Water and Admixtures

CE 165: Concrete Materials and Concrete Construction

Water
municipal water is fine for concrete. salt water can be used for plain concrete but causes problems for reinforced and prestressed concrete. mining water can cause problems due to the presence of salts, acids, oil, sugar, and organic matter. Take the unknown water and make concrete cylinders and compare the time of set and strength to the concrete made with good water. The strength difference should be less than 10%. almost any water is good for the curing of concrete. Some may cause discoloration, though.

ADMIXTURES

Reasons (1) Improve or modify some or several properties of portland concrete. (2) Compensate for some deficiency

CE 165: Concrete Materials and Concrete Construction

Admixtures
Classification (pages 257-258) Surfactants (0.05-0.5%; new ones 2%) Chemical Admixtures (1-4% by weight of cement) Mineral Admixtures (> 15% by weight of cement)
CE 165: Concrete Materials and Concrete Construction

A short (but important detour into surface chemistry)

The presence of a surface breaks the molecular symmetry that exists inside a material. The molecules at the surface have different energy than the molecules inside the bulk material.

CE 165: Concrete Materials and Concrete Construction

Surface energy
Surface energy, Usurf, is the difference between the energy of the molecules at the surface and the energy that they would have within the body.

Usurf S

where S is the area of the interface and a is the surface tension.

CE 165: Concrete Materials and Concrete Construction

Nature brings a body to its minimum energy. Small spherical drops of liquid and gas bubbles are good examples of surface minimization for a given volume. The decrease in surface induces a contraction of the drop, increasing its internal pressure and making it higher than the external pressure. A balance of energy requires that the reduction in surface energy (dS) be equal to the work done by the surface forces in reducing the surface. The work done can be expressed as where is the volume change.

dS psurf dV

Applications
3 2 V 4 r 3 S 4 r Sphere of radius r,

psurf 2 r
Cylinder of radius r and height h S 2 r h
V r2 h

psurf r
as the size of the sphere or the cylinder decreases, the magnitude of the surface pressure increases greatly

CE 165: Concrete Materials and Concrete Construction

Consider a thin layer of liquid between two parallel plates

2 cos psurf r d

Remember sand castles

http://www.philipshelley.com/words/ CE 165: Concrete Materials and Concrete Construction

Mechanism of Detergents

soiled surface

addition of water containing a surfactant

detergent gets adsorbed in all surfaces

during agitation

From Hunter, Introduction to Modern Colloid Science, (1995).

Soap bubble
A soap bubble consists of a thin sphere of water in contact with the polar heads of soap molecules on both sides. From R. Cotterill, The Cambridge Guide to the Material World, 1989.
CE 165: Concrete Materials and Concrete Construction

A simple demonstration

CE 165: Concrete Materials and Concrete Construction

Nearly all glues are plastic polymers-giant molecules that cling to themselves and the surfaces they touch, like sauceless spaghetti noodles left overnight in a bowl. But while the plastic molecules in most household glues are dissolved in a liquid that evaporates as the glue dries, the molecules in Krazy Glue--and other instant glues--do not form until you squirt the liquid out of the tube.
From A. Bloomfield , Am. Scien

Cont.
Krazy Glue is remarkable because it is almost pure ethyl-2-cyanoacrylate, a simple molecule that polymerizes rapidly when exposed to moisture. Each glue molecule contains an unusually fragile double bond between carbon atoms, one that is easily attacked by the hydroxyl ions found in most airborne moisture.
CE 165: Concrete Materials and Concrete Construction

From A. Bloomfield , Am. Scien

From A. Bloomfield , Am. Scien

Surface - Active Chemicals (Surfactants)

long-chain organic molecules, one end of each is hydrophilic (waterattracting) and the other hydrophobic (water-repelling). hydrophilic end contains one or more polar groups, such as -COO-SO3-, or -NH3+.
CE 165: Concrete Materials and Concrete Construction

Air-Entraining Surfactants
Salts of wood resins, protainaceous materials and petroleum acids, and some synthetic detergents.

CE 165: Concrete Materials and Concrete Construction

Air-Entraining Surfactants

CE 165: Concrete Materials and Concrete Construction

Advantages of Using AirEntrained Surfactants

Freezing and thawing cycles Improve workability Reduce tendency for segregation and bleeding

CE 165: Concrete Materials and Concrete Construction

Ice Formation in Concrete

CE 165: Concrete Materials and Concrete Construction

Air Voids

CE 165: Concrete Materials and Concrete Construction

Ice Forming in Air Voids

Disadvantages of Using AirEntrained Surfactants

Loss in strength ( for each 1% of air causes 5% loss in strength) Increase permeability In case of overdoses, they cause delay in setting and hardening

CE 165: Concrete Materials and Concrete Construction

Effect of air-entrainment

CE 165: Concrete Materials and Concrete Construction

Water Reducing Agents

Salts and derivatives of lignosulfonic acids, hydroxylated carnoxylic acids, and polysaccharides. The anionic polar group is joined to hydrocarbon chain which itself is polar or hydrophilic.
CE 165: Concrete Materials and Concrete Construction

Water Reducing Agents

Salts and derivatives of lignosulfonic acids, hydroxylated carnoxylic acids, and polysaccharides.

The anionic polar group is joined to hydrocarbon chain which itself is polar or hydrophilic.
CE 165: Concrete Materials and Concrete Construction

Examples

CE 165: Concrete Materials and Concrete Construction

Mechanism

The polar chain is adsorbed alongside the cement particle; instead of directing a nonpolar end toward water, in this case the surfactant directs a polar end, lowering the surface tension of the water and making the cement particle hydrophilic.
CE 165: Concrete Materials and Concrete Construction

Consequence

As a result of layers of water dipoles surrounding the hydrophilic cement particles, their flocculation is prevented and a well-dispersed system is obtained.
CE 165: Concrete Materials and Concrete Construction

Advantages of Using WaterReducing Admixtures Increase the consistency Achieve higher compressive strength Cement saving Important: not all three benefits can be obtained at the same time
CE 165: Concrete Materials and Concrete Construction

Lignosulfonate as a Water Reducer

OH H3 CO HO O SO 3 Na H3 CO

Courtesy from Carmel JOLICOEUR

CE 165: Concrete Materials and Concrete Construction

Superplasticizers
Consist of sulfonated slats of melamine or napthalene formaldehyde condensates. Also called high range water-reducing admixtures because they are able to reduce 3 to 4 times water compared to normal water-reducing admixtures.
CE 165: Concrete Materials and Concrete Construction

Superplasticizers
Long-chain, high-molecular mass anionic surfactants with a large number of polar groups in the hydrocarbon chain.

Normal dosage: 1-2% by weight of cement.

CE 165: Concrete Materials and Concrete Construction

Superplasticizers
25 to 30% of water reduction for a given consistency (normal plasticizer: 5 to 10% of water reduction). No problem with bleeding and segregation because of the colloidal size of the long-chain particles of the admixture which obstructs the path of the bleed water.
CE 165: Concrete Materials and Concrete Construction

Mode of Action of Superplasticizers "Physical" binding and dispersion flocculated deflocculated

Courtesy from Carmel JOLICOEUR

dispersed in less water

Low fluidity

High fluidity

Intermediate fluidity

"Physical" effects operative in any slurry or paste

Illustration of Physical Dispersion Effect

+10 % water

Mineral Paste

+0.1 wt% PNS

Courtesy from Carmel JOLICOEUR

CE 165: Concrete Materials and Concrete Construction

HRWR or Superplasticizers: Synthetic Water-Soluble Polyelectrolytes (building blocks)

Type of monomer Length (Mw) Branching, crosslinking Charge, counter-ions Co-polymers

- -

- -

M+n

Courtesy from Carmel JOLICOEUR

Structure of PolyNaphthaleneSulfonate (PNS)

CH2

SO3Na

n
Courtesy from Carmel JOLICOEUR

CE 165: Concrete Materials and Concrete Construction

Structure of PolyMelamineSulfonate (PMS)

NH

NH

HN

SO3Na

n
Courtesy from Carmel JOLICOEUR

CE 165: Concrete Materials and Concrete Construction

Structure of a Co-Polymer
COONa CH O C NH CH CH2 CH N O

SO3Na

Courtesy from Carmel JOLICOEUR

CE 165: Concrete Materials and Concrete Construction

Structure of PolyAcrylic Esters (PAE)

R1 CH2 C COONa CH2 R1 C CO O CH2 R1 C X

Courtesy from Carmel JOLICOEUR

CE 165: Concrete Materials and Concrete Construction

Characterization of Superplasticizers
Bulk pH, conductivity % solid viscosity specific gravity surface tension loss on ignition, TGA Physico-chemical elemental and ionic analysis acid-base titration charge density molar mass distribution NMR, IR, UV spectroscopy Functional rheology of pastes (inert or reactive minerals) zeta potential on reference minerals (dilute) adsorption on various minerals (dilute and pastes) influence on hydration reactions specific interactions

Courtesy from Carmel JOLICOEUR

Typical Scale of Components in SF-Cement Paste

SF
50X

Cement

SF

500X

SO4

Courtesy from Carmel JOLICOEUR

Influence of PNS on Ettringite Morphology

Without PNS With PNS

Courtesy from Carmel JOLICOEUR

CE 165: Concrete Materials and Concrete Construction

Mode of Action of Superplasticizers "Chemical" Effects: Changes in morphology

Courtesy from Carmel JOLICOEUR

SEM micrographs of a high alkali cement paste

0% PNS; 30 min hydr.

4% PNS; 30 min hydr.

CE 165: Concrete Materials and Concrete Construction

OPTIONS IN SP APPLICATIONS
60

with SP Flow table spread (cm) 50

Increased workability

40

Increased strength

without SP

30 120 140 160 180 200

3

220

240

Water content (kg/m )

Courtesy from Carmel JOLICOEUR

New Generation of Superplasticizers

CE 165: Concrete Materials and Concrete Construction

Mechanism

CE 165: Concrete Materials and Concrete Construction

Mechanism 2

CE 165: Concrete Materials and Concrete Construction

Mechanism 3

CE 165: Concrete Materials and Concrete Construction

Mechanism 4

CE 165: Concrete Materials and Concrete Construction

ASTM Categories (C494) : Water Reducers

Low range: water reduction of 5% (minimum) WR (e.g. lignosulfonate) Type A : normal Type D : WR and retarding Type E : WR and accelerating High range: water reduction of 12% (minimum) HRWR, Superplasticizer (synthetic polymers: naphthalene-, melamine- or acrylate- based) Type F : normal Type G : HRWR and retarding
CE 165: Concrete Materials and Concrete Construction

Set-Controlling Chemicals
Rheological changes in a fresh concrete mixture Stiffening: loss of consistency by the plastic cement paste

CE 165: Concrete Materials and Concrete Construction

Set-Controlling Chemicals
Setting: beginning of solidification. At the initial set the paste becomes unworkable so the placement, compaction and finishing of concrete beyond this point becomes difficult (4 to 6 hrs. at 70 F). Final set is the time required for the paste to solidify completely. Hardening: strength gain with time.
CE 165: Concrete Materials and Concrete Construction

Classification
Accelerator: decreases the setting time. Retarder: increases the setting time.

CE 165: Concrete Materials and Concrete Construction

Mechanism of Action (I)

The action of set-controlling chemicals on portland cement can be attributed mainly to dissolving of the anhydrous constituents forming anions (silicate and aluminate) and cations (calcium), the solubility of each being dependent on the type and concentration of the acid and base ions present in the solution.
CE 165: Concrete Materials and Concrete Construction

Mechanism of Action (II)

An accelerating admixture must promote the dissolution of the cations (calcium ions) and anions from the cement. A retarding admixture must impede the dissolution of the cement cations (calcium ions) and anions.
CE 165: Concrete Materials and Concrete Construction

Mechanism of Action (III)

The presence of monovalent cations in solution (i.e., K+ or Na+) reduces the solubility of Ca2+ ions but tends to promote the solubility of silicate and aluminate ions. In small concentrations, the former effect is dominant; in large concentrations, the latter effect becomes dominant.
CE 165: Concrete Materials and Concrete Construction

Mechanism of Action (IV)

The presence of certain monovalent anions in solution (i.e., Cl, N03-, or S042-) reduces the solubility of silicates and aluminates but tends to promote the solubility of calcium ions. In small concentrations, the former effect is dominant; in large concentrations, the latter effect becomes dominant.
CE 165: Concrete Materials and Concrete Construction

Accelerating admixtures
Useful for modifying the properties of concrete, particularly in cold weather, to: (a) expedite the start of finishing operations and, when necessary, the application of insulation for protection; (b) reduce the time required for proper curing and protection; (c) increase the rate of early strength development so as to permit earlier removal of forms and earlier opening of the construction for service; and (d) permit more efficient plugging of leaks against hydraulic pressures.

CE 165: Concrete Materials and Concrete Construction

Accelerating admixtures
Calcium chloride is by far the best known and most widely used accelerator. See Table 8.3 for the potential problems in using such admixture. There are accelerators that do not contain choride: calcium formate, formic acid.
CE 165: Concrete Materials and Concrete Construction

Retarding admixtures
Compensation for adverse ambient temperature conditions particularly in hot weather. Extensive use is made of retarding admixtures to permit proper placement and finishing and to overcome damaging and accelerating effects of high temperatures.
CE 165: Concrete Materials and Concrete Construction

Retarding admixtures
Control of setting of large structural units to keep concrete workable throughout the entire placing period. This is particularly important for the elimination of cold joints and discontinuities in large structural units. Also control of setting may prevent cracking of concrete beams, bridge decks, and composite construction due to form deflection of movement associated with placing of adjacent units.
CE 165: Concrete Materials and Concrete Construction

Chemical Admixtures

Type A: Type B: Type C: Type D: Type E: Type F: Type G:

water-reducing retarding accelerating water-reducing and retarding water-reducing and accelerating high-range water-reducing high-range and retarding

CE 165: Concrete Materials and Concrete Construction

Case Study
Highly Variable Air Content On a recent job we found large variations in the air content of our concretes. The mixture contained 500 lb of cement per cubic yard and was made with a 1 in. aggregate. The air content had to be between 5% and 7%, but in certain cases the air content was considerably higher or very low. What could be causing this phenomenon?

Solution
The air content of concrete can vary for any of a number of reasons. Increasing fineness of the sand can reduce the air content; the presence of organic matter in the sand, which can act as an air entraining agent can increase air content. By mixing dyes or organic materials into the concrete, one can lower the concrete's air content. An overdose of admixture or a reduction of cement can increase air content. Changing the brand or type of cement, or the kind of supplementary cementitious material used, can raise or lower the amount of air. Calcium chloride increases air content in mixes rich in cement, but not so in lean mixes.
CE 165: Concrete Materials and Concrete Construction

Cont
In certain cases, water hardness can effect the air content. Also, changing the sequence of introducing the admixture can cause variations in air content. Overloading the mixing truck diminishes the mixing efficiency, which in turn reduces the air content. In the beginning, increasing the mixing time increases air content, but if the mixing is greatly prolonged, the air content decreases. Temperature changes influence air content: in general, less air-entraining agent is needed in the morning than later in the day, during fairly hot weather.

CE 165: Concrete Materials and Concrete Construction

Case Study
Too Much Air For many years, we've notice that our concrete has a tendency to contain too much air, a phenomenon which has recently become worse We have tried, without success, reducing the amount of air entraining agent, we've even changed the supplier without any success. We've always used aggregates which come from a quarry and a sand pit near our site (3 to 4 miles away). Given that we are in a fairly remote region, it is economically impossible for us to change suppliers (the next closest sand pit is 50 m away, while the next closest quarry is 60 miles away). What should we do?
CE 165: Concrete Materials and Concrete Construction