EP3408423B1 - Verfahren zum wärmebehandeln eines aus einem metallwerkstoff bestehenden bauteils mit mindestens einem mit einer glasur- oder emaille-beschichtung beschichteten flächenabschnitt - Google Patents

Verfahren zum wärmebehandeln eines aus einem metallwerkstoff bestehenden bauteils mit mindestens einem mit einer glasur- oder emaille-beschichtung beschichteten flächenabschnitt Download PDF

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Publication number
EP3408423B1
EP3408423B1 EP17716981.0A EP17716981A EP3408423B1 EP 3408423 B1 EP3408423 B1 EP 3408423B1 EP 17716981 A EP17716981 A EP 17716981A EP 3408423 B1 EP3408423 B1 EP 3408423B1
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EP
European Patent Office
Prior art keywords
glaze
enamel coating
temperature
component
cooling
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP17716981.0A
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German (de)
English (en)
French (fr)
Other versions
EP3408423A1 (de
Inventor
Bernhard Stauder
Jurij GONTAREV
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nemak SAB de CV
Original Assignee
Nemak SAB de CV
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Filing date
Publication date
Application filed by Nemak SAB de CV filed Critical Nemak SAB de CV
Publication of EP3408423A1 publication Critical patent/EP3408423A1/de
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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
    • C23D—ENAMELLING OF, OR APPLYING A VITREOUS LAYER TO, METALS
    • C23D7/00—Treating the coatings, e.g. drying before burning
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/02—Alloys based on aluminium with silicon as the next major constituent
    • C22C21/04—Modified aluminium-silicon alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/04—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon
    • C22F1/043—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of aluminium or alloys based thereon of alloys with silicon as the next major constituent
    • 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
    • C23D—ENAMELLING OF, OR APPLYING A VITREOUS LAYER TO, METALS
    • C23D13/00—After-treatment of the enamelled articles
    • 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
    • C23D—ENAMELLING OF, OR APPLYING A VITREOUS LAYER TO, METALS
    • C23D1/00—Melting or fritting the enamels; Apparatus or furnaces therefor

Definitions

  • the invention relates to a method for heat treatment of a component consisting of a metal alloy, in particular a light metal material, in or on which at least one surface section is coated with a glaze or enamel coating.
  • enamel coatings are glass layers that have been adapted to the carrier materials intended for them, especially with regard to the melting temperature and the coefficient of thermal expansion. They combine the properties of a glass surface with the material and processing properties of metals. In contrast to other coatings, when the respective enamel coating is burned in, a glass-metal bond is formed in which intermediate layers, so-called intermetallic phases, are formed between the glass material and the metal substrate. These ensure particularly intensive adhesion of the coating to the metal. For this purpose, modern enamels are now multicomponent mixtures which, using their eutectic, achieve very good mechanical hardness and chemical resistance at low stoving temperatures.
  • the glaze or enamel coating described on surfaces of components made of light metal has shown that such a coating can withstand the thermal and mechanical loads reliably and reliably protects the light metal substrate when the temperature of the component in question is exposed during operation on the surface provided with the enamel coating, is much higher than the melting temperature of the light metal material and the coating itself.
  • Such enamel powder is particularly suitable for coating surfaces that are exposed to a hot exhaust gas flow during use. Such surfaces are typically present in the area of the exhaust-gas ducts of components of internal combustion engines, cylinder heads, turbochargers and others. Components of this type are regularly produced by casting in practice.
  • the component as a whole or at least in the area of the respective surface section is then heated to a stoving temperature. At this temperature, the glass matrix of the coating melts and a chemical bond is created between the coating and the base material of the component.
  • the mechanical properties of cast parts made from light metal materials, in particular aluminum alloys, can be adjusted in a targeted manner by means of a suitable heat treatment. So can through a Solution annealing with subsequent quenching, in which the component is cooled at high speed to a low target temperature, for example room temperature, the strength of the component is significantly increased. It has proven to be particularly economical if the baking and heating to the quenching temperature from which the quenching takes place are carried out in one go.
  • the glaze or enamel coating can flake off if, after heating to a temperature above the usual baking temperature of the glaze or enamel coating, quenching takes place at very high cooling rates, as is the case, for example occur in a water quench.
  • quenching takes place at very high cooling rates, as is the case, for example occur in a water quench.
  • a deterrent with such high cooling rates must be used regularly, especially for components that are exposed to high mechanical loads during use, such as cylinder heads of internal combustion engines.
  • these components are the typical application examples for components that are coated with a glaze or enamel coating of the type in question in areas that are subject to high thermal loads.
  • the task has arisen to name a method with which it is possible to heat-treat components made of metal materials, in particular light metal materials, and provided with a glaze or enamel coating on at least one surface section, in such a way that, on the one hand, maximum strengths of the Component reached and on the other hand a flaking of the glaze or enamel coating is reliably avoided.
  • the invention has achieved this object by the method specified in claim 1.
  • the respective component is in accordance with the prior art explained at the beginning on a Heating temperature heated that is at least equal to a minimum quenching temperature.
  • the component is then quenched starting from a temperature that is in turn at least equal to the minimum quenching temperature in order to produce a higher-strength structure in the component.
  • the heating temperature to which the component is heated prior to quenching is measured in such a way that the temperature of the component at the beginning of the quenching process is at least equal to the minimum quenching temperature, also taking into account possible temperature losses that occur due to the transport of the component or other intermediate work steps .
  • the glaze or enamel coating is pre-cooled at least on its free surface to a pre-cooling temperature prior to quenching, which corresponds at most to the temperature at which the glaze or enamel coating begins to soften.
  • the cooling rate at which the glaze or enamel coating is pre-cooled is, according to the invention, lower than the cooling rate achieved during quenching.
  • the glaze or enamel coating precooled sufficiently slowly prior to quenching to a temperature lower than the component temperature, typically lower than the minimum quenching temperature, and at which the glaze or enamel coating resolidifies.
  • the target temperature of the pre-cooling in the sense of the invention is generally the temperature above which there is a softening of the glass matrix and the chemical processes explained at the beginning, due to which the glaze or enamel coating adheres permanently to the metal material of the component.
  • the coating is cooled, at least in its area of its free surface, to a temperature below this target temperature.
  • the method according to the invention proves to be particularly suitable for the heat treatment of components which are made of a light metal material, in particular an aluminum-based material.
  • the glaze or enamel coating After the glaze or enamel coating has been softened as a result of the heating to the heating temperature corresponding to at least the minimum quenching temperature and thus above the baking temperature typically set when baking the glaze or enamel coating, it thus at least solidifies through the pre-cooling according to the invention again so far that they are stuck adheres to the metal substrate of the component and can thus withstand the rapid temperature change during the subsequent quenching of the entire component without flaking.
  • the pre-cooling of the glaze or enamel coating is carried out after the component has been heated to the heating temperature, it can happen that the component also cools to a certain extent during the pre-cooling.
  • the minimum quenching temperature from which the component is quenched is lower than the originally reached heating temperature or the heating temperature is set so high that the component temperature is still above the minimum quenching temperature even after the temperature decrease that occurs in the course of the pre-cooling lies.
  • the pre-cooling temperature to which the glaze or enamel coating is pre-cooled can typically be at least 30 ° C., in particular at least 50 ° C. lower than the minimum quenching temperature.
  • suitable baking temperatures and thus the temperatures at which the glass matrix of the glaze or enamel coating begins to soften are typically in the range of 480-650 ° C, in particular 510-540 ° C.
  • the glaze or enamel coating can therefore be prevented from flaking off in a particularly reliable manner if the pre-cooling temperature is a maximum of 480 ° C, in particular a maximum of 470 ° C or 450 ° C.
  • typical minimum quenching temperatures for components made of Al materials are at least 480 ° C., in particular at least 500 ° C., quenching temperatures of at least 520 ° C., in particular at least 530 ° C., have proven to be particularly advantageous in practice.
  • the pre-cooling temperature can be achieved by a fluid flowing against the glaze or enamel coating.
  • a suitably tempered gas stream is particularly suitable for this.
  • Compressed air has proven to be particularly advantageous here as a cooling gas, since it is readily available in the operational environment in which the method according to the invention is used and the compressed air flow can be adjusted without problems in such a way that it effects the required cooling.
  • gases such as a protective gas, for example nitrogen or the like, can also be used if they are available or if this is indicated, for example, to avoid reactions of the metal substrate with the incoming gas.
  • the respective gas flow can be directed against the glaze or enamel coating by means of a nozzle device in order to ensure a concentrated cooling on the surface section coated with the glaze or enamel coating.
  • the layer thickness and the thermophysical data result in a propagation speed of the temperature wave caused by the cooling medium, the progress of which is determined by the so-called thermal conductivity or thermal diffusivity of the glaze or enamel coating.
  • the metal substrate of the component is not affected as long as the heat wave does not penetrate the casting surface as a result of the pre-cooling.
  • cooling times of a maximum of 60 seconds, in particular a maximum of 40 seconds are generally sufficient.
  • a cooling below the required minimum quenching temperature with conventional coating thicknesses can be prevented particularly reliably by limiting the duration of the pre-cooling to a maximum of 20 seconds, in particular 5-20 seconds.
  • Typical layer thicknesses of the glaze or enamel coating are in the range of up to 5 mm, in particular up to 2 mm.
  • the specific required duration of the pre-cooling of the glaze or enamel coating can be determined in a manner customary for a person skilled in the art by means of experimental measurements on test pieces of the components to be heat-treated. For this purpose, on the one hand, the temperature decrease of the glaze or enamel coating that occurs during pre-cooling and, on the other hand, the temperature profile in the area of the boundary layer between the glaze or enamel coating and the metal material of the component carrying it is recorded or theoretically determined. Optimally, the duration of the pre-cooling is set so that the temperature of the light metal material of the component on the surface section that is coated with the glaze or enamel coating is at least equal to the minimum quenching temperature.
  • the glaze or enamel coating is only cooled on its free surface to the pre-cooling temperature, so that in the area of the glaze or enamel coating adjoining the metal substrate there is a higher temperature adjacent to the minimum quenching temperature. Even a pre-cooling limited to the free surface of the coating and thus to the layers of the glaze or enamel coating close to this surface prevents the glaze or enamel coating from cracking during the subsequent quenching. Since the surface of the coating has already cooled down at the same time, the unit formed in this way from component and layer base is under compressive stress, which further increases its resistance.
  • Practical cooling rates of the pre-cooling are in the range of less than 5 K / s, whereby at cooling rates of at least 0.5 K / s the pre-cooling can take place so quickly that during the pre-cooling of the glaze or enamel coating there is no excessive cooling of the rest Component occurs.
  • the heat treatment carried out according to the invention can usually be carried out as solution heat treatment with subsequent quenching.
  • the typical glow durations are 0.5-5 hours.
  • the component can then be quenched at cooling rates of at least 5 K / s, in particular at least 7 K / s or at least 10 K / s.
  • cooling rates of up to 50 K / s have proven effective, whereby the cooling rates actually achieved for components with strongly changing wall thicknesses and local material accumulations can vary widely over the component volume.
  • the components themselves can be quenched in the customary manner after the glaze or enamel coating has been pre-cooled according to the invention.
  • a particularly suitable quenching medium here is water.
  • other quenching media such as spray mist, polymers, oils or gases can also be used if necessary.
  • the cooling rate achieved in each case can be set in an equally known manner via the temperature of the quenching medium. If water is used as the quenching medium, the water temperature can, for example, reach the boiling point in order to avoid excessively high cooling rates in the component.
  • the method according to the invention is particularly suitable for the heat treatment of components for internal combustion engines in which at least one channel is provided on which at least one surface section is coated with the glaze or enamel coating.
  • the components heat-treated according to the invention can undergo further treatment steps in a manner known per se, such as aging, in order to further optimize their properties with regard to the respective use.
  • the single figure shows, as an example of a component of the type to be heat-treated according to the invention, schematically, a cylinder head 1 for an internal combustion engine in a section oriented transversely to the longitudinal extension of the cylinder head 1.
  • the cylinder head 1 which is cast from a cast aluminum material usually used for this purpose, for example an AISi11 or AISi10Cu0.5Mg alloy, has a flat contact surface 2 with which, when in use, a cylinder head gasket (not shown here) can be placed on a cylinder head gasket shown engine block of the respective internal combustion engine is.
  • the internal combustion engine has combustion chambers arranged in a row and pistons which move up and down in them and are likewise not visible here.
  • dome-like recesses 3 are formed, which form the upper end of the combustion chambers of the internal combustion engine in the stroke direction of the pistons of the internal combustion engine.
  • each of the recesses 3 there opens an inlet channel 5 which is brought up from one longitudinal side 4 'of the cylinder head 1 and via which the respective fuel-air mixture is admitted into the combustion chamber during operation.
  • an exhaust gas duct 6 leads from the respective recess 3, which is led to the opposite longitudinal side 4 ′′ of the cylinder head 1 and via which the exhaust gas produced during the combustion process is discharged from the combustion chamber of the internal combustion engine.
  • the inner surfaces 7 of the exhaust gas channel 6 surrounding the exhaust gas channel 6 are exposed to high thermal and mechanical loads during operation, particularly in the area adjoining its inlet opening 8, due to the hot exhaust gas flowing into the exhaust gas channel 6 at high flow rates when the inlet opening is open.
  • the inner surfaces 7 are covered with an enamel coating 9, the thickness of which is on average 400 ⁇ m and which covers the inner surfaces 7 over the entire length of the exhaust gas duct 6.
  • the cylinder head 1 has a large number of exhaust gas ducts 6 corresponding to the number of combustion chambers and associated valves, which are arranged one behind the other in the longitudinal direction of the cylinder head 1 and are each coated with an enamel coating 9.
  • the cylinder head 1 is first heated to a burn-in temperature of 520 ° C. in order to burn in the enamel coating 9 in such a way that it adheres firmly to the Al substrate of the component.
  • the cylinder head 1 has been solution-annealed for an annealing period of 1.5 hours at a heating temperature of 535.degree.
  • the cylinder head 1 is removed from the annealing furnace (not shown here) and placed on a holding device 10 within 10 s.
  • the holding device 10 is part of a pre-cooling device which additionally comprises a nozzle arrangement 11.
  • the nozzle arrangement 11 has nozzles 12, one of which is directed into the outlet opening 13 of the respective exhaust gas duct 6 formed on one longitudinal side 4 ′′.
  • the surfaces of the longitudinal side 4 ′′ adjoining the outlet opening 13 are made of a heat-resistant material Aperture 14 thermally shielded from the environment.
  • the nozzle arrangement 11 is connected to a central compressed air supply 15, via which compressed air at room temperature reaches the nozzle arrangement 11.
  • a compressed air flow D is directed directly against the free surface 9 ′ of the enamel coating 9 via the nozzles 12 assigned to the individual exhaust gas ducts 6 of the cylinder head.
  • the enamel coating 9 is pre-cooled in this way to a pre-cooling temperature of less than 470 ° C. within 30-40 s.
  • the cylinder head 1 is then removed from the holding device 10 and immersed in a water bath, the temperature of which is 95 ° C., for 5 s. In this way, the cylinder head 1 is quenched to room temperature.
  • the quenching can be followed by artificial aging at 200 ° C for a period of 1-200 hours.
  • an aging time of 5 hours was selected.
  • the measure of the hardening achieved by the heat treatment is the yield point of the material from which the cylinder heads 1 are made.
  • cylinder heads 1 cast from the AISi10Cu0.5Mg alloy had the following yield strengths, depending on the quenching medium used, at a quenching temperature of 535 ° C in each case: Quenching medium Stretch limit water 280 N / mm 2 Combi-Quench (water / air) 262 N / mm 2 Air shower 220 N / mm 2

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Cylinder Crankcases Of Internal Combustion Engines (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Heat Treatments In General, Especially Conveying And Cooling (AREA)
  • Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
EP17716981.0A 2016-03-03 2017-03-02 Verfahren zum wärmebehandeln eines aus einem metallwerkstoff bestehenden bauteils mit mindestens einem mit einer glasur- oder emaille-beschichtung beschichteten flächenabschnitt Active EP3408423B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102016103866.0A DE102016103866B3 (de) 2016-03-03 2016-03-03 Verfahren zum Wärmebehandeln eines aus einem Metallwerkstoff bestehenden Bauteils mit mindestens einem mit einer Glasur- oder Emaille-Beschichtung beschichteten Flächenabschnitt
PCT/IB2017/000192 WO2017149380A1 (de) 2016-03-03 2017-03-02 Verfahren zum wärmebehandeln eines aus einem metallwerkstoff bestehenden bauteils mit mindestens einem mit einer glasur- oder emaille-beschichtung beschichteten flächenabschnitt

Publications (2)

Publication Number Publication Date
EP3408423A1 EP3408423A1 (de) 2018-12-05
EP3408423B1 true EP3408423B1 (de) 2021-05-19

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EP17716981.0A Active EP3408423B1 (de) 2016-03-03 2017-03-02 Verfahren zum wärmebehandeln eines aus einem metallwerkstoff bestehenden bauteils mit mindestens einem mit einer glasur- oder emaille-beschichtung beschichteten flächenabschnitt

Country Status (10)

Country Link
US (1) US20190085466A1 (ru)
EP (1) EP3408423B1 (ru)
JP (1) JP2019507830A (ru)
KR (1) KR102190321B1 (ru)
CN (1) CN108779540B (ru)
BR (1) BR112018016765A2 (ru)
DE (1) DE102016103866B3 (ru)
RU (1) RU2724268C2 (ru)
WO (1) WO2017149380A1 (ru)
ZA (1) ZA201805487B (ru)

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1919136A (en) * 1933-02-15 1933-07-18 Smith Lloyd Raymond Enameled metal articles and method of producing them
GB580689A (en) * 1943-08-13 1946-09-17 Du Pont Improvements in or relating to the application of enamel compositions to aluminium base alloys
US3149001A (en) * 1962-04-05 1964-09-15 Aluminum Co Of America Enameled aluminous metal product
DE3277585D1 (en) * 1981-09-05 1987-12-10 Lucas Ind Plc Coated metal substrate and method of coating a metal substrate
SU1353549A1 (ru) * 1986-07-01 1987-11-23 Казахский Государственный Научно-Исследовательский И Проектный Институт Нефтяной Промышленности Способ изготовлени трубопроводов из эмалированных труб
DE102010025286B4 (de) * 2010-06-28 2013-08-01 Nemak Linz Gmbh Leichtmetallgussteil für einen Verbrennungsmotor
CN102206828B (zh) * 2011-05-20 2013-05-08 大庆高新区北油创业科技有限公司 一种抽油杆表面合金化高综合性能改性处理工艺
CN102605378A (zh) * 2012-01-13 2012-07-25 浙江吉利汽车研究院有限公司 一种齿轮的渗碳淬火方法
CN103011600B (zh) * 2012-12-27 2015-01-14 广东潮宏基实业股份有限公司 一种用于贵金属饰品表面涂层的珐琅
DE102013108428A1 (de) * 2013-08-05 2015-02-05 Tenedora Nemak, S.A. De C.V. Emaillepulver, Metallbauteil mit einem mit einer Emaillebeschichtung versehenen Flächenabschnitt und Verfahren zum Herstellen eines solchen Metallbauteils

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
DE102016103866B3 (de) 2017-05-18
RU2724268C2 (ru) 2020-06-22
US20190085466A1 (en) 2019-03-21
ZA201805487B (en) 2019-06-26
CN108779540B (zh) 2021-10-08
JP2019507830A (ja) 2019-03-22
CN108779540A (zh) 2018-11-09
RU2018134476A (ru) 2020-04-03
RU2018134476A3 (ru) 2020-04-03
EP3408423A1 (de) 2018-12-05
KR102190321B1 (ko) 2020-12-14
KR20180121952A (ko) 2018-11-09
WO2017149380A1 (de) 2017-09-08
BR112018016765A2 (pt) 2018-12-26

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