EP0921541A1 - Fabrication process of a soft nanocrystalline magnetic core for use in a differentiel circuit breaker - Google Patents
Fabrication process of a soft nanocrystalline magnetic core for use in a differentiel circuit breaker Download PDFInfo
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- EP0921541A1 EP0921541A1 EP98402804A EP98402804A EP0921541A1 EP 0921541 A1 EP0921541 A1 EP 0921541A1 EP 98402804 A EP98402804 A EP 98402804A EP 98402804 A EP98402804 A EP 98402804A EP 0921541 A1 EP0921541 A1 EP 0921541A1
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- alloy
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- heat treatment
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- 238000000034 method Methods 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 238000002425 crystallisation Methods 0.000 claims abstract description 18
- 230000008025 crystallization Effects 0.000 claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 229910052796 boron Inorganic materials 0.000 claims abstract description 12
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 11
- 229910001004 magnetic alloy Inorganic materials 0.000 claims abstract description 10
- 230000005284 excitation Effects 0.000 claims abstract description 9
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 9
- 230000006698 induction Effects 0.000 claims abstract description 9
- 230000035699 permeability Effects 0.000 claims abstract description 9
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 8
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 18
- 239000000956 alloy Substances 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- 239000010703 silicon Substances 0.000 claims description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 11
- 239000010955 niobium Substances 0.000 claims description 11
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 10
- 238000011282 treatment Methods 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 8
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910000808 amorphous metal alloy Inorganic materials 0.000 abstract 2
- 229910000521 B alloy Inorganic materials 0.000 abstract 1
- NFCWKPUNMWPHLM-UHFFFAOYSA-N [Si].[B].[Fe] Chemical compound [Si].[B].[Fe] NFCWKPUNMWPHLM-UHFFFAOYSA-N 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 230000035945 sensitivity Effects 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- 238000002070 Raman circular dichroism spectroscopy Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/147—Alloys characterised by their composition
- H01F1/153—Amorphous metallic alloys, e.g. glassy metals
- H01F1/15341—Preparation processes therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/147—Alloys characterised by their composition
- H01F1/153—Amorphous metallic alloys, e.g. glassy metals
- H01F1/15333—Amorphous metallic alloys, e.g. glassy metals containing nanocrystallites, e.g. obtained by annealing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0206—Manufacturing of magnetic cores by mechanical means
- H01F41/0213—Manufacturing of magnetic circuits made from strip(s) or ribbon(s)
- H01F41/0226—Manufacturing of magnetic circuits made from strip(s) or ribbon(s) from amorphous ribbons
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H83/00—Protective switches, e.g. circuit-breaking switches, or protective relays operated by abnormal electrical conditions otherwise than solely by excess current
- H01H83/14—Protective switches, e.g. circuit-breaking switches, or protective relays operated by abnormal electrical conditions otherwise than solely by excess current operated by imbalance of two or more currents or voltages, e.g. for differential protection
- H01H83/144—Protective switches, e.g. circuit-breaking switches, or protective relays operated by abnormal electrical conditions otherwise than solely by excess current operated by imbalance of two or more currents or voltages, e.g. for differential protection with differential transformer
Definitions
- the present invention relates to a magnetic core of magnetic alloy soft nanocrystalline usable in particular for the manufacture of a circuit breaker Class A differential.
- Class A RCDs are self-contained RCDs sensitive not only to sinusoidal fault currents, but also to pulsed fault currents.
- These differential circuit breakers comprise a magnetic core made of soft magnetic alloy having a maximum magnetic permeability of impedance ⁇ z at 50 Hertz high and a Br / Bm ratio of the residual induction to the induction at saturation of less than 0.2, and a good temperature stability of the magnetic properties in the operating temperature range which extends from - 25 ° C to + 100 ° C.
- the maximum magnetic permeability of impedance ⁇ z must be high, because the higher it is, the more it is possible to reduce the dimensions of the magnetic core and therefore to miniaturize the differential circuit breaker; the Br / Bm ratio must remain low to preserve the sensitivity of the circuit breaker to pulsed currents.
- the sensitivity of the circuit breaker to pulsed fault currents is all the better as the magnitudes ⁇ B stat and ⁇ B dyn are higher; ⁇ B stat and ⁇ B dyn being the amplitudes of variation of the magnetic induction generated by an alternating excitation field rectified half-wave in the first case and full wave in the second.
- Magnetic cores for class A residual current devices can be manufactured using a soft magnetic alloy of the type comprising more than 60 atoms% of iron, copper, silicon, boron and an element chosen from niobium, titanium, zirconium, hafnium, vanadium, tantalum, chromium, molybdenum, tungsten and manganese.
- These magnetic cores are obtained by casting the alloy in the form of an amorphous ribbon which is wound to form a torus, then subjected to a crystallization heat treatment intended to give the alloy a nanocrystalline structure, and, finally, subjected to a heat treatment under transverse magnetic field applied continuously throughout the heat treatment, the heat treatment being carried out at around 400 ° C.
- the magnetic cores thus obtained have satisfactory temperature stability and a Br / Bm ratio of less than 0.2. However, they do not make it possible to obtain a magnetic permeability of impedance ⁇ z measured at 50 Hz in a maximum excitation field of 10 mA / cm (peak value) at 25 ° C greater than 170,000 or values of ⁇ B stat and ⁇ B dyn greater than 0.19 Tesla for an excitation field with a maximum amplitude of 10 mA / cm, which limits the possibilities of miniaturization.
- the object of the present invention is to remedy this drawback by proposing a means for manufacturing a magnetic core usable in a class A differential circuit breaker having both a magnetic permeability of impedance ⁇ z measured at 50 Hz in a field d '' maximum excitation of 10 mA / cm (peak value) greater than 200,000 and values of ⁇ B stat and ⁇ B dyn greater than 0.2 Tesla for an excitation field of maximum amplitude of 10 mA / cm.
- the invention relates to a process for the manufacture of a core magnetic nanocrystalline soft magnetic alloy with a chemical composition contains more than 60 atom% of iron, from 10 to 20 atom% of silicon, from 0.1 to 2 atom% of copper, 5 to 20 atom% of boron, 0.1 to 10 atom% of at least minus one element taken from niobium, titanium, zirconium, hafnium, vanadium, tantalum, chromium, molybdenum, tungsten and manganese, as well only impurities resulting from processing; the sum of the silicon and boron being less than 30 atom%; the nanocrystalline alloy being obtained by a heat treatment for crystallization of the alloy in an amorphous state.
- a thermal treatment is carried out on the magnetic core transverse magnetic at a temperature between 250 ° C and 450 ° C, the magnetic field being applied in the form of slots.
- the heat treatment under transverse magnetic field is carried out at a temperature between 300 ° C and 400 ° C.
- This process applies more particularly to soft magnetic alloys nanocrystalline whose chemical composition comprises from 10 to 17 atom% of silicon, from 0.5 to 1.5 atom% of copper, from 5 to 14 atom% of boron and from 2 to 4% at least one element taken from niobium, titanium, zirconium, hafnium, vanadium, tantalum, chromium, molybdenum, tungsten and manganese.
- the thermal relaxation treatment consists of maintaining at a temperature between 250 ° C and 480 ° C for a time between 0.1 and 10 hours.
- the magnetic core obtained by the process according to the invention can be used advantageously for the manufacture of a differential circuit breaker with its own current class A.
- the sum of the silicon and boron contents should preferably remain less than 30 at% and, better still, remain less than 25 at%.
- the crystallization annealing consists of maintaining at a temperature higher than the start of crystallization temperature and lower than the temperature from the onset of secondary phases which deteriorate the properties magnetic.
- the crystallization annealing temperature is understood between 500 ° C and 600 ° C, but it can be optimized for each ribbon, by example, by determining by tests the temperature which leads to permeability maximum magnetic. The crystallization annealing temperature can then be chosen equal to this temperature.
- the heat treatment carried out under magnetic field is carried out at a temperature between 250 ° C and 450 ° C, and preferably between 300 ° C and 400 ° C.
- the magnetic field is applied in the form of a succession of slots.
- One slot corresponds to one period during which the applied magnetic field is maximum, followed by a period during which it is zero or very weak (less than 10% of the magnetic field reached during treatment).
- the applied magnetic field can be continuous or alternating, in the latter case the intensity of the magnetic field is peak intensity (maximum intensity reached at each alternation).
- the intensity of magnetic field can be constant throughout the period of application of the field (rectangular slots) or variable. All slots can be from same intensity or on the contrary of variable intensity from one niche to another.
- the heat treatment can end at the end of the field application period magnetic of the last slot; the main thing is that the treatment involves at least two periods during which the applied magnetic field separated by a period during which the magnetic field is not applied.
- the the inventors have in fact found that by doing so, the temperature stability magnetic properties of the magnetic core were very noticeably improved.
- a magnetic core is obtained whose magnetic permeability of impedance ⁇ z measured at 50 Hertz in a magnetic field of maximum excitation of 10 mA / cm (peak value) at 25 ° C is greater than 200,000, and whose magnetic permeability varies by less than 25% over the temperature range between - 25 ° C and + 100 ° C.
- the Br / Bm ratio of the residual induction to the saturation induction is less than 0.2
- ⁇ B stat and ⁇ B dyn are both greater than 0.2 Tesla, the ⁇ B stat / ⁇ B dyn ratio being close to 1.
- Such a magnetic core can be used in a class A differential circuit breaker. Because of its magnetic properties, at equal sensitivity of the circuit breaker, the section of the core can be reduced significantly compared to the section of a core magnetic according to the prior art.
- the other series, B was subjected to a heat treatment of 1 hour at 350 under transverse magnetic field applied in the form of slots of 5 min under magnetic field separated by periods of 15 min without magnetic field .
- the magnitudes ⁇ z , ⁇ B stat and ⁇ B dyn were measured at 25 ° C for an alternating excitation magnetic field at 50 Hertz with a maximum amplitude of 10 mA / cm; the Br / Bm ratio was also measured.
- the results were as follows: series ⁇ (10 mA / cm ° ⁇ B stat (T) ⁇ B dyn (T) ⁇ B stat / ⁇ B dyn Br / Bm To compare. 153,000 0.172 0.169 1.017 0.05 B invention 230,000 0.240 0.234 1.025 0.1
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Soft Magnetic Materials (AREA)
Abstract
Description
La présente invention concerne un noyau magnétique en alliage magnétique doux nanocristallin utilisable notamment pour la fabrication d'un disjoncteur différentiel de la classe A.The present invention relates to a magnetic core of magnetic alloy soft nanocrystalline usable in particular for the manufacture of a circuit breaker Class A differential.
Les disjoncteurs différentiels de la classe A sont des disjoncteurs différentiels à propre courant sensible non seulement aux courants de défaut sinusoïdaux, mais également aux courants de défauts pulsés. Ces disjoncteurs différentiels comportent un noyau magnétique en alliage magnétique doux ayant une perméabilité magnétique maximale d'impédance µz à 50 Hertz élevée et un rapport Br/Bm de l'induction rémanente à l'induction à saturation inférieure à 0,2, et une bonne stabilité en température des propriétés magnétiques dans la plage de température de fonctionnement qui s'étend de - 25 °C à + 100 °C. La perméabilité magnétique maximale d'impédance µz doit être élevée, car, plus elle est élevé, plus il est possible de réduire les dimensions du noyau magnétique et donc de miniaturiser le disjoncteur différentiel ; le rapport Br/Bm doit rester faible pour préserver la sensibilité du disjoncteur aux courants pulsés. De plus, la sensibilité du disjoncteur aux courants de défaut pulsés est d'autant meilleur que les grandeurs ΔBstat et ΔBdyn sont plus élevés ; ΔBstat et ΔBdyn étant les amplitudes de variation de l'induction magnétique engendrées par un champ d'excitation alternatif redressé demi-onde dans le premier cas et pleine onde dans le second.Class A RCDs are self-contained RCDs sensitive not only to sinusoidal fault currents, but also to pulsed fault currents. These differential circuit breakers comprise a magnetic core made of soft magnetic alloy having a maximum magnetic permeability of impedance μ z at 50 Hertz high and a Br / Bm ratio of the residual induction to the induction at saturation of less than 0.2, and a good temperature stability of the magnetic properties in the operating temperature range which extends from - 25 ° C to + 100 ° C. The maximum magnetic permeability of impedance µ z must be high, because the higher it is, the more it is possible to reduce the dimensions of the magnetic core and therefore to miniaturize the differential circuit breaker; the Br / Bm ratio must remain low to preserve the sensitivity of the circuit breaker to pulsed currents. In addition, the sensitivity of the circuit breaker to pulsed fault currents is all the better as the magnitudes ΔB stat and ΔB dyn are higher; ΔB stat and ΔB dyn being the amplitudes of variation of the magnetic induction generated by an alternating excitation field rectified half-wave in the first case and full wave in the second.
On peut fabriquer des noyaux magnétiques pour disjoncteurs différentiels de la classe A en utilisant un alliage magnétique doux du type comprenant plus de 60 atomes % de fer, du cuivre, du silicium, du bore et un élément pris parmi le niobium, le titane, le zirconium, le hafnium, le vanadium, le tantale, le chrome, le molybdène, le tungstène et le manganèse. Ces noyaux magnétiques sont obtenus en coulant l'alliage sous forme d'un ruban amorphequi est enroulé pour former un tore, puis soumis à un traitement thermique de cristallisation destiné à conférer à l'alliage une structure nanocristalline, et, enfin, soumis à un traitement thermique sous champ magnétique transverse appliqué de façon continue tout au long du traitement thermique, le traitement thermique se faisant vers 400 °C. Les noyaux magnétiques ainsi obtenus ont une stabilité en température satisfaisante et un rapport Br/Bm inférieur à 0,2. Mais ils ne permettent pas d'obtenir une perméabilité magnétique d'impédance µz mesurée à 50 Hz dans un champ d'excitation maximale de 10 mA/cm (valeur de crête) à 25 °C supérieure à 170 000 ni des valeurs de ΔBstat et ΔBdyn supérieures à 0,19 Tesla pour un champ d'excitation d'amplitude maximale de 10 mA/cm, ce qui limite les possibilités de miniaturisation.Magnetic cores for class A residual current devices can be manufactured using a soft magnetic alloy of the type comprising more than 60 atoms% of iron, copper, silicon, boron and an element chosen from niobium, titanium, zirconium, hafnium, vanadium, tantalum, chromium, molybdenum, tungsten and manganese. These magnetic cores are obtained by casting the alloy in the form of an amorphous ribbon which is wound to form a torus, then subjected to a crystallization heat treatment intended to give the alloy a nanocrystalline structure, and, finally, subjected to a heat treatment under transverse magnetic field applied continuously throughout the heat treatment, the heat treatment being carried out at around 400 ° C. The magnetic cores thus obtained have satisfactory temperature stability and a Br / Bm ratio of less than 0.2. However, they do not make it possible to obtain a magnetic permeability of impedance μ z measured at 50 Hz in a maximum excitation field of 10 mA / cm (peak value) at 25 ° C greater than 170,000 or values of ΔB stat and ΔB dyn greater than 0.19 Tesla for an excitation field with a maximum amplitude of 10 mA / cm, which limits the possibilities of miniaturization.
Le but de la présente invention est de remédier à cet inconvénient en proposant un moyen pour fabriquer un noyau magnétique utilisable dans un disjoncteur différentiel de la classe A ayant à la fois une perméabilité magnétique d'impédance µz mesurée à 50 Hz dans un champ d'excitation maximale de 10 mA/cm (valeur de crête) supérieure à 200 000 et des valeurs de ΔBstat et ΔBdyn supérieures à 0,2 Tesla pour un champ d'excitation d'amplitude maximale de 10 mA/cm.The object of the present invention is to remedy this drawback by proposing a means for manufacturing a magnetic core usable in a class A differential circuit breaker having both a magnetic permeability of impedance μ z measured at 50 Hz in a field d '' maximum excitation of 10 mA / cm (peak value) greater than 200,000 and values of ΔB stat and ΔB dyn greater than 0.2 Tesla for an excitation field of maximum amplitude of 10 mA / cm.
A cet effet, l'invention a pour objet un procédé pour la fabrication d'un noyau magnétique en alliage magnétique doux nanocristallin dont la composition chimique comprend plus de 60 atomes % de fer, de 10 à 20 atomes % de silicium, de 0,1 à 2 atomes % de cuivre, de 5 à 20 atomes % de bore, de 0,1 à 10 atomes % d'au moins un élément pris parmi le niobium, le titane, le zirconium, le hafnium, le vanadium, le tantale, le chrome, le molybdène, le tungstène et le manganèse, ainsi que des impuretés résultant de l'élaboration; la somme des teneurs en silicium et en bore étant inférieure à 30 atomes %; l'alliage nanocristallin étant obtenu par un traitement thermique de cristallisation de l'alliage à l'état amorphe. Selon ce procédé, on effectue sur le noyau magnétique un traitement thermique sous champ magnétique transverse à une température comprise entre 250 °C et 450 °C, le champ magnétique étant appliqué sous forme de créneaux.To this end, the invention relates to a process for the manufacture of a core magnetic nanocrystalline soft magnetic alloy with a chemical composition contains more than 60 atom% of iron, from 10 to 20 atom% of silicon, from 0.1 to 2 atom% of copper, 5 to 20 atom% of boron, 0.1 to 10 atom% of at least minus one element taken from niobium, titanium, zirconium, hafnium, vanadium, tantalum, chromium, molybdenum, tungsten and manganese, as well only impurities resulting from processing; the sum of the silicon and boron being less than 30 atom%; the nanocrystalline alloy being obtained by a heat treatment for crystallization of the alloy in an amorphous state. According to this process, a thermal treatment is carried out on the magnetic core transverse magnetic at a temperature between 250 ° C and 450 ° C, the magnetic field being applied in the form of slots.
De préférence, le traitement thermique sous champ magnétique transverse est effectué à une température comprise entre 300 °C et 400 °C.Preferably, the heat treatment under transverse magnetic field is carried out at a temperature between 300 ° C and 400 ° C.
Ce procédé s'applique plus particulièrement aux alliages magnétiques doux nanocristallins dont la composition chimique comprend de 10 à 17 atomes % de silicium, de 0,5 à 1,5 atomes % de cuivre, de 5 à 14 atomes % de bore et de 2 à 4 % d'au moins un élément pris parmi le niobium, le titane, le zirconium, le hafnium, le vanadium, le tantale, le chrome, le molybdène, le tungstène et le manganèse. This process applies more particularly to soft magnetic alloys nanocrystalline whose chemical composition comprises from 10 to 17 atom% of silicon, from 0.5 to 1.5 atom% of copper, from 5 to 14 atom% of boron and from 2 to 4% at least one element taken from niobium, titanium, zirconium, hafnium, vanadium, tantalum, chromium, molybdenum, tungsten and manganese.
Avant d'effectuer le traitement thermique de cristallisation de l'alliage à l'état amorphe, on peut effectuer sur l'alliage à l'état amorphe un traitement thermique de relaxation à une température inférieure à la température de début de cristallisation de l'alliage à l'état amorphe. De préférence, le traitement thermique de relaxation consiste en un maintien à une température comprise entre 250 °C et 480 °C pendant un temps compris entre 0,1 et 10 heures.Before carrying out the heat treatment of crystallization of the alloy in the state amorphous, one can carry out on the alloy in the amorphous state a heat treatment of relaxation at a temperature below the temperature at the start of crystallization of the alloy in the amorphous state. Preferably, the thermal relaxation treatment consists of maintaining at a temperature between 250 ° C and 480 ° C for a time between 0.1 and 10 hours.
Le noyau magnétique obtenu par le procédé selon l'invention peut être utilisé avantageusement pour la fabrication d'un disjoncteur différentiel à propre courant de la classe A.The magnetic core obtained by the process according to the invention can be used advantageously for the manufacture of a differential circuit breaker with its own current class A.
L'invention va maintenant être décrite plus en détails et illustrée par un exemple.The invention will now be described in more detail and illustrated by a example.
Pour fabriquer un noyau magnétique en alliage magnétique doux nanocristallin, on coule l'alliage sous forme d'un ruban amorphe, puis on enroule un segment de ruban de longueur appropriée autour d'un mandrin de façon à former une bobine torique de section rectangulaire ou carrée. La bobine qui va constituer le noyau magnétique est alors soumise à un traitement thermique de cristallisation destiné à déstabiliser la structure amorphe et à provoquer la formation de cristaux dont la taille est inférieure à 100 nanomètres, voire inférieure à 20 nanomètres, et, ainsi, obtenir une structure appelée « nanocristalline ». Ce traitement est, ensuite, complété par un traitement thermique sous champ magnétique transverse, c'est à dire, sous un champ magnétique parallèle à l'axe du noyau. L'alliage est du type décrit notamment dans les demandes de brevet européen EP 0 271 657 et EP 0 299 498. Il est constitué principalement de fer en une teneur supérieure à 60 atomes %, et contient en outre :
- de 0,1 à 2 at %, et de préférence, de 0,5 à 1,5 at % de cuivre ;
- de 10 à 20 at %, et de préférence, moins de 17 at % de silicium ;
- de 5 à 20 at %, et de préférence, moins de 14 at % de bore ;
- de 0,1 à 10 at % d'au moins un élément pris parmi le niobium, le titane, le zirconium, le hafnium, le vanadium, le tantale, le chrome, le molybdène, le tungstène et le manganèse; de préférence de 2 et 4 at % de niobium .
- 0.1 to 2 at%, and preferably 0.5 to 1.5 at% copper;
- from 10 to 20 at%, and preferably, less than 17 at% of silicon;
- from 5 to 20 at%, and preferably less than 14 at% boron;
- from 0.1 to 10 at% of at least one element chosen from niobium, titanium, zirconium, hafnium, vanadium, tantalum, chromium, molybdenum, tungsten and manganese; preferably 2 and 4 at% niobium.
La somme des teneurs en silicium et en bore doit, de préférence, rester inférieure à 30 at % et, mieux encore, rester inférieure à 25 at %.The sum of the silicon and boron contents should preferably remain less than 30 at% and, better still, remain less than 25 at%.
Le recuit de cristallisation consiste en un maintien à une température supérieure à la température de début de cristallisation et inférieure à la température de début d'apparition des phases secondaires qui détériorent les propriétés magnétiques. En général, la température de recuit de cristallisation est comprises entre 500 °C et 600 °C, mais elle peut être optimisée pour chaque ruban, par exemple, en déterminant par des essais la température qui conduit à la perméabilité magnétique maximale. La température de recuit de cristallisation peut alors être choisie égale à cette température.The crystallization annealing consists of maintaining at a temperature higher than the start of crystallization temperature and lower than the temperature from the onset of secondary phases which deteriorate the properties magnetic. In general, the crystallization annealing temperature is understood between 500 ° C and 600 ° C, but it can be optimized for each ribbon, by example, by determining by tests the temperature which leads to permeability maximum magnetic. The crystallization annealing temperature can then be chosen equal to this temperature.
Le traitement thermique effectué sous champ magnétique est effectué à une température comprise entre 250 °C et 450 °C, et de préférence entre 300 °C et 400 °C. Pendant le maintien en température, le champ magnétique est appliqué sous forme d'une succession de créneaux. Un créneau correspond à une période pendant laquelle le champ magnétique appliqué est maximal, suivi d'une période pendant la quelle il est nul ou très faible (inférieur à 10 % du champ magnétique maximal atteint pendant le traitement). Le champ magnétique appliqué peut être continu ou alternatif, dans ce dernier cas, l'intensité du champ magnétique est l'intensité de crête (intensité maximale atteinte à chaque alternance). L'intensité du champ magnétique peut être constante pendant toute la période d'application du champ (créneaux rectangulaires) ou variable. Tous les créneaux peuvent être de même intensité ou au contraire d'intensité variable d'un créneau à l'autre. Le traitement thermique peut se terminer à la fin de la période d'application du champ magnétique du dernier créneau ; l'essentiel étant que le traitement comporte au moins deux périodes pendant lesquelles le champ magnétique appliqué séparées par une période pendant laquelle le champ magnétique n'est pas appliqué. Les inventeurs ont, en effet, constaté qu'en procédant ainsi, la stabilité en température des propriétés magnétiques du noyau magnétique étaient très sensiblement améliorées.The heat treatment carried out under magnetic field is carried out at a temperature between 250 ° C and 450 ° C, and preferably between 300 ° C and 400 ° C. During temperature maintenance, the magnetic field is applied in the form of a succession of slots. One slot corresponds to one period during which the applied magnetic field is maximum, followed by a period during which it is zero or very weak (less than 10% of the magnetic field reached during treatment). The applied magnetic field can be continuous or alternating, in the latter case the intensity of the magnetic field is peak intensity (maximum intensity reached at each alternation). The intensity of magnetic field can be constant throughout the period of application of the field (rectangular slots) or variable. All slots can be from same intensity or on the contrary of variable intensity from one niche to another. The heat treatment can end at the end of the field application period magnetic of the last slot; the main thing is that the treatment involves at least two periods during which the applied magnetic field separated by a period during which the magnetic field is not applied. The the inventors have in fact found that by doing so, the temperature stability magnetic properties of the magnetic core were very noticeably improved.
Par ce procédé on obtient un noyau magnétique dont la perméabilité magnétique d'impédance µz mesurée à 50 Hertz dans un champ magnétique d'excitation maximale de 10 mA/cm (valeur de crête) à 25 °C est supérieur à 200 000, et dont la perméabilité magnétique varie de moins de 25 % sur la plage de température comprise entre - 25 °C et + 100 °C. De plus, le rapport Br/Bm de l'induction rémanente à l'induction à saturation est inférieure à 0,2, ΔBstat et ΔBdyn sont tous les deux supérieures à 0,2 Tesla, le rapport ΔBstat/ΔBdyn étant voisin de 1. Un tel noyau magnétique peut être utilisé dans un disjoncteur différentiel de la classe A. Du fait de ses propriétés magnétiques, à sensibilité égale du disjoncteur, la section du noyau peut être réduite sensiblement par rapport à la section d'un noyau magnétique selon l'art antérieur.By this process, a magnetic core is obtained whose magnetic permeability of impedance µ z measured at 50 Hertz in a magnetic field of maximum excitation of 10 mA / cm (peak value) at 25 ° C is greater than 200,000, and whose magnetic permeability varies by less than 25% over the temperature range between - 25 ° C and + 100 ° C. In addition, the Br / Bm ratio of the residual induction to the saturation induction is less than 0.2, ΔB stat and ΔB dyn are both greater than 0.2 Tesla, the ΔB stat / ΔB dyn ratio being close to 1. Such a magnetic core can be used in a class A differential circuit breaker. Because of its magnetic properties, at equal sensitivity of the circuit breaker, the section of the core can be reduced significantly compared to the section of a core magnetic according to the prior art.
En complément des traitements thermiques qui viennent d'être décrit, on peut, avant le traitement thermique de cristallisation, effectuer sur le noyau un traitement thermique de relaxation à une température inférieure à la température de début de cristallisation de la bande amorphe, et, de préférence, comprise entre 250°C et 480 °C. Ce recuit de relaxation a pour avantage de réduire encore la sensibilité des propriétés magnétiques des noyaux à la température, de réduire la dispersion des propriétés magnétiques de noyaux fabriqués en série et de réduire la sensibilité des propriétés magnétiques aux contraintes.In addition to the heat treatments which have just been described, it is possible, before the crystallization heat treatment, carry out a treatment on the core thermal relaxation at a temperature below the start temperature of crystallization of the amorphous band, and preferably between 250 ° C and 480 ° C. This relaxation annealing has the advantage of further reducing the sensitivity of magnetic properties of cores at temperature, reduce the dispersion of magnetic properties of mass-produced cores and reduce the sensitivity of magnetic properties under stress.
A titre d'exemple, à partir d'un ruban en alliage Fe73,5Si13,5B9Cu1Nb3, (73,5
at % de fer, 13,5 at % de silicium, etc.), de 20 µm d'épaisseur et 10 mm de largeur
obtenus par trempe directe sur une roue refroidie, on a fabriqué deux séries A et B
de noyaux magnétiques qui ont été soumises toutes les deux à un traitement de
cristallisation de 1 heures à 530 °C (sans traitement de relaxation). A titre de
comparaison, la première série A de noyaux a été soumise à un traitement
thermique de 1 heure à 350 °C sous champ magnétique transverse appliqué de
façon continue. Conformément à l'invention, l'autre série, B, a été soumise à un
traitement thermique de 1 heure à 350 sous champ magnétique transverse appliqué
sous forme de créneaux de 5 mn sous champ magnétique séparées par des
périodes de 15 mn sans champ magnétique. Pour l'une des séries, on a mesuré à
25 °C les grandeurs µz, ΔBstat et ΔBdyn pour un champ magnétique d'excitation
alternatif à 50 Hertz d'amplitude maximale de 10 mA/cm ; on a également mesuré le
rapport Br/Bm. Les résultats ont été les suivants :
Ces exemples montrent bien l'amélioration de propriétés magnétiques apportées par le procédé selon l'invention : µz supérieur à 200 000, ΔBstat et ΔBdyn supérieurs à 0,2 Tesla, avec ΔBstat/ΔBdyn voisin de 1 et Br/Bm inférieur à 0,2.These examples clearly show the improvement in magnetic properties provided by the method according to the invention: μ z greater than 200,000, ΔB stat and ΔB dyn greater than 0.2 Tesla, with ΔB stat / ΔB dyn close to 1 and Br / Bm less than 0.2.
Claims (7)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9715273 | 1997-12-04 | ||
FR9715273A FR2772181B1 (en) | 1997-12-04 | 1997-12-04 | METHOD FOR MANUFACTURING A NANOCRYSTALLINE SOFT MAGNETIC ALLOY MAGNETIC CORE FOR USE IN A CLASS A DIFFERENTIAL CIRCUIT BREAKER AND MAGNETIC CORE OBTAINED |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0921541A1 true EP0921541A1 (en) | 1999-06-09 |
EP0921541B1 EP0921541B1 (en) | 2004-05-06 |
Family
ID=9514143
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98402804A Expired - Lifetime EP0921541B1 (en) | 1997-12-04 | 1998-11-13 | Fabrication process of a soft nanocrystalline magnetic core for use in a differential circuit breaker |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0921541B1 (en) |
AT (1) | ATE266245T1 (en) |
DE (1) | DE69823621T2 (en) |
FR (1) | FR2772181B1 (en) |
PL (1) | PL186806B1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19948897A1 (en) * | 1999-10-11 | 2001-04-19 | Vacuumschmelze Gmbh | Interface modules for local data networks |
EP1710812A1 (en) * | 2005-02-25 | 2006-10-11 | Magnetec GmbH | Fault-current circuit breaker and magnetic core for a fault-current circuit breaker |
US8699190B2 (en) | 2010-11-23 | 2014-04-15 | Vacuumschmelze Gmbh & Co. Kg | Soft magnetic metal strip for electromechanical components |
CN107419200A (en) * | 2017-06-30 | 2017-12-01 | 江苏理工学院 | A kind of soft magnetic iron-based nano-amorphous alloy containing manganese and preparation method thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0271657A2 (en) * | 1986-12-15 | 1988-06-22 | Hitachi Metals, Ltd. | Fe-base soft magnetic alloy and method of producing same |
EP0299498A1 (en) * | 1987-07-14 | 1989-01-18 | Hitachi Metals, Ltd. | Magnetic core and method of producing same |
EP0392204A2 (en) * | 1989-04-08 | 1990-10-17 | Vacuumschmelze GmbH | Use of a microcrystalline iron-based alloy as a magnetic material for a fault current-protective switch |
DE4019636A1 (en) * | 1989-07-01 | 1991-02-28 | James C M Li | METHOD FOR IMPROVING THE MAGNETIC PROPERTIES BY APPLYING AC OR PULSED CURRENT |
EP0563606A2 (en) * | 1992-04-01 | 1993-10-06 | Vacuumschmelze GmbH | Current transformer for earth-leakage circuit breakers which are sensitive to current pulses |
WO1996033505A1 (en) * | 1995-04-18 | 1996-10-24 | Schneider Electric S.A. | Current transformer, in particular for a fault current tripping device sensitive to pulsating currents and tripping device equipped with such a transformer |
-
1997
- 1997-12-04 FR FR9715273A patent/FR2772181B1/en not_active Expired - Fee Related
-
1998
- 1998-11-13 AT AT98402804T patent/ATE266245T1/en not_active IP Right Cessation
- 1998-11-13 EP EP98402804A patent/EP0921541B1/en not_active Expired - Lifetime
- 1998-11-13 DE DE69823621T patent/DE69823621T2/en not_active Expired - Lifetime
- 1998-12-04 PL PL98330101A patent/PL186806B1/en not_active IP Right Cessation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0271657A2 (en) * | 1986-12-15 | 1988-06-22 | Hitachi Metals, Ltd. | Fe-base soft magnetic alloy and method of producing same |
EP0299498A1 (en) * | 1987-07-14 | 1989-01-18 | Hitachi Metals, Ltd. | Magnetic core and method of producing same |
EP0392204A2 (en) * | 1989-04-08 | 1990-10-17 | Vacuumschmelze GmbH | Use of a microcrystalline iron-based alloy as a magnetic material for a fault current-protective switch |
DE4019636A1 (en) * | 1989-07-01 | 1991-02-28 | James C M Li | METHOD FOR IMPROVING THE MAGNETIC PROPERTIES BY APPLYING AC OR PULSED CURRENT |
EP0563606A2 (en) * | 1992-04-01 | 1993-10-06 | Vacuumschmelze GmbH | Current transformer for earth-leakage circuit breakers which are sensitive to current pulses |
WO1996033505A1 (en) * | 1995-04-18 | 1996-10-24 | Schneider Electric S.A. | Current transformer, in particular for a fault current tripping device sensitive to pulsating currents and tripping device equipped with such a transformer |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19948897A1 (en) * | 1999-10-11 | 2001-04-19 | Vacuumschmelze Gmbh | Interface modules for local data networks |
EP1710812A1 (en) * | 2005-02-25 | 2006-10-11 | Magnetec GmbH | Fault-current circuit breaker and magnetic core for a fault-current circuit breaker |
US8699190B2 (en) | 2010-11-23 | 2014-04-15 | Vacuumschmelze Gmbh & Co. Kg | Soft magnetic metal strip for electromechanical components |
CN107419200A (en) * | 2017-06-30 | 2017-12-01 | 江苏理工学院 | A kind of soft magnetic iron-based nano-amorphous alloy containing manganese and preparation method thereof |
CN107419200B (en) * | 2017-06-30 | 2019-11-22 | 江苏理工学院 | A kind of soft magnetic iron-based nanocrystalline and amorphous alloy and preparation method thereof containing manganese |
Also Published As
Publication number | Publication date |
---|---|
DE69823621D1 (en) | 2004-06-09 |
FR2772181B1 (en) | 2000-01-14 |
PL330101A1 (en) | 1999-06-07 |
EP0921541B1 (en) | 2004-05-06 |
ATE266245T1 (en) | 2004-05-15 |
FR2772181A1 (en) | 1999-06-11 |
PL186806B1 (en) | 2004-02-27 |
DE69823621T2 (en) | 2005-05-19 |
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