A Report On

MAGNESIUM CEMENTS IN THE CONSTRUCTION INDUSTRY

By Mohammad Shihabuddin Khan Roll no 131515

ENGINEERING STRUCTURES DIVISION DEPARTMENT OF CIVIL ENGINEERING NATIONAL INSTITUTE OF TECHNOLOGY, WARANGAL 506004, ANDHRA PRADESH (INDIA) November 2013

INTRODUCTION
Before the widespread 20th century use of Portland cement magnesium oxide and magnesium chloride based cements were numbered amongst the worlds popular cement products. Once the introduction of Portland cement essentially cornered the market in the latter part of the 19th century, serious public health issues began to be quietly recognized, documented, and scientifically verified as being directly linked to the use of limestone/gypsum based cement and concrete products. In contrast to this sobering reality magnesium cements have consistently proven to be superior in strength, versatility, and environmental integrity. In general their properties can be summarized as follows They do not require wet curing (Non Hydraulic Cement). They have high fire resistance Low thermal conductivity Good resistance to abrasion. It has excellent load bearing capacity because of its high transverse and crushing strengths upto 47.5 68.0 Mpa. They also bond very well to a variety of inorganic and organic aggregates High early strength, insectidal properties, resilient. Non Conducting Reduced Carbon Footprint So why were these magnesium cements virtually abandoned over the past 175 years? Durability problems with sustained contact with water (Leaching & Expansion) Durability problems with exposure to acids. Relatively higher cost of raw materials. Highly exothermic reaction of setting

PORTLAND CEMENTS AND SEARCH FOR AN ALTERNATIVE

Since the development of Portland cement over 175 years ago, it has become the dominant binder used in concrete for construction. Annual worldwide Portland cement production is approaching 3 Gt. Praised for its versatility, durability, and economic value, Portland cement concrete is receiving increasing recognition for its relatively low embodied energy compared to other building materials and for its use of local materials, thereby reducing energy and pollution costs associated with material transport. However, Portland cement is not without problems. Because such vast quantities are produced, manufacturing of Portland cement consumes 1011 EJ of energy annually, approximately 23% of global primary energy use. Furthermore, Portland cement production results in approximately 0.87 t of carbon dioxide for every tonne of cement produced, this accounts for 5% of manmade CO2 emissions. The cement industry is under pressure to reduce both energy use and greenhouse gas emissions and is actively seeking alternatives to this familiar and reliable material. Coupled with the interest in seeking low-energy, low-CO2 binders is an interest in finding reuse for waste materials from other industries. Portland cement concrete already ccommodates a wide variety of waste materials used as supplementary cementing materials, including fly ash from coal combustion, ground granulated blast furnace slag from iron production, and silica fume from ferrosilicon production. However, these are used to replace only a portion of the cement in concrete, typically on the order of 1050% (although sometimes used in greater quantities). There is interest in pushing this envelope further, to create binders made entirely oralmost entirely from waste materials or other sustainable sources. Additional motivation for exploring alternatives to Portland cement can be derived from its shortcomings in certain applications and environments. For instance, rapid-repair applications demand a faster strength gain than Portland cement concrete can provide. Similarly, environmental conditions with high acidity or high sulfate concentrations can cause substantial degradation of Portland cement concrete. For such cases, there is a demand for Portland cement alternatives. Durable Magnesium Cements represent new binders are being developed for concrete that promise to reduce the environmental impact of construction, use a greater proportion of waste materials, and/or improve concrete performance. These materials represent a substantial departure from the traditional chemistry of Portland cement, and therefore do not benefit directly from the many years of research into its reaction mechanisms, property development and durability. Furthermore, they have difficulty finding acceptance in the construction industry, making implementation challenging. In this paper we discuss some of these alternative binders which are attracting increasing attention in research and practice, summarizing the current understanding, gaps in knowledge and challenges.

MAGNESIA CEMENTS
Sorel in 1867 announced the discovery of an excellent cement formed from the combination of magnesium oxide and magnesium chloride solution. This cement type is known by many different names, such as Sorel, magnesite and magnesium oxychloride cement. This cement has many superior properties to Portland cement. However, there are two other known magnesia cements. The first is magnesium oxysulfate (MOS), which is the sulfate analogue of magnesium oxychloride and is formed by the combination of magnesium oxide and magnesium sulfate solution. The second is magnesium phosphate cement (MAP), formed by the reaction between magnesium oxide and a soluble phosphate, such as ammonium phosphate monobasic (NH4H2PO4) MAGNESIUM OXYCHLORIDE CEMENT As mentioned above, magnesium oxychloride has many superior properties compared to Portland cement. It does not need wet curing, has high fire resistance, low thermal conductivity, good resistance to abrasion. It also has high transverse and crushing strengths, 7,000-10,000 psi are not uncommon. Magnesium oxychloride also bonds very well to a variety of inorganic and organic aggregates, such as, saw dust, wood flour, marble flour, sand and gravel, giving a cement that has high early strength, insectcidal properties, resilient, conducting and is unaffected by oil, grease and paints. The major commercial applications of magnesium oxychloride cement, are industrial flooring, fire protection, grinding wheels, and because of it's resemblance to marble, have been used for rendering wall insulation panels and for stuccos. The main bonding phases found in hardened cement pastes are Mg(OH)2, 3Mg(OH)2 .MgCl2 .8H2O (3-form) and 5Mg(OH)2.MgCl2 .8H2O (5-form). 5-form is the phase with superior mechanical properties and is formed using a molar ratio of MgO:MgCl2:H2O = 5:1:13 with a slight excess of MgO and the amount of water as close as possible to theoretical required for formation of the 5-form and hydration of the excess MgO to form Mg(OH)2. The reactivity of the MgO influence reaction rates and products, thus affecting the development of strengths. The magnesium oxide should conform to certain requirements of chemical and physical properties. Conditions of calcination, particle size and active lime content must be carefully controlled. The main reason why magnesium oxychloride cement has not remained popular in the building industry is that the magnesium oxychloride phase is not stable in prolonged contact with water, and will result in the leaching of magnesium chloride. Various additives have been added to MOC cements to try and combat this problem of water resistance, with varying degrees of success. Over a period of time, atmospheric carbon dioxide will react with magnesium oxychloride to form a surface layer of Mg2(OH)ClCO3.3H2O. This layer serves to slow the leaching process. Eventually additional leaching results in the formation of hydromagnesite, 4MgO.3CO3.4H2O, which is insoluble and enables the cement to maintain structural integrity.

MAGNESIUM OXYSULFATE CEMENTS Magnesium oxysulfates (MOS) are formulated by the reaction between magnesium oxide and magnesium sulfate solution, and like that of magnesium oxychloride has very good binding properties. The resistance of MOS cements to abrasion is about 1.5 times that of Portland cement, but only 50% that of MOC cement. Its compressive and transverse strengths are superior to Portland cement but not as good as MOC cement. Four oxysulfate phases are formed at temperatures between 30 and 120oC; 5Mg(OH)2.MgSO4.3H2O (5-form), 3Mg(OH)2.MgSO4.8H2O (3-form), Mg(OH2.MgSO4.5H2O, and Mg(OH)2.2MgSO4.3H2O. Only the 3-form is stable below 35oC. The major use of MOS cement is in the manufacture of lightweight insulating panels. MOS cement suffers from the same lack of water resistance as do MOC cements. MAGNESIUM PHOSPHATE CEMENTS Magnesium phosphate cements are formed by the reaction of magnesium oxide with a soluble phosphate, such as ammonium phosphate, either the mono or dibasic salt; or an agricultural fertilizer solution known as 10-34-0 (NPK designation) can also be used. This magnesia cements rapid set and very high early strength has found utility as a rapid patching mortar for road and aircraft run-ways, which can typically be re-opened after about 45 minutes. It has very good adhesion to a wide variety of aggregates and substrates. In contrast to MOC and MOS cements, this cement system has good water and freeze thaw resistance. Commercial magnesium phosphate cements typically reach a compressive strength of about 2900 psi after 1 hour, with an ultimate strength of 8000 psi. The reaction mechanism is thought to be an acid-base reaction between the MgO and the acid phosphate. This results in an initial gel formation followed by the crystallization of this gel into an insoluble phosphate, mainly magnesium ammonium phosphate hexahydrate, NH4MgPO4.6H2O. The magnesium oxide used in this system is a fairly unreactive MgO, either hard or dead-burnt, and is used in conjunction with a set retarder, typically either borax or boric acid, to afford a workable set time.

GRANCRETE Commercial Magnesium Phosphate Cement

Grancrete, a sprayable ceramic which hardens quickly into a solid form, is... ...stronger than concrete, is fire resistant and withstands both tropical and below-freezing temperatures, the developers said; it keeps homes in arid regions cool, and those in frigid regions warm. To build a home, Grancrete is sprayed onto Styrofoam walls, to which it adheres and dries, according to the developers. The Styrofoam remains in place as an effective insulator, although Wagh suggests simpler walls, such as woven fiber mats, also would work well and further reduce the raw materials required. Grancrete is made from local materials, including sand or sandy soil, ash, magnesium oxide and postassium phosphate, found in fertilizer. It's still in testing, however, particularly for earthquake and hurricane resistance. The developer, Dr. Arun Wagh (at Argonne National

Laboratory), is originally from India, and hopes to see Grancrete used as an inexpensive and quick building material for the poor. Grancrete was a 2004 winner of R&D Magazine's top 100 innovations.

RESEARCH SCOPE
Although not a new material, but the reinvention of magnesium cements is a novel idea and there is considerable amount of research work to be done for widespread acceptance of these cements. Some areas of future work could be, Research on Magnesium Cements as a potential additive for OPC Mortars and Concrete. Commercialized repair material development. Study of effect of reactivity of Magnesia on Magnesium Cement Properties. Study of Impact of hydrated magnesium carbonate (HMC) additives on the carbonation of MgO cements. Magnesium Phosphate Cements (MPC) using reactive Magnesia. Microstructural Studies of Magnesium and OPC Blends. Seismic Response Analysis and Response to blast loadings for military applications

REFERENCES
1. A K MISRA and RENU MATHUR from Central Road Research Institute, India (Bull. Mater. Sci., Vol. 30, No. 3, June 2007, pp. 239246. Indian Academy of Sciences) 2. Deng Dehua*, Zhang Chuanmei (Cement and Concrete Research 29 (1999) 1365 1371) 3. C.K. Chau, Fei Qiao, Zongjin Li, The Hong Kong University of Science and Technology, Hong Kong (Construction and Building Materials 25 (2011) 2911 2917) 4. MAGNESIA CEMENTS by Dr. Mark A. Shand of Premier Chemicals 5. Zhu Dinga, Biqin Donga, Feng Xinga, Ningxu Hana, Zong jin Li, China (Ceramics International 38 (2012) 62816288) 6. Li Yue, Chen Bing, Shanghai Jiaotong University, PR China (Construction and Building Materials 47 (2013) 977983) 7. Y. Karimi and A. Monshi, Isfahan University of Technology, Iran (Journal of Ceramic Processing Research. Vol. 13, No. 6, pp. 725~729 (2012) 725) 8. Quanbing Yang , Xueli Wu, College of Materials Science and Engineering, Tongji University, China (Cement and Concrete Research 29 (1999) 389396) 9. Fei Qiao, C.K. Chau, Zongjin Li, The Hong Kong University of Science and Technology, China (Construction and Building Materials 24 (2010) 695700) 10. Dehua Deng, Central South University, Peoples Republic of China (Cement and Concrete Research 33 (2003) 1311 1317)