Extruded gypsum-based materials

Information

  • Patent Grant
  • 9890083
  • Patent Number
    9,890,083
  • Date Filed
    Wednesday, March 5, 2014
    10 years ago
  • Date Issued
    Tuesday, February 13, 2018
    6 years ago
Abstract
An extrudable gypsum-based material is formed from a mixture that includes gypsum in the range of about 40 to 90% by dry weight percent, a secondary material in the range of about 0.1 to 50% by dry weight percent, a reinforcement fiber in the range of about 1 to 20% by dry weight percent, a rheology modifying agent in the range of about 0.5 to 10% by dry weight percent, a retarder in the range of about 0.1 to 8% by dry weight percent, a water in the range of 10 to 50% of a total wet material weight.
Description
FIELD OF INVENTION

The present invention relates in general to the production of gypsum-based materials, and more particularly to products made by extruding gypsum-based materials (e.g., roofing tiles, wall panels, etc.).


BACKGROUND ART

Gypsum products are generally produced using large amounts of water to form a slurry that is too wet to extrude. As a result, various water-reducing elements have been developed to reduce the water content such that an extrusion process can be used to produce gypsum-based materials. See for example, U.S. Pat. No. 7,172,403 which is hereby incorporated by reference in its entirety.


There is, however, a need for a rheology-modified gypsum-based material (e.g., roofing tiles, wall panels, etc.) that can be extruded.


SUMMARY OF THE INVENTION

The present invention provides a rheology-modified gypsum-based material (e.g., roofing tiles, wall panels, etc.) that can be extruded.


More specifically, the present invention provides an extrudable gypsum-based material that is formed from a mixture that includes gypsum in the range of about 40 to 90% by dry weight percent, a secondary material in the range of about 0.1 to 50% by dry weight percent, a reinforcement fiber in the range of about 1 to 20% by dry weight percent, a rheology modifying agent in the range of about 0.5 to 10% by dry weight percent, a retarder in the range of about 0.1 to 8% by dry weight percent, a water in the range of 10 to 50% of a total wet material weight.


In addition, the present invention provides a method for manufacturing an extrudable gypsum-based material by mixing a gypsum, a secondary material, a reinforcement fiber, a rheology modifying agent and a retarder with water, extruding the mixture through a die using an extruder, and allowing the extruded mixture to set.


BRIEF DESCRIPTION OF THE DRAWINGS

For a more complete understanding of the features and advantages of the present invention, reference is now made to the detailed description of the invention along with the accompanying figures and in which:


Not applicable.







DESCRIPTION OF THE INVENTION

While the making and using of various embodiments of the present invention are discussed in detail below, it should be appreciated that the present invention provides many applicable inventive concepts that can be embodied in a wide variety of specific contexts. The specific embodiments discussed herein are merely illustrative of specific ways to make and use the invention and do not delimit the scope of the invention.


As will be described below, the present provides an extrudable gypsum-based material that is formed from a mixture that includes gypsum in the range of about 40 to 90% by dry weight percent, a secondary material in the range of about 0.1 to 50% by dry weight percent, a reinforcement fiber in the range of about 1 to 20% by dry weight percent, a rheology modifying agent in the range of about 0.5 to 10% by dry weight percent, a retarder in the range of about 0.1 to 8% by dry weight percent, a water in the range of 10 to 50% of a total wet material weight.


Gypsum (Plaster of Paris, Calcium Sulfate hemihydrate) in its wet state before setting, can be rheologically modified in to a clay-like material, which allows the use of the conventional clay production methods known as extrusion.


For extrusion, the gypsum material with approx. 10-50 wt. % water and a suitable rheology modifying admixture is made to feel and behave similar to plastic clay. The material feels plastic/deformable to the touch and can be extruded similar to clay with the use of a clay extruder where the material is conveyed forward by an auger through a barrel and is formed continuously through a die into a final shape with form stability.


Depending on the water content and the amount of rheology modifying admixture, the extruded material can have more or less form stability.


To allow enough time of the gypsum-based material to be extruded before setting (hardening), the setting time can be retarded up to several hours with the use of small additions of suitable set retarders such as Sodate™ (USG Product) or sodium citrate. Sodate™ is a mixture of Plaster of Paris, sodium citrate and crystalline silica. Following extrusion, the material will within a few hours develop the final strength of the finished product.


The gypsum can be used as a binder with water in a composite composition in combination with a multitude of secondary materials such as sand, cement, fly ash, slag, rock, expanded light weight aggregate, etc., or a combination thereof, which when rheologically modified can be extruded as described above.


The rheology-modifying agents fall into the following categories: (1) polysaccharides and derivatives thereof, (2) proteins and derivatives thereof, and (3) synthetic organic materials. Polysaccharide rheology-modifying agents can be further subdivided into (a) cellulose-based materials and derivatives thereof, (b) starch-based materials and derivatives thereof, and (c) other polysaccharides.


Suitable cellulose-based rheology-modifying agents include, for example, methylhydroxyethylcellulose (MHEC), hydroxymethylethylcellulose (HMEC), carboxymethylcellulose (CMC), methylcellulose (MC), ethylcellulose (EC), hydroxyethylcellulose (HEC), hydroxyethylpropylcellulose (HEPC), or hydroxypropoylmethylcelluose (HPMC), etc.


Suitable starch-based materials include, for example, wheat starch, pre-gelled wheat starch, potato starch, pre-gelled potato starch, amylopectin, amylose, seagel, starch acetates, starch hydroxyethyl ethers, ionic starches, long-chain alkylstarches, dextrins, amine starches, phosphate starches, and dialdehyde starches.


The currently preferred rheology-modifying agent is methylhydroxypropylcellulose, examples of which are Methocel™ 240 and Methocel™ 240S, both of which are available from DOW Chemicals, USA.


In one embodiment of the present invention, the compositional ranges of gypsum-based material can be:













Component
Wt. % Range of Dry







Gypsum (CaSO4•½H2O)
40-90


Secondary material (e.g., sand, rock, fly ash, slag,
0.1-50 


cement, calcium carbonate, light weight aggregate,


etc.)


Reinforcement fiber
 1-20


Rheology modifying agent
0.5-10 


Retarder
0.1-8  


Water wt. % of total wet material
10-50









The gypsum can be 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89% or 90% by weight or other incremental percentage between.


The water can be 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49% or 50% by weight or other incremental percentage between.


The secondary material can be 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43% 44%, 45%, 46%, 47%, 48%, 49% or 50% by weight or other incremental percentage between.


The reinforcement fiber can be 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20% by weight or other incremental percentage between.


The rheology modifying agent can be 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5.0%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6.0%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7%, 6.8%, 6.9%, 7.0%, 7.1%, 7.2%, 7.3%, 7.4%, 7.5%, 7.6%, 7.7%, 7.8%, 7.9%, 8.0%, 8.1%, 8.2%, 8.3%, 8.4%, 8.5%, 8.6%, 8.7%, 8.8%, 8.9%, 9.0%, 9.1%, 9.2%, 9.3%, 9.4%, 9.5%, 9.6%, 9.7%, 9.8%, 9.9%, 10.0% by weight or other incremental percentage between.


The retarder can be 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5.0%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6.0%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7%, 6.8%, 6.9%, 7.0%, 7.1%, 7.2%, 7.3%, 7.4%, 7.5%, 7.6%, 7.7%, 7.8%, 7.9% or 8.0% by weight or other incremental percentage between.


In addition, the present invention provides a method for manufacturing an extrudable gypsum-based material by mixing a gypsum, a secondary material, a reinforcement fiber, a rheology modifying agent and a retarder with water, extruding the mixture through a die using an extruder, and allowing the extruded mixture to set (e.g., up to 2 to 3 hours, etc).


Additional steps may include: (1) drying the extruded mixture; (2) curing the extruded mixture; (3) molding, cutting, trimming, sanding or routing the extruded mixture into a specified shape (e.g., a roofing tile, wall panel, etc.); (4) spraying the extruded mixture with a water repellent; and/or (5) decorating one or more surfaces of the extruded mixture by printing at least one image on the one or more surfaces or laminating a veneer on the one or more surfaces, or etching the at least one image on the one or more surfaces.


Roofing Tiles


Gypsum-based roofing tiles can be produced from Plaster of Paris (Calcium Sulfate hemihydrate) that in it's wet state with water (16-25 wt. %) has been rheologically modified to have clay-like properties.


The roofing tiles can be produced in a number of ways that is known in the art of clay and concrete technology:

    • 1) Extrusion with a clay extruder through a die into the final shape of the roofing tiles.
    • 2) Extrusion with a clay extruder through a die into a sheet of thickness equal to or bigger than the final thickness of the tiles and a width that allows for the width of one or multiple tiles. The sheet is formed into the shape of the final tiles either by placing the sheet over a bottom mold half in a vertical press or running the sheet through forming calenders.
    • 3) Extruding cylindrical pieces of material that are subsequently formed into the final tile shape between bottom and top molds in a vertical press or similar.
    • 4) By mixing the rheologically modified material and placing finite metered pieces of the material that are subsequently formed into the final tile shape between bottom and top molds in a vertical press or similar.


Following setting within a couple of hours, the roofing tiles are dried in an oven. Typically the roofing tiles will have a thickness range of 5 mm to 40 mm.


The mechanical properties are modified to generate a ductile (non-brittle) material by the addition of fiber reinforcement such as cellulose fiber, glass fiber, polypropylene fiber, polyvinyl alcohol (PVA) fiber, Dolanit® fiber (generic name: homopolymer acrylic or alkali-resistant fiber), or similar, or combination thereof.


The tiles are made water resistant by treating the surface of the product to a water repellent silane or water resistant surface coating known in state-of-the-art. Freeze-Thaw resistance can be accomplished by incorporating micro-balloons in the composite composition.


Compared to state-of-the-art roofing tiles, the roofing tiles of the present invention are lighter, thinner, more ductile, more durable and less costly.


Wall Panels


Gypsum-based wall panels can be produced from Plaster of Paris (Calcium Sulfate hemihydrate) that in it's wet state with water (16-25 wt. %) has been rheologically modified to have clay-like properties.


A wall for a bathroom stall interior passage hall is made from a composite material using gypsum (Plaster of Paris, Calcium Sulfate hemihydrate) as the binder.


The composite material in it's wet state before setting of the gypsum, is rheologically modified into a clay-like material, which allows the use of the conventional clay production methods known as extrusion to form the shape of the wall.


The composition of the composite material can be formulated to make the wall: lightweight, dense, fire resistant, sound resistant, durable and non-brittle. Typically the wall panels will have a thickness range of 5 mm to 250 mm.


Following setting and drying of the finished product, the surface of the wall element can be made water resistant with the use of silanes or surface coatings. Further, the surface can be decorated by printing onto the surface, by laminating veneer onto the surface or by printing “Nerewood” onto the surface. For example, U.S. Pat. No. 6,964,722 entitled “Method for Producing a Wood Substrate Having an Image on at Least One Surface” or U.S. Patent Application Ser. No. 61/713,240 and PCT Patent Application Serial No. PCT/US2013/064435 entitled “Method for Producing a Substrate Having an Image on at Least One Surface”, all of which are hereby incorporated herein by reference in their entirety.


It may be understood that particular embodiments described herein are shown by way of illustration and not as limitations of the invention. The principal features of this invention can be employed in various embodiments without departing from the scope of the invention. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, numerous equivalents to the specific procedures described herein. Such equivalents are considered to be within the scope of this invention and are covered by the claims.


All publications, patents and patent applications mentioned in the specification are indicative of the level of skill of those skilled in the art to which this invention pertains. All publications, patents and patent applications are herein incorporated by reference to the same extent as if each individual publication, patent or patent application was specifically and individually indicated to be incorporated by reference.


The use of the word “a” or “an” when used in conjunction with the term “comprising” in the claims and/or the specification may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.” The use of the term “or” in the claims is used to mean “and/or” unless explicitly indicated to refer to alternatives only or the alternatives are mutually exclusive, although the disclosure supports a definition that refers to only alternatives and “and/or.” Throughout this application, the term “about” is used to indicate that a value includes the inherent variation of error for the device, the method being employed to determine the value, or the variation that exists among the study subjects.


As used in this specification and claim(s), the words “comprising” (and any form of comprising, such as “comprise” and “comprises”), “having” (and any form of having, such as “have” and “has”), “including” (and any form of including, such as “includes” and “include”) or “containing” (and any form of containing, such as “contains” and “contain”) are inclusive or open-ended and do not exclude additional, unrecited elements or method steps.


The term “or combinations thereof” as used herein refers to all permutations and combinations of the listed items preceding the term. For example, “A, B, C, or combinations thereof” is intended to include at least one of: A, B, C, AB, AC, BC, or ABC, and if order is important in a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB. Continuing with this example, expressly included are combinations that contain repeats of one or more item or term, such as BB, AAA, AB, BBC, AAABCCCC, CBBAAA, CABABB, and so forth. The skilled artisan will understand that typically there is no limit on the number of items or terms in any combination, unless otherwise apparent from the context.


All of the compositions and/or methods disclosed and claimed herein can be made and executed without undue experimentation in light of the present disclosure. While the compositions and methods of this invention have been described in terms of preferred embodiments, it may be apparent to those of skill in the art that variations may be applied to the compositions and/or methods and in the steps or in the sequence of steps of the method described herein without departing from the concept, spirit and scope of the invention. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims.

Claims
  • 1. An extrudable gypsum-based material formed from a mixture comprising: a calcium sulfate hemihydrate in the range of about 40 to 90% by dry weight percent;a secondary material in the range of about 0.1 to 50% by dry weight percent selected from sand, cement, fly ash, slag, rock, expanded light weight aggregate, or a combination thereof;a reinforcement fiber in the range of about 1 to 20% by dry weight percent;a rheology modifying agent in the range of about 0.5 to 10% by dry weight percent selected from a polysaccharide, a polysaccharide derivative, a protein, a protein derivative, a synthetic organic material, a synthetic organic material derivative, or a combination thereof;a retarder in the range of about 0.1 to 8% by dry weight percent;a water in the range of 16 to 25% of a total wet material weight; andthe mixture is extrudable.
  • 2. The extrudable gypsum-based material as recited in claim 1, the reinforcement fiber comprising cellulose fiber, glass fiber, polypropylene fiber, polyvinyl alcohol (PVA) fiber, homopolymer acrylic or alkali-resistant fiber, or a combination thereof.
  • 3. The extrudable gypsum-based material as recited in claim 1, the polysaccharide comprising a cellulose-based material, a cellulose-based material derivative, a starch-based material, a starch-based material derivative, or a combination thereof.
  • 4. The extrudable gypsum-based material as recited in claim 3, the cellulose-based material is selected from the group consisting of methylhydroxyethylcellulose (MHEC), hydroxymethylethylcellulose (HMEC), carboxymethylcellulose (CMC), methylcellulose (MC), ethylcellulose (EC), hydroxyethylcellulose (HEC), hydroxyethylpropylcellulose (HEPC) and hydroxypropylmethylcellulose (HPMC).
  • 5. The extrudable gypsum-based material as recited in claim 3, the starch-based material is selected from the group consisting of wheat starch, pre-gelled wheat starch, potato starch, pre-gelled potato starch, amylopectin, amylose, seagel, starch acetates, starch hydroxyethyl ethers, ionic starches, long-chain alkylstarches, dextrins, amine starches, phosphate starches, or dialdehyde starches.
  • 6. The extrudable gypsum-based material as recited in claim 1, the retarder comprising sodium citrate, or a mixture of Plaster of Paris, sodium citrate and crystalline silica.
  • 7. The extrudable gypsum-based material as recited in claim 1, wherein the extrudable gypsum-based material comprises a roofing tile or a wall panel.
  • 8. A method for manufacturing an extrudable gypsum-based material comprising the steps of: mixing a calcium sulfate hemihydrate in the range of about 40 to 90% by dry weight percent, a secondary material in the range of about 0.1 to 50% by dry weight percent selected from sand, cement, fly ash, slag, rock, expanded light weight aggregate, or a combination thereof, a reinforcement fiber in the range of about 1 to 20% by dry weight percent, a rheology modifying agent in the range of about 0.5 to 10% by dry weight percent selected from a polysaccharide, a polysaccharide derivative, a protein, a protein derivative, a synthetic organic material, a synthetic organic material derivative, or a combination thereof, and a retarder in the range of about 0.1 to 8% by dry weight percent with water in the range of 16 to 25% of a total wet material weight;extruding the mixture through a die using an extruder; andallowing the extruded mixture to set.
  • 9. The method as recited in claim 8, the reinforcement fiber comprising cellulose fiber, glass fiber, polypropylene fiber, polyvinyl alcohol (PVA) fiber, homopolymer acrylic or alkali-resistant fiber, or a combination thereof.
  • 10. The method as recited in claim 8, the polysaccharide comprising a cellulose-based material, a cellulose-based material derivative, a starch-based material, a starch-based material derivative, or a combination thereof.
  • 11. The method as recited in claim 10, the cellulose-based material is selected from the group consisting of methylhydroxyethylcellulose (MHEC), hydroxymethylethylcellulose (HMEC), carboxymethylcellulose (CMC), methylcellulose (MC), ethylcellulose (EC), hydroxyethylcellulose (HEC), hydroxyethylpropylcellulose (HEPC) and hydroxypropylmethylcellulose (HPMC).
  • 12. The method as recited in claim 10, the starch-based material is selected from the group consisting of wheat starch, pre-gelled wheat starch, potato starch, pre-gelled potato starch, amylopectin, amylose, seagel, starch acetates, starch hydroxyethyl ethers, ionic starches, long-chain alkylstarches, dextrins, amine starches, phosphate starches, or dialdehyde starches.
  • 13. The method as recited in claim 8, the retarder comprising sodium citrate, or a mixture of Plaster of Paris, sodium citrate and crystalline silica.
  • 14. The method as recited in claim 8, wherein the extruded mixture is allowed to set for 2 to 3 hours.
  • 15. The method as recited in claim 8, further comprising the step of curing the extruded mixture.
  • 16. The method as recited in claim 8, further comprising the step of drying the extruded mixture.
  • 17. The method as recited in claim 8, further comprising the step of molding, cutting, trimming, sanding or routing the extruded mixture into a specified shape.
  • 18. The method as recited in claim 17, wherein the specified shape comprises a roofing tile or a wall panel.
  • 19. The method as recited in claim 18, wherein: the roofing tile has a thickness of between about 5 mm to 40 mm; andthe wall panel has a thickness of between about 5 mm to 250 mm.
  • 20. The method as recited in claim 8, further comprising the step of spraying the extruded mixture with a water repellent.
  • 21. The method as recited in claim 8, further comprising the step of decorating one or more surfaces of the extruded mixture by printing at least one image on the one or more surfaces or laminating a veneer on the one or more surfaces, or etching the at least one image on the one or more surfaces.
CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to, and is the National Phase of International Application No. PCT/US2014/020865, filed on Mar. 5, 2014, which claims the benefit under 35 U.S.C. § 119(e) of U.S. Provisional Application Nos. 61/772,646 filed Mar. 5, 2013 and 61/772,648 filed Mar. 5, 2013 and 61/772,653 filed Mar. 5, 2013.

PCT Information
Filing Document Filing Date Country Kind
PCT/US2014/020865 3/5/2014 WO 00
Publishing Document Publishing Date Country Kind
WO2014/138283 9/12/2014 WO A
US Referenced Citations (293)
Number Name Date Kind
570391 Fox Oct 1896 A
1048923 Wheeler Dec 1912 A
3517468 Woods Jun 1970 A
3852083 Yang Dec 1974 A
3908062 Roberts Sep 1975 A
3987600 Baehr Oct 1976 A
3994110 Ropella Nov 1976 A
4014149 Yamamoto Mar 1977 A
4045937 Stucky Sep 1977 A
4075804 Zimmerman Feb 1978 A
4084571 McFarland Apr 1978 A
4159302 Greve et al. Jun 1979 A
4225247 Hodson Sep 1980 A
4225357 Hodson Sep 1980 A
4284119 Martin et al. Aug 1981 A
4302127 Hodson Nov 1981 A
4308065 Walls-Muycelo Dec 1981 A
4339487 Mullet Jul 1982 A
4343127 Greve et al. Aug 1982 A
4347653 Martin et al. Sep 1982 A
4398842 Hodson Aug 1983 A
4428775 Johnson et al. Jan 1984 A
4434899 Rivkin Mar 1984 A
4443992 Shechter Apr 1984 A
4489121 Luckanuck Dec 1984 A
4552463 Hodson Nov 1985 A
4660338 Wagner Apr 1987 A
4664707 Wilson et al. May 1987 A
4695494 Fowler et al. Sep 1987 A
4704834 Turner Nov 1987 A
4716700 Hagemeyer Jan 1988 A
4716702 Dickson Jan 1988 A
4800538 Passmore et al. Jan 1989 A
4811538 Lehnert et al. Mar 1989 A
4864789 Thorn Sep 1989 A
4889428 Hodson Dec 1989 A
4896471 Turner Jan 1990 A
4922674 Thorn May 1990 A
4944595 Hodson Jul 1990 A
4946504 Hodson Aug 1990 A
4998598 Mardian et al. Mar 1991 A
5061319 Hodson Oct 1991 A
5074087 Green Dec 1991 A
5100586 Jennings et al. Mar 1992 A
5108677 Ayres Apr 1992 A
5154358 Hartle Oct 1992 A
5169566 Stucky et al. Dec 1992 A
5232496 Jennings et al. Aug 1993 A
5239799 Bies et al. Aug 1993 A
5242078 Haas et al. Sep 1993 A
5305577 Richards et al. Apr 1994 A
5311381 Lee May 1994 A
5317119 Ayres May 1994 A
5339522 Paquin et al. Aug 1994 A
5344490 Roosen et al. Sep 1994 A
5347780 Richards et al. Sep 1994 A
5356579 Jennings et al. Oct 1994 A
5358676 Jennings et al. Oct 1994 A
5376320 Tiefenbacher et al. Dec 1994 A
5385764 Andersen et al. Jan 1995 A
5395571 Symons Mar 1995 A
5401588 Garvey et al. Mar 1995 A
5417024 San Paolo May 1995 A
5433189 Bales et al. Jul 1995 A
5440843 Langenhorst Aug 1995 A
5453310 Andersen et al. Sep 1995 A
5482551 Morris et al. Jan 1996 A
5505987 Jennings et al. Apr 1996 A
5506046 Andersen et al. Apr 1996 A
5508072 Andersen et al. Apr 1996 A
5514430 Andersen et al. May 1996 A
5522195 Bargen Jun 1996 A
5527387 Andersen et al. Jun 1996 A
5540026 Gartland Jul 1996 A
5543186 Andersen et al. Aug 1996 A
5545297 Andersen et al. Aug 1996 A
5545450 Andersen et al. Aug 1996 A
5549859 Andersen et al. Aug 1996 A
5557899 Dube et al. Sep 1996 A
5569514 Ayres Oct 1996 A
5580409 Andersen et al. Dec 1996 A
5580624 Andersen et al. Dec 1996 A
5582670 Andersen et al. Dec 1996 A
5601888 Fowler Feb 1997 A
5614307 Andersen et al. Mar 1997 A
5618341 Andersen et al. Apr 1997 A
5626954 Andersen et al. May 1997 A
5631052 Andersen et al. May 1997 A
5631053 Andersen et al. May 1997 A
5631097 Andersen et al. May 1997 A
5635292 Jennings et al. Jun 1997 A
5637412 Jennings et al. Jun 1997 A
5641584 Andersen et al. Jun 1997 A
5644870 Chen Jul 1997 A
5653075 Williamson Aug 1997 A
5654048 Andersen et al. Aug 1997 A
5658603 Andersen et al. Aug 1997 A
5658624 Andersen et al. Aug 1997 A
5660900 Andersen et al. Aug 1997 A
5660903 Andersen et al. Aug 1997 A
5660904 Andersen et al. Aug 1997 A
5662731 Andersen et al. Sep 1997 A
5665439 Andersen et al. Sep 1997 A
5665442 Andersen et al. Sep 1997 A
5676905 Andersen et al. Oct 1997 A
5679145 Andersen et al. Oct 1997 A
5679381 Andersen et al. Oct 1997 A
5683772 Andersen et al. Nov 1997 A
5691014 Andersen et al. Nov 1997 A
5695811 Andersen et al. Dec 1997 A
5702787 Andersen et al. Dec 1997 A
5705203 Andersen et al. Jan 1998 A
5705237 Andersen et al. Jan 1998 A
5705238 Andersen et al. Jan 1998 A
5705239 Andersen et al. Jan 1998 A
5705242 Andersen et al. Jan 1998 A
5707474 Andersen et al. Jan 1998 A
5709827 Andersen et al. Jan 1998 A
5709913 Andersen et al. Jan 1998 A
5711908 Andersen et al. Jan 1998 A
5714217 Andersen et al. Feb 1998 A
5716675 Andersen et al. Feb 1998 A
5720142 Morrison Feb 1998 A
5720913 Andersen et al. Feb 1998 A
5736209 Andersen et al. Apr 1998 A
5738921 Andersen et al. Apr 1998 A
5740635 Gil et al. Apr 1998 A
5746822 Espinoza May 1998 A
5749178 Garmong May 1998 A
5753308 Andersen et al. May 1998 A
5766525 Andersen et al. Jun 1998 A
5776388 Andersen et al. Jul 1998 A
5782055 Crittenden Jul 1998 A
5783126 Andersen et al. Jul 1998 A
5786080 Andersen et al. Jul 1998 A
5798010 Richards et al. Aug 1998 A
5798151 Andersen et al. Aug 1998 A
5800647 Andersen et al. Sep 1998 A
5800756 Andersen et al. Sep 1998 A
5810961 Andersen et al. Sep 1998 A
5830305 Andersen et al. Nov 1998 A
5830548 Andersen et al. Nov 1998 A
5843544 Andersen et al. Dec 1998 A
5849155 Gasland Dec 1998 A
5851634 Andersen et al. Dec 1998 A
5868824 Andersen et al. Feb 1999 A
5879722 Andersen et al. Mar 1999 A
5887402 Ruggie et al. Mar 1999 A
5916077 Tang Jun 1999 A
5928741 Andersen et al. Jul 1999 A
5976235 Andersen et al. Nov 1999 A
6030673 Andersen et al. Feb 2000 A
6067699 Jackson May 2000 A
6083586 Andersen et al. Jul 2000 A
6090195 Andersen et al. Jul 2000 A
6115976 Gomez Sep 2000 A
6119411 Mateu Gil et al. Sep 2000 A
6161363 Herbst Dec 2000 A
6168857 Andersen et al. Jan 2001 B1
6180037 Andersen et al. Jan 2001 B1
6200404 Andersen et al. Mar 2001 B1
6231970 Andersen et al. May 2001 B1
6268022 Schlegel et al. Jul 2001 B1
6299970 Richards et al. Oct 2001 B1
6311454 Kempel Nov 2001 B1
6327821 Chang Dec 2001 B1
6347934 Andersen et al. Feb 2002 B1
6379446 Andersen et al. Apr 2002 B1
6402830 Scrapper Jun 2002 B1
6434899 Fortin et al. Aug 2002 B1
6475275 Nebesnak et al. Nov 2002 B1
6485561 Dattel Nov 2002 B1
6494704 Andersen et al. Dec 2002 B1
6503751 Hugh Jan 2003 B2
6528151 Shah et al. Mar 2003 B1
6572355 Bauman et al. Jun 2003 B1
6573340 Khemani et al. Jun 2003 B1
6581588 Wiedemann et al. Jun 2003 B2
6619005 Chen Sep 2003 B1
6643991 Moyes Nov 2003 B1
6665997 Chen Dec 2003 B2
6668499 Degelsegger Dec 2003 B2
6684590 Frumkin Feb 2004 B2
6688063 Lee et al. Feb 2004 B1
6696979 Manten et al. Feb 2004 B2
6743830 Soane et al. Jun 2004 B2
6745526 Autovino Jun 2004 B1
6764625 Walsh Jul 2004 B2
6766621 Reppermund Jul 2004 B2
6779859 Koons Aug 2004 B2
6818055 Schelinski Nov 2004 B2
6843543 Ramesh Jan 2005 B2
6866081 Nordgard et al. Mar 2005 B1
6886306 Churchill et al. May 2005 B2
6890604 Daniels May 2005 B2
6961998 Furchheim et al. Nov 2005 B2
6964722 Taylor et al. Nov 2005 B2
6981351 Degelsegger Jan 2006 B2
7059092 Harkin et al. Jun 2006 B2
7090897 Hardesty Aug 2006 B2
RE39339 Andersen et al. Oct 2006 E
7185468 Clark et al. Mar 2007 B2
7241832 Khemani et al. Jul 2007 B2
7279437 Kai et al. Oct 2007 B2
7297394 Khemani et al. Nov 2007 B2
7386368 Andersen et al. Jun 2008 B2
7598460 Roberts, IV et al. Oct 2009 B2
7617606 Robbins et al. Nov 2009 B2
7669383 Darnell Mar 2010 B2
7721500 Clark et al. May 2010 B2
7775013 Bartlett et al. Aug 2010 B2
7803723 Herbert et al. Sep 2010 B2
7832166 Daniels Nov 2010 B2
7886501 Bartlett et al. Feb 2011 B2
7897235 Locher et al. Mar 2011 B1
7927420 Francis Apr 2011 B2
7964051 Lynch et al. Jun 2011 B2
8037820 Daniels Oct 2011 B2
8097544 Majors Jan 2012 B2
8209866 Daniels Jul 2012 B2
8381381 Daniels Feb 2013 B2
8650834 Hardwick et al. Feb 2014 B2
8915033 Daniels Dec 2014 B2
9027296 Daniels May 2015 B2
9475732 Daniels Oct 2016 B2
20010032367 Sasage et al. Oct 2001 A1
20010047741 Gleeson et al. Dec 2001 A1
20020053757 Andersen et al. May 2002 A1
20020078659 Hunt Jun 2002 A1
20020100996 Moyes et al. Aug 2002 A1
20020124497 Fortin et al. Sep 2002 A1
20020128352 Soane et al. Sep 2002 A1
20020166479 Jiang Nov 2002 A1
20030015124 Klus Jan 2003 A1
20030033786 Yulkowski Feb 2003 A1
20030084980 Seufert et al. May 2003 A1
20030115817 Blackwell et al. Jun 2003 A1
20030205187 Carlson et al. Nov 2003 A1
20030209403 Daniels Nov 2003 A1
20030211251 Daniels Nov 2003 A1
20030211252 Daniels Nov 2003 A1
20040026002 Weldon Feb 2004 A1
20040231285 Hunt et al. Nov 2004 A1
20040258901 Luckevich Dec 2004 A1
20050092237 Daniels May 2005 A1
20050227006 Segall Oct 2005 A1
20050241541 Hohn et al. Nov 2005 A1
20050284030 Autovino et al. Dec 2005 A1
20060070321 Au Apr 2006 A1
20060096240 Fortin May 2006 A1
20060168906 Tonyan et al. Aug 2006 A1
20060287773 Andersen et al. Dec 2006 A1
20070021515 Glenn et al. Jan 2007 A1
20070092712 Hodson Apr 2007 A1
20070053852 Khashoggi May 2007 A1
20070095570 Roberts, IV et al. May 2007 A1
20070125043 Clark et al. Jun 2007 A1
20070125044 Clark et al. Jun 2007 A1
20070157537 Nicolson et al. Jul 2007 A1
20070175139 Nicolson et al. Aug 2007 A1
20070193220 Daniels Aug 2007 A1
20070283660 Blahut Dec 2007 A1
20080016820 Robbins, Sr. et al. Jan 2008 A1
20080027583 Andersen et al. Jan 2008 A1
20080027584 Andersen et al. Jan 2008 A1
20080027685 Andersen et al. Jan 2008 A1
20080041014 Lynch et al. Feb 2008 A1
20080066653 Andersen et al. Mar 2008 A1
20080086982 Parenteau et al. Apr 2008 A1
20080099122 Andersen et al. May 2008 A1
20080145580 McAllister et al. Jun 2008 A1
20080152945 Miller Jun 2008 A1
20080156225 Bury Jul 2008 A1
20080286519 Nicolson et al. Nov 2008 A1
20090151602 Francis Jun 2009 A1
20090197991 Bury Aug 2009 A1
20100064943 Guevara et al. Mar 2010 A1
20100071597 Perez-Pena Mar 2010 A1
20100095622 Niemoller Apr 2010 A1
20100136269 Andersen et al. Jun 2010 A1
20110040401 Daniels Feb 2011 A1
20110120349 Andersen et al. May 2011 A1
20110131921 Chen Jun 2011 A1
20110167753 Sawyers et al. Jul 2011 A1
20120276310 Andersen et al. Jan 2012 A1
20120164402 Murakami Jun 2012 A1
20120208003 Beard Aug 2012 A1
20130008115 Bierman Jan 2013 A1
20130086858 Daniels et al. Apr 2013 A1
20130216802 Leung et al. Aug 2013 A1
20140000193 Daniels et al. Jan 2014 A1
20140000195 Daniels et al. Jan 2014 A1
20140000196 Daniels et al. Jan 2014 A1
Foreign Referenced Citations (28)
Number Date Country
2799983 Dec 2012 CA
101113077 Jan 2008 CN
101132999 Feb 2008 CN
101239838 Aug 2008 CN
102001832 Nov 2010 CN
102220829 Oct 2011 CN
102643013 Aug 2012 CN
102712531 Oct 2012 CN
10200601544 Oct 2007 DE
1266877 Dec 2002 EP
2189612 May 2010 EP
2230075 Sep 2010 EP
2314462 Apr 2011 EP
2583954 Apr 2013 EP
1265471 Mar 1972 GB
1508866 Apr 1978 GB
H05-052075 Mar 1993 JP
H06-56497 Mar 1994 JP
2004332401 Nov 2004 JP
2008036549 Feb 2008 JP
0231306 Apr 2002 WO
03004432 Jan 2003 WO
2006138732 Dec 2006 WO
2007051093 May 2007 WO
2007053852 May 2007 WO
20080144186 Nov 2008 WO
2011066192 Jun 2011 WO
2012084716 Jun 2012 WO
Non-Patent Literature Citations (11)
Entry
Search Report PCT/US07/04605, dated Oct. 4, 2007.
Search Report PCT US12/059053 dated Mar. 12, 2013.
International Search Report (KIPO) PCT/US2013/048642 dated Sep. 2, 2013.
International Search Report (KIPO) PCT/US2013/048712 dated Sep. 10, 2013.
International Search Report [KIPO] PCT/US2014/035313 dated Aug. 19, 2014.
International Search Report [KIPO] PCT/US2014/035277 dated Sep. 2, 2014.
China Office Action CN201380034441.7 [English Translation] dated Sep. 6, 2015.
EP 14759514.4 Extended European Search Report dated Sep. 23, 2016.
Extended Search Report EP 13845068 dated Oct. 16, 2016.
Kralj et al: 11 Experimental study of recycling lightweight concrete with aggregates containing expanded glass 11 Process Safety and Environmental Protection Institution of Chemical Engineers, Rugby, GB, vol. 87, No. 4, Jul. 1, 2809 (Jul. 1, 2009), pp. 267-273.
European Extended Search Report for EP 14854429.9 dated Jun. 1, 2017.
Related Publications (1)
Number Date Country
20160122247 A1 May 2016 US
Provisional Applications (3)
Number Date Country
61772646 Mar 2013 US
61772648 Mar 2013 US
61772653 Mar 2013 US