TITLE:
Phase-Transitions at High, Very High, and Very Low Temperatures upon Nano-Indentations: Onset Forces and Transition Energies
AUTHORS:
Gerd Kaupp
KEYWORDS:
Aluminum Alloy, Aviation, Cosmology, Epochal News, High and Liquid Nitrogen Temperature Indentations, Negative-Energy-Content Polymorph, Molybdenum, Phase-Transition-Energy
JOURNAL NAME:
Advances in Materials Physics and Chemistry,
Vol.13 No.6,
June
27,
2023
ABSTRACT: This paper describes the phase-transition energies from published loading curves on the basis of the physically deduced FN = k-h3/2 law that does not violate the energy law by assuming h2 instead, as still do ISO-ASTM 14,577 standards. This law is valid for all materials and all “one-point indentation” temperatures. It detects initial surface effects and phase-transition kink-unsteadiness. Why is that important? The mechanically induced phase-transitions form polymorph interfaces with increased risk of crash nucleation for example at the pickle forks of airliners. After our published crashing risk, as nucleated within microscopic polymorph-interfaces via pre-cracks, had finally appeared (we presented microscopic images (5000×) from a model system), 550 airliners were all at once grounded for 18 months due to such microscopic pre-cracksat their pickle forks (connection device for wing to body). These pre-cracks atphase-transition interfaces were previously not complained at the (semi)yearlycheckups of all airliners. But materials with higher compliance against phase- transitions must be developed for everybody’s safety, most easily by checking with nanoindentations, using their physically correct analyses. Unfortunately, non-physical analyses, as based on the after all incredible exponent 2 on h for the FN versus h loading curve are still enforced by ISO-ASTM standards that cannot detect phase-transitions. These standards propagate that all of the force, as applied to the penetrating cone or pyramid shall be used for the depth formation, but not also in part for the pressure to the indenter environment. However, the remaining part of pressure (that was not consumed for migrations, etc.) is always used for the elastic modulus detection routine. That severely violates the energy-law! Furthermore, the now physically analyzed published loading curves contain the phase-transition onsets and energies information, because these old-fashioned authors innocently (?) published (of course correct) experimental loading curves. These follow as ever the physically deduced FN = k-h3/2 relation that does not violate the energy law. Nevertheless, the old-fashioned authors stubbornly assume h2instead of h3/2 as still do ISO-ASTM 14,577 standards according to an Oliver-Pharr publication of 1992 and textbooks. The present work contributes to understanding the temperature dependence of phase-transitions under mechanical load, not only for aviation and space flights, which is important. The physical calculations use exclusively regressions and pure algebra (no iterations, no fittings, and no simulations) in a series of straightforward steps by correcting for unavoidable initial effects from the axis cuts of the linear branches from the above equation exhibiting sharp kink unsteadiness at the onset of phase transitions. The test loading curves are from Molybdenum and Al 7075 alloy. The valid published loading curves strictly follow the FN = k-h3/2 relation. Full applied work, conversion work, and conversion work per depth unit show reliable overall comparable order of magnitude values at temperature increase by 150°C (Al 7075) and 980°C (Mo) when also considering different physical hardnesses and penetration depths. It turns out how much the normalized endothermic phase-transition energy decreases upon temperature increase. For the only known 1000°C indentation we provide reason that the presented loading curves changes are only to a minor degree caused by the thermal expansion. The results with Al 7075 up to 170°C are successfully compared. Al 7075 alloy is also checked by indentation with liquid nitrogen cooling (77 K). It gives two endothermic and one very prominent exothermic phase transition with particularly high normalized phase-transition energy. This indentation loading curve at liquid nitrogen temperature reveals epochal novelties. The energy requiring endothermic phase transitions (already seen at 20°C and above) at 77 K is shortly after the start of the second polymorph (sharply at 19.53 N loading force) followed by a strongly exothermic phase-transition by producing (that is losing) energy-content. Both processes at 77 K are totally unexpected. The produced energy per depth unit is much higher energy than the one required for the previous endothermic conversions. This exothermic phase-transition profits from the inability to provide further energy for the formation of the third polymorph as endothermic obtained at 70°C and above. That is only possible because the very cold crystal can no longer support endothermic events but supports exothermic ones. Both endothermic and exothermic phase-transitions at 77 K under load are unprecedented and were not expected before. While the energetic support at 77 K for endothermic processes under mechanical load is unusual but still understandable (there are also further means to produce lower temperatures). But strongly exothermicphase-transition under mechanical load for the production of new modification with negative energy content (less than the energy content of the ambient polymorph) at very low temperature is an epochal event here on earth. It leads to new global thinking and promises important new applications. The energy content of strongly exothermic transformed material is less than the thermodynamic standard zero energy-content on earth. And it can only be reached when there is no possibility left to produce an endothermic phase-transition. Such less than zero-energy-content materials should be isolated, using appropriate equipment. Their properties must be investigated by chemists, crystallographers, and physicists for cosmological reasons. It could be that such materials will require cooling despite their low energy content (higher stability!) and not survive at ambient temperatures and pressures on earth, but only because we do not know of such negative-energy-content materials with our arbitrary thermodynamic standard zeros on earth. At first one will have to study how far we can go up with temperature for keeping them stable. Thus, the apparently never before considered unprecedented result opens up new thinking for the search of new polymorphs that can, of course, not be reached by heating. Various further applications including cosmology and space flight explorations are profiting from it.