The efficiency of a refrigerator may, at least in part, rely on the refrigerator's ability to keep items within the refrigerator cool and prevent heat from entering the refrigerator. Accordingly, new methods and materials of insulating a refrigerator are sought.
According to one aspect of the present disclosure, a method for manufacturing a vacuum insulated structure includes positioning an inner liner within an external wrapper and defining a gap between the inner liner and the external wrapper, drawing a vacuum to seal the gap, and injecting a first insulator into the gap. The method further includes positioning a filter proximate to the first insulator within the gap and injecting a second insulator into the gap proximate to the filter.
According to another aspect of the present disclosure, a method for manufacturing a cabinet for a refrigerator includes positioning a liner within a wrapper to define a gap and dispensing a first insulator within the gap through a back aperture of the wrapper. The method further includes positioning a filter on the first insulator and dispensing a second insulator within the gap through the back aperture and proximate to the filter.
These and other features, advantages, and objects of the present disclosure will be further understood and appreciated by those skilled in the art by reference to the following specification, claims, and appended drawings.
The foregoing summary, as well as the following detailed description of the disclosure, will be better understood when read in conjunction with the appended drawings. For the purpose of illustrating the disclosure, there are shown in the drawings, certain embodiment(s). It should be understood, however, that the disclosure is not limited to the precise arrangements and instrumentalities shown. Drawings are not necessarily to scale. Certain features of the disclosure may be exaggerated in scale or shown in schematic form in the interest of clarity and conciseness.
As required, detailed embodiments of the present disclosure are disclosed herein. However, it is to be understood that the disclosed embodiments are merely exemplary of the disclosure that may be embodied in various and alternative forms. The figures are not necessarily to a detailed design and some schematics may be exaggerated or minimized to show function overview. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for teaching one skilled in the art to variously employ the present disclosure.
As used herein, the term “and/or,” when used in a list of two or more items, means that any one of the listed items can be employed by itself, or any combination of two or more of the listed items can be employed. For example, if a composition is described as containing components A, B, and/or C, the composition can contain A alone; B alone; C alone; A and B in combination; A and C in combination; B and C in combination; or A, B, and C in combination.
It is to be understood that the present disclosure is not limited to the particular embodiments described below, as variations of the particular embodiments may be made and still fall within the scope of the appended claims. It is also to be understood that the terminology employed is for the purpose of describing particular embodiments, and is not intended to be limiting. Instead, the scope of the present disclosure will be established by the appended claims.
For purposes of description herein, the terms “upper,” “lower,” “right,” “left,” “rear,” “front,” “vertical,” “horizontal,” and derivatives thereof shall relate to the disclosure as oriented in
Referring to
Referring now to
The inner liner 18 is shaped and configured to mate, couple or otherwise be positioned within the external wrapper 22. The external wrapper 22 includes a plurality of wrapper walls 58 to which a wrapper flange 62 is coupled. The wrapper flange 62 and the liner flange 46 are configured to be coupled when the cabinet 14 is in an assembled configuration. The coupling of the liner flange 46 and the wrapper flange 62 may be performed such that an airtight, or hermetic, seal is formed between the inner liner 18 and the external wrapper 22. The hermetic seal of the wrapper flange 62 and the liner flange 46 may be achieved through use of adhesives, welding, an elastomeric gasket under compression and/or crimping. The coupling of the liner flange 46 to the wrapper flange 62 may be performed proximate a front flange area 64 (
The external wrapper 22 may be formed of and by any of the materials and processes listed above in connection with the inner liner 18. The wrapper walls 58 of the external wrapper 22 may have a thickness ranging from between about 0.1 mm to about 3.0 mm. In a specific embodiment, the wrapper walls 58 have a thickness of about 0.5 mm. The wrapper walls 58 of the external wrapper 22 may define an injection port 66 and/or a vacuum port 70. The external wrapper 22 may include one or multiple injection ports 66 and/or vacuum ports 70. The injection ports 66 and/or vacuum ports 70 may be positioned as illustrated or in a variety of positions about the external wrapper 22. It will be understood that in alternative embodiments, the injection ports 66 and/or vacuum ports 70 may be disposed on both the external wrapper 22 and inner liner 18, or solely on the inner liner 18. The injection port 66 and the vacuum port 70 may be used to access (e.g., to inject an insulator, draw a vacuum and/or perform maintenance within) the gap 26 once the inner liner 18 and the external wrapper 22 are bonded. The injection port 66 and the vacuum port 70 may have a diameter of between about 10 mm and about 50 mm, or between about 12.5 mm and about 25 mm. In various embodiments, the injection port 66 and the vacuum port 70 may have different diameters than one another. Similarly, in embodiments utilizing more than one injection port 66 and vacuum port 70, the sizes of the injection ports 66 and the vacuum ports 70 may vary.
Referring now to
Referring now to
In embodiments where the first and/or second insulators 30, 34 include organic spheres, the organic spheres may include polystyrene, polythiophenes, polyethylene, rubber and/or combinations thereof. In embodiments where the first and/or second insulators 30, 34 include inorganic spheres, the spheres may include glasses, ceramics and combinations thereof. In embodiments where the first and/or second insulators 30, 34 include beads or spheres, the beads or spheres may have an average outer diameter ranging from about 50 nm to about 300 μm, or from about 1 μm to about 300 μm, or from about 50 nm to about 1000 nm. In various embodiments, the diameter size distribution of the spheres is low. Sphere embodiments of the first and/or second insulators 30, 34 may be filled with a single gas (e.g., H2, O2, N2, noble gases, volatile organic compounds, CO2, SO, SO2) or a mixture of gases (e.g., atmosphere, noble gases, O2, SO2, SO). The spheres may be sealed and have a gas pressure within the spheres of between about 0.1 atm and about 1.0 atm, or between about 0.2 atm and about 0.5 atm, or between about 0.25 atm and about 0.35 atm. The first and/or second insulators 30, 34 are positioned within the gap 26 and in contact with both the wrapper walls 58 and the liner walls 50. The packing factor of the first and/or second insulators 30, 34 within the gap 26 may be greater than about 60%, greater than about 62%, greater than about 65%, or greater than about 70%.
In embodiments where the first and/or second insulators 30, 34 include fumed silica, the fumed silica may be hydrophobic and/or hydrophilic. The fumed silica may have a particle size ranging from less than about 0.005μ to greater than about 1.0μ. The fumed silica may have a density of between about 32 kg/m3 to about 80 kg/m3. When positioned within the gap 26, the fumed silica may have a density between about 50 kg/m3 to about 300 kg/m3, or between about 80 kg/m3 to about 250 kg/m3 or between about 150 kg/m3 to about 200 kg/m3.
The first and second insulators 30, 34 are configured not only to thermally insulate the inner liner 18 from the external wrapper 22, but also to resist the inward directed force of the atmosphere on the lower than atmosphere pressure of the gap 26. Atmospheric pressure on the inner liner 18 and the external wrapper 22 may cause distortions which are unsightly and may lead to a rupture in either of the inner liner 18 or the external wrapper 22 thereby causing a loss of vacuum in the gap 26. Further, drawing the vacuum in the gap 26 may cause an impact or shock loading of the first and second insulators 30, 34 as the inner liner 18 and the external wrapper 22 contract around the first and second insulators 30, 34. Accordingly, the first and second insulators 30, 34 should have sufficient crush resistance to resist deformation of the inner liner 18 and the external wrapper 22 due to a pressure gradient between the atmosphere and an air pressure of the gap 26.
The first insulator 30 may be positioned within, and proximate to, the front flange area 64 of the cabinet 14 and the second insulator 34 may fill the rest of the gap 26. In the depicted embodiment, a filter 74 is positioned between the first insulator 30 and the second insulator 34. The filter 74 may be made of paper, a polymeric material, a ceramic and/or a metal. The filter 74 may be porous, solid and/or coupled to the inner liner 18 and/or the external wrapper 22. Use of the filter 74 may resist or prevent the migration and mixing of the first and second insulators 30, 34 such that the first and second insulators 30, 34 remain segregated. The front flange area 64, due to its thinner cross section and being surrounded by atmosphere on three sides, may suffer from a thermal, or heat, bridging effect. Such a thermal bridging across the front flange area 64 may result in an overall reduced efficiency of the refrigerator 10. Accordingly, in various embodiments the first insulator 30 may have a higher insulating property than the second insulator 34. In such an embodiment, the higher insulating property of the first insulator 30 may be sufficient to reduce, or eliminate any thermal bridging taking place through the front flange area 64.
Referring now to
Referring now to
Next, step 92 of injecting the first insulator 30 into the gap 26 is performed. Injection of the first insulator 30 into the gap 26 may be accomplished by feeding the first insulator 30 into a hopper 100 which in turn supplies the first insulator 30 to a transfer mechanism 104. The transfer mechanism 104 may be a powder pump, a vacuum transfer device, pneumatic pump, flexible screw conveyor, auger feeder and/or other devices capable of transferring or moving the first and second insulators 30, 34. The transfer mechanism 104 pumps or otherwise injects the first insulator 30 into the gap 26 of the cabinet 14 (
Next, step 96 of vibrating at least one of the inner liner 18 and the external wrapper 22 is performed. Vibration of the inner liner 18 and/or the external wrapper 22 may cause the first insulator 30 to increase its packing factor. During steps 84, 88, 92, 94 and/or 96 the inner liner 18 and/or external wrapper 22 may be supported by one or more supports 106 such that relative motion between the inner liner 18 and the external wrapper 22 is minimized or prevented. The supports 106 may allow the thickness of the gap 26 to remain constant through filling and vibration. It will be understood that although method 80 was described in a specific order, the steps may be performed in any order or simultaneously without departing from the spirit of this disclosure.
Referring now to
Once the front flange area 64 of the gap 26 between the inner liner 18 and the external wrapper 22 is filled with the insulator 30 and sufficiently packed with the first insulator 30, step 118 of dispensing the second insulator 34 is performed. Dispensing of the second insulator 34 may be accomplished in a substantially similar manner to that described in connection with the first insulator 30 in step 116. Next, step 120 of positioning a back plate 142 over the back aperture 132 is performed. The back plate 142 may be constructed of the same or similar material as the external wrapper 22, or a different material. Once the back plate 142 is positioned over the back aperture 132, the back plate 142 is sealed to the external wrapper 22 to form an airtight, or hermetic, seal. After step 120 is completed, step 124 of drawing a vacuum within the gap 26 is performed. The vacuum may be drawn through the vacuum port 70 (
Use of the present disclosure may offer several advantages. For example, use of the present disclosure allows for the formation of vacuum insulated cabinets 14, panels, and structures without noticeable deformation of the inner liner 18 and the external wrapper 22. By filling the gap 26, deformation of the inner liner 18 and the external wrapper 22 from the pressure differential between the atmosphere and the gap 26 is resisted by the first and second insulators 30, 34. Vacuum insulated cabinets 14, panels and structures may provide enhanced insulative properties as compared to traditional foam filled insulating structures in addition to a reduced size (e.g., thickness decrease of greater than about 55%, 60% or 70%). Additionally, use of the disclosure may allow for the construction of a less dense cabinet 14 while also providing increased rigidity due to the use of the first and second insulators 30, 34. Further strategic use of the first insulator 30 in more critical insulation areas (e.g., in the front flange area 64, in corners and/or thin locations) and the second insulator 34 in the rest of the cabinet 14 may allow for a cost savings in embodiments where the first insulator 30 is more expensive (e.g., fumed silica) than the second insulator 34 (e.g., precipitated silica). Even further, in embodiments where the first insulator 30 has a lower increase in thermal conductivity per unit pressure increase than the second insulator 34, use of the first insulator 30 proximate the front flange area 64 allows for a greater resistance to thermal bridging as the pressure within the gap 26 increases over the service life of the refrigerator 10. It will be understood that although the disclosure was described in terms of a refrigerator, the disclosure may equally be applied to coolers, ovens, dishwashers, laundry applications, water heaters, household insulation systems, ductwork, piping insulation, acoustical insulation and other thermal and acoustical insulation applications.
In this specification and the appended claims, the singular forms “a,” “an” and “the” include plural reference unless the context clearly dictates otherwise. For the purposes of describing and defining the present teachings, it is noted that the terms “substantially” and “approximately” are utilized herein to represent the inherent degree of uncertainty that may be attributed to any quantitative comparison, value, measurement, or other representation. The terms “substantially” and “approximately” are also utilized herein to represent the degree by which a quantitative representation may vary from a stated reference without resulting in a change in the basic function of the subject matter at issue.
It is to be understood that variations and modifications can be made on the aforementioned structure without departing from the concepts of the present disclosure, and further it is to be understood that such concepts are intended to be covered by the following claims unless these claims by their language expressly state otherwise.
The present application is a Divisional of U.S. patent application Ser. No. 17/037,855, entitled, “VACUUM INSULATION STRUCTURES WITH MULTIPLE INSULATORS,” filed Sep. 30, 2020, now U.S. Pat. No. 11,555,643, which is a Continuation of U.S. patent application Ser. No. 15/776,276, entitled “VACUUM INSULATION STRUCTURES WITH MULTIPLE INSULATORS,” filed May 15, 2018, now U.S. Pat. No. 10,808,987, which is a national stage entry of PCT/US2016/063966, filed on Nov. 29, 2016, which claims the benefit under 35 U.S.C. § 119(e) to U.S. Provisional Patent Application No. 62/265,055 filed Dec. 9, 2015. The entire disclosures of each are incorporated herein by reference in their entirety.
Number | Name | Date | Kind |
---|---|---|---|
1849369 | Frost | Mar 1932 | A |
1921576 | Muffly | Aug 1933 | A |
2191659 | Hintze | Feb 1940 | A |
2432042 | Richard | Dec 1947 | A |
2451884 | Stelzer | Oct 1948 | A |
2729863 | Kurtz | Jan 1956 | A |
3290893 | Haldopoulos | Dec 1966 | A |
3338451 | Kesling | Aug 1967 | A |
3353301 | Heilweil et al. | Nov 1967 | A |
3353321 | Heilweil et al. | Nov 1967 | A |
3408316 | Mueller et al. | Oct 1968 | A |
3597850 | Jenkins | Aug 1971 | A |
3607169 | Coxe | Sep 1971 | A |
3632012 | Kitson | Jan 1972 | A |
3633783 | Aue | Jan 1972 | A |
3634971 | Kesling | Jan 1972 | A |
3670521 | Dodge, III et al. | Jun 1972 | A |
3769770 | Deschamps et al. | Nov 1973 | A |
3862880 | Feldman | Jan 1975 | A |
3868829 | Mann et al. | Mar 1975 | A |
3875683 | Waters | Apr 1975 | A |
3910658 | Lindenschmidt | Oct 1975 | A |
3933398 | Haag | Jan 1976 | A |
3935787 | Fisher | Feb 1976 | A |
4005919 | Hoge et al. | Feb 1977 | A |
4170391 | Bottger | Oct 1979 | A |
4242241 | Rosen et al. | Dec 1980 | A |
4260876 | Hochheiser | Apr 1981 | A |
4303730 | Torobin | Dec 1981 | A |
4303732 | Torobin | Dec 1981 | A |
4330310 | Tate, Jr. et al. | May 1982 | A |
4396362 | Thompson et al. | Aug 1983 | A |
4529368 | Makansi | Jul 1985 | A |
4583796 | Nakajima et al. | Apr 1986 | A |
4681788 | Barito et al. | Jul 1987 | A |
4781968 | Kellerman | Nov 1988 | A |
4865875 | Kellerman | Sep 1989 | A |
4870735 | Jahr et al. | Oct 1989 | A |
4914341 | Weaver et al. | Apr 1990 | A |
5066437 | Barito et al. | Nov 1991 | A |
5084320 | Barito et al. | Jan 1992 | A |
5094899 | Rusek, Jr. | Mar 1992 | A |
5121593 | Forslund | Jun 1992 | A |
5168674 | Molthen | Dec 1992 | A |
5171346 | Hallett | Dec 1992 | A |
5227245 | Brands et al. | Jul 1993 | A |
5251455 | Cur et al. | Oct 1993 | A |
5361598 | Roseen | Nov 1994 | A |
5375428 | LeClear et al. | Dec 1994 | A |
5500287 | Henderson | Mar 1996 | A |
5500305 | Bridges et al. | Mar 1996 | A |
5505810 | Kirby et al. | Apr 1996 | A |
5509248 | Dellby et al. | Apr 1996 | A |
5532034 | Kirby et al. | Jul 1996 | A |
5533311 | Tirrell et al. | Jul 1996 | A |
5599081 | Revlett et al. | Feb 1997 | A |
5600966 | Valence et al. | Feb 1997 | A |
5768837 | Sjoholm | Jun 1998 | A |
5792801 | Tsuda et al. | Aug 1998 | A |
5826780 | Nesser et al. | Oct 1998 | A |
5834126 | Sheu | Nov 1998 | A |
5918478 | Bostic et al. | Jul 1999 | A |
5950395 | Takemasa et al. | Sep 1999 | A |
5952404 | Simpson et al. | Sep 1999 | A |
6013700 | Asano et al. | Jan 2000 | A |
6063471 | Dietrich et al. | May 2000 | A |
6163976 | Tada et al. | Dec 2000 | A |
6164739 | Schultz et al. | Dec 2000 | A |
6187256 | Aslan et al. | Feb 2001 | B1 |
6209342 | Banicevic et al. | Apr 2001 | B1 |
6210625 | Matsushita et al. | Apr 2001 | B1 |
6244458 | Frysinger et al. | Jun 2001 | B1 |
6266970 | Nam et al. | Jul 2001 | B1 |
6294595 | Tyagi et al. | Sep 2001 | B1 |
6485122 | Wolf et al. | Jan 2002 | B2 |
6428130 | Banicevic et al. | Aug 2002 | B1 |
6430780 | Kim et al. | Aug 2002 | B1 |
6629429 | Kawamura et al. | Oct 2003 | B1 |
6655766 | Hodges | Dec 2003 | B2 |
6689840 | Eustace et al. | Feb 2004 | B1 |
6736472 | Banicevic | May 2004 | B2 |
6860082 | Yamamoto et al. | Mar 2005 | B1 |
7008032 | Chekal et al. | Mar 2006 | B2 |
7197792 | Moon | Apr 2007 | B2 |
7197888 | LeClear et al. | Apr 2007 | B2 |
7207181 | Murray et al. | Apr 2007 | B2 |
7234247 | Maguire | Jun 2007 | B2 |
7263744 | Kim et al. | Sep 2007 | B2 |
7360371 | Feinauer et al. | Apr 2008 | B2 |
7475562 | Jackovin | Jan 2009 | B2 |
7517031 | Laible | Apr 2009 | B2 |
7614244 | Venkatakrishnan et al. | Nov 2009 | B2 |
7665326 | LeClear et al. | Feb 2010 | B2 |
7703217 | Tada et al. | Apr 2010 | B2 |
7703824 | Kittelson et al. | Apr 2010 | B2 |
7757511 | LeClear et al. | Jul 2010 | B2 |
7794805 | Aumaugher et al. | Sep 2010 | B2 |
7845745 | Gorz et al. | Dec 2010 | B2 |
7938148 | Carlier et al. | May 2011 | B2 |
7992257 | Kim | Aug 2011 | B2 |
8049518 | Wern et al. | Nov 2011 | B2 |
8074469 | Hamel et al. | Dec 2011 | B2 |
8079652 | Laible et al. | Dec 2011 | B2 |
8108972 | Bae et al. | Feb 2012 | B2 |
8157338 | Seo et al. | Apr 2012 | B2 |
8162415 | Hagele et al. | Apr 2012 | B2 |
8182051 | Laible et al. | May 2012 | B2 |
8197019 | Kim | Jun 2012 | B2 |
8266923 | Bauer et al. | Sep 2012 | B2 |
8382219 | Hottmann et al. | Feb 2013 | B2 |
8434317 | Besore | May 2013 | B2 |
8439460 | Laible et al. | May 2013 | B2 |
8491070 | Davis et al. | Jul 2013 | B2 |
8516845 | Wuesthoff et al. | Aug 2013 | B2 |
8590992 | Lim et al. | Nov 2013 | B2 |
8717029 | Chae et al. | May 2014 | B2 |
8752921 | Gorz et al. | Jun 2014 | B2 |
8763847 | Mortarotti | Jul 2014 | B2 |
8764133 | Park et al. | Jul 2014 | B2 |
8776390 | Hanaoka et al. | Jul 2014 | B2 |
8840204 | Bauer et al. | Sep 2014 | B2 |
8881398 | Hanley et al. | Nov 2014 | B2 |
8905503 | Sahasrabudhe et al. | Dec 2014 | B2 |
8943770 | Sanders et al. | Feb 2015 | B2 |
8944541 | Allard et al. | Feb 2015 | B2 |
9009969 | Choi et al. | Apr 2015 | B2 |
RE45501 | Maguire | May 2015 | E |
9056952 | Eilbracht et al. | Jun 2015 | B2 |
9074811 | Korkmaz | Jul 2015 | B2 |
9080808 | Choi et al. | Jul 2015 | B2 |
9102076 | Doshi et al. | Aug 2015 | B2 |
9103482 | Fujimori et al. | Aug 2015 | B2 |
9125546 | Kleemann et al. | Sep 2015 | B2 |
9140480 | Kuehl et al. | Sep 2015 | B2 |
9140481 | Cur et al. | Sep 2015 | B2 |
9170045 | Oh et al. | Oct 2015 | B2 |
9170046 | Jung et al. | Oct 2015 | B2 |
9188382 | Kim et al. | Nov 2015 | B2 |
8955352 | Lee et al. | Dec 2015 | B2 |
9221210 | Wu et al. | Dec 2015 | B2 |
9228386 | Thielmann et al. | Jan 2016 | B2 |
9267727 | Lim et al. | Feb 2016 | B2 |
9303915 | Kim et al. | Apr 2016 | B2 |
9328951 | Shin et al. | May 2016 | B2 |
9353984 | Kim et al. | May 2016 | B2 |
9410732 | Choi et al. | Aug 2016 | B2 |
9423171 | Betto et al. | Aug 2016 | B2 |
9429356 | Kim et al. | Aug 2016 | B2 |
9448004 | Kim et al. | Sep 2016 | B2 |
9463917 | Wu et al. | Oct 2016 | B2 |
9482463 | Choi et al. | Nov 2016 | B2 |
9506689 | Carbajal et al. | Nov 2016 | B2 |
9518777 | Lee et al. | Dec 2016 | B2 |
9568238 | Kim et al. | Feb 2017 | B2 |
D781641 | Incukur | Mar 2017 | S |
D781642 | Incukur | Mar 2017 | S |
9605891 | Lee et al. | Mar 2017 | B2 |
9696085 | Seo et al. | Jul 2017 | B2 |
9702621 | Cho et al. | Jul 2017 | B2 |
9759479 | Ramm et al. | Sep 2017 | B2 |
9777958 | Choi et al. | Oct 2017 | B2 |
9791204 | Kim et al. | Oct 2017 | B2 |
9833942 | Wu et al. | Dec 2017 | B2 |
20020004111 | Matsubara et al. | Jan 2002 | A1 |
20020114937 | Albert et al. | Aug 2002 | A1 |
20020144482 | Henson et al. | Oct 2002 | A1 |
20030056334 | Finkelstein | Mar 2003 | A1 |
20030157284 | Tanimoto et al. | Aug 2003 | A1 |
20030167789 | Tanimoto et al. | Sep 2003 | A1 |
20030173883 | Koons | Sep 2003 | A1 |
20040144130 | Jung | Jul 2004 | A1 |
20040226141 | Yates et al. | Nov 2004 | A1 |
20050042247 | Gomoll et al. | Feb 2005 | A1 |
20050229614 | Ansted | Oct 2005 | A1 |
20060064846 | Espendola et al. | Mar 2006 | A1 |
20060261718 | Miseki et al. | Nov 2006 | A1 |
20060266075 | Itsuki et al. | Nov 2006 | A1 |
20070266654 | Noale | Nov 2007 | A1 |
20080044488 | Zimmer et al. | Feb 2008 | A1 |
20080048540 | Kim | Feb 2008 | A1 |
20080138458 | Ozasa et al. | Jun 2008 | A1 |
20080196441 | Ferreira | Aug 2008 | A1 |
20090032541 | Rogala et al. | Feb 2009 | A1 |
20090131571 | Fraser et al. | May 2009 | A1 |
20090205357 | Lim et al. | Aug 2009 | A1 |
20090302728 | Rotter et al. | Dec 2009 | A1 |
20090322470 | Yoo et al. | Dec 2009 | A1 |
20100206464 | Heo et al. | Aug 2010 | A1 |
20100218543 | Duchame | Sep 2010 | A1 |
20100287843 | Oh | Nov 2010 | A1 |
20100287974 | Cur et al. | Nov 2010 | A1 |
20110011119 | Kuehl et al. | Jan 2011 | A1 |
20110023527 | Kwon et al. | Feb 2011 | A1 |
20110095669 | Moon et al. | Apr 2011 | A1 |
20110215694 | Fink et al. | Sep 2011 | A1 |
20110220662 | Kim et al. | Sep 2011 | A1 |
20110309732 | Horil et al. | Dec 2011 | A1 |
20120011879 | Gu | Jan 2012 | A1 |
20120060544 | Lee et al. | Mar 2012 | A1 |
20120099255 | Lee et al. | Apr 2012 | A1 |
20120240612 | Wusthoff et al. | Sep 2012 | A1 |
20120280608 | Park et al. | Nov 2012 | A1 |
20130026900 | Oh et al. | Jan 2013 | A1 |
20130043780 | Ootsuka et al. | Feb 2013 | A1 |
20130221819 | Wing | Aug 2013 | A1 |
20130270732 | Wu et al. | Oct 2013 | A1 |
20130285527 | Choi et al. | Oct 2013 | A1 |
20130293080 | Kim et al. | Nov 2013 | A1 |
20140009055 | Cho et al. | Jan 2014 | A1 |
20140097733 | Seo et al. | Apr 2014 | A1 |
20140166926 | Lee et al. | Jun 2014 | A1 |
20140190978 | Bowman et al. | Jul 2014 | A1 |
20140216706 | Melton et al. | Aug 2014 | A1 |
20140232250 | Kim et al. | Aug 2014 | A1 |
20140346942 | Kim et al. | Nov 2014 | A1 |
20150011668 | Kolb et al. | Jan 2015 | A1 |
20150015133 | Carbajal et al. | Jan 2015 | A1 |
20150017386 | Kolb et al. | Jan 2015 | A1 |
20150059399 | Hwang et al. | Mar 2015 | A1 |
20150115790 | Ogg | Apr 2015 | A1 |
20150159936 | Oh et al. | Jun 2015 | A1 |
20150176888 | Cur et al. | Jun 2015 | A1 |
20150184923 | Jeon | Jul 2015 | A1 |
20150190840 | Muto et al. | Jul 2015 | A1 |
20150224685 | Amstutz | Aug 2015 | A1 |
20150241115 | Strauss et al. | Aug 2015 | A1 |
20150241118 | Wu | Aug 2015 | A1 |
20150285551 | Aiken et al. | Oct 2015 | A1 |
20160084567 | Fernandez et al. | Mar 2016 | A1 |
20160116100 | Thiery et al. | Apr 2016 | A1 |
20160123055 | Jeyama | May 2016 | A1 |
20160161175 | Benold et al. | Jun 2016 | A1 |
20160178267 | Hao et al. | Jun 2016 | A1 |
20160178269 | Hiemeyer et al. | Jun 2016 | A1 |
20160235201 | Soot | Aug 2016 | A1 |
20160240839 | Umeyama et al. | Aug 2016 | A1 |
20160258671 | Allard et al. | Sep 2016 | A1 |
20160290702 | Sexton et al. | Oct 2016 | A1 |
20160348957 | Hitzelberger et al. | Dec 2016 | A1 |
20170038126 | Lee et al. | Feb 2017 | A1 |
20170157809 | Deka et al. | Jun 2017 | A1 |
20170176086 | Kang | Jun 2017 | A1 |
20170184339 | Liu et al. | Jun 2017 | A1 |
Number | Date | Country |
---|---|---|
626838 | May 1961 | CA |
201748744 | Feb 2011 | CN |
102717578 | Oct 2012 | CN |
202973713 | Jun 2013 | CN |
104816478 | Aug 2015 | CN |
105115221 | Dec 2015 | CN |
204963379 | Jan 2016 | CN |
9204365 | Jul 1992 | DE |
4110292 | Oct 1992 | DE |
4409091 | Sep 1995 | DE |
69401889 | Sep 1997 | DE |
19648305 | May 1998 | DE |
19914105 | Sep 2000 | DE |
10114633 | Sep 2002 | DE |
102011051178 | Dec 2012 | DE |
102014206559 | Oct 2015 | DE |
0645576 | Mar 1995 | EP |
1602425 | Dec 2005 | EP |
1624263 | Aug 2006 | EP |
2543942 | Jan 2013 | EP |
2878427 | Jun 2015 | EP |
2991698 | Dec 2013 | FR |
860138381 | Jul 1985 | JP |
04165197 | Jun 1992 | JP |
04165197 | Oct 1992 | JP |
04309778 | Nov 1992 | JP |
11159693 | Jun 1999 | JP |
H11201627 | Jul 1999 | JP |
2000320958 | Nov 2000 | JP |
2002068853 | Mar 2002 | JP |
3438948 | Aug 2003 | JP |
2005069596 | Mar 2005 | JP |
2005098637 | Apr 2005 | JP |
2006161834 | Jun 2006 | JP |
2006200685 | Aug 2006 | JP |
2008190815 | Aug 2008 | JP |
2009287791 | Dec 2009 | JP |
2013050267 | Mar 2013 | JP |
2013076471 | Apr 2013 | JP |
20050095357 | Sep 2005 | KR |
100620025 | Sep 2006 | KR |
1020070065743 | Jun 2007 | KR |
20090026045 | Mar 2009 | KR |
20150089495 | Aug 2015 | KR |
2061925 | Jun 1996 | RU |
2077411 | Apr 1997 | RU |
2081858 | Jun 1997 | RU |
2132522 | Jun 1999 | RU |
2162576 | Jan 2001 | RU |
2166158 | Apr 2001 | RU |
2187433 | Aug 2002 | RU |
2234645 | Aug 2004 | RU |
2252377 | May 2005 | RU |
2253792 | Jun 2005 | RU |
2349618 | Mar 2009 | RU |
2414288 | Mar 2011 | RU |
2422598 | Jun 2011 | RU |
142892 | Jul 2014 | RU |
2529525 | Sep 2014 | RU |
2571031 | Dec 2015 | RU |
203707 | Dec 1967 | SU |
00476407 | Jul 1975 | SU |
547614 | May 1977 | SU |
648780 | Feb 1979 | SU |
01307186 | Apr 1987 | SU |
9204301 | Mar 1992 | WO |
9614207 | May 1996 | WO |
9721767 | Jun 1997 | WO |
9920961 | Apr 1999 | WO |
9920964 | Apr 1999 | WO |
200160598 | Aug 2001 | WO |
200202987 | Jan 2002 | WO |
2002052208 | Apr 2002 | WO |
02060576 | Aug 2002 | WO |
03072684 | Sep 2003 | WO |
2004010042 | Jan 2004 | WO |
2006045694 | May 2006 | WO |
2006073540 | Jul 2006 | WO |
2007033836 | Mar 2007 | WO |
2007106067 | Sep 2007 | WO |
2008065453 | Jun 2008 | WO |
2008077741 | Jul 2008 | WO |
2008118536 | Oct 2008 | WO |
2008122483 | Oct 2008 | WO |
2009013106 | Jan 2009 | WO |
2009112433 | Sep 2009 | WO |
2010007783 | Jan 2010 | WO |
2010127947 | Nov 2010 | WO |
2011058678 | May 2011 | WO |
2012152646 | Nov 2012 | WO |
2013116103 | Aug 2013 | WO |
2013116302 | Aug 2013 | WO |
2014038150 | Mar 2014 | WO |
2014121893 | Aug 2014 | WO |
2014184393 | Nov 2014 | WO |
2013140816 | Aug 2015 | WO |
2016082907 | Jun 2016 | WO |
2017029782 | Feb 2017 | WO |
Entry |
---|
Cai et al., “Generation of Metal Nanoparticles By Laser Ablation of Microspheres,” J. Aerosol Sci., vol. 29, No. 5/6 (1998), pp. 627-636. |
Raszewski et al., “Methods For Producing Hollow Glass Microspheres,” Powerpoint, cached from Google, Jul. 2009, 6 pages. |
Number | Date | Country | |
---|---|---|---|
20230137842 A1 | May 2023 | US |
Number | Date | Country | |
---|---|---|---|
62265055 | Dec 2015 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 17037855 | Sep 2020 | US |
Child | 18087266 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 15776276 | US | |
Child | 17037855 | US |