Patent Grant
10262777
This application is a 35 U.S.C. § 371 national phase application of PCT Application No. PCT/SE2014/051434 filed Dec. 2, 2014, which claims priority to Swedish Application No. 1351428-6 filed Dec. 2, 2013, the entire contents of each of which is incorporated by reference herein.
The technical field is generally directed to a new compound having exponential temperature dependent electrical conductivity.
Materials having a positive temperature coefficient (PTC) experience an increase in electrical resistance when their temperature is raised. Materials which have useful engineering applications usually show a relatively rapid increase with temperature, i.e. a higher coefficient. The higher the coefficient, the greater an increase in electrical resistance for a given temperature increase.
PTC ceramics are known in the art. Most ceramics have a negative coefficient, whereas most metals have positive values. While metals do become slightly more resistant at higher temperatures, the PTC ceramics (often barium titanate and lead titanate composites) have a highly nonlinear thermal response, so that it becomes extremely resistive above a composition-dependent threshold temperature. This behavior causes the material to act as its own thermostat, since the material conducts current below a certain temperature, and does essentially not conduct current above a certain temperature.
There are constantly demands for new PTC materials, which have improved electrical and mechanical performance, and which can be used in existing applications as well as new applications, in which present PTC materials are unsuitable.
A first aspect refers to a novel compound having exponential temperature dependent electrical resistivity, preferably exponentially increasing resistivity (or exponentially decreasing conductivity) with temperature. Such compound may be referred to as a novel PTC material.
The novel compound comprises an electrically insulating bulk material, electrically conductive particles of a first kind, and electrically conductive particles of a second kind. The bulk material holds the particles of the first and second kinds in place therein; the particles of the second kind are smaller than the particles of the first kind; the particles of the second kind are more in number than the particles of the first kind; and the particles of the second kind have higher surface roughness than the particles of the first kind, wherein the particles of the second kind comprise tips and the particles of the first kind comprise even surface portions. The particles of the first and second kinds are arranged to form a plurality of current paths through the compound, wherein each of the current paths comprises galvanically connected particles of the first and second kinds and a gap between a tip of one of the particles of the second kind and an even surface portion of one of the particles of the first kind, which gap is narrow enough, e.g. less than 100 nm, to allow electrons to tunnel through the gap via the quantum tunneling effect. The bulk material has a thermal expansion capability such that it expands with temperature, thereby increasing the gap widths of the current paths, which in turn increases the electrical resistivity of the compound exponentially. At a certain gap width of the current paths, the quantum tunneling effect disappears and the compound does not conduct any longer.
The bulk material may comprise a cross-linked polymer or elastomer, such as for example a silicone, e.g. polydimethyl siloxane, and the particles of the first and second kinds may be carbon-containing particles, such as for example carbon blacks. The bulk material may also comprise a filler, thickener, or stabilizer, such as for example silica.
The particles of the second kind may have a size which is at least 5 times, preferably at least 10 times, more preferably at least 50 times, and most preferably at least 500 times smaller than a size of the particles of the first kind, wherein the sizes are volume based or weight based particle sizes. The sizes may be statistically determined sizes, such as e.g. median sizes or average sizes, of the particles of the first and second kinds.
The number of particles of the second kind may be at least 5 times, preferably at least 10 times, more preferably at least 50 times, and most preferably at least 500 times more than the number of the particles of the first kind.
The particles of the second kind may have at least 5 times, preferably at least 10 times, more preferably at least 50 times, and most preferably at least 500 times higher surface roughness than the particles of the first kind, wherein the surface roughness is measured as any of the arithmetic average of absolute values, root mean squared, maximum valley depth, maximum peak height, maximum height of the profile, skewness, kurtosis, average distance between the highest peak and lowest valley in each sampling length, or Japanese Industrial Standard based on the five highest peaks and lowest valleys over the entire sampling length.
The particles of the second kind may have highly irregular shape and tips, which are so sharp that the very ends of the tips comprise a single atom or a few atoms only, whereas the electrically conducting particles of the first kind have a more regular shape.
The bulk material may have a linear or volumetric thermal expansion coefficient of at least 50×10−6 K−1, preferably at least 100×10−6 K−1, and more preferably at least 200×10−6 K−1.
A second aspect refers to the use of the novel compound as a self-regulated heating element.
A third aspect refers to a self-regulating heating element comprising the novel compound and two terminals electrically connected thereto. The compound may be provided in the form of a layer and the two terminals may comprise each a patterned electrically conducting layer. In one embodiment the patterned electrically conducting layers are formed on opposite sides of the compound layer, and in another embodiment the patterned electrically conducting layers are formed on a single side of the compound layer, wherein a protective layer is formed on the side of the compound layer, which is opposite to the side, on which the patterned electrically conducting layers are formed.
A fourth aspect refers to a method of forming a novel compound having exponential temperature dependent electrical resistivity. According to the method, an electrically insulating bulk material being capable of holding particles in place therein and having a thermal expansion capability such that it expands with temperature is provided; and electrically conductive particles of a first kind and electrically conductive particles of a second kind are provided, wherein the particles of the second kind (i) are smaller than the particles of the first kind; (ii) are more in number than the particles of the first kind, and (iii) have higher surface roughness than the electrically conducting particles of the first kind; and the particles of the second kind comprise tips and the particles of the first kind comprise even surface portions.
The particles of the first and second kinds are arranged in the bulk material to form a plurality of current paths through the compound, wherein each of the current paths comprises galvanically connected particles of the first and second kinds and a gap between a tip of one of the electrically conducting particles of the second kind and an even surface portion of one of the electrically conducting particles of the first kind, which gap is narrow enough, e.g. less than 100 nm, to allow electrons to tunnel through the gap via the quantum tunneling effect.
Hereby, the electrical resistivity of the compound is exponentially increasing with the temperature.
The bulk material may be a polymer or elastomer, such as for example a silicone, e.g. polydimethyl siloxane, as disclosed above. The polymer or elastomer is cross-linked or hardened after that the electrically conducting particles of the first and second kinds have been arranged in the electrically insulating bulk material. The cross-linking may be performed by irradiating the compound with electrons, by platinum-catalyzed curing, by vulcanization, or by any other method.
The particles of the first and second kinds may be carbon-containing particles, such as for example carbon blacks, wherein the particles of the second kind may have highly irregular shape and tips, which may be so sharp that the very ends of the tips comprise a single atom or a few atoms only, whereas the particles of the first kind may have more regular shape.
The surface of the particles of the second kind may be covered by a lubricant, such as for example a homo-oligomer, e.g. vinylmethoxysiloxane homo-oligomer, before the particles of the first and second kinds are arranged in the bulk material, and a filler, thickener, or stabilizer, such as for example silica, may be mixed with the bulk material to obtain a compound having a desired consistence and flexibility. The use of the lubricant is important in order to have the particles of the first and second kinds appropriately arranged in the bulk material to form the desired current paths.
The number of the current paths through the compound and the widths of the gaps therein at any given temperature are provided depending on the thermal expansion capability of the electrically insulating bulk material to obtain an exponential temperature dependent electrical resistivity of the compound in a selected temperature interval and optionally to obtain a non-conducting compound above a selected temperature (at which temperature, the gaps are wide enough to not allow electrons to tunnel through the gap via the quantum tunneling effect).
Advantages of the novel compound include the following:
Further characteristics and advantages will be evident from the detailed description of embodiments given hereinafter, and the accompanying
The compound comprises an electrically insulating bulk material 11, electrically conductive particles 12 of a first kind, and electrically conductive particles 13 of a second kind arranged in the bulk material 11.
The bulk material 11 may comprise an amorphous cross-linked polymer or elastomer, such as for example a siloxane elastomer (often called silicone elastomer) such as polyfluorosiloxane or polydimethyl siloxane and possibly also a filler, thickener, or stabilizer.
The bulk material holds the particles of the first and second kinds firmly in place in the bulk material.
The filler, thickener, or stabilizer may be mixed with the bulk material to obtain a compound having a desired consistence, flexibility, and/or elasticity.
The electrically conducting particles 12, 13 of the first and second kinds may be carbon-containing particles, such as for example carbon blacks.
The particles 13 of the second kind may (i) be smaller, (ii) be more in number, (iii) have higher surface roughness, and (iv) have more irregular shape than the particles 12 of the first kind as being schematically illustrated in
More in detail, the particles 13 of the second kind may have a size which is at least 5 times, preferably at least 10 times, more preferably at least 50 times, and most preferably at least 500 times smaller than a size of the particles 12 of the first kind, wherein the sizes are volume based or weight based particle sizes. The sizes may be statistically determined sizes, such as e.g. median sizes or average sizes, of the particles of the first and second kinds.
In one example the particles may have the following average size (given in nm):
It shall be appreciated that the individual sizes of the particles of each kind may vary quite much, such as e.g. by a factor 10. Therefore it is advantageous that the sizes are given as some kind of statistical sizes, such as e.g. average sizes.
The number of g particles 13 of the second kind may be at least 5 times, preferably at least 10 times, more preferably at least 50 times, and most preferably at least 500 times more than the number of the particles 12 of the first kind.
The particles 13 of the second kind may have at least 5 times, preferably at least 10 times, more preferably at least 50 times, and most preferably at least 500 times higher surface roughness than the particles 12 of the first kind, wherein the surface roughness is measured as any of the arithmetic average of absolute values, root mean squared, maximum valley depth, maximum peak height, maximum height of the profile, skewness, kurtosis, average distance between the highest peak and lowest valley in each sampling length, or Japanese Industrial Standard based on the five highest peaks and lowest valleys over the entire sampling length.
The particles 13 of the second kind may have highly irregular shape, whereas the particles 12 of the first kind may have regular shape.
The particles 12, 13 of the first and second kinds may have different properties with respect to surface energies and electrical conductivities.
It can be seen that the highly irregularly shaped particles 13 of the second kind comprise tips 13a and the more regularly shaped particles 12 of the first kind comprise even surface portions 12a. The tips 13a of the particles 13 of the second kind may be so sharp that the very ends of the tips 13a comprise a single atom or a few atoms only.
If the width w of a gap 14a between a tip 13a of one of the particles 13 of the second kind and an even surface portion 12a of one of particles 12 of the first kind is narrow enough, electrons are enabled to tunnel through the gap via the quantum tunneling effect.
In one embodiment, the surface of the particles 13 of the second kind may be covered by a lubricant, such as for example a homo-oligomer, e.g. vinylmethoxysiloxane homo-oligomer, as being illustrated for one of the particles 13 of the second kind in
The bulk material 11 has a thermal expansion capability such that it expands with temperature, thereby increasing the gap widths w of the current paths 14, which in turn increases the electrical resistivity of the compound exponentially. As a non-limiting example, the bulk material 11 may have a linear or volumetric thermal expansion coefficient of at least 50×10−6 K−1, preferably at least 100×10−6 K−1, and more preferably at least 200×10−6 K−1.
The number of the current paths 14 through the compound and the widths w of the gaps therein at any given temperature are provided depending on the thermal expansion capability of the bulk material 11 to obtain an exponential temperature dependent electrical resistivity of the compound in a selected temperature interval.
The number of current paths is obtained by suitable densities of the particles 12, 13 of the first and second kinds. The selected temperature interval depends on the application, for which the compound is to be used, but may be in the interval −20° C. to 170° C.
The novel compound may be provided as a thin film having a thickness of e.g. about 0.1-1 mm.
The compound disclosed above may be used as a self-regulated heating element, wherein no thermostat is required. When using the compound as a heating element, a current is flown through the compound, and heat generated proportional to the resistance of the compound and proportional to the square of the current flown through the compound. As the temperature is increased the resistivity is increased exponentially with temperature, which means that the resistance is increased exponentially with temperature causing the compound to become essentially non-conduction, and the heating element is turned off automatically.
By way of example, the electrically conducting layers may be about 0.01-0.1 mm thick and may be covered by electrically insulating protective films, e.g. plastic films.
The heating elements disclosed with reference to
An electrically insulating bulk material is, in a step 61, provided. The bulk material is capable of holding particles in place therein and has a thermal expansion capability such that it expands with temperature.
Electrically conductive particles of a first kind and electrically conductive particles of a second kind are, in a step 62, provided, wherein (a) the particles of the second kind (i) are smaller than the particles of the first kind; (ii) are more in number than the particles of the first kind, and (iii) have higher surface roughness than the particles of the first kind; and (b) the particles of the second kind comprise tips 13a and the particles of the first kind comprise even surface portions.
The particles of the first and second kinds are, in a step 63, arranged in the bulk material to form a plurality of current paths through the compound, wherein each of the current paths comprises galvanically connected particles of the first and second kinds and a gap between a tip of one of the electrically conducting particles of the second kind and an even surface portion of one of the electrically conducting particles of the first kind, and the gap has a width which is small enough to allow electrons to tunnel through the gap via the quantum tunneling effect.
The bulk material may comprise a polymer or elastomer, such as for example a silicone, e.g. polydimethyl siloxane, which may be cross-linked after that the particles of the first and second kinds have been arranged in the electrically insulating bulk material. The cross-linking may for instance be performed by irradiating the compound with electrons, by platinum-catalyzed curing, or by vulcanization.
A filler, thickener, or stabilizer, such as for example silica, may be mixed with the polymer or elastomer to obtain a compound having a desired consistence, flexibility, and/or elasticity.
The particles of the first and second kinds may be carbon-containing particles, such as for example carbon blacks, wherein the tips of the particles of the second kind may be so sharp that the very ends of the tips comprise a single atom or a few atoms only.
The particles of the second kind may be provided of a highly irregular shape, whereas the particles of the first kind may be provided of regular shape.
The particles of the first kind may be mixed with the polymer or elastomer.
The particles of the second kind may be covered by a lubricant, such as for example a homo-oligomer, e.g. vinylmethoxysiloxane homo-oligomer, before the particles of the first and second kinds are arranged in the bulk material. To this end, the particles of the second kind and the lubricant are mixed together in a solvent, after which the solvent is removed.
The mixture of the particles of the second kind and the lubricant may be mixed with the filler, thickener, or stabilizer in a solvent, after which the solvent is removed.
The mixture of the particles of the second kind, the lubricant and the filler, thickener, or stabilizer may be mixed with the mixture of the particles of the first kind and the polymer or elastomer to obtain the compound.
Alternatively, the filler, thickener, or stabilizer may be mixed with the particles of the first kind and/or the polymer or elastomer, to which the mixture of the particles of the second kind and the lubricant is added.
The number of the current paths through the compound and the widths of the gaps therein at any given temperature are provided depending on the thermal expansion capability of the compound to obtain an exponential temperature dependent electrical resistivity of the compound in a selected temperature interval.
The number of the current paths through the compound, the widths of the gaps therein, and the thermal expansion capability of the compound can be controlled by adjusting the various ingredients of the compound, varying the amounts of the various ingredients of the compound, varying the order and manner in which they are mixed, and/or varying the cross-linking of the polymer or elastomer comprised in the bulk material.
In one example the compound is made up the following ingredients and amounts thereof (as given in weight percentages based on the weight of the compound):
It shall be appreciated by a person skilled in the art that the above disclosed embodiments may be combined to form further embodiment falling within the terms of the claims, and that any measures are purely given as example measures.
| Number | Date | Country | Kind |
|---|---|---|---|
| 1351428 | Dec 2013 | SE | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/SE2014/051434 | 12/2/2014 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2015/084241 | 6/11/2015 | WO | A |
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| Entry |
|---|
| International Search Report for PCT/SE2014/051434 dated Mar. 9, 2015. |
| Written Opinion of the International Searching Authonty for PCT/SE2014/051434 dated Mar. 9, 2015. |
| Number | Date | Country | |
|---|---|---|---|
| 20160260529 A1 | Sep 2016 | US |
