Hypothetical transformation of Ca(OH)<Subscript>2</Subscript> into CaCO<Subscript>3</Subscript> in solid-state reactions of portland cement

Summary Previous study of the hydration and ageing products of two cement pastes created the basis for the postulate of the course of solid-state reactions between the portlandite Ca(OH)₂ and the CO₂ from air in the hydrated and air dry cement. XRD basal spacing d(001) of portlandite exceeded the nominal value and increased with ageing, with the wetting and drying procedure and with carbonate content of the paste, indicating that a part of OH^- ions was gradually substituted by CO₃^2- ions, which are about twice bigger. IR spectroscopy showed a considerable content of portlandite, of CO₃^2- of water and silicates. Also HCO₃^- H₂O and CO₂ in cavities between hexagonal rings and hexagonal hydrates were indicated. By MS (mass spectrometry) in vacuum the evaporation of sorbed water was detected at 100-120°C, of gel water at 350°C of portlandite water at 400°C and of high temperature water between 500 and 700°C, simultaneously with CO₂ escape. Slightly higher peak temperatures were found by the TG test either in air or in argon. From these results and from geometric considerations it is postulated that the solid-state reactions take place on ageing of the cement paste and on its heating: hexagonal portlanditecalcium carbonate hydroxy hydratecalcium carbonate hydratehexagonal vaterite and/or orthorhombic aragoniterhombohedral calcite The analysis of the standard files of the calcium carbonate hydroxy hydrates supports this postulate and indicates a gradual transformation.     

Hydration products in two aged cement pastes

The hydration products in two aged cement pastes (DTA/DTG/TG) were compared with those in fresh ones (static heating, SH) and were also studied by mass spectrometry (MS), IR and thermo XRD-analysis. The products considered here were: the sorbed water, the CSH gel including hydrates, portlandite, calcite, aragonite and vaterite. Except carbonates their content was higher in the stronger paste C-43, than in C-33, but lowered with ageing (only the CSH gel water remained approximately unchanged). The sorbed water content became with time lower and similar in both pastes (it evaporated up to 155-185°C in TG); the escape of the rest moved to higher temperatures (500-700°C). The three DTG peaks at 200-400°C indicated jennite-like phase in the CSH gel; the mass loss (155-460°C) was higher on ageing due to development of organic matter, especially in C-43 (DTA, TG, IR). Portlandite content changed little and carbonate content increased considerably. They decomposed in air at 470 and 720-740°C, in argon at 450 and 680-710°C and in vacuum at 400 and 630°C, respectively (DTG peak, XRD). Between 500 and 700°C the simultaneous evolution of H₂O and CO₂was observed by MS, which is attributed to dehydroxylation of jennite-like phase and/or to decomposition of some carbonate hydrate and/or hydrocarbonate (three peaks on CO₂evolution curve, MS). The d(001) peak of portlandite exceeded the nominal value and will be analyzed separately.     

Investigation on the stability,electronic, optical,and mechanical properties of novel calcium carbonate hydrates via first-principles calculations

Calcium carbonate (CaCO₃) is an inorganic compound which is widely used in industry, chemistry, construction, ocean acidification, and biomineralization due to its rich constituent on earth and excellent performance, in which calcium carbonate hydrates are important systems. In Zou et al's work (Science, 2019, 363, 396-400), they found a novel calcium carbonate hemihydrate phase, but the structural stability, optical, and mechanical properties have not been studied. In this work, the stability, electronic, optical, and mechanical properties of novel calcium carbonate hydrates were investigated by using the first-principles calculations using density functional theory. CaCO₃·xH₂O (x = 1/2, 1 and 6) are determined dynamically stable phases by phonon spectrum, but the Gibbs energy of reaction of CaCO₃·1/2H₂O is higher than other calcium carbonate hydrates. That is why CaCO₃·1/2H₂O is hard to synthesize in the experiments. In addition, the optical and mechanical properties of CaCO₃·xH₂O (x = 1/2, 1 and 6) are expounded in detail. It shows that the CaCO₃·1/2H₂O has the largest bulk modulus, shear modulus, and Young's modulus with the values 60.51 GPa, 36.56 GPa, and 91.28 GPa. This work will provide guidance for experiments and its applications, such as biomineralization, geology, and industrial processes.     

Phase transformation on heating of an aged cement paste

The standard cement paste (C-43-St) was studied previously by static heating, SH, immediately after 1 month hydration at w/c = 0.4 [J. Therm. Anal. Calorim. 69 (2002) 187]. This paste after 5-year ageing (unprotected from contact with air) was subject to thermal analysis in air and in argon (DTA, DTG and TG), to XRD at various temperatures, T, in a high temperature chamber, to mass spectroscopy (MS) and to IR spectroscopy. The aim of this study was to compare the results of SH (fresh paste) and of TG (the aged one), to verify the assumptions made on SH interpretation and to check the change in hydration products with ageing as measured by phase transformation on heating (ΔM versus the final mass). The sorbed water (EV), escaping at 110 °C from the fresh paste, was bound on ageing with a higher energy and escaped at higher temperatures. The joint water content of hydrates and of C-S-H gel increased on ageing by 1–2% in the dense paste C-43-St and did not change in the less compact one C-43-I. C-S-H gel transformed on heating above 600 °C into C₂S and C₃S. Portlandite content did not change on ageing. In the air atmosphere it became partly carbonated, which was accompanied by an increase in mass between 500 and 600 °C. Carbon dioxide and/or carbonate ions to form carbonates, were sorbed during ageing and were present in the aged paste in some form undetectable by XRD (amorphous or crypto-crystalline). Sensitivity to carbonation ΔM(700–800 °C) increased highly with ageing.     

Degree of hydration in cement paste and C<Subscript>3</Subscript>A-sodium carbonate-water systems

This research provides a fundamental understanding of the early stage hydration of Portland cement paste, tricalcium aluminate (C₃A) paste at water to cement ratio of 0.5 and C₃A suspension at water to cement ratio of 5.0 modified by 2 or 4 mass% of sodium carbonate. A high conversion of unreacted clinker minerals to gel-like hydration products in the cement-Na₂CO₃ pastes takes place rapidly between 1^st to 24^th h. Contrary the Ca(OH)₂ formation within the same time interval is retarded in the excess of CO₃²⁻ ions due to intensive rise and growth of CaCO₃ crystals in hydrated cement. Later, the conversion of clinker minerals to the hydrate phase is reduced and higher contents of calcite and vaterite relative to that of Ca(OH)₂ in comparison with those found in the Portland cement paste are observed. As a consequence a decrease in strength and an increase in porosity between hardened Portland cement paste without sodium carbonate and those modified by Na₂CO₃ are observed. C₃A hydrates very quickly with sodium carbonate between 1^st and 24^th h forming hydration products rich in bound water and characterized also by complex salts of (x)C₃A·(y)CO₂·(zH₂O type, whereas C₃A-H₂O system offers C₃AH₆ as the main hydration product. Higher content of the formed calcium aluminate hydrates in C₃A-Na₂CO₃-H₂O system also contributes to early strength increase of Portland cement paste.     

Theory of Microbial Carbonate Precipitation and Its Application in Restoration of Cement-based Materials Defects

Bacterial induced carbonate mineralization has been demonstrated as a new potential method for restoration of limestones in historic buildings and monuments. We claim here the formation of calcium carbonate was controlled by extracellular polymeric substances (EPS) isolated from Bacillus pasteurii. The process of crystallization nucleation was accelerated in the presence of cells and inhibited in the presence of EPS. The CaCO₃ film deposited on cement paste surface was about 100 µm after 7 d treatment. The results of various restoring methods showed that higher decrease of water absorption of cement paste was gained in brushing application in the presence of agar, which could maintain urease with high activity in long term compared to spraying method. The coefficient of capillary suction of cement paste treated with brushing method was reduced by 90%. Mixed media consisted of sands, urea, Ca²⁺ and concentrated biomass, was injected into artificial cracks of cement paste followed by continual nutrient supplement, and CaCO₃ particles were precipitated gradually between sands particles which were combined with cement matrix. The results showed that the compressive strength of recovered specimens was restored to 84%, which demonstrated that this kind of bio‐restoration method is effective in repairing surface defects of cement‐based materials.     

Heat capacity and transition phenomena of structure I and II trimethylene oxide clathrate hydrates

Heat capacities of structure I and II trimethylene oxide (TMO) clathrate hydrates doped with small amount of potassium hydroxide (x=1.8×10^–4 to water) were measured by an adiabatic calorimeter in the temperature range 11–300 K. In the str. I hydrate (TMO·7.67H₂O), a glass transition and a higher order phase transition were observed at 60 K and 107.9 K, respectively. The glass transition was considered to be due to the freezing of the reorientation of the host water molecules, which occurred around 85 K in the pure sample and was lowered owing to the acceleration effect of KOH. The relaxation time of the water reorientation and its distribution were estimated and compared with those of other clathrate hydrates. The phase transition was due to the orientational ordering of the guest TMO molecules accommodated in the cages formed by water molecules. The transition was of the higher order and the transition entropy was 1.88 J·K^–1(TMO-mol)^–1, which indicated that at least 75% of orientational disorder was remaining in the low temperature phase. In the str. II hydrates (TMO·17H₂O), only one first-order phase transition appeared at 34.5 K. This transition was considered to be related to the orientational ordering of the water molecules as in the case of the KOH-doped acetone and tetrahydrofuran (THF) hydrates. The transition entropy was 2.36 JK^–1(H₂O-mol)^–1, which is similar to those observed in the acetone and THF hydrates. The relations of the transition temperature and entropy to the guest properties (size and dipole moment) were discussed.Contribution No 57 from the Microcalorimetry Research CenterThe authors would like to express their sincere thanks to the Nissan Science Foundation for their financial support.     

Study of the nature of the crystallization water in some magnesium hydrates by thermal methods

The nature of the crystallization water in MgSO₄·7H₂O, Mg(NO₃)₂·6H₂O and MgCl₂·6H₂O has been studied with the nonisothermal methods of thermogravimetry (TG), derived thermogravimetry (DTG) and differential thermal analysis (DTA). Analysis of the characteristic thermogravimetric data (T _M,W _∞) and the kinetic parameters (n, E _a), together with the DTA results, with CuSO₄·5H₂O as control sample, provided evidence of the existence of coordinated water and of the nature of the anions in these hydrates. The results are confirmed by the observation of a real compensation effect. For the compensation effect, the following equation is proposed: InA=0.220E-0.8 Structures explaining the presence of the coordinated water and the nature of the anions in these hydrates are also proposed.     

An unusual isotopic fractionation of boron in synthetic calcium carbonate precipitated from seawater and saline water

Inorganic calcium carbonate precipitation from natural seawater and saline water at various pH values was carried out experimentally. The results show the clear positive relationships between boron concentration and δ11B of inorganic calcium carbonate with the pH of natural seawater and saline water. However, the variations of boron isotopic fractionation between inorganic calcite and seawater/saline water with pH are inconsistent with the hypothesis that B(OH)4- is the dominant spe-cies incorporated into the biogenic calcite structure. The isotopic fractionation factors α between synthetic calcium carbonate precipitate and parent solutions increase systematically as pH increases, from 0.9884 at pH 7.60 to 1.0072 at pH 8.60 for seawater and from 0.9826 at pH 7.60 to 1.0178 at pH 8.75 for saline water. An unusual boron isotopic fractionation factor of larger than 1 in synthetic calcium carbonate precipitated from seawater/saline water at higher pH is observed, which implies that a substantial amount of the isotopically heavier B(OH)3 species must be incorporated preferentially into synthetic inorganic carbonate. The results propose that the incorporation of B(OH)3 is attributed to the formation of Mg(OH)2 at higher pH of calcifying microenvironment during the synthetic calcium carbonate precipitation. The preliminary experiment of Mg(OH)2 precipitated from artificial seawater shows that heavier 11B is enriched in Mg(OH)2 precipitation, which suggests that isotopically heavier B(OH)3 species incorporated preferentially into Mg(OH)2 precipitation. This result cannot be applied to explain the boron isotopic fractionation of marine bio-carbonate because of the possibility that the unusual environment in this study appears in formation of marine bio-carbonate is infinitesimal. We, however, must pay more attention to this phenomenon observed in this study, which accidentally appears in especially natural environment.     

The study of 'DSP' binding systems by thermogravimetry and differential thermal analysis

The so-called DSP (Densified Systems containing homogenously arranged Particles) systems represent a high-performance class of inorganic binders. The hydration and hardening processes of some DSP systems, based on calcium silicates (C₃S and C₂S) or Portland cement/clinker with silica fume additions, were assessed, in this paper, using the thermogravimetry (TG) and differential thermal analysis (DTA). These data permit a qualitative and quantitative study of the formed hydrates as well as the estimation of hydration process kinetics. This revised version was published online in August 2006 with corrections to the Cover Date.     

Hydrate inclusion compounds

There are three general classes of hydrate inclusion compounds: the gas hydrates, the per-alkyl onium salt hydrates, and the alkylamine hydrates. The first are clathrates, the second are ionic inclusion compounds, the third are semi-clathrates. Crystallization occurs because the H₂O molecules, like SiO₂, can form three-dimensional four-connected nets. With water alone, these are the ices. In the inclusion hydrates, nets with larger voids are stabilized by including other guest molecules. Anions and hydrogen-bonding functional groups can replace water molecules in these nets, in which case the guest species are cations or hydrophobic moieties of organic molecules. The guest must satisfy two criteria. One is dimensional, to ensure a comfortable fit within the voids. The other is functional. The guest molecules cannot have either a single strong hydrogen-bonding group, such as an amide or a carboxylate, or a number of moderately strong hydrogen-bonding groups, as in a polyol or a carbohydrate.The common topological feature of these nets is the pentagonal dodecahedra: i.e., 5¹²-hedron. These are combined with 5¹²6²-hedra, 5¹²6³-hedra, 5¹²6⁴-hedra and combinations of these polyhedra, to from five known nets. Two of these are the well-known 12 and 17 Å cubic gas hydrate structures,Pm3n, Fd3m; one is tetragonal,P4 ₂/mnm, and two are hexagonal,P6 ₃/mmc andP6/mmm. The clathrate hydrates provide examples of the two cubic and the tetragonal structures. The alkyl onium salt hydrates have distorted versions of thePm3n cubic, the tetragonal, and one of the hexagonal structures. The alkylamine hydrate structures hitherto determined provide examples of distorted versions of the two hexagonal structures.There are also three hydrate inclusion structures, represented by single examples, which do not involve the 5¹²-hedra. These are 4(CH₃)₃CHNH₂·39H₂O which is a clathrate; HPF₆·6H₂O and (CH₃)₄NOH·5H₂O which are ionic-water inclusion hydrates. In the monoclinic 6(CH₃CH₂CH₂NH₂)·105H₂O and the orthorhombic 3(CH₂CH₂)₂NH·26H₂O, the water structure is more complex. The idealization of these nets in terms of the close-packing of semi-regular polyhedra becomes difficult and artificial. There is an approach towards the complexity of the water salt structures found in the crystals of proteins.     

Variable temperature 1H, 23Na,and 29Si MAS NMR studies on sodium silicate hydrates of composition Na2O · SiO2 · nH2O (n = 9, 6, 5): Local structure in crystals,melts, supercooled melts,and glasses

The local structure in crystals, melts, supercooled melts, and glasses of sodium silicate hydrates of composition Na₂O · SiO₂ · nH₂O (n = 9, 6, 5) is studied by variable temperature ¹H, ²³Na, and ²⁹Si MAS NMR spectroscopy. Detailed in situ investigations on the melting process of the crystalline materials reveal the importance of H₂O motion in the melting mechanism. Depending on the local coordination, crystallographically distinct Na sites show different behaviour during the melting process. Upon melting, the monomer silicate anions present in the crystalline hydrates undergo condensation reactions to oligomeric silicate anions. No recrystallization but glass formation occurs at low temperature if the melts were heated initially about 10 K above the melting point. In the glasses also oligomeric silicate anions are present with a preference for cyclotrimer species. In situ MAS NMR investigations and electric conductivity measurements of the melts, supercooled melts, and glasses suggest the distinction of three temperature ranges characterized by different local structure and dynamics of the sodium cations, water and silicate anions. These ranges comprise a glass and glass transition range A at low temperatures, an aggregation region B at intermediate temperatures, and a solution or electrolyte region C at high temperatures. In region B aggregation of sodium water complexes to hydrated polycation clusters is suggested, the dynamic behaviour of which is clearly different to that of the silicate anions, indicating that no long-lived contact ion pairs between sodium cations and silicate anions are formed.     

High Lithium Ionic Conductivity in the Lithium Halide Hydrates Li3‐n(OHn)Cl (0.83≤n≤2) and Li3‐n(OHn)Br (1≤n≤2) at Ambient Temperatures

Lithium ionic conductivity and phase transitions in a series of lithium halides hydrates and hydroxides with general formula Li_3‐n(OH_n)X (0.83≤n≤2; X=Cl,Br) were studied using impedance measurements and ¹H and ⁷Li NMR spectroscopy. All compounds studied in this work crystallize in the antiperovskite structure or are closely related to this structure type. With the exception of LiCl?H₂O, all compounds with integer lithium content exhibit good lithium ionic conductivity in their high temperature cubic phases above T=33 °C. Lithium doping of samples LiX?H₂O and Li₂(OH)X leads to a suppression of the phase transition into the noncubic phases and the good ionic conductivity is extended down to lower temperatures (T<0 °C). Thus, lithium doping of the lithium halide hydrates provides a promising tool for tailoring the ionic conductivity at ambient temperatures to its optimum value.     

Selective water sorbents for multiple applications, 1. CaCl2 confined in mesopores of silica gel: Sorption properties

This paper presents sorption properties of a selective water sorbent based on mesoporous KSKG silica gel as a host matrix and calcium chloride as a hygroscopic salt. Sorption isobars, isochores and isotherms at T=20–150°C and vapor partial pressures of 8–133 mbar clearly showed two types of water sorption: 1) the formation of solid crystal hydrates at low amounts N of sorbed water, and 2) vapor absorption mainly by the salt solution at higher N. Sorption properties of CaCl₂ crystal hydrates were found to change strongly due to their impregnation into mesoporous silica gel, whereas the solution confinement to the mesopores did not change its water sorption properties with respect to the bulk solution. Isosteric sorption heat was measured to depend on water sorption and to change from 62.5 kJ/mol for solid hydrates to 42.2–45.6 kJ/mol for solution.     

Specific surface of two hydrated cements differing in strength

Specific surface, S, of CSH-gel particles of disordered layered structure, was studied by water sorption/retention in two cement pastes differing in strength, i.e. C-33 (weaker) and C-43 (stronger), w/c=0.4. Hydration time in liquid phase was t _h=1 and 6 months, followed by hydration in water vapour either on increasing stepwise the relative humidity, RH=0.5→0.95→1.0 (WS) or on its lowering in an inverse order (WR). Specific surface was estimated from evaporable (sorbed) water content, EV (110°C), assuming a bi- and three-molecular sorbed water layer at RH=0.5 or 0.95, respectively (WS). On WR it was three- and three- to four-molecular (50 to 75%), respectively, causing a hysteresis of sorption isotherm. At RH=0.5 the S increased with cement strength from 146 m² g^-1 (C-33, 1 m) to 166 m² g^-1 (C-43, 1 m) and with hydration time to 163 (C-33, 6 m) and to 204 m² g^-1 (C-43, 6 m). At RH=1.0 (and 0.95), higher S-value were measured but these differences were smaller: S amounted to 190-200 m² g^-1 in C-33 (1 and 6 m) and 198-210 m² g-1 in C-43 (1 and 6 m). Thus no collapse occurred on air drying of paste C-43 (6 m). This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal behaviors of amorphous calcium carbonates prepared in aqueous and ethanol media

Two different samples of amorphous calcium carbonate (ACC) hydrates were prepared respectively by mixing aqueous solutions of CaCl₂ and Na₂CO₃-NaOH and by allowing the diffusion of (NH₄)₂CO₃ sublimate into ethanol solution of CaCl₂. Thermal behaviors of the synthetic ACCs were investigated comparatively by means of thermoanalytical techniques complimented by powder X-ray diffraction, FTIR spectrometry and microscopic observations. The anhydrous ACCs produced by the thermal dehydration of the respective samples were crystallized to calcite in different ways. The sample prepared in aqueous medium was crystallized at around 600 K in a single step. Crystallization in two separated steps at around 600 and 825 K was observed for the sample prepared in ethanol medium. Characteristics of the crystallization processes were discussed from thermodynamic and kinetic points of view.     

碳酸岩矿化菌诱导碳酸钙晶体形成机理研究

选用碳酸盐矿化菌(芽孢杆菌系), 分别研究了不同浓度细菌液、细菌体及其分泌物对碳酸钙晶体形成的影响. 研究表明, 细菌液浓度越高, 控制碳酸钙晶体形貌作用越显著; 细菌体为碳酸钙结晶提供异相成核点而对形貌并没有实质影响; 细菌分泌物可诱导出球形、纺锤形等多种形态亚稳态球霰石; 在微生物环境的长期作用下可形成有机-无机复合碳酸钙硬质膜. 通过对电导率测定结果和碳酸钙红外图谱分析得出, 生物有机质分子链的极性基团(COOH, C＝O等)与Ca^2＋产生静电、配位等一系列作用, 调控晶体的生长. 本研究对于微生物诱导碳酸钙的工程性应用, 如混凝土微裂缝修复、古建筑表面防护处理、微纳米碳酸钙颗粒制备等具有一定指导意义.     

Calcium Carbonate–Gold Nanocluster Hybrid Spheres: Synthesis and Versatile Application in Immunoassays

Fluorescent gold nanoclusters (AuNCs) were incorporated into porous calcium carbonate spheres through electrostatic interaction. The resulting CaCO₃/AuNCs hybrid material exhibited interesting properties, such as porous structure, excellent biocompatibility, good water solubility, and degradability. These properties make the CaCO₃/AuNCs hybrid material a promising template to assemble horseradish peroxidase/antibody conjugates (HRP‐Ab₂). By using CaCO₃/AuNCs/HRP‐Ab₂ bioconjugates as probes, a versatile immunosensor was developed for fluorescent and electrochemical detection of the cancer biomarker neuron‐specific enolase (NSE). The detection limits of the sensor were 2.0 and 0.1 pg mL^?1 for fluorescent and electrochemical detection, respectively. The immunosensor shows high sensitivity and offers an alternative strategy for the detection of other proteins and DNA.     

Gas Hydrate Frameworks of Allen's Polyhedra. 3. Chemical and Structural Implications of the Topological Properties of the Frameworks

The topology of frameworks of 5¹²(D), 5¹²6² (T) 5¹²6³ (P), and 5¹²6⁴ (H) polyhedra, belonging to the most widespread class of gas hydrate frameworks, is discussed. The frameworks of formula (D₃T₂P₂)_x (D₄H₂)_y (D₂T₆)_z, where x, y, and z are integers, have low strain energies of hydrogen bonds. For these frameworks, formulas relating their topological characteristics (the number of water molecules and hydrogen bonds in the unit cell, etc.) to x, y, and z are given. The tendencies of variation of hydration numbers in clathrate and semiclathrate hydrates are considered. Compounds with new structures of water frameworks are predicted, and approaches to selection of possible chemical systems with such compounds are discussed. The structural regularities found for the frameworks and the relationships between their topological characteristics may be used for analyzing Frank–Kasper structures of intermetallic compounds that are dualists of the polyhedral frameworks under study.     

The formation of clathrate-like hydrates of tetrabutylammonium halogenated carboxylates

The solid-liquid phase diagrams of binary mixtures of tetrabutylammonium halogenated carboxylates with water were examined in order to confirm the formation of clathrate-like hydrates. It was found that, among thirteen carboxylates examined, four carboxylates having CH₂FCOO^–, CHF₂COO^–, CF₃COO^–, and CH₂ClCOO^–, formed a hydrate with hydration numbers around 30 and seven carboxylates having CHCl₂COO^–, CCl₃COO^–, CH₂BrCOO^–, CHBr₂COO^–, CBr₃COO^–, CH₃CHClCOO^–, and CH₃CHBrCOO^– formed a hydrate with hydration numbers around 23. The latter hydrate has not been reported earlier. The melting points of these newly found hydrates were fairly high: they lie between 10 and 16°C. The effect of Cl and Br atoms attached to the carbon atom of the-position of a carboxylate anion both on the type of hydrate formed and on its stability was greatly different from that of a CH₃ group attached to the same position of the carboxylate anion.Dedicated to Dr D. W. Davidson in honor of his great contributions to the sciences of inclusion phenomena.