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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 addressing practical supply chain and economic issues including energy 17/07/2015 www.tececo.com www.propubs.com Why Future Concretes? • What’s 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 don’t necessarily produce more and those producing them will make more money. • Concrete made for purpose = Higher Margin? – Architectural façade, insulative properties, permeable pavement etc. 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 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. – That’s 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. 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. Increases in Business Performance from the Previous Year, by Innovation Status 2008-9 Some of the Issues? The Techno Process Primary Production Process Build, & Manufacture Use Dispose Underlying Molecular Flows Primary Production Methane NOX & SOX Heavy Metals CO2 etc. Embodied & Process Energy Process, Build & Manufacture NOX & SOX Heavy Metals CO2 etc. Embodied & Process Energy Use NOX & SOX Heavy Metals CO2 etc. Lifetime Energy Dispose or Waste Methane NOX & SOX Heavy Metals CO2 etc. Process Energy 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/Conference%20Downloads/Low%20Carbon%20Cemen ts%20Nov%2010/Sulphoaluminate_Cements_Keith_Quillin_R.ashx 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 Global Waste – An Underestimate! The challenge is to convert waste to resource. 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 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 what’s important and what is not Example of a Decision Matrix to Help us Improve the Future ALTERNATIVES Mg Hydraulic Decision Model Criterion Weight Rating Ea se of Pla cement PC Score Rating Geopolymer Score Rating MgCarbonate Score Rating MgO Score Rating C4 A 3 S Score Rating Score 10 9 90 8.5 85 3 30 7 70 0 0 7 70 Cost 8 8 64 8.5 68 9 72 7 56 0 0 7 56 Sa fety 7 8 56 8 56 4 28 8 56 0 0 8 56 Compressive Strength 6 8 48 7.5 45 7.5 45 6 36 6 36 6 36 Tensile Strength 5 9 45 7.5 37.5 7.5 37.5 6 30 6 30 6 30 Dura bility 5 9 45 7 35 7 35 8 40 8 40 8 40 Use of Pozzola nic Wa stes 5 9 45 7 35 7 35 4 20 4 20 4 20 Use of Other Wa stes 5 9 45 4 20 5 25 9 45 9 45 4 20 Embodied Energy 8 7 56 7 56 8 64 7 56 7 56 7 56 Embodied Emissions 8 7 56 7 56 9 72 5 40 5 40 5 40 Therma l Ma ss 4 8 32 8 32 8 32 7 28 7 28 7 28 Therma l Flow 4 8 32 8 32 4 16 9 36 9 36 9 36 Supply Cha in 7 8 56 9 63 4 28 5 35 4 28 5 35 82 107 670 97 621 83 520 88 548 65 359 83 523 Total Score = Rati ng * Wei ght Rating 700 Score 600 500 400 Scores 300 200 100 0 Mg - Hydraulic Alternatives Score PC Rating Geopolymer Decision Model Future Cement Contenders Portland Cement PC Current Methods PC Permeable Block .369 formulation PC Split Process – Lime then .369 clinker .369 0.498 0.498 0.498 .868 .868 .868 None .369 .369 .001 .144 .001 1. http://www.tececo.com/files/spreadsheets/TecEcoCementLCA12Oct2011.xls Apply to Comment Notes Cements Process Based on Net Absorpti Emissions Emission on (Sequestrat Emissions s (kiln (tonnes ion – No Process (if no kiln capture– CO2 / kiln CO2 Decarbonat capture– tonnes tonne Capture) (tonnes ion CO2 tonnes Compoun Example of CO2 / CO2 / (tonnes CO2 (tonnes CO2 / d, Cement Type tonne tonne / tonne CO / tonne tonne Compoun Assuming 2 Compound Compound) Compound, Compoun d) 100% ) carbonati Assuming d) 100% on 1 carbonatio year) n 1 year) .867 Split process lime with recapture then clinker No supplementary Most dense cementitious or pozzolanic concretes materials 1 .724 No supplementary Ordinary Most dense cementitious or pozzolanic Portland Cement concretes materials 1 .368 Split process lime with recapture then clinker 1 No supplementary Most dense cementitious or pozzolanic concretes materials The Potential of CO2 Release and Capture - Portland Cements No Capture during Manufacture CO2 capture (e.g. N-Mg process etc.) CO2 in atmosphere Hydrated Cement Paste H 2O Clinker Net Energy 3962 kJ/kg product Hydrated Cement Paste Carbon positive. Chemical and process emissions Carbon positive. Chemical and process emissions CO2 capture (e.g. N-Mg process etc.) CaCO3 CaCO3 + Clays CaCO3 + Clays Net Energy 3962 kJ/kg product Net Emissions (Sequestration) 0.369 Kg CO2/Kg product Net Emissions (Sequestration) 0.369 kg CO2/kg product Net Emissions (Sequestration) 0.867 kg CO2/kg product H 2O Split Process with Capture during Manufacture Capture during Manufacture H 2O Clinker Net Energy 3962 kJ/kg product Hydrated Cement Paste CaO + Clays Clinker Net sequestration less carbon from process emissions Use of non fossil fuels => Low or no process emissions Source Data: http://www.tececo.com/files/spreadsheets/TecEcoCementLCA12Oct2011.xls Future Cement Contenders Mg Group Absorpti on (tonnes CO2 / tonne Compou nd, Assumin g 100% carbonati on 1 year) Net Emission s (Sequestr ation) (tonnes CO2 / Example of Cement tonne Apply to Type Compou nd, Assumin g 100% carbonati on 1 year) Cements Process Based on Emission Emission s (kiln Decarbona s (if no capture– Process tion CO2 kiln tonnes CO2 (tonnes capture– CO2 / (tonnes CO2 / tonnes tonne CO2 / tonne tonne CO2 / Compou Compound) Compoun tonne nd) Compou d) nd) <750 oC MgCO3 .403 1.092 1.495 .403 -1.092 .-.688 Eco-cement concrete, TecEco Eco-Cement TecEco, Cambridge pure MgO concretes. Force carbonated & Novacem Novacem concretes pure MgO 3 <450 oC MgCO3.3H2O .693 1.092 1.784 .693 -1.092 -.399 Eco-cement concrete, TecEco, Cambridge N-Mg route pure MgO concretes. & Novacem University of Rome Novacem concretes? 3 .693 1.092 1.784 .693 -2.184 -1.491 Eco-cement concrete, TecEco, Cambridge N-Mg route pure MgO concretes. & Novacem University of Rome Novacem concretes? 3 <450 oC Modified Ternary Blends (50% PC) MgCO3.3H2O Including capture during production of nesquehonite Silicate route Split Process – Lime (with capture) then clinker ? .185 Novacem .185 .002 .183 1. http://www.tececo.com/files/spreadsheets/TecEcoCementLCA12Oct2011.xls 2. http://www.tececo.com/files/newsletters/Newsletter93.php Ternary mix with MgO Most dense additive. concretes Notes Comment After Klaus Lackner? Faster setting and 2 higher early strength The Potential of CO2 Release and Capture Magnesium Carbonating System MgCO3 Route using TecEco Tec-Kiln No Capture during Manufacture With Capture during Manufacture <7250C CO2 CO2 from atmosphere Net Emissions (Sequestration) 0.403 Kg CO2/Kg product Net Emissions (Sequestration) .085 kg CO2/kg product CO2 capture (e.g. N-Mg process etc.) MgCO3 MgCO3 H2O H2O Net Energy 4084 kJ/kg product MgO H2O H2O Net Energy 4084 kJ/kg product MgO Mg(OH)2 Mg(OH)2 H2O Carbon neutral except for carbon from process emissions H2O Net sequestration less carbon from process emissions Use of non fossil fuels => Low or no process emissions Source Data: http://www.tececo.com/files/spreadsheets/TecEcoCementLCA14Feb2011.xls The Potential of CO2 Release and Capture Magnesium Carbonating System MgCO3.3H20 Route using TecEco Tec Kiln No Capture during Manufacture With Capture during Manufacture <4200C CO2 CO2 from atmosphere Net Emissions (Sequestration) 0.693 Kg CO2/Kg product CO2 capture (e.g. N-Mg process etc.) MgCO3.3H2O MgCO3.3H2O H2O H2O Net Energy 7140 kJ/kg product Net Emissions (Sequestration) .399kg CO2/kg product MgO H2O H2O Net Energy 7140 kJ/kg product MgO Mg(OH)2 Mg(OH)2 H2O Carbon neutral except for carbon from process emissions H2O Net sequestration less carbon from process emissions Use of non fossil fuels => Low or no process emissions Source Data: http://www.tececo.com/files/spreadsheets/TecEcoCementLCA14Feb2011.xls Gaia Engineering kg CO2-e/kg product 1 -1.092 2 -.399 3 -1.092 >2 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). The N-Mg Process HCl NH3 and a small amount of CO2 CO2 H2O Tec-Kiln Mg rich water Ammoniacal Mg rich water MgCO3.3H2O MgO MgO Mg(OH)2 Steam MgCO3.3H2O Filter Filter NH4Cl and a small amount of NH4HCO3 A Modified Solvay Process for Nesquehonite 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 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 Gaia Engineering Portland Cement Manufacture CaO Industrial CO2 Brine, Sea water, Oil Process water, De Sal Waste Water etc . N-Mg Process TecEco Tec-Kiln MgO MgCO3.3H2O Clays TecEco Cement Manufacture GBFS Fly ash Fresh Water EcoCements NH4Cl or HCl Building components & aggregates Other wastes TecCements Man Made Carbonate Aggregate? Tonnes 20,000,000,000 18,000,000,000 16,000,000,000 World Production PC 14,000,000,000 Tonnes CO2 from unmodified PC 12,000,000,000 World Production Concrete 10,000,000,000 8,000,000,000 Calculated Proportion Aggregate 6,000,000,000 4,000,000,000 CO2 Sequestered in Mg Carbonate Aggregate 2,000,000,000 Net Sequestration 2009 2006 2003 2000 1997 1994 1991 1988 1985 1982 1979 1976 1973 1970 1967 1964 1961 1958 1955 1952 1949 1946 0 Assumptions - 50% non PC N-Mg mix and Substitution by Mg Carbonate Aggregate Percentage by Weight of Cement in Concrete Percentage by weight of MgO in cement Percentage by weight CaO in cement Proportion Cement Flyash and/or GBFS 1 tonne Portland Cement Proportion Concrete that is Aggregate CO2 captured in 1 tonne aggregate Source USGS: Cement Pages 15.00% 6% 29% 50% 0.867Tonnes CO2 85% 1.092Tonnes CO2 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. 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 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. 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. Energy could be saved using a two stage calcination process using waste energy for the first stage. 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? Criteria Good Energy Requirements and Chemical Releases, Use >50% replacements and still set like “normal” Reabsorption (Sequestration?) concrete! Speed and Ease of Implementation Rapid adoption possible Barriers to Deployment Cost/Benefit Use of Wastes? or Allow Use of Wastes? Performance Engineering Thermal Architectural Safety Audience 1 Audience 2 Bad Permissions and rewards systems see http://www.tececo.com/sustainability.permissions_rewa rds.php Excellent until fly ash runs out! Uses GBFS and fly ash and manufactured nesquehonite based aggregate Excellent all round High thermal capacity Excellent No issues 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 Energy Requirements and Chemical Releases, Reabsorption (Sequestration?) The MgO used could be made without releases Speed and Ease of Implementation Rapid adoption possible Barriers to Deployment Cost/Benefit Use of Wastes? or Allow Use of Wastes? Performance Engineering Thermal Architectural Safety Audience 1 Audience 2 Economies of scale issue for MgO to overcome With technology could use waste phosphate reducing water pollution Excellent all round High thermal capacity No issues Bad There is not much phosphate on the planet If barrier overcome (see below) Permissions and rewards systems see http://www.tececo.com/sustainability.permissions_rewa rds.php. Must find a way to extract phosphate from organic pollution. 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 Energy Requirements and Chemical Releases, Reabsorption (Sequestration?) The MgO used could be made without releases Speed and Ease of Implementation More could be used Barriers to Deployment Cost/Benefit Economies of scale issue for MgO to overcome Use of Wastes? or Allow Use of Wastes? Performance Engineering Excellent except Thermal High thermal capacity Architectural Safety No issues Audience 1 Audience 2 Bad If barrier overcome (see below) Not waterproof even with modification. Not waterproof Not waterpoof, salt affect metals Future Cement Contenders (tonnes CO2 / Example of tonne Cement Type Compoun d, Assuming 100% carbonati on 1 year) 0.785 -0.332 >0.578 >0.511 ? ? >0.578 >0.511 0.594 >0.594 ? >0.594 0.216 >0.216 ? ? CaO Conventional .453 0.785 1.237 C3S C2S Conventional ? Conventional ? 0.578 0.511 C3A Conventional ? C4A3S Conventional ? .453 Net Emissions (Sequestr ation) Carbonating lime mortar Apply to Comment Notes Cements Process Based on Absorpt ion Emission Emission (tonnes Decarbon s (kiln s (if no CO2 / ation capture– Process kiln tonne CO2 tonnes CO2 capture– Compou (tonnes CO2 / (tonnes CO2 tonnes nd, CO2 / tonne / tonne CO2 / Assumi tonne Compou tonne ng Compound) Compoun nd) Compou 100% d) carbona nd) tion 1 year) Small net Calera, British Lime sequestration Assn. & many others with TecEco kiln Belite cement Chinese & others Tri calcium aluminate Increased proportion cement Calcium sulfoaluminate Chinese & others cement 1. http://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. 1 3 3 3 Future Cement Contenders Cements Based on Process Alakali Activated Ground Granulate d Blast Furnace Slag (GBFS) GBFS (“slag”) is a waste product Nil to from the cement manuf industry acture of iron and steel Net Emissions (Sequestr ation) (tonnes CO2 / Example of tonne Cement Type Compoun d, Assuming 100% carbonati on 1 year) Apply to Comment Notes Absorpt ion Emission Emission (tonnes Decarbon s (kiln s (if no CO2 / ation capture– Process kiln tonne CO2 tonnes CO2 capture– Compou (tonnes CO2 / (tonnes CO2 tonnes nd, CO2 / tonne / tonne CO2 / Assumi tonne Compou tonne ng Compound) Compoun nd) Compou 100% d) carbona nd) tion 1 year) GBFS with MgO activator Patented by TecEco Many other activators 1 Not patented Geopolymer Alliance, Geo polymers Fly ash + NaOH 0.16 1. http://www.tececo.com/files/spreadsheets/TecEcoCementLCA12Oct2011.xls 4. http://www.geopolymers.com.au/science/sustainability 0.16 Geopolymer Institute, University Melbourne 6 CaO-Lime Criteria Good Energy Requirements and Chemical Releases, Reabsorption (Sequestration?) The CaO used could be made without Speed and Ease of Implementation Barriers to Deployment Cost/Benefit Use of Wastes? or Allow Use of Wastes? Performance Engineering Thermal Architectural Safety Audience 1 Audience 2 Easily implemented as no carbonation rooms etc reqd. Good Engineered thermal capacity and conductivity. An irritating dust Bad Permissions and rewards systems see http://www.tececo.com/sustainability.permissions_rewa rds.php. We need carbon trading! Geopolymers Criteria Good Energy Requirements and Chemical Releases, Reabsorption (Sequestration?) Low provided we do not run out of fly ash Speed and Ease of Implementation Barriers to Deployment Cost/Benefit Use of Wastes? or Allow Use of Wastes? Performance Engineering Thermal Architectural Safety Audience 1 Audience 2 Process issues to be overcome Bad Permissions and rewards systems see http://www.tececo.com/sustainability.permissions_rewa rds.php. We need carbon trading! Good but inconsistent Engineered thermal capacity and conductivity. Caustic liquors 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. 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) 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. 2530% 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 (SCM’s). Amazingly very little real research has been done on optimised blends particularly with cements other than Portland cement.