WO2018021409A1 - ニッケル-クロム-鉄基鋳造合金 - Google Patents
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- WO2018021409A1 WO2018021409A1 PCT/JP2017/027051 JP2017027051W WO2018021409A1 WO 2018021409 A1 WO2018021409 A1 WO 2018021409A1 JP 2017027051 W JP2017027051 W JP 2017027051W WO 2018021409 A1 WO2018021409 A1 WO 2018021409A1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/04—Manufacture of glass fibres or filaments by using centrifugal force, e.g. spinning through radial orifices; Construction of the spinner cups therefor
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/04—Manufacture of glass fibres or filaments by using centrifugal force, e.g. spinning through radial orifices; Construction of the spinner cups therefor
- C03B37/047—Selection of materials for the spinner cups
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/053—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 30% but less than 40%
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
Definitions
- the present invention relates to a Ni—Cr—Fe based cast alloy having excellent mechanical strength and corrosion resistance against molten glass.
- the alloy of the present invention is in contact with a high temperature liquid inorganic material such as molten glass, for example for the production of parts such as a centrifugal spinner for breaking molten glass into fibers in a rotating fiberization process, preferably casting.
- a high temperature liquid inorganic material such as molten glass
- a centrifugal spinner for breaking molten glass into fibers in a rotating fiberization process, preferably casting.
- high temperature resistant cobalt (Co) and nickel (Ni) alloys are typically centrifuged, for example, to fiberize molten glass in a rotating fiberization process. In spinners, it is typically used to manufacture parts that come into contact with molten glass. Such alloys are disclosed in Patent Documents 6 and 7, for example.
- Ni-based alloys are superior to Co-based alloys from an economical point of view because the price of Ni is much lower than that of Co. For example, in the current transaction price of metal bullion (as of July 2016), 1 kg of Ni and 1 troy ounce (about 31 g) of Co are about the same price.
- An object of the present invention is to solve the above-mentioned problems, and to provide a novel casting alloy useful for parts such as a centrifugal spinner for fiberizing molten glass in a rotating fiberizing process.
- the cast alloy of the present invention allows for the casting of parts in contact with the molten glass and facilitates production due to excellent corrosion resistance and durability in the molten glass for a long time. Accordingly, the present invention provides a nickel-chromium-iron based cast alloy having improved high temperature mechanical strength and corrosion resistance in high temperature molten glass.
- the inventors of the present invention actively added iron (Fe) in a mass range of 15-30% to a Ni—Cr-based alloy for casting spinner material so that the alloy has desirable creep strength and corrosion resistance at high temperatures. I found out that Further, according to the present invention, it is very easy to produce a Ni—Cr base alloy for casting to which Fe is added by appropriately controlling the composition of main constituent elements such as Ni, Cr and Fe. They found out.
- the Ni—Cr—Fe base cast alloy according to the first aspect of the present invention is a Ni—Cr—Fe base cast alloy suitable for use in the manufacture of parts that come into contact with molten glass, and has a mass percentage.
- Cr 15-30%
- Fe 15-30%
- Co 2.5-5.0%
- W 3.0-6.0%
- Ti 0.0-2.0%
- Nb 0.5 to 2.5%
- Mo 0.5 to 2.0%
- C 0.5 to 1.2%, with the balance being nickel and inevitable impurities To do.
- the content of each composition element is at least one of the following. Cr: 24.5 to 28.5%, Fe: 15 to 25%, Co: 3.0 to 4.5%, W: 3.0 to 5.0%, Ti: 0.7 to 1.5% Nb: 0.5 to 1.4%, Mo: 1.0 to 1.5%, and C: 0.7 to 1.0%.
- the 0.2% compressive yield strength at 1000 ° C. is 100 MPa or more, and at 1050 ° C. at 35 MPa.
- the rate of stable compression creep should be about 7.5 ⁇ 10 ⁇ 8 s ⁇ 1 or less, and the estimated corrosion rate in molten glass at 1050 ° C. should be about 10 mm / year or less.
- the Ni—Cr—Fe base casting alloy according to the second aspect of the present invention is a Ni—Cr—Fe base casting alloy suitable for use in the manufacture of a part in contact with molten glass, and has a mass percentage.
- Cr 22-30%
- Fe 15-30%
- Co 2.5-4.5%
- W 4.0-6.0%
- Ti 0.0-2.0%
- Nb 0.5 to 1.4%
- Mo 0.5 to 2.0%
- C 0.5 to 1.2%, with the balance being nickel and inevitable impurities To do.
- the content of each composition element is at least one of the following. Cr: 24.5-28.5%, Fe: 15-25%, Co: 3.0-4.0%, W: 4.0-5.0%, Ti: 0.7-1.5% Mo: 1.0-1.5% and C: 0.7-1.0%.
- the 0.2% compressive yield strength at 1000 ° C. is 100 MPa or more, and at 1050 ° C. at 35 MPa.
- the rate of stable compression creep should be less than about 5.5 ⁇ 10 ⁇ 8 s ⁇ 1 and the estimated corrosion rate in molten glass at 1050 ° C. should be less than about 8.5 mm / year.
- a method for producing a cast product using the Ni—Cr—Fe based cast alloy of the present invention is a production method for use as a spinner for fiberizing molten glass in a rotating fiberizing process including the following steps. is there; (A) providing the Ni—Cr—Fe based cast alloy according to (1), (2), (4), or (5), (B) melting the alloy and solidifying the alloy to ambient temperature in air to obtain an article free from defects in thermal casting; (C) A step of obtaining a final article by heat-treating the article at a temperature at least 20 ° C. lower than the melting start temperature of the alloy.
- the heat treatment step (c) is between 1150 ° C. and 1250 ° C., and the melting of the alloy Heating the article for 2 to 4 hours at a temperature at least 20 ° C. below the starting temperature, cooling the article at a rate of 65 ° C. to 30 ° C. per minute to 550 ° C. or less, and then ambient temperature in air A step of cooling the article up to.
- FIG. 1 is a graph showing the results of a compression test and a corrosion test at 1050 ° C. performed on Ni—Cr—Fe based alloys of Examples, Conventional Examples and Comparative Examples of the present invention.
- Fe improves the workability of the alloy and is inexpensive, so adding a large amount reduces the cost of the alloy.
- the Fe content is preferably in the range of 15 to 30%, and particularly preferably, if the addition is in the range of 15% to 25%, the strength, oxidation resistance, and corrosion resistance of the alloy are not deteriorated. It has been found to improve processability. For oxidation resistance, multiple alloys were checked and found to add a slight mass during the 500 hour test when iron was added.
- Nb is an element that greatly contributes to strength improvement. In order to achieve this effect, Nb is preferably contained in an amount of 0.5% or more. When Nb is 2.5% or more, macrosegregation occurs during melting and harmful topological close packed (TCP) phases such as delta and Laves phases appear in the alloy. Therefore, the Nb content is preferably 0.5 to 2.5%, particularly preferably 0.5 to 1.4%.
- TCP topological close packed
- Titanium (Ti) contributes to strengthening of grain boundaries. In order to achieve this effect, Ti is preferably contained in an amount of 0.5% or more. However, when Ti is contained in excess of 2.0%, the hot workability and weldability of the alloy are significantly reduced. Therefore, the Ti content is preferably 0.0 to 2.0%, particularly preferably 0.7 to 1.5%.
- Carbon (C) is bonded to Nb, W and Ti for forming MC type carbides.
- MC type carbide suppresses the movement of grain boundaries by a pinning effect.
- the C content is preferably 0.5 to 1.2%, particularly preferably 0.7 to 1.0%.
- Co is an element that lowers the stacking fault energy, adjusts the distribution of carbides, and refines the crystal grain size of the Fe—Cr heat resistant alloy.
- the Co content is preferably 2.5 to 5.0%, particularly preferably 3.0 to 4.5%.
- the Co content is preferably 2.5 to 4.5%, particularly preferably 3.0 to 4.0%. It is.
- Mo and W are added to improve the strength of the alloy at high temperature by solid solution strengthening in the matrix phase.
- the lower limit of the content of these elements is preferably 0.5% for Mo and 3.0% for W.
- the upper limit of the content of these elements is preferably 2.0% for Mo and 6.0% for W. . Therefore, the Mo content is preferably 0.5 to 2.0%, particularly preferably 1.0 to 1.5%.
- the W content is preferably 3.0 to 6.0%, particularly preferably 3.0 to 5.0%.
- the W content is preferably 4.0 to 6.0%, particularly preferably 4.0 to 5.0%. It is.
- Chromium (Cr) Cr is an effective element for improving oxidation resistance and corrosion resistance. Further, Cr contributes to improvement of hot workability in the alloy defined in the present invention. In order to achieve these effects, Cr is preferably contained in an amount of 15% or more. On the other hand, when Cr is excessively contained, a harmful TCP phase is formed. Therefore, the Cr content is preferably in the range of 15 to 30%, particularly preferably in the range of 24.5% to 28.5%. In order to maintain high temperature creep characteristics and corrosion resistance to molten glass, the Cr content is preferably in the range of 22% to 30%, and more preferably in the range of 24.5% to 28.5%. It is. The oxidation resistance of alloys with a high chromium content is about the same level as alloys with or without iron (15% to 25% iron).
- alloys A to G having the compositions shown in Table 1 below were manufactured by melt casting.
- Alloy A is a conventional example
- Alloys B to E are examples included in the first aspect of the present invention
- Alloys F and G contain elements exceeding the range specified in the present invention. It is a comparative example having a quantity.
- each alloy was tested by static immersion in molten glass at 1050 ° C. for 100 hours to evaluate the corrosion resistance.
- the corrosion rate calculated by the average of the corrosion depth is shown in Table 2.
- the alloys B to E of the present invention are slightly better than those of the conventional alloy A and the comparative alloys F and G.
- about the corrosion rate by a molten glass it showed with the amount of corrosion per year, and is an estimated value based on an experimental value.
- the corrosion rate by molten glass is calculated by calculating the amount of corrosion per year using experimental values for 100 hours.
- FIG. 1 is a graph showing the results of a compression test and a corrosion test at 1050 ° C. performed on Ni—Cr—Fe based alloys of Examples, Conventional Examples and Comparative Examples of the present invention.
- the 0.2% compressive yield strength at 1000 ° C. is 100 MPa or more, and 1050 ° C.
- the rate of stable compression creep at 35 MPa is about 7.5 ⁇ 10 ⁇ 8 s ⁇ 1 or less, and the estimated corrosion rate in molten glass at 1050 ° C. is about 10 mm / year or less.
- the Ni—Cr—Fe based cast alloy according to the second aspect of the present invention uses the alloys B and DE having the compositions shown in Table 1 as examples. The composition range is not included. According to the second aspect of the present invention, compared with the first aspect of the present invention, it has superior high temperature strength, creep resistance, and corrosion resistance in molten glass. That is, according to the Ni—Cr—Fe based cast alloy of the second aspect of the present invention, as shown in Table 2 and FIG. 1, the 0.2% compressive yield strength at 1000 ° C. is 100 MPa or more, The rate of stable compression creep at 35 MPa at 1050 ° C. is less than about 5.5 ⁇ 10 ⁇ 8 s ⁇ 1 and the estimated corrosion rate in molten glass at 1050 ° C. is less than about 8.5 mm / year.
- Ni—Cr—Fe based cast alloy of the present invention is equivalent to or more than the conventional alloy and the comparative alloy outside the scope of the present invention in terms of high temperature strength, creep resistance, and corrosion resistance in molten glass. It is clear that it is excellent (FIG. 1).
- a novel Ni—Cr—Fe based cast alloy for parts in contact with molten glass is provided.
- An example of a component that comes into contact with molten glass is a centrifugal spinner for fiberizing molten glass in a rotating fiberizing process.
- the Ni—Cr—Fe based cast alloy of the present invention is not limited to this, and is a high temperature liquefied inorganic substance similar to molten glass, for example, an inorganic substance such as silicon or quartz, and this liquefied inorganic substance is used as a fiber. It can be applied to the use of manufacturing, preferably casting, a part that can be transformed.
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Abstract
Description
したがって、本発明は、高温の溶融ガラス中で改善された高温機械的強度と耐食性を有するニッケル-クロム-鉄基鋳造合金を提供する。
Cr:24.5~28.5%、Fe:15~25%、Co:3.0~4.5%、W:3.0~5.0%、Ti:0.7~1.5%、Nb:0.5~1.4%、Mo:1.0~1.5%、および、C:0.7~1.0%。
Cr:24.5~28.5%、Fe:15~25%、Co:3.0~4.0%、W:4.0~5.0%、Ti:0.7~1.5%、Mo:1.0~1.5%、および、C:0.7~1.0%。
(a)上記(1)、(2)、(4)、または(5)に記載のNi-Cr-Fe基鋳造合金を提供する工程と、
(b)前記合金を溶融させ、空気中で周囲温度まで前記合金を凝固させて熱鋳造の欠陥が存在しない物品を得る工程と、
(c)前記合金の溶融開始温度より少なくとも20℃低い温度で前記物品を熱処理して最終物品を得る工程。
本発明の第1の態様のNi-Cr-Fe基鋳造合金によれば、表2および図1に示すように、1000℃での0.2%の圧縮降伏強度が100MPa以上であり、1050℃で35MPaでの安定した圧縮クリープの速度が約7.5x10-8s-1以下であり、1050℃での溶融ガラス中推定される腐食速度が約10mm/年以下である。
Claims (8)
- 溶融ガラスと接触する部品の製造に使用するのに適したNi-Cr-Fe基鋳造合金であって、質量パーセントで、
Cr:15~30%、
Fe:15~30%、
Co:2.5~5.0%、
W:3.0~6.0%、
Ti:0.0~2.0%、
Nb:0.5~2.5%、
Mo:0.5~2.0%、および、
C:0.5~1.2%、
を含有し、残部がニッケル及び不可避的不純物からなることを特徴とするNi-Cr-Fe基鋳造合金。 - 請求項1に記載のNi-Cr-Fe基鋳造合金において、各組成元素の含有率は、下記の少なくとも何れか一つ以上であることを特徴とするNi-Cr-Fe基鋳造合金。
Cr:24.5~28.5%、
Fe:15~25%、
Co:3.0~4.5%、
W:3.0~5.0%、
Ti:0.7~1.5%、
Nb:0.5~1.4%、
Mo:1.0~1.5%、および、
C:0.7~1.0%。 - 1000℃での0.2%の圧縮降伏強度が100MPa以上であり、
1050℃で35MPaでの安定した圧縮クリープの速度が約7.5x10-8s-1以下であり、
1050℃での溶融ガラス中推定される腐食速度が約10mm/年以下である、
ことを特徴とする請求項1又は2に記載のNi-Cr-Fe基鋳造合金。 - 溶融ガラスと接触する部品の製造に使用するのに適したNi-Cr-Fe基鋳造合金であって、質量パーセントで、
Cr:22~30%、
Fe:15~30%、
Co:2.5~4.5%、
W:4.0~6.0%、
Ti:0.0~2.0%、
Nb:0.5~1.4%、
Mo:0.5~2.0%、および、
C:0.5~1.2%、
を含有し、残部がニッケル及び不可避的不純物からなることを特徴とするNi-Cr-Fe基鋳造合金。 - 請求項4に記載のNi-Cr-Fe基鋳造合金において、各組成元素の含有率は、下記の少なくとも何れか一つ以上であることを特徴とするNi-Cr-Fe基鋳造合金。
Cr:24.5~28.5%、
Fe:15~25%、
Co:3.0~4.0%、
W:4.0~5.0%、
Ti:0.7~1.5%、
Mo:1.0~1.5%、および、
C:0.7~1.0%。 - 1000℃での0.2%の圧縮降伏強度が100MPa以上であり、
1050℃で35MPaでの安定した圧縮クリープの速度が約5.5x10-8s-1以下であり、
1050℃での溶融ガラス中推定される腐食速度が約8.5mm/年以下である、
ことを特徴とする請求項4又は5に記載のNi-Cr-Fe基鋳造合金。 - 以下の工程を含む回転繊維化プロセスで溶融ガラスを繊維化するためのスピナーとして使用するためのNi-Cr-Fe基鋳造合金を用いた鋳造品の製造方法。
(a)請求項1、2、4、又は5に記載のNi-Cr-Fe基鋳造合金を提供する工程と、
(b)前記合金を溶融させ、空気中で周囲温度まで前記合金を凝固させて熱鋳造の欠陥が存在しない物品を得る工程と、
(c)前記合金の溶融開始温度より少なくとも20℃低い温度で前記物品を熱処理して最終物品を得る工程。 - 請求項7に記載のNi-Cr-Fe基鋳造合金を用いた鋳造品の製造方法において、
前記熱処理工程(c)は、
1150℃から1250℃の間であって、前記合金の溶融開始温度より少なくとも20℃低い温度で、前記物品を2~4時間加熱する工程と、
550℃以下まで、毎分65℃~30℃の速度で前記物品を冷却し、その後、空気中で周囲温度まで前記物品を冷却する工程
を含むことを特徴とする鋳造品の製造方法。
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SI201731110T SI3517642T1 (sl) | 2016-07-27 | 2017-07-26 | Zlitina za ulivanje na podlagi niklja, kroma in železa |
JP2018530354A JP6746110B2 (ja) | 2016-07-27 | 2017-07-26 | ニッケル−クロム−鉄基鋳造合金 |
US16/320,831 US10934608B2 (en) | 2016-07-27 | 2017-07-26 | Nickel-chromium-iron-based casting alloy |
EP17834411.5A EP3517642B1 (en) | 2016-07-27 | 2017-07-26 | Nickel-chromium-iron-based casting alloy |
KR1020197005343A KR102380633B1 (ko) | 2016-07-27 | 2017-07-26 | 니켈-크로뮴-철-기반 주조 합금 |
ES17834411T ES2910091T3 (es) | 2016-07-27 | 2017-07-26 | Aleación de colada a base de níquel-cromo-hierro |
PL17834411T PL3517642T3 (pl) | 2016-07-27 | 2017-07-26 | Stop odlewniczy na bazie niklu, chromu i żelaza |
DK17834411.5T DK3517642T3 (da) | 2016-07-27 | 2017-07-26 | Nikkel-chrom-jern-baseret støbelegering |
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US11939646B2 (en) | 2018-10-26 | 2024-03-26 | Oerlikon Metco (Us) Inc. | Corrosion and wear resistant nickel based alloys |
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JPH10195566A (ja) * | 1996-12-26 | 1998-07-28 | Shinhoukoku Seitetsu Kk | 高温耐食性および耐酸化性に優れた遠心紡糸用Ni基合金 |
KR101280114B1 (ko) * | 2008-06-16 | 2013-06-28 | 신닛테츠스미킨 카부시키카이샤 | 오스테나이트계 내열 합금 및 이 합금으로 이루어지는 내열 내압 부재와 그 제조 방법 |
EP2860272B1 (en) * | 2012-06-07 | 2017-10-04 | Nippon Steel & Sumitomo Metal Corporation | Ni-BASED ALLOY |
-
2017
- 2017-07-26 SI SI201731110T patent/SI3517642T1/sl unknown
- 2017-07-26 US US16/320,831 patent/US10934608B2/en active Active
- 2017-07-26 WO PCT/JP2017/027051 patent/WO2018021409A1/ja unknown
- 2017-07-26 JP JP2018530354A patent/JP6746110B2/ja active Active
- 2017-07-26 PL PL17834411T patent/PL3517642T3/pl unknown
- 2017-07-26 DK DK17834411.5T patent/DK3517642T3/da active
- 2017-07-26 KR KR1020197005343A patent/KR102380633B1/ko active IP Right Grant
- 2017-07-26 EP EP17834411.5A patent/EP3517642B1/en active Active
- 2017-07-26 ES ES17834411T patent/ES2910091T3/es active Active
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US6266979B1 (en) | 1999-09-02 | 2001-07-31 | Johns Manville International, Inc. | Spinner disc alloy |
US20020073742A1 (en) | 2000-12-20 | 2002-06-20 | Johnson Walter A. | Spinner disc and rotary fiberization process |
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US11939646B2 (en) | 2018-10-26 | 2024-03-26 | Oerlikon Metco (Us) Inc. | Corrosion and wear resistant nickel based alloys |
Also Published As
Publication number | Publication date |
---|---|
EP3517642A1 (en) | 2019-07-31 |
US20190153572A1 (en) | 2019-05-23 |
US10934608B2 (en) | 2021-03-02 |
EP3517642B1 (en) | 2022-02-23 |
DK3517642T3 (da) | 2022-03-14 |
PL3517642T3 (pl) | 2022-05-02 |
JPWO2018021409A1 (ja) | 2019-05-23 |
ES2910091T3 (es) | 2022-05-11 |
KR102380633B1 (ko) | 2022-03-30 |
SI3517642T1 (sl) | 2022-05-31 |
KR20190065242A (ko) | 2019-06-11 |
JP6746110B2 (ja) | 2020-08-26 |
EP3517642A4 (en) | 2020-06-10 |
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