO 20743. The results showed that papers with 0.30 g of incorporated CuMPs have antimicrobial activity, independent of particle morphology, with effects observed towards Gram (+) and Gram (−) bacteria and fungus. Furthermore, the evaluation of antimicrobial activity at different times of exposure to the microorganisms showed differences in effects that were dependent on the shape of the CuMPs incorporated into paper, where laminar particles exerted a sufficient effect, while no or a slight effect was observed for mixed CuMPs against Aspergillus niger. [ABSTRACT FROM AUTHOR]

In this work, tension and fracture behaviors of cellulose nanopaper (CNP) made from two different preparation approaches are comparatively studied. The CNP are prepared by casting (or C-CNP) and filtration (or F-CNP) of CNF suspension. The resulting CNP are mechanically characterized using the vision-based full-field optical method of Digital Image Correlation. Tension tests show that F-CNP has a higher strength and greater nonlinearity than the C-CNP. The crack initiation and growth characteristics of the two types of CNP are investigated using optical measurements. The data are analyzed under small-scale-yielding conditions to quantify the fracture parameters such as stress intensity factors and energy release rates at crack initiation as well as during crack growth. The results indicate that both C-CNP and F-CNP show significant crack growth resistance in the post-crack initiation regime. The F-CNP particularly offers substantial resistance to crack growth relative to the C-CNP demonstrating that filtration is the preferred method to make CNP with higher tensile strength and better fracture properties. [ABSTRACT FROM AUTHOR]

Generated in the pulp and paper production process, cellulosic pulp fines are fibrous cellulosic materials capable of passing a 200 mesh screen. Processed pulp fines remain in the pulp and affect pulp and paper sheet properties. Their specific morphology promotes interactions with fibers and alters sheet properties. Nevertheless, the 3D distribution of fines in paper sheets has not been revealed so far. Localizing fines within a matrix of fibers is challenging since both elements have the same chemical composition and fines have small dimensions. It is required to increase the contrast of pulp fines, while avoiding any alteration of initial fines morphology. In this study, fines were first separated and labeled with Rhodamine B isothiocyanate, a fluorescent dye. Labeled fines were blended with pulp at different concentrations and paper sheets were produced from each mixture. Prior to imaging, pulps and handsheets were characterized by standard pulp and paper tests and compared with references, showing no significant differences between sheets containing labeled and untreated fines. Thus, mechanical and physical tests indicated that no, or only minor alteration of fines properties by the labeling process occurred. We then applied two imaging techniques to detect the labeled pulp fines in the paper network, namely confocal laser scanning microscopy and multiphoton microscopy, visualizing the 3D distribution of fluorescent fines within the fiber network. The results obtained also allowed a differentiation between morphologically different fines showing fiber fragments more attached to single fibers whereas more fibrillar fines concentrate in fiber–fiber joints, thereby strengthening bonding. [ABSTRACT FROM AUTHOR]

The ability to pattern highly conductive features on paper substrates is critically important for applications in radio frequency identification (RFID) tags, displays, sensors, printed electronics, and diagnostics. Ink-jet printing particle-free reactive silver inks is an additive, material efficient and versatile strategy for fabrication of highly conductive patterns; however, the intrinsic wetting properties of cellulose based papers are not suitable to serve as substrates for this process. This study reports one-step and practical modification of the surface of paper substrates using industrially available materials. The paper substrates were dip-coated with films of hydrocarbon and fluorocarbon based polymeric resins. Ink-jet printing particle-free reactive silver inks on the modified paper substrates followed by fast thermal annealing resulted in highly conductive patterns. The coatings improved the conductivity of the patterns and reduced the number of printing layers required to obtain conductivity. We finally demonstrated fabrication of a printed RFID tag on the coated paper substrates operating at the frequency range of 865–870 MHz. [ABSTRACT FROM AUTHOR]

Abstract: A novel silicone release liner was prepared from porous base paper with a simple biogenic polymeric pre-coat. The introduced method does not require the typical complex pretreatment processes for a paper sheet, such as calendering or pre-coating with clay. Biogenic polymers, hydroxyethyl cellulose and methylcellulose, were used to close the pores of the paper sheet. In addition, we used polyvinyl alcohol (PVA), a commonly used barrier coating with known film-forming capabilities, as a reference to close the pores and prevent silicone penetration into the base paper. In particular, hydroxyethyl cellulose showed promising barrier properties similar to those of PVA coatings. Methyl cellulose is less appropriate for release liner production due to poor film stability and insufficient adhesion to the underlying base paper. Barrier-coatings should be applied by a blade coater rather than a roller coater to obtain homogenous coatings. When a thin silicone layer was applied to the barrier-coated papers, the measured release forces were significantly reduced from 6.5 N/25 mm, for siliconized papers without any pre-coat, to less than 1 N/25 mm after pre-coating, particularly with hydroxyethyl cellulose.Graphical abstract: [ABSTRACT FROM AUTHOR]

Abstract: In this study, we investigate the “chemical welding” of paper with the ionic liquid (IL) 1-ethyl-3-methylimidazolium acetate ([EMIM]OAc) using a two-step process. First, the IL is transported into the structure of the paper as a water solution. Then, partial dissolution is achieved by activation with heat (80-95 °C), where the water evaporates and the surfaces of the fibres partially dissolve. The activated paper is washed with water to remove IL, and dried to fuse fibre surfaces into each other. The “chemically welded” paper structure has both elevated dry and wet strength. The treatment conditions can be adjusted to produce both paper-like materials and films. The most severe treatment conditions produce films that are fully transparent and their oxygen and grease barrier properties are excellent. As an all-cellulose material, the “chemically welded” paper is fully biodegradable and is a potential alternative to fossil fuel-based plastics.Graphical abstract: [ABSTRACT FROM AUTHOR]

Abstract: Cellulose-based paper is a versatile material with a diverse array of applications. While paper is not commonly thought of as a material that shrinks, here we present a method for miniaturizing paper via periodate oxidation. Chromatography paper was exposed to varying concentrations of periodate (0.1-0.5 M) over a 96-h period. Following optimization of miniaturization parameters, fourteen different types of paper were miniaturized and reductions in surface area ranging from 60 to 80% were observed. All cellulose paper types, but not cellulose-derivatives, displayed successful miniaturization. Results were highly tunable dependent upon periodate concentration and reaction time. Potential applications of the technique are discussed, including its use as a microfabrication method.Graphical Abstract: [ABSTRACT FROM AUTHOR]

Abstract: The objective of the presented research was to determine the influence of cellulose coating, obtained from the cellulose solution in N-Methylmorpholine N-oxide (NMMO), on the structural and mechanical properties of paper. The effect of heating time of paper samples coated with cellulose dissolved in NMMO was also investigated. Depending on the heating time of the coating, a continuous or porous layer was obtained. Coating without any heating stage yielded a continuous cellulose layer of hydrophobic properties (higher contact angle in comparison to base paper), and paper of higher smoothness and increased tear resistance. Analysis of the paper samples showed that cellulose coating not only changed the surface properties of paper, but also significantly improved paper strength properties, such as the tensile index, elongation, bursting strength index and double folds number. Despite the process’ limitations (e.g. necessity of removing the NMMO), this method can be considered as a novel approach for paper property modification.Graphical Abstract: [ABSTRACT FROM AUTHOR]

A cellulose paper sheet, chemically modified with azide functions, is described to be a versatile molecular platform for copper-catalyzed 1,3-dipolar cycloaddition with terminal alkynes. This 3-step methodology was carefully optimized at each stage of the process with the support of experimental and physical evidences. Our approach allows the surface coverage of structurally diverse molecular architectures through a covalent grafting with non-hydrolysable chemical linkers. This robust linkage is highlighted with the surface hydrophobization of cellulose paper through the click ligation of cholesterol units as renewable and inexpensive hydrophobic agents. The resulting water-resistant and water-repellent paper-based material shows powerful oleophilicity properties and displays a high contact angle of 139.6°. [ABSTRACT FROM AUTHOR]

To protect forest resources and increase the value of agro-industrial residues, it would be helpful to produce paper-based materials from non-woody or recycled fiber resources. This study investigated the reinforcement mechanism of bacterial cellulose (BC) on paper sheets made from different sources including softwood, hardwood, sugarcane bagasse, bamboo, wheat straw, and recycled fiber, which represent a selection of high quality, medium quality, and low quality fibers. The results showed that by maintaining BC addition at a low level of 0.5-1.5% (total paper dry weight), the paper sheets made from high and medium quality fibers have the maximum tensile index improvement, with 5-25%. The tensile index of low quality fiber including wheat straw pulp and recycled fiber pulp increased slightly and gradually with the level of BC addition; at 5% BC addition, the tensile indexes increased by 9 and 40%, respectively. To investigate the BC reinforcement mechanism, different fiber characteristics, SEM images of BC reinforced paper, BC retention rate on paper, and the effects of dispersant addition were evaluated. It was found that high BC addition or retention rate in paper sheets do not necessarily result in good BC reinforcement effects but that proper dispersion of BC is important. [ABSTRACT FROM AUTHOR]

In museums, libraries and archives, some of the paper relics, upon ageing, are very brittle and even cannot be handled without destroying the material. This is because of the depolymerization of cellulose and, consequently, the loss of mechanical strength. To prolong the life expectancy of paper relics, the poly(methyl methacrylate- co-butyl acrylate- co-styrene) (MMA-BA-ST) was used to strengthen the fragile paper fibers in this work. The relation between the mass concentration of MMA-BA-ST emulsion and the specific properties of papers (e.g., folding endurance, tensile strength, tearing strength, whiteness and glossiness) and the ageing resistance were investigated. In addition, the effect of MMA-BA-ST on different types of paper was also studied. Furthermore, the reinforcing mechanism of MMA-BA-ST on paper was also investigated by dissipative particle dynamics simulations. The results showed that MMA-BA-ST could significantly improve the mechanical properties and ageing resistance of papers. [ABSTRACT FROM AUTHOR]

Paper with color changes caused by applied electric voltages was fabricated by combining the electric heating feature of conductive polypyrrole (PPy) and the temperature response color-changing feature of thermochromic ink. Highly conductive PPy was deposited selectively on the graphite-coated side of the paper via electrochemical polymerization. Thermochromic ink was coated on the reverse side with white color. The conductive coatings were tightly covered on the paper due to the hydrogen bonding between the pyrrole rings and the hydroxyl groups of cellulose. The obtained paper could be heated to about 45 °C and change its color significantly under an applied voltage of 4 V. [ABSTRACT FROM AUTHOR]

Chemically modified cellulose micro- and nanofibrils were successfully used as paper strength additives. Three different kinds of cellulose nanofibrils (CNFs) were studied: carboxymethylated CNFs, periodate-oxidised carboxymethylated CNFs and dopamine-grafted carboxymethylated CNFs, all prepared from bleached chemical fibres of dissolving grade, and one microfibrillated cellulose from unbleached kraft fibres. In addition to mechanical characterization of the final paper sheets the fibril retention, sheet density and sheet morphology were also studied as a function of addition of the four different cellulose fibrils. In general, the cellulose fibrils, when used as additives, significantly increased the tensile strength, Young's modulus and strain-at-break of the paper sheets. The effects of the different fibrils on these properties were compared and evaluated and used to analyse the underlying mechanisms behind the strengthening effect. The strength-enhancing effect was most pronounced for the periodate-oxidised CNFs when they were added together with polyvinyl amine (PVAm) or poly(dimethyldiallylammonium chloride) (pDADMAC). The addition of periodate-oxidised CNFs, with pDADMAC as retention aid, resulted in a 37% increase in tensile strength at a 2 wt% addition and an 89% increase at a 15 wt% addition (from 67 to 92 and 125 kNm/kg, respectively) compared to a reference with only pDADMAC. Wet-strong sheets with a wet tensile index of 30 kNm/kg were also obtained when periodate-oxidised CNFs and PVAm were combined. This significant increase in wet strength is suggested to be the result of a formation of cross-links between the aldehyde groups, introduced by the periodate oxidation, and hydroxyl groups on the lignocellulosic fibres and the primary amines of PVAm. Even though less significant, there was also an increase in wet tensile strength when pDADMAC was used together with periodate-oxidised fibrils which shows that the aldehyde groups are able to increase the wet strength without the presence of the primary amines of the PVAm. As an alternative method to strengthen the fibre network, carboxymethylated CNFs grafted with dopamine, by an ethyl dimethylaminopropyl carbodiimide coupling, were used as a strength additive. When used as an additive, these CNFs showed a strong propensity to form films on and around the fibres and significantly increased the mechanical properties of the sheets. Their addition resulted in an increase in the Young´s modulus by 41%, from 5.1 to 7.2 GPa, and an increase in the tensile strength index of 98% (from 53 to 105 kNm/kg) with 5 wt% retained dopamine-grafted CNFs. [ABSTRACT FROM AUTHOR]

Cellulose fines are-in general-small particles removed from natural cellulose fibres during refining process which is typically carried out in papermaking industry. Fines have been recognized as a separate component of papermaking fibrous raw material since their properties differ considerably from those of cellulosic fibres. Fines are characterized by low dewatering ability, very high specific surface area, and high swelling ability. Knowledge about the possibility of effective control over fines generation and swelling during refining process are nowadays of key importance. Beside its significance in papermaking process (e.g. impact on paper structure and mechanical properties and dewatering properties of the pulp), nowadays the cellulose fines fraction is considered as a raw material for the production of novel materials e.g. microfibrilled cellulose and nanocellulose. The main objective of the presented study was to determine the impact of the most important refining parameters (e.g. net refining energy, rotor speed, and pulp consistency) which could be used to control the fines development and their swelling degree. On the basis of presented research results it may be concluded that the amount of the fines generated during refining process was mainly affected by the effective refining power (net power) and the rotational speed of the refiner rotor. Also, the final swelling degree of fines varies depending on the refining operating conditions used. It was found that the swelling degree of fines was mostly influenced by the rotational speed of the refiner rotor, refined pulp consistency, and-for very low consistency (1-2%)-also pulp volumetric flow rate through the refiner. As a result, it could be concluded that-for more effective control of the refining process-greater attention to the control of these parameters should be paid. [ABSTRACT FROM AUTHOR]

Water diffusion in cellulose was studied via two-phase Kärger model and the propagator method. In addition to ruling out anomalous diffusion, the mean squared displacements obtained at different diffusion times from the Kärger model allowed to characterize the system's phases by their average confining sizes, average connectivity and average apparent diffusion coefficients. The two-phase scheme was confirmed by the propagator method, which has given insights into the confining phase-geometry, found consistent with a parallel-plane arrangement. Final results indicate that water in cellulose is confined in two different types of amorphous domains, one placed at fiber surfaces, the other at fiber cores. This picture fully corresponds to the phenomenological categories so far used to identify water in cellulose fibers, namely, free and bound water, or freezing and non-freezing water. [ABSTRACT FROM AUTHOR]

Mass deacidification has been an important topic in cellulose science and will continue to be a critical issue as long as acidic books and paper-based materials are-a often major-part of library and archive stocks. Different means are available to judge the result of a deacidification treatment and to address its sustainability and efficacy. The present study compares deacidification by dispersed particles with procedures that apply homogeneously dissolved alkaline compounds, both under humid and dry accelerated aging conditions. Analysis by size-exclusion chromatography coupled to light scattering detection is used in combination with accelerated aging. The number of chain scissions, i.e. cellulose degradation, is the parameter used for evaluation, expressed as stabilization factors relative to the non-treated specimen. Upon deacidification with homogeneous solutions stability factors of about four were reached, while deacidification with dispersed particles gave only two times longer life times (stability factor of two). Mechanistic aspects are discussed in terms of alkaline reserve, cellulose degradation and mobilities of deacidification agents. [ABSTRACT FROM AUTHOR]

The binding mechanisms of two reactive sizing agents, alkenyl succinic anhydride (ASA) and maleated sunflower oil high-oleic (MSOHO), with cellulose were studied. While ASA is produced from olefins out of fossil resources, MSOHO is a green sizing agent based on renewable plant materials. In contrast to common assumptions, that ASA is mostly covalently bound to cellulose, this study showed the largest part of ASA to be bound only by physisorption and only a rather small fraction, typically about 0.5 %, to be covalently attached by ester bonds. In the case of MSOHO, the covalent binding was only slightly higher, with about 3 % of the total amount being covalently linked. In both cases, covalently bound sizing agents were found to be almost uniformly distributed over the whole DP range of the cellulose as seen by carboxyl-selective fluorescence labeling in combination with size exclusion chromatography ('FDAM method'). [ABSTRACT FROM AUTHOR]

The combination of biopolymer science and technology with surface engineering of paper-based cellulosic materials has a lot of potential in stepping forward to a sustainable future. Various biopolymers such as oxidized starch, carboxymethyl cellulose, and polylatic acid have been commercially used to engineer paper surface. The paper-based cellulosic products are widely used for printing/writing and packaging applications. However, the production of these products are currently dependent mainly upon the use of petroleum-based materials including synthetic pigment coating latexes and barrier coating materials. The major challenges associated with some biopolymers are their relatively high costs and unsatisfactory performances. Continuing efforts are being made to enable the increased and value-added use of various biopolymers in paper surface engineering. These polymers can be based on cellulose, hemicelluloses, chitosan, alginate, protein, polylactic acid, and polyhydroxyalkanoate. The biopolymer-engineered paper products can be tailored for use as substitutes for various non-renewable materials including plastics and metals as well. Future development in the area of biopolymers for paper surface engineering is likely to lead to new possibilities and breakthroughs, paving the way for a substantially sustainable and green future. [ABSTRACT FROM AUTHOR]

Composites of cellulose fibers were made with paper-making technology. Two types of microfibrillated cellulose (MFC), obtained by with either homogenization or ball milling, were blended with hardwood fibers to give composites having high strength and low air permeability. The strengthening effects of the MFCs were compared with strengthening by cellulose microparticles (CMPs) made by cryogenic milling, with and without polyamideamine-epichlorohydrin addition. The MFC from homogenization was fully retained on the fiber web due to a broad size distribution; in contrast, the retention ratio for MFC produced by ball milling was lower than 50 % because of its smaller particle size. The small size caused the resulting paper to display a more compact and denser structure. The main distinction between the papers made with the two types of MFC was the elongation at break under wet conditions, suggesting that they reinforce the paper in different ways. On the other hand, CMPs act as mechanical debonders and could find application in tissue paper, increasing paper bulk and decreasing the density and thus improve tissue softness. [ABSTRACT FROM AUTHOR]

Hydrophilic paper was rendered with hydrophobic and superhydrophobic property after the treatment with solutions and nanoparticles of cellulose stearoyl ester (CSE), respectively. Cellulose stearoyl ester with a degree of substitution of 2.99 was synthesized from cellulose using stearoyl chloride. By dip-coating paper in CSE solution of at least 3 mg/ml in toluene, paper became hydrophobic with stable water contact angles of more than 120°. After further spray-coating using CSE nanoparticles that were prepared from CSE solution via nanoprecipitation, paper surface became superhydrophobic with water contact angles of larger than 150°. These superhydrophobic surfaces also exhibited self-cleaning character. Furthermore, the superhydrophobic paper surfaces showed a temperature-responsive character and could be turned hydrophobic after a heat-treatment at 70 °C for 5 min. [ABSTRACT FROM AUTHOR]

Vegetable oils were combined with recent nanotechnology as a sustainable method for tuning the hydrophobicity of cellulose and paper surfaces. Different soy-, sunflower-, corn-, castor-, rapeseed- and hydrogenated oils were incorporated into an aqueous dispersion of hybrid styrene maleimide nanoparticles. Here, we investigate the formation of novel coatings from these dispersions and their performance on paper and paperboard, compared with model aluminum substrates. The coated papers are evaluated by static and dynamic contact angles, microscopy, atomic force microscopy, infrared and Raman spectroscopy. The nanoparticle pigments form a porous coating after drying, while the water repellence and hydrophobicity of paperboard and paper improved with contact angles of 90-99° after drying and 98-112° after ageing. The coatings with poly(unsaturated) oils have best hydrophobicity for dispersions with an optimum viscosity of 115-150 cp required for good coverage of the paper. While homogeneous coverage of the cellulose fibers is a primary requirement, thin coatings often provide higher contact angles on paper due to roughness of the underlaying fibrous surface. After ageing, the coatings are chemically stable without oil leakage and constant imide content, while an increase in contact angles is attributed to variations in coating morphology through local re-arrangements over the paper substrate. [ABSTRACT FROM AUTHOR]

Degradation of cellulose under alkaline conditions is involved either involuntarily or deliberately in many different cellulose processing steps, such as pulping, bleaching, or aging within the viscose process, and the underlying chemistry has been the topic of numerous studies. When it comes to aging under alkaline conditions-either natural or accelerated (artificial)-the degradation processes are by far less investigated and understood. A prominent example of moderately alkaline cellulosic material is deacidified book paper from libraries which had undergone a mass-deacidification treatment. We studied their aging behavior under accelerated conditions in comparison to non-deacidified duplicates in order to better understand how the alkaline reserve, which was introduced by the deacidification treatment, affects the stability of the books on the long run. GPC analysis of cellulose and determination of carbonyl functionalities were performed, which were critical parameters to achieve a deeper insight into hydrolytic and oxidative changes of cellulose structure upon deacidification treatment and subsequent aging. Also, model book papers impregnated with different amounts of alkaline reserve were used to support the findings from the original book samples. Hydrolytic degradation rates of the original book papers were significantly reduced after mass deacidification compared to the non-deacidified duplicates. The beneficial effect of mass deacidification on cellulose stability was found to be strongly related to the amount of alkaline reserve deposited, independent of varying parameters of book papers. Although some indication of alkali-induced β-elimination was found (a minor decrease of the along-chain carbonyl content in the original deacidified book papers during aging), it did not occur to an extent that significantly influenced the molar mass of cellulose. The beneficial effect of retarded hydrolytic degradation by mass deacidification thus clearly outweighed possible negative alkalinity effects of the deposited alkaline reserve. [ABSTRACT FROM AUTHOR]

As papers become acidic and brittle over time, libraries apply mass deacidification processes to their collections in order to neutralize acids and deposit an alkaline reserve in the paper. Books commonly treated by mass deacidification have undergone natural aging of up to 150 years. The risk of alkali-induced degradation of cellulosic material upon mass deacidification remains uncertain. In the present study, the extent of β-elimination-type degradation reactions was investigated by comparing deacidified and non-deacidified counterparts, using deacidified library materials and identical issues of non-deacidified books from second-hand book shops. The study dealt with only naturally-aged papers focusing on investigation of immediate effects of mass deacidification rather than a long-term impact. Gel permeation chromatography coupled with carbonyl group labeling gave insight into cellulose chain cleavage as well as into the behavior of oxidized functionalities. Processes occurring under natural aging conditions were compared to those upon artificial oxidation of model pulps. Library books did not show a significant reduction in molecular weight after mass deacidification compared to the non-deacidified controls, which stands in contrast to oxidized model pulps. The models showed a more pronounced loss of molecular weight upon deacidification treatments. A decrease in carbonyl groups other than reducing ends was found to occur. Thus, oxidized functionalities were found to be reactive in mass-deacidification reactions; the different behavior was traced down to particular regions of oxidative damage along the cellulose chains. In general, β-elimination processes did not pose a large risk factor upon mass deacidification treatments of the naturally-aged library material tested. [ABSTRACT FROM AUTHOR]

Different types of microfibrillated cellulose (MFC) and fines suspensions were produced, characterized, and then added to a papermaking pulp suspension. High and medium molar mass cationic polyelectrolytes were used as fixatives. The drainage behavior of the pulp suspensions with additives were evaluated against the strength properties of hand sheets made thereof. The effects of salt concentration, pH, fixative type, dosage and type of fibrillar material on drainage were examined. All the MFC and fines samples produced had clearly different properties due to their dissimilar production methods, and they also introduced specific responses on the measured drainage and paper strength. Generally, the addition of MFC decreased the drainage rate of pulp suspension and increased the strength of paper. However, it was shown that by optimum selection of materials and process conditions an enhancement of the strength properties could be achieved without simultaneously deteriorating the drainage. [ABSTRACT FROM AUTHOR]

The preparation of microfibrillar cellulose (MFC) films by filtration on a polyamide filter cloth, in a dynamic sheet former and as a surface layer on base paper is described. Experimental evidence of the high tensile strength, density and elongation of films formed by MFC is given. Typically, a MFC film with basis weight 35 g/m2 had tensile index 146 ± 18 Nm/g and elongation 8.6 ± 1.6%. The E modulus (17.5 ± 1.0 GPa) of a film composed of randomly oriented fibrils was comparable to values for cellulose fibres with a fibril angle of 50°. The strength of the films formed in the dynamic sheet former was comparable to the strength of the MFC films prepared by filtration. The use of MFC as surface layer (0–8% of total basis weight) on base paper increased the strength of the paper sheets significantly and reduced their air permeability dramatically. FEG-SEM images indicated that the MFC layer reduced sheet porosity, i.e. the dense structure formed by the fibrils resulted in superior barrier properties. Oxygen transmission rates (OTR) as low as 17 ml m−2 day−1 were obtained for films prepared from pure MFC. This result fulfils the requirements for oxygen transmission rate in modified atmosphere packaging. [ABSTRACT FROM AUTHOR]

Cellulose in historic paper documents is often damaged by the writing media used, especially iron gall ink or copper pigments. Degradation induced by iron gall ink is suggested to be a synergistic process comprising both hydrolytic and oxidative reactions. These processes were studied on very low sample amounts according to the CCOA and FDAM method, i.e. by fluorescence labeling of carbonyl and carboxyl groups in combination with GPC-MALLS, respectively. This study focused on preventive means to stop the deterioration induced by iron gall ink of cellulose and to prevent further damage, keeping in mind that a suitable conservation treatment has to hinder both, hydrolytic and oxidative processes, at the same time. A combination of the complexing agent calcium phytate and calcium hydrogencarbonate in aqueous solution was proved to give optimum results. To gain insight into long term stability, an aging step was performed after treatment and different ink modifications were tested. Recording the molecular weight distributions and the carbonyl group content over time GPC analysis verified for the first time the preventive effect of this treatment. This effect was not only seen for the ink-covered areas, but extended also to areas remote from the ink lines. Ink containing copper ions responded equally positively to the calcium phytate/hydrogencarbonate treatment as the iron gall ink papers did. Gelatine, sometimes used in a similar way due to an alleged cellulose-stabilizing effect did not have a beneficial influence on cellulose integrity when metal ions were present. [ABSTRACT FROM AUTHOR]

The hygroexpansion of paper was significantly reduced, up to 28% lower amplitude of change when the paper was subjected to a change in relative humidity from 20 to 85% RH, by oxidation of the fibre wall. Never-dried bleached kraft fibres were oxidised with sodium periodate, which specifically oxidises the C2–C3 bond of 1,4-glucans so that the cellulose is partly converted into dialdehyde cellulose. Since both the dry and wet strength of laboratory sheets were significantly improved, the dry tensile strength increased from 24 kNm/kg up to 66 kNm/kg and the relative wet tensile strength increased from 1.5% up to 40%, it is suggested that the aldehydes form hemiacetal linkages within the fibre wall during the consolidation and drying of the sheets. The mechanical, hygroexpansive and moisture sorptive properties of the sheets made from the oxidised fibres were studied. The results showed that the main reason for the reduced hygroexpansion was a decrease in moisture sorptivity, i.e. when the sheets made of fibres with different degrees of cross-linking were subjected to the same change in relative humidity, the more cross-linked fibres showed a smaller change in moisture content. It was also shown that the hygroexpansion coefficient, i.e. the moisture-normalised dimensional change, was not significantly changed by the periodate oxidation, i.e. indicating that there are no improvement in dimensional stability if the paper is subjected to a specific amount of water. [ABSTRACT FROM AUTHOR]

Abstract  In this paper we present a time-temperature superposition method for predicting the permanence of paper by extrapolating accelerated paper ageing data to ambient conditions. The presented method includes a test for the presence of shift factors to superpose all of the raw accelerated ageing data over the temperature range studied to obtain a master curve, a numerical fit of the master curve for producing a master equation representing the kinetics of paper degradation, a critical examination of applying Arrhenius equation for explaining the relationship between the empirically determined shift factors and the accelerated ageing temperature, and a verification of the Arrhenius activation energy extrapolation assumption. Unlike the usual approach that extrapolates the Arrhenius relationship between lifetime and temperature, without corroborating evidence, to ambient temperatures, we test the Arrhenius activation energy extrapolation assumption by determining the influence of acidity on cellulose hydrolysis reactions, and have found that detection and identification of the acid-sensitive linkages in cellulose substances is an ultra-sensitive and reliable method to measure degradation of cellulose and paper in what is normally the extrapolation region (ambient temperatures). Taking the examples of natural ageing data in literature from 18 bleached kraft dry-lap pulps for 22 years under ambient conditions and three handsheet samples for 22 years under controlled conditions, comparison of the predictions with natural ageing results has been addressed. [ABSTRACT FROM AUTHOR]

A link is drawn between paper hornification and low temperature thermally-accelerated ageing of paper based on a review of existing research. Similarities between treatment temperature, humidity, resultant physical properties, and possible degradation mechanisms are enumerated. Hornification can be explained by irreversible intra-fibre hydrogen bonding, whereas accelerated ageing is normally attributed to chain scission and cross linking. However, in the light of the similar experimental protocols used to investigate each, the possibility of both mechanisms occurring in both experiments should be considered. The short timescales of hornification would seem to preclude chain scission and cross linking, but it seems possible that irreversible hydrogen bonding occurs during dry accelerated ageing. [ABSTRACT FROM AUTHOR]

Calculations of Hamaker constants using Lifshitz theory require the availability of accurate dielectric data, especially in the visible-ultraviolet region. We present spectroscopic ellipsometry data on well-defined cellulose films of a limited thickness range (100–140 layers) deposited on an oxidised and hydrophobised silicon substrate. The spectral data, representing measurements from a perpendicular orientation to the fibre deposition direction, was used for estimates of the necessary spectral parameters, i.e. the oscillator strengths and characteristic frequencies in the UV-range. Our calculations show that cellulose has a relatively low Hamaker constant in air (58 zJ) and water (8.0 zJ). The implications for the surface energy estimates of cellulose and colloidal interactions between cellulose and various types of fillers and coating colours are indicated. [ABSTRACT FROM AUTHOR]