EP3202945A1 - Method for nitrocarburizing of metallic workpieces - Google Patents
Method for nitrocarburizing of metallic workpieces Download PDFInfo
- Publication number
- EP3202945A1 EP3202945A1 EP16154353.3A EP16154353A EP3202945A1 EP 3202945 A1 EP3202945 A1 EP 3202945A1 EP 16154353 A EP16154353 A EP 16154353A EP 3202945 A1 EP3202945 A1 EP 3202945A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- urea
- furnace chamber
- treatment
- water
- workpieces
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000004202 carbamide Substances 0.000 claims abstract description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 32
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 16
- 229910021529 ammonia Inorganic materials 0.000 abstract description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 8
- 239000001569 carbon dioxide Substances 0.000 abstract description 8
- VPKDCDLSJZCGKE-UHFFFAOYSA-N methanediimine Chemical compound N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 abstract description 4
- 230000007062 hydrolysis Effects 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 3
- 238000001149 thermolysis Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000001321 HNCO Methods 0.000 description 2
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 206010003497 Asphyxia Diseases 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/28—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases more than one element being applied in one step
- C23C8/30—Carbo-nitriding
- C23C8/32—Carbo-nitriding of ferrous surfaces
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/06—Surface hardening
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
- C21D1/76—Adjusting the composition of the atmosphere
Definitions
- the invention relates to a method for heat treating metallic workpieces in a furnace chamber, in particular for nitrocarburizing, wherein the workpieces are exposed to a treatment atmosphere at a treatment temperature during at least one treatment phase, with nitrogen and carbon diffusing into the workpieces.
- Nitrocarburizing is a heat treatment process for surface hardening workpieces made of steel, in which the workpieces are heated in a furnace chamber of an industrial furnace in a heating phase and exposed to a treatment atmosphere during a holding phase at a treatment temperature of about 500 ° C to 600 ° C, wherein nitrogen and carbon atoms diffuse into the surface layer of the workpieces. This is followed by a cooling phase. This results in the edge region of the workpieces, a bonding layer and a diffusion layer. Nitrocarburizing focuses on the formation of the bonding layer. The two layers are relatively thin. The aim of this thermochemical process is to improve the wear resistance and corrosion resistance, in particular of unalloyed, low to medium-alloyed steels.
- a treatment atmosphere customary in practice for the gas nitrocarburizing of metallic workpieces or components is a gas mixture of carbon dioxide (CO 2 ), ammonia (NH 3 ), hydrogen (H 2 ) and nitrogen (N 2 ).
- the CO 2 serves as a carbon donor and the NH 3 as a nitrogen donor.
- the treatment atmosphere is generated in practice in the furnace room of the industrial furnace.
- gaseous ammonia (NH 3 ), carbon dioxide (CO 2 ) and nitrogen (N 2 ) are fed directly into the furnace chamber.
- NH 3 gaseous ammonia
- CO 2 carbon dioxide
- N 2 nitrogen
- H 2 hydrogen
- the nitrogen and the carbon For introduction of nitrogen and carbon by diffusion into the edge region of workpieces made of steel or of steel components, the nitrogen and the carbon must be present in atomic form.
- the generation of atomic nitrogen takes place under predetermined temperature and pressure conditions by cleavage of ammonia in the furnace chamber.
- Ammonia (NH 3 ) in gaseous form is a very unpleasant-smelling, irritating and poisonous gas which can cause irritation, poisoning and asphyxiation. Occupational safety during the heat treatment is therefore in need of improvement. In addition, ammonia is relatively expensive, so that the heat treatment costs are high.
- the object of the invention is therefore to improve a method for heat treating metallic workpieces, in particular for nitrocarburizing, in such a way that the aforementioned problems are avoided.
- the object is achieved by a method according to claim 1.
- the treatment atmosphere is produced from urea or carbonic acid diamide (CH 4 N 2 O) and water (H 2 O).
- Urea with the chemical formula CH 4 N 2 O, has a molecular weight of 60.06 g / mol and is water-soluble.
- the invention is based on the finding that urea contains carbon and nitrogen and thus provides both necessary for the nitrocarburizing reactants C and N.
- Urea unlike ammonia, is non-toxic and relatively inexpensive.
- the urea decomposes into ammonia (NH 3 ) and isocyanic acid (HNCO). This in turn reacts with water (molar mass 18.015 g / mol) by hydrolysis to ammonia (NH 3 ) and carbon dioxide (CO 2 ).
- Urea CH 4 N 2 O in combination with a metered addition of water (H 2 O) ideally creates a treatment atmosphere of 66% ammonia (NH 3 ) and 33% carbon dioxide (CO 2 ). This makes urea, in combination with water, ideal for nitrocarburizing.
- the CO 2 is used during the heat treatment as a carbon donor and the NH 3 as a nitrogen donor.
- the molar ratio of urea (CH 4 N 2 O) to water (H 2 O) is about 1 to 1.
- a preferred embodiment is characterized in that the urea (CH 4 N 2 O) and the water (H 2 O) are fed directly into the furnace chamber and the treatment atmosphere is generated directly in the furnace chamber.
- the water (H 2 O) is fed in liquid form into the furnace chamber. But it is also possible to feed the water (H 2 O) in vapor form into the furnace chamber.
- the urea (CH 4 N 2 O) can be introduced in solid form into the furnace chamber.
- the inventive method is characterized in that the urea (CH 4 N 2 O) dissolved in the water (H 2 O) and the urea (CH 4 N 2 O) fed in the form of an aqueous solution in the furnace chamber, preferably sprayed, becomes.
- urea (CH 4 N 2 O) in the form of an aqueous solution and additionally urea (CH 4 N 2 O) in solid form in the furnace chamber can be introduced in order to change the composition of the treatment atmosphere.
- a variant of the method is characterized in that the urea (CH 4 N 2 O) and the water (H 2 O) are fed into a presplitter, which is heated to a temperature of at least 130 ° C, preferably at least 140 ° C, that the treatment atmosphere is generated in the presplitter and that the treatment atmosphere is passed from the presplitter into the furnace space.
- a presplitter which is heated to a temperature of at least 130 ° C, preferably at least 140 ° C, that the treatment atmosphere is generated in the presplitter and that the treatment atmosphere is passed from the presplitter into the furnace space.
- the Vorspalter is produced by chemical reaction, the desired gaseous treatment atmosphere.
- urea (CH 4 N 2 O) decomposes into isocyanic acid (HNCO) and ammonia (NH 3 ).
- the carbon availability of the treatment atmosphere can be increased by adding a carbon-containing additional gas.
- Carbon monoxide, carbon dioxide or propane, for example, can be used as additional gas.
- the workpieces are exposed during a holding phase at a treatment temperature of 500 ° C to 600 ° C of the treatment atmosphere.
- the holding phase is preceded by a warm-up phase.
- the holding phase is followed by a cooling phase.
- the workpieces At the end of the heat treatment, the workpieces have an increased surface hardness and good corrosion resistance.
- nitrocarburizing workpieces made of steel are heated in a furnace chamber during a heating phase and exposed during a holding phase at a treatment temperature of 500 ° C to 600 ° C a gaseous treatment atmosphere.
- the holding phase is followed by a cooling phase.
- According to the treatment atmosphere of urea or carbonic acid diamide (CH 4 N 2 O) and water (H 2 O) is generated directly in the furnace chamber.
- Urea (CH 4 N 2 O) contains carbon and nitrogen and thus both necessary for the nitrocarburizing reactants C and N.
- the urea (CH 4 N 2 O) is dissolved outside the furnace chamber in the water (H 2 O) and the urea ( CH 4 N 2 O) in the form of an aqueous solution sprayed directly into the furnace chamber at the beginning of the holding phase.
- the molar ratio of urea (CH 4 N 2 O) to water (H 2 O) is about 1 to 1.
- the molar ratio of urea (CH 4 N 2 O) to water (H 2 O) can also be changed, however only to a small extent.
- the urea decomposes by thermolysis in ammonia (NH 3 ) and isocyanic acid (HNCO). This in turn reacts with water (molar mass 18.015 g / mol) by hydrolysis to ammonia (NH 3 ) and carbon dioxide (CO 2 ).
- NH 3 + CO 2 ⁇ 2 [N] + 3H 2 + CO 2 is known per se and is therefore not described in detail.
- the aqueous urea solution ideally reacts in the furnace chamber to a treatment atmosphere of 66% ammonia (NH 3 ) and 33% carbon dioxide (CO 2 ).
- nitrogen and carbon atoms diffuse into the edge area of the workpieces.
- the result is an outer connection layer and a diffusion layer.
- Nitrocarburizing focuses on the formation of the bonding layer.
- the carbon atoms only diffuse into the bonding layer.
- the workpieces At the end of the heat treatment, the workpieces have an increased surface hardness and good corrosion resistance.
- urea (CH 4 N 2 O) in the form of an aqueous solution and additionally urea (CH 4 N 2 O) in solid form in order to increase the nitrogen availability of the treatment atmosphere.
- the carbon availability of the treatment atmosphere can be increased by adding a carbon-containing additional gas into the furnace chamber.
- the urea (CH 4 N 2 O) and the water (H 2 O) is fed into a presplitter, which is heated to a temperature of at least 130 ° C, preferably at least 140 ° C.
- a presplitter which is heated to a temperature of at least 130 ° C, preferably at least 140 ° C.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
Abstract
Die Erfindung betrifft ein Verfahren zum Wärmebehandeln metallischer Werkstücke in einem Ofenraum, insbesondere zum Nitrocarburieren, wobei die Werkstücke während mindestens einer Behandlungsphase einer Behandlungsatmosphäre bei einer Behandlungstemperatur ausgesetzt sind, wobei Stickstoff und Kohlenstoff in die Werkstücke diffundieren. Erfindungsgemäß wird die Behandlungsatmosphäre unter Verwendung von Harnstoff (CH 4 N 2 O) und Wasser (H 2 O) erzeugt. Durch Thermolyse im Ofenraum bei Behandlungstemperaturen von 500°C bis 600°C zerfällt der Harnstoff in Ammoniak (NH 3 ) und Isocyansäure (HNCO). Diese wiederum reagiert mit Wasser (Molmasse 18,015 g/mol) durch Hydrolyse zu Ammoniak (NH 3 ) und Kohlenstoffdioxid (CO 2 ).The invention relates to a method for heat treating metallic workpieces in a furnace chamber, in particular for nitrocarburizing, wherein the workpieces are exposed to a treatment atmosphere at a treatment temperature during at least one treatment phase, with nitrogen and carbon diffusing into the workpieces. According to the invention, the treatment atmosphere is generated using urea (CH 4 N 2 O) and water (H 2 O). By thermolysis in the furnace chamber at treatment temperatures of 500 ° C to 600 ° C, the urea decomposes into ammonia (NH 3) and isocyanic acid (HNCO). This in turn reacts with water (molar mass 18.015 g / mol) by hydrolysis to ammonia (NH 3) and carbon dioxide (CO 2).
Description
Die Erfindung betrifft ein Verfahren zum Wärmebehandeln metallischer Werkstücke in einem Ofenraum, insbesondere zum Nitrocarburieren, wobei die Werkstücke während mindestens einer Behandlungsphase einer Behandlungsatmosphäre bei einer Behandlungstemperatur ausgesetzt sind, wobei Stickstoff und Kohlenstoff in die Werkstücke diffundieren.The invention relates to a method for heat treating metallic workpieces in a furnace chamber, in particular for nitrocarburizing, wherein the workpieces are exposed to a treatment atmosphere at a treatment temperature during at least one treatment phase, with nitrogen and carbon diffusing into the workpieces.
Das Nitrocarburieren ist ein Wärmebehandlungsverfahren zum Randschichthärten von Werkstücken aus Stahl, bei dem die Werkstücke in einem Ofenraum eines Industrieofens in einer Aufheizphase aufgeheizt und während einer Haltephase bei einer Behandlungstemperatur von ca. 500°C bis 600°C einer Behandlungsatmosphäre ausgesetzt sind, wobei Stickstoff- und Kohlenstoffatome in die Randschicht der Werkstücke eindiffundieren. Anschließend folgt eine Abkühlphase. Es entstehen im Randbereich der Werkstücke eine Verbindungsschicht und eine Diffusionsschicht. Beim Nitrocarburieren steht die Ausbildung der Verbindungsschicht im Vordergrund. Die beiden Schichten sind relativ dünn. Ziel dieses thermochemischen Verfahrens ist es, die Verschleißfestigkeit und die Korrosionsbeständigkeit, insbesondere von unlegierten, niedrig bis mittellegierten Stählen zu verbessern.Nitrocarburizing is a heat treatment process for surface hardening workpieces made of steel, in which the workpieces are heated in a furnace chamber of an industrial furnace in a heating phase and exposed to a treatment atmosphere during a holding phase at a treatment temperature of about 500 ° C to 600 ° C, wherein nitrogen and carbon atoms diffuse into the surface layer of the workpieces. This is followed by a cooling phase. This results in the edge region of the workpieces, a bonding layer and a diffusion layer. Nitrocarburizing focuses on the formation of the bonding layer. The two layers are relatively thin. The aim of this thermochemical process is to improve the wear resistance and corrosion resistance, in particular of unalloyed, low to medium-alloyed steels.
Eine in der Praxis übliche Behandlungsatmosphäre zum Gasnitrocarburieren von metallischen Werkstücken oder Bauteilen ist ein Gasgemisch aus Kohlenstoffdioxid (CO2), Ammoniak (NH3) Wasserstoff (H2) und Stickstoff (N2). Dabei dient das CO2 als Kohlenstoffspender und das NH3 als Stickstoffspender.A treatment atmosphere customary in practice for the gas nitrocarburizing of metallic workpieces or components is a gas mixture of carbon dioxide (CO 2 ), ammonia (NH 3 ), hydrogen (H 2 ) and nitrogen (N 2 ). The CO 2 serves as a carbon donor and the NH 3 as a nitrogen donor.
Die Behandlungsatmosphäre wird in der Praxis in dem Ofenraum des Industrieofens erzeugt. Dazu wird gasförmiges Ammoniak (NH3), Kohlenstoffdioxid (CO2) und Stickstoff (N2) direkt in den Ofenraum eingespeist. In bestimmten Fällen erfolgt aus regelungstechnischen Gründen zusätzlich eine Einspeisung von Wasserstoff (H2).The treatment atmosphere is generated in practice in the furnace room of the industrial furnace. For this purpose, gaseous ammonia (NH 3 ), carbon dioxide (CO 2 ) and nitrogen (N 2 ) are fed directly into the furnace chamber. In certain cases, for technical reasons, there is an additional supply of hydrogen (H 2 ).
Zum Einbringen von Stickstoff und Kohlenstoff durch Diffusion in den Randbereich von Werkstücken aus Stahl bzw. von Stahlbauteilen müssen der Stickstoff und der Kohlenstoff in atomarer Form vorliegen. Die Erzeugung von atomarem Stickstoff erfolgt unter vorbestimmten Temperatur- und Druckbedingungen durch Spaltung von Ammoniak im Ofenraum.For introduction of nitrogen and carbon by diffusion into the edge region of workpieces made of steel or of steel components, the nitrogen and the carbon must be present in atomic form. The generation of atomic nitrogen takes place under predetermined temperature and pressure conditions by cleavage of ammonia in the furnace chamber.
Ammoniak (NH3) ist in gasförmiger Form ein stark unangenehm riechendes, reizendes und giftiges Gas, welches zu Reizungen, Vergiftungen und Erstickungen führen kann. Die Arbeitssicherheit während der Wärmebehandlung ist daher verbesserungsbedürftig. Zudem ist Ammoniak relativ teuer, so dass die Wärmebehandlungskosten hoch sind.Ammonia (NH 3 ) in gaseous form is a very unpleasant-smelling, irritating and poisonous gas which can cause irritation, poisoning and asphyxiation. Occupational safety during the heat treatment is therefore in need of improvement. In addition, ammonia is relatively expensive, so that the heat treatment costs are high.
Die Aufgabe der Erfindung besteht demgemäß darin, ein Verfahren zum Wärmebehandeln metallischer Werkstücke, insbesondere zum Nitrocarburieren, dahingehend zu verbessern, dass die vorgenannten Problematiken vermieden werden.The object of the invention is therefore to improve a method for heat treating metallic workpieces, in particular for nitrocarburizing, in such a way that the aforementioned problems are avoided.
Gemäß der Erfindung wird die Aufgabe durch ein Verfahren nach Anspruch 1 gelöst. Erfindungsgemäß wird die Behandlungsatmosphäre aus Harnstoff bzw. Kohlensäurediamid (CH4N2O) und Wasser (H2O) erzeugt. Harnstoff, mit der chemische Summenformel CH4N2O, hat eine Molmasse von 60,06 g/mol und ist wasserlöslich. Der Erfindung liegt die Erkenntnis zugrunde, dass Harnstoff Kohlenstoff und Stickstoff enthält und somit beide für das Nitrocarburieren notwendige Reaktionspartner C und N liefert. Harnstoff ist im Gegensatz zu Ammoniak ungiftig und relativ preisgünstig. Durch Thermolyse im Ofenraum bei Behandlungstemperaturen von 500°C bis 600°C zerfällt der Harnstoff in Ammoniak (NH3) und Isocyansäure (HNCO). Diese wiederum reagiert mit Wasser (Molmasse 18,015 g/mol) durch Hydrolyse zu Ammoniak (NH3) und Kohlenstoffdioxid (CO2).According to the invention, the object is achieved by a method according to claim 1. According to the invention, the treatment atmosphere is produced from urea or carbonic acid diamide (CH 4 N 2 O) and water (H 2 O). Urea, with the chemical formula CH 4 N 2 O, has a molecular weight of 60.06 g / mol and is water-soluble. The invention is based on the finding that urea contains carbon and nitrogen and thus provides both necessary for the nitrocarburizing reactants C and N. Urea, unlike ammonia, is non-toxic and relatively inexpensive. By thermolysis in the furnace chamber at treatment temperatures of 500 ° C to 600 ° C, the urea decomposes into ammonia (NH 3 ) and isocyanic acid (HNCO). This in turn reacts with water (molar mass 18.015 g / mol) by hydrolysis to ammonia (NH 3 ) and carbon dioxide (CO 2 ).
Die ablaufenden Reaktionen sind:
CH4N2O → NH3 + HNCO
HNCO + H2O → NH3 + CO2
CH4N2O + H2O → 2NH3 + CO2
The ongoing reactions are:
CH 4 N 2 O → NH 3 + HNCO
HNCO + H 2 O → NH 3 + CO 2
CH 4 N 2 O + H 2 O → 2NH 3 + CO 2
Harnstoff (CH4N2O) erzeugt in Verbindung mit einer dosierten Zugabe von Wasser (H2O) idealerweise eine Behandlungsatmosphäre aus 66 % Ammoniak (NH3) und 33 % Kohlenstoffdioxid (CO2). Damit ist Harnstoff in Kombination mit Wasser zum Nitrocarburieren ideal verwendbar. Das CO2 dient während der Wärmebehandlung als Kohlenstoffspender und das NH3 als Stickstoffspender.Urea (CH 4 N 2 O) in combination with a metered addition of water (H 2 O) ideally creates a treatment atmosphere of 66% ammonia (NH 3 ) and 33% carbon dioxide (CO 2 ). This makes urea, in combination with water, ideal for nitrocarburizing. The CO 2 is used during the heat treatment as a carbon donor and the NH 3 as a nitrogen donor.
Vorzugsweise beträgt das molare Verhältnis von Harnstoff (CH4N2O) zu Wasser (H2O) etwa 1 zu 1.Preferably, the molar ratio of urea (CH 4 N 2 O) to water (H 2 O) is about 1 to 1.
Eine bevorzugte Ausführungsvariante ist dadurch gekennzeichnet, dass der Harnstoff (CH4N2O) und das Wasser (H2O) unmittelbar in den Ofenraum eingespeist werden und die Behandlungsatmosphäre direkt in dem Ofenraum erzeugt wird.A preferred embodiment is characterized in that the urea (CH 4 N 2 O) and the water (H 2 O) are fed directly into the furnace chamber and the treatment atmosphere is generated directly in the furnace chamber.
Vorzugsweise wird das Wasser (H2O) in flüssiger Form in den Ofenraum eingespeist. Es ist aber auch möglich, das Wasser (H2O) in dampfförmiger Form in den Ofenraum einzuspeisen.Preferably, the water (H 2 O) is fed in liquid form into the furnace chamber. But it is also possible to feed the water (H 2 O) in vapor form into the furnace chamber.
Im Rahmen der Erfindung kann der Harnstoff (CH4N2O) in fester Form in den Ofenraum eingebracht werden. Alternativ ist das erfindungsgemäße Verfahren dadurch gekennzeichnet, dass der Harnstoff (CH4N2O) in dem Wasser (H2O) gelöst und der Harnstoff (CH4N2O) in Form einer wässrigen Lösung in den Ofenraum eingespeist, vorzugsweise eingesprüht, wird.In the context of the invention, the urea (CH 4 N 2 O) can be introduced in solid form into the furnace chamber. Alternatively, the inventive method is characterized in that the urea (CH 4 N 2 O) dissolved in the water (H 2 O) and the urea (CH 4 N 2 O) fed in the form of an aqueous solution in the furnace chamber, preferably sprayed, becomes.
Je nach Anforderung kann in den Ofenraum Harnstoff (CH4N2O) in Form einer wässrigen Lösung und zusätzlich Harnstoff (CH4N2O) in fester Form eingebracht werden, um die Zusammensetzung der Behandlungsatmosphäre zu verändern.Depending on requirements, urea (CH 4 N 2 O) in the form of an aqueous solution and additionally urea (CH 4 N 2 O) in solid form in the furnace chamber can be introduced in order to change the composition of the treatment atmosphere.
Eine Verfahrensvariante ist dadurch gekennzeichnet, dass der Harnstoff (CH4N2O) und das Wasser (H2O) in einen Vorspalter eingespeist werden, der auf eine Temperatur von mindestens 130°C, vorzugsweise mindestens 140°C, beheizt ist, dass die Behandlungsatmosphäre in dem Vorspalter erzeugt wird und dass die Behandlungsatmosphäre von dem Vorspalter in den Ofenraum geleitet wird. In dem Vorspalter wird durch chemische Reaktion die gewünschte gasförmige Behandlungsatmosphäre erzeugt. Beim Erhitzen über den Schmelzpunkt von 406 K zerfällt Harnstoff (CH4N2O) in Isocyansäure (HNCO) und Ammoniak (NH3).A variant of the method is characterized in that the urea (CH 4 N 2 O) and the water (H 2 O) are fed into a presplitter, which is heated to a temperature of at least 130 ° C, preferably at least 140 ° C, that the treatment atmosphere is generated in the presplitter and that the treatment atmosphere is passed from the presplitter into the furnace space. In the Vorspalter is produced by chemical reaction, the desired gaseous treatment atmosphere. When heated above the melting point of 406 K, urea (CH 4 N 2 O) decomposes into isocyanic acid (HNCO) and ammonia (NH 3 ).
Die Kohlenstoffverfügbarkeit der Behandlungsatmosphäre kann mittels Zugabe eines kohlenstoffhaltigen Zusatzgases erhöht werden. Als Zusatzgas kann beispielsweise Kohlenmonoxid, Kohlendioxid oder Propan verwendet werden.The carbon availability of the treatment atmosphere can be increased by adding a carbon-containing additional gas. Carbon monoxide, carbon dioxide or propane, for example, can be used as additional gas.
Vorzugsweise werden die Werkstücke während einer Haltephase bei einer Behandlungstemperatur von 500°C bis 600°C der Behandlungsatmosphäre ausgesetzt. Der Haltephase geht eine Aufheizphase voraus. Ferner schließt sich an die Haltephase eine Abkühlphase an. Am Ende der Wärmebehandlung weisen die Werkstücke eine gesteigerte Oberflächenhärte und eine gute Korrosionsbeständigkeit auf.Preferably, the workpieces are exposed during a holding phase at a treatment temperature of 500 ° C to 600 ° C of the treatment atmosphere. The holding phase is preceded by a warm-up phase. Furthermore, the holding phase is followed by a cooling phase. At the end of the heat treatment, the workpieces have an increased surface hardness and good corrosion resistance.
Die Erfindung wird im Folgenden anhand eines bevorzugten Ausführungsbeispiels näher erläutert.The invention will be explained in more detail below with reference to a preferred embodiment.
Beim Nitrocarburieren werden Werkstücke aus Stahl in einem Ofenraum während einer Aufheizphase aufgeheizt und während einer Haltephase bei einer Behandlungstemperatur von 500°C bis 600°C einer gasförmigen Behandlungsatmosphäre ausgesetzt. An die Haltephase schließt sich eine Abkühlphase an. Erfindungsgemäß wird die Behandlungsatmosphäre aus Harnstoff bzw. Kohlensäurediamid (CH4N2O) und Wasser (H2O) direkt im Ofenraum erzeugt. Harnstoff (CH4N2O) enthält Kohlenstoff und Stickstoff und somit beide für das Nitrocarburieren notwendigen Reaktionspartner C und N. Der Harnstoff (CH4N2O) wird außerhalb des Ofenraums in dem Wasser (H2O) gelöst und der Harnstoff (CH4N2O) in Form einer wässrigen Lösung zu Beginn der Haltephase direkt in den Ofenraum gesprüht. Das molare Verhältnis von Harnstoff (CH4N2O) zu Wasser (H2O) beträgt etwa 1 zu 1. Das molare Verhältnis von Harnstoff (CH4N2O) zu Wasser (H2O) kann auch verändert werden, allerdings nur in einem geringen Maß.In nitrocarburizing workpieces made of steel are heated in a furnace chamber during a heating phase and exposed during a holding phase at a treatment temperature of 500 ° C to 600 ° C a gaseous treatment atmosphere. The holding phase is followed by a cooling phase. According to the treatment atmosphere of urea or carbonic acid diamide (CH 4 N 2 O) and water (H 2 O) is generated directly in the furnace chamber. Urea (CH 4 N 2 O) contains carbon and nitrogen and thus both necessary for the nitrocarburizing reactants C and N. The urea (CH 4 N 2 O) is dissolved outside the furnace chamber in the water (H 2 O) and the urea ( CH 4 N 2 O) in the form of an aqueous solution sprayed directly into the furnace chamber at the beginning of the holding phase. The molar ratio of urea (CH 4 N 2 O) to water (H 2 O) is about 1 to 1. The molar ratio of urea (CH 4 N 2 O) to water (H 2 O) can also be changed, however only to a small extent.
Bei Behandlungstemperaturen von 500°C bis 600°C im Ofenraum zerfällt der Harnstoff durch Thermolyse in Ammoniak (NH3) und Isocyansäure (HNCO). Diese wiederum reagiert mit Wasser (Molmasse 18,015 g/mol) durch Hydrolyse zu Ammoniak (NH3) und Kohlenstoffdioxid (CO2). Die daraufhin folgende Spaltung des Ammoniaks im Ofenraum nach der Formel
2NH3 + CO2 → 2[N] + 3H2 + CO2
ist an sich bekannt und wird daher nicht näher beschrieben.At treatment temperatures of 500 ° C to 600 ° C in the furnace chamber, the urea decomposes by thermolysis in ammonia (NH 3 ) and isocyanic acid (HNCO). This in turn reacts with water (molar mass 18.015 g / mol) by hydrolysis to ammonia (NH 3 ) and carbon dioxide (CO 2 ). The subsequent cleavage of the ammonia in the furnace chamber according to the formula
2NH 3 + CO 2 → 2 [N] + 3H 2 + CO 2
is known per se and is therefore not described in detail.
Die wässrige Harnstofflösung reagiert im Ofenraum idealerweise zu einer Behandlungsatmosphäre aus 66% Ammoniak (NH3) und 33 % Kohlenstoffdioxid (CO2).The aqueous urea solution ideally reacts in the furnace chamber to a treatment atmosphere of 66% ammonia (NH 3 ) and 33% carbon dioxide (CO 2 ).
Während der Haltephase diffundieren Stickstoff- und Kohlenstoffatome in den Randbereich der Werkstücke. Es entsteht eine äußere Verbindungsschicht und eine Diffusionsschicht. Beim Nitrocarburieren steht die Ausbildung der Verbindungsschicht im Vordergrund. Die Kohlenstoffatome diffundieren nur in die Verbindungsschicht. Am Ende der Wärmebehandlung weisen die Werkstücke eine gesteigerte Oberflächenhärte und eine gute Korrosionsbeständigkeit auf.During the holding phase, nitrogen and carbon atoms diffuse into the edge area of the workpieces. The result is an outer connection layer and a diffusion layer. Nitrocarburizing focuses on the formation of the bonding layer. The carbon atoms only diffuse into the bonding layer. At the end of the heat treatment, the workpieces have an increased surface hardness and good corrosion resistance.
Je nach Anforderung besteht im Rahmen der Erfindung die Möglichkeit, in den Ofenraum Harnstoff (CH4N2O) in Form einer wässrigen Lösung und zusätzlich Harnstoff (CH4N2O) in fester Form einzubringen, um die Stickstoffverfügbarkeit der Behandlungsatmosphäre zu erhöhen.Depending on the requirement, within the scope of the invention it is possible to introduce urea (CH 4 N 2 O) in the form of an aqueous solution and additionally urea (CH 4 N 2 O) in solid form in order to increase the nitrogen availability of the treatment atmosphere.
Im Rahmen der Erfindung kann die Kohlenstoffverfügbarkeit der Behandlungsatmosphäre mittels Zugabe eines kohlenstoffhaltigen Zusatzgases in den Ofenraum erhöht werden.In the context of the invention, the carbon availability of the treatment atmosphere can be increased by adding a carbon-containing additional gas into the furnace chamber.
Bei einer Verfahrensvariante wird der Harnstoff (CH4N2O) und das Wasser (H2O) in einen Vorspalter eingespeist, der auf eine Temperatur von mindestens 130°C, vorzugsweise mindestens 140°C, beheizt ist. Durch die Temperatureinwirkung entsteht in dem Vorspalter die gasförmige Behandlungsatmosphäre, welche aus dem Vorspalter in den Ofenraum geleitet wird.In one process variant, the urea (CH 4 N 2 O) and the water (H 2 O) is fed into a presplitter, which is heated to a temperature of at least 130 ° C, preferably at least 140 ° C. As a result of the effect of temperature, the gaseous treatment atmosphere which is conducted from the presplitter into the furnace space is produced in the presplitter.
Claims (10)
dadurch gekennzeichnet,
dass die Behandlungsatmosphäre unter Verwendung von Harnstoff (CH4N2O) und Wasser (H2O) erzeugt wird.Method for heat treating metal workpieces in a furnace chamber, in particular for nitrocarburizing, wherein the workpieces are exposed to a treatment atmosphere at a treatment temperature during at least one treatment phase, nitrogen and carbon diffusing into the workpieces,
characterized,
that the treatment atmosphere using urea (CH 4 N 2 O) is produced and water (H 2 O).
dadurch gekennzeichnet, dass das molare Verhältnis von Harnstoff (CH4N2O) zu Wasser (H2O) etwa 1 zu 1 beträgt.Method according to claim 1,
characterized in that the molar ratio of urea (CH 4 N 2 O) to water (H 2 O) is about 1 to 1.
dadurch gekennzeichnet, dass der Harnstoff (CH4N2O) und das Wasser (H2O) unmittelbar in den Ofenraum eingespeist werden und die Behandlungsatmosphäre in dem Ofenraum erzeugt wird.Method according to at least one of the preceding claims,
characterized in that the urea (CH 4 N 2 O) and the water (H 2 O) are fed directly into the furnace chamber and the treatment atmosphere is generated in the furnace chamber.
dadurch gekennzeichnet, dass das Wasser (H2O) in flüssiger Form in den Ofenraum eingespeist wird.Method according to at least one of the preceding claims,
characterized in that the water (H 2 O) is fed in liquid form into the furnace chamber.
dadurch gekennzeichnet, dass der Harnstoff (CH4N2O) in fester Form in den Ofenraum eingebracht wird.Method according to at least one of the preceding claims,
characterized in that the urea (CH 4 N 2 O) is introduced in solid form into the furnace chamber.
dadurch gekennzeichnet, dass der Harnstoff (CH4N2O) in dem Wasser (H2O) gelöst und der Harnstoff (CH4N2O) in Form einer wässrigen Lösung in den Ofenraum eingespeist, vorzugsweise eingesprüht, wird.Method according to at least one of the preceding claims 1 to 4,
characterized in that the urea (CH 4 N 2 O) dissolved in the water (H 2 O) and the urea (CH 4 N 2 O) is fed in the form of an aqueous solution in the furnace chamber, preferably sprayed, is.
dadurch gekennzeichnet, dass in den Ofenraum Harnstoff (CH4N2O) in Form einer wässrigen Lösung und zusätzlich Harnstoff (CH4N2O) in fester Form eingebracht wird, um die Stickstoffverfügbarkeit der Behandlungsatmosphäre zu erhöhen.Method according to claim 6,
characterized in that in the furnace chamber urea (CH 4 N 2 O) in the form of an aqueous solution and additionally urea (CH 4 N 2 O) is introduced in solid form in order to increase the nitrogen availability of the treatment atmosphere.
dadurch gekennzeichnet, dass der Harnstoff (CH4N2O) und das Wasser (H2O) in einen Vorspalter eingespeist werden, der auf eine Temperatur von mindestens 130°C, vorzugsweise 140°C, beheizt ist, dass die Behandlungsatmosphäre in dem Vorspalter erzeugt wird und dass die Behandlungsatmosphäre von dem Vorspalter in den Ofenraum geleitet wird.Method according to claim 1 or 2,
characterized in that the urea (CH 4 N 2 O) and the water (H 2 O) are fed into a presplitter, which is heated to a temperature of at least 130 ° C, preferably 140 ° C, that the treatment atmosphere in the Preswitch is generated and that the treatment atmosphere is passed from the presplitter in the furnace chamber.
dadurch gekennzeichnet, dass die Kohlenstoffverfügbarkeit der Behandlungsatmosphäre mittels Zugabe eines kohlenstoffhaltigen Zusatzgases erhöht wird.Method according to at least one of the preceding claims,
characterized in that the carbon availability of the treatment atmosphere is increased by adding a carbon-containing additional gas.
dadurch gekennzeichnet, dass die Werkstücke während einer Behandlungssphase in Form einer Haltephase bei einer Behandlungstemperatur von 500°C bis 600°C der Behandlungsatmosphäre ausgesetzt sind und dass der Haltephase eine Aufheizphase vorausgeht und eine Abkühlphase anschließt.Method according to at least one of the preceding claims,
characterized in that the workpieces are exposed during a treatment phase in the form of a holding phase at a treatment temperature of 500 ° C to 600 ° C of the treatment atmosphere and that the holding phase precedes a heating phase and followed by a cooling phase.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP16154353.3A EP3202945B1 (en) | 2016-02-04 | 2016-02-04 | Method for nitrocarburizing of metallic workpieces |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP16154353.3A EP3202945B1 (en) | 2016-02-04 | 2016-02-04 | Method for nitrocarburizing of metallic workpieces |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3202945A1 true EP3202945A1 (en) | 2017-08-09 |
EP3202945B1 EP3202945B1 (en) | 2019-04-24 |
Family
ID=55345697
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP16154353.3A Active EP3202945B1 (en) | 2016-02-04 | 2016-02-04 | Method for nitrocarburizing of metallic workpieces |
Country Status (1)
Country | Link |
---|---|
EP (1) | EP3202945B1 (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1521167A1 (en) * | 1966-06-18 | 1969-07-31 | Bbc Brown Boveri & Cie | Process for soft nitriding steel with gases |
DE19719225C1 (en) * | 1997-05-07 | 1998-08-06 | Volker Dipl Ing Leverkus | Method and apparatus for controlling a nitriding or nitro-carburising atmosphere |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB311588A (en) * | 1928-07-04 | 1929-05-16 | Julius Leonard Fox Vogel | Improvements in the hardening of molybdenum irons or steels |
DE2647668C2 (en) * | 1975-12-15 | 1982-10-21 | Ford-Werke AG, 5000 Köln | Process for nitriding metal parts |
-
2016
- 2016-02-04 EP EP16154353.3A patent/EP3202945B1/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1521167A1 (en) * | 1966-06-18 | 1969-07-31 | Bbc Brown Boveri & Cie | Process for soft nitriding steel with gases |
DE19719225C1 (en) * | 1997-05-07 | 1998-08-06 | Volker Dipl Ing Leverkus | Method and apparatus for controlling a nitriding or nitro-carburising atmosphere |
Also Published As
Publication number | Publication date |
---|---|
EP3202945B1 (en) | 2019-04-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102471864A (en) | Method of activating an article of passive ferrous or non-ferrous metal prior to carburizing, nitriding and/or nitrocarburising | |
DE2521903C2 (en) | Process for keeping the cyanide content low in molten salt baths with cyanate anions as the active ingredient | |
EP3202945B1 (en) | Method for nitrocarburizing of metallic workpieces | |
DE69902169T2 (en) | METHOD FOR LOW PRESSURE NITROCARBURING METAL WORKPIECES | |
DE2116267C3 (en) | Process for the production of urea | |
DE3853064T2 (en) | Treatment method for a liquid waste containing cyanide. | |
DE2652382B2 (en) | Process for carbonitriding steel and pig iron products | |
DE4442328C1 (en) | Pretreating chrome or nickel alloy steels prior to nitro:carburisation in a salt bath | |
DE2133284A1 (en) | Heat treatment of steel and cast iron in a gas atmosphere | |
DE1233836B (en) | Process for the production of ammonia gas | |
DE2000060A1 (en) | Accelerating carburization of steel workpie - ces with generator carrier gas | |
EP1230415B1 (en) | Method for nitro-carburization of metal workpieces | |
RU2600612C1 (en) | Method of carbonitriding parts made from structural and tool steels | |
DD156877A3 (en) | REGENERATIVE FOR NITRIERSALZBAEDER | |
DE102006048434A1 (en) | Procedure for the production of a protective gas- or treatment atmosphere in a heat treatment furnace, comprises vaporizing ethanol by electrically heated evaporator, introducing ethanol and carbon dioxide into the furnace | |
DE299141C (en) | ||
DE936566C (en) | Process for the production of hydrogen cyanide | |
DE335240C (en) | Process for the production of ammonia from cyanides | |
DE2041624A1 (en) | Vanadium carbonitride and/or nitride prepn | |
DE569485C (en) | Process for the production of calcium cyanide | |
DE2228746A1 (en) | Low temp carbonitrided coatings - on iron alloys using partly dissociated ammonia at mos | |
CH410904A (en) | Process for preventing corrosion in urea synthesis | |
DE936389C (en) | Process for the production of hydrocyanic acid | |
SU1694690A1 (en) | Compound for gaseous nitriding-carburizing of steel products | |
CH332227A (en) | Process for cementing iron and steel and their alloys in a gas atmosphere |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
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: THE APPLICATION HAS BEEN PUBLISHED |
|
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 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17P | Request for examination filed |
Effective date: 20180202 |
|
RBV | Designated contracting states (corrected) |
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 |
|
17Q | First examination report despatched |
Effective date: 20180228 |
|
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: C21D 1/74 20060101ALI20181120BHEP Ipc: C21D 1/06 20060101ALI20181120BHEP Ipc: C23C 8/32 20060101AFI20181120BHEP Ipc: C21D 1/76 20060101ALI20181120BHEP |
|
INTG | Intention to grant announced |
Effective date: 20181217 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAJ | Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted |
Free format text: ORIGINAL CODE: EPIDOSDIGR1 |
|
GRAL | Information related to payment of fee for publishing/printing deleted |
Free format text: ORIGINAL CODE: EPIDOSDIGR3 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
GRAR | Information related to intention to grant a patent recorded |
Free format text: ORIGINAL CODE: EPIDOSNIGR71 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: GRANT OF PATENT IS INTENDED |
|
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 |
|
INTC | Intention to grant announced (deleted) | ||
INTG | Intention to grant announced |
Effective date: 20190313 |
|
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 Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 1124252 Country of ref document: AT Kind code of ref document: T Effective date: 20190515 Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 502016004293 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: MP Effective date: 20190424 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20190424 |
|
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: 20190424 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: 20190424 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: 20190424 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: 20190424 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: 20190424 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: 20190424 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: 20190724 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: 20190824 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20190424 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: 20190424 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: 20190725 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: 20190424 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: 20190724 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IS 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: 20190824 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R097 Ref document number: 502016004293 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
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: 20190424 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: 20190424 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: 20190424 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: 20190424 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: 20190424 |
|
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: 20190424 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: 20190424 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR 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: 20190424 |
|
26N | No opposition filed |
Effective date: 20200127 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI 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: 20190424 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20200204 |
|
REG | Reference to a national code |
Ref country code: BE Ref legal event code: MM Effective date: 20200229 |
|
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: 20190424 Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200204 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200229 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200229 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200204 Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200229 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20200204 |
|
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: 20200229 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT 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: 20190424 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: 20190424 |
|
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: 20190424 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20240119 Year of fee payment: 9 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20240117 Year of fee payment: 9 |