Hicks Publication - Durable Green Cements From CCPs Final A

7/31/2019 Hicks Publication - Durable Green Cements From CCPs Final A

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Durable "Green" Concrete from Activated Pozzolan Cement

James Hicks, P.E.

CeraTech, Inc.,3501 Brehms Lane, Suite D,Baltimore, MD 21213, (936) 697-2893, FAX (443) 524-4411, email:[email protected]

Abstract

Concrete is the most widely used man-made material, and the manufacture of portland
mailto:[email protected]:[email protected]


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cement - the active ingredient of concrete - accounts for 6 to 8 percent worldwide of allanthropogenic emissions of carbon dioxide, a leading greenhouse gas involved inglobal warming.

Globally, nearly 2.77 billion metric tons (t) (3.05 billion st) of portland and hydrauliccement was produced in 2007. The concrete construction sector has a responsibility totake immediate action to reduce its environmental impacts, including the generationreduction of CO2. This responsibility also brings the opportunity to develop innovativetechnologies, including use of materials from Coal Combustion Products (CCPs).

These newly developed activated fly ash based products leave virtually no carbonfootprint. Updated cementitious binder technology eliminates approximately 0.9 t (1 st)of CO2 emitted into the atmosphere per ton of portland cement produced. These

cements have been engineered for use in fast track concrete repairs and construction,conventional paving, walls and concrete block masonry, new construction and repairprojects.

Activated pozzolanic material cements and resulting products are comprised of up to 95percent green sustainable industrial waste stream materials, primarily fly ash. They aremanufactured via a low energy, powder blending process. Key to green cementdevelopment was creating a material matrix that has a very dense crystal structure. Thisgreen cement technology possesses excellent performance and durabilitycharacteristics, including high early strengths and 28-day strengths over 70 MPa

(10,000 psi). Moreover, they can be placed effectively with ambient temperaturesranging from -1C to 49C (30F to 120F).

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1. Introduction

2.

Coal is a relatively abundant, reliable and inexpensive energy source for worldwidepower generation. However, it is also one of the main producers of Carbon Dioxide(CO2). Fossil-fuel combustion in power plants, vehicles and heaters around the planetreleased 31.5 billion t (34.7 billion st) of the greenhouse gas (Bloomberg, 2009). TheU.S. alone produces approximately 1.5 billion tons of CO2 annually from all sources;globally, coal is attributed to one third of all CO2 emissions (USEPA, 2009).

Coal when used as a fuel, is also one of the main producers of Carbon Dioxide (CO2).Coal combustion has been brought into question regarding other noxious wasteproducts like Mercury, Nitrogen Oxide and Sulphur Dioxide. Economically and

technically, viable mitigation technologies exist for the above mentioned pollutantswith the exception of CO2 (Hicks, et. al. 2009).

Another large producer of CO2 emissions is portland cement kilns. For instance, the useof fly ash (a by-product of coal burning in power generation and most common CCP)in the cement-making process could reduce substantial amounts of CO2 emitted by acement kiln. Worldwide, the production of portland cement alone accounts for 6 to 8percent of all human generated CO2 greenhouse gases (Huntzinger, Deborah N. andEatmon, Thomas D., 2009). Portland cement production is not only a source ofcombustion-related CO2 emissions, but it is also one of the largest sources of industrialprocess-related emissions in the United States. Combustion related emissions from the

U.S. [portland] cement industry were estimated at approximately 36 Tg of CO2accounting for approximately 3.7 percent of combustion-related emissions in the U.S.industrial sector in 2001 (USGS, 2002)

In 2007, a survey of 161 US coal-fired power plants (out of 500 operating coal firedpower plants) showed production of 118 million t (131 million st) of CCPs. Of thisamount, only 12.4 million t (13.7 million st) were used in concrete or as a concreteproduct. The survey reported that more than 45.4 million t (50 million st) of fly ash isstill being disposed of in US landfills annually. (ACAA, 2008) Clearly, the use ofotherwise waste materials for beneficial use can reduce the need for more landfills andthe amount of CO2 produced.

Extensive research is underway to find more economically feasible alternatives forcarbon dioxide capture and storage (CCS). However, until financially andenvironmentally sustainable alternatives are in use, the toxic byproducts of pulverizedcoal-based power generation (conventional) will be an issue for decades to come. Asuccessful CO2 mitigation process presently lies in private-public strategy thatcombines existing power plants (revamped to capture, geologically store and/or

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enhance oil recovery), and new ones using more advanced coal power generationtechnologies like the Integrated Coal Gasification Combined Cycle (IGCC). Theseapproaches alongside proactive regulation could build a relatively sustainablealternative for the future (Floris, Vinio, 2009).

Not all current power plants will be refurbished as mentioned above; yet CCPs fromplants that do not convert to CCS technologies could still be put to good use throughinnovative ways in order to assist in the decrease of greenhouse gases. For instance, flyash (a by-product that largely ends up in landfills) can substitute for portland cementand improve structural changes to the end product (concrete and others). The use ofone unit of fly ash reduces approximately one unit of CO2 emitted by a cement kiln. Flyash and other CCPs in the cement-making process could also avoid the use of the highenergy requirement and significantly reduce the volume of useable material taken towaste management sites (Floris, Vinio and Hicks James K., 2009).

Governments and corporations are beginning to see the benefits of using CCPs formitigating greenhouse emissions. For instance, in the State of California CaliforniaAssembly Bill 32 (AB 32) was signed into law in 2006. AB 32 is seeking reductions in

greenhouse gas emissions from the production of portland cement, primarily carbondioxide. The California Air Resources Board has already passed regulations requiringannual reporting of greenhouse gases-related emissions data from portland cementmanufacturing plants. California expects a potential 1.1 million tons reduction in CO2emissions by 2020 from cement manufacturing (with a 9% reduction by 2011) and apotential 0.54 to 1.6 million t (0.6 to 1.8 million st) reduction in CO2 emissions by 2020from concrete manufacturing (with 9 percent to 27 percent replacement of portlandcement with CCPs). By 2050 an 80 percent reduction in greenhouse gas emissionsbelow 1990 levels is targeted. (www.arb.ca.gov/climatechange).

Fly ash can be used as a component in the manufacture of cement while improving the

end products of concrete, mortars and grouts (NRMCA and PCA, 2006). Use of fly ashallows their durability factors to be substantially improved. Although fly ash is a verygood substitute for cement when used as a pozzolan in portland cement concrete andother cementitious products, importantly, fly ash can be used in very high quantitieswith activated fly ash cements. These cements have been engineered for use inconventional paving, walls and concrete block masonry, new construction and repairprojects.

3. Coal-based Power Generation

Around the world, coal is primarily used as a solid fuel to produce electricity and heatthrough combustion. Globally, 25% of total energy sources come from coal while inthe US it is about 50%.Approximately, 82 percent of coal reserves (data of 2008) were concentrated in sixcountries (in descending order: USA, Russia, China, India, Australia, and SouthAfrica). The US has 29% of the reserves, 216,189 million t (238,308 million st), whileRussia and China hold 19% and 14%, respectively.

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The US produced 20% of the worlds total in 2008 while China and India produced 2.8billion and 512 million tons, respectively. China is currently the largest producer ofmined coal (41% of the worlds total). (British Petroleum, 2009)

Global coal consumption is projected to jump nearly 50% by 2030. On a tonnage basis,world coal consumption is projected to grow 47% from 6,117 Mt in 2006 to 8,995 Mtin 2030, an average annual growth rate of 1.6%. The dramatic increase in global use ofcoal is the result of a predicted 44% jump in world energy consumption (2006-2030).73% of that projected increase in world energy consumption is the result of expectedstrong economic growth in non-Organization for Economic Co-operation andDevelopment (OECD) countries. Despite the current near-term economic slump, EIAexpects demand for energy for manufacturing and consumer products to rebound after2010. EIA anticipates a 15% growth rate in OECD countries during the same period.(EIA, 2009)

Coal prices have significantly risen since the 1980s after decades of steady pricing.Appendix Figure 1 shows coal prices (US$/st) for Northwest Europe, Central

Appalachian US and Japan. US prices were about US $70/st in early 2009. Coal is,compared to other energy sources, the least expensive commodity for powergeneration. (ACAA Fact Sheet)

In 2006, there were 1,493 coal-powered units at electrical utilities across the US with atotal nominal capacity of 335.8 GW The US average generated annual power from coal(in 2006) was 227.1 GW. In 2006, China produced 195 GW and it is estimated that ithas currently surpassed the US (USEPA, 2006).

Without any global climate policies, it is expected that coal production (mainly drivenby Australia, China, Russia, Ukraine, Kazakhstan and South Africa) and consumption

may increase 30 to 50% by year 2025 (from 2007 data) (US Energy InformationAdministration, 2009).

Until more economically feasible alternatives are developed for capturing andsequestering CO2, conventional coal-based power generation will continue for decadesto come. New electric power production technologies and a resurgence in nuclearpower electric likely will begin to effect the reductions in CO2 emissions.

4. Problems, U. Environmental Protection Agency (EPA) and Fly Ash

In 1980, Congress charged the EPA to prepare a detailed study of the health and

environmental impact of coal ash. The report was presented in Year 2000 and afterdiscussion at different levels EPA determined that it did not warrant regulations as ahazardous waste under the provisions of the Resource Conservation Recovery Act.

After studying coal-fired utility wastes in 1993, the EPA decided to permanentlyexclude large volume coal fired utility wastes, including fly ash, bottom ash, boiler slagand flue gas emission control waste from the definition of hazardous waste. Studieshave shown that although trace elements may leach from coal ash in prolonged contact

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with the water table, they do not migrate far from the ash site and are present in verylow concentrations, and therefore do not present a health threat.

The 2008, a large Kingston, Tennessee TVA coal combustion residue containmentstructure collapse opened the discussion considering the amounts of arsenic, lead,barium, chromium and manganese found on that pond (Schlesinger, 2009). However,the ranges of major elements in coal fly ash and soils have been evaluated and areavailable in National Bureau of Standards Certificate of Analysis (Standard ReferenceMaterial 1633a, January 5, 1985). The comparison shows that the constituents in coalfly ash fall within the typical ranges of those in soils found across the U.S.Furthermore, fly ash is commonly used as an additive to concrete building products,not significantly different from that of more conventional concrete additives or otherbuilding materials such as granite and red brick.

CCP are considered a waste product for power generation facilities. Waste material,however, should be removed and land filled appropriately. The authors have witnessedwell-run facilities that do not pose any threats to health and the environment. Stringentregulations likely will move in that direction, but should not to the point to make the

product a hazardous material. Such an outcome would seriously affect (and most likelyend) the cement/concrete, road base and gypsum board industry that is providing asignificant benefit to the environment. Even so, utilizing the fly ash in a positivemanner such an blending to become hydraulic cement utilizes those otherwisediscarded materials.

5. Cement and Concrete

Concrete is the most widely used man-made material in the world. In 2008 nearly 2.6billion t (3 billion st) of portland and hydraulic cement was produced worldwide (PCA,2009). Cement production generates carbon-dioxide emissions because it requires fossil

fuels to heat the powdered mixture of limestone, clay, ferrous and siliceous materials totemperatures of 1,500C (2700F). Limestone (Calcium Carbonate - CaCO3) is theprinciple ingredient of cement. During the portland cement clinker calcining process,CaCO3 is changed to CaO. This conversion releases one mole of CO2 (carbon dioxide)for every mole of CaCO3 consumed in the production process. Approximately one tonof CO2 is released in the production of one ton of portland cement. In the United States,portland cement production alone constitutes about 2-3 percent of CO2 gassesgenerated annually. Given the impact that portland cement production has on theenvironment, it is incumbent on concrete manufacturers to actively pursue immediateprograms and/or practices that reduce the generation of CO2 emissions. The concreteindustry shouldnt consider this obligation a negative, however, because this

responsibility also brings the opportunity to develop innovative technological advancesin both material and a production processes.

Portland cement has long been used in standard building materials. Over the years,various modifiers have been developed for cement formulations to provide particularproperties or advantages, such as more rapid curing, compatibility with and resistanceto certain materials, and varying strengths, etc. In the past, at times the modifiedformulations have worked at cross purposes, so that a cement formulation that initially

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cures more rapidly results in a final product with a lower ultimate strength, while thehigher late strength portland cement formulations frequently cannot be demolded forsubstantial periods of time because there is not sufficient early strength.

Over the past thirty years, scientists have pursued various methods to produce a class offly ash based cement known as geo-polymers. These early precursors to presentproducts were found - even though mineral in composition - to provide many of theproperties of molding resins, such as epoxies and polyurethanes.

Some geopolymeric cementitious products are in used still today in various parts of theworld. Such geopolymers are described and claimed, for example, US Patents.(Davidovits, 1982). These geo-polymers are primarily composed of silicas andaluminas, mixed and reacted in particular ways to provide the desired structure. While,in general, these geopolymers are perfectly adequate for the purposes intended, as such,they do not always provide the types of strengths sought in a concrete composition.Furthermore, geopolymers typically require post reaction thermal processing for up to24 hours in order to achieve desirable strengths.

Below is a recent historical summary of earlier versions of pozzolan based cements:

Alkali activation of solid, non-portland cement precursors (usually high-calcium slags) was first demonstrated in reasonably modern times by Purdon in1940, and was developed on a larger scale primarily in Eastern Europe in thesucceeding decades, (vanDeventer, Jannie S.J. et. al, 2010)

1970s: Geo-polymers from fly ash, cements high in Al-Si. J. Davidovits makesreferences to their use in historical construction techniques.

1980s: Activated fly ashes blended with cement, e.g. mostly two step mixesunconditionally require addition of the activator at the jobsite.

1990s through mid-decade beginning in 2000: development of one step mixes,activator in product package or cement. The cementitious compositions typicallyconsisted of harsh acids and bases such as citric acids (pH~2.2) and alkali metalactivators including alkali hydroxides (pH~12-14) and metal carbonates(pH~11.6). These included patents by Gravitt, Kirkpatrick, Styron, Hicks andothers. There were some drawbacks to these materials. The prior art required acid-base reactions. These reactions sometimes were non-uniform and difficult tocontrol.

The art has needed and continued to seek a hydraulic cement composition, whichprovides for utilization in standard situations, while providing both a high earlystrength and an ultimate, very high strength. In particular, compositions having aminimum strength of 28 MPa (4,000 psi) at 4 hours, the release strength necessary forprestress work, have been sought.

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1970s: Geo-polymers from fly ash, cements high in Al-Si. J. Davidovits makesreferences to their use in historical construction techniques.

1980s: Activated fly ashes blended with cement, e.g. mostly two step mixesunconditionally require addition of the activator at the jobsite.

6. The New Generation of Cement Technology

This new generation of fly ash based cements offers the user a unique set of mechanicaland dimensional properties competitive in cost to current cementitious productofferings, providing the user with a value added alternative solution for todays mostchallenging construction cementitious repair, product and paving applications. The

technology is built around a highly flexible chemistry that allows for the inclusion of awide array of waste materials as part of its binder matrix, establishing it as a truly greensustainable construction material with unique performance and application advantages.

This new green cement technology is based upon an all fly ash cement design thatrequires no portland cement in its matrix. Through a detailed study of various types ofchemistry and reactive fly ash-based cement pastes, key aspects of the mineralogy havebeen identified for determining the usefulness of various fly ash sources as highperformance cements, including non acid-alkali activated cements.

Key to green cement development was creating a material matrix that had a very densecrystal structure eliminating the movement of water and other chemicals through thematerial matrix; water being the catalyst for many of the reactions that occur in theconcrete matrix.

This is accomplished through the simultaneous dissolution and retardation of theCalcium Oxide phase to solubilize both the silicate and aluminate amorphous phases.The minerals recombine to the desired structure providing desired mechanical anddimensional properties.

Thusly, pozzolanic materials are modified with chemicals to produce the desired

structure. This is denoted by the phase diagram in accompanying Figure 7. At thecorners of the diagram are the key minerals that are found in typical cements.

The red-hatched zone in the upper half of the diagram represents what is theorized tobe the perfect cement. It characterized by a very dense crystal structure exhibiting theoptimum chemical ratio of calcium to silicates to aluminates.

The micro pore structure is very small, greatly limiting the movement of liquids within

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the material matrix.

The crystal structure of portland cement is dominated by Tricalcium Silicate (C3S) andDicalcium Silicate (C2S) components producing a crystal structure that is not as denseleading to relatively a large voids structure within the material matrix. The chemicaland mineralogical improvements, coupled with the much higher fineness of pozzolanbased cements ground leads to much lower porosity in the concrete. The lowerporosity provides for very low water to cementitious ratios and improved durabilityfactors.

Having developed a technique to fingerprint raw materials as well as a road map ofgood fly ash sources, the new approach is able to maintain quality assurance on productlines using a broad array of fly ash sources, and blends of sources.

The improved activated hydraulic cement technology is the principal backbonechemistry for a range of product offerings from small area repair packaged goods tonew construction concretes. Products from the non acid-alkali activated cements weredeveloped specifically to satisfy user or application performance requirements. Each

product is water mixed, single component activated, turnkey concrete, mortar or groutwith flexible working times from 15 minutes to three hours. The products wereengineered to allow for mixing, hauling, placing and finishing using standard industryequipment and practices. The products were designed for applications where speed,strength and durability were desirable performance characteristics. Compressivestrengths of more than 17 MPa (2,500 psi) in as little as 60 minutes supported by bondstrengths of over 21 MPa (3,000 psi) and flexural strengths over 10 MPa (1,500 psi) in7 days frame the technologys mechanical properties. Dimensional stability ishighlighted by shrinkage of less than 0.04% length change in 28 days.

Principle benefits of this new class of products include:

Non-shrink.

Exceptional sustained bond strengths (slant shear and direct tension).

Low coefficient of thermal expansion.

Modulus of elasticity consistent with Portland cement concrete.

Low permeability.

High resistance to freezing and thawing.

High resistance to scaling. High resistance to sulfate and chemical attack.

Exceptional durability.

Placement temperature tolerant. No epoxy resins are contained.

Specific areas of products developed meeting objective criteria fall into several areas:

Rapid Repair Ready Mix including paving

Volumetric mixer concrete and mortar

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Concrete block/grout/mortar

Precast

High Temperature Resistant Materials.

Chemical Resistant Materials

Some of the more specific examples descriptions are:

Rapid repair products all have cementitious components greater than 90 percentcoal ash, and contain no portland cement. Based upon the size of the repair,products range in working time from 15 to 45 minutes, offering return to serviceranging from 1 to 4 hours (See Table 1). All products can be mixed withconventional mixing equipment and placed like portland cement products, however

without the requirement of bond coats.

Ready-mix truck delivery. For large placements such as roadway slabs, ash-basedpozzolanic cements have been adapted to ready-mix batch plant/transit truckmixing and placement. These products are able to be site activated (up to 4 hourstransit time), and adjusted to placement times from 1 to 3 hours. Return to servicecan be achieved in as little as 6 to 12 hours (See Table 2). Slump control can beadjusted to range from roller-compacted concrete (RCC) to a self-consolidatingconcrete (SCC).

Volumetric mobile mixer use. The volumetric pozzolanic product utilizes the same

backbone chemistry as the rapid repair products. For larger placements that alsorequire fast return to service, the pozzolans have been adapted to work in avolumetric mixer, allowing from 20 to 50 minutes of placement time, with return toservice in as little as 1 hour depending upon the user requirements. With DOT andDOD applications, the principal benefit of volumetric placement is the ability toplace larger volumes while still taking advantage of the quick return to service.One version of this product can be used as a flowable grout capable of providing upto three hours of working time, yet providing up to 35 MPa (5000 psi) incompressive strength in 24 hours.

Among the general construction and precast benefits are:

For vertical construction markets, including columns, flooring, and tilt-upconstruction, ash-based pozzolanic cements have been adapted to perform as self-consolidating concrete (SCC). These products permit easy pumping and longworking times, yet can suspend aggregate, provide sufficient placement time, andoffer early return to service. These are placed with a conventional batching andmixer system. Precast. Additional benefits of non acid-alkali activated ash-based pozzolanic

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cements also extend to precast concrete applications. Higher strength precastcomponents can be developed, offering the ability to strip molds much earlier thanwith cement based concrete. This ability permits faster turn-around and throughputto the manufacturer. High Temperature Resistant Materials. A unique benefit of ash-basedpozzolanic cements is their high temperature resistance capabilities. Ash-basedcements are naturally refractory given their amorphous glass chemistry. Coupledwith other high-temperature admixtures, these products are the only materials thathave passed Mach 1 shock testing at 1700F (927 C) for 300 cycles. This resulthas qualified the material for use as a run-up and takeoff pad for current emergingvertical takeoff aircraft (VTOL) including the AV-8, V-22 Osprey, and the newJoint Strike Fighter. Armor and Protective Materials. Non acid-alkali activated fly ash-basedpozzolanic cements are not only able to achieve high-early strength, but very highstrengths overall. In one development area, a class of cements has been developedcapable of achieving over 69 MPa (10,000) psi in 24 hours, and up to 152 MPa(22,000 psi) within 28 days. These products are in development with the US ArmyCorps of Engineers as a field emplaced armor material capable of withstanding

both blast and fragment penetration. Concrete block/grout/mortar. The non acid-alkali activated fly-ash basedpozzolanic cements have also been optimized to product both normal strength andhigh strength concrete masonry units (CMUs). Products have been able to achievestrengths ranging from 14 to 69 MPa (2,000 to 10,000 psi) using conventionalconcrete block manufacturing facilities, techniques, and cement percentages equalto those used by conventional cement.

7. Conclusions

Despite all global warming concerns and being in the midst of a financial crisis, an

approximate growth of 30-50 percent of coal power generation is expected betweenYears 2007 to 2025. The installed capacity would jump to approximately 2.1 millionMW. Initial estimates were even higher but the US and Europe are scaling back due tostrong environmental pressures. China alone would add approximately 350,000 MWduring this period while India would follow with more than 100,000 MW.

As it was examined in Sections 2, 3 and 4, it is essential to emphasize that the use ofCCP could make key reductions in CO2 emissions by using byproducts to makecement, substituting for portland cement in concrete, and reducing energy given theenergy-efficient nature of concrete structures. It is important to point out that the CCPoption is only available for pulverized coal plants. IGCC units follow a different

technique and do not produce any cementitious materials as by-products.

These cutting-edge, next-generation green non acid-alkali activated fly-ash basedpozzolanic cements provide the construction a value added alternative to traditionalcement product offers. The extent of engineering that has been done with the productoffers widest range of end-use applications from any pozzolan, removing it from itsprevious limited use as a short-life rapid repair product only. Moreover, the amount ofresearch that has been conducted on understanding fly-ash chemistry and mineralogy

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has extended the ability to use a much wider range of high calcium coal ash whilemaintaining predictable product performance. These truly green building materials arecomprised largely of renewable, recyclable or reusable resources. They are the onlycements in the world whose chemical matrix is comprised of more than 95% wastematerials. See Figure 5.

This new generation of all ash-based pozzolanic cements also furthers the ability toutilize green building technology for the widest range of end-use markets, includingmost DOT, DOD, and building construction market applications while meetingInternational Building Code and ASTM Standards.

It is important to note that although the environmental and even economic benefitsfrom using CCPs are apparent, they are still underutilized. The American Coal AshAssociation reported that less than 40 percent of CCP are used. The Association onlyreports affiliated utilities. The authors estimate that less than those amounts arecurrently used and end up in landfills, creating a burden to the environment and theeconomy of different enterprises.

We all need to understand that we must adopt sustainable energy policies to avoidendangering energy security and control carbon emissions. Without any intervention,CO2 could increase 42.4 Gigatons in 2035 from 29.7 in 2007 (EIA, 2010). Thisincrease is a real and immense challenge that has to be managed promptly.1

KEYWORDS: Recycled, cement, green, concrete, CO2 reduction, CCP, Sustainable

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8. References

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promptly.

Figure 4. 1996-2007 CCP Beneficial Use versus production. Source: American Coal Ash Association.

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References

American Coal Ash Association. 2005.ACAA Fly Ash basics Quick Reference Card.

American Coal Ash Association.Coal Combustion Products: Not a Hazardous Waste.

British Petroleum. 2009.BP Statistical Review of World Energy.

Floris, Vinio, Hicks James K., 2009.Environmental Benefits of Coal Combustion Products,Pittsburgh, Coal Conference.

Floris, Vinio. 2009. Challenges and Achievements of Coal-Based Power Generation:Moving Towards a Holistic and Sustainable Approach. Proceedings of the InternationalAssociation of Energy Economics, Santiago, Chile.

Hicks, James K., Mike Riley, Glenn Schumacher, Raj Patel and Paul Sampson. 2009.

Utilization of Recovered Materials for High Quality Cements and Products.

Massachusetts Institute of Technology. 2007. The future of Coal.

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Schlesinger, Richard. April/March 2009. Coal Ash Piles Up. Energybiz.

US Energy Information Administration. 2007. US Coal Supply and Demand, 2007 Review.

US Environmental Protection Agency. 2008.Inventory of U.S. Greenhouse Gas Emissionsand Sinks: 1990-2006, Report No. 430-R-08-005.

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1

World CO2-Emissions Growth Keeps Focus on Coal,Bloomberg Business Week, June 10, 2009United States Environmental Protection Agency (USEPA),Recent Trends in U.S. Greenhouse Gas,

Climate Change, Emissions, 2010 Inventory of Greenhouse Gas Emissions and Sinks ,www.epa.gov/climatechange/emissions

British Petroleum,BP Statistical Review of World Energy, (2009)

EIA International Energy Outlook, EIA predicts surge in world coal consumption, www.im-mining.com/2009/06/07/eia-predicts-surge-in-world-coal-consumption/2009American Coal Ash Association (ACAA), 2007 Fly Ash Survey, (2008)Hicks, James K., Mike Riley, Glenn Schumacher, Raj Patel and Paul Sampson, Utilization of Recovered

Materials for High Quality Cements and Products, World of Coal Ash, University of KentuckyCenter for Applied Energy Research, Lexington, KY, 2009.

Van Ost, Hendrik G, United States Geological Survey, Cement, 2002Huntzinger, Deborah N and Eatmon, Thomas D.,Journal of Cleaner Production, Elsevier, (2009) 668

675Floris, Vinio, Challenges and Achievements of Coal-Based Power Generation: Moving Towards a

Holistic and Sustainable Approach.Proceedings of the International Association of Energy

Economics, Santiago, Chile (2009).Floris, Vinio, Hicks James K., Environmental Benefits of Coal Combustion Products, Pittsburgh CoalConference, University of Pittsburg, PA (2009).

California Environmental Protection Agency, Air Resources Board, www.arb.ca.gov/climatechange(2010)

Ready Mixed Concrete (RMC) Research Foundation and the Portland Cement Association (PCA), TheReady Mixed Concrete Industry LEED Reference Guide,nrmca.org/greenconcrete/LEEDreference guide (2009)

US Coal Supply and Demand, 2007 Review, www.eia.doe.gov.coal, 2007

US Environmental Protection Agency. 2008. Inventory of U.S. Greenhouse Gas Emissions and Sinks:1990-2006,Report No. 430-R-08-005,www.epa.gov/climatechange/emissions/usgginventory.html

US Energy Information Administration. www.eia.doe.gov 2007

Schlesinger, Richard.Energybiz, Coal Ash Piles Up (April/March 2009)Portland Cement Association (PCA),Economic Research, Market Data Reports, www.cement.org (2009)Davidovits, Joseph, United States Patent Office (USPTO), U.S. Pat. Nos. 4,349,386 (1982) and

4,472,199 (1984), www.USPTO.gov

van Deventer, Jannie S.J., et. al, The role of research in the commercial development of geopolymerconcrete, International Cement Microscopy Association, March 2010 Conference,www.cemmicro.org

U. S. Energy Information Administration, 2010 CO2 Forecast Highlights, www.eia.doe.gov/international(2010)
http://www.epa.gov/climatechange/emissionshttp://www.arb.ca.gov/climatechangehttp://www.eia.doe.gov.coal/http://www.cement.org/http://www.google.com/url?q=http://www.eia.doe.gov/emeu/international/contents.html&sa=X&ei=c0c2TPbXIeXtnQf1-LH4Aw&ved=0CCkQ6QUoAA&usg=AFQjCNEZvVp_hoWLn-FM3W46lHntlhpvOwhttp://www.epa.gov/climatechange/emissionshttp://www.arb.ca.gov/climatechangehttp://www.eia.doe.gov.coal/http://www.cement.org/http://www.google.com/url?q=http://www.eia.doe.gov/emeu/international/contents.html&sa=X&ei=c0c2TPbXIeXtnQf1-LH4Aw&ved=0CCkQ6QUoAA&usg=AFQjCNEZvVp_hoWLn-FM3W46lHntlhpvOw


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LIST OF TABLES AND FIGURES

Figure 1. Price changes of coal in different regions of the world.Figure 2. 2006 US sources of CO2 emissions.Figure 3. 1996-2007 CCP Beneficial Use versus production.Figure 4. World net Electricity generation by fuel, 2007-2035Figure 5. Construction of base for a heat treating facility in Houston, Texas.Figure 6. Micrograph of CSH Formation in Activated Fly Ash Cement.Figure 7. CeraTech Cement design.Figure 8. Marine Corps Concrete Installation

Table 1. Performance characteristics of an activated pozzolan based cement repair materialTable 2. Characteristics of an activated pozzolan cement fast return to service ready mixed concrete


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0.00

40.00

80.00

120.00

160.00

200.00

1990 1994 1998 2002 2006

Years

Price(US$/ton

ne)

Northwest Europe marker price

US Central Appalachian coal spot price

indexJapan coking coal import cif price

Japan steam coal import cif price

Figure 1. Price changes of coal in different regions of the world.Source: British Petroleum, Statistical Review of World Energy 2008.


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Figure 2: Teragrams of CO2 Equivalents

Source: US EPA, 2006 US sources of CO2 emissions.Inventory of U.S. Greenhouse Gas Emissions and Sinks: 1990-200


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Figure 3. 1996-2007 CCP Beneficial Use versus production.

Source: American Coal Ash Association


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Figure 4. World net Electricity generation by fuel, 2007-2035

(trillion kilowatt hours)

Source, U. S Energy Administration 2010 CO2 forecast highlights


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Figure 5.Construction of base for a heat treating facility in Houston, Texas. Cycling of

temperatures caused severe breakdown of conventional concrete.

Source: James K. Hicks, et al (2009).


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Figure 6. Micrograph of CSH Formation in Activated Fly Ash Cement, Sample age is 14 months

from addition of water

Source: James K. Hicks, et. al. (2009).


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Figure 7. Ternary phase diagram showing theoretical cement, CeraTech Cement design.

Source: CeraTech, Inc.


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Figure 8. Marine Corps Engineers training for fast track construction and repair prior to

deployment. Marine Corps Base Concrete Installation

Source: James K. Hicks, et al (2009).

Table 1. Performance characteristics of an activated pozzolan based cement repair material. All

testing was performed with air cured specimens.Source: CeraTech, Inc.


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Table 2. Characteristics of an activated pozzolan cement fast return to service ready mixed

concrete. 1

Source, CeraTech, Inc.


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Notes:

1. Strength development and working times can be adjustedby varying the cement ratio and by use of various proprietary activatoradmixtures.2. Test results based on 846 lbs. of cement per cubic yard mix design and Fast Set Activator3. Test results based on 564 lbs. of cement per cubic yard mix design and Fast Set Activator

Hicks Publication - Durable Green Cements From CCPs Final A

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