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	<front>
		<journal-meta>
			<journal-id journal-id-type="publisher-id">MC</journal-id>
			<journal-title-group>
				<journal-title>Materiales de Construcci&#xf3;n</journal-title>
				<abbrev-journal-title abbrev-type="publisher">Mater. construcc.</abbrev-journal-title>
			</journal-title-group>
			<issn publication-format="electronic">1988-3226</issn>
			<issn-l>0465-2746</issn-l>
			<publisher>
				<publisher-name>Consejo Superior de Investigaciones Cient&#xed;ficas</publisher-name>
			</publisher>
		</journal-meta>
		<article-meta>
			<article-id pub-id-type="publisher-id">mc.2023.298122</article-id>
			<article-id pub-id-type="doi">10.3989/mc.2023.298122</article-id>
			<article-categories>
				<subj-group subj-group-type="heading">
					<subject>Art&#xed;culos</subject>
				</subj-group>
			</article-categories>
			<title-group>
				<article-title>Development of magnesium/calcium oxalate cements</article-title>
				<trans-title-group xml:lang="es">
					<trans-title>Desarrollo de cementos de oxalato de magnesio/calcio</trans-title>
				</trans-title-group>
			</title-group>
			<contrib-group>
				<contrib contrib-type="author" corresp="yes">
					<contrib-id contrib-id-type="orcid">https://orcid.org/0000-0003-2922-5521</contrib-id>
					<name>
						<surname>Bilginer</surname>
						<given-names>B.A.</given-names>
					</name>
					<role content-type="http://credit.niso.org/contributor-roles/investigation/">Investigation</role>
					<role content-type="http://credit.niso.org/contributor-roles/methodology/">Methodology</role> 
					<role content-type="http://credit.niso.org/contributor-roles/writing-original-draft/">Writing, original draft</role> 
					<role content-type="http://credit.niso.org/contributor-roles/writing-review-editing/">Writing, review &amp; editing</role>
					<email xlink:href="aykutb@metu.edu.tr">aykutb@metu.edu.tr</email>
					<aff id="aff1"><institution content-type="department">Dept. of Civil Engineering</institution>, <institution content-type="university">Middle East Technical University (METU)</institution>, (<addr-line>Ankara</addr-line>, <country>Turkey</country>)</aff>
				</contrib>
				<contrib contrib-type="author">
					<contrib-id contrib-id-type="orcid">https://orcid.org/0000-0003-0769-1249</contrib-id>
					<name>
						<surname>Erdo&#x11f;an</surname>
						<given-names>S.T.</given-names>
					</name>
					<role content-type="http://credit.niso.org/contributor-roles/conceptualization/">Conceptualization</role> 
					<role content-type="http://credit.niso.org/contributor-roles/investigation/">Investigation</role>
					<role content-type="http://credit.niso.org/contributor-roles/methodology/">Methodology</role> 
					<role content-type="http://credit.niso.org/contributor-roles/supervision/">Supervision</role> 
					<role content-type="http://credit.niso.org/contributor-roles/writing-original-draft/">Writing, original draft</role> 
					<role content-type="http://credit.niso.org/contributor-roles/writing-review-editing/">Writing, review &amp; editing</role>
					<aff id="aff2"><institution content-type="department">Dept. of Civil Engineering</institution>, <institution content-type="university">Middle East Technical University (METU)</institution>, (<addr-line>Ankara</addr-line>, <country>Turkey</country>)</aff>
				</contrib>
			</contrib-group>
			<pub-date pub-type="epub">
				<day>02</day>
				<month>04</month>
				<year>2023</year>
			</pub-date>
			<pub-date pub-type="collection">
				<month>06</month>
				<year>2023</year>
			</pub-date>
			<volume>72</volume>
			<issue>350</issue>
			<elocation-id>e310</elocation-id>
			<history>
				<date date-type="received">
					<day>19</day>
					<month>07</month>
					<year>2022</year>
				</date>
				<date date-type="accepted">
					<day>18</day>
					<month>01</month>
					<year>2023</year>
				</date>
				<date date-type="pub">
					<day>11</day>
					<month>04</month>
					<year>2023</year>
				</date>
			</history>
			<permissions>
				<copyright-statement>&#xa9;2023 CSIC</copyright-statement>
				<copyright-year>2023</copyright-year>
				<license license-type="open-access" xlink:href="https://creativecommons.org/licenses/by/4.0/">
					<license-p>This is an open-access article distributed under the terms of the Creative Commons Attribution 4.0 International (CC BY 4.0) License.</license-p>
				</license>
			</permissions>
			<self-uri xlink:href="http://materconstrucc.revistas.csic.es/index.php/materconstrucc/article/view/XXXX/XXXX"/>
			<abstract>
				<title>Abstract</title>
				<p>Magnesium oxalate cement, a novel alternative to portland cement, can be made at room temperature by reacting dead-burned magnesia and salts of oxalic acid. Since oxalic acid can be made using captured carbon dioxide, oxalate cements may even be carbon negative. However, emissions related with the decarbonation of magnesite at high temperatures make this hard to achieve. This study investigates the effect of replacing magnesia with granulated blast furnace slag on some physical and mechanical properties, as well as the mineralogy and microstructure of oxalate cements. Whewellite and Weddellite are identified when slag is used, in addition to Glushinskite which forms from magnesia. Slag-only mortars undergo faster but less complete reactions and show lower resistance to water than their magnesium oxalate counterparts. An equal-part combination of dead-burned magnesia and slag gives the highest 28-d strength (&gt; 35 MPa), pH~7, and high water resistance.</p>
			</abstract>
			<trans-abstract xml:lang="es">
				<title>Resumen</title>
				<p>El cemento de oxalato de magnesio, una alternativa novedosa al cemento portland, puede fabricarse a temperatura ambiente haciendo reaccionar magnesia calcinada y sales de &#xe1;cido ox&#xe1;lico. Dado que el &#xe1;cido ox&#xe1;lico se puede fabricar utilizando di&#xf3;xido de carbono capturado, los cementos de oxalato pueden incluso tener una huella de carbono negativa. Sin embargo, las emisiones relacionadas con la descarbonataci&#xf3;n de la magnesita a altas temperaturas dificultan su consecuci&#xf3;n. Este estudio investiga el efecto de reemplazar la magnesia con escoria granulada de alto horno en algunas propiedades f&#xed;sicas y mec&#xe1;nicas, as&#xed; como en la mineralog&#xed;a y la microestructura de los cementos de oxalato. Whewellite y Weddellite se identifican cuando se utiliza escoria, adem&#xe1;s de Glushinskite que se forma a partir de magnesia. Los morteros solo con escoria experimentan reacciones m&#xe1;s r&#xe1;pidas, pero menos completas y muestran una menor resistencia al agua que los correspondientes de oxalato de magnesio. Una combinaci&#xf3;n a partes iguales de magnesia calcinada y escoria proporciona la mayor resistencia a 28 d&#xed;as (&gt; 35 MPa), pH~7 y alta resistencia al agua.</p>
			</trans-abstract>
			<kwd-group>
				<kwd>Cement</kwd>
				<kwd>Oxalate</kwd>
				<kwd>Slag</kwd>
				<kwd>Magnesia</kwd>
				<kwd>Carbon dioxide</kwd>
			</kwd-group>
			<kwd-group xml:lang="es">
				<kwd>Cemento</kwd>
				<kwd>Oxalato</kwd>
				<kwd>Escoria</kwd>
				<kwd>Magnesio</kwd>
				<kwd>Di&#xf3;xido de carbono</kwd>
			</kwd-group>
			<counts>
				<fig-count count="12"/>
				<table-count count="4"/>
				<equation-count count="7"/>
				<ref-count count="68"/>
				<page-count count="18"/>
			</counts>
		</article-meta>
	</front>
	<body>
		<sec id="sec1" sec-type="intro">
			<label>1.</label>
			<title>Introduction</title>
			<p>Portland cement (PC), the ubiquitous construction binder, has a considerable environmental impact. Despite its many excellent technical properties (<xref ref-type="bibr" rid="B1">1</xref>), its high carbon footprint and embodied energy have led to an ongoing search for lower-environmental-impact alternative binders (<xref ref-type="bibr" rid="B2 B3 B4 B5 B6 B7 B8 B9 B10">2-10</xref>). Many of these systems are low-carbon in comparison to PC but not carbon-neutral or negative, or require higher-than-room temperature curing, or sequester carbon into a prefabricated block, limiting versatility (<xref ref-type="bibr" rid="B11 B12 B13 B14">11-14</xref>). A carbon-neutral/negative yet practical binder needs to use a low-cost, powder with a low carbon footprint, to be able to trap large amounts of CO<sub>2</sub>, to be cast on site, and yield a reaction product with sufficient physical and mechanical properties. Recent studies (<xref ref-type="bibr" rid="B15 B16 B17 B18">15-18</xref>) have proposed magnesium oxalate cement (MgOx) as a new alternative to PC. MgOx is an acid-base cement, similar to the well-known magnesium phosphate cements (MPC) (<xref ref-type="bibr" rid="B19 B20 B21 B22">19-22</xref>). MPCs are made by reacting salts of phosphoric acid, like KH<sub>2</sub>PO<sub>4</sub>, with dead-burned MgO, and possess useful properties such as rapid setting, high early and ultimate strength, the ability to set and harden at very low temperatures, low shrinkage, high abrasion resistance, etc. (<xref ref-type="bibr" rid="B23">23</xref>). The acid-base neutralization results in a paste with near-neutral pH. These properties lend MPCs to diverse fields like biomaterials, toxic waste stabilization, and concrete repair (<xref ref-type="bibr" rid="B24 B25 B26">24-26</xref>). MgOx relies on acid-base reactions between oxalic acid salts and dead-burned MgO. Oxalic acid (C<sub>2</sub>H<sub>2</sub>O<sub>4</sub>) is a multi-carbon chemical that is relatively easy to obtain from captured CO<sub>2</sub> (<xref ref-type="bibr" rid="B27 B28 B29 B30 B31 B32 B33">27-33</xref>). Schuler et al. (<xref ref-type="bibr" rid="B34">34</xref>) compared many methods to produce oxalic acid (H<sub>2</sub>C<sub>2</sub>O<sub>4</sub>) or oxalate (C<sub>2</sub>O<sub>4</sub>
				<sup>2-</sup>). Over ten of these methods started with CO<sub>2</sub> and were assessed, using green chemistry principles, as being among the most sustainable paths to oxalic acid. The &#x201c;CO<sub>2</sub> equivalent&#x201d;/cation is 2/1 (molar) in Ca- and Mg-oxalates. This is higher than the 1/1 ratio in Ca/Mg carbonates allowing greater amounts of CO<sub>2</sub> to be bound, and a low-carbon cement to be achieved. Ca- and Mg- oxalates also show low solubility in water (<xref ref-type="bibr" rid="B35">35</xref>). Calcium phosphate cements are widely reported, mainly as biomaterials. The precipitation of calcium oxalate crystals (CaOx) has been studied widely as they form the most prevalent type of kidney stones (<xref ref-type="bibr" rid="B36">36</xref>). CaOx precipitation can also be used for water proofing portland cement concrete by forming a thin surface film or by filling pores (<xref ref-type="bibr" rid="B37">37</xref>, <xref ref-type="bibr" rid="B38">38</xref>). However, there are no accounts of calcium oxalate cements. Ca analogues of MgOx, such as those made with hydrated lime as the basic powder, can also set and harden, but high water demand and dimensional stability issues lead to high porosity and low strength. MgOx are rapid setting, can reach medium-to-high ultimate strength, and are water-resistant (<xref ref-type="bibr" rid="B15">15</xref>). However, like MPCs, they use dead-burned MgO. Since low-cost MgO is typically obtained by decarbonating MgCO<sub>3</sub> and burning MgO at ~1500 &#xb0;C leads to significant fuel-related emissions, MgOx cements can be made low carbon but not carbon negative (<xref ref-type="bibr" rid="B15">15</xref>). Replacement of dead-burned MgO with a less carbon-intense waste or natural material is needed to further decrease the carbon footprint of oxalate cements. Luo et al. (<xref ref-type="bibr" rid="B39">39</xref>) recently reported a ferrous oxalate cement paste made with copper slag and oxalic acid. Medium to high compressive strengths were measured on 2 cm cube paste specimens but water resistance or reaction temperatures of the pastes were not reported. Various studies on MPCs have found that dead burned MgO can be replaced with up to 50 % industrial byproducts such blast furnace slag, steel slag, red mud, or fly ash, without negative effects on mechanical properties and/or water resistance (<xref ref-type="bibr" rid="B40 B41 B42 B43">40-43</xref>). This study attempts to partially or fully replace dead-burned MgO with ground granulated blast furnace slag, as an alkaline powder with a low carbon footprint and low cost.</p>
		</sec>
		<sec id="sec2" sec-type="materials|methods">
			<label>2.</label>
			<title>Materials and methods</title>
			<sec id="sec2.1">
				<label>2.1.</label>
				<title>Materials</title>
				<p>Low-grade magnesia (MgO) was purchased in powder form. As this powder dissolves too quickly in an acidic solution, it was calcined for 1 h at 1500 &#xb0;C to obtain dead-burned magnesia (MgO1500) (<xref ref-type="bibr" rid="B44">44</xref>). After calcination, the hard mass obtained was ground to a powder. Ground granulated blast furnace slag (GGBFS) was received, in powder form, from Kardemir Iron and Steel Plant in Karab&#xfc;k, Turkey. The magnesia and slag were used as the alkaline component of the acid-base mixtures. The fly ash (FA) used was received from Af&#x15f;in-Elbistan Thermal Power Plant in Turkey. Technical grade oxalic acid dihydrate (OxAc) was received from Balmumcu Chemical Industries in Ankara, Turkey. Reagent grade borax, Na<sub>2</sub>B<sub>4</sub>O<sub>7</sub>&#xb7;10H<sub>2</sub>O (Merck), was also used, as a set retarder. The oxide compositions of the main ingredients (MgO, MgO1500, FA, and GGBFS) determined using X-ray fluorescence spectrometry (XRF, Rigaku ZSX Primus), are provided in <xref ref-type="table" rid="t1">Table 1</xref>.</p>
				<table-wrap id="t1">
					<label>Table 1</label>
					<caption>
						<title>Oxide composition and density of the main ingredients.</title>
					</caption>
					<table>
						<colgroup>
							<col/>
							<col/>
							<col/>
							<col/>
							<col/>
						</colgroup>
						<thead>
							<tr>
								<th align="justify" rowspan="2">Oxide</th>
								<th align="center" colspan="4">Mass (%) </th>
							</tr>
							<tr>
								<th align="center">MgO</th>
								<th align="center">MgO1500</th>
								<th align="center">FA</th>
								<th align="center">GGBFS</th>
							</tr>
						</thead>
						<tbody>
							<tr>
								<td align="justify">MgO</td>
								<td align="center">81.30</td>
								<td align="center">82.80</td>
								<td align="center">2.26</td>
								<td align="center">5.90</td>
							</tr>
							<tr>
								<td align="justify">SiO<sub>2</sub>
								</td>
								<td align="center">9.35</td>
								<td align="center">10.60</td>
								<td align="center">40.09</td>
								<td align="center">39.70</td>
							</tr>
							<tr>
								<td align="justify">CaO</td>
								<td align="center">1.74</td>
								<td align="center">1.85</td>
								<td align="center">21.24</td>
								<td align="center">36.90</td>
							</tr>
							<tr>
								<td align="justify">Al<sub>2</sub>O<sub>3</sub>
								</td>
								<td align="center">0.06</td>
								<td align="center">0.08</td>
								<td align="center">16.24</td>
								<td align="center">10.50</td>
							</tr>
							<tr>
								<td align="justify">Fe<sub>2</sub>O<sub>3</sub>
								</td>
								<td align="center">0.60</td>
								<td align="center">0.72</td>
								<td align="center">7.21</td>
								<td align="center">1.10</td>
							</tr>
							<tr>
								<td align="justify">CO<sub>2</sub>
								</td>
								<td align="center">6.89</td>
								<td align="center">3.82</td>
								<td align="center">-</td>
								<td align="center">-</td>
							</tr>
							<tr>
								<td align="justify">NiO</td>
								<td align="center">0.12</td>
								<td align="center">0.13</td>
								<td align="center">-</td>
								<td align="center">-</td>
							</tr>
							<tr>
								<td align="justify">SO<sub>3</sub>
								</td>
								<td align="center">-</td>
								<td align="center">-</td>
								<td align="center">6.71</td>
								<td align="center">1.20</td>
							</tr>
							<tr>
								<td align="justify">TiO<sub>2</sub>
								</td>
								<td align="center">-</td>
								<td align="center">-</td>
								<td align="center">0.77</td>
								<td align="center">0.68</td>
							</tr>
							<tr>
								<td align="justify">P<sub>2</sub>O<sub>5</sub>
								</td>
								<td align="center">-</td>
								<td align="center">-</td>
								<td align="center">0.40</td>
								<td align="center">0.01</td>
							</tr>
							<tr>
								<td align="justify">K<sub>2</sub>O</td>
								<td align="center">-</td>
								<td align="center">-</td>
								<td align="center">1.33</td>
								<td align="center">0.78</td>
							</tr>
							<tr>
								<td align="justify">MnO</td>
								<td align="center">-</td>
								<td align="center">-</td>
								<td align="center">-</td>
								<td align="center">2.20</td>
							</tr>
							<tr>
								<td align="justify">Density (g/cm<sup>3</sup>)</td>
								<td align="center">3.10</td>
								<td align="center">3.40</td>
								<td align="center">2.00</td>
								<td align="center">3.00</td>
							</tr>
							<tr>
								<td align="justify">Loss on ignition (%)</td>
								<td align="center">8.0</td>
								<td align="center">0</td>
								<td align="center">4.0</td>
								<td align="center">0.5</td>
							</tr>
							<tr>
								<td align="justify">Blaine Fineness (cm<sup>2</sup>/g)</td>
								<td align="center">10000</td>
								<td align="center">2000</td>
								<td align="center">3300</td>
								<td align="center">4100</td>
							</tr>
						</tbody>
					</table>
				</table-wrap>
				<p>As expected, calcination does not greatly affect the oxide composition of the magnesia but mainly decreases the measured CO<sub>2</sub> content. Loss on ignition measurements parallel this loss upon calcination. Nevertheless, MgO1500 still contains some CO<sub>2</sub>. This could be due to some organic impurities in the as-received magnesia forming carbon upon calcination or due to problems with detecting/measuring the lightweight (and low x-ray fluorescence yield) element carbon with semi-quantitative XRF.</p>
				<p>The fly ash is &#x201c;high-lime&#x201d; as per ASTM C 618 (45) with ~21 % CaO and &gt; 50 % SiO<sub>2</sub>+Fe<sub>2</sub>O<sub>3</sub>+Al<sub>2</sub>O<sub>3</sub>. More than 3 million tons/year of this ash are produced, and its high SO<sub>3</sub> content makes it unsuitable for use as a pozzolan in PC systems. The slag is &#x201c;hydraulically active&#x201d; with (CaO + MgO) / SiO<sub>2</sub> &gt; 1.0, as per EN 197-1 (<xref ref-type="bibr" rid="B46">46</xref>). The fly ash was used to produce a low-cost intermediate oxalic acid salt (FAOx), analogous to KH<sub>2</sub>PO<sub>4</sub> used in magnesium phosphate cements. It was used to provide oxalate ions to the system in a controlled fashion. <xref ref-type="fig" rid="f1">Figure 1</xref> summarizes the production method for FAOx.</p>
				<fig id="f1">
					<label>Figure 1</label>
					<caption>
						<title>The production of FAOx.</title>
					</caption>
					<graphic id="gra-1" xlink:href="MC-72-350-e310-gf1.png"/>
				</fig>
				<p>FA:OxAc:water are mixed at 1.0:1.5:1.0 by mass as in (<xref ref-type="bibr" rid="B15">15</xref>). The resulting paste heats up and within minutes sets into a strong but water-soluble solid. The paste is oven-dried at 105 &#xb0;C for 24 h, crushed, and then ground for 45 min in a laboratory ball mill to obtain a powder. The specific gravity of FAOx was measured as 1.96. <xref ref-type="fig" rid="f2">Figure 2</xref> shows the mineralogies of the raw materials and FAOx, determined using x-ray powder diffraction (XRD). Periclase is the main phase in MgO1500 with major peaks at ~42.5 and ~37 &#xba;2&#x3b8;. Forsterite (Mg<sub>2</sub>SiO<sub>4</sub>) is formed by the solid-state reaction of MgO and SiO<sub>2</sub> at high temperatures (<xref ref-type="bibr" rid="B47">47</xref>). FAOx shows peaks for whewellite (~24 &#xba;2&#x3b8;) and quartz (~27 &#xba;2&#x3b8;). Whewellite (CaC<sub>2</sub>O<sub>4</sub>&#xb7;H<sub>2</sub>O) is a calcium oxalate formed by calcium in the FA used and oxalic acid. Quartz carries from the fly ash itself. The slag is amorphous, with a characteristic hump around ~30 &#xba;2&#x3b8;.</p>
				<fig id="f2">
					<label>Figure 2</label>
					<caption>
						<title>X-ray diffractograms of:</title>
						<p>a) the alkaline materials; b) the acid salt FAOx and the raw materials used to produce it.</p>
					</caption>
					<graphic id="gra-2" xlink:href="MC-72-350-e310-gf2.png"/>
				</fig>
				<p>The particle size distributions for MgO1500, slag, and FAOx were measured using laser diffraction (Malvern Mastersizer 2000) on dry powders (<xref ref-type="fig" rid="f3">Figure 3</xref>). All three powders have median particle sizes 10-20 &#xb5;m.</p>
				<fig id="f3">
					<label>Figure 3</label>
					<caption>
						<title>Particle size distributions of the powders used.</title>
					</caption>
					<graphic id="gra-3" xlink:href="MC-72-350-e310-gf3.png"/>
				</fig>
			</sec>
			<sec id="sec2.2">
				<label>2.2.</label>
				<title>Methods</title>
				<p>The mixture proportions given in <xref ref-type="table" rid="t2">Table 2</xref> were used to prepare mortar and paste (same proportions but without sand) samples for various characterization tests.</p>
				<table-wrap id="t2">
					<label>Table 2</label>
					<caption>
						<title>Mixture proportions used to prepare mortar samples.</title>
					</caption>
					<table>
						<colgroup>
							<col/>
							<col/>
							<col/>
							<col/>
							<col/>
							<col/>
							<col/>
						</colgroup>
						<thead>
							<tr>
								<th align="center">Mixture</th>
								<th align="center">FAOx</th>
								<th align="center">MgO1500</th>
								<th align="center">Slag</th>
								<th align="center">Borax<sup>*</sup>
								</th>
								<th align="center">Sand</th>
								<th align="center">Water</th>
							</tr>
						</thead>
						<tbody>
							<tr>
								<td align="justify">MgOx-6/4</td>
								<td align="center">6</td>
								<td align="center">4</td>
								<td align="center">-</td>
								<td align="center">0.5</td>
								<td align="center">20</td>
								<td align="center">3</td>
							</tr>
							<tr>
								<td align="justify">MgOx-7/3</td>
								<td align="center">7</td>
								<td align="center">3</td>
								<td align="center">-</td>
								<td align="center">0.5</td>
								<td align="center">20</td>
								<td align="center">3</td>
							</tr>
							<tr>
								<td align="justify">SlOx-6/4</td>
								<td align="center">6</td>
								<td align="center">-</td>
								<td align="center">4</td>
								<td align="center">1</td>
								<td align="center">20</td>
								<td align="center">3</td>
							</tr>
							<tr>
								<td align="justify">SlOx-7/3</td>
								<td align="center">7</td>
								<td align="center">-</td>
								<td align="center">3</td>
								<td align="center">1</td>
								<td align="center">20</td>
								<td align="center">3</td>
							</tr>
							<tr>
								<td align="justify">MgSlOx</td>
								<td align="center">7</td>
								<td align="center">1.5</td>
								<td align="center">1.5</td>
								<td align="center">0.5</td>
								<td align="center">20</td>
								<td align="center">3</td>
							</tr>
							<tr>
								<td align="justify" colspan="7">*i.e. 10 % of binder (FAOx+Slag) mass for SlOx </td>
							</tr>
						</tbody>
					</table>
				</table-wrap>
				<p>The mixture proportions in <xref ref-type="table" rid="t2">Table 2</xref> were chosen to achieve a low estimated carbon footprint and adequate mechanical performance. The FAOx-to-alkaline binder ratio influences the strength and water resistance of oxalate binders and a ratio close to 2 is close to optimum when MgO1500 is used (<xref ref-type="bibr" rid="B15">15</xref>). The calcination of MgCO<sub>3</sub> to produce 1 g MgO emits ~1.1 g chemical CO<sub>2</sub>. Assuming 0.4 g fuel-related CO<sub>2</sub> is released to obtain dead-burned MgO (at a temperature similar to PC clinker production) (<xref ref-type="bibr" rid="B48">48</xref>), the total emitted CO<sub>2</sub> becomes ~1.5 g per 1 g of MgO1500. FAOx (1 part FA and 1.5 parts OxAc) has FA:C<sub>2</sub>O<sub>4</sub>
					<sup>2-</sup> ~1.0, which means half of the FAOx mass is equivalent CO<sub>2</sub>. Hence, carbon neutrality/negativity can be achieved only when FAOx:MgO1500 &#x2265; 3.0. Slag has a chemical carbon footprint of zero but operations like grinding make it slightly positive. Hence the two SlOx mixtures and the MgSlOx mixture in <xref ref-type="table" rid="t2">Table 2</xref> may be carbon-negative but the two MgOx mixtures are not. Acid-base mixtures exhibit different behavior than portland cement pastes in the fresh state. Their stronger shear-thinning character and their short setting times do not provide a long time period over which flow is constant (especially for SlOx mixtures). The water-to-binder ratio (W/B) of 0.30 chosen for all mixtures is roughly the lowest value that allows adequate mixing and compaction of fresh mortars. The sand-to-binder ratio was chosen as 2.0 to give a paste/aggregate ratio similar to that in standard PC mortars. 5 % borax was used in MgOx to sufficiently retard setting. SlOx mixtures react more rapidly than MgOx, so a higher amount of borax was needed.</p>
				<sec id="sec2.2.1">
					<label>2.2.1.</label>
					<title>Compressive strength development</title>
					<p>50-mm mortar cubes were tested as in ASTM C109 (<xref ref-type="bibr" rid="B49">49</xref>), but sample preparation slightly differed in that the mixture was mixed by hand in batches of ~300 cm<sup>3</sup>. FAOx was first mixed with water to obtain a paste to which sand was added, followed by further mixing and the addition of the alkaline powder (MgO1500 or slag). The samples were demolded after 1 h, cured at ~24 &#xb0;C and ~35 % RH, and tested at 4 h, 1 d, 7 d, and 28 d using a 250 kN Universal Testing Machine, at a loading rate of 1.5 kN/s.</p>
				</sec>
				<sec id="sec2.2.2">
					<label>2.2.2.</label>
					<title>Investigation of mineralogy and microstructure</title>
					<p>XRD analysis (BTX II, Olympus, Japan) was performed between 5 and 55 &#xb0;2&#x3b8;, with a resolution of 0.25 &#xb0;2&#x3b8;, on &lt; 150 &#xb5;m powders obtained from reacted pastes at 1, 7, and 28 d to investigate mineralogical changes due to reactions. Cu K&#x3b1; radiation was selected with a current of 330 &#x3bc;A and a tube voltage of 30 kV. The nature and quantity of solid phases in the reacted pastes were also investigated using thermogravimetric analysis, TGA (SDT 650, TA Instruments, USA), for paste samples air-cured for 1 d and 35 d by heating in a N<sub>2</sub> environment to 900 &#xb0;C at 20 &#xb0;C/min. The microstructures of the reacted pastes were studied with scanning electron microscopy, SEM (Quanta 400F, FEI Philips, USA), on 35-d-old samples.</p>
				</sec>
				<sec id="sec2.2.3">
					<label>2.2.3.</label>
					<title>Change in pH</title>
					<p>The pH of paste samples was measured, initially on the fresh paste (time ~zero) and subsequently on hardened samples at 1 h, 24 h, and 7 d, with a pH meter (pH/CON 300, Oakton Instruments, USA). The fresh pastes were diluted by adding an equal mass of distilled water to obtain a more repeatable reading. Hardened samples were ground with a mortar and pestle, and pH was measured on suspensions of 10 g of ground paste and 10 g of distilled water (<xref ref-type="bibr" rid="B50">50</xref>).</p>
				</sec>
				<sec id="sec2.2.4">
					<label>2.2.4</label>
					<title>Mercury Intrusion Porosimetry (MIP)</title>
					<p>Mercury intrusion porosimetry, MIP (Poremaster 60, Quantachrome Instruments, USA) was used to analyze the pore size distribution of paste samples, cured at ~24 &#xb0;C and ~35 % RH for 25 d. The maximum pressure was selected as 345 MPa. The contact angle and surface tension of mercury were assumed to be 140 &#xb0; and 480x10<sup>-3</sup> N/m.</p>
				</sec>
				<sec id="sec2.2.5">
					<label>2.2.5.</label>
					<title>Temperature change</title>
					<p>The change in the temperature of the mixtures due to ongoing reaction was recorded using a semi-adiabatic setup (<xref ref-type="bibr" rid="B51">51</xref>). Extruded polystyrene containers with lids (with an opening to introduce materials and another for a thermocouple) were used. W/B was chosen as 0.45 to ensure adequate mixing. The recording was started, and FAOx and borax were subsequently added to the water, and the mix was stirred for 60 s. The alkaline powder was then introduced, the obtained paste stirred for another 60 s. The opening was shut, and temperature was measured up to 30 min. The effect on temperature of introducing the alkaline powder at different times (0, 1, 5, or 10 minutes) after mixing FAOx and water was also investigated.</p>
				</sec>
				<sec id="sec2.2.6">
					<label>2.2.6.</label>
					<title>Water resistance</title>
					<p>The water resistance of the mortars was evaluated by determining the retained strength (%) after water submersion. The 28-d air-cured strength of each mixture was used as the reference strength. Specimens were then kept under water at ~24 &#xb0;C for another 28 d, removed from water, their surfaces dried using a towel, and tested without delay (within minutes).</p>
				</sec>
			</sec>
		</sec>
		<sec id="sec3" sec-type="results|discussion">
			<label>3.</label>
			<title>Results and discussion</title>
			<sec id="sec3.1">
				<label>3.1</label>
				<title>Setting times of oxalate mortars</title>
				<p>The setting times of the mixtures are given in <xref ref-type="table" rid="t3">Table 3</xref>.</p>
				<table-wrap id="t3">
					<label>Table 3</label>
					<caption>
						<title>Final setting times of mixtures with and without the retarder.</title>
					</caption>
					<table>
						<colgroup>
							<col/>
							<col/>
							<col/>
						</colgroup>
						<thead>
							<tr>
								<th align="justify">Mixtures</th>
								<th align="justify">Setting time without borax (min.)</th>
								<th align="justify">Setting time with borax (min.)</th>
							</tr>
						</thead>
						<tbody>
							<tr>
								<td align="justify">MgOx-6/4</td>
								<td align="center">5.5</td>
								<td align="center">11.0</td>
							</tr>
							<tr>
								<td align="justify">MgOx-7/3</td>
								<td align="center">6.5</td>
								<td align="center">12.0</td>
							</tr>
							<tr>
								<td align="justify">SlOx-6/4</td>
								<td align="center">1.0</td>
								<td align="center">5.0</td>
							</tr>
							<tr>
								<td align="justify">SlOx-7/3</td>
								<td align="center">1.0</td>
								<td align="center">6.0</td>
							</tr>
							<tr>
								<td align="justify">MgSlOx</td>
								<td align="center">2.0</td>
								<td align="center">5.0</td>
							</tr>
						</tbody>
					</table>
				</table-wrap>
				<p> SlOx mixtures have shorter setting times than MgOx mixtures. The alkaline powder reacted with the acid salt affects the initial pH of oxalate cement pastes (<xref ref-type="fig" rid="f5">Figure 5</xref>), which changes the relative amounts of the different oxalate species present in the solution. SlOx pastes have higher initial pH and form calcium oxalates while MgOx have lower initial pH and form magnesium oxalates, resulting in the observed differences in setting time. Addition of borax prolongs setting times of all mixtures. The mechanism is likely similar for MgOx and SlOx to the retardation it causes in MPCs. At low pH, tetraborate ions from borax dissolution are adsorbed on the surface of MgO particles. This produces a layer which slows the dissolution of MgO (<xref ref-type="bibr" rid="B52">52</xref>).</p>
			</sec>
			<sec id="sec3.2">
				<label>3.2.</label>
				<title>Influence of mixture proportions on strength development</title>
				<p>The strength development of the mortars are compared in <xref ref-type="fig" rid="f4">Figure 4</xref>.</p>
				<fig id="f4">
					<label>Figure 4</label>
					<caption>
						<title>Compressive strength development of MgOx and SlOx mortars (inset shows the first 4 h).</title>
					</caption>
					<graphic id="gra-4" xlink:href="MC-72-350-e310-gf4.png"/>
				</fig>
				<p>The very early-age (4 h) strengths of both types of mortars are &lt; 8 MPa. Although this appears low in comparison with the analogous MPC, most such high early strengths reported for MPC are measured on pastes, which allows very low W/B to be employed (<xref ref-type="bibr" rid="B20">20</xref>, <xref ref-type="bibr" rid="B24">24</xref>). Initial comparisons indicate that oxalate cements have slightly greater water need than phosphate cements. 1-d strength is higher for MgOx than SlOx, reaching ~17.5 MPa for MgOx-7/3. The higher amount of borax used in the SlOx mixtures contributes to the lower early strength. Borax not only retards the reactions but also contributes some water (W/B becomes ~0.31 and ~0.33 for mixtures with 5 % and 10 % borax). MgOx mortars reach their ultimate strengths at ~7 d, and MgOx-7/3 even shows a slight drop in strength beyond 7 d. The fact that MgOx-6/4, which reaches &gt; 30 MPa ultimate strength, does not show a similar drop in strength after 7 d, suggests a critical magnesium-to-oxalate ratio may have been exceeded in MgOx-7/3, leading to volume instabilities. The strength of SlOx mortars reach 24-27 MPa, and MgSlOx, with an equal mass combination of the two alkaline powders has the highest 28-d strength among all mortars. More importantly, the strengths of all slag-containing mortars have an upward trend from 7 d to 28 d, indicating their ultimate strengths may be even higher. Much as early-age strength gain is related with the formation of crystalline reaction products, later-age strength is related with the formation of pore-filling amorphous phases and this may explain the delayed but continuing strength gain of slag-bearing mortars.</p>
			</sec>
			<sec id="sec3.3">
				<label>3.3.</label>
				<title>Change in pH</title>
				<p>The change in the pH of the pastes is compared in <xref ref-type="fig" rid="f5">Figure 5</xref>. The increase of the low initial pH of acid-base paste mixtures is related with the amount of reaction hence corresponding neutralization.</p>
				<fig id="f5">
					<label>Figure 5</label>
					<caption>
						<title>Change in pH for the paste samples.</title>
					</caption>
					<graphic id="gra-5" xlink:href="MC-72-350-e310-gf5.png"/>
				</fig>
				<p>The initial pH of FAOx in water is low (~1), due to the dissolution of oxalates in water. MgOx pastes have lower initial pH (1-2) than SlOx pastes (~4). Initial pH is related to early mortar strength, higher for SlOx than MgOx. For both mixture types, pH quickly rises as Mg<sup>2+</sup> and Ca<sup>2+</sup> from the dissolution of the alkaline powders react with the available oxalate species (the oxalate and hydrogen oxalate anions). The pH of MgOx rises quickly to 8-9 within 24 h, after which it more or less plateaus, similar to the pH development reported for ferrous oxalate cement pastes (<xref ref-type="bibr" rid="B39">39</xref>). The rise in pH is much less for SlOx, only to ~5, suggesting less complete neutralization reactions, and explaining the lower 7 or 28 d strengths. Despite little change in pH after 1 h for SlOx pastes, strength increases up to 28 d (<xref ref-type="fig" rid="f4">Figure 4</xref>). The moderately acidic environment is hence suitable for continued dissolution of slag particles and formation of more reaction products. The ultimate pH of MgSlOx paste is ~7, in between the values for MgO1500-only and slag-only pastes. This neutral value suggests a better balance between acidic and alkaline starting powders and a lower amount of materials left unreacted after the rapid reactions.</p>
			</sec>
			<sec id="sec3.4">
				<label>3.4.</label>
				<title>Influence of mixture proportions on mineralogy</title>
				<p>
					<xref ref-type="fig" rid="f6">Figure 6</xref> compares the mineralogical development of the pastes. MgOx pastes, as expected, contain a hydrated magnesium oxalate, glushinskite (MgC<sub>2</sub>O<sub>4</sub>&#xb7;2H<sub>2</sub>O) as their main reaction products. Whewellite (CaC<sub>2</sub>O<sub>4</sub>&#xb7;H<sub>2</sub>O) and quartz are also found in the final paste. Quartz carries from the unreacted part of FAOx. Whewellite is also present in FAOx but it is not clear whether it partly dissolves in the acidic condition achieved when FAOx is added to water and then reforms as pH increases. Also present are unreacted magnesia (periclase) and forsterite, coming from MgO1500. Small amounts of magnesiow&#xfc;stite (Fe<sub>x</sub>Mg<sub>1-x</sub>O), and magnesioferrite (Fe<sub>2</sub>MgO<sub>4</sub>) are also detected but their peaks partly overlap with those of whewellite and forsterite. The diffractograms of the SlOx pastes suggest whewellite and another calcium oxalate, weddellite (CaC<sub>2</sub>O<sub>4</sub>&#xb7;2H<sub>2</sub>O), as well as a small amount of portlandite.</p>
				<fig id="f6">
					<label>Figure 6</label>
					<caption>
						<title>XRD of MgOx and SlOx pastes.</title>
						<p>a) MgOx-6/4; b) MgOx-7/3; c) SlOx-6/4; d) SlOx-7/3; e) MgSlOx.</p>
					</caption>
					<graphic id="gra-6" xlink:href="MC-72-350-e310-gf6.png"/>
				</fig>
				<p>MAUD (<xref ref-type="bibr" rid="B53">53</xref>) was used to analyze the 28-d XRD spectra using the Rietveld method. Glushinskite, whewellite, periclase, quartz, and forsterite were considered as the only phases existing in MgOx pastes. Whewellite, weddellite, quartz, and portlandite are considered as the crystalline phases in SlOx, with additional amorphous content. Diffraction data of the selected phases taken from the &#x201c;crystallography open database&#x201d; were loaded into MAUD. Background substraction, scaling, and noise cancellation operations were performed. Analysis of MgOx-6/4 suggested ~35 % glushinskite, ~20 % whewellite, and ~25 % periclase, as well as ~4 % quartz and ~16 % forsterite. The fit parameter, R<sub>w</sub>, was 7.1 %. The amorphous content of MgOx pastes was determined, using an internal standard, to be negligible. For MgOx-7/3, slightly greater amounts of the oxalates (~40 % glushinskite and ~25 % whewellite), and less periclase (~18 %) are calculated, consistent with its higher FAOx/MgO1500. The amounts of the remnant phases also change as expected, quartz increases to 5 % and forsterite decreases to 11 %. R<sub>w</sub> was calculated as 8.9 %. Further inspection of these results suggested that the calculated amounts of phases may be slightly under/overestimated. The amount of non-volatile oxides in the starting mixture should equal their amounts in the final paste. For example, in the starting mixture for MgOx-6/4, MgO is mostly in MgO1500, SiO<sub>2</sub> is in MgO1500 (in Forsterite) and in FAOx (from FA), while CaO and C<sub>2</sub>O<sub>4</sub> are mostly in FAOx. Since the amounts of each material in the starting mixture is known (<xref ref-type="table" rid="t2">Table 2</xref>), using the oxide composition for each (<xref ref-type="table" rid="t1">Table 1</xref>), and assuming FAOx contains 49 % FA and 51 % C<sub>2</sub>O<sub>4</sub> (verified approximately by XRF tests), the amounts of glushinskite, whewellite, periclase, quartz, and forsterite (total 100 %) that best satisfy the &#x201c;mass of oxide in initial mixture equals mass of oxide in final paste&#x201d; objective for MgO, SiO<sub>2</sub>, CaO, and C<sub>2</sub>O<sub>4</sub> are calculated using the Solver add-in program in MS Excel as 35 %, 22 %, 18 %, 11 %, 14 %. Hence, there is probably a smaller amount of (unreacted) periclase and a greater amount of quartz in the reacted paste than quantified from the diffractogram in <xref ref-type="fig" rid="f6">Figure 6a</xref>. The same analysis for MgOx-7/3 calculates 38 %, 25 %, 10 %, 11 %, 14 % for of glushinskite, whewellite, periclase, quartz, and forsterite, again suggesting unreacted periclase was initially overestimated and quartz was underestimated. This may be partly related with certain minor phases not being considered for the quantification or measurement parameters leading to insufficient intensity for some peaks i.e. low signal-to-noise ratio. Reviewing these calculated amounts of each phase and <xref ref-type="table" rid="t1">Tables 1</xref> and <xref ref-type="table" rid="t2">2</xref>, it can be deduced that the amount of forsterite increases while quartz decreases from the starting mixture to the final paste. Hence, some of the quartz in FAOx (from FA) reacts with dissolved MgO1500 to form new forsterite. It is unclear whether the forsterite initially available in MgO1500 ever partly dissolves in the acidic solution. This makes it difficult to calculate a degree of reaction for MgO1500. However, the initial fractions of MgO1500 in the starting mixture and the final unreacted periclase contents indicate that the degree of reaction of MgO1500 is higher in MgOx-7/3 than in MgOx-6/4, consistent with its higher 7-d strength (<xref ref-type="fig" rid="f4">Figure 4</xref>, ignoring the subsequent drop in strength due to durability problems). Tracking MgO only (starting in MgO1500 and ending up in Glushinskite, Forsterite, and unreacted Mg1500), degrees of hydration for MgO1500 in MgOx-6/4 and MgOx-7/3 are 45 % and 55 %, respectively. Similar low degrees of reaction for MgO have been reported for magnesium phosphate cements (<xref ref-type="bibr" rid="B54">54</xref>). The amorphous natures of the slag and some reaction products complicate the quantitative interpretation of XRD for the SlOx and MgSlOx pastes. The amorphous content in SlOx-7/3 is determined as ~45 %. Even if the slag used is fully amorphous, this would mean part of the reaction products, ~20 % of the total mass, is amorphous as well. The weddellite/whewellite ratio is higher in SlOx-6/4 than in SlOx-7/3 as expected due to its lower FAOx content (<xref ref-type="fig" rid="f6">Figures 6c</xref> and <xref ref-type="fig" rid="f6">d</xref>). Whewellite is the more stable one of the two calcium oxalates. The initial crystallization phase from aqueous solution is a calcium oxalate trihydrate, which loses water of crystallization to either the monohydrate or dihydrate, depending on conditions, such as the calcium to oxalate ion ratio or the presence of substances which form complexes with either calcium or oxalate ions, such as citric acid and magnesium (<xref ref-type="bibr" rid="B55">55</xref>). Weddellite precipitates under excess of calcium ions in the medium. This is consistent with no weddellite being detected in MgSlOx, which contained much less slag, hence much less calcium, than either SlOx. The total whewellite and weddellite content is ~46 % in SlOx-6/4 and ~49 % in SlOx-7/3. The total amount of whewellite and weddellite that can be formed can be estimated considering the total calcium in the slag and in the fly ash used to produce FAOx. 1 g of the slag in <xref ref-type="table" rid="t1">Table 1</xref> can produce 1.06 g whewellite or 1.17 g weddellite. Similarly, 1 g of FA in <xref ref-type="table" rid="t1">Table 1</xref> can produce 0.60 g whewellite or 0.66 g weddellite. Assuming equal amounts of each are formed, the maximum total amount of whewellite and weddellite that can be produced in SlOx-6/4 is calculated as ~49 %. Although the calculated total is below this value, it is probably high, since it is unlikely that all the calcium forms one of the two calcium oxalates.</p>
			</sec>
			<sec id="sec3.5">
				<label>3.5.</label>
				<title>Thermogravimetric analyses</title>
				<p>
					<xref ref-type="fig" rid="f7">Figure 7</xref> presents the mass loss and heat flow measured for paste samples heated to 900 &#xb0;C.</p>
				<fig id="f7">
					<label>Figure 7</label>
					<caption>
						<title>Mass loss and corresponding derived weight curves at.</title>
						<p>(a,b,c,d) 1 d; (e,f,g,h) 35 d.</p>
					</caption>
					<graphic id="gra-7" xlink:href="MC-72-350-e310-gf7.png"/>
				</fig>
				<p>Mass loss takes place in three main steps for all pastes, which contrasts with the one step decomposition of K-struvite in MPCs (<xref ref-type="bibr" rid="B56">56</xref>). Although glushinskite decomposes in two steps, the presence of whewellite coming from FAOx in the MgOx pastes causes a third mass loss step. <xref ref-type="fig" rid="f8">Figure 8</xref> summarizes the decomposition steps for the calcium and magnesium oxalates and the theoretical mass losses associated with each step (<xref ref-type="bibr" rid="B57 B58 B59">57-59</xref>).</p>
				<fig id="f8">
					<label>Figure 8</label>
					<caption>
						<title>Thermal decomposition of oxalate minerals (losses are percentage of initial mineral mass).</title>
					</caption>
					<graphic id="gra-8" xlink:href="MC-72-350-e310-gf8.png"/>
				</fig>
				<p>Up to ~100 &#xb0;C, mass loss is related with free water in all pastes. The rest of the mass loss in step 1 is due to loss of crystal water in the magnesium and calcium oxalates. <xref ref-type="fig" rid="f7">Figures 7b</xref> and <xref ref-type="fig" rid="f7">7f</xref> show two mass loss peaks for MgOx, one at 150 &#xb0;C due to the decomposition of whewellite and another at 210-220 &#xb0;C (higher than suggested in <xref ref-type="fig" rid="f8">Figure 8</xref>). For SlOx, the dominant loss peak is at ~160 &#xb0;C, as expected for whewellite (<xref ref-type="fig" rid="f7">Figures 7d</xref> and <xref ref-type="fig" rid="f7">7h</xref>). Although XRD suggests presence of weddellite, a related lower temperature peak is not observed. The second step (400-500 &#xb0;C) is related with the decomposition of anhydrous magnesium and calcium oxalates. The break-down of MgC<sub>2</sub>O<sub>4</sub> releases CO and CO<sub>2</sub> leaving behind MgO. Decomposition of CaC<sub>2</sub>O<sub>4</sub> releases CO and leaves behind CaCO<sub>3</sub>. The main peaks for SlOx (whewellite decomposition) in this step have shoulder peaks (weddellite decomposition) on their lower temperature sides, most noticeable for SlOx-7/3, in <xref ref-type="fig" rid="f7">Figure 7h</xref>. The third step (600-800 &#xb0;C) breaks down the remaining carbonate, releasing CO<sub>2</sub>.</p>
			</sec>
			<sec id="sec3.6">
				<label>3.6.</label>
				<title>Influence of mixture proportioning on the microstructure</title>
				<p>
					<xref ref-type="fig" rid="f9">Figure 9</xref> presents SEM images of reacted pastes.</p>
				<fig id="f9">
					<label>Figure 9</label>
					<caption>
						<title>SEM images of the pastes.</title>
						<p>a) MgOx-6/4; b) MgOx-7/3; c) SlOx-6/4; d) SlOx-7/3; e) MgSlOx.</p>
					</caption>
					<graphic id="gra-9" xlink:href="MC-72-350-e310-gf9.png"/>
				</fig>
				<p>Many loosely connected prismatic crystals of 4-5 &#xb5;m size are observed in MgOx-6/4 among unreacted magnesia particles (<xref ref-type="fig" rid="f9">Figure 9a</xref>). Crystals in MgOx-7/3 are smaller and cube-like (<xref ref-type="fig" rid="f9">Figure 9b</xref>). SlOx shows smaller, mostly sub-micrometer crystals dispersed in a glassy background (<xref ref-type="fig" rid="f9">Figures 9c</xref> and <xref ref-type="fig" rid="f9">9d</xref>). Notably, cracks are observed in MgOx-7/3 (<xref ref-type="fig" rid="f9">Figure 9b</xref>), which could explain the strength loss recorded for this mixture from 7 to 28 d. In MgSlOx (<xref ref-type="fig" rid="f9">Figure 9e</xref>), the amorphous material produced by reactions of the slag envelops the crystals, leading to a denser microstructure explaining the higher ultimate strength measured on mortar samples.</p>
			</sec>
			<sec id="sec3.7">
				<label>3.7.</label>
				<title>Pore size distribution and porosity</title>
				<p>
					<xref ref-type="fig" rid="f10">Figure 10</xref> presents the pore size distributions of the prepared pastes.</p>
				<fig id="f10">
					<label>Figure 10</label>
					<caption>
						<title>Pore size distribution curves obtained by mercury intrusion porosimetry.</title>
						<p>a) Total volume intruded vs. Pore size; b) Normalized volume vs. Pore size.</p>
					</caption>
					<graphic id="gra-10" xlink:href="MC-72-350-e310-gf10.png"/>
				</fig>
				<p>MgOx-6/4 has the lowest porosity (<xref ref-type="fig" rid="f10">Figure 10a</xref>) among all mixtures. MgOx-7/3 has the highest of all mixtures which could be related with the cracks observed in <xref ref-type="fig" rid="f9">Figure 9b</xref>. This paste also contains an unexpectedly high amount of pores of nearly 1 &#xb5;m size which could be microcracks. All samples appear to contain two dominant sizes of pores, larger than ~0.1 &#xb5;m and smaller than ~0.02 &#xb5;m. Both MgOx pastes have greater average pore size than SlOx samples, as well as a wider range of pore sizes. The amorphous products in the slag-containing pastes may be refining their larger pores. Differences in the amount of small and large pores in <xref ref-type="fig" rid="f10">Figure 10</xref> may explain the differences in strength better than total porosity. MgSlOx, the paste with the highest strength, has a smaller amount of such large pores and a greater amount of smaller pores.</p>
			</sec>
			<sec id="sec3.8">
				<label>3.8.</label>
				<title>Temperature changes</title>
				<p>There are two distinct heat-evolving steps in the reactions of MgOx and SlOx: i) the wetting and dissolution of FAOx in water, and ii) the contact of the alkaline powder (MgO1500 or slag) with the FAOx and water mixture. The contact of the alkaline powder alone with water evolves heat but is insignificant in comparison with the other two steps. <xref ref-type="fig" rid="f11">Figure 11a</xref> shows the change in temperature of the various oxalate pastes prepared. Temperature rises sharply by 7-8 &#xb0;C when FAOx and water are mixed (time zero). This is considerable for the small paste volume (~7 cm<sup>3</sup>) used. After ~1 min, the slurry begins to cool slowly.</p>
				<fig id="f11">
					<label>Figure 11</label>
					<caption>
						<title>a) Change in the temperature of the paste samples (5 min delay between addition of FAOx and alkaline powder); b) Maximum temperature of paste samples vs. time delay between adding FAOx and adding alkaline powder (lines are the best-fits to the data points for each paste).</title>
					</caption>
					<graphic id="gra-11" xlink:href="MC-72-350-e310-gf11.png"/>
				</fig>
				<p>The addition of the alkaline powder creates a second (maximum) temperature peak. The time delay of the alkaline powder addition affects this maximum temperature. <xref ref-type="fig" rid="f11">Figure 11b</xref> shows the change in this maximum temperature with the amount of time elapsed before adding the alkaline powder. A longer wait period reduces the overlap of the two separate heat-evolving events, and a slightly lower maximum temperature is recorded. However, the FAOx + water paste begins to stiffen in time hence a very long wait period may require additional water to be added, influencing hardened properties. MgOx pastes reach slightly higher temperatures than SlOx. The temperature peak occurs 2-3 min after all materials have been added. Hence, setting which takes place after 5-10 minutes follows the temperature peak with a minor delay.</p>
			</sec>
			<sec id="sec3.9">
				<label>3.9.</label>
				<title>Water resistance</title>
				<p>The resistance of MgOx, SlOx, and MgSlOx mortars to water are compared in <xref ref-type="fig" rid="f12">Figure 12</xref>. MgOx mortars cured in air and then kept under water do not show significant changes in compressive strength (observed differences being within experimental uncertainty). In contrast, both SlOx mortars lose ~70 % of their air-dried strengths. This decrease could be related with the dissolution of the reaction products present. Hydraulic pressure inside pores within the sample could also negatively affect strength since these samples are tested immediately after removal from water, without any time to dry. Small increases in the strengths of MgOx-6/4 and MgSlOx may be due to continued reaction in mortars which had not reached their ultimate strengths prior to submersion in water.</p>
				<fig id="f12">
					<label>Figure 12</label>
					<caption>
						<title>The strengths 28-d air-cured samples and their retained strengths after additional 28-d water-cur</title>
					</caption>
					<graphic id="gra-12" xlink:href="MC-72-350-e310-gf12.png"/>
				</fig>
			</sec>
			<sec id="sec3.10">
				<label>3.10.</label>
				<title>Reaction mechanism of magnesium/calcium oxalate cements</title>
				<p>There are two main steps in the reaction of MgOx cements with water. In the first step, the dissolution of FAOx in water yields oxalate ion species and H<sup>+</sup>, which makes the solution acidic. A diprotic acid, oxalic acid has pKa<sub>1</sub> = 1.27 and pKa<sub>2</sub> = 4.27. Hence, at the initial low pH of ~2 (<xref ref-type="fig" rid="f5">Figure 5</xref>) more HC<sub>2</sub>O<sub>4</sub>
					<sup>-</sup> and some H<sub>2</sub>C<sub>2</sub>O<sub>4</sub> are present in the solution (<xref ref-type="bibr" rid="B39">39</xref>).</p>
				<disp-formula id="e1">
					<mml:math id="mml-1">
						<mml:mrow>
							<mml:msub>
								<mml:mi>H</mml:mi>
								<mml:mn>2</mml:mn>
							</mml:msub>
							<mml:msub>
								<mml:mi>C</mml:mi>
								<mml:mn>2</mml:mn>
							</mml:msub>
							<mml:msub>
								<mml:mi>O</mml:mi>
								<mml:mn>4</mml:mn>
							</mml:msub>
							<mml:mo>&#x2192;</mml:mo>
							<mml:msup>
								<mml:mi>H</mml:mi>
								<mml:mo>+</mml:mo>
							</mml:msup>
							<mml:mo>+</mml:mo>
							<mml:mi>H</mml:mi>
							<mml:msub>
								<mml:mi>C</mml:mi>
								<mml:mn>2</mml:mn>
							</mml:msub>
							<mml:msubsup>
								<mml:mi>O</mml:mi>
								<mml:mn>4</mml:mn>
								<mml:mo>&#x2212;</mml:mo>
							</mml:msubsup>
							<mml:mfenced>
								<mml:mrow>
									<mml:mi>p</mml:mi>
									<mml:msub>
										<mml:mi>K</mml:mi>
										<mml:mrow>
											<mml:mi>a</mml:mi>
											<mml:mn>1</mml:mn>
										</mml:mrow>
									</mml:msub>
									<mml:mo>=</mml:mo>
									<mml:mn>1.27</mml:mn>
								</mml:mrow>
							</mml:mfenced>
						</mml:mrow>
					</mml:math>
					<label>[1]</label>
				</disp-formula>
				<p>In the second step, the periclase in MgO1500 begins to dissociate in the acidic solution and reacts with HC<sub>2</sub>O<sub>4</sub>
					<sup>-</sup>. pH rises and HC<sub>2</sub>O<sub>4</sub>
					<sup>-</sup> further dissociates into C<sub>2</sub>O<sub>4</sub>
					<sup>2-</sup>. At pH~4-4.5, approximately equal amounts of HC<sub>2</sub>O<sub>4</sub>
					<sup>-</sup> and C<sub>2</sub>O<sub>4</sub>
					<sup>2-</sup> are present in the solution (<xref ref-type="bibr" rid="B39">39</xref>).</p>
				<disp-formula id="e2">
					<mml:math id="mml-2">
						<mml:mrow>
							<mml:mi>H</mml:mi>
							<mml:msub>
								<mml:mi>C</mml:mi>
								<mml:mn>2</mml:mn>
							</mml:msub>
							<mml:msubsup>
								<mml:mi>O</mml:mi>
								<mml:mn>4</mml:mn>
								<mml:mo>&#x2212;</mml:mo>
							</mml:msubsup>
							<mml:mo>&#x2192;</mml:mo>
							<mml:msup>
								<mml:mi>H</mml:mi>
								<mml:mo>+</mml:mo>
							</mml:msup>
							<mml:mo>+</mml:mo>
							<mml:msub>
								<mml:mi>C</mml:mi>
								<mml:mn>2</mml:mn>
							</mml:msub>
							<mml:msubsup>
								<mml:mi>O</mml:mi>
								<mml:mn>4</mml:mn>
								<mml:mrow>
									<mml:mn>2</mml:mn>
									<mml:mo>&#x2212;</mml:mo>
								</mml:mrow>
							</mml:msubsup>
							<mml:mfenced>
								<mml:mrow>
									<mml:mi>p</mml:mi>
									<mml:msub>
										<mml:mi>K</mml:mi>
										<mml:mrow>
											<mml:mi>a</mml:mi>
											<mml:mn>2</mml:mn>
										</mml:mrow>
									</mml:msub>
									<mml:mo>=</mml:mo>
									<mml:mn>4.27</mml:mn>
								</mml:mrow>
							</mml:mfenced>
						</mml:mrow>
					</mml:math>
					<label>[2]</label>
				</disp-formula>
				<p>The continued dissolution of MgO1500 (forsterite and periclase) releases amorphous silica and Mg<sup>2+</sup> into solution (<xref ref-type="bibr" rid="B60">60</xref>), resulting in a rapid increase in pH (the first hour in <xref ref-type="fig" rid="f5">Figure 5</xref>). HC<sub>2</sub>O<sub>4</sub>
					<sup>-</sup> and C<sub>2</sub>O<sub>4</sub>
					<sup>2-</sup> react with the Mg<sup>2+</sup> ions to form glushinskite (<xref ref-type="fig" rid="f6">Figures 6a</xref> and <xref ref-type="fig" rid="f6">6b</xref>):</p>
				<disp-formula id="e3">
					<mml:math id="mml-3">
						<mml:mrow>
							<mml:mi>M</mml:mi>
							<mml:mi>g</mml:mi>
							<mml:mi>O</mml:mi>
							<mml:mo>+</mml:mo>
							<mml:mn>2</mml:mn>
							<mml:msup>
								<mml:mi>H</mml:mi>
								<mml:mo>+</mml:mo>
							</mml:msup>
							<mml:mo>&#x2192;</mml:mo>
							<mml:mi>M</mml:mi>
							<mml:msup>
								<mml:mi>g</mml:mi>
								<mml:mrow>
									<mml:mn>2</mml:mn>
									<mml:mo>+</mml:mo>
								</mml:mrow>
							</mml:msup>
							<mml:mo>+</mml:mo>
							<mml:msub>
								<mml:mi>H</mml:mi>
								<mml:mn>2</mml:mn>
							</mml:msub>
							<mml:mi>O</mml:mi>
						</mml:mrow>
					</mml:math>
					<label>[3]</label>
				</disp-formula>
				<disp-formula id="e4">
					<mml:math id="mml-4">
						<mml:mrow>
							<mml:mi>M</mml:mi>
							<mml:msup>
								<mml:mi>g</mml:mi>
								<mml:mrow>
									<mml:mn>2</mml:mn>
									<mml:mo>+</mml:mo>
								</mml:mrow>
							</mml:msup>
							<mml:mo>+</mml:mo>
							<mml:mo>&#xa0;</mml:mo>
							<mml:mi>H</mml:mi>
							<mml:msub>
								<mml:mi>C</mml:mi>
								<mml:mn>2</mml:mn>
							</mml:msub>
							<mml:msubsup>
								<mml:mi>O</mml:mi>
								<mml:mn>4</mml:mn>
								<mml:mo>&#x2212;</mml:mo>
							</mml:msubsup>
							<mml:mo>+</mml:mo>
							<mml:mn>2</mml:mn>
							<mml:msub>
								<mml:mi>H</mml:mi>
								<mml:mn>2</mml:mn>
							</mml:msub>
							<mml:mi>O</mml:mi>
							<mml:mo>&#x2192;</mml:mo>
							<mml:mi>M</mml:mi>
							<mml:mi>g</mml:mi>
							<mml:msub>
								<mml:mi>C</mml:mi>
								<mml:mn>2</mml:mn>
							</mml:msub>
							<mml:msub>
								<mml:mi>O</mml:mi>
								<mml:mn>4</mml:mn>
							</mml:msub>
							<mml:mo>&#x22c5;</mml:mo>
							<mml:mn>2</mml:mn>
							<mml:msub>
								<mml:mi>H</mml:mi>
								<mml:mn>2</mml:mn>
							</mml:msub>
							<mml:mi>O</mml:mi>
							<mml:mo>+</mml:mo>
							<mml:msup>
								<mml:mi>H</mml:mi>
								<mml:mo>+</mml:mo>
							</mml:msup>
						</mml:mrow>
					</mml:math>
					<label>[4]</label>
				</disp-formula>
				<disp-formula id="e5">
					<mml:math id="mml-5">
						<mml:mrow>
							<mml:mi>M</mml:mi>
							<mml:msup>
								<mml:mi>g</mml:mi>
								<mml:mrow>
									<mml:mn>2</mml:mn>
									<mml:mo>+</mml:mo>
								</mml:mrow>
							</mml:msup>
							<mml:mo>+</mml:mo>
							<mml:mo>&#xa0;</mml:mo>
							<mml:msub>
								<mml:mi>C</mml:mi>
								<mml:mn>2</mml:mn>
							</mml:msub>
							<mml:msubsup>
								<mml:mi>O</mml:mi>
								<mml:mn>4</mml:mn>
								<mml:mrow>
									<mml:mn>2</mml:mn>
									<mml:mo>&#x2212;</mml:mo>
								</mml:mrow>
							</mml:msubsup>
							<mml:mo>+</mml:mo>
							<mml:mn>2</mml:mn>
							<mml:msub>
								<mml:mi>H</mml:mi>
								<mml:mn>2</mml:mn>
							</mml:msub>
							<mml:mi>O</mml:mi>
							<mml:mo>&#x2192;</mml:mo>
							<mml:mi>M</mml:mi>
							<mml:mi>g</mml:mi>
							<mml:msub>
								<mml:mi>C</mml:mi>
								<mml:mn>2</mml:mn>
							</mml:msub>
							<mml:msub>
								<mml:mi>O</mml:mi>
								<mml:mn>4</mml:mn>
							</mml:msub>
							<mml:mo>&#x22c5;</mml:mo>
							<mml:mn>2</mml:mn>
							<mml:msub>
								<mml:mi>H</mml:mi>
								<mml:mn>2</mml:mn>
							</mml:msub>
							<mml:mi>O</mml:mi>
						</mml:mrow>
					</mml:math>
					<label>[5]</label>
				</disp-formula>
				<p>The role of <xref ref-type="disp-formula" rid="e4">Eqns. 4</xref> and <xref ref-type="disp-formula" rid="e5">5</xref> in glushinskite formation depends on pH. As pH increases, <xref ref-type="disp-formula" rid="e5">Equation 5</xref> predominates and glushinskite continues to precipitate at a slowing pace. Unreacted periclase is found in the final solid, as well as quartz and whewellite (CaC<sub>2</sub>O<sub>4</sub>.H<sub>2</sub>O) remaining from unreacted FAOx. In the case of SlOx, the reaction of slag in FAOx + water begins at pH ~ 4-5 where C<sub>2</sub>O<sub>4</sub>
					<sup>2-</sup> is abundant in the solution. The acidic conditions lead to dissolution of Ca<sup>2+</sup> from the slag which react with C<sub>2</sub>O<sub>4</sub>
					<sup>2-</sup> to form weddellite (<xref ref-type="fig" rid="f6">Figures 6c</xref> and <xref ref-type="fig" rid="f6">6d</xref>). Calcium ions can also come from whewellite in FAOx, the solubility of which increases markedly at pH &lt; 5 (<xref ref-type="bibr" rid="B61">61</xref>). The reactions in SlOx can be simplified as:</p>
				<disp-formula id="e6">
					<mml:math id="mml-6">
						<mml:mrow>
							<mml:mi>C</mml:mi>
							<mml:mi>a</mml:mi>
							<mml:mi>O</mml:mi>
							<mml:mo>+</mml:mo>
							<mml:mn>2</mml:mn>
							<mml:msup>
								<mml:mi>H</mml:mi>
								<mml:mo>+</mml:mo>
							</mml:msup>
							<mml:mo>&#x2192;</mml:mo>
							<mml:mi>C</mml:mi>
							<mml:msup>
								<mml:mi>a</mml:mi>
								<mml:mrow>
									<mml:mn>2</mml:mn>
									<mml:mo>+</mml:mo>
								</mml:mrow>
							</mml:msup>
							<mml:mo>+</mml:mo>
							<mml:msub>
								<mml:mi>H</mml:mi>
								<mml:mn>2</mml:mn>
							</mml:msub>
							<mml:mi>O</mml:mi>
						</mml:mrow>
					</mml:math>
					<label>[6]</label>
				</disp-formula>
				<disp-formula id="e7">
					<mml:math id="mml-7">
						<mml:mrow>
							<mml:mi>C</mml:mi>
							<mml:msup>
								<mml:mi>a</mml:mi>
								<mml:mrow>
									<mml:mn>2</mml:mn>
									<mml:mo>+</mml:mo>
								</mml:mrow>
							</mml:msup>
							<mml:mo>+</mml:mo>
							<mml:msub>
								<mml:mi>C</mml:mi>
								<mml:mn>2</mml:mn>
							</mml:msub>
							<mml:msubsup>
								<mml:mi>O</mml:mi>
								<mml:mn>4</mml:mn>
								<mml:mrow>
									<mml:mn>2</mml:mn>
									<mml:mo>&#x2212;</mml:mo>
								</mml:mrow>
							</mml:msubsup>
							<mml:mo>+</mml:mo>
							<mml:mn>2</mml:mn>
							<mml:msub>
								<mml:mi>H</mml:mi>
								<mml:mn>2</mml:mn>
							</mml:msub>
							<mml:mi>O</mml:mi>
							<mml:mo>&#x2192;</mml:mo>
							<mml:mi>C</mml:mi>
							<mml:mi>a</mml:mi>
							<mml:msub>
								<mml:mi>C</mml:mi>
								<mml:mn>2</mml:mn>
							</mml:msub>
							<mml:msub>
								<mml:mi>O</mml:mi>
								<mml:mn>4</mml:mn>
							</mml:msub>
							<mml:mo>&#x22c5;</mml:mo>
							<mml:mn>2</mml:mn>
							<mml:msub>
								<mml:mi>H</mml:mi>
								<mml:mn>2</mml:mn>
							</mml:msub>
							<mml:mi>O</mml:mi>
						</mml:mrow>
					</mml:math>
					<label>[7]</label>
				</disp-formula>
			</sec>
			<sec id="sec3.11">
				<label>3.11.</label>
				<title>Carbon neutrality and feasibility of MgOx and SlOx cements</title>
				<p>The argument that oxalate cements can be carbon neutral or even negative relies on the availability of oxalic acid produced from captured CO<sub>2</sub>. Hence, a natural supposition is that carbon-negative oxalate cements would be cost-prohibitive. Although production of oxalic acid from CO<sub>2</sub> has been shown at the laboratory scale, since no large-scale production exists, the overall cost of this step is not easy to predict (<xref ref-type="bibr" rid="B15">15</xref>). However, simple calculations and various assumptions can be used to estimate a rough cost and carbon footprint for MgOx and SlOx systems. The production of the alkaline powder is the main contributor to the carbon emissions related with oxalate cements. As stated in Section 2.2, ~1.5 g chemical and fuel related CO<sub>2</sub> is emitted during the production of 1 g dead-burned MgO from pure MgCO<sub>3</sub>. Hence, FAOx:MgO1500 must be greater than 3 to obtain a carbon neutral or negative mixture. The CO<sub>2</sub> emissions related with grinding, which are relatively small (<xref ref-type="bibr" rid="B62">62</xref>) or with the preparation of FAOx (mainly heating and grinding) can further increase this ratio. Conversely, this ratio can decrease if the MgO used has a low carbon footprint, like one derived from seawater (<xref ref-type="bibr" rid="B63">63</xref>) is used, or if a higher OxAc:FA is used to prepare FAOx. However, varying OxAc:FA causes changes in the rate and heat of reaction of the overall system. When slag is used as the alkaline powder, the main factor that increases the CO<sub>2</sub> footprint becomes the grinding of granulated slag. Since the oxalate salt portion of the system remains unchanged, SlOx cements can be carbon negative, as long as the emissions due to grinding are below 1 g CO<sub>2</sub> per 1 g ground slag. This reinforces the importance of identifying a low-carbon-footprint alkaline powder to replace dead-burned MgO in making oxalate cements.</p>
				<p>The cost of MgSlOx concrete is assessed (<xref ref-type="table" rid="t4">Table 4</xref>) by making assumptions about the unit costs of various materials or operations (<xref ref-type="bibr" rid="B15">15</xref>). 300 kg of powder (MgO1500+slag+FAOx) is assumed per 1 m<sup>3</sup> of concrete. Using the proportions in <xref ref-type="table" rid="t2">Table 2</xref>, 210 kg of the powder is FAOx, so ~153.3 kg OxAc (dihydrate) is needed (~0.73 g OxAc is required to make 1 g of the FAOx in this study). The production of OxAc from CO<sub>2</sub> is not done at a large scale outside of the lab, so it is most difficult to assign a cost to this process. The current cost of sustainable OxAc production from CO<sub>2</sub> (including the cost of CO<sub>2</sub>) was estimated in a European research Project (<xref ref-type="bibr" rid="B34">34</xref>) as &gt; 1100 $/t. However the cost was projected to drop to &lt; 450 $/t beyond 2030, with lower or negative CO<sub>2</sub> cost (with incentives), a reduction in cell cost, and improved current densities, and a reduced electricity price. Another study (<xref ref-type="bibr" rid="B31">31</xref>) estimated the cost of electrochemical production of OxAc from CO<sub>2</sub> as being equal to the market price of oxalic acid made from other sources, which can be taken as 450-600 $/t (<xref ref-type="bibr" rid="B64">64</xref>). They did not include the cost of capturing CO<sub>2</sub> needed to produce OxAc which is also difficult to estimate. As an example, for one of the methods, direct air capture, Keith et al. (<xref ref-type="bibr" rid="B65">65</xref>) estimate levelized costs of 94-232 $/t. Based on these studies, 450 $/t, 750 $/t, and 1100 $/t are chosen as the unit price of OxAc made from captured CO<sub>2</sub>. Hence, the cost of OxAc used to produce MgSlOx concrete becomes 69-168.6 $/m<sup>3</sup>.</p>
				<table-wrap id="t4">
					<label>Table 4</label>
					<caption>
						<title>Simple cost analysis for 1 m<sup>3</sup> MgSlOx concrete.</title>
					</caption>
					<table>
						<colgroup>
							<col/>
							<col/>
							<col/>
							<col/>
							<col/>
							<col/>
							<col/>
							<col/>
						</colgroup>
						<thead>
							<tr>
								<th align="center" rowspan="2">Material /process</th>
								<th align="center" rowspan="2">Amount in concrete (kg/m<sup>3</sup>)</th>
								<th align="center" colspan="3">Unit price ($/t) </th>
								<th align="center" colspan="3">Estimated cost ($/m<sup>3</sup>) </th>
							</tr>
							<tr>
								<th align="center">Low</th>
								<th align="center">Intermediate</th>
								<th align="center">High</th>
								<th align="center">Low</th>
								<th align="center">Intermediate</th>
								<th align="center">High</th>
							</tr>
						</thead>
						<tbody>
							<tr>
								<td align="center" rowspan="2">OxAc (includes CO<sub>2</sub> capture)</td>
								<td align="center">107.1</td>
								<td align="center" rowspan="2">450</td>
								<td align="center" rowspan="2">750</td>
								<td align="center" rowspan="2">1100</td>
								<td align="center" rowspan="2">69.0</td>
								<td align="center" rowspan="2">115.0</td>
								<td align="center" rowspan="2">168.6</td>
							</tr>
							<tr>
								<td align="center">(from 153.3 kg H<sub>2</sub>C<sub>2</sub>O<sub>4</sub>.2H<sub>2</sub>O)</td>
							</tr>
							<tr>
								<td align="left">MgO1500</td>
								<td align="center">45</td>
								<td align="center" colspan="3">150 </td>
								<td align="center" colspan="3">6.8 </td>
							</tr>
							<tr>
								<td align="left">Slag</td>
								<td align="center">45</td>
								<td align="center" colspan="3">20 </td>
								<td align="center" colspan="3">0.9 </td>
							</tr>
							<tr>
								<td align="left">Borax</td>
								<td align="center">15</td>
								<td align="center" colspan="3">500 </td>
								<td align="center" colspan="3">7.5 </td>
							</tr>
							<tr>
								<td align="left">FA</td>
								<td align="center">102.9</td>
								<td align="center" colspan="3">20 </td>
								<td align="center" colspan="3">2.1 </td>
							</tr>
							<tr>
								<td align="left">Production of FAOx</td>
								<td align="center" rowspan="2">-</td>
								<td align="center" colspan="3" rowspan="2">15 </td>
								<td align="center" colspan="3" rowspan="2">3.2 </td>
							</tr>
							<tr>
								<td align="left">(heating 210 kg/m<sup>3</sup>)</td>
							</tr>
							<tr>
								<td align="left">Aggregates</td>
								<td align="center">2000</td>
								<td align="center" colspan="3">10 </td>
								<td align="center" colspan="3">20 </td>
							</tr>
							<tr>
								<td align="left">Water</td>
								<td align="center">150</td>
								<td align="center" colspan="3">5 </td>
								<td align="center" colspan="3">0.8 </td>
							</tr>
							<tr>
								<td align="left">Total</td>
								<td align="center">2465</td>
								<td align="center" colspan="3">- </td>
								<td align="center">110.1 </td>
								<td align="center">156.1</td>
								<td align="center">209.8</td>
							</tr>
						</tbody>
					</table>
				</table-wrap>
				<p>A low-purity MgO1500 obtained like the one in this study, assumed to cost 150 $/t (<xref ref-type="bibr" rid="B66">66</xref>), adds another 6.8 $/m<sup>3</sup> (four tenths of the powder binder is MgO1500). Costs of 20 $/t for ground slag (<xref ref-type="bibr" rid="B67">67</xref>), 10 $/t for aggregates, 5 $/t for mixing water (W/B = 0.5), and 500 $/t for borax are assumed. The cost of 102.9 kg/m<sup>3</sup> FA (~49 % of FAOx) is assumed to be 2.1 $/m<sup>3</sup> even though the FA in this study is a waste (not suitable for PC concrete). The production cost of FAOx is assumed as 15 $/t by comparison with similar low-temperature processes (e.g. production of gypsum) which adds another 3.2 $/m<sup>3</sup> (for 210 kg/m<sup>3</sup> FAOx). The total cost of MgSlOx concrete becomes ~110-210 $/m<sup>3</sup>. This does not consider mixing, delivery etc. which would have to differ from PC systems because of differences in properties like setting time, or profit. Similar calculations for MgOx-6/4 yield a cost range of 110-195 $/m<sup>3</sup>, slightly lower because of the decreased amount of oxalic acid used. In comparison, ready-mixed concrete can cost &gt; 150 $ in many developed countries (<xref ref-type="bibr" rid="B68">68</xref>). These calculations show that the cost of oxalate cement is dominated by the cost of producing oxalates from captured CO<sub>2</sub> and that changing the alkaline powder does not influence cost as much as it does the carbon footprint. Nevertheless, the identification of an effective low-carbon base may allow the amount of OxAc in these systems to be slightly reduced and still achieve carbon neutrality (e.g. FAOx/basic powder &lt; 6:4) which could further decrease the overall cost.</p>
			</sec>
		</sec>
		<sec id="sec4" sec-type="conclusions">
			<label>4.</label>
			<title>Conclusions</title>
			<p>The development of oxalate cements made with ground granulated blast furnace slag were introduced and compared with magnesium oxalate cements. The following conclusions were reached:</p>
			<list list-type="bullet">
				<list-item>
					<p>The setting times of SlOx are shorter than those of MgOx. The use of borax can increase setting time &gt; 10 min for MgOx. </p>
				</list-item>
				<list-item>
					<p>The final products in both systems are hydrated oxalates and unreacted raw materials. MgOx contains glushinskite and whewellite, while SlOx contains whewellite and weddellite. Microscopy reveals prismatic crystals of 3-5 &#xb5;m size in MgOx. Slag-containing pastes contain smaller crystals in a glassy background.</p>
				</list-item>
				<list-item>
					<p>Unlike MgOx mortars which show greater early strength, SlOx mortars continue to gain strength beyond 7 d. MgSlOx hybrid mortar reaches ~37 MPa, the highest strength at 28 d.</p>
				</list-item>
				<list-item>
					<p>SlOx contains smaller pores (&lt; 0.2 &#xb5;m) than MgOx (&lt; 1 &#xb5;m). Despite their smaller pores, the resistance of SlOx to water is significantly lower than MgOx or MgSlOx.</p>
				</list-item>
				<list-item>
					<p>The final pH of the pastes is ~9 for MgOx and ~5 for SlOx. An equal part combination of the two alkaline powders gives MgSlOx a pH of ~7, indicating a better balance between acidic and alkaline components.</p>
				</list-item>
				<list-item>
					<p>Both slag and dead-burned magnesia can be reacted with oxalic acid salts to yield a fast-setting cement paste or mortar with medium strength. Replacement of dead-burned magnesia with slag reduces the CO<sub>2</sub> footprint of the binder, which can be truly carbon neutral if made using oxalic acid made from captured CO<sub>2</sub>.</p>
				</list-item>
			</list>
		</sec>
	</body>
	<back>
		<ack>
			<title>Acknowledgements</title>
			<p>This research did not receive any specific grant from funding agencies in the public, commercial, or not-for-profit sectors.</p>
		</ack>
		<fn-group>
			<title>Author contributions</title>
			<fn fn-type="con" id="fn1">
				<p>
					<bold>Conceptualization:</bold> S.T. Erdo&#x11f;an. <bold>Investigation:</bold> S.T. Erdo&#x11f;an, B.A. Bilginer. <bold>Methodology:</bold> S.T. Erdo&#x11f;an, B.A. Bilginer. <bold>Supervision:</bold> S.T. Erdo&#x11f;an. <bold>Writing, original draft:</bold> S.T. Erdo&#x11f;an, B. A. Bilginer. <bold>Writing, review &amp; editing:</bold> S.T. Erdo&#x11f;an, B.A. Bilginer.</p>
				</fn>
		</fn-group>
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