4.7 Article

Preparation and characterization of ferrous oxalate cement-A novel acid-base cement

Journal

JOURNAL OF THE AMERICAN CERAMIC SOCIETY
Volume 104, Issue 2, Pages 1120-1131

Publisher

WILEY
DOI: 10.1111/jace.17511

Keywords

copper slag; ferrous oxalate cement; oxalic acid; reaction mechanism; setting; strength

Funding

  1. Missouri University of Science and Technology
  2. National Natural Science Foundation of China [51662024, 21866018]
  3. Kunming University of Science and Technology [KKSY201605021]
  4. Yunnan Ten Thousand Talents Plan Young & Elite Talents Project [YNWR-QNBJ-2018-388]

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This study investigates the influence of precursor proportions on the setting behavior and compressive strength of Ferrous oxalate cement (FOC) paste. The optimal conditions were found to yield high compressive strength values, while extending the setting time by adding borax. Iron oxalate hydrate was identified as the exclusive hydration product of FOC, due to the chemical reaction between iron-rich copper slag and oxalic acid solution.
Ferrous oxalate cement (FOC), a new type of acid-base cement, is prepared at room temperature through reactions between iron-rich copper slag (CS) and oxalic acid (OA). In this work, the influences of precursor proportions, including the copper slag-to-oxalic acid mass ratio (CS/OA), borax-to-cement mass ratio (B/C), and water-to-cement mass ratio (W/C), on the setting behavior and compressive strength of FOC paste are investigated. Furthermore, the evolutions of pH and ions concentrations are traced to understand the reaction mechanism of FOC. The results show that the compressive strength decreases with an increase in W/C; when W/C is fixed, with an increase in CS/OA, the compressive strength first increases and then decreases, giving an optimal value. The compressive strengths of specimens at 3, 7, and 28 days can reach 33, 41, and 55 MPa, respectively, under the optimal conditions (CS/OA = 3.6, B/C = 0.03, and W/C = 0.18). The setting time is also a function of W/C and CS/OA, and can be extended by adding borax. Iron oxalate hydrate (FeC2O4 center dot 2H(2)O) has been identified as the exclusive hydration product of FOC due to the chemical reaction between Fe(2)SiO(4)or Fe(3)O(4)contained in CS and OA solution. At the initial stage of reaction, OA is dissolved to release protons, HC(2)O(4)(-)and C2O42-, which facilitate the dissolution of Fe(2)SiO(4)and Fe(3)O(4)and the release of Fe(2+)in the aqueous phase. Then the Fe(2+)ions combine with HC(2)O(4)(-)and C(2)O(4)(2-)to precipitate FeC2O4 center dot 2H(2)O, acting as the cementitious phase to bond the unreacted CS particles.

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