This disclosure relates to composite pavement structures, and systems and methods for making composite pavement structures comprising silylated glass aggregate and polymeric binder compositions.
Waste or recycled glass is commonly provided for secondary uses through widespread recycling programs. One such secondary use of this type of glass is as a constituent component in pavement structures, for example parking surfaces. However, the amount of recycled glass typically must be limited in many pavement structures in order to satisfy minimum performance criteria such as crush strength and flexural strength. If a pavement structure fails to meet such criteria, the pavement structure can fail and show signs of cracking and spalling. Improvements in pavement structures that can maximize the incorporation of recycled glass while meeting acceptable performance criteria are desired.
One aspect of this disclosure relates to a process for making a composite pavement structure wherein glass aggregate particles ranging from about 0.1 to about 0.5 inch in diameter are provided. The glass aggregate particles are exposed to a coupling agent, for example an aqueous aminosilane solution, in an amount of about 1 to about 10 parts by weight of solution based on 100 parts by weight of the glass aggregate particles wherein the aqueous aminosilane solution contains about 0.01 to about 5.0 parts by weight aminosilane based on 100 parts by weight of solution. After exposure, the aminosilane is allowed to react and bond with the glass aggregate particles for a predetermined time period to provide primed or silylated glass particles. The primed or silylated glass particles are then dried and subsequently made available for mixing with a polymeric binder composition. Once the silylated glass and polymeric binder composition are mixed, they are allowed react and bond to provide a composite pavement structure.
In accordance with the above described process, a pavement structure produced by applying about 0.002 to about 10 pounds of aminosilane dispersed in about 19 to about 190 pounds of water per 2,000 pounds of glass aggregate particles can be produced having a crush strength exceeding 1,500 psi and a flexural strength exceeding 700 psi. This is possible because the glass aggregate particles have exposed surfaces that are reacted with and bonded to aminosilane. In turn, the polymeric binder composition is reacted with and bonded to at least some of the aminosilane. This type of bonding is stronger than bonding where a polymeric binder composition is bonded directly to unsilylated glass where the crush strength is typically only about 1,000 psi and the flexural strength is less than 500 psi. Thus, a 50% increase in crush strength and flexural is realized by silylating the glass aggregate particles before mixing them with a polymeric binder composition. Additionally, the disclosed pavement structure can be made water pervious or water impervious by adjusting the quantity of polymeric binder composition along with the addition of more fine particles, such as glass sand particles produced by a glass crusher.
A system is also disclosed for providing primed glass aggregate particles, such as silylated glass aggregate particles. The system includes a conveying system constructed and arranged to support and transport glass aggregate particles at a first transport rate and an application system constructed and arranged to expose a coupling agent, for example an aqueous aminosilane solution, to the glass aggregate particles present on the conveying system. A dryer, spaced from the application system and configured to direct at least one of forced air and heat onto the glass aggregate present on the conveying system, also provided. With the disclosed system the first transport rate can be set such that the glass aggregate present on the conveying system is first exposed to the dryer after a predetermined time period following the application of aqueous aminosilane solution to the glass aggregate particles.
This disclosure relates to a process for making a composite pavement structure comprising primed glass aggregate particles and a polymeric binder composition. One example of such a process is shown in
In one step of the process, glass is provided and subsequently modified into glass aggregate particles. The glass may be of any type and may be clear, tinted, and/or colored. Preferably, the glass is post-consumer waste recycled glass such that overall costs and environmental costs are minimized. The waste glass can be modified in a variety of ways, such as in the manner described in U.S. Patent Application Publications 2009/0067924 and 2009/0067925 to Kaul, both of which are hereby incorporated by reference. The glass aggregate particles are formed from glass that has been crushed, tumbled and heated to round its edges and remove non-glass impurities. A suitable recycled glass is described in U.S. Pat. No. 7,041,221 to Arnott, which is hereby incorporated by reference. Waste glass is prepared by crushing the glass to desired dimensions, e.g., 1/16 inch to about 1 inch, preferably about ¼ inch to about ½ inch, more preferably about ⅜ inch. It is believed that reducing the average diameter of the glass reduces spalling of the aggregate from the composite pavement structure, once installed. The glass may be crushed using an impact crusher, hammer mill, cone crusher or a roller crusher. Preferably, the recyclable glass is crushed using roller crusher as better oil adsorption can be achieved.
Any order of pre-crushing, pre-screening, crushing, cleaning and drying may be used. In a preferred embodiment however, the crushed glass is first pre-crushed and pre-screened. If the glass is clean, no pre-crushing or pre-screening is required. The pre-crushed glass is pre screened through a mesh, which may include an inch mesh, a combination of double or triple deck screens or at least two meshes. Once pre-screened through the mesh, preferably the glass is further crushed using a roller crusher and subsequently, the crushed glass is dried, after cleaning, preferably at a temperature of at least 100° F. or, more preferably, at a temperature of at least 350° F. Subsequently, the crushed glass is screened, preferably through at least a 40 mesh screen, or more preferably through a 30 mesh screen, or most preferably through a 20 mesh screen. It is noted that the above described crushing process can result in about 50 percent by weight glass aggregate particles and about 50 percent by weight glass sand particles. Suitable grades of glass are commercially available from Glass Plus Inc. of Tomahawk, Wis.
Once the waste or recycled glass has been modified to form glass aggregate particles, the particles are then exposed to a coupling agent wherein the coupling agent reacts with and bonds to the glass to form primed glass aggregate particles. As used in this application, the phrase “primed glass aggregate particles” is meant to describe glass aggregate particles whose exterior surfaces have been at least partially coated by a substance that has chemically reacted with and bonded to the exterior surfaces. As used in this application, the phrase “coupling agent” is meant to include any substance that chemically reacts and bonds with glass and a polymeric binder composition to form a stronger bond between the glass and polymeric binder composition, as compared to a direct bond between glass and the polymeric binder composition. Exemplary coupling agents include silanes with functional groups of hydroxyl, thiol, epoxy, and/or primary and secondary amines. A particularly useful example of a coupling agent is aminosilane which will cause glass aggregate particles to become primed, or more specifically, silylated or silanized. It is noted that any silane or silanol functional group will operate to prime or silylate the glass aggregate particles. However, aminosilane is preferred because aminosilane is readily soluble in water meaning that an organic solvent is not required. As such, the use of amino silane in an aqueous solution lowers the overall expense of the described process. Aminosilane concentrate is available commercially from Momentive Performance Materials of Albany, N.Y., examples of which are sold as SILQUEST® A-1100 and SILQUEST® A-1120. In order to maximize silylation of the glass aggregate particles, the aminosilane is further diluted with water to form an aqueous aminosilane solution. Preferably, the solution contains about 0.01 to about 5.0 parts by weight aminosilane, and more preferably contains about 0.3 parts by weight aminosilane, each based on 100 parts by weight solution. It has been discovered that using about 0.3 by weight SILQUEST® A-1120 results in optimally silylated glass aggregate particles that have a higher bonding strength with a polymeric binder composition. It is believed that this greater strength arises from a mono-layer being formed between the reacted aminosilane and the glass aggregate particles, rather than the formation of multiple layers. As such, a higher performing composite pavement structure will result with optimally silylated glass aggregate particles. Where the concentration of aminosilane is too low, less of the exposed surfaces of the glass aggregate particles will become primed or silylated and the composite pavement structure will not be as strong as a larger fraction of the exposed surfaces of the glass aggregate particles will become directly bonded to the polymeric binder composition. Conversely, where the concentration of aminosilane is excessive, it is more likely that more of the exposed surfaces of the primed or silylated glass aggregate particles will form multiple layers and also become bonded to each other rather than to the polymeric binder composition, and thus form a reduced strength composite pavement structure.
Where aqueous aminosilane solution is used as the coupling agent to prime the glass aggregate particles, the solution may be applied at a ratio of about 1 to about 10 parts by weight solution based on 100 parts by weight of glass aggregate particles. Most preferably, the aqueous aminosilane solution is applied in a ratio of about 5 parts by weight aqueous aminosilane solution to 100 parts by weight glass aggregate. At this ratio, optimal silylation of the glass aggregate particles can occur while waste of the solution is minimized.
There are many ways in which the glass aggregate particles may be exposed to the coupling agent. For example, a batch process may be used wherein the aggregate and the coupling agent, in an aqueous solution, are tumbled together for a predetermined period of time, such as for five minutes. Alternatively, and as described in more detail later with respect to
Once the aqueous aminosilane solution comes into contact with the glass aggregate particles, the aminosilane will begin to react and bond with the glass aggregate particles. In order to optimize the silylation of the glass, the aminosilane solution should remain in contact with the glass aggregate particles for a predetermined time period. Preferably, the predetermined time period is about 15 seconds to two minutes such that a sufficient reaction has occurred before proceeding with drying the now silylated glass aggregate particles.
Once the glass aggregate particles are sufficiently silylated, the silylated glass aggregate particles may be dried. Drying may be performed in a variety of ways. For example, the silylated glass aggregate particles can be separated from the solution, for example by draining, and allowed to air dry in ambient conditions. Where accelerated drying is desired, a blower can be used to direct forced air over the silylated glass aggregate particles. Where even further accelerated drying is desired, a heater may be used to direct forced air and/or heat over the silylated glass aggregate particles. When dried without heat, the silylation process will continue to occur for a time period up to about 24 hours. As such, it is preferred to store the silylated glass particles for a sufficient period of time to allow full silylation to occur before using the glass aggregate particles in a composite pavement structure. When heat is used, generally about 120° F. to 200° F., the reaction time is significantly shortened to allow for immediate use of the silylated glass aggregate particles in a composite pavement structure. During and after this time period, the silylated glass aggregate particles may be stored or transported to an end use location, such as a construction site. The particles may be stored in a variety of discrete containers, such as superstacks and drums. Alternatively, the particles may be held in larger bulk quantities, as is the case with railcars and tankers.
Once the silylated glass aggregate particles have been transported to an end use site, the aggregate may be mixed with a polymeric resin binder to form a composite pavement structure. A full discussion of polymeric resin binders, and their use in mixing with aggregates to form a composite pavement structure, is provided in Patent Cooperation Treaty Application PCT/PCT/EP2010/058989, filed on Jun. 24, 2010, the entirety of which is incorporated by reference herein. A further discussion of such binders and their use is provided in U.S. Patent Application Publications 2009/0067924 and 2009/0067295 to Kaul. Other suitable binder compositions, for purposes of the present invention, are disclosed as “elastomeric compositions” in U.S. Provisional patent Application Ser. No. 61/288,637, the disclosure of which is incorporated by reference herein.
One example of a polymeric binder composition is the reaction product of a two-part composition comprising a first component and a second component. As such, it is to be appreciated that the term two-component refers to these components. Other additional components may be used. The binder composition may be referred to in the art as a 2K system. The first and second components are mixed to form the reaction product of the binder composition. The term reaction product as used herein is intended to encompass all stages of interaction and/or reaction between the first and second components, including reaction products of the first and second components, even when the reaction product contacts the aggregate to form the composite material. Generally, the reaction product begins to form when the first and second components come into contact with each other. In one embodiment, the reaction product is a polyurethane wherein the first component is an isocyanate component and the second component is an isocyanate-reactive component.
Once the polymeric binder composition is mixed with the silylated glass aggregate particles, the polymeric binder composition will react and bond with the silylated glass to form a composite pavement structure. While the composition is still workable, the composite pavement structure may be applied to a compacted surface and subsequently screeded and troweled. Once the polymeric binder composition has fully cured, the composite pavement structure will be ready for use.
Two examples of a composite pavement structure were prepared and tested wherein each example was comprised of an isocyanate based polymeric binder composition and an aggregate, 100% of which was glass aggregate having an average size of about ¼ inch in combination. In the first example, unprimed/unsilylated glass aggregate particles were used while in the second example, primed/silylated glass aggregate particles were used. Table 1 below shows the constituents and properties of the polymeric binder composition used in both the first and second examples.
To prepare the primed glass aggregate particles for the second example, the glass was silylated by tumbling the glass particles with an aqueous solution comprising 0.3 wt. % SILQUEST® A-1120, commercially available from Momentive Performance Products. To prime or silylate the glass, 5 parts of the aqueous solution was tumbled with 100 parts of the glass for about 5 minutes. The aqueous solution was then drained off and the glass was allowed to dry. To form the composite pavement material of the two examples, 4.2 wt. % of the polymeric binder composition was mixed with 95.8 wt. % aggregate. The first and second examples of the composite pavement material were allowed to fully cure and were sub subsequently tested. The test results are presented in Table 2 below.
As can be readily appreciated by viewing the above data, the use of primed or silylated glass instead of raw glass in a composite pavement structure significantly enhances crush strength and flexural strength without compromising porosity and permeability in a pervious pavement application. For example, the test data shows that the crush strength of the composite pavement material increased by about 50% when silylated glass aggregate particles were used instead of untreated glass aggregate particles. In field prepared applications of the composite pavement structure, each of the above values are readily obtainable while a minimum crush strength of at least about 1,300 psi can be repeatedly achieved, even with some variances in the constituent components of the composite. At least two implications arising from the use of the disclosed porous composite pavement structure using primed glass are: 1) the thickness of the composite pavement structure may be reduced; and 2) the composite pavement structure can be used in applications not currently suitable for prior art glass aggregate based pavement structures.
With reference to
Another aspect of system 100 is conveying system 120. Conveying system 120 is for supporting and transporting the glass aggregate particles 101 from the glass aggregate source 110 to the aggregate collection station 150. Conveying system 120 is also for supporting the glass aggregate particles 101 while they become primed or silylated and subsequently dried. Many types of conveying systems are suitable for this purpose. In the exemplary embodiment shown in
Yet another aspect of system 100 is application system 130. Application system 130 is for exposing the glass aggregate particles present on the conveying system 120 to the coupling agent in solution, for example an aqueous aminosilane solution. Many types of systems are suitable for this purpose. In the example shown in
Another aspect of system 100 is dryer 140. Dryer 140 is for drying water away from the primed or silylated glass aggregate and, where heat is used, accelerating the reaction process between the glass aggregate particles and the coupling agent. Many types of dryers are suitable for this purpose. In the exemplary embodiment shown in
With reference to
One aspect of system 200 is that conveying system 120 includes two conveyors instead of the single conveyor shown in
With reference to
The above are example principles. Many embodiments can be made.
This application is a continuation of U.S. patent application Ser. No. 13/517,935, filed on Aug. 28, 2012, which is the National Stage of International Patent Application No. PCT/US2010/058582, filed on Dec. 1, 2010, which claims priority to and all the advantages of U.S. Provisional Patent Application No. 61/288,637, filed on Dec. 21, 2009, the contents of which are incorporated herein by reference.
Number | Name | Date | Kind |
---|---|---|---|
3240736 | Beckwith | Mar 1966 | A |
3272098 | Buchholtz et al. | Sep 1966 | A |
3396644 | Banks | Aug 1968 | A |
3577893 | Towner | May 1971 | A |
3690021 | Glass et al. | Sep 1972 | A |
3690227 | Welty | Sep 1972 | A |
3711444 | Allen et al. | Jan 1973 | A |
3850537 | Bynum, Jr. | Nov 1974 | A |
3909474 | Borchert et al. | Sep 1975 | A |
3911667 | Komiyama | Oct 1975 | A |
3958891 | Eigenmann | May 1976 | A |
4021401 | Jeppsen | May 1977 | A |
4063839 | Brown | Dec 1977 | A |
4076917 | Swift et al. | Feb 1978 | A |
4088633 | Gurney | May 1978 | A |
4097423 | Dieterich | Jun 1978 | A |
4112176 | Bailey | Sep 1978 | A |
4114382 | Kubens et al. | Sep 1978 | A |
4139676 | Janssen et al. | Feb 1979 | A |
4157907 | Kroyer | Jun 1979 | A |
4247933 | Nakamura | Jan 1981 | A |
4433701 | Cox et al. | Feb 1984 | A |
4441821 | Burkhart et al. | Apr 1984 | A |
4452551 | Amdt et al. | Jun 1984 | A |
4550153 | Carver | Oct 1985 | A |
4559239 | Cenegy | Dec 1985 | A |
4630963 | Wyman | Dec 1986 | A |
4659748 | Boddie | Apr 1987 | A |
4721493 | Lane | Jan 1988 | A |
4761099 | Mann et al. | Aug 1988 | A |
4792262 | Kapps et al. | Dec 1988 | A |
4797026 | Webster | Jan 1989 | A |
4915539 | Yoshikane et al. | Apr 1990 | A |
4922463 | Del Zotto et al. | May 1990 | A |
5001190 | Carpenter et al. | Mar 1991 | A |
5043955 | Dubois et al. | Aug 1991 | A |
5044819 | Kilheffer et al. | Sep 1991 | A |
5106227 | Ahmad et al. | Apr 1992 | A |
5123778 | Bohnhoff | Jun 1992 | A |
5149192 | Hamm et al. | Sep 1992 | A |
5182137 | Allen | Jan 1993 | A |
5225210 | Shimoda | Jul 1993 | A |
5250340 | Bohnhoff | Oct 1993 | A |
5298539 | Singh et al. | Mar 1994 | A |
5364672 | Schultze-Kraft | Nov 1994 | A |
5432213 | Kim et al. | Jul 1995 | A |
5447388 | Rouse | Sep 1995 | A |
5480256 | Itsekson et al. | Jan 1996 | A |
5494741 | Fekete et al. | Feb 1996 | A |
5590976 | Kilheffer et al. | Jan 1997 | A |
5648421 | Thiele et al. | Jul 1997 | A |
5693413 | Hesterman et al. | Dec 1997 | A |
5788407 | Hwang | Aug 1998 | A |
5836715 | Hendrix et al. | Nov 1998 | A |
5848856 | Bohnhoff | Dec 1998 | A |
5891938 | Williams | Apr 1999 | A |
5936015 | Bums | Aug 1999 | A |
5956294 | Takizawa et al. | Sep 1999 | A |
6007233 | Cairns | Dec 1999 | A |
6206607 | Medico, Jr. et al. | Mar 2001 | B1 |
6225371 | Prerre | May 2001 | B1 |
6235367 | Holmes et al. | May 2001 | B1 |
6370087 | Akahane et al. | Apr 2002 | B1 |
6372135 | Kohlstadt et al. | Apr 2002 | B1 |
6495652 | Reichelt et al. | Dec 2002 | B1 |
6702514 | Kaneko et al. | Mar 2004 | B2 |
6826122 | Zaugg | Nov 2004 | B2 |
6887922 | Roddis | May 2005 | B1 |
6962463 | Chen | Nov 2005 | B2 |
7041221 | Amott | May 2006 | B2 |
7168884 | Hart | Jan 2007 | B2 |
7172145 | Knepp | Feb 2007 | B2 |
7342056 | Patel et al. | Mar 2008 | B2 |
7496003 | Muller | Feb 2009 | B2 |
7782717 | Gil et al. | Aug 2010 | B2 |
7879921 | Cummins | Feb 2011 | B2 |
8025456 | Kaul | Sep 2011 | B2 |
8710135 | Bower et al. | Apr 2014 | B2 |
9464003 | Hicks et al. | Oct 2016 | B2 |
9505931 | Hicks et al. | Nov 2016 | B2 |
20020016421 | Goeb et al. | Feb 2002 | A1 |
20020022086 | Hughes et al. | Feb 2002 | A1 |
20030090016 | Petrovic et al. | May 2003 | A1 |
20040074421 | Anderson | Apr 2004 | A1 |
20040091712 | Marohn | May 2004 | A1 |
20040109730 | Moss et al. | Jun 2004 | A1 |
20060293428 | Singh et al. | Dec 2006 | A1 |
20070091727 | Bonvin et al. | Apr 2007 | A1 |
20070093602 | Thompson-Colon et al. | Apr 2007 | A1 |
20070172590 | Hoffmann et al. | Jul 2007 | A1 |
20070189109 | Long | Aug 2007 | A1 |
20070213456 | Singh et al. | Sep 2007 | A1 |
20080058461 | Cummins | Mar 2008 | A1 |
20080118637 | Serwin | May 2008 | A1 |
20080144444 | Mahler et al. | Jun 2008 | A1 |
20080151698 | Gil et al. | Jun 2008 | A1 |
20080253235 | Hiraga et al. | Oct 2008 | A1 |
20090062432 | Doesburg et al. | Mar 2009 | A1 |
20090067924 | Kaul | Mar 2009 | A1 |
20090067925 | Kaul | Mar 2009 | A1 |
20100212552 | Stratton et al. | Aug 2010 | A1 |
20120329943 | Hicks et al. | Dec 2012 | A1 |
20140106124 | Hicks et al. | Apr 2014 | A1 |
Number | Date | Country |
---|---|---|
2 037 214 | Sep 1991 | CA |
1609340 | Apr 2005 | CN |
1968982 | May 2007 | CN |
1994955 | Jul 2007 | CN |
101357828 | Feb 2009 | CN |
651 167 | Oct 1937 | DE |
2713984 | Oct 1978 | DE |
200 00 015 | May 2000 | DE |
102 31 858 | Jan 2004 | DE |
0 445 578 | Sep 1991 | EP |
0 583 086 | Feb 1994 | EP |
0 911 304 | Apr 1999 | EP |
1 176 257 | Jan 2002 | EP |
1 462 571 | Sep 2004 | EP |
2 188 596 | Jan 1974 | FR |
2 653 360 | Apr 1991 | FR |
2 791 692 | Oct 2000 | FR |
1 604 405 | Dec 1981 | GB |
1604405 | Dec 1981 | GB |
S 63-319223 | Dec 1988 | JP |
H 04-001309 | Jan 1992 | JP |
H 10-102444 | Apr 1998 | JP |
H 11-80304 | Mar 1999 | JP |
2002-021011 | Jan 2002 | JP |
2003-267953 | Sep 2003 | JP |
2004-076527 | Mar 2004 | JP |
2007-132020 | May 2007 | JP |
2007-285045 | Nov 2007 | JP |
2007-289869 | Nov 2007 | JP |
2008-502773 | Jan 2008 | JP |
2009-293326 | Dec 2009 | JP |
96-0011358 | Aug 1996 | KR |
10-2007-0020328 | Feb 2007 | KR |
10-1395451 | May 2014 | KR |
10-1669716 | Oct 2016 | KR |
WO 9500569 | Jan 1995 | WO |
WO 9829356 | Jul 1998 | WO |
WO 02076900 | Oct 2002 | WO |
WO 03062532 | Jul 2003 | WO |
WO 2004014815 | Feb 2004 | WO |
WO 2009033037 | Mar 2009 | WO |
WO 2010149737 | Dec 2010 | WO |
WO 2011084274 | Jul 2011 | WO |
WO 2011084793 | Jul 2011 | WO |
WO 2011084802 | Jul 2011 | WO |
WO 2011084807 | Jul 2011 | WO |
WO 2012091707 | Jul 2012 | WO |
2008110222 | Sep 2018 | WO |
Entry |
---|
Anna Wypych, Databook of Adhesion Promoters, ChemTec Publishing—Toronto, 2018, p. 329. (Year: 2018). |
International Search Report for Application No. PCT/US2010/061587 dated Mar. 1, 2011, 2 pages. |
International Search Report for Application No. PCT/US2010/061558 dated Mar. 3, 2011, 3 pages. |
International Search Report for Application No. PCT/US2010/061574 dated Mar. 4, 2011, 2 pages. |
International Search Report for Application No. PCT/US2010/058582 dated Apr. 27, 2011, 4 pages. |
International Search Report for Application No. PCT/EP2010/08989 dated Aug. 19, 2011, 4 pages. |
Crouch, L.K. et al. “Measuring the Effective Air Void Content of Portland Cement Pervious Pavements,” ASTM Journal of Cement, Concrete, and Aggregates, 25(1), 2003, 5 pages. |
Montes, Felipe et al., “A New Test Method for Porosity Measurements of Portland Cement Pervious Concrete,” J. ASTM Int. 2(1), 2005, 13 pages. |
Montes, Felipe et al., “Measuring Hydraulic Conductivity in Pervious Concrete,” Env. Eng. Sci. 23(6), 2006, 10 pages. |
Schaefer, V. et al., “Mix Design Development for Pervious Concrete in Cold Weather Climates,” Final Report, Civil Engineering, Iowa State University, 2006, 85 pages. |
Yamaguchi, H. et al. “Manufacture of Colored Artificial Stones with High Strength”, Database Chemical Abstracts, Chemi [Online], Oct. 7, 1991, 2 pages. |
English language abstract for CN 1609340 extracted from espacenet.com database dated Dec. 29, 2014, 2 pages. |
English language abstract for CN 1968982 extracted from espacenet.com database dated Dec. 2, 2015, 1 page. |
English language abstract and machine-assisted English translation for CN 1994955 extracted from espacenet.com database dated Jan. 22, 2015, 20 pages. |
English language abstract and machine-assisted English translation for CN 101357828 extracted from espacenet.com database dated Nov. 9, 2016, 15 pages. |
Machine-assisted English translation for DE 651 167 extracted from the espacenet.com database dated Jun. 4, 2012, 9 pages. |
Machine-assisted English translation for DE 200 00 015 extracted from the espacenet.com database dated Jun. 4, 2012, 24 pages. |
Machine-assisted English language abstract and machine-assisted English translation for DE 102 31 858 extracted from the espacenet.com database dated Mar. 18, 2014, 12 pages. |
English language abstract for EP 0 445 578 extracted from the espacenet.com database dated Jun. 4, 2012, 1 page. |
English language abstract for EP 0 911 304 extracted from the espacenet.com database dated Aug. 23, 2012, 1 pages. |
English language abstract and machine-assisted translation for EP 1 176 257 extracted from the espacenet.com database dated Jun. 4, 2012, 14 pages. |
English language abstract and machine-assisted translation for EP 1 462 571 extracted from the espacenet.com database dated Jun. 4, 2012, 9 pages. |
Machine-Assisted English translation for FR 2 188 596 extracted from the espacenet.com database dated Aug. 23, 2012, 11 pages. |
English language abstract and machine-assisted translation for FR 2 653 360 extracted from the espacenet.com database dated Jun. 4, 2012, 17 pages. |
English language abstract and machine-assisted translation for FR 2 791 692 extracted from the espacenet.com database dated Jun. 4, 2012, 9 pages. |
English language abstract and machine-assisted translation for JPS 63-319223 extracted from the espacenet.com database dated Aug. 24, 2016, 6 pages. |
English language abstract and machine-assisted English translation for JPH 04-001309 extracted from the PAJ database dated Apr. 21, 2016, 6 pages. |
English language abstract and machine-assisted English translation for JPH 10-102444 extracted from espacenet.com database dated Apr. 21, 2016, 17 pages. |
English language abstract and machine-assisted English translation for JPH 11-80304 extracted from espacenet.com database dated Apr. 21, 2016, 13 pages. |
English language abstract and machine-assisted English translation for JP 2002-021011 extracted from the PAJ database dated Apr. 21, 2016, 17 pages. |
English language abstract and machine-assisted English translation for JP 2003-267953 extracted from the PAJ database dated Jan. 19, 2015, 27 pages. |
English language abstract and machine-assisted translation for JP 2004-076527 extracted from the PAJ database dated Jun. 4, 2012, 30 pages. |
English language abstract and machine-assisted English translation for JP 2007-132020 extracted from the PAJ database dated Jan. 19, 2015, 21 pages. |
English language abstract and machine-assisted English translation for JP 2007-285045 extracted from the PAJ database dated Jan. 19, 2015, 13 pages. |
English language abstract and machine-assisted English translation for JP 2007-289869 extracted from the PAJ database dated Aug. 24, 2016, 13 pages. |
English language abstract for JP 2008-502773 extracted from the PAJ database dated Jan. 19, 2015, 1 page. |
English language abstract and machine-assisted English translation for JP 2009-293326 extracted from espacenet.com database dated Aug. 27, 2015, 44 pages. |
English language abstract for KR 96-0011358 extracted from espacenet.com database dated Aug. 24, 2016 and machine-assisted English translation for KR 96-0011358 extracted from KIPO.com database dated Aug. 24, 2016, 7 pages. |
English language abstract and machine-assisted English translation for KR 10-2007-0020328 extracted from espacenet.com database dated Jan. 2, 2017, 33 pages. |
English language abstract not found for KR 10-11395451; however, see English language equivalent U.S. Pat. No. 8,710,135. Original document extracted from espacenet.com database dated Dec. 3, 2016, 13 pages. |
English language abstract not found for KR 10-1669716; however, see English language equivalent U.S. Pat. No. 9,505,931. Original document extracted from espacenet.com database dated Dec. 1, 2016, 13 pages. |
English language abstract and machine-assisted translation for WO 95/00569 extracted from the espacenet.com database dated Jun. 4, 2012, 37 pages. |
English language abstract and machine-assisted translation for WO 98/29356 extracted from the espacenet.com database dated Jun. 4, 2012, 28 pages. |
English language abstract for WO 02/076900 extracted from the espacenet.com database dated Aug. 23, 2012, 16 pages. |
English language abstract and machine-assisted English translation for WO 2004/014815 extracted from espacenet.com database dated Apr. 21, 2016, 20 pages. |
U.S. Appl. No. 61/288,637, filed Dec. 21, 2009. |
U.S. Appl. No. 15/255,688, filed Sep. 2, 2016. |
Number | Date | Country | |
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20170152180 A1 | Jun 2017 | US |
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61288637 | Dec 2009 | US |
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Parent | 13517935 | US | |
Child | 15344673 | US |