EP3358026B1 - Fonte à graphite sphéroïdal présentant une excellente résistance aux défauts gazeux - Google Patents

Fonte à graphite sphéroïdal présentant une excellente résistance aux défauts gazeux Download PDF

Info

Publication number
EP3358026B1
EP3358026B1 EP16850700.2A EP16850700A EP3358026B1 EP 3358026 B1 EP3358026 B1 EP 3358026B1 EP 16850700 A EP16850700 A EP 16850700A EP 3358026 B1 EP3358026 B1 EP 3358026B1
Authority
EP
European Patent Office
Prior art keywords
cast iron
spheroidal graphite
graphite cast
less
content
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP16850700.2A
Other languages
German (de)
English (en)
Other versions
EP3358026A4 (fr
EP3358026A1 (fr
Inventor
Masahide Kawabata
Hideya Yamane
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Proterial Ltd
Original Assignee
Hitachi Metals Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=58423018&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP3358026(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Hitachi Metals Ltd filed Critical Hitachi Metals Ltd
Publication of EP3358026A1 publication Critical patent/EP3358026A1/fr
Publication of EP3358026A4 publication Critical patent/EP3358026A4/fr
Application granted granted Critical
Publication of EP3358026B1 publication Critical patent/EP3358026B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C37/00—Cast-iron alloys
    • C22C37/10—Cast-iron alloys containing aluminium or silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C37/00—Cast-iron alloys
    • C22C37/04—Cast-iron alloys containing spheroidal graphite
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C1/00—Refining of pig-iron; Cast iron
    • C21C1/10—Making spheroidal graphite cast-iron
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/08—Making cast-iron alloys

Definitions

  • the present invention relates to a spheroidal graphite cast iron excellent in gas defect resistance.
  • Spheroidal graphite cast iron which has excellent mechanical characteristics and good castability is widely used for various automobile parts and machine parts.
  • main raw materials pig iron, steel scrap, return scrap (casting return material) and the like are used.
  • pig iron for castings was conventionally the main material as the raw material of the spheroidal graphite cast iron; however, in recent years, from the viewpoint of economical use of resources, it has been common to mainly use steel scrap instead of pig iron the price of which has risen.
  • Steel scrap has been more and more heavily used as a raw material of cast iron in general including spheroidal graphite cast iron since it is caused in large amount with the growth of the automobile industry and is supplied inexpensively.
  • the steel scrap caused in the automobile industry is formed of machining scrap for automobile bodies and the like, and in recent years, as the steel material thereof, the ratio of high-tensile steel plates has been increasing.
  • the reason therefor is that for automobile bodies and the like, while weight reduction is required from the viewpoint of environmental preservation by improvement of fuel efficiency, securement of strength and rigidity is also required from the viewpoint of securement of passengers' safety at the time of a collision. For this reason, it is required that automobile bodies and the like attain both weight reduction and strength enhancement/rigidity enhancement, and to respond thereto, high-tensile steel plates containing high levels of Mn, Cr, Mo and the like tend to be used heavily.
  • Some high-tensile steel plates are enhanced in strength by containing N (nitrogen) in addition to Mn, Cr and Mo and undergoing precipitation hardening with a carbonitride or by undergoing nitriding. Some of these high-tensile steel plates contain as much as several hundreds of ppm of N.
  • N nitrogen
  • spheroidal graphite cast iron is manufactured by using, as the raw material, steel scrap inevitably containing a large amount of N like this, there is a possibility that free N contained in the melt into which this raw material is melted increases.
  • free N indicates a nitrogen atom in a free state not constituting an atom constituting a solid phase or a solid solution
  • N indicates nitrogen as an element.
  • the melt (raw melt) formed in the melting process of spheroidal graphite cast iron is deoxidized at the stage of the melting process since it contains Si and Mn, and thereafter, is further thoroughly deoxidized by the Mg added in the spheroidizing processing performed after the raw melt is shifted to a ladle and the Si added in the inoculation processing.
  • the thus deoxidized melt for spheroidal graphite cast iron has the property of readily absorbing or occluding the free N in the atmosphere when the melt is exposed to the atmosphere in the process of tapping from a melting furnace into a ladle or in the process of pouring from the ladle into a mold.
  • Patent Document 1 has a description of a spheroidal graphite cast iron containing, in mass ratio, 2.0 to 4.0% carbon, 0.01 to 0.1% spheroidization promoting element formed of one or more than one of magnesium, calcium and a rare-earth element, 1.0 to 3.0% silicon and not more than 0.02% sulfur with the remnant consisting of iron and inevitable impurities and in which the amount of elements other than cobalt, copper and nickel in the inevitable impurities is made as small as possible so that the absorption energy value in a Charpy impact test at -60 degrees C or -80 degrees C is not less than 14 J/cm 2 on a V notch test piece by doing the following: An alloy having, in mass ratio, 2.0 to 4.0% carbon, 1.0 to 3.0% silicon and not more than 0.02% sulfur with the remnant consisting of iron and a very small amount of inevitable impurities is introduced into
  • Patent Document 1 in melting the raw material, after the melting furnace chamber is evacuated, argon gas is introduced to make the inside of the melting furnace chamber an argon atmosphere and by using a water-cooled highly pure copper crucible and using a cold crucible melting furnace which is an apparatus that simulatively brings the copper crucible and the molten metal into a non-contact state and melts them (levitation melting), the immixture of impurities from the crucible or the gas phase (environment) into the molten metal as in the conventional melting process is prevented and a highly pure material can be produced.
  • the inclusion can be further reduced and a spheroidal graphite cast iron where the internal brittle part is reduced can be provided.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2004-169167 Document EP 2799565 discloses a spheroidal graphite cast iron having a) a composition comprising by mass 3.4-4% of C, 1.9-2.8% of Si, 0.02-0.06% of Mg, 0.2-1% of Mn, 0.2-2% of Cu, 0-0.1% of Sn, 0.85-3% of (Mn+Cu+10*Sn), 0.05% or less of P, 0.02% or less of S, the balance being Fe and inevitable impurities.
  • Document JP 2011038183 discloses a cast iron component for vehicule in which the spheroidal graphite cast iron includes the spheroidal graphites, a ferrite phase produced around the spheroidal graphite and a pearlite phase produced among adjacent ferrite phases.
  • the manufacturing method thereof is provided by making the inside of the melting furnace chamber the argon atmosphere and using a cold crucible melting furnace which is a special apparatus formed of a water-cooled highly pure copper crucible.
  • the cold crucible melting furnace is generally used for the manufacture of a highly pure material such as the manufacture of a highly pure alloy ingot.
  • the manufacturing method of Patent Document 1 after the raw material is melted in the copper crucible and the spheroidizing agent is added, cooling and solidification of the melt are performed in the copper crucible.
  • the obtained spheroidal graphite cast iron is a massive cast product of a shape copying the shape of the space in the crucible.
  • the present invention is made in view of the above-described conventional problems, and an object thereof is to provide spheroidal graphite cast iron having excellent gas defect resistance where gas defects such as pinholes attributable to the free N are small in number and having mechanical characteristics and machinability equal to or greater than the conventional ones.
  • the spheroidal graphite cast iron of the present invention has excellent gas defect resistance with few gas defects such as pinholes attributable by the free N.
  • composition of the spheroidal graphite cast iron of the present invention will be described below in detail.
  • the contents of the elements constituting the alloy are expressed by mass ratios (%) unless otherwise specified.
  • reduction in the gas defect attributable to the free N derived from steel scrap is described as an embodiment of the present invention.
  • C is an element that contributes to the flowability of the melt and the crystallization of graphite.
  • the C content is less than 3.3%, the flowability at the time of casting decreases and the number of graphite grains decreases so that chill (Fe 3 C: cementite) is apt to be formed, which decreases the elongation of the spheroidal graphite cast iron.
  • chill Fe 3 C: cementite
  • the C content exceeds 4%, shrinkage cavity is apt to appear and abnormal graphite is apt to be formed, so that strength decreases.
  • the C content is made 3.3 to 4%.
  • the lower limit of the C content is preferably 3.4%, and is more preferably 3.6%.
  • the upper limit of the C content is preferably 3.9%, and is more preferably 3.8%.
  • Si is necessary for promoting the crystallization of graphite and enhancing the flowability of the melt.
  • the Si content is less than 2%, chill is apt to be formed, so that the machinability and elongation of the spheroidal graphite cast iron decrease.
  • the Si content exceeds 3%, the matrix of the spheroidal graphite cast iron becomes brittle, so that ductility (impact value) and elongation extremely decrease and strength and machinability deteriorate.
  • the Si content is made 2 to 3%.
  • the lower limit of the Si content is preferably 2.1%, and is more preferably 2.2%.
  • the upper limit of the Si content is preferably 2.9%, and is more preferably 2.8%.
  • P is an element inevitably immixed from the raw material. P inhibits the spheroidization of graphite, and is solid-solved in the matrix to embrittle the structure. For this reason, the P content is made not more than 0.05%. On the other hand, although no lower limit is set, since it is not economical to reduce it, for example, to not more than the detection limit, it is desirable that the lower limit thereof be approximately 0.005%.
  • the upper limit of the P content is preferably 0.03%.
  • S is an element inevitably immixed from the raw material.
  • S is a graphite spheroidization inhibiting element, and the content thereof is made not more than 0.02%.
  • the lower limit thereof be approximately 0.005%.
  • the upper limit of the S content is preferably 0.01%.
  • Mn which is an element inevitably immixed from the raw material, precipitates a pearlite phase as a pearlite phase stabilizing element.
  • the Mn content be not less than 0.2%.
  • the content thereof exceeds 0.8%, the formation of chill is conspicuous, so that the ductility, elongation and machinability of the spheroidal graphite cast iron are deteriorated.
  • the Mn content is made not more than 0.8%.
  • the upper limit of the Mn content is preferably 0.5%.
  • Cu which is a pearlite phase stabilizing element
  • a pearlite phase stabilizing element is an element that is effective when a spheroidal graphite cast iron containing a pearlite phase in the matrix structure and having its strength improved is obtained.
  • the Cu content is not less than 0.1%.
  • the Cu content exceeds 0.8%, the spheroidal graphite cast iron becomes too hard, and graphite spheroidization is inhibited, so that the elongation and ductility of the spheroidal graphite cast iron decrease.
  • the Cu content is set to not more than 0.8%.
  • the upper limit of the Cu content is preferably 0.6%.
  • Mg is an element necessary for graphite spheroidization that is important in improving mechanical characteristics such as the strength and elongation of the spheroidal graphite cast iron, and when the content thereof is less than 0.02%, the effect of graphite spheroidization is insufficient.
  • the Mg content exceeds 0.06%, chill and shrinkage cavity are apt to be formed, so that the machinability and ductility of the spheroidal graphite cast iron decrease. For this reason, the Mg content is made 0.02 to 0.06%.
  • the lower limit of the Mg content is preferably 0.025%, and is more preferably 0.03%.
  • the upper limit of the Mg content is preferably 0.05%, and is more preferably 0.04%.
  • Ti titanium: 0.01 to 0.04%
  • V vanadium
  • Nb niobium
  • Ti, V and Nb are essential elements that are most important as constituents constituting the spheroidal graphite cast iron of the present invention.
  • the free N contained in the melt of the spheroidal graphite cast iron is considered to be finally released as nitrogen gas without being fixed (1) in the matrix phase, (2) in a nitride or a carbonitride or (3) to the structural elements of the above (1) and (2) and exist as N mainly in these three structural elements in the gas defect formed of the nitrogen gas.
  • the upper limit of the amount of N that can be contained in the matrix phase of (1) is the solid solubility limit of the austenite phase generated in the neighborhood of 1000 degrees C which is the austenitizing temperature.
  • Ti, V and Nb are powerful carbonitride forming elements (hereinafter, the three elements of Ti, V and Nb will sometimes be referred to as carbonitride forming elements), and by these elements being contained in not less than a predetermined amount, a nitride or a carbonitride (hereinafter, these will sometimes be collectively called carbonitride) is formed by a chemical combination with the free N in the melt.
  • the crystallization temperature of the carbonitride formed by the above-mentioned carbonitride forming elements is higher than the crystallization start temperature of the austenite phase (matrix phase), and in the process of the melt being cooled to solidify, the carbonitride is formed earlier than the matrix phase.
  • the free N excessively dissolved in the melt beyond the solid solubility limit of N of the austenite phase is fixed as a carbonitride.
  • the free N exceeding the solid solubility limit of the austenite phase is inhibited from being released as nitrogen gas from inside the melt at the time of solidification, so that the occurrence of the gas defect is prevented.
  • an effect can also be produced in that variation in the mechanical characteristics of the obtained spheroidal graphite cast iron can be reduced by suppressing variation in the amount of N solid-solved in the austenite phase by the fixing of the free N in the melt by the carbonitride forming elements. That is, N is a powerful pearlite phase stabilizing element together with Mn and Cu, and promotes the precipitation of the pearlite phase from the austenite phase.
  • N is a powerful pearlite phase stabilizing element together with Mn and Cu, and promotes the precipitation of the pearlite phase from the austenite phase.
  • the precipitation amount of the pearlite phase can be controlled by adjusting the additive amounts of elements such as Mn and Cu the contents of which can be comparatively easily controlled.
  • the present invention pearlitization by N is suppressed by reducing the amount of N solid-solved in the austenite phase by the fixing of the free N by the carbonitride forming elements as described above.
  • the precipitation amount of the pearlite phase can be stably adjusted by controlling the contents of Mn and Cu, so that variation in the mechanical characteristics of the spheroidal graphite cast iron can be reduced.
  • the contents of Ti, V and Nb be not less than 0.01%, not less than 0.001% and not less than 0.001%, respectively.
  • the contents of Ti, V and Nb exceed 0.04%, 0.01% and 0.01%, respectively, an extremely hard carbide or nitride is formed, so that the machinability and mechanical characteristics (strength and elongation) of the spheroidal graphite cast iron decrease.
  • the Ti content is made 0.01 to 0.04%
  • the V content is made 0.001 to 0.01%
  • the Nb content is made 0.001 to 0.01%.
  • the lower limit of the Ti content is preferably 0.012%, and is more preferably 0.013%.
  • the upper limit of the Ti content is preferably 0.035%, and is more preferably 0.025%.
  • the lower limit of the V content is preferably 0.002%. Moreover, the upper limit of the V content is preferably 0.004%, and is more preferably 0.003%.
  • the lower limit of the Nb content is preferably 0.002%, and is more preferably 0.004%.
  • the upper limit of the Nb content is preferably 0.006%, and is more preferably 0.005%.
  • a spheroidal graphite cast iron By the carbonitride forming elements being contained in a predetermined amount as described above and fixing the free N as a carbonitride, a spheroidal graphite cast iron can be obtained that has an excellent gas defect resistance with few gas defects such as pinholes attributable by the free N and further, has mechanical characteristics (strength and elongation) and machinability equal to or greater than the conventional ones by the variation in its mechanical characteristics being reduced and the excessive carbonitride formation being suppressed.
  • one significant feature of the present invention is that Ti, V and Nb are not contained singly but these three elements are contained in combination and the contents thereof are controlled to appropriate amounts.
  • Ti, V and Nb being all contained in the above-mentioned numerical ranges as described above, the total amount of these carbonitride forming elements can be reduced more than when these are contained singly or only two kinds are contained.
  • the total amount of contained carbonitride forming elements can be suppressed compared with when they are contained singly or only two kinds are contained.
  • the amount of carbonitride that affects the mechanical characteristics and machinability is made in an appropriate range while the above-described effect of fixing the free N by the carbonitride formed by the carbonitride forming elements is sufficiently produced, and consequently, a spheroidal graphite cast iron can be obtained where both gas defect resistance, and mechanical characteristics and machinability are obtained.
  • the total amount of contents of Ti, V and Nb in combination can be in a range of 0.012 to 0.06% from the total amount of upper limits and lower limits of the respective elements.
  • the total content of Ti, V and Nb is not less than 0.015%.
  • the total amount of Ti, V and Nb exceeds 0.045%, a tendency to form a hard carbide or nitride increases, so that the deterioration of the machinability and mechanical characteristics (strength and elongation) of the spheroidal graphite cast iron is conspicuous.
  • the total content of Ti, V and Nb is made 0.015 to 0.045%.
  • the lower limit of the total content of Ti, V and Nb is preferably 0.02%.
  • the upper limit of the total content of Ti, V and Nb is preferably 0.03%.
  • N is an element immixed mainly from steel scrap such as a high-tensile steel plate.
  • the melt of the spheroidal graphite cast iron obtained through a melting process with such steel scrap as the raw material contains approximately 0.008 to 0.015% free N.
  • the free N in the melt is fixed to the carbonitride formed by the carbonitride forming elements.
  • the content of N contained in the spheroidal graphite cast iron, together with the N fixed (solid-solved) to the matrix phase is not less than 0.004%.
  • the N content is made not less than 0.004%.
  • the N content exceeds 0.008%, the carbonitride fixing N also increases, so that there is a possibility that the machinability and mechanical characteristics (strength and elongation) of the obtained spheroidal graphite cast iron decrease. For this reason, the N content is made not more than 0.008%. Therefore, the N content is made 0.004 to 0.008%.
  • the upper limit of the N content is preferably 0.007%, and is more preferably 0.006%.
  • the spheroidal graphite cast iron of the present invention to further improve the gas defect resistance and further improve the mechanical characteristics (strength and elongation) and machinability, it is preferable to satisfy the expression (1) with the above-described composition range requirements being satisfied.
  • the element symbols in the expression (1) represent the contents [mass ratio (%)] of the elements in the spheroidal graphite cast iron.
  • Ti, V and Nb which are carbonitride forming elements are united with N in one-to-one correspondence in the number of atoms, if the ratio between the total amount of substance (T) of carbonitride forming elements shown in the following expressions (2) and (3) and the amount of substance (N) of N, that is, the amount of substance ratio (molar ratio) T/N is within a predetermined range, the balance between the carbonitride forming elements and N is appropriate, so that the total content of Ti, V and Nb is one that is necessary and sufficient for the N content.
  • the amount of substance ratio (molar ratio) T/N being within a predetermined range, in the spheroidal graphite cast iron obtained by using a melt with plenty of free N, the formation of excessive carbonitride is also suppressed while N exceeding the solid solubility limit of the austenite phase is fixed as a carbonitride by Ti, V and Nb, so that the gas defect resistance, the mechanical characteristics (strength and elongation) and the machinability are further improved.
  • the amount of substance ratio T/N between the total amount of substance (T) of the carbonitride forming elements and the amount of substance (N) of N, which is straightened up in consideration of the atomic weight, is (0.29Ti+0.27V+0.15Nb)/N in the expression (1).
  • the coefficients by which the carbonitride forming elements are multiplied are coefficients obtained from the ratio between the atomic weightf N and the elements; 0.29 represents the ratio between the atomic weights of N and Ti (14/48), 0.27 represents the ratio between the atomic weights of N and V (14/51), and 0.15 represents the ratio between the atomic weights of N and Nb (14/93).
  • the value of the expression (1) is not less than 0.8, since an appropriate amount of carbonitride forming elements for N is contained, even in a spheroidal graphite cast iron obtained by using a melt with plenty of free N, N exceeding the solid solubility limit of the austenite phase is fixed neither too much nor too little by the carbonitride forming elements, so that sufficient gas defect resistance is obtained.
  • the value of the expression (1) is not more than 2.0, the formation of a carbonitride is suppressed to the minimum, so that the mechanical characteristics (strength and elongation) and machinability improve.
  • the value of (0.29Ti+0.27V+0.15Nb)/N be in a range of 0.8 to 2.0.
  • the value of the expression (1) is 1, that is, the value of the expression (1) is 1, N is formed as a carbonitride neither too much nor too little and there is no solid-solving of N into the austenite phase; however, when in consideration of the yield of formation of the carbonitride, the promotion of precipitation of the pearlite phase by appropriate solid-solving of N into the austenite phase, and the point that two free Ns (atoms) are necessary for molecularization as nitrogen gas, in actuality, a range of 0.8 to 2.0 is suitable.
  • the value of the left side of the expression (1) is more preferably 1.0, and is most preferably 1.2.
  • the tensile strength be not less than 600 MPa and the elongation be not less than 12%.
  • the spheroidal graphite cast iron having mechanical characteristics where the tensile strength is not less than 600 MPa and the elongation is not less than 12% is suitable for use for constructional members and the like similarly to the conventional spheroidal graphite cast iron since it has mechanical characteristics equal to or greater than the conventional ones.
  • the tensile strength is more preferably not less than 610 MPa, and is most preferably not less than 620 Pa.
  • the elongation is more preferably not less than 13%, and is most preferably not less than 14%.
  • the additive amounts of elements such as Mn and Cu the contents of which are comparatively easily controlled, and specifically, it is preferable that the Mn content be 0.2 to 0.5% and the Cu content be 0.2 to 0.6%.
  • a melt was formed by melting pig iron, steel scrap and return scrap of spheroidal graphite cast iron as the raw material in a high frequency melting furnace with a capacity of 100 kg and adding a recarburizing agent and Fe-Ti, Fe-V, Fe-Nb and Fe-Si alloys for ingredient adjustment.
  • the steel scrap was a high-tensile steel plate with an N content of 0.05%, and of the compounded amount ratio 100% of the raw material which was the total of the pig iron, the steel scrap and the return scrap, the compounded amount ratio of the steel scrap was 40% in first to sixteenth Examples 1 to 16 and Comparative examples 1 to 11 described later, and was 0% in the Reference example where they were not compounded.
  • This melt was tapped at approximately 1500 degrees C into a ladle where an Fe-Si-Mg alloy and a cover member made of steel scrap covering this were placed as a graphite spheroidizing agent, and spheroidizing processing by a sandwiching method was performed.
  • the amount of N (free N) contained in the melt having undergone the spheroidizing processing was in a range of 0.005 to 0.009% in all the Examples and Comparative examples described below, and was 0.003% in the Reference example.
  • the melt having undergone the spheroidizing processing was poured into a sand mold at approximately 1400 degrees C, and was cast into a plurality of one-inch Y blocks, a mold for a flat test piece for a gas defect area ratio evaluation described later and a mold for a cylindrical test piece for a machinability evaluation.
  • Fe-Si alloy powder was added to the flow of the melt to perform inoculation.
  • spheroidal graphite cast irons having the compositions shown in Table 1 were obtained.
  • the Examples 1, 2, 4, 6-11 are spheroidal graphite cast irons within the composition range defined by the present invention
  • Examples 3, 5, 12-16 are reference examples and the Comparative examples 1 to 11 (Com.1 to Com.11) and the Reference example (Ref.) are spheroidal graphite cast irons outside the composition range defined by the present invention.
  • the Comparative example 1 and the Comparative examples 7 to 11 are spheroidal graphite cast irons where the content of one or more than one element of Ti, V, Nb and N is too large
  • the Comparative examples 2 to 6 and the Reference example are spheroidal graphite cast irons where the content of one or more than one element of Ti, V, Nb and N is too small.
  • the compositions of the obtained spheroidal graphite cast irons were checked by a glow-discharge mass spectrometer (manufactured by VG, the trade name: VG9000, hereinafter, referred to merely as GDMS).
  • the GDMS cannot measure, of the N existing in the above-described structural elements, the N contained in the gas defect of (3).
  • the amount (mass ratio) of N shown in Table 1 is the amount of N solid-solved in the matrix phase of (1) and N fixed to the carbonitride of (2).
  • Table 1 Composition (mass ratio (%)) (1) No. C Si P S Mn Cu Mg Ti V Nb N Ex.1 3.55 2.45 0.018 0.010 0.35 0.41 0.035 0.015 0.002 0.005 0.004 Ex.2 3.65 2.35 0.021 0.009 0.42 0.37 0.034 0.035 0.006 0.002 0.007 Ex.3 3.66 2.38 0.025 0.008 0.44 0.38 0.036 0.040 0.009 0.010 0.008 Ex.4 3.56 2.41 0.028 0.009 0.41 0.39 0.038 0.037 0.004 0.002 0.006 Ex.5 3.68 2.40 0.022 0.007 0.38 0.41 0.036 0.037 0.005 0.007 0.007 Ex.6 3.57 2.39 0.019 0.008 0.45 0.40 0.039 0.025
  • Test pieces were cut from samples of the spheroidal graphite cast irons obtained by the above-described casting, and the following evaluations were performed.
  • FIGS. 1A and 1B are schematic views of the flat test pieces for measuring the gas defect, FIG. 1A is a plan view, and FIG. 1B is a side view. These flat test pieces 10 were 60 mm in width, 150 mm in length and 10 to 15 mm in thickness.
  • the flat test pieces 10 were each obtained by doing as follows: After the melts same as the one-inch Y blocks were each poured from the sprue at not less than 1400 degrees C into a sand mold defining a cavity formed of the flat test piece 10, a riser 11 with a diameter of 45 mm and a height of 60 mm, the sprue (not shown), a runner 12a with a width of 35 mm and a thickness of 3 mm and an ingate 12b with a width of 40 mm and a thickness of 9 mm, cooling and shake-out were performed, the riser 11 was cut to be separated, and shot blast processing was performed.
  • the test pieces of the Examples 1, 2, 4, 6-11 where the contents of Ti, V, Nb and N were within the composition range of the present invention were lower in gas defect area ratio than the test pieces of the Comparative examples 2 to 6 where the content of one or more than one element of Ti, V, Nb and N was too small. It was confirmed that even in the spheroidal graphite cast iron obtained by using a melt containing excessive free N, the gas defect occurrence tendency could be reduced by defining the lower limits of the contents of Ti, V and Nb as described above.
  • the gas defect area ratio is preferably not more than 11%, is more preferably not more than 10.5%, and is most preferably not more than 10%.
  • the tool life improvement rate is a value (A/B) obtained by dividing the tool life A of each of the spheroidal graphite cast irons of the Examples and the Comparative examples by the tool life B of the spheroidal graphite cast iron of the Reference example (Ref.) representative of the conventional technical level.
  • the tool life improvement rates (times) of the Examples 1 to 16, the Comparative examples 1 to 11 and the Reference example (Ref.) are shown in Table 2.
  • the tool life improvement rates of the Examples 1, 2, 4, 6-11 within the composition range of the present invention were all in a range of 1.0 to 1. 4 times. From the results of the Examples 1, 2, 4, 6-11 it is apparent that the spheroidal graphite cast iron of the present invention has machinability equal to or greater than the conventional one. On the other hand, the tool life improvement rates of the Comparative example 1 and the Comparative examples 7 to 11 where the content of one or more than one element of Ti, V, Nb and N was too large were all less than 1.0 time, and machinability was poor.
  • the tool life improvement rate is preferably not less than 1.1 times, is more preferably not less than 1.2 times, and is most preferably 1.3 times.
  • a test piece of 14A of JIS Z 2201 was made from a one-inch Y block, a tensile test was performed at room temperature by an Amsler tensile testing machine (AG-IS250kN manufactured by Shimadzu Corporation) according to JIS Z 2241, and the tensile strength, the 0.2% yield strength and the elongation were measured. The results are shown in Table 2.
  • the tensile strength was not less than 600 MPa, the 0.2% yield strength was not less than 350 MPa and the elongation was not less than 12%, and it was confirmed that all had mechanical characteristics equal to or greater than the conventional ones shown in the Reference example (Ref.) .
  • the tensile strength was as low as less than 600 MPa, and in all of the Comparative example 1 and the Comparative examples 7 to 11 where the content of one or more than one element of Ti, V, Nb and N was too large, the elongation was as low as less than 12%.
  • the spheroidal graphite cast iron of the present invention was a spheroidal graphite cast iron having mechanical characteristics and machinability equal to or greater than the conventional ones and further, having excellent gas effect resistance at the same time.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)

Claims (7)

  1. Fonte à graphite sphéroïdal (10) présentant une excellente résistance aux défauts gazeux, caractérisée en ce qu'elle est constituée de, en rapport massique :
    C : 3,3 à 4 %;
    Si : 2 à 3 %;
    P : pas plus de 0,05 %;
    S : pas plus de 0,02 %;
    Mn : pas plus de 0,8 %;
    Cu : pas plus de 0,8 % et pas moins de 0,1 %;
    Mg : 0,02 à 0,06 %;
    Ti : 0,01 à 0,04 %;
    V : 0,001 à 0,01 %;
    Nb : 0,001 à 0,01 %, la teneur totale en Ti, V et Nb étant comprise entre 0,015 et 0,045 %; et
    N : 0,004 à 0,008 %,
    le reste étant constitué de Fe et d'inévitables impuretés.
  2. Fonte à graphite sphéroïdal selon la revendication 1,
    dans laquelle la fonte à graphite sphéroïdal contient Ti, V, Nb et N de manière à satisfaire l'expression suivante (1): 0,8 ≤ ( 0,29 Ti + 0,27 V + 0,15 Nb / N ≤ 2,0
    Figure imgb0005
     ici, les symboles d'éléments dans l'expression (1) représentent la teneur en rapport massique en % des éléments dans la fonte à graphite sphéroïdal.
  3. Fonte à graphite sphéroïdal selon la revendication 1 ou 2,
    dans laquelle la fonte à graphite sphéroïdal contient, en rapport massique, pas moins de 0,005 % de P et pas moins de 0,005 % de S.
  4. Fonte à graphite sphéroïdal selon l'une quelconque des revendications 1 à 3,
    dans laquelle la fonte à graphite sphéroïdal contient, en rapport massique, pas moins de 0,2 % de Mn et pas moins de 0,1 % de cuivre.
  5. Fonte à graphite sphéroïdal selon l'une quelconque des revendications 1 à 4,
    dans laquelle la fonte à graphite sphéroïdal présente une résistance à la traction pas inférieure à 600 MPa et un allongement pas inférieur à 12 %, qui sont mesurés selon la norme JIS Z 2241.
  6. Fonte à graphite sphéroïdal selon l'une quelconque des revendications 1 à 5,
    dans laquelle le rapport surfacique de défauts gazeux de la fonte à graphite sphéroïdal n'est pas supérieur à 11 %, mesuré tel que défini dans la description.
  7. Fonte à graphite sphéroïdal selon l'une quelconque des revendications 1 à 6,
    dans laquelle le taux d'amélioration de durée de vie d'outil de la fonte à graphite sphéroïdal n'est pas inférieur à 1,0 fois, mesuré tel que défini dans la description.
EP16850700.2A 2015-09-30 2016-02-29 Fonte à graphite sphéroïdal présentant une excellente résistance aux défauts gazeux Active EP3358026B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015192682 2015-09-30
PCT/JP2016/055973 WO2017056522A1 (fr) 2015-09-30 2016-02-29 Fonte à graphite sphéroïdal présentant une excellente résistance aux défauts gazeux

Publications (3)

Publication Number Publication Date
EP3358026A1 EP3358026A1 (fr) 2018-08-08
EP3358026A4 EP3358026A4 (fr) 2019-04-17
EP3358026B1 true EP3358026B1 (fr) 2021-06-02

Family

ID=58423018

Family Applications (1)

Application Number Title Priority Date Filing Date
EP16850700.2A Active EP3358026B1 (fr) 2015-09-30 2016-02-29 Fonte à graphite sphéroïdal présentant une excellente résistance aux défauts gazeux

Country Status (6)

Country Link
US (1) US20190055631A1 (fr)
EP (1) EP3358026B1 (fr)
JP (1) JP6191781B1 (fr)
KR (1) KR102539284B1 (fr)
CN (1) CN108138275B (fr)
WO (1) WO2017056522A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116200647B (zh) * 2023-03-17 2023-08-22 阜新力达钢铁铸造有限公司 铁素体球墨铸铁、铸件及其制备方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0813079A (ja) * 1994-07-01 1996-01-16 Mazda Motor Corp 球状黒鉛鋳鉄とその製造方法
DE19654893C2 (de) * 1996-07-25 1999-06-10 Federal Mogul Burscheid Gmbh Kolbenringe von Verbrennungskraftmaschinen aus einer Gußeisenlegierung
JP3960378B2 (ja) 2002-11-22 2007-08-15 福岡県 低温靱性に優れた球状黒鉛鋳鉄及びその製造方法
FI118738B (fi) * 2005-01-05 2008-02-29 Metso Paper Inc Pallografiittivalurauta ja menetelmä pallografiittivaluraudan valmistamiseksi lujuutta ja sitkeyttä vaativia koneenrakennusosia varten
JP4835424B2 (ja) * 2006-12-22 2011-12-14 Ｊｆｅスチール株式会社 高強度球状黒鉛鋳鉄
CN101748325B (zh) * 2009-12-30 2011-05-18 山东省汇丰机械集团总公司章丘市铸造厂 一种高强度耐磨球铁卷筒及其制造方法
JP5712525B2 (ja) * 2010-08-09 2015-05-07 Ｊｆｅスチール株式会社 耐摩耗性に優れた球状黒鉛鋳鉄品
JP5208175B2 (ja) * 2010-09-02 2013-06-12 アイシン高丘株式会社 車両鋳鉄部品
JP2012122085A (ja) * 2010-12-06 2012-06-28 Suzuki Motor Corp フェライト系球状黒鉛鋳鉄およびこれを用いた自動車の排気系部品
EP2471960B1 (fr) * 2010-12-30 2014-06-18 Casa Maristas Azterlan Procédé d'élaboration de pièces en fonte à graphite sphéroïdal
CN104024450B (zh) * 2011-12-28 2017-03-29 日立金属株式会社 强度和韧性优异的球状石墨铸铁及其制造方法
JP6162364B2 (ja) * 2012-02-24 2017-07-12 株式会社リケン 高剛性球状黒鉛鋳鉄

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Gusseisen mit Kugelgraphit", WIKIPEDIA, 29 July 2015 (2015-07-29), XP055913979

Also Published As

Publication number Publication date
JP6191781B1 (ja) 2017-09-06
EP3358026A4 (fr) 2019-04-17
WO2017056522A1 (fr) 2017-04-06
KR102539284B1 (ko) 2023-06-02
KR20180059459A (ko) 2018-06-04
JPWO2017056522A1 (ja) 2017-10-05
CN108138275B (zh) 2020-10-27
EP3358026A1 (fr) 2018-08-08
US20190055631A1 (en) 2019-02-21
CN108138275A (zh) 2018-06-08

Similar Documents

Publication Publication Date Title
EP3121302B1 (fr) Alliage d'aluminium pour coulée sous pression et alliage d'aluminium coulé sous pression l'utilisant
EP2184372B9 (fr) Fonte austénitique, son procédé de fabrication, pièces moulées en fonte austénitique, et pièces de système d'échappement
US11466349B2 (en) Spheroidal graphite cast iron
CN101798660A (zh) 冷轧辊钢以铸代锻的精炼、变质及铸造方法
KR20180008612A (ko) 주철 용탕 처리 방법
EP2573199B1 (fr) Fonte austénitique, produit coulé de fonte austénitique et procédé de fabrication de produit coulé
JP4145242B2 (ja) 鋳物用アルミニウム合金、アルミニウム合金製鋳物およびアルミニウム合金製鋳物の製造方法
US6908589B2 (en) High manganese cast iron containing spheroidal vanadium carbide and method for making therof
EP3358026B1 (fr) Fonte à graphite sphéroïdal présentant une excellente résistance aux défauts gazeux
KR20140116326A (ko) 가공성이 우수한 고강도 편상 흑연 주철 및 그 제조방법
EP3434799B1 (fr) Procédé de fabrication d'un article moulé comprenant de la fonte à graphite sphéroïdal
JP6793583B2 (ja) 低熱膨張合金
JP5282546B2 (ja) 耐摩耗性に優れた高強度厚肉球状黒鉛鋳鉄品
JP5282547B2 (ja) 耐摩耗性に優れた高強度厚肉球状黒鉛鋳鉄品
JP6793574B2 (ja) 低熱膨張合金
Larrañaga et al. Gray Cast Iron with High Austenite-to-Eutectic Ratio Part II–Increasing the Austenite-to-Eutectic Ratio through Austenite Nucleation
Polishko Influence of multifunctional modification on stabilization of chemical composition of wheel steels
JP6949352B2 (ja) 低熱膨張合金
JPS6056056A (ja) 加工硬化性オ−ステナイト系マンガン鋼およびその製造方法
KR101657850B1 (ko) 경화능이 우수한 중탄소 쾌삭강 및 그 제조방법
KR102353612B1 (ko) 마그네슘 합금, 이를 이용한 마그네슘 합금 판재 및 이의 제조방법
WO2016157574A1 (fr) Fonte à graphite sphérique à haute rigidité
JP2009001865A (ja) 球状黒鉛鋳鉄部材
EP3239314B1 (fr) Fonte à graphite sphéroïdal, son procédé de fabrication et composant de dispositif hydraulique fabriqué à partir de cette dernière
KR20230025184A (ko) 제조성이 우수한 cgi 주철 및 그 제조방법

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20180403

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20190319

RIC1 Information provided on ipc code assigned before grant

Ipc: C22C 33/08 20060101ALI20190313BHEP

Ipc: C22C 37/10 20060101ALI20190313BHEP

Ipc: C22C 33/10 20060101ALI20190313BHEP

Ipc: C21C 1/10 20060101ALI20190313BHEP

Ipc: C22C 37/04 20060101AFI20190313BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: C22C 37/10 20060101ALI20201217BHEP

Ipc: C22C 37/04 20060101AFI20201217BHEP

Ipc: C21C 1/10 20060101ALI20201217BHEP

Ipc: C22C 33/08 20060101ALI20201217BHEP

INTG Intention to grant announced

Effective date: 20210115

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

RIN1 Information on inventor provided before grant (corrected)

Inventor name: KAWABATA, MASAHIDE

Inventor name: YAMANE, HIDEYA

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1398479

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210615

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602016058950

Country of ref document: DE

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210602

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210602

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210602

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210902

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20210602

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1398479

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210602

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210903

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210602

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210902

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210602

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210602

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210602

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210602

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210602

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210602

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210602

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210602

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20211004

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210602

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210602

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210602

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 602016058950

Country of ref document: DE

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

26 Opposition filed

Opponent name: KSB SE & CO. KGAA

Effective date: 20220302

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210602

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210602

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210602

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210602

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20220228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220228

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220228

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20160229

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210602

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210602

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20231229

Year of fee payment: 9

Ref country code: GB

Payment date: 20240109

Year of fee payment: 9