Limitations of Thermal Stability Analysis via In-Situ TEM/Heating Experiments

This work highlights some limitations of thermal stability analysis via in-situ transmission electron microscopy (TEM)-annealing experiments on ultrafine and nanocrystalline materials. We provide two examples, one on nanocrystalline pure copper and one on nanocrystalline HT-9 steel, where in-situ TEM-annealing experiments are compared to bulk material annealing experiments. The in-situ TEM and bulk annealing experiments demonstrated different results on pure copper but similar output in the HT-9 steel. The work entails discussion of the results based on literature theoretical concepts, and expound on the inevitability of comparing in-situ TEM annealing experimental results to bulk annealing when used for material thermal stability assessment.

The closure temperature(s) of zircon Raman dating

Zircon Raman dating based on irradiation damage is a debated concept but not an established geo-/thermochronological method. One issue is the temperature range of radiation-damage annealing over geological timescales. We conducted isochronal and isothermal annealing experiments on radiation-damaged zircons between 500 and 1000 ∘C for durations between 10 min and 5 d to describe the annealing kinetics. We measured the widths (Γ) and positions (ω) of the ν1(SiO4), ν2(SiO4), and ν3(SiO4) internal Raman bands, and the external rotation Raman band at ∼974, 438, 1008, and 356 cm−1 after each annealing step. We fitted a Johnson–Mehl–Avrami–Kolmogorov and a distributed activation energy model to the fractional annealing data, calculated from the widths of the ν2(SiO4), ν3(SiO4), and external rotation bands. From the kinetic models, we determined closure temperatures Tc for damage accumulation for each Raman band. Tc ranges from 330 to 370 ∘C for the internal ν2(SiO4) and ν3(SiO4) bands; the external rotation band is more sensitive to thermal annealing (Tc∼260 to 310 ∘C). Our estimates are in general agreement with previous ones, but more geological evidence is needed to validate the results. The Tc difference for the different Raman bands offers the prospect of a multi-closure-temperature zircon Raman thermochronometer.

Confirmation of slow Ti diffusion in quartz by diffusion couple experiments and evidence from natural samples

Titanium diffusion profiles in natural quartz crystals have become an increasingly popular tool to reconstruct the time scales of various magmatic, metamorphic, and hydrothermal processes. However, the original calibration of Ti diffusion rates in quartz has recently been challenged, and diffusivities were found to be about three orders of magnitude lower. We performed annealing experiments on crystal-crystal diffusion couples consisting of Ti-free synthetic quartz seeds over which Ti-rich quartz (100–3000 μg/g Ti) was grown hydrothermally. The annealing experiments were performed at 1000–1600 °C and 0.1 MPa to 2.0 GPa, and they lasted for 3–84 days. The resulting diffusion profiles were mapped by cathodoluminescence (CL), transmission electron microscope–energy-dispersive X-ray spectroscopy (TEM-EDXS), and, for the first time, by helium ion microscope–secondary ion mass spectrometry (HIM-SIMS). Obtained diffusion coefficients range from values similar to the lower range in previous research to values up to two orders of magnitude lower. In addition, inversely zoned quartz and sanidine phenocrysts in a natural rhyolite were studied. Comparison of the diffusion profiles suggests that at ~735 °C, the Ti diffusivity in quartz is ~1.5 and 3.0 orders of magnitude lower than that of Ba and Sr, respectively, in sanidine. The combined evidence confirms that Ti diffusion in quartz is very slow, potentially even slower than proposed earlier. Consequently, previous time scales derived from Ti diffusion profiles in quartz are likely orders of magnitude too short, and further experiments are necessary to fully clarify the issue.

Diamonds from the Mir Pipe (Yakutia): Spectroscopic Features and Annealing Studies

For this study, 21 samples of colorless octahedral diamonds (weighing 5.4–55.0 mg) from the Mir pipe (Yakutia) were investigated with photoluminescence (PL), infrared (IR), and electron paramagnetic resonance (EPR) spectroscopies. Based on the IR data, three groups of diamonds belonging to types IIa, IaAB, and IaB were selected and their spectroscopic features were analyzed in detail. The three categories of stones exhibited different characteristic PL systems. The type IaB diamonds demonstrated dominating nitrogen–nickel complexes S2, S3, and 523 nm, while they were less intensive or even absent in the type IaAB crystals. The type IIa diamonds showed a double peak at 417.4+418.7 nm (the 418 center in this study), which is assumed to be a nickel–boron defect. In the crystals analyzed, no matter which type, 490.7, 563.5, 613, and 676.3 nm systems of various intensity could be detected; moreover, N3, H3, and H4 centers were very common. The step-by-step annealing experiments were performed in the temperature range of 600–1700 °C. The treatment at 600 °C resulted in the 563.5 nm system’s disappearance; the interstitial carbon vacancy annihilation could be considered as a reason. The 676.5 nm and 613 nm defects annealed out at 1500 °C and 1700 °C, respectively. Furthermore, as a result of annealing at 1500 °C, the 558.5 and 576 nm centers characteristic of superdeep diamonds from São Luis (Brazil) appeared. These transformations could be explained by nitrogen diffusion or interaction with the dislocations and/or vacancies produced.

Thermodynamics of Mg–Al Order-Disorder Reaction in MgAl2O4-Spinel: Constrained by Prolonged Annealing Experiments at 773–1123 K

MgAl2O4-spinel has wide industrial and geological applications due to its special structural and physical–chemical features. It is presumably the most important endmember of complex natural spinel solid solutions, and therefore provides a structural model for a large group of minerals with the spinel structure. There exists a well known but still inadequately understood phenomenon in the structure of MgAl2O4-spinel, the Mg–Al cations readily exchanging their positions in response to variations of temperature, pressure, and composition. A large number of experiments were performed to investigate the Mg–Al cation order-disorder process usually quantified by the inversion parameter x (representing either the molar fraction of Al on the tetrahedral T-sites or the molar fraction of Mg on the octahedral M-sites in the spinel structure), and some thermodynamic models were thereby constructed to describe the x-T relation. However, experimental data at some key T were absent, so that the different performance of these thermodynamic models could not be carefully evaluated. This limited the interpolation and extrapolation of the thermodynamic models. By performing some prolonged annealing experiments with some almost pure natural MgAl2O4-spinel plates and quantifying the x values with single-crystal X-ray diffraction technique, we obtained some critical equilibrium x values at T down to 773 K. These new x-T data, along with those relatively reliable x values at relatively high T from early studies, clearly indicate that the CS94 Model (a model constructed by Carpenter and Salje in 1994) better describes the Mg–Al cation order-disorder reaction in MgAl2O4-spinel for a wide range of T. On the basis of the CS94 Model, a geothermometer was established, and its form is T-closure = 21362 × x3 − 12143 × x2 + 6401 × x − 10 (T-closure standing for the closure temperature of the Mg–Al cation exchange reaction). This geothermometer can be used to constrain the thermal history of the geological bodies containing MgAl2O4-spinel.

The closure temperature(s) of zircon Raman dating

We conducted isochronal and isothermal annealing experiments on radiation-damaged zircons between 500 and 1000 °C for durations between ten minutes and five days. We measured the widths (Γ) and positions (ω) of the internal ν1(SiO4), ν2(SiO4), ν3(SiO4), and external rotation Raman bands at ~ 974, 438, 1008, and 356 cm−1. We fitted a Johnson-Mehl-Avrami-Kolmogorov and a distributed activation energy model to the fractional annealing data, calculated from the widths of the ν2(SiO4), ν3(SiO4), and external rotation bands. From the kinetic models, we determined closure temperatures Tc for damage accumulation for each Raman band. Tc range from 330 to 370 °C for the internal ν2(SiO4) and ν3(SiO4) bands; the external rotation band is more sensitive to thermal annealing (Tc ~ 260 to 310 °C). Our estimates are in general agreement with previous ones, but more geological evidence is needed to validate the results. The Tc difference for the different Raman bands offers the prospect of a multi-closure-temperature zircon Raman thermochronometer.

A Defect Study and Classification of Brown Diamonds with Deformation-Related Color

For this study, the properties of a large sample of various types of brown diamonds with a deformation-related (referred to as “DR” in this work) color were studied to properly characterize and classify such diamonds, and to compare them to pink to purple to red diamonds. The acquisition of low temperature NIR spectra for a large range of brown diamonds and photoexcitation studies combined with various treatment experiments have opened new windows into certain defect characteristics of brown diamonds, such as the amber centers and naturally occurring H1b and H1c centers. It was determined that the amber centers (referred to as “AC” in this work) exhibit rather variable behaviors to annealing and photoexcitation; the annealing temperature of these defects were determined to range from 1150 to >1850 °C and it was found that the 4063 cm−1 AC was the precursor defect of many other ACs. It is suggested that the amber centers in diamonds that contain at least some C centers are essentially identical to the ones seen in diamonds without C centers, but that they likely have a negative charge. The study of the naturally occurring H1b and H1c link them to the amber centers, specifically to the one at 4063 cm−1. Annealing experiments have shown that the H1b and H1c defects and the 4063 cm−1 AC were in line with each other. The obvious links between these defects points towards our suggestion that the H1b and H1c defects are standalone defects that consist of multiple vacancies and nitrogen and that they are—in the case of brown diamonds—a side product of the AC formation. A new classification of DR brown diamonds was elaborated that separates the diamonds in six different classes, depending on type and AC. This classification had been completed recently with the classification of brown diamonds with a non-deformation-related color (referred to as “NDR”), giving a total of 11 classes of brown diamonds.

Magma water content of Pico Volcano (Azores Islands, Portugal): a clinopyroxene perspective

Clinopyroxenes from the Pico Volcano (Pico Island, Azores Archipelago) have been used as a proxy to define the water content of primitive magmas and the volcanological history of the erupted rocks. This very young volcano (53 ± 5 ka) is at a primordial stage of its evolution in comparison with the other volcanoes of the Azores. Clinopyroxenes from Pico Volcano underwent important dehydration processes and after annealing experiments under H2 gas flux, a pre-eruptive H2O content between 93 and 182 ppm was recovered. A moderately high cooling rate for the cpx-host lavas expressed by the clinopyroxene closure temperature (Tc = 755–928 °C ± 20 °C) correlates with the dehydration, suggesting that this process may have occurred during magma ponding at the Moho Transition Zone (17.3–17.7 km) and/or after the eruption. By applying an IVAl-dependent partition coefficient to the measured H amount in clinopyroxene, the pre-eruptive water content of the parental magma was calculated to vary between 0.71 and 1.20 (average of 1.0) wt%. Clinopyroxene geobarometry performed by combining X-ray diffraction with mineral chemistry points to a general crystallisation from the mantle lithosphere (~ 8–9 kbar) to the oceanic mantle/crust boundary (~ 4–5 kbar). The similar major and trace chemistry, water content and Fe3+/Fetot ratio of clinopyroxene, suggest similar conditions of oxygen fugacity, water content and fractional crystallisation of the magma from which clinopyroxene cores crystallised during the Pico Volcano central eruptions from 40 ka to historical times.

Effect of cross cold rolling and annealing on microstructure and texture in pure nickel

The microstructure and texture in pure nickel were investigated during multi-step cross cold rolling (CCR) and subsequent annealing. It was found that the deformation texture in the CCR nickel was dominated by Brass and rotated Brass about normal direction (ND) (BsND) texture components, along with marginal cube textures. The resulted deformation textures had a significant effect on the recrystallization behavior. Annealing of the CCR nickel at 550°C for 1 h led to the formation of dominant <012> // ND fiber accompanied by minor rotated cube textures, rather than strong cube texture. Increasing the annealing temperature up to 800°C resulted in further enhancement of <012> // ND fiber textures. The possible reasons for recrystallization behavior in annealed CCR sample were discussed based on in-situ annealing experiments from two aspects of oriented nucleation and oriented growth theories.