CL305 Concrete Technology

Term Paper I: Construction Chemicals and Admixtures

Retarders

Prepared by
Ronak Kamdar
(13BCL033)

Nirma University
Institute of Technology
October 2014

Table of Content

What are Retarders?

Composition of Retardation

Mechanism of Retardation

Interaction of Retarder with Cement

Effects of Retarders on the Drying Shrinkage of Cement Paste at Various

Stages of Hydration
Result of Setting Time Experiments

1) Commercial Retarders
2) Pure Retarders

Effects of large retarder overdose

Applications
Usage of retarders as per IS 9103:1999
Usage of retarders as per ASTM C494
Cost of retarders
References

What are Retarders?

According to IS 9103:1999,
An admixture which delays the setting of cement paste, and hence of mixtures, such
as mortar or concrete containing cement.
So basically retarders are chemical formulations which retard, but do not "kill" the set
of the mortar at the surface of concrete. When the underlying concrete has
hardened, the retarded mortar surface can be flushed off with a stream of water
and/or removed by scrubbing with a stiff brush. Since these compounds do no "kill"
the set, if they are left on the concrete or unintentionally splashed on other fresh
concrete, they will permit the concrete to eventually attain a set and achieve full
strength.
Retarders are classified as type B or type D chemical admixtures for portland cement
concrete in ASTM Designation C494. Their primary function is, as the name implies,
to retard the setting time of concrete. Many problems of hot weather concreting,
mass concrete, multi-lift concreting, continuous placement, and others have been
helped by the use of retarders.
As a secondary effect, many retarders reduce the water requirement to produce a
concrete of desired workability and produce a concrete of higher strength with equal
cement content. Some retarders, additionally, produce many small air bubbles, much
the same as those produced by air-entraining agents in concrete mixtures. Hence,
the use of retarders is also beneficial to other properties of concrete such as
workability, strength, and durability.

Composition of Retardation

Retarder can be formed by organic and inorganic material. The organic material
consists of unrefined Ca, Na, NH4, salts of lignosulfonic acids, hydroxycarboxylic
acids, and carbohydrates. The inorganic material consists of oxides of Pb and Zn,
phosphates, magnesium salts, fluorates, and borates. Commonly used retarders are
lignosulfonates acids and hydroxylated carboxylic (HC) acids, which act as Type D
(Water Reducing and Retarding Admixtures). The use of lignosulfonates acids and
hydroxylated carboxylic acids retard the initial setting time for at least an hour and
no more than three hours when used at 65 to 100 oF.
A study performed on the influence of air temperature over the retardation of the
initial set time (measured by penetration resistance as prescribed in ASTM C 403
92) shows that decreasing effect with higher air temperature. The table below
describes the effect of air temperature on retardation of setting time:
Table: Air Temperature and Retardation of Initial Setting Time

Admixture
Type

Description

Retardation of initial setting time (h:min) at

temperature of
30oC

40oC

50oC

Hydroxylic acid

4:57

1:15

1:10

Lignin

2:20

0:42

0:53

Lignosulfonates

3:37

1:07

1:25

Phosphate-based

---

3:20

2:30

Mechanism of Retardation

Many water reducers have a retarding tendency. Therefore, some of the ingredients
in water reducers, such as lignosulfate acids and hydroxycarboxylic acids, are also a
basis for set-retarding admixtures. Other important materials used in producing set
retarders are sugars and their derivatives.
Mechanisms of set retardation were studied by many researchers. Several theories
have been offered to explain this mechanism. A review of these theories was
presented by Young (1972). The role of retarding admixtures can be explained in a
simple way: the admixtures form a film around the cement compounds (e.g., by
absorption), thereby preventing or slowing the reaction with water. The thickness of
this film will dictate how much the rate of hydration is retarded. After a while, this film
breaks down, and normal hydration proceeds. However, in some cases when the
dosage of admixtures exceeds a certain critical point, hydration of cement
compounds will never proceed beyond a certain stage, and the cement paste will
never set. Thus, it is important to avoid overdosing a concrete with a retarding
admixture.
Other factors influencing the degree of retardation include the w/c, cement content,
C3A and alkali contents in cement, the type and dosage of the admixture, and the
stage at which the retarder is added to the mix. The effectiveness of retarder is
increased if its addition to the fresh concrete is delayed for a few minutes.

Interaction of Retarder with Cement

1. C3A, C4AF, hydrated C3S , and, possibly, hydrated C3A adsorb retarders from
solution.
2. Retarders that have chemically different structures act differently in their effects on
cement hydration.
3. Not only the aluminate phase but also the silicate phase in cement plays a
significant role in the setting process.
4. Retarders are more effective when they are added to cement of low C3A and low
alkali content.

Effects of Retarders on the Drying Shrinkage of Cement Paste at Various

Stages of Hydration
Figures 1 and Figure 2 show, respectively, the shrinkage of the cement paste bars as
affected by the addition of commercial retarders and selected pure chemicals when
the pastes were dried in a vacuum oven at 105 to 110C for 24 hours. The shrinkage
values were plotted against the degree of hydration of the samples, determined as
previously explained. For clarity, data points are not shown in the figure. For citric
acid, however, data points only are shown in Figure 2 because of the lack of enough
points to draw a complete curve.
At the degree of hydration of about 50%, which roughly corresponds to an age of 2
days, all the samples shrank practically an equal amount, approximately 0.8%. The
cement paste alone, with no admixture, always had a smaller shrinkage than the
others at this point and at most later ages. At the degree of hydration of 85 to 90%,
the rate of increase in shrinkage was reduced for all pastes except that with calcium
chloride.
When the degree of hydration was between 2 and 4 5% the shrinkage behavior of
the samples was changed significantly. All hydroxycarboxylic acids such as retarder
A, glycolic acid and citric acid increased the shrinkage considerably. Sucrose had an
effect about equal to that of these acids, but the carbohydrate retarder (S) ,
conversely, minimized the shrinkage. The cement paste with lignosulfonate retarder
(L) shrank more or less in the same way as did the cement paste with no admixture,
but showed less shrinkage at early ages. Addition of 3-hydroxy-2-butanone or
hydroquinone , which have no acid group, but only hydroxyl1 or carbonyl groups,
resulted in a smaller shrinkage of 79 cement paste at this early age. Calcium
chloride increased the shrinkage at all stages of hydration and showed the largest
shrinkage of all hydrations higher than 50%. When either the concentration of citric
acid was increased enough to result in a relative retardation of 200% or the watercement ratio of plain paste was changed from 0.40 to 0.43, the shrinkage of the
pastes was practically unchanged.

Figure 1 Shrinkage of vaccum over-dried cement pastes at various stages of

hydration (commercial retarders)

Figure 2 Shrinkage of vaccum over-dried cement pastes at various stages of

hydration (pure retarders)

Result of Setting Time Experiments

Commercial Retarders

Figures 3, 4, and 5 show the results of setting time experiments for the three
commercial retarders when they were used at different concentrations, expressed as
weight per cent of the retarder-solids based on the cement. In these figures, values
of penetration resistance are plotted against elapsed time after initial contact of the
cement with mixing water (plus admixture). The general expectation that the higher
the concentration of retarder, the longer the setting time, is apparent. However, it is
noteworthy that the retarders A (hydroxycarboxylic acid) and S (carbohydrate) tend
to accelerate the initial hydration of cement when they were added at the highest
concentration whereas the retarder L (lignosulfonate) retards all stages of the
hydration evenly up to 4000 psi even at higher concentration
.
In order to compare the effects of concentration of retarders at different penetration
levels, Figures 6, 7, and 8 were made from the same results. It is observed that
relative retardation of the mortars is smaller at higher penetration resistances. This is
an important and necessary property for properly retarded concrete. Another
interesting point is that the increases in setting time at the penetration resistance
levels of 500, 1000, and 4000 psi are in close agreement and the retardation at 500
psi level appears to be a mean retardation in the resistance range of 100 to 4000 psi.
Since initial setting time corresponds approximately to the last time when revibration
of concrete can be made, the result would indicate that initial setting time is a
practical and convenient standard point for evaluating retarders. Manufacturer's
suggested dosages are also shown in each figure by a shaded range. These
dosages produce increases in setting time of roughly 30 to 90% for all the retarders.

The resulting range of retardation is typical of that of concrete (49) . This result
implicitly affirms the adequacy of the penetration resistance test as conducted on
mortar specimens in this work. In the same figures, it should be noted that the
lignosulfonate retarder (L) required more than twice as much dosage as the others
(A and S) did to obtain a certain amount of retardation.

Figure 3 - Penetration Resistance vs Elapsed Time for Mortar with Retarder L

Figure 4 - Penetration Resistance vs Elapsed Time for Mortar with Retarder A

Figure 5 - Penetration Resistance vs Elapsed Time for Mortar with Retarder S

Figure 6 - Effect of Concentration of Retarder L on Setting Time of Mortar

Figure 7 - Effect of Concentration of Retarder A on Setting Time of Mortar

Figure 8 - Effect of Concentration of Retarder S on Setting Time of Mortar

Pure Chemicals

Strong retarders such as tartronic acid, d-tartaric acid, mucic acid, gluconic acid, 2ketoglutaric acid, citric acid, sucrose, and 2 ,4 ,6-trihydroxybenzoic acid have large
values of T500/T50. T500 is defined as the initial setting time of each sample relative
to that of a control sample, and was obtained as follows: A relationship between
elapsed time and penetration resistance was drawn for each sample in the same
way as was done for the commercial retarders, and an initial setting time was
determined. This time was then expressed in terms of a percentage of that of an
appropriate control sample without admixture. In the same way, T50, T100, and T4
0Q0, which are relative setting times at the penetration resistance of 50, 100, and
4000 psi, respectively, were determined. Again, calcium lignosulfonate is not a strong
retarder. Glycolic acid, methyl glycolate and a-hydroxyacetamide are strong
retarders at higher concentrations. Only l,3-dihydroxy-2-propanone showed an
unusual setting when it was added at the rate of 0.5%. It accelerated early
72 hydration of the cement to reach a penetration resistance of 2 00 psi in 2 hr , but
extremely retarded the later hydration. This behavior was similar to that observed in
the hydration of a Type I cement clinker without any gypsum addition (Figure 8).

Figures 9 and 10 show the effects of concentration of admixture on the relative initial
setting time of mortar specimens. It is seen that strong retarders can delay the
setting of mortars almost indefinitely even at a relatively low concentration while
some other chemicals accelerate the setting when added at higher concentration.
The results seem to divide themselves into two groups. In Figure 14, whatever the
magnitude of the retardation, additional increments of concentration produced an
increasingly larger relative retardation, i.e., the curves are concave downward. In
Figure 15, on the other hand the opposite is true; the instances showed less
additional effect at higher concentrations. Indeed, sometimes the effect was
reversed.

Figure 9 - Penetration Resistance vs Elapsed Time for Mortar with 1, 3-Dihydroxy-2Butanone

Figure 10 Concentration of admixture vs initial setting time of mortar (No. 1)

Figure 11 Concentration of admixture vs initial setting time of mortar (No. 2)

Effects of large retarder overdose

A large amount of retarding admixtures is available in the market. Some of their

desirable effects are described by the manufacturers, but there is no information
regarding some other effects such as the effect of overdosing, with no allowable over
dosage limit being specified. Such overdosing can ocuur in practice due to faults in a
retarder dispenser at a batching plant.
The following main conclusions can be drawn based on this investigation that used
the retarder Pozzolith 300R, an admixture made to satisfy the ASTM Type B and D
requirements.
1. An overdose of retarder up to 3 times the normal dosage can be easily
accommodated in concrete strength gain nit being appreciably affected.
2. Concrete with retarder overdoses of up to even 6 times the normal dosage will
eventually reach or even exceed their corresponding 28 day strengths.
3. Equivalent cube strength results from cores are progressively lower than the
corresponding cube tests results as retarder dosages increase
4. Reductionsin cement setting time for the specimens with a retarder are
greater for the effect of a 2.5m/s wind than for a temperature increase of 22 0C
above the ambient 31oC
5. The question as to whether the interior quality of retarder overdosed
concretes is better or poorer than the surface quality could not be resolved
unambiguously, and requires further investigation.

Applications

Creation of exposed aggregate surfaces

Precast panels

Decorative sidewalks and walkways

Bond improvement for water-proofing materials

Slip-resistant surfaces

Formulations for both horizontal and vertical

To offset the accelerating effect of hot weather on the setting time of concrete

Placing concrete in large piers and foundations, cementing oil wells, or

pumping grout or concrete over considerable distances

Usage of retarders as per IS 9103:1999

Usage of retarders as per ASTM C494

Note:
A: Water Reducing
B: Retarding
C: Accelerating
D: Water Reducing and Retarding
E: Water Reducing and Accelerating
F: Water Reducing, High Range
G: Water Reducing, High Range and Retarding

Cost of retarders

Sodium Gluconate retarder concrete admixture agent

US $700-800 / Metric Ton ( FOB Price)

20 Metric Tons (Min. Order)
150000 Metric Ton/Metric Tons per Year (Supply Ability)
Polycarboxylate retarder concrete admixture purity higher than 40%
US $1000-2000 / Ton ( FOB Price)
10 Tons (Min. Order)
100000 Ton/Tons per Month (Supply Ability)
Sodium Lignosulphate retarder concrete admixture shampoo sls
US $190-290 / Metric Ton ( FOB Price)
1 Metric Ton (Min. Order)
5000 Metric Ton/Metric Tons per Month (Supply Ability)
PCE 50% concrete retarder admixture
US $2250-2280 / Ton ( FOB Price)
16 Tons (Min. Order)
1500 Ton/Tons per Month (Supply Ability)
JK-06 SG Sodium Gluconate Set Retarding concrete admixture
14 Tons (Min. Order)
300,000 Ton/Tons per Year (Supply Ability)

References

http://www.alibaba.com/showroom/retarder-concrete-admixture.html
http://www.engr.psu.edu/ce/courses/ce584/concrete/library/materials/Ad
mixture/AdmixturesMain.htm
http://en.wikipedia.org/wiki/Retarder_(chemistry)
www.euclidchemical.com/.../Concrete%20Surface%20Retarder.pdf
www.euclidchemical.com/...retarders/concrete-surface-retarders/
www.basf-admixtures.com Home Product Search
www.cement.org/cement-concrete-basics/concrete.../chemical-admixtures
www.sfu.ca/~nmallika/Nuwan/.../Effect_of_large_retarder_overdose.pdf
docs.lib.purdue.edu/cgi/viewcontent.cgi?article=2188&context=jtrp
http://sintef.se/upload/Hardening%20Retarders%20for%20Massive
%20Concrete.pdf
https://law.resource.org/pub/in/bis/S03/is.9103.1999.pdf
http://www.engr.psu.edu/ce/courses/ce584/concrete/library/materials/Ad
mixture/LinkTab.htm