Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon
• • 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
  • B29C48/07—Flat, e.g. panels
  • B29C48/08—Flat, e.g. panels flexible, e.g. films
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
  • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon
  • C08K3/041—Carbon nanotubes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
  • C08L81/02—Polythioethers; Polythioether-ethers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
  • C08J2381/02—Polythioethers; Polythioether-ethers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/001—Conductive additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K2201/00—Specific properties of additives
  • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K

Definitions

• the present disclosure relates to polyphenylene sulfide (PPS)-based polymers, and in particular to PPS-based polymers including at least two carbon-based fillers that have improved electrical conductivity properties and that are suitable for use in battery electrode plates.
• PPS polyphenylene sulfide
• the composition should contain at least 15 parts by weight of a finely divided conductive carbon powder per hundred parts (pph) of the copolymer. It also provides that 35 pph of the conductive carbon should not be employed; otherwise, the composition is too brittle and also less easily extrudable into thin nonporous sheets. Also, increasing the amount of carbon to about 35 pph tends to increase the permeability of the thin sheets manufactured from such compositions to liquids such as bromine, as an example. It is preferred that the finely divided conductive carbon black has a surface area greater than about 500 m 2 /g, such as those manufactured under the tradename Ketjenblack EC.
• materials were prepared using a lamination process, known as glass-mat reinforced thermoplastics technology or, in a different embodiment, the substrate is made using a slurry process.
• Bromination unlike chlorination, is extremely selective to the chemistry of the polymer matrix used, and the tertiary hydrogens of polypropylene systems react approximately twenty thousand times faster with bromine than the secondary hydrogens in polyethylene.
• Three carbon blacks were used in the compositions of this disclosure, but the Ketjenblack EC 300 J grade offered the best combination of electrical conductivity and processability properties for the amount of carbon used.
• the 362 Patent describes wide carbon black and fiber loadings ranging from 5- 40 wt% and 10-70 wt%, respectively, but also exemplifies a composition having a carbon loading of 18 wt% (identical to Exxon), so it is likely that the carbon and fiber loadings used in the Johnson Controls patent are close to those disclosed in the 816 Patent.
• thermoplastic compositions including: from about 35 wt% to about 65 wt% of at least one polyphenylene sulfide (PPS) polymer; and a combination of at least two carbon-based fillers, including a first carbon-based filler including graphite and a second carbon-based filler including carbon powder, carbon nanotubes, or a combination thereof.
• the first carbon-based filler includes graphite in an amount from about 30 wt% to about 59 wt%.
• the composition exhibits a volume electrical resistivity of less than about 5 Ohm.cm as measured by ASTM D991. The combined weight percent value of all components does not exceed 100 wt%, and all weight percent values are based on the total weight of the composition.
• compositions including from about 35 wt% to about 65 wt% of at least one polyphenylene sulfide (PPS) polymer and a combination of at least two carbon-based fillers, the method including: combining the at least one PPS polymer and the at least two carbon-based fillers to form a mixture; and extruding the mixture to form the composition.
• the at least two carbon-based fillers include a first carbon-based filler including graphite and a second carbon-based filler including carbon powder, carbon nanotubes, or a combination thereof.
• the graphite is present in an amount from about 30 wt% to about 59 wt%.
• the composition exhibits a volume electrical resistivity of less than about 5 Ohm.cm as measured by ASTM D991. The combined weight percent value of all components does not exceed 100 wt%, and all weight percent values are based on the total weight of the composition.
• FIG. 1 is a diagram of an apparatus used for determining shielding effectiveness (SE) according to aspects of the disclosure.
• FIG. 2 is a graph of SE as a function of frequency for example compositions Ex2. 1 and Ex2.2 according to aspects of the disclosure.
• the present disclosure relates to highly-filled plastic materials used, for example, to replace metallic electrode plates of flow batteries, such as zinc bromide and vanadium redox flow batteries.
• These materials include at least one polyphenylene sulfide (PPS) and mixtures of synthetic graphite, carbon nanotubes and conductive carbon powder (e.g., carbon black).
• PPS polyphenylene sulfide
• Compositions according to aspects of the disclosure include high electrical conductivity, good heat and chemical resistance, and processability into thin plastic sheets using conventional polymer processing methods.
• the compositions could replace metals and metalized polymeric materials in the EMI shielding of coaxial cables, cell phones, computers, laptops, monitors, and other sensitive electronic equipment requiring isolation from outside electromagnetic fields.
• Ranges can be expressed herein as from one value (first value) to another value (second value). When such a range is expressed, the range includes in some aspects one or both of the first value and the second value. Similarly, when values are expressed as approximations, by use of the antecedent ‘about,’ it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.
• the terms “about” and “at or about” mean that the amount or value in question can be the designated value, approximately the designated value, or about the same as the designated value. It is generally understood, as used herein, that it is the nominal value indicated ⁇ 10% variation unless otherwise indicated or inferred. The term is intended to convey that similar values promote equivalent results or effects recited in the claims. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but can be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art.
• an amount, size, formulation, parameter or other quantity or characteristic is “about” or “approximate” whether or not expressly stated to be such. It is understood that where “about” is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.
• compositions of the disclosure Disclosed are the components to be used to prepare the compositions of the disclosure as well as the compositions themselves to be used within the methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds cannot be explicitly disclosed, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed and a number of modifications that can be made to a number of molecules including the compounds are discussed, specifically contemplated is each and every combination and permutation of the compound and the modifications that are possible unless specifically indicated to the contrary.
• references in the specification and concluding claims to parts by weight of a particular element or component in a composition or article denotes the weight relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed.
• X and Y are present at a weight ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the compound.
• a weight percent of a component is based on the total weight of the formulation or composition in which the component is included.
• weight percent As used herein the terms “weight percent,” “wt%,” and “wt. %,” which can be used interchangeably, indicate the percent by weight of a given component based on the total weight of the composition, unless otherwise specified. That is, unless otherwise specified, all wt% values are based on the total weight of the composition. It should be understood that the sum of wt% values for all components in a disclosed composition or formulation are equal to 100.
• compositions disclosed herein have certain functions. Disclosed herein are certain structural requirements for performing the disclosed functions and it is understood that there are a variety of structures that can perform the same function that are related to the disclosed structures, and that these structures will typically achieve the same result.
• aspects of the disclosure relate to highly-filled plastic materials that are suitable to replace titanium in electrode plates of zinc bromide flow batteries.
• these materials include at least one polyphenylene sulfide (PPS) and mixtures of synthetic graphite, carbon nanotubes and conductive carbon powder (e.g., carbon black) in different ratios.
• PPS polyphenylene sulfide
• the use of carbon nanotubes in these compositions could allow for a reduction of graphite and carbon powder loadings, thus producing materials of similar electrical conductivity but of improved flow compared to the compositions containing only graphite and carbon powder.
• Three desirable properties for such compounds include high electrical conductivity, chemical resistance, and processability into thin plastic sheets using conventional polymer processing methods.
• Polyphenylene sulfide (PPS) compounds suitable for use in aspects of the disclosure include, but are not limited to FORTRON® 0203 and FORTRON® 0205, both available from Celanese.
• FORTRON® 0203 is a low viscosity, unfilled PPS resin that flows very easily in compounding operations.
• FORTRON® 0205 is an unfilled, medium-range viscosity PPS resin intended for compounding with various fillers. These two grades demonstrate excellent chemical resistance and thermal stability, exhibiting a melting temperature of about 280 °C and a glass transition temperature of about 90 °C.
• Polyphenylene sulfide is a high-temperature semicrystalline polymer that has a symmetrical, rigid backbone chain including recurring aromatic rings linked by sulfides. PPS provides high thermal stability, very high chemical resistance, stiffness, strength and creep resistance.
• Adding glass fibers and glass fiber/mineral mixtures to standard PPS allows service temperatures up to about 240 °C, very good resistance to chemicals and solvents, inherent flame resistance, very low moisture absorption, and excellent creep resistance even at elevated temperatures.
• the chemical structure of PPS provides excellent chemical and thermal resistance, insolubility in all known solvents below 200°C (392°F), and very good stability in both typical and alternative automotive fuels.
• the carbon nanotubes suitable for use in aspects of the disclosure may be added in a form of a custom-made PPS-based masterbatch.
• masterbatches are available from NANOCYL under the PLASTICYLTM trade name. They include 10 wt% of NC7000TM multiwall carbon nanotubes produced by a Catalytic Chemical Vapor Deposition (CCVD) process.
• CCVD Catalytic Chemical Vapor Deposition
• Carbon nanotubes are tube-shaped materials including carbon atoms having a nanometer size diameter. Carbon nanotubes, while appearing as a black powder, have a spaghetti like structure at the nanoscale level.
• Exemplary carbon nanotubes suitable for aspects of the present disclosure have an average diameter of about 10 nanometers (nm), an average length of about 1.5 micron (pm), a surface area of about 250-300 square meters per gram (m 2 /gr), and a volume resistivity of about 10' 4 Ohm-centimeters (Ohm. cm).
• Carbon nanotubes have a high aspect ratio resulting in a relatively low amount of nanotubes needed to reach a specific electrical conductivity. Further, they typically increase viscosity of compositions more than carbon powder at an equal loading, but much lower quantities of nanotubes are typically required. Carbon nanotubes also offer high electrical conductivity, good processability, retention of mechanical properties, high recyclability, and thermal dissipation properties.
• thermoplastic compositions including: from about 35 wt% to about 65 wt% of at least one polyphenylene sulfide (PPS) polymer; and a combination of at least two carbon-based fdlers, including a first carbonbased filler including graphite and a second carbon-based filler including carbon powder, carbon nanotubes, or a combination thereof.
• the first carbon-based filler includes graphite in an amount from about 30 wt% to about 59 wt%.
• the composition exhibits a volume electrical resistivity of less than about 5 Ohm.cm as measured by ASTM D991. The combined weight percent value of all components does not exceed 100 wt%, and all weight percent values are based on the total weight of the composition.
• the composition includes at least 35 wt% of the PPS polymer, or at least 37 wt%, or at least 39 wt%, or at least 41 wt%, or at least 43 wt%, or at least 44 wt%, or at least 45 wt%, or at least 46 wt%, or at least 47 wt%, or at least 48 wt%, or at least 49 wt%, or at least 50 wt%, of the at least one PPS polymer.
• the composition includes at most 65 wt%, or at most 64 wt%, or at most 63 wt%, or at most 62 wt%, or at most 61 wt%, or at most 60 wt%, or at most 59 wt%, or at most 58 wt%, or at most 57 wt%, or at most 56 wt%, or at most 55 wt%, of the at least one PPS polymer.
• the graphite is present in an amount of at least 30 wt%, or at least 31 wt%, or at least 32 wt%, or at least 33 wt%, or at least 34 wt%, or at least 35 wt%, or at least 36 wt%, or at least 37 wt%, or at least 38 wt%, or at least 39 wt%, or at least 40 wt%.
• the graphite is present in an amount of at most 59 wt%, or at most 58 wt%, or at most 57 wt%, or at most 56 wt%, or at most 55 wt%, or at most 54 wt%, or at most 53 wt%, or at most 52 wt%, or at most 51 wt%, or at most 50 wt%.
• the second carbon-based filler includes carbon powder in an amount of from about 2 wt% to about 8 wt%.
• the second carbon-based filler includes carbon powder in an amount of from about 2 wt% to about 8 wt%, or from 2 wt% to 8 wt%, or from 3 wt% to 8 wt%, or from 4 wt% to 8 wt%, or from 5 wt% to 8 wt%, or from 6 wt% to 8 wt%, or from 2 wt% to 7 wt%, or from 2 wt% to 6 wt%, or from 2 wt% to 5 wt%.
• the second carbon-based filler includes carbon nanotubes in an amount of from about 2 wt% to about 6 wt%. In further aspects the second carbon-based filler includes carbon nanotubes in an amount of from about 2 wt% to about 6 wt%, or from 2 wt% to 6 wt%, or from 3 wt% to 6 wt%, or from 4 wt% to 6 wt%, or from 2 wt% to 5 wt%.
• the composition exhibits a volume electrical resistivity of less than 4 Ohm.cm as measured by ASTM D991. In further aspects the composition exhibits a volume electrical resistivity of less than 3 Ohm.cm, or less than 2 Ohm.cm, or less than 1 Ohm.cm, or less than 0.9 Ohm.cm, or less than 0.8 Ohm.cm, or less than 0.7 Ohm.cm, or less than 0.6 Ohm. cm, or less than 0.5 Ohm.cm, or less than 0.4 Ohm. cm, or less than 0.3 Ohm.
• the composition has a Through-plane thermal conductivity of at least 0.6 watts per meter-Kelvin (W/mK) as determined in accordance with ISO 22007- 2.
• W/mK watts per meter-Kelvin
• the composition has a Through-plane thermal conductivity of at least 0.7 W/mK, or at least 0.8 W/mK, or at least 0.9 W/mK, or at least 1.0 W/mK, or at least 1.1 W/mK, or at least 1.2 W/mK, or at least 1.3 W/mK, or at least 1.4 W/mK, or from 0.6 to 1.5 W/mK.
• the composition may in certain aspects have an In-plane thermal conductivity of at least 5.0 W/mK as determined in accordance with ISO 22007-2.
• the composition has an In-plane thermal conductivity of at least 5.4 W/mK, or at least 6 W/mK, or at least 7 W/mK, or at least 8 W/mK, or at least 9 W/mK, or at least 10 W/mK, or at least 11 W/mK, or at least 12 W/mK, or at least 13 W/mK, or at least 14 W/mK, or at least 15 W/mK, or at least 16 W/mK, or from 5-20 W/mK.
• the composition may in some aspects have a bulk thermal conductivity of at least 1.8 W/mK. In further aspects the composition has a bulk thermal conductivity of at least 2.0 W/mK, or at least 2.5 W/mK, or at least 3.0 W/mK, or at least 3.5 W/mK, or at least 4.0 W/mK, or at least 4.5 W/mK, or from 1.8-5 W/mK.
• the composition has a far field electromagnetic wave shielding effectiveness (SE) of at least 80 decibels (dB) at a frequency of from 3 GHz to 6 GHz as tested in accordance with ASTM D4935.
• SE far field electromagnetic wave shielding effectiveness
• the composition has a far field electromagnetic wave SE of at least 85 dB, or at least 90 dB, or at least 95 dB, or at least 100 dB, at a frequency of from 3 GHz to 6 GHz.
• the composition includes at least one additional additive.
• the at least one additional additive may include, but is not limited to, an acid scavenger, an antidrip agent, an antioxidant, an antistatic agent, a chain extender, a colorant, a release agent, a flow promoter, a lubricant, a plasticizer, a quenching agent, a flame retardant, a UV reflecting additive, an impact modifier, a blowing agent, a reinforcing agent, or a combination thereof.
• the composition includes graphite, carbon powder and carbon nanotubes.
• the one or any foregoing components described herein may be first dry blended with each other, or dry blended with any combination of foregoing components, then fed into an extruder from one or multi-feeders, or separately fed into an extruder from one or multi -feeders.
• the fillers used in the disclosure may also be first processed into a masterbatch, then fed into an extruder.
• the components may be fed into the extruder from a throat hopper or any side feeders.
• the extruders used in the disclosure may have a single screw, multiple screws, intermeshing co-rotating or counter rotating screws, non-intermeshing co-rotating or counter rotating screws, reciprocating screws, screws with pins, screws with screens, barrels with pins, rolls, rams, helical rotors, co-kneaders, disc-pack processors, various other types of extrusion equipment, or combinations including at least one of the foregoing.
• the components may also be mixed together and then melt-blended to form the thermoplastic compositions.
• the melt blending of the components involves the use of shear force, extensional force, compressive force, ultrasonic energy, electromagnetic energy, thermal energy or combinations including at least one of the foregoing forces or forms of energy.
• the barrel temperature on the extruder during compounding can be set at the temperature where at least a portion of the polymer has reached a temperature greater than or equal to about the melting temperature, if the resin is a semi -crystalline organic polymer, or the flow point (e.g., the glass transition temperature) if the resin is an amorphous resin.
• thermoplastic composition may first be extruded and formed into pellets. The pellets may then be fed into a molding machine where it may be formed into any desirable shape or product.
• thermoplastic composition emanating from a single melt blender may be formed into sheets or strands and subjected to post-extrusion processes such as annealing, uniaxial or biaxial orientation.
• the temperature of the melt in the present process may in some aspects be maintained as low as possible in order to avoid excessive thermal degradation of the components.
• the melt temperature is maintained between about 230°C and about 350°C, although higher temperatures can be used provided that the residence time of the resin in the processing equipment is kept relatively short.
• the melt processed composition exits processing equipment such as an extruder through small exit holes in a die.
• the resulting strands of molten resin may be cooled by passing the strands through a water bath.
• the cooled strands can be chopped into pellets for packaging and further handling.
• a method for forming a composition including from about 35 wt% to about 65 wt% of at least one polyphenylene sulfide (PPS) polymer and a combination of at least two carbon-based fillers, the method including: combining the at least one PPS polymer and the at least two carbon-based fillers to form a mixture; and extruding the mixture to form the composition.
• the at least two carbon-based fillers include a first carbon-based filler including graphite and a second carbon-based filler including carbon powder, carbon nanotubes, or a combination thereof.
• the graphite is present in an amount from about 30 wt% to about 59 wt%.
• the composition exhibits a volume electrical resistivity of less than about 5 Ohm. cm as measured by ASTM D991. The combined weight percent value of all components does not exceed 100 wt%, and all weight percent values are based on the total weight of the composition.
• one or more of the carbon-based fillers is provided in a form of a PPS-based masterbatch composition.
• Thermoplastic compositions formed according to these methods may include the components and amounts described herein, and may have one or more of the properties described herein.
• the present disclosure pertains to shaped, formed, or molded articles including the thermoplastic compositions.
• the thermoplastic compositions can be molded into useful shaped articles by a variety of means such as injection molding, extrusion, rotational molding, blow molding and thermoforming to form articles and structural components of, for example, personal or commercial electronics devices, including but not limited to cellular telephones, tablet computers, personal computers, notebook and portable computers, and other such equipment, medical applications, RFID applications, automotive applications, and the like.
• the article is extrusion molded.
• the article is injection molded.
• the article is an electrically conductive electrode plate of a flow battery, a thermally conductive plate of a heat exchanger used to transfer heat between two fluids, or an enclosure or package to protect electronic devices used in medical, military, and aerospace electronics from the damaging effect of electromagnetic radiation.
• thermoplastic compositions may be extruded into a sheet.
• thermoplastic compositions may be extruded, injection molded, compression molded, injection-compression molded, or some combination of these processes.
• Sheets of varying thickness may be formed.
• the compositions may be formed into sheets having a thickness of up to 3 mm or greater.
• thin sheets of from 0.020 inches to 0.060 inches may be formed.
• thin sheets have a thickness of no more than 0.125 inches.
• extrusion forming may be a desirable process for making these thin sheets.
• Thin sheets having a thickness of no more than 0.125 inches may in some aspects be suitable for use in flow batteries (e.g., bipolar electrode plates in such batteries). In other applications - for example heat exchanger plates and enclosures for automotive radar sensors - thicker sheets may be desirable.
• the present disclosure pertains to and includes at least the following aspects.
• a thermoplastic composition comprising, consisting of, or consisting essentially of: from about 35 wt% to about 65 wt% of at least one polyphenylene sulfide (PPS) polymer; and a combination of at least two carbon-based fillers, comprising a first carbon-based filler comprising graphite and a second carbon-based filler comprising carbon powder, carbon nanotubes, or a combination thereof, wherein the first carbon-based filler comprises graphite in an amount from about 30 wt% to about 59 wt%, wherein the composition exhibits a volume electrical resistivity of less than about 5 Ohm. cm as measured by ASTM D991, and wherein the combined weight percent value of all components does not exceed 100 wt%, and all weight percent values are based on the total weight of the composition.
• PPS polyphenylene sulfide
• thermoplastic composition according to Aspect 1 wherein the second carbon-based filler comprises carbon powder in an amount of from about 2 wt% to about 8 wt%.
• Aspect 3 The thermoplastic composition according to Aspect 1 or 2, wherein the second carbon-based filler comprises carbon nanotubes in an amount of from about 2 wt% to about 6 wt%.
• Aspect 4 The thermoplastic composition according to any of Aspects 1 to 3, wherein the composition exhibits a volume electrical resistivity of less than 1 Ohm. cm as measured by ASTM D991.
• Aspect 5 The thermoplastic composition according to any of Aspects 1 to 4, wherein the composition has a Through-plane thermal conductivity of at least 0.8 W/mK as determined in accordance with ISO 22007-2, or wherein the composition has an In-plane thermal conductivity of at least 5.4 W/mK as determined in accordance with ISO 22007-2.
• Aspect 6 The thermoplastic composition according to any of Aspects 1 to 5, wherein the composition has a bulk thermal conductivity of at least 1.8 W/mK.
• Aspect 7 The thermoplastic composition according to any of Aspects 1 to 6, wherein the composition has a far field electromagnetic wave shielding effectiveness (SE) of at least 80 decibels (dB) at a frequency of from 3 GHz to 6 GHz as tested in accordance with ASTM D4935.
• SE far field electromagnetic wave shielding effectiveness
• Aspect 8 The thermoplastic composition according to any of Aspects 1 to 7, wherein the composition comprises at least one additional additive.
• thermoplastic composition according to Aspect 8 wherein the at least one additional additive comprises an acid scavenger, an anti-drip agent, an antioxidant, an antistatic agent, a chain extender, a colorant, a release agent, a flow promoter, a lubricant, a plasticizer, a quenching agent, a flame retardant, a UV reflecting additive, an impact modifier, a blowing agent, a reinforcing agent, or a combination thereof.
• the at least one additional additive comprises an acid scavenger, an anti-drip agent, an antioxidant, an antistatic agent, a chain extender, a colorant, a release agent, a flow promoter, a lubricant, a plasticizer, a quenching agent, a flame retardant, a UV reflecting additive, an impact modifier, a blowing agent, a reinforcing agent, or a combination thereof.
• Aspect 10 The thermoplastic composition according to any of Aspects 1 to 9, wherein the composition comprises graphite, carbon powder and carbon nanotubes.
• Aspect 11 An extruded sheet comprising the composition according to any of Aspects 1 to 10.
• Aspect 12 The extruded sheet according to Aspect 11, wherein the sheet has a thickness of no more than 0.125 inches (in).
• a method for forming a composition comprising, consisting of, or consisting essentially of, from about 35 wt% to about 65 wt% of at least one polyphenylene sulfide (PPS) polymer and a combination of at least two carbon-based fillers, the method comprising, consisting of, or consisting essentially of: combining the at least one PPS polymer and the at least two carbon-based fillers to form a mixture; and extruding the mixture to form the composition, wherein the at least two carbon-based fillers comprise a first carbon-based filler comprising graphite and a second carbon-based filler comprising carbon powder, carbon nanotubes, or a combination thereof, wherein the graphite is present in an amount from about 30 wt% to about 59 wt%, wherein the composition exhibits a volume electrical resistivity of less than about 5 Ohm. cm as measured by ASTM D991, and wherein the combined weight percent value of all components does not exceed 100 wt%
• PPS polyphen
• Aspect 14 The method according to Aspect 13, wherein one or more of the carbon-based fillers is provided in a form of a PPS-based masterbatch composition.
• Aspect 15 An article comprising the thermoplastic composition according to any of Aspects 1 to 10, wherein the article comprises: an electrically conductive electrode plate of a flow battery; a thermally conductive plate of a heat exchanger used to transfer heat between two fluids; or an enclosure or package to protect electronic devices used in medical, military, or aerospace electronics from electromagnetic radiation.
• reaction conditions e.g., component concentrations, desired solvents, solvent mixtures, temperatures, pressures and other reaction ranges and conditions that can be used to optimize the product purity and yield obtained from the described process. Only reasonable and routine experimentation will be required to optimize such process conditions.
• the PPS-based masterbatch used in the aspects of the disclosure was diluted with fresh, unfilled polyphenylene sulfide resin (e.g., FORTRON® 0203B6).
• FORTRON® 0203B6 is a low viscosity, unfilled grade that flows very easily in compounding operations.
• Compositions according to aspects of the disclosure included from about 45 wt% to about 65 wt% of the masterbatch; the amount of fresh PPS resin was kept at 15 wt% for most of the conditions investigated.
• These polymer/masterbatch ratios produced materials including from about 4.5 weight % to about 6.5 weight % of carbon nanotubes in the final formulation.
• the degree of crystallinity of both PPS resins was investigated by DSC, and it was found to be 63.8% for FORTRON® 0203B6 and 56.6% for FORTRON® 0205B4. These values were calculated using the heat of melting, which was equal to 48.83 Joules per gram (J/g) for FORTRON® 0203B6 and 43.30 J/g for FORTRON® 0205B4, and the theoretical melting enthalpy obtained from literature, which is equal to 76.5 J/g for a PPS having 100% crystallinity.
• PPS-based compositions described herein were injection molded into 150 millimeter (mm) x 108 mm plaques having a thickness of 2.50 mm and 2.00 mm; the plaques were tested for physical and electrical conductivity properties.
• the graphite used in the compositions was a highly crystalline material of high purity, which is produced at ultra- high temperatures that vaporize impurities such as metal oxides, sulfur, iron, aluminum and many others to render 99%+ pure carbon synthetic graphite in particle sizes from less than 1 micron to several hundreds of microns.
• the carbon powder (carbon black) used in the compositions has a primary/basic particle size of some 10-50 nanometers (nm), with aggregates of several hundred nanometers in size, and agglomerates as large as 100-200 microns.
• compositions were formed, injection molded and extruded into plaques and certain properties were tested according to Table 1 .
• compositions were injection moldable under conventional molding conditions. All of the compositions except comparative composition Cl.7 were extrudable at conventional extrusion temperatures ( ⁇ 350 degrees Celsius (°C)) and pressures ( ⁇ 200 pounds per square inch (PSI)) for Exl.6 and ⁇ 35 psi for Exl.2-Exl.5). Composition Cl.7 was difficult to extrude and required an extrusion melt temperature of about 367 °C and a die melt pressure of about 600 psi. In view of these required extrusion conditions composition Cl.7 containing an amount of total carbon filler in excess of 60 wt% is not practical for injection molded articles.
• comparative composition Cl . 1 having less than 35 wt% carbon-based filler including 30 wt% graphite had high volume electrical resistivity of greater than 5 Ohm. centimeters (Ohm.cm) as determined in accordance with ASTM D991.
• the composition also had low thermal conductivity properties - less than 0.6 watts per meter Kelvin (W/mK) in the Through-plane direction, less than 5.4 W/mK in the In-plane direction, and a bulk thermal conductivity of less than 1.8 W/mK.
• Bulk thermal conductivity is calculated as the square root of the product of Through-plane thermal conductivity and In-plane thermal conductivity.
• the example compositions Exl.2 through Exl.6 having at least 35 wt% carbon-based fdler including at least 30 wt% graphite had relatively low volume resistivity (less than 5 Ohm.com), high Through-plane thermal conductivity (above 0.6 W/mK), high In-plane thermal conductivity (above 5.4 W/mK) and high bulk conductivity (above 1.8 W/mK).
• the thermal conductivity of these materials was measured according to ISO 22007-2 for Through and In-plane conductivities (measured on 60 mm x 60 mm x 3 mm plaques).
• the bulk thermal conductivity was calculated from the values of the Through-plane Thermal Conductivity and the In-plane Thermal Conductivity.
• Some of the example compositions exhibited a surface electrical resistivity of less than 4 Ohm/sq as determined in accordance with ASTM D257, and a Total Shielding Effectiveness of at least 35 dB as determined in accordance with SABIC’s modified ASTM D4935 test method which is based on the so-called FaradexTM meter.
• the modified ASTM D4935 method uses a pulsed magnetic field through a conductive material to measure the electrical conductivity of the material. This conductivity measuring system reports both square resistivity and far field shielding. The electromagnetic shielding of the far field, in dB, is calculated from the square resistance measured in Ohm.
• the test requires the evaluation of at least 5 plaques of 3 in x 5 in dimensions. It has been observed that for carbon-based materials the FaradexTM meter is less reliable than the standard method because the modified method for calculating SE only takes the reflection (and not the absorption) portion of the radiation into account.
• compositions were formed, injection molded and extruded into plaques and certain properties were tested according to Table 2.
• compositions Ex2.1 to Ex2.3 had a volume electrical resistivity of less than 0.3 Ohm.cm as determined in accordance with ASTM D991 (0.180 Ohm.cm, 0.202 Ohm.cm and 0.089 Ohm.cm, respectively). Also, the Through-plane Thermal Conductivity (W/mK) varied between 1.09 and 1.42, the In-plane Thermal Conductivity (W/mK) between 11.12 and 16.90, and the Bulk Thermal Conductivity (W/mK) between 3.97 and 4.54.
• W/mK Through-plane Thermal Conductivity
• W/mK In-plane Thermal Conductivity
• W/mK Bulk Thermal Conductivity
• Shielding Effectiveness properties were also determined for compositions Ex2.1 and Ex2.2 in accordance with ASTM D4935 using the testing apparatus of FIG. 1. Specifically, the far field electromagnetic wave shielding effectiveness (SE) was evaluated for a frequency range of from about 30 megahertz (MHz) to about 6 gigahertz (GHz). The SE results are shown in FIG. 2. The results show that compositions Ex2. 1 and Ex2.2 have similar shielding effectiveness. In particular it was observed that both samples had a SE of at least 90 dB at a frequency of 3 GHz and above.
• SE electromagnetic wave shielding effectiveness
• compositions were formed, injection molded and extruded into plaques and certain properties were tested according to Table 3:
• Comparative composition C3. 1 was not extrudable; it was too viscous and plugged the die head of the extruder in a short amount of time.
• Example compositions Ex3.2 and Ex3.3 were extrudable at conventional extrusion temperatures and pressures.
• compositions Ex3.2 and Ex3.3 were measured according to ASTM D991, with the results shown in Table 3; the compositions had a volume electrical resistivity of 0.24 Ohm. cm and 0.15 Ohm. cm, respectively.
• melt flow rate (MFR) of Ex3.2 and Ex3.3 could not be measured due to the die of the testing machine getting completely plugged when trying to flow the melt out of the tester. It is speculated that since the polymer crystallizes rapidly above the Tg, it solidifies before it can exit out of the die thus plugging the orifice of the MFR tester. This situation may be aggravated by the fact that the high loadings of carbon filler present in these materials may lead to even higher crystallization speeds thus helping the polymer to solidify faster when cooling.

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