Thursday, September 9, 2010

Admixtures

Admixtures

An admixture is defined as a material other than water, aggregate, used as an ingredient of concrete or mortar and added to the batch immediately before or during mixing.

Admixtures vary in composition from surfactants and soluble salts and polymers to insoluble minerals. The purposes for which they are generally used in concrete include

  • Improvement of workability
  • Acceleration or retardation of setting time
  • Control of strength development
  • Enhancement of resistance to frost action and thermal cracking, Alkali-aggregate expansion, and acidic and sulfate solutions.

The admixtures can be broadly divided into two types:

  • Chemical admixtures

· Air-entraining admixtures

These air entraining agents incorporate millions of no-coalescing air bubbles, which will act as flexible ball bearings and will modify the properties of plastic concrete regarding workability, segregation, bleeding and finishing quality of concrete. It also

modifies the properties of hardened concrete regarding its resistance to frost action and permeability.

The following types of air entraining agents are used for making air entrained concrete.

(a) Natural wood resins

(b) Animal and vegetable fats and oils, such as tallow, olive oil and their fatty acids such as stearic and oleic acids.

(c) Various wetting agents such as alkali salts or sulphated and sulphonated organic

compounds.

(d) Water soluble soaps of resin acids, and animal and vegetable fatty acids.

(e) Miscellaneous materials such as the sodium salts of petroleum sulphonic acids,

hydrogen peroxide and aluminium powder, etc.

· Water reducing admixtures

    • Plasticizers

A high degree of workability is required in situations like deep beams, thin walls of water retaining structures with a high percentage of steel reinforcement, column and beam junctions, pumping of Concrete, hot weather Concreting.

Today, we have plasticizers which can help in difficult conditions for obtaining higher workability without using excess of water. The organic substances or the combinations of organic and inorganic substances, which allow a high reduction in water content for the given workability or give a higher workability at the same water content, are termed as Plasticizing Admixtures.

The basic products constituting plasticizers are:

1. Anionic surfactants such as lignosulphonates and their modifications and derivatives, salts of sulphonates hydrocarbons.

2. Nonionic surfactants such as polyglycol esters, acid of hydroxylated

carboxyl acids and their modifications and derivatives.

3. Other products, such as carbohydrates etc.

Among these, calcium, sodium and ammonium lignosulphonates are the most used.

Plasticizers are used in the amount of 0.1% to 0.4% by weight of cement. At these doses, at constant workability the reduction in mixing water is expected to be of the order of 5% to 15%. This naturally increases the strength.

The increase in workability that can be expected, at the same w/c ratio, may be anything from 30 mm to 150 mm slump, depending on the dosage, initial slump of concrete, cement content and type.

    • Superplasticizers (High Range Water Reducers)

Use of superplasticizer permits the reduction of water to the extent up to 30 per cent without reducing workability in contrast to the possible reduction up to 15 per cent in case of plasticizers.

The use of superplasticizer is practiced for production of flowing, self leveling, and self compacting and for the production of high strength and high performance concrete.

The mechanism of action of super plasticizers is more or less same in case of ordinary plasticizer. Only thing is that the super plasticizers are more powerful as dispersing agents and they are high range water reducers. They are called High Range Water Reducers in American literature. It is the use of superplasticizer which has made it possible to use w/c as low as 0.25 or even lower and yet to make flowing concrete to obtain strength of the order 120 Mpa or more. It is the use of superplasticizer which has made it possible to use fly ash, slag and particularly silica fume to make high performance concrete.

Super plasticizers can produce:

· At the same w/c ratio much more workable concrete than the plain ones,

· For the same workability, it permits the use of lower w/c ratio,

· As a consequence of increased strength with lower w/c ratio, it also permits a reduction of cement content.

The super plasticizers also produce a homogeneous, cohesive concrete generally without any tendency for segregation and bleeding.

Classification of Superplasticizer: Following are a few polymers which are commonly used as base for super plasticizers.

    • Sulphonated melamine-formaldehyde condensates (SMF)
    • Sulphonated naphthalene-formaldehyde condensates (SNF)
    • Modified lignosulphonates (MLS)

· Retarding admixtures

A Retarder is an admixture that slows down the chemical process of hydration so that concrete remains plastic and workable for a longer time than concrete without the retarder.

Retarders are used to overcome the accelerating effect of high temperature on setting properties of concrete on hot weather concreting. The Retarders are used in casting and consolidating large number of pours without the formation of cold joints.

They are also used in grouting oil wells. Oil wells are sometimes taken up to a depth of about 6000 meter deep where the temperature may be about 2000C. The annular spacing between the steel tube and the wall of the well will have to be sealed with cement grout. Sometimes at that depth stratified or porous rock strata may also require to be grouted to prevent the entry of gas or oil into some other strata... for all these works cement grout is required to be in mobile condition for about 3 to 4 hours, even at that high temperature without getting set. Use of retarding agent is often used for such requirements.

Sometimes concrete may have to be placed in difficult conditions and delay may occur in transporting and placing. In ready mixed concrete practices, concrete is manufactured in central batching plant and transported over a long distance to the job sites which may take considerable time. In the above cases the setting of concrete will have to be retarded, so that concrete when finally placed and compacted is in perfect plastic state.

Retarding admixtures are sometimes used to obtain exposed aggregate look in concrete. The Retarder sprayed to the surface of the formwork, prevents the hardening of matrix at the interface of concrete and formwork, whereas the rest of the concrete gets hardened. On removing the formwork after one day of so, the unhardened matrix can be just washed off by a jet of water which will expose the aggregates. The above are some of the instances where a retarding agent is used.

Perhaps the most common known Retarder is calcium sulphate. It is interground to retard the setting of cement. The appropriate amount of gypsum to be used must be determined carefully for the given job. Use of gypsum for the purpose of retarding setting time is only recommended when adequate inspection and control is available, otherwise, addition of excess amount may cause undesirable expansion and indefinite delay in the setting of concrete.

In addition to gypsum there are number of other materials found to be suitable for this purpose. They are: starches, cellulose products, sugars, acids or salts of acids. These chemicals may have variable action on different types of cement when used in different quantities. Unless experience has been had with a retarder, its use as an admixture should not be attempted without technical advice. Any mistake made in this respect may have disastrous consequences.

Common sugar is one of the most effective retarding agents used as an admixture for delaying the setting time of concrete without detrimental effect on the ultimate strength. Addition of excessive amounts will cause indefinite delay in setting. At normal temperatures addition of sugar 0.05 to 0.10 percent have little effect on the rate of hydration, but if the quantity is increased to 0.2 percent, hydration can be retarded to such an extent that final set may not take place for 72 hours or more. Skimmed milk powder (casein) has a retarding effect mainly

due to sugar content.

Other admixtures which have been successfully used as retarding agents are Ligno sulphonic acids and their salts, hydroxylated carboxylic acids and their salts which in addition to the retarding effect also reduce the quantity of water requirement for a given workability. This also increases 28 days compressive strength by 10 to 20 percent. Materials like mucic acid, calcium acetate and commercial products by name “Ray lig binder” are used for set retarding purposes.

· Accelerating admixtures

Accelerating admixtures are added to concrete to increase the rate of early strength development in concrete to

    • permit earlier removal of formwork;
    • reduce the required period of curing;
    • advance the time that a structure can be placed in service;
    • partially compensate for the retarding effect of low temperature during cold weather concreting;
    • in the emergency repair work.

In the past one of the commonly used materials as an accelerator was calcium chloride. But, now a days it is not used. Instead, some of the soluble carbonates, silicates, fluosilicates and some of the organic compounds such as riethenolamine are used.

Accelerators such as fluosilicates and triethenolamine are comparatively expensive. The recent studies have shown that calcium chloride is harmful for reinforced concrete and prestressed concrete. It may be used or plain cement concrete in comparatively high dose.

Some of the accelerators produced these days are so powerful that it is possible to make the cement set into stone hard in a matter of five minutes are less. With the availability of such powerful accelerator, the under water concreting has become easy.

Similarly, the repair work that would be carried out to the waterfront structures in the region of tidal variations has become easy. The use of such powerful accelerators have facilitated, the basement waterproofing operations. In the field of prefabrication also it has become an invaluable material. As these materials could be used up to -100C, they find an unquestionable use in cold weather concreting.

· Water reducing and set retarding admixtures

· Water reducing and set accelerating admixtures.

  • Pozzolanic or Mineral admixtures.

Ancient Greeks and Romans used certain finely divided siliceous materials which when mixed with lime produced strong cementing material having hydraulic properties and such cementing materials were employed in the construction of aqueducts, arch, bridges etc. One such material was consolidated volcanic ash or tuff found near Pozzuoli (Italy) near Vesuvius. This came to be designated as Pozzuolana, a general term covering similar materials of volcanic origin found in other deposits in Italy, France and Spain. Later, the term pozzolan was employed throughout Europe to designate any materials irrespective of its origin which possessed similar properties.

It has been amply demonstrated that the best pozzolans in optimum proportions mixed with Portland cement improves many qualities of concrete, such as:

(a) Lower the heat of hydration and thermal shrinkage;

(b) Increase the water tightness;

(c) Reduce the alkali-aggregate reaction;

(d) Improve resistance to attack by sulphonate soils and sea water;

(e) Improve extensibility;

(f) Lower susceptibility to dissolution and leaching;

(g) Improve workability;

(h) Lower costs.

In addition to these advantages, contrary to the general opinion, good pozzolans will not unduly increase water requirement or drying shrinkage.

· Fly ash

Fly ash is finely divided residue resulting from the combustion of powdered coal and

transported by the flue gases and collected by electrostatic precipitator. Fly ash is the most widely used pozzolanic material all over the world.

In India, Fly ash was used in Rihand dam construction replacing cement upto about 15 per cent.

In the recent time, the importance and use of fly ash in concrete has grown so much that it has almost become a common ingredient in concrete, particularly for making high strength and high performance concrete.

The use of fly ash as concrete admixture not only extends technical advantages to the properties of concrete but also contributes to the environmental pollution control. In India alone, we produce about 75 million tons of fly ash per year, the disposal of which has become a serious environmental problem. The effective utilization of fly ash in concrete making is, therefore, attracting serious considerations of concrete technologies and government departments.

There are two ways that the fly ash can be used: one way is to intergrind certain percentage of fly ash with cement clinker at the factory to produce Portland pozzolana cement (PPC) and the second way is to use the fly ash as an admixture at the time of making concrete at the site of work. The latter method gives freedom and flexibility to the user regarding the percentage addition of fly ash.

· Ground granulated blast-furnace slag

Ground granulated blast-furnace slag is a non metallic product consisting essentially of silicates and aluminates of calcium and other bases. The molten slag is rapidly chilled by quenching in water ton form a glassy sand like granulated material. The granulated material when further ground to less than 45 micron will have specific surface of about 400-600m2/kg

Chemical composition:

o Calcium oxide 30-45%

o Silicon dioxide 30-38%

o Aluminium oxide 15-25%

o Ferrous oxide 0.5-2.0

o Specific gravity 2.9

In India, we produce about 7.8 million tons of blast furnace slag. All the blast furnace slags are granulated by quenching the molten slag by high power water jet, making 100% glassy slag granules of 0.4 mm size. The blast furnace slag is mainly used in India for manufacturing slag cement.

There are two methods for making blast furnace slag cement. In the first method blast furnace slag is interground with cement clinker along with gypsum. In the second method blast furnace slag is separately ground and then mixed with the cement.

Clinker is hydraulically more active than slag. It follows then that slag should be ground finer than clinker, in order to fully develop its hydraulic potential. However, since slag is much harder and difficult to grind compared to clinker, it is ground relatively coarser during the process of inter grinding. This leads to waste of hydraulic potential of slag. Not only that the inter-grinding seriously restricts the flexibility to optimize slag level for different uses.

· Silica fumes

Silica fume, also referred to as micro silica or condensed silica fume, is another material that is used as an artificial pozzolanic admixture.

It is a product resulting from reduction of high purity quartz with coal in an electric arc furnace in the manufacture of silicon or ferrosilicon alloy. Silica fume rises as an oxidized vapor. It cools, condenses and is collected on cloth bags. It is further processed to remove impurities and to control particle size. Condensed silica fume is essentially silicon dioxide in noncrystalline form. Since it is an airborne material like fly ash, it has spherical shape. It is extremely fine with particle size less than 1 micron and with an average diameter of about 0.1 micron, about 100 times smaller than average cement particles. Silica fume has specific surface area of about 20000 m2/kg, as against 230 to 300 m2/kg that of cement.

· Rice husk ash

· Metakoline

The above are cementitious and pozzolanic materials.

Fineness Modulus:

In 1925, Duff Abrams introduced the concept of fineness modulus (FM) for estimating the proportions of fine and coarse aggregates in concrete mixtures.

The principle:

“Aggregate of the same fineness modulus will require the same quantity of water to produce a mix of the same consistency and give a concrete of the same strength.”

Because FM is such a widely used index for aggregate proportioning, most testing labs report the FM for fine aggregate with each sieve analysis.

Limits may be taken as guidance is:

  • Fine Sand - 2.2 to 2.6
  • Medium Sand - 2.6 to 2.9
  • Coarse Sand - 2.9 to 3.2

The higher the FM, the coarser the aggregate. FM doesn’t define the grading curve, however, since different gradings can have the same FM.

How aggregate fineness affects concrete properties?

Fine aggregate affects many concrete properties, including workability and finishability. Experience has shown that very coarse sand or very fine sand produces poor concrete mixes.

Coarse sand results in harsh concrete mixes prone to bleeding and segregation.

Fine sand requires a comparatively large amount of water to achieve the desired concrete workability, is prone to segregation, and may require higher cement contents.

Decreasing FM for sand used in mortar requires considerably more cement content when the water-cement ratio and slump are held constant. However, a changing FM has little influence on the cement content required in concrete. Usually, a lower FM results in more paste, making concrete easier to finish.

For the high cement contents used in the production of high-strength concrete, coarse sand with an FM around 3.0 produces concrete with the best workability and highest compressive strength.

In general, manufactured sands require more fines than natural sands for equal workability.

Sieve Analysis: (Calculating FM)

This is done by sieving the aggregates as per IS: 2386 (Part I) – 1963. In this we use different sieves as standardized by the IS code and then pass aggregates through them and thus collect different sized particles left over different sieves.

The apparatus used are –


i) A set of IS Sieves of sizes – 80mm, 63mm, 50mm, 40mm,31.5mm, 25mm, 20mm, 16mm, 12.5mm, 10mm, 6.3mm,4.75mm, 3.35mm, 2.36mm, 1.18mm, 600µm, 300µm, 150µm and 75µm.

ii) Balance or scale with an accuracy to measure 0.1 percent of the weight of the test sample.

The sample for sieving should be prepared from the larger sample either by quartering or by means of a sample divider.

Procedure to determine particle size distribution of Aggregates:


i) The test sample is dried to a constant weight at a temperature of 110 + 5oC and weighed.
ii) The sample is sieved by using a set of IS Sieves.

iii) On completion of sieving, the material on each sieve is weighed.

iv) Cumulative weight passing through each sieve is calculated as a percentage of the total sample weight.

v) Fineness modulus is obtained by adding cumulative percentage of aggregates retained on each sieve and dividing the sum by 100.

Sieves used for gradation test

A mechanical shaker used for sieve analysis

Reporting of Results


The results should be calculated and reported as:

i) the cumulative percentage by weight of the total sample

ii) the percentage by weight of the total sample passing through one sieve and retained on the next smaller sieve, to the nearest 0.1 percent. The results of the sieve analysis may be recorded graphically on a semi-log graph with particle size as abscissa (log scale) and the percentage smaller than the specified diameter as ordinate.

Chemical Composition of Cement

Chemical composition of Portland cement

Portland cement (often referred to as OPC, from Ordinary Portland Cement) is the most common type of cement in general use around the world because it is a basic ingredient of concrete, mortar, stucco and most non-specialty grout.

The essential raw ingredients of Portland cement are

· Lime

· Silica

· Alumina

· Iron Oxide

Excess of clay (Silica + Alumina) causes a cement to "set" quickly, while excess of lime causes it to "set" slowly or imperfectly. Iron oxide gives cement its color. Portland cement is improved in dry storage, as any excess of lime particles are air slaked.

The oxides present in raw materials when subjected to high clinkering temperature (around 1200Oc) combine with each other to form complex compounds.

There are four chief minerals present in a Portland cement grain:

(Bogues’s Compounds)

· tricalcium silicate (Ca3SiO5),

· dicalcium silicate (Ca2SiO4),

· tricalcium aluminate (Ca3Al2O5) and

· calcium aluminoferrite (Ca4AlnFe2-nO7).

The formula of each of these minerals can be broken down into the basic calcium, silicon, aluminum and iron oxides

Cement chemists use abbreviated nomenclature based on oxides of various elements to indicate chemical formulae of relevant species, i.e., C = CaO, S = SiO2, A = Al2O3, F = Fe2O3. Hence, traditional cement nomenclature abbreviates each oxide as shown in Table 1.

Mineral

Chemical formula

Oxide composition

Abbreviation

Tricalcium silicate (alite)

Ca3SiO5

3CaO.SiO2

C3S

Dicalcium silicate (belite)

Ca2SiO4

2CaO.SiO2

C2S

Tricalcium aluminate

Ca3Al2O4

3CaO.Al2O3

C3A

Tetracalcium aluminoferrite

Ca4AlnFe2-nO7

4CaO.AlnFe2-nO3

C4AF

TABLE 1: Chemical formulae and cement nomenclature for major constituents of Portland cement. Abbreviation notation: C = CaO, S = SiO2, A = Al2O3, F = Fe2O3.

The composition of cement is varied depending on the application. A typical example of cement contains

50–70% C3S,

15–30% C2S,

5–10% C3A,

5–15% C4AF, and

3–8% other additives or minerals (such as oxides of calcium and magnesium).

It is the hydration of the calcium silicate, aluminate, and aluminoferrite minerals that causes the hardening, or setting, of cement.

The ratio of C3S to C2S helps to determine how fast the cement will set, with faster setting occurring with higher C3S contents. Lower C3A content promotes resistance to sulfates. Higher amounts of ferrite lead to slower hydration. The ferrite phase causes the brownish gray color in cements, so that “white cements” (i.e., those that are low in C4AF) are often used for aesthetic purposes.

The calcium aluminoferrite (C4AF) forms a continuous phase around the other mineral crystallites, as the iron containing species act as a fluxing agent in the rotary kiln during cement production and are the last to solidify around the others. It is worth noting that a given cement grain will not have the same size or even necessarily contain all the same minerals as the next grain. The heterogeneity exists not only within a given particle, but extends from grain to grain, batch-to-batch, plant to plant.

There are three fundamental stages in the production of Portland cement:

1. Preparation of the raw mixture

2. Production of the clinker

3. Preparation of the cement