The invention relates to a composite material having great thermal and electrical conductive performances.
An electrical conductive rubber is formed of an insulative rubber material with electrical conductive powder dispersed therein to have a pressure-sensitive electrical conductive performance, which exhibits insulative property in the absence of an external pressure applied thereon, but exhibits an electrical conductive performance in the presence of an external pressure applied thereon, and thus becomes widely utilized as switches and sensors of electrical and electronic devices. In addition, the electrical conductive rubber has also attracted attention in a rapidly developing robotics field as a material having a haptic function such as an artificial skin.
For instance, Japanese Patent Publication No. 1989-193342 proposes a pressure-sensitive electrical conductive rubber comprising a natural (or synthetic) rubber, an electrical conductive carbon, an insulative mica flake, a bloom agent such as fats and oils, and a surface-dry agent. The rubber is formed to enlarge the gap between the electric resistances in the absence and presence of the external pressure for improving the pressure-sensitive electrical conductive performance. Furthermore, Japanese Patent Publication No. 1993-81924 proposes an electrical conductive rubber composed of a rubber elastic binder and an alloy powder having an average composition formula of AgxM1-x (M means one or more metals selected from Ni, Co, Cu, and Fe. x ranges 0.001 to 0.4) and having an Ag concentration increasing toward its core. The electrical conductive rubber can prevent a time-dependent decrease of the electrical conductive performance, thereby improving its reliability.
However, the electrical conductive rubber is required to enhance thermal characteristic, such as thermal conductivity and the like, in addition to its durability and electrical conductivity when adapted for use in an application where a haptic performance is relied upon. From the viewpoint, it remains necessary to improve the conventional pressure-sensitive electrical conductive material.
In view of the above problem, the present invention has been accomplished and has an object of providing a composite material having great thermal conductivity as well as pressure-sensitive electrical conductivity.
An electrical conductive composite material of the present invention is obtained by curing a mixture of a liquid elastic polymeric material and a magnetic compound fluid containing a magnetic fluid, Ni and Cu in a magnetic field.
In the present invention, the magnetic compound fluid (abbreviated as MCF) possesses an intermediate characteristic between the magnetic fluid (abbreviated as MF) and a magnetorheological fluid (abbreviated as MRF). Generally, the MF has small saturation magnetization, while the MRF is difficult to treat hydrodynamically due to sedimentation of its fluid particles and its powder-like behavior, causing problems in their engineering applications. In view of the above problems, the MCF is a developed functional fluid formed of a metallic material (metallic fine particle) and the MF.
The particularly preferable electrical conductive composite material of the present invention is obtained by curing the mixture of the liquid elastic polymeric material and the MCF with Ni powder and Cu powder dispersed therein in the magnetic field.
Preferably, the MF is a kerosene-based MF for the purpose of forming the electrical conductive composite material.
In addition, it is preferable that the liquid elastic polymeric material is a silicone rubber, especially a silicone-oil rubber for the purpose of forming the electrical conductive composite material.
Additionally, both contents of the Cu powder and the Ni powder are preferably in a range of 14-19 wt % of the electrical conductive composite material.
Furthermore, content of the MF is preferably in a range of 9-26 wt % of the electrical conductive composite material.
The present invention has another object of providing a method of producing the above electrical conductive composite material. Namely, a production method comprises a step of preparing the MCF including the MF, Ni, and Cu, a step of mixing the MCF with the liquid elastic polymeric material, and a step of curing the resultant mixture in the magnetic field.
In the curing step, the mixed material is preferably disposed between permanent magnets facing each other while being kept in a sheet-like form having a thickness of 1 mm or less.
It is particularly preferred that Ni particle and Cu particle respectively have an elongated shape with an average diameter of 3-7 μm and a dendritic shape with an average diameter of 8-10 μm.
Further features and advantages of the present invention will be clearly understood by the following best mode for carrying out the invention and examples.
Hereafter, an electrical conductive composite material of the present invention and a production method thereof will be described in detail.
The electrical conductive composite material of the present invention is obtained by curing a mixture of a liquid elastic polymeric material and a magnetic compound fluid (MCF) containing a magnetic fluid (MF), Ni and Cu, in a magnetic field. Preferably, the electrical conductive composite material of the present invention is obtained by curing the mixture of the liquid elastic polymeric material and the MCF formed of the MF with Ni powder and Cu powder dispersed therein in the magnetic field.
In the present invention, both of Ni and Cu are utilized for the following reasons; Ni is more ferromagnetic than Fe or the like, combination use of Cu is suitable to enhance both thermal and electrical conductivities, and a characteristic structure of cluster is formed by aggregation of Ni and Cu in the electrical conductive composite material cured in the magnetic field, as further mentioned below.
For the purpose of obtaining the MCF, the Ni powder is preferably added as Ni to the MF. It is particularly preferred that a Ni particle has of a non-spherical granular shape (shown in
In addition, the Cu powder is preferably mixed as Cu with the MF for the purpose of obtaining the MCF. Especially, a Cu particle preferably has a dendritic shape (e.g. having an average diameter of 8-10 μm), as shown in
A kerosene-based MF is preferably utilized as the MF forming the MCF, as being compatible with silicone rubber suitable for the liquid elastic polymeric material. The MF may be the kerosene-based MF includes nm-sized (e.g. 10 nm-sized) spherical magnetite particles (Fe3O4) dispersed therein, or an alkylnaphthalene-based MF compatible with the silicone rubber. As explained above, the MF is composed of the magnetite particles and a base liquid, and the magnetite particles can aggregate the Ni particles and the Cu particles to form cluster while the base liquid is possibly trapped in polymers of the rubber provided as the liquid elastic polymeric material described below.
The MCF can be obtained by mixing the Ni powder, the Cu powder, and the MF at a predetermined mixing ratio. The mixing ratio is appropriately determined based on required thermal and electrical conductivity. Preferably, the weight percent ratios of the Cu powder, the Ni powder, and the MF are respectively in ranges of 14-19, 14-19, and 9-26 wt % of the weight of the electrical conductive composite material. Especially, high conductive performance can be achieved when the Cu powder and the Ni powder are added in equal amounts. As an example of manufacturing condition for achieving the best performance, the weight ratio of Ni to MF is preferably 3 to 4.
For the purpose of forming the electrical conductive composite material of the present invention, the elastic polymeric material is preferably the silicone rubber, especially a silicone-oil rubber. The elastic polymeric material may be another rubber material, but the silicone-oil rubber is especially preferable for its high elasticity and stretchability. The weight percentage of the elastic polymeric material is preferably in a range of 36-63 wt % of the electrical conductive composite material. As an example of manufacturing condition for achieving the best performance, the weight ratio of the MF to the elastic polymeric material is preferably 4 to 10. Since the mixture of the MCF and the liquid elastic polymeric material can be compulsorily performed by changes in mixing time and mixing force, viscosity of the liquid elastic polymeric material can be appropriately controlled based on mixing method and the like.
In the present invention, it is particularly essential that the mixture of the MCF and the elastic polymeric material is cured in the magnetic field. In the applied magnetic field, the Cu particles and the Ni particles can be aggregated to form a plurality of primary structures of cluster, i.e., linear structures of cluster respectively having dendritic forms. Then, the plurality of the linear structures of cluster comes in contact with each other to form three-dimensional huge network cluster (secondary cluster) in the electrical conductive composite material in the direction of the applied magnetic field. Since the linear structures of cluster are not to be bonded to each other, when expanded or contracted due to resiliency of the elastic polymeric material, the electrical conductive composite material is assumed to cause the linear structure of cluster to come into contact with different one or ones of linear structure of cluster. The structures of cluster will be now explained in details in the following examples, and can be visually understood with reference to
Although the formation mechanism of the cluster is currently investigated, it can be mainly attributed to the following properties: the Ni particles magnetically attracting to other Ni particles or magnetite particles in the MF for a remanent magnetization of Ni, the dendritic structure of the Cu particle suited to form the network cluster, the projections on the non-spherical surface of the Ni particles highly influenced by the magnetic field, and so on. In the electrical conductive composite material, the network cluster is not randomly, but regularly oriented in the direction of the applied magnetic field, as shown in
In the present invention, the non-conductive silicone-oil rubber utilized as the elastic polymeric material can include the above conductive network cluster, enabling to acquire not only the electrical conductive performance but also greater stretchability than conventional pure silicone-oil rubbers. The conductive silicone-oil rubber can be arranged to shorten an apparent total length of the network cluster formed of metal particles, that is, a “conductive wire” conducting electrons, so as to achieve small electric resistance. In the present invention, the electrical conductive composite material (rubber made of a MCF composite material) can be obtained by curing the mixture of the MCF and the silicone-oil rubber utilized as the elastic polymeric material in the magnetic field. The electrical conductive composite material can be referred to as an MCF electrical conductive rubber.
Next, an explanation is made as to a method of manufacturing the electrical conductive composite material. The production method comprises a step of preparing the MCF by dispersing Ni and Cu in the MF, a step of mixing the MCF with the liquid elastic polymeric material, and a step of curing the resultant mixture in the magnetic field.
In the manufacturing process, it is particularly important that Ni (e.g. the Ni powder) and Cu (e.g. the Cu powder) are sufficiently mixed with the MF to prepare uniform MCF, and then the elastic polymeric material is added to the resultant MCF.
For the purpose of heightening formation density of the cluster, the applied magnetic field in the curing step preferably has a strength of 5 kGauss or more, e.g. in a range of 5-5.8 kGauss, by use of a neodymium magnet or the like under the condition that the mixture of the MCF and the elastic polymeric material is kept in a sheet-like form having a thickness of 1 mm or less. In addition, a preparatory experiment clarifies that a lowered magnetic field reduces the formation density of the cluster, showing a tendency to decrease the electrical and thermal conductivities of the electrical conductive composite material. Therefore, a further strong magnetic field is preferably applied to a sheet-like form having a thickness of 1 mm or more. Under the above magnetic conditions, an electrical conductive composite material sheet can be provided with high electrical and thermal conductive performances.
In the curing step to form a thin MCF electrical conductive rubber having a thickness of 1 mm or less, the applied magnetic field can substantially heighten cluster density thereof in the vicinity of magnets. The high-density portions of the cluster can be partially cut down to be utilized. The high-density portions of the cluster can contribute to improving the thermal and electrical conductivities of the MCF electrical conductive rubber.
On exposure to air in ambient temperature, the above mixture begins to stiffen as well as general adhesive agents. The cluster is formed in the applied magnetic field before the mixture is cured. Thus, the structure of cluster is formed independent of the curing condition. The curing step is not limited to the above process but may be based on heat curing or chemical curing by curing agent and the like.
As a particularly preferred application of the electrical conductive composite material in the present invention, the electrical conductive composite material can be utilized as a detecting portion of a pressure-sensitive sensor, and as a contact of a pressure-sensitive switch. The electrical conductive composite material sheet can smoothly conduct electric current and heat in its thickness direction, and is preferably arranged to detect the electricity and heat in its thickness direction.
Hereafter, detailed explanations is given as to an electrical conductive composite material in the present invention and a production method thereof with the reference to the following examples.
At first, 3 g of Ni powder (available from Yamaishi Metal Corporation Ltd. as “123”, an average particle diameter of 3-7 μm) and 3 g of Cu powder (available from Yamaishi Metal Corporation Ltd. as “MF-D2”, an average particle diameter of 8-10 μm) were put into a beaker, and mixed with 4 g of an MF (available from Ferrotec Corporation Ltd., kerosene-based, weight percentage of 50 wt %), and then stirred for several minutes by use of supersonic stirrer to sufficiently mix the MF with the Ni powder and the Cu powder. Next, 10 g of a silicone-oil rubber (available from Dow Corning Toray Silicone Corporation Ltd. as “SH9550”) was added to a mixture, and stirred for about 15 minutes by use of a propeller-type stirrer, and then degassed by a vacuum deaerator. (In this example, the degassing is performed for about 45 minutes.) Subsequently, a resultant mixture was poured between a pair of non-magnetic plates 10 with permanent magnets 12 being N-pole and S-pole disposed respectively on opposite sides of the magnet plates, as shown in
In the resultant electrical conductive composite material sheet, cluster is formed by aggregation of Ni particles and Cu particles. The structures of the cluster were investigated by the following procedures. While magnetic field was applied in a predetermined strength to the mixture (not including silicone-oil rubber) of the MF with the Ni powder and the Cu powder dispersed thereinto, the MF was washed out with a washing solvent a plurality of times to extract only network cluster (skeleton structure) formed by the aggregation of the Ni particles and the Cu particles.
Next, thermal conductivity was evaluated for the resultant electrical conductive composite material sheet. Here, a thermal sensitivity refers to a time-dependent change in temperature of the composite material in contact with a highly-heated member having a certain temperature. The thermal sensitivity was measured by following procedures. As shown in
Next, in the manufacturing process of the electrical conductive composite material sheet 1, its thickness dependence on the thermal sensitivity was measured by a change in a distance between the nonmagnetic plates 10 as well as strength of the applied magnetic field in the curing step. This experiment was conducted on four kinds of the electrical conductive composite material sheets respectively having thicknesses of 0.298, 0.5, 0.601, 0.949 mm. Table 1 shows a relation among the thickness, the strength of the applied magnetic field, and ΔT/(Δt·δ). (ΔT, Δt, δ are respectively a change of temperature, a change of time, and the thickness)
The observation of the resultant cluster shows the cluster density is increased with a decrease in the thickness. As shown in Table 1, the reduction in the thickness increases ΔT/(Δt·δ), and thus improves the thermal sensitivity. As to the electrical conductive composite material sheet, a temperature slope can be predicted based on its thickness by use of formula (1) below. In other words, the thickness of the electrical conductive composite material sheet can be appropriately determined for achieving a predetermined thermal sensitivity, easing a material design thereof.
ΔT/(Δt·δ)=6.81 exp−5.41δ (1)
Next, a thickness dependence of pressure-sensitive electrical conductivity was evaluated as to the composite material sheet. Several kinds of the electrical conductive composite material sheets 1 were prepared in a variety of the thickness, and arranged to mount thereon a probe 30 having a dimension of 2 mm×2 mm, as shown in
Next, the pressure-sensitive electrical conductivity was compared between the electrical conductive composite material sheet in this example and a conventional pressure-sensitive electrical conductive rubber (available from Yokohama Image System Corporation Ltd. as “CSA”). For the purpose of measuring the pressure-sensitive electrical conductivity, the electrical conductive composite material sheet 1 was disposed between a pair of metal plates 40, and compressed by a vice 42 on both external sides of the pair of metal plates, as shown in
In the displacement amount of 20 μm or less by the applied external pressure, the electrical conductive composite material sheet in this example shows a higher electric resistance than the conventional pressure-sensitive electrical conductive rubber. In excess of 20 μm for the displacement amount, however, the electrical conductive composite material sheet shows a lower electric resistance and a greater electrical conductivity than the conventional pressure-sensitive electrical conductive rubber which hardly changes the electric resistance for its poor pressure sensitivity. These results enclose the electrical conductive composite material sheet shows higher pressure-sensitivity for greater change in the electric resistance than the conventional pressure-sensitive electrical conductive rubber.
The electrical conductive composite material sheets of examples 2 to 4 were prepared by the abovementioned procedures in mixing ratios of the Ni powder and the Cu powder, the MF, and the silicone-oil rubber shown in Table 2, when its thickness was kept constant.
As a preferred application example of the electrical conductive composite material sheet in the present invention, a brief explanation is made as to a haptic sensor formed of the electrical conductive composite material sheet in example 1. As shown in
As a further preferred application example of the electrical conductive composite material in the present invention, a brief explanation is made as to a pressure-sensitive sensor chip 70 formed of the electrical conductive composite material sheet in example 1. As shown in
An apparatus shown in
Furthermore, the electrical conductive composite material in the present invention can be obtained by curing the mixture of the liquid elastic polymeric material and the MCF containing the MF, Ni and Cu in the magnetic field, forming the characteristic network cluster by aggregation of the Cu particles and the Ni particles. Thus, the magnetic field can be applied only to predetermined portions of the mixture in the curing step, enabling to provide a rubber sheet 80 at the predetermined portions with the electrical conductive composite material 1, as shown in
Although the explanation in the above examples is given as to the electrical conductive composite material made of the Cu powder and the Ni powder, the technical concept of the present invention is to form the structures of the network cluster and to provide the great thermal and electrical conductive composite material, and not intended to exclude the use of any powder of Ni or Cu containing particles (e.g. alloy powder), any powder of Ni or Cu coated particles, or the like. Metallic powder other than Ni and Cu may be added to the MF for preparing the MCF when needed.
As described above, the present invention enables to provide a composite material having great thermal and electrical conductivity combined with a haptic function. The composite material is expected to become widely applicable in technical fields, for example a cellular phone, remote controllers, a mobile music player, a small-sized device requiring power-saving function as well as slimness and cheapness such as an electronic tag apparatus, a device requiring thermal conductivity and buffering capacity such as a contact detecting sensor in a stove, an apparatus requiring great elasticity such as a jointing portion of robot, a haptic sensor in a welfare robot supporting people, a pressure-sensitive switch, a haptic sensor such as an artificial skin, and the like.
This is a continuation-in-part patent application of International Application No. PCT/JP2007/055107 filed on Mar. 14, 2007.
Number | Date | Country | |
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Parent | PCT/JP2007/055107 | Mar 2007 | US |
Child | 12185010 | US |