The role of relative humidity on crystallization of calcium carbonate from calcium acetoacetate precursor

Abstract Calcium acetoacetate, Ca(OAcAc)2, was exposed 7, 30 and 365 days to different values of relative humidity (33%, 48%, 75% and 96%) at 40 °C in order to study its transformation to CaCO3. The resulting Ca(OAcAc)2 decomposition and the time dependence of the phase transformations were monitored and critically evaluated by Fourier transform infrared spectroscopy, field emission scanning electron microscopy and X-ray powder diffraction. The impact of relative humidity on CaCO3 polymorph formation was thoroughly assessed. In all of the conditions used and for all ageing periods, the formed crystal structure is found to be vaterite. At the lowest relative humidity (33%), the amorphous CaCO3 remains more or less almost untransformed even after one year of exposure. It is proposed that the reason for the stability of amorphous CaCO3 is due to the limited amount of physisorbed water on the surfaces of the particles, which is considered the driving force for its transformation. However, the carbonation process is faster in the case of the highest humidity (96%). The findings are not only important for better solutions in the field of cultural heritage, but also shed new light on the fundamental mechanism of CaCO3 crystallization

Stabilization of fish protein‐based adhesive by reduction of its hygroscopicity

Protein-based fish adhesives have historically been used in various bonding applicationshowever, due to the protein’s high affinity for water absorption, these adhesives become destabilized in high-moisture environments, resulting in reduced bondline strength and early failure. This limitation makes them unsuitable for industrial applications with higher demands. To address this issue, water-insoluble raw powder materials such as iron, copper, or zeolite were incorporated into natural fish adhesives. In this study, the hygroscopicity, dry matter content, thermal analysis (TGA/DSC), FT-IR spectroscopy, surface tension measurements, vapour permeability, and scanning electron microscope (SEM) of the modified adhesives were determined. In addition, the bonding properties of the modified adhesives were evaluated by the tensile shear strength of the lap joints, and mould growth was visually inspected. The resulting modified protein-based adhesives demonstrated improved stability in high humidity environments. Enhancing the hygroscopic properties of protein-based fish adhesives has the potential to unlock new opportunities and applications, providing a healthier and more environmentally sustainable alternative to petroleum-based adhesives

Flexible polymer connections for clt structures

This paper explores the possibility of using flexible polymer adhesives to dissipate energy in CLT buildings during earthquakes. In the first series of tests, pull-off tests of various polyurethane (PUR) adhesives were performed. The connection was tested in pull-pull configuration using monotonic, tension-only loading. The tests have shown that the adhesive can resist large deformations already in tension loading and with small thicknesses of the bond-line. Based on the pull-off test results, one adhesive has been selected for further testing. Monotonic lap-shear tests were performed with the selected adhesive and thick bond-line (3 mm and 6 mm). The results show, that the standard method for lap-shear testing (EN 205) needs to be adapted for thick glue-line. It was found that the strength of 3 mm glue-line is higher than 6mm one, which is in agreement with adhesion theory. The flexible PUR adhesives could potentially be used in CLT structures for anchoring the CLT wall with “flexible” glued-in rods or as a “flexible” vertical shear connection between the CLT walls. Such systems have a potential to dissipate energy in seismic areas

Shear strength of fish glue bonds of glued wood evaluated by the ABES method

V prispevku smo s pomočjo sistema za avtomatizirano vrednotenje zlepljenosti (ABES) ugotavljali razvoj strižne trdnosti ribjega kleja pri lepljenju lesa. Uporabili smo bukov (Fagus sylvatica L.) furnir, ki smo ga lepili pri konstantnem tlaku 12 barov, medtem ko smo spreminjali temperaturo in čas stiskanja. Temperatura je znašala med25 °C in 100 °C, z intervalom 25 °C, čas stiskanja pa od 1 minute do 60 minut. Dosežena maksimalna strižna trdnost je znašala okoli 10 N/mm², dosegli smo jo pri vseh štirih proučevanih temperaturah stiskanja. Na podlagi rezultatov študije smo ugotovili, da strižna trdnost ribjega kleja pri različnih temperaturah segrevanja neenakomerno narašča. Pri višjih temperaturah segrevanja hitreje dosežemo maksimalne strižne trdnosti. Strižne trdnosti spoja lepila iz ribjega kleja smo ugotavljali tudi po standardih EN 204 in EN 205.Detail of the development of the shear strength of fish glue in wood bonding using an automated bonding evaluation system (ABES) are presented. Beech (Fagus sylvatica L.) veneer was used, which was compressed at constant pressure of 12 bars while the temperature and pressing time were varied. The temperature ranged between25°C and 100°C with an interval of 25°C, while the time period was between 1 minute and 60 minutes. The achieved maximum shear strength was approximately 10 N/mm², which was reached at all four studied pressing temperature intervals. Based on the study results, we found that the shear strength of fish glue increases unevenly at different heating temperatures. Maximum shear strength values are reached faster at higher heating temperatures. The shear strength of the fish glue bonds was also determined according to the EN 204 and EN 205 standards

Improved synthetic route of incorporation of nanosilicon species into phenol-formaldehyde resin and preparation of novel ZnAl-layered double-hydroxide hybrid phenol-formaldehyde resin

Hybrid phenol-formaldehyde (PF) resins represent one of the most important niche groups of binding systems for composites. New industrial needs, environmental requirements, and price fluctuations have led to further research on materials with enhanced mechanical and thermal properties. The preparation of novel hybrid materials can be achieved by inclusion of various elements or functional groups in the organic polymer phenolic framework. Herein, we report the synthesis and characterization of a PF-based hybrid material with different nanoscale silicone species and ZnAl-layered double hydroxide (LDH). The main goals of this study were to improve the synthetic pathways of hybrid resin, as well as to prepare granulated composite materials and test samples and determine their characterization. Added inorganic species increased the glass-transition temperature by a minimum of 8 °C, which was determined using differential scanning calorimetry (DSC). Rheological properties (melting viscosity and flow distance) of the hybrid resin were measured. The homogeneity of distribution of added species across the organic matrix was evaluated with scanning electron microscopy (SEM). With synthesized new hybrid-binding systems, we prepared different granulated composite materials and evaluated them with the measurements of rheological properties (flow curing characteristics). Tensile strength of samples, prepared from granulated composite material, improved by more than 5%

Improving the flame retardancy of wood using an eco-friendly mineralisation process

A novel environmentally friendly method for in situ formation of CaCO3 deep inside a wood’s structure is presented. The method is based on vacuum-pressure impregnation using a one-component treatment medium – a water solution of calcium acetoacetate - and a single stage process to significantly improve the fire retardancy of the treated material

Improved synthetic route of incorporation of nanosilicon species into phenol-formaldehyde resin and preparation of novel ZnAl-layered double-hydroxide hybrid phenol-formaldehyde resin

Hybrid phenol-formaldehyde (PF) resins represent one of the most important niche groups of binding systems for composites. New industrial needs, environmental requirements, and price fluctuations have led to further research on materials with enhanced mechanical and thermal properties. The preparation of novel hybrid materials can be achieved by inclusion of various elements or functional groups in the organic polymer phenolic framework. Herein, we report the synthesis and characterization of a PF-based hybrid material with different nanoscale silicone species and ZnAl-layered double hydroxide (LDH). The main goals of this study were to improve the synthetic pathways of hybrid resin, as well as to prepare granulated composite materials and test samples and determine their characterization. Added inorganic species increased the glass-transition temperature by a minimum of 8 °C, which was determined using differential scanning calorimetry (DSC). Rheological properties (melting viscosity and flow distance) of the hybrid resin were measured. The homogeneity of distribution of added species across the organic matrix was evaluated with scanning electron microscopy (SEM). With synthesized new hybrid-binding systems, we prepared different granulated composite materials and evaluated them with the measurements of rheological properties (flow curing characteristics). Tensile strength of samples, prepared from granulated composite material, improved by more than 5%

Environmentally friendly protection of European beech against fire and fungal decay using a combination of thermal modification and mineralisation

The demand for construction timber is continuously increasing, due to its favourable characteristics. However, the adequate protection of wood is key to its successful use, as it is flammable and susceptible to biodegradation. Given that thermal modification enhances the durability of wood, and mineralisation with CaCO3 considerably improves its fire properties, it is worth considering the combined effects of the two methods. European beech (Fagus sylvatica) was selected to determine the effects of a) thermal modification, b) mineralisation through the in-situ formation of CaCO3, and c) a combination of the two procedures, on resistance to decay fungi, reaction to fire and the mechanical properties of the wood. Microscopic analysis and comparisons of the samples before and after exposure to fungi were also conducted. Mineralised wood generally had a slightly alkaline pH value and higher equilibrium moisture content, while thermal modification lowered the equilibrium moisture content. The present study demonstrated the combined effect of thermal modification and mineralisation: the best response to fire as well as resistance to fungi was achieved when the two treatments were combined. Results from the Brinell hardness and three-point bending tests indicate that both modification procedures can slightly impair the mechanical properties of the wood

Dependence of binder and photocatalyst in photocatalytically active printing ink

Photocatalytically active printing ink changes its colour when exposed to UV light. The ink is based on photocatalyst which decomposes organic dye in presence of UV light causing the changes in colour. Such process can be used as a simple UV dosimeter as its colour change depends on duration to UV light exposure. We have prepared such an ink based on redox dye 2,6-dichloroindophenol (DCIP), photocatalyst titanium dioxide (nanodimensional anatase), reducing agent (glycerol) and two different water based binders – hydroxyethylcellulose (HEC) and polyvinyl alcohol (PVA). Prepared ink was applied onto a substrate, exposed to UV light and analysed by UV/Visible spectra. When the ink was exposed to UV light, the colour of the redox dye DCIP was changing from blue to colourless that belongs to the dihydro DCIP form. The colour change depends on several factors: on the amount of TiO2 and UV exposure, as well as on the type of binder. In this work the influence of two selected binders and the amount of photocatalyst on the properties of ink was observed. The results show that the ink based on polyvinyl alcohol has a greater initial absorption and absorbs at higher wavelength. Colour changes were faster when higher amount of photocatalyst and HEC as a binder were used. Nevertheless, it has been confirmed that both binders are appropriate for preparation of UV active functional printing inks