Hydric behavior of earth materials and the effects of their stabilization with cement or lime: study on repair mortars for historical rammed earth structures

Earthen building materials bear interesting environmental advantages and are the most appropriate to conserve historical earth constructions. To improve mechanical properties, these materials are often stabilized with cement or lime, but the impact of the stabilizers on the water transport properties, which are also critical, has been very rarely evaluated. We have tested four earth-based repair mortars applied on three distinct and representative rammed earth surfaces. Three mortars are based on earth collected from rammed earth buildings in south of Portugal and the fourth mortar is based on a commercial clayish earth. The main objective of the work was over the commercial earth mortar, applied stabilized and not stabilized on the three rammed earth surfaces to repair, to assess the influence of the stabilizers. The other three earth mortars (not stabilized) were applied on each type of rammed earth, representing the repair only made with local materials. The four unstabilized earth materials depicted nonlinear dependence on t1/2 during capillary suction. This behaviour was probably due to clay swelling. Stabilization with any of the four tested binders enabled the linear dependence of t1/2 expected from Washburn's equation, probably because the swelling did not take place in this case. However, the stabilizers also increased significantly the capillary suction and the capillary porosity of the materials. This means that, in addition to increasing the carbon footprint, stabilizers like cement and lime have functional disadvantages that discourage its use in repair mortars for raw earth construction.

Applications of synchrotron x-ray powder diffraction in hydrated cements: high-resolution and high-pressure studies

The main aim of this study is to apply synchrotron radiation techniques for the study of hydrated cement pastes. In particular, the tetracalcium aluminoferrite phase, C4AF in cement nomenclature, is the major iron-containing phase in Ordinary Portland Cement (OPC) and in iron rich belite calcium sulfoaluminate cements. In a first study, the hydration mechanism of pure tetracalcium aluminoferrite phase with water-to-solid ratio of 1.0 has been investigated by HR-SXRPD (high resolution synchrotron X-ray powder diffraction). C4AF in the presence of water hydrates to form mainly an iron-containing hydrogarnet-type (katoite) phase, C3A0.84F0.16H6, as single crystalline phase. Its crystal structure and stoichiometry were determined by the Rietveld method and the final disagreement factors were RWP=8.1% and RF=4.8% [1]. As the iron content in the product is lower than that in C4AF, it is assumed that part of the iron also goes to an amorphous iron rich gel, like the hydrated alumina-type gel, as hydration proceeds. Further results from the high-resolution study will be discussed. In a second study, the behavior of pure and iron-containing katoites (C3AH6 and C3A0.84F0.16H6) under pressure have been analyzed by SXRPD using a diamond anvil cell (DAC) and then their bulk moduli were determined. The role of the pressure transmitting medium (PTM) has also been studied. In this case, silicone oil as well as methanol/ethanol mixtures have been used as PTM. Some “new peaks” were detected in the pattern for C3A0.84F0.16H6 as pressure increases, when using ethanol/methanol as PTM. These new peaks were still present at ambient pressure after releasing the applied pressure. They may correspond to crystalline nordstrandite or doyleite from the crystallization of amorphous aluminium hydroxide. The results from the high-pressure study will also be discussed.

Elimination of urine in response to water intake is consistent in well-hydrated individuals

A simple method has been recently proposed to assess acute hydration status in humans; however, several questions remain regarding its reliability, validity, and practicality. Objective: Establish reliability of a simple method to assess euhydration, that is, to analyze whether this method can be used as a consistent indicator of a person´s hydration status. In addition, the study sought to assess the effect exercise has on urine volume when euhydration is maintained and a standardized volume of water is ingested. Methods: Five healthy physically active men and five healthy physically active women, 22.5 ± 2.3 years of age (mean ± standard deviation) reported to the laboratory after fasting for 10 hours or more on three occasions, each one week apart. During the two identical resting euhydration conditions (EuA and EuB), participants remained seated for 45 minutes. During the exercise condition (EuExer), participants exercised intermittently in an environmental chamber (average temperature and relative humidity = 32 ± 3°C and 65 ± 7%, respectively) for a period of 45 minutes and drank water to offset loss due to sweating. The order of treatments was randomized. Upon finishing the treatment period, they ingested a volume of water equivalent to 1.43% body mass (BM) within 30 minutes. Urine was collected and measured henceforth every 30 minutes for 3 hours. Results: Urine volume eliminated during EuExer (1205 ± 399.5 ml) was not different from EuB (1072.2±413.1 ml) or EuA (1068 ± 382.87 ml) (p-value = 0.44). Both resting conditions were practically identical (p-value = 0.98) and presented a strong intraclass correlation (r = 0.849, p-value = 0.001). Conclusions: This method, besides simple, proved to be consistent in all conditions; therefore, it can be used with the certainty that measurements are valid and reliable.

Annual crop rotation of tropical pastures with no-till soil as affectedby lime surface application.

Soil acidity and low natural fertility are the main limiting factors for grain production in tropical regionssuch as the Brazilian Cerrado. The application of lime to the surface of no-till soil can improve plant nutrition, dry matter production, crop yields and revenue. The present study, conducted at the Lageado Experimental Farm in Botucatu, State of São Paulo, Brazil, is part of an ongoing research project initi-ated in 2002 to evaluate the long-term effects of the surface application of lime on the soil?s chemical attributes, nutrition and kernel/grain yield of peanut (Arachis hypogaea), white oat (Avena sativa L.) and maize (Zea mays L.) inter cropped with palisade grass (Urochloa brizantha cv. Marandu), as well as the forage dry matter yield of palisade grass in winter/spring, its crude protein concentration, estimated meat production, and revenue in a tropical region with a dry winter during four growing seasons. The experiment was designed in randomized blocks with four replications. The treatments consisted of four rates of lime application (0, 1000, 2000 and 4000 kg ha−1), performed in November 2004. The surface application of limestone to the studied tropical no-till soil was efficient in reducing soil acidity from the surface down to a depth of 0.60 m and resulted in greater availability of P and K at the soil surface. Ca and Mg availability in the soil also increased with the lime application rate, up to a depth of 0.60 m. Nutrient absorption was enhanced with liming, especially regarding the nutrient uptake of K, Ca and Mg by plants.Significant increases in the yield components and kernel/grain yields of peanut, white oat and maize were obtained through the surface application of limestone. The lime rates estimated to achieve the maximum grain yield, especially in white oat and maize, were very close to the rates necessary to increase the base saturation of a soil sample collected at a depth of 0?0.20 m to 70%, indicating that the surface liming of 2000 kg ha−1is effective for the studied tropical no-till soil. This lime rate also increases the forage dry matter yield, crude protein concentration and estimated meat production during winter/spring in the maize-palisade grass inter cropping, provides the highest total and mean net profit during the four growing seasons, and can improve the long-term sustainability of tropical agriculture in the Brazilian Cerrado.

Development of tahiti acid lime [Citrus latifolia (YU. Tanaka) Tanaka] budded trees in combination with different rootstocks.

2016

Growth, mineral composition, fruit yield, and mycorrhizal colonization of feijoa in response to lime and phosphorus application.

2016

Different doses of phosphorous and lime on Paspalum regnellii crop.

2016

An infrared spectroscopic study of the some Autunite minerals

A series of selected autunites with phosphate as the anion have been studied using infrared spectroscopy. Each autunite mineral has its own characteristic spectrum. The spectra for different autunites with the same composition are different. It is proposed that this difference is due to the structure of water and hydrated cations in the interlayer region between the uranyl phosphate sheets. This structure is different for different autunites. The position of the water hydroxyl stretching bands is related to the strength of the hydrogen bonds as determined by hydrogen bond distance. The highly ordered structure of water is also observed in the water HOH bending modes where a high wavenumber bands are observed. The phosphate and uranyl stretching vibrations overlap and are obtained by curve resolution.

Raman spectroscopic study of the magnesium carbonate minerals– artinite and dypingite

Magnesium minerals are important in the understanding of the concept of geosequestration. The two hydrated hydroxy magnesium carbonate minerals artinite and dypingite have been studied by Raman spectroscopy. Intense bands are observed at 1092 cm-1 for artinite and at 1120 cm-1 for dypingite attributed CO32- ν1 symmetric stretching mode. The CO32- ν3 antisymmetric stretching vibrations are extremely weak and are observed at1412 and 1465 cm-1 for artinite and at 1366, 1447 and 1524 cm-1 for dypingite. Very weak Raman bands at 790 cm-1 for artinite and 800 cm-1 for dypingite are assigned to the CO32- ν2 out-of-plane bend. The Raman band at 700 cm-1 of artinite and at 725 and 760 cm-1 of dypingite are ascribed to CO32- ν2 in-plane bending mode. The Raman spectrum of artinite in the OH stretching region is characterised by two sets of bands: (a) an intense band at 3593 cm-1 assigned to the MgOH stretching vibrations and (b) the broad profile of overlapping bands at 3030 and 3229 cm-1 attributed to water stretching vibrations. X-ray diffraction studies show the minerals are disordered. This is reflected in the difficulty of obtaining Raman spectra of reasonable quality and explains why the Raman spectra of these minerals have not been previously or sufficiently described.

Anisotropy of spin relaxation of water protons in cartilage and tendon

Transverse spin relaxation rates of water protons in articular cartilage and tendon depend on the orientation of the tissue relative to the applied static magnetic field. This complicates the interpretation of magnetic resonance images of these tissues. At the same time, relaxation data can provide information about their organisation and microstructure. We present a theoretical analysis of the anisotropy of spin relaxation of water protons observed in fully hydrated cartilage. We demonstrate that the anisotropy of transverse relaxation is due almost entirely to intramolecular dipolar coupling modulated by a specific mode of slow molecular motion: the diffusion of water molecules in the hydration shell of a collagen fibre around the fibre, such that the molecular director remains perpendicular to the fibre. The theoretical anisotropy arising from this mechanism follows the “magic-angle” dependence observed in magnetic-resonance measurements of cartilage and tendon and is in good agreement with the available experimental results. We discuss the implications of the theoretical findings for MRI of ordered collagenous tissues.

Strategies for zonal cartilage repair using hydrogels

Articular cartilage is a highly hydrated tissue with depth-dependent cellular and matrix properties that provide low-friction load bearing in joints. However, the structure and function are frequently lost and there is insufficient repair response to regenerate high-quality cartilage. Several hydrogel-based tissue-engineering strategies have recently been developed to form constructs with biomimetic zonal variations to improve cartilage repair. Modular hydrogel systems allow for systematic control over hydrogel properties, and advanced fabrication techniques allow for control over construct organization. These technologies have great potential to address many unanswered questions involved in prescribing zonal properties to tissue-engineered constructs for cartilage repair.

Unusual hydrate stabilization in the two-dimensional layered structure of quinacrinium bis(2-carboxy-4,5-dichlorobenzoate) tetrahydrate, a proton-transfer compound of the drug quinacrine

The crystal structure of the hydrated proton-transfer compound of the drug quinacrine [rac-N'-(6-chloro-2-methoxyacridin-9-yl)-N,N-diethylpentane-1,4-diamine] with 4,5-dichlorophthalic acid, C23H32ClN3O2+ . 2(C8H3Cl2O4-).4H2O (I), has been determined at 200 K. The four labile water molecules of solvation form discrete ...O--H...O--H... hydrogen-bonded chains parallel to the quinacrine side chain, the two N--H groups of which act as hydrogen-bond donors for two of the water acceptor molecules. The other water molecules, as well as the acridinium H atom, also form hydrogen bonds with the two anion species and extend the structure into two-dimensional sheets. Between these sheets there are also weak cation--anion and anion--anion pi-pi aromatic ring interactions. This structure represents only the third example of a simple quinacrine derivative for which structural data are available but differs from the other two in that it is unstable in the X-ray beam due to efflorescence, probably associated with the destruction of the unusual four-membered water chain structures.

Raman spectroscopic study of the hydroxy-arsenate mineral geminite Cu(AsO3OH)•H2O

The mineral geminite, an hydrated hydroxy-arsenate mineral of formula Cu(AsO3OH)•H2O, has been studied by Raman and infrared spectroscopy. Two minerals from different origins were investigated and the spectra proved quite similar. In the Raman spectra of geminite, four bands are observed at 813, 843, 853 and 885 cm-1. The assignment of these bands is as follows: (a) The band at 853 cm-1 is assigned to the AsO43- ν1 symmetric stretching mode (b) the band at 885 cm-1 is assigned to the AsO3OH2- ν1 symmetric stretching mode (c) the band at 843 cm-1 is assigned to the AsO43- ν3 antisymmetric stretching mode (d) the band at 813 cm-1 is ascribed to the AsO3OH2- ν3 antisymmetric stretching mode. Two Raman bands at 333 and 345 cm-1 are attributed to the ν2 AsO4 3- bending mode and a set of higher wavenumber bands are assigned to the ν4 AsO43- bending mode. A very complex set of overlapping bands is observed in both the Raman and infrared spectra. Raman bands are observed at 2288, 2438, 2814, 3152, 3314, 3448 and 3521 cm-1. Two Raman bands at 2288 and 2438 cm-1 are ascribed to very strongly hydrogen bonded water. The broader Raman bands at 3152 and 3314 cm-1 may be assigned to adsorbed water and not so strongly hydrogen bonded water in the molecular structure of geminate. Two bands at 3448 and 3521 cm-1 are assigned to the OH stretching vibrations of the (AsO3OH)2- units. Raman spectroscopy identified Raman bands attributable to AsO43- and AsO3OH2- units.

Synthesis and characterisation of cobalt hydroxy carbonate Co2CO3(OH)2 Nanomaterials

In an attempt to make nanofibres based upon cobalt oxides, a novel compound a hydrated cobalt hydroxy carbonate was formed. This compound is related to the minerals of the rosasite mineral group. X-ray diffraction showed that the formed compound was a cobalt hydroxy carbonate and SEM displayed bundles of fibres on the micron scale in length and nanoscale in width. The morphology was compared with that of the rosasite mineral group. XPS proved two bond energies for cobalt and three for oxygen in the compound. The compound was characterised by vibrational spectroscopy and the spectra related to minerals of the rosasite mineral group. The stability of the synthetic mineral was limited to temperatures below 200°C.

Raman spectroscopic study of the magnesium carbonate mineral– hydromagnesite Mg5[(CO3)4(OH)2]•4H2O

Magnesium minerals are important for the understanding of the concept of geosequestration. One method of studying the hydrated hydroxy magnesium carbonate minerals is through vibrational spectroscopy. A combination of Raman and infrared spectroscopy has been used to study the mineral hydromagnesite. An intense band is observed at 1121 cm-1 attributed CO32- ν1 symmetric stretching mode. A series of infrared bands at 1387, 1413, 1474 cm-1 are assigned to the CO32- ν3 antisymmetric stretching modes. The CO32- ν3 antisymmetric stretching vibrations are extremely weak in the Raman spectrum and are observed at 1404, 1451, 1490 and 1520 cm-1. A series of Raman bands at 708, 716, 728, 758 cm-1 are assigned to the CO32- ν2 in-plane bending mode. The Raman spectrum in the OH stretching region is characterised by bands at 3416, 3516 and 3447 cm-1. In the infrared spectrum a broad band is found at 2940 cm-1 assigned to water stretching vibrations. Infrared bands at 3430, 3446, 3511, 2648 and 3685 cm-1 are attributed to MgOH stretching modes.