This application claims priority from United Kingdom Patent Application No. GB 17 06 363.7, filed on 21 Apr. 2017, the entire disclosure of which is incorporated herein by reference in its entirety.
The present invention relates to a method of producing a composite material and method of producing a plurality of agglomerates, and an electrically responsive composite material and agglomerates for use in an electrically responsive composite material.
User input devices are known that are substantially flat and are responsive to movement of a stylus or finger in an xy plane, and in some cases, also sensitive to pressure applied in the z dimension. When incorporated into touch screens, it has previously proved difficult to produce transparent touch screens which operate in both the xy plane and the z dimension, this problem being previously identified in the applicant's patent EP 2 689 431.
EP 2 689 431 provides a pressure sensitive composite material which comprises a plurality of agglomerates dispersed within a carrier layer. In manufacture, these agglomerates are spontaneously formed by a process of mixing conductive or semi-conductive particles in combination with a polymeric material to produce the composite material in question. During mixing, the conductive or semi-conductive particles combine with other conductive or semi-conductive particles to form the agglomerates within the carrier layer. Thus, the formed agglomerates are dependent on the mixing process of the composite material and require a limitation of hyper-dispersant levels so that the agglomerates can form. The resulting agglomerates are often irregular with varying mechanical and electrical properties and the composite material often includes small agglomerates which provide limited conduction through the carrier layer and optical haze through an otherwise transparent or translucent material.
According to an aspect of the present invention, there is provided a method of producing a plurality of agglomerates for inclusion in an electrically responsive composite material, comprising the steps of: obtaining a plurality of electrically conductive or semi-conductive particles; mixing said plurality of electrically conductive or semi-conductive particles in a centrifugal mixer, said mixing step comprising operating said centrifugal mixer at a Froude number of between 220 and 1100; and adhering said plurality of electrically conductive or semi-conductive particles by adding a granulation binder and mixing said granulation binder with said plurality of electrically conductive or semi-conductive particles to form a plurality of agglomerates; wherein each said step of obtaining, mixing and adhering said electrically conductive or semi-conductive particles pre-forms said plurality of agglomerates prior to introduction of said plurality of agglomerates into said electrically responsive composite material.
Embodiments of the invention will be described, by way of example only, with reference to the accompanying drawings. The detailed embodiments show the best mode known to the inventor and provide support for the invention as claimed. However, they are only exemplary and should not be used to interpret or limit the scope of the claims. Their purpose is to provide a teaching to those skilled in the art.
Components and processes distinguished by ordinal phrases such as “first” and “second” do not necessarily define an order or ranking of any sort.
An electrically responsive composite material 101 is illustrated in
Each of the agglomerates 102 comprise a plurality of electrically conductive or semi-conductive particles 103 which are adhered together to form the agglomerates 102. In manufacture, the agglomerates are pre-formed and then dispersed within the carrier layer in the manner of
The size and dispersion of the agglomerates (shown greatly enlarged in
In order to produce the plurality of agglomerates 102, a plurality of electrically conductive or semi-conductive particles 201 are obtained and are placed into a granulation vessel 202. A granulation binder 203 is also added into the granulation vessel 202. The granulation vessel 202 is configured to perform a mixing process so that the plurality of electrically conductive or semi-conductive particles 201 adhere to each other during the mixing process. In the embodiment, particles 201 adhere together due to the presence of binder 203. In this way, the plurality of agglomerates 102 comprise a plurality of electrically conductive or semi-conductive particles 201 which have been adhered together by the mixing process performed by the granulation vessel 202.
In the embodiment, the ratio of the plurality of electrically conductive or semi-conductive particles 201 to granulation binder 203 is 10:1 weight/weight. Thus, it is appreciated that the amount of granulation binder used to adhere the particles together is relatively small compared to the amount of particles which form each agglomerate. It is further appreciated that, in alternative embodiments, alternative ratios which allow the electrically conductive and/or semi-conductive particles to adhere to each other are used.
In an embodiment, the conductive particles comprise antimony doped tin oxide particles. These are illustrated as spherical particles; however, it is appreciated that, in alternative embodiments, the particles are acicular (or needle shaped). The electrically conductive or semi-conductive particles typically have a largest dimension of between ten (10) and one hundred (100) nanometres (nm).
In an embodiment, granulation binder 203 comprises a silicone liquid binder, and in particular, comprises a two-part translucent high consistency rubber of which the main constituent is polydimethylsiloxane (PDMS). In an alternative embodiment, the granulation binder comprises a carbon-based (organic) binder such as an alcohol/petrol resistant (APR) varnish. In a further alternative embodiment, the granulation binder comprises a water-based binder, for example a transparent screen-printable ink containing no organic solvent. In still further embodiments, other suitable granulation binders may be used.
Granulation vessel 202 is configured to mix the particles and granulation binder at relatively high energies so as to produce agglomerates which do not break up easily. In an embodiment, the granulation vessel is a centrifugal mixer. In a particular embodiment, the centrifugal mixer has a dual axis of rotation, such as a SpeedMixer™ DAC 150.1 FVZ dual asymmetric centrifugal laboratory mixer as will be described in further detail with respect to
A schematic representation of a granulation vessel in the form of a dual axis centrifugal mixer which is suitable for performing a granulation process in accordance with the present invention is shown with respect to
A sample container 301 is provided into which the plurality of electrically conductive or semi-conductive particles 201 can be added along with the corresponding granulation binder 203. Sample container 301 is positioned at one end of a rotational arm 302 which is inclined at an angle 303 to the horizontal 304 about the cylindrical vessel having a radius 305. In an embodiment, angle 303 is set at forty degrees (40°) to the horizontal 304, with the radius being eighty millimetres (80 mm).
In use, rotational arm 302 is rotated about a central rotation axis 306, so that the sample container 301, due to its position at the end of rotational arm 302, moves in a circular manner in the direction of arrows 307. The dual axis centrifugal mixer 202 is further configured to rotate sample container 301 about a secondary rotation axis 308, in an opposed direction to that of the central rotation 306. This is indicated by the arrow 309.
The use of a dual asymmetric centrifuge of this type is advantageous as it promotes rapid homogenisation of the sample in the container and reduces air bubbles in the sample. This is due to the high acceleration and opposing centripetal forces imposed by the opposing axes. Traditionally, this type of mixer is not used for granulation processes, but for mixing two separate liquids together. The applicant has found, however, that a dual axis mixer of this type produces suitable agglomerates for use in an electrically responsive composite material.
The nature of this particular granulation vessel is that parameters such as the radius of rotation and speed of rotation can be varied to provide suitable results. In the embodiment, while the radius of rotation is maintained as a function of a particular mixer, the speed of rotation is relatively high which produces a high Froude number as will described in detail with respect to
The dual axis centrifugal mixer as described in respect of
In conventional granulation vessels, it is typical for Froude numbers to range between 0.2 to around 100, and therefore the present invention imparts much higher energies into the sample (i.e. the granulation binder and electrically conductive or semi-conductive particles) than would normally be expected in a granulation process.
While a dual axis centrifugal mixer is described here, it is appreciated that alternative granulation vessels may be used provided that they are able to input a suitably high Froude number to provide suitable agglomerates by means of a substantially similar granulation process.
To further illustrate the parameters used in the method of production of pre-formed agglomerates suitable for use in an electrically responsive conductive material, a graph of rotational speed (revolutions per minute−rpm) against the granulation time (minutes) is shown in
The graph illustrates three regions, 501, 502 and 503 indicating the relationship between the two parameters and the corresponding size of agglomerates produced. In region 501, agglomerates were produced of sizes having a greatest dimension of less than ten micrometres (10 μm). Thus, in this region, the agglomerates produced are relatively small. In region 502, the agglomerates larger, surface-smooth agglomerates are produced which typically have a largest dimension of between twenty and forty micrometres (20-40 μm). In region 503, the agglomerates are larger and may be more than forty micrometres (40 μm) across their largest dimension. Agglomerates in region 503 have been noted to include a plurality of indentations on their surface which provides an appearance similar to a golf-ball.
Thus, in an embodiment, the agglomerates have a largest dimension of between four and twenty micrometres (4-20 μm) and preferably between four and ten micrometres (4-10 μm) and typically have a smooth surface and relatively consistent overall size. However, in an alternative embodiment, the agglomerates produced are larger and have indentations on their surface, as will be described in further detail in
Example agglomerates in accordance with the present invention are shown in
In this embodiment, the agglomerates have been produced in line with the parameters of region 3 of the graph of
A method of producing a plurality of agglomerates of the types previously described herein is shown in diagrammatic form in
At step 701, electrically conductive or semi-conductive particles 201 are obtained. In an embodiment, the particles 201 comprise antimony doped tin oxide spherical particles. In an alternative embodiment, the antimony doped tin oxide particles are acicular or needle-shaped. Each particle typically has a largest dimension of between ten and one hundred nanometres (10-100 nm).
At step 702 a granulation binder 203 is obtained. The granulation binder is in the form of a liquid and is typically a silicone liquid binder such as one which comprises a two-part translucent high consistency rubber of which the main constituent is polydimethylsiloxane (PDMS). In an alternative embodiment, granulation binder 203 comprises a carbon-based (organic) binder such as an alcohol/petrol resistant (APR) varnish. In a further alternative embodiment, the granulation binder comprises a water-based binder, for example a transparent screen-printable ink containing no organic solvent.
The particles and granulation binder are introduced into a granulation vessel in the manner of
At step 705, the agglomerates undergo a further size selection process which ensures that each said agglomerate is within a predetermined size range. For example, in an embodiment, the agglomerates are sieved at twenty micrometres (20 μm) so maintain the agglomerates as being smaller than twenty micrometres (20 μm). This assists in ensuring that the agglomerates are of a suitable size for any future applications, such as the inclusion into an electrically responsive composite material. It is appreciated that other size selection processes may be utilised that allow the agglomerates to be sorted in accordance with their future applications.
Once the plurality of agglomerates have been suitably formed as described, they are then able to be used in the production of a composite material, which in turn can form part of a touch screen or other electronic device.
In order to produce a composite material, the plurality of agglomerates are introduced into a liquid carrier and mixed into the liquid carrier to produce the composite material which will now be described with respect to
A composite material 801 having a plurality of agglomerates, such as agglomerates 802 and 803, which have been pre-formed by the method herein described, is shown in
The plurality of agglomerates (802, 803) have been introduced into a liquid carrier which has been solidified to produce a solidified polymeric material. In an embodiment, the carrier layer comprises any suitable liquid carrier which comprises a component capable of solidifying to produce a solidified polymeric material and in order to produce the composite material, the agglomerates are introduced into the liquid carrier and mixed to disperse the agglomerates within the liquid carrier before solidification takes place.
The resultant carrier layer 804 has a length and a width and a thickness 805 which is relatively small compared to the width. In the embodiment, the thickness 805 is between four and six micrometres (4-6 μm).
The plurality of agglomerates (802, 803) have a largest dimension of between four and twenty micrometres (4-20 μm), but in the embodiment, the largest dimension is typically between four and ten micrometres (4-10 μm). In particular, the thickness 805 of carrier layer 804 is smaller than the largest dimension of each agglomerate. For example, the agglomerates have a largest dimension of between eight and ten micrometres (8-10 μm) for a carrier layer thickness of six micrometres (6 μm). Thus, in this way, the agglomerates protrude slightly from the solidified carrier layer so that they are able to provide a conductive path.
In contrast to previous method of manufacture, because the agglomerates have been pre-formed prior to their inclusion into the liquid binder, the agglomerates are able to be provided with consistent properties, both mechanical and electrical. Thus, this reduces the number of particles which do not form usable agglomerates, for example, those which are too small to provide a conductive path through the carrier layer.
A diagrammatic illustration of conduction paths through a composite material in accordance with the invention is shown in
When a low force is applied to deformable electrode 901, indicated by arrow 906, agglomerate 905 is brought into contact with electrode 901 which creates a limited conduction path indicated by arrow 907, as shown in
A graph of force against resistance for samples corresponding to composite materials of the type previously manufactured in accordance with the applicant's patent EP 2 689 431, and composite materials in accordance with the present invention is shown in
Line 1001 shows the force-resistance response of a sample in accordance with the present invention, where the agglomerates have been pre-formed. Line 1002 shows the force-resistance response of a sample in accordance with the previously known method which creates agglomerates spontaneously. In the sample used here, the agglomerates were pre-formed using a centrifugal mixer as described with respect to
It is noted that the present invention produces a less sensitive force-resistance response at low forces, meaning the composite material operates less like a switch than conventional methods. This can be useful in digital on/off applications. Visible light transmission is also improved as there is reduced haze from lack of non-conducting smaller agglomerates.
Thus, the present invention not only provides a suitable method for controlling the parameters of the agglomerates to suit a particular application, but also provides characteristics that are not provided by spontaneous agglomerate formation.
Number | Date | Country | Kind |
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1706363.7 | Apr 2017 | GB | national |
Filing Document | Filing Date | Country | Kind |
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PCT/GB2018/000069 | 4/18/2018 | WO | 00 |