KerneosTM

Aluminates Technologies Primary Functions

 Kerneos Aluminates Technologies are providing 8 key primary
functions to the building chemistry applications

Aluminate Technologies
Rapid drying
Quick setting and rapid
Environment friendly
hardening

Mechanical performances
Shrinkage compensation
& resistance to abrasion

Colours Resistance to corrosion

Non efflorescence

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 Quick setting & rapid hardening characteristics are achieved
through the right mineral composition of the binder

C$ strength
3
Calcium Sulfate

3
CAC as major
binder
2 1
1 2 OPC

CAC OPC
Calcium Aluminate Portland cement time

OPC as major binder

Three main zones of formulation:

1 = quick set
2 = early strength + shrinkage compensation
3 = early strength + quick drying + size variation control

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 In all cases, performance result from hydrate formation

OPC CSH
CH

C3S C3A
• Strength given by C3S hydration
leading to CSH and CH
C$Hx Ettringite shell
neutralisation of
C3A

1 ettringite •CAC reacts with OPC calcium sulfate and C3A

C4AH13 to form structuring ettringite and C4AH13 =
quick set
• A shell of C4AH13 is formed around C3S and
CAC
partially block C3S hydration

2 • Added CAC and calcium sulfate react together

to form structuring ettringite without disturbing
OPC hydration

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 In all cases, performance result from hydrate formation

OPC
CH
CSH
C3S C3A
• Strength given by C3S hydration
leading to CSH and CH

C$Hx Ettringite shell

neutralisation of
C3A

3
ettringite •The role of OPC is to bring Ca (lime) to
AH3 form ettringite.
C$Hx •The matrix is formed of Ettringite and
alumina hydrates

CAC
OPC

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 In all cases, performance result from hydrate formation
Most Building Chemistry applications rely on ettringite formation

Natural Portland hydrates Hydrates formed with CAC

CSH Ettringite

CH

CSH C4AH13

Ettringite

Ettringite = C3A(CaSO4)3H32: is an hydrate made from combination of

calcium aluminate and calcium sulfate,
which combines a lot of water of crytallization thus responsible
for high strengths, size variation control and drying capacity
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Calcium Aluminate is the most flexible Technology to achieve the Building
Chemistry technical requirements, through the formation of ettringite

1- OPC / CAC : Quick setting

Quick set mortars

2- OPC / CAC / C$ : Quick setting

& improved hardening
Repair mortars, tile adhesives, self
levellers, screeds

3- CAC / C$ / OPC : Rapid

hardening, rapid drying &
shrinkage compensation
Technical Segmentation - 100% binder
CAC OPC C$ Self levellers, screeds, tile adhesives
1 < 40% > 60% 0% ( natural stones, porous tiles… ),
2 < 40% > 50% 5 - 20% repair mortars, ...
3 > 60% < 20% 10 - 30%

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 Rapid set

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 Quick set results from simple addition of Calcium Aluminate Cement
to the Portland cement

Mix Portland-Fondu

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 Rapid hardening

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 Quick set and rapid hardening, will result from higher dosages of
Calcium Aluminate Cement

Characteristics of Main Performance Criteria

Mortars Based on Ternary Binder Systems Quick Setting
Quick Setting Quick Hardening
Quick Setting Rapid Drying
Quick Hardening Dim ensional
Stability
Components of the Composition
Aggregates and Fillers 60% 60% 60 - 65 %
Portland Cement 30% 25 - 30 % <5%
Calcium Alum inate Cem ent 10% 10% 20 - 25 %
Calcium Sulfate Anhydrite --- 0-5% ---
Calcium Sulfate Gypsum or Hemihydrate --- --- 7 - 10 %
Additives yes yes yes
Performance Characteristic
Setting Time 1 - 30 min 20 - 45 m in 10 - 60 min
Early Compressive Strength at 2 - 4 h 2 - 5 MPa 3 - 5 MPa 5 - 15 MPa
Compressive Strength at 24 h 10 - 15 MPa 10 - 25 MPa 20 - 40 MPa

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Rapid hardening behaviour according to the mineral binder composition
can be exemplified through basic Self leveller formulation

SL 1 SL 2 SL 3

Ternal RG 8,5 8,5 20

Portland cement 16,5 16,5 4
Hydrated lime 0,8 1,5 0,4
Alpha hemihydrate 0 0 7
Anhydrite 0 4 0
Casein 0,3 0,3 0,2
Calcium Carbonate Durcal 15 21 21 19
Clacium carbonate Durcal 130 11 11 9
Silica Sand Sifraco NE14 40 40 37
Redispersible powder Wacker RE 523Z 1 1 3
Li2CO3 0 0 0,1
Na2CO3 0,05 0,05 0
NaHCO3 0 0 0,2
Trisodium Citrate 0,12 0,12 0,2
Cellulose ether Wolff Walsrode MT 400 PFV 0,1 0,15 0,06
Defoaming agent Dehydran 1922 0,1 0,1 0,05

Eau 24% 23% 24%

Gel time 36 33 40
Initial set 1h10 1h05 1h20
Final Set 1h20 1h35 1h40

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 Rapid hardening behaviour according to the mineral binder composition
can be exemplified through basic Self leveller formulation

Hardening Kinetics of Self Levellers

25
SL 3
SL 1
Compressive strength, MPa

20
SL 2

15

10

time, hours
0
0 2 4 6 8 10 12 14 16 18 20 22 24

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 Rapid drying

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 Drying through water crystallization into hydrates is the only efficient
way to guarantee the achievement of the mortar characteristics

On the job site, a mortar is exposed to varying uncontrolled conditions having a

direct impact on the drying speed:

Absorption into
the substrate

Evaporation
to ambience

Wind Amb. T ℃ Amb. RH Thickness

of application

Size variations
Water Evaporation

Risk of Self Levelling

Sedimentation Compound

Water Absorption
Substrate
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 Drying through water crystallization into hydrates is the only efficient
way to guarantee the achievement of the mortar characteristics

To avoid that the mortar performance ( i.e strengths, drying speed, size variations,
aspect… ) varies according to these conditions, it is critical that the mortar
composition ensures a good balance between hydration speed & capacity

Formulation levers
Lower it is, lower is the amount of water to evaporate.
However, minimum water is required for rheological and
Water addition hydration purposes. On the other side, higher water / solids
ratio means higher porosity of the material thus higher
dyring speed… Not an easy lever to manage.

Ettringite is an hydrate combining a lot of water into its

crystalline structure.
Crystallisation Ettringite formation being fast, good hydrate formation is
ensured prior to drying due to external parameters.
on water into
Thus, the use of Calcium Aluminate Technology, is
hydrates the key lever to get both fast drying & hardening
characteristics together with reliable final
performance

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 Rapid drying through rapid crystallisation of ettringite in
Self Leveling Compounds

e.g: CAC Based self leveller / 3 mm thickness, containing:

OPC CAC CaSO4
5% 20 % 7-8 %

24
20 Evaporation / Absorption
% of water

16
12 Crystallised water
8
4
Residual moisture
0
0 6 12 18 24 30 36 42 48
time in hours

The mineral binder composition is a key factor

determining the overall level of performance.
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 Size variations control

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• Shrinkage can be seen as one of the weak points of cementitious
flooring products

Problems resulting from shrinkage include :

- cracking
- de-bonding from the substrate

These two phenomena can create job-site failures

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 There are two major types of shrinkage :
the chemical and the drying shrinkage

Chemical shrinkage is due to the hydration of the mineral binders ( volume

of hydrates < volume of anhydrous particles + water )

Expansion may also be observed due to repulsive forces between the crystals during
their growth:

Formation of ettringite from calcium aluminates and the right proportions

between constituents is a well known technique to control expansion

The balance shrinkage / expansion is influenced by type of binders, hydrates,

additives, kinetics…

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 Chemical shrinkage is due to the hydration of the binders.

Absolute volume variations : chemical shrinkage

During liquid and soft solid state we
observe a decrease of the apparent water
volume hydrates
we measure a plastic shrinkage binders

(during the soft liquid phase)

t=0 hydration
Mineral skeleton percolation

After the soft solid-solid transition,

the material starts resisting to this
volume variation. We observe the gas

appearance of air voids inside the

solid matrix.
Apparent volume variations
we don’t measure a plastic
shrinkage anymore Liquid paste Soft solid Solid
Barcelo-01
OPC hydration example

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 There are two major types of shrinkage :
the chemical and the drying shrinkage

Drying shrinkage is due to the evaporation of water from the hardened

material;
Internal stresses result from water loss ( porosity creation in small capillaries )
Influenced by T°, %RH, Air convection, microstructure, water amount, hydration
kinetics

Chemical shrinkage starts first, drying shrinkage can start very fast
depending on the curing conditions. Both shrinkage type generally occur
simultaneously.

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Aluminate Technologies efficiently contribute to size variations control through
ettringite formation

In an OPC based formulation

2 mechanisms contribute to shrinkage :
Plastic shrinkage of the mix before setting.
Drying shrinkage following evaporation from the hardened product.

In a CAC / calcium sulphate based formulation

the formation of ettringite compensates for this shrinkage.
800

400

0 CAC / calcium sulphate based system

-400

-800 Portland cement based system

-1200

-1600
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 Size variations of Self Levelling compounds according to their
mineral composition

Size variations of selflevellers, stored at 20°C-70%HR

1500
1000 Time in days
Shrinkage in microns/meter

500
0
-500 0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
-1000
-1500
-2000
-2500
-3000 CMortar
- High A
% Ciment Fondu®
-3500
BMortar
- Medium
B % Ciment Fondu®
-4000
-4500 A - High % Ciment Fondu®
-5000 Mortar C
-5500
-6000
-6500

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 Drying shrinkage for the three systems

Drying shrinkage
rate (µ/m/ day)
450

400

350

300

250

200

150

100 OPC based - Syst 1

50

0 OPC based - Syst 2

1
day 1-7
days 7 - 14 CAC based - Syst 3
days 14 - 28
days 28 - 90
days
Time segment

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Due to their unique contribution to 4 main properties, Calcium Aluminates
are a key technology for the design of self leveling underlayments

Rapid Self Leveling Underlayment

Aluminate Technologies

Rapid drying

Quick setting and rapid

Environment friendly
hardenning

Mechanical performances &

Shrinkage compensation
resistance to abrasion

Colours Resistance to corrosion

Non efflorescence

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 Appendix

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 Drying shrinkage is due to the evaporation of water from the material

1. Free water
1. Meniscus with high
2. Effect on mechanical resistance and
superficial tension
permeability
2. Participate to drying up to
3. No participation to drying shrinkage
50%RH

2.5nm 10nm 50nm 15µm 1mm

Micro-pores Small capillaries Medium capillaries Big capillaries Big spherical voids

1. Water is highly linked to the solid 1. Meniscus with moderate

structure superficial tension
2. No meniscus 2. Participate to drying at high
3. Participate to drying shrinkage at RH amount
low relative humidity (%RH<50%)

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 These two shrinkages will have different effects depending if the material has
an adhesion or not with its substrate

Setting shrinkage Drying shrinkage

crystal growth creates
mechanical links between Body cracks and/or debonding due to
the substrate and the layer non homogenous drying versus thickness
Surface cracks appearance if too fast
Adhesive application Product is young, mechanical drying (air convection on the surface)
properties are still low, Body cracks appearance if shrinkage
important shrinkage could is too high depending of the material
create a debonding of the mechanical properties
new layer

curling due to non homogenous

free to move drying versus thickness
effect limited if substrate Surface cracks appearance if too fast
Non adhesive application drying (air convection on the surface)
roughness of waviness
Body cracks appearance if shrinkage is
is not too high too high depending of the material
mechanical properties

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The growth of ettringite crystals mobilised an important amount of water and
help creating bigger porosity

6Ca2+ + 2Al(OH)4- + 3SO42- + 4OH- + 26H2O 3CaOAl2O3.3CaSO4.32H2O

1. An ettringite crystal fixes 32 water

molecule
2. This chemically trapped water will not
participate to the drying of the material
3. For the same amount of initial mixing
water, there is less water free to
evaporate, thus less meniscus tension
800
inside the material
400

Dimensional variations
4. Ettringite is growing instead of C-S-H 0 CAC / calcium sulphate
based system
which are a large contributor to the -400
porosity bellow 10nm Portland cement
-800
5. In a OPC-CAC-C$ mix, C-S-H are still based system
present but in a much lower amount [µm/m] -1200

6. The drying shrinkage will not be -1600

entirely suppressed but largely 0 1 2 3 4 5 6 7

diminished Time [d]

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