Fractionation of wood due to industrial chipping: effects and potential for Kraft pulping of European spruce.

The research conducted on kraft cooking of for different chip sizes is often not representative for the industrial process since the chip size fractions were made of high-quality wood without impurities. We evaluated the effects and the potential of cooking non ideal spruce chip fractions after industrial chipping and screening. The chips were classified according to SCAN 40:01, and the respective fractions were cooked under the identical conditions to mimic the effect of a joint cooking in the industrial digester. For the undersized chips we found higher bark content, a lower screened yield, a higher Kappa number, lower fiber length and lower tensile strength. For the oversized chips, the fiber length and tensile index were also considerably lower. A lower wood quality due to high knot content in the larger fractions was found to be the reason for that. Based on the data obtained from the experiments and literature, different process options for increased yield and reduced chemical consumption are discussed, e.g., separate cooking of different chip fractions. Improved chip screening seems to be the process improvement with lowest costs and highest impact.

Assessing Fire-Damage in Historical Papers and Alleviating Damage with Soft Cellulose Nanofibers.

The conservation of historical paper objects with high cultural value is an important societal task. Papers that have been severely damaged by fire, heat, and extinguishing water, are a particularly challenging case, because of the complexity and severity of damage patterns. In-depth analysis of fire-damaged papers, by means of examples from the catastrophic fire in a 17th-century German library, shows the changes, which proceeded from the margin to the center, to go beyond surface charring and formation of hydrophobic carbon-rich layers. The charred paper exhibits structural changes in the nano- and micro-range, with increased porosity and water sorption. In less charred areas, cellulose is affected by both chain cleavage and cross-linking. Based on these results and conclusions with regard to adhesion of auxiliaries, a stabilization method is developed, which coats the damaged paper with a thin layer of cellulose nanofibers. It enables the reliable preservation of the paper and-most importantly-retrieval of the contained historical information: the nanofibers form a flexible, transparent film on the surface and adhere strongly to the damaged matrix, greatly reducing its fragility, giving it stability, and enabling digitization and further handling.

Two-dimensional talc as a van der Waals material for solid lubrication at the nanoscale.

Talc is a van der Waals and naturally abundant mineral with the chemical formula Mg3Si4O10(OH)2. Two-dimensional (2D) talc could be an alternative to hBN as van der Waals dielectric in 2D heterostructures. Furthermore, due to its good mechanical and frictional properties, 2D talc could be integrated into various hybrid microelectromechanical systems, or used as a functional filler in polymers. However, properties of talcas one of the main representatives of the phyllosilicate (sheet silicates) group are almost completely unexplored when ultrathin crystalline films and monolayers are considered. We investigate 2D talc flakes down to single layer thickness and reveal their efficiency for solid lubrication at the nanoscale. We demonstrate by atomic force microscopy based methods and contact angle measurements that several nanometer thick talc flakes have all properties necessary for efficient lubrication: a low adhesion, hydrophobic nature, and a low friction coefficient of 0.10 ± 0.02. Compared to the silicon-dioxide substrate, 2D talc flakes reduce friction by more than a factor of five, adhesion by around 20%, and energy dissipation by around 7%. Considering our findings, together with the natural abundance of talc, we put forward that 2D talc can be a cost-effective solid lubricant in micro- and nano-mechanical devices.

Combining adhesive contact mechanics with a viscoelastic material model to probe local material properties by AFM.

Viscoelastic properties are often measured using probe based techniques such as nanoindentation (NI) and atomic force microscopy (AFM). Rarely, however, are these methods verified. In this article, we present a method that combines contact mechanics with a viscoelastic model (VEM) composed of springs and dashpots. We further show how to use this model to determine viscoelastic properties from creep curves recorded by a probe based technique. We focus on using the standard linear solid model and the generalized Maxwell model of order 2. The method operates in the range of 0.01 Hz to 1 Hz. Our approach is suitable for rough surfaces by providing a defined contact area using plastic pre-deformation of the material. The very same procedure is used to evaluate AFM based measurements as well as NI measurements performed on polymer samples made from poly(methyl methacrylate) and polycarbonate. The results of these measurements are then compared to those obtained by tensile creep tests also performed on the same samples. It is found that the tensile test results differ considerably from the results obtained by AFM and NI methods. The similarity between the AFM results and NI results suggests that the proposed method is capable of yielding results comparable to NI but with the advantage of the imaging possibilities of AFM. Furthermore, all three methods allowed a clear distinction between PC and PMMA by means of their respective viscoelastic properties.

Functionalizing Surfaces by Physical Vapor Deposition To Measure the Degree of Nanoscale Contact Using FRET.

Adhesion between solid materials is caused by intermolecular forces that only take place if the adhering surfaces are at nanoscale contact (NSC) (i.e., 0.1-0.4 nm. To study adhesion, NSC can be evaluated with Förster Resonance Energy Transfer (FRET). FRET uses the interaction of compatible fluorescence molecules to measure the nanometer distance between bonded surfaces. For this, each surface is labeled with one fluorescence dye, named the Donor or Acceptor. If these molecules are in NSC, a nonradiative Donor-Acceptor energy transfer will occur and can be detected using FRET spectroscopy. Here, for the first time, we introduce an innovative concept of a FRET-based NSC measurement employing dye-nanolayer films prepared by a physical vapor deposition (PVD). The dye nanolayers were prepared by PVD from the vaporization of the Donor and Acceptor molecules separately. The selected molecules, 7-Amino-4-methyl-cumarin (C120) and 5(6)-Carboxy-2',7'-dichlor-fluorescein (CDCF), present high quantum yields (QY, QYD = 0.91 and QYA = 0.64) and a low FRET distance range of 0.6-2.2 nm, adequate for the study of NSC. The produced dye-nanolayer films exhibit a uniform dye distribution (verified by atomic force microscopy) and suitable fluorescence intensities. To validate the NSC measurements, FRET spectroscopy experiments were performed with bonded dye-nanolayer films prepared under different loads (from 1.5 to 140 bar), thus creating different degrees of NSC. The results show an increase in FRET intensity (R 2 = 0.95) with the respective adhesion energy between the films, which is directly related to the degree of NSC. Hence, this work establishes FRET as an experimental technique for the measurement of NSC, and its relation to surface adhesion. Additionally, thanks to the FRET dye-nanolayer approach, the method can be employed on arbitrary surfaces. Essentially, any sufficiently transparent substrate can be functionalized with FRET compatible dyes to evaluate NSC, which represents a breakthrough in contact mechanics investigations of soft and hard solid materials.

The effect of the strain rate on the longitudinal modulus of cellulosic fibres.

The longitudinal stiffness of cellulosic fibres plays an important role in the mechanical performance of many products these fibres are used for. Especially, the fibres' viscoelastic properties are having an influence on the product performance. In this work, tensile testing at different strain rates was performed on single fibres to investigate the rate dependence of their moduli. Four different fibre types were tested: chemi-thermomechanical softwood pulp (CTMP), bleached chemical softwood pulp (CP), unbleached softwood kraft pulp (UKP), and viscose (VIS). For each fibre sample, ten strain rates ranging from 0.113% s-1 to 800% s-1 were applied. The rate-dependent modulus E r of each fibre at each strain rate was calculated by linearly fitting the stress-strain curves. By obtaining the values of the normalized modulus, a slope value per decade was calculated to quantify the rate dependence. To exclude possible plastic and relaxation effects, two additional experiments were used: a force-controlled loading-unloading experiment and a reverse rate protocol. All cellulosic fibres tested exhibited rate-dependent behaviour with a log-linear relationship between loading rate and modulus. For each tenfold increase in loading rate we found an increase in modulus up to nearly 20%-depending on the fibre type. Viscose fibres exhibit the highest rate dependence, whereas chemical softwood pulp fibres exhibit the lowest. Supplementary Information: The online version contains supplementary material available at 10.1007/s10853-022-07722-7.

The transverse and longitudinal elastic constants of pulp fibers in paper sheets.

Cellulose fibers are a major industrial input, but due to their irregular shape and anisotropic material response, accurate material characterization is difficult. Single fiber tensile testing is the most popular way to estimate the material properties of individual fibers. However, such tests can only be performed along the axis of the fiber and are associated with problems of enforcing restraints. Alternative indirect approaches, such as micro-mechanical modeling, can help but yield results that are not fully decoupled from the model assumptions. Here, we compare these methods with nanoindentation as a method to extract elastic material constants of the individual fibers. We show that both the longitudinal and the transverse elastic modulus can be determined, additionally enabling the measurement of fiber properties in-situ inside a sheet of paper such that the entire industrial process history is captured. The obtained longitudinal modulus is comparable to traditional methods for larger indents but with a strongly increased scatter as the size of the indentation is decreased further.

Design of Friction, Morphology, Wetting, and Protein Affinity by Cellulose Blend Thin Film Composition.

Cellulose derivate phase separation in thin films was applied to generate patterned films with distinct surface morphology. Patterned polymer thin films are utilized in electronics, optics, and biotechnology but films based on bio-polymers are scarce. Film formation, roughness, wetting, and patterning are often investigated when it comes to characterization of the films. Frictional properties, on the other hand, have not been studied extensively. We extend the fundamental understanding of spin coated complex cellulose blend films via revealing their surface friction using Friction Force Microscopy (FFM). Two cellulose derivatives were transformed into two-phase blend films with one phase comprising trimethyl silyl cellulose (TMSC) regenerated to cellulose with hydroxyl groups exposed to the film surface. Adjusting the volume fraction of the spin coating solution resulted in variation of the surface fraction with the other, hydroxypropylcellulose stearate (HPCE) phase. The film morphology confirmed lateral and vertical separation and was translated into effective surface fraction. Phase separation as well as regeneration contributed to the surface morphology resulting in roughness variation of the blend films from 1.1 to 19.8 nm depending on the film composition. Friction analysis was successfully established, and then revealed that the friction coefficient of the films could be tuned and the blend films exhibited lowered friction force coefficient compared to the single-component films. Protein affinity of the films was investigated with bovine serum albumin (BSA) and depended mainly on the surface free energy (SFE) while no direct correlation with roughness or friction was found. BSA adsorption on film formed with 1:1 spinning solution volume ratio was an outlier and exhibited unexpected minimum in adsorption.