Patent Grant
10172387
The present disclosure relates to aerosol delivery devices such as smoking articles, and more particularly to electrically resistive heaters useful in such devices. The electrically resistive heaters may be configured to heat a material, which may be made or derived from tobacco or otherwise incorporate tobacco, to form an inhalable substance for human consumption.
Many smoking devices have been proposed through the years as improvements upon, or alternatives to, smoking products that require combusting tobacco for use. Many of those devices purportedly have been designed to provide the sensations associated with cigarette, cigar, or pipe smoking, but without delivering considerable quantities of incomplete combustion and pyrolysis products that result from the burning of tobacco. To this end, there have been proposed numerous smoking products, flavor generators, and medicinal inhalers that utilize electrical energy to vaporize or heat a volatile material, or attempt to provide the sensations of cigarette, cigar, or pipe smoking without burning tobacco to a significant degree. See, for example, the various alternative smoking articles, aerosol delivery devices and heat generating sources set forth in the background art described in U.S. Pat. No. 7,726,320 to Robinson et al., U.S. patent application Ser. No. 13/432,406, filed Mar. 28, 2012, U.S. patent application Ser. No. 13/536,438, filed Jun. 28, 2012, U.S. patent application Ser. No. 13/602,871, filed Sep. 4, 2012, and U.S. patent application Ser. No. 13/647,000, filed Oct. 8, 2012, which are incorporated herein by reference.
Certain tobacco products that have employed electrical energy to produce heat for smoke or aerosol formation, and in particular, certain products that have been referred to as electronic cigarette products, have been commercially available throughout the world. Representative products that resemble many of the attributes of traditional types of cigarettes, cigars or pipes have been marketed as ACCORD® by Philip Morris Incorporated; ALPHA™, JOYE 510™ and M4™ by InnoVapor LLC; CIRRUS™ and FLING™ by White Cloud Cigarettes; COHITA™, COLIBRI™, ELITE CLASSIC™, MAGNUM™, PHANTOM™ and SENSE™ by Epuffer® International Inc.; DUOPRO™, STORM™ and VAPORKING® by Electronic Cigarettes, Inc.; EGAR™ by Egar Australia; eGo-C™ and eGo-T™ by Joyetech; ELUSION™ by Elusion UK Ltd; EONSMOKE® by Eonsmoke LLC; GREEN SMOKE® by Green Smoke Inc. USA; GREENARETTE™ by Greenarette LLC; HALLIGAN™, HENDU™, JET™, MAXXQ™, PINK™ and PITBULL™ by Smoke Stik®; HEATBAR™ by Philip Morris International, Inc.; HYDRO IMPERIALT™ and LXE™ from Crown7; LOGIC™ and THE CUBAN™ by LOGIC Technology; LUCI® by Luciano Smokes Inc.; METRO® by Nicotek, LLC; NJOY® and ONEJOY™ by Sottera, Inc.; NO. 7™ by SS Choice LLC; PREMIUM ELECTRONIC CIGARETTE™ by PremiumEstore LLC; RAPP E-MYSTICKT™ by Ruyan America, Inc.; RED DRAGON™ by Red Dragon Products, LLC; RUYAN® by Ruyan Group (Holdings) Ltd.; SMART SMOKER® by The Smart Smoking Electronic Cigarette Company Ltd.; SMOKE ASSIST® by Coastline Products LLC; SMOKING EVERYWHERE® by Smoking Everywhere, Inc.; V2CIGS™ by VMR Products LLC; VAPOR NINE™ by VaporNine LLC; VAPOR4LIFE® by Vapor 4 Life, Inc.; VEPPO™ by E-CigaretteDirect, LLC and VUSE® by R. J. Reynolds Vapor Company. Yet other electrically powered aerosol delivery devices, and in particular those devices that have been characterized as so-called electronic cigarettes, have been marketed under the tradenames BLU™; COOLER VISIONS™; DIRECT E-CIG™; DRAGONFLY™; EMIST™; EVERSMOKE™; GAMUCCI®; HYBRID FLAME™; KNIGHT STICKS™; ROYAL BLUES™; SMOKETIP® and SOUTH BEACH SMOKET™.
It would be desirable to provide a smoking article that employs heat produced by electrical energy to provide the sensations of cigarette, cigar, or pipe smoking, that does so without combusting tobacco to any significant degree, that does so without the need of a combustion heat source, and that does so without necessarily delivering considerable quantities of incomplete combustion and pyrolysis products. Further, advances with respect to manufacturing electronic smoking articles would be desirable.
The present disclosure relates to materials and combinations thereof useful in aerosol formation, particularly in an electronic smoking article or like vapor forming device. In various embodiments, the materials useful in aerosol formation can be comprised largely from carbon materials. Such materials in particular can be used in a cartridge of an electronic smoking article and, in some embodiments, the dry components of the cartridge can be formed predominately or completely from carbon. Such structuring can beneficially improve the disposable nature of the cartridge. In particular, slow degrading materials, such as metal and synthetic polymer components, that are typically present in cartridges for electronic smoking articles can be avoided.
In one aspect, the present disclosure provides an electrically resistive heater formed of a porous carbon material, such as a carbon foam. The porous carbon heater can be adapted for use in an electronic smoking article or a component thereof. For example, in certain embodiments, the present disclosure provides an atomizer of an electronic smoking article. Specifically, the atomizer can comprise the electrically resistive heater formed of a porous carbon. Preferably, the porous carbon can comprise about 90% or greater of the dry mass of the electrically resistive heater. In some embodiments, the electrically resistive heater consists essentially of the porous carbon. In other embodiments, the electrically resistive heater consists of the porous carbon. In further embodiments, the electrically resistive heater can expressly exclude electrically conductive materials that are not porous carbon, such as metals and graphite.
The porous carbon used as the electrically resistive heating element can be characterized by specific properties. For example, the dry mass of the porous carbon can be about 90% or greater carbon. The porous carbon can be characterized as comprising a plurality of pores. Preferably, a majority of the pores are closed pores. More specifically, about 80% or greater by volume of the pores can be closed pores. In additional embodiments, the porous carbon heater can have a density of about 0.1 g/cm3 to about 0.5 g/cm3. Further, the porous carbon heater can have an aqueous liquid retention capacity that less than or equal to about 100% of the dry mass of the porous carbon heater.
In further embodiments, the porous carbon heater can be characterized by its resistivity and effective heating upon application of an electrical current. For example, the porous carbon heater can exhibit a resistivity of about 1.0×10−3 Ω·m to about 1.0×10−4 Ω·m. As such, the porous carbon heater can be adapted to achieve a temperature of about 150° C. to about 550° C. when subjected to an electrical current of about 0.2 amps to about 12 amps for a time of about 1 second to about 3 seconds.
In some embodiments, the porous carbon heater may also function as a reservoir for an aerosol precursor material. Specifically, an aerosol precursor material may be contained by, coated on, absorbed by, or adsorbed on the carbon foam heater.
In other embodiments, an atomizer may include, in addition to the porous carbon heater, an aerosol precursor transport element. Specifically, the aerosol precursor transport element can be arranged so as to be in direct contact with the porous carbon heater. In some embodiments, the aerosol precursor transport element can surround the porous carbon heater. In other embodiments, the aerosol precursor transport element can be a fibrous material. In additional embodiments, the aerosol precursor transport element can comprise a capillary. In further embodiments, the aerosol precursor transport element can be at least partially embedded within the carbon foam heater.
In particular embodiments, the aerosol precursor transport element can be formed of carbon fibers. The carbon fiber aerosol precursor transport element can have a dry mass of about 85% or greater carbon. More specifically, the carbon fiber aerosol precursor transport element can comprise a carbonized fabric. The aerosol precursor transport element further can comprise an aerosol precursor material.
In some embodiments, the porous carbon heater can be elongated having a first end and having a second, opposing end. One end or both ends can be adapted for electrical connection with an electrical power source.
The aerosol precursor transport element can take on a variety of conformations useful for facilitating transfer of the aerosol precursor material to the porous carbon heater. In one embodiment, the aerosol precursor transport element can be substantially arc-shaped so as to only partially surround the porous carbon heater. For example, the arc-shaped aerosol precursor transport element can have an inner arc surface in at least partial contact with the porous carbon heater and an outer arc surface spaced apart from the inner arc surface. The thus shaped component may be described as a partial disc and can have a defined width measured from the inner arc surface to the outer arc surface and a thickness measured from a first face to an opposing, second face. The aerosol precursor transport element can be positioned proximate the first end of the porous carbon heater. As further described herein, the above is only exemplary of the nature of the aerosol precursor transport element in some embodiments and should not be viewed as limiting the shape of the component.
In additional embodiments, an electrical connector can be utilized and can have a first end in electrical connection with the second end of the porous carbon heater and can have a second, opposing end adapted for electrical connection with the electrical power source. In specific embodiments, the electrical connector can be non-metallic. For example, the electrical connector can be formed of graphite. Other electrically conductive materials, however, may also be used. As further discussed herein, additional elements can be included to complete an electrical circuit with the battery, the electrical connector, and the porous carbon heater.
In another aspect, the present disclosure also relates to a cartridge of an electronic smoking article. A cartridge can comprise an outer housing or shell and can be adapted for attachment to a control body. A cartridge may include a variety of components such as (separately or in various combinations) a heater, a liquid storage element, a liquid transport element, electrical connections, an insulator, and a filter material.
In certain embodiments, a cartridge of an electronic smoking article according to the present disclosure can comprise an elongated, electrically resistive heater formed of a porous carbon, such as a carbon foam, the porous carbon heater having a first end and a second, opposing end adapted for electrical connection with an electrical power source. The cartridge also can include an aerosol precursor transport element arranged so as to be in direct contact with the porous carbon heater. The cartridge further can comprise an electrical connector having a first end in electrical connection with the second end of the porous carbon heater and having a second, opposing end adapted for electrical connection with an electrical power source. The cartridge also can comprise a housing having a first end proximate the first end of the porous carbon heater and a second end proximate the second end of the electrical connector. The cartridge further can comprise a fibrous material surrounding at least a portion of the cartridge. The fibrous material can be a filter, and the filter can include a filter extension that extends beyond the first end of the housing. The filter and/or the filter extension can include one or more flavor capsules. The cartridge also can comprise an aerosol precursor material.
In additional embodiments, a cartridge according to the disclosure can be defined by a variety of characteristics that may be embodied singly or in several combinations. For example, a cartridge may be defined by one or more of the following:
In further embodiments, the second end of the housing can be adapted for forming a structural connection with a first end of a power unit including the electrical power source. In particular, the structural connection can be a threaded connection. Alternatively, the structural connection can be a press fit connection or snap-fit connection.
In certain embodiments, the first end of the housing can comprise a wall comprising an alignment recess adapted to engage the first end of the porous carbon heater. The engagement can form an electrical connection between the porous carbon heater and the housing. The housing wall at the first end can include one or more through holes adapted for passage of an aerosol therethrough.
In other embodiments, the second end of the housing can include a flange. In particular, the flange can have a greater diameter than the diameter of the remaining portion of the housing. The housing can be formed of a carbon material. For example, the carbon material can be graphite.
In some embodiments, a cartridge further can comprise a fibrous material surrounding at least a portion of the cartridge. The fibrous material can comprise a filter material.
In certain embodiments, the electrical connector, the porous carbon heater, and the housing can form an electrical circuit, which may also include a power source and one or more control elements (e.g., a microcontroller).
A cartridge according to the present disclosure can be defined in yet further manners. For example, the cartridge can be free of metal. A majority of the total dry mass of all components of the cartridge can be carbon. More specifically, the total dry mass of all components of the cartridge can be about 75% or greater carbon. In an exemplary embodiment, a cartridge of an electronic smoking article according to the present disclosure can comprise an electrically resistive heater, an aerosol precursor transport element, and a housing, wherein a majority of the total dry mass all components of the cartridge is carbon. More particularly, such cartridge can be free of metal.
In another aspect, the present disclosure can relate to an electronic smoking article. Such smoking article can comprise a housing or shell. Specifically, the smoking article can comprise a cartridge having an outer housing and a separate control body having an outer housing, the cartridge and the control body being detachably connected. In certain embodiments, an electronic smoking article according to the present disclosure can comprise an electrical power source and an elongated, electrically resistive heater formed of a porous carbon, such as a carbon foam, the porous carbon heater having a first end and a second, opposing end adapted for electrical connection with the electrical power source. The smoking article further can comprise an aerosol precursor transport element arranged so as to be in direct contact with the porous carbon heater. In further embodiments, the smoking article can comprise an electrical connector having a first end in electrical connection with the second end of the porous carbon heater and having a second, opposing end adapted for electrical connection with the electrical power source. The porous carbon heater particularly can be arranged within a cartridge housing and the electrical power source particularly can be arranged within a separate control body housing. The cartridge housing can have a first end proximate the first end of the porous carbon heater and a second end proximate the second end of the electrical connector. Further, the second end of the housing can be adapted for forming a structural connection with a first end of the control body housing. In some embodiments, the first end of the cartridge housing can comprise a wall comprising an alignment recess adapted to engage the first end of the porous carbon heater, and the engagement can form an electrical connection between the porous carbon heater and the housing. In particular, the electrical connector, the porous carbon heater, and the housing can form an electrical circuit.
In further embodiments, an electronic smoking article according to the present disclosure can comprise an aerosol precursor material. Moreover, such electronic smoking article can be defined in relation to the specific description of components of the electronic smoking as otherwise provided herein. Thus, the description of an atomizer and its components, the description of a cartridge and its components, and the description of a control body and its components all can apply to the electronic smoking article in a variety of combinations. In one embodiment, an electronic smoking article can comprise an electrical power source and an electrically resistive heater formed of a porous carbon, such as a carbon foam, wherein the porous carbon heater is in a metal-free (e.g., wire-free) electrical connection with the electrical power source.
In still another aspect, the present disclosure also can relate to a method of heating an aerosol precursor material and forming an aerosol, such as in an electronic smoking article. In one embodiment, such method can comprise the step of connecting a cartridge of the electronic smoking article to a control body of the electronic smoking article. In particular, the control body can comprise an electrical power source, a pressure sensor, an electronic controller, and a control body housing. The cartridge can comprise: an elongated, electrically resistive heater formed of a porous carbon, such as a carbon foam, the porous carbon heater having a first end and a second, opposing end; an aerosol precursor transport element arranged so as to be in direct contact with the porous carbon heater; an electrical connector having a first end in electrical connection with the second end of the porous carbon heater and having a second, opposing end adapted for electrical connection with the electrical power source; and a cartridge housing having a first end including an end wall with an alignment recess adapted to engage the first end of the porous carbon heater and a second end proximate the second end of the electrical connector, the second end of the housing being adapted for forming a structural connection with a first end of the control body housing, and wherein the electrical connector, the porous carbon heater, and the cartridge housing form an electrical circuit. The method further can comprise the following steps: causing a pressure change within the electronic smoking article such that the pressure sensor signals the electronic controller to cause a flow of electrical current from the electrical power source to the cartridge; causing the electrical current to flow through the electrical circuit of the cartridge so as to cause heating of the porous carbon heater; and causing the aerosol precursor material in the aerosol precursor transport element to vaporize, mix with air, and form an aerosol.
Having thus described the disclosure in the foregoing general terms, reference will now be made to the accompanying drawings, which are not necessarily drawn to scale, and wherein:
The present disclosure will now be described more fully hereinafter with reference to exemplary embodiments thereof. These exemplary embodiments are described so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art. Indeed, the disclosure may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will satisfy applicable legal requirements. As used in the specification, and in the appended claims, the singular forms “a”, “an”, “the”, include plural referents unless the context clearly dictates otherwise.
The present disclosure provides descriptions of aerosol delivery devices that use electrical energy to heat a material (preferably without combusting the material to any significant degree) to form an inhalable substance; such articles most preferably being sufficiently compact to be considered “hand-held” devices. In certain highly preferred embodiments, the aerosol delivery devices can be characterized as smoking articles. As used herein, the term “smoking article” is intended to mean an article or device that provides some or all of the sensations (e.g., inhalation and exhalation rituals, types of tastes or flavors, organoleptic effects, physical feel, use rituals, visual cues such as those provided by visible aerosol, and the like) of smoking a cigarette, cigar, or pipe, without any substantial degree of combustion of any component of that article or device. As used herein, the term “smoking article” does not necessarily mean that, in operation, the article or device produces smoke in the sense of the aerosol resulting from by-products of combustion or pyrolysis of tobacco, but rather, that the article or device yields vapors (including, e.g., vapors within aerosols that can be considered to be visible aerosols that might be considered to be described as smoke-like) resulting from volatilization or vaporization of certain components of the article or device. In highly preferred embodiments, articles or devices characterized as smoking articles incorporate tobacco and/or components derived from tobacco.
Articles or devices of the present disclosure also can be characterized as being vapor-producing articles, aerosol delivery articles or medicament delivery articles. Thus, such articles or devices can be adapted so as to provide one or more substances (e.g., flavors and/or pharmaceutical active ingredients) in an inhalable form or state. For example, inhalable substances can be substantially in the form of a vapor (i.e., a substance that is in the gas phase at a temperature lower than its critical point). Alternatively, inhalable substances can be in the form of an aerosol (i.e., a suspension of fine solid particles or liquid droplets in a gas). For purposes of simplicity, the term “aerosol” as used herein is meant to include vapors, gases and aerosols of a form or type suitable for human inhalation, whether or not visible, and whether or not of a form that might be considered to be smoke-like.
In use, smoking articles of the present disclosure may be subjected to many of the physical actions employed by an individual in using a traditional type of smoking article (e.g., a cigarette, cigar or pipe that is employed by lighting and inhaling tobacco). For example, the user of a smoking article of the present disclosure can hold that article much like a traditional type of smoking article, draw on one end of that article for inhalation of aerosol produced by that article, take puffs at selected intervals of time, etc.
Smoking articles of the present disclosure generally include a number of components provided within an outer shell or body. The overall design of the outer shell or body can vary, and the format or configuration of the outer body defining the overall size and shape of the smoking article can vary. Typically, an elongated body resembling the shape of a cigarette or cigar can be a formed from a single, unitary shell; or the elongated body can be formed of two or more separable pieces. For example, a smoking article can comprise an elongated shell or body that can be substantially tubular in shape and, as such, resemble the shape of a conventional cigarette or cigar. In one embodiment, all of the components of the smoking article can be contained within one outer body or shell. Alternatively, a smoking article can comprise two or more shells that are joined and are separable. For example, a smoking article can possess at one end a control body comprising a shell containing one or more reusable components (e.g., a rechargeable battery and various electronics for controlling the operation of that article), and at the other end and removably attached thereto a shell containing a disposable portion (e.g., a disposable flavor-containing cartridge). More specific formats, configurations and arrangements of components within the single shell type of unit or within a multi-piece separable shell type of unit will be evident in light of the further disclosure provided herein. Additionally, various smoking article designs and component arrangements can be appreciated upon consideration of the commercially available electronic smoking articles, such as those representative products listed in the background art section of the present disclosure.
Smoking articles of the present disclosure most preferably comprise some combination of a power source (i.e., an electrical power source), at least one control component (e.g., means for actuating, controlling, regulating and ceasing power for heat generation, such as by controlling electrical current flow from the power source to other components of the article), a heater or heat generation component (e.g., an electrical resistance heating element or component commonly referred to as an “atomizer”), and an aerosol precursor composition (e.g., commonly a liquid capable of yielding an aerosol upon application of sufficient heat, such as ingredients commonly referred to as “smoke juice,” “e-liquid” and “e-juice”), and a mouthend region or tip for allowing draw upon the smoking article for aerosol inhalation (e.g., a defined air flow path through the article such that aerosol generated can be withdrawn therefrom upon draw).
Alignment of the components within the article can vary. In specific embodiments, the aerosol precursor composition can be located near an end of the article (e.g., within a cartridge, which in certain circumstances can be replaceable and disposable), which may be proximal to the mouth of a user so as to maximize aerosol delivery to the user. Other configurations, however, are not excluded. Generally, the heating element can be positioned sufficiently near the aerosol precursor composition so that heat from the heating element can volatilize the aerosol precursor (as well as one or more flavorants, medicaments, or the like that may likewise be provided for delivery to a user) and form an aerosol for delivery to the user. When the heating element heats the aerosol precursor composition, an aerosol is formed, released, or generated in a physical form suitable for inhalation by a consumer. It should be noted that the foregoing terms are meant to be interchangeable such that reference to release, releasing, releases, or released includes form or generate, forming or generating, forms or generates, and formed or generated. Specifically, an inhalable substance is released in the form of a vapor or aerosol or mixture thereof. Additionally, the selection of various smoking article components can be appreciated upon consideration of the commercially available electronic smoking articles, such as those representative products listed in the background art section of the present disclosure.
A smoking article incorporates a battery or other electrical power source to provide current flow sufficient to provide various functionalities to the article, such as resistive heating, powering of control systems, powering of indicators, and the like. The power source can take on various embodiments. Preferably, the power source is able to deliver sufficient power to rapidly heat the heating member to provide for aerosol formation and power the article through use for the desired duration of time. The power source preferably is sized to fit conveniently within the article so that the article can be easily handled; and additionally, a preferred power source is of a sufficiently light weight to not detract from a desirable smoking experience.
The presently disclosed smoking articles particularly incorporate a heating element that is carbon-based. The carbon-based heater can be predominately formed of carbon (i.e., greater than 50% carbon based on the dry weight of the heater). In specific embodiments, the carbon can comprise about 75% or greater, about 80% or greater, about 90% or greater, about 95% or greater, or about 99% or greater of the dry mass of the heater. The heater thus may be defined by comprising substantially completely carbon. The heater may be defined as consisting essentially of carbon in that the heater does not include any further electrically conductive material. In some embodiments, the carbon-based heater may include a minor content of one or more materials useful in forming the structure of the heater but that do not substantially contribute to electrical conductivity of the heater. For example, a binder material may be included with the carbon material to assist in maintaining the structure of the heater. Preferably, the dry mass of the carbon-based heater is about 75% or greater, about 80% or greater, about 90% or greater, about 95% or greater, or about 99% or greater carbon.
The carbon-based heater is electrically conductive and exhibits a sufficient resistance so as to heat to a temperature effective for vaporization of aerosol precursor materials. In some embodiments, the resistance can be about 0.1 ohms to about 20 ohms, about 0.25 ohms to about 15 ohms, or about 0.5 ohms to about 10 ohms. The resistance of the heater is a function of the resistivity of the material, cross-sectional area, and length. In some embodiments, the porous carbon heater material can exhibit a resistivity of about 1.0×10−3 Ω·m to about 1.0×10−4 Ω·m. The carbon-based heater also is suitable for heating under application of an electrical current of about 0.1 amps to about 15 amps, about 0.2 amps to about 12 amps, or about 0.25 amps to about 10 amps. Voltage can be about 2V to about 6V, about 2.25V to about 5.5V, or about 2.5V to about 5V. The carbon-based heater can be adapted for heating in a temperature range of about 100° C. to about 600° C., about 150° C. to about 550° C., or about 175° C. to about 500° C.
A carbon heater useful according to various embodiments of the present disclosure may particularly be characterized by the physical nature of the material. As further described below, the carbon-based heater may particularly be a porous carbon material. In various embodiments, porous carbon materials can be particularly useful in the evolution of vapor through heating of a liquid composition. The porous carbon materials specifically can efficiently release liquid materials absorbed therein or adsorbed thereon while simultaneously providing resistive heating at temperature ranges and response times advantageous for use in on-demand aerosolization devices. In some embodiments, the porous carbon material may particularly be a carbon foam. In some exemplary embodiments herein, a carbon foam is specifically described. It is understood, however, that the scope of porous carbon materials is not limited to carbon foam and can in fact encompass any number of porous carbon materials exhibiting properties and functions as described herein.
An illustration of a porous carbon rod 10 that can be useful as a heater according to the present disclosure is shown in
The porous carbon heater can have a density of about 0.005 g/cm3 to about 0.8 g/cm3, about 0.01 g/cm3 to about 0.6 g/cm3, or about 0.05 g/cm3 to about 0.4 g/cm3. The porous carbon heater can have a porosity of about 50% to about 95%, about 60% to about 90%, or about 70% to about 88% based on volume. For example, in one embodiment, the carbon heater can comprise about 13% carbon by volume and 87% air by volume. The porous carbon heater particularly can be defined by its closed cell nature. In other words, the pores or cells in the porous carbon are predominately closed pore (e.g., air filled pores). An illustration of a segment of an ideal, closed pore system is shown in
The porous carbon useful as a heater according to the present disclosure may be prepared according to any useful method. Exemplary methods of preparing porous carbon materials, such as carbon foam, and the materials produced thereby (which may be useful in a device as presently disclosed herein) are described in U.S. Pat. No. 6,033,506 to Klett, U.S. Pat. No. 6,037,032 to Klett et al., U.S. Pat. No. 6,729,269 to Ott et al., and U.S. Pat. No. 8,372,510 to Miller et al., the disclosures of which are incorporated herein by reference in their entireties.
The porous carbon has been found according to certain embodiments of the present disclosure to be a particularly good electrical conductor and is thus useful as a heater element, such as in an atomizer. In some embodiments, a material for vaporization, such as an aerosol precursor material as otherwise described herein, may be directly applied to the porous carbon heater—e.g., by coating, absorption, adsorption, or the like. In other embodiments, a separate aerosol precursor transport element can be provided. If desired, the aerosol precursor transport element may form a fluid connection between the heater and a secondary liquid storage element (i.e., a liquid reservoir). In preferred embodiments, the aerosol precursor transport element can function simultaneously as a reservoir and a wick. For example, the aerosol precursor transport element can have an initial charge of liquid aerosol precursor composition applied thereto and can also transport liquid composition from the secondary liquid storage element. This can be particularly beneficial to reduce the number of necessary elements in an electronic smoking article or other article incorporating the porous carbon heater. Preferably, the aerosol precursor transport element is arranged so as to be in direct contact with the porous carbon heater. The direct contact can vary. For example, the aerosol precursor transport element may be arranged so as to only contact the porous carbon heater at one or a plurality of discrete points. The aerosol precursor transport element may be arranged so as to at least partially pass through the porous carbon heater axially, perpendicular to the lengthwise axis, at an angle to the lengthwise axis, or any combination thereof. In some embodiments, the aerosol precursor transport element can substantially surround all or a section of the porous carbon heater. Three exemplary arrangements of the aerosol precursor transport element relative to the carbon foam heater are shown in
In the embodiment of
In the embodiment of
In the embodiment of
In further embodiments, an aerosol precursor transport element can be positioned relative a porous carbon heater in even further conformations. For example, an aerosol precursor transport element can substantially surround all or a portion of a porous carbon heater. Alternately, an aerosol precursor transport element can be elongated and be positioned along the length of the porous carbon heater. Moreover, a plurality of individual aerosol precursor transport elements having shapes and formed of materials as otherwise described herein may be positioned relative to the porous carbon heater.
An aerosol precursor transport element useful according to the present disclosure can be formed of a variety of materials as otherwise described herein, such as in relation to wicks and liquid reservoirs. In preferred embodiments, the aerosol precursor transport element combined with a porous carbon heater also is formed predominately of carbon (i.e., greater than 50% of the dry mass of the aerosol precursor transport element comprising carbon). In specific embodiments, about 75% or greater, about 85% or greater, about 90% or greater, or about 95% or greater of the dry mass of the aerosol precursor transport element is carbon. In an exemplary embodiment, the aerosol precursor transport element can be formed of carbon fibers.
A carbon fiber aerosol precursor transport element particularly can be formed of a carbonized fabric. For example, fibrous tow, yarn, or a woven or non-woven fabric formed of natural and/or synthetic fibers may be carbonized through application of high heat so as to substantially drive off all non-carbon components of the materials. Cellulose fibers, in particular, may be useful for forming a carbonized fabric. One method for forming carbonized fabrics is disclosed in U.S. Publ. No. 2009/0011673 to Huang et al., the disclosure of which is incorporated herein by reference in its entirety. Carbonized fabrics that can be used according to the present disclosure are commercially available from Morgan AM&T (Greenville, S.C.).
Carbonized fabrics can be particularly useful as an aerosol precursor transport element, a reservoir, or both according to the present disclosure in light of their open cell porosity. Preferred carbonized fabrics can have an open cell porosity of about 80% or greater, about 85% or greater, or about 90% or greater. Useful carbonized fabrics also can exhibit a great liquid retention capacity. In relation to a polar liquid, such as an aerosol precursor material as described herein, a carbonized fabric aerosol precursor transport element can exhibit a liquid retention capacity of 200% or greater, 400% or greater, or 600% or greater of the dry mass of the carbonized fabric aerosol precursor transport element. As such, the carbonized fabric aerosol precursor transport element can store and rapidly transfer an aerosol precursor material to a porous carbon heater, which can preferentially vaporize the aerosol precursor material. Because of the nature of the porous carbon in some embodiments as discussed above, the porous carbon heater does not significantly absorb the aerosol precursor material from the carbonized fabric. As such, the aerosol precursor material preferentially only is withdrawn from the carbonized fabric aerosol precursor transport element at the point of contact or other fluid connection with the porous carbon heater as the heated porous carbon vaporizes the aerosol precursor material.
An exemplary embodiment of an aerosol precursor transport element 20 in the form of a carbonized fabric 100 is shown in
In exemplary embodiments, a carbonized fabric useful according to the disclosure can have a width of about 0.5 mm to about 4 mm, about 1 mm to about 3.75 mm, or about 1.5 mm to about 3.5 mm. The carbonized fabric can have a thickness of about 0.25 mm to about 15 mm, about 0.5 mm to about 12 mm, or about 1 mm to about 10 mm. The carbonized fabric can have a density of about 0.1 g/cm3 to about 0.4 g/cm3, about 0.15 g/cm3 to about 0.35 g/cm3, or about 0.17 g/cm3 to about 0.3 g/cm3.
An image of an exemplary embodiment of a carbonized fabric 100 useful as an aerosol precursor transport element according to the present disclosure is shown in
The fibrous nature of the carbonized fabric useful in certain embodiments of the present disclosure is illustrated in the SEM image provided in
In certain embodiments, a carbonized fabric 100 can be positioned relative a porous carbon heater 10 as shown in
Further materials useful as conductive substrates may also be utilized according to the present disclosure. For example, conductive substrates as described in U.S. patent application Ser. No. 13/432,406, filed Mar. 28, 2012, may be used, and the disclosure of said patent application is incorporated herein by reference in its entirety.
A heater and an aerosol precursor transport element as substantially described above may be incorporated into a cartridge that is useful as a component of, for example, an electronic smoking article. Beneficially, a cartridge according to the present disclosure can be formed substantially completely of carbon.
In an exemplary embodiment, a cartridge can comprise an elongated, electrically resistive porous carbon heater having a first end and a second, opposing end adapted for electrical connection with an electrical power source. The porous carbon heater can be substantially defined as otherwise described herein. The cartridge also can comprise an aerosol precursor transport element arranged so as to be in direct contact or other fluid connection with the porous carbon heater. In some embodiments, the aerosol precursor transport element can at least partially surround the porous carbon heater. Alternatively, the aerosol precursor transport element can be in a different spatial arrangement with the porous carbon heater and can take on any structure as otherwise described herein. In a preferred embodiment, the aerosol precursor transport element can be formed of carbon fibers, such as a carbonized fabric.
The cartridge further can comprise an electrical connector 300 as illustrated in
A cartridge according to the present disclosure further can comprise a housing. One embodiment of a housing is shown in
In some embodiments, the second end of the housing can be adapted for forming a structural connection with a first end of a control body that includes the electrical power source. As such, the housing 400 may include a raised flange 450, and the interior thereof may be adapted form forming a threaded connection or a press fit connection with the control body. In embodiments where the electrical connector facilitates the structural connection with the control body, the flange 450 of the housing 400 may be absent or may function to substantially cover the connection and formed by the electrical connector and the control body. In some embodiments, the housing flange and the second end of the electrical connector may function together to form the structural and/or electrical connection with the control body. In an exemplary embodiment, a housing can have a total length of about 15 mm to about 35 mm, about 18 mm to about 32 mm, or about 20 mm to about 30 mm, a diameter of about 5 mm to about 15 mm, about 6 mm to about 13 mm, or about 7 mm to about 12 mm, and a wall thickness of about 0.1 mm to about 2 mm, about 0.25 nm to about 1.75 mm, or about 0.5 mm to about 1.5 mm. The flange may have a width of about 1 mm to about 8 mm, about 1.5 mm to about 7 mm, or about 2 mm to about 6 mm.
In some embodiments, the housing 400 can be covered with a filter and, optionally, a wrapping element. For example, a hollow tube filter 800 (e.g., formed of cellulose acetate or similar material) can be fitted around the external housing 400 in a manner that creates a flush junction to the raised flange 450 as illustrated in
In further embodiments, as seen in
In specific embodiments, as illustrated in
In further embodiments, the shortened housing can be covered with a hollow tube filter 800 that can extend beyond the end of the housing while maintaining the same diameter as the embodiment illustrated in
The first end 420 of the housing can comprise a wall 410 (which may include the one or more openings for passage of vapor or aerosol). The wall may function to provide a structural connection and/or an electrical connection of the heater to the housing. For example, in the embodiment of a cartridge 600 illustrated in the cross-section of
Further components of a cartridge according to an embodiment of the present disclosure are also illustrated in
A cartridge as described herein can be particularly advantageous in that the base materials of the cartridge can form the complete electrical circuit. For example, the electrical connector, the porous carbon heater, and the cartridge housing can form an electrical circuit. This is further illustrated in
In some embodiments, a cartridge according to the present disclosure may include a microchip, microcontroller, or like electronic element. For example, electronic components that may be useful are described in U.S. patent application Ser. No. 13/647,000, filed Oct. 8, 2012, and U.S. patent application Ser. No. 13/826,929, filed Mar. 14, 2013, the disclosures of which are incorporated herein by reference in their entireties.
In additional embodiments, the present disclosure can specifically relate to an electronic smoking article. Such smoking article in particular can include a carbon heater as otherwise described herein. Such smoking article in particular can comprise a cartridge as otherwise described herein. In certain embodiments, an electronic smoking article can comprise an electrical power source and an elongated, electrically resistive heater formed of a porous carbon, such as a carbon foam, the porous carbon heater having a first end and a second, opposing end adapted for electrical connection with the electrical power source. The electronic smoking article also can comprise an aerosol precursor transport element, such as a carbon fabric, as otherwise described herein. The electronic smoking article further can comprise an electrical connector, such as a graphite connector, as otherwise described herein. The electronic smoking article additionally can comprise a housing, such as a graphite housing, as otherwise described herein. Still further, the electronic smoking article can include a sheath and/or a housing wrapper as otherwise described herein.
In electronic smoking articles according to the present disclosure, all elements of the device can be present in a single housing. In certain embodiments, the porous carbon heater can be arranged within a cartridge housing and the electrical power source can be arranged within a separate control body housing.
One example embodiment of a smoking article 1000 is provided in
In specific embodiments, one or both of the control body 700 and the cartridge 600 may be referred to as being disposable or as being reusable. For example, the control body may have a replaceable battery or may be rechargeable and thus may be combined with any type of recharging technology, including connection to a typical electrical outlet, connection to a car charger (i.e., cigarette lighter receptacle), and connection to a computer, such as through a USB cable.
In the exemplified embodiment, the control body 700 includes a control component 706, a flow sensor 708, and a battery 710, which can be variably aligned, and can include a circuit board 712 at a distal end 714 of an external shell 716, the circuit board being useful for inclusion of one or more indicators of function of the device. The indicators can be provided in varying numbers and can take on different shapes and can even be an opening in the body (such as for release of sound when such indicators are present).
A proximal attachment end 722 of the control body 700 can be arranged for attachment to the second end 425 of the cartridge so as to form a structural and/or an electrical connection therewith. A first electrical attachment point 701 is adapted to form an electrical connection with the electrical connector 300, and a second electrical attachment point 702 is adapted to form an electrical connection with the flange 450 of the housing 400 when pressed into the cavity within the flange. The cartridge 600 is arranged as otherwise described herein. In particular, the cartridge 600 includes openings 410 arranged in the front wall 410 of the housing 400 to allow passage of air and entrained vapor (i.e., the components of the aerosol precursor composition in an inhalable form) from the cartridge to a consumer during draw on the smoking article 1000. The smoking article 1000 may be substantially rod-like or substantially tubular shaped or substantially cylindrically shaped in some embodiments. The housing 400 of the cartridge 600 has a first end 420 proximate the first end 1020 of the porous carbon heater 10 and a second end 425 proximate the second end 325 of the electrical connector 300, and the second end of the housing is adapted for forming a structural connection with the proximal attachment end 722 of the control body housing.
The cartridge 600 includes an atomizer comprising the porous carbon heater 10 and the carbon fabric aerosol precursor transport element 100. While the porous carbon is a preferred heater material, non-limiting examples of further materials that may be used as a heater include other tunable conductive/resistive materials, such as Kanthal (FeCrAl), Nichrome, Molybdenum disilicide (MoSi2), molybdenum silicide (MoSi), Molybdenum disilicide doped with Aluminum (Mo(Si,Al)2), and ceramic (e.g., a positive temperature coefficient ceramic). The liquid transport element may also be formed from a variety of materials configured to transport a liquid. For example, the liquid transport element may comprise cotton and/or fiberglass in some embodiments. The control body 700 can include appropriate wiring or circuitry (not illustrated) to form an electrical connection of the battery 710 with the porous carbon heater 10 when the cartridge 600 is connected to the control body 700. When the cartridge 600 is connected to the control body 70, the flange 450 and the electrical connector 350 engage the electrical attachment points 701, 702 on the control body 700 to form an electrical connection such that current controllably flows from the battery 710, through the first electrical contact point 701, to the electrical connector 300, through the porous carbon heater 10, through the housing 400, and to the second electrical connector 702 to form the complete electrical circuit.
In use, when a user draws on the article 1000, the heating element 10 is activated (e.g., such as via a puff sensor), and the components for the aerosol precursor composition are vaporized at the junction between the porous carbon heater 10 and the carbon fabric aerosol precursor transport element 100. Drawing upon the article 1000 causes ambient air to enter the article around the junction between the cartridge 600 and the control body 700 and enter the control body and the cartridge. In the cartridge 600, the drawn air combines with the formed vapor to form an aerosol. The aerosol may be whisked away and pass through the openings 440 in the front wall 410 of the housing 400 of the cartridge. As illustrated, the cartridge 600 also includes an outer wrapper 550 that can be, for example, a filter material, and the aerosol exiting the openings 440 pass through the wrapper for inhalation by a user.
It is understood that a smoking article that can be manufactured according to the present disclosure can encompass a variety of combinations of components useful in forming an electronic smoking article. For example, alternate heaters that may be useful according to the present disclosure are described in U.S. patent application Ser. No. 13/602,871, filed Sep. 4, 2012, the disclosure of which is incorporated herein by reference in its entirety. Further to the above, representative heating elements and materials for use therein are described in U.S. Pat. No. 5,060,671 to Counts et al.; U.S. Pat. No. 5,093,894 to Deevi et al.; U.S. Pat. No. 5,224,498 to Deevi et al.; U.S. Pat. No. 5,228,460 to Sprinkel Jr., et al.; U.S. Pat. No. 5,322,075 to Deevi et al.; U.S. Pat. No. 5,353,813 to Deevi et al.; U.S. Pat. No. 5,468,936 to Deevi et al.; U.S. Pat. No. 5,498,850 to Das; U.S. Pat. No. 5,659,656 to Das; U.S. Pat. No. 5,498,855 to Deevi et al.; U.S. Pat. No. 5,530,225 to Hajaligol; U.S. Pat. No. 5,665,262 to Hajaligol; U.S. Pat. No. 5,573,692 to Das et al.; and U.S. Pat. No. 5,591,368 to Fleischhauer et al., the disclosures of which are incorporated herein by reference in their entireties. A variable pitch heater that may be useful according to the present disclosure is provided in U.S. patent application Ser. No. 13/827,994, the disclosure of which is incorporated herein by reference in its entirety. Further, a single-use cartridge for use with an electronic smoking article is disclosed in U.S. patent application Ser. No. 13/603,612, filed Sep. 5, 2012, which is incorporated herein by reference in its entirety.
The various components of a smoking article according to the present disclosure can be chosen from components described in the art and commercially available. Examples of batteries that can be used according to the disclosure are described in U.S. Pat. App. Pub. No. 2010/0028766, the disclosure of which is incorporated herein by reference in its entirety.
An exemplary mechanism that can provide puff-actuation capability includes a Model 163PC01D36 silicon sensor, manufactured by the MicroSwitch division of Honeywell, Inc., Freeport, Ill. Further examples of demand-operated electrical switches that may be employed in a heating circuit according to the present disclosure are described in U.S. Pat. No. 4,735,217 to Gerth et al., which is incorporated herein by reference in its entirety. Further description of current regulating circuits and other control components, including microcontrollers that can be useful in the present smoking article, are provided in U.S. Pat. Nos. 4,922,901, 4,947,874, and 4,947,875, all to Brooks et al., U.S. Pat. No. 5,372,148 to McCafferty et al., U.S. Pat. No. 6,040,560 to Fleischhauer et al., U.S. Pat. No. 7,040,314 to Nguyen et al., U.S. patent application Ser. No. 13/788,455, filed Mar. 7, 2013, and U.S. patent application Ser. No. 13/837,542, filed Mar. 15, 2013, all of which are incorporated herein by reference in their entireties.
The aerosol precursor material, which may also be referred to as an aerosol precursor composition or a vapor precursor composition, can comprise one or more different components. For example, the aerosol precursor material can include a polyhydric alcohol (e.g., glycerin, propylene glycol, or a mixture thereof). Representative types of further aerosol precursor compositions are set forth in U.S. Pat. No. 4,793,365 to Sensabaugh, Jr. et al.; U.S. Pat. No. 5,101,839 to Jakob et al.; PCT WO 98/57556 to Biggs et al.; and Chemical and Biological Studies on New Cigarette Prototypes that Heat Instead of Burn Tobacco, R. J. Reynolds Tobacco Company Monograph (1988); the disclosures of which are incorporated herein by reference.
Still further components can be utilized in the smoking article of the present disclosure. For example, U.S. Pat. No. 5,261,424 to Sprinkel, Jr. discloses piezoelectric sensors that can be associated with the mouth-end of a device to detect user lip activity associated with taking a draw and then trigger heating; U.S. Pat. No. 5,372,148 to McCafferty et al. discloses a puff sensor for controlling energy flow into a heating load array in response to pressure drop through a mouthpiece; U.S. Pat. No. 5,967,148 to Harris et al. discloses receptacles in a smoking device that include an identifier that detects a non-uniformity in infrared transmissivity of an inserted component and a controller that executes a detection routine as the component is inserted into the receptacle; U.S. Pat. No. 6,040,560 to Fleischhauer et al. describes a defined executable power cycle with multiple differential phases; U.S. Pat. No. 5,934,289 to Watkins et al. discloses photonic-optronic components; U.S. Pat. No. 5,954,979 to Counts et al. discloses means for altering draw resistance through a smoking device; U.S. Pat. No. 6,803,545 to Blake et al. discloses specific battery configurations for use in smoking devices; U.S. Pat. No. 7,293,565 to Griffen et al. discloses various charging systems for use with smoking devices; U.S. Pat. App. Pub. No. 2009/0320863 by Fernando et al. discloses computer interfacing means for smoking devices to facilitate charging and allow computer control of the device; U.S. Pat. App. Pub. No. 2010/0163063 by Fernando et al. discloses identification systems for smoking devices; and WO 2010/003480 by Flick discloses a fluid flow sensing system indicative of a puff in an aerosol generating system; all of the foregoing disclosures being incorporated herein by reference in their entireties. Further examples of components related to electronic aerosol delivery articles and disclosing materials or components that may be used in the present article include U.S. Pat. No. 4,735,217 to Gerth et al.; U.S. Pat. No. 5,249,586 to Morgan et al.; U.S. Pat. No. 5,666,977 to Higgins et al.; U.S. Pat. No. 6,053,176 to Adams et al.; U.S. Pat. No. 6,164,287 to White; U.S. Pat. No. 6,196,218 to Voges; U.S. Pat. No. 6,810,883 to Felter et al.; U.S. Pat. No. 6,854,461 to Nichols; U.S. Pat. No. 7,832,410 to Hon; U.S. Pat. No. 7,513,253 to Kobayashi; U.S. Pat. No. 7,896,006 to Hamano; U.S. Pat. No. 6,772,756 to Shayan; U.S. Pat. No. 8,156,944 to Hon; U.S. Pat. App. Pub. Nos. 2006/0196518, 2009/0126745, and 2009/0188490 to Hon; U.S. Pat. App. Pub. No. 2009/0272379 to Thorens et al.; U.S. Pat. App. Pub. Nos. 2009/0260641 and 2009/0260642 to Monsees et al.; U.S. Pat. App. Pub. Nos. 2008/0149118 and 2010/0024834 to Oglesby et al.; U.S. Pat. App. Pub. No. 2010/0307518 to Wang; and WO 2010/091593 to Hon. A variety of the materials disclosed by the foregoing documents may be incorporated into the present devices in various embodiments, and all of the foregoing disclosures are incorporated herein by reference in their entireties.
The present invention is more fully illustrated by the following examples, which are set forth to illustrate the present invention and are not to be construed as limiting.
A cylindrical rod 3 mm in diameter and 10 mm in length was made from 0.17 g/cm3 carbon foam. Three equally spaced holes about 1 mm in diameter were drilled in the carbon. The holes went through the entire width of the foam. A cotton fiber was threaded through the holes as shown in
A cylindrical rod of 3 mm in diameter and 10 mm in length was made from 0.17 g/cc carbon foam. A hole of about 1.5 mm in diameter and 1.5 mm in depth was drilled at the center of the carbon foam. A cotton ball saturated with an aerosol precursor solution was inserted in the hole as shown
A cylindrical rod 3 mm in diameter and 10 mm in length was made from 0.17 g/cm3 carbon foam. The rod was inserted in the center of a disk formed of carbon fabric having a thickness of about 2 mm and a diameter of about 4 mm. About 0.6 mL of an aerosol precursor solution as applied to the assembly. A current of 4.2 volts and 0.7 amps was applied to the carbon foam heater, and more than 120 puffs of aerosol were generated. An illustration of the exemplary atomizer assembly 2000 formed of the carbon foam heater 2010 and the carbon fabric aerosol precursor transport element 2100 is shown in
An atomizer according to an embodiment of the present disclosure substantially as illustrated in
Many modifications and other embodiments of the disclosure will come to mind to one skilled in the art to which this disclosure pertains having the benefit of the teachings presented in the foregoing descriptions and the associated drawings. Therefore, it is to be understood that the disclosure is not to be limited to the specific embodiments disclosed herein and that modifications and other embodiments are intended to be included within the scope of the appended claims. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
| Number | Name | Date | Kind |
|---|---|---|---|
| 1771366 | Wyss et al. | Jul 1930 | A |
| 2057353 | Whittemore, Jr. | Oct 1936 | A |
| 2104266 | McCormick | Jan 1938 | A |
| 2805669 | Meriro | Sep 1957 | A |
| 3200819 | Gilbert | Aug 1965 | A |
| 3316919 | Green et al. | May 1967 | A |
| 3398754 | Tughan | Aug 1968 | A |
| 3419015 | Wochnowski | Dec 1968 | A |
| 3424171 | Rooker | Jan 1969 | A |
| 3476118 | Luttich | Nov 1969 | A |
| 4054145 | Berndt et al. | Oct 1977 | A |
| 4106891 | Schladitz | Aug 1978 | A |
| 4131117 | Kite et al. | Dec 1978 | A |
| 4150677 | Osborne | Apr 1979 | A |
| 4190046 | Virag | Feb 1980 | A |
| 4219032 | Tabatznik et al. | Aug 1980 | A |
| 4259970 | Green, Jr. | Apr 1981 | A |
| 4284089 | Ray | Aug 1981 | A |
| 4303083 | Burruss, Jr. | Dec 1981 | A |
| 4449541 | Mays et al. | May 1984 | A |
| 4506682 | Muller | Mar 1985 | A |
| 4635651 | Jacobs | Jan 1987 | A |
| 4674519 | Keritsis et al. | Jun 1987 | A |
| 4708151 | Shelar | Nov 1987 | A |
| 4714082 | Banerjee et al. | Dec 1987 | A |
| 4735217 | Gerth et al. | Apr 1988 | A |
| 4756318 | Clearman et al. | Jul 1988 | A |
| 4771795 | White et al. | Sep 1988 | A |
| 4776353 | Lilja et al. | Oct 1988 | A |
| 4793365 | Sensabaugh, Jr. et al. | Dec 1988 | A |
| 4800903 | Ray et al. | Jan 1989 | A |
| 4819665 | Roberts et al. | Apr 1989 | A |
| 4821749 | Toft et al. | Apr 1989 | A |
| 4830028 | Lawson et al. | May 1989 | A |
| 4836224 | Lawson et al. | Jun 1989 | A |
| 4836225 | Sudoh | Jun 1989 | A |
| 4848374 | Chard et al. | Jul 1989 | A |
| 4848376 | Lilja et al. | Jul 1989 | A |
| 4874000 | Tamol et al. | Oct 1989 | A |
| 4880018 | Graves, Jr. et al. | Nov 1989 | A |
| 4887619 | Burcham, Jr. et al. | Dec 1989 | A |
| 4907606 | Lilja et al. | Mar 1990 | A |
| 4913168 | Potter et al. | Apr 1990 | A |
| 4917119 | Potter et al. | Apr 1990 | A |
| 4917128 | Clearman et al. | Apr 1990 | A |
| 4922901 | Brooks | May 1990 | A |
| 4924888 | Perfetti et al. | May 1990 | A |
| 4928714 | Shannon | May 1990 | A |
| 4938236 | Banerjee et al. | Jul 1990 | A |
| 4941483 | Ridings et al. | Jul 1990 | A |
| 4941484 | Clapp et al. | Jul 1990 | A |
| 4945931 | Gori | Aug 1990 | A |
| 4947874 | Brooks et al. | Aug 1990 | A |
| 4947875 | Brooks et al. | Aug 1990 | A |
| 4972854 | Kiernan et al. | Nov 1990 | A |
| 4972855 | Kuriyama et al. | Nov 1990 | A |
| 4986286 | Roberts et al. | Jan 1991 | A |
| 4987906 | Young et al. | Jan 1991 | A |
| 5005593 | Fagg | Apr 1991 | A |
| 5019122 | Clearman et al. | May 1991 | A |
| 5022416 | Watson | Jun 1991 | A |
| 5042510 | Curtiss et al. | Aug 1991 | A |
| 5056537 | Brown et al. | Oct 1991 | A |
| 5060669 | White et al. | Oct 1991 | A |
| 5060671 | Counts et al. | Oct 1991 | A |
| 5065775 | Fagg | Nov 1991 | A |
| 5072744 | Luke et al. | Dec 1991 | A |
| 5074319 | White et al. | Dec 1991 | A |
| 5076296 | Nystrom et al. | Dec 1991 | A |
| 5093894 | Deevi et al. | Mar 1992 | A |
| 5095921 | Losee et al. | Mar 1992 | A |
| 5097850 | Braunshteyn et al. | Mar 1992 | A |
| 5099862 | White et al. | Mar 1992 | A |
| 5099864 | Young et al. | Mar 1992 | A |
| 5103842 | Strang et al. | Apr 1992 | A |
| 5121757 | White et al. | Jun 1992 | A |
| 5129409 | White et al. | Jul 1992 | A |
| 5131415 | Munoz et al. | Jul 1992 | A |
| 5144962 | Counts et al. | Aug 1992 | A |
| 5143097 | Sohn et al. | Sep 1992 | A |
| 5146934 | Deevi et al. | Sep 1992 | A |
| 5159940 | Hayward et al. | Nov 1992 | A |
| 5159942 | Brinkley et al. | Nov 1992 | A |
| 5179966 | Losee et al. | Jan 1993 | A |
| 5211684 | Shannon et al. | May 1993 | A |
| 5220930 | Gentry | Jun 1993 | A |
| 5224498 | Deevi et al. | Jul 1993 | A |
| 5228460 | Sprinkel, Jr. et al. | Jul 1993 | A |
| 5230354 | Smith et al. | Jul 1993 | A |
| 5235992 | Sensabaugh | Aug 1993 | A |
| 5243999 | Smith | Sep 1993 | A |
| 5246018 | Deevi et al. | Sep 1993 | A |
| 5249586 | Morgan et al. | Oct 1993 | A |
| 5261424 | Sprinkel, Jr. | Nov 1993 | A |
| 5269327 | Counts et al. | Dec 1993 | A |
| 5285798 | Banerjee et al. | Feb 1994 | A |
| 5293883 | Edwards | Mar 1994 | A |
| 5301694 | Raymond | Apr 1994 | A |
| 5303720 | Banerjee et al. | Apr 1994 | A |
| 5318050 | Gonzalez-Parra et al. | Jun 1994 | A |
| 5322075 | Deevi et al. | Jun 1994 | A |
| 5322076 | Brinkley et al. | Jun 1994 | A |
| 5339838 | Young et al. | Aug 1994 | A |
| 5345951 | Serrano et al. | Sep 1994 | A |
| 5353813 | Deevi et al. | Oct 1994 | A |
| 5357984 | Farrier et al. | Oct 1994 | A |
| 5360023 | Blakley et al. | Nov 1994 | A |
| 5369723 | Counts et al. | Nov 1994 | A |
| 5372148 | McCafferty et al. | Dec 1994 | A |
| 5377698 | Litzinger et al. | Jan 1995 | A |
| 5388574 | Ingebrethsen et al. | Feb 1995 | A |
| 5388594 | Counts et al. | Feb 1995 | A |
| 5408574 | Deevi et al. | Apr 1995 | A |
| 5435325 | Clapp et al. | Jul 1995 | A |
| 5445169 | Brinkley et al. | Aug 1995 | A |
| 5468266 | Bensalem et al. | Nov 1995 | A |
| 5468936 | Deevi et al. | Nov 1995 | A |
| 5479948 | Counts et al. | Jan 1996 | A |
| 5498850 | Das | Mar 1996 | A |
| 5498855 | Deevi et al. | Mar 1996 | A |
| 5499636 | Baggett, Jr. et al. | Mar 1996 | A |
| 5501237 | Young et al. | Mar 1996 | A |
| 5505214 | Collins et al. | Apr 1996 | A |
| 5530225 | Hajaligol | Jun 1996 | A |
| 5551450 | Hemsley | Sep 1996 | A |
| 5551451 | Riggs et al. | Sep 1996 | A |
| 5564442 | MacDonald et al. | Oct 1996 | A |
| 5573692 | Das et al. | Nov 1996 | A |
| 5591368 | Fleischhauer et al. | Jan 1997 | A |
| 5593792 | Farrier et al. | Jan 1997 | A |
| 5595577 | Bensalem et al. | Jan 1997 | A |
| 5596706 | Sikk et al. | Jan 1997 | A |
| 5611360 | Tang | Mar 1997 | A |
| 5613504 | Collins et al. | Mar 1997 | A |
| 5613505 | Campbell et al. | Mar 1997 | A |
| 5649552 | Cho et al. | Jul 1997 | A |
| 5649554 | Sprinkel et al. | Jul 1997 | A |
| 5659656 | Das | Aug 1997 | A |
| 5665262 | Hajaligol et al. | Sep 1997 | A |
| 5666976 | Adams et al. | Sep 1997 | A |
| 5666977 | Higgins et al. | Sep 1997 | A |
| 5666978 | Counts et al. | Sep 1997 | A |
| 5692525 | Counts et al. | Dec 1997 | A |
| 5692526 | Adams et al. | Dec 1997 | A |
| 5708258 | Counts et al. | Jan 1998 | A |
| 5711320 | Martin | Jan 1998 | A |
| 5726421 | Fleischhauer et al. | Mar 1998 | A |
| 5727571 | Meiring et al. | Mar 1998 | A |
| 5730158 | Collins et al. | Mar 1998 | A |
| 5750964 | Counts et al. | May 1998 | A |
| 5799663 | Gross et al. | Sep 1998 | A |
| 5816263 | Counts et al. | Oct 1998 | A |
| 5819756 | Mielordt | Oct 1998 | A |
| 5829453 | White et al. | Nov 1998 | A |
| 5865185 | Collins et al. | Feb 1999 | A |
| 5865186 | Volsey, II | Feb 1999 | A |
| 5878752 | Adams et al. | Mar 1999 | A |
| 5880439 | Deevi et al. | Mar 1999 | A |
| 5915387 | Baggett, Jr. et al. | Jun 1999 | A |
| 5934289 | Watkins et al. | Aug 1999 | A |
| 5954979 | Counts et al. | Sep 1999 | A |
| 5967148 | Harris et al. | Oct 1999 | A |
| 6026820 | Baggett, Jr. et al. | Feb 2000 | A |
| 6164287 | White | Feb 2000 | A |
| 6033506 | Klett | Mar 2000 | A |
| 6033623 | Deevi et al. | Mar 2000 | A |
| 6037032 | Klett et al. | Mar 2000 | A |
| 6040560 | Fleischhauer et al. | Mar 2000 | A |
| 6043468 | Toya | Mar 2000 | A |
| 6053176 | Adams et al. | Apr 2000 | A |
| 6089857 | Matsuura et al. | Jul 2000 | A |
| 6095153 | Kessler et al. | Aug 2000 | A |
| 6116247 | Banyasz et al. | Sep 2000 | A |
| 6119700 | Fleischhauer et al. | Sep 2000 | A |
| 6125853 | Susa et al. | Oct 2000 | A |
| 6125855 | Nevett et al. | Oct 2000 | A |
| 6125866 | Nichols et al. | Oct 2000 | A |
| 6155268 | Takeuchi | Dec 2000 | A |
| 6182670 | White | Feb 2001 | B1 |
| 6196218 | Voges | Mar 2001 | B1 |
| 6216706 | Kumar et al. | Apr 2001 | B1 |
| 6289898 | Fournier et al. | Sep 2001 | B1 |
| 6349729 | Pham | Feb 2002 | B1 |
| 6357671 | Cewers | Mar 2002 | B1 |
| 6418938 | Fleischhauer et al. | Jul 2002 | B1 |
| 6446426 | Sweeney et al. | Aug 2002 | B1 |
| 6532965 | Ahhulimen et al. | Mar 2003 | B1 |
| 6598607 | Adiga et al. | Jul 2003 | B2 |
| 6601776 | Oljaca et al. | Aug 2003 | B1 |
| 6615840 | Fournier et al. | Sep 2003 | B1 |
| 6688313 | Wrenn et al. | Feb 2004 | B2 |
| 6701936 | Shafer et al. | Mar 2004 | B2 |
| 6715494 | McCoy | Apr 2004 | B1 |
| 6729269 | Ott et al. | May 2004 | B2 |
| 6730832 | Dominguez et al. | May 2004 | B1 |
| 6722756 | Shayan | Aug 2004 | B2 |
| 6772756 | Shayan | Aug 2004 | B2 |
| 6803545 | Blake et al. | Oct 2004 | B2 |
| 6803550 | Sharpe et al. | Oct 2004 | B2 |
| 6810883 | Felter et al. | Nov 2004 | B2 |
| 6854461 | Nichols | Feb 2005 | B2 |
| 6854470 | Pu | Feb 2005 | B1 |
| 6994096 | Rostami et al. | Feb 2006 | B2 |
| 7011096 | Li et al. | Mar 2006 | B2 |
| 7017585 | Li et al. | Mar 2006 | B2 |
| 7025066 | Lawson et al. | Apr 2006 | B2 |
| 7117867 | Cox et al. | Oct 2006 | B2 |
| 7163015 | Moffitt | Jan 2007 | B2 |
| 7173322 | Cox et al. | Feb 2007 | B2 |
| 7185659 | Sharpe et al. | Mar 2007 | B2 |
| 7234470 | Yang | Jun 2007 | B2 |
| 7290549 | Banerjee et al. | Nov 2007 | B2 |
| 7293565 | Griffin et al. | Nov 2007 | B2 |
| 7392809 | Larson et al. | Jul 2008 | B2 |
| 7513253 | Kobayashi et al. | Apr 2009 | B2 |
| 7647932 | Cantrell et al. | Jan 2010 | B2 |
| 7690385 | Moffitt | Apr 2010 | B2 |
| 7692123 | Baba et al. | Apr 2010 | B2 |
| 7726320 | Robinson et al. | Jun 2010 | B2 |
| 7810505 | Yang | Oct 2010 | B2 |
| 7832410 | Hon | Nov 2010 | B2 |
| 7878209 | Newbery et al. | Feb 2011 | B2 |
| 7896006 | Hamano et al. | Mar 2011 | B2 |
| 8066010 | Newbery et al. | Nov 2011 | B2 |
| 8079371 | Robinson et al. | Dec 2011 | B2 |
| 8372510 | Miller et al. | Feb 2013 | B2 |
| 20020146242 | Vieira | Oct 2002 | A1 |
| 20030098299 | Hiramatsu | May 2003 | A1 |
| 20030131859 | Li et al. | Jul 2003 | A1 |
| 20030226837 | Blake et al. | Dec 2003 | A1 |
| 20040020500 | Wrenn et al. | Feb 2004 | A1 |
| 20040129280 | Woodson et al. | Jul 2004 | A1 |
| 20040149296 | Rostami et al. | Aug 2004 | A1 |
| 20040200488 | Felter et al. | Oct 2004 | A1 |
| 20040224435 | Shibata et al. | Nov 2004 | A1 |
| 20040226568 | Takeuchi et al. | Nov 2004 | A1 |
| 20040255965 | Perfetti et al. | Dec 2004 | A1 |
| 20050016549 | Banerjee et al. | Jan 2005 | A1 |
| 20050016550 | Katase | Jan 2005 | A1 |
| 20050066986 | Nestor et al. | Mar 2005 | A1 |
| 20050151126 | Yamakawa et al. | Jul 2005 | A1 |
| 20050172976 | Newman et al. | Aug 2005 | A1 |
| 20050274390 | Banerjee et al. | Dec 2005 | A1 |
| 20060016453 | Kim | Jan 2006 | A1 |
| 20060032501 | Hale et al. | Feb 2006 | A1 |
| 20060070633 | Rostami et al. | Apr 2006 | A1 |
| 20060162733 | McGrath et al. | Jul 2006 | A1 |
| 20060185687 | Hearn et al. | Aug 2006 | A1 |
| 20060196518 | Hon | Sep 2006 | A1 |
| 20070074734 | Braunshteyn et al. | Apr 2007 | A1 |
| 20070102013 | Adams et al. | May 2007 | A1 |
| 20070215167 | Crooks et al. | Sep 2007 | A1 |
| 20070283972 | Monsees et al. | Dec 2007 | A1 |
| 20080149118 | Oglesby et al. | Jun 2008 | A1 |
| 20080245377 | Marshall et al. | Oct 2008 | A1 |
| 20080257367 | Paterno et al. | Oct 2008 | A1 |
| 20080276947 | Martzel | Nov 2008 | A1 |
| 20080302374 | Wengert et al. | Dec 2008 | A1 |
| 20090011673 | Ko et al. | Jan 2009 | A1 |
| 20090065010 | Shands | Mar 2009 | A1 |
| 20090095311 | Hon | Apr 2009 | A1 |
| 20090095312 | Herbrich et al. | Apr 2009 | A1 |
| 20090126745 | Hon | May 2009 | A1 |
| 20090188490 | Hon | Jul 2009 | A1 |
| 20090230117 | Fernando et al. | Sep 2009 | A1 |
| 20090260641 | Monsees et al. | Oct 2009 | A1 |
| 20090260642 | Monsees et al. | Oct 2009 | A1 |
| 20090272379 | Thorens et al. | Nov 2009 | A1 |
| 20090283103 | Nielsen et al. | Nov 2009 | A1 |
| 20090293892 | Williams et al. | Dec 2009 | A1 |
| 20090320863 | Fernando et al. | Dec 2009 | A1 |
| 20090324206 | Young et al. | Dec 2009 | A1 |
| 20100006113 | Urtsev et al. | Jan 2010 | A1 |
| 20100024834 | Oglesby et al. | Feb 2010 | A1 |
| 20100043809 | Magnon | Feb 2010 | A1 |
| 20100059070 | Potter et al. | Mar 2010 | A1 |
| 20100059073 | Hoffmann et al. | Mar 2010 | A1 |
| 20100065075 | Banerjee et al. | Mar 2010 | A1 |
| 20100083959 | Siller | Apr 2010 | A1 |
| 20100163063 | Fernando et al. | Jul 2010 | A1 |
| 20100200006 | Robinson et al. | Aug 2010 | A1 |
| 20100229881 | Hearn | Sep 2010 | A1 |
| 20100242974 | Pan | Sep 2010 | A1 |
| 20100242976 | Katayama et al. | Sep 2010 | A1 |
| 20100258139 | Onishi et al. | Oct 2010 | A1 |
| 20100300467 | Kuistilla et al. | Dec 2010 | A1 |
| 20100307518 | Wang | Dec 2010 | A1 |
| 20100313901 | Fernando et al. | Dec 2010 | A1 |
| 20110005535 | Xiu | Jan 2011 | A1 |
| 20110011396 | Fang | Jan 2011 | A1 |
| 20110036363 | Urtsev et al. | Feb 2011 | A1 |
| 20110036365 | Chong et al. | Feb 2011 | A1 |
| 20110073121 | Levin et al. | Mar 2011 | A1 |
| 20110088707 | Hajaligol | Apr 2011 | A1 |
| 20110094523 | Thorens et al. | Apr 2011 | A1 |
| 20110120480 | Brenneise | May 2011 | A1 |
| 20110126847 | Zuber et al. | Jun 2011 | A1 |
| 20110126848 | Zuber et al. | Jun 2011 | A1 |
| 20110155153 | Thorens et al. | Jun 2011 | A1 |
| 20110155718 | Greim et al. | Jun 2011 | A1 |
| 20110162663 | Bryman | Jul 2011 | A1 |
| 20110168194 | Hon | Jul 2011 | A1 |
| 20110180082 | Banerjee et al. | Jul 2011 | A1 |
| 20110265806 | Alarcon et al. | Nov 2011 | A1 |
| 20110309157 | Yang et al. | Dec 2011 | A1 |
| 20120042885 | Stone et al. | Feb 2012 | A1 |
| 20120060853 | Robinson et al. | Mar 2012 | A1 |
| 20120132643 | Choi et al. | May 2012 | A1 |
| 20120231464 | Yu et al. | Sep 2012 | A1 |
| 20120318882 | Abehasera | Dec 2012 | A1 |
| 20130081642 | Safari | Apr 2013 | A1 |
| 20130192620 | Tucker et al. | Aug 2013 | A1 |
| 20130306084 | Flick | Nov 2013 | A1 |
| 20130340775 | Juster et al. | Dec 2013 | A1 |
| 20140238422 | Plunkett | Aug 2014 | A1 |
| Number | Date | Country |
|---|---|---|
| 276250 | Jul 1965 | AU |
| 2 641 869 | May 2010 | CA |
| 1040914 | Apr 1990 | CN |
| 1541577 | Nov 2004 | CN |
| 2719043 | Aug 2005 | CN |
| 1778673 | May 2006 | CN |
| 200997909 | Jan 2008 | CN |
| 101116542 | Feb 2008 | CN |
| 101176805 | May 2008 | CN |
| 201379072 | Jan 2010 | CN |
| 10 2006 004 484 | Aug 2007 | DE |
| 20 2009 010 400 | Nov 2009 | DE |
| 0 295 122 | Dec 1988 | EP |
| 0 845 220 | Jun 1998 | EP |
| 1 618 803 | Jan 2006 | EP |
| 2 316 286 | May 2011 | EP |
| 2 468 116 | Jun 2012 | EP |
| 1444461 | Jul 1976 | GB |
| WO 198602528 | May 1986 | WO |
| WO 199748293 | Dec 1997 | WO |
| WO 0237990 | May 2002 | WO |
| WO 2004043175 | May 2004 | WO |
| WO 2007131449 | Nov 2007 | WO |
| WO 2009105919 | Sep 2009 | WO |
| WO 2009155734 | Dec 2009 | WO |
| WO 2010003480 | Jan 2010 | WO |
| WO 2010045670 | Apr 2010 | WO |
| WO 2010091593 | Aug 2010 | WO |
| WO 2010118644 | Oct 2010 | WO |
| WO 2010140937 | Dec 2010 | WO |
| WO 2011010334 | Jan 2011 | WO |
| WO 2010073122 | Jul 2011 | WO |
| WO 2011081558 | Jul 2011 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20150059780 A1 | Mar 2015 | US |
