Patent Grant
11203132
The present disclosure relates generally to a method and system for forming composite materials and the composite materials formed thereby. More particularly, the present disclosure relates to a method and a system for forming composites from a viscoelastic matrix material or a composite that exhibits induced viscoelastic behaviour with fillers incorporated therein.
The production of composite materials, particularly involving plastics, emerged at the beginning of the 20th century and has continued to experience significant growth ever since. Today, there is strong pressure to make composite materials, such as plastic blends, which often have improved properties over conventional plastics and are cost effective. These demands have placed substantial pressure on the plastics industry to improve polymer processing technology and resultant materials.
In general, composite materials may be stronger, lighter weight, less expensive, and less susceptible to breakage than traditional materials. For instance, polymer based composites have shown great promise in many industries including aerospace, electrical, medical, transportation, and environmental compared to other traditional materials. Manufacturers of composite materials are tasked with determining the best balance of properties, processing characteristics, and economic considerations for a given specific application. Particularly, they must determine the proper combination of micro-sized and nano-sized fillers for the desired property of the material.
Conventional processing methods include mixing micro-sized and nano-sized fillers in polymer composites. Conventional mixing technologies, such as high shear mixers and extrusion compounders, generally rely on classical mechanical forces for dispersive mixing. However, these techniques are typically limited to micro-sized fillers as it can be difficult to breakup nano-sized agglomerations using these techniques. In order to use nano-sized fillers, surfactants are conventionally used to reduce the surface energy between fillers, which may make it easier to break nano-sized agglomerations. However, the addition of surfactants may undesirably alter the properties of the final composite materials and may not solve the problem of limitation of loading level of micro- and/or nano-fillers in the matrix material. In this document, the viscoelastic matrix material will sometimes be referred to as a matrix material.
It is an object of the present disclosure to obviate or mitigate at least one disadvantage of previous systems and methods for dispersing micro- and/or nano fillers into matrix materials such as polymers.
In a first aspect, there is provided a method for forming a composite material, the method includes: combining a first component element with a second component element to form a composite mixture; subjecting the composite mixture to a first force to in order to form ligaments and disperse the first component element and second component element in relation to each other, wherein the first force is a mechanical force; subjecting the ligaments to at least one second force in order to form attenuated ligaments and further disperse the first component element and second component element in relation to each other, wherein the at least one second force imparts both shear flow deformation and extensional flow deformation to the ligaments to form the attenuated ligaments; and collecting the attenuated ligaments.
In a particular case, the at least one second force is a continuation of the first force.
In another case, the first component element is viscoelastic material and the second component element is a filler.
In yet another case, the viscoelastic material is a polymer.
In yet another case, the first force is a centrifugal force and the at least one second force are a centrifugal force and an electrostatic force.
In yet another case, the combining the first component element and the second component element includes pre-mixing the first component element and the second component element.
In yet another case, the composite mixture is a film.
In a further aspect, there is provided A system for forming a composite from at least a first component element and a second component element, the system includes: a feeder for feeding the first component element and the second component element as a composite mixture; a first disperser for dispersing the first component element and second component element in relation to each other within the composite mixture using a first force to form ligaments, wherein the first force is a mechanical force; a second disperser for dispersing the first component element and second component element in relation to each other within the ligaments using one or more second forces to form attenuated ligaments, wherein the at least one second force imparts both shear flow deformation and extensional flow deformation to the ligaments to form the attenuated ligaments; and a collector for collecting the attenuated ligament.
In a particular case, the first component element is a polymer and the second component element is a filler.
In another case, the first component element is a first polymer and the second component element is a second polymer.
In yet another case, the feeder includes a first feeder for the first component element and a second feeder for the second component element and the first component element and second component element are pre-mixed in the feeder.
In yet another case, the composite mixture is a film.
In a further embodiment, the first disperser and the second disperser include a rotating surface configured to receive the composite mixture from the feeder at approximately the center of the rotating surface; the first force comprises a centrifugal force imparted to the composite mixture in a first predetermined portion of the rotating surface; the at least one second force includes a centrifugal force imparted to the ligaments at a second predetermined portion near the edge of the rotating surface and is configured to be sufficient to eject the ligaments off of the rotating surface; and the collector is a predetermined distance from the rotating surface
In a particular case, the at least one second force further is an electrical force provided between the rotating surface and the collector.
In another aspect, there is provided a composite material prepared using the method described above.
In a particular case, the resulting loading level of the first or second component element in the composite material is greater than approximately 10 wt %.
In another case, the resulting loading level of the first or second component element in the composite material is greater than approximately 50 wt %.
Other aspects and features of the present disclosure will become apparent to those ordinarily skilled in the art upon review of the following description of specific embodiments in conjunction with the accompanying figures.
Embodiments of the present disclosure will now be described, by way of example only, with reference to the attached Figures:
Generally, the present disclosure provides a method and a system for forming composites by mixing fillers and matrix materials (e.g., polymers) using a combination of shear and extension forces.
Typically, plastic processing can be characterized by: (1) mixing or homogenization, (2) blending of polymers, and (3) compounding. Compounding is generally the act of incorporating additives such as fillers into a polymer matrix. Mixing, blending, and compounding can be complex processes involving specialized machinery and know-how to produce materials with desired properties.
Machinery for polymer processing typically employs a combination of two forms of mixing to make polymer composites: (1) distributive mixing and (2) dispersive mixing. Distributive mixing is typically the act of homogeneously distributing properties of a polymer compound, such as one with uniform temperature. Dispersive mixing can be more complex as it typically involves the application of stresses, often shear stress. The stress is applied to break up the domains of the dispersed phase, such as fillers, to be embedded in the polymer matrix. Irrespective of filler type, it may be difficult to dispersively mix and break up micro and/or nano fillers since they tend to agglomerate due to their surface energy arising from Van der Waals forces.
Consequently, filler agglomerations restrict loading levels (that is, the amount of filler that can be added) and adversely affect the processability of a compound due to the increase in viscosity. The input mixing energy intensity may be dependent on the mode of deformation, which generally arises from either shear or extensional flow deformations. Efficient deformation of a compound generates a polymer filler interfacial surface so that the input mixing energy can infiltrate, for example locally-attack, and overcome the surface energy barrier of agglomerated filler structures. The relationship between required input energy, for example mixing energy, and the surface generation, for example interfacial growth, was examined by Utracki (L. A. Utracki, “Polymer blends handbook,” Vol. 1, 2002, p. 577-585). The results of the Utracki examination are shown in
Some polymer processing technologies for compounding micro and/or nano composites may include direct use of high shear mixers, roll mixers, Banbury mixers, and extruders such as counter-rotating twin-screw extruders. These approaches typically use mechanical forces for distributive and dispersive mixing and are typically designed to exploit deformation based on shear flows rather than extensional flows.
Certain processing technologies for production of advanced composites with nanoscale fillers may leverage extensional flows. For instance, extruder screw and high shear mixing blade designs have been modified to generate extensional flow fields. However, in these devices, extensional flow deformation is generally applied to a bulk-material due to restrictions of the mature technology architectures. When extensional flow deformation is applied to bulk-material, polymer film generation is limited by the imposed stress; thus, the imposed input energy is often ineffective in breaching the energy barrier to breakup agglomerated filler structures.
Contrary to classical mechanical methods, other techniques, such as dual asymmetric centrifugal (DAC) mixers, may also be used for dispersing fillers in liquids and compounds. However, DACs typically may suffer from poor scalability and are generally only capable of achieving filler loading levels similar to that of classical mechanical methods.
High pressure homogenization and sonication may be effective for filler dispersion; however, these methods are only suitable for dispersion of fillers in low viscosity liquids, such as solvents, rather than polymers.
Chemical treatments such as surfactants, dispersant aids, and filler surface treatments may also be used, often in conjunction with conventional mechanical methods. Chemical treatments may reduce the surface energy between fillers, and the interfacial tension between fillers and the polymer. This reduction may make it easier to break up agglomerations during mixing. However, these chemical treatments may be expensive. As well, these chemical treatments may alter the final composite properties and can also manifest as contaminants and volatile organic compounds (VOCs) which are harmful to humans and the environment. Further, using these chemical treatments, the loading level of nanostructured fillers in the final composite may still be limited. Consequently, conventional approaches for exploiting extensional flow deformation for dispersive mixing have a number of limitations. Thus, there is a strong market demand for improved polymer composites than what can be provided with conventional processing approaches.
When dispersing nano and/or micro fillers in a polymer matrix, a difficulty may arise when attempting to achieve a better dispersion of fillers in the matrix. Very small size fillers, generally in the range of micro and/or nano scales, normally tend to agglomerate due to their surface energy arising from Van der Waals forces. Thus, agglomerations are typically difficult to breakup. Breaking these agglomerations may be even more difficult in a polymer matrix due to the higher viscosity of polymers compared to the lower viscosity liquids. Thus, better dispersion and a lower degree of agglomerated fillers, namely agglomeration occurrence, size, and distribution, may be needed to achieve a desired set of properties for the final composite material.
Certain mixing technologies, such as high shear mixers and extrusion compounders, rely on classical mechanical forces for dispersive mixing, for example shear flow deformation, to break up agglomerated fillers. However, these techniques are typically limited to micro-sized fillers as it becomes increasingly difficult to breakup nano agglomerations. In certain cases, surfactants may be used to reduce agglomeration of nano-fillers. Surfactants reduce the surface energy between particles, which may make it easier to break agglomerations. However, the addition of surfactants alters the properties of the final composite material and the loading levels of nanofillers in the final composite will generally still be limited.
Typically, a combination of micro and nano fillers may result in a desired compromise between material property enhancement and cost. Nano fillers are typically more expensive than their micro filler counterparts. Nano fillers are generally dispersed first in the polymer matrix and then micro fillers are dispersed. However, this sequence of adding nano fillers to the polymer first increases the mixture viscosity, thereby possibly adversely affecting how well micro fillers are subsequently dispersed. As a consequence, the final composite properties imparted by the fillers may be restricted. Due to the challenges faced with rising compound viscosity with nano fillers, nano filler loading levels are conventionally low and the mixing process is energy intensive.
Polymer composite compounding may be used to implement and utilize the principles of extensional flow deformation. Conventionally, extensional flow deformation may be used for making nonwoven fiber materials. Conventional uses of extensional flow deformation for this purpose generally do not involve the mixing of materials, but rather the formation of small fibers. However, extensional flow deformation of a fiber-shaped polymer, namely liquid jets, was determined to be applicable for the dispersion of fillers in matrix materials, and thereby applicable for the formation of composites.
Specifically, as described herein, embodiments of a system and method for forming a composite material are provided. Fillers are added to a polymer matrix, and then the composite mixture is deposited as a film on a rotating surface. The film flow is then ejected or spun from the rotating surface in the form of finger-like ligaments such that the mixture undergoes shear and extensional flow deformation. The ligaments may also be subjected to an applied electric field (or other forces) situated between the rotating surface and a collecting surface, further contributing to shear and extensional flow deformation and filler dispersion. The process is intended to be highly intensive as the composite can be broken-down into hundreds of nanometre scale ligaments where fillers are dispersed within each ligament. Hence, dispersion may be performed simultaneously on all ligaments, nearly at the microscopic level, rather than at a bulk level like that of an extrusion process. This process is intended to result in better dispersion of micro and/or nano fillers at higher loading levels and higher production rates than conventional processes.
Multiple aspects of the formation process are intended to assist with dispersal of the fillers, including, material feeding, rotating surface, ligament formation process and ligaments themself. At various times in the formation process, the agglomerated fillers may be acted upon by various forces, for example, mechanical, electrical, electrophoretic, dielectrophoretic, magnetic, and the like. For instance, forces may be applied: at a pre-mixing stage; during film flow on a rotating surface that includes distributive and dispersive mixing via shear flow deformation due to centrifugal force; during ligament formation that includes shear flow deformation due to centrifugal force; during ligament thinning at the edge of the rotating surface that includes shear and extensional flow deformation due to centrifugal, aerodynamic, electrostatic, electrophoretic, and/or dielectrophoretic force; and while subject to a region where the ligaments undergo bending instability that includes direct filler dispersion and distribution via Coulomb force. It is intended that these various forces and times of application of forces result in greater filler distribution and dispersion compared to conventional methods.
During the entirety, or majority, of the formation process, ligaments are intended to remain in a liquid-phase or amorphous-phase, which is typically contrary to conventional techniques. This phase may permit filler dispersion in ligaments under the application of an electrostatic field and mechanical forces.
In some conventional approaches, the objective is generally to produce a nonwoven matrix of dry fibers. In this process, a volatile component is usually required to evaporate from the mixture, making a phase change from liquid to solid, so that polymer ligaments solidify before depositing on the collection surface.
In contrast, in the embodiments described herein, since ligaments can remain in liquid phase, the ligaments may be deposited on the collection surface and coalesce back into a bulk heterogeneous and well-dispersed composite. The simultaneous production of a plurality of ligaments may be generally greater from a rotating surface than from conventional devices. Thus, it is intended that dispersed composite production rates are higher with the use of embodiments such as those described herein. In addition, a change in the rotating surface speed can modulate the ligament geometry, and ultimately affect filler dispersion in the polymer. A variation in the rotational speed of the rotating surface provides a means to tune filler dispersion since the ligament geometry is modulated by the rotational speed, a parameter that cannot otherwise be controlled using conventional devices.
Turning to
Fillers may include both micro-sized and nano-sized objects that exist in defined singular form and have at least one dimension in either approximately the nano scale range or the micro scale range. These objects may include particles that have three dimensions in the nano and/or micro scale ranges, fibres or tubes that have two dimensions in the nano and/or micro scale ranges, and plates or flakes that have one dimension in the nano and/or micro scale ranges. In some cases, mixtures may contain only nano-sized fillers, only micro-sized fillers, or nano-sized and micro-sized fillers. The physical state of the filler may be solid, liquid, or gaseous. During the preparation of the filler colloid at 202, efficient filler dispersion techniques, such as ultrasound sonication or high-shear mixing, may be used to disperse fillers in a low viscosity compliant liquid. Fillers may be mixed into a low viscosity compliant liquid in order to generally facilitate easier dispersion. In this way, dispersion of the fillers can be undertaken prior to the fillers being introduced into the polymer; as there may be difficulty if one were to directly disperse fillers in a higher viscosity material such as a polymer. In further cases, where high viscosity liquids are used, a high shear mixer may be employed to disperse the fillers.
At 204, a mixer pre-mixes the prepared filler colloid with at least one polymer, for example, a polymer solution, liquid polymer, or polymer melt, to form composite mixture (herein generally referred to as a composite mixture). The composite mixture may be mixed using a conventional mixing technique, for example using shear flow deformation. In some cases, such as higher viscosity polymers high shear mixing may be used. The mixing of the filler colloids, or composite mixture, may be undertaken at room temperature or at an elevated temperature, for example, below the degradation temperature of the matrix material in the composite mixture. Elevated temperatures can be supplied by quiescent air sources, convecting air sources, or any other heating methods known in the art. It is intended that increasing the temperatures may decrease the viscosity of polymer ligaments; or in the case of polymer melts, keep the polymer in a melted state. In other cases, the mixing can be undertaken at sub-ambient temperatures. Sub-ambient temperatures may allow predetermined regulation of the viscosity or amorphousness of the composite mixture. Polymers, for example some rubbers, may be amorphous below ambient temperature and cure a relatively moderate ambient temperatures.
In some cases, preparation of the liquid-filler colloid at 202 may be omitted and the method 200 may begin with preparation of the composite mixture at 204. For instance, a composite mixture can be prepared by directly mixing fillers with polymer.
Surfactants can be added to improve constituent dispersion. Surfactants may be added during preparation of the liquid-filler colloids at 202 or during preparation of the composite mixture at 204. A suitable surfactant may be used, for example, Triton™ X 100, Tween™ 80, Tween™ 20, Span™ 80, ionic surfactants, non-ionic surfactants, or the like.
At 206, a system for forming a composite material such as a ligament generation device, of the type illustrated by the rotary disperser described herein, generates ligaments. In this example and other herein, the ligaments are generally liquid or amorphous. A ligament is generally a thin stream/section of the composite mixture. Although the focus of the description herein is on a rotary disperser, there may be several techniques for generating ligaments. For example, other techniques, systems or devices may employ various mechanical forces to generate ligaments, for example centrifugal force, pressure, or the like. In an example, pressure may be applied to a polymer/filler mixture in a chamber, thereby squeezing the polymer through a die plate containing an array of one or more holes. Upon passing through the die plate, the polymer composite emerges as one or more ligaments. As well, upon exiting the die plate, air jets may be actuated parallel to the ligaments, in the direction of ligament propagation, in order to further propel the ligaments through the air. In these cases, the ligaments may be generally liquid. For reference, devices that employ pressure and aerodynamic forces for generating ligaments may be generally referred to as melt blowing or melt spraying devices.
Other techniques, systems and devices may also employ atomization techniques to generate the ligaments. A polymer-filler composite ejected from the atomization nozzle or rotating surface may inherently form ligaments rather than droplets due to the viscoelastic behaviour of the polymer.
In further cases, ligaments can also be formed by employing electrical forces. In yet further cases, there may be other devices that may be employed which combine electrical, mechanical and/or other forces in order to generate ligaments. A commonality of the above described devices and associated force mechanisms are that the ligaments are strongly subjected to shear and extensional flow deformation mechanisms. In general, embodiments of a system and method for forming a composite material are intended to involve ligaments being subject to a mechanical force, ejected from a source location, and are subject to a further force or forces such that the ligaments propagate in a way that the ligaments are further attenuated until the attenuated ligaments are deposited at a collection site.
At 208, multiple force mechanisms, as described herein, provide filler dispersion in the ligaments. While in the disperser, the fillers may be strongly dispersed in the ligaments by subjecting the ligaments to multiple force mechanisms during the ligaments' movement/flight path. The dispersion in the ligaments may be through one or more of the force mechanisms described below.
Force may be applied to the ligaments by an electric field. The electric field may be generated across the ligaments' flight path from the source to collection location by, for example, applying a high voltage at the ligament generation location, namely the disperser, and grounding the collection location, namely a collection surface. The centrifugal, pressure, and/or aerodynamic forces described above may impose shear and extensional flow deformation, thereby thinning the ligaments. The electric field may then induce further ligament thinning by extensional and shear flow deformation via electrostatic, electrophoretic, and/or dielectrophoretic forces on the ligaments.
The ligaments may then be subjected to further extensional and shear flow deformation via a bending instability. The bending instability is intended to be due to the Coulomb forces of electrically charging the ligaments and/or mechanical forces arising from aerodynamic instability of the ligaments, resulting in very thin ligaments with sub-micronic dimensions. During the flight path, the dispersion can be very significant due to strong extensional and shear flow deformation acting on a vigorously whipping ligament. Due in part to the ligaments possibly being on the order of nanometres in cross-section, the velocity of the ligaments in this region can be several times the speed of sound. In addition, since the ligaments diametral dimensions may be on the nanoscale, charging of fillers with the same polarity within the ligament can result in strong repulsion of the charged fillers, which may further enhance the dispersion. In some cases, the medium in which the ligaments are immersed during the flight path can be at a predetermined temperature; for example, at ambient temperature, at elevated temperatures, or at sub-ambient temperatures. Elevated temperatures can be supplied by quiescent air sources, convecting air sources, or any other heating methods known in the art. It is intended that increasing the temperatures may decrease the viscosity of polymer ligaments; or in the case of polymer melts, keep the polymer in a melted state. Sub-ambient temperatures may allow predetermined regulation of the viscosity or amorphousness of the composite mixture. Polymers, for example some rubbers, may be amorphous below ambient temperature and cure a relatively moderate ambient temperatures.
At 210, the ligaments are deposited on a collection surface. During filler dispersion in the ligaments, compliant liquid may or may not evaporate while the remaining composite mixture constituents will be deposited on the collection surface. It is intended that the ligaments remain in liquid or an amorphous phase during the entirety, or majority, of the process. As a consequence, when the ligaments deposit on the collection surface, the ligaments can coalesce to form or reform a well-dispersed heterogeneous bulk material, film, porous material, or the like.
Turning to
With the rotary disperser 300, polymer and filler composites can be formed either by pre-mixing the composite mixture, or by direct mixing of the fillers and polymers at the feeder 304 or on the rotating surface 308.
Fillers may be dispersed in a compliant liquid first, forming liquid-filler colloids, prior to integration with a polymer to form the composite mixture. In the alternative, fillers may be directly integrated with the polymer to form the composite mixture.
The composite mixture is then delivered to the feeder 304. The feeder 304 may be, for example, a tube, valved conduit, or the like. The feeder 304 deposits the composite mixture onto the rotating surface 308. The rotary disperser shown in
The rotating surface 308 rotates via mechanical connection to the motor drive 314. In further cases, any arrangement or mechanism to rotate the rotating surface 308 may be used. In the example of
In the embodiment of
In some cases, after deposition of the ligaments on the collection surface 310, the ligaments can undergo various types of post-processing to make a desired composite. Post-processing may include, for example, cross-linking, curing, or the like.
In the embodiment of a rotary disperser 400 shown in
In the embodiments of
In further embodiments, as shown in the rotary disperser 500 of
The composite mixture can be deposited at room temperature or elevated temperature. In addition, the rotating surface 308 and collection surface 310 can be operated at room temperature or elevated temperature. It is intended that operating at an elevated temperature may decrease the viscosity of polymer ligaments; or in the case of polymer melts, keeps the polymer in a melted state. In other cases, the composite mixture can be deposited, and/or the rotating surface 308 and collection surface 310 can be operated, at sub-ambient temperatures. Sub-ambient temperatures may allow predetermined regulation of the viscosity or amorphousness of the composite mixture. Polymers, for example some rubbers, may be amorphous below ambient temperature and cure a relatively moderate ambient temperatures.
Due to the centrifugal force acting on the freely movable film 306 imparted by the rotating surface 308, ligaments are formed on the rotating surface 308 and, in particular, at or near the edge 316 thereof; in this case, at the edge of the rotating cone shape. The composite mixture is subjected to shear flow deformation as it nears and propagates over the edge 316 of the rotating surface 308. Due to this deformation, the composite mixture breaks up from a film 306 into ligaments, which further disperses the fillers in the composite mixture. In particular, in this process, the ligaments are stretched a significant amount such that the ligaments exit the edge 316 as attenuated ligaments. Along with the centrifugal forces acting on the composite mixture due to the rotating surface 308, the composite mixture is also subject to viscous forces and surface-tension forces; which all impart shear and extensional deformation on the mixture.
Once the ligaments are spun or ejected from the edge 316 of the rotating surface 308, the ligaments are subject to the same or additional forces and further filler dispersion takes place via strong extensional and shear flow deformation to produce attenuated ligaments, as described above. The attenuated ligaments then reach the collection surface 310 where the composite material is deposited. The collection surface 310 can be configured to have any arrangement, shape or structure needed to ensure that substantially all of the material in the attenuated ligaments gets deposited on the collection surface 310.
It is intended that the collection surface 310 be configured to be at a distance and arrangement to substantially collect the ligaments after being ejected from the edge 316. However, where there is a voltage applied, the collection surface 310 should not be so close as to cause arcing between the rotating surface 308 and the collection surface 310.
Turning to
In one application of the dual-feeder arrangement, filler colloid and polymer solution, liquid or melt can be mixed concurrently with the dispersion caused by the rotating surface 308. Two distinct mixtures are deposited by each of the feeders 602, 604 on to the rotating surface 308. For example, a liquid polymer by the first feeder 602 and a liquid-filler colloid by the second feeder 604. In this case, prior mixing of the prepared liquid-filler colloid with the polymer, as described above, may not be required (i.e., see 204 in
In a further application of the dual-feeder arrangement, the first and second feeders 602, 604 may be used to mix polymers. In this case, fillers may not be required or fillers can be introduced in the mixture by a further feeder. In a further application of a multi-feeder arrangement, the first and second feeders 602, 604 may be used to feed two different filler colloids and a third feeder can be introduced to feed the polymer solution, liquid, or melt. Similar to described herein, there can be multiple arrangements to feed polymer or any other viscoelastic material, filler, filler-colloids, and other additives on to the rotating surface 308.
In further embodiments, for both single-feeder and multiple-feeder arrangements, the fillers and polymers may be mixed by combining streams of polymer and fillers in a feeder.
In some embodiments of a feeder, the premixed mixture may pass through a static mixer to further enhance mixing. An example of a static mixer feeder 800 is shown in
In a further embodiment, the filler and polymers may be mixed by combining streams of polymer and filler in the annulus of a concentric tube feeder, as shown in
In any of the feeder arrangements, the flow stream inputs may generally be interchangeable. For instance, for the concentric tube feeder 900 of
For each of the above feeder arrangements, fillers may be transported from a source location to the feeder by liquid fluidization, gravity feed, and/or any other known techniques. A liquid-fluidized dosing stream may consist of fillers with identical characteristic features or a plurality thereof. In addition, there may be a plurality of filler dosing streams with identical filler characteristic features or a plurality thereof. Moreover, the filler loading level and flow rate of each dosing stream may be the same or may be different. The carrier liquid in each liquid-fluidized dosing stream may also either be the same or be different. There may be a singular characteristic type of host polymer, for example chemical type, viscosity, molecular weight, or there may be a plurality thereof.
The composite mixture passes through the dispersion element due the centrifugal force acting on the composite mixture before the mixture emerges from the rotating surfaces 1304, 1306 where it is then collected by a collection surface (not shown). In further cases, the arrangement and location of the static mixer 1302, or dispersion element, can differ from that shown in the embodiment in
An example of an application of the rotary disperser described herein is for composite formation in insulator applications. Composites in insulator applications commonly use two types of fillers. Fumed silica (SiO2) in nano-size may be used as reinforcement filler to lend physical strength to a polymer. Alumina trihydrate (ATH) in micro-size may be used to improve arc resistance. However, the use of nano-sized fumed silica in a silicone matrix typically limits the processing capability and final filler loading. This is due to the fumed silica, when compared to the other nano-sized fillers, significantly increasing the viscosity in the case of, for example, liquid silicone rubber (LSR) or room temperature vulcanize (RTV), or silicone rubber gums, for example high temperature vulcanize (HTV) or high consistency rubber (HCR).
Irrespective of filler type, it is conventionally inherently difficult to disperse fillers in a polymer matrix, especially as the filler size decreases to the micro and nano scales. This is primarily due to the particles tending to agglomerate because of their surface energy arising from Van Der Waals forces. As well, a silica particle-particle interaction mechanism exists that further increases the difficulty of dispersing this type of filler. There is a strong affinity between silica arising from hydrogen bonding, which results in a tendency for silica particles to aggregate in small chain-like structures. According to Raghavan & Khan (S. R. Raghavan, and S. A. Khan, “Shear-induced microstructural changes in flocculated suspensions of fumed silica,” J. Rheology, Vol. 39, No. 6, pp. 1311-1325, 1995), at low to moderate filler loading levels, aggregates form interconnected structures referred to as flocs. An example of a silica floc structure is shown in
It is intended that the properties of composite insulators can be significantly improved by employing embodiments of the rotary disperser 300, 600 and method described herein. The rotary disperser 300, 600 is intended to allow particle aggregations to be directly, locally, and efficiently broken down, thereby increasing the absolute filler loading level that can be incorporated into the composite insulator materials. Very high loading levels of fillers into polymer matrices may be used and the output may be a bulk composite. For example, in the case of fumed silica in liquid silicone rubber, the maximum filler loading level may be greater than 30 wt % in contrast to conventional techniques. In contrast to conventional techniques, the filler percentage in liquid silicone rubber will typically be a significantly lower value. This is due to higher loading levels typically increasing the viscosity For example, in the case of fumed silica in silicone rubber, the typical maximum filler loading level is approximately less than 10 wt %. As such, embodiments of the dispenser and method herein have been shown to able to provide loading levels above approximately 7 wt %, above approximately 10 wt %, above approximately 15 wt %, above approximately 30 wt %, and above approximately 50 wt %. It is believed that there may be no theoretical upper limit on loading level using the embodiments described herein.
With the high filler loading levels available using the embodiments disclosed herein, the rotary disperser and method may be used for coating polymers or coating fillers. At high loading levels, the fillers may effectively become coatings on the polymer particles or vise versa. As shown in the example illustration 1500 of
In the case of fumed silica in silicone rubber, the material may remain at a lower viscosity while having a high loading level in comparison to matching materials prepared using conventional mixing equipment. This property is contrary to conventional techniques which typically convert the composite mixture to be a solid or semi-solid. In some cases, the composite can retain approximately the same viscosity while having the higher loading level. This property may allow the composite to be used in various types of machinery.
Examples of applications for high loading level mixtures may include, for example, emulsions, paints, nanocomposites, tire rubber compounds, or the like.
Materials formed using the embodiments described herein may be able to possess higher electrical permittivity and thermal conductivity, and less viscosity, than for conventional materials with the same loading level. As well, the embodiments described herein permit keeping the viscosity relatively low for a given loading level.
The determinations and results presented below are intended to demonstrate the effect of embodiments of the dispersion system and method described above on aggregate physical properties; such physical properties will be examined since they are linked to the filler microstructure in a composite. For instance, with an increasing degree of filler dispersion, it is understood that agglomerated structures, for example large aggregated groups, flocs, or networks, may be broken down into small structures or even individual isolated filler particles in the polymer matrix. As a result, composites were prepared using two different mixing techniques: (1) with a conventional high shear mixing and (2) with multiple force mechanism dispersion as described herein. It is intended that the composites prepared with these two mixing techniques should exhibit different aggregate physical properties as a consequence of differences in the filler microstructure, which in turn, arises from the distinct differences in the degree of dispersion.
The following examples were conducted by the applicants to technically validate that: 1) the multi-force dispersion process (MFD) does not negatively alter the compound constituents, and 2) filler dispersion and final composite properties are improved over compounds prepared with conventional processing counterparts.
Polymer compounds, namely, uncured/flowable composites, were prepared using room temperature vulcanized (RTV) silicone elastomer (RTV 615) and reinforcing fumed silica nano fillers (Aerosil 300VS) with MFD technology. Molecular weight (MW) measurements were carried out from Gel Permeation Chromatography (GPC) before (Sample 1) and after (Sample 2) MFD are shown in Table 1. Polymer MW measurements after MFD were made by removing fillers from the compound according to standard GPC techniques. As shown in Table 1, since the polymer mass average molecular weight (Mw), number average molecular weight (Mn) and Polydispersity index (PDI) are nearly unchanged before and after dispersion, the findings suggest that the polymer is not subjected to any process-related degradation, for example, chain scission or thermal degradation.
Polymer compounds with a highly aggregating filler, nano fumed silica (Aerosil 300VS), in RTV 615 were prepared with conventional high shear mixing (Ross HSM-100LSK) and MFD in order to examine differences in filler dispersability between the two technologies.
As shown in Table 2, a maximum loading level of 10 weight percent was reached with high shear (Sample 4), while the further inclusion of fillers was restricted due to the very high compound viscosity, likely due to the significant extent of filler aggregation. The addition of fillers transforms the compound into a gel-like high viscosity material and therefore, the viscosity was not measurable using a standard Malvern-Bohlin controlled stress/strain rheometer. Meanwhile, as shown in Table 2, loading levels above 10 weight percent were prepared with MFD (Samples 5 & 6) with a lower viscosity than that of the high shear mixed compounds at 10 weight percent. Since the lower reported viscosities with MED cannot be a consequence of process-induced degradation such as polymer chain-breaking (as evidenced by Example 1), the reported findings substantiate that the reduced viscosity and tolerance for higher loading levels of MFD are linked to filler dispersion and distribution occurring at microscopic levels, enhancing the filler-polymer interaction. In addition, scanning electron microscopy (SEM) images for composites with 10 weight percent fumed silica filler in RTV 615 are shown in
As summarized in Table 3, polymer composites with a highly aggregating filler, nano fumed silica (Aerosil 300VS), in RTV 615 were prepared with conventional high shear mixing (Sample 8) and MFD (Samples 9-12) in order to examine the effect of filler dispersability and loading level on mechanical properties for both mixing technologies. The test samples were prepared by adding the RTV 615 curing agent (part B) to the primary mixture (fumed silica and RTV 615A) and then curing the samples at elevated temperature (175 deg. C.) and pressure (3300 psi). As described in Example 2, a maximum loading level of 10 weight percent (Sample 8) was reached with high shear, while the further increase of filler loading level was restricted due to the significant increase of compound viscosity. Meanwhile, dispersion of more than 25 weight percent fumed silica in RTV 615 was possible with MFD. As shown in Table 3, the hardness of the composite increases with the increase in filler loading level. Notably, the hardness increases from 55 (Shore A) to 80 (Shore A) by increasing the filler weight percent from 10 to 25, respectively, with MFD compared to high shear mixing. A decrease in tensile strength and elongation of the composites were observed with the addition of more crystalline ceramic fillers. However, a marked increase in tensile strength was observed with further increase in loading level of fillers (Sample 12) with MFD technology.
In accordance with materials used for high voltage insulators, composite samples in Table 4 were prepared using different concentrations of micro and nano silica and ATH fillers in a polymer matrix of liquid silicone rubber (RTV 615). The samples were cured by adding the curing agent (RTV 615 B) and elevating the temperature (175 deg. C.) and pressure (3300 psi). The temporal change in temperature at a fixed location on the surface of a cured composite sample was measured (measurement location) for samples with silica filler (silica composites) and samples with ATH filler (ATH composites). Temperature profiles were used to indirectly examine differences in thermal conductivity behaviour between the composite samples. A constant incident heat flux on the composite surface was generated by subjecting each sample to a laser beam (4000 mW) focused on the composite surface oppose to that of the measurement location (i.e., on the back surface of the sample). The sample and laser separation distance was 70 mm. A thermal imaging camera was used to measure the surface temperature at the measurement location. In addition, the thermal erosion of the composite was quantified by measuring the weight of eroded mass due to the laser heating by subjecting the samples to a 9400 mW laser for a duration of 10 minutes.
As shown in Table 4, three different samples were prepared for each composite type, for example silica and ATH, to compare the composite properties: 1) at matching loading levels prepared using conventional high shear mixing and MFD, and 2) at high loading levels only achievable with MFD against maximum loading with conventional high shear mixing.
Temperature profiles of silica composites and ATH composites are shown in
Differences in thermal behaviour for the two mixing methods can be understood by examining the filler microstructure as depicted in
Polymer compounds were prepared with nano and micro titanium dioxide (TiO2) to demonstrate the effect of dispersibility and loading level on the dielectric properties of polymer composites. Polymer composites (RTV 615) were prepared using micro and nano fillers with conventional high shear mixing and MFD as reported in Table 5. Higher loading level compositions were only achievable with MFD technology as the loading level of composites prepared with high shear mixing were restricted due to the significant increase in compound viscosity. After mixing, the test samples, as shown in Table 5, were cured at elevated temperature (175 deg. C.) and pressure (3300 psi).
Comparing samples prepared using conventional mixing for 30 wt % micro fillers (Sample 19) and 30 wt % micro and 10 wt % nano fillers (Sample 20) shown in
As shown in the graph of
It is intended that silicone composite based insulators generally have better hydrophobicity and lower surface energy than most organic/inorganic materials based insulators. The surface properties of silicone are unique, in that it recovers its hydrophobicity between contamination and/or corona episodes, while other materials progressively deteriorate. However, the polymer-filler combination is important in silicone based insulators. Processing and performances, including physical, electrical, and thermal, are all affected by the properties of the polymer. These properties may include, for example, molecular weight and structure, as well as properties of fillers, such as filler type, size, shape, surface treatment, and residual catalyst or contaminants. In determining the optimum formulation for specific applications, device manufacturers and material suppliers generally determine the best balance of properties, processing characteristics, and economic considerations.
Conventionally, reinforcing fillers are hard to mix into a silicone based polymer with any dispersion method. Silicone is hydrophobic while fillers are typically hydrophilic. This hydrophilic property may be good for reinforcing the material but it becomes difficult to add to the hydrophobic silicone. It was determined by the applicants that by adding the hydrophobic material to the mixture first followed by the hydrophilic material, the dispersion and the loading level of the hydrophilic material can be increased when compared with conventional approaches. As well, by adding the hydrophobic material to the mixture first, the size of particles may be controlled.
In the embodiments described herein, it is intended that a mechanical force such as centrifugal force may be used to form ligaments with diameters in the approximate range of several microns. The ligaments are then subject to additional or further forces to attenuate the ligaments to cause further dispersion of the filler in the polymer matrix. Compatible solvents and/or additives may serve as functional additives to promote filler dispersion via electric forces, for example, ligament whipping and filler repulsion. Using embodiments of the system and method herein, dispersion can occur without the need for precise handling of the composite mixture and allow for larger scale formation of composite materials with real-time dispersion occurring by ligament formation and attenuation of the ligaments.
It is intended that a large population of ligaments may be generated from the film 306 on the rotating surface 308. The applicants have determined that a rotating cone surface can generate multiple ligaments simultaneously, for example, up to 600 depending on the composite mixture viscosity, rotational speed, and feed rate. Hence, the production rate may be enhanced significantly relative to the dispersion approach using conventional techniques.
It is also intended that the embodiments described herein may provide greater versatility in filler selection. Both micro and nano fillers can be incorporated into a polymer matrix using this described approach. In further embodiments, other nano and/or micro structures, such as nanotubes, nanofibers, nano flakes, or the like, may likewise be dispersed into a polymer matrix.
It is also intended that the embodiments described herein will provide greater versatility in polymer selection, including the use of with polymer melts.
It is also intended that the embodiments described herein provide a greater range of mixture viscosities. The film flow generated from the composite mixture while on the rotating surface 308 due to centrifugal force serves to initiate ligaments for a wide range of polymer viscosities, particularly high viscosities, which suffer from poor flowability and deformation. Thus, it is intended that an inherent limitation in dispersions prepared using conventional mechanical mixing technologies and various other conventional approaches can be overcome.
It is also intended that, in the embodiments described herein, the combination of multiple force mechanisms simultaneously applied to ligaments are able to breakup filler agglomerations. As stated, conventional dispersion technologies generally apply stress arising from mechanical shear flow deformation to break up filler agglomerations. These techniques face barriers in achieving high loading levels and adequate dispersion, largely due to the inefficiency in generating a polymer-filler interfacial surface necessary to break up filler agglomerations. As well, dispersions prepared using conventional techniques suffer from low production rates and poor filler loading levels. In the embodiments described herein, electric forces applied to ligaments may be an effective technique to leverage stresses arising from shear and extensional flow deformation to disperse fillers in a polymer matrix. Further, the force mechanisms, from mechanical and electric forces, may be combined. Ligaments in the presence of mechanical and electrical forces are subjected to strong shear and extensional deformation arising from stretching, thinning, and whipping. As well, fillers are directly subjected to charge repulsion. This combination of forces and physical ligament whipping behaviour have been found to improve filler dispersion and loading levels in compounds compared to conventional dispersion approaches. These findings indicate that extensional flow deformation can be strongly exploited by combining mechanical forces, namely a centrifugal force, with electrical forces on ligaments to enhance filler dispersion and loading.
It is also intended that the embodiments described herein may use liquid polymer (thermosets) or melts (thermoplastics). The embodiments may incorporate fillers into the polymer using a liquid carrier, which can be a solvent, liquid, or using direct injection during the process. In that way, fillers may be pre-dispersed in a liquid carrier rather than a polymer matrix.
In an aspect of the embodiments described herein, a method for forming a composite material is provided that includes: combining and pre-mixing at least one 1st and at least one 2nd component elements to form a composite mixture; dispersing the 2nd component element in the 1st component element using a first force in order to form ligaments, wherein the first force is mechanical; further dispersing the 2nd component element in the 1st component element using one or more second forces in order to form attenuated ligaments; and collecting the attenuated ligaments.
In a particular case, the mechanical first force may be, for example, centrifugal force, high pressure force, or the like. The mechanical first force may be provided by, for example, squeezing the composite mixture under the application of pressure through a die plate with at least one orifice; using a melt blower; using a sprayer machine; using an atomization device, for example, a rotating surface device, or the like.
Further, the one or more second forces may include centrifugal, pressure, aerodynamic, electrical, electrostatic, electrophoretic, dielectrophoretic, magnetic, Coulomb, or the like, or a combination thereof. The first and second forces may be similar or different.
In a particular case, the 1st component element may be a viscoelastic material or may be a material that exhibits viscoelastic behaviour, for example, when mixed with the 2nd component elements. The 1st component element may be selected from: polymer melt; polymer solution; liquid polymer; flowable polymer, or a combination thereof.
The 2nd component element (sometimes referred to as filler) may have one or more of the following properties:
In some cases, prior to mixing the 2nd component element with the 1st component element, the 2nd component element may be made into a filler colloid or the like by, for example, combining the 2nd component element with a compliant liquid. The compliant liquid may be, for example, miscible/immiscible in the 1st component element, a solvent, or the like.
In another case, the 1st component element and 2nd component element may be pre-mixed prior to application of the first force or the one or more second forces.
In some cases, there may be a plurality of 1st component elements and/or a plurality of 2nd component elements. It will further be understood that the 1st component element and 2nd component element may include objects having a plurality of sizes, dimensions, or physical states. Further, each 2nd component element may not be mixed with the 1st component objects at the same time, for example, one 2nd component element (e.g., a hydrophobic filler) may be added prior to a subsequent 2nd component element (e.g., a hydrophilic filler), and the like
In some particular cases, the method or portions thereof may be performed at predetermined temperatures.
In another aspect of the embodiments herein, a system for forming a composite material is provided that includes: a feeder for combining and pre-mixing at least one 1st component element and at least one 2nd component element to form a composite mixture; a first disperser for dispersing the 1st component element in the 2nd component element using a mechanical first force in order to form ligaments; a second disperser for further dispersing the 1st component element in the 2nd component element using one or more second forces in order to form attenuated ligaments; and a collector for collecting the attenuated ligaments.
In a particular case, the feeder may be one or more feeder modules that feed the component elements and may include pre-mixers for pre-mixing the component elements.
Further, the first disperser and second disperser may be a rotating surface configured to receive the first component element and the second component element from the feeder, the rotating surface configured to impart a centrifugal force to the first component element and the second component element to both mix the component elements using both shear and extensional deformation to form the ligaments and force a predetermined portion of the composite to the edge of and off the rotating surface in order to form the attenuated ligaments.
In a particular case, the feeder, first disperser, second disperser and collector may be at predetermined temperatures.
In some cases, the second disperser may include an electric field applied between the feeder or rotating surface and the collector in order to provide an additional second force.
In some of the above cases, the rotary surface may be a flat disk; a cone; a parabolic surface; a plurality of rotating surfaces; a rotating surface with grooves to guide the formation of ligaments, or the like.
Composite materials created using the method or system described herein are intended to have properties that are different from conventional composite materials. For example, composite materials may have a loading level of the 2nd component element in the composite of between 0.001 wt % and 100 wt %. In particular, the loading level may be greater than 7 wt %, greater than 10 wt %, greater than 20 wt %, greater than 30 wt %, greater than 40 wt %, greater than 50 wt %, greater than 60 wt %, greater than 70 wt %, greater than 80 wt %, greater than 85 wt % or an appropriate wt % in or above these ranges.
In the preceding description, for purposes of explanation, numerous details are set forth in order to provide a thorough understanding of the embodiments. However, it will be apparent to one skilled in the art that these specific details may not be required. In other instances, well-known structures may be shown in block diagram form in order not to obscure the understanding. For example, specific details are not provided as to whether the embodiments described herein or elements thereof are implemented as a software routine, hardware circuit, firmware, or a combination thereof.
The above-described embodiments are intended to be examples only. Alterations, modifications and variations can be effected to the particular embodiments by those of skill in the art. The scope of the claims should not be limited by the particular embodiments set forth herein, but should be construed in a manner consistent with the specification as a whole.
This application is a National Stage filing under 35 U.S.C. § 371 of International Application No. PCT/CA2014/051110, filed Nov. 20, 2014, which claims the benefit of U.S. Provisional Patent Application No. 61/962,964 filed Nov. 20, 2013 which is hereby incorporated herein by reference.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CA2014/051110 | 11/20/2014 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2015/074151 | 5/28/2015 | WO | A |
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| 20160297100 A1 | Oct 2016 | US |
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| 61962964 | Nov 2013 | US |
