WO2017214108A1 - Adjuvants améliorant la résistance pour ciments hydrauliques - Google Patents

Adjuvants améliorant la résistance pour ciments hydrauliques Download PDF

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Publication number
WO2017214108A1
WO2017214108A1 PCT/US2017/036101 US2017036101W WO2017214108A1 WO 2017214108 A1 WO2017214108 A1 WO 2017214108A1 US 2017036101 W US2017036101 W US 2017036101W WO 2017214108 A1 WO2017214108 A1 WO 2017214108A1
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WO
WIPO (PCT)
Prior art keywords
hydrogen atom
cement
group
astm
hydraulic
Prior art date
Application number
PCT/US2017/036101
Other languages
English (en)
Inventor
Joseph J. Biernacki
Ojas Arun CHAUDHARI
Donald P. VISCO
Hamed M. KAYELLO
Original Assignee
The University Of Akron
Tennessee Tech University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The University Of Akron, Tennessee Tech University filed Critical The University Of Akron
Publication of WO2017214108A1 publication Critical patent/WO2017214108A1/fr

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Classifications

    • 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
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/04—Carboxylic acids; Salts, anhydrides or esters thereof
    • C04B24/045—Esters, e.g. lactones
    • 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
    • C04B28/04—Portland cements
    • 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
    • C04B2111/70—Grouts, e.g. injection mixtures for cables for prestressed concrete

Definitions

  • the present invention relates to strength enhancing admixtures for hydraulic cements and methods of making the same. More particularly, this invention relates to chemicals of the glycol ether acetate family for which compressive strength enhancement is demonstrated in hydraulic cement concrete. These admixtures of the glycol ether acetate family have also shown some shrinkage reducing activity in hydraulic cement concrete.
  • Concrete is a composite material that primarily consists of hydraulic cement, aggregates such as sand and stone, and water.
  • concrete is one of the most affordable construction materials and is used twice (on a volume basis) as much as the sum of all other construction materials, including steel, aluminum, wood, and plastic.
  • Hydraulic cement an essential part of concrete, is the matrix and binder for the aggregate material.
  • the properties and overall performance of concrete depends on many factors including the chemical composition of the cement, the relative properties of the constituent materials, the physical and chemical nature of the aggregates, the way in which the fluid mixture was process and placed, and the curing conditions among other factors.
  • One of the major hydraulic cements is Portland cement.
  • Ordinary portland cement (OPC) is a mixture of synthetic and natural mineral phases including tricalcium silicate, dicalcium silicate, tricalcium aluminate, tetra calcium ferrate and gypsum along with much smaller amounts of other phases.
  • tricalcium silicate comprises the majority (50-75%) in OPC and it is the phase primarily responsible for the ultimate strength of hydrated-cement pastes.
  • stage (I) as soon as tricalcium silicate comes into contact with water, calcium and hydroxyl ions are released into the solution. Thus, this state represents initial dissolution of the tricalcium silicate.
  • stage (II) the reaction becomes very slow therefore it is referred to as the dormant or induction stage. In this stage, dissolution of calcium and hydroxyl ions continues but at a very slow rate.
  • Stage (III) involves initial crystallization (precipitation) of calcium hydroxide and acceleration in the rate of hydration of tricalcium silicate. Thus, this stage is called the acceleration stage.
  • the mechanism that causes the end of induction and the onset of acceleration is largely unknown.
  • Stage (IV) is characterized by continuous formation of the hydration products (CH and C-S-H). Likewise, the onset of stage (IV) hydration is largely unknown.
  • stage (V) the reaction continues with the slower rates for a prolonged period of time likely caused by the reaction becoming diffusion controlled.
  • Shrinkage is a major disadvantage of hydraulic cement concrete during the hydration (curing) process.
  • shrinkage frequently produces cracking when the concrete is restrained, such as with steel reinforcements or aggregate material.
  • This form of shrinkage cracking is a common source of distress in concrete structures. These cracks serve to accelerate other forms of damage in concrete including corrosion, freeze-thaw related degradation and leaching of soluble hydration products, thereby altering the structural integrity and shortening the service life of the structure.
  • a chemical admixture can be defined as an organic or inorganic (solid or liquid) chemical that is added to concrete before or during its mixing to alter or control property development.
  • Admixtures can alter the properties of concrete by many mechanisms including but not limited to: reduction in surface tension of water in the pores of concrete; adsorption onto various solid surfaces; altering the solubility of one or more species; and complexing with various soluble species.
  • the present invention provides a cement admixture composition for cementitious compositions comprising the chemical structure:
  • R, R', and R" are each the same or different and selected from the group consisting of a hydrogen atom, a C 1-10 alkyl group, and a hydroxyl group (OH), and n represents an integer from 1 to 4.
  • the present invention provides a cement admixture as in any of the forgoing embodiments, wherein R is a hydrogen atom, R' is a hydrogen atom, R" is a hydrogen atom, and n is 1.
  • the present invention provides a cement admixture composition of any of the forgoing embodiments, wherein R is a hydrogen atom, R' is a hydrogen atom, R" is a hydrogen atom, and n is 2. [0016] In a fourth embodiment, the present invention provides a cementitious composition comprising a hydraulic cementitious mix; an aggregate material; water; and a cement admixture comprising the chemical structure:
  • R, R', and R" are each the same or different and selected from the group consisting of a hydrogen atom, a Ci-io alkyl group, and a hydroxyl group (OH), and n represents an integer from 1 to 4.
  • the present invention provides a cementitious composition of any foregoing embodiments, wherein R is a hydrogen atom, R' is a hydrogen atom, R" is a hydrogen atom, and n is 1 for the cement admixture.
  • the present invention provides a cementitious composition of any foregoing embodiments, wherein R is a hydrogen atom, R' is a hydrogen atom, R" is a hydrogen atom, and n is 2 for the cement admixture.
  • the present invention provides a cementitious composition of any foregoing embodiments, wherein the hydraulic cementitious mix is selected from the group consisting of portland cement concretes, grouts and mortars; high alumina cement concretes, grouts and mortars; and dry mixes for making such concretes, grouts, and mortars.
  • the hydraulic cementitious mix is selected from the group consisting of portland cement concretes, grouts and mortars; high alumina cement concretes, grouts and mortars; and dry mixes for making such concretes, grouts, and mortars.
  • the present invention provides a cementitious composition of any foregoing embodiments, wherein the aggregate material is selected from the group consisting of fine aggregate materials that almost entirely pass through a Number 4 sieve according to ASTM C 125 and ASTM C 33, or coarse aggregate materials that are retained on a Number 4 sieve according to ASTM C 125 and ASTM C 33.
  • the present invention provides a cementitious composition of any foregoing embodiments, wherein the course aggregate material is selected from the group consisting of silica, quartz, crushed round marble, glass spheres, granite, limestone, calcite, feldspar, alluvial sands, sands or any other durable aggregate, and mixtures thereof.
  • the present invention provides a method of preparing a cementitious composition comprising: mixing water; aggregate material; hydraulic cement; and a cement admixture comprising the chemical structure:
  • R, R', and R" are each the same or different and selected from the group consisting of a hydrogen atom, a Ci-io alkyl group, and a hydroxyl group (OH), and n represents an integer from 1 to 4.
  • the present invention provides a method as in any of the forgoing embodiments, wherein said step of mixing includes: adding the water, aggregate material, and cement admixture together to form a pre-mixture; and mixing the pre-mixture together with the hydraulic cement to form the cementitious composition.
  • the present invention provides a method as in any of the forgoing embodiments, wherein the pre-mixture contains from 0.5 wt % or more to 4 wt% or less of the cement admixture for every one part of the hydraulic cement.
  • the present invention provides a method as in any of the foregoing embodiments, wherein the pre-mixture contains from 0.30 or more to about 0.60 or less parts of water for every one part of the hydraulic cement, and from 0.30 or more to about 0.70 or less parts of the aggregate material for every one part of the hydraulic cement.
  • the present invention provides a method as in any of the foregoing embodiments, wherein R is a hydrogen atom, R' is a hydrogen atom, R" is a hydrogen atom, and n is 1 for the cement admixture.
  • the present invention provides a method as in any of the foregoing embodiments, wherein R is a hydrogen atom, R' is a hydrogen atom, R" is a hydrogen atom, and n is 2 for the cement admixture.
  • the present invention provides a method as in any of the foregoing embodiments, wherein the hydraulic cementitious mix is selected from the group consisting of portland cement concretes, grouts and mortars; high alumina cement concretes, grouts and mortars; and dry mixes for making such concretes, grouts, and mortars.
  • the present invention provides a method as in any of the foregoing embodiments, wherein the aggregate material is selected from the group consisting of fine aggregate materials that almost entirely pass through a Number 4 sieve according to ASTM C 125 and ASTM C 33, or coarse aggregate materials that are retained on a Number 4 sieve according to ASTM C 125 and ASTM C 33.
  • the present invention provides a method as in any of the foregoing embodiments, wherein the aggregate material is course aggregate material and is selected from the group consisting of silica, quartz, crushed round marble, glass spheres, granite, limestone, calcite, feldspar, alluvial sands, sands or any other durable aggregate, and mixtures thereof.
  • the aggregate material is course aggregate material and is selected from the group consisting of silica, quartz, crushed round marble, glass spheres, granite, limestone, calcite, feldspar, alluvial sands, sands or any other durable aggregate, and mixtures thereof.
  • the present invention provides a method as in any of the foregoing embodiments, wherein mixing in said step of mixing is carried out for between 1 or more and 10 or less minutes.
  • An admixture for hydraulic cement mixes is provided, as well as a novel hydraulic cement composition containing such an admixture composition and a method for preparing such a hydraulic cement composition.
  • the admixture shows strength enhancing properties, and in some embodiments, shrinkage reducing properties, and in some embodiments both shrinkage reducing and strength-enhancing properties.
  • the cement admixture of the present invention is of the following generic chemical structure: wherein R, R', and R" are each the same or different and selected from the group consisting of a hydrogen atom, a Ci-io alkyl group, and a hydroxyl group (OH), and n represents an integer from 1 to 4.
  • the cement admixture is 2- butoxyethyl acetate wherein R is a hydrogen atom, R' is a hydrogen atom, R" is a hydrogen atom, and n is 1. This has been shown to reduce shrinkage.
  • the cement admixture is 2-2-(butoxyethoxy)ethyl acetate wherein R is a hydrogen atom, R' is a hydrogen atom, R" is a hydrogen atom, and n is 2. This has been shown to reduce shrinkage and increase strength.
  • the cement admixture of the present invention is added to hydraulic cement mixes, such as portland cement concretes, grouts and mortars, high alumina cement concretes, grouts and mortars, and dry mixes for making such concretes, grouts, and mortars in amounts sufficient to increase the compressive strength of the hydraulic cement mix and/or to reduce the shrinkage.
  • hydraulic cement it is meant those cements that set as a result of a chemical reaction with water.
  • the present invention employs a cementitious compositions which has a high content of tricalcium silicate and includes portland cement and cements that are chemically similar or analogous to portland cement, the specification for which is set forth in ASTM specification C 150-00.
  • cementitious materials are materials that alone have hydraulic cementing properties, and set and harden in the presence of water. Included in cementitious materials are ground granulated blast-furnace slag, natural cement, hydraulic hydrated lime, and combinations of these and other materials.
  • Aggregate can be included in the cementitious formulation to provide mortars including fine aggregate, and concretes including coarse aggregate.
  • the fine aggregate are materials that almost entirely pass through a Number 4 sieve (ASTM C 125 and ASTM C 33), such as silica sand.
  • the coarse aggregate are materials that are predominantly retained on a Number 4 sieve (ASTM C 125 and ASTM C 33), such as silica, quartz, crushed round marble, glass spheres, granite, limestone, calcite, feldspar, alluvial sands, sands or any other durable aggregate, and mixtures thereof.
  • cementitious composition described herein may contain other additives or ingredients and should not be limited to the stated formulations.
  • Cement additives that may be added include, but are not limited to: retarders, accelerators, air-entraining or air detraining agents, corrosion inhibitors, pigments, damp- proofing admixtures, gas formers, permeability reducers, pumping aids, fungicidal admixtures, germicidal admixtures, insecticidal admixtures, fibers, alkali-reactivity reducer, bonding admixtures, shrinkage reducing admixtures, pigment and any other admixture or additive that does not adversely affect the properties of the admixture of the present invention.
  • strength-enhancing fibers may be used in lesser amounts in light of the strength enhancement resulting from the glycol ether acetate admixtures of this invention.
  • the cement admixtures of the present invention have been shown to increase compressive strength in hydraulic cement compositions such as portland cement concretes.
  • the cement admixtures of the present invention have also been shown to reduce the surface tension of the pore solution (water remaining in the porosity of hydrating or hydrated cement) and thus inhibit shrinkage under sealed or evaporative drying conditions.
  • the cement admixtures of the present invention have less environmental impact and are more workplace safe than existing cement admixtures, such as amine-based compounds.
  • the cement admixture of the present invention is introduced into the hydraulic cement composition at the job site or at a ready-mix batching plant as part of the water of hydration.
  • the amount of the cement admixture may be governed by factors such as cement type and reactivity, ambient temperature, and concrete mixture proportions.
  • the admixture is employed at from 0.5 wt% or more to 4 wt% or less based on the total weight of hydraulic cement added, in other embodiments from about 0.8 wt. % to about 3 wt. %, and in yet other embodiments from about 1 wt. % to about 2 wt. %.
  • a mortar mix is prepared by adding from about 0.30 to about 0.60 parts of water for every one part of cement, in other embodiments from about 0.40 to about 0.55 parts of water for every one part of cement, and in yet other embodiments from about 0.45 to about 0.50 parts of water for every one part of cement. In one embodiment, the mortar mix is prepared by adding 0.46 part of water for every one part of cement.
  • the mortar mix is prepared by adding from about 0.30 to about 0.70 parts of aggregate sand for every one part of cement, in other embodiments from about 0.40 to about 0.60 parts of aggregate sand for every one part of cement, and in yet other embodiments 0.45 to about 0.55 parts of aggregate sand for every one part of cement. In one embodiment, the mortar mix is prepared by adding 0.5 parts aggregate sand to every one part cement.
  • the mortar mix is prepared by adding from about 0.5 wt. % to about 4 wt. % of the cement admixture for every one part of cement, in other embodiments from about 0.8 wt. % to about 3 wt. % of the cement admixture for every one part of cement, and in yet other embodiments from about 1 wt. % to about 2 wt. % of the cement admixture for every one part of cement.
  • the mortar mix is prepared by adding 1 wt. % of the cement admixture for every one part of cement.
  • the mortar mix is prepared by adding 0.46 parts water to every one part cement, 0.50 parts aggregate sand to every one part cement, and 1 wt. % of the cement admixture to every one part cement.
  • the mixing of all the ingredients of the mortar mix including but not limited to water, aggregate sand, the cement admixture of the present invention, and cement, are mixed from about 1 to about 10 minutes, in other embodiments from about 2 to about 8 minutes, and in yet other embodiments from about 3 to about 6 minutes. In one embodiment the mixing is performed for about 4 minutes. In one or more embodiments the mixing takes place on the slowest speed of a commercial stand mixer fit with a mixing hoop.
  • the cement admixture is used with an hydraulic cement mixture to create a novel hydraulic cement composition that can be used to increase the strength of an ultimately formed concrete object and/or to reduce the surface tension of the cement so as to reduce shrinkage.
  • the hydraulic cement mixture is based on ordinary portland cement, and contains the following ingredients:
  • the admixture is added to this portland cement of Table 1 to create the novel hydraulic cement composition,
  • the admixture is employed at from 0.5 wt% or more to 4 wt% or less based on the total weight of portland cement, in other embodiments from about 0.8 wt. % to about 3 wt. %, and in yet other embodiments from about 1 wt. % to about 2 wt. % to create portland cement premixtures.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

L'invention concerne une composition d'adjuvant pour ciment destinée à des compositions cimentaires, laquelle composition est à base d'acétates d'éther de glycol et comprend en particulier de l'acétate de 2-butoxyéthyle et de l'acétate de 2-2-(butoxyéthoxy)éthyle. Cet adjuvant peut améliorer la résistance d'une composition cimentaire ainsi obtenue et réduire le retrait pendant le durcissement.
PCT/US2017/036101 2016-06-06 2017-06-06 Adjuvants améliorant la résistance pour ciments hydrauliques WO2017214108A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201662346008P 2016-06-06 2016-06-06
US62/346,008 2016-06-06
US201662419162P 2016-11-08 2016-11-08
US62/419,162 2016-11-08

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4119519A1 (fr) 2021-07-12 2023-01-18 Mapei S.p.A. Adjuvant améliorant la résistance des compositions cimentaires à faible teneur en carbone
EP4353699A1 (fr) 2022-10-12 2024-04-17 Mapei S.p.A. Adjuvant pour beton a faible teneur en carbone

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1075459A (en) * 1964-12-04 1967-07-12 Pollycell Products Ltd Cementitious compositions
EP3006423A1 (fr) * 2013-05-29 2016-04-13 Silkroad C&T Co., LTD Macromonomère pour préparer un adjuvant pour ciment et son procédé de préparation, et adjuvant pour ciment comprenant un copolymère d'acide polycarboxylique, dérivé du macromonomère, et hydroxyde double lamellaire et son procédé de préparation

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1075459A (en) * 1964-12-04 1967-07-12 Pollycell Products Ltd Cementitious compositions
EP3006423A1 (fr) * 2013-05-29 2016-04-13 Silkroad C&T Co., LTD Macromonomère pour préparer un adjuvant pour ciment et son procédé de préparation, et adjuvant pour ciment comprenant un copolymère d'acide polycarboxylique, dérivé du macromonomère, et hydroxyde double lamellaire et son procédé de préparation

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4119519A1 (fr) 2021-07-12 2023-01-18 Mapei S.p.A. Adjuvant améliorant la résistance des compositions cimentaires à faible teneur en carbone
WO2023285386A1 (fr) 2021-07-12 2023-01-19 Mapei S.P.A. Adjuvant améliorant la résistance pour compositions cimentaires à faible teneur en carbone
EP4353699A1 (fr) 2022-10-12 2024-04-17 Mapei S.p.A. Adjuvant pour beton a faible teneur en carbone
WO2024078964A1 (fr) 2022-10-12 2024-04-18 Mapei S.P.A. Mélange de béton à faible teneur en carbone

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