CN102719783B - Preparation method forming protective film by alloy surface in-situ oxidation reaction - Google Patents

Preparation method forming protective film by alloy surface in-situ oxidation reaction Download PDF

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CN102719783B
CN102719783B CN2012101901966A CN201210190196A CN102719783B CN 102719783 B CN102719783 B CN 102719783B CN 2012101901966 A CN2012101901966 A CN 2012101901966A CN 201210190196 A CN201210190196 A CN 201210190196A CN 102719783 B CN102719783 B CN 102719783B
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temperature
oxidation
layer
furnace
preparation
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CN102719783A (en
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刘京雷
颜磊
徐宏
叶先勇
王志远
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East China University of Science and Technology
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Abstract

The invention relates to a preparation method forming a protective film by an alloy surface in-situ oxidation reaction by means of precision control. The compact and stable oxide protective film of a three-layer structure is formed on the surfaces of materials by means of control of oxygen partial pressure and oxidation temperature in an oxidation atmosphere, and comprises a MnxCr3-xO4 (0.5</=x</=1.5) spinel layer, a chromic oxidation layer and a silicon oxidation layer from outside to inside, wherein the spinel layer mainly plays a role in protection, the chromic oxidation layer can provide Cr oxides for self repair of the spinel layer, and the silicon oxidation layer serves as a protective layer and a diffusion barrier for elements among substrates. The protective film can effectively inhibit surface oxidation, carburization or coking of the materials in service, and the service life or decoking period of the materials is prolonged.

Description

A kind of alloy surface in-situ oxidation reaction forms the preparation method of protective membrane
[technical field]
The present invention relates to a kind of accurate control and prepare the preparation method that the reaction of alloy surface in-situ oxidation forms protective membrane; be suitable for the alloy containing high Cr and a certain amount of Mn, especially be applicable in nuclear reaction the nickel-based superalloy pipe in high-temperature gas cooling reactor flue (VHTR) and interchanger as Pintsch process boiler tube in Haynes230, ethylene unit as the metallic interconnect materials Fe-Cr-Mn alloy in HP40, solid fuel cell (SOFC) etc.
[background technology]
In high-temperature oxidation environment, alloy surface forms fine and close NiO, Cr 2O 3Oxide film and there is excellent high temperature oxidation resisting corrosive nature.As the nickel based super alloy of VHTR structured material, 1000 ℃ of its working temperatures, pressure 9MPa, reach 60 years life.Under the hot environment of VHTR, these materials are exposed to and contain CO, CO 2, H 2O, CH 4And H 2In nitrogen cooling gas Deng impurity, surface C r 2O 3Spalling of oxide layer, volatilization and higher atomic diffusion speed, make surface oxide layer can not well protect matrix, even worsens the performance of matrix.
Chromium base bearing alloy can form the protective membrane of chromated oxide, therefore is generally used for the metal connecting piece in solid fuel cell (SOFC).Cr in chromated oxide 2O 3O is being arranged 2Or H 2Under the condition that O exists, can produce gaseous state Cr oxide compound as CrO 3, this gaseous oxygen compound can be deposited on the electrode of fuel cell, causes the Efficiency Decreasing of battery.
The alloys such as HP40, HK40 and Incoloy800 are the materials that ethane cracking furnace is commonly used, and in the operational process of boiler tube, the coking of its internal surface and carburizing cause serious consequence, as increased energy consumption, reduce productive rate, shorten that the boiler tube life-span even lost efficacy etc.In the cracking of ethylene process, Cr 2O 3Protective membrane easily reacts the carbide Cr that generates fragility with carbon xC yAt H 2O and O 2In the common hot environment existed, easily generate the CrO of gaseous state 2(OH) 2, cause the destruction of protective membrane and lose the protection effect.
Therefore prepare a kind of Performance Ratio Cr in the urgent need to the surface at high-chromium alloy 2O 3Better protective membrane, improve material in performances such as anti-oxidant, the impervious carbon as under above-mentioned severe condition and anti-cokings.Take ethylene cracking tube as example, and the coke of boiler tube internal surface, mainly come from catalysis Jiao that in cracked gas and furnace tube material, the catalytic ionic reactions such as Fe, Ni form.The method of preparation table surface protective film mainly is divided into two classes at present: the first kind is the coat preparing technology of offing normal.By chromated oxide, aluminum oxide, or wherein one or more such as brick oxide compound, by vapour deposition, sintering, or bury the method for oozing, form protective membrane at internal surface, to avoid catalysis Jiao's formation.But this type of protective membrane is thicker, with the coefficient of expansion of matrix, very large difference is arranged, so heat-shock resistance is poor, easily peels off.Equations of The Second Kind is the original position coat preparing technology; at a certain temperature; the boiler tube internal surface passes into certain atmosphere; make the nearly upper layer of boiler tube that optionally oxidation occur and generate the protective membrane of excellent performance; the composition through-thickness of this type of protective membrane changes continuously; be similar to gradient material, therefore high with basic bonding force, heat-shock resistance is strong.
In patent US7156979, NOVA company adopts hydrogen and water vapor mixture atmosphere, in 800-1100 ℃, at stainless steel surface, prepares one deck Mn xCr 3-xO 4(0.5≤x≤1.5) spinel structure protective membrane; In patent US6899966, the protective membrane of preparing is mainly Mn xCr 3-xO 4Spinel, separately contain MnO, MnSiO 3And MnSi 2O 4The mixture of one or more, not containing or containing the Cr oxide compound of minute quantity.
In Chinese patent CN101565807A, CN101565808A, adopt H 2, CO, N 2Deng, introduce a certain amount of water vapour by water or ammonia soln.600-1000 ℃ of insulation 5～80 hours, on the boiler tube surface, prepare Mn xCr 3-xO 4Spinel layer (0.5≤x≤1.5).
Adopt the standby oxide film of above-mentioned patent system to play certain provide protection to matrix, but still there is following deficiency:
(1) high oxidizing temperature is unfavorable for Mn xCr 3-xO 4The growth of spinel.In above-mentioned patent, the directly rise to>=a certain temperature of 600 ℃ of material is carried out oxidation, from the kinetics of reaction process, is unfavorable for particularly Mn of surface film oxide xCr 3-xO 4The generation of spinel.From thermodynamics, under low oxygen partial pressure, the generation of oxide compound is mainly by O 2-Perhaps OH -Deng negatively charged ion by the external world along crystal boundary to inner diffusion control.When temperature during higher than 600～800 ℃, Mn xCr 3-xO 4Spinel occurs, negatively charged ion spread coefficient therein is lower than the spread coefficient in matrix, Mn oxide compound and Cr oxide compound, therefore fine and close spinel layer can hinder the continuation diffusion of Sauerstoffatom, and then hinders the continued growth of spinel layer, oxidization time that therefore need to be very long.
(2) above-mentioned patent is the single zone of oxidation that has formed the poor Fe of rich Cr, Mn, Ni on surface.This protective membrane in the hot operation process, due to the existence of concentration difference, the element generation phase mutual diffusion in oxide film and matrix, the protective membrane attenuation, even lost efficacy.
(3) work as Mn xCr 3-xO 4After the spinel oxide film is destroyed, can not selfreparing, be difficult to form new Mn xCr 3-xO 4Spinel.
(4) adjusting of the related oxygen partial pressure of above-mentioned patent, can only regulate by the temperature of water or ammoniacal liquor, so its application has certain limitation.
[summary of the invention]
The object of the invention is to overcome the deficiencies in the prior art, provide a kind of alloy surface in-situ oxidation reaction to form the preparation method of protective membrane; Present technique, by controlling oxygen partial pressure and the oxidizing temperature in oxidizing atmosphere, is accurately controlled the in-situ oxidation of alloy surface, forms the three-layer composite structure of oxide compound at alloy surface, obviously improves anti-oxidant, impervious carbon and anti-coking performance.
The objective of the invention is to be achieved through the following technical solutions:
A kind of alloy surface in-situ oxidation reaction forms the preparation method of protective membrane, and its concrete steps are:
(1) alloy material or tube surfaces are done to the degreasing and rust removal pre-treatment, in the heat treatment furnace of then packing into;
Described alloy material is the alloy containing Cr and Mn, as nickel-based superalloy, HP, HK and Incoloy series alloy and stainless steel commonly used etc.By percentage to the quality, Cr5～30%, Mn0.2～5%, Si0.2～4%, Ni0.01～50%, trace element 0.01～5%, surplus is Fe; Trace element comprises one or more in Nb, Ti, V, W, Al, C etc.;
(2) gas is passed through to electrolyte solution, adopt Bubbling method to introduce water vapour, the electrolyte solution temperature is controlled by thermostatical water bath; Gaseous tension is controlled at 1～5 normal atmosphere.Then gas is passed in the process furnace that alloy material or tubing are housed;
Described gas is selected from one or more in hydrogen, nitrogen, helium, argon gas, ammonia, carbon monoxide etc.;
Solute in described electrolyte solution is mainly salt or bases, as NaCl, NH 4Cl, K 2SO 4, NaH 2PO 4, NaOH, CH 3COOK, MgCl 2Deng; The temperature of solution is controlled by temperature controller, can be freezing point of solution to boiling point, and concentration is 0 saturation concentration to corresponding temperature; By the parameters such as concentration, solute species and temperature of regulating above-mentioned solution, can be in a big way the content of water vapour in adjustments of gas, control the oxygen partial pressure in oxidizing atmosphere; For example 20 ℃ the time, adopt K 2SO 4The water vapour content that the aqueous solution is introduced can reach and adopt CH 34 times of COOK aqueous solution introduction volume;
(3) furnace temperature is risen to 300～600 ℃ and carry out low-temperature oxidation, preferably 350～550 ℃, 5～20 ℃/min of temperature rise rate, be incubated 2～50h after reaching preset temperature, preferably 5～10h;
(4) furnace temperature is risen to 700～1200 ℃ and carry out high temperature oxidation, preferably 800～1100 ℃, 10～30 ℃/min of temperature rise rate, be incubated 1～20h after reaching preset temperature, preferably 2～5h;
(5) cool to room temperature with the furnace or, below 150 ℃, close gas, film is protected.
In the present invention, 300～600 ℃ of low-temperature oxidation stages, the oxygen concn controlled range is wider, improves the concentration of oxygen and can accelerate alloy surface SiO 2, MnO, Cr 2O 3The formation of oxidation products; 700～1200 ℃ of high temperature oxidation stages, MnO, the Cr that form early stage 2O 3Generate MnCr by solid state reaction 2O 4Spinel layer is positioned at outermost layer; Superfluous Cr 2O 3As repair layer, mediate; The SiO of innermost layer 2As the diffusion barrier layer.
Alloy surface of the present invention has the three-decker oxide film formed by the in-situ oxidation method, and protective membrane is by outer and respectively interior: spinel layer, main component is Mn xCr 3-xO 4(0.5≤x≤1.5); The selfreparing layer of compensation, main component is Cr 2O 3The diffusion barrier layer, main component is SiO 2.
Compared with prior art, positively effect of the present invention is:
Use the present invention, can effectively control the carrying out of alloy surface oxidizing reaction, formed oxide film is three-layer composite structure, by being respectively in outer reaching: MnCr 2O 4The spinel protective layer, Cr 2O 3Repair layer and SiO 2The diffusion barrier layer.This composite structure makes protective membrane have certain self-reparing capability.Compare single layer structure, this three-decker makes the performance of protective membrane be further enhanced, as the bonding force of oxide film and matrix, and the heat-shock resistance of protective membrane, outermost MnCr 2O 4The compactness of spinel and the life-span of protective membrane etc.The method easy handling also can operate in simple equipment, with low cost.
[accompanying drawing explanation]
Fig. 1 oxidation products XRD diffraction analysis; (a) the common diffractogram of grazing-incidence diffraction figure (b);
Fig. 2 oxidation products cross section; (a) cross section SEM figure (b) Si unit vegetarian noodles scanning;
Fig. 3 oxidation products EDS ultimate analysis; (a) after low-temperature oxidation is processed rear (b) high temperature oxidation process.
[embodiment]
Below provide a kind of alloy surface in-situ oxidation reaction of the present invention to form the preparation method's of protective membrane embodiment.
Embodiment 1
Example has prepared the oxidation products protective membrane with three-decker at the HP40 alloy surface.
After the HP40 alloy material is adopted to alkali cleaning, pickling and the rust cleaning of neutralizing treatment surface degreasing, be placed in the tubular type heat treatment furnace, hydrogen is as protective atmosphere, and gas flow rate is made as 50ml/min, first passes into K 2SO 4In saturated aqueous solution, solution temperature is 20 ℃.Rear gas causes in heat treatment furnace.Heat treatment furnace is warming up to 500 ℃ with 20 ℃/min speed, is incubated 8 hours, and then be heated to 1000 ℃, be incubated 4 hours.After insulation finishes, cooling with stove, close gas after 150 ℃.
After oxide treatment, specimen surface forms the oxide film of three-decker, by outer and respectively interior: MnCr 2O 4The spinel protective layer, Cr 2O 3Repair layer and SiO 2The diffusion barrier layer.
Take the HP40 material as example, and the XRD analysis of the oxide on surface protective membrane that adopts this patent to prepare as shown in Figure 1.Fig. 1 (a) is grazing-incidence diffraction figure, and Fig. 1 (b) is common XRD diffractogram.Fig. 1 (a) shows that the outermost layer of oxide film is single MnCr 2O 4Spinel oxide.Because the XRD detection is darker, characterized oxidation products except MnCr in Fig. 1 (b) 2O 4Also has Cr than depths outward, 2O 3.The element distribution analysis figure that Fig. 2 is the oxidation products cross section.Characterized the most inboard near the oxidation products of matrix in figure, due to SiO 2The existence of layer, have higher Si enrichment.Fig. 3 shows the difference of the element of the detectable product of different oxidation stage EDS.After the low-temperature in-site oxidation, Fig. 3 (a) shows that the matrix principal elements such as Fe, Cr, Ni are not only arranged in oxidation products, the enrichment of Si, Mn element also occurred.After further high-temp in-situ oxidation, Fig. 3 (b) shows, the top layer oxidation products only has Cr, Mn element.Generating MnCr 2O 4In the time of the spinel protective layer, also effectively suppressed coking is played to the Fe, Ni element of katalysis in surperficial appearance.
When this protective membrane can suppress material military service effectively, surface oxidation, carburizing or coking, increase the service life or coke cleaning period.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.

Claims (3)

1. the preparation method of an alloy surface in-situ oxidation reaction formation protective membrane, is characterized in that, concrete steps are:
(1) alloy material surface is done to the degreasing and rust removal pre-treatment, in the heat treatment furnace of then packing into;
Described alloy material is the alloy containing Cr and Mn, by percentage to the quality, Cr5～30%, Mn0.2～5%, Si0.2～4%, Ni0.01～50%, trace element 0.01～5%, surplus is Fe; Trace element comprises one or more in Nb, Ti, V, W, Al, C;
(2) gas is passed through to electrolyte solution, adopt Bubbling method to introduce water vapour, the electrolyte solution temperature is controlled by thermostatical water bath; Gaseous tension is controlled at 1～5 normal atmosphere; Then gas is passed in the process furnace that alloy material or tubing are housed;
Described gas is selected from one or more in hydrogen, nitrogen, helium, argon gas, ammonia, carbon monoxide;
Solute in described electrolyte solution is NaCl, NH 4Cl, K 2SO 4, NaH 2PO 4, NaOH, CH 3COOK, MgCl 2
(3) furnace temperature is risen to 300～600 ℃ and carry out low-temperature oxidation, 5～20 ℃/min of temperature rise rate, be incubated 2～50h after reaching preset temperature;
(4) furnace temperature is risen to 700～1200 ℃ and carry out high temperature oxidation, 10～30 ℃/min of temperature rise rate, be incubated 1～20h after reaching preset temperature;
(5) cool to room temperature with the furnace or, below 150 ℃, close gas, film is protected.
2. a kind of alloy surface in-situ oxidation reaction as claimed in claim 1 forms the preparation method of protective membrane; it is characterized in that, in described step (3), furnace temperature is risen to 350～550 ℃ and carry out low-temperature oxidation; 5～20 ℃/min of temperature rise rate, be incubated 5～10h after reaching preset temperature.
3. a kind of alloy surface in-situ oxidation reaction as claimed in claim 1 forms the preparation method of protective membrane; it is characterized in that, in described step (4), furnace temperature is risen to 800～1100 ℃ and carry out high temperature oxidation; 10～30 ℃/min of temperature rise rate, be incubated 2～5h after reaching preset temperature.
CN2012101901966A 2012-06-11 2012-06-11 Preparation method forming protective film by alloy surface in-situ oxidation reaction Expired - Fee Related CN102719783B (en)

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CN103993306A (en) * 2014-05-13 2014-08-20 陕西省石油化工研究设计院 Preparation method for in-situ growth metallic oxide film through flowing oxidation
CN106554800B (en) * 2015-09-29 2019-02-19 中国石油化工股份有限公司 A kind of processing method of pyrolysis furnace nichrome boiler tube
CN106011743B (en) * 2016-06-24 2018-03-13 华东理工大学 A kind of preparation method of alloy material surface manganese chromium ceramic coating
CN106835110B (en) * 2017-01-23 2018-12-25 海南省环境科学研究院 A kind of environment-friendly type antiradar reflectivity membrane material and preparation method thereof
WO2018181348A1 (en) * 2017-03-27 2018-10-04 新日鐵住金株式会社 Stainless steel material, constituent member, cell, and fuel cell stack
WO2019222950A1 (en) 2018-05-24 2019-11-28 GM Global Technology Operations LLC A method for improving both strength and ductility of a press-hardening steel
CN112534078A (en) 2018-06-19 2021-03-19 通用汽车环球科技运作有限责任公司 Low density press hardened steel with enhanced mechanical properties
CN109451605B (en) * 2018-10-29 2021-03-16 温州科博达汽车部件有限公司 Surface treatment method for electric heating belt of preheater
EP3898896A1 (en) * 2018-12-20 2021-10-27 ExxonMobil Chemical Patents Inc. Erosion resistant alloy for thermal cracking reactors
US11530469B2 (en) 2019-07-02 2022-12-20 GM Global Technology Operations LLC Press hardened steel with surface layered homogenous oxide after hot forming

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