Die vorliegende Arbeit zeigt einen Weg, Kupfer und einphasige Kupferlegierungen mit stark verzwillingten Gefügen durch ein technisch relevantes Umformverfahren herzustellen. Der Drahtzug bildet dabei aufgrund seines Spannungszustands und der entsprechenden Texturentwicklung in kubischflächenzentrierten Metallen ein ideales Umformverfahren, um einen Großteil des Gefüges durch mechanische Zwillingsbildung zu verfeinern. Für die Aktivierung der Zwillingsbildung in reinem Kupfer unter den untersuchten Werkstoffvarianten sind Temperaturen nahe der Temperatur des flüssigen Stickstoffs notwendig. Um den Drahtzug in flüssigem Stickstoff umzusetzen, wurden verschiedene Feststoffschmiermittel auf ihre Eignung hin getestet. Die Textur der mit Stickstoffkühlung hergestellten Halbzeuge ist durch eine dreifache Fasertextur bestehend aus <111>-, <001>- und <115>-Fasertexturkomponente charakterisiert. Anhand der strengen Orientierungsverhältnisse konnte der Volumenanteil von verzwillingtem Material bestehend aus Matrixkörnern und Verformungszwillingen auf 71 vol% durch röntgenografische Globaltexturmessungen abgeschätzt werden, wobei das Volumenverhältnis von Zwillingen zu Matrix bei knapp 0,7:1 liegt. Die Zwillinge zeigen eine breite Zwillingslamellenweitenverteilung von wenigen Nanometern bis einige 100 nm im höchstverformten Stadium. Durch die Absenkung der Umformtemperatur und die daraus resultierende Aktivierung der Zwillingsbildung kann die Zugfestigkeit von reinem Kupfer um 140 MPa im Vergleich zu einem ohne Kühlung hergestellten Draht auf 582 MPa erhöht werden. Dabei reduziert sich die elektrische Leitfähigkeit um 6,5% gegenüber einem grobkorngeglühten Kupfer. Eine Absenkung der Stapelfehlerenergie auf 30 mJ/m² in CuAl2 führt zur Aktivierung der mechanischen Zwillingsbildung beim Drahtzug ohne Kühlung. Durch diese Aktivierung der Zwillingsbildung kann bei fortschreitender Verringerung der Stapelfehlerenergie wie in CuAl7 die Zugfestigkeit des umgeformten Drahtes auf weit über 1 GPa erhöht werden. Das entsprechende Gefüge ist dabei ultrafeinkörnig.

Sanicro 28 and Alloy 625 are corrosion-resistant nickel alloys with a fully austenitic structure and a very low carbon content, which means they are both well suited for cold working. Since the millennium shift deformation twinning has been a live research issue as it enhances strength and ductility simultaneously. As nickel has been pointed out as a high stacking fault energy element and deformation twinning should be promoted by a low stacking fault energy level they have been considered as opposite poles. Nonetheless, it is known since long that deformation twins can emerge in high stacking fault face centred cubic elements at low temperatures. In this thesis, we have investigated deformation twinning behaviour in corrosion-resistant nickel alloys. The objective is trying to distinguish between deformation twinning in TWIP steel and corrosion resistant nickel alloys regarding for instance size and bundles. Interrupted uniaxial tensile tests have been performed at several cold working temperatures for the alloys: Sanicro 28 (31% nickel) and Alloy 625 (61% nickel). The microstructure has been characterized in homogeneous deformation volume, by scanning electron microscopy electron backscattering diffraction and electron channelling contrast imaging, transmission electron microscopy and X-ray diffraction. In one investigation fracture behaviour has also been studied with secondary electrons. Ab initio calculations, crystal plasticity modelling and DAMASK simulations have been performed to support emphasizing active deformation mechanisms. It has been revealed that deformation twinning can occur in high Ni alloys. With increasing deformation twinning levels, the diffuse necking decreases. Ab initio calculations indicates that the initiation of deformation twins cannot be determined solely by the stacking fault energy. Distinct features were discovered at low strains that could be rejected from being neither deformation twins nor stacking faults. Level of texture increases with increasing strain and decreasing temperature and the texture modes are changed with decreasing temperature. / Sanicro 28 och Alloy 625 är två legeringar med ett imponerande korrosionsmotstånd, ett lågt kolinnehåll och en helaustenitisk struktur. Det gör dem väl lämpade för kallbearbetning. Sedan millenieskiftet har aktivten varit mycket hög inom forskningsområdet: deformationstvillingar. TWIP (twinning induced plasticity)-effekten har den så eftertraktade egenskapen att både styrkan och duktiliteten förbättras på samma gång. Eftersom nickel har en hög staplingsfelsenergi och TWIP-effekten har uppmätts/beräknats till att aktiveras vid ett snävt och lågt värde, för densamma, har ett ökande nickelinnehåll och TWIP-effekten setts som direkta motpoler. Trots det, har man länge vetat om att deformationstvillingar också framträder, om än, vid låga temperaturer, i legeringar med kubiskt ytcentrerat gitter och hög staplingsfelsenergi. I den här avhandlingen har vi undersökt hur deformationstvillingar utvecklas, om de ens kan bildas i korrosionsbeständiga legeringar med ett högt nickelinnehåll. Målet är att se om det finns några större skillnader i tvillingbeteendet i TWIP-stål i jämförelse med korrosionsbeständiga legeringar med ett högt nickelinnehåll. Några egenskaper vi har tänkt att undersöka är: tjocklek på tvillingarna och om tvillingarna bildas i grupper. Vi hoppas på så sätt kunna svara på den övergripande forskningsfrågan: är det möjligt att designa ett rostfritt TWIP-stål, baserat på det vanligaste legeringssystemet för rostfria austenitiska stål, nämligen: järn-krom-nickel? Enaxliga dragprov har genomförts vid flera kallbearbetningstemperatuer; de har utförts både till brott och till förutbestämda töjningsnivåer. Legeringarna som har testats är: Sanicro 28 (31% nickel) och Alloy 625 (61% nickel). Mikrostrukturen har framför allt karakteriserats i material uttaget från volym där deformationen har varit homogen. De analysmetoder som har använts är: svepelektronmikroskopi, mer specifikt: ”electron backscatter diffraction” och ”electron channelling contrast imaging”. Transmissionselektronmikroskop och röntgendiffraktion har också använts. I en undersökning har också brottbeteende studerats med hjälp av "secondary electrons". Ab initioberäkningar, modellering av kristallplasticitet och materialbeteende med hjälp av DAMASK har också utförts för att kunna se vilka deformationsmekanismer som är aktiva. Vi upptäckte att deformationstvillingar faktiskt kan bildas i korrosionsbeständiga legeringar med ett högt nickelinnehåll. Den diffusa midjebildningen minskar på samma gång som andelelen deformationstvillingar ökar. Ab initioberäkningarnas resultat indikerar också på att deformationstvillingarnas inträde inte enbart kan bestämmas med staplingsfelsenergin. Tydliga mikrostrukturmönster upptäcktes med hjälp av transmissionsmiroskop och vid låga töjningsnivåer. De mikrostrukturmönstren kunde avfärdas från att vara både deformationstvillingar och staplingsfel. Texturnivån ökar med ökande töjningsnivå och sjunkande temperatur. Typen av textur förändras också med sjunkande temperatur. / <p>Funding agency: Tube division, Alleima AB</p>

Plastic deformation of metals and alloys are invariably accompanied by the development of texture. The origin of texture is attributed to the deformation micro-mechanisms associated with processing. The face-centered cubic (FCC) metals and alloys are known to exhibit two distinct types of textures when subjected to large strain rolling deformation, namely, (i) Cu-type texture, commonly seen in high/medium stacking fault energy (SFE) materials, (ii) Bs-type texture in low SFE materials. The circumstances that could result in the formation of Bs-type texture in low SFE materials still remains an open question and no definite mechanism has been uniquely agreed upon. Apart from the SFE, grain size could also influence the deformation mechanism and hence the deformation texture. It is well known that in materials with grain sizes less than 100 nm (referred to as nano-crystalline materials), the microstructures contain large fraction of grain boundaries. This subsequently introduces a variety of deformation mechanisms in the microstructure involving grain boundary-mediated processes such as grain boundary sliding and grain rotation, in addition to slip and twinning. A clear understanding of texture evolution in nano-crystalline materials, particularly at large strains, is a topic that remains largely unexplored. The present work is an attempt to address the aforementioned issues pertaining to the evolution of deformation texture, namely, (i) the effect of SFE and (ii) the effect of grain size, in FCC metals and alloys. Nickel-cobalt alloys are chosen as the model system for the present investigation. The addition of cobalt to nickel leads to a systematic reduction of SFE as a function of cobalt content. In this thesis, three alloys of Ni-Co system have been considered, namely, nickel – 20 wt.% cobalt, nickel – 40 wt.% cobalt and nickel – 60 wt.% cobalt. For a comparison, pure nickel has also been subjected to similar study. Chapter 1 of the thesis presents a detailed survey of literature pertaining to the evolution of rolling textures in FCC metals and alloys, and chapter 2 includes the details of the experimental techniques and characterization procedures, which are commonly employed for the entire work. Chapter 3 addresses the effect of stacking fault energy on the evolution of rolling texture. The materials subjected to study in this chapter are microcrystalline Ni-Co alloys. The texture evolution in Ni-20Co is very similar to pure Ni, and a characteristic Cu-type rolling texture is observed. The evolution of texture in these materials is primarily attributed to the intense dislocation activity throughout the deformation stages. In Ni-40Co, a medium SFE material, the rolling texture was predominantly Cu-type up to a strain of ε = 3 (95% thickness reduction). However, beyond this strain level, namely at ε = 4 (98%), the texture gets transformed to Bs-type with orientations maxima predominantly close to Goss ({110} <001>) position. Simultaneously, the Cu component which was dominant until 95% reduction has completely disappeared. The analysis of microstructures indicate that deformation is mostly accommodated by dislocation slip up to 95%, however, at ε > 3, Cu-type shear bands get initiated, preferably in the Cu-oriented ({112} <111>) grains. The sub-grains within the shear bands show preferred orientation towards Goss, which indicates that the Cu component should have undergone transformation and resulted in high fraction of Goss component. In Ni-60Co alloy, Bs-type texture forms in the early stages of deformation (ε ~ 0.5) itself and further deformation results in strengthening of the texture with an important difference that the maximum in orientation distribution has been observed at a location close to Goss component, rather than at exact Bs-location. The development of Bs-type texture is accompanied by the complete absence of Cu and S components. Extensive EBSD analyses show that the deformation twinning gets initiated beyond 10% reduction and was found extensively in most of the grains up to 50% reduction. At higher strains, tendency for twinning ceases and extensive shear banding is observed. A non-random distribution of orientations close to Goss orientation was found within the shear bands. The near-Goss component in the Ni-60Co alloy can be explained on the basis of deformation twinning and shear banding. Thus, a reasonable understanding of the deformation texture transition in the extreme SFE range has been developed. In chapter 4, the effect of fine grain size on the evolution of rolling texture has been addressed. Nanocrystalline (nc) nickel-cobalt alloys with a mean grain size of ~20 nm have been prepared by pulse electro-deposition method. For a comparison, nc Nickel (without cobalt) with similar grain size has also been deposited. For all the materials, a weakening of the initial fiber texture is observed in the early stage of room temperature rolling (ε ~ 0.22). A combination of equiaxed grain microstructure and texture weakening suggests grain boundary sliding as an operative mechanism in the early stage of rolling. At large strain (ε = 1.2), Ni-20Co develops a Cu-type texture with high fractions of S and Cu components, similar to pure Ni. The texture evolution in Ni-40Co and Ni-60Co alloys is more towards Bs-type. However, the texture maximum occurs at a location 10° away from the Goss. The evolution of Cu and S components in nc Ni-60Co alloy takes place simultaneously along with the α-fiber components during rolling. Microstructural investigation by TEM indicates deformation twinning to be more active in all the materials up to 40% reduction. However, no correlation could be drawn between the texture evolution and the density of twins. The deformation of nc Ni-20Co alloy, is also accompanied by significant grain growth at all the stages of rolling. The increase in grain size, subsequently, renders the texture to be of Cu-type. However, Ni-40Co and Ni-60Co alloys show high grain stability. The absence of strain heterogeneities such as shear bands, and the lack of significant fraction of deformation twins indicate that the observed Bs-type texture could be due to planar slip. The increase in deformation beyond 70% reduction caused a modest reduction in the intensity of deformation texture. The microstructural observation indicates the occurrence of restoration mechanisms such as recovery/ recrystallization at large strains. The overall findings of the investigation have been summarized in chapter 5. The deformation mechanism maps relating stacking fault energy with amount of strain and with grain size are proposed for micro- and nano- crystalline materials respectively.

In this work we study the interesting physics of the rare earths, and the microscopic state after ultrafast magnetization dynamics in iron. Moreover, this work covers the development, examination and application of several methods used in solid state physics. The first and the last part are related to strongly correlated electrons. The second part is related to the field of ultrafast magnetization dynamics. In the first part we apply density functional theory plus dynamical mean field theory within the Hubbard I approximation to describe the interesting physics of the rare-earth metals. These elements are characterized by the localized nature of the 4f electrons and the itinerant character of the other valence electrons. We calculate a wide range of properties of the rare-earth metals and find a good correspondence with experimental data. We argue that this theory can be the basis of future investigations addressing rare-earth based materials in general. In the second part of this thesis we develop a model, based on statistical arguments, to predict the microscopic state after ultrafast magnetization dynamics in iron. We predict that the microscopic state after ultrafast demagnetization is qualitatively different from the state after ultrafast increase of magnetization. This prediction is supported by previously published spectra obtained in magneto-optical experiments. Our model makes it possible to compare the measured data to results that are calculated from microscopic properties. We also investigate the relation between the magnetic asymmetry and the magnetization. In the last part of this work we examine several methods of analytic continuation that are used in many-body physics to obtain physical quantities on real energies from either imaginary time or Matsubara frequency data. In particular, we improve the Padé approximant method of analytic continuation. We compare the reliability and performance of this and other methods for both one and two-particle Green's functions. We also investigate the advantages of implementing a method of analytic continuation based on stochastic sampling on a graphics processing unit (GPU).

Hoch manganhaltige Eisenbasislegierungen sind bei Raumtemperatur austenitisch und antiferromagnetisch (afm). Dabei besteht die Besonderheit, dass sich durch Legierung die afm Übergangstemperatur (Néeltemperatur) so einstellen lässt, dass sie nahe Raumtemperatur liegt. FeMn-Basislegierungen zeigen in Abhängigkeit von der Zusammensetzung Transformation Induced Plasticity (TRIP) und/oder Twinning Induced Plasticity (TWIP), d.h. die niedrige Stapelfehlerenergie dieser Legierungen führt zu verformungsinduzierter, metastabiler Phasenbildung (TRIP) bzw. zur Bildung von Verformungszwillingen (TWIP) und dadurch zu außerordentlich hoher Duktilität bei gleichzeitig hoher Verfestigung. Darüber hinaus haben FeMn-Basislegierungen einen ausgeprägten Magnetovolumeneffekt und magnetoelastischen Effekt durch magnetische Ordnung. Daher sind die untersuchten FeMnNiCr-Basislegierungen auch prototypisch für afm Élinvarlegierungen. Da Élinvar jedoch für invariable Elastizität steht, bedingt eine Anwendung als temperaturkompensierte Konstantmodullegierungen die Glättung der ausgeprägten magnetischen Anomalien, die industriell noch in keiner Anwendung realisiert wurde. Der Vorteil dies für eine Anwendung zu erreichen, läge in der Unempfindlichkeit feinmechanischer Bauelemente, gegenüber magnetischen Feldern, die bei den industriell verfügbaren ferromagnetischen Élinvarlegierungen nicht gewährleistet ist. Mit Bezug zu feinmechanischen Schwingsystemen spielen dabei neben der Einstellung der magnetoelastischen Eigenschaften die Prozessierbarkeit, Kaltumformbarkeit und Festigkeit sowie deren wechselseitige Beeinflussung eine große Rolle. Die vorliegende Arbeit befasst sich daher mit der Anwendbarkeit der untersuchten FeMnNiCr-Legierungen. Dabei wurden grundlegende Untersuchungen zur Plastizität durchgeführt, die die mechanische Zwillingsbildung in diesen Legierungen charakterisiert und ein Modell der mechanischen Zwillingsbildung bei kleinen plastischen Dehnungen vorschlägt, das eine Abschätzung der Stapelfehlerenergie erlaubt. Die Untersuchung des Antiferromagnetismus umgeformter Proben zeigt das Auftreten thermoremanenter Magnetisierung (TRM), deren Größe mit dem Umformgrad der untersuchten Proben skaliert. Sie wird den durch Umformdefekte erzeugten unkompensierten Momenten in der afm Spinstruktur zugeschrieben. Diese werden durch eine magnetische Feldkühlung magnetisiert und koppeln durch Austauschwechselwirkung an die umgebende antiferromagnetische Matrix unterhalb der Néeltemperatur. Das komplexe thermomagnetische Verhalten der unkompensierten Momente wird experimentell beschrieben und phänomenologisch gedeutet. Die Weiterentwicklung und Bewertung technischer, ausscheidbarer FeMnNiCrBe- und FeMnNiCr(Ti, Al)-Legierungen wird mit Bezug zu den grundlegenden Untersuchungen dargestellt. Es wird gezeigt, dass die neu entwickelten ausscheidbaren FeMnNiCr(Ti, Al)-Legierungen eine vielversprechende Ausgangsbasis darstellen, afm Élinvarlegierungen technisch umzusetzen. / High manganese iron-base alloys are austenitic and antiferromagnetic (afm) at room temperature. By further alloying it is possible to tune the afm transition temperature (Néel temperature) near room temperature. FeMn-base alloys show extraordinary strain hardening as well as ductility because of Transformation Induced Plasticity (TRIP) and/or Twinning Induced Plasticty (TWIP), i.e. in dependence on composition the generally low stacking fault energy in these alloys allows for the mechanically induced formation of metastable phases (TRIP) or deformation twinning (TWIP). Furthermore, magnetic order causes distinct magnetovolume and magnetoelastic effects in these afm FeMn-base alloys. The investigated FeMnNiCr-base alloys are therefore prototypic for afm Élinvar alloys. However, as Élinvar is meant for invariant elasticity, an application as temperature compensated alloy with constant elastic modulus requires the smoothing of the pronounced magnetic anomalies, that is not industrially available yet. The advantage of afm Élinvar alloys in precision mechanics applications, would be their impassiveness with respect to magnetic fields that is not achievable by their ferromagnetic counterparts. For precision components like mechanic oscillators not only the tuning of the magnetoelastic properties but also the processing, cold formability and mechanical properties as well as their interplay have strong influence. Therefore this work addresses the applicability of the studied FeMnNiCr alloys. Elementary investigations on plasticity characterise the occurrence of TWIP in these alloys and propose a modell for deformation twinning at low plastic strains that allows for an estimation of the stacking fault energy. The investigations on the antiferromagnetism of deformed samples show the appearance of thermoremanent magnetisation (TRM). Its magnitude scales with the degree of deformation. The TRM is therefore attributed to uncompensated moments in the afm spin structure due to deformation induced defects. These are magnetised by a magnetic field cooling and couple to the afm matrix by exchange interaction below the Néel temperature. The complex thermomagnetic behaviour of the uncompensated moments is experimentally described and phenomenologically explained. The further development and assessment of engineering-grade pecipitable FeMnNiCrBe and FeMnNiCr(Ti, Al) alloys is presented in relation to the aforementioned elementary investigations. It is shown that the newly developped precipitable FeMnNiCr(Ti, Al) alloys are good candidates for afm Élinvar alloys in application.

FCC組織を有する純金属と合金において強ひずみ加工法の1つである側方押出し加工（ECAP）法を用いて超微細結晶材を作製し，ECAPの各段階における力学特性と微細組織を調査した．微細組織形成過程におけるセル壁の形成から結晶粒界の形成に着目し，積層欠陥エネルギーと固溶原子による固溶強化の効果の観点から，強ひずみ加工における加工硬化ステージの推移と微細組織形成の関係を議論した. / 博士(工学) / Doctor of Philosophy in Engineering / 同志社大学 / Doshisha University

<p>Co and Ni are two major elements in high temperature structural alloys that include superalloys for turbine engines and hard metals for cutting tools. The recent development of complex concentrated alloys (CCAs), loosely defined as alloys without a single principal element (e.g. CoNiFeMn), offers additional opportunities in designing new alloys through extensive composition and structure modifications. Within CCAs and Co- and Ni-based superalloys, solid-solution strengthening and stacking fault energy engineering are two of the most important strengthening mechanisms. While studied for decades, the potency and quantitative materials properties of these mechanisms remain elusive. </p> <p><br></p> <p>Solid-solution strengthening originates from stress field interactions between dislocations and solute of various species in the alloy. These stress fields can be engineered by composition modification in CCAs, and therefore a wide range of alloys with promising mechanical strength may be designed. This thesis initially reports on experimental and computational validation of newly developed theories for solid-solution strengthening in 3d transition metal (MnFeCoNi) alloys. The strengthening effects of Al, Ti, V, Cr, Cu and Mo as alloying elements are quantified by coupling the Labusch-type strengthening model and experimental measurements. With large atomic misfits with the base alloy, Al, Ti, Mo, and Cr present strong strengthening effects comparable to other Cantor alloys. </p> <p> </p> <p>Stacking fault energy engineering can enable novel deformation mechanisms and exceptional strength in face-centered cubic (FCC) materials such as austenitic TRIP/TWIP steels and CoNi-based superalloys exhibiting local phase transformation strengthening via Suzuki segregation. We employed first-principles calculations to investigate the Suzuki segregation and stacking fault energy of the FCC Co-Ni binary alloys at finite temperatures and concentrations. We quantitatively predicted the Co segregation in the innermost plane of the intrinsic stacking fault (ISF). We further quantified the decrease of stacking fault energy due to segregation.  </p> <p><br></p> <p>We further investigated the driving force of segregation and the origin of the segregation behaviors of 3d, 4d and 5d elements in the Co- and Ni-alloys. Using first-principles calculations, we calculated the ground-state solute-ISF interaction energies and revealed the trends across the periodic table. We discussed the relationships between the interaction energies and the local lattice distortions, charge density redistribution, density of states and local magnetization of the solutes. </p> <p><br></p> <p>Finally, this thesis reports on new methodologies to accelerate first-principles calculations utilizing active learning techniques, such as Bayesian optimization, to efficiently search for the ground-state energy line of the system with limited computational resources. Based on the expected improvement method, new acquisition strategies were developed and will be compared and presented. </p>