Sorption Calorimetry Research Articles

Effect of acetylation on wood-water interactions studied by sorption calorimetry

Sorption of water has a profound effect on the material properties of wood. The uptake of water vapour in wood and other materials releases more heat than the condensation of vapour to liquid water. This excess energy provides insights to the interactions and energy state of the absorbed water molecules. Modification of wood by acetylation is a common way of altering the wood-water interactions; however, very few data exist on how this and other types of modification affect the energy state of absorbed water in wood. This study is the first to use sorption calorimetry on modified wood to explore the effect of acetylation on wood-water interactions. Acetylation decreased the strength of the interactions between wood and water as seen from a decrease in differential enthalpy of mixing, both overall and in the dry state. It appears that acetylation removes or hinders the most-energetic interactions or bonding configurations of water in wood, perhaps because acetylation reduces the number of water-accessible hydroxyls more than it reduces the amount of absorbed water molecules.

Hygrothermal Properties and Performance of Bio-Based Insulation Materials Locally Sourced in Sweden.

In recent years, there has been a paradigm shift in the building sector towards more sustainable, resource efficient, and renewable materials. Bio-based insulation derived from renewable resources, such as plant or animal fibres, is one promising group of such materials. Compared to mineral wool and polystyrene-based insulation materials, these bio-based insulation materials generally have a slightly higher thermal conductivity, and they are significantly more hygroscopic, two factors that need to be considered when using these bio-based insulation materials. This study assesses the hygrothermal properties of three bio-based insulation materials: eelgrass, grass, and wood fibre. All three have the potential to be locally sourced in Sweden. Mineral wool (stone wool) was used as a reference material. Hygrothermal material properties were measured with dynamic vapour sorption (DVS), transient plane source (TPS), and sorption calorimetry. Moisture buffering of the insulation materials was assessed, and their thermal insulation capacity was tested on a building component level in a hot box that exposed the materials to a steady-state climate, simulating in-use conditions in, e.g., an external wall. The tested bio-based insulation materials have significantly different sorption properties to stone wool and have higher thermal conductivity than what the manufacturers declared. The hot-box experiments showed that the insulating capacity of the bio-based insulators cannot be reliably calculated from the measured thermal conductivity alone. The results of this study could be used as input data for numerical simulations and analyses of the thermal and hygroscopic behaviour of these bio-based insulation materials.

Lysozyme-Sucrose Interactions in the Solid State: Glass Transition, Denaturation, and the Effect of Residual Water.

The freeze-drying of proteins, along with excipients, offers a solution for increasing the shelf-life of protein pharmaceuticals. Using differential scanning calorimetry, thermogravimetric analysis, sorption calorimetry, and synchrotron small-angle X-ray scattering (SAXS), we have characterized the properties at low (re)hydration levels of the protein lysozyme, which was freeze-dried together with the excipient sucrose. We observe that the residual moisture content in these samples increases with the addition of lysozyme. This results from an increase in equilibrium water content with lysozyme concentration at constant water activity. Furthermore, we also observed an increase in the glass transition temperature (Tg) of the mixtures with increasing lysozyme concentration. Analysis of the heat capacity step of the mixtures indicates that lysozyme does not participate in the glass transition of the sucrose matrix; as a result, the observed increase in the Tg of the mixtures is the consequence of the confinement of the amorphous sucrose domains in the interstitial space between the lysozyme molecules. Sorption calorimetry experiments demonstrate that the hydration behavior of this formulation is similar to that of the pure amorphous sucrose, while the presence of lysozyme only shifts the sucrose transitions. SAXS analysis of amorphous lysozyme-sucrose mixtures and unfolding of lysozyme in this environment show that prior to unfolding, the size and shape of lysozyme in a solid sucrose matrix are consistent with its native state in an aqueous solution. The results obtained from our study will provide a better understanding of the low hydration behavior of protein-excipient mixtures and support the improved formulation of biologics.

On the bioprotective effects of 3-hydroxybutyrate: Thermodynamic study of binary 3HB-water systems

Microorganisms must face various inconvenient conditions; therefore, they developed several approaches for protection. Such a strategy also involves the accumulation of compatible solutes, also called osmolytes. It has been proved that the monomer unit 3-hydroxybutyrate (3HB), which is present in sufficient concentration in poly(3-hydroxybutyrate) (PHB)-accumulating cells, serves as a chemical chaperone protecting enzymes against heat and oxidative stress and as a cryoprotectant for enzymes, bacterial cells, and yeast. The stress robustness of the cells is also strongly dependent on the behavior and state of intracellular water, especially during stress exposure. For a better understanding of the protective mechanism and effect of strongly hydrophilic 3HB in solutions at a wide range of temperatures, a binary phase diagram of system sodium 3HB (Na3HB)-water in equilibrium and the state diagrams showing the glass transitions in the system were constructed. To investigate the activity of water in various compositions of the Na3HB/water system, three experimental techniques have been used (dynamic water sorption analysis, water activity measurements, and sorption calorimetry). First, Na3HB proved its hydrophilic nature, which is very comparable with known compatible solutes (trehalose). Results of differential scanning calorimetry demonstrated that Na3HB is also highly effective in depressing the freezing point and generating a large amount of nonfrozen water (1.35 g of water per gram of Na3HB). Therefore, Na3HB represents a very effective cryoprotectant that can be widely used for numerous applications.

Hydration and dehydration induced changes in porosity of starch microspheres

Characterization and tuning of the porosity of amorphous starch materials are important for many applications, including controlled release of encapsulated proteins. The porosities of these materials in dry and hydrated states can have different physicochemical origins and properties. Here, porosities of dry cross-linked starch microspheres and their hydration-induced transformations were characterized by small angle X-ray scattering, scanning electron and optical microscopies, thermogravimetric analysis, sorption calorimetry, nitrogen sorption, and helium-pycnometry. The analyses revealed that dry microspheres consist of porous cores with pore diameters below 100 nm and shells which appeared to be denser but contained wider pores (100–300 nm). The outer crust of the microspheres shell is non-porous, which restricts diffusion of nitrogen, water, and ethanol. Partial hydration triggered an irreversible collapse of dry porosity at 12 wt% water. Further hydration resulted in interfacial changes and promoted wet porosity, related to characteristic distances between polymer chains.

Hydration enthalpies of amorphous sucrose, trehalose and maltodextrins and their relationship with heat capacities.

The mechanisms of glass transitions and the behavior of small solute molecules in a glassy matrix are some of the most important topics of modern thermodynamics. Water plays an important role in the physical and chemical stability of lyophilized biologics formulations, in which glassy carbohydrates act as cryoprotectants and stabilizers. In this study, sorption calorimetry was used for simultaneous measurements of water activity and the enthalpy of water sorption by amorphous sucrose, trehalose and maltodextrins. Moreover, the heat capacity of these carbohydrates in mixtures with water was measured by DSC in a broad range of water contents. The hydration enthalpies of glassy sucrose, trehalose and maltodextrins are exothermic, and the enthalpy change of water-induced isothermal glass transitions is higher for small molecules. The partial molar enthalpy of mixing of water in slow experiments is about -18 kJ mol-1, but less exothermic in the case of small molecules at fast hydration scan rates. By measuring the heat capacities of disaccharides and maltodextrins as a function of water content, we separated the contributions of carbohydrates and water to the total heat capacities of the mixtures. The combination of these data allowed testing of thermodynamic models describing the hydration-induced glass transitions. The heat capacity changes calculated by the fitting of the hydration enthalpy data for disaccharides are in good agreement with the heat capacity data obtained by DSC, while for maltodextrins, the effect of sub-Tg transitions should be taken into account. Combining the data obtained by different techniques, we found a distinct difference in the behavior of water in glassy polymers compared to that in glassy disaccharides. By understanding the behavior of water in glassy carbohydrates, these results can be used to improve the design of freeze-dried formulations of proteins and probiotics.

On the calculation of thermodynamic parameters in sorption calorimetric experiments

The sorption calorimetry method developed by Wadsö and co-workers is one of the most successful methods for studying the enthalpy of vapor sorption by solids and gels. A unique feature of this method is a simultaneous measurement of the water sorption isotherm and the sorption enthalpy. The accuracy of the enthalpy measurements in sorption calorimetric experiments can be affected by diffusion of water vapour through the injection channel tube and potentially through small leaks in the sorption cell. At high water activities this leads to an apparent drift of the measured enthalpies towards endothermic values. In this work we propose an improvement of the enthalpy calculation method, that eliminates these effects and substantially improves the accuracy of the enthalpy measurements. The new method is successfully tested on previously published sorption calorimetric data and can be recommended for use in future experiments.

Measuring the Heat of Interaction between Lignocellulosic Materials and Water

Research Highlights: When investigating the sorption of water on lignocellulosic materials, the sorption or mixing enthalpy is an interesting parameter that, together with the sorption isotherms commonly measured, can be used to characterize and understand the sorption process. We have compared different methods to assess these enthalpies. Additionally, we propose a sorption nomenclature. Background and Objectives: Sorption enthalpies are non-trivial to measure. We have, for the first time, measured sorption enthalpies on the same materials with four different methods, to be able to compare the method’s strengths and weaknesses. Materials and Methods: The following four methods were used on beech and Scots pine wood: isosteric heat, solution calorimetry, sorption calorimetry, and RH perfusion calorimetry. Results: The results for beech and pine were similar, and were in general agreement with the literature. We do not recommend one of the methods over the others, as they are quite different, and they can therefore be used to elucidate different aspects of the interactions between water and, for example, novel biobased materials (modified woods, cellulose derivatives, and regenerated cellulose).

Alcohols react with MCM-41 at room temperature and chemically modify mesoporous silica

Mesoporous silica has received much attention due to its well-defined structural order, high surface area, and tunable pore diameter. To successfully employ mesoporous silica for nanotechnology applications it is important to consider how it is influenced by solvent molecules due to the fact that most preparation procedures involve treatment in various solvents. In the present work we contribute to this important topic with new results on how MCM-41 is affected by a simple treatment in alcohol at room temperature. The effects of alcohol treatment are characterized by TGA, FTIR, and sorption calorimetry. The results are clear and show that treatment of MCM-41 in methanol, ethanol, propanol, butanol, pentanol, or octanol at room temperature introduces alkoxy groups that are covalently bound to the silica surface. It is shown that alcohol treated MCM-41 becomes more hydrophobic and that this effect is sequentially more prominent going from methanol to octanol. Chemical formation of alkoxy groups onto MCM-41 occurs both for calcined and hydroxylated MCM-41 and the alkoxy groups are hydrolytically unstable and can be replaced by silanol groups after exposure to water. The results are highly relevant for mesoporous silica applications that involve contact or treatment in protic solvents, which is very common.

Novel approach to determination of sorption in pervaporation process: a case study of isopropanol dehydration by polyamidoimideurea membranes

Development of novel membranes with optimal performance, selectivity, and stability is a key research area in membrane technology. In the present work aromatic polyamidoimideurea (PAIU) is synthesized and tested as promising membrane material for separation of water and alcohol mixtures. The PAIU membrane structure, density, and transport properties are studied. Mass transfer of water and isopropanol through the membrane is estimated by sorption and pervaporation tests to determine equilibrium sorption degree, diffusion coefficients, flux through the membrane, and separation factor. Two techniques of sorption study from liquid and from vapor phases are used as novel approach to experimental study of mass transfer. The vapor sorption calorimetry permits to analyze the behavior of the polymer material in sorption process. In pervaporation of water–isopropanol mixture, almost pure water mainly permeates through PAIU membrane. To improve the performance, a double layer membrane containing a thin PAIU layer on the surface of porous poly(phenylene oxide) support is developed. The double layer membrane is extremely effective in dehydration of isopropanol.

Effect of Oligomerization of Counterions on Water Activity in Aqueous Cationic Surfactant Systems

A sorption calorimetry study of cationic cetyltrimethyl ammonium surfactants with four different counterions was performed. The counterions were acetate, succinate, citrate, and butyl tetracarboxylate with formal charges ranging from 1 to 4, respectively. The counterions with 2-4 charges can be considered as oligomers. In all the cases, hydration experiments started with dry solid phases that upon water uptake went through solid-state phase transitions and hexagonal to micellar cubic phase transitions. It was found that in liquid-crystalline phases the activity of water increased with the degree of oligomerization or, equivalently, the formal charge of the counterions. The results are discussed in terms of the forces acting between the colloidal aggregates. It is argued that under the conditions investigated, the so-called strong-coupling theory can be used to describe the electrostatic forces between the charged colloidal objects. Therefore, we suggest that the observed dependence of water activity on the degree of polymerization is due to the entropy of mixing of the counterions in the water volume, which we describe using Flory-Huggins theory.

Effect of hydration and dehydration on the properties of SBA-15 layer studied by humidity scanning QCM-D

Surface deposited layers of mesoporous silica particles could function as support for bio-sensing or drug release applications. It is crucial to control the surface deposition process and employ relevant techniques to characterize the properties of the particles on the surface. Here, we deposit SBA-15 particles on native silica or cationic surfaces and characterize the hydration and dehydration by employing a novel method based on humidity scanning quartz crystal microbalance with dissipation (HS QCM-D). SBA-15 platelets are deposited with mesopores oriented parallel to the surface normal using drop deposition. SEM shows a monolayer on the surface, which is established as stable. Water sorption-desorption isotherms of the SBA-15 layer from HS QCM-D are compared with isotherms from water sorption calorimetry and nitrogen sorption on bulk material. We demonstrate that HS QCM-D provides results in good agreement with results obtained with the reference methods. The properties of SBA-15 particles are retained during the deposition process and unaffected by the presence of the surface. In addition, HS QCM-D is a fast technique that requires significantly lower amount of material (∼5000 times) compared to experiments on bulk material. HS QCM-D provides complete characterization of the pore size distribution of SBA-15.

Impact of water activity on the stability of ettringite

The stability of ettringite as function of temperature and water vapour pressure was studied on synthetic samples using X-ray diffraction, thermogravimetric analysis, sorption balance measurements and different calorimetry techniques. Crystalline ettringite has a water content per mol of Al2O3, n, varying from 30 to 32 H2O, while the amorphous product formed on drying it, metaettringite, has only 9 to 13 H2O. Very large hysteresis was observed during the desorption and absorption cycles. The total enthalpy values associated with the decomposition and reformation of ettringite were consistent and similar. During rehydration, different absorption stages were identified and quantified with sorption calorimetry. Due to the hysteresis it was not possible to model the absorption/desorption behaviour using the enthalpies determined by calorimetry, so the values calculated with the van't Hoff equation were used. The area of performance of ettringite-based systems recommended in this work has been extended compared to previously reported data.

Hydration and swelling of amorphous cross-linked starch microspheres

Hydration of cross-linked starch microspheres, commercially available as a medical device, was investigated using a multi-method approach. We found that the uptake of water is accompanied by substantial swelling and changes of the polymer structure. Sorption calorimetry provided information about thermodynamics of water sorption, revealed presence of isothermal glass transition and absence of hydration-induced crystallization, observed in non-cross linked starch material. The changes in the surface and bulk properties of microspheres at different water–starch concentrations were investigated using synchrotron radiation X-ray scattering and analyzed using concept of fractals. The obtained information, combined with the results of differential scanning calorimetry, was used to construct a phase diagram of the studied material. Finally, hydration induced evolution of polymer structure revealed by the X-ray scattering was linked to the changes observed during swelling with optical microscopy.

Hydration of hyaluronan: effects on structural and thermodynamic properties.

Hyaluronan (HA) is a frequently occurring biopolymer with a large variety of functions in nature. During the past 60 years, there have been numerous reports on structural and dynamic behavior of HA in water. Nevertheless, studies covering a wider concentration range are still lacking. In this work, we use isothermal scanning sorption calorimetry for the first time to investigate hydration-induced transitions in HA (sodium hyaluronate, 17 kDa). From this method, we obtain the sorption isotherm and the enthalpy and the entropy of hydration. Thermotropic events are evaluated by differential scanning calorimetry (DSC), and structure analysis is performed with X-ray scattering (SWAXS) and light and scanning electron microscopy. During isothermal hydration, HA exhibits a glass transition, followed by crystallization and subsequent dissolution of HA crystals and formation of a one-phase solution. Structural analysis reveals that the crystal may be indexed on an orthorhombic unit cell with space group P212121. Crystallization of HA was found to occur either through endothermic or exothermic processes, depending on the temperature and water content. We propose a mechanism of crystallization that explains this phenomenon based on the interplay between the hydrophobic effect and strengthening of hydrogen bonds during formation of crystals. The combined results were used to construct a binary phase diagram for the HA-water system.

Hydration and the phase diagram of acid hydrolyzed potato starch

We investigated hydration of acid hydrolyzed potato starch (maltodextrin) employing a multi-method approach. In particular, synchrotron radiation X-ray scattering and differential scanning calorimetry were used, and, for the first time, the material was investigated with sorption calorimetry and a newly developed quartz crystal microbalance with humidity scanning. The dry starch was found to be in an amorphous state. During hydration it exhibits a glass transition in both bulk and thin film samples, followed by an exothermic event where the starch crystallized. Recrystallized bulk samples displayed neither a pronounced glass transition nor crystallization upon hydration whereas both events occurred in thin film samples. The hydration-driven crystallization resulted in an X-ray pattern consistent with the coexistence of A and B type crystallites; however, at higher water concentrations only the B form occurred. The results were used to construct the first ever acid hydrolyzed starch–water phase diagram.

Determination of Sorption Isotherm and Rheological Properties of Lysozyme Using a High-Resolution Humidity Scanning QCM-D Technique

The high-resolution humidity scanning QCM-D technique enables investigation of hydration of soft matter films using a quartz crystal microbalance with dissipation monitoring (QCM-D) equipped with a humidity module. Based on a continuous increase of relative humidity, properties of soft matter films can be investigated depending on the water content of the surrounding atmosphere. Determination of complete water sorption isotherms is possible via analysis of the overtone dependence of the resonance frequencies. Rheological properties are monitored via measurement of the dissipation. The glass transition can be identified from the change of viscoelastic properties of the film reflected in changes of the dissipation. A high-resolution water sorption isotherm of lysozyme was measured and compared with results from water sorption calorimetry. Analysis of the rheological behavior during hydration of lysozyme films revealed the presence of two separate sharp transitions at the water activities 0.67 and 0.91, which are connected to the glass transition. In previous works, only the existence of a broad glass transition has been reported so far. Combining the QCM-D data with Raman scattering data presented earlier, a new mechanism of isothermal glass transition in lysozyme is proposed.

Porosity and surface properites of SBA-15 with grafted PNIPAAM: a water sorption calorimetry study.

Mesoporous silica SBA-15 was modified in a three-step process to obtain a material with poly-N-isopropylacrylamide (PNIPAAM) grafted onto the inner pore surface. Water sorption calorimetry was implemented to characterize the materials obtained after each step regarding the porosity and surface properties. The modification process was carried out by (i) increasing the number of surface silanol groups, (ii) grafting 1-(trichlorosilyl)-2-(m-/p-(chloromethylphenyl) ethane, acting as an anchor for (iii) the polymerization of N-isopropylacrylamide. Water sorption isotherms and the enthalpy of hydration are presented. Pore size distributions were calculated on the basis of the water sorption isotherms by applying the BJH model. Complementary measurements with nitrogen sorption and small-angle X-ray diffraction are presented. The increase in the number of surface silanol groups occurs mainly in the intrawall pores, the anchor is mainly located in the intrawall pores, and the intrawall pore volume is absent after the surface grafting of PNIPAAM. Hence, PNIPAAM seals off the intrawall pores. Water sorption isotherms directly detect the presence of intrawall porosity. Pore size distributions can be calculated from the isotherms. Furthermore, the technique provides information regarding the hydration capability (i.e., wettability of different chemical surfaces) and thermodynamic information.

Effect of Residual Solvent on Physicochemical Properties of Poly(Phenylene Isophtalamide) Membrane

The influence of a plasticizer in the form of the residual solvent dimethylacetamide on pervaporation and sorption properties of membranes based on poly(phenylene isophtalamide) (PA) was investigated. To analyze the influence of the plasticizer on membrane transport properties, pervaporation of binary water–ethyl acetate mixtures was studied. The method of sorption calorimetry was used to investigate water sorption properties of the studied membranes and PA powder. Moreover, to characterize the PA membranes, contact angle measurements and thermogravimetric analysis (TGA) were applied. It is shown that the presence of a residual organic solvent significantly changes the sorption and transport characteristics of the membranes. The residual organic solvent increases the amount of water absorbed by the polymer membrane. In pervaporation of water/ethyl acetate mixtures, the presence of the residual solvent dimethylacetamide makes the membrane more permeable but less selective for water separation.

Assessment of Porosities of SBA-15 and MCM-41 Using Water Sorption Calorimetry

Water sorption calorimetry has been used for characterization of 2D hexagonally ordered mesoporous silica SBA-15. Experimental data on water sorption isotherm, the enthalpy, and the entropy of hydration of SBA-15 are presented. The results were compared with previously published results on MCM-41 obtained using the same technique. The water sorption isotherm of SBA-15 consists of four regimes, while the sorption isotherm of MCM-41 consists only of three. The extra regime in the water sorption isotherm for SBA-15 arises from filling of intrawall pores, that are present in SBA-15 but absent in MCM-41. The water sorption isotherms of the two types of mesoporous silica were analyzed using the Barrett-Joyner-Halenda approach. For the BJH analysis, t-curves of silica with different degrees of hydroxylation were proposed. Comparison of water and nitrogen t-curves shows that, independent of hydroxylation of silica surface, the adsorbed film of water is much thinner than the adsorbed film of nitrogen at similar relative pressures. This fact decreases the uncertainty of the assessment of porosity with water sorption originated from variations in surface properties. The pore size distribution of SBA-15 calculated with BJH treatment of water sorption data is in good agreement with nitrogen NLDFT results on the same material.