Chemical and Mineral Admixtures

Chemical admixtures used in concrete generally serve as water reducers, accelerators, set retarders, or a combination. ASTM C494, Standard Specification for Chemical Admixtures for Concrete, contains the following classification:

High-range admixtures reduce the amount of water needed to produce a concrete of a specific consistency by 12% or more.

Water-Reducing Admixtures

These decrease water requirements for a concrete mix by chemically reacting with early hydration products to form a monomolecular layer of admixture at the cementwater interface. This layer isolates individual particles of cement and reduces the energy required to cause the mix to flow. Thus, the mix is lubricated and exposes more cement particles for hydration.
The Type A admixture allows the amount of mixing water to be reduced while maintaining the same mix slump. Or at a constant water-cement ratio, this admixture allows the cement content to be decreased without loss of strength. If the amount of water is not reduced, slump of the mix will be increased and also strength will  be increased because more of the cement surface area will be exposed for hydration.
Similar effects occur for Type D and E admixtures. Typically, a reduction in mixing water of 5 to 10% can be expected.
Type F and G admixtures are used where there is a need for high-workability concrete. A concrete without an admixture typically has a slump of 2 to 3 in. After the admixture is added, the slump may be in the range of 8 to 10 in without segregation of mix components. These admixtures are especially useful for mixes with a low water-cement ratio. Their 12 to 30% reduction in water allows a corresponding reduction in cementitious material.
The water-reducing admixtures are commonly manufactured from lignosulfonic acids and their salts, hydroxylated carboxylic acids and their salts, or polymers of derivatives of melamines or naphthalenes or sulfonated hydrocarbons. The combination of admixtures used in a concrete mix should be carefully evaluated and tested to ensure that the desired properties are achieved. For example, depending on the dosage of admixture and chemistry of the cement, it is possible that a retarding admixture will accelerate the set. Note also that all normal-set admixtures will retard the set if the dosage is excessive. Furthermore, because of differences in percentage of solids between products from different companies, there is not always a direct correspondence in dosage between admixtures of the same class. Therefore, it is important to consider the chemical composition carefully when evaluating competing admixtures.

Superplasticizers are high-range water-reducing admixtures that meet the requirements of ASTM C494 Type F or G. They are often used to achieve highstrength concrete by use of a low water-cement ratio with good workability and low segregation. They also may be used to produce concrete of specified strengths with less cement at constant water-cement ratio. And they may be used to produce self-compacting, self-leveling flowing concretes, for such applications as longdistance pumping of concrete from mixer to formwork or placing concrete in forms congested with reinforcing steel. For these concretes, the cement content or watercement ratio is not reduced, but the slump is increased substantially without causing segregation. For example, an initial slump of 3 to 4 in for an ordinary concrete mix may be increased to 7 to 8 in without addition of water and decrease in strength.
Superplasticizers may be classified as sulfonated melamine-formaldehyde condensates, sulfonated naphthaline-formaldehyde condensates, modified lignosulfonates, or synthetic polymers.

Air-Entraining Admixtures

These create numerous microscopic air spaces within concrete to protect it from degradation due to repeated freezing and thawing or exposure to aggressive chemicals.
For concrete exposed to repeated cycles of freezing and thawing, the air gaps provide room for expansion of external and internal water, which otherwise would damage the concrete.
Since air-entrained concrete bleeds to a lesser extent than non-air-entrained, there are fewer capillaries extending from the concrete matrix to the surface. Therefore, there are fewer avenues available for ingress of aggressive chemicals into the concrete.
The Standard Specification for Air-Entraining Admixtures for Concrete, ASTM C260, covers materials for use of air-entraining admixtures to be added to concrete in the field. Air entrainment may also be achieved by use of Types IIA and IIIA portland cements (Art. 4.2.2).

Set-Accelerating Admixtures

These are used to decrease the time from the start of addition of water to cement to initial set and to increase the rate of strength gain of concrete. The most commonly used set-accelerating admixture is calcium chloride. Its use, however, is controversial in cases where reinforcing or prestressing steel is present. The reason is that there is a possibility that the accelerator will introduce free chloride ions into the concrete, thus contributing to corrosion of the steel. An alternative is use of one of many admixtures not containing chloride that are available.

Retarding Admixtures

To some extent, all normal water-reducing admixtures retard the initial set of concrete.
A Type B or D admixture will allow transport of concrete for a longer time before initial set occurs. Final set also is delayed. Hence, precautions should be taken if retarded concrete is to be used in walls.
Depending on the dosage and type of base chemicals in the admixture, initial set can be retarded for several hours to several days. A beneficial side effect of retardation of initial and final sets is an increase in the compressive strength of the concrete. A commonly used Type D admixture provides higher 7- and 28-day strengths than a Type A when used in the same mix design.

Mineral Admixtures

Fly ashes, pozzolans, and microsilicates are included in the mineral admixture classification (Arts. 4.9 and 4.10). Natural cement (Art. 4.4) is sometimes used as an admixture.

Corrosion Inhibitors

Reinforcing steel in concrete usually is protected against corrosion by the high alkalinity of the concrete, which creates a passivating layer at the steel surface.
This layer is composed of ferric oxide, a stable compound. Within and at the surface of the ferric oxide, however, are ferrous-oxide compounds, which are more reactive.
When the ferrous-oxide compounds come into contact with aggressive substances, such as chloride ions, they react with oxygen to form solid, iron-oxide corrosion products. These produce a fourfold increase in volume and create an expansion force greater than the concrete tensile strength. The result is deterioration of the concrete.
For corrosion to occur, chloride in the range of 1.0 to 1.5 lb /yd3 must be present.
If there is a possibility that chlorides may be introduced from outside the concrete matrix, for example, by deicing salts, the concrete can be protected by lowering the water-cement ratio, or increasing the amount of cover over the reinforcing steel, or entraining air in the concrete, or adding a calcium-nitrate admixture, or adding an internal-barrier admixture, or cathodic protection, or a combination of these methods.
To inhibit corrosion, calcium-nitrate admixtures are added to the concrete at the time of batching. They do not create a physical barrier to chloride ion ingress.
Rather, they modify the concrete chemistry near the steel surface. The nitrite ions oxidize ferrous oxide present, converting it to ferric oxide. The nitrite is also absorbed at the steel surface and fortifies the ferric-oxide passivating layer. For a calcium-nitrite admixture to be effective, the dosage should be adjusted in accordance with the exposure condition of the concrete to corrosive agents. The greater the exposure, the larger should be the dosage. The correct dosage can only be determined on a project-by-project basis with data for the specific admixture proposed.
Internal-barrier admixtures come in two groups. One comprises waterproofing and dampproofing compounds (Art. 4.15). The second consists of agents that create an organic film around the reinforcing steel, supplementing the passivating layer.
This type of admixture is promoted for addition at a fixed rate regardless of expected chloride exposure.

Coloring Admixtures

Colors are added to concrete for architectural reasons. They may be mineral oxides or manufactured pigments. Raw carbon black, a commonly used material for black color, greatly reduces the amount of entrained air in a mix. Therefore, if black concrete is desired for concrete requiring air-entrainment (for freeze-thaw or aggressive chemical exposure), either the carbon black should be modified to entrain air or an additional air-entraining agent may be incorporated in the mix. The mix design should be tested under field conditions prior to its use in construction. Use  of color requires careful control of materials, batching, and water addition in order to maintain a consistent color at the jobsite.

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