MAGNESIUM CEMENTS IN CONSTRUCTION

A SEMINAR PRESENTATION BY MOHAMMAD SHIHABUDDIN KHAN (131515), M. TECH., ENGINEERING STRUCTURES NATIONAL INSTITITE OF TECHNOLOGY, WARANGAL, INDIA

CONTENTS

1. HISTORY OF MAGNESIUM CEMENTS 2. REINVENTION OF MAGNESIUM CEMENTS 3. MAGNESIUM OXYCHLORIDE CEMENTS 4. MAGNESIUM OXYSUPLHATE CEMENTS 5. MAGNESIUM PHOSPHATE CEMENTS 6. GRANCRETE 7. RESEARCH SCOPE

8. REFERENCES

A little history of magnesium & Magnesium cements

Magnesium is the second most abundant element on earth (roughly 8% of the earths crust). Most popularly used cements before Portland cements. Integral part of the Roman Cements. First produced by Frenchman Stanislas Sorel in 1867.

Historic Applications Terracotta Army, China

"Terracotta Warriors and Horses", is a collection of terracotta sculptures depicting the armies of Qin Shi Huang, the first Emperor of China. 210-209 BC

Large amounts of MgO

Historic Applications Great Wall of China

MgO based mortar, and soil brick stabilizer, is used extensively on The Wall, and in many places, has outperformed, and outlived even some stone. 220-206 BC

Historic Applications The Roman Pantheon

The pozzolana they used for the cement in many Roman buildings contain large amounts of MgO and other Metal Oxides.

Historic Applications The Brooklyn Bridge

The base of the Brooklyn Bridge is made from a locally mined cement called, Rosendale Natural Cement, that is CaO and a little MgO. Also used in the pedestal of the Statue of Liberty, Federal Hall, and one of the wings of the United States Capitol building.

Properties of Magnesia Cements

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 what went wrong?

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

Reinvention of Magnesium Cements

1. Magnesium Oxychloride Cements (MOC) 2. Magnesium Oxysulphate Cements (MOSC) 3. Magnesium Phosphate Cements (MPC)

MAGNESIUM OXYCHLORIDE CEMENTS

Formed from a combination of Magnesia (MgO) and Brine (MgCl2.6H2O)solution. 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
MgCl2 + 5MgO + 13H2O = (Mg(OH)2)5.MgCl2.8H2O

MAGNESIUM OXYCHLORIDE CEMENTS Applications

1. industrial flooring, floor tiles 2. fire protection, fire proofing materials 3. grinding wheels 4. wall insulation panels, thermal insulation 5. Solidification of Municipal Wastes

MAGNESIUM OXYCHLORIDE CEMENTS - Properties

It does 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. Low Coefficient of Thermal Expansion. High Volume Expansion High Water Solubility

MAGNESIUM OXYCHLORIDE CEMENTS Properties

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) MORTAR - Dry Mixes of Magnesia and Dolomite Powder 1:3, 1:4, 1:5 with MgCl2 concentrations varying from 16-36 Be CONCRETE -

PREPARATION OF SPECIMENS

MAGNESIUM OXYCHLORIDE CEMENTS Properties

CONCLUSIONS

MOC is an early setting, high strength Cement and it can bind high proportions of aggregates and fillers. It has good rheological properties with excellent workability.

MAGNESIUM OXYCHLORIDE CEMENTS Properties

It has very high compressive strength and flexural strength

MAGNESIUM OXYCHLORIDE CEMENTS Properties

MAGNESIUM OXYCHLORIDE CEMENTS Properties

MAGNESIUM OXYCHLORIDE CEMENTS Properties

MAGNESIUM OXYCHLORIDE CEMENTS Properties

MAGNESIUM OXYCHLORIDE CEMENTS Properties

Replacement of 10% Magnesium Chloride Solution with Magnesium Sulphate solution of the same concentration makes the concrete resistant to extreme weather conditions.

MAGNESIUM OXYCHLORIDE CEMENTS Limitations

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 OXYSULPHATE CEMENTS

Magnesium oxysulfates (MOS) are formulated by the reaction between magnesium oxide and magnesium sulfate solution,

Very Good binding properties.

Hardening properties are due to the following phases - Four oxysulfate phases are formed at temperatures between 30C and 120C;

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 3MgO + MgSO4 +11H2O = 3(Mg(OH)2).MgSO4.8H2O (Formation of 3 phase)

MAGNESIUM OXYSULPHATE CEMENTS

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. The major use of MOS cement is in the manufacture of lightweight insulating panels. Generally a blend of magnesium oxysulfates and chlorides are considered the most waterproof.

MAGNESIUM PHOSPHATE CEMENTS

The main problem with Sorel cements is that both magnesium oxy chlorides and magnesium oxy sulfates tend to break down in water and particularly in acids. Corrosion of steel reinforcing also occurs. The use of soluble silicates such as sodium silicate has been described as a means of improving the water resistance of Sorel type cements. These cements are of little practical use however because of the high cost of soluble silicates. The use of phosphates has also been advocated as a means of improving the water resistance of Sorel type cements. Such cements are expensive due to the shortage of economic deposits of phosphate and as a result widespread use is limited.

MAGNESIUM PHOSPHATE CEMENTS

Magnesium phosphate cements are formed by the reaction of magnesium oxide with a soluble phosphate, such as ammonium phosphate or a monodibasic salt like potassium di-hydrogen phosphate (KH2PO4) In contrast to MOC and MOS cements, this cement system has good water and freeze thaw resistance. 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. 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 (Struvite), 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.

MAGNESIUM PHOSPHATE CEMENTS

During the reaction of magnesia and ammonium dihydrogen phosphate, however, some ammonia is liberated as a gas, which may lead to container corrosion and create an unpleasant environmental odor. Therefore, the utilization of this cement is limited.

Potassium dihydrogen phosphate (KDP) has recently been identified as a good candidate for replacing ammonium phosphate

MAGNESIUM PHOSPHATE CEMENTS

(1) very rapid setting (2) high early strength (3) ability to set and harden at temperatures as low as 20 C (4) high bonding strength and (5) very good durability, including chemical attack resistance, deicer scaling resistance and permeation resistance. Therefore, the applications of MPC as a repair material has been received increased attention.

MAGNESIUM PHOSPHATE CEMENTS evaluation as a repair material

MATERIALS - Dead burned magnesia, fly ash (FA), Chemical grade potassium dihydrogen phosphate (KH2PO4 or KDP) and borax (Na2-B4O710H2O) were adopted in this study.

MAGNESIUM PHOSPHATE CEMENTS evaluation as a repair material

MAGNESIUM PHOSPHATE CEMENTS evaluation as a repair material

MAGNESIUM PHOSPHATE CEMENTS evaluation as a repair material

MPC mortars have distinctly higher bond strength than OPC mortar, with a 77120% enhancement in flexural bond strength and a 85180% increment in tensile bond strength.

MAGNESIUM PHOSPHATE CEMENTS evaluation as a repair material

The shrinkage of MPC mortars at 28 days is around 2050% less than that of OPC mortar. CONCLUSION It is found that an M/P ratio of 8 and a S/B ratio of 1.5 can be regarded as optimum for MPC mortar formulation for patch repair in terms of mechanical strength, workability, as well as cost consideration.

MAGNESIUM PHOSPHATE CEMENTS GRANCRETE

It is a new Building Material. Grancrete is a fine powder with fibres. It is 50% sand, 25% ash and 25% Binding Material (Magnesium Oxide and Potassium Phosphate). Developed at Argonne National Laboratory, Chicago, Illinois, United States of America. Developed by Jim Paul (President of Casa Grande LLC) and Dr. Arun Wagh (Argonne National Laboratory).

MAGNESIUM PHOSPHATE CEMENTS GRANCRETE

MAGNESIUM PHOSPHATE CEMENTS GRANCRETE

The shell of the building is constructed using expandable polystyrene (EPS) foam panels, such as Styrofoam-brand EPS panels, which are held in place using lightweight aluminum channels anchored to the foundation.

MAGNESIUM PHOSPHATE CEMENTS GRANCRETE

Lightweight aluminum channels also are used at the corners and between every 4-foot by 8-foot panel to hold them in position during spraying. From start to finish, all of the foam panels for the walls and roof can be installed and ready to be covered by Grancrete cement in just a few hours.

MAGNESIUM PHOSPHATE CEMENTS GRANCRETE

The roof is also constructed of foam panels that are held in place by aluminum channels. Once covered with Grancrete, the roof becomes an integral, water-tight part of the home.

MAGNESIUM PHOSPHATE CEMENTS GRANCRETE

The window and door openings are cut out of the foam, and the frames installed. Conduit and pipes for electrical and plumbing utilities can be attached to the foam and then sprayed over with Grancrete to conceal and protect them.

MAGNESIUM PHOSPHATE CEMENTS GRANCRETE

Both the exterior and interior of the walls and roof are sprayed to a thickness of about one-half inch. Grancrete is sprayed around the windows and door frames to ensure a weather-proof seal.

MAGNESIUM PHOSPHATE CEMENTS GRANCRETE

A few hours later the Grancrete has hardened and is ready to be occupied.

RESEARCH SCOPE

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) 13651371) 3. C.K. Chau, Fei Qiao, Zongjin Li, The Hong Kong University of Science and Technology, Hong Kong (Construction and Building Materials 25 (2011) 29112917) 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)