US20060213599A1 - Fiber adhesive material - Google Patents

Fiber adhesive material Download PDF

Info

Publication number
US20060213599A1
US20060213599A1 US11/441,472 US44147206A US2006213599A1 US 20060213599 A1 US20060213599 A1 US 20060213599A1 US 44147206 A US44147206 A US 44147206A US 2006213599 A1 US2006213599 A1 US 2006213599A1
Authority
US
United States
Prior art keywords
fibers
nanofibrils
fiber
carbon
velvet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US11/441,472
Inventor
Timothy Knowles
Christopher Seaman
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US09/593,587 external-priority patent/US6913075B1/en
Application filed by Individual filed Critical Individual
Priority to US11/441,472 priority Critical patent/US20060213599A1/en
Publication of US20060213599A1 publication Critical patent/US20060213599A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B08CLEANING
    • B08BCLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B1/00Cleaning by methods involving the use of tools, brushes, or analogous members
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B08CLEANING
    • B08BCLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B7/00Cleaning by methods not provided for in a single other subclass or a single group in this subclass
    • B08B7/0028Cleaning by methods not provided for in a single other subclass or a single group in this subclass by adhesive surfaces
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28FDETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F3/00Plate-like or laminated elements; Assemblies of plate-like or laminated elements
    • F28F3/02Elements or assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with recesses, with corrugations
    • F28F3/022Elements or assemblies thereof with means for increasing heat-transfer area, e.g. with fins, with recesses, with corrugations the means being wires or pins
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/34Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/34Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/36Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
    • H01L23/373Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00Details of semiconductor or other solid state devices
    • H01L23/34Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
    • H01L23/42Fillings or auxiliary members in containers or encapsulations selected or arranged to facilitate heating or cooling
    • H01L23/427Cooling by change of state, e.g. use of heat pipes
    • H01L23/4275Cooling by change of state, e.g. use of heat pipes by melting or evaporation of solids
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00Additional features of adhesives in the form of films or foils
    • C09J2301/30Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/31Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive effect being based on a Gecko structure
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001Technical content checked by a classifier
    • H01L2924/0002Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/903Microfiber, less than 100 micron diameter
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/23907Pile or nap type surface or component
    • Y10T428/23957Particular shape or structure of pile
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/23907Pile or nap type surface or component
    • Y10T428/23993Composition of pile or adhesive
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24132Structurally defined web or sheet [e.g., overall dimension, etc.] including grain, strips, or filamentary elements in different layers or components parallel
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2918Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]
    • Y10T428/292In coating or impregnation
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2933Coated or with bond, impregnation or core
    • Y10T428/2935Discontinuous or tubular or cellular core
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/2933Coated or with bond, impregnation or core
    • Y10T428/294Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/29Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913Rod, strand, filament or fiber
    • Y10T428/298Physical dimension
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/603Including strand or fiber material precoated with other than free metal or alloy
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/608Including strand or fiber material which is of specific structural definition
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/608Including strand or fiber material which is of specific structural definition
    • Y10T442/614Strand or fiber material specified as having microdimensions [i.e., microfiber]

Definitions

  • the invention relates to adhesive materials such as tapes that provide a dry and reusable medium for adhering two surfaces together.
  • Much of thermal management involves the transfer of heat from one element to another. While individual elements might have very high conductance, the heat transfer rate between contact surfaces of the two elements can limit overall performance of the thermal control system. Similarly, the strength of an adhesive bond formed between the two elements is often dependent on the contacting surfaces. The heat transfer rate and adhesive strength between the two elements can improve by maximizing the contact region between the two elements.
  • a different form of adhesive is found in a foot of a Tokay gecko.
  • the foot includes a structure which allows the gecko to run over glass ceilings or climb wet glass walls.
  • the toes of the Tokay gecko have pads consisting of thousands of 5 um-diameter keratinous fibers (called setae). The ends of the setae split into hundreds of 100-nm diameter fibrils. Each nanofibril terminates in an ellipsoidal structure called a “spatula.” Each spatula has a diameter ranging from 200-500 nm.
  • the adhesive force of a single seta against Si was measured to be 200 ⁇ N (20 mg).
  • a manufactured adhesive that could provide the adhesion properties of the gecko foot is desirable.
  • Such an adhesive would be compliant and could stick by intermolecular (van der Waals) forces resulting from its intimate contact with the surface.
  • Such an adhesive would provide broad utility as an adhesive or attachment mechanism.
  • the adhesive could be strong, dry, removable, reusable, and lightweight, combining many of the most desirable properties of the gecko foot.
  • Such an adhesive may also have enhanced thermal and/or electrical conductance, providing an effective thermal/electrical interface with a built-in attach mechanism that is strong, removable, and reusable.
  • One aspect of the invention is an adhesive material that comprises a base, an array of first fibers bonded to the base, each having a cross sectional diameter of less than approximately 15 microns, and an array of second fibers bonded predominantly to a portion of at least some of the first fibers and having a cross sectional diameters of less than about 1 micron, the second fibers being arranged and configured to form a strong VdW bond when pressed against a mating surface.
  • Another aspect of the present invention is a method for making an adhesive material.
  • the method comprises growing aligned whiskers having a diameter of less than about 1 micron from the tips of carbon fibers having a diameter of greater than about 3 microns and less than about 15 microns, and optionally depositing a material on a portion of the whiskers to form non-planar tips.
  • Another aspect of the present invention is an adhesive material tape that comprises a first plurality of fibers having first and second ends, the first plurality of fibers being predominantly aligned such that the first ends are bonded to a base surface of the tape, and a second plurality of fibers having first and second ends, the second plurality of fibers being predominantly aligned such that the first ends are bonded to the second ends of the first plurality of fibers and the second ends of the second plurality of fibers being arranged to adhere to a mating surface by intermolecular attraction.
  • Yet another aspect of the present invention is a method for enhancing the performance of an adhesive tape made from a plurality of predominantly aligned carbon fibers having diameters of less than approximately 15 microns.
  • the method comprises placing a plurality of nanofibrils having diameters of approximately 1 micron proximate to at least some tips of the predominantly aligned carbon fibers, and depositing a film on an end portion of the nanofibrils.
  • Still another aspect of the present invention is an adhesive tape that comprises a central support, and a plurality of nanofibrils extending from one or both major surface(s) of the central support, wherein at least some of the nanofibrils have a diameter of less than about 1 micron, the nanofibrils being arranged and configured to form a strong vdW bond when pressed against a mating surface.
  • FIG. 1A is a side view of one embodiment of a thermally conductive gasket incorporating nanofibrils.
  • FIG. 1B is a side view of another embodiment of a thermally conductive gasket incorporating nanofibrils.
  • FIG. 2 is a perspective view of a carbon fiber having a nanofibrils attached to the tip.
  • FIG. 3A is a scanning electron microscope image of a 7 micron diameter fiber with a mop of nanofibrils attached to the tip.
  • FIG. 3B is an increased magnification of the fiber of FIG. 3A .
  • FIG. 4 is a scanning electron microscope image of a mop of nanofibrils which has been mechanically compressed.
  • FIG. 5 is a scanning electron microscope image of the tips of the fibers of a thermal gasket prior to the deposition of nanofibrils.
  • FIG. 6A is a scanning electron microscope image the tip of one fiber of the gasket of FIG. 5 after lapping.
  • FIG. 6B is a scanning electron microscope image the tip of one fiber of the gasket of FIG. 5 after lapping and carbon CVD deposition.
  • FIG. 6C is a scanning electron microscope image the tip of one fiber of the gasket of FIG. 5 after lapping, carbon CVD deposition, and nanofibril deposition.
  • FIG. 6D is a higher magnification of the nanofibril mop of FIG. 6C .
  • FIG. 7A is a side view of a single-sided fiber velvet that comprises an array of fibers canted at an angle.
  • FIG. 7B is a detailed view of one of the fibers from FIG. 7A showing nanofibrils attached to the tip of a single fiber.
  • FIG. 7C is a detailed view of the nanofibrils from FIG. 7B .
  • FIG. 8 is a perspective view of two biased carbon fibers having nanofibrils grown at an acute angle to the carbon fiber shafts.
  • a compliant thermal interface material developed by the applicant which is presently marketed as VEL-THERM, is superior to existing commercial thermal interface gaskets.
  • This material is a soft, carbon fiber velvet consisting of numerous high- ⁇ (as high as 1000 W/mK) carbon fibers aligned perpendicularly to the interface plane.
  • a “brush” of predominantly aligned carbon fibers is embedded in an adhesive substrate such that the tips of the fibers are attached to the surface of the substrate at one end, and are exposed at the other end.
  • Free-standing “interleaf” gaskets can also be fabricated. These have fiber tips on both major surfaces, and the fibers are held together with an encapsulant such as a silicone or epoxy material.
  • Pitch fibers are formed from either pitch or PAN precursor material and drawn onto fiber tow. Each fiber typically has diameter ⁇ 10 ⁇ m, but which may vary between approximately 3 and 15 microns. Pitch fibers are graphitized by heating to high temperatures (near 3000° C.), giving them high thermal conductivities ⁇ ⁇ 1000 W/mK.
  • each fiber When placed between two surfaces, each fiber provides a high thermal conductivity path from one surface to the other. For uneven gaps, each fiber can bend independently in order to span the local gap. Low pressures are necessary to allow each fiber to touch both surfaces. Contact is maintained by either clamping or pressing the fiber tips into adhesive and bonding in place.
  • high- ⁇ fibers oriented in the direction of heat flow such gaskets have a high ⁇ (as high as 200 W/mK), while at the same time being even more compliant than conventional, particle-filled gaskets.
  • Such velvet gaskets also work better than copper foil (at comparable pressures) because they provide a greater area of contact, conforming to uneven surfaces.
  • the velvet can be bonded to one or both surfaces with various adhesives or PSA “tapes” including metal foils.
  • the highest measured total thermal conductance has been achieved by a high- ⁇ carbon fiber interleaf “gasket” in which the fibers are encapsulated in a silicone gel encapsulant.
  • the total joint resistance is dominated by the contact resistance between the fiber tips and the contacting surfaces.
  • Each interface has h interface ⁇ 20,000 W/m 2 K. If the contact conductance is increased to values comparable to the bulk conductance, the total conductance of the interface can be dramatically improved.
  • some embodiments of the invention utilize very small diameter fibers having diameters less than about 1 micron either in conjunction with, or as an alternative to, the typically 3-15 micron diameter conventional carbon fibers. These small diameter fibers are referred to herein as nanofibrils or whiskers.
  • Conventional carbon and silica whiskers may be utilized.
  • Conventional carbon whiskers may be grown from a Ni or Fe catalyst by CVD processing. However, they have typically relatively large diameters of ⁇ 1 ⁇ m. Furthermore, in order for conventional carbon whiskers to have high ⁇ , they must be graphitized by heating to ⁇ 3000° C.
  • the whiskers comprise single or multi-walled carbon “nanotubes”.
  • a nanotube is a recently discovered form of carbon that is basically an elongated version of a C 60 molecule, also known as a Buckminster Fullerene, and commonly referred to as a “Buckyball”.
  • a single-walled nanotube consists of a rolled graphene sheet, forming a tube of diameter 1.4 nm, and capped at each end. Nanotubes display many interesting and useful properties including very high thermal conductivity and high stiffness. They are highly robust; they elastically buckle, rather than fracture or plastically deform, when bent to large angles.
  • Multiwalled nanotubes which have larger diameters of up to about 500 nanometers, can also be grown, with similar properties. These properties make both single and multi-walled nanotubes surprisingly useful as components of thermal interfaces. Their thermal conductivity provides excellent heat transfer characteristics, and their mechanical properties provide the capacity to form large areas of compliant contact with adjacent surfaces.
  • FIGS. 1A and 1B One embodiment of a thermal interface constructed in accordance with these principles is illustrated in FIGS. 1A and 1B .
  • the thermal interface comprises a base 20 which has extending therefrom an array of nanofibrils 22 having diameters of less than about 1 micron.
  • FIG. 1B illustrates a two sided nanofibril gasket.
  • the base 24 forms a central support, nanofibrils 26 , 28 extend in opposite directions from both major surfaces.
  • the central support 24 or base 20 may, for example, be about 1 to 20 or mils thick, depending on the desired mechanical properties.
  • PECVD plasma-enhanced chemical vapor deposition
  • the nanotubes grew from a nickel film catalyst in the presence of acetylene (C 2 H 2 ), ammonia (NH 3 ), and nitrogen (N 2 ) at temperatures less than 666° C.
  • Multiwalled nanotubes with diameters from 20-400 nm and lengths from 0.1-50 ⁇ m were obtained. Thicker Ni films resulted in larger diameter nanotubes.
  • Transmission electron microscopy (TEM) images showed that the nanotubes were multiwalled, centrally hollow tubes, not solid fiber.
  • Each wall is presumed to be a highly thermally conductive graphitic layer. Key to their success seems to be the introduction of ammonia, which Ren et al. conjectured participated with the nickel in the catalytic reaction.
  • the plasma enables growth at lower temperatures.
  • the electric field of the plasma may also play a role in forming the nanotube array.
  • the base 20 or membrane 24 is aluminum, and the arrays of nanofibrils are created by forming a film of porous alumina on the aluminum substrate, growing nanotubes within the pores of the alumina film, and then etching away the alumina.
  • This method is described in detail in J. Li et al., Applied Physics Letters , Volume 75, Number 3 (Jul. 19, 1999), the disclosure of which is hereby incorporated by reference in its entirety.
  • a hexagonally ordered array of substantially axially aligned carbon multi-walled nanotubes on aluminum is fabricated using a hexagonal “nanochannel alumina” (NCA) membrane as a template.
  • NCA nanochannel alumina
  • the template is formed on pure aluminum by anodization and consists of alumina with long, cylindrical pores with diameters from 10-500 nm diameter and lengths that span the thickness of the “membrane”.
  • Cobalt catalyst “nanoseeds” are deposited in the bottom of each pore by electrodeposition.
  • Multi-walled nanotubes are then grown in each of the pores by hot-wall CVD at 650° C. (just below the melting point of Al).
  • the alumina is then etched away, leaving an array of multiwalled nanotubes on an aluminum substrate.
  • Double sided thermal gaskets as shown in FIG. 1B may be created by forming the alumina template on both sides of an aluminum sheet, and growing nanotubes on both sides.
  • a thick porous alumina membrane may comprise the support.
  • outstanding features of this array are (1) uniformity of nanotube diameters, (2) near perfect alignment perpendicular to the substrate, (3) regularly spaced nanotubes in a highly ordered hexagonal lattice, (4) uniformity of nanotube lengths. Furthermore, this technique allows independent control of the nanotube diameter, length, and packing fraction.
  • the fabrication technique has advantages over others. It eliminates the need to use a plasma, hot filament, and photolithography, involving only wet chemistry and hot-wall CVD. It can be scaled up for large areas. Furthermore, the parameters are in the proper range for application as a thermal interface, with the nanotubes being about 10-500 nanometers is diameter, a 50% packing fraction, and lengths from 1-100 microns.
  • nanofibrils are placed in contact with one or both ends of at least some of the fibers of an array of predominantly aligned larger diameter carbon fibers.
  • the performance of a carbon fiber brush/velvet which is formed from a predominantly aligned array of 3-15 micron diameter fibers is enhanced by the addition of nanofibrils to the tip region of the larger diameter fibers.
  • a conducting whisker array on the fiber tip removes the heat flow bottleneck, greatly alleviating the constriction resistance.
  • Attaching whiskers to the fiber tips improves thermal conductance of the gasket for several reasons.
  • the whiskers at the fiber tip will reduce the constriction resistance of the fiber contact point.
  • heat is conducted through the physical contact area between the fiber tips and the contacting surface, which is often only a small fraction of the fiber cross sectional area.
  • the contact pressure P is low compared to the hardness H of the contacting materials (P ⁇ 10 ⁇ 4 H), which therefore do not deform very much.
  • the fiber tip is not flat, being highly irregular in shape.
  • the second term dominates; that is, most of the heat conducts from the sides of the fiber near the tip through the conducting medium to the flat surface.
  • a fiber tip enhanced with a nanofibril or whisker array would fill the gap with a medium with a higher effective ⁇ , thereby improving h interface .
  • an unaligned discontinuous powder of nanofibrils is used to coat the tip region of the large fiber velvet.
  • These powders are commercially available as, for example, type Pyrograf III whiskers from Applied Sciences, Inc. This material is a powder of cut whiskers with diameters of about 50-300 nanometers and lengths of about 20 to 80 microns.
  • the nanofibril powder may be used as filler for thermally conductive grease, for example, which is applied to the tips of the velvet fibers.
  • the powder is placed directly on the tips by soaking them in a solution of Pyrograf III in ethanol.
  • the solution is advantageously ultrasonically vibrated to better disperse and disentangle the whiskers.
  • the presence of the nanofibrils in the tip region of the larger fibers improves heat transfer at the interface between the larger fiber tips and the surface of the component the tips are in contact with.
  • nanofibril powder is not an aligned array of nanofibrils, there are many inter fibril interfaces which still interfere with efficient heat transfer. Thermal conductance will be improved further if the nanofibrils formed a more ordered array with the nanofibrils spanning the gap between the tip of the larger diameter fiber and the component surface from end to end. This is shown conceptually in FIG. 2 . As shown in this Figure, a mop of nanofibrils 36 is attached to the tip portion of a larger diameter fiber 38 . The nanofibrils 36 preferably extend predominantly away from the larger diameter fiber 38 and toward the component surface 40 .
  • the nanofibrils may be configured to span the gap between each fiber and the mating surface, forming a high conductivity ( ⁇ ⁇ 200 W/mK), soft mop that effectively thermally shorts out the resistive gap.
  • ⁇ ⁇ 200 W/mK high conductivity
  • heat transfer efficiency between the tip of the larger fiber 38 and the component surface 40 may be expected to be better with better nanofibril alignment, even relatively poorly aligned masses of nanofibrils may be used to improve fiber tip heat transfer performance.
  • nanofibrils were formed onto larger diameter fibers and fiber velvets.
  • a CVD apparatus comprising a stainless steel (SS) vacuum chamber was utilized.
  • SS stainless steel
  • a controlled gas mixture of ammonia and hydrocarbon flows down through a SS tube from the top, fills the chamber, and is pumped from the bottom with a mechanical pump.
  • the gas flow is controlled and monitored with MKS mass flow controllers.
  • the pressure is controlled by a needle valve above the pump and monitored with a MKS Baratron gauge.
  • a quartz window allows visual monitoring of the experiment.
  • the plasma is sustained between two 2′′-diameter, graphite electrodes.
  • the bottom electrode is mounted on a ceramic (mullite) tube.
  • a SS-sheathed thermocouple runs up the inside of the tube in order to monitor the temperature of the bottom electrode.
  • the top electrode is mounted to the SS gas inlet tube; its height can be adjusted to control the gap.
  • the bottom electrode (anode) is grounded through the thermocouple sheath.
  • the top electrode (cathode) is electrically isolated from the chamber and carries the (negative) high voltage, powered by a 1 kW DC power supply capable of 1000V/1 A.
  • a hot filament is used for three purposes: (1) thermal nonequilibrium heating of the sample (2) emission of electrons to stabilize the glow discharge and prevent arcing (3) cracking of the hydrocarbon gas.
  • Tungsten wire 15 mil diameter, is wound into a coil and mounted between the electrodes. The support and electrical connections are made through an electrical feedthrough in the back. The filament is powered through an isolation transformer at 60 Hz. In the later CVD runs, the W coil was prevented from “drooping” when heated by supporting the coil with an alumina tube running through it, thus allowing better control of its position. Typical power applied through the coil was 200 W.
  • the sample including substrate and catalyst coating
  • the chamber is sealed and leak tested with a He leak detector with a mass spectrometer.
  • a gas flow of 160 sccm ammonia is established with a pressure of a few torr.
  • An ammonia plasma is initiated between the electrodes and the tungsten filament is heated to ⁇ 1500° C., as monitored by an optical pyrometer.
  • the filament radiatively heats the sample.
  • the temperature of the anode is monitored, although the sample is hotter than this.
  • the sample is heated and etched for 10-15 mins.
  • 80 sccm of hydrocarbon gas propylene or acetylene
  • the deposition is ceased and the chamber allowed to cool, after which the sample is removed and examined.
  • FIGS. 3A and 3B illustrate nanofibril “mops” 40 grown onto nickel coated 7 micron diameter carbon fibers. These nanofibrils appear to be similar in structure to commercial vapor grown carbon fibers comprising tubes of concentric, graphitic layers. However, they tend to have a high defect density, exemplified by their not being straight, and causing them to have a lower thermal conductivity than ideal. The ⁇ of these nanofibrils has not been measured, but they are most likely graphitizable, and if necessary, heat treatment at 2800° C. would likely give them a ⁇ of ⁇ 2000 W/mK.
  • one of the “befuzzed” fibers was singled out for investigating how the nanotube mop responds to pressure exerted by a surface with which it comes into contact.
  • the befuzzed fiber tip was contacted with flat-bladed tweezers with enough force to bend the fiber, as observed under the optical microscope.
  • the sample was then placed in the SEM to examine the effect. Shown in FIG. 4 is an SEM image of the pressed befuzzed fiber tip. Although the diameter of the fiber is only 7 ⁇ m, the diameter of the befuzzed fiber is approximately 40 ⁇ m. Although a bit flattened, the mop can still be seen around the fiber tip, indicating some degree of mechanical resilience.
  • high thermal conductivity gaskets were made out of high- ⁇ ( ⁇ 1000 W/mK), pitch carbon fibers ( ⁇ 10 micron diameter), The fibers are preferentially aligned in the z-direction such that each fiber spans the entire thickness of 1 mm. The fibers are held together with a light, epoxy wash coat. Capillary forces cause the epoxy to collect at the nodes where fibers contact each other.
  • the packing fraction of fibers is about 10%, which implies a theoretical bulk thermal conductivity value of ⁇ ⁇ 100 W/mK and a bulk conductance of h ⁇ 100,000 W/m 2 K.
  • Gaskets of a high- ⁇ velvet (100 W/mK) attached to a POCO carbon substrate may be made by electroflocking high- ⁇ (generally about 100-1000 W/mK) pitch fibers (for example, 10 micron diameter ⁇ 0.5 mm length) into high- ⁇ ( ⁇ 2 W/mK) carbonizable polymer such as polyimide. Electroflocking is a known technique for forming aligned fiber arrays. Pneumatic or mechanical flocking techniques may also be used. A variety of carbon fiber types may also be utilized, such as are commercially available from Amoco Corp. or Toray. A nickel film is ion beam sputtered into the velvet, most notably on the fiber tips. Carbon whisker arrays are then grown on the nickel coated fibers via PECVD processing.
  • the carbon fibers are precision cut from a continuous spool. Although the mean length of the pitch fibers will be controlled (typically 0.5 mm), there is some variation in length of 50 micron or more, which is comparable to the average distance between adjacent fibers. A few psi pressure is required to bend the longer fibers so that the tips of the shorter fibers contact the interfacing surface.
  • the velvet samples may be lapped and polished before deposition of the Ni film so that the fiber tips are more co-planar (within a few microns). This can be accomplished by EDM cutting or by potting the velvet in a removable medium and then lapping and polishing it flat. The potting medium is then removed.
  • Co-planar tips may allow the “whiskerized” velvets to have high conductivity using less than 1 psi pressure since there is no need to compress the velvet in order for all of the tips to contact the interfacing surface. Co-planar tips may also have an effect on the quality or uniformity of the whisker arrays on the tips.
  • gaskets were potted in a removable polymer and lapped on both sides with fine sandpaper (600 grit). The potting medium was then removed. These gaskets were processed in a carbon CVD reactor in order to carbonize the epoxy wash coat and deposit a thin carbon CVD layer ( ⁇ 2 micron-thick) that would hold the fibers together. The resulting gaskets are then able to withstand the PE-HF CVD process. A 55 ⁇ 5 nm-thick film of Ni catalyst was ion-beam sputtered onto both sides of four of the carbon CVD'ed gaskets.
  • Pitch carbon fiber gasket sample cs7-144 was processed in the PE-HF CVD reactor under the conditions listed in Table 1 TABLE 1 PE-HF CVD deposition conditions of pitch fiber gasket sample Sample# cs7-144 Mounting Lying flat on anode conditions Plasma power 160 W HF power 300 W Max temperature 527° C. Plasma etch time 12 min Deposition time 5 min Hydrocarbon gas Acetylene Mass gain 4.6 mg (5%) Resulting deposit Heavy, bottom side
  • Sample cs7-144 was covered with carbon deposit that was visible under the optical microscope.
  • the 90.5 mg sample had gained 4.6 mg, which corresponds to a 4 micron-thick, uniform layer of carbon over one surface. Some areas displayed thicker deposits than others did.
  • the variation may reflect variation in local temperature, hydrocarbon concentration, and/or catalyst microstructure.
  • FIG. 5 is a 250 ⁇ SEM image of a pitch carbon fiber gasket, looking from above, prior to the deposit of nanofibrils to the larger diameter fibers. The preferential alignment of the fibers is evident.
  • FIGS. 6A-6C show the tip of a single pitch fiber of Sample cs7-144 after various processing steps, FIG. 6A after lapping, FIG. 6B after carbon CVD, and FIG. 6C after PE-HF CVD. Many of the pitch fibers form a “pac-man”-shaped cross section during their manufacture. The fibers are remarkably flat after lapping.
  • the carbon CVD deposited a uniform layer of ⁇ 2 ⁇ m of carbon, increasing the diameter of each fiber from ⁇ 12 ⁇ m to ⁇ 16 ⁇ m.
  • FIG. 6C it is seen that the PE-HF CVD did indeed deposit an array of carbon nanofibrils on the tips and along the shafts of the fibers.
  • FIG. 6D shows an ⁇ 10 k view of the nanofibrils. They are not straight, but form a “mop” which appears to be highly packed. The nanofibril diameters are on the order of 100 nm.
  • phase change material is commercially available from several vendors. It is typically sold in sheet form with thicknesses from 1 to several mils. It consists of a wax (high molecular weight hydrocarbon), filled with thermally conductive solid particles such as BN, alumina, diamond, silver flake, etc. As described above with reference to thermal grease, the phase change material may also include cut carbon nanofibrils. These particles typically have characteristic sizes from 1 to several microns. In addition, there may be wetting agents added so that the wax wets the particles, as well as the tips of the fibers.
  • PCM phase change material
  • Useful PCM is a solid at room temperature, and softens and melts at elevated temperatures. It may or may not be molten at operating temperatures.
  • the PCM sheet is typically supported by release liner paper that is eventually peeled away before application.
  • the melting point of the material is between about 30 degrees C. and 100 degrees C. In some cases, the melting point is between about 40 degrees C. and 70 degree C.
  • the PCM can be added to the fiber tips by a number of methods.
  • the fibers can be flocked into a sheet of PCM that is heated to just the right temperature so that the tips of the flocked fibers adhere to it and remain vertically oriented.
  • the fibers can then be anchored to the PCM sheet by melting the PCM further and/or pushing the fiber tips further into the PCM.
  • the resulting velvet may or may not then be partially encapsulated with silicone gel, PCM, acrylic spray, foam, or other means of encapsulation.
  • the purpose of encapsulation is to (1) hold the fibers together, providing structural support, and (2) preventing fibers from escaping as potentially harmful debris. The latter is of special concern if the fibers are electrically conductive.
  • a PCM sheet can by placed on top of the resulting velvet, and the entire PCM/velvet/PCM sandwich pressed together and/or heated to fuse everything together.
  • the nanofibril material described above which may advantageously include coupling nanofibrils to the larger fibers to form a fiber velvet, can also be used as an adhesive material.
  • fiber velvets can form compliant interface pads. These pads can be effective as a thermal interface since they make contact at their fiber tips. For uneven gaps, most or all of the fibers can bend independently in order to span the local gap. Low pressures are sufficient to allow substantially all of the fibers to touch both surfaces. These same attributes are also desirable in an adhesive.
  • An adhesive material that incorporates a fiber velvet provides a dry and reusable medium for adhering to a mating surface.
  • FIG. 7A is a perspective view of a single-sided fiber velvet 50 that comprises an array of fibers.
  • FIG. 7B is a detailed conceptual view of one of the fibers from FIG. 7A showing an array of nanofibrils 36 attached to the tip of a single fiber 38 .
  • the end of the fiber 38 that is distal to the nanofibrils 36 is fixedly attached to a base or substrate material 20 using one of the methods described above.
  • the ends of the nanofibrils 36 that are distal to the fiber 38 are available for adhering to a mating surface.
  • the fibers can be bonded to one or both surfaces of a central support with various adhesives or pressure sensitive adhesive (PSA) “tapes” including metal foils and polymers.
  • PSA pressure sensitive adhesive
  • a single-sided velvet 50 shown in FIG. 7A forms a flexible one-sided tape.
  • a second array of fibers may be attached to a lower surface of the base 20 to form a two-sided tape.
  • Previously described exemplary materials for the substrate or base 20 include a POCO graphite substrate a foil of aluminum, or a plastic film.
  • the fibers 38 can be, for example, any commercially available type.
  • Commercially available carbon fiber include those formed from either pitch or PAN precursor material and drawn onto fiber tow.
  • the carbon fibers 38 may be precision cut from a continuous spool.
  • fiber refers to a structure with greater than a 1:1 aspect ratio.
  • nanofiber or “nanofibril” as used herein refers to a fiber with a diameter of equal to or less than about 1 ⁇ m (micrometer).
  • Each fiber typically has a diameter of 6-10 ⁇ m, but which may vary between approximately 3 and 15 microns.
  • the fibers 38 of the carbon fiber velvet 50 have diameters that range from approximately 5 um to 10 um with lengths that range from approximately 1 ⁇ 2 mm to 3 mm. Electroflocking can be used to form the aligned fiber arrays 38 on the base 20 . Pneumatic or mechanical flocking techniques may also be used.
  • various geometric and material attributes of the fibers 38 can be selected. These attributes include material properties of the fibers and substrate, for example adhesive strength, modulus, Hamaker constant, dielectric constant, surface energy, and tensile strength and modulus and temperature regimes. These attributes also include geometry, for example, fiber length, fiber diameter, fiber number density, fiber angular bias, and pad thickness, For example, the diameters and lengths of the fibers 38 can be selected depending on the desired compliance of the adhesive material produced with them. To create a more compliant adhesive, fibers with a smaller diameter, longer length, or smaller modulus can be selected.
  • the fibers 38 can be precision cut to the desired length and assembled into the velvet using the techniques described above.
  • 6-um diameter ⁇ 1.5-mm long ex-polyacrylonitrile (ex-PAN) carbon fibers are selected for the carbon fibers 38 .
  • ex-PAN fibers are a glassy carbon and have the advantages of a small diameter, are easy to bend, bend elastically, and do not break easily.
  • the fiber density of the fibers 38 also affects the properties of the adhesive material. Fiber density is the density of the fibers 38 in the fiber velvet 50 . Fiber density is also referred to as a packing fraction. Thus, the packing fraction selected may also be based on the desired properties of the carbon fiber velvet 50 . For example, a high (20%) packing fraction could be used if relatively low compliance but high adhesive strength was desired. However, for an adhesive application, the packing fraction can be selected as low as a few percent. A lower packing fraction increases the compliance of the resulting carbon fiber velvet 50 .
  • arrays of carbon nanotubes/whiskers/nanofibrils 36 are deposited onto or grown from the tips of the carbon fibers 38 .
  • the deposited nanofibrils 36 can be arranged in a “mop” or in an aligned configuration on the tips of the carbon fibers 38 .
  • the aligned configuration has similarities to the contact ends of the setae of the gecko foot and is illustrated in FIGS. 7B and 7C .
  • the characteristics or attributes of the nanofibrils 36 for example, diameter, length, packing fraction, location, as well as their properties, for example, thermal and mechanical, can vary. Many of the characteristics of the nanofibrils 36 can be controlled by the growth process and tailored to match or surpass that of the split nanofibrils at the end of a Gecko's seta.
  • An exemplary process for growing nanofibrils 36 on a substrate will now be described.
  • a thin film of nickel or cobalt catalyst was deposited onto the substrate by ion-beam sputtering.
  • the substrate can be ion-beam cleaned prior to deposition.
  • the resulting film thickness was monitored with a quartz crystal thickness monitor and varied from 1-13 nm thick. Thinner films promote growth of smaller diameter nanofibrils 36 .
  • An optional step in the process for growing nanofibrils 36 comprises the deposition of a buffer layer between the substrate and the thin film prior to catalyst deposition.
  • the addition of the buffer layer may promote formation of Ni nanodots upon heating.
  • the inclusion of a buffer layer may facilitate bonding of the nanofibrils 36 to the substrate.
  • a titanium (Ti) buffer layer can form a TiC “weld” between the nanofibrils 36 and the substrate.
  • the nanofibrils 36 were grown on the substrate in a PECVD reactor.
  • the PECVD included a 1200° C. tube furnace with a 3′′-diameter quartz tube. Cylindrical graphite electrodes were machined and assembled within the PECVD reactor. The substrate and deposited catalyst was placed on a lower electrode. The quartz tube was evacuated to less than 10 mtorr with a mechanical pump, and continued pumping as the temperature was raised to 700 or 750° C. Once the setpoint temperature was reached, an etchant gas (NH 3 ) was fed at a controlled rate (typically 200 sccm/min) with the pressure being adjusted to a few torr.
  • NH 3 etchant gas
  • High voltage typically 600 V
  • a plasma was then applied between the electrodes and a plasma was initiated.
  • the NH 3 plasma is allowed to etch the substrate and deposited catalyst for several minutes before starting nanofibril 36 growth.
  • the heating and/or etching step is critical in breaking up the catalyst film on the substrate to form nanodot seeds. Etching reduces the size of the nanodot seeds and breaks up larger nanodot seeds into smaller nanodot seeds.
  • the size and density of the nanodot seeds determine the diameter and density of the nanofibrils that subsequently grow from the nanodot seeds. On silicon substrates, the diameter and density of the nanofibrils correlate with the Ni film thickness.
  • a controlled flow of feed gas for example acetylene, is then fed to initiate nanofibril growth. Details of the Ni-substrate interaction determine whether and how the nanodots form.
  • the nanofibrils 36 may grow in base-growth or tip-growth modes.
  • Base-growth mode occurs when the catalyst seed remains attached to the substrate and the nanofibril grows out of the catalyst seed.
  • Tip-growth mode occurs when the catalyst seed is carried with the tip of the nanofibril as the nanofibril grows from the catalyst seed).
  • Adhesion of the Ni catalyst to the substrate promotes base growth. After about 15 minutes, the plasma was turned off and the gas flow stopped. The substrate and grown nanofibrils were allowed to cool in vacuum.
  • a combined packing fraction for the velvet 50 is calculated by multiplying the packing fraction of the carbon fibers 38 with the packing fraction of the nanofibrils 36 .
  • the combined packing fraction for the exemplary velvet 50 described below is 2% (10% carbon fiber ⁇ 20% nanofibrils).
  • the carbon fibers 38 can be lapped and polished to form a carbon fiber velvet 50 with a uniform length and flat tips.
  • Lapping and polishing before attaching or growing nanofibrils 36 results in the fiber tips being more co-planar (within a few microns).
  • This geometry provides a flat surface from where to grow the nanofibrils or nanotubes 36 .
  • Such controlled tip geometry enhances the consistency of the adhesive surface of the nanotubes or nanofibrils 36 that grow on the flat tips of the carbon fibers 38 .
  • One method of lapping the fiber tips involves potting the fibers 38 during lapping of the carbon fiber tips. After lapping, the potting media is removed from between the carbon fibers 38 .
  • FIG. 8 illustrates a single fiber 38 that is at a bias angle ⁇ with respect to the base material 20 .
  • a biased velvet has fibers 38 which are not perpendicular to the underlying base 20 .
  • Embodiments of the velvet include fibers 38 that are biased in the same direction with respect to the base 20 . Angles between 0 and 90 degrees could be selected. Biasing the carbon fibers 38 can further increase the compliance of the carbon fiber velvet 50 . In one embodiment of the carbon fiber velvet 50 , an angle of about 45 degrees is formed between the underlying base 20 and the carbon fibers 38 .
  • the nanofibrils 36 can be grown or attached at a particular angle to the carbon fiber 38 shafts as shown in FIG. 8 .
  • the nanofibrils can be grown or attached at an angle that is complementary to the angle ⁇ so that the nanofibrils 36 are normal to the base 20 and/or a mating surface 40 .
  • the nanofibrils 36 are grown or attached at an angle with respect to the carbon fiber shafts so that the nanofibrils 36 are not perpendicular or normal to the base 20 and/or the mating surface 40 .
  • These angled nanofibrils 36 with respect to the carbon fiber shafts may be more compliant than the carbon fibers 38 when contacting the mating surface 40 .
  • any of the deposition techniques previously described, including CVD, PECVD, or using an AO template, can be used to grow carbon nanofibrils 36 on the tips of carbon fibers 38 .
  • These deposition techniques utilize a nano-sized metal catalyst (e.g. nickel, iron, or cobalt) particle on the carbon fiber 38 tip from which the carbon nanotube grows. The catalyst might remain to provide a strong bond to the carbon fiber 38 tip. The strength of the base attachment can be improved by, for example, heat treatment.
  • Another means by which the nanofibril can remain strongly attached to the fiber tip is by reacting the carbon nanofibril with a layer of Ti or other metal to form TiC or other appropriate carbide as a weld.
  • Still another method of strongly attaching the carbon nanofibrils to the carbon fiber tip is by encapsulating with a conformal coating of carbon by chemical vapor deposition (CVD).
  • CVD chemical vapor deposition
  • One method of depositing the catalyst particles on the ends of the carbon fibers 38 is by ion beam sputtering a thin film of catalyst metal onto the carbon fiber 38 tips, and then appropriate heat treatment and/or etching in order to create nanometer-sized catalyst particles.
  • the nanofibril 36 arrays then grow on the catalyst coated fibers 38 via PECVD processing.
  • a carbonizable adhesive can be used to attach the carbon fibers 38 to a carbon (e.g. POCO graphite) substrate.
  • a carbon e.g. POCO graphite
  • the nanotubes 36 can be coated for specific environments. For example, coating the nanotubes with SiC enhances their high temperature capability in an oxidizing atmosphere (such as air).
  • the diameter of the nanofibrils 36 affects the adhesive strength between the tips of the nanofibrils 36 and the mating surface 40 . It is postulated that once intimate contact between the nanofibrils 36 of the adhesive material and the mating surface 40 occurs, the compliance of the nanofibrils 36 allows the adhesive material to stick to the mating surface 40 by intermolecular (van der Waals) forces.
  • the van der Waals (vdW) force occurs between the uncharged atoms of the mating surface 40 and the uncharged atoms of the nanofibrils 36 . These vdW forces occur due to the mutual induction of an electric dipole moment in each atom.
  • the nanotubes 36 be relatively straight or slightly curved, have high packing fraction, small, uniform diameters, and long, uniform lengths.
  • the vdW force between macroscopic bodies is the sum of all forces between atoms of one body and those of the other. While the vdW force is usually thought to be small between two atoms, it can be quite large between macroscopic bodies, especially when in close contact.
  • the density or packing fraction of the nanofibrils 36 affects the adhesive strength between the tips of the nanofibrils 36 and the mating surface 40 . While the gecko foot has of the order 10 6 nanofibrils per mm 2 , the nanotube arrays 36 have typical densities of 10 7 -10 8 /mm 2 as described in Ren et al. and Li et al. For a carbon fiber 38 packing fraction of 10%, this would give a nanofibril 36 density of 10 6 -10 7 , which is comparable to or higher than the density for the gecko foot.
  • the aspect ratio of the nanofibrils 36 can be selected such that they will be able to bend and conform to any contacting mating surface 40 .
  • a nanotube array 36 with 50 nm diameter ⁇ 5 um length would include such attributes.
  • Depositing additional material on the contact surface of the nanofibrils 36 can further enhance their adhesive strength to the mating surface 40 .
  • the nanofibrils 36 are open at the ends and have insufficient tip area for high adhesive strength, the nanofibril 36 tips can be encapsulated or filled. This filling can be accomplished by, for example, depositing a thin film with a thickness that is comparable to the nanofibril 36 diameter.
  • the encapsulating material could be, for example, a metal or a compliant polymer such as parylene.
  • the encapsulating material can comprise, for example, conductive particles. The electrical characteristics of these conductive particles can be varied depending on the attributes desired of the adhesive material.
  • the deposited thin film can be thickest at the tips and thinned out on the upper surface area shafts of the nanofibrils 36 .
  • Such an enhanced tip of the nanofibril 36 serves a similar purpose as a gecko spatula to the setae. If a non-planar or rounded geometry is attained for the tip of the nanofibril 36 , such a rounded tip may adhere well in various orientations.
  • the microstructure may be susceptible to clogging by dirt or other particles.
  • the attributes of the microfibrils 36 can be further selected to enhance self-cleaning whereby the contaminants are expelled from the microstructure. For example, it may be important for the material to be hydrophobic to enable this self-cleaning feature, and or comprise a certain packing fraction of nanofibrils. These features are used by the lotus plant to keep it clean. In this way, the attributes of the fibers can be optimized to reduce the effect of contaminants on the adhesive properties of the material.
  • the adhesive material is compliant and therefore able to conform to both flat and nonflat or rough surfaces with a minimal amount of applied pressure.
  • Another advantage is that the adhesive material makes dry contact, sticking by intermolecular (van der Waals) forces, without leaving a sticky residue.
  • Other advantages include: controlled design and manufacture, enabling tailoring and optimizing of array features by modifying fiber and nanotube diameters, lengths, packing fractions, orientation, and location.
  • Exemplary applications of the adhesive material described herein include a wide range of ambient, and even hostile conditions: submarine, high temperature, space vacuum, and chemically corrosive environments.
  • the thermal conductivity and/or electrical conductivity of the carbon fibers can be combined with the adhesive properties. This can produce an electrical or thermal gasket/interface material that sticks without glue or mechanical fasteners to the components it is in contact with.

Abstract

A fiber velvet comprising nano-size fibers or nanofibrils attached to micro-size fibers is disclosed. Methods of manufacturing the velvet as well as various uses of the velvet are also described. For example, the fiber velvet can be used as a thermal interface or as an adhesive material. The nanofibrils may be attached to a flat base or membrane, or may be attached to the tip portions of the micro-size or larger diameter fibers. Various attributes of the micro-size fibers and of the nano-size fibers, for example, geometry (e.g. size, length, packing density) material type (e.g. carbon, metal, polymer, or ceramic) and properties (e.g. conductivity, modulus, surface energy, dielectric constant, surface roughness) can be selected depending on the desired attributes of the fiber velvet. The nanofibrils have a diameter of less than about 1 micron, and may advantageously be formed from single walled and/or multi-walled carbon nanotubes.

Description

    CROSS REFERENCE TO RELATED APPLICATIONS
  • This application is a divisional of U.S. patent application Ser. No. 10/464,830, titled Fiber Adhesive Material, and filed on Jun. 17, 2003, which claims priority to U.S. Provisional Patent Application Ser. No. 60/390,239, titled Dendritic Adhesive, and filed on Jun. 17, 2002 and is a continuation-in-part of U.S. patent application Ser. No. 09/593,587, titled Thermal Interface, and filed on Jun. 13, 2000, which claims priority to U.S. Provisional Patent Application Ser. No. 60/139,443, entitled Thermal Interface, and filed on Jun. 14, 1999. The entire disclosures of all of these applications are hereby incorporated by reference in their entirety.
  • BACKGROUND OF THE INVENTION
  • 1. Field of the Invention
  • The invention relates to adhesive materials such as tapes that provide a dry and reusable medium for adhering two surfaces together.
  • 2. Description of Related Art
  • Much of thermal management involves the transfer of heat from one element to another. While individual elements might have very high conductance, the heat transfer rate between contact surfaces of the two elements can limit overall performance of the thermal control system. Similarly, the strength of an adhesive bond formed between the two elements is often dependent on the contacting surfaces. The heat transfer rate and adhesive strength between the two elements can improve by maximizing the contact region between the two elements.
  • Existing methods of bonding include brazing, soldering, gluing, bolting, taping, sewing, zippering, and use of Velcro® fasteners. Desirable properties include high strength of attachment, easy removability, reliability, and reusability. Other considerations include chemical compatibility, outgassing, and mass. Brazing and gluing with adhesive is strong, but not reusable nor easily removable. Bolts can be heavy and require special fixturing for attaching. Tape is not very strong, tends to leave a residue, and loses its sticking ability with use. It does not work well in wet environments.
  • A different form of adhesive is found in a foot of a Tokay gecko. The foot includes a structure which allows the gecko to run over glass ceilings or climb wet glass walls. The toes of the Tokay gecko have pads consisting of thousands of 5 um-diameter keratinous fibers (called setae). The ends of the setae split into hundreds of 100-nm diameter fibrils. Each nanofibril terminates in an ellipsoidal structure called a “spatula.” Each spatula has a diameter ranging from 200-500 nm. The adhesive force of a single seta against Si was measured to be 200 μN (20 mg). It has been hypothesized that van der Waal forces are responsible for the gecko's amazing ability to climb up smooth vertical surfaces. If utilized to full capacity, the 100 mm2 area of a gecko's foot, consisting of 500,000 such setae, should then be able to produce 100 N (10 kg) of adhesive force. The corresponding effective adhesive strength is 106 MPa (15,000 psi). This adhesive strength is well suited for many applications. The micron-size setae serve as a compliant support which conforms to the surface to allow the nanometer-sized tips (themselves compliant on a small scale) to make intimate contact with the surface.
  • A manufactured adhesive that could provide the adhesion properties of the gecko foot is desirable. Such an adhesive would be compliant and could stick by intermolecular (van der Waals) forces resulting from its intimate contact with the surface. Such an adhesive would provide broad utility as an adhesive or attachment mechanism. The adhesive could be strong, dry, removable, reusable, and lightweight, combining many of the most desirable properties of the gecko foot. Such an adhesive may also have enhanced thermal and/or electrical conductance, providing an effective thermal/electrical interface with a built-in attach mechanism that is strong, removable, and reusable.
  • SUMMARY OF THE INVENTION
  • The systems and methods of the present invention have several features, no single one of which is solely responsible for its desirable attributes. Without limiting the scope of this invention as expressed by the claims which follow, its more prominent features will now be discussed briefly. After considering this discussion, and particularly after reading the section entitled “Detailed Description” one will understand how the features of this invention provide several advantages over traditional paper coupon systems.
  • One aspect of the invention is an adhesive material that comprises a base, an array of first fibers bonded to the base, each having a cross sectional diameter of less than approximately 15 microns, and an array of second fibers bonded predominantly to a portion of at least some of the first fibers and having a cross sectional diameters of less than about 1 micron, the second fibers being arranged and configured to form a strong VdW bond when pressed against a mating surface.
  • Another aspect of the present invention is a method for making an adhesive material. The method comprises growing aligned whiskers having a diameter of less than about 1 micron from the tips of carbon fibers having a diameter of greater than about 3 microns and less than about 15 microns, and optionally depositing a material on a portion of the whiskers to form non-planar tips.
  • Another aspect of the present invention is an adhesive material tape that comprises a first plurality of fibers having first and second ends, the first plurality of fibers being predominantly aligned such that the first ends are bonded to a base surface of the tape, and a second plurality of fibers having first and second ends, the second plurality of fibers being predominantly aligned such that the first ends are bonded to the second ends of the first plurality of fibers and the second ends of the second plurality of fibers being arranged to adhere to a mating surface by intermolecular attraction.
  • Yet another aspect of the present invention is a method for enhancing the performance of an adhesive tape made from a plurality of predominantly aligned carbon fibers having diameters of less than approximately 15 microns. The method comprises placing a plurality of nanofibrils having diameters of approximately 1 micron proximate to at least some tips of the predominantly aligned carbon fibers, and depositing a film on an end portion of the nanofibrils.
  • Still another aspect of the present invention is an adhesive tape that comprises a central support, and a plurality of nanofibrils extending from one or both major surface(s) of the central support, wherein at least some of the nanofibrils have a diameter of less than about 1 micron, the nanofibrils being arranged and configured to form a strong vdW bond when pressed against a mating surface.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1A is a side view of one embodiment of a thermally conductive gasket incorporating nanofibrils.
  • FIG. 1B is a side view of another embodiment of a thermally conductive gasket incorporating nanofibrils.
  • FIG. 2 is a perspective view of a carbon fiber having a nanofibrils attached to the tip.
  • FIG. 3A is a scanning electron microscope image of a 7 micron diameter fiber with a mop of nanofibrils attached to the tip.
  • FIG. 3B is an increased magnification of the fiber of FIG. 3A.
  • FIG. 4 is a scanning electron microscope image of a mop of nanofibrils which has been mechanically compressed.
  • FIG. 5 is a scanning electron microscope image of the tips of the fibers of a thermal gasket prior to the deposition of nanofibrils.
  • FIG. 6A is a scanning electron microscope image the tip of one fiber of the gasket of FIG. 5 after lapping.
  • FIG. 6B is a scanning electron microscope image the tip of one fiber of the gasket of FIG. 5 after lapping and carbon CVD deposition.
  • FIG. 6C is a scanning electron microscope image the tip of one fiber of the gasket of FIG. 5 after lapping, carbon CVD deposition, and nanofibril deposition.
  • FIG. 6D is a higher magnification of the nanofibril mop of FIG. 6C.
  • FIG. 7A is a side view of a single-sided fiber velvet that comprises an array of fibers canted at an angle.
  • FIG. 7B is a detailed view of one of the fibers from FIG. 7A showing nanofibrils attached to the tip of a single fiber.
  • FIG. 7C is a detailed view of the nanofibrils from FIG. 7B.
  • FIG. 8 is a perspective view of two biased carbon fibers having nanofibrils grown at an acute angle to the carbon fiber shafts.
  • DETAILED DESCRIPTION
  • Embodiments of the invention will now be described with reference to the accompanying Figures, wherein like numerals refer to like elements throughout. The terminology used in the description presented herein is not intended to be interpreted in any limited or restrictive manner, simply because it is being utilized in conjunction with a detailed description of certain specific embodiments of the invention. Furthermore, embodiments of the invention may include several novel features, no single one of which is solely responsible for its desirable attributes or which is essential to practicing the inventions herein described.
  • The inventions described herein relate to materials and associated devices that transfer heat between and/or adhere one device/surface and another. For example, a compliant thermal interface material developed by the applicant, which is presently marketed as VEL-THERM, is superior to existing commercial thermal interface gaskets. This material is a soft, carbon fiber velvet consisting of numerous high-κ (as high as 1000 W/mK) carbon fibers aligned perpendicularly to the interface plane. In some embodiments, such a “brush” of predominantly aligned carbon fibers is embedded in an adhesive substrate such that the tips of the fibers are attached to the surface of the substrate at one end, and are exposed at the other end. Free-standing “interleaf” gaskets can also be fabricated. These have fiber tips on both major surfaces, and the fibers are held together with an encapsulant such as a silicone or epoxy material.
  • Commercially available carbon fibers are formed from either pitch or PAN precursor material and drawn onto fiber tow. Each fiber typically has diameter ˜10 μm, but which may vary between approximately 3 and 15 microns. Pitch fibers are graphitized by heating to high temperatures (near 3000° C.), giving them high thermal conductivities κ˜1000 W/mK.
  • When placed between two surfaces, each fiber provides a high thermal conductivity path from one surface to the other. For uneven gaps, each fiber can bend independently in order to span the local gap. Low pressures are necessary to allow each fiber to touch both surfaces. Contact is maintained by either clamping or pressing the fiber tips into adhesive and bonding in place. By using high-κ fibers oriented in the direction of heat flow, such gaskets have a high κ (as high as 200 W/mK), while at the same time being even more compliant than conventional, particle-filled gaskets. Such velvet gaskets also work better than copper foil (at comparable pressures) because they provide a greater area of contact, conforming to uneven surfaces.
  • Many configurations are possible depending on the application requirements. Thus, the velvet can be bonded to one or both surfaces with various adhesives or PSA “tapes” including metal foils. The highest measured total thermal conductance has been achieved by a high-κ carbon fiber interleaf “gasket” in which the fibers are encapsulated in a silicone gel encapsulant.
  • The total thermal resistance of a thermal gasket interface is the sum of three contributions: the resistance of the bulk material itself, and the resistances of each interface where the material comes in contact with the interfacing surface. In terms of conductance (inverse of resistance) this may be written as:
    h total −1 =h bulk −1 +h interface1 −1 +h interface2 −1
  • In some embodiments, hbulkbulk/t=400,000 W/m2 K, which is 40× higher than htotal. Thus, the total joint resistance is dominated by the contact resistance between the fiber tips and the contacting surfaces. Each interface has hinterface˜20,000 W/m2K. If the contact conductance is increased to values comparable to the bulk conductance, the total conductance of the interface can be dramatically improved.
  • To improve this contact conductance, some embodiments of the invention utilize very small diameter fibers having diameters less than about 1 micron either in conjunction with, or as an alternative to, the typically 3-15 micron diameter conventional carbon fibers. These small diameter fibers are referred to herein as nanofibrils or whiskers. Conventional carbon and silica whiskers may be utilized. Conventional carbon whiskers may be grown from a Ni or Fe catalyst by CVD processing. However, they have typically relatively large diameters of ˜1 μm. Furthermore, in order for conventional carbon whiskers to have high κ, they must be graphitized by heating to ˜3000° C.
  • In some advantageous embodiments of the invention, the whiskers comprise single or multi-walled carbon “nanotubes”. A nanotube is a recently discovered form of carbon that is basically an elongated version of a C60 molecule, also known as a Buckminster Fullerene, and commonly referred to as a “Buckyball”. A single-walled nanotube consists of a rolled graphene sheet, forming a tube of diameter 1.4 nm, and capped at each end. Nanotubes display many interesting and useful properties including very high thermal conductivity and high stiffness. They are highly robust; they elastically buckle, rather than fracture or plastically deform, when bent to large angles. Multiwalled nanotubes, which have larger diameters of up to about 500 nanometers, can also be grown, with similar properties. These properties make both single and multi-walled nanotubes surprisingly useful as components of thermal interfaces. Their thermal conductivity provides excellent heat transfer characteristics, and their mechanical properties provide the capacity to form large areas of compliant contact with adjacent surfaces.
  • One embodiment of a thermal interface constructed in accordance with these principles is illustrated in FIGS. 1A and 1B. Referring now to FIG. 1A, the thermal interface comprises a base 20 which has extending therefrom an array of nanofibrils 22 having diameters of less than about 1 micron. FIG. 1B illustrates a two sided nanofibril gasket. In this embodiment, the base 24 forms a central support, nanofibrils 26, 28 extend in opposite directions from both major surfaces. The central support 24 or base 20 may, for example, be about 1 to 20 or mils thick, depending on the desired mechanical properties.
  • Several methods of growing arrays of nanofibrils/whiskers on substrate surfaces are known in the art. Chemical vapor deposition techniques have been used to grow relatively aligned nanotubes on nickel and nickel coated glass substrates as reported in Ren, et al., Science, Volume 282, pages 1105-1107 (Nov. 6, 1998) and in Huang et al., Applied Physics Letters, Volume 73, Number 26, pages 3845-3847 (Dec. 28, 1998), the disclosures of which are hereby incorporated by reference in their entireties. Ren et al. used a plasma-enhanced chemical vapor deposition (PECVD) process in which the nanotubes grew from a nickel film catalyst in the presence of acetylene (C2H2), ammonia (NH3), and nitrogen (N2) at temperatures less than 666° C. Multiwalled nanotubes with diameters from 20-400 nm and lengths from 0.1-50 μm were obtained. Thicker Ni films resulted in larger diameter nanotubes. Transmission electron microscopy (TEM) images showed that the nanotubes were multiwalled, centrally hollow tubes, not solid fiber. Each wall is presumed to be a highly thermally conductive graphitic layer. Key to their success seems to be the introduction of ammonia, which Ren et al. conjectured participated with the nickel in the catalytic reaction. The plasma enables growth at lower temperatures. The electric field of the plasma may also play a role in forming the nanotube array.
  • In one advantageous embodiment, the base 20 or membrane 24 is aluminum, and the arrays of nanofibrils are created by forming a film of porous alumina on the aluminum substrate, growing nanotubes within the pores of the alumina film, and then etching away the alumina. This method is described in detail in J. Li et al., Applied Physics Letters, Volume 75, Number 3 (Jul. 19, 1999), the disclosure of which is hereby incorporated by reference in its entirety. With this method, a hexagonally ordered array of substantially axially aligned carbon multi-walled nanotubes on aluminum is fabricated using a hexagonal “nanochannel alumina” (NCA) membrane as a template. The template is formed on pure aluminum by anodization and consists of alumina with long, cylindrical pores with diameters from 10-500 nm diameter and lengths that span the thickness of the “membrane”. Cobalt catalyst “nanoseeds” are deposited in the bottom of each pore by electrodeposition. Multi-walled nanotubes are then grown in each of the pores by hot-wall CVD at 650° C. (just below the melting point of Al). The alumina is then etched away, leaving an array of multiwalled nanotubes on an aluminum substrate. Double sided thermal gaskets as shown in FIG. 1B may be created by forming the alumina template on both sides of an aluminum sheet, and growing nanotubes on both sides. Alternatively, a thick porous alumina membrane may comprise the support.
  • Outstanding features of this array are (1) uniformity of nanotube diameters, (2) near perfect alignment perpendicular to the substrate, (3) regularly spaced nanotubes in a highly ordered hexagonal lattice, (4) uniformity of nanotube lengths. Furthermore, this technique allows independent control of the nanotube diameter, length, and packing fraction. The fabrication technique has advantages over others. It eliminates the need to use a plasma, hot filament, and photolithography, involving only wet chemistry and hot-wall CVD. It can be scaled up for large areas. Furthermore, the parameters are in the proper range for application as a thermal interface, with the nanotubes being about 10-500 nanometers is diameter, a 50% packing fraction, and lengths from 1-100 microns.
  • In another embodiment, nanofibrils (or whiskers) are placed in contact with one or both ends of at least some of the fibers of an array of predominantly aligned larger diameter carbon fibers. In this embodiment, rather than enhancing the thermal interface performance of a foil by adding nanofibrils to one or both surfaces of a foil membrane, the performance of a carbon fiber brush/velvet which is formed from a predominantly aligned array of 3-15 micron diameter fibers is enhanced by the addition of nanofibrils to the tip region of the larger diameter fibers.
  • An analysis of heat transfer in the tip region of a carbon fiber gasket illustrates the importance of this region to the overall heat transfer efficiency. For small temperature differences, radiation exchange can be neglected. When the contact area is small compared to the contacting bodies, there is an extra “constriction resistance” due to bottlenecking of the heat flow through the constriction, given by:
    Rconstriction˜1/(4 κa)
  • where κ is the harmonic mean of the contacting materials: κ−11 −12 −1, and a is the diameter of the contact area (taken to be circular). For small a, which depends on applied pressure, material hardness, tip geometry, and surface roughness, this resistance can be quite large. A conducting whisker array on the fiber tip removes the heat flow bottleneck, greatly alleviating the constriction resistance.
  • Attaching whiskers to the fiber tips improves thermal conductance of the gasket for several reasons. In applications where the interface is in a vacuum, the whiskers at the fiber tip will reduce the constriction resistance of the fiber contact point. In a vacuum, heat is conducted through the physical contact area between the fiber tips and the contacting surface, which is often only a small fraction of the fiber cross sectional area. The contact pressure P is low compared to the hardness H of the contacting materials (P<<10−4 H), which therefore do not deform very much. In addition, the fiber tip is not flat, being highly irregular in shape.
  • In the presence of air or other fluid surrounding medium, and at low contact pressures (P<10−4H), heat is mostly conducted through the fluid-filled gap; that is, the solid spot conduction is small compared to conduction through the fluid. Furthermore, convective heat transfer in air is usually negligible for gap widths less than ˜6 mm. For an irregularly-shaped fiber tip, the average gap 6 between the bottom of the fiber and the contacting surface is of the order of the fiber radius (5 microns). Assuming conditions are such that the mean free path is small (˜0.3 microns for air at STP) compared to δ, we may use Fourier's law of heat conduction. The conductance through the bottom of the fiber is then q/ΔT=κδ.
  • The thermal conductance through a medium of conductivity K between an isothermal flat surface and an isothermal vertical cylinder of length L and diameter D may be approximated as: q / Δ T = κ 2 π L ln ( 4 L / D ) , if D / L 1.
  • We take the effective length to be about the average interfiber distance L˜Dφ−1/2, where φ is the fiber packing fraction. The total thermal conductance per unit area of one of the interfaces of a velvet is then approximated as: h interface = 2 κ ϕ D ( 1 + 4 L / D ln ( 4 L / D ) 2 κ ϕ D ( 1 + 4 ϕ - 1 / 2 ln ( 4 ϕ - 1 / 2 ) )
  • The second term dominates; that is, most of the heat conducts from the sides of the fiber near the tip through the conducting medium to the flat surface. For φ=20%, hinterface˜12φκ/D ˜6000 W/m2K for air (κ=0.025 W/mK) and ˜24,000 W/m2K for silicone encapsulant (κ=0.1 W/mK).
  • Thus, a fiber tip enhanced with a nanofibril or whisker array would fill the gap with a medium with a higher effective κ, thereby improving hinterface. This may be accomplished in a variety of ways. In one embodiment, an unaligned discontinuous powder of nanofibrils is used to coat the tip region of the large fiber velvet. These powders are commercially available as, for example, type Pyrograf III whiskers from Applied Sciences, Inc. This material is a powder of cut whiskers with diameters of about 50-300 nanometers and lengths of about 20 to 80 microns. The nanofibril powder may be used as filler for thermally conductive grease, for example, which is applied to the tips of the velvet fibers. Alternatively, the powder is placed directly on the tips by soaking them in a solution of Pyrograf III in ethanol. The solution is advantageously ultrasonically vibrated to better disperse and disentangle the whiskers. After application, the presence of the nanofibrils in the tip region of the larger fibers improves heat transfer at the interface between the larger fiber tips and the surface of the component the tips are in contact with.
  • Because the nanofibril powder is not an aligned array of nanofibrils, there are many inter fibril interfaces which still interfere with efficient heat transfer. Thermal conductance will be improved further if the nanofibrils formed a more ordered array with the nanofibrils spanning the gap between the tip of the larger diameter fiber and the component surface from end to end. This is shown conceptually in FIG. 2. As shown in this Figure, a mop of nanofibrils 36 is attached to the tip portion of a larger diameter fiber 38. The nanofibrils 36 preferably extend predominantly away from the larger diameter fiber 38 and toward the component surface 40. In this embodiment, the nanofibrils may be configured to span the gap between each fiber and the mating surface, forming a high conductivity (κ˜200 W/mK), soft mop that effectively thermally shorts out the resistive gap. Although heat transfer efficiency between the tip of the larger fiber 38 and the component surface 40, may be expected to be better with better nanofibril alignment, even relatively poorly aligned masses of nanofibrils may be used to improve fiber tip heat transfer performance.
  • In one set of gasket fabrication procedures performed by the inventors, nanofibrils were formed onto larger diameter fibers and fiber velvets. In these procedures a CVD apparatus comprising a stainless steel (SS) vacuum chamber was utilized. In this chamber, a controlled gas mixture of ammonia and hydrocarbon (propylene or acetylene) flows down through a SS tube from the top, fills the chamber, and is pumped from the bottom with a mechanical pump. The gas flow is controlled and monitored with MKS mass flow controllers. The pressure is controlled by a needle valve above the pump and monitored with a MKS Baratron gauge. A quartz window allows visual monitoring of the experiment.
  • The plasma is sustained between two 2″-diameter, graphite electrodes. The bottom electrode is mounted on a ceramic (mullite) tube. A SS-sheathed thermocouple runs up the inside of the tube in order to monitor the temperature of the bottom electrode. The top electrode is mounted to the SS gas inlet tube; its height can be adjusted to control the gap. The bottom electrode (anode) is grounded through the thermocouple sheath. The top electrode (cathode) is electrically isolated from the chamber and carries the (negative) high voltage, powered by a 1 kW DC power supply capable of 1000V/1 A.
  • A hot filament is used for three purposes: (1) thermal nonequilibrium heating of the sample (2) emission of electrons to stabilize the glow discharge and prevent arcing (3) cracking of the hydrocarbon gas. Tungsten wire, 15 mil diameter, is wound into a coil and mounted between the electrodes. The support and electrical connections are made through an electrical feedthrough in the back. The filament is powered through an isolation transformer at 60 Hz. In the later CVD runs, the W coil was prevented from “drooping” when heated by supporting the coil with an alumina tube running through it, thus allowing better control of its position. Typical power applied through the coil was 200 W.
  • In a typical procedure, the sample, including substrate and catalyst coating, is placed on the bottom electrode. The chamber is sealed and leak tested with a He leak detector with a mass spectrometer. A gas flow of 160 sccm ammonia is established with a pressure of a few torr. An ammonia plasma is initiated between the electrodes and the tungsten filament is heated to ˜1500° C., as monitored by an optical pyrometer. The filament radiatively heats the sample. The temperature of the anode is monitored, although the sample is hotter than this. The sample is heated and etched for 10-15 mins. Then 80 sccm of hydrocarbon gas (propylene or acetylene) is introduced to start the CVD deposition, i.e. growth of carbon nanofibrils. After ˜5 mins, the deposition is ceased and the chamber allowed to cool, after which the sample is removed and examined.
  • Dozens of PE-HF CVD runs have been performed using the techniques described by Ren et al. and Huang et al. set forth above using a number of substrates including commercially available nickel coated carbon fibers, as well as nickel coated pitch and PAN carbon fiber velvet gaskets. FIGS. 3A and 3B illustrate nanofibril “mops” 40 grown onto nickel coated 7 micron diameter carbon fibers. These nanofibrils appear to be similar in structure to commercial vapor grown carbon fibers comprising tubes of concentric, graphitic layers. However, they tend to have a high defect density, exemplified by their not being straight, and causing them to have a lower thermal conductivity than ideal. The κ of these nanofibrils has not been measured, but they are most likely graphitizable, and if necessary, heat treatment at 2800° C. would likely give them a κ of ˜2000 W/mK.
  • Under an optical microscope, one of the “befuzzed” fibers was singled out for investigating how the nanotube mop responds to pressure exerted by a surface with which it comes into contact. The befuzzed fiber tip was contacted with flat-bladed tweezers with enough force to bend the fiber, as observed under the optical microscope. The sample was then placed in the SEM to examine the effect. Shown in FIG. 4 is an SEM image of the pressed befuzzed fiber tip. Although the diameter of the fiber is only 7 μm, the diameter of the befuzzed fiber is approximately 40 μm. Although a bit flattened, the mop can still be seen around the fiber tip, indicating some degree of mechanical resilience.
  • In another set of fabrication procedures, high thermal conductivity gaskets were made out of high-κ (˜1000 W/mK), pitch carbon fibers (˜10 micron diameter), The fibers are preferentially aligned in the z-direction such that each fiber spans the entire thickness of 1 mm. The fibers are held together with a light, epoxy wash coat. Capillary forces cause the epoxy to collect at the nodes where fibers contact each other. The packing fraction of fibers is about 10%, which implies a theoretical bulk thermal conductivity value of κ˜100 W/mK and a bulk conductance of h˜100,000 W/m2K.
  • Gaskets of a high-κ velvet (100 W/mK) attached to a POCO carbon substrate may be made by electroflocking high-κ (generally about 100-1000 W/mK) pitch fibers (for example, 10 micron diameter×0.5 mm length) into high-κ (˜2 W/mK) carbonizable polymer such as polyimide. Electroflocking is a known technique for forming aligned fiber arrays. Pneumatic or mechanical flocking techniques may also be used. A variety of carbon fiber types may also be utilized, such as are commercially available from Amoco Corp. or Toray. A nickel film is ion beam sputtered into the velvet, most notably on the fiber tips. Carbon whisker arrays are then grown on the nickel coated fibers via PECVD processing.
  • The carbon fibers are precision cut from a continuous spool. Although the mean length of the pitch fibers will be controlled (typically 0.5 mm), there is some variation in length of 50 micron or more, which is comparable to the average distance between adjacent fibers. A few psi pressure is required to bend the longer fibers so that the tips of the shorter fibers contact the interfacing surface. In some embodiments, the velvet samples may be lapped and polished before deposition of the Ni film so that the fiber tips are more co-planar (within a few microns). This can be accomplished by EDM cutting or by potting the velvet in a removable medium and then lapping and polishing it flat. The potting medium is then removed.
  • Co-planar tips may allow the “whiskerized” velvets to have high conductivity using less than 1 psi pressure since there is no need to compress the velvet in order for all of the tips to contact the interfacing surface. Co-planar tips may also have an effect on the quality or uniformity of the whisker arrays on the tips.
  • In one specific process, six gaskets were potted in a removable polymer and lapped on both sides with fine sandpaper (600 grit). The potting medium was then removed. These gaskets were processed in a carbon CVD reactor in order to carbonize the epoxy wash coat and deposit a thin carbon CVD layer (˜2 micron-thick) that would hold the fibers together. The resulting gaskets are then able to withstand the PE-HF CVD process. A 55±5 nm-thick film of Ni catalyst was ion-beam sputtered onto both sides of four of the carbon CVD'ed gaskets.
  • Example
  • Pitch carbon fiber gasket sample cs7-144 was processed in the PE-HF CVD reactor under the conditions listed in Table 1
    TABLE 1
    PE-HF CVD deposition conditions of pitch fiber gasket
    sample
    Sample# cs7-144
    Mounting Lying flat on anode
    conditions
    Plasma power 160 W
    HF power 300 W
    Max temperature 527° C.
    Plasma etch time 12 min
    Deposition time  5 min
    Hydrocarbon gas Acetylene
    Mass gain 4.6 mg (5%)
    Resulting deposit Heavy, bottom side
  • After the chamber cooled, the sample was removed and examined under the microscope. The bottom of Sample cs7-144 was covered with carbon deposit that was visible under the optical microscope. The 90.5 mg sample had gained 4.6 mg, which corresponds to a 4 micron-thick, uniform layer of carbon over one surface. Some areas displayed thicker deposits than others did. The variation may reflect variation in local temperature, hydrocarbon concentration, and/or catalyst microstructure.
  • FIG. 5 is a 250× SEM image of a pitch carbon fiber gasket, looking from above, prior to the deposit of nanofibrils to the larger diameter fibers. The preferential alignment of the fibers is evident. FIGS. 6A-6C show the tip of a single pitch fiber of Sample cs7-144 after various processing steps, FIG. 6A after lapping, FIG. 6B after carbon CVD, and FIG. 6C after PE-HF CVD. Many of the pitch fibers form a “pac-man”-shaped cross section during their manufacture. The fibers are remarkably flat after lapping. The carbon CVD deposited a uniform layer of ˜2 μm of carbon, increasing the diameter of each fiber from ˜12 μm to ˜16 μm. It also formed a nodular structure at the tip which is no longer flat. In FIG. 6C, it is seen that the PE-HF CVD did indeed deposit an array of carbon nanofibrils on the tips and along the shafts of the fibers. FIG. 6D shows an ×10 k view of the nanofibrils. They are not straight, but form a “mop” which appears to be highly packed. The nanofibril diameters are on the order of 100 nm.
  • Another means of enhancing the conductance at the tips is to add phase change material (PCM) at and around the tips. Thermally-conductive PCM is commercially available from several vendors. It is typically sold in sheet form with thicknesses from 1 to several mils. It consists of a wax (high molecular weight hydrocarbon), filled with thermally conductive solid particles such as BN, alumina, diamond, silver flake, etc. As described above with reference to thermal grease, the phase change material may also include cut carbon nanofibrils. These particles typically have characteristic sizes from 1 to several microns. In addition, there may be wetting agents added so that the wax wets the particles, as well as the tips of the fibers.
  • Useful PCM is a solid at room temperature, and softens and melts at elevated temperatures. It may or may not be molten at operating temperatures. The PCM sheet is typically supported by release liner paper that is eventually peeled away before application. In some advantageous embodiments, the melting point of the material is between about 30 degrees C. and 100 degrees C. In some cases, the melting point is between about 40 degrees C. and 70 degree C.
  • The PCM can be added to the fiber tips by a number of methods. The fibers can be flocked into a sheet of PCM that is heated to just the right temperature so that the tips of the flocked fibers adhere to it and remain vertically oriented. The fibers can then be anchored to the PCM sheet by melting the PCM further and/or pushing the fiber tips further into the PCM. The resulting velvet may or may not then be partially encapsulated with silicone gel, PCM, acrylic spray, foam, or other means of encapsulation. The purpose of encapsulation is to (1) hold the fibers together, providing structural support, and (2) preventing fibers from escaping as potentially harmful debris. The latter is of special concern if the fibers are electrically conductive. Next, a PCM sheet can by placed on top of the resulting velvet, and the entire PCM/velvet/PCM sandwich pressed together and/or heated to fuse everything together.
  • This material has several advantages over the use of thermal grease and elastomer potted velvets. Similar to grease, high thermal conductivity PCM improves interface conductance. However, the PCM may be localized preferentially near the tips. This makes gasket very compliant, unlike velvet that is totally filled with elastomer. Furthermore, solid PCM is not messy at room temperature like thermal grease, it supports velvet at room temperature when in solid form, and PCM acts as an adhesive that prevents fibers from escaping as debris.
  • Adhesive Material
  • The nanofibril material described above, which may advantageously include coupling nanofibrils to the larger fibers to form a fiber velvet, can also be used as an adhesive material. As explained above, fiber velvets can form compliant interface pads. These pads can be effective as a thermal interface since they make contact at their fiber tips. For uneven gaps, most or all of the fibers can bend independently in order to span the local gap. Low pressures are sufficient to allow substantially all of the fibers to touch both surfaces. These same attributes are also desirable in an adhesive. An adhesive material that incorporates a fiber velvet provides a dry and reusable medium for adhering to a mating surface.
  • FIG. 7A is a perspective view of a single-sided fiber velvet 50 that comprises an array of fibers. FIG. 7B is a detailed conceptual view of one of the fibers from FIG. 7A showing an array of nanofibrils 36 attached to the tip of a single fiber 38. The end of the fiber 38 that is distal to the nanofibrils 36 is fixedly attached to a base or substrate material 20 using one of the methods described above. The ends of the nanofibrils 36 that are distal to the fiber 38 are available for adhering to a mating surface.
  • Many configurations are possible depending on the application requirements. Thus, the fibers can be bonded to one or both surfaces of a central support with various adhesives or pressure sensitive adhesive (PSA) “tapes” including metal foils and polymers. A single-sided velvet 50 shown in FIG. 7A forms a flexible one-sided tape. Alternatively, a second array of fibers may be attached to a lower surface of the base 20 to form a two-sided tape. Previously described exemplary materials for the substrate or base 20 include a POCO graphite substrate a foil of aluminum, or a plastic film.
  • The fibers 38 can be, for example, any commercially available type. Commercially available carbon fiber include those formed from either pitch or PAN precursor material and drawn onto fiber tow. The carbon fibers 38 may be precision cut from a continuous spool.
  • The term “fiber” as used herein refers to a structure with greater than a 1:1 aspect ratio. The terms “nanofiber” or “nanofibril” as used herein refers to a fiber with a diameter of equal to or less than about 1 μm (micrometer).
  • Each fiber typically has a diameter of 6-10 μm, but which may vary between approximately 3 and 15 microns. In some embodiments, the fibers 38 of the carbon fiber velvet 50 have diameters that range from approximately 5 um to 10 um with lengths that range from approximately ½ mm to 3 mm. Electroflocking can be used to form the aligned fiber arrays 38 on the base 20. Pneumatic or mechanical flocking techniques may also be used.
  • Depending on the desired attachment scheme between the fiber velvet 50 and the mating surface, various geometric and material attributes of the fibers 38 can be selected. These attributes include material properties of the fibers and substrate, for example adhesive strength, modulus, Hamaker constant, dielectric constant, surface energy, and tensile strength and modulus and temperature regimes. These attributes also include geometry, for example, fiber length, fiber diameter, fiber number density, fiber angular bias, and pad thickness, For example, the diameters and lengths of the fibers 38 can be selected depending on the desired compliance of the adhesive material produced with them. To create a more compliant adhesive, fibers with a smaller diameter, longer length, or smaller modulus can be selected.
  • Once the material and diameter are selected, the fibers 38 can be precision cut to the desired length and assembled into the velvet using the techniques described above. For one embodiment in an adhesive application, 6-um diameter×1.5-mm long ex-polyacrylonitrile (ex-PAN) carbon fibers are selected for the carbon fibers 38. These ex-PAN fibers are a glassy carbon and have the advantages of a small diameter, are easy to bend, bend elastically, and do not break easily.
  • The fiber density of the fibers 38 also affects the properties of the adhesive material. Fiber density is the density of the fibers 38 in the fiber velvet 50. Fiber density is also referred to as a packing fraction. Thus, the packing fraction selected may also be based on the desired properties of the carbon fiber velvet 50. For example, a high (20%) packing fraction could be used if relatively low compliance but high adhesive strength was desired. However, for an adhesive application, the packing fraction can be selected as low as a few percent. A lower packing fraction increases the compliance of the resulting carbon fiber velvet 50.
  • To substantially improve the adhesive strength of the carbon fiber velvet 50 with a mating surface, arrays of carbon nanotubes/whiskers/nanofibrils 36 are deposited onto or grown from the tips of the carbon fibers 38. The deposited nanofibrils 36 can be arranged in a “mop” or in an aligned configuration on the tips of the carbon fibers 38. The aligned configuration has similarities to the contact ends of the setae of the gecko foot and is illustrated in FIGS. 7B and 7C. As with the fibers 38, the characteristics or attributes of the nanofibrils 36, for example, diameter, length, packing fraction, location, as well as their properties, for example, thermal and mechanical, can vary. Many of the characteristics of the nanofibrils 36 can be controlled by the growth process and tailored to match or surpass that of the split nanofibrils at the end of a Gecko's seta.
  • An exemplary process for growing nanofibrils 36 on a substrate will now be described. In this process, a thin film of nickel or cobalt catalyst was deposited onto the substrate by ion-beam sputtering. The substrate can be ion-beam cleaned prior to deposition. The resulting film thickness was monitored with a quartz crystal thickness monitor and varied from 1-13 nm thick. Thinner films promote growth of smaller diameter nanofibrils 36. An optional step in the process for growing nanofibrils 36 comprises the deposition of a buffer layer between the substrate and the thin film prior to catalyst deposition. The addition of the buffer layer may promote formation of Ni nanodots upon heating. The inclusion of a buffer layer may facilitate bonding of the nanofibrils 36 to the substrate. For example, a titanium (Ti) buffer layer can form a TiC “weld” between the nanofibrils 36 and the substrate.
  • The nanofibrils 36 were grown on the substrate in a PECVD reactor. The PECVD included a 1200° C. tube furnace with a 3″-diameter quartz tube. Cylindrical graphite electrodes were machined and assembled within the PECVD reactor. The substrate and deposited catalyst was placed on a lower electrode. The quartz tube was evacuated to less than 10 mtorr with a mechanical pump, and continued pumping as the temperature was raised to 700 or 750° C. Once the setpoint temperature was reached, an etchant gas (NH3) was fed at a controlled rate (typically 200 sccm/min) with the pressure being adjusted to a few torr. High voltage (typically 600 V) was then applied between the electrodes and a plasma was initiated. Optionally, the NH3 plasma is allowed to etch the substrate and deposited catalyst for several minutes before starting nanofibril 36 growth. The heating and/or etching step is critical in breaking up the catalyst film on the substrate to form nanodot seeds. Etching reduces the size of the nanodot seeds and breaks up larger nanodot seeds into smaller nanodot seeds. The size and density of the nanodot seeds determine the diameter and density of the nanofibrils that subsequently grow from the nanodot seeds. On silicon substrates, the diameter and density of the nanofibrils correlate with the Ni film thickness.
  • A controlled flow of feed gas, for example acetylene, is then fed to initiate nanofibril growth. Details of the Ni-substrate interaction determine whether and how the nanodots form. Depending on the adhesion between the Ni catalyst and the substrate, the nanofibrils 36 may grow in base-growth or tip-growth modes. Base-growth mode occurs when the catalyst seed remains attached to the substrate and the nanofibril grows out of the catalyst seed. Tip-growth mode occurs when the catalyst seed is carried with the tip of the nanofibril as the nanofibril grows from the catalyst seed). Adhesion of the Ni catalyst to the substrate promotes base growth. After about 15 minutes, the plasma was turned off and the gas flow stopped. The substrate and grown nanofibrils were allowed to cool in vacuum.
  • Other methods for growing well-aligned nanofibrils on a substrate are described in U.S. Pat. No. 6,361,861 to Gao et al., which is hereby incorporated by reference in its entirety and by Li et al., Appl. Phys. Lett. 75, 367 (1999).
  • The attributes of an exemplary fiber velvet 50 that comprises arrays of nanofibrils 36 attached to carbon fibers 38 are described below. A combined packing fraction for the velvet 50 is calculated by multiplying the packing fraction of the carbon fibers 38 with the packing fraction of the nanofibrils 36. The combined packing fraction for the exemplary velvet 50 described below is 2% (10% carbon fiber×20% nanofibrils).
    Carbon Nanotube (CNT) array
    on a carbon fiber tip
    Carbon fiber
    38
    Diameter, D 5 μm
    Length, L 500-1000 μm
    Aspect ratio, α = L/D 100-200
    Packing fraction, φ 10%
    Young's modulus, E 234 GPa
    Pad Compliance (Eφ/α2) ˜106 Pa
    Multi-Walled Nanotube
    (MWNT) array 36
    Diameter, D 20-200 nm
    Length, L 10-50 μm
    Aspect ratio, α = L/D 1000
    Packing fraction, φ 20%
    Young's modulus, E 1000 GPa (est)
    Pad Compliance (Eφ/α2) ˜105 Pa
  • As explained with reference to FIGS. 6A-6C, the carbon fibers 38 can be lapped and polished to form a carbon fiber velvet 50 with a uniform length and flat tips. Lapping and polishing before attaching or growing nanofibrils 36 results in the fiber tips being more co-planar (within a few microns). This geometry provides a flat surface from where to grow the nanofibrils or nanotubes 36. Such controlled tip geometry enhances the consistency of the adhesive surface of the nanotubes or nanofibrils 36 that grow on the flat tips of the carbon fibers 38. One method of lapping the fiber tips involves potting the fibers 38 during lapping of the carbon fiber tips. After lapping, the potting media is removed from between the carbon fibers 38. An example of such a removable potting medium is mothballs. However, lapping and polishing of the carbon fiber tips is not required for the subsequent attachment of the nanofibrils 36 thereon. Alternatively, electro-discharge machining (EDM) can be used to flatten the ends of the carbon fibers 38 prior to attachment of the nanofibrils 36.
  • FIG. 8 illustrates a single fiber 38 that is at a bias angle θ with respect to the base material 20. A biased velvet has fibers 38 which are not perpendicular to the underlying base 20. Embodiments of the velvet include fibers 38 that are biased in the same direction with respect to the base 20. Angles between 0 and 90 degrees could be selected. Biasing the carbon fibers 38 can further increase the compliance of the carbon fiber velvet 50. In one embodiment of the carbon fiber velvet 50, an angle of about 45 degrees is formed between the underlying base 20 and the carbon fibers 38.
  • By biasing the carbon fibers 38 at a particular angle and then lapping the tips of the carbon fibers 38, the nanofibrils 36 can be grown or attached at a particular angle to the carbon fiber 38 shafts as shown in FIG. 8. For example, as illustrated in FIG. 8, the nanofibrils can be grown or attached at an angle that is complementary to the angle θ so that the nanofibrils 36 are normal to the base 20 and/or a mating surface 40. Alternatively, the nanofibrils 36 are grown or attached at an angle with respect to the carbon fiber shafts so that the nanofibrils 36 are not perpendicular or normal to the base 20 and/or the mating surface 40. These angled nanofibrils 36 with respect to the carbon fiber shafts may be more compliant than the carbon fibers 38 when contacting the mating surface 40.
  • Any of the deposition techniques previously described, including CVD, PECVD, or using an AO template, can be used to grow carbon nanofibrils 36 on the tips of carbon fibers 38. These deposition techniques utilize a nano-sized metal catalyst (e.g. nickel, iron, or cobalt) particle on the carbon fiber 38 tip from which the carbon nanotube grows. The catalyst might remain to provide a strong bond to the carbon fiber 38 tip. The strength of the base attachment can be improved by, for example, heat treatment. Another means by which the nanofibril can remain strongly attached to the fiber tip is by reacting the carbon nanofibril with a layer of Ti or other metal to form TiC or other appropriate carbide as a weld. Still another method of strongly attaching the carbon nanofibrils to the carbon fiber tip is by encapsulating with a conformal coating of carbon by chemical vapor deposition (CVD).
  • One method of depositing the catalyst particles on the ends of the carbon fibers 38, is by ion beam sputtering a thin film of catalyst metal onto the carbon fiber 38 tips, and then appropriate heat treatment and/or etching in order to create nanometer-sized catalyst particles. The nanofibril 36 arrays then grow on the catalyst coated fibers 38 via PECVD processing. In embodiments where the nanofibrils 36 are grown at ˜650 degrees C., a carbonizable adhesive can be used to attach the carbon fibers 38 to a carbon (e.g. POCO graphite) substrate. Such a configuration for the carbon fibers 38 and nanofibrils 36 results in comparable size, length, and packing fraction values to that of Tokay gecko setae.
  • The nanotubes 36 can be coated for specific environments. For example, coating the nanotubes with SiC enhances their high temperature capability in an oxidizing atmosphere (such as air).
  • The diameter of the nanofibrils 36 affects the adhesive strength between the tips of the nanofibrils 36 and the mating surface 40. It is postulated that once intimate contact between the nanofibrils 36 of the adhesive material and the mating surface 40 occurs, the compliance of the nanofibrils 36 allows the adhesive material to stick to the mating surface 40 by intermolecular (van der Waals) forces. The van der Waals (vdW) force occurs between the uncharged atoms of the mating surface 40 and the uncharged atoms of the nanofibrils 36. These vdW forces occur due to the mutual induction of an electric dipole moment in each atom. These mutually-induced electrical dipoles attract the nanofibril 36 to the mating surface 40 and vice versa. To maximize the vdW adhesion, it is desirable that the nanotubes 36 be relatively straight or slightly curved, have high packing fraction, small, uniform diameters, and long, uniform lengths.
  • The dipole-dipole pair potential for the vdW forces is given by V=−C/r6, where C is a constant roughly proportional to the polarizabilities of the atoms. The vdW force between macroscopic bodies is the sum of all forces between atoms of one body and those of the other. While the vdW force is usually thought to be small between two atoms, it can be quite large between macroscopic bodies, especially when in close contact.
  • The vdW force between a sphere of radius R and a flat surface, separated by distance D is: F = AR 6 D 2 ;
    where A is the Hamaker constant defined as A=πCρ1ρ2, ρ1 and ρ2 are the number of atoms per volume in the two bodies, and C is the coefficient in the atom-atom pair potential V=−C/r6. Because C is roughly proportional to the polarizabilities of the two materials, A is approximately constant (i.e. independent of density) for all materials, lying in the range 0.3-6×10−19 J for solid bodies. For further discussion see Israelachvili, J. N., Intermolecular and Surface Forces, published by Academic Press, San Diego, 1985 which is hereby incorporated by reference in its entirety.
  • The adhesive pressure over the projected area of the sphere is therefore: P = F π R 2 = A 6 π D 2 R .
  • For an array of spheres with packing fraction φ, the adhesive force per area becomes: P = A ϕ 6 π D 2 R .
  • Taking A=10−19 J, D=0.3 nm, and φ=6%, the calculated adhesive strength for spheres, or fibers with hemispherical tips, as a function of sphere/fiber radius are listed below.
    Fiber radius, R Force per fiber, F (N) P (psi)
    2 micron 3.70E−07 0.26
    200 nm 3.70E−08 2.6
    20 nm 3.70E−09 26
    2 nm 3.70E−10 260
  • This model shows that more smaller fibers adhere more strongly than fewer large fibers of equal area because more atoms are in closer contact with the flat mating surface 40. Furthermore, as the fiber radius reaches the nanometer range as with nanofibrils 36, the adhesive strength can reach hundreds of psi.
  • The density or packing fraction of the nanofibrils 36 affects the adhesive strength between the tips of the nanofibrils 36 and the mating surface 40. While the gecko foot has of the order 106 nanofibrils per mm2, the nanotube arrays 36 have typical densities of 107-108/mm2 as described in Ren et al. and Li et al. For a carbon fiber 38 packing fraction of 10%, this would give a nanofibril 36 density of 106-107, which is comparable to or higher than the density for the gecko foot.
  • The aspect ratio of the nanofibrils 36 can be selected such that they will be able to bend and conform to any contacting mating surface 40. In one embodiment, a nanotube array 36 with 50 nm diameter×5 um length would include such attributes.
  • Depositing additional material on the contact surface of the nanofibrils 36 can further enhance their adhesive strength to the mating surface 40. For example, if the nanofibrils 36 are open at the ends and have insufficient tip area for high adhesive strength, the nanofibril 36 tips can be encapsulated or filled. This filling can be accomplished by, for example, depositing a thin film with a thickness that is comparable to the nanofibril 36 diameter. The encapsulating material could be, for example, a metal or a compliant polymer such as parylene. The encapsulating material can comprise, for example, conductive particles. The electrical characteristics of these conductive particles can be varied depending on the attributes desired of the adhesive material.
  • For line of sight deposition on the tips of the nanofibrils 36 by sputtering or evaporation, the deposited thin film can be thickest at the tips and thinned out on the upper surface area shafts of the nanofibrils 36. Such an enhanced tip of the nanofibril 36 serves a similar purpose as a gecko spatula to the setae. If a non-planar or rounded geometry is attained for the tip of the nanofibril 36, such a rounded tip may adhere well in various orientations.
  • Depending on the microstructure of the carbon fiber velvet 50, the microstructure may be susceptible to clogging by dirt or other particles. The attributes of the microfibrils 36 can be further selected to enhance self-cleaning whereby the contaminants are expelled from the microstructure. For example, it may be important for the material to be hydrophobic to enable this self-cleaning feature, and or comprise a certain packing fraction of nanofibrils. These features are used by the lotus plant to keep it clean. In this way, the attributes of the fibers can be optimized to reduce the effect of contaminants on the adhesive properties of the material.
  • One of the advantages of this nanostructure is that the adhesive material is compliant and therefore able to conform to both flat and nonflat or rough surfaces with a minimal amount of applied pressure. Another advantage is that the adhesive material makes dry contact, sticking by intermolecular (van der Waals) forces, without leaving a sticky residue. Other advantages include: controlled design and manufacture, enabling tailoring and optimizing of array features by modifying fiber and nanotube diameters, lengths, packing fractions, orientation, and location.
  • Exemplary applications of the adhesive material described herein include a wide range of ambient, and even hostile conditions: submarine, high temperature, space vacuum, and chemically corrosive environments. In some advantageous embodiments of the invention, the thermal conductivity and/or electrical conductivity of the carbon fibers can be combined with the adhesive properties. This can produce an electrical or thermal gasket/interface material that sticks without glue or mechanical fasteners to the components it is in contact with.
  • The foregoing description details certain embodiments of the invention. It will be appreciated, however, that no matter how detailed the foregoing appears in text, the invention can be practiced in many ways. As is also stated above, it should be noted that the use of particular terminology when describing certain features or aspects of the invention should not be taken to imply that the terminology is being re-defined herein to be restricted to including any specific characteristics of the features or aspects of the invention with which that terminology is associated. The scope of the invention should therefore be construed in accordance with the appended claims and any equivalents thereof.

Claims (14)

1. A method of producing a substantial intermolecular (e.g. vdW) force over a selected area comprising placing an plurality of fabricated fibers distributed over said selected area in close proximity to a mating surface, wherein said fabricated fibers are configured and oriented to produce a resulting average intermolecular force per unit area that is greater than or equal to 2.6 psi over said selected area.
2. The method of claim 1, wherein at least some of said fabricated fibers have diameters of less than about 1 micron.
3. The method of claim 1, wherein the plurality of fibers has similar sizes.
4. The method of claim 1, wherein the plurality of fibers has different sizes.
5. The method of claim 4, wherein the plurality of fibers comprise a first size fiber attached to a second size fiber.
6. The method of claim 5, wherein the first size fiber has a cross sectional diameter of less than approximately 15 microns and the second size fiber has a cross sectional diameters of less than about 1 micron.
7. A method of adhering a first surface to a second surface, the method comprising:
contacting a plurality of fabricated fibers that are coupled to said first surface with said second surface; and
producing an average intermolecular force per unit area of greater than or equal to 2.6 psi between the plurality of fabricated fibers and the second surface.
8. The method of claim 7, wherein the plurality of fabricated fibers has similar sizes.
9. The method of claim 7, wherein the plurality of fabricated fibers has different sizes.
10. The method of claim 9, wherein the plurality of fabricated fibers comprise a first size fiber attached to a second size fiber.
11. The method of claim 10, wherein the first size fiber has a cross sectional diameter of less than approximately 15 microns and the second size fiber has a cross sectional diameters of less than about 1 micron.
12. A method of forming an adherent interface comprising producing an intermolecular force of greater than or equal to 2.6 psi over a selected area by placing a fabricated plurality of fibers in close proximity to a mating surface.
13. A method of thermally and/or electrically coupling first and second components comprising contacting at least one of said components with a compliant array of a plurality of nanofibrils, wherein said nanofibrils are arranged and configured to transfer heat and/or electrical current from said first component to said second component, and wherein said nanofibrils are also arranged and configured to support an average intermolecular adhesive force per unit area of at least 2.6 psi such that plurality of nanofibrils adhere to the component they are in contact.
14. The method of claim 13, wherein said nanofibrils comprise carbon.
US11/441,472 1999-06-14 2006-05-26 Fiber adhesive material Abandoned US20060213599A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US11/441,472 US20060213599A1 (en) 1999-06-14 2006-05-26 Fiber adhesive material

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US13944399P 1999-06-14 1999-06-14
US09/593,587 US6913075B1 (en) 1999-06-14 2000-06-13 Dendritic fiber material
US39023902P 2002-06-17 2002-06-17
US10/464,830 US7132161B2 (en) 1999-06-14 2003-06-17 Fiber adhesive material
US11/441,472 US20060213599A1 (en) 1999-06-14 2006-05-26 Fiber adhesive material

Related Parent Applications (2)

Application Number Title Priority Date Filing Date
US09/593,587 Continuation-In-Part US6913075B1 (en) 1999-06-14 2000-06-13 Dendritic fiber material
US10/464,830 Division US7132161B2 (en) 1999-06-14 2003-06-17 Fiber adhesive material

Publications (1)

Publication Number Publication Date
US20060213599A1 true US20060213599A1 (en) 2006-09-28

Family

ID=32074235

Family Applications (2)

Application Number Title Priority Date Filing Date
US10/464,830 Expired - Lifetime US7132161B2 (en) 1999-06-14 2003-06-17 Fiber adhesive material
US11/441,472 Abandoned US20060213599A1 (en) 1999-06-14 2006-05-26 Fiber adhesive material

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US10/464,830 Expired - Lifetime US7132161B2 (en) 1999-06-14 2003-06-17 Fiber adhesive material

Country Status (1)

Country Link
US (2) US7132161B2 (en)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040009353A1 (en) * 1999-06-14 2004-01-15 Knowles Timothy R. PCM/aligned fiber composite thermal interface
US20050181629A1 (en) * 2003-09-08 2005-08-18 Anand Jagota Fibrillar microstructure and processes for the production thereof
US20060068195A1 (en) * 2004-05-19 2006-03-30 Arun Majumdar Electrically and thermally conductive carbon nanotube or nanofiber array dry adhesive
US20080292840A1 (en) * 2004-05-19 2008-11-27 The Regents Of The University Of California Electrically and thermally conductive carbon nanotube or nanofiber array dry adhesive
US20090098671A1 (en) * 2004-09-10 2009-04-16 Dong-Wook Kim Nanotube assembly including protective layer and method for making the same
US20090233058A1 (en) * 2008-02-29 2009-09-17 Kenji Hata Carbon nanotube structure and method for producing the same
US20100021647A1 (en) * 2006-12-14 2010-01-28 Carnegie Mellon University Dry adhesives and methods for making dry adhesives
US20100136281A1 (en) * 2006-12-14 2010-06-03 Carnegie Mellon University Dry adhesives and methods for making dry adhesives
US20100319111A1 (en) * 2009-06-19 2010-12-23 Under Armour, Inc. Nanoadhesion structures for sporting gear
US20110104430A1 (en) * 2008-03-17 2011-05-05 Avery Dennison Corporation Functional Micro- and/or Nano-Structure Bearing Constructions and/or Methods for Fabricating Same
US20120276327A1 (en) * 2006-10-17 2012-11-01 Purdue Research Foundation Electrothermal interface material enhancer
US9120953B2 (en) 2008-09-18 2015-09-01 Carnegie Mellon University Methods of forming dry adhesive structures
CN108474109A (en) * 2016-01-13 2018-08-31 应用材料公司 Method for keeping the holding arrangement of substrate, the method and release substrate of the carrier for being used to support substrate, vacuum flush system, holding substrate
JP2018172589A (en) * 2017-03-31 2018-11-08 日本ゼオン株式会社 Bonding method
US10418306B1 (en) * 2018-06-22 2019-09-17 Trw Automotive U.S. Llc Thermal interface for electronics
US11040379B2 (en) * 2007-09-17 2021-06-22 Bruker Nano, Inc. Debris removal in high aspect structures
US11391664B2 (en) 2007-09-17 2022-07-19 Bruker Nano, Inc. Debris removal from high aspect structures
US11964310B2 (en) 2023-01-06 2024-04-23 Bruker Nano, Inc. Debris removal from high aspect structures

Families Citing this family (135)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7132161B2 (en) * 1999-06-14 2006-11-07 Energy Science Laboratories, Inc. Fiber adhesive material
US6737160B1 (en) * 1999-12-20 2004-05-18 The Regents Of The University Of California Adhesive microstructure and method of forming same
US8815385B2 (en) * 1999-12-20 2014-08-26 The Regents Of The University Of California Controlling peel strength of micron-scale structures
US7847207B1 (en) * 2000-03-17 2010-12-07 University Of Central Florida Research Foundation, Inc. Method and system to attach carbon nanotube probe to scanning probe microscopy tips
US7462498B2 (en) * 2001-10-19 2008-12-09 Applied Nanotech Holdings, Inc. Activation of carbon nanotubes for field emission applications
US6872439B2 (en) * 2002-05-13 2005-03-29 The Regents Of The University Of California Adhesive microstructure and method of forming same
DE10223234B4 (en) * 2002-05-24 2005-02-03 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Process for the preparation of microstructured surfaces with increased adhesion and adhesion-enhancing modified surfaces
CN1656189A (en) * 2002-05-29 2005-08-17 纳幕尔杜邦公司 Fibrillar microstructure for conformal contact and adhesion
US20050221072A1 (en) * 2003-04-17 2005-10-06 Nanosys, Inc. Medical device applications of nanostructured surfaces
US7972616B2 (en) 2003-04-17 2011-07-05 Nanosys, Inc. Medical device applications of nanostructured surfaces
US7074294B2 (en) * 2003-04-17 2006-07-11 Nanosys, Inc. Structures, systems and methods for joining articles and materials and uses therefor
US20060122596A1 (en) * 2003-04-17 2006-06-08 Nanosys, Inc. Structures, systems and methods for joining articles and materials and uses therefor
US7056409B2 (en) * 2003-04-17 2006-06-06 Nanosys, Inc. Structures, systems and methods for joining articles and materials and uses therefor
US7803574B2 (en) 2003-05-05 2010-09-28 Nanosys, Inc. Medical device applications of nanostructured surfaces
DE10325372B3 (en) * 2003-05-27 2004-10-21 Gottlieb Binder Gmbh & Co. Kg Production of an adhesion closure part for diapers or hospital clothing comprises providing a support with a number of stalks connected to it
FR2858465A1 (en) * 2003-07-29 2005-02-04 Commissariat Energie Atomique POROUS STRUCTURES USED AS BIPOLAR PLATES AND METHODS OF PREPARING SUCH POROUS STRUCTURES
US7416019B2 (en) * 2003-08-13 2008-08-26 The Johns Hopkins University Thermal interface and switch using carbon nanotube arrays
US20050089638A1 (en) * 2003-09-16 2005-04-28 Koila, Inc. Nano-material thermal and electrical contact system
WO2005025734A2 (en) * 2003-09-17 2005-03-24 Molecular Nanosystems, Inc. Methods for producing and using catalytic substrates for carbon nanotube growth
US20050214197A1 (en) * 2003-09-17 2005-09-29 Molecular Nanosystems, Inc. Methods for producing and using catalytic substrates for carbon nanotube growth
US20050119640A1 (en) * 2003-10-03 2005-06-02 The Regents Of The University Of California Surgical instrument for adhering to tissues
WO2005033237A2 (en) * 2003-10-03 2005-04-14 The Regents Of The University Of California Apparatus for friction enhancement of curved surfaces
CN1886537B (en) * 2003-10-16 2013-07-24 阿克伦大学 Carbon nanotubes on carbon nanofiber substrate
US8025960B2 (en) 2004-02-02 2011-09-27 Nanosys, Inc. Porous substrates, articles, systems and compositions comprising nanofibers and methods of their use and production
US20110039690A1 (en) * 2004-02-02 2011-02-17 Nanosys, Inc. Porous substrates, articles, systems and compositions comprising nanofibers and methods of their use and production
US7527222B2 (en) * 2004-04-06 2009-05-05 The Boeing Company Composite barrel sections for aircraft fuselages and other structures, and methods and systems for manufacturing such barrel sections
US20050271870A1 (en) * 2004-06-07 2005-12-08 Jackson Warren B Hierarchically-dimensioned-microfiber-based dry adhesive materials
US7622066B2 (en) 2004-07-26 2009-11-24 The Boeing Company Methods and systems for manufacturing composite parts with female tools
US20060029697A1 (en) * 2004-08-05 2006-02-09 Bruce Robbins Food wraps and bags with cling properties and method of manufacture
US7325771B2 (en) 2004-09-23 2008-02-05 The Boeing Company Splice joints for composite aircraft fuselages and other structures
US7306450B2 (en) 2004-09-29 2007-12-11 The Boeing Company Apparatuses, systems, and methods for manufacturing composite parts
US7914912B2 (en) * 2004-11-10 2011-03-29 The Regents Of The University Of California Actively switchable nano-structured adhesive
US7799423B2 (en) * 2004-11-19 2010-09-21 The Regents Of The University Of California Nanostructured friction enhancement using fabricated microstructure
US7503368B2 (en) 2004-11-24 2009-03-17 The Boeing Company Composite sections for aircraft fuselages and other structures, and methods and systems for manufacturing such sections
US20060130294A1 (en) * 2004-12-16 2006-06-22 Adams William E Fastener and method of making same
US7269015B2 (en) * 2005-02-01 2007-09-11 Tyco Electronics Corporation Heat sink interface insert
US7476982B2 (en) * 2005-02-28 2009-01-13 Regents Of The University Of California Fabricated adhesive microstructures for making an electrical connection
CN1837147B (en) * 2005-03-24 2010-05-05 清华大学 Thermal interface material and its production method
US7479198B2 (en) * 2005-04-07 2009-01-20 Timothy D'Annunzio Methods for forming nanofiber adhesive structures
US8601694B2 (en) 2008-06-13 2013-12-10 The Boeing Company Method for forming and installing stringers
US8557165B2 (en) 2008-10-25 2013-10-15 The Boeing Company Forming highly contoured composite parts
FR2885210A1 (en) * 2005-04-29 2006-11-03 Univ Joseph Fourier Etablissem METHOD FOR PRODUCING A WALL, ESPECIALLY A THERMAL MICRO-EXCHANGER, AND A HEAT MICRO-EXCHANGER, COMPRISING PARTICULARLY NANOTUBES
US20070116957A1 (en) * 2005-05-11 2007-05-24 Molecular Nanosystems, Inc. Carbon nanotube thermal pads
US7763353B2 (en) * 2005-06-10 2010-07-27 Ut-Battelle, Llc Fabrication of high thermal conductivity arrays of carbon nanotubes and their composites
US9771264B2 (en) * 2005-10-25 2017-09-26 Massachusetts Institute Of Technology Controlled-orientation films and nanocomposites including nanotubes or other nanostructures
WO2007061854A2 (en) * 2005-11-18 2007-05-31 The Regents Of The University Of California Compliant base to increase contact for micro- or nano-fibers
US8148276B2 (en) * 2005-11-28 2012-04-03 University Of Hawaii Three-dimensionally reinforced multifunctional nanocomposites
US7655168B2 (en) * 2006-01-31 2010-02-02 The Boeing Company Tools for manufacturing composite parts and methods for using such tools
GB2435719A (en) * 2006-03-03 2007-09-05 Darrell Lee Mann Gripping device with a multitude of small fibres using van der Waals forces
JP4884050B2 (en) * 2006-03-30 2012-02-22 富士フイルム株式会社 Drive device
KR100870207B1 (en) * 2007-03-15 2008-11-25 이진 The directional adhesive structures to be controllable adhesion force and the manufacturing method thereof
EP2385016B1 (en) 2006-05-19 2018-08-08 Massachusetts Institute of Technology Continuous process for the production of nanostructures
US8337979B2 (en) 2006-05-19 2012-12-25 Massachusetts Institute Of Technology Nanostructure-reinforced composite articles and methods
US20070298168A1 (en) * 2006-06-09 2007-12-27 Rensselaer Polytechnic Institute Multifunctional carbon nanotube based brushes
US20080280085A1 (en) * 2006-06-25 2008-11-13 Oren Livne Dynamically Tunable Fibrillar Structures
US8563117B2 (en) * 2006-08-04 2013-10-22 Phillip B. Messersmith Biomimetic modular adhesive complex: materials, methods and applications therefore
JP4509981B2 (en) * 2006-08-11 2010-07-21 日東電工株式会社 Cleaning member, conveying member with cleaning function, and cleaning method for substrate processing apparatus
EP2050515B1 (en) * 2006-08-11 2013-02-27 Nitto Denko Corporation Cleaning member, delivery member with cleaning function, and method of cleaning substrate processing apparatus
US8309201B2 (en) * 2006-08-23 2012-11-13 The Regents Of The University Of California Symmetric, spatular attachments for enhanced adhesion of micro- and nano-fibers
US20080292835A1 (en) * 2006-08-30 2008-11-27 Lawrence Pan Methods for forming freestanding nanotube objects and objects so formed
JP2010504268A (en) * 2006-09-21 2010-02-12 アイメック Growth of carbon nanotubes using metal-free nanoparticles
US20080169003A1 (en) * 2007-01-17 2008-07-17 Nasa Headquarters Field reactive amplification controlling total adhesion loading
US8388795B2 (en) * 2007-05-17 2013-03-05 The Boeing Company Nanotube-enhanced interlayers for composite structures
US20080310114A1 (en) * 2007-06-18 2008-12-18 Lucent Technologies Inc. Heat-transfer device for an electromagnetic interference (emi) shield using conductive bristles
US20090002949A1 (en) * 2007-06-29 2009-01-01 Lucent Technologies Inc. Heat transfer for electronic component via an electromagnetic interference (emi) shield having shield deformation
US7743763B2 (en) * 2007-07-27 2010-06-29 The Boeing Company Structurally isolated thermal interface
US8042767B2 (en) * 2007-09-04 2011-10-25 The Boeing Company Composite fabric with rigid member structure
US20100252177A1 (en) * 2007-10-26 2010-10-07 Bae Systems Plc Adhesive microstructures
US7968184B2 (en) * 2007-12-03 2011-06-28 Schlumberger Technology Corporation Erosion resistant surface and method of making erosion resistant surfaces
CN101883545B (en) 2007-12-06 2013-08-07 纳诺西斯有限公司 Resorbable nanoenhanced hemostatic structures and bandage materials
US8319002B2 (en) 2007-12-06 2012-11-27 Nanosys, Inc. Nanostructure-enhanced platelet binding and hemostatic structures
US7479590B1 (en) 2008-01-03 2009-01-20 International Business Machines Corporation Dry adhesives, methods of manufacture thereof and articles comprising the same
US7881785B2 (en) 2008-03-26 2011-02-01 Cardiac Science Corporation Method and apparatus for defrosting a defibrillation electrode
US8025971B2 (en) * 2008-04-16 2011-09-27 Nitto Denko Corporation Fibrous columnar structure aggregate and pressure-sensitive adhesive member using the aggregate
KR101015293B1 (en) 2008-04-16 2011-02-15 닛토덴코 가부시키가이샤 Fibrous columnar structure assembly and adhesive member using the same
US8728602B2 (en) 2008-04-28 2014-05-20 The Charles Stark Draper Laboratory, Inc. Multi-component adhesive system
KR101420680B1 (en) * 2008-09-22 2014-07-17 삼성전자주식회사 Apparatus and method for surface treatment of carbon fiber using resistive heating
JP5239768B2 (en) * 2008-11-14 2013-07-17 富士通株式会社 Heat dissipating material, electronic equipment and manufacturing method thereof
JP2010171200A (en) * 2009-01-22 2010-08-05 Shinko Electric Ind Co Ltd Heat radiator of semiconductor package
US20100195263A1 (en) * 2009-02-02 2010-08-05 Space Charge, LLC Capacitors using carbon-based extensions
US9111658B2 (en) 2009-04-24 2015-08-18 Applied Nanostructured Solutions, Llc CNS-shielded wires
JP2012525012A (en) * 2009-04-24 2012-10-18 アプライド ナノストラクチャード ソリューションズ リミテッド ライアビリティー カンパニー CNT leaching EMI shielding composite and coating
WO2010129234A2 (en) * 2009-04-27 2010-11-11 Lockheed Martin Corporation Cnt-based resistive heating for deicing composite structures
JP5578699B2 (en) * 2009-04-28 2014-08-27 日東電工株式会社 Carbon nanotube assembly
CN102428763A (en) 2009-05-19 2012-04-25 纳米***公司 Nanostructured materials for battery applications
US20130258600A1 (en) * 2009-06-30 2013-10-03 General Electric Company Thermal interface element and article including the same
EP2452063B1 (en) 2009-07-10 2016-06-01 Etalim Inc. Stirling cycle transducer for converting between thermal energy and mechanical energy
US9290388B2 (en) * 2009-08-03 2016-03-22 Inje University Industry-Academic Cooperation Foundation Carbonaceous nanocomposite having novel structure and fabrication method thereof
CA2717633C (en) * 2009-10-14 2018-06-19 Simon Fraser University Biomimetic dry adhesives and methods of production therefor
US20110123735A1 (en) * 2009-11-23 2011-05-26 Applied Nanostructured Solutions, Llc Cnt-infused fibers in thermoset matrices
AU2010321536A1 (en) * 2009-11-23 2012-04-19 Applied Nanostructured Solutions, Llc CNT-tailored composite space-based structures
US20110124253A1 (en) * 2009-11-23 2011-05-26 Applied Nanostructured Solutions, Llc Cnt-infused fibers in carbon-carbon composites
JP5374354B2 (en) * 2009-12-25 2013-12-25 日東電工株式会社 Carbon nanotube composite structure and adhesive member
US9167736B2 (en) * 2010-01-15 2015-10-20 Applied Nanostructured Solutions, Llc CNT-infused fiber as a self shielding wire for enhanced power transmission line
WO2011146151A2 (en) * 2010-02-02 2011-11-24 Applied Nanostructured Solutions, Llc Fiber containing parallel-aligned carbon nanotubes
EP2543052B1 (en) * 2010-03-02 2019-11-27 Applied NanoStructured Solutions, LLC Electrical devices containing carbon nanotube-infused fibers and methods for production thereof
WO2011109480A2 (en) 2010-03-02 2011-09-09 Applied Nanostructed Solution, Llc Spiral wound electrical devices containing carbon nanotube-infused electrode materials and methods and apparatuses for production thereof
US8440926B2 (en) 2010-06-09 2013-05-14 Apple Inc. Low profile tape structures
US8780526B2 (en) 2010-06-15 2014-07-15 Applied Nanostructured Solutions, Llc Electrical devices containing carbon nanotube-infused fibers and methods for production thereof
JP2012040664A (en) * 2010-08-23 2012-03-01 Nitto Denko Corp Fibrous columnar structure aggregate and adhesive member
US9017854B2 (en) 2010-08-30 2015-04-28 Applied Nanostructured Solutions, Llc Structural energy storage assemblies and methods for production thereof
JP2014508370A (en) * 2010-09-23 2014-04-03 アプライド ナノストラクチャード ソリューションズ リミテッド ライアビリティー カンパニー CNT-infused fibers as self-shielding wires for reinforced transmission lines
AU2011338963A1 (en) 2010-10-21 2013-05-30 University Of Massachusetts High capacity easy release extended use adhesive devices
CN103562535A (en) 2010-11-18 2014-02-05 埃塔里姆有限公司 Stirling cycle transducer apparatus
US9390828B2 (en) * 2011-07-01 2016-07-12 The University Of Kentucky Research Foundation Crystallographically-oriented carbon nanotubes grown on few-layer graphene films
JP2013014449A (en) 2011-07-01 2013-01-24 Nitto Denko Corp Aggregation of fibrous columnar structure
US9388513B2 (en) * 2011-07-01 2016-07-12 The University Of Kentucky Research Foundation Crystallographically-oriented carbon nanotubes grown on few-layer graphene films
JP5893374B2 (en) 2011-12-08 2016-03-23 日東電工株式会社 Carbon nanotube aggregate and viscoelastic body using the same
CN104094000B (en) 2012-01-19 2016-09-28 马萨诸塞大学 Two-sided and multiaspect adhering apparatus
JP2013160589A (en) * 2012-02-03 2013-08-19 Nitto Denko Corp Sample fixing member for nano indenter
US9085464B2 (en) 2012-03-07 2015-07-21 Applied Nanostructured Solutions, Llc Resistance measurement system and method of using the same
US9506194B2 (en) 2012-09-04 2016-11-29 Ocv Intellectual Capital, Llc Dispersion of carbon enhanced reinforcement fibers in aqueous or non-aqueous media
JP2014098107A (en) * 2012-11-15 2014-05-29 Nitto Denko Corp Holding material used in outer space
CN104981526B (en) 2013-02-06 2017-07-04 马萨诸塞大学 Load-bearing adhesion material with adjustable angle
CA2901173A1 (en) 2013-02-14 2014-08-21 Kellie K Apparel Llc Brassiere
ES2663666T3 (en) 2013-02-28 2018-04-16 N12 Technologies, Inc. Nanostructure film cartridge based dispensing
JP2016519178A (en) 2013-03-14 2016-06-30 ユニバーシテイ・オブ・マサチユセツツ Application and load bearing device and method of use
US9603419B2 (en) 2013-03-15 2017-03-28 University Of Massachusetts High capacity easy release extended use adhesive closure devices
US9474188B2 (en) 2013-04-30 2016-10-18 Lumentum Operations Llc Sliding thermal contact for pluggable optic modules
US9859199B2 (en) 2013-12-18 2018-01-02 Taiwan Semiconductor Manufacturing Co., Ltd. Method for forming semiconductor package using carbon nano material in molding compound
US9072343B1 (en) 2014-01-02 2015-07-07 John W. Ogilvie Multigrip touch closure fasteners
US8899318B1 (en) 2014-04-24 2014-12-02 Ronald C. Parsons Applying an aggregate to expandable tubular
JP6405914B2 (en) * 2014-11-11 2018-10-17 株式会社デンソー HEAT EXCHANGE DEVICE AND HEAT EXCHANGE DEVICE MANUFACTURING METHOD
KR102281850B1 (en) * 2015-02-25 2021-07-26 삼성디스플레이 주식회사 Touch sensor, manufacturing method thereof and display device including the same
US10147921B2 (en) * 2015-07-06 2018-12-04 KULR Technology Corporation System, method, and apparatus for battery protection
US20170108297A1 (en) * 2015-10-19 2017-04-20 KULR Technology Corporation Fiber Thermal Interface
EP3463826B1 (en) 2016-05-31 2023-07-05 Massachusetts Institute of Technology Composite articles comprising non-linear elongated nanostructures and associated methods
WO2018156878A1 (en) * 2017-02-24 2018-08-30 Lintec Of America, Inc. Nanofiber thermal interface material
US20190085138A1 (en) 2017-09-15 2019-03-21 Massachusetts Institute Of Technology Low-defect fabrication of composite materials
US11031657B2 (en) 2017-11-28 2021-06-08 Massachusetts Institute Of Technology Separators comprising elongated nanostructures and associated devices and methods, including devices and methods for energy storage and/or use
US11373833B1 (en) * 2018-10-05 2022-06-28 Government Of The United States, As Represented By The Secretary Of The Air Force Systems, methods and apparatus for fabricating and utilizing a cathode
WO2020195977A1 (en) * 2019-03-22 2020-10-01 国立研究開発法人物質・材料研究機構 Composite body, unmanned aircraft, method for manufacturing composite body, and structure
WO2020216802A1 (en) * 2019-04-23 2020-10-29 Dsm Ip Assets B.V. A method to removably connect a carpet product to a surface and a double face tape for use in the method
CN111508914B (en) * 2020-06-18 2020-11-13 上海大陆天瑞激光表面工程有限公司 Double-sided plush heat conduction blanket for electronic packaging thermal interface material
JP2022026160A (en) * 2020-07-30 2022-02-10 パナソニックIpマネジメント株式会社 Heat sink and manufacturing method therefor

Citations (83)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2542637A (en) * 1946-05-10 1951-02-20 Gen Motors Corp Method of rectifying a neutral salt heat-treating bath
US3294880A (en) * 1964-04-21 1966-12-27 Space Age Materials Corp Continuous method of manufacturing ablative and refractory materials
US3375308A (en) * 1964-04-21 1968-03-26 Space Age Materials Corp Method of making high purity and non-melting filaments
US3531249A (en) * 1966-11-07 1970-09-29 Pfizer Pyrolytic graphite filaments
US3543842A (en) * 1966-10-13 1970-12-01 Bolkow Gmbh Device for elastic and heat conducting connection of thermo-couples
US3609992A (en) * 1969-06-21 1971-10-05 Philips Corp Hermetically sealed box for maintaining a semiconductor radiation detector at a very low temperature
US3969754A (en) * 1973-10-22 1976-07-13 Hitachi, Ltd. Semiconductor device having supporting electrode composite structure of metal containing fibers
US4161747A (en) * 1978-02-24 1979-07-17 Nasa Shock isolator for operating a diode laser on a closed-cycle refrigerator
US4414142A (en) * 1980-04-18 1983-11-08 Vogel F Lincoln Organic matrix composites reinforced with intercalated graphite
US4415025A (en) * 1981-08-10 1983-11-15 International Business Machines Corporation Thermal conduction element for semiconductor devices
US4424145A (en) * 1981-06-22 1984-01-03 Union Carbide Corporation Calcium intercalated boronated carbon fiber
US4435375A (en) * 1981-03-27 1984-03-06 Shohei Tamura Method for producing a carbon filament and derivatives thereof
US4470063A (en) * 1980-11-19 1984-09-04 Hitachi, Ltd. Copper matrix electrode having carbon fibers therein
US4482912A (en) * 1981-02-06 1984-11-13 Hitachi, Ltd. Stacked structure having matrix-fibered composite layers and a metal layer
US4485429A (en) * 1982-06-09 1984-11-27 Sperry Corporation Apparatus for cooling integrated circuit chips
US4591659A (en) * 1983-12-22 1986-05-27 Trw Inc. Multilayer printed circuit board structure
US4630174A (en) * 1983-10-31 1986-12-16 Kaufman Lance R Circuit package with external circuit board and connection
US4749514A (en) * 1985-10-12 1988-06-07 Research Development Corp. Of Japan Graphite intercalation compound film and method of preparing the same
US4816289A (en) * 1984-04-25 1989-03-28 Asahi Kasei Kogyo Kabushiki Kaisha Process for production of a carbon filament
US4849858A (en) * 1986-10-20 1989-07-18 Westinghouse Electric Corp. Composite heat transfer means
US4867235A (en) * 1986-10-20 1989-09-19 Westinghouse Electric Corp. Composite heat transfer means
US4878152A (en) * 1987-06-16 1989-10-31 Thomson-Csf Mounting for printed circuits forming a heat sink with controlled expansion
US4933804A (en) * 1984-01-19 1990-06-12 The Rank Organisation Plc Interference suppression for semi-conducting switching devices
US4966226A (en) * 1989-12-29 1990-10-30 Digital Equipment Corporation Composite graphite heat pipe apparatus and method
US4985805A (en) * 1986-11-21 1991-01-15 Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. Device for the cooling of optoelectronic components and use of a flange joint used thereof
US5014161A (en) * 1985-07-22 1991-05-07 Digital Equipment Corporation System for detachably mounting semiconductors on conductor substrate
US5077637A (en) * 1989-09-25 1991-12-31 The Charles Stark Draper Lab., Inc. Solid state directional thermal cable
US5111359A (en) * 1991-04-17 1992-05-05 E-Systems Inc. Heat transfer device and method
US5150748A (en) * 1990-06-18 1992-09-29 Mcdonnell Douglas Corporation Advanced survivable radiator
US5212625A (en) * 1988-12-01 1993-05-18 Akzo Nv Semiconductor module having projecting cooling fin groups
US5224030A (en) * 1990-03-30 1993-06-29 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Semiconductor cooling apparatus
US5260124A (en) * 1991-11-25 1993-11-09 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Intercalated hybrid graphite fiber composite
US5316080A (en) * 1990-03-30 1994-05-31 The United States Of America As Represented By The Administrator Of The National Aeronautics & Space Administration Heat transfer device
US5323294A (en) * 1993-03-31 1994-06-21 Unisys Corporation Liquid metal heat conducting member and integrated circuit package incorporating same
US5389400A (en) * 1993-04-07 1995-02-14 Applied Sciences, Inc. Method for making a diamond/carbon/carbon composite useful as an integral dielectric heat sink
US5402004A (en) * 1990-08-14 1995-03-28 Texas Instruments Incorporated Heat transfer module for ultra high density and silicon on silicon packaging applications
US5424916A (en) * 1989-07-28 1995-06-13 The Charles Stark Draper Laboratory, Inc. Combination conductive and convective heatsink
US5424054A (en) * 1993-05-21 1995-06-13 International Business Machines Corporation Carbon fibers and method for their production
US5428601A (en) * 1990-07-23 1995-06-27 U.S. Philips Corporation Method of operating a communications system, a communications system and a secondary station for use in the system
US5494753A (en) * 1994-06-20 1996-02-27 General Electric Company Articles having thermal conductors of graphite
US5520976A (en) * 1993-06-30 1996-05-28 Simmonds Precision Products Inc. Composite enclosure for electronic hardware
US5523260A (en) * 1993-08-02 1996-06-04 Motorola, Inc. Method for heatsinking a controlled collapse chip connection device
US5542471A (en) * 1993-11-16 1996-08-06 Loral Vought System Corporation Heat transfer element having the thermally conductive fibers
US5566752A (en) * 1994-10-20 1996-10-22 Lockheed Fort Worth Company High heat density transfer device
US5591312A (en) * 1992-10-09 1997-01-07 William Marsh Rice University Process for making fullerene fibers
US5608267A (en) * 1992-09-17 1997-03-04 Olin Corporation Molded plastic semiconductor package including heat spreader
US5698175A (en) * 1994-07-05 1997-12-16 Nec Corporation Process for purifying, uncapping and chemically modifying carbon nanotubes
US5753088A (en) * 1997-02-18 1998-05-19 General Motors Corporation Method for making carbon nanotubes
US5805424A (en) * 1996-09-24 1998-09-08 Texas Instruments Incorporated Microelectronic assemblies including Z-axis conductive films
US5814290A (en) * 1995-07-24 1998-09-29 Hyperion Catalysis International Silicon nitride nanowhiskers and method of making same
US5830326A (en) * 1991-10-31 1998-11-03 Nec Corporation Graphite filaments having tubular structure and method of forming the same
US5849130A (en) * 1996-07-10 1998-12-15 Browne; James M. Method of making and using thermally conductive joining film
US6054198A (en) * 1996-04-29 2000-04-25 Parker-Hannifin Corporation Conformal thermal interface material for electronic components
US6063243A (en) * 1995-02-14 2000-05-16 The Regents Of The Univeristy Of California Method for making nanotubes and nanoparticles
US6119573A (en) * 1997-01-27 2000-09-19 Raytheon Company Carbon fiber flocking for thermal management of compact missile electronics
US6143445A (en) * 1998-08-07 2000-11-07 Ferment; George R. Composite electrodes containing chopped conductive fibers
US6156256A (en) * 1998-05-13 2000-12-05 Applied Sciences, Inc. Plasma catalysis of carbon nanofibers
US6177213B1 (en) * 1998-08-17 2001-01-23 Energy Conversion Devices, Inc. Composite positive electrode material and method for making same
US6183854B1 (en) * 1999-01-22 2001-02-06 West Virginia University Method of making a reinforced carbon foam material and related product
US6197859B1 (en) * 1993-06-14 2001-03-06 The Bergquist Company Thermally conductive interface pads for electronic devices
US6256996B1 (en) * 1999-12-09 2001-07-10 International Business Machines Corporation Nanoscopic thermoelectric coolers
US6303094B1 (en) * 1997-03-21 2001-10-16 Japan Fine Ceramics Center Process for producing carbon nanotubes, process for producing carbon nanotube film, and structure provided with carbon nanotube film
US6318954B1 (en) * 1997-03-19 2001-11-20 Jagenberg Papiertechnik Gmbh Device for stacking sheets, in particular sheet-fed paper or cardboard sheets delivered onto pallets
US6361861B2 (en) * 1999-06-14 2002-03-26 Battelle Memorial Institute Carbon nanotubes on a substrate
US6436506B1 (en) * 1998-06-24 2002-08-20 Honeywell International Inc. Transferrable compliant fibrous thermal interface
US6542371B1 (en) * 2000-11-02 2003-04-01 Intel Corporation High thermal conductivity heat transfer pad
US20030124312A1 (en) * 2002-01-02 2003-07-03 Kellar Autumn Adhesive microstructure and method of forming same
US20030152764A1 (en) * 2002-02-06 2003-08-14 Bunyan Michael H. Thermal management materials having a phase change dispersion
US6617199B2 (en) * 1998-06-24 2003-09-09 Honeywell International Inc. Electronic device having fibrous interface
US20030203188A1 (en) * 2002-02-06 2003-10-30 H. Bunyan Michael Thermal management materials
US20030203139A1 (en) * 1998-06-19 2003-10-30 Zhifeng Ren Free-standing and aligned carbon nanotubes and synthesis thereof
US20030208888A1 (en) * 2002-05-13 2003-11-13 Fearing Ronald S. Adhesive microstructure and method of forming same
US6713151B1 (en) * 1998-06-24 2004-03-30 Honeywell International Inc. Compliant fibrous thermal interface
US20040081843A1 (en) * 2002-10-29 2004-04-29 Bunyan Michael H. High temperature stable thermal interface material
US6737160B1 (en) * 1999-12-20 2004-05-18 The Regents Of The University Of California Adhesive microstructure and method of forming same
US6835453B2 (en) * 2001-01-22 2004-12-28 Parker-Hannifin Corporation Clean release, phase change thermal interface
US6913075B1 (en) * 1999-06-14 2005-07-05 Energy Science Laboratories, Inc. Dendritic fiber material
US6965513B2 (en) * 2001-12-20 2005-11-15 Intel Corporation Carbon nanotube thermal interface structures
US20050255304A1 (en) * 2004-05-14 2005-11-17 Damon Brink Aligned nanostructure thermal interface material
US20060216599A1 (en) * 2004-03-23 2006-09-28 Boden David P Cureless battery paste and method for producing battery plates
US20060234056A1 (en) * 2005-04-14 2006-10-19 Tsinghua University Thermal interface material and method for making the same
US20060231970A1 (en) * 2005-04-14 2006-10-19 Tsinghua Unversity Method for manufacturing a thermal interface material
US7132161B2 (en) * 1999-06-14 2006-11-07 Energy Science Laboratories, Inc. Fiber adhesive material

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2542537A (en) * 1945-10-04 1951-02-20 William F Klemm Protractor compass
US4318954A (en) 1981-02-09 1982-03-09 Boeing Aerospace Company Printed wiring board substrates for ceramic chip carriers
JP2768706B2 (en) 1988-12-05 1998-06-25 株式会社日立製作所 Heat transfer tube device
US5136080A (en) * 1989-12-04 1992-08-04 Burroughs Wellcome Co. Nitrile compounds
JP2526408B2 (en) 1994-01-28 1996-08-21 工業技術院長 Carbon nano tube continuous manufacturing method and apparatus

Patent Citations (90)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2542637A (en) * 1946-05-10 1951-02-20 Gen Motors Corp Method of rectifying a neutral salt heat-treating bath
US3294880A (en) * 1964-04-21 1966-12-27 Space Age Materials Corp Continuous method of manufacturing ablative and refractory materials
US3375308A (en) * 1964-04-21 1968-03-26 Space Age Materials Corp Method of making high purity and non-melting filaments
US3543842A (en) * 1966-10-13 1970-12-01 Bolkow Gmbh Device for elastic and heat conducting connection of thermo-couples
US3531249A (en) * 1966-11-07 1970-09-29 Pfizer Pyrolytic graphite filaments
US3609992A (en) * 1969-06-21 1971-10-05 Philips Corp Hermetically sealed box for maintaining a semiconductor radiation detector at a very low temperature
US3969754A (en) * 1973-10-22 1976-07-13 Hitachi, Ltd. Semiconductor device having supporting electrode composite structure of metal containing fibers
US4161747A (en) * 1978-02-24 1979-07-17 Nasa Shock isolator for operating a diode laser on a closed-cycle refrigerator
US4414142A (en) * 1980-04-18 1983-11-08 Vogel F Lincoln Organic matrix composites reinforced with intercalated graphite
US4470063A (en) * 1980-11-19 1984-09-04 Hitachi, Ltd. Copper matrix electrode having carbon fibers therein
US4482912A (en) * 1981-02-06 1984-11-13 Hitachi, Ltd. Stacked structure having matrix-fibered composite layers and a metal layer
US4435375A (en) * 1981-03-27 1984-03-06 Shohei Tamura Method for producing a carbon filament and derivatives thereof
US4424145A (en) * 1981-06-22 1984-01-03 Union Carbide Corporation Calcium intercalated boronated carbon fiber
US4415025A (en) * 1981-08-10 1983-11-15 International Business Machines Corporation Thermal conduction element for semiconductor devices
US4485429A (en) * 1982-06-09 1984-11-27 Sperry Corporation Apparatus for cooling integrated circuit chips
US4630174A (en) * 1983-10-31 1986-12-16 Kaufman Lance R Circuit package with external circuit board and connection
US4591659A (en) * 1983-12-22 1986-05-27 Trw Inc. Multilayer printed circuit board structure
US4933804A (en) * 1984-01-19 1990-06-12 The Rank Organisation Plc Interference suppression for semi-conducting switching devices
US4816289A (en) * 1984-04-25 1989-03-28 Asahi Kasei Kogyo Kabushiki Kaisha Process for production of a carbon filament
US5014161A (en) * 1985-07-22 1991-05-07 Digital Equipment Corporation System for detachably mounting semiconductors on conductor substrate
US4749514A (en) * 1985-10-12 1988-06-07 Research Development Corp. Of Japan Graphite intercalation compound film and method of preparing the same
US4849858A (en) * 1986-10-20 1989-07-18 Westinghouse Electric Corp. Composite heat transfer means
US4867235A (en) * 1986-10-20 1989-09-19 Westinghouse Electric Corp. Composite heat transfer means
US4985805A (en) * 1986-11-21 1991-01-15 Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. Device for the cooling of optoelectronic components and use of a flange joint used thereof
US4878152A (en) * 1987-06-16 1989-10-31 Thomson-Csf Mounting for printed circuits forming a heat sink with controlled expansion
US5212625A (en) * 1988-12-01 1993-05-18 Akzo Nv Semiconductor module having projecting cooling fin groups
US5424916A (en) * 1989-07-28 1995-06-13 The Charles Stark Draper Laboratory, Inc. Combination conductive and convective heatsink
US5077637A (en) * 1989-09-25 1991-12-31 The Charles Stark Draper Lab., Inc. Solid state directional thermal cable
US4966226A (en) * 1989-12-29 1990-10-30 Digital Equipment Corporation Composite graphite heat pipe apparatus and method
US5316080A (en) * 1990-03-30 1994-05-31 The United States Of America As Represented By The Administrator Of The National Aeronautics & Space Administration Heat transfer device
US5224030A (en) * 1990-03-30 1993-06-29 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Semiconductor cooling apparatus
US5150748A (en) * 1990-06-18 1992-09-29 Mcdonnell Douglas Corporation Advanced survivable radiator
US5428601A (en) * 1990-07-23 1995-06-27 U.S. Philips Corporation Method of operating a communications system, a communications system and a secondary station for use in the system
US5402004A (en) * 1990-08-14 1995-03-28 Texas Instruments Incorporated Heat transfer module for ultra high density and silicon on silicon packaging applications
US5111359A (en) * 1991-04-17 1992-05-05 E-Systems Inc. Heat transfer device and method
US5287248A (en) * 1991-04-17 1994-02-15 E-Systems, Inc. Metal matrix composite heat transfer device and method
US5830326A (en) * 1991-10-31 1998-11-03 Nec Corporation Graphite filaments having tubular structure and method of forming the same
US5260124A (en) * 1991-11-25 1993-11-09 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Intercalated hybrid graphite fiber composite
US5608267A (en) * 1992-09-17 1997-03-04 Olin Corporation Molded plastic semiconductor package including heat spreader
US5591312A (en) * 1992-10-09 1997-01-07 William Marsh Rice University Process for making fullerene fibers
US5323294A (en) * 1993-03-31 1994-06-21 Unisys Corporation Liquid metal heat conducting member and integrated circuit package incorporating same
US5389400A (en) * 1993-04-07 1995-02-14 Applied Sciences, Inc. Method for making a diamond/carbon/carbon composite useful as an integral dielectric heat sink
US5604037A (en) * 1993-04-07 1997-02-18 Applied Sciences, Inc. Diamond/carbon/carbon composite useful as an integral dielectric heat sink
US5424054A (en) * 1993-05-21 1995-06-13 International Business Machines Corporation Carbon fibers and method for their production
US6197859B1 (en) * 1993-06-14 2001-03-06 The Bergquist Company Thermally conductive interface pads for electronic devices
US5520976A (en) * 1993-06-30 1996-05-28 Simmonds Precision Products Inc. Composite enclosure for electronic hardware
US5523260A (en) * 1993-08-02 1996-06-04 Motorola, Inc. Method for heatsinking a controlled collapse chip connection device
US5542471A (en) * 1993-11-16 1996-08-06 Loral Vought System Corporation Heat transfer element having the thermally conductive fibers
US5494753A (en) * 1994-06-20 1996-02-27 General Electric Company Articles having thermal conductors of graphite
US5698175A (en) * 1994-07-05 1997-12-16 Nec Corporation Process for purifying, uncapping and chemically modifying carbon nanotubes
US5566752A (en) * 1994-10-20 1996-10-22 Lockheed Fort Worth Company High heat density transfer device
US6063243A (en) * 1995-02-14 2000-05-16 The Regents Of The Univeristy Of California Method for making nanotubes and nanoparticles
US5814290A (en) * 1995-07-24 1998-09-29 Hyperion Catalysis International Silicon nitride nanowhiskers and method of making same
US6054198A (en) * 1996-04-29 2000-04-25 Parker-Hannifin Corporation Conformal thermal interface material for electronic components
US5849130A (en) * 1996-07-10 1998-12-15 Browne; James M. Method of making and using thermally conductive joining film
US5805424A (en) * 1996-09-24 1998-09-08 Texas Instruments Incorporated Microelectronic assemblies including Z-axis conductive films
US6119573A (en) * 1997-01-27 2000-09-19 Raytheon Company Carbon fiber flocking for thermal management of compact missile electronics
US5753088A (en) * 1997-02-18 1998-05-19 General Motors Corporation Method for making carbon nanotubes
US6318954B1 (en) * 1997-03-19 2001-11-20 Jagenberg Papiertechnik Gmbh Device for stacking sheets, in particular sheet-fed paper or cardboard sheets delivered onto pallets
US6303094B1 (en) * 1997-03-21 2001-10-16 Japan Fine Ceramics Center Process for producing carbon nanotubes, process for producing carbon nanotube film, and structure provided with carbon nanotube film
US6156256A (en) * 1998-05-13 2000-12-05 Applied Sciences, Inc. Plasma catalysis of carbon nanofibers
US20030203139A1 (en) * 1998-06-19 2003-10-30 Zhifeng Ren Free-standing and aligned carbon nanotubes and synthesis thereof
US6713151B1 (en) * 1998-06-24 2004-03-30 Honeywell International Inc. Compliant fibrous thermal interface
US6617199B2 (en) * 1998-06-24 2003-09-09 Honeywell International Inc. Electronic device having fibrous interface
US6676796B2 (en) * 1998-06-24 2004-01-13 Honeywell International Inc. Transferrable compliant fibrous thermal interface
US6436506B1 (en) * 1998-06-24 2002-08-20 Honeywell International Inc. Transferrable compliant fibrous thermal interface
US6143445A (en) * 1998-08-07 2000-11-07 Ferment; George R. Composite electrodes containing chopped conductive fibers
US6177213B1 (en) * 1998-08-17 2001-01-23 Energy Conversion Devices, Inc. Composite positive electrode material and method for making same
US6183854B1 (en) * 1999-01-22 2001-02-06 West Virginia University Method of making a reinforced carbon foam material and related product
US7132161B2 (en) * 1999-06-14 2006-11-07 Energy Science Laboratories, Inc. Fiber adhesive material
US6913075B1 (en) * 1999-06-14 2005-07-05 Energy Science Laboratories, Inc. Dendritic fiber material
US7144624B2 (en) * 1999-06-14 2006-12-05 Energy Science Laboratories, Inc. Dendritic fiber material
US6361861B2 (en) * 1999-06-14 2002-03-26 Battelle Memorial Institute Carbon nanotubes on a substrate
US6256996B1 (en) * 1999-12-09 2001-07-10 International Business Machines Corporation Nanoscopic thermoelectric coolers
US6737160B1 (en) * 1999-12-20 2004-05-18 The Regents Of The University Of California Adhesive microstructure and method of forming same
US6542371B1 (en) * 2000-11-02 2003-04-01 Intel Corporation High thermal conductivity heat transfer pad
US6835453B2 (en) * 2001-01-22 2004-12-28 Parker-Hannifin Corporation Clean release, phase change thermal interface
US6965513B2 (en) * 2001-12-20 2005-11-15 Intel Corporation Carbon nanotube thermal interface structures
US20030124312A1 (en) * 2002-01-02 2003-07-03 Kellar Autumn Adhesive microstructure and method of forming same
US20030203188A1 (en) * 2002-02-06 2003-10-30 H. Bunyan Michael Thermal management materials
US6946190B2 (en) * 2002-02-06 2005-09-20 Parker-Hannifin Corporation Thermal management materials
US20030152764A1 (en) * 2002-02-06 2003-08-14 Bunyan Michael H. Thermal management materials having a phase change dispersion
US6872439B2 (en) * 2002-05-13 2005-03-29 The Regents Of The University Of California Adhesive microstructure and method of forming same
US20030208888A1 (en) * 2002-05-13 2003-11-13 Fearing Ronald S. Adhesive microstructure and method of forming same
US20040081843A1 (en) * 2002-10-29 2004-04-29 Bunyan Michael H. High temperature stable thermal interface material
US6956739B2 (en) * 2002-10-29 2005-10-18 Parker-Hannifin Corporation High temperature stable thermal interface material
US20060216599A1 (en) * 2004-03-23 2006-09-28 Boden David P Cureless battery paste and method for producing battery plates
US20050255304A1 (en) * 2004-05-14 2005-11-17 Damon Brink Aligned nanostructure thermal interface material
US20060234056A1 (en) * 2005-04-14 2006-10-19 Tsinghua University Thermal interface material and method for making the same
US20060231970A1 (en) * 2005-04-14 2006-10-19 Tsinghua Unversity Method for manufacturing a thermal interface material

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040009353A1 (en) * 1999-06-14 2004-01-15 Knowles Timothy R. PCM/aligned fiber composite thermal interface
US20050181629A1 (en) * 2003-09-08 2005-08-18 Anand Jagota Fibrillar microstructure and processes for the production thereof
US7479318B2 (en) * 2003-09-08 2009-01-20 E.I. Du Pont De Nemours And Company Fibrillar microstructure and processes for the production thereof
US20060068195A1 (en) * 2004-05-19 2006-03-30 Arun Majumdar Electrically and thermally conductive carbon nanotube or nanofiber array dry adhesive
US20080292840A1 (en) * 2004-05-19 2008-11-27 The Regents Of The University Of California Electrically and thermally conductive carbon nanotube or nanofiber array dry adhesive
US20090098671A1 (en) * 2004-09-10 2009-04-16 Dong-Wook Kim Nanotube assembly including protective layer and method for making the same
US20120276327A1 (en) * 2006-10-17 2012-11-01 Purdue Research Foundation Electrothermal interface material enhancer
US8524092B2 (en) 2006-12-14 2013-09-03 Carnegie Mellon University Dry adhesives and methods for making dry adhesives
US10774246B2 (en) 2006-12-14 2020-09-15 Carnegie Mellon University Dry adhesives and methods for making dry adhesives
US8142700B2 (en) 2006-12-14 2012-03-27 Carnegie Mellon University Dry adhesives and methods for making dry adhesives
US20100021647A1 (en) * 2006-12-14 2010-01-28 Carnegie Mellon University Dry adhesives and methods for making dry adhesives
US20100136281A1 (en) * 2006-12-14 2010-06-03 Carnegie Mellon University Dry adhesives and methods for making dry adhesives
US11577286B2 (en) 2007-09-17 2023-02-14 Bruker Nano, Inc. Debris removal in high aspect structures
US11391664B2 (en) 2007-09-17 2022-07-19 Bruker Nano, Inc. Debris removal from high aspect structures
US11040379B2 (en) * 2007-09-17 2021-06-22 Bruker Nano, Inc. Debris removal in high aspect structures
US20090233058A1 (en) * 2008-02-29 2009-09-17 Kenji Hata Carbon nanotube structure and method for producing the same
US20110104430A1 (en) * 2008-03-17 2011-05-05 Avery Dennison Corporation Functional Micro- and/or Nano-Structure Bearing Constructions and/or Methods for Fabricating Same
US9061892B2 (en) 2008-03-17 2015-06-23 Avery Dennison Corporation Functional micro- and/or nano-structure bearing constructions and/or methods for fabricating same
US10065209B2 (en) 2008-03-17 2018-09-04 Avery Dennison Corporation Functional micro- and/or nano-structure bearing constructions and/or methods for fabricating same
US9120953B2 (en) 2008-09-18 2015-09-01 Carnegie Mellon University Methods of forming dry adhesive structures
US8424474B2 (en) 2009-06-19 2013-04-23 Under Armour, Inc. Nanoadhesion structures for sporting gear
US10966469B2 (en) 2009-06-19 2021-04-06 Under Armour, Inc. Nanoadhesion structures for sporting gear
US20100319111A1 (en) * 2009-06-19 2010-12-23 Under Armour, Inc. Nanoadhesion structures for sporting gear
US11339469B2 (en) 2016-01-13 2022-05-24 Applied Materials, Inc. Vacuum processing system with holding arrangement
CN108474109A (en) * 2016-01-13 2018-08-31 应用材料公司 Method for keeping the holding arrangement of substrate, the method and release substrate of the carrier for being used to support substrate, vacuum flush system, holding substrate
US11814721B2 (en) 2016-01-13 2023-11-14 Applied Materials, Inc. Method for holding and releasing a substrate
JP2018172589A (en) * 2017-03-31 2018-11-08 日本ゼオン株式会社 Bonding method
CN110634821A (en) * 2018-06-22 2019-12-31 Zf主动安全和电子美国有限责任公司 Thermal interface for electronic devices
US10418306B1 (en) * 2018-06-22 2019-09-17 Trw Automotive U.S. Llc Thermal interface for electronics
US11964310B2 (en) 2023-01-06 2024-04-23 Bruker Nano, Inc. Debris removal from high aspect structures

Also Published As

Publication number Publication date
US20040071870A1 (en) 2004-04-15
US7132161B2 (en) 2006-11-07

Similar Documents

Publication Publication Date Title
US7132161B2 (en) Fiber adhesive material
US7144624B2 (en) Dendritic fiber material
US20040009353A1 (en) PCM/aligned fiber composite thermal interface
US8389119B2 (en) Composite thermal interface material including aligned nanofiber with low melting temperature binder
AU2009203053B2 (en) Interface-infused nanotube interconnect
US8093715B2 (en) Enhancement of thermal interface conductivities with carbon nanotube arrays
US7416019B2 (en) Thermal interface and switch using carbon nanotube arrays
US7776445B2 (en) Graphene-diamond hybrid material and method for preparing same using chemical vapor deposition
US20120107597A1 (en) Embedded arrays of vertically aligned carbon nanotube carpets and methods for making them
JP5628312B2 (en) Nanotube thermal interface structure
US20090246507A1 (en) Systems and methods for fabrication and transfer of carbon nanotubes
US9562284B2 (en) Materials and methods for thermal and electrical conductivity
US20070116626A1 (en) Methods for forming carbon nanotube thermal pads
US20060258054A1 (en) Method for producing free-standing carbon nanotube thermal pads
Hu et al. Fabrication and characterization of vertically aligned carbon nanotubes on silicon substrates using porous alumina nanotemplates
Yu et al. Patterned carbon nanotube field emitter using the regular array of an anodic aluminium oxide template
WO2013084580A1 (en) Carbon nanotube assembly and viscoelastic body using same
JP3417869B2 (en) Method of forming carbon bonded body
US8808857B1 (en) Carbon nanotube array interface material and methods
JP7105234B2 (en) Nanofiber thermal interface materials
Zhu et al. In-situ opening aligned carbon nanotubes and applications for device assembly and field emission
Chen et al. Growth of carbon nanotubes at low powers by impedance-matched microwave plasma enhanced chemical vapor deposition method
TWI295317B (en) Method for making thermal interface material
Wu et al. Growth and characteristics of vertically-aligned carbon nanotubes by thermal CVD on various Si-based substrates for micro-DMFC
Zhu et al. Well-Aligned In-situ Formed Open-End Carbon Nanotube for Device and Assembly Applications

Legal Events

Date Code Title Description
STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION