Magnesium oxide explained

Magnesium oxide (MgO), or magnesia, is a white hygroscopic solid mineral that occurs naturally as periclase and is a source of magnesium (see also oxide). It has an empirical formula of MgO and consists of a lattice of Mg²⁺ ions and O²⁻ ions held together by ionic bonding. Magnesium hydroxide forms in the presence of water (MgO + H₂O → Mg(OH)₂), but it can be reversed by heating it to remove moisture.

Magnesium oxide was historically known as magnesia alba (literally, the white mineral from Magnesia), to differentiate it from magnesia nigra, a black mineral containing what is now known as manganese.

Related oxides

While "magnesium oxide" normally refers to MgO, the compound magnesium peroxide MgO₂ is also known. According to evolutionary crystal structure prediction,^[1] MgO₂ is thermodynamically stable at pressures above 116 GPa (gigapascals), and a semiconducting suboxide Mg₃O₂ is thermodynamically stable above 500 GPa. Because of its stability, MgO is used as a model system for investigating vibrational properties of crystals.^[2]

Electric properties

Pure MgO is not conductive and has a high resistance to electric current at room temperature. The pure powder of MgO has a relative permittivity inbetween 3.2 to 9.9

k with an approximate dielectric loss of tan(δ) > 2.16x10³ at 1kHz.^{[3] [4] [5]}

Production

Magnesium oxide is produced by the calcination of magnesium carbonate or magnesium hydroxide. The latter is obtained by the treatment of magnesium chloride solutions, typically seawater, with limewater or milk of lime.

Mg²⁺ + Ca(OH)₂ → Mg(OH)₂ + Ca²⁺Calcining at different temperatures produces magnesium oxide of different reactivity. High temperatures 1500 – 2000 °C diminish the available surface area and produces dead-burned (often called dead burnt) magnesia, an unreactive form used as a refractory. Calcining temperatures 1000 – 1500 °C produce hard-burned magnesia, which has limited reactivity and calcining at lower temperature, (700–1000 °C) produces light-burned magnesia, a reactive form, also known as caustic calcined magnesia. Although some decomposition of the carbonate to oxide occurs at temperatures below 700 °C, the resulting materials appear to reabsorb carbon dioxide from the air.

Applications

Refractory insulator

MgO is prized as a refractory material, i.e. a solid that is physically and chemically stable at high temperatures. It has the useful attributes of high thermal conductivity and low electrical conductivity. According to a 2006 reference book:^[6]

MgO is used as a refractory material for crucibles. It is also used as an insulator in heat-resistant electrical cable.

Biomedical

Among metal oxide nanoparticles, magnesium oxide nanoparticles (MgO NPs) have distinct physicochemical and biological properties, including biocompatibility, biodegradability, high bioactivity, significant antibacterial properties, and good mechanical properties, which make it a good choice as a reinforcement in composites. ^[7]

Heating elements

It is used extensively as an electrical insulator in tubular construction heating elements as in electric stove and cooktop heating elements. There are several mesh sizes available and most commonly used ones are 40 and 80 mesh per the American Foundry Society. The extensive use is due to its high dielectric strength and average thermal conductivity. MgO is usually crushed and compacted with minimal airgaps or voids.

Cement

MgO is one of the components in Portland cement in dry process plants.

Sorel cement uses MgO as the main component in combination with MgCl₂ and water.

Fertilizer

MgO has an important place as a commercial plant fertilizer^[8] and as animal feed.^[9]

Fireproofing

It is a principal fireproofing ingredient in construction materials. As a construction material, magnesium oxide wallboards have several attractive characteristics: fire resistance, termite resistance, moisture resistance, mold and mildew resistance, and strength, but also a severe downside as it attracts moisture and can cause moisture damage to surrounding materials ^{[10] [6]} https://www.building-supply.dk/article/view/227159/de_fugtige_mgoplader_en_guide_til_problemstillingen

Medical

Magnesium oxide is used for relief of heartburn and indigestion, as an antacid, magnesium supplement, and as a short-term laxative. It is also used to improve symptoms of indigestion. Side effects of magnesium oxide may include nausea and cramping.^[11] In quantities sufficient to obtain a laxative effect, side effects of long-term use may rarely cause enteroliths to form, resulting in bowel obstruction.^[12]

Waste treatment

Magnesium oxide is used extensively in the soil and groundwater remediation, wastewater treatment, drinking water treatment, air emissions treatment, and waste treatment industries for its acid buffering capacity and related effectiveness in stabilizing dissolved heavy metal species.

Many heavy metals species, such as lead and cadmium, are least soluble in water at mildly basic conditions (pH in the range 8–11). Solubility of metals increases their undesired bioavailability and mobility in soil and groundwater. Granular MgO is often blended into metals-contaminating soil or waste material, which is also commonly of a low pH (acidic), in order to drive the pH into the 8–10 range. Metal-hydroxide complexes tend to precipitate out of aqueous solution in the pH range of 8–10.

MgO is packed in bags around transuranic waste in the disposal cells (panels) at the Waste Isolation Pilot Plant, as a getter to minimize the complexation of uranium and other actinides by carbonate ions and so to limit the solubility of radionuclides. The use of MgO is preferred over CaO since the resulting hydration product is less soluble and releases less hydration heat. Another advantage is to impose a lower pH value (about 10.5) in case of accidental water ingress into the dry salt layers, in contast to the more soluble which would create a higher pH of 12.5 (strongly alkaline conditions). The cation being the second most abundant cation in seawater and in rocksalt, the potential release of magnesium ions dissolving in brines intruding the deep geological repository is also expected to minimize the geochemical disruption.^[13]

Niche uses

• As a food additive, it is used as an anticaking agent. It is known to the US Food and Drug Administration for cacao products; canned peas; and frozen dessert.^[14] It has an E number of E530.
• As a reagent in the installation of the carboxybenzyl (Cbz) group using benzyl chloroformate in EtOAc for the N-protection of amines and amides.^[15]
• Doping MgO (about 1–5% by weight) into hydroxyapatite, a bioceramic mineral, increases the fracture toughness by migrating to grain boundaries, where it reduces grain size and changes the fracture mode from intergranular to transgranular.^{[16] [17]}
• Pressed MgO is used as an optical material. It is transparent from 0.3 to 7 μm. The refractive index is 1.72 at 1 μm and the Abbe number is 53.58. It is sometimes known by the Eastman Kodak trademarked name Irtran-5, although this designation is obsolete. Crystalline pure MgO is available commercially and has a small use in infrared optics.^[18]
• An aerosolized solution of MgO is used in library science and collections management for the deacidification of at-risk paper items. In this process, the alkalinity of MgO (and similar compounds) neutralizes the relatively high acidity characteristic of low-quality paper, thus slowing the rate of deterioration.^[19]
• Magnesium oxide is used as an oxide barrier in spin-tunneling devices. Owing to the crystalline structure of its thin films, which can be deposited by magnetron sputtering, for example, it shows characteristics superior to those of the commonly used amorphous Al₂O₃. In particular, spin polarization of about 85% has been achieved with MgO^[20] versus 40–60 % with aluminium oxide.^[21] The value of tunnel magnetoresistance is also significantly higher for MgO (600% at room temperature and 1,100 % at 4.2 K^[22]) than Al₂O₃ (ca. 70% at room temperature^[23]).

Historical uses

• It was historically used as a reference white color in colorimetry, owing to its good diffusing and reflectivity properties.^[24] It may be smoked onto the surface of an opaque material to form an integrating sphere.
• Early gas mantle designs for lighting, such as the Clamond basket, consisted mainly of magnesium oxide.

Precautions

Inhalation of magnesium oxide fumes can cause metal fume fever.^[25]

External links

• Data page at UCL
• Ceramic data page at NIST
• NIOSH Pocket Guide to Chemical Hazards at CDC

Notes and References

1. Zhu. Qiang. Oganov A.R.. Lyakhov A.O.. Novel stable compounds in the Mg-O system under high pressure. Phys. Chem. Chem. Phys.. 2013. 15. 20. 7696–7700. 10.1039/c3cp50678a. 23595296. 2013PCCP...15.7696Z. 2013-11-06. 2013-12-03. https://web.archive.org/web/20131203011451/http://uspex.stonybrook.edu/pdfs/Mg-O-paper-2013.pdf. dead.
2. Mei. AB. O. Hellman. C. M. Schlepütz. A. Rockett. T.-C. Chiang. L. Hultman. I. Petrov. Ivan Georgiev Petrov. J. E. Greene. J. E. Greene. Reflection Thermal Diffuse X-Ray Scattering for Quantitative Determination of Phonon Dispersion Relations.. Physical Review B. 92. 17. 2015. 174301. 10.1103/physrevb.92.174301. 2015PhRvB..92q4301M. free.
3. A P . Johnson . November 1986 . Structural and electrical properties of magnesium oxide powders . Durham University. Masters .
4. Subramanian . M. A. . Shannon . R. D. . Chai . B. H. T. . Abraham . M. M. . Wintersgill . M. C. . November 1989 . Dielectric constants of BeO, MgO, and CaO using the two-terminal method . Physics and Chemistry of Minerals . en . 16 . 8 . 741–746 . 10.1007/BF00209695 . 1989PCM....16..741S . 95280958 . 0342-1791.
5. Hornak . Jaroslav . Trnka . Pavel . Kadlec . Petr . Michal . Ondřej . Mentlík . Václav . Šutta . Pavol . Csányi . Gergely . Tamus . Zoltán . 2018-05-30 . Magnesium Oxide Nanoparticles: Dielectric Properties, Surface Functionalization and Improvement of Epoxy-Based Composites Insulating Properties . Nanomaterials . en . 8 . 6 . 381 . 10.3390/nano8060381 . 2079-4991 . 6027305 . 29848967. free .
6. Book: Mark A. Shand . The chemistry and technology of magnesia . 10 September 2011 . 2006 . John Wiley and Sons . 978-0-471-65603-6.
7. Saberi A, Baltatu MS, Vizureanu P . Recent Advances in Magnesium-Magnesium Oxide Nanoparticle Composites for Biomedical Applications . Bioengineering . 11 . 5 . 508 . May 2024 . 38790374 . 11117911 . 10.3390/bioengineering11050508 . free.
8. https://web.archive.org/web/20160422171902/http://www.fertilizer101.org/science/?seq=10 Nutrient Science
9. https://web.archive.org/web/20150303043215/http://www.lehvoss.de/eng/1039.htm Magnesium oxide for the Animal Feed Industry
10. Mármol. Gonzalo. Savastano. Holmer. July 2017. Study of the degradation of non-conventional MgO-SiO 2 cement reinforced with lignocellulosic fibers. Cement and Concrete Composites. 80. 258–267. 10.1016/j.cemconcomp.2017.03.015.
11. https://www.nlm.nih.gov/medlineplus/druginfo/meds/a601074.html Magnesium Oxide
12. Tatekawa Y. Small bowel obstruction caused by a medication bezoar: report of a case. Surgery Today. 26. 1. 68–70. 1996. 8680127. 10.1007/BF00311997. vanc. Nakatani K. Ishii H. 3. Paku. Shuuichi. Kasamatsu. Minoru. Sekiya. Nao. Nakano. Hiroshige. 24976010.
13. http://www.wipp.energy.gov/fctshts/wastehandling.pdf wipp.energy.gov Step-By-Step Guide for Waste Handling at WIPP
14. Web site: Compound Summary for CID 14792 – Magnesium Oxide . PubChem.
15. Dymicky. M.. 1989-02-01. Preparation of Carbobenzoxy-L-Tyrosine Methyl and Ethyl Esters and of the Corresponding Carbobenzoxy Hydrazides. Organic Preparations and Procedures International. 21. 1. 83–90. 10.1080/00304948909356350. 0030-4948.
16. 10.1016/j.ceramint.2013.04.098 . Tan . C.Y. . Yaghoubi . A. . Ramesh . S. . Adzila . S. . Purbolaksono . J. . Hassan . M.A. . Kutty . M.G. . December 2013 . Sintering and mechanical properties of MgO-doped nanocrystalline hydroxyapatite . Ceramics International . 39 . 8 . 8979–8983 . 2015-08-08 . 2017-03-12 . https://web.archive.org/web/20170312033742/http://www.aun.edu.eg/reserches_files/13211.pdf . dead .
17. Tan . Chou Yong . Singh . Ramesh . Tolouei . R. . Sopyan . Iis . Teng . Wan Dung . Synthesis of High Fracture Toughness of Hydroxyapatite Bioceramics . Advanced Materials Research . 264-265 . 2011 . 1662-8985 . 10.4028/www.scientific.net/amr.264-265.1849 . 1849–1855. 137578750 .
18. Index of Refraction of Magnesium Oxide. Stephens, Robert E.. Malitson, Irving H.. amp. Journal of Research of the National Bureau of Standards. 49. 4. 1952. 249–252. 10.6028/jres.049.025. free.
19. Web site: Mass Deacidification: Saving the Written Word. Library of Congress. 26 September 2011.
20. Parkin . S. S. P. . Kaiser . C. . Panchula . A. . Rice . P. M. . Hughes . B. . Samant . M. . Yang . S. H. . 10.1038/nmat1256 . Giant tunnelling magnetoresistance at room temperature with MgO (100) tunnel barriers . Nature Materials . 3 . 12 . 862–867 . 2004 . 15516928 . 2004NatMa...3..862P . 33709206 .
21. Monsma . D. J. . Parkin . S. S. P. . 10.1063/1.127097 . Spin polarization of tunneling current from ferromagnet/Al₂O₃ interfaces using copper-doped aluminum superconducting films . Applied Physics Letters . 77 . 5 . 720 . 2000 . 2000ApPhL..77..720M .
22. Ikeda . S. . Hayakawa . J. . Ashizawa . Y. . Lee . Y. M. . Miura . K. . Hasegawa . H. . Tsunoda . M. . Matsukura . F. . Ohno . H. . 10.1063/1.2976435 . Tunnel magnetoresistance of 604% at 300 K by suppression of Ta diffusion in CoFeB/MgO/CoFeB pseudo-spin-valves annealed at high temperature . Applied Physics Letters . 93 . 8 . 082508 . 2008 . 2008ApPhL..93h2508I . 122271110 .
23. Wang . D. . Nordman . C. . Daughton . J. M. . Qian . Z. . Fink . J. . Wang . D. . Nordman . C. . Daughton . J. M. . Qian . Z. . 10.1109/TMAG.2004.830219 . Fink . J. . 70% TMR at Room Temperature for SDT Sandwich Junctions with CoFeB as Free and Reference Layers . IEEE Transactions on Magnetics . 40 . 4 . 2269 . 2004 . 10.1.1.476.8544 . 2004ITM....40.2269W . 20439632 .
24. Reflectance of Magnesium Oxide. Peter A.. Tellex. Waldron, Jack R.. JOSA. 1955. 45. 1. 10.1364/JOSA.45.000019. 19. 1955JOSA...45...19T .
25. http://www.npi.gov.au/substances/magnesium-oxide-fume/index.html Magnesium Oxide