US20150158997A1 - Gypsum composite modifiers - Google Patents

Gypsum composite modifiers Download PDF

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US20150158997A1
US20150158997A1 US14/561,242 US201414561242A US2015158997A1 US 20150158997 A1 US20150158997 A1 US 20150158997A1 US 201414561242 A US201414561242 A US 201414561242A US 2015158997 A1 US2015158997 A1 US 2015158997A1
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calcium sulfate
whiskers
alpha
composite
slurry
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Mianxue Wu
Jeffrey T. Fields
Pierre Donaldson
Bill Bodiford
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Georgia Pacific Gypsum LLC
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Georgia Pacific Gypsum LLC
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Assigned to GEORGIA-PACIFIC GYPSUM LLC reassignment GEORGIA-PACIFIC GYPSUM LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FIELDS, JEFFREY T, WU, MIANXUE
Assigned to FLINT HILLS RESOURCES, LP reassignment FLINT HILLS RESOURCES, LP ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BODIFORD, Bill, DONALDSON, PIERRE
Assigned to GEORGIA-PACIFIC GYPSUM LLC reassignment GEORGIA-PACIFIC GYPSUM LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FLINT HILLS RESOURCES, LP
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/08—Oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates
    • C01F11/466—Conversion of one form of calcium sulfate to another
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
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    • C30B29/10—Inorganic compounds or compositions
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    • C30—CRYSTAL GROWTH
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    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C30B29/62—Whiskers or needles
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/02—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent
    • C30B7/04—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent using aqueous solvents
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    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
    • C—CHEMISTRY; METALLURGY
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    • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
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    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
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    • C08K2201/00—Specific properties of additives
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    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K2201/00—Specific properties of additives
    • C08K2201/016—Additives defined by their aspect ratio
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/298—Physical dimension

Definitions

  • the present disclosure relates generally to the field of calcium sulfate-based products and manufacturing, and more particularly to calcium sulfate whiskers and composites and methods for their use and manufacturing.
  • fillers are known for use as reinforcement, opacification and/or additives in paint, coatings, papermaking, and plastics.
  • fillers such as fiberglass, carbon black, calcium carbonate, silica, talc, kaolin, and aluminum hydroxide are currently used in these applications.
  • fibrous fillers generally provide improved stiffness, strength, and thermal stability properties to composites, as compared to particulate and platelet shaped fillers.
  • whiskers Single crystal fibers, also known as “whiskers,” have been shown to provide improved properties in composites as compared to traditional fibers.
  • whiskers may provide improved surface quality and aesthetics for composites, because they are typically finer and smoother than fibers. Whiskers may also provide improved dimensional and thermal stability, increased strength and toughness, and higher fluidity (e.g., for improved mold casting). However, whiskers are difficult to economically manufacture, due to the slow growth rate of whiskers.
  • a method of making anhydrite calcium sulfate whiskers including: (i) combining alpha calcium sulfate hemihydrate and water to form a slurry; (ii) autoclaving the slurry to form alpha calcium sulfate hemihydrate whiskers in water; (iii) dewatering the alpha calcium sulfate hemihydrate whiskers; and (iv) heating the alpha calcium sulfate hemihydrate whiskers to form anhydrite calcium sulfate whiskers.
  • Anhydrite calcium sulfate whiskers made by this method are also provided.
  • a method of making a composite including combining alpha-derived anhydrite calcium sulfate whiskers with a base material to form a composite.
  • a composite including alpha-derived anhydrite calcium sulfate whiskers and a base material.
  • FIG. 1 is a micrograph showing alpha-derived anhydrite calcium sulfate whiskers prepared in accordance with one embodiment of the methods disclosed herein.
  • FIG. 2 is a micrograph showing beta-derived anhydrite calcium sulfate whiskers.
  • FIG. 3 is a graph showing the elastic modulus of composite samples prepared in accordance with one embodiment of the methods disclosed herein, as tested according to three measuring methods.
  • whiskers Disclosed herein are calcium sulfate-based whiskers and composites and methods for their use and manufacturing. These whiskers, composites, and methods meet one or more of the above-described needs by providing single crystal fibers and composites made therewith, having improved properties. For example, the whiskers may have an improved aspect ratio compared to known fibers and/or a faster growth rate.
  • whiskers are provided.
  • the term “whiskers” refers to single crystal fibers.
  • the whiskers disclosed herein are made using calcium sulfate, which may also be referred to as gypsum or plaster.
  • Calcium sulfate may exist as a hemihydrate (CaSO 4 *1/2H 2 O), a dihydrate (CaSO 4 *2H 2 O), or an anhydrite (CaSO 4 ).
  • the beta calcium sulfate hemihydrate which is obtained from the calcination of dihydrate calcium sulfate under an elevated temperature at ambient temperature, may be used to prepare calcium sulfate whiskers.
  • alpha calcium sulfate hemihydrate provides surprising advantages to whisker processing and properties.
  • Alpha calcium sulfate hemihydrate which has the same chemical composition as the beta form, has gone through a pressurized calcination process, which produces well-crystallized, prismatic particles.
  • the pressurized calcination process may be an autoclave process.
  • the present disclosure generally relates to alpha calcium sulfate whiskers, the use of other suitable materials is also envisioned and intended to fall within the scope of this disclosure.
  • other particles that have been subjected to a pressurized hydrothermal reaction process may also be used.
  • methods of making anhydrite calcium sulfate whiskers include: (i) combining alpha calcium sulfate hemihydrate and water to form a slurry; (ii) autoclaving the slurry to form alpha calcium sulfate hemihydrate whiskers in water; (iii) dewatering the alpha calcium sulfate hemihydrate whiskers; and (iv) heating the alpha calcium sulfate hemihydrate whiskers to form anhydrite calcium sulfate whiskers.
  • the step of combining the alpha calcium sulfate hemihydrate and water includes combining the alpha calcium sulfate hemihydrate with the water such that the alpha calcium sulfate is present in the slurry in an amount from about 1 to about 30 percent by weight of the slurry.
  • the alpha calcium sulfate hemihydrate may be combined with the water such that the alpha calcium sulfate is present in the slurry in an amount from about 1 to about 20 percent by weight of the slurry, from about 2 to about 15 percent by weight of the slurry, or from about 2 to about 10 percent by weight of the slurry.
  • the alpha calcium sulfate hemihydrate may be combined with the water such that the alpha calcium sulfate is present in the slurry in an amount from about 5 to about 8 percent by weight of the slurry. Without being bound by a particular theory, it is believed that the combination of alpha calcium sulfate hemihydrate and water results in dihydrate crystals in the slurry.
  • the alpha calcium sulfate hemihydrate has a median particle size from about 1 micron to about 100 micron, such as from about 1 micron to about 20 micron.
  • the alpha calcium sulfate hemihydrate may have a median particle size from about 2 to about 5 micron.
  • methods of making anhydrite calcium sulfate whiskers further include sizing the alpha calcium sulfate hemihydrate to a median particle size from about 1 micron to about 10 micron, prior to combining the alpha calcium sulfate hemihydrate and water to form a slurry.
  • the alpha calcium sulfate hemihydrate may be sized by jet milling or other suitable sizing or grinding processes known to those in the art.
  • the slurry is autoclaved to form alpha calcium sulfate hemihydrate whiskers in water.
  • the step of autoclaving the slurry includes subjecting the slurry to saturated steam at a pressure from about 0 psig to about 50 psig and a temperature from about 100° C. to about 150° C. for a duration from about 30 minutes to about 8 hours.
  • the step of autoclaving the slurry may include subjecting the slurry to saturated steam at a pressure from about 1 psig to about 30 psig and a temperature from about 101° C. to about 134° C. for a duration from about 30 minutes to about 8 hours.
  • such autoclave parameters may be applied in a small-scale production setting, such as in the lab.
  • the step of autoclaving the slurry may include subjecting the slurry to saturated steam at a pressure from about 30 psig to about 52 psig and a temperature from about 134° C. to about 150° C. for a duration from about 30 minutes to about 8 hours.
  • such autoclave parameters may be applied in an industrial-scale production setting. Without being bound by a particular theory, it is believed that the calcium sulfate dihydrate crystals dissolve during the autoclave process and reform as hemihydrate whiskers at the high pressure.
  • the alpha calcium sulfate hemihydrate whiskers may then be dewatered, i.e., the whiskers may be separated from water.
  • the step of dewatering the alpha calcium sulfate hemihydrate whiskers includes filtering, vacuuming, centrifuging, or a combination thereof.
  • a screen filter may be used to dewater the whiskers.
  • the step of dewatering the alpha calcium sulfate hemihydrate whiskers includes filtering the alpha calcium sulfate hemihydrate whiskers
  • the alpha calcium sulfate hemihydrate whiskers may then be heated, or “dead burned,” to achieve a stable, insoluble anhydrite form.
  • the step of heating the alpha calcium sulfate hemihydrate whiskers to form anhydrite calcium sulfate whiskers includes heating the alpha calcium sulfate hemihydrate whiskers at a temperature from about 500° C. to about 900° C. for a duration from about 1 to about 24 hours.
  • Anhydrite calcium sulfate whiskers may be produced by the methods disclosed herein.
  • the whiskers have a Mohs hardness from about 3 to about 3.5.
  • the whiskers are thermally stable up to at least 1450° C.
  • the whiskers have a mean aspect ratio of at least 30.
  • the term “aspect ratio” refers to the ratio of the length of a calcium sulfate whisker to its diameter, and the “mean aspect ratio” is the ratio of the average whisker length to the average whisker diameter for a plurality of whiskers.
  • composites including whiskers are also provided.
  • the whiskers described herein may be lightweight and have desirable properties for structural reinforcement, and thermal and acoustic insulation.
  • the whiskers may provide improved dimensional and thermal stability, increased strength and toughness, and higher fluidity (e.g., for improved mold casting).
  • the whiskers may provide improved surface quality and aesthetics for composites, because they are typically finer and smoother than fibers.
  • methods of making composites include combining alpha-derived anhydrite calcium sulfate whiskers with a base material to form a composite.
  • composites include alpha-derived anhydrite calcium sulfate whiskers and a base material.
  • the base material may include a material selected from the group consisting of paints, coatings, paper, paper precursors, films, plastics, resins, gypsum wallboard, facers (including fiberglass mat), cement and concrete, and combinations thereof.
  • alpha-derived anhydrite calcium sulfate whiskers may be used in any applications where traditional fillers, opacification agents, or reinforcing additives, such as but not limited to fiberglass, carbon black, calcium carbonate, silica, talc, kaolin, or aluminum hydroxide, are currently used.
  • alpha-derived anhydrite calcium sulfate whiskers may be combined with paper materials, plastics, including elastomers, thermoplastics, and thermosets, and/or resins, including epoxies, and thermoset resins.
  • the base material is polyethylene, polypropylene, polybutylene, polyester, polyethylene terephthalate (PET), nylon 6, nylon 66, polyurethane, epoxy, nitrile rubber, butyl rubber, silicone rubber, PTFE, or a phenolic.
  • the step of combining the alpha-derived anhydrite calcium sulfate whiskers and the base material includes combining the alpha-derived anhydrite calcium sulfate whiskers with the base material such that the alpha-derived anhydrite calcium sulfate whiskers are present in the composite in an amount from about 1 to about 50 percent by weight of the composite, such as from about 3 to about 40 percent by weight of the composite, or from about 3 to about 10 percent by weight of the composite.
  • a composite includes from about 3 to about 10 percent by weight alpha-derived anhydrite calcium sulfate whiskers.
  • the base material includes polypropylene
  • the composite includes from about 2 to about 20 percent by weight alpha-derived anhydrite calcium sulfate whiskers, such as from about 4 to about 10 percent by weight alpha-derived anhydrite calcium sulfate whiskers, and the composite has an elastic modulus of at least 1000 MPa.
  • whisker-reinforced polymer composites may be further improved by a proper treatment of the whisker surface before they are introduced into the base material.
  • silane coupling agents or other additives capable of coupling or compatibilizing inorganic materials to organic resins, such as 3-methacryloxypropyltrimethoxysilane, may be used.
  • Embodiments of the calcium sulfate whiskers and composites disclosed herein were manufactured and tested. The results are shown below and at FIGS. 1-3 .
  • Calcium sulfate whiskers were prepared using alpha and beta hemihydrate particles mined from the same location, according to the following method. Calcium sulfate hemihydrate was combined with water to form a slurry containing 5 weight percent calcium sulfate. The slurry was autoclaved at a pressure of 10 psig and a temperature of 115° C. for 2 hours to form whiskers. The resulting whiskers were dewatered by screen filtering for 5 minutes. The dewatered whiskers were heated at a temperature of 600° C. for 3 hours to form stable, insoluble calcium sulfate anhydrite whiskers. The resulting alpha and beta calcium sulfate anhydrite whiskers were then photographed.
  • FIG. 1 is a micrograph (600 ⁇ 400 microns) taken by optical microscopy showing the alpha-derived anhydrite calcium sulfate whiskers prepared according to the above method.
  • FIG. 2 is a micrograph (600 ⁇ 400 microns) taken by optical microscopy showing the beta-derived anhydrite calcium sulfate whiskers prepared by the same method as the alpha whiskers.
  • These micrographs show the distinct morphology (e.g., length, diameter) of the alpha versus beta whiskers. For example, the alpha whiskers are much longer than the beta whiskers, and have a greater aspect ratio than the beta whiskers. Furthermore, the micrographs reveal that the growth rate is much faster for alpha whiskers than beta whiskers.
  • the alpha calcium sulfate has a crystal growth rate of at least 3-5 times that of beta calcium sulfate.
  • the autoclave time needed to make whiskers of identical length is much shorter with the alpha calcium sulfate, reducing the necessary processing time.
  • alpha calcium sulfate is able to more quickly grow into elongated whiskers under the autoclave environment.
  • Alpha and beta calcium sulfate whiskers were prepared in accordance with the method of Example 1. The whiskers were combined with polypropylene to form composites and the stiffness/flexural modulus of each composite was measured according to the Chord method and compared against the stiffness/flexural modulus of the polypropylene alone. The results are shown below in Table 1.
  • the whiskers were either premixed or side fed with the polypropylene. Premixed refers to the whiskers being combined with extruded polypropylene pellets prior to melting to form a composite. Side fed refers to the whiskers being fed into the extruder when the polypropylene is already molten.
  • FIG. 3 shows the elastic modulus of polypropylene versus a composite of polypropylene and 4.39 wt. % alpha calcium sulfate whiskers, measured according to the Flexural Chord, Flexural Tangent, and Flexural Secant methods. As shown, the stiffness of the polypropylene composite increases significantly (up to 65%) with the addition of the alpha whiskers.
  • the commercially obtained alpha calcium sulfate particles used in the foregoing examples had a median particle size of 15.4 micron and a maximum particle size of 120 micron.
  • Micronized alpha calcium sulfate particles were also prepared and tested. Specifically, commercially obtained alpha calcium sulfate particles were ground in a jet mill to a median particle size of 3.06 micron and a maximum particle size of about 12 micron. Thus, the micronized particles were smaller and more uniform in size than the commercially obtained calcium sulfate particles, as shown in Table 2.
  • the particles were jet milled on a fluid energy mill employing compressed air to produce the smaller particles. High-speed rotation within the mill subjects the calcium sulfate particles to particle-on-particle impact. As shown in Table 2, the micronized particles displayed a maximum size 10 times smaller than the commercially obtained particles. Also, the micronized particles had a maximum particle size less than 4 times the average particle size.
  • Calcium sulfate whiskers were prepared by the method of Example 1, using the micronized alpha particles. Whiskers were also prepared using the commercially obtained alpha particles and the micronized alpha particles, but at a lower concentration of 2.5 wt. % in the slurry. Comparative samples of alpha whiskers made using commercially obtained calcium sulfate were made at a concentration of 5 wt. % in the slurry. Commercially available magnesium oxysulfate whiskers were also obtained for comparative purposes. The average length and diameter was measured by scanning electron microscopy for the resulting whiskers, and the aspect ratio was calculated. The results are shown in Table 3.
  • the micronized alpha whiskers surprisingly had a significantly higher aspect ratio than the standard alpha whiskers (almost 40% greater), with a slightly shorter length and a smaller diameter.
  • the low concentration commercial particle-derived whiskers also showed a slightly higher aspect ratio than the standard whiskers, while the low concentration micronized particle-derived whiskers showed a significantly higher aspect ratio than all other samples.
  • the magnesium sulfate whiskers are much shorter than the calcium sulfate whiskers, and have an even smaller diameter.
  • an aspect ratio above 30 is desirable for reinforcement applications, with higher aspect ratios providing better structural reinforcement.
  • a method of making anhydrite calcium sulfate whiskers comprising:
  • step of combining the alpha calcium sulfate hemihydrate and water comprises combining the alpha calcium sulfate hemihydrate with the water such that the alpha calcium sulfate is present in the slurry in an amount from about 1 to about 30 percent by weight of the slurry.
  • step of autoclaving the slurry comprises subjecting the slurry to saturated steam at a pressure from about 5 psig to about 55 psig and a temperature from about 100° C. to about 150° C. for a duration from about 30 minutes to about 8 hours.
  • step of dewatering the alpha calcium sulfate hemihydrate whiskers comprises filtering, vacuuming, centrifuging, or a combination thereof.
  • step of dewatering the alpha calcium sulfate hemihydrate whiskers comprises filtering the alpha calcium sulfate hemihydrate whiskers for a duration from about 1 to about 10 minutes.
  • a method of making a composite comprising combining alpha-derived anhydrite calcium sulfate whiskers with a base material to form a composite.
  • the base material comprises a material selected from the group consisting of paints, coatings, paper, paper precursors, films, plastics, resins, gypsum wallboard, facers, cement and concrete, and combinations thereof.
  • the base material is selected from the group consisting of polyethylene, polypropylene, polybutylene, polyester, polyethylene terephthalate (PET), nylon 6, nylon 66, polyurethane, epoxy, nitrile rubber, butyl rubber, silicone rubber, PTFE, phenolics, and combinations thereof.
  • step of combining the alpha-derived anhydrite calcium sulfate whiskers and the base material comprises combining the alpha-derived anhydrite calcium sulfate whiskers with the base material such that the alpha-derived anhydrite calcium sulfate whiskers are present in the composite in an amount from about 1 to about 50 percent by weight of the composite.
  • a composite comprising alpha-derived anhydrite calcium sulfate whiskers and a base material.
  • the base material comprises a material selected from the group consisting of paints, coatings, paper, paper precursors, films, plastics, resins, gypsum wallboard, facers, cement and concrete, and combinations thereof.
  • the base material comprises polypropylene
  • the composite comprises from about 2 to about 20 percent by weight alpha-derived anhydrite calcium sulfate whiskers;
  • the composite has an elastic modulus of at least 1000 MPa.
  • the base material is selected from the group consisting of polyethylene, polypropylene, polybutylene, polyester, polyethylene terephthalate (PET), nylon 6, nylon 66, polyurethane, epoxy, nitrile rubber, butyl rubber, silicone rubber, PTFE, phenolics, and combinations thereof.

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