Patent Application
20140124711
The invention generally relates to conductive and non-conductive materials that are used in conjunction with providing an electric field at one side of such a material responsive to an electric field on the other side of the material for biomedical applications.
The design of an electrically conductive pressure sensitive adhesive (PSA) for biomedical applications has long presented challenges at least because adhesive strength and flexibility generally decrease with increased electrical conductivity. The materials that are typically used (e.g., added) to provide good electrical conductivity are generally less flexible and inhibit adhesion. A conventional way to prepare a conductive coating is to fill a polymeric material with conductive particles, e.g., graphite, silver, copper, etc., then coat, dry and cure the polymeric binder. In these cases, the conductive particles are in such a concentration that there is a conductive network formed when the particles are each in physical contact with at least one other neighboring particle. In this way, a conductive path is provided through the composite.
For pressure sensitive adhesives (PSAs), however, if the particle concentration is high enough to form a network in which particle-to-particle contact is maintained then there is little chance that the polymer (e.g., elastomer) system of the PSA component is present in high enough concentrations to flow out to make surface-to-surface contact between the substrates and an electrode, i.e., act as an adhesive. Conversely, if the PSA component is in sufficient concentration to make sufficient surface contact to the substrate, it would have to interrupt adjacent conductive particles such that particle-to-particle contact is disrupted.
Another type of electrically conductive PSA includes conductive spherical particles with diameters equal to or greater than the thickness of the PSA. In this fashion the signal or current may be carried along the surface of the particles, thus providing current flow anisotropically in the z dimension of the adhesive. Such a composite has not been shown in the prior art to be usable for a biomedical adhesive.
Salts, such as sodium or potassium chloride, readily dissolve when in an aqueous medium, and their ions dissociate (separate into positive and negative ions). The dissociated ions may then convey an electrical current or signal. For this reason, salts have long been added to water, which then may be added to polymeric and elastomeric materials, to provide good electrical conductivity. For example, U.S. Pat. No. 6,121,508 discloses a pressure sensitive adhesive hydrogel for use in a biomedical electrode. The gel material is disclosed to include at least water, potassium chloride and polyethylene glycol, and is disclosed to be electrically conductive. U.S. Pat. No. 5,800,685 also discloses an electrically conductive adhesive hydrogel that includes water, salt, an initiator or catalyst and a cross linking agent. The use of such hydrogels however, also generally requires the use of a conductive surface at one side of the hydrogel (away from the patient) that is capable of receiving the ionicly conductive charge, such as silver/silver chloride, which is relatively expensive.
While these hydrogel/adhesives can have good electrically conductive properties, they often have only fair adhesion properties. Another downside is that the electrical conductivity changes with changing water content, such as changes caused by evaporation, requiring that the hydrogels be maintained in a sealed environment prior to use, and then used for a limited period of time due to evaporation.
U.S. Pat. No. 7,651,638 discloses a water insensitive alternating current responsive composite that includes a polymeric material and a polar material (such as a salt) that is substantially dispersed within the polymeric material. The polar material however, is not employed to provide electrical conductivity via ionic conduction. The polymeric material and the polar material are chosen such that the two materials each exhibit a mutual attraction that is substantially the same as the attraction within the individual materials. Because of this, the polar material neither clumps together nor blooms to a surface of the polymeric material, but remains suspended within the polymeric material. This is in contrast to the use of these salts in other applications that are intended to bloom to a surface to provide a conductive layer along a surface, e.g., for static discharge.
The composites of U.S. Pat. No. 7,651,638, however, remain dielectrics and have high resistance, and are therefore not suitable for use in certain applications, such as providing electrical stimulus to a human subject (defibrillation and/or transcutaneous electrical nerve stimulations, etc.) due to the high resistance of the material. This type of signal detecting adhesive is also not capable of dissipating the charge overload in a timely enough fashion as per AAMI EC12-2000-4.2.2.4, which is directed to defibrillation overload recovery (DOR). The materials are therefore not suitable for use as a monitoring electrode through which a signal may be needed to be detected after a defibrillation charge is applied to a patient. The failure to pass AAMI EC 12-2000-4.2.2.4 is due to the high impedance of these capacitively coupled adhesives.
There remains a need, therefore, for a composite for use in conducting a representative signal and/or current through at least the z dimension of a PSA in a biomedical electrode, such that the use of conductive particles may be minimized, while preserving the adhesive's properties, so that both good electrical performance and good adhesive properties may be maintained.
The invention provides an alternating electric field responsive composite for use in a biomedical electrode that provides capacitive coupling through the composite in accordance with an embodiment. The composite includes a binder material, a polar material that is substantially dispersed within the binder material, and electrically conductive particles within the binder material. The polar material is responsive to the presence of an alternating electric field, and the electrically conductive particles are not of sufficient concentration to form a conductive network through the composite, yet will provide an overcharge protection in the event, for example, of a defibrillation procedure.
In accordance with an embodiment, the overcharge protection is provided by having the electrically conductive particles migrate via electrophoresis to form electrically conductive paths through the composite.
In accordance with another embodiment, the binder material and the polar material exhibit mutual molecular compatibility, and the electrically conductive particles remain substantially isolated from one another within the binder material.
In accordance with a further embodiment, the electrically conductive particles may be carbon or graphite in the form of powder, flakes granules, nanotubes, etc.
In accordance with a further embodiment, the invention provides a method of providing overcharge protection in a biomedical electrode using electrophoresis.
The following description may be further understood with reference to the accompanying drawings in which:
The drawings are shown for illustrative purposes only and are not to scale.
Applicants have discovered that although the composites of U.S. Pat. No. 7,651,638 are disclosed to function by capacitive coupling, conductive particles may be added to such composites with surprising results; although they are not added in such quantity that they form a conductive network, the electrically conductive composites undergo electrophoresis when the composite is exposed to an overcharge voltage such as, for example, the 200 volts DC as used in AAMI EC12-2000-4.2.2.2.4. Such an overvoltage charge would occur if a defibrillation procedure was performed on a patient being monitored. Failure to dissipate the charge from the electrode in a timely enough fashion so that the electrodes can again pickup ECG signals, may result in additional defibrillation procedures being done due to the absence of an ECG signal. Further, a capacitive discharge from the electrode to the patient may cause burns to the patient's skin.
It has been found however, that the electrically conductive particles, when in the presence of the overcharge voltage, migrate within the binder so as to form independent conductive paths through the composite, thereby causing the resistivity through the composite to drop significantly. This functionality provides an overcharge protection to the biomedical electrode.
The impedance may be measured by the method described in AAMI EC12-2000-4.2.2.1 (AC Impedance), which provides a maximum of 3000 Ohms permitted for any single value and an average not to exceed 2000 Ohms. The AC impedance method used herein was modified to 20 Hz rather than 10 Hz, using a QuadTech 1920 Precision LCR meter sold by QuadTech, Inc. of Marlborough, Mass.
It has been found however, that examples of composites of the invention including just 5% by weight carbon particles have resistances of less than 1000 Ohms following overcharging, meaning that the composites pass AAMI EC12-2000-4.2.2.4, yet function by the capacitive coupling techniques disclosed in U.S. Pat. No. 7,651,638 before being subjected to an overcharge electric field. It has further been found, in fact, that by adding as little as (1%) of a conductive particle either randomly dispersed or position specific within a polymeric material including a polar material as described above, composites may be formed that pass AAMI EC12-2000-4.2.2.1 and AAMI EC12-2000-4.2.2.4 following overcharging. Lower resistance mixtures (following overcharging) were obtained using a 2.5% conductive particle addition, and still lower resistance mixtures (following overcharging) were obtained using a 5% conductive particle addition.
A further aspect of the present invention is that since the representative signal from the aligning/relaxing electric fields of the polar material is present in the z direction, a large area (in the x and y directions) material may be employed that contains multiple receiver contacts on the common large area material. The material, therefore, is anisotropic in that sensor contacts may be adjacent one another on the common composite material without cross signal detection. Moreover, the composite material remains anisotropic following overcharging since the conductive paths formed by electrophoresis are discrete from one another as discussed further below.
The requirements for the binder material (e.g., polymeric material or elastomeric material), the polar material and the conductive material are that the materials interact in such a way that neither the polar material nor the conductive material clumps together within the binder material or blooms to a surface of the binder material. If the conductive material has a surface energy similar to that of the binder material, then it will remain suspended within the binder material yet not be in sufficient concentrations to provide electrical conductivity through the material prior to any overcharging.
In accordance with an embodiment of the invention, the polymeric material may, for example, be an acrylic adhesive such as may be represented as
where R may vary and may be any of an ethyl, or a butyl or a 2-ethylhexyl or other organic moiety, and n is a number of repeating units. For example, the polymeric material may be a FLEXcon V95 pressure sensitive adhesive as sold by FLEXcon Company, Inc. of Spencer, Mass.
In an embodiment, the polar material may be a quaternary ammonium salt such as may be represented as:
where R=H or some carbon based moiety, and where any of the R groups may be the same or different. For example, the polar material may be an Arquad HTL8-MS quaternary ammonium salt sold by Akzo Nobel Surfactants of Chicago, Ill.
An objective of the selection of the combination of the binder material and the polar material is that the two materials each exhibit a mutual attraction that is very similar to the attraction that each material has to its own molecules. This results in the polar material being homogeneously dispersed within the binder material. The suitability of the combination of the polymeric material and the polar material may be identified by the following procedure. First, a polar material is combined with the polymeric material in about five different concentrations (typically between about 5% to about 45% by weight). Then the adhesive and salt composite is drawn onto a release liner (of about 1.5 mil), and permitted to dry and cure. The surface of the composite is then inspected after a short period of time. If the polar material has crystallized out or bloomed to the surface, then the combination of components is not compatible. If, on the other hand, the composite is clear, it is subjected to the next level of compatibility testing. The samples should then be subjected an exposure test in which the samples are exposed to 100 F with 95% relative humidity for 3 days. The samples are then again inspected to determine whether the polar material has migrated toward either surface. If there has been no migration of the polar material and the composite is clear, then the dielectric constant for the composite is determined and the composite is tested for use as a medical monitoring material.
With reference again to the diagrammatic enlarged view 16 of
As shown in
The voltage at the electrode on the surface 26, therefore, alternates in the presence of an alternating electric field at the opposite surface 24. In this way, an alternating electric field from the first side of the composite may be represented by a second alternating electric field provided at the electrode 28. Note that the capacitance may vary depending upon the size (e.g., the X-Y plane and the total distance between conductive surfaces.
The conductive particles should have a surface energy that is at least slightly greater than that of the binder material to ensure that the binder material sufficiently wets the surface of the conductive particles. The density and surface area of the conductivity of the particles 14 are important considerations. Applicants have found, for example, that carbon (e.g., graphite powder, flakes, granules or nanotubes etc.) having densities in the range of, for example, about 0.35 g/cm3 to about 1.20 g/cm3, and preferably between about 0.5 g/cm3 to 1.0 g/cm3, are suitable for use as the conductive material. The surface energy of the graphite is, again, preferably higher than that of the binder to ensure sufficient wetting of the surfaces of the particles 14. In the above example, the graphite particles have a specific surface energy of 55 dynes/cm and the binder disclosed above has a surface energy of less than 40 dynes/cm.
In particular,
As shown in
Regardless of whether the overvoltage charge is DC or AC, the higher the voltage, the faster the particles align, but with a relatively low voltage (e.g., about 5 volts or higher), the particles align more slowly, but do still eventually align.
As shown in
In accordance with a further embodiment, a composite 50 of the invention may include a first portion 52 that exhibits capacitive coupling as described above, while another portion 54 of the composite includes conductive paths, e.g., formed of spheres 56 of carbon, that extend just slightly through the binder material as shown in
In accordance with an embodiment, in one example, a polar material (Arquad HTL-8 (AkzoNobel), 20% by weight on solids) was added to a liquid sample of FLEXcon's V-95 acrylic PSA. To this, 5% by weight (solids of the V-95 FLEXcon and Arquad blend) of a carbon particle (the Aquablack 5909 carbon particles from Solution Dispersions Inc., Cynthiana Ky.), was uniformly dispersed. This mixture was coated onto a 2 mil (50 micron) siliconized one side PET film, dried and cured for 10 min in a 160° F. vented laboratory oven, to a dried deposition of 2 mil (50 micron).
It has been found that after performing the test procedure in AAMI E12-2000-4.2.2.4 the adhesive composite with the conductive particles dispersed within undergoes a change. Post device overload recovery (DOR) tested materials will now pass AAMI E12-2000-4.2.2.1. It has also been found that like the capacitively coupled binder material, which has Z dimension signal receptivity, the post DOR material maintains this Z dimension signal receptivity. In addition the conductive particle variant, post DOR test, material also conveys current in the Z dimension. Interestingly this maintenance of Z dimensionality allows this adhesive to be used in applications as disclosed in U.S. Patent Application Publication No. 2010-0036230 which teaches the formation of a bio-sensor array fashioned with one continuous layer of adhesive, the disclosure of which is hereby incorporated by reference in its entirety.
Composites in accordance with certain embodiments of the present invention, begin with substantially separated particles uniformly dispersed within the adhesive, then requires a second step, i.e., applying an electric field to form the conductive structures. This is a decided advantage as it allows for the placement of conductive structures, i.e., in the Z dimension and if needed, place the Z dimensioned structures at specific X,Y, locations thus allowing for a specific point to point electrical contact.
The following Examples demonstrate the effect of the conductive particle addition to the binder material discussed above.
To a liquid sample of FLEXcon's V-95 acrylic PSA, is added the polar material, Arquad HTL-8 (AkzoNobel), 20% by weight on solids, to this 5% by weight (solids of the V-95 and Arquad blend) of a carbon particle (Aquablack 5909 from Solution Dispersions Inc., Cynthiana Ky.), was uniformly dispersed and designated as Sample 1. This mixture was coated on a 2 mil (50 micron) siliconized one side PET film, dried and cured for 10 min in a 160° F. vented laboratory oven, to a dried deposition of 2 mil (50 micron).
Also prepared at this time was the composite of just the V-95 acrylic adhesive and the Arquad (20% by solids weight), no carbon, as per the teachings in U.S. Pat. No. 7,651,638. This mixture was also 2 mil (50 microns) siliconized one side PET film, dried and cured for 10 min in a 160° F. vented laboratory oven, to a dried deposition of 2 mil (50 microns) and was designated as Sample 2.
Similarly a third sample was prepared consisting of only V-95 arcylic adhesive and 5% carbon, with no polar material (Arquad). The sample was processed in the same manner as for samples 1 and 2, and this sample was designated as Sample 3.
All three samples were tested on a conductive base material consisting of a carbon filled polymeric film with a surface resistance of ˜100 ohms/square, using the experimental product designated EXV-215, 90 PFW (as sold by FLEXcon Company, Inc. of Spencer, Mass.). The samples were tested using a QuadTech LCR Model 1900 testing device as sold by QuadTech, Inc. of Marlborough, Mass.
In particular, all three samples were then tested as per AAMI EC 12-2000-4.2.2.1 (modified) and AAMI EC12-2000-4.2.2.4. The AAMI EC12-2000-4.2.2.1 test has an upper limit of 3000 Ohms for the face to face double adhesive part of the test, for a single point and a max average (12 test samples) of 2000 Ohms.
The AAMI EC12-2000-4.2.2.4 calls for retaining less than 100 mV in 5 sec after a 200 DC volt charge, again using a face to double adhesive layer.
Note the Table 1 below, which shows impedance (EC 12-2000-4.2.2.1) tested first; DOR (EC 12-2000-4.2.2.4) was run next on the same samples.
To determine the signal receptivity of this invention, the samples prepared for Example 1 were tested in accordance to the procedure outlined below. The samples used in testing as per AAMI EC12-2000-4.2.2.1 were used connected in series to a Wave Form Generator (Hewlett Packard 33120A 15 MHz Function/Arbitrary Waveform Generator) and in series an Oscilloscope (BK Precision 100 MHz Oscilloscope 2190), schematically shown below. Samples were tested at 3, 10 and 100 Hz; results are given below in Table 2 in % of transmitted signal received.
Samples that passed the DOR test (AAMI EC12-2000s-4.2.2.4) were retested for impedance as per AAMI EC12-2000-4.2.2.1 (modified), upon rechecking, samples 1 & 3 had a remarkable change. Samples 1 and 3 now had an impedance of less than 1K Ohms. In sample 2, the signal receptive medium was unchanged post DOR test; only those samples with the dispersed conductive particles changed. Further, the resulting lower impedance was still anisotropic, i.e., in the Z direction (noting Example 4 as to how the anisotropic property was determined). In addition the parallel capacitance (CP) of the post DOR material actually increases as the Z impedance decreases, as shown below in Table 3.
80K
The anisotropic property was validated by the following test procedure. Signals at 3, 10, 100, Hz were generated, and fed to a first copper shunt, which was placed on the conductive adhesive. A second copper shunt was placed on the same conductive adhesive ˜0.004″ (100 microns) apart from the first shunt, which was connected (in series) to an oscilloscope. The base substrate was a dielectric material (PET film) Following electrophoresis therefore, the composite may have a resistance of less than about 3,000 Ohms, less than about 2,000 Ohms, less than about 1,000 Ohms or even less than about 500 Ohms.
If the Sample 1 adhesive was isotropic it would have been expected to pick up a signal on the oscilloscope. If the Sample 1 adhesive was anisotropic it would have been expected that no signal would be received on the oscilloscope. The result was that no signal was detected.
The electrophoresis result does not appear to rely on the presence of the polar material in the composite. It is believed that the carbon particles are agglomerated by the electric field applied during the DOR test; that the electric field generated by the 200 DC volts being applied across the conductive particle containing SRM and/or the conductive particles just with a PSA (no polar organo-salt), is sufficient to cause the particles to agglomerate together.
The agglomerated structures spanning from one electrode to the other are the reason an anisotropic conductive PSA is formed. To examine these agglomerations, reference is made to
This particle migration effect can be shown in more detail by looking at
It is significant, however, that in this case the agglomeration occurs in a non-aqueous high viscosity medium. In accordance with the present invention, the continuous medium is a dielectric and is in full contact with the conductive particles (at the particle loading levels) and the medium is a viscoelastic liquid, i.e., has a very high viscosity, five times plus orders of magnitude higher (as measured in centipoises) than water dispersions (often measured in the only the 10 s of centipoises).
Again, what is postulated here is that, as in the case of particle agglomeration via an overcharge electric field in an aqueous continuous medium, a slight charge is induced on a nearby particle near an electrode. With the continuous medium being less polar and more dielectric than water however, a greater charge build-up can occur on a particle in the electric field.
With water as the continuous medium the higher polarity would mitigate the charge build up, further if the applied electric field were increased (higher voltage) electrolysis of the water would become a competing complication. With a PSA (FLEXcon's V-95 acrylic adhesive) as the continuous medium there is much less charge mitigation and no substantial electro-chemical process that occurs.
This charge build-up on the particle increases the attractive forces between the particle and the electrode, thus drawing the particle to the electrode in spite of the higher viscosity of the continuous medium. Further, the first particle that reaches the electrode forms an incremental high spot on said electrode thus the electric field is moved closer to the other electrode, as more particles join the agglomeration the field strength increase as the distance to the opposite electrode decreases, thus accelerating the agglomeration growth.
The DOR test involves a plane to plane electrode arrangement; after a few conductive structures are formed therefore, the electric field between the two electrodes is mostly dissipated due to the contacts already made between the electrodes. Thus the first structure will form, where there is one spot where the two planes are closer to one another or there is an uneven distribution of carbon such that a slightly higher density of the conductive particles are at one increment, between the plane, in other words that point of least resistance.
As a result using the plane to plane method in forming these structures has some limits as to the position and number of conductive structures formed. When a point-to-plane or point-to-point method is used to introduce the electric field however, more discrete in position and number of conductive structures would be formed as each point has its own electric field which is not readily dissipated when nearby conductive structures are formed.
This was demonstrated by using a lab corona treating device on a conductive substrate that was grounded. The lab corona treating device acted like a series of point sources to a plane receiving substrate. What resulted was a uniformly distributed conductive structure across the surface of the adhesive.
The testing of the stability of the in situ formed electrically conductive structures was accomplished by placing post DOR test samples in an oven at 160° F. (71° C.) for 16 hours and retesting the impedance (AAMI EC 12-2000-4.2.2.1.) and signal receptive properties. In all cases the samples maintained the lower impedance.
The invention therefore provides that an overload protected capacitively coupled, water content insensitive, composite may be provided that includes a polymer and a polar material dispersed therein, and electrically conductive particles, such that in the event of overcharging, the impedance as measured by AAMI EC12-2000-4.2.2.1 becomes less than 3,000 Ohms. The conductive particles may be in the form of carbon, and may be provided in a concentration greater than 1% on solids, dry weight. The composite may be anisotropic, and the polymer may be a pressure sensitive adhesive for use in an ECG electrode that satisfies the standards of AAMI EC-12-2000-422.4 for overload recovery
The use of the composite 92 of the present invention, however, provides that the conductive layer 94 does not need to be formed of an expensive material such as silver/silver chloride (AglAgCl) as is required with hydrogels. Hydrogels require such specialized conductive layers because the ionic conductivity of the hydro gel must ionically couple to the electrode. In accordance with the present invention on the other hand, the conductive layer 94 may be formed of an inexpensive deposited layer (e.g., vacuum deposited or sputter coated) of, for example, conductive particles such as those discussed above but in a much higher concentration to form a conductive layer upon deposition. Such less expensive materials may be used for the conductive layer because the mechanism for conduction (whether by the polar material or the conductive material) is not ionic conductivity.
The use of inexpensive materials for the conductive layer also permits that a variety of connection options may be provided on a single biomedical electrode. For example,
Composites of further embodiments of the invention may employ carbon nanotubes. Such composites also undergo the electrophoresis process discussed above during overcharging, but the agglomeration results in a jumbled nest of the nanotubes given the very high aspect ratio of the nanotubes (e.g., upwards of 1000 to 1). For example, a composite 150 may include carbon nanotubes 152 dispersed within a binder material 154 as shown in
In accordance with a further example therefore, an adhesive mixture including FLEXcon's V-95 acrylic adhesive, a polar material (Arquad HTL-8 sold by AkzoNobel, 20% solids on solids of the V-95 adhesive, and 0.04% single walled semi-conductive carbon nanotubes (CNTs). The mixture was provided in a 3% solids paste in a 72/28 solvent blend isopropyl alcohol/n-butyl alcohol (sold by Southwest Nanotechnologies of 2501 Technology Place, Norman, Okla. The mixture was sonicated for 30 minutes to evenly disperse the CNTs throughout the adhesive/arquad premixture.
The mixture was then coated, dried and cured as discussed above to a 2 mil (50 micron) dried thickness. The adhesive composites were made and tested as discussed above. The results were that the pre-DOR test (as per EC12-2000-4.2.2.1) showed an impedance of 100 k Ohms. The DOR test (as per EC12-2000-4.2.2.4) was pass, and that the impedance post EC12-2000-4.2.2.1 was 5 K Ohms. The signal receptivity was tested as in Example 1 to be both 95% before and after DOR. The anisotropy test as discussed above with respect to Example 3, found that there was an X and Y conductivity component to the composite post DOR. It is expected that more uniform istropic conductive coatings may be formed.
As noted above, if the particle concentration in a pressure sensitive adhesive is high enough to form a network in which particle-to-particle contact is maintained then there is little chance that the adhesive component is present in high enough concentrations to flow out to make surface-to-surface contact between the substrates and an electrode, i.e., act as an adhesive. In a further example, to the adhesive material of Sample 1 (the V-95 PSA and polar material) was added 25% by weight of the carbon particles of Sample 1. The composite was then coated and dried onto a polyester based siliconized release liner to a 2 mil (50 micron) dry deposition. The resulting coating had substantially no measurable PSA properties (tack, peel, shear). An electrically conductive network, however, had formed in the composite, and this composite was found to have a DC resistance of about 100 Ohms both before and after electrophoresis.
Those skilled in the art will appreciate that numerous modifications and variations may be made to the above disclosed embodiments without departing from the spirit and scope of the present invention.
| Number | Date | Country | |
|---|---|---|---|
| Parent | 13272545 | Oct 2011 | US |
| Child | 14094993 | US |
