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    <id>64078</id>
    <completedYear/>
    <publishedYear>2025</publishedYear>
    <thesisYearAccepted/>
    <language>eng</language>
    <pageFirst>18227</pageFirst>
    <pageLast>18236</pageLast>
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    <edition/>
    <issue>36</issue>
    <volume>46</volume>
    <type>article</type>
    <publisherName>American Chemical Society (ACS)</publisherName>
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    <title language="eng">Temperature-Induced Phase Transitions of Vivianite: In Situ Analysis of a Redox-Driven Crystallization</title>
    <abstract language="eng">We document a solid-state, temperature-dependent (25−700 °C), multistage redox transformation of crystalline ferrous iron phosphate, vivianite (Fe3(PO4)2·8H2O). Under anoxic conditions, vivianite breaks down at T &gt; 250 °C into an anhydrous, amorphous intermediate Fe3(PO4)2 phase, yet the bulk shape and morphology of the  starting vivianite crystals were retained. This amorphous intermediate phase remained stable until T &gt; 500 °C, after which a redox-dependent crystallization into two different minerals was observed. Under anoxic conditions, the amorphous ferrous intermediate (Fe3(PO4)2) transformed into the crystalline ferrous phosphate (graftonite, (Fe2+)3(PO4)2), while under oxic conditions it crystallized into a ferric phosphate (rodolicoite, Fe3+PO4). Graftonite formation occurs via an exothermic molar enthalpy (ΔHcryst) of −16.7 ± 0.2 kJ mol−1. Rietveld refinements of the two crystalline endmembers (vivianite and graftonite) revealed a unit cell volume decrease of ∼3.1% during the transformation, which was observed by in situ electron microscopic observations as an overall shrinking of the initial vivianite crystals. Despite volume loss and bubble-like features, the original vivianite shape was preserved, indicating a solid-state pseudomorphic transformation. Ex situ XRD and TEM-EELS analyses confirmed the ferrous-to-ferric oxidation, forming rodolicoite, through changes in the Fe geometry and oxidation state.</abstract>
    <parentTitle language="eng">Inorganic Chemistry</parentTitle>
    <identifier type="issn">0020-1669</identifier>
    <identifier type="doi">10.1021/acs.inorgchem.5c02399</identifier>
    <identifier type="urn">urn:nbn:de:kobv:b43-640782</identifier>
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    <enrichment key="date_peer_review">16.09.2025</enrichment>
    <licence>Creative Commons - CC BY - Namensnennung 4.0 International</licence>
    <author>Alice Paskin</author>
    <author>Thaïs Couasnon</author>
    <author>Roberts Blukis</author>
    <author>Jeffrey Paulo H. Perez</author>
    <author>Stefan Reinsch</author>
    <author>Vladimir Roddatis</author>
    <author>Marcin Syczewski</author>
    <author>Liane G. Benning</author>
    <subject>
      <language>eng</language>
      <type>uncontrolled</type>
      <value>Vivianite</value>
    </subject>
    <subject>
      <language>eng</language>
      <type>uncontrolled</type>
      <value>Graftonite</value>
    </subject>
    <subject>
      <language>eng</language>
      <type>uncontrolled</type>
      <value>Crystallization enthalpy</value>
    </subject>
    <subject>
      <language>eng</language>
      <type>uncontrolled</type>
      <value>Ferrous phosphates</value>
    </subject>
    <collection role="ddc" number="620">Ingenieurwissenschaften und zugeordnete Tätigkeiten</collection>
    <collection role="institutes" number="">5 Werkstofftechnik</collection>
    <collection role="institutes" number="">5.6 Glas</collection>
    <collection role="themenfelder" number="">Material</collection>
    <collection role="themenfelder" number="">Degradationsmechanismen</collection>
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    <collection role="fulltextaccess" number="">Datei für die Öffentlichkeit verfügbar ("Open Access")</collection>
    <collection role="unnumberedseries" number="">Wissenschaftliche Artikel der BAM</collection>
    <thesisPublisher>Bundesanstalt für Materialforschung und -prüfung (BAM)</thesisPublisher>
    <file>https://opus4.kobv.de/opus4-bam/files/64078/2025_Paskin-et-al_temperature-induced-phase-transitions-of-vivianite.pdf</file>
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