WO2022177560A1 - Polymer composition for use in an antenna system - Google Patents
Polymer composition for use in an antenna system Download PDFInfo
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- WO2022177560A1 WO2022177560A1 PCT/US2021/018492 US2021018492W WO2022177560A1 WO 2022177560 A1 WO2022177560 A1 WO 2022177560A1 US 2021018492 W US2021018492 W US 2021018492W WO 2022177560 A1 WO2022177560 A1 WO 2022177560A1
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- WIPO (PCT)
- Prior art keywords
- polymer composition
- mol
- polymer
- antenna
- antenna system
- Prior art date
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- 229920000642 polymer Polymers 0.000 title claims abstract description 131
- 239000000203 mixture Substances 0.000 title claims abstract description 100
- 239000000463 material Substances 0.000 claims abstract description 30
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- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
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- 239000006229 carbon black Substances 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
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- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
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- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
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- ZZBBCSFCMKWYQR-UHFFFAOYSA-N copper;dioxido(oxo)silane Chemical compound [Cu+2].[O-][Si]([O-])=O ZZBBCSFCMKWYQR-UHFFFAOYSA-N 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- FNIATMYXUPOJRW-UHFFFAOYSA-N cyclohexylidene Chemical group [C]1CCCCC1 FNIATMYXUPOJRW-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- QNSNRZKZPUIPED-UHFFFAOYSA-N dibenzo-p-dioxin-1,7-diol Chemical compound C1=CC=C2OC3=CC(O)=CC=C3OC2=C1O QNSNRZKZPUIPED-UHFFFAOYSA-N 0.000 description 1
- LMFFOBGNJDSSOI-UHFFFAOYSA-N dibenzofuran-3,6-diol Chemical compound C1=CC=C2C3=CC=C(O)C=C3OC2=C1O LMFFOBGNJDSSOI-UHFFFAOYSA-N 0.000 description 1
- TUPADZRYMFYHRB-UHFFFAOYSA-N dibenzothiophene-3,6-diol Chemical compound C1=CC=C2C3=CC=C(O)C=C3SC2=C1O TUPADZRYMFYHRB-UHFFFAOYSA-N 0.000 description 1
- 235000019821 dicalcium diphosphate Nutrition 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- SUNVJLYYDZCIIK-UHFFFAOYSA-N durohydroquinone Chemical compound CC1=C(C)C(O)=C(C)C(C)=C1O SUNVJLYYDZCIIK-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004404 heteroalkyl group Chemical group 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000004446 heteroarylalkyl group Chemical group 0.000 description 1
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000003116 impacting effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
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- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical group II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
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- 238000003801 milling Methods 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- TVIDDXQYHWJXFK-UHFFFAOYSA-N n-Dodecanedioic acid Natural products OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- VAWFFNJAPKXVPH-UHFFFAOYSA-N naphthalene-1,6-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC2=CC(C(=O)O)=CC=C21 VAWFFNJAPKXVPH-UHFFFAOYSA-N 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229960005489 paracetamol Drugs 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
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- 230000001902 propagating effect Effects 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- QKYIPVJKWYKQLX-UHFFFAOYSA-N pyrene-2,7-diol Chemical compound C1=C(O)C=C2C=CC3=CC(O)=CC4=CC=C1C2=C43 QKYIPVJKWYKQLX-UHFFFAOYSA-N 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229920006012 semi-aromatic polyamide Polymers 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Natural products OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 1
- KOJDPIMLHMVCDM-UHFFFAOYSA-N thianthrene-1,7-diol Chemical compound C1=CC=C2SC3=CC(O)=CC=C3SC2=C1O KOJDPIMLHMVCDM-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- GWBUNZLLLLDXMD-UHFFFAOYSA-H tricopper;dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Cu+2].[Cu+2].[Cu+2].[O-]C([O-])=O.[O-]C([O-])=O GWBUNZLLLLDXMD-UHFFFAOYSA-H 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 150000004684 trihydrates Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q1/00—Details of, or arrangements associated with, antennas
- H01Q1/12—Supports; Mounting means
- H01Q1/22—Supports; Mounting means by structural association with other equipment or articles
- H01Q1/24—Supports; Mounting means by structural association with other equipment or articles with receiving set
- H01Q1/241—Supports; Mounting means by structural association with other equipment or articles with receiving set used in mobile communications, e.g. GSM
- H01Q1/246—Supports; Mounting means by structural association with other equipment or articles with receiving set used in mobile communications, e.g. GSM specially adapted for base stations
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q1/00—Details of, or arrangements associated with, antennas
- H01Q1/36—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith
- H01Q1/38—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith formed by a conductive layer on an insulating support
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q21/00—Antenna arrays or systems
- H01Q21/06—Arrays of individually energised antenna units similarly polarised and spaced apart
- H01Q21/061—Two dimensional planar arrays
-
- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Definitions
- a polymer composition that comprises a semiconductive material distributed within a polymer matrix.
- the semiconductive material includes inorganic particles and an electrically conductive material, the inorganic particles having an average particle size of from about 0.1 to about 100 pm and an electrical conductivity about 500 pS/cm or less.
- the polymer matrix contains at least one thermoplastic high performance polymer having a deflection under load of about 40°C or more.
- the polymer composition exhibits a dielectric constant of about 4 or more and a dissipation factor of about 0.3 or less, as determined at a frequency of 2 GHz.
- FIGs. 1 -2 are respective front and rear perspective views of one embodiment of an electronic component that can employ an antenna system;
- Fig. 3 is a top view of an illustrative inverted-F antenna resonating element for one embodiment of an antenna system;
- Fig. 4 is a top view of an illustrative monopole antenna resonating element for one embodiment of an antenna system;
- FIG. 5 is a top view of an illustrative slot antenna resonating element for one embodiment of an antenna system
- FIG. 6 is a top view of an illustrative patch antenna resonating element for one embodiment of an antenna system
- Fig. 7 is a top view of an illustrative multibranch inverted-F antenna resonating element for one embodiment of an antenna system
- Fig. 8 depicts a 5G antenna system including a base station, one or more relay stations, one or more user computing devices, one or more or more Wi Fi repeaters according to aspects of the present disclosure
- Fig. 9A illustrates a top-down view of an example user computing device including 5G antennas according to aspects of the present disclosure
- Fig. 9B illustrates a side elevation view of the example user computing device of Fig. 9A including 5G antennas according to aspects of the present disclosure
- FIG. 10 illustrates an enlarged view of a portion of the user computing device of FIG. 9A
- Fig. 11 illustrates a side elevation view of co-planar waveguide antenna array configuration according to aspects of the present disclosure
- Fig. 12A illustrates an antenna array for massive multiple-in-multiple- out configurations according to aspects of the present disclosure
- Fig. 12B illustrates an antenna array formed with laser direct structuring according to aspects of the present disclosure
- Fig. 12C illustrates an example antenna configuration according to aspects of the present disclosure.
- Figs. 13A through 13C depict simplified sequential diagrams of a laser direct structuring manufacturing process that can be used to form an antenna system.
- the present invention is directed to a polymer composition that contains a semiconductive material that includes a combination of inorganic particles and an electrically conductive material.
- the semiconductive material is distributed within a polymer matrix that includes a high performance polymer.
- the polymer composition may exhibit a high dielectric constant of about 4 or more, in some embodiments about 8 or more, in some embodiments about 10 or more, in some embodiments from about 10 to about 30, in some embodiments from about 11 to about 25, and in some embodiments, from about 12 to about 24, as determined by the split post resonator method at a frequency of 2 GHz.
- a high dielectric constant can facilitate the ability to form a thin substrate and also allow multiple conductive elements (e.g., antennae) to be employed that operate simultaneously with only a minimal level of electrical interference.
- the dissipation factor, a measure of the loss rate of energy may also be relatively low, such as about 0.3 or less, in some embodiments about 0.1 or less, in some embodiments about 0.06 or less, in some embodiments about
- the present inventor has also surprisingly discovered that the dielectric constant and dissipation factor can be maintained within the ranges noted above even when exposed to various temperatures, such as a temperature of from about -30°C to about 100°C.
- the ratio of the dielectric constant after heat cycling to the initial dielectric constant may be about 0.8 or more, in some embodiments about 0.9 or more, and in some embodiments, from about 0.95 to about 1.1.
- the ratio of the dissipation factor after being exposed to the high temperature to the initial dissipation factor may be about 1.3 or less, in some embodiments about 1.2 or less, in some embodiments about 1.1 or less, in some embodiments about 1.0 or less, in some embodiments about 0.95 or less, in some embodiments from about 0.1 to about 0.95, and in some embodiments, from about 0.2 to about 0.9.
- the change in dissipation factor i.e. , the initial dissipation factor - the dissipation factor after heat cycling
- polymer compositions that possess the combination of a high dielectric constant and low dissipation factor would not also possess sufficiently good mechanical properties and ease in processing (i.e. , low viscosity) to enable their use in certain types of applications. Contrary to conventional thought, however, the polymer composition has been found to possess both excellent mechanical properties and processability. For example, the polymer composition may possess a high impact strength, which is useful when forming thin substrates.
- the composition may, for instance, possess a Charpy notched impact strength of about 0.5 kJ/m 2 or more, in some embodiments from about 1 to about 60 kJ/m 2 , in some embodiments from about 2 to about 50 kJ/m 2 , and in some embodiments, from about 5 to about 45 kJ/m 2 , as determined at a temperature of 23°C in accordance with ISO Test No. ISO 179- 1 :2010.
- the tensile and flexural mechanical properties of the composition may also be good.
- the polymer composition may exhibit a tensile strength of from about 20 to about 500 MPa, in some embodiments from about 50 to about 400 MPa, and in some embodiments, from about 70 to about 350 MPa; a tensile break strain of about 0.4% or more, in some embodiments from about 0.5% to about 10%, and in some embodiments, from about 0.6% to about 3.5%; and/or a tensile modulus of from about 5,000 MPa o about 20,000 MPa, in some embodiments from about 8,000 MPa to about 20,000 MPa, and in some embodiments, from about 10,000 MPa to about 20,000 MPa.
- the tensile properties may be determined at a temperature of 23°C in accordance with ISO Test No. 527:2019.
- the polymer composition may also exhibit a flexural strength of from about 20 to about 500 MPa, in some embodiments from about 50 to about 400 MPa, and in some embodiments, from about 100 to about 350 MPa; a flexural elongation of about 0.4% or more, in some embodiments from about 0.5% to about 10%, and in some embodiments, from about 0.6% to about 3.5%; and/or a flexural modulus of from about 5,000 MPa o about 20,000 MPa, in some embodiments from about 8,000 MPa to about 20,000 MPa, and in some embodiments, from about 10,000 MPa to about 15,000 MPa.
- the flexural properties may be determined at a temperature of 23°C in accordance with 178:2019.
- the polymer matrix contains one or more thermoplastic high performance polymers, generally in an amount of from about 15 wt.% to about 85 wt.%, in some embodiments from about 20 wt.% to about 75 wt.%, and in some embodiments, from about 30 wt.% to about 50 wt.% of the entire polymer composition.
- the high performance polymers have a high degree of heat resistance, such as reflected by a deflection temperature under load (“DTUL”) of about 40°C or more, in some embodiments about 50°C or more, in some embodiments about 60°C or more, in some embodiments from about from about 100°C to about 320°C, in some embodiments from about 150°C to about 310°C, and in some embodiments, from about 220°C to about 300°C, as determined in accordance with ISO 75-2:2013 at a load of 1.8 MPa.
- DTUL deflection temperature under load
- the polymers also typically have a high glass transition temperature, such as about 40°C or more, in some embodiments about 50°C or more, in some embodiments about 60°C or more, in some embodiments about 70°C or more, in some embodiments about 80°C or more, and in some embodiments, from about 100°C to about 320°C.
- the high performance polymers may also have a high melting temperature, such as about 140°C or more, in some embodiments from about 150°C to about 420°C, and in some embodiments, in some embodiments from about 200°C to about 410°C, and in some embodiments, from about 300°C to about 400°C.
- the glass transition and melting temperatures may be determined as is well known in the art using differential scanning calorimetry ("DSC"), such as determined by ISO 11357-2:2020 (glass transition) and 11357- 3:2018 (melting).
- Suitable high performance, thermoplastic polymers for this purpose may include, for instance, polyamides (e.g., aliphatic, semi-aromatic, or aromatic polyamides), polyesters, polyarylene sulfides, liquid crystalline polymers (e.g., wholly aromatic polyesters, polyesteramides, etc.), polycarbonates, polyphenylene ethers, polyphenylene oxides, etc., as well as blends thereof.
- polyamides e.g., aliphatic, semi-aromatic, or aromatic polyamides
- polyesters e.g., polyarylene sulfides
- liquid crystalline polymers e.g., wholly aromatic polyesters, polyesteramides, etc.
- polycarbonates e.g., wholly aromatic polyesters, polyesteramides, etc.
- polyphenylene ethers e.g., polyphenylene oxides, etc.
- Aromatic polymers are particularly suitable for use in the polymer matrix.
- the aromatic polymers can be substantially amorphous, semi crystalline, or crystalline in nature.
- a suitable semi-crystalline aromatic polymer for instance, is an aromatic polyester, which may be a condensation product of at least one diol (e.g., aliphatic and/or cycloaliphatic) with at least one aromatic dicarboxylic acid, such as those having from 4 to 20 carbon atoms, and in some embodiments, from 8 to 14 carbon atoms.
- Suitable diols may include, for instance, neopentyl glycol, cyclohexanedimethanol, 2, 2-dimethyl-1 ,3- propane diol and aliphatic glycols of the formula HO(CH2)nOH where n is an integer of 2 to 10.
- Suitable aromatic dicarboxylic acids may include, for instance, isophthalic acid, terephthalic acid, 1 ,2-di(p-carboxyphenyl)ethane, 4,4'- dicarboxydiphenyl ether, etc., as well as combinations thereof. Fused rings can also be present such as in 1 ,4- or 1 ,5- or 2,6-naphthalene-dicarboxylic acids.
- aromatic polyesters may include, for instance, polyethylene terephthalate) (PET), poly(1, 4-butylene terephthalate) (PBT), poly(1 ,3-propylene terephthalate) (PPT), poly(1, 4-butylene 2,6-naphthalate) (PBN), poly(ethylene 2,6-naphthalate) (PEN), poly(1 ,4-cyclohexylene dimethylene terephthalate) (PCT), as well as mixtures of the foregoing.
- PET polyethylene terephthalate
- PBT poly(1, 4-butylene terephthalate)
- PPT poly(1 ,3-propylene terephthalate)
- PBN poly(1, 4-butylene 2,6-naphthalate)
- PEN poly(ethylene 2,6-naphthalate)
- PCT poly(1 ,4-cyclohexylene dimethylene terephthalate)
- modifying acid and/or diol may be used to form a derivative of such polymers.
- modifying acid and modifying diol are meant to define compounds that can form part of the acid and diol repeat units of a polyester, respectively, and which can modify a polyester to reduce its crystallinity or render the polyester amorphous.
- modifying acid components may include, but are not limited to, isophthalic acid, phthalic acid, 1,3- cyclohexanedicarboxylic acid, 1 ,4-cyclohexane dicarboxylic acid, 2,6-naphthaline dicarboxylic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, suberic acid, 1,12-dodecanedioic acid, etc.
- a functional acid derivative thereof such as the dimethyl, diethyl, or dipropyl ester of the dicarboxylic acid.
- the anhydrides or acid halides of these acids also may be employed where practical.
- modifying diol components may include, but are not limited to, neopentyl glycol, 1 ,4-cyclohexanedimethanol, 1,2- propanediol, 1,3-propanediol, 2-methy-1 ,3-propanediol, 1 ,4-butanediol, 1,6- hexanediol, 1 ,2-cyclohexanediol, 1 ,4-cyclohexanediol, 1 ,2-cyclohexanedimethanol, 1 ,3-cyclohexanedimethanol, 2,2,4,4-tetramethyl 1,3-cyclobutane diol, Z,8- bis(hydroxymethyltricyclo-[5.2.1.0]-decane wherein Z represents 3, 4, or 5; 1,4- bis(2-hydroxyethoxy)benzene, 4,4'-bis(2-hydroxyethoxy) diphenylether [bis- hydroxyethyl
- diethylene glycol triethylene glycol, dipropylene glycol, tripropylene glycol, etc.
- these diols contain 2 to 18, and in some embodiments, 2 to 8 carbon atoms.
- Cycloaliphatic diols can be employed in their cis- or trans configuration or as mixtures of both forms.
- aromatic polyesters such as described above, typically have a
- DTUL value of from about 40°C to about 80°C, in some embodiments from about
- the aromatic polyesters likewise typically have a glass transition temperature of from about
- 30°C to about 120°C in some embodiments from about 40°C to about 110°C, and in some embodiments, from about 50°C to about 100°C, such as determined by ISO 11357-2:2020, as well as a melting temperature of from about 170°C to about 300°C, in some embodiments from about 190°C to about 280°C, and in some embodiments, from about 210°C to about 260°C, such as determined in accordance with ISO 11357-2:2018.
- the aromatic polyesters may also have an intrinsic viscosity of from about 0.1 dl/g to about 6 dl/g, in some embodiments from about 0.2 to about 5 dl/g, and in some embodiments from about 0.3 to about 1 dl/g, such as determined in accordance with ISO 1628-5:1998.
- Polyarylene sulfides are also suitable semi-crystalline aromatic polymers.
- the polyarylene sulfide may be homopolymers or copolymers.
- selective combination of dihaloaromatic compounds can result in a polyarylene sulfide copolymer containing not less than two different units.
- a polyarylene sulfide copolymer can be formed containing segments having the structure of formula: and segments having the structure of formula: or segments having the structure of formula:
- the polyarylene sulfide may be linear, semi-linear, branched or crosslinked.
- Linear polyarylene sulfides typically contain 80 mol% or more of the repeating unit -(Ar-S)-.
- Such linear polymers may also include a small amount of a branching unit or a cross-linking unit, but the amount of branching or cross- linking units is typically less than about 1 mol% of the total monomer units of the polyarylene sulfide.
- a linear polyarylene sulfide polymer may be a random copolymer or a block copolymer containing the above-mentioned repeating unit.
- Semi-linear polyarylene sulfides may likewise have a cross-linking structure or a branched structure introduced into the polymer a small amount of one or more monomers having three or more reactive functional groups.
- monomer components used in forming a semi-linear polyarylene sulfide can include an amount of polyhaloaromatic compounds having two or more halogen substituents per molecule which can be utilized in preparing branched polymers.
- Such monomers can be represented by the formula R'X n , where each X is selected from chlorine, bromine, and iodine, n is an integer of 3 to 6, and R' is a polyvalent aromatic radical of valence n which can have up to about 4 methyl substituents, the total number of carbon atoms in R' being within the range of 6 to about 16.
- Examples of some polyhaloaromatic compounds having more than two halogens substituted per molecule that can be employed in forming a semi-linear polyarylene sulfide include 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3- dichloro-5-bromobenzene, 1 ,2,4-triiodobenzene, 1 ,2,3,5-tetrabromobenzene, hexachlorobenzene, 1 ,3,5-trichloro-2,4,6-trimethylbenzene, 2, 2', 4,4'- tetrachlorobiphenyl, 2,2',5,5'-tetra-iodobiphenyl, 2,2',6,6'-tetrabromo-3,3',5,5'- tetramethylbiphenyl, 1 ,2,3,4-tetrachloronaphthalene, 1 ,2,4-tribromo-6- methylna
- the polyarylene sulfides typically have a DTUL value of from about 70°C to about 220°C, in some embodiments from about 90°C to about 200°C, and in some embodiments, from about 120°C to about 180°C as determined in accordance with ISO 75-2:2013 at a load of 1.8 MPa.
- the polyarylene sulfides likewise typically have a glass transition temperature of from about 50°C to about 120°C, in some embodiments from about 60°C to about 115°C, and in some embodiments, from about 70°C to about 110°C, such as determined by ISO 11357-2:2020, as well as a melting temperature of from about 220°C to about 340°C, in some embodiments from about 240°C to about 320°C, and in some embodiments, from about 260°C to about 300°C, such as determined in accordance with ISO 11357-3:2018.
- substantially amorphous polymers may also be employed that lack a distinct melting point temperature.
- Suitable amorphous polymers may include, for instance, aromatic polycarbonates, which typically contains repeating structural carbonate units of the formula -R 1 -0-C(0)-0-.
- the polycarbonate is aromatic in that at least a portion (e.g., 60% or more) of the total number of R 1 groups contain aromatic moieties and the balance thereof are aliphatic, alicyclic, or aromatic.
- R 1 may a C6-30 aromatic group, that is, contains at least one aromatic moiety.
- R 1 is derived from a dihydroxy aromatic compound of the general formula HO-R 1 -OH, such as those having the specific formula referenced below:
- a 1 and A 2 are independently a monocyclic divalent aromatic group; and Y 1 is a single bond or a bridging group having one or more atoms that separate A 1 from A 2 .
- the dihydroxy aromatic compound may be derived from the following formula (I): wherein,
- R a and R b are each independently a halogen or C1-12 alkyl group, such as a C1-3 alkyl group (e.g., methyl) disposed meta to the hydroxy group on each arylene group; p and q are each independently 0 to 4 (e.g., 1); and
- X a represents a bridging group connecting the two hydroxy-substituted aromatic groups, where the bridging group and the hydroxy substituent of each C6 arylene group are disposed ortho, meta, or para (specifically para) to each other on the C6 arylene group.
- Exemplary groups of this type include methylene, cyclohexylmethylene, ethylidene, neopentylidene, and isopropylidene, as well as 2-[2.2.1]-bicycloheptylidene, cyclohexylidene, cyclopentylidene, cyclododecylidene, and adamantylidene.
- X a is a substituted cycloalkylidene is the cyclohexylidene-bridged, alkyl- substituted bisphenol of the following formula (II): wherein, R a' and R b' are each independently C1-12 alkyl (e.g., C1-4 alkyl, such as methyl), and may optionally be disposed meta to the cyclohexylidene bridging group;
- R g is C1-12 alkyl (e.g., C1-4 alkyl) or halogen; r and s are each independently 1 to 4 (e.g., 1 ); and t is 0 to 10, such as 0 to 5.
- the cyclohexylidene-bridged bisphenol can be the reaction product of two moles of o-cresol with one mole of cyclohexanone.
- the cyclohexylidene-bridged bisphenol can be the reaction product of two moles of a cresol with one mole of a hydrogenated isophorone (e.g., 1 ,1 ,3-trimethyl-3- cyclohexane-5-one).
- a hydrogenated isophorone e.g., 1 ,1 ,3-trimethyl-3- cyclohexane-5-one.
- Such cyclohexane-containing bisphenols for example the reaction product of two moles of a phenol with one mole of a hydrogenated isophorone, are useful for making polycarbonate polymers with high glass transition temperatures and high heat distortion temperatures.
- X a may be a C1-18 alkylene group, a C3-18 cycloalkylene group, a fused C6-18 cycloalkylene group, or a group of the formula - B 1 -W-B 2 -, wherein B 1 and B 2 are independently a C1-6 alkylene group and W is a C3-12 cycloalkylidene group or a C6-16 arylene group.
- X a may also be a substituted C3-18 cycloalkylidene of the following formula (III): wherein,
- R r , R p , R q , and R l are each independently hydrogen, halogen, oxygen, or Ci- 12 organic groups;
- I is a direct bond, a carbon, or a divalent oxygen, sulfur, or -N(Z)-, wherein Z is hydrogen, halogen, hydroxy, C1-12 alkyl, C1-12 alkoxy, or C1-12 acyl; h is 0 to 2; j is 1 or 2; i is 0 or 1 ; and k is 0 to 3, with the proviso that at least two of R r , R p , R q , and R l taken together are a fused cycloaliphatic, aromatic, or heteroaromatic ring.
- R h is independently a halogen atom (e.g., bromine), C1-10 hydrocarbyl (e.g., C1-10 alkyl group), a halogen-substituted C1-10 alkyl group, a Ce-io aryl group, or a halogen-substituted Ce-io aryl group; n is 0 to 4.
- halogen atom e.g., bromine
- C1-10 hydrocarbyl e.g., C1-10 alkyl group
- n is 0 to 4.
- bisphenol compounds of formula (I) include, for instance, 1 ,1-bis(4-hydroxyphenyl) methane, 1,1-bis(4-hydroxyphenyl) ethane, 2,2- bis(4-hydroxyphenyl)propane (hereinafter “bisphenol A” or “BPA”), 2,2-bis(4- hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, 1 ,1-bis(4- hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl) n-butane, 2,2-bis(4-hydroxy-1- methylphenyl)propane, 1 ,1-bis(4-hydroxy-t-butylphenyl)propane, 3,3-bis(4- hydroxyphenyl)phthalimidine, 2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine (PPPBP), and 1 ,1-bis(4-hydroxy-3-methylphen
- aromatic dihydroxy compounds may include, but not limited to, 4,4'-dihydroxybiphenyl, 1 ,6-dihydroxynaphthalene, 2,6- dihydroxynaphthalene, bis(4-hydroxyphenyl)methane, bis(4- hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)-1-naphthylmethane, 1 ,2- bis(4-hydroxyphenyl)ethane, 1 ,1-bis(4-hydroxyphenyl)-1-phenylethane, 2-(4- hydroxyphenyl)-2-(3-hydroxyphenyl)propane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 1 ,1-bis (hydroxyphenyl)cyclopentane,
- Aromatic polycarbonates such as described above, typically have a
- DTUL value of from about 80°C to about 300°C, in some embodiments from about 100°C to about 250°C, and in some embodiments, from about 140°C to about 220°C, as determined in accordance with ISO 75-2:2013 at a load of 1.8
- the glass transition temperature may also be from about 50°C to about 250°C, in some embodiments from about 90°C to about 220°C, and in some embodiments, from about 100°C to about 200°C, such as determined by ISO 11357-2:2020.
- Such polycarbonates may also have an intrinsic viscosity of from about 0.1 dl/g to about 6 dl/g, in some embodiments from about 0.2 to about 5 dl/g, and in some embodiments from about 0.3 to about 1 dl/g, such as determined in accordance with ISO 1628-4:1998.
- highly crystalline aromatic polymers may also be employed in the polymer composition.
- Particularly suitable examples of such polymers are liquid crystalline polymers, which have a high degree of crystallinity that enables them to effectively fill the small spaces of a mold.
- Liquid crystalline polymers are generally classified as “thermotropic” to the extent that they can possess a rod-like structure and exhibit a crystalline behavior in their molten state (e.g., thermotropic nematic state).
- Such polymers typically have a DTUL value of from about 120°C to about 340°C, in some embodiments from about 140°C to about 320°C, and in some embodiments, from about 150°C to about 300°C, as determined in accordance with ISO 75-2:2013 at a load of 1.8 MPa.
- the polymers also have a relatively high melting temperature, such as from about 250°C to about 400°C, in some embodiments from about 280°C to about 390°C, and in some embodiments, from about 300°C to about 380°C.
- Such polymers may be formed from one or more types of repeating units as is known in the art.
- a liquid crystalline polymer may, for example, contain one or more aromatic ester repeating units generally represented by the following Formula (I): wherein, ring B is a substituted or unsubstituted 6-membered aryl group (e.g., 1,4- phenylene or 1 ,3-phenylene), a substituted or unsubstituted 6-membered aryl group fused to a substituted or unsubstituted 5- or 6-membered aryl group (e.g., 2,6-naphthalene), or a substituted or unsubstituted 6-membered aryl group linked to a substituted or unsubstituted 5- or 6-membered aryl group (e.g., 4,4- biphenylene); and
- Formula (I) wherein, ring B is a substituted or unsubstituted 6-membered aryl group (e.g., 1,4- phenylene or 1 ,3-phenylene), a substitute
- Yi and Y2 are independently 0, C(O), NH, C(0)HN, or NHC(O).
- At least one of Yi and Y2 are C(O).
- aromatic ester repeating units may include, for instance, aromatic dicarboxylic repeating units (Yi and Y2 in Formula I are C(O)), aromatic hydroxycarboxylic repeating units (Yi is O and Y2 is C(O) in Formula I), as well as various combinations thereof.
- Aromatic hydroxycarboxylic repeating units may be employed that are derived from aromatic hydroxycarboxylic acids, such as, 4- hydroxybenzoic acid; 4-hydroxy-4'-biphenylcarboxylic acid; 2-hydroxy-6-naphthoic acid; 2-hydroxy-5-naphthoic acid; 3-hydroxy-2-naphthoic acid; 2-hydroxy-3- naphthoic acid; 4'-hydroxyphenyl-4-benzoic acid; 3'-hydroxyphenyl-4-benzoic acid; 4'-hydroxyphenyl-3-benzoic acid, etc., as well as alkyl, alkoxy, aryl and halogen substituents thereof, and combination thereof.
- aromatic hydroxycarboxylic acids such as, 4- hydroxybenzoic acid; 4-hydroxy-4'-biphenylcarboxylic acid; 2-hydroxy-6-naphthoic acid; 2-hydroxy-5-naphthoic acid; 3-hydroxy-2-naphthoic acid; 2-
- aromatic hydroxycarboxylic acids are 4-hydroxybenzoic acid (‘ ⁇ BA”) and 6-hydroxy-2- naphthoic acid (‘ ⁇ NA”).
- ⁇ BA 4-hydroxybenzoic acid
- ⁇ NA 6-hydroxy-2- naphthoic acid
- repeating units derived from hydroxycarboxylic acids typically constitute about 20 mol.% to about 80 mol.%, in some embodiments from about 25 mol.% to about 75 mol.%, and in some embodiments, from about 30 mol.% to 70 mol.% of the polymer.
- Aromatic dicarboxylic repeating units may also be employed that are derived from aromatic dicarboxylic acids, such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl ether-4, 4'-dicarboxylic acid, 1 ,6- naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4'- dicarboxybiphenyl, bis(4-carboxyphenyl)ether, bis(4-carboxyphenyl)butane, bis(4- carboxyphenyl)ethane, bis(3-carboxyphenyl)ether, bis(3-carboxyphenyl)ethane, etc., as well as alkyl, alkoxy, aryl and halogen substituents thereof, and combinations thereof.
- aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxy
- aromatic dicarboxylic acids may include, for instance, terephthalic acid (“TA”), isophthalic acid (“IA”), and 2,6- naphthalenedicarboxylic acid (“NDA”).
- TA terephthalic acid
- IA isophthalic acid
- NDA 2,6- naphthalenedicarboxylic acid
- repeating units derived from aromatic dicarboxylic acids typically constitute from about 1 mol.% to about 50 mol.%, in some embodiments from about 5 mol.% to about 40 mol.%, and in some embodiments, from about 10 mol.% to about 35 mol.% of the polymer.
- repeating units may also be employed in the polymer.
- repeating units may be employed that are derived from aromatic diols, such as hydroquinone, resorcinol, 2,6- dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1 ,6-dihydroxynaphthalene, 4,4'- dihydroxybiphenyl (or 4,4’-biphenol), 3,3'-dihydroxybiphenyl, 3,4'- dihydroxybiphenyl, 4,4'-dihydroxybiphenyl ether, bis(4-hydroxyphenyl)ethane, etc., as well as alkyl, alkoxy, aryl and halogen substituents thereof, and combinations thereof.
- aromatic diols such as hydroquinone, resorcinol, 2,6- dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1 ,6-dihydroxynaphthalene, 4,4'- dihydroxybipheny
- aromatic diols may include, for instance, hydroquinone (“HQ”) and 4,4’-biphenol (“BP”).
- HQ hydroquinone
- BP 4,4’-biphenol
- repeating units derived from aromatic diols typically constitute from about 1 mol.% to about 40 mol.%, in some embodiments from about 2 mol.% to about 35 mol.%, and in some embodiments, from about 5 mol.% to about 30 mol.% of the polymer.
- Repeating units may also be employed, such as those derived from aromatic amides (e.g., acetaminophen (“APAP”)) and/or aromatic amines (e.g., 4- aminophenol (“AP”), 3-aminophenol, 1 ,4-phenylenediamine, 1,3- phenylenediamine, etc.).
- aromatic amides e.g., APAP
- aromatic amines e.g., AP
- repeating units derived from aromatic amides (e.g., APAP) and/or aromatic amines (e.g., AP) typically constitute from about 0.1 mol.% to about 20 mol.%, in some embodiments from about 0.5 mol.% to about 15 mol.%, and in some embodiments, from about 1 mol.% to about 10 mol.% of the polymer.
- the polymer may contain one or more repeating units derived from non-aromatic monomers, such as aliphatic or cycloaliphatic hydroxycarboxylic acids, dicarboxylic acids, diols, amides, amines, etc.
- non-aromatic monomers such as aliphatic or cycloaliphatic hydroxycarboxylic acids, dicarboxylic acids, diols, amides, amines, etc.
- the polymer may be “wholly aromatic” in that it lacks repeating units derived from non-aromatic (e.g., aliphatic or cycloaliphatic) monomers.
- the liquid crystalline polymer may be a “low naphthenic” polymer to the extent that it contains a relatively high content of repeating units derived from naphthenic hydroxycarboxylic acids and naphthenic dicarboxylic acids, such as naphthalene-2, 6-dicarboxylic acid (“NDA”), 6-hydroxy-
- HNA 2-naphthoic acid
- the total amount of repeating units derived from naphthenic hydroxycarboxylic and/or dicarboxylic acids is typically about 10 mol.% or less, in some embodiments about 8 mol.% or less, in some embodiments about 6 mol.% or less, and in some embodiments, from about 1 mol.% to about 5 mol.% of the polymer.
- the repeating units derived from naphthalene-2, 6-dicarboxylic acid (“HNA”) may be present in an amount of only from about 0.5 mol.% to about 15 mol.%, in some embodiments from about 1 mol.% to about 10 mol.%, and in some embodiments, from about 2 mol.% to about 8 mol.% of the polymer.
- the liquid crystalline polymer may also contain various other monomers, such as aromatic hydroxycarboxylic acid(s) (e.g., HBA) in an amount of from about 30 mol.% to about 70 mol.%, and in some embodiments, from about 40 mol.% to about 65 mol.%; aromatic dicarboxylic acid(s) (e.g., IA and/or TA) in an amount of from about 2 mol.% to about 30 mol.%, and in some embodiments, from about 5 mol.% to about 25 mol.%; and/or aromatic diol(s) (e.g., BP and/or HQ) in an amount of from about 2 mol.% to about 40 mol.%, and in some embodiments, from about 5 mol.% to about 35 mol.%.
- aromatic hydroxycarboxylic acid(s) e.g., HBA
- aromatic dicarboxylic acid(s) e.g., IA and/or TA
- the liquid crystalline polymer may be a “high naphthenic” polymer to the extent that it contains a relatively high content of repeating units derived from naphthenic hydroxycarboxylic acids and naphthenic dicarboxylic acids, such as naphthalene-2, 6-dicarboxylic acid (“NDA”),
- NDA 6-dicarboxylic acid
- HNA 6-hydroxy-2-naphthoic acid
- the total amount of repeating units derived from naphthenic hydroxycarboxylic and/or dicarboxylic acids is typically greater than about 10 mol.%, in some embodiments about 15 mol.% or more, and in some embodiments, from about 20 mol.% to about 60 mol.% of the polymer.
- the repeating units derived from naphthalene-2, 6-dicarboxylic acid (“NDA”) may constitute from about 10 mol.% to about 40 mol.%, in some embodiments from about 12 mol.% to about 35 mol.%, and in some embodiments, from about 15 mol.% to about 30 mol.% of the polymer.
- the liquid crystalline polymer may also contain various other monomers, such as aromatic hydroxycarboxylic acid(s) (e.g., HBA) in an amount of from about 20 mol.% to about 60 mol.%, and in some embodiments, from about 30 mol.% to about 50 mol.%; aromatic dicarboxylic acid(s) (e.g., IA and/or TA) in an amount of from about 2 mol.% to about 30 mol.%, and in some embodiments, from about 5 mol.% to about 25 mol.%; and/or aromatic diol(s) (e.g., BP and/or HQ) in an amount of from about 2 mol.% to about 40 mol.%, and in some embodiments, from about 5 mol.% to about 35 mol.%.
- aromatic hydroxycarboxylic acid(s) e.g., HBA
- aromatic dicarboxylic acid(s) e.g., IA and/or TA
- all of the liquid crystalline polymers are “low naphthenic” polymers such as described above. In other embodiments, all of the liquid crystalline polymers are “high naphthenic” polymers such as described above. In some cases, blends of such polymers may also be used.
- low naphthenic liquid crystalline polymers may constitute from about 1 wt.% to about 50 wt.%, in some embodiments from about 2 wt.% to about 40 wt.%, and in some embodiments, from about 5 wt.% to about 30 wt.% of the total amount of liquid crystalline polymers in the composition
- high naphthenic liquid crystalline polymers may constitute from about 50 wt.% to about 99 wt.%, in some embodiments from about 60 wt.% to about 98 wt.%, and in some embodiments, from about 70 wt.% to about 95 wt.% of the total amount of liquid crystalline polymers in the composition.
- the polymer composition also contains a semiconductive material.
- the semiconductive material is typically employed in an amount of from about 10 wt.% to about 70 wt.%, in some embodiments from about 20 wt.% to about 60 wt.%, and in some embodiments, from about 30 wt.% to about 50 wt.% of the composition.
- the volume resistivity of the semiconductive material may be selectively controlled so that it is, for example, within a range of from about 0.1 ohm-cm to about 1 x 10 12 ohm-cm, in some embodiments about 0.5 ohm-cm to about 1 x 10 11 ohm-cm, in some embodiments from about 1 to about 1 x 10 10 ohm-cm, and in some embodiments, from about 2 to about 1 x 10 8 ohm-cm, such as determined at a temperature of about 20°C in accordance with ASTM D257-14 (technically equivalent to IEC
- the volume resistivity of the resulting polymer composition may be from about 1 x 10 11 ohm-m to about 1 x 10 17 ohm-m, in some embodiments from about 1 x 10 12 ohm-m to about 1 x 10 16 ohm-m, and in some embodiments, from about 1 x 10 13 ohm-m to about 1 x 10 15 ohm-m, such as determined at a temperature of about 20°C in accordance with ASTM D257-14 (technically equivalent to IEC 62631 -3-1 ).
- the surface resistivity of the polymer composition may likewise range from about 1 x 10 13 ohm to about 1 x 10 19 ohm, in some embodiments from about 1 x 10 14 ohm to about 1 x 10 18 ohm, and in some embodiments, from about 1 x 10 15 ohm to about 1 x 10 17 ohm, such as determined at a temperature of about 20°C in accordance with ASTM D257-14 (technically equivalent to IEC 62631 -3-1 ).
- the semiconductive material contains inorganic particles and an electrically conductive material to help achieve the desired volume resistance.
- the ratio of the weight percentage of the inorganic particles in the polymer composition to the weight percentage of the electrically conductive material in the composition is typically from about 3 to about 100, in some embodiments from about 3 to about 50, in some embodiments from about 3 to about 20, in some embodiments from about 7 to about 18, and in some embodiments, from about 8 to about 15.
- the electrically conductive material may constitute from about 1 wt.% to about 20 wt.%, in some embodiments from about 3 wt.% to about 18 wt.%, and in some embodiments, from about 5 wt.% to about 15 wt.% of the semiconductive material, while the inorganic particles may constitute from about 80 wt.% to about 99 wt.%, in some embodiments 82 wt.% to about 97 wt.%, and in some embodiments, from about
- the electrically conductive material may constitute from about 0.1 wt.% to about 15 wt.%, in some embodiments from about 0.5 wt.% to about 12 wt.%, and in some embodiments, from about 1 wt.% to about 10 wt.% of the polymer composition, while the inorganic particles may constitute from about 20 wt.% to about 60 wt.%, in some embodiments 25 wt.% to about 55 wt.%, and in some embodiments, from about 30 wt.% to about 50 wt.% of the polymer composition.
- the inorganic particles generally have a low electrical conductivity, such as about 500 pS/cm or less, in some embodiments about 350 pS/cm or less, and in some embodiments, from about 50 to about 200 pS/cm, as determined at a temperature of about 25°C.
- the inorganic particles also have a controlled size, such as a median particle size (D50) of from about 0.1 to 100 micrometers, in some embodiments from about 0.1 to about 50 micrometers, in some embodiments from about 0.1 to about 25 micrometers, in some embodiments from about 0.1 to about 10 micrometers, in some embodiments from about 0.1 to about 5 micrometers, in some embodiments from about 0.2 to about 4 micrometers, and in some embodiments, from about 0.5 to about 3 micrometers, such as measured with ISO 13317-3:2001 (sedigraph).
- D50 median particle size
- the particles may also have a narrow size distribution.
- At least about 70% by volume of the particles in some embodiments at least about 80% by volume of the particle material, and in some embodiments, at least about 90% by volume of the material may have a size within the ranges noted above.
- the shape of the particles may vary as desired, such as flake, spherical, platy, etc.
- inorganic particles with the characteristics noted above may be employed in the present invention, such as carbonates (e.g., calcium carbonate, copper carbonate hydroxide, etc.), fluorides (e.g., calcium fluoride), phosphates (e.g., calcium pyrophosphate), silicates (e.g., silica, potassium aluminum silicate, copper silicate, talc, mica, etc.), borates (e.g., calcium borosilicate hydroxide), alumina, sulfates (e.g., calcium sulfate, barium sulfate, etc.), as well as combinations of any of the foregoing. Barium sulfate is particularly suitable for use in the present invention.
- carbonates e.g., calcium carbonate, copper carbonate hydroxide, etc.
- fluorides e.g., calcium fluoride
- phosphates e.g., calcium pyrophosphate
- silicates e.g., silica
- the electrically conductive material likewise generally has a volume resistivity of less than about 0.1 ohm-cm, and in some embodiments, from about 1 x 10 8 to about 1 x 10 2 ohm-cm, and the insulative materials generally have a volume resistivity of greater than about 1 x 10 12 ohm-cm, and in some embodiments, from about 1 x 10 13 to about 1 x 10 18 ohm-cm.
- Suitable electrically conductive materials may include, for instance, electrically conductive carbon materials (e.g., graphite, carbon black, carbon fibers, graphene, nanotubes, etc.), metals, etc.
- additives can also be included in the polymer composition, such as lubricants, fibrous filler, thermally conductive fillers, pigments, antioxidants, stabilizers, surfactants, waxes, flame retardants, anti-drip additives, nucleating agents (e.g., boron nitride), flow modifiers, laser activatable additives, and other materials added to enhance properties and processability.
- lubricants such as lubricants, fibrous filler, thermally conductive fillers, pigments, antioxidants, stabilizers, surfactants, waxes, flame retardants, anti-drip additives, nucleating agents (e.g., boron nitride), flow modifiers, laser activatable additives, and other materials added to enhance properties and processability.
- fibrous filler such as lubricants, fibrous filler, thermally conductive fillers, pigments, antioxidants, stabilizers, surfactants, waxes, flame retardants, anti-drip additives, nucleating agents
- the polymer composition may be “laser activatable” in the sense that it contains an additive that can be activated by a laser direct structuring (“LDS”) process to form an antenna element.
- LDS laser direct structuring
- the additive is exposed to a laser that causes the release of metals.
- the laser draws the pattern of conductive elements onto the part and leaves behind a roughened surface containing embedded metal particles. These particles act as nuclei for the crystal growth during a subsequent plating process (e.g., copper plating, gold plating, nickel plating, silver plating, zinc plating, tin plating, etc.).
- laser activatable additives typically constitute from about 0.1 wt.% to about 30 wt.%, in some embodiments from about 0.5 wt.% to about 20 wt.%, and in some embodiments, from about 1 wt.% to about 10 wt.% of the polymer composition.
- the laser activatable additive generally includes spinel crystals, which may include two or more metal oxide cluster configurations within a definable crystal formation.
- the overall crystal formation may have the following general formula:
- A is a metal cation having a valance of 2, such as cadmium, chromium, manganese, nickel, zinc, copper, cobalt, iron, magnesium, tin, titanium, etc., as well as combinations thereof; and
- B is a metal cation having a valance of 3, such as chromium, iron, aluminum, nickel, manganese, tin, etc., as well as combinations thereof.
- a in the formula above provides the primary cation component of a first metal oxide cluster and B provides the primary cation component of a second metal oxide cluster.
- These oxide clusters may have the same or different structures.
- the first metal oxide cluster has a tetrahedral structure and the second metal oxide cluster has an octahedral cluster.
- the clusters may together provide a singular identifiable crystal type structure having heightened susceptibility to electromagnetic radiation.
- Suitable spinel crystals include, for instance, MgAteC , ZnAteC , FeAteC , CuFe204, CuC C , MnFe204, NiFe204, TiFe204, FeCr204, MgC C , etc.
- Copper chromium oxide (CuCr204) is particularly suitable for use in the present invention and is available from Shepherd Color Co. under the designation “Shepherd Black 1GM.”
- a fibrous filler may also be employed in the polymer composition to improve the thermal and mechanical properties of the composition without having a significant impact on electrical performance.
- the fibrous filler typically includes fibers having a high degree of tensile strength relative to their mass.
- the ultimate tensile strength of the fibers is typically from about 1,000 to about 15,000 Megapascals (“MPa”), in some embodiments from about 2,000 MPa to about 10,000 MPa, and in some embodiments, from about 3,000 MPa to about 6,000 MPa.
- MPa Megapascals
- such high strength fibers may be formed from materials that are generally insulative in nature, such as glass, ceramics (e.g., alumina or silica), aramids (e.g., Kevlar® marketed by E. I. duPont de Nemours, Wilmington, Del.), polyolefins, polyesters, etc. Glass fibers are particularly suitable, such as E-glass, A-glass, C-glass, D-glass, AR-glass, R- glass, S1 -glass, S2-glass, etc.
- fibers employed in the fibrous filler may have a variety of different sizes
- fibers having a certain aspect ratio can help improve the mechanical properties of the resulting polymer composition. That is, fibers having an aspect ratio (average length divided by nominal diameter) of from about 5 to about 50, in some embodiments from about 6 to about 40, and in some embodiments, from about 8 to about 25 are particularly beneficial.
- Such fibers may, for instance, have a weight average length of from about 100 to about
- the fibers may likewise have a nominal diameter of about 6 to about 35 micrometers, and in some embodiments, from about 9 to about 18 micrometers.
- the relative amount of the fibrous filler may also be selectively controlled to help achieve the desired mechanical and thermal properties without adversely impacting other properties of the composition, such as its flowability and dielectric properties, etc.
- the fibrous filler may constitute from about 1 wt.% to about 40 wt.%, in some embodiments from about 3 wt.% to about 30 wt.%, and in some embodiments, from about 5 wt.% to about 20 wt.% of the polymer composition.
- the fibrous filler may also be employed in a sufficient amount so that the weight ratio of the fibrous filler to the combined amounts of the dielectric and laser activatable materials is from about 0.05 to about 1 , in some embodiments from about 0.05 to about 0.5, in some embodiments from about 0.06 to about 0.4, and in some embodiments from about 0.1 to about 0.3.
- thermoplastic high performance polymer, inorganic particles, electrically conductive material, and other optional additives are melt processed as a mixture within an extruder to form the polymer composition.
- the mixture may be melt-kneaded in a single screw or multi-screw extruder at a temperature of from about 250°C to about 450°C.
- the mixture may be melt processed in an extruder that includes multiple temperature zones. The temperature of individual zones is typically set within about -60°C to about 25°C relative to the melting temperature of the liquid crystalline polymer.
- the mixture may be melt processed using a twin screw extruder such as a Leistritz 18-mm co-rotating fully intermeshing twin screw extruder.
- a general purpose screw design can be used to melt process the mixture.
- the mixture including all of the components may be fed to the feed throat in the first barrel by means of a volumetric feeder.
- different components may be added at different addition points in the extruder, as is known.
- the liquid crystalline polymer may be applied at the feed throat, and certain additives (e.g., inorganic particles, electrically conductive material, etc.) may be supplied at the same or different temperature zone located downstream therefrom.
- the resulting mixture can be melted and mixed then extruded through a die.
- the extruded polymer composition can then be quenched in a water bath to solidify and granulated in a pelletizer followed by drying.
- the melt viscosity of the resulting composition is generally low enough that it can readily flow into the cavity of a mold to form the small-sized circuit substrate.
- the polymer composition may have a melt viscosity of from about 5 to about 100 Pa-s, in some embodiments from about 10 to about 95 Pa-s, and in some embodiments, from about 15 to about 90 Pa-s, determined at a shear rate of 1,000 seconds 1 .
- Melt viscosity may be determined in accordance with 11443:2014.
- the polymer composition may be molded into the desired shape of a substrate for use in an antenna system. Due to the beneficial properties of the polymer composition, the resulting substrate may have a very small size, such as a thickness of about 5 millimeters or less, in some embodiments about 4 millimeters or less, and in some embodiments, from about 0.5 to about 3 millimeters.
- the shaped parts are molded using a one- component injection molding process in which dried and preheated plastic granules are injected into the mold.
- the conductive elements may be formed in a variety of ways, such as by plating, electroplating, laser direct structuring, etc.
- activation with a laser may cause a physio-chemical reaction in which the spinel crystals are cracked open to release metal atoms.
- metal atoms can act as a nuclei for metallization (e.g., reductive copper coating).
- the laser also creates a microscopically irregular surface and ablates the polymer matrix, creating numerous microscopic pits and undercuts in which the copper can be anchored during metallization.
- the conductive elements may be antenna elements (e.g., antenna resonating elements) so that the resulting part forms an antenna system.
- the conductive elements can form antennas of a variety of different types, such as antennae with resonating elements that are formed from patch antenna elements, inverted-F antenna elements, closed and open slot antenna elements, loop antenna elements, monopoles, dipoles, planar inverted-F antenna elements, hybrids of these designs, etc.
- the resulting antenna system can be employed in a variety of different electronic components.
- the antenna system may be formed in electronic components, such as desktop computers, portable computers, handheld electronic devices, automotive equipment, etc.
- the antenna system is formed in the housing of a relatively compact portable electronic component in which the available interior space is relatively small.
- Suitable portable electronic components include cellular telephones, laptop computers, small portable computers (e.g., ultraportable computers, netbook computers, and tablet computers), wrist-watch devices, pendant devices, headphone and earpiece devices, media players with wireless communications capabilities, handheld computers (also sometimes called personal digital assistants), remote controllers, global positioning system (GPS) devices, handheld gaming devices, etc.
- the antenna could also be integrated with other components such as camera module, speaker or battery cover of a handheld device.
- Figs. 1-2 is a handheld device 10 with cellular telephone capabilities.
- the device 10 may have a housing 12 formed from plastic, metal, other suitable dielectric materials, other suitable conductive materials, or combinations of such materials.
- a display 14 may be provided on a front surface of the device 10, such as a touch screen display.
- the device 10 may also have a speaker port 40 and other input-output ports.
- One or more buttons 38 and other user input devices may be used to gather user input.
- an antenna system 26 is also provided on a rear surface 42 of device 10, although it should be understood that the antenna system can generally be positioned at any desired location of the device.
- the antenna system may be electrically connected to other components within the electronic device using any of a variety of known techniques.
- the housing 12 or a part of housing 12 may serve as a conductive ground plane for the antenna system 26.
- Fig. 3 shows the antenna system 26 as being fed by a radio frequency source 52 at a positive antenna feed terminal 54 and a ground antenna feed terminal 56.
- the positive antenna feed terminal 54 may be coupled to an antenna resonating element 58
- the ground antenna feed terminal 56 may be coupled to a ground element 60.
- the resonating element 58 may have a main arm 46 and a shorting branch 48 that connects main arm 46 to ground 60.
- the antenna system is based on a monopole antenna configuration and the resonating element 58 has a meandering serpentine path shape.
- the feed terminal 54 may be connected to one end of resonating element 58, and the ground feed terminal 56 may be coupled to housing 12 or another suitable ground plane element.
- conductive antenna elements are also contemplated.
- the antenna formed from structures 62 may be fed using positive antenna feed terminal 54 and ground antenna feed terminal 56.
- slots 64 and 66 serve as antenna resonating elements for the antenna element 26.
- the sizes of the slots 64 and 66 may be configured so that the antenna element 26 operates in desired communications bands (e.g., 2.4 GHz and 5 GHz, etc.).
- Another possible configuration for the antenna system 26 is shown in Fig. 6.
- the antenna element 26 has a patch antenna resonating element 68 and may be fed using positive antenna feed terminal 54 and ground antenna feed terminal 56.
- the ground 60 may be associated with housing 12 or other suitable ground plane elements in device 10.
- Fig. 7 shows yet another illustrative configuration that may be used for the antenna elements of the antenna system 26.
- antenna resonating element 58 has two main arms 46A and 46B.
- the arm 46A is shorter than the arm 46B and is therefore associated with higher frequencies of operation than the arm 46A.
- the antenna resonating element 58 can be configured to cover a wider bandwidth or more than a single communications band of interest.
- the polymer composition may be particularly well suited for high frequency antennas and antenna arrays for use in base stations, repeaters (e.g., “femtocells”), relay stations, terminals, user devices, and/or other suitable components of 5G systems.
- repeaters e.g., “femtocells”
- relay stations e.g., terminals, user devices, and/or other suitable components of 5G systems.
- 5G generally refers to high speed data communication over radio frequency signals.
- 5G networks and systems are capable of communicating data at much faster rates than previous generations of data communication standards
- 5G frequencies can refer to frequencies that are 1.5 GHz or more, in some embodiments about 2.0 GHz or more, in some embodiments about 2.5 GHz or higher, in some embodiments about
- the IMT-2020 standard specifies various data transmission criteria (e.g., downlink and uplink data rate, latency, etc.) for 5G.
- the IMT-2020 Standard defines uplink and downlink peak data rates as the minimum data rates for uploading and downloading data that a 5G system must support.
- the IMT-2020 standard sets the downlink peak data rate requirement as 20 Gbit/s and the uplink peak data rate as 10 Gbit/s.
- 3GPP 3 rd Generation Partnership Project
- 3GPP published “Release 15” in 2018 defining “Phase 1” for standardization of 5G NR.
- 3GPP defines 5G frequency bands generally as “Frequency Range 1” (FR1) including sub-6GHz frequencies and “Frequency Range 2” (FR2) as frequency bands ranging from 20-60 GHz.
- antenna elements and arrays may employ small feature sizes/spacing (e.g., fine pitch technology) that can improve antenna performance.
- the feature size spacing between antenna elements, width of antenna elements etc. is generally dependent on the wavelength (“l”) of the desired transmission and/or reception radio frequency propagating through the substrate dielectric on which the antenna element is formed (e.g., hl/4 where n is an integer).
- beamforming and/or beam steering can be employed to facilitate receiving and transmitting across multiple frequency ranges or channels (e.g., multiple-in- multiple-out (MIMO), massive MIMO).
- the high frequency 5G antenna elements can have a variety of configurations.
- the 5G antenna elements can be or include co- planar waveguide elements, patch arrays (e.g., mesh-grid patch arrays), other suitable 5G antenna configurations.
- the antenna elements can be configured to provide MIMO, massive MIMO functionality, beam steering, and the like.
- massive MIMO functionality generally refers to providing a large number transmission and receiving channels with an antenna array, for example 8 transmission (Tx) and 8 receive (Rx) channels (abbreviated as 8x8).
- Massive MIMO functionality may be provided with 8x8, 12x12, 16x16, 32x32, 64x64, or greater.
- the antenna elements can have a variety of configurations and arrangements and can be fabricated using a variety of manufacturing techniques.
- the antenna elements and/or associated elements e.g., ground elements, feed lines, etc.
- feature dimensions and/or spacing between antenna elements can be about 1 ,500 micrometers or less, in some embodiments 1,250 micrometers or less, in some embodiments 750 micrometers or less (e.g., center-to-center spacing of 1.5 mm or less), 650 micrometers or less, in some embodiments 550 micrometers or less, in some embodiments 450 micrometers or less, in some embodiments 350 micrometers or less, in some embodiments 250 micrometers or less, in some embodiments 150 micrometers or less, in some embodiments 100 micrometers or less, and in some embodiments 50 micrometers or less.
- feature sizes and/or spacings that are smaller and/or larger may be employed within the scope of this disclosure.
- an antenna array can have an average antenna element concentration of greater than 1 ,000 antenna elements per square centimeter, in some embodiments greater than 2,000 antenna elements per square centimeter, in some embodiments greater than 3,000 antenna elements per square centimeter, in some embodiments greater than 4,000 antenna elements per square centimeter, in some embodiments greater than 6,000 antenna elements per square centimeter, and in some embodiments greater than about 8,000 antenna elements per square centimeter.
- Such compact arrangement of antenna elements can provide a greater number of channels for MIMO functionality per unit area of the antenna area.
- the number of channels can correspond with (e.g., be equal to or proportional with) the number of antenna elements.
- a 5G antenna system 100 also includes a base station 102, one or more relay stations 104, one or more user computing devices 106, one or more Wi-Fi repeaters 108 (e.g., “femtocells”), and/or other suitable antenna components for the 5G antenna system 100.
- the relay stations 104 can be configured to facilitate communication with the base station 102 by the user computing devices 106 and/or other relay stations 104 by relaying or “repeating” signals between the base station 102 and the user computing devices 106 and/or relay stations 104.
- the base station 102 can include a MIMO antenna array 110 configured to receive and/or transmit radio frequency signals 112 with the relay station(s) 104, Wi-Fi repeaters 108, and/or directly with the user computing device(s) 106.
- the user computing device 106 is not necessarily limited by the present invention and include devices such as 5G smartphones.
- the MIMO antenna array 110 can employ beam steering to focus or direct radio frequency signals 112 with respect to the relay stations 104.
- the MIMO antenna array 110 can be configured to adjust an elevation angle 114 with respect to an X-Y plane and/or a heading angle 116 defined in the Z-Y plane and with respect to the Z direction.
- one or more of the relay stations 104, user computing devices 106, Wi-Fi repeaters 108 can employ beam steering to improve reception and/or transmission ability with respect to MIMO antenna array 110 by directionally tuning sensitivity and/or power transmission of the device 104, 106, 108 with respect to the MIMO antenna array 110 of the base station 102 (e.g., by adjusting one or both of a relative elevation angle and/or relative azimuth angle of the respective devices).
- Figs. 9A and 9B illustrate a top-down and side elevation view, respectively, of an example user computing device 106.
- the user computing device 106 may include one or more antenna elements 200, 202 (e.g., arranged as respective antenna arrays).
- the antenna elements 200, 202 can be configured to perform beam steering in the X-Y plane (as illustrated by arrows 204, 206 and corresponding with a relative azimuth angle).
- the antenna elements 200, 202 can be configured to perform beam steering in the Z-Y plane (as illustrated by arrows 204, 206).
- Fig. 9A the antenna elements 200, 202 can be configured to perform beam steering in the X-Y plane (as illustrated by arrows 204, 206 and corresponding with a relative azimuth angle).
- the antenna elements 200, 202 can be configured to perform beam steering in the Z-Y plane (as illustrated by arrows 204, 206).
- the antenna arrays 302 can be mounted to a side surface 306 of a substrate 308, which may be formed from the polymer composition of the present invention.
- the antenna arrays 302 can include a plurality of vertically connected elements (e.g., as a mesh-grid array).
- the antenna array 302 can generally extend parallel with the side surface 306 of the substrate 308.
- Shielding can optionally be provided on the side surface 306 of the substrate 308 such that the antenna arrays 302 are located outside of the shielding with respect to the substrate 308.
- the vertical spacing distance between the vertically connected elements of the antenna array 302 can correspond with the “feature sizes” of the antenna arrays 302. As such, in some embodiments, these spacing distances may be relatively small (e.g., less than about 750 micrometers) such that the antenna array 302 is a “fine pitch” antenna array 302.
- Fig. 11 illustrates a side elevation view of a co-planar waveguide antenna 400 configuration.
- One or more co-planar ground layers 402 can be arranged parallel with an antenna element 404 (e.g., a patch antenna element).
- Another ground layer 406 may be spaced apart from the antenna element by a substrate 408, which may be formed from the polymer composition of the present invention.
- One or more additional antenna elements 410 can be spaced apart from the antenna element 404 by a second layer or substrate 412, which may also be formed from the polymer composition of the present invention.
- “G” and “W” may correspond with “feature sizes” of the antenna 400.
- the “G” dimension may correspond with a distance between the antenna element 404 and the co-planar ground layer(s) 406.
- the “W” dimension can correspond with a width (e.g., linewidth) of the antenna element 404.
- dimensions “G” and “W” may be relatively small (e.g., less than about 750 micrometers) such that the antenna 400 is a “fine pitch” antenna 400.
- Fig. 12A illustrates an antenna array 500 according to another aspect of the present disclosure.
- the antenna array 500 can include a substrate 510, which may be formed from the polymer composition of the present invention, and a plurality of antenna elements 520 formed thereon.
- the plurality of antenna elements 520 can be approximately equally sized in the X- and/or Y-directions (e.g., square or rectangular).
- the plurality of antenna elements 520 can be spaced apart approximately equally in the X- and/or Y-directions.
- the dimensions of the antenna elements 520 and/or spacing therebetween can correspond with “feature sizes” of the antenna array 500.
- the dimensions and/or spacing may be relatively small (e.g., less than about 750 micrometers) such that the antenna array 500 is a “fine pitch” antenna array 500.
- the number of columns of antenna elements 520 illustrated in Fig. 12 is provided as an example only.
- the number of rows of antenna element 520 is provided as an example only.
- the tuned antenna array 500 can be used to provide massive MIMO functionality, for example in a base station (e.g., as described above with respect to Fig. 8). More specifically, radio frequency interactions between the various elements can be controlled or tuned to provide multiple transmitting and/or receiving channels. Transmitting power and/or receiving sensitivity can be directionally controlled to focus or direct radio frequency signals, for example as described with respect to the radio frequency signals 112 of Fig. 8.
- the tuned antenna array 500 can provide a large number of antenna elements 522 in a small footprint.
- the tuned antenna 500 can have an average antenna element concentration of 1 ,000 antenna elements per square cm or greater.
- Such compact arrangement of antenna elements can provide a greater number of channels for MIMO functionality per unit area.
- the number of channels can correspond with (e.g., be equal to or proportional with) the number of antenna elements.
- Fig. 12B illustrates an antenna array 540 formed with laser direct structuring, which may optionally be employed to form the antenna elements.
- the antenna array 540 can include a plurality of antenna elements 542 and plurality of feed lines 544 connecting the antenna elements 542 (e.g., with other antenna elements 542, a front end module, or other suitable component).
- the antenna elements 542 can have respective widths “w” and spacing distances “Si” and “S2” therebetween (e.g., in the X-direction and Y-direction, respectively). These dimensions can be selected to achieve 5G radio frequency communication at a desired 5G frequency.
- the dimensions can be selected to tune the antenna array 540 for transmission and/or reception of data using radio frequency signals that are within the 5G frequency spectrum.
- the dimensions can be selected based on the material properties of the substrate. For example, one or more of “w”, “Si,” or “S2” can correspond with a multiple of a propagation wavelength (“l”) of the desired frequency through the substrate material (e.g., hl/4 where n is an integer).
- l can be calculated as follows: where c is the speed of light in a vacuum, e R is the dielectric constant of the substrate (or surrounding material), is the desired frequency.
- Fig. 12C illustrates an example antenna configuration 560 according to aspects of the present disclosure.
- the antenna configuration 560 can include multiple antenna elements 562 arranged in parallel long edges of a substrate 564, which may be formed from the polymer composition of the present invention.
- the various antenna elements 562 can have respective lengths, “L” (and spacing distances therebetween) that tune the antenna configuration 560 for reception and/or transmission at a desired frequency and/or frequency range. More specifically, such dimensions can be selected based on a propagation wavelength, l, at the desired frequency for the substrate material, for example as described above with reference to Fig. 12B.
- Figs. 13A through 13C depict simplified sequential diagrams of a laser direct structuring manufacturing process that can be used to form antenna elements and/or arrays according to aspects of the present disclosure.
- a substrate 600 can be formed from the polymer composition of the present invention using any desired technique (e.g., injection molding).
- a laser 602 can be used to activate the laser activatable additive to form a circuit pattern 604 that can include one or more of the antenna elements and/or arrays.
- the laser can melt conductive particles in the polymer composition to form the circuit pattern 604.
- the substrate 600 can be submerged in an electroless copper bath to plate the circuit pattern 604 and form the antenna elements, elements arrays, other components, and/or conductive lines therebetween.
- the present invention may be better understood with reference to the following examples.
- the melt viscosity may be determined in accordance with ISO Test No. 11443:2014 at a shear rate of 400 s _1 and temperature 15°C above the melting temperature (e.g., about 350°C) using a Dynisco LCR7001 capillary rheometer.
- the rheometer orifice (die) had a diameter of 1 mm, length of 20 mm, L/D ratio of 20.1, and an entrance angle of 180°.
- the diameter of the barrel was 9.55 mm + 0.005 mm and the length of the rod was 233.4 mm.
- Tm The melting temperature (“Tm”) may be determined by differential scanning calorimetry (“DSC”) as is known in the art.
- the melting temperature is the differential scanning calorimetry (DSC) peak melt temperature as determined by ISO Test No. 11357-3:2018. Under the DSC procedure, samples were heated and cooled at 20°C per minute as stated in ISO Standard 10350 using DSC measurements conducted on a TA Q2000 Instrument.
- DSC differential scanning calorimetry
- Deflection Temperature Under Load The deflection under load temperature may be determined in accordance with ISO Test No. 75-2:2013 (technically equivalent to ASTM D648). More particularly, a test strip sample having a length of 80 mm, thickness of 10 mm, and width of 4 mm may be subjected to an edgewise three-point bending test in which the specified load (maximum outer fibers stress) was 1.8 Megapascals. The specimen may be lowered into a silicone oil bath where the temperature is raised at 2°C per minute until it deflects 0.25 mm (0.32 mm for ISO Test No. 75-2:2013).
- Tensile Modulus, Tensile Stress, and Tensile Elongation Tensile properties may be tested according to ISO Test No. 527:2019 (technically equivalent to ASTM D638). Modulus and strength measurements may be made on the same test strip sample having a length of 80 mm, thickness of 10 mm, and width of 4 mm. The testing temperature may be 23°C, and the testing speeds may be 1 or 5 mm/min.
- Flexural properties may be tested according to ISO Test No. 178:2019 (technically equivalent to ASTM D790). This test may be performed on a 64 mm support span. Tests may be run on the center portions of uncut ISO 3167 multi purpose bars. The testing temperature may be 23°C and the testing speed may be 2 mm/min.
- Charpy Impact Strength Charpy properties may be tested according to ISO Test No. ISO 179-1 :2010) (technically equivalent to ASTM D256-10,
- Method B This test may be run using a Type 1 specimen size (length of 80 mm, width of 10 mm, and thickness of 4 mm).
- the notch When testing the notched impact strength, the notch may be a Type A notch (0.25 mm base radius). Specimens may be cut from the center of a multi-purpose bar using a single tooth milling machine. The testing temperature may be 23°C.
- Dielectric Constant (“Dk”) and Dissipation Factor (“Df’) ⁇ The dielectric constant (or relative static permittivity) and dissipation factor are determined using a known split-post dielectric resonator technique, such as described in Baker-Jarvis, et al., IEEE Trans on Dielectric and Electrical Insulation, 5(4), p. 571 (1998) and Krupka, et al., Proc. 7 th International Conference on Dielectric Materials: Measurements and Applications, IEEE Conference Publication No. 430 (Sept. 1996). More particularly, a plaque sample having a size of 80 mm x 90 mm x 3 mm was inserted between two fixed dielectric resonators.
- the resonator measured the permittivity component in the plane of the specimen. Five (5) samples are tested and the average value is recorded.
- the split-post resonator can be used to make dielectric measurements in the low gigahertz region, such as 1 GHz from 2 GHz.
- Heat Cycle Test Specimens are placed in a temperature control chamber and heated/cooled within a temperature range of from -30°C and 100°C.
- the samples are heated until reaching a temperature of 100°C, when they were immediately cooled.
- the temperature reaches -30°C
- the specimens are immediately heated again until reaching 100°C.
- Twenty three (23) heating/cooling cycles may be performed over a 3-hour time period.
- the surface and volume resistivity values may be determined in accordance with IEC 62631-3-1:2016 or ASTM
- volume resistivity is also determined as the ratio of the potential gradient parallel to the current in a material to the current density. In SI units, volume resistivity is numerically equal to the direct-current resistance between opposite faces of a one- meter cube of the material (ohm-m or ohm-cm).
- LCP 1 is formed from 43% HBA, 20% NDA, 9% TA, and 28% HQ.
- LCP 2 is formed from 73% HBA and 27% HNA.
- LCP 3 is formed from 60% HBA, 5% HNA, 17.5% TA, 2.5% BP, and 5% APAP. Compounding was performed using an 18-mm single screw extruder. Parts are injection molded the samples into plaques (60 mm x 60 mm).
- Samples 1 -3 were also subjected to a heat cycle test as described above. Upon testing, it was determined that the resulting dissipation factor for the samples was 0.013, 0.017, and 0.018, respectively. Thus, the ratio of the dissipation factor after heat cycle testing to the initial dissipation factor for Samples 1 , 2, and 3 was 0.86, 0.86, and 0.76, respectively. Upon testing, it was also determined that the resulting dielectric constant for the samples was 9.0, 12.2, and 15.1, respectively. Thus, the ratio of the dielectric constant after heat cycle testing to the initial dielectric constant for Samples 1 , 2, and 3 was 1.01, 1.01 , and 1.03, respectively.
Abstract
Description
Claims
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JP2023550000A JP2024510883A (en) | 2021-02-18 | 2021-02-18 | Polymer compositions for use in antenna systems |
KR1020237031735A KR20230147152A (en) | 2021-02-18 | 2021-02-18 | Polymeric compositions for use in antenna systems |
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US20190161612A1 (en) * | 2015-08-17 | 2019-05-30 | Ticona Llc | Liquid Crystalline Polymer Composition for Camera Modules |
US20210057827A1 (en) * | 2019-08-21 | 2021-02-25 | Ticona Llc | Antenna System Including a Polymer Composition having a Low Dissipation Factor |
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2021
- 2021-02-18 JP JP2023550000A patent/JP2024510883A/en active Pending
- 2021-02-18 KR KR1020237031735A patent/KR20230147152A/en active Search and Examination
- 2021-02-18 CN CN202180097199.2A patent/CN117203277A/en active Pending
- 2021-02-18 WO PCT/US2021/018492 patent/WO2022177560A1/en active Application Filing
-
2022
- 2022-02-17 TW TW111105713A patent/TW202244179A/en unknown
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US20140080952A1 (en) * | 2012-09-19 | 2014-03-20 | Momentive Performance Materials Inc. | Thermally conductive plastic compositions, extrusion apparatus and methods for making thermally conductive plastics |
US20140171567A1 (en) * | 2012-12-14 | 2014-06-19 | Sabic Innovative Plastics Ip B.V. | Thermally conductive flame retardant polymer compositions and uses thereof |
US20190161612A1 (en) * | 2015-08-17 | 2019-05-30 | Ticona Llc | Liquid Crystalline Polymer Composition for Camera Modules |
WO2018119153A2 (en) * | 2016-12-21 | 2018-06-28 | Intel Corporation | Wireless communication technology, apparatuses, and methods |
US20210057827A1 (en) * | 2019-08-21 | 2021-02-25 | Ticona Llc | Antenna System Including a Polymer Composition having a Low Dissipation Factor |
Also Published As
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CN117203277A (en) | 2023-12-08 |
TW202244179A (en) | 2022-11-16 |
KR20230147152A (en) | 2023-10-20 |
JP2024510883A (en) | 2024-03-12 |
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