CN103302235B - A kind of method of cast(ing) surface reactive cladding alumina base coating - Google Patents
A kind of method of cast(ing) surface reactive cladding alumina base coating Download PDFInfo
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- CN103302235B CN103302235B CN201310240215.6A CN201310240215A CN103302235B CN 103302235 B CN103302235 B CN 103302235B CN 201310240215 A CN201310240215 A CN 201310240215A CN 103302235 B CN103302235 B CN 103302235B
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- powder
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- coated
- cladding
- alumina base
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- 239000011248 coating agent Substances 0.000 title claims abstract description 43
- 238000000576 coating method Methods 0.000 title claims abstract description 43
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000005253 cladding Methods 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 230000000704 physical effect Effects 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000011812 mixed powder Substances 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000004576 sand Substances 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000905 alloy phase Inorganic materials 0.000 claims description 4
- 229940067573 brown iron oxide Drugs 0.000 claims description 4
- 238000005187 foaming Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- 230000009970 fire resistant effect Effects 0.000 claims description 2
- 230000006698 induction Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000002345 surface coating layer Substances 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 1
- 229910000480 nickel oxide Inorganic materials 0.000 claims 1
- 238000005266 casting Methods 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 2
- 229940068984 polyvinyl alcohol Drugs 0.000 abstract 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000005524 ceramic coating Methods 0.000 description 3
- 244000035744 Hura crepitans Species 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Other Surface Treatments For Metallic Materials (AREA)
- Mold Materials And Core Materials (AREA)
Abstract
Reactive cladding prepares a method for alumina base coating, belongs to metal-base composites preparing technical field.First coated powder is configured, wherein containing self-propagating reaction system powder and metal promoter powder.Then, add poly-vinyl alcohol solution and stir, reaction coating powder is mixed into paste, be coated on EPS apperance surface, dry after being coated with fireproof coating, finally bury case casting and obtain alumina base coating.The feature of the method causes self-propagating reaction by casting heat, due to product in-situ preparation, avoids extraneous pollution and be mingled with, ensure that mechanics and physical property; The high product that makes of exothermic temperature is melt, and cladding ensures the compactness of coating and the bond strength at interface in metal surface, can prepare reactive cladding alumina base coating of good performance.
Description
Technical field
The invention belongs to metal-base composites preparing technical field, particularly a kind of method preparing alumina base reactive cladding coating.
Technical background
The wearing and tearing of wearing and tearing under particularly high temperature are one of factors of part dominant failure, cause workpiece replacing or production line frequent maintenance, cause huge energy consumption and economic loss.The main method of current alleviation part impact wear under evil slightly operating mode is surface-coating technology, and it has the huge advantage of low-cost and high-performance.
Aluminium oxide ceramics Mohs' hardness is 9, has high rigidity, high-melting-point, high corrosion resistant, has stable high-temperature performance simultaneously, can be used as desirable face coat.In ceramic-lined steel pipe, alumina base coating has achieved and has applied widely, excellent performance.
Self-propagating high-temperature synthesis utilizes the outside energy of necessity that provides to bring out thermal chemical reaction, and form combustion wave, reaction after this just can proceed under the heat support of reacting before, the material after reaction spreads and terminates needed for formation.Adopt self-propagating method at metal surface preparation feedback cladding ceramic coating, product is in-situ preparation, and combination interface is clean, avoids extraneous pollution and is mingled with, and ensure that mechanics and physical property; The high product that makes of exothermic temperature is melt, and cladding ensures the compactness of coating and the bond strength at interface in metal surface.Save the energy simultaneously, reduce production cost, enhance productivity, be suitable for industrialized mass production.
Summary of the invention
The object of the present invention is to provide a kind of method preparing cast(ing) surface reactive cladding alumina base coating.The feature of this method be simple to operate, production efficiency is high, coating performance is excellent.
Principle of the present invention is: utilize in casting cycle the heat of liquid of casting to ignite self-propagating reaction, in-situ preparation alumina ceramic grain, is uniformly distributed in high-temperature fusant, and cladding finally forms ceramic coating in cast(ing) surface.
Concrete steps of the present invention are as follows:
(1) brown iron oxide or nickel monoxide powder, aluminium powder, alumina powder and metal promoter powder are prepared burden according to mass ratio 15-67%:10-23%:0-20%:10-60%, mix 1-24 hour and make mixed-powder in ball mill;
(2) in mixed-powder, add binding agent, the mass ratio of binding agent and mixed-powder is 1:10-1:50, stirs and makes paste coating;
(3) paste coating be coated in the surface of foundry goods EPS plastic foaming mold or be coated on assigned address and at 40-50 DEG C of dry 1-10 hour;
(4) by step 3) be coated with the fire-resistant Sand sticking-resistant coating of one deck outside the cast model that obtains, dry 4-20 hour at 50-60 DEG C;
(5) melting copper liquid in medium-frequency induction furnace, casts, and utilizes the high temperature of copper liquid to cause self-propagating reaction: Fe
2o
3+ Al=Fe+Al
2o
3, 3NiO+2Al=3Ni+Al
2o
3, form alumina-based ceramic hard phase;
(6) foundry goods is heat-treated, and carries out removing surface, polishing after being cooled to room temperature, obtains the foundry goods of surface for self-propagating reaction cladding alumina base coating.
Wherein casting technique is founding casing with vacuum; Melting object is fine copper; The metal promoter powdery components mass ratio that coating uses is: Ni:0-60%, Cr:0-30%, Si:0-10%, B:0-5%, Fe:0-15%, and all the other are copper; Powder size used is: brown iron oxide 1-50 μm, aluminium powder 1-50 μm, alumina powder 1-100 μm, metal promoter powder 1-100 μm; Binding agent is the polyvinyl alcohol water solution of 3wt%; Cast(ing) surface coating layer thickness is 2-10mm; Foundry goods coating comprises intermediate alloy phase and the distribution aluminium oxide hard-phase particles wherein of Binder Phase matrix, generation, and the percentage by volume of aluminium oxide hard phase is 10-60%, and the percentage by volume of intermediate alloy phase is 1-20%, and all the other are Binder Phase matrix; Coating hardness is HRC53-70.
The invention has the advantages that: reactive cladding ceramic coating combination interface is clean, has higher mechanics and physical property; The compactness of coating and the bond strength at interface well, show good wear resistance and corrosion resistance under arms in process.Raw material sources are extensive simultaneously, and reduce production cost, the introducing of founding casing with vacuum further increases production efficiency, is suitable for industrialized mass production.
Detailed description of the invention
Embodiment 1:
(1) the nickel monoxide powder 6.0kg of particle mean size 20-25 μm is taken, the aluminium powder 1kg of 45 μm, metal dust (the Ni:60wt% of alumina powder 2kg and 45 μm of 45 μm, Cr:4wt%, Si:5wt%, B:3wt%, Fe:10wt%, all the other are copper) 1.5kg, batch mixing 8 hours in ball mill;
(2) in mixed-powder, add the polyvinyl alcohol water solution 750g of 3wt%, stir and make paste coating;
(3) paste coating is coated in the assigned address on EPS plastic foaming mold surface, i.e. the position of foundry goods generation fretting wear, coat thickness is 4mm, is placed in 50 DEG C of environment dry 3 hours;
(4) by step 3) magnesia powder Sand sticking-resistant coating that the mould external-hanging 3mm that obtains is thick, be placed in 60 DEG C of environment dry 4 hours;
(5) bury sand vibration molding, and vacuumize sandbox, vacuum is 0.07MPa, and in intermediate frequency furnace, smelting pure copper liquid, casts, cast temperature 1300 DEG C, utilizes the heat of copper liquid in casting cycle to ignite self-propagating reaction;
(6) when foundry goods is cooled to 700 DEG C, mould turnover knockout, is placed in 920 DEG C of environment insulations 3 hours, shrend solution treatment (water temperature 25 DEG C) after taking out by foundry goods, be placed in 480 DEG C of environment insulations 4 hours again, air cooling is to room temperature subsequently, and effects on surface polishing cleaning, namely obtains surperficial self-propagating reaction cladding alumina base coating, coating and matrix metallurgical binding, any surface finish is fine and close, coating layer thickness 4.5mm, hardness HRC67.4.
Embodiment 2:
(1) the croci 6.0kg of particle mean size 20-25 μm is taken, the aluminium powder 2kg of 45 μm, metal dust (the Ni:60wt% of alumina powder 2kg and 45 μm of 45 μm, Cr:4wt%, Si:5wt%, B:3wt%, Fe:10wt%, all the other are copper) 1.5kg, batch mixing 8 hours in ball mill;
(2) in mixed-powder, add the polyvinyl alcohol water solution 750g of 3wt%, stir and make paste coating;
(3) paste coating is coated in the assigned address on EPS plastic foaming mold surface, i.e. the position of foundry goods generation fretting wear, coat thickness is 4mm, is placed in 50 DEG C of environment dry 3 hours;
(4) by step 3) magnesia powder Sand sticking-resistant coating that the mould external-hanging 3mm that obtains is thick, be placed in 60 DEG C of environment dry 4 hours;
(5) bury sand vibration molding, and vacuumize sandbox, vacuum is 0.07MPa, and in intermediate frequency furnace, smelting pure copper liquid, casts, cast temperature 1300 DEG C, utilizes the heat of copper liquid in casting cycle to ignite self-propagating reaction;
(6) when foundry goods is cooled to 700 DEG C, mould turnover knockout, is placed in 920 DEG C of environment insulations 3 hours, shrend solution treatment after taking out by foundry goods, be placed in 480 DEG C of environment insulations 4 hours again, air cooling is to room temperature subsequently, and effects on surface polishing cleaning, namely obtains surperficial self-propagating reaction cladding alumina base coating, coating and matrix metallurgical binding, surface light is fine and close, coating layer thickness 4.5mm, hardness HRC66.4.
The alumina base reactive cladding coating product of above-mentioned preparation, technique is simple, and coating hard phase is evenly distributed, and is combined well with matrix, has good high-temperature behavior and higher intensity hardness and wearability.
Claims (1)
1. reactive cladding prepares a method for alumina base coating, it is characterized in that: react and caused by cast temperature, without the need to outside resources; Product is in-situ preparation, and combination interface is clean, avoids extraneous pollution and is mingled with, and ensure that mechanics and physical property; The high product that makes of exothermic temperature is melt, and cladding ensures the compactness of coating and the bond strength at interface in metal surface, and its concrete steps are as follows:
1) brown iron oxide or nickel oxide powder, aluminium powder, alumina powder and metal promoter powder are prepared burden according to mass ratio 15-67%:10-23%:0-20%:10-60%, mix 1-24 hour and make mixed-powder in ball mill;
2) in mixed-powder, add binding agent, the mass ratio of binding agent and mixed-powder is 1:10-1:50, stirs and makes paste coating;
3) paste coating be coated in the surface of foundry goods EPS plastic foaming mold or be coated on assigned address and at 40-50 DEG C of dry 1-10 hour;
4) by step 3) be coated with the fire-resistant Sand sticking-resistant coating of one deck outside the cast model that obtains, dry 4-20 hour at 50-60 DEG C;
5) melting copper liquid in medium-frequency induction furnace, casts, and utilizes the high temperature of copper liquid to cause self-propagating reaction: Fe
2o
3+ Al=Fe+Al
2o
3, 3NiO+2Al=3Ni+Al
2o
3, form alumina-based ceramic hard phase;
6) foundry goods is heat-treated, and carries out removing surface, polishing after being cooled to room temperature, obtains the foundry goods of surface for self-propagating reaction cladding alumina base coating;
Wherein step 1) described in metal promoter powder be low melting point from molten metal, constituent mass ratio is: Ni:0-60%, Cr:0-30%, Si:0-10%, B:0-5%, Fe:0-15%, and all the other are copper;
Step 5) in pouring technology be founding casing with vacuum; Melting object is fine copper; The granularity of the powder that coating uses is: brown iron oxide 1-50 μm, aluminium powder 1-50 μm, alumina powder 1-100 μm, metal promoter powder 1-100 μm; Binding agent is the polyvinyl alcohol water solution of 3wt%; Cast(ing) surface coating layer thickness is 2-10mm; Foundry goods coating comprises intermediate alloy phase and the distribution aluminium oxide hard-phase particles wherein of Binder Phase matrix, generation, and the percentage by volume of aluminium oxide hard phase is 10-60%, and the percentage by volume of intermediate alloy phase is 1-20%, and all the other are Binder Phase matrix; Coating hardness is HRC53-70.
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| CN103506564A (en) * | 2013-09-28 | 2014-01-15 | 无锡阳工机械制造有限公司 | High aluminum powder casting coating |
| CN104942268A (en) * | 2015-05-11 | 2015-09-30 | 北京科技大学 | Preparation method of copper-based titanium carbide/aluminum oxide surface particle strengthening composite material |
| CN104999053B (en) * | 2015-08-04 | 2017-05-24 | 东南大学 | Ferric-oxide-containing paint used for aluminum alloy cast-infiltration, and method for manufacturing cast-infiltration coating by using same |
| CN108555467B (en) * | 2018-01-09 | 2020-12-25 | 山东科技大学 | Method for rapidly repairing worn groove of middle plate of chute |
| CN110560629B (en) * | 2019-09-20 | 2021-11-30 | 宁波江丰电子材料股份有限公司 | Coating for smelting and casting high-purity aluminum and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101214539A (en) * | 2008-01-07 | 2008-07-09 | 吉林大学 | Method for preparing TiC granule partial reinforced abrasion-proof manganese steel composite material |
| CN102274951A (en) * | 2011-08-04 | 2011-12-14 | 广东新劲刚超硬材料有限公司 | Method for synthesizing titanium carbide-base hard alloy coating on surfaces of castings in situ |
| CN102274923A (en) * | 2011-08-04 | 2011-12-14 | 广东新劲刚超硬材料有限公司 | Method for in situ synthesis of tungsten carbide-based hard alloy coating on surface of cast |
| CN102423799A (en) * | 2011-12-12 | 2012-04-25 | 广东新劲刚超硬材料有限公司 | Method of in situ synthetic steel bond hard alloy casting composite hammerhead and hammerhead |
-
2013
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101214539A (en) * | 2008-01-07 | 2008-07-09 | 吉林大学 | Method for preparing TiC granule partial reinforced abrasion-proof manganese steel composite material |
| CN102274951A (en) * | 2011-08-04 | 2011-12-14 | 广东新劲刚超硬材料有限公司 | Method for synthesizing titanium carbide-base hard alloy coating on surfaces of castings in situ |
| CN102274923A (en) * | 2011-08-04 | 2011-12-14 | 广东新劲刚超硬材料有限公司 | Method for in situ synthesis of tungsten carbide-based hard alloy coating on surface of cast |
| CN102423799A (en) * | 2011-12-12 | 2012-04-25 | 广东新劲刚超硬材料有限公司 | Method of in situ synthetic steel bond hard alloy casting composite hammerhead and hammerhead |
Non-Patent Citations (1)
| Title |
|---|
| 自蔓延离心法研究;魏世丞等;《材料导报》;20000915;第14卷(第09期);17-18 * |
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