CN103938206B - Liquid zinc corrosion resistant sintering metal laser melting coating powder - Google Patents
Liquid zinc corrosion resistant sintering metal laser melting coating powder Download PDFInfo
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- CN103938206B CN103938206B CN201310019098.0A CN201310019098A CN103938206B CN 103938206 B CN103938206 B CN 103938206B CN 201310019098 A CN201310019098 A CN 201310019098A CN 103938206 B CN103938206 B CN 103938206B
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Abstract
The invention discloses a kind of liquid zinc corrosion resistant sintering metal laser melting coating powder, comprise Al
2o
3powder, Ti powder, Mo powder and B powder, weight percent is 60 ~ 70%Al
2o
3powder, 20 ~ 30%Ti powder, 3 ~ 10%Mo powder and 1 ~ 4%B powder.The corrosion resistant metal ceramic coating that this powder is formed through laser melting coating and austenite stainless steel substrate good combination, hardness is high, liquid zinc corrosion resistant is strong, do not crack, pore, the defect such as to be mingled with, and non-environmental-pollution, the corrosion-resistant effect in zinc liquid has very important innovative value and engineer applied meaning.
Description
Technical field:
The present invention relates to cladding laser surfaces technology, particularly relate to a kind of laser melting coating cermet material with liquid zinc corrosion resistant characteristic.
Background technology:
Metallic corrosion in recent years brings massive losses to national economy; the demand of zinc coating is in rising trend year by year; along with the continuous increase of the zinc-plated demand of the section bars such as steel plate and output; cause the container of zinc bath, dress zince & zinc alloy solution, liquid Zn transport pipe and thermometric protective casing etc. increasing by the waste of material; carry out the research of the material of liquid zinc corrosion resistant, improve its corrosion resistance nature and there is very important engineer applied value.For existing dress metallic zinc liquid, the high fragility of the conventional integral materials such as zinc liquid transport pipe and thermocouple temperature measurement protective casing, high cost and the preparation problems such as difficulty is large, the research of surface Zinc-corrosion resistant material more and more receives great concern, China Intellectual Property Office discloses 00123690.3 1 kinds of composite spray of metal and ceramics, its chemical composition consists of: 7.0 ~ 10.0%Co, 49.0 ~ 60.0%W, 2.5 ~ 4.5%C, 5.2 ~ 9.5%Fe, 0.8 ~ 2.0%B, 20.0 ~ 29.0%Mo, above-mentioned Chemical Composition composition calculates according to weight percent.Have excellent liquid zinc corrosion resistant, wear-resistingly undermine anti-stick zinc performance, effectively improve the work-ing life of Continuous Hot Dip Galvanizing spare part-sinking roller and stabilizing roller, the time that uses on the machine continuously can reach 21 ~ 27 days, reduces production cost.China Intellectual Property Office discloses 200510030979.8 1 kinds of large granular spherical metal ceramic nano composite spraying powders, and component and weight percent thereof are: 50 ~ 70% TiB2s, 10 ~ 24% cobalts, 6 ~ 13% chromium powders, 5 ~ 11% tungsten borides, surplus are rare earth powder.The granularity of TiB2, tungsten boride and rare earth powder is all between 0.5 micron to 1 micron, and cobalt and chromium powder granularity are all less than 100 nanometers.Be mixed in proportion by above powder, the powder granularity prepared according to wet ball grinding, centrifugal or press atomization granulation, vacuum heat treatment process and gradation program is respectively 20 ~ 45 microns and 45 ~ 75 microns, spherical in shape or subsphaeroidal structure.Utilize the roll surface coating that this powder is prepared by hot-spraying techniques, there is excellent wear-resistant, high temperature resistant, alumite liquid zinc corrosion ability, on continuous zinc/aluminium/aluminium zinc coating unit, duration of service is 18 ~ 29 days, reduces generation and maintenance cost, improves aluminum-zinc alloy strip quality.
On hot dip zinc-aluminium production line, zinc pot is used for liquid metal heating and insulation.Adopting thermopair continuous temperature measurement and temperature control method, is ensure one of hot dip quality product and the key factor reducing the energy and resource and materials consumption.Now conventional thermocouple protective casing adopts stainless-steel pipe material, and one end makes through shutoff welding and machining.Thermopair is immersed in high temperature zinc-aluminium fluid for a long time, and because the corrosive nature of zinc-aluminium fluid is strong, iron can react with plating solution and mainly generate Fe in zinc pot
2al
5damage is caused Deng intermetallic compound, the work-ing life of thermopair is generally 3 ~ 5 days, and the shortest time is only 12 hours, and not only the consumption of thermopair is large, and be easy to the larger fluctuation causing temperature in thermocouple break process, have influence on the stability contorting to production technique.And conventional nonmetal thermocouple protective casing is as Al
2o
3although its corrosion resisting property is good, thermal shock resistance is poor very easily there is crack damage, and graphite material sleeve pipe is then lower due to its physical strength, easily causes impact failure manually fishing in cadmia operation process.Therefore, existing thermocouple protective casing is owing to can not solve corrosion resistance nature, thermal shock resistance and problems of mechanical strength simultaneously, and using in zinc-aluminium fluid cannot practical requirement.China Intellectual Property Office also discloses 200510029204.9 and relates to thermocouple protective casing and manufacture method thereof.A kind of thermo-couple composite protective sleeve; comprise base tube cylindrical shell and coating; the end of base tube cylindrical shell is processed to arc-shaped curved surface; base tube cylindrical shell is made of metal; coating is made up of melts combine bottom, intermediate layer and work layer on surface; melts combine bottom is the cermet material close with base tube cylindrical shell metallicity or alloy material, and work layer on surface is oxide ceramic material, and intermediate layer is cermet material and oxide ceramic material mixture.Thermo-couple composite protective sleeve of the present invention can meet corrosion resistance nature, thermal shock resistance, heat conductivility and sufficient mechanical strength in liquid metal zinc-aluminium fluid simultaneously.But there is the defect that soft, high cost and preparation difficulty are large equally.
Summary of the invention:
The object of the present invention is to provide the liquid zinc corrosion resistant sintering metal laser melting coating powder that a kind of metal-ceramic coating is combined well with austenite stainless steel substrate, liquid zinc corrosion resistant is strong, hardness is high.
The present invention is achieved by the following technical solution:
Liquid zinc corrosion resistant sintering metal laser melting coating powder, comprises Al
2o
3powder, Ti powder, Mo powder and B powder, weight percent is 60 ~ 70%Al
2o
3powder, 20 ~ 30%Ti powder, 3 ~ 10%Mo powder and 1 ~ 4%B powder, described Al
2o
3the granularity < of powder 50 microns, the granularity < of described Ti powder, Mo powder and B powder 20 microns.
Described Al
2o
3the purity > 97.9% of powder.
The purity > 97.9% of described Ti powder, Mo powder and B powder.
Described Al
2o
3the purity > of powder 99.9%, granularity < 10 micron.
The purity > of described ti powder, molybdenum powder and boron powder 99.9%, granularity < 5 micron.
The present invention compared with prior art has following row beneficial effect:
The corrosion resistant metal ceramic coating that liquid zinc corrosion resistant sintering metal laser melting coating powder of the present invention is formed through laser melting coating and austenite stainless steel substrate good combination, hardness is high, liquid zinc corrosion resistant is strong, do not crack, pore, the defect such as to be mingled with, and non-environmental-pollution, the cermet composition formed can be allocated, adopt laser melting and coating technique, energy density is high, heat input is little, austenite stainless steel substrate and cermet coating Interface adhesive strength strong, stainless steel liquid zinc corrosion resistant can be significantly improved, the corrosion-resistant effect of this coated material in zinc liquid has very important innovative value and engineer applied meaning, also can be used for the manufacture of thermocouple protective casing.
Accompanying drawing illustrates:
Fig. 1 is the macro surface pattern photo of the embodiment of the present invention one metal-ceramic coating;
Fig. 2 is the metallographic microstructure photo of the embodiment of the present invention one metal-ceramic coating cross section;
Fig. 3 is the X-ray spectrogram of the embodiment of the present invention one metal-ceramic coating;
Fig. 4 is that the embodiment of the present invention one metal-ceramic coating is by the microhardness curve of surface to subsurface.
Sequence number in figure: 1, Laser Cladding Metal-ceramic Composite Coating, 2, stainless steel substrate.
Embodiment:
Below in conjunction with the drawings and specific embodiments, the invention will be further described.
Embodiment one:
See Fig. 1, Fig. 2, Fig. 3 and Fig. 4, a kind of liquid zinc corrosion resistant sintering metal laser melting coating powder, comprises Al
2o
3powder, Ti powder, Mo powder and B powder, weight percent is 60%Al
2o
3powder, 30%Ti powder, 6%Mo powder and 4%B powder, described Al
2o
3the granularity of powder 20 microns, the granularity of described Ti powder, Mo powder and B powder 15 microns, described Al
2o
3the purity > 99.9% of powder, ti powder, molybdenum powder and boron powder.Its laser cladding process is as follows: A) the surface 240# emery paper for the treatment of the austenite stainless steel substrate 304 of laser melting coating polishes, object is the surface of alligatoring austenite stainless steel substrate 304, be beneficial to the inlaying of powder and stainless steel substrate, clog, and with washes of absolute alcohol, remove by the various impurity greasy dirts on cladding surface, be beneficial to the wetting and metallurgical binding of powder and matrix surface; B) by Al
2o
3powder, Ti powder, Mo powder, B powder mix according to weight percent, and the granularity being ground to mixed powder is less than 10 microns; C) by step B) mixed powder after gained grinding is placed in 120 DEG C dries after 2 hours, is that mixed powder is coated in steps A by the synchronous powder feeding system mode of 0.4g/s with powder sending quantity) surface to the coat thickness of gained austenite stainless steel substrate is 1 millimeter; D) adopt that optical maser wavelength is 10.6 microns, laser power is 3kW, sweep velocity is 500mm/min, spot diameter is 6 millimeters, defocusing amount is 60 millimeters and be under the argon shield of 12L/h at flow; to step C) surface coating layer of gained austenite stainless steel substrate carries out laser melting coating, namely completes the surface laser cladding process to austenitic stainless steel.
Austenite stainless steel substrate 2 surface quality can be made after Laser Cladding Treatment good, form inner flawless, pore, the cladding coating of defect such as be mingled with, and there is high rigidity and liquid zinc corrosion resistant performance.
The corrosion resistance nature of Laser Cladding Metal-ceramic Composite Coating 1, by by laser melting coating ceramic coating, ferroboron were put into the liquid zinc corrosion of melting after 10 hours, takes out mensuration corrosion layer thickness and has come.
The corrosion of the resistance to aluminium Performance comparision of table one or two kind of differing materials
| Containing the austenite stainless steel substrate of Laser Cladding Metal-ceramic Composite Coating | Ferroboron | |
| Average corrosion rate (mm/h) | 8.3Х10 -5 | 2.5Х10 -1 |
Embodiment two:
A kind of liquid zinc corrosion resistant sintering metal laser melting coating powder, comprise Al2O3 powder, Ti powder, Mo powder and B powder, weight percent is 70%Al
2o
3powder, 20%Ti powder, 9%Mo powder and 1%B powder, described Al
2o
3the granularity < of powder 20 microns, the granularity < of described Ti powder, Mo powder and B powder 15 microns, described Al
2o
3the purity > 97.9% of powder, ti powder, molybdenum powder or boron powder.Its laser cladding process is as follows: A) surface for the treatment of the austenite stainless steel substrate 304 of laser melting coating carries out sandblasting, object is the surface of alligatoring austenite stainless steel substrate 304, be beneficial to the inlaying of powder and stainless steel substrate, clog, and with washes of absolute alcohol, remove by the various impurity greasy dirts on cladding surface, be beneficial to the wetting and metallurgical binding of powder and matrix surface; B) by Al
2o
3powder, Ti powder, Mo powder, B powder mix according to weight percent, and the granularity being ground to mixed powder is less than 10 microns; C) by step B) mixed powder after gained grinding is placed in 100 DEG C dries after 3 hours, is that mixed powder is coated in steps A by the synchronous powder feeding system mode of 0.35g/s with powder sending quantity) surface to the coat thickness of gained austenite stainless steel substrate is 1 millimeter; D) adopt that optical maser wavelength is 10.6 microns, laser power is 4kW, sweep velocity is 450mm/min, spot diameter is 6 millimeters, defocusing amount is 55 millimeters and be under the argon shield of 12L/h at flow; to step C) surface coating layer of gained austenite stainless steel substrate carries out laser melting coating, namely completes the surface laser cladding process to austenitic stainless steel.
After testing, coating structure is made up of the alumina-ceramic phase of liquid zinc corrosion resistant and the Ti metal of a bonding effect, and austenite stainless steel substrate 2 sample after visible laser cladding has excellent liquid zinc corrosion resistant performance, can be used as liquid zinc corrosion resistant material.
The corrosion resistance nature of Laser Cladding Metal-ceramic Composite Coating 1, by by laser melting coating ceramic coating, ferroboron were put into the liquid zinc corrosion of melting after 10 hours, takes out mensuration corrosion layer thickness and has come.
The corrosion of the resistance to aluminium Performance comparision of table two two kinds of differing materials
| Containing the austenite stainless steel substrate of Laser Cladding Metal-ceramic Composite Coating | Ferroboron | |
| Average corrosion rate (mm/h) | 8.1Х10 -5 | 2.5Х10 -1 |
Embodiment three:
A kind of liquid zinc corrosion resistant sintering metal laser melting coating powder, comprises Al
2o
3powder, Ti powder, Mo powder and B powder, weight percent is 65%Al
2o
3powder, 27%Ti powder, 6%Mo powder and 2%B powder, described Al
2o
3the granularity < of powder 20 microns, the granularity < of described Ti powder, Mo powder and B powder 15 microns, described Al
2o
3the purity > 99.9% of powder, ti powder, molybdenum powder or boron powder.Its laser cladding process is as follows: A) the surface 240# emery paper for the treatment of the austenite stainless steel substrate 304 of laser melting coating polishes, object is the surface of alligatoring austenite stainless steel substrate 304, be beneficial to the inlaying of powder and stainless steel substrate, clog, and with washes of absolute alcohol, remove by the various impurity greasy dirts on cladding surface, be beneficial to the wetting and metallurgical binding of powder and matrix surface; B) by Al
2o
3powder, Ti powder, Mo powder, B powder mix according to weight percent, and the granularity being ground to mixed powder is less than 10 microns; C) by step B) mixed powder after gained grinding is placed in 110 DEG C dries after 2 hours, is that mixed powder is coated in steps A by the synchronous powder feeding system mode of 0.4g/s with powder sending quantity) surface to the coat thickness of gained austenite stainless steel substrate is 1 millimeter; D) adopt that optical maser wavelength is 10.6 microns, laser power is 3.5kW, sweep velocity is 400mm/min, spot diameter is 5.5 millimeters, defocusing amount is 55 millimeters and be under the argon shield of 12L/h at flow; to step C) surface coating layer of gained austenite stainless steel substrate carries out laser melting coating, namely completes the surface laser cladding process to austenitic stainless steel.
Austenite stainless steel substrate 2 surface quality can be made after Laser Cladding Treatment good, form inner flawless, pore, the cladding coating of defect such as be mingled with, and there is high rigidity and liquid zinc corrosion resistant performance.
The corrosion resistance nature of Laser Cladding Metal-ceramic Composite Coating 1, by by laser melting coating ceramic coating, ferroboron were put into the liquid zinc corrosion of melting after 10 hours, takes out mensuration corrosion layer thickness and has come.
The corrosion of the resistance to aluminium Performance comparision of table three two kinds of differing materials
| Containing the austenite stainless steel substrate of Laser Cladding Metal-ceramic Composite Coating | Ferroboron | |
| Average corrosion rate (mm/h) | 7.8Х10 -5 | 2.5Х10 -1 |
The Laser Cladding Metal-ceramic Composite Coating obtained embodiment one below carries out contextual analysis of organization and various performance test, and the superiority of its performance is described:
1, contextual analysis of organization
Use metaloscope to observe microstructure of surface cladding layer, as shown in Figure 2, between 304 stainless steel bases and aluminum oxide, titanium composite cermet coating, create metallurgical binding.
Adopt X-ray diffractometer to analyze the thing phase composite of metal-ceramic coating, result is as shown in the X-ray spectral line of Fig. 3, and X-ray diffraction analysis shows, metal-ceramic coating is primarily of aluminum oxide, titanium composition.
2, microhardness
Utilize HMV-2t microhardness tester Laser Measurement cladding layer microhardness, take clad layer surface as starting point (0 point), also cross the bonding surface of cladding layer and matrix to intrinsic silicon, from a left side, the right side is got different distance successively and is beaten microhardness, averages after same aspect being made a call to three points always.Loaded load 100g, loads 10 seconds time length.The durometer level of laser cladding coating is in HV243 ~ 1430, and hardness profile as shown in Figure 4.
Embodiment is just for the ease of understanding technical scheme of the present invention; do not form limiting the scope of the invention; every do not depart from technical solution of the present invention interior perhaps above scheme is done according to technical spirit of the present invention any simple modification, equivalent variations and modification, all still belong within scope.
Claims (5)
1. liquid zinc corrosion resistant sintering metal laser melting coating powder, is characterized in that: comprise Al
2o
3powder, Ti powder, Mo powder and B powder, weight percent is 60 ~ 70%Al
2o
3powder, 20 ~ 30%Ti powder, 3 ~ 10%Mo powder and 1 ~ 4%B powder, described Al
2o
3the granularity < of powder 50 microns, the granularity < of described Ti powder, Mo powder and B powder 20 microns.
2. liquid zinc corrosion resistant sintering metal laser melting coating powder according to claim 1, is characterized in that: described Al
2o
3the purity > 97.9% of powder.
3. liquid zinc corrosion resistant sintering metal laser melting coating powder according to claim 1 and 2, is characterized in that: the purity > 97.9% of described Ti powder, Mo powder and B powder.
4. liquid zinc corrosion resistant sintering metal laser melting coating powder according to claim 1, is characterized in that: described Al
2o
3the purity > of powder 99.9%, granularity < 10 micron.
5. the liquid zinc corrosion resistant sintering metal laser melting coating powder according to claim 1 or 4, is characterized in that: the purity > of described ti powder, molybdenum powder and boron powder 99.9%, granularity < 5 micron.
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| CN201310019098.0A CN103938206B (en) | 2013-01-20 | 2013-01-20 | Liquid zinc corrosion resistant sintering metal laser melting coating powder |
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| CN103938206B true CN103938206B (en) | 2015-12-23 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2182349A (en) * | 1985-11-05 | 1987-05-13 | Sec Dep For Trade & Industry T | Laser coating with inorganic materials |
| CN101265575A (en) * | 2008-05-09 | 2008-09-17 | 天津市汇利通金属表面技术有限公司 | Metallurgical cast iron roll surface laser nanometer ceramic alloying processing method |
| CN102146563A (en) * | 2011-03-08 | 2011-08-10 | 张昆 | Production process for intelligent temperature adjusting steel rail with laser cladding layer and heat insulation coating |
| CN102212820A (en) * | 2011-05-25 | 2011-10-12 | 石家庄华鼎高科强化合金设备制造有限公司 | High-temperature-wear-resistant lining plate for coke pot for coke dry quenching and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62246885A (en) * | 1986-04-17 | 1987-10-28 | 三菱マテリアル株式会社 | Ceramic coating method |
| US20020110649A1 (en) * | 2000-05-09 | 2002-08-15 | Skszek Timothy W. | Fabrication of alloy variant structures using direct metal deposition |
-
2013
- 2013-01-20 CN CN201310019098.0A patent/CN103938206B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2182349A (en) * | 1985-11-05 | 1987-05-13 | Sec Dep For Trade & Industry T | Laser coating with inorganic materials |
| CN101265575A (en) * | 2008-05-09 | 2008-09-17 | 天津市汇利通金属表面技术有限公司 | Metallurgical cast iron roll surface laser nanometer ceramic alloying processing method |
| CN102146563A (en) * | 2011-03-08 | 2011-08-10 | 张昆 | Production process for intelligent temperature adjusting steel rail with laser cladding layer and heat insulation coating |
| CN102212820A (en) * | 2011-05-25 | 2011-10-12 | 石家庄华鼎高科强化合金设备制造有限公司 | High-temperature-wear-resistant lining plate for coke pot for coke dry quenching and preparation method thereof |
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