Cody R. Morelock

Negative thermal expansion and compressibility of Sc1–xYxF3 (x≤0.25)

Scandium fluoride displays isotropic negative thermal expansion (NTE) from at least 10 to 1100 K and retains a cubic ReO3-type structure over this range; the NTE is most pronounced at low temperatures. Control of thermal expansion was explored by forming Sc1–xYxF3 (x≤0.25), which were characterized with synchrotron powder diffraction at ambient pressure from 100 to 800 K. The behavior of the solid solutions under pressure (≤0.276 GPa) was also examined while heating from 298 to 523 K. Insertion of the relatively large Y3+ ion into ScF3 results in a cubic-to-rhombohedral phase transition upon cooling from ambient temperature to 100 K, even at low substitution levels (5%). The coefficient of thermal expansion (CTE) of the solid solutions in the rhombohedral phase is strongly dependent on both composition and temperature; however, above 400 K, where all samples are cubic, the CTE appears to be largely independent of composition. The isothermal bulk modulus and CTE of ScF3, but not those of the solid solution...

Dramatic softening of the negative thermal expansion material HfW2O8 upon heating through its WO4 orientational order-disorder phase transition

HfW2O8 undergoes a dramatic softening where the average bulk modulus (P = 52–414 MPa) drops from 69 GPa at 298 K to 48 GPa at 430 K as the temperature of the WO4 orientation order-disorder transition is approached. This is accompanied by increasingly negative thermal expansivity (−10 ppm·K−1 to −15 ppm·K−1) and reversible WO4 orientational disordering upon compression in α-HfW2O8. Additionally, α-HfW2O8 becomes elastically softer upon compression at constant temperature. The α→β phase transition temperature decreases by ∼30 K between 52 and 414 MPa. Above this phase transition, no further temperature-dependent softening or pressure-dependent changes in the coefficient of thermal expansion occurred.

Reducing the background from pressure vessels using a BRIM

A collimator and beam-stop assembly that can be inserted inside a temperature-controlled pressure vessel, to reduce dramatically the parasitic Bragg scattering from the vessel, has been designed and evaluated. High-energy X-ray powder diffraction data, suitable for the Rietveld refinement of simple crystal structures, were collected using this background-reducing internal mask (BRIM). ZrW2O8 was examined at up to 540 K and 124 MPa, using quite large pressure and temperature steps. No pressure dependence of the order–disorder transition temperature of this material was apparent. An orthorhombic to monoclinic phase transition (onset ∼83 MPa) was observed for Al2W3O12. Upon going through the transition, the bulk modulus of the material decreased from 41.8 to 20.8 GPa. Bulk moduli estimated for CaF2 and α-Al2O3, from data collected at up to 280 MPa, were in good agreement with prior literature.

A cautionary tale on the use of GE-7031 varnish: low-temperature thermal expansion studies of ScF3

GE-7031 varnish, a commonly used low-temperature adhesive and electrical insulator owing to its high thermal conductivity and mechanical strength at low temperatures, was used as a sample matrix for low-temperature powder X-ray diffraction measurements of the negative thermal expansion (NTE) material ScF3. When ScF3 powder was mixed with GE-7031 varnish, an unexpected cubic to rhombohedral phase transition in the ScF3 sample was observed at ∼50 K, and it exhibited smaller low-temperature unit-cell volumes than samples without the varnish matrix. Experimental observations and quantitative estimates suggest that these anomalies are the result of stress induced by a thermal expansion mismatch between the varnish matrix (large positive coefficient of thermal expansion, CTE) and ScF3 (quite large negative CTE). The use of GE-7031 varnish as a sample matrix for low-temperature measurements should be approached with caution if a large thermal expansion mismatch is expected.