Amine sacrificial agents and methods and products using same

Abstract

A method of producing cementitious mixtures containing fly ash as one of the cementitious components, under air entrainment conditions is described. The method involves forming a mixture comprising water, cement, fly ash, optionally other cementitious materials, aggregate, conventional chemical admixtures, and an air entrainment agent and agitating the mixture to entrain air therein. Additionally, at least one amine sacrificial agent is included in the mixture. The cementitious mixtures and hardened concretes resulting from the method and fly ash treated with sacrificial agent, or air entrainment agent / sacrificial agent combinations, are also described.

Description

BACKGROUND AND FIELD[0001]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.[0002]The partial replacement of portland cement by fly ash is growing rapidly, driven simultaneously by more demanding performance specifications on the properties of concrete and by increasing environmental pressures to reduce portland cement consumption. 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, ...

AI Technical Summary

Benefits of technology

[0020]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.

[0021]According to some embodiments, there is provided 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.

Problems solved by technology

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.

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.

Entrained air provides an air void system capable of protecting against freeze / thaw cycles, while entrapped air provide no protection against such phenomena.

When using 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.

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.

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. >2 wt %), or in the presence of low contents of highly reactive carbon or other detrimental fly ash components, 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.

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 %.

Furthermore, recent studies indicate that, while fly ash carbon content, as measured by loss on ignition (LOI) values, provides a primary indicator of fly ash behavior with respect to air entrainment, it does not reliably predict the impact that a fly ash will have on air entrainment in concrete.

Therefore, there currently exist no means, suitable for field quality control, capable of reliably predicting the influence that a particular fly ash sample will have on air entrainment, relative to another fly ash sample with differing LOI's, sources, or chemistries.

In practice, the inability to predict fly ash behavior translates into erratic concrete air contents, which is currently the most important problem in fly ash-containing concrete.

Obviously, variations in fly ash-carbon, which would lead to erratic variations in air contents, can have serious negative consequences on the concrete strength.

The 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.

This situation threatens to make an increasingly larger portion of the available fly ash materials unsuitable for use in concrete.

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%.

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.

To date, the proposed 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.

None of these proposed solutions have found significant acceptance in the industry, either because of their complexity and cost, or because of their limited performance in actual use.

For example, a clear limitation to the addition of a second surfactant (e.g., C8 fatty acid salt), to compensate for the adsorption of the air entrainment agents surfactant, simply shifts the problem to controlling air content with a combination of surfactants instead of a single one.

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