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 damage.     

Assessment of the Effects of Freeze–Thaw and Salt Crystallization Ageing Tests on Anahita Temple Stone,Kangavar, West of Iran

Building stone of Anahita Temple seriously suffers from weathering due to long term freezing-thawing and salt crystallization processes. This article investigates possible changes of physical and mechanical characteristics of this stone subjected to freeze–thaw and salt crystallization ageing tests. Fresh samples obtained from the Chelmaran quarry (the main quarry supplying for Anahita Temple stone) were tested under freeze–thaw and salt crystallization experiments. The freeze–thaw and sodium sulfate salt crystallization are suggested to be the most effective factors affecting in apparent deterioration of the stone in compare to the magnesium sulfate salt crystallization test. Significant decreases in mechanical properties of the stone were observed after freeze–thaw and salt crystallization tests. However, more mechanical losses were recorded after the salt crystallization cycles than the freeze–thaw cycles. This is probably due to crystallization pressure of salt crystals in compare to ice wedging force, which promoted more development of micro-fractures in the specimens. Probably, intrinsic factors of the stone such as frequent calcite veins and stylolites, are the main factors that control the durability of Anahita Temple stone. Preferential weakening along these features during freeze–thaw and salt crystallization cycles led to physical destruction and strength loss of the stone. Based on comparison between experimentally induced damages and field observations, reasonably freeze–thaw process is major factor in weathering of Anahita Temple stone. It should be noted that recorded 102 frozen days for the region imply high destruction potential of the stone during freeze–thaw cycles.     

Alteration kinetics of natural stones due to sodium sulfate crystallization: can reality match experimental simulations?

Salt decay is a very destructive mechanism that affects frequently the porous building materials of our architectural heritage. Sodium sulfate is one of the salts found in this context. It usually demonstrates high destructive power in salt crystallization tests because it can crystallize not only during evaporative processes but also when the temperature drops or when the salt solution comes into contact with pre-existing crystals. However, the use of extreme temperatures or successive wet/dry cycles also makes these tests unrepresentative of reality. To verify whether sodium sulfate can also be so destructive in field conditions, we have performed crystallization tests consisting of a single isothermal drying event. Three natural stones, relevant for the architectural heritage, were used for the purpose: Bentheimer sandstone, Ançã limestone, and a current Portuguese limestone of low porosity. The stones gave rise to distinct salt decay patterns: efflorescence, multilayer delamination and unilayer delamination, respectively. These morphological alterations were characterized at the micrometer scale by a new method based on what we have called the alteration kinetics curve. Such curve is calculated from topographic profiles obtained by a non-contact optical technique. The multilayer and unilayer delamination decay were also monitored by time-lapse photography. The work led us to conclude that sodium sulfate can indeed be also very destructive in field-representative conditions. Moreover, it showed that the optical method can be a valuable aid in the development of more realistic salt crystallization tests.     

硫酸盐对麦积山砂砾岩风化影响的试验研究

麦积山石窟砂砾岩在盐分参与下出现粉化、剥落等现象,这大大加速了石窟岩体的风化进程。通过对砂砾岩进行毛细迁移及循环劣化试验,研究了硫酸盐在砂砾岩中的运移规律,分析了盐分参与下砂砾岩的破坏特征,并得出了其产生的结晶压力。结果表明：硫酸钠结晶使砂砾岩发生显著破坏;硫酸盐在砂砾岩中的运移呈现一定的规律性;硫酸钠溶液的浓度达到0.95～1.13 mol/L区间时,砂砾岩开始破坏,并且得出试验条件下结晶压力理论最大值可以达到33 MPa。     

Crystallization of sodium sulfate salts in limestone

Crystallization pressure of salt crystals growing in confined pores is found to be the main cause for damage to stone and masonry. In this work, the crystallization of sodium sulfate salts in Cordova Cream and Indiana limestones is investigated using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The DSC experiments indicate that sodium heptahydrate always precipitates prior to the decahydrate (mirabilite), at a temperature between 15 and 7°C in the selected stones. The threshold supersaturation for the nucleation of heptahydrate is less than 2. In constrast, mirabilite precipitates close to or below 0°C and its crystallization pattern is completely different: precipitation takes place abruptly when the threshold supersaturation is reached, which is greater than 7. Indeed, the DSC and the DMA experiments reveal the rare nature of the nucleation of mirabilite for the investigated stones. The crystallization pressure exerted by heptahydrate does not cause damage under the conditions of the cooling experiments. In contrast, mirabilite exerts a very high crystallization pressure on the pore wall causing damage of the stone; moreover, the transient stress can remain for a long period of time since the relaxation process is slow.     

An integrated methodology for salt damage assessment and remediation: the case of San Jerónimo Monastery (Granada, Spain)

San Jerónimo Monastery (Granada, Spain) was selected as a case study for the investigation of the effect of indoor environmental conditions on salt weathering and for on-site testing of a remediation treatment using crystallization inhibitors on account of the extreme salt damage affecting both the building stone, a biomicritic limestone, calcarenite and wall paintings. A methodology combining several analysis techniques, phenomenological observations, salt and moisture analysis, environmental monitoring and thermodynamic simulations, was adopted in order to study the salt damage problems affecting this building. Within the collected samples, the majority of salts were found to be magnesium sulphate in the form of either hexahydrite or epsomite, depending on the climate conditions, together with minor amounts of gypsum, nitrates and chlorides. Comparison of empirical observations with thermodynamic simulations of the salt mixture behaviour clearly showed that salt-induced damage events take place during the seasonal changes from spring to summer and winter to spring. An aqueous solution of an organic phosphonate, which in laboratory experiments was found to be an effective inhibitor of magnesium sulphate crystallization, was sprayed over a selected test area of unpainted stonework at the site. Preliminary results seem to indicate that after the application of the treatment both the amount of efflorescence and ongoing damage to the stone support is reduced. However, long-term monitoring of the future condition of the test area is needed to confirm whether indeed this treatment is appropriate and effective in reducing salt damage at this case study site. The outcome of this study extends beyond the particular problems at San Jerónimo Monastery, as it demonstrates a methodological approach for the study and evaluation of salt weathering problems affecting cultural heritage.     

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 solution.     

Crystallization of sodium sulfate phases in porous materials: The phase diagram Na2SO4-H2O and the generation of stress

Mechanical disintegration by crystal growth of salts in pores is generally considered as an important mechanism of rock breakdown both on Earth and on Mars. Crystal growth is also a major cause of damage in porous building materials. Sodium sulfate is the most widely used salt in accelerated weathering tests of natural rocks and building materials. This paper provides an updated phase diagram of the Na₂SO₄-H₂O system based on a careful review of the available thermodynamic data of aqueous sodium sulfate and the crystalline phases. The phase diagram includes both the stable phases thenardite, Na₂SO₄(V), and mirabilite, Na₂SO₄·10H₂O, and, the metastable phases Na₂SO₄(III) and Na₂SO₄·7H₂O. The phase diagram is used to discuss the crystallization pathways and the crystallization pressures generated by these solids in common laboratory weathering experiments and under field conditions. New crystallization experiments carried out at different temperatures are presented. A dilatometric technique is used to study the mechanical response of sandstone samples in typical wetting-drying experiments as in the standard salt crystallization test. Additional experiments with continuous immersion and evaporation were carried out with the same type of sandstone. Both, the theoretical treatment and the results of the crystallization experiments confirm that the crystallization of mirabilite from highly supersaturated solutions is the most important cause of damage of sodium sulfate in porous materials.     

硫酸（亚硫酸）盐渍土单次盐胀和冻胀发育规律研究

对盐胀和冻胀规律的研究有助于深入认识硫酸（亚硫酸）盐渍土的工程性质。通过对天山北麓水磨河流域细土平原区硫酸（亚硫酸）盐渍土盐胀和冻胀试验研究发现：（1）随着温度的降低,试样盐胀和冻胀率逐渐增大。试样冻结前土体产生的膨胀是盐胀,试样冻结后产生的膨胀是盐胀和冻胀,当土体达到-15℃以后,土体盐胀和冻胀趋于稳定。（2）硫酸钠含量不变的情况下,随着含水量的增大,其起胀温度降低。土体起胀温度取决于土体中硫酸钠析水结晶温度、硫酸钠结晶含量的多少、土体结构、内摩阻力、粘聚力、土颗粒间的引力、土体孔隙间和孔隙接触间吸收结晶硫酸钠的程度。（3）硫酸钠含量增加,其单次盐胀和冻胀率变化区间增大。     

降温速率对硫酸钠溶液晶体析出影响的试验研究

为探讨硫酸钠盐渍土盐胀机理,研究了十水硫酸钠晶体在硫酸钠溶液中的析出规律.针对不同浓度的硫酸钠溶液,在1℃·min^-1、0.1℃·min^-1和0.02℃·min^-13种降温速率下,通过降温试验对晶体初始析出温度进行观测.试验表明：十水硫酸钠晶体的析出受降温速率的影响,随着降温速率的减小,晶体初始析出温度升高;降温速率的大小对晶体析出后溶液浓度变化几乎没有影响,但其会影响晶体形态,降温速率越小,晶体形态更为稳定;晶体析出受到相变驱动力作用,相变驱动力与降温速率大小呈正比,降温速率越大,晶体初始析出结晶力越大.     

Amorphous silica solubilities—II. Effect of aqueous salt solutions at 25°C

The solubility of amorphous silica was measured at 25°C in ten separate sets of aqueous salt solutions—potassium chloride, potassium nitrate, sodium chloride, lithium chloride, lithium nitrate, magnesium chloride, calcium chloride, magnesium sulfate, sodium bicarbonate and sodium sulfate. The concentrations of the salts were varied from zero to saturation with both salt and amorphous silica. With increasing concentration of salt, the solubility of amorphous silica always decreased as expected from an average value of 0.00218 m in water. Nevertheless, the extent of decrease differed greatly from a 6% decrease in a solution saturated with NaHCO₃ to a 95.7% decrease in a solution saturated with CaCl₂. A striking correlation was observed: In the 1-1 and 2-1 electrolyte salt solutions at a given molality the effect on the solubility of silica depended upon the cation in the order Mg²⁺, Ca²⁺ > Li⁺ > Na⁺ > K ⁺.     

Crystallization behavior of Na2SO4–MgSO4 salt mixtures in sandstone and comparison to single salt behavior

We report on the crystallization behavior and the salt weathering potential of Na₂SO₄, MgSO₄ and an equimolar mixture of these salts in natural rock and porous stone. Geochemical modeling of the phase diagram of the ternary Na₂SO₄–MgSO₄–H₂O system was used to determine the equilibrium pathways during wetting (or deliquescence) of incongruently soluble minerals and evaporation of mixed electrolyte solutions. Model calculations include stable and metastable solubilities of the various hydrated states of the single salts and the double salts Na₂Mg(SO₄)₂·4H₂O (bloedite), Na₂Mg(SO₄)₂·5H₂O (konyaite), Na₁₂Mg₇(SO₄)₁₃·15H₂O (loeweite) and Na₆Mg(SO₄)₄ (vanthoffite). In situ Raman spectroscopy was used to study the phase transformations during wetting of pure MgSO₄·H₂O (kieserite) and of the incongruently soluble salts bloedite and konyaite. Dissolution of kieserite leads to high supersaturation resulting in crystallization of higher hydrated phases, i.e. MgSO₄·7H₂O (epsomite) and MgSO₄·6H₂O (hexahydrite). This confirms the high damage potential of magnesium sulfate in salt damage of building materials. The dissolution of the incongruently soluble double salts leads to supersaturation with respect to Na₂SO₄·10H₂O (mirabilite). However, the supersaturation was insufficient for mirabilite nucleation. The damage potential of the two single salts and an equimolar salt mixture was tested in wetting–drying experiments with porous sandstone. While the high damage potential of the single salts is confirmed, it appears that the supersaturation achieved during wetting of the double salts at room temperature is not sufficient to generate high crystallization pressures. In contrast, very high damage potentials of the double salts were found in experiments at low temperature under high salt load.1     

Patterns of halite (NaCl) crystallisation in building stone conditioned by laboratory heating regimes

The crystallisation of soluble salts within the pores of the stone is widely recognised as a major mechanism causing the deterioration of the stone-built architectural heritage. Temperature, in turn, is one of the main controls on this process, including salt precipitation, the pressure of crystallisation and the thermal expansion of salts. Most laboratory experiments on decay generated by salts are just carried out with convective heating regimes, while in natural environments building stones can undergo radiative and convective heating regimes. The thermal response of stone to these different heating regimes is noticeably different and might influence the crystallisation patterns of a salt within a stone. The aim of this work is to raise awareness on the different patterns of crystallisation of NaCl within a porous stone tested with different heating regimes (convection and radiation) and the implications that this could have on the design of experimental modelling of natural weathering conditions in laboratory simulations. Results show that heating regime affects the sodium chloride distribution within a stone with high percentage of microporosity. In this case, radiation heating facilitates the generation of subefflorescences, while convection heating promotes efflorescences. This has a clear implication both on the stone decay in natural environments and on the methodologies for testing salt decay, as subefflorescences are more destructive than efflorescences. In this sense, the use of convective heating in laboratory experimentation might underestimate the potential damage that sodium chloride may generate. This counsels the use of radiation heating test methods in addition to convection for the laboratory study of salt crystallisation.     

Quantification of salt weathering in porous stones using an experimental continuous partial immersion method

In this study, an experimental salt weathering simulation and porous stone durability classification are proposed. There are many laboratory tests that quantify durability against salt crystallisation weathering action. These are usually based on the total immersion of samples into a saline solution, which is not representative of the salt weathering mechanism. An experimental test based on partial immersion is suggested. This is a comparable study of weight loss and degradation of visual appearance due to salt crystallisation using, on the one hand, a standard durability test (UNE), and, on the other, the proposed durability test. The weight loss and visual appearance in our test is comparable to the degradation of building stone. The differences between weight loss data in both tests depend on the petrophysical properties: porous media and degree of coherence.

From this testing, a new durability classification as a function of dry weight loss in the partial immersion test is proposed. Four divisions of different types of materials can be made in this classification, which quantifies salt weathering action mainly in environments and mild climatic conditions.     

含NaCl和Na2SO4双组分盐渍土的水盐相变温度研究

盐渍土相变温度是判断土体中水分冻结与融化、盐分结晶与溶解的重要参数。不同盐分含量相变温度的差异,给盐渍土在降温过程中的水盐迁移过程及变形规律的模拟带来极大的不确定性。通过降温试验,研究了降温过程中氯盐和硫酸盐综合作用盐渍土中水盐相变温度的变化情况。结果表明：全盐量相同时,盐结晶温度随NaCl和Na₂SO₄比例的不同而不同。随NaCl的加入,在Na⁺同离子效应的影响下,Na₂SO₄更容易结晶,但土体的冰和芒硝共晶点温度下降,使得冰含量显著减少,从而降低了孔隙溶液中固相的产生比例,起到抑制Na₂SO₄盐渍土盐冻胀变形的作用。当土中只含Na₂SO₄盐时,随Na₂SO₄浓度的增加,冰和芒硝共晶点的温度先上升而后缓慢下降,二次相变前冰盐的累积量是导致冰和芒硝共晶点产生这种变化的主要原因。盐渍土三相共晶点温度随NaCl含量的增加呈现上升趋势,这是因为随着NaCl的加入,在发生三相共晶前,孔隙溶液发生相变的固相含量减少,从而使孔隙结构对三相共晶点的影响减小。此外,含有NaCl与Na₂SO₄双组分的盐渍土,水分和盐分可能以单固相、双固相以及三固相状态析出。研究结果可为深入认识盐渍土的相变规律及物理性质提供理论支撑。     

A comparison of the properties and salt weathering susceptibility of natural and reconstituted stones of the Orval Abbey (Belgium)

The Orval Abbey, a major monument of southern Wallonia, Belgium, was partly destroyed and rebuilt several times between the Middle Ages and the present time. The oldest parts are made of natural stones of local origin (Bajocian and Sinemurian limestones) and the most recent parts are mostly made of reconstituted stone. The process of reconstituted stone making is not known. Although confronting the same environmental conditions, the reconstituted stone is much more susceptible to weathering than the natural limestones, especially to salt crystallisation. The present study compared the mineralogical and petrophysical properties of these building materials to gather information on the making of the reconstituted stone and to understand the difference in salt susceptibility between natural and reconstituted stones. Microscopic observations and petrophysical measurements showed that the reconstituted stone is composed of debris of Sinemurian and Bajocian limestone and cement, and the salt efflorescences were thenardite. Within the cement, amorphous grains were found that may correspond to grains of clinker, which have not reacted during stone making. Although its porosity and water transfer properties were close to that of the Bajocian limestone, its pore access distribution was centred around 0.1 μm. Furthermore, the details of the pore size distribution allowed calculating salt susceptibility indices that were very high in the case of the reconstituted stone. Thus, the composition of the cement and the pore size distribution are likely the two factors explaining a high susceptibility of the reconstituted stone to salt weathering.     

Amorphous silica solubilities IV. Behavior in pure water and aqueous sodium chloride,sodium sulfate,magnesium chloride,and magnesium sulfate solutions up to 350°C

Solubilities of amorphous silica were determined in separate aqueous solutions of sodium chloride, sodium sulfate, magnesium chloride, and magnesium sulfate at temperatures up to 350°C. These salts, of strong interest in hydrothermal oceanography and geothermal energy, generally ranged in concentration from zero to saturation. Solubilities in the sodium chloride solutions followed closely earlier observed decreases in sodium nitrate solutions at high temperatures.Amorphous silica solubilities were depressed most by magnesium chloride, followed by magnesium sulfate, and less by sodium chloride. As the temperature rose the relative decrease in solubility caused by added salt became smaller. Surprisingly, sodium sulfate solutions, showing little effect at 25°C, sharply raised the solubility as the temperature increased to 350°C. Plots of the logarithms of derived activity coefficients against molalities of added salt gave approximately straight lines. These plots allow simple predictions of amorphous silica solubility in single salt solutions.     

Laboratory simulation showing the influence of salt efflorescence on the weathering of composite building materials

A common decay scenario in old and new buildings was simulated: the effects on masonry structures of salt efflorescence or subefflorescence produced by the rise of saline solution. Eight different types of masonry wall each made up of a combination of different construction materials (brick, calcarenite and four types of mortar were combined as follows: pure lime mortar, mortar + air entraining agent, mortar + pozzolana, mortar + air entraining agent + pozzolana) have been tested. These materials have different textures (strong anisotropy in brick, irregular-shaped pores in calcarenite, retraction fissures or rounded pores in mortars which also show a reduction of porosity along the contact area with the stone), different hydric behaviours (under total immersion brick + mortar specimens absorb water faster than calcarenite + mortar specimens) and different pore size distribution (brick shows unimodal pore distribution, whereas calcarenite and mortars are bimodal). In the salt weathering test, mortars interlayered with masonry blocks did not act as sacrificial layers. In fact, they allowed salts to rise through them and crystallize on the brick or calcarenite pieces causing the masonry structure to decay. Only the addition of an air-entraining agent partially hindered the capillary rise of the salt-laden solutions.     

Performance of limestones laden with mixed salt solutions of Na2SO4–NaNO3 and Na2SO4–K2SO4

The behaviour of two types of limestones having a different porosity, Maastricht and Euville limestone, laden with aqueous solutions of equimolar mixtures of sodium sulphate/sodium nitrate or sodium sulphate/potassium sulphate was investigated. At 50 % RH, the efflorescences on Maastricht samples during the first 30 h of drying consisted of similar amounts of thenardite and darapskite in case of an equimolar mixture of sodium sulphate/sodium nitrate while those on Euville samples under the same conditions contained mainly darapskite. After drying at 20 °C and 85 % RH, thenardite, formed through the precipitation and dehydration of mirabilite, was mostly detected in the efflorescences on both Maastricht and Euville samples. Re-wetting by increasing the RH from 50 to 85 % resulted in substantial damage on Maastricht stone laden with an equimolar mixture of sodium sulphate/sodium nitrate as a consequence of high supersaturation of mirabilite. In case of a contamination with equimolar amounts of sodium sulphate and potassium sulphate, the efflorescence on both limestones during drying at 50 % RH contained predominantly aphthitalite. The observed crystallisation behaviour is compared to the theoretical behaviour. The results indicate a strong influence of stone properties on the crystallisation behaviour of salt mixtures.     

Changing climate, changing process: implications for salt transportation and weathering within building sandstones in the UK

Salt weathering is a crucial process that brings about a change in stone, from the scale of landscapes to stone outcrops and natural building stone façades. It is acknowledged that salt weathering is controlled by fluctuations in temperature and moisture, where repeated oscillations in these parameters can cause re-crystallisation, hydration/de-hydration of salts, bringing about stone surface loss in the form of, for example, granular disaggregation, scaling, and multiple flaking. However, this ‘traditional’ view of how salt weathering proceeds may need to be re-evaluated in the light of current and future climatic trends. Indeed, there is considerable scope for the investigation of consequences of climate change on geomorphological processes in general. Building on contemporary research on the ‘deep wetting’ of natural building stones, it is proposed that (as stone may be wetter for longer), ion diffusion may become a more prominent mechanism for the mixing of molecular constituents, and a shift in focus from physical damage to chemical change is suggested. Data from ion diffusion cell experiments are presented for three different sandstone types, demonstrating that salts may diffuse through porous stone relatively rapidly (in comparison to, for example, dense concrete). Pore water from stones undergoing diffusion experiments was extracted and analysed. Factors controlling ion diffusion relating to ‘time of wetness’ within stones are discussed, (continued saturation, connectivity of pores, mineralogy, behaviour of salts, sedimentary structure), and potential changes in system dynamics as a result of climate change are addressed. System inputs may change in terms of increased moisture input, translating into a greater depth of wetting front. Salts are likely to be ‘stored’ differently in stones, with salt being in solution for longer periods (during prolonged winter wetness). This has myriad implications in terms of the movement of ions by diffusion and the potential for chemical change in the stone (especially in more mobile constituents), leading to a weakening of the stone matrix/grain boundary cementing. The ‘output’ may be mobilisation and precipitation of elements leading to, for example, uneven cementing in the stone. This reduced strength of the stone, or compromised ability of the stone to absorb stress, is likely to make crystallisation a more efficacious mechanism of decay when it does occur. Thus, a delay in the onset of crystallisation while stonework is wet does not preclude exaggerated or accelerated material loss when it finally happens.