ANISOTROPIC CONDUCTING BODY AND METHOD FOR MANUFACTURE

Abstract

A layer of the mixture that contains polymer and conductive particles is applied over a first surface, when the mixture has a first viscosity that allows the conductive particles to rearrange within the layer. An electric field is applied over the layer, so that a number of the conductive particles are aligned with the field and thereafter the viscosity of the layer is changed to a second, higher viscosity, in order to mechanically stabilise the layer. This leads to a stable layer with enhanced and anisotropic conductivity.

Claims

1-12. (canceled)

13. A method for forming a body comprising a mixture of a matrix and conductive particles having a low aspect ratio, the method comprising: a) providing a mixture comprising a matrix capable of being stabilized and conductive particles; b) aligning the conductive particles into conductive pathways by applying an electric field between alignment electrodes, wherein the electric field is an alternating current field; and c) stabilizing the mixture, wherein the conductive particles are at least one infusible conductive particle, a metallic particle, a metal oxide particle, and a colloidal metal particle.

14. The method in accordance with claim 13, wherein one or more of the alignment electrodes are not in direct contact with the mixture during the aligning.

15. The method in accordance with claim 14, wherein one or more of the alignment electrodes are insulated from the mixture.

16. The method in accordance with claim 13, wherein the alignment electrodes are in-plane, out-of-plane or arbitrary oriented in relation to the body.

17. The method in accordance with claim 13, further comprising: second aligning the conductive particles into the conductive pathways by applying an electric field between the alignment electrodes to repair defective conductive pathways, wherein the electric field applied is in the order of 0.1-20 kV/cm.

18. The method in accordance with claim 13, wherein the matrix is a UV curable polymer.

19. The method in accordance with claim 13, wherein the matrix is an adhesive.

20. The method in accordance with claim 13, wherein a concentration of the conductive particles in the mixture is below a percolation threshold.

21. The method in accordance with claim 13, wherein one or more of the electrodes are in contact with the mixture, and the aligning is interrupted before the conductive pathway has reached through the mixture.

22. A method for forming a body comprising a mixture of a matrix and conductive particles having a low aspect ratio, the method comprising: a) aligning the conductive particles into conductive pathways by applying an electric field between alignment electrodes to the mixture, wherein the electric field is an alternating current field and the alignment electrodes are not in direct contact with the mixture during the aligning; and b) thereafter, stabilizing the mixture, wherein a concentration of the conductive particles in the mixture is below a percolation threshold and wherein the conductive particles are at least one infusible conductive particle, a metallic particle, a metal oxide particle, and a colloidal metal particle.

23. The method in accordance with claim 13, wherein said conductive particles have an aspect ratio ranging from 1-4.

24. The method in accordance with claim 13, wherein said conductive particles have an aspect ratio ranging from 1-5.

25. The method in accordance with claim 13, wherein said conductive particles have an aspect ratio ranging from 1-10.

26. The method in accordance with claim 13, wherein said conductive particles have an aspect ratio ranging from 1-20.

27. The method in accordance with claim 13, wherein said electric field applied is in the order of 0.1-20 kV/cm.

28. The method in accordance with claim 13, wherein said electric field applied is in the order of 0.1-5 kV/cm.

29. The method in accordance with claim 13, wherein said electric field applied is in the order of 0.1-1 kV/cm.

30. The method in accordance with claim 13, wherein said electric field is an alternating filed having a frequency of 1-Hz to 10 kHz.

31. The method in accordance with claim 13, wherein conductive particle is an infusible conductive particle.

32. The method in accordance with claim 13, wherein the infusible conductive particle is a carbon particle selected from the group consisting of spherical carbon black, carbon cones, carbon discs, and a mixture thereof.

33. The method in accordance with claim 13, wherein the conductive particles comprise a member selected from the group consisting of a metallic particle, a metal oxide particle, and a colloidal metal particle.

34. A method for forming a body comprising a mixture of a matrix and conductive particles, the method comprising: a) providing a mixture comprising a matrix capable of being stabilized and conductive particles; b) aligning the conductive particles into conductive pathways by applying an electric field between alignment electrodes, wherein the electric field is an alternating current field; and c) stabilizing the mixture, wherein the conductive particles have an aspect ratio ranging from 1-20.

35. The method in accordance with claim 34, wherein one or more of the alignment electrodes are not in direct contact with the mixture during the aligning.

36. The method in accordance with claim 35, wherein one or more of the alignment electrodes are insulated from the mixture.

37. The method in accordance with claim 34, wherein the alignment electrodes are in-plane, out-of-plane or arbitrary oriented in relation to the body.

38. The method in accordance with claim 34, further comprising: second aligning the conductive particles into the conductive pathways by applying an electric field between the alignment electrodes to repair defective conductive pathways, wherein the electric field applied is in the order of 0.1-20 kV/cm.

39. The method in accordance with claim 34, wherein the matrix is a UV curable polymer.

40. The method in accordance with claim 34, wherein the matrix is an adhesive.

41. The method in accordance with claim 34, wherein a concentration of the conductive particles in the mixture is below a percolation threshold.

42. The method in accordance with claim 34, wherein one or more of the electrodes are in contact with the mixture, and the aligning is interrupted before the conductive pathway has reached through the mixture.

43. A method for forming a body comprising a mixture of a matrix and conductive particles having a low aspect ratio, the method comprising: a) aligning the conductive particles into conductive pathways by applying an electric field between alignment electrodes to the mixture, wherein the electric field is an alternating current field and the alignment electrodes are not in direct contact with the mixture during the aligning; and b) thereafter, stabilizing the mixture, wherein a concentration of the conductive particles in the mixture is below a percolation threshold and wherein the conductive particles have an aspect ratio ranging from 1-20.

44. The method in accordance with claim 34, wherein said conductive particles have an aspect ratio ranging from 1-4.

45. The method in accordance with claim 34, wherein said conductive particles have an aspect ratio ranging from 1-5.

46. The method in accordance with claim 34, wherein said conductive particles have an aspect ratio ranging from 1-10.

47. The method in accordance with claim 34, wherein said electric field applied is in the order of 0.1-20 kV/cm.

48. The method in accordance with claim 34, wherein said electric field applied is in the order of 0.1-5 kV/cm.

49. The method in accordance with claim 34, wherein said electric field applied is in the order of 0.1-1 kV/cm.

50. The method in accordance with claim 34, wherein said electric field is an alternating filed having a frequency of 1-Hz to 10 kHz.

51. The method according to claim 34, wherein the conductive particles are infusible conductive particles.

52. The method according to claim 43, wherein the conductive particles are infusible conductive particles.

Description

LIST OF DRAWINGS

[0037] FIG. 1 show optical micrographs of assemblies of 0.2 vol-% CNC particles dispersed into the adhesive (FIG. 1A) and aligned by the electric field (FIG. 1B) as well as the schematic of the situation (FIG. 1C)

[0038] FIG. 2 plots the dependence of DC conductivity of 0.2 vol-% CNC particles dispersed into the adhesive against the alignment time. The solid line is guide to the eye.

[0039] FIG. 3 shows aligned film with (FIG. 3A-FIG. 3B) and without (FIG. 3C-FIG. 3D) electrical contacts between electrodes

[0040] FIG. 4 shows schematics of the UV curing technique.

[0041] FIG. 5A to FIG. 5F shows optical micrographs showing the healing of a scratch.

[0042] FIG. 6A to FIG. 6C shows aligned and cured conductive particle polymer system in in-plane geometry.

[0043] FIG. 7 shows aligned material with arbitrary alignment geometry and arbitrary electrode shape.

[0044] FIG. 8 shows an optical micrograph of aligned and cured film of nanocone adhesives in in-plane geometry after pyrolysis.

[0045] FIG. 9 illustrates the steps to produce aligned conducting.

[0046] FIG. 10 illustrates dendritic structures maximizing the contact area between conductive item and matrix.

DETAILED DESCRIPTION OF THE INVENTION

[0047] The present invention will be described below with reference to examples and figures. It is to be understood that the present invention is by no means limited to these examples and figures.

[0048] The method can be used in a production line for ESD (electrostatic dissipation or discharge, also known as antistatic) devices, such as films for antistatic packaging or antistatic mats or boards. A thermally conductive film can also be made, that can e.g. be used for lighting reflectors or electronic parts, or a thermally conductive mat that e.g. can be used for form a heat sink. The method comprises the following steps: [0049] i. a matrix is formed from epoxy mixed with conducting particles, according to the present invention [0050] ii. the matrix is applied to a substrate e.g. by spraying, pouring or dipping [0051] iii. an electrical field in the range of 0.01 to 20 kV/cm is applied [0052] iv. the matrix is cured, using e.g. UV light or heat [0053] v. optionally the matrix is reduced, so as to expose the conducting pathways [0054] vi. optionally steps ii to v is repeated to create several layers, e.g. for creating conductive pathways in different directions.

[0055] The method can also be used in a production line for e.g. solar cells or electronics. The method comprises the following steps: [0056] i. epoxy is mixed with conducting particles to form a matrix with conducting particles [0057] ii. the matrix is applied between surfaces that shall be electrically and mechanically connected [0058] iii. an electrical field in the range of 0.01 to 20 kV/cm is applied over the matrix [0059] iv. the matrix is cured, using e.g. UV light or heat

Example 1

[0060] This example concerns the preparation of a mixture of conductive particles and polymer matrix that in this example is an thermally cured polymer adhesive; as well as determination of conductivity as a function of particle load; and how the step-like increase in conductivity with increasing particle load can be explained by formation of conductive paths between particles when the contacts are formed with increased particle fraction.

[0061] This example concerns moreover the preparation of the same mixture when the particle load is low, for example 10 times less than the observed percolation threshold, the limit where the isotropic non-aligned mixture is not conductive; as well as the alignment of this mixture using electric field so that the aligned particles form conductive paths resulting in a conductive material, whose conductivity is directional. The example, moreover, shows change of the viscosity of so obtained material, by curing, so that the alignment and directional conductivity obtained in the alignment step is maintained.

[0062] The employed conductive particles were CB from Alfa Aesar, CNC from n-Tec AS (Norway) and iron oxide (FeO.Fe.sub.2O.sub.3) from Sigma-Aldrich.

[0063] The employed polymer matrix was a two component low viscosity adhesive formed by combining Araldite AY 105-1 (Huntsman Advanced Materials GmbH) with low viscosity epoxy resin with Ren HY 5160 (Vantico AG).

[0064] The conductive particles were mixed in the adhesive by stirring for 30 minutes. Due to the high viscosity of mixture, efficient mixing is possible only up to 20 vol-%. of particles.

[0065] Estimated percolation threshold of these materials are at 2 vol-%. The mixtures are conductive above and insulators below this threshold. The conductivity is due to the conductive particles and the polymer is essentially insulator.

[0066] To illustrate the benefit of alignment, the particle loads of 1/10 of the estimated percolation threshold were used.

[0067] FIG. 1 illustrates, using optical micrographs, the mixing of assemblies of 0.2 vol-% CNC particles dispersed into the example adhesive before (FIG. 1A) and after an electric field alignment and curing (FIG. 1B).

[0068] The scheme shows the applied alignment (out-of-plane) geometry (FIG. 1C). This alignment geometry was used to cover conductive path distances from 10 m to 2 mm. For an out-of-plane alignment 2 mm3 cm wide layer of material is injected between two metal electrodes with spacing of <2 mm.

[0069] Mixture was aligned using an AC source. In this example the alignment procedure 1 kHz AC-field (0.6-4 kV/cm, rms value) was employed for >10 minutes for >1 mm electrode spacing and <10 minutes for <1 mm electrode spacing.

[0070] FIG. 2 shows the conductivity as a function of alignment time illustrating orders of magnitudes conductivity enhancement.

[0071] The curing was performed immediately afterwards at 100 C. for 6 minutes.

[0072] The material remains aligned after curing and conductivity level obtained by alignment is maintained.

Example 2

[0073] This example concerns versatile choice of alignment conditions and illustrates how the present invention can be employed not only with electrodes connected to the orientation material but also with electrodes electrically isolated from the material.

[0074] The procedure was otherwise similar to that in example 1, but instead of having material directly connected to the alignment electrodes, the electrodes were electrically disconnected from the material by an insulating layer, for example by 0.127 mm Kapton foils. Alignment occurred exactly as in Example 1.

[0075] This procedure allows removal of electrodes after alignment and thus freestanding aligned film even in the case where the matrix is adhesive. The alignment also occurs if the electrodes do not touch the material and so the alignment can be performed from the distance. When the material and electrodes are moved, continuous or stepwise, with respect to each others during the alignment, this allows continuous alignment processing. Three possible options for the alignment settings are illustrated in FIG. 3 that shows aligned film with (A-B) and without (C-D) electrical contacts between electrodes (a) and material (b). In the case (A) the aligned film forms permanent connection between the electrodes. In the case (B) the electrodes and material are only loosely joined together and can be moved apart after alignment. In the case (C) there are insulating layers (c) between the material and electrodes and they are easily moved apart after the alignment even in the case where the material is an adhesive. In this case the obtained material is a multilayer consisting of aligned layer (b) and two insulating layers (c) In the case (D) the alignment is carried out from the distance and the mutual location of electrodes and film can be additionally moved during the alignment.

Example 3

[0076] This example concerns the applicability of the alignment method, the use of alignment for particular application of UV-curing. This emphasises the benefit of low particle fraction which makes the material more transparent for UV light for curing.

[0077] The procedure was otherwise similar to that in example 1 or 2 but the thermally cured polymer matrix was replaced by UV-curable Dymax Ultra Light-Weld 3094 adhesive and the curing step was done by the UV-light with the wavelength 300-500 nm.

[0078] FIG. 4 illustrates the alignment of 0.2 vol-% CNC dispersion in out-of-plane geometry. The mixture was formed following the guideline of example 1 (FIG. 4a) but spread on the alignment electrode using RK Print Paint Applicator that uses a moving bird applicator to level the adhesive layer to the predetermined thickness (the idea is schematically illustrated in FIG. 4b). This admixture was aligned following the method outlined in example 2 but the upper electrode was not in contact with the material by use of an insulating layer such as Kapton (FIG. 4c); this allows removal of electrodes after alignment and thus freestanding aligned film even in the case where the matrix is adhesive. After alignment, the upper alignment electrode is removed and aligned admixture cured by UV or blue light. (FIG. 4d). The lower electrode can be optionally removed (FIG. 4e) to form a fully free-standing film.

[0079] FIG. 4 also gives the schematics of UV curing. Conductive particles are dispersed with UV-curable polymer matrix (a). This mixture is spread to form a predetermined layer on the substrate (that acts also as an alignment electrode) using an applicator (b). The material is aligned by electric field using lower electrode and another top-electrode that does not touch the material (c). The upper electrode is removed and the aligned mixture is cured using a light (UV/vis) source, which leads to a semi-freestanding aligned film (d). If required, the lower electrode can be additionally removed leading to a fully free-standing aligned film (e).

Example 4

[0080] This example shows how the present invention can be employed with thermoplastic or thermotropic polymer matrix.

[0081] The procedure was otherwise similar to that in Example 1 or 2 but thermoplastic or thermotropic polymer is used instead of thermoset polymer. In this example alignment was performed when the material was fluid at elevated temperature above the melting point of material. Permanent alignment was achieved when the temperature of fluid matrix with aligned particles was decreased below its glass transition or melting point, which resulted in the stabilization of material.

[0082] The used matrix material was polyfluorene polymer (American Dye Source, with melting point at 180 C.)

Example 5

[0083] This example illustrates how the invention can be employed with polymer matrix and co-solvent.

[0084] The procedure was otherwise similar to that in examples 1, 2, 3, or 4 but the polymer matrix contains solvent. The alignment was performed with the presence of solvent and the solvent was evaporating off after alignment. This can occur with or without curing of thermoset polymer or cooling thermoplastic or thermotropic polymer.

[0085] In the case of thermoset polymer matrix this solvent decreases the viscosity of matrix polymer. This means that the solvent acts as thinner. An example solvent in the thermocured polymer in example 1 is benzylalcohol that is a good solvent for epoxy resin and hardener.

[0086] In the case of thermoplastic or thermotropic polymer matrix in example 1 this solvent makes the mixture fluid already below the melting point of matrix and allows thus alignment at lower temperature. A possible solvent in example 4 is toluene that is a good solvent for polyfluorene.

Example 6

[0087] This example shows the robustness of the procedure and shows how electric field heals macroscopic defects in a conductive particle adhesive mixture.

[0088] The materials and procedure was similar to that in examples 1, 2, 3, 4, or 5, but a macroscopic scratch defect was made by a sharp spike; and the electric field was reapplied. FIG. 5 a-f are optical micrographs showing the healing of the scratch in the case of CNC particle mixture.

Example 7

[0089] This example concerns versatile choice of alignment geometries and illustrates how the invention can be employed not only in the geometry shown in Example 1 but also in (i) thin films and (ii) in in-plane geometry. This example underlines the generality of the method.

[0090] The material was the same and the procedure similar as in Example 1, but instead of out-of-plane alignment geometry, in-plane alignment geometry was used.

[0091] For the in-plane alignment 10 m thick layer was spread either by spin-coating or by plastic spatula over 1 cm1 cm area of metal finger grid where the thickness and width of fingers, respectively, were 50-200 nm and 2-10 The spacing between fingers was 10-100 m.

[0092] FIG. 6 illustrates aligned and cured conductive CNC adhesives in in-plane geometry. FIG. 6a shows an optical micrograph 0.2 vol-% aligned material. Schematic (FIG. 6b) illustrates the alignment setting. In this geometry the alignment occurs typically in seconds or tens of seconds.

[0093] In another version the alignment electrodes were electrically insulated for example by SiO.sub.2 layer following the idea of example 2. Alignment was achieved exactly as without insulating layer.

Example 8

[0094] This example concerns versatile choice of alignment geometries and illustrates how the invention can be employed not only in the out-of-plane and in-plane geometries with flat well defined electrodes but also when the geometry and electrode shape is arbitrary. This example underlines the generality of the method. This also illustrates that the alignment does not require a surface or interface parallel to the emerging aligned pathways.

[0095] The materials were otherwise the same and the procedure similar as in Example 1, 2, 3, 4, or 5 but instead of out-of-plane or in-plane alignment geometry and flat electrodes, arbitrary geometry and arbitrary electrode shape were used. FIG. 7 shows an optical micrograph of aligned material when arbitrary geometry and arbitrary electrode shapes have been used.

Example 9

[0096] This example concerns another feature of the invention, the reduction of matrix after alignment and stabilization. This illustrates how the present invention can be employed in (i) thin films and (ii) in in-plane geometry so that the outcome forms solitary network of aligned pure conductive particles or aligned channels with conductive core and insulating mantle.

[0097] The material was otherwise the same and the procedure similar as in example 1 but all or part of the matrix was removed from the aligned and cured film. In typical procedure the aligned and cured film was heated at 450 C. from 10 minutes to 2 hours. As a result of this procedure step, the thickness of matrix was greatly reduced between the conductive channels and instead of a uniform film with aligned conductive channels embedded into it, a film with distinctive solitary network was achieved (see FIG. 8).

[0098] This procedure can be performed similarly to the materials examples shown in examples 1, 2, 3, 4, or 5. Alternative overall steps are illustrated in FIG. 9, which illustrates the steps to produce aligned conducting film. From left to right: Molecules are dispersed into fluid which can be thermoset, thermoplastic or lyotropic material. Thin film of this dispersion is spread over a substrate. Aligned particle channels forming conductive channels are formed by applying an electric field. Solid uniform film with aligned conductive channels is formed by changing the viscosity. In the case of thermoset matrix this is achieved by curing the matrix polymer. In the case of thermoplastic matrix this is achieved by decreasing the alignment temperature below a phase transition such as melting point or glass transition of the matrix. In the lyotropic case the alignment is performed with the presence of solvent and the solidification obtained by evaporating solvent off. A network of separated aligned wires may be formed by removing part or the entire matrix, for instance by a selective solvent or by pyrolysing a part of the solid matrix.

Example 10

[0099] This example concerns further versatility of the invention, the use of electric field alignment when preparing electrodes with very large contact area dendrimer surface.

[0100] The procedure was otherwise similar to that in examples 1, 2, 3, 4, 5, 7, 8, or 9 but the alignment was terminated before the chains reached from electrode to electrode. FIG. 10 shows so obtained electrodes with dendritic surface.