Elucidating the Dehydration Pathways of K2CO3·1.5H2O.

Potassium carbonate sesquihydrate has previously been identified as a promising material for thermochemical energy storage. The hydration and cyclic behavior have been extensively studied in the literature, but detailed investigation into the different processes occurring during dehydration is lacking. In this work, a systematic investigation into the different dehydration steps is conducted. It is found that at higher temperatures, dehydration of pristine material occurs as a single process since water removal from the pristine crystals is difficult. After a single cycle, due to morphological changes, dehydration now occurs as two processes, starting at lower temperatures. The morphological changes open new pathways for water removal at the newly generated edges, corners, and steps of the crystal surface. The observations from this work may contribute to material design as they elucidate the relation between material structure and behavior.

The Effect of Nanoconfinement on Deliquescence of CuCl2 Is Stronger than on Hydration.

The hydration of salts has gained particular interest within the frame of thermochemical energy storage. Most salt hydrates expand when absorbing water and shrink when desorbing, which decreases the macroscopic stability of salt particles. In addition, the salt particle stability can be compromised by a transition to an aqueous salt solution, called deliquescence. The deliquescence often leads to a conglomeration of the salt particles, which can block the mass and heat flow through a reactor. One way of macroscopically stabilizing the salt concerning expansion, shrinkage, and conglomeration is the confinement inside a porous material. To study the effect of nanoconfinement, composites of CuCl2 and mesoporous silica (pore size 2.5-11 nm) were prepared. Study of sorption equilibrium showed that the pore size had little or no effect on the onsets of (de)hydration phase transition of the CuCl2 inside the silica gel pores. At the same time, isothermal measurements showed a significant lowering of the deliquescence onset in water vapor pressure. The lowering of the deliquescence onset leads to its overlap with hydration transition for the smallest pores (<3.8 nm). A theoretical consideration of the described effects is given in the framework of nucleation theory.

Impact of Atmospheric CO2 on Thermochemical Heat Storage Capabilities of K2CO3.

This work investigates the reactions occurring in K2CO3-H2O-CO2 under ambient CO2 pressures in temperature and vapor pressure ranges applicable for domestic thermochemical heat storage. The investigation shows that depending on reaction conditions, the primary product of a reaction is K2CO3·1.5H2O, K2CO3·2KHCO3·1.5H2O, or a mixture of both. The formation of K2CO3·1.5H2O is preferred far above the equilibrium conditions for the hydration reaction. On the other hand, the formation of double salt is preferred at conditions where hydration reaction is inhibited or impossible, as the thermogravimetric measurements identified a new phase transition line below the hydration equilibrium line. The combined X-ray diffraction, thermogravimetric analysis, and Fourier-transform infrared spectroscopy study indicates that this transition line corresponds to the formation of K2CO3·2KHCO3, which was not observed in any earlier study. In view of thermochemical heat storage, the formation of K2CO3·2KHCO3·(1.5H2O) increases the minimum charging temperature by approximately 40 °C. Nevertheless, the energy density and cyclability of the storage material can be preserved if the double salt is decomposed after each cycle.

Hyphal growth of Penicillium rubens in changing relative humidity.

When considering mold prevention strategies, the environmental conditions in which fungi grow need to be taken into consideration. This environment is often characterized by a time-dependent relative humidity, and porous substrate. Growth has mainly been investigated in steady-state experiments. Therefore, the goal of this study is to understand the hyphal growth of Penicillium rubens on porous gypsum, under dynamic humidity conditions. Spores of P. rubens were inoculated on porous gypsum containing nutrients, and placed in a small incubation chamber, allowing for microscopic hyphal observation. The relative humidity in this chamber varied multiple times between a high (close to 100%) and low value (35%, 55%, or 75%). The hyphae reacted to a lowered relative humidity by an immediate growth stop and dehydration. When the relative humidity was increased again, the hyphae re-hydrated and three responses were found: regrowing after approximately 4 h, after a time equal to the germination time, or no regrowth at all. No substantial regrowth was found for fluctuations faster than 4 h. This time-scale was found for multiple decreases in relative humidity, and has been reported for the first time. KEY POINTS: • Hyphae restart growth after a characteristic time of approximately 4 h. • Relative humidity fluctuations of 3 h can suppress hyphal growth. • Hyphae do not regrow after a severe desiccation and short periods of high humidity.

Penicillium rubens germination on desiccated and nutrient-depleted conditions depends on the water activity during sporogenesis.

Fungal growth often appears in a surrounding where water and nutrients are scarce. The impact of this environment during sporogenesis on subsequent growth is often neglected. This study investigates the effect of water availability during sporogenesis on subsequent early growth. Therefore, a carbon-depleted substrate was constructed. Humidity is then the only parameter of interest. The water conditions during sporogenesis, and during subsequent growth, were varied. This is a stressing environment: no carbon source is present, and water provided solely via the vapour. The lag time, tl, and initial growth rate, µfp, of the germ tubes were monitored. The effect of aw history on germination and initial growth depends on the RH of the environment. Only at low RH do spores produced at low aw have a smaller tl and higher µfp compared to those grown at high aw. This result was remarkably pronounced when the substrate was also made hydrophobic: growth only occurred when spores were developed at low aw and placed in high RH. Spores grown on lowered aw attract more water. It is hypothesized that this attraction affects subsequent growth behaviour, and is the reason why growth on hydrophobic glass only prevails in the condition of high RH and lowered aw history. We demonstrate the influence of cultivation conditions on germination, which becomes more pronounced in a more desiccated environment.

Surface characterization of drying acrylic latex dispersions with variable methacrylic acid content using surface dilatational rheology.

HYPOTHESIS: Drying of latex dispersions often results in particle gradients at the latex-air interface. We expect that, by increasing the carboxylic acid content of latex particles, inter-particle interactions at the interface change. With dilatational rheology one could detect particle-particle interactions in an early stage of the drying process and elucidate the nature of these interactions. EXPERIMENTS: Acrylic latex dispersions were prepared with different amounts of methacrylic acid (MAA), ranging from 2 to 10 wt% on dry mass. Dilatational rheology studies during drying at different relative humidities RH were performed using profile analysis tensiometry. Visco-elastic properties of latex surfaces were used to identify inter-particle interactions at the surfaces depending on the drying rate and particle composition. FINDINGS: Drying at 85% RH did not show significant changes of the mechanical properties of the latex surfaces. Drying at 65 and 53% RH resulted in a change of the mechanical properties, ultimately showing non-linear visco-elastic behavior. This indicates that capillary and/or Van der Waals forces were operating between particles at the surface. With increasing MAA content the viscous contribution decreased, possibly due to the formation of more gel-like structures at the particle surface due to higher solubility of polymer segments near to the surface.

Film Formation of High Tg Latex Using Hydroplasticization: Explanations from NMR Relaxometry.

The film formation of acrylic latex dispersions, containing different amounts of carboxylic acid functional groups by the incorporation of methacrylic acid (MAA), was studied with GARField 1H NMR at various relative humidities (RH). Polymer particles with glass-transition temperatures in the range from 26 to 50 °C formed films at room temperature because of hydroplasticization. It was found that with an increased drying rate due to lower RH, the evaporation flux of water was limited by the latex polymer. Only in the second stage of drying this phenomenon was more obvious with increasing MAA content. 1H NMR relaxometry was used to study the change of hydrogen mobilities during film formation and hardening of the films. This showed that the drying rate itself had no impact on the hydrogen mobility in the latex films as measured via the T2 relaxation time. Hydrogen mobilities of water and the mobile polymer phase only significantly decrease after most water has evaporated. This implies that the rigidity of the polymers increases with the evaporation of water that otherwise plasticizes the polymer through hydrogen bonding with the carboxylic acid groups. This hardening of the polymer phase is essential for applications in a coating. The hydrogen mobilities were affected by the MAA concentration. Densities of mobile hydrogens increase with increasing MAA content. This is expected if the mobile protons are contained in the MAA groups. The result thus confirms the role of carboxylic acid groups in hydrogen bonding and plasticization of the copolymers. Hydrogen mobilities, however, decrease with increasing MAA content, which is hypothesized to be caused by the formation of dimers of carboxylic acid groups that still hold water. They still enable short-range polymer hydrogen mobility due to hydroplasticization but limit long-range polymer mobility due to interaction between the carboxylic acid groups.

Vegetable oils as carbon and energy source for Aureobasidium melanogenum in batch cultivation.

Dark homogenous fungal-based layers called biofinishes and vegetable oils are key ingredients of an innovative wood protecting system. The aim of this study was to determine which of the vegetable oils that have been used to generate biofinishes on wood will provide carbon and energy for the biofinish-inhabiting fungus Aureobasidium melanogenum, and to determine the effect of the oil type and the amount of oil on the cell yield. Aureobasidium melanogenum was cultivated in shake flasks with different types and amounts of carbon-based nutrients. Oil-related total cell and colony-forming unit growth were demonstrated in suspensions with initially 1% raw linseed, stand linseed, and olive oil. Oil-related cell growth was also demonstrated with raw linseed oil, using an initial amount of 0.02% and an oil addition during cultivation. Nile red staining showed the accumulation of fatty acids inside cells grown in the presence of oil. In conclusion, each tested vegetable oil was used as carbon and energy source by A. melanogenum. The results indicated that stand linseed oil provides less carbon and energy than olive and raw linseed oil. This research is a fundamental step in unraveling the effects of vegetable oils on biofinish formation.

Oil type and cross-linking influence growth of Aureobasidium melanogenum on vegetable oils as a single carbon source.

Aureobasidium melanogenum is the main fungus found in a spontaneously formed biofilm on a oil-treated wood. This dark colored biofilm functions as a protective coating. To better understand biofilm formation, in this study A. melanogenum was cultured on olive oil and raw linseed oil. Metabolic activity and oil conversion were measured. The results show that A. melanogenum is able to grow on linseed oil and olive oil as a single carbon source. The fungus produces the enzyme lipase to convert the oil into fatty acids and glycerol. Metabolic activity and oil conversion were equal on linseed oil and olive oil. The fungus was not able to grow on severe cross-linked linseed oil, meaning that the degree of cross-linking of the oil is important for growth of A. melanogenum. Dark coloring of the colony was seen on linseed oil, which might be a stress response on the presence of autoxidation products in linseed oil. The colony on olive oil showed delayed melanin production indicating an inhibitory effect of olive oil on melanin production.

The fungal composition of natural biofinishes on oil-treated wood.

BACKGROUND: Biofinished wood is considered to be a decorative and protective material for outdoor constructions, showing advantages compared to traditional treated wood in terms of sustainability and self-repair. Natural dark wood staining fungi are essential to biofinish formation on wood. Although all sorts of outdoor situated timber are subjected to fungal staining, the homogenous dark staining called biofinish has only been detected on specific vegetable oil-treated substrates. Revealing the fungal composition of various natural biofinishes on wood is a first step to understand and control biofinish formation for industrial application. RESULTS: A culture-based survey of fungi in natural biofinishes on oil-treated wood samples showed the common wood stain fungus Aureobasidium and the recently described genus Superstratomyces to be predominant constituents. A culture-independent approach, based on amplification of the internal transcribed spacer regions, cloning and Sanger sequencing, resulted in clone libraries of two types of biofinishes. Aureobasidium was present in both biofinish types, but was only predominant in biofinishes on pine sapwood treated with raw linseed oil. Most cloned sequences of the other biofinish type (pine sapwood treated with olive oil) could not be identified. In addition, a more in-depth overview of the fungal composition of biofinishes was obtained with Illumina amplicon sequencing that targeted the internal transcribed spacer region 1. All investigated samples, that varied in wood species, (oil) treatments and exposure times, contained Aureobasidium and this genus was predominant in the biofinishes on pine sapwood treated with raw linseed oil. Lapidomyces was the predominant genus in most of the other biofinishes and present in all other samples. Surprisingly, Superstratomyces, which was predominantly detected by the cultivation-based approach, could not be found with the Illumina sequencing approach, while Lapidomyces was not detected in the culture-based approach. CONCLUSIONS: Overall, the culture-based approach and two culture-independent methods that were used in this study revealed that natural biofinishes were composed of multiple fungal genera always containing the common wood staining mould Aureobasidium. Besides Aureobasidium, the use of other fungal genera for the production of biofinished wood has to be considered.

Conidia of Penicillium rubens formed at low water activities can attract more water.

To address the problem of indoor fungal growth, understanding the influence of moisture conditions on the fungal colonization process is crucial. This paper explores the influence of past moisture conditions on current processes. Specifically, it studies the growth and water sorption of conidia of Penicillium rubens formed at lower water activities (ranging from 0.86 to 0.99). For the first time, dynamic vapor sorption (DVS) is applied as a tool to quantify the water sorption of conidia as a function of the water activity at conidiation. Furthermore, growth experiments on agar and gypsum substrates are reported that relate hyphal growth rates of the mycelium from pretreated conidia to the water activity at conidiation. No effect of the conidiation water activity on mycelial growth rates is found on either gypsum or agar. It is found, however, that conidia formed at lower activities have a higher dry weight and attract more water from humid air. It is shown that both phenomena can be explained by conidia from lower activities carrying higher amounts of compatible solutes, glycerol in particular. The enhanced sorption observed in this study might constitute a mechanism through which solute reserves contribute to survival during the early steps of fungal colonization.

The Indoor Fungus Cladosporium halotolerans Survives Humidity Dynamics Markedly Better than Aspergillus niger and Penicillium rubens despite Less Growth at Lowered Steady-State Water Activity.

UNLABELLED: Indoor fungi cause damage in houses and are a potential threat to human health. Indoor fungal growth requires water, for which the terms water activity (aw) and relative humidity (RH) are used. The ability of the fungi Aspergillus niger, Cladosporium halotolerans, and Penicillium rubens at different developmental stages to survive changes in aw dynamics was studied. Fungi grown on media with high aw were transferred to a controlled environment with low RH and incubated for 1 week. Growth of all developmental stages was halted during incubation at RHs below 75%, while growth continued at 84% RH. Swollen conidia, germlings, and microcolonies of A. niger and P. rubens could not reinitiate growth when retransferred from an RH below 75% to a medium with high aw All developmental stages of C. halotolerans showed growth after retransfer from 75% RH. Dormant conidia survived retransfer to medium with high aw in all cases. In addition, retransfer from 84% RH to medium with high aw resulted in burst hyphal tips for Aspergillus and Penicillium Cell damage of hyphae of these fungi after incubation at 75% RH was already visible after 2 h, as observed by staining with the fluorescent dye TOTO-1. Thus, C. halotolerans is more resistant to aw dynamics than A. niger and P. rubens, despite its limited growth compared to that of these fungi at a lowered steady-state aw The survival strategy of this phylloplane fungus in response to the dynamics of aw is discussed in relation to its morphology as studied by cryo-scanning electron microscopy (cryo-SEM). IMPORTANCE: Indoor fungi cause structural and cosmetic damage in houses and are a potential threat to human health. Growth depends on water, which is available only at certain periods of the day (e.g., during cooking or showering). Knowing why fungi can or cannot survive indoors is important for finding novel ways of prevention. Until now, the ability of fungi to grow on media with little available water at steady state (unchanging conditions) has been important for evaluating whether a fungus can grow indoors. In the present study, we found that the fungus Cladosporium halotolerans, a common indoor fungus, is more resistant to changes in available water than the fungi Aspergillus niger and Penicillium rubens, despite the fact that the latter fungi can grow on media with low water availability. We concluded that the ability of fungi to deal with changes in humidity is at least as important as the ability to grow on low-water media.

A microscopy study of hyphal growth of Penicillium rubens on gypsum under dynamic humidity conditions.

To remediate indoor fungal growth, understanding the moisture relations of common indoor fungi is crucial. Indoor moisture conditions are commonly quantified by the relative humidity (RH). RH is a major determinant of the availability of water in porous indoor surfaces that fungi grow on. The influence of steady-state RH on growth is well understood. Typically, however, the indoor RH constantly changes so that fungi have to endure frequent periods of alternating low and high RH. Knowledge of how common indoor fungi survive and are affected by the low-RH periods is limited. In particular, the specific effects of a drop in RH on the growth of the mycelium remain unclear. In this work, video microscopy was used to monitor hyphal growth of Penicillium rubens on gypsum substrates under controlled dynamic humidity conditions. The effect of a single period of low RH (RH = 50-90%) interrupting favourable conditions (RH = 97%) was tested. It was found that hyphal tips ceased to extend when exposed to any tested decrease in RH. However, new hyphal growth always emerges, seemingly from the old mycelium, suggesting that this indoor fungus does not rely only on conidia to survive the humidity patterns considered. These findings are a fundamental step in unravelling the effect of RH on indoor fungal growth.

Aureobasidium melanogenum: a native of dark biofinishes on oil treated wood.

The genus Aureobasidium, which is known as a wood staining mould, has been detected on oil treated woods in the specific stain formation called biofinish. This biofinish is used to develop a new protective, self-healing and decorative biotreatment for wood. In order to understand and control biofinish formation on oil treated wood, the occurrence of different Aureobasidium species on various wood surfaces was studied. Phenotypic variability within Aureobasidium strains presented limitations of morphological identification of Aureobasidium species. PCR amplification and Sanger sequencing of ITS and RPB2 were used to identify the culturable Aureobasidium species composition in mould stained wood surfaces with and without a biofinish. The analysed isolates showed that several Aureobasidium species were present and that Aureobasidium melanogenum was predominantly detected, regardless of the presence of a biofinish and the type of substrate. A. melanogenum was detected on wood samples exposed in the Netherlands, Cameroon, South Africa, Australia and Norway. ITS-specific PCR amplification, cloning and sequencing of DNA extracted from biofinish samples confirmed results of the culturing based method: A. melanogenum is predominant within the Aureobasidium population of biofinishes on pine sapwood treated with raw linseed oil and the outdoor placement in the Netherlands.

Separate effects of moisture content and water activity on the hyphal extension of Penicillium rubens on porous media.

To prevent indoor fungal growth, understanding the moisture relations of fungi is a key element. Indoor moisture is quantified by the relative humidity (RH). RH controls the water activity of the indoor materials that fungi grow on, a well-studied parameter known to limit fungal growth. RH, however, also controls the amount of water present in these materials, the moisture content. The significance of the moisture content of these materials to indoor fungal growth is currently overlooked. In the work reported here, growth experiments with the indoor fungus Penicillium rubens on gypsum substrates were performed to test whether the moisture content influences growth on porous materials. Second, we report the development of a video microscopy method that for the first time quantified hyphal growth on a porous material. It is found that a higher moisture content leads to earlier colonization and higher hyphal extension rates. This is a fundamental step in unravelling the effect of RH on indoor fungal growth. The real-time monitoring of colonization of gypsum provides a new view of growth on indoor surfaces.

T2 distribution spectra obtained by continuum fitting method using a mixed Gaussian and Exponential kernel function.

Static (1)H NMR Free Induction Decay (FID) signals of polymer solids contain a lot of information about the molecular dynamics. A T2 analysis of the FID has generally been performed in terms of discrete two- or three-component models. However, this requires a priori assumption of the number of proton species before analysis. This paper presents a method of analyzing the FIDs of the polymer solid samples in terms of a continuous T2 distribution. A mixed Gaussian and Exponential kernel function was used to represent the true characteristic of FIDs of the polymer solids. A simple and realistic assumption has been made to reduce the number of degrees of freedom in the continuum fitting and to make the fitting stable. An experimental static (1)H NMR FID of a typical polymer solid sample was analyzed as an example in the end to demonstrate the application of this method.

Water plasticizes only a small part of the amorphous phase in nylon-6.

It is known that Polyamide 6 absorbs water in its amorphous phase. The exact composition of the amorphous phase will determine the uptake process. The heterogeneity in the amorphous phase with respect to plasticization by water uptake is quantified in this paper using NMR relaxometry. It is shown that water occupies and plasticizes only a small part (∼6%) of the nylon matrix. This part is located in between the crystalline domains where polymer chain mobility is higher. At low moisture content (<4%) water molecules are tightly bound to the polymer and have the same dynamics. A highly mobile pool of guest-hydrogen nuclei is detected starting at a moisture content of 4%. Here, water is absorbed in clusters and the interaction between the polymer chains and water molecules decreases, leading to decoupling of the dynamics of water and polymer.

High spatial resolution NMR imaging of polymer layers on metallic substrates.

High spatial resolution NMR imaging techniques have been developed recently to measure the spatial inhomogeneity of a polymer coating film. However, the substrates of the polymer coatings for such experiments are generally required to be non-metallic, because metals can interact with static magnetic fields B(0) and RF fields B(1) giving rise to artifacts in NMR images. In this paper we present a systematic study on the effects of metallic substrates on 1D profiles obtained by high resolution NMR imaging. The off-resonance effect is discussed in detail in terms of the excitation profile of the RF pulses. We quantitatively show how the NMR signal intensities change with frequency offset at different RF pulse lengths. The complete NMR profiles were simulated using a Finite Element Analysis method by fully considering the inhomogeneities in both B(1) and B(0). The excellent agreement between the calculated and measured NMR profiles on both metallic and non-metallic substrates indicates that the experimental NMR profiles can be reproduced very well by numerical simulations. The metallic substrates can disturb the RF field of the coil by eddy current effect and therefore change the NMR profiles. To quantitatively interpret the NMR profile of a polymer layer on a metallic substrate, the profile has to be divided by the profile of a reference on the same metallic substrate located at the same distance from the coil.

Elements that contribute to healthy building design.

BACKGROUND: The elements that contribute to a healthy building are multifactorial and can be discussed from different perspectives. OBJECTIVES: WE PRESENT THREE VIEWPOINTS OF DESIGNING A HEALTHY BUILDING: the importance of sustainable development, the role of occupants for ensuring indoor air quality, and ongoing developments related to indoor finishes with low chemical emissions and good fungal resistance. DISCUSSION: Sustainable design rediscovers the social, environmental, and technical values of pedestrian and mixed-use communities, using existing infrastructures including "main streets" and small-town planning principles and recapturing indoor-outdoor relationships. This type of design introduces nonpolluting materials and assemblies with lower energy requirements and higher durability and recyclability. Building occupants play a major role in maintaining healthy indoor environments, especially in residences. Contributors to indoor air quality include cleaning habits and other behaviors; consumer products, furnishings, and appliances purchases, as well as where and how the occupants use them. Certification of consumer products and building materials as low-emitting products is a primary control measure for achieving good indoor air quality. Key products in this respect are office furniture, flooring, paints and coatings, adhesives and sealants, wall coverings, wood products, textiles, insulation, and cleaning products. Finishing materials play a major role in the quality of indoor air as related to moisture retention and mold growth. CONCLUSIONS: Sustainable design emphasizes the needs of infrastructure, lower energy consumption, durability, and recyclability. To ensure good indoor air quality, the product development for household use should aim to reduce material susceptibility to contaminants such as mold and should adopt consumer-oriented product labeling.

In search of a common European approach to a healthy indoor environment.

Increasingly, policymakers in Europe and around the world are realizing the importance of healthy indoor environments for public health. Certain member states of the European Union (EU) have already achieved successes in improving indoor environmental quality, such as controlling certain contaminants (e.g., environmental tobacco smoke) or developing nationwide policies that address indoor air generally. However, a common European approach to achieving healthy indoor environments is desirable for several reasons including providing a broader recognition of the problem of unhealthy indoor air, setting a policy example for all 27 EU member states, and achieving greater public health equity across the different European nations. In this article we address the question "Why is it so difficult in the EU to develop a coherent approach on indoor environment?" We identify and describe four main barriers: a) the subsidiarity principle in EU policymaking, introducing decentralization of decision making to the member states; b) fragmentation of the topic of the indoor environment; c) the differences in climate and governance among different member states that make a common policy difficult; and d) economic issues. We discuss potential lessons and recommendations from EU and U.S. successes in achieving healthier indoor environments through various policy mechanisms.