Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B19/00—Other methods of shaping glass
  • C03B19/10—Forming beads
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
  • C03C11/002—Hollow glass particles
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
  • C03B19/00—Other methods of shaping glass
  • C03B19/10—Forming beads
  • C03B19/107—Forming hollow beads
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C12/00—Powdered glass; Bead compositions
• • 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
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P40/00—Technologies relating to the processing of minerals
  • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
  • Y02P40/57—Improving the yield, e-g- reduction of reject rates

Definitions

• Hollow glass beads having a mean diameter of less than about 500 micrometers are widely used in industry, for example, as additives to polymeric compounds where they may serve as modifiers, enhancers, rigidifiers, and/or fillers.
• glass microbubbles be strong to avoid being crushed or broken during further processing of the polymeric compound, such as by high pressure spraying, kneading, extrusion or injection molding.
• Glass microbubbles are typically made by heating milled frit, commonly referred to as "feed”, that contains a blowing agent such as, for example, sulfur or a compound of oxygen and sulfur.
• feed that contains a blowing agent such as, for example, sulfur or a compound of oxygen and sulfur.
• the resultant product (that is, “raw product") obtained from the heating step typically contains a mixture of glass microbubbles (including broken glass microbubbles) and solid glass beads, the solid glass beads generally resulting from milled frit particles that failed to form glass microbubbles for whatever reason.
• the milled frit is typically obtained as a relatively broad distribution of particle sizes.
• the larger particles tend to form glass microbubbles that are more fragile than the mean, while the smaller particles tend to increase the density of the hollow glass bead distribution.
• the average density of the glass bead distribution containing the broken bead portions also generally increases.
• the present invention provides a method of forming glass microbubbles comprising heating feed under conditions sufficient to convert at least a portion of the feed into raw product comprising glass microbubbles, wherein the feed has a size distribution with a span of less than 0.9.
• the feed is provided by a method comprising: milling frit to provide milled frit; and classifying the milled frit.
• the present invention provides a raw product comprising glass microbubbles, wherein on a weight basis a majority of the raw product comprises glass microbubbles, and wherein the plurality of raw product has a size distribution with a span of less than 0.80.
• the density of the resultant hollow glass bead distribution correlates with the throughput rate at which the feed is converted into glass microbubbles.
• the present invention generally achieves at least one of the following: (1) a low density distribution of glass microbubbles having an average crush strength comparable to higher density distributions of glass microbubbles; or (2) an increased throughput rate while obtaining glass microbubbles of average density and/or crush strengths typically associated with glass microbubbles produced at lower throughput rates using the same heating apparatus and conditions.
• Frit may be prepared, for example, by crushing and/or milling a suitable glassy material, typically a relatively low melting silicate glass containing a suitable amount of blowing agent.
• a suitable glassy material typically a relatively low melting silicate glass containing a suitable amount of blowing agent.
• Silicate glass compositions suitable for forming frit are described, for example, in U.S. Pat. Nos. 2,978,340 (Veatch et al.); 3,030,215 (Veatch et al.); 3,129,086 (Veatch et al.); and 3,230,064 (Veatch et al.); 3,365,315 (Beck et al.); and 4,391,646 (Howell).
• the frit and/or the feed may have any composition that is capable of forming a glass, typically, on a total weight basis
• the frit comprises from 50 to 90 percent of Si ⁇ 2, from 2 to 20 percent of alkali metal oxide, from 1 to 30 percent of B2O3, from 0.005-0.5 percent of sulfur (for example, as elemental sulfur, sulfate or sulfite), from 0 to 25 percent divalent metal oxides (for example, CaO, MgO, BaO, SrO, ZnO, or PbO), from 0 to 10 percent of tetravalent metal oxides other than Si ⁇ 2 (for example, ⁇ O2, Mn ⁇ 2, or Zr ⁇ 2), from 0 to 20 percent of trivalent metal oxides (for example, AI2O3, Fe2 ⁇ 3, or Sb2 ⁇ 3), from 0 to 10 percent of oxides of pentavalent atoms (for example, P2O5 or V2O5), and from 0 to 5 percent fluorine (as fluoride) which may
• frit compositions can be included in the frit, for example, to contribute particular properties or characteristics (for example, hardness or color) to the resultant glass microbubbles.
• sulfur presumably combined with oxygen serves as a blowing agent that, upon heating, causes expansion of molten frit particles to form glass microbubbles.
• the frit generally includes sulfur within a range of 0.005 to 0.7 weight percent, more typically, the sulfur content of the frit is in a range of from 0.01 to 0.64 percent by weight, or even in a range of from 0.05 to 0.5 percent by weight.
• the frit is typically milled, and optionally classified, to produce feed of suitable particle size for forming glass microbubbles of the desired size.
• Methods that are suitable for milling the frit include, for example, milling using a bead or ball mill, attritor mill, roll mill, disc mill, jet mill, or combination thereof.
• the frit may be coarsely milled (for example, crushed) using a disc mill, and subsequently finely milled using a jet mill.
• Jet mills are generally of three types: spiral jet mills, fluidized-bed jet mills, and opposed jet mills, although other types may also be used.
• Spiral jet mills include, for example, those available under the trade designations "MICRONIZER JET MILL” from Sturtevant, Inc., Hanover, Massachusetts; "MICRON- MASTER JET PULVERIZER” from The Jet Pulverizer Co., Moorestown, New Jersey; and "MICRO-JET” from Fluid Energy Processing and Equipment Co., Plumsteadville, Pennsylvania.
• a spiral jet mill a flat cylindrical grinding chamber is surrounded by a nozzle ring.
• the material to be ground is introduced as particles inside the nozzle ring by an injector.
• the jets of compressed fluid expand through the nozzles and accelerate the particles, causing size reduction by mutual impact.
• Fluidized-bed jet mills are available, for example, under the trade designations "CGS FLUIDIZED BED JET MILL” from Netzsch Inc., Exton, Pennsylvania; and "ROTO-JET” from Fluid Energy Processing and Equipment Co.
• the lower section of this type of machines is the grinding zone.
• a ring of grinding nozzles within the grinding zone is focused toward a central point, and the grinding fluid accelerates particles of the material being milled. Size reduction takes place within the fluidized bed of material, and this technique can greatly improve energy efficiency.
• Opposed jet mills are similar to fluidized-bed jet mills, except at least two opposed nozzles accelerate particles, causing them to collide at a central point.
• Opposed jet mills may be commercially obtained, for example, from CCE Technologies, Cottage Grove, Minnesota.
• the width of a particle size distribution can be expressed by the following formula:
• the gradation quotient is also commonly known in the art by the term "span".
• the milled frit is classified to yield a distribution of having a span of less than 0.9, which is then used as feed for forming glass microbubbles.
• the feed may have a span of less than 0.85, 0.80, or even less than 0.75; the span may also be at least 0.7.
• the feed typically has a mean particle size of from at least 3 to 100 micrometers, more typically from at least 3 to 50 micrometers, and more typically from at least 5 to 25 micrometers.
• the present invention provides an additional degree of control that may be used in the production of glass microbubbles as compared to current methods for forming glass microbubbles known in the art.
• the main process variables in the formation of glass microbubbles are the equipment, sulfur content, and the feed rate, and median feed size. Controlling the feed size distribution according to the present invention advantageously provides an additional process variable that may be varied to achieve a desired result.
• Classification is performed such that at least one fraction, typically the coarsest classified portion, of the feed has a span of less than 0.9. This fraction is therefore isolated and used as the feed for the manufacture of the glass microbubbles. Remaining finer and/or coarser fraction(s) may be, for example, used to make glass microbubbles having physical properties comparable to existing glass microbubbles or reprocessed into frit.
• each technique produces feed having a distribution of particle sizes.
• feed obtained from milling will not have a span of less than 0.9, and in such cases additional classification according to the present invention is desirable.
• Suitable apparatus for classifying the feed include, for example, vibrating screens (including sieves), air classifiers, and wet classifiers. Other methods of classifying the feed may also be used.
• Suitable screens include, for example, sieves having a designation of from 35 mesh through at least 400 mesh according to ASTM Designation: El 1-04 entitled "Standard Specification for Wire Cloth and Sieves for Testing Purposes". Such sieves may be obtained from commercial suppliers such as, for example, Newark Wire Cloth Company, Newark, New Jersey.
• Air classifiers include, for example, gravitational classifiers, inertial classifiers, and centrifugal classifiers.
• Air classifiers are readily available from commercial sources, for example, as available from Hosokawa Micron Powder Systems under the trade designations "MICRON SEPARATOR”, “ALPINE MODEL 100 MZR”, “ALPINE TURBOPLEX ATP”, “ALPINE STRATOPLEX ASP", or “ALPINE VENTOPLEX”; or from Sepor, Inc., Wilmington, California under the trade designation "GAYCO CENTRIFUGAL SEPARATOR”.
• the feed is fed into a heat source (for example, a gas/air flame, approximately stoichiometric) and then cooled.
• a heat source for example, a gas/air flame, approximately stoichiometric
• the feed typically softens and the blowing agent causes at least a portion of the softened feed to expand and, after cooling, form a raw product that comprises glass microbubbles, optionally in combination with broken microbubble glass fragments and/or solid glass beads that did not expand during heating.
• a majority by weight of the raw product comprises glass microbubbles. More typically, at least 60, 70, 80, or even 90 percent by weight of the raw product comprises glass microbubbles.
• at least a portion of the glass microbubbles may be isolated from the raw product, for example, by using flotation techniques as described in U.S. Pat. No. 4,391,646 (Howell).
• Glass microbubbles may be prepared on apparatus such as those described, for example, in U.S. Pat. Nos. 3,230,064 (Veatch et al.) or 3,129,086 (Veatch et al.). Further details concerning heating conditions may be found for example in U.S. Pat. Nos. 3,365,315 (Beck et al.) and 4,767,726 (Marshall).
• the raw product typically has a mean particle size in a range of from 5 to 250 micrometers, more typically 30 to 150 micrometers, more typically 30 to 110 micrometers. In some embodiments, the raw product may have a mean particle size of at least 70 micrometers. The raw product has a span of less than 0.80, or in some embodiments, less than 0.75, 0.70, 0.65, or even less than 0.60.
• the glass microbubbles may have a weight ratio of alkaline earth metal oxide to alkali metal oxide weight ratio in a range of 1.2:1 to 3.0:1, and wherein at least 97 percent by weight of the combined weight of the alkaline earth metal oxide and alkali metal oxide comprises, on a weight basis, of 70 to 80 percent Si ⁇ 2, 8 to 15 percent CaO, 3 to 8 percent Na2 ⁇ , and 2 to 6 percent B2O3.
• Glass microbubbles prepared according to the present invention may be included in polymeric materials and may optionally be mixed with solid glass beads.
• suitable polymeric materials include thermoset, thermoplastic, and elastomeric polymeric materials.
• borax refers to anhydrous borax; Na2 ⁇ : 2B2O3, 90 percent smaller than 590 micrometers, obtained from US Borax, Boron, California;
• CaCC>3 refers to calcium carbonate, 97 percent smaller than 44 micrometers, obtained from Imerys, Sylacauga, Alabama;
• Li2CO3 refers to lithium carbonate; finer than 420 micrometers obtained from Lithium Corp. of America, Gastonia, North Carolina; "Si ⁇ 2” refers to silica flour, obtained from US Silica, Berkeley Springs, West
• Na2CO3 refers to soda ash, obtained from FMC Corp., Greenvine, Wyoming;
• Na2SO4 refers to sodium sulfate, 60 percent smaller than 74 micrometers, obtained from Searles Valley Mineral, Trona, California; and “Na4P2 ⁇ 7” refers to tetrasodium pyrophosphate, 90 percent smaller than 840 micrometers, obtained from Astaris, St. Louis, Missouri.
• Particle size distribution was determined using a particle size analyzer available under the trade designation "COULTER COUNTER LS-130" from Beckman Coulter, Fullerton, California.
• the strength of the glass microbubbles is measured using ASTM D3102 -72; "Hydrostatic Collapse Strength of Hollow Glass Microspheres" with the exception that the sample size of glass microbubbles is 10 mL, the glass microbubbles are dispersed in glycerol (20.6 g) and data reduction was automated using computer software. The value reported is the hydrostatic pressure at which 10 percent by volume of the raw product collapses.
• Frit GFC-I Frit was prepared by combining the following components: Si ⁇ 2 (600.0 g), Na2 ⁇ •
• Frits GFC-2 to GFC-10 and GF-I through GF-4 were prepared according to the procedure described for frit GFC-I, except that the glass composition was varied as reported in Table 1 (below).
• Frit GFC-I prepared above, was partially crushed using a disc mill (available under the trade designation "PULVERIZING DISC MILL” from Bico, Inc., Burbank, California) equipped with ceramic discs and having a 0.030-inch (0.762-mm) outer gap.
• feedstock FSC-I feedstock FSC-I
• frits GFC-3, GFC-4, GFC-6, GFC-7, and GFC-9 in place of GFC-I resulting in feedstocks FSC-3, FSC-4, FSC-6, FSC-7, and FSC-9, respectively, with median size and span values as reported in Table 2.
• feed FSC-I was followed using to generate feeds FSC-2, FSC-5, FSC-8 and FS-I through FS-4 from frits GFC-2, GFC-5, GFC-8 and GF-I through GF-4, respectively, except that after milling, each milled frit was classified into two portions using a centrifugal air classifier (available under the trade designation "ALPINE CLASSIFIER MODEL 100 MZR" from Hosokawa Micron Powder Systems). Typically, a coarse fraction and a fine fraction were isolated. Feeds FS-I through FS-6 correspond to the coarse fraction and Feedstocks FSC-2, FSC-5, and FSC-8 correspond to the fine fraction. After classification, FS-4 was screened through a 230 mesh (U.S. mesh size) sieve. PREPARATION OF GLASS MICROBUBBLES
• Feed FSC-I prepared above, was passed through a natural gas/air flame of approximately stoichiometric proportions with a combustion air flow calculated to be about 25.7 liters/minute at standard temperature and pressure and an output rate of approximately 2.75 pounds/hr (1.25 kg/hr). The ai ⁇ gas ratio was adjusted to yield the lowest total product density.
• the flame-formed product was cooled by mixing with ambient temperature air and then separated from the resulting gas stream with a cyclone device.
• the resulting glass microbubbles (glass microbubbles RPC-I) had a median size of 74.8 with a span of 1.72.
• Glass Microbubbles RPC-2 through RPC-9 and RP-I through RP-4 Glass microbubbles RPC-2 to RPC-9 and RP-I through RP-4 were prepared according to the procedure used for preparing glass microbubbles RPC-I (above) except using Feedstocks FSC-2 through FSC-9 and FS-I through FS-4, respectively, instead of Feed FSC- 1, and using the values of gas flow and output rate reported in Table 2 (below). Further, in preparing RP-4, the flame temperature was increased by enrichment with oxygen.

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• Geochemistry & Mineralogy (AREA)
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• 2004
  • 2004-12-03 US US11/004,385 patent/US20060122049A1/en not_active Abandoned
• 2005
  • 2005-09-15 MX MX2007006391A patent/MX2007006391A/es unknown
  • 2005-09-15 WO PCT/US2005/032887 patent/WO2006062566A1/en not_active Ceased
  • 2005-09-15 BR BRPI0518722-2A patent/BRPI0518722A2/pt not_active Application Discontinuation
  • 2005-09-15 EP EP05797410.7A patent/EP1833767B1/en not_active Expired - Lifetime
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