To understand and predict the effects of a thermal pulse induced by a radioactive waste repository on clinoptilolite-bearing rocks, the lattice parameters of 6 natural and 3 cation-exchanged (Ca, K, Na) clinoptilolites were studied as a function of temperature. The samples were examined at room temperature, under vacuum, and at 50°C increments to 300°C using a high-temperature X-ray powder diffractometer. The unit cell of all samples decreased in volume between 20° and 300°C Na-saturated clinoptilolite underwent the greatest volume decrease (8.4%) and K-saturated clinoptilolite the smallest (1.6%), of the clinoptilolites studied. The volume decrease for the Ca-saturated clinoptilolite was 3.6%. The highest percentage decrease for each sample was along the b axis, generally 80–90% of the total volume decrease. The change in the a axis was the smallest and was usually <5%, although 26.5% of the contraction of the Na-exchanged clinoptilolite was along a. The bulk of the volume contraction of many samples occurred on evacuation at room temperature, demonstrating that the observed changes were due to water loss and not to temperature-induced structural changes. Low-angle scattering was significantly reduced upon evacuation for every sample, and the 110 reflection of clinoptilolite at 7.45°2θ became obvious, whereas it was not in the untreated samples.

These data show that the effects of heating on the unit-cell volume of clinoptilolite depend strongly on the exchangeable cation content. Significant reductions in the unit-cell volumes of natural, mixed Na-K-Ca clinoptilolites could take place in rocks in a repository environment, particularly if the clinoptilolites occurred in unsaturated, dehydrated rock. The unit-cell volumes of clinoptilolites in partially saturated rocks at temperatures below 100°C, however, should not decrease significantly.

The high-temperature behaviour of a feldspar-group mineral, filatovite (with the simplified formula: K(Al,Zn)2(As,Si)2O8), in which the Al:As:Si ratio is close to 2:1:1), was studied by in situ high-temperature single-crystal X-ray diffraction and in situ high-temperature (hot stage) Raman spectroscopy up to 600°C. In the temperature range studied (25–600°С) filatovite does not undergo any phase transition, whereas at 800°C it decomposes to X-ray amorphous phase(s). The evolution of 12 main Raman bands was traced during heating, which indicates a gradual change in the crystal structure. The thermal expansion coefficients of filatovite demonstrate a sharply anisotropic character of thermal expansion: the maximal expansion is close to the a axis (α11 = 17.7(1) × 10–6 °C–1), whereas along the b and c axes the thermal expansion coefficients are close to zero. Such behaviour is typical for minerals with a similar crystal structure topology; it indicates the dominant role of structure geometry in the thermal behaviour of the mineral.

The lattice parameters and the crystal and magnetic structures of Fe2SiO4 have been determined from 10 K to 1453 K by high-resolution time-of-flight neutron powder diffraction. Fe2SiO4 undergoes two antiferromagnetic phase transformations on cooling from room temperature: the first, at 65.4 K, is to a collinear antiferromagnet with moments on two symmetry-independent Fe ions; the second transition, at ~23 K, is to a structure in which the moments on one of the sets of Fe ions (those on the ‘M1 site’) become canted. The magnetic unit cell is identical to the crystallographic (chemical) unit cell and the space group remains Pbnm throughout. The magnetic structures have been refined and the results found to be in good agreement with previous studies; however, we have determined the spontaneous magnetostrictive strains, which have not been reported previously. In the paramagnetic phase of Fe2SiO4, at temperatures of 70 K and above, we find that the temperature dependence of the linear thermal expansion coefficient of the b axis takes an unusual form. In contrast to the behaviour of the expansion coefficients of the unit-cell volume and of the a and c axes, which show the expected reduction in magnitude below ~300 K, that of the b axis remains almost constant between ~70 K and 1000 K.

Kainite, KMg(SO4)Cl⋅2.75H2O, is one of the most common hydrated sulfate minerals, and it plays an important role as a source of potassium. However, its properties and structure have, to date, been insufficiently studied. In our present work, kainite was investigated using multiple techniques, including single-crystal and powder X-ray diffraction, thermogravimetry, differential scanning calorimetry (DSC), and infrared spectroscopy (IR). The mineral is monoclinic, C2/m, a = 19.6742(2), b = 16.18240(10), c = 9.49140(10) Å, β = 94.8840(10)°, V = 3010.86(5) Å3 and Z = 16. The structure was refined to R1 = 0.0230 for 3080 unique observed reflections with |Fo| ≥ 4σF. The complex hydrogen bonding system for kainite is described for the first time. The structure of kainite contains seven symmetrically independent sites occupied by water molecules, six of which are strongly bonded to Mg2+ cations while the seventh resides in the framework cavities. The acceptors of the hydrogen bonds are either chloride anions, neighbouring water molecules or oxygens atoms of sulfate groups. A bifurcated hydrogen bond was described for one of the water molecules. Based on the analysis of the crystal structure, we have confirmed and propose the correct formula for kainite as KMg(SO4)Cl⋅2.75H2O. The thermal studies of kainite in the temperature range of –150°C to +600°C indicate its stability to 190°C. The decomposition products are K2Mg2(SO4)3, KCl and K2SO4. The thermal expansion was calculated, which for kainite has a character typical for monoclinic crystals and similar to the compressibility tensor described earlier.

Thermal behaviour of fibrous tremolite from Maryland, USA has been investigated in situ up to breakdown temperature. Tremolite can be found both as primary constituent and as contaminant in Asbestos Containing Materials (ACMs). The products of breakdown are subcalcic diopside and calcium-rich clinoenstatite in a 2:1 ratio, traces of hematite plus minor silica-rich amorphous material. Thermal expansion follows a regular trend up to 723 K before the onset of Fe2+ oxidation/OH– deprotonation which is completed at 1023 K. At 923 K the Fe3+ migration starts towards M(1) and the corresponding counter-migration of Mg to M(2) and M(3). At T close to structure breakdown, M(2) shows a significant site-scattering reduction possibly consistent with the occurrence of minor vacancies. In fully oxidised tremolite, Fe3+ is allocated prevalently at M(1) and subordinately at M(3). As it is well-known that M(1), along with M(2), is the most exposed octahedral site at the surface of amphiboles, most of the Fe3+ is available for participating in the Fenton-like reactivity of oxidised tremolite, potentially making it dangerous for human health. This point should be properly taken into account in the evaluation of the safety of thermally decomposed tremolite-containing ACMs, in particular in the case of accidentally incomplete treatments.

Ag3O was synthesized by jet-milling magnetron-sputtered Ag–Ag2O thin films. Heating the jet-milled powders in air and N2 from 40 to 148 °C at ambient pressure produced Ag3O-rich powders. The phase composition and unit-cell parameters of the jet-milled powders were measured as a function of temperature with in situ X-ray powder diffraction experiments from −186 to 293 °C. Ag3O was also produced by ball milling and sonicating jet-milled films at ambient conditions. The phase composition, unit-cell parameters, and thermal-reaction rates indicate nonstoichiometric Ag3O was produced from the reaction of metastable, nonstoichiometric Ag2O (cuprite structure) and ccp Ag. The thermal expansion of Ag3O is anisotropic; below 25 °C, the a-axis expansion is about twice the c-axis expansion resulting in a negative slope of c/a(T). The reversal of the sign of c/a(T) near 25 °C is dramatic. The thermal reaction is arrested when the temperature is rapidly increased from ambient to 130 °C. Ag3O is metastable and decreases its unit-cell volume during kinetic decomposition to Ag when heated above ambient temperature in air and nitrogen. The relative volume expansion of Ag3O is about 80% less than Ag at room temperature and below. The suite of nonstoichiometric Ag3O produced by heating displays a linear relation between c/a and unit-cell volume at room temperature. The c/a and unit-cell volume of a hydrothermally grown Ag3O single crystal reported in a published structure determination was the Ag-rich, low-volume end member of the linear series. The c/a and unit-cell volume are sensitive indicators of the oxygen content and state of disorder.

The thermal expansion coefficient (TEC) of nano-B4C having 50 nm mean particle size was measured as a function of applied direct current (DC) electric field strength varying from 0 to 12.7 V/mm and over a temperature range from 298 K up to 1273 K. The TEC exhibits a linear variation with temperature despite being measured over a range that is well below 50% of B4C’s normal melting temperature. The zeroth- and first-order TEC coefficients under zero-field condition are 4.8220 ± 0.009 × 10−6 K−1 and 1.462 ± 0.004 × 10−9 K−1, respectively. Both TECs exhibit applied DC electric field dependence. The higher the applied field strength, the steeper the linear thermal expansion response in nano-B4C, which suggests that the applied field affects the curvature of the interatomic potentials at the equilibrium bond length at a given temperature. No anisotropic thermal expansion with and without applied electric field was observed, although nano-B4C has a rhombohedral unit cell symmetry. The rhombohedral unit cell angle was determined as δR= 65.7046° (0.0007), and it remains unaffected by a change in temperature and applied electric field strength, which we attribute to B4C nanoparticle size and its carbon saturation.

To study thermal desulfurization of pyrite (FeS2), we conducted in situ neutron diffraction experiments in the temperature range 298–1073 K. On heating, pyrite remained stable up to 773 K, at which it started to decompose into pyrrhotite (Fe1−xS) and S2 gas. Rietveld analysis of the neutron data from 298 to 773 K allowed determination of the thermal expansion coefficient of pyrite (space group Pa$\bar 3$) to be αV = 3.7456 × 10−5 K−1, which largely results from the expansion of the Fe–S bond. With further increase in temperature to 1073 K, all the pyrite transformed to pyrrhotite (Fe1−xS) at 873 K. Unit-cell parameters of Fe1−xS (space group P63/mmc) increase on heating and decrease on cooling. However, the rates in cell expansion are larger than those in contraction. This hysteresis behavior can be attributed to continuous desulfurization of pyrrhotite (i.e., x in Fe1−xS decreases) with increasing temperature until the stoichiometric troilite (FeS) was formed at 1073 K. On cooling, troilite underwent a magnetic transition to an orthorhombic structure (space group Pnma) between 473 and 573 K. In addition, using differential thermal analysis (DTA) and thermogravimetric analysis (TGA) implemented with a differential scanning calorimeter, we performed kinetic measurements of pyrite decomposition. Detailed peak profile and Arrhenius (k = A exp(−Ea/RT)) analyses yielded an activation energy Ea of 302.3 ± 28.6 kJ/mol (based on DTA data) or 302.5 ± 26.4 kJ/mol (based on TGA data) and a ln(A) of 35.3 ± 0.1.

The high-temperature (HT) behaviour of a sample of natural alunite was investigated by means of in situ HT single-crystal X-ray diffraction from room temperature up to the dehydroxylation temperature and consequent collapse of the crystal structure. In the temperature range 25–500°C, alunite expands anisotropically, with most of the contribution to volume dilatation being produced by expansion in the c direction. The thermal expansion coefficients determined over the temperature range investigated are: αa = 0.61(2) × 10–5 K–1 (R2 = 0.988), αc = 4.20(7) × 10–5 K–1 (R2 = 0.996), αc/αa = 6.89, αV = 5.45(7) × 10–5 K–1 (R2 = 0.998). At ∼275–300°C, a minor discontinuity in the variation of unit-cell parameters with temperature is observed and interpreted on the basis of loss of H3O+ that partially substitutes for K+ at the monovalent A site in the alunite structure. Increasing temperature causes the Al(O,OH)6 sheets, which remain almost unaltered along the basal plane, to move further apart, and this results in an expansion of the coordination polyhedron around the intercalated potassium cation. Sulfate tetrahedra act as nearly rigid units, they contract a little in the lower temperature range to accommodate the elongation of the Al octahedra.

The atomic structure of chkalovite, Na2BeSi2O6, has been determined and refined by Simonov et al. (1976). It is orthorhombic, space group Fdd2, with cell parameters: a = 21.129 (5), b = 6.881 (2), and c = 21.188 (5)/Å. The structure is very similar to that of alpha-cristobalite (Dollase, 1965), comprising a framework of ordered BeO4 and SiO4 tetrahedra with the sodium atoms occupying sites within the cavities of the beryllosilicate framework. Taylor (1972) developed a tilting model for the cristobalite structure assuming regular tetrahedra. In addition to the single tilt system deduced for cristobalite (Taylor, 1972, 1984a) chkalovite has secondary tilt systems involving a slight adjustment of the structure by a small cooperative tilt or twist of some tetrahedra about one or more of their three-fold axes (see fig. 1 of Simonov et al., 1976).

The unit-cell parameters of andalusite and sillimanite have been measured by high-T powder X-ray diffraction up to 1000°C at ambient pressure. Within the temperature range investigated, all the unit-cell parameters varied smoothly, indicating no phase transition. The volume-temperature data were fitted with a polynomial expression for the thermal expansion coefficient (αT = a0 + a1T + a2T-2). yielding a0 = 2.55(2) × 10–5K–1, al = 0 and a2 = 0 for andalusite, and a0 = 1.40(4) × 10–5K–1a1 = 7.1(8) × 10–9K–2 and a2 = 0 for sillimanite. Using the new thermal expansion data determined in the present study and compressional data from the literature, the P-T phase relations of the kyanite-andalusite-sillimanite system were calculated thermodynamically, with the invariant point located at ∼523°C and 3.93 kbar.

The thermal expansion coefficients for natural troilite, FeS, Ni-rich pyrrhotite, Fe0.84Ni0.11S, and Ni-poor pyrrhotite, Fe0.87Ni0.02S, were measured during cooling by in situ neutron powder diffraction over the temperature range 873–373 K. Between 873 and 573 K, the mean thermal expansion coefficients for the three compositions are 7.4(3)×10−5 {FeS}, 8.0(4)×10−5 {Fe0.84Ni0.11S} and 8.5(4)×10−5 K−1 {Fe0.87Ni0.02S}. Below 573 down to 373 K, the first two increase considerably to 14.1(7)×10−5 {FeS} and 9.3(5)×10−5 {Fe0.84Ni0.11S} while the latter sample shows no significant variation, 8.4(5)×10−5 K−1. Below 573 K, the thermal expansion is highly anisotropic, with Δa/100 K−1 ranging from 0.89(9)% {FeS} to 0.48(12)% {Fe0.87Ni0.02S} while Δc/100 K−1 ranges from −0.39(11)% {FeS} to −0.13(2)% {Fe0.87Ni0.02S}.

Upon cooling through 573 K, troilite and pyrrhotite undergo a transition where the FeS6 octahedra distort and in the case of pyrrhotite, cation-vacancy clustering occurs. The thermal expansion coefficients are bigger for low cation-vacancy concentrations and decrease as the pyrrhotites become less stoichiometric. This indicates that the thermal expansion in these minerals is damped by vacancy ordering or clustering. The thermal expansion coefficients for troilite and pyrrhotite are amongst the largest reported for sulphide minerals and their role in the formation of ore textures is discussed briefly.

The structural modifications with temperature of libethenite, Cu2(PO4)(OH), were determined by single-crystal X-ray diffraction up to dehydration and consequent decomposition of the crystal under investigation. In the temperature range 25–475°C, libethenite shows positive and linear expansion. The axial thermal expansion coefficients, determined over this temperature range, are: αa = 6.6(1)·10–6 K–1, αb = 1.21(2)·10–5 K–1, αc = 9.0(2)·10–6 K–1, αv = 2.78(3)·10–5 K–1. Axial expansion is then anisotropic with αa:αb:αc = 1:1.83:1.33.

Structure refinements of X-ray diffraction data collected at different temperatures allowed us to characterize the mechanisms by which the libethenite structure accommodates variations in temperature. Increasing temperature induces expansion of both Cu polyhedra and no significant variation of the PO4 tetrahedron, which acts as a rigid unit. Cu(1) octahedra expand mostly as a consequence of the increase of the axial bonds, and become more distorted. Starting from T = 500°C, precursor signs of incoming dehydration are visible: two adjacent OH groups approach each other and cause dramatic changes in the whole structure. Concomitantly, the libethenite crystal begins to deteriorate and, at T = 600°C, broad and weak diffraction effects of polycrystalline material are observed.

In situ high temperature single crystal X-ray diffraction (XRD) experiments have been performed on a chemically quasi-ideal omphacite sample up to 1000°C. The lattice parameters were studied as a function of temperature, and their thermal expansion coefficients determined. The b and c cell edges show discontinuities as a function of temperature which are interpreted here in terms of intracrystalline cation diffusion processes. Structure refinements have been carried out using data collected at room temperature, at 800°C and at ambient conditions after cooling. The structural behaviour as a function of temperature of chemically quasi-ideal omphacites is compared with those of jadeite and diopside.

Thermal expansion coefficients were measured for a cancrinite from Bancroft, Ontario, Canada. Measurements of cell parameters and unit-cell volumes were obtained at room temperature and at heating intervals of 50°C over the temperature range from 50 to 1400°C. The unit-cell parameters for cancrinite increase non-linearly with temperature up to 1200°C and shortly thereafter, the mineral melted. The c parameter increases more rapidly than the a parameter, and the c/a ratio increases linearly with temperature. A plausible thermal expansion mechanism for cancrinite, which is based on the framework expansion that occurs as a function of cavity content, is presented. In the thermal expansion of cancrinite, the short Na-H2O in the H2O-Na—H2O chain expands to form equal distances to the two H2O molecules in the chain. This causes the Na atoms to move towards the plane of the six-membered rings and forces the tetrahedra to rotate and the rings become more planar. The Na atoms then form bonds to all six (O1 and O2) oxygen atoms in a ring; the Na-O1 bonds become shorter and the Na-O2 bonds become longer. These effects cause an increase in both a and c, and thus an increase in the c/a ratio. A similar thermal expansion mechanism operates in the sodalite-group minerals where the six-membered rings and Na-Cl bond are involved.

The structure of hibonite from Myanmar (space group P63/mmc, Z = 2, at room temperature a = 5.5909(1), c = 21.9893(4) Å), with simplified formula CaAl12O19 and composition (Ca0.99Na0.01)Σ1.00 was investigated between temperatures of 100 K and 923 K by single-crystal X-ray diffraction methods. Structure refinements have been performed at 100, 296, 473 and 923 K. In hibonite from Myanmar, Ti substitutes for Al mainly at the octahedral Al4 site and, to a lesser degree, at the trigonal bipyramidal site, Al2. The Al4 octahedra build face-sharing dimers. If Ti4+ substitutes at Al4, adjacent cations repulse each other for electrostatic reasons, leading to off-centre cation displacement associated with significant bond-length distortion compared to synthetic (Ti-free) CaAl12O19. Most Mg and smaller proportions of Zn and Si are assigned to the tetrahedral Al3 site. 12-coordinated Ca in hibonite replaces oxygen in a closest-packed layer. However, Ca is actually too small for this site and engages in a ‘rattling-type’ motion with increasing temperature. For this reason, Ca does not significantly increase thermal expansion coefficients of hibonite. The expansion of natural Ti,Mg-rich hibonite between 296 and 923 K along the x and the z axes is αa = 7.64×10–6 K–1 and αc = 11.19×10–6 K–1, respectively, and is thus very similar to isotypic, synthetic CaAl12O19 and LaMgAl11O19 (LMA).

We have investigated the thermal expansion of nepheline-kalsilite crystalline solutions having 12.5% excess silicon relative to the stoichiometric composition. It is proposed that differences in the thermal expansion among various members of the series, and also between this series and a previously studied low-Si series, can be explained by three factors: (1) shrinkage of the tetrahedral rings caused by the substitution of Na for K, especially in the case of kalsilite, allows for greater expansion from the increased vibrational amplitude of Na ions with increasing temperature. (2) The occupancy of alkali sites by ions rather than vacancies draws tetrahedral rings inward via electrical attraction to these ions, providing the potential for greater expansion with ionic vibration as temperature increases. (3) Structural differences between nepheline and kalsilite, in particular the existence of two alkali sites in nepheline, account for the increased thermal expansion of K-enriched nepheline relative to Na-nepheline, as the occupation of the larger alkali position by K+ results in greater thermal expansion than is the case with Na+ occupancy of the same sites.