An overview of Future Concretes

1
An overview of Future Concretes

• An overview of the alternative mineral binder
  systems and composites made with them including
  novel concrete technologies addressing practical
  supply chain and economic issues including energy

2
Why Future Concretes?

• Whats wrong with the concrete we use made with
  Portland Cement?
• Embodied energy and emissions, shrinkage,
  durability, placement, tensile strength etc. etc.
  Not optimised for lifetime energy reduction.
• We can make better more environmentally friendly
  materials but what about the cost?
• Better concretes dont necessarily produce more
  and those producing them will make more money.
• Concrete made for purpose Higher Margin?
• Architectural façade, insulative properties,
  permeable pavement etc.

3
The Business Model

• The industry model is like Woolworths or Coles.
  Head on competition. Low margins resulting in a
  reliance on turnover volume and cost control to
  produce profits.
• This model is past its use by date.
• "Firms need to embrace innovation to remain
  competitive. Future job creation will come as
  companies transform and adopt new practices.
  Putting it simply, firms that innovate will
  survive and be the market leaders of tomorrow."
  Source Senator the Hon Kim Carr 24 Aug 2011
• The need to innovate under a carbon price and
  trading system is significantly greater than
  without.
• Given our problems the need to innovate goes
  beyond the immediate needs of the industry. There
  are other stakeholders
• Innovation recognises new markets

4
Making Money Through Innovation

• In Australia rules relating to the new R D Tax
  Incentive have changed. The new scheme effective
  1 July 2011 is more generous.
• Make a 1 and pay 30c corporate tax
• Spend a 1 to innovate thereby ensuring future
  profits and adding value to your balance sheet
  and the government will give you either 40 or 45c
  as a grant.
• Thats a 70 - 75c difference!
• Given the changes the industry business model
  needs to change.
• TecEco are also changing their business model. We
  are going to register as a Research Service
  Provider (RSP) and become more aligned with the
  University of Tasmania to attract student power
  under my supervision.
• The leverage provided by students will increase
  the value of investing in R D to well over a
  dollar.

5
What we Sell in the Industry

• Managers in the concrete industry seem to
  misunderstand what we sell.
• They think we sell Portland cement and concrete
  made with it.
• My analysis is that what we sell is the technical
  confidence in a liquid that sets as a solid
  material and it really would not matter what
  either was provided we could demonstrate
  technical merit and suitable properties.

6
Increases in Business Performance from the
Previous Year, by Innovation Status 2008-9
7
Some of the Issues?
The Techno Process
Primary Production Process Build,
Manufacture Use Dispose
Underlying Molecular Flows
8
Predicted Global Cement Demand and Emissions
Source Quillin K. Low-CO2 Cements based on
Calcium Sulfoaluminate Internet. Available
from http//www.soci.org/News//media/Files/Confe
rence20Downloads/Low20Carbon20Cements20Nov201
0/Sulphoaluminate_Cements_Keith_Quillin_R.ashx
9
Energy Outlook to 2035
Source U.S. Energy Information Administration.
International Energy Outlook 2010 Internet.
U.S. Energy Information Administration 2010
cited 2010 Sep 5. Available from
www.eia.gov./oiaf/ieo/index.html
10
Global Waste An Underestimate!
The challenge is to convert waste to resource.
11
There are Huge Change Opportunities

• A wide variety of possible end uses with higher
  potential margins for which current solutions are
  sub-optimal.
• E.g. Addessing properties affecting lifetime
  energy.
• E.g. Mineral composites with higher R value
• E.g. Particle boards made with mineral binders
• E.g. Exterior structural panels with insulating
  properties
• Huge opportunities for reducing the cost base and
  improving the properties of concretes by focusing
  on the process by which they are made and what
  they are made with.
• A few tweaks to the formulations
• Major changes to the process and some
• Lateral thinking in relation to aggregates.
• Every improvement counts but quantum improvements
  really matter If implemented!
• Implementation issue because of the low level of
  skills in the industry

12
Our Mantra

• Think outside the square.
• Spend more time thinking (R D) less time doing
  (earning low margins).
• We cannot solve problems doing the same old thing
  in the same old way.
• The technology paradigm defines what is or is not
  a resource.
• Improvements through innovation profit!
• Think whole of material and whole of system
• Refine definition of whats important and what is
  not

13
Example of a Decision Matrix to Help us Improve
the Future
14
Future Cement ContendersPortland Cement
Cements Based on Process Process CO2(tonnes CO2 / tonne Compound) Decarbonation CO2(tonnes CO2 / tonne Compound) Emissions (if no kiln capture tonnes CO2 / tonne Compound) Emissions (kiln capture tonnes CO2 / tonne Compound) Absorption (tonnes CO2 / tonne Compound, Assuming 100 carbonation 1 year) Net Emissions (Sequestration No kiln Capture) (tonnes CO2 / tonne Compound, Assuming 100 carbonation 1 year) Example of Cement Type Apply to Comment Notes
PC Current Methods .369  0.498 .868 None .001 .867 Split process lime with recapture then clinker Most dense concretes No supplementary cementitious or pozzolanic materials 1
PC Permeable Block formulation .369 0.498 .868 .369 .144 .724 Ordinary Portland Cement Most dense concretes No supplementary cementitious or pozzolanic materials 1
PC Split Process Lime then clinker .369  0.498 .868 .369 .001 .368 Split process lime with recapture then clinker Most dense concretes No supplementary cementitious or pozzolanic materials 1

1. http//www.tececo.com/files/spreadsheets/TecEcoCem
   entLCA12Oct2011.xls

15
The Potential of CO2 Release and Capture -
Portland Cements
Split Process with Capture during Manufacture
No Capture during Manufacture
Capture during Manufacture
CO2 capture (e.g. N-Mg process etc.)
CO2 capture (e.g. N-Mg process etc.)
CO2 in atmosphere
Net Emissions (Sequestration) 0.369 Kg CO2/Kg
product
Net Emissions (Sequestration) 0.867 kg CO2/kg
product
Net Emissions (Sequestration) 0.369 kg CO2/kg
product
CaCO3
CaCO3 Clays
CaCO3 Clays
CaO Clays
H2O
H2O
H2O
Net Energy 3962 kJ/kg product
Net Energy 3962 kJ/kg product
Net Energy 3962 kJ/kg product
Clinker
Clinker
Clinker
Hydrated Cement Paste
Hydrated Cement Paste
Hydrated Cement Paste
Net sequestration less carbon from process
emissions
Carbon positive. Chemical and process emissions
Carbon positive. Chemical and process emissions
Use of non fossil fuels gt Low or no process
emissions
Source Data http//www.tececo.com/files/spreadshe
ets/TecEcoCementLCA12Oct2011.xls
16
Future Cement ContendersMg Group
Cements Based on Process Process CO2(tonnes CO2 / tonne Compound) Decarbonation CO2(tonnes CO2 / tonne Compound) Emissions (if no kiln capture tonnes CO2 / tonne Compound) Emissions (kiln capture tonnes CO2 / tonne Compound) Absorption (tonnes CO2 / tonne Compound, Assuming 100 carbonation 1 year) Net Emissions (Sequestration) (tonnes CO2 / tonne Compound, Assuming 100 carbonation 1 year) Example of Cement Type Apply to Comment Notes
lt750 oC MgCO3 .403  1.092 1.495 .403 -1.092 .-.688 Eco-cement concrete, pure MgO concretes. Novacem concretes TecEco, Cambridge Novacem TecEco Eco-CementForce carbonated pure MgO 3
lt450 oC MgCO3.3H2O .693  1.092 1.784 .693 -1.092 -.399 Eco-cement concrete, pure MgO concretes. Novacem concretes? TecEco, Cambridge Novacem N-Mg route University of Rome 3
lt450 oC MgCO3.3H2O Including capture during production of nesquehonite .693  1.092 1.784 .693 -2.184 -1.491 Eco-cement concrete, pure MgO concretes. Novacem concretes? TecEco, Cambridge Novacem N-Mg route University of Rome 3
  Silicate route  ?           Novacem After Klaus Lackner?  
Modified Ternary Blends (50 PC) Split Process Lime (with capture) then clinker .185   .185 .002 .183 Ternary mix with MgO additive. Most dense concretes Faster setting and higher early strength 2

1. http//www.tececo.com/files/spreadsheets/TecEcoCem
   entLCA12Oct2011.xls
2. http//www.tececo.com/files/newsletters/Newsletter
   93.php

17
The Potential of CO2 Release and Capture
Magnesium Carbonating SystemMgCO3 Route using
TecEco Tec-Kiln
No Capture during Manufacture
With Capture during Manufacture
lt7250C
CO2 capture (e.g. N-Mg process etc.)
CO2
Net Emissions (Sequestration) .085 kg CO2/kg
product
CO2 from atmosphere
Net Emissions (Sequestration) 0.403 Kg CO2/Kg
product
MgCO3
MgCO3
H2O
H2O
H2O
Net Energy 4084 kJ/kg product
H2O
Net Energy 4084 kJ/kg product
MgO
MgO
Mg(OH)2
Mg(OH)2
H2O
H2O
Net sequestration less carbon from process
emissions
Carbon neutral except for carbon from process
emissions
Use of non fossil fuels gt Low or no process
emissions
Source Data http//www.tececo.com/files/spreadshe
ets/TecEcoCementLCA14Feb2011.xls
18
The Potential of CO2 Release and Capture
Magnesium Carbonating SystemMgCO3.3H20 Route
using TecEco Tec Kiln
No Capture during Manufacture
With Capture during Manufacture
lt4200C
CO2 capture (e.g. N-Mg process etc.)
Net Emissions (Sequestration) - .399kg CO2/kg
product
CO2
CO2 from atmosphere
Net Emissions (Sequestration) 0.693 Kg CO2/Kg
product
MgCO3.3H2O
MgCO3.3H2O
H2O
H2O
H2O
Net Energy 7140 kJ/kg product
H2O
Net Energy 7140 kJ/kg product
MgO
MgO
Mg(OH)2
Mg(OH)2
H2O
H2O
Net sequestration less carbon from process
emissions
Carbon neutral except for carbon from process
emissions
Use of non fossil fuels gt Low or no process
emissions
Source Data http//www.tececo.com/files/spreadshe
ets/TecEcoCementLCA14Feb2011.xls
19
Gaia Engineering

• kg CO2-e/kg product
• -1.092
• -.399
• -1.092
• gt2 kg CO2-e/kg Mg product

2
3
1
Or similar. The annual world production of HCl
is about 20 million tons, most of which is
captive (about 5 million tons on the merchant
market). 
20
The N-Mg Process
HCl
NH3 and a small amount of CO2
MgCO3.3H2O
CO2
Mg rich water
MgO
Tec-Kiln
Ammoniacal Mg rich water
Mg(OH)2
H2O
MgO
Steam
MgCO3.3H2O
Filter
NH4Cl and a small amount of NH4HCO3
Filter
A Modified Solvay Process for Nesquehonite
21
The Tec-Reactor HydroxideCarbonate Capture Cycle

• The solubility of carbon dioxide gas in seawater
• Increases as the temperature approached zero and
• Is at a maxima around 4oC
• This phenomenon is related to the chemical nature
  of CO2 and water and
• Can be utilised in a carbonate hydroxide slurry
  process to capture CO2 out of the air and release
  it for storage or use in a controlled manner

22
Gaia Engineering
Portland CementManufacture
CaO
TecEcoTec-Kiln
Industrial CO2
MgO
Clays
Brine, Seawater, Oil Process water, De Sal Waste
Water etc .
GBFS
TecEcoCementManufacture
N-Mg Process
MgCO3.3H2O
Fly ash
Eco-Cements
Tec-Cements
NH4Cl or HCl
FreshWater
Buildingcomponents aggregates
Other wastes
23
Man Made CarbonateAggregate?
Source USGS Cement Pages
Assumptions - 50 non PC N-Mg mix and Substitution by Mg Carbonate Aggregate Assumptions - 50 non PC N-Mg mix and Substitution by Mg Carbonate Aggregate Assumptions - 50 non PC N-Mg mix and Substitution by Mg Carbonate Aggregate
Percentage by Weight of Cement in Concrete 15.00
Percentage by weight of MgO in cement 6
Percentage by weight CaO in cement 29
Proportion Cement Flyash and/or GBFS 50
1 tonne Portland Cement 0.867 Tonnes CO2
Proportion Concrete that is Aggregate 85
CO2 captured in 1 tonne aggregate 1.092 Tonnes CO2
24
Magnesium Carbonate Cements

• Magnesite (MgCO3) and the di, tri, and
  pentahydrates known as barringtonite
  (MgCO32H2O), nesquehonite (MgCO33H2O), and
  lansfordite (MgCO35H2O), respectively.
• Some basic forms such as artinite
  (MgCO3Mg(OH)23H2O),hydromagnestite
  (4MgCO3Mg(OH)24H2O) and dypingite (4MgCO3
  Mg(OH)25H2O) also occur as minerals.
• We pointed out as early as 2001 that magnesium
  carbonates are ideal for sequestration as
  building materials mainly because a higher
  proportion of CO2 than with calcium can be bound
  and significant strength can be achieved.
• The significant strength is a result of increased
  density through carbonation (high molar volume
  increases) and the microstructure developed by
  some forms.

25
TecEco Eco-Cements
Eco-Cements are blends of one or more hydraulic
cements and relatively high proportions of
reactive magnesia with or without pozzolans and
supplementary cementitious additions. They will
only carbonate in gas permeable substrates
forming strong fibrous minerals. Water vapour and
CO2 must be available for carbonation to
ensue. Eco-Cements can be used in a wide range
of products from foamed concretes to bricks,
blocks and pavers, mortars renders, grouts and
pervious concretes such as our own permeacocrete.
Somewhere in the vicinity of the Pareto
proportion (80) of conventional concretes could
be replaced by Eco-Cement.
Left Recent Eco-Cement blocks made, transported
and erected in a week. Laying and Eco-Cement
floor. Eco-Cement mortar Eco-cement mud bricks.
Right Eco-Cement permeacocretes and foamed
concretes
26
TecEco Tec-Kiln, N-Mg route
The calcination of nesquehonite has a relatively
high enthalpy but there is significant scope for
reducing energy using waste heat Initial weight
loss below 1000 C consists almost entirely
of water (1.3 molecules per molecule of
nesquehonite). Between 100 and 1500C
volatilization of further water is associated
with a small loss of carbon dioxide (3-5
). From 1500C to 2500C, the residual water
content varies between 0-6 and 0-2 molecules per
molecule of MgC03. Above 3000C, loss of
carbon dioxide becomes appreciable and is
virtually complete by 4200C, leaving MgO with a
small residual water content. Energy could be
saved using a two stage calcination process using
waste energy for the first stage.
Dell, R. M. and S. W. Weller (1959). "The Thermal
Decomposition of Nesquehonite MgCO3 3H20 And
Magnesium Ammonium Carbonate MgCO3 (NH4)2CO3
4H2O." Trans Faraday Soc 55(10) 2203 - 2220.
27
Modified PC 50 Ternary Mix withN-Mg Route Mg
Carbonate Aggregate

• 25-30 improvement in strength
• Fast first set
• Better Rheology
• Less shrinkage less cracking
• Less bleeding
• Long term durability
• Solve autogenous shrinkage?

Criteria Good Bad
Energy Requirements and Chemical Releases, Reabsorption (Sequestration?) Use gt50 replacements and still set like normal concrete!
Speed and Ease of Implementation Rapid adoption possible
Barriers to Deployment Permissions and rewards systems see http//www.tececo.com/sustainability.permissions_rewards.php
Cost/Benefit Excellent until fly ash runs out!
Use of Wastes? or Allow Use of Wastes? Uses GBFS and fly ash and manufactured nesquehonite based aggregate
Performance
Engineering Excellent all round
Thermal High thermal capacity
Architectural Excellent
Safety No issues
Audience 1
Audience 2
28
Magnesium Phosphate Cements

• Chemical cements that rely on the precipitation
  of insoluble magnesium phosphate from a mix of
  magnesium oxide and a soluble phosphate.
• Some of the oldest binders known (dung MgO)
• Potentially very green
• if the magnesium oxide used is made with no
  releases or via the nesquehonite (N-Mg route) and
• a way can be found to utilise waste phosphate
  from intensive agriculture and fisheries e.g.
  feedlots. (Thereby solving another environmental
  problem)

Criteria Good Bad
Energy Requirements and Chemical Releases, Reabsorption (Sequestration?) The MgO used could be made without releases There is not much phosphate on the planet
Speed and Ease of Implementation Rapid adoption possible If barrier overcome (see below)
Barriers to Deployment Permissions and rewards systems see http//www.tececo.com/sustainability.permissions_rewards.php. Must find a way to extract phosphate from organic pollution.
Cost/Benefit Economies of scale issue for MgO to overcome
Use of Wastes? or Allow Use of Wastes? With technology could use waste phosphate reducing water pollution
Performance
Engineering Excellent all round
Thermal High thermal capacity
Architectural
Safety No issues
Audience 1
Audience 2
29
Sorel Type Cements and Derivatives
Sorel Type Cements and Derivatives are all nano
or mechano composites relying on a mix of ionic,
co-valent and polar bonding. There are a very
large number of permutations and combinations and
thus a large number of patents
Criteria Good Bad
Energy Requirements and Chemical Releases, Reabsorption (Sequestration?) The MgO used could be made without releases
Speed and Ease of Implementation More could be used If barrier overcome (see below)
Barriers to Deployment Not waterproof even with modification.
Cost/Benefit Economies of scale issue for MgO to overcome
Use of Wastes? or Allow Use of Wastes? Not waterproof
Performance
Engineering Excellent except Not waterpoof, salt affect metals
Thermal High thermal capacity
Architectural
Safety No issues
Audience 1
Audience 2
30
Future Cement Contenders
Cements Based on Process Process CO2(tonnes CO2 / tonne Compound) Decarbonation CO2(tonnes CO2 / tonne Compound) Emissions (if no kiln capture tonnes CO2 / tonne Compound) Emissions (kiln capture tonnes CO2 / tonne Compound) Absorption (tonnes CO2 / tonne Compound, Assuming 100 carbonation 1 year) Net Emissions (Sequestration) (tonnes CO2 / tonne Compound, Assuming 100 carbonation 1 year) Example of Cement Type Apply to Comment Notes
CaO Conventional .453 0.785 1.237 .453 0.785 -0.332 Carbonating lime mortar Calera, British Lime Assn. many others Small net sequestration with TecEco kiln 1
C3S Conventional ? 0.578 gt0.578 ? gt0.578       3
C2S Conventional ? 0.511 gt0.511 ? gt0.511 Belite cement Chinese others   3
C3A Conventional ? 0.594 gt0.594 ? gt0.594 Tri calcium aluminate cement Increased proportion  
C4A3S Conventional ? 0.216 gt0.216 ? ? Calcium sulfoaluminate cement Chinese others   3

• http//www.tececo.com/files/spreadsheets/TecEcoCem
  entLCA12Oct2011.xls
• Quillin, K. and P. Nixon (2006). Environmentally
  Friendly MgO-based cements to support sustainable
  construction - Final report, British Research
  Establishment.

31
Future Cement Contenders
Cements Based on Process Process CO2(tonnes CO2 / tonne Compound) Decarbonation CO2(tonnes CO2 / tonne Compound) Emissions (if no kiln capture tonnes CO2 / tonne Compound) Emissions (kiln capture tonnes CO2 / tonne Compound) Absorption (tonnes CO2 / tonne Compound, Assuming 100 carbonation 1 year) Net Emissions (Sequestration) (tonnes CO2 / tonne Compound, Assuming 100 carbonation 1 year) Example of Cement Type Apply to Comment Notes
Alakali Activated Ground Granulated Blast Furnace Slag (GBFS) GBFS (slag) is a waste product from the manuf acture of iron and steel Nil to cement industry GBFS with MgO activator Many other activators Patented by TecEco Not patented 1
Geo polymers Fly ash NaOH 0.16       0.16   Geopolymer Alliance, Geopolymer Institute, University Melbourne   6

• http//www.tececo.com/files/spreadsheets/TecEcoCem
  entLCA12Oct2011.xls
• http//www.geopolymers.com.au/science/sustainabili
  ty

32
CaO-Lime
Criteria Good Bad
Energy Requirements and Chemical Releases, Reabsorption (Sequestration?) The CaO used could be made without
Speed and Ease of Implementation Easily implemented as no carbonation rooms etc reqd. Permissions and rewards systems see http//www.tececo.com/sustainability.permissions_rewards.php.
Barriers to Deployment We need carbon trading!
Cost/Benefit
Use of Wastes? or Allow Use of Wastes?
Performance
Engineering Good
Thermal Engineered thermal capacity and conductivity.
Architectural
Safety An irritating dust
Audience 1
Audience 2
33
Geopolymers
Criteria Good Bad
Energy Requirements and Chemical Releases, Reabsorption (Sequestration?) Low provided we do not run out of fly ash
Speed and Ease of Implementation Process issues to be overcome Permissions and rewards systems see http//www.tececo.com/sustainability.permissions_rewards.php.
Barriers to Deployment We need carbon trading!
Cost/Benefit
Use of Wastes? or Allow Use of Wastes?
Performance
Engineering Good but inconsistent
Thermal Engineered thermal capacity and conductivity.
Architectural
Safety Caustic liquors
Audience 1
Audience 2
Geopolymers as a future concrete suffer from two
basic flaws on one very high risk Flaw. 1. The
nanoporisity flaw which leads to durability
problems and Flaw. 2. The fact that water is not
consumed in the geopolymerisation process
resulting in the almost impossible task of making
them fluid enough for placement. Too much water
reduces alkalinity and hence the high risk.
34
Other Contenders

• Slag cements a variant of Portland cement as CSH
  is the main product.
• Supersulfated cements have potential as they are
  made mostly from GBFS and gypsum which are wastes
  and only a small amount of PC or lime. The main
  hydration product is ettringite and they show
  good resistance to aggressive agents including
  sulphate but are slow to set. (A derivative)
• Calcium aluminate cements are hydraulic cements
  made from limestone and bauxite. The main
  components are monocalcium aluminate CaAl2O4 (CA)
  and mayenite Ca12Al14O33 (C12A7) which hydrate to
  give strength. Calcium aluminate cements are
  chemically resistant and stable to quite high
  temperatures.
• Calcium sulfoaluminate cements belite calcium
  sulfoaluminate cements are low energy cements
  that have the potential to be made from
  industrial by products such as low calcium fly
  ash and sulphur rich wastes. The main hydration
  product producing strength is ettringite. Their
  use has been pioneered in China (A derivative)

35
Other Contenders

• Belite cements can be made at a lower temperature
  and contains less lime than Portland cement and
  therefore has much lower embodied energy and
  emissions. Cements containing predominantly
  belite are slower to set but otherwise have
  satisfactory properties. Many early Portland type
  cements such as Rosendale cement were rich in
  belite like phases. (a variant, See
  http//www.tececo.com/links.cement_rosendale.php.)
  
• PC - MgO GBFS fly ash blends. MgO is the most
  powerful new tool in hydraulic cement blends
  since the revelation that reactive magnesia can
  be blended with other hydraulic cements such as
  Portland cement. 25-30 improvements in
  compressive strength and greater improvements in
  tensile strength, faster first set, better
  rheology and less shrinkage and cracking less
  bleeding and long term durability have been
  demonstrated. It is also possible autogenous
  shrinkage has been solved.
• MgO blended with other hydraulic cements,
  pozzolans and supplementary cementitious
  materials (SCMs). Amazingly very little real
  research has been done on optimised blends
  particularly with cements other than Portland
  cement.