US20170096719A1 - Extremely high conductivity low cost steel - Google Patents
Extremely high conductivity low cost steel Download PDFInfo
- Publication number
- US20170096719A1 US20170096719A1 US15/126,931 US201515126931A US2017096719A1 US 20170096719 A1 US20170096719 A1 US 20170096719A1 US 201515126931 A US201515126931 A US 201515126931A US 2017096719 A1 US2017096719 A1 US 2017096719A1
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- steel
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- 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
- C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/002—Bainite
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/003—Cementite
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
Definitions
- the present invention relates to steels, in particular hot work tool steels which present an extremely high conductivity while maintaining high levels of mechanical properties.
- Tool steels of the present invention are able to undergo low temperature hardening treatments and can be obtained at low cost.
- thermal conductivity is of extreme importance; when this heat extraction is discontinuous, it becomes crucial.
- Thermal conductivity is related to fundamental material properties like the bulk density, specific heat and thermal diffusivity. Traditionally for tool steels, this property has been considered opposed to hardness and wear resistance since the only way to improve it was by means of decreasing alloying content.
- hot work applications like plastic injection, hot stamping, forging, metal injection, composite curing among many others, extremely high thermal conductivity is often simultaneously required with wear resistance, strength at high temperatures and toughness.
- big cross-section tools are required, for which high hardenability of the material is also necessary.
- thermal fatigue is the main failure mechanism. Thermal fatigue and thermal shock are caused by thermal gradients within the material. In many applications steady transmission states are not achieved due to low exposure times or limited amounts of energy from the source that causes a temperature gradient.
- the magnitude of thermal gradient for tool materials is also a function of their thermal conductivity (inverse proportionality applies to all cases with a sufficiently small Biot number).
- a material with a superior thermal conductivity is subject to a lower surface loading, since the resultant thermal gradient is lower.
- the thermal expansion coefficient is lower and the Young's modulus is lower. Therefore an increase in thermal conductivity implies an increase of the tool life.
- cycle time decreases. Both facts lead to a productivity increase.
- toughness typically fracture toughness and CVN.
- CVN chemical vapor deposition
- high toughness levels were just attainable for low levels of hardness, the same applying for thermal conductivity, decreasing other properties like wear resistance.
- substrate base material has high hardness in order to support the coating, and again high levels of hardness are required.
- the inventors have surprisingly found that when performing the present invention, it is possible to obtain tool steels with high levels of hardness together with high toughness, good wear resistance and improved thermal conductivity. If performed particularly good, extremely high thermal conductivity levels are attainable in combination with the mentioned mechanical properties.
- the cost of the material is decisive for its election but without renouncing at mechanical properties. It is possible with the present invention to obtain tool steels with high toughness and high thermal conductivity with a homogeneous microstructure through the whole cross section and for big thicknesses, very adequate for applications requiring low cost materials such as plastic injection, amongst many others.
- the invention is related to a process to manufacture a steel, in particular a hot work tool steel, characterized in that the steel is subjected to a martensitic, bainitic or martensitic-bainitic treatment with at least one tempering cycle at temperature above 590° C., so that a steel having a hardness above 47 HRc with the structure at the atomic level (atomic arrangement) prescribed in the present invention whose implementation can be monitored by a thermal diffusivity value greater than 12 mm 2 /s or more.
- steel having hardness above 50 HRc with a structure at the atomic level (atomic arrangement) prescribed in the present invention whose implementation can be unequivocally measured by a thermal diffusivity value greater than 10 mm 2 /s or more is obtainable.
- the steel is subjected to at least one tempering cycle at temperature above 640° C., so that steel having a hardness of 40 HRc or more presents a with the structure at the sub-nanometric scale prescribed in the present invention whose implementation can be monitored by a thermal diffusivity value greater than 17 mm 2 /s or more.
- the steel it is also possible to subject the steel to at least one tempering cycle at a temperature above 660° C., so that the steel having a hardness of 35 HRc or more presents a structure at the sub-nanometric scale (regarding the optimization of density of states and mobility of carriers in all phases) prescribed in the present invention whose implementation can be monitored by a thermal diffusivity value greater than 18 mm 2 /s or more.
- thermo-mechanical treatments Some of the selection rules of the alloy within the range and thermo-mechanical treatments required to obtain the desired high thermal conductivity to a high hardness level and wear resistance, are presented in the detailed description of the invention section. Obviously, a detailed description of all possible combinations is out of reach.
- the thermal diffusivity is regulated by the mobility of the heat energy carriers, which unfortunately cannot be correlated to a singular compositional range and a thermo-mechanical treatment.
- Tool steels of the present invention have a structure at the atomic level (atomic arrangement) prescribed in the present invention whose implementation can be monitored by a thermal diffusivity value greater than 12 mm 2 /s and, often, above 14 mm 2 /s for hardness over 50 HRc, and even more than 17 mm 2 /s for hardness over 42 HRc, furthermore presenting a very good toughness and at low cost.
- thermal conductivity tool steels where developed for this purpose.
- thermal conductivity is commonly used in conjunction with other thermodynamic properties.
- thermal diffusivity is a parameter describing a structural feature in the sub-nanometric scale (atomic arrangement, regarding the optimization of density of states and mobility of carriers in all phases).
- thermal diffusivity is a parameter describing a structural feature in the sub-nanometric scale (atomic arrangement, regarding the optimization of density of states and mobility of carriers in all phases).
- the applicant referring to the Guidelines C-II, 4.11 (nowadays Guidelines 2012, Part F, Chapter IV, point 4.11, “Parameters”) realized that almost all parameters (available) to describe this structural feature in the sub-nanometric scale are unusual parameters and that would be prima facie objectionable on grounds of lack of clarity.
- the sole exception for unequivocally describe mentioned structural feature in the sub-nanometric scale is thermal diffusivity and therefore this parameter is chosen to reasonably describe the structural feature.
- thermal diffusivity refers to measures at room temperature, otherwise indicated.
- thermal diffusivity is a fundamental property, one preferred way of measuring it is according to international standards ASTM-E1461 and ASTM-E2585 by means of the Flash Method.
- the present invention is especially interesting for a broad range of applications where extreme thermal conductivity is needed, either at high hardness or low ones.
- a structure at the sub-nanometric scale prescribed in the present invention whose implementation can be monitored by a thermal diffusivity value greater than 16 mm 2 /s, preferably above 17 mm 2 /s, more preferably more than 18 mm 2 /s and even more preferably more than 18.5 mm 2 /s is attainable.
- structures at the sub-nanometric scale prescribed in the present invention whose implementation can be monitored by a thermal diffusivity value greater than 12.5 mm 2 /s, preferably more than 13.6 mm 2 /s, more preferably more than 14.4 mm 2 /s and even more preferably more than 14.8 mm2/s are attainable.
- structures at the sub-nanometric scale prescribed in the present invention whose implementation can be monitored by a thermal diffusivity value greater than even above 15.2 mm2/s are attainable.
- desired microstructure is mainly a bainite microstructure; for some less demanding applications, bainite should be at least 20% vol %, preferably 30% vol %, more preferably 50% vol % and even more preferably more than 80% vol %.
- High Temperature bainite refers to any microstructure formed at temperatures above the temperature corresponding to the bainite nose in the TIT diagram but below the temperature where the ferritic/perlitic transformation ends, but it excludes lower bainite as referred in the literature, which can occasionally form in small amounts also in isothermal treatments at temperatures above the one of the bainitic nose.
- the high temperature bainite should be at least 20% vol %, preferably 28% vol %, more preferably 33% vol % and even more preferably more than 45% vol %.
- the high temperature bainite should be the majoritary type of bainite and thus from all bainite is preferred at least 50% vol %, preferably 65% vol %, more preferably 75% vol % and even more preferably more than 85% vol % to be High Temperature Bainite.
- high temperature bainite is predominantly Upper Bainite, which refers to the coarser bainite microstructure formed at the higher temperatures range within the bainite region, to be seen in the TTT temperature-time-transformation diagram, which in turn, depends on the steel composition.
- the inventors have found that a way to increase the toughness of the High Temperature Bainite, including the Upper Bainite is to reduce the grain size, and thus for the present invention when Tough Upper Bainite is required, grain sizes of ASTM 7 or more, preferably 8 or more, more preferably 10 or more and even more preferably 13 or more are advantageous.
- the present invention it is possible with the present invention to obtain steels, in particular tool steels of extremely high conductivity; the inventors have observed that if following some compositional rules and general considerations in the selection of the composition ranges and thermomechanical treatments, the steels of the present invention can also attain very good toughness and good resistance to wear with considerably low alloy content.
- Main microstrucuture of the steels of the present invention consist on martensitic or bainitic or at least partially martensitic or bainitic (with some ferrite, perlite or even some retained austenite). It is also possible with the present invention to obtain steels with such improved properties at very low costs.
- M 3 Fe 3 C carbides type are one of the most interesting ones because they have high electron density, where M is any metallic element, but most preferably M is Mo and/or W.
- the amount of Mo and W is of great importance as well as their ratio.
- One general rule to fix Mo and W content in order to obtain high thermal conductivity as well as preserve high mechanical properties consists on % Mo+1 ⁇ 2% W>1.2.
- % Mo should be preferably more than 2.3%, more preferably more than 3.2% and even more preferably more than 3.9%.
- the usage of only % Mo is advantageous for thermal conductivity. Therefore, for applications requiring extremely high thermal conductivity % Mo can be even more than 4.1%, preferably more than 4.4%, more preferably more than 4.6% and even more preferably more than 4.8%.
- % W is convenient to be smaller than 0.9%, preferably smaller than 0.7%, more preferably smaller than 0.4 or even no intentional % W at all.
- % W has also an effect on the deformation during heat treatment attainable, since the atomic radii mismatch is greater than that of % Mo.
- W is not absent, preferably present at least in an amount of 0.4%, more preferably more than 0.8% and even more preferably more than 1.2%.
- the inventors have found that there are also some elements which dissolve into these types of carbides inducing almost no distortion to the crystalline structure. This is the example of Hf and Zr. These elements have also very high affinity to carbon tending to form separate MC type carbides which also releases C from solid solution on the matrix.
- Zr is desirable to have at least 0.03% Zr, preferably more than 0.09%, preferably more than 0.18% Zr, more preferably more than 0.52% Zr and even more preferably more than 0.82% Zr.
- Hf serving as strong carbide former also provides with grain-boundary ductility and increase on oxidation resistance. It is also used to increase strength at high temperatures and also both Hf and Zr owe an inherent resistance to corrosion. Therefore, for applications requiring some ambient resistance, it is desirable to have even more Hf and/or Zr present than the one necessary to combine with nominal C to attain some corrosion and oxidation resistance.
- % Hf is desirable to be less than 0.53%, preferably less than 0.48%, more preferably less than 0.36% and even more preferably less than 0.24%.
- % Zr it is desirable to have less than 0.54%, preferably less than 0.46%, more preferably less than 0.28% and even more preferably less than 0.12%.
- % Hf and/or % Zr is totally or partially replaced by % Ta, preferably more than 25% of the amount of Hf and/or Zr, more preferably more than 50% of Hf and/or Zr, even more preferably more than 75% of the of Hf and/or Zr, and even totally replaced.
- Hf is obtained as a by-product Zr refining. Due to their similar chemical properties this process is extremely difficult and therefore very costly. Hf is also well known for having high neutron absorption ability which makes it a perfect candidate for nuclear applications. The limited Hf availability leaves very little material for uses other than nuclear applications and therefore in its pure state is one of the most expensive elements in the market. On the other hand, the rejected product coming from this refinement is Zr which in consequence can be found at really low cost. Due to the similar chemical properties of both elements, in some cases where product cost is of great importance, Hf can be partially or even totally, depending on the application, substituted by Zr, sometimes in detriment of losing some thermal conductivity.
- Zr is preferred to be more than 0.06%, preferably more than 0.22% and more preferable more than 0.33%. In some special cases it can be desirable to have even more than 0.42% Zr, whereas Hf is desired to be less than 0.15%, preferably less than 0.08%, more preferably less than 0.05% Hf and even absence of it.
- no other metallic element besides the mentioned Fe, Mo, W, Hf, and/or Zr should exceed 20% of the weight percent of the metallic elements of the carbide. Preferably it should not be more than 10% or even better 5%.
- % B is desirable to be at least 1 ppm, preferably 5 ppm, more preferably more than 10 ppm and even more preferably more than 50 ppms.
- the % B content has to be kept below 598 ppm, preferably below 196 ppm, more preferably below 68 ppms and even more preferably below 27 ppms.
- % Cr and % V are elements which have a negative effect in terms of high thermal conductivity because they cause a lot off lattice distortion when dissolved into the carbide matrix.
- % V should be kept below 0.23%, preferably below 0.15%, more preferably below 0.1% and even more preferably below 0.05%.
- % Cr has to be kept as low as possible, preferably below 0.28%, more preferably below 0.08% and even more preferably below 0.02%.
- % Si is as low as possible.
- % Si is a bit different, since its content can at least be reduced by the usage of refining processes like ESR, but here it is very technologically difficult, due to the small process window, to reduce the % Si under 0.2%, preferably under 0.16%, more preferably under 0.09% and even more preferably under 0.03% and simultaneously attain a low level of inclusions (specially oxides).
- the highest thermal conductivity can only be attained when the levels of % Si and % Cr lay below 0.1% and even better if the lay below 0.05%.
- undesired impurities such as O, N, P and/or S should be kept as low as possible for extremely high thermal conductivity, preferably below 0.1%, more preferably below 0.08% and even more preferably below 0.01%.
- the present invention it is possible to obtain a structure at the atomic level (atomic arrangement, regarding the optimization of density of states and mobility of carriers in all phases) prescribed in the present invention whose implementation can be unequivocally measured by a thermal diffusivity value greater than 13 mm 2 /s, preferably more than 14 mm 2 /s and even more preferably more than 14.7 mm 2 /s for harnesses more than 48 HRc, preferably more than 50 HRc or even more preferably more than 53 HRc.
- thermal diffusivity value greater than 4.18 mm 2 /s, preferably more than 4.87 mm 2 /s, more preferably more than 5.70 mm 2 /s and even more preferably more than 6.05 mm 2 /s are attainable.
- the steels specially the extremely high thermal conductivity steels, can have the following composition, all percentages being indicated in weight percent:
- composition of steels is normally given in terms of Ceq, which is defined as carbon upon the structure considering not only carbon itself, or nominal carbon, but also all elements which have a similar effect on the cubic structure of the steel, normally being B and/or N.
- trace elements refer to any element, otherwise indicated, in a quantity less than 2%.
- trace elements are preferable to be less than 1.4%, more preferable less than 0.9% and sometimes even more preferable to be less than 0.78%.
- Possible elements considered to be trace elements are H, He, Xe, Be, O, F, Ne, Na, Mg, P, S, Cl, Ar, K, Ca, Fe, Zn, Ga, Ge, As, Se, Br, Kr, Rb, Sr, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Xe, Cs, Ba, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Po, At, Rn, Fr, Ra, Ac, Th, Pa, U, Np, Pu, Am, Cm, Bk, Cf, Es, Fm, Md, No, Lr, Rf, Db, Sg, Bh, Hs, Mt alone and/
- trace elements or even trace elements in general can be quite detrimental for a particular relevant property (like it can be the case sometimes for thermal conductivity and toughness).
- Needless to say being below a certain quantity includes also the absence of the element.
- the absence of most of the trace elements or even all of them is obvious and/or desirable.
- every trace element is considered a single entity and thus very often for a given application different trace elements will have different maximum weight percent admissible values.
- Trace elements can be added intentionally to search for a particular functionality including also cost reduction or its presence (when present) can be unintentional and related mostly to impurity of the alloying elements and scraps used for the production of the alloy. The reason for the presence of different trace elements can be different for one same alloy.
- the steels described above are especially suited for applications requiring extremely high thermal conductivity for drastically decrease cycle time during forming process such as die casting among many others, where the cost associated to productivity is relevant.
- Some applications require high hardness combined with very high thermal conductivity, like is the case of hot stamping of uncoated sheets. Some of those applications require on top quite high levels of toughness and even fracture toughness and are often very sensible to tooling manufacturing costs. For such applications the requirements are so high that very tight composition rules and very strict requirements on the microstructure especially at the sub-nanometric scale, have to be observed.
- high thermal diffusivity is solely related to the availability and freedom of movement of the present carriers in all phases.
- the tool steels of the present invention have two main phase-types: matrix-type phases which are metallic and carbide (nitride boride or even oxide) type phases which are rather ceramic in their nature.
- matrix-type phases which are metallic
- carbide (nitride boride or even oxide) type phases which are rather ceramic in their nature.
- density of states and mean free paths for carriers should be maximized in all present phases.
- the implementation of such optimizations and the attaining of the prescribed structure at the sub-nanometric scale can be monitored by the thermal diffusivity values obtainable at different hardness levels.
- EP 1887096 A1 teaches the best way to maximize thermal conductivity is then to make sure that in the final microstructure carbides with high metallic character are present and even more important their cristaline structure should have a very high level of perfection.
- carbides or nitrides, borides, oxides or mixtures thereof for the same purpose.
- the attaining of such structural features at the atomic level can be monitored by values of thermal diffusivity attained.
- % Ceq has to be higher than 0.27%, preferably higher than 0.32%, more preferably higher than 0.38% and even more preferably higher than 0.52%.
- too high levels of % Ceq lead to impossibility to attain the required nature and perfection of carbides (nitrides, borides, oxides or combinations) regardless of the heat treatment applied. Therefore % Ceq has to be lower than 1.2%, preferably lower than 0.78%, more preferably lower than 0.67% and even more preferably lower than 0.58%. For this unexpected effect to take place it is important to have a precise level of % Mo.
- % Mo can be partially replaced with % W but not completely, thus the values is referred here as % Mo_eq
- This replacement takes place in terms of % Mo_eq, thus every % Mo replaced takes about twice as much % W.
- the replacement of % Mo with % W will remain lower than 75%, preferably lower than 64%, more preferably lower than 38% and even more preferably lower than 18%.
- Trace elements can be added intentionally to search for a particular functionality including also cost reduction or its presence can be unintentional and related mostly to impurity of the alloying elements and scraps used for the production of the alloy.
- % W Even the absence, or presence just as impurity (impurity is one of the types of trace elements) of % W, which could be denominated as absence of % W, can be very advantageous when the minimum cost of alloying is pursued. Therefore, for some cases, % W is desired to be less than 1%.
- the inventors have seen that for this unexpected result to take place, and having high thermal conductivity with high tolerance to deviations in the alloying from the nominal one allowing a less precise manufacturing route, requires a minimum level of % Mo_eq below which the carbides that can be formed are not capable of attaining high perfection levels when the % Ceq is not tightly adjusted.
- % Mo_eq will have to be higher than 2.8%, preferably higher than 3.2%, more preferably more than 3.7% and even more preferably more than 4.2% for this effect to take place.
- too high levels of % Mo_eq will lead to situations where there will not exist any heat treatment that can avoid a considerable scattering of carriers in at least one of the matrix phases, and thus extremely high thermal conductivity even when the teachings of EP 1887096 A1 are applied, will only be attainable for a very precise level of % Ceq, often impracticable at industrial scale.
- % Mo_eq will have to be lower than 6.8%, preferably lower than 5.7%, more preferably lower than 4.8% and even more preferably lower than 3.9%.
- the inventors have seen that for some applications requiring good wear resistance in combination with high toughness within the present invention, the following rule should apply:
- Ceq should be higher than 0.38%, preferably higher than 0.4%, more preferably higher than 0.42% and even more preferably higher than 0.48%. Ceq should be lower than 0.72%, preferably lower than 0.65%, more preferably lower than 0.62% and even more preferably lower than 0.58% and either % Moeq should be moderate or % V should be present as follows: % Moeq than 9.8%, preferably less than 9.5%, more preferably less than 8.9% and even more preferably less than 7.6%; when it comes to % V more than 0.12, preferably more than 0.15%, more preferably more than 0.18% and even more preferably more than 0.23%.
- % Moeq should be less than 4.4%, preferably less than 3.7%, more preferably less than 2.5% and even more preferably less than 1.2% and % Ni should be less than 0.75%, preferably less than 0.62%, more preferably less than 0.58% and even more preferably less than 0.43%.
- % Moeq should be less than 4.2%, preferably less than 3.7%, more preferably less than 2.8% and even more preferably less than 1.6% and % V should be present in an amount higher than 0.05%, preferably higher than 0.12%, more preferably higher than 0.18% and even more preferably higher than 0.29%
- % Zr is the strong carbide former with highest concentration.
- % Zr is the strong carbide former with highest concentration.
- % Zr is higher than 0.05%, preferably higher than 0.1, more preferably higher than 0.22% and even more preferably higher than 0.4%.
- % Zr is higher than 0.67%, preferably higher than 1.5%, more preferably more than 3.7% and even more preferably even more than 4%.
- toughness there is a limitation to % Zr which will often be below %0.78 preferably below 0.42, more preferably below 0.28% and even below 0.18%.
- % Zr can be partially or totally replaced by % Hf and/or % Ta.
- the inventors have seen that the alloying rules commented so far can lead to the unexpected results commented so far, but can only be implemented for moderate cross sections if high mechanical strength in combination with high toughness are required, since the hardenability in the ferritic/perlitic regime is quite moderate. With this respect the authors have made three unexpected discoveries.
- the first relates to the usage of % B for the increase of hardenability.
- Ad in the present invention a factor much higher than 2.0 (almost factor 10 as can be seen in table 7) can be attained with % B above 25 ppm in contrary to what is the case for conventional steels as can be seen in FIG. 1 where the effect of % B diminishes for % B above 20 ppm and becomes almost constant at 2.0 for % B above 25 ppm.
- the second unexpected observation relates to the effect of % Ni in low concentrations which can be strongly increased in the presence of other elements and which can be done with a minimal effect on the scattering in the matrix for high hardness levels !!!.
- the third surprising effect is that of % V which had proved before as even negative for the hardenability in this regime but which has a positive effect if % V is not too high and specially in the presence of % Ni and/or % B.
- % B has a positive effect although the % Ceq values are much higher than those reported in the literature, as can be seen in table 7.
- Literature also describes the maximum positive effect of % B to take place at around 20 ppm as can be seen in FIG. 1 . In the present invention and as can be seen in table 7 the positive effect of % B takes place at higher % B values.
- % B is desired at levels above 1 ppm, preferably above 25 ppm, more preferably above 45 ppm, even more preferably above 58 ppm and even sometimes above 72 ppm.
- An excess of % B can have the contrary effect depending on the availability of boride forming elements.
- the effect on the toughness can be quite detrimental if excessive borides are formed.
- % B is desired below 0.2%, preferably below 88 ppm, more preferably below 68 ppm, and even sometimes below 48 ppm
- % Ni might make it impossible to attain extremely low scattering of carriers levels in at least one of the matrix phases, for his reason when extremely high conductivity is desired, then % Ni is present in an amount below 2.7%, preferably below 1.8%, more preferably below 0.8% and even sometimes below 0.68% and even below 0.48% wt.
- % B has also positive effect on hardenability.
- the combination of % B and % Ni has to be well balanced because otherwise their effect is the cancelled resulting in a decrease of hardenability. If both % B and % Ni are well balanced, it has been surprisingly observed that their effect is additive, leading to high values of hardenability.
- % B is often desirable to be more than 7 ppm, preferably more than 12 ppm, more preferably more than 31 ppm and even more preferably more than 47 ppm. For some applications, excessive % B can be detrimental to hardenability also when moderate % Ni contents are present. In these cases it is desirable to have % B less than 280 ppm, preferably less than 180 ppm, more preferably less than 90 ppm and even less than 40 ppm.
- % V above 1.5% has rather a negative effect on the hardenability
- the authors have seen that to this purpose for some applications it is desirable to have % V more than 0.12, preferably more than 0.22%, more preferably more than 0.42%, more preferably more than 0.52% and even more preferably more than 0.82%.
- % Cu has the advantage of increasing the ambient resistance against certain environments, but if present in excessive amounts it affects toughness negatively. While the effects of % Ni and % Cu seem to be additive for the steels of the present invention, this is not the case for % Ni and % Mn when both present in high enough amounts. For some applications % Cu is desirable to be more than 0.05%, preferably more than 0.12%, more preferably more than 0.54% and even more preferably more than 0.78%.
- % Cu+% Ni is preferred to be more than 0.1%, preferably more than 0.34%, more preferably more than 0.47% and even more preferably more than 0.6%
- Nb and/or Zr help having high thermal and mechanical properties while maintaining the combined effect of % B and % Ni on hardenability.
- the presence of % Nb alone is preferred and there are also applications where the presence of % Zr alone is preferred.
- On this respect often is desirable to have at least 1 ppm, preferably 2 ppm, more preferably more than 4 ppm and even more preferably more than 12 ppm. If they are used in too much quantity, then they might have a negative effect and the balance between demanded compromise is lost. Then, it is desirable that % Nb and/or % Zr are kept below 105 ppm, preferably less than 64 ppm, more preferably less than 30 ppm and even more preferably less than 16 ppm.
- % Cr is desirable to be more than 2.4%, preferably more than 3.7%, more preferably more than 4.6% and even more preferably more than 5.7%.
- % Zr will often be desirable to be present, at least, more than 0.1%, preferably more than 0.87%, more preferably more than 1.43% and even more preferably more than 2.23%.
- % B has to be present in somewhat higher contents that what is required for the increase of the hardenability in the ferrite/perlite domain.
- heat treatments like those described in WO2013167580A1 the inventors have seen that at least 56 ppm of % B, preferably 62 ppm of % B or more, preferably 83 ppm of % B or more, more preferably 94 ppm of % B or more, and even 112 ppm of % B or more are required to have this particular effect, the exact minimum content depending on the specific chemical composition and heat treatment chosen.
- % Ni can have an effect in the morphology of high temperature bainite and also an effect on the role of % B.
- % B rather be kept above 82 ppm, preferably above 92 ppm, more preferably above 380 ppm and even more preferably above 560 ppm but below 35000 ppm, preferably below 1400 ppm, more preferably below 740 ppm, more preferably below 520 ppm and even more preferably below 440 ppm.
- % Ni on its own also can present a positive effect on the morphology of bainite leading to superior toughness for a given grain size.
- compositional rules can be taken into account for an improved performance in certain other applications. For example, when it comes to wear resistance the presence of Hf and/or Zr have a positive effect. If this is to be greatly increased, then other strong carbide formers with little lattice distortion, like Ta or even Nb can also be used. Then Zr+% Hf+% Nb+% Ta should be above 0.12%, preferably above 0.35%, more preferably above 0.41% and even more preferably above 1.2%. Also % V is good carbide former that tends to form quite fine colonies but as said has a higher incidence on thermal conductivity than other carbide formers.
- thermal conductivity should be high but is not required to be extremely high and wear resistance and toughness are both important, it will generally be used with content of more than 0.09%, preferably more than 0.18%, more preferably more than 0.28% and even more preferably more than 0.41%.
- carbide former preferably Zr and/or Hf
- this combination is highly desirable as the percentage of V as the percentage of Zr, Hf and Ta tend to significantly improve the wear resistance compared to a steel that has only carbides (Fe, Mo, W), the same applied for % Nb.
- % C When increasing carbide forms content, also % C has to be increased in order to combine with those elements. For applications requiring improved wear resistance it is desirable that % C is above 0.38%, more preferably above 0.4% and even more preferably above 0.51%. This combination of elements provides good wear and abrasion resistance for low % W content which also until the moment was unexpected.
- M s 539 ⁇ 423 ⁇ % C.
- higher values of % C is desirable for either high wear resistance applications as described and/or will help for applications where a fine bainite is desirable. In such cases it is desirable to have a minimum of 0.41% of Ceq often more than 0.52% and even more than 0.81%.
- rare earth elements As defined by IUPAC, a rare earth element (from now on REE) or rare earth metal is one of a set of seventeen chemical elements in the periodic table, specifically the fifteen lanthanides, as well as scandium and yttrium. Scandium and yttrium are considered rare earth elements because they tend to occur in the same ore deposits as the lanthanides and exhibit similar chemical properties.
- the seventeen rare earth elements known until the moment are Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu.
- the quantity of REE has to be carefully chosen: the inventors have observed that too less of them does not bring any difference in any remarkable property; on the contrary, too much may have a detrimental effect. Therefore, in general terms it is often desired that the sum of all REE is at least more than 7 ppm, preferably more than 12 ppm, preferably more than 55 ppm, more preferably more than 220 ppm and even more preferably more than 330 ppm or even more than 430 ppm. For special applications, it might be preferable to have even more than 603 ppm.
- the inventors have seen that the most interesting ones for such purposes are Ce, La, Sm, Y, Ne and Ge, in pure form or in the form of oxide.
- % La for some applications it is desirable to have at least 4 ppm, preferably more than 10 ppm, more preferably more than 23 ppm and even more preferably more than 100 ppms.
- the inventors have seen that it is desirable to have at least 0.1% wt, preferably more than 0.5% wt, more preferably more than 0.9% wt and even more preferably more than 1%.
- % La is not uses as the only REE and it is combined with other REE, then it is desirable that % La accounts to at least 30% of the total amount of REEs, preferably more than 45% of the total amount of REEs, more preferably more than 67% of the total amount of REEs and even more preferably more than 80% of the total amount of the REEs. In some instances, it is desirable that % La accounts for even more than 91% of the total amount of the REEs and the rest remain as trace elements.
- % Ce for some applications it is desirable to have at least 5 ppm, preferably more than 15 ppm, more preferably more than 53 ppm and even more preferably more than 150 ppms.
- the inventors have seen that it is desirable to have at least 0.09% wt, preferably more than 0.2% wt, more preferably more than 0.7% wt and even more preferably more than 0.9%.
- % Ce is not used as the only REE and it is combined with other REE, then it is desirable that % La accounts to at least 25% of the total amount of REEs, preferably more than 47% of the total amount of REEs, more preferably more than 73% of the total amount of REEs and even more preferably more than 91% of the total amount of the REEs. In some instances, it is desirable that % Ce accounts for even more than 95% of the total amount of the REEs and the rest remain as trace elements.
- Ce-mischmetal or mischmetal which is an alloy of REE; it is mainly composed of Ce and La (typical composition is about 50% Ce, about 45% La, with traces of Nd and Pr). If this alloy is preferred to be used, then it is desirable to use about 0.5% wt, preferably more than 1.6%, more preferably more than 3.1% and even more preferably more than 4.5% wt.
- % Sm for some applications it is desirable to have at least 2 ppm, preferably more than 9 ppm, more preferably more than 43 ppm and even more preferably more than 90 ppms.
- the inventors have seen that it is desirable to have at least 0.02% wt, preferably more than 0.2% wt, more preferably more than 0.51% wt and even more preferably more than 0.9%.
- % Sm is not uses as the only REE and it is combined with other REE, then it is desirable that % Sm accounts to at least 10% of the total amount of REEs, preferably more than 15% of the total amount of REEs, more preferably more than 22% of the total amount of REEs and even more preferably more than 45% of the total amount of the REEs. In some instances, it is desirable that % Sm accounts for even more than 53% of the total amount of the REEs and the rest remain as trace elements.
- % Y for some applications it is desirable to have at least 9 ppm, preferably more than 34 ppm, more preferably more than 67 ppm and even more preferably more than 200 ppms.
- the inventors have seen that it is desirable to have at least 0.12% wt, preferably more than 0.22% wt, more preferably more than 0.9% wt and even more preferably more than 1%.
- % Y is not uses as the only REE and it is combined with other REE, then it is desirable that % Y accounts to at least 30% of the total amount of REEs, preferably more than 45% of the total amount of REEs, more preferably more than 67% of the total amount of REEs and even more preferably more than 80% of the total amount of the REEs. In some instances, it is desirable that % Y accounts for even more than 91% of the total amount of the REEs and the rest remain as trace elements.
- % Gd for some applications it is desirable to have at least 2 ppm, preferably more than 27 ppm, more preferably more than 53 ppm and even more preferably more than 98 ppms.
- the inventors have seen that it is desirable to have at least 0.01% wt, preferably more than 0.1% wt, more preferably more than 0.29% wt and even more preferably more than 0.88%.
- % Gd is not used as the only REE and it is combined with other REE, then it is desirable that % Gd accounts to at least 14% of the total amount of REEs, preferably more than 26% of the total amount of REEs, more preferably more than 37% of the total amount of REEs and even more preferably more than 45% of the total amount of the REEs. In some instances, it is desirable that % Gd accounts for even more than 69% of the total amount of the REEs and the rest remain as trace elements.
- % Nd for some applications it is desirable to have at least 16 ppm, preferably more than 38 ppm, more preferably more than 98 ppm and even more preferably more than 167 ppms.
- the inventors have seen that it is desirable to have at least 0.04% wt, preferably more than 0.14% wt, more preferably more than 0.48% wt and even more preferably more than 1.34%.
- % Nd is not uses as the only REE and it is combined with other REE, then it is desirable that % Nd accounts to at least 35% of the total amount of REEs, preferably more than 49% of the total amount of REEs, more preferably more than 71% of the total amount of REEs and even more preferably more than 83% of the total amount of the REEs. In some instances, it is desirable that % Nd accounts for even more than 93% of the total amount of the REEs and the rest remain as trace elements.
- % Nd present, with a minimum content of 100 ppm, preferably more than 243 ppm, more preferably more than 350 ppm and even more preferably more than 520 ppms.
- % W can also be replaced with.
- % Mo it is often desirable that its content is more than 2.5%, preferably more than 3.5%, more preferably more than 4.6% and even more preferably more than 6.7%.
- % Mo is desirable to be less than 2.6%, preferably less than 1.5%, more preferably less than 0.5% or even less than 0.2%. In some cases even absence of it.
- % W it is often desirable that its content is more than 1.21%, preferably more than 2.3%, more preferably more than 2.7% and even more preferably more than 3.1%.
- % W is desirable to be less than 1.6%, preferably less than 0.9%, more preferably less than 0.43% or even less than 0.11%. In some cases even absence of it.
- % Moeq it is often desirable that its content is more than 2.0%, preferably more than 3.7%, more preferably more than 5.3% and even more preferably more than 6.7%.
- % Moeq is often desirable to be less than 2.3%, preferably less than 1.97%, more preferably less than 0.67% or even less than 0.31%.
- % Ceq it is often desirable that it's content is more than 0.18%, preferably more than 0.28%, more preferably more than 0.34% and even more preferably more than 0.39%.
- % Ceq some other times is desirable to be less than 0.60%, preferably less than 0.56%, more preferably less than 0.48% or even less than 0.43%.
- % Ni it is often desirable that its content is more than 0.1%, preferably more than 0.5%, more preferably more than 1.3% and even more preferably more than 2.9%. On the other hand, depending on the properties sought, % Ni is often desirable to be less than 4%, preferably less than 3.8%, more preferably less than 3.01% or even less than 2.8%. In some cases even absence of it. In the case of % B, it is often desirable that it's content is more than 3 ppm, preferably more than 14 ppm, more preferably more than 50 ppm and even more preferably more than 150 ppm %.
- % B is often desirable to be less than 1.64%, preferably less than 0.4%, more preferably less than 0.1% or even less than 0.02%. In some cases even absence of it.
- % Cr it is often desirable that it is less than 2.9%, preferably less than 1.7%, more preferably less than 0.8% or even less than 0.3%. For precise applications even less than 0.1% or even absence of it.
- % Cr is often desirable to be more than 2.8%, preferably more than 3.7%, more preferably more than 5.7% and even more preferably more than 9.7%.
- % V it is often desirable that its content is more than 0.2%, preferably more than 0.5%, more preferably more than 1.1% and even more preferably more than 2.04%. On the other hand, depending on the properties sought, % V is often desirable to be less than 12%, preferably less than 8.7%, more preferably less than 6.4% or even less than 4.3%. In some cases even absence of it. In the case of % Zr, it is often desirable that it's content is more than 0.03%, preferably more than 0.2%, more preferably more than 0.8% and even more preferably more than 0.99%. On the other hand, depending on the properties sought, % Zr is then desirable to be less than 3%, preferably less than 2.4%, more preferably less than 1.7% or even less than 1.2%. In some cases even absence of it.
- % Mo will often be desirable to be of more than 0.98% wt, preferably more than 1.2% wt, more preferably more than 1.34% wt and even more preferably more than 1.57% wt.
- % Cr it is often desirable to be less than 5.2% wt, preferably less than 4.8%, more preferably less than 4.2% wt and even more preferably less than 3.95% wt.
- % Cr is even lower, less than 2.8% wt, preferably less than 2.69% wt, more preferably less than 1.8% wy and even more preferably less than 1.76% wt.
- % Cr For certain cases, it is desirable to have simultaneously low % Cr and high % Mo. For some other applications it has also been observed that it is desirable to have % Cr and The authors have observed that for intermediate % Cr, that is more than 0.4% wt, preferably more than 2.2% wt, more preferably more than 3.2% wt and even more preferably more than 4.2% wt, then high levels of thermal conductivity can be achieved if following the indications of the present invention and drawing special attention to % Zr, where % Zr is desirable to be more than 0.4% wt, preferably more than 0.8% wt, more preferably more than 1.2% wt and even more preferably more than 1.6% wt.
- % Cr should not be very high, as then it will tend to form primary carbides which is detrimental for some applications. In such cases, it is desirable that % Cr is less than 8.6%, preferably less than 7.7% more preferably less than 7.2% wt, more preferably less than 6.8% wt and even more preferably less than 5.8% wt.
- Such embodiments only work for certain C contents which cannot be too low, that is that preferred % C is more than 0.26% wt, preferably more than 0.32% wt, more preferably more than 0.36% wt and even more preferably more than 0.42% wt.
- % B is present in an amount of more than 3 ppm, preferably more than 12 ppm, more preferably more than 60 ppm and even more preferably more than 100 ppm, then excessive % Co are detrimental for several applications. Then % Co is desirable to be ⁇ 9% wt, preferably less than 7% wt, more preferably less than 5% wt and even more preferably less than 3% wt.
- % Zr is desirable to be >0.01% wt but less than 0.1% wt, preferably less than 0.12% wt, more preferably less than 0.08% wt and even more preferably less than 0.06% wt.
- % C is not too low, that is more than 0.26% wt, preferably more than 0.32% wt, more preferably more than 0.36% wt and even more preferably more than 0.42% wt.
- % Co is not exaggerated high, that is less than 6% wt, preferably less than 4.8% wt, more preferably less than 2.8% wt and even more preferably less than 1.8% wt.
- % B For some applications, where there is % B present, more than 6% wt, preferably more than 17% wt, more preferably more than 52% and even more preferably more than 222 ppm, REE are present in an amount of more than 60 ppm, preferably more than 120 ppm and even more preferably more than 220 ppm and % Cr is high, more than 2.8% wt, preferably more than 3.8% wt and even more preferably more than 4.8% wt, it is preferable that % Mn is low, less than 1.2%, preferably less than 0.8% wt and more preferably less than 0.4% wt.
- the steels, especially high thermal conductivity and high wear resistance steels can have the following composition, all percentages being indicated in weight percent:
- the steels described above can be particularly interesting for applications requiring steel with high thermal conductivity, especially when high levels of wear resistance are desirable.
- the preferred microstructure is predominantly bainitic, at least 50% vol %, preferably 65% vol %, more preferably 76% vol % and even more preferably more than 92% vol %, since is normally the type of microstructure easier to attain in heavy sections and also because is the microstructure normally presenting the highest secondary hardness difference upon proper tempering.
- bainite is any microstructure obtained after a heat treatment which is not martensite, ferrite, retained austenite or any other non-equilibrium microstrucuture like trostite, sorbite . . . , which preferably forms below 700° C.
- low temperature bainite which is known as Lower Bainite and refers to the finer bainite microstructure formed at lower temperature range within bainite region, to be seen in the TTT temperature-time-transformation diagram, which in turn, depends on the steel composition.
- the present invention is advantageous when applying the thermal treatment described in WO2013/167628, where the thermal treatment can be followed by at least one tempering cycle desirably above 500° C., preferably above 550° C., more preferably above 600° C. and even more preferably above 620° C. Often more than one cycle is desirable, more preferably more than one cycle to separate the alloy cementite to dissolve the cementite in solid solution and to separate the carbide formers stronger than iron.
- the problem can be solved with the presence of enough alloying elements and the proper tempering strategy to replace most Fe3C with other carbides and thus attaining high toughness even for coarser bainite.
- the steel is tempered with at least one tempering cycle at a temperature above 500° C. to ensure that a significant portion of the cementite is replaced by carbide-like structures containing carbide formers stronger than iron.
- the traditional way can be used in certain instances, consisting in avoiding coarse Fe3C and/or its precipitation on grain boundaries with the additions of elements that promote its nucleation like Al, Si . . . .
- At least 70% of the bainitic transformation is made at temperatures below 400° C. and/or the thermal treatment includes at least one tempering cycle at a temperature above 500° C. to ensure separation of stronger carbide formers carbides, so that most of the attained microstructure, with the exception of the eventual presence of primary carbides, is characterized by the minimization of rough secondary carbides, in particular at least 60% in volume of the secondary carbides has a size of 250 nm or less, such that a toughness of 10 J CVN or more is attained.
- the composition and tempering strategy is chosen so that high temperature separation secondary carbide types such as types MC, MC-like type as M4C3, M6C and M2C are formed, in such a manner that a hardness above 47 HRc is obtainable even after holding the material for 2 h at a temperature of 600° C. or more.
- Steels of the present invention are also well suited for undergoing surface hardening treatments. Diffusion processes, like nitriding (plasma, gas . . . ), carbonitriding . . . amongst many others are appropriate for thin layer thicknesses. Also thermal spray technologies are suited (plasma, HVOF, cold spray, . . . ). It is particularly advantageous for steels of the present invention when the steel requires a harder surface for the application and the nitriding or coating step is made coincide with the hardening step described in the lines above.
- % Mo is desirable to be more than 4.5%, more preferably more than 4.8% and even more than 5.8%. In such cases it can be also desirable to lower % W content, preferably less than 3% W, more preferably less than 1.5% W and depending on the application even absence of % W.
- Ceq is desirable to be more than 0.15%, preferably more than 0.18%, more preferably more than 0.22% and even more preferably more than 0.26%.
- Ceq is desirable to be less than 0.68%, preferably less than 0.54%, more preferably less than 0.48% and even more preferably less than 0.32%.
- C is desirable to be more than 0.15%, preferably more than 0.14%, more preferably more than 0.24% and even more preferably more than 0.28%.
- C is desirable to be less than 0.72%, preferably less than 0.58%, more preferably less than 0.42% and even more preferably less than 0.38%.
- Moeq is desirable to be more than 1.5%, preferably more than 1.8%, more preferably more than 2.2% and even more preferably more than 2.8%.
- Moeq is desirable to be less than 5.2%, preferably less than 4.2%, more preferably less than 3.6% and even more preferably less than 2.8%.
- Mo is desirable to be more than 1.5%, preferably more than 2.1%, more preferably more than 2.9% and even more preferably more than 3.2%.
- Mo is desirable to be less than 5.4%, preferably less than 4.8%, more preferably less than 3.2% and even more preferably less than 2.5%.
- the steels can have the following composition, all percentages being indicated in weight percent:
- the steels described above can be particularly interesting for applications requiring steel with high thermal conductivity while production costs have to be maintained as low as possible.
- Tool steel of the present invention can be manufactured with any metallurgical process, among which the most common are sand casting, lost wax casting, continuous casting, melting in electric furnace, vacuum induction melting. Powder metallurgy processes can also be used along with any type of atomization and subsequent compacting as the HIP, CIP, cold or hot pressing, sintering (with or without a liquid phase), thermal spray or heat coating, to name a few of them.
- the alloy can be directly obtained with the desired shape or can be improved by other metallurgical processes. Any refining metallurgical process can be applied, like ESR, AOD, VAR . . . . Forging or rolling are frequently used to increase toughness, even three-dimensional forging of blocks.
- Tool steel of the present invention can be obtained in the form of bar, wire or powder for use as solder alloy. Even, a low-cost alloy steel matrix can be manufactured and applying steel of the present invention in critical parts of the matrix by welding rod or wire made from steel of the present invention. Also laser, plasma or electron beam welding can be conducted using powder or wire made of steel of the present invention.
- the steel of the present invention could also be used with a thermal spraying technique to apply in parts of the surface of another material.
- the steel of the present invention can be used as part of a composite material, for example when embedded as a separate phase, or obtained as one of the phases in a multiphase material. Also when used as a matrix in which other phases or particles are embedded whatever the method of conducting the mixture (for instance, mechanical mixing, attrition, projection with two or more hoppers of different materials . . . ).
- the present invention is especially well suited to obtain steels for the hot stamping tooling applications.
- the steels of the present invention perform especially well when used for plastic injection tooling. They are also well fitted as tooling for die casting applications.
- Another field of interest for the steels of the present document is the drawing and cutting of sheets or other abrasive components. Also for medical, alimentary and pharmaceutical tooling applications the steels of the present invention are of especial interest.
- v is cooling rate at which ferritic transformation occurs at k/s, considering an austenitizing temperature between 1040° C.-1120° C. v (k/s) ID36 0.06 ID91 0.5 iD115 0.08 iD102 0.1 iD104 0.1 iD105 0.05 iD106 0.1 iD107 0.08 iD40 0.08 iD42 0.08 iD96 0.08 iD49 0.05 iD50 0.05 iD51 0.05 iD44 0.2 iD45 0.1 iD46 0.05 iD47 0.05
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Also Published As
Publication number | Publication date |
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PL3119918T3 (pl) | 2023-06-12 |
CA2942442C (en) | 2022-12-13 |
KR20240032146A (ko) | 2024-03-08 |
JP2017512913A (ja) | 2017-05-25 |
PT3119918T (pt) | 2023-05-18 |
EP3119918B1 (de) | 2023-02-15 |
EP4219783A1 (de) | 2023-08-02 |
MX2016012019A (es) | 2017-04-27 |
JP7072268B2 (ja) | 2022-05-20 |
WO2015140235A1 (en) | 2015-09-24 |
KR20160141734A (ko) | 2016-12-09 |
US20200291496A1 (en) | 2020-09-17 |
JP2020111829A (ja) | 2020-07-27 |
US11421290B2 (en) | 2022-08-23 |
ES2944566T3 (es) | 2023-06-22 |
KR20220102152A (ko) | 2022-07-19 |
EP3119918A1 (de) | 2017-01-25 |
SI3119918T1 (sl) | 2023-07-31 |
CA2942442A1 (en) | 2015-09-24 |
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