Quaternary Cement

low carbon rapid set GGBS cement binder

 European Commission aims to make
the EU climate neutral by 2050

By 2030 - CO2 emissions should be reduced by at least 55 %

compared to 1990 !
China is estimated to produce 50 percent of world’s production, being world’s
biggest cement producer.
not all of it is consumed in China, but an increasing amount is exported
world wide
mandatory reduction of
Cement production
silica and limestone are mixed and sintered together in a
kiln at 1400–1500 degrees Celsius , about 2,500 degrees
Fahrenheit.

Limestone at this temperature transforms to quick lime or

calcium oxyde reacting with silica to form tricalcium
silicate so called cement clinker.

Most of the carbon dioxide is emitted ;

After cooling this clinker is ground to a fine powder.

Gypsum is added to slow down the reaction speed.

When water is added it hardens to a rock-like material

binding fillers to make mortar or concrete
 Cement clinker
• cement production contributes
7% of world wide CO2 emission
mainly through decarbonation of
limestone
• 1 ton of cement clinker emits
~ 800 kg of CO2
• carbon dioxide emission tax
expected to double within next
decade
• currently ~ € 90,= per ton
• carbon dioxide emissions tripled in
last three decades to
3 billion tons /y.
• cement production consumes most
of natural resources
 • replacing clinker amount by SCM’s – fillers

• using alternative binders like CSA cement or

geopolymers

• lowering cement amount by volume

Actions concrete, mortar

• reduction concrete volume (3D-printing,GRC)

• improving efficiency of binder system

Reducing clinker content

1. Pozzolans

natural/waste materials rich in silica reactive in the presence of lime

When water is added it reacts like cement with following
characteristics;

• slow set
• long time to build up strength
• improved flexural strength
• low ultimate compressive strength
• more durable in time

Today more pozzolan materials are derivate from industrial waste like
fly ash making it more sustainable construction material
To provide sufficient strength they are often mixed with
Portlandcement
Reducing clinker content

2. GGBS Ground Granulated Blast-furnace Slag)

an aluminosilicate / cementitious material a by product from iron

making.
When water is added it reacts like cement with following
characteristics;

• slow set (needs alkali activator Portladcement ,sodium

hydroxide(NaOH)sodium silicate(Na 2SiO3)
• low initial strength
• low temperature on hydration
• low alkali (reduced risk on ASR Alkali Aggregate Reaction)
• improved dense matrix (better water impermeability)
• better corrosion and sulphate resistant
• more durable in time
Reducing clinker content

3. Limestone

fine ground calcium carbonate an inert filler with a high surface

area to even fine particle distribution to improve compacting

4. Chemicals

Superplasticizers (SPs), also known as high range water reducers, are

additives used for making high-strength concrete or to place self-
compacting concrete

polymer dispersions, latexes and redispersible powders

In this case strength is improved in low clinker content cementitious binders

by reducing the water to cement ratio – and/or adding organic compounds to
the matrix
So if we can produce cement with the least materials through mixing some of the
supplementary materials—as I said, fly ash or slag with the cement—during production, that's
another way to produce cement that has the least of the effective material that results in the
larger emissions of CO₂. Canada has lots of work in this, and they produce what we call slag
cement, and there are other countries as well. But that was since early 2000; they produced
cement that has a considerable percentage of it as slag, and it works well for different
construction purposes. So, these are the two basic ways for reducing the CO ₂ emissions in
cement.

That's a good question. The two key trade-offs

for the construction industry are: how fast the
cement hardens and how strong it becomes.

GGBS is a vitrified substance which is a

byproduct of iron production in a blast furnace.
It consists primarily of oxides of calcium,
silicon, aluminium and magnesium.
SGGBS
(Special Ground Granulated Blast-furnace
Slag)
 Clinker production

• quarring, transport
• grinding, preparation
of raw materials
• cooling, grinding, mixing

cement in making concrete world wide most abundant

building material
Source:McKinsey Laying the foundation for zero-carbon cement
 AACM
Alkali Activated Cementitious Materials cements
hydrating through a chemical reaction between a
crystalline aluminosilicate; fly ash , GGBS (precursor)
and an alkaline or caustic solution sodium-,
potassium hydroxides or sodium silicate(activator)
Ternary Cement
blend of limestone filler GGBS and Portlandcement
clinker
Alternatives
Quaternary Cement
Portland cement blended with minimal three other
materials f.i. ground limestone, GGBS, fly ash, silica fume,
calcined clay, metakaolin, gypsum, calcium aluminate etc.

LC3 Cement
blend of limestone filler, calcined clay
and ground Portlandcement clinker
 cement standard
call for 2 day strength
hybride cements
•nowadays developed hybride cements reduce
carbon footprint by replacing the content of ground cement clinker
by often less reactive materials SCM’s, like ground steel slag ,
limestone , calcined clays etc.

•this has however a big impact on setting times and / or early

strength development of the binder.

•In practice the binder content is kept at the same volume

•modification is needed to guarantee a stable binder to overcome

slow hydration and loss of early strength
GGBS

Ground
Granulated
Blast-furnace
Slag
Ground Granulated Blast-furnace Slag

decomposition
limestone
iron
steel
making

cooling

grinding
different production
Carbon emissions ;

• from the manufacturing

of 1 ton of cement cement ~800 kg.

• from the manufacturing

of 1 ton GGBS is ~35kg.

slow hydration

low heat release on hydration

not favorable to use in precast factories

or winter concreting
PORTLAND SLAG CEMENT
CEM II / B-S EN 197-1:2011

CEM II/B-S CEM II/B-S

CEM II/B-S 32,5 N 42,5 N 52,5 N
compressive
strength
Mpa Mpa Mpa
2 days - ≥ 10,0 ≥ 20,0
7 days > 16,0
28 days ≥ 32,5 ≥ 42,5 ≥ 52,5
 Low Carbon cement

Ternary cement
Portland cement blended with two other materials f.i. ground limestone, GGBS, fly ash, silica
fume, calcined clay, metakaolin etc.

generally these binders are latent hydraulic and generate a lower initial strength

Quaternary Cement
Portland cement blended with minimal three other materials f.i. ground limestone, GGBS,
fly ash, silica fume, calcined clay, metakaolin, gypsum, calcium aluminate etc.

modified to garantee a stable binder overcome slow hydration and loss of early strength
 testing cement free binder

tested were two different types of GGBS

with addition of calcium sulfate
 Table 1. Data for regular GGBS-RG used in this study.
Table 1. Data for regular GGBS-RG used in this study.
GGBS-RG
Table 1. Data for regular GGBS-RG used in this study.

Chemical Compound
SiO2 35,40%
Al2O3 11,20%
Fe2O3 0,70%
Na2O 0,50%
CaO 42,50%
MgO 8,10%
TiO2 0,50%
SO 10,00%
Physical Characteristics
D50 11 μm
Blaine 4500 gr/cm2
Density 2,865 g/cm3
 Table 2. Data for GGBS-XF used in this study.
GGBS-XF

Chemical Compound
SiO2 1,92%
Al2O3 24,21%
Fe2O3 0,72%
Na2O 0,06%
CaO 45,46%
MgO 5,69%
TiO2 0,50%
SO 1,92%
CaF2 4,57%
Physical Characteristics
D50 9,6 μm
Blaine 6500 cm/gr
Density 2,965 g/cm3
 Table 2. Data for GGBS-XF used in this study.
GGBS-XF
Chemical Compound
SiO2 1,92%
Al2O3 24,21%
Fe2O3 0,72%
Na2O 0,06%
CaO 45,46%
MgO 5,69%
TiO2 0,50%
SO 1,92%
CaF2 4,57%
Physical Characteristics
D50 9,6 μm
Blaine 6500 cm/gr
Density 2,965 g/cm3
 Table 2. Data for GGBS-XF used in this study.
GGBS-XF

Chemical Compound
SiO2 1,92%
Al2O3 24,21%
Fe2O3 0,72%
Na2O 0,06%
CaO 45,46%
MgO 5,69%
TiO2 0,50%
SO 1,92%
CaF2 4,57%
Physical Characteristics
D50 9,6 μm
Blaine 6500 cm/gr
Density 2,965 g/cm3
Anhydrous Calcium Sulfate

Chemical Compound
SiO2 0,20%
Al2O3 0,15%
Fe2O3 0,10%
K2O 0,01%
Ca(OH)2 0,90%
MgO 0,10%
TiO2 0,50%
CaSO4 96,80%
CaF2 1,74%
Physical Characteristics
D50
10 μm
Blaine 6750 cm/gr
Density 2,965 g/cm3
 XRD analysis

XRD analysis show both types of GGBS are mainly crystalline.

GGBS XF showed a content around double amount of Al2O3
and significant lower amount of SiO2
CaO content is slightly higher.

Markable ; contains calcium fluoride

Experimental

all compositions tested included both types of GGBS.

To facilitate the usage 1% of citric acid as set retarder was added

extreme fineness leads to a significant increase of water demand

for this reason 0,45% by weight of a super plasticizing agent is
used

Testing various different ratio of these three constituents

following formulation was chosen to be tested further.
 Initial Experiment
Set min initial final Temp C. Time

GGBS-RG 440 gr >1440 x x x

water 176 ml after 2 days no strength was noticed

GGBS-XF 440 gr 03:30 04:30 30,7 06:40 min

water 176 ml

GGBS-RG 220 gr 10:00 21:00 45 01:53:10 H

GGBS-XF 220 gr
water 176 ml
 Strength Testing

Strength testing was done at 24 hours, 2 and 7 days on

40x40x160mm prims confectioned in compliance with EN 196-1
Methods of testing cement — Part 1: Determination of strength.

Mentioned formulation was mixed with 1350 gr.

CEN Standard sand EN-196-1 Normsand mixed according standard

Mortar test

GGBS-RG 140 gr

GGBS-XF 200 gr

Anhydrite 100 gr

Normsand 1350 gr

water 180 ml
Note: a higher water/cement ratio was used.
Mortar test results

24 hours 2 days 7 days

Flex Comp Flex Comp Flex Comp

MPa 3.44 16,2 2,34 32,08 5,91 40,92

 Shrinkage / Expansion

In order to measure the shrinkage or expansion of the mixtures as

mentioned were placed into 40x40x160mm prisms according to
EN196-1.

prisms were connected to a micrometer, which digitally measured

the linear length change every hour, and followed for 7 days and
after.

results up to 7 days show a relative small reduction of volume.

contributes in improving early strength and
accelerates drying and setting times
Solutions in the presence of lime, alumina, calcium
sulfate complex hydrates are formed ;

AFt (ettringite)

3CaO . Al2O3 . 2CaSO4 . 32H2O

AFm (mono sulfo aluminate)

3CaO . Al2O3 . CaSO4 . 12H2O 4CaO . Al2O3 . 19H2O

This formation improves the early strength and accelerates drying of

the binder.
As this chemical reaction takes place expansion occurs compensating
drying shrinkage.
Amorphous Calcium Aluminate Cement
Crystaline
C12A7

one of the best precursors in forming

AFt and AFm phase
(3 x more reactive calcium aluminate)

on hydration of main phase C12A7 (Mayenite)

Alumina ions are released quickly

reacting instantly with available sulphate

Amorphous Calcium Aluminate Cement
one of the best precursors in forming AFt and AFm phase – 3 x more
reactive calcium aluminate

hydration of main phase C12A7 (Mayenite) reacts

quickly with available sulphate to form

ettringite and mono calcium aluminate;

• account for high initial strength

• high density
• positive expansion, compensation of shrinkage
• bound excess water accelerate drying
Crystaline C11A7 · CaF2
Amorphous Calcium Aluminate C12A7

C11A7 · CaF2 compound is isostructural with C12A7

forming a complete solid solution

Tests are ongoing to investigate the effect of combing amorphous

calcium aluminate and crystaline GGBS-XF and calcium sulfate

Results are to be published at a later stage

FINDINGS
• regular GGBS marked RG showed no initial reactivity on its own,
and clearly needs some form of activation.
• results found in this empirical study show that regarding strength
development the fine ground special form of GGBS marked XF
achieved a relative high flexural and compressive strength.
• blending the two types lead to more than satisfying results
• addition of sulphate helps in a improving the early strength
development
• formation of ettringite crystals lead to a minimal expansion i.e.
reduction of shrinkage.
• small retardation in set times was noticed.
• XRD analysis of fine GGBS-XF showed presence of calcium
fluoride it is expected this contributed to activating the regular
slag used.
• C11A7.C phase is expected to have the most impact on hydration
performance of type XF.

• grinding this type to a finer particle size further boosted the

reactivity.
• it did increase the water consumption!
• pore structure and pore size were only marginally effected, and
strength development was satisfactory.
CONCLUSION

In conclusion, data shows that the optimum blends are the GGBS RG and XF
types combined with anhydrous sulfate.
GGBS can be activated by Type XF. Depending on the requirements the
addition can be varied and depends largely on the chemistry of the slag
available.
GGBS XF + calcium sulphate outperforms in all areas, achieving the highest
compressive and flexural strengths, and the most stable shrinkage
compensation. This is confirmed by the amount of ettringite formed found in
XRD analysis.
The research showed that fineness has a significant impact on result, which
can only in part be compensated by increasing the dosage.
In all cases it is essential to find the right equilibrium of all components in the
matrix.
Effects aimed to be achieved depend to a large extend to the type of raw
materials being used.
practical use

• Cement fiber panels

• GRC
• Pre-fabricated concrete
• 3D printing
• Winter concreting
• Dry-Mix
• Volumetric concrete
demolding of prefabricated concrete

• fast setting reactive binder

• no heating molds
• no increase ambient temperature
• high initial strength
demolding of prefabricated concrete
3d3 D printing

• fast setting
• low alkali
• no volume hange
• high initial strength
winter concreting

• fast setting reactive binder

• working at low ambient
temperatures
• no addition of accelerators
• high initial strength
 drymix

• stable reactive binder

• low carbon footprint
• reduction binder content
• fast setting
• initial strength
• compensation of shrinkage
• low alkalinity
• high density
VOLUMETRIC CONCRETE

• fast setting binder

• low carbon footprint
• reduction binder content
• high initial strength
• compensation of shrinkage
• low alkalinity
• high density