Electroformed nickel-chromium alloy

Information

  • Patent Grant
  • 11732372
  • Patent Number
    11,732,372
  • Date Filed
    Monday, August 12, 2019
    5 years ago
  • Date Issued
    Tuesday, August 22, 2023
    a year ago
Abstract
An article comprising a turbine component formed of a nickel-chromium (Ni—Cr) alloy including from 2 to 50 wt % chromium balanced by nickel is disclosed. The Ni—Cr alloy is thicker than at least 125 μm to make a self-supporting turbine component, and the turbine component includes a rotor blade, a stator, or a vane. The Ni—Cr alloy is electroformed on a mandrel by providing an external supply of current to an anode and a cathode in a plating bath containing a solvent, a surfactant, and an ionic liquid including choline chloride, nickel chloride, and chromium chloride.
Description
FIELD OF USE

The present disclosure relates to an electroformed nickel-chromium (Ni—Cr) alloy suitable for making a turbine component intended to operate in hostile environments. The present disclosure also relates to processes for the production of a thick electroformed Ni—Cr alloy component.


BACKGROUND

High and low pressure turbine components including rotor blades, vanes, and stators are generally made of nickel based alloys to stand hostile environments including high temperature. Electroformed Ni has been used in non-high temperature applications. Nickel has excellent high temperature creep resistance, but poor oxidation resistance. Thus, the addition of chromia or alumina formers to increase the oxidation resistance of the nickel based alloys is desirable, particularly for high temperature environment such gas turbine engines.


Electroforming is a metal forming process that builds up metal components through electrodeposition. The part or component is produced by depositing a metal skin onto a base form, known as a mandrel which is removed after the electrodeposition is done. Electroforming differs from electroplating in that the deposit (e.g., Ni—Cr alloy) is much thicker and can exist as a self-supporting structure when the mandrel is removed.


Electroformed Ni—Cr alloys can provide a cost-effective technique to fabricate high temperature-resistant structures with complex geometries, tighter tolerance, and oxidation resistance. Typically, electrodeposition in the conventional plating chemistry has not been successful in forming Ni—Cr alloys with high chromium content (>8% wt., 20% wt. preferred) that is substantially thicker than 10 μm.


Accordingly, it is desirable is to electroform Ni—Cr alloys thicker than at least 10 μm to make high temperature and oxidation-resistant turbine engine parts having complex geometries and requiring tighter tolerance. Further desirable considerations include the cost effectiveness and environmental impact of the deposition process.


SUMMARY

According to an aspect of the present disclosure, an electroformed nickel-chromium (Ni—Cr) alloy suitable for making turbine engine components is disclosed. The electroformed Ni—Cr alloy comprises from 2 to 50 wt % chromium balanced by nickel, wherein the electroformed Ni—Cr alloy is thicker than 10 μm. The addition of chromium increases the oxidation resistance of the nickel based alloys.


According to an aspect of the present disclosure, an article comprising a Ni—Cr alloy including from 2 to 50 wt % chromium balanced by nickel is disclosed. The article includes a turbine component, and the Ni—Cr alloy is thicker than 125 μm to make a self-supporting turbine component.


According to another aspect of the present disclosure, a method for electroforming a thick nickel-chromium (Ni—Cr) alloy that is suitable for making turbine components is disclosed. The method includes providing a plating bath containing a solvent, a surfactant, and an ionic liquid including choline chloride, nickel chloride, and chromium chloride, wherein a molar ratio of the choline chloride and chromium chloride ranges from 0.5 to 3.5, and the solvent comprises from 5 to 80 vol. % relative to a mixture of the choline chloride and metal chlorides including the nickel and chromium chlorides. The method further includes electroforming the Ni—Cr alloy on a mandrel, i.e. cathode by providing an external supply of current to an anode and the cathode, wherein the mandrel is removed after the Ni—Cr alloy is electroformed. Optionally, the method further comprises applying a protective coating on the Ni—Cr alloy to impart oxidation resistance to the turbine component.


The method further includes electroforming a Ni—Cr alloy on a metallic mandrel cathode while using an anode that is either insoluble or soluble such as nickel under electrolytic conditions. Specifically, the insoluble anode is used to promote the oxidation of water to produce oxygen as the main by-product while other minor products can be produced concurrently as well. The soluble nickel anode is used to replenish the nickel deposited onto the cathode.


The foregoing features and elements may be combined in various combinations without exclusivity, unless expressly indicated otherwise. These features and elements as well as the operation thereof will become more apparent in light of the following description and the accompanying drawings. It should be understood, however, that the following description and drawings are intended to be exemplary in nature and non-limiting.


The details of one or more embodiments of the present disclosure are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the present disclosure will be apparent from the description and drawings, and from the claims.





BRIEF DESCRIPTION OF THE DRAWINGS


FIG. 1 illustrates a plating bath filled with an electrolytic solution for electroforming a Ni—Cr alloy according to an embodiment of the present disclosure.



FIG. 2 illustrates an article comprising an electroformed Ni—Cr alloy according an embodiment of the present disclosure.



FIG. 3 is a flow chart of an electroforming Ni—Cr alloy process of the present disclosure.





The drawing(s) depict various preferred embodiments of the present invention for purposes of illustration only. One skilled in the art will readily recognize from the following discussion that alternative embodiments of the structures and methods illustrated herein may be employed without departing from the principles of the invention described herein.


DETAILED DESCRIPTION

Electroforming is a metal forming process that forms self-supporting metal parts or components through electrodeposition. Electroforming a Ni—Cr alloy is a cost-effective and environmentally friendly method to make some high temperature-resistant turbine engine components with complex geometries and tighter tolerance.


According to an aspect of the present disclosure, an electroformed nickel-chromium (Ni—Cr) alloy for use as a turbine component is disclosed. The Ni—Cr alloy comprises from 2 to 50 wt % chromium and the balance nickel, and can be made thicker than at least 10 μm to form self-supporting turbine components. The Figure illustrates a plating bath containing an electrolyte solution for electroforming a Ni—Cr alloy according to an aspect of the present invention.



FIG. 1 illustrates a plating bath filled with an electrolytic solution for electroforming a Ni—Cr alloy according to an embodiment of the present disclosure Referring now to FIG. 1, there is provided a plating bath 102 containing an electrolytic solution that consists of a room temperature ionic liquid, namely deep eutectic solvent, including choline chloride, nickel chloride, chromium chloride, solvents, and surfactants like anionic, cationic, or Zwitterionic (amphoteric) surfactants. The surfactant can be one of sodium dodecyl surfate, fluorosurfactants, cetyl trimethylammonium bromide (CTAB), or cetyl trimethylammonium chloride (CTAC). It is noted that the choline chloride based metal processing is low-cost and environmentally friendly. In one embodiment, a molar ratio of the choline chloride and chromium chloride ranges from 0.5 to 3.5. A turbine component is produced by depositing a metal onto a base form, known as a mandrel 104 which is removed after electroforming is done.


In the embodiment, polar aprotic and polar protic solvents are used to adjust the viscosity and conductivity of the plating bath 102 to attain high quality Ni—Cr alloy deposits. Specifically, protic solvents are preferred due to their ability to donate hydrogen bonds. The solvents include formic acid, citric acid, Isopropanol (IPA), water, acetic acid, and ethylene glycol.


According to one embodiment, preferred solvent content is from 10 to 80 vol % relative to the mixture of choline chloride and metal chlorides including the nickel and chromium chlorides on a pre-mixing basis. Referring to FIG. 1, electroforming the Ni—Cr alloy begins by providing an external supply of current to an anode and a cathode. The mandrel is the cathode. The current can be a direct current (DC) or an alternating current (AC) including a pulse or pulse reverse current (not shown). The regime and/or magnitude of the current can be controlled during the deposition to achieve desired coating composition, density, and morphology.


When the current is supplied, the metal at the soluble anode is oxidized from the zero valence state to form cations with a positive charge. Metal cations, generally in complex forms in the presence of anions in the solution, are reduced at the cathode to deposit in the metallic, zero valence state. The result is the effective reduction and transfer of Ni and Cr ionic species from the electrolytic solution to the mandrel 104. The mandrel 104 is removed after the electroforming is done.


The turbine component to be made is electroformed on the mandrel 104 which is a cathode during electrodeposition. The anode is made of the metal to be plated on the mandrel, and includes a Ni—Cr alloy anode, a Ni and/or Cr anode, or any combination of these materials can be chosen to satisfy different requirements. An insoluble catalytic anode (catalyzing oxygen evolution, hexavalent chromium formation) is preferable, but the anode used is not specifically limited. A combination of soluble Ni anode and an insoluble catalytic anode can be used to control bath composition during the course of electrodeposition as well.


The mandrel is pre-treated prior to electrodeposition. The pre-treatment includes degreasing, cleaning the surface, and activation before being placed in the plating bath for electrodeposition. To enhance mass transport, the mandrel 104 can be moved in either a rotating or reciprocating mode or the electrolytic solution can be agitated during the electroforming process. The electroforming process inevitably decomposes water in the bath 102, and thus the solution in the bath is replenished to maintain consistent deposition quality.



FIG. 2 illustrates an article comprising an electroformed Ni—Cr alloy according an embodiment of the present disclosure. Feasibility of thick electroformed Ni—Cr alloys has been demonstrated by electroforming a Ni—Cr alloy which is thicker than 125 μm to make turbine components. In one embodiment, an article 200 comprises an electroformed Ni—Cr alloy 202 that includes from 2 to 50 wt % chromium balanced by nickel, and is thicker than at least 10 μm which was not attainable through the conventional methods.


In another embodiment, although not specifically limited, an electroformed Ni—Cr alloy 202 comprises from 8 to 20 wt % chromium balanced by nickel. In the embodiment, the Ni—Cr alloy is thicker than 125 μm to make a self-supporting turbine component. Optionally, a protective coating 206 can be applied on a surface 204 of the Ni—Cr alloy 202 to impart further oxidation resistance to the article 200. The protective coating 206 may include aluminum and a bond coat and other thermal barrier coatings. Heat treatment may be performance on the structure.



FIG. 3 is a flow chart of an electroformed Ni—Cr process of the present disclosure. Referring now to FIG. 3, forming a thick electroformed Ni—Cr alloy to make turbine parts begins at step 300 where a part to be made or a mandrel is pre-treated prior to electroforming a Ni—Cr alloy to remove foreign materials on the surface of the part of mandrel. At step 302, a plating bath filled with a solution including a solvent, a surfactant, and an ionic liquid is provided. At step 304, the Ni—Cr alloy is electroformed on the part or mandrel by providing an external supply of current to an anode and a cathode. The mandrel can be moved in a rotating or reciprocating mode during the electroforming process to increase the deposition rate. The electroforming step 304 is done when the Ni—Cr alloy reaches the desired thickness.


After the electroforming is done at step 304, optionally, a protective coating 206 may be applied at step 306. In one embodiment, the protective coating 206 may include a bond coat or a thermal barrier coating. The protective coating 206 may be applied to a surface 204 of the electroformed Ni—Cr alloy 202 at step 306 to impart oxidation resistance to the Ni—Cr alloy 202. The disclosed choline chloride based electroforming is a metal forming process that is cost-effective to make high temperature-resistant turbine parts with complex geometries and tighter tolerance, and is environmentally friendly.


It is to be understood that the disclosure of the present invention is not limited to the illustrations described and shown herein, which are deemed to be merely illustrative of the best modes of carrying out the disclosure, and which are susceptible to modification of form, size, arrangement of parts, and details of operation. The disclosure is intended to encompass all such modifications which are within its spirit and scope of the invention as defined by the following claims.

Claims
  • 1. An article comprising a self-supporting turbine component electroformed of a nickel-chromium (Ni-Cr) alloy including from 30 to 50 wt% chromium balanced by nickel, wherein the Ni-Cr alloy is thicker than 10 μm; and wherein the electroformed component includes an electrodeposited metal skin removed from a mandrel.
  • 2. The article of claim 1, wherein the Ni-Cr alloy comprises from 40 to 50 wt% chromium balanced by nickel.
  • 3. The article of claim 1, wherein the Ni-Cr alloy is thicker than 125 μm.
  • 4. The article of claim 1, wherein the turbine component is a rotor blade or a stator.
  • 5. The article of claim 1, wherein the turbine component is a vane.
  • 6. The article of claim 1, wherein the Ni-Cr alloy comprises from 50 wt% chromium balanced by nickel.
  • 7. The article of claim 1 further comprising a protective coating applied on a surface of the Ni-Cr alloy, the protective coating imparting oxidation resistance to the self-supporting turbine component.
  • 8. The article of claim 7, wherein the protective coating includes aluminum.
  • 9. The article of claim 7, wherein the protective coating includes a bond coat.
  • 10. The article of claim 7, wherein the protective coating includes a thermal barrier coating.
CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. Non-Provisional Application No. 15/103,777, filed on Jun. 10, 2016, which is a National Stage application of PCT/US2014/068447, filed Dec. 3, 2014, which claims the benefit of U.S. Provisional Application No. 61/914,548, filed Dec. 11, 2013, all of which are incorporated by reference in their entirety herein.

US Referenced Citations (39)
Number Name Date Kind
2763921 Turner et al. Sep 1956 A
3338733 Rowady Aug 1967 A
3748110 Hodshire et al. Jul 1973 A
3763002 Skomoroski et al. Oct 1973 A
3810782 Gallmiche May 1974 A
3917517 Jordan et al. Nov 1975 A
3998603 Rairden, III Dec 1976 A
4153453 Hart et al. May 1979 A
4259037 Anderson Mar 1981 A
4461680 Lashmore Jul 1984 A
5126213 Restall Jun 1992 A
5543183 Streckert et al. Aug 1996 A
5881972 Smith et al. Mar 1999 A
5908285 Graff Jun 1999 A
6015630 Padture Jan 2000 A
6331217 Burke Dec 2001 B1
7285337 Narita et al. Oct 2007 B2
20020130047 Allen et al. Sep 2002 A1
20040054231 Abbott et al. Mar 2004 A1
20060029723 Rigney et al. Feb 2006 A1
20060251916 Arikawa et al. Nov 2006 A1
20070059486 Anton et al. Mar 2007 A1
20080017280 Vargas et al. Jan 2008 A1
20090162209 Wortman et al. Jun 2009 A1
20100158681 Nemoto Jun 2010 A1
20100252446 Kuzmanovic et al. Oct 2010 A1
20110065804 Diddario et al. Mar 2011 A1
20130122317 Cheruvu May 2013 A1
20130168825 Bhattacharya Jul 2013 A1
20130199934 Parkos, Jr. et al. Aug 2013 A1
20140007988 Ozbaysal Jan 2014 A1
20140044986 Pillhoefer et al. Feb 2014 A1
20160002803 Sklar Jan 2016 A1
20160031186 Mourer et al. Feb 2016 A1
20160312614 Chen et al. Oct 2016 A1
20160312627 Chen et al. Oct 2016 A1
20170100804 Goncharov Apr 2017 A1
20200291780 Chen et al. Sep 2020 A1
20200291797 Chen et al. Sep 2020 A1
Foreign Referenced Citations (4)
Number Date Country
2854367 May 2013 CA
2623644 Aug 2013 EP
749909 Jun 1956 GB
1233090 May 1971 GB
Non-Patent Literature Citations (21)
Entry
Endres et al., Electrodeposition from Inoic Liquids 353 (Year: 2008), 15 pages.
Lou et al., Electroplating, Encyclopedia of Chem. Proc. (Year: 2006), 10 pages.
“INCONEL alloy 625”; Aug. 13, 2013; Special Metals Corportation, Table 1; 18 pgs.
Andrew P. Abbott et al: “Ionic Liquid Analogues Formed from Hydrated Metal Salts”, Chemistry—A European Journal, vol. 10, No. 15, Aug. 6, 2004 (Aug. 6, 2004), pp. 3769 3774.
European Search Report for European Application No. 14869187.6, dated Jul. 11, 2017, 10 pages.
European Search Report for European Application No. 14869585.1 dated Jul. 11, 2017, 25 pages.
European Search Report for European Application No. 14869585.1 dated Jul. 11, 2017, 8 pages.
European Search Report for European Application No. 14870576.7, dated Jul. 11, 2017, 10 pages.
International Search Report and Written Opinion for International Application No. PCT/US2014/068580, dated Feb. 11, 2015.
International Search Report for Application No. PCT/US14/68447; dated Feb. 11, 2015.
International Search Report for International application No. PCT/US14/68445; International filing date: Dec. 3, 2014; dated Oct. 16, 2015; 4 pgs.
International Written Opinion for International application No. PCT/US14/68445; International filing date: Dec. 3, 2014; dated Oct. 16, 2015; 4 pgs.
Liana Anicia, Andreea Florea and Teodor Visan (2011). Steudies Regarding teh Nickel Electrodeposition Choline Chloride Based Ionic Liquids, Applications of Ionic Liquids in Science and Technology, Prof. Scott Handy (Ed.), ISBN: 978-953-307-605-8 (Year: 2011).
Saravanan et al., “Electrodeposition of Fe—Ni—Cr alloy from Deep Eutectic System containing Choline chloride and Ethylene Glycol”, International Journal of Electrochemical Science, vol. 6, 2011, pp. 1468-1478.
Written Opinion for International Application No. PCT/US14/68447; dated Feb. 11, 2015.
Xu et al., “Ni—Cr alloy electrodepositing technology on Fe substrate and coating performance”, Journal of Central South University of Technology, vol. 14, No. 2, 2007, pp. 181-185.
Y.H. You et al./Surface & Coatings Technology 206 (2012) 3632-3638 (Year: 2012).
Non-Final Office Action issued in U.S. Appl. No. 16/889,248 dated May 9, 2022, 21 pages.
Non-Final Office Action issued in U.S. Appl. No. 16/889,281 dated May 9, 2022, 22 pages.
U.S. Non-Final Office Action issued in U.S. Appl. No. 16/889,248 dated Feb. 1, 2023, pp. 1-22.
U.S. U.S. Non-Final Office Action issued in U.S. Appl. No. 16/889,281 dated Feb. 1, 2023, pp. 1-23.
Related Publications (1)
Number Date Country
20190368061 A1 Dec 2019 US
Provisional Applications (1)
Number Date Country
61914548 Dec 2013 US
Divisions (1)
Number Date Country
Parent 15103777 US
Child 16538493 US