US20100286312A1 - Amine Sacrificial Agents and Methods and Products Using Same - Google Patents

Amine Sacrificial Agents and Methods and Products Using Same Download PDF

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US20100286312A1
US20100286312A1 US12/436,648 US43664809A US2010286312A1 US 20100286312 A1 US20100286312 A1 US 20100286312A1 US 43664809 A US43664809 A US 43664809A US 2010286312 A1 US2010286312 A1 US 2010286312A1
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Prior art keywords
fly ash
substituted
unsubstituted
alkoxylated
air
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US12/436,648
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Zhaozhou Zhang
Russell L. Hill
Brian Shaw
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Ruetgers Polymers Ltd
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Boral Material Technologies LLC
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Priority to US12/436,648 priority Critical patent/US20100286312A1/en
Assigned to BORAL MATERIAL TECHNOLOGIES INC. reassignment BORAL MATERIAL TECHNOLOGIES INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HILL, RUSSELL L., SHAW, BRIAN, ZHANG, ZHAOZHOU
Priority to PCT/US2010/033765 priority patent/WO2010129700A2/fr
Priority to CA 2755558 priority patent/CA2755558A1/fr
Priority to AU2010245946A priority patent/AU2010245946A1/en
Publication of US20100286312A1 publication Critical patent/US20100286312A1/en
Priority to US13/329,782 priority patent/US20120085264A1/en
Assigned to RUETGERS POLYMERS LTD. reassignment RUETGERS POLYMERS LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BORAL MATERIALS TECHNOLOGIES INC.
Priority to US13/725,076 priority patent/US8652249B2/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B16/00—Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
    • C04B18/08—Flue dust, i.e. fly ash
    • C04B18/084—Flue dust, i.e. fly ash obtained from mixtures of pulverised coal and additives, added to influence the composition of the resulting flue dust
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
    • C04B2111/1087—Carbon free or very low carbon content fly ashes; Fly ashes treated to reduce their carbon content or the effect thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • This application relates to the use of sacrificial agents in cementitious mixtures containing ash including fly ash concrete, and to the resulting mixtures and compositions. More particularly, this application relates to sacrificial agents that reduce or eliminate the detrimental effects of ash such as fly ash on the air entrainment properties of cementitious mixtures.
  • fly ash can impart many beneficial properties to concrete such as improved rheology, reduced permeability and increased later-age strength; however, it also may have a negative influence on bleed characteristics, setting time and early strength development. Many of these issues can be managed by adjusting mixture proportions and materials, and by altering concrete placement and finishing practices. However, other challenging problems encountered when using certain fly ash are not always easily resolved. The most important difficulties experienced when using fly ash are most often related to air entrainment in concrete.
  • Air entrained concrete has been utilized in the United States since the 1930's. Air is purposely entrained in concrete, mortars and grouts as a protective measure against expansive forces that can develop in the cement paste associated with an increase in volume resulting from water freezing and converting to ice. Adequately distributed microscopic air voids provide a means for relieving internal pressures and ensuring concrete durability and long term performance in freezing and thawing environments. Air volumes (volume fraction) sufficient to provide protective air void systems are commonly specified by Building Codes and Standard Design Practices for concrete which may be exposed to freezing and thawing environments. Entrained air is to be distinguished from entrapped air (air that may develop in concrete systems as a result of mixing or the additions of certain chemicals). Entrained air provides an air void system capable of protecting against freeze/thaw cycles, while entrapped air provide no protection against such phenomena.
  • Air is also often purposely entrained in concrete and other cementitious systems because of the properties it can impart to the fresh mixtures. These can include: improved fluidity, cohesiveness, improved workability and reduce bleeding.
  • the air void systems are generated in concrete, mortar, or paste mixtures by introducing air entrainment admixtures (referred to as air entrainment agents or air-entraining agents) which are a class of specialty surfactants.
  • air entrainment agents or air-entraining agents
  • fly ash the difficulties in producing air-entrained concrete are related to the disruptive influence that some fly ashes have on the generation of sufficient air volumes and adequate air void systems.
  • the primary influencing factor is the occurrence of residual carbon, or carbonaceous materials (hereafter designated as fly ash-carbon), which can be detected as a discrete phase in the fly ash, or can be intimately bound to the fly ash particles. Detrimental effects on air entrainment by other fly ash components may also occur, and indeed air entrainment problems are sometimes encountered with fly ash containing very low amounts of residual carbon.
  • fly ash-carbon a residue of incomplete coal or other hydrocarbon combustion, is in many ways similar to an “activated carbon.” For example, like activated carbon, fly ash-carbon can adsorb organic molecules in aqueous environments. In cement paste containing organic chemical admixtures, the fly ash-carbon can thus adsorb part of the admixture, interfering with the function and performance of the admixture. The consequences of this adsorption process are found to be particularly troublesome with air entrainment admixtures (air entrainment agents) which are commonly used in only very low dosages. In the presence of significant carbon contents (e.g.
  • the air entrainment agents may be adsorbed, interfering with the air void formation and stability; this leads to tremendous complications in consistently obtaining and maintaining specified concrete air contents.
  • ASTM guidelines have limited the fly ash carbon content to less than 6 wt %.
  • Other institutions such as AASHTO and state departments of transportation have more stringent limitations.
  • Industry experience indicates that, in the case of highly active carbon (for example, high specific surface area), major interferences and problems can still be encountered, even with carbon contents lower than 1 wt %.
  • fly ash carbon content as measured by loss on ignition (LOI) values
  • LOI loss on ignition
  • Variations in fly ash performance are important, not only because of their potential impact on air entrainment and resistance to freeze thaw conditions, but also because of their effects related to concrete strength.
  • concrete is designed according to building standards for a particular environment, specifications are also provided for physical performance requirements.
  • a common performance requirement is compressive strength.
  • An increase in entrained air content can result in a reduction in compressive strength of 3-6% for each additional percentage of entrained air.
  • variations in fly ash-carbon which would lead to erratic variations in air contents, can have serious negative consequences on the concrete strength.
  • fly ash-carbon air entrainment problem is an on-going issue that has been of concern since fly ash was first used nearly 75 years ago. Over the past ten years, these issues have been further exacerbated by regulations on environmental emissions which impose combustion conditions yielding fly ash with higher carbon contents. This situation threatens to make an increasingly larger portion of the available fly ash materials unsuitable for use in concrete. Considering the economic impact of such a trend, it is imperative to develop practical corrective schemes that will allow the use, with minimal inconvenience, of fly ash with high carbon contents (e.g., up to 10 wt %) in air-entrained concrete.
  • high carbon contents e.g., up to 10 wt %
  • Air entrainment in fly ash-concrete may become yet more complicated by pending regulations that will require utilities to reduce current mercury (Hg) emissions by 70-90%.
  • Hg current mercury
  • One of the demonstrated technologies for achieving the Hg reduction is the injection of activated carbon into the flue gas stream after combustion so that volatile Hg is condensed on the high surface area carbon particles and discarded with the fly ash.
  • Current practices are designed such that the added activated carbon is generally less than 1% by mass of the fly ash, but preliminary testing indicates this is disastrous when using the modified fly ash in air-entrained concrete.
  • fly ash treatment approaches have found limited application due to their inherent limitations (e.g., separation techniques have limited efficiency in low carbon fly ash; secondary combustion processes are most suitable for very high carbon contents), or due to their associated costs.
  • the methods and compositions described herein facilitate the formation of cementitious mixtures containing fly ash and other combustion ashes, and solid products derived therefrom. Further, these methods and compositions facilitate air entrainment into such mixtures in a reliable and predictable fashion.
  • a method of reducing or eliminating the effect of fly ash or other combustion ashes on air-entrainment in an air-entraining cementitious mixture containing fly ash or another combustion ash comprising the steps of: forming a cementitious mixture comprising water, cement, fly ash or another combustion ash, (and optionally other cementitious components, sand, aggregate, etc.) and an air entrainment agent (and optionally other concrete chemical admixtures); and entraining air in the mixture; wherein an amount of at least one sacrificial agent is also included in the cementitious mixture in at least an amount necessary to neutralize the detrimental effects of components of said fly ash or other combustion ash on air entrainment activity, the sacrificial agent comprising a material or mixture of materials that, when present in the same cementitious mixture without fly ash or the other combustion ash in said amount, causes less than 2 vol. % additional air content in the cementitious mixture.
  • the amount of the sacrificial agent used in the cementitious mixture can, in some embodiments, exceed the amount necessary to neutralize the detrimental effects of the components of the fly ash or other combustion ash.
  • the fly ash varies in content of the detrimental components from a minimum content to a maximum content according to the source or batch of the fly ash or other combustion ash, the amount of the at least one sacrificial agent can exceed the amount necessary to neutralize the detrimental effects of the components of the fly ash when present at their maximum content.
  • the sacrificial agent is a primary amine, secondary amine, or tertiary amine compound, or any combination thereof.
  • the sacrificial agent can be a compound selected from the group consisting of the structure NR 1 R 2 R 3 .
  • R 1 is substituted or unsubstituted non-alkoxylated C 5-22 alkyl, substituted or unsubstituted non-alkoxylated C 5-22 alkenyl, substituted or unsubstituted non-alkoxylated C 5-22 alkynyl, substituted or unsubstituted C 2-22 alkoxylated alkyl, substituted or unsubstituted C 2-22 alkoxylated alkenyl, or substituted or unsubstituted C 2-22 alkoxylated alkynyl.
  • R 2 and R 3 are each independently selected from hydrogen, substituted or unsubstituted C 1-22 alkyl, substituted or unsubstituted C 2-22 alkenyl, or substituted or unsubstituted C 2-22 alkynyl.
  • R 2 and R 3 can be optionally alkoxylated.
  • One or more of R 1 , R 2 , or R 3 can be an alkoxylated or non-alkoxylated, substituted or unsubstituted, fatty acid residue.
  • the fatty acid residues can be saturated fatty acid residues, monounsaturated fatty acid residues, polyunsaturated fatty acid residues, or mixtures thereof.
  • R 1 , R 2 , and R 3 can be amino-substituted including NR 4 R 5 as a substituent.
  • the sacrificial agent can be polyoxypropylenediamine or triethyleneglycol diamine.
  • the sacrificial agent is an alcoholamine.
  • the sacrificial agent is a mixture of two or more compounds.
  • the HLB value of the sacrificial agent or the mixture of sacrificial agents is in the range of 5 to 20 (e.g., 4 to 18).
  • the Log K ow for the sacrificial agent can be in the range of ⁇ 3 to +2 (e.g. ⁇ 2 to +2).
  • the sacrificial agent is a compound selected from tridodecylamine, dodecyldimethylamine, octadecyldimethylamine, cocoalkyldimethylamine, hydrogenated tallowalkyldimethylamines, oleyldimethylamine, dicocoalkylmethylamine, N-oleyl-1,1′-iminobis-2-propanol, N-tallowalkyl-1,1′-iminobis-2-propanol, polyoxypropylenediamine, triethyleneglycol diamine, and mixtures thereof.
  • the sacrificial agent includes dodecyldimethylamine.
  • the sacrificial agent includes one or more compounds selected from N-oleyl-1,1′-iminobis-2-propanol and N-tallowalkyl-1,1′-iminobis-2-propanol. In some embodiments, the sacrificial agent includes a polyetheramine.
  • the dosage, or amount, of the sacrificial agent can vary from 0.005% to 5% by weight based on the weight of the fly ash or other combustion ash. In some embodiments, the amount is from 0.01 to 2%, 0.02-1% and 0.05-0.5% (e.g. 0.1-0.3%) by weight based on the weight of the fly ash or other combustion ash.
  • the sacrificial agent can be added directly to the fly ash by pre-treating the fly ash or can be added to the cementitious composition or with other components of the cementitious composition.
  • the fly ash or other combustion ash is provided in the cementitious composition in an amount of from 5% to 55% by weight of the total amount of cementitious materials in the cementitious composition (cement and fly ash or other combustion ash), depending on the type and composition of the fly ash or other combustion ash.
  • the amount of fly ash or other combustion ash is from 10% to 50% or 15% to 30% by weight (e.g. 25% by weight) of the total amount of cementitious materials in the cementitious composition.
  • the sacrificial agent can be mixed with the air entrainment agent prior to mixing the sacrificial agent and air entrainment agent with the fly ash or other combustion ash, cement, and water.
  • the sacrificial agent can be mixed with the fly ash or other combustion ash prior to mixing the sacrificial agent and the fly ash or other combustion ash with the cement, water, and the air entrainment agent.
  • the sacrificial agent can be added to the fly ash or other combustion ash by spraying a liquid containing the sacrificial agent onto the fly ash or other combustion ash, or by mixing a spray-dried solid sacrificial agent formulation with the fly ash or other combustion ash.
  • the sacrificial agent can be added after the fly ash or other combustion ash, cement, water, and air entrainment agent have been mixed together.
  • an additional material selected from sand, aggregate, concrete modifier, and combinations thereof, can be incorporated into the mixture.
  • the cementitious mixture can be formed by mixing an amount of the sacrificial agent with the fly ash or other combustion ash to form a pre-treated fly ash or other combustion ash, and then mixing the pre-treated fly ash or other combustion ash with the water, air entrainment agent and cement.
  • the cementitious mixture is formed by mixing the air entrainment agent and the sacrificial agent to form a component mixture, and then mixing the component mixture with the water, fly ash or other combustion ash and cement, and entraining the air in the mixture.
  • water, cement, fly ash or other combustion ash, air entrainment agent and sacrificial agent are mixed together simultaneously while entraining the air in the mixture.
  • the sacrificial agent is mixed with the water, cement and fly ash or other combustion ash before the air entrainment agent is added. In some embodiments, the sacrificial agent is mixed with the water, cement, and fly ash or other combustion ash at the same time as the air entrainment agent.
  • the fly ash or other combustion ash consists essentially of fly ash. In some embodiments, the fly ash or other combustion ash comprises a blend of fly and another combustion ash. In some embodiments, the sacrificial agent, when present in the same cementitious mixture without fly ash or the other combustion ash in the appropriate amount causes less than 1 vol. % additional air content in the cementitious mixture.
  • the method further includes the step of selecting a sacrificial agent including a material or mixture of materials to reduce or eliminate the effect of fly ash or another combustion ash on air entrainment in a cementitious mixture and selecting an amount of the sacrificial agent such that the amount is at least an amount necessary to neutralize the detrimental effects of components of the fly ash on air entrainment activity and the amount of sacrificial agent causes less than 2 vol. % additional air content in the same cementitious mixture without fly ash or the other combustion ash.
  • the fly ash or other combustion ash has a predetermined maximum carbon content and the amount of sacrificial agent exceeds the amount necessary to neutralize the maximum carbon content in the fly ash or other combustion ash.
  • the sacrificial agent amount used does not result in a substantial increase in air entrainment compared to providing the sacrificial agent in an amount necessary to neutralize the detrimental effects of components of the fly ash on air entrainment activity.
  • the sacrificial agent causes less than 2 vol. % additional air content in the cementitious mixture without fly ash.
  • the components to be neutralized are carbon content.
  • a method of reducing or eliminating the effect of fly ash on air entrainment in an air-entraining cementitious mixture comprising the steps of: forming a cementitious mixture comprising water, cement, fly ash, and an air entrainment agent, and entraining air in the mixture; wherein a sacrificial agent is also included in the cementitious mixture in at least the amount necessary to neutralize the detrimental effects of the carbon content of said fly ash on air entrainment activity, the sacrificial agent comprising a material or mixture of materials that, when present in the same cementitious mixture without fly ash in said amount causes less than 2 vol. % additional air content in the cementitious mixture.
  • a method of addressing the variance of carbon content in fly ash used in cementitious compositions to provide a cementitious composition with a substantially constant level of air entrainment comprising: forming a cementitious mixture comprising water, cement, fly ash, an air entrainment agent, and a sacrificial agent and entraining air in the mixture, wherein the fly ash has a maximum carbon content; and selecting a sacrificial agent for the cementitious mixture and an amount of the sacrificial agent such that the amount of the sacrificial agent exceeds the amount necessary to neutralize the maximum carbon content in the fly ash, wherein the sacrificial agent comprises a material or mixture of materials that, when present in the same cementitious mixture without fly ash in said amount causes less than 2 vol. % additional air content in the cementitious mixture.
  • a method of pre-treating fly ash or another combustion ash to reduce or eliminate the effect the fly ash or the other combustion ash has on air entrainment in an air-entraining cementitious mixture comprising the fly ash or other combustible fly ash and an air-entraining agent comprising: mixing a sacrificial agent with fly ash or another combustion ash to form a pre-treated ash, wherein the sacrificial agent is combined with the fly ash or the other combustion ash in at least an amount necessary to neutralize the detrimental effects of components of the fly ash or the other combustion ash on air entrainment activity in the air-entraining cementitious mixture, the sacrificial agent comprising a material or mixture of materials that, when present in a cementitious mixture without fly ash or another combustion ash in said amount causes less than 2 vol. % additional air content in the cementitious mixture.
  • a method of addressing the variance of carbon content in fly ash used in cementitious compositions to provide a cementitious composition with a substantially constant level of air entrainment comprising: selecting a sacrificial agent and an amount of the sacrificial agent such that the amount of the sacrificial agent exceeds the amount necessary to neutralize the maximum carbon content in the fly ash, mixing the sacrificial agent with fly ash or another combustion ash to form a pre-treated ash, wherein the sacrificial agent is combined with the fly ash or the other combustion ash in at least an amount necessary to neutralize the detrimental effects of components of the fly ash or the other combustion ash on air entrainment activity in the air-entraining cementitious mixture, the sacrificial agent comprising a material or mixture of materials that, when present in a cementitious mixture without fly ash or another combustion ash in said amount causes less than 2 vol. % additional air content in the cementitious mixture
  • compositions comprising fly ash or another combustion ash that reduces or eliminates the effect the fly ash or the other combustion ash has on air entrainment in an air-entraining cementitious mixture comprising the fly ash or the other combustion ash and an air-entraining agent, the composition comprising fly ash or another combustion ash and a sacrificial agent, the sacrificial agent present in at least an amount necessary to neutralize the detrimental effects of components of the fly ash or the other combustion ash on air entrainment activity in the air-entraining cementitious mixture, the sacrificial agent comprising a material or mixture of materials that, when present in a cementitious mixture without fly ash or another combustion ash in said amount causes less than 2 vol. % additional air content in the cementitious mixture.
  • compositions that addresses the variance of carbon content in fly ash or another combustion ash used in cementitious compositions to provide a cementitious composition with a substantially constant level of air entrainment, comprising fly ash or another combustion ash and a sacrificial agent, the sacrificial agent present in at least an amount necessary to neutralize the detrimental effects of components of the fly ash or the other combustion ash on air entrainment activity in the air-entraining cementitious mixture, the sacrificial agent comprising a material or mixture of materials that, when present in a cementitious mixture without fly ash or another combustion ash in said amount causes less than 2 vol. % additional air content in the cementitious mixture.
  • an air-entraining cementitious mixture comprising fly ash or another combustion ash that reduces or eliminates the effect the fly ash or other combustion ash has on air entrainment in the air-entraining cementitious mixture;
  • the air-entraining cementitious mixture comprising air, water, cement, fly ash, an air entrainment agent and a sacrificial agent, wherein the sacrificial agent is present in at least an amount necessary to neutralize the detrimental effects of components of the fly ash or the other combustion ash on air entrainment activity in the air-entraining cementitious mixture, the sacrificial agent comprising a material or mixture of materials that, when present in a cementitious mixture without fly ash or another combustion ash in said amount causes less than 2 vol. % additional air content in the cementitious mixture.
  • an air-entraining cementitious mixture comprising fly ash or another combustion ash that addresses the variance of carbon content in fly ash used in cementitious compositions to provide a cementitious composition with a substantially constant level of air entrainment
  • the air-entraining cementitious mixture comprising air, water, cement, fly ash, an air entrainment agent and a sacrificial agent, wherein the sacrificial agent is present in at least an amount necessary to neutralize the detrimental effects of components of the fly ash or the other combustion ash on air entrainment activity in the air-entraining cementitious mixture
  • the sacrificial agent comprising a material or mixture of materials that, when present in a cementitious mixture without fly ash or another combustion ash in said amount causes less than 2 vol.
  • the sacrificial agent is present in at least an amount necessary to neutralize the detrimental effects of components of the fly ash or the other combustion ash on air entrainment activity in the air-entraining cementitious mixture, the sacrificial agent comprising a material or mixture of materials that, when present in a cementitious mixture without fly ash or another combustion ash in said amount causes less than 2 vol. % additional air content in the cementitious mixture.
  • an air-entrained hardened cementitious mass comprising fly ash or another combustion ash that reduces or eliminates the effect the fly ash or other combustion ash has on air entrainment in the air-entrained hardened cementitious mass
  • the air-entrained hardened cementitious mass comprising air, cement, fly ash, an air entrainment agent and an amount of a sacrificial agent, wherein the sacrificial agent is present in at least an amount necessary to neutralize the detrimental effects of components of the fly ash or the other combustion ash on air entrainment activity in the air-entraining cementitious mixture
  • the sacrificial agent comprising a material or mixture of materials that, when present in a cementitious mixture without fly ash or another combustion ash in said amount causes less than 2 vol. % additional air content in the cementitious mixture.
  • the sacrificial agents can be used to eliminate or drastically reduce air entrainment problems encountered in concrete containing fly ash.
  • Such additives, or combinations of such additives can be added before (e.g. in the fly ash material), during, or after the concrete mixing operation.
  • the use of these materials can have the following advantages. They:
  • the cementitious mixtures can contain conventional ingredients such as sand and aggregate, as well as specific known additives.
  • combustion ash refers to a by product of coal combustion.
  • other combustion ashes can be employed which are fine ashes or flue dusts resulting from co-firing various fuels with coal, or resulting from the combustion of other fuels that produce an ash having pozzolanic qualities (the ability to form a solid when mixed with water and an activator such ash lime or alkalis) or hydraulic qualities (the ability to form a solid when mixed with water and set).
  • the ash itself has pozzolanic/hydraulic activity and can be used as a cementitious material to replace a portion of portland cement in the preparation of concrete, mortars, and the like.
  • the term “fly ash and other combustion ash” as used herein includes:
  • fly ash concrete means concrete containing fly ash and portland cement in any proportions, but optionally additionally containing other cementitious materials such as blast furnace slag, silica fume, or fillers such as limestone, etc.
  • surfactants is also well understood in the art to mean surface active agents. These are compounds that have an affinity for both fats (hydrophobic) and water (hydrophilic) and so act as foaming agents (although some surfactants are non-foaming, e.g. phosphates), dispersants, emulsifiers, and the like, e.g. soaps.
  • air entrainment agent means a material that results in a satisfactory amount of air being entrained into a cementitious mixture, e.g. 5-9 vol % air, when added to a cementitious formulation.
  • air entrainment agents are surfactants (i.e. they reduce the surface tension when added to aqueous mixtures), and are often materials considered to be soaps.
  • the performance of surfactants as concrete air entrainment admixture depends on the composition of the surfactant: the type of hydrophilic group (cationic, anionic, zwitterionic, or non-ionic), the importance of its hydrophobic residue (number of carbon groups, molecular weight), the chemical nature of this residue (aliphatic, aromatic) and the structure of the residue (linear, branched, cyclic), and on the balance between the hydrophilic and lipophilic portions of the surfactant molecule (HLB).
  • Cationic and non-ionic surfactants are reported to entrain more air than anionic surfactants because the latter are often precipitated as insoluble calcium salts in the paste solution; however, the stability of the air void has also been reported to be greater with anionic surfactant than with cationic or non-ionic surfactants.
  • Typical examples of compounds used as surface active agents are sodium salts of naturally occurring fatty acid such as tall oil fatty acid, and sodium salts of synthetic n-alkylbenzene sulfonic acid.
  • Common concrete air entrainment (or air-entraining) agents include those derived from the following anionic surfactants: neutralized wood resins, fatty acids salts, alkyl-aryl sulfonates, and alkyl sulfates.
  • sacrificial agent means a material, or a mixture of materials, that interacts with (and/or neutralizes the detrimental effects of) components of fly ash that would otherwise interact with an air entrainment agent and reduce the effectiveness of the air entrainment agent to incorporate air (or other gas) into the cementitious mixture.
  • the sacrificial agents are not “air entrainment agents” as they are understood in the art and, in the amounts used in the cementitious mixture, do not cause more than 2 vol % additional air content (or even less than 1 vol % additional air content) into the same mixture containing no fly ash.
  • the sacrificial agent in the amounts employed in fly ash-containing mixtures, is responsible for introducing less than 0.5 vol % or even substantially no additional air content into the same mixture containing no fly ash. In some embodiments, the sacrificial agent neither promotes nor inhibits the functioning of the air entrainment agent compared with its functioning in a similar mixture containing no fly ash.
  • cementitious mixture means a mixture such as concrete mix, mortar, paste, grout, etc., that is still in castable form and that, upon setting, develops into a hardened mass suitable for building and construction purposes.
  • cement means a product (other than fly ash) that is capable of acting as the principal hardenable ingredient in a cementitious mixture.
  • the cement is portland cement, but at least a portion can include blast furnace slag, gypsum, and the like.
  • percent or “%” as used herein in connection with a component of a composition means percent by weight based on the cementitious components (cement and fly ash) of a cementitious mixture (unless otherwise stated). When referring to air content, the term % means percent by volume or vol %.
  • alkyl can include straight-chain and branched monovalent substituents. Examples include methyl, ethyl, isobutyl, 2-propenyl, 3-butynyl, and the like.
  • substituted indicates the main substituent has attached to it one or more additional components, such as, for example, amino, hydroxyl, carbonyl, or halogen groups.
  • unsubstituted indicates that the main substituent has a full compliment of hydrogens, i.e., commensurate with its saturation level, with no substitutions, e.g., linear decane (—(CH 2 ) 9 —CH 3 ).
  • alkoxylated as used herein is an adjective referring to a compound having an “alkoxyl” linkage having the formula —(OR) n — wherein R can be an alkyl, alkenyl, or alkynyl group.
  • R can be an alkyl, alkenyl, or alkynyl group.
  • suitable “R” groups include ethyl (ethoxylate), propyl (propoxylate), or butyl (butoxylate)groups.
  • the value for n is an average value and can vary for the sacrificial agent (where alkoxylation is present) from 1 to 10, 1.5 to 9 or 2 to 8.
  • FIG. 1 is a graph illustrating the competitive absorption by activated carbon with various sacrificial agents at saturated concentrations.
  • FIG. 2 is a graph illustrating the percentage of air in concrete with increasing concentrations of an air entrainment agent with various activated carbon samples at varying amounts.
  • FIG. 3 is a graph illustrating the dosage of an air entrainment agent at 6% air in concrete with increasing amounts of carbon contents.
  • FIG. 4 is a graph illustrating the percentage of air in concrete with increasing concentrations of an air entrainment agent with various amounts of activated carbon.
  • FIG. 5 is a graph illustrating the percentage of air in concrete with increasing concentrations of an air entrainment agent with sacrificial agents and activated carbon.
  • FIG. 6 is a graph illustrating the percentage of air in concrete with increasing concentrations of an air entrainment agent with sacrificial agent-treated fly ash combined with activated carbon.
  • FIG. 7 is a graph illustrating the percentage of air in concrete with increasing concentrations of an air entrainment agent with sacrificial agent-treated fly ash with and without activated carbon.
  • FIG. 8 is a graph illustrating the percentage of air in concrete with increasing percentages of activated carbon in the presence of an air entrainment agent and with and without sacrificial agents.
  • FIG. 9 is a graph illustrating the percentage of air in concrete with increasing concentrations of an air entrainment agent with and without sacrificial agents.
  • FIG. 10 is a graph illustrating the percentage of air in concrete with increasing concentrations of an air entrainment agent with concrete friendly activated carbon and varying quality fly ash samples.
  • FIG. 11 is a graph illustrating the percentage of air in concrete with increasing concentrations of an air entrainment agent with high and poor quality fly ash , concrete friendly activated carbon, and sacrificial agents.
  • air entrainment in concrete and cementitious mixtures In the following description, reference is made to air entrainment in concrete and cementitious mixtures. It will be realized by persons skilled in the art that other inert gases, such as nitrogen, that act in the same way as air, can be entrained in concrete and cementitious mixtures. The use of air rather than other gases is naturally most frequently carried out for reasons of simplicity and economy. Techniques for entraining air in cementitious mixtures using air-entraining agents are well known to persons skilled in the art. Generally, when an air entrainment agent is used, sufficient air is entrained when the ingredients of the mixture are simply mixed together and agitated in conventional ways, such as stirring or tumbling sufficient to cause thorough mixing of the ingredients.
  • fly ash concrete has been traced to undesirable components contained in the fly ash materials, particularly residual carbon.
  • fly ash components can adsorb and/or react or interact with the air entrainment agent (surface active compounds, e.g. soaps) used for entrainment air in concrete, thereby neutralizing or diminishing the functionality of such agents and consequently reducing the uptake of air.
  • the air entrainment agent surface active compounds, e.g. soaps
  • Fly ash without activated carbon may be used as a partial replacement for portland cement in concrete if it meets certain specifications (such as those found in ASTM C618-05 “Standard Specification for Coal Fly Ash and Raw or Calcined Natural Pozzolan for Use in Concrete”).
  • the most common reason fly ash without activated carbon cannot be used in concrete is excess unburned carbon content in the ash. Excess unburned carbon is not allowed because it absorbs additives used in concrete making and makes them ineffective.
  • activated carbon for Hg capture ash is generally unusable even if it meets the unburned carbon specifications. This is because the activated carbon absorbs the concrete additives to a much large degree than the unburned carbon normally found in fly ash.
  • an amine sacrificial agent is used to neutralize or eliminate the effect of the harmful components of fly ash on the air entrainment agent.
  • the sacrificial agent acts preferentially (i.e. when present at the same time as the air entrainment agent, or even after the contact of the air entrainment agent with the fly ash, the sacrificial agent interacts with the fly ash), does not itself entrain air in significant amounts, and does not harm the setting action or properties of the cementitious material in the amounts employed.
  • the inventors have now found certain amines capable of “neutralizing” the detrimental fly ash components, while having little or no influence on the air entrainment process provided by conventional air entrainment agents and having no adverse effects on the properties of the concrete mix and hardened concrete product. These amine sacrificial agents, introduced into the mixture at an appropriate time, render fly ash concrete comparable to normal concrete with respect to air entrainment.
  • primary, secondary, and tertiary non-aromatic amines are the most suitable as sacrificial agents, namely compounds selected from the group consisting of the structure NR 1 R 2 R 3 , wherein R 1 is substituted or unsubstituted non-alkoxylated C 5-22 alkyl, substituted or unsubstituted non-alkoxylated C 5-22 alkenyl, substituted or unsubstituted non-alkoxylated C 5-22 alkynyl, substituted or unsubstituted C 2-22 alkoxylated alkyl, substituted or unsubstituted C 2-22 alkoxylated alkenyl, or substituted or unsubstituted C 2-22 alkoxylated alkynyl.
  • R 2 and R 3 are each independently selected from hydrogen, substituted or unsubstituted C 1-22 alkyl, substituted or unsubstituted C 2-22 alkenyl, or substituted or unsubstituted C 2-22 alkynyl.
  • the Log K ow is in the range of ⁇ 3 to +2 (e.g., ⁇ 2 to +2) and/or the HLB value is in the range of 5 to 20 (e.g., 4 to 18).
  • the alkyl, alkenyl or alkynyl chains can be branched or straight chains.
  • R 2 and R 3 can be optionally alkoxylated.
  • the R 1 , R 2 and R 3 can be substituted with groups such as halogen, carbonyl, hydroxyl, amine, and the like. In some embodiments, these compounds are used in pure or substantially pure form.
  • R 1 , R 2 , and R 3 is independently an alkoxylated or non-alkoxylated, substituted or unsubstituted fatty acid residue.
  • R 1 , R 2 , and R 3 can be selected from the group consisting of saturated fatty acids, monounsaturated fatty acids, polyunsaturated fatty acids, and mixtures thereof.
  • R 1 is a higher alkyl, alkenyl or alkynyl group having 7 or more carbon atoms (e.g, C8-C25 or C10-C20) and is generally an alkyl or alkenyl group.
  • the R 2 and R 3 groups can also be a higher alkyl, alkenyl or alkynyl group although, in some embodiments, are lower alkyl, alkenyl or alkenyl groups (e.g. C1-C5) such as C1-C3 alkyl or hydrogen.
  • Exemplary compounds include tridodecylamine, dodecyldimethylamine, octadecyldimethylamine, cocoalkyldimethylamines, hydrogenated tallowalkyldimethylamines, oleyldimethylamine, dicocoalkylmethylamine, and mixtures thereof.
  • the compounds can also be polyetheramines including the groups for R 1 , R 2 and R 3 described above and further being alkoxylated to the levels described herein.
  • one or more of R 1 , R 2 , and R 3 is independently amino-substituted (e.g. with a NR 4 R 5 group where R 4 and R 5 are H or substituted or unsubstituted, alkoxylated or non-alkoxylated, alkyl, alkenyl or alkynyl groups).
  • the amine sacrificial agent can be a diamine compound wherein R 1 is amino-substituted.
  • Exemplary diamines include polyetherdiamines (such as polyoxypropylenediamines and polyoxyethylene diamines) wherein the average level of alkoxylation is from 1 to 10, from 1.5 to 9 or from 2 to 8.
  • Suitable alkoxylated diamines can have the formula NH 2 —R—(R 1 O) x —NH 2 wherein R is C1-C5 alkyl, R 1 is C2-C4 alkyl, and x is the level of alkoxylation.
  • R is C1-C5 alkyl
  • R 1 is C2-C4 alkyl
  • x is the level of alkoxylation.
  • polyoxypropylenediamines are commercially available as Jeffamine D 400 and Jeffamine D 230; and triethyleneglycol diamine is commercially available as Jeffamine EDR 148, all from Huntsman International LLC.
  • the diamines are non-alkoxylated wherein x is 0 and R can be C5 or greater (e.g. C8-C25 or C10-C20).
  • the diamines are alkoxylated and have the formula R 3 ((R 4 O) w H)N—R 2 —N((R 5 O) y H)((R 6 O) z H) wherein R 2 is C1-C5 alkyl, R 3 is C1-C25 alkyl, alkenyl or alkynyl, R 4 , R 5 and R 6 are independently C2-C4 alkyl, one or more of x, y and z is greater than 0, and the total level of alkoxylation (w+y+z) is 1 to 10, 1.5 to 9 or 2 to 8.
  • R 3 is C5-C25 alkyl, alkenyl, or alkynyl (e.g.
  • Exemplary alkoxylated diamines include N-oleyl-1,1′-iminobis-2-propanol and N-tallowalkyl-1,1′-iminobis-2-propanol.
  • One commercially available example is N-tallowalkyl-1,1′-iminobis-2-propanol available from Akzo Nobel as Ethoduomeen T/13N.
  • the amine is hydroxyl substituted (e.g. at one, two or three of R 1 , R 2 and R 3 ) and is an alcoholamine.
  • R 1 is higher alkyl as described above and can be optionally substituted with a carbonyl group and one or more of R 2 and R 3 are hydroxyl substituted.
  • Amadol 1017 commercially available from Akzo Nobel and having the formula CH 3 (CH 2 ) 10 C( ⁇ O)N(CH 2 CH 2 OH) 2 can be used.
  • R 1 and one or more of R 2 and R 3 can be hydroxyl substituted.
  • the amine sacrificial agent has a particular “Hydrophilic Lipophilic Balance” (HLB) rating, or oil/water (or octanol/water) partition coefficients (K OW ).
  • HLB Hydrophilic Lipophilic Balance
  • K OW partition coefficients
  • the HLB value of the sacrificial agent or the mixture of sacrificial agents is in the range of S to 20 (e.g., 4 to 18).
  • the Log Kow for the sacrificial agent can be in the range of ⁇ 3 to +2 (e.g. ⁇ 2 to +2).
  • amine sacrificial agents can be used as the sacrificial agent composition.
  • dodecyldimethylamine, polyoxypropylenediamine, triethyleneglycol diamine, and mixtures thereof are used as the sacrificial agent.
  • the sacrificial agent can two or more amine sacrificial agents in weight a ratio of 1:1-1:50 wherein the total sacrificial agent is as described herein.
  • the sacrificial agent can include a first component having a compound A from the group of tridodecylamine, dodecyldimethylamine, octadecyldimethylamine, cocoalkyldimethylamines, hydrogenated tallowalkyldimethylamines, oleyldimethylamine, dicocoalkylmethylamine, and mixtures thereof (e.g. dodecyldimethylamine), and a second compound B from the group of polyetheramines, diamines, alcoholamines, all as described above, and mixtures thereof (e.g.
  • polyoxypropylenediamine wherein the weight ratio of compound A to compound B is 2:1 to 1:50, 1.25:1 to 1:25, or 1:1 to 1:5.
  • a sacrificial agent having different HLB values e.g. high and low values
  • HLB values e.g. high and low values
  • the amounts of such sacrificial agents are sufficient to neutralize the harmful components of the fly ash that adsorb or react with the air entrainment agents.
  • the required minimum dosage can be determined experimentally through air entrainment protocols since, as discussed earlier and shown below, the deleterious effects of fly ash components are not necessarily directly related to their carbon content or LOI.
  • the sacrificial agents can be used in reasonable excess over the neutralizing amounts without entrainment of excess air (or reduction of such entrainment) or harming the concrete mixture or the subsequent setting action or properties of the hardened concrete. This means that an amount can be determined which exceeds the neutralizing amount required for a fly ash containing the highest amount of the harmful components likely to be encountered, and this amount can then be safely used with any fly ash cement mixture.
  • the amine sacrificial agents can be used in combination with one or more sacrificial agents described in U.S. Pat. No. 7,485,184, which is incorporated by reference herein in its entirety.
  • additional sacrificial agents can include sodium naphthoate, sodium naphthalene sulfonate, sodium diisopropyl naphthalene sulfonate, sodium cumene sulfonate, sodium dibutyl naphthalene sulfonate, ethylene glycol phenyl ether, ethylene glycol methyl ether, butoxyethanol, diethylene glycol butyl ether, dipropylene glycol methyl ether, polyethylene glycol and phenyl propylene glycol and combinations thereof
  • sodium diisopropyl naphthalene sulfonate is included with the amine sacrificial agent in the sacrificial agent composition.
  • the additional sacrificial agent can be included
  • the amine sacrificial agents can be used in combination with a water reducer.
  • a water reducer For example, lignosulfonates and polynaphthalene sulfonates have been found to particularly enhance the properties of the amine sacrificial agents.
  • the water reducer can be included in a weight ratio of water reducer to amine sacrificial agent of 40:1 to 1:1.25 or 15:1 to 2:1.
  • the sacrificial agents can be added at any time during the preparation of the concrete mix. In some embodiments, they are added before or at the same time as the air entrainment agents so that they can interact with the fly ash before the air entrainment agents have an opportunity to do so.
  • the mixing in this way can be carried out at ambient temperature, or at elevated or reduced temperatures if such temperatures are otherwise required for particular concrete mixes.
  • the sacrificial agents can also be premixed with the fly ash or with the air entrainment agent.
  • the sacrificial agent can commence the interaction with the harmful components of the fly ash even before the cementitious mixture is formed.
  • the sacrificial agent can simply be sprayed or otherwise added in liquid form onto a conventional fly ash and left to be absorbed by the fly ash and thus to dry. If necessary, the sacrificial agent can be dissolved in a volatile solvent to facilitate the spraying procedure. Fly ash treated in this way can be prepared and sold as an ingredient for forming fly ash cement and fly ash concrete.
  • the sacrificial agent is even effective when added after the mixing of the other components of the cementitious mixture (including the air entrainment agent).
  • the sacrificial agent can reverse any preliminary deactivation of the air entrainment agent caused by contact with the fly ash, and thus reactivate the air entrainment agent for further air entrainment. It is observed, however, that the beneficial effect of the sacrificial agents is somewhat lower when added at this stage rather than when added before or during the mixing of the other components.
  • the chemical additives used as sacrificial agents are not effective air entrainment agents in the amounts employed, so that they do not contribute directly to air entrainment and can thus also be used in normal concrete containing no fly ash. This confers on the sacrificial agents the particularly important feature that these sacrificial agents can be introduced at dosages higher than the minimum dosage required to restore normal air entrainment without leading to erratic air entrainment and excessive air entrained levels.
  • one of the sacrificial agents used in a combination of sacrificial agents exhibits some surfactant (air entrainment) properties, it can be proportioned in such a way that the combination of sacrificial agents will entrain less than 2% air (or less than 1% air, or substantially no air), above the control values, in normal concrete without any fly ash. That is to say, when a concrete formulation is produced without fly ash, but with an air entrainment agent, the extra amount of air entrained when a sacrificial agent is added represents the extra air entrained by the sacrificial agent.
  • the amount of air entrained in a cementitious mixture can be measured by determination of specific gravity of the mixture, or other methods prescribed in ASTM procedures (ASTM C231, C 173, and C138—the most recent disclosures of which are incorporated herein by reference in their entirety).
  • Typical concrete air entrainment agents are n-dodecylbenzene sulfonate salts (referred to as Air 30) and tall oil fatty acid salts (referred to as Air 40).
  • Air 30 n-dodecylbenzene sulfonate salts
  • Air 40 tall oil fatty acid salts
  • the typical dosage range of these ingredients in portland cement concrete mixes is 0.002 to 0.008 wt % of the cementitious components.
  • the targeted air entrainment for the cementitious composition is typically 6-8 vol % air.
  • cementitious mixtures are water, cement and fly ash. These can be used in proportions that depend on the type of material desired (e.g., pastes, grouts, mortars, concrete) and on the required fresh and hardened properties of the finished material.
  • material desired e.g., pastes, grouts, mortars, concrete
  • Such systems and their composition, as well as equipment and protocols for their preparation, are well known in the art; for mortars and concrete, these are adequately described in standard reference texts, such as ASTM Cement and Concrete (e.g., 4.01, 4.02); Design and Control of Concrete Mixtures—Portland Cement Association; and American Concrete Institute—Manual of Concrete Practice (the disclosures of which are incorporated herein by reference).
  • ASTM Cement and Concrete e.g., 4.01, 4.02
  • Design and Control of Concrete Mixtures Portableland Cement Association
  • American Concrete Institute Manual of Concrete Practice
  • the cementitious mixture can be used in any conventional way, e.g. poured into a form and allowed to harden and set.
  • the hardened product will contain fly ash and entrained air, but no excess of air entrainment agent that could adversely affect the air content and properties of the hardened product.
  • the cementitious mixtures can include other standard or specialized concrete ingredients known to persons skilled in the art.
  • a sacrificial agent formulation is prepared by mixing polyoxypropylenediamine, dodecyldimethylamine, and optionally sodium diisopropylnapthalenesulfonate.
  • PACT sacrificial agent formulation
  • PACT was formulated as follows: 0.05% dodecyldimethylamine and 0. 15% polyoxypropylenediamine, by weight of fly ash.
  • the aggregate is mixed with partial water followed by the portland cement.
  • Fly ash combined with activated carbon is then added followed by the PACT formulation and the air entrainment agent.
  • the PACT formulation can be added directly to the fly ash. Additional water is added to obtain a 4-6 inch slump.
  • the composition is then mixed using a rotary mixer, and tested for volume percentage of air using a pressure meter according to the ASTM C 231 method.
  • PAC-A Norit HgLH (Norit Americas Inc., Marshall, Tex.)
  • PAC-B ADA-ES (ADA Environmental Solutions, Littleton, Colo.)
  • PAC-C Calgon MC Plus (Calgon Carbon, Pittsburgh, Pa.)
  • the air entrainment agent used in the following examples was MB-AE 90 (BASF Construction Chemicals, Shakopee, Minn.) and is labeled as AEA-1.
  • the competitive absorption by PAC-C with various sacrificial agents at saturated concentrations was determined ( FIG. 1 ).
  • the trace labeled Model AEA (DDBS) displays the absorption of an air entrainment agent (dodecylbenzenesulfonate (DDBS)) by MC activated carbon without the presence of a sacrificial agent.
  • the trace labeled DDBS (with SA-A2) displays the absorption of DDBS by PAC-C and Jeffamine EDR-148.
  • the trace labeled DDBS (with SA-C) displays the absorption of DDBS by MC activated carbon and Jeffamine 230.
  • the trace labeled DDBS (with SA-J4) displays the absorption of DDBS by MC activated carbon and Jeffamine 400.
  • the percentage of air in concrete with increasing concentrations of air entraining agent AEA-1 with varying amounts of activated carbon samples PAC-A, PAC-B, and PAC-C was determined.
  • the amounts tested for each activated carbon sample include 0.75% and 1.5% ( FIG. 2 ).
  • Cement and fly ash cement independently served as controls. All activated carbon samples increased the air entraining agent demand.
  • the percentage of air in concrete with increasing concentrations of an air entrainment agent (AEA-1) with varying amounts of activated carbon (PAC-A) with and without PACT (as formed in Example 1) was determined ( FIG. 5 ).
  • the amounts tested include 0.75% PAC, 2% PAC, 3% PAC, 0.75% PAC with PACT, 2% PAC with PACT, and 3% PAC with PACT.
  • Fly ash served as the control.
  • the inclusion of PACT in the activated carbon formulations reduced the air entraining admixture demand to acceptable levels.
  • the percentage of air in concrete with increasing concentrations of an air entrainment agent (AEA-1) with fly ash treated with activated carbon (PAC-A) in the presence of PACT was determined ( FIG. 6 ).
  • the amounts tested included fly ash treated with 1.5% activated carbon and fly ash treated with 3% activated carbon.
  • the PACT was present in constant, high dosage. Untreated fly ash served as the control. Increasing the dosage of PACT resulted in a performance comparable to that of untreated fly ash.
  • the percentage of air in concrete with varying amounts of activated carbon (PAC-A) with a constant concentration (1 oz/cwt) of an air entrainment agent (AEA-1) was determined ( FIG. 8 ).
  • the air entrainment agent was treated with PACT.
  • Untreated AEA-1 served as the control.
  • PACT treatment was shown to minimize air fluctuations over a broad range of PAC contamination levels.
  • the percentage of air in concrete with increasing concentrations of air entrainment agent was determined for untreated activated carbon and activated carbon treated with PACT ( FIG. 9 ).
  • the activated carbon samples were obtained from three different sources (PAC-A, PAC-B, and PAC-C). PACT was effective for all of the PAC samples tested; however, in some cases, it may be better to adjust the formulation depending upon the PAC source.
  • the percentage of air in concrete with increasing concentrations of air entrainment agent (AEA-1) was determined for high quality fly ash having a LOI of about 1% and a low quality fly ash having a LOI of about 2.5% with or without the addition of CF PAC-C activated carbon, a concrete friendly activated carbon available from Calgon Corp. and present in an amount of 3% ( FIG. 10 ).
  • the concrete friendly activated carbon influenced air entrainment, but did not compensate for underlying ash quality issues related to high or varying native carbon content.
  • the percentage of air in concrete with increasing concentrations of air entrainment agent (AEA-1) was determined for the same high quality and low quality fly ashes from Example 11 with or without the addition of CF PAC-C activated carbon and/or PACT ( FIG. 11 ). PACT effectively decreased the negative influence of carbon.

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102965077A (zh) * 2012-11-23 2013-03-13 东南大学 一种粉体矿粉添加剂
WO2014168633A1 (fr) * 2013-04-12 2014-10-16 Boral Ip Holdings (Australia) Pty Limited Composites formés à partir d'une charge absorbante et d'un polyuréthane
JP2015163753A (ja) * 2014-02-28 2015-09-10 小松精練株式会社 融雪用ブロック
US20160002108A1 (en) * 2013-12-23 2016-01-07 W.R. Grace & Co.-Conn. Targeted Air Control for Carbon Containing Fly Ash
US20160340840A1 (en) * 2013-12-10 2016-11-24 Kangwon National University University-Industry Cooperation Foundation Two-layer concrete pavement device and pavement method using normal concrete and high-perpormance concrete
US9988317B2 (en) 2016-08-16 2018-06-05 Go Team CCR LLC Structures constructed using coal combustion materials
US10472281B2 (en) 2015-11-12 2019-11-12 Boral Ip Holdings (Australia) Pty Limited Polyurethane composites with fillers
US10584062B2 (en) 2014-08-05 2020-03-10 Boral Ip Holdings (Australia) Pty Limited Use of sacrificial agents in manufacture of gypsum wallboard
US10752549B2 (en) 2015-02-27 2020-08-25 Gcp Applied Technologies Inc. Modifying cementitious compositions using ketone alcohol oil waste
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2012318528A1 (en) 2011-10-07 2014-05-22 Boral Ip Holdings (Australia) Pty Limited Inorganic polymer/organic polymer composites and methods of making same
EP3055677B1 (fr) * 2013-10-11 2019-03-06 Headwaters Incorporated Procédés et dispositif permettant de déterminer la capacité d'adsorption d'agents entraîneurs d'air
US9752015B2 (en) 2014-08-05 2017-09-05 Boral Ip Holdings (Australia) Pty Limited Filled polymeric composites including short length fibers
US9988512B2 (en) 2015-01-22 2018-06-05 Boral Ip Holdings (Australia) Pty Limited Highly filled polyurethane composites
US9806985B2 (en) 2015-03-02 2017-10-31 Cisco Technology, Inc. Symmetric routing enforcement
US10030126B2 (en) 2015-06-05 2018-07-24 Boral Ip Holdings (Australia) Pty Limited Filled polyurethane composites with lightweight fillers
CN109133706B (zh) * 2018-09-10 2021-01-15 广东潮泰建设有限公司 一种混凝土引气剂及其制备方法
CN110330281A (zh) * 2019-07-17 2019-10-15 广西大学 一种蔗渣灰混凝土及其制备方法

Citations (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4828619A (en) * 1987-02-18 1989-05-09 Fujisawa Pharmaceutical Co., Ltd. Air-entraining agent for flyash cement composition
US5413634A (en) * 1993-08-06 1995-05-09 Arco Chemical Technology, L.P. Cement composition
US5654352A (en) * 1995-05-16 1997-08-05 Maxflow Environmental Corp. Air-entraining agent and method of producing same
US5672203A (en) * 1996-08-07 1997-09-30 Halliburton Company Set retarded cementing compositions and methods
US5732643A (en) * 1994-04-29 1998-03-31 Neuhaus; Dietmar Sail for wind-powered conveyances
US5904764A (en) * 1995-05-19 1999-05-18 Ciments Francais Cementitious product and method for producing same
US5948157A (en) * 1996-12-10 1999-09-07 Fording Coal Limited Surface treated additive for portland cement concrete
US6048393A (en) * 1998-05-26 2000-04-11 W.R. Grace & Co. -Conn. Processing additives for hydraulic cements
US6149725A (en) * 1998-03-09 2000-11-21 Sika Ag, Vorm. Kaspar Winkler & Co. Injection cement comprising corrosion inhibitors
US6302955B1 (en) * 1998-11-04 2001-10-16 W. R. Grace & Co.-Conn. Composition for improving freeze/thaw durability of masonry containing fatty acid-based efflorescence control agents
US6355100B1 (en) * 1998-06-23 2002-03-12 Mbt Holding Ag Corrosion inhibitor for cement compositions
US6358311B1 (en) * 1997-03-28 2002-03-19 Taiheiyo Cement Corporation Additives for cement materials and cement materials
US6372038B1 (en) * 1998-04-28 2002-04-16 New Tokyo International Airport Authority Concrete composition for overlay method and hardened product therefrom
US6398866B1 (en) * 1999-01-29 2002-06-04 Sika Ag, Vorm. Kaspar Winkler & Co. Method for the reduction of the degree of shrinkage of hydraulic binders
US6461424B1 (en) * 2001-02-21 2002-10-08 Wisconsin Electric Power Company Electrically conductive concrete and controlled low-strength materials
US20030136307A1 (en) * 2000-03-02 2003-07-24 W .R. Grace & Co.-Conn. Air management in cementitious mixtures having plasticizer and a clay-activity modifying agent
US6616751B1 (en) * 2000-11-13 2003-09-09 Schlumberger Technology Corporation Water-selective cementing composition
US20040144287A1 (en) * 2003-01-24 2004-07-29 Boral Material Technologies Inc. System and method for treating fly ash
US6869474B2 (en) * 2002-08-29 2005-03-22 United States Gypsum Company Very fast setting cementitious composition
US6919388B2 (en) * 2000-08-11 2005-07-19 Nippon Shokubai Co., Ltd. Cement admixture and cement composition
US20070051277A1 (en) * 2005-09-02 2007-03-08 Boral Material Technologies Inc. Method of removing ammonia from fly ash and fly ash composition produced thereby
US20080156225A1 (en) * 2006-12-06 2008-07-03 Bury Jeffrey R Rheology modifying additive for cementitious compositions
US20090050023A1 (en) * 2001-06-22 2009-02-26 Christian Buerge Method for accelerating the setting and hardening of hydraulic binding agents and mixtures containing the same
US7556684B2 (en) * 2004-02-26 2009-07-07 Construction Research & Technology Gmbh Amine containing strength improvement admixture

Family Cites Families (55)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3615784A (en) 1969-08-04 1971-10-26 John Godfrey Compositions for producing improved concrete
US4116706A (en) 1977-07-01 1978-09-26 W. R. Grace & Co. Additive composition for hydraulic cement compositions
US4188231A (en) 1977-06-17 1980-02-12 Valore Rudolph C Methods of preparing iron oxide mortars or cements with admixtures and the resulting products
JPS5819618B2 (ja) 1978-09-25 1983-04-19 花王株式会社 Ａｅコンクリ−トまたはａｅモルタル用混和剤
US4257815A (en) 1979-07-13 1981-03-24 Edw. C. Levy Co. Air entraining mortar and process of manufacture
JPS6041630B2 (ja) 1979-08-02 1985-09-18 日本油脂株式会社 空気連行剤組成物
US4328145A (en) 1979-10-26 1982-05-04 American Admixtures And Chemicals Corporation Additive for air-entrained super plasticized concrete, concrete produced thereby and method of producing air-entrained super plasticized concrete
US4318744A (en) 1980-06-06 1982-03-09 W. R. Grace & Co. Strength enhancing admixture for concrete compositions
DE3152665C2 (en) 1981-03-02 1989-06-29 Nihon Cement Cement or concrete mass
US4351671A (en) 1981-04-15 1982-09-28 W. R. Grace & Co. Water reducing agent with reduced air
JPS5855353A (ja) 1981-09-22 1983-04-01 太平洋セメント株式会社 Ａｅフライアツシユコンクリ−トの製造方法
EP0159322B1 (fr) 1983-09-29 1987-10-21 Sandoz Ag Additif pour gachees de ciment hydraulique
GB8811171D0 (en) 1988-05-11 1988-06-15 Unilever Plc Cement compositions
JP2684399B2 (ja) 1989-01-06 1997-12-03 東邦化学工業株式会社 Ａｅフライアッシュコンクリート用混和剤組成物
US5181961A (en) 1989-05-22 1993-01-26 Nihon Cement Co., Ltd. Cement composition
US4948429A (en) 1989-06-14 1990-08-14 W. R. Grace & Co.-Conn. Method of controlling air entrainment in concrete compositions
US5116420A (en) 1990-09-07 1992-05-26 Schneider John F Homogeneous composition of cementitious and tar components and process for forming shaped articles therefrom
JPH04317447A (ja) 1991-04-15 1992-11-09 Kao Corp コンクリートの製造方法及びコンクリート用混和剤
JP2648255B2 (ja) 1991-07-23 1997-08-27 株式会社クボタ 窯業系製品の寸法安定化方法
US5221343A (en) 1992-04-10 1993-06-22 Henkel Corporation Dispersant, setting retarder and air entrainment additive for cement
FR2693719B1 (fr) 1992-07-15 1994-10-07 Roquette Freres Agent augmentant la vitesse de durcissement des ciments, des mortiers et des bétons tout en maintenant leur maniabilité.
US5527387A (en) 1992-08-11 1996-06-18 E. Khashoggi Industries Computer implemented processes for microstructurally engineering cementious mixtures
US5389143A (en) 1993-07-29 1995-02-14 W. R. Grace & Co.-Conn. Low shrinkage cement composition
US5326397A (en) 1993-07-29 1994-07-05 W. R. Grace & Co.-Conn. Low shrinkage cement composition
US5326396A (en) 1993-07-29 1994-07-05 W. R. Grace & Co.-Conn. Low shrinkage cement composition
CA2117585C (fr) 1993-09-14 2001-06-05 Edward T. Shawl Composition de liant
US5431729A (en) 1994-04-12 1995-07-11 Henkel Corporation Air entrainment compositions for cement compositions
JP3504346B2 (ja) 1994-08-12 2004-03-08 株式会社エヌエムビー セメント組成物用空気連行剤およびセメント組成物
US5618344A (en) 1995-03-06 1997-04-08 W. R. Grace & Co.-Conn. Cement composition
JPH08295546A (ja) 1995-04-25 1996-11-12 Lion Corp セメント組成物用空気連行剤
JP3624008B2 (ja) 1995-04-25 2005-02-23 四国電力株式会社 フライアッシュ含有セメント組成物用空気連行剤
JP2714640B2 (ja) 1995-06-09 1998-02-16 中国電力株式会社 石炭灰の高品質化方法及び装置
US5603760A (en) 1995-09-18 1997-02-18 W. R. Grace & Co.-Conn. Cement admixture capable of inhibiting drying shrinkage and method of using same
US5604273A (en) 1995-09-18 1997-02-18 W. R. Grace & Co.-Conn. Drying shrinkage cement admixture
US5622558A (en) 1995-09-18 1997-04-22 W.R. Grace & Co.-Conn Drying shrinkage cement admixture
US5556460A (en) 1995-09-18 1996-09-17 W.R. Grace & Co.-Conn. Drying shrinkage cement admixture
US5679150A (en) 1996-08-16 1997-10-21 Kerkar; Awdhoot Vasant Drying shrinkage cement admixture
JP3936765B2 (ja) 1996-12-06 2007-06-27 株式会社エヌエムビー ポンプ施工に用いるセメント組成物用添加剤
NZ502141A (en) 1997-06-25 2001-12-21 W Admixture and method for optimizing addition of EO/PO superplasticizer to concrete containing smectite clay-containing aggregates
TW416937B (en) 1997-10-01 2001-01-01 Grace W R & Co Improved processing additives for hydraulic cements
AU4681299A (en) 1998-06-18 2000-01-05 W.R. Grace & Co.-Conn. Air entrainment with polyoxyalkylene copolymers for concrete treated with oxyalkylene sra
US6136089A (en) 1998-08-31 2000-10-24 Brown University Research Foundation Apparatus and method for deactivating carbon in fly ash
AUPP970099A0 (en) 1999-04-09 1999-05-06 James Hardie International Finance B.V. Concrete formulation
US6706111B1 (en) 1999-08-03 2004-03-16 Mainland Laboratory, Ltd. Method for pretreating components of a cementitious composition to control adsorption potential
NZ517540A (en) 1999-08-03 2004-03-26 Mainland Lab Ltd Method for pretreating carrier components of a cementitious composition to control adsorption potential
US6277189B1 (en) 1999-08-31 2001-08-21 The Board Of Trustees Of Southern Illinois University Coal combustion by-products-based lightweight structural materials and processes for making them
US6599358B1 (en) 2000-03-13 2003-07-29 Mainland Laboratory, Ltd. Carbon scavenger fly ash pretreatment method
US6641661B1 (en) 2000-05-26 2003-11-04 W. R. Grace & Co.-Conn. High early strength cement and additives and methods for making the same
JP4626915B2 (ja) 2001-02-06 2011-02-09 花王株式会社 コンクリート硬化体の黒ずみ抑制方法
US20040200389A1 (en) 2001-04-24 2004-10-14 Young Robert Douglas Method for pretreating components of a cementitious composition to control adsorption potential
US6858661B2 (en) * 2001-05-01 2005-02-22 W. R. Grace & Co.-Conn. Defoamer for water reducer admixture
CN1318344C (zh) 2001-05-28 2007-05-30 株式会社日本触媒 水泥掺合料和水泥组合物
US6626663B1 (en) 2002-08-16 2003-09-30 Fosbal Intellectual Ag Processes for redistributing heat flux on process tubes within process heaters, and process heaters including the same
AU2003279125A1 (en) 2002-10-09 2004-05-04 Leslie A. Jardine Amine-containing cement processing additives
MY141254A (en) 2003-01-24 2010-03-31 Handy Chemicals Ltd Sacrificial agents for fly ash concrete

Patent Citations (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4828619A (en) * 1987-02-18 1989-05-09 Fujisawa Pharmaceutical Co., Ltd. Air-entraining agent for flyash cement composition
US5413634A (en) * 1993-08-06 1995-05-09 Arco Chemical Technology, L.P. Cement composition
US5732643A (en) * 1994-04-29 1998-03-31 Neuhaus; Dietmar Sail for wind-powered conveyances
US5654352A (en) * 1995-05-16 1997-08-05 Maxflow Environmental Corp. Air-entraining agent and method of producing same
US5904764A (en) * 1995-05-19 1999-05-18 Ciments Francais Cementitious product and method for producing same
US5672203A (en) * 1996-08-07 1997-09-30 Halliburton Company Set retarded cementing compositions and methods
US5871577A (en) * 1996-08-07 1999-02-16 Halliburton Company Methods of retarding cementitious compositions
US5948157A (en) * 1996-12-10 1999-09-07 Fording Coal Limited Surface treated additive for portland cement concrete
US6358311B1 (en) * 1997-03-28 2002-03-19 Taiheiyo Cement Corporation Additives for cement materials and cement materials
US6149725A (en) * 1998-03-09 2000-11-21 Sika Ag, Vorm. Kaspar Winkler & Co. Injection cement comprising corrosion inhibitors
US6372038B1 (en) * 1998-04-28 2002-04-16 New Tokyo International Airport Authority Concrete composition for overlay method and hardened product therefrom
US6048393A (en) * 1998-05-26 2000-04-11 W.R. Grace & Co. -Conn. Processing additives for hydraulic cements
US6355100B1 (en) * 1998-06-23 2002-03-12 Mbt Holding Ag Corrosion inhibitor for cement compositions
US6302955B1 (en) * 1998-11-04 2001-10-16 W. R. Grace & Co.-Conn. Composition for improving freeze/thaw durability of masonry containing fatty acid-based efflorescence control agents
US6398866B1 (en) * 1999-01-29 2002-06-04 Sika Ag, Vorm. Kaspar Winkler & Co. Method for the reduction of the degree of shrinkage of hydraulic binders
US20030136307A1 (en) * 2000-03-02 2003-07-24 W .R. Grace & Co.-Conn. Air management in cementitious mixtures having plasticizer and a clay-activity modifying agent
US6919388B2 (en) * 2000-08-11 2005-07-19 Nippon Shokubai Co., Ltd. Cement admixture and cement composition
US6616751B1 (en) * 2000-11-13 2003-09-09 Schlumberger Technology Corporation Water-selective cementing composition
US6461424B1 (en) * 2001-02-21 2002-10-08 Wisconsin Electric Power Company Electrically conductive concrete and controlled low-strength materials
US20090050023A1 (en) * 2001-06-22 2009-02-26 Christian Buerge Method for accelerating the setting and hardening of hydraulic binding agents and mixtures containing the same
US6869474B2 (en) * 2002-08-29 2005-03-22 United States Gypsum Company Very fast setting cementitious composition
US20040144287A1 (en) * 2003-01-24 2004-07-29 Boral Material Technologies Inc. System and method for treating fly ash
US7556684B2 (en) * 2004-02-26 2009-07-07 Construction Research & Technology Gmbh Amine containing strength improvement admixture
US20070051277A1 (en) * 2005-09-02 2007-03-08 Boral Material Technologies Inc. Method of removing ammonia from fly ash and fly ash composition produced thereby
US20080110374A1 (en) * 2005-09-02 2008-05-15 Boral Material Technologies Inc. Method of removing ammonia from fly ash and fly ash composition produced thereby
US20080156225A1 (en) * 2006-12-06 2008-07-03 Bury Jeffrey R Rheology modifying additive for cementitious compositions

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102965077A (zh) * 2012-11-23 2013-03-13 东南大学 一种粉体矿粉添加剂
WO2014168633A1 (fr) * 2013-04-12 2014-10-16 Boral Ip Holdings (Australia) Pty Limited Composites formés à partir d'une charge absorbante et d'un polyuréthane
US9932457B2 (en) 2013-04-12 2018-04-03 Boral Ip Holdings (Australia) Pty Limited Composites formed from an absorptive filler and a polyurethane
US10324978B2 (en) 2013-04-12 2019-06-18 Boral Ip Holdings (Australia) Pty Limited Composites formed from an absorptive filler and a polyurethane
US20160340840A1 (en) * 2013-12-10 2016-11-24 Kangwon National University University-Industry Cooperation Foundation Two-layer concrete pavement device and pavement method using normal concrete and high-perpormance concrete
US10000896B2 (en) * 2013-12-10 2018-06-19 Kangwon National University University-Industry Cooperation Foundation Two-layer concrete pavement forming device and pavement method using normal concrete and high-performance concrete
US20160002108A1 (en) * 2013-12-23 2016-01-07 W.R. Grace & Co.-Conn. Targeted Air Control for Carbon Containing Fly Ash
JP2015163753A (ja) * 2014-02-28 2015-09-10 小松精練株式会社 融雪用ブロック
US10584062B2 (en) 2014-08-05 2020-03-10 Boral Ip Holdings (Australia) Pty Limited Use of sacrificial agents in manufacture of gypsum wallboard
US10941076B2 (en) 2014-08-05 2021-03-09 Boral Ip Holdings (Australia) Pty Limited Use of sacrificial agents in manufacture of gypsum wallboard
US10752549B2 (en) 2015-02-27 2020-08-25 Gcp Applied Technologies Inc. Modifying cementitious compositions using ketone alcohol oil waste
US10472281B2 (en) 2015-11-12 2019-11-12 Boral Ip Holdings (Australia) Pty Limited Polyurethane composites with fillers
US10301223B2 (en) 2016-08-16 2019-05-28 Go Team CCR LLC Beneficial use structures
US9988317B2 (en) 2016-08-16 2018-06-05 Go Team CCR LLC Structures constructed using coal combustion materials
JP2021160963A (ja) * 2020-03-31 2021-10-11 三菱マテリアル株式会社 コンクリートの製造管理方法
JP7429588B2 (ja) 2020-03-31 2024-02-08 Ｕｂｅ三菱セメント株式会社 コンクリートの製造管理方法

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US20120085264A1 (en) 2012-04-12
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