Toward a Reversible Consolidation of Paper Materials Using Cellulose Nanocrystals.
ABSTRACT: An innovative consolidation strategy for degraded paper is presented based on the reversible application of cellulose nanocrystals as sustainable fillers to reinforce mechanical properties and resistance to further degradation. The compatibility and efficacy of the proposed consolidation treatment are assessed first on pure cellulose paper, used as a model, by reliable techniques such as field emission scanning electron microscopy, atomic force microscopy, tensile tests, X-ray powder diffraction, and Fourier transform infrared spectroscopy, evidencing the influence of the surface functionalization of nanocellulose on the consolidation and protection effects. Then, the consolidation technique is applied to real aged paper samples from Breviarium romanum ad usum Fratrum Minorum S.P. (1738), demonstrating the promising potential of the suggested approach. Amperometric measurements, carried out with a smart electrochemical tool developed in our laboratory, demonstrate the reversibility of the proposed treatment by removal of the nanocrystalline cellulose from the paper surface with a suitable cleaning hydrogel. This completely new feature of the consolidation treatment proposed here satisfies a pivotal requisite in cultural heritage conservation because the methodological requirement for the ″reversibility″ of any conservation measure is a fundamental goal for restorers. A paper artifact, in fact, is subject to a number of natural and man-made hazards, inducing continuous degradation. With time, monitoring and consolidation actions need to be often performed to ensure conservation, and this tends to modify the status quo and compromise the artifact integrity. Removable treatments can potentially avoid erosion of the artifact integrity.
Project description:Alternative cementitious binders, based on industrial side streams, characterized by a low carbon footprint, are profitably proposed to partially replace Portland cement. Among these alternatives, alkali-activated materials have attracted attention as a promising cementitious binder. In this paper, the chemical stability of the matrix, in fiber-reinforced slag-based alkali-activated composites, was studied, in order to assess any possible effect of the presence of the reinforcement on the chemistry of polycondensation. For this purpose, organic fiber, cellulose, and an inorganic fiber, basalt, were chosen, showing a different behavior in the alkaline media that was used to activate the slag fine powders. The novelty of the paper is the study of consolidation by means of chemical measurements, more than from the mechanical point of view. The evaluation of the chemical behavior of the starting slag in NaOH, indeed, was preparatory to the understanding of the consolidation degree in the alkali-activated composites. The reactivity of alkali-activated composites was studied in water (integrity test, normed leaching test, pH and ionic conductivity), and acids (leaching in acetic acid and HCl attack). The presence of fibers does not favor nor hinder the geopolymerization process, even if an increase in the ionic conductivity in samples containing fibers leads to the hypothesis that samples with fibers are less consolidated, or that fiber dissolution contributes to the conductivity values. The amorphous fraction was enriched in silicon after HCl attack, but the structure was not completely dissolved, and the presence of an amorphous phase is confirmed (C-S-H gel). Basalt fibers partly dissolved in the alkaline environment, leading to the formation of a C-N-A-S-H gel surrounding the fibers. In contrast, cellulose fiber remained stable in both acidic and alkaline conditions.
Project description:When a fire strikes libraries or archives, physical deterioration of the paper is so severe that its chemical properties are often regarded as less important. However, knowledge of the chemical changes of the papers upon nearly burning is necessary to design a subsequent conservation treatment. In the present study, we have examined a rag paper object, which partially survived a fire, and analysed its chemical properties by various methods. The polymeric state of cellulose, as well as its low-molar mass degradation products, were assessed. Comparison to an identical, unharmed duplicate provided a more profound understanding of the changes caused by the fire. Light scattering analysis revealed conformational changes of the cellulose molecule after high-temperature impact, and a chemical cross-linking was observed. In our study, we found the integrity of cellulose to depend on the temperature profile induced by the fire. The low thermal conductivity of cellulose protects the material even in close proximity to the burned edges.
Project description:Ring artifact elimination is one of the popular problems in computed tomography (CT). It appears in the reconstructed image in the form of bright or dark patterns of concentric circles. In this paper, based on the compressed sensing theory, we propose a method for eliminating the ring artifact during the image reconstruction. The proposed method is based on representing the projection data by a sum of two components. The first component contains ideal correct values, while the latter contains imperfect error values causing the ring artifact. We propose to minimize some sparsity-induced norms corresponding to the imperfect error components to effectively eliminate the ring artifact. In particular, we investigate the effect of using different sparse models, i.e. different sparsity-induced norms, on the accuracy of the ring artifact correction. The proposed cost function is optimized using an iterative algorithm derived from the alternative direction method of multipliers. Moreover, we propose improved versions of the proposed algorithms by incorporating a smoothing penalty function into the cost function. We also introduce angular constrained forms of the proposed algorithms by considering a special case as follows. The imperfect error values are constant over all the projection angles, as in the case where the source of ring artifact is the non-uniform sensitivity of the detector. Real data and simulation studies were performed to evaluate the proposed algorithms. Results demonstrate that the proposed algorithms with incorporating smoothing penalty and their angular constrained forms are effective in ring artifact elimination.
Project description:In this study, Spirulina platensis (S.p.) polysaccharide (PSP) was obtained by ultrasonic-microwave-assisted extraction (UMAE) and purified by an aqueous two-phase system (ATPS). Two different methods were applied to purified Spirulina platensis (S.p.) polysaccharide (PSP), respectively, due to PSP as a complex multi-component system. Three polysaccharide fractions (PSP-1, PSP-2, and PSP-3) with different acidic groups were obtained after PSP was fractionated by the diethyl aminoethyl (DEAE)-52 cellulose chromatography, and two polysaccharide fractions (PSP-L and PSP-H) with different molecular weight were obtained by ultrafiltration centrifugation. The chemoprotective effects of PSP in cyclophosphamide (Cy) treated mice were investigated. The results showed that PSP could significantly increase spleen and thymus index, peripheral white blood cells (PWBC), and peripheral blood lymphocytes (PBL). The in vivo immunostimulatory assays demonstrated that PSP could in dose-dependent increase of TNF-?, IL-10, and IFN-? production in sera. The in vitro immunostimulatory assays showed that PSP and its fractions (PSPs) could evidently enhance the proliferation of splenocytes and RAW 264.7 cells and increase the productions of nitric oxide (NO), tumor necrosis factor-? (TNF-?), and interleukin 6 (IL-6). PSPs could also enhance phagocytic activity of RAW 264.7 cells. The acidic polysaccharide fractions of PSP-2, PSP-3, and PSP-L with small molecular weight had the higher immunostimulatory activity. Signaling pathway research results indicated that PSP-L activated RAW264.7 cells through MAPKs, NF-?B signaling pathways via TLR4 receptor.
Project description:For centuries mankind has stored its knowledge on paper, a remarkable biomaterial made of natural cellulose fibers. However, spontaneous cellulose degradation phenomena weaken and discolorate paper over time. The detailed knowledge of products arising from cellulose degradation is essential in understanding deterioration pathways and in improving durability of cultural heritage. In this study, for the first time, products of cellulose degradation were individually detected in solid paper samples by means of an extremely powerful proton HR-MAS NMR set-up, in combination to a wise use of both ancient and, as reference, artificially aged paper samples. Carboxylic acids, in addition to more complex dicarboxylic and hydroxy-carboxylic acids, were found in all samples studied. Since these products can catalyze further degradation, their knowledge is fundamental to improve conservation strategies of historical documents. Furthermore, the identification of compounds used in ancient production techniques, also suggests for artifacts dating, authentication and provenance.
Project description:Several sinogram inpainting based metal artifact reduction (MAR) methods have been proposed to reduce metal artifact in CT imaging. The sinogram inpainting method treats metal trace regions as missing data and estimates the missing information. However, a general assumption with these methods is that data truncation does not occur and that all metal objects still reside within the field-of-view (FOV). These assumptions are usually violated when the FOV is smaller than the object. Thus, existing inpainting based MAR methods are not effective. In this paper, we propose a new MAR method to effectively reduce metal artifact in the presence of data truncation. The main principle of the proposed method involves using a newly synthesized sinogram instead of the originally measured sinogram. The initial reconstruction step involves obtaining a small FOV image with the truncation artifact removed. The final step is to conduct sinogram inpainting based MAR methods, i.e., linear and normalized MAR methods, on the synthesized sinogram from the previous step. The proposed method was verified for extended cardiac-torso simulations, clinical data, and experimental data, and its performance was quantitatively compared with those of previous methods (i.e., linear and normalized MAR methods directly applied to the originally measured sinogram data). The effectiveness of the proposed method was further demonstrated by reducing the residual metal artifact that were present in the reconstructed images obtained using the previous method.
Project description:Scientific investigations of artworks are crucial in terms of preservation since they provide a measurable evaluation of the materials and the state of conservation. This is the case of Antonello da Messina's painting "Ecce Homo": its delicate state of conservation, with the need for constant monitoring, required a broad and in-depth diagnostic campaign to support the restorers. The project was carried out entirely in situ using non-invasive cutting-edge techniques and proposes a multimodal and data-centric approach, integrating 3D and 2D methodologies. The surface irregularities and the support were analysed with a structured-light 3D scanner and X-ray tomography. The painting materials were investigated with X-ray fluorescence scanning (MA-XRF) and reflectance hyperspectral imaging (HSI). Primarily, the data were jointly used for a scientific scope and provided new knowledge of the painting in terms of materials and painting techniques. In addition, two web-based interactive platforms were developed: one to provide restorers and experts with a new perspective of the hidden geometries of the painting, and the other targeted at the general public for dissemination purposes. The results of the Ecce Homo scientific analysis were exhibited, using a touch-screen interface, and developed for different user levels, from adults to kids.
Project description:Groundtruth is a Matlab Graphical User Interface (GUI) developed for the identification of key features and artifacts within physiological signals. The ultimate aim of this GUI is to provide a simple means of assessing the performance of new sensors. Secondary, to this is providing a means of providing marked data, enabling assessment of automated artifact rejection and feature identification algorithms. With the emergence of new wearable sensor technologies, there is an unmet need for convenient assessment of device performance, and a faster means of assessing new algorithms. The proposed GUI allows interactive marking of artifact regions as well as simultaneous interactive identification of key features, e.g., respiration peaks in respiration signals, R-peaks in Electrocardiography signals, etc. In this paper, we present the base structure of the system, together with an example of its use for two simultaneously worn respiration sensors. The respiration rates are computed for both original as well as artifact removed data and validated using Bland-Altman plots. The respiration rates computed based on the proposed GUI (after artifact removal process) demonstrated consistent results for two respiration sensors after artifact removal process. Groundtruth is customizable, and alternative processing modules are easy to add/remove. Groundtruth is intended for open-source use.
Project description:The presence of pressure-sensitive tapes (PSTs) on paper artworks, either fortuitous or specifically applied for conservation purposes, is one of the most frequent and difficult issues encountered during restoration. Aged PSTs can damage or disfigure artworks, compromising structural integrity, readability, and enjoyment. Current procedures are often inherently hazardous for artistic media and paper support. Challenged by the necessity to remove PSTs from a contemporary and an ancient drawing (20th century, by artists da Silva and Hayter, and a 16th-century drawing of one figure from the Sistine Chapel by Michelangelo), we addressed this issue from a physicochemical perspective, leveraging colloid and interface science. After a characterization of the specific PSTs present on the artifact, we selected a highly water-retentive hydrogel as the host of 23% wt/wt of "green" organic solvents uniformly dispersed within the gel in the form of nanosized droplets. The double confinement of the organic solvent in the nanodroplets and into the gel network promotes a tailored, controlled removal of PSTs of different natures, with virtually no interaction with the solvent-sensitive artwork. This noninvasive procedure allows complete retrieval of artwork readability. For instance, in the ancient drawing, the PST totally concealed the inscription, "<i>di mano di Michelangelo</i>" ("from Michelangelo's hand"), a possibly false attribution hidden by a collector, which is now perfectly visible and whose origin is currently under investigation. Remarkably, the same methodology was successful for the removal of aged PST adhesive penetrated inside paper fibers of a drawing from the celebrated artist Lucio Fontana.
Project description:Waterlogged archaeological wood comes from submerged archaeological sites (in lake, sea, river, or wetland) or from land waterlogged sites. Even if the wooden object seems to have maintained the original size and shape, the wood is more or less severely decayed because of chemical and biological factors which modify the normal ratio of cellulose and lignin in the cell wall. Drying procedures are necessary for the musealization but potentially cause severe shrinkages and collapses. The conservation practices focus not only on removing water from wood but also on substituting it with materials able to consolidate the degraded wood cell walls like polymers (e.g., PEG), sugars (e.g., lactitol), or resins (e.g., Kauramin). In the present work three different nano-scale consolidants were tested: lignin nanoparticles (LNPs) obtained form beech wood via a non-solvent method involving dialysis; bacterial nanocellulose (BC) obtained from cultures fed with agro-alimentary waste; cellulose nanocrystals (CNC) chemically extracted from native cellulose. Waterlogged archaeological wood samples of different species (oak, elm, stone pine, and silver fir) characterized by different levels of degradation were impregnated with the consolidants. The treatments efficiency was evaluated in terms of macroscopic observation of treated samples, anti-shrink efficiency (ASE) and equilibrium moisture content (EMC). The results obtained for the three consolidants showed substantial differences: LNPs and CNCs penetrated only about a millimeter inside the treated wood, while BC formed a compact layer on the surface of the cell walls throughout the thickness of the samples. In spite of successful BC penetration, physical evaluation of treatment efficiency showed that BC nanoparticles did not obtain a satisfying consolidation of the material. Based on the reported results more focused test protocols are optimized for future consolidation experiments.