CN111279003B - Low-temperature superplastic deformation titanium alloy sheet material - Google Patents
Low-temperature superplastic deformation titanium alloy sheet material Download PDFInfo
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Abstract
The technical result achieved by the implementation of the invention is the production of sheets from titanium alloys, the chemical composition of which is best balanced with the production capacity of the known current techniques of end products having low-temperature superplastic deformation characteristics. This result is achieved by a low temperature superplastically deforming sheet material based on a titanium alloy comprising: 4.5-5.5Al, 4.5-5.5V, 0.1-1.0Mo, 0.8-1.5Fe, 0.1-0.5Cr, 0.1-0.5Ni, 0.16-0.25O, and the balance titanium and impurities, wherein the molybdenum structure equivalent value [ Mo ] equivalent is higher than 5, and the aluminum structure equivalent value [ Al ] equivalent is lower than 8; the equivalent weight is determined using the formula: [ Mo ] equivalent ═ Mo ] + [ V ]/1.5+ [ Cr ] × 1.25+ [ Fe ] × 2.5+ [ Ni ]/0.8; [ Al ] equivalent ═ Al ] + [ O ] x 10+ [ Zr ]/6.
Description
Technical Field
Disclosed herein are materials and products, such as sheet materials and sheet semi-finished products, including titanium alloys, suitable for product preparation by processes including low temperature superplastic forming (SPF) at a temperature of 775 ℃. The material and product can be used as a cost effective alternative to sheet products made from Ti-6Al-4V alloys.
Background
The term "superplastic forming" generally applies to the process of superplastic forming of materials (alloys) beyond the conventional limit of plastic strain (over 500%). SPF can be applied in limited temperature and stressCertain materials exhibit superplastic properties over a range of transmission rates. For example, titanium alloy sheets can typically be formed at temperatures in the range of about 3-10 ℃ in the range of about 900 to 1010 ℃-4s-1Is superplastic formed (deformed) at a strain rate of (f).
From a production point of view, significant advantages are obtained due to the reduced forming temperature at SPF. For example, a reduction in SPF forming temperature can result in a reduction in mold cost, an increase in its life, and can potentially result in the introduction of less expensive steel dyes. In addition, the formation of oxygen rich layers (α case) and scale can be mitigated, thereby improving product yield and reducing or eliminating the need for chemical etching. In addition, the advantage of retaining the presence of finer grains after SPF operation is complete may result in lower deformation temperatures, which may result in limiting grain growth.
Currently, there are two known methods to improve the superplastic forming capability of titanium alloy sheet materials. The first involves developing a special thermomechanical process to produce fine grains of sizes just between 2 μm and 1 μm and finer, resulting in enhanced grain boundary sliding. Specifically, there is a known method of manufacturing a sheet deformed at a temperature lower than that of a conventional product formed of a Ti-6Al-4V material (patent RF No. 2243833, IPC B21B1/38, published on 10/1/2005).
The second approach involves developing a new titanium alloy sheet material system that exhibits superplasticity at coarser material grain sizes because:
-two-phase volume fraction and morphological enhancement,
the diffusion process is faster, which accelerates the grain boundary sliding due to the presence of e.g. Fe and Ni as fast diffusants in the alloy.
the-Beta Transition Temperature (BTT) is relatively low.
Thus, with effective selection of the alloy chemical composition, satisfactory low-temperature superplastic forming (deformation) properties can be obtained without using special processing techniques required for ultra-fine grain formation.
Two-phase (α + β) -titanium alloys are divided into molybdenum structural equivalents-m o equivalents-equal to 2.5 up to 10% of the alloy according to the level of alloying element addition (Kolachev b.a., Polkin i.s., Talalayev v.d. titanium alloys of variaous centers: Reference book, moscow. vils.2000.316p. -p.13-16). Such alloys are typically alloyed with aluminum and a beta-stabilizer to retain the beta-phase. In annealed alloys belonging to this class, the amount of β -phase may vary between 5% and 50%. Thus, the mechanical properties vary over a relatively wide range. These alloys have found widespread use in both Russia and foreign countries due to the successful addition of alloying elements, particularly the Ti-6A1-4V alloys (Materials Properties Handbook: Titanium alloys. R. Boyer, G.Welsch, E.Collings. ASM International,1998.1048p. -p.486-488). In such alloys, aluminum tends to increase strength and heat resistance, while vanadium is one of the few elements that not only increases strength properties but also improves plasticity. Alloys belonging to the Ti-6A1-4V group are used for the production of bars, tubes, parts (sections), open and closed dye forgings, plates, sheets, strips and foils. It is used for the preparation of welded and prefabricated structures in aeronautical vehicles, various aeronautical and rocket structural members, and for the preparation of medical implants for applications in traumatology, orthopedics and dentistry.
There is a known method of manufacturing a semi-finished product of a titanium alloy sheet suitable for low-temperature superplastic forming from VT5 alloy, which is an analogue of Ti-6Al-4V alloy (patent RF No. 2224047, IPC 22F1/18, B21B3/00, published 2/20/2004). The method allows the production of titanium alloy sheet semi-finished products with uniform submicron crystalline structure (grain size below 1 μm) suitable for low-temperature superplastic forming. This approach can be costly, inefficient, and requires the availability of specialized equipment.
Ti-6A1-4V alloys are known to have a sub-microcrystalline structure that is produced by Severe Plastic Deformation (SPD) using a full-scale forging technique and exhibits superplastic properties. The alloy microstructure is defined by: alpha-phase and beta-phase grains and subgrains with an average size of 0.4 μm, high levels of lattice internal stress and elastic distortion (as evidenced by non-uniform diffraction contrast), and high density dislocations on structural images obtained by electron microscopy (S. ZHEREBTsov, G. Salishchev, R. Galeyev, K. Maekawa, Mechanical properties of Ti-6Al-4V titanium alloy with sub-microscopic crystal structure produced by silicon layer transformation// Materials transformations.2005; V.46(9):2020 2025). To make sheet semi-finished products from this alloy requires non-intensive and low-cost SPD operations using full-face forging techniques, which significantly increases the price of the finished product.
There are known methods of manufacturing thin sheets from two-phase titanium alloys and products from said sheets. The method involves preparing a sheet semi-finished product from an alloy having the following% wt. element content: 3.5-6.5Al, 4.0-5,5V, 0.05-1.0Mo, 0.5-1.5Fe, 0.10-0.2O, 0.01-0.03C, 0.005-0.07Cr, 0.01-0.5Zr, 0.001-0.02N and the balance of titanium; and the chemical composition was adjusted with the following values: aluminium
And molybdenum
Strength equivalent (patent RF No. 2555267, IPC C22F1/18B21B3/00, published on 7/10/2015) -prototype.
The sheet semi-finished product manufactured in this patent with a thickness of less than 3mm may not be suitable for industrial production due to the low stability of the properties required for SPF. The reason is that the use of strength equivalents as a tuning factor for the alloy chemistry does not allow the desired tuning and proper relationship between the alloying elements in the alloy and the alloy structural properties required for SPF performance of the sheet blank. In addition, the presence of Si and Zr in the alloy can form silicides on the grain surfaces, thereby hindering intergranular sliding and causing processing instability.
Disclosure of Invention
Disclosed herein is the manufacture of (α + β) -titanium alloy sheet material with low temperature superplastic forming capability with a grain size exceeding 2 μm. The sheet material exhibits stable properties and in the example is a cost-effective choice of a sheet semi-finished product made of a Ti-6Al-4V alloy with finer grains.
Disclosed herein is the manufacture of sheet materials from titanium alloys that are effectively balanced in chemical composition and manufacturability based on known conventional manufacturing techniques for finished products exhibiting low temperature superplastic forming properties.
Drawings
Fig. 1 and 2 show the alloy structure in the initial condition.
Figures 3, 4 and 5 are load curves obtained during SPF.
FIG. 6 is a graph showing true stress vs. strain curves at strain levels of 0.2 and 1.1 (machine direction) according to [ Mo ] equivalent.
Detailed Description
Examples of low temperature superplastic formed sheet materials can be made from titanium alloys having the following% wt. elemental contents: 4.5-5.5Al, 4.5-5.5V, 0.1-1.0Mo, 0.8-1.5Fe, 0.1-0.5Cr, 0.1-0.5Ni, 0.16-0.25O, the remainder being titanium and the balance elements, and wherein the molybdenum structural equivalent [ Mo ] equivalent >5 and the aluminum structural equivalent [ Al ] equivalent < 8; the equivalent value is calculated according to the following expression:
[ Mo ] equivalent [ + [ V ]/1.5+ [ Cr ] × 1.25+ [ Fe ] × 2.5+ [ Ni ]/0.8
[ Al ] equivalent ═ Al ] + [ O ] x 10+ [ Zr ]/6.
The low-temperature superplastic forming sheet material has a structure composed of crystal grains having a size of 8 μm or less.
The low temperature superplastic forming sheet material may exhibit superplastic properties at a temperature of 775 ± 10 ℃.
The low temperature superplastic formed sheet material exhibits an alpha/beta ratio of from 0.9 to 1.1 at a temperature of 775 ± 10 ℃.
A low temperature superplastic formed sheet material, wherein the amount of alloying elements diffusible between an alpha-phase and a beta-phase during SPF is equal to at least 0.5%, and which is determined by the following relation:
wherein:
the amount,% wt, of diffusible alloying elements in the material during Q-SPF.
n-the amount of alloying elements in the material,
absolute value of change,% wt. of the content of alloying elements of beta-phase and alpha-phase in the process of |. DELTA.m | -SPF.
| Δ m | -is calculated by:
|Δm|＝(mβ1-mα1)-(mβ2-mα2)，％wt.
wherein:
the content,% wt. of the alloying elements of the beta-phase before m beta 1-SPF,
the content,% wt. of the alloying elements of the beta-phase after m beta 2-SPF,
content,% wt. of alloying elements of the alpha-phase before m alpha 1-SPF,
content,% wt. of alloying elements of the alpha-phase after m alpha 2-SPF.
In the examples herein, the provided sheet materials exhibit a set of high processing and structural properties. This is achieved by an efficient selection of the alloying elements and their proportions in the material alloy.
Group a-stabilizers.
Aluminum, which is used in substantially all commercial alloys, is the most effective reinforcing agent and increases the strength and heat resistance of titanium. Oxygen increases the allotropic transformation temperature of titanium. The presence of oxygen in the range of 0.16% to 0.25% increases the strength of the alloy and does not have a significant negative impact on plasticity.
Beta-stabilizers (V, Mo, Cr, Fe, Ni) are widely used in commercial alloys.
Vanadium in an amount of 4.5% to 5.5%, iron in an amount of 0.8% to 1.5%, and chromium in an amount of 0.1% to 0.5% increase the strength of the alloy and have relatively little or no negative effect on the plasticity.
The introduction of molybdenum in the range of 0.1% to 1.0% ensures that it is almost completely to completely dissolved in the alpha-phase, so that the desired strength properties can be achieved in the examples with little to zero negative effect on plasticity.
The alloy provided contains iron in an amount of 0.8% to 1.5 or 1.0% to 1.5% and nickel in an amount of 0.1% to 0.5%. These elements are the most diffusive β -stabilizers, which have a positive effect on intergranular slip in SPF.
Among the structural factors having an effect on SPF efficiency, the first factor to be distinguished is that the grain size of the provided material does not exceed 8 μm (experimental data).
It is known that superplastic flow of materials can occur due to phase transformation in two-phase titanium alloys provided that the alpha/beta ratio at SPF temperatures is close to 1(Kaibyshev o. superplastic properties of commercial alloys. moshow. metallic. 1984. p.179-218.). This promotes the formation of equiaxed structures, which facilitate inter-grain sliding. The driving force for structural spheriodization is the tendency of surface energy to decrease. The intergranular boundary growth caused by the increase of the β -phase causes a change in the surface energy level at the intergranular boundary, which in turn causes activation of spheroidization. To have the desired amount of beta-phase at an alpha/beta ratio approaching 1 during SPF, the molybdenum structural equivalent [ Mo ] equivalent value should be greater than 5 and the aluminum structural equivalent [ Al ] equivalent value should not exceed 8. Furthermore, aluminum equivalent values exceeding the above values lead to an increase in BTT and thus an increase in SPF temperature.
The optimum temperature to produce superplastic properties of the provided materials is equal to 775 ± 10 ℃.
The amount of alloying elements that can diffuse between the alpha-and beta-phases should be not less than 0.5%. This is due to the fact that: the activation energy of the grain boundary diffusion is smaller than that of the volume diffusion, and the diffusion transport of atoms is performed at the grain boundaries. Those regions of the grain boundaries are affected by normal tensile stress and exhibit an increase in vacancy concentration. Those regions affected by compressive stress exhibit a smaller vacancy concentration: resulting in a concentration difference that causes direct diffusion of vacancies. Since vacancy migration involves exchange with atoms, the latter will move in the opposite direction, causing increased intergranular sliding.
Examples
For research purposes, a sheet blank with a thickness of 2mm was used. To make sheet material, six experimental alloys of various chemical compositions as shown in table 1 were melted.
Sheet material of 2mm thickness was manufactured according to known manufacturing methods aimed at superplastic forming. The material was subjected to annealing at a temperature of 720 ℃ for 30 minutes, followed by subsequent air cooling, before testing for superplastic properties. After the processing steps are completed, samples are taken from the sheet in the machine and cross directions for tensile strength testing at room temperature and elevated temperatures, and then the samples are subjected to general testing at room temperature to determine strength, elastic and plastic properties.
Evaluation of the material structure in the initial condition (fig. 1 and 2) shows that the structure is similar to an equiaxed structure and is composed mainly of alpha-phase and beta-phase alternating grains of the element which appear darker (alpha) or lighter (beta). It should be noted that as the [ Mo ] equivalent in the alloy increases, the volume fraction of the beta-phase grains tends to increase from the estimated alpha/beta ratio of 2/1 in alloy 2 to a value near 1/1 in alloys 3 and 4. The average size of the phase grains measured on the microstructure photograph by the intercept method tended to increase with the [ Mo ] equivalent increase and was in the range of 2.8 to 3.8 μm (the grain size of alloy 2 was determined to be the smallest). It should be noted that the grain structure of material 1 is less uniform in the initial condition compared to the other experimental alloys. In addition to the equiaxed grains, material 1 also shows regions consisting of sufficiently large elongated grains. It may also be noted that the morphology of the beta-phase varies from alloy to alloy in some manner. Alloy 2 has a minimum amount of alloying elements and the beta-phase is mainly located as individual clusters between the alpha-phase particles; but the beta-phase has a well-defined coherence starting from alloy 5 and, in addition to grain texture, it is shaped as a relatively thin layer between the alpha-phase grains. As the [ Mo ] equivalent increases, these layers tend to thicken.
Comparative examples
At SPF (temperature 775 ℃, and 3X 10)-4s-1Strain rate, sheet longitudinal) post-forging (narrow) state (reduced portion) and non-forging state (head region) show that deformation of the narrow portion causes some grain growth-compared to a nearly non-forged head, and composition evolution from more complex shaped alpha-and beta-phase grains.
Evaluation of grain size showed that in the most beta-stabilizer added alloys, the addition of alloying elements did not significantly affect the size of the phase grains and ranged between 3.5 ± 0.5 μm (unforged part) and 4 ± 0.5 μm (forged part). Meanwhile, in the case of alloy 2 having the smallest content of alloying elements, the grain size in the reduced portion was almost two-fold increased as much as 5 μm and more compared to the initial condition.
Checking the distribution of alloying elements between the alpha-phase and the beta-phase in the material by an electron microprobe analysis (EMPA) method under initial conditions and investigation after testing of superplastic properties; the examination was performed on the forged reduced portion and the head portion of the longitudinal sample, and the results are shown in tables 2, 3, and 4.
The amount of diffusible alloying elements in the material during SPF is determined by the following formula:
wherein:
the amount,% wt, of diffusible alloying elements in the material during Q-SPF.
n-the amount of alloying elements in the material,
absolute value of change,% wt. of the content of alloying elements of the alpha-phase and beta-phase in the process, | Δ m | -SPF.
| Δ m | -is calculated by:
|Δm|＝(mβ1-mα1)-(mβ2-mα2)，％wt.
wherein:
the content,% wt. of the alloying elements of the beta-phase before m beta 1-SPF,
the content,% wt. of the alloying elements of the beta-phase after m beta 2-SPF,
content,% wt. of alloying elements of the alpha-phase before m alpha 1-SPF,
content,% wt. of alloying elements of the alpha-phase after m alpha 2-SPF.
Table 4 includes calculated data relating to the amount of diffusible alloying elements in the SPF process.
Analysis of the changes in the alpha-phase and beta-phase in the investigated wrought sheet materials demonstrated a greater difference in the alloying element content between the alpha-and beta-phases in the reduced portion of the sample compared to the sample head that was not plastically deformed (tables 2, 3, and 4).
The EMPA results obtained were also used to evaluate the phase volume fraction in the material at the superplastic property test temperature of 775 ℃ and are shown in Table 5.
The load curves obtained during the test are shown in figures 3, 4 and 5.
Alloy properties under superplasticity testing are shown in table 6.
The true stress vs. strain curves as a function of [ Mo ] equivalent at strain rates of 0.2 and 1.1 (machine direction) are shown in FIG. 6.
The material 1 (fig. 3) with the lowest content of alloying elements has the most unstable SPF process at a temperature of 775 ℃, which is described by the general waviness of the stress-strain curve caused by the formation of the floating neck (floating neck). This material performance at SPF is due to the relatively large initial grains (over 2.5 μm), which have high growth rates (up to 5 μm) at SPF, the α/β ratio (2/1) is not efficient and results in activation of intra-grain sliding, which is less preferred for SPF-instead of efficient inter-grain sliding.
Material 2 (fig. 3) has more beta-stabilizer addition, so the instability of the SPF process in the form of stress-strain curve waviness is reduced compared to alloy 1 due to the increase of beta-phase volume fraction in the structure. Moreover, due to the evolution of dynamic recrystallization in the region of the incompletely machined structure (presence of elongated grains), no significant hardening was observed with a strain degree in the range of 0.6 to 0.8, and this was not typical for all other alloys under investigation.
The materials 3, 5 and 6 (fig. 4, 5) with the highest content of beta-stabilizer, except for molybdenum (alloy 5), chromium (alloy 6), have improved cohesion and easier intergranular sliding due to the increase of beta-phase in the alloy structure, which is described as the waviness of the stress-strain curve is smaller compared to materials 1 and 2; also the hardening was more pronounced with increasing true strain (table 3, fig. 6). This waviness remains at a strain level of up to 0.6, particularly in the transverse test, which can be attributed to the sheet initial texture and not having a sufficiently effective α/β ratio (3 close to 3 to 2). The absence of chromium in material 6 has an effect on the stress-strain curve compared to material 3 to a lesser extent than the absence of molybdenum in material 5. One of the reasons may be because molybdenum addition has a stronger impact on the stability of the SPF process than chromium addition (which is 2 to 2.5 times or less).
Material 4 contains the maximum amount of beta-stabilizer and is additionally alloyed with 0.3% nickel; it exhibits a more stable superplastic behaviour both in the transverse and longitudinal directions at a temperature of 775 ℃, minimal stress at the start of flow, absence of significant waviness and monotonic hardening with increasing strain. This is due to the almost effective α/β ratio at deformation temperatures (1/1) and the maximum content of diffusible β -stabilizers (nickel, iron) compared to all alloys investigated, thus facilitating the mass transport process at intergranular sliding (total difference in alloying element content between α -phase and β -phase in SPF process over 1.9% wt.).
Among the alloys examined, material 4 showed the best results that fully met the material requirements (table 7). Constant strain rate and (775 + -7) DEG C test temperature (strain 3X 10)-4In/s) is shown in table 7 below.
A comparison of the mechanical properties of the annealed sheets is shown in table 8.
The data shown in tables 7 and 8 show that, as a result of the exemplary embodiment, sheet materials having a chemical composition effectively balanced with manufacturability were manufactured from titanium alloys based on known conventional manufacturing techniques for semi-finished products having grain sizes in excess of 2 μm and meeting requirements for aerospace materials.
It should be noted that products made in accordance with the present disclosure may have a variety of designs. The design provided in the specification should be considered as illustrative and not restrictive, and the limitations of the invention are determined by the claims provided.
Claims (4)
1. A low temperature superplastic forming sheet material made of a titanium alloy having the following% wt. elemental content: 4.5-5.5Al, 4.5-5.5V, 0.1-1.0Mo, 0.8-1.5Fe, 0.1-0.5Cr, 0.1-0.5Ni, 0.16-0.25O, the balance being titanium and the balance being elements, the structural equivalent of molybdenum [ Mo ] being >5 and the structural equivalent of aluminum [ Al ] being < 8; the equivalent value is calculated by the following expression:
[ Mo ] structural equivalent = [ Mo ] + [ V ]/1.5+ [ Cr ] × 1.25+ [ Fe ] × 2.5+ [ Ni ]/0.8
[ Al ] structural equivalent = [ Al ] + [ O ] x 10+ [ Zr ]/6,
wherein the low-temperature superplastically formed sheet material has a structure consisting of grains having a size of 8 μm or less.
2. The low temperature superplastic forming sheet material of claim 1, exhibiting superplastic properties at a temperature of 775 ± 10 ℃.
3. The low temperature superplastic forming sheet material of claim 1, exhibiting an α/β ratio of 0.9 to 1.1 at a temperature of 775 ± 10 ℃.
4. The low temperature superplastic forming sheet material of any of claims 1 to 3, wherein the amount of diffusible alloying elements between the alpha and beta phases in the SPF process is equal to at least 0.5% and is determined by the following relation:
wherein:
the amount,% wt, of diffusible alloying elements in the material during Q-SPF.
n-the amount of alloying elements in the material,
absolute change value,% wt. of the content of the alloy elements of the beta phase and the alpha phase in the |. m | -SPF process,
Δ m | -is calculated by:
|∆m|= (mβ1-mα1)-(mβ2-mα2)，% wt.
wherein:
the content,% wt. of the alloying elements of the beta-phase before m beta 1-SPF,
the content,% wt. of the alloying elements of the beta-phase after m beta 2-SPF,
content,% wt. of alloying elements of the alpha-phase before m alpha 1-SPF,
content,% wt. of alloying elements of the alpha-phase after m alpha 2-SPF.
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| DE69024418T2 (en) * | 1989-07-10 | 1996-05-15 | Nippon Kokan Kk | Titanium-based alloy and process for its superplastic shaping |
| US5256369A (en) * | 1989-07-10 | 1993-10-26 | Nkk Corporation | Titanium base alloy for excellent formability and method of making thereof and method of superplastic forming thereof |
| JPH0819502B2 (en) * | 1990-02-20 | 1996-02-28 | 日本鋼管株式会社 | Titanium alloy excellent in superplastic workability, its manufacturing method, and superplastic working method of titanium alloy |
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| EP1658389B1 (en) * | 2003-08-25 | 2008-01-23 | The Boeing Company | Method for manufacturing thin sheets of high-strength titanium alloys |
| RU2250806C1 (en) * | 2003-08-25 | 2005-04-27 | ОАО Верхнесалдинское металлургическое производственное объединение (ВСМПО) | Method for making thin sheets of high-strength titanium alloys |
| RU2243833C1 (en) | 2003-08-25 | 2005-01-10 | ОАО Верхнесалдинское металлургическое производственное объединение (ВСМПО) | Method for making thin sheets of high strength titanium alloys |
| GB2470613B (en) * | 2009-05-29 | 2011-05-25 | Titanium Metals Corp | Alloy |
| RU2425164C1 (en) * | 2010-01-20 | 2011-07-27 | Открытое Акционерное Общество "Корпорация Всмпо-Ависма" | Secondary titanium alloy and procedure for its fabrication |
| EP2721187B1 (en) * | 2011-06-17 | 2017-02-22 | Titanium Metals Corporation | Method for the manufacture of alpha-beta ti-al-v-mo-fe alloy sheets |
| RU2555267C2 (en) | 2013-06-25 | 2015-07-10 | Открытое Акционерное Общество "Корпорация Всмпо-Ависма" | Method of fabrication of thin sheets from two-phase titanium alloy and product from these sheets |
| RU2549804C1 (en) * | 2013-09-26 | 2015-04-27 | Открытое Акционерное Общество "Корпорация Всмпо-Ависма" | Method to manufacture armoured sheets from (alpha+beta)-titanium alloy and items from it |
| US10000826B2 (en) * | 2016-03-10 | 2018-06-19 | Titanium Metals Corporation | Alpha-beta titanium alloy having improved elevated temperature properties and superplasticity |
| CN107858558B (en) * | 2017-11-23 | 2019-09-03 | 北京有色金属研究总院 | A kind of Superplastic Titanium Alloys plate and preparation method thereof |
-
2017
- 2017-04-25 EP EP17907725.0A patent/EP3617335B1/en active Active
- 2017-04-25 US US16/607,592 patent/US20200149133A1/en not_active Abandoned
- 2017-04-25 CA CA3062762A patent/CA3062762A1/en active Pending
- 2017-04-25 WO PCT/RU2017/000266 patent/WO2018199791A1/en active Application Filing
- 2017-04-25 JP JP2019558569A patent/JP7028893B2/en active Active
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| WO2018199791A1 (en) | 2018-11-01 |
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| BR112019022330A2 (en) | 2020-05-26 |
| JP2020517834A (en) | 2020-06-18 |
| EP3617335B1 (en) | 2021-11-17 |
| JP7028893B2 (en) | 2022-03-02 |
| EP3617335A4 (en) | 2020-08-19 |
| US20200149133A1 (en) | 2020-05-14 |
| RU2017139320A3 (en) | 2019-05-13 |
| EP3617335A1 (en) | 2020-03-04 |
| RU2691434C2 (en) | 2019-06-13 |
| CA3062762A1 (en) | 2019-11-28 |
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