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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)
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
7
Ash from coal fired power plants
1-20 m
8
Production of Portland cement
▪ Raw materials and fuel fed into a huge rotating oven:
• Limestone
• Clay
• Sand
• Coal, oil, … 1450 oC
Grinding +
Portland Gypsum (3%) Particle size
clinker Cement
10-20m
9 9
Chemistry of Portland cement production
CaCO3 ⎯→ CaO + CO2
Limestone Burnt lime Carbon dioxide (gas)
(CaO)3 Al2O3
• Calcium aluminate
10 10
Clinker phases in Portland cement
Simplified Amount
Chemical name Chemical formula
formula Wt-%
11
Portland + Water + Ash (Pozzolan)
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
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%
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
16
Definition of a chemical admixture
17 17
Properties to be modified
While the concrete is still fresh
Workability
Rheology, fluidity
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
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%
24
Electrostatic repulsion vs. steric hindrance
25
Fluid concrete with low water/cement ratio
26
Demo: Effect of superplasticiser
Cementitious mix:
Portland cement
Water
Low water/cement ratio!
TamCem 60 (superplasticiser)
27
Cement hydration and admixtures
Retarder Accelerator
Hardening
Heat
evolution Reference Setting
Setting
Hardening
Reference
Time
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)
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
30
Retarder and slump flow retention
680
580
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
32
Set accelerators
33
Set accelerator for cast concrete
Calcium nitrate, Ca(NO3)2
34
Hardening accelerators
35
Hardening accelerators for cast concrete
Today
Sodium thiocyanate, NaSCN
Sometimes blended with other constituents like Triethanolamine
R&D triggered by the introduction of slow reacting blended cements
36
Dosage can be tricky – Triethanolamine
Reference
0.25%
1.0% 0.02%
Strength /
Hardness
0.50%
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’)
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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
41
Conventional (old) accelerator issues
42
Today’s non-alkaline accelerators
EN 934-5 definition
• Non-alkaline if Na2O-equivalent 1.0% (= Na2O + 0.658 K2O)
43
Aluminium sulphate causes flash setting
Al2(SO4)3 + C3A + Ca(OH)2 + H2O
44
Water/cement ratio and set times
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!
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%)
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”
49
Two ways of utilising Fly Ash (FA)
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
51
Alkaline activation of FA
52
New binders need new admixtures
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
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
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
Water 9.7
Total: 100.0
58
Setting and strength development
Setting times and early age compressive strength (MPa) of fly ash mix at 20C
59
Chemical resistance (28 days cured samples)
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
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
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
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
Age 2h 4h
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
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