Patent Grant
10865148
The following is directed to particulate materials, such as, particulate materials including a first phase and a second phase, and methods of forming such particulate materials.
Abrasive particles and abrasive articles made from abrasive particles are useful for various material removal operations including grinding, finishing, and polishing. Depending upon the type of abrasive material, such abrasive particles can be useful in shaping or grinding a wide variety of materials and surfaces in the manufacturing of goods. Certain types of abrasive particles have been formulated to date that have particular geometries, such as triangular shaped abrasive particles and abrasive articles incorporating such objects. See, for example, U.S. Pat. Nos. 5,201,916; 5,366,523; and 5,984,988.
Three basic technologies that have been employed to produce abrasive particles having a specified shape are (1) fusion, (2) sintering, and (3) chemical ceramic. In the fusion process, abrasive particles can be shaped by a chill roll, the face of which may or may not be engraved, a mold into which molten material is poured, or a heat sink material immersed in an aluminum oxide melt. See, for example, U.S. Pat. No. 3,377,660, disclosing a process comprising the steps of flowing molten abrasive material from a furnace onto a cool rotating casting cylinder, rapidly solidifying the material to form a thin semisolid curved sheet, densifying the semisolid material with a pressure roll, and then partially fracturing the strip of semisolid material by reversing its curvature by pulling it away from the cylinder with a rapidly driven cooled conveyor.
In the sintering process, abrasive particles can be formed from refractory powders having a particle size of up to 10 micrometers in diameter. Binders can be added to the powders along with a lubricant and a suitable solvent, e.g., water. The resulting mixtures, mixtures, or slurries can be shaped into platelets or rods of various lengths and diameters. See, for example, U.S. Pat. No. 3,079,242, which discloses a method of making abrasive particles from calcined bauxite material comprising the steps of (1) reducing the material to a fine powder, (2) compacting under affirmative pressure and forming the fine particles of said powder into grain sized agglomerations, and (3) sintering the agglomerations of particles at a temperature below the fusion temperature of the bauxite to induce limited recrystallization of the particles, whereby abrasive grains are produced directly to size.
Chemical ceramic technology involves converting a colloidal dispersion or hydrosol (sometimes called a sol), optionally in a mixture, with solutions of other metal oxide precursors, to a gel or any other physical state that restrains the mobility of the components, drying, and firing to obtain a ceramic material. See, for example, U.S. Pat. Nos. 4,744,802 and 4,848,041.
Still, there remains a need in the industry for improving performance, life, and efficacy of abrasive particles, and the abrasive articles that employ abrasive particles.
According to one aspect, a particulate material includes a body including a first phase including alumina having an average crystallite size of not greater than 5 microns, and wherein the body further comprises a second phase having a platelet shape.
In another aspect, a particulate material includes a body having a first phase including alumina and a second phase having a platelet shape, wherein the second phase comprises Sr in a range of at least 0.2 wt % and not greater than 5 wt % for a total weight of the body.
According to another aspect, a particulate material includes a body having a first phase including alumina and a second phase having a platelet shape and containing Sr and Ce, wherein the second phase comprises a Sr content within a range of at least 0.2 wt % and not greater than 5 wt % for a total weight of the body, and wherein the second phase comprises a Ce content within a range of at least 0.05 wt % and not greater than 2 wt % for a total weight of the body.
In yet another aspect, a particulate material includes a body having a first phase including alumina and a second phase having a platelet shape and containing Sr and Ce, wherein the second phase comprises Sr and Ce, and wherein the second phase comprises a ratio of Sr:Ce within a range of at least 1:1 to not greater than 100:1.
The present disclosure may be better understood, and its numerous features and advantages made apparent to those skilled in the art by referencing the accompanying drawings.
The following is directed to methods of forming a particulate material having certain compositions, including a particulate material in the form of abrasive particles, shaped abrasive particles, and the like. The particulate material may be used in various articles, such as abrasive articles, and more particularly, fixed abrasives, such as bonded abrasive articles, coated abrasive articles, non-woven abrasive articles and the like. Still, in other instances, the particulate material may be used as a free abrasive material, wherein the particulate material is not necessarily attached to a substrate or incorporated into a matrix material.
As noted herein, the raw material powder can included a seeded material, such as material processed through a seeded processing pathway. That is, for example, the raw material may be include a seed material, which may be a compound, complex, or element configured to control the growth of particular crystalline phases within the raw material powder. The seeded raw material powder may include a minority content of seed material, which may facilitate the formation of particular crystalline phases during further processing of the raw material powder. One non-limiting seeded processing pathway is described herein. In other instances, the raw material powder may include an unseeded material, and can be essentially free of seed material.
Providing a raw material powder can include synthesis of a particulate material by obtaining an aluminous raw material. While certain aluminous raw materials can be sourced commercially, in other instances, the aluminous raw material may be manufactured. In accordance with an embodiment, the process of forming the raw material powder can include processes such as, dispersing, mixing, gelling, seeding, calcining, shaping, printing, molding, extruding, pressing, drying, crushing, sieving, sorting, and a combination thereof.
As noted herein, the raw material powder may be obtained by manufacturing an aluminous raw material according to a seeded pathway. In one embodiment, the aluminous raw material can include a boehmite precursor and boehmite seeds in a suspension (alternatively sol or slurry), that can be heat-treated (such as by hydrothermal treatment) to convert the boehmite precursor into boehmite particulate material formed of particles or crystallites. The term “boehmite” is generally used herein to denote alumina hydrates including mineral boehmite, typically being Al2O3.H2O and having a water content on the order of 15%, as well as pseudoboehmite, having a water content higher than 15%, such as 20-38% by weight. It is noted that boehmite (including pseudoboehmite) has a particular and identifiable crystal structure, and accordingly unique X-ray diffraction pattern, and as such, is distinguished from other aluminous materials including other hydrated aluminas such as ATH (aluminum trihydroxide) a common precursor material used for the fabrication of boehmite particulate materials.
After forming suitable boehmite particulate material, a heat treatment process can be carried out to effect polymorphic transformation, which removes water and forms an alumina material. According to one aspect, the boehmite particulate material can have a relatively elongated morphology, and such morphology of the boehmite may be largely preserved in the particulate material.
Primary aspect ratio is defined as the ratio of the longest dimension to the next longest dimension (i.e., width) perpendicular to the longest dimension but in the same plane as the longest dimension and is generally not less than 2:1. Such particles may be referred to as needle-like or needle-shaped particles, particularly when the thickness of the particles (a dimension perpendicular to the length and extending out of the plane of the length and width) is less than the length of the particles.
Alternatively, the boehmite particulate material can have a platy or platelet-shaped contour, generally have an elongated structure having the primary aspect ratios described above in connection with the needle-shaped particles. However, platelet-shaped particles generally have opposite major surfaces, the opposite major surfaces being generally planar and generally parallel to each other.
The morphology of the boehmite particulate material formed through a seeding process can have a relatively fine particle or crystallite size. Generally, the average boehmite material particle size is not greater than about 1000 nanometers, such as within a range of at least 100 to not greater than 1000 nanometers. Other embodiments have even finer average particle sizes, such as not greater than about 800 nanometers or not greater than 750 nanometers or not greater than 600 nanometers or not greater than 500 nanometers or not greater than 400 nanometers or even not greater than 300 nanometers. As used herein, the “average particle size” in connection with high aspect ratio boehmite particulate material is used to denote the average longest or length dimension of the particles.
In addition to aspect ratio and average particle size of the boehmite particulate material, morphology of the boehmite particulate material may be further characterized in terms of specific surface area. Here, the commonly available BET technique was utilized to measure specific surface area of the boehmite particulate material. According to embodiments herein, the boehmite particulate material may have a relatively high specific surface area, such as not less than about 10 m2/g, such as not less than about 50 m2/g or not less than 70 m2/g or even not less than about 90 m2/g. In a non-limiting embodiment, the specific surface area of the boehmite particulate material can be not greater than about 400 m2/g, such as not greater than 350 m2/g or even not greater than 300 m2/g. The specific surface area can be within a range including any of the minimum and maximum values noted above.
Turning to the details of the processes by which the seeded boehmite particulate material may be manufactured, generally ellipsoid, needle, or platelet-shaped boehmite is formed from a boehmite precursor, typically an aluminous material including bauxitic minerals, by hydrothermal treatment as generally described in the commonly owned patent described above, U.S. Pat. No. 4,797,139. More specifically, the boehmite particulate material may be formed by combining the boehmite precursor and boehmite seeds in suspension, exposing the suspension (alternatively sol or slurry) to heat treatment to cause conversion of the raw material into boehmite particulate material, further influenced by the boehmite seeds provided in suspension. Heating may be conducted in an autogenous environment, such that an elevated pressure is generated during processing. The pH of the suspension is generally selected from a value of less than 7 or greater than 8, and the boehmite seed material can have a particle size finer than about 0.5 microns. Generally, the seed particles are present in an amount greater than about 1% by weight of the boehmite precursor (calculated as Al2O3), and heating is carried out at a temperature greater than about 120° C., such as greater than about 125° C., or even greater than about 130° C., and at a pressure that is autogenously generated, typically around 30 psi.
Following heat treatment, such as by hydrothermal treatment, the liquid content is generally removed, such as through an ultrafiltration process or by heat treatment to evaporate the remaining liquid. Thereafter, the resulting mass is generally crushed to a particular average particle size. It is noted that the particulate size described herein generally describes the individual particles formed through processing, rather than the aggregates which may remain in certain embodiments (e.g., for those products that call for an aggregated material).
Certain processing variables may be modified during the formation of the boehmite particulate material, to affect the desired morphology. These variables include the ratio of boehmite precursor to boehmite seed, the particular type or species of acid or base used during processing (as well as the relative pH level), and the temperature (which is directly proportional to pressure in an autogenous hydrothermal environment) of the system.
Suitable acids and bases include mineral acids such as nitric acid, organic acids such as formic acid, halogen acids such as hydrochloric acid, and acidic salts such as aluminum nitrate and magnesium sulfate. Effective bases include, for example, amines including ammonia, alkali hydroxides such as potassium hydroxide, alkaline hydroxides such as calcium hydroxide, and basic salts.
After forming the boehmite particulate material, which can be the raw material powder used in later processes according to embodiments herein, the process can further include heat-treatment of the boehmite particulate material to form an aluminous material. In accordance with a particular embodiment, the heat-treatment can include calcination of the boehmite particulate material at a temperature sufficient to cause transformation into a particular phase of alumina (e.g., gamma, delta, theta, alpha) or combination of phases of alumina providing a suitable aluminous material. For purposes of clarification, an aluminous material is one that comprises a majority content (wt %) of alumina (Al2O3) and preferably, at least about 80 wt %, at least 90 wt %, at least 95 wt % or even consisting essentially of alumina. Still, the boehmite particulate material may be used for other processes before heat-treatment, including for example the provision of an additive, which is described in more detail herein.
Referring again to
The process of calcination can include heating the raw material powder to a temperature suitable to remove particular volatile components and facilitate the formation of a porous raw material. In one particular instance, the process of calcining can be conducted at a temperature of at least about 300° C. In other instances, the calcining temperature may be greater, such as at least about 600° C., at least about 700° C., or even at least about 750° C. Still, the process of calcining may be conducted at a temperature not greater than about 1200° C., such as not greater than about 1000° C. or even not greater than about 900° C. It will be appreciated that the process of calcining can be conducted at a temperature within a range between any of the minimum and maximum values noted above.
In certain instances, the process of impregnating can include saturation of the porosity of the raw material powder with the additive. Saturation can include filling at least a portion of the pore volume of the raw material powder with the additive. Still, a saturation process may include filling a majority of the porosity with the additive, and more particularly, may include filling substantially all of the total pore volume of the raw material powder with the additive. The saturation process, which may further include an over-saturation process, can utilize processes including, but not limited to, soaking, mixing, stirring, increased pressure above atmospheric conditions, decreased pressure below atmospheric conditions, particular atmospheric conditions (e.g., inert atmosphere, reducing atmosphere, oxidizing atmosphere), heating, cooling, and a combination thereof. In at least one particular embodiment, the process of including can include soaking the raw material powder in a solution containing the additive.
In certain instances, the additive can include one or more components. For example, the additive may include a first component and a second component distinct from the first component. In accordance with an embodiment, the first component may include strontium. According to certain embodiments, the first component may include a salt, and may be present as a solution including the at least one element. For example, the first component may include a nitrate salt solution. In one particular embodiment, the additive can include strontium nitrate, which may be added in the form of a solution.
In certain instances, the additive may include a second component, which can be distinct from the first component. For example, the second component may include an element such as cerium. In addition, the second component may be present as a compound including cerium. According to a particular embodiment, the second component can include cerium, and more particularly, may include a salt compound including cerium, such as cerium nitrate, which may be added in the form of a solution.
The process of including the additive can include particular combinations of the first component and the second component into the raw material powder. For example, in one embodiment, the process of including the additive can include providing the first component at a first time and the second component at a second time. The first time and second time may be the same as each other, such that the first component and second component can be added to the raw material powder simultaneously. Still, in another embodiment, the first component and second component can be added to the raw material powder at different times. For example, the first component may be added before the second component. Alternatively, the first component may be added after the second component.
The process of including an additive can include performing at least one process between the addition of the first component and the addition of the second component to the raw material powder. For example, some exemplary processes that may be conducted between the addition of the first component and the second component can include mixing, drying, heating, calcining and a combination thereof. In one particular embodiment, the process of including the additive may include providing the first component to the raw material powder, heating the raw material powder after the addition of the first component to the raw material powder, and providing the second component to the raw material powder and first component after heating the raw material and first component. It will be appreciated that such a heating process may include a calcining process.
According to alternative embodiment, the process of including an additive can include a process of doping. Doping can include a process wherein the additive is combined with the raw material powder prior to conducting certain processes, particularly calcination of the raw material powder. The doping process may also utilize an additive including a first component and a second component, according to embodiments herein. In particular, the first component and second component may both be added to the raw material powder prior to a calcination process.
Referring again to
The process of forming can include combining the first component and second component of the additive as precursors to form the second phase within the particulate material. In at least one embodiment, the process of forming can include combining the first and second components to form a second phase in the body of the particulate material. The process of forming may also include converting the precursor material of the additives into the second phase. For example, the first and second components may be added to the mixture as precursors (e.g., salts including the desired elements). In one embodiment, the process of converting the precursor into the second phase can include the application or alteration of at least one of temperature, pressure, atmosphere, or any combination thereof. Converting the precursor to a second phase can include volatilization of certain species, including for example, water. Moreover, the process of converting can include crystallization or a change in crystalline structure of the precursor of the second phase. In still another embodiment, the process of converting can include densification.
According to a particular embodiment, the process of converting the precursor to the second phase can include firing the raw material and precursor of the second phase. The firing process may include a sintering process, including densification of the material and formation of high temperature phases of the first phase, including for example, alpha alumina. Firing may be conducted at a temperature of at least 800° C., such as at least 1000° C. or at least 1200° C. or even at least 1400° C. Still, firing may be conducted at a temperature that is not greater than 1700° C., such as not greater than 1600° C. or even not greater than 1500° C. It will be appreciated that firing may be conducted at a temperature within a range between any of the above minimum and maximum temperatures. Firing may also include sintering, which includes densification of the body.
Furthermore, it will be appreciated that firing may be conducted for a particular time and under a particular atmosphere. For example, firing may be conducted for at least about 1 minute at ambient conditions, or even at least about 4 minutes, at least about one hour, such as at least about two hours, or even at least about three hours. Furthermore, the atmosphere utilized during firing may include an oxidizing atmosphere, a reducing atmosphere, or an inert atmosphere.
In accordance with an embodiment, after conducting the forming process, the particulate material can have a density of at least about 95% theoretical density. In other instances, the particulate material may have a greater density, such as at least about 96% or even at least about 97% or at least 98% or at least 99% or at least 99.5% or at least 99.9% theoretical density.
After conducting the forming process the particulate material may have a specific surface area, such as not greater than about 100 m2/g. In still other embodiments, the specific surface area of the particulate material maybe not greater than about 90 m2/g, such as not greater than 80 m2/g, or even not greater than about 10 m2/g, or even not greater than about 1 m2/g. Still, the specific surface area of the particulate material may be at least about 0.01 m2/g, or even at least about 0.05 m2/g. It will be appreciated that the specific surface area of the particulate material maybe be within a range between any of the above minimum and maximum values.
In yet another embodiment, the particulate material can have a body having an average particle size, which may be selected from a group of predetermined sieve sizes. For example, the body can have an average particle size of not greater than about 5 mm, such as not greater than about 3 mm, not greater than about 2 mm, not gather than about 1 mm, or even not greater than about 0.8 mm Still, in another embodiment, the body may have an average particle size of at least about 0.1 μm. It will be appreciated that the body may have an average particle size within a range between any of the minimum and maximum values noted above.
Particles for use in the abrasives industry are generally graded to a given particle size distribution before use. Such distributions typically have a range of particle sizes, from coarse particles to fine particles. In the abrasive art this range is sometimes referred to as a “coarse”, “control”, and “fine” fractions. Abrasive particles graded according to abrasive industry accepted grading standards specify the particle size distribution for each nominal grade within numerical limits. Such industry accepted grading standards (i.e., abrasive industry specified nominal grade) include those known as the American National Standards Institute, Inc. (ANSI) standards, Federation of European Producers of Abrasive Products (FEPA) standards, and Japanese Industrial Standard (JIS) standards. ANSI grade designations (i.e., specified nominal grades) include: ANSI 4, ANSI 6, ANSI 8, ANSI 16, ANSI 24, ANSI 36, ANSI 40, ANSI 50, ANSI 60, ANSI 80, ANSI 100, ANSI 120, ANSI 150, ANSI 180, ANSI 220, ANSI 240, ANSI 280, ANSI 320, ANSI 360, ANSI 400, and ANSI 600. FEPA grade designations include P8, P12, P16, P24, P36, P40, P50, P60, P80, P100, P120, P150, P180, P220, P320, P400, P500, P600, P800, P1000, and P1200. JIS grade designations include JIS8, JIS12, JIS 16, JIS24, JIS36, JIS46, JIS54, JIS60, JIS80, JIS 100, JIS150, JIS180, JIS220, JIS240, JIS280, JIS320, JIS360, JIS400, JIS600, JIS800, JIS 1000, JIS 1500, JIS2500, JIS4000, JIS6000, JIS8000, and JIS10,000. Alternatively, the shaped abrasive particles 20 can graded to a nominal screened grade using U.S.A. Standard Test Sieves conforming to ASTM E-1 1 “Standard Specification for Wire Cloth and Sieves for Testing Purposes.” ASTM E-1 1 prescribes the requirements for the design and construction of testing sieves using a medium of woven wire cloth mounted in a frame for the classification of materials according to a designated particle size. A typical designation may be represented as −18+20 meaning that the particles pass through a test sieve meeting ASTM E-1 1 specifications for the number 18 sieve and are retained on a test sieve meeting ASTM E-1 1 specifications for the number 20 sieve. In various embodiments, the particulate material can have a nominal screened grade comprising: −18+20, −20/+25, −25+30, −30+35, −35+40, −40+45, −45+50, −50+60, −60+70, −70/+80, −80+100, −100+120, −120+140, −140+170, −170+200, −200+230, −230+270, −270+325, −325+400, −400+450, −450+500, or −500+635. Alternatively, a custom mesh size could be used such as −90+100. The body of the particulate material may be in the form of a shaped abrasive particle, as described in more detail herein.
In accordance with one aspect, the particulate material can have a body including a first phase and a second phase, wherein the second phase can have a platelet shape. The second phase can be distributed throughout the first phase. Further details on the morphology and chemistry of the particulate material is provided in the embodiments below.
According to one embodiment, the first phase may include alumina, such as alpha alumina. The first phase may be primarily alpha alumina, and more particularly, may consist essentially of alpha alumina. In certain instances, the body may be formed such that it is not greater than about 1 wt % of low-temperature alumina phases for the total weight of the body. As used herein, low temperature alumina phases can include transition phase aluminas, bauxites or hydrated alumina, including for example gibbsite, boehmite, diaspore, and mixtures containing such compounds and minerals. Certain low temperature alumina materials may also include some content of iron oxide. Moreover, low temperature alumina phases may include other minerals, such as goethite, hematite, kaolinite, and anastase. In particular instances, the particulate material can consist essentially of alpha alumina as the first phase and may be essentially free of low temperature alumina phases.
Furthermore, the particulate material may be formed such that the body includes not greater than about 1 wt % of impurity elements for the total weight of the body. Some exemplary impurity elements can include transition metal elements, alkaline earth elements, alkaline elements, and a combination thereof. In one particular instance, the body can include a limited amount of water, such as a content within the body of not greater than about 1 wt % water for the total weight of the body. Moreover, the body can be essentially free of water.
In one aspect, the particulate material may have a body including a first phase having at least about 51 wt % alumina for a total weight of the first phase. For other embodiments, the body can include at least about 60 wt % alumina for the total weight of the first phase, such as least about 70 wt % or at least about 80 wt % or at least about 83 wt % or at least about 85 wt % or at least about 90 wt % or at least about 93 wt %, at least about 95 wt % or at least 97 wt % alumina for the total weight of the body. In at least one embodiment, the first phase consists essentially of alumina. For yet another embodiment, the body may include a seeded alumina material, and the first phase may include alpha alumina formed from the seeded alumina material.
In another embodiment, the body can include a particular content of alumina, which may facilitate particulate material having improved properties. For example, the body can include at least 51 wt % alumina for the total weight of the body, such as at least 60 wt % alumina or at least 70 wt % alumina or at least 80 wt % alumina or at least 90 wt % alumina or at least 95 wt % alumina or at least 97 wt % alumina. Still, in another non-limiting embodiment, the body may include not greater than 99.9 wt % alumina for the total weight of the body, such as not greater than 99.5% alumina or not greater than 99 wt % alumina or not greater than 98.5 wt % alumina. It will be appreciated that the body can include a content of alumina within a range including any of the minimum and maximum percentages noted above.
Furthermore, the particulate material can have a body including at least about 50 wt % of the first phase for the total weight of the body. In other instances, the content of the first phase within the body may be greater, such as at least about 55 wt % or at least about 60 wt % or at least about 70 wt % or at least about 80 wt % or at least about 85 wt % or at least about 90 wt % or at least about 93 wt % or even at least about 95 wt % for the total weight of the body. Still, the body may include not greater than about 99.5 wt % of the first phase for the total weight of the body, such as not greater than about 99 wt % or not greater than about 98 wt % or even not greater than 95 wt % of the first phase for the total weight of the body. It will be appreciated that the content of the first phase within the body can be within a range between any of the minimum and maximum percentages noted above.
In yet another embodiment, the particulate material can include a first phase having grains defining individual single crystal domains or crystallites having an average crystallite size of not greater than about 5 microns. Still, in other instances, the average crystallite size of the first phase may be not greater than 4 microns or not greater than 3 microns or not greater than 2 microns or not greater than 1 micron or not greater than 0.9 microns or not greater than 0.8 microns or not greater than 0.7 microns or not greater than 0.6 microns or not greater than 0.5 microns or not greater than 0.4 microns. In one non-limiting embodiment, the average crystallite size of the first phase can be at least 0.01 microns or at least 0.05 microns or at least 0.1 microns. It will be appreciated that the average crystallite size of the first phase can be within a range between any of the minimum and maximum values noted above. A domain can include a single crystal or a group of crystals having the same or substantially the same alignment when viewed in two dimensions.
The average crystallite size of the first phase can be measured using scanning electron microscope (SEM) photomicrographs and imaging analysis software, such as ImageJ. Samples of abrasive grains are prepared by making a bakelite mount in epoxy resin then polished with one or more polishing slurries in a manner to make the crystal grains clearly visible when viewed by SEM. For example, a series of polishing pads and polishing slurries from 45 microns to a submicron polishing slurry were used at a speed of approximately 200-300 RPMs under a weight of 20-30 lbs. Individual grains (5-10 grits) are mounted on the SEM mount then gold coated for SEM preparation. SEM photomicrographs of five individual abrasive particles are taken at approximately 50,000× magnification. The average crystallite size is calculated using the following steps: 1) using image analysis software, for each image, six horizontal lines are drawn across the image at regularly spaced intervals 2) the user marks the points at which any of the lines cross grain boundaries; 3) using the imaging software or similar computer aided analysis tool, the length of each of the lines between the intersection points is measured and identified as a crystal length, 4) the raw data of crystal length is exported to a spreadsheet for calculation of an average that represents the average crystal size for the sample image. The same process is conducted for each of the five individual abrasive particles and the results are averaged to determine the average crystallite size for the first phase.
As noted herein, the body can further include a second phase. For certain particulate materials according to embodiments herein, the body can consist essentially of the first phase and the second phase. In one instance, the body can include at least 0.1 wt % of the second phase for the total weight of the body. For other embodiments, the content of the second phase within the body can be greater, such as at least about 0.2 wt % or at least about 0.5 wt % or at least about 0.8 wt % or at least about 1 wt % or at least about 1.3 wt % or at least about 1.5 wt % or at least about 1.8 wt % or at least about 2 wt % or at least 2.2 wt % or at least 2.5 wt %. Still, the content of the second phase within the body may be limited, such that it may be not greater than about 10 wt %, such as not greater than about 8 wt % or not greater than about 7 wt % or not greater than about 6 wt % or not greater than about 5 wt % or not greater than about 4 wt % or not greater than about 3.5 wt % or not greater than about 3 wt % or not greater than about 2.8 wt % or not greater than about 2.6 wt % or not greater than about 2.5 wt %. It will be appreciated that the content of the second phase within the body can be within a range between any of the minimum and maximum percentages noted above.
The second phase can be distinct from the first phase by at least one of average grain size, composition, content, crystal structure, aspect ratio, or any combination thereof. In accordance with an embodiment, the second phase can include an oxide. In certain instances, the second phase can include strontium (Sr), cerium (Ce), or any combination thereof. The strontium and cerium may be in the form of one or more chemical compounds, and particularly, an oxide compound. For example, the strontium and cerium may be in the form of a magnetoplumbite structure, such as CeSrAl11O19. In at least one embodiment, the second phase consists essentially of strontium and cerium, and more particularly, strontium and cerium in the form of an oxide compound. The second phase may include a crystalline material, and more particularly, may consist essentially of a crystalline material or polycrystalline material. The second phase may be free of any amorphous phase material.
In one embodiment, the second phase may be disposed at the grain boundaries of any of the other phases, such as the first phase. A majority of the second phase may be disposed as an intergranular phase (i.e., between grains at the grain boundaries) between any of the phases described in embodiments herein. For example, at least 60% of the total content of the second phase can be disposed at the grain boundaries of the first phase. In other embodiments, the amount of second phase disposed at the grain boundaries can be greater, such as at least about 70% of the second phase, at least about 80% of the second phase, at least about 90% of the second phase, or even in some instances essentially all of the second phase can be disposed at the grain boundary of the first phase.
According to a particular embodiment, the second phase comprises a platelet shape. The platelet shape of the second phase can have a particular aspect ratio when viewed in two-dimensions, such as by scanning electron microscope based on a surface of a polished sample. Platelet shaped phases can have an aspect ratio of at least 1.1:1 for the length relative to the width, wherein the length is the longest dimension of the phase as viewed in two dimensions and the width is the longest dimension extending perpendicular to the length as viewed in the same plane as the length. The second phase can have a platelet shape, whereas the first phase may have a more equiaxed shape as viewed in two-dimensions.
According to one embodiment, the second phase can include platelets having a length (l) and a width (w), wherein the length is greater than the width. More particularly, the platelets of the second phase can have an average primary aspect ratio of length:width of at least 1.2:1, such as at least 1.3:1 or at least 1.3:1 or at least 1.4:1 or at least 1.5:1 or at least 1.7:1 or at least 1.8:1 or at least 1.9:1 or at least 2:1 or at least 2.3:1 or at least 2.5:1 or at least 3:1 or at least 4:1 or at least 5:1 or at least 7:1 or at least 10:1. In still another embodiment, the platelets of the second phase can have an average primary aspect ratio of length:width of not greater than 1000:1 or not greater than 750:1 or not greater than 500:1 or not greater than 100:1 or not greater than 50:1 or not greater than 20:1 or not greater than 10:1. It will be appreciated that the platelets of the second phase can have an average primary aspect ratio within a range including any of the minimum and maximum ratios noted above.
In more particular instances, the platelets of the second phase can have an average length of at least 0.2 microns, such as at least 0.3 microns or at least 0.4 microns or at least 0.5 microns or at least 0.6 microns or at least 0.7 microns or at least 0.8 microns or at least 0.9 microns or at least 1 microns or at least 1.2 microns or at least 1.5 microns. Still, in another non-limiting embodiment, the average length of the platelets of the second phase can be not greater than 10 microns or not greater than 9 microns or not greater than 8 microns or not greater than 7 microns or not greater than 6 microns or not greater than 5 microns or not greater than 4 microns or not greater than 3 microns or not greater than 2 microns or not greater than 1.5 microns. It will be appreciated that the average length can be within a range including any of the minimum and maximum values noted above.
It will be appreciated that the length and width of the platelets is measured according to the following process. A sample of the material is prepared in the same manner as described above for the measurement of the average crystallite size, including preparation and imaging of five randomly selected abrasive particles. For each of the particles, a random region of the particle is viewed using a scanning electron microscope at approximately 20,000×. An image of the sample is obtained and analyzed using imaging software, such as ImageJ. For each crystallite of the second phase presented in the image, a line is drawn along the length of the crystallite, wherein the length represents the longest dimension. The line may be drawn with the assistance of imaging software such as ImageJ. The process is repeated five times for each of the five samples of particles. The results are tabulated and averaged to calculate the average length of the crystallites of the second phase.
In another embodiment, the platelets of the second phase can have an average width of at least 0.02 microns, such as at least 0.05 microns or at least 0.08 microns or at least 0.1 microns or at least 0.12 microns or at least 0.15 microns or at least 0.18 microns or at least 0.2 microns or at least 0.22 microns or at least 0.25 microns or at least 0.3 microns. Still, in another non-limiting embodiment, the average width of the platelets of the second phase can be not greater than 5 microns or not greater than 3 microns or not greater than 2 microns or not greater than 1 micron or not greater than 0.8 microns or not greater than 0.6 microns or not greater than 0.4 microns or not greater than 0.3 microns or not greater than 0.2 microns or not greater than 0.15 microns. It will be appreciated that the average width can be within a range including any of the minimum and maximum values noted above.
The average width of the platelets of the second phase can be measured using the same procedure as noted above for the measurement of the length of the platelets of the second phase. However, the width was measured at the midpoint of the line used to measure the length. The line representing the width was drawn in a direction perpendicular to the line representing the length as close as possible to the midpoint of the line representing the length.
The particulate material can have a body that includes a particular ratio of size of grains of the first phase and second phase. For example, the body can include a first phase having a first average crystallite size and a second phase having an average length of the platelets. In certain instances, the average length of the platelets can be greater than the first average crystallite size of the first phase. Moreover, in at least one aspect, the body can have a ratio (G2/G1) wherein G1 represents the average grain size of the first phase and G2 represents the average length of the platelets of the second phase. In accordance with a particular embodiment, the ratio (G2/G1) can have a value of at least about 1.1, such as at least about 1.5, at least about 2, at least about 3, at least about 5, at least about 8, at least about 10, at least about 15, a least about 20, or even at least about 50. Still, in at least one embodiment, the ratio (G2/G1) may be not greater than about 500, such as not greater than about 200, or even not greater than about 100. It will be appreciated that the body can include a ratio (G2/G1) within a range between any of the above minimum and maximum values.
The second phase may be formed from one or more additives that may be added to the raw material powder. According to one embodiment, the body can include a particular content of strontium and cerium, which may facilitate formation of the second phase, and more particularly, the desired microstructure and content of platelets. It will be appreciated that reference herein to a second phase including strontium (Sr) and cerium (Ce) includes oxides including strontium and cerium, including for example strontium oxide and cerium oxide. The second phase may include strontium oxide, cerium oxide, and/or a compound or complex oxide including strontium and cerium in an oxide form. The second phase may be a monocrystalline, polycrystalline or amorphous material. In one particular embodiment, the platelets of the second phase are polycrystalline material.
As noted herein, the body can include a particular content of strontium (Sr), such as at least 0.2 wt % for a total weight of the body. In certain other instances, the content of strontium (Sr) in the body can be at least 0.3 wt % for a total weight of the body, such as at least 0.4 wt % Sr or at least 0.5 wt % or at least 0.6 wt % or at least 0.7 wt % or at least 0.8 wt % or at least 0.9 wt % or at least 1 wt % or at least 1.1 wt % or at least 1.2 wt % or at least 1.3 wt % or at least 1.4 wt % or at least 1.5 wt % or at least 1.6 wt % or at least 1.7 wt % or at least 1.8 wt % or at least 1.9 wt % or at least 2 wt % or at least 2.1 wt % or at least 2.2 wt % or at least 2.3 wt % or at least 2.4 wt % or at least 2.5 wt %. Still, in one non-limiting embodiment, the content of strontium (Sr) within the body can be not greater than 4.9 wt % for a total weight of the body, such as not greater than 4.8 wt % or not greater than 4.7 wt % or not greater than 4.6 wt % or not greater than 4.5 wt % or not greater than 4.4 wt % or not greater than 4.3 wt % or not greater than 4.2 wt % or not greater than 4.1 wt % or not greater than 4 wt % or not greater than 3.9 wt % or not greater than 3.8 wt % or not greater than 3.7 wt % or not greater than 3.6 wt % or not greater than 3.5 wt % or not greater than 3.4 wt % or not greater than 3.3 wt % or not greater than 3.2 wt % or not greater than 3.1 wt % or not greater than 3 wt % or not greater than 2.9 wt % or not greater than 2.8 wt % or not greater than 2.7 wt % or not greater than 2.6 wt % or not greater than 2.5 wt %. It will be appreciated that the content of strontium (Sr) in the body can be within a range including any of the minimum and maximum percentages noted above. It will also be appreciated that the foregoing contents of strontium in the body may be as part of a compound, such as an oxide compound.
In at least one embodiment, all of the strontium in the body can be contained within the second phase, and more particularly, the platelets of the second phase. The second phase may have a majority content of strontium, such that it includes at least 51 wt % strontium for the total content of the second phase.
The body may include a particular content of cerium (Ce), which may facilitate formation of the second phase, and more particularly, a particular microstructure with the desired content and/or shape of the platelets. According to one embodiment, the body can include at least 0.05 wt % cerium (Ce) for a total weight of the body. For example, the body can include at least 0.3 wt % cerium (Ce) for a total weight of the body or at least 0.4 wt % or at least 0.5 wt % or at least 0.6 wt % or at least 0.7 wt % or at least 0.8 wt % or at least 0.9 wt % or at least 1 wt % or at least 1.1 wt % or at least 1.2 wt % or at least 1.3 wt % or at least 1.5 wt %. Still, in one non-limiting embodiment, the body can include a content of cerium (Ce) that is not greater than 1.9 wt % for a total weight of the body, such as not greater than 1.8 wt % or not greater than 1.7 wt % or not greater than 1.6 wt % or not greater than 1.5 wt % or not greater than 1.4 wt % or not greater than 1.3 wt % or not greater than 1.2 wt % or not greater than 1.1 wt % or not greater than 1 wt % or not greater than 0.9 wt % or not greater than 0.8 wt % or not greater than 0.7 wt % or not greater than 0.6 wt % or not greater than 0.5 wt %. It will be appreciated that the content of cerium (Ce) in the body can be within a range including any of the minimum and maximum percentages noted above. The foregoing contents of cerium may be contents of cerium in a compound, such as an oxide compound.
In at least one embodiment, essentially all of the cerium in the body can be contained within the second phase, and more particularly, the platelets of the second phase. The second phase may have a minimum content of cerium, such that it includes at least 49 wt % cerium for the total content of the second phase.
According to one aspect, the body may have a particular ratio of strontium (Sr) and cerium (Ce) that may facilitate formation of the second phase, and more particularly, the desired microstructure and content and/or shape of the platelets. For example, the body can include a ratio of strontium to cerium (Sr:Ce) of at least 1:1, such as at least at least 1.5:1 or at least 1.8:1 or at least 2:1 or at least 2.5:1 or at least 3:1 or at least 3.5:1 or at least 4:1 or at least 4.5:1 or at least 5:1 or at least 6:1 or at least 8:1 or even at least 10:1. Still, in another embodiment, the body can include a ratio of strontium to cerium (Sr:Ce) of not greater than 10:1 or not greater than 9:1 or not greater than 8:1 or not greater than 7:1 or not greater than 6:1 or not greater than 5:1 or not greater than 4:1. It will be appreciated that the ratio of strontium to cerium (Sr:Ce) in the body can be within a range including any of the minimum and maximum percentages noted above. The ratio of strontium and cerium will be understood to be calculated from the weight percent of these materials in the oxide form, which may be measured via ICP analysis.
In another particular embodiment, the second phase consists essentially of strontium and cerium. Moreover, the ratio of strontium to cerium in the second phase can be controlled to facilitate formation of the desired microstructure and content and/or shape of the platelets. In such instances, the ratio of strontium to cerium (Sr:Ce) in the second phase can be at least 1:1, such as at least at least 1.5:1 or at least 1.8:1 or at least 2:1 or at least 2.5:1 or at least 3:1 or at least 3.5:1 or at least 4:1 or at least 4.5:1 or at least 5:1 or at least 6:1 or at least 8:1 or even at least 10:1. Still, in another embodiment, the ratio of strontium to cerium (Sr:Ce) in the second phase can be not greater than 10:1 or not greater than 9:1 or not greater than 8:1 or not greater than 7:1 or not greater than 6:1 or not greater than 5:1 or not greater than 4:1. It will be appreciated that the ratio of strontium to cerium (Sr:Ce) in the second phase, and more particularly, within the platelets can be within a range including any of the minimum and maximum percentages noted above.
According to one embodiment, the body of the particulate material may have a limited content of platelet clusters. For example, the body may include not greater than 50 platelet clusters per 500 square microns, such as not greater than 40 platelet clusters per 500 square microns or not greater than 30 platelet clusters per 500 square microns or not greater than 20 platelet clusters per 500 square microns 10 platelet clusters per 500 square microns 5 platelet clusters per 500 square microns. Still, in one non-limiting embodiment, the body may be essentially free of platelet clusters. In yet another non-limiting embodiment, the body may include at least 1 platelet cluster per 500 square microns, such as at least 2 platelet clusters per 500 microns or at least 3 platelet clusters per 500 microns or at least 5 platelet clusters per 500 microns or at least 8 platelet clusters per 500 microns or at least 10 platelet clusters per 500 microns or at least 12 platelet clusters per 500 microns or at least 15 platelet clusters per 500 microns. It will be appreciated that the body can include a content of platelet clusters within a range including any of the minimum and maximum values noted above. In some instances, the content of the platelet clusters may be controlled to control the hardness and friability of the abrasive particulate.
In certain instances, the second phase may be non-uniformly dispersed within the body. For example, in one embodiment, the body can have a different content of the second phase at a peripheral region of the body as compared to a content of the second phase at a central region of the body. In certain instances, the body can have a greater content of the second phase at the peripheral region of the body as compared to the content of the second phase at a central region. In another embodiment, the body may have a greater content of the second phase at an exterior surface as compared to a central region of the body. Still, in one alternative embodiment, the content of the second phase may be greater at a central region as compared to the content of the second phase at a peripheral region.
It will be appreciated that foregoing embodiments describing certain distributions of the second phase within the body can be the same for other phases of the particulate material. For example, as will be described in more detail herein, the particulate material can include additional phases distinct from the first and second phases (e.g., a third phase, a fourth phase, a fifth phase, etc.), and such phases can be substantially uniformly dispersed through the volume of the body, or alternatively, may be distributed in a non-uniform manner. For example, in one embodiment, the particulate material can include a body having a non-uniform distribution of a second phase and a third phase within the volume of the body. More particularly, the body can have a greater content of the second phase at a peripheral region compared to a central region, and the body may also have a greater content of the third phase at the central region compared to the peripheral region. Still, in other instances, the body can include multiple phases having different distribution characteristics. For example, the second phase may be substantially, uniformly distributed throughout the volume of the body and a third phase may be non-uniformly distributed throughout the body.
In at least one aspect, the body may consist essentially of only the first phase and the second phase. In such instances, the body may be essentially free of any other phases except for the first phase and second phase. For such embodiments, the body may include only impurity contents of other elements, compounds, and phases.
However, as illustrated in
In certain instances, the body may include a third phase, which may facilitate improved manufacturing and/or performance of the particulate material. According to one embodiment, the third phase may include at least one of an oxide, carbide, nitride, boride, or any combination thereof. In certain instances, the third phase may include strontium, cerium, or any combination thereof. In another embodiment, the third phase may include a composition, such as an oxide compound, including at least one element selected from the group consisting of Li, Na, K, Mg, Ca, Sr, Ba, Y, Zr, Ti, Mn, Fe, Nb, Mo, Hf, Ta, La, Cr, Co, Ni, Cu, Zn, or any combination thereof. Certain embodiments herein can include a particulate material having a body consisting essentially of the first phase, second phase, and the third phase.
The body may include a particular content of the third phase, which may facilitate improved manufacturing and/or performance of the particulate material. For example, the third body may include not greater than 5 wt % of the third phase for the a total weight of the body, such as not greater than 4 wt % or not greater than 3 wt % or not greater than 2 wt % or not greater than 1 wt % or not greater than 0.5 wt % or not greater than 0.1 wt %. Still, in one non-limiting embodiment, the body can include at least 0.1 wt % of the third phase for the total weight of the body, such as at least 0.5 wt % or at least 1 wt % or even at least 2 wt %.
In one aspect, the third phase may have a particular average crystallite size relative to the first and second phases. For example, the third phase can have an average crystallite size that is less than the average crystallite size of the first phase. Reference herein to the average crystallite size of the third phase is reference to the average size of the crystallites or domains of the third phase and is measured in the same manner as noted for the first phase. Moreover, the third phase may have an average crystallite size that is less than the average length of the platelets of the second phase. In yet another embodiment, the third phase may have an average crystallite size that is less than the average width of the platelets of the second phase.
The third phase may be an integral phase within the body. As noted herein, the third phase may be substantially uniformly dispersed through the entire volume of the body. Alternatively, the third phase may be non-uniformly dispersed within the body, including for example, but not limited to, disposed in a “halo” manner as described in embodiments herein. Additionally, a majority of the third phase may be disposed as an intergranular phase (i.e., between grains at the grain boundaries) between any of the phases described in embodiments herein.
In certain instances, the particulate material includes a body having a particular ratio (W1/W3), wherein W1 represents the weight percent of the first phase of the body and W3 represents the weight percent of the third phase within the body. In at least one aspect, the ratio (W1/W3), can be at least about 1, such as at least about 1.1, at least about 1.5, at least about 2, at least about 3, at least about 5, at least about 8, at least about 10, at least about 15, at least about 20, at least about 50, or even at least about 70. Still, in another embodiment the ratio (W1/W3) can be not greater than about 100, or even not greater than about 95. It will be appreciated that the body can have a ratio (W1/W3) within a range between any of the minimum and maximum values provided above.
Furthermore, in another aspect, the particulate material can include a body having a ratio (W3/W2), wherein W2 represents a weight percent of the second phase with the body and W3 represents a weight percent of the third phase within the body. In particular instances, the ratio (W3/W2) can be at least about 0.1, such as at least about 0.3, at least about 0.5, at least about 0.7, at least about 0.9, at least about 1, at least about 1.1, at least about 1.5, at least about 2, at least about 4, at least about 6, or even at least about 10. Still, in yet another embodiment, the body can have a ratio (W3/W2) that is not greater than about 10, for example, not greater than about 7, not greater than about 5, not greater than about 3, not greater than about 2.5, not greater than about 2.2, not greater than about 2, not greater than about 1.5, not greater than about 1, not greater than about 0.9, or even not greater than about 0.7. It will be appreciated that the ratio (W3/W2) can be within a range between any of the above minimum or maximum values.
In accordance with another aspect, the particulate material can be formed such that the average crystallite size of the third phase has a particular relationship to the average crystallite size of the first phase and/or the average length of the platelets of the second phase. For example, the particulate material can include a body having a first phase including a first average crystallite size and a third phase having a third average crystallite size. In certain instances, the first phase can have a first average crystallite size that is different than the third average crystallite size of the third phase. More particularly, the body can include a ratio (G1/G3) wherein G1 represents the average crystallite size of the first phase and G3 represents the average crystallite size of the third phase. In at least one instance, the ratio (G1/G3) can be at least 0.2, such as at least 0.5 or at least about 0.8 or at least 1 or at least about 1.1 or at least 1.5 or at least 2 or at least 3 or even at least 5. Still, in another embodiment, the ratio (G1/G3) can be not greater than 5, such as not greater than 2 or not greater than 1 or not greater than 0.8 or not greater than about 0.5. It will be appreciated that the ratio (G1/G3) can have a value within a range between any of the minimum or maximum values noted above.
For certain embodiments, the second phase can have an average length of the platelets that is different than the third average crystallite size of the third phase, and more particularly, may be greater than the third average crystallite size of the third phase. In at least one instance, the body can have a ratio (G2/G3) wherein G2 represents the average length of the platelets of the second phase and G3 represents the third average crystallite size of the third phase. The ratio (G2/G3) can be at least 1, such as at least 2 or at least 3 or at least 4 or at least 5 or at least 8 or at least 10. Still, in one non-limiting embodiment, the ratio (G2/G3) may not be greater than 30, such as not greater than about 25 or not greater than 20 or not greater than 15 or not greater than about 10 or even not greater than 5. It will be appreciated that the ratio (G2/G3) can be within a range between any of the minimum and maximum values note above.
The body can include a third phase having an average crystallite size of not greater than 100 μm. In other instances, the average grain size of the third phase may be less, such as not greater than 50 μm or not greater than 20 μm or not greater than 10 μm or not greater than 1 μm or not greater than 0.8 μm or not greater than 0.5 μm or even not greater than about 0.2 μm. Still, the average crystallite size of the third phase may be at least 0.1 μm, such as at least about at least 0.5 μm or at least about 1 μm. It will be appreciated that the third phase can have an average crystallite size within a range of the minimum and maximum values noted above.
In yet another embodiment, the particulate material can have a body that can be in the form of a non-shaped abrasive particle, a shaped abrasive particle, or any combination thereof.
The shaped abrasive particle 400 of
The shaped abrasive particles of the embodiments herein, including thin shaped abrasive particles can have a primary aspect ratio of length:width such that the length can be greater than or equal to the width. Furthermore, the length of the body 401 can be greater than or equal to the height. Finally, the width of the body 401 can be greater than or equal to the height. In accordance with an embodiment, the primary aspect ratio of length:width can be at least 1:1, such as at least 1.1:1, at least 1.2:1, at least 1.5:1, at least 1.8:1, at least 2:1, at least 3:1, at least 4:1, at least 5:1, at least 6:1, or even at least 10:1. In another non-limiting embodiment, the body 401 of the shaped abrasive particle can have a primary aspect ratio of length:width of not greater than 100:1, not greater than 50:1, not greater than 10:1, not greater than 6:1, not greater than 5:1, not greater than 4:1, not greater than 3:1, not greater than 2:1, or even not greater than 1:1. It will be appreciated that the primary aspect ratio of the body 401 can be with a range including any of the minimum and maximum ratios noted above.
Furthermore, the body 401 can have a secondary aspect ratio of width:height that can be at least 1:1, such as at least 1.1:1, at least 1.2:1, at least 1.5:1, at least 1.8:1, at least 2:1, at least 3:1, at least 4:1, at least 5:1, at least 8:1, or even at least 10:1. Still, in another non-limiting embodiment, the secondary aspect ratio width:height of the body 401 can be not greater than 100:1, such as not greater than 50:1, not greater than 10:1, not greater than 8:1, not greater than 6:1, not greater than 5:1, not greater than 4:1, not greater than 3:1, or even not greater than 2:1. It will be appreciated the secondary aspect ratio of width:height can be with a range including any of the minimum and maximum ratios of above.
In another embodiment, the body 401 can have a tertiary aspect ratio of length:height that can be at least 1.1:1, such as at least 1.2:1, at least 1.5:1, at least 1.8:1, at least 2:1, at least 3:1, at least 4:1, at least 5:1, at least 8:1, or even at least 10:1. Still, in another non-limiting embodiment, the tertiary aspect ratio length:height of the body 401 can be not greater than 100:1, such as not greater than 50:1, not greater than 10:1, not greater than 8:1, not greater than 6:1, not greater than 5:1, not greater than 4:1, not greater than 3:1. It will be appreciated that the tertiary aspect ratio the body 401 can be with a range including any of the minimum and maximum ratios noted above.
The abrasive particles of the embodiments herein, including the shaped abrasive particles can include a crystalline material, and more particularly, a polycrystalline material including those compositions and morphologies described in embodiments herein. The particulate material can be formed such that the body includes a crystalline material, and more particularly, a polycrystalline material. Notably, the polycrystalline material can include abrasive grains. In one embodiment, the body can be essentially free of an organic material, including for example, a binder. More particularly, the body can consist essentially of a polycrystalline material.
It will be appreciated that like the thin shaped abrasive particle of
As further illustrated in
As will be appreciated, the abrasive particle can have a length defined by the longitudinal axis 652, a width defined by the lateral axis 653, and a vertical axis 654 defining a height. As will be appreciated, the body 651 can have a primary aspect ratio of length:width such that the length is equal to or greater than the width. Furthermore, the length of the body 651 can be equal to or greater than or equal to the height. Finally, the width of the body 651 can be greater than or equal to the height 654. In accordance with an embodiment, the primary aspect ratio of length:width can be at least 1.1:1, at least 1.2:1, at least 1.5:1, at least 1.8:1, at least 2:1, at least 3:1, at least 4:1, at least 5:1, at least 6:1, or even at least 10:1. In another non-limiting embodiment, the body 651 of the elongated shaped abrasive particle can have a primary aspect ratio of length:width of not greater than 100:1, not greater than 50:1, not greater than 10:1, not greater than 6:1, not greater than 5:1, not greater than 4:1, not greater than 3:1, or even not greater than 2:1. It will be appreciated that the primary aspect ratio of the body 651 can be within a range including any of the minimum and maximum ratios noted above.
Furthermore, the body 651 can include a secondary aspect ratio of width:height that can be at least 1.1:1, such as at least 1.2:1, at least 1.5:1, at least 1.8:1, at least 2:1, at least 3:1, at least 4:1, at least 5:1, at least 8:1, or even at least 10:1. Still, in another non-limiting embodiment, the secondary aspect ratio width:height of the body 651 can be not greater than 100:1, such as not greater than 50:1, not greater than 10:1, not greater than 8:1, not greater than 6:1, not greater than 5:1, not greater than 4:1, not greater than 3:1, or even not greater than 2:1. It will be appreciated the secondary aspect ratio of width:height can be with a range including any of the minimum and maximum ratios of above.
In another embodiment, the body 651 can have a tertiary aspect ratio of length:height that can be at least 1.1:1, such as at least 1.2:1, at least 1.5:1, at least 1.8:1, at least 2:1, at least 3:1, at least 4:1, at least 5:1, at least 8:1, or even at least 10:1. Still, in another non-limiting embodiment, the tertiary aspect ratio length:height of the body 651 can be not greater than 100:1, such as not greater than 50:1, not greater than 10:1, not greater than 8:1, not greater than 6:1, not greater than 5:1, not greater than 4:1, not greater than 3:1, It will be appreciated that the tertiary aspect ratio the body 651 can be with a range including any of the minimum and maximum ratios and above.
The elongated non-shaped abrasive particle 650 can have certain attributes of the other abrasive particles described in the embodiments herein, including for example but not limited to, composition, microstructural features (e.g., average grain size), hardness, porosity, and the like.
As further illustrated, the body 681 of the abrasive particle 680 can have a side surface 684 having an irregular two-dimensional shape as viewed in the plane of the first or second major surfaces 682 or 683. An irregular two-dimensional shape is one in which the shape does not have a recognizable shape, such as a polygonal shape. The irregular two-dimensional shape is characterized by a side surface 684 that can have a random or unpredictable contour. Such an abrasive particle can be formed according to the processes of the embodiments herein, including for example, a process that include creating a thin layer of a material, patterning a portion of the material (e.g., the upper or lower surface), and drying the patterned layer of material in a manner to cause controlled cracking of the material. The controlled cracking may occur generally along the lines or indentations created during patterning. The body 681 can have external corners 671, 672, 673, 674, 675, 676, and 677 (771-777). The external corners 671-677 are portions that would cause significant deflection of an imaginary rubber band around the side surface 684 of the body 681 by at least 10 degrees or greater.
As noted herein, the particulate material can be an abrasive material. As such, the particulate material may be deployed in various manners for use in abrasive articles. For example, the particulate material may be part of a fixed abrasive article such as a coated abrasive article, bonded abrasive article, and a combination thereof. In particular instances, the particulate material can be coupled to a bond material, and further coupled to a backing or substrate via the bond material. The bond material may include compositions such as vitrified materials, ceramic materials, metal alloy, organic material, a resin, a polymer, and a combination thereof. In at least one instance, the particulate material can be part of a coated abrasive forming a single layer of abrasive particles coupled to a backing. In an alternative embodiment, the abrasive particles can be used as free abrasive particles.
According to one embodiment, the substrate 701 can include an organic material, inorganic material, and a combination thereof. In certain instances, the substrate 701 can include a woven material. However, the substrate 701 may be made of a non-woven material. Particularly suitable substrate materials can include organic materials, including polymers, and particularly, polyester, polyurethane, polypropylene, polyimides such as KAPTON from DuPont, paper. Some suitable inorganic materials can include metals, metal alloys, and particularly, foils of copper, aluminum, steel, and a combination thereof.
A polymer formulation may be used to form any of a variety of layers of the abrasive article such as, for example, the frontfill, the pre-size coat, the make coat, the size coat, and/or the supersize coat. When used to form the frontfill, the polymer formulation may generally include a polymer resin, fibrillated fibers (preferably in the form of pulp), filler material, and other optional additives. Suitable formulations for some frontfill embodiments can include material such as a phenolic resin, wollastonite filler, defoamer, surfactant, a fibrillated fiber, and a balance of water. Suitable polymeric resin materials include curable resins selected from thermally curable resins including phenolic resins, urea/formaldehyde resins, phenolic/latex resins, as well as combinations of such resins. Other suitable polymeric resin materials may also include radiation curable resins, such as those resins curable using electron beam, UV radiation, or visible light, such as epoxy resins, acrylated oligomers of acrylated epoxy resins, polyester resins, acrylated urethanes and polyester acrylates and acrylated monomers including monoacrylated, multiacrylated monomers. The formulation can also comprise a non-reactive thermoplastic resin binder which can enhance the self-sharpening characteristics of the deposited abrasive composites by enhancing the erodibility. Examples of such thermoplastic resin include polypropylene glycol, polyethylene glycol, and polyoxypropylene-polyoxyethene block copolymer, etc. Use of a frontfill on the backing can improve the uniformity of the surface, for suitable application of the make coat and improved application and orientation of shaped abrasive particles in a predetermined orientation.
The make coat 703 can be applied to the surface of the substrate 701 in a single process, or alternatively, the abrasive particulate material 710 can be combined with a make coat 703 material and applied as a mixture to the surface of the substrate 701. Suitable materials of the make coat 703 can include organic materials, particularly polymeric materials, including for example, polyesters, epoxy resins, polyurethanes, polyamides, polyacrylates, polymethacrylates, poly vinyl chlorides, polyethylene, polysiloxane, silicones, cellulose acetates, nitrocellulose, natural rubber, starch, shellac, and mixtures thereof. In one embodiment, the make coat 703 can include a polyester resin. The coated substrate can then be heated in order to cure the resin and the abrasive particulate material to the substrate. In general, the coated substrate 701 can be heated to a temperature of between about 100° C. to less than about 250° C. during this curing process.
The abrasive particulate material 710 can include shaped abrasive particles according to embodiments herein. In particular instances, the abrasive particulate material 710 may include different types of shaped abrasive particles. The different types of shaped abrasive particles can differ from each other in composition, two-dimensional shape, three-dimensional shape, size, and a combination thereof as described in the embodiments herein. As illustrated, the coated abrasive 700 can include a shaped abrasive particle 705 having a generally triangular two-dimensional shape.
The other type of abrasive particles 707 can be non-shaped abrasive particles, which may include diluent particles that are different than the shaped abrasive particles 705. For example, the diluent particles can differ from the shaped abrasive particles 705 in composition, two-dimensional shape, three-dimensional shape, size, and a combination thereof. For example, the abrasive particles 707 can represent conventional, crushed abrasive grit having random shapes. The abrasive particles 707 may have a median particle size less than the median particle size of the shaped abrasive particles 705.
After sufficiently forming the make coat 703 with the abrasive particulate material 710, the size coat 704 can be formed to overlie and bond the abrasive particulate material 710 in place. The size coat 704 can include an organic material, may be made essentially of a polymeric material, and notably, can use polyesters, epoxy resins, polyurethanes, polyamides, polyacrylates, polymethacrylates, poly vinyl chlorides, polyethylene, polysiloxane, silicones, cellulose acetates, nitrocellulose, natural rubber, starch, shellac, and mixtures thereof.
Many different aspects and embodiments are possible. Some of those aspects and embodiments are described herein. After reading this specification, skilled artisans will appreciate that those aspects and embodiments are only illustrative and do not limit the scope of the present invention. Embodiments may be in accordance with any one or more of the embodiments as listed below.
Embodiment 1. A particulate material comprising a body including a first phase including alumina having an average crystallite size of not greater than 5 microns, and wherein the body further comprises a second phase having a platelet shape.
Embodiment 2. A particulate material comprising a body including a first phase including alumina and a second phase having a platelet shape, wherein the second phase comprises Sr in a range of at least 0.2 wt % and not greater than 5 wt % for a total weight of the body.
Embodiment 3. A particulate material comprising a body including a first phase including alumina and a second phase having a platelet shape and containing Sr and Ce, wherein the second phase comprises a Sr content within a range of at least in a range of at least 0.2 wt % and not greater than 5 wt % for a total weight of the body, and wherein the second phase comprises a Ce content within a range of at least 0.05 wt % and not greater than 2 wt % for a total weight of the body.
Embodiment 4. A particulate material comprising a body including a first phase including alumina and a second phase having a platelet shape and containing Sr and Ce, wherein the second phase comprises a Sr and Ce, and wherein the second phase comprises a ratio of Sr:Ce within a range of at least 1:1 to not greater than 100:1.
Embodiment 5. The particulate material of any one of embodiments 1, 2, 3, and 4, wherein the platelets have a length (l) and a width (w) as viewed in two dimensions and wherein l>w.
Embodiment 6. The particulate material of embodiment 5, wherein the platelets have an average primary aspect ratio of length:width of at least 1.2:1 or at least 1.3:1 or at least 1.3:1 or at least 1.4:1 or at least 1.5:1 or at least 1.7:1 or at least 1.8:1 or at least 1.9:1 or at least 2:1 or at least 2.3:1 or at least 2.5:1 or at least 3:1 or at least 4:1 or at least 5:1 or at least 7:1 or at least 10:1.
Embodiment 7. The particulate material of embodiment 5, wherein the platelets have an average primary aspect ratio of length:width of not greater than 1000:1 or not greater than 750:1 or not greater than 500:1 or not greater than 100:1 or not greater than 50:1 or not greater than 20:1 or not greater than 10:1.
Embodiment 8. The particulate material of any one of embodiments 1, 2, 3, and 4, wherein the platelets have a length (l) and width (w) as measured in two-dimensions, and wherein the length is within a range of at least 0.2 microns to not greater than 10 microns.
Embodiment 9. The particulate material of any one of embodiments 1, 2, 3, and 4, wherein the platelets have a length (l), width (w) and wherein the width is within a range of at least 0.02 microns to not greater than 5 microns.
Embodiment 10. The particulate material of any one of embodiments 1, 2, 3, and 4, wherein the platelets are uniformly distributed throughout the body.
Embodiment 11. The particulate material of any one of embodiments 1, 2, 3, and 4, wherein the body comprises not greater than 50 platelet clusters per 500 square microns or not greater than 40 platelet clusters per 500 square microns or not greater than 30 platelet clusters per 500 square microns or not greater than 20 platelet clusters per 500 square microns or not greater than 10 platelet clusters per 500 square microns or not greater than 5 platelet clusters per 500 square microns.
Embodiment 12. The particulate material of any one of embodiments 1, 2, 3, and 4, wherein the body is essentially free of platelet clusters.
Embodiment 13. The particulate material of any one of embodiments 1, 2, 3, and 4, wherein the body comprises at least 51 wt % alumina for the total weight of the body or least 60 wt % alumina or at least 70 wt % alumina or at least 80 wt % alumina or at least 90 wt % alumina or at least 95 wt % alumina or at least 97 wt % alumina.
Embodiment 14. The particulate material of any one of embodiments 1, 2, 3, and 4, wherein the body comprises not greater than 99.9 wt % alumina for the total weight of the body or not greater than 99.5% alumina or not greater than 99 wt % alumina or not greater than 98.5 wt % alumina.
Embodiment 15. The particulate material of any one of embodiments 1, 2, 3, and 4, wherein the body comprises a theoretical density of at least 95% or at least 96% or at least 97% or at least 98% or at least 99% or at least 99.5% or at least 99.9%.
Embodiment 16. The particulate material of any one of embodiments 2, 3, and 4, wherein the first phase comprises an average crystallite size of not greater than 5 microns.
Embodiment 17. The particulate material of any one of embodiments 1 and 16, wherein the average crystallite size of the first phase is not greater than 4 microns or not greater than 3 microns or not greater than 2 microns or not greater than 1 micron or not greater than 0.9 microns or not greater than 0.8 microns or not greater than 0.7 microns or not greater than 0.6 microns or not greater than 0.5 microns or not greater than 0.4 microns.
Embodiment 18. The particulate material of any one of embodiments 1 and 16, wherein the average crystallite size of the first phase is at least 0.01 microns or at least 0.05 microns or at least 0.1 microns.
Embodiment 19. The particulate material of any one of embodiments 1, 2, 3, and 4, wherein the body comprises a seeded alumina material.
Embodiment 20. The particulate material of any one of embodiments 1 and 4, wherein the body comprises Sr in a range of at least 0.2 wt % and not greater than 5 wt % for a total weight of the body.
Embodiment 21. The particulate material of any one of embodiments 2, 3, and 20, wherein the body comprises at least 0.3 wt % Sr for a total weight of the body or at least 0.4 wt % Sr or at least 0.5 wt % or at least 0.6 wt % or at least 0.7 wt % or at least 0.8 wt % or at least 0.9 wt % or at least 1 wt % or at least 1.1 wt % or at least 1.2 wt % or at least 1.3 wt % or at least 1.4 wt % or at least 1.5 wt % or at least 1.6 wt % or at least 1.7 wt % or at least 1.8 wt % or at least 1.9 wt % or at least 2 wt % or at least 2.1 wt % or at least 2.2 wt % or at least 2.3 wt % or at least 2.4 wt % or at least 2.5 wt %.
Embodiment 22. The particulate material of any one of embodiments 2, 3, and 20, wherein the body comprises not greater than 4.9 wt % Sr for a total weight of the body or not greater than 4.8 wt % or not greater than 4.7 wt % or not greater than 4.6 wt % or not greater than 4.5 wt % or not greater than 4.4 wt % or not greater than 4.3 wt % or not greater than 4.2 wt % or not greater than 4.1 wt % or not greater than 4 wt % or not greater than 3.9 wt % or not greater than 3.8 wt % or not greater than 3.7 wt % or not greater than 3.6 wt % or not greater than 3.5 wt % or not greater than 3.4 wt % or not greater than 3.3 wt % or not greater than 3.2 wt % or not greater than 3.1 wt % or not greater than 3 wt % or not greater than 2.9 wt % or not greater than 2.8 wt % or not greater than 2.7 wt % or not greater than 2.6 wt % or not greater than 2.5 wt %.
Embodiment 23. The particulate material of any one of embodiments 1, 2, and 4, wherein the body comprises a Ce content within a range of at least 0.05 wt % and not greater than 2 wt % for a total weight of the body.
Embodiment 24. The particulate material of any one of embodiments 3 and 23, wherein the body comprises a content of Ce of at least 0.3 wt % for a total weight of the body or at least 0.4 wt % or at least 0.5 wt % or at least 0.6 wt % or at least 0.7 wt % or at least 0.8 wt % or at least 0.9 wt % or at least 1 wt % or at least 1.1 wt % or at least 1.2 wt % or at least 1.3 wt % or at least 1.5 wt %.
Embodiment 25. The particulate material of any one of embodiments 3 and 23, wherein the body comprises a content of Ce of not greater than 1.9 wt % for a total weight of the body or not greater than 1.8 wt % or not greater than 1.7 wt % or not greater than 1.6 wt % or not greater than 1.5 wt % or not greater than 1.4 wt % or not greater than 1.3 wt % or not greater than 1.2 wt % or not greater than 1.1 wt % or not greater than 1 wt % or not greater than 0.9 wt % or not greater than 0.8 wt % or not greater than 0.7 wt % or not greater than 0.6 wt % or not greater than 0.5 wt %.
Embodiment 26. The particulate material of any one of embodiments 1, 2, and 3, wherein the body comprises a Sr and Ce in a ratio of Sr:Ce within a range of at least 1:1 and not greater than 100:1.
Embodiment 27. The particulate material of any one of embodiments 4 and 26, wherein the body comprises a ratio of Sr:Ce of at least 1.5:1 or at least 1.8:1 or at least 2:1 or at least 2.5:1 or at least 3:1 or at least 3.5:1 or at least 4:1 or at least 4.5:1 or at least 5:1 or at least 6:1 or at least 8:1 or at least 10:1.
Embodiment 28. The particulate material of any one of embodiments 4 and 26, wherein the body comprises a ratio of Sr:Ce of not greater than 10:1 or not greater than 9:1 or not greater than 8:1 or not greater than 7:1 or not greater than 6:1 or not greater than 5:1 or not greater than 4:1.
Embodiment 29. The particulate material of any one of embodiments 1, 2, 3, and 4, wherein the body comprises not greater than 5 wt % of a third phase comprising Ce for a total weight of the body or not greater than 4 wt % or not greater than 3 wt % or not greater than 2 wt % or not greater than 1 wt % or not greater than 0.5 wt % or not greater than 0.1 wt %.
Embodiment 30. The particulate material of any one of embodiments 1, 2, 3, and 4, wherein the body consists essentially of the first phase and the second phase.
Embodiment 31. The particulate material of any one of embodiments 1, 2, 3, and 4, wherein the body is free of a third phase.
Embodiment 32. The particulate material of any one of embodiments 1, 2, 3, and 4, wherein the body includes at least 0.5 wt % of a third phase for a total weight of the body, wherein the third phase comprises at least one of an oxide, carbide, nitride, boride, or any combination thereof.
Embodiment 33. The particulate material of embodiment 32, wherein the third phase comprises an oxide including at least one element selected from the group consisting of Li, Na, K, Mg, Ca, Sr, Ba, Y, Zr, Ti, Mn, Fe, Nb, Mo, Hf, Ta, La, Cr, Co, Ni, Cu, Zn, or any combination thereof.
Embodiment 34. The particulate material of embodiment 32, wherein the third phase is disposed at the grain boundaries between the first and second phases.
Embodiment 35. The particulate material of embodiment 32, wherein the third phase comprises an average crystallite size that is less than the average crystallite size of the first phase.
Embodiment 36. The particulate material of embodiment 32, wherein the third phase comprises an average crystallite size that is less than the average length of the platelets of the second phase.
Embodiment 37. The particulate material of any one of embodiments 1, 2, 3, and 4, further comprising a fixed abrasive article including the particulate material.
Embodiment 38. The particulate material of embodiment 37, wherein the fixed abrasive is selected from the group consisting of a coated abrasive, a bonded abrasive, a non-woven abrasive, an abrasive brush, or a combination thereof.
Embodiment 39. The particulate material of embodiment 37, wherein the fixed abrasive is a coated abrasive article including the particulate material arranged in a single layer overlying a substrate.
Embodiment 40. The particulate material of any one of embodiments 1, 2, 3, and 4, wherein the particulate material is a shaped abrasive particle comprising a body with a two-dimensional shape as defined by a major surface of the body from the group of shapes including polygons, irregular polygons, irregular polygons including arcuate or curved sides or portions of sides, ellipsoids, numerals, Greek alphabet characters, Latin alphabet characters, Russian alphabet characters, Kanji characters, complex shapes having a combination of polygons shapes, shapes including a central region and a plurality of arms, or any combination thereof.
Embodiment 41. The particulate material of any one of embodiments 1, 2, 3, and 4, wherein the particulate material is a controlled thickness abrasive particle having a body of a substantially uniform thickness and an irregular two dimensional shape when viewed in the plane defined by the length and width of the body.
Five different samples were made with various compositions as provided in Table 1 below. These five samples (S1, S2, S3, S4 and S5) were prepared from a gel including 41.5 wt % boehmite, which is commercially available as Catapal B, and seeded with 1% alpha alumina seeds and dopants in the weight percentages as provided in Table 1.
The mixture also included 55 wt % water and 2.5 wt % nitric acid. The mixture was extruded into equilateral triangular shaped openings in a production tool, wherein the triangular shaped openings had a length (side of triangle) of 2.77 mm, a width of 2.4 mm and a depth (height) of 0.53 mm. The production tool was made of metal. The surfaces of the openings in the production tool were coated with a lubricant of olive oil to facilitate removal of the precursor shaped abrasive particles from the production tool. The mixture was dried in the openings at approximately 50° C. for 10 minutes. The mixture was then removed from the openings of the production tool.
The dried particles were then calcined at a calcination temperature of approximately 1000° C. for 10 minutes in a rotary tube furnace of standard atmospheric pressure and an atmosphere of air. The calcined particulate material was made primarily of transition phase alumina. The pore volume was measured using BET to determine saturation and over-saturation conditions for the calcined particles.
For each sample, an additive solution was created using the contents of cerium nitrate, strontium nitrate and deionized water as provided in Table 1. The additive solution was mixed until the salts were completely dissolved. The calcined particles were placed in a beaker and rotated to stir the calcined particles. The entire additive solution was sprayed as a mist into the beaker while the calcined particles were mixing to impregnate the calcined particles with the additive solution. After impregnation, the impregnated powder was dried for approximately 12-15 hours in an oven set at 80° C. The impregnated particles were sintered in a Lindberg rotary furnace operating at 8 rpms and set at a temperature of 1430° C. for approximately 3 minutes. The resulting shaped abrasive particles were generally in the shape of equilateral triangles as viewed top down on the major surfaces, and had a length (along a side) of approximately 1650 microns and a height of approximately 300 microns.
SEM images of each of the Samples S1-S5 are provided in
Notably, Sample S1 demonstrated a uniform distribution of platelets of the second phase. Sample 2 had a significant number of platelet clusters.
The grinding performance of the shaped abrasive particles of Samples S1-S5 was evaluated according to a standardized single-grit grinding test (SGGT). In conducting the SGGT, one single shaped abrasive particle was held in a grit holder by a bonding material of epoxy. The shaped abrasive particle was secured in the desired orientation (i.e., major surface orientation or side surface orientation) and moved across a workpiece of 304 stainless steel for a scratch length of 8 inches, at a wheel speed of 22 m/s, and an initial scratch depth of 30 microns. The shaped abrasive particles were mounted such that the tips of the triangles were pointing up and configured to strike the workpiece first. The shaped abrasive particle produced a groove in the workpiece having a cross-sectional area (AR). For each sample set, each shaped abrasive particle completed 15 passes across the 8 inch length, 10 individual particles were tested for each of the orientations and the results were analyzed. The test measured the tangential force exerted by the grit on the workpiece, in the direction that is parallel to the surface of the workpiece and the direction of the groove, and the net change in the cross-sectional area of the groove from beginning to the end of the scratch length was measured to determine the shaped abrasive particle wear. The net change in the cross-sectional area of the groove for each pass was measured. For the SGGT, a minimum threshold value of at least 1000 microns2 for the cross-sectional area of the groove was set for each pass. If the particle failed to form a groove having the minimum threshold cross-sectional area, the data was not recorded for that pass.
The SGGT was conducted using two different orientations of the shaped abrasive particles relative to the workpiece. For each of the samples, the SGGT was conducted with a first sample set of shaped abrasive particles in a major surface orientation, wherein a major surface of each shaped abrasive particle was oriented perpendicular to the grinding direction such that the major surface initiated grinding on the workpiece. A second sample set of shaped abrasive particles were oriented in a side surface orientation, wherein a side surface of each shaped abrasive particle was oriented perpendicular to the direction of grinding and was the leading surface during grinding.
The present application represents a departure from the state of the art. While the industry has recognized that alumina materials may have certain additives, the effect of certain combinations of additives, the phases created by such additives, and the microstructures created by controlled contents of such additives continues to be an area of significant research. The particulate material of the embodiments herein can be formed through particular processes and results in particular microstructures, which may facilitate improved performance of the particulate material, especially as an abrasive material.
The above-disclosed subject matter is to be considered illustrative, and not restrictive, and the appended claims are intended to cover all such modifications, enhancements, and other embodiments, which fall within the true scope of the present invention. Thus, to the maximum extent allowed by law, the scope of the present invention is to be determined by the broadest permissible interpretation of the following claims and their equivalents, and shall not be restricted or limited by the foregoing detailed description.
The Abstract of the Disclosure is provided to comply with Patent Law and is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims. In addition, in the foregoing Detailed Description, various features may be grouped together or described in a single embodiment for the purpose of streamlining the disclosure. This disclosure is not to be interpreted as reflecting an intention that the claimed embodiments require more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive subject matter may be directed to less than all features of any of the disclosed embodiments. Thus, the following claims are incorporated into the Detailed Description, with each claim standing on its own as defining separately claimed subject matter.
This application claims priority under 35 U.S.C. § 119(e) to U.S. Patent Application No. 62/522,800 entitled “Particulate Materials and Methods of Forming Same,” by Samuel S. MARLIN, et al., filed Jun. 21, 2017, which is assigned to the current assignee hereof and incorporated herein by reference in its entirety.
| Number | Name | Date | Kind |
|---|---|---|---|
| 345604 | Semper | Jul 1886 | A |
| 1910444 | Nicholson | May 1933 | A |
| 2036903 | Webster | Apr 1936 | A |
| 2049874 | Sherk | Aug 1936 | A |
| 2148400 | Crompton, Jr. | Feb 1939 | A |
| 2248064 | Carlton et al. | Jul 1941 | A |
| 2248990 | Heany | Jul 1941 | A |
| 2290877 | Heany | Jul 1942 | A |
| 2318360 | Benner et al. | May 1943 | A |
| 2376343 | Carlton | May 1945 | A |
| 2563650 | Heinemann et al. | Aug 1951 | A |
| 2880080 | Rankin et al. | Mar 1959 | A |
| 3041156 | Rowse et al. | Jun 1962 | A |
| 3067551 | Maginnis | Dec 1962 | A |
| 3079242 | Glasgow | Feb 1963 | A |
| 3079243 | Ueltz | Feb 1963 | A |
| 3123948 | Kistler et al. | Mar 1964 | A |
| 3141271 | Fischer et al. | Jul 1964 | A |
| 3276852 | Lemelson | Oct 1966 | A |
| 3377660 | Marshall et al. | Apr 1968 | A |
| 3379543 | Norwalk | Apr 1968 | A |
| 3387957 | Howard | Jun 1968 | A |
| 3454385 | Amero | Jul 1969 | A |
| 3477180 | Robertson, Jr. | Nov 1969 | A |
| 3480395 | McMullen et al. | Nov 1969 | A |
| 3481723 | Kistler et al. | Dec 1969 | A |
| 3491492 | Ueltz | Jan 1970 | A |
| 3495359 | Smith et al. | Feb 1970 | A |
| 3536005 | Derrickson | Oct 1970 | A |
| 3590799 | Guuchowicz | Jul 1971 | A |
| 3608050 | Carman et al. | Sep 1971 | A |
| 3608134 | Cook | Sep 1971 | A |
| 3615308 | Amero | Oct 1971 | A |
| 3619151 | Sheets, Jr. et al. | Nov 1971 | A |
| 3637360 | Ueltz | Jan 1972 | A |
| 3670467 | Walker | Jun 1972 | A |
| 3672934 | Larry | Jun 1972 | A |
| 3808747 | Kenagy | May 1974 | A |
| 3819785 | Argyle et al. | Jun 1974 | A |
| 3859407 | Blanding et al. | Jan 1975 | A |
| 3874856 | Leeds | Apr 1975 | A |
| 3909991 | Coes, Jr. | Oct 1975 | A |
| 3940276 | Wilson | Feb 1976 | A |
| 3950148 | Fukuda | Apr 1976 | A |
| 3960577 | Prochazka | Jun 1976 | A |
| 3977132 | Sekigawa | Aug 1976 | A |
| 3986885 | Lankard | Oct 1976 | A |
| 3991527 | Maran | Nov 1976 | A |
| 4004934 | Prochazka | Jan 1977 | A |
| 4037367 | Kruse | Jul 1977 | A |
| 4045919 | Moritomo | Sep 1977 | A |
| 4055451 | Cockbain et al. | Oct 1977 | A |
| 4073096 | Ueltz et al. | Feb 1978 | A |
| 4114322 | Greenspan | Sep 1978 | A |
| 4150078 | Miller et al. | Apr 1979 | A |
| 4194887 | Ueltz et al. | Mar 1980 | A |
| 4252544 | Takahashi | Feb 1981 | A |
| 4261706 | Blanding et al. | Apr 1981 | A |
| 4286905 | Samanta | Sep 1981 | A |
| 4304576 | Hattori et al. | Dec 1981 | A |
| 4314827 | Leitheiser et al. | Feb 1982 | A |
| 4341663 | Derleth et al. | Jul 1982 | A |
| 4393021 | Eisenberg et al. | Jul 1983 | A |
| 4452911 | Eccles et al. | Jun 1984 | A |
| 4457767 | Poon et al. | Jul 1984 | A |
| 4469758 | Scott | Sep 1984 | A |
| 4505720 | Gabor et al. | Mar 1985 | A |
| 4541842 | Rostoker | Jul 1985 | A |
| 4548617 | Miyatani et al. | Oct 1985 | A |
| 4570048 | Poole | Feb 1986 | A |
| 4618349 | Hashimoto et al. | Oct 1986 | A |
| 4623364 | Cottringer et al. | Nov 1986 | A |
| 4656330 | Poole | Apr 1987 | A |
| 4657754 | Bauer et al. | Apr 1987 | A |
| 4659341 | Ludwig et al. | Apr 1987 | A |
| 4678560 | Stole et al. | Jul 1987 | A |
| 4711750 | Scott | Dec 1987 | A |
| 4728043 | Ersdal et al. | Mar 1988 | A |
| 4744802 | Schwabel | May 1988 | A |
| 4770671 | Monroe | Sep 1988 | A |
| 4786292 | Janz et al. | Nov 1988 | A |
| 4797139 | Bauer | Jan 1989 | A |
| 4797269 | Bauer et al. | Jan 1989 | A |
| 4799939 | Bloecher et al. | Jan 1989 | A |
| 4829027 | Cutler et al. | May 1989 | A |
| 4832706 | Yates | May 1989 | A |
| 4848041 | Kruschke | Jul 1989 | A |
| 4858527 | Masanao | Aug 1989 | A |
| 4863573 | Moore et al. | Sep 1989 | A |
| 4876226 | Fuentes | Oct 1989 | A |
| 4881951 | Wood et al. | Nov 1989 | A |
| 4917852 | Poole et al. | Apr 1990 | A |
| 4918116 | Gardziella et al. | Apr 1990 | A |
| 4925457 | Dekok et al. | May 1990 | A |
| 4925815 | Tani et al. | May 1990 | A |
| 4930266 | Calhoun et al. | Jun 1990 | A |
| 4942011 | Bolt et al. | Jul 1990 | A |
| 4954462 | Wood | Sep 1990 | A |
| 4960441 | Pellow et al. | Oct 1990 | A |
| 4961757 | Rhodes et al. | Oct 1990 | A |
| 4963012 | Tracy | Oct 1990 | A |
| 4964883 | Morris et al. | Oct 1990 | A |
| 4970057 | Wilkens et al. | Nov 1990 | A |
| 4997461 | Markhoff-Matheny et al. | Mar 1991 | A |
| 5009675 | Kunz et al. | Apr 1991 | A |
| 5009676 | Rue et al. | Apr 1991 | A |
| 5011508 | Wald et al. | Apr 1991 | A |
| 5011510 | Hayakawa et al. | Apr 1991 | A |
| 5014468 | Ravipati et al. | May 1991 | A |
| 5024795 | Kennedy et al. | Jun 1991 | A |
| 5032304 | Toyota | Jul 1991 | A |
| 5035723 | Kalinowski et al. | Jul 1991 | A |
| 5035724 | Pukari et al. | Jul 1991 | A |
| 5042991 | Kunz et al. | Aug 1991 | A |
| 5049166 | Kirkendall | Sep 1991 | A |
| 5049645 | Nagaoka et al. | Sep 1991 | A |
| 5053367 | Newkirk et al. | Oct 1991 | A |
| 5053369 | Winkler et al. | Oct 1991 | A |
| 5076991 | Poole et al. | Dec 1991 | A |
| 5078753 | Broberg et al. | Jan 1992 | A |
| 5081082 | Hai-Doo et al. | Jan 1992 | A |
| 5085671 | Martin et al. | Feb 1992 | A |
| 5090968 | Pellow | Feb 1992 | A |
| 5094986 | Matsumoto et al. | Mar 1992 | A |
| 5098740 | Tewari | Mar 1992 | A |
| 5103598 | Kelly | Apr 1992 | A |
| 5108963 | Fu et al. | Apr 1992 | A |
| 5114438 | Leatherman et al. | May 1992 | A |
| 5120327 | Dennis | Jun 1992 | A |
| 5123935 | Kanamaru et al. | Jun 1992 | A |
| 5129919 | Kalinowski et al. | Jul 1992 | A |
| 5131926 | Rostoker et al. | Jul 1992 | A |
| 5132984 | Simpson | Jul 1992 | A |
| 5139978 | Wood | Aug 1992 | A |
| 5152917 | Pieper et al. | Oct 1992 | A |
| 5160509 | Carman et al. | Nov 1992 | A |
| 5164744 | Yoshida et al. | Nov 1992 | A |
| 5173457 | Shorthouse | Dec 1992 | A |
| 5178849 | Bauer | Jan 1993 | A |
| 5180630 | Giglia | Jan 1993 | A |
| 5185012 | Kelly | Feb 1993 | A |
| 5185299 | Wood et al. | Feb 1993 | A |
| 5190568 | Tselesin | Mar 1993 | A |
| 5194072 | Rue et al. | Mar 1993 | A |
| 5201916 | Berg et al. | Apr 1993 | A |
| 5203886 | Sheldon et al. | Apr 1993 | A |
| 5213591 | Celikkaya et al. | May 1993 | A |
| 5215552 | Sung | Jun 1993 | A |
| 5219462 | Bruxvoort et al. | Jun 1993 | A |
| 5219806 | Wood | Jun 1993 | A |
| 5221294 | Carman et al. | Jun 1993 | A |
| 5224970 | Harakawa et al. | Jul 1993 | A |
| 5227104 | Bauer | Jul 1993 | A |
| 5244477 | Rue et al. | Sep 1993 | A |
| 5244849 | Roy et al. | Sep 1993 | A |
| 5273558 | Nelson et al. | Dec 1993 | A |
| 5277702 | Thibault et al. | Jan 1994 | A |
| 5282875 | Wood | Feb 1994 | A |
| 5288297 | Ringwood | Feb 1994 | A |
| 5300130 | Rostoker | Apr 1994 | A |
| 5304331 | Leonard et al. | Apr 1994 | A |
| 5312789 | Wood | May 1994 | A |
| 5312791 | Coblenz et al. | May 1994 | A |
| 5314513 | Miller et al. | May 1994 | A |
| 5366523 | Rowenhorst et al. | Nov 1994 | A |
| 5366525 | Fujiyama | Nov 1994 | A |
| 5372620 | Rowse et al. | Dec 1994 | A |
| 5373786 | Umaba | Dec 1994 | A |
| 5376598 | Preedy et al. | Dec 1994 | A |
| 5376602 | Nilsen | Dec 1994 | A |
| 5383945 | Cottringer et al. | Jan 1995 | A |
| 5395407 | Cottringer et al. | Mar 1995 | A |
| 5409645 | Torre, Jr. et al. | Apr 1995 | A |
| 5429648 | Wu | Jul 1995 | A |
| 5431967 | Manthiram | Jul 1995 | A |
| 5435816 | Spurgeon et al. | Jul 1995 | A |
| 5437754 | Calhoun | Aug 1995 | A |
| 5441549 | Helmin | Aug 1995 | A |
| 5443603 | Kirkendall | Aug 1995 | A |
| 5447894 | Yasuoka et al. | Sep 1995 | A |
| 5453106 | Roberts | Sep 1995 | A |
| 5454844 | Hibbard et al. | Oct 1995 | A |
| 5470806 | Krstic et al. | Nov 1995 | A |
| 5479873 | Shintani et al. | Jan 1996 | A |
| 5482756 | Berger et al. | Jan 1996 | A |
| 5486496 | Talbert et al. | Jan 1996 | A |
| 5489318 | Erickson et al. | Feb 1996 | A |
| 5496386 | Broberg et al. | Mar 1996 | A |
| 5500273 | Holmes et al. | Mar 1996 | A |
| 5514631 | Cottringer et al. | May 1996 | A |
| 5516347 | Garg | May 1996 | A |
| 5516348 | Conwell et al. | May 1996 | A |
| 5523074 | Takahashi et al. | Jun 1996 | A |
| 5525100 | Kelly et al. | Jun 1996 | A |
| 5527369 | Garg | Jun 1996 | A |
| 5543368 | Talbert et al. | Aug 1996 | A |
| 5549962 | Holmes et al. | Aug 1996 | A |
| 5551963 | Larmie | Sep 1996 | A |
| 5560745 | Roberts | Oct 1996 | A |
| 5567150 | Conwell et al. | Oct 1996 | A |
| 5567214 | Ashley | Oct 1996 | A |
| 5567251 | Peker et al. | Oct 1996 | A |
| 5571297 | Swei et al. | Nov 1996 | A |
| 5576409 | Mackey | Nov 1996 | A |
| 5578095 | Bland et al. | Nov 1996 | A |
| 5578222 | Trischuk et al. | Nov 1996 | A |
| 5582625 | Wright et al. | Dec 1996 | A |
| 5584896 | Broberg et al. | Dec 1996 | A |
| 5584897 | Christianson et al. | Dec 1996 | A |
| 5591685 | Mitomo et al. | Jan 1997 | A |
| 5593468 | Khaund et al. | Jan 1997 | A |
| 5599493 | Ito et al. | Feb 1997 | A |
| 5603738 | Zeiringer et al. | Feb 1997 | A |
| 5609706 | Benedict et al. | Mar 1997 | A |
| 5611829 | Monroe et al. | Mar 1997 | A |
| 5618221 | Furukawa et al. | Apr 1997 | A |
| 5628952 | Holmes et al. | May 1997 | A |
| 5641469 | Garg et al. | Jun 1997 | A |
| RE35570 | Rowenhorst et al. | Jul 1997 | E |
| 5645619 | Erickson et al. | Jul 1997 | A |
| 5651925 | Ashley et al. | Jul 1997 | A |
| 5656217 | Rogers et al. | Aug 1997 | A |
| 5667542 | Law et al. | Sep 1997 | A |
| 5669941 | Peterson | Sep 1997 | A |
| 5669943 | Horton et al. | Sep 1997 | A |
| 5672097 | Hoopman | Sep 1997 | A |
| 5672554 | Mohri et al. | Sep 1997 | A |
| 5683844 | Mammino | Nov 1997 | A |
| 5690707 | Wood et al. | Nov 1997 | A |
| 5702811 | Ho et al. | Dec 1997 | A |
| 5725162 | Garg et al. | Mar 1998 | A |
| 5736619 | Kane et al. | Apr 1998 | A |
| 5738696 | Wu | Apr 1998 | A |
| 5738697 | Wu et al. | Apr 1998 | A |
| 5751313 | Miyashita et al. | May 1998 | A |
| 5759481 | Pujari et al. | Jun 1998 | A |
| 5776214 | Wood | Jul 1998 | A |
| 5779743 | Wood | Jul 1998 | A |
| 5785722 | Garg et al. | Jul 1998 | A |
| 5810587 | Bruns et al. | Sep 1998 | A |
| 5820450 | Calhoun | Oct 1998 | A |
| 5830248 | Christianson et al. | Nov 1998 | A |
| 5840089 | Chesley et al. | Nov 1998 | A |
| 5849646 | Stout et al. | Dec 1998 | A |
| 5855997 | Amateau | Jan 1999 | A |
| 5863306 | Wei et al. | Jan 1999 | A |
| 5866254 | Peker et al. | Feb 1999 | A |
| 5871555 | Wood | Feb 1999 | A |
| 5876793 | Sherman et al. | Mar 1999 | A |
| 5885311 | McCutcheon et al. | Mar 1999 | A |
| 5893935 | Wood | Apr 1999 | A |
| 5902647 | Venkataramani | May 1999 | A |
| 5908477 | Harmer et al. | Jun 1999 | A |
| 5908478 | Wood | Jun 1999 | A |
| 5919549 | Van et al. | Jul 1999 | A |
| 5924917 | Benedict et al. | Jul 1999 | A |
| 5946991 | Hoopman | Sep 1999 | A |
| 5975987 | Hoopman et al. | Nov 1999 | A |
| 5980678 | Tselesin | Nov 1999 | A |
| 5984988 | Berg et al. | Nov 1999 | A |
| 5989301 | Laconto, Sr. et al. | Nov 1999 | A |
| 5997597 | Hagan | Dec 1999 | A |
| 6016660 | Abramshe | Jan 2000 | A |
| 6019805 | Herron | Feb 2000 | A |
| 6024824 | Krech | Feb 2000 | A |
| 6027326 | Cesarano, III et al. | Feb 2000 | A |
| 6048577 | Garg | Apr 2000 | A |
| 6053956 | Wood | Apr 2000 | A |
| 6054093 | Torre, Jr. et al. | Apr 2000 | A |
| 6080215 | Stubbs et al. | Jun 2000 | A |
| 6080216 | Erickson | Jun 2000 | A |
| 6083622 | Garg et al. | Jul 2000 | A |
| 6096107 | Caracostas et al. | Aug 2000 | A |
| 6110241 | Sung | Aug 2000 | A |
| 6129540 | Hoopman et al. | Oct 2000 | A |
| 6136288 | Bauer et al. | Oct 2000 | A |
| 6146247 | Nokubi et al. | Nov 2000 | A |
| 6179887 | Barber, Jr. et al. | Jan 2001 | B1 |
| 6206942 | Wood | Mar 2001 | B1 |
| 6228134 | Erickson | May 2001 | B1 |
| 6238450 | Garg et al. | May 2001 | B1 |
| 6258137 | Garg et al. | Jul 2001 | B1 |
| 6258141 | Sung et al. | Jul 2001 | B1 |
| 6261682 | Law | Jul 2001 | B1 |
| 6264710 | Erickson | Jul 2001 | B1 |
| 6277160 | Stubbs et al. | Aug 2001 | B1 |
| 6277161 | Castro et al. | Aug 2001 | B1 |
| 6283997 | Garg et al. | Sep 2001 | B1 |
| 6284690 | Nakahata et al. | Sep 2001 | B1 |
| 6287353 | Celikkaya | Sep 2001 | B1 |
| 6306007 | Mori et al. | Oct 2001 | B1 |
| 6312324 | Mitsui et al. | Nov 2001 | B1 |
| 6319108 | Adefris et al. | Nov 2001 | B1 |
| 6331343 | Perez et al. | Dec 2001 | B1 |
| 6371842 | Romero | Apr 2002 | B1 |
| 6391812 | Araki et al. | May 2002 | B1 |
| 6401795 | Cesarano, III et al. | Jun 2002 | B1 |
| 6403001 | Hayashi | Jun 2002 | B1 |
| 6413286 | Swei et al. | Jul 2002 | B1 |
| 6451076 | Nevoret et al. | Sep 2002 | B1 |
| 6475253 | Culler et al. | Nov 2002 | B2 |
| 6511938 | Liu | Jan 2003 | B1 |
| 6524681 | Seitz et al. | Feb 2003 | B1 |
| 6531423 | Schwetz et al. | Mar 2003 | B1 |
| 6537140 | Miller et al. | Mar 2003 | B1 |
| 6579819 | Hirosaki et al. | Jun 2003 | B2 |
| 6582623 | Grumbine et al. | Jun 2003 | B1 |
| 6583080 | Rosenflanz | Jun 2003 | B1 |
| 6599177 | Nevoret et al. | Jul 2003 | B2 |
| 6646019 | Perez et al. | Nov 2003 | B2 |
| 6652361 | Gash et al. | Nov 2003 | B1 |
| 6669745 | Prichard et al. | Dec 2003 | B2 |
| 6685755 | Ramanath et al. | Feb 2004 | B2 |
| 6696258 | Wei | Feb 2004 | B1 |
| 6702650 | Adefris | Mar 2004 | B2 |
| 6737378 | Hirosaki et al. | May 2004 | B2 |
| 6749496 | Mota et al. | Jun 2004 | B2 |
| 6750173 | Rizkalla | Jun 2004 | B2 |
| 6755729 | Ramanath et al. | Jun 2004 | B2 |
| 6802878 | Monroe | Oct 2004 | B1 |
| 6821196 | Oliver | Nov 2004 | B2 |
| 6833014 | Welygan et al. | Dec 2004 | B2 |
| 6843815 | Thurber et al. | Jan 2005 | B1 |
| 6846795 | Lant et al. | Jan 2005 | B2 |
| 6878456 | Castro et al. | Apr 2005 | B2 |
| 6881483 | McArdle et al. | Apr 2005 | B2 |
| 6888360 | Connell et al. | May 2005 | B1 |
| 6913824 | Culler et al. | Jul 2005 | B2 |
| 6942561 | Mota et al. | Sep 2005 | B2 |
| 6949128 | Annen | Sep 2005 | B2 |
| 6974930 | Jense | Dec 2005 | B2 |
| 7022179 | Dry | Apr 2006 | B1 |
| 7044989 | Welygan et al. | May 2006 | B2 |
| 7141522 | Rosenflanz et al. | Nov 2006 | B2 |
| 7168267 | Rosenflanz et al. | Jan 2007 | B2 |
| 7169198 | Moeltgen et al. | Jan 2007 | B2 |
| 7267604 | Yoshizawa et al. | Sep 2007 | B2 |
| 7267700 | Collins et al. | Sep 2007 | B2 |
| 7294158 | Welygan et al. | Nov 2007 | B2 |
| 7297170 | Welygan et al. | Nov 2007 | B2 |
| 7297402 | Evans et al. | Nov 2007 | B2 |
| 7364788 | Kishbaugh et al. | Apr 2008 | B2 |
| 7373887 | Jackson | May 2008 | B2 |
| 7384437 | Welygan et al. | Jun 2008 | B2 |
| 7488544 | Schofalvi et al. | Feb 2009 | B2 |
| 7507268 | Rosenflanz | Mar 2009 | B2 |
| 7553346 | Welygan et al. | Jun 2009 | B2 |
| 7556558 | Palmgren | Jul 2009 | B2 |
| 7560062 | Gould et al. | Jul 2009 | B2 |
| 7560139 | Thebault et al. | Jul 2009 | B2 |
| 7563293 | Rosenflanz | Jul 2009 | B2 |
| 7611795 | Aoyama et al. | Nov 2009 | B2 |
| 7618684 | Nesbitt | Nov 2009 | B2 |
| 7662735 | Rosenflanz et al. | Feb 2010 | B2 |
| 7666344 | Schofalvi et al. | Feb 2010 | B2 |
| 7666475 | Morrison | Feb 2010 | B2 |
| 7669658 | Barron et al. | Mar 2010 | B2 |
| 7670679 | Krishna et al. | Mar 2010 | B2 |
| 7695542 | Drivdahl et al. | Apr 2010 | B2 |
| 7858189 | Wagener et al. | Dec 2010 | B2 |
| 7867302 | Nevoret et al. | Jan 2011 | B2 |
| 7906057 | Zhang et al. | Mar 2011 | B2 |
| 7968147 | Fang et al. | Jun 2011 | B2 |
| 7972430 | Millard et al. | Jul 2011 | B2 |
| 8021449 | Seth et al. | Sep 2011 | B2 |
| 8034137 | Erickson et al. | Oct 2011 | B2 |
| 8049136 | Mase et al. | Nov 2011 | B2 |
| 8070556 | Kumar et al. | Dec 2011 | B2 |
| 8123828 | Culler et al. | Feb 2012 | B2 |
| 8141484 | Ojima et al. | Mar 2012 | B2 |
| 8142531 | Adefris et al. | Mar 2012 | B2 |
| 8142532 | Erickson et al. | Mar 2012 | B2 |
| 8142891 | Culler et al. | Mar 2012 | B2 |
| 8251774 | Joseph et al. | Aug 2012 | B2 |
| 8256091 | Duescher | Sep 2012 | B2 |
| 8440602 | Gonzales et al. | May 2013 | B2 |
| 8440603 | Gonzales et al. | May 2013 | B2 |
| 8445422 | Gonzales et al. | May 2013 | B2 |
| 8470759 | Gonzales et al. | Jun 2013 | B2 |
| 8480772 | Welygan et al. | Jul 2013 | B2 |
| 8530682 | Sachs | Sep 2013 | B2 |
| 8628597 | Palmgren et al. | Jan 2014 | B2 |
| 8783589 | Hart et al. | Jul 2014 | B2 |
| 8852643 | Gonzales et al. | Oct 2014 | B2 |
| 8920527 | Seider et al. | Dec 2014 | B2 |
| 8921687 | Welser et al. | Dec 2014 | B1 |
| 9017439 | Yener et al. | Apr 2015 | B2 |
| 9079154 | Rosendahl | Jul 2015 | B2 |
| 9181477 | Collins et al. | Nov 2015 | B2 |
| 9259726 | Gopal | Feb 2016 | B2 |
| 9375826 | Tian et al. | Jun 2016 | B2 |
| 9758724 | Collins et al. | Sep 2017 | B2 |
| D849066 | Hanschen et al. | May 2019 | S |
| D849067 | Hanschen et al. | May 2019 | S |
| D862538 | Hanschen et al. | Oct 2019 | S |
| D870782 | Hanschen et al. | Dec 2019 | S |
| 10556323 | Alkhas et al. | Feb 2020 | B2 |
| 10557068 | Oldenkotte et al. | Feb 2020 | B2 |
| 10655038 | Martinez et al. | May 2020 | B2 |
| 10710211 | Lehuu et al. | Jul 2020 | B2 |
| 10717908 | Hejtmann et al. | Jul 2020 | B2 |
| 20010027623 | Rosenflanz | Oct 2001 | A1 |
| 20020026752 | Culler et al. | Mar 2002 | A1 |
| 20020068518 | Cesena et al. | Jun 2002 | A1 |
| 20020084290 | Materna | Jul 2002 | A1 |
| 20020090891 | Adefris et al. | Jul 2002 | A1 |
| 20020151265 | Adefris | Oct 2002 | A1 |
| 20020170236 | Larson et al. | Nov 2002 | A1 |
| 20020174935 | Burdon et al. | Nov 2002 | A1 |
| 20020177391 | Fritz et al. | Nov 2002 | A1 |
| 20030008933 | Perez et al. | Jan 2003 | A1 |
| 20030022961 | Kusaka et al. | Jan 2003 | A1 |
| 20030029094 | Moeltgen et al. | Feb 2003 | A1 |
| 20030085204 | Lagos | May 2003 | A1 |
| 20030109371 | Pujari et al. | Jun 2003 | A1 |
| 20030110707 | Rosenflanz et al. | Jun 2003 | A1 |
| 20030126800 | Seth et al. | Jul 2003 | A1 |
| 20040003895 | Amano et al. | Jan 2004 | A1 |
| 20040148868 | Anderson et al. | Aug 2004 | A1 |
| 20040148967 | Celikkaya et al. | Aug 2004 | A1 |
| 20040202844 | Wong | Oct 2004 | A1 |
| 20040224125 | Yamada et al. | Nov 2004 | A1 |
| 20040235406 | Duescher | Nov 2004 | A1 |
| 20040244675 | Kishimoto et al. | Dec 2004 | A1 |
| 20050020190 | Schutz et al. | Jan 2005 | A1 |
| 20050060941 | Provow et al. | Mar 2005 | A1 |
| 20050060947 | McArdle et al. | Mar 2005 | A1 |
| 20050064805 | Culler et al. | Mar 2005 | A1 |
| 20050081455 | Welygan et al. | Apr 2005 | A1 |
| 20050118939 | Duescher | Jun 2005 | A1 |
| 20050132655 | Anderson et al. | Jun 2005 | A1 |
| 20050218565 | DiChiara, Jr. | Oct 2005 | A1 |
| 20050223649 | O'Gary et al. | Oct 2005 | A1 |
| 20050232853 | Evans et al. | Oct 2005 | A1 |
| 20050245179 | Luedeke | Nov 2005 | A1 |
| 20050255801 | Pollasky | Nov 2005 | A1 |
| 20050266221 | Karam et al. | Dec 2005 | A1 |
| 20050271795 | Moini et al. | Dec 2005 | A1 |
| 20050284029 | Bourlier et al. | Dec 2005 | A1 |
| 20060049540 | Hui et al. | Mar 2006 | A1 |
| 20060126265 | Crespi et al. | Jun 2006 | A1 |
| 20060135050 | Petersen et al. | Jun 2006 | A1 |
| 20060177488 | Caruso et al. | Aug 2006 | A1 |
| 20060185256 | Nevoret et al. | Aug 2006 | A1 |
| 20070020457 | Adefris | Jan 2007 | A1 |
| 20070051355 | Sung | Mar 2007 | A1 |
| 20070072527 | Palmgren | Mar 2007 | A1 |
| 20070074456 | Orlhac et al. | Apr 2007 | A1 |
| 20070087928 | Rosenflanz et al. | Apr 2007 | A1 |
| 20070234646 | Can et al. | Oct 2007 | A1 |
| 20080017053 | Araumi et al. | Jan 2008 | A1 |
| 20080098659 | Sung | May 2008 | A1 |
| 20080121124 | Sato | May 2008 | A1 |
| 20080172951 | Starling | Jul 2008 | A1 |
| 20080176075 | Bauer et al. | Jul 2008 | A1 |
| 20080179783 | Liu et al. | Jul 2008 | A1 |
| 20080230951 | Dannoux et al. | Sep 2008 | A1 |
| 20080262577 | Altshuler et al. | Oct 2008 | A1 |
| 20080286590 | Besida et al. | Nov 2008 | A1 |
| 20080299875 | Duescher | Dec 2008 | A1 |
| 20090016916 | Rosenzweig et al. | Jan 2009 | A1 |
| 20090017736 | Block et al. | Jan 2009 | A1 |
| 20090098365 | Moeltgen | Apr 2009 | A1 |
| 20090165394 | Culler et al. | Jul 2009 | A1 |
| 20090165661 | Koenig et al. | Jul 2009 | A1 |
| 20090169816 | Erickson et al. | Jul 2009 | A1 |
| 20090208734 | Macfie et al. | Aug 2009 | A1 |
| 20090246464 | Watanabe et al. | Oct 2009 | A1 |
| 20100000159 | Walia et al. | Jan 2010 | A1 |
| 20100003900 | Sakaguchi et al. | Jan 2010 | A1 |
| 20100003904 | Duescher | Jan 2010 | A1 |
| 20100040767 | Uibel et al. | Feb 2010 | A1 |
| 20100056816 | Wallin et al. | Mar 2010 | A1 |
| 20100068974 | Dumm | Mar 2010 | A1 |
| 20100146867 | Boden et al. | Jun 2010 | A1 |
| 20100151195 | Culler et al. | Jun 2010 | A1 |
| 20100151196 | Adefris et al. | Jun 2010 | A1 |
| 20100151201 | Erickson et al. | Jun 2010 | A1 |
| 20100190424 | Francois et al. | Jul 2010 | A1 |
| 20100201018 | Yoshioka et al. | Aug 2010 | A1 |
| 20100251625 | Gaeta | Oct 2010 | A1 |
| 20100292428 | Meador et al. | Nov 2010 | A1 |
| 20100307067 | Sigalas et al. | Dec 2010 | A1 |
| 20100319269 | Erickson | Dec 2010 | A1 |
| 20110008604 | Boylan | Jan 2011 | A1 |
| 20110081848 | Chen | Apr 2011 | A1 |
| 20110111563 | Yanagi et al. | May 2011 | A1 |
| 20110124483 | Shah et al. | May 2011 | A1 |
| 20110136659 | Allen et al. | Jun 2011 | A1 |
| 20110146509 | Welygan et al. | Jun 2011 | A1 |
| 20110152548 | Sachs | Jun 2011 | A1 |
| 20110160104 | Wu et al. | Jun 2011 | A1 |
| 20110244769 | David et al. | Oct 2011 | A1 |
| 20110289854 | Moren et al. | Dec 2011 | A1 |
| 20110314746 | Erickson et al. | Dec 2011 | A1 |
| 20120000135 | Eilers et al. | Jan 2012 | A1 |
| 20120034847 | Besse et al. | Feb 2012 | A1 |
| 20120055098 | Ramanath et al. | Mar 2012 | A1 |
| 20120137597 | Adefris et al. | Jun 2012 | A1 |
| 20120144754 | Culler et al. | Jun 2012 | A1 |
| 20120144755 | Erickson et al. | Jun 2012 | A1 |
| 20120153547 | Bauer et al. | Jun 2012 | A1 |
| 20120167481 | Yener et al. | Jul 2012 | A1 |
| 20120168979 | Bauer et al. | Jul 2012 | A1 |
| 20120227333 | Adefris et al. | Sep 2012 | A1 |
| 20120231711 | Keipert et al. | Sep 2012 | A1 |
| 20120308837 | Schlechtriemen et al. | Dec 2012 | A1 |
| 20130000212 | Wang et al. | Jan 2013 | A1 |
| 20130000216 | Wang et al. | Jan 2013 | A1 |
| 20130009484 | Yu | Jan 2013 | A1 |
| 20130036402 | Mutisya et al. | Feb 2013 | A1 |
| 20130045251 | Cen et al. | Feb 2013 | A1 |
| 20130067669 | Gonzales et al. | Mar 2013 | A1 |
| 20130072417 | Perez-Prat et al. | Mar 2013 | A1 |
| 20130074418 | Panzarella et al. | Mar 2013 | A1 |
| 20130125477 | Adefris | May 2013 | A1 |
| 20130180180 | Yener et al. | Jul 2013 | A1 |
| 20130186005 | Kavanaugh | Jul 2013 | A1 |
| 20130186006 | Kavanaugh et al. | Jul 2013 | A1 |
| 20130199105 | Braun et al. | Aug 2013 | A1 |
| 20130203328 | Givot et al. | Aug 2013 | A1 |
| 20130236725 | Yener et al. | Sep 2013 | A1 |
| 20130255162 | Welygan et al. | Oct 2013 | A1 |
| 20130267150 | Seider et al. | Oct 2013 | A1 |
| 20130283705 | Fischer et al. | Oct 2013 | A1 |
| 20130296587 | Rosendahl | Nov 2013 | A1 |
| 20130305614 | Gaeta et al. | Nov 2013 | A1 |
| 20130337262 | Bauer et al. | Dec 2013 | A1 |
| 20130337725 | Monroe | Dec 2013 | A1 |
| 20130344786 | Keipert | Dec 2013 | A1 |
| 20140000176 | Moren et al. | Jan 2014 | A1 |
| 20140007518 | Yener et al. | Jan 2014 | A1 |
| 20140080393 | Ludwig | Mar 2014 | A1 |
| 20140106126 | Gaeta et al. | Apr 2014 | A1 |
| 20140107356 | Gopal | Apr 2014 | A1 |
| 20140182216 | Panzarella et al. | Jul 2014 | A1 |
| 20140182217 | Yener et al. | Jul 2014 | A1 |
| 20140186585 | Field, III et al. | Jul 2014 | A1 |
| 20140250797 | Yener et al. | Sep 2014 | A1 |
| 20140256238 | Van et al. | Sep 2014 | A1 |
| 20140287658 | Flaschberger et al. | Sep 2014 | A1 |
| 20140290147 | Seth et al. | Oct 2014 | A1 |
| 20140352721 | Gonzales et al. | Dec 2014 | A1 |
| 20140352722 | Gonzales et al. | Dec 2014 | A1 |
| 20140357544 | Gonzales et al. | Dec 2014 | A1 |
| 20140378036 | Cichowlas et al. | Dec 2014 | A1 |
| 20150000209 | Louapre et al. | Jan 2015 | A1 |
| 20150000210 | Breder et al. | Jan 2015 | A1 |
| 20150007399 | Gonzales et al. | Jan 2015 | A1 |
| 20150007400 | Gonzales et al. | Jan 2015 | A1 |
| 20150089881 | Stevenson et al. | Apr 2015 | A1 |
| 20150126098 | Eilers et al. | May 2015 | A1 |
| 20150128505 | Wang et al. | May 2015 | A1 |
| 20150183089 | Iyengar et al. | Jul 2015 | A1 |
| 20150209932 | Lehuu et al. | Jul 2015 | A1 |
| 20150218430 | Yener et al. | Aug 2015 | A1 |
| 20150232727 | Erickson | Aug 2015 | A1 |
| 20150291865 | Breder et al. | Oct 2015 | A1 |
| 20150291866 | Arcona et al. | Oct 2015 | A1 |
| 20150291867 | Breder et al. | Oct 2015 | A1 |
| 20150343603 | Breder et al. | Dec 2015 | A1 |
| 20160177152 | Braun | Jun 2016 | A1 |
| 20160177153 | Josseaux | Jun 2016 | A1 |
| 20160177154 | Josseaux et al. | Jun 2016 | A1 |
| 20160186027 | Sarangi | Jun 2016 | A1 |
| 20160186028 | Louapare et al. | Jun 2016 | A1 |
| 20160214903 | Humpal et al. | Jul 2016 | A1 |
| 20160298013 | Bock et al. | Oct 2016 | A1 |
| 20160303704 | Chou et al. | Oct 2016 | A1 |
| 20160303705 | Chou et al. | Oct 2016 | A1 |
| 20160304760 | Bock et al. | Oct 2016 | A1 |
| 20160311081 | Culler et al. | Oct 2016 | A1 |
| 20160311084 | Culler et al. | Oct 2016 | A1 |
| 20160326416 | Bauer et al. | Nov 2016 | A1 |
| 20160340564 | Louapre et al. | Nov 2016 | A1 |
| 20160354898 | Nienaber et al. | Dec 2016 | A1 |
| 20160362589 | Bauer et al. | Dec 2016 | A1 |
| 20170066099 | Nakamura | Mar 2017 | A1 |
| 20170114260 | Bock et al. | Apr 2017 | A1 |
| 20170129075 | Thurber et al. | May 2017 | A1 |
| 20170225299 | Keipert et al. | Aug 2017 | A1 |
| 20170349797 | Yener et al. | Dec 2017 | A1 |
| 20180086957 | Sahlin et al. | Mar 2018 | A1 |
| 20180161960 | Wilson et al. | Jun 2018 | A1 |
| 20180169837 | Liu | Jun 2018 | A1 |
| 20180215975 | Marazano et al. | Aug 2018 | A1 |
| 20180215976 | Cotter et al. | Aug 2018 | A1 |
| 20180318983 | Wilson et al. | Nov 2018 | A1 |
| 20190022826 | Franke et al. | Jan 2019 | A1 |
| 20190030684 | Van et al. | Jan 2019 | A1 |
| 20190091835 | Culler et al. | Mar 2019 | A1 |
| 20190126436 | Westberg et al. | May 2019 | A1 |
| 20190217442 | Gaeta et al. | Jul 2019 | A1 |
| 20190249052 | Eckel et al. | Aug 2019 | A1 |
| 20190270182 | Eckel et al. | Sep 2019 | A1 |
| 20190322915 | Jiwpanich et al. | Oct 2019 | A1 |
| 20190330505 | Bujnowski et al. | Oct 2019 | A1 |
| 20190337124 | Liu et al. | Nov 2019 | A1 |
| 20190338172 | Erickson et al. | Nov 2019 | A1 |
| 20190338173 | Yener et al. | Nov 2019 | A1 |
| 20190351531 | Nelson et al. | Nov 2019 | A1 |
| 20190366511 | Huber | Dec 2019 | A1 |
| 20190382637 | Braun et al. | Dec 2019 | A1 |
| 20200139512 | Culler et al. | May 2020 | A1 |
| 20200148927 | Arcona et al. | May 2020 | A1 |
| 20200156215 | Jusuf et al. | May 2020 | A1 |
| 20200157396 | Cotter et al. | May 2020 | A1 |
| 20200157397 | Stevenson et al. | May 2020 | A1 |
| 20200199426 | Yener et al. | Jun 2020 | A1 |
| Number | Date | Country |
|---|---|---|
| 743715 | Oct 1966 | CA |
| 2423788 | Jul 2002 | CA |
| 685051 | Mar 1995 | CH |
| 102281992 | Dec 2011 | CN |
| 103189164 | Jul 2013 | CN |
| 102123837 | Jul 2014 | CN |
| 104125875 | Oct 2014 | CN |
| 104994995 | Oct 2015 | CN |
| 105713568 | Jun 2016 | CN |
| 102012023688 | Apr 2014 | DE |
| 202014101739 | Jun 2014 | DE |
| 202014101741 | Jun 2014 | DE |
| 102013202204 | Aug 2014 | DE |
| 102013210158 | Dec 2014 | DE |
| 102013210716 | Dec 2014 | DE |
| 102013212598 | Dec 2014 | DE |
| 102013212622 | Dec 2014 | DE |
| 102013212634 | Dec 2014 | DE |
| 102013212639 | Dec 2014 | DE |
| 102013212644 | Dec 2014 | DE |
| 102013212653 | Dec 2014 | DE |
| 102013212654 | Dec 2014 | DE |
| 102013212661 | Dec 2014 | DE |
| 102013212666 | Dec 2014 | DE |
| 102013212677 | Dec 2014 | DE |
| 102013212680 | Dec 2014 | DE |
| 102013212687 | Dec 2014 | DE |
| 102013212690 | Dec 2014 | DE |
| 102013212700 | Dec 2014 | DE |
| 102014210836 | Dec 2014 | DE |
| 0078896 | May 1983 | EP |
| 0152768 | Sep 1987 | EP |
| 0293163 | Nov 1988 | EP |
| 0480133 | Apr 1992 | EP |
| 0652919 | May 1995 | EP |
| 0662110 | Jul 1995 | EP |
| 0500369 | Jan 1996 | EP |
| 0609864 | Nov 1996 | EP |
| 0771769 | May 1997 | EP |
| 0812456 | Dec 1997 | EP |
| 0651778 | May 1998 | EP |
| 0614861 | May 2001 | EP |
| 0931032 | Jul 2001 | EP |
| 0833803 | Aug 2001 | EP |
| 1356152 | Oct 2003 | EP |
| 1371451 | Dec 2003 | EP |
| 1383631 | Jan 2004 | EP |
| 1015181 | Mar 2004 | EP |
| 1492845 | Jan 2005 | EP |
| 1851007 | Nov 2007 | EP |
| 1960157 | Aug 2008 | EP |
| 2176031 | Apr 2010 | EP |
| 2184134 | May 2010 | EP |
| 2242618 | Oct 2010 | EP |
| 2390056 | Nov 2011 | EP |
| 1800801 | Mar 2012 | EP |
| 2445982 | May 2012 | EP |
| 2507016 | Oct 2012 | EP |
| 2537917 | Dec 2012 | EP |
| 2567784 | Mar 2013 | EP |
| 2631286 | Aug 2013 | EP |
| 2692813 | Feb 2014 | EP |
| 2692814 | Feb 2014 | EP |
| 2692815 | Feb 2014 | EP |
| 2692816 | Feb 2014 | EP |
| 2692817 | Feb 2014 | EP |
| 2692818 | Feb 2014 | EP |
| 2692819 | Feb 2014 | EP |
| 2692820 | Feb 2014 | EP |
| 2692821 | Feb 2014 | EP |
| 2719752 | Apr 2014 | EP |
| 2720676 | Apr 2014 | EP |
| 2012972 | Jun 2014 | EP |
| 3342839 | Jul 2015 | EP |
| 3319758 | May 2018 | EP |
| 3342839 | Jul 2018 | EP |
| 3444313 | Jul 2020 | EP |
| 2354373 | Jan 1978 | FR |
| 986847 | Mar 1965 | GB |
| 1466054 | Mar 1977 | GB |
| 53064890 | Jun 1978 | JP |
| 60-006356 | Jan 1985 | JP |
| 62002946 | Jan 1987 | JP |
| 63036905 | Jul 1988 | JP |
| 3079277 | Apr 1991 | JP |
| 03-287687 | Dec 1991 | JP |
| 5285833 | Nov 1993 | JP |
| 6114739 | Apr 1994 | JP |
| 7008474 | Feb 1995 | JP |
| 10113875 | May 1998 | JP |
| 2779252 | Jul 1998 | JP |
| 10330734 | Dec 1998 | JP |
| H10315142 | Dec 1998 | JP |
| 2957492 | Oct 1999 | JP |
| 2000091280 | Mar 2000 | JP |
| 2000-336344 | Dec 2000 | JP |
| 2000354967 | Dec 2000 | JP |
| 3160084 | Apr 2001 | JP |
| 2001162541 | Jun 2001 | JP |
| 03194269 | Jul 2001 | JP |
| 2001180930 | Jul 2001 | JP |
| 2001207160 | Jul 2001 | JP |
| 2002-038131 | Feb 2002 | JP |
| 2002210659 | Jul 2002 | JP |
| 2003-049158 | Feb 2003 | JP |
| 2004-510873 | Apr 2004 | JP |
| 2004209624 | Jul 2004 | JP |
| 2006130586 | May 2006 | JP |
| 2006130636 | May 2006 | JP |
| 2006159402 | Jun 2006 | JP |
| 2006-192540 | Jul 2006 | JP |
| 2008132560 | Jun 2008 | JP |
| 2008194761 | Aug 2008 | JP |
| 2008531305 | Aug 2008 | JP |
| 2012512046 | May 2012 | JP |
| 2012512047 | May 2012 | JP |
| 2012512048 | May 2012 | JP |
| 2012530615 | Dec 2012 | JP |
| 5238725 | Jul 2013 | JP |
| 5238726 | Jul 2013 | JP |
| 2014503367 | Feb 2014 | JP |
| 2017518889 | Jul 2017 | JP |
| 2017538588 | Dec 2017 | JP |
| 2018510073 | Apr 2018 | JP |
| 171464 | Nov 1982 | NL |
| 1994002559 | Feb 1994 | WO |
| 9503370 | Feb 1995 | WO |
| 9518192 | Jul 1995 | WO |
| 1995020469 | Aug 1995 | WO |
| 9627189 | Sep 1996 | WO |
| 9711484 | Mar 1997 | WO |
| 1997014536 | Apr 1997 | WO |
| 9720011 | Jun 1997 | WO |
| 1997020011 | Jun 1997 | WO |
| 9720011 | Jun 1997 | WO |
| 1999006500 | Feb 1999 | WO |
| 9938817 | Aug 1999 | WO |
| 1999038817 | Aug 1999 | WO |
| 9954424 | Oct 1999 | WO |
| 0114494 | Mar 2001 | WO |
| 0123323 | Apr 2001 | WO |
| 2002097150 | Dec 2002 | WO |
| 03087236 | Oct 2003 | WO |
| 2005080624 | Sep 2005 | WO |
| 2006027593 | Mar 2006 | WO |
| 2007041538 | Apr 2007 | WO |
| 2009085578 | Jul 2009 | WO |
| 2010077509 | Jul 2010 | WO |
| 2010085587 | Jul 2010 | WO |
| 2010151201 | Dec 2010 | WO |
| 2011005425 | Jan 2011 | WO |
| 2011068724 | Jun 2011 | WO |
| 2011068714 | Jun 2011 | WO |
| 2011087649 | Jul 2011 | WO |
| 2011109188 | Sep 2011 | WO |
| 2011139562 | Nov 2011 | WO |
| 2011149625 | Dec 2011 | WO |
| 2012018903 | Feb 2012 | WO |
| 2012061016 | May 2012 | WO |
| 2012061033 | May 2012 | WO |
| 2012092590 | Jul 2012 | WO |
| 2012092605 | Jul 2012 | WO |
| 2012112305 | Aug 2012 | WO |
| 2012112322 | Aug 2012 | WO |
| 2010070294 | Aug 2012 | WO |
| 2012141905 | Oct 2012 | WO |
| 2013003830 | Jan 2013 | WO |
| 2013003831 | Jan 2013 | WO |
| 2013009484 | Jan 2013 | WO |
| 2013036402 | Mar 2013 | WO |
| 2013040423 | Mar 2013 | WO |
| 2013045251 | Apr 2013 | WO |
| 2013049239 | Apr 2013 | WO |
| 2013070576 | May 2013 | WO |
| 2013101575 | Jul 2013 | WO |
| 2013102170 | Jul 2013 | WO |
| 2013102176 | Jul 2013 | WO |
| 2013102177 | Jul 2013 | WO |
| 2013106597 | Jul 2013 | WO |
| 2013106602 | Jul 2013 | WO |
| 2013151745 | Oct 2013 | WO |
| 2013177446 | Nov 2013 | WO |
| 2013186146 | Dec 2013 | WO |
| 2013188038 | Dec 2013 | WO |
| 2014005120 | Jan 2014 | WO |
| 2014161001 | Feb 2014 | WO |
| 2014020068 | Feb 2014 | WO |
| 2014020075 | Feb 2014 | WO |
| 2014022453 | Feb 2014 | WO |
| 2014022462 | Feb 2014 | WO |
| 2014022465 | Feb 2014 | WO |
| 2014057273 | Apr 2014 | WO |
| 2014062701 | Apr 2014 | WO |
| 2014070468 | May 2014 | WO |
| 2014106173 | Jul 2014 | WO |
| 2014106211 | Jul 2014 | WO |
| 2014124554 | Aug 2014 | WO |
| 2014137972 | Sep 2014 | WO |
| 2014140689 | Sep 2014 | WO |
| 2014165390 | Oct 2014 | WO |
| 2014176108 | Oct 2014 | WO |
| 2014206739 | Dec 2014 | WO |
| 2014206890 | Dec 2014 | WO |
| 2014206967 | Dec 2014 | WO |
| 2014209567 | Dec 2014 | WO |
| 2014210160 | Dec 2014 | WO |
| 2014210442 | Dec 2014 | WO |
| 2014210532 | Dec 2014 | WO |
| 2014210568 | Dec 2014 | WO |
| 2015050781 | Apr 2015 | WO |
| 2015073346 | May 2015 | WO |
| 2015048768 | Jun 2015 | WO |
| 2015088953 | Jun 2015 | WO |
| 2015089527 | Jun 2015 | WO |
| 2015089528 | Jun 2015 | WO |
| 2015089529 | Jun 2015 | WO |
| 2015100018 | Jul 2015 | WO |
| 2015100020 | Jul 2015 | WO |
| 2015100220 | Jul 2015 | WO |
| 2015102992 | Jul 2015 | WO |
| 2015112379 | Jul 2015 | WO |
| 2015130487 | Sep 2015 | WO |
| 2015158009 | Oct 2015 | WO |
| 2015160854 | Oct 2015 | WO |
| 2015160855 | Oct 2015 | WO |
| 2015160857 | Oct 2015 | WO |
| 2015164211 | Oct 2015 | WO |
| 2015165122 | Nov 2015 | WO |
| 2015167910 | Nov 2015 | WO |
| 2015179335 | Nov 2015 | WO |
| 2015180005 | Dec 2015 | WO |
| 2015184355 | Dec 2015 | WO |
| 2016028683 | Feb 2016 | WO |
| 2016044158 | Mar 2016 | WO |
| 2016064726 | Apr 2016 | WO |
| 2016089675 | Jun 2016 | WO |
| 2016105469 | Jun 2016 | WO |
| 2016105474 | Jun 2016 | WO |
| 2016160357 | Oct 2016 | WO |
| 2016161157 | Oct 2016 | WO |
| 2016161170 | Oct 2016 | WO |
| 2016167967 | Oct 2016 | WO |
| 2016187570 | Nov 2016 | WO |
| 2016196795 | Dec 2016 | WO |
| 2016201104 | Dec 2016 | WO |
| 2016205133 | Dec 2016 | WO |
| 2016205267 | Dec 2016 | WO |
| 2016210057 | Dec 2016 | WO |
| 2017007703 | Jan 2017 | WO |
| 2017007714 | Jan 2017 | WO |
| 2017062482 | Apr 2017 | WO |
| 2017083249 | May 2017 | WO |
| 2017083255 | May 2017 | WO |
| 2016105543 | Sep 2017 | WO |
| 2017151498 | Sep 2017 | WO |
| 2018010730 | Jan 2018 | WO |
| 2018026669 | Feb 2018 | WO |
| 2018057465 | Mar 2018 | WO |
| 2018057558 | Mar 2018 | WO |
| 2018063902 | Apr 2018 | WO |
| 2018063958 | Apr 2018 | WO |
| 2018063960 | Apr 2018 | WO |
| 2018063962 | Apr 2018 | WO |
| 2018064642 | Apr 2018 | WO |
| 2018080703 | May 2018 | WO |
| 2018080704 | May 2018 | WO |
| 2018080705 | May 2018 | WO |
| 2018080755 | May 2018 | WO |
| 2018080756 | May 2018 | WO |
| 2018080765 | May 2018 | WO |
| 2018080778 | May 2018 | WO |
| 2018080784 | May 2018 | WO |
| 2018081246 | May 2018 | WO |
| 2018118688 | Jun 2018 | WO |
| 2018118690 | Jun 2018 | WO |
| 2018118695 | Jun 2018 | WO |
| 2018118699 | Jun 2018 | WO |
| 2018134732 | Jul 2018 | WO |
| 2018136268 | Jul 2018 | WO |
| 2018136269 | Jul 2018 | WO |
| 2018136271 | Jul 2018 | WO |
| 2018207145 | Nov 2018 | WO |
| 2018207145 | Nov 2018 | WO |
| 2019001908 | Jan 2019 | WO |
| 2019069157 | Apr 2019 | WO |
| 2019102312 | May 2019 | WO |
| 2019102328 | May 2019 | WO |
| 2019102329 | May 2019 | WO |
| 2019102330 | May 2019 | WO |
| 2019102331 | May 2019 | WO |
| 2019167022 | Sep 2019 | WO |
| 2019197948 | Oct 2019 | WO |
| 2019207415 | Oct 2019 | WO |
| 2019207416 | Oct 2019 | WO |
| 2019207417 | Oct 2019 | WO |
| 2019207423 | Oct 2019 | WO |
| 2019215571 | Nov 2019 | WO |
| 2020035764 | Feb 2020 | WO |
| 2020075005 | Apr 2020 | WO |
| 2020079522 | Apr 2020 | WO |
| 2020084382 | Apr 2020 | WO |
| 2020084483 | Apr 2020 | WO |
| 2020089741 | May 2020 | WO |
| 2020128794 | Jun 2020 | WO |
| Entry |
|---|
| “Investigation of Shaped Abrasive Particles vol. 1: Review of U.S. Pat. No. 6,054,093 Apr. 25, 2000” © Apr. 2011, 5 pages. |
| Austin, Benson M., “Thick-Film Screen Printing,” Solid State Technology, Jun. 1969, pp. 53-58. |
| Avril, Nicholas Joseph, “Manufacturing Glass-fiber Reinforcement for Grinding Wheels,” Massachusetts Institute of Technology, 1996, 105 pgs. |
| Bacher, Rudolph J., “High Resolution Thick Film Printing,” E.I. du Pont de Nemours & Company, Inc., pp. 576-581, date unknown. |
| Besse, John R., “Understanding and controlling wheel truing and dressing forces when rotary plunge dressing,” Cutting Tool Engineering, Jun. 2012, vol. 64, Issue 6, 5 pages. |
| Brewer, L. et al., Journal of Materials Research, 1999, vol. 14, No. 10, pp. 3907-3912. |
| Ciccotti, M. et al., “Complex dynamics in the peeling of an adhesive tape,” International Journal of Adhesion & Adhesives 24 (2004) pp. 143-151. |
| Dupont, “Kevlar Aramid Pulp”, Copyright 2011, DuPont, 1 page. |
| Wu, J. et al., Friction and Wear Properties of Kevlar Pulp Reinforced Epoxy. |
| J. European Ceramic Society 31, Abstract only (2011) 2073-2081. |
| Riemer, Dietrich E., “Analytical Engineering Model of the Screen Printing Process: Part II,” Solid State Technology, Sep. 1988, pp. 85-90. |
| Miller, L.F., “Paste Transfer in the Screening Process,” Solid State Technology, Jun. 1969, pp. 46-52. |
| Morgan, P. et al., “Ceramic Composites of Monazite and Alumina,” J. Am. Ceram. Soc., 78, 1995, 1553-63. |
| Riemer, Dietrich E., “Analytical Engineering Model of the Screen Printing Process: Part I,” Solid State Technology, Aug. 1988, pp. 107-111. |
| Winter Catalogue No. 5, Dressing tools, WINTER diamond tools for dressing grinding wheels, 140 pages. |
| Badger, Jeffrey, “Evaluation of Triangular, Engineered-Shape Ceramic Abrasive in Cutting Discs,” Supplement to the Welding Journal, Apr. 2014, vol. 93, pp. 107-s to 115-s. |
| 3M Cubitron II Abrasive Belts Brochure, Shaping the Future, Jan. 2011, 6 pages. |
| Vanstrum et al., Precisely Shaped Grain (PSG): 3M's Innovation in Abrasive Grain Technology, date unknown, 1 page. |
| Graf, “Cubitron II: Precision-Shaped Grain (PSG) Turns the Concept of Gear Grinding Upside Down,” gearsolutions.com, May 2014, pp. 36-44. |
| DOW Machine Tool Accessories, Grinding & Surface Finishing, www.1mta.com, Nov. 2014, 72 pages. |
| Kumar et al., “Composites by rapid prototyping technology”, Material & Design, Feb. 2010, vol. 31, Issue 2, pp. 850-856. |
| Lewis et al., “Direct Ink Writing of Three-Dimensional Ceramic Structures”, Journal of the American Ceramic Society, US, Nov. 30, 2006, vol. 89, Issue 12, pp. 3599-3609. |
| International Search Report and Written Opinion for Application No. PCT/US2016/036701, dated Sep. 1, 2016, 12 pages. |
| Number | Date | Country | |
|---|---|---|---|
| 20180370857 A1 | Dec 2018 | US |
| Number | Date | Country | |
|---|---|---|---|
| 62522800 | Jun 2017 | US |
