Polymer Technology in

Admixture Systems

Nov 20, 2012

History of Concrete Admixtures

 1824 Production of Portland-Cement

 1935 Plasticizers based on Ligno and Naphtalenesulph.
 1945 First air-entraining agent (AEA) in the USA
 1955 Plasticizers become commodities
 1966 First Superplasticizers on Melamine base (SKW)
 1986 First polycarboxylates in Japan
 1992 Polyacrylates in Switzerland
 1997 Polycarboxylates in Europe
Admixture Definitions

Admixtures are material other than water, aggregates, hydraulic

cement, and fiber reinforcement, used as an ingredient of
concrete or mortar, and added to the batch immediately before
or during its mixing
ACI 116.R-2

3
Admixture Classifications

According ASTM C 494

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 Water Reducing and Retarding

4
Admixture Classfications
Admixture Systems

Water/Cement < A
Water/Cement < A Slump = B
Slump < B Strength > C
Strength > C

To Increase
CEMENT Strength

+ - WATER
To Increase
W/C = A
Water/Cement = A Workability
Slump = B + ADMIXTURE Slump > B
Strength = C Water Reducer
Strength = C
+

WATER -CEMENT
-WATER

Water/Cement >A Water/Cement = A

Slump > B Slump = B
Strength < C Strength = C
6
Typical performances of water reducing
admixtures:

 Modified ligninsulphonates up to 15 %
 Melamine sulphonates up to 25 %
 Naphtalene Sulphonates up to 25 %
 Polyacrylics up to 30 %
 Polycarboxylic ethers up to 40 %
Plasticity Curve

12
10

SLUMP, In.
8
w/c - 0.36 - 0.40
6
w/c - 0.23 - 0.27 4

W/c Ratio 2

-2
Water For
Hydration

0 Water Content
Plasticity Curve

12
10

SLUMP, In.
Conventional
8 Water Reducers
w/c - 0.36 - 0.40
6
w/c - 0.23 - 0.27 4

W/c Ratio 2

-2
Water For
Hydration

0 Water Content
Plasticity Curve

12
10

SLUMP, In.
Conventional
8 Water Reducers
w/c - 0.36 - 0.40
6
w/c - 0.23 - 0.27 4

W/c Ratio 2

-2
Mid-range
Water For Water Reducers
Hydration

0 Water Content
Plasticity Curve

12
10

SLUMP, In.
Conventional
w/c - 0.36 - 0.40 8 Water Reducers

w/c - 0.26 - 0.31 6

w/c - 0.23 - 0.27 4

W/c Ratio 2

-2
Mid-range
Water For Water Reducers
Hydration

0 Water Content
Extended Workability

100
90
80
workability [%]

70 MS
60
NS
50
40 Lignosulfonates
30 Polycarboxylates
20
10
0
0 30 60 90 120 150 180
workability time in minutes
Development of Strength

100
with GLENIUM
80 with traditional plasticiser
with admixture
compressive strength

60

40
MPa

20

0
0 7 14 21 28

time [d ]
Hydration Process
Hydration Stages

Hydration of Portland cement

C-S-H gel
cement
grain

After mixing with water

 Hydration Stages

H2O

Ca(OH)2

C-S-H gel
Semi-permeable
membrane

C3S (and C2S) + Water C-S-H Gel + Calcium Hydroxide

Mechanism of Works without Admixture

WATER+CEMENT SYSTEMS WITHOUT ADMIXTURE

hydration
cement grains products

LOSS OF FLUIDITY LOSS OF FLUIDITY

& WORKABILITY
Dispersion obtained Attractive forces
due to the presence between cement
of water
Mechanism of Works without Admixture

Ca2+ Ca2+ Ca2+ O-

-O Ca2+
Ca2+ Ca2+
Ca2+ Ca2+ O-
-O Ca2+
-O Ca2+ Ca2+ Ca2+
O-
Ca2+ Ca2+ Ca2+
cement grain

cement grain
Ca2+
-O Ca2+
Ca2+
Ca2+ Ca2+
Ca2+ O-
Ca2+ Ca2+
-O Ca2+
formationCa 2+
O-
Ca 2+

of positively charged
Ca Ca 2+
2+ 2+ O-
Ca
-O Ca 2+
sufaces
Ca
2+
2+

Ca
-O Ca2+
Ca2+
O-
Ca2+ Ca2+

-O Ca2+ Ca2+

Ca2+
O-
Ca2+ Ca2+
Ca2+
Ca2+ Ca2+ O-
-O Ca2+ Ca2+
Ca2+
Ca2+ O-
-O Ca2+ Ca2+ Ca2+
Ca2+
Compressive non Admixture

Unvibrated Vibrated
Water/Cement Compressive Strength Compressive
Ratio = 0.35 1400 psi Strength
9800 psi
Mechanism of Works Admixture

WATER+CEMENT SYSTEMS WITH ADMIXTURE AS DISPERSANT

dispersant molecules

Dispersion With fluidity loss and a

caused by electrostatic repulsion decrease in workability
decrease of the W/C ratio

Example: Pozzolith, Rheobuild, Polyheed

Mechanism of Works 1st Generation
Admixture


Ca O-
2+

-O
Ca2+
negatively charged functional groups
-O
Ca 2+
provide waterCa
solubility
O-
2+
and affinity to
cement grain

-O positively charged surfaces

cement grain
Ca 2+

O-
Ca 2+

-O
Ca 2+


O-
Ca2+

addition
-O
Ca of 2+ 1st generation plasticizers
O-
Ca 2+

e.g. lignine sulfonates,

naphthaline-sulfonate-formaldehyde resins
Ca2+
O-

Ca2+
-O melamine-formaldehyde-sulfonate resins
-O
Ca 2+

Ca2+
O-
-O
Ca 2+

Ca2+
O-
Ca O-
-O
Ca 2+ 2+

2+
O-
-O
Ca2+ Ca
Mechanism of Works with Admixture


Ca2+
O-
-O
Ca 2+

 O-
-O 2+ Ca2+
Ca

-O
cement grain

cement grain
Ca 2+


Ca2+
O-
-O
Ca2+


Ca O-
2+

-O
Ca2+ O-
Ca 2+

1stgeneration:
 O-
-O
Ca2+ Coulomb Ca2+

-O
Ca 2+
repulsion only! 
Ca2+
O-
-O
Ca 2+

Ca2+
O-
 O-
-O
Ca 2+ Ca2+

 O-
-O 2+ Ca2+
Ca
Loss of Workability Overtime

2+
Ca O-
-O 2+
Ca
Loss of dispersing effect! 
-O  2+
Ca Ca2+
O-

-OCa 2+

2+
Ca O-
cement grain

cement grain
-O Ca2+

2+
Ca O-
-O Ca2+ O-
Ca 2+


Ca2+
O-
-O
Ca2+


-OCa 2+

Ca2+
O-

-OCa 2+
2+
Ca O-
Incorporation of superplasticizers 
-O  2+
Ca
into growing hydrate phases
Ca2+
O-
 2+
Ca O-
-OCa 2+
Compressive with Admixture

Unvibrated Vibrated
Water/Cement Compressive Strength Compressive Strength
Ratio = 0.35 7000 psi 9800 psi
Mechanism of Works

WATER+CEMENT SYSTEMS WITH NEW GENERATION ADMIXTURE

AS DISPERSANT OF POLYMERS BASED

Polymer Dispersant

Improved dispersion improved dispersion stability

due to electrostatic and better workability retention
steric repulsion
low W/C ratio

Example: Glenium
Mechanism of Works with Admixtures



Ca
Ca2+
2+
O-
-O
Ca 2+
2+
Introduction of

 O-
-O 2+
2+ Ca
Ca 2+
2+
Ca
polyether
-O
cement grain

cement grain
Ca 2+
2+

side chains: 

Ca
Ca2+
2+
O-
-O
Ca2+
2+



Ca
Ca O-
2+
2+

-O
Ca2+
2+

st

O-
Ca
Ca 2+
2+

21ndgeneration:

 O-
Coulomb Ca
Ca2+
2+

-O
Ca2+
2+
polyether carboxylates
-O
Ca 2+
2+
repulsion
Coulomb andonly!
steric 

Ca
Ca2+
2+
O-
-O
Ca 2+
2+
repulsion 

Ca
Ca2+
2+
O-

 O-
-O
Ca 2+
2+ Ca
Ca2+
2+

more effective! 

-O
Ca2+
2+ Ca
Ca 2+
2+
O-
Surface finish
Water Reducing Admixtures

No Admixture
Conventional

Mid-range Water Reducer High-range Water Reducer

 Versatile polymer technology by BASF

R1O CH3
(CH2CH2O)n (CH2CH2O)m H
O +
Radical
R2
polymerization
Acrylic monomers Reactive macro-monomers

Spacious side chains

Cement slurry

Cement surface
Carboxylic functions in the backbone
Positive z-potential
11/20/2012 30
 Versatile polymer technology by BASF

 Specific performances are designed by adjusting functional building blocks,

molecular weight, side chain length, charge density, graft density.
Side chain

Water reduction capability

Functional building blocks

Viscosity Workability
control retention
C C C
O O- O O- O O-
COOM
+ +
Thixotropy Cement Cement Surface +
control affinity
11/20/2012 31
2nd Generation of PCE:
Maintaining Workability More Longer

2+ Ca
2+Ca
2+ Ca 2+ 2+
2+ Ca
CaCa Ca2+
Ca2+
Ca2+
Ca2+
Ca2+Ca2+

2+ Ca
2+Ca
2+ Ca 2+ 2+
2+ Ca
CaCa Ca2+
Ca2+
Ca2+
Ca2+
Ca2+Ca2+
2+ Ca
2+Ca
2+ Ca 2+ 2+
2+ Ca
CaCa
Ca2+
Ca2+
Ca2+
Ca2+
Ca2+Ca2+
2+ Ca
Ca 2+ Ca
2+Ca 2+ 2+
2+ Ca
Ca
cement grain

cement grain
Ca2+
Ca2+
Ca2+
Ca2+
Ca2+Ca2+
2+ Ca
2+Ca 2+ 2+
2+ Ca
Polymer molecules remain at the
2+ Ca
CaCa surface
2+ 2+ 2+
Ca Ca Ca Ca Ca Ca 2+ 2+ 2+

for a longer period of time

2+ Ca
2+Ca
2+ Ca 2+ 2+
2+ Ca Ca2+
Ca2+
Ca2+
Ca2+
Ca2+Ca2+
CaCa

2+ Ca
2+Ca
2+ Ca 2+ 2+
2+ Ca
CaCa
Ca2+
Ca2+
Ca2+
Ca2+
Ca2+Ca2+
2+ Ca
2+Ca
2+ Ca 2+ 2+
2+ Ca
CaCa
Ca2+
Ca2+
Ca2+
Ca2+
Ca2+Ca2+

2+ Ca
2+Ca
2+ Ca 2+ 2+
2+ Ca
CaCa Ca2+
Ca2+
Ca2+
Ca2+
Ca2+Ca2+

2+ Ca
2+Ca
2+ Ca 2+ 2+
2+ Ca
CaCa Ca2+
Ca2+
Ca2+
Ca2+
Ca2+Ca2+
3rd Generations of PCE : Tailor Made
Admixture

GLENIUM 170

PLASTICITY
WATER
RETAINER
REDUCER
GLENIUM 181

GLENIUM ACE 8
SURETEC

STRENGTH VISCOSITY
ENHANCER And More ….. CONTROLLER
3rd Generations of PCE: Versatile Polymer
Technology Allows Formulations of Tailor-
Made PCE molecules
Polymer based Admixture Applications

 Suretec (Super Retention Technology) - maintain workability more longer

 SDC (Smart Dynamic Concrete) - flowing concrete with less cementitous
usage without segregation and bleeding
 UHSC (Ultra High Strength Concrete)
 4 x 4 Concrete - 400 psi flexural strength in 4 hours
 Cement Additive - increase productivity, less energy consumption,
strength enhancer
THANK YOU