An Introduction to Metakaolins

Virginie Soleil-Raynaut
Imerys -- Product Manager Kaolins & Chamottes

Geopolymer Camp
Saint-Quentin, 09 July 2019
 An Introduction to Metakaolins

What is Metakaolin?
The Manufacture of Metakaolin
The Properties of Metakaolin

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 What is Metakaolin? -- The structure of kaolinite

■ Kaolinite is a hydrous aluminium silicate:

Al2Si2O5(OH)4 or Al2O3 . 2 (SiO2) . 2 (H2O)

■ With heat, water is released from the crystalline structure and the structure is modified.

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 What is Metakaolin? -- The transformation of kaolinite

Kaolinite: Al2Si2O5(OH)4 Kaolin

550 °C
Loss of water; loss of crystalline order

Metakaolin: Al2Si2O7(OH2)2(1-α) amorphous

(with α dehydroxylation ratio)
Metakaolin

975 °C
Loss of water; new crystalline order
Al-Si Spinel: Al2Si2O7
Calcined
kaolin
1150 °C

Mullite (3 Al2O3 : 2 SiO2) + excess of SiO2 Chamotte

Temperature (°C)

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 What is Metakaolin? -- The transformation of kaolinite

The DTA curve shows a broad

endothermic peak at 550°C and a
sharp exothermic peak at 983°C.

The main endothermic peak

(∼550◦C) is associated with the loss
of weight on the TG curve.

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 What is Metakaolin? -- Structural characterisation

XRD shows the disappearance of the crystalline structure of kaolinite. The structure of
metakaolin is amorphous.

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 What is Metakaolin? -- Structural characterisation

27Al NMR shows the presence of AlV, a five-coordinate

species. This species is very reactive and is characteristic of
metakaolin.

Kaolinite Metakaolin

Structure • Al3+ in • Destruction of Al3+

octahedra. octahedra.
• Si4+ in • Si4+ in a polymer of
tetrahedra. tetrahedra.

27Al NMR • AlVI signal • AlVI transforms into

(–3 ppm). AlIV (70 ppm)
& AlV (35 ppm).
29Si NMR • SiIV signal • “metakaolin signal”
(–90 ppm). (–100 ppm).

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 An Introduction to Metakaolins
What is Metakaolin?
The Manufacture of Metakaolin
The Properties of Metakaolin

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 Manufacture of Metakaolin

Feed Kaolin Calcination Milling

- Mining - Rotary Kiln - Ball Mill
- Preparation - Flash Kiln - Hammer Mill
- Roll-press Mill

Key performance factors Key performance factors Key performance factor

- Mineralogy - Time - Particle size
- Chemistry - Temperature
- Specific Surface - Redox conditions

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 Manufacture of Metakaolin: Processes of Calcination

■ There are several industrial processes to calcine a kaolin clay, some known since
Antiquity.

■ Two main processes used within Imerys:

o Continuous furnaces: wherein loads are moved through temperature zones continuously of
intermittently
‒ Herreshoff multilevel kiln: UK, USA
‒ Rotary kiln: France (Clérac), Ukraine (Vatutine), USA (Andersonville)

o Flash kilns:
‒ Torbed calciner: UK
‒ Flash kiln FCB type: France (Clérac)

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 Manufacture of Metakaolin: Rotary Kiln

www.cementkilns.co.uk Rotary kiln at Imerys Refractory Minerals

Clérac (France)
L= 34 m; ø 2,5 m

Residence time: Throughput: 10 tonnes per hour

4 hours Fuel oil + Biogas + Sawdust

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 Manufacture of Metakaolin: Rotary Kiln

Advantages Drawbacks

■ The technology is reliable and robust (similar ■ Dehydroxylation control after heating: need
to a cement plant). to have a good knowledge of the process.

■ Efficient energy consumption: 800-1200 kWh/t ■ The feed material is shaped as pellets
→ temperature gradient in the pellet.
■ Good throughput rate: 10-12 tonnes/h
■ Product has to be milled after calcination.

■ The kiln has to be run continuously so need

of a certain volume or combination with other
materials.

Product available:
❖ ARGICAL M-1000 (France)
❖ MK-40 (Ukraine)
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 Manufacture of Metakaolin: Herreshoff Kiln

Advantages Drawbacks

■ Technology is reliable and robust (similar as ■ Dehydroxylation control after heating: means
rotary kiln). to have a good knowledge of the process

■ Efficient energy consumption: 600-1200 kWh/t ■ Thermal inertia of the kiln

■ Very good control of temperature of ■ Huge investment: 1.5-2 times more than a
calcination rotary kiln.

Residence time:
40 -- 60 minutes

Product available:
❖ METASTAR 501 (USA)

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 Manufacture of Metakaolin: Flash Kiln

Advantages Drawbacks

■ Really flexible: Target temperature quickly ■ Complex operational system.

reached.
■ Important cost of investment.
■ Precise control of temperature, thus of
dehydroxylation. ■ Milled material needed for feed.

■ Limited energy consumption: 400 to 800 Residence time:

kWh/t less than 1 second

■ Capacity of kiln adapted by initial design

(1 tonne/h at Clérac).

■ Can produce very fine metakaolin (pre

milling).

Product available:
❖ ARGICAL M-1200S (France)

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 Manufacture of Metakaolin: Imerys Clérac

Extraction / stockpiling

Shredding Rotary Kiln Calcination Milling (hammer mill)

Drying + Milling
+ Air classification ARGICAL M-1000

Flash Calcination ARGICAL M-1200S

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 An Introduction to Metakaolins
What is Metakaolin?
The Manufacture of Metakaolin
The Properties of Metakaolin

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 Properties of Metakaolin: Pozzolanic Activity

■ Pozzolans are inorganic material composed mainly by rich siliceous or silico-

aluminous amorphous phases.
■ Pozzolans themselves possess no binder properties.
■ In the presence of water, pozzolans chemically react with calcium hydroxide to
produce compounds with binder properties.

Pozzuoli

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 Properties of Metakaolin: Pozzolanic Activity

■ Metakaolin is an amorphous state of kaolinite obtained by firing the mineral at a

temperature between 700 and 950°C.

■ It is a pozzolanic material, i.e. it reacts with lime in the presence of water.

◆ In cementious materials, metakaolin reacts with the lime released by the cement during its
hydratation; it also reacts with the lime added in some mortars.
◆ Pozzolanic reaction:
free lime
Ordinary Portland Cement + H2O → CSH + CH

CH + AS2 → C2ASH8 + CSH

metakaolin binder
new phase (dense)
due to metakaolin

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 Properties of Metakaolin: Pozzolanic Activity

■ On a day-to-day basis, the pozzolanic activity is measured via the modified Chapelle
test.
■ It is an indirect measurement, based on the consumption of Ca(OH)2 in a saturated
water medium.

1: Condenser
2: Circulation of water
3: Stopper with 2 holes
4: Thermometre
5: Stainless steel erlanmeyer
6: Magnetic stirring bar
7: Heating plate with magnetic stirrer
8: CO2-free distilled water
9: CaO (2g)
10: Metakaolin (1 g)

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 Metakaolins from Imerys

MetaStar 501 ARGICAL M- ARGICAL M- MK-40

1200S 1000

Origin USA France France Ukraine

Calcination Herreshoff kiln flash kiln rotary kiln rotary kiln

Pozzolanic 1400 1400 1100 1000

index [mg
Ca(OH)2 / g]

Surface area 14 23 20 15
(BET) [m²/g]

D50 [µm] 1.0 1.5 6.0 20.0

Brightness 85 72 69 65

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