HYDRATION OF CRYSTALLINE MgO and CaO & CORROSION prepared by Hikmet ERDL

A review of Types of chemical reactions responsible for concrete deterioration.

part C shown in the figure indicates the corrosion of steel in concrete, hydration of crystalline MgO and CaO.

chemical interactions between the aggressive agents in the environment and the constituents of the cement paste is called as the deterioration processes that caused by chemical reactions. Reactions Involving the Formation of Expansive Products These chemical reactions can lead to harmful effects. Expansion may take place without any damage to concrete, but the increasing of the internal stress manifests itself by closing of the expansion joints, deformations, and displacements in different parts of the structure, cracking, spalling, and pop-outs

Deterioration of Concrete by Chemical Reactions

We will deal with the two of the four phenomena associated with expansive chemical reactions:
hydration of free CaO and MgO corrosion of steel in concrete.

(the other phenomena are sulfate attack, alkali-aggregate attack)

Hydration of Crystalline MgO and CaO

Hydrolysis of the cement paste components

Waters from the ground, lakes, and rivers contain small amounts of chlorides, sulfates, and bicarbonates of calcium and magnesium. These so-called hard waters generally do not attack the constituents of the portland cement paste. Pure water (from condensation of fog or water vapor) and soft water from (rain or from melting of snow and ice) contain little or no calcium ions. When these waters come into contact with portland cement paste they tend to hydrolyze or dissolve the calcium-containing products. The contact solution attains chemical equilibrium, further hydrolysis of the cement paste stops.

However, in the case of flowing water or seepage under pressure, dilution of the contact solution will take place, thus providing the condition for continuous hydrolysis. Calcium hydroxide is one of the constituent of hydrated portland cement pastes which, because of its relatively high solubility in pure water (1230 mg/l), is most susceptible to hydrolysis. CaO (lime) + H2O(water) Ca(OH)2 (calcium hydroxide) Magnesium hydroxide is generally low, and it rises with low temperature and large specific surface area MgO(periclase) + H2O Mg(OH)2(magnesium hydroxide)

History Cases

The expansive effect of high MgO in cement was first recognized in 1884 when a number of concrete bridges and viaducts in France failed two years after the construction with the cement contained 16 to 30 percent MgO

About the same time, the town hall of Kassel in Germany had to be rebuilt as a result of expansion and cracking attributed to crystalline MgO in cement with the cement contained 27 percent MgO,

This led to restrictions on the maximum permissible MgO in cement. ASTM Standard Specification for Portland Cement (ASTM C 150-83) requires that the MgO content in cement shall not exceed 6 percent.

Although expansion due to hydration of crystalline CaO has been known for a long time in the United States, the deleterious effect associated with the phenomenon was recognized in the 1930s when certain 2- to 5-year-old concrete pavements cracked. Initially suspected to be due to MgO, the expansion and cracking were attributed later to the presence of hard-burnt CaO in the cement used for the construction of the pavements. Laboratory tests showed that the cement pastes made with a low-MgO portland cement, which contained 2.8 percent hard-burnt CaO, showed considerable expansion

The phenomenon is unknown with modern concrete because control of quality of Portland Cement clinker have assured that the content of uncombined or free CaO in clinker exceeds 1 percent. The crystalline MgO in a PC clinker that has been exposed to 1400 to 1500C is essentially inert to moisture at room temp. because the reactivity of crystalline MgO drops sharply when it is heated above 900C. No cases of structural distress due to the presence of crystalline MgO in modern Portland Cements are reported from countries, where raw material limitations compel some cement producers to manufacture portland cements containing more than 6 percent MgO.

Corrosion

Corrosion of Embedded Steel in Concrete

Corrosion occurs when two different metals, or

metals in different environments, are electrically connected in a moist or damp concrete. The resulting rust occupies a greater volume than the steel. This expansion creates tensile stresses in the concrete, which can eventually cause expantion, cracking, and spalling.

Steel, is thermodynamically unstable under normal atmospheric conditions and will release energy and revert back to its natural stateiron oxide, or rust. This process is called corrosion.

1.

2. 3.

For corrosion to occur, three elements must be present: There must be at least two metals (or two locations on a single metal) at different energy levels an electrolyte a metallic connection

Corrosion will occur when: 1. Steel reinforcement is in contact with an aluminium conduit. 2. Concrete pore water composition varies between adjacent or along reinforcing bars. 3. Where there is a variation in alloy composition between or along reinforcing bars. 4. Where there is a variation in residual or applied stress along or between reinforcing bars. 5. Where there are imposed stray electrical currents.

Corrosion of reinforced concrete

Concrete acts as the electrolyte, and the metallic connection is provided by wire ties, chair supports, or the rebar itself.

Electrochemical process of steel

corrosion in concrete

Corrosion is an electrochemical process involving the flow of charges (electrons and ions). At active sites on the bar, called anodes, iron atoms lose electrons and move into the surrounding concrete as ferrous ions. This process is called the anodic reaction, and is represented as: 2Fe 2Fe2+ + 4e-

The electrons remain in the bar and flow to sites called cathodes, where they combine with water and oxygen in the concrete. The reaction at the cathode is called a the cathodic reaction or

reduction reaction
A common reduction reaction is: 2H2O + O2 + 4e- 4OH To maintain electrical neutrality, the ferrous ions migrate through the concrete pore water to these cathodic sites where they combine to form iron hydroxides or rust 2Fe2+ + 4OH- 2Fe(OH)2

This initial precipitated hydroxide tends to react further with oxygen to form higher oxides. The increases in volume as the reaction products react further with dissolved oxygen leads to internal stress within the concrete that may be sufficient to cause cracking and spalling of the concrete cover.

depending on the oxidation state, the corrosion of metallic iron can result in up to six times increase in the solid volume.

Volumetric change

Absence of Chloride Ions in Solution

the protective film on steel is reported to be stable as long as the pH of the solution stays above 11.5. Under some conditions (e.g., when concrete has high permeability and alkalies and most of the calcium hydroxide have either been carbonated or leached away), the pH of concrete in the vicinity of steel may have been reduced to less than 11.5. This would destroy the passivity of steel and set the stage for the corrosion process.

depending on the Cl/OH ratio, it is reported that the protective film is destroyed even at pH values considerably above 11.5. when Cl/OH molar ratio is higher than 0.6, steel is no longer protected against corrosion probably because the iron-oxide film becomes either permeable or unstable under these conditions. The chloride content to initiate corrosion is reported to be in the range 0.6 to 0.9 kg Cl per cubic meter of concrete.

Presence of Chloride Ions in Solution

Corrosion Potential

The corrosion potential of the steel in reinforced concrete can be measured as the voltage difference between the steel and a reference electrode in contact with the surface of the concrete. Half-cell measurements may be made relatively easily, using only a high impedance voltmeter and a standard reference electrode, such as a copper-copper sulfate electrode.

System for measuring the halfcell potential

The potential recorded in the half-cell measurement can be used to indicate the probability of corrosion of the steel reinforcement

Results affected by

Degree of humidity in concrete. The

measurement is very sensitive to the humidity existing in the concrete. More negative potentials result for concrete with higher degree of saturation. Stray currents. The presence of stray currents will significantly affect the measurements of the half-cell potential.

Oxygen content near the reinforcement. The

lack of oxygen near the reinforcement results in more negative potentials as compared to more aerated zones.

Microcracks. Localized corrosion can be

generated by microcracks, which also modify the concrete resistivity, consequently affecting the corrosion potential measurement.

Diagrammatic representation of the cracking-corrosion-cracking cycle

Can corrosion be avoided in reinforced concrete? -Yes if: (a) Concrete is always dry, then there is no H2O to form rust. Also aggressive agents cannot easily diffuse into dry concrete. (b) Concrete is always wet, then there is no oxygen to form rust. (c) Cathodic protection is used to convert all the reinforcement into a cathode using a battery. This is not easy to implement because anodic mesh is expensive, and this technology is not easy to install and maintain.

(d) A polymeric coating is applied to the concrete member to keep out aggressive agents. These are expensive and not easy to apply and maintain. (e) A polymeric coating is applied to the reinforcing bars to protect them from moisture and aggressive agents. This is expensive and there is some debate as to its long- term effectiveness. (f) Stainless steel or cladded stainless steel is used in lieu of conventional black bars. This is much more expensive than black bars.

Can we avoid corrosion? - No, not entirely: Concrete is not usually under water or continuously dry. Aggressive agents such as carbon dioxide, deicing agents and/or sea water can diffuse into the best of moist concrete, and corrosion will eventually result. If corrosion cannot always be avoided and economical solutions are required, the effects of corrosion can be minimized by making a better concrete. For example; Fly Ash added to a low w/c concrete produces a much enhanced corrosion resisting structure with no significant increase in cost.

Corrosion damages

Corroded reinforcing steel in concrete pile

Corroded reinforcing steel in concrete deck