EP3202945B1 - Method for nitrocarburizing of metallic workpieces - Google Patents

Method for nitrocarburizing of metallic workpieces Download PDF

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Publication number
EP3202945B1
EP3202945B1 EP16154353.3A EP16154353A EP3202945B1 EP 3202945 B1 EP3202945 B1 EP 3202945B1 EP 16154353 A EP16154353 A EP 16154353A EP 3202945 B1 EP3202945 B1 EP 3202945B1
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urea
treatment
treatment atmosphere
water
phase
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German (de)
French (fr)
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EP3202945A1 (en
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Heinrich-Peter Lankes
Peter Haase
Dirk Miller
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Iva Schmetz GmbH
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Iva Schmetz GmbH
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    • 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 nitrocarburizing metallic workpieces in a furnace chamber, the workpieces being exposed to a treatment atmosphere at a treatment temperature during at least one treatment phase, with nitrogen and carbon diffusing into the workpieces.
  • the GB 311 588 A shows a process for surface hardening of molybdenum steel in which a nitrogen-containing solid which decomposes at temperatures below the temperatures at which nitriding takes place with nitrogen in the presence of the steel to be hardened with or without addition of air, water or steam and nitrogen releases.
  • the metal parts to be hardened are embedded in an embedding material, which is impregnated with a nitrogen-containing carrier material.
  • the nitrogen-containing carrier material used is urea or a urea derivative.
  • the amount of nitrogenous carrier material which is bound in solid form to the potting material is initially predetermined and can not be changed during nitriding.
  • 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 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.
  • hydrogen (H 2 ) there is an additional supply of hydrogen (H 2 ).
  • nitrogen and 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 urea (CH 4 N 2 O) is dissolved in the water (H 2 O), the urea (CH 4 N 2 O) is fed into the furnace chamber in the form of an aqueous solution and the treatment atmosphere is generated in the furnace chamber or 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, wherein the treatment atmosphere is generated in the Vorspalter and is passed from the presplitter in the furnace chamber.
  • the desired gaseous treatment atmosphere is generated by chemical reaction in the presplitter.
  • urea CH 4 N 2 O
  • isocyanic acid HNCO
  • ammonia NH 3
  • the molar ratio of urea (CH 4 N 2 O) to water (H 2 O) is about 1 to 1.
  • the inventive method is characterized in that the urea (CH 4 N 2 O) is sprayed in the form of an aqueous solution 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) 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 presplinter is heated to a temperature of preferably 140 ° C.
  • 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.
  • 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.

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  • 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)

Description

Die Erfindung betrifft ein Verfahren zum Nitrocarburieren metallischer Werkstücke in einem Ofenraum, 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 nitrocarburizing metallic workpieces in a furnace chamber, the workpieces being exposed to a treatment atmosphere at a treatment temperature during at least one treatment phase, with nitrogen and carbon diffusing into the workpieces.

Die GB 311 588 A zeigt ein Verfahren zum Oberflächenhärten von Molybdänstahl, bei dem ein stickstoffhaltiger fester Stoff, der bei Temperaturen, unterhalb der Temperaturen, bei denen eine Nitrierung mit Stickstoff stattfindet, in Gegenwart des zu härtenden Stahls mit oder ohne Beigabe von Luft, Wasser oder Wasserdampf zerfällt und Stickstoff freisetzt.The GB 311 588 A shows a process for surface hardening of molybdenum steel in which a nitrogen-containing solid which decomposes at temperatures below the temperatures at which nitriding takes place with nitrogen in the presence of the steel to be hardened with or without addition of air, water or steam and nitrogen releases.

Bei einem aus der DE 26 47 668 A1 bekannten Verfahren zur Nitrierhärtung werden die zu härtenden Metallteile in ein Einbettmaterial eingebettet, welches mit einem stickstoffhaltigen Trägermaterial, imprägniert ist. Als stickstoffhaltiges Trägermaterial wird Harnstoff oder ein Harnstoffderivat eingesetzt. Die Menge des stickstoffhaltigen Trägermaterials, welches in fester Form an das Einbettmaterial gebunden ist, ist anfänglich vorgegeben und kann während der Nitrierhärtung nicht geändert werden.At one of the DE 26 47 668 A1 known processes for nitriding the metal parts to be hardened are embedded in an embedding material, which is impregnated with a nitrogen-containing carrier material. The nitrogen-containing carrier material used is urea or a urea derivative. The amount of nitrogenous carrier material which is bound in solid form to the potting material is initially predetermined and can not be changed during nitriding.

In der DE 15 21 167 A1 wird ein Verfahren beschrieben, bei dem eine Flüssigkeit zur Erzeugung einer Gasatmoshäre zum Weichnitrieren von Stählen mit Gas offenbart, bei dem die Flüssigkeit ausser gelöstem Ammoniak, Alkohole, Amine, Wasser und Harnstoff enthalten kann.In the DE 15 21 167 A1 describes a method in which a liquid for generating a Gasatmoshäre for soft nitriding of steels with gas disclosed, in which the liquid may contain dissolved ammonia, alcohols, amines, water and urea.

Aus der DE 187 19 225 C1 ist ein Verfahren und eine Vorrichtung zur Regelung einer Nitrier-bzw. Nitrocarburier-Atmospäre bekannt, bei dem mittels eines Vorspalters ein Spaltgas erzeugt wird, indem Ammoniak bei Temperaturen zwischen 400°C und 1000°C über einen Katalysator geleitet und dabei in 25% Stickstoff und 75% Wasserstoff gespaltet wird.From the DE 187 19 225 C1 is a method and apparatus for controlling a nitriding or. Nitrocarburier Atmospäre known in which by means of a Vorspalters a fission gas is generated by ammonia at temperatures between 400 ° C and 1000 ° C passed over a catalyst and thereby split into 25% nitrogen and 75% hydrogen.

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 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).
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.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 ).
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.According to the invention, the object is achieved by a method according to claim 1.

Erfindungsgemäß wird die Behandlungsatmosphäre aus Harnstoff bzw. Kohlensäurediamid (CH4N2O) und Wasser (H2O) erzeugt. Harnstoff, mit der chemischen 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 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.

Erfindungsgemäß wird der Harnstoff (CH4N2O) in dem Wasser (H2O) gelöst, der Harnstoff (CH4N2O) in Form einer wässrigen Lösung in den Ofenraum eingespeist und die Behandlungsatmosphäre in dem Ofenraum erzeugt oder der Harnstoff (CH4N2O) und das Wasser (H2O) werden in einen Vorspalter eingespeist, der auf eine Temperatur von mindestens 130°C beheizt ist, wobei die Behandlungsatmosphäre in dem Vorspalter erzeugt wird und von dem Vorspalter in den Ofenraum geleitet wird.According to the invention, the urea (CH 4 N 2 O) is dissolved in the water (H 2 O), the urea (CH 4 N 2 O) is fed into the furnace chamber in the form of an aqueous solution and the treatment atmosphere is generated in the furnace chamber or 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, wherein the treatment atmosphere is generated in the Vorspalter and is passed from the presplitter in the furnace chamber.

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). Vorzugsweise beträgt das molare Verhältnis von Harnstoff (CH4N2O) zu Wasser (H2O) etwa 1 zu 1.The desired gaseous treatment atmosphere is generated by chemical reaction in the presplitter. When heated above the melting point of 406 K, urea (CH 4 N 2 O) decomposes into isocyanic acid (HNCO) and ammonia (NH 3 ). Preferably, the molar ratio of urea (CH 4 N 2 O) to water (H 2 O) is about 1 to 1.

Alternativ ist das erfindungsgemäße Verfahren dadurch gekennzeichnet, dass der Harnstoff (CH4N2O) in Form einer wässrigen Lösung in den Ofenraum eingesprüht wird.
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.Alternatively, the inventive method is characterized in that the urea (CH 4 N 2 O) is sprayed in the form of an aqueous solution in the furnace chamber.
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 Vorspalter auf eine Temperatur von vorzugsweise 140°C beheizt ist.A variant of the method is characterized in that the presplinter is heated to a temperature of preferably 140 ° C.

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.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.

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.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 (7)

  1. Method for nitrocarburizing metallic workpieces in a furnace space, wherein during at least one treatment phase the workpieces are exposed to a treatment atmosphere at a treatment temperature, wherein nitrogen and carbon to diffuse into the work pieces,
    characterised in that,
    the treatment atmosphere is produced from urea (CH4N2O) and water (H2O) and
    - the urea (CH4N2O) is dissolved in the water (H2O), the urea (CH4N2O) is fed into the furnace space in the form of an aqueous solution and the treatment atmosphere is generated in the furnace space, or
    - the urea (CH4N2O) and the water (H2O) are fed into a pre-splitter, which is heated to a temperature of at least 130°C, that the treatment atmosphere is generated in the pre-splitter and is guided from the pre-splitter into the furnace space.
  2. Method according to claim 1,
    characterized in that the molar ratio of urea (CH4N2O) to water (H2O) is about 1 to 1.
  3. Method according to at least one of the preceding claims 1 or 2,
    characterized in that the urea (CH4N2O) is sprayed into the furnace space in the form of an aqueous solution.
  4. Method according to claim 3,
    characterized in that urea (CH4N2O) in the form of an aqueous solution and additionally urea (CH4N2O) in a solid form are introduced into the furnace space, in order to increase the nitrogen availability of the treatment atmosphere.
  5. Method according to claims 1 or 2,
    characterized in that the pre-splitter is preheated to a temperature of preferably 140°C.
  6. Method according to at least one of the preceding claims,
    characterized in that the carbon availability of the treatment atmosphere is increased by the addition of a carbon-containing additional gas.
  7. Method according to at least one of the preceding claims,
    characterized in that during a treatment phase in the form of a holding phase the work pieces are exposed to the treatment atmosphere at a treatment temperature of 500° C to 600°C and that the holding phase is preceded by a heat-up phase and followed by a cool-down phase.
EP16154353.3A 2016-02-04 2016-02-04 Method for nitrocarburizing of metallic workpieces Active EP3202945B1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
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
DE2647668A1 (en) * 1975-12-15 1977-06-16 Ford Werke Ag PROCESS FOR NITRIFICATION OF METAL PARTS

Family Cites Families (2)

* Cited by examiner, † Cited by third party
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
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
DE2647668A1 (en) * 1975-12-15 1977-06-16 Ford Werke Ag PROCESS FOR NITRIFICATION OF METAL PARTS

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