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An overview of Future Concretes An overview of the alternative mineral binder systems and composites made with them including novel concrete technologies.

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Presentation on theme: "An overview of Future Concretes An overview of the alternative mineral binder systems and composites made with them including novel concrete technologies."— Presentation transcript:

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 28/01/2014

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 c 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

7 Some of the Issues? Primary Production Process Build, & Manufacture Use Dispose Underlying Molecular Flows Primary Production Methane NOX & SOX Heavy Metals CO 2 etc. Embodied & Process Energy Process, Build & Manufacture NOX & SOX Heavy Metals CO 2 etc. Embodied & Process Energy Use NOX & SOX Heavy Metals CO 2 etc. Lifetime Energy Dispose or Waste Methane NOX & SOX Heavy Metals CO 2 etc. Process Energy The Techno Process

8 Predicted Global Cement Demand and Emissions Source: Quillin K. Low-CO2 Cements based on Calcium Sulfoaluminate [Internet]. Available from: ts%20Nov%2010/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:

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 Contenders Portland Cement 1.http://www.tececo.com/files/spreadsheets/TecEcoCementLCA12Oct2011.xlshttp://www.tececo.com/files/spreadsheets/TecEcoCementLCA12Oct2011.xls Cements Based on Process Process CO 2 (tonnes CO 2 / tonne Compound ) Decarbonat ion CO 2 (tonnes CO 2 / tonne Compound) Emissions (if no kiln capture– tonnes CO 2 / tonne Compoun d) Emission s (kiln capture– tonnes CO 2 / tonne Compoun d) Absorpti on (tonnes CO 2 / tonne Compoun d, Assuming 100% carbonati on 1 year) Net Emissions (Sequestrat ion – No kiln Capture) (tonnes CO 2 / tonne Compound, Assuming 100% carbonatio n 1 year) Example of Cement Type Apply toComment Notes PC Current Methods None Split process lime with recapture then clinker Most dense concretes No supplementary cementitious or pozzolanic materials 1 PC Permeable Block formulation Ordinary Portland Cement Most dense concretes No supplementary cementitious or pozzolanic materials 1 PC Split Process – Lime then clinker Split process lime with recapture then clinker Most dense concretes No supplementary cementitious or pozzolanic materials 1

15 H2OH2O The Potential of CO 2 Release and Capture - Portland Cements Split Process with Capture during Manufacture No Capture during Manufacture CO 2 in atmosphere Carbon positive. Chemical and process emissions Net sequestration less carbon from process emissions Use of non fossil fuels => Low or no process emissions Clinker H2OH2O Hydrated Cement Paste CaCO 3 + Clays CaCO 3 Hydrated Cement Paste Net Emissions (Sequestration) kg CO 2 /kg product Net Emissions (Sequestration) Kg CO 2 /Kg product CO 2 capture (e.g. N-Mg process etc.) Source Data: CaO + Clays Capture during Manufacture Net Energy 3962 kJ/kg product Carbon positive. Chemical and process emissions Clinker H2OH2O Hydrated Cement Paste CaCO 3 + Clays Net Emissions (Sequestration) kg CO 2 /kg product Net Energy 3962 kJ/kg product CO 2 capture (e.g. N-Mg process etc.)

16 Future Cement Contenders Mg Group 1.http://www.tececo.com/files/spreadsheets/TecEcoCementLCA12Oct2011.xlshttp://www.tececo.com/files/spreadsheets/TecEcoCementLCA12Oct2011.xls 2.http://www.tececo.com/files/newsletters/Newsletter93.phphttp://www.tececo.com/files/newsletters/Newsletter93.php Cements Based on Process Process CO 2 (tonnes CO 2 / tonne Compound) Decarbona tion CO 2 (tonnes CO 2 / tonne Compoun d) Emission s (if no kiln capture– tonnes CO 2 / tonne Compou nd) Emission s (kiln capture– tonnes CO 2 / tonne Compou nd) Absorpti on (tonnes CO 2 / tonne Compou nd, Assumin g 100% carbonati on 1 year) Net Emission s (Sequestr ation) (tonnes CO 2 / tonne Compou nd, Assumin g 100% carbonati on 1 year) Example of Cement Type Apply toComment Notes <750 o CMgCO Eco-cement concrete, pure MgO concretes. Novacem concretes TecEco, Cambridge & Novacem TecEco Eco-Cement Force carbonated pure MgO 3 <450 o CMgCO 3.3H 2 O Eco-cement concrete, pure MgO concretes. Novacem concretes? TecEco, Cambridge & Novacem N-Mg route University of Rome 3 <450 o C MgCO 3.3H 2 O Including capture during production of nesquehonite Eco-cement concrete, pure MgO concretes. Novacem concretes? TecEco, Cambridge & Novacem N-Mg route University of Rome 3 Silicate route ? NovacemAfter Klaus Lackner? Modified Ternary Blends (50% PC) Split Process – Lime (with capture) then clinker Ternary mix with MgO additive. Most dense concretes Faster setting and higher early strength 2

17 The Potential of CO 2 Release and Capture Magnesium Carbonating System MgCO 3 Route using TecEco Tec-Kiln With Capture during Manufacture No Capture during Manufacture CO 2 CO 2 from atmosphere CO 2 capture (e.g. N-Mg process etc.) Carbon neutral except for carbon from process emissions Net sequestration less carbon from process emissions Use of non fossil fuels => Low or no process emissions MgO Mg(OH)2 H2OH2O H2OH2O H2OH2O H2OH2O H2OH2O MgCO 3 Net Emissions (Sequestration) Kg CO 2 /Kg product Net Emissions (Sequestration).085 kg CO 2 /kg product Source Data: MgCO 3 H2OH2O Net Energy 4084 kJ/kg product < C

18 The Potential of CO 2 Release and Capture Magnesium Carbonating System MgCO 3.3H 2 0 Route using TecEco Tec Kiln With Capture during Manufacture No Capture during Manufacture CO 2 CO 2 from atmosphere CO 2 capture (e.g. N-Mg process etc.) Carbon neutral except for carbon from process emissions Net sequestration less carbon from process emissions Use of non fossil fuels => Low or no process emissions MgO Mg(OH)2 H2OH2O H2OH2O H2OH2O H2OH2O H2OH2O MgCO 3.3H 2 O Net Emissions (Sequestration) Kg CO 2 /Kg product Net Emissions (Sequestration) -.399kg CO 2 /kg product Source Data: MgCO 3.3H 2 O H2OH2O Net Energy 7140 kJ/kg product < C

19 Gaia Engineering kg CO2-e/kg product >2 kg CO2-e/kg Mg product 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 Tec-Kiln NH 3 and a small amount of CO 2 MgCO 3.3H 2 O MgO Mg(OH) 2 CO 2 H2OH2O Steam NH 4 Cl and a small amount of NH 4 HCO 3 Filter Mg rich water Ammoniacal Mg rich water MgCO 3.3H 2 O HCl A Modified Solvay Process for Nesquehonite

21 The Tec-Reactor Hydroxide Carbonate Capture Cycle The solubility of carbon dioxide gas in seawater – Increases as the temperature approached zero and – Is at a maxima around 4 o C This phenomenon is related to the chemical nature of CO 2 and water and Can be utilised in a carbonate – hydroxide slurry process to capture CO 2 out of the air and release it for storage or use in a controlled manner

22 Gaia Engineering MgCO 3.3H 2 O N-Mg Process NH4Cl or HCl Industrial CO 2 MgO TecEco Tec-Kiln Eco- Cements Building components & aggregates TecEco Cement Manufacture CaO Clays Portland Cement Manufacture Brine, Sea water, Oil Process water, De Sal Waste Water etc. Tec- Cements Other wastes Fresh Water GBFS Fly ash

23 Man Made Carbonate Aggregate? Source USGS: Cement Pages Assumptions - 50% non PC N-Mg mix and Substitution by Mg Carbonate Aggregate Percentage by Weight of Cement in Concrete15.00% Percentage by weight of MgO in cement6% Percentage by weight CaO in cement29% Proportion Cement Flyash and/or GBFS50% 1 tonne Portland Cement0.867Tonnes CO2 Proportion Concrete that is Aggregate85% CO2 captured in 1 tonne aggregate1.092Tonnes CO2

24 Magnesium Carbonate Cements Magnesite (MgCO3) and the di, tri, and pentahydrates known as barringtonite (MgCO3·2H2O), nesquehonite (MgCO3·3H2O), and lansfordite (MgCO3·5H2O), respectively. Some basic forms such as artinite (MgCO3·Mg(OH)2·3H2O), hydromagnestite (4MgCO3·Mg(OH)2·4H2O) and dypingite (4MgCO3· Mg(OH)2·5H2O) 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 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 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.

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 C consists almost entirely of water (1.3 molecules per molecule of nesquehonite). Between 100 and C volatilization of further water is associated with a small loss of carbon dioxide (~3-5 %). From C to C, the residual water content varies between 0-6 and 0-2 molecules per molecule of MgC03. Above C, loss of carbon dioxide becomes appreciable and is virtually complete by C, 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):

27 Modified PC 50% Ternary Mix with N-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? CriteriaGoodBad Energy Requirements and Chemical Releases, Reabsorption (Sequestration?) Use >50% replacements and still set like normal concrete! Speed and Ease of Implementation Rapid adoption possible Barriers to Deployment Permissions and rewards systems see rds.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) CriteriaGoodBad Energy Requirements and Chemical Releases, Reabsorption (Sequestration?) The MgO used could be made without releasesThere is not much phosphate on the planet Speed and Ease of Implementation Rapid adoption possibleIf barrier overcome (see below) Barriers to Deployment Permissions and rewards systems see rds.php. Must find a way to extract phosphate from organic pollution. rds.php 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 CriteriaGoodBad Energy Requirements and Chemical Releases, Reabsorption (Sequestration?) The MgO used could be made without releases Speed and Ease of Implementation More could be usedIf 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 exceptNot waterpoof, salt affect metals Thermal High thermal capacity Architectural Safety No issues Audience 1 Audience 2

30 Future Cement Contenders 1.http://www.tececo.com/files/spreadsheets/TecEcoCementLCA12Oct2011.xlshttp://www.tececo.com/files/spreadsheets/TecEcoCementLCA12Oct2011.xls 3.Quillin, K. and P. Nixon (2006). Environmentally Friendly MgO-based cements to support sustainable construction - Final report, British Research Establishment. Cements Based on Process Process CO 2 (tonnes CO 2 / tonne Compound) Decarbon ation CO 2 (tonnes CO 2 / tonne Compoun d) Emission s (if no kiln capture– tonnes CO 2 / tonne Compou nd) Emission s (kiln capture– tonnes CO 2 / tonne Compou nd) Absorpt ion (tonnes CO 2 / tonne Compou nd, Assumi ng 100% carbona tion 1 year) Net Emissions (Sequestr ation) (tonnes CO 2 / tonne Compoun d, Assuming 100% carbonati on 1 year) Example of Cement Type Apply toComment Notes CaOConventional Carbonating lime mortar Calera, British Lime Assn. & many others Small net sequestration with TecEco kiln 1 C3SC3SConventional?0.578>0.578? 3 C2SC2SConventional?0.511>0.511? Belite cementChinese & others 3 C3AC3AConventional?0.594>0.594? Tri calcium aluminate cement Increased proportion C4A3SC4A3SConventional?0.216>0.216?? Calcium sulfoaluminate cement Chinese & others 3

31 Future Cement Contenders 1.http://www.tececo.com/files/spreadsheets/TecEcoCementLCA12Oct2011.xlshttp://www.tececo.com/files/spreadsheets/TecEcoCementLCA12Oct2011.xls 4.http://www.geopolymers.com.au/science/sustainability Cements Based on Process Process CO 2 (tonnes CO 2 / tonne Compound) Decarbon ation CO 2 (tonnes CO 2 / tonne Compoun d) Emission s (if no kiln capture– tonnes CO 2 / tonne Compou nd) Emission s (kiln capture– tonnes CO 2 / tonne Compou nd) Absorpt ion (tonnes CO 2 / tonne Compou nd, Assumi ng 100% carbona tion 1 year) Net Emissions (Sequestr ation) (tonnes CO 2 / tonne Compoun d, Assuming 100% carbonati on 1 year) Example of Cement Type Apply toComment Notes Alakali Activated Ground Granulate d 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 Geopolymer Alliance, Geopolymer Institute, University Melbourne 6

32 CaO-Lime CriteriaGoodBad 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 rds.php. rds.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 CriteriaGoodBad 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 rds.php. rds.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 CaAl 2 O 4 (CA) and mayenite Ca 12 Al 14 O 33 (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 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 % 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.


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