1. Field
Disclosed herein are elements of superhard polycrystalline material synthesized in a high-temperature, high-pressure process and used for wear, cutting, drawing, and other applications. These elements have specifically placed superhard surfaces at locations where wear resistance may be required. In particular, disclosed herein are polycrystalline diamond and polycrystalline diamond-like (collectively called PCD) cutting elements with tailored wear and impact toughness resistance and methods of manufacturing them. One particular form of PCD cutting elements which may be used in drill bits for drilling subterranean formations are called polycrystalline diamond cutters (PDC's).
2. Description of the Related Art
U.S. Pat. No. 6,861,098 discloses methods for fabrication of PCD cutting elements, inserts, and tools. Polycrystalline diamond and polycrystalline diamond-like cutting elements are generally known, for the purposes of this specification, as PCD cutting elements. PCD cutting elements may be formed from carbon based materials with short inter-atomic distances between neighboring atoms. One type of polycrystalline diamond-like material known as carbonitride (CN) is described in U.S. Pat. No. 5,776,615. Another, form of PCD is described in more detail below. In general, PCD cutting elements are formed from a mix of materials processed under high-temperature and high-pressure (HTHP) into a polycrystalline matrix of inter-bonded superhard carbon based crystals. A trait of PCD cutting elements may be the use of catalyzing materials during their formation, the residue from which may impose a limit upon the maximum useful operating temperature of the PCD cutting element while in service.
One manufactured form of PCD cutting element is a two-layer or multi-layer PCD cutting element where a facing table of polycrystalline diamond is integrally bonded to a substrate of less hard material, such as cemented tungsten carbide. The PCD cutting element may be in the form of a circular or part-circular tablet, or may be formed into other shapes, suitable for applications such as hollow dies, heat sinks, friction bearings, valve surfaces, indenters, tool mandrels, etc. PCD cutting elements of this type may be used in applications where a hard and abrasive wear and erosion resistant material may be required. The substrate of the PCD cutting element may be brazed to a carrier, which may also be made of cemented tungsten carbide. This configuration may be used for PCD's used as cutting elements, for example, in fixed cutter or rolling cutter earth boring bits when received in a socket of the drill bit, or when fixed to a post in a machine tool for machining PCD cutting elements that are used for this purpose may be called polycrystalline diamond cutters (PDC's).
PCD cutting elements may be formed by sintering diamond powder with a suitable binder-catalyzing material with a substrate of less hard material in a high-pressure, high-temperature press. One method of forming this polycrystalline diamond is disclosed, for example, in U.S. Pat. No. 3,141,746, the entire contents of which are hereby incorporated by reference. In one process for manufacturing PCD cutting elements, diamond powder is applied to the surface of a preformed tungsten carbide substrate incorporating cobalt. The assembly may then be subjected to high temperatures and pressures in a press. During this process, cobalt migrates from the substrate into the diamond layer and acts as a binder-catalyzing material, causing the diamond particles to bond to one another with diamond-to-diamond bonding, and also causing the diamond layer to bond to the substrate.
The completed PCD cutting element may have at least one matrix of diamond crystals bonded to each other with many interstices containing a binder-catalyzing material metal as described above. The diamond crystals may form a first continuous matrix of diamond, and the interstices may form a second continuous matrix of interstices containing the binder-catalyzing material. In addition, there may be some areas where the diamond to diamond growth has encapsulated some of the binder-catalyzing material. These “islands” may not be part of the continuous interstitial matrix of binder-catalyzing material.
In one particular form, the diamond element may constitute 85% to 95% by volume of the PDC and the binder-catalyzing material the other 5% to 15%. Although cobalt may be used as the binder-catalyzing material, other group VIII elements, including cobalt, nickel, iron, and alloys thereof, may be employed.
U.S. Pat. No. 7,407,012 describes the fabrication of a highly impact resistant tool that has a sintered body of diamond or diamond-like particles in a metal matrix bonded to cemented metal carbide substrate at a non-planar interface. The catalyst for enabling diamond-to-diamond sintering may be provided by the substrate. The general manufacture of a PDC, insert, or cutting tool may use a cemented carbide substrate to provide a catalyst to aid in the sintering of the diamond particles.
Published US Patent Application US 2005/0044800, describes the use of a meltable sealant barrier to cleanse the PCD cutting element constituent assembly via vacuum thermal reduction followed by melting the sealant to provide a hermetic seal in a can used for the further high temperature, high pressure (HTHP) processing—with a temperature which may be higher than 1300C and a pressure which may be greater than 65 KBar. The sealing of the can may be required to limit contamination of the diamond particle bed during HTHP processing, and to also maintain a high vacuum in the can to limit oxidation and other contamination. The HTHP can assemblies may help to prevent contamination of the PCD cutting element table and may also be sealed by using processes, such as EB welding, used for standard production of cutters and inserts.
U.S. Pat. No. 6,045,440 describes a structured PDC that is oriented for use in earth boring where formation chips and debris are funneled away from the cutting edge via the use of raised top surfaces on the PDC. The redirection of the debris may be achieved by creation of high and low surfaces on the PDC cutting surface. A method used to form the protrusion on the PDC is not described in detail in this patent, the surface texture and geometry of this cutter surface may be limited to the ability to extrude and/or form sealing can surfaces that are a negative of the desired PDC front face extrusions, or alternatively formed by post HTHP processing, such as EDM and Laser cutting—as may be necessary to form the surfaces on the cutter face.
Described herein is a process for making PCD cutting elements in a ‘double pressing’ operation. This process may provide PCD cutting elements with improvements in wear life over prior PCD cutting elements. Previously, high temperature, high pressure (HTHP) sintering of round discs into a PCD (polycrystalline diamond) material (or segments) manufactured in a second HTHP press cycle tended to result in cracking of the diamond material on the face of the PDC due to the stresses developed during the forming process.
The present ‘double pressed’ HTHP sintered PDC disclosed herein may have enhanced physical characteristics. The method for making a double pressed HTHP sintered PDC uses a previously HTHP pressed PCD material that may be leached or rendered free of all or substantially all of the metallic material is provided. This PCD material may then be crushed and sized to form a PCD grit that may be layered or dispersed with other materials and then canned & sintered into a final product PDC in a second HTHP pressing operation.
In one preferred embodiment, these canned & sintered PDC's made from previously pressed PCD cutting elements may be formed into tiles or segments (rectangular or arc shaped) and then may be leached (or substantially rendered free) of all metallic material, laid out in single or multiple layers, packed with a diamond filler (e.g., traditional diamond feedstock or diamond powder), and then HTHP sintered a second time in the normal fashion into a PDC of the present disclosure.
This method for making a double pressed HTHP sintered PDC may begin by arranging segments of previously pressed PCD segments that are leached (as described above) and laid out in a single layer or multiple layers, packed with a diamond filler (e.g., traditional diamond feedstock), and then HTHP sintered in the normal fashion into a PDC.
In another embodiment, other assorted shapes of previously pressed PCD may be selected, designed, and/or configured for advantageously arranging the stress fields within the PDC when in operation. These previously pressed PCD cutting elements may be leached or otherwise rendered free of metals and then may be combined with various combinations of diamond grit, diamond ‘chunks’, and/or shaped PCD segments and geometrically arranged in a pattern optimized for performance and subjected to a second HTHP cycle, cleaned up and made ready for use in earth-boring, or other related operations known in the industry.
An alternative forming process for manufacturing a PDC in accordance with the present disclosure may utilize a spark plasma sintering process (SPS) in place of the second HTHP pressing cycle. A forming process utilizing a spark plasma sintering process (SPS) may also be provided as an additional or alternative process in PDC manufacture. In this process, the powder materials may be stacked between a die and punch on a sintering stage in a chamber and held between a set of electrodes. When a pulse or a pulse stream is provided under pressure, the temperature may rapidly rise to a sintering temperature, say from about 1000 to about 2500° C. resulting in the production of a sintered PDC in only a few minutes.
In the following description, the sintered composite described hereafter may be formed of polycrystalline diamond (or PCD). However, this process may also be applicable to other super hard abrasive materials, including, but not limited to, synthetic or natural diamond, cubic boron nitride, and other related materials.
Polycrystalline diamond cutters (PDC's) may be used as cutting elements in drilling bits used to form boreholes into the earth, and may be used for, but not limited to, drilling tools for exploration and production of hydrocarbon minerals from the earth.
For illustrative purposes only, a typical drilling operation is shown in
As the drill bit 1 is rotated from the surface and/or by the downhole motor 9, it drills into the earth allowing the drill string 2 to advance, forming the borehole 6. For the purpose of understanding how these systems may be operated for the type of drilling system illustrated in
A more detailed view of a PCD cutting element 10 of the present disclosure is shown in
The PCD cutting element 10 may have a body in the form of a circular tablet having a thin front facing, diamond table 22 of diamond bonded in a ‘double press’ process which may be, for example, a high-pressure high-temperature (HPHT) process. The double press process may be used to press the diamond table 22 to a substrate 24 of less hard material, such as cemented tungsten carbide or other metallic material—as will be explained in detail. The cutting element 10 may be preformed (as will also be described) and then may be bonded onto a generally cylindrical carrier 26 which may also be formed from cemented tungsten carbide, or may alternatively be attached directly to the blade 16. The cutting element 10 may also have a non-planar interface 27 between the diamond table 22 and the substrate 24. Furthermore, the PCD cutting element 10 may have a peripheral working surface 28 and an end working surface 30 which, as illustrated, may be substantially perpendicular to one another.
The cylindrical carrier 26 is received within a correspondingly shaped socket or recess in the blade 16. The carrier 26 may be brazed, shrink fit or press fit into the socket (not shown) in the drill bit 1. Where brazed, the braze joint may extend over the carrier 26 and part of the substrate 24. In operation, the fixed cutter drill bit 1 is rotated and weight is applied. This forces the cutting elements 10 into the earth being drilled, effecting a cutting and/or drilling action.
These PCD cutting elements 10 may be made in a conventional very high temperature and high pressure (HTHP) pressing (or sintering) operation (which is well known in the industry), and then finished machined into the cylindrical shapes shown. One such process for making these PCD cutting elements 10 may involve combining mixtures of various sized diamond crystals, which are mixed together, and processed into the PCD cutting elements 10 as previously described.
Forming these cutting elements 10 with more than one HTHP cycle may be called ‘double pressing’. ‘Double pressing’ of cutters has been attempted in the past and may provide some improvement in wear life results of the products, but the process for manufacture may entail difficulties and internal defects. These defects may involve limited wear life of the resulting product. In particular, HTHP sintering of round discs into a PDC in a second press cycle may lead to cracking of the diamond layer due to stresses developed during the process.
An alternate process for double pressing PCD cutting elements as described herein involves double pressing an HTHP sintered PDC. Previously pressed PCD material may have all metallic materials removed from its crystalline structure by, for example, acid leaching. The PCD material may then be crushed and sized to form a fine PCD grit. This PCD grit may be layered (or otherwise dispersed) in a normally canned and sintered PCD cutting element. Optionally, the grit may be mixed with ‘virgin’ diamond crystals of selected shapes and sizes before being canned and sintered. The previously pressed PCD material may be leached before and/or after it is crushed and/or formed.
In another embodiment, previously pressed PDC segments (or tiles) of various shapes, including but not limited to triangular, rectangular, circular, oval and arc shaped, are first rendered substantially free of all catalyzing and other metallic material, typically in a leaching process, and laid out in a mold with a single or multiple layer configuration. The spaces between these tiles may then be packed with diamond filler (e.g., traditional diamond feedstock) of one or more selected sizes and shapes, and HTHP sintered a second time to form the new PDC of the present disclosure.
In one particular example, a number of ‘pie’ shaped previously pressed PDC segments were fully leached of catalyzing material and then laid out in a single (or alternately multiple) layer(s) in a mold, and the intervening spaces were then packed with fine grained, traditional diamond feedstock. The resulting product was then HTHP sintered a second time in the normal fashion into a PDC.
Additionally, ‘stress engineered’ shapes (e.g., geometries of PCD cutting elements that make advantageous use of the operating behavior of the PCD cutting element) of previously pressed PCD may also be utilized. These ‘recycled’ PCD cutting elements may be leached of substantially all of the metallic and/or catalyzing material they may have remaining These ‘recycled’ PCD cutting elements may then be combined with, or selectively used in, various combinations of crushed diamond grits and/or solid shapes to form a PDC. In this manner, the PDC may then be patterned for optimized performance.
As shown in
In another example, the manufacturing process may begin with a fine (˜5 micron distribution) HTHP diamond feedstock made into a large diameter circular PDC blank, as may be used with cutting tools. This large PDC blank may then be cut into a number of smaller pieces (or segments) that may be, but not limited to, pie-shaped tiles, cylinders, blocks, or one of many other geometric shapes. The diagonal dimension of these pieces may be, but is not limited to, sizes smaller than about 1.0 mm. These pieces may then be leached to remove all or substantially all of the metallic materials that may be present, such as tungsten carbide (WC) substrate, cobalt (Co), and any other metallic materials which may be present. These pressed and leached pieces (or segments) of PCD may then be combined with fine powdered diamond feedstock as described above and pressed a second time in the HTHP process as previously described, resulting in a preformed PCD cutting element of the present disclosure.
This preformed PCD cutting element was comparison tested to the ‘standard product’ known prior art PCD cutting element in a two part internal standard wear test procedure known as a G-ratio test.
Based on historical data, an unleached ‘standard product’ PCD cutting element may have a G-ratio (which is a number indicative of the wear resistance of the PCD material) of about 20×105 (volume of diamond removed/volume of granite removed). If the cutting surface of this ‘standard product’ PCD cutting element is leached substantially free of catalyzing material, the typical G-ratio may increase to about 80×105. This increased G-ratio may be a number typical for conventional leached prior art cutting elements. By way of comparison, a 5 micron ‘double pressed’ cutting tool made in accordance with the present disclosure using a 5 micron average particle size diamond feedstock and tested in a similar fashion as described above may have a G-ratio of 50×105 before leaching and a G-ratio of 150×105 upon leaching—nearly a 100% improvement over the ‘standard product’ PDC cutting element. During the second pressing operation, some of the pore spaces of the previously pressed & leached portion of the diamond table may be re-filled with the binder/catalyzing material (e.g., cobalt) to drop the G-ratio.
In another example, before leaching, abrasion testing of the double pressed PDC cutting element may yield a G-ratio of about 100×105. Upon leaching, the G-ratio of this previously pressed, leached, double pressed & re-leached PDC cutting element may increase to about 1000×105, yielding over a tenfold increase in wear resistance over the ‘standard product’ leached PDC. It should be noted that laboratory tests may not account for all the variability's of PDC cutting elements as they are run in the field. Therefore, although laboratory test results may be helpful for selecting which of the cutting elements may be better, field testing may be performed for confirmation.
The new PDC may provide improved abrasion resistance over existing PDC cutting elements. In addition, the loose diamond feedstock packing within the PCD material pieces may provide a form of stress relief in the final product. In addition, tiling the diamond layer may result in a relatively stress free, yet very thick PCD layer. In addition, the fine feedstock of the previously pressed PCD cutting element may provide an additional incremental increase to the abrasion resistance of the resulting PDC without using a significantly higher pressure during processing.
The PCD grit may be varied in grit size, quantity, and layer thickness to vary the physical properties of the final product, as may be required. The comparable wear patterns of the various PCD grit options may reveal differential wear rates between the previously pressed, leached, double pressed, and re-leached product and the loose feedstock packed around that grit, HTHP sintered and leached for the first time. These differential wear rates may allow the PDC cutting edge to become ‘self-sharpening’ for a more efficient cutting action at the rock.
The various grit options may also be useful in cases where an edge of the PDC were to chip during operation. The differential wear rate of the PDC may favor smaller pieces being dislodged rather than creating larger chunks. This may be characteristic of a more homogenous, traditionally produced diamond table. In addition, the ‘double pressed’ product may provide a way to reuse the ‘used’ PDC material recovered from ‘dull’, previously used cutters. The initial pressed feedstock for double HTHP pressing may be made into pie, tiled or block shapes. Alternatively, the PDC's may be free standing—thereby potentially reducing the need for finishing & cutting.
In the manufacturing process for the PCD 50, it may be desirable to control the feedstock of the double pressed PDC, the grit size of the previously pressed PCD grit, the mix ratio of the PCD grit with loose diamond feedstock, the particle size of the loose feedstock, the layer thickness, and (where present), and the geometrical arrangement of the PCD segments or tiles. This may be used to minimize the residual stress for providing a stress free product, controlled layer thickness of the PCD grit mix, leaching process, and leach depth.
In performing the present applications, it may be necessary to control a number of process parameters. These may include, for example, origin of feedstock of the double pressed PDC, the previously pressed grit size, the mix of the PCD grit with loose diamond feedstock, and the size of the loose feedstock. Other process parameters to control may involve controlling the layer thickness, and designing the geometrical arrangement of the segments or tiles for a stress free product. In addition, the layer thickness of the PCD grit mix, the leaching process, and the leach depth may require close control.
In some circumstances, it may also be desirable to treat the PCD produced in a further leaching process to remove all of, or selected portion(s) of, any catalyst infiltrant that may have re-infiltrated the PCD layer.
In addition to being useful for PCD cutting elements 10 with an integral face (or working surface 30) as shown in
As shown in
In an alternate embodiment, as shown, in
For instance, the above described PCD cutting element 50 may have non-leached PCD segments 52 between leached PCD segments 54 and may be used as PCD cutting elements in much the same manner as the PCD cutting element 10 with integrally formed faces.
In still other embodiments, the pre-leached PCD material 54 may have selected shapes and sizes for the PCD 50, for example as shown in
Alternately, the individual blocks of leached PCD material 54 may be shaped and laid in an arc around the periphery (or peripheral working surface 28) of the PCD cutting element 50 as shown in
Finally, in another embodiment as shown in
In each of these embodiments, as described herein, the entirety of the working surfaces 28, 30 (or portions thereof) of the PDC 50 may be leached a second time in a leaching process, and then assembled into a drill bit 1, or other wear component.
In addition, an alternative forming process for manufacturing a PCD cutting element 50 may utilize a spark plasma sintering process (SPS) as illustrated in
When moderate mechanical pressure is applied to the ‘stack’ 100, as shown by the letter ‘P’, and the voltage is maintained across the stack through upper electrode 200 and lower electrode 210, the combination of the pressure P, and sparking allows the ‘stack’ 100 to form diamond-to-diamond bonds of PCD, similar to those formed in the traditional HTHP process commonly used for diamond synthesis. Since the electric pulse (or pulses) is (are) provided to the discs 100 under moderate compressive pressure P, the temperature within the discs 100 may rapidly rise to sintering temperature, for example, at about 1000° C. to about 2500° C., resulting in the production of a near finished sintered PCD cutting element 50 in only a few minutes. The PCD cutting element 50 may be finished (e.g., trimmed) following various stages of the manufacture, such as after a first pressing, after a second pressing and/or after SPS.
This SPS process or other microwave process may be used to bond or attach a diamond layer, such as a partially (or fully) leached diamond wafer, to a carbide substrate. These processes may be used with low temperature, low pressure bonding or attaching methods. The bonding may be performed using an alloy or compound, such as a nano-alloy compound (e.g., Ni-nano-WC, or a Ni-nano diamond alloy). For example, Ni-nano-WC (Nickel-nano-tungsten carbide) may be used to join 20 μm diamond powders with a WC—Co substrate. In another example, SPS is used to bond a partially (or fully) leached flat diamond wafer to a carbide substrate with nano-WC 65%+NiCrFeBSi.
Whereas the present invention has been described in particular relation to the drawings attached hereto, it should be understood that other and further modifications apart from those shown or suggested herein, may be made within the scope and spirit of the present disclosure.
This application claims the benefit of U.S. Provisional Patent Application No. 61/406,273, filed on Oct. 25, 2010, the entire contents of which are hereby incorporated by reference herein.
Number | Name | Date | Kind |
---|---|---|---|
2992900 | Bovenkerk | Jul 1961 | A |
3141746 | De Lai | Jul 1964 | A |
3141885 | Ross | Jul 1964 | A |
3148161 | Wentorf, Jr. et al. | Sep 1964 | A |
3574580 | Stromberg et al. | Apr 1971 | A |
3744982 | Bovenkerk et al. | Jul 1973 | A |
3831428 | Wentorf, Jr. et al. | Aug 1974 | A |
3913280 | Hall | Oct 1975 | A |
4268276 | Bovenkirk | May 1981 | A |
4288248 | Bovenkirk et al. | Sep 1981 | A |
4534773 | Phaal et al. | Aug 1985 | A |
4726718 | Meskin et al. | Feb 1988 | A |
5011509 | Frushour | Apr 1991 | A |
5011514 | Cho et al. | Apr 1991 | A |
5106391 | Lloyd | Apr 1992 | A |
5127923 | Bunting et al. | Jul 1992 | A |
5205684 | Meskin et al. | Apr 1993 | A |
5433280 | Smith | Jul 1995 | A |
5510193 | Cerutti et al. | Apr 1996 | A |
5544550 | Smith | Aug 1996 | A |
5645617 | Frushour | Jul 1997 | A |
5722497 | Gum et al. | Mar 1998 | A |
5776615 | Wong et al. | Jul 1998 | A |
5839329 | Smith et al. | Nov 1998 | A |
5957006 | Smith | Sep 1999 | A |
5981057 | Collins | Nov 1999 | A |
6041875 | Rai et al. | Mar 2000 | A |
6045440 | Johnson et al. | Apr 2000 | A |
6063333 | Dennis | May 2000 | A |
6193001 | Eyre et al. | Feb 2001 | B1 |
6200514 | Meister | Mar 2001 | B1 |
6209420 | Butcher et al. | Apr 2001 | B1 |
6353771 | Southland | Mar 2002 | B1 |
6454030 | Findley et al. | Sep 2002 | B1 |
6544308 | Griffin et al. | Apr 2003 | B2 |
6601662 | Matthias et al. | Aug 2003 | B2 |
6655481 | Findley et al. | Dec 2003 | B2 |
6852414 | Frushour | Feb 2005 | B1 |
6861098 | Griffin et al. | Mar 2005 | B2 |
7384436 | Sung | Jun 2008 | B2 |
7407012 | Keshavan et al. | Aug 2008 | B2 |
7435478 | Keshavan | Oct 2008 | B2 |
7493973 | Keshavan et al. | Feb 2009 | B2 |
7533740 | Zhang et al. | May 2009 | B2 |
7540181 | Memmott | Jun 2009 | B1 |
7588108 | Miyao | Sep 2009 | B2 |
7775107 | Holmquist | Aug 2010 | B2 |
7862634 | Belnap et al. | Jan 2011 | B2 |
7862932 | Eguchi et al. | Jan 2011 | B2 |
7963348 | Laird et al. | Jun 2011 | B2 |
7972409 | Fujino et al. | Jul 2011 | B2 |
8919463 | Setlur et al. | Dec 2014 | B2 |
20050044800 | Hall et al. | Mar 2005 | A1 |
20050115744 | Griffin et al. | Jun 2005 | A1 |
20060042172 | Sung | Mar 2006 | A1 |
20060060391 | Eyre et al. | Mar 2006 | A1 |
20060060392 | Eyre | Mar 2006 | A1 |
20070023206 | Keshavan | Feb 2007 | A1 |
20070039762 | Achilles | Feb 2007 | A1 |
20070187155 | Middlemiss | Aug 2007 | A1 |
20070277651 | Calnan et al. | Dec 2007 | A1 |
20080028891 | Calnan et al. | Feb 2008 | A1 |
20080073126 | Shen et al. | Mar 2008 | A1 |
20080142275 | Griffin et al. | Jun 2008 | A1 |
20090166094 | Keshavan et al. | Jul 2009 | A1 |
20100200305 | Griffin et al. | Aug 2010 | A1 |
20100012391 | Shamburger | Sep 2010 | A1 |
20100243336 | Dourfaye et al. | Sep 2010 | A1 |
20100282519 | Zhang | Nov 2010 | A1 |
20100288045 | Holmquist | Nov 2010 | A1 |
20100294571 | Belnap | Nov 2010 | A1 |
20110171414 | Sreshta et al. | Jul 2011 | A1 |
20110212303 | Fuller et al. | Sep 2011 | A1 |
20120097458 | Voronin et al. | Apr 2012 | A1 |
20130146369 | Voronin et al. | Jun 2013 | A1 |
Number | Date | Country |
---|---|---|
1190791 | Mar 2002 | EP |
2442135 | Mar 2008 | GB |
2453425 | Apr 2009 | GB |
2455425 | Jun 2009 | GB |
2463975 | Apr 2010 | GB |
2463975 | Apr 2010 | GB |
200224601 | Mar 2002 | WO |
200224603 | Mar 2002 | WO |
Entry |
---|
United Arab Emirates Patent Application No. 447/2013 First Rejection dated Jun. 6, 2016 (11 pages). |
SPS, ‘What's SPS?’ [online], 8 pages, Japan, [retreived Oct. 24, 2011], Retrieved from Internet<URL: http://www.scm-sps.com/e_htm/whats_e_htm/whatsps_e.htm>. |
English Translation of Chinese Third Office Action dated Aug. 21, 2015 for Chinese Application No. 201180061290.5, 14 pages. |
International Preliminary Report on Patentability and Written Opinion for PCT Application No. PCT/GB2011/001531 dated May 21, 2013, 6 pages. |
Examination Report for Canadian Patent Application No. 2,828,956 dated Sep. 23, 2014, 2 pages. |
Examination Report for Canadian Patent Application No. 2,814,903 dated Jul. 31, 2014, 2 pages. |
First Office Action and Translation for Chinese Patent Application No. 201180061290.5 dated Jul. 9, 2014, 23 pages. |
International Search Report for PCT Application No. PCT/GB2011/001531 dated May 15, 2013, 4 pages. |
United Arab Emirates Patent Application No. 447/2013, Second Examination Report dated May 9, 2017 (5 pages). |
United Kingdom Patent Application No. GB1306962.0 Examination Report dated Jul. 31, 2017 (4 pages). |
Second Chinese Office Action and Translation dated Feb. 16, 2015 for Chinese Application No. 201180061290.5, 12 pages. |
Number | Date | Country | |
---|---|---|---|
20150075877 A1 | Mar 2015 | US |
Number | Date | Country | |
---|---|---|---|
61406273 | Oct 2010 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 13279553 | Oct 2011 | US |
Child | 14553849 | US |