WO2001079132A1 - Compositions cimentaires a haute resistance initiale contenant de la poudre de verre - Google Patents

Compositions cimentaires a haute resistance initiale contenant de la poudre de verre Download PDF

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Publication number
WO2001079132A1
WO2001079132A1 PCT/US2001/011863 US0111863W WO0179132A1 WO 2001079132 A1 WO2001079132 A1 WO 2001079132A1 US 0111863 W US0111863 W US 0111863W WO 0179132 A1 WO0179132 A1 WO 0179132A1
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WIPO (PCT)
Prior art keywords
cementitious
glass
composition according
cementitious composition
cement
Prior art date
Application number
PCT/US2001/011863
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English (en)
Inventor
Tarig M. Monawar
Original Assignee
Zstone Technologies, Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zstone Technologies, Llc filed Critical Zstone Technologies, Llc
Priority to AU2001253389A priority Critical patent/AU2001253389A1/en
Publication of WO2001079132A1 publication Critical patent/WO2001079132A1/fr
Priority to US10/272,130 priority patent/US20030037708A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • 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
    • 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
    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02—Granular materials, e.g. microballoons
    • C04B14/04—Silica-rich materials; Silicates
    • C04B14/22—Glass ; Devitrified glass

Definitions

  • mixed color waste glass waste glass that is of mixed colors
  • mixed color waste glass is costly to sort by color and type.
  • Alternative uses for waste glass that cannot be used in the production of new glass articles have been developed, such as the use of waste glass in the production of fiberglass, in the process of sand-blasting, and in the production of abrasive materials. Nonetheless, this still leaves large amounts of potentially recyclable mixed color waste glass that must be disposed of in landfills, exacerbating the shortage of landfill space, particularly in the vicinity of large cities.
  • a more constructive use for the waste glass is as a pozzolan.
  • a pozzolan is a cementitious material added to a cement composition to prevent deterioration and increase the long-term strength of concrete and mortar products made from the cement composition.
  • waste glass has been little used as a pozzolan in the construction industry because products based on cementitious compositions that contain waste glass as a pozzolan are typically inferior to products formed from cementitious compositions containing only conventional cements, such as Portland cement.
  • cement formulations that include waste glass powder as a pozzolan produce low early strength properties because of the low pozzolanic reactivity of waste glass powder, and consequently such cement formulations can be used only in construction applications where low early strength properties are not detrimental, such as in stabilizing mine backfills.
  • the present invention relates to a cementitious composition that comprises cement, glass powder and an alkali metal aluminate.
  • the present invention also includes a cementitious binder composition comprising a mixture of water and the cementitious composition.
  • the present invention also includes a solidifiable cementitious composition, such as a mortar or concrete, comprising the cementitious binder composition and an aggregate.
  • a solidifiable cementitious composition such as a mortar or concrete, comprising the cementitious binder composition and an aggregate.
  • cement is meant an inorganic compound that when combined with water sets to form a hard product as a result of the hydration of the inorganic compound.
  • a “cementitious composition” is a material that has binding properties when mixed with water and includes both conventional cements, like Portland cement, and also glass powder as a pozzolan as well as other, optional components, such as cement additives.
  • early strength properties is meant the strength properties and performance that a material exhibits 24 hours after completion of molding.
  • the cementitious compositions of the present invention contain glass powder as a pozzolan and alkali metal aluminate, as well as conventional cement such as Portland cement. This glass powder is often less expensive than conventional cement and by replacing a portion of the conventional cement with the powder, the cost of the overall cementitious composition can be reduced.
  • Glass powder suitable for use in the present invention is formed from glass material including soda-lime glass, borosilicate glass, and lead glass.
  • Soda-lime glass which is a mixture of silica, Na2 ⁇ , and CaO is the most common form of glass used today and the most common form of post-consumer waste glass.
  • Borosilicate glass which is a mixture of silica and B2O3, is less common but still widely used in materials because of its resistance to chemical and temperature degradation.
  • the most common form of borosilicate glass is PYREX glass.
  • Lead glass a mixture of silica, Na2 ⁇ , and PbO, may also be used, although it is less common than the previous two types in post-consumer waste glass.
  • These glass materials may include optional modifiers and additives such as metal oxides and gallium or tin, which contribute to glass vitrification.
  • the glass materials may also include various chemical impurities such as ceramic and metal wastes.
  • Metal wastes include quantities of iron and lead, which have not been added to the glass material as chemical modifiers.
  • the glass material used herein may be of any color, and may be mixed by color, and must itself be freed of contaminants such as paper, foils, glues, foodstuffs and the like by a thorough cleaning of the glass material. Suitable processes for removing these contaminants from glass material are well-known to those of ordinary skill in the art.
  • the glass material added to the cementitious compositions does not contain high quantities of certain modifiers and intermediates. Notably, it is preferred that the glass material contains less than 10 wt% of K2O, and less than 2 wt% of
  • the present cementitious compositions be free of quaternary ammonium silicates.
  • the resulting material is a specialized structural material that is a "glass" only in a specific physical and chemical sense, i.e. it is an amorphous solid lacking long-range order and containing SiO . It is not a "glass” as the term is most typically used to generically refer to common structural materials such as silicate glass, soda-lime glass, borosilicate glass, and lead glass as described above.
  • the "glass” in U.S. Pat. Nos. 4,440,576, 3,720,527, and 3,743,525 is a specially formulated and processed amorphous solid that has hydraulic and cementitious properties, while in the present invention the glass material is common commercial glass material.
  • the source of the glass material is not critical to the present invention, and may even include freshly manufactured glass, but it is preferred that the glass material be post- consumer waste glass, as this may increase the cost-effectiveness and economic viability of the presently disclosed materials as well as provide an alternative to dumping the waste glass in landfills.
  • post-consumer waste glass is meant glass that is no longer necessary to perform the function for which it was formulated and formed.
  • Glass containers that have been emptied of a consumable product, as well as glass containers or other glass articles that are broken or no longer usable for some other reason are all examples of post-consumer waste glass.
  • the glass material is obtained and thoroughly cleaned, it is crushed, ground, pulverized or otherwise processed into glass powder.
  • Various types of crushing and grinding equipment and other like equipment can be used to produce particulate glass powders. Examples of such equipment include the ball-medium type, medium agitating type, fluid- energy type, impact-pulverizing type, and other like machines. It is preferred that substantially all of the glass particles used in the present invention will pass through a No. 70 mesh sieve (as designated in the U.S.
  • the cementitious compositions of the present invention also include alkali metal aluminate, preferably sodium aluminate (NaAl ⁇ 2) or
  • the alkali metal aluminate component which functions as an activator, may be added in either liquid or dry powder form.
  • a co-activator may be added along with the alkali metal aluminate to enhance activation of the glass material.
  • Suitable co-activators include alkali metal silicates, sodium carbonate, and alkali hydroxides or salts of alkali hydroxides.
  • Preferred alkali metal silicates include lithium silicate, sodium silicate and sodium polysilicate.
  • the cementitious compositions also include cement.
  • the most preferred cements are Portland cement and high alumina cement or a mixture of these cements.
  • the present cementitious compositions may also include optional cement additives.
  • a particularly suitable additive is a superplasticizer (also known as water-reducer).
  • Superplasticizer compounds reduce the amount of water necessary to mix with the cement composition to produce a cementitious binder of acceptable workability and thus increase the strength of concrete products formed from such cement.
  • Conventional superplasticizers include lignosulfonate derivatives, condensed naphthalene sulfonates, or carbohydrate esters.
  • POZZOLITH 440-NTM produced by Master Builders Technologies and DARACEM 100TM produced by the W.R. Grace & Co. are suitable commercially available examples of superplasticizers.
  • Suitable additives include retardants, which delay setting time and are particularly useful for forming operations in high-temperature environments, and accelerants, which accelerate setting times and are useful for forming in low-temperature environments. Air entrainers, which improve workability, may also be used.
  • the cementitious compositions of the present invention preferably include about
  • the present cementitious compositions are mixed with water to form a cementitious binder composition, which can be solidified or used as the basis for a solidifiable cementitious composition.
  • the weight ratio of water to cement in the binder is from about 0.1:1 to about 1:1, preferably about 0.3:1 to about 0.5:1.
  • cementitious binder compositions may be mixed with mineral aggregate particles to form a solidifiable cementitious composition, such as a concrete or mortar.
  • This binder forms a matrix in concrete or mortar products to hold together the aggregate particles.
  • Aggregate particles are inert solid bodies that form most of the volume of a concrete article.
  • the cementitious binder composition forms a binder matrix that holds the aggregate together.
  • mineral fillers such as silica flour, kaolin, shales, bentonites, feldspar and the like can be added in various amounts as extenders and to enhance physical properties .
  • Such solidifiable cementitious compositions are typically classified as concretes or mortars, depending on the particle size of the aggregate. Concretes usually contain both coarse and fine aggregates, whereas mortars contain fine aggregate but no coarse aggregate. The proportions of coarse and fine aggregate used in a concrete depend on the required properties and intended use, which are well-known to those of ordinary skill in the art. [0030] Aggregates for use in concrete are described in ASTM C33-90 "Standard
  • coarse aggregates which include gravel and crushed limestone, fall within the range of 2 inches to 2/3 inch mesh; and fine aggregates, such as sand, fall in the range of No. 4 mesh to No. 200 mesh of ASTM C-l 1.
  • fibers or other strength-enhancing additives commonly-known to those skilled in the art can be added to the present solidifiable cementitious compositions to enhance the tensile strength, impact resistance or beneficially affect other important properties.
  • ferro-cement composites in which shapes of reinforcing metal bars or rods are embedded in the solidifiable cementitious compositions. As the concrete cures, the reinforcing bars and the concrete bond together.
  • a particularly preferred reinforcing material is a ribbed steel rod coated with an epoxy to prevent corrosion.
  • a metal wire mesh may also be used as the reinforcement material.
  • the use of reinforcing metallic rods and/or meshes may also be used in mortars, as well as in concretes.
  • Suitable fibers include steel or polymeric fibers (e.g., nylon fibers).
  • the cementitious compositions of the present invention may be made by using any standard mixing and forming processes commonly-known to those skilled in the art.
  • the manner of combining and mixing ingredients to form the hydraulic cement compositions and the cementitious binders and solidifiable compositions is not restricted to any particular embodiment. These components may be mixed and combined in any order, at a variety of different temperatures and in a variety of different machine and apparatus configurations according to the needs of the user.
  • the present invention also contemplates the use of suitable inter-grinding processes, i.e., grinding of the unmixed combination of the ingredients together into a mixture, so that mixing occurs simultaneously with grinding. An example of this is when the glass material is ground into powder along with the cement clinker.
  • the solidifiable cementitious composition is "placed", meaning it is poured, pressed, or otherwise processed into the shape into which it is to set or “solidify".
  • the solidifiable cementitious composition may be placed by pouring it into a wooden or steel form so that it hardens into the desired shape. Alternatively, the solidifiable cementitious composition may be placed by hand-troweling it into the desired shape.
  • the solidifiable cementitious composition that has "set” or “hardened” into its desired shape may be referred to as the "solidified solidifiable cementitious composition".
  • the process for setting and hardening of the solidifiable cementitious composition into the solidified solidifiable cementitious composition is not restricted to any particular embodiment, and any suitable process known to those of ordinary skill in the art may be used.
  • the preferred process includes applying a protective medium to retain moisture, wet curing, or autoclave curing.
  • the use of higher curing temperatures and higher amounts of relative humidity during curing accelerates the rate of hardening and allows for high compressive strengths to be more rapidly attained.
  • the degree of relative humidity preferably exceeds 90%.
  • Curing temperatures of over about 22°C (room temperature) are suitable, preferably the curing temperature exceeds about 85°C, more preferably the curing temperature exceeds about 200°C.
  • a solidified and cured solidifiable cementitious composition prepared according to the present invention has a compressive strength of at least about 45 MPa.
  • cementitious compositions By formulating and processing cementitious compositions as described above, it has been determined that waste glass can be used as a pozzolan and a partial replacement for a portion of the cement in the cementitious composition, so that solidified concrete and mortar products made from such a cementitious composition have short-term and long-term strength properties superior to the strength properties of similar products made with conventional cements. [0037] Additionally, solidifiable cementitious compositions made from these cementitious compositions may have a desirable "white" color. White cement or white concrete is highly desirable for use in applications where aesthetics and design appeal are an important factor. Thus, the present formulations for cementitious compositions offer many benefits over the conventional cement compositions that are well-known in the art.
  • the solidifiable cementitious composition in the form of mortars, concretes, and the like
  • the gain in strength is attributed to the continuous formation of additional stable calcium compounds from the lime released by the cement.
  • the excellent durability is related to the stabilization of the cement lime, which would otherwise react with chemicals in the environment to weaken the solidified concrete or mortar products made from the cementitious composition.
  • EXAMPLE I Tests were carried out to determine the early strength properties of cementitious binder compositions containing different formulations of cement, glass powder and an alkaline metal aluminate (viz., sodium aluminate), as well as to determine the early (24 hours) and 7 days strength of solidifiable cementitious compositions (i.e., mortars), which are a combination of the aforementioned cementitious binder compositions , an aggregate and other optional components such as reinforcing fiber materials.
  • solidifiable cementitious compositions i.e., mortars
  • Several different solidifiable cementitious compositions and cementitious binder compositions were prepared according to ASTM C109/C-109M-99. In the control composition, 100% of the cementitious material was Portland cement.
  • compositions 1-7 from 50% to 70% of the Portland cement was replaced with a mixture of glass powder and an alkali metal aluminate, specifically sodium aluminate.
  • Compositions 3 and 5 also included steel or nylon reinforcing fibers, to increase compressive strength, impact strength, and durability.
  • the superplasticizer used was DARCEM 100®.
  • the glass material consisted of cleaned, post-consumer mixed color waste glass ground into a powder such that 80% to 100%) passed through a No. 325 (U.S.) mesh sieve.
  • the sodium aluminate was also prepared to pass through a No. 325 mesh sieve.
  • Various water-cementitious composition weight ratios were used as indicated in the Tables.
  • ASTM C109/C109 M-99 the materials for each of the compositions were first mixed together with water in a laboratory mixer to obtain a homogeneous cementitious binder composition.
  • compositions 2-3 and 5-7 sand or a mixture of sand and gravel aggregate was then added to further form a solidifiable cementitious composition.
  • the superplasticizer was the last ingredient added to the composition.
  • the compositions were placed into 2 inch cube molds and compacted to eliminate entrapped air pockets.
  • one set of cubes was moist cured at room temperature and 100% humidity for 12 hours to solidify, and then further steam cured for an additional 8 hours at 85°C.
  • a second set of cubes was cured at 22°C and 100%) relative humidity for 7 days. Each cube was then tested for compressive strength using a standard universal testing machine, as directed by ASTM C 109/C 109M-99. The results were as follows.
  • cementitious binder compositions and solidifiable cementitious compositions containing a mixture of Portland cement, sodium aluminate and glass powder had high compressive strength performance.
  • the compressive strength performance of these compositions was superior to conventional compositions that contain Portland cement alone. This increase in the compressive strength of a cementitious composition or cementitious binder composition resulting from the use of Portland cement in combination with glass powder and sodium aluminate would not have been expected or predicted by those of skill in the art.
  • cementitious binder compositions formed from cementitious compositions comprising cement, glass powder and sodium aluminate have high early compressive strength that is comparable or superior to mortar and concrete products that are made from conventional cementitious compositions. Additionally, solidifiable cementitious compositions formed from cementitious binder compositions prepared according to the present invention have substantially improved early strength performance compared to mortar and concrete products that are made from conventional cementitious compositions that contain cement, but neither sodium aluminate or glass powder. Such results would be unexpected by one of ordinary skill in the art.

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

Abstract

L'invention concerne des compositions cimentaires dans lesquelles on peut utiliser des déchets de verre, qui comprennent un matériau du type verre, de l'aluminate de métal alcalin et un ciment. L'invention concerne également des liants cimentaires et des compositions cimentaires solidifiables (tels que des mortiers et des bétons) qui contiennent lesdites compositions cimentaires. Une telle composition cimentaire est mélangée avec de l'eau pour former un liant cimentaire, et un agrégat est ajouté au liant cimentaire pour former les compostions cimentaires solidifiables. Les compositions cimentaires solidifiables formées à partir des compositions cimentaires présentent une résistance initiale et une résistance à long terme plus élevées.
PCT/US2001/011863 2000-04-12 2001-04-12 Compositions cimentaires a haute resistance initiale contenant de la poudre de verre WO2001079132A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2001253389A AU2001253389A1 (en) 2000-04-12 2001-04-12 High early strength cementitious compositions containing glass powder
US10/272,130 US20030037708A1 (en) 2001-04-12 2002-10-15 High early strength cementitous compositions containing glass powder

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US19637700P 2000-04-12 2000-04-12
US60/196,377 2000-04-12

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1422206A1 (fr) * 2002-11-25 2004-05-26 Esportec- Espaces Sports Technologies Liant hydraulique notamment destine a la fabrication de betons decoratifs
WO2008138050A1 (fr) * 2007-05-10 2008-11-20 Christopher George Fraser Composition cimentaire durcissable et ses utilisations
US7811377B2 (en) 2001-03-02 2010-10-12 Albacem Llc Low alkali, non-crystalline, vitreous silica fillers
EP2978723A4 (fr) * 2013-03-28 2016-12-07 Socpra Sciences Et Genie Sec Béton translucide ultra-haute performance et procédé de production de celui-ci

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5588990A (en) * 1995-11-03 1996-12-31 Universal Cement & Concrete Products, Inc. Pozzolan cement compositions and admixtures therefor
US6153674A (en) * 1998-01-30 2000-11-28 3M Innovative Properties Company Fire barrier material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5588990A (en) * 1995-11-03 1996-12-31 Universal Cement & Concrete Products, Inc. Pozzolan cement compositions and admixtures therefor
US6153674A (en) * 1998-01-30 2000-11-28 3M Innovative Properties Company Fire barrier material

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7811377B2 (en) 2001-03-02 2010-10-12 Albacem Llc Low alkali, non-crystalline, vitreous silica fillers
EP1422206A1 (fr) * 2002-11-25 2004-05-26 Esportec- Espaces Sports Technologies Liant hydraulique notamment destine a la fabrication de betons decoratifs
FR2847574A1 (fr) * 2002-11-25 2004-05-28 Espaces Sports Technologies Es Liant hydraulique notamment destine a la fabrication de betons decoratifs
WO2008138050A1 (fr) * 2007-05-10 2008-11-20 Christopher George Fraser Composition cimentaire durcissable et ses utilisations
EP2978723A4 (fr) * 2013-03-28 2016-12-07 Socpra Sciences Et Genie Sec Béton translucide ultra-haute performance et procédé de production de celui-ci
US9856171B2 (en) 2013-03-28 2018-01-02 Socpra Sciences Et Génie S.E.C. Ultra-high performance glass concrete and method for producing same

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Publication number Publication date
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