• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Corrosion damage to tubes made of copper or copper alloys by local pitting is usually triggered by the residues of drawing oil located on the inner surface and/or by oxide layers of poor adhesion. To achieve an especially high resistance of internally oxidised tubes to pitting or to prevent an uneven formation or detachment of the oxides located on the inner surface, according to the invention the thickness of the copper-oxide layer adhering to the basic metal is limited to values of between 0.01 and 0.2 mu m. Preferably, the copper-oxide crystals have a maximum grain size of 0.5 mu m and possess an oriented structure. The good adhesion of the copper-oxide layer formed on the inner surface of the tube preferably by continuous annealing is preserved even when the tubes have been subjected to a machining reducing their cross-section, for example by bending or drawing.
    公开号:SU1716974A3
    申请号:SU894614651
    申请日:1989-07-26
    公开日:1992-02-28
    发明作者:Баукло Ахим；Райтер Ульрих；Трике Кристиан
    申请人:Км-Кабельметал Аг (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to pipes with an oxidized inner surface of copper or copper alloys, in particular, for use in the field of sanitation, in particular, to a method for producing pipes with an oxidized inner surface.
    Copper or copper alloy pipes are used as pipelines in the field of sanitation, for example, for cold and hot water, as well as in condensers and heat exchangers. To prevent corrosion damage due to the occurrence of localized pitting corrosion sites, to a significant extent, before annealing, residual drawing oil, which is prone to carbon deposition, is located on the inner surface of the pipes, due to degreasing agents, such as organic solvents such as tri- or perchlorethylene.
    Known methods, which provide for the implementation of annealing in a reducing atmosphere and then release the inner surface of the pipe from the possibility of
    yu VI
    -fcb

    Ca
    no carbon film by shot blasting. At the same time, shot blasting is introduced into the pipe either by using compressed air or pressurized water.
    In addition, it is known to establish a low content of residual carbon due to the fact that, after degreasing the pipes, heat treatment is carried out in an oxygen-containing atmosphere, such as a certain gas mixture of oxygen, gels and argon. When heat-treated under oxidizing conditions, in particular in a stationary manner, there is a risk that the oxide films formed have poor adhesion, have an increased thickness and under certain circumstances are porous, as a result of which it is not possible to prevent negative effects — anti-corrosion properties. In addition, oxide films with a thickness greater than or equal to 0.2 µm can be easily cracked or peeled off during subsequent processing of the pipe, for example during bending.
    Similar problems exist when pipes after heat treatment under oxidizing conditions for the production of a semi-solid state still have to undergo treatment to reduce the cross-section. Then the deformation forces also lead to cracks and peeling of the oxide layer formed on the inner surface. Delaminated oxides can then lead to faults in the individual units of the plant.
    The purpose of the invention is to increase the service life by eliminating flaking and cracking.
    The invention is based on the task of providing pipes with an oxidized inner surface of copper or copper alloys with high resistance to pitting corrosion, whose oxides present on the inner surface do not result from adverse formation or exfoliation of the corrosive effects. pipe durability or reliability of the installation.
    According to the invention, the thickness of the oxide layer adhering to the base metal is in the range from 0.01 to 0.2 µm, and this layer is free from cracks and has no delaminations when the pipes are deformed by drawing or bending.
    According to the proposed method, pipes with an oxidized inner surface have a thickness of copper oxide
    layer, preferably in the range from 0.03 to less than 0.1 microns. By varying the parameters of the method, it is possible to establish in a very precise way almost
    any value within this range. In this case, it is possible to establish appropriate operating conditions for annealing, in particular, the duration of annealing under oxidizing conditions, as well as the composition and pressure required for this gas mixture. For the economical manufacture of pipes, as well as for the uniform formation of an oxide film on the inner surface of pipes
    5, transmission annealing should be realized, i.e. using the continuous mode.
    The insignificant thicknesses of the oxide layer on the inner surface of the pipes also
    0 in aggressive waters provide adequate protection against pitting corrosion. After deformation of the cross section by up to 20% or after extreme bending by up to 180 °, there is no deterioration5 of the anti-corrosion properties.
    Determining whether an oxide layer on the inner surface of pipes is damaged by cracks or delaminations can easily be carried out with the naked eye. For these studies, the pipes are divided in the longitudinal direction after they have been previously deformed, for example, bent by up to 180 °. The oxide layer is evaluated as adhering to the base metal if the inner surface of the pipes after deformation shows no signs of damage due to cracks or delaminations.
    0 The control of the oxide layer located on the base metal using a scanning electron microscope showed that the size of the copper oxide crystal grains does not exceed the value of 0.05 µm. Visual
    5, the oxide layer, as opposed to the inner surfaces of the pipes studied so far, has a uniform surface. The oxide layer has a light red color and has a high reflectivity when light hits. The crystals of the oxide layer consist of CaO (cuprite) and mainly have an oriented (1,1,1) structure.
    5 There is a simple relationship between the thickness of the oxide layer and the residual carbon content on the inner surface of the pipes. The thinner the oxide layer is, the lower the residual carbon content. but
    A decrease in the residual carbon content to less than 0.03 mg / dm2 has so far been achieved only due to the exceptionally expensive degreasing of the inner surface of the pipe before annealing under oxidizing conditions. In this case, the oxidizing annealing itself was to be carried out in an atmosphere that contains approximately 85% of a mixture of inert gases from helium and argon.
    A residual carbon content of less than or equal to 0.05 mg / dm is not necessary to prevent corrosion damage. In contrast, the uniformity and small thickness of the oxidation are essential, with the layer thickness being less than 0.2 µm, preferably less than 0.1 µm.
    Example. In order to manufacture pipes with an oxidized inner surface according to the invention, the inner surface was first degreased in ring-shaped copper pipes, for example from phosphorus-deoxidized copper. The residual content of the fatty substance on the inner surface of the pipe before oxidizing annealing was less than 0.4 mg / dm2. Accordingly, individual sections of copper pipes, connected to each other on the side of the end by means of gas-permeable fittings, were annealed during continuous transmission using resistive or inductive heating at a temperature in the range from 600 to 730 ° C, and controlled gas was introduced into the pipes mixture. Depending on the transmission rate set in the range between 50 and 220 m / min, as well as the cross-section of the pipes, an atmosphere was established inside the pipes. The gas mixture mainly consists of oxygen in an amount of from 5 to approximately 15 vol.% And an inert gas in an amount of 85 to 95 vol.%, Favorable at the price of nitrogen. Due to the constant control of the temperature and rate of continuous annealing, as well as the oxygen content in the gas atmosphere, it was possible to achieve uniformity of the copper oxide layer, the thickness of which is in the required range.
    The predominant thickness of the layer of copper oxide adhering to the base metal was generally in the range between 0.03 and 0.09 µm. The full adhesion of this thin copper oxide film is also maintained after the copper tube is deformed with a reduction in cross section by up to 20% or bend by up to 180 °. No detachments or cracks in the oxide layer were found after deformation.
    using the naked eye, or under a microscope at 40x magnification.
    Good adhesion of copper oxides is also of particular importance when semisolid copper pipes are to be manufactured. In order to establish the state of semi-solid copper pipes that have undergone incomplete annealing, they must be deformed with a decrease in the cross section, while they, for example, extend from a size of 18 mm to a diameter of 15 mm. Hard copper copper tubes are usually deformed to the desired final size without the inclusion of recrystallization annealing between the steps of the drawing. To create a thin copper oxide film on the inner surface of the pipes, these pipes undergo heat treatment at temperatures of approximately 250 ° C so briefly that their mechanical properties cannot change in a negative way.
    权利要求:
    Claims (9)
    [1]
    1. A pipe with an oxidized inner surface made of copper or copper alloys, in particular, of sanitary-technical purpose, characterized in that, in order to increase the service life by eliminating flaking and cracking, the oxide layer is made 0.01-0.2 μm thick ..
    [2]
    2. A tube according to claim 1, characterized in that the copper oxide layer has a thickness in the range of 0.03-0.1 μm.
    [3]
    3. A tube according to claims 1 or 2, characterized in that the maximum grain size of the copper oxide crystals in the layer is 0.05 µm.
    [4]
    4. A pipe according to claim 3, characterized in that the copper oxide crystals have an oriented (1,1,1) structure.
    [5]
    5. A tube according to claims 1-4, characterized in that it is made in the state of incomplete annealing after the last deformation operation.
    [6]
    6. A tube according to claims 1-4, which is characterized by the fact that it has a semi-solid state.
    [7]
    7. A pipe according to claim 1-4, characterized in that it has a hard state.
    [8]
    8. A tube according to claims 1 to 7, characterized in that it is made on resistant to pitting corrosion with a residual carbon content of less than 0.15 mg / dm and a layer of copper oxide from 0.03 to 0.09 microns.
    [9]
    9. A method of manufacturing a tube with an oxidized inner surface, including the removal of fatty substances with a solvent and annealing in an atmosphere containing oxygen and inertial gas, characterized by that. what's annealing
    717169748
    lead at 600-730 ° C with a flow rate of less than 15 vol. % and inert gas 75-99 about. %, pipe ekani 50-220 m / min with a content of mostly 85-95% vol., while in oxygen 1-25% vol., mostly 5 - nitrogen is used as an inert gas.
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    同族专利:
    公开号 | 公开日
    PT91428A|1990-03-08|
    RO109463B1|1995-02-28|
    EP0356732A1|1990-03-07|
    DE3827353A1|1990-02-22|
    NO177688C|1995-11-15|
    TNSN89088A1|1991-02-04|
    DE58901399D1|1992-06-17|
    AR247013A1|1994-10-31|
    DZ1349A1|2004-09-13|
    MX173263B|1994-02-14|
    ES2036763T3|1993-06-01|
    DD284078A5|1990-10-31|
    DK388089A|1990-02-13|
    AT76175T|1992-05-15|
    EP0356732B1|1992-05-13|
    IE892217L|1990-02-12|
    JPH0261054A|1990-03-01|
    PT91428B|1995-08-09|
    IL91145A|1995-07-31|
    JP2895095B2|1999-05-24|
    HUT54786A|1991-03-28|
    IL91145D0|1990-03-19|
    KR940010772B1|1994-11-11|
    CZ280990B6|1996-05-15|
    GR3004809T3|1993-04-28|
    FI90136B|1993-09-15|
    FI893785A|1990-02-13|
    CA1324584C|1993-11-23|
    MA21591A1|1990-04-01|
    NO893246L|1990-02-13|
    NO177688B|1995-07-24|
    KR900003417A|1990-03-26|
    PL161517B1|1993-07-30|
    DK388089D0|1989-08-08|
    CS8904206A2|1991-09-15|
    FI893785A0|1989-08-10|
    SK278911B6|1998-04-08|
    DK169750B1|1995-02-13|
    IE61097B1|1994-09-21|
    YU46649B|1994-01-20|
    NO893246D0|1989-08-11|
    HU214381B|1998-03-30|
    FI90136C|1993-12-27|
    YU118689A|1991-02-28|
    ZA896043B|1990-05-30|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    LU80891A1|1979-02-07|1980-09-24|Liege Usines Cuivre Zinc|SANITARY TUBES OF PHOSPHORUEX COPPER OR CORROSION-RESISTANT PHOSPHORUS COPPER ALLOYS AND PROCESS FOR THEIR PRODUCTION|
    DE3003228C2|1980-01-30|1981-11-26|Wieland-Werke Ag, 7900 Ulm|Process for improving the corrosion resistance of installation pipes made of copper|
    LU83165A1|1981-02-25|1982-09-10|Liege Usines Cuivre Zinc|TUBES FOR CONDENSERS OR HEAT EXCHANGERS OF CORROSION RESISTANT COPPER ALLOYS AND METHOD FOR THE PRODUCTION THEREOF|
    AT45993T|1987-03-07|1989-09-15|Wieland Werke Ag|METHOD FOR IMPROVING THE CORROSION RESISTANCE OF HARDEN OR. SEMI-HARD COUPLING PIPES.|JP3155365B2|1992-08-10|2001-04-09|日本ケーブル・システム株式会社|Accelerator operation device|
    DE4417455C2|1994-05-19|1997-09-25|Wieland Werke Ag|Use of a corrosion-resistant tube with inner oxide layers|
    DE19819925A1|1998-05-05|1999-11-11|Km Europa Metal Ag|Process for creating a protective layer on the inner surface of a copper pipe|
    FI107543B|1998-07-30|2001-08-31|Outokumpu Oy|Process for making a copper tube|
    US6293336B1|1999-06-18|2001-09-25|Elkay Manufacturing Company|Process and apparatus for use with copper containing components providing low copper concentrations portable water|
    KR100466182B1|2002-09-16|2005-01-13|허봉락|Anti-shocking member|
    FI120359B|2002-12-18|2009-09-30|Cupori Group Oy|Method and apparatus for treating an inner surface of a copper or copper alloy tube|
    DE102007055446A1|2007-11-12|2009-05-14|Hansgrohe Ag|Provision of water-bearing components from brass alloys with reduced metal ion release|
    法律状态:
    2010-07-20| REG| Reference to a code of a succession state|Ref country code: RU Ref legal event code: MM4A Effective date: 20080727 |
    优先权:
    申请号 | 申请日 | 专利标题
    DE3827353A|DE3827353A1|1988-08-12|1988-08-12|INTERNAL OXIDIZED TUBES|
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