Can drying and re-wetting of magnesium sulfate salts lead to damage of stone?

Magnesium sulfate salts have been linked to the decay of stone in the field and in laboratory experiments, but the mechanism of damage is still poorly understood. Thermomechanical analysis shows that expansion of stone contaminated with magnesium sulfate salts occurs during drying, followed by relaxation of the stress during dehydration of the precipitated salts. We applied thermogravimetric analysis and X-ray diffractometry to identify the salt phases that precipitate during drying of bulk solutions. The results show the formation of 11 different crystal phases. A novel experiment in which a plate of salt-laden stone is bonded to a glass plate is used to demonstrate the existence of crystallization pressure: warping of the composite reveals significant deformation of the stone during re-wetting of lower hydrates of magnesium sulfate. Environmental scanning electronic microscope (ESEM)/STEM experiments show that hydration of single crystals of the lower hydrates of magnesium sulfate is a through-solution crystallization process that is only visible at a small scale (~μm). It is followed by growth of the crystal prior to deliquescence. This demonstrates that crystallization pressure is the main cause of the stress induced by salt hydration. In addition, we found that drying-induced crystallization is kinetically hindered at high concentration, which we attribute to the low nucleation rate in a highly viscous magnesium sulfate solutio

Impact of in-pore salt crystallization on transport properties

Precipitation of salts in confined spaces is the key mechanism for rock weathering and damage to building materials. To date there is no comprehensive study of the parameters influencing the reduction of pore space by salt crystals and the consequences for transport and damage by crystallization pressure. A novel method is presented to quantify pore clogging (i.e., the degree to which crystallization of salts interferes with transport of solution in porous materials). After drying capillary-saturated stone specimens containing salt solutions, the rate of capillary uptake of decane into the salt-contaminated specimens is measured. By treating the salt-contaminated material as a bilayer, the width of the crystallization front and the degree of pore filling can be determined. Two model materials with different pore size distributions (Indiana and Highmoor limestone) and three salts (sodium chloride, sodium sulfate and magnesium sulfate) are selected for this study. It is shown that pore clogging results from the interplay between pore size distribution and salt properties. Different scenarios are discussed to link pore clogging with salt damag

The chemomechanics of crystallization during rewetting of limestone impregnated with sodium sulfate

Breakdown of porous materials by salts occurs when growing crystals exert pressure on the pore walls, inducing stress in the material that exceeds its tensile strength. In this work, we quantify the mechanical stresses caused by a particularly destructive mechanism: the dissolution of an anhydrate (thenardite, Na2SO4) followed by precipitation of a hydrated salt (mirabilite, Na2SO4·10H2O). Stresses are measured using a composite specimen consisting of a plate of glass bonded to a plate of limestone (CaCO3) whose pores are impregnated with thenardite. As water wicks into the limestone, thenardite dissolves and mirabilite precipitates. The limestone expands from the pressure exerted by the salt resulting in deflection of the composite, and the stresses can be obtained from an elastic analysis. Synchrotron x-ray diffraction reveals the dissolution-crystallization rate. Numerical modeling shows that the stresses are affected by the kinetics of crystallization and dissolution, permeability, and mechanical properties of the stone, allowing us to determine the amount of salt that causes material fractur

Influence of chain stiffness, grafting density and normal load on the tribological and structural behavior of polymer brushes: a nonequilibrium-molecular-dynamics study

We have performed coarse-grained molecular-dynamics simulations on both flexible and semiflexible multi-bead-spring model polymer brushes in the presence of explicit solvent particles, to explore their tribological and structural behaviors. The effect of stiffness and tethering density on equilibrium-brush height is seen to be well reproduced within a Flory-type theory. After discussing the equilibrium behavior of the model brushes, we first study the shearing behavior of flexible chains at different grafting densities covering brush and mushroom regimes. Next, we focus on the effect of chain stiffness on the tribological behavior of polymer brushes. The tribological properties are interpreted by means of the simultaneously recorded density profiles. We find that the friction coefficient decreases with increasing persistence length, both in velocity and separation-dependency studies, over the stiffness range explored in this work

Water in the electrical double layer of ionic liquids on graphene

The performance of electrochemical devices using ionic liquids (ILs) as electrolytes can be impaired by water uptake. This work investigates the influence of water on the behavior of hydrophilic and hydrophobic ILs─with ethylsulfate and tris(perfluoroalkyl)trifluorophosphate or bis(trifluoromethyl sulfonyl)imide (TFSI) anions, respectively─on electrified graphene, a promising electrode material. The results show that water uptake slightly reduces the IL electrochemical stability and significantly influences graphene's potential of zero charge, which is justified by the extent of anion depletion from the surface. Experiments confirm the dominant contribution of graphene's quantum capacitance (CQ) to the total interfacial capacitance (Cint) near the PZC, as expected from theory. Combining theory and experiments reveals that the hydrophilic IL efficiently screens surface charge and exhibits the largest double layer capacitance (CIL ∼ 80 μF cm-2), so that CQ governs the charge stored. The hydrophobic ILs are less efficient in charge screening and thus exhibit a smaller capacitance (CIL ∼ 6-9 μF cm-2), which governs Cint already at small potentials. An increase in the total interfacial capacitance is observed at positive voltages for humid TFSI-ILs relative to dry ones, consistent with the presence of a satellite peak. Short-range surface forces reveal the change of the interfacial layering with potential and water uptake owing to reorientation of counterions, counterion binding, co-ion repulsion, and water enrichment. These results are consistent with the charge being mainly stored in a ∼2 nm-thick double layer, which implies that ILs behave as highly concentrated electrolytes. This knowledge will advance the design of IL-graphene-based electrochemical devices

Consolidation with ethyl silicate: how the amount of product alters the physical properties of the bricks and affects their durability

We evaluated the consolidating capacity of ethyl silicate in three types of bricks fired at 800, 950 and 1100 °C. We chose two concentrations of product, at 25% and 50%, diluting the product in white spirit to estimate whether greater dilution enables the product to penetrate deeper into the bricks, or whether a higher concentration leads to better consolidation of bricks. The application of ethyl silicate caused bricks porosity to decline and their compactness to increase. These changes were more accentuated as the concentration of the product increased. The pore size distribution not changed substantially except that there were fewer of the smallest pores. The color and the lightness of the pieces changed after application of the consolidant, albeit slightly. The durability of bricks improved as manifested by the results of the salt crystallization test. In general, the longest-lasting pieces were those treated with 25% ethyl silicate.Se ha evaluado la capacidad consolidante del silicato de etilo en tres tipos de ladrillos cocidos a 800, 950 y 1100 °C. Se eligieron dos concentraciones de producto, al 25% y 50%, diluyéndolo en white spirit para estimar si más dilución favorece una penetración más en profundidad del producto o si una mayor concentración produce una mejor consolidación de los ladrillos. El silicato de etilo ha causado una disminución de la porosidad y un aumento de la compacidad de los ladrillos, acentuándose estas modificaciones con mayor concentración de producto. La distribución porométrica no ha cambiado de forma sustancial, disminuyendo los poros más pequeños. Color y luminosidad de las piezas han modificado ligeramente tras la aplicación del consolidante. Los ladrillos consolidados han mejorado su durabilidad frente al envejecimiento acelerado producido por las sales. En general, las piezas más duraderas han resultado ser las tratadas con el 25% de silicato de etilo.This study was financially supported by Research Group RNM179 of the Junta de Andalucía and by Research Project MAT2016-75889-R

Micrometre and nanometre scale patterning of binary polymer brushes, supported lipid bilayers and proteins

Binary polymer brush patterns were fabricated via photodeprotection of an aminosilane with a photo-cleavable nitrophenyl protecting group. UV exposure of the silane film through a mask yields micrometre-scale amine-terminated regions that can be derivatised to incorporate a bromine initiator to facilitate polymer brush growth via atom transfer radical polymerisation (ATRP). Atomic force microscopy (AFM) and imaging secondary ion mass spectrometry (SIMS) confirm that relatively thick brushes can be grown with high spatial confinement. Nanometre-scale patterns were formed by using a Lloyd's mirror interferometer to expose the nitrophenyl-protected aminosilane film. In exposed regions, protein-resistant poly(oligo(ethylene glycol)methyl ether methacrylate) (POEGMEMA) brushes were grown by ATRP and used to define channels as narrow as 141 nm into which proteins could be adsorbed. The contrast in the pattern can be inverted by (i) a simple blocking reaction after UV exposure, (ii) a second deprotection step to expose previously intact protecting groups, and (iii) subsequent brush growth via surface ATRP. Alternatively, two-component brush patterns can be formed. Exposure of a nitrophenyl-protected aminosilane layer either through a mask or to an interferogram, enables growth of an initial POEGMEMA brush. Subsequent UV exposure of the previously intact regions allows attachment of ATRP initiator sites and growth of a second poly(cysteine methacrylate) (PCysMA) brush within photolithographically-defined micrometre or nanometre scale regions. POEGMEMA brushes resist deposition of liposomes, but fluorescence recovery after photobleaching (FRAP) studies confirm that liposomes readily rupture on PCysMA “corrals” defined within POEGMEMA “walls”. This leads to the formation of highly mobile supported lipid bilayers that exhibit similar diffusion coefficients to lipid bilayers formed on surfaces such as glass

Evaporative sodium salt crust development and its wind tunnel derived transport dynamics under variable climatic conditions

Playas (or ephemeral lakes) can be significant sources of dust, but they are typically covered by salt crusts of variable mineralogy and these introduce uncertainty into dust emission predictions. Despite the importance of crust mineralogy to emission potential, little is known about (i) the effect of short-term changes in temperature and relative humidity on the erodibility of these crusts, and (ii) the influence of crust degradation and mineralogy on wind speed threshold for dust emission. Our understanding of systems where emission is not driven by impacts from saltators is particularly poor. This paper describes a wind tunnel study in which dust emission in the absence of saltating particles was measured for a suite of climatic conditions and salt crust types commonly found on Sua Pan, Botswana. The crusts were found to be non-emissive under climate conditions characteristic of dawn and early morning, as compared to hot and dry daytime conditions when the wind speed threshold for dust emission appears to be highly variable, depending upon salt crust physicochemistry. Significantly, sodium sulphate rich crusts were found to be more emissive than crusts formed from sodium chloride, while degraded versions of both crusts had a lower emission threshold than fresh, continuous crusts. The results from this study are in agreement with in-situ field measurements and confirm that dust emission from salt crusted surfaces can occur without saltation, although the vertical fluxes are orders of magnitude lower (∼10 μg/m/s) than for aeolian systems where entrainment is driven by particle impact

Effect of crosslinking on the microtribological behavior of model polymer brushes

Polymer brushes in good solvents are known to exhibit excellent tribological properties. We have modeled polymer brushes and their gels using a multibead-spring model and studied their tribological behavior via nonequilibrium molecular-dynamics (MD) simulations. Simulations of brush- against-wall systems were performed using an implicit solvent-based approach. Polymer chains were modeled as linear chains, randomly grafted on a planar surface. Quantities extracted from the simulations are the normal stress, shear stress and concentration profiles. We find that while an increase in the degree of crosslinking leads to an increase in the coefficient of friction, an increase of the length of crosslinker chains does the opposite. Effect of crosslinking can be understood in two ways: (i) there are fewer polymer chains in the outer layer as the degree of crosslinking increases to take part in brush-assisted lubrication, and (ii) crosslinked polymer chains are more resistant to shear than non-crosslinked ones