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WO2005028569A2 - Noirs de carbone thermiquement modifies pour diverses applications et procede de production associe - Google Patents

Noirs de carbone thermiquement modifies pour diverses applications et procede de production associe Download PDF

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Publication number
WO2005028569A2
WO2005028569A2 PCT/US2004/029881 US2004029881W WO2005028569A2 WO 2005028569 A2 WO2005028569 A2 WO 2005028569A2 US 2004029881 W US2004029881 W US 2004029881W WO 2005028569 A2 WO2005028569 A2 WO 2005028569A2
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WIPO (PCT)
Prior art keywords
furnace
carbon black
thermally modified
blacks
modified carbon
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US2004/029881
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English (en)
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WO2005028569A3 (fr
Inventor
Jorge Armando Ayala
Weidong Wang
Charles Edwards
Charles R. Herd
Rakshit Lamba
Deepak Tandon
Rodney I. Taylor
Mark S. Zak
Igor V. Barsukov
Joseph E. Doninger
Peter R. Booth
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Columbian Chemicals Co
Superior Graphite Co
Original Assignee
Columbian Chemicals Co
Superior Graphite Co
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Filing date
Publication date
Priority claimed from US10/666,048 external-priority patent/US20050063892A1/en
Application filed by Columbian Chemicals Co, Superior Graphite Co filed Critical Columbian Chemicals Co
Priority to JP2006526961A priority Critical patent/JP2007505975A/ja
Priority to EP04783920A priority patent/EP1675917A2/fr
Priority to BRPI0414310-8A priority patent/BRPI0414310A/pt
Publication of WO2005028569A2 publication Critical patent/WO2005028569A2/fr
Publication of WO2005028569A3 publication Critical patent/WO2005028569A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C09C1/56—Treatment of carbon black ; Purification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/46—Graphite
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C09C1/50—Furnace black ; Preparation thereof
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B15/00—Fluidised-bed furnaces; Other furnaces using or treating finely-divided materials in dispersion
    • F27B15/02—Details, accessories or equipment specially adapted for furnaces of these types
    • F27B15/08—Arrangements of devices for charging
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B15/00—Fluidised-bed furnaces; Other furnaces using or treating finely-divided materials in dispersion
    • F27B15/02—Details, accessories or equipment specially adapted for furnaces of these types
    • F27B15/09—Arrangements of devices for discharging
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B15/00—Fluidised-bed furnaces; Other furnaces using or treating finely-divided materials in dispersion
    • F27B15/02—Details, accessories or equipment specially adapted for furnaces of these types
    • F27B15/10—Arrangements of air or gas supply devices
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/19—Oil-absorption capacity, e.g. DBP values

Definitions

  • LAMBA Rakshit, a citizen of India, 6087 Braidwood Bend, Acworth, GA 30101.
  • the present invention relates to heat-treated carbon blacks. More particularly, the present invention relates to thermally modified carbon blacks which possess improved performance properties in food contact type applications, moisture cured polymer systems, zinc-carbon "dry cell” batteries, alkaline Zinc-Manganese Dioxide batteries, other electrochemical power sources and electronic applications and for semi- conductive wire and cable applications, and providing curing bladder compounds exhibiting superior properties, and additional applications; the carbon blacks produced by a proprietary continuous heat treatment process. 2.
  • Carbon blacks are used in insulated electric power cable semi-conducting shields. The volume resistivity of these semiconducting materials is typically in the range of 10 "1 to 10 8 ohm-cm.
  • These materials typically contain a polyolefin, a conductive carbon black, an antioxidant and other additives.
  • the main objective of these shields is to ensure long life of the primary insulation via prevention of accumulation of static charge. Longer cable life is desirable and is achieved through interfacial smoothness of the conductor shield. Surface smoothness can be achieved by using larger particle size (low surface area) carbon blacks. However, the larger particle carbon blacks have higher resistivity. Acetylene carbon black is commonly used to provide superior interfacial smoothness in semiconductor compounds. However, this type of black is difficult to produce and process, and available in only a very limited range of morphologies compared to furnace carbon blacks.
  • Electrochemical Power Sources Under the term “Electrochemical power sources” we understand devices that can produce electric current as a result of chemical or electrochemical reaction. Carbonaceous materials are widely used in the stationary and portable power sources. There are about 50 commercially viable electrochemical power sources on the worldwide market. Most of them use carbons for one or more reasons in their design.
  • Carbon additives which enhance electronic conductivity of battery active materials: Used in nearly all alkaline primary and rechargeable, lead-acid and Lithium primary battery systems, as well as in the positive electrodes of the Lithium-Ion and Lithium-Polymer batteries.
  • Graphitic carbon as electrode active material Used in the Lithium-Ion, Lithium-Ion Polymer, some metal-free and semi-metal batteries.
  • Catalysts of chemical and electrochemical reactions in batteries and fuel cells An example of such an application is the gas diffusion electrode of the zinc-air or "hearing aid" battery system as well as a gas diffusion layer of Fuel cells.
  • Carbon as battery assembly components and "processing aid" additives Applications include separator plates of the Fuel Cells, carbon rods of the carbon/zinc ("heavy duty") cells, carbon-carbon composite batteries, supercapacitors, etc.
  • Application of carbonaceous materials as an ingredient of the coatings used in power sources Some examples of the carbon coating applications are listed below: the double layer electronic capacitors, electrochemical ultracapacitors "supercapacitors",
  • Zinc-carbon batteries current collector substrate coating of: Lithium-Ion polymer cathodes and anodes, Lithium-Ion batteries with liquid electrolyte (foil coating for positive and negative electrodes), Zinc-air primary and rechargeable batteries, can coating of the Zinc Alkaline Manganese Dioxide primary and rechargeable batteries.
  • the invention which is described in the present application, relates to all of the above-mentioned applications and includes all commercially viable and development- stage portable and stationary types of power sources. A few substantiating examples of the carbonaceous material' s properties needed in power sources can be seen below.
  • Acetylene carbon black is typically used in dry cell (Zinc-carbon) batteries to impart conductivity to the cathode (manganese dioxide) and also to hold (absorb) the electrolyte. This ability to hold more electrolyte in the cathode mix makes acetylene black an attractive material. However, care must be exercised during the mixing process so as to prevent intense shearing of carbon black aggregates (structural breakdown), as this will reduce its ability to hold the electrolyte. Acetylene black has a high but weak aggregate structure.(See D. Linden, Handbook of Batteries and Fuel Cells, 3 rd ed., McGraw-Hill Book Co., Inc. New York, N.Y. 1995).
  • acetylene black The desirable properties of acetylene black are low sulfur, low moisture pickup and high electrolyte absorption capacity. It would be beneficial, therefore, to produce thermally modified carbon blacks which possess all the desired properties of acetylene black, plus a stronger aggregate structure and superior resistance to thermal oxidation.
  • Alkaline battery systems Primary and secondary alkaline batteries of the electrochemical system Zn ⁇ KOH ⁇ MnO 2 represent the largest segment of this category of power sources. In those, carbonaceous powdered materials are used for the purpose of conductivity enhancement of the MnO 2 (electrolytic manganese dioxide (EMD) or chemical manganese dioxide (CMD) cathodes.
  • EMD electrolytic manganese dioxide
  • CMD chemical manganese dioxide
  • the carbon-containing conductive suspensions often referred to as "can coating" are used in these batteries as a processing aid and a conductivity bridge at the interface: EMD cathode-positive current collector.
  • Conventional carbon (and/or acetylene) blacks have been phased out from most of the zinc-alkaline manganese dioxide batteries in mid 1980s, at least from the conductivity enhancement application in this battery system.
  • some battery companies sometimes still add small percentages of carbon (acetylene) black (0.01 — 8 wt% to the MnO 2 based electrodes) in order to enhance high discharge current density performance of certain power sources.
  • the use of the thermally heat treated or modified carbon blacks in cure bladder compounds provides a long bladder service life (as predicted by fatigue properties) and an improved thermal transfer compared to conventional cure bladder compounds.
  • existing cure bladder compounds use N300 series of carbon black or a combination of acetylene carbon blacks with N300 series blacks.
  • N300 black provides the reinforcement to the bladder compound while the acetylene black offers very good thermal conductivity, which is an important factor for cure bladders.
  • the heat treated blacks provide an improved thermal conductivity to bladder compound in comparison to acetylene black. Consequently, the cure bladder compounds containing the combination of these blacks and N300 Series blacks exhibit a better thermal conductivity and longer fatigue life.
  • the blacks may be individual or a combination of blacks, including but not limited to heat treated blacks and N300 Series carbon blacks. Other applications for heat treated graphitic carbon black. There are a number of applications, where heat treated carbon black that is subject of this invention, could be used alone or as part of the blend (or engineered composite)with other materials, as a viable alternative to conventional carbon blacks.
  • the list includes, but is not limited to the Ingredients of the electronic resistance dependent applications (examples: Ingredient of microphones, resistors, strain-, temperature- and current - sensitive resistors), oil drilling additive (example: application for stop loss circulation well and oil drilling market to be used as is or together with other stop loss additives, including but not limited to graphite, other forms of carbon black, glass beads, etc.).
  • the Current Furnace Treatment Process One important aspect of producing carbon blacks of sufficient purity to meet the applications as recited above, and many other potential applications, concerns the method in which the carbon blacks are thermally modified under the heat treatment process.
  • Heat-treated carbon blacks can also be used as the ingredients for thermal conductivity improvement (example - cure bladder compounds, heat- transfer fluid, etc.) It is known to use an electro thermal fluidized bed (EFB) furnace for the high temperature purification of carbonaceous materials and for high temperature chemical synthesis as disclosed in US Patent Nos.4,160,813 and 4,547,430, respectively. These processes use a fluidized bed furnace, as illustrated in US Patent No.
  • EFB electro thermal fluidized bed
  • 4,543,240 in which the cross-section of the fluidized bed portion of the EFB furnace is substantially constant along its height and the fluidizing gas is introduced into the furnace through a multiplicity of generally vertically oriented gas nozzles extending through a plate distributor at the bottom of the furnace.
  • This type of EFB furnace is commonly referred to as a "bubble" EFB furnace.
  • the methods of purification and thermal treatment using a bubble EFB furnace worked for particles as small as 106 ⁇ m (140 mesh). However, bubble EFB furnaces have not performed well with respect to smaller than 75 ⁇ m (200 mesh)materials.
  • Such furnaces are not effective for use with irregularly shaped particles such as flakes, needles, and other shapes, or with particles having a wide range of particle-size distribution ("polydispersed"), particularly where the material comprises a high content (greater than 30%) of fine particles with sizes less than 150 ⁇ m (100 mesh).
  • polydispersed particles having a wide range of particle-size distribution
  • the use of bubble EFB furnaces to treat and/or synthesize polydispersed materials has resulted in the entrainment of particles smaller than 106 ⁇ m (140 mesh). That is, the particles are circulated by the fluidizing gas outside of the active area of the EFB furnace. This results in a low recovery rate of treated product as a percent of raw material.
  • the plate gas distributor and its plurality of vertically oriented gas nozzles create a number of local circulating zones that have an upward flow of particle/gas mixture and a downward flow of particles, with each zone being formed around a single nozzle or group of nozzles on the distribution plate.
  • a novel electro thermal fluidized bed furnace in which the furnace body has upper and lower cylindrical portions, with the upper cylindrical portion having a diameter larger than that of the lower cylindrical portion.
  • a conical portion is disposed below the lower cylindrical portion so that the conical portion and the lower cylindrical portion define a fluidizing zone while the upper cylindrical portion defines an overbed zone.
  • the furnace includes at least one electrode extending through the upper and lower cylindrical portions and a treated material discharge pipe at the lower end of the conical portion.
  • a feed pipe is provided for introducing raw material into the lower cylindrical portion, and at least one gas flue is provided at the top of the furnace body for discharging fluidizing gas.
  • a plurality of nozzles is disposed in the conical section for introducing fluidizing gas into the furnace, with the nozzles being arranged in a generally horizontal plane and orientated so that the streams of the fluidizing gas introduced there through cross and form an upward flow in the central portion furnace body.
  • Such an electro thermal fluidized bed furnace is adapted to be used in a novel process for continuously heat treating of fine particulate matter, such as carbon black material, by continuously introducing a non-reactive fluidizing gas through the nozzles of the furnace at the pre-determined rate, continuously introducing untreated carbon black material through the feed pipe of the furnace at a predetermined rate so that it forms a fluidized bed, energizing the electrode so as to heat the fluidized bed, and continuously collecting the treated carbon black from the discharge pipe.
  • the resultant heat treated carbon black has reduced metals and ash content, better flow properties, increased pH, improved thermal conductivity, and is more resilient.
  • the resultant furnace carbon blacks can have a particle size of 7-lOOnm and an oil absorption number of 50-300 ml/100g.
  • the thermal blacks can have a particle size of 200-500 nm and an oil absorption number of less than 50 ml/lOOg.
  • the aforedescribed continuous process is capable of producing this full morphological range of thermally modified furnace and thermal carbon blacks in commercially useful quantities and with process economics consistent with their use in the intended applications.
  • thermally modified carbon blacks having such properties and of such purity so as to provide improved performance properties in food contact type applications, moisture cured polymer systems, zinc-carbon "dry cell” batteries, electrochemical applications such as alkaline batteries, other electrochemical power sources and other electronic applications, and for semi-conductive wire and cable applications; curing bladder compounds which show both improved thermal conductivity and improved processability; and other applications which may apply but are not necessarily specified herein; the carbon blacks produced by the aforesaid proprietary continuous heat treatment process, or a variation of that process as it may develop.
  • the heat treatment process it is an object of the present invention to provide a method for thermally modifying fine particulate matter, such as carbon black material, in a proprietary electro thermal fluidized bed furnace process, hereinafter sometimes referred to as "the heat treatment process;” It is a further object of the present invention to provide thermally modified carbon blacks produced from the heat treatment process which meet FDA regulations in food contact type applications; It is a further object of the present invention to provide thermally modified carbon blacks produced from the heat treatment process which improve performance properties of the carbon black for moisture cured polymer systems; e.g., polyurethane foam applications; polyurethane acrylates, cyanoacrylates, epoxies and silicones; It is a further object of the present invention to provide thermally modified carbon blacks produced from the heat treatment process to be used in zinc-carbon dry cell applications which possess all the desired properties of acetylene black or high structure carbon black, plus a higher conductivity in electrode matrixes, a stronger structure, controlled resilience, electrolyte absorption, and superior
  • Fig. 1 is a vertical cross-sectional view of a fountain EFB furnace according to the present invention.
  • Fig. 2 is a top view of the fountain EFB furnace of Fig. 1.
  • Fig. 3 is a cross-sectional view of the EFB furnace taken along line 3-3 of Fig. 1, showing the fluidizing gas distribution nozzles.
  • Fig. 4 illustrates an alternative arrangement for the fluidizing gas distribution nozzles.
  • Fig. 5 is a cross section of the LR2016 cell.
  • Fig. 1 is a vertical cross-sectional view of a fountain EFB furnace according to the present invention.
  • Fig. 2 is a top view of the fountain EFB furnace of Fig. 1.
  • Fig. 3 is a cross-sectional view of the EFB furnace taken along line 3-3 of Fig. 1, showing the fluidizing gas distribution nozzles.
  • Fig. 4 illustrates an alternative arrangement for the fluidizing gas distribution nozzles.
  • Fig. 5 is a cross section of the LR2016 cell.
  • Table 5 A is the galvanic discharge curves for LR2016 batteries.
  • Table 1 is a Matrix of Carbon Black Properties Imparted as a Result of Thermal Modification and Their Effect on Various Applications.
  • Table 2 is Moisture Pickup data for as-is and heat-treated carbon blacks.
  • Table 3 is Metal Impurities, Ash and Sulfur Content of as-is and heat-treated
  • Table 4 Colloidal Properties of Heat-Treated Carbon Black and Acetylene Carbon Black.
  • Table 5 is structure stability of VHS blacks.
  • Table 6 is Moisture Pickup (MPU) and Melt Flow Properties at 30% loading in lO MI LDPE.
  • Table 7 is Volume resistivity versus processability in polyethylene.
  • Table 8 is Combustion Rate and Activation Energy of 975U before and after heat treatment.
  • Table 9 is a listing of PAH Compounds regulated by FDA.
  • Table 10 is PAH Content (ppb) of FDA Compliant Competitive Carbon Black, Heat-treated CDX-975U, heat treated N700 Series Carbon Black and Control N700 Series Carbon Black.
  • Table 11 is PAH content for N220, N330 Heat-treated N220 and Heat-treated N330 Heat-treated CB Samples.
  • Table 12 is Summary of Maximum Discharge capacity of as-is and heat-treated carbon black samples at three discharge rates.
  • Table 13 shows the Colloidal Properties of Acetylene black_(Control) and Thermally modified carbon blacks A and B, and N330.
  • Table 14 shows the Curing Bladder Formulations of a Control compound and compounds containing Thermally modified carbon blacks.
  • Table 15 shows the Processing Characteristics of a Control compound and compounds containing Thermally modified carbon blacks.
  • Table 16 shows the Capillary Rheometer Prossability Characteristics of a Control compound and compounds containing Thermally modified carbon blacks.
  • Table 17 shows the MDR Curing Profiles of a Control compound and compounds containing Thermally modified carbon blacks.
  • Table 18 shows the Surface Analyzer Dispersion Properties of a Control compound and compounds containing_Thermally modified carbon blacks.
  • Table 19 shows the Stress-Strain, Aged and Unaged, Properties of a Control compound and compounds containing Thermally modified carbon blacks.
  • Table 20 shows the Performance Properties of a Control compound and compounds containing Thermally modified carbon blacks.
  • thermally modified carbon blacks of the present invention possess such properties and are of such purity so as to provide improved performance properties in food contact type applications, moisture cured polymer systems, dry cell batteries, alkaline, zinc air, Lithium-ion, nickel-metal hydrade, nickel cadmium batteries and other electrochemical power sources as well as electrochemical applications, and for semi-conductive wire and cable applications; and other applications which may apply but are not necessarily provided herein.
  • FIG. 1 illustrates an electro thermal fluidized bed furnace and the process through which the aforesaid carbon blacks are thermally modified to provide their unique qualities in their various applications.
  • a fountain-type EFB furnace generally designated 10
  • the principal characteristic of a fountain fluidized bed is that it has a single strong circulating contour with a central upward flow of particle-gas mixture in the center of the fluidized bed and an outer downward flow of particles along the furnace walls.
  • the furnace includes a furnace body shell 10, typically made of steel and encased with a insulating material 14.
  • the furnace body 12 is typically made of graphite.
  • the furnace body comprises a lower cylindrical portion 16, an upper cylindrical portion 18 disposed above the lower cylindrical portion and having a larger diameter than the central cylindrical portion 16.
  • a conical gas distributor 20 is disposed below the central cylindrical portion 16, with the gas distributor 20 having a plurality of fluidizing gas distribution nozzles 22.
  • the nozzles 22 are in fluid communication with a plenum 24 into which the fluidizing gas is introduced through an inlet 26.
  • the conical gas distributor 20 defines a central angle (alpha) of from 30 to 90, and preferably of from 40 to 60.
  • the space above the gas distribution nozzles 22 to the top of the lower cylindrical portion 16 generally define the fluidized bed zone 28.
  • the space above the fluidized bed zone, coinciding generally with the upper cylindrical portion 18, is known as the overbed space or free board zone 30.
  • the operational height H ⁇ of the fluidized bed area 28 generally coincides with the distance between the nozzles 22 and the upper end of the lower cylindrical portion 18.
  • H fl is preferably less than or equal to one and one-half to twice the inside diameter IDj, of the lower cylindrical portion 16.
  • the minimal height of the free board or overbed space H ov s is preferably one and one-half times the height of the fluidized bed H fo to ensure that any entrained particles are separated from the gas flow and returned to the fluidized bed space of the furnace.
  • each of the cylindrical portions 16, 18 and the conical gas distributor 20 has a circular or an elliptical cross-section. Other shaped cross-sections (such as square, rectangular, octagonal, etc.) may exhibit satisfactory hydro-dynamic characteristics.
  • An elongated electrode 32 extends into the furnace body 12 from the top 34 through the upper and lower cylindrical portions 18, 16, respectively.
  • the electrode 32 is preferably fabricated from an electronically conductive, heat-resistant material such as graphite. When a single electrode is used it must be located centrally within the furnace body and aligned with a vertical axis Y thereof. Alternatively, a plurality of electrodes may be used, in which case the electrodes are arranged symmetrically about the central axis Y.
  • the lower cylindrical portion 16 includes a second, sleeve- type electrode 36 disposed substantially coaxially relative to the elongated electrode 32.
  • the sleeve type electrode is also preferably constructed of a heat resistant and electronically conductive material, such as graphite.
  • the electrodes 32, 36 are adapted be connected to the opposite terminals of a source of electronic power (not shown), the power source typically providing 20 to 200 volts between the two electrodes 32, 36.
  • the application of voltage between the electrodes causes fluidized material to be rapidly heated by direct electronic resistance in accordance with the I 2 r conversion of electronic energy into heat.
  • a feed pipe 38 is provided for continuously supplying raw material into the fluidized bed zone 28 of the furnace body 12. As illustrated, the feed pipe 38 is vertically orientated and extends through the top 34 of the furnace body 12, down through the upper cylindrical portion 18, and has its outlet adjacent to the wall either at or below the top of the lower cylindrical portion 16.
  • raw material is introduced from the feed pipe 38 into the fluidized bed, or at least at the top surface thereof, in the area of the downward flow of solid particles being circulated in the fluidized bed.
  • the bottom of the furnace body includes a discharge port 40 through which effluent solids may be continuously withdrawn by gravity flow without need for mechanical devices or moving parts.
  • the discharge port 40 depends from the conical gas distributor 20, with the inlet to the discharge port 40 generally coinciding with the apex of the conical gas distributor 20.
  • Gaseous effluent can be withdrawn through one or more exhaust pipes or gas flues 42 in the top 34 of the furnace body 12. This effluent gas can be readily cleaned and treated to control particulate and gaseous pollutants as required.
  • the conical gas distributor 20 includes a plurality of fluidizing gas inlet nozzles 22 (8 shown), through which fluidizing gas is introduced into the furnace body 12.
  • the fluidizing gas is typically nitrogen, argon or other non-reactive gas.
  • the nozzles 22 are orientated so that fluidizing gas forms crossing sprays, with a strong uniform upward flow.
  • the velocity at which the fluidizing gas exits the nozzles depends on the particle size of the material being fluidized.
  • the nozzles 22 are arranged so that their axes X are aligned radially, with the fluidizing gas being directed toward the center of the conical gas distributor 20.
  • the nozzles 22 are orientated so that their axes X form an angle ⁇ (beta) of from 10 to 20° with respect to the tangent to the conical gas distributor 20 at the location of the nozzle, as best seen in Fig. 4.
  • the arrangement of the nozzles 22 so that their axes X are generally tangential to nozzle circle provides for a rotation of the fluidized bed, making it more stable and less sensitive to any deviation of the elongated electrode 32 from the central axis Y. This also helps to prevent the fluidized particles from being brought into contact with the conical gas distributor 20 at high velocity, which could result in undue wear from abrasion.
  • the nozzles 22 are preferably disposed at a heigh H N above the conjunction of the gas distributor 20 and the inlet to the discharge port 40.
  • H N is from 0.5 to 0.75 of the total height H ⁇ c of the conical gas distributor 20, and more preferably from 0.6 to 0.65 H ⁇ c .
  • Each of the nozzles 22 has a ring diameter perpendicular to its X axis at which is defined a free cross-sectional area.
  • the sum of the free cross-sectional areas of the nozzles 22 should be from 0.15 to 0.5% of the cross-sectional area of the cylindrical portion of the fluidized bed, that is the cross-sectional area of the lower cylindrical portion 16.
  • the free cross-sectional area of the nozzles 22 should be between 0.25 and 0.4% of the cross-sectional area of the fluidized bed.
  • untreated particulate material is continuously fed by gravity through the feed pipe 38 into the reaction zone of the EFB furnace 10.
  • the untreated particulate material may comprise fine, irregularly shaped or polydispersed materials.
  • the polydispersed material has comprised particles sized from between 1.7mm (12 mesh), and as small as 5 ⁇ m.
  • the untreated particulate may be an electroconductive or semiconductive material, such as carbonaceous materials like carbon black, coke (fluid coke, green flexi-bed coke, delayed coke, etc.), and graphite.
  • the untreated particulate matter is discharged from the feed pipe 38 at the top of, or just inside, the fluidizing zone in the downward flow of particles.
  • the material from the feed pipe is maintained in a fluidized state in the region of the furnace corresponding approximately to the lower cylindrical portion 16, and electronic current is passed through the fluidized bed to uniformly heat the material to a high temperature, typically from 2,200-2,400°C.
  • Treated particulate material is continuously withdrawn by gravity through the discharge pipe 40 at about the same rate at which the untreated particulate is introduced. The rate is such that the treatment time of the particulate material within the fluidized bed is sufficient to result in the desired heat treatment.
  • the present EFB furnace there is no need for mechanical devices or moving parts within the furnace 10 to effect the discharge of the treated material.
  • the treated material After being discharged through the pipe 40, the treated material may be cooled in a cooling chamber (not shown).
  • gaseous effluent can be withdrawn through the gas flue 42 at the top 34 of the furnace body 12. This gaseous effluent can be readily cleaned and treated to control pollutants to the extent required.
  • significantly better recovery rates (of 90+% in pilot runs) for treated particulate have resulted, in contrast to the recovery rates when using the prior art, bubble-type EFB's, (in which the recovery rate is typically less than 66%).
  • the critical velocity of fluidization has been reduced over that of a bubble-type EFB furnace from approximately 0.30 ft./sec. to approximately 0.25 ft/sec.
  • the range of the furnace and thermal process carbon blacks would have been heat treated to within the range 800 to 3000°C for the purpose of improving their performance properties.
  • the furnace carbon blacks would have a particle size of 7-100 nm and an oil abso ⁇ tion number of around 50-300 ml/lOOg.
  • the thermal blacks would have a particle size of 250-500 nm and an oil absorption number of less than 50 ml/lOOg.
  • the heat-treatment of carbon blacks in the continuous furnace process as described above substantially removes sulfur, graphitizes the carbon black and makes the carbon black more oxidation resistant.
  • each of the carbon blacks referred to in Table 2 are carbon blacks produced by Columbian Chemicals Company.
  • Metallic impurities (salts) in carbon black can also contribute to moisture pick- up.
  • Table 3 illustrates the reduction in metal and ash contents of the carbon blacks
  • thermally Modified Carbon Black for Semi-conductive Wire and Cable Applications In the background of the invention, reference is made to the fact that carbon blacks are used in insulated electric power cable semiconducting shields. Acetylene carbon black is commonly used to provide the superior interfacial smoothness in semiconductor compounds. However, this type of black is difficult to produce and process compared to furnace carbon blacks. In utilizing the process for heat treating carbon blacks as was described in reference to Figure 1, thermally modified furnace carbon blacks were produced which provide compounds with interfacial smoothness at least equivalent to that obtained with acetylene carbon black.
  • thermally modified carbon blacks are easy to process and provide better conductivity and melt flow properties.
  • thermally modified carbon blacks can be produced with a much broader range of morphologies as compared to acetylene black and have lower moisture absorption characteristics, which is a highly desirable property in semiconductor compounds.
  • Table 4 entitled "Colloidal Properties.” Table 4 compares three different blacks: CDX-975U, (a furnace carbon black used in semiconductive compounds acetylene black, and CDX975U which was heat treated according to the heat treatment process as described above, at approximately 2,000 degrees centigrade.
  • the iodine value (mg/g) of the heat treated black is 98.8.
  • the SA (m 2 /g) is 71.9.
  • the DBPA (ml/100g) is 156.8.
  • the sulfur content is 0.01%.
  • the pH is 10.6 and the moisture percentage is 0.0.
  • the MPU at one hour is 0.17%; and tlie equilibrium MPU is 0.27%; the equilibrium MPU of the compound is 0.01%; and the melt flow index (g/lOml) is 7.0.
  • melt flow index it should be noted that there was 10 kilogram load at 190 degrees centigrade.
  • Table 7 there is illustrated the volume resistivity versus the processibility in polyethylene of the two blacks, namely, the acetylene black, and the heat treated CDX-975U.
  • the samples were first heated to the target combustion temperature and equilibrated for 10 minutes under inert atmosphere followed by switching to either pure oxygen or air for two to four hours.
  • the activation energy for combustion is calculated from the slope of arrhenius plots and is given also in Table 8.
  • the heat treated carbon black samples are seen to have a higher activation energy than that of the CDX-975U control.
  • Relevant Test Methods Sulfur.
  • the method used in the determination of the total sulfur content of carbon black involves a carbon black sample combusted in an oxygen enriched atmosphere in order to convert any sulfur present into SO 2 .
  • the SO 2 is then detected and quantified by infrared detection. This is set forth in "Standard Test Methods for Carbon Black- sulphur Content", in the book ASTM Standards. Vol.
  • the sulfur content of the carbon black is directly related to the sulfur level of the feedstock oil. Most feedstock oil available contains a relatively high sulfur level, typically greater than 2%. The majority of sulfur in carbon black is chemically combined and not reactive. However, even small quantities of sulfur species can have significant effects in a variety of rubber and industrial applications.
  • the sample is weighed at regular intervals (every 15 minutes for first 1 hour, then every 4 hours for next 24 hours and then every 24 hours) in order to determine the moisture pick-up of the compound, the process typically takes over 100 hours.
  • the equilibrium moisture absorption of the compound is determined from graphical treatment of the data. The tendency of carbon black to adsorb atmospheric moisture after being compounded into plastics can affect the properties of the plastics during processing.
  • the vacuum is removed and the black is immediately transferred to a preweighed aluminum dish and the carbon black is weighed.
  • the sample is weighed at regular intervals (every 15 minutes for first 1 hour, then every 4 hours for next 24 hours, and then every 24 hours) in order to determine the moisture pickup.
  • the equilibrium MPU for a carbon black is typically measured at regular intervals over a one week period.
  • the amount of moisture absorbed by a black is influenced by several physical and chemical characteristics of the carbon black.
  • Carbon blacks are used quite often as colorants for polymers in producing, manufacturing, packing, processing, preparing, treating, packaging, transporting or holding food under all temperatures.
  • Typical furnace blacks have PAH levels that are higher than allowed under the FDA regulations.
  • furnace carbon black grades available that meet the FDA limits. However, these grades are of only limited morphology.
  • Channel blacks which are also used in such applications are exempt from the FDA regulations, but are also increasingly difficult to access. In addition they have very poor processing characteristics.
  • the thermally modified carbon blacks of the present invention possess the necessary properties to meet all FDA guidelines for food contact applications, including lower PAH levels within limits that are allowed under the FDA regulations.
  • GC-MS Gas Chromatography-Mass Spectroscopy
  • PAH Polycyclic Aromatic Hydrocarbon
  • Carbon blacks are invariably formed in a high temperature gas stream, a process involving pyrolysis. Such pyrolysis of carbonaceous raw material results, in aromatization (ring formation). During the process of carbon black formation it is possible that the ring formation may lead to condensation of these aromatic rings, yielding PAH compounds that may be retained within the carbon black.
  • FDA Food Addition Regulation The high-purity furnace blacks that meet the FDA regulation are those containing a total of 22 specified PAH compounds (see Table 9) not exceeding 500 ppb (parts per billion) and benzo(a)pyrene not exceeding 5 ppb.
  • the method for determination of PAH content is gas Chromatography Mass Spectrometry (GC-MS).
  • Example #1 Zinc-carbon Dry Cell Applications Carbon blacks are used in dry cell (zinc-carbon batteries). The application for tlie carbon black is in both the positive electrode and in carbon rods of this battery system. In this application in the present invention, there is utilized the continuous heat treatment process as disclosed therein, for thermally modifying a range of furnace carbon blacks by heat treating to 800-3,000 degrees centigrade for the purpose of improving their performance properties in dry cell batteries. In the battery mockup test results work (performed at Center for Energy
  • Example #2 Heat Treated carbon black in alkaline cells.
  • the alkaline cells of the electrochemical system Zn KOH/MnO 2 have been built and tested. The findings are reported herein.
  • LR2016 size have been manufactured and tested at the Superior Graphite Co.
  • the abstracts below describe battery design and the procedures used for manufacturing and testing of batteries.
  • the typical electrochemical device used for testing was a coin cell of a standard 2016 size (20 mm diameter and 1.6 mm high), please see Fig. 5.
  • the stainless steel housing for such cells is available from Hoshen, a Japan corporation.
  • Fig. 5 schematically represents the cutaway view of the cell.
  • the construction of such cells can be referenced to the published literature such as D. Linden. Handbook of Batteries and Fuel Cells., McGraw-Hill Book Co., Inc., New York, 1995, P. 10.10.
  • the battery shown in Fig. 5 consists of the following main components.
  • Stainless steel anode cup (1), cathode cup (6) and a nylon gasket (7) represent a housing of the battery.
  • the interior of the cathode cup is airbrushed with graphite containing can coating (4).
  • Such coating for instance, is available from Superior Graphite Co., and is called "Formula 39A".
  • the cathode (3) consists of the active material, EMD.
  • An example of such material is AB - standard alkaline battery grade available from Kerr McGee, a US company.
  • the amount of EMD in the cathodes was either 0.35 g or 0.3 g.
  • the separator is impregnated with KOH electrolyte prior to placing it in the battery.
  • the anode (2) is based on Zinc powder, available from Doral Distribution, a Swiss company (grade: Zinc Doralloy 104 ⁇ 0.036 mm). Its amount is balanced to be equal to the amount of EMD in the counter electrode.
  • the anode paste as well is impregnated with KOH electrolyte prior to assembling of the cell.
  • the battery is sealed by the means of a crimping device available for this type of cells from Hoshen Corp.
  • thermally modified carbon blacks will work more efficiently than other conventional graphites in the zinc-air "hearing aid" primary batteries, Li-Ion and Li-Ion polymer secondary batteries, industrial nickel cadmium rechargeable batteries, reserve cells, electrochemical ultracapacitors, fuel cells, and other power sources.
  • Fig 5A the enclosed chart containing the discharge curves of the five samples of carbon black.
  • Fig. 5 A illustrates the Galvanostatic discharge curves for LR2016 batteries having various carbon blacks and/or their heat treated versions. Curves for the two most typical cells of each formula are shown. One can see from the graph on Fig. 5 A that heat-treated thermal black offers at least a 5 times better conductivity enhancement efficiency than the as-is thermal black.
  • the as-is and heat-treated thermal blacks are plotted in comparison with a Furnace Black used on the furnaces in KY and ARK.
  • the similarities between the as-is thermal black and the furnace black are obvious.
  • Furnace Black is known to be more insulating than conducting, hence we did not expect even its heat-treated version to outperform high structure carbons Super S, as-is CDX- 975U and heat-treated CDX-975U.
  • a Super S grade of carbon black from Erachem which is known to give a high capacity in batteries and performs as well as expanded graphite (GA-17, a product of Superior Graphite Co.
  • CDX-975U As derived from Fig. 5A, heat-treated CDX-975U containing cells show the record for highest discharge capacity by a wide margin. It is noteworthy that its precursor, CDX-975U, due to its high surface area (- 170 m 2 /g) demonstrates higher average discharge voltage of the cells than the batteries containing heat-treated CDX- 975U (surface area is 68 m 2 /g). At the same time, CDX-975U cannot be used due to its high affinity to enter in the thermodynamically unstable reaction with MnO 2 partially because of its high surface area.
  • Example #3 Resistivity and springback characteristics of the heat treated and ungraphitized carbon black powders for use in energy applications.
  • surface areas resistivities and resiliencies of carbon black powders before and after graphitization. All 3 physicochemical properties are of great importance for electrochemical applications.
  • the description of test methods is provided below.
  • Resiliency Percent expansion
  • a sample is compressed between two plugs within a cylindrical mold. This mold assembly is subjected to a loading of 690 bar (10,000 psi). When stable at this loading, the height of the assembly is measured. The load is then released and the assembly allowed to expand vertically until a stable height is reached. The percentage increase in height over the original compacted height is calculated.
  • thermally enhanced carbon black could find wide use in a number of stationary and portable power sources. Its application can be split into the six major groups, which are described below: 1. Thermally enhanced carbon black carbon additives; which enhance electronical conductivity of battery active materials. 2.
  • thermally enhanced carbon black as electrode active material. 3. Thermally enhanced carbon black as a catalyst of chemical and electrochemical reactions in batteries. 4. Thermally enhanced carbon black as battery assembly components. 5. Thermally enhanced carbon black as an ingredient of the coatings used in power sources. 6. Thermally enhanced carbon black as an ingredient of the electronical resistance dependent applications.
  • the thermally enhanced carbon black could be used in any of the above applications alone, or in combination with any type and quality of graphite and/or carbon black, and/or other chemicals.
  • the thermally enhanced carbon black carbon used in the above applications processed together with other materials or deposited onto, or smeared into them.
  • the thermally enhanced carbon black carbon will have application specific spec ranges, which are not fully known at this time.
  • thermally enhanced carbon black additives which enhance electronical conductivity of battery active materials: Zinc-carbon primary batteries; Magnesium and Aluminum primary batteries; Alkaline Manganese Dioxide batteries; Mercuric oxide batteries; Silver oxide batteries; Zine-air batteries (bottom and cylindrical configurations); Lithium batteries (LitMurn/Sulfur Dioxide Primary batteries, Lithium Thionyl chloride primary batteries, Lithium/Oxychloride batteries, Lithium/manganese dioxide batteries (primary and rechargeable), Lithium/carbon monofluoride batteries, Lithium/Iron disulfide batteries, Lithium/Copper oxide batteries, Lithium/copper oxyphosphate batteries, Lithium /Silver vanadium oxide primary and secondary batteries; Solid electrolyte batteries (Li/LiI(A1203)/metal salt batteries, Lithium-Iodine batteries; Ag/RbAg415/Me4Nin,
  • thermally enhanced carbon as electrode active material.
  • Application examples for thermally enhanced carbon black as an ingredient of the electronic resistance dependent applications Ingredient of the microphones, resistors, strain-, temperature- and current- sensitive resistors. TV tube and "black matrix" coatings.
  • Tables 13 through 20 provide evidence of the improved qualities of carbon blacks thermally treated by the heat treatment process herein disclosed that provide curing bladder compounds with a longer service life and increased thermal conductivity. In general, for this application, the heat treated blacks provide improved thermal conductivity and fatigue life to bladder compounds than an acetylene black control.
  • Tables 13 through 20 two thermally modified carbon blacks were compared for certain properties against a control black commonly used by cure bladder applications, acetylene black. Both the thermally modified and acetylene blacks were used in combination with N330 carbon black. Table 13 provides the colloidal properties of the carbon blacks used in the compounds of Table 14 and to generate the application results in Tables 15-20.
  • Carbon blacks "A” and “B” were thermally modified by heat treatment to 2000°C.
  • Table 14 provides the curing bladder formulations evaluated.
  • Tables 15 and 16 indicate the compounds formulated with the thermally modified blacks to be slightly more viscous than the control compound.
  • Table 17 demonstrates that the cure characteristics of the compounds prepared using the thermally modified carbon blacks are reasonably close to those of the control compound.
  • Table 18 it is demonstrated that the compounds being compared against the control black are well dispersed, while Table 19 shows the modulus of the compound prepared with the thermally modified carbon black to be somewhat below that of the control; the modulus could be made equivalent by slightly increasing the carbon loading, which would further enhance thermal conductivity.
  • Table 20 demonstrates the superior thermal conductivity of the compounds prepared with the thermally modified carbon black and also shows them to offer advantages in characteristic fatigue life.

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Abstract

Un four à lit fluidisé électro-thermique est adapté pour servir dans un procédé de traitement thermique continu d'une matière particulaire fine, telle que le noir de carbone. Ce procédé consiste à: introduire d'abord en continu un gaz de fluidisation non réactif par les buses du four, à une vitesse prédéterminée; introduire ensuite en continu du noir de carbone non traité par le tuyau d'alimentation du four à une vitesse prédéterminée, de manière à ce qu'il forme un lit fluidisé; et enfin, mettre l'électrode sous tension pour chauffer le lit fluidisé, et recueillir en continu le noir de carbone ainsi traité du tuyau d'évacuation. Le noir de carbone ainsi recueilli du tuyau d'évacuation est caractérisé en ce que: les PAH et le soufre sont éliminés; le noir de carbone a subi une graphitisation; l'humidité captée par le noir de carbone est éliminée et le noir de carbone est plus résistant à l'oxydation. Par ailleurs, les noirs de carbone obtenus du four présentent un calibre de grain compris entre 7 et 100 nm et un indice d'absorption d'huile compris entre 50 et 300 ml/100g, alors que les noirs de carbone thermiques présentent un calibre de grain compris entre 200 et 500 nm et un indice d'absorption d'huile inférieur à 50 ml/100g. L'invention permet d'obtenir des noirs de carbone thermiquement modifiés qui possèdent des performances améliorés dans des applications pour contact alimentaire, des systèmes polymères de réticulation par l'humidité, des applications de piles sèches zinc-carbone, d'autres sources d'alimentation électrochimiques et d'autres applications électroniques, des applications de câbles et fils semiconducteurs, ainsi que dans des composés de vessies qui présentent une conductivité thermique et une transformabilité améliorées.
PCT/US2004/029881 2003-09-18 2004-09-10 Noirs de carbone thermiquement modifies pour diverses applications et procede de production associe Ceased WO2005028569A2 (fr)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1983021A1 (fr) 2007-04-18 2008-10-22 Continental Aktiengesellschaft Mélange de caoutchouc, de préférence pour bandes de roulement de pneus
JP2010509466A (ja) * 2006-11-07 2010-03-25 キャボット コーポレイション 低ｐａｈ量を有するカーボンブラックおよび製造方法
WO2013175488A3 (fr) * 2012-03-30 2014-02-27 Aditya Birla Science And Technology Company Ltd. Procédé permettant d'obtenir de la poudre de noir de carbone à teneur en soufre réduite
EP2777091A4 (fr) * 2011-11-07 2015-07-22 Basf Se Piles électrochimiques rechargeables
US9287565B2 (en) 2011-12-22 2016-03-15 Cabot Corporation Carbon blacks and use in electrodes for lead acid batteries
EP3031867A4 (fr) * 2013-08-08 2017-04-19 Lion Specialty Chemicals Co., Ltd. Noir de carbone et procédé de production associé, et dispositif de stockage d'électricité et composition de résine conductrice
US9873797B2 (en) 2011-10-24 2018-01-23 Aditya Birla Nuvo Limited Process for the production of carbon black
US9985281B2 (en) 2015-06-24 2018-05-29 Cabot Corporation Carbonaceous materials for lead acid batteries
WO2019016322A1 (fr) 2017-07-19 2019-01-24 Imerys Graphite & Carbon Switzerland Ltd. Polymères thermiquement conducteurs comprenant un matériau de noir de carbone
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WO2011019184A2 (fr) * 2009-08-10 2011-02-17 엔바로테크 주식회사 Procédé et appareil permettant la production d’un matériau d’échelle nanométrique présentant une structure de graphène
DE102009045060A1 (de) * 2009-09-28 2011-03-31 Evonik Degussa Gmbh Ruß, ein Verfahren zu seiner Herstellung sowie seine Verwendung
JP2012012450A (ja) * 2010-06-30 2012-01-19 Denki Kagaku Kogyo Kk カーボンブラック及びそれを含有してなる低臭性組成物。
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WO2013190624A1 (fr) * 2012-06-18 2013-12-27 電気化学工業株式会社 Noir de carbone pour batteries secondaires non aqueuses, électrode, et batterie secondaire non aqueuse
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US20140377659A1 (en) * 2013-06-21 2014-12-25 Cabot Corporation Active materials for lithium ion batteries
WO2015116943A2 (fr) 2014-01-31 2015-08-06 Monolith Materials, Inc. Conception de torche à plasma
CA2975731C (fr) 2015-02-03 2024-01-02 Monolith Materials, Inc. Systeme de generation de noir de carbone
CA3032246C (fr) 2015-07-29 2023-12-12 Monolith Materials, Inc. Procede et appareil de conception d'alimentation electrique de torche a plasma a courant continu
CN108290738A (zh) 2015-09-09 2018-07-17 巨石材料公司 圆形多层石墨烯
JP6668800B2 (ja) * 2016-02-12 2020-03-18 住友ゴム工業株式会社 ゴム組成物およびタイヤ
EP3676901B1 (fr) * 2017-08-28 2024-10-02 Monolith Materials, Inc. Systèmes et procédés de particules
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Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1091895A (fr) * 1975-07-01 1980-12-23 William M. Goldberger Methode et appareil pour le traitement thermique de matieres carbonees en lit fluidise
US6482386B2 (en) * 1999-12-02 2002-11-19 Cabot Corporation Carbon blacks useful in wire and cable compounds
US7358004B2 (en) * 2001-10-30 2008-04-15 N. E. Chemcat Corporation Carbon black, electrocatalyst carrier formed from carbon black, and electrocatalyst and electrochemical device using carrier
US20050062205A1 (en) * 2003-09-18 2005-03-24 Zak Mark S. Method and apparatus for heat treatment of particulates in an electrothermal fluidized bed furnace and resultant products

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US9410042B2 (en) 2012-03-30 2016-08-09 Aditya Birla Science And Technology Company Ltd. Process for obtaining carbon black powder with reduced sulfur content
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US11352536B2 (en) 2016-02-01 2022-06-07 Cabot Corporation Thermally conductive polymer compositions containing carbon black
US11732174B2 (en) 2016-02-01 2023-08-22 Cabot Corporation Thermally conductive polymer compositions containing carbon black
US12180412B2 (en) 2016-02-01 2024-12-31 Cabot Corporation Thermally conductive polymer compositions containing carbon black
WO2019016322A1 (fr) 2017-07-19 2019-01-24 Imerys Graphite & Carbon Switzerland Ltd. Polymères thermiquement conducteurs comprenant un matériau de noir de carbone
US11993693B2 (en) 2018-03-28 2024-05-28 Dow Global Technologies Llc Composite of non-polar organic polymer and ultra-low-wettability carbon black

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BRPI0414310A (pt) 2006-11-07
KR20060123120A (ko) 2006-12-01
WO2005028569A3 (fr) 2006-03-09
JP2007505975A (ja) 2007-03-15

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