CN101994077A - High-temperature oxidation resisting intermetallic compound coating and preparation method thereof - Google Patents
High-temperature oxidation resisting intermetallic compound coating and preparation method thereof Download PDFInfo
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- CN101994077A CN101994077A CN2010105207359A CN201010520735A CN101994077A CN 101994077 A CN101994077 A CN 101994077A CN 2010105207359 A CN2010105207359 A CN 2010105207359A CN 201010520735 A CN201010520735 A CN 201010520735A CN 101994077 A CN101994077 A CN 101994077A
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Abstract
The invention discloses a high-temperature oxidation resisting intermetallic compound coating and a preparation method thereof. A microcrystal intermetallic compound coating with metallurgical bonding is arranged on a metallic matrix, wherein the crystallite dimension of microcrystal is 0.1-10mu m, the thickness of the coating is not more than 150mu m, and the coating material is a Ti-Al series, an Ni-Al series and an Fe-Al series intermetallic compounds. The coating is prepared by adopting a high-energy differential arc alloying technology and has the parameters that the output power is 50-2000W, the voltage is 40-100V, the frequency is not more than 2000Hz and the preparation is not more than 30min/cm<2>. The preparation environment of the coating is protected by non-reactive gases at room temperature, such as nitrogen, argon and the like. The intermetallic compound coating prepared by using the method can not only maintain high-temperature mechanical property of the metallic matrix, but also greatly improves the high-temperature oxidization property.
Description
Technical field
The present invention relates to the intermetallic compound coating field, more particularly, relate to a kind of high temperature oxidation resisting intermetallic compound coating and preparation method thereof.
Background technology
Progress along with science and technology development and production technology, the running of processing units, machining energy, production efficiency and automatization level improve day by day, product military service performance demands is also more and more stricter, the particularly requirement of the corrosion resisting property of high-temperature component, and only depend on the performance that improves substrate alloy to be difficult to satisfy service requirements sometimes.In addition, common superalloy must satisfy the requirement of two aspects simultaneously: excellent mechanical behavior under high temperature and elevated temperature corrosion resistant.Al and Cr are important resistance to high temperature corrosion elements, but in high-intensity alloy, will generate the deleterious phase of mechanical property if Cr content is too high, and the too high alloy plasticity that will make of Al content descends, and processing characteristics worsens.Solve the contradiction between alloy high-temp mechanical property and the corrosive nature, a kind of valid approach applies protective coating at alloy surface exactly.
The preparation method of coating is a lot, as diffusion coating Al, CVD or PVD, plating, thermospray, sputter etc.Diffusion coating Al is a coating preparation mode commonly used, but its working temperature is higher, and oxidation can take place material; Combine poorly between the coating of CVD or PVD technology preparation and matrix, and the EB-PVD(electro beam physics vapour deposition) though coating adhesion is strong, few to coating contamination, equipment complexity, coating production cost height.When coated component complexity or fusing point were higher, sputtering method prepares coating obvious superiority, but this kind mode sedimentation effect is low, and cost is higher.The spraying of early stage atmospheric plasma, the coating porosity height, bonding force is poor, develops into the low-voltage vacuum plasma spraying afterwards, coating sedimentation effect height, improved performance, but this makes the equipment complexity, the coating preparation cost improves.
Coat preparing technology with low cost, easy to operate, excellent property comes into one's own always.High energy differential of the arc alloying process (HEMAA) is a kind of metal material surface treatment process simple and easy to do, with low cost, can form high rigidity, wear-resisting, strengthening layer at alloy surface with specific physical, chemical property, and be metallurgical binding between coating and the base material, very little in the coating preparation to the base material heat affected zone.And HEMAA can prepare crystallite or nanocrystalline coating, and the refinement of crystal grain helps the selective oxidation of element, increases the resistance to high temperature corrosion performance of coating.
Intermetallic compound has many good performances, comprises high-melting-point, high resistance to high temperature corrosion performance, higher high temperature strength and creep resistance and high specific tenacity, and has the positive temperature effect of peak temperature with lower yield strength.But room temperature fragility is still its major obstacle as practical high-temperature structural material.Intermetallic compound as coating material, then can be avoided the machine-shaping to the bad intermetallic compound of toughness, give full play to the performance advantage of intermetallic compound, improve the military service performance on base metals surface.
Summary of the invention
Mechanical behavior under high temperature and high temperature oxidation resistance in order to satisfy the material excellence simultaneously the invention provides a kind of high temperature oxidation resisting intermetallic compound coating and preparation method thereof.
Technical scheme of the present invention is: a kind of high temperature oxidation resisting intermetallic compound coating, on metallic matrix, be provided with crystallite intermetallic compound coating with metallurgical binding, the grain-size of crystallite is 0.1 ~ 10 μ m, the thickness of coating is≤150 μ m, and described coated material is Ti-Al system, Ni-Al system, Fe-Al series intermetallic compound.
Described metallic matrix is any one in common stainless material, superalloy, the intermetallic compound.
The method for preparing described high temperature oxidation resisting intermetallic compound coating; in the nonreactive gas protection; under the room temperature; use high energy differential of the arc alloying process and prepare intermetallic compound coating at the metal base surface of cleaning; the parameter area of preparation is: output rating is 50 ~ 2000W; output voltage is 40 ~ 100V, and output frequency is≤2000Hz preparation time≤30min/cm
2Coated material is Ti-Al system, Ni-Al system, Fe-Al series intermetallic compound.
The parameter area of the high energy differential of the arc alloying process preparation of being adopted is preferably: output rating is 900 ~ 2000W, and output voltage is 60 ~ 80V, and output frequency is 1000 ~ 2000Hz, and preparation time is 2 ~ 7min/cm
2
Preferred scheme is: before end, output voltage is adjusted into 40 ~ 60V, and then inswept whole coatingsurface once.
Described non-reactive gas is nitrogen or argon gas.
Beneficial effect:
1, the present invention adopts high energy differential of the arc alloying process to prepare the intermetallic compound coating of high temperature oxidation resisting at metal base surface, and resulting coating and metallic matrix belong to metallurgical binding.Coating is when carrying out the high temperature oxidation experiment for 900 ℃ and 1000 ℃, oxide film cracking and peeling phenomenon can appear as compound between the former as cast metal of coated material, and be prepared into after the coating, its oxidation rate constant can reduce an order of magnitude, last all can form continuously fine and close, good adhesion and than the Al that approaches
2O
3Film, this layer oxide film has extraordinary stability and protectiveness, behind experiment 600h, any defective do not occur and thickens phenomenon.This shows the intermetallic compound coating that the present invention prepares, and not only can keep the mechanical behavior under high temperature of matrix metal, and high temperature oxidation resistance improves greatly.
2, technology of the present invention is simple, processing cost is cheap.
Description of drawings
Fig. 1 is Fe
3Al is coated with the layer cross section metallograph.
Fig. 2 is Fe
3The Al coating is 900
oOxidation 200h cross section scanning electron microscope pattern in the C air.
Fig. 3 is Ni
3Al is coated with the layer cross section metallograph
Fig. 4 is Ni
3The Al coating is 1000
oOxidation 200h cross section scanning electron microscope pattern magnification is 5 μ m in the C air.
Fig. 5 is Ni
3The Al coating is 1000
oOxidation 200h cross section scanning electron microscope pattern magnification is 20 μ m in the C air.
Embodiment
A kind of high temperature oxidation resisting intermetallic compound coating is provided with the crystallite intermetallic compound coating with metallurgical binding on metallic matrix, the grain-size of crystallite is 0.1 ~ 10 μ m, and the thickness of coating is≤150 μ m; Described coated material is Ti-Al system, Ni-Al system, Fe-Al series intermetallic compound.
Described metallic matrix is common stainless material as 304,316,310 etc., in superalloy such as K3 steel, intermetallic compound such as Ti-Al system, Ni-Al system, the Fe-Al system any one.
The method for preparing described high temperature oxidation resisting intermetallic compound coating; in the nonreactive gas protection; under the room temperature; use high energy differential of the arc alloying process and prepare intermetallic compound coating at the metal base surface of cleaning; the parameter area of preparation is: output rating is 50 ~ 2000W; output voltage is 40 ~ 100V, and output frequency is≤2000Hz preparation time≤30min/cm
2Coated material is Ti-Al system, Ni-Al system, Fe-Al series intermetallic compound.
The parameter area of the high energy differential of the arc alloying process preparation of being adopted is preferably: output rating is 900 ~ 2000W, and output voltage is 60 ~ 80V, and output frequency is 1000 ~ 2000Hz, and preparation time is 2 ~ 7min/cm
2
Preferred scheme is: before end, output voltage is adjusted into 40 ~ 60V, and then inswept whole coatingsurface once.
Described non-reactive gas is nitrogen or argon gas.
The preparation method of described high temperature oxidation resisting intermetallic compound coating, step is more specifically:
The first step: metallic matrix carry out pre-treatment in the usual way.Metallic matrix can select stainless material as 304,316,310 etc., or superalloy such as K3 steel, also can be intermetallic compound such as Ti-Al system, Ni-Al system, Fe-Al system etc., selects to get final product according to employed environment needs.Metallic matrix polishes off outer oxide layer in advance, adopts the silicon carbide paper polishing to 0 ~ 2000#, preferred 1000 ~ 2000#, and the clean metal matrix can adopt dehydrated alcohol or acetone to clean then, preferred acetone.It is stand-by to obtain clean metallic matrix after drying.
Second step: the preparing in the usual way and handling of coated material.It is any one intermetallic compound that coated material can be selected Ti-Al system, Ni-Al system, Fe-Al, cuts into the pole that diameter is 3 ~ 5mm, and sand papering acetone clean surface.
The 3rd step: the preparation of intermetallic compound coating.Use high energy differential of the arc alloying process (HEMAA) and prepare intermetallic compound coating at metal base surface.The equipment output rating is 50 ~ 2000W, preferred 900 ~ 2000W; Output voltage is 40 ~ 100V, preferred 60 ~ 80V; Output frequency is≤2000Hz preferred 1000 ~ 2000Hz; Preparation time≤30min/cm
2, preferred 2-7 min/cm
2In order to make the coating deposited surface Paint Gloss, under the constant condition of other processing parameter, voltage is transferred to 40 ~ 60V, inswept whole coatingsurface at last.Different according to selected coated material and preparation parameter, the gained coated grains is of a size of 0.1 ~ 10 μ m, and the thickness of coating is≤150 μ m, preferred 20 ~ 100 μ m.Feed the non-reactive gas protection in preparation process, non-reactive gas is nitrogen or argon gas, is preferably argon gas.Preparation temperature is a room temperature.
Embodiment 1
Metallic matrix is selected 304 stainless materials, and polishing also adopts silicon carbide paper to polish to 2000#, cleans with dehydrated alcohol then.Coated material is selected Fe
3The Al intermetallic compound cuts into the pole that diameter is 4mm, and sand papering acetone clean surface.Use high energy differential of the arc alloying process and prepare intermetallic compound coating at metal base surface.Used parameter is: equipment output rating 2000W; Output voltage is 80V, and output frequency is 2000Hz, preparation time 7 min/cm
2, at room temperature feed argon shield.In order to make the coating deposited surface Paint Gloss, under the constant condition of other processing parameter, voltage is transferred to 60V, inswept whole coatingsurface at last.The coated grains size is about 15 μ m, and coat-thickness is about 75 μ m, fine and close zero defect, and belong to metallurgical binding between matrix.
The gained coating is carried out high temperature oxidation experiment, no matter 900 ℃ still 1000 ℃, all can generate the good Al of densification and protectiveness
2O
3Film has good mechanical behavior under high temperature and high temperature oxidation resistance.
Embodiment 2
Metallic matrix is selected the K3 superalloy, and polishing also adopts silicon carbide paper to polish to 800#, cleans with dehydrated alcohol then.Coated material is selected Ni
3The Al intermetallic compound cuts into the pole that diameter is 3.5mm, and sand papering acetone clean surface.Use high energy differential of the arc alloying process and prepare intermetallic compound coating at metal base surface.Used parameter is: equipment output rating 1500W; Output voltage is 100V, and output frequency is 1000Hz, preparation time 20 min/cm
2, at room temperature feed nitrogen protection.In order to make the coating deposited surface Paint Gloss, under the constant condition of other processing parameter, voltage is transferred to 40V, inswept whole coatingsurface at last.The coated grains size is about 0.5 μ m, and coat-thickness is about 120 μ m, omits defectiveness, and belongs to metallurgical binding between matrix.
The gained coating is carried out high temperature oxidation experiment, no matter 900 ℃ and 1000 ℃, all can generate successional Al
2O
3Film, oxide film are slightly thick, have good mechanical behavior under high temperature and high temperature oxidation resistance preferably.
Embodiment 3
Metallic matrix is selected the NiAl intermetallic compound, and polishing also adopts silicon carbide paper to polish to 100#, cleans with acetone then.Coated material is also selected the NiAl intermetallic compound, cuts into the pole that diameter is 3mm, and sand papering is also used the acetone clean surface.Use high energy differential of the arc alloying process and prepare intermetallic compound coating at metal base surface.Used parameter is: equipment output rating 2000W; Output voltage is 80V, and output frequency is 1500Hz, preparation time 2min/cm
2, at room temperature feed argon shield.In order to make the coating deposited surface Paint Gloss, under the constant condition of other processing parameter, voltage is transferred to 60V, inswept whole coatingsurface at last.The coated grains size is about 0.1 μ m, and coat-thickness is about 25 μ m, fine and close zero defect, and belong to metallurgical binding between matrix.
The gained coating is carried out high temperature oxidation experiment, no matter 900 ℃ and 1000 ℃, all can generate the good Al of densification and protectiveness
2O
3Film has good mechanical behavior under high temperature and high temperature oxidation resistance.
Embodiment 4
Metallic matrix is selected Ti
3The Al intermetallic compound, polishing also adopts silicon carbide paper to polish to 600#, cleans with acetone then.Coated material is selected Fe
3The Al intermetallic compound cuts into the pole that diameter is 5mm, and sand papering acetone clean surface.Use high energy differential of the arc alloying process and prepare intermetallic compound coating at metal base surface.Used parameter is: equipment output rating 1000W; Output voltage is 40V, and output frequency is 200Hz, preparation time 30min/cm
2, at room temperature feed argon shield.The coated grains size is about 10 μ m, and coat-thickness is about 50 μ m, fine and close zero defect, and belong to metallurgical binding between matrix.
The gained coating is carried out high temperature oxidation experiment, no matter 900 ℃ and 1000 ℃, all can generate the good Al of densification and protectiveness
2O
3Film has good mechanical behavior under high temperature and high temperature oxidation resistance.
Embodiment 5
Metallic matrix is selected 310 stainless materials, and polishing also adopts silicon carbide paper to polish to 50#, cleans with dehydrated alcohol then.Coated material is selected Ti
3The Al intermetallic compound cuts into the pole that diameter is 4mm, and sand papering acetone clean surface.Use high energy differential of the arc alloying process and prepare intermetallic compound coating at metal base surface.Used parameter is: equipment output rating 2000W; Output voltage is 60V, and output frequency is 2000Hz, preparation time 5 min/cm
2, at room temperature feed argon shield.The coated grains size is about 0.4 μ m, and coat-thickness is about 45 μ m, fine and close zero defect, and belong to metallurgical binding between matrix.
The gained coating is carried out high temperature oxidation experiment, no matter 900 ℃ and 1000 ℃, all can generate the good Al of densification and protectiveness
2O
3Film has good mechanical behavior under high temperature and high temperature oxidation resistance.
Embodiment 6
Metallic matrix is selected the K3 superalloy, and polishing also adopts silicon carbide paper to polish to 200#, cleans with acetone then.Coated material is selected the FeAl intermetallic compound, cuts into the pole that diameter is 3.5mm, and sand papering acetone clean surface.Use high energy differential of the arc alloying process and prepare intermetallic compound coating at metal base surface.Used parameter is: equipment output rating 500W; Output voltage is 80V, and output frequency is 500Hz, preparation time 4 min/cm
2, at room temperature feed argon shield.In order to make the coating deposited surface Paint Gloss, under the constant condition of other processing parameter, voltage is transferred to 40V, inswept whole coatingsurface at last.The coated grains size is about 4 μ m, and coat-thickness is about 30 μ m, omits defectiveness, and belongs to metallurgical binding between matrix.
The gained coating is carried out high temperature oxidation experiment, no matter 900 ℃ and 1000 ℃, all can generate densification but slightly thick Al
2O
3Film has good mechanical behavior under high temperature and high temperature oxidation resistance.
Embodiment 7
Metallic matrix is selected 310 stainless materials, and polishing also adopts silicon carbide paper to polish to 1200#, cleans with dehydrated alcohol then.Coated material is selected the TiAl intermetallic compound, cuts into the pole that diameter is 4mm, and sand papering acetone clean surface.Use high energy differential of the arc alloying process and prepare intermetallic compound coating at metal base surface.Used parameter is: equipment output rating 1600W; Output voltage is 80V, and output frequency is 1000Hz, preparation time 9min/cm
2, at room temperature feed nitrogen protection.In order to make the coating deposited surface Paint Gloss, under the constant condition of other processing parameter, voltage is transferred to 60V, inswept whole coatingsurface at last.The coated grains size is about 0.1 μ m, and coat-thickness is about 55 μ m, fine and close zero defect, and belong to metallurgical binding between matrix.
The gained coating is carried out high temperature oxidation experiment, no matter 900 ℃ and 1000 ℃, all can generate the good Al of densification and protectiveness
2O
3Film has good mechanical behavior under high temperature and high temperature oxidation resistance.
Claims (6)
1. a high temperature oxidation resisting intermetallic compound coating is characterized in that, is provided with the crystallite intermetallic compound coating with metallurgical binding on metallic matrix, and the grain-size of crystallite is 0.1 ~ 10 μ m, and the thickness of coating is≤150 μ m; Described coated material is Ti-Al system, Ni-Al system, Fe-Al series intermetallic compound.
2. high temperature oxidation resisting intermetallic compound coating as claimed in claim 1 is characterized in that, described metallic matrix is any one in common stainless material, superalloy, the intermetallic compound.
3. the method for preparing the described high temperature oxidation resisting intermetallic compound coating of claim 1; it is characterized in that; in the nonreactive gas protection; under the room temperature; use high energy differential of the arc alloying process and prepare intermetallic compound coating at the metal base surface of cleaning, the parameter area of preparation is: output rating is 50 ~ 2000W, and output voltage is 40 ~ 100V; output frequency is≤2000Hz preparation time≤30min/cm
2Coated material is Ti-Al system, Ni-Al system, Fe-Al series intermetallic compound.
4. the method for preparing the high temperature oxidation resisting intermetallic compound coating as claimed in claim 3, it is characterized in that, the parameter area of described high energy differential of the arc alloying process preparation is: output rating is 900 ~ 2000W, output voltage is 60 ~ 80V, output frequency is 1000 ~ 2000Hz, and preparation time is 2 ~ 7min/cm
2
5. as claim 3 or the 4 described methods that prepare the high temperature oxidation resisting intermetallic compound coating, it is characterized in that, before end, output voltage is adjusted into 40 ~ 60V, and then inswept whole coatingsurface once.
6. the method for preparing the high temperature oxidation resisting intermetallic compound coating as claimed in claim 3 is characterized in that, described non-reactive gas is nitrogen or argon gas.
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| CN102534604A (en) * | 2012-02-09 | 2012-07-04 | 常州大学 | Method for prolonging service life of piercing plug for seamless steel tubes |
| CN102634790A (en) * | 2012-05-03 | 2012-08-15 | 华北电力大学 | Fe-Ti and Fe-Al complex-phase intermetallic compound anti-corrosion layer and preparation method thereof |
| CN103233219A (en) * | 2013-03-22 | 2013-08-07 | 常州大学 | Metal TiN ceramic coating preparation process method |
| CN103255365A (en) * | 2013-05-22 | 2013-08-21 | 北京工业大学 | Corrosion and wear resistant coating for magnesium alloy surface and preparation method of corrosion and wear resistant coating |
| CN105821459A (en) * | 2016-03-29 | 2016-08-03 | 常州大学 | Method for preparing boride coating on stainless steel surface |
| CN106282887A (en) * | 2015-05-26 | 2017-01-04 | 中国科学院金属研究所 | The in-situ preparation method of the dispersed particle-strengthened alloy coat of oxide crystallite |
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| CN102534604B (en) * | 2012-02-09 | 2014-04-09 | 常州大学 | Method for prolonging service life of piercing plug for seamless steel tubes |
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| CN103233219B (en) * | 2013-03-22 | 2015-06-03 | 常州大学 | Metal TiN ceramic coating preparation process method |
| CN103233219A (en) * | 2013-03-22 | 2013-08-07 | 常州大学 | Metal TiN ceramic coating preparation process method |
| CN103255365B (en) * | 2013-05-22 | 2016-01-20 | 北京工业大学 | A kind of Mg alloy surface corrosion-proof wear coating and preparation method thereof |
| CN103255365A (en) * | 2013-05-22 | 2013-08-21 | 北京工业大学 | Corrosion and wear resistant coating for magnesium alloy surface and preparation method of corrosion and wear resistant coating |
| CN106282887A (en) * | 2015-05-26 | 2017-01-04 | 中国科学院金属研究所 | The in-situ preparation method of the dispersed particle-strengthened alloy coat of oxide crystallite |
| CN106282887B (en) * | 2015-05-26 | 2018-12-21 | 中国科学院金属研究所 | The in-situ preparation method of the dispersed particle-strengthened alloy coat of oxide crystallite |
| CN105821459A (en) * | 2016-03-29 | 2016-08-03 | 常州大学 | Method for preparing boride coating on stainless steel surface |
| CN105821459B (en) * | 2016-03-29 | 2018-06-26 | 常州大学 | A kind of method for preparing boride coating in stainless steel surface |
| CN108866536A (en) * | 2018-06-26 | 2018-11-23 | 新余学院 | A kind of nanometer crystalline Ni Al/Ni of fabricated in situ3The preparation method of compound coat between Al bimetallic |
| CN108866536B (en) * | 2018-06-26 | 2020-06-16 | 新余学院 | In-situ synthesized nanocrystalline NiAl/Ni3Preparation method of Al bimetal compound coating |
| CN109128199A (en) * | 2018-11-14 | 2019-01-04 | 广东石油化工学院 | A kind of electrode being used to prepare intermetallic Fe-Al compound coating and method |
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Open date: 20110330 |