Chemical Admixture

Chemical Admixtures
Chemical Admixture
P.K. Mehta and P.J.M. Monteiro, Concrete: Microstructure, Properties, and Materials
Admixtures
Reasons
(1) Improve or modify some or several
properties of portland concrete.
(2) Compensate for some deficiency
Chemical Admixture
Admixtures
Classification
Surfactants (0.05-0.5%; new ones 2%)
Chemical Admixtures (1-4% by weight of cement)
Mineral Admixtures (> 15% by weight of cement)
Chemical Admixture
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.
Chemical Admixture
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.
U
surf
= S
Where S is the area of the interface and a is the surface tension.
Chemical Admixture
Surface Energy
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.
Chemical Admixture
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 = p
surf
dV
Surface Energy
Chemical Admixture
Applications
p
surf
= 2 r
Cylinder of radius r and height h
S = 2 r h
V = r
2
h
p
surf
= r
as the size of the sphere or the cylinder decreases, the magnitude of
the surface pressure increases greatly
S = 4 r
2
V = 4 r
3
3
Sphere of radius r,
Chemical Admixture
Consider a thin layer of liquid between two parallel plates
p
surf
=

r
=
2 cos
d
Chemical Admixture
Ice Formation in Concrete
Chemical Admixture
Air Voids
Chemical Admixture
Ice Forming in Air Voids
Chemical Admixture
Air-Entraining Surfactants
Salts of wood resins, protainaceous materials and
petroleum acids, and some synthetic detergents.
Chemical Admixture
Air-Entraining Surfactants
Chemical Admixture
Advantages of Using Air-Entrained Surfactants
Freezing and thawing cycles
Improve workability
Reduce tendency for segregation and bleeding
Chemical Admixture
Disadvantages of Using Air-Entrained 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
Chemical Admixture
Surface - Active Chemicals (Surfactants)
long-chain organic molecules, one end of each is
hydrophilic (water-attracting) and the other hydrophobic
(water-repelling).
hydrophilic end contains one or more polar groups, such
as -COO- -SO3-, or -NH3+.
Chemical Admixture
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
Chemical Admixture
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.
Chemical Admixture
Examples
Chemical Admixture
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.
Chemical Admixture
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.
Chemical Admixture
Advantages of Using Water-Reducing Admixtures
Increase the consistency
Achieve higher compressive strength
Cement saving
Important: not all three benefits can be obtained at the
same time
Chemical Admixture
Lignosulfonate as a Water Reducer
O
H
3
CO
O
OH
H
3
CO
SO
3
Na
HO
n
Courtesy from Carmel JOLICOEUR
Chemical Admixture
Superplasticizers
Consist of sulfonated slats of melamine or napththalene
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.
Chemical Admixture
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.
Chemical Admixture
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.
flocculated deflocculated dispersed in less water
"Physical" effects operative in any slurry or paste
High
fluidity
Intermediate
fluidity
Low
fluidity
Mode of Action of Superplasticizers
"Physical" binding and dispersion
Illustration of Physical Dispersion Effect
Mineral Paste +10 % water +0.1 wt% PNS

Chemical Admixture
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
500X
SF
SF
50X
SO
4
Typical Scale of Components in
SF-Cement Paste
SF
Cement
SF
Chemical Admixture
Influence of PNS on Ettringite Morphology
Without PNS With PNS
Chemical Admixture
Mode of Action of Superplasticizers
"Chemical" Effects: Changes in morphology
SEM micrographs of a high alkali cement paste
0% PNS; 30 min hydr.
4% PNS; 30 min hydr.
Chemical Admixture
OPTIONS IN SP APPLICATIONS
30
40
50
60
120 140 160 180 200 220 240
Water content (kg/m
3
)
F
l
o
w

t
a
b
l
e

s
p
r
e
a
d

(
c
m
)
with SP
without SP
Increased
strength
Increased
workability
Chemical Admixture
Mechanism
Chemical Admixture
Mechanism 2
Chemical Admixture
Mechanism 3
Chemical Admixture
Mechanism 4
Chemical Admixture
M
+n
HRWR or Superplasticizers:
Synthetic Water-Soluble Polyelectrolytes
Type of monomer
Length (Mw)
Branching, cross-
linking
Charge,
counter-ions
- - - - - -
Co-polymers
(building blocks)
Chemical Admixture
Structure of PolyNaphthaleneSulfonate (PNS)
CH
2
SO
3
Na
n
Chemical Admixture
Structure of PolyMelamineSulfonate (PMS)
N N
N NH NH
HN
O
SO
3
Na
n
Chemical Admixture
Structure of a Co-Polymer
CH
C
CH CH
2
COONa
NH
CH
N
SO
3
Na
n
O
O
Chemical Admixture
Structure of PolyAcrylic Esters (PAE)
CH
2
C
R
1
COONa
CH
2
C
R
1
CO
O
n
m
R
CH
2
C
R
1
X
o
Chemical Admixture
Set-Controlling Chemicals
Rheological changes in a fresh concrete mixture
Stiffening: loss of consistency by the plastic cement paste
Chemical Admixture
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.
Chemical Admixture
Classification
Accelerator: decreases the setting time.
Retarder: increases the setting time.
Chemical Admixture
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.
Chemical Admixture
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.
Chemical Admixture
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.
Chemical Admixture
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.
Chemical Admixture
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.
Chemical Admixture
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.
Chemical Admixture
Accelerating Admixtures
Chemical Admixture
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.
Chemical Admixture
Retarding admixtures
Control of setting of large structural units to keep concrete
workable through-out 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.
Chemical Admixture
Chemical Admixtures
Type A: water-reducing
Type B: retarding
Type C: accelerating
Type D: water-reducing and retarding
Type E: water-reducing and accelerating
Type F: high-range water-reducing
Type G: high-range and retarding

Chemical Admixture

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Chemical Admixtures

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