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To respond to the rapid introduction and development of calcined clays as supplementary cementitious material (SCM), the toolbox of characterization methods for cementitious materials requires extension to raw clay characterization. Borrowing concepts and methods developed in the field of clay mineralogy, this paper outlines the merits and limits of widely accessible characterization techniques for raw clays intended for use as SCM, when calcined. The paper focuses mainly on the identification and quantification of the raw clay mineral components, as these characteristics have important implications for further material processing and performance. General notes are provided on clay sampling and pre-treatment as well as bulk chemical analysis. The main techniques considered are X-ray diffraction, thermal analysis and infrared spectroscopy. Their application on raw clays is introduced, highlighting clay-specific aspects of sample preparation, data acquisition, and processing. Guidelines and interpretation tables are provided to aid in the analysis of the acquired data, while limitations and potential interferences are identified. Options for remote prospection by infrared spectroscopy are included as well. To illustrate the type of information to be gained and the complementarity of the techniques, two representative raw clays are fully characterised. This paper aims to highlight that mineralogical characterization is a feasible and often necessary step in the study and assessment of raw clays that can deliver a wealth of informative data if carried out appropriately.

In the present work, the physicochemical, mineralogical, and morphological characteristics of coal combustion residues (CCRs) collected from two different Pulp and Paper Mills of Assam, India, have been investigated. CCRs from both the sources were mechanically sieved to obtain various size-classified fractions and their physical properties were determined using standard methods. X-ray diffraction (XRD), Fourier Transformation Infrared (FTIR) Spectroscopy, Scanning Electron Microscopy (SEM) etc. techniques were employed to study the mineralogical and morphological characteristics of each size classified fraction. The loss on ignition (LOI) values of the coarser fractions were found to be unexceptionally high, implying the presence of a huge amount of unburned carbon, and indicating the incomplete combustion of feed coal. From the utilization point of view, coarser fractions may be recycled (as domestic fuels) and less-coarse fractions may be used as adsorbents of toxic organic chemicals. Due to th...

Cellulose oxidative and hydrolytical degradation is one of the greatest problems for the conservation of paper supports. To contrast these degradation processes, both deacidification and reduction of the oxidized functions are needed. Dealing with original documents, it is often impossible to perform the two mentioned treatments in aqueous solutions and in a distinct subsequent way, because of the fragility of the artifacts. After studying, in a separate way, an effective deacidifier (calcium propionate) soluble in ethyl alcohol and many reducers (boron complexes), able to act in different non-aqueous solvents, it was decided to test a simultaneous method of deacidification and reduction in ethanol. This paper presents the chemical-physical results obtained by applying simple deacidification and simultaneous deacidification-reduction on laboratory paper samples that were artificially aged and then re-measured after 10 and 15 years of natural aging. Results show that all alcoholic treatments are very effective: papers are stable also after a long period of both artificial and natural aging.

The use of clays as resource of supplementary cementitious materials (SCMs) for a new generation of low-carbon cements and concretes is currently the subject of intense research efforts. To this purpose, a large number of clay resources have been explored, characterized and evaluated. This paper introduces the basic knowledge and concepts on clay occurrence and clay mineralogy, before presenting up-to-date knowledge on properties and occurrence of clay resources suitable for use as SCMs. Occurrence, distribution and chemical and mineralogical selection criteria are discussed for kaolinitic clays, which often show superior reactivity and performance. 2:1 clay mineral resources have received somewhat less attention as SCM resources, however recent developments indicate significant potential for calcined impure common clays, and are reviewed. An overview of ubiquitous clay mineral-bearing waste materials also identifies important opportunities for alternative clay sourcing in mining or extraction residues, and dredged or excavated sediments.

Hybrid material based on halloysite nanotubes (HNTs) and sodium perfluorooctanoate (NaPF8) was used as a consolidant for paper treatment. The consolidation efficiency was determined by thermogravimetry as well as by paper grammage determination. Morphological analysis of the treated paper was performed by means of scanning electron microscopy while the effect of modified HNTs on the thermal behaviour of the cellulose fibres was investigated by differential scanning calorimetry which determined the combustion enthalpy of the paper.Water contact angle measurements were performed to study the paper wettability. The physico-chemical properties investigated (mesoscopic structure, thermal stability and wettability) of the treated paper were correlated successfully with the consolidation loading and, consequently, to the affinity between the fluorinated modified HNTs and the fibrous cellulose structure. This study proposes a new green protocol for paper consolidation based on natural tubular nanoparticles with a flame retardant effect.

The subject of this present work is a group of nine historical pictures shot in Palermo by the Sicilian photographer E. Interguglielmi in 1912. They are nine matte-collodion prints mounted on the original cardboard supports and all of them show foxing stains affecting the paper surface. In order to characterise the chemical composition of the supports and investigate foxing spots, non-destructive and micro-destructive analysis were carried out. X-rays fluorescence (XRF) analysis was used to characterise the elemental composition of all the mounting boards, allowing a comparison between the foxing spots and non-affected areas. Laser-Induced Breakdown Spectroscopy was used to investigate the presence of lower atomic number elements, not detectable by XRF, while SEM imaging allowed the investigation of surface appearance and nature of original paper samples from the cardboards.

This report deals with the effects of various chemical-treatments - carboxymethylcellulose-grafted (CMC) pulp in different ionic forms (Na+, Ca2+, and Al3+), cationic starch, anionic polyacrylamide ...

Needs for high ash loading in printing paper increase as green house gas (GHG) emission regulation becomes more stricter and pressure of lowering paper production cost increases. To meet the needs, a new type of filler was developed. The mixture of ground calcium carbonate (GCC) and calcium oxide was pre-floccuated with polyelectrolyte and further treated with carbon dioxide to form new calcium carbonate between GCCs. The final products were called as hybrid calcium carbonate (HCC), and its properties were compared to the GCC and the pre-flocculated GCC. Results showed increase in tensile, smoothness, opacity, and bulk for HCC.

A method to predict optical variations from high resolution measurementsof paper properties is evaluated in this work. The method combines thepoint-wise values of high resolution maps of filler content and grammagewith an empirical model derived in an earlier study to predict thespatial optical variations in paper.The method has been applied on two paper samples, a laboratory paper anda commercial 80 g/m(2) copy paper. The optical variations have beenpredicted at a scale of 1 mm(2). Validation has been made by using ahigh resolution spectrophotometric setup to measure the spatialreflectance variations in the paper. The results show that for thesamples used, the influence of filler content variations and densityvariations on the optical variations is small compared to influence ofthe grammage variations.

Latent fingerprint deposits on thermal paper sourced from the U.S., China, the U.K., and Australia have been visualized by heating. U.S. and Chinese sourced paper produced two distinct types of fingerprint development. In one type (type 1), the paper dye colors where the deposit is present (as previously reported) and in the other type (type 2) the 'inverse' of this gives paper coloring only in areas not coincident with the deposit. Both development types gave identifiable fingerprints, the majority fading within 24 h of heating. Fingerprint development from U.K. and Australian sourced paper was exclusively type 1 and resistant to fading. Temperatures for fingerprint visualization were higher for U.S. paper (64-71°C) and Chinese paper (75-95°C) than for U.K. and Australian sourced paper (43-50°C). Particularly for Chinese sourced paper, these temperatures were within a few degrees of the normal paper color temperature. A mechanism for type 2 fingerprint development is proposed.

The aim of this study was to optimize the modification of Egyptian kaolinite for application in paper coating. The study focused on four modification methods; sedimentation process, chemical bleaching, calcination, and dealumination. The effect of these methods on the structure of kaolinite was studied using X-ray fluorescence (XRF), X-ray diffractometer (XRD), Fourier transform infrared spectrometer analysis, and field emission SEM. The original and modified kaolinites were applied in paper coating mixtures. The results of XRF analysis showed that the Fe2O3 and TiO2 in Egyptian kaolinite were reduced chemically via sodium dithionite from 0.41% to 0.25% and 2.20% to 2.00%, respectively. Calcination at 900°C, followed by acid activation and bleaching, showed a further decrease in Fe2O3 and TiO2 impurities to 0.012 and 1.45 (wt%), respectively. XRD results revealed that all characteristics reflection of kaolinite disappeared upon calcination. SEM investigation showed a significant reduction in kaolinite particle size. Calcination and dealumination of kaolinite did not improve coated paper roughness, while air permeance and optical properties significantly increased in comparison with commercial kaolinite. In addition, a significant improvement was observed in coated paper mechanical properties including burst, tensile strength, stretch, and tensile energy absorption with respect to original and commercial kaolinite. In contrast, the kaolinite fraction

The saltwater immersion method was developed to inhibit mould growth on flood- or tsunami-damaged paper. Commercially available fine paper used for printing and writing showed decreased tensile indices after saltwater immersion. The salt remaining in the paper tended to increase the moisture content because of the salt deliquescence and moisture in the air. The tensile index was restored by removing salt from the paper. Crystallization and distribution of salt in interfibre pores were also considered to influence interfibre rebonding. The difference in the fibre responses to saltwater depended on the relationship between nano-scaled pores in the fibre walls, osmotic pressure, and the degree of sizing, which resulted in low water retention values. More of the starch applied as a surface sizing agent was dissolved or dispersed during distilled water immersion than saltwater immersion. This loosened the fibre network, which was a factor that decreased the sizing degree of the paper.

A highly preferred orientation of I 2 -LiI(HPN) 2 film on the paper was found. The electrochemical property of a new flexible all-solid-state Li/I 2 -LiI(HPN) 2 film paper battery was examined at wide temperatures for the first time. This paper battery is capable of achieving a high discharge energy of 250 Wh/kg with a plateau potential region at 2.70 V versus Li/Li + at 70 °C. The interfacial layer of (LiI) (1+ x ) I (2− x ) (HPN) 2 instead of LiI between lithium and I 2 -LiI(HPN) 2 film should be responsible for the high electrochemical activity of the lithium–iodine paper battery.

Summary Surface textures of a large collection of photographic papers dating from 1896 to the present were measured using a laser scanning confocal microscope (LSCM) with four different objective lenses. Roughness characterization parameters were calculated from the texture measurements and were compared with gloss measurements. Characterization by the area-scale fractal dimension (Das) and the area-scale fractal complexity (Asfc) provided the strongest correlations between gloss reflectance and surface texture. The measurements with the 5× and 10× objectives, which contained many large-scale, spiky measurement artifacts that distorted the measurement, resulted in the strongest correlations (R2 > 0.8) compared to the 20× and 50× (R2

In this study, perennial fast growth Napier grass fibers were used for pulp and papermaking. Chlorination and alkaline processes were carried out using sodium chlorite and sodium hydroxide respectively, for pulp extraction from Napier grass. Detailed chemical composition analysis of the Napier grass fibers and the extracted pulp was carried out and a comparison with other perennial grasses was made. The extracted fibers and pulp obtained from Napier grass were characterized using scanning electron microscopy and Fourier transform infrared spectroscopy. The physical, optical, and mechanical properties of Napier grass pulp handmade paper sheets produced in the laboratory were investigated by finding the opacity, brightness, tensile index, breaking length, and burst index. Handmade paper sheets made from Napier grass pulp were compared to paper made from other perennial grasses. The superior properties of paper produced from Napier grass pulp indicate the suitability of Napier grass as an alternative non-woo...

In this study, uncoated paper was characterized. Three-dimensional structure of the layer was reconstructed using imaging results of micro-CT scanning with a relatively high resolution $$(0.9~\upmu \hbox {m})$$ . Image analysis provided the pore space of the layer, which was used to determine its porosity and pore size distribution. Representative elementary volume (REV) size was determined by calculating values of porosity and permeability values for varying domain sizes. We found that those values remained unchanged for domain sizes of $$400\times 400\times 150\,\upmu \hbox {m}^{3}$$ and larger; this was chosen as the REV size. The determined REV size was verified by determining capillary pressure–saturation imbibition curves for various domain sizes. We studied the directional dependence of curves by simulating water penetration into the layer from various directions. We did not find any significant difference between curves in different directions. We studied the effect of compression of paper on curves. We found that up to 30% compression of the paper layer had very small effect on the curve. Relative permeability as a function of saturation was also calculated. Water penetration into paper was visualized using confocal laser scanning microscopy. Dynamic visualization of water flow in the paper showed that water moves along the fibers first and then fills the pores between them.

The purpose of this article is to evaluate the potential risk of exposure to nanoparticles of workers in paper mills. In the final stage of the paper production, the very large sheets are wound onto large reels, where these are processed depending on their ultimate use. Paper is smoothed and compacted by passing through metal rollers. During these mechanical treatments nanometric ultrafine particles are generated. In particular, the nanoparticle presence, size and morphology were investigated and differences between particles produced either in summer or winter seasons were explored. To this aim Atomic Force Microscopy (AFM) and Dynamic Light Scattering (DLS) were employed to analyze nano powders filtered in environments of different paper mills to determine structural morphology and sizes. Large breathable particles, with size in the range from 4 μm to 250 nm have been sampled to evaluate the mean level of exposure. By comparing nanoparticles collected from paper mills in summer and in winter we revealed that the number of nanoparticles collected in winter is strictly related to heat generated by the heating system.

The modification of low quality Egyptian kaolinite to be acceptable as a pigment for paper coating was reported in this work. Sedimentation, chemical bleaching, preparation of organo kaolinite and preparation of nano-kaolinite were the modification methods used in this study. The modified pigments were characterized using X-ray fluorescence, an X-ray diffractometer, Fourier-transform infrared spectroscopy and scanning electron microscopy. The original and modified kaolinites were applied in paper coating mixture. The results of XRF analysis showed that Fe 2 O 3 impurities reduced by using sodium dithionite from 0.41 to 0.25 (wt %). XRD data revealed shifting of basal space of kaolinite from 7.14 to 11.8 A with an intercalation ratio of 80% upon grinding with urea for 5 h. Meanwhile, IR spectra showed that NH–CO molecule (refer to urea molecule) exists in the intercalated kaolinite. The characteristic peak of kaolinite completely disappeared during dispersion of kaolinite–urea in paper coating suspension which showed the exfoliation of kaolinite–urea layers through the binder (nano-kaolinite). The SEM images of intercalated kaolinite–urea and exfoliated kaolinite/binder revealed thin flacks with particle size ranging from 500 nm and 300 nm, respectively. Nano-kaolinite caused a significant decrease in coated paper roughness and an increase in optical properties compared with the original and commercial kaolinite. Air permeability of coated paper increased and was better than commercial kaolinite. Although, nano-kaolinite reduced the mechanical properties of coated paper, it produced coated paper having print density and print gloss higher than the ones containing the original and commercial kaolinite.

The aim of this study was to evaluate the effects of dose and dose rate of gamma irradiation on the physical properties of commercial papers commonly used in libraries and archives to optimize the irradiation conditions. Three different brands of paper of different fiber compositions were treated, using a 32 factorial design with four replicates of the center point, with doses ranging from 2 to 11 kGy and dose rates between 1 and 11 kGy/h. Chemical, mechanical and optical properties were determined on the samples. With some differences between the different kinds of papers, tensile strength, elongation, TEA, and air resistance were in general, unaffected by the treatment. The minimum loss of tear resistance and brightness were obtained with doses in the range 4–6 kGy at any dose rate for all three kinds of paper. These conditions are ideal to remove insects and sufficient to eliminate fungus. Fil: Area, Maria Cristina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Materiales de Misiones. Universidad Nacional de Misiones. Facultad de Cs.exactas Químicas y Naturales. Instituto de Materiales de Misiones; Argentina Fil: Calvo, Ana María. Comisión Nacional de Energía Atómica; Argentina Fil: Felissia, Fernando Esteban. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Materiales de Misiones. Universidad Nacional de Misiones. Facultad de Cs.exactas Químicas y Naturales. Instituto de Materiales de Misiones; Argentina Fil: Docters, Andrea. Comisión Nacional de Energía Atómica; Argentina Fil: Miranda, María V.. Comisión Nacional de Energía Atómica; Argentina

The physical structure of coating layer have an important influence on transferring and setting of the printing ink. In this study, the effect of pigment on surface microstructure and surface free energy was investigated. The findings indicated that the pigment affected the pore size, depth and distribution of the coated paper surface. Kaolin pigment compared with calcium carbonate pigment was good to improve the paper surface smoothness. Surface free energy of kaolin pigment coating was higher than calcium carbonate pigment coating, which showed that surface wettability of coating with kaolin pigment was better than calcium carbonate pigment.

We investigated the behaviour of salt solutions during the drying process in porous stone and the extraction of salts by paper pulp poultices (PPP). The investigations were carried out at a 300 year old boundary wall of the Worcester College in Oxford, UK, as well as under laboratory conditions. The laboratory blocks of porous, bioclastic limestone (Aflenzer stone, Austria) were cut into stone cubes and prisms (5 × 5 × 5 and 5 × 5 × 20 cm) and soaked first with ultrapure H2O and second with different concentrations (0.1, 0.5 and 1 mol l−1) of a saline solution of NaCl and Na2SO4 to determine their behaviour during the dehydration process under different conditions. After determining the capillary absorption coefficient and the capillary rise behaviour of the stone cubes, we sampled material by PPP and by drilling. The samples were immersed in ultrapure water and the salt ion content was measured via conductivity and ion chromatography (IC). The main aim of the laboratory analysis was to investigate the effectivity of the PPP in extracting salts from the stone and to derive a semi-quantitative calibration (PPP results vs. original salt content). The field work at the college boundary wall comprised sampling (PPP and stone surface material) at surfaces of different weathering features. Finally, the field work results were compared to the laboratory work. The lab experiment results show that approximately 24% of the salts within a 100% saturated stone cube moved into the poultice within the 1 h of application. At 75% and lower saturation degrees, only 14–11% of the salts moved into the respective poultices. For the field setting, the amount of anions extracted by PPP is 6–63% (mean 20.7%) of the amount found in the stone samples. The spatial distribution of salt ion concentrations, collected by poultices, corresponds with the ‘hot spots’ of weathering.

Causticizing precipitated calcium carbonate (CPCC) as a by-product of the green liquor causticizing process can be used as paper filler to save resources and reduce costs. In this study, CPCC was prepared with green liquor and quicklime, which were obtained from an alkali recovery line of a paper mill. The factors influencing crystal morphology of CPCC, such as slaking temperature, slaking time, and causticizing time were investigated. The morphology of CPCC was observed and analyzed for optimizing reaction conditions. The following were compared: properties of CPCC obtained in this study, conventional CPCC (white mud) from a paper mill, and commercial PCC as fillers. The results showed that slaking time and causticizing time were important for morphology control. Spindle-like and rod-like CPCC obtained in this study had better drainability and retention, higher paper bulk, opacity, and physical strength compared to conventional CPCC, and had nearly the same performances as commercial PCC.

This paper presents a study into the potential of visible spectroscopy with chemometrics as an approach to dating blue ball tip inks on paper documents. Analysis of six inks left under various conditions found that the majority of those kept in the dark could still be matched to the source pen after 32 months of ageing. Conversely, the majority of those exposed to light exhibited rapid spectral changes that continued throughout the 32 month period. Partial least squares regression (PLSR) was used to generate dating models for inks aged with exposure to light. Evaluation using an external test set found absolute dating to be challenging for these ink deposits within the first 2–6 months of ageing. However, predictive accuracy was found to improve for long-term ageing, with two-year old samples yielding age estimates with a maximum error of 6 months. This rapid, non-destructive methodology could assist document examiners in the relative ageing or approximate age determination of questioned documents, as well as the identification of document alterations.

In a case study to assess the possibilities and limitations of determining the exact age of paper, we measured radiocarbon (14C) concentrations in bulk-paper cellulose and starch extracts from 20 known-age paper samples of the last 65 yr. As expected, 14C concentrations in single-seasonal grown starch extracts are in reasonably good agreement with post-bomb atmospheric 14C. In contrast, 14C concentrations in bulk-paper cellulose indicate apparent admixtures of tree-ring fibers spanning up to >50 yr. In a forensic investigation, combining 14C results from single-seasonal components like starch with those from long-lived fibers, could potentially enhance the precision of paper production-date estimates for samples made after 1955.

For casework applications, understanding the source processes used to create a material and the effects of those sources on the results obtained by Isotope Ratio Mass Spectrometry (IRMS) of a bulk material is important. Likewise, understanding the effect of environment, home/office printing processes and some forensic testing in at least a basic context, ensures that in casework, enough information on the effects of these variables is available during comparison and interpretation. In this study, which focuses on oxygen isotopic abundance measurements, both fractionation and mixing effects were observed within the pulping and production process. Also observed in the carbon isotopic experiments, sampling that included toner changed the measured isotopic abundance values of the paper and should be avoided in casework. Inkjet printing processes were not shown to have an effect on the paper oxygen abundance values. Samples that were treated for fingerprints using 1,2-Indandione-Zn prior to sampling showed the greatest risk for misinterpretation of whether two samples had originated from the same source. While this study provides a good basis and understanding of the effects of a range of factors on document paper oxygen isotope values, further testing for a range of specific casework scenarios is required and should be undertaken on a case by case basis as the need arises.

Paper and paperboard manufacturers need to quantify the carbon footprint and environmental impact of their products to satisfy market, social and government demands. Coated paper products contain minerals, such as kaolin and calcium carbonate, at significant levels; some coated paper grades have mineral contents as high as 45% by weight. Some uncoated paper has no mineral content, but most uncoated paper contains some mineral to improve appearance, process efficiency and cost. Super-calendared paper grades can contain levels of mineral up to 35% by weight. This paper describes how to calculate the carbon footprint of kaolin and calcium carbonate minerals used for white pigments. The carbon footprint of these minerals strongly correlates to the primary energy sources, final product form and energy used to calcine kaolin and lime. Kaolin and calcium carbonate pigments have a favorable impact on the carbon footprint of paper and paperboard products by directly substituting for fiber and by reducing the energy needed for paper making.

Accurate evaluations of beta dose rates are crucial in luminescence and electron spin resonance (ESR) thermochronology. Most igneous rocks are heterogeneous and have complex mineralogical structures that render them unsuitable for the conventional methods of beta dose rate calculations based on infinite matrix assumptions. The recently developed software DosiVox-2D provides a Monte-Carlo approach for calculating beta dose rates in realistic heterogeneous geometries. In this paper, we present 2D simulations of uniform and layered igneous rocks. For the modelling, mineral distribution maps were obtained by QEM-EDS (quantitative evaluation of minerals using energy dispersive spectroscopy) and radionuclide concentrations in minerals were determined by laser ablation (LA) ICP-MS. The results show that the skewness of beta dose rate distributions in quartz reduces as the K concentration in a rock increases, and the estimation of the beta dose rate can be critically influenced by the U and Th concentrations and distributions.

Paper coating pigment plays an essential role in the achievement of the desired end paper qualities. Different pigment varieties are available for paper coating. Ground calcium carbonate (GCC) is the major one used frequently in coating formulations. Precipitated calcium carbonate (PCC) is gradually gaining importance in paper coating, as it can be prepared in different shapes and sizes. The present study was carried out to determine the influence of PCC pigments with different shapes and sizes on paper properties, and their limitations and advantages when blended with finer grade GCC. PCC pigments of calcite and aragonite crystalline polymorphs having rhombohedral, orthorhombic, and scalenohedral habits were selected for the study. It was observed that the viscosity and water-holding capacity of the coating color was reduced with the introduction of PCC in the coating formulation. The PCC pigments showed greater light scattering, opacity, and smoothness of the coated paper as compared to the GCC pigment. The clustered (rosette) shape of scalenohedral habit calcite PCC results in the greatest light scattering, opacity, and surface strength amongst all PCCs. The aragonite PCC of orthorhombic habit and calcite PCC of rhombohedral habit show an almost similar trend in coated paper properties with the greatest smoothness and paper gloss.

Large numbers of soil samples are routinely analyzed using methylene blue (MB) titration to determine clay content. Although, the MB filter paper spot test titration is simple, it is labor-intensive, subjective, and leaves no record for subsequent re-examination. Preliminary thermometric monitoring of the titration indicated a switch from endothermic to exothermic reaction during titration. We examined this nearly universal property of physicochemical processes as a potential replacement method to automate the MB clay titration, making use of literature data. We translated the isothermal enthalipmetric titration of montmorillonite using MB by Rytwo and Ruiz-Hitzky to an adiabatic thermometric titration (2003). The plot of temperature versus titrant volume gave two intersecting linear segments dependent on the titrated percentage of the clay's cation exchange capacity (CEC). The MB filter paper spot test endpoint reflects the first excess MB that persists in the solid suspension, which also happens to be a function of the clay's CEC. The spot test endpoint is correlated to the thermometric indicator point and, for montmorillonite, the two are related by an exact factor of two. Although this factor will naturally be dependent on the clay minerals in the samples, the analyses show that the thermometric indicator titration method is a viable replacement for the spot test. The proposed automation is commonplace as it is practiced with other types of titrations.

The surface composition of 18th century papers was investigated by means of ToF-SIMS and XPS. The aim of the present study was to explore the possibility of using these surface sensitive methods to obtain information which can help to determine the manufacturing process, provenance and state of conservation of ancient papers. The ToF-SIMS results indicate that the analyzed papers were sized by gelatin and that alum was added as hardening agent. The paper sheets produced in near geographical areas but in different paper mills exhibit a similar surface composition and morphology of the fibers as shown by the ToF-SIMS measurements. The ToF-SIMS and the XPS results indicate that a significant fraction of the cellulose fibers is not covered by the gelatin layer. This was observed for the ancient papers and for a modern handmade paper manufactured according to the old recipes.