CN112154220A - Novel austenitic alloy - Google Patents
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- CN112154220A CN112154220A CN201980034146.9A CN201980034146A CN112154220A CN 112154220 A CN112154220 A CN 112154220A CN 201980034146 A CN201980034146 A CN 201980034146A CN 112154220 A CN112154220 A CN 112154220A
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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
- C22C19/053—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%
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- C22C1/02—Making non-ferrous alloys by melting
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- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- 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%
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- 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
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Abstract
The invention relates to an austenitic alloy comprising the following elements in weight%: c is less than or equal to 0.03; si is less than or equal to 1.0; mn is less than or equal to 1.5; s is less than or equal to 0.03; p is less than or equal to 0.03; cr 25.0 to 33.0; ni 42.0 to 52.0; mo 6.0 to 9.0; n is 0.07-0.11; cu is less than or equal to 0.4; the remainder is Fe and inevitable impurities; and in that the austenitic alloy satisfies the following conditions: eNi>1.864*ECr-19.92, wherein ECr＝[wt％Cr]+[wt％Mo]+1.5*[wt％Si]And E isNi＝[wt％Ni]+30*[wt％C]+30*[wt％N]+0.5*[wt％Mn]+0.5*[wt％Cu]. The invention also relates to a method of manufacturing and an object comprising said alloy. The alloy and objects made therefrom have less than 0.3% intermetallic phases after solidification.
Description
Technical Field
The present invention relates to austenitic alloys with high contents of Ni, Mo and Cr, which after solidification will have a low content of intermetallic phases (less than 0.3%). The invention also relates to the use of said austenitic alloy in different products and to a method for manufacturing such an alloy.
Background
Nickel-based alloys are used in many corrosive applications where the corrosion resistance and microstructural stability of current stainless steels are inadequate. However, these alloys have problems associated with them in that they tend to form micro-segregation during the solidification process, thereby forming deleterious intermetallic phases. These in turn lead to poor ductility and poor corrosion properties. By using certain manufacturing methods, such as remelting and soaking, it is possible to reduce the content of intermetallic phases, but these methods are very expensive.
Thus, there is a need for nickel-base alloys with low intermetallic phase content that can be produced by conventional metallurgical methods.
Disclosure of Invention
It is therefore an aspect of the present invention to solve or at least reduce the above problems. Accordingly, the present invention provides an austenitic alloy comprising, in weight percent (wt%):
the remainder is Fe and inevitable impurities;
and wherein the austenitic alloy satisfies the following conditions:
ENi>1.864*ECr-19.92
wherein
ECr＝[wt％Cr]+[wt％Mo]+1.5*[wt％Si]，
ENi＝[wt％Ni]+30*[wt％C]+30*[wt％N]+0.5*[wt％Mn]+0.5*[wt％Cu]。
An austenitic alloy as defined above or below will have a good corrosion resistance and a high ductility, since the austenitic alloy after solidification will contain less than 0.3% intermetallic phases, which means that less intermetallic phases will be present in the austenitic alloy. Intermetallics have a negative impact on any process performed after solidification.
The invention also relates to an object comprising an austenitic alloy as defined above or below. Examples of objects are, but are not limited to, tubes (tube), pipes (pipe), rods, hollow bodies, billets (billet), blooms, bars, wires, plates and sheets.
Furthermore, the invention provides a method for producing an austenitic alloy comprising the following elements in wt.%:
the remainder being Fe and unavoidable impurities,
wherein the austenitic alloy will have a content of intermetallic phases after solidification of less than 0.3%,
wherein the method comprises the steps of:
-providing a melt;
-analyzing said melt to obtain the weight% (wt%) of the elements contained therein;
-substituting the values obtained from the analysis into the following equation:
ENi>1.864*ECr-19.92
wherein
ECr＝[wt％Cr]+[wt％Mo]+1.5*[wt％Si]，
ENi＝[wt％Ni]+30*[wt％C]+30*[wt％N]+0.5*[wt％Mn]+0.5*[wt％Cu]
-optionally adding one or more alloying elements to the austenitic alloy until the equation is satisfied;
-solidifying the austenitic alloy.
By incorporating the above steps into a conventional metallurgical manufacturing process, the final object obtained will have a low intermetallic phase content, e.g. < 0.3%.
Drawings
FIG. 1 discloses a Delong diagram, wherein the X-axis and Y-axis show the Cr equivalent (E)Cr) And Ni equivalent (E)Ni). The open squares in the figure are charges (heats) with less than 0.3% intermetallic phase in the interdendritic region after solidification, i.e. alloys meeting the conditions of the invention.
FIG. 2A shows an optical microscopy (LOM) photograph of the as-cast structure and intermetallic phases of an austenitic alloy (sample 3) outside the scope of the present invention;
FIG. 2B shows a LOM photograph of the as-cast structure and intermetallic phases of an austenitic alloy (sample 2) as defined above or below;
FIG. 3A shows a LOM photograph of the as-cast structure and intermetallic phases of an austenitic alloy (sample 4) outside the scope of the present invention;
fig. 3B shows a LOM photograph of the as-cast structure and intermetallic phases of the austenitic alloy (sample 7) as defined above or below.
Detailed Description
The invention relates to an austenitic alloy comprising the following elements in wt.%:
the remainder is Fe and inevitable impurities;
the austenitic alloy satisfies the following conditions:
ENi>1.864*ECr-19.92
wherein
ECr＝[wt％Cr]+[wt％Mo]+1.5*[wt％Si]，
ENi＝[wt％Ni]+30*[wt％C]+30*[wt％N]+0.5*[wt％Mn]+0.5*[wt％Cu]。
The austenitic alloys of the present invention will have a low fraction (amount) (less than 0.3%) of intermetallic phases formed in the interdendritic regions during the solidification process. The fraction is calculated by dividing the volume of the intermetallic phase in the interdendritic region by the total volume of the material. Examples of intermetallic phases are sigma, laves (laves phase) and chi phases.
Solidification is a phase change in which the alloy will transform from a liquid phase to a solid, crystal-structure phase. The solidification process starts with the formation of dendrites and micro-segregation will occur during the solidification process. Microsegregation is the uneven distribution of alloying elements between solidified dendrites that will promote the formation of deleterious intermetallic phases. The region between dendrites is called the interdendritic region. Typical solidification processes are, but are not limited to, casting such as ingot casting, continuous casting, and remelting.
An austenitic alloy as defined above or below will have good corrosion resistance and good ductility due to the low content of intermetallic phases in the intermetallic region. Therefore, the austenitic alloy will be well suited for use in applications requiring a high degree of corrosion resistance, such as the oil and gas industry, the petrochemical industry, and the chemical industry. Furthermore, according to an embodiment of the present invention, in order to provide better corrosion resistance of the alloy, the austenitic alloy as defined above or below may also satisfy the condition that the Critical Pitting Temperature (CPT) is greater than 88 ℃.
The invention also relates to an object comprising an austenitic alloy as defined above or below. Examples of objects are, but are not limited to, tubes, rods, hollow bodies, billets, blooms, bars, wires, plates, and sheets. Further examples include production tubing and heat exchanger tubes.
In the following, the contribution of the alloying elements of the austenitic alloy to the alloying properties as defined above or below is discussed. It should be noted that the alloying elements may also contribute to other properties of the austenitic alloy, even if not mentioned herein. The numbers given herein are given in weight percent (wt%):
carbon (C): less than or equal to 0.03wt percent
C is an impurity contained in the austenitic alloy. When the content of C exceeds 0.03 wt%, corrosion resistance is lowered due to precipitation of chromium carbide in grain boundaries. Thus, the content of C is 0.03 wt.% or less, for example 0.02 wt.% or less.
Silicon (Si): less than or equal to 1.0wt percent
Si is an element that can be added for deoxidation. However, Si promotes the precipitation of intermetallic phases such as sigma phase, and therefore Si is contained in an amount of 1.0 wt% or less, for example 0.5 wt% or less, for example 0.3 wt% or less. According to one embodiment, the lower limit of Si is 0.01 wt%.
Manganese (Mn): less than or equal to 1.5wt percent
Mn is often used to bind sulfur by forming MnS, thereby increasing the hot ductility of the austenitic alloy. Mn will also improve the strain hardening of the austenitic alloy during cold working. However, too high a Mn content will reduce the strength of the austenitic alloy. Therefore, the Mn content is set to 1.5 wt.% or less, for example 1.2 wt.% or less. According to one embodiment, the lower limit of Mn is 0.01 wt%.
Phosphorus (P): less than or equal to 0.03wt percent
P is an impurity contained in the austenitic alloy, and is known to have negative effects on hot workability and thermal cracking resistance. Thus, the content of P is 0.03 wt.% or less, for example 0.02 wt.% or less.
Sulfur (S): less than or equal to 0.03wt percent
S is an impurity contained in the austenitic alloy, which deteriorates hot workability. Thus, the allowable content of S is 0.03 wt.% or less, for example 0.02 wt.% or less.
Copper (Cu): less than or equal to 0.4wt percent
Copper can reduce the corrosion rate in sulfuric acid. However, Cu will reduce hot workability, so the maximum content of Cu is 0.4 wt% or less, for example 0.25 wt% or less. According to one embodiment, the lower limit of Cu is 0.01 wt%.
Nickel (Ni): 42.0 to 52.0 wt.%
Ni is an austenite stabilizing element. In addition, nickel will also contribute to stress corrosion cracking resistance in both chloride and hydrogen sulfide environments. Therefore, the Ni content is required to be 42.0 wt% or more. However, an increase in the Ni content will decrease the solubility of N, so the maximum content of Ni is 52.0 wt%. According to one embodiment of the present austenitic alloy, the Ni content is 43.0 wt.% to 51.0 wt.%, such as 44.0 wt.% to 51.0 wt.%.
Chromium (Cr): 25.0 to 33.0 wt.%
Cr is an alloying element that will improve pitting corrosion resistance. Furthermore, the addition of Cr will increase the solubility of N. When the content of Cr is less than 25.0 wt%, the effect of Cr is insufficient for corrosion resistance, and when the content of Cr exceeds 33.0 wt%, secondary phases as nitrides and intermetallic phases are formed, which adversely affect corrosion resistance. Thus, the content of Cr is 25.0 wt% to 33.0 wt%, for example 25.5 wt% to 32.0 wt%.
Molybdenum (Mo): 6.0 to 9.0 wt.%
Mo is an alloying element that effectively stabilizes the passive film formed on the surface of the austenitic alloy. In addition, Mo effectively improves pitting corrosion. When the content of Mo is less than 6.0 wt%, pitting corrosion resistance in a severe environment is not sufficiently high, and when the content of Mo exceeds 9.0 wt%, hot workability is deteriorated. Thus, the content of Mo is 6.0 wt% to 9.0 wt%, such as 6.1 wt% to 9.0 wt%, such as 6.4 wt% to 8.0 wt%.
Nitrogen (N): 0.07 wt% to 0.11 wt%
N is an effective alloying element for increasing the strength of austenitic alloys by utilizing solution hardening, and is also useful for improving structural stability. The addition of N will also improve the strain hardening during cold working. In order to have these effects in the present alloy, the content of N must exceed 0.07 wt%. However, when the content of N is more than 0.11 wt%, the flow stress will be too high for efficient hot working and the pitting corrosion resistance will be reduced. Therefore, the content of N is 0.07 wt% to 0.11 wt%.
The austenitic alloy as defined above or below may optionally comprise one or more of the following elements Al, Mg, Ca, Ce and B. These elements may be added during the manufacturing process to improve, for example, deoxidation, corrosion resistance, hot ductility or machinability. However, as is known in the art, the addition of these elements and their amounts will depend on which alloying elements are present in the alloy and which effects are desired. Thus, if added, the total content of these elements is ≦ 1.0 wt%, e.g., ≦ 0.5 wt%.
According to one embodiment, the austenitic alloy consists of all alloying elements mentioned above or below within the ranges mentioned above or below.
The term "impurities" as referred to herein refers to substances that, when an austenitic alloy is industrially produced, will contaminate the austenitic alloy due to raw materials such as ores and scrap, and due to various other factors in the production process, and are allowed to contaminate within a range that does not adversely affect the properties of the austenitic alloy as defined above or below. Examples of alloying elements that are considered as impurities are Co and Sn. Carbide-forming elements, such as Nb and W, are considered in the present invention as impurities and/or trace elements, which if present are present only at very low levels, meaning that they do not form any carbides and therefore do not have an effect on the final properties of the austenitic alloy.
The present invention also provides a method of making an austenitic alloy having the following elemental composition in weight percent (wt%):
the remainder being Fe and unavoidable impurities,
wherein the austenitic alloy will have a content of intermetallic phases after solidification of less than 0.3%,
wherein the method comprises the steps of:
-providing a melt;
-analyzing the melt to obtain the weight% of alloying elements contained therein;
-substituting the values obtained from the analysis into the following equation:
ENi>1.864*ECr-19.92
wherein
ECr＝[wt％Cr]+[wt％Mo]+1.5*[wt％Si]，
ENi＝[wt％Ni]+30*[wt％C]+30*[wt％N]+0.5*[wt％Mn]+0.5*[wt％Cu]
-optionally adding alloying elements to the melt until the equation is satisfied;
-solidifying the melt.
The inventors have surprisingly found through intensive studies that by incorporating the method into a conventional metallurgical manufacturing process, the object obtained thereof will have a low intermetallic phase content after solidification, which will have a positive effect on the results of the other metallurgical processes used.
According to one embodiment of the present method as defined above or below, said equation may also be used when designing the austenitic alloy, i.e. before the austenitic alloy is melted.
The melt analysis can be performed using, for example, X-ray fluorescence spectroscopy, spark discharge emission spectroscopy, combustion analysis, extraction analysis, and inductively coupled plasma emission spectroscopy. The elemental content obtained from the analysis is then substituted into the equation. If the condition (equation) is not satisfied, the alloying element is added until the equation is satisfied. When additional alloying elements are added, the melt may be analyzed again, and these steps may be repeated several times until the equation (condition) is satisfied.
According to yet another embodiment of the method, optionally a sample may be taken from the austenitic alloy after solidification to measure and verify the intermetallic phases.
According to one embodiment of the method as defined above or below, the solidification method is casting.
After the solidification step, the method may include conventional metal fabrication steps, such as hot working and/or cold working. The method may optionally include a heat treatment step and/or an aging step. Examples of hot working processes are hot rolling, forging and extrusion. Examples of cold working processes are pilgering, drawing and cold rolling. Examples of heat treatment processes are soaking and annealing, such as solution annealing or quench annealing. Examples of objects that can be obtained by the method as defined above or below are, but not limited to, tubes, pipes, bars, rods, hollow bodies, billets, blooms, bars, wires, plates and sheets.
The invention is further illustrated by the following non-limiting examples.
Examples
Example 1
The alloys of table 1 were made by melting in a 270kg HF (high frequency) induction furnace and then cast into ingots by casting into 9 "molds. After casting and solidification, the mold was removed and the ingot was quenched in water. The composition of the experimental charge, the Cr and Ni equivalents and the fraction of intermetallic phases in the interdendritic region are given in tables 1 and 2.
Samples were cut from the upper part of the ingot, metallographically prepared and etched in Beraha etchant 9 b. The corrosion shows a dendritic structure and intermetallic phases. To study the intermetallic phases, an optical microstructure (LOM) study (Nikon optical microscope) was performed. The percentage (%) of intermetallic phases in the interdendritic regions was measured by using a 10 x 10 row plug-in grid at 200 x magnification, then counting the number of intersections in the grid that hit the intermetallic phases in the interdendritic regions and dividing by the total number of intersections. A total of 10 randomly located fields of view on the metallographic sample were measured to determine the intermetallic phase fraction in the interdendritic region.
Two typical examples of microstructures, one with intermetallic phases in the interdendritic regions, see fig. 2A, and one without intermetallic phases in the interdendritic regions, see fig. 2B. The composition of the intermetallic phases was measured by EDS (energy dispersive X-ray spectroscopy) in a FEG-SEM (field emission gun-scanning electron microscope), Zeiss Σ IGMA VP. Fig. 2A shows (sample 3), which is outside the present invention, and it can be seen that its amount of intermetallic phase after solidification is more than 0.3%. Fig. 2B shows the invention (sample 2) and it can be seen that it has no intermetallic phases after solidification. Further examples are shown in fig. 3A to 3B, where fig. 3A (sample 4) is outside the scope of the present invention, while fig. 3B (sample 7) is within the scope of the present invention and has no intermetallic phases.
The Cr-and Ni-equivalents of the charge are plotted in FIG. 1, which shows a Delong diagram, where the X-axis and Y-axis are the Cr equivalents (E)Cr) And Ni equivalent (E)Ni). The open squares in the figure are charges with less than 0.3% intermetallic phase in the interdendritic region after solidification, i.e. alloys fulfilling the conditions according to the invention.
TABLE 2 measured Intermetallic Phase (IP) fractions for each sample
Example 2
Three samples were obtained from cold rolled and solution annealed materials and were treated with 3M MgCl according to ASTM G1502Pitting corrosion was tested as an electrolyte. The following table shows the average pitting temperature (CPT) values for each charge:
table 3: CPT of each sample
| Sample (I) | CPT |
| 1 | 95 |
| 2 | 106 |
| 3 | 73 |
| 4 | 68 |
| 5 | 77 |
| 6 | 84 |
| 7 | 84 |
| 8 | 75 |
| 9 | 93 |
| 10 | 96 |
| 11 | 85 |
| 12 | 89 |
| 13 | 90 |
| 14 | 90 |
| 15 | 92 |
| 16 | 95 |
Claims (13)
1. An austenitic alloy comprising the following elements in weight%:
C≤0.03；
Si≤1.0；
Mn≤1.5；
S≤0.03；
P≤0.03；
cr 25.0 to 33.0;
ni 42.0 to 52.0;
mo 6.0 to 9.0;
N 0.07–0.11；
Cu≤0.4；
the remainder is Fe and inevitable impurities;
characterized in that the austenitic alloy satisfies the following conditions:
ENi>1.864*ECr-19.92
wherein
ECr＝[wt％Cr]+[wt％Mo]+1.5*[wt％Si]，
ENi＝[wt％Ni]+30*[wt％C]+30*[wt％N]+0.5*[wt％Mn]+0.5*[wt％Cu]。
2. The austenitic alloy of claim 1, wherein the Cu content is ≦ 0.25 wt%.
3. The austenitic alloy of any of claims 1 to 2, wherein the Mn content is ≤ 1.2 wt%.
4. The austenitic alloy of any of claims 1 to 3, wherein the Si content is ≦ 0.5 wt%.
5. The austenitic alloy of any of claims 1 to 4, wherein the Cr content is between 25.5 wt% and 32.0 wt%.
6. The austenitic alloy of any of claims 1 to 5, wherein the Mo content is between 6.1 wt% and 9.0 wt%, such as between 6.4 wt% and 8.0 wt%.
7. The austenitic alloy of any of claims 1 to 6, wherein the Ni content is between 43.0 wt% and 51.0 wt%, such as between 44.0 wt% and 51.0 wt%.
8. The austenitic alloy of any of claims 1 to 7, wherein the austenitic alloy has a CPT greater than 88 ℃ (ASTM G150, with 3M MgCl2As an electrolyte).
9. A method of manufacturing an austenitic alloy having the following elemental composition in weight%:
C≤0.03；
Si≤1.0；
Mn≤1.5；
S≤0.03；
P≤0.03；
cr 25.0 to 33.0;
ni 42.0 to 52.0;
mo 6.0 to 9.0;
N 0.07–0.11；
cu is less than or equal to 0.4; 0.01 to 0.4
The remainder is Fe and inevitable impurities;
the austenitic alloy will have an intermetallic content of less than 0.3% after solidification,
wherein the method comprises the steps of:
-providing a melt;
-analyzing the melt to obtain the weight% of the elements contained therein;
-substituting the value obtained from the melt into the following equation:
ENi>1.864*ECr-19.92
wherein
ECr＝[wt％Cr]+[wt％Mo]+1.5*[wt％Si]，
ENi＝[wt％Ni]+30*[wt％C]+30*[wt％N]+0.5*[wt％Mn]+0.5*[wt％Cu]
-optionally adding alloying elements to the melt until the equation is satisfied;
-solidifying the melt.
10. The method of claim 9, wherein the solidification method is casting.
11. The method according to claim 9 or 10, wherein the method further comprises at least one thermal processing step.
12. The method of any of claims 9-11, wherein the method further comprises at least one cold working step.
13. The method according to any one of claims 9 to 12, wherein the method further comprises at least one heat treatment step.
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| EP18173865 | 2018-05-23 | ||
| EP18173865.9 | 2018-05-23 | ||
| PCT/EP2019/063297 WO2019224287A1 (en) | 2018-05-23 | 2019-05-23 | New austenitic alloy |
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| EP (1) | EP3797179B1 (en) |
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| US20200087759A1 (en) * | 2016-06-28 | 2020-03-19 | Nippon Steel & Sumitomo Metal Corporation | Austenitic Alloy Material and Austenitic Alloy Pipe |
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2019
- 2019-05-23 KR KR1020207033439A patent/KR20210014631A/en not_active Application Discontinuation
- 2019-05-23 CN CN201980034146.9A patent/CN112154220B/en active Active
- 2019-05-23 US US17/054,648 patent/US20210079499A1/en not_active Abandoned
- 2019-05-23 WO PCT/EP2019/063297 patent/WO2019224287A1/en unknown
- 2019-05-23 EP EP19724876.8A patent/EP3797179B1/en active Active
- 2019-05-23 JP JP2020565265A patent/JP2021525310A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US4400211A (en) * | 1981-06-10 | 1983-08-23 | Sumitomo Metal Industries, Ltd. | Alloy for making high strength deep well casing and tubing having improved resistance to stress-corrosion cracking |
| CN1977060A (en) * | 2004-06-30 | 2007-06-06 | 住友金属工业株式会社 | Fe-Ni alloy pipe stock and method for manufacturing the same |
| CN1993488A (en) * | 2004-08-02 | 2007-07-04 | 住友金属工业株式会社 | Weld joint and weld material thereof |
| CN101583733A (en) * | 2007-01-15 | 2009-11-18 | 住友金属工业株式会社 | Austenitic stainless steel welded joint and austenitic stainless steel welding material |
| CN101613833A (en) * | 2008-06-25 | 2009-12-30 | 宝山钢铁股份有限公司 | Peracidity deep-well Ni base alloy tubing and casing and manufacture method |
| CN102686757A (en) * | 2009-12-10 | 2012-09-19 | 住友金属工业株式会社 | Austenitic heat-resistant alloy |
| CN105723009A (en) * | 2013-11-12 | 2016-06-29 | 新日铁住金株式会社 | Ni-cr alloy material and oil well seamless pipe using same |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3797179B1 (en) | 2024-01-17 |
| CN112154220B (en) | 2022-07-08 |
| US20210079499A1 (en) | 2021-03-18 |
| EP3797179C0 (en) | 2024-01-17 |
| JP2021525310A (en) | 2021-09-24 |
| EP3797179A1 (en) | 2021-03-31 |
| KR20210014631A (en) | 2021-02-09 |
| WO2019224287A1 (en) | 2019-11-28 |
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