CN102634790B - Fe-Ti and Fe-Al complex-phase intermetallic compound anti-corrosion layer and preparation method thereof - Google Patents
Fe-Ti and Fe-Al complex-phase intermetallic compound anti-corrosion layer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an Fe-Ti and Fe-Al complex-phase intermetallic compound anti-corrosion layer and a preparation method thereof and belongs to the field of surface engineering. The anti-corrosion layer is the iron-rich Fe-Ti and Fe-Al complex-phase intermetallic compound anti-corrosion layer which is generated in situ by adopting laser treatment technology on pearlite heat-resistant steel. The anti-corrosion layer is prepared according to the method which comprises the following steps: firstly, performing oil-removing and de-rusting treatment on a pearlite heat-resistant steel substrate, and then forming the iron-rich Fe-Ti and Fe-Al complex-phase intermetallic compound anti-corrosion layer in situ on the pearlite heat-resistant steel substrate by titanium aluminum powder mixture through laser. By designing the iron-rich Fe-Ti and Fe-Al complex-phase intermetallic compound anti-corrosion layer by the invention, on one hand, the high-temperature corrosion resistance under high-temperature chloric oxidation condition is obviously increased in comparison with an aluminum-rich Fe-Al intermetallic compound anti-corrosion layer, on the other hand, a more effective anti-corrosion layer for resisting biomass ash high-temperature corrosion is supplied for solving the problem of serious high-temperature corrosion of a boiler overheat pipe.
Description
Technical field
The invention belongs to field of surface engineering technique, particularly a kind of Fe-Ti and Fe-Al complex phase intermetallic compound anticorrosion layer and preparation method thereof.
Background technology
Biomass power generation is one of the important means of development low-carbon economy and recycling economy and mode.In order to improve the generating efficiency of biomass electric power plant, China has produced and has moved the biomass boiler (540 ℃ of vapor temperatures, vapor pressure 9.2 MPa) of high-temp and-pressure.But, along with the raising of steam parameter, biomass boiler superheater tube heavy corrosion problem has appearred.This is owing in the yellow stalk of biomass boiler burning and grey stalk, containing higher alkali metal chloride, discharge the material of chloride low melting point in combustion processes, cause the superheating surface Serious Slagging, under the effect of lime-ash and flue gas, make superheater tube produce serious high temperature alkali metal chloride corrosion.
The serious High Temperature Corrosion for superheater tube, the boiler producer selects austenitic heat-resistance steel to manufacture superheater tube usually.Although select austenitic heat-resistance steel that cost is high can improve to a certain extent the high temperature chlorine corrosion resistant performance of superheater tube, but the serious High Temperature Corrosion of superheater tube still happens occasionally, the operation of the biomass boiler that even has less than within 15 months, just occur superheater tube corrosion pipe explosion accident (Li Qing etc. generating set, 2009(3): 214).The biomass boiler superheater tubes burst is not because the hot strength deficiency of superheater tube steel but high temperature relate to due to the high temperature corrosion of chlorine environment.And that the characteristic of austenitic heat-resistance steel is hot strength is higher, high-temperature oxidation resistance is better, but the resistance to high temperature corrosion ability is general in chloride well-oxygenated environment.It is the effective way with raising boiler superheater tube high-temperature corrosion resistance life-span of better economy that pearlite type superheater tube steel is carried out to surface modification treatment.Boi1er tube is carried out to aluminizing pipe that aluminising makes for coal-fired power station boiler water wall tube and superheater tube, its good anti-fiery side high temperature corrosion property obtained preferably benefit (Cai Zhigang, Xie Tao. thermal power generation, 1996, (1): 3).In current aluminizing pipe aluminized coating be organized as the Fe-Al intermetallic compound, be mainly FeAl and Fe
2al
5.
Summary of the invention
The shortcoming that the present invention is directed to above-mentioned boiler overheating tube material has been carried out the improvement of novelty, has proposed a kind of Fe-Ti and Fe-Al complex phase intermetallic compound anticorrosion layer and preparation method thereof.
The invention provides a kind of Fe-Ti and Fe-Al complex phase intermetallic compound anticorrosion layer, wherein the ratio of aluminium element and titanium elements is 1:19 ~ 1:4, and this anticorrosion layer is by the Fe of rich iron
2ti and Fe
3al complex phase intermetallic compound forms.
The invention still further relates to the preparation method of above-mentioned Fe-Ti and Fe-Al complex phase intermetallic compound anticorrosion layer, the method concrete steps are as follows:
By granularity, be 100 orders～200 orders, the aluminium powder of purity >=99.5% is put into mixed powder machine with titanium valve and is mixed 20 minutes, and wherein the content of aluminium powder is 5 wt%～20 wt%, and all the other are titanium valve.Powder mix is modulated into to pasty state, on the 20 g pearlite heatproof steel matrixes that the geometrical dimension that is coated in oil removing, rust cleaning is 100 mm * 200 mm * 3 mm, coat is dried and is placed on the cladding worktable.The laser work head that employing is connected with optical fiber is done horizontal uniform motion, the fixing method of workpiece, directly titanium aluminium mixed powder and pearlite heatproof steel matrix generation in-situ synthesized reaction are generated to Fe-Ti and the Fe-Al complex phase intermetallic compound anticorrosion layer of rich iron by LASER HEATING, this anticorrosion layer is by the Fe of rich iron
2ti and Fe
3al complex phase intermetallic compound forms.The laser work head is done linear uniform motion at the x direction of principal axis, and the y direction of principal axis is done adjustable step motion.The concrete cladding parameter of LASER HEATING is: laser output power 500 W, and spot diameter 3 mm, laser frequency 10 Hz, pulsewidth 3.2 ms, laser beam flying speed 4 mm/s, overlapping rate 50%, shielding gas is argon gas, shield gas flow rate is 10 ml/s.The anticorrosion layer thickness made is 300 μ m ~ 400 μ m.
Beneficial effect: the present invention is by Fe-Ti and the Fe-Al complex phase intermetallic compound anticorrosion layer of a kind of rich iron of design, and this anticorrosion layer is by the Fe of rich iron
2ti and Fe
3al complex phase intermetallic compound forms.One side is with respect to the Fe-Al intermetallic compound anticorrosion layer of rich aluminium, at high temperature, relate in the well-oxygenated environment of chlorine, its high-temperature corrosion resistance performance has had and has significantly improved, for solving the serious High Temperature Corrosion of boiler overheating pipe, provide a kind of anticorrosion layer of the more effective lime-ash of anti-biomass high temperature corrosion on the other hand.
The accompanying drawing explanation
Fig. 1 a ~ Fig. 1 e is respectively embodiment 1 ~ embodiment 5 and FeAl-Fe in the time of 600 ℃
2al
5oxidation kinetics curve comparison figure.
Fig. 2 is the cross section backscattered electron composition picture of the anticorrosion layer of embodiment 1 preparation, and wherein left side is matrix, and right side is surface reforming layer.
Fig. 3 is the XRD figure spectrum of the anticorrosion layer of embodiment 2 preparations.
Embodiment
The invention provides a kind of Fe-Ti and Fe-Al complex phase intermetallic compound anticorrosion layer and preparation method thereof, below in conjunction with the drawings and specific embodiments, the present invention will be further described.
Embodiment 1
Take aluminium powder (granularity is 100 orders～200 orders, purity >=99.5%) 5 grams, titanium valve (granularity is 100 orders～200 orders, purity >=99.5%) 95 grams, put into mixed powder machine and mix 20 minutes.Powder mix is modulated into to pasty state, on the 20 g pearlite heatproof steel matrixes that the geometrical dimension that is coated in oil removing, rust cleaning is 100 mm * 200 mm * 3 mm, controls and apply approximately 0.5 mm of bed thickness, coat is dried and is placed on the cladding worktable.The laser work head that employing is connected with optical fiber is done horizontal uniform motion, the fixing method of workpiece, directly titanium aluminium mixed powder and pearlite heatproof steel matrix generation in-situ synthesized reaction are generated to Fe-Ti and the Fe-Al complex phase intermetallic compound anticorrosion layer of rich iron by LASER HEATING, this anticorrosion layer is by the Fe of rich iron
2ti and Fe
3al complex phase intermetallic compound forms.The laser work head is done linear uniform motion at the x direction of principal axis, and the y direction of principal axis is done adjustable step motion.The concrete cladding parameter of LASER HEATING is: laser output power 500 W, and spot diameter 3 mm, laser frequency 10 Hz, pulsewidth 3.2 ms, laser beam flying speed 4 mm/s, overlapping rate 50%, shielding gas is argon gas, shield gas flow rate is 10 ml/s.The anticorrosion layer thickness made is 300 μ m ~ 400 μ m, sees Fig. 2.Be embedded in the biomass lime-ash after 600 ℃ of high temperature oxidation and corrosion 214 h, its solidity to corrosion is FeAl-Fe
2al
53.7 times of anticorrosion layer, be shown in Fig. 1 a.
Embodiment 2
Take aluminium powder (granularity is 100 orders～200 orders, purity >=99.5%) 10 grams, titanium valve (granularity is 100 orders～200 orders, purity >=99.5%) 90 grams, put into mixed powder machine and mix 20 minutes.Powder mix is modulated into to pasty state, on the 20 g pearlite heatproof steel matrixes that the geometrical dimension that is coated in oil removing, rust cleaning is 100 mm * 200 mm * 3 mm, controls and apply approximately 0.5 mm of bed thickness, coat is dried and is placed on the cladding worktable.The laser work head that employing is connected with optical fiber is done horizontal uniform motion, the fixing method of workpiece, directly titanium aluminium mixed powder and pearlite heatproof steel matrix generation in-situ synthesized reaction are generated to Fe-Ti and the Fe-Al complex phase intermetallic compound anticorrosion layer of rich iron by LASER HEATING, this anticorrosion layer is by the Fe of rich iron
2ti and Fe
3al complex phase intermetallic compound forms.The laser work head is done linear uniform motion at the x direction of principal axis, and the y direction of principal axis is done adjustable step motion.The concrete cladding parameter of LASER HEATING is: laser output power 500 W, and spot diameter 3 mm, laser frequency 10 Hz, pulsewidth 3.2 ms, laser beam flying speed 4 mm/s, overlapping rate 50%, shielding gas is argon gas, shield gas flow rate is 10 ml/s.Anticorrosion layer thickness is 300 μ m ~ 400 μ m, and Fig. 3 is shown in the phase composite of anticorrosion layer, is embedded in the biomass lime-ash after 600 ℃ of high temperature oxidation and corrosion 214 h, and its solidity to corrosion is FeAl-Fe
2al
54.0 times of anticorrosion layer, be shown in Fig. 1 b.
Embodiment 3
Take aluminium powder (granularity is 100 orders～200 orders, purity >=99.5%) 20 grams, titanium valve (granularity is 100 orders～200 orders, purity >=99.5%) 80 grams, put into mixed powder machine and mix 20 minutes.Powder mix is modulated into to pasty state, on the 20 g pearlite heatproof steel matrixes that the geometrical dimension that is coated in oil removing, rust cleaning is 100 mm * 200 mm * 3mm, controls and apply approximately 0.5 mm of bed thickness, coat is dried and is placed on the cladding worktable.The laser work head that employing is connected with optical fiber is done horizontal uniform motion, the fixing method of workpiece, directly titanium aluminium mixed powder and pearlite heatproof steel matrix generation in-situ synthesized reaction are generated to Fe-Ti and the Fe-Al complex phase intermetallic compound anticorrosion layer of rich iron by LASER HEATING, this anticorrosion layer is by the Fe of rich iron
2ti and Fe
3al complex phase intermetallic compound forms.The laser work head is done linear uniform motion at the x direction of principal axis, and the y direction of principal axis is done adjustable step motion.The concrete cladding parameter of LASER HEATING is: laser output power 500 W, and spot diameter 3 mm, laser frequency 10 Hz, pulsewidth 3.2 ms, laser beam flying speed 4 mm/s, overlapping rate 50%, shielding gas is argon gas, shield gas flow rate is 10 ml/s.Anticorrosion layer thickness is 300 μ m ~ 400 μ m, is embedded in the biomass lime-ash after 600 ℃ of high temperature oxidation and corrosion 214 h, and its solidity to corrosion is FeAl-Fe
2al
53.9 times of anticorrosion layer, be shown in Fig. 1 c.
Embodiment 4
Take aluminium powder (granularity is 100 orders～200 orders, purity >=99.5%) 15 grams, titanium valve (granularity is 100 orders～200 orders, purity >=99.5%) 85 grams, put into mixed powder machine and mix 20 minutes.Powder mix is modulated into to pasty state, on the 20 g pearlite heatproof steel matrixes that the geometrical dimension that is coated in oil removing, rust cleaning is 100 mm * 200 mm * 3 mm, controls and apply approximately 0.5 mm of bed thickness, coat is dried and is placed on the cladding worktable.The laser work head that employing is connected with optical fiber is done horizontal uniform motion, the fixing method of workpiece, directly titanium aluminium mixed powder and pearlite heatproof steel matrix generation in-situ synthesized reaction are generated to Fe-Ti and the Fe-Al complex phase intermetallic compound anticorrosion layer of rich iron by LASER HEATING, this anticorrosion layer is by the Fe of rich iron
2ti and Fe
3al complex phase intermetallic compound forms.The laser work head is done linear uniform motion at the x direction of principal axis, and the y direction of principal axis is done adjustable step motion.The concrete cladding parameter of LASER HEATING is: laser output power 500 W, and spot diameter 3 mm, laser frequency 10 Hz, pulsewidth 3.2 ms, laser beam flying speed 4 mm/s, overlapping rate 50%, shielding gas is argon gas, shield gas flow rate is 10 ml/s.Anticorrosion layer thickness is 300 μ m ~ 400 μ m, is embedded in the biomass lime-ash after 600 ℃ of high temperature oxidation and corrosion 214 h, and its solidity to corrosion is FeAl-Fe
2al
54.2 times of anticorrosion layer, be shown in Fig. 1 d.
Take aluminium powder (granularity is 100 orders～200 orders, purity >=99.5%) 12 grams, titanium valve (granularity is 100 orders～200 orders, purity >=99.5%) 88 grams, put into mixed powder machine and mix 20 minutes.Powder mix is modulated into to pasty state, on the 20 g pearlite heatproof steel matrixes that the geometrical dimension that is coated in oil removing, rust cleaning is 100 mm * 200 mm * 3 mm, controls and apply approximately 0.5 mm of bed thickness, coat is dried and is placed on the cladding worktable.The laser work head that employing is connected with optical fiber is done horizontal uniform motion, the fixing method of workpiece, directly titanium aluminium mixed powder and pearlite heatproof steel matrix generation in-situ synthesized reaction are generated to Fe-Ti and the Fe-Al complex phase intermetallic compound anticorrosion layer of rich iron by LASER HEATING, this anticorrosion layer is by the Fe of rich iron
2ti and Fe
3al complex phase intermetallic compound forms.The laser work head is done linear uniform motion at the x direction of principal axis, and the y direction of principal axis is done adjustable step motion.The concrete cladding parameter of LASER HEATING is: laser output power 500 W, and spot diameter 3 mm, laser frequency 10 Hz, pulsewidth 3.2 ms, laser beam flying speed 4 mm/s, overlapping rate 50%, shielding gas is argon gas, shield gas flow rate is 10 ml/s.Anticorrosion layer thickness is 300 μ m ~ 400 μ m, is embedded in the biomass lime-ash after 600 ℃ of high temperature oxidation and corrosion 214 h, and its solidity to corrosion is FeAl+Fe
2al
54.2 times of anticorrosion layer, be shown in Fig. 1 e.
Claims (5)
1. a Fe-Ti and Fe-Al complex phase intermetallic compound anticorrosion layer, it is characterized in that: this anticorrosion layer is consisted of Fe-Ti and the Fe-Al complex phase intermetallic compound of rich iron, and wherein the ratio of aluminium element and titanium elements is 1:19～1:4;
This anticorrosion layer is by the Fe of rich iron
2ti and Fe
3al complex phase intermetallic compound forms.
2. the preparation method of a Fe-Ti claimed in claim 1 and Fe-Al complex phase intermetallic compound anticorrosion layer, it is characterized in that: the method concrete steps are as follows:
By granularity, be 100 orders～200 orders, the aluminium powder of purity >=95% is put into mixed powder machine with titanium valve and is mixed 20 minutes, wherein in titanium aluminium mixed powder, the content of aluminium powder is 5wt%～20wt%, all the other are titanium valve, powder mix is modulated into to pasty state, be coated on the pearlite heatproof steel matrix of oil removing, rust cleaning, coat is dried and to be placed on the cladding worktable, by LASER HEATING, directly titanium aluminium mixed powder and pearlite heatproof steel matrix generation in-situ synthesized reaction are generated to Fe-Ti and the Fe-Al complex phase intermetallic compound anticorrosion layer of rich iron.
3. the preparation method of Fe-Ti according to claim 2 and Fe-Al complex phase intermetallic compound anticorrosion layer, it is characterized in that: the laser work head that described LASER HEATING process employing is connected with optical fiber is done horizontal uniform motion, the fixing method of workpiece prepares anticorrosion layer, the laser work head is done linear uniform motion at the x direction of principal axis, and the y direction of principal axis is done adjustable step motion.
4. the preparation method of Fe-Ti according to claim 2 and Fe-Al complex phase intermetallic compound anticorrosion layer; it is characterized in that: the concrete cladding parameter of described LASER HEATING is: laser output power 500W; spot diameter 3mm; laser frequency 10Hz; pulsewidth 3.2ms, laser beam flying speed 4mm/s, overlapping rate 50%; shielding gas is argon gas, and shield gas flow rate is 10ml/s.
5. the preparation method of Fe-Ti according to claim 2 and Fe-Al complex phase intermetallic compound anticorrosion layer, it is characterized in that: described anticorrosion layer thickness is 300 μ m～400 μ m.
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