Chemistry of Concrete + Demos

Roar Myrdal [email protected]

R&D Director Construction Chemicals, Normet International Ltd., Hünenberg, Switzerland
Adjunct Professor, Norwegian University of Science and Technology, Trondheim, Norway

Shuyuan Liu [email protected]

GCCT R&D Manager, Normet R&D Centre, Coventry, UK

Luis Senorans [email protected]

GCCT R&D Engineer, Normet R&D Centre, Coventry, UK

University of Warwick, 29th October 2019

1
 Normet in a nutshell
Global supplier of Machinery, Equipment and Construction Chemicals
primarily for underground space (tunnelling and mining)

50 locations in 28 countries worldwide

1000+ employees, annual turnover 250 million Euros

R&D Centre for Construction Chemicals in Coventry, UK

Production of concrete admixtures and other construction chemicals:

USA, Chile, UK, Scandinavia, South Africa, India, Taiwan, Singapore, Indonesia, Australia

2
 Contents
History of concrete (Roman cement)
Portland clinker and Portland cement
Chemical reactions between cement and water
Blended cements and pozzolanic reactions
Admixtures for concrete
Types and what they do
Admixtures for sprayed concrete
Demos
Cement and CO2
Geopolymer concrete, or “concrete without cement”
Organic polymers / resins for tunnelling
Demos

3
 A typical concrete mix design
Percentage by volume
Chemical admixtures 1%
Air 4%
Cement, binder 12%

Water 18%
The annual global volume of
concrete is ….. ?
Sand 25%
10 km3
10,000,000,000 m3
Stone and gravel 40%

4
 Definition of cement (EN 197-1)
“Finely ground inorganic material which, when mixed with
water, forms a paste which sets and hardens by means of
hydration reactions and processes and which, after
hardening, retains its strength and stability even under
water.” Hydration reaction = Reaction with water (’hydro’)
EN 197-1 defines 27 cement types
Final Strength classification 32.5, 42.5 and 52.5
Early strength classification L, N and R
Examples: CEM I 52.5N and CEM II/A-V (6-20% siliceous fly ash)

It started more than 2000 years ago

Around 25 BC the Roman architect Vitruvius designed 29
concrete recipes based on Roman cement

5
 Dome of Pantheon, Rome
Opus
Ceamenticium

▪ Vitruvius (63 BC – 14 AD, Roman architect and advisor for the Emperor Augustus)
"There is also a kind of powder from which natural causes produces astonishing results. This
substance, when mixed with lime and rubble, not only lends strength to buildings of other kinds, but
even when piers are constructed of it in the sea, they set hard under water.“

▪ Powder = Pozzuolania = Volcanic ash found in Pozzuoli region by the Bay of Naples

6
 The Roman pozzolanic binder
SiO2 + Ca(OH)2 + H2O → C-S-H
Volcanic ash Lime Water Calcium-Silicate-Hydrate
Amorphous/ Ca3Si2O7·4H2O
glassy silica

▪ The reaction rate is very slow (no strength the first week after mixing)
▪ Knowledge disappeared when the Roman empire declined around
400 AD
▪ More than 1000 years later some research on cementing materials (UK)
▪ Breakthrough in 1824: Joseph Aspdin invented Portland cement

▪ Some industrial wastes have pozzolanic properties:

Fly ash from coal fired power plants
Silica fume from production of silicon and ferrosilicon alloys
▪ Fly ash is blended into today’s Portland cement

7
 Ash from coal fired power plants

1-20 m

Used in CEM II/A-V

8
 Production of Portland cement
▪ Raw materials and fuel fed into a huge rotating oven:
• Limestone
• Clay
• Sand
• Coal, oil, … 1450 oC

▪ Out of the oven:

• Lumps (calcium silicates and aluminates) that are grinded to fine grey powder
• In the grinding process gypsum is added
• Without gypsum the powder will set immediately when mixed with water

Grinding +
Portland Gypsum (3%) Particle size
clinker Cement
10-20m

9 9
 Chemistry of Portland cement production
CaCO3 ⎯→ CaO + CO2 
Limestone Burnt lime Carbon dioxide (gas)

+ SiO2 / Al2O3 / Fe2O3 Sand / clay / …

(CaO)2 SiO2 / (CaO)3 SiO2

• • Calcium silicates

(CaO)3 Al2O3
• Calcium aluminate

(CaO)4 Al2O3 Fe2O3

• • Calcium aluminoferrite

10 10
 Clinker phases in Portland cement

Simplified Amount
Chemical name Chemical formula
formula Wt-%

Tricalcium silicate (’Alite’) (CaO)3 • SiO2 C 3S 50 – 70

Dicalcium silicate (’Belite’) (CaO)2 • SiO2 C 2S 15 – 30

Tricalcium aluminate (CaO)3 • Al2O3 C 3A 5 – 10

Tetracalcium aluminoferrite (CaO)4 • Al2O3 • Fe2O3 C4AF 5 – 15

11
 Portland + Water + Ash (Pozzolan)

Main Portland cement reaction:

(CaO)n SiO2 + H2O
• → CSH + Ca(OH)2
Main component The binder No binding effect (25%)

Roman Pozzolanic reaction:

SiO2 + Ca(OH)2 + H2O → CSH Isle of Portland

Ash Binder
✓ More binder
Typical blended cement (CEM II):
✓ Stronger concrete
✓ Denser (less permeable) concrete 80% Portland
✓ More durable concete 20% Ash

12
 27 different cement types in EN-197

• Fly ash
• Slag
• Silica fume
• Pozzolana

13
 China and the rest of the world

for the next five years complete the report.

https://mcgroup.co.uk/researches/cement
Washington Post, 24th March 2015

14
 Chemical admixtures for concrete
Percentage by volume

Admixtures 1%
Air 4%
Cement 12%

Water 18%

Sand 25%

Stone and gravel 40%

15 15
 Admixtures are as old as concrete itself
Roman admixtures:
Fibres Horse hair and straw
Plasticisers Animal fat, blood, milk
Air entrainer Animal fat
Retarder ? Urine

Air entrainer - Accident or Design?

Romans were known to throw leftover food into the
concrete mix to help keep the work area clean.
Due to the high pH of the mix, the fat in the food
was converted to soap.
Soap makes bubbles.

16
 Definition of a chemical admixture

▪ European standard EN 934-2:

”Material added during the mixing process of concrete in a
quantity not more than 5 % by mass of the cement content
of the concrete, to modify the properties of the mix in the
fresh and/or hardened state.”

▪ The standard defines 11 different classes

Accelerators for sprayed concrete (EN 934-5) are normally

added at higher amounts, about 6-10%

17 17
 Properties to be modified
While the concrete is still fresh
Workability
Rheology, fluidity

During setting and hardening

Reduction or increase in setting / stiffening time
Increased rate of hardening
Decreased rate of hardening?

After the concrete is well cured

High strength
High density, low permeability
Frost resistance
Non-corrosive environment for steel reinforcement
Durability
Less shrinkage
Colour
…

18
 Types of Admixtures

Superplasticising/
Plasticising/water
Air-entraining high range water Accelerating
reducing
reducing

Corrosion-
Retarding Water resisting Bond Improving
inhibiting

Viscosity Shrinkage
Colouring Air-detraining
modifying reducing

Consistence
Foaming Water retaining Pumping Aid
controlling

19
 Total UK admixture sales in 2011
Other
13 %
Air Entrainer
Retarder 4%
2%
Superplasticiser
45%
Accelerator
2%

Plasticiser
34 %
(Minson and Berrie, 2013)

20
 Effect of water/cement ratio
Low water/cement ratio High water/cement ratio
Cement particles closely packed in clusters Cement particles dispersed evenly
Low fluidity High fluidity
High Strength Low strength
Low porosity and low permeability High porosity and high permeability

More water added

21
 Low water/cement ratio !!!
Cement + water = cement paste (the glue in concrete)
To make the concrete workable, more water than required for the
reaction is normally added to the mix
But a lot of water (high water/cement ratio) gives a porous concrete
Low water/cement ratio gives (after curing and hardening):
• Higher strength
• Denser concrete
• Less permeable concrete
We want:
• A concrete that is workable/fluid in the fresh state
• And at the same time a concrete with low water/cement ratio
Only possible with water reducing / plasticising admixtures

22
 Water reducers / plasticisers
By far the most used admixtures for concrete (dosage 0.5-1.0% by
weight of cement)
Organic polymers dissolved in water
Mechanism of action: Dispersion of clustered cement particles and fines
in water
Water reduction (lowering w/c ratio), or higher slump/flow if water
amount is kept constant
Plasticiser

Plasticiser

23
 Plasticiser (P) / Superplasticiser (SP)
Water reduction capacity: P 5-12% SP 12%

Conventional (old) products Modern products

1930: Lignosulphonate P 8% 1995: Polycarboxylate SP 40%!
1940: Naphthalene SP 15%
1975: Melamine SP 15%

- By-products from chemical industries - Designed for concrete only

- Allround products - Many types, tailor-made for
different actions in concrete

Electrostatic repulsion Steric hindrance

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 Electrostatic repulsion vs. steric hindrance

Electrostatic Repulsion Steric Hindrance

−
−
− −
−
−
− −

Negatively charged molecules Polycarboxylate polymers adsorb

attach to the cement particles on to the cement particles creating
making them repel each other. a physical barrier between them.

25
 Fluid concrete with low water/cement ratio

1. Fill the cone

2. Lift cone
3. Give table 15 drops and measure

26
 Demo: Effect of superplasticiser

Cementitious mix:
Portland cement
Water
Low water/cement ratio!
TamCem 60 (superplasticiser)

The mix is not workable without the superplasticiser

TamCem 60 makes the mix fluid without adding extra water!

27
 Cement hydration and admixtures

Retarder Accelerator
Hardening
Heat
evolution Reference Setting
Setting

Hardening
Reference

Time

Hydro (Greek) = Water

Hydration = Reaction with water

28
 Set retarding admixtures
A barrier of adsorbed molecules or precipitates on the cement particles
stops the water getting in contact with the cement.

Sugars
Sucrose, corn syrup, saccharin (artificial sweetener)

Hydroxycarboxylic acids and their salts

Sodium gluconate, citric acid, tartaric acid

Phosphorous compounds
Phosphates and phosphonates

Used a lot in sprayed concrete mix designs to allow long transport of the
concrete and unforeseen delays in the concrete spraying; often called
Hydration Control Admixture

29
 Effect or retarder (w/c=0.43)
16

14

12
Open time (hours)

10

0
0 0,2 0,4 0,6 0,8 1

TamCem HCA dosage (% by weight of cem.)

30
 Retarder and slump flow retention
680

580

w/c Material Type Dose quantity

480
Flow mm

Cement CKC (CEM I, 52.5N) 4,200 kg

380
0-4 mm
Sand Hanson 10,985 kg
0,42
280 Gravel 6 mm Hanson 7,405 kg
Retarder TamCem HCA 0,50 % 21,00 g
180
SP TamCem 60 1,00 % 42,00 g

80
0 1 2 3 4 5 6

Time hours

31
 How to speed up the cement raction

Set accelerator
Shortening of set time

Hardening accelerator
Increasing early strength with or without affecting the setting time

Accelerator for sprayed concrete (”shotcrete”)

Flash set and high early strength

32
 Set accelerators

Why add a set accelerator?

Earlier finishing of surfaces
Reduction of hydraulic pressure on forms
Possibility to apply sprayed concrete to vertical and overhead
substrates

Two classes of set accelerators

For cast concrete
For sprayed concrete

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 Set accelerator for cast concrete
Calcium nitrate, Ca(NO3)2

Final set time

(hours)

Dosage, % by weight of cement

34
 Hardening accelerators

Why add a hardening accelerator?

Earlier removal of forms
Earlier placement in service of a structure
Counteract the bad effect of low temperature on strength
development
Speed up the reaction rate of slow reactive binders containing
pozzolanic materials (fly ash)

Two classes of hardening accelerators

For cast concrete
For sprayed concrete (both setting and hardening)

35
 Hardening accelerators for cast concrete

The classic (since 1886!)

Calcium chloride, CaCl2
Seldom used due to corrosion hazards (steel reinforcement)

Today
Sodium thiocyanate, NaSCN
Sometimes blended with other constituents like Triethanolamine
R&D triggered by the introduction of slow reacting blended cements

Alternatives: High temp, rapid hardening cement

Calcium aluminate cement
Magnesium phosphate cement
Rapid hardening cement + accelerator DEMO

36
 Dosage can be tricky – Triethanolamine

Reference
0.25%
1.0% 0.02%

Strength /
Hardness

0.50%

V. Dodson, Concrete Admixtures,

Chapter 4, Van Nostrand Reinhold,
Time - Hours New York, 1990.

37
 What is Sprayed Concrete?
Sprayed concrete is a mixture of cement, aggregate and
water projected pneumatically from a nozzle into place to
produce a dense homogeneous mass. Sprayed concrete
normally incorporates admixtures and may also include
additions or fibres or a combination of these (EFNARC
guidelines).
Invented by Carl Ackley in 1907 (‘Gunite’)

38
 Standards / guidelines for sprayed concrete

39
 How to spray concrete
Compressed air
and accelerator

Concrete

40
 Accelerators for sprayed concrete
High dosage, 6-10% by weight of cement
Accelerates both setting and hardening
Conventional (old) alkaline types, used for many decades:
Sodium silicate, pH  11
Sodium aluminate, pH  14

Modern non-alkaline types, since mid 1990s

Aluminium sulphate ++, pH 2-3 (weakly acidic)
Low pH due to hydrolysis of dissolved aluminium salt
Al3+ + H2O = Al(OH)2+ + H+

41
 Conventional (old) accelerator issues

Sodium silicate Sodium aluminate

• Relatively low early age • Health hazards associated with
strength handling highly caustic materials
• Reduced final strength at high • Risk of promotion of damaging alkali-
dosages aggregate reactions (high alkali
content)
• Decrease in final strength

42
 Today’s non-alkaline accelerators
EN 934-5 definition
• Non-alkaline if Na2O-equivalent  1.0% (= Na2O + 0.658 K2O)

Developed in the 1990s to:

• Improve working conditions for the personnel/operators
• Improve mechanical properties of the sprayed concrete

Chemical charateristics of non-alkaline accelerators

• pH  2-3
• Main ingredient is aluminium sulphate
• Typical additional constituents: Diethanolamine
Aluminium hydroxide
Organic acids, typically formic acid
Fluorides

43
 Aluminium sulphate causes flash setting
Al2(SO4)3 + C3A + Ca(OH)2 + H2O

3CaO · Al2O3 · 3CaSO4 · 32H2O + Al(OH)3

Ettringite Aluminium hydroxide

Ettringite responsible for rapid setting

Aluminium hydroxide accelerates hardening

44
 Water/cement ratio and set times

Ref: Aldrian et al, Felsbau 18 (2000) No.6

45
 Early age strength development

1,2
Compressive Strength (MPa)

1,1

0,9

0,8

0,7

0,6
0 20 40 60 80

Time (minutes)

46
 Demo: Accelerator for sprayed concrete

Cementitious mix:
Fluid mix: Portland cement + Water + Superplasticiser
Adding an accelerator for sprayed concrete
Flash setting!

The mix will not stick to the substrate and develop

high early strength unless an accelerator is added
in the nozzle of the sprayer

47
 Cement and CO2
The cement industry is responsible for 8% of the global man-made CO2
emission
This is 2-3 times the amount from the global aviation industry
CO2 emission from cement kilns:
Heating limestone: CaCO3 → CaO + CO2 (60%)
Burning fossil fuel: C + O2 → CO2 (40%)

1 kg ordinary Portland cement = 1 kg CO2

Therefore, “Low-carbon Cement” is an important research field today
✓ Blended cements (Portland clinker + fly ash)
✓ Binders without Portland clinker (Geopolymers)

48
 Non-Portland cementitious binders
There are industrial wastes and natural minerals with cementitious
properties, like the Fly Ash (FA) and the Roman Pozzolana
Almost 1 billion tonnes of FA are generated every year and the amount
will increase in future
NY Times 25.09.2011: “China and India together are building four coal-
fired power plants a week”

Ash pond (lake) in Suradevi, India, October 2009

The ash content in Indian coal

is as high as 40 %

49
 Two ways of utilising Fly Ash (FA)

1. FA + Portland cement or Lime (Pozzolanic reaction)

SiO2 + Ca(OH)2 + H2O → Calcium-Silicate-Hydrate
Ash Lime Binder

2. FA + Highly alkaline solution (no cement, no lime!)

Calcium-free aluminosilicate (Glukovsky, 1967)
Alkali-activated FA (aluminosilicate)
Geopolymer (Davidovits, 1982)

50
 What is a Geopolymer?
A cementitious binder made of two components:
1. Aluminosilicate Fly ash, calcined clay (metakaolin)
which dissolves and then polymerises in an

2. Alkaline solution Sodium silicate, sodium hydroxide

and forms an inorganic three-dimensional polymeric network of
aluminosilicate (-Si-O-Al-O- bonds), without chemically bonded water
in the ‘molecular structure’

A cured Geopolymer is an equivalent to geological feldspar

A durable material with up to 80% less CO2 emission compared to

Portland cement

Needs thermal curing in order to develop strength

51
 Alkaline activation of FA

Caijun Shi , A. Fernández Jiménez , Angel Palomo:

“New cements for the 21st century: The pursuit of an alternative to Portland cement”
Cement and Concrete Research, Volume 41, Issue 7, 2011, 750-763
http://dx.doi.org/10.1016/j.cemconres.2011.03.016

52
 New binders need new admixtures

“There is a need to develop a whole set of new admixtures

for the geopolymer system, which presents a significant
challenge for an emerging industry with a lack of scale, but
which is still required to compete with the well-established
OPC industry”

J.S.J. van Deventer, J. L. Provis, P. Duxson, “Technical and commercial

progress in the adoption of geopolymer cement”, Minerals Engineering,
Volume 29, 2012, pp 89-104.

53
 Normet – Warwick Uni cooperation
Vivienne Yeung Project ES327 (2014)
Project Title Geopolymers – An investigation into the effect of admixtures developed
for Ordinary Portland Cement on the properties of Geopolymer Concrete

54
 Geopolymers: Benefits and Disadvantages
Benefits
Eco-friendly and ‘green’
Up to 80% reduction in CO2 emission compared to OPC
Calcium-free, or at least low-calcium
No formation of Calcium Silicate / Aluminate Hydrates (gels)
Durable
Chemical resistant, Fire resistant, …

Disadvantages
Need of thermal curing to obtain acceptable strength
It is ‘User-hostile’ (handling of very caustic material, pH≥14)
Lack of standardisation,
but guidelines do exist “Recommended Practice:
Geopolymer Concrete”,
Concrete Institute of
Australia, 2011, 31 pages

55
 Normal practice to overcome the Disadvantages

Add a calcium source (slag, OPC, lime,…)

Curing at ambient temperature is possible
‘User-friendly’ instead of ‘User-hostile’ (if alkali hydroxide is taken out)

‘User-friendly geopolymer cement’ that cures properly at

room temperature (Davidovits, 2013):

Sodium silicate + Fly Ash + Blast furnace slag

Formation of Calcium Silicate / Aluminate Hydrates (gels)
Negative effect on durability

Therefore:
A low-calcium fly ash / sodium silicate binder cured at ambient
temperature would be highly appreciated

56
 Challenges
To make a calcium-free or low-calcium fly ash / sodium silicate binder
that cures and develops strength at ambient temperature using neither
alkali hydroxides nor any source of calcium:
Non-caustic and ‘User-friendly’ binder (from pH ≥ 14 to pH = 10-11)
No formation of Calcium Silicate/Aluminate Hydrates (gels)
A more durable binder

To develop an accelerator for this binder

To develop a sprayed concrete without Portland cement

57
 First Normet attempts
Ratio 3.25 is high Non-classified
Material Low ratio ( 2.5) means caustic Corrosive % by weight
Fly ash 64.5

Sodium silicate, SiO2/Na2O molar ratio 3.25, 38% solution 25.8

Water 9.7

Total: 100.0

Initial testing in lab with an accelerating admixture (still under development)

- Accelerator
- Clear, non-aqueous, non-hazardous liquid (blend of organic compounds found
among polyols and esters)
- Dosage 4-6% by weight of fly ash
- Tests
- Set times and strength development
- Chemical resistance (10% sulphuric acid)
- Fire resistance (propane torch, 1300C)

58
 Setting and strength development

Setting times and early age compressive strength (MPa) of fly ash mix at 20C

Material Initial set Final set 1h strength 4h strength 24h strength

Reference  30h > 100h - - -

4% accel. 3m10s 5m48s 1.5 1.8 2.2

6% accel. 1m32s 4m0s 1.5 2.6 2.7

s=seconds, m=minutes, h=hours

☺ 
This resembles the setting behaviour and early age strength of sprayed
OPC concrete when using an alkali-free accelerator

Can the binder be used in sprayed grout / mortar / concrete?

59
 Chemical resistance (28 days cured samples)

40x40x40mm cubes after 2 days in 10% sulphuric acid

OPC paste Fly ash paste (sample 6% accel.)

R Myrdal and D Galloway, ”Accelerating Admixture for Fly Ash / Sodium Silicate Binders Cured at Ambient
Temperature”, paper presented at 11th High Performance Concrete & 2nd Concrete Innovation Conference, Tromsö,
Norway, 6-8 March 2017, Conference Proceedings, Paper No. 59, 8 pages.

60
 Fire resistance (28 days cured samples)

Cooling

Video

Propane flame (1300C for 2 minutes), Fly ash

OPC exposed to same heat

suffered from explosive spalling

R Myrdal and D Galloway, ”Accelerating Admixture for Fly Ash / Sodium Silicate Binders
Cured at Ambient Temperature”, paper presented at 11th High Performance Concrete & 2nd
Concrete Innovation Conference, Tromsö, Norway, 6-8 March 2017, Conference Proceedings,
Video Paper No. 59, 8 pages.

61
 Fly ash grout for spray trial

Material % by weight
Fine Silica sand 34.3

Fly ash 34.3

Sodium silicate solution 24.5

Water 6.9

Total: 100.0

- Accelerator
- Clear, non-aqueous, non-hazardous liquid (blend of organic compounds found
among polyols and esters)
- Dosage 5-6% by weight of fly ash
- Spray test
- Early age strength development

62
 Fly ash grout and sprayer

Fly ash grout Normet SSL 15 sprayer

63
 Spraying of fly ash grout

64
 Sprayability and early age strength

Sprayability
The fly ash grout set fast (less than 60 seconds)
The rebound was low
Optimum accelerator dosage 5.5%
Sprayed only up to 25 mm thickness, but instant setting behaviour indicates
that much thicker layers could be sprayed

Early age strength

Measured on 100x100x100 mm cubes
6% accelerator dosage

Age 2h 4h

Compressive strength (MPa) 1.8 2.5

Ref: R Myrdal and S Tong, “Sprayed Concrete without Portland Cement”, paper presented at 8th
International Symposium on Sprayed Concrete – Modern Use of Wet Mix Sprayed Concrete for
Underground Support, Trondheim, Norway, 11-14 June 2018, Conference Proceedings (ISBN:
978-82-8208-060-6), pp 244-251.
65
 Demo - TamPur 150
Single component hydrophilic polyurethane. Only reacts when in
contact with water.
Forms flexible seal
Can be injected into leaking crack

66
 Demo - TamAcryl 2000
2 component Acrylic gel
Open time controlled by addition of
retarder or Accelerator
Low Viscosity
Leak sealing
Soil stabilisation

67