Admixtures Olek

Prepared for the International Conference on Advances in Concrete Technology and Sustainability Issues January 11, 2012, Quito,
Ecuador
International Conference on Advances in Concrete Technology and Sustainability Issues, January 11. 2012, Quito, Ecuador Slide 1 of 36
Compatibility and Incompatibility

Compatibility:
Every admixture present in a cementitious mixture performs its expected role without negative effects.
Incompatibility:
Upon addition of admixture the concrete mixture does not behave as expected
The effects of admixtures can be:

detrimental (one or more admixtures do not perform as expected), or synergistic (combination of admixtures performs better than when used separately)
Robustness The Robust system small variations in the dosage of cement, water or admixture have little effect on the properties of the mixture The Non-Robust system small variations in the cement, water or admixture dosage result in significant (sometimes dramatic) changes in concrete properties
International Conference on Advances in Concrete Technology and Sustainability Issues, January 11. 2012, Quito, Ecuador
Slide 3 of 36
Introduction
Lack of in-depth knowledge of the materials interactions may lead to incompatibilities between various ingredients of the mixture.
Courtesy of Csar A. Constantino, Titan America
Slide 4 of 36
Admixture - Cementitious Materials Interactions Admixtures interact with components of cementitious materials and influence cement hydration Effects depend on:
Type and dosage Composition Sequence of addition Courtesy of PCA w/cm and temperature Compatibility of admixtures (mixtures of admixtures) Chemistry and specific surface area of cem. mat.
Background. Materials incompatibility problems do not occur in every concrete mixture. However, when they arise, concrete may experience undesirable effects, primarily premature stiffening or severe set retardation. In addition, difficulties with creating an adequate air void system may be experienced, resulting in durability problems.
Types of Incompatibilities Resulting from Direct Interactions

Cement-Admixture interaction Admixture-Admixture interaction
Resulting from Indirect Interactions

Typically involve interactions between 2 (or more) admixtures and 1 or more component of cementitious system
Slide 7 of 36
General Trends Role of C3A:

Uncontrolled hydration of C3A is the major reason for early stiffening behavior flash set. Delays setting time by preventing hydration of silicates
Role of sulfates:
Sulfate deficient systems - the rapid hydration of C3A - flash set Excessive sulfate nucleation and growth of gypsum crystals - false setting behavior. The level of soluble sulfates affects adsorption of admixtures
General Trends
Role of alkalis:
Higher alkali cements react faster higher rate of stiffening higher slump loss Dosage requirement of admixtures are directly related to alkali content of the system. Low alkali content systems exhibited lower stability of air void system. Low alkali cement & synthetic air entrainer combination resulted in severe strength loss
Slide 9 of 36
General Trends
Role of Fly Ashes:

May introduce reactive aluminate phases (like C3A and Kleins compound) Sulfates and alkalis in fly ash - disturb the sulfate balance High LOI class F (low lime) ashes problems with generation and stability of air voids Calcium and magnesium ions in the fly ash affect the air entrainment precipitates with AEAs
General Trends
Role of Admixtures:
High alkali contents -increase the amount of polycarboxylate type of superplasticizers optimum fluidity Lignin based admixtures reduce the solubility of sulfates thus disturbing the C3A sulfate balance Sugar content of the lignin based, waterreducers linked to set retardation and air entrainment difficulties VR + Lignin based WRA - high entrapped air & reduction in specific surface area of the air void system
Stages in Hydration Reaction

Jolicoeur et al. 1994, ACI SP-148,pp. 63-88
Solubilization of cement phases
Cement particles become coated with layer of hydrates Critical role of reactions of aluminate and gypsum phases
Iinitial hydration processes (015 min); IIinduction period (15 min4 h); IIIacceleration and setting (48 h); IVdeceleration and hardening (824 h); Vcuring beyond 1 day.
Admixture-binder Interactions Admixtures that modify the properties of fresh concrete may cause early stiffening or retardation of the setting time. Early stiffening is often caused by changes in the rate of reaction between tricalcium aluminate (C3A) and sulfate in the cement. Retardation can result from an overdose of admixture or from a decrease in the ambient temperature. Both delay calcium silicates hydration.
Example: Change in the Rate of Hydration
Jolicoeur et al. 1994, ACI SP-148,pp. 63-88
Change in the rate of hydration at three different dosages of chemical admixture

Critical Role of Sulfate in Controlling Hydration of C3A
Courtesy of C. Jolicoeur
Forms of Sulfates
Forms of CaSO4 CaSO4 . 0 H20 Anhydrite* CaSO4 . 1/2 H20 Hemihydrate CaSO4 . 2 H20 Dihydate (gypsum) Solubility (g/100g) 0.63 0.71 0.21
K2SO4, Na2SO4
Highly soluble
*Anhydrite can be synthetic (soluble) and natural (less soluble) . Natural anhydrite has slower rate of solution than gypsum, hemihydrate or synthetic (soluble) anhydrite
SO4 Supply/Demand Equilibrium
Superplasticizing Chemicals
Class
Lignosulphonates
Origin Derived from neutralization, precipitation, and fermentation processes of the waste liquor obtained during production of papermaking pulp from wood Manufactured by normal resinification of melamine formaldehyde
Structure (typical repeat unit)
Sulphonated melamine formaldehyde (SMF) or Polymelamine sulfonate (PMS)
Slide 18 of 36
Superplasticizing Chemicals
Origin Produced from naphthalene by oleum or Sulphonated SO3 sulphonation; naphthalene subsequent reaction with formaldehyde (SNF) formaldehyde leads to or Polynaphtalene polymerization and the Sulfonate (PNS) sulphonic acid is neutralized with sodium hydroxide or lime Polycarboxylic ether Free radical mechanism (PCE) or using peroxide initiators is Polycarboxylate used for polymerization (PC type) process in these systems Class Structure (Typical Repear Unit)
Slide 19 of 36
Sulfate related Cement Admixture Incompatibility
Effect of Calcium Lignosulfonate (CLS)
Dodson, V. 1990. Concrete admixtures,

PNS adsorption vs. Sulfate Content
Slide 22 of 36
Role of Alkalis The soluble alkali content is a key parameter when studying the compatibility between a cement and a superplasticizer, The addition of a small amount of sodium sulfate can reduce the slump loss of a superplasticized cement paste.
Slide 23 of 36
Compatibility between cements and PNS and relation to adsorption behavior
Alkalies
Na2O eq. Soluble Alkalies
C1
0.31 0.19
C2
0.52 0.41
C3
0.92 0.57
C4
0.74 0.72
C5
0.35 0.07
C6
0.31 0.06
B.-G. Kim et al. / Cement and Concrete Research 30 (2000) 887893

Percent of PNS adsorbed and mini-slump area at 30 min for cement pastes with various Na2SO4 contents.
Alkalies
Na2O eq. Soluble Alkalies
C1
0.31 0.19
C5
0.35 0.07
C6
0.31 0.06

Percent of PNS adsorbed and mini-slump area at 30 min for cement pastes with various Na2SO4 contents.

Example of multi-source interactions Potential incompatibility problems arising in the cementitious systems containing broad collection of cements, fly ashes and chemical admixtures. Focus on abnormal early age stiffening, setting behavior and quality of the air void system.
Chemical properties C3A % SO3 % Na2Oeqv %
Cements C1 9 (M) 3.0(M) 0.29(L) C2 10(M) 2.4(L) 0.3(L) C3 10.1(M) 3.6(H) 1.04(H) C4 7.7(L) 3.6(H) 0.97(H)
Fly ashes Properties F1 Class C ash LOI SO3 Na2Oeqv 0.38 (M) 0.53(M) 2.18(M) F2 Class C ash 0.25(L) 1.14(H) 1.94(M) F3 Class F ash 3.89(H) 0.69(M) 2.21(M)
Slide 28 of 36
Chemical Admixtures
Water Reducing Admixtures: (WRA) Lignin based Type A WRA (W1) Polycarboxylate Type F superplasticizer (W2)
Air Entraining Admixtures: (AEA) Synthetic AEA (A1) Vinsol resin (VR) based AEA (A2)
Work Plan
PHASE I
Study related to rapid slump loss and abnormal set More than 100 paste and mortar mixtures evaluated
PHASE II
Study related to problems with generation &stability of air void system 18 mortars and slurries evaluated
PHASE III
Verification of findings from pastes and mortars 10 concrete mixtures evaluated
Statistical Modeling
DEVELOPMENT OF RECOMMENDATIONS
Slide 30 of 36
Admixture Driven Incompatibilities

W1 + plain C2 severe acceleration while W2 + C2 severe retardation W1 or W2 + C2 fly ash cementitious system severe acceleration of set
110 Temperature (F) 100 90 80 70 60 0 20 40 Time (hrs) 60 80 C2F1 C2F1W1 C2F1W2
Slide 31 of 36
Double Dosage of WRA

Aggravated stiffening problem in all the early stiffening mixtures Significant changes in SAC curves in 5 out 6 mixtures
110 Temperature (F) 100 90 80 70 60 0 10 20 30 Time (hrs) 40 50
Semi Adiabatic Calorimetry Curves Early Stiffening Mixtures

C1F2W1 C2F1W2 C2F2W1 C1F2W1(DD) C2F1W2(DD) C2F2W1(DD)
Slide 32 of 36
Fly Ash Driven Problems
W2+A2
W1+A2
A2 0 200 300 400 500 Dosage of AEA - A2 (ml /100kg) 60% fly ash mixes 20% fly ash mixes 0% fly ash mixes 100
As the fly ash content increased, the amount of A1 or A2 (required to attain 18+/-2 % air content) also increased
Effect of Class C Ash Content

110
100
C2F1(20)W2A1 C2F1(20)W1A2
Temperature (F)
90
C2F1(20)W1A1
80
C2F1(20)W2A2 C2F1(30)W2A1
70
C2F1(50)W1A2 C2F1(50)W1A1
60 0 10 20 30 40 50
C2F1(70)W2A2 Time (hrs)
94% of high (>30%) volume fly ash (HVFA) mixtures significant acceleration of set 70% HVFA mixtures set time less than 45mins
Steps to Identify Incompatibility
New Reactive Materials:

Cement: C3A , sulfate & alkali content SCMs: sulfate% & LOI WRAs & AEAs : Varying chemical nature
Air Void System:

Air content in mortars (ASTM C 185) or Foam index testing Foam drainage testing
Potential incompatible combination ???

Steps to Mitigate Incompatibility

Potentially incompatible combinations ???
Vary the following (one or more at a time) and test again for potential problems. Air Void System:
Select a fly ash with low LOI Change the percentage of fly ash replacement Change the type of air entraining agent (AEA) Change the type of Water reducing agent (WRA)
Test the new combination for incompatibility


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Prepared for the International Conference on Advances in Concrete Technology and Sustainability Issues January 11, 2012, Quito,

Compatibility and Incompatibility

The effects of admixtures can be:

Courtesy of Csar A. Constantino, Titan America

Types of Incompatibilities Resulting from Direct Interactions

Resulting from Indirect Interactions

General Trends Role of C3A:

Role of Fly Ashes:

Stages in Hydration Reaction

Solubilization of cement phases

Example: Change in the Rate of Hydration

Jolicoeur et al. 1994, ACI SP-148,pp. 63-88

Change in the rate of hydration at three different dosages of chemical admixture

Critical Role of Sulfate in Controlling Hydration of C3A

SO4 Supply/Demand Equilibrium

Structure (typical repeat unit)

Sulphonated melamine formaldehyde (SMF) or Polymelamine sulfonate (PMS)

Sulfate related Cement Admixture Incompatibility

Effect of Calcium Lignosulfonate (CLS)

Dodson, V. 1990. Concrete admixtures,

PNS adsorption vs. Sulfate Content

Compatibility between cements and PNS and relation to adsorption behavior

B.-G. Kim et al. / Cement and Concrete Research 30 (2000) 887893

B.-G. Kim et al. / Cement and Concrete Research 30 (2000) 887893

B.-G. Kim et al. / Cement and Concrete Research 30 (2000) 887893

Chemical properties C3A % SO3 % Na2Oeqv %

Admixture Driven Incompatibilities

Double Dosage of WRA

Semi Adiabatic Calorimetry Curves Early Stiffening Mixtures

Fly Ash Driven Problems

Effect of Class C Ash Content

C2F1(70)W2A2 Time (hrs)

Steps to Identify Incompatibility

New Reactive Materials:

Air Void System:

Potential incompatible combination ???

Steps to Mitigate Incompatibility

Test the new combination for incompatibility

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