EVOLUTION OF

SUPERPLASTICIZERS

Francesco Surico
R&D Admixtures for Concrete
Mapei SpA, Milano
HISTORY OF SUPERPLASTICIZERS

1936
 NAPHTALENESULFONATE
PNS BNS bNS CH2
NSFC NS
Condensation polymer between
-
naphthalenesulfonic acid and SO3Na
formaldehyde

-
SO3Na
-
SO3Na
Negative
charged
CH2 CH2 CH2 CH2 CH2 group

- SO3Na - SO3Na - SO3Na

US Pat. N. 2,052,586 Sept. 1, 1936 G. Tucker (GRACE)

HISTORY OF SUPERPLASTICIZERS

1938
 OH OH
LIGNOSULFONATE O C C C
LGS LS
H S O3Na OCH3
- HO
n

Chemical modification
(sulfonation) Negative
of natural lignine charged
- group
SO3Na
OH H OH OH OH OH H OH

O C C C O C C C O C C C

H SO3Na H H H H H SO3Na H
HO OCH3 HO OCH3 HO OCH3

- -

US Pat. N. 2,141,570 Dec. 27, 1938 Jacob G. Mark

HISTORY OF SUPERPLASTICIZERS

60’s
 NAPHTALENESULFONATE
PNS BNS bNS CH2

NSFC NS

Condensation polymer between -

naphthalenesulfonic acid and SO3Na
formaldehyde n
-
SO3Na
-
SO3Na
Negative
charged
CH2 CH2 CH2 CH2 CH2 group

- SO3Na - SO3Na - SO3Na

GB Pat. N. 1391818 Kenichi Hattori (KAO Corp.)

MELAMINE SULFONATE
CONDENSATE
OCH2 HN N NH CH2
MS MSFC
N N
Condensation polymers
between melamine CH2 SO3 Na
-
sulfonate and n

formaldehyde
Negative
-
CH2 SO3 Na
-
CH2 SO3 Na charged
N N N N
group
OCH2 HN N NH CH2 OCH2 HN N NH CH2 OCH2 HN OCH2 HN N
N NH CH2 NH CH2

N N
N N

-
CH2 SO3 Na
-
CH2 SO3 Na

German Patent # 1745441 Aignesberger (SKW)

 HISTORY OF SUPERPLASTICIZERS
Reasons of the success of Super’s in the 80’s
1. improvement of the quality and efficiency of the new
polymers with consequent enhancement of the
performance-cost factor;
2. Evidence that superplasticizers do not create long
term problems in concrete;
3. Establishment of technical requirements for higher
performance concrete with need of superplasticizers;

4. Rapid growth of the demand for either “flowing

concrete” and/or high strength/high performance
concrete by the construction industry
HISTORY OF SUPERPLASTICIZERS

9 3
19 D
N S
- O
C Z EE R
3 6 E
S CI G
1 9 D I A
N ST N
A A IO
ST PL AT
I R ER R
F P NE
SU GE
1994
 In 1994 MAPEI, first in Europe, starts the
production of MAPEFLUID X404

Copolymer of acrylic C C C C C C

acids and acrylic

ethoxylate esters
C O C O C O

X O
_
MAPEFLUID X404
starts the new age of
Negative
third generation Third
charged
monomer
superplasticizers in group
Europe n

Non ionic
group
 Different technology may be used to
produce this class of molecules.

O O

O C O C

C C C C C C C C C C C C C C C C

C O C O C O C O C O C O

ONa

- - - -
O ONa ONa O ONa

Polycarboxylates - Polyethers - Acrylics

CAE PCA PCE
 The key factors differentiating
the polymers are:

-Length of the Main

chain
- - - - -

- Length of the side

chain

- Charge density on the

- - - - - - - - - - main chain
CEMENT-SUPERPLASTICIZER
INTERACTION

Cement dispersion
Cement Hydration
Retention of workability
ETTRINGITE

ANHYDROUS CEMENT

C-S-H FIBERS
 POLYMER ONTO THE CEMENT
1
-----

-----
SURFACE (ADSORPTION)

-----
-----

POLYMER INTO ETTRINGITE

2 (ORGANOMINERAL PHASE -
----- ----- OMP)
-----
-----

3 UNADSORBED POLYMER IN
-----

-----
----- THE SOLUTION
-----

-----

----
-----

----

-----

-----
-----

-----

-----
-----

-----
-----

-----
-----
-----
-----

-----
-----
 The polymer fractions left in the solution and
that incorporated into the early hydration phase
have been always considered lost as
superplasticizers because not active in terms of
fluidification effect

Since 1994 MAPEI studied the

interactions of these fractions with
cement and found that they can affect
many other properties of the
cementitious systems
 Polymer
Polymer onto incorporated in Polymer in
cement the hydration solution
surface products

è
è
è

ADSORPTION HYDRATION EQUILIBRI UM

è

è
è
FLUIDIFYING MECHANICAL RETENTION OF
EFFECT STRENGTH WORKABILITY
 RHEOLOGY OF CEMENT
WITHOUT SUPERPLAS TICIZERS
+ - + -
- -
+ - + -
- + - +
+ - + -
- + - +
Potential Energy

REPULSION
Distance

ATTRACTION
 RHEOLOGY OF CEMENT
WITHOUT SUPERPLAS TICIZERS
+ - + -
- -
+ +- -
- FLOCCULATION
-+ +
+ -+ -
- + - +
Potential Energy

REPULSION
Distance

ATTRACTION

HIGH VISCOSITY
 MECHANISM OF WORKING OF FIRST AND
SECOND GENERATION SUPERPLASTICIZERS
DISPERSION OF CEMENT PARTICLES BY
ELECTROSTATIC REPULSION

Sulfonic groups ADSORPTION

(negatively charged)
“anchoring groups ”

Main polymer chain Cement particle

 RHEOLOGY OF CEMENT WITH
1° AND 2° GENERATION SUPERPL ASTICIZERS
- - - - --- -- - - - - - - --- -- - -
---- -- - ---- -- -
- -- -- - -- --

- - - - - - - - - - - ----

- - - - - - - - - - - ----
-- - -- -
- -

- - -- - -

- - -- - -
- - -- - - - - - - -
--

- - -- - - - - - - -
--
-

-
- - --

- - --
- -

- -- - -

- -- - -
- -- - - - -- - -

-
-- - - - - - - -- - - - - - -
- - -- - - --
Potential Energy

REPULSION
Distance

ATTRACTION
 RHEOLOGY OF CEMENT WITH
1° AND 2° GENERATION SUPERPL ASTICIZERS
- - - - --- --- - - - - - --- -- - -
---- -- - ---- -- -
- -- -- - -- --

- - - - - - - - - - - ----

- - - - - - - - - - - ----
-- - -- -
- -

- - -- - -

- - -- - -
- - -- - - - - - - -
--

- -- -- - - - - - - -
-
ELECTROSTATIC
-

-
REPULSION
- - --

----
- -
- -- - -

- -- - -
- -- - - - -- - -
-

-
-- - - - - - - -- - - - - - -
- - -- - - --

REPULSION
Potentiual
Energy

Distance

ATTRACTION

LOW VISCOSITY
 MECHANISM OF WORKING OF THIRD
GENERATION SUPERPLASTICIZERS
DISPERSION OF CEMENT PARTICLES BY
ELECTRO-STERIC REPULSION
Carboxylate groups ADSORPTION
(negative charges) Polymer
“anchoring groups ” backbone chain

Cement grain
Neutral side chains
“steric springs”
RHEOLOGY OF CEMENT WITH 3^ GENERAT ION
SUPERPL ASTICIZERS

-- - -- - - - -- - -- - - -
-- --

--

--
- - --- -- -
--- - -- -- -

- - --

- - --
-- - -

-- - -
-

--
-

-
-- - - -- - - - - -- - - -- - - - -

-
--

--
Potential Energy

REPULSION
Distance

ATTRACTION
 RHEOLOGY OF CEMENT WITH 3^ GENERAT ION
SUPERPL ASTICIZERS

The
- - - -- - - -
simultaneous -- - -- - - -
-- --
--

--
presence of ELECTROSTERIC

- - --- -- -
--- - -- - - -

- - - - - - ---

- - --
negative REPULSION
---

-- - -
-

--
charges and

-
--- - --- -- - -- - - -- - -- -

- --
non ionic
groups in the
polymer
Potential Energy

molecule REPULSION
enhance the
dispersing Distance
capability of the
polymer ATTRACTION

VERY LOW VISCOSITY

92 % r.h.
OPC type I paste after 5
min

0 5 10 15 20 25
OPC type I paste after 1
hour

0 5 10 15 20 25
OPC type I paste after 5
hours

0 5 10 15 20 25
- - - - -

- - - - -
 ALUMINA PHASE HYDRATION - OMP

--
---

-
--

-- -
- - --
FORMATION

--
---
-
- - -- -
T(°C) 30 - - --
-
SILICEOUS PHASE HY DRATION -- - -

-- -
-- - - - -- - - - -- - - -

-
28 C-S-H FORMATION - MECHANICAL
--

-
-- - - - --
-- - - - -
STRENGTH DEVELOPMENT

-
-- - -
-- - - - -- - - - -- - - -
26
C3S, C 2S

24
DORMANT PERIOD

22

20
0 5 10 15 20 25
time (h)
 ---- -
---- -
----
ALUMINA PHASE HYDRATION - OMP

-
FORMATION ---
--

---- -
T(°C) 30 ----
- ---- -
----
SILICEOUS PHASE HY DRATION -
---- - ---- - ---- - ---- -

---- - ---- -
---- -
C-S-H FORMATION - MECHANICAL

-
28

-------
--
STRENGTH DEVELOPMENT
---- - ------- - ---- - ---- -
-
---- - - ---- -
26 C3S, C 2S
DORMANT
24 PERIOD

22

20
0 5 10 15 20 25
time (h)
T(°C) 30,00

28,00 HYDRATION OF SILICEOUS PHASE CONTROLS

THE MECHANICAL STRENGTH DEVELOPMENT

26,00

ACCELERATED
24,00

RETARDING
NORMAL
22,00

20,00
0 5 10 15 20 25
time (h)
workability retention is controlled
by the adsorption
rate of the polymer

-
-
-

-
-

-
-
-

-
 TheThe
Influence of Carbox
key factor to have ylicthese
Acid -properties
Carboxylic is Ester Ratio of
to control theCarbox ylic Acid
adsorption
Ester
kinetics. Superplasticizer
Polymers designedon to the Characteristics
have low affinity tooftheCement Mixturessurface
cementitious
divideG.themselves in notP.uniform
Ferrari, T. Cerulli, Clemente,wayM.between
Dragoni, cement
M. Gamba andandwater,
F. Suribeing
co in
the latter to a great er extent.
MapeiAfter
SpA,the initial
Milano phase, s the cementitious
Italy
phase grows and renew,
Sixth ACI/CANMET theseConference
International moleculeson areSuperplas
adsorbed progressively
ticizers and other
givingadmixtures
chemical their fluidification effect
for concrete, Nice,with time.2000
France

120

100 CE II/A-L 42,5R

POLYMER ADSORPTION
(% by weight of cement)

80

60 CE II/A-L 32,5R

40

RESULTS - ADSORPTION TESTS

20
DOS. 0.3% active/cem
0
INCREASING MOLAR CA/CE
 Adsorption kinetics on CEM I 52,5R
100

80
% Residual fraction

60
in

40

20
Dyn SP1 Dyn SX Dyn SR1
0
0 10 20 30 40
Time from mixing (Min)
 Precast DYNAMON SYSTEM
Early age mechanical strenghts
NRG
SP
Ready Mix

SX
SR
Workability retention
MONOMERS
AND RAW
MATERIALS
SYNTHESIS
SYNTHESIS
INTERMEDIATES
INTERMEDIATES
PRODUCTION
PRODUCTION

R&D

SELL POLYMER
POLYMER
PRODUCTION
PRODUCTION
 Superplasticizers with the desired
characteristics may be obtained by properly
selecting and combining the raw materials in
order to meet the requirements for the
specific application
1. RETENTION OF THE
WORKABILITY FOR MORE THAN
120 MINUTES

2. NO RETARDATION IN
MECHANICAL STRENGTH
DEVELOPMENT
 Chronos are based on the combination of chemically
reactive monomers with time -controlled mechanism of
activation and long side chain monomers for
nanostructural effect in earl y ages mechanical strength
development

CH2 CH CH2 CH CH2 CH

C OO R 1 O C OO R 2

( E O )r H
m n p

R 1 , R 2 = S h o rt ch a in o xye th yle n e ra d ica ls

M w = 7 1 ,0 0 0 M n = 2 4 ,0 0 0 M z = 2 0 3 ,0 0 0
 - -
- - - -
- - -
- - -
 250

200

SLUMP (mm)
150

100

50

0
0 30 60 90 120 150

TIME (minutes)

- -
- - -
- - -
- - -
Reference: Conventi onal Acrylic Superplasticizer

80
CHR POLYMER
ADSORPTION (%)

60

40
REFERENCE

20

0
0 50 100 150 200 250

TIME OF MIXING (MINUTES)