Fries, Maximilian (2017)
Phase transitions of borides and phosphides for application in magnetic energy conversion.
Technische Universität Darmstadt
Ph.D. Thesis, Primary publication
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Item Type: | Ph.D. Thesis | ||||
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Type of entry: | Primary publication | ||||
Title: | Phase transitions of borides and phosphides for application in magnetic energy conversion | ||||
Language: | English | ||||
Referees: | Gutfleisch, Prof. Dr. Oliver ; Cohen, Prof. Dr. Lesley | ||||
Date: | 2017 | ||||
Place of Publication: | Darmstadt | ||||
Date of oral examination: | 17 July 2017 | ||||
Abstract: | Thermomagnetic energy conversion promises to be an energy efficient way of converting sources of energy needed in our modern society. For this purpose three different magnetocaloric material classes namely iron and manganese base monoborides, Co2B and Fe2P based materials are discussed in terms of their structural, magnetic and thermomagnetic properties and evaluated for their viability in a thermomagnetic power conversion device. The class of transition metal monoborides based on Fe and Mn is proposed for potential use in a thermomagnetic generator based on experimental and theoretical findings. Especially the system MnB exhibits a sharp, hysteresis-free, second-order magnetic phase transition resulting in a large isothermal entropy change ΔSt in moderate magnetic fields. The second-order nature of the phase transition in MnB and FeB was validated by temperature dependent neutron diffraction. The tunability of the transition temperature Tt was demonstrated by gradual doping of Co and Fe in the system Mn1−xFe/CoxB. The high magnetization change in a small temperature interval together with the hysteresis free second-order magnetic phase transition makes MnB a very interesting candidate for thermomagnetic power conversion. The magnetic properties of Co2B, including spin reorientation and magnetocrystalline anisotropy, are discussed based on measurements on high quality single crystals. Additionally, the negative impact of magnetocrystalline anisotropy is studied by means of calculations of ΔSt and measurements of the adi- abatic temperature change ΔTad; then a simple phenomenological model is proposed. The structural and magnetic properties of Co2−xMnxB are studied and it was found that both magnetization Ms and Curie temperature TC rise with doping small amounts of Mn and eventually drop with increasing the Mn content above x=0.3 allowing for tuning of T C to room temperature. The possible non-magnetic Mn-Mn interaction with increasing Mn content leads to a lowering of Ms rendering the system Co2−xMnxB impractical for magnetocaloric energy conversion both due to a low performance and the criticality and high price of Co. Microstructural and thermomagnetic properties of Mn-Fe-P-Si, Fe2P-type alloys, revealed that the cubic Heusler-like secondary phase occurring in the system has a large influence on the magnetic and thermomagnetic properties as it alters the composition of the main phase significantly. The origin of the secondary phase could be traced by EBSD measurements and is ascribed to a cubic high temperature Fe2P-phase. Furthermore, the effect of the metal to non-metal (M/NM) ratio on the sharpness of the phase transition is discussed by comparing different single-phase samples with different M/NM ratios. It could also be shown that all samples are highly porous and brittle when prepared with the powder-metallurgical method commonly proposed in literature, making them unsuitable for a direct application in a magnetocaloric heat exchanger. Additionally, by temperature dependent light microscopy the embrittlement of the sample while passing through the virgin effect could directly be observed which is related to internal stresses accumulating in the material when being cooled down through the structural magnetic phase transition for the first time after preparation. This observation is supported by measurements of single particles revealing that the virgin effect vanishes if particles are as small as the single grain size. By measuring ΔTad under different field application rates it could be shown that the phase transformation in these types of alloys is field-rate dependent, contrary to the literature, resulting in a growing field-hysteresis. Furthermore, it could be demonstrated that hydrostatic pressure only has little effect on the transition temperature due the anisotropic lattice change resulting in small volume change of the material. Overall it could be shown that the Fe2P-type alloys are comparable in thermomagnetic performance to La-Fe-Si-based magnetocaloric alloys and can be considered as one of the most commercially viable materials. In summary MnB was proposed as a new and promising material for thermomagnetic power conversion. Additionally, a method of improving the efficiency of thermomagnetic materials by orienting them with their magnetic easy axis parallel to the applied field was demonstrated. Furthermore, a pathway for preparing Fe2P alloys of highest quality was established. |
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URN: | urn:nbn:de:tuda-tuprints-67865 | ||||
Classification DDC: | 500 Science and mathematics > 500 Science 500 Science and mathematics > 530 Physics 500 Science and mathematics > 540 Chemistry 600 Technology, medicine, applied sciences > 620 Engineering and machine engineering |
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Divisions: | 11 Department of Materials and Earth Sciences > Material Science > Functional Materials | ||||
Date Deposited: | 06 Oct 2017 07:37 | ||||
Last Modified: | 09 Jul 2020 01:51 | ||||
URI: | https://tuprints.ulb.tu-darmstadt.de/id/eprint/6786 | ||||
PPN: | 417600461 | ||||
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