Magnetocaloric Materials

Stinus Jeppesen

    Research output: Book/ReportPh.D. thesisResearch

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    New and improved magnetocaloric materials are one of the cornerstones in the development of room temperature magnetic refrigeration. Magnetic refrigeration has been used since the 1930's in cryogenic applications, but has since the discovery of room temperature refrigerants received enormous attention. This Ph.D. work has been mainly concerned with developing a new technique to characterize the magnetocaloric effect (MCE) and using this technique in the investigations on new and improved magnetocaloric materials. For this purpose a novel differential scanning calorimeter (DSC) with applied magnetic fields was developed for measuring heat capacity as function of magnetic field. Measurements using the developed DSC demonstrate a very high sensitivity, fast measurements and good agreement with results obtained by other techniques. Furthermore, two material systems have been described in this work. Both systems take basis in the mixed-valence manganite system La1-xCaxMnO3 well known from research on colossal magnetoresistance (CMR). The mixed-valence manganite crystallizes in the perovskite structure of general formula ABO3. The first material system is designed to investigate the influence of low level Cu doping on the B-site. Six different samples were prepared with over-stoichiometric compositions La0.67Ca0.33Mn1.05CuxO3, x=0, 1, 2, 3, 4 and 5%. All compositions crystallized well in the same perovskite structure, but the morphology of the samples changed drastically with doping. Investigation on the magnetocaloric properties revealed that small levels of Cu up to around 3% could improve the magnetocaloric performance of the materials. Furthermore, Cu could be used to tune the temperature interval without deteriorating the MCE, which is a much desired characteristic for potential use in magnetic refrigerators. A less comprehensive part of the work has been concerned with the investigation of doping on the A-site in the structure. The possibility of substituting the lanthanum content of the material with a lanthanide mix (Ln) consisting of La, Ce, Nd and Pr was investigated due to the potential of making more cost-effective materials. Four samples with compositions (La1-xLnx)0.67Ca0.33Mn1.05O3 with x=0, 0.33, 0.67 and 1.00, were synthesized to investigate the effect on the magnetocaloric properties. It was found that the perovskite structure could be maintained even at the highest level of doping (x=1.00), and that the maximum magnetic entropy change, ΔSM, quantifying the magnetocaloric effect was actually enhanced to an optimum at x=0.67. Furthermore, the relative cooling power (RCP) was calculated for this series, and it was demonstrated that RCP increases continuously with doping and reaches the highest value in the composition, where the entire lanthanum content has been replaced by the lanthanide mix. These observations make promise of compositions, which could be competitive both in terms of cost-effectiveness and MCE. The work on the latter materials have been disclosed in a US and UK patent application.
    Original languageEnglish
    Place of PublicationRoskilde
    PublisherRisø National Laboratory for Sustainable Energy
    Number of pages179
    ISBN (Print)978-87-550-3706-9
    Publication statusPublished - Oct 2008


    • Magnetic refrigeration
    • Fuel Cells and hydrogen
    • Risø-PhD-43(EN)
    • Risø-PhD-43
    • Risø-PhD-0043


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