CA2136846C - Cellular concrete - Google Patents
Cellular concrete Download PDFInfo
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- CA2136846C CA2136846C CA002136846A CA2136846A CA2136846C CA 2136846 C CA2136846 C CA 2136846C CA 002136846 A CA002136846 A CA 002136846A CA 2136846 A CA2136846 A CA 2136846A CA 2136846 C CA2136846 C CA 2136846C
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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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/08—Fats; Fatty oils; Ester type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
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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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/0076—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials characterised by the grain distribution
- C04B20/008—Micro- or nanosized fillers, e.g. micronised fillers with particle size smaller than that of the hydraulic binder
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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
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/02—Agglomerated materials, e.g. artificial aggregates
- C04B18/027—Lightweight materials
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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
- C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
- C04B22/08—Acids or salts thereof
- C04B22/12—Acids or salts thereof containing halogen in the anion
- C04B22/124—Chlorides of ammonium or of the alkali or alkaline earth metals, e.g. calcium chloride
-
- 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
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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
- 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
- C04B28/24—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 alkyl, ammonium or metal silicates; containing silica sols
- C04B28/26—Silicates of the alkali metals
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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
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/34—Non-shrinking or non-cracking materials
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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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/40—Porous or lightweight materials
- C04B2111/42—Floating materials
Abstract
A more economical, stable, non-shrinking cellular concrete is provided by the addition of cementitious or non-cementitious fines to a cellular concrete mix. The improved cellular concrete is attained by reducing the amount of cement and replacing it with an equal amount of cementitious or non-cimentitious fines. The partial replacement of the more expensive cement for the less expensive fines results in a more economical choice of cellular concrete suitable for use in structural applications, for insula-tion purposes, and for use in producing lightweight aggregate.
Description
pGT/US93/05194 This invention relates to the field of 6 concrete technology and to compositions useful in producing cellular (foamed) concrete and to a 8 process for producing same. The invention also relates to producing cellular concrete suitable for use in producing lightweight aggregate material 11 therefrom, especially lightweight aggregate for use 12 in poured concrete and concrete block mixes and for 13 lightweight insulation mixes.
Concrete, composed of cement, aggregate 16 and water, is a well known building material having 17 considerable compressive strength. There are 18 multiplicities of application where low density 19 concrete is a suitable, useful or desirable material since it has the advantage of light weight and 21 favorable insulation properties.
22 In general there have been several methods 23 to produce such low density concrete and lightweight 24 aggregate. In one way, lightweight aggregate material, such as cinders available in ash heaps 26 from coal-burning power plants, was used to produce 27 such low density concrete products. However, a 28 decade ago or more, when such cinders were no longer 29 generally available, manufacturers substituted bloated slate, clays and shale, fly ash, pumice and 31 the like which they produced in rotary kilns or 32 sintering machines. While such kilned or sintered 33 materials and methods using such heat-expanded 34 materials are still currently in use, they are not 5 PCT/US93/0~ a 1 very satisfactory or efficient as well as being 2 increasingly very expensive due to material costs, 3 fuel costs and labor costs. The expensive massive 4 kilns or sintering equipment produce only relatively small amounts of product per working shift.
Concrete, composed of cement, aggregate 16 and water, is a well known building material having 17 considerable compressive strength. There are 18 multiplicities of application where low density 19 concrete is a suitable, useful or desirable material since it has the advantage of light weight and 21 favorable insulation properties.
22 In general there have been several methods 23 to produce such low density concrete and lightweight 24 aggregate. In one way, lightweight aggregate material, such as cinders available in ash heaps 26 from coal-burning power plants, was used to produce 27 such low density concrete products. However, a 28 decade ago or more, when such cinders were no longer 29 generally available, manufacturers substituted bloated slate, clays and shale, fly ash, pumice and 31 the like which they produced in rotary kilns or 32 sintering machines. While such kilned or sintered 33 materials and methods using such heat-expanded 34 materials are still currently in use, they are not 5 PCT/US93/0~ a 1 very satisfactory or efficient as well as being 2 increasingly very expensive due to material costs, 3 fuel costs and labor costs. The expensive massive 4 kilns or sintering equipment produce only relatively small amounts of product per working shift.
6 Moreover, such heat-expanded aggregate making 7 methods have not produced products with uniformly 8 satisfactory properties. Besides requiring 9 expensive and cumbersome machinery, heat-expansion processes create highly undesirable air pollution.
11 Additionally, the specialized raw materials for 12 producing such heat-expanded products are only 13 available in certain limited geographic areas, often 14 remote from the desired site for use.
Another manufactured lightweight aggregate 16 is expanded slag. Hot dross is separated from the 17 molten iron in steel production and is put in 18 contact with water to cause bloating. Since the 19 residue is a by-product, the aggregate is economical, but since it is dross it is neither 21 uniform nor stable and therefore does not produce 22 sufficiently uniform low density concrete.
23 Additionally, it has been suggested that 24 low density concrete could be produced by making a "cellular concrete" by adding air-bubble containing 26 foam to a concrete mix and trapping the air-bubbles 27 therein. However, much of these bubbles are 28 generally lost during the step in which the foamed 29 composition is mixed with the concrete or during pouring of the concrete mix. The foamed 31 compositions tend to break down or bubbles collapse 32 and are lost during mechanical mixing of the 33 compositions resulting in a large loss of air.
34 Additionally, bubbles of the foamed composition tend -° WO 93/24425 236846 PGT/US93/05194 1 to coalesce into each other and form relatively 2 large and unstable air pockets, resulting in loss of 3 cell integrity. Moreover, such cellular concretes 4 have generally suffered from undesirable, unpredictable shrinkage and cracking during the 6 curing or setting operation which tends to be 7 erratic. All these factors tend to produce weakened 8 cellular concrete. Also, such cellular concrete 9 requires specialized on-the-job mixing apparatus, and the foam mix specifications must be tailorized 11 for the necessary foam fluidity characteristics with 12 increased water content needed to avoid undue loss 13 of bubbles, rather than for the ultimate desired 14 low-slump structural concrete mix specifications.
Accordingly, such cellular concrete has found use 16 primarily only in floor fills and roof deck 17 applications, providing insulation and some modicum 18 of fire protection, but due to the shrinkage and 19 cracking or due to the need for specialized apparatus and the foam mix characteristics as 21 described, conventional foamed concrete is generally 22 unsuitable for use as a structural concrete.
23 One method of attempting to produce 24 lightweight aggregate has been to provide a body of cured cellular concrete, breaking the body into 26 fragments, coating the fragments with a thin layer 27 of cement which is allowed to cure and incorporating 28 the coated fragments in a cement matrix to form low 29 density concrete. Such a method is disclosed for example in U.S. Pat. No. 4,351,670 issued Sept. 28, 31 1982 to Harold E. Grice. However, such products are 32 not sufficiently stable and require a cumbersome 33 process for preparation. In addition, such cellular 34 concrete suffers from erratic curing or setting that 213846 .
WO 93/24425 PCT/US93/0: 4 1 results in setting-shrinkage or coalescing of cells 2 and loss of cell integrity as discussed previously.
3 Moreover, the use of such cellular 4 concrete to produce lightweight aggregate by heretofore employed methods has required the use of 6 massive crushing equipment to transform the cellular 7 concrete into suitable lightweight aggregate.
8 Another method of producing lightweight 9 aggregate has been to add a colloidal solution or sol-gel of sodium bentonite, peptized calcium li bentonite, attapulgite or a gelled silica, such as 12 a sodium silicate-CaCl2 sol-gel, to a cellular 13 concrete mix. Such a method is disclosed in U.S.
14 Patent No. 4,900,349 issued February 13, 1990, to Lawrence F. Gelbman. Setting-shrinkage in the 16 resulting cellular concrete is substantially 17 eliminated as is cell coalescing so that cell 18 integrity of the cellular concrete is maintained.
19 This particular cellular concrete is characterized by an increased strength to weight ratio and 21 therefore is much more suitable for use in 22 structural applications as well as for insulation 23 purposes. Additionally, this cellular concrete 24 absorbs substantially no water in the cells since the cells have not coalesced and are not 26 interconnected. Moreover, such cellular concrete 27 may be converted to substantially uniform and stable 28 lightweight aggregate by heretofore known crushing 29 methods. However, such cellular concrete is still quite expensive to produce in commercial quantities 31 because cellular concretes of this type require 32 substantial quantities of cement, generally the 33 costliest ingredient in cellular concrete.
34 It is therefore an object of this ~136~46 1 invention to provide an economically manufactured 2 lightweight aggregate that can be produced in commercial 3 quantities to meet the increasing demand.
4 SUMMP.RY OF THE INVENTION
It has been discovered that an economical, 6 stable, non-shrinking cellular concrete can be produced 7 by the substitution of cementitious fines, such as kiln 8 dust, or non-cementitious fines, such as limestone, for a 9 portion of the cement in a cellular concrete mix. The improved cellular concrete of this invention is 11 characterized by a partial replacement of the expensive 12 cement component with an equal amount of the less 13 expensive fines. Such improved cellular concrete can 14 then be crushed to produce a substantially uniform and lightweight aggregate.
16 Accordingly, in one aspect the present 17 invention resides in a cellular concrete mix for the 18 preparation of cellular concrete aggregate comprising:
19 (a) cement;
(b) water;
21 (c) an additive comprising a colloidal 22 solution or sol-gel composition selected from the group 23 consisting of suspensions of water-sodium bentonite, 24 water-peptized calcium bentonite, water-attapulgite and a gelled silica based sol-gel;
26 (d) fines having a particle size of about 74um 27 or less; and 28 (e) a stable small-celled foam composition 29 comprising a foam-making agent, the water being present in an amount to hydrate 31 the cement and sustain the foam, the fines being present 32 in an amount between 10~ and 70~ of the combined weight 33 of fines and cement, and the additive being present in an 213fi~46 - Sa -1 amount sufficient to substantially eliminate setting-2 shrinkage of the cellular concrete and prevent cell 3 coalescing.
4 In another aspect, the present invention resides in a cellular concrete aggregate produced by the 6 process comprising substantially uniformly mixing 7 together:
8 (a) cement;
9 (b) water;
(c) an additive comprising a colloidal 11 solution or sol-gel composition selected from the group 12 consisting of suspensions of water-sodium bentonite, 13 water peptized calcium bentonite, water attapulgite and a 14 gelled silica based sol-gel;
(d) fines having a particle size of about 74um 16 or less;
17 (e) a stable small-celled foam composition 18 comprising a foam-making agent, 19 the water being present in an amount to hydrate the cement and sustain the foam, the fines being present 21 in an amount of between 10$ and 70~ by weight of the 22 combined weight of fines and cement, and the additive 23 being present in an amount sufficient to substantially 24 eliminate setting-shrinkage of the cellular concrete and present cell coalescing, to form a cellular cement mix 26 and thereafter permitting cellular cement mix to set 27 forming a cellular concrete substantially free of 28 setting-shrinkage and loss of cell integrity due to 29 coalescing of cells.
More preferably, the cellular concrete is 31 buoyant so as to be adapted to float on the surface of 32 water for at least two, and more preferably several 33 months .
B
-sb- ~'~3fi~46 1 In another aspect, the present invention resides in 2 a cellular concrete mix for the preparation of cellular 3 concrete aggregate, comprising:
4 (a) cement, s (b) water, 6 (c) an additive comprising a gelled silica 7 based sol-gel of silica-calcium chloride, 8 (d) fines having a particle size of about 74um 9 or less; and (e) a stable small-celled foam composition 11 comprising a foam-making agent, 12 the water being present in an amount to hydrate 13 the cement and sustain the foam, the fines being present 14 in an amount of between 10~ and 70~ by weight of the is combined weight of fines and cement, and the additive 16 being present in an amount sufficient to substantially 17 eliminate setting-shrinkage of the cellular concrete and 18 prevent cell coalescing.
I have discovered that so-called fines, either 21 cementitious or non-cementitious, may be substituted for 22 a portion of the cement in a cellular concrete mix such 23 as described and claimed in U.S. Patent No. 4,900,359 to 24 produce an improved, low cost, cellular concrete which Zs provides a more economical alternative for yielding 26 commercial quantities. As used herein the term "fines"
27 means particles that can pass through a screen no coarser 28 than about 200 mesh, namely as having a particle size of 29 about 74pm or less. The term "cellular cement mix" is inclusive of a mix as defined in U.S. Patent No.
31 4,900,359 and includes Portland cement, or cement and 32 sand, or cement and crushed stone or cement, sand and 33 crushed stone or such mixes with other typical cement mix -s~- 213646 1 ingredients which any suitable air-bubble containing foam 2 as well as sufficient water to hydrate the cement mix and 3 sustain the B
"~.... WO 93/24425 PGT/US93/05194 1 foam. However, these prior art mixes are modified 2 by adding cementitious fines to the cellular 3 concrete mix such as, for example, flyash (Type C or 4 F), slag cement or kiln dust, or non-cementitious fines such as, for example, limestone, silica or 6 granitic fines. This enables the amount of the 7 cement component in the cellular concrete mix to be 8 reduced, the cementitious fines employed being added 9 in an amount not to exceed about 70% of the total weight of cement and cementitious fines, or 50% of 11 the total weight of cement and non-cementitious 12 fines. The preferred ratio of cement to fines is 13 7:3, and the minimum amount of fines, either 14 cementitious or non-cementitious, should not be below about 10% of the total weight of cement and 16 fines.
17 The concrete mix also includes an additive 18 which preferably comprises a colloidal suspension 19 (hereinafter referred to as mixture) of sodium bentonite, peptized calcium bentonite or attapulgite 21 with water in a weight ratio of about 1:10 (about 22 9.1% solids) the ratio of the two respective 23 components can range from about 1:4 (about 20.0%
24 solids) to about 1:20 (about 4.8% solids). The 1:10 mixture is preferred since it forms an extremely 26 stable, non-separating mixture having a viscosity 27 enabling the mixture to be most easily handled that 28 is easily pumped and dispensed. Additionally, such 29 an additive product can be stored for indefinite periods before use without separation occurring.
31 Such a product can even be frozen and when thawed 32 can be used as described herein without requiring 33 any additional mixing or stirring. However, richer 34 additive mixtures, for example, the 1:4 ratio . _7_ 1 mixture, while too viscous to easily handle through 2 ordinary pumps may still be used where pumping is 3 not required, where special dispensing capabilities 4 are present or can be used as a concentrate in special cases. On the other hand, much leaner 6 additive mixtures, for example, at a 1:20 ratio 7 mixture, are much less viscous and while easily 8 handled require much more additive to be added to 9 the cellular cement mix to achieve the same effect as obtained with the preferred 1:10 ratio mixture.
11 Also, as the 1:20 ratio of components in the 12 additive is approached, the additive mixture tends 13 to show an increasing proportion of separation on I4 standing. However, with stirring of this 1:20 ratio additive before use, it is again rendered homogenous 16 and can be used as discussed.
17 While any suitable sodium bentonite can be 18 employed in the additive, in the cellular concrete 19 mix formulation and in the process of this invention, it is preferred that granular sodium 21 bentonite having an average particle size ranging 22 from about 20 to 70 mesh (840 micron to 210 micron) 23 be employed. Such a granular sodium bentonite is 24 available as GPG 30T"~' sodium bentonite from America Colloid Company, Industrial Division, of Skokie, 26 I11. GPG 30T"' sodium bentonite is preferred since, 27 among other reasons, it causes substantially less 28 dust during handling and mixing.
29 The sodium bentonite useful in the additive of this invention can be any suitable 31 colloid clay (silicate of alumina) comprised 32 principally of the clay mineral montmorillonite and 33 can generally be in a granular form of any suitable 34 gradation or in a powder form, although as indicated B
_8- .
1 a granular form thereof is preferred. However, even 2 highly milled powdered forms thereof can be 3 employed.
4 The preferred GPG 30T"' granular sodium bentonite has the approximate chemical formula (A1, 6 Fe~.b~, Mgo.~) Si'O~o(OH)2 Na+Ca+ +0.33 and has a 7 typical analysis (moisture free) of:
8 silicon: 63.02% as Si02 9 alumina : 21. 08 % as A1Z03 iron (ferric) : 3.25% as FeZPi 11 iron (ferrous): 0.35% as Ff0 12 magnesium: 2.67% as Mg0 13 sodium and potassium: 2.57% as Nato 14 calcium: 0.65% as Ca0 crystal water: 5.64% as Hz0 16 trace elements: 0.72%
I7 Any suitable attapulgite can be employed 18 in the additive for the cellular concrete mix 19 formulation and in the process of this invention.
Attapulgite is a hydrated aluminum-magnesium 21 silicate (Mg,Al)SSi80u(OH)4.4-HzO. It is preferred 22 that powdered attapulgite be employed as the 23 attapulgite component of this invention, although 24 granular attapulgite may also be employed. As examples of attapulgites found useful in this 26 invention there may be mentioned, for example, 27 attapulgite powder such as X-2059T"~ or Attagel 40T"', 28 both available from the Minerals and Chemicals 29 Division of Englehard, Edison, N.J., and granular attapulgite such as AEG GranularTM from America 31 Colloid Company, Industrial Division, Skokie, I11.
32 While any suitable peptized calcium 33 bentonite can be employed in the additive for the 34 cellular concrete mix formulation and in the process 1 of this invention, it is preferred that powdered peptized 2 calcium bentonite having an average particle size such 3 that 99% minimum passes through a 200 mesh (74 microns) 4 screen be employed. Such a powdered peptized calcium bentonite is available as Polarqel TT"" and Polarcrel IT""
6 from American Colloid Company, Industrial Division, of 7 Skokie, Ill.
8 The peptized calcium bentonite useful in the 9 additive of this invention can be any suitable colloid clay (silicate of alumina) comprised principally of the 11 clay mineral montmorillonite and can generally be in a 12 granular form of any suitable gradation or in a powder 13 form, although as indicated a powdered form thereof is 14 preferred. Calcium bentonite which has not been peptized does not provide a suitable additive according to this 16 invention.
17 The preparation of the colloidal suspension of 18 sodium bentonite, peptized calcium bentonite or 19 attapulgite additive is described in the aforementioned Gelbman Patent No. 4,900,349.
21 Additionally, the additive can be any suitable 22 gelled silica based sol-gel composition, such as for 23 example a silica-calcium chloride sol-gel. An especially 24 preferred silica based sol-gel is provided by mixing together a solution of about 21.1 grams of calcium 26 chloride flakes and 300 grams of water with a mixture of 27 about 100 grams 42 degree sodium silicate and 300 grams 28 of water. It will be appreciated, however, that other 29 suitable silica based sol-gel can be similarly provided and employed in this invention.
B
i f' ~~,v .~.., ....r ,.~ WO 93/24425 2~.3~8~6 PCT/US93/05194 1 The additive mixtures of the invention are 2 employed in cellular concrete mixes to provide the 3 improved cellular concrete mix formulations of this 4 invention. Generally it has been found that the use of from about 1 quart to about 36 quarts of the 6 heretofore described additive mixture per cubic yard 7 of cellular concrete mix provides the benefits of 8 this invention as discussed hereinbefore and 9 hereinafter. As little as 1 quart of the additive mixture can be used to provide the benefits of this 11 invention for cellular concrete. More than about 36 12 quarts of additive can be used per cubic yard of 13 cellular concrete mix, but such large portions of 14 the additive become more expensive and require more mixing time and do not produce increased benefits, 16 and thus are generally uneconomic and wasteful. It 17 is preferred that about 1 to about 16 quarts, most 18 preferably about 2 to about 12 quarts, of the 19 additive mixture per cubic yard of cellular concrete mix be employed for optimum results and optimum 21 economics.
22 The improved cellular concrete of this 23 invention is produced by addition of the 24 hereinbefore described additive to a cellular concrete mix before the addition of the air-bubble 26 foam composition. That is, the additive is added to 27 and homogeneously mixed with a mixture of either a 28 Portland cement or a cement and sand and/or crushed 29 stone mix, and cementitious or non-cementitious fines to which sufficient water is added to hydrate 31 the mixture, and thereafter a stable foam 32 composition containing multitudes of tiny bubbles 33 necessary to produce a cellular concrete is added to 34 the hydrated mixture. Mixing of all the ingredients 1 is continued until the formed, hydrated mix is 2 uniform. The thus foamed cellular concrete mix is 3 then discharged into suitable setting containers or 4 forms, preferably wide and shallow setting containers, for example mortar tubs, and permitted 6 to set. If the cellular concrete is to be employed 7 as lightweight aggregate, the set cellular concrete 8 material is then broken up if necessary, as by a 9 jack hammer, and is then introduced into a suitable l0 crushing apparatus, such as an impact jaw or roll 11 crusher or front end loader or the like or is 12 subjected to a grinding process and crushed into 13 lumps of lightweight aggregate.
14 The stable foam composition used to produce the cellular concrete products of this 16 invention is preferably first prepared as a 17 preformed stable foam composition and then 18 subsequently mixed with the hereinbefore described 19 cement mixture containing the fines of this invention, an additive and additional water if 21 needed. Alternatively, the cellular concrete may be 22 formed directly by producing the stable foam in situ 23 by mixing together the hereinbefore described cement 24 mixture containing fines of this invention, an additive, water if necessary and the required amount 26 of components for producing the stable foam in a 27 "whipping" type mixer. The hydrated mixture with 28 additive is then whipped until the desired amount of 29 foaming has been achieved whereupon the foamed mix is discharged into setting containers, permitted to 31 set.
32 The preformed foam method provides for 33 extremely accurate control of the amount of foam, 34 particularly for large sized batches. Moreover, WO 93/24425 2~36~'~6., PCT/US93/05~4 1 since the foam has already been preformed in a small 2 batch, such method requires only standard and 3 relatively inexpensive mixing equipment that is 4 readily available in both small and large batch sizes up to 3 cubic yards and in the very large 6 batch sizes of 10 cubic yards or more provided by 7 the already-mixed concrete delivery trucks in wide 8 usage. The in situ method on the other hand 9 requires special, expensive type whipping mixers which are generally very limited in size. It is now il preferred that the improved cellular concrete of 12 this invention be produced in a continuous process 13 wherein the fines, the additive and stable foam 14 compositions are continuously added to the hereinbefore described cement or cement and/or sand 16 or crushed stone in a continuous process line for 17 producing concrete. In the presently employed 18 continuous process, the cement and cementitious or 19 non-cementitious fines are fed to a mixing system via a pneumatic feed or a screw auger. A high 21 energy mixing system is employed in which the 22 cement, fines, additive and water are mixed to a 23 smooth slurry. A positive displacement pump 24 continuously withdraws the smooth slurry from the mixing system and foam is injected continuously into 26 the slurry at the discharge head of the pump. Thus 27 a uniform cellular concrete is continuously produced 28 and pumped into molds or into a large bounded area 29 forming a pond. After curing, the molds are disassembled or the large bounded area of cellular 31 concrete is broken up with suitable equipment such 32 as a front end loader and the material is placed in 33 inventory or is immediately crushed into 34 appropriately sized lightweight aggregate.
,.-. WO 93/24425 1 In the preformed foam batch mix method, 2 the hereinbefore described cement mix containing 3 fines of this invention and an additive is mixed in 4 the usual manner for mixing a conventional batch of concrete, then just a brief time interval before 6 delivery of the batch into a mold or building site, 7 the preformed foam is introduced into the batch 8 being mixed. This brief time interval is of 9 sufficiently short duration to enable the preformed foam to become thoroughly mixed with the batch but 11 not significantly longer than that brief duration, 12 because the mixing agitation does tend to collapse 13 some of the desired air-bubbles. For example, the 14 overall mixing cycle for the batch as a whole may be of the order of about 4 to 6 minutes. Then, for 16 example, the preformed foam is preferred to be f 17 introduced into this batch being mixed for the brief 18 time of about 1 to 3 minutes before the end of this 19 overall mixing cycle.
The stable foam compositions for use in 21 this invention may be prepared from any suitable 22 foaming agent (air-bubble foam-making agent) that 23 when suitably mixed and agitated with water produces 24 a foam of small cell structure which foam is stable enough to maintain cell structure without 26 significant collapsing during the setting of the 27 concrete with which it is mixed. As foam-making 28 agents suitable for producing such stable foams 29 according to this invention one can employ any suitable soap and non-soap surfactants or 31 emulsifiers. Any suitable non-soap foam-making 32 agent can be employed including anionic, nonionic, 33 amphoteric, zwitterionic and cationic types.
34 Examples of suitable soaps are the sodium, WO 93/24425 2.~.i~~l~~~
PGT/US93/0~4 1 potassium, ammonium and alkanol ammonium salts of 2 higher fatty acids (those having 10-20 carbon 3 atoms). Anionic non-soap surfactants can be 4 exemplified by the alkali metal salts of organic sulfuric reaction products having in their molecular 6 structure an alkyl radical containing from 8-22 7 carbon atoms and a sulfonic acid or sulfuric acid 8 ester radical (included in the term alkyl is the 9 alkyl portion of higher acyl radicals). Preferred are the sodium, ammonium, potassium or il triethanolamine alkyl sulfates, especially those 12 obtained by sulfating the higher alcohols (c8-C~8 13 carbon atoms), sodium coconut oil fatty acid 14 monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid esters of the 16 reaction product of 1 mole of a higher fatty alcohol 17 (e.g., tallow or coconut oil alcohols) and 1 to 12 18 moles of ethylene oxide: sodium or potassium salts 19 of alkyl phenol ethylene oxide ether sulfate with 1 to 10 units of ethylene oxide per molecule and in 21 which the alkyl radicals contain from 8 to 12 carbon 22 atoms, sodium alkyl glyceryl ether sulfonates; the 23 reaction product of fatty acids having from 10 to 22 24 carbon atoms esterified with isethionic acid and neutralized with sodium hydroxide; and water soluble 26 salts of condensation products of fatty acids with 27 sarcosine.
28 Nonionic surfactants can be broadly 29 defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with 31 an organic hydrophobic compound, which may be 32 aliphatic or alkyl aromatic in nature. Examples of 33 classes of nonionic surfactants are set forth in 34 detail in the aforementioned Gelbman Patent No.
11 Additionally, the specialized raw materials for 12 producing such heat-expanded products are only 13 available in certain limited geographic areas, often 14 remote from the desired site for use.
Another manufactured lightweight aggregate 16 is expanded slag. Hot dross is separated from the 17 molten iron in steel production and is put in 18 contact with water to cause bloating. Since the 19 residue is a by-product, the aggregate is economical, but since it is dross it is neither 21 uniform nor stable and therefore does not produce 22 sufficiently uniform low density concrete.
23 Additionally, it has been suggested that 24 low density concrete could be produced by making a "cellular concrete" by adding air-bubble containing 26 foam to a concrete mix and trapping the air-bubbles 27 therein. However, much of these bubbles are 28 generally lost during the step in which the foamed 29 composition is mixed with the concrete or during pouring of the concrete mix. The foamed 31 compositions tend to break down or bubbles collapse 32 and are lost during mechanical mixing of the 33 compositions resulting in a large loss of air.
34 Additionally, bubbles of the foamed composition tend -° WO 93/24425 236846 PGT/US93/05194 1 to coalesce into each other and form relatively 2 large and unstable air pockets, resulting in loss of 3 cell integrity. Moreover, such cellular concretes 4 have generally suffered from undesirable, unpredictable shrinkage and cracking during the 6 curing or setting operation which tends to be 7 erratic. All these factors tend to produce weakened 8 cellular concrete. Also, such cellular concrete 9 requires specialized on-the-job mixing apparatus, and the foam mix specifications must be tailorized 11 for the necessary foam fluidity characteristics with 12 increased water content needed to avoid undue loss 13 of bubbles, rather than for the ultimate desired 14 low-slump structural concrete mix specifications.
Accordingly, such cellular concrete has found use 16 primarily only in floor fills and roof deck 17 applications, providing insulation and some modicum 18 of fire protection, but due to the shrinkage and 19 cracking or due to the need for specialized apparatus and the foam mix characteristics as 21 described, conventional foamed concrete is generally 22 unsuitable for use as a structural concrete.
23 One method of attempting to produce 24 lightweight aggregate has been to provide a body of cured cellular concrete, breaking the body into 26 fragments, coating the fragments with a thin layer 27 of cement which is allowed to cure and incorporating 28 the coated fragments in a cement matrix to form low 29 density concrete. Such a method is disclosed for example in U.S. Pat. No. 4,351,670 issued Sept. 28, 31 1982 to Harold E. Grice. However, such products are 32 not sufficiently stable and require a cumbersome 33 process for preparation. In addition, such cellular 34 concrete suffers from erratic curing or setting that 213846 .
WO 93/24425 PCT/US93/0: 4 1 results in setting-shrinkage or coalescing of cells 2 and loss of cell integrity as discussed previously.
3 Moreover, the use of such cellular 4 concrete to produce lightweight aggregate by heretofore employed methods has required the use of 6 massive crushing equipment to transform the cellular 7 concrete into suitable lightweight aggregate.
8 Another method of producing lightweight 9 aggregate has been to add a colloidal solution or sol-gel of sodium bentonite, peptized calcium li bentonite, attapulgite or a gelled silica, such as 12 a sodium silicate-CaCl2 sol-gel, to a cellular 13 concrete mix. Such a method is disclosed in U.S.
14 Patent No. 4,900,349 issued February 13, 1990, to Lawrence F. Gelbman. Setting-shrinkage in the 16 resulting cellular concrete is substantially 17 eliminated as is cell coalescing so that cell 18 integrity of the cellular concrete is maintained.
19 This particular cellular concrete is characterized by an increased strength to weight ratio and 21 therefore is much more suitable for use in 22 structural applications as well as for insulation 23 purposes. Additionally, this cellular concrete 24 absorbs substantially no water in the cells since the cells have not coalesced and are not 26 interconnected. Moreover, such cellular concrete 27 may be converted to substantially uniform and stable 28 lightweight aggregate by heretofore known crushing 29 methods. However, such cellular concrete is still quite expensive to produce in commercial quantities 31 because cellular concretes of this type require 32 substantial quantities of cement, generally the 33 costliest ingredient in cellular concrete.
34 It is therefore an object of this ~136~46 1 invention to provide an economically manufactured 2 lightweight aggregate that can be produced in commercial 3 quantities to meet the increasing demand.
4 SUMMP.RY OF THE INVENTION
It has been discovered that an economical, 6 stable, non-shrinking cellular concrete can be produced 7 by the substitution of cementitious fines, such as kiln 8 dust, or non-cementitious fines, such as limestone, for a 9 portion of the cement in a cellular concrete mix. The improved cellular concrete of this invention is 11 characterized by a partial replacement of the expensive 12 cement component with an equal amount of the less 13 expensive fines. Such improved cellular concrete can 14 then be crushed to produce a substantially uniform and lightweight aggregate.
16 Accordingly, in one aspect the present 17 invention resides in a cellular concrete mix for the 18 preparation of cellular concrete aggregate comprising:
19 (a) cement;
(b) water;
21 (c) an additive comprising a colloidal 22 solution or sol-gel composition selected from the group 23 consisting of suspensions of water-sodium bentonite, 24 water-peptized calcium bentonite, water-attapulgite and a gelled silica based sol-gel;
26 (d) fines having a particle size of about 74um 27 or less; and 28 (e) a stable small-celled foam composition 29 comprising a foam-making agent, the water being present in an amount to hydrate 31 the cement and sustain the foam, the fines being present 32 in an amount between 10~ and 70~ of the combined weight 33 of fines and cement, and the additive being present in an 213fi~46 - Sa -1 amount sufficient to substantially eliminate setting-2 shrinkage of the cellular concrete and prevent cell 3 coalescing.
4 In another aspect, the present invention resides in a cellular concrete aggregate produced by the 6 process comprising substantially uniformly mixing 7 together:
8 (a) cement;
9 (b) water;
(c) an additive comprising a colloidal 11 solution or sol-gel composition selected from the group 12 consisting of suspensions of water-sodium bentonite, 13 water peptized calcium bentonite, water attapulgite and a 14 gelled silica based sol-gel;
(d) fines having a particle size of about 74um 16 or less;
17 (e) a stable small-celled foam composition 18 comprising a foam-making agent, 19 the water being present in an amount to hydrate the cement and sustain the foam, the fines being present 21 in an amount of between 10$ and 70~ by weight of the 22 combined weight of fines and cement, and the additive 23 being present in an amount sufficient to substantially 24 eliminate setting-shrinkage of the cellular concrete and present cell coalescing, to form a cellular cement mix 26 and thereafter permitting cellular cement mix to set 27 forming a cellular concrete substantially free of 28 setting-shrinkage and loss of cell integrity due to 29 coalescing of cells.
More preferably, the cellular concrete is 31 buoyant so as to be adapted to float on the surface of 32 water for at least two, and more preferably several 33 months .
B
-sb- ~'~3fi~46 1 In another aspect, the present invention resides in 2 a cellular concrete mix for the preparation of cellular 3 concrete aggregate, comprising:
4 (a) cement, s (b) water, 6 (c) an additive comprising a gelled silica 7 based sol-gel of silica-calcium chloride, 8 (d) fines having a particle size of about 74um 9 or less; and (e) a stable small-celled foam composition 11 comprising a foam-making agent, 12 the water being present in an amount to hydrate 13 the cement and sustain the foam, the fines being present 14 in an amount of between 10~ and 70~ by weight of the is combined weight of fines and cement, and the additive 16 being present in an amount sufficient to substantially 17 eliminate setting-shrinkage of the cellular concrete and 18 prevent cell coalescing.
I have discovered that so-called fines, either 21 cementitious or non-cementitious, may be substituted for 22 a portion of the cement in a cellular concrete mix such 23 as described and claimed in U.S. Patent No. 4,900,359 to 24 produce an improved, low cost, cellular concrete which Zs provides a more economical alternative for yielding 26 commercial quantities. As used herein the term "fines"
27 means particles that can pass through a screen no coarser 28 than about 200 mesh, namely as having a particle size of 29 about 74pm or less. The term "cellular cement mix" is inclusive of a mix as defined in U.S. Patent No.
31 4,900,359 and includes Portland cement, or cement and 32 sand, or cement and crushed stone or cement, sand and 33 crushed stone or such mixes with other typical cement mix -s~- 213646 1 ingredients which any suitable air-bubble containing foam 2 as well as sufficient water to hydrate the cement mix and 3 sustain the B
"~.... WO 93/24425 PGT/US93/05194 1 foam. However, these prior art mixes are modified 2 by adding cementitious fines to the cellular 3 concrete mix such as, for example, flyash (Type C or 4 F), slag cement or kiln dust, or non-cementitious fines such as, for example, limestone, silica or 6 granitic fines. This enables the amount of the 7 cement component in the cellular concrete mix to be 8 reduced, the cementitious fines employed being added 9 in an amount not to exceed about 70% of the total weight of cement and cementitious fines, or 50% of 11 the total weight of cement and non-cementitious 12 fines. The preferred ratio of cement to fines is 13 7:3, and the minimum amount of fines, either 14 cementitious or non-cementitious, should not be below about 10% of the total weight of cement and 16 fines.
17 The concrete mix also includes an additive 18 which preferably comprises a colloidal suspension 19 (hereinafter referred to as mixture) of sodium bentonite, peptized calcium bentonite or attapulgite 21 with water in a weight ratio of about 1:10 (about 22 9.1% solids) the ratio of the two respective 23 components can range from about 1:4 (about 20.0%
24 solids) to about 1:20 (about 4.8% solids). The 1:10 mixture is preferred since it forms an extremely 26 stable, non-separating mixture having a viscosity 27 enabling the mixture to be most easily handled that 28 is easily pumped and dispensed. Additionally, such 29 an additive product can be stored for indefinite periods before use without separation occurring.
31 Such a product can even be frozen and when thawed 32 can be used as described herein without requiring 33 any additional mixing or stirring. However, richer 34 additive mixtures, for example, the 1:4 ratio . _7_ 1 mixture, while too viscous to easily handle through 2 ordinary pumps may still be used where pumping is 3 not required, where special dispensing capabilities 4 are present or can be used as a concentrate in special cases. On the other hand, much leaner 6 additive mixtures, for example, at a 1:20 ratio 7 mixture, are much less viscous and while easily 8 handled require much more additive to be added to 9 the cellular cement mix to achieve the same effect as obtained with the preferred 1:10 ratio mixture.
11 Also, as the 1:20 ratio of components in the 12 additive is approached, the additive mixture tends 13 to show an increasing proportion of separation on I4 standing. However, with stirring of this 1:20 ratio additive before use, it is again rendered homogenous 16 and can be used as discussed.
17 While any suitable sodium bentonite can be 18 employed in the additive, in the cellular concrete 19 mix formulation and in the process of this invention, it is preferred that granular sodium 21 bentonite having an average particle size ranging 22 from about 20 to 70 mesh (840 micron to 210 micron) 23 be employed. Such a granular sodium bentonite is 24 available as GPG 30T"~' sodium bentonite from America Colloid Company, Industrial Division, of Skokie, 26 I11. GPG 30T"' sodium bentonite is preferred since, 27 among other reasons, it causes substantially less 28 dust during handling and mixing.
29 The sodium bentonite useful in the additive of this invention can be any suitable 31 colloid clay (silicate of alumina) comprised 32 principally of the clay mineral montmorillonite and 33 can generally be in a granular form of any suitable 34 gradation or in a powder form, although as indicated B
_8- .
1 a granular form thereof is preferred. However, even 2 highly milled powdered forms thereof can be 3 employed.
4 The preferred GPG 30T"' granular sodium bentonite has the approximate chemical formula (A1, 6 Fe~.b~, Mgo.~) Si'O~o(OH)2 Na+Ca+ +0.33 and has a 7 typical analysis (moisture free) of:
8 silicon: 63.02% as Si02 9 alumina : 21. 08 % as A1Z03 iron (ferric) : 3.25% as FeZPi 11 iron (ferrous): 0.35% as Ff0 12 magnesium: 2.67% as Mg0 13 sodium and potassium: 2.57% as Nato 14 calcium: 0.65% as Ca0 crystal water: 5.64% as Hz0 16 trace elements: 0.72%
I7 Any suitable attapulgite can be employed 18 in the additive for the cellular concrete mix 19 formulation and in the process of this invention.
Attapulgite is a hydrated aluminum-magnesium 21 silicate (Mg,Al)SSi80u(OH)4.4-HzO. It is preferred 22 that powdered attapulgite be employed as the 23 attapulgite component of this invention, although 24 granular attapulgite may also be employed. As examples of attapulgites found useful in this 26 invention there may be mentioned, for example, 27 attapulgite powder such as X-2059T"~ or Attagel 40T"', 28 both available from the Minerals and Chemicals 29 Division of Englehard, Edison, N.J., and granular attapulgite such as AEG GranularTM from America 31 Colloid Company, Industrial Division, Skokie, I11.
32 While any suitable peptized calcium 33 bentonite can be employed in the additive for the 34 cellular concrete mix formulation and in the process 1 of this invention, it is preferred that powdered peptized 2 calcium bentonite having an average particle size such 3 that 99% minimum passes through a 200 mesh (74 microns) 4 screen be employed. Such a powdered peptized calcium bentonite is available as Polarqel TT"" and Polarcrel IT""
6 from American Colloid Company, Industrial Division, of 7 Skokie, Ill.
8 The peptized calcium bentonite useful in the 9 additive of this invention can be any suitable colloid clay (silicate of alumina) comprised principally of the 11 clay mineral montmorillonite and can generally be in a 12 granular form of any suitable gradation or in a powder 13 form, although as indicated a powdered form thereof is 14 preferred. Calcium bentonite which has not been peptized does not provide a suitable additive according to this 16 invention.
17 The preparation of the colloidal suspension of 18 sodium bentonite, peptized calcium bentonite or 19 attapulgite additive is described in the aforementioned Gelbman Patent No. 4,900,349.
21 Additionally, the additive can be any suitable 22 gelled silica based sol-gel composition, such as for 23 example a silica-calcium chloride sol-gel. An especially 24 preferred silica based sol-gel is provided by mixing together a solution of about 21.1 grams of calcium 26 chloride flakes and 300 grams of water with a mixture of 27 about 100 grams 42 degree sodium silicate and 300 grams 28 of water. It will be appreciated, however, that other 29 suitable silica based sol-gel can be similarly provided and employed in this invention.
B
i f' ~~,v .~.., ....r ,.~ WO 93/24425 2~.3~8~6 PCT/US93/05194 1 The additive mixtures of the invention are 2 employed in cellular concrete mixes to provide the 3 improved cellular concrete mix formulations of this 4 invention. Generally it has been found that the use of from about 1 quart to about 36 quarts of the 6 heretofore described additive mixture per cubic yard 7 of cellular concrete mix provides the benefits of 8 this invention as discussed hereinbefore and 9 hereinafter. As little as 1 quart of the additive mixture can be used to provide the benefits of this 11 invention for cellular concrete. More than about 36 12 quarts of additive can be used per cubic yard of 13 cellular concrete mix, but such large portions of 14 the additive become more expensive and require more mixing time and do not produce increased benefits, 16 and thus are generally uneconomic and wasteful. It 17 is preferred that about 1 to about 16 quarts, most 18 preferably about 2 to about 12 quarts, of the 19 additive mixture per cubic yard of cellular concrete mix be employed for optimum results and optimum 21 economics.
22 The improved cellular concrete of this 23 invention is produced by addition of the 24 hereinbefore described additive to a cellular concrete mix before the addition of the air-bubble 26 foam composition. That is, the additive is added to 27 and homogeneously mixed with a mixture of either a 28 Portland cement or a cement and sand and/or crushed 29 stone mix, and cementitious or non-cementitious fines to which sufficient water is added to hydrate 31 the mixture, and thereafter a stable foam 32 composition containing multitudes of tiny bubbles 33 necessary to produce a cellular concrete is added to 34 the hydrated mixture. Mixing of all the ingredients 1 is continued until the formed, hydrated mix is 2 uniform. The thus foamed cellular concrete mix is 3 then discharged into suitable setting containers or 4 forms, preferably wide and shallow setting containers, for example mortar tubs, and permitted 6 to set. If the cellular concrete is to be employed 7 as lightweight aggregate, the set cellular concrete 8 material is then broken up if necessary, as by a 9 jack hammer, and is then introduced into a suitable l0 crushing apparatus, such as an impact jaw or roll 11 crusher or front end loader or the like or is 12 subjected to a grinding process and crushed into 13 lumps of lightweight aggregate.
14 The stable foam composition used to produce the cellular concrete products of this 16 invention is preferably first prepared as a 17 preformed stable foam composition and then 18 subsequently mixed with the hereinbefore described 19 cement mixture containing the fines of this invention, an additive and additional water if 21 needed. Alternatively, the cellular concrete may be 22 formed directly by producing the stable foam in situ 23 by mixing together the hereinbefore described cement 24 mixture containing fines of this invention, an additive, water if necessary and the required amount 26 of components for producing the stable foam in a 27 "whipping" type mixer. The hydrated mixture with 28 additive is then whipped until the desired amount of 29 foaming has been achieved whereupon the foamed mix is discharged into setting containers, permitted to 31 set.
32 The preformed foam method provides for 33 extremely accurate control of the amount of foam, 34 particularly for large sized batches. Moreover, WO 93/24425 2~36~'~6., PCT/US93/05~4 1 since the foam has already been preformed in a small 2 batch, such method requires only standard and 3 relatively inexpensive mixing equipment that is 4 readily available in both small and large batch sizes up to 3 cubic yards and in the very large 6 batch sizes of 10 cubic yards or more provided by 7 the already-mixed concrete delivery trucks in wide 8 usage. The in situ method on the other hand 9 requires special, expensive type whipping mixers which are generally very limited in size. It is now il preferred that the improved cellular concrete of 12 this invention be produced in a continuous process 13 wherein the fines, the additive and stable foam 14 compositions are continuously added to the hereinbefore described cement or cement and/or sand 16 or crushed stone in a continuous process line for 17 producing concrete. In the presently employed 18 continuous process, the cement and cementitious or 19 non-cementitious fines are fed to a mixing system via a pneumatic feed or a screw auger. A high 21 energy mixing system is employed in which the 22 cement, fines, additive and water are mixed to a 23 smooth slurry. A positive displacement pump 24 continuously withdraws the smooth slurry from the mixing system and foam is injected continuously into 26 the slurry at the discharge head of the pump. Thus 27 a uniform cellular concrete is continuously produced 28 and pumped into molds or into a large bounded area 29 forming a pond. After curing, the molds are disassembled or the large bounded area of cellular 31 concrete is broken up with suitable equipment such 32 as a front end loader and the material is placed in 33 inventory or is immediately crushed into 34 appropriately sized lightweight aggregate.
,.-. WO 93/24425 1 In the preformed foam batch mix method, 2 the hereinbefore described cement mix containing 3 fines of this invention and an additive is mixed in 4 the usual manner for mixing a conventional batch of concrete, then just a brief time interval before 6 delivery of the batch into a mold or building site, 7 the preformed foam is introduced into the batch 8 being mixed. This brief time interval is of 9 sufficiently short duration to enable the preformed foam to become thoroughly mixed with the batch but 11 not significantly longer than that brief duration, 12 because the mixing agitation does tend to collapse 13 some of the desired air-bubbles. For example, the 14 overall mixing cycle for the batch as a whole may be of the order of about 4 to 6 minutes. Then, for 16 example, the preformed foam is preferred to be f 17 introduced into this batch being mixed for the brief 18 time of about 1 to 3 minutes before the end of this 19 overall mixing cycle.
The stable foam compositions for use in 21 this invention may be prepared from any suitable 22 foaming agent (air-bubble foam-making agent) that 23 when suitably mixed and agitated with water produces 24 a foam of small cell structure which foam is stable enough to maintain cell structure without 26 significant collapsing during the setting of the 27 concrete with which it is mixed. As foam-making 28 agents suitable for producing such stable foams 29 according to this invention one can employ any suitable soap and non-soap surfactants or 31 emulsifiers. Any suitable non-soap foam-making 32 agent can be employed including anionic, nonionic, 33 amphoteric, zwitterionic and cationic types.
34 Examples of suitable soaps are the sodium, WO 93/24425 2.~.i~~l~~~
PGT/US93/0~4 1 potassium, ammonium and alkanol ammonium salts of 2 higher fatty acids (those having 10-20 carbon 3 atoms). Anionic non-soap surfactants can be 4 exemplified by the alkali metal salts of organic sulfuric reaction products having in their molecular 6 structure an alkyl radical containing from 8-22 7 carbon atoms and a sulfonic acid or sulfuric acid 8 ester radical (included in the term alkyl is the 9 alkyl portion of higher acyl radicals). Preferred are the sodium, ammonium, potassium or il triethanolamine alkyl sulfates, especially those 12 obtained by sulfating the higher alcohols (c8-C~8 13 carbon atoms), sodium coconut oil fatty acid 14 monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid esters of the 16 reaction product of 1 mole of a higher fatty alcohol 17 (e.g., tallow or coconut oil alcohols) and 1 to 12 18 moles of ethylene oxide: sodium or potassium salts 19 of alkyl phenol ethylene oxide ether sulfate with 1 to 10 units of ethylene oxide per molecule and in 21 which the alkyl radicals contain from 8 to 12 carbon 22 atoms, sodium alkyl glyceryl ether sulfonates; the 23 reaction product of fatty acids having from 10 to 22 24 carbon atoms esterified with isethionic acid and neutralized with sodium hydroxide; and water soluble 26 salts of condensation products of fatty acids with 27 sarcosine.
28 Nonionic surfactants can be broadly 29 defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with 31 an organic hydrophobic compound, which may be 32 aliphatic or alkyl aromatic in nature. Examples of 33 classes of nonionic surfactants are set forth in 34 detail in the aforementioned Gelbman Patent No.
..m..
'136846 1 4,900,349.
2 In addition amphoteric surfactants and cationic 3 surfactants may also be used in the compositions of the 4 present invention and these are also fully described in said Gelbman Patent No. 4,900,349.
6 Many additional nonsoap surfactants are 7 described in McCUTCHEON'8, DETERGENTS AND EMULSIFIERS, 8 1979 ANNUAL, published by Allured Publishing Corporation.
9 The above-mentioned surfactants can be used alone or in combination in the foam compositions of the 11 present invention.
12 Preferably as foam-making agents it is 13 preferred to employ MEARLT"" liquid foaming agent, a 14 proteinaceous material compatible with Portland cement, available from Mearl Corporation of Roselle Park, N.J.;
'136846 1 4,900,349.
2 In addition amphoteric surfactants and cationic 3 surfactants may also be used in the compositions of the 4 present invention and these are also fully described in said Gelbman Patent No. 4,900,349.
6 Many additional nonsoap surfactants are 7 described in McCUTCHEON'8, DETERGENTS AND EMULSIFIERS, 8 1979 ANNUAL, published by Allured Publishing Corporation.
9 The above-mentioned surfactants can be used alone or in combination in the foam compositions of the 11 present invention.
12 Preferably as foam-making agents it is 13 preferred to employ MEARLT"" liquid foaming agent, a 14 proteinaceous material compatible with Portland cement, available from Mearl Corporation of Roselle Park, N.J.;
16 IVORYT"" dish-liquid, a detergent mixture of anionic and 17 nonionic surfactants with ethyl alcohol as a dispersion 18 ingredient available from the Procter & Gamble Co.; and 19 CALIMULSET"" PRS, an isopropylamine sulfate foaming agent.
Especially preferred is MEARLT"" liquid foaming agent.
21 sufficient foam-making agent is mixed with 22 water to produce the stable foam of small cell 23 structures. An effective foam-making amount, generally 24 from about 2% to about 10% by weight, preferably from about 2 1/2 % to about 5%, and most preferably from about 26 3% to about 3.5% of foam-making agent based on the weight 27 of water is employed. It is to be understood that the 28 optimal amount of foam-making agent will be dependent 29 upon the specific foam-making agent selected for use.
B
W ,~ ~r~ ~
i.. :, .' ,~", WO 93/24425 '2~.3~8,~6 PCT/US93/05194 ~2 1 The foam-making agent and water are mixed in any 2 suitable mixing vessel to produce the stable foam 3 composition. For example these ingredients can be 4 mixed into foam with multitudes of tiny bubbles therein in a MIXMASTER"' mixer or by mixing in a 6 commercially available foam generator, such as is 7 available from Mearlcrete Corporation of Roselle 8 Park, N.J.
9 As an example of a stable foam composition suitable for use in producing the improved cellular 11 concrete of this invention there can be mentioned 12 the stable foam produced by suitably mixing 3 grams 13 of MEARL"' liquid foaming agent and 90 milliliters of 14 water. This exemplary stable foam composition has been utilized to prepare exemplary cellular concrete 16 products of this invention. It will be appreciated, 17 however, that any suitable stable foam composition 18 can be employed to produce the cellular concrete 19 products of this invention.
~ It will be appreciated that by varying the 21 mixed materials ratios, variable yet controlled 22 cellular concrete densities and strengths can be 23 achieved over a relatively wide range of density as 24 measured in pounds per cubic foot. Thus, cellular concrete can be readily designed to fit any 26 particular end use design parameter desired. For 27 example, it is possible to obtain suitable cellular 28 concrete having any desired predetermined bulk 29 density in the range of from about 15 to about 95 3 0 lbs/ ft3 .
31 The amount of foam employed in the cement 32 or cement mix will be determined by the amount and 33 type other conventional cement or cement mix 34 ingredients employed and the bulk density that one 2~.3684~
.--~ WO 93/24425 PCT/US93/05194 1 desires to obtain. The less foam one employs 2 generally the higher the bulk density of the product 3 and correspondingly the more foam employed the lower 4 the bulk density of the product. For example, to obtain a cellular concrete having a bulk density of 6 about 95 lb/ft3 one would employ about 10 to 15% foam 7 by volume based on the volume of the total cement 8 mix. To obtain an especially light cellular 9 concrete, such as one with a bulk density of about 15 to 25 lb/ft3, one would employ from about 50 to il about 60% by volume of foam based on the total 12 volume of the cement mix.
13 As examples of the controllable weight 14 ranges of cellular concrete that one can produce according to this invention the following three 16 exemplary mixes are given. Each of the exemplary 17 mixes described hereinafter contains about 2 quarts 18 of the additive, a colloidal sodium bentonite, per 19 cubic yard of concrete mix. Mix I is designed to yield an aggregate of minimum weight, yet still 21 strong enough for use in some structural 22 applications such as steel fireproofing and for 23 partition block. Mixes II and III are designed to 24 yield aggregates of median density.
WO 93/24425 PCT/US93/0~'~4 4 (parts by volume) 6 Portland Cement 0.50 0.70 0.85 8 Fines 0.50 0.30 0.15 Sand - 1.74 3 12 Foam 2.25 2.34 2.4 14 Mixing Water .59 .66 .84 16 Fresh poured 17 density (lb/ft3) 39.9 69.5 69.8 19 Crushed, graded*
aggregate density 21 (lb/ft3) ** 23.4 43. 0 38. 0 23 * Aggregates are all - ~" and graded to duplicate 24 the sieve analysis of a commercially available expanded shale aggregate example.
26 ** All bulk density weights are calculated from 27 "jigged" volumes of material.
28 As previously indicated, a preferred use 29 for the lightweight concrete hereinbefore described is as an aggregate for concrete. That is to say, 31 while the concrete could be employed without further 32 processing, it is presently preferred to break it up 33 into small chunks and then to use it as an aggregate 34 for another concrete that is formed including such 2~.36~46 ,.~-,WO 93/24425 PCT/US93/05194 1 lightweight aggregate. In this preferred use, as 2 already noted, the lightweight concrete is broken 3 up, first to a size that can be handled by a 4 crusher, which breaking up can be done in any suitable well known manner such as by the use of 6 jackhammers. Thereafter the broken up chunks of 7 concrete are placed in a crusher where they are 8 crushed to a satisfactory chunk size. The chunk 9 size to which they are broken up is dependent upon the nature of the end use of the concrete including il the lightweight aggregate. The choice of such chunk 12 size is well known to persons of ordinary skill in 13 the art and requires no specific description herein.
14 Thus, for example, if the aggregate is to be employed in the production of lightweight concrete 16 block, then it has been found that the lightweight 17 concrete should be broken up by the crusher to a 18 particle size of -s", that is to a size in which the 19 broken up concrete chunks will pass through a sieve. Then the lightweight aggregate may be mixed 21 with cement and other ingredients to form a 22 lightweight concrete which is poured into suitable 23 block configurations in manners well known to those 24 skilled in the art.
By way of example, two formulations for 26 making concrete block including lightweight 27 aggregate screened to -~" are presented below.
29 Cement 500 lbs Limestone Screenings 2,650 lbs 31 Aggregate 1,000 lbs 2~36Qqs ~..
WO 93/24425 PCT/US93/05'-""'~
Especially preferred is MEARLT"" liquid foaming agent.
21 sufficient foam-making agent is mixed with 22 water to produce the stable foam of small cell 23 structures. An effective foam-making amount, generally 24 from about 2% to about 10% by weight, preferably from about 2 1/2 % to about 5%, and most preferably from about 26 3% to about 3.5% of foam-making agent based on the weight 27 of water is employed. It is to be understood that the 28 optimal amount of foam-making agent will be dependent 29 upon the specific foam-making agent selected for use.
B
W ,~ ~r~ ~
i.. :, .' ,~", WO 93/24425 '2~.3~8,~6 PCT/US93/05194 ~2 1 The foam-making agent and water are mixed in any 2 suitable mixing vessel to produce the stable foam 3 composition. For example these ingredients can be 4 mixed into foam with multitudes of tiny bubbles therein in a MIXMASTER"' mixer or by mixing in a 6 commercially available foam generator, such as is 7 available from Mearlcrete Corporation of Roselle 8 Park, N.J.
9 As an example of a stable foam composition suitable for use in producing the improved cellular 11 concrete of this invention there can be mentioned 12 the stable foam produced by suitably mixing 3 grams 13 of MEARL"' liquid foaming agent and 90 milliliters of 14 water. This exemplary stable foam composition has been utilized to prepare exemplary cellular concrete 16 products of this invention. It will be appreciated, 17 however, that any suitable stable foam composition 18 can be employed to produce the cellular concrete 19 products of this invention.
~ It will be appreciated that by varying the 21 mixed materials ratios, variable yet controlled 22 cellular concrete densities and strengths can be 23 achieved over a relatively wide range of density as 24 measured in pounds per cubic foot. Thus, cellular concrete can be readily designed to fit any 26 particular end use design parameter desired. For 27 example, it is possible to obtain suitable cellular 28 concrete having any desired predetermined bulk 29 density in the range of from about 15 to about 95 3 0 lbs/ ft3 .
31 The amount of foam employed in the cement 32 or cement mix will be determined by the amount and 33 type other conventional cement or cement mix 34 ingredients employed and the bulk density that one 2~.3684~
.--~ WO 93/24425 PCT/US93/05194 1 desires to obtain. The less foam one employs 2 generally the higher the bulk density of the product 3 and correspondingly the more foam employed the lower 4 the bulk density of the product. For example, to obtain a cellular concrete having a bulk density of 6 about 95 lb/ft3 one would employ about 10 to 15% foam 7 by volume based on the volume of the total cement 8 mix. To obtain an especially light cellular 9 concrete, such as one with a bulk density of about 15 to 25 lb/ft3, one would employ from about 50 to il about 60% by volume of foam based on the total 12 volume of the cement mix.
13 As examples of the controllable weight 14 ranges of cellular concrete that one can produce according to this invention the following three 16 exemplary mixes are given. Each of the exemplary 17 mixes described hereinafter contains about 2 quarts 18 of the additive, a colloidal sodium bentonite, per 19 cubic yard of concrete mix. Mix I is designed to yield an aggregate of minimum weight, yet still 21 strong enough for use in some structural 22 applications such as steel fireproofing and for 23 partition block. Mixes II and III are designed to 24 yield aggregates of median density.
WO 93/24425 PCT/US93/0~'~4 4 (parts by volume) 6 Portland Cement 0.50 0.70 0.85 8 Fines 0.50 0.30 0.15 Sand - 1.74 3 12 Foam 2.25 2.34 2.4 14 Mixing Water .59 .66 .84 16 Fresh poured 17 density (lb/ft3) 39.9 69.5 69.8 19 Crushed, graded*
aggregate density 21 (lb/ft3) ** 23.4 43. 0 38. 0 23 * Aggregates are all - ~" and graded to duplicate 24 the sieve analysis of a commercially available expanded shale aggregate example.
26 ** All bulk density weights are calculated from 27 "jigged" volumes of material.
28 As previously indicated, a preferred use 29 for the lightweight concrete hereinbefore described is as an aggregate for concrete. That is to say, 31 while the concrete could be employed without further 32 processing, it is presently preferred to break it up 33 into small chunks and then to use it as an aggregate 34 for another concrete that is formed including such 2~.36~46 ,.~-,WO 93/24425 PCT/US93/05194 1 lightweight aggregate. In this preferred use, as 2 already noted, the lightweight concrete is broken 3 up, first to a size that can be handled by a 4 crusher, which breaking up can be done in any suitable well known manner such as by the use of 6 jackhammers. Thereafter the broken up chunks of 7 concrete are placed in a crusher where they are 8 crushed to a satisfactory chunk size. The chunk 9 size to which they are broken up is dependent upon the nature of the end use of the concrete including il the lightweight aggregate. The choice of such chunk 12 size is well known to persons of ordinary skill in 13 the art and requires no specific description herein.
14 Thus, for example, if the aggregate is to be employed in the production of lightweight concrete 16 block, then it has been found that the lightweight 17 concrete should be broken up by the crusher to a 18 particle size of -s", that is to a size in which the 19 broken up concrete chunks will pass through a sieve. Then the lightweight aggregate may be mixed 21 with cement and other ingredients to form a 22 lightweight concrete which is poured into suitable 23 block configurations in manners well known to those 24 skilled in the art.
By way of example, two formulations for 26 making concrete block including lightweight 27 aggregate screened to -~" are presented below.
29 Cement 500 lbs Limestone Screenings 2,650 lbs 31 Aggregate 1,000 lbs 2~36Qqs ~..
WO 93/24425 PCT/US93/05'-""'~
2 Cement 500 lbs 3 Block Sand 2,800 lbs 4 Aggregate 1,000 lbs 6 After the mix is made in accordance with 7 either of these examples, water is added in an 8 appropriate amount as would be well known to the 9 person of ordinary skill, the watered mix is mixed to render it substantially uniform, and the blocks 11 are fonaed in a conventional manner. In this way 12 the lightweight concrete of the present invention 13 may be employed.
14 It should be understood that the preferred embodiments and examples described herein are for 16 illustrative purposes only and are not to be 17 construed as limiting the scope of the present 18 invention which is properly delineated only in the 19 appended claims.
14 It should be understood that the preferred embodiments and examples described herein are for 16 illustrative purposes only and are not to be 17 construed as limiting the scope of the present 18 invention which is properly delineated only in the 19 appended claims.
Claims (36)
1. A cellular concrete mix for the preparation of cellular concrete aggregate comprising (a) cement;
(b) water;
(c) an additive comprising a colloidal solution or sol-gel composition selected from the group consisting of suspensions of water-sodium bentonite, water-peptized calcium bentonite, water-attapulgite and a gelled silica based sol-gel;
(d) fines having a particle size of 74 µm or less; and (e) a stable small-celled foam composition comprising a foam-making agent, the water being present in an amount to hydrate the cement and sustain the foam, the fines being present in an amount between 10% and 70% of the combined weight of fines and cement, and the additive being present in an amount sufficient to substantially eliminate setting-shrinkage of the cellular concrete and prevent cell coalescing.
(b) water;
(c) an additive comprising a colloidal solution or sol-gel composition selected from the group consisting of suspensions of water-sodium bentonite, water-peptized calcium bentonite, water-attapulgite and a gelled silica based sol-gel;
(d) fines having a particle size of 74 µm or less; and (e) a stable small-celled foam composition comprising a foam-making agent, the water being present in an amount to hydrate the cement and sustain the foam, the fines being present in an amount between 10% and 70% of the combined weight of fines and cement, and the additive being present in an amount sufficient to substantially eliminate setting-shrinkage of the cellular concrete and prevent cell coalescing.
2. A cellular concrete mix according to claim 1, further comprising sand.
3. A cellular concrete mix according to claim 1, wherein the fines are cementitious fines selected from the group consisting of flyash (Type F and C), slag cement and kiln dust.
4. A cellular concrete mix according to claim 1, wherein the fines are non-cementitious fines selected from the group consisting of limestone, silica and granitic fines, and the amount by weight of said non-cementitious fines does not exceed 50% of the combined weight of said cement and non-cementitious fines.
5. A cellular concrete mix according to claim 1, wherein the additive is present in an amount of from 1 quart to 36 quarts per cubic yard of cellular concrete mix.
6. A cellular concrete mix according to claim 1, wherein the additive is present in an amount of from 2 quarts to 12 quarts par cubic yard of cellular concrete mix.
7. A cellular concrete mix according to claim 1, wherein the additive comprises a colloidal suspension of sodium bentonite, peptized calcium bentonite or attapulgite in water in a weight ratio of sodium bentonite, peptized calcium bentonite or attapulgite to water of from 1:4 to 1:20.
8. A cellular concrete mix according to claim 5, wherein the additive comprises a colloidal suspension of sodium bentonite, peptized calcium bentonite or attapulgite in water in a weight ratio of sodium bentonite, peptized calcium bentonite or attapulgite to water of from 1:4 to 1:20.
9. A cellular concrete mix according to claim 6, wherein the additive comprises a colloidal suspension of sodium bentonite, peptized calcium bentonite or attapulgite in water in a weight ratio of sodium bentonite, peptized calcium bentonite or attapulgite to water of from 1:4 to 1:20.
10. A cellular concrete mix according to claim 1, wherein the weight ratio of the cement to the fines is 7:3.
11. A cellular concrete aggregate produced by the process comprising substantially uniformly mixing together:
(a) cement;
(b) water;
(c) and additive comprising a colloidal solution or sol-gel composition selected from the group consisting of suspensions of water-sodium bentonite, water peptized calcium bentonite, water attapulgite and a gelled silica based sol-gel;
(d) fines having a particle size of 74 µm or less;
and uniformly mixing therewith:
(e) a stable small-celled foam composition comprising a foam-making agent, the water being present in an amount to hydrate the cement and sustain the foam, the fines being present in an amount of between 10% and 70% by weight of the combined weight of fines and cement, and the additive being present in an amount sufficient to substantially eliminate setting-shrinkage of the cellular concrete and prevent cell coalescing, to form a cellular cement mix and thereafter permitting cellular cement mix to set forming a cellular concrete substantially free of setting-shrinkage an loss of cell integrity due to coalescing of cells.
(a) cement;
(b) water;
(c) and additive comprising a colloidal solution or sol-gel composition selected from the group consisting of suspensions of water-sodium bentonite, water peptized calcium bentonite, water attapulgite and a gelled silica based sol-gel;
(d) fines having a particle size of 74 µm or less;
and uniformly mixing therewith:
(e) a stable small-celled foam composition comprising a foam-making agent, the water being present in an amount to hydrate the cement and sustain the foam, the fines being present in an amount of between 10% and 70% by weight of the combined weight of fines and cement, and the additive being present in an amount sufficient to substantially eliminate setting-shrinkage of the cellular concrete and prevent cell coalescing, to form a cellular cement mix and thereafter permitting cellular cement mix to set forming a cellular concrete substantially free of setting-shrinkage an loss of cell integrity due to coalescing of cells.
12. A cellular concrete according to claim 11, wherein the fines are cementitious fines selected from the group consisting of flyash (Type F and C), slag cement and kiln dust.
13. A cellular concrete according to claim 11, wherein the fines are non-cementitious fines selected from the group consisting of limestone, silica and granitic fines.
14. A cellular concrete of claim 11 which is buoyant an floats on the surface of water for at least two months.
15. Lightweight aggregate comprising cellular concrete of claim 11 which has been crushed.
16. A cellular concrete mix for the preparation of cellular concrete aggregate, comprising:
(a) cement, (b) water, (c) and additive comprising a gelled silica based sol-gel of silica-calcium chloride, (d) fines having a particle size of 74 µm or less; and (e) a stable small-celled foam composition comprising a foam-making agent, the water being present in an amount to hydrate the cement and sustain the foam, the fines being present in an amount of between 10% and 70% by weight of the combined weight of fines and cement, and the additive being present in an amount sufficient to substantially eliminate setting-shrinkage of the cellular concrete and prevent cell coalescing.
(a) cement, (b) water, (c) and additive comprising a gelled silica based sol-gel of silica-calcium chloride, (d) fines having a particle size of 74 µm or less; and (e) a stable small-celled foam composition comprising a foam-making agent, the water being present in an amount to hydrate the cement and sustain the foam, the fines being present in an amount of between 10% and 70% by weight of the combined weight of fines and cement, and the additive being present in an amount sufficient to substantially eliminate setting-shrinkage of the cellular concrete and prevent cell coalescing.
17. A cellular concrete mix according to claim 16, wherein the fines are cementitious fines selected from the group consisting of flyash (Type F and C) , slag cement and kiln dust.
18. A cellular concrete mix according to claim 16, wherein the fines are non-cementitious fines selected from the group consisting of limestone, silica and granitic fines, and the amount by weight of said non-cementitious fines does not exceed 50% of the combined weight of said cement and non-cementitious fines.
19. A cellular concrete mix according to claim 16, wherein the additive is present in an amount of from 1 quart to 36 quarts per cubic yard of cellular concrete mix.
20. A cellular concrete mix according to claim 16, wherein the additive is present in an amount of from 2 quarts to 12 quarts per cubic yard of cellular concrete mix.
21. A cellular concrete according to claim 11, wherein the additive is present in an amount of from 1 quart to 36 quarts per cubic yard of cellular concrete mix.
22. A cellular concrete according to claim I1, wherein the additive is present in an amount of from 2 quarts to 12 quarts per cubic yard of cellular concrete mix.
23. A cellular concrete according to claim 11, wherein the additive comprises a colloidal suspension of sodium bentonite, peptized calcium bentonite or attapulgite in water in a weight ratio of sodium bentonite, peptized calcium bentonite or attapulgite to water of from 1:4 to 1:20.
24. A cellular concrete according to claim 21, wherein the additive comprises a colloidal suspension of sodium bentonite, peptized calcium bentonite or attapulgite in water in a weight ratio of sodium bentonite, peptized calcium bentonite or attapulgite to water of from 1:4 to 1:20.
25. A cellular concrete according to claim 22, wherein the additive comprises a colloidal suspension of sodium bentonite, peptized calcium bentonite or attapulgite in water in a weight ratio of sodium bentonite, peptized calcium bentonite or attapulgite to water of from 1:4 to 1:20.
26. A cellular concrete according to claim 11, wherein the additive is a sol-gel of silica-calcium chloride.
27. A cellular concrete according to claim 21, wherein the additive is a sol-gel of silica-calcium chloride.
28. A cellular concrete according to claim 22, wherein the additive is a sol-gel of silica-calcium chloride.
29. Lightweight aggregate comprising the cellular concrete of claim 21 which has been crushed.
30. Lightweight aggregate comprising the cellular concrete of claim 22 which has been crushed.
31. Lightweight aggregate comprising the cellular concrete of claim 23 which has been crushed.
32. Lightweight aggregate comprising the cellular concrete of claim 24 which has been crushed.
33. Lightweight aggregate comprising the cellular concrete of claim 25 which has been crushed.
34. Lightweight aggregate comprising the cellular concrete of claim 26 which has been crushed.
35. Lightweight aggregate comprising the cellular concrete of claim 27 which has been crushed.
36. Lightweight aggregate comprising the cellular concrete of claim 28 which has been crushed.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/889,481 | 1992-05-27 | ||
| US07/889,481 US5183505A (en) | 1992-05-27 | 1992-05-27 | Cellular concrete |
| PCT/US1993/005194 WO1993024425A1 (en) | 1992-05-27 | 1993-05-27 | Cellular concrete |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2136846A1 CA2136846A1 (en) | 1993-12-09 |
| CA2136846C true CA2136846C (en) | 2001-08-28 |
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ID=25395196
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002136846A Expired - Fee Related CA2136846C (en) | 1992-05-27 | 1993-05-27 | Cellular concrete |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US5183505A (en) |
| EP (1) | EP0642479B1 (en) |
| JP (1) | JPH07507531A (en) |
| KR (1) | KR0165873B1 (en) |
| AT (1) | ATE178300T1 (en) |
| AU (1) | AU668199B2 (en) |
| BR (1) | BR9306435A (en) |
| CA (1) | CA2136846C (en) |
| DE (1) | DE69324252T2 (en) |
| ES (1) | ES2131113T3 (en) |
| NZ (1) | NZ254325A (en) |
| WO (1) | WO1993024425A1 (en) |
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| GB1209462A (en) * | 1967-03-30 | 1970-10-21 | Bp Chemicals U K Ltd Formerly | An expanded magnesia cement |
| US3563930A (en) * | 1968-04-01 | 1971-02-16 | Atlantic Richfield Co | Cement composition |
| US3615784A (en) * | 1969-08-04 | 1971-10-26 | John Godfrey | Compositions for producing improved concrete |
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| US3663287A (en) * | 1969-11-04 | 1972-05-16 | Denki Kagaku Kogyo Kk | Cement additive comprising calcium sulfo-aluminate, an organic adhesive, a foaming agent, and a dispersing agent |
| US3852084A (en) * | 1970-03-30 | 1974-12-03 | C Smith | Cementitious composition containing activated lime-fly ash mixture |
| US3867159A (en) * | 1970-10-22 | 1975-02-18 | Stanley Works | Foamed concrete structures |
| US3669701A (en) * | 1970-10-29 | 1972-06-13 | Cities Service Oil Co | Lightweight cements for oil wells |
| US3989534A (en) * | 1973-03-19 | 1976-11-02 | Mark Plunguian | Foamed cementitious compositions and method of producing same |
| DE2325090C3 (en) * | 1973-05-17 | 1980-11-06 | Bayer Ag, 5090 Leverkusen | Process for the production of an inorganic-organic polymer-polysilicic acid composite material in the form of a colloidal xerosol |
| JPS5315525B2 (en) * | 1973-05-29 | 1978-05-25 | ||
| DE2345692B1 (en) * | 1973-09-11 | 1975-03-06 | Wasagchemie Ag | Structural lightweight concrete of particularly low density |
| DE2547908A1 (en) * | 1975-10-25 | 1977-04-28 | Perlmooser Zementwerke Ag | Synthetic aggregate for lightweight concrete - consists of porous cement which is hardened, then crushed into powder |
| GB1511398A (en) * | 1975-12-26 | 1978-05-17 | Shikoko Kaken Kogyo Kk | Process for preparing a foamed body |
| US4113913A (en) * | 1976-05-13 | 1978-09-12 | Rohm And Haas Company | Foamed cementitious material and composite |
| JPS5316410A (en) * | 1976-07-29 | 1978-02-15 | Nisso Master Builders Kk | Shrinkageefree grout material |
| JPS5390325A (en) * | 1977-01-19 | 1978-08-09 | Shinichi Suzuki | Granulation of substance having hardening property into porous spherical one |
| US4116703A (en) * | 1977-09-30 | 1978-09-26 | Corning Glass Works | Composite foamable cements |
| DE2828506C2 (en) * | 1978-06-29 | 1980-04-17 | Bayer Ag, 5090 Leverkusen | Method and device for producing a foamable mixture of at least two flowable, foam-forming reaction components and additives |
| US4268316A (en) * | 1979-07-27 | 1981-05-19 | Martin Marietta Corporation | Masonry cement composition |
| US4351670A (en) * | 1980-04-04 | 1982-09-28 | Grice Harold E | Lightweight concrete and method of making same |
| US4336069A (en) * | 1981-02-17 | 1982-06-22 | W. R. Grace & Co. | High strength aggregate for concrete |
| EP0164416B1 (en) * | 1983-12-02 | 1989-02-22 | Shikoku Kaken Kogyo Kabushiki Kaisha | Method of applying fire-resistant coverings to steel frame |
| US4673437A (en) * | 1984-06-25 | 1987-06-16 | Gelbman Lawrence F | Concrete block additive and improved concrete blocks produced therewith |
| US4568390A (en) * | 1984-06-25 | 1986-02-04 | Gelbman Lawrence F | Concrete block additive and improved concrete blocks produced therewith |
| US4900359A (en) * | 1984-06-25 | 1990-02-13 | Lisa Concrete Inc. | Cellular concrete |
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| JPS6221775A (en) * | 1985-07-18 | 1987-01-30 | 東北電力株式会社 | Manufacture of foamed hardened body based on coal ash |
| JPH02311341A (en) * | 1989-05-26 | 1990-12-26 | Dunckel Joachim | Production of porous light-weight aggregate, cast unit or composite of light-weight ag- gregate and light weight concrete |
| JPH03275134A (en) * | 1990-03-23 | 1991-12-05 | Nippon Jiryoku Senko Kk | Utilization of coal ash |
-
1992
- 1992-05-27 US US07/889,481 patent/US5183505A/en not_active Expired - Fee Related
-
1993
- 1993-05-27 CA CA002136846A patent/CA2136846C/en not_active Expired - Fee Related
- 1993-05-27 NZ NZ254325A patent/NZ254325A/en unknown
- 1993-05-27 EP EP93916419A patent/EP0642479B1/en not_active Expired - Lifetime
- 1993-05-27 AU AU45978/93A patent/AU668199B2/en not_active Ceased
- 1993-05-27 DE DE69324252T patent/DE69324252T2/en not_active Expired - Fee Related
- 1993-05-27 KR KR1019940704251A patent/KR0165873B1/en not_active IP Right Cessation
- 1993-05-27 ES ES93916419T patent/ES2131113T3/en not_active Expired - Lifetime
- 1993-05-27 JP JP6500834A patent/JPH07507531A/en active Pending
- 1993-05-27 BR BR9306435A patent/BR9306435A/en not_active IP Right Cessation
- 1993-05-27 WO PCT/US1993/005194 patent/WO1993024425A1/en active IP Right Grant
- 1993-05-27 AT AT93916419T patent/ATE178300T1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07507531A (en) | 1995-08-24 |
| DE69324252T2 (en) | 1999-09-23 |
| EP0642479A1 (en) | 1995-03-15 |
| KR0165873B1 (en) | 1998-12-15 |
| EP0642479B1 (en) | 1999-03-31 |
| KR950701606A (en) | 1995-04-28 |
| BR9306435A (en) | 1998-06-30 |
| NZ254325A (en) | 1997-03-24 |
| ES2131113T3 (en) | 1999-07-16 |
| DE69324252D1 (en) | 1999-05-06 |
| WO1993024425A1 (en) | 1993-12-09 |
| AU668199B2 (en) | 1996-04-26 |
| ATE178300T1 (en) | 1999-04-15 |
| CA2136846A1 (en) | 1993-12-09 |
| US5183505A (en) | 1993-02-02 |
| AU4597893A (en) | 1993-12-30 |
| EP0642479A4 (en) | 1996-04-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |