CN105154776B - Electrothermal alloy material with excellent high temperature oxidation resistance and preparation method thereof - Google Patents

Electrothermal alloy material with excellent high temperature oxidation resistance and preparation method thereof Download PDF

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CN105154776B
CN105154776B CN201510516555.6A CN201510516555A CN105154776B CN 105154776 B CN105154776 B CN 105154776B CN 201510516555 A CN201510516555 A CN 201510516555A CN 105154776 B CN105154776 B CN 105154776B
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alloy material
high temperature
electrothermal alloy
oxidation resistance
excellent high
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CN105154776A (en
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倪高金
肖学山
刘青欢
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JIANGSU JINDA ELECTRIC HEATING ELECTRICAL APPLIANCE CO Ltd
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JIANGSU JINDA ELECTRIC HEATING ELECTRICAL APPLIANCE CO Ltd
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Abstract

The invention discloses a kind of electrothermal alloy material with excellent high temperature oxidation resistance and preparation method thereof, the electrothermal alloy material has following composition and mass percent(%):C≤0.06, Cr:19.5 23.5, Al:5.5 6.5, N≤0.03, Si≤0.5, Mn≤0.5, P≤0.03, S≤0.03, Co:0.5 2.5, Nb:0.1 1.0, Zr:0.1 0.25, Y:0.02 0.2, surplus is Fe and inevitable impurity;Using vacuum induction melting technique, cast molding after melting is finally made through hot forging, hot rolling, dynamic recrystallization treatment, cold rolling and cold-drawn.The electrothermal alloy material not only overcomes the high-temperature embrittlement of existing Fe Cr Al alloys, improves inoxidizability, and its heat resistance is also improved, resistance to high temperature corrosion ability enhancing, with excellent combination property.

Description

Electrothermal alloy material with excellent high temperature oxidation resistance and preparation method thereof
Technical field
The invention belongs to steel alloy material technical field, and in particular to a kind of electrothermal alloy material and preparation method thereof.
Background technology
Fe-Cr-Al electrothermal alloys belong to superhigh temperature rank electrothermal alloy, because containing substantial amounts of chromium, aluminium element in alloy, close Gold utensil has excellent high-temperature oxidation resistance.Fe-Cr-Al electrothermal alloys are the most widely used electrothermal alloys of China, and it has Good heat resistance, high temperature oxidation resistance, resistivity coefficient are larger, and temperature-coefficient of electrical resistance is small, power stability, in oxidizing atmosphere The fine and close Al2O3 and Cr2O3 oxide-films of middle generation, play a good protection, and cheap, are primarily used to manufacture Various medium and high temperature heating insets.High resistivity can effectively convert electrical energy into heat energy, can also save electric heating material Material.Fe-Cr-Al electrothermal alloys typically contain 13-27wt.%Cr, and 3.5-7wt.%Al, matrix has body-centered cubic structure.Often Fe-Cr-Al alloy materials have 0Cr23Al5,0Cr21Al6 and 0Cr27Al7Mo2 etc..The ratio that current Fe-Cr-Al alloys are done The model Kanthal A-1 alloys that preferably the KANTHAL companies of Sweden produce, its temperature in use can reach 1400 °C, and with very high resistivity and excellent high-temperature oxidation resistance;And China production such as 0Cr27Al7Mo2 Normal temperature in use compares also a certain distance with same kind of products at abroad at 1200-1300 °C.The Fe-Cr-Al of domestic production Electrothermal alloy elevated temperature strength is low, easily produces the deformation of creep, after applied at elevated temperature, and crystal grain is grown up significantly, abnormal thick crystal grain Easily cause the brittle failure of heater.At present, when Fe-Cr-Al electrothermal alloys are used to manufacture the electric furnace heating wire of heating furnace, what is existed is main Problem is exactly that service life is too short.If replacing Fe-Cr-Al alloys with Ni-Cr alloy, temperature in use is difficult to meet;If with hardly possible Molten metal or non-metal electric heating body substitution, price is again expensive.Therefore, the development of industrial furnace is in the urgent need to developing new Fe-Cr- Al electrothermal alloys, improve its elevated temperature strength, inoxidizability and service life.
The content of the invention
It is an object of the invention to provide a kind of electrothermal alloy material with excellent high temperature oxidation resistance and its preparation Electrothermal alloy in method, the composition range is used primarily in powder metallurgy sintering furnace, high temperature of the operating temperature at 1000-1300 °C The electric heating element of heat-treatment furnace etc..
The present invention is achieved by the following technical solution:
Electrothermal alloy material with excellent high temperature oxidation resistance, with following composition and mass percent(%):C ≤ 0.06, Cr:19.5-23.5, Al:5.5-6.5, N≤0.03, Si≤0.5, Mn≤0.5, P≤0.03, S≤0.03, Co: 0.5-2.5, Nb:0.1-1.0, Zr:0.1-0.25, Y:0.02-0.2, surplus is Fe and inevitable impurity.
With following composition and mass percent(%):0.025 < C≤0.06, Cr:21.6-23.5, Al:5.5-6.5, N≤0.03, Si≤0.5,0.21 < Mn≤0.5, P≤0.03, S≤0.03, Co:0.5-2.5, Nb:0.1-1.0, Zr:0.16- 0.25, Y:0.02-0.2, surplus is Fe and inevitable impurity.
The preparation method of the electrothermal alloy material with excellent high temperature oxidation resistance, using vacuum induction melting work Cast molding after process, melting, different-diameter needed for being finally made through hot forging, hot rolling, dynamic recrystallization treatment, cold rolling and cold-drawn Electrothermal alloy material.After steel in the composition range is after cold rolling and cold-drawn, increase in the oxidation in 360 hours of 1300 °C of isothermal oxidations It is less than 10mg/cm again2, and its oxidation weight gain curve follows parabola rule.
Al is added in the form of pure Al, and Zr is added in the form of pure Zr, and Co is added in the form of pure Co, and Cr passes through micro- carbon chromium The form of iron is added, and Y is added in the form of Fe-Y intermediate alloys, and Nb is added with Fe-Nb alloy forms.
The mechanism of the present invention is as described below:The appropriate Zr of addition and Rare Earth Y can promote the formation of protective oxide film, show The low-alloyed isothermal oxidation weightening of drop is write, the resistance to flaking of oxide-film is improved, improves antioxygen of the alloy under harsh service condition Change performance;And it can suppress crystal grain with crystal grain thinning, pinning crystal boundary and grow up, so that it is brilliant to slow down Fe-Cr-Al electrothermal alloys high temperature The speed of grain roughening, extends high temperature life.
The present invention has the advantages that compared with prior art:
The present invention improves the brittle energy of inoxidizability, high temperature life and anti-heater by adding Zr and Rare Earth Y Power.The present invention relates to a kind of electrothermal alloy material with excellent high temperature oxidation resistance containing Zr and Rare Earth Y, not only overcome The high-temperature embrittlement of existing Fe-Cr-Al alloys, improves inoxidizability, and its heat resistance is also improved, resistance to high temperature corrosion Ability strengthens, with excellent combination property.Addition certain Zr and Y can reduce the speed of Fe-Cr-Al Aluminum in Alloy consumption Degree, improves high temperature oxidation resistance and elevated temperature strength, improves service life.Electrothermal alloy material in the range of present component is cold Roll with after cold-drawn, be less than 10mg/cm in 1300 °C of isothermal oxidations, 360 hours oxidation weight gains2, and its oxidation weight gain curve follows throwing Thing line gauge is restrained.
Brief description of the drawings
Fig. 1 is the electrothermal alloy of embodiment 1 and embodiment 2 in embodiment in 1300 °C of isothermal oxidations 360 hours Oxidation weight gain curve.
Embodiment
Technical scheme is described in further detail below by embodiment, and with reference to accompanying drawing.
Embodiment 1:
In the present embodiment, using the composition and mass percent of the electrothermal alloy material with excellent high temperature oxidation resistance It is as follows:
Cr 21.23%
Al 6.03%
Co 1.33%
Zr 0.14%
Rare Earth Y 0.04%
Nb 0.43%
Mn 0.23%
Si 0.18%
C 0.016%
N 0.015%
S 0.008%
P 0.009%
Fe surpluses
Using vacuum induction melting, through comprehensive metering calculate and dispensing melting after, cast molding, then through hot forging, hot rolling, again Crystallization heat treatment, cold rolling and cold-drawn, are finally made the electricity with excellent high temperature oxidation resistance containing Zr and Rare Earth Y alloying element Thermalloy material, it is about 6.98 mg/cm in 1300 °C of isothermal oxidations, 360 hours oxidation weight gains2, and its oxidation weight gain curve Follow parabola rule.
Embodiment 2:
Electrothermal alloy material does not include Zr and Rare Earth Y alloying element, the composition of electrothermal alloy material and again in the present embodiment Measure percentage as follows:
Cr 21.34%
Al 5.98%
Co 1.41%
Nb 0.48%
Mn 0.21%
Si 0.19%
C 0.016%
N 0.017%
S 0.009%
P 0.007%
Fe surpluses
Using vacuum induction melting, through comprehensive metering calculate and dispensing melting after, cast molding, then through hot forging, hot rolling, again Crystallization heat treatment, cold rolling and cold-drawn, the final electrothermal alloy material being made without Zr and Rare Earth Y alloying element, it is at 1300 °C 360 hours oxidation weight gains of isothermal oxidation are about 12.17 mg/cm2, its oxidation weight gain curve is also in compliance with parabola rule.
Shown in Figure 1, the electrothermal alloy without Zr and Rare Earth Y is after 1300 °C of isothermal processes 360 hours in embodiment 2 Oxidation weight gain is higher than in embodiment 1 oxidation weight gain containing appropriate Zr and Rare Earth Y alloying element electrothermal alloy.
Embodiment 3:
In the present embodiment, using the composition and mass percent of the electrothermal alloy material with excellent high temperature oxidation resistance It is as follows:
Cr 22.65%
Al 5.68%
Co 0.6%
Zr 0.18%
Rare Earth Y 0.04%
Nb 0.12%
Mn 0.33%
Si 0.18%
C 0.029%
N 0.015%
S 0.008%
P 0.009%
Fe surpluses
Using vacuum induction melting, through comprehensive metering calculate and dispensing melting after, cast molding, then through hot forging, hot rolling, again Crystallization heat treatment, cold rolling and cold-drawn, are finally made the electricity with excellent high temperature oxidation resistance containing Zr and Rare Earth Y alloying element Thermalloy material, it is about 7.39 mg/cm in 1300 °C of isothermal oxidations, 360 hours oxidation weight gains2, and its oxidation weight gain curve Follow parabola rule.
Embodiment 4:
In the present embodiment, using the composition and mass percent of the electrothermal alloy material with excellent high temperature oxidation resistance It is as follows:
Cr 23.45%
Al 6.33%
Co 2.4%
Zr 0.23%
Rare Earth Y 0.04%
Nb 0.96%
Mn 0.46%
Si 0.18%
C 0.057%
N 0.015%
S 0.008%
P 0.009%
Fe surpluses
Using vacuum induction melting, through comprehensive metering calculate and dispensing melting after, cast molding, then through hot forging, hot rolling, again Crystallization heat treatment, cold rolling and cold-drawn, are finally made the electricity with excellent high temperature oxidation resistance containing Zr and Rare Earth Y alloying element Thermalloy material, it is about 8.01 mg/cm in 1300 °C of isothermal oxidations, 360 hours oxidation weight gains2, and its oxidation weight gain curve Follow parabola rule.
Electrothermal alloy material of the present invention with excellent high temperature oxidation resistance is in 1250-1300 °C of isothermal antioxygenic property It is substantially better than the high temperature oxidation resistance for the electrothermal alloy material for not adding Zr and Rare Earth Y element.Such tool containing Zr and Rare Earth Y The electrothermal alloy material for having excellent high temperature oxidation resistance may be used as sintering furnace, Re Chu of the operating temperature at 1000-1300 °C Manage the electric heating element of stove etc..
Embodiment does not constitute the limit to the scope of the present invention only to facilitate understand technical scheme System, it is every without departing from any letter perhaps made in technical solution of the present invention according to the technical spirit of the present invention to above scheme Single modification, equivalent variations and modification, still fall within the scope of the present invention.

Claims (3)

1. the electrothermal alloy material with excellent high temperature oxidation resistance, it is characterised in that:With following composition and quality hundred Divide than (%):C≤0.06, Cr:19.5-21.34, Al:5.5-6.5,0.015≤N≤0.03, Si≤0.19, Mn≤0.23, P ≤ 0.03, S≤0.03, Co:1.33-2.5, Nb:0.1-0.48, Zr:0.1-0.25, Y:0.02-0.2, surplus is Fe and can not The impurity avoided.
2. there is the preparation method of the electrothermal alloy material of excellent high temperature oxidation resistance, its feature according to claim 1 It is:Using vacuum induction melting process, cast molding after melting, through hot forging, hot rolling, dynamic recrystallization treatment, it is cold rolling and The electrothermal alloy material of different-diameter needed for cold-drawn is finally made.
3. there is the preparation method of the electrothermal alloy material of excellent high temperature oxidation resistance, its feature according to claim 2 It is:Al is added in the form of pure Al, and Zr is added in the form of pure Zr, and Co is added in the form of pure Co, and Cr passes through chromic carbide iron Form add, Y adds in the form of Fe-Y intermediate alloys, and Nb is with the addition of Fe-Nb alloy forms.
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CN106350766A (en) * 2016-08-27 2017-01-25 江苏金达电热电器有限公司 Aluminized Ni-Cr alloy resistance wire and preparing method thereof
CN107454689A (en) * 2017-07-29 2017-12-08 江苏华海冶金机械设备有限公司 Anti-oxidant electrothermal radiation tube
CN109207870A (en) * 2018-11-16 2019-01-15 陈万勤 A kind of Fe-Cr-Al system alloy and its production method
CN113073234B (en) * 2021-03-23 2022-05-24 成都先进金属材料产业技术研究院股份有限公司 Nickel-chromium high-resistance electrothermal alloy and preparation method thereof

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CN101892434A (en) * 2010-06-12 2010-11-24 北京首钢吉泰安新材料有限公司 Ultra-high temperature electrothermal alloy and preparation method thereof
CN102912238A (en) * 2012-11-22 2013-02-06 丹阳兄弟合金有限公司 Electrothermal alloy
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CN104726778A (en) * 2015-03-25 2015-06-24 上海大学兴化特种不锈钢研究院 Rare-earth La containing electrothermal alloy material having excellent high-temperature oxidation resistance

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Denomination of invention: Electrothermal alloy material with excellent high temperature oxidation resistance and its preparation method

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