CN110453170B - Method for forming compact oxide layer on surface of Fe-Cr-Si series alloy - Google Patents

Method for forming compact oxide layer on surface of Fe-Cr-Si series alloy Download PDF

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CN110453170B
CN110453170B CN201910850347.8A CN201910850347A CN110453170B CN 110453170 B CN110453170 B CN 110453170B CN 201910850347 A CN201910850347 A CN 201910850347A CN 110453170 B CN110453170 B CN 110453170B
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alloy
layer
oxide layer
oxygen pressure
oxidation
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CN110453170A (en
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苏旭平
江靖琛
刘亚
王建华
吴长军
涂浩
彭浩平
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Changzhou University
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Changzhou University
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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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/123—Spraying molten metal
    • 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

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
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  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Coating By Spraying Or Casting (AREA)

Abstract

The invention belongs to a surface coating technology, in particular to a method for forming a compact oxide layer on the surface of Fe-Cr-Si series alloy. The invention utilizes the technology that after a layer of Fe-Cr-Si alloy with the same component ratio is sprayed on the surface of the obtained Fe-Cr-Si alloy, the powder pile is utilized to control the oxygen pressure to prepare the oxidation film, under the environment of low oxygen pressure, the outer side of the plating layer is preferentially oxidized to form an oxidation layer, the internal diffusion of oxygen atoms is prevented to a certain extent, and the ultra-low oxygen pressure is generated between the plating layer and the alloy surface, thereby causing the selective oxidation to occur on the interface and improving the corrosion resistance of the matrix in a corrosion medium.

Description

Method for forming compact oxide layer on surface of Fe-Cr-Si series alloy
Technical Field
The invention belongs to the field of alloy oxidation, and particularly relates to selective oxidation work on an alloy surface, in particular to a selective oxidation method of Fe-Cr-Si alloy under spray plating.
Background
Most alloys used as structural materials are severely damaged when exposed to low oxygen atmospheres and relatively high sulfur partial pressures at high temperatures (e.g., coal gasification). The unprotected sulfides grow rapidly on the surface of the alloy, resulting in rapid degradation of the alloy. Researchers have spent a great deal of time and effort to solve this problem for decades. Binary alloys such as Fe-Mn, Fe-Si, Fe-Y, Ni-Nb, Co-Y, Fe-Nb have been reported to fail to form protective scale in atmospheres containing O and S.
Therefore, the research focus is changed into ternary alloy, and the oxidation and vulcanization behaviors of the ternary alloy are more complex than those of the binary alloy. In the existing research, Fe-Cr-Ni alloy is in H2/H2O/H2Rapid degradation occurs in the S/Ar mixed atmosphere. In particular cases, Ti-Cr-Al alloys may exhibit good corrosion resistance. For example, when Cr is present2O3When having thermodynamic stability, the Ti-Cr-Al alloy has good corrosion resistance. The preparation of a protective coating on the surface of the alloy is an advantageous method for improving the corrosion resistance of a substrate. Dudziak et al report that multilayer CrAlYN/CrN coatings can be applied at H2/H2S/H2A protective layer was locally induced on the Ti-45Al-8Nb in the O mixture. In addition, nano-or micro-coatings have been reported to improve the oxidation and sulfidation resistance of the alloy.
According to our investigations on the oxidation of alloys, the formation of protective scale has a good corrosion resistance to alloys exposed to harsh environments, such as SiO2And Cr2O3The formation of a protective scale on the alloy surface can be effectively improved. Thus, the content of Cr or Si in the alloy can be increased, or a coating containing high content of Cr and Si can be prepared on the surface of the alloy. Cr is added into Fe-Si alloy to induce SiO formation in pure oxygen atmosphere2And (3) a layer. Secondly, we can also reduce the grain size of the alloy to improve the out-diffusion of Cr and Si to achieve selective oxidation of Si and form a protective film.
Disclosure of Invention
The invention aims to provide a selective oxidation method for Fe-Cr-Si series alloy under spray plating, which is simple to operate, economical and practical and is suitable for industrial continuous production, so as to improve the corrosion resistance of the Fe-Cr-Si series alloy in a corrosive medium.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for forming a dense oxide layer on the surface of Fe-Cr-Si series alloy comprises the following steps: firstly, spraying a layer of Fe-Cr-Si plating layer with the same component ratio on the surface of Fe-Cr-Si alloy, wherein the thickness of the Fe-Cr-Si plating layer is 15-20 mu m; then controlling oxygen pressure by using a powder pile to form low oxygen pressure of 0.05-0.2 Mpa between the surface of the Fe-Cr-Si alloy and the Fe-Cr-Si plating layer, heating and carrying out constant temperature selective oxidation to obtain continuous compact Cr formed on the surface of the Fe-Cr-Si alloy2O3+SiO2And oxidizing the layer.
Compared with the prior art, the invention sprays a layer of same composition ratio on the surface of the Fe-Cr-Si series alloyThe thickness of the Fe-Cr-Si coating is controlled to be 15-20 mu m, and the micron-sized coating can improve certain oxidation resistance and sulfuration resistance of the alloy. In addition, the internal oxygen pressure is controlled within the range of 0.05-0.2 Mpa by a method for preparing an oxidation film by powder stack controlled oxidation, and because an oxidation layer is preferentially formed outside the Fe-Cr-Si coating, the internal diffusion of oxygen atoms is prevented to a certain extent, the ultra-low oxygen pressure is formed between the alloy surface and the coating, the selective oxidation is carried out at the interface, and continuous Cr is generated2O3+SiO2And the oxide layer increases the corrosion resistance of the matrix. The Fe-Cr-Si alloy of the invention is selectively oxidized under the condition of spray plating, a new selective oxidation mode is provided for metal corrosion protection, and the interface is selectively oxidized at the joint of a substrate and a plating layer due to the formation of low oxygen pressure, thereby generating continuous Cr2O3+SiO2And the oxidation layer organizes the inward diffusion of oxygen atoms to play a role of protection. Fundamentally improving the condition that the Fe-Cr-Si matrix alloy is corroded and damaged when being used in special atmosphere, prolonging the service life of the Fe-Cr-Si matrix alloy and having considerable social and economic benefits.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate schematically the invention and do not constitute a limitation on the invention, the scope of the invention not being limited to the following schematic drawings.
FIG. 1 is a cross-sectional view (SEI) of a Fe-5Cr-5Si alloy after thermal spraying
FIG. 2 is a graph of the morphology (SEI) of a dense oxide layer produced on the surface of an as-cast Fe-5Cr-5Si alloy that was not thermally sprayed in accordance with an embodiment of the present invention.
Detailed Description
The invention is described in more detail below with reference to the following examples:
the invention is described in detail below with reference to specific embodiments and with reference to the following figures: the present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a process are given, but the scope of the present invention is not limited to the following embodiments. The magnetic control arc furnace device in the following embodiment is a device commonly used in the field, and comprises an FD-118 molecular pump controller, an inverter type direct current manual arc welding machine HM400 II, an arc furnace, a high-vacuum manual flapper valve, an ultrahigh-vacuum manual flapper valve, a water circulating device and an argon bottle.
The Fe-Cr-Si alloys selected for use in the following examples were Fe-5Cr-5Si as-cast alloys, compared to samples that were thermally sprayed and not thermally sprayed and oxidized.
The method for forming the compact oxide layer on the surface of the Fe-5Cr-5Si as-cast alloy comprises the following steps:
step 1, weighing high-purity metal particles of each component required by the preparation of the alloy according to the mass ratio of each component in Fe-5Cr-5Si by using a weighing balance.
Step 2, opening circulating water in the magnetic control arc furnace, placing all weighed metal particles at the position of an inner smelting tank, placing a titanium particle at the middle position of the smelting tank to absorb residual oxygen in the furnace, smearing vacuum grease on the joint of the furnace and the outside, closing the furnace, opening a molecular pump, screwing a diagonal bolt, opening a low-vacuum baffle valve after the molecular pump rotates to 27000 full revolutions, closing the low-vacuum baffle valve after the controller displays that the pressure value in the furnace reaches 2E0, opening a high-vacuum baffle valve until the display shows 2E-3, closing high vacuum, opening an argon bottle valve to introduce argon into the furnace to restore atmospheric pressure in the furnace, then closing the argon to open the low vacuum, circulating for three times, stabilizing the furnace in a high-vacuum state, igniting by an arc welding machine to smelt the metal particles, taking out a sample after smelting is finished, the cast Fe-5Cr-5Si alloy is prepared, annealed for 1 week in vacuum, and cut into pieces for thermal spraying operation with size of 10X 8X 1.5mm by using a wire cutter.
And 3, spraying a layer of Fe-Cr-Si coating with the same composition ratio as the Fe-5Cr-5Si as-cast alloy on the surface of one of the Fe-5Cr-5Si as-cast alloy sheets prepared in the step 2 by using a thermal spraying machine, wherein the thickness of the Fe-Cr-Si coating is controlled to be 15-20 mu m.
Step 4, preparing two quartz tubes, and respectively putting the two quartz tubes into the pre-prepared Cr-Cr tubes2O3Powder pile (namely chromium powder and trioxide)The molar ratio of chromium to chromium oxide is 2:1), then vacuumizing is carried out to burn and recess the middle part of the quartz tube but not close the quartz tube, and after the quartz tube is cooled, the Fe-5Cr-5Si cast alloy sheet after spraying in the step 3 and the other Fe-5Cr-5Si cast alloy sheet prepared in the step 2 are respectively placed into the quartz tube for vacuumizing and sealing.
And 5, putting the two quartz tubes into a deep well furnace set, heating to 900 ℃, preserving heat for 2 hours, and taking out.
The microstructure images of the interface after alloy spraying are observed by a Scanning Electron Microscope (SEM), and are shown in figures 1 and 2.
As shown in FIG. 1, the Fe-Cr-Si alloy of the substrate and the Fe-Cr-Si alloy sprayed on the outer side have a clear gap therebetween, and an oxide layer is formed on both sides of the gap, and the oxide layer is Cr as measured by energy spectroscopy2O3+SiO2. The implementation of the invention can effectively reduce the corrosion oxidation of the base alloy and form a continuous Cr layer below the sprayed layer2O3+SiO2The oxide layer prevents the inward diffusion of cations and ensures the corrosion resistance of the alloy structure. Compared with the cast Fe-Cr-Si alloy without the spraying step, the cast Fe-Cr-Si alloy is directly oxidized. As shown in fig. 2, it was found that the oxide film on the surface of the alloy substrate was broken off due to the external stress (the broken off portion is shown in detail in the circle). Therefore, by spraying a layer of Fe-Cr-Si alloy and then selectively oxidizing, two oxide films are formed inside and outside, and the inner oxide film is formed between the coating and the alloy substrate, so that the inner oxide film is not broken and peeled off under the action of external stress, thereby fully improving the corrosion resistance of the alloy.
Observing that a uniform oxide film is formed on the surface of the sample which is not sprayed, and carrying out component test on the sample, wherein the oxide film is mainly SiO2In addition, part of Cr2O3. However, the surface of the sample was broken and peeled off, and once the oxide film was peeled off, the protective effect of the oxide film on the substrate was greatly reduced. The micron coating of the thermal spraying sample can improve certain oxidation resistance and sulfidization resistance of the matrix, and the selective oxidation caused by the ultra-low oxygen pressure formed at the gap can form an oxidation filmThe division is more uniform. In addition, because the selective oxidation of the thermal spraying sample occurs at the joint of the coating and the substrate, the formed oxide film is not easy to be damaged and peeled off due to external stress. Compared with a sample which is not sprayed, the practicability of preparing the film by selective oxidation can be effectively improved, and the protective effect on the matrix is better.
The Fe-Cr-Si alloy of the invention is selectively oxidized under the condition of spray plating, a new selective oxidation mode is provided for metal corrosion protection, and the interface is selectively oxidized at the joint of a substrate and a plating layer due to the formation of low oxygen pressure, thereby generating continuous Cr2O3+SiO2And the oxide layer prevents the inward diffusion of oxygen atoms and plays a role of protection. Fundamentally improving the condition that the Fe-Cr-Si matrix alloy is corroded and damaged when being used in special atmosphere, prolonging the service life of the Fe-Cr-Si matrix alloy and having considerable social and economic benefits.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and their concepts should be equivalent or changed within the technical scope of the present invention.

Claims (3)

1. A method for forming a compact oxide layer on the surface of Fe-Cr-Si series alloy is characterized in that: the method comprises the following steps: firstly, spraying a Fe-Cr-Si coating with the same composition ratio on the surface of Fe-Cr-Si alloy, wherein the thickness of the Fe-Cr-Si coating is 15-20 mu m; then using Cr-Cr2O3Controlling oxygen pressure by powder pile to form low oxygen pressure of 0.05-0.2 MPa between the surface of the Fe-Cr-Si alloy and the Fe-Cr-Si plating layer, heating at constant temperature for selective oxidation to obtain continuous compact Cr formed on the surface of the Fe-Cr-Si alloy2O3+SiO2And oxidizing the layer.
2. The method for forming a dense oxide layer on a surface of an Fe-Cr-Si based alloy according to claim 1, wherein: the selective oxidation temperature is 900 ℃, and the selective oxidation time is 2 h.
3. The method for forming a dense oxide layer on a surface of an Fe-Cr-Si based alloy according to claim 1, wherein: the powder pile composition for controlling oxygen pressure by using the powder pile is designed into Cr powder and Cr2O3Powder of Cr and Cr2O3The molar ratio of the powders was 2: 1.
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JP2000178707A (en) * 1998-12-09 2000-06-27 Taiho Kogyo Co Ltd Thermal-sprayed layer excellent in sliding characteristic
CN101195901A (en) * 2007-12-06 2008-06-11 上海交通大学 Reaction spray coating metal ceramic composite powder and method for producing the same

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CN105420659A (en) * 2015-11-03 2016-03-23 江苏奇纳新材料科技有限公司 Preparation process for ceramic oxidation film resistant to fused salt corrosion
CN106086601A (en) * 2016-08-25 2016-11-09 安徽丰源车业有限公司 High-strength wearable alloy car door hinge and preparation method thereof
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Publication number Priority date Publication date Assignee Title
JP2000178707A (en) * 1998-12-09 2000-06-27 Taiho Kogyo Co Ltd Thermal-sprayed layer excellent in sliding characteristic
CN101195901A (en) * 2007-12-06 2008-06-11 上海交通大学 Reaction spray coating metal ceramic composite powder and method for producing the same

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