The present invention is directed to formulations and manufactured products. More particularly, the present invention is directed to composite formulations and composite products having metal or conductive particles.
Electrically conductive metal-plastic composite materials are useful in a variety of components. Lower resistivity or higher conductivity is desirable for improving such components. Extended useful life of such components and easy electrical contact either by soldering or by other industry standard methods (for example, c-clips or pogo pins) to the components are also desirable. Further improvements to such components permit wider use in different environments.
Copper particles can be used in materials to produce relatively good electrically conductive composite formulations. However, such materials are not capable of use in certain applications, are not environmentally-stable when exposed to different extreme conditions required for various electronic, automotive product applications, and are not as conductive as materials including silver. However, silver is expensive and includes operational complexities.
Decreasing the composite resistivity and increasing conductivity of materials, without sacrificing cost, operational complexity, or operational properties continues to be desirable in the art. Also, having low electrical contact resistances and/or stability at extreme environments continues to be desirable in the art.
A composite formulation and composite product that show one or more improvements in comparison to the prior art would be desirable in the art.
In an embodiment, a composite formulation includes a polymer matrix having metal particles, the metal particles including dendritic particles and tin-containing particles. The metal particles are blended within the polymer matrix at a temperature greater than the melt temperature of the polymer matrix. The tin containing particles are at a concentration in the composite formulation of, by volume, between 10% and 36%, and the dendritic particles are at a concentration in the composite formulation of, by volume, between 16% and 40%. The temperature at which the metal particles are blended generates metal-metal diffusion of the metal particles, producing intermetallic phases, the temperature being at least the intermetallic annealing temperature of the metal particles.
In another embodiment, a composite formulation includes a polymer matrix and metal particles, the metal particles including copper particles and tin particles. The metal particles are blended within the polymer matrix at a temperature higher than the melt temperature of the polymer matrix. The temperature at which the metal particles are blended generates metal-metal diffusion of the metal particles, producing one or both of intermetallic phases and alloy phases. The metal particles include morphologies selected from the group consisting of dendrites, spheroid particles, flakes, and blends thereof. The copper particles have a maximum dimension of between 5 micrometers and 50 micrometers. The tin particles have a maximum dimension of between 2 micrometers and 50 micrometers. The tin particles are at a concentration in the composite formulation of, by volume, between 10% and 36%. The copper particles are at a concentration in the composite formulation of, by volume, between 16% and 40%. The composite formulation has a resistivity of less than 0.0006 ohm·cm at 23° C.
In another embodiment, a composite product produced from a composite formulation having metal particles blended within a polymer matrix at a temperature less than an intermetallic annealing temperature includes the polymer matrix and the metal particles, the metal particles, including tin particles and copper particles, and intermetallic compounds formed from at least a portion of the metal particles, the intermetallic compounds being formed by the composite formulation being treated at a temperature of at least the intermetallic annealing temperature during the producing of the composite product.
Other features and advantages of the present invention will be apparent from the following more detailed description, taken in conjunction with the accompanying drawings which illustrate, by way of example, the principles of the invention.
Wherever possible, the same reference numbers will be used throughout the drawings to represent the same parts.
Provided are a composite formulation and a composite product produced from a composite formulation. Embodiments of the present disclosure, for example, in comparison to similar concepts failing to disclose one or more of the features disclosed here, have lower resistivity (higher conductivity), have lower contact force requirements for achieving utilizing such lower resistivity (higher conductivity), have extended operational life (for example, based upon aging data), are capable of being soldered, are capable of being extruded, are capable of being molded, include increased intermetallics and/or alloy phases (such as, based upon similar or different metal particles disclosed herein), include metal-metal diffusion and/or micro-welding (such as, between similar or different metal particles disclosed herein), include increased particle-particle connectivity, and/or are capable of other advantages and distinctions apparent from the present disclosure. As used herein, the term “micro-welding” fusion techniques for small thicknesses (for example, less than 0.5 mm) and small cross-sections (for example, less than 10 mm2), including, but not limited to, welding techniques such as pressure-contact, electric, electrostatic, cold, ultrasonic, thermo-compression, electron-beam, laser, as well as their combinations.
Referring to
The polymer matrix 101 includes any suitable material capable of having the metal particles 103 blended within it. Suitable materials include, but are not limited to, polyvinylidene fluoride, polyethylene, polyethylene terephthalate, polybutylene terephthalate, liquid crystal polymer, and polymer-copolymer blends with or without process aids. In one embodiment, the polymer matrix 101 permits the composite formulation 100 to be extruded and/or molded (for example, injection molded, thermo-molded, sintered, or a combination thereof).
The composite formulation 100 includes any other suitable constituents. In one embodiment, a process aid is blended within the polymer matrix 101, for example, at a concentration, by volume, of between 3% and 10%, between 6% and 8%, between 7% and 8%, 6%, 7%, 7.5%, 8%, or any suitable combination, sub-combination, range, or sub-range therein. One suitable process aid is a lubricant, such as, dioctyl sebacate silicon-dioxide blend. Other suitable constituents capable of being blended within the polymer matrix 101 include, but are not limited to, a filler (for example, to increase viscosity and/or density), a curing agent (for example, for solvent-based curing and/or for radiation curing), a wetting agent, a defoamer, a dye or coloring agent, or a combination thereof.
The metal particles 103 in the composite formulation 100 include dendritic particles 501 (see
In one embodiment, the molding or extrusion temperature are above the melt temperature of the polymer 101 and above or below melt temperature of the tin-containing particles 701 to further complete the intermetallic diffusion and phase formation. Suitable temperature ranges for the molding or the extrusion include, but are not limited to, less than 300° C., less than 270° C., less than 250° C., less than 210° C., less than 180° C., between 210° C. and 170° C., between 180° C. and 220° C., between 190° C. and 230° C., between 200° C. and 240° C., between 230° C. and 270° C., between 260° C. and 300° C., or any suitable combination, sub-combination, range, or sub-range therein.
The metal particles 103 include two or more types of metals. The metal particles 103 are any suitable dimensions and morphologies capable of being blended within the polymer matrix 101. Suitable values for the maximum dimension of the metal particles 103 include, but are not limited to, 100 micrometers, 80 micrometers, 50 micrometers, 30 micrometers, 10 micrometers, 5 micrometers, 2 micrometers, less than 100 micrometers, less than 80 micrometers, between 50 micrometers and 100 micrometers, between 50 micrometers and 80 micrometers, between 30 micrometers and 100 micrometers, between 30 micrometers and 80 micrometers, between 30 micrometers and 50 micrometers, or any suitable combination, sub-combination, range, or sub-range therein.
The dendritic particles 501 and the tin-containing particles 701 are similar in size or different in size. Suitable maximum dimensions for the dendritic particles 501 include, but are not limited to, between 25 micrometers and 50 micrometers, between 25 micrometers and 50 micrometers, between 15 micrometers and 25 micrometers, or any suitable combination, sub-combination, range, or sub-range therein. Suitable maximum dimensions for the tin-containing particles 701 include, but are not limited to, between 2 micrometers and 50 micrometers, between 10 micrometers and 30 micrometers, between 5 micrometers and 25 micrometers, or any suitable combination, sub-combination, range, or sub-range therein.
Suitable morphologies for the metal particles 103 include, but are not limited to, dendrites, spheroid particles, flakes, powder, or a combination of morphologies. In one embodiment, the dendritic particles 501 and the tin-containing particles 701 differ in morphologies. In one embodiment, the tin-containing particles 701 include a morphology of spherical or cylindrical powder and/or the dendrites 501, for example, having copper particles, as shown in
The concentration of the metal particles 103, such as, the dendritic particles 501 and the tin-containing particles 701, provides desired properties for the composite formulation 100. The metal particles 103 are at a concentration in the composite formulation 100 of, by volume, between 30% and 50%, between 35% and 45%, between 38% and 42%, between 39% and 41%, 38%, 39%, 40%, 41%, 42%, or any suitable combination, sub-combination, range, or sub-range therein.
In one embodiment, the dendritic particles 501 and/or the copper are at a concentration in the composite formulation 100 of, by volume, between 16% and 40%, between 16% and 20%, between 20% and 24%, between 10% and 30%, between 18% and 22%, 10%, 16%, 18%, 20%, 22%, 24%, 30%, or any suitable combination, sub-combination, range, or sub-range therein.
In one embodiment, the tin-containing particles 701 are at a concentration in the composite formulation 100 of, by volume, between 10% and 36%, between 16% and 30%, between 25% and 36%, between 10% and 40%, between 20% and 30%, between 24% and 28%, 10%, 16%, 20%, 24%, 25%, 28%, 30%, 36%, 40%, or any suitable combination, sub-combination, range, or sub-range therein.
In one embodiment, a molded or extruded composite product 102 made of the composite formulation 100 has intermetallic or alloy phases or compositions 901 at the metal particle interfaces (see
The mixing or molding or extrusion process parameters affect the particle distribution, mixing, intermetallic or alloy phase formation of the composite formulation (See
The composite formulation 100 permits electrical connection at a level of force that is less than that which is necessary for electrically connecting with a comparative formulation (not shown) having copper but not tin or a tin alloy, for example, with the comparative formulation having resistivity of between 0.0005 to 0.001 ohm·cm. As shown in
The composite formulation 100 is capable of maintaining electrical resistivity and hence, the percolated network connection at temperatures of 85° C. or 150° C. for a longer duration than the comparative formulation (not shown) having copper but not tin or tin alloys, for example, with the comparative formulation having resistivity of between 0.0005 to 0.001 ohm·cm. For example, although the comparative formulation increase from 0.0005 ohm·cm to 0.005 ohm·cm over a period of 100 hours at 150° C. air, in one embodiment, the composite formulation 100 maintains resistivity (and corresponding conductivity) of less than 0.0006 ohm·cm over 12 days in 85° C. air less than 0.0006 ohm·cm over 10 days in 85° C. and 85% relative humidity, as shown in
The composite product 102 is capable of maintaining electrical contact resistance when exposed to various exposure conditions.
In one embodiment, the composite product 102 is post-treated below or above the melt temperature of the tin-containing particles 701 in a controlled vacuum or gas atmosphere. The treating is during the production of the composite product 102 from the composite formulation 100, for example, during extruding and/or during molding or is after the producing of the composite product 102. In one embodiment, the treating is in a controlled atmosphere, for example, being inert, substantially consisting of argon and/or nitrogen, any other suitable inert atmosphere, or being in a vacuum. In one embodiment, the treating permits the composite formulation 100 to further form and/or stabilize intermetallic or alloy compounds (see
In comparison to the composite product 102 when produced without the treating, the treating decreases resistivity (and increases corresponding conductivity), for example, by a factor of 2 to 10 times. Additionally or alternatively, in one embodiment, the treating decreases contact force requirements, for example, to a force of 25 to 50 gm, such as 30 gm, being capable of maintaining a contact resistance of less than 0.1 ohm. In one embodiment, the operational life of the composite product 102 is extended in comparison to the composite product 102 when produced without the treating.
Referring to
In one embodiment, the composite formulation 100 or the composite product 102 is reflowed or hand-soldered, for example, at least 6 times while maintaining resistivity within 30% of an initial electrical resistivity. Referring to
In a first example, according to an embodiment of the disclosure, the composite product is exposed to various wiping distances under 200 gm of force at temperatures of 85° C. or 150° C. in air for 10 days. The resulting electrical contact resistance is shown by the first set of conditions 801 in
In a second example, according to an embodiment of the disclosure, the composite product is exposed to various wiping distances under 200 gm of force at temperatures of 85° C. and 85% relative humidity for 10 days. The resulting electrical contact resistance is shown by the second set of conditions 803 in
In a third example, according to an embodiment of the disclosure, the composite product is exposed to various wiping distances under 200 gm of force and temperature cycles from 25° C. to 65° C. at 95% relative humidity for 10 days. The resulting electrical contact resistance is shown by the third set of conditions 805 in
In a fourth example, according to an embodiment of the disclosure, the composite product is exposed to various wiping distances under 200 gm of force and mixed flowing gas (for example, MFG class IIa) for 2 days at conditions which metallic copper generally corrodes. The resulting electrical contact resistance is shown by the fourth set of conditions 807 in
In a fifth example, according to an embodiment of the disclosure, the composite formulation includes, by volume, polyvinylidene fluoride (PVDF) at 52.5%, dioctyl sebacate silicon-dioxide at 7.5%, copper dendrite at 24%, and tin powder at 16%. Prior to heat treatment, the bulk resistivity is 5×10−4 ohm·cm and the contact resistance at 100 gm force is 350 milliohm. After heat treatment, the bulk resistivity is 2×10−4 ohm·cm and the contact resistance at 100 gm force is 15-40 milliohm.
In a sixth example, according to an embodiment of the disclosure, the composite formulation includes, by volume, polyvinylidene fluoride (PVDF) at 52.5%, dioctyl sebacate silicon-dioxide at 7.5%, copper dendrite at 16%, and tin powder at 24%. Prior to heat treatment, the bulk resistivity is 3×10−4 ohm·cm and the contact resistance at 100 gm force is 15-40 milliohm.
While the invention has been described with reference to one or more embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. In addition, all numerical values identified in the detailed description shall be interpreted as though the precise and approximate values are both expressly identified.