Effect of pressure on the crystal structure of ettringite

X-ray diffraction and infrared data have been collected from a sample of ettringite from ambient pressure to 6.4 GPa. The sample was found to reversibly transform to an amorphous phase at 3 GPa. The isothermal bulk modulus of ettringite was found to be 27(7) GPa and the incompressibilities of the lattice parameters were found to be 71(30) GPa along a and 108(36) GPa along c.     

Investigation by neutron diffraction of texture induced by the cooling process of zirconia refractories

New fused cast refractories with a high content of zirconia have been developed to face corrosion in glass furnaces. The controlled cooling process is responsible for thermal gradients. So, thermal mismatches appear between core and edge zones of blocks. Besides, the multiphasic nature of ZrO₂ based refractories is associated to thermal mismatches during cooling. Finally, the expansive transformation of ZrO₂ can lead to stress generation.This paper is an application of neutron diffraction to study texture generated during the cooling process of zirconia based materials. In fact, it is shown that ZrO₂ crystallographic variants have particular crystallographic texture regarding the main direction of the thermal gradient in the block. It was hypothesized that a selection of crystallographic variants could be done depending on the field stress. Tensile-compressive tests at high temperature have been done, to reproduce stress environment during the transformation of zirconia.     

A neutron diffraction study of ice and water within a hardened cement paste during freeze–thaw

A 1-month-old, saturated rod of hardened Portland cement paste with w/c=0.40 was formed with, and stored under, heavy water. This rod was studied undergoing two freeze–thaw cycles over the range 227–297 K, using neutron diffraction, at slow rates of heating and cooling. Neutron diffraction gives a direct and independent quantification of the amount of ice and liquid water in the pore system of hardened cement paste as a function of temperature. The amount of ice that formed was totally reproducible over two freeze–thaw cycles, implying negligible changes to the pore size distribution and geometry. An analysis of some of the factors that may contribute to the freeze–thaw hysteresis is given. There is significant broadening of the diffraction peaks of the ice, which corresponds to a small correlation length of crystalline order in the ice. Water was observed to be “irreversibly” expelled during the first freeze, above ca. 250 K.     

Effect of Fe doping on structure,magnetic and electrical properties La0.7Ca0.3Mn0.5Fe0.5O3 manganite

The crystal and magnetic structures of La_0.7Ca_0.3Mn_0.5Fe_0.5O₃ compound have been studied by neutron powder diffraction in the temperature range of 10–300 К. The magnetization and electrical resistivity measurements have been also performed in the temperature range of 5–300?K in magnetic fields up to 1?T. These experimental results indicate a formation of a complex magnetic state in which the long-range antiferromagnetic G-type phase coexists with the short-range ferromagnetic clusters. The electrical conductivity of La_0.7Ca_0.3Mn_0.5Fe_0.5O₃ demonstrates an anomalous temperature behavior suggesting a switching between different states. The origin of the unconventional magnetic state, the mechanisms of the electrical conductivity, and correlation between magnetic and transport properties in this manganite have been discussed.     

Time-resolved powder neutron diffraction study of the phase transformation sequence of kaolinite to mullite

Mullite formation from kaolinite was studied by means of high-temperature in situ powder neutron diffraction by heating from room temperature up to 1370 °C. Neutron diffractometry under this non-isothermal conditions is suitable for studying high-temperature reaction kinetics and to identify short-lived species which otherwise might escape detection. Data collected from dynamic techniques (neutron diffraction, DTA, TGA and constant-heating rate sintering) were consistent with data gathered in static mode (conventional X-ray diffraction and TEM). The full process occurs in successive stages: (a) kaolinite dehydroxylation yielding metakaolinite in the ∼400–650 °C temperature range, (b) nucleation of mullite in the temperature range ∼980–992 to ∼1121 °C (primary mullite) side by side with a crystalline cubic phase (Si-Al spinel) detected in the ∼983–1030 °C temperature interval; (c) growth of mullite crystals from ∼1136 °C, (d) high (or β) cristobalite crystallization at T > ∼1200 °C and (e) secondary mullite crystallization at T > ∼1300 °C. The calculated activation energy for the kaolinite dehydration was 115 kJ/mol; for the mullite nucleation was 278 kJ/mol and for the growth of mullite process was 87 kJ/mol; finally for cristobalite nucleation the calculated apparent activation energy was 481 kJ/mol.     

Hydrothermal transformation of the calcium aluminum oxide hydrates CaAl2O4·10H2O and Ca2Al2O5·8H2O to Ca3Al2(OH)12 investigated by in situ synchrotron X-ray powder diffraction

The hydrothermal transformation of calcium aluminate hydrates were investigated by in situ synchrotron X-ray powder diffraction in the temperature range 25 to 170 °C. This technique allowed the study of the detailed reaction mechanism and identification of intermediate phases. The material CaAl₂O₄·10H₂O converted to Ca₃Al₂(OH)₁₂ and amorphous aluminum hydroxide. Ca₂Al₂O₅·8H₂O transformed via the intermediate phase Ca₄Al₂O₇·13H₂O to Ca₃Al₂(OH)₁₂ and gibbsite, Al(OH)₃. The phase Ca₄Al₂O₇·19H₂O reacted via the same intermediate phase to Ca₃Al₂(OH)₁₂ and mainly amorphous aluminum hydroxide. The powder pattern of the intermediate phase is reported.     

Structural transformations of Muscovite at high temperature by X-ray and neutron diffraction

Structural transformations of Muscovite at temperature up to 1095 °C were determined using powder X-ray and neutron diffraction. Data were collected at room temperature from preliminary heated and quenched samples at 650 °C, 980 °C and 1095 °C. X-ray data were interpreted by either Rietveld method and neutron data, which complete the structural information by a better assignation of oxygen positions. With neutron data atom position was refined by fitting Pair Distribution Functions. It was found to be a progressive but continuous microstructural change, with the formation of an increasingly disorganized structure, but the layered organization of muscovite is maintained up to 1095 °C. Rietveld refinements from X-ray confirm the 6 to 5 coordination of Al atoms above 650 °C. It induces some structural changes as the orientation and mutual position of tetrahedrons in silicate layers. Pair Distribution Function refinements show the weakening of the long range structural organization, above 5 Å. At lower distance, a local order is maintained and the preferential alignments of both alumina unit pairs and silica tetrahedron were observed. This residual structural order of high-temperature muscovite is favorable to the achievement of textured ceramics.     

A comparative structural study of wet and dried ettringite

Two different techniques were used to compare structural characteristics of “wet” ettringite (stored in the synthesis mother liquid) and “dried” ettringite (dried to 35% relative humidity over saturated CaCl₂ solution). Lattice parameters and the water content in the channel region of the structure (site occupancy factor of the water molecule not bonded to cations) as well as microstructure parameters (size and strain) were determined from a Rietveld refinement on synchrotron powder diffraction data. Local environment of sulphate anions and of the hydrogen bonding network was characterized by Raman spectroscopy. Both techniques led to the same conclusion: the “wet” ettringite sample immersed in the mother solution from the synthesis presents similar structural features as ettringite dried to 35% relative humidity. An increase of the a lattice parameter combined with a decrease of the c lattice parameter occurs on drying. The amount of structural water, the point symmetry of sulphate and the hydrogen bond network are unchanged when passing from the wet to the dried ettringite powder. Ettringite does not form a high-hydrate polymorph in equilibrium with alkaline solution, in contrast to the AFm phases that lose water molecules on drying. According to these results we conclude that ettringite precipitated in aqueous solution at the early hydration stages is of the same chemical composition as ettringite present in the hardening concrete.     

Ettringite formation and microstructure of rapid hardening cement

This paper reports the formation and microstructure development of ettringite during hydration of two rapid hardening cements under various handling times. The rapid hardening component of one of these cements is crystalline calcium fluoroaluminate while that of the other is an amorphous calcium aluminate. During hydration, the crystalline fluoroaluminate component forms ettringite from the very beginning. The amount of ettringite increases with time producing needle-shaped crystal of various sizes. The amorphous calcium aluminate component, on the other hand, exhibits an initial induction period after which there is a rapid formation of needle-shaped ettringite crystals of nearly uniform size.     

Investigation of the residual stress in UO2-Mo composites via a neutron diffraction method

UO₂-Mo composites with a core-shell structure have been considered candidates for the thermal conductivity (TC)-enhanced UO₂ pellets and have demonstrated commercial potential for use in novel high-level safety reactors. Nevertheless, UO₂-Mo composites tend to form micro-cracks that are caused by the presence of residual stress (RS) during manufacturing. In this work, neutron diffraction measurements were employed to analyse the RS in UO₂-Mo core-shell structured composites fabricated by spark plasma sintering (SPS) for the first time. It was found that in the UO₂-Mo composites, the RS state present in the UO₂ matrix was tensile in nature. The RS in the UO₂ matrix increased with increaseing Mo content. There was a maximum value of 148 ± 15 MPa in the UO₂-10 vol% Mo composite. The micro-cracks produced in the high-Mo content composites were explained by the results of the neutron diffraction measurements. These results could provide significant guidance for the manufacturing and improvement of the operational performance of UO₂-Mo composites as next-generation fuels.     

In-situ monitoring the realkalisation process by neutron diffraction: Electroosmotic flux and portlandite formation

Even though the electroosmotic flux through hardened cementitious materials during laboratory realkalisation trials had been previously noticed, it has never been in-situ monitored, analysing at the same time the establishment of the electroosmotic flux and the microstructure changes in the surroundings of the rebar. In this paper, two series of cement pastes, cast with CEM I and CEM I substituted in a 35% by fly ash, previously carbonated at 100% CO₂, were submitted to realkalisation treatments followed on line by simultaneous acquisition of neutron diffraction data. As a result, it has been possible to confirm the electroosmosis as the driving force of carbonates towards the rebar and to determine the range of pH in the anolyte in which most of the relevant electroosmotic phenomena takes place. On the other hand, the behaviour of the main crystalline phases involved in the process has been monitored during the treatment, with the precipitation of portlandite as main result.     

X射线粉末衍射法鉴定无标签化学试剂

运用X射线粉末衍射法，再结合红外光谱、形貌观察等方法来对失落标签的结晶化学试剂进行鉴定，从而为其使用或合理的回收打下基础。     

Accelerated carbonation of cement pastes in situ monitored by neutron diffraction

In-situ monitoring of the changes that take place in the phase composition of cement pastes during accelerated carbonation (100% CO₂) for different binders, has been carried out, by taking Neutron Diffraction patterns in parallel with the carbonation experiments. The variation of the intensity of chosen reflections for each phase along the experiment has been used to monitor concentration changes and has supplied data, in real time, for fractional conversion of different phases (Portlandite, Ettringite and CSH gel) of the hydrated cement pastes. Fitting of these results has allowed to make a qualitative approach to the kinetics of the carbonation of the different phases and extracting conclusions on the microstructural changes that takes place during the carbonation of cement pastes.     

The influence of calcium lignosulphonate-sodium bicarbonate on the status of ettringite crystallization in fly ash cement paste

Calcium lignosulphonate (CL)-sodium bicarbonate (SB) (a total of 0.7% by weight of cement and CL to SB ratio of 1:1.8) will cause the fluidity of fly ash cement paste to decrease rapidly. It is the variation of the status of ettringite crystallization that causes this phenomenon. Experimental results show that CL-SB affects the liquid-phase composition of fly ash cement paste remarkably. As a result, ettringite crystallizes out in the shape of needles from the solution. These needle-like crystal particles are distributed in the solution at a certain distance from the surface of clinker particles. At the initial hydration stage, the crystallization of ettringite is stronger in fly ash cement with calcined gypsum than in fly ash cement with gypsum.     

Petrographical analysis of calcium aluminate cement mortars: Scanning electron microscopy and transmitted light microscopy

The samples studied for this paper were obtained from experimentally induced carbonation and alkaline hydrolysis of calcium aluminate cement (CAC) mortars. The mineralogical composition of phases present was studied from X-ray diffraction (XRD) spectra. Scanning electron microscopy (SEM) and transmitted light microscopy (TLM) were used to obtain some morphological (size and shape) and fabric data of mineralogical phases to improve the interpretation of damage processes. SEM is a useful tool to examine the evolution of mineral phases in cavities and discontinuity zones. The interpretation of the degree of carbonation and the distribution of carbonated phases in the samples, the presence of C₃AH₆ and CAH₁₀, as well as possible alterations of aggregates are well differentiated and defined using TLM method. The main objective of the present paper is to validate the use of both microscopic techniques (TLM and SEM) for the study of phase evolution in the CAC mortar during curing and degenerative processes.     

The location of pyridine in sodium–silver–Y zeolite by powder synchrotron X-ray diffraction

The powder synchrotron X-ray diffraction pattern of a mixed sodium–silver–Y zeolite, Ag_56−xNa_xSi₁₃₆Al₅₆O₃₈₄ x≈19, saturated with pyridine, has been analysed by the Rietveld method to reveal positions for the adsorbed molecules. Cations are distributed over three sites, SII, constrained to 100% occupancy, with 17.2(1) and 14.8(1) Ag(1) and Na(1) ions per unit cell, respectively, SI′ with 18.3(1) Ag(2) ions per cell, and SI with 1.8(1) Ag(3) ions per cell. The refinement suggests that approximately 7.5 pyridine molecules are adsorbed per supercage, located in two sites within the cavities of the zeolite. Pyridine(1) is in the 12-ring window connecting supercages. Three molecules project through each window and approach the SII cations in a supercage, with an average Ag(1)–N distance of 3.17(2) Å. An SII cation can be linked to three pyridine(1) molecules from three separate windows. These sites are full with 5.98(2) molecules per supercage. Pyridine(2) is found in the supercage, oriented with its π electron density towards the SII cations, with its centre at 2.87(2) Å from Ag(1). The average occupancy was fixed at 1.5 molecules per supercage, corresponding to 20% of the pyridine content. A local ordering scheme can be postulated, whereby alternate supercages are filled by pyridine(1) and pyridine(2) molecules, efficiently filling the channels of the zeolite.     

Quantitative Rietveld analysis of CAC clinker phases using synchrotron radiation

The quantitative Rietveld analyses of twenty samples of CAC from four different manufacturers over the world, one synthetic mixture and a NIST standard were performed using synchrotron radiation. As compared with conventional XRD, synchrotron powder diffraction permitted to find new minor phases, improve the characterization of solid solutions of iron rich CAC phases and reduce preferential orientation and microabsorption effects. Diffraction data were complemented with XRF and TG/DT analyses. Synchrotron results were used as a reference test to improve the performance of conventional powder diffraction, by an accurate selection of refinable profile and structural parameters, and permitted to extract several recommendations for conventional quantitative Rietveld procedures. It is shown that with these recommendations in mind, conventional XRD based Rietveld analyses are comparable to those obtained from synchrotron data. In summary, quantitative XRD Rietveld analysis is confirmed as an excellent tool for the CAC cement industry.     

Atomic structure of chlorine containing calcium silicate glasses by neutron diffraction and 29Si solid-state NMR

Bioactive glasses are of great importance for medical and dental applications. In order to understand, model, and predict the behavior of these materials, and ultimately improve their design, it is important to understand the structure of these glasses. Ion dissolution is known to be the crucial first step in bioactivity and is strongly dependent upon the atomic-scale structure and network connectivity. While significant progress has been made understanding the structure of oxide-based glasses, relatively little is known about the structure of bioactive glasses containing halides. Recently, a series of novel chloride-based bioactive glasses has been developed. Chlorapatite converts to hydroxyapatite in water and these glasses are therefore of interest for novel toothpastes. This study reports the first detailed structural investigation of these bioactive chloride glasses using neutron diffraction and solid-state NMR. Chlorine was found to bond to calcium within the glass, and no evidence of Si-Cl bonding was detected. Furthermore, the absence of a chemical shift in the ²⁹Si NMR upon the addition of CaCl₂ helped confirm the absence of detectable amounts of Si-Cl bonding. Given that chlorine does not disrupt the Si-O-Si network, widely used network connectivity models are therefore still valid in oxychloride glasses.     

The impact of Al2O3 amount on the synthesis of CASH samples and their influence on the early stage hydration of calcium aluminate cement

In this work the impact of Al₂O₃ amount on the synthesis (200?°C; 4–8?h) of calcium aluminium silicate hydrates (CSAH) samples and their influence on the early stage hydration of calcium aluminate cement (CAC) was examined. It was found that the amount of Al₂O₃ plays an important role in the formation of calcium aluminate hydrates (CAH) because in the mixtures with 2.7% Al₂O₃ only calcium silicate hydrates (CSH) intercalated with Al³⁺ ions were formed. While in the mixtures with a higher amount of Al₂O₃ (5.3–15.4%), calcium aluminate hydrate – C₃AH₆, is formed under all experimental conditions. It is worth noting that the largest quantity of mentioned compound was obtained after 4?h of hydrothermal treatment, in the mixtures with 15.4% of Al₂O₃. It was proved that synthesized C₃AH₆ remain stable up to 300?°C and at higher temperature (945?°C) recrystallized to mayenite (Ca₁₂Al₁₄O₃₃), which reacted with the rest part of CaO and amorphous structure compound, resulting in the formation of gehlenite (Ca₂Al₂SiO₇). Moreover, the synthesized C₃AH₆ addition induced the early stage of CAC hydration. Besides, in the samples with an addition, the induction period was effectively shortened: in a case of pure CAC (G70) paste, hydration takes about 6–6.5?h, while with addition – only 2–2.5?h. The synthesized and calcinated compounds was characterized by using XRD and STA analysis.     

Visualization of the shear region in a cohesive powder by scanning with a polarized neutron beam

The flow of cohesive powder occurs by the formation of shear planes or zones. How these form and how particles microscopically behave in a shear zone is fundamental for understanding powder flow. In this work Neutron Depolarization has been used to study in-line particles in a powder sample. The Neutron Depolarization technique gives a unique insight in the particle rotations and width of the shear zone. It has been shown that rotation of particles during a normal consolidation becomes less when the sample is more compacted. Shear displacement experiments showed that particles rotate in a preferred direction. The width of the region in which the preferred rotation takes place is found to be at least 1000 to 2000 particle diameters.