Compatibility Issues in Concrete Chemical Admixtures

Carmel Jolicoeur
Department of Chemistry Universit de Sherbrooke Sherbrooke, Qc, Canada J1K 2R1

CANMET/ACI INTERNATIONAL CONFERENCE ON ADVANCES IN CONCRETE TECHNOLOGY IN THE MIDDLE EAST

Dubai, November 19-20, 2008

1

Scope of Presentation
Defining incompatibility: type and origin Chemical admixtures: Types Function Mode of action Interactions between admixtures Cement-admixture interactions Avoiding incompatibilities
2

Compatibility / Incompatibility
Compatibility: Every admixture in a cementitious mix performs its expected specific role. Incompatibility: When the cementitious mix does not behave as expected, for whatever reason, the admixtures are incompatible.
Detrimental: One or more admixture does not perform adequately
or predictably. Synergistic: When several admixtures are used simultaneously, some of the admixtures perform better than when used individually.
3

Compatible vs Incompatible
Hardened concrete results from Reactions and Interactions between Water and cement components: C3S, C2S, C3A, C4AF, CaSO4, Alkali Sulfates, Silica Fume, Fly Ash, CSH, Ettringite, AFm, etc.

In the presence of chemical admixtures the evolution of

the Reactions / Interactions may be influenced predictably (Compatible) or unpredictably (Incompatible)

Origin of Incompatibilities ?
DIRECT INTERACTIONS Cement-Admixture interaction Admixture-Admixture interaction INDIRECT INTERACTIONS Interactions involving 2 or more admixtures and 1 or more component of cements

A Classical Example: Cement-SP Compatibility

Compatibility reflected by concrete rheology

Ideal
Slump Compatible Incompatible
0 1 2
6

Time (hrs)

Common Chemical Admixture Types

AEA : Air-Entraining SRA: Shrinkage-Reducing WR: Water-Reducing

SP: Superplasticizers
VEA: Viscosity-Enhancing Others: Set-Controlling, Corrosion-Inhibiting, Sealing, etc.
7

AEA Air-Entraining Agent

Air-Entraining Agent (Surfactant)

Hydrophobic chain (water insoluble) Hydrophylic head group (water soluble) Anionic COO SO42 SO3Ex: Sodium dodecylbenzenesulfonate (DDBS)
SO3-Na+

CH2 CH3 CH2

CH2 CH2

CH2 CH2

CH2 CH2

CH2 CH2

CH2

AEA
9

Surfactants in Solution and at Interfaces

CMC
10

Surface tension

Function of AEA

Promote the incorporation of air voids in cementitious systems for frost resistance

11

SRA Shringkage-Reducing-Admixtures

12

SRA Shringkage-Reducing-Admixtures

CH2 CH3 CH2

CH2 O

CH2 CH2

O CH2

CH2 OH

Ex: N-Butyl-diEthylene Glycol

SRA

Note: similarity to AEA

13

Function of SRA
SRAs reduce surface tension thus reduce capillary pressure and internal strain

SRA

14

Water Reducers and Superplasticizers

15

Poly Naphthalene Sulfonate (PNS)

CH2

PNS

PNS

- - - - - - - - - -

- -

SO3Na

16

Lignosulfonate and Poly Melamine Sulfonate

OH H3CO HO O
3Na SOSO 3Na

LS

H3CO

NH

NH

LS / PMS

PMS

HN

SO3 SO 3Na

Na

17

Polycarboxylate

* * NaO n O O m O

- -

PC

O CH3

18

Mode of Action of SP
Adsorption -- - - - -- - - - - - - -- - - -- PNS type Electrical charging - -----

---- ----

--

PC type
19

Mode of Action of PNS, PMS and Ligno

Inducing Particle-Particle repulsion - -- - - - - - -- - - - - - - - - -- - -- - - --- 20

Electrostatic (mostly) and Steric repulsions

10

Mode of Action of PC
Inducing Particle-Particle repulsion

Electrostatic Steric Mostly steric repulsion

21

Mode of Action of PC
Control of nucleation and growth processes

Heterogeneous (Topochemical)

Homogeneous (from solution)

22

11

Function of Superplasticizers
Deflocculation and Dispersion
Floculated Defloculated Dispersed in less water

Low fluidity

High fluidity

Intermediate fluidity

Defloculating effect of SP operative in any slurry or paste

23

Illustration of SP Dispersion Effect

+10 % water

Cement Paste

+0.1 wt% PNS

24

12

VEA Viscosity-Enhancing-Admixtures

25

VEA Viscosity-Enhancing-Admixtures

Cellulose

Welan Gum

VEA

Starch

26

13

VEA in Action
Formation of gel network by polymer molecules

Water retention by adsorption and swelling

27

VEA in Action

Polymer hydration and particle bridging

28

14

Function of VEA
Water retention and immobilization of fines

VEA

VEA prevent bleeding and segregation in concrete

29

Illustration of Different Admixture Types

-- -- - - - - - LS/PMS

PNS

- AEA SRA

- -

- - -

VEA

1X

PC

10 X

1000 X

Note approximate relative Size, Charge density and Hydrophilic character

30

15

Compatibility / Incompatibility Manifestations of Admixture-Admixture Incompatibilities

SP AEA Compatibility
Excess entrained air, increasing with time
Concrete W/C 0.45 35MPa
16 14 12 10 8 6 4 2 0 0 16 14 12 10 8 6 4 2 0 0 20 40 Time (min)
32 S. Moffat-Bergeron and R. Gagne, 2008

Air at 10 min (%)

PC PNS No SP

200 400 600 AEA (ml/100 kg cement)

Air (%)

60

16

VEA SP Compatibility (bleeding)

Cement paste, W/C 0.65 Welan
80
Bleed (ml)
80 PNS PC 60
Bleed (ml)

Methocel
PNS PC

60 40 20 0 0

40 20 0

0.02 0.04 0.06 0 VEA dosage (%)

0.05 0.1 0.15 VEA dosage (%)

33

N. Mikanovic and C. Jolicoeur, unpublished, 2006

VEA SP Compatibility (stability)

Cement paste, W/C 0.65
Welan
1 0.9 0.8 0.7 0.6 0.5 0

Methocel
1 0.9

Stability

Stability

0.8

PNS0.7 PC 0.6
0.02 0.04 VEA dosage (%) 0.06 0

PNS PC
0.05 0.1 0.15 VEA dosage (%)
34

N. Mikanovic and C. Jolicoeur, unpublished, 2006

17

SP / WR performance
Dosage = 1% wet basis; Concrete
300 250
PC (0.3% dry)

Slump (mm)

200 150 100 50 0 0 25 50 Time (min) 75

35

LS PNS 0.4% PMS

Coppola, p203, ACI-SP173, 1997

PC - SP Compatibility in Mixtures
Dosage = 1% wet basis; Concrete
250

250

Slump (mm)

Slump (mm)

200 150 100 50 0 0

LS PMS PNS

200 150 100

PMS LS PNS

50

5 min
25 50 75 PC (%)

0 100 0

30 min
25 50 75 PC (%) 100
36

Coppola, p203, ACI-SP173, 1997

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Compatibility / Incompatibility
Manifestations of Cement - Admixture Incompatibilities

Cement AEA Compatibility

Surfactant Na salt n-Octanoate n-Nonanoate n-Decanoate n-Undecanoate n-Dodecanoate n-Octyl sulfonate n-Decyl sulfonate n-Dodecyl sulfonate n-Octyl sulfate n-Decyl sulfate n-Dodecyl sulfate Formula CMC of Na salt (mM) 345 230 95 50 25 148 40 9.8 130 33 8.2 Solubility of Ca salt (mM) 9.5 (20) 3.95 (20) 1.31 0.12 0.09 (15) na 3.21 0.2 na na 4.57 (50)
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n-C7H15COONa n-C8 n-C9 n-C10 n-C11 n-C8H17SO3Na n-C10 n-C12 n-C8H17OSO3Na n-C10 n-C12

19

Comparative Performance of AEA Series

35 30
% Air at 36 min
C10SO3, C10SO4

25 20 15 10 5 0 0 5 10 Surfactant (mM) 15 20
39

C8SO3, C8SO4 C12SO4 C7, 8,

9COO C11COO

Comparative Performance of AEA Series

2.50 2.00

Maximum AE at intermediate chain length

2.50

- Log [CMC (M)]

1.50 1.00 0.50 0.00

-2.00 -2.50 -3.00 -3.50 -4.00 -4.50 6 8 10 12 14 Number of carbons

RCOOLog [solubility (M)]

2.00
- Log [CMC (M)]

1.50 1.00 0.50 0.00 6 8 10 Number of carbons 12 14

Log [solubility (M)]

40

20

Over-Fluiditification with PC Superplasticizers

Mortar, W/C 0.4; PC 0.16%
340 300 280 260 240 220 200 0 10 20 30 Time (min) 40 9 8 7 6 5 4 3 2 1 0 0

Paste, W/C 0.5; PC 0.16%

Over-fluidification

% of PC-ini. ads

320

30C

Spread (mm)

20C

10C

10 20 30 40 50 % Over-fluidification

60

Weak PC cement-binding and variable fluidification

41 Regnaud et al, p389, ACI-SP239, 2006

Cement Admixture Sulfate-related Incompatibility

SO4

SO4
Buffer solution

SO4
consumption in hydration products

supply

42

21

Crucial Role of Sulfate in C3A Hydration

w/o SO4 2C3A + 21H C4AH13 + C2AH8 ... CAH

with SO4 C3A + 3CSH2 + 26H

2C3A + C6AS3H32 + 4H Sulfate supply Available in solution from: Sulfate demand C3A - amount - reactivity Sulfate balance Supply / Demand

C6AS3H32 (Aft)
3C4ASH12 (Afm)

- CaSO4xH2O - Na2SO4, K2SO4 Ettringite (Aft) Monosulfoaluminate (Afm) Critical Equilibrium

43

Portland Cements: Clinker + (x%) Ca Sulfates

Type C2S C3S C3A C4AF I II 25 30 50 45 12 7 8 12 CaSO4 form CaSO40 H2O anhydrite Solubility g/100 g 0.63

III
IV V

15
50 40

60
25 40

10
5 4

8
12 10

CaSO4 H2O hemihydrate

CaSO42 H2O dihydrate,gypsum

0.71

0.21

44

22

SO4 Supply / Demand Equilibrium

SO4 / C3A Ratio (in first min-hrs)

SO4/C3A
Product formed

Too low
CAH gel

Balanced
Ettringite

Too high
Secondary gypsum False set rapid, reversible slump loss

Behaviour of concrete

Flash set rapid, Controlled C3A irreversible loss hydration, of slump adequate slump retention

45

Cement Admixture Sulfate-related Incompatibility

C2S C3A
SO4 SO4

SO4 SO4

C3S

SO4

SO4

Competitive adsorption of PNS and SO4 at most reactive sites of cement particles

C4AF

46

23

PNS Adsorption and Sulfate Competition

300

C3A 300

C4AF

12 10

C3S

PNS (mg/g) PNS (mg/g) ads ads

200

200
+CaSO4 .1/2 H2O

+Na2SO4

8 6 4

100
+Na2SO4

100

+CaSO4 .1/2 H2O

2 0

0 0 0.5 1

0
0 0.5 1

0.5

1
47

[PNS]soln (wt%)

Sulfate Deficient Cement High PNS Adsorption

Addition of SO4 (Na2SO4) Mini-slump area at 30min

C1

C5

C6

Adsorbed PNS (%) With Na2SO4 : PNS adsorption Slump area

48

Kim et al, Cem. Conc. Res., 30, p. 887-983, 2000

24

Sulfate-Balanced Cement
Influence of Sulfate on PNS or PC Adsorption and Paste Fluidity
RF Ads

Relative flow area, G

Relative flow area, G

12 10 8 6 4 2 0 0.0 0.2 Sulfate (mol/L)

121.0 100.8 8 0.6 6 0.4 4 20.2

Adsorption ratio

1.0 0.8 0.6 0.4 0.2

Adsorption ratio
49

PNS

PC
0.0 0.2 0.4 Sulfate (mol/L)

00.0 0.4 0

Yamada, p367, ACI-SP195, 2000

Illustration of Cement-SP Incompatibility

Due to Sulfate Deficiency
SP(SO3) SO4 CaSO4xH2O K2SO4, Na2SO4 Modified ettringite incorporating SP

C3A
(C4AF)

Low SO4 in solution SP(SO3) excessively bound Formation of ettringite (modified) strongly repressed Rapid loss of fluidity 50

25

Illustration of Cement-SP Incompatibility

Due to Excess Sulfate
CaSO4xH2O K2SO4, Na2SO4 Excess SO4 in soln

SP(SO3) SO4

C3A
(C4AF)

SP inhibits growth of gypsum (syngenite) Extensive precipitation of gypsum (or syngenite) Rapid loss of fluidity
51

Origin of Cement-SP Incompatibility

C3A
(C4AF)

SP adsorption C3A content C3A reactivity (type) Cement fineness SP molecular properties SO4 balance in solution Type of CaSO4 (G, H, A) Alkali sulfate content Ettringite formation (rate, type) Gypsum (syngenite) precipitation

52

26

Avoiding Incompatibility Situations through

Adequate specification/qualification of the cement, SCMs, aggregates Relevant characterization of the molecular properties of the admixtures (and variability in the latter) Better understanding on the mode of action of the admixtures in order to anticipate incompatibility issues Development of more robust chemical admixtures, or combinations of admixtures; examples with sulfonated PC Extensive quality control and concrete testing.
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