WO2011104370A1 - Klebstoff mit anisotroper elektrischer leitfähigkeit sowie verfahren zu dessen herstellung und verwendung - Google Patents
Klebstoff mit anisotroper elektrischer leitfähigkeit sowie verfahren zu dessen herstellung und verwendung Download PDFInfo
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- WO2011104370A1 WO2011104370A1 PCT/EP2011/052862 EP2011052862W WO2011104370A1 WO 2011104370 A1 WO2011104370 A1 WO 2011104370A1 EP 2011052862 W EP2011052862 W EP 2011052862W WO 2011104370 A1 WO2011104370 A1 WO 2011104370A1
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- adhesive
- macrostructures
- matrix
- carbon nanotubes
- joining surface
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/50—Testing of electric apparatus, lines, cables or components for short-circuits, continuity, leakage current or incorrect line connections
- G01R31/66—Testing of connections, e.g. of plugs or non-disconnectable joints
- G01R31/67—Testing the correctness of wire connections in electric apparatus or circuits
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
- H01R4/04—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation using electrically conductive adhesives
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- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S977/00—Nanotechnology
- Y10S977/70—Nanostructure
- Y10S977/734—Fullerenes, i.e. graphene-based structures, such as nanohorns, nanococoons, nanoscrolls or fullerene-like structures, e.g. WS2 or MoS2 chalcogenide nanotubes, planar C3N4, etc.
- Y10S977/742—Carbon nanotubes, CNTs
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- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
Definitions
- the invention relates to an electrically conductive adhesive comprising an adhesively active, curable and electrically non-conductive matrix material and a distributed in the matrix material phase of electrically conductive carbon nanotubes.
- Another aspect of the invention is a method for producing such an electrically conductive adhesive and a method for electrically conductive bonding of two components as well as for checking the quality of an adhesive bond formed in this way.
- Electrically conductive adhesives are used in a variety of applications. Such an application is, for example, the bonding of two printed circuit boards on which a plurality of individual conductive structures are respectively formed and these conductive structures are to be brought into electrical contact with one another via the adhesive gap. Another application is the bonding of electrical components on a printed circuit board and the case formed electrical connection between electrical contact points on the device with electrical contact points on the circuit board.
- JP 2001 31 66 55 A discloses an electrically conductive adhesive and its production method.
- This adhesive contains carbon powder, a binder resin and water and is in the form of a paste.
- a disadvantage of this adhesive is its low ability to wet large areas with a thin layer, to enclose small structures or to penetrate into small structures without causing air bubbles and the need to use a high proportion of carbon powder as an aggregate additive to an electrical To provide conductivity with a sufficiently low resistance across the adhesive layer for safe operation of electrical circuits.
- a further disadvantage of this previously known adhesive is that, for a discrete resolution of a plurality of electrical contact points within the adhesive gap and their electrical isolation, time-sequential process steps in the separate production of the individual contact points are required, whereby the method on the one hand has to follow a complicated sequence of steps. on the other hand takes a long time to form such a plurality of discrete contact points isolated.
- an anisotropically conductive adhesive which contains finely divided, conductive particles of gold, nickel, gold-plated nickel, silver or gold-coated polystyrene balls in a film in finely divided form.
- the electrical contact is in this case achieved by applying pressure by means of a punch and a heating of the system to a temperature of about 150 to 230 ° C, thereby allowing that electrically conductive structures press into the film and in contact with the particles to step.
- a disadvantage of this type of adhesive film is, on the one hand, that the particles induce a significant mechanical disruptive effect in the total adhesive and cohesive force provided by the adhesive film, which results in the adhesive compound as a whole not being able to absorb high mechanical forces, but moreover In particular in the area of the electrical contacts, a considerable impurity is generated by the particles, which can lead to delaminations and consequently contact interruptions if mechanical influences act on the two components to be connected.
- a further disadvantage of this prior art technology is that the provision of the adhesive in the form of a film with finely divided particles is only suitable for the adhesive bond of substantially planar components and thus the range of use is limited.
- US 2009/001 1232 A1 discloses a dry adhesive in which oriented carbon nanotubes (CNTs) are present. These nanotubes are in a parallel longitudinal orientation in dry form and are applied to surfaces under pressure to connect them.
- CNTs carbon nanotubes
- a disadvantage of this dry material is on the one hand its elaborate Production of the parallel structures of carbon nanotubes, the high costs associated with the carbon nanotubes of great length required for this purpose and the insufficient adhesive effect of the dry adhesive on highly loaded adhesive bonds.
- Another disadvantage is that with this type of dry adhesive in addition to the pronounced directional properties in mechanical terms and in a certain way directed properties are achieved in electrical terms, but no sufficiently reliable electrical circuitry for anisotropy is achievable to discrete contact points in a mutually electrically insulated form electrically connect via the bonding gap.
- DE 10 2005 063 403 A1 discloses an adhesive on an epoxy resin matrix with carbon nanofibers contained therein, which can be used to form an electrically conductive adhesive.
- a disadvantage of this previously known adhesive is, on the one hand, the high percentage of nanofiber material based on carbon, which must be introduced for sufficient electrical connection properties in the matrix material, resulting in a high viscosity and consequent poor processability and wetting properties, on the other hand high costs for the adhesive follow.
- a further disadvantage is that when the electrical properties for contacting over the bonding gap are sufficient, an anisotropic electrical connection with mutually insulated electrical contact points at discrete intervals with the adhesive material is not achievable.
- the invention is compared to this prior art, the object to provide an adhesive, on the one hand enables a cost-effective production of the adhesive connection, on the other hand can form a reliable electrical contact between electrical contact points of two components in a reliable manufacturing technology, but at the same time a high spatial Resolution of individual, isolated from each other electrical contact points allows.
- Another object of the invention is to provide an adhesive which, in addition to these electrical requirements Contacting at discrete points or the isolation of these discrete points from each other also achieved a mechanically reliable adhesive bond.
- the carbon nanotubes are present in a plurality of individual macrostructures, each macrostructure consists of a multiplicity of agglomerated and an electrical contact with each other forming carbon nanotubes and the macrostructures in the matrix material preferably in a concentration below the percolation threshold of the Macrostructures lies within the matrix material.
- a matrix material in particular a monomer, prepolymer or polymer, with electrically conductive carbon nanotubes distributed therein is used as adhesive material, which is characterized in that the carbon nanotubes are not present in a random or deliberate uniform distribution within the matrix material, but instead in one aggregated form exist as a macrostructure and a plurality of such macrostructures are present in the matrix material. It may be advantageous that the macrostructures in the matrix material are present in such a concentration that they are below the percolation threshold.
- the percolation threshold is to be understood here as the state in which elements which are in a liquid phase touch each other to an extent that allows the elements to pass along the elements from one end of the material to the other without stretching in the matrix material in the way to have to integrate.
- a matrix material mixed with electrically conductive elements is therefore isotropically electrically conductive when the elements are present in or above the percolation threshold.
- percolation can be defined for both individual elements, such as carbon nanotubes, and macro-elements composed of multiple individual elements, such as multiple carbon nanotube macrostructures.
- the macrostructures for anisotropically conductive adhesives are below the percolation threshold in the matrix material, ie the macrostructures have no tendency and no sufficient volume fraction to accumulate on each other and thus form larger coherent structures bridging greater distances without external influence.
- the electrically conductive adhesive according to the invention is distinguished by a multiplicity of carbon nanotube agglomerates which form a conductive structure.
- These agglomerates can be adjusted specifically in terms of their shape and in terms of their dimensions in the manufacturing process of the adhesive according to the invention or during the bonding process with the adhesive according to the invention.
- two successive shears of the adhesive spherical shapes of the agglomerates can be adjusted when the shear directions of these shears are at right angles to each other. The sharper the angle between the two shearing directions, the more the shape moves away from the spherical shape and approaches an elongated shape.
- a circular shear direction agglomerates can be produced with different shapes.
- the size of the agglomerates can be influenced, for example, by the size of the shearing gap in which the adhesive is subjected to shear.
- These electrically conductive macrostructures are randomly distributed in an electrically non-conductive matrix material and do not tend to agglomerate with each other.
- the adhesive provided in this way makes it possible to form a local electrical connection between them by selectively using the macrostructures between two contacts to be electrically connected. Due to the compact dimensioning of the macrostructures in this case a high spatial resolution of the electrical contacts is achieved, whereby it is possible to form with the electrically conductive adhesive very small discrete distances between two electrical connections to be electrically insulated from each other by the adhesive.
- this makes it possible, with the aid of the matrix material, on the one hand, to provide a region between the macrostructures which is free from electrically conductive carbon nanotubes, which ensures reliable electrical insulation and, moreover, a provides high adhesive and cohesive force transfer between the two components to be joined, whereby a mechanically reliable adhesive bond can be made.
- the tendency of carbon nanotubes to agglomerate is used specifically for the provision of a specific conductivity.
- the carbon nanotubes are only agglomerated to a certain extent by limiting the concentration of the resulting macrostructures themselves. This prevents the formation of loosely contiguous, fractal structures observed in the prior art which provide conductivity over an indefinable and unpredictable range.
- the adhesive of the invention is therefore characterized by a plurality of separated macro structures with high concentration of carbon nanotubes and intervening matrix areas with greatly depleted carbon nanotube concentration.
- the invention is advantageous in terms of contact geometry, since the contact surfaces often do not form a uniformly smooth surface at the microscopic level, but are characterized by a certain roughness.
- the macronuclei of carbon nanotubes according to the invention provide a connection structure which is conventional in terms of current density is superior by orders of magnitude in conductance.
- the extremely fine and fibrous geometry of the carbon nanotubes is particularly advantageous.
- the carbon nanotubes Due to their flexibility, the carbon nanotubes can cling to the surface contours and settle in the microscopic gaps, which leads to multi-dimensional contacts and to a significantly larger effective contact area. Due to the structure of the macrostructures, a rough surface can get into the macrostructure. protrude, so that the possible contact surface again increases many times.
- the matrix material is usually applied in a liquid form on the adhesive surfaces, but in certain applications, the application in solid form, for example as a film, is advantageous.
- the viscosity and wetting ability of the adhesive which is on the one hand immanent due to the viscosity of the matrix material, and on the other hand due to the size, structure and concentration of the macrostructures therein and furthermore directly influenced by external influences such as temperature, pressure, can preferably be set such that a complete Wetting of the adhesive surfaces is achieved and this penetration of the adhesive is achieved in small structures of the components to be bonded. It is intended that the adhesive for the adhesive state can be transferred to a cured state.
- the curing can be carried out in principle by a chemical reaction or a physical setting, moreover, a reactive hot melt adhesive can be used.
- curable is meant a property of the adhesive to transition to a state in which mechanical stresses can be transferred through the adhesive.
- the adhesive may be elastic or substantially rigid in this.
- the electrically conductive adhesive according to the invention is characterized in that macrostructures are contained therein, which in turn are composed of a plurality of carbon nanotubes and interspersed by the matrix material.
- macrostructures are contained therein, which in turn are composed of a plurality of carbon nanotubes and interspersed by the matrix material.
- an interface problem is avoided by the macrostructures in the adhesive, since the macrostructures are present in an ideally integrated manner within the matrix material and influence the mechanical force flows only in a small way, in particular as fiber reinforcement. Delaminations or mechanical failure due to the macrostructures can therefore not occur in the adhesive according to the invention or only to a much lesser extent than in the case of previously known adhesives.
- the electrically conductive adhesive has an advantageous concentration in a specific concentration.
- An anisotropic electrical conductivity capability can be used to electrically connect discreetly spaced electrical contact points in isolated form from each other to other correspondingly discretely spaced electrical contact points on a second adhesive surface.
- the adhesive according to the invention is preferably composed of the matrix material and the macrostructures with carbon nanotubes contained therein and preferably a surface coating of the macrostructures or the carbon nanotubes is dispensed with in order thus to achieve both the mechanical properties and the electrical properties Properties to optimally use the potential of the materials used.
- the macrostructures are present in a substantially spherical geometry and that the values of height, width and length of a macrostructure in any of the values deviate by more than 50% from one of the other values.
- an anisotropic conductivity is promoted in which there is no conductivity in the direction of the plane of the adherend, but conductivity is provided orthogonally therethrough.
- the macrostructures deviate from each other in their geometrical dimensions as little as possible, ie the standard deviation of the measured length, width and / or height or the overall size characterize-
- the values, such as diameter, cross-sectional area or total volume of a macrostructure are as small as possible over a large number of measured macrostructures, whereby a monomodal size distribution of the macrostructures with a pronounced maximum of a certain macrostructure size and only a small proportion of macrostructures with smaller or larger size is available.
- Such a distribution enables a reliable bonding and electrical contacting with a low reject rate by the adhesive according to the invention, in that the electrical contacting can be produced in a reproducible manner with predetermined process parameters by the defined macrostructures. If, for example, a limited anisotropy in the adhesive surface is intended, for example to connect pairs arranged, short-spaced contacts, but not to connect these pairs with each other, a multimodal distribution may be desired.
- the adhesive according to the invention is used, for example, for a typical adhesive gap thickness of 10 to 70 ⁇ m, in which case the adhesive gap thickness is understood to mean the average distance between the two bonded electrically contacting surfaces in the fully bonded state.
- the macrostructures can be present, for example, in a concentration of up to 40% by volume, preferably 10-20% by volume.
- Each macrostructure has a maximum dimension of 1 to 3 times the gluing gap thickness, preferably 1, 1 to 2 times the gluing gap thickness. In special cases, the maximum dimension may also be below the adhesive gap thickness, for example in the range of 0.5 to 0.9 times the adhesive gap thickness. In these special cases, a special measure is required in order to bring about agglomeration of two or a few macrostructures in the region of the electrically contacting surfaces, despite their concentration below the percolation threshold.
- the macrostructures are in a form obtained by shearing a liquid having carbon nanotubes distributed therein, in particular at least by a first shearing of the liquid in a first direction followed by a second shearing in a second direction, which differs from the one of the first direction is different, in particular non-parallel lel or antiparallel to the first direction.
- the invention is based on the finding that the agglomeration of carbon nanotubes into macrostructures can lead to an advantageous embodiment and better properties of an electrically conductive adhesive. In this case, this agglomeration is generated in an advantageous manner by shearing in at least one direction.
- such a shear can create a macrostructure that has a pronounced longitudinal orientation transverse to the shear direction.
- the macrostructure is generated by an additional second shear, which runs in a different direction than the first shear.
- the macrostructures produced in the first shearing can either be transformed into macrostructures or further agglomerated, which have a geometry which deviates from the elongated structure and points more towards the ideal spherical shape.
- the shear can be accomplished by placing the matrix material having carbon nanotubes therein between two surfaces by first moving these surfaces in a first direction relative to each other and then moving them in a second direction relative to each other.
- the adhesive according to the invention is distinguished by elongated macrostructures in the case of one-dimensional shearing and, in the case of two-dimensional shearing, by shorter macrostructures approximating the spherical shape.
- the carbon nanotubes be present in the matrix material in a concentration above the percolation threshold of the carbon nanotubes in the matrix material.
- the carbon nanotubes can be present in the matrix material both below and above or exactly in the percolation threshold and the agglomeration can be achieved by a corresponding mechanical or otherwise induced effect.
- a particularly advantageous To achieve a low electrical conductivity effect it is particularly advantageous to introduce the carbon nanotubes in such a concentration that, taken in isolation, they would already provide an isotropic conductivity of the adhesive, which is then modified to anisotropic conductivity by the formation of the macrostructures.
- the carbon nanotubes can thereby tend to agglomeration without external influences and this agglomeration can optionally be controlled by additional foreign influences, for example mechanical shearing in one or two directions, as explained above, in such a way that advantageously shaped macrostructures are formed by this agglomeration.
- an electrically conductive adhesive is achieved, which has no tendency to agglomeration of the macrostructures without external influence, but overall macrostructures in such a concentration and within the macrostructures carbon nanotubes in such an amount and packing density, that on the one hand, the electrical conductivity through the adhesive and on the other hand, the adhesive and cohesive action of the adhesive is ideally achieved.
- the adhesive has basically no electrical conductivity without macrostructures formed, it becomes anisotropically electrically conductive due to the formation of the macrostructures.
- a macrostructure at least one substance is contained, which is functionally effective for connection to a joint surface area, in particular a magnetic substance.
- anisotropic electrical connection can be achieved solely by providing the macrostructures in their size and defined concentration.
- the adhesive may be processed such that it achieves sufficient electrical connection of defined electrical conductor structures to two components based on a statistical distribution of the macrostructures in the adhesive.
- the joining surface region can also be processed mechanically, chemically or physically in a specific manner in order to bring about or promote this targeted attachment of the macrostructures.
- a magnetic function between the macrostructure and the joint surface area to be electrically connected can be used, but other effects, such as, for example, chemical affinity, electrostatic effects or the like, can also be applied in the form of a functional element in the macrostructures.
- Another aspect of the invention is a method of making an electrically conductive adhesive comprising the steps of:
- an electrically conductive adhesive is produced, which consists of at least two starting materials in two phases.
- a first phase is an adhesive matrix, which can be transferred from a usually liquid state by curing in a cured state and then in this cured state exerts adhesive forces to the joining surfaces and internally transfer cohesive forces, which is required for the connection of the two components to be joined are.
- the second phase consists of carbon nanotubes agglomerated into macrostructures, which in this adhesive matrix in such a concentration in distributed form be present that a percolation of these macrostructures does not occur without external influence.
- the macrostructures can in principle be produced in a production aid matrix which is chemically different from, or chemically coincident with, the adhesive matrix, for example, but otherwise differently concentrated or overall matching.
- the production assist matrix preferably has a lower viscosity than the adhesive matrix to thereby promote the formation of macrostructures from the carbon nanotubes. After the macrostructures are formed in the production assist matrix, they can be incorporated into the adhesive matrix and finely dispersed therein to thereby produce the ideal processing state of the adhesive to be produced.
- the macrostructures can already be formed in the adhesive matrix before the adhesive is introduced into the adhesive gap or can be formed only after this introduction and then during the joining process.
- the method can be developed by carrying out the following steps between steps c and d:
- Extracting the macrostructures from the production assist matrix preferably by distillation, and
- the adhesive matrix in particular has a different chemical composition from the production aid matrix.
- the macrostructures together with the production aid matrix can be introduced into the adhesive matrix and the production aid matrix thereby either becomes part of the adhesive or is removed from the adhesive in a later process step, it is advantageously provided according to this development that the macrostructures are isolated from the production aid matrix after being made in it.
- This isolation can be carried out in particular by distillation, in which the production aid matrix is converted by heating in a gaseous state and thereby the macrostructures remain in an isolated solid form.
- This extraction of the macrostructures from the production aid matrix is particularly advantageous if the production aid matrix and adhesive matrix are of a different chemical composition, but at least of different concentration and thus viscosity. This opens up the possibility of selecting a production auxiliary matrix that is ideally suited for the process step of producing the macrostructures and then introducing the macrostructures produced therein into an adhesive matrix that is ideally suited for the desired adhesive effect.
- the production aid matrix is chemically consistent with the adhesive matrix and after step c, the concentration of the macrostructures is optionally increased by distillation or reduced by the addition of adhesive matrix.
- the concentration of the macrostructures is optionally increased by distillation or reduced by the addition of adhesive matrix.
- this process variant which is technically simpler and more economical than the previously described variant with extraction of the macrostructures from the production aid matrix, is already used as a production aid matrix suitable for the subsequent adhesive effect adhesive matrix and these only optionally with regard to their viscosity by dilution or concentration to one for the Education of macrostructures brought ideal value.
- an ideal viscosity for the processing of the adhesive may then be set by either distillation with consequent removal of adhesive matrix portions or dilution by addition of adhesive matrix portions.
- the carbon nanotubes in step c. by introducing a shear into the production aid matrix, in particular of temporally successive shear in two different directions, are agglomerated to the macrostructures, preferably with the simultaneous introduction of compressive forces. With this training, a particularly efficient production of the macrostructures is achieved.
- the agglomeration of the carbon nanotubes in step c. is supported by a reduction in viscosity, in particular by heating, the production assist matrix.
- the carbon nanotubes in step b. is introduced in a concentration in the production aid matrix, which is above the Perkolationsschwelle the carbon nanotubes in the production aid matrix.
- the carbon nanotubes have to be introduced into the production aid matrix in such a concentration that agglomeration can either be brought about by external influences or it takes place without such external influences, ie. the concentration is above the percolation threshold of the carbon nanotubes in the production aid matrix.
- the macrostructures themselves may be present below the percolation threshold in the production assistive matrix when made, that is, in the production assisting matrix. There is no agglomeration of the macrostructures to larger structures without external influences.
- Another aspect of the invention is a method for electrically conductive bonding of two components, comprising the steps of: a. Providing an adhesive comprising an adhesive matrix of an adhesive substance and a plurality of carbon nanotubes, Introducing the adhesive onto at least one joining surface of one of the two components to be joined,
- a mechanical connection is effected due to adhesive effects between an adhesive and joining surfaces of two components and cohesive force transmission within the adhesive and at the same time produces an anisotropic electrical connection of electrically conductive joining surface regions.
- an anisotropic electrical connection is here an electrical connection between two typically opposite electrical contact points on the one hand the one and the other
- the anisotropic electrical connection consists of a channeled, outwardly shielded connection of two discreetly outlined contact pads.
- this anisotropic electrical connection is achieved by providing an adhesive with macrostructures of agglomerated carbon nanotubes contained therein by placing this adhesive in an adhesive gap.
- the thickness of the adhesive gap in at least those adhesive gap sections which are provided for an anisotropic electrically conductive connection is less than or equal to a dimension of the macrostructures.
- dimension means a height, width or length of the macrostructures, in particular, provided that the macrostructures approximate the ball shape which is particularly suitable for the inventive design of the method, to understand a diameter of the macrostructures.
- the method according to the invention is based on a mean measured extent, however, in alternative embodiments it is also advantageous to use a lower or upper limit dimension instead of the averaged dimension as a minimum or maximum value of the dimension and to align the thickness of the adhesive gap thereto.
- the joining surfaces are flat and the distance between a first joint surface region on a component and a second joining surface region on the same component, both of which are to be electrically connected to respective opposite joining surface regions on the other component via respective respective adhesive gap sections, greater than one
- the dimension of the macrostructures is larger, in particular, than the largest dimension of the macrostructures, so that the adhesive gap section between the first joining face region and its opposite joining face region on the other component is electrically insulated from the bonding gap section between the second joining face region and its opposite joining face region on the other component.
- a plurality of joining surface regions are electrically connected to one component with correspondingly more joining surface regions on the other component, wherein each individual one of these electrical connections within the adhesive is electrically insulated from the other electrical connections.
- This electrical isolation is achieved by appropriate choice of geometry by the distance between two adjacent joining surface regions on a component is selected to be larger than a dimension, in particular the largest dimension of the macrostructures, thereby preventing a macrostructure, in electrical contact at the one joining surface region rests, extends laterally so far that it also forms an electrical contact with the other joining surface region or arranged thereon, in electrical contact thereto macrostructure.
- the further development can be designed in such a way that the distance between two adjacent joint surface regions of a component to be insulated from one another is greater than the diameter of the macrostructures. It is even further preferred that at least one adhesive gap section has a smaller thickness between two mutually opposite joining surface regions to be electrically connected than an adhesive gap section between opposing joining surface regions between which no electrical connection is to be formed via the adhesive gap.
- the smaller thickness of the adhesive gap is produced between the two mutually opposite joining surface regions to be electrically connected, in that at least one of the two joining surface regions is raised in relation to the joining surface regions surrounding the same joining surface.
- a three-dimensional structure of at least one joining surface region, preferably both joining surface regions is attained by appropriate techniques, in which the joint surface regions to be electrically connected are raised in relation to the joining surface regions, which are not to be electrically connected.
- the joining method according to the invention can be carried out by virtue of the macrostructures having one or more functional elements which bring about or convey an attachment to the joining surface regions to be electrically connected.
- a mandrel structure may be provided which can achieve a Verhakungs Koch in a direction of movement, which is parallel to the joint surface and thereby macrostructures which flow in the course of a rinse of adhesive through the adhesive gap on the electrically connected joining surface attached thereto.
- the targeted attachment of the macrostructures to joining areas to be electrically connected is achieved by mechanical clamping, entanglement, jamming or fastening achieved in another manner, by forming a corresponding structure on the joining area to be electrically connected , which is designed for a corresponding attachment of the macrostructure thereto.
- the hardening of the matrix material takes place by the action of an eddy current on the adhesive present in the adhesive gap.
- the curing of the matrix material in addition to the known curing of one example, chemical curing by a two-component matrix material, photo-induced curing or by reacting a component with the environment, In particular ambient air generated curing also be achieved by eddy current, in particular by the heat generated by eddy current induced curing of the matrix material.
- the corresponding eddy current can be generated in particular by the action of a magnetic field on the adhesive gap.
- a further aspect of the invention is a method for checking the quality of an adhesive bond produced according to the joining method described above, wherein it is provided that a measurement of the electrical resistance between different points of a component or the one and the other component under the influence of a mechanical strain on the joint takes place, the ratio of the electrical resistance, the impedance, or the admittance to strain with predetermined values, in particular values from previous measurements on the same adhesive bonds, values which characterize the ratio or the curve and / or absolute values, which are geometric or electrical properties are compared and closed in a deviation of the ratio beyond a certain tolerance range or the occurrence of discontinuities in the resistance-strain curve on a partial failure of the adhesive bond will be.
- the invention makes use of the fact that the electrical connection formed by the macro-structures of carbon nanotubes changes its electrical resistance across the bonding gap when a mechanical strain is applied to the bonding gap or cracks occur and in a measurement of the electrical resistance over the expansion between the effects in that, upon existing and intact adhesive and cohesive bond across the bond gap, the change in resistance produced by the expansion can be differentiated into a separation produced by a local, partial delamination of a macrostructure from a bonding area or a failure within the adhesive by exceeding the allowable cohesive stress.
- the macrostructures according to the invention exhibit a proportional increase in their electrical resistance under the action of a mechanical expansion. However, if delamination or adhesive breaks occur, they show up, on the one hand, by a sudden increase in resistance characterized by a discontinuity, and, on the other hand, by an increase in the resistance over the strain formed over the sum of such delaminations.
- a specific application of the adhesive according to the invention is the use for electromagnetic or electrostatic shielding.
- it may in particular be provided to select the type of carbon nanotubes, the concentration of the carbon nanotubes in each macrostructure, the concentration of the macrostructures in the matrix, the shape and size of the macrostructure as a function of the wavelength to be shielded or wavelength ranges of an electromagnetic radiation.
- the shape and size of the macrostructures may preferably correspond to the wavelength or to an integer multiple of half the wavelength.
- Fig. 1 is a schematic, sectional side view of a first embodiment of the invention.
- Fig. 2 is a schematic, sectional side view of a second embodiment of the invention.
- Fig. 3 is a schematic representation of the sequence of production of an adhesive according to the invention.
- two components which are to be glued together and form an anisotropic electrical connection via the adhesive gap are arranged such that the joining surface region 11 of a first component 10 is arranged opposite the joining surface region 21 of a second component 20 , Between the two joining surfaces 1 1, 21, an adhesive gap 30 is formed.
- first joint surface 1 1 electrically conductive joining surface areas 1 1 a, b, c are formed.
- These joining surface regions 11a, b, c are confronted with corresponding joining surface regions 21a, b, c, which are formed on the second joining surface 21.
- the joining surface regions 11a-c lie in one plane with the joining surface 11, in the same way the joining surface regions 21a-c lie in one plane with the joining surface 21.
- the distance d between two adjacent joining surface regions 11a-c or 21a-c is greater than the diameter of a macrostructure 40a-c which is arranged in the adhesive gap 30.
- the macrostructures 40a, b, c consist of a multiplicity of agglomerated carbon nanotubes and are agglomerated into a spherical shape with a diameter D2.
- the macrostructures 40a-c are surrounded by an adhesive matrix 41 which in the region between the joining surface regions 11a-c and 21a-c has attached to the joining surfaces 11, 21 with an adhesive force and produces an adhesive bond.
- the adhesive matrix may in particular be an adhesive from the group of chemically reacting adhesives, ie cold or thermosetting polycondensation, polymerization or polyaddition adhesives.
- an epoxy resin is used as the adhesive matrix.
- the macrostructures 40a-c are located in the region of the joining surface regions 11a-c and 21a-c and in this way connect in each case the joining surface regions 11a, 21a and 11b, as well as 11c, 21c.
- the diameter D of the macrostructures is greater than the adhesive gap thickness s and smaller than the distance d. In this way, it is ensured that an electrical contact is achieved via the macrostructures 40a-c by direct attachment to the joining surface regions 11a-c, 21a-c and at the same time there is no electrical connection produced in the adhesive gap longitudinal direction, which originates from a macrostructure 40a an adjacent macrostructure 40b could make electrical connection.
- joining surface regions 1 1 1 1 a - c and 121 a - c can be provided on the joining surfaces 1 1 1, 121, which are raised in relation to past surface portions 1 1 1 'and 121'.
- the adhesive gap between two joining surface regions to be electrically connected to one another is reduced to a small degree when the components 1 10, 120 approach and an electrical connection is achieved by macrostructures 140a-c.
- the macrostructures 140a-c hereby have a dimension which prevents the risk of an undesired electrical cross-connection between adjacent joining surface regions 11a-c on a component 110 or 121a-c on a component 120, even if macrostructures 140d, e in these insulating intermediate regions are arranged in the adhesive matrix. In this way, an overall finer structure of the electrical connection can be achieved.
- a preferred manufacturing method for the adhesive of the present invention is shown.
- a) a number of carbon nanotubes 1 are initially introduced into a production aid matrix 2, and in this case a concentration of the carbon nanotubes 1 in the production aid matrix 2 is reached which is above the percolation threshold.
- the agglomeration of the carbon nanotubes, which then begins without external influence, to form larger agglomerates is controlled by shearing the production aid matrix with the carbon nanotubes distributed therein in such a way that macrostructures of a geometry advantageous for the desired effect of the adhesive arise.
- This shear is introduced by arranging the production aid matrix together with the carbon nanotubes distributed therein between two surfaces 3, 4 b), c) and moving these surfaces in a first direction relative to one another in a first step d) and in a second step e) be moved in a second direction relative to each other.
- the macrostructures 5 thus obtained are now present f) in a concentration in the production aid matrix 2 which is below the percolation threshold, ie the macrostructures 5 are dispersed in the process control matrix 2, are not electrically interconnected, and do not tend to agglomerate to form larger macrostructures.
- the macrostructures 5 thus formed are then extracted therefrom by distillation of the production aid matrix 2 and are now present in a pourable form.
- the macrostructures are then introduced h) into an adhesive matrix 6 in turn in such a concentration that they are below the percolation threshold and consequently can assume a finely divided dispersion within the adhesive matrix.
- the macrostructures are introduced into only one of two components of the adhesive matrix or introduced into both components of the adhesive matrix and then the two components at a time which is short before the intended processing, are mixed together to thereby induce a time-delayed chemical reaction that leads to the curing of the adhesive matrix.
- a photo-induced, heat-induced or induced by reaction with ambient air or the like curing of the adhesive matrix is provided, is worked with a one-component adhesive matrix and curing by appropriate action on the adhesive matrix brought about, as soon as this in the bonding gap in the distributed in the desired manner.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP11704803A EP2566926A1 (de) | 2010-02-26 | 2011-02-25 | Klebstoff mit anisotroper elektrischer leitfähigkeit sowie verfahren zu dessen herstellung und verwendung |
CN2011800212847A CN102933676A (zh) | 2010-02-26 | 2011-02-25 | 具有各向异性导电性能的胶粘剂及其制造和使用方法 |
JP2012554359A JP2013520544A (ja) | 2010-02-26 | 2011-02-25 | 異方導電性を持つ接着剤ならびにその製造方法および使用 |
US13/581,300 US20130076371A1 (en) | 2010-02-26 | 2011-02-25 | Adhesive with anisotropic electrical conductivity and methods of producing and using same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102010002447.3 | 2010-02-26 | ||
DE102010002447A DE102010002447A1 (de) | 2010-02-26 | 2010-02-26 | Klebstoff mit anisotroper elektrischer Leitfähigkeit sowie Verfahren zu dessen Herstellung und Verwendung |
Publications (1)
Publication Number | Publication Date |
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WO2011104370A1 true WO2011104370A1 (de) | 2011-09-01 |
Family
ID=44259652
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2011/052862 WO2011104370A1 (de) | 2010-02-26 | 2011-02-25 | Klebstoff mit anisotroper elektrischer leitfähigkeit sowie verfahren zu dessen herstellung und verwendung |
Country Status (6)
Country | Link |
---|---|
US (1) | US20130076371A1 (de) |
EP (1) | EP2566926A1 (de) |
JP (1) | JP2013520544A (de) |
CN (1) | CN102933676A (de) |
DE (1) | DE102010002447A1 (de) |
WO (1) | WO2011104370A1 (de) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1401734B1 (it) * | 2010-06-29 | 2013-08-02 | St Microelectronics Srl | Dispositivo elettronico comprendente uno strato di interfaccia di connessione basato su nanotubi, e procedimento di fabbricazione |
DE102011082425A1 (de) * | 2011-09-09 | 2013-03-14 | Hochschule für Nachhaltige Entwicklung Eberswalde | Vorrichtung und Verfahren zur permanenten Prüfung von Klebeverbindungen |
CN103165211B (zh) * | 2011-12-15 | 2015-09-30 | 清华大学 | 起搏器电极线及起搏器 |
US20170028514A1 (en) * | 2014-04-10 | 2017-02-02 | GM Global Technology Operations LLC | Systems and Methods for Reinforced Adhesive Bonding |
DE102015113123B4 (de) * | 2015-08-10 | 2017-03-16 | Sma Solar Technology Ag | Vorrichtung zur Herstellung einer mehrphasigen elektrischen Verbindung sowie eine Anordnung mit entsprechenden Vorrichtungen |
US10308002B2 (en) * | 2017-05-23 | 2019-06-04 | The Boeing Company | Bondline control adhesive spacer |
CN108878678A (zh) * | 2018-06-14 | 2018-11-23 | 武汉华星光电半导体显示技术有限公司 | 导电胶结构制作方法、导电胶结构及显示面板组件 |
KR102127229B1 (ko) * | 2018-11-27 | 2020-06-29 | 주식회사 아이에스시 | 전기접속용 커넥터 |
CN114235900B (zh) * | 2021-12-22 | 2024-02-27 | 浙江大学 | 太赫兹器件用碳纳米管取向度测量装置及方法 |
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-
2011
- 2011-02-25 WO PCT/EP2011/052862 patent/WO2011104370A1/de active Application Filing
- 2011-02-25 CN CN2011800212847A patent/CN102933676A/zh active Pending
- 2011-02-25 US US13/581,300 patent/US20130076371A1/en not_active Abandoned
- 2011-02-25 EP EP11704803A patent/EP2566926A1/de not_active Withdrawn
- 2011-02-25 JP JP2012554359A patent/JP2013520544A/ja not_active Withdrawn
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EP0748507B1 (de) | 1994-02-28 | 1999-06-16 | Robert Bosch Gmbh | Anisotrop leitender kleber |
JP2001316655A (ja) | 2000-04-28 | 2001-11-16 | Matsushita Electric Ind Co Ltd | 導電性接着剤およびその製造方法 |
WO2005017012A1 (en) * | 2003-08-06 | 2005-02-24 | World Properties, Inc. | Electrically conductive pressure sensitive adhesives, method of manufacture, and use thereof |
DE102005063403A1 (de) | 2005-12-23 | 2007-09-06 | Electrovac Ag | Kleber oder Bondmaterial |
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Also Published As
Publication number | Publication date |
---|---|
US20130076371A1 (en) | 2013-03-28 |
JP2013520544A (ja) | 2013-06-06 |
EP2566926A1 (de) | 2013-03-13 |
CN102933676A (zh) | 2013-02-13 |
DE102010002447A1 (de) | 2011-09-01 |
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