CN106567004B - A kind of toughened glass furnace thermo electric material and its preparation method - Google Patents

A kind of toughened glass furnace thermo electric material and its preparation method Download PDF

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CN106567004B
CN106567004B CN201610980359.9A CN201610980359A CN106567004B CN 106567004 B CN106567004 B CN 106567004B CN 201610980359 A CN201610980359 A CN 201610980359A CN 106567004 B CN106567004 B CN 106567004B
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thermo electric
toughened glass
electric material
glass furnace
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CN106567004A (en
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陶科
尤同吉
李刚
王彦杰
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BEIJING SHOUGANG GITANE NEW MATERIALS Co Ltd
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BEIJING SHOUGANG GITANE NEW MATERIALS Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/04—Making ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

The present invention provides a kind of toughened glass furnace thermo electric material and its preparation method, belongs to technical field of metal material.The chemical composition mass percent of the thermo electric material is：C≤0.05%；Si 1‑2%；Cr 20‑23%;Ni 33‑35%;Al 1‑3%；Ti：0.01‑0.05%；O≤0.0025%；Ce 0.001‑0.005%；Mn 0.5‑1%;P≤0.20%;S≤0.015%;Pb≤0.001%；N≤0.015%;H≤0.0005%;Fe surpluses.The preparation method of the material is using chromic carbide iron, electrolytic nickel, silicon metal, aluminium block, metallic cerium as primary raw material, there is lining electroslag furnace to smelt ∮ 85mm diameter alloy steel rods using three-phase, alloy pig is made through the purification of single-phase electroslag refining furnace, heat turns steel rolling line rolling wire rod, surface coating after pickling, drawing is simultaneously heat-treated, and finally gives the 4mm of diameter 3 oxidizing annealing state heating wire.Material provided by the invention has advantage of the low nickel high resistivity using not de- black oxidation skin.

Description

A kind of toughened glass furnace thermo electric material and its preparation method
Technical field
The present invention relates to technical field of metal material, particularly relates to a kind of toughened glass furnace thermo electric material and its side of producing Method.
Background technology
700 DEG C or so of toughened glass furnace actual work temperature, to reduce cost, many producers use ferrum-chromium-aluminum as electric heating Element.In actual use, Aludirome is found as toughened glass furnace electric heating element material, in safety glass furnaceman During work, often there is electric heating element material surface and the phenomenon that black oxidation skin monoblock comes off occur, as stripping onion-skin Come off in layer, the life-span terminates rapidly.And these oxide skins to come off can pollute glass, or even the ceramic roller of stove is made Into damage.
Using nickel chromium triangle class electrothermal alloy, the phenomenon of similar siderochrome aluminum scaling damage does not occur for surface, but existing The electrothermal alloy of nickel chromium triangle and nickel chromium iron class, mainly includes：Tetra- trades mark of Cr20Ni30Cr20Ni35Cr15Ni60Cr20Ni80, The alloy of two trades mark of Cr15Ni60Cr20Ni80, because it contains very high nickel, price is sufficiently expensive.And Cr20Ni30 and Although two trade mark nickel contents of Cr20Ni35 are relatively low, price can be received by toughened glass furnace enterprise, and also not fall casting skin Phenomenon, but because its resistivity is only 1.0-1.05 Ω .m, it is impossible to meet toughened glass furnace requirement.It is a kind of both low to be badly in need of exploitation Nickel, high resistivity, the new thermo electric material that black oxidation skin is used to fall in toughened glass furnace as electric heating element.
The content of the invention
The present invention provides a kind of toughened glass furnace thermo electric material and its preparation method, solves and uses existing high resistance The ferrum-chromium-aluminum class alloy of rate is easily peeled failure, or and use nickel chromium iron class Langaloy expensive, or resistivity is relatively low The problem of toughened glass furnace electric heating element space requirement can not be met.
The chemical composition mass percent of the thermo electric material is：C≤0.05%；Si 1-2%；Cr 20-23%；Ni 33- 35%；Al 1-3%；Ti：0.01-0.05%；O≤0.0025%；Ce 0.001-0.005%；Mn 0.5-1%；P≤ 0.20%；S≤0.015%；Pb≤0.001%；N≤0.015%；H≤0.0005%；Fe surpluses.
Wherein, the room temperature resistivity of thermo electric material is 1.10-1.14 Ω .m.
The method for producing the toughened glass furnace thermo electric material, key step are as follows：
First, with ingot iron (purity 99.9%), chromic carbide iron VCr6 (chromium content >=60%, carbon≤0.06%), electricity Solve nickel (nickel of Jinchuan 1, purity 99.9%), electrolytic manganese (purity 99.8%), silicon metal (purity is not less than 99.9%), aluminium block (purity is not less than 99.2%) and metallic cerium (purity is not less than 99%) are raw material, and addition Aludirome returns to material, uses 1.8T three-phases have lining electroslag furnace alloy smelting rod iron, and single stove feeds intake total amount 1200-2000kg, wherein, chromic carbide iron 350- 583kg, silicon metal 15-26kg, electrolytic manganese 3-5kg, aluminium block 22-36kg, Aludirome return to material 60-100kg, electrolytic nickel 388-648kg, metallic cerium 2-4kg, ingot iron 386-643kg；Using aluminium, bag Bottom Argon Stirring technology is added in bag, ensure aluminium Distributing homogeneity, 2kg aluminium powder deoxidations are used in metallurgical process；
Secondly, alloy pig is made through the purification of single-phase electroslag refining furnace, insulation is small not less than 12 in the stove not less than 500 DEG C Shi Hou, direct split rolling method, start rolling temperature are not less than 1150 DEG C；
Again, after being rolled into wire rod, 3-5 minutes is soaked into 700 DEG C of molten sodium hydroxides in surface, are not less than with concentration 180g/L sulfuric acid washing is no less than 40 minutes, is washed down with water.Wire rod after pickling, 1.2 anhydrous slufuric acid is not less than with proportion Sodium solution coating, in solution plus 1% tertiary sodium phosphate, coating is no less than 5 minutes every time more than 80 DEG C, repeatedly for three times, after coating It is sent into the drying oven drying that temperature is 150 DEG C to be no less than 35 minutes, carries out drawing afterwards；Drawing is using calcium basis soap powder as lubrication Agent, in concentration it is 10% after pulling out, temperature is after immersion is no less than 60 minutes in 80 DEG C of sodium hydroxide solution, is washed down with water；
Finally, drawing finished product is heat-treated using well formula heat-treatment furnace, not small in 950-1050 DEG C of temperature range insulation After 3 hours, water cooling of coming out of the stove, diameter 3-4mm oxidizing annealing state heating wire is obtained.In bag BOTTOM ARGON BLOWING, strong argon blowing time 3 is divided Clock, soft argon blowing to cast terminate.
The material is mainly used for coiling toughened glass furnace electric heating element, the surface work of toughened glass furnace electric heating element Temperature is actual at 700-900 DEG C, if in this temperature range from siderochrome aluminium class material as electric heating element, because of its generation The more loose easily decortication of oxide-film, causes short life and pollution glass.It is expensive from the higher nickel chromium triangle class alloy of nickel content, The electric heating element resistivity of low nickel is again too low.There is material provided by the invention low nickel high resistivity to use not de- black oxidation skin Advantage.
The above-mentioned technical proposal of the present invention has the beneficial effect that：
(1) in 700-900 DEG C of work of toughened glass furnace, material is less prone to decortication compared with ferrum-chromium-aluminum class electric heating element and lost Effect.Material provided by the invention is non-brittle for a long time after use, and weldability can be better than Aludirome.
(2) compared with nichrome Cr15Ni60Cr20Ni80, containing relatively low nickel 33-35%, be advantageous to save nickel Resource and client cost.Compared with Cr20Ni30Cr20Ni35 alloys, there is higher resistivity (Cr20Ni30Cr20Ni35 electricity Resistance rate is 1.04 Ω .m), the resistivity of alloy of the present invention is 1.1-1.14 Ω .m, can meet that toughened glass furnace component space designs Need.
(3) 900 DEG C of 100 hourly average oxidation weight gain rate of material of the present invention is 0.129g/m2.h, 100 hours oxidation weight gains Experiment is compared with ferrum-chromium-aluminum without decortication phenomenon.
(4) room temperature does tensile strength and is not more than 750MPa, is easily wound in electric heating element.
Embodiment
To make the technical problem to be solved in the present invention, technical scheme and advantage clearer, below in conjunction with specific implementation Example is described in detail.
The present invention is directed to easily to be peeled failure using the ferrum-chromium-aluminum class alloy of existing high resistivity, and uses nickel chromium iron class height Either nickel alloy is expensive, or resistivity relatively low the problem of can not meeting toughened glass furnace electric heating element space requirement, A kind of toughened glass furnace thermo electric material and its preparation method are provided.
The chemical composition mass percent of the thermo electric material is：C≤0.05%；Si 1-2%；Cr 20-23%；Ni 33- 35%；Al 1-3%；Ti：0.01-0.05%；O≤0.0025%；Ce 0.001-0.005%；Mn 0.5-1%；P≤ 0.20%；S≤0.015%；Pb≤0.001%；N≤0.015%；H≤0.0005%；Fe surpluses.
Wherein, the room temperature resistivity of thermo electric material is 1.10-1.14 Ω .m.
The preparation method of the toughened glass furnace thermo electric material, it is specific as follows：
First, with ingot iron (purity 99.9%) chromic carbide iron VCr6 (chromium content >=60%, carbon≤0.06%), electrolysis Nickel (nickel of Jinchuan 1, purity 99.9%), electrolytic manganese (purity 99.8%), silicon metal (purity is not less than 99.9%), aluminium block are (pure Degree is not less than 99.2%) and metallic cerium (purity is not less than 99%) is raw material, has lining electroslag furnace alloy smelting using 1.8T three-phases Rod iron, single stove feed intake total amount 2000kg, VCr6 583kg, silicon metal 26kg, electrolytic manganese 5kg, aluminium block 36kg, and Aludirome returns Feed back 100kg, electrolytic nickel 648kg, metallic cerium 4kg, ingot iron 643kg.Using in bag plus aluminium, bag Bottom Argon Stirring technology, Ensure aluminium distributing homogeneity, 2kg aluminium powder deoxidations are used in metallurgical process；
Secondly, alloy pig is made through the purification of single-phase electroslag refining furnace, insulation is small not less than 12 in the stove not less than 500 DEG C Shi Hou, direct split rolling method, start rolling temperature are not less than 1150 DEG C；
Again, after being rolled into wire rod, 3-5 minutes is soaked into 700 DEG C of molten sodium hydroxides in surface, are not less than with concentration 180g/L sulfuric acid washing is no less than 40 minutes, is washed down with water.Wire rod after pickling, 1.2 anhydrous slufuric acid is not less than with proportion Sodium solution coating, in solution plus 1% tertiary sodium phosphate, coating is no less than 5 minutes every time more than 80 DEG C, repeatedly for three times, after coating It is sent into the drying oven drying that temperature is 150 DEG C to be no less than 35 minutes, carries out drawing afterwards；Drawing is using calcium basis soap powder as lubrication Agent, in concentration it is 10% after pulling out, temperature is after immersion is no less than 60 minutes in 80 DEG C of sodium hydroxide solution, is washed down with water；
Finally, drawing finished product is heat-treated using well formula heat-treatment furnace, not small in 950-1050 DEG C of temperature range insulation After 3 hours, water cooling of coming out of the stove, diameter 3-4mm oxidizing annealing state heating wire is obtained.
Specific embodiment situation such as following table.
First, respectively each batch assay chemistry used composition is taken in rolling process
2nd, in finished silk sampling and testing room temperature resistivity, normal temperature mechanical property and 900 DEG C of oxidation weight gain rates
Described above is the preferred embodiment of the present invention, it is noted that for those skilled in the art For, on the premise of principle of the present invention is not departed from, some improvements and modifications can also be made, these improvements and modifications It should be regarded as protection scope of the present invention.

Claims (4)

  1. A kind of 1. toughened glass furnace thermo electric material, it is characterised in that：The chemical composition mass percent of the thermo electric material is：C ≤ 0.05%；Si 1-2%；Cr 20-23%；Ni 33-35%；Al 1-3%；Ti：0.01-0.05%；O≤0.0025%； Ce 0.001-0.005%；Mn 0.5-1%；P≤0.20%；S≤0.015%；Pb≤0.001%；N≤0.015%；H≤ 0.0005%；Fe surpluses；
    The method for producing above-mentioned toughened glass furnace thermo electric material is as follows：
    First, using the ingot iron of purity 99.9%, chromic carbide iron, electrolytic nickel, electrolytic manganese, silicon metal, aluminium block and metallic cerium as Raw material, addition Aludirome return to material, have lining electroslag furnace alloy smelting rod iron using 1.8T three-phases, single stove feeds intake total amount 1200-2000kg, wherein, chromic carbide iron 350-583kg, silicon metal 15-26kg, electrolytic manganese 3-5kg, aluminium block 22-36kg, siderochrome Aluminium alloy returns to material 60-100kg, electrolytic nickel 388-648kg, metallic cerium 2-4kg, ingot iron 386-643kg；Add using in bag Aluminium, bag Bottom Argon Stirring technology, ensure aluminium distributing homogeneity, aluminium powder deoxidation is used in metallurgical process；
    Secondly, alloy pig is made through the purification of single-phase electroslag refining furnace, insulation was not less than 12 hours in the stove not less than 500 DEG C Afterwards, direct split rolling method, start rolling temperature are not less than 1150 DEG C；
    Again, after being rolled into wire rod, 3-5 minutes is soaked into 700 DEG C of molten sodium hydroxides in surface, are not less than 180g/L with concentration Sulfuric acid washing be no less than 40 minutes, washed down with water；Wire rod after pickling, 1.2 anhydrous slufuric acid sodium solution is not less than with proportion Coating, in solution plus 1% tertiary sodium phosphate, coating is no less than 5 minutes every time more than 80 DEG C, repeatedly for three times, temperature is sent into after coating Spend and be no less than 35 minutes for 150 DEG C of drying oven drying, carry out drawing afterwards；Drawing, as lubricant, is drawn using calcium basis soap powder In concentration it is 10% after pulling out, temperature is after immersion is no less than 60 minutes in 80 DEG C of sodium hydroxide solution, is washed down with water；
    Finally, drawing finished product is heat-treated using well formula heat-treatment furnace, small not less than 3 in 950-1050 DEG C of temperature range insulation Shi Hou, water cooling of coming out of the stove, obtain diameter 3-4mm oxidizing annealing state heating wire.
  2. 2. toughened glass furnace thermo electric material according to claim 1, it is characterised in that：The room temperature electricity of the thermo electric material Resistance rate is 1.10-1.14 Ω .m.
  3. 3. toughened glass furnace thermo electric material according to claim 1, it is characterised in that：The alloy steel rod of the smelting is straight Footpath is ∮ 85-90mm.
  4. 4. toughened glass furnace thermo electric material according to claim 1, it is characterised in that：In the bag BOTTOM ARGON BLOWING, blow by force 3 minutes argon time, soft argon blowing to cast terminates.
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CN112575249A (en) * 2020-10-29 2021-03-30 江苏新核合金科技有限公司 Electrothermal alloy material and preparation method thereof
CN112575247A (en) * 2020-10-29 2021-03-30 江苏新核合金科技有限公司 Preparation method of electrothermal alloy for high-voltage resistance box
CN115652169A (en) * 2022-11-10 2023-01-31 张家港快工品科技有限公司 Preparation method of electric resistance band for heat treatment equipment
CN116005038B (en) * 2022-12-08 2024-08-02 北京首钢吉泰安新材料有限公司 Nickel-chromium-iron alloy and preparation method thereof

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CN101595236A (en) * 2007-01-31 2009-12-02 蒂森克鲁普德国联合金属制造有限公司 Iron-nickel-chromium-silicon alloy
CN101892436A (en) * 2009-05-19 2010-11-24 朱耀霄 Fe-Ni-Cr-Al system electrothermal alloy and manufacturing method and application thereof

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JPS5844145B2 (en) * 1979-07-16 1983-10-01 株式会社リケン Austenitic electric heating alloy
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CN101892436A (en) * 2009-05-19 2010-11-24 朱耀霄 Fe-Ni-Cr-Al system electrothermal alloy and manufacturing method and application thereof

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