WO1997005079A1 - Compacted units of cement admixtures - Google Patents
Compacted units of cement admixtures Download PDFInfo
- Publication number
- WO1997005079A1 WO1997005079A1 PCT/EP1996/003315 EP9603315W WO9705079A1 WO 1997005079 A1 WO1997005079 A1 WO 1997005079A1 EP 9603315 W EP9603315 W EP 9603315W WO 9705079 A1 WO9705079 A1 WO 9705079A1
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- WIPO (PCT)
- Prior art keywords
- admixture
- cementitious composition
- compacted
- additive
- admixture material
- Prior art date
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Classifications
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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
- 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
- C04B40/0641—Mechanical separation of ingredients, e.g. accelerator in breakable microcapsules
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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
- 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
Definitions
- the present invention is directed to admixture materials and a process for their introduction into cement, mortar or grout. More particularly, the present invention is directed to an article comprising compacted units of admixture materials in preselected amount, and a process for the introduction of the article into a cementitious composition for modifying or enhancing the properties of a resulting cementitious product.
- an admixture is a material other than hydraulic cement, water, and aggregate that is used as an ingredient of concrete or mortar and is added to the batch immediately before or during its mixing. Admixtures are used to modify the properties of the concrete in such a way as to make it more suitable for a particular purpose or for economy.
- Admixtures are commercially available as water-soluble solids or powders, requiring job mixing at the point of usage, or ready-to-use liquids added at bulk blending stations. The successful use of admixtures depends upon the accuracy with which they are prepared and batched. Batching means the weighing or volumetric measuring of the ingredients for a batch of either concrete or mortar and introducing them into the mixer.
- the amount of admixture added during batching must be carefully controlled.
- Solid powdered admixtures are conventionally packaged and sold in bags, boxes and drums, and, conventionally, the admixture is added to the concrete mixture by opening the package and shoveling or dumping the admixture directly into a concrete mixer, or similar apparatus, during the concrete mixing operation.
- This labor intensive task is often messy and can be inaccurate within a particular mixer truck and/or between different trucks. Accordingly, it is desirable to have a method of dispersing admixture which is less labor intensive, less messy and more effective at uniformly dispersing or distributing the admixture throughout the cementitious composition mixture.
- U.S. Patent No. 4,961,790 to Smith et al discloses solid or powdered concrete admixture contained in a water soluble container which is released upon agitation in a wet mixer.
- the concrete is modified by the introduction of the preweighed admixture contained in the water soluble container and the agitation of the mix.
- the water soluble containers, or bags are stored in water insoluble receptacles prior to use.
- Smith et al note that for powdered solid admixtures, it is particularly cumbersome to weigh the required amount of solid admixtures at the job site, because an additional scale or weighing apparatus must always be kept handy.
- Smith et al proposed using premeasured bags of concrete admixture to minimize human error in handling and preweighing the solid admixture.
- U.S. Patent No. 5,203,629 to Valle et al disclose a method for introducing a solid admixture, contained in a paper package, into a fresh concrete and mixing the fresh concrete in a batch type mixer to cause the packaging material to disintegrate and distribute the admixture throughout the fresh concrete.
- U.S. Patent No. 5,320,851 to DeMars et al disclose a gelatin or wax encapsulated packaging and dispensing system for semifluid or fluid concrete and cement admixtures.
- the encapsulated capsule of the semifluid, fluid or perhaps solid admixture is intended to disintegrate or rupture when mechanically agitated and/or exposed to cementitious compositions.
- the disclosures of U.S. Patents 4,961,790; 5,203,629; and, 5,320,851 are inco ⁇ orated herein as if fully written out below.
- the present invention relates to the modification of the properties of a concrete, mortar or grout, by introducing an admixture into a fresh cementitious composition.
- the admixture may include at least one of air-entraining admixtures, air detrainer admixtures, accelerating admixtures, alkali-reactivity reducers, superplasticizers, pumping aids, water-reducing admix-tures, corrosion inhibitors, permeability reducers, grouting agents, gas formers, retarding ad-mixtures, bonding admixtures, colorants, biocidals, fibers, minerals, and mixtures thereof.
- the fresh cementitious composition, to which the admixture is introduced is mixed for sufficient time to cause the admixture to be dispersed uniformly throughout the fresh concrete.
- the present invention provides an additive for concrete, mortar or grout comprising at least one admixture material wherein the admixture comprises a compacted unit of a selec-ted amount of the admixture material, having strength sufficient to maintain structural integrity during handling and storage, but having sufficient solubility or friability upon mechanical agitation within a wet mixing environment of a cementitious composition mixture to dissolve or fragment for uniform dispersal throughout said cementitious composition mixture.
- the admixture material is a powder or flake admixture material for portland cement.
- the compacted unit contains inert filler as means for facilitating compaction or fragmentation of the admixture material.
- the admixture material is a liquid admixture material adsorbed onto a solid carrier, such as an inert filler.
- the unit is severable into selected, structurally stable fractions.
- An example of a cementitious composition capable of modification by the use of an additive according to the present invention is a controlled low strength material (CLSM).
- CLSM controlled low strength material
- the present invention further includes an additive for concrete, mortar or grout prepared by a) providing a selected amount of admixture material, and b) compacting the admixture material into a unit having structural stability for handling and storage, but retaining sufficient solubility or friability for dissolving or fragmenting upon mechanical agitation within a wet mixing environment of a cementitious composition mixture.
- Such additives may be advantageously prepared by adding a liquid to a premeasured amount of powder or flake admixture prior to compacting.
- the admixture material is compacted in combination with an inert filler.
- a liquid admixture is adsorbed onto a solid carrier prior to compacting.
- the additive according to the present invention may be compacted by molding, extrusion molding, pressing, tabletting, or the like.
- the present invention also includes a process for preparing a cementitious mixture including a) providing at least one cementitious composition and a liquid, b) at least partially mixing the cementitious composition and the liquid; c) introducing at least one admixture material to the at least partially mixed cementitious composition, wherein the admixture material comprises at least one compacted unit of a selected amount of the admixture material, having strength sufficient to maintain structural integrity during handling and storage, but having sufficient solubility or friability upon mechanical agitation within a wet mixing environment of the cementitious composition mixture to dis ⁇ solve or fragment for uniform dispersal throughout the cementitious composition mixture, and d) mixing the at least partially mixed cementitious composition and the at least one compacted unit to dissolve or fragment the at least one compacted unit to substantially disperse the admixture material throughout the cementitious composition.
- the present invention further includes a process for preparing a cementitious mixture including a) providing as ingredients i) at least one cementitious composition ii) at least one admixture material and iii) a liquid; wherein the admixture material comprises at least one compacted unit of a selected amount of the admixture material, having strength sufficient to maintain structural integrity during handling and storage, but having sufficient solubility or friability upon mechanical agitation within a wet mixing environment of a cementitious composition mixture to dissolve or fragment for uniform dispersal throughout said cementitious composition mixture; and b) combining ingredients i), ii) and iii) and c) mixing the ingredients to dissolve or fragment the at least one compacted unit to substantially disperse the admixture material throughout the ingredients i) and iii).
- the term "effective amount" of admixtures means an adequate quantity of material per cubic meter of hardened concrete to impart the desired improvement in the wet or dry concrete. Often, more than one unit of admixture material is added to the cementitious composition being processed in a commercial concrete mixer. As a result, the total amount of admixture must "cumulatively” result in an effective amount.
- admixture material is added to a cementitious composition mixture in a compacted unit, the same effective amount of active admixture material is added as would be added according to the conventional poured or pumped systems.
- uniform dispersal or “uniform distribution” means that the admixture is distributed in such a manner that the desired property, i.e. air entrainment, retardation, acceleration, etc., can be observed or measured in samples taken from the beginning, middle and end of the concrete mixture.
- batch type concrete mixer means any batch mixer suitable for thoroughly mixing cement and aggregate so as to obtain a homogeneous mass and coat all particles with cement paste.
- Preferred concrete mixers are: (1) rotating mixers, consisting of a revolving drum or a square box revolving about its diagonal axis and usually provided with deflectors and blades to improve the mixing; or (2 ) paddle mixers, consisting of a stationary box with movable paddles which perform the mixing. Rotating mixers are most preferred for use in the present invention.
- the method of the present invention allows a selected amount of flake or powder admixture to be added or dispensed into a wet mixer expediently, economically and accurately, as a solid, compacted unit. Additionally, according to the present invention, conventional liquid admixture material can be added or dispersed into a wet mixer as a solid, compacted unit, as detailed below.
- Some admixtures are used to modify the fluid properties of fresh concrete, mortar and grout, while others are used to modify hardened concrete, mortar, and grout.
- the various admixtures used in the present invention are materials that can be used in concrete mortar or grout for the following purposes: (1) to increase workability without increasing water content or to decrease the water content at the same workability: (2) to retard or accelerate the time of initial setting; (3) to reduce or prevent settlement of the finished material or to create slight expansion thereof; (4) to modify the rate and/or capacity for bleeding; (5) to reduce segregation of constituent ingredients; (6) to improve penetration and pumpability; (7) to reduce the rate of slump loss; (8) to retard or reduce heat evolution during early hardening; (9) to accelerate the rate of strength development at early stages; (10) to increase the strength of the finished material (compressive, tensile, or flexural); (11) to increase durability or resistance to severe conditions of atmospheric exposure, including application of deicing salts; (12 ) to decrease the capillary flow of water within the material; (13) to decrease permeability of
- Concrete admixtures are classified by function as follows: Accelerators are used to accelerate the setting and early strength development of concrete. Some of the common materials that can be used to achieve this function are calcium chloride, triethanolamine, sodium thiocyanate, calcium formate, calcium nitrite, and calcium nitrate.
- Retarding, or delayed-setting, admixtures are used to retard, delay, or slow the rate of setting of concrete. They can be added to the concrete mix upon initial batching or sometime after the hydration process has begun. Retarders are used to offset the accelerating effect of hot weather on the setting of concrete, or delay the initial set of concrete or grout when difficult conditions of placement occur, or problems of delivery to the job site, or to allow time for special finishing processes or to aid in the reclamation of concrete left over at the end of the work day. Most retarders also act as water reducers and can also be used to entrain some air into concrete.
- Lignosulfonates, hydroxylated carboxylic acids, lignin, borax, gluconic, tartaric and other organic acids and their corresponding salts, phosphonates, certain carbohydrates and mixtures thereof can be used as retarding admixtures.
- Air detrainers are used to decrease the air content in the mixture of concrete.
- Tributyl phosphate, dibutyl phthalate, octyl alcohol, water-insoluble esters of carbonic and boric acid, and silicones are some of the common materials that can be used to achieve this effect.
- Air-entraining admixtures are used to purposely entrain microscopic air bubbles into concrete. Air-entrainment dramatically improves the durability of concrete exposed to moisture during cycles of freezing and thawing. In addition, entrained air greatly improves a concrete's resistance to surface scaling caused by chemical deicers. Air entrainment also increases the workability of fresh concrete while eliminating or reducing segregation and bleeding.
- Materials used to achieve these desired effects can be selected from salts of wood resin; (Vinsol resin); some synthetic detergents; salts of sulfonated lignin; salts of petroleum acids; salts of proteinaceous material; fatty and resinous acids and their salts; alkylbenzene sulfonates; and salts of sulfonated hydrocarbons.
- Alkali-reactivity reducers can reduce alkali-aggregate expansion of these reducers, pozzolans (fly ash, silica fume), blast-furnace slag, salts of lithium and barium, and other air-entraining agents are especially effective.
- Bonding admixtures are usually added to portland cement mixtures to increase the bond strength between old and new concrete and include organic materials such as rubber, polyvinyl chloride, polyvinyl acetate, acrylics, styrene butadiene copolymers, and other powdered polymers.
- Water-reducing admixtures are used to reduce the amount of mixing water required to produce concrete of a certain slump, to reduce the ratio of water and cement, or to increase slump. Typically, water reducers will reduce the water content of the concrete mixture by approximately 5% to 10%.
- Superplasticizers are high-range water reducers, or water-reducing admixtures. They are added to concrete to make high-slump flowing concrete, and thus reduce the water-cement ratio. These admixtures produce large water reduction or great flowability without causing undue set retardation or entrainment of air in mortar or concrete.
- materials that can be used as superplasticizers are sulfonated melamine formaldehyde condensates, sulfonated naphthalene formaldehyde condensates, certain organic acids, lignosulfonates, and/or blends thereof.
- Natural and synthetic admixtures are used to color concrete for aesthetic and safety reasons. These coloring admixtures are usually composed of pigments and include carbon black, iron oxide, phthalocyanine, umber, chromium oxide, titanium oxide and cobalt blue.
- Co ⁇ osion inhibitors in concrete serve to protect embedded reinforcing steel from co ⁇ osion due to its highly alkaline nature.
- the high alkaline nature of the concrete causes a passive and nonco ⁇ oding protective oxide film to form on the steel.
- carbonation or the presence of chloride ions from deicers or seawater can destroy or penetrate the film and result in co ⁇ osion.
- Co ⁇ osion-inhibiting admixtures chemically arrest this co ⁇ osion reaction.
- the materials most commonly used to inhibit co ⁇ osion are calcium nitrite, sodium nitrite, sodium benzoate, certain phosphates or fluorosilicates, fluoroaluminates, amines and related chemicals.
- Dampproofing admixtures reduce the permeability of concrete that have low cement contents, high water-cement ratios, or a deficiency of fines in the aggregate.
- These admixtures retard moisture penetration into dry concrete and include certain soaps, stearates, and petroleum products.
- Grouting agents such as air-entraining admixtures, accelerators, retarders, and non-shrink and workability agents, adjust grout properties to achieve a desired result for specific applications.
- portland cement grouts are used for a variety of different purposes, each of which may require a different agent to stabilize foundations, set machine bases, fill cracks and joints in concrete work, cement oil wells, fill cores of masonry walls, and grout pre-stressing tendons and anchor bolts, and fill the voids in pre- placed aggregate concrete.
- Gas formers, or gas-forming agents are sometimes added to concrete and grout in very small quantities to cause a slight expansion prior to hardening. The amount of expansion is dependent upon the amount of gas-forming material used and the temperature of the fresh mixture.
- Aluminum powder, resin soap and vegetable or animal glue, saponin or hydrolyzed protein can be used as gas formers.
- Permeability reducers are used to reduce the rate at which water under pressure is transmitted through concrete.
- Silica fume, fly ash, ground slag, natural pozzolans, water reducers, and latex can be employed to decrease the permeability of the concrete.
- Pozzolan is a siliceous or siliceous and aluminous material, which in itself possesses little or no cementitious value. However, in finely divided form and in the presence of moisture, pozzolan will chemically react with calcium hydroxide at ordinary temperatures to form compounds possessing cementitious properties.
- Pumping aids are added to concrete mixes to improve pumpability. These admixtures thicken the fluid concrete, i.e., increase its viscosity, to reduce de-watering of the paste while it is under pressure from the pump.
- materials used as pumping aids in concrete are organic and synthetic polymers, hydroxyethylcellulose (HEC) or HEC blended with dispersants, organic flocculents, organic emulsions of paraffin, coal tar, asphalt, acrylics, bentonite and pyrogenic silicas, natural pozzolans, fly ash and hydrated lime.
- Bacteria and fungal growth on or in hardened concrete may be partially controlled through the use of fungicidal, germicidal, and insecticidal admixtures.
- the most effective materials for these purposes are polyhalogenated phenols, dialdrin emulsions, and copper compounds.
- Fresh concrete can sometimes be harsh because of faulty mixture proportions or certain aggregate characteristics such as particle shape and improper grading. Under these conditions, entrained air which acts like a lubricant, can be used as a workability improving agent.
- Other workability agents are water reducers and certain finely divided admixtures.
- Finely divided mineral admixtures are materials in powder or pulverized form added to concrete before or during the mixing process to improve or change some of the plastic or hardened properties of portland cement concrete.
- Portland cement as used in the trade, means a hydraulic cement produced by pulverizing clinker, consisting essentially of hydraulic calcium silicates, all usually containing one or more of the forms of calcium sulfate as an interground addition with ASTM types, I, ⁇ , HI, IV, or V.
- the finely divided mineral admixtures can be classified according to their chemical or physical properties as: cementitious materials; pozzolans; pozzonaic and cementitious materials; and nominally inert materials.
- 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. As discussed above, pozzolan is a siliceous or aluminosiliceous material that possesses little or no cementitious value but will, in the presence of water and in finely divided form, chemically react with the calcium hydroxide released by the hydration of portland cement to form materials with cementitious properties. Diatomaceous earth, opaline cherts, clays, shales, fly ash, silica fume, volcanic tuffs and pumicites are some of the known pozzolans.
- Nominally inert materials can also include finely divided raw quartz, dolomites, limestones, marble, granite, and others.
- Fibers can be made of zirconium materials, steel, fiberglass, or synthetic mate ⁇ rials, e.g., polypropylene, nylon, polyethylene, polyester, rayon, high-strength aramid, (i.e. Kevlar®), or mixtures thereof.
- Prefe ⁇ ed fibers of the present invention are synthetic fibers.
- Mixtures of two or more admixtures are also contemplated by the present invention.
- the present invention provides a means for introducing liquid or solid, e.g., powder or flake, admixtures for concrete, mortar or grout to a cementitious composition.
- the cementitious composition may include a cement composition for the production of a concrete, mortar or grout, but is preferably a hydraulic cement and most preferably is a portland cement.
- cementitious composition mixtures include aggregate, sand, pozzolans, fly ash, fibers, plastic, and the like.
- a liquid, primarily water, is an ingredient of the cementitious composition mixture.
- the admixture comprises powder or flake materials that have been compressed or otherwise molded under pressure into a generally cylindrical or briquette shaped unit.
- the particular shape of the unit is not critical, but it is advantageously of a shape which is capable of packing in a minimum volume so as to optimize storage considerations.
- One such advantageous shape is a cube or rectangular polygon.
- a liquid such as a (poly)ethylene glycol or (poly)propylene glycol, a liquid binder, and/or preferably water, to a premeasured amount of powder or flake admixture, in an amount which is sufficient to dampen and thus provide adhesion of the admixture material under pressure, but does not result in the dissolution of the admixture material or fragmenting of the compacted unit prior to introduction into the wet cementitious composition mixture environment.
- a liquid such as a (poly)ethylene glycol or (poly)propylene glycol, a liquid binder, and/or preferably water
- Suitable binders which are one means for maintaining structural stability of the admixture materials, include but are not limited to celluloses such as carboxymethylcellulose (CMC) and ethylcellulose, starches including pregelatinized starch, dextrin, maltodextrin, natural gums, polyvinyl alcohols, polyvinyl acetates, (poly)ethylene glycols, (poly)propylenes, clays such as bentonite, sugars such as liquid glucose, gelatin, guar gum, acacia gum, alginic acid, alginates such as sodium alginate, magnesium aluminum silicate, crosslinked polyacrylates such as Carbomer, polyvinyl py ⁇ olidones such as povidone, and Zein.
- CMC carboxymethylcellulose
- ethylcellulose starches including pregelatinized starch, dextrin, maltodextrin, natural gums, polyvinyl alcohols, polyvinyl acetates, (poly
- inert fillers to the admixture materials for compaction to i) render individual units structurally stable physically for physical handling and storage, and/or ii) facilitate the rapid breakdown by dissolution and/or fragmentation, of the unit when added to a (wet) cementitious composition mixture (e.g. cement, aggregate, water, etc.) which is being mechanically mixed or agitated.
- a cementitious composition mixture e.g. cement, aggregate, water, etc.
- the filler therefore, is included as means for maintaining structural stability as well as means for facilitating dissolution and fragmenting of the admixture material.
- suitable fillers include silica sand, silica fume, other natural or synthetic silica-based materials, Micro-Cell E silica (Celite Corp.), silicates, calcium aluminosilicate, aluminosilicates, clays, alumina, Alundum aluminosilicates (Norton), zeolites, ceramic spheres, fly ash, calcium carbonate (limestone powder), finely divided or powdered plastic, calcium sulfate, compressible sugar, confectioner's sugar, dextrates, dextrin, dextrose, dibasic calcium phosphate dihydrate, hydrogenated vegetable oil, kaolin, lactose, magnesium carbonate, magnesium oxide, maltodextrin, mannitol, cellulose, polymethacrylate, potassium chloride, powdered cellulose, starch, talc and tribasic calcium phosphate.
- Micro-Cell E silica Celite Corp.
- silicates calcium alumi
- Known methods of compacting powdered or flake solid materials may be used to produce the compacted admixture material units. Examples of such methods include extrusion molding of the admixture material, pressing, stamping or tabletting, and molding, such as by melting and pouring into a shaped mold, with or without added binder or filler. The latter molding technique may be utilized in the presence of a binder, but without compaction, to produce a unitized admixture article.
- anti-caking agents may be used.
- Suitable materials include, but are not limited to, fumed silica, colloidal silicon dioxide, magnesium trisilicate, talc, tribasic calcium phosphate, dibasic calcium phosphate dihydrate and bentonite.
- Glidants may also be useful in forming the compacted units of the instant invention.
- Suitable materials include, but are not limited to, colloidal silicon dioxide, magnesium trisilicate, powdered cellulose, starch, talc and tribasic calcium phosphate.
- Suitable lubricants include, but are not limited to, calcium stearate, glyceryl monostearate, hydrogenated castor oil, light mineral oil, hydrogenated vegetable oil, magnesium stearate, mineral oil, polyethylene glycol, sodium benzoate, sodium laurel sulfate, sodium stearyl fumarate, stearic acid, talc and zinc stearate.
- a disintegrant may be added to the admixture prior to compaction.
- disintegrants there are two types of disintegrants which may be useful: i) materials that swell upon contact with water - the expansion of these materials upon contact with water creates stress on the compacted unit thereby aiding its breakdown; and ii) materials which generate gas, i.e. gas release agents, when contacted with water at the appropriate pH - the gas release aids the breakdown of the compacted unit.
- Suitable materials include, but are not limited to, alginic acid and salts thereof such as sodium alginate, calcium or sodium carboxymethylcellulose, colloidal silicon dioxide, sodium Croscarmellose, guar gum, magnesium aluminum silicate, methylcellulose, microcrystalline cellulose, starch, bentonite and super absorbing polymers such as crosslinked poly(vinyl pyrrolidone), e.g. CrosPovidone, crosslinked polyacrylic acid or polyacrylate, maleic anhydride copolymers, cellulosic polymers, polyvinyl alcohol and similar materials.
- alginic acid and salts thereof such as sodium alginate, calcium or sodium carboxymethylcellulose, colloidal silicon dioxide, sodium Croscarmellose, guar gum, magnesium aluminum silicate, methylcellulose, microcrystalline cellulose, starch, bentonite and super absorbing polymers such as crosslinked poly(vinyl pyrrolidone), e.g. CrosPovidone, crosslinked polyacrylic acid or polyacrylate,
- Suitable gas release agents include oxygen release agents such as hydrogen peroxide, sodium peroxide, organic peroxides, sodium perborate monohydrate and sodium percarbonate; hydrogen release agents such as sodium borohydride, aluminum powder, lithium aluminum hydride and calcium hydride; and effervescent systems, e.g. those that release carbon dioxide as the product of the reaction between an acid and a carbonate.
- Materials useful as the acid source include, but are not limited to, citric acid, tartaric acid, malic acid, adipic acid, succinic acid, acid anhydrides such as sodium dihydrogen phosphate, disodium dihydrogen pyrophosphate and sodium bisulfite.
- Carbonate sources include, but are not limited to, sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, sodium sesquicarbonate and sodium glycine carbonate.
- liquid admixture materials are processed into solid compacted units by adsorbing the liquid admixture materials onto earners.
- the carriers may advantageously be the inert fillers described above.
- the carriers are contacted by the liquid admixture materials, and preferably at least partially dried, such as by air drying, prior to compacting the admixture containing ca ⁇ iers.
- soluble solid admixture materials are dissolved in a suitable liquid solvent, such as water, and the resulting solution is impregnated or adsorbed onto ca ⁇ iers by contacting the carrier with the solution, and preferably at least partially drying, prior to compacting the admixture containing carriers.
- a suitable liquid solvent such as water
- the carriers may advantageously be the inert fillers described above.
- insoluble solid admixture may be slurried in a liquid and the carrier contacted with the slurry to form a coated carrier prior to compacting.
- the admixture material units are sized so as to deliver a selected amount of pre-measured active admixture material to a desired or standardized volume of cementitious composition mixture.
- Admixture can be added to the cementitious mixture in a batch type concrete mixer at a central batch plant, where conventional admixture materials must be weighed, measured and poured, or as advantageously enabled by the present invention, can be added directly to a batch type concrete mixer truck or ready mix truck, at the job site.
- adding the compacted units of admixture material at the job site does not require weighing and pouring, such that dusting, spillage and contamination are avoided.
- admixture material it is within the scope of the invention to use multiple units for a given volume of cementitious composition mixture. It is further within the scope of the present invention for the admixture material to be compacted into a unit which is severable, such as by providing perforations of the compact unit or the like, to provide selected, structurally stable fractions for smaller volumes of cementitious composition mixture, or to provide supplemental dosages of admixture which may be required because of the elapse of time from initial introduction and diminution of the desired effect.
- the unit size is preferably small, so as to provide the most efficient packing of the units in terms of units per box, or other container.
- a small size is preferable for handleability on a job site, for example, several small units being capable of being carried in a worker's pocket while the worker climbs a ladder onto a batch type concrete mixer (truck) to deliver the unit(s) into the mixer.
- a preferable size of the unit would be sufficient to deliver active admixture material for at least one to two cubic meters of cementitious composition mixture per unit. If a severable unit is used, it may advantageously be sized to provide sufficient active admixture material for at least four cubic meters of cementitious composition mixture, and be severable into two or more selected, structurally stable fractions.
- a starting batch of cementitious composition mixture in a ready mix truck may typically be 4 to 6 cubic meters.
- air entrainer admixture When air entrainer admixture is added to the mixture, it expands in volume with the generation of 20-35% air, to 8 to 10 cubic meters. If required to be added at the central batch plant, the full load, with air, would be required to be transported by truck to the job site.
- the present invention permits a smaller volume to be transported, with volume expansion due to air entrainment being accomplished at the job site without requiring bulky admixture measuring and dispensing equipment to be transported from site to site.
- the admixture material compacted units should be somewhat moisture resistant. Such moisture resistance may be imparted by the use of a binder in the formation of the compacted unit, preferably one which breaks down at a pH experienced by the unit in the wet cementitious composition mix, that is, pH 1 1 and above.
- a binder in the formation of the compacted unit, preferably one which breaks down at a pH experienced by the unit in the wet cementitious composition mix, that is, pH 1 1 and above.
- the units may be stored individually, but preferably in number, in a sealable plastic bag such as a Zip-Loc bag. Any water insoluble container, however, is suitable for such storage, so long as it is water-impermeable and is not water-degradable.
- the compacted unit is coated with a material that is at least partially insoluble in water.
- a material which is substantially insoluble in water such as celluloses, clays, partially hydrolyzed starches, latexes, polyvinyl alcohols, polystyrenes, polyurethanes and the like, enhances the storage capabilities of the compacted unit in a moist environment, or would otherwise protect hydroscopic admixture material.
- a water-insoluble coating must be capable, however, of breaking or dissolving in the high pH, agitated mixing environment of the cementitious composition, and is preferably thin, on the order of about 1-10 mils.
- the material may not be deleterious to the properties desired for the final product.
- the coating may be selected so as to protect the compacted unit, and/or to protect the user from an unfriendly material.
- a cementitious mixture can be prepared according to the present invention, by providing at least one cementitious composition, such as a hydraulic cement and preferably portland cement, and a liquid, such as water, at least partially mixing the cementitious composition and the liquid, introducing at least one admixture material compacted unit into the at least partially mixed cementitious composition, and mixing the resulting combination to dissolve and/or fragment the unit in order to disperse the admixture material throughout the cementitious composition.
- Other materials such as the ingredients set out above including aggregate, sand, fiber reinforcement, and the like, can be added to the mixture at an appropriate time.
- the ingredients i) at least one cementitious composition, ii) at least one admixture material compacted unit, and iii) a liquid can be combined in any order, prior to, during, or after a mixing cycle, and thereafter mixed to dissolve and/or fragment the compacted unit, and/or substantially disperse the admixture material throughout the other ingredients to form a cementitious composition mixture.
- Admixture material linear dodecylbenzene sulfonate (Witconate LX, obtained from Witco Chemical, New York, New York) was compacted into a physical unit using a Blaine Cell and plunger. 3.0 grams of dodecylbenzene sulfonate was compacted in the cell using heavy finger pressure. The material was compacted in a sturdy, small cylinder.
- Admixture material powder compaction was evaluated using several materials, with and without the addition of inert filler.
- the admixture powders and fillers (if any) were preblended prior to compacting by shaking in a closed container.
- the compaction process utilized a Blaine Cell and Penetrometer to apply known compression loads.
- the Blaine Cell was filled with powder and tapped to consolidate the material.
- the plunger was in- serted and a load was applied using the number 2 pin in the Penetrometer.
- the plunger diameter was 1.26 cm, providing a compacted unit, or pellet having a surface area of 3J7 cm 3 .
- Penetrometer compaction loads described throughout this specification relate to Mega Pascals (MPa) according to the following Table A.
- Table I describes the admixture materials which were tested according to this procedure, including the physical form before compaction, the loose weight, the compaction pressure used, the filler level utilized, if any, and the characteristics of the pellets which were produced.
- the admixture materials of examples B-2 to B-4 were obtained from Stepan Chemical Co. (Northfield, Illinois).
- the size of the compacted units for one specific admixture material is included for purposes of exemplification, the size of compacted units of other admixture materials is not to be limited to these sizes.
- the only critical constraints upon the size of the compacted units are the dosage of active material needed to impart the desired property to a given amount of cementitious composition mixture, the amount of inert filler desired to impart structural stability and solubility/fragmentibility, and the range of the pressures of compaction useful for making a stable, yet soluble/friable compact.
- the dose response of admixture liquid, powder, and compacted powder unit samples were evaluated to produce high air content ready mix mortar known as controlled low strength material (CLSM).
- CLSM controlled low strength material
- the cementitious composition mixture was prepared using a high fly ash content, and the admixture material was prepared in 88.7 mL and 177.4 mL equivalent dosages, as discussed below, corrected for activity.
- the effective mixing time using the liquid and powder admixture materials in a concrete mixture was evaluated at 5 minutes and 8 minutes.
- the compacted, or pelletized admixture material was evaluated at a mixing time of 12 and 17 minutes, to permit fragmenting and dissolution of the pellet.
- Table III the admixture material compositions identified were utilized for purposes of this demonstration.
- Table III indicates the percent activity of the admixture material, and the adjusted amount of grams necessary to provide an equivalent to 88.7 mL and 177.4 mL respectively of the commercial liquid admixture material (Cocamide DEA).
- the material dose for use in the mixture design including the active percent per 45.4 Kg of cement, and grams per cubic meter as well as the active grams per 79.4 Kg batch, being equivalent to 88.7 mL and 177.4 mL of the above comparative admixture material.
- Table IV describes the cementitious composition mixture design utilized for testing according to Example D, describing the ingredients, amounts in kilograms per cubic meter, with volume and weight percent as well as the amounts in a 79.4 Kg batch and its corresponding volume.
- Example D-5 a compacted pellet of the admixture material of Example D-2 was prepared such that the pellet size containing the powder and inert filler were such that two pellets would deliver the same dose as the 88.7 mL equivalents above, and were compacted to 81.7 Kg (Penetrometer) 2.92 grams of the alpha olefin sulfonate and .58 grams of silica flour were utilized for the test.
- Example D-5 it was determined that the particular filler used, silica flour, was too fine, and the compaction pressure of over 6.21 MPa was too high, to provide equivalent performance in equal mixing times. Adjustment of filler type and compaction pressure was thereafter shown to produce a less hard, and therefore, more easily fragmented and dissolved compacted unit to reduce the required mixing time for the cementitious composition mixture.
- Example No. DJ D-2 D-3 D-4 D-5 admixture equiv. mL/m 3 1 16.0 1 16.0 232.1 232.1 1 16.0 % by wt. cement 0.099 0.099 0.198 0.198 0.099 cement (Kg/m 3 ) 30.3 28.5 30.3 27.9 30.3 f fly ash (Kg/m 3 ) 90.8 86.0 90.2 83.7 90.2 sand (Kg/m 3 ) 1510.5 1428.6 1499.8 1398.4 1504.0 water (Kg/m 3 ) 201.1 190.4 199.9 186.3 200.5 unit wt(8min)(Kg/m 3 ) 1832.6 1733.2 1819.7 1696.4 1824.5 yield (m 3 ) 20.73 21.92 20.88 22.40 20.83 slump@5min 22.2 cm 23.5 cm 22.2 cm 22.2 cm 19.7 cm* slump@8min 24.1 cm 23.5 cm 26.7 cm 22.2 cm 22.9 cm*
- Admixtures added at 1 minute to wet mixture.
- liquid admixture material of Examples Dl and D3 are conventionally delivered into a cementitious composition mix in a capsule as disclosed in U.S. Patent No. 5,320,851.
- the admixture material was delivered directly to the mixture, without an external capsule. If the capsule had been used to deliver the admixture for Examples Dl and D3, then additional mixing time would also have been required to rupture the capsule and disperse the admixture.
- E-3 Cocamide DEA liquid surfactant (removed from capsule). The mix water content was held constant for each mix with each admixture material being added after one minute mixing, to the wet mix. Air content was measured by an ASTM C231 type B pressure meter and gravimetrically, and slump was determined after 5 and 8 minutes of mixing. Test results are shown in Table VI.
- E-3 achieved air content with less mixing than compacted E-2, under these test conditions E-3 had a favorable bias in that it was added directly to the mix. This removed the capsule breakage and gradual release of the viscous surfactant from the time needed to generate air.
- the powdered surfactant E-l achieved higher air content values than the liquid for the same amount of mixing. It is therefore projected that with continued mixing, the compacted unit E-2 will generate air content values at least equivalent to those generated by E-l, and thus exceed the values for E-3.
- Example F A test was conducted to determine the amount of air present over time in an admixture-treated cementitious composition mixture.
- the admixture surfactant of Example F was added in equivalent dosages to the following cementitious composition mixtures as a powder and as a compacted unit.
- the compacted unit was prepared with 30% silica sand at 27.22 Kg Penetrometer pressure (2J4 MPa).
- the general mix design was as follows:
- the percent water content was held constant for these mixes as tested.
- the admixtures were added at 1 minute to the wet mix.
- the mix was tested at 5 and 8 minutes at regular mix speed, and then at 15 minute intervals at slow mix speed, to demonstrate air loss in a batch type concrete mixer truck over a period of time.
- the results of the test show that the low pressure, filler containing compacted unit achieved substantially the same air content in the cementitious mixture as the powdered air entrainment admixture material.
- the additional ingredients to the cementitious composition mixture namely fly ash and/or sand, were of the same type and grading within each example. It should be noted that the presence, type and quality of fly ash can influence air generation and loss, set time, and compressive strength. The sand grading can also affect air content and water demand, influencing set time and compressive strength performance.
- Compacted units of the air entrainment admixture powder of Example F were prepared to evaluate the effects of filler level and compacting load on the time required for complete dissolution of the sample.
- the three compacting loads and the three filler levels are shown below.
- Unit specimens were placed in beakers containing 300 mL of 21°C tap water and mechanically stirred at slow speed.
- the use of a multiple position magnetic stir plate allowed 5 samples to be evaluated at the same time under identical conditions. The time required for total dissolution of the sample was recorded. It should be noted that this test provides a relative comparison of solubility only, as the amount of admixture being dissolved in the quantity of water for this test is substantially more than under actual CLSM mix conditions (2.46g/300 mL vs.
- Compacted cylinder units of the admixture material of Example F were prepared to evaluate their physical stability under a variety of storage conditions. Multiple specimens were placed in either wirl-pak or Zip-Lock plastic bags in order to provide some protection from any outer packaging, closely simulating actual storage conditions.
- the storage conditions evaluated were: 21 °C, 32°C, 49°C, and 21 °C in a moist room (100% humidity).
- the physical condition was monitored over time, specifically evaluating certain properties such as: softening, feel (stickiness), fusing (sticking together of specimens in the bag), and general breakdown of the specimen.
- softening feel (stickiness)
- fusing sticking together of specimens in the bag
- general breakdown of the specimen.
- a further advantage of the compacted units of admixture material according to the present invention is their avoidance of the tendency of liquid or semiliquid admixture materials to freeze, slush or separate at low temperature.
- the use of compacted units of admixture according to the present invention overcomes job site dusting problems associated with powder admixture materials, avoids the use of bulky measuring dispensing equipment at the job site for liquid or solid free flowing admixture materials, and overcomes spillage concerns associated with conventional admixture materials.
- Examples J-1 and J-2 were compacted using an Instron materials testing machine, Model 4204, equipped with a 4,536 Kg load cell, in a compression mode at a rate of 5.1 mm second.
- Example J-3 was compressed using a Satec Compression Machine, Model 400CTL, utilizing a Baldwin Universal Testing System controller available from Satec Systems, Inc., Grove City, PA, while Examples J-4, J-5 and J-6 were handpressed using a hydraulic Buehler handpress.
- Three lab scale concrete mixes were prepared in order to evaluate and compare the retardation effect of two compacted retarding admixtures according to the present invention with a liquid retarding admixture.
- the three lab scale mixes were prepared such that the weights of materials per 1.0 cubic ft. of concrete were
- the total mixing time was five minutes.
- the admixtures added to the cement mixes were as follows:
- K-1 Two solid discs, pressed at 48.3 MPa in a 2.54 mm diameter die using a Buehler hydraulic handpress. Each disc contained 0.64 g sodium gluconate, 0.24 g phosphonate (ADPA-6OSH, available from Albright and Wilson) and 1J7 g bentonite.
- K-2 Two solid discs, prepared as above except each disc contained 0.77 g phosphonate (ADPA-60SH), 0.49 g citric acid, 0.49 g bentonite and 0.97 g sodium bicarbonate.
- ADPA-60SH phosphonate
- citric acid 0.49 g citric acid
- bentonite 0.97 g sodium bicarbonate.
- K-3 Liquid mixture containing 0.47 g sodium gluconate and 1.28 g phosphonate (ATMP, available from Monsanto) dosed at 12.7 mL per lab batch (equivalent to 130 mL/100 Kg).
- a retarding admixture compacted unit according to the present invention was prepared by combining the materials indicated in Table IX and compressing at 34.5-41.4 MPa to give a 6.67 cm diameter disc having a compacted density of approximately 1.41 g/cm 3 .
- the dissolution time of the disc was found to be 4 min. 10 sec.
- the dissolution time was determined by placing the disc in approximately 10 liters of a saturated lime solution and visually determining the time it took for it to dissolve.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Analytical Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Preparation Of Clay, And Manufacture Of Mixtures Containing Clay Or Cement (AREA)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP50723997A JP4500371B2 (ja) | 1995-07-28 | 1996-07-26 | セメント混和剤のコンパクト化ユニット |
CA002201124A CA2201124C (en) | 1995-07-28 | 1996-07-26 | Compacted units of cement admixtures |
MX9702294A MX9702294A (es) | 1995-07-28 | 1996-07-26 | Unidades compactadas de mezclas de cemento. |
EP96927615A EP0784602A1 (en) | 1995-07-28 | 1996-07-26 | Compacted units of cement admixtures |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US163495P | 1995-07-28 | 1995-07-28 | |
US55636695A | 1995-11-13 | 1995-11-13 | |
US08/556,366 | 1995-11-13 | ||
US60/001,634 | 1995-11-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997005079A1 true WO1997005079A1 (en) | 1997-02-13 |
Family
ID=26669300
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1996/003315 WO1997005079A1 (en) | 1995-07-28 | 1996-07-26 | Compacted units of cement admixtures |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0784602A1 (es) |
JP (1) | JP4500371B2 (es) |
CA (1) | CA2201124C (es) |
MX (1) | MX9702294A (es) |
WO (1) | WO1997005079A1 (es) |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6648962B2 (en) | 2001-09-06 | 2003-11-18 | W. R. Grace & Co.-Conn. | Micro-granulose particulates |
US7086466B2 (en) | 2004-02-10 | 2006-08-08 | Halliburton Energy Services, Inc. | Use of substantially hydrated cement particulates in drilling and subterranean applications |
GB2427613B (en) * | 2004-03-29 | 2008-02-27 | Robert Frederick Barber | Saccharide/cement coating compositions |
US7341104B2 (en) | 2004-02-10 | 2008-03-11 | Halliburton Energy Services, Inc. | Methods of using substantially hydrated cement particulates in subterranean applications |
FR2909375A1 (fr) * | 2006-12-04 | 2008-06-06 | Stylroc Sarl | Kit de composants pour la fabrication d'elements d'amenagement de la chaussee et procede de fabrication de tels elements |
US8183186B2 (en) | 2004-02-10 | 2012-05-22 | Halliburton Energy Services, Inc. | Cement-based particulates and methods of use |
US8603952B2 (en) | 2007-05-10 | 2013-12-10 | Halliburton Energy Services, Inc. | Cement compositions and methods utilizing nano-clay |
US8741818B2 (en) | 2007-05-10 | 2014-06-03 | Halliburton Energy Services, Inc. | Lost circulation compositions and associated methods |
US8940670B2 (en) | 2007-05-10 | 2015-01-27 | Halliburton Energy Services, Inc. | Cement compositions comprising sub-micron alumina and associated methods |
US9199879B2 (en) | 2007-05-10 | 2015-12-01 | Halliburton Energy Serives, Inc. | Well treatment compositions and methods utilizing nano-particles |
US9206344B2 (en) | 2007-05-10 | 2015-12-08 | Halliburton Energy Services, Inc. | Sealant compositions and methods utilizing nano-particles |
US9512351B2 (en) | 2007-05-10 | 2016-12-06 | Halliburton Energy Services, Inc. | Well treatment fluids and methods utilizing nano-particles |
US9512346B2 (en) | 2004-02-10 | 2016-12-06 | Halliburton Energy Services, Inc. | Cement compositions and methods utilizing nano-hydraulic cement |
CN109467331A (zh) * | 2018-12-12 | 2019-03-15 | 中国电力科学研究院有限公司 | 一种混凝土含气量补偿剂及其制备方法 |
WO2022203901A1 (en) * | 2021-03-26 | 2022-09-29 | Summa-Magna 1 Corporation | Cementitious composition |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009173498A (ja) * | 2008-01-25 | 2009-08-06 | Taiheiyo Cement Corp | 水硬性組成物及び硬化体 |
JP2012077205A (ja) * | 2010-10-01 | 2012-04-19 | Nippon Kagaku Toryo Kk | 水膨潤性摩擦低減組成物 |
CN110467369B (zh) * | 2018-05-10 | 2021-11-16 | 北新建材(嘉兴)有限公司 | 一种生石膏促凝剂及其制备方法和纸面石膏板 |
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EP0191278A2 (de) * | 1984-09-25 | 1986-08-20 | ALCHEM Metallchemie Produktionsges.m.b.H. | Farbpräparation, enthaltend eines oder mehrere farbgebende anorganische Metalloxide, für die Massefärbung von Baustoffen |
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DE2817080C3 (de) * | 1978-04-19 | 1985-04-04 | Skw Trostberg Ag, 8223 Trostberg | Feste Zusatzmittel für mit Wasser erhärtende Bindemittel und deren Verwendung |
JPS56140057A (en) * | 1980-03-31 | 1981-11-02 | Kao Corp | Cement admixing agent |
JPS616164A (ja) * | 1984-06-18 | 1986-01-11 | 昭和電工株式会社 | セメント混和剤 |
JPS6126541A (ja) * | 1984-07-16 | 1986-02-05 | 花王株式会社 | コンクリ−ト混和材 |
DE4342331A1 (de) * | 1993-12-11 | 1995-06-14 | Krueger Gmbh & Co Kg | Pigmentgranulat zum Einfärben von Baustoffen |
-
1996
- 1996-07-26 JP JP50723997A patent/JP4500371B2/ja not_active Expired - Fee Related
- 1996-07-26 CA CA002201124A patent/CA2201124C/en not_active Expired - Lifetime
- 1996-07-26 WO PCT/EP1996/003315 patent/WO1997005079A1/en not_active Application Discontinuation
- 1996-07-26 EP EP96927615A patent/EP0784602A1/en not_active Withdrawn
- 1996-07-26 MX MX9702294A patent/MX9702294A/es active IP Right Grant
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0191278A2 (de) * | 1984-09-25 | 1986-08-20 | ALCHEM Metallchemie Produktionsges.m.b.H. | Farbpräparation, enthaltend eines oder mehrere farbgebende anorganische Metalloxide, für die Massefärbung von Baustoffen |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6648962B2 (en) | 2001-09-06 | 2003-11-18 | W. R. Grace & Co.-Conn. | Micro-granulose particulates |
US9018147B2 (en) | 2004-02-10 | 2015-04-28 | Halliburton Energy Services, Inc. | Cement-based particulates and methods of use |
US7086466B2 (en) | 2004-02-10 | 2006-08-08 | Halliburton Energy Services, Inc. | Use of substantially hydrated cement particulates in drilling and subterranean applications |
US7341104B2 (en) | 2004-02-10 | 2008-03-11 | Halliburton Energy Services, Inc. | Methods of using substantially hydrated cement particulates in subterranean applications |
US8183186B2 (en) | 2004-02-10 | 2012-05-22 | Halliburton Energy Services, Inc. | Cement-based particulates and methods of use |
US9512346B2 (en) | 2004-02-10 | 2016-12-06 | Halliburton Energy Services, Inc. | Cement compositions and methods utilizing nano-hydraulic cement |
GB2427613B (en) * | 2004-03-29 | 2008-02-27 | Robert Frederick Barber | Saccharide/cement coating compositions |
FR2909375A1 (fr) * | 2006-12-04 | 2008-06-06 | Stylroc Sarl | Kit de composants pour la fabrication d'elements d'amenagement de la chaussee et procede de fabrication de tels elements |
WO2008067986A1 (fr) * | 2006-12-04 | 2008-06-12 | Stylroc | Kit de composants pour la fabrication d'elements d'amenagement de la chaussee et procede de fabrication de tels elements |
US8741818B2 (en) | 2007-05-10 | 2014-06-03 | Halliburton Energy Services, Inc. | Lost circulation compositions and associated methods |
US8940670B2 (en) | 2007-05-10 | 2015-01-27 | Halliburton Energy Services, Inc. | Cement compositions comprising sub-micron alumina and associated methods |
US9199879B2 (en) | 2007-05-10 | 2015-12-01 | Halliburton Energy Serives, Inc. | Well treatment compositions and methods utilizing nano-particles |
US9206344B2 (en) | 2007-05-10 | 2015-12-08 | Halliburton Energy Services, Inc. | Sealant compositions and methods utilizing nano-particles |
US9512351B2 (en) | 2007-05-10 | 2016-12-06 | Halliburton Energy Services, Inc. | Well treatment fluids and methods utilizing nano-particles |
US8603952B2 (en) | 2007-05-10 | 2013-12-10 | Halliburton Energy Services, Inc. | Cement compositions and methods utilizing nano-clay |
US9512352B2 (en) | 2007-05-10 | 2016-12-06 | Halliburton Energy Services, Inc. | Well treatment fluids and methods utilizing nano-particles |
CN109467331A (zh) * | 2018-12-12 | 2019-03-15 | 中国电力科学研究院有限公司 | 一种混凝土含气量补偿剂及其制备方法 |
CN109467331B (zh) * | 2018-12-12 | 2022-08-19 | 中国电力科学研究院有限公司 | 一种混凝土含气量补偿剂及其制备方法 |
WO2022203901A1 (en) * | 2021-03-26 | 2022-09-29 | Summa-Magna 1 Corporation | Cementitious composition |
Also Published As
Publication number | Publication date |
---|---|
CA2201124C (en) | 2008-03-18 |
MX9702294A (es) | 1997-06-28 |
JPH10506876A (ja) | 1998-07-07 |
CA2201124A1 (en) | 1997-02-13 |
EP0784602A1 (en) | 1997-07-23 |
JP4500371B2 (ja) | 2010-07-14 |
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