EP2864520B1 - Process for the anti-oxidising surface treatment of steel parts - Google Patents

Process for the anti-oxidising surface treatment of steel parts Download PDF

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Publication number
EP2864520B1
EP2864520B1 EP12766159.3A EP12766159A EP2864520B1 EP 2864520 B1 EP2864520 B1 EP 2864520B1 EP 12766159 A EP12766159 A EP 12766159A EP 2864520 B1 EP2864520 B1 EP 2864520B1
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EP
European Patent Office
Prior art keywords
steel parts
oxidising
components
nitriding
washing
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EP12766159.3A
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German (de)
French (fr)
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EP2864520A1 (en
Inventor
Fabrizio CAVINA FULVIO
Guido ROVETTO
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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
    • C23C8/02—Pretreatment of the material to be coated
    • 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
    • C23C8/08—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 only one element being applied
    • C23C8/10—Oxidising
    • C23C8/12—Oxidising using elemental oxygen or ozone
    • C23C8/14—Oxidising of ferrous surfaces
    • 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
    • C23C8/08—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 only one element being applied
    • C23C8/10—Oxidising
    • C23C8/16—Oxidising using oxygen-containing compounds, e.g. water, carbon dioxide
    • C23C8/18—Oxidising of ferrous surfaces
    • 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
    • C23C8/08—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 only one element being applied
    • C23C8/24—Nitriding
    • C23C8/26—Nitriding of ferrous surfaces
    • 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
    • C23C8/34—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 more than one step
    • 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
    • C23C8/80—After-treatment

Definitions

  • the present invention refers to a process for the anti-oxidising surface treatment of steel parts.
  • a galvanic treatment can be performed, such as chromium-plating, nickel-plating or partially zinc-plating, etc.
  • Another type of treatment, this time of the thermal type, is nitriding, followed by an oxidising step performed in salt baths at the presence of cyanide, cyanate and sodium carbonate, which therefore is rather obnoxious from the ecological and working safety points of view.
  • the corrosion resistance feature is important, and is obtained, using the current technology, by painting such envelopes with a suitable corrosion-preventing paint: also this treatment has severe ecological problems, due to the toxic materials being used.
  • Object of the present invention is solving the above prior art problems, by providing a new process for the anti-oxidising treatment of steel parts that is ecological, does not show the above pollution and working safety problems and provides the same levels of wear and corrosion resistance of current technologies; such process further allows extending the length of such resistance, in components such as filters, because it will not be necessary any more to paint them, since such property will be embedded into the structure itself of the material being treated.
  • Another object of the present invention is providing a process as mentioned above that has a better resistance to saline mist, and allows a better oxidising, with respect to known processes.
  • a further benefit of such process is that it is much safer than the previous ones, using a step of pre-heating with nitrogen instead of air, as happened in prior processes.
  • the process of the invention is used for the anti-oxidising surface treatment of steel parts, and comprises the steps of:
  • the steel parts can be components for motor vehicle use, or for oil platforms, or still more to be used in mechanics.
  • inventive process is also applied to several other types of components that need nitriding and oxidising.
  • the mixture with which the sub -step of maintaining at the same temperature of 520 - 600 °C is performed contains, in volume, 70% of NH 3 , from 10% to 15% of N 2 and, respectively, from 20% to 15% of CO 2 .
  • the mixture with which the sub-step of maintaining at the same temperature of 520 - 600 °C is performed can contain, in volume, 70% of NH 3 , 10% of N 2 and 20% of CO 2 .
  • a plant for performing the above-described anti-oxidising surface treatment of steel parts substantially comprises:
  • the oxidising means 9 are connected to the pit furnace 7 in order to perform in a single plant the step of steam oxidising after the step of washing with nitrogen the furnace 7.
  • the charge 3 is extracted from the furnace 7, through the handling means 2, and is sent to following workings.
  • FIG 2 describes a typical pit furnace 7 used for the plant of Figure 1 .
  • the furnace 7 comprises an external structure 11 for support and heat insulation, composed of ceramic fiber and containing, inside, on its side walls and its lower wall, a plurality of electric resistances 13 for heating the internal environment.
  • the charge 3 is inserted centrally and coaxially into the furnace 7 using its upper opening; the charge 3 is slinged in a supporting structure 15 ending with a cover 17 that facilitates its various handling operations.
  • the furnace 7 is closed by a plug 19, modelled in order to support a motored fan 21, whose blades 23 work in order to move the gas mixture contained inside the furnace, in order to keep its temperature uniform.
  • the furnace 7 is further equipped, in its upper part, with an exhausting device 25, which is a barrel from which reaction gases from various processes go out: such gases are burnt by the flame generated by such exhausting device 25.
  • Function of the exhausting device 25 is also signalling the moment in which the oxidising step (that has different operating times according to the number and sizes of treated parts) ends, because at such time the small flame contained therein is extinguished.
  • the oxidising means 9 can be composed of an intermittence-type pump suitable to send distilled water onto the charge 3 for its oxidation, or be composed of a steam generator adapted to steam-oxidise the charge 3, or still more be oxidising means adapted to perform the oxidising of the charge 3 by using the same CO 2 already present in the nitriding plant.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)

Description

  • The present invention refers to a process for the anti-oxidising surface treatment of steel parts.
  • Various types of anti-oxidising surface treatments are known in the art, to which steel parts are subjected, which, at the end of such treatment, are put in such a condition as to efficiently resist to wear and corrosion, to which they are subjected according to the working environment in which they operate. IT TO 930 489 A1 describes an anti-oxidising surface treatment of steel parts.
  • In particular, for components used in the motor vehicle field, such as filters, gas springs, etc., a galvanic treatment can be performed, such as chromium-plating, nickel-plating or partially zinc-plating, etc. Another type of treatment, this time of the thermal type, is nitriding, followed by an oxidising step performed in salt baths at the presence of cyanide, cyanate and sodium carbonate, which therefore is rather obnoxious from the ecological and working safety points of view.
  • In the field of parts and components for motor vehicle filters, in order to build the external envelopes for protecting and containing such filters, the corrosion resistance feature is important, and is obtained, using the current technology, by painting such envelopes with a suitable corrosion-preventing paint: also this treatment has severe ecological problems, due to the toxic materials being used.
  • Object of the present invention is solving the above prior art problems, by providing a new process for the anti-oxidising treatment of steel parts that is ecological, does not show the above pollution and working safety problems and provides the same levels of wear and corrosion resistance of current technologies; such process further allows extending the length of such resistance, in components such as filters, because it will not be necessary any more to paint them, since such property will be embedded into the structure itself of the material being treated.
  • Another object of the present invention is providing a process as mentioned above that has a better resistance to saline mist, and allows a better oxidising, with respect to known processes. A further benefit of such process is that it is much safer than the previous ones, using a step of pre-heating with nitrogen instead of air, as happened in prior processes.
  • The above and other objects and advantages of the invention, as will appear from the following description, are obtained with a process as claimed in the independent claim. Preferred embodiments and non-trivial variations of the present invention are the subject matter of the dependent claims.
  • It is intended that all enclosed claims are an integral part of the present description.
  • The present invention will be better described by some preferred embodiments thereof, provided as a non-limiting example, with reference to the enclosed drawings, in which:
    • Figure 1 is a schematic view of an embodiment of the plant according to the present invention; and
    • Figure 2 is a side sectional view of a pit furnace used in the plant of Figure 1.
  • With reference to the Figure, a preferred embodiment of the process and plant of the present invention is shown and described.
  • The process of the invention is used for the anti-oxidising surface treatment of steel parts, and comprises the steps of:
    • washing or de-greasing a charge of steel components to be treated;
    • nitriding under gaseous phase the charge, after its washing, wherein the step of nitriding is composed of the sub-steps of:
      • pre-heating with nitrogen till a temperature of 350 °C;
      • heating from 350 °C to 450 °C in an atmosphere composed of CO2;
      • heating from 450 °C to 520 - 600 °C for half an hour in an atmosphere containing N2;
      • maintaining, at the same temperature of 520 - 600 °C, for a period from 2 to 10 hours, in an atmosphere composed of a mixture containing NH3, CO2 and N2;
    • washing with nitrogen the environment where nitriding occurred; and
    • steam oxidising, consisting in the immission of overheated steam at a temperature in the range between 490 °C and 540 °C for the necessary time to obtain a complete oxygen-iron exchange.
  • Preferably, but not in a limiting way, the steel parts can be components for motor vehicle use, or for oil platforms, or still more to be used in mechanics. Obviously, the inventive process is also applied to several other types of components that need nitriding and oxidising. The mixture with which the sub -step of maintaining at the same temperature of 520 - 600 °C is performed, contains, in volume, 70% of NH3, from 10% to 15% of N2 and, respectively, from 20% to 15% of CO2. In particular, the mixture with which the sub-step of maintaining at the same temperature of 520 - 600 °C is performed, can contain, in volume, 70% of NH3, 10% of N2 and 20% of CO2. A plant for performing the above-described anti-oxidising surface treatment of steel parts substantially comprises:
    • a washing machine 5;
    • a pit furnace 7;
    • oxidising means 9; and
    • handling means 2 (of the winch type) of a charge 3 with the parts to be treated;
    wherein, through the handling means 2, the charge 3 is first inserted into the washing machine 5, to be washed and de-greased (removing impurities from previous working, such as for example oil), and is then inserted into the pit furnace 7 to be subjected to the steps of nitriding and washing the furnace 7 with nitrogen.
  • The oxidising means 9 are connected to the pit furnace 7 in order to perform in a single plant the step of steam oxidising after the step of washing with nitrogen the furnace 7.
  • At the end of the nitriding process, the charge 3 is extracted from the furnace 7, through the handling means 2, and is sent to following workings.
  • Figure 2 describes a typical pit furnace 7 used for the plant of Figure 1. With reference to Figure 2, the furnace 7 comprises an external structure 11 for support and heat insulation, composed of ceramic fiber and containing, inside, on its side walls and its lower wall, a plurality of electric resistances 13 for heating the internal environment. The charge 3 is inserted centrally and coaxially into the furnace 7 using its upper opening; the charge 3 is slinged in a supporting structure 15 ending with a cover 17 that facilitates its various handling operations. After having inserted the charge 3, the furnace 7 is closed by a plug 19, modelled in order to support a motored fan 21, whose blades 23 work in order to move the gas mixture contained inside the furnace, in order to keep its temperature uniform. The furnace 7 is further equipped, in its upper part, with an exhausting device 25, which is a barrel from which reaction gases from various processes go out: such gases are burnt by the flame generated by such exhausting device 25. Function of the exhausting device 25 is also signalling the moment in which the oxidising step (that has different operating times according to the number and sizes of treated parts) ends, because at such time the small flame contained therein is extinguished. The oxidising means 9 can be composed of an intermittence-type pump suitable to send distilled water onto the charge 3 for its oxidation, or be composed of a steam generator adapted to steam-oxidise the charge 3, or still more be oxidising means adapted to perform the oxidising of the charge 3 by using the same CO2 already present in the nitriding plant.

Claims (5)

  1. Process for the anti-oxidising surface treatment of steel parts comprising the steps of:
    - washing or de-greasing a charge of steel components to be treated;
    - nitriding under gaseous phase said charge, after its washing, said step of nitriding being composed of the sub-steps of:
    • pre-heating with nitrogen till a temperature of 350 °C;
    • heating from 350 °C to 450 °C in an atmosphere composed of CO2;
    • heating from 450 °C to 520 - 600 °C for half an hour in an atmosphere containing N2;
    • maintaining, at the same temperature of 520 - 600 °C, for a period from 2 to 10 hours, in an atmosphere composed of a mixture containing NH3, CO2 and N2, wherein the mixture with which the sub-step of maintaining at the same temperature of 520 - 600 °C is performed, contains, in volume, 70% of NH3, from 10% to 15% of N2 and, respectively, from 15% to 20% of CO2;
    - washing with nitrogen the environment where said nitriding occurred; and
    - steam oxidising, consisting in the immission of overheated steam at a temperature in the range between 490 °C and 540 °C for the necessary time to obtain a complete oxygen-iron exchange.
  2. Process according to claim 1, wherein the steel parts are components for motor vehicle use.
  3. Process according to claim 1, wherein the steel parts are components for oil platforms.
  4. Process according to claim 1, wherein the steel parts are components to be used in mechanics.
  5. Process according to claim 1, wherein the mixture with which the sub-step of maintaining at the same temperature of 520 - 600 °C is performed, contains, in volume, 70% of NH3, 10% of N2 and 20% of CO2.
EP12766159.3A 2012-06-26 2012-06-26 Process for the anti-oxidising surface treatment of steel parts Active EP2864520B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IT2012/000198 WO2014002120A1 (en) 2012-06-26 2012-06-26 Process and plant for the anti-oxidising surface treatment of steel parts

Publications (2)

Publication Number Publication Date
EP2864520A1 EP2864520A1 (en) 2015-04-29
EP2864520B1 true EP2864520B1 (en) 2018-09-26

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EP (1) EP2864520B1 (en)
CN (1) CN104603319B (en)
BR (1) BR112014032480A2 (en)
IN (1) IN2015MN00144A (en)
WO (1) WO2014002120A1 (en)

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Publication number Priority date Publication date Assignee Title
CN104928619A (en) * 2014-08-28 2015-09-23 浙江长兴天盛工业炉有限公司 Pit-type nitriding furnace
CN105063549B (en) * 2015-07-17 2017-08-04 东莞市海瀚防静电器材有限公司 Nitriding anticorrosion composition metal lean tube preparation method and preparation facilities
CN106482523B (en) * 2016-05-30 2019-03-08 丁文江 Use superheated steam as the heat treatment system and heat treatment method of heat transfer carrier
CN109576634A (en) * 2018-12-28 2019-04-05 宁波合力模具科技股份有限公司 A kind of high vacuum squeezes the process for surface oxidation of compression mod
CN110724902A (en) * 2019-11-18 2020-01-24 惠州市鑫洪柏精密五金制品有限公司 Pollution-free steel gas blackening process
CN110952061A (en) * 2019-12-16 2020-04-03 上海始金新材料科技有限公司 Horizontal oxynitriding furnace
EP4008802A1 (en) * 2020-12-02 2022-06-08 Linde GmbH Method of and apparatus for oxidative post-processing of a nitrided or nitrocarburized article
CN113604772A (en) * 2021-08-18 2021-11-05 盛瑞传动股份有限公司 Workpiece steam treatment process
CN114293139A (en) * 2021-12-07 2022-04-08 江苏聚源电气有限公司 Low-temperature soft nitriding process

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EP0229325B1 (en) * 1981-10-15 1995-01-04 LUCAS INDUSTRIES public limited company Method of manufacturing a corrosion resistant steel component
GB8310102D0 (en) * 1983-04-14 1983-05-18 Lucas Ind Plc Corrosion resistant steel components
JPH01298146A (en) * 1988-05-26 1989-12-01 Toray Eng Co Ltd Treatment for metal surface
IT1261077B (en) * 1993-07-06 1996-05-08 Procedure for a rust-proofing surface treatment of steel parts, especially for filter parts or components
DE50001540D1 (en) * 2000-02-04 2003-04-30 Ipsen Int Gmbh Process for nitriding and / or nitrocarburizing higher alloy steels
CN101050517A (en) * 2007-05-15 2007-10-10 上海工业大学嘉定通用机械有限公司 Technique method of treatment for modifying surface of ferrous material

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Publication number Publication date
IN2015MN00144A (en) 2015-10-16
EP2864520A1 (en) 2015-04-29
CN104603319A (en) 2015-05-06
CN104603319B (en) 2017-10-10
BR112014032480A2 (en) 2017-06-27
WO2014002120A1 (en) 2014-01-03

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