EXPRESS: Two-Trace Two-Dimensional Correlation Spectroscopy (2T2D-COS) Study of the Crystallization Behavior of Bioplastics

A pair of ATR IR spectra obtained during the crystallization of bioplastic copolymer poly[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyhexanoate] or PHBHx from the melt by spontaneous cooling were examined using the two-trace two-dimensional correlation spectroscopy (2T2D-COS) analysis. Unlike conventional difference spectra, 2T2D spectra showed unexpected details for the patterns of spectral intensity changes, clearly revealing the existence of two distinct populations of crystalline contributions, attributed to the well-ordered primary crystals and the less ordered secondary crystals, in addition to the amorphous component. The 2T2D spectrum sorts out highly overlapped bands associated with different constituents of the system, based on the fundamental properties and constraint imposed on a pair of spectra. Hetero-mode asynchronous 2T2D correlation analysis between the congested CH-stretching region and better resolved carbonyl-stretching region further indicates that the increase in the intensities of certain methyl and methylene bands during the crystallization process is mostly associated with the growth of the well-ordered primary crystals of PHBHx instead of the formation of the secondary crystals in the confined inter-lamellar space.

Petrofabric and geochemical features of ultramafic rocks on the example of restite metamorphites of the Kuznetsk Alatau (Western Siberia), olivine cumulates of the Yoko-Dovyren layered massif (Northern Cisbaikalia) and their analogues from ultrabasic xenoliths of the Canary Islands (Spain)

The article presents the results of petrostructural and mineralogical studies of olivine grains from ultrabasic and basic rocks of different genesis. In particular, they correspond to cumulative dunites of the Yoko-Dovyren layered massif (Northern Cisbaikalia), restite hyperbasites of the Velvet massif (Kuznetskiy Alatau), and xenoliths of peridotites from basalts of the Canary Islands (Spain). The relationship between the petrostructural and mineralogical features of ultrabasic rocks is shown, which makes it possible to identify their cumulative and restite varieties. An important element of the petrostructure of ultrabasites is the orientation of olivine, which reflects either the conditions for the formation of primary crystals in the magmatic melt, or the conditions for its recrystallization as a result of plastic deformations during exhumation to the Earth's surface. The mineral composition of rocks is an additional feature that reflects the real conditions of formation. In the presence of basic plagioclase, it is already quite difficult to speak about the restitic nature of these ultrabasic rocks. On the other hand, plastic deformations of olivine are characteristic of restitic hyperbasites, in which plagioclase is absent. The results of mineralogical studies in ultrabasic xenoliths of the Canary Islands showed the presence of basic plagioclase (labradorite), as well as chrysolite-type olivine (12-16 Fa), which corresponds to the attributes of ultrabasic layered intrusions such as the Yoko-Dovyren dunite-troctolite-gabbro pluton. For restite hyperbasites (by the example of the Kuznetsk Alatau), the iron content of olivine does not exceed 9-10% of the fayalite end, while plagioclase and clinopyroxene are absent. A characteristic feature of the xenoliths of the Canary Islands is the presence of endiopside, which is present in layered intrusions, but is absent in the restrained fragments of the upper and lower mantle. It is assumed that the xenoliths in the basalts of the Canary Islands are not of a mantle nature, but are fragments of a deep magma chamber. The studies of the optical orientation of olivine in xenoliths of the rocks of Lanzarote Island confirm these conclusions. The geochemical parameters of ultramafic xenoliths on Tenerife Island may well correspond to deeper formations.

Features of structure formation in Al–Fe–Mn alloy during crystallization at different cooling rates

The paper studies specific features of the Al–2.5%Fe–1.5%Mn alloy microstructure formation depending on the cooling rate during casting and laser melting. As-cast microstructure analysis showed that with an increase in the cooling rate during crystallization from 0.5 to 940 K/s, the primary crystallization of the Al6(Mn,Fe) phase is almost completely suppressed with the non-equilibrium eutectic volume increasing to 43 %. The Al–2.5%Fe–1.5%Mn alloy microstructure after laser melting features by the presence of dendritic-type aluminum matrix crystals with an average cell size of 0.56 μm surrounded by an iron-manganese phase of eutectic origin with an average plate size of 0.28 μm. The primary crystallization of the Al6(Mn,Fe) phase is completely suppressed. Such a microstructure is formed at cooling rates of 1.1·104 to 2.5·104 K/s, which corresponds to the cooling rates implemented in additive technologies. Regions consisting of Al6(Mn,Fe) phase primary crystals formed by the epitaxial growth mechanism were revealed at the boundary between the track and the base metal and at the remelting boundary. The smaller the eutectic plates and dendritic cell located in the epitaxial layer, the more disperse the primary crystals in the remelting zone. The Al–2.5%Fe–1.5%Mn alloy after laser melting has high hardness at room temperature (93 HV) and good thermal stability after heating up to 300 °C (hardness slightly decreases to 85 HV), and its calculated yield strength is 227 MPa. Combined with the ultra-fine microstructure formed, high processibility during laser melting, hardness at room temperature, and high calculated yield strength, Al–2.5%Fe–1.5%Mn is a promising alloy for use in additive technologies.

To question about Fe5B3 boride formation in boron-rich Fe–В alloys

The structure of boron-rich iron alloys in the concentration range of 9.0–15.0 wt. % В, 0.01–0.17 wt. % C, Fe – the balance (with charge impurities of Si, Al, Mn) was investigated in this work. The methods of metallographic, X-ray, stop-quenching, scanning electron microscopic, energy dispersive, and fluorescent spectral analyses were applied. The FeB- and Fe2B-based solid solutions are proved to be the major constituents of the investigated alloys. No evidence is found for the possible formation of the Fe5B3 boride via peritectic reaction L+FeB→Fe5B3 at 1650 K and its further decomposition via eutectoid reaction Fe5B3→FeB+Fe2B at 1410 K. It is shown that the phase under consideration is iron hemiboride alloyed mainly by silicon which peritectically forms from primary crystals of iron monoboride and the rest of liquid at 1650 K. The thermal effect at 1410 K is assumed to be caused by a heat production connected with polymorphic transformation α-FeB→β-FeB in the presence of carbon.

Solid Fraction Examination at Flow Cessation and Flow Cessation Mechanism of Al-Si-Mg Alloy

The aim of this study is to experimentally determine the solid fraction at the cessation of the flow of a molten Al-Si-Mg alloy (JIS-AC4CH) ceases. In this study, an experimental apparatus to measure the melt temperature during flow was developed and was used to perform highly accurate temperature measurements. An immersion-type optical-fiber radiation thermometer without emissivity correction was used for the temperature measurement device in this apparatus. The solid fraction was calculated from the area of primary crystals when the molten metal at any temperature was quenched. The melt temperature at flow cessation was higher than the eutectic reaction temperature, and the solid fraction in the melt front was approximately 0.2. However, the maximum solid fraction was found at a position slightly away from the melt front toward the pouring gate, and was approximately 0.3. It was inferred for this Al-Si-Mg alloy, that the flow cessation mechanism was a mixture of skin formation and mushy formation types.

Percolation of Primary Crystals in Cell Walls of Aluminum Alloy Foam via Semi-Solid Route

Herein, a uniform aluminum alloy foam was fabricated by the addition of TiH2 as a blowing agent to Al-6.4 mass % Si in the semi-solid state and subsequent solidification. This was aimed at propounding the stabilization mechanism of the proposed foaming process. The microscopic images, which were the cross section on the center of the foam etched with Weck’s reagent, showed the primary crystals in the semi-solid state and solidifying segregation surrounding the crystals. Thus, it became evident that the area ratio of primary crystals in the semi-solid state approximately equals to the set solid fraction. According to the percolation theory for the cell wall model, the drainage in the cell walls with primary crystals above the percolation threshold was found to be inhibited. By considering that each cell wall is a flow path of the foam, the percentage of the cell walls with inhibited drainage to all the other cell walls was observed to exceed the percolation threshold of the lattice model (0.33) as per the percolation theory. Therefore, it can be concluded that the primary crystals inhibit drainage in some cell walls, ensuring that the stability of the foam is maintained.

Stabilization Mechanism of Semi-Solid Film Simulating the Cell Wall during Fabrication of Aluminum Foam

Semi-solid route is a fabrication method of aluminum foam where the melt is thickened by primary crystals. In this study, semi-solid aluminum alloy films were made to observe and evaluate the stabilization mechanism of cell walls in Semi-solid route. Each film was held at different solid fractions and holding times. In lower solid fractions, as the holding time increases, the remaining melt in the films lessens and this could be explained by Poiseuille flow. However, the decreasing tendency of the remaining melt in the films lessens as the solid fraction increases. Moreover, when the solid fraction is high, decreasing tendency was not observed. These are because at a certain moment, clogging of primary crystals occurs under the thinnest part of the film and drainage is largely suppressed. Moreover, clogging is occurring in solid fraction of 20–45% under the thinnest part of the film. Moreover, the time to occur clogging becomes earlier as the solid fraction increases.

Ultrasonic processing of aluminium alloys above the liquidus: the role of Zr

Ultrasonic melt processing (USP) is gaining quite an interest in recent years due to the benefits of this technology to the melt quality and structure refinement. A number of mechanisms have been identified that govern the effects of USP at different stages of melt processing. Technologically it is advantageous to apply USP to the fluid melt rather than to a mushy solidifying alloy. In this case heterogeneous nucleation on available or activated/multiplied substrates is the main mechanism. Among these substrates, primary crystals of Al3Zr phase were shown to be potent and effective. This paper gives a review of the own research into the role of Al3Zr in structure refinement in various groups of Al alloys, from solid-solution type to hypereutectic. This overview includes the evidence of a possible eutectic reaction between Al and Al3Zr in Al-rich alloys, mechanisms of Al3Zr formation and refinement under USP (that enables these primary crystals to be active substrates for Al and some other primary phases), the role of USP in facilitating primary solidification of Al3Zr in the Al-Zr system, and the additional benefits of solute Ti presence. The paper is illustrated with the data obtained over the last 15 years of research led by the author.

Liquidus Surface and Spinodal of Fe-B-C Alloys

In this work the study is performed for the specimens of Fe-B-C alloys with boron content of 0.005–7.0 wt. % and carbon content of 0.4–6.67 wt. %, the rest is iron. According to the findings of microstructure analysis, XRD and differential thermal analyses, the primary phases and the temperatures of their formation are determined. Depending on boron content (in the range of 1.5–8.80 wt. %) and carbon content (0.5–6.67 wt. %) in the Fe-B-C alloys, the primary phases in the process of crystallization are γ-Fe, boron cementite Fe3(CB) and boride Fe2В. The outcomes of the experiment carried out in this work determine the phase composition and phase transformations occurring in the alloys and the liquidus surface is constructed. The findings show that the liquidus temperature for Fe-B-C system alloys is low compared to binary Fe-B and Fe-C alloys. At the liquidus surface of the Fe-B-C alloys, there is a point at boron content of 2.9 wt. % and carbon content of 1.3 wt. % with the lowest temperature of 1375 K and it is the point of intersection of monovariant eutectics. This fact is in a good agreement with the results of other authors. The microstructure of alloys located at the curves of monovariant eutectics is represented by the γ–Fe+Fe2B and γ–Fe+Fe3(CB) eutectics and the primary crystals of Fe2B iron boride in the shell of Fe3(BC) boron cementite. In this paper it is shown experimentally the existence of a quasi-binary section and the coordinates of the peritectic point are fixed: the boron content is 5.0 wt. %, carbon content is 3.0 wt. % and the temperature is 1515 K. The free energy of the Fe-B-C melt is calculated for the first time by the quasi-chemical method and the surface of thermodynamic stability of the Fe-B-C melt is plotted, depending on temperature and boron and carbon content in the alloy. The results obtained in the paper show that in order to obtain a homogeneous Fe-B-C melt, which does not contain any microheterogeneous structure in the form of short-order microregions, it is necessary to perform the overheating more than to 180 K for the region where the primary phase is iron, and no less than to 200 K for the regions with boron cementite and boride.