Thermoplastic composite for an antenna component and an article comprising the composite

Abstract

In one embodiment, a thermoplastic composite material comprises polypropylene; a plurality of glass fibers; wherein the glass fibers comprise boron trioxide and CaO, both based on the total weight of the glass fibers; a plurality of clay flakes; and a plurality of clay nanorods; wherein, based on the total weight of the thermoplastic composite material, the sum of the plurality of clay flakes and the plurality of clay nanorods comprises 0.5 to 10% by weight. In another embodiment, an article comprises an antenna array; a reflective layer located on the surface of the antenna array; and a spacer layer comprising a thermoplastic composite material located between the antenna array and the reflective layer, wherein the thermoplastic composite material comprises a thermoplastic polymer; a plurality of glass fibers; a plurality of clay flakes; and a plurality of clay nanorods.

Description

[Technical Field]

[0001] This invention relates to a thermoplastic composite material that can be used as a spacer layer in an antenna. [Previous Technology]

[0002] Spacers are used in antennas to maintain a constant gap between the antenna array and the external reflector. Developing such a material for use as a spacer layer is challenging because the spacer material must have a low coefficient of thermal expansion (CTE) to match the copper cladding that constitutes the antenna array, a low dielectric constant, and high melt flowability to fill large multichannel cavities. Although different polymers have been considered for this spacer layer, they generally do not meet one or more of the required specifications. For example, although polyethylene has a low dielectric constant, it has a CTE as high as 200 parts per million per degree Celsius (ppm / °C), which is significantly higher than copper's 17 ppm / °C. Conversely, although polystyrene with E-glass filler shows a lower CTE value, these compositions generally do not have the required dielectric constant or flowability.

[0003] Therefore, there is a need for an improved thermoplastic composite material that can be used as an intermediate spacer layer in an antenna. [Summary of the Invention]

[0004] This invention discloses a thermoplastic composite material that can be used as a spacer layer.

[0005] In one sample, based on the total weight of the thermoplastic composite material, the thermoplastic composite material contains 50 to 80 weight percent of polypropylene; based on the total weight of the thermoplastic composite material, the thermoplastic composite material contains 10 to 45 weight percent of a plurality of glass fibers; wherein the glass fibers contain greater than or equal to 12 weight percent of boric acid (B2O3) and less than or equal to 15 weight percent of CaO, both based on the total weight of the glass fibers; the plurality of The thermoplastic composite material comprises: clay flakes; wherein the average maximum length of the clay flakes is less than or equal to 200 nanometers; wherein the average thickness of the clay flakes is 1 to 10 nanometers; and a plurality of clay rods; wherein the average length of the clay rods is 50 to 600 nanometers; and the average diameter of the clay rods is 5 to 70 nanometers; and wherein, based on the total weight of the thermoplastic composite material, the thermoplastic composite material comprises a plurality of clay flakes and a plurality of clay nanorods totaling 0.5 to 10% by weight.

[0006] In another embodiment, an article comprises an antenna array; a reflective layer located on the surface of the antenna array; and a spacer layer comprising a thermoplastic component located between the antenna array and the reflective layer; wherein the thermoplastic composite comprises a thermoplastic polymer comprising at least one of a polyolefin, a polyphenylene ether, a polymethylpentene, or a para-polystyrene; a plurality of glass fibers; a plurality of clay flakes; and a plurality of clay rods.

[0007] The above and other features of the present invention are illustrated by the following figures, embodiments and claims.

Implementation Method

[0010] A thermoplastic composite material comprising a thermoplastic polymer, a plurality of glass fibers, and clay comprising a plurality of clay flakes and a plurality of clay rods has been discovered, exhibiting good balance properties, thus making it suitable for use as a spacer layer in antennas. This thermoplastic composite material exhibits enhanced flowability due to the mixed form of the clay and improved dielectric properties due to the glass fibers, thus forming a flowable thermoplastic composite material with excellent dielectric properties at 10 GHz. Importantly, this thermoplastic composite material achieves a coefficient of thermal expansion closer to that of copper. According to ASTM E1545-11 (2016), when measured at 40 to 100°C, the difference between the coefficient of thermal expansion of this thermoplastic composite material and that of copper is less than or equal to 30 parts per million per degree Celsius, or 15 to 25 parts per million per degree Celsius.

[0011] It should be noted that although this invention is primarily used for antenna spacers, this thermoplastic composite material can also be used in other applications requiring low coefficient of thermal expansion (CTE), low dielectric constant, and good melt flow properties. For example, this thermoplastic composite material can be used in blow molding or injection molding applications. This thermoplastic composite material can be used as a lens or radome.

[0012] The thermoplastic polymer may contain at least one of polyolefin, polyphenylene ether, polymethylpentene, or para-polystyrene. The presence of polymethylpentene or para-polystyrene may increase the thermal resistance of the thermoplastic polymer. The thermoplastic polymer may contain at least one of polyolefin, polymethylpentene, or para-polystyrene. According to ASTM D1238-20, the thermoplastic polymer, when measured at a temperature of 230°C and a weight of 2.16 kg, may have a melt flow index of 0.3 to 70 grams per 10 minutes (g / 10 min), or 10 to 30 grams per 10 minutes.

[0013] The thermoplastic polymer may contain a polyolefin. The polyolefin may contain a homopolymer (e.g., polyethylene (such as low-density polyethylene or high-density polyethylene), polypropylene, or an α-olefin polymer (such as a C3-10 α-olefin polymer)), a copolymer containing at least two ethylene, propylene, or C3-10 α-olefin units), or at least a portion thereof or a fully halogenated analogue. The polyolefin may contain polypropylene. The polypropylene may contain at least one polypropylene homopolymer or polypropylene copolymer. The polypropylene copolymer may contain at least one random copolymer, block copolymer, or heterogeneous copolymer. The heterogeneous propylene copolymer may contain an elastic propylene copolymer (E) dispersed in a polypropylene matrix.

[0014] The polypropylene may contain acid- or anhydride-modified polypropylene. The addition of a small amount of acid- or anhydride-modified polypropylene may contain 1 to 10 weight percent of acid- or anhydride-modified polypropylene based on the total weight of the polypropylene.

[0015] The polypropylene may comprise clarified polypropylene. Clarified polypropylene refers to polypropylene that is generally more transparent than polypropylene homopolymer or polypropylene block copolymer. The clarified polypropylene may contain 1 to 5 moles of repeating units derived from ethylene. The clarified polypropylene may contain at least one of clarifying additives or nucleation inhibitors to prevent or reduce the crystallinity of the clarified polypropylene.

[0016] Based on the total weight of the thermoplastic composite material, the thermoplastic composite material may contain 50 to 80 wt% or 55 to 70 wt% of thermoplastic polymer.

[0017] The thermoplastic composite material may comprise a plurality of glass fibers. The glass fibers are chopped glass fibers. The glass fibers may have an average length of 0.5 to 50 mm, or 1 to 25 mm, or 5 to 10 mm. The average fiber diameter of the glass fibers may be 2 to 50 micrometers, or 10 to 15 micrometers. The plurality of glass fibers may comprise at least one of NE glass, D glass, pure silica glass, or quartz fiber.

[0018] The plurality of glass fibers may contain greater than or equal to 12% by weight, or 15 to 25% by weight of boric acid (B₂O₃). The plurality of glass fibers may contain less than or equal to 15% by weight, or 0 to 10% by weight, or 0 to 1% by weight of CaO. Examples of such glass fibers include NE glass and D glass. Compared to conventional E glass, NE glass and D glass may contain lower alkaline earth metal content (such as CaO and MgO) and higher boric acid content. E glass typically contains 5 to 10% by weight of boric acid, 16 to 25% by weight of CaO, and 0 to 5% by weight of MgO. Therefore, compared to conventional E glass, the NE glass and the D glass may have lower dielectric constants and lower dielectric loss tangents. The NE glass may have at least one dielectric constant less than 5, or a dielectric loss tangent less than 0.002 at 1 GHz. The D-type glass may have at least one dielectric constant less than 4.5, or a dielectric loss tangent of less than 0.0032 at 10 GHz.

[0019] The thermoplastic composite material may contain 10 to 45 percent or 25 to 35 percent glass fiber based on the total weight of the thermoplastic composite material.

[0020] The thermoplastic composite material may contain clay. The clay may contain the organophilic folinic silicate. The clay may contain bentonite. The clay may contain kaolinite. The clay may contain montmorillonite. The clay may contain at least one of soapstone, silicon, aluminum bentonite, or lithium bentonite, and the clay may be untreated.

[0021] The clay may comprise a plurality of clay flakes and a plurality of clay rods. The average maximum length of the clay flakes and the clay rods may be less than or equal to 600 nanometers, or less than or equal to 500 nanometers. The average maximum length of the clay flakes may be 50 to 600 nanometers, or 50 to 200 nanometers, or 75 to 150 nanometers. The average thickness of the clay flakes may be 1 to 10 nanometers, or 1 to 5 nanometers. The average length of the clay rods may be 50 to 600 nanometers, or 100 to 500 nanometers. The average diameter of the clay rods may be 5 to 70 nanometers, or 10 to 50 nanometers.

[0022] Based on the total weight of the thermoplastic composite material, the thermoplastic composite material may contain a plurality of clay flakes and a plurality of clay nanorods totaling 0.5 to 10% by weight, or 1 to 5% by weight.

[0023] The thermoplastic composite material may be a solid material without pore spaces. Conversely, the thermoplastic composite material may be a foamed material, for example, with a porosity of 1 to 80 volume percentages or 10 to 50 volume percentages based on the total volume of the thermoplastic composite material. The foamed material may comprise at least one of chemically foamed materials, physically foamed materials, or synthetic foamed materials comprising a plurality of hollow spheres.

[0024] If a blowing agent is used, the blowing agent may contain at least one of a physical blowing agent or a chemical blowing agent. The physical blowing agent may contain at least one of a hydrocarbon (e.g., a C1-6 hydrocarbon comprising a straight-chain C1-6 alkane, a branched C1-6 alkane, a cyclic C1-6 alkane, an ether, or an ester), a partially halogenated hydrocarbon (e.g., a straight-chain, branched, or cyclic C1-6 fluoroalkane), nitrogen, oxygen, argon, or carbon dioxide. Specific physical blowing agents include chlorofluorocarbons (e.g., 1,1-dichloro-1-fluoroethane, 1,1-dichloro-2,2,2-trifluoroethane, monochlorodifluoromethane, or 1-chloro-1,1-difluoroethane); and fluorocarbons (e.g., 1,1,1,3,3,3-hexafluoropropane, 2,2,4,4-tetrafluorobutane, 1,1,1,3,3,3-hexafluoro-2-methylpropane, 1,1,1,3,3-pentafluoropropane, 1,1,1,2,2-pentafluoropropane, 1,1,1,2,3-pentafluoropropane, 1,1,2,3 ... 2,3-Pentafluoropropane, 1,1,1,3,3,4-Hexafluorobutane, 1,1,1,3,3-Pentafluorobutane, 1,1,1,4,4,4-Hexafluorobutane, 1,1,1,4,4-Pentafluorobutane, 1,1,2,2,3,3-Hexafluoropropane, 1,1,1,2,3,3-Hexafluoropropane, 1,1-Difluoroethane, 1,1,1,2-Tetrafluoroethane, or Pentafluoroethane; fluoroethers (e.g., methyl-1,1,1-trifluoroethyl ether, or difluoromethyl-1,1,1-trifluoroethyl ether); or hydrocarbons (e.g., n-pentane, isopentane, or cyclopentane). The physical blowing agent may contain at least one of carbon dioxide or nitrogen.

[0025] Examples of chemical blowing agents include blowing agents that can decompose to form gas. The chemical blowing agent may contain at least one of water, azoisobutyronitrile, azodimethylamine (e.g., azobismethylamine), barium azodiacarboxylate, substituted hydrazides (e.g., diphenylsulfonyl-3,3'-disulfonylhydrazine, 4,4'-hydroxybis(benzenesulfonylhydrazine), trihydrazine triazine, or arylbis(sulfonylhydrazine)), amine urea (e.g., p-methylbenzenesulfonylurea, or 4,4'-hydroxy-bis(benzenesulfonylurea)), triazoles (e.g., 5-morpholino-1,2,3,4-thiotriazole), N-nitroso compounds (e.g., N,N'-dinitrospentamethylenetetramine, or N,N-dimethyl-N,N'-dinitrosophthalamide), or benzoxazines (e.g., o-carboxyaniline carboxycarbamate). The chemical foaming agent may contain an endothermic foaming agent, such as at least one of sodium monocitrate or sodium bicarbonate.

[0026] The foam material may comprise a synthetic foam material, which refers to a solid material filled with hollow particles, particularly spheres or hollow nanotubes (e.g., hollow kaolin nanotubes). The hollow particles may comprise at least one of ceramic hollow particles, polymer hollow particles, or glass hollow particles (e.g., particles made of basic borosilicate glass). Based on the total volume of the foam layer, the synthetic foam material may comprise 1 to 70 volume percent, or 5 to 70 volume percent, or 10 to 50 volume percent of hollow particles. The average diameter of the particles may be less than or equal to 300 micrometers, or 15 to 200 micrometers, or 20 to 70 micrometers. Compared to other types of foam materials, the synthetic foam material may have one or more superior mechanical stability, a better coefficient of thermal expansion, or reduced hygroscopicity.

[0027] The thermoplastic composite material may contain one or more optional additives. The additive may contain at least one of the following: polyhedral oligomeric silsesquioxane, dielectric filler (e.g., silica (e.g., colloidal or fumed silica) or wollastonite), hydrogen-terminated nanodiamond, graphene, stabilizer (e.g., amine-resistant light stabilizer), acid scavenger, antioxidant, metal deactivator, slip agent, colorant, flame retardant, or release agent. The additive may contain at least one of the following: hydrogen-terminated nanodiamond, graphene, polyhedral oligomeric silsesquioxane, silica, or wollastonite.

[0028] The thermoplastic composite material may comprise a polyhedral oligomeric silsesquioxane (commonly referred to as "POSS," also known as "silsesquioxane"). The silsesquioxane is a nanoscale inorganic material with a silicon dioxide core and reactive functional groups on its surface. The silsesquioxane may have a cubic or similar cubic structure, comprising silicon atoms at the vertices and interconnected oxygen atoms. Each silicon atom may be covalently bonded to a dangling R group. A silsesquioxane, such as octa(dimethylsiloxane)silsesquioxane (R8Si8O12), comprises a cage consisting of silicon and oxygen atoms surrounding a core with eight dangling R groups. Each R group may independently be hydrogen, hydroxyl, alkyl, aryl, or alkenyl, wherein the R group may contain 1 to 12 carbon atoms and one or more heteroatoms (e.g., oxygen, nitrogen, phosphorus, silicon, or halogen). Each R group may independently contain at least one reactive group, such as an alcohol, epoxy group, ester, amine, ketone, ether, or halide. Each R group may independently contain at least one of silanol, alkoxide, or chloride. The silsesquioxane may contain at least one of trisilylphenyl POSS, dodecyl POSS, octaisobutyl POSS, or octamethyl POSS. The silsesquioxane may contain trisilylphenyl POSS. Based on the total weight of the thermoplastic composite, the amount of the silsesquioxane may be 0.05 to 5% by weight, or 0.5 to 2% by weight.

[0029] According to ASTM-D1238-20, when the thermoplastic polymer is measured at a temperature of 230°C and a weight of 2.16 kg, the thermoplastic composite may have a gravity melt index (MFI) greater than or equal to 20 grams per 10 minutes (grams / 10 minutes) or 20 to 30 grams per 10 minutes.

[0030] According to ASTM-D1238-20, when the thermoplastic composite is measured at a temperature of 230°C and a weight of 2.6 kg, the thermoplastic composite may have a melt volume flow rate (MVR) of greater than or equal to 15 cubic centimeters per 10 minutes (cubic centimeters / 10 minutes) or 15 to 30 cubic centimeters / 10 minutes.

[0031] According to ASTM E1545-11 (2016), the thermoplastic composite material is measured in the flow direction for a 0.40-inch (1.02 mm) sample at 40 to 100°C. The thermoplastic composite material may have a coefficient of thermal expansion of less than or equal to 30 ppm / °C or 15 to 25 ppm / °C.

[0032] The dielectric constant (Dk) of this thermoplastic composite material at 10 GHz can be 1.5 to 10, or 1.5 to 4, or 1.5 to 3, or 1.5 to 2.8. The dielectric loss tangent (Df) of this thermoplastic composite material can be less than or equal to 0.005, or 0.0005 to 0.005. Its dielectric properties can be determined at 10 GHz according to ASTM D3380-14.

[0033] An article may include the thermoplastic composite material. The article may be an antenna, and the thermoplastic composite material may be used as a spacer layer in the antenna. For example, the article may include an antenna array; a reflective layer located on the surface of the antenna array; and a spacer layer containing a thermoplastic component located between the antenna array and the reflective layer. Figure 1 is a diagram of the article 10, which includes an antenna array 20; a reflective layer 40 located on the surface 22 of the antenna array 20; and a spacer layer 30 containing a thermoplastic component located between the antenna array 20 and the reflective layer 40.

[0034] The thermoplastic composite material may comprise a thermoplastic polymer (e.g., polypropylene), a plurality of glass fibers, a plurality of clay flakes, and a plurality of clay rods. Based on the total weight of the thermoplastic composite material, the thermoplastic composite material may comprise 50 to 80 weight percent, or 55 to 70 weight percent, of polypropylene. Based on the total weight of the thermoplastic composite material, the thermoplastic composite material may contain 10 to 45 weight percent, or 25 to 35 weight percent, of a plurality of glass fibers. The glass fibers may comprise greater than or equal to 12 weight percent, or 15 to 25 weight percent, of boric acid (B₂O₃), and less than or equal to 15 weight percent, or 0 to 10 weight percent, or 0 to 1 weight percent, of CaO, both based on the total weight of the glass fibers. The clay flakes may have an average maximum length of 200 nanometers, or 75 to 150 nanometers. The clay flakes may have an average thickness of 1 to 10 nanometers, or 1 to 5 nanometers. The clay rods may have an average length of 50 to 600 nanometers, or 100 to 500 nanometers. The clay rods may have an average diameter of 5 to 70 nanometers, or 10 to 50 nanometers. Based on the total weight of the thermoplastic composite, the thermoplastic composite comprises a plurality of clay flakes and a plurality of clay nanorods totaling 0.5 to 10% by weight, or 1 to 5% by weight. According to ASTM E1545-11 (2016), the thermoplastic composite, measured at 40 to 100°C, may have a coefficient of thermal expansion less than or equal to 30 parts per million (ppm) or 15 to 25 ppm. The polypropylene may be a copolymer comprising repeating units from ethylene. The glass fiber has an average length of at least one of 0.5 to 50 mm, 1 to 25 mm, or 5 to 10 mm; or the average fiber diameter of the glass fiber may be 2 to 50 micrometers, or 10 to 15 micrometers. At least one of the plurality of clay flakes or the plurality of clay rods may contain montmorillonite. Based on the total volume of the thermoplastic composite, the thermoplastic composite may have a porosity of 1 to 80 volume percent, or 10 to 50 volume percent. The thermoplastic composite may further contain at least one of hydrogen-terminated nanodiamonds, polyhedral oligomeric silsesquioxanes, silica, or wollastonite.

[0035] An article may include an antenna array; a reflective layer located on the surface of the antenna array; and a spacer layer comprising a thermoplastic component located between the antenna array and the reflective layer. The thermoplastic composite material may include a thermoplastic polymer comprising at least one of a polyolefin, polyphenylene ether, polymethylpentene, or para-polystyrene; a plurality of glass fibers; a plurality of clay flakes; and a plurality of clay rods. The thermoplastic composite material may be a thermoplastic composite material as described above. According to ASTM E1545-11 (2016), the thermoplastic composite material may have a coefficient of thermal expansion of less than or equal to 30 parts per million (ppm) or 15 to 25 ppm when measured at 40 to 100°C. The thermoplastic polymer may comprise polypropylene comprising repeating units derived from ethylene. Based on the total weight of the thermoplastic composite material, the thermoplastic polymer may be present in an amount of 50 to 80% by weight, or 55 to 70% by weight. The glass fiber may comprise at least one of pure silica glass fiber or quartz fiber. The glass fiber may comprise greater than or equal to 12% by weight, or 15 to 25% by weight, boric acid (B₂O₃), and less than or equal to 15% by weight, or 0 to 10% by weight, or 0 to 1% by weight, both based on the total weight of the glass fiber. The average length of the glass fiber may be at least one of 0.5 to 50 mm, or 1 to 25 mm, or 5 to 10 mm. The average fiber diameter of the glass fiber may be 2 to 50 micrometers, or 10 to 15 micrometers. The plurality of clay flakes or the plurality of clay rods may contain montmorillonite. The average maximum length of the clay flakes may be 200 nanometers, or 75 to 150 nanometers. The average thickness of the clay flakes can be 1 to 10 nanometers, or 1 to 5 nanometers. The average length of the clay rods can be 50 to 600 nanometers, or 100 to 500 nanometers. The average diameter of the clay rods can be 5 to 70 nanometers, or 10 to 50 nanometers. Based on the total weight of the thermoplastic composite, the thermoplastic composite may contain a plurality of clay flakes and a plurality of clay nanorods totaling 0.5 to 10 weight percent, or 1 to 5 weight percent. Based on the total volume of the thermoplastic composite, the porosity of the thermoplastic composite is 1 to 80 volume percent, or 10 to 50 volume percent. The thermoplastic composite may further contain at least one of hydrogen-terminated nanodiamonds, polyhedral oligomeric silsesquioxanes, silica, or wollastonite.

[0036] An article may include an antenna array; a reflective layer located on the surface of the antenna array; and a spacer layer comprising a thermoplastic component located between the antenna array and the reflective layer. The thermoplastic composite material may comprise 55 to 70 weight percent of polypropylene; 25 to 35 weight percent of a plurality of glass fibers; wherein the glass fibers have at least one of an average length of 0.5 to 50 mm, or 1 to 25 mm, or 5 to 10 mm, or the average fiber diameter of the glass fibers may be 2 to 50 micrometers, or 10 to 15 micrometers; and wherein the glass fibers comprise greater than or equal to 12 weight percent, or 15 to 25 weight percent of boric acid and less than or equal to 15 weight percent, or 0 to 10 weight percent, or 0 to 1 weight percent of CaO, both based on the total weight of the glass fibers; and a plurality of clay. Clay flakes; wherein the average maximum length of the clay flakes is less than or equal to 200 nm, or 75 to 150 nm; or the average thickness of the clay flakes is 1 to 10 nm, or 1 to 5 nm; and a plurality of clay rods; wherein the average length of the clay rods is 50 to 600 nm, or 100 to 500 nm; or the average diameter of the clay rods is 5 to 70 nm, or 10 to 50 nm; and wherein, based on the total weight of the thermoplastic composite, the thermoplastic composite comprises a plurality of clay flakes and a plurality of clay nanorods totaling 0.5 to 10% by weight, or 1 to 5% by weight; and wherein, according to ASTM E1545-11 (2016), the thermoplastic composite, measured at 40 to 100°C, has a coefficient of thermal expansion less than or equal to 30 parts per million, or 15 to 25 parts per million, of thermal expansion.

[0037] The formation of the thermoplastic composite material is not particularly limited. For example, the formation may include mixing or extrusion in a melt mixer. The thermoplastic composite material may be prepared by extruding a composition comprising at least the thermoplastic polymer, the plurality of glass fibers, and the plurality of clay flakes; and the plurality of clay rods. Extrusion may be performed using a twin-screw extruder having a plurality of material feed ports. The method may include feeding the thermoplastic polymer into the main feed throat of the extruder to form a melt, feeding the plurality of clay flakes and the plurality of clay rods into the melt, and feeding the glass fibers into the melt. The feeding of the glass fibers may occur downstream of the respective clay feeds. The feeding of the glass fibers may occur upstream of the die joint. Adding the glass fibers downstream of the nano-clay and optional stabilizers may minimize at least one of the sintering of the nano-clay or the breakage of the glass fibers. The thermoplastic composite material can be formed into strands, for example, by being pushed by a mold plate, cooled in a water bath, forced to dry, and cut into granules.

[0038] The thermoplastic composite material can be cast into articles of the required size and shape. For example, strands or particles of the thermoplastic composite material can be fed into an injection molding machine, where they can be melted, compacted, and forcibly fed into a mold cavity to form an article.

[0039] The following embodiments are provided to illustrate the present invention. These embodiments are for illustrative purposes only and are not intended to limit the apparatus manufactured according to the present invention to the materials, conditions, or process parameters listed herein. [Examples]

[0040] In an embodiment, at the 4th minute, when the temperature was 230 degrees Celsius (°C) and the mixing speed was 75 revolutions per minute (rpm), the mixing torque was measured in milligrams (mg).

[0041] The gravity melt flow index (MFI) was measured according to ASTM-D1238-20 at a temperature of 230°C and a weight of 2.16 kg. The melt volumetric flow rate (MVR) was measured according to ASTM-D1238-20 at a temperature of 230°C and a weight of 2.16 kg. The melt flow properties were measured on a Tinius Olsen Extrusion Plastometer Model MP600.

[0042] The coefficient of thermal expansion is measured in parts per million per degree Celsius according to ASTM E1545-11 (2016). The CTE test is conducted on a compression-molded plate with an induced flow direction and is performed on a TA instrument TMA450 at temperatures ranging from -40°C to 110°C.

[0043] The dielectric constant (Dk) and dielectric loss tangent (Df) are measured on a compression-formed plate using the long strip (LSL) method ASTM D3380-14.

[0044] Table 1 shows the ingredients used in the examples. Table 1 Element describe source Random polypropylene 5122C3, a clarified random copolymer Pinnacle NE glass fiber NE glass, shredded glass fiber Nittobo E glass fiber E-glass, shredded glass fiber SILMIM LLC Max CT Nano Clay BYK-MAX CT 4270, an organophilic foliated silicate BYK-Chemie GmbH Cloisite 20 nanometer clay CLOISITE 20, bis(hydrogenated tallow alkyl)dimethyl, bentonite salt BYK-Chemie GmbH

[0045] Examples 1 to 5: Preparation of three thermoplastic composite materials. Thermoplastic composite materials were prepared by synthesizing the components shown in Table 2 in a CW BRABENDER Intelli-Torque rheometer, which has three 50 cubic centimeter (cc) mixing bowls with drum stirring blades. The temperature of the stirrer was set to 220°C, and the speed of the stirrer blades was 75 revolutions per minute (rpm). The polypropylene copolymer was melted in the mixer, and if glass and nano-clay were present, they were added next. After stirring for 5 minutes, the stirrer was stopped, disassembled, and the molten composition was removed and cooled to form the thermoplastic composite material. Table 2 Example 1 2 3 Polypropylene (by weight) 100 69 65 NE glass fiber (by weight) - 31 31 Max CT Nano Clay (by weight) - - 4

[0046] The properties of the thermoplastic composite material, as measured, are shown in Table 3. In Examples 4 and 5, these properties were compared with two commercially available materials. In Example 4, the thermoplastic component was NORYL PPX 630, available from SABIC. In Example 5, the thermoplastic component was THERMYLENE P6-4OFG-0100, available from Asahi Kasei. Table 3 shows the measured values, or values ​​obtained from their respective data sheets using the test methods disclosed therein. Table 3 Example 1 2 3 4 5 Mixed torque (mg) - 476 389 - - MFI (g / 10 minutes) 12 15.3 23.6 - 7 MVR (cc / 10 minutes) 13.3 13.6 21.1 3* 5.6 CTE (ppm / °C) ~170 37 18 20 - Dielectric constant at 10 GHz - 2.56 2.61 ~2.8 2.8 Dielectric loss at 10 GHz - 0.002 0.003 - 0.003 *(Measured at 260°C / 5 kg)

[0047] When comparing Example 3 with Examples 1 and 2, Table 3 shows that adding a small amount of nano-clay to the thermoplastic composite material can significantly reduce the CTE. Comparing Example 3 with commercially available products of Examples 4 and 5, it can be seen that Example 3 has a lower CTE value and a lower dielectric constant at 10 GHz.

[0048] Examples 6 to 11 The thermoplastic composites of Examples 6 to 11 were prepared in the amounts shown in Table 4, and the properties of each thermoplastic composite were measured. Table 4 Example 2 3 6 7 8 9 10 11 Polypropylene (wt%) 69 65 69 65 65 65 65 65 NE glass fiber (wt%) 31 31 - - 35 - 31 - E glass fiber (wt%) - - 31 31 - 35 - 31 Max CT Nano Clay (wt%) - 4 - 4 - - - - Cloisite 20 nanometer clay (wt%) - - - - - - 4 4 nature Mixed torque (mg) 476 389 288 361 370 299 388 387 MFI (g / 10 minutes) 15.3 23.6 32.3 10.4 22.0 30.7 10.1 11.4 MVR (cc / 10 minutes) 13.6 21.1 28.8 9.0 19.6 26.3 9.0 9.8 CTE (ppm / °C) 37 18 twenty three 29 95 64 73 33 Dielectric constant at 10 GHz 2.56 2.61 2.67 2.72 2.58 2.71 2.64 2.68 Dielectric loss at 10 GHz 0.002 0.003 0.003 0.003 0.004 0.004 0.003 0.003

[0049] Table 4 shows that the thermoplastic composite of Example 4 exhibits the lowest CTE value, while maintaining good flow properties and good dielectric properties at 10 GHz. Compared to Example 7, which contains E glass fiber instead of NE glass fiber, Example 3 reduces the CTE value by nearly 40%. Compared to Example 10, which contains Cloisite 20 nm clay instead of Max CT nano clay, Example 3 reduces the CTE value by nearly 75%.

[0050] The following are non-limiting embodiments of the present invention.

[0051] Sample 1: A thermoplastic composite material comprising: 50 to 80 weight percent of polypropylene, or 55 to 70 weight percent of polypropylene, based on the total weight of the thermoplastic composite material; and 10 to 45 weight percent, or 25 to 35 weight percent of a plurality of glass fibers, based on the total weight of the thermoplastic composite material; wherein the glass fibers comprise greater than or equal to 12 weight percent, or 15 to 25 weight percent of boric acid (B2O3), and less than or equal to 15 weight percent, or 0 to 10 weight percent, or 0 to 1 weight percent of CaO, both based on the total weight of the glass fibers; The thermoplastic composite comprises several clay flakes; wherein the average maximum length of the clay flakes is less than or equal to 200 nanometers, or 75 to 150 nanometers; wherein the average thickness of the clay flakes is 1 to 10 nanometers, or 1 to 5 nanometers; and a plurality of clay rods; wherein the average length of the clay rods is 50 to 600 nanometers, or 100 to 500 nanometers; and the average diameter of the clay rods is 5 to 70 nanometers, or 10 to 50 nanometers; and wherein, based on the total weight of the thermoplastic composite, the thermoplastic composite comprises a plurality of clay flakes and a plurality of clay nanorods totaling 0.5 to 10% by weight, or 1 to 5% by weight.

[0052] Sample 2: The thermoplastic composite material as described in Sample 1, wherein, according to ASTM E1545-11 (2016), the coefficient of thermal expansion of the thermoplastic composite material is less than or equal to 30 parts per million per degree Celsius when measured at 40 to 100°C.

[0053] State 3: A thermoplastic composite material as described in any of the preceding states, wherein the polypropylene is a copolymer comprising repeating units from ethylene.

[0054] Form 4: The thermoplastic composite material as described in any of the preceding forms, wherein the glass fiber has at least one of an average length of 0.5 to 50 mm, or 1 to 25 mm, or 5 to 10 mm; or the average fiber diameter of the glass fiber may be 2 to 50 micrometers, or 10 to 15 micrometers.

[0055] State 5: The thermoplastic composite material as described in any of the preceding states, wherein at least one of the plurality of clay flakes or the plurality of clay rods contains montmorillonite.

[0056] State 6: The thermoplastic composite material as described in any of the preceding states, wherein, based on the total volume of the thermoplastic composite material, the porosity of the thermoplastic composite material is 1 to 80 volume percentages or 10 to 50 volume percentages.

[0057] State 7: The thermoplastic composite material as described in any of the preceding states, wherein it further comprises at least one of hydrogen-terminated nanodiamond, polyhedral oligomeric silsesquioxane, silica or wollastonite.

[0058] Sample 8: An article comprising: an antenna array; a reflective layer located on the surface of the antenna array; and a spacer layer comprising a thermoplastic component located between the antenna array and the reflective layer, wherein the thermoplastic composite material comprises a thermoplastic polymer comprising at least one of polyolefin, polyphenylene ether, polymethylpentene, or para-polystyrene; a plurality of glass fibers; a plurality of clay flakes; and a plurality of clay rods; wherein the thermoplastic composite material may optionally be the thermoplastic composite material described in any of the preceding samples.

[0059] Sample 9: The article as described in Sample 8, wherein, according to ASTM E1545-11 (2016), the thermoplastic composite material has a coefficient of thermal expansion of less than or equal to 30 parts per million or 15 to 25 parts per million when measured at 40 to 100°C.

[0060] Form 10: An article as described in any one of Forms 8 to 9, wherein the thermoplastic polymer comprises polypropylene containing repeating units from ethylene.

[0061] Form 11: An article as described in any one of Forms 8 to 10, wherein the thermoplastic polymer is present in an amount of 50 to 80% by weight or 55 to 70% by weight based on the total weight of the thermoplastic composite material.

[0062] Form 12: An article as described in any one of Forms 8 to 11, wherein the glass fiber comprises at least one of pure silica glass fiber or quartz fiber; or wherein the glass fiber comprises greater than or equal to 12% by weight, or 15 to 25% by weight of boric acid (B2O3), and less than or equal to 15% by weight, or 0 to 10% by weight, or 0 to 1% by weight of CaO, both based on the total weight of the glass fiber.

[0063] Form 13: An article as described in any one of Forms 8 to 12, wherein the glass fiber has an average length of at least one of 0.5 to 50 mm, or 1 to 25 mm, or 5 to 10 mm; or the average fiber diameter of the glass fiber may be 2 to 50 micrometers, or 10 to 15 micrometers.

[0064] Sample 14: an article of any one of the portions 8 to 13, wherein at least one of the plurality of clay flakes or the plurality of clay rods contains montmorillonite.

[0065] State 15: an article of any one of states 8 to 14, wherein the average maximum length of the clay piece is less than or equal to 200 nanometers, or 75 to 150 nanometers; or wherein the average thickness of the clay piece is 1 to 10 nanometers, or 1 to 5 nanometers.

[0066] State 16: The article described in any one of States 8 to 15, wherein the average length of the clay rod is 50 to 600 nanometers or 100 to 500 nanometers; or wherein the average diameter of the clay rod is 5 to 70 nanometers or 10 to 50 nanometers.

[0067] Form 17: An article as described in any one of Forms 8 to 16, wherein, based on the total weight of the thermoplastic composite material, the thermoplastic composite material comprises a plurality of clay flakes and a plurality of clay nanorods totaling 0.5 to 10 percent by weight, or 1 to 5 percent by weight.

[0068] State 18: an article as described in any of the states 8 to 17, wherein the porosity of the thermoplastic composite material is 1 to 80 volume percentage or 10 to 50 volume percentage based on the total volume of the thermoplastic composite material.

[0069] Form 19: an article of any one of Forms 8 to 18, wherein it further comprises at least one of hydrogen-terminated nanodiamond, polyhedral oligomeric silsesquioxane, silica or wollastonite.

[0070] Sample 20: An article comprising: an antenna array; a reflective layer located on the surface of the antenna array; and a spacer layer comprising a thermoplastic component located between the antenna array and the reflective layer; wherein the thermoplastic composite comprises 55 to 70 weight percent of polypropylene; 25 to 35 weight percent of a plurality of glass fibers; wherein the glass fibers have an average length of at least one of 0.5 to 50 mm, or 1 to 25 mm, or 5 to 10 mm, or the average fiber diameter of the glass fibers may be 2 to 50 micrometers, or 10 to 15 micrometers; and wherein the glass fibers comprise greater than or equal to 12 weight percent, or 15 to 25 weight percent of boric acid, and less than or equal to 15 weight percent, or 0 to 10 weight percent of boric acid. The thermoplastic composite comprises, or 0 to 1 weight percent of CaO, both based on the total weight of the glass fiber; a plurality of clay flakes; wherein the average maximum length of the clay flakes is less than or equal to 200 nm, or 75 to 150 nm; or wherein the average thickness of the clay flakes is 1 to 10 nm, or 1 to 5 nm; and a plurality of clay rods; wherein the average length of the clay rods is 50 to 600 nm, or 100 to 500 nm; or wherein the average diameter of the clay rods is 5 to 70 nm, or 10 to 50 nm; and wherein, based on the total weight of the thermoplastic composite, the thermoplastic composite comprises, 0.5 to 10 weight percent, or 1 to 5 weight percent, of the plurality of clay flakes and the plurality of clay nanorods; and wherein, according to ASTM E1545-11(2016), the thermoplastic composite material is measured at 40 to 100°C and has a coefficient of thermal expansion of less than or equal to 30 parts per million or 15 to 25 parts per million.

[0071] The foregoing composition, method, and article may alternatively comprise, be composed of, or substantially comprise of any suitable material, step, or component disclosed herein. The foregoing composition, method, and article may additionally or alternatively be formulated to be free of or substantially free of any material (or type), step, or component that is not essential for achieving the function or purpose of the foregoing composition, method, and article.

[0072] Unless otherwise expressly stated herein, the terms "a," "an," "the," "the," and "at least one" as used in this invention do not imply a limitation of quantity and are intended to cover both singular and plural forms. For example, unless otherwise expressly stated herein, "an element" and "at least one element" have the same meaning. The term "combination" includes blends, mixtures, alloys, reaction products, and the like. Furthermore, "at least one of" refers to a combination of each of the listed individual elements and any two or more of the listed elements, as well as a combination of at least one of the listed elements and a similar element not listed. Unless otherwise expressly stated herein, the term "or" means "and / or." Throughout this specification, references to "an aspect," "another aspect," "some aspects," etc., refer to specific elements (e.g., features, structures, steps, or properties) described in association with that aspect, which are included in at least one aspect described in this invention, and may or may not be present in other aspects. Furthermore, it should be understood that these elements can be combined in any suitable manner across the various aspects.

[0073] Unless otherwise stated herein, all test standards are the most recent valid standards as of the filing date of this application, or, if priority is claimed, the most recent valid standards as of the filing date of the earliest priority application for which such test standard is claimed.

[0074] All endpoints of ranges for the same component or property include the endpoint, can be combined independently, and include all intermediate points and ranges. For example, the range of "up to 25% by weight, or 5 to 20% by weight" includes the endpoint and all intermediate values ​​of the "5 to 25% by weight" range, such as 10 to 23% by weight.

[0075] Unless otherwise defined, the technical and scientific terms used in this invention have the same meanings as commonly understood by one of ordinary skill in the art to which this invention pertains. Compounds are described using standard nomenclature.

[0076] All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if any terminology of this invention contradicts or conflicts with the terminology in the incorporated references, the terminology of this invention shall take precedence over the conflicting terminology in the incorporated references.

[0077] Although a particular embodiment has been described, the applicant or others skilled in the art may conceive of alternatives, modifications, variations, improvements, and substantially equivalents that are not currently foreseen or may not be foreseen. Therefore, the scope of the appended patent application, which is to be amended, is intended to encompass all such alternatives, modifications, variations, improvements, and substantially equivalents.

[0078] This application claims priority to U.S. Provisional Patent Application No. 63 / 186,511, filed May 10, 2021. The full text of that application is hereby provided. [Simplified Explanation of the Diagram]

[0008] The following figures are illustrative embodiments provided to illustrate the present invention. These figures are not intended to limit the apparatus manufactured according to the present invention to the materials, conditions, or process parameters listed herein.

[0009] This diagram includes an antenna with a spacer layer.

Claims

1. A thermoplastic composite material, characterized in that it comprises: based on the total weight of the thermoplastic composite material, 50 to 80 weight percent of polypropylene homopolymer or polypropylene copolymer; based on the total weight of the thermoplastic composite material, a plurality of glass fibers comprising 10 to 45 weight percent; wherein, The glass fiber comprises greater than or equal to 12 weight percent of boron trioxide (B2O3) and less than or equal to 15 weight percent of CaO, both based on the total weight of the glass fiber; a plurality of clay flakes; wherein the average maximum length of the clay flakes is less than or equal to 200 nanometers; wherein the average thickness of the clay flakes is 1 to 10 nanometers; and a plurality of clay nanorods; wherein the average length of the clay nanorods is 50 to 600 nanometers; and the average diameter of the clay nanorods is 5 to 70 nanometers; and wherein, based on the total weight of the thermoplastic composite material, the thermoplastic composite material comprises a total of 0.5 to 10 weight percent of the plurality of clay flakes and the plurality of clay nanorods.

2. The thermoplastic composite material as described in claim 1, wherein, According to ASTM E1545-11 (2016), the coefficient of thermal expansion of this thermoplastic composite material is less than or equal to 30 parts per million per degree Celsius when measured at 40 to 100°C.

3. The thermoplastic composite material as described in claim 1 or 2, wherein, This polypropylene copolymer is a copolymer containing repeating units derived from ethylene.

4. The thermoplastic composite material as described in claim 1 or 2, wherein, The glass fiber has at least one of an average length of 0.5 to 50 millimeters; or the average fiber diameter of the glass fiber may be 2 to 50 micrometers.

5. The thermoplastic composite material as described in claim 1 or 2, wherein, At least one of the plurality of clay flakes or the plurality of clay nanorods contains montmorillonite.

6. The thermoplastic composite material as described in claim 1 or 2, wherein, Based on the total volume of the thermoplastic composite material, the porosity of the thermoplastic composite material is 1 to 80% by volume.

7. The thermoplastic composite material as described in claim 1 or 2, wherein, It further includes at least one of hydrogen-terminated nanodiamonds, polyhedral oligomeric silica silsesquioxanes, silica, or wollastonite.

8. An article comprising a thermoplastic composite material, characterized in that it comprises: an antenna array; a reflective layer located on the surface of the antenna array; and a spacer layer comprising the thermoplastic composite material located between the antenna array and the reflective layer; wherein, The thermoplastic composite material comprises: a thermoplastic polymer comprising at least one of a polyolefin, a polyphenylene ether, a polymethylpentene, or a para-polystyrene; a plurality of glass fibers; a plurality of clay flakes; and a plurality of clay nanorods.

9. The article of manufacture as described in claim 8, wherein, According to ASTM E1545-11 (2016), the coefficient of thermal expansion of this thermoplastic composite material is less than or equal to 30 parts per million per degree Celsius when measured at 40 to 100°C.

10. The article of manufacture as described in any one of claims 8 to 9, wherein, The thermoplastic polymer comprises the polypropylene copolymer containing repeating units derived from ethylene.

11. The article of manufacture as described in any one of claims 8 to 9, wherein, Based on the total weight of the thermoplastic composite, the thermoplastic polymer is present in an amount of 50 to 80% by weight of the thermoplastic composite.

12. The article of manufacture as described in any one of claims 8 to 9, wherein, The glass fiber comprises at least one of pure silica glass fiber or quartz fiber; or wherein the glass fiber comprises greater than or equal to 12 weight percent of boron trioxide (B2O3) and less than or equal to 15 weight percent of CaO, both based on the total weight of the glass fiber.

13. The article of manufacture as described in any one of claims 8 to 9, wherein, The glass fiber has at least one of an average length of 0.5 to 50 millimeters; or the average fiber diameter of the glass fiber may be 2 to 50 micrometers.

14. The article of manufacture as described in any one of claims 8 to 9, wherein, At least one of the plurality of clay flakes or the plurality of clay nanorods contains montmorillonite.

15. The article of manufacture as described in any one of claims 8 to 9, wherein, The average maximum length of the clay fragment is less than or equal to 200 nanometers; or the average thickness of the clay fragment is 1 to 10 nanometers.

16. The article of manufacture as described in any one of claims 8 to 9, wherein, The average length of the clay nanorod is 50 to 600 nanometers; or the average diameter of the clay nanorod is 5 to 70 nanometers.

17. The article of manufacture as described in any one of claims 8 to 9, wherein, Based on the total weight of the thermoplastic composite material, the total weight of the plurality of clay flakes and the plurality of clay nanorods in the thermoplastic composite material is 0.5 to 10% by weight.

18. The article of manufacture as described in any one of claims 8 to 9, wherein, Based on the total volume of the thermoplastic composite material, the porosity of the thermoplastic composite material is 1 to 80% by volume.

19. The article of manufacture as described in any one of claims 8 to 9, wherein, It further includes at least one of hydrogen-terminated nanodiamonds, polyhedral oligomeric silica silsesquioxanes, silica, or wollastonite.

20. An article comprising a thermoplastic composite material, characterized in that it comprises: an antenna array; a reflective layer located on the surface of the antenna array; and a spacer layer comprising the thermoplastic composite material located between the antenna array and the reflective layer; wherein, The thermoplastic composite material comprises: 55 to 70 weight percent of polypropylene homopolymer or polypropylene copolymer; 25 to 35 weight percent of a plurality of glass fibers; wherein the glass fibers have at least one of an average length of 0.5 to 50 mm, or the average fiber diameter of the glass fibers may be 2 to 50 micrometers; and wherein the glass fibers comprise greater than or equal to 12 weight percent of boron trioxide and less than or equal to 15 weight percent of CaO, both based on the total weight of the glass fibers. The thermoplastic composite comprises a plurality of clay flakes; wherein the average maximum length of the clay flakes is less than or equal to 200 nanometers; or wherein the average thickness of the clay flakes is 1 to 10 nanometers; and a plurality of clay nanorods; wherein the average length of the clay nanorods is 50 to 600 nanometers; or wherein the average diameter of the clay nanorods is 5 to 70 nanometers; and wherein, based on the total weight of the thermoplastic composite, the thermoplastic composite comprises a total of 0.5 to 10% by weight of the plurality of clay flakes and the plurality of clay nanorods; and wherein, according to ASTM E1545-11 (2016), the coefficient of thermal expansion of the thermoplastic composite, when measured at 40 to 100°C, is less than or equal to 30 parts per million per degree Celsius.

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