Cold-spray nozzle

Information

  • Patent Grant
  • 11292056
  • Patent Number
    11,292,056
  • Date Filed
    Friday, July 6, 2018
    5 years ago
  • Date Issued
    Tuesday, April 5, 2022
    2 years ago
Abstract
Systems, apparatus, and method for manufacturing are disclosed. In an aspect, the apparatus may be a cold-spray nozzle. The cold-spray nozzle may include a variable diameter convergent part. The cold-spray nozzle may also include a variable diameter divergent part. The variable diameter divergent part may form a diffuser. Additionally, The cold-spray nozzle may include a ring portion. The ring portion may couple the variable diameter convergent part and the variable diameter divergent part. Additionally, the ring portion may control the opening to the diffuser.
Description
BACKGROUND
Field

The present disclosure relates generally to manufacturing techniques, and more specifically 3-D-printing methods using spray forming and particularly to nozzles for 3-D-printing methods using cold-spray processes.


Background

Key technological developments and advances in manufacturing have been made in recent years with the increasingly widespread use of three dimensional (3-D) printing for a variety of applications. Such applications are especially prevalent in the context of manufacturing numerous types of sophisticated mechanical structures. Similar advances have recently been made, and milestones achieved, relative to the advancement of 3-D printing technologies themselves. The plethora of modern 3-D printing techniques that have been the subject of such recent advances include, for example, stereolithography (SLA), digital light processing (DLP), fused deposition modeling (FDM), selective laser sintering (SLS), selective laser melting (SLM), and the like.


One example of 3-D printing may use cold-spray forming as part of a manufacturing process of components. Spray forming may direct a solid phase powder material into a base material at high speed. Cold-spray forming may generally be an additive manufacturing process by spraying one or more materials to form a manufactured article. With the cold-spray manufacturing process, a material being deposited may be kept below the material's melting point. The material being deposited may be sprayed at a base material at a speed high enough to induce solid-state welding on impact. The material may be sprayed using a nozzle, e.g., a cold-spray nozzle. Cold-spray may be used to deposit a metal (or metal alloy, plastics, ceramics, or mixtures thereof) structure to join, for example, a number of off-the-shelf parts or manufactured parts such as extruded parts, 3-D printed parts, cold-spray 3-D printed parts or other manufactured parts.


Conventional cold-spray nozzles have fixed opening profiles. Accordingly, when different size cold-spray nozzles are needed for a particular spray pattern for the solid powder material, the cold-spray process will need to be stopped so that one nozzle may be changed for another nozzle. Stopping the cold-spray process to change nozzles may slow down the manufacturing of parts.


SUMMARY

Several aspects of methods will be described more fully hereinafter with reference to three-dimensional (3-D) printing techniques. One aspect relates to manufacturing techniques that include 3-D-printing methods using spray forming and more particularly to nozzles for cold-spray processes.


Systems, apparatus, and method for manufacturing a structure are disclosed. An apparatus may be a cold-spray nozzle. The cold-spray nozzle includes a variable diameter convergent part. Additionally, the cold-spray nozzle includes a variable diameter divergent part forming a diffuser. The cold-spray nozzle also includes a ring portion coupling the variable diameter convergent part and the variable diameter divergent part and controlling the opening to the diffuser.


An apparatus may be a cold-spray device. The cold-spray device includes a material hopper. Additionally, the cold-spray device includes a pressurized gas feed coupled to the material hopper. The cold-spray device also includes a cold-spray nozzle coupled to the pressurized gas feed and configured to receive material from the material hopper. The cold-spray nozzle includes a variable diameter convergent part. Additionally, the cold-spray nozzle includes a variable diameter divergent part forming a diffuser. The cold-spray nozzle also includes a ring portion coupling the variable diameter convergent part and the variable diameter divergent part and controlling the opening to the diffuser.


A method of cold-spray forming a part includes cold-spraying at least a first portion of a first layer of the part. Additionally, the method of cold-spray forming includes adjusting a variable diameter convergent part and a variable diameter divergent part in a nozzle including the variable diameter convergent part and the variable diameter divergent part forming a diffuser and a ring portion coupling the variable diameter convergent part and the variable diameter divergent part. The method of cold-spray forming also includes cold-spraying at least a second portion of a second layer of the part using the adjusted variable diameter convergent part and the adjusted variable diameter divergent part and controlling the opening to the diffuser.


It will be understood that other aspects of 3-D printing using spray forming will become readily apparent to those skilled in the art from the following detailed description, wherein it is shown and described only several embodiments by way of illustration. As will be realized by those skilled in the art, the manufactured structures and the methods for manufacturing these structures are capable of other and different embodiments, and its several details are capable of modification in various other respects, all without departing from the invention. Accordingly, the drawings and detailed description are to be regarded as illustrative in nature and not as restrictive.





BRIEF DESCRIPTION OF THE DRAWINGS

Various aspects of 3-D printing using spray forming to manufacture, and more particular, to nozzles for such manufacturing will now be presented in the detailed description by way of example, and not by way of limitation, in the accompanying drawings, wherein:



FIGS. 1A-B illustrate a diagram of a 3-D printer using fused deposition modeling (FDM).



FIG. 2 is a flow diagram illustrating an exemplary process of 3-D printing.



FIG. 3 is a diagram of a 3-D printer employing spray forming.



FIG. 4 is a diagram of a 3-D printer integrating spray forming and fused deposition modeling (FDM) printing.



FIG. 5 is a diagram of a cold-spray nozzle that may be used in conjunction with a 3-D printer employing spray forming such as the 3-D printer employing spray forming illustrated with respect to FIGS. 3-4.



FIG. 6 is a diagram of a cold-spray nozzle that may be used in conjunction with a 3-D printer employing spray forming such as the 3-D printer employing spray forming illustrated with respect to FIGS. 3-4.



FIG. 7 is a flow diagram illustrating an exemplary method of cold-spray forming a part.





DETAILED DESCRIPTION

The detailed description set forth below in connection with the appended drawings is intended to provide a description of various exemplary embodiments of 3-D printing using spray forming to manufacture and is not intended to represent the only embodiments in which the invention may be practiced. The term “exemplary” used throughout this disclosure means “serving as an example, instance, or illustration,” and should not necessarily be construed as preferred or advantageous over other embodiments presented in this disclosure. The detailed description includes specific details for the purpose of providing a thorough and complete disclosure that fully conveys the scope of the invention to those skilled in the art. However, the invention may be practiced without these specific details. In some instances, well-known structures and components may be shown in block diagram form, or omitted entirely, in order to avoid obscuring the various concepts presented throughout this disclosure.



FIGS. 1A-B illustrate a diagram of a 3-D printer that may use fused deposition modeling (FDM). FDM is an additive manufacturing technique wherein a thermoplastic or other material, e.g., metal, may be extruded through a temperature-controlled print nozzle 102. The print nozzle 102 can be moved in both horizontal and vertical directions by a mechanical device that is under the control of a computer-aided manufacturing (CAM) software package. The 3-D part to be constructed is built one layer at a time, and the layers successively overlap each other in a prescribed manner to manufacture a part 121.


The 3-D printer of FIG. 1A also includes a first spool 104 for providing a first material 106 that is fed to the extrusion head 102 and a second spool for providing a second material that is fed to the extrusion head 102. While in some configurations the material 114 may constitute a build material for forming the successive layers of the part and the material 116 a support material for providing temporary support to accommodate spatial vacancies created by the predetermined shapes of certain structures whose shape may otherwise be compromised by gravity prior to solidifying, the 3-D printing techniques contemplated in this disclosure may obviate the need for a support material by using complex matrix arrays as backing structures.


3-D printer 100 may also include a substrate or base 112 upon which the printing may occur, and a vertically movable build platform 110. During the 3-D printing process wherein the material 114 is extruded onto a surface of part 121 to manufacture successive layers, the build platform 110 may be configured under software control to gradually move lower in the vertical direction (as indicated by the arrow on support arm 123) to accommodate the space occupied by the increasing number of layers of part 121.



FIG. 1B shows an expanded view of extrusion head 102. Materials 114 and 116 may be fed using rotating drive wheels 125 into extrusion nozzles 126 and 128, respectively. The materials 114 and 116 are melted by the application of heat in respective extrusion nozzles 126 and 128 and thereupon ejected under software control from the nozzles onto the substrate 110, or onto the layers previously disposed on the substrate.


While an FDM printing technique has been described here for illustration purposes, the disclosure herein is not so limited, and any suitable 3-D printing technique may be employed in connection with the description that follows.



FIG. 2 is a flow diagram 200 illustrating an exemplary process of 3-D printing. A data model of the desired 3-D object to be printed is rendered (step 210). A data model is a virtual design of the 3-D object. Thus, the data model may reflect the geometrical and structural features of the 3-D object, as well as its material composition. The data model may be created using a variety of methods, including 3-D scanning, 3-D modeling software, photogrammetry software, and camera imaging.


3-D scanning methods for creating the data model may also use a variety of techniques for generating a 3-D model. These techniques may include, for example, time-of-flight, volumetric scanning, structured light, modulated light, laser scanning, triangulation, and the like.


3-D modeling software, in turn, may include one of numerous commercially available 3-D modeling software applications. Data models may be rendered using a suitable computer-aided design (CAD) package, for example in an STL format. STL files are one example of a file format associated with commercially available CAD software. A CAD program may be used to create the data model of the 3-D object as an STL file. Thereupon, the STL file may undergo a process whereby errors in the file are identified and resolved.


Following error resolution, the data model can be “sliced” by a software application known as a slicer to thereby produce a set of instructions for 3-D printing the object, with the instructions being compatible and associated with the particular 3-D printing technology to be utilized (step 220). Numerous slicer programs are commercially available. Generally, the slicer program converts the data model into a series of individual layers representing thin slices (e.g., 100 microns thick) of the object being printed, along with a file containing the printer-specific instructions for 3-D printing these successive individual layers to produce an actual 3-D printed representation of the data model.


A common type of file used for this purpose is a G-code file, which is a numerical control programming language that includes instructions for 3-D printing the object. The G-code file, or other file constituting the instructions, is uploaded to the 3-D printer (step 230). Because the file containing these instructions is typically configured to be operable with a specific 3-D printing process, it will be appreciated that many formats of the instruction file are possible depending on the 3-D printing technology used.


In addition to the printing instructions that dictate what and how an object is to be rendered, the appropriate physical materials necessary for use by the 3-D printer in rendering the object are loaded into the 3-D printer using any of several conventional and often printer-specific methods (step 240). In fused deposition modeling (FDM) 3-D printers, as indicated above, materials may be loaded as filaments on spools, which are placed on one or more spool holders. The filaments are typically fed into an extruder apparatus which, in operation, heats the filament into a melted form before ejecting the material onto a build plate or other substrate. In selective laser sintering (SLS) printing and other methods, the materials may be loaded as powders into chambers that feed the powder to a build platform. Depending on the 3-D printer, other techniques for loading printing materials may be used.


The respective data slices of the 3-D object are then printed based on the provided instructions using the material(s) (step 250). In 3-D printers that use laser sintering, a laser scans a powder bed and melts the powder together where structure is desired and avoids scanning areas where the sliced data indicates that nothing is to be printed. This process may be repeated thousands of times until the desired structure is formed, after which the printed part is removed from a fabricator. In fused deposition modeling, as described above, parts are printed by applying successive layers of model and support materials to a substrate. In general, any suitable 3-D printing technology may be employed for purposes of this disclosure.


Like other 3-D printing techniques, the FDM technique has a minimum layer resolution, which may in some configurations be on the order of 0.127 mm or thereabouts, depending on the printer resolution and other factors. As a consequence of this minimum resolution, it becomes apparent that the attempted 3-D printing of an angled surface will result in often unwanted “stair-stepped” artifacts caused by the finite thickness of the successive layers.


Conventional spray forming involves manufacturing metal components with homogeneous microstructures via the inert gas atomization of a liquid metal stream into droplets and the deposition of semi-solid sprayed droplets onto a shaped substrate. The substrate collects the droplets and solidifies them into a coherent preform. In one example of the process, an alloy is melted, normally in an induction furnace, then the molten metal is slowly poured through a conical tundish into a small-bore ceramic nozzle. The molten metal exits the furnace and is broken up into droplets by an atomizer. The droplets then proceed downwards to impact a substrate. The process is arranged such that the droplets strike the substrate while in the semi-solid condition. This process provides sufficient liquid fraction to ‘stick’ the solid fraction together. Deposition continues, gradually building up a spray formed part, such as a billet, of metal on the substrate. Spray forming may use a chamber in the shape of the part to be manufactured.


Spray forming may involve applying finishing procedures on metal structures as indicated above or forming metal structures in a chamber. More specifically, metal parts may be spray formed in a temperature controlled chamber, which is typically in a shape that is consistent with that of the final part. In current metal spray forming processes, dedicated equipment is needed such as the chamber, nozzle, atomizer, etc. In addition, the metal parts are limited by the constraints of the chamber and can only be shaped to substantially adhere to the geometry of the chamber.


Accordingly, in one embodiment, a spray forming technique is incorporated as part of a 3-D printer. The 3-D printer includes a flexible, computer-controlled nozzle having six degrees of freedom that is capable of being manipulated in all three X-Y-Z directions and inclined at a variety of angles relative to the printer build plate. The 3-D printer incorporating the spray former may, depending on the embodiment, be used for both for finishing of surfaces of existing parts and for wholesale construction of parts. In other exemplary embodiments, the spray forming 3-D printer is not limited to spray forming of metals and may additionally or alternatively employ spray forming of plastics and other materials, e.g., metal. Thus, the 3-D printer may incorporate a spray former that broadly includes one or more mechanical assemblies for converting a desired material into droplets and spray forming the material in a manner specified by the 3-D printing instructions and/or the CAM program associated with the 3-D printer.



FIG. 3 shows a conceptual diagram of a 3-D printer 300 employing spray forming. The 3-D printer includes support arm 302, build plate 304, and substrate 306. In this embodiment, a tooling shell 308 is disposed on a surface of substrate 306. In one exemplary embodiment, the tooling shell 308 was previously machined, or 3-D printed and was placed on the substrate 308 after its construction.


In another exemplary embodiment as described further below with reference to FIG. 4, the tooling shell 308 may be 3-D printed on 3-D printer 300. For example, 3-D printer 300 may include a conventional computer-controlled print extruder (not shown) which may 3-D print the mold using any of a variety of known methods (SLS, FDM, etc.). In another exemplary embodiment, the mold is spray formed using 3-D printer 300.


A robotic arm 314 under computer control of the 3-D printer may be used to spray form a part 310, such as a panel, on a surface of the tooling shell 308. In other exemplary embodiments, the spray forming is deposited directly on substrate 306 to spray form the part 310. The nozzle 316 of the robotic arm 314 shoots droplets 312 of material onto the tooling shell 308 to thereby create the part 310 as described above.


As the part 310 is formed by the 3-D printer using spray forming, it will be appreciated that the angled or inclined sections 318 and 320 of part 310 can be created without any appreciable stair-stepped effect. Accordingly, the use of spray forming as part of, and under computer control of, the 3-D printer enables a manufacturer to form a part 310 that requires no further finishing step. Accordingly, a smoothened part may be provided in a single step or on a single 3-D printer.


In an exemplary embodiment, robotic arm 314 can be manipulated in a variety of directions and angles. For example, robotic arm 314 may be moved in one or more of the A, B or C directions (or directions at any point in between), which may correspond respectively to coordinate axes X, Y, Z of the 3-D printer. For example, in another exemplary embodiment, robotic arm 314 can be inclined at substantially any angle in order to perform spray forming at a variety of angles. In yet another embodiment, robotic arm 314 may be configured to rotate or twist as shown by the arrow and corresponding designation D. In an exemplary embodiment, the robotic arm 314 is equipped with six degrees of freedom. In one embodiment, the robotic arm 314 is designed to be thin relative to the generally bulky print extruder 402 (see FIG. 4) and associated mechanical assembly. This gives the robotic arm 314 additional flexibility to move about the substrate.


Conventional 3-D printers that perform plastic extrusion generally have a limited ability to alter angles of the print extruder. Such conventional printers typically employ a pivot point for the print nozzle in lieu of a thin, flexible robotic arm. For this reason, the extruders on 3-D printers typically do not have the six degrees of freedom such that they can have significant flexibility in their degrees of movement. One reason for this limitation is that conventional print nozzles typically have thicker diameters and cannot be manipulated easily about different axes, in contrast to the sleek robotic arm 314, whose range of diameters may be made very thin due in part to the intrinsic nature of the spray forming technique and the small size of droplets required from the spray nozzle.


In addition, due to the thickness of the extruded material and other constraints, material extruded from conventional printers may be adversely affected by gravity when the extruder angle is changed, for example, to a slightly angled position to deposit material. That is, the print extruder in the conventional 3-D printer is often bulky, carries more inertia, and is limited in motion due to its pivot point connection to the remainder of the extrusion system so that its flexibility to change angles and directions are accordingly limited. This phenomenon is similar in principle to attempting to write upside down with a ballpoint pen. 3-D printing using spray forming lacks this limitation. The spray forming technologies enables the 3-D printer to spray the light droplets on the substrate or part at essentially any angle, including in an upward direction, and the spray mechanic is not substantially adversely affected by gravity.


Because the robotic arm 314 and spray forming capability is incorporated as part of the 3-D printer, the arm 314 can be controlled and directed under computer control using instructions provided directly to the 3-D printer. In addition, in contrast to the conventional spray forming method wherein a chamber constrains the part formation to adhere to a single or a limited geometry, the 3-D printer as disclosed herein can spray form parts in three dimensions, with such parts having a variety of possible geometries and features under software control.


The mechanical assembly of the robotic arm 314 and printer may vary depending on the embodiment. Where spray forming of metals is performed, the assembly may incorporate a mechanism for heating the metal, an atomizer, and other elements. In another embodiment, robotic arm 314 of the 3-D printer may be configured to spray resins onto a mold or a substrate for forming or finishing parts. Generally, in considering the spray forming of different types of materials, molten materials should not be overly viscous to thereby render them too difficult for nozzle 316 to eject the droplets. Accordingly, in an exemplary embodiment, nozzle 316 of robotic arm 314 may include an assembly for adjusting the viscosity of the target material to be used in the spray forming process. In one embodiment, the assembly may be dynamically adjusted according to software as a function of the material to be used in the spray forming process. In addition, for plastics, a heating mechanism may be included in or proximate to nozzle 316 for facilitating the flow of the material.


Where thermoset resins are used, the resin and the hardener are generally mixed in some ratio and then applied. Pre-mixing the resin and the hardener and then attempting to spray form the resulting viscous material gives rise to inherent difficulties. For example, pre-mixing the resin and hardener and spray forming the combined material may cause the material to cure within the nozzle, thereby clogging the nozzle.


Accordingly, in another exemplary embodiment, robotic arm 314 may include two nozzles 316 (only one shown), each of which constitutes a separate spray forming head. A first such nozzle may spray the resin and the second nozzle may spray the hardener. This technique obviates the difficulties inherent in pre-mixing and spraying the combined resin and hardener.


The above-described 3-D printing techniques can be used either to smooth (finish) a part such as a panel using spray forming or to create a part.


In spray forming plastics, the diameter of the nozzle 316 is generally very small, in some embodiments being on the order of approximately 50 μm. Because the diameter of nozzle 316 is small, the corresponding thickness of the material exiting nozzle 316 may be negligible, such that substantially no stair-stepped effect is observed when 3-D printing parts using the spray forming technique.


The robotic arm 314 is advantageous for incorporation into the 3-D printer 300 for use in spray forming because, among other reasons, such robotic assemblies may be controlled by a data model and related instructions as are used in 3-D printers.


Referring back to FIG. 3, in an example where the part 310 to be formed constitutes an exterior body panel of a vehicle, the material forming the panel can be sprayed over the 3-D printed tooling shell 308 (or the substrate 306 in other embodiments). In this manner, imperfections that arise due to surface properties of the 3-D printed tooling shell 308 are present only on the B side of the final panel where the part 310 meets the surface of tooling shell 308. In contrast, the A side (surface 318, 320 of part 310) of the panel may be made to be substantially flawlessly smooth, thereby satisfying Class A vehicular surface requirements.


In another exemplary embodiment, the 3-D printer as described above can be used to spray resin on metal or plastic 3-D printed tools to smoothen the surface of the tools.


In the embodiments involving spray forming of metals, various techniques and processes may be suitable for use in conjunction therewith including plasma deposition, physical vapor deposition, chemical vapor deposition, and the like.



FIG. 4 shows a diagram of a 3-D printer 400 integrating spray forming and FDM printing capability. While an FDM assembly is shown for purposes of illustration, it will be appreciated that any conventional 3-D printing technique may be integrated with the spray forming mechanism. The spray forming mechanism includes robotic arm 414, nozzle 416, and associated control mechanism (not shown) guided by printer software. As previously shown with reference to FIG. 3, robotic arm 414 of FIG. 4 may be under control of the 3-D printer instructions and can be manipulated at a variety of angles and directions, including in the A, B, C, and D directions.


In the embodiment shown, part 408 is 3-D printed on build plate 404 (or an intervening substrate or foam base) using print extruder 402 and one or both of print materials 414 and 418. As discussed in connection with previous embodiments, the angled portions of part 408 are characterized by a stair-stepped effect, the scale of which is exaggerated here for clarity. After part 408 is 3-D printed via print extruder 402, nozzle 416 of robotic arm applies spray forming to finish the part and thereby reduce or eliminate the stair-stepped effect, such that part 408 will have smooth angled surfaces. Depending on the embodiment, metals, plastics, or composites may be spray formed.



FIG. 5 is a diagram of a cold-spray nozzle 500 that may be used in conjunction with a 3-D printer (e.g., 300, 400) employing spray forming such as the 3-D printer (e.g., 300, 400) employing spray forming illustrated with respect to FIGS. 3-4.


An aspect of the systems and methods described herein presents a technique that may enable print resolution control. The print resolution control may be mid-print, e.g., the resolution may be changed during the course of printing a particular item, e.g., using the 3-D printer (e.g., 300, 400). The print resolution control may be used for cold-spray additive manufacturing. For example, the systems and methods described herein may include a cold-spray nozzle 500 with a variable diameter convergent part 502 and a variable diameter divergent part 504 forming a diffuser (e.g., variable diameter divergent part 504).


For example, one aspect may include a series of hinges 506 and overlapping sheets 508 to control the diameter (d1) of the converging section (e.g., variable diameter convergent part 502) and the diameter (d2) of the diverging sections (e.g., variable diameter divergent part 504) of a cold-spray gun (cold-spray nozzle 500). In an aspect, the resolution of metal deposited depends on a resulting particle flow. The resulting particle flow may depend strongly on the choke point 510 and outlet diameter (d2). By varying both the choke point 510 and outlet diameter (d2), it is possible to change, mid-print, the resulting area of deposition, e.g., by an order of magnitude. Previous cold-spray guns have machined converging-diverging nozzles and require switching the physical nozzle to change the deposition area.


In an aspect, a cold-spray nozzle 500 includes a variable diameter convergent part 502. Additionally, the cold-spray nozzle 500 includes a variable diameter divergent part 504 forming a diffuser. The cold-spray nozzle 500 also includes a ring portion 510 coupling the variable diameter convergent part 502 and the variable diameter divergent part 504. The ring portion 510 controls the opening to the diffuser, e.g., the variable diameter divergent part 504.


In an aspect, the variable diameter convergent part 502 comprises a nozzle 500 containing a series of hinges 506 and overlapping sheets 508 within the nozzle 500, the hinges 506 and overlapping sheets 508 configured to control the diameter (d1) of the variable diameter convergent part 502.


In an aspect, the variable diameter divergent part 504 comprises a nozzle containing a series of hinges 506 and overlapping sheets 508 within the nozzle, the hinges 506 and overlapping sheets 508 configured to control the diameter (d2) of the variable diameter divergent part 504.


In an aspect, the size of the ring portion 510 is variable. The size of the ring portion 510 controls a flow of a cold-spray.



FIG. 6 is another diagram of a cold-spray nozzle 600 that may be used in conjunction with a 3-D printer (e.g., 300, 400) employing spray forming such as the 3-D printer (e.g., 300, 400) employing spray forming illustrated with respect to FIGS. 3-4.


As discussed above, an aspect of the systems and methods described herein presents a technique that may enable print resolution control. The print resolution control may be mid-print, e.g., resolution may be changed during the course of printing a particular item, e.g., using the 3-D printer (e.g., 300, 400). The print resolution control may be used for cold-spray additive manufacturing. For example, the systems and methods described herein may include a cold-spray nozzle 600 with a variable diameter divergent part that includes a plug nozzle.


For example, one aspect may include a plug nozzle 602 inside the cold-spray nozzle 600 to control the usable diameter where the converging section 606 and the divergent section 608 meet. The choke point 610 has a diameter, d1. The portion of the choke point 610 that is actually available for a flow of cold-spray material out of the cold-spray nozzle 600 may be adjusted using the plug nozzle 602. For example, as the plug nozzle 602 moves in and out within the cold-spray nozzle 600, the, usable portion allowing material flow enlarges or decreases within a choke point 610. The outer diameter of the choke point 610 may remain a diameter, d1. More specifically, As the plug nozzle 602 moves out, the usable portion of the choke point 610 having the diameter (d1) increases. As the plug nozzle 602 moves in, the usable portion of the choke point 610 having the diameter (d1) decreases.


As discussed above, in an aspect, the resolution of metal deposited depends on a resulting particle flow. The resulting particle flow may depend strongly on the portion of the choke point 610 available for material flow. While the diameter (d1) and the outlet diameter (d2) may be fixed, flow through the choke point may be adjusted by moving the plug nozzle 602. By varying the position of the plug nozzle 602, it may be possible to change, mid-print, the resulting area of deposition, e.g., by an order of magnitude.


In an aspect, a cold-spray nozzle 600 includes a variable usable diameter convergent part 606. Referring back to FIGS. 1A-1B, 3, and 4, a cold-spray device (100, 300, 400) may include a material hopper (or spool 104). The cold-spray device (100, 300, 400) may also include a pressurized gas feed (not shown) coupled to the material hopper. Additionally, the cold-spray device (100, 300, 400) may include a cold-spray nozzle (126, 128, 316, 416, 500, 600) coupled to the pressurized gas feed and configured to receive material from the material hopper. The cold-spray nozzle (126, 128, 316, 416, 500, 600) may include a variable diameter convergent part (502, 606), a variable diameter divergent part (504, 604) forming a diffuser, and a ring portion (510) coupling the variable diameter convergent part (502, 606) and the variable diameter divergent part (504, 604) and controlling the opening to the diffuser, e.g., variable diameter divergent part (504, 608).



FIG. 7 is a flow diagram illustrating an exemplary method of cold-spray forming a part. At 710, cold-spray at least a first portion of a first layer of the part. For example, cold-spray (e.g., using a cold-spray nozzle 126, 128, 316, 416, 500, 600 on a cold-spray device 100, 300, 400) at least a first portion of a first layer of the part. In an aspect, the first layer and the second layer may be different layers. In another aspect, the first layer and the second layer may be a same layer.


At 720, a determination is made if an adjustment of a variable diameter convergent part and a variable diameter divergent part in a nozzle is needed. The nozzle includes the variable diameter convergent part. For example, a processing system on a cold-spray device (100, 300, 400) or connected to a cold-spray device (100, 300, 400) may determine if an adjustment of a variable diameter convergent part (502, 606) and a variable diameter divergent part (504) is needed. The nozzle (126, 128, 316, 416, 500, 600) includes the variable diameter convergent part (502, 606) is needed.


In an aspect, the adjusting occurs continuously over the same layer. In other words, the adjusting may be without interruption or without gaps, e.g., over a particular interval when spray-forming is occurring. In another aspect, the adjusting occurs continually over the same layer. In other words, the adjusting may frequently be repeated in the same way, or regularly, e.g., over a particular interval when spray-forming is occurring. For example, when an adjustment is needed, the method may proceed to block 730 (below). When an adjustment is not needed, the method may continue cold-spraying, e.g., return to block 710, e.g., over a particular interval when spray-forming is occurring. Alternatively, the cold-spray may end (not shown), e.g., when a part is completed, a device implementing the method needs adjustment, fixing, replenishment of materials, or some other change, alteration, modification, adjustment, variation, or adaptation.


At 730, a variable diameter convergent part and a variable diameter divergent part in a nozzle are adjusted. The nozzle may include the variable diameter convergent part and the variable diameter divergent part. The variable diameter divergent part forms a diffuser. A ring portion couples the variable diameter convergent part and the variable diameter divergent part. For example, a processing system on or connected to a cold-spray device 100, 300, 400 may control a nozzle (126, 128, 316, 416, 500, 600) such that the nozzle (126, 128, 316, 416, 500, 600) is adjusted. The nozzle (126, 128, 316, 416, 500, 600) may include a variable diameter convergent part (502, 606) and a variable diameter divergent part (504) in a nozzle (126, 128, 316, 416, 500, 600) including the variable diameter convergent part (502, 606). The variable diameter divergent part (504) forms a diffuser. A ring portion (510) couples the variable diameter convergent (502, 606) part and the variable diameter divergent part (504). In an aspect, a convergent part (606) may vary using a plug nozzle (602).


At 740, at least a second portion of a second layer of the part is cold-sprayed using the adjusted variable diameter convergent part and the adjusted variable diameter divergent part. For example, a cold-spray device 100, 300, 400 may cold-spray at least a second portion of a second layer of the part using the adjusted variable diameter convergent part (502, 606) and the adjusted variable diameter divergent part (504). After the block 740, the method may repeat with subsequent first layers and the first portion or a subsequent “first” portion. In other words, a subsequent execution of block 710 may follow block 714. Alternatively, the method may end after execution of block 740 (not shown).


The previous description is provided to enable any person skilled in the art to practice the various aspects described herein. Various modifications to these exemplary embodiments presented throughout this disclosure will be readily apparent to those skilled in the art, and the concepts disclosed herein may be applied to 3-D printing techniques using spray forming. Thus, the claims are not intended to be limited to the exemplary embodiments presented throughout the disclosure but are to be accorded the full scope consistent with the language claims. All structural and functional equivalents to the elements of the exemplary embodiments described throughout this disclosure that are known or later come to be known to those of ordinary skill in the art are intended to be encompassed by the claims. Moreover, nothing disclosed herein is intended to be dedicated to the public regardless of whether such disclosure is explicitly recited in the claims. No claim element is to be construed under the provisions of 35 U.S.C. § 112(f), or analogous law in applicable jurisdictions, unless the element is expressly recited using the phrase “means for” or, in the case of a method claim, the element is recited using the phrase “step for.”

Claims
  • 1. A cold-spray device comprising: a material hopper;a pressurized gas feed coupled to the material hopper; anda cold-spray nozzle coupled to the pressurized gas feed and configured to receive material from the material hopper, the cold-spray nozzle including: a variable diameter convergent part;a variable diameter divergent part forming a diffuser; anda ring portion coupling the variable diameter convergent part and the variable diameter divergent part, wherein a size of the ring portion controls a flow of a cold-spray through an opening between the variable diameter convergent part and the variable diameter divergent part;wherein the nozzle contains a series of hinges and overlapping sheets within the nozzle, the hinges and overlapping sheets configured to control a diameter of the variable diameter divergent part.
  • 2. The cold-spray device of claim 1, wherein the variable diameter convergent part comprises a nozzle.
  • 3. The cold-spray device of claim 1, further comprising a movable build platform.
US Referenced Citations (359)
Number Name Date Kind
2982089 Egbert May 1961 A
3146669 Wolf Sep 1964 A
5203226 Hongou et al. Apr 1993 A
5742385 Champa Apr 1998 A
5975493 Ellingson et al. Nov 1999 A
5990444 Costin Nov 1999 A
6010155 Rinehart Jan 2000 A
6046426 Jeantette et al. Apr 2000 A
6096249 Yamaguchi Aug 2000 A
6140602 Costin Oct 2000 A
6250533 Otterbein et al. Jun 2001 B1
6252196 Costin et al. Jun 2001 B1
6318642 Goenka et al. Nov 2001 B1
6365057 Whitehurst et al. Apr 2002 B1
6391251 Keicher et al. May 2002 B1
6409930 Whitehurst et al. Jun 2002 B1
6468439 Whitehurst et al. Oct 2002 B1
6554345 Jonsson Apr 2003 B2
6585151 Ghosh Jul 2003 B1
6644721 Miskech et al. Nov 2003 B1
6811744 Keicher et al. Nov 2004 B2
6866497 Saiki Mar 2005 B2
6919035 Clough Jul 2005 B1
6926970 James et al. Aug 2005 B2
6935096 Haiun Aug 2005 B2
7152292 Hohmann et al. Dec 2006 B2
7344186 Hausler et al. Mar 2008 B1
7500373 Quell Mar 2009 B2
7586062 Heberer Sep 2009 B2
7637134 Burzlaff et al. Dec 2009 B2
7710347 Gentilman et al. May 2010 B2
7716802 Stern et al. May 2010 B2
7745293 Yamazaki et al. Jun 2010 B2
7766123 Sakurai et al. Aug 2010 B2
7852388 Shimizu et al. Dec 2010 B2
7908922 Zarabadi et al. Mar 2011 B2
7951324 Naruse et al. May 2011 B2
8094036 Heberer Jan 2012 B2
8163077 Eron et al. Apr 2012 B2
8286236 Jung et al. Oct 2012 B2
8289352 Vartanian et al. Oct 2012 B2
8297096 Mizumura et al. Oct 2012 B2
8354170 Henry et al. Jan 2013 B1
8383028 Lyons Feb 2013 B2
8408036 Reith et al. Apr 2013 B2
8429754 Jung et al. Apr 2013 B2
8437513 Derakhshani et al. May 2013 B1
8444903 Lyons et al. May 2013 B2
8452073 Taminger et al. May 2013 B2
8599301 Dowski, Jr. et al. Dec 2013 B2
8606540 Haisty et al. Dec 2013 B2
8610761 Haisty et al. Dec 2013 B2
8631996 Quell et al. Jan 2014 B2
8675925 Derakhshani et al. Mar 2014 B2
8678060 Dietz et al. Mar 2014 B2
8686314 Schneegans et al. Apr 2014 B2
8686997 Radet et al. Apr 2014 B2
8694284 Berard Apr 2014 B2
8720876 Reith et al. May 2014 B2
8752166 Jung et al. Jun 2014 B2
8755923 Farahani et al. Jun 2014 B2
8787628 Derakhshani et al. Jul 2014 B1
8818771 Gielis et al. Aug 2014 B2
8873238 Wilkins Oct 2014 B2
8978535 Ortiz et al. Mar 2015 B2
9006605 Schneegans et al. Apr 2015 B2
9071436 Jung et al. Jun 2015 B2
9101979 Hofmann et al. Aug 2015 B2
9103503 Odenthal et al. Aug 2015 B2
9104921 Derakhshani et al. Aug 2015 B2
9126365 Mark et al. Sep 2015 B1
9128476 Jung et al. Sep 2015 B2
9138924 Yen Sep 2015 B2
9149988 Mark et al. Oct 2015 B2
9156205 Mark et al. Oct 2015 B2
9186848 Mark et al. Nov 2015 B2
9244986 Karmarkar Jan 2016 B2
9248611 Divine et al. Feb 2016 B2
9254535 Buller et al. Feb 2016 B2
9266566 Kim Feb 2016 B2
9269022 Rhoads et al. Feb 2016 B2
9327452 Mark et al. May 2016 B2
9329020 Napoletano May 2016 B1
9332251 Haisty et al. May 2016 B2
9346127 Buller et al. May 2016 B2
9389315 Bruder et al. Jul 2016 B2
9399256 Buller et al. Jul 2016 B2
9403235 Buller et al. Aug 2016 B2
9418193 Dowski, Jr. et al. Aug 2016 B2
9457514 Schwärzler Oct 2016 B2
9469057 Johnson et al. Oct 2016 B2
9478063 Rhoads et al. Oct 2016 B2
9481402 Muto et al. Nov 2016 B1
9486878 Buller et al. Nov 2016 B2
9486960 Paschkewitz et al. Nov 2016 B2
9502993 Deng Nov 2016 B2
9525262 Stuart et al. Dec 2016 B2
9533526 Nevins Jan 2017 B1
9555315 Aders Jan 2017 B2
9555580 Dykstra et al. Jan 2017 B1
9557856 Send et al. Jan 2017 B2
9566742 Keating et al. Feb 2017 B2
9566758 Cheung et al. Feb 2017 B2
9573193 Buller et al. Feb 2017 B2
9573225 Buller et al. Feb 2017 B2
9586290 Buller et al. Mar 2017 B2
9595795 Lane et al. Mar 2017 B2
9597843 Stauffer et al. Mar 2017 B2
9600929 Young et al. Mar 2017 B1
9609755 Coull et al. Mar 2017 B2
9610737 Johnson et al. Apr 2017 B2
9611667 GangaRao et al. Apr 2017 B2
9616623 Johnson et al. Apr 2017 B2
9626487 Jung et al. Apr 2017 B2
9626489 Nilsson Apr 2017 B2
9643361 Liu May 2017 B2
9662840 Buller et al. May 2017 B1
9665182 Send et al. May 2017 B2
9672389 Mosterman et al. Jun 2017 B1
9672550 Apsley et al. Jun 2017 B2
9676145 Buller et al. Jun 2017 B2
9684919 Apsley et al. Jun 2017 B2
9688032 Kia et al. Jun 2017 B2
9690286 Hovsepian et al. Jun 2017 B2
9700966 Kraft et al. Jul 2017 B2
9703896 Zhang et al. Jul 2017 B2
9713903 Paschkewitz et al. Jul 2017 B2
9718302 Young et al. Aug 2017 B2
9718434 Hector, Jr. et al. Aug 2017 B2
9724877 Flitsch et al. Aug 2017 B2
9724881 Johnson et al. Aug 2017 B2
9725178 Wang Aug 2017 B2
9731730 Stiles Aug 2017 B2
9731773 Gami et al. Aug 2017 B2
9741954 Bruder et al. Aug 2017 B2
9747352 Karmarkar Aug 2017 B2
9764415 Seufzer et al. Sep 2017 B2
9764520 Johnson et al. Sep 2017 B2
9765226 Dain Sep 2017 B2
9770760 Liu Sep 2017 B2
9773393 Velez Sep 2017 B2
9776234 Schaafhausen et al. Oct 2017 B2
9782936 Glunz et al. Oct 2017 B2
9783324 Embler et al. Oct 2017 B2
9783977 Alqasimi et al. Oct 2017 B2
9789548 Golshany et al. Oct 2017 B2
9789922 Dosenbach et al. Oct 2017 B2
9796137 Zhang et al. Oct 2017 B2
9802108 Aders Oct 2017 B2
9809977 Carney et al. Nov 2017 B2
9817922 Glunz et al. Nov 2017 B2
9818071 Jung et al. Nov 2017 B2
9821339 Paschkewitz et al. Nov 2017 B2
9821411 Buller et al. Nov 2017 B2
9823143 Twelves, Jr. et al. Nov 2017 B2
9829564 Bruder et al. Nov 2017 B2
9846933 Yuksel Dec 2017 B2
9854828 Langeland Jan 2018 B2
9858604 Apsley et al. Jan 2018 B2
9862833 Hasegawa et al. Jan 2018 B2
9862834 Hasegawa et al. Jan 2018 B2
9863885 Zaretski et al. Jan 2018 B2
9870629 Cardno et al. Jan 2018 B2
9879981 Dehghan Niri et al. Jan 2018 B1
9884663 Czinger et al. Feb 2018 B2
9898776 Apsley et al. Feb 2018 B2
9914150 Pettersson et al. Mar 2018 B2
9919360 Buller et al. Mar 2018 B2
9931697 Levin et al. Apr 2018 B2
9933031 Bracamonte et al. Apr 2018 B2
9933092 Sindelar Apr 2018 B2
9957031 Golshany et al. May 2018 B2
9958535 Send et al. May 2018 B2
9962767 Buller et al. May 2018 B2
9963978 Johnson et al. May 2018 B2
9971920 Derakhshani et al. May 2018 B2
9976063 Childers et al. May 2018 B2
9987792 Flitsch et al. Jun 2018 B2
9988136 Tiryaki et al. Jun 2018 B2
9989623 Send et al. Jun 2018 B2
9990565 Rhoads et al. Jun 2018 B2
9994339 Colson et al. Jun 2018 B2
9996890 Cinnamon et al. Jun 2018 B1
9996945 Holzer et al. Jun 2018 B1
10002215 Dowski et al. Jun 2018 B2
10006156 Kirkpatrick Jun 2018 B2
10011089 Lyons et al. Jul 2018 B2
10011685 Childers et al. Jul 2018 B2
10012532 Send et al. Jul 2018 B2
10013777 Mariampillai et al. Jul 2018 B2
10015908 Williams et al. Jul 2018 B2
10016852 Broda Jul 2018 B2
10016942 Mark et al. Jul 2018 B2
10017384 Greer et al. Jul 2018 B1
10018576 Herbsommer et al. Jul 2018 B2
10022792 Srivas et al. Jul 2018 B2
10022912 Kia et al. Jul 2018 B2
10027376 Sankaran et al. Jul 2018 B2
10029415 Swanson et al. Jul 2018 B2
10040239 Brown, Jr. Aug 2018 B2
10046412 Blackmore Aug 2018 B2
10048769 Selker et al. Aug 2018 B2
10052712 Blackmore Aug 2018 B2
10052820 Kemmer et al. Aug 2018 B2
10055536 Maes et al. Aug 2018 B2
10058764 Aders Aug 2018 B2
10058920 Buller et al. Aug 2018 B2
10061906 Nilsson Aug 2018 B2
10065270 Buller et al. Sep 2018 B2
10065361 Susnjara et al. Sep 2018 B2
10065367 Brown, Jr. Sep 2018 B2
10068316 Holzer et al. Sep 2018 B1
10071422 Buller et al. Sep 2018 B2
10071525 Susnjara et al. Sep 2018 B2
10072179 Drijfhout Sep 2018 B2
10074128 Colson et al. Sep 2018 B2
10076875 Mark et al. Sep 2018 B2
10076876 Mark et al. Sep 2018 B2
10081140 Paesano et al. Sep 2018 B2
10081431 Seack et al. Sep 2018 B2
10086568 Snyder et al. Oct 2018 B2
10087320 Simmons et al. Oct 2018 B2
10087556 Gallucci et al. Oct 2018 B2
10099427 Mark et al. Oct 2018 B2
10100542 GangaRao et al. Oct 2018 B2
10100890 Bracamonte et al. Oct 2018 B2
10107344 Bracamonte et al. Oct 2018 B2
10108766 Druckman et al. Oct 2018 B2
10113600 Bracamonte et al. Oct 2018 B2
10118347 Stauffer et al. Nov 2018 B2
10118579 Lakic Nov 2018 B2
10120078 Bruder et al. Nov 2018 B2
10124546 Johnson et al. Nov 2018 B2
10124570 Evans et al. Nov 2018 B2
10137500 Blackmore Nov 2018 B2
10138354 Groos et al. Nov 2018 B2
10144126 Krohne et al. Dec 2018 B2
10145110 Carney et al. Dec 2018 B2
10151363 Bracamonte et al. Dec 2018 B2
10152661 Kieser Dec 2018 B2
10160278 Coombs et al. Dec 2018 B2
10161021 Lin et al. Dec 2018 B2
10166752 Evans et al. Jan 2019 B2
10166753 Evans et al. Jan 2019 B2
10171578 Cook et al. Jan 2019 B1
10173255 TenHouten et al. Jan 2019 B2
10173327 Kraft et al. Jan 2019 B2
10178800 Mahalingam et al. Jan 2019 B2
10179640 Wilkerson Jan 2019 B2
10183330 Buller et al. Jan 2019 B2
10183478 Evans et al. Jan 2019 B2
10189187 Keating et al. Jan 2019 B2
10189240 Evans et al. Jan 2019 B2
10189241 Evans et al. Jan 2019 B2
10189242 Evans et al. Jan 2019 B2
10190424 Johnson et al. Jan 2019 B2
10195693 Buller et al. Feb 2019 B2
10196539 Boonen et al. Feb 2019 B2
10197338 Melsheimer Feb 2019 B2
10200677 Trevor et al. Feb 2019 B2
10201932 Flitsch et al. Feb 2019 B2
10201941 Evans et al. Feb 2019 B2
10202673 Lin et al. Feb 2019 B2
10204216 Nejati et al. Feb 2019 B2
10207454 Buller et al. Feb 2019 B2
10209065 Estevo, Jr. et al. Feb 2019 B2
10210662 Holzer et al. Feb 2019 B2
10213837 Kondoh Feb 2019 B2
10214248 Hall et al. Feb 2019 B2
10214252 Schellekens et al. Feb 2019 B2
10214275 Goehlich Feb 2019 B2
10220575 Reznar Mar 2019 B2
10220881 Tyan et al. Mar 2019 B2
10221530 Driskell et al. Mar 2019 B2
10226900 Nevins Mar 2019 B1
10232550 Evans et al. Mar 2019 B2
10234342 Moorlag et al. Mar 2019 B2
10237477 Trevor et al. Mar 2019 B2
10252335 Buller et al. Apr 2019 B2
10252336 Buller et al. Apr 2019 B2
10254499 Cohen et al. Apr 2019 B1
10257499 Hintz et al. Apr 2019 B2
10259044 Buller et al. Apr 2019 B2
10268181 Nevins Apr 2019 B1
10269225 Velez Apr 2019 B2
10272860 Mohapatra et al. Apr 2019 B2
10272862 Whitehead Apr 2019 B2
10275564 Ridgeway et al. Apr 2019 B2
10279580 Evans et al. May 2019 B2
10285219 Fetfatsidis et al. May 2019 B2
10286452 Buller et al. May 2019 B2
10286603 Buller et al. May 2019 B2
10286961 Hillebrecht et al. May 2019 B2
10289263 Troy et al. May 2019 B2
10289875 Singh et al. May 2019 B2
10291193 Dandu et al. May 2019 B2
10294552 Liu et al. May 2019 B2
10294982 Gabrys et al. May 2019 B2
10295989 Nevins May 2019 B1
10303159 Czinger et al. May 2019 B2
10307824 Kondoh Jun 2019 B2
10310197 Droz et al. Jun 2019 B1
10313651 Trevor et al. Jun 2019 B2
10315252 Mendelsberg et al. Jun 2019 B2
10336050 Susnjara Jul 2019 B2
10337542 Hesslewood et al. Jul 2019 B2
10337952 Bosetti et al. Jul 2019 B2
10339266 Urick et al. Jul 2019 B2
10343330 Evans et al. Jul 2019 B2
10343331 McCall et al. Jul 2019 B2
10343355 Evans et al. Jul 2019 B2
10343724 Polewarczyk et al. Jul 2019 B2
10343725 Martin et al. Jul 2019 B2
10350823 Rolland et al. Jul 2019 B2
10356341 Holzer et al. Jul 2019 B2
10356395 Holzer et al. Jul 2019 B2
10357829 Spink et al. Jul 2019 B2
10357957 Buller et al. Jul 2019 B2
10359756 Newell et al. Jul 2019 B2
10369629 Mendelsberg et al. Aug 2019 B2
10382739 Rusu et al. Aug 2019 B1
10384393 Xu et al. Aug 2019 B2
10384416 Cheung et al. Aug 2019 B2
10389410 Brooks et al. Aug 2019 B2
10391710 Mondesir Aug 2019 B2
10392097 Pham et al. Aug 2019 B2
10392131 Deck et al. Aug 2019 B2
10393315 Tyan Aug 2019 B2
10400080 Ramakrishnan et al. Sep 2019 B2
10401832 Snyder et al. Sep 2019 B2
10403009 Mariampillai et al. Sep 2019 B2
10406750 Barton et al. Sep 2019 B2
10412283 Send et al. Sep 2019 B2
10416095 Herbsommer et al. Sep 2019 B2
10421496 Swayne et al. Sep 2019 B2
10421863 Hasegawa et al. Sep 2019 B2
10422478 Leachman et al. Sep 2019 B2
10425793 Sankaran et al. Sep 2019 B2
10427364 Alves Oct 2019 B2
10429006 Tyan et al. Oct 2019 B2
10434573 Buller et al. Oct 2019 B2
10435185 Divine et al. Oct 2019 B2
10435773 Liu et al. Oct 2019 B2
10436038 Buhler et al. Oct 2019 B2
10438407 Pavanaskar et al. Oct 2019 B2
10440351 Holzer et al. Oct 2019 B2
10442002 Benthien et al. Oct 2019 B2
10442003 Symeonidis et al. Oct 2019 B2
10449696 Elgar et al. Oct 2019 B2
10449737 Johnson et al. Oct 2019 B2
10461810 Cook et al. Oct 2019 B2
20040065502 Yamamoto Apr 2004 A1
20060108783 Ni et al. May 2006 A1
20120096769 Tyll Apr 2012 A1
20140277669 Nardi et al. Sep 2014 A1
20160319678 Staroselsky et al. Nov 2016 A1
20170113344 Schönberg Apr 2017 A1
20170341309 Piepenbrock et al. Nov 2017 A1
20170355018 Karlen Dec 2017 A1
Foreign Referenced Citations (39)
Number Date Country
102016012348 Apr 2018 DE
1996036455 Nov 1996 WO
1996036525 Nov 1996 WO
1996038260 Dec 1996 WO
2003024641 Mar 2003 WO
2004108343 Dec 2004 WO
2005093773 Oct 2005 WO
2007003375 Jan 2007 WO
2007110235 Oct 2007 WO
2007110236 Oct 2007 WO
2008019847 Feb 2008 WO
2007128586 Jun 2008 WO
2008068314 Jun 2008 WO
2008086994 Jul 2008 WO
2008087024 Jul 2008 WO
2008107130 Sep 2008 WO
2008138503 Nov 2008 WO
2008145396 Dec 2008 WO
2009083609 Jul 2009 WO
2009098285 Aug 2009 WO
2009112520 Sep 2009 WO
2009135938 Nov 2009 WO
2009140977 Nov 2009 WO
2010125057 Nov 2010 WO
2010125058 Nov 2010 WO
2010142703 Dec 2010 WO
2011032533 Mar 2011 WO
2014016437 Jan 2014 WO
2014187720 Nov 2014 WO
2014195340 Dec 2014 WO
2015193331 Dec 2015 WO
2016116414 Jul 2016 WO
2017036461 Mar 2017 WO
2019030248 Feb 2019 WO
2019042504 Mar 2019 WO
2019048010 Mar 2019 WO
2019048498 Mar 2019 WO
2019048680 Mar 2019 WO
2019048682 Mar 2019 WO
Non-Patent Literature Citations (6)
Entry
US 9,202,136 B2, 12/2015, Schmidt et al. (withdrawn)
US 9,809,265 B2, 11/2017, Kinjo (withdrawn)
US 10,449,880 B2, 10/2019, Mizobata et al. (withdrawn)
https://www.sciencedirect.com/science/article/pii/S0257897211007535#f0005 (Year: 2011).
International Search Report & Written Opinion received in PCT/US2019/040344 dated Sep. 30, 2019.
Supplementary European Search Report issued for corresponding application No. EP 19830834.8, dated Dec. 8, 2021, 9 pages.
Related Publications (1)
Number Date Country
20200009657 A1 Jan 2020 US