S. M. Klotsman

Crystallite-conjugation regions and adjacent lattice regions in polycrystalline iridium: I. Composition and properties of adjacent lattice regions formed in polycrystalline iridium during annealing in an ultrahigh vacuum

In this work, we have studied the characteristics of regions in which atomic probes (APs) 57Co(57Fe) were diffusionally localized in polycrystalline iridium (poly-Ir) using a previously developed method based on Mössbauer spectroscopy. Poly-Ir becomes alloyed with oxygen during annealing even in an ultrahigh vacuum already at a temperature of 0.18Tm (Tm is the melting point of the matrix). After the annealing temperature reaches a certain value, there arises a “compensated” state of lattice regions adjacent to crystallite-conjugation regions (“adjacent zones,” or AZs) in poly-Ir. Such a state of AZs arises due to the mutual compensation of positive relaxation volumes of oxygen atoms and negative relaxation volumes of oxygen-vacancy complexes that are formed during each annealing. Therefore, in the “compensated” state of AZs the isomer shifts δ2 of components 2 of Mössbauer spectra of 57Fe APs become equal to “intrinsic” isomer shifts δintrs, 2 of the Mössbauer spectra of 57Fe APs located in the AZs of impurity-free metals. The “intrinsic” isomer shifts depend parabolically on the charges Z of the matrix-atom nuclei.

Crystallite-conjugation regions and adjacent lattice regions in polycrystalline iridium: II. Composition and properties of cores of crystallite-conjugation regions in polycrystalline iridium during annealing in an ultrahigh vacuum

Composition and properties of cores of crystallite-conjugation regions (CCRs) formed during annealing of polycrystalline iridium (poly-Ir) in an ultrahigh vacuum (UHV) have been studied using the method of intercrystalline diffusion in combination with Mössbauer spectroscopy (ID+MS) that has been developed in our previous works. Upon annealing in a UHV, poly-Ir is doped with oxygen from the atmosphere of the vacuum chamber. Complexes containing two vacancies per oxygen atom are formed in the CCR cores of poly-Ir because of a rearrangement of the atomic structure of the CCR cores upon their doping with oxygen. Using the ID+MS method, we for the first time revealed a “compensated” state of CCR cores in poly-Ir samples annealed in a UHV and of CCR cores in poly-Cr annealed in technical vacuum. The cause of the appearance of “compensated” states in CCR cores is the mutual compensation of relaxation volumes with opposite signs characteristic of different point defects. The relaxation volume of an oxygen atom in the CCR core of poly-Ir is by an order of magnitude greater than that in poly-Cr.

Crystallite-conjugation regions and adjacent lattice regions in polycrystalline iridium: III. Enthalpies of formation of vacancies and the energies of interaction of partners in vacancy complexes with oxygen formed in the cores of crystallite-conjugation regions in polycrystalline iridium

The interatomic spacings in the cores of crystallite-conjugation regions (CCRs) and adjacent lattice regions (ALRs) of polycrystals either decrease or increase upon alloying of nominally pure metals with oxygen and vacancy complexes with oxygen (mVacO, where m is the number of vacancies in the complex) that are formed during annealing. These changes in the interatomic spacings lead to an increase or decrease in the isomer shifts δ of the components of the Mössbauer spectra of atomic probes 57Fe that are localized in the CCR cores and ALRs of polycrystals [1–6]. The enthalpies Qmcmpl1, of formation of vacancy-oxygen complexes mVacO in the CCR cores have been measured for Ir and Cr polycrystals, and the enthalpies QVac,1 of formation of vacancies in CCR cores have been determined for Ta, W, Ir, and Cr polycrystals. The enthalpies Emcmpl of the interaction between the partners of the complexes increase with increasing number m of vacancies in the complexes.

Changes in the potential energy upon the formation of vacancies in the volume and in the cores of crystallite-conjugation regions in cubic polycrystalline metals

Changes in the potential energy of atoms that constitute the nearest neighborhood of vacancies formed in the bulk of d transition and precious cubic metals have been determined. These changes agree with the available first-principles calculations of changes in the potential energy of atoms of the nearest neighborhood of vacancies. In the cores of crystallite-conjugation regions (CCRs) of bcc polycrystalline d transition metals, the formation of vacancies is accompanied by positive changes in the potential energy of atoms of their nearest neighborhood. The absolute magnitudes of these changes are several times less than the changes in the potential energy of atoms of the nearest neighborhood of vacancies in the bulk of these metals, in accordance with the relationship between the enthalpies of formation of vacancies in these regions of polycrystals. The changes in the potential energy of atoms of the nearest neighborhood of vacancies formed in the cores of CCRs of fcc polycrystalline metals are negative because of the split structure of vacancies in the CCR cores of such metals.

Recrystallization of deformed single crystals of iridium

The X-ray diffractometric method was used to analyze crystalline textures that appear during rolling of pure single-Ir and annealing of the said crystals in ultrahigh vacuum (UHV) at successively elevating temperatures. Observing alteration of the texture of the deformed pure single-Ir after UHV annealing, the primary recrystallization temperature T{sub 1recr} of pure Ir was found not to exceed 670 K (0.25 T{sub m}).

Effect of the magnetism of impurities on their diffusion in metals: Bulk diffusion of iron, cobalt, and rhodium in iridium single crystals

The coefficients and parameters of the temperature dependences of the coefficients of bulk diffusion of Fe, Co, Rh, and Au atomic probes (APs) in iridium single crystals (mono-Ir) have been determined from the diffusion profiles obtained using secondary-ion mass spectrometry of the diffusion zones. The enthalpies of activation of diffusion of Fe, Co, and Rh APs are considerably lower than the enthalpy of activation of selfdiffusion in mono-Ir. This is caused by the negative contributions of the intraatomic exchange energy and energy of relaxation of the environment of the d transition APs to the enthalpy of interaction of magnetically active APs with the vacancies in the iridium lattice. The interaction energy of partners in such complexes and the relationships between the magnetic moments of d transition APs in complexes with vacancies have been estimated. The Rh APs in complexes with vacancies in iridium possess stable magnetic moments.

Changes in the vibrational energies and interatomic spacings upon the formation of vacancies in the volumes and in the cores of crystallite-conjugation regions of polycrystalline transition metals with cubic lattices

The changes in the vibrational energies and the signs of changes in the interatomic spacings upon the formation of vacancies in the bulk of metal and in the cores of the crystallite-conjugation regions (CCR) in polycrystalline transition metals with bcc and fcc lattices have been determined. The vibrational energy increases upon the formation of a vacancy in the bulk of metal because of a positive “relaxation” contribution to the change in the force constant of the atoms surrounding a vacancy. Positive “relaxation” contributions to the changes in the force constants and, correspondingly, an increase in the vibrational energy of the atoms surrounding a vacancy arise also upon the formation of “split” vacancies (S vacancies) in the cores of CCRs of polycrystalline transition metals with a face-centered cubic lattice. The positive “relaxation” contributions to the changes of the force constant of atoms in the region of localization of S vacancies are caused by a decrease in the interatomic spacings upon their formation, just as upon the formation of conventional vacancies in the bulk of metals. The vibrational energy of the nearest environment of the vacancies that are formed in the CCR cores in the polycrystalline d transition metals with a bcc lattice decreases because of a negative “relaxation” contribution to the change in the force constants. The cores of the high-angle CCRs in polycrystalline d transition metals with a bcc lattice are characterized by a negative internal pressure. Therefore, vacancies with positive relaxation volumes νBCC > 0 are formed in them, causing an increase in the interatomic distances in the nearest environment of such vacancies.

Changes in the Potential and Vibrational Energies upon the Formation of Vacancies in the Oxygen-Alloyed Cores of Crystallite-Conjugation Regions of Polycrystalline Cr, Cu, and Ir

The changes in the potential and vibrational energies upon the formation of vacancies in the oxygen-alloyed (OA) cores of crystallite-conjugation regions (CCRs) in polycrystals of d transition metals Cr, Cu, and Ir have been determined. The potential energy increases upon the formation of vacancies (upon the formation of complexes of vacancies with oxygen atoms) in the OA cores of CCRs in the polycrystalline Cr, Cu, and Ir. However, the vibrational energy decreases upon the formation of vacancies in the OA cores of CCRs in these polycrystals, as in the OA cores of CCRs in polycrystals of the 4d and 5d transition bcc metals Mo, Ta, and W. The volume of the OA cores of CCRs in polycrystals of Cr, Cu, and Ir decreases upon the formation of vacancies. The changes in the interatomic interactions and dynamic properties in the regions of vacancy localization in the OA cores of CCRs coincide with analogous changes introduced into the lattices of metals by split interstitials.