The present disclosure relates generally to thermal interface materials, and more particularly to gel-type thermal interface materials.
Thermal interface materials (TIMs) are widely used to dissipate heat from electronic components, such as central processing units, video graphics arrays, servers, game consoles, smart phones, LED boards, and the like. Thermal interface materials are typically used to transfer excess heat from the electronic component to a heat spreader, such as a heat sink.
A typical electronics package structure 10 including thermal interface materials is illustrated in
Traditional thermal interface materials include components such as gap pads. However, gap pads have certain disadvantages, such as inability to meet very small thickness requirements and being difficult to use in automated production.
Other thermal interface materials include gel products. Gel products may be automatically dispensed for large scale production, and can be formed to desired shapes and thicknesses. However, typical gel products with good flow properties may potentially experience oil leaking (also known as “bleeding”). Improvements in the foregoing are desired.
The present disclosure provides thermal interface materials that are useful in transferring heat from heat generating electronic devices, such as computer chips, to heat dissipating structures, such as heat spreaders and heat sinks. The thermal interface material includes at least one silicone oil, at least one catalyst, at least one thermally conductive filler having a relatively large surface area, a solvent, at least one inhibitor, and at least one crosslinker. The at least one thermally conductive filler reduces the oil leakage of the TIM, and the solvent increases the flow rate of the TIM without negating the reduction of oil leakage realized by the thermally conductive fillers.
In one exemplary embodiment, a thermal interface material is provided. The thermal interface material includes a low molecular weight silicone oil having a weight (Mw) average molecular weight less than 50,000 Daltons; at least one thermally conductive filler having a surface area greater than 1.0 m2/g; and a high molecular weight silicone oil, wherein the high molecular weight silicone oil comprises a vinyl functional silicone oil having a weight (Mw) average molecular weight of at least 60,000 Daltons.
In one more particular embodiment, the thermal interface material has a viscosity greater than 1500 Pa.s. In one more particular embodiment, the thermal interface material further includes a solvent having a boiling point between 60° C. and 220° C. and a viscosity between 0.2 cSt and 50 cSt. In one more particular embodiment, the thermal interface material has a viscosity between 150 Pa.s and 650 Pa.s. In one more particular embodiment, the at least one thermally conductive filler includes a first thermally conductive filler, a second thermally conductive filler, and a third thermally conductive filler, wherein the first thermally conductive filer is a metal oxide having a surface area between 0.1 m2/g to 1.0 m2/g, the second thermally conductive filler is a metal oxide having a surface area between 0.5 m2/g and 2.0 m2/g, and the third thermally conductive filler is a metal oxide having a surface area between 5.0 m2/g and 10.0 m2/g. In one more particular embodiment, the first thermally conductive filler has an average particle size of at least 10 microns, the second thermally conductive filler has an average particle size between 1 micron and 10 microns, and the third thermally conductive filler has an average particle size less than 1 micron.
In one more particular embodiment, the thermal interface material comprises: from 2 wt. % to 10 wt. % of the low molecular weight silicone oil; from 50 wt. % to 95 wt. % of the at least one thermally conductive filler; and from 0.1 wt. % to 5 wt. % of the high molecular weight silicone oil; from 0.1 wt. % to 5 wt. % of a solvent; from 0.1 wt. % to 5 wt. % of a coupling agent; from 0.1 wt. % to 1 wt. % of a crosslinker; from 0.1 wt. % to 5 wt. % of an inhibitor; and from 0.1 wt. % to 5 wt. % of a catalyst. In one more particular embodiment, the at least one thermally conductive filler includes: from 25 wt. % to 50 wt. % of a first thermally conductive filler having a surface area between 0.1 m2/g to 1.0 m2/g; from 25 wt. % to 50 wt. % of a second thermally conductive filler having a surface area between 0.5 m2/g and 2.0 m2/g; and from 25 wt. % to 50 wt. % of a third thermally conductive filler having a surface area between 5.0 m2/g and 10.0 m2/g. In one more particular embodiment, the thermal interface material has a viscosity between 150 Pa.s and 650 Pa.s.
In one embodiment, a thermal interface material is provided. The thermal interface material includes: a low molecular weight silicone oil having a weight (Mw) average molecular weight less than 50,000 Daltons; a first thermally conductive filler, a second thermally conductive filler, and a third thermally conductive filler, wherein the first thermally conductive filer is a metal oxide having a surface area between 0.1 m2/g to 1.0 m2/g, the second thermally conductive filler is a metal oxide having a surface area between 0.5 m2/g and 2.0 m2/g, and the third thermally conductive filler is a metal oxide having a surface area between 5.0 m2/g and 10.0 m2/g; and a high molecular weight silicone oil, wherein the high molecular weight silicone oil comprises a vinyl functional silicone oil having a weight (Mw) average molecular weight of at least 60,000 Daltons; and a solvent having a boiling point between 60° C. and 220° C. and a viscosity between 0.2 cSt and 50 cSt.
In one more particular embodiment, the thermal interface material comprises: from 2 wt. % to 10 wt. % of the low molecular weight silicone oil; from 25 wt. % to 50 wt. % of a first thermally conductive filler having a surface area between 0.1 m2/g to 1.0 m2/g; from 25 wt. % to 50 wt. % of a second thermally conductive filler having a surface area between 0.5 m2/g and 2.0 m2/g; and from 25 wt. % to 50 wt. % of a third thermally conductive filler having a surface area between 5.0 m2/g and 10.0 m2/g; from 0.1 wt. % to 5 wt. % of the high molecular weight silicone oil; from 0.1 wt. % to 5 wt. % of a solvent; from 0.1 wt. % to 5 wt. % of a coupling agent; from 0.1 wt. % to 1 wt. % of a crosslinker; from 0.1 wt. % to 5 wt. % of an inhibitor; and from 0.1 wt. % to 5 wt. % of a catalyst. In one more particular embodiment, the low molecular weight silicone oil comprises a vinyl functional silicone oil and the high molecular weight silicone oil is a vinyl silicone oil having a kinematic viscosity of 2,000,000 cSt. In one more particular embodiment, the first thermally conductive filler has an average particle size of at least 10 microns, the second thermally conductive filler has an average particle size between 1 micron and 10 microns, and the third thermally conductive filler has an average particle size less than 1 micron. In one more particular embodiment, the thermal interface material has a bleeding trace value of between 1 mm and 5 mm and a flowrate between 20 g/min and 50 g/min. In one more particular embodiment, the thermal interface material has a viscosity between 150 Pa.s and 650 Pa.s.
In one embodiment, an electronic component is provided. The electronic component includes: a heat sink; an electronic chip; a thermal interface material positioned between the heat sink and electronic chip, the thermal interface material including: a low molecular weight silicone oil having a weight (Mw) average molecular weight less than 50,000 Daltons; at least one thermally conductive filler having a surface area greater than 1.0 m2/g; and a high molecular weight silicone oil, wherein the high molecular weight silicone oil comprises a vinyl functional silicone oil having a weight (Mw) average molecular weight of at least 60,000 Daltons.
In one more particular embodiment, the thermal interface material has a viscosity greater than 1500 Pa.s. In one more particular embodiment, the electronic component further includes: a solvent having a boiling point between 60° C. and 220° C. and a viscosity between 0.2 cSt and 50 cSt. In one more particular embodiment, the thermal interface material has a viscosity between 150 Pa·s and 650 Pa·s. In one more particular embodiment, the at least one thermally conductive filler includes a first thermally conductive filler, a second thermally conductive filler, and a third thermally conductive filler, wherein the first thermally conductive filer is a metal oxide having a surface area between 0.1 m2/g to 1.0 m2/g, the second thermally conductive filler is a metal oxide having a surface area between 0.5 m2/g and 2.0 m2/g, and the third thermally conductive filler is a metal oxide having a surface area between 5.0 m2/g and 10.0 m2/g.
In one more particular embodiment, the electronic component further comprises a heat spreader positioned between the heat sink and the electronic chip, wherein the first surface layer is in contact with a surface of the electronic chip and the second surface layer is in contact with the heat spreader. In one more particular embodiment, the electronic component further comprises a heat spreader positioned between the heat sink and the electronic chip, wherein the first surface layer is in contact with a surface of the heat spreader and the second surface layer is in contact with the heat sink.
The above-mentioned and other features and advantages of this disclosure, and the manner of attaining them, will become more apparent and the invention itself will be better understood by reference to the following description of embodiments of the invention taken in conjunction with the accompanying drawings, wherein:
Corresponding reference characters indicate corresponding parts throughout the several views. The exemplifications set out herein illustrate exemplary embodiments of the invention and such exemplifications are not to be construed as limiting the scope of the invention in any manner.
The present invention relates to thermal interface materials (TIMs) useful in transferring heat away from electronic components. In one exemplary embodiment, the TIM comprises at least one silicone oil, at least one catalyst, at least one thermally conductive filler having a relatively larger surface area, a solvent, at least one inhibitor, and at least one crosslinker. The at least one thermally conductive filler reduces the oil leakage of the TIM, and the solvent increases the flow rate of the TIM without negating the reduction of oil leakage realized by the thermally conductive fillers.
The present disclosure provides a matrix for a TIM material that includes at least one low molecular weight silicone oil and at least one high molecular weight silicone oil. The silicone oil includes one or more crosslinkable groups, such as vinyl, hydride, hydroxyl and acrylate functional groups, that are crosslinked by a catalyst. In one embodiment, one or more silicone oils include a first silicone oil and a second silicone oil, where the first silicone oil is a vinyl functional silicone oil and the second silicone oil is a hydride functional silicone oil. The silicone oil wets the thermally conductive filler and forms a dispensable fluid for the TIM.
In one exemplary embodiment, the silicone oil includes a silicone rubber such as the KE series products available from Shin-Etsu, such as SILBIONE® available from Bluestar, such as ELASTOSIL®, SilGel®, SILPURAN®, and SEMICOSIL® available from Wacker, such as Silopren® available from Momentive, such as Dow Corning®, Silastic®, XIAMETER®, Syl-off® and SYLGARD® available from Dow Corning, such as SQUARE® available from Square Silicone, such as Andril® available from AB specialty Silicones. Other polysiloxanes are available from Wacker, Shin-etsu, Dowcoring, Momentive, Bluestar, RUNHE, AB Specialty Silicones, Gelest, and United Chemical Technologies.
The TIM includes a low weight average molecular weight silicone oil as measured by gel permeation chromatography (GPC). The low molecular weight silicone oil wets the thermally conductive filler to form a dispensable fluid for the TIM. Exemplary low molecular weight silicone oils may include a vinyl silicone oil having a general formula as shown below:
An exemplary low molecular weight vinyl silicone oil may also include a small amount of platinum catalyst.
Vinyl functional silicone oils include an organo-silicone component with Si—CH═CH2 groups. Exemplary vinyl functional silicone oils include vinyl-terminated silicone oils and vinyl-grafted silicone oils in which the Si—CH=CH2 group is grafted onto the polymer chain, and combinations thereof.
Exemplary vinyl-terminated silicone oils include vinyl terminated polydimethylsiloxane, such as DMS-V00 (having a weight average molecular weight (Mw) of 186 Daltons), DMS-V03 (having a Mw of about 500 Daltons), DMS-V05 (having a Mw of about 800 Daltons), DMS-V21 (having a Mw of about 6,000 Daltons), DMS-V22 (having a Mw of about 9400 Daltons), DMS-V25 (having a Mw of about 17,200 Daltons), DMS-V25R (having a Mw of about 17,200 Daltons), DMS-V35 (having a Mw of about 49,500 Daltons), DMS-V35R (having a Mw of about 49,500 Daltons), each available from Gelest, Inc. Exemplary vinyl-terminated silicone oils include vinyl terminated diphenylsiloxane-dimethylsiloxane copolymer, such as PDV-0325 (having a Mw of about 15,500 Daltons), PDV-0331 (having a Mw of about 27,000 Daltons), PDV-0525 (having a Mw of about 14,000 Daltons), PDV-1625 (having a Mw of about 9,500 Daltons), PDV-1631 (having a Mw of about 19,000 Daltons), PDV-2331 (having a Mw of about 12,500 Daltons), each available from Gelest, Inc. Exemplary vinyl-terminated silicone oils include vinyl terminated polyphenylmethylsiloxane, such as PMV-9925 (having a Mw of about 2000-3000 Daltons) available from Gelest, Inc. Exemplary vinyl-terminated silicone oils include vinyl terminated diethylsiloxane-dimethylsiloxane copolymer, such as EDV-2025(having a Mw of about 16,500-19,000 Daltons) available from Gelest, Inc.
Exemplary vinyl-grafted silicone oils include vinylmethylsiloxane homopolymers, such as VMS-005 (having a Mw of about 258-431 Daltons), VMS-T11 (having a Mw of about 1000-1500 Daltons), both available from Gelest, Inc. Exemplary vinyl-grafted silicone oils include vinylmethylsiloxane-dimethylsiloxane copolymers, such as trimethylsiloxyl terminated silicone oils, silanol terminated silicone oils, and vinyl terminated silicone oils.
In one exemplary embodiment, the vinyl-grafted silicone oil is a vinylmethylsiloxane terpolymers, including a vinylmethylsiloxane-octylmethylsiloxane-dimethylsiloxane terpolymer, such as VAT-4326(having a Mw of about 10,000-12,000 Daltons), or a vinylmethylsiloxane-methoxypolyethylenoxypropylmethylsiloxane-dimethylsiloxan e terpolymer, such as VBT-1323(having a Mw of about 8,000-12,000 Daltons), or a vinylmethylsiloxane-phenylmethylsiloxane-dimethylsiloxane(having a Mw of about 2,500-3,000 Daltons); each available from Gelest, Inc.
In one exemplary embodiment, the vinyl-functional silicone oil comprises a vinyl T resin or a vinyl Q resin.
In one exemplary embodiment, the silicone oil is a vinyl functional oil, such as RH-Vi303, RH-Vi301 from RUNHE, such as Andril® VS 200, Andril® VS 1000 from AB Specialty Silicones.
Exemplary low molecular weight silicone oils may have a weight (Mw) average molecular weight as little as 50 Daltons, 500 Daltons, 1000 Daltons, as great as 5000 Daltons, 10,000 Daltons, 50,000 Daltons, or within any range defined between any two of the foregoing values such as between 50 Daltons to 50,000 Daltons, 500 Daltons to 50,000 Daltons, or 1,000 Daltons to 50,000 Daltons, for example.
Exemplary low molecular weight silicone oils may have a kinematic viscosity as little as 0.5 cSt, 5 cSt, 100 cSt, as great as 5,000 cSt, 10,000 cSt, 50,000 cSt, or within any range defined between any two of the foregoing values, such as 0.5 cSt to 50,000 cSt, 5 cSt to 10,000 cSt, or 100 cSt to 5,000 cSt, for example, as measured according to ASTM D445. In one exemplary embodiment, an exemplary low molecular weight silicone oil is a low molecular weight vinyl silicone oil having a kinematic viscosity of 1,000 cSt. In another exemplary embodiment, an exemplary low molecular weight silicone oil is a low molecular weight vinyl silicone oil having a kinematic viscosity above 1,500 cSt.
The TIM comprises one or more low molecular weight silicone oils in an amount as little as 0.1 wt. %, 0.5 wt. %, 0.67 wt. %, 1 wt. %, as great as 3 wt. %, 5 wt. %, 10 wt. %, 20 wt. %, or within any range defined between any two of the foregoing values, based on the total weight of the TIM, such as 0.1 wt. % to 15 wt. %, 0.1 wt. % to 10 wt. %, or 0.67 wt. % to 10 wt. %.
The TIM includes a high molecular weight silicone oil as measured by gel permeation chromatography (GPC). The high molecular weight silicone oil functions to prevent cracking of the TIM during thermal cycling. Exemplary high molecular weight silicone oils may include a vinyl silicone oil having a general formula as shown below, similar to the low molecular weight silicone oils described above:
Vinyl functional silicone oils include an organo-silicone component with Si—CH═CH2 groups. Exemplary vinyl functional silicone oils include vinyl-terminated silicone oils and vinyl-grafted silicone oils in which the Si—CH=CH2 group is grafted onto the polymer chain, and combinations thereof.
Exemplary vinyl-terminated silicone oils include vinyl terminated polydimethylsiloxane, such as DMS-V41 (having a Mw of about 62,700 Daltons), DMS-V42 (having a Mw of about 72,000 Daltons), DMS-V46 (having a Mw of about 117,000 Daltons), DMS-V51 (having a Mw of about 140,000 Daltons), and DMS-V52 (having a Mw of about 155,000 Daltons), each available from Gelest, Inc.
Exemplary vinyl-grafted silicone oils include vinylmethylsiloxane-dimethylsiloxane copolymers, such as trimethylsiloxyl terminated silicone oils, silanol terminated silicone oils, and vinyl terminated silicone oils.
In one exemplary embodiment, the vinyl-grafted silicone oil is a vinylmethylsiloxane terpolymers. In one exemplary embodiment, the vinyl-functional silicone oil comprises a vinyl T resin or a vinyl Q resin.
Another exemplary high molecular weight silicone oil may include a hydride functional silicone oil having an organo-silicone component and Si—H groups. Exemplary hydride functional silicone oils include hydride-terminated silicone oils, hydride-grafted silicone oils in which the Si—H group is grafted onto the polymer chain, and combinations thereof.
In one exemplary embodiment, the hydride-terminated silicone oil is a hydride terminated polydimethylsiloxane such as DMS-H41(having a Mw of about 62,700 Daltons), available from Gelest, Inc. In one exemplary embodiment, the hydride-terminated silicone oil is a methylhydrosiloxane-dimethylsiloxane copolymer, such as a trimethylsiloxyl terminated or hydride terminated. Exemplary trimethylsiloxyl terminated copolymers include HMS-064 (having a Mw of about 60,000-65,000 Daltons), available from Gelest, Inc.
Exemplary low molecular weight silicone oils may have a weight (Mw) average molecular weight as little as 100,000 Daltons, 300,000 Daltons, 500,000 Daltons, as great as 1,000,000 Daltons, 10,000,000 Daltons, 100,000,000 Daltons, or within any range defined between any two of the foregoing values, such as 100,000 Daltons to 100,000,000 Daltons, 300,000 Daltons to 10,000,000 Daltons, or 500,000 Daltons to 1,000,000 Daltons, for example.
Exemplary high molecular weight silicone oils may have a kinematic viscosity as little as 10,000 cSt, 20,000 cSt, 100,000 cSt, as great as 1,000,000 cSt, 10,000,000 cSt, 100,000,000 cSt, or within any range defined between any two of the foregoing values, such as 10,000 cSt to 100,000,000 cSt, 20,000 cSt to 10,000,000 cSt, or 100,000 cSt to 1,000,000 cSt, for example, as measured according to ASTM D445. In one exemplary embodiment, an exemplary high molecular weight silicone oil is a high molecular weight vinyl silicone oil having a kinematic viscosity of 2,000,000 cSt.
The TIM may comprise one or more high molecular weight silicone oils in an amount as little as 0.01 wt %, 0.1 wt. %, 0.25 wt. %, 0.5 wt. %, 0.67 wt. %, 0.75 wt. %, as great as 1 wt. %, 1.5 wt. %, 2 wt. %, 5 wt. %, or within any range defined between any two of the foregoing values, based on the total weight of the TIM, such as 0.1 wt. % to 5 wt. %, 0.1 wt. % to 1 wt. %, or 0.25 wt. % to 0.67 wt. %. In one exemplary embodiment, the TIM includes a high molecular weight silicone oil in the amount of about 1.5 wt. %.
The TIM further includes one or more catalyst for catalyzing the addition reaction. Exemplary catalysts comprise platinum containing materials and rhodium containing materials. Exemplary platinum containing catalysts may have the general formula shown below:
Exemplary platinum contain catalysts include: Platinum cyclovinylmethylsiloxane complex(Ashby Karstedt Catalyst), Platinum carbonyl cyclovinylmethylsiloxane complex(Ossko catalyst), Platinum divinyltetramethyldisiloxane dimethyl fumarate complex, Platinum divinyltetramethyldisiloxane dimethyl maleate complex and the like. Exemplary of Platinum carbonyl cyclovinylmethylsiloxane complexes include SIP6829.2, exemplary of Platinum divinyltetramethyldisiloxane complex include SIP6830.3 and SIP6831.2, exemplary of platinum cyclovinylmethylsiloxane complex include SIP6833.2, all available from Gelest, Inc. Further exemplary platinum containing material catalysts include Catalyst OL available from Wacker Chemie AG, and PC065, PC072, PC073, PC074, PC075, PC076, PC085, PC086, PC087, PC088 available from United Chemical Technologies Inc.
Exemplary rhodium containing materials include Tris(dibutylsulfide)Rhodium trichloride with product code INRH078, available from Gelest, Inc.
Without wishing to be held to any particular theory it is believed that the platinum catalyst reacts with a vinyl silicone oil and a hydrosilicone oil as shown below.
The TIM may comprise the one or more catalyst in an amount as little as 5 ppm, 10 ppm, 15 ppm, 20 ppm, as great as 25 ppm, 30 ppm, 40 ppm, 50 ppm, 100 ppm, 200 ppm, 500 ppm, 1000 ppm, or within any range defined between any two of the foregoing values, based on the total weight of the silicone oil, such as 10 ppm to 30 ppm, 20 ppm to 100 ppm, or 5 ppm to 500 ppm, for example.
In one exemplary embodiment, the catalyst is provided as a mixture with one or more of the silicone oils. In one exemplary embodiment, the platinum containing material catalyst is combined to a functional silicone oil, such as KE-1012-A, KE-1031-A, KE-109E-A, KE-1051J-A, KE-1800T-A, KE1204A, KE1218A available from Shin-Etsu, such as SILBIONE® RT Gel 4725 SLD A available from Bluestar, such as SilGel® 612 A, ELASTOSIL® LR 3153A, ELASTOSIL® LR 3003A, ELASTOSIL® LR 3005A, SEMICOSIL® 961A, SEMICOSIL® 927A, SEMICOSIL® 205A, SILPURAN® 2440 available from Wacker, such as Silopren® LSR 2010A available from Momentive, such as XIAMETER® RBL-9200 A, XIAMETER® RBL-2004 A, XIAMETER® RBL-9050 A, XIAMETER® RBL-1552 A, Silastic® FL 30-9201 A, Silastic® 9202 A, Silastic® 9204 A, Silastic® 9206 A, SYLGARD® 184A, Dow Corning® QP-1 A, Dow corning® C6 A, Dow Corning® CV9204 A available from Dow Corning.
The TIM may comprise a catalyst in an amount as little as 0.01 wt %, 0.1 wt. %, 0.2 wt. %, as great as 0.3 wt. %, 0.4 wt. %, 0.5 wt. %, or within any range defined between any two of the foregoing values, based on the total weight of the TIM, such as 0.01 wt. % to 0.5 wt. %, 0.01 wt. % to 0.4 wt. %, or 0.01 wt. % to 0.3 wt. %, for example. In one exemplary embodiment, the TIM includes a catalyst in the amount of about 0.01 wt. %. In another exemplary embodiment, the TIM includes a catalyst in the amount of about 0.3 wt. %.
In another embodiment, the platinum containing material catalyst is combined to a high molecular weight vinyl functional silicone oil.
The TIM includes one or more thermally conductive fillers. The thermally conductive filler provides a thermally conductive material to conduct heat through the thermal interface material. Exemplary thermally conductive fillers include metals, alloys, nonmetals, metal oxides and ceramics, and combinations thereof. The metals include, but are not limited to, aluminum, copper, silver, zinc, nickel, tin, indium, and lead. The nonmetal include, but are not limited to, carbon, graphite, carbon nanotubes, carbon fibers, graphenes, boron nitride and silicon nitride. The metal oxide or ceramics include but not limited to alumina (aluminum oxide), aluminum nitride, boron nitride, zinc oxide, and tin oxide.
The TIM may comprise the one or more thermally conductive fillers in an amount as little as 10 wt. %, 20 wt. %, 25 wt. %, 50 wt. %, as great as 75 wt. %, 80 wt. %, 85 wt. %, 90 wt. %, 95 wt. %, 97 wt. %, or within any range defined between any two of the foregoing values, based on the total weight of the TIM, such as 10 wt. % to 95 wt. %, 20 wt. % to 95 wt. %, or 25 wt. % to 90 wt. %, for example.
Exemplary thermally conductive fillers may have an average particle size of as little as 0.1 microns, 1 micron, 10 microns, as great as 50 microns, 75 microns, 100 microns or within any range defined between any two of the foregoing values, such as 0.1 microns to 100 microns, 0.1 microns to 75 microns, or 0.1 microns to 50 microns, for example.
Exemplary thermally conductive fillers may have a surface area as little as 0.10 m2/g, 0.50 m2/g, 1.0 m2/g, as great as 5.0 m2/g, 7.0 m2/g, 8.5 m2/g, 10.0 m2/g, or within any range defined between any two of the foregoing values, such as 0.1 m2/g to 0.5 m2/g, 0.10 m2/g to 10.0 m2/g, or 0.10 m2/g to 8.5 m2/g as measured by Brunauer-Emmett-Teller (BET) Procedure, ASTM C1274-2012, or ASTM B922-2010. In one exemplary embodiment, an exemplary thermally conductive filler has a surface area of 0.15 m2/g. In another embodiment, an exemplary thermally conductive filler has a surface area of 1.1 m2/g. In yet another exemplary embodiment, an exemplary thermally conductive filler has a surface area of 7.6 m2/g.
Without wishing to be held to a particular theory, it is believed that the higher surface area thermally conductive fillers used in the TIM controls the oil bleeding of the TIM because such high surface area filler(s) reduce the flow rate of the thermal gel (i.e., more viscous). Moreover, a larger surface area filler can absorb oil molecules and because of the intermolecular forces involved with absorption, oil is unable to freely flow from the TIM, thereby reducing oil bleeding. Furthermore, the use of smaller fillers results in short distances between the fillers and forms a capillary network within the TIM. The capillary network absorbs the oil and therefore, reduces the oil bleeding.
In one exemplary embodiment, the TIM may include a first thermally conductive filler, a second thermally conductive filler, and a third thermally conductive filler, wherein the first thermally conductive filer has a surface area as little as 0.1 m2/g, 0.2 m2/g, 0.5 m2/g, as great as 0.6 m2/g, 0.8 m2/g, 1.0 m2/g, or within any range defined therebetween, the second thermally conductive filler has a surface area as little as 0.5 m2/g, 0.7 m2/g, 0.9 m2/g as great as 1.5 m2/g, 1.7 m2/g, 2.0 m2/g, or within any range defined therebetween, and the third thermally conductive filler has a surface area as little as 5.0 m2/g, 6.0 m2/g, 7.0 m2/g, as great as 8.0 m2/g, 9.0 m2/g, 10.0 m2/g or within any range therebetween.
In one exemplary embodiment, the TIM includes a first thermally conductive filler in the amount of as little as 20 wt. %, 25 wt. %, 30 wt. %, as great as 45 wt. %, 50 wt. %, 60 wt % or within any range defined between any two of the foregoing values with respect to the total TIM composition, such as 20 wt. % to 60 wt. %, 25 wt. % to 50 wt. %, or 30 wt. % to 45 wt. %, for example. The first thermally conductive filler has an average particle size of as little as 10 microns. 35 microns, 40 microns, as great as 45 microns, 50 microns, 60 microns, or within any range defined between any two of the foregoing values, such as 10 microns to 60 microns, 10 microns to 50 microns, or 10 microns to 45 microns, for example. The first thermally conductive filler has a surface area as little as 0.1 m2/g, 0.2 m2/g, 0.5 m2/g, as great as 0.6 m2/g, 0.8 m2/g, 1.0 m2/g, or within any range defined therebetween, such as 0.1 m2/g to 1.0 m2/g, 0.1 m2/g to 0.8 m2/g, or 0.1 m2/g to 0.6 m2/g for example.
The exemplary TIM can further include a second thermally conductive filler in the amount of as little as 20 wt. %, 25 wt. %, 30 wt. %, as great as 45 wt. %, 50 wt. %, 60 wt % or within any range defined between any two of the foregoing values with respect to the total TIM composition, such as 20 wt. % to 60 wt. %, 25 wt. % to 50 wt. %, or 25 wt. % to 45 wt. %, for example. The second thermally conductive filler has an average particle size of as little as 1 micron, 3, microns. 5 microns, as great as 10 microns, 15 microns, 20 microns, or within any range defined between any two of the foregoing values, such as 1 micron to 20 microns, 3 microns to 15 microns, or 5 microns to 15 microns, for example. The second thermally conductive filler has a surface area as little as 0.5 m2/g, 0.7 m2/g, 0.9 m2/g as great as 1.5 m2/g, 1.7 m2/g, 2.0 m2/g, or within any range defined therebetween, such as 0.5 m2/g to 2.0 m2/g, 0.7 m2/g to 1.7 m2/g, or 0.9 m2/g to 1.5 m2/g, for example.
The exemplary TIM further includes a third thermally conductive filler in the amount of as little as 20 wt. %, 25 wt. %, 30 wt. %, as great as 45 wt. %, 50 wt. %, 60 wt % or within any range defined between any two of the foregoing values with respect to the total TIM composition, such as 20 wt. % to 60 wt. %, 25 wt. % to 50 wt. %, or 30 wt. % to 45 wt. %, for example. The third thermally conductive filler has an average particle size of as little as 0.1 microns, 0.3, microns. 0.5 microns, as great as 1 micron, 1.5 microns, 2 microns, or within any range defined between any two of the foregoing values, such as 0.1 microns to 2 microns, 0.3 microns to 1.5 microns, or 0.5 microns to 1 micron, for example. The third thermally conductive filler has a surface area as little as 5.0 m2/g, 6.0 m2/g, 7.0 m2/g, as great as 8.0 m2/g, 9.0 m2/g, 10.0 m2/g or within any range therebetween, such as 5.0 m2/g to 10 m2/g, 6.0 m2/g to 9.0 m2/g, or 7.0 m2/g to 8.0 m2/g, for example.
Exemplary TIMs may include a single thermally conductive filler wherein the single thermally conductive filler is one of the first, second, or third thermally conductive fillers as described herein. In another exemplary TIM, the TIM includes a first and a second thermally conductive filler wherein the first thermally conductive filler and the second thermally conductive filler are the first thermally conduct filler and the second thermally conduct filler, the first thermally conduct filler and the third thermally conduct filler, or the second thermally conduct filler and the third thermally conduct filler as described herein. In a further exemplary TIM, the TIM includes the first thermally conduct filler, the second thermally conduct filler, and the third thermally conduct filler as described herein.
Exemplary thermal conductive fillers include alumina oxide.
The TIM comprises one or more addition inhibitors for inhibiting or limiting crosslinking of the silicone oils. The addition inhibitor forms a complex with the catalyst to stop the reaction of the silicone oils. The addition inhibitors includes at least one alkynyl compound, and optionally, the addition inhibitor further includes a multi-vinyl functional polysiloxane.
Exemplary addition inhibitors include acetylenic alcohols such as 1-ethynyl-1-cyclohexanol, 2-methyl-3-butyn-2-ol, 2-phenyl-3-butyn-2-ol, 2-ethynyl-isopropanol, 2-ethynyl-butane-2-ol, and 3,5-dimethyl-1-hexyn-3-ol; silylated acetylenic alcohols such as trimethyl (3,5-dimethyl-1-hexyn-3-oxy)silane, dimethyl-bis-(3-methyl-1-butyn-oxy)silane, methylvinylbis(3-methyl-1-butyn-3-oxy)silane, and ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane; unsaturated carboxylic esters such as diallyl maleate, dimethyl maleate, diethyl fumarate, diallyl fumarate, and bis-2-methoxy-1-methylethylmaleate, mono-octylmaleate, mono-isooctylmaleate, mono-allyl maleate, mono-methyl maleate, mono-ethyl fumarate, mono-allyl fumarate, 2-methoxy-1-methylethylmaleate; fumarate/alcohol mixtures, such as mixtures where the alcohol is selected from benzyl alcohol or 1-octanol and ethenyl cyclohexyl-1-ol; conjugated ene-ynes such as 2-isobutyl-1-butene-3-yne, 3,5-dimethyl-3-hexene-1-yne, 3-methyl-3-pentene-1-yne, 3-methyl-3-hexene-1-yne, 1-ethynylcyclohexene, 3-ethyl-3-butene-1-yne, and 3-phenyl-3-butene-1-yne; vinylcyclosiloxanes such as 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, and mixtures of conjugated ene-yne and vinylcyclosiloxane. In one exemplary embodiment, the addition inhibitor is selected from 2-methyl-3-butyn-2-ol or 3-methyl-1-pentyn-3-ol.
In some exemplary embodiments, the addition inhibitor further includes a multi-vinyl functional polysiloxane. An exemplary multi-vinyl functional polysiloxane is a vinyl terminated polydimethylsiloxane in ethynyl cyclohexanol, such as Pt Inhibitor 88 available from Wacker Chemie AG. Without wishing to be held to any particular theory it is believed that the platinum catalyst forms a complex with ethynyl cyclohexanol and vinyl terminated polydimethylsiloxane as shown below.
The formation of the complex is believed to decrease the catalyst activity in room temperature, and thus maintaining the dispensability and wettability of the TIM. At the higher temperatures of the curing step, the Pt is released from the complex and help the hydrosilylation of vinyl functional silicone oil and hydride functional silicone oil, provides greater control over the “crosslinking”.
In some exemplary embodiments, the TIM may comprise the one or more addition inhibitors in an amount as little as 0.01 wt. %, 0.02 wt. %, 0.05 wt. %, 0.1 wt. %, 0.15 wt. %, as great as 0.2 wt. %, 0.25 wt. %, 0.3 wt. %, 0.5 wt. %, 1 wt. %, 3 wt. %, 5 wt. %, or within any range defined between any two of the foregoing values, based on the total weight of the TIM, such as 0.01 wt. % to 1 wt. %, 0.01 wt. % to 0.5 wt. %, or 0.01 wt. % to 3 wt. %, for example. In one exemplary embodiment, the TIM includes an addition inhibitor in the amount of 0.1 wt. %. In another exemplary embodiment, the TIM includes an addition inhibitor in the amount of 0.01 wt. %.
Without wishing to be held to any particular theory, it is believed that, in the absence of an addition inhibitor, the vinyl functional silicone oil reacts with the hydride functional silicone oil very quickly based on the addition hydrosilylation mechanism to form a solid phase that cannot be automatically dispensed by typical methods.
In one exemplary embodiment, the addition inhibitor is combined to functional silicone oils, such as KE-1056, KE-1151, KE-1820, KE-1825, KE-1830, KE-1831, KE-1833, KE-1842, KE-1884, KE-1885, KE-1886, FE-57, FE-61 available from Shin-Etsu, such as Syl-off® 7395, Syl-off® 7610, Syl-off® 7817, Syl-off® 7612, Syl-off® 7780 available from Dow Corning.
In an exemplary embodiment, the thermal gel includes one or more coupling agents that function to interact with both the filler and the polymer matrix of the silicone oils to promote a strong bond at the interface of the two materials. This helps to separate filler particle aggregates and disperse the filler particles into the polymer matrix. create better adhesion of thermally conductive filler(s) to the polyol polymer matrix. Exemplary coupling agents include silane coupling agents and organometallic compounds, such as include titanate coupling agents and zirconate coupling agents. Exemplary silane coupling agents include silane coupling agents with an aliphatic group. Exemplary coupling agents include titanium IV 2,2 (bis 2-propenolatomethyl)butanolato, tris(dioctyl)pyrophosphato-O; titanium IV 2-propanolato, tris(dioctyl)-pyrophosphato-O) adduct with 1 mole of diisooctyl phosphite; titanium IV bis(dioctyl)pyrophosphato-O, oxoethylenediolato, (Adduct), bis(dioctyl) (hydrogen)phosphite-O; titanium IV bis(dioctyl)pyrophosphato-O, ethylenediolato (adduct), bis(dioctyl)hydrogen phosphite; zirconium IV 2,2 (bis 2-propenolatomethyl)butanolato, tris(diisooctyl)pyrophosphato-O; zirconium IV 2,2-bis(2-propenolatomethyl) butanolato, cyclo di[2,2-(bis 2-propenolatomethyl) butanolato], pyrophosphato-O,O, and hexadecyltrimethoxysilane. In another exemplary embodiment, the coupling agent is KR-TTS available from Kenrich Chemical Company.
In some exemplary embodiments, the thermal gel comprises the one or more coupling agents in an amount as little as 0.1 wt. %, 0.2 wt. %, 0.3 wt. %, as great as 0.5 wt. %, 1.0 wt. %, 1.5 wt. %, 2.0 wt. %, or within any range defined between any two of the foregoing values, such as 0.1 wt. % to 2.0 wt. %, 0.2 wt. % to 1.5 wt. %, or 0.3 wt. % to 0.5 wt. %, for example, based on the total weight of the thermal interface material.
In exemplary embodiments, the TIM includes a crosslinker to enable crosslinking between silicone oils. An exemplary crosslinker includes a hydrosilicone oil Exemplary crosslinkers include. Andisil XL-1B, Andisil XL-10, Andisil XL-11, Andisil XL 12, Andisil XL-13, and Andisil XL-17.
In some exemplary embodiments, the TIM comprises the one or more crosslinker in an amount as little as 0.10%, 0.20 wt. %, 0.30 wt. %, as great as 0.4 wt. %, 0.60 wt. %, 0.70 wt. %, 1.0 wt. %, or within any range defined between any two of the foregoing values, such as 0.10 wt. % to 1.0 wt. %, 0.20 wt. % to 0.70 wt. %, or 0.30 wt. % to 0.60 wt. %, for example, based on the total weight of the thermal gel.
In exemplary embodiments, the TIM includes a solvent to increase the flowrate of the TIM. An exemplary solvent includes hydrocarbon solvents such as toluene, xylene, p-xylene, m-xylene, mesitylene, solvent naphtha H, solvent naphtha A, Isopar H and other paraffin oils and isoparaffinic fluids, alkanes, such as pentane, hexane, isohexane, heptane, nonane, octane, dodecane, 2-methylbutane, hexadecane, tridecane, pentadecane, cyclopentane, 2,2,4-trimethylpentane, petroleum ethers, halogenated hydrocarbons, such as chlorinated hydrocarbons, nitrated hydrocarbons, benzene, 1,2-dimethylbenzene, 1,2,4-trimethylbenzene, mineral spirits, kerosene, isobutylbenzene, methylnaphthalene, ethyltoluene, ligroin.
Exemplary solvents have a boiling point temperature as little as 60° C., 90° C., 110° C., as great as 130° C., 180° C., 220° C. or within any range defined between any two of the foregoing values, such as 60° C. to 220° C., 90° C. to 180° C., or 110° C. to 130° C., for example.
Exemplary solvents have a viscosity as little as 0.2 cSt, 1 cSt, 2 cSt, as great as 5 cSt, 10 cSt, 50 cSt or within any range defined between any two of the foregoing values, such as 0.2 cSt to 50 cSt, 1 cSt to 10 cSt, or 2 cSt to 5 cSt, for example.
In some exemplary embodiments, the thermal interface material may comprise the one or more solvents in an amount as little as 0.1 wt. %, 0.2 wt. %, 0.3 wt. % as great as 5 wt. %, 10 wt. %, 20 wt. %, or within any range defined between any two of the foregoing values, such as 0.1 wt. % to 20 wt. %, 0.1 wt. % to 10 wt. %, or 0.1 wt. % to 5 wt. %, for example, based on the total weight of the formulation.
In a first non-limiting illustrative embodiment, the TIM includes a first low molecular silicone oil of as little as 2 wt. %, 3 wt. %, 4 wt. %, as great as 8 wt. %, 9 wt. %, 10 wt. % or within any range defined between any two of the foregoing values, such as about 2 wt. % to about 10 wt. %, for example, a high molecular weight silicone oil of as little as 0.1 wt. %, 1 wt. %, 2 wt. %, as great as 3 wt. %, 4 wt. %, 5 wt. % or within any range defined between any two of the foregoing values, such as about 0.1 wt. % to about 5 wt. %, for example, a coupling agent of as little as 0.1 wt. %, 1 wt. %, 2 wt. %, as great as 3 wt. %, 4 wt. %, 5 wt. % or within any range defined between any two of the foregoing values, such as about 0.1 wt. % to about 5 wt. %, for example, a crosslinker of as little as 0.1 wt. %, 0.2 wt. %, 0.3 wt. %, as great as 0.8 wt. %, 0.9 wt. %, 1.0 wt. % or within any range defined between any two of the foregoing values, such as about 0.1 wt. % to about 1 wt. %, for example, a catalyst of as little as 0.1 wt. %, 1 wt. %, 2 wt. %, as great as 3 wt. %, 4 wt. %, 5 wt. % or within any range defined between any two of the foregoing values, such as about 0.1 wt. % to about 5 wt. %, for example, an inhibitor of as little as 0.1 wt. %, 1 wt. %, 2 wt. %, as great as 3 wt. %, 4 wt. %, 5 wt. % or within any range defined between any two of the foregoing values, such as about 0.1 wt. % to about 5 wt. %, for example, a first thermally conductive filler of as little as 25 wt. %, 30 wt. %, 35 wt. %, as great as 40 wt. %, 45 wt. %, 50 wt. % or within any range defined between any two of the foregoing values, such as about 25 wt. % to about 50 wt. %, for example, a second thermally conductive filler of as little as 25 wt. %, 30 wt. %, 35 wt. %, as great as 40 wt. %, 45 wt. %, 50 wt. % or within any range defined between any two of the foregoing values, such as about 25 wt. % to about 50 wt. %, for example, a third thermally conductive filler of as little as 25 wt. %, 30 wt. %, 35 wt. %, as great as 40 wt. %, 45 wt. %, 50 wt. % or within any range defined between any two of the foregoing values, such as about 25 wt. % to about 50 wt. %, for example, and of a solvent of as little as 0.1 wt. %, 1 wt. %, 2 wt. %, as great as 3 wt. %, 4 wt. %, 5 wt. % or within any range defined between any two of the foregoing values, such as about 0.1 wt. % to about 5 wt. %, for example.
In a second non-limiting illustrative embodiment, the TIM includes a first low molecular silicone oil of as little as 0.1 wt. %, 1 wt. %, 2 wt. %, as great as 13 wt. %, 14 wt. %, 15 wt. % or within any range defined between any two of the foregoing values, such as about 0.1 wt. % to about 15 wt. %, for example, a high molecular weight silicone oil of as little as 0.1 wt. %, 1 wt. %, 2 wt. %, as great as 3 wt. %, 4 wt. %, 5 wt. % or within any range defined between any two of the foregoing values, such as about 0.1 wt. % to about 5 wt. %, for example, a first thermally conductive filler of as little as 25 wt. %, 30 wt. %, 35 wt. %, as great as 40 wt. %, 45 wt. %, 50 wt. % or within any range defined between any two of the foregoing values, such as about 25 wt. % to about 50 wt. %, for example, a second thermally conductive filler of as little as 25 wt. %, 30 wt. %, 35 wt. %, as great as 40 wt. %, 45 wt. %, 50 wt. % or within any range defined between any two of the foregoing values, such as about 25 wt. % to about 50 wt. %, for example, a third thermally conductive filler of as little as 25 wt. %, 30 wt. %, 35 wt. %, as great as 40 wt. %, 45 wt. %, 50 wt. % or within any range defined between any two of the foregoing values, such as about 25 wt. % to about 50 wt. %, for example, an addition inhibitor of as little as 0.1 wt. %, 1 wt. %, 2 wt. %, as great as 3 wt. %, 4 wt. %, 5 wt. % or within any range defined between any two of the foregoing values, such as about 0.1 wt. % to about 5 wt. %, for example, an addition catalyst of as little as 0.1 wt. %, 1 wt. %, 2 wt. %, as great as 3 wt. %, 4 wt. %, 5 wt. % or within any range defined between any two of the foregoing values, such as about 0.1 wt. % to about 5 wt. %, for example, and a crosslinker or within any range defined between any two of the foregoing values, such as about 0.1 wt. % to about 1 wt. %, for example.
In some exemplary embodiments, a thermal interface material as described above has excellent resistance to oil bleeding while increasing the flow rate of the TIM. Oil bleeding is the distance of oil leakage from the TIM and is typically understood to be inversely related to the viscosity of the thermal interface material. That is, greater the viscosity of the TIM generally relates to a lower oil bleeding of the TIM.
Exemplary thermal interface materials are curable to form a solid pad for use with electronic components. Exemplary thermal interface materials have a cure time at room temperature of as little as 1 hour, 5 hours, 24 hours, as great as 2 days, 3 days, 5 days, or within any range defined between any two of the foregoing values such as between 1 hour and 5 days, between 5 hours and 3 days, or between 24 hours and 1 days, for example. A higher temperature will accelerate the curing time of the exemplary thermal interface materials. For example, when the ambient temperature is 100° C., the curing time for the exemplary thermal interface material is between 1 minute and 30 minutes.
Exemplary thermal interface materials have a thickness of as little as 0.03 mm, 0.05 mm, 0.07 mm, as great as 0.1 mm, 0.5 mm. 1 mm, or within any range defined between any two of the foregoing values, such as 0.03 mm to 1 mm, 0.05 mm to 0.5 mm, or 0.07 mm to 0.1 mm, for example
Exemplary thermal interface materials without the added solvent as described above have a viscosity of as little as 1000 Pa.s, 1500 Pa.s, 2000 Pa.s, as great as 2500 Pa.s, 3000 Pa.s, 3500 Pa.s, or within any range defined between any two of the foregoing values such as between 1000 Pa.s and 3500 Pa.s, between 1500 Pa.s and 3000 Pa.s, or between 2000 Pa.s and 2500 Pa.s at 23° C. and a shear rate of 10 s−1, for example.
Exemplary thermal interface materials with the added solvent as described above have a viscosity of as little as 150 Pa.s, 200 Pa.s, 250 Pa.s, 300 Pa.s, as great as 500 Pa.s, 550 Pa.s, 600 Pa.s, 650 Pa.s or within any range defined between any two of the foregoing values such as between 150 Pa.s and 650 Pa.s or between 200 Pa.s and 600 Pa.s at 25° C. and a shear rate of 10 s−1.
Exemplary TIMs have a bleeding value of as little as 0.25 mm, 0.50 mm, 1.0 mm, as great as 1.25 mm, 1.40 mm. 1.50 mm, or within any range defined between any two of the foregoing values, such as 0.25 mm to 1.50 mm, 0.50 mm to 1.40 mm, or 1.0 mm to 1.25 mm, for example.
Exemplary TIMs have a flowrate of as little as 20 g/min, 25 g/min, 30 g/min, as great as 35 g/min, 40 g/min. 50 g/min, or within any range defined between any two of the foregoing values, such as 20 g/min to 50 g/min, 25 g/min to 40 g/min, or 30 g/min to 35 g/min, for example.
In some exemplary embodiments, the TIM is prepared by combining the individual components with the exception of the solvent in a speed mixer and blending the composition together. The blended composition may then be applied directly to the substrate without baking.
More specifically, referring to
At step 112, solvent is added to the reaction vessel and mixing is continued. In an exemplary embodiment, half of the third thermally conductive filler is added, and the mixture is mixed at 10 revolutions per minute (rpm) for 30 minutes. At step 114, a vacuum of the reaction vessel is started and mixing is continued. In an exemplary embodiment, the mixture is mixed at 54 revolutions per minute (rpm) for 30 minutes. At step 116, the vacuum is stopped and the mixture is transferred to a discharger. Finally, at step 118, the vacuum is started to remove air in the TIM, and then the vacuum is stopped, and the resulting material is compressed into a syringe 50 (
Referring again to
A thermal interface material (Example 1) was prepared according to the formulation provided in Table 1. The properties of Example 1 were then compared with those of a Comparative Example 1 (Comp. Ex. 1). Comp. Ex. 1 is also a silicone based TIM with Al2O3 filler and without complete cure.
In Example 1, the low molecular weight(MW) silicone oil was a low molecular weight liquid silicone oil with vinyl functional group. The molecular weight of the low MW silicone oil was below 50,000 Daltons. The high MW silicone oil had a molecular weight greater than 100,000 Daltons. The silane coupling agent used was hexadecyltrimethoxysilane.
Furthermore, the hydrosilicone oil was used as a cross linker, and the cross linker was Andisil XL 12 available from AB Specialty silicones Nantong Co., Ltd. The catalyst was an addition platinum catalyst was available from Wacker Chemie AG, and the addition inhibitor was a Pt Inhibitor 88 available from Wacker Chemie AG. The thermally conductive filler A comprised aluminum oxide particles having a particle diameter of about 10 microns. The thermally conductive filler B comprised aluminum oxide particles having a particle diameter of about 5 microns, and the thermally conductive filler C included aluminum oxide particles having a particle diameter of about 0.6 microns. The surface area of all particles in the thermally conductive fillers A-C was about 1.25 m2/g. Finally, the solvent used was Isopar H available from Multisol limited.
To prepare the formulation of Example 1, the organic components with the exception of the volatile solvent were combined and blended with a speed mixer. The thermally conductive fillers were then added, and the mixture was subsequently blended. Finally, the volatile solvent was added and blended once more resulting in the formulation of Example 1.
The formulation was then filled into a 10 cubic centimeter syringe 50 (
To measure the flow rate of a TIM sample, a 30 cubic centimeter (cc) syringe 50 without a nozzle is used, and the TIM sample is dispensed via dispenser tool 52 for 1 minute under a pressure of 0.6 MPa. After 1 minute, the dispensed TIM sample is weighed. The measured flow rate of the Example 1 formulation was 31 g/min.
The formulation was then printed as a gel onto a piece of A4 paper. The formulation's dimensions were 25.4 mm×25.4 mm×1.5 mm. The Ex. 1 formulation was then placed under room temperature until the oil bleeding from the formulation no longer expanded away from the formulation. Then, the distance from the formulation was measured to determine the distance of oil bleeding trace. As shown in
Without wishing to be held to a particular theory, it is believed that the addition of higher surface area fillers reduce the bleeding of the TIM. These fillers also reduce the flowrate (i.e., increase the viscosity) of the TIM. However, the addition of the solvent serves to increase the flowrate of the TIM to increase the applicability of the TIM. In addition, the amount of solvent added is minimal (e.g., less than 0.5 wt. %) which prevents the solvent from impacting the advantageous benefit of reduced bleeding realized with the addition of high surface area fillers to the TIM.
Furthermore, oil bleeding is a slow process—it can be observed after at least 6 hours. By contrast, the volatility of the solvent used is high (i.e., the solvent evaporates quickly) such that the solvent completely evaporates during oil bleeding (e.g., in about 1 or 2 hours). Therefore, addition of the solvent increases the flow rate of the TIM when the TIM is dispensed, but once dispensed and after a period of time (e.g., about 2 hours), the solvent will completely evaporate from the TIM and will be unable to impact the oil bleeding properties of the TIM.
As used herein, the phrase “within any range defined between any two of the foregoing values” literally means that any range may be selected from any two of the values listed prior to such phrase regardless of whether the values are in the lower part of the listing or in the higher part of the listing. For example, a pair of values may be selected from two lower values, two higher values, or a lower value and a higher value.
While this invention has been described as having exemplary designs, the present invention can be further modified within the spirit and scope of this disclosure. This application is therefore intended to cover any variations, uses, or adaptations of the invention using its general principles. Further, this application is intended to cover such departures from the present disclosure as come within known or customary practice in the art to which this invention pertains and which fall within the limits of the appended claims.
This application claims priority to U.S. Provisional Patent Application Ser. No. 62/630,928 filed Feb. 15, 2018, which is herein incorporated by reference in its entirety.
Number | Name | Date | Kind |
---|---|---|---|
1655133 | Clase | Jan 1928 | A |
2451600 | Woodcock | Oct 1948 | A |
2810203 | Bachofer | Oct 1957 | A |
3262997 | Cameron et al. | Jul 1966 | A |
4006530 | Nicolas | Feb 1977 | A |
4087918 | Schmid et al. | May 1978 | A |
4180498 | Spivack | Dec 1979 | A |
4265026 | Meyer | May 1981 | A |
4446266 | von Gentzkow et al. | May 1984 | A |
4459185 | Obata et al. | Jul 1984 | A |
4559709 | Beseme et al. | Dec 1985 | A |
4565610 | Nobel et al. | Jan 1986 | A |
4604424 | Cole et al. | Aug 1986 | A |
4787149 | Possati et al. | Nov 1988 | A |
4816086 | Oleske | Mar 1989 | A |
4832781 | Mears | May 1989 | A |
4839955 | Vannier | Jun 1989 | A |
4910050 | Oldham et al. | Mar 1990 | A |
5162555 | Remmers et al. | Nov 1992 | A |
5167851 | Jamison et al. | Dec 1992 | A |
5294923 | Juergens et al. | Mar 1994 | A |
5391924 | Uchida et al. | Feb 1995 | A |
5403580 | Bujanowski et al. | Apr 1995 | A |
5562814 | Kirby | Oct 1996 | A |
5660917 | Fujimori et al. | Aug 1997 | A |
5816699 | Keith et al. | Oct 1998 | A |
5930115 | Tracy et al. | Jul 1999 | A |
5950066 | Hanson et al. | Sep 1999 | A |
6040362 | Mine et al. | Mar 2000 | A |
6054198 | Bunyan et al. | Apr 2000 | A |
6090484 | Bergerson | Jul 2000 | A |
6096414 | Young | Aug 2000 | A |
6165612 | Misra | Dec 2000 | A |
6197859 | Hanson et al. | Mar 2001 | B1 |
6238596 | Nguyen et al. | May 2001 | B1 |
6339120 | Misra et al. | Jan 2002 | B1 |
6372337 | Takahashi et al. | Apr 2002 | B2 |
6372997 | Hill et al. | Apr 2002 | B1 |
6391442 | Duvall et al. | May 2002 | B1 |
6400565 | Shabbir et al. | Jun 2002 | B1 |
6432320 | Bonsignore et al. | Aug 2002 | B1 |
6432497 | Bunyan | Aug 2002 | B2 |
6451422 | Nguyen | Sep 2002 | B1 |
6475962 | Khatri | Nov 2002 | B1 |
6496373 | Chung | Dec 2002 | B1 |
6500891 | Kropp et al. | Dec 2002 | B1 |
6506332 | Pedigo | Jan 2003 | B2 |
6562180 | Bohin et al. | May 2003 | B1 |
6597575 | Matayabas et al. | Jul 2003 | B1 |
6605238 | Nguyen et al. | Aug 2003 | B2 |
6610635 | Khatri | Aug 2003 | B2 |
6616999 | Freuler et al. | Sep 2003 | B1 |
6617517 | Hill et al. | Sep 2003 | B2 |
6620515 | Feng et al. | Sep 2003 | B2 |
6624224 | Misra | Sep 2003 | B1 |
6645643 | Zafarana et al. | Nov 2003 | B2 |
6649325 | Gundale et al. | Nov 2003 | B1 |
6657297 | Jewram et al. | Dec 2003 | B1 |
6673434 | Nguyen | Jan 2004 | B2 |
6706219 | Nguyen | Mar 2004 | B2 |
6761928 | Hill et al. | Jul 2004 | B2 |
6764759 | Duvall et al. | Jul 2004 | B2 |
6783692 | Bhagwagar | Aug 2004 | B2 |
6791839 | Bhagwagar | Sep 2004 | B2 |
6797382 | Nguyen et al. | Sep 2004 | B2 |
6797758 | Misra et al. | Sep 2004 | B2 |
6811725 | Nguyen et al. | Nov 2004 | B2 |
6815486 | Bhagwagar et al. | Nov 2004 | B2 |
6835453 | Greenwood et al. | Dec 2004 | B2 |
6838182 | Kropp et al. | Jan 2005 | B2 |
6841757 | Marega et al. | Jan 2005 | B2 |
6874573 | Collins et al. | Apr 2005 | B2 |
6900163 | Khatri | May 2005 | B2 |
6901675 | Edwards et al. | Jun 2005 | B2 |
6908669 | Nguyen | Jun 2005 | B2 |
6908682 | Mistele | Jun 2005 | B2 |
6913686 | Hilgarth | Jul 2005 | B2 |
6921780 | Ducros et al. | Jul 2005 | B2 |
6924027 | Matayabas et al. | Aug 2005 | B2 |
6926955 | Jayaraman et al. | Aug 2005 | B2 |
6940721 | Hill | Sep 2005 | B2 |
6946190 | Bunyan | Sep 2005 | B2 |
6956739 | Bunyan | Oct 2005 | B2 |
6975944 | Zenhausern | Dec 2005 | B1 |
6984685 | Misra et al. | Jan 2006 | B2 |
7013965 | Zhong et al. | Mar 2006 | B2 |
7038009 | Sagal et al. | May 2006 | B2 |
7056566 | Freuler et al. | Jun 2006 | B2 |
7074490 | Feng et al. | Jul 2006 | B2 |
7078109 | Hill et al. | Jul 2006 | B2 |
7119143 | Jarnjevic et al. | Oct 2006 | B2 |
7135232 | Yamada et al. | Nov 2006 | B2 |
7147367 | Balian et al. | Dec 2006 | B2 |
7172711 | Nguyen | Feb 2007 | B2 |
7208191 | Freedman | Apr 2007 | B2 |
7241707 | Meagley et al. | Jul 2007 | B2 |
7244491 | Nguyen | Jul 2007 | B2 |
7253523 | Dani et al. | Aug 2007 | B2 |
7262369 | English | Aug 2007 | B1 |
7291396 | Huang et al. | Nov 2007 | B2 |
7294394 | Jayaraman et al. | Nov 2007 | B2 |
RE39992 | Misra et al. | Jan 2008 | E |
7326042 | Alper et al. | Feb 2008 | B2 |
7328547 | Mehta et al. | Feb 2008 | B2 |
7369411 | Hill et al. | May 2008 | B2 |
7440281 | Bailey et al. | Oct 2008 | B2 |
7446158 | Okamoto et al. | Nov 2008 | B2 |
7462294 | Kumar et al. | Dec 2008 | B2 |
7463496 | Robinson et al. | Dec 2008 | B2 |
7465605 | Raravikar et al. | Dec 2008 | B2 |
7538075 | Yamada et al. | May 2009 | B2 |
7550097 | Tonapi et al. | Jun 2009 | B2 |
7572494 | Mehta et al. | Aug 2009 | B2 |
7608324 | Nguyen et al. | Oct 2009 | B2 |
7641811 | Kumar et al. | Jan 2010 | B2 |
7646778 | Sajassi | Jan 2010 | B2 |
7682690 | Bunyan et al. | Mar 2010 | B2 |
7695817 | Lin et al. | Apr 2010 | B2 |
7700943 | Raravikar et al. | Apr 2010 | B2 |
7732829 | Murphy | Jun 2010 | B2 |
7744991 | Fischer et al. | Jun 2010 | B2 |
7763673 | Okamoto et al. | Jul 2010 | B2 |
RE41576 | Bunyan et al. | Aug 2010 | E |
7765811 | Hershberger et al. | Aug 2010 | B2 |
7807756 | Wakabayashi et al. | Oct 2010 | B2 |
7816785 | Iruvanti et al. | Oct 2010 | B2 |
7842381 | Johnson | Nov 2010 | B2 |
7846778 | Rumer et al. | Dec 2010 | B2 |
7850870 | Ahn et al. | Dec 2010 | B2 |
7867609 | Nguyen | Jan 2011 | B2 |
7893170 | Wakioka et al. | Feb 2011 | B2 |
7955900 | Jadhav et al. | Jun 2011 | B2 |
7960019 | Jayaraman et al. | Jun 2011 | B2 |
7973108 | Okamoto et al. | Jul 2011 | B2 |
8009429 | Sundstrom et al. | Aug 2011 | B1 |
8039961 | Suhir et al. | Oct 2011 | B2 |
8076773 | Jewram et al. | Dec 2011 | B2 |
8081468 | Hill et al. | Dec 2011 | B2 |
8093331 | Fukui | Jan 2012 | B2 |
8102058 | Hsieh et al. | Jan 2012 | B2 |
8105504 | Gerster et al. | Jan 2012 | B2 |
8110919 | Jewram et al. | Feb 2012 | B2 |
8112884 | Tullidge et al. | Feb 2012 | B2 |
8115303 | Bezama et al. | Feb 2012 | B2 |
8138239 | Prack et al. | Mar 2012 | B2 |
8167463 | Loh | May 2012 | B2 |
8223498 | Lima | Jul 2012 | B2 |
8308861 | Rolland et al. | Nov 2012 | B2 |
8324313 | Funahashi | Dec 2012 | B2 |
8362607 | Scheid et al. | Jan 2013 | B2 |
8373283 | Masuko et al. | Feb 2013 | B2 |
8431647 | Dumont et al. | Apr 2013 | B2 |
8431655 | Dershem | Apr 2013 | B2 |
8445102 | Strader et al. | May 2013 | B2 |
8518302 | Gerster et al. | Aug 2013 | B2 |
8535478 | Pouchelon et al. | Sep 2013 | B2 |
8535787 | Lima | Sep 2013 | B1 |
8557896 | Jeong et al. | Oct 2013 | B2 |
8586650 | Zhang et al. | Nov 2013 | B2 |
8587945 | Hartmann et al. | Nov 2013 | B1 |
8618211 | Bhagwagar et al. | Dec 2013 | B2 |
8632879 | Weisenberger | Jan 2014 | B2 |
8633478 | Cummings et al. | Jan 2014 | B2 |
8638001 | Kimura et al. | Jan 2014 | B2 |
8647752 | Strader et al. | Feb 2014 | B2 |
8758892 | Bergin et al. | Jun 2014 | B2 |
8796068 | Stender et al. | Aug 2014 | B2 |
8837151 | Hill et al. | Sep 2014 | B2 |
8865800 | Stammer et al. | Oct 2014 | B2 |
8917510 | Boday et al. | Dec 2014 | B2 |
8937384 | Bao et al. | Jan 2015 | B2 |
9055694 | Lima | Jun 2015 | B2 |
9070660 | Lowe et al. | Jun 2015 | B2 |
9080000 | Ahn et al. | Jul 2015 | B2 |
9222735 | Hill et al. | Dec 2015 | B2 |
9260645 | Bruzda | Feb 2016 | B2 |
9353304 | Merrill et al. | May 2016 | B2 |
9392730 | Hartmann et al. | Jul 2016 | B2 |
9481851 | Matsumoto et al. | Nov 2016 | B2 |
9527988 | Habimana et al. | Dec 2016 | B2 |
9537095 | Stender et al. | Jan 2017 | B2 |
9593209 | Dent et al. | Mar 2017 | B2 |
9593275 | Tang et al. | Mar 2017 | B2 |
9598575 | Bhagwagar et al. | Mar 2017 | B2 |
10155894 | Liu et al. | Dec 2018 | B2 |
10287471 | Zhang et al. | May 2019 | B2 |
10312177 | Zhang et al. | Jun 2019 | B2 |
10501671 | Zhang et al. | Dec 2019 | B2 |
10781349 | Zhang et al. | Sep 2020 | B2 |
20020018885 | Takahashi et al. | Feb 2002 | A1 |
20020132896 | Nguyen | Sep 2002 | A1 |
20020140082 | Matayabas | Oct 2002 | A1 |
20020143092 | Matayabas | Oct 2002 | A1 |
20030031876 | Obeng et al. | Feb 2003 | A1 |
20030068487 | Nguyen et al. | Apr 2003 | A1 |
20030112603 | Roesner et al. | Jun 2003 | A1 |
20030128521 | Matayabas et al. | Jul 2003 | A1 |
20030151030 | Gurin | Aug 2003 | A1 |
20030159938 | Hradil | Aug 2003 | A1 |
20030171487 | Ellsworth et al. | Sep 2003 | A1 |
20030178139 | Clouser et al. | Sep 2003 | A1 |
20030203181 | Ellsworth et al. | Oct 2003 | A1 |
20030207064 | Bunyan et al. | Nov 2003 | A1 |
20030207128 | Uchiya et al. | Nov 2003 | A1 |
20030230403 | Webb | Dec 2003 | A1 |
20040037965 | Salter | Feb 2004 | A1 |
20040053059 | Mistele | Mar 2004 | A1 |
20040069454 | Bonsignore et al. | Apr 2004 | A1 |
20040097635 | Fan et al. | May 2004 | A1 |
20040149587 | Hradil | Aug 2004 | A1 |
20040161571 | Duvall et al. | Aug 2004 | A1 |
20040206941 | Gurin | Oct 2004 | A1 |
20050020738 | Jackson et al. | Jan 2005 | A1 |
20050025984 | Odell et al. | Feb 2005 | A1 |
20050045855 | Tonapi et al. | Mar 2005 | A1 |
20050072334 | Czubarow et al. | Apr 2005 | A1 |
20050110133 | Yamada et al. | May 2005 | A1 |
20050148721 | Tonapi et al. | Jul 2005 | A1 |
20050228097 | Zhong | Oct 2005 | A1 |
20050256291 | Okamoto et al. | Nov 2005 | A1 |
20050287362 | Garcia-Ramirez et al. | Dec 2005 | A1 |
20060040112 | Dean et al. | Feb 2006 | A1 |
20060057364 | Nguyen | Mar 2006 | A1 |
20060094809 | Simone et al. | May 2006 | A1 |
20060122304 | Matayabas | Jun 2006 | A1 |
20060155029 | Zucker | Jul 2006 | A1 |
20060208354 | Liu et al. | Sep 2006 | A1 |
20060228542 | Czubarow | Oct 2006 | A1 |
20060260948 | Zschintzsch et al. | Nov 2006 | A2 |
20060264566 | Cassar et al. | Nov 2006 | A1 |
20070013054 | Ruchert et al. | Jan 2007 | A1 |
20070051773 | Ruchert et al. | Mar 2007 | A1 |
20070097651 | Canale et al. | May 2007 | A1 |
20070116626 | Pan et al. | May 2007 | A1 |
20070131913 | Cheng et al. | Jun 2007 | A1 |
20070161521 | Sachdev et al. | Jul 2007 | A1 |
20070164424 | Dean et al. | Jul 2007 | A1 |
20070166554 | Ruchert et al. | Jul 2007 | A1 |
20070179232 | Collins et al. | Aug 2007 | A1 |
20070219312 | David | Sep 2007 | A1 |
20070241303 | Zhong et al. | Oct 2007 | A1 |
20070241307 | Nguyen | Oct 2007 | A1 |
20070249753 | Lin et al. | Oct 2007 | A1 |
20070293604 | Frenkel et al. | Dec 2007 | A1 |
20080021146 | Komatsu et al. | Jan 2008 | A1 |
20080023665 | Weiser et al. | Jan 2008 | A1 |
20080044670 | Nguyen | Feb 2008 | A1 |
20080110609 | Fann et al. | May 2008 | A1 |
20080116416 | Chacko | May 2008 | A1 |
20080141629 | Alper et al. | Jun 2008 | A1 |
20080149176 | Sager et al. | Jun 2008 | A1 |
20080269405 | Okamoto et al. | Oct 2008 | A1 |
20080291634 | Weiser et al. | Nov 2008 | A1 |
20080302064 | Rauch | Dec 2008 | A1 |
20090053515 | Luo et al. | Feb 2009 | A1 |
20090072408 | Kabir et al. | Mar 2009 | A1 |
20090111925 | Burnham et al. | Apr 2009 | A1 |
20090184283 | Chung et al. | Jul 2009 | A1 |
20100040768 | Dhindsa | Feb 2010 | A1 |
20100048435 | Yamagata et al. | Feb 2010 | A1 |
20100048438 | Carey et al. | Feb 2010 | A1 |
20100075135 | Kendall et al. | Mar 2010 | A1 |
20100129648 | Xu et al. | May 2010 | A1 |
20100197533 | Kendall et al. | Aug 2010 | A1 |
20100256280 | Bruzda | Oct 2010 | A1 |
20100304152 | Clarke | Dec 2010 | A1 |
20110000516 | Hershberger et al. | Jan 2011 | A1 |
20110038124 | Burnham et al. | Feb 2011 | A1 |
20110121435 | Mitsukura et al. | May 2011 | A1 |
20110141698 | Chiou et al. | Jun 2011 | A1 |
20110187009 | Masuko et al. | Aug 2011 | A1 |
20110192564 | Mommer et al. | Aug 2011 | A1 |
20110204280 | Bruzda | Aug 2011 | A1 |
20110205708 | Andry et al. | Aug 2011 | A1 |
20110265979 | Chen et al. | Nov 2011 | A1 |
20110294958 | Ahn et al. | Dec 2011 | A1 |
20110308782 | Merrill et al. | Dec 2011 | A1 |
20120048528 | Bergin et al. | Mar 2012 | A1 |
20120060826 | Weisenberger | Mar 2012 | A1 |
20120087094 | Hill et al. | Apr 2012 | A1 |
20120142832 | Varma et al. | Jun 2012 | A1 |
20120174956 | Smythe et al. | Jul 2012 | A1 |
20120182693 | Boday et al. | Jul 2012 | A1 |
20120195822 | Werner et al. | Aug 2012 | A1 |
20120253033 | Boucher et al. | Oct 2012 | A1 |
20120280382 | Im et al. | Nov 2012 | A1 |
20120285673 | Cola et al. | Nov 2012 | A1 |
20120288725 | Tanaka et al. | Nov 2012 | A1 |
20120292005 | Bruzda et al. | Nov 2012 | A1 |
20130127069 | Boday et al. | May 2013 | A1 |
20130199724 | Dershem | Aug 2013 | A1 |
20130248163 | Bhagwagar et al. | Sep 2013 | A1 |
20130265721 | Strader et al. | Oct 2013 | A1 |
20130285233 | Bao et al. | Oct 2013 | A1 |
20130288462 | Stender et al. | Oct 2013 | A1 |
20130299140 | Ling et al. | Nov 2013 | A1 |
20140043754 | Hartmann et al. | Feb 2014 | A1 |
20140150844 | Azechi | Jun 2014 | A1 |
20140190672 | Swaroop et al. | Jul 2014 | A1 |
20140264818 | Lowe, Jr. et al. | Sep 2014 | A1 |
20150000151 | Roth et al. | Jan 2015 | A1 |
20150008361 | Hattori | Jan 2015 | A1 |
20150125646 | Tournilhac et al. | May 2015 | A1 |
20150138739 | Hishiki | May 2015 | A1 |
20150158982 | Saito et al. | Jun 2015 | A1 |
20150183951 | Bhagwagar et al. | Jul 2015 | A1 |
20150275060 | Kuroda et al. | Oct 2015 | A1 |
20150279762 | Lowe et al. | Oct 2015 | A1 |
20150307743 | Ireland et al. | Oct 2015 | A1 |
20160009865 | Jiang et al. | Jan 2016 | A1 |
20160096984 | Matsumoto | Apr 2016 | A1 |
20160160102 | Minegishi et al. | Jun 2016 | A1 |
20160160104 | Bruzda et al. | Jun 2016 | A1 |
20160226114 | Hartmann et al. | Aug 2016 | A1 |
20160272839 | Yamamoto et al. | Sep 2016 | A1 |
20170009362 | Werner et al. | Jan 2017 | A1 |
20170018481 | Zeng et al. | Jan 2017 | A1 |
20170107415 | Shiono | Apr 2017 | A1 |
20170137685 | Liu et al. | May 2017 | A1 |
20170167716 | Ezaki et al. | Jun 2017 | A1 |
20170226396 | Yang et al. | Aug 2017 | A1 |
20170243849 | Sasaki et al. | Aug 2017 | A1 |
20170317257 | Ezaki et al. | Nov 2017 | A1 |
20170321100 | Zhang et al. | Nov 2017 | A1 |
20180030327 | Zhang et al. | Feb 2018 | A1 |
20180030328 | Zhang et al. | Feb 2018 | A1 |
20180085977 | Ezaki | Mar 2018 | A1 |
20180194982 | Ezaki et al. | Jul 2018 | A1 |
20180267315 | Yonemura | Sep 2018 | A1 |
20180358283 | Zhang et al. | Dec 2018 | A1 |
20180370189 | Tang et al. | Dec 2018 | A1 |
20190048245 | Liu et al. | Feb 2019 | A1 |
20190078007 | Zhang et al. | Mar 2019 | A1 |
20190085225 | Zhang et al. | Mar 2019 | A1 |
20190092993 | Naik et al. | Mar 2019 | A1 |
20190119544 | Shen et al. | Apr 2019 | A1 |
20190122954 | Bruzda et al. | Apr 2019 | A1 |
Number | Date | Country |
---|---|---|
2311067 | Jan 2001 | CA |
2433637 | Dec 2002 | CA |
1407141 | Apr 2003 | CN |
1456710 | Nov 2003 | CN |
1549875 | Nov 2004 | CN |
1580116 | Feb 2005 | CN |
1638952 | Jul 2005 | CN |
1940007 | Apr 2007 | CN |
1970666 | May 2007 | CN |
1972988 | May 2007 | CN |
100351075 | Nov 2007 | CN |
101067030 | Nov 2007 | CN |
101090922 | Dec 2007 | CN |
101113241 | Jan 2008 | CN |
101126016 | Feb 2008 | CN |
100394566 | Jun 2008 | CN |
101288353 | Oct 2008 | CN |
101445627 | Jun 2009 | CN |
101525489 | Sep 2009 | CN |
101735619 | Jun 2010 | CN |
101835830 | Sep 2010 | CN |
101942197 | Jan 2011 | CN |
102134474 | Jul 2011 | CN |
102341474 | Feb 2012 | CN |
102348763 | Feb 2012 | CN |
102627943 | Aug 2012 | CN |
102634212 | Aug 2012 | CN |
103087389 | May 2013 | CN |
103102552 | May 2013 | CN |
103102689 | May 2013 | CN |
103131138 | Jun 2013 | CN |
103214848 | Jul 2013 | CN |
103254647 | Aug 2013 | CN |
103333447 | Oct 2013 | CN |
103409116 | Nov 2013 | CN |
103436027 | Dec 2013 | CN |
103709757 | Apr 2014 | CN |
103756631 | Apr 2014 | CN |
103773322 | May 2014 | CN |
103849356 | Jun 2014 | CN |
103865271 | Jun 2014 | CN |
103923463 | Jul 2014 | CN |
104098914 | Oct 2014 | CN |
104136569 | Nov 2014 | CN |
104140678 | Nov 2014 | CN |
104152103 | Nov 2014 | CN |
104194733 | Dec 2014 | CN |
104449550 | Mar 2015 | CN |
104471012 | Mar 2015 | CN |
104497574 | Apr 2015 | CN |
104513487 | Apr 2015 | CN |
104804705 | Jul 2015 | CN |
104861661 | Aug 2015 | CN |
105111750 | Dec 2015 | CN |
105349113 | Feb 2016 | CN |
105419339 | Mar 2016 | CN |
104479623 | May 2016 | CN |
105566920 | May 2016 | CN |
105670555 | Jun 2016 | CN |
105838322 | Aug 2016 | CN |
105925243 | Sep 2016 | CN |
105980512 | Sep 2016 | CN |
106221236 | Dec 2016 | CN |
106243720 | Dec 2016 | CN |
107057370 | Aug 2017 | CN |
102007037435 | Feb 2009 | DE |
102009001722 | Sep 2010 | DE |
0466188 | Jan 1992 | EP |
0519138 | Dec 1992 | EP |
0816423 | Jan 1998 | EP |
1099734 | May 2001 | EP |
1149519 | Oct 2001 | EP |
1224669 | Jul 2002 | EP |
1291913 | Mar 2003 | EP |
1414063 | Apr 2004 | EP |
1514956 | Mar 2005 | EP |
1629059 | Mar 2006 | EP |
2194165 | Jun 2010 | EP |
2848215 | Jun 2004 | FR |
2508320 | Apr 2014 | GB |
57027188 | Jun 1982 | JP |
0543116 | May 1986 | JP |
06-209057 | Jul 1994 | JP |
02611364 | May 1997 | JP |
3662715 | Jan 1999 | JP |
2000143808 | May 2000 | JP |
2001139818 | May 2001 | JP |
2002003830 | Jan 2002 | JP |
2003-218296 | Jul 2003 | JP |
4016326 | Mar 2004 | JP |
4288469 | Oct 2004 | JP |
2005-032468 | Feb 2005 | JP |
2006-502248 | Jan 2006 | JP |
2007002002 | Jan 2007 | JP |
2007-106809 | Apr 2007 | JP |
2007-131798 | May 2007 | JP |
2008063412 | Mar 2008 | JP |
5269366 | Mar 2009 | JP |
2009102577 | May 2009 | JP |
5137538 | Jun 2009 | JP |
2009138036 | Jun 2009 | JP |
2009-209230 | Sep 2009 | JP |
5607298 | Mar 2010 | JP |
2010-120979 | Jun 2010 | JP |
4480457 | Jun 2010 | JP |
5390202 | Aug 2010 | JP |
2010-248349 | Nov 2010 | JP |
2010248277 | Nov 2010 | JP |
2010278115 | Dec 2010 | JP |
5463116 | Apr 2011 | JP |
5318733 | Jun 2011 | JP |
2011-144234 | Jul 2011 | JP |
2011165792 | Aug 2011 | JP |
2012-119725 | Jun 2012 | JP |
2012-201106 | Oct 2012 | JP |
5687167 | Apr 2013 | JP |
2014105283 | Jun 2014 | JP |
5944306 | Jul 2014 | JP |
5372270 | Sep 2014 | JP |
2014194006 | Oct 2014 | JP |
2015-212318 | Nov 2015 | JP |
2016-506992 | Mar 2016 | JP |
2016-216523 | Dec 2016 | JP |
2019-522711 | Aug 2019 | JP |
100479857 | Jul 2003 | KR |
10-2007-0089169 | Aug 2007 | KR |
20070116654 | Dec 2007 | KR |
10-0820902 | Apr 2008 | KR |
0953679 | Apr 2010 | KR |
1175948 | Aug 2012 | KR |
10-2015-0049376 | May 2015 | KR |
10-2016-0130273 | Nov 2016 | KR |
569348 | Jan 2004 | TW |
200907040 | Feb 2009 | TW |
201033268 | Sep 2010 | TW |
201527309 | Jul 2015 | TW |
201546257 | Dec 2015 | TW |
8706492 | Nov 1987 | WO |
1997026297 | Jul 1997 | WO |
0120618 | Mar 2001 | WO |
0193648 | Dec 2001 | WO |
03052818 | Jun 2003 | WO |
2003064148 | Aug 2003 | WO |
2004001844 | Dec 2003 | WO |
2004008497 | Jan 2004 | WO |
2004022330 | Mar 2004 | WO |
2005011146 | Feb 2005 | WO |
2005021257 | Mar 2005 | WO |
2005111146 | Nov 2005 | WO |
2005119771 | Dec 2005 | WO |
2006014171 | Feb 2006 | WO |
2006023860 | Mar 2006 | WO |
2007027670 | Mar 2007 | WO |
2008014171 | Jan 2008 | WO |
2008103219 | Aug 2008 | WO |
2008121491 | Oct 2008 | WO |
2008121970 | Oct 2008 | WO |
2009032212 | Mar 2009 | WO |
2010104534 | Sep 2010 | WO |
2010104542 | Sep 2010 | WO |
2013074920 | May 2013 | WO |
2013129600 | Sep 2013 | WO |
2013168291 | Nov 2013 | WO |
2013191116 | Dec 2013 | WO |
2014007119 | Jan 2014 | WO |
2014021980 | Feb 2014 | WO |
2014160067 | Oct 2014 | WO |
2015120773 | Aug 2015 | WO |
2015131370 | Sep 2015 | WO |
2015179056 | Nov 2015 | WO |
2016004565 | Jan 2016 | WO |
2016103424 | Jun 2016 | WO |
2016111139 | Jul 2016 | WO |
2018022288 | Feb 2018 | WO |
2018022293 | Feb 2018 | WO |
2018068222 | Apr 2018 | WO |
Entry |
---|
Silicone Fluid KF-96 data sheet, 2021. |
English language translation JP 2009-209230, Sep. 2009. |
Phase Change Material: DAPCM80-1′\MH&W International Corp., May 2012, http://mhw-thermal.com, 1 pages. |
Extended European Search Report issued in EP Application 15749120.0, dated Aug. 11, 2017, 6 pages. |
International Search Report and Written Opinion issued in PCT/CN2015/072202, dated Apr. 29, 2015, 14 pages. |
International Preliminary Report on Patentability received for PCT Patent Application No. PCT/US17/41447, dated Feb. 7, 2019, 8 pages. |
International Search Report and Written Opinion issued in PCT/US2009/069090, dated Aug. 17, 2010, 6 pages. |
International Search Report and Written Opinion received for PCT Patent Application No. PCT/US17/41447, dated Oct. 19, 2017, 10 pages. |
International Search Report and Written Opinion received for PCT Patent Application No. PCT/US2019/017743, dated May 28, 2019, 10 pages. |
Search Report issued in Chinese patent application 201410411725X (with English Translation), report dated Jul. 6, 2016, 4 pages. |
Singaporean Written Opinion issued in SG Application No. 11201704238Y, completed Apr. 11, 2019, 5 pages. |
“Dynasylan 1146: Oligomeric Diamino-Silane-System” Evonik Industries, pp. 1-3, 2008. |
“Hi-Flow 225F-AC Reinforced, Phase Change Thermal Interface Material,” The Bergquist Company, 1 page, available at least as early as Aug. 31, 2017. |
“Semicosil 9212A.” Wacker Silicones Material Safety Data Sheet, pp. 1-8, printed Dec. 11, 2009. |
“Semicosil 9212B.” Wacker Silicones Material Safety Data Sheet, pp. 1-8, printed Dec. 11, 2009. |
“THERM-A-GAP HCS10,569,570,579 and 580 Thermally Conductive Gap Filler Pads,” Parker Chomerics, Engineering Your Success, pp. 11-12, available at least as early as the filing date of the present application. |
Aranzabe, Estibaliz, et al. “More than Color: Pigments with Thermal Storage Capacity; Processing and Degradation Behavior.” Advances in Materials Physics and Chemistry, 5:171-184, 2015. |
Dow Corning® Two-Part RTV Silicone Sealant: Total Assembly Solutions for Home Appliance Production; www.dowcorning.com; Form No. 80-3375-01; 6 pages. |
Evonik, Silanes for Adhesives and Sealants, 2013, p. 1-24. |
Extended European Search Report issued in EP Application 14867847.7, dated Jun. 26, 2017, 7 pages. |
Extended European Search Report issued in EP Application No. 14897036.1, dated Jul. 2, 2018, 7 pages. |
Extended Search Report issued in EP Application 14907530.1, dated Jun. 27, 2018, 9 pages. |
Fink, Johannes Karl. “Chapter 18: Metal Deactivators.” in: A Concise Introduction to Additives for Thermoplastic Polymers, Wiley-Scrivener, pp. 165-171, Jan. 1, 2010. |
Gowda, Arun, et al. “Choosing the Right Thermal Interface Material.” Solid State Technology, Insights for Electronics Manufacturing, Online Blog, 9 pages, 2005. Retrieved May 25, 2017 from the Internet <http://electroiq.com/blog/2005/03/choosing-the-right-thermal-interface-material/. |
International Preliminary Report on Patentability issued in PCT/CN2016/075827, dated Sep. 20, 2018, 5 pages. |
International Search Report and Written Opinion issued in PCT/CN2014/081724. dated Apr. 1, 2015, 12 pages. |
International Search Report and Written Opinion issued in PCT/CN2014/093138, dated Sep. 6, 2015, 8 pages. |
International Search Report and Written Opinion issued in PCT/CN2016/075827, dated Dec. 1, 2016, 7 pages. |
International Search Report and Written Opinion issued in PCT/CN2016/101874, dated Apr. 28, 2017, 12 pages. |
International Search Report and Written Opinion issued in PCT/US2014/068033, dated Mar. 26, 2015, 12 pages. |
International Search Report and Written Opinion issued in PCT/US2017/041498, dated Oct. 20, 2017, 10 pages. |
International Search Report and Written Opinion issued in PCT/US2018/049218, dated Dec. 28, 2018, 13 pages. |
International Search Report and Written Opinion issued in PCT/US2018/056870, dated Feb. 8, 2019, 9 pages. |
Martyak et al., On the oxidation of tin(II) in methanesulfonate solutions and the role of sulfate, Galvanotechnik (2005), 96(3), 594-601 (Abstract). |
Ping, Ding, et al. “Preparation and Application Research of Novel Silicone Gel for High-Power IGBT.” Insulating Materials, 47(2):52-55, Chinese text with English translation of Abstract, 2014. |
Ramaswamy, C., et al. “Phase Change Materials as a Viable Thermal Interface Material for High-Power Electronic Applications.” The Ninth Intersociety Conference on Thermal and Thermomechanical Phenomena in Electronic Systems, IEEE, 2:687-691, 2004. |
Search Report issued in CN application 201480066502.2, dated May 18, 2017, 2 pages. |
Singaporean Search Report and Written Opinion issued in SG Application No. 11201704238Y, completed May 18, 2018, 9 pages. |
Singaporean Written Opinion issued in SG Application No. 11201704238Y, completed Feb. 7, 2019, 7 pages. |
Wacker Silicones, Catalyst EP/Inhibitor PT 88 product data sheet, p. 1-3, Oct. 6, 2008. |
Yasuhiro Aoyagi et al., “Effects of antioxidants and the solild component on the thermal stability of polyol-ester-based thermal pastes”, J Mater Sci (2007) 42:2358-2375; Mar. 12, 2007. |
Yasuhiro Aoyagi et al., “Polyol-Based Phase-Change Thermal Interface Materials”, Journal of Electronic Materials, vol. 35, No. 3, (2006); pp: 416-424. |
Yunsheng Xu et al., “Lithium Doped Polyethylene-Glycol-Based Thermal Interface Pastes for High Thermal Contact Conductance”, Transactions of the ASME; Journal of Electronic Packagiing, vol. 124, Sep. 2002; pp: 188-191. |
Number | Date | Country | |
---|---|---|---|
20190249007 A1 | Aug 2019 | US |
Number | Date | Country | |
---|---|---|---|
62630928 | Feb 2018 | US |