WO2018125861A2 - Systèmes de réaction d'extrusion et procédés de fabrication de particules de céramique dérivées de polymères - Google Patents

Systèmes de réaction d'extrusion et procédés de fabrication de particules de céramique dérivées de polymères Download PDF

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Publication number
WO2018125861A2
WO2018125861A2 PCT/US2017/068404 US2017068404W WO2018125861A2 WO 2018125861 A2 WO2018125861 A2 WO 2018125861A2 US 2017068404 W US2017068404 W US 2017068404W WO 2018125861 A2 WO2018125861 A2 WO 2018125861A2
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WO
WIPO (PCT)
Prior art keywords
polymer derived
derived ceramic
barrel
ceramic precursor
extruder
Prior art date
Application number
PCT/US2017/068404
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English (en)
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WO2018125861A3 (fr
Inventor
Richard Landtiser
Andrew R. HOPKINS
David BENING
Wen P. Liao
Douglas Dukes
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Melior Innovations Inc.
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Application filed by Melior Innovations Inc. filed Critical Melior Innovations Inc.
Publication of WO2018125861A2 publication Critical patent/WO2018125861A2/fr
Publication of WO2018125861A3 publication Critical patent/WO2018125861A3/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/60—Component parts, details or accessories; Auxiliary operations for feeding, e.g. end guides for the incoming material
    • B29B7/603—Component parts, details or accessories; Auxiliary operations for feeding, e.g. end guides for the incoming material in measured doses, e.g. proportioning of several materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • B29B7/482—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws provided with screw parts in addition to other mixing parts, e.g. paddles, gears, discs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • B29B7/488—Parts, e.g. casings, sealings; Accessories, e.g. flow controlling or throttling devices
    • B29B7/489—Screws
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/82—Heating or cooling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/94—Liquid charges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/285—Feeding the extrusion material to the extruder
    • B29C48/29—Feeding the extrusion material to the extruder in liquid form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/252—Drive or actuation means; Transmission means; Screw supporting means
    • B29C48/2526—Direct drives or gear boxes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/256—Exchangeable extruder parts
    • B29C48/2564—Screw parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/285—Feeding the extrusion material to the extruder
    • B29C48/297—Feeding the extrusion material to the extruder at several locations, e.g. using several hoppers or using a separate additive feeding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B29C48/405—Intermeshing co-rotating screws
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/535—Screws with thread pitch varying along the longitudinal axis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/54—Screws with additional forward-feeding elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/55—Screws having reverse-feeding elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/505—Screws
    • B29C48/57—Screws provided with kneading disc-like elements, e.g. with oval-shaped elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2089/00—Use of proteins, e.g. casein, gelatine or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2101/00—Use of unspecified macromolecular compounds as moulding material
    • B29K2101/10—Thermosetting resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2309/00—Use of inorganic materials not provided for in groups B29K2303/00 - B29K2307/00, as reinforcement
    • B29K2309/02—Ceramics

Definitions

  • the present inventions relate to methods and systems for
  • Polymer derived ceramics are ceramic materials that are derived from, e.g., obtained by, the pyrolysis of polymeric materials. These materials are typically in a solid or semi-solid state that is obtained by curing an initial liquid polymeric precursor, e.g., PDC precursor, PDC precursor formulation, precursor batch, and precursor.
  • the cured, but unpyrolized, polymer derived material can be referred to as a preform, a PDC preform, the cured material, and similar such terms.
  • Polymer derived ceramics may be derived from many different kinds of precursor formulations, e.g., starting materials, starting formulations.
  • PDCs may be made of, or derived from, carbosilane or polycarbosilane (Si-C), silane or polysilane (Si-Si), silazane or polysilazane (Si-N-Si), silicon carbide (SiC), carbosilazane or polycarbosilazane (Si-N- Si-C-Si), siloxane or polysiloxanes (Si-O), to name a few.
  • a preferred PDC is "polysilocarb", e.g., material containing silicon (Si), oxygen (O) and carbon (C).
  • Polysilocarb materials may also contain other elements.
  • Polysilocarb materials can be made from one or more polysilocarb precursor formulation or precursor formulation.
  • the polysilocarb precursor formulations can contain, for example, one or more functionalized silicon polymers, other polymers, non- silicon based cross linking agents, monomers, as well as, potentially other ingredients, such as for example, inhibitors, catalysts, initiators, modifiers, dopants, fillers, reinforcers and combinations and variations of these and other materials and additives.
  • %, weight % and mass % are used interchangeably and refer to the weight of a first component as a percentage of the weight of the total, e.g., formulation, mixture, material or product.
  • volume % and % volume and similar such terms refer to the volume of a first component as a percentage of the volume of the total, e.g., formulation, material or product.
  • a system for making small volumetric structures from a polymer derived ceramic precursor including: a polymer derived ceramic precursor delivery apparatus including: an injection port; and, an extruder barrel having a plurality of sections; wherein a section of the plurality of sections is a mixing section having a temperature from about 70 C to about 300 C; wherein, the system is capable of receiving a liquid polymer derived ceramic precursor; and whereby the system is capable of curing the liquid polymer derived ceramic precursor in the extruder barrel to form a cured polymer derived ceramic material.
  • the injection port is filled with a liquid polymer derived ceramic precursor; wherein the extruder barrel is filled with the polymer derived ceramic precursor formulation; wherein the extruder barrel has a distal end and a proximal end, wherein the proximal end is adjacent the injunction port; and wherein the distal end of the barrel is filled with cured polymer derived ceramic material; wherein the extruder barrel has 8 zones, the zones including: an input zone having a temperature of 200-400 F; a first mix zone having a temperature of 200-400 F; a second mix zone having a temperature of 350-500 F; a third mix zone having a temperature of 350-500 F; a first mix/transfer zone having a temperature of 375-500 F; a second mix/transfer zone having a temperature of 375-550 F; a first transfer zone having a temperature of 375-425 F; and a die zone having a
  • an extruder system for making cured polysiloxane polymer derived ceramic materials
  • the extruder including: a drive section; the drive section mechanically engaging a gear box; and the gear box mechanically engaging a first and a second screw; whereby the drive section and gear box form an assembly capable of rotating the screws; the screws being located within an extruder barrel; the extruder barrel having a distal end and a proximal end; the extruder barrel and screws configured to form a plurality of sections; a first barrel section including an injection port having a liquid polymer derived ceramic precursor, the injunction port in fluid communication with a holding tank for the liquid polymer derived ceramic precursor; the first barrel section filled with the liquid polymer derived ceramic precursor; the first barrel section configured to cure the liquid polymer derived ceramic precursor; the screws in the first barrel section configured to advance the liquid precursor distally toward a second barrel section; the second barrel section configured to cure the liquid into a partially cured gelatinous polymer derived ceramic precursor;
  • the polymer derived ceramic precursor is methyl hydrogen fluid; wherein the polymer derived ceramic precursor is DCPD; wherein the polymer derived ceramic precursor is DCPD and methyl hydrogen fluid; wherein the first barrel section is a second injection port; wherein the second injection port contains a second material that is different from the liquid polymer derived ceramic precursor in the first injection port; wherein the second material is a liquid polymer derived ceramic precursor; wherein the second material is a catalysis; and, wherein the second material is a silicon having a cyclic structure.
  • volumetric structures wherein each structure defines a volume, in a reaction extruder, the method including: adding a liquid polymer derived ceramic into an extruder, the extruder including a barrel, mixing and curing the liquid polymer derived ceramic in the barrel, and delivering from the barrel a cured polymer derived ceramic material.
  • the extruder barrel has 8 zones, the zones including: an input zone having a temperature of 200-400 F; a first mix zone having a temperature of 200-400 F; a second mix zone having a temperature of 350- 500 F; a third mix zone having a temperature of 350-500 F; a first mix/transfer zone having a temperature of 375-500 F; a second mix/transfer zone having a temperature of 375-550 F; a first transfer zone having a temperature of 375-425 F; and a die zone having a temperature of 50-80 F; and, wherein the liquid polymer derived ceramic precursor is selected from the group consisting of silanes, polysilanes, silazanes, polysilazanes, carbosilanes, polycarbosilanes, siloxanes, and polysiloxanes.
  • a method for making a volumetric structure, having a volume, in a reaction extruder including: adding a liquid polymer derived ceramic precursor into an extruder, the extruder including a barrel, mixing and curing the liquid polymer derived ceramic in the barrel, and delivering at least about 95% of the liquid polymer derived ceramic precursor from the barrel as cured polymer derived ceramic material.
  • a method for making a volumetric structure, having a volume, in a reaction extruder including: adding a liquid polymer derived ceramic precursor into an extruder, the extruder including a barrel, mixing and curing the liquid polymer derived ceramic in the barrel, and delivering at least about 99% of the liquid polymer derived ceramic precursor from the barrel as cured polymer derived ceramic material.
  • a method for making a volumetric structure, having a volume, in a reaction extruder including: adding a liquid polymer derived ceramic precursor into an extruder, the extruder including a barrel, mixing and curing the liquid polymer derived ceramic in the barrel, and delivering at least about 99.5% of the liquid polymer derived ceramic precursor from the barrel as cured polymer derived ceramic material.
  • a method for making a volumetric structure, having a volume, in a reaction extruder including: adding a liquid polymer derived ceramic precursor into an extruder, the extruder including a barrel, mixing and curing the liquid polymer derived ceramic in the barrel, and delivering at least about 99.9% of the liquid polymer derived ceramic precursor from the barrel as cured polymer derived ceramic material.
  • the volume is less than about 0.25 inch 3 ; wherein the volume is less than about 500 mm 3 ; wherein the volume is than about 50 microns 3 ; wherein the preform is green cured.; wherein the cured material is hard cured; wherein the liquid polymer derived ceramic precursor is a polysilocarb and contains hydride groups; wherein the liquid polymer derived ceramic precursor is a polysilocarb, is solvent free, and contains hydride groups; wherein the liquid polymer derived ceramic precursor is a polysilocarb and contains vinyl groups; wherein the liquid polymer derived ceramic precursor is a polysilocarb having hydride and vinyl groups and wherein the molar ratio of hydride groups to vinyl groups is about 1.50 to 1 ; wherein the liquid polymer derived ceramic precursor is a polysilocarb having hydride and vinyl groups and wherein the molar ratio of hydride groups to vinyl groups is about 1.50 to 1 ; wherein the liquid polymer derived ceramic precursor is
  • a method for making small volumetric structures from a polymer derived ceramic precursor including: adding a liquid polymer derived ceramic precursor to an extruder apparatus, the extruder including: an injection port; and, an extruder barrel having a plurality of sections;
  • a section of the plurality of sections is a mixing section having a temperature from about 70 C to about 300 C; wherein, the liquid polymer derived ceramic precursor is cured in the extruder barrel to form a cured polymer derived ceramic material.
  • the extruder barrel has 3 zones; wherein the extruder barrel has 5 zones; wherein the extruder barrel has 8 zones, the zones including: an input zone having a temperature of 200-400 F; a first mix zone having a temperature of 200-400 F; a second mix zone having a temperature of 350- 500 F; a third mix zone having a temperature of 350-500 F; a first mix/transfer zone having a temperature of 375-500 F; a second mix/transfer zone having a temperature of 375-550 F; a first transfer zone having a temperature of 375-425 F; and a die zone having a temperature of 50-80 F; wherein the extruder barrel has 8 zones, the zones including: an input zone; a first mix zone; a second mix zone having a temperature of 350-500 F; a third mix zone having a temperature of 350-500 F; a first mix/transfer zone having a temperature of
  • polycarbosilanes siloxanes, and polysiloxanes.
  • a method of making cured volumetric shapes of a polysilocarb polymer derived ceramic including: providing an extruder having a drive section; the drive section mechanically engaging a gear box; and the gear box mechanically engaging a first and a second screw; whereby the drive section and gear box form an assembly capable of rotating the screws; the screws being located within an extruder barrel; the extruder barrel having a distal end and a proximal end; the extruder barrel and screws configured to form a plurality of sections; adding a liquid polymer derived ceramic precursor to a first barrel section including an injection port, the injunction port in fluid communication with a holding tank for the liquid polymer derived ceramic precursor; the first barrel section filled with the liquid polymer derived ceramic precursor; and curing the liquid polymer derived ceramic material in the first barrel section; the screws in the first barrel section advancing the liquid precursor distally toward a second barrel section; the second barrel section curing the liquid into a partially cured gelatin
  • FIG. 1 is schematic diagram of an embodiment of a process and forming system in accordance with the present inventions.
  • FIG. 2 is a schematic diagram of an embodiment of a three in-feed extruder of a process and forming system in accordance with the present inventions.
  • FIG. 3 is a table setting out embodiments of methods in accordance with the present inventions.
  • FIG. 4 is a table setting out embodiments of methods in accordance with the present inventions.
  • FIG. 5 is an SEM of an embodiment of a cured polymer derived ceramic material (PDC) in accordance with the present inventions.
  • FIG. 6 is an SEM of an embodiment of a cured polymer derived ceramic material (PDC) in accordance with the present inventions.
  • FIG. 7 is an SEM of an embodiment of a cured polymer derived ceramic material (PDC) in accordance with the present inventions.
  • FIG. 8 is an SEM of an embodiment of a pyrolized extruded polymer derived ceramic material (PDC) in accordance with the present inventions.
  • FIG. 9 is an SEM of an embodiment of a pyrolized extruded polymer derived ceramic material (PDC) in accordance with the present inventions.
  • FIG. 10 is an SEM of an embodiment of a pyrolized extruded polymer derived ceramic material (PDC) in accordance with the present inventions.
  • FIG. 11 is a perspective view of an embodiment of a reaction extruder in accordance with the present inventions.
  • FIG. 12 is a perspective view of components of the extruder of FIG. 1 1 .
  • FIG. 13 is a cross sectional view of components of the extruder of FIG.
  • FIG 14 is a cross sectional view of components of the extruder of FIG.
  • FIG 14A is a cross sectional view of components of the extrud
  • FIG. 11 is a cross sectional view of components of the extruder of FIG. 11 .
  • FIG. 15 is a cross sectional view of an embodiment of a reaction extruder in accordance with the present inventions.
  • FIG. 16 is a cross sectional view of an embodiment of a component of the extruder of FIG. 15.
  • FIG. 17 is a cross sectional view of an embodiment of a component of the extruder of FIG. 15.
  • FIG. 18 is a cross sectional view of an embodiment of a component of the extruder of FIG. 15.
  • FIG. 19 is a cross sectional view of an embodiment of a component of the extruder of FIG. 15.
  • FIG. 20 is a cross sectional view of an embodiment of a component of the extruder of FIG. 15.
  • FIG. 21 is a perspective view of an embodiment of a reaction extruder in accordance with the present inventions.
  • FIG. 22 is a schematic of an embodiment of a reaction extrusion system in accordance with the present inventions. DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • the present inventions relate to methods, systems, apparatus, and process for making small volumetric shapes from PDC precursors, and to provide small volumetric shaped PDC preforms and polymer derived ceramics.
  • embodiments of the present inventions make small shapes from PDC precursors a high rates and when extruders are configured with other forming or shaping apparatus can make these shapes with high levels of uniformity, e.g. same weight, same volume, same shape and variations and combinations of these attributes.
  • Embodiments of the present inventions make volumetric shapes of PDC precursors, PDC preforms, PDC plastics, PDC cured materials, and polymer derived ceramics, at high rates of production, in large quantities, and with long run times.
  • embodiments of the present invention are directed toward extrusion processes in which one or more PDC precursors, as well as, potentially other materials are added into an extruder.
  • the PDC precursors are reacted together in the extruder forming a PDC precursor batch, after which the PDC precursor batch is cured into a green, e.g., plastic, PDC material.
  • This PDC material can then be further curried, proceeds, and pyrolized.
  • a final PDC product such as a SiOC pigment is provided, requirement no further processing and can be packaged for shipment to a customer.
  • FIG. 1 there is a schematic flow diagram of a reaction extrusion system and method (which systems and methods may also be called reactive extruders, reaction extrusion, and similar such terms).
  • the reaction extrusion system 100 has a reaction extruder 101.
  • the reaction extruder 101 has a drive motor 102 and an extruder drive assembly 103, which drives, i.e., turns the extrusion screws (not shown) in barrel 104.
  • Barrel 104 may have several zones, having different temperatures, different pressure, different screw configurations, different rates of screw rotation, and combinations and variations of these and other conditions known or used in a reaction extrusion process.
  • the barrel has four zones 104a, 104b, 104c, and 104d.
  • the zones may have space between them in the barrel, e.g., see zone 104a and zone 104b, or they may be abutting, see zone 104b and zone 104c.
  • the screw configurations are selected primarily based upon the polymer derived ceramic precursors that are being used, including factors such as the level of catalysis used, the desired level of cure, the presence of an exothermic, and the viscosity of the precursor as it is reacted and proceeds to a cured material.
  • Twin screw, with counter rotating screws are an embodiment that can be used, and in some situations may be preferable.
  • Other embodiments of screws, and screw configurations include, for example, co-rotating, self wiping co-rotating, triple screw extruders, and combinations and variations of these.
  • the screws can be made from, for example, steel, stainless steel, ceramics, alloys and and combinations and variations of these and other materials know to the art
  • the length of the barrel may be greater than 30 in ("inches"), greater than 40 in, greater than 50 in, and greater than 100 in, the barrels may be from about 50 to about 240 in, about 50 to about 96 in, about 50 to about 166 in, about 96 in to about 150 in, and about 150 in to about 240 in.
  • the barrels may be from about 50 to about 240 in, about 50 to about 96 in, about 50 to about 166 in, about 96 in to about 150 in, and about 150 in to about 240 in.
  • the diameter of the barrel may be greater than about 1/2 in, greater than about 1 in, greater than about 2 in, and greater than about 5 in, from about 1 in to about 7 in.
  • L/D The ratio of the barrel length to barrel diameter
  • L/D which is typically the manner in which extruder barrels can be referred to, can be, for example 36/1 , 48/1 , 50/1 , 60/1 and other L/D ratios.
  • Two, or more, barrels can be combined into a single extruder system.
  • two 44/1 barrels can be combined in series to provide an 88/1 system.
  • One, two, three, four or more barrels can be combined in series in this manner.
  • the temperatures in the barrel and in the various zones can vary from room temperature to about 600° C.
  • Various temperature heating profiles can be obtained within the barrel, e.g., a zone have a temperature increase of about ⁇ , from the proximal to the distal end of the zone, a adjacent zone, where the temperature is held constant, and then subsequent zones where the ⁇ can be increased, decreases or held to zero.
  • cooling zones are contemplated, i.e., where the temperature is maintained below room temperature, or below a prior zone, to facilitate cooling of the material.
  • ⁇ in degree C for a zone in the barrel can be about 0, about 100, about 150, about 300, and about 400 or more.
  • the lengths of these zones can be, for example, from about 10 in to 100 in, about 30 in to about 50 in, greater than 20 in, greater than 30 in, greater than 50 in.
  • a throttling mechanism 107 At the distal end 122 of the barrel 104 there is located a throttling mechanism 107. This mechanism is designed to provide sufficient back pressure during the startup of the reaction extrusion process, to enable a steady state in the barrel 104 to be achieved.
  • the mechanism 107 can be any time of valve, plate or other restriction know in the art, in some configurations it may not be needed, as the later, more distal zones, e.g., 104d, may provide sufficient back pressure at the beginning of a run.
  • an infeed device 105 Near the proximal end 121 of the barrel 104 there is an infeed device 105, and a closure or restriction device 106, which form an injection port or injector.
  • the infeed device 105 receives the various PDC precursors, which typically are in liquid form at room temperature, and the restriction device 106, if needed, can control the infeed of the precursor material into the extruder 104, prevents flow back out of the extruder 104, and perform other operations as needed regarding the infeed of the precursor.
  • a premixing zone 120 where one or more of the precursors or the in feed materials can be premixed is contemplated.
  • the system 100 can have several infeed material holding tanks, in the embodiment of FIG. 1 there four infeed holding tanks, 109, 110, 111 1 12. More or less infeed holding takes can be used. While the SiOC precursors are typically liquids at room temperature, and will be contained in the infeed tanks as a liquids, other PDC materials, and cross linkers, and additives may be solids, e.g., powders, emulsions, pastes, or in other forms. Additionally, other additives or fillers can be used, and held in the infeed tanks for use. In some embodiments it is desirable, and preferred to preheat the solid material to melt it forming a liquid for use in the injection or infeed port of the extruder. For example DCPD which is a solid at room temperature, preferable is melted and added as a liquid to the extruder with a PDC precursor.
  • DCPD which is a solid at room temperature
  • tank 109 holds a first PDC precursor material
  • tank 1 10 holds a cross-linking agent
  • tank 111 holds a second PDC precursor
  • tank 112 holds a catalyst solution.
  • Each infeed tank as a metering device 109a, 110a, 1 11 a and 112a and infeed line 109b, 110b, 1 11 b, and 112b associated with it for delivery of the infeed material, preferably in a controlled and monitored manner, to the infeed assembly 105.
  • the first PDC precursor infeed material in tank 109 is a linear SiOC precursor
  • the cross-linking agent infeed material in tank 1 10 is a non-silicon based cross linking agent
  • the second PDC precursor infeed material in tank 111 is a cyclic silicon based material.
  • the infeed materials of tanks 109, 11 1 can be feed into the extruder 104 in proportions, by weight, of about 0% to 100% of the total infeed material.
  • the cross-linking agent of tank 1 10 can be feed into the extruder 104 in propositions by weight of about 0% to 85% of the total infeed material.
  • the catalyst based upon weight of active catalyst, can be from about 0% to about 10% of the weight of the other infeed materials.
  • the cross-linking agents can be the reaction product of a non-silicon based cross linking agent and a siloxane backbone additive, and combinations and variation of these.
  • the non-silicon based cross-linking agents are intended to, and provide, the capability to cross-link during curing.
  • non-silicon based cross-linking agents that can be used include: cyclopentadiene (CP),
  • methylcyclopentadiene (MeCP), dicyclopentadiene (“DCPD”), methyldicyclopentadiene (MeDCPD), tricyclopentadiene (TCPD), piperylene, divnylbenzene, isoprene, norbornadiene, vinylnorbornene, propenylnorbornene, isopropenylnorbornene, methylvinylnorbornene, bicyclononadiene, methylbicyclononadiene, propadiene, 4- vinylcyclohexene, 1 ,3-heptadiene, cycloheptadiene, 1 ,3-butadiene, cyclooctadiene and isomers thereof.
  • Some organic materials containing oxygen, nitrogen, and sulphur may also function as cross-linking moieties.
  • a material receiving unit 108 At the distal end 122 of the extruder 104 there is a material receiving unit 108.
  • the solid polymer derived ceramic material is delivered from the distal end 122 of the extruder 104 to the receiving until 108.
  • the solid polymer derived ceramic material from the distal end 122 of the extruder 104 can be initially cured, finally cured or hard cured.
  • This PDC material can be a final product, e.g., a proppant bead or flake, or can be subject to later shaping, grinding, curing, molding, pyrolzing, etc..
  • the unit 108 can, for example, be a simple bin to hold the cured material, it can be a packaging device, it can be an forming or shaping device, such as those disclosed in US Patent Applications serial numbers 15/210,590 and 15/002,773, the entire disclosures of each of which are incorporated herein by reference.
  • the unit 108 can be a curing furnace, it can be a pyrolysis furnace, or both.
  • conditions inside the barrel of the extruder are essentially under conditions with little to no atmosphere, and thus little to no oxygen or nitrogen.
  • the conditions inside of the barrel are essentially inert.
  • gasses may be added, for example for the purpose of further controlling the reaction, modifying the infeed materials or formulations, and combinations of these and other purposes.
  • propylene, butene, other alkenes, or other organics in gaseous form can be added to the injection port.
  • the gas is preferably capable of reacting with the of the precursor material, and added under conditions where this reaction can take place without bubble formation.
  • the reaction of the gas and the precursor material are completed by the time the precursor material is in a gel state. More preferably the gas reacts with the backbone of the precursor material.
  • FIG. 2 shows an embodiment of an extruder system having three injection ports, e.g., infeeds. Two, three, four and up to six injection ports can typically be used in injection systems, although more could be used. This provides the ability to have, and combine many different types of polysilocarb starting materials, cross linkers, and other components.
  • the use of the extruder for the processing of the polysilocarb precursors provides the ability to have a large number of different starting materials. It provides for having the starting materials mixed before being injected into the extruder (pre-mixed), to have them mixed in the extruder, and combinations and variations of these.
  • volumetric shapes made by embodiments of the present invention are small, e.g., having cross sections from about 2 inches to 0.01 microns ( ⁇ ), of less than about 1 inch, less than about 3 ⁇ 4 inch, less than about 1/3 inch, less than about 5,000 microns, less than about 4,000 microns, less than about 2,000 microns, less than about 1 ,000 microns, less than about 500 microns, less than about 100 microns, less than about 10 microns, less than about 1 micron, less than about 0.5 microns and about 0.1 micron.
  • ⁇ microns
  • the volumetric shapes may have volumes of from about 4.25 inch 3 to about 0.0004 microns 3 , of less than about 0.25 inch 3 , of less than about 525 mm 3 , of less than about 100 mm 3 , of less than about 50 mm 3 , of less than about 4,000 microns 3 , of less than about 2,000 microns 3 , of less than about 100 microns 3 , of less than about 50 microns 3 , of less than about 0.5 microns 3 and of less than about 0.00005 microns 3 .
  • the small volumetric shapes may individually weight, less than about 30 grams, less than about 15 grams, less than about 10 grams, less than about 1 gram, less than about 0.5 grams, less than about 0.1 grams, and less than about 0.01 grams, less than about 0.0001 grams, less than about 0.00001 grams, less then about 10 "8 g, less than about 10 "10 g, and less than about 10 "15 g.
  • These sizes and volumes per shape may be obtained at the distal end of the extruder, or by later process steps.
  • the small volumetric shapes of PDC cured materials that come from the end of the barrel of the extruder are particles, pellet like, crumb like, or randomly shaped particles.
  • the extruder however may be use with other forming apparatus, and the extruder may provide partially cured, slightly cured, or green cured material to this other forming apparatus, to make small volumetric shapes, that may be substantially uniform, they may be entirely random, they may be within a predetermined range, for one of more physical property, e.g., shape, size, weight, roughness, density, porosity, strength, electrical, conductivity, optical, thermodynamic, ionic, etc., and combinations and variations of these.
  • the extruder may provide partially cured, slightly cured, or green cured material to this other forming apparatus, to make small volumetric shapes, that may be substantially uniform, they may be entirely random, they may be within a predetermined range, for one of more physical property, e.g., shape, size, weight, roughness, density, porosity, strength, electrical, conductivity, optical, thermodynamic, ionic, etc., and combinations and variations of these.
  • the final volumetric shapes may be any shape, including for example, spheres, platelets, sheets, flakes, pellets, rings, lenses, disks, panels, cones, frustoconical shapes, squares, rectangles, trusses, angles, channels, hollow sealed chambers, hollow spheres, blocks, sheets, coatings, balls, squares, prolate spheroids, ellipsoids, spheroids, eggs, cones, multifaceted structures, films, skins, particulates, beams, rods, angles, columns, fibers, staple fibers, tubes, cups, pipes, polyhedrons (e.g., octahedron, dodecahedron, icosidodecahedron, rhombic triacontahedron, and prism), and combinations and various of these and other more complex shapes, both engineering and architectural.
  • polyhedrons e.g., octahedron, dodecahedron, icosidodecahedron, r
  • the polymer derived ceramics and their cured preforms may be any volumetric shape, and preferably are any predetermined volumetric shape.
  • the cured preforms may be the same shape, or a different volumetric shape, from the ceramics.
  • a precursor batch may be shaped into, for example, platelets, sheets, flakes, balls, spheres, squares, prolate spheroids, ellipsoids, spheroids, eggs, cones, rods, boxes, multifaceted structures, and polyhedrons (e.g., octahedron, dodecahedron, icosidodecahedron, rhombic triacontahedron, and prism), as well as, other such structures for, or upon, curing, and pyrolysis.
  • polyhedrons e.g., octahedron, dodecahedron, icosidodecahedron, rhombic triacontahedron, and prism
  • the polymeric derived ceramics may be made into the shape of any particle, that is used as, or suggested to be used as, for example, a pigment, an additive, an abrasive, a filler, and an hydraulic fracturing proppant.
  • Spherical type structures are examples of a presently preferred shape for proppants.
  • Embodiments of the systems, apparatus and methods provide the ability to make highly random sized particles of the same type, e.g., all shapes are substantially perfect spheres but have random and varied volumes, to make highly random shapes with high random particle sizes, e.g., many different shapes with varied volumes, and combinations and variations of these.
  • Embodiments of the systems, apparatus and methods preferably provide the ability to make highly uniform shapes, as to type, as to volume and both. Preferably, these levels of uniformity in the production of the volumetric shapes, both the ceramic and cured preform, is obtained without the need for filtering, sorting or screening the cured shapes, and without the need for filtering, sorting or screening the pyrolized shapes.
  • embodiments of the present processes provide the ability to make a large number of highly uniform predetermined shapes, e.g., at least about 90%, at least about 95% and at least about 99% of the shapes produced meet the targeted or predetermined shape. For example, at least about 98% of the beads, e.g., proppants, made from a precursor batch can be essentially spherical.
  • the precursor formulation is initially a liquid. This liquid precursor formulation is then cured to form a solid or semi-sold material, e.g., a plastic, which is also called the preform or cured preform. The preform is then pyrolized into a ceramic.
  • the extrusion reaction systems can be used to produce cured PDC materials of very high purity, including high pure SiOC. These materials can then be used to product high purity SiC.
  • embodiments of the present inventions provide for the formation of SiC that is at least about 99.9%, at least about 99.99%, at least about 99.999%, and least about 99.9999% and at least about 99.99999% or greater purity. These purity values are based upon the amount of SiOC, or SiC, as the case may be, verse all materials that are present or contained within a given sample of SiOC or SiC product.
  • polymer derived high purity SiC and in particular polysilocarb derived high purity SiOC, as well as, the high purity SiC that the SiOC is converted into, has a purity of at least about 99.9%, at least about 99.99%, at least about 99.999%, and least about 99.9999% and at least about 99.99999% or greater.
  • embodiments of the present invention include polymer derived SiC, and SiOC, of any purity level, including lower levels of purity, such as 99.0%, 95%, 90% and lower. It is believe that these lower, e.g., non-high, purity embodiments have, and will find, substantial uses and applications. Similarly, it is believe that embodiments of the high purity SiC will find applications, uses, and provide new and surprising benefits to applications that prior to the present inventions were restricted to Si or materials other than SiC.
  • Embodiments of the present inventions include the use of high purity SiC in making wafers for applications in electronics and semiconductor applications. In both the vapor deposition apparatus and processes to create the boules and wafers for later use, high purity SiC is required.
  • high purity polymer derived SiOC and SiC can preferably have low levels of one, more than one, and all elements in Table 1 , which in certain vapor deposition apparatus, electronics applications, semiconductor and other applications are considered to be impurities.
  • embodiments of polysilocarb derived SiC can be free of impurities, substantially free of impurities, and contain some but have no more than the amounts, and combinations of amounts, set out in Table 1.
  • excess carbon i.e., beyond stoichiometric SiC
  • excess carbon may have little to no effect on the application or product, and thus, would not be considered an impurity.
  • excess carbon may be beneficial, e.g., carbon can act as a sintering aid; excess carbon can be used to address and compensate for irregularities in vapor deposition apparatus and processes.
  • embodiments of polysilocarb derived SiC and SiOC can have less than about 1000 ppm, less than about 100 ppm, less than about 10 ppm, less than about 1 ppm and less than about 0.1 ppm nitrogen, and lower.
  • the reaction extrusion system can be placed in a clean room environment, when making high purity SiOC for use in making high purity SiC, the activities associated with making, curing, pyrolizing and converting the material are conducted in, under, clean room conditions, e.g., under an ISO 14644-1 clean room standard of at least ISO 5, of at least ISO 4, of at least ISO 3, of at least ISO 2, and at least ISO 1 .
  • the material handling steps are conducted in the cleanroom of at least ISO 5, while a less clean area (ISO >5) is used for the pyrolysis and conversion steps
  • polymer derived ceramic precursor formulations can generally be made by three types of processes, although other processes, and variations and combinations of these processes may be utilized. These process, in part, or in total, can all be carried out in embodiments of the present reaction extrusion systems and processes. These processes generally involve combining precursors to form a precursor formulation.
  • One type of process generally involves the mixing together of precursor materials in preferably a solvent free process with essentially no chemical reactions taking place, e.g., "the mixing process.”
  • the other type of process generally involves chemical reactions, e.g., "the reaction type process,” to form specific, e.g., custom, precursor formulations, which could be monomers, dimers, trimers and polymers.
  • a third type of process has a chemical reaction of two or more components in a solvent free environment, e.g., "the reaction blending type process.”
  • the reaction blending type process essentially all, and preferably all, of the chemical reactions take place during subsequent processing, such as during curing, pyrolysis and both.
  • reaction type process reaction blending type process
  • mixing type process - are used for convenience and as a short hand reference. These terms are not, and should not be viewed as, limiting.
  • the reaction process can be used to create a precursor material that is then used in the mixing process with another precursor material.
  • These three processes and PDC precursor formulations are disclosed and taught in US Patent Publication Nos. 2014/0343220, 2014/0274658, 2014/0326453, and 2015/0175750 the entire disclosures of each of which are incorporated herein by reference.
  • a formulation from the mixing type process may be used as a precursor, or component in the reaction type process, or the reaction blending type process.
  • a formulation from the reaction type process may be used in the mixing type process and the reaction blending process.
  • a formulation from the reaction blending type process may be used in the mixing type process and the reaction type process.
  • Precursor materials may be methyl hydrogen, and substituted and modified methyl hydrogens, siloxane backbone additives, reactive monomers, reaction products of a siloxane backbone additive with a silane modifier or an organic modifier, and other similar types of materials, such as silane based materials, silazane based materials, carbosilane based materials, phenol/formaldehyde based materials, non- silicon based cross-linkers, and combinations and variations of these.
  • the precursors are preferably liquids at room temperature, although they may be solids that are melted, or that are soluble in one of the other precursors.
  • the precursors are mixed together and provided to an infeed hold tank, or they can be premixed, e.g., premix zone 120 of the embodiment of FIG. 1 , or they can be mixed in the extruder.
  • no solvents e.g., water, organic solvents, polar solvents, non-polar solvents, hexane, THF, toluene
  • each precursor material is miscible with the others, e.g., they can be mixed at any relative amounts, or in any proportions, and will not separate or precipitate.
  • the "precursor mixture” or "polysilocarb precursor formulation” is compete (noting that if only a single precursor is used the material would simply be a "polysilocarb precursor” or a “polysilocarb precursor formulation” or a “formulation”).
  • fillers and reinforcers may be added to the formulation, for example at the infeed to the extruder.
  • essentially no, and more preferably no chemical reactions, e.g., crosslinking or polymerization takes place within the formulation, when the formulation is mixed, or when the formulation is being held in a vessel, on a prepreg, or over a time period, prior to being cured.
  • the precursors can be mixed under numerous types of atmospheres and conditions, e.g., air, inert, is , Argon, flowing gas, static gas, reduced pressure, elevated pressure, ambient pressure, and combinations and variations of these.
  • atmospheres and conditions e.g., air, inert, is , Argon, flowing gas, static gas, reduced pressure, elevated pressure, ambient pressure, and combinations and variations of these.
  • inhibitors such as cyclohexane, 1-Ethynyl-1 -cyclohexanol (which may be obtained from ALDRICH), Octamethylcyclotetrasiloxane, and
  • tetramethyltetravinylcyclotetrasiloxane may be added to the polysilocarb precursor formulation, e.g., an inhibited polysilocarb precursor formulation.
  • Other materials, as well, may be added to the polysilocarb precursor formulation, and preferably at the infeed to the extruder, e.g., a filled polysilocarb precursor formulation, at this point in processing, including fillers such as SiC powder, carbon black, sand, polymer derived ceramic particles, pigments, particles, nano-tubes, whiskers, or other materials, discussed in this specification or otherwise known to the arts.
  • a catalyst or initiator may be used, and can be added at the time of, prior to, shortly before, or at an earlier time before the precursor formulation is formed or made into a structure, prior to curing.
  • the catalysis assists in, advances, and promotes the curing of the precursor formulation to form a preform.
  • pot life e.g., how long can the catalyzed formulation remain in its holding vessel before it should be used.
  • the catalyst can be any platinum (Pt) based catalyst, which can, for example, be diluted to a ranges of: about 0.01 parts per million (ppm) Pt to about 250 ppm Pt, about 0.03 ppm Pt, about 0.1 ppm Pt, about 0.2 ppm Pt, about 0.5 ppm Pt, about 0.02 to 0.5 ppm Pt, about 1 ppm to 200 ppm Pt and preferably, for some applications and embodiments, about 5 ppm to 50 ppm Pt.
  • Pt platinum
  • the catalyst can be a peroxide based catalyst with, for example, a 10 hour half life above 90 C at a concentration of between 0.1 % to 3% peroxide, and about 0.5% and 2% peroxide. It can be an organic based peroxide. It can be any organometallic catalyst capable of reacting with Si-H bonds, Si-OH bonds, or unsaturated carbon bonds, these catalysts may include: dibutyltin dilaurate, zinc octoate, peroxides, organometallic compounds of for example titanium, zirconium, rhodium, iridium, palladium, cobalt, iron or nickel.
  • Catalysts may also be any other rhodium, rhenium, iridium, palladium, nickel, and ruthenium type or based catalysts. Combinations and variations of these and other catalysts may be used. Catalysts may be obtained from ARKEMA under the trade name LUPEROX, e.g., LUPEROX 231 ; and from Johnson Matthey under the trade names: Karstedt's catalyst, Ashby's catalyst, Speier's catalyst.
  • custom and specific combinations of these and other catalysts may be used, such that they are matched to specific formulations, extruder conditions, and cured or end product properties; and in this way selectively and specifically catalyze the reaction of specific constituents.
  • the use of these types of matched catalyst-formulations— extruder systems may be used to provide predetermined product features, such as for example, pore structures, porosity, densities, density profiles, high purity, ultra high purity, and other morphologies or features of cured structures and ceramics.
  • this mixing type process for making a precursor formulation preferably chemical reactions or molecular rearrangements only take place during the making of the starting materials, the curing process, in the extruder barrel, and in the pyrolizing process. Chemical reactions, e.g., polymerizations, reductions, condensations, substitutions, take place or are utilized in the making of a starting material or precursor. In making a polysilocarb precursor formulation by the mixing type process, preferably no and essentially no, chemical reactions and molecular rearrangements take place.
  • polymerization, crosslinking or other chemical reactions take place primarily, preferably essentially, and more preferably solely during the curing process in the extruder barrel, or during subsequent or further curing after the material is ejected from the extruder barrel.
  • the precursor may be a siloxane backbone additive, such as, methyl terminated hydride substituted polysiloxane, which can be referred to herein as methyl hydrogen (MH), which formula is shown below.
  • siloxane backbone additive such as, methyl terminated hydride substituted polysiloxane, which can be referred to herein as methyl hydrogen (MH), which formula is shown below.
  • the MH may have a molecular weight ("mw” which can be measured as weight averaged molecular weight in amu or as g/mol) from about 400 mw to about 10,000 mw, from about 600 mw to about 3,000 mw, and may have a viscosity preferably from about 20 cps to about 60 cps.
  • the percentage of methylsiloxane units "X" may be from 1 % to 100%.
  • the percentage of the dimethylsiloxane units "Y” may be from 0% to 99%.
  • This precursor may be used to provide the backbone of the cross-linked structures, as well as, other features and characteristics to the cured preform and ceramic material. This precursor may also, among other things, be modified by reacting with unsaturated carbon compounds to produce new, or additional, precursors.
  • methyl hydrogen fluid (MHF) has minimal amounts of "Y", and more preferably "Y” is for all practical purposes zero.
  • the precursor may be a siloxane backbone additive, such as vinyl substituted polydimethyl siloxane, which formula is shown below.
  • This precursor may have a molecular weight (mw) from about 400 mw to about 10,000 mw, and may have a viscosity preferably from about 50 cps to about 2,000 cps.
  • the percentage of methylvinylsiloxane units "X" may be from 1 % to 100%.
  • the percentage of the dimethylsiloxane units ⁇ " may be from 0% to 99%.
  • X is about 100%.
  • This precursor may be used to decrease cross-link density and improve toughness, as well as, other features and characteristics to the cured preform and ceramic material.
  • the precursor may be a siloxane backbone additive, such as vinyl substituted and vinyl terminated polydimethyl siloxane, vinyl substituted and hydrogen terminated polydimethyl siloxane, allyl terminated polydimethyl siloxane, vinyl terminated polydimethyl siloxane ("VT"), silanol (hydroxy) terminated polydimethyl siloxane, silanol (hydroxy) terminated vinyl substituted dimethyl siloxane, and hydrogen (hydride) terminated polydimethyl siloxane, di-phenyl terminated siloxane, a mono- phenyl terminated siloxane, diphenyl dimethyl polysiloxane, vinyl terminated diphenyl dimethyl polysiloxane, and hydroxy terminated diphenyl dimethyl polysiloxane.
  • siloxane backbone additive such as vinyl substituted and vinyl terminated polydimethyl siloxane, vinyl substituted and hydrogen terminated polydimethyl siloxane, allyl terminated poly
  • the precursor batch may also contain non-silicon based cross-linking agents, be the reaction product of a non-silicon based cross linking agent and a siloxane backbone additive, and combinations and variation of these.
  • the non-silicon based cross-linking agents are intended to, and provide, the capability to cross-link during curing.
  • non-silicon based cross-linking agents that can be used include: cyclopentadiene (CP), methylcyclopentadiene (MeCP), dicyclopentadiene (“DCPD”), methyldicyclopentadiene (MeDCPD), tricyclopentadiene (TCPD), piperylene, divnylbenzene, isoprene, norbornadiene, vinylnorbornene, propenylnorbornene, isopropenylnorbornene, methylvinylnorbornene, bicyclononadiene,
  • CP cyclopentadiene
  • MeCP methylcyclopentadiene
  • DCPD dicyclopentadiene
  • MeDCPD methyldicyclopentadiene
  • TCPD tricyclopentadiene
  • piperylene divnylbenzene, isoprene, norbornadiene, vinylnorbornene, propenylnorborn
  • Some organic materials containing oxygen, nitrogen, and sulphur may also function as cross-linking moieties.
  • This precursor may be used, among other things, in a dual-cure system; in this manner the dual-cure can allow the use of multiple cure mechanisms in a single formulation.
  • both condensation type cure and addition type cure can be utilized.
  • This provides the ability to have complex cure profiles, which for example may provide for an initial cure via one type of curing and a final cure via a separate type of curing.
  • the various condition in the extruder barrel zones can be predetermined and maintained to provide for this type of separate curing.
  • this type of separate curing profiles can be obtained with a single system and in a continuous process.
  • the precursor may be a reactive monomer. These would include molecules, such as tetramethyltetravinylcyclotetrasiloxane ("TV”), which formula is shown below.
  • TV tetramethyltetravinylcyclotetrasiloxane
  • This precursor may be used to provide a branching agent, a three- dimensional cross-linking agent, as well as, other features and characteristics to the cured preform and ceramic material. (It is also noted that in certain formulations, e.g., above 2%, and certain temperatures, e.g., about from about room temperature to about 60° C, this precursor may act as an inhibitor to cross-linking, e.g., in may inhibit the cross-linking of hydride and vinyl groups.)
  • the precursor may be a reactive monomer, for example, such as trivinyl cyclotetrasiloxane, divinyl cyclotetrasiloxane, trivinyl monohydride
  • the precursor may be a silane modifier, such as vinyl phenyl methyl silane, diphenyl silane, diphenyl methyl silane, and phenyl methyl silane (some of which may be used as an end capper or end termination group).
  • silane modifiers can provide chain extenders and branching agents. They also improve toughness, alter refractive index, and improve high temperature cure stability of the cured material, as well as improving the strength of the cured material, among other things.
  • a precursor, such as diphenyl methyl silane may function as an end capping agent, that may also improve toughness, alter refractive index, and improve high temperature cure stability of the cured material, as well as, improving the strength of the cured material, among other things.
  • the precursor may be a reaction product of a silane modifier with a vinyl terminated siloxane backbone additive.
  • the precursor may be a reaction product of a silane modifier with a hydroxy terminated siloxane backbone additive.
  • the precursor may be a reaction product of a silane modifier with a hydride terminated siloxane backbone additive.
  • the precursor may be a reaction product of a silane modifier with TV.
  • the precursor may be a reaction product of a silane.
  • the precursor may be a reaction product of a silane modifier with a cyclosiloxane, taking into consideration steric hindrances.
  • the precursor may be a partially hydrolyzed tertraethyl orthosilicate, such as TES 40 or Silbond 40.
  • the precursor may also be a
  • methylsesquisiioxane such as SR-350 available formerly from General Electric
  • the precursor may also be a phenyl methyl siloxane such as 604 from Wacker Chemie AG.
  • the precursor may also be a methylphenylvinylsiloxane, such as H62 C from Wacker Chemie AG.
  • the precursors may also be selected from the following:
  • a precursor may be a compound of the following general formula.
  • the R groups Ri , R 2 , R 3 , and R 4 may all be different, or one or more may be the same.
  • R2 is the same as R3, R 3 is the same as R 4 , Ri and R 2 are different with R 3 and R 4 being the same, etc.
  • embodiments of formulations for polysilocarb formulations may for example have from about 0% to 50% MH, about 20% to about 99% MH, about 0% to about 30% siloxane backbone additives, about 1 % to about 60% reactive monomers, about 30% to about 100% TV, and, about 0% to about 90% reaction products of a siloxane backbone additives with a silane modifier or an organic modifier reaction products.
  • the formulations In mixing the formulations sufficient time should be used to permit the precursors to become effectively mixed and dispersed. Generally, mixing of about 15 minutes to an hour is sufficient. Typically, the precursor formulations are relatively, and essentially, shear insensitive, and thus the type of pumps or mixing are not critical. It is further noted that in higher viscosity formulations additional mixing time may be required. However, the use of the reaction extruder provides the ability to achieve this in greatly reduced times compared to other production systems and methods. This benefits of the extruder, typically and in embodiments, can be obtained because of the mixing action precursor throughout its time in the barrel.
  • the temperature of the formulations, during mixing should preferably be kept below about 45° C, and preferably about 10° C. (It is noted that these mixing conditions are for the pre-catalyzed formulations.)
  • reaction type process in general, a chemical reaction is used to combine one, two or more precursors, typically in the presence of a solvent, to form a precursor formulation that is essentially made up of a single polymer that can then be, catalyzed, cured and pyrolized.
  • This entire process up to and excluding pyrolysis, can take place in the extruder barrel of a reaction extruder.
  • This process provides the ability to build custom precursor formulations that when cured can provide plastics having unique and desirable features such as high temperature, flame resistance and retardation, strength and other features.
  • the cured materials can also be pyrolized to form ceramics having unique features.
  • the reaction type process allows for the predetermined balancing of different types of functionality in the end product by selecting functional groups for incorporation into the polymer that makes up the precursor formulation, e.g., phenyls which typically are not used for ceramics but have benefits for providing high temperature capabilities for plastics, and styrene which typically does not provide high temperature features for plastics but provides benefits for ceramics.
  • functional groups for incorporation into the polymer that makes up the precursor formulation e.g., phenyls which typically are not used for ceramics but have benefits for providing high temperature capabilities for plastics, and styrene which typically does not provide high temperature features for plastics but provides benefits for ceramics.
  • a custom polymer for use as a precursor formulation is made by reacting precursors in a condensation reaction to form the polymer precursor formulation. This precursor formulation is then cured into a preform through a hydrolysis reaction. The condensation reaction forms a polymer of the type shown below.
  • Ri and R 2 may be the same or different.
  • the custom precursor polymers can have several different polymeric units, e.g., Ai , A 2 , A n , and may include as many as 10, 20 or more units, or it may contain only a single unit, for example, MHF made by the reaction process may have only a single unit.
  • Embodiments may include precursors, which include among others, a triethoxy methyl silane, a diethoxy methyl phenyl silane, a diethoxy methyl hydride silane, a diethoxy methyl vinyl silane, a dimethyl ethoxy vinyl silane, a diethoxy dimethyl silane.
  • the end units, Si End 1 and Si End 2 can come from the precursors of dimethyl ethoxy vinyl silane, ethoxy dimethyl phenyl silane, and trimethyl ethoxy silane. Additionally, if the polymerization process is properly controlled a hydroxy end cap can be obtained from the precursors used to provide the repeating units of the polymer. [00118] In general, the precursors are added to the extruder barrel and the entire reaction including curing takes place in the extruder barrel.
  • a catalyst is used in the curing process of the polymer precursor formulations from the reaction type process.
  • the same polymers, as used for curing the precursor formulations from the mixing type process can be used. It is noted that, generally unlike the mixing type formulations, a catalyst is not necessarily required to cure a reaction type polymer. Inhibitors may also be used. However, if a catalyst is not used, reaction time and rates will be slower.
  • the curing and the pyrolysis of the cured material from the reaction process is essentially the same as the curing and pyrolysis of the cured material from the mixing process and the reaction blending process.
  • the barrel is filled with a liquid, then rubber like or gel material, then solid.
  • the reaction type process can be conducted under numerous types of atmospheres and conditions, e.g., air, inert, N 2 , Argon, flowing gas, static gas, ambient pressure, elevated pressure, and combinations and variations of these.
  • reaction blending type process precursor are reacted to from a precursor formulation, in the absence of a solvent.
  • a reaction blending type process has a precursor formulation that is prepared from MHF and Dicyclopentadiene ("DCPD").
  • DCPD Dicyclopentadiene
  • a MHF/DCPD polymer is created and this polymer is used as a precursor formulation. (It can be used alone to form a cured or pyrolized product, or as a precursor in the mixing or reaction processes.) This entire process can take place in the extruder.
  • the extruder barrel is the reaction vessel and mixer, that can be used for the reaction.
  • the reaction is conducted in the extruder barrel, and preferably in a predetermined zone(s) of the barrel, and then is further cured to a plastic PDC material in later, more distal, zones of the extrusion barrel.
  • the reaction and curing can also be conducted in a single zone, e.g., over the entirety of the length of the extruder barrel.
  • the reaction is conducted at atmospheric pressure, but higher and lower pressures can be utilized, and pressures above atmospheric pressure are typically seen in the reaction extrusion processes, as these pressures are developed by back pressure in the barrel.
  • the reaction blending type process can be conducted under numerous types of atmospheres and conditions, e.g., air, inert, N 2 , Argon, flowing gas, static gas, ambient pressure, elevated pressure, and combinations and variations of these.
  • the polysilocarb precursor formulation may be processed through an initial cure, to provide a partially cured material, which may also be referred to, for example, as a preform, green material, or green cure (not implying anything about the material's color).
  • the green material may then be further cured, either in a later zone of the extruder or in a subsequent heating step.
  • the material may be "end cured,” i.e., being cured to that point at which the material has the necessary physical strength and other properties for its intended purpose.
  • the amount of curing may be to a final cure (or "hard cure"), i.e., that point at which all, or essentially all, of the chemical reaction has stopped (as measured, for example, by the absence of reactive groups in the material, or the leveling off of the decrease in reactive groups over time).
  • the material may be cured to varying degrees, depending upon its intended use and purpose. For example, in some situations the end cure and the hard cure may be the same. Curing conditions such as, , screw design, rotation speed, temperature, length, relationship of different zones, and atmosphere may effect the composition of the cured material.
  • volumetric shapes from the extruder, or from subsequent processing, such as an extrusion die, liquid extrusion, molding, pressing, and other operations or apparatus may include for example, the following: spheres, pellets, platelets, sheets, flakes, rings, lenses, disks, panels, cones, frustoconical shapes, squares, rectangles, trusses, angles, channels, blocks, sheets, films, skins, particulates, beams, rods, angles, slabs, columns, fibers, staple fibers, tubes, cups, pipes, and combinations and various of these and other more complex shapes, both engineering and architectural.
  • the forming step, the curing steps, and the pyrolysis steps may be conducted in batch processes, serially, continuously, with time delays (e.g., material is stored or held between steps), and combinations and variations of these and other types of processing sequences.
  • time delays e.g., material is stored or held between steps
  • the curing process is conducted continuously.
  • the precursors can be partially cured, or the cure process can be initiated and on going, prior to the precursor being formed into a volumetric shape.
  • predetermined conditions e.g., the material is exposed to a predetermined atmosphere, and temperature profile during the entirely of its processing, e.g., reduced oxygen, temperature of cured preform held at about 140° C prior to pyrolysis.
  • system, equipment, or processing steps, for forming, curing and pyrolizing may be the same equipment, continuous equipment, batch and linked equipment, and combinations and variations of these and other types of industrial processes.
  • an embodiment of a reaction extrusion technique could form cured particles that are feed directly into a fluidized bed reactor, a rotary kiln, a multihearth kiln, or a tunnel kiln for pyrolysis.
  • the polysilocarb precursor formulations used in the extrusion reaction systems and processes, can be made into neat, non-reinforced, non-filled, composite, reinforced, and filled structures, intermediates, end products, and combinations and variations of these and other compositional types of materials. Further, these structures, intermediates and end products can be cured (e.g., green cured, end cured, or hard cured), uncured, pyrolized to a ceramic, and combinations and variations of these (e.g., a cured material may be filled with pyrolized material derived from the same polysilocarb as the cured material).
  • the precursor formulations may be used to form a "neat” material, (by “neat” material it is meant that all, and essentially all of the structure is made from the precursor material or unfilled formulation; and thus, there are no fillers or
  • the polysilocarb precursor formulations may be used to coat or impregnate a woven or non-woven fabric, made from for example carbon fiber, glass fibers or fibers made from a polysilocarb precursor formulation (the same or different formulation), to from a prepreg material. In this manner very lightly cured, e.g., soft, semi-solid material, from the extruder barrel, is forced into the woven or non-woven fabric.
  • the polysilocarb precursor formulations in the reaction extruder systems may be used to form composite materials, e.g., reinforced products.
  • the semi-solid cured extrudate may be forced into, impregnated into, absorbed by or otherwise combined with a reinforcing material, such as carbon fibers, glass fiber, woven fabric, grapheme, carbon nanotubes, thin films, precipitates, sand, non-woven fabric, copped fibers, fibers, rope, braided structures, ceramic powders, glass powders, carbon powders, graphite powders, ceramic fibers, metal powders, carbide pellets or components, staple fibers, tow, nanostructures of the above, polymer derived ceramics, any other material that meets the temperature requirements of the process and end product, and combinations and variations of these.
  • a reinforcing material such as carbon fibers, glass fiber, woven fabric, grapheme, carbon nanotubes, thin films, precipitates, sand, non-woven fabric, copped fibers, fibers, rope, braided structures, ceramic powders, glass powders, carbon powders, graphite powders, ceramic fibers, metal powders, carbide pellets
  • the polysilocarb precursor formulation in the reaction extrusion systems of the present inventions may be used to form a filled material.
  • a filled material would be any material having other solid, or semi-solid, materials added to the polysilocarb precursor formulation.
  • the filler material may be selected to provide certain features to the cured product, the ceramic product and both. Preferably the fillers are added to the extruder infeed along with the precursors. These features may relate to, or be, for example, aesthetic, tactile, thermal, density, radiation, chemical, cost, magnetic, electric, and combinations and variations of these and other features. These features may be in addition to strength. Thus, the filler material may not affect the strength of the cured or ceramic material, it may add strength, or could even reduce strength in some situations.
  • the filler material could impart color, magnetic capabilities, fire resistances, flame retardance, heat resistance, electrical conductivity, anti-static, optical properties (e.g., reflectivity, refractivity and iridescence), aesthetic properties (such as stone like appearance in building products), chemical resistivity, corrosion resistance, wear resistance, reduced cost, abrasions resistance, thermal insulation, UV stability, UV protective, and other features that may be desirable, necessary, and both, in the end product or material.
  • filler materials could include carbon black, copper lead wires, thermal conductive fillers, electrically conductive fillers, lead, optical fibers, ceramic colorants, pigments, oxides, sand, dyes, powders, ceramic fines, polymer derived ceramic particles, pore-formers, carbosilanes, silanes, silazanes, silicon carbide, carbosilazanes, siloxane, powders, ceramic powders, metals, metal complexes, carbon, tow, fibers, staple fibers, boron containing materials, milled fibers, glass, glass fiber, fiber glass, and nanostructures (including nanostructures of the forgoing) to name a few.
  • the polysilocarb formulation and products derived or made from that formulation may have metals and metal complexes, which can be added in the infeed to the extruder. Filled materials would include reinforced materials. In many cases, cured, as well as pyrolized polysilocarb filled materials can be viewed as composite materials. Generally, under this view, the polysilocarb would constitute the bulk or matrix phase, (e.g., a continuous, or substantially continuous phase), and the filler would constitute the dispersed (e.g., non-continuous), phase.
  • the filler can be evenly distributed in the precursor formulation, unevenly distributed, distributed over a predetermined and controlled distribution gradient (such as from a predetermined rate of settling), and can have different amounts in different formulations, which can then be formed into a product having a predetermined amounts of filler in predetermined areas (e.g., striated layers having different filler concentration).
  • a predetermined and controlled distribution gradient such as from a predetermined rate of settling
  • the ratio (either weight or volume) of polysilocarb to filler material could be from about 0.1 :99.9 to 99.9:0.1.
  • reaction extrusion systems and processes can be used to form non-reinforced polysilocarb materials, which are materials that are made of primarily, essentially, and preferably only from the precursor materials; but may also include formulations having fillers or additives that do not impart strength.
  • the curing may be done at standard ambient temperature and pressure ("SATP", 1 atmosphere, 25° C), and preferably in the reaction extrusion systems at temperatures above that temperature, at pressures above that pressure, and over varying time periods.
  • SATP standard ambient temperature and pressure
  • the curing can be conducted over various heatings, rate of heating, and temperature profiles (e.g., hold times and temperatures, continuous temperature change, cycled temperature change, e.g., heating followed by maintaining, cooling, reheating, etc.).
  • the time for the curing can be from a few seconds (e.g., less than about 1 second, less than 5 seconds), to less than a minute, to minutes, to hours, to days (or potentially longer).
  • the furnace, containers, handling equipment, atmosphere, and other components of the curing apparatus and process are clean, essentially free from, and do not contribute any elements or materials, that would be considered impurities or contaminants, to the cured material.
  • the curing environment e.g., the furnace, the atmosphere, the container and combinations and variations of these can have materials that contribute to or effect, for example, the composition, catalysis, stoichiometry, features, performance and combinations and variations of these in the preform, the ceramic and the final applications or products.
  • the curing takes place at temperatures in the range of from about 5°C or more, from about 20°C to about 250°C, from about 20°C to about 150°C, from about 75°C to about 125°C, and from about 80°C to 90°C.
  • temperatures in the range of from about 5°C or more, from about 20°C to about 250°C, from about 20°C to about 150°C, from about 75°C to about 125°C, and from about 80°C to 90°C.
  • rate of temperature change over time e.g., ⁇ degrees/time
  • hold times e.g., hold times, and temperatures
  • the cure conditions may be dependent upon, and in some embodiments can be predetermined, in whole or in part, by the formulation to match, for example the size of the preform, the shape of the preform, or the mold holding the preform to prevent stress cracking, off gassing, or other phenomena associated with the curing process.
  • the reaction extrusion process adds additional manufacturing flexibility, it provides the ability to avoid changing (or in combination with changing) a formulation; change the extruder properties, e.g., screw configuration, heating, rotation rate, etc.
  • a cross linking reaction takes place that provides in some embodiments a cross-linked structure having, among other things, an -Ri-Si-C-C-Si-0-Si-C-C-Si-R2- where Ri and R2 vary depending upon, and are based upon, the precursors used in the formulation.
  • Ri and R2 vary depending upon, and are based upon, the precursors used in the formulation.
  • the cured materials may have a cross-linked structure having 3- coordinated silicon centers to another silicon atom, being separated by fewer than 5 atoms between silicon atoms.
  • these compositions will be found in the extruder, and may also be the extradite.
  • the PDC formulation is run in the extruder under conditions that create minimal, no appreciable and preferably no off gassing.
  • the extruder may be run at temperature equal to, but no exceeding 210 C for a precursor formulation, e.g., 50:50 HF:DCPD, where no off gassing will occur and the extrusion operation will have %100 yield in going from liquid starting material to green cured material.
  • a precursor formulation e.g., 50:50 HF:DCPD
  • the extrusion process for forming cured material from PDC precursors provides the ability to have at least 80 yield, at least 90 yield, at least 95 yield, at least 98% yield, and at least 99% yield and greater.
  • the extruder can be vented to an appropriate gas handling, collection or cleaning system.
  • some formulations may exhibit an exotherm, i.e., a self heating reaction, that can produce a small amount of heat to assist or drive the curing reaction, or that may produce a large amount of heat that may need to be managed and removed in order to avoid problems, such as stress fractures.
  • an exotherm i.e., a self heating reaction
  • the cure off gassing typically occurs and results in a loss of material, which loss is defined generally by the amount of material remaining, e.g., cure yield.
  • Embodiments of the formulations, cure conditions, and polysilocarb precursor formulations of embodiments of the present inventions can have cure yields of at least about 90%, about 92%, about 100%.
  • the materials may have cure yields above 100%, e.g., about 101 -105%, as a result of oxygen being absorbed from the air.
  • this shrinkage may be, depending upon the formulation, cure conditions, and the nature of the preform shape, and whether the preform is reinforced, filled, neat or unreinforced, from about 20%, less than 20%, less than about 15%, less than about 5%, less than about 1 %, less than about 0.5%, less than about 0.25% and smaller.
  • the desired level of curing is obtained in the extruder.
  • subsequent curing of the material may be accomplished by any type of heating apparatus, or mechanisms, techniques, or morphologies that has the requisite level of temperature and environmental control, for example, heated water baths, electric furnaces, microwaves, gas furnaces, furnaces, forced heated air, towers, spray drying, falling film reactors, fluidized bed reactors, lasers, indirect heating elements, direct heating, infrared heating, UV irradiation, RF furnace, in-situ during emulsification via high shear mixing, in-situ during emulsification via ultrasonication.
  • the cured material (e.g., green material, initial cure, final cure, or hard cure) may be held under a controlled environment, for example the cured material may be held at a control temperature, in a predetermined environment (e.g., water bath, low 0 2 environment, high 0 2 environment, liquid bath, liquid bath having additives, inert atmosphere, misting, gaseous atmosphere having additives, etc.).
  • a control temperature e.g., water bath, low 0 2 environment, high 0 2 environment, liquid bath, liquid bath having additives, inert atmosphere, misting, gaseous atmosphere having additives, etc.
  • This control hold step can be used to affect the properties of the end product (cured, pyrolized and both), such as strength, and can be used to provide additives, or additional features to the end material or product.
  • the reaction extruder may be connected directly to a pyrolysis system, or the cured material from the extruder can be stored and pyrolized at a different location or time.
  • the preform, or cured structure, or cured material In pyrolizing the preform, or cured structure, or cured material, it is heated to about 600° C to about 2,300° C; from about 650° C to about 1 ,200° C, from about 800°C to about 1300°C, from about 900°C to about 1200°C and from about 950°C to 1150°C. At these temperatures typically all organic structures are either removed or combined with the inorganic constituents to form a ceramic. Typically at temperatures in the about 650° C to 1 ,200° C range the resulting material is an amorphous glassy ceramic.
  • the material When heated above about 1 ,200° C the material typically may from nano crystalline structures, or micro crystalline structures, such as SiC, Si3N 4 , SiCN, ⁇ SiC, and above 1 ,900° C an a SiC structure may form, and at and above 2,200° C ⁇ SiC is typically formed.
  • the pyrolized, e.g., ceramic materials can be single crystal, polycrystalline, amorphous, and combinations, variations and subgroups of these and other types of morphologies.
  • the pyrolysis may be conducted under may different heating and environmental conditions, which preferably include thermo control, kinetic control and combinations and variations of these, among other things.
  • the pyrolysis may have various heating ramp rates, heating cycles and environmental conditions.
  • the temperature may be raised, and held a predetermined temperature, to assist with known transitions (e.g., gassing, volatilization, molecular rearrangements, etc.) and then elevated to the next hold temperature corresponding to the next known transition.
  • the pyrolysis may take place in reducing atmospheres, oxidative atmospheres, low C1 ⁇ 2, gas rich (e.g., within or directly adjacent to a flame), inert, N 2 , Argon, air, reduced pressure, ambient pressure, elevated pressure, flowing gas (e.g., sweep gas, having a flow rate for example of from about from about 15.0 GHSV to about 0.1 GHSV, from about 6.3 GHSV to about 3.1 GHSV, and at about 3.9 GHSV), static gas, and combinations and variations of these.
  • gas rich e.g., within or directly adjacent to a flame
  • inert e.g., N 2 , Argon
  • air reduced pressure
  • ambient pressure e.g., elevated pressure
  • flowing gas e.g., sweep gas, having a flow rate for example of from about from about 15.0 GHSV to about 0.1 GHSV, from about 6.3 GHSV to about 3.1 GHSV, and at about 3.9 GHSV
  • static gas e.
  • the pyrolysis is conducted over a time period that preferably results in the complete pyrolysis of the preform.
  • the furnace, containers, handling equipment, and other components of the pyrolysis apparatus are clean, essentially free from, free from and do not contribute any elements or materials, that would be considered impurities or contaminants, to the pyrolized material.
  • a constant flow rate of "sweeping" gas can help purge the furnace during volatile generation.
  • the pyrolysis environment e.g., the furnace, the atmosphere, the container and combinations and variations of these, can have materials that contribute to or effect, for example, the composition, stoichiometry, features, performance and combinations and variations of these in the ceramic and the final applications or products.
  • char yield or pyrolysis yield
  • the formulations and polysilocarb precursor formulations of embodiments of the present formulations can have char yields for SiOC formation of at least about 60%, about 70%, about 80%, and at least about 90%, at least about 91 % and greater. In fact, with air pyrolysis the materials may have char yields well above 91 %, which can approach 100%.
  • formulations high in phenyl content at least about 1 1 %, and preferably at least about 20% by weight phenyls
  • formulations high in allyl content at least about 15% to about 60%
  • the pyrolysis may be conducted in any heating apparatus that maintains the request temperature and environmental controls.
  • pyrolysis may be done with gas fired furnaces, electric furnaces, direct heating, indirect heating, fluidized beds, kilns, tunnel kilns, box kilns, shuttle kilns, coking type apparatus, lasers, microwaves, and combinations and variations of these and other heating apparatus and systems that can obtain the request temperatures for pyrolysis.
  • Custom and predetermined control of when chemical reactions, arrangements and rearrangements, occur in the various stages of the process from raw material to final end product can provide for reduced costs, increased process control, increased reliability, increased efficiency, enhanced product features, increased purity, and combinations and variation of these and other benefits.
  • the sequencing of when these transformations take place can be based upon the conditions of the reaction extrusion process and the reaction extruder system, in this manner the processing or making of precursors, and the processing or making of precursor formulations; and may also be based upon cure and pyrolysis conditions. Further, the custom and
  • the pumping unit 52, the transfer assembly 55, and both are an extruder.
  • the extruder can further be used to admix, mix, react, blend and other wise combine several different starting materials to provide a PDC precursor batch. In this manner the PDC processor formulation is made at the forming unit.
  • extrusion and underwater i.e., in liquid, extrusion and cutting are focused on in this section of the specification, it should be understood that the extrusion can take place in any fluid, including, liquids, water, gases, air, nitrogen, under reduced pressure, under increased pressure, in a flowing fluid environment, and other forming environments disclose and taught in the disclosures that are incorporated into this specification by reference.
  • the extruder and in particular when used as a blending or reaction device to make a PDC formulation does not require and in embodiments may not have a die.
  • FIG. 21 there is shown a perspective view of an underwater pelletizing system 51.
  • the system 51 has a pumping unit 52 that has a base 54 and a liquid PDC precursor feed line 53.
  • the feed line 53 is connected to a PDC precursor source, e.g., a make up system, tank, etc. (not shown in the figure).
  • a transfer assembly 55 e.g., a line, pipe, pump discharge, etc., provides the PDC precursor to the formation section or formation head 56.
  • the formation section 56 has a die assembly 57 and a cutter assembly 58, and a fluid in-flow line 514, and a fluid out-flow line 515.
  • the formation section 6 has a cutter force unit 9 and a cutter drive system 510.
  • Those units have a power/control line 51 1 .
  • the formation section 6 has a heater powered by line 13 and a temperature sensor having a temperature sensor line 512.
  • line 513, line 512 and line 51 1 are in communication with a control system, that controls the operation of the system.
  • the reaction extrusion system of US 9,302,419 can be used to make PDC cured material.
  • the entire disclosure of US Patent No. 9,302,419 is incorporated herein by reference.
  • the system of this Example can be used to make PDC cured volumetric shaped PDC materials, including polysilocarb cured volumetric shaped materials, such as particles, pellets and beads.
  • an extruder having an operative unit composed of a cylinder and at least two screw shafts which are rotatably accommodated therein, a gear unit having at least two output shafts, wherein each output shaft, via a connecting element, is connected in a rotationaily fixed manner to one screw shaft, a motor which drives the gear unit and is coupled to the gear unit via a clutch, and a controller installation, wherein each connecting element or each output shaft is assigned a separate measuring installation for determining the applied torque, wherein the measuring installations communicate with the controller installation which, depending on the individual determined torques, controls the clutch which is implemented as a switchable clutch, wherein the controller installation is configured for opening the clutch both when a determined torque exceeds a torque limit value and also when the difference between the two determined torques exceeds a limit value.
  • the extruder comprises an operative unit composed of a cylinder and at least two screw shafts which are rotatably accommodated therein, a gear unit having at least two output shafts, wherein each output shaft, via a connecting element, is connected in a rotationaily fixed manner to one screw shaft, a motor which drives the gear unit and is coupled to the gear unit via a dutch, and a controller installation.
  • extruders of this type serve for preparing compounds which, in the operative unit or the cylinder, respectively, are processed via one or more screw shafts, also referred to as extruder screws, rotating therein, in only an exemplary manner, mention may be made of PDC precursor materials, which are compounded or reacted and cured in the extruder in order to be subsequently further processed, for example for forming PDC plastic granules or in the context of injection-molding or for manufacturing components and similar.
  • PDC materials are compounded or reacted and cured to form neat volumetric shapes.
  • PDC materials are compounded or reacted and cured to form filled volumetric shapes.
  • the corresponding materials are processed and mixed etc. via the screws and other elements in the cylinder, in order to achieve the desired homogenous composition of the extruded product.
  • one or more installations such as, for example, corresponding infeed installations, via which the materials to be processed, e.g., PDC precursors, fillers, non-silicon based cross- linkers, etc., are added in a metered manner, or heating installations, which serve for temperature-controlling the cylinder or the cylinder sections from which such a cylinder is typically assembled, or similar is/are provided on the operative unit or assigned to the operative unit, respectively.
  • corresponding compounds are often prepared using an extruder.
  • the drive of the at least two screw shafts is, of course, an essential aspect in the functioning of the extruder, since both the torque of the screws and also the revolutions of the screws, which are relevant to the energy introduced into the material to be prepared, are adjusted via the drive.
  • the motor is typically coupled to the gear unit via an overload clutch, wherein the overload clutch, having a corresponding given overload on the screws, opens and separates the gear unit from the motor.
  • the clutch in the case of an overload, the clutch only opens when the cumulative torque of the two screw shafts that is applied via the output shafts and the gear unit to one side of the clutch is greater than the cut-out torque defined by the concept and the dimensions of the overload clutch. Then, and only then, does the overload clutch open, which overload clutch is a mechanically-separating clutch in which, for example, spring- loaded balls assigned to one side of the clutch engage in corresponding calottes assigned to the other side of the clutch and, when a cut-out torque is applied, migrate out of the calottes, causing the clutch to slip and open, respectively.
  • overload clutch is a mechanically-separating clutch in which, for example, spring- loaded balls assigned to one side of the clutch engage in corresponding calottes assigned to the other side of the clutch and, when a cut-out torque is applied, migrate out of the calottes, causing the clutch to slip and open, respectively.
  • the cutout torque has to be applied directly to the dutch; as a result, the actual torque given on the screw shafts is somewhat higher, since there is a certain loss of torque in the mechanical train from the screw shafts to the clutch, and respectively a certain time factor also plays a part, since any increase of the torque on the screw shafts is transmitted with some time delay to the clutch.
  • An overload may thus already exist with the screw shafts but not be applied yet to the clutch. This may have disadvantages for the operation of the extruder and, in particular, aiso for the screw shafts and wear thereof.
  • FIG. 22 showing the embodiment of this Example, an in- principle illustration of an extruder 71 is shown, comprising an operative unit 72 having a cylinder 73 which, as is usual in most cases, is composed of a plurality of individual cylinder segments which are lined up next to one another and interconnected. As is shown in a highlighted manner here, two screw shafts 75a, 75h are rotatably
  • the cylinder 3 has a cylinder bore which is implemented as a figure-eight barrel bore, as is known per se.
  • a further installation in the form of an infeed installation 6 is disposed on, or assigned to, respectively, the operative unit 72, wherein, of course, a plurality of such infeed installations 78 may also be provided.
  • the material(s) to be processed is/are added via the infeed installation 76.
  • a heating installation 77 via which the cylinder 73 can be temperature- controlled and which is also indicated in only an exemplary manner.
  • the gear unit 710 a reduction gear unit, is coupled to the motor 712 via a switchable clutch 71 1 which is a pneumatically switchable clutch or an electromagnetically switchable clutch.
  • the rotation of the motor output shaft is thus transmitted via the clutch 71 1 to the gear unit 710 which is transmitted via the gear unit output shafts 79a, 795 and the connecting elements 78a, 7Qb to the screw shafts 75a, 75b.
  • controller installation 713 which controls the operation of the essential or of all components of the extruder 71 .
  • said controller installation 713 may control the operation of the infeed installation 76, on the one hand, and also the heating installation 7.
  • Said controller installation 713 via an inverter 714, moreover also controls the operation of the motor 712, in order to control the torque generated, or supplied, respectively, by the motor 712, and the revolutions of said motor 712.
  • the controller installation 713 furthermore also controls the switchable clutch 711 . If said clutch is a pressure-loaded friction clutch, it may be actively switched in that the air pressure by way of which the friction-clutch disks are pressed together is controlled via the controller installation. Depending on how high the compression of the disks is, a variable level of torque may be transmitted, or a variably high cut-out torque in the case of any overload may be set, respectively. If the clutch 71 1 is an
  • electromagneticaliy switchable clutch via an electromagnet, two gear-tooth disks may be pressed together in a form-fitting manner, wherein, depending on how forcibly the disks are compressed, a variable level of torque may be transmuted, or a variably high cut-out torque, respectively, may be set.
  • the cluich 71 1 may also be actively opened by corresponding activation of the same via the controller installation 713.
  • measuring installations 715a, 715b which, in the example shown, are assigned to the connecting elements 78a, 78b, that is to say to the two collar couplings. However, in the same manner, they may also be assigned to the output shafts 79a. 79b.
  • the measuring installations 715a, ' 5o serve for individually registering separate actual torques on the connecting elements 78a, 78b, or, if disposed thereon, on the output shafts 79a, 79b, respectively.
  • These measuring installations 715a, 715b communicate with the controller installation 713, such that the registered actual torques are continuously relayed to the latter.
  • the measuring installations 715a, 715b are preferably measuring installations which operate in a non-contacting manner, preferably such which enable registration of a magnetic field, or the registration of a modification of the magnetic field, respectively.
  • the connecting elements 78a, 78b are expediently entirely, or at least in portions, provided with permanent magnetization, such that, in consequence, they generate a permanent magnetic field.
  • the output shafts are correspondingly magnetized.
  • mechanical loading of the respective connecting elements 78a, 78.6, or of the output shafts 79a, 79.6, respectively takes place, said loading in turn leading to a modification of the magnetic field.
  • the measuring installations 715a, 715b comprise corresponding magnetic sensors, for example in the form of Hall-type sensors, which register this magnetic field, or the modification of the field, respectively.
  • the respective measuring installation 715a, 715/3, or latest the controller installation 713 can now determine the respective actuai torque being applied to the connecting element 8 a, 8 b, or to the output shaft 79a, 79.d.
  • This respective actual torque may be assigned to the respective screw shaft 75a, 75fc»; the actual torque being applied there essentially corresponds to the measured torque, since measuring takes place directly in the connecting region between the screw elements and the gear unit, and not in the clutch region.
  • the controller installation is now capable of registering whether or not an operative situation exists that requires actively opening the clutch 71 and thus separating the gear unit 710 from the motor 712.
  • Such a condition may exist when one of the determined actual torques is higher than a torque limit value.
  • Each screw shaft 75a, 75b is assigned a torque limit value which should not be exceeded. However, this may take place during operation, for example, when, by way of the infeed installation 76, only one of the screw shafts 75a, 75b is loaded. In this case, the cumulative value of the two individual actual torques may still be very much below the defined cumulative cutout torque of the clutch 711. Nevertheless, overloading of a screw shaft 75a, 75b has to be attended to. if this is identified by the controller installation 713, the clutch 711 is actively opened.
  • the controller installation 13 can also determine any difference between the two actual torques, that is to say any torque differential. If the latter is greater than a limit value, an extreme difference in the loading of the individual screw shafts 75a, 75b likewise exists. This may also indicate an overload situation which leads to actively opening the clutch 71 .
  • the controller installation 713 Since the actuai torques are continuously relayed via the measuring installations 715a, 7151? to the controller installation 713, the latter can consequently register the temporal profile of the measured values determined in each case. Should a sufficiently steep increase, or gradient, respectively, of a determined torque value occur now, the controller installation can determine the gradient and compare it with a comparison gradient. If the increase is sufficiently steep, which would be established by way of the comparison, this may likewise display an overload situation; again, the controller installation 713 switches the clutch 711 so as to open.
  • any potential oscillation of torque values may also be registered and the amplitude thereof may be determined. Slight oscillation typically exists; but if oscillation is excessive, this may also indicate a potential overload situation. If the comparison of the determined actual oscillation amplitude with a comparison amplitude now shows that the actual oscillation amplitude exceeds the comparison amplitude, this may also lead to actively opening the clutch.
  • An extruder screw includes a screw shaft with several screw elements which can be or have been detachably slipped onto this shaft, the screw shaft having an external gearing and the screw elements having an internal gearing which engage the external gearing.
  • the profile of the teeth of the external and the internal gearing are asymmetric, whereby in relation to a preferred direction of rotation of the extruder screw, the torque-transferring flanks of the teeth of the external and the internal gearing make a smaller angle with the perpendicular to the axis of rotation than do respective opposing flanks, at the teeth, of the external and internal gearing.
  • This Example relates primarily to an extruder screw consisting of a screw shaft with several screw elements, which can be or have been detachably slipped onto this shaft, the screw shaft having an external gearing and the screw elements having an internal gearing, which engages the external gearing.
  • extruder screws which are also referred to as plug-in screws
  • plug-in screws are known and make a variable construction of an extruder screw possible in that, depending on the requirements, different screw elements, such as conveying, kneading or mixing elements may be disposed in different sequences on the screw shaft.
  • screw elements such as conveying, kneading or mixing elements
  • a shaft hub gearing is provided between the screw shaft and the shaft elements, that is, the screw shaft has an external gearing
  • the screw elements, functioning as hub have an internal gearing on the inside of their borehole, both gearings meshing with one another.
  • shaft hub connections conforming to the Standards DIN 5480, DIN 5464 or ISO 4156 in the form of an evolving gearing, are used for extruder screws.
  • This positive, symmetrical gearing enables an appreciable torque to be transferred, while, at the same time, the screw elements are easy to install and to dismantle.
  • Extruders generally must meet the requirements of the highest possible efficiency, which is reflected primarily in the achievable throughput.
  • the available torque that is, the torque that can be transferred effectively over the screw shaft to the screw elements, the rpm of the screw and, with that, the drive performance, as well as the available free screw volume represent the deciding design criteria.
  • a high available torque is an advantage, because it permits, on the one hand, a higher degree of filling.
  • lower average shear velocities and lower product temperatures are achieved.
  • the residence time of the product in the extruder is shortened, the stress on the product, on the whole, is less than in comparable process steps with a lower torque. On the whole, a higher torque permits a higher screw rpm and, with that, also a higher throughput.
  • a further possibility for increasing the throughput is to increase the available volume, which is usually given as the volumeness in the form of the ratio of the outer diameter of the screw D a to the internal diameter of the screw D,.
  • Usual volumenesses of double screw extruders, rotating in the same direction range from 1 .4 to 1 .6, to a maximum of 2.0, for instance. Enlarging the volume by deepening the screw channels while keeping the distance between the axles the same admittedly offers an improved feed and less shear. At the same time, lower material temperatures are reached because of the lower input of energy, so that finally, the extruder can be run at a higher rpm, thus increasing the throughput.
  • FIG. 1 1 there is shown an extruder 1 with a motor 2, to which is connected a transmission 3 and an extrusion cylinder 4, consisting of several cylinder sections 5, in the interior of which, in the examples shown, two extruder screws are accommodated in appropriate boreholes and are driven over the transmission 3, with which they are coupled over a well-known coupling, the details of which are not shown.
  • the extrusion cylinder 4, together with all necessary cooling agent pipes, power leads and control leads, which are placed in an appropriate built-in box 6, are built-up on a carrier 7, which, in turn, is supported on a bearer 8 of the machine frame 9.
  • a supply and control cabinet 10 contains the cooling agent and supply facilities, as well as the control devices, over which the individual components are supplied. The construction of such an extruder is adequately known.
  • extruder screws are disposed in the interior of the extrusion cylinder and consist of several cylinder sections 5 which are connected detachably with one another.
  • the extruder screws under discussion are so-called plug- in screws, which can be constructed and/or configured especially with regard to the material to be processed or the product to be produced. If necessary, they can be removed from the extrusion cylinder 4.
  • FIG. 12 shows an extruder screw 11 , consisting of a shaft 12, which, at its rear wider end, has, on the one hand, a first external gearing 13, over which it can be coupled with and driven by the transmission 3.
  • a shaft section 15 with an external gearing 16 adjoins at a stop 14.
  • Separate screw elements which differ depending on the material to be processed and the product to be produced, can be slipped onto this shaft section 15 and placed against the stop 14.
  • FIG. 12 shows an example with three screw elements 16 a, 16 ⁇ b and 16 c.
  • the screw element 16 a may, for example, be a conveying element, which has a screw 17, in the screw flight of which the material is conveyed.
  • the screw element 16 b may, for example, be a mixing element, which also has a screw 18, which has apertures 19.
  • the screw element 16 c may be a kneading element which has appropriate kneading sections 20.
  • the material, which is to be processed, is worked with a high input of energy by such a kneading element and, for example, plasticized or melted, depending on the application.
  • Each screw elements 16 a, 16 b, 16 c has a central borehole 21 a, 21 b, 21 c, by means of which it can be slipped onto the shaft section 15 and at the inside of which, that is, the hub, an internal gearing 22 a, 22 b, 22 c is provided, with which it is slipped onto the external gearing 16 of the shaft section 15, so that the internal gearing and the external gearing can mesh with one another.
  • the connection is a positive shaft- hub connection, which is described in detail in the following.
  • FIG. 13 shows two extruder screws 23 a, 23 b, which are shown parallel next to one another in the manner in which they are positioned relative to one another in the extrusion cylinder 4.
  • the screw shafts 24 a, 24 b are separated by the axial distance "a" from one another.
  • the external screw diameter D a is shown.
  • the volumeness of the screw or of the extruder results from the ratio D s /Di, the volumeness being a characteristic quantity of an extruder.
  • the external gearing 25 a and 25 b of the respective shaft 24 a and 24 b is shown, as well as the internal gearings 26 a and 26 b at the hub of the respective screw elements 27 a and 27 b.
  • the screw profiles in each case are asymmetric and are designed especially in relation to a particular preferred direction of rotation of the extruder screws 23 a, 23 b, which is shown by the two arrows marked R. Details of the gearing geometry arise out of FIGS. 14 to 14A.
  • FIG. 14 shows a section of the external gearing 25 a of the screw shaft 24 a, the same applying correspondingly also to the gearing of shaft 24 b.
  • the teeth 28 are shown in a detailed view.
  • each tooth 28 has a leading tooth flank 29 which interacts or engages with a corresponding tooth flank of the internal gearing at the screw element.
  • the trailing rear flank 30 of a tooth 28 which, during movement in the preferred direction of rotation R, usually has a minimum distance (flank clearance) from the corresponding, opposite tooth flank of the internal gearing of the order of a few one hundredths of a millimeter.
  • the asymmetric tooth profile is distinguished owing to the fact that the leading, torque-transferring or load-transferring tooth flank 29, which is constructed having a plane surface at least in its upper region towards the free tooth head, makes an angle of 0° with a line N perpendicular to the axis of rotation A of the screw shaft. This means that the tooth flank 29 extends radially to the axis of rotation A in the load- carrying region engaging the opposite flank.
  • the trailing tooth flank 30 makes an angle a of 30° with the perpendicular N to the axis of rotation A.
  • This tooth flank 30 also has a plane surface up to the transition into the base of a tooth.
  • a very broad tooth foot Z is formed, according to which the tooth flanks move apart in the direction of the tooth base 31 .
  • the base 31 of the tooth furthermore is rounded completely. This is possible because of the width of the tooth foot Z and the space between the teeth, which tapers in the direction of the shaft core.
  • the rounding radius r is, for example, 0.35 m.
  • the tooth head 32 itself essentially has a plane surface; it is merely arched slightly to correspond to the external radius of the external gearing.
  • the resulting tooth foot Z is very broad in comparison to a conventional, symmetrical, spline gearing. As described, this can be attributed to the tooth flanks, which move apart in the direction of the tooth base. Likewise, the tooth base 36 is rounded off completely, the radius r being approximately 0.4 m here. The possibility of rounding completely is also attributable here to the very broad tooth foot Z and the therefrom resulting, tapering tooth base 36. The complete rounding
  • the tooth head 37 of the internal gearing is profiled.
  • a recess 38 is provided, which extends from the leading tooth flank 35, which is at an angle of 30°, to the trailing, 0° load flank 34, but runs out over a radius, so that a tooth bridge 39 remains, which extends up to the load flank 34.
  • This tooth bridge 39 which results from a material recess, makes possible a strong decay particularly of compressive stresses, which arise in particular in this region during the transfer of torque, by a plastic flow of the tooth bridge material. By these means, the effect of the edge pressure excess in this region can advantageously be minimized because of the decrease in stress.
  • FIG. 14B diagrammatically shows the two gearings engaging one another. If the screw shaft 24 a rotates in the preferred direction R, torque is transferred from the 0° tooth flank 29 to the 0° tooth flank 34. It is evident that, because of their plane surfaces and their angle, which is identical everywhere, the tooth flanks are in contact with one another over a large area, so that the surface pressure is reduced. Reducing the surface pressure is furthermore useful since, because of the asymmetric profile, the number of teeth of the respective gearings can be increased clearly, that is, as a result of the profile symmetry, the modulus selected can be larger than that in the case of a comparable, symmetrical standard gearing.
  • the 0° tooth flank permits thermal expansion preferably in the radial direction, parallel to the load flank. Moreover, a clearance-free transfer of torque is possible. For this reason, the asymmetric profile is also suitable for temperature-related changes in stress. Furthermore, the 0° flank leads to a minimization of expanding forces in the hub, that is, of the internal gearing of the screw element. Because of the position of the flanks to one another, forces, which are introduced in the respective teeth of the internal gearing, are almost exclusively tangential forces and not radial forces, which are introduced in the case of the usual serrated shaft profiles.
  • a further advantage of the asymmetric tooth profile lies therein that, at least in the upper region of the tooth head, a tooth is somewhat elastic in bending, since it tapers clearly from the foot to the head, as shown in the Figures.
  • This elasticity in bending is beneficial and promotes a deviation-tolerant behavior optionally with utilization of a slight, partially plastic de-formation of the tooth foot region.
  • a material with a high yield stress is selected for the screw and leads to an increased fatigue strength even under dynamic loads.
  • An increase in torque can, moreover, generally be attained, for example, by shot blasting, additional rolling, cold rolling or the like of the gear parts in the region of the external as well as of the internal gearing.
  • an extruder has a casing with at least one bore.
  • One screw each is arranged in the bore in a rotatably drivable manner and is provided with a screw tip adjoining a nozzle plate.
  • a shearing tool is arranged at the screw tip directly in front of the nozzle plate and is provided with at least one arm, with a shearing gap being formed between said arm and the nozzle plate.
  • FIG. 15 of this Example shows a schematic longitudinal section of an extruder
  • FIG. 16 of this Example shows a front view of the extruder corresponding to the arrow II in FIG. 15
  • FIG. 17 of this Example shows a front view of the extruder according to the arrow I I in FIG. 15 with the nozzle plate removed
  • FIG. 18 of this Example shows a partial longitudinal section of the extruder corresponding to the section line IV-IV in FIG.
  • FIG. 19 of this Example shows a front view corresponding to FIG. 17 of a modified embodiment
  • FIG. 20 of this Example shows a section according to FIG. 18 of the modified embodiment but corresponding to the section line IV-IV in FIG. 19.
  • An extruder 1501 the basic structure of which is designed in the usual manner, is provided with a casing 1502 in which two bores 1503, 1503' having parallel axes 1504, 1504' are formed, said bores 1503, 1503' inter-engaging in a figure-eight- type manner.
  • screws 1505, 1505' are arranged which are composed of individual screw elements 1506, 1506' and, if necessary, kneading elements and the like which are not shown here.
  • the screw elements 1506, 1506' are arranged on toothed shafts 1507, which are only indicated, in a rotationally fixed manner.
  • Each of the last screw elements 1506, 1506' in the direction of flow 1508 is a so-called screw tip 1509, 1509'. All screw elements 1506, 1506', including the screw tip 1509, 1509', are clamped on the respective toothed shaft 1507 in the direction of the respective axis 1504, 150 4' by means of a clamping screw 1510, 1510'.
  • the screws 1505, 1505' are configured in a closely intermeshing manner, i.e. with inter-engaging screw stems 151 1.
  • the screws 1505, 1505' are driven by an electric motor 1512 connected to a reduction and distribution gearbox 1513, with the casing 1502 also being flange-mounted thereto.
  • the screws 1505, 1505' are driven in the same direction, i.e. their direction of rotation 1514 is the same.
  • a feeding funnel 15 projects into the casing 1502.
  • Degassing openings 1516, 1517 projecting out of the casing 2 may be provided behind the funnel 1515 in the direction of flow 1508 and may, for example, be connected to a vacuum pump not shown.
  • Retaining devices 1518, 1519 in the shape of screw elements conveying in a direction counter to the direction of flow 1508 may also be provided.
  • kneading elements may be provided.
  • the casing 1502 is supported on a foundation 1521 by means of columns 1520.
  • the screw elements 1506, 1506' arranged in front of the screw tips 1509, 1509— in relation to the direction of flow 1508— have a single flight, while the screw tips 1509, 1509' have two screw stems 1522, 1522 a and are thus are provided with a double flight.
  • the stem diameter Di of the screw elements 1506, 1506' and the screw tips 1509, 1509' is constant over the entire length.
  • the external diameter Da of the screw elements 1506, 1506' is constant over the length of the casing 1502. In practice, it is configured in a way as to equal the diameter of the bores 1503, 1503'.
  • the screw stems 1522, 1522 a of the screw tips 1509, 1509' taper down towards the stem diameter Di in the direction of flow 1508, i.e. they taper off in the screw stem 1523. Seen in the direction of flow 1508, the last screw-stem half 1522£>, 1522c, which equals the stem diameter Di, increases again until it equals the external diameter Da.
  • the bores 1503, 1503' of the casing are closed by nozzles in the shape of one nozzle plate 1524, 1524' each which are provided with a plurality of nozzle holes 1525.
  • a shearing tool 1526 or 1526', respectively, is arranged between each last screw stem 1522b or 1522c, respectively, and the respective nozzle plate 1524, 1524', said shearing tool 1526, 1526' being configured in a wing-like design.
  • the two wings or arms, respectively, 1527, 1527 a are disposed in a diametrical arrangement. They extend outwards from a hub 1528 in a substantially radial manner.
  • the diameter Dmin of this hub 1528 is considerably smaller than the stem diameter Di of the screw stem 1523.
  • the arms 1527, 1527 a of the shearing tools 1526, 1526' are provided with a conveying surface 1529, 1529 a which is inclined backwards towards the respective axis 1504 or 1504', respectively, in relation to the direction of rotation 1514, thus exerting a radial displacement effect in the direction of the hub 1528 on a material to be conveyed.
  • the conveying surfaces 1529, 1529 a are inclined backwards— in relation to the direction of rotation 1514— towards the nozzle plate 1524 or 1524', respectively, in a way that the conveyed material is fed into a shearing gap 1530 which is formed between the arms 1527, 1527 a and the facing side of the nozzle plate 1524 or 1524', respectively, and has a gap width s in the direction of the axes 1504, 1504' to which applies: 1 mm ⁇ s 3 mm.
  • the nozzle holes 25 are arranged on the nozzle plates 1524, 1524' over the entire annular surface which is confined by the hub diameter Dmin and the external diameter Da.
  • each of the shearing tools 1526 or 1526' forms a single part and is thus integral with the adjacent screw tip 1509, 1509'.
  • the shearing tool 1526, 1526' is configured as an individual component and is fastened to the clamping screw 1510 by means of a screw 1531.
  • Zones 1 and 2 are configured in multiple sub zones consisting of combinations of extruder elements intended to initially mix incoming feed and maximize residence time in these zones at controlled temperature to properly initiate the reaction for ingredients and catalyst to gel material and drive to cure.
  • the extruder elements are combinations of kneading elements and paddles to mix and create shear, transition elements, forward conveying elements and reverse conveying elements which will create back pressure and manage residence time.
  • Zone 3 also contains mixing, and both forward and reverse conveying elements which are adjacently positioned in alternating sequence to control the residence time.
  • Zone 4 is configured with a mixing zone and conveying elements to move the crosslinked polymer to the exit of the extruder. This outlet may be equipped with a die or throat to further create back pressure and control total residence time in the extruder.
  • the non-silicon based cross-linker is DCPD and a linear polysilocarb is MHF.
  • the extruder has 8 temp control zones and is using a 50:50 MHF:DCPD PDC precursor to form a PDC cured material, with the following temperature profile, per zone type:
  • Table 2 provides extruder conditions for a PDC formulation [00301] Table 2
  • a twin screw extruder is used to produce cured PDC material from a precursor formulation of 50% methyl hydrogen fluid and 50% DCPD.
  • the cured polysilocarb material is a white crumb that can be further worked, e.g., shaped, ground, cured, pyrolized.
  • a 3% catalyst loading is used.
  • the catalyst can be mixed with DCPD before going into the extruder.
  • a shaker table or conveyor belt moving material away from the extruder is used to move the cured material away from the extruder.
  • the cured material is still curing as it leaves the extruder, and can continue to cure for some time.
  • the material upon leaving the extruder should be separated, and preferably not permitted to agglomerate or pile up.
  • Example 9 The material of Example 9, is hard cured.
  • Example 9 The material of Example 9 is green cured.
  • Example 9c The material of Example 9c is shaped into beads and the bead are pyrolized to form a ceramic polysilocarb material.
  • a polysilocarb batch having 75% MH, 15% TV, 10% VT and 1 % catalyst (10 ppm platinum and 0.5% Luprox 231 peroxide) is used in a system of EXAMPLES 1 to 5 to form a cured material.
  • a polysilocarb batch having 70% MH, 20% TV, 10% VT and 1 % catalyst (10 ppm platinum and 0.5% Luprox 231 peroxide) is used in a system of EXAMPLES 1 to 5 to form a cured material.
  • a polysicocarb batch having 50% by volume fly ash is added to a polysilocarb batch having 70% MH, 20% TV, 10% VT and 1 % catalyst (10 ppm platinum and 0.5% Luprox 231 peroxide) is used in a system of EXAMPLES 1 to 5 to form a cured material.
  • a polysilocarb batch having 100% TV is used in a system of
  • a polysilocarb batch having 10% of the MH precursor (molecular weight of about 800), 73% of the methyl terminated phenylethyl polysiloxane precursor (molecular weight of about 1 ,000), and 16% of the TV precursor, and 1 % of the OH terminated is used in a system of EXAMPLES 1 to 5 to form a cured material.
  • a polysilocarb batch having 100% TV and less than about 0.5% peroxide catalysis is used in a system of EXAMPLES 1 to 5 to form a cured material.
  • a polysilocarb reaction blend batch having 85/15 MHF/DCPD is used in a system of EXAMPLES 1 to 5 to form a cured material.
  • a polysilocarb reaction blend batch having 85/15 MHF/DCPD with 1 % P01 catalyst and 1 % peroxide catalyst is used in a system of EXAMPLES 1 to 5 to form a cured material.
  • a polysilocarb reaction blend batch having 85/15 MHF/DCPD with 1 % P01 catalyst and 3% TV (which functions as a curie rate accelerator) is used in a system of EXAMPLES 1 to 5 to form a cured material is used in a system of
  • a polysilocarb reaction blend batch having 65/35 MHF/PCPD is used in a system of EXAMPLES 1 to 5 to form a cured material is used in a system of EXAMPLES 1 to 5 to form a cured material.
  • a polysilocarb reaction blend batch having 70/30 MHF/PCPD is used in a system of EXAMPLES 1 to 5 to form a cured material is used in a system of EXAMPLES 1 to 5 to form a cured material.
  • a polysilocarb batch having 50 - 65% MHF; 5 - 10% Tetravinyl; and 25 - 40% Diene (Dene Dicyclopentadiene or Isoprene or Butadiene), preferably catalyzed with P01 or other Platinum catalyst is used in a system of EXAMPLES 1 to 5 to form a cured material.
  • a polysilocarb batch having 50 - 65% MHF and 35 - 50% Tetravinyl, preferably catalyzed with P01 or other Platinum catalyst is used in a system of EXAMPLES 1 to 5 to form a cured material.
  • a polysilocarb reaction blend batch having 85/15 MHF/DCPD, and preferably using P01 and Luperox® 231 catalysts is used in a system of EXAMPLES 1 to 5 to form a cured material.
  • a polysilocarb reaction blend batch having 65/35 MHF/DCPD, and preferably using P01 and Luperox® 231 catalysts is used in a system of EXAMPLES 1 to 5 to form a cured material.
  • a polysilocarb formulation has 0-20% MHF, 0-30% TV, 50-100% H62 C and 0-5% a hydroxy terminated dimethyl polysiloxane is used in a system of
  • a polysilocarb formulation has 40% MHF, 40% TV, and 20% VT and has a hydride to vinyl molar ratio of 1.12:1 , and may be used as to form strong ceramic beads, e.g., proppants for use in hydraulically fracturing hydrocarbon producing formations is used in a system of EXAMPLES 1 to 5 to form a cured material.
  • a polysilocarb formulation has 42% MHF, 38% TV, and 20% VT and has a hydride to vinyl molar ratio of 1.26:1 , and may be used as to form strong ceramic beads, e.g., proppants for use in hydraulically fracturing hydrocarbon producing formations is used in a system of EXAMPLES 1 to 5 to form a cured material.
  • a polysilocarb formulation has 55% MHF, 25% TV, and 20% VT and has a hydride to vinyl molar ratio of 2.36:1 , and may be used as to form strong ceramic beads, e.g., proppants for use in hydraulically fracturing hydrocarbon producing formations is used in a system of EXAMPLES 1 to 5 to form a cured material.
  • the reactive extrusion equipment is a twin screw extruder with the following configuration and operating conditions: precursor is 50:50 MHF:DCPD; a 28 mm extruder; 48:1 L/D; 7 potential temperature zones; mechanical pump with feed rates from 5-50 Ib/hr; heat traced addition lines (@ 90-110 °F); mixing at the injection port; injection port at 100 psi
  • All pumps are calibrated to deliver the appropriated volumes of material and the P01 catalyst is added to the DCPD raw material.
  • the raw materials are mixed just before the injection port and added to the extruder. There were 100 psi check valves just prior to the injection port to prevent premature mixing of raw materials. Finally, the injection port is not heated but slow increases in temperature due to contact with the extruder barrel.
  • the screw is set at 100 RPM with a material total feed rate of 5 lbs/hour.
  • the catalyst loading is 3% to produce a white crumb like cured material (e.g., white crumb rubber) at the end of the extruder. This crumb cured material is still curing upon exit of the extruder. It is cooled on a shaker table and packaged into 1 liter glass bottles for analysis.
  • FIG. 3 sets forth embodiments of formulations and extruder conditions.
  • FIG. 4 sets forth embodiments of formulations and extruder conditions. HEADINGS AND EMBODIMENTS

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Silicon Polymers (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne des procédés de formation de petites formes volumétriques de matériaux céramiques dérivés de polymères, comprenant des systèmes et des procédés d'extrusion réactionnelle. L'invention concerne des systèmes et un appareil pour former de petites formes volumétriques de matériaux céramiques dérivés de polymère, de matériaux durcis et de matériaux pyrolysés, comprenant des extrudeuses. L'invention concerne en outre des formulations de précurseur de céramique dérivées de polymère polysilocarb.
PCT/US2017/068404 2016-12-27 2017-12-26 Systèmes de réaction d'extrusion et procédés de fabrication de particules de céramique dérivées de polymères WO2018125861A2 (fr)

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WO2019113388A3 (fr) * 2017-12-06 2019-08-01 Melior Innovations, Inc. Appareil de refroidissement et de transport pneumatique pour la fabrication par réaction d'extrusion de céramiques dérivées de polymères
CN110126123A (zh) * 2019-06-03 2019-08-16 杭州致爱包装制品有限公司 一种用与制造聚乙烯的生产系统
CN111152354A (zh) * 2020-01-13 2020-05-15 林智勇 环保再生砖智能生产线
US10836682B2 (en) 2017-07-22 2020-11-17 Melior Innovations, Inc. Methods and apparatus for conducting heat exchanger based reactions
CN113075049A (zh) * 2021-04-02 2021-07-06 山东科技大学 一种变频变强度动静组合加载岩石力学试验机及试验方法
CN113453860A (zh) * 2018-12-12 2021-09-28 佩加索实业股份公司 用于处理聚合材料的设备
CN115096076A (zh) * 2021-04-07 2022-09-23 江苏天海特种装备有限公司 乙炔瓶填料蒸养固化用隧道式推杆加热炉及连续固化工艺

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US7666338B2 (en) * 2004-03-25 2010-02-23 Ppg Industries Ohio, Inc. Focused heat extrusion process for manufacturing powder coating compositions
US7417094B2 (en) * 2004-11-18 2008-08-26 Pripro Polymer, Inc. Cross-linked thermoplastic polyurethane/polyurea and method of making same
PL2346657T3 (pl) * 2008-10-31 2013-09-30 Corning Inc Dwuobwodowa kontrola wsadu wytłaczania prekursora ceramicznego
US9266274B2 (en) * 2010-10-18 2016-02-23 Davis Standard, LLC Heater-cooler system for a barrel of an extruder and a method of using the same
US20160280607A1 (en) * 2013-05-02 2016-09-29 Melior Innovations, Inc. Methods of manufacturing polymer derived ceramic particles.
CN109562530A (zh) * 2016-08-03 2019-04-02 康宁股份有限公司 陶瓷前体批料流变控制的设备和方法

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US10836682B2 (en) 2017-07-22 2020-11-17 Melior Innovations, Inc. Methods and apparatus for conducting heat exchanger based reactions
WO2019113388A3 (fr) * 2017-12-06 2019-08-01 Melior Innovations, Inc. Appareil de refroidissement et de transport pneumatique pour la fabrication par réaction d'extrusion de céramiques dérivées de polymères
CN113453860A (zh) * 2018-12-12 2021-09-28 佩加索实业股份公司 用于处理聚合材料的设备
CN110126123A (zh) * 2019-06-03 2019-08-16 杭州致爱包装制品有限公司 一种用与制造聚乙烯的生产系统
CN111152354A (zh) * 2020-01-13 2020-05-15 林智勇 环保再生砖智能生产线
CN113075049A (zh) * 2021-04-02 2021-07-06 山东科技大学 一种变频变强度动静组合加载岩石力学试验机及试验方法
CN115096076A (zh) * 2021-04-07 2022-09-23 江苏天海特种装备有限公司 乙炔瓶填料蒸养固化用隧道式推杆加热炉及连续固化工艺

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