WO1999044966A1 - Adjuvant pour melanges, coulis et ciments a ressuage nul - Google Patents

Adjuvant pour melanges, coulis et ciments a ressuage nul Download PDF

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Publication number
WO1999044966A1
WO1999044966A1 PCT/US1999/004915 US9904915W WO9944966A1 WO 1999044966 A1 WO1999044966 A1 WO 1999044966A1 US 9904915 W US9904915 W US 9904915W WO 9944966 A1 WO9944966 A1 WO 9944966A1
Authority
WO
WIPO (PCT)
Prior art keywords
biopolymer
admixture
bleed
zero
water reducer
Prior art date
Application number
PCT/US1999/004915
Other languages
English (en)
Inventor
Christine A. Langton
Rajendran Narasimhan
David G. Karraker
Original Assignee
Westinghouse Savannah River Company
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 Westinghouse Savannah River Company filed Critical Westinghouse Savannah River Company
Priority to AU28979/99A priority Critical patent/AU2897999A/en
Publication of WO1999044966A1 publication Critical patent/WO1999044966A1/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
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • 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
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/06—Inhibiting the setting, e.g. mortars of the deferred action type containing water in breakable containers ; Inhibiting the action of active ingredients
    • C04B40/0633—Chemical separation of ingredients, e.g. slowly soluble activator
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
    • C04B2103/0082—Segregation-preventing agents; Sedimentation-preventing agents
    • C04B2103/0083—Bleeding-preventing agents

Definitions

  • Admixtures are materials added to cemental mixtures such as concrete or mortar and which modify the properties so as to make the mixture more suitable for a particular purpose and/or to achieve a useful property at a more economical cost.
  • admixtures are commercially available in the form of water-soluble solids or powders. These materials are typically designed to be mixed at the job site into the mixer. Other admixtures include liquid formulations which are added at bulk blending stations. The amount of admixtures, whether solid or liquid, must be carefully controlled. For many admixtures, slight inaccuracies in the batching of the admixture may impair or defeat the original properties for which the admixture was selected.
  • Admixtures which are known within the art include accelerators, retarders, air detrainers, air-entrainers, alkali-reactivity reducers, bonding enhancers, water reducers, corrosion inhibitors, dampproffing additives, grouting agents, gas formers, permeability reducers, pumping aids, and reinforcing agents.
  • accelerators accelerators, retarders, air detrainers, air-entrainers, alkali-reactivity reducers, bonding enhancers, water reducers, corrosion inhibitors, dampproffing additives, grouting agents, gas formers, permeability reducers, pumping aids, and reinforcing agents.
  • Superplasticizers are a type of high range water reducing admixture used to make high-slump flowing cement-containing mixtures.
  • the superplasticizers operate by reducing the water-to-cement ratio needed while still providing a mixture having a useful set time and other desirable properties.
  • Various superplasticizers are known in the art as described in U.S. Patent No. 5,728,207 entitled "Cement Admixture Product having Improved
  • biopolymers such as Welan gum in cement-containing mixtures where the gum serves as a suspension agent.
  • Such biopolymers serve to hydrate, expand and support the other materials within the mix as is taught in U.S. Patent No. 5,004,506 entitled “Welan Gum in Cement Compositions", and which is incorporated herein by reference.
  • one aspect of the present invention is to provide an admixture which provides for zero-bleed cured cement-containing mixes. It is a further object to provide for zero-bleed concrete mixes such as CLSM mixes, grouts, and concretes which maintain useful working properties including cohesiveness, flowability, self- compacting, and self-leveling.
  • admixture suitable for use with mixing equipment as well as more controlled batch production. It is a further object to provide a zero-bleed admixture and a resulting cement-containing composition having the admixture, which is useful for tank closings, mine closings, shaft closures, pipeline closings and non-shrink slabs.
  • cement mixture encompasses controlled low strength material (CLSM) mixes, grouts, and concretes.
  • CLSM controlled low strength material
  • the admixture comprises a superplasticizer such as a high range water reducer (HRWR) .
  • HRWR high range water reducer
  • An HRWR of an ASTM standard C494, type F, is provided by a polycarboxylic acid such as Advaflow or Adva Cast brands (W. R. Grace & Company, New York, N.Y.). This product has been found to work well and was used in the examples which follow.
  • the HRWR was used to suspend the powdered biopolymer Welan gum (Kelco Crete, Kelco Company) . Welan gum is fully described in U.S. Patent No. 4,342,866, which is incorporated herein by reference.
  • welan gum is attracted to certain short chain branch molecules present on the polycarboxylic acid. It is believed that through steric hindrance, such as formation of a micelle- type structure, a lattice structure, or some other stericly hindered placement, the polycarboxylic acid protects the associated gum particles from hydration.
  • an admixture of an effective amount of a Welan gum may be suspended, using a shear mixer at medium speed, within a solution of an HRWR polycarboxylic acid. Once suspended, the admixture is stable and protects the gum from hydration when exposed to agents which would normally cause hydration to occur. Upon introduction of the admixture to a cement slurry, the admixture is rapidly dispersed within the slurry. Continued agitation within the abrasive slurry releases the gum from the polycarboxylic acid where the gum is immediately hydrated.
  • the hydration and enhanced dispersion of the gum, combined with the water- reducing activity of the HRWR, may provide a zero- bleed concrete material. Surprisingly, it has been found that the admixture is operative with a wide variety of varying concrete mixtures.
  • the admixture is useful for use with CLSM and grouts having reactive materials designed to interact with leachable components of mixed waste.
  • Suitable reactive materials which may included within the cement mixtures includes ion exchange resins, zeolites (natural and synthetic) , clays, modified clays, cements, reducing agents, reactive blast furnace slag, reagent chemicals, sodium titanate, magnesium phosphate, amorphous silica, amorphous alumina, calcium hydroxide, kiln dust, and surface active refractories.
  • the amount of reactive agent added to the cement mixtures includes ion exchange resins, zeolites (natural and synthetic) , clays, modified clays, cements, reducing agents, reactive blast furnace slag, reagent chemicals, sodium titanate, magnesium phosphate, amorphous silica, amorphous alumina, calcium hydroxide, kiln dust, and surface active refractories.
  • the amount of reactive agent added to the cement mixtures includes ion
  • CLSM cement
  • concentration, volume, and type of hazardous material Additional factors include the volume of the reactive backfill to be added to the hazardous material storage area.
  • concrete mixtures suitable for use in waste tank closures and backfill for waste stabilization would produce varying amounts of bleed water.
  • Bleed water is the result of migration of water to a surface boundary of a freshly placed concrete composition and is attributed to the settlement of solid materials (cement, sand, or fly ash) within the composition.
  • the percentage of bleed water is, in part, a function of the amount of mixing water and the amount of cement. Mixes with higher water content will generate a higher percentage of bleed water. Concrete composition mixes with higher cement content will generate a lower percentage of bleed water.
  • a process for stabilizing a confined space container has the steps of mixing a concrete composition so that the concrete composition provides zero-bleed water, placing the concrete composition in a confined space, and sealing the confined space. This process can also include the step of mixing a reactive component with the concrete composition before placing it into the confined space.
  • Examples of useful concrete compositions for use with the admixture are set forth in Table 1.
  • CTL control reducing grout
  • RG reducing grout
  • the RG mixtures have reactive materials designed to stabilize and encapsulate incidental amounts of high level waste present in the closure tanks.
  • Standard mixing protocols were followed using a continuous auger batch plant.
  • the admixtures used the indicated proportions of the Welan gum powder suspended within the indicated volume of the polycarboxylic reducer (Advaflow) .
  • a mix time on the order of several minutes was found sufficient to disperse the reducer and achieve hydration of the gum.
  • Table 2 Set forth in Table 2 is test data conforming to the mixtures made according to Table 1. Flow determinations for the CLSM and RG mixtures conform to ASTM reference D-6103. For tank closures, a minimum flow of 10 inches is desired. The CTL grout flow was determined by the Kordan flow cone method.
  • ASTM measurements include: Bleed water, reference C-232; Air content, reference C-231; Unit weight, C-138; and compressive strength, C-39.
  • the ASTM standards are well known within the industry.
  • Test mix formulation RG3 was further field tested in waste tank closure operations. In field use, the RG3 mixture proved workable and resulted in multiple tank closures with zero-bleed.
  • Table 3 is a formulation for a CLSM zero-bleed formulation also found to be useful.
  • Table 4 is a comparison of a control grout using a type V cement in reference to the RG3 grout having a type I Portland cement.
  • the ratio of the superplasticizer to the biopolymer thickener is in the range of about 65- 130 grams per liter superplasticizer.
  • the individual amounts of superplasticizer to polycarboxylic acid vary depending on the type of concrete composition in which the admixture is to be placed.
  • a zero-bleed composition for a controlled strength material comprises about 50-600 pounds per cubic yard cement, about 2000-2500 pounds per cubic yard sand, about 0-600 pounds per cubic yard fly ash, about 0-600 pounds per cubic yard ground blast furnace slag, about 55-75 gallons cubic yard water, about 220-350 grams per cubic yard gum thickener, about 70-140 ounces per cubic yard superplasticizer and about 2-10 pounds per cubic yard reactive component.
  • An example of a zero-bleed, CLSM mix is about 150 pounds of cement per cubic yard, about 2300 pounds of sand per cubic yard, about 500 pounds of fly ash per cubic yard, about 63 gallons of water per cubic yard, and about 275 grams of gum thickener per cubic yard which is preblended in about 90 ounces of the HRWR superplasticizer per cubic yard of mix.
  • the zero-bleed, controlled low strength material is ideal for filling containers where there will be relatively low compressive forces upon the concrete composition.
  • cement type can vary in each of these formulations. It can be any one from type I, type II, type III, type IV, type V or any Portland cement. Different cements are selected for different needs, the selection, production, and use of which is well known in the art. Minor modifications to the formulations may be made depending on the type of cement that is used and the desired compressive strength of the concrete composition.
  • a reactive component may be added to any of these concrete compositions.
  • reactive components are sodium thiosulphate, calcium sulfite and sodium sulfite. These chemicals are useful to react with sludge left in a confined space so that even though the concrete hardens and there is zero-bleed water, the reactive chemicals react with hazardous material inside the sludge found in the bottom of a confined space. The chemical reaction ensures that the harmful chemicals in the sludge are precipitated out into a less harmful form.
  • ASTM blast furnace slag when mixed in the chemically reactive concrete composition, reacts with the alkalis in the waste and calcium from the cement to chemically reduce protechnetate (Tc +7 ) to Tc +4 which is then precipitated as a hydroxide and/or sulfide in the basic environment of the concrete composition.

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

Abstract

L'invention concerne un procédé et un produit permettant l'introduction et la dispersion d'un biopolymère, tel qu'une gomme de Welan dans un mélange cémenteux liquide. Un liquide porteur, constitué d'un superplastifiant réducteur d'eau de qualité, est utilisé pour la suspension et le maintien du biopolymère à l'état non hydraté dans une structure treillis à encombrement stérique. Lors de son introduction dans le mélange aqueux contenant du ciment, le liquide porteur répartit de manière homogène le biopolymère non hydraté. Par un mélangeage continu de la boue, la structure à encombrement stérique du liquide porteur est dégradée physiquement sous l'effet d'un mélangeage abrasif, le biopolymère non hydraté étant ainsi libéré. Lors de sa libération, le biopolymère hautement dispersé s'hydrate. La dispersion homogène du biopolymère, avant son hydratation, permet la production d'un produit fini qui durcit avec de l'eau à ressuage nul.
PCT/US1999/004915 1998-03-05 1999-03-05 Adjuvant pour melanges, coulis et ciments a ressuage nul WO1999044966A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU28979/99A AU2897999A (en) 1998-03-05 1999-03-05 Admixture for zero-bleed mixtures, grouts, and cements

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US7684598P 1998-03-05 1998-03-05
US60/076,845 1998-03-05

Publications (1)

Publication Number Publication Date
WO1999044966A1 true WO1999044966A1 (fr) 1999-09-10

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Family Applications (1)

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PCT/US1999/004915 WO1999044966A1 (fr) 1998-03-05 1999-03-05 Adjuvant pour melanges, coulis et ciments a ressuage nul

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AU (1) AU2897999A (fr)
WO (1) WO1999044966A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003018505A2 (fr) * 2001-08-24 2003-03-06 Rmc Group P.L.C. Melange pour compositions a base de ciment
US6800129B2 (en) 2003-01-30 2004-10-05 W. R. Grace & Co.-Conn. High solids pumpable cement additives
US8097666B2 (en) 2007-05-30 2012-01-17 W. R. Grace & Co.-Conn. Cement additive for stucco applications
US8168701B2 (en) 2008-04-24 2012-05-01 W. R. Grace & Co.-Conn. Concrete or mortar admixture composition
US20170107149A1 (en) * 2014-03-28 2017-04-20 Dow Europe Gmbh Stable pce and polysaccharide vma compositions for concrete admixtures and their uses
CN112592112A (zh) * 2020-12-09 2021-04-02 中建三局集团有限公司 一种可自密实固化黄土肥槽回填材料及回填方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0254603A1 (fr) * 1986-06-19 1988-01-27 Rhone-Poulenc Chimie Granules de biopolymère à dispersabilité et dissolution rapides
US4997487A (en) * 1990-03-07 1991-03-05 Halliburton Company High temperature set retarded well cement compositions and methods
US5180430A (en) * 1991-10-16 1993-01-19 W.R. Grace & Co.-Conn. Concrete surface air void reduction admixture
EP0650941A1 (fr) * 1993-10-29 1995-05-03 Sandoz Ltd. Mélanges réducteurs d'eau pour compositions de ciment
WO1996040598A1 (fr) * 1995-06-07 1996-12-19 The Nutrasweet Company Suspension stable d'hydrocolloides et de superplastifiant
WO1997027152A1 (fr) * 1996-01-26 1997-07-31 The Nutrasweet Company Addition de sucre et ou d'acide a des formulations de ciment contenant des polysaccharides anioniques

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0254603A1 (fr) * 1986-06-19 1988-01-27 Rhone-Poulenc Chimie Granules de biopolymère à dispersabilité et dissolution rapides
US4997487A (en) * 1990-03-07 1991-03-05 Halliburton Company High temperature set retarded well cement compositions and methods
US5180430A (en) * 1991-10-16 1993-01-19 W.R. Grace & Co.-Conn. Concrete surface air void reduction admixture
EP0650941A1 (fr) * 1993-10-29 1995-05-03 Sandoz Ltd. Mélanges réducteurs d'eau pour compositions de ciment
WO1996040598A1 (fr) * 1995-06-07 1996-12-19 The Nutrasweet Company Suspension stable d'hydrocolloides et de superplastifiant
WO1997027152A1 (fr) * 1996-01-26 1997-07-31 The Nutrasweet Company Addition de sucre et ou d'acide a des formulations de ciment contenant des polysaccharides anioniques

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003018505A2 (fr) * 2001-08-24 2003-03-06 Rmc Group P.L.C. Melange pour compositions a base de ciment
WO2003018505A3 (fr) * 2001-08-24 2003-10-16 Rmc Group P L C Melange pour compositions a base de ciment
US6800129B2 (en) 2003-01-30 2004-10-05 W. R. Grace & Co.-Conn. High solids pumpable cement additives
US8097666B2 (en) 2007-05-30 2012-01-17 W. R. Grace & Co.-Conn. Cement additive for stucco applications
US8168701B2 (en) 2008-04-24 2012-05-01 W. R. Grace & Co.-Conn. Concrete or mortar admixture composition
US20170107149A1 (en) * 2014-03-28 2017-04-20 Dow Europe Gmbh Stable pce and polysaccharide vma compositions for concrete admixtures and their uses
CN112592112A (zh) * 2020-12-09 2021-04-02 中建三局集团有限公司 一种可自密实固化黄土肥槽回填材料及回填方法

Also Published As

Publication number Publication date
AU2897999A (en) 1999-09-20

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