CN104789815A - High-resistant chromium-nickel electric heating alloy and preparation process thereof - Google Patents
High-resistant chromium-nickel electric heating alloy and preparation process thereof Download PDFInfo
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Abstract
The invention discloses a high-resistant chromium-nickel electric heating alloy and a preparation process thereof. The chemical formula of the high-resistant chromium-nickel electric heating alloy is Cr20Ni80Al; the raw material formula of the high-resistant chromium-nickel electric heating alloy comprises the following components in percentage by weight: less than or equal to 0.03 percent of C, 1.40 to 1.60 percent of Si, less than or equal to 0.30 to 0.50 percent of Mn, less than or equal to 0.020 percent of P, less than or equal to 0.015 percent of S, 20.5 to 21.50 percent of Cr, less than or equal to 0.10 percent of Ti, less than or equal to 3.5 to 3.7 percent of AL, less than or equal to 1.00 percent of Fe, less than or equal to 0.2 percent of Zr, and the balance of Ni and inevitable impurities. According to the high-resistant chromium-nickel electric heating alloy, the electrical resistivity of the electric heating alloy is improved; the electrical characteristics are better; the anti-oxidation performance of an alloy material is improved; the high-temperature strength of the alloy is improved; the service life of the alloy is prolonged.
Description
Technical field
The present invention relates to nichrome technical field, particularly relate to a kind of high resistance chromium nickel electrical heating alloys and preparation technology thereof.
Background technology
Electrical heating alloys divides two large class nickel chromium triangle system's electrical heating alloys and ferrum-chromium-aluminum system electrical heating alloyss, this two be greatly electrical heating alloys respectively owing to organizing difference to have different relative merits: nickel chromium triangle system electrical heating alloys is single phase austenite tissue, its advantage is the stability that high temperature does not exist phase transformation, high hot strength, plasticity, good moldability, good in oxidation resistance, have high creep rupture strength and high temperature life, shortcoming is that resistivity is not as good as ferrum-chromium-aluminum system electrical heating alloys; Ferrum-chromium-aluminum system electrical heating alloys is single phase ferrite, its advantage be can be used in ultrahigh-temperature more than 1100 DEG C environment, there is higher resistivity, good in oxidation resistance, shortcoming is that plasticity is poor, easy-formation, non-weldability, creep rupture strength and work-ing life is not as good as nickel chromium triangle system electrical heating alloys.In order to obtain with the same resistivity of ferrum-chromium-aluminum system electrical heating alloys and the better oxidation-resistance of nickel chromium triangle system electrical heating alloys, creep rupture strength and work-ing life can be obtained.Develop under the demand of particular electrical heating industry and obtained there is the high resistivity the same with 0Cr25Al5 by the adjustment of composition and than the better hot strength of Cr20Ni80, antioxidant property and better creep rupture strength and high temperature creep strength on Cr20Ni80 basis.Its over-all properties is further improved, is widely used in the heating components and parts of special purpose.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the invention provides a kind of high resistance chromium nickel electrical heating alloys and preparation technology thereof, object is resistivity, better electrical specification in order to improve electrical heating alloys, strengthen the antioxidant property of alloy material, carry heavy alloyed hot strength and work-ing life, provide a kind of novel high-resistance electrothermic alloy Cr20Ni80Al.
The technical solution adopted in the present invention is: a kind of high resistance chromium nickel electrical heating alloys, and its chemical formula is Cr20Ni80Al, and its composition of raw materials, count by weight percentage, contained amount composition is as follows:
C：≤0.03%； Si：1.40~1.60 Mn：≤0.30~0.50%
P：≤0.020% S：≤0.015% Cr：20.5~21.50%
Ti ≤0.10% AL ≤3.5~3.7% Fe：≤1.00%
Zr :≤0.2%; Surplus is Ni and inevitable impurity.
The preparation technology of above-mentioned high-resistance electrothermic alloy, its concrete steps are as follows:
A, first by above-mentioned design mix batching;
B, vacuum induction furnace smelting;
C, forging;
D, hot rolling;
E, wire rod are annealed and are carried out pickling;
F, multi-pass: drawing-annealing-drawing;
G, drawing adopt bicycle to carry out.
Further, the refining temperature of step B is 1460-1500 DEG C; Refining time: be greater than 30 minutes, tapping temperature 1500-1520 DEG C.
Further, after step B completes, before step C starts, carry out reconditioning process.
Further, after the forging of step C completes, before the hot rolling of step D starts, ultrasonic test is carried out.
Further, it is 1110 DEG C-1130 DEG C that forging temperature is opened in the forging of step C, final forging temperature >=960 DEG C.
Further, the hot-rolled temperature of step D is 1130 DEG C-1150 DEG C, finishing temperature >=950 DEG C
Again further, step e carries out the temperature of wire rod annealing is 950 DEG C-970 DEG C.
Compared with prior art, the invention has the beneficial effects as follows: 1. reduce original electrical heating alloys C, Si content, add AL, Zr, ree content, reduce C and Si content can increase material plasticity, reduce the brittlement phase formation raising life-span, increase Al content and can increase the resistivity of material, hot strength and antioxidant property, increase Zr and rare earth element can improve the high-order creep rupture strength of material and work-ing life; Adopt the direct smelting process of vacuum induction furnace, composition of steel good uniformity, molten steel are pure, and alloy is fully degassed, and ingot quality is good; Forging adopts heating by electric cooker, and temperature rise rate and soaking time are effectively controlled, and can improve homogeneity and the lumber recovery of the rear crystal grain of forging.Drawing adopts to be carried out at a slow speed, adopts the drawing of multi-pass small deformation amount.(process annealing is bright heat treatment annealing, temperature 1020 DEG C)
Drawing passes is:
Φ8.0*—7.2—6.5*—6.0—5.5—5.0*—4.5—4.0*—3.5—3.0*—2.5—2.2—
2.0-1.8-Φ 1.6*-1.4-1.2-1.0*-0.95, wherein " * " is process annealing passage.
2. compare Cr20Ni80 in GB GB/T1234-2012 standard and there is higher resistivity, work-ing life, good processability, excellent antioxidant performance, thermal expansivity is little, hot strength is good premium properties.
3. adopt vacuum induction furnace smelting, forging, hot rolling adopt heating by electric cooker reduce material oxidation and promote homogeneity.
4. its various use properties is all better than Cr20Ni80 alloy material.The premium propertiess such as high-resistance electrothermic alloy Cr20Ni80Al resistivity of the present invention is high, good processability, excellent antioxidant performance, thermal expansivity is little, hot strength good, high work-ing life.
Electrical heating alloys is the functional material of heat energy by electric energy conversion, and its maximum operation (service) temperature can reach 1400 DEG C, metallurgy, machinery, petrochemical industry, electrically, in the field such as building, military project, household electrical appliances for the manufacture of various electrical heating element.Current electrical heating alloys material oneself become a kind of important engineering alloy material, occupy an important position in national economy.There are Sweden, Russia, Germany, the U.S. and Japan in the country that external production electrical heating alloys quantity is larger.Some country accounts for 50% one 90% due to ratio that nickel resources relatively enriches nickel one Chrome metal powder in its electrical heating alloys.Wherein Sweden is the country that electrical heating alloys output is maximum in the world, its health Dynea Austria GmbH of electrical heating alloys manufacturing enterprise famous under producing and mainly concentrating on Sandvik special steel house flag.
China started to produce the ferroelectric thermalloy product of nickel one chromium one in phase early 1950s.Adopted induction furnace smelting technology at that time.Enter the sixties in 20th century, along with the demand of industrial development to electrical heating alloys constantly increases.Through the developments of nearly 40 years and perfect, establish the electrical heating alloys system with China's feature at present.Can produce now nickel one chromium, nickel one chromium one iron, the electrical heating alloys wire rod of the whole trade mark of iron one chromium one aluminium, band and flat filament.China in 1966 electrical heating alloys annual production is about 7000 tons, and 2005 annual production can reach 150,000 tons.Wherein nickel one chromium and nickel one chromium one iron alloy account for 10%.The output of current China electrical heating alloys ranks first in the world, and is also the country that whole world electrical heating alloys kind is the most complete.China's electrical heating alloys also needs continuous adjustment on product structure.The portioned product quality of Some Enterprises has met or exceeded the quality level of same kind of products at abroad.Along with the development of scientific and technical research and improving constantly of people's living standard, each field constantly increases high-resistance electrothermic alloy demand, and the market outlook of electrical heating alloys are by boundless.
Accompanying drawing explanation
Fig. 1 is the front view of the Service Life of Electrothermal Alloy test of an embodiment;
Fig. 2 is the vertical view of Fig. 1.
Embodiment
In order to deepen the understanding of the present invention, below in conjunction with drawings and Examples, the present invention is further described, and this embodiment, only for explaining the present invention, not forming protection scope of the present invention and limiting.
A kind of high resistance chromium nickel electrical heating alloys, its chemical formula is Cr20Ni80Al, and its composition of raw materials, count by weight percentage, contained amount composition is as follows:
C：≤0.03%； Si：1.40~1.60 Mn：≤0.30~0.50%
P：≤0.020% S：≤0.015% Cr：20.5~21.50%
Ti ≤0.10% AL ≤3.5~3.7% Fe：≤1.00%
Zr :≤0.2%; Surplus is Ni and inevitable impurity.
The preparation technology of above-mentioned high-resistance electrothermic alloy, its concrete steps are as follows:
A, first by above-mentioned design mix batching;
B, vacuum induction furnace smelting;
C, forging;
D, hot rolling;
E, wire rod are annealed and are carried out pickling;
F, multi-pass: drawing-annealing-drawing;
G, drawing adopt bicycle to carry out.
The refining temperature of step B is 1460-1500 DEG C in the present invention; Refining time: be greater than 30 minutes, tapping temperature 1500-1520 DEG C.After step B completes, before step C starts, carry out reconditioning process.
And after the forging of step C completes, before the hot rolling of step D starts, carry out ultrasonic test.And the forging of step C open forging temperature be 1110 DEG C-1130 DEG C, final forging temperature >=960 DEG C.
Hot-rolled temperature for step D is 1130 DEG C-1150 DEG C, finishing temperature >=950 DEG C.The temperature that step e carries out wire rod annealing is 950 DEG C-970 DEG C.
Principle and the effect of composition designed by high-resistance electrothermic alloy Cr20Ni80Al of the present invention are described further:
(1) effect of carbon: carbon is in normal-temperature dissolution amount≤0.01 of nickel chromium triangle system electrical heating alloys, and surplus carbon forms carbide intercrystalline precipitation and causes plasticity to reduce.
(2) effect of chromium: the key element of high alloy high-temperature oxidation resistance, also affects the electrical specification of electric heating.The protection oxide film that alloy is formed at high temperature is primarily of Cr
2o
3composition.With Cr
2o
3the oxide film being master is finer and close, and tack is also comparatively strong, can ensure alloy at high temperature life-time service.When Cr content 20% ~ 23%, alloy has minimum temperature factor.
(3) effect of silicon: silicon produces SiO2 after high temperature oxidation, is distributed in the interface of oxide film and matrix metal, oxygen can be stoped to infiltrate, fall low-alloyed oxidation rate.When silicon and rare earth element exist simultaneously, the effect that silicon improves antioxidant property is more remarkable.Improve the compactness of oxidation-resistant film.
(4) effect of manganese and iron: low-alloyed antioxidant property can fall in manganese and iron, increases oxidation rate.In alloy, content should strictly control to be each defined in Mn0.6%; Below Fe1% can obtain.
(5) effect of nickel: nickel is face-centered cubic lattice, i.e. austenite lattice, its fusing point is higher, and plasticity is good, good toughness, and room temperature is comparatively hard, and high temperature has some strength, and it is not oxidizable in atmosphere, and stable chemical nature, is only soluble in nitric acid.Nickel is parent in Ni-based electrical heating alloys, and the characteristic of itself plays a leading role.The resistivity of nickel is than large 3 one 4 times of aluminium, copper, and linear expansivity is less, and high-temperature oxidation resistant corrodibility is good, is good electrical heating alloys body material.Nickel is austenizer, can provide good over-all properties, can form sosoloid, have higher hot strength most, have high plasticity when normal temperature under good stability high temperature with chromium, good complete processing character.
(6) effect of rare earth element: rare earth is strong reducing property element, adds the antioxidant property that rare earth element may significantly improve alloy in the alloy.There is the effect of protection and purification molten drop in arc transfer process; rare earth and sulphur have very large avidity; in bath, not only there is desoxydatoin; also there is obvious desulfurization and improve the size of sulfide inclusion, form and distribution effect; rare earth element can fall oxygen in alloy, hydrogen richness when adding 0.10 ~ 0.40% rare earth alloy in alloy, significantly improves and improves the antioxidant property of alloy below 1100 DEG C.The present invention's rare earth used is the rare mishmetal of lanthanum, and its content is: La lanthanum 35%, Ce cerium 65%.Add bulk to add.
(7) effect of aluminium: aluminium is the key factor improving antioxidant property, and can significantly improve resistivity, and aluminium can form Ni3Al phase with nickel in nickel chromium triangle system superalloy, improves alloy high-temp intensity.
(8) S, P: be inevitable detrimental impurity element in material, its content is more low better, its Ingredients Weight %, S≤0.015%, P≤0.020%.
(9) adopt the novel high-resistance electrothermic alloy of one (trade mark: Cr20Ni80Al) designed by the present invention compared with existing high-resistance electrothermal alloy material, there is high resistivity, excellent electrical specification, high work-ing life, good processability, excellent antioxidant performance, thermal expansivity is little, hot strength is good premium properties.
Embodiment
Below by employing three horizontal quadrature table L
9(3
4) contrived experiment:
(1) Al, Si, Cr content is on the impact of resistivity of material
According to having in experience and electrical heating alloys handbook, the resistivity that Al, Si, Cr content directly can affect material is described.And adopting three groups of variablees of these three factors to carry out enforcement research according to principle that element design is rolled off the production line, detailed process describes in table 1.
Table 1 Al, Si, Cr content is on the impact of resistivity
Above-mentioned nine groups of embodiment preparation technologies are: select Ni, Cr, Mn, Fe, Si, AL, Ti, Zr content to be greater than 99% pure metal material and manufacture as raw material, all the other elements control in proportion.
(2) material preparation
According to the present invention's five groups of embodiment design mix batchings, vacuum induction furnace smelting (refining temperature: 1460--1500 DEG C; Refining time: be greater than 30 minutes, tapping temperature 1500--1520 DEG C) → reconditioning → forging (opening forging temperature >=1120 DEG C, final forging temperature >=960 DEG C) → ultrasonic test → hot rolling (hot-rolled temperature: 1100--1160 DEG C; Finishing temperature >=950 DEG C) → wire rod annealing (temperature 960 DEG C) pickling → multi-pass (drawing-annealing-drawing); Drawing adopts bicycle to carry out.
(3) service check
According to Standard: GB/T1234-2012 high-resistance electrothermic alloy, diameter is the Ni-Cr alloy silk tensile strength >=650MPa of 0.10-3.00mm, and elongation after fracture is not less than 20%.Following table 2 tensile property all meets GB, but analysis 5#, 7#, 8#, 9# elongation decreases, its toughness index declines to some extent and an intensity rises to some extent therefore can reject this 5 samples.
The mechanical property of the correspondence of the different heat (batch) number of table 2 nine groups of Cr20Ni80Al alloys and content
(4) technological property test
According to Standard: GB/T 1234-2012 high-resistance electrothermic alloy, carry out wrapping test to silk material, after Φ 4.0mm plug is wound around 5 circles, surface does not have the defect such as layering and crackle to occur, every batch time does 3, illustrate the plasticity of alloy and processability fine.
Physicals resistivity measurement
Meter resistance test and resistivity measurement is carried out according to GB/T 1234-2012 standard 6.4.Adopt precision to be not less than the surveying instrument of 0.2%, use me company Kelvin double bridge resistance meter (SB2233) to measure by the regulation of GB/T 6146.Observed value is in table 1, and show that Al content is the key factor affecting resistivity by resistivity measurement result in table 1 and analysis, Cr content is the key factor affecting lumber recovery, and Si content partly can promote resistivity.Need resistance to be the bigger the better according to our design and therefore can reject 1#, 2#, 3#, then can show that 4#, 6# can meet design invention needs according to production lumber recovery and mechanical property integration test situation.
(5) accelerated life test
Foundation is according to Standard: GB T 1234-2012 high-resistance electrothermic alloy life cycle test requirements is pressed as shown in table 3 to 4# and 6# sample.
Table 3 Cr20Ni80 lifetime testing conditions
By testing as depicted in figs. 1 and 2: by diameter be the silk material sample 3 of 0.8mm take the shape of the letter U hang over (electrical heating alloys) longevity test instrument 1 hanger 2 on, experimental temperature is 1200 DEG C. carry out 2min energising by prescribed condition, 2min power-off (difference both it should be not more than 3s) add up by cold cycling the quick life-span that hours is sample.
Life test result shows, gets wherein in two stove 113-0007,113-0009 tetra-samples (two samples got by every stove), and the test life-span, test result was in table 4 all more than 140 hours.
Table 4 life test contrasts
(6) high temperature tension test
4#, 6# sample is selected to carry out its hot strength of contrast test as following table 5 with Cr20Ni80 in production GB/T 1234-2012.
Table 5 4#, 6# sample carries out its hot strength of contrast test with Cr20Ni80 in production GB/T 1234-2012 and contrasts
As can be seen from Table 5, high temperature tension test shows that Cr20Ni80Al is higher than Cr20Ni80 hot strength, and 4# sample is slightly higher than 6# sample hot strength, therefore adopts better 4# sample ingredient to form.
(7) Test Summary
New grades Cr20Ni80Al is studied according to orthogonal design method, adopt national regulations and other multiple detection meanss compare the impact of various composition and technique and draw to draw a conclusion: analyzing Al content is key factor affect resistivity, but too high aluminium content particularly can forge lumber recovery and has a strong impact on event Al content and should control≤4.0% processing lumber recovery; Cr content can be put forward heavy alloyed heat resistance and can improve material pyro-oxidation resistance, but too high Cr can reduce the lumber recovery of material; Si content partly can promote resistivity and can improve material pyro-oxidation resistance, and too high Si red brittleness increases therefore Si content should control≤1.8%.Comprehensive consideration selects the element of Al content 3.6%, Cr content 21%, Si content 1.5% to arrange in pairs or groups.
In addition, the present invention adopts vacuum pouring once shaped forging process, avoid the composition fluctuation problem because electroslag occurs, and its degasifying effect its toughness good has clear improvement.
Detected by above embodiment and alloy mechanical property, novel high-resistance electrothermic alloy Cr20Ni80Al designed by the present invention is compared with existing electrical heating alloys, there is more high resistivity, higher work-ing life, very good processability, excellent antioxidant performance, thermal expansivity is little, hot strength is good premium properties.To enhancing productivity, ensureing quality product, reducing production cost and there is very important economic implications.
What embodiments of the invention were announced is preferred embodiment, but is not limited thereto, those of ordinary skill in the art; very easily according to above-described embodiment, understand spirit of the present invention, and make different amplifications and change; but only otherwise depart from spirit of the present invention, all in protection scope of the present invention.
Claims (8)
1. a high resistance chromium nickel electrical heating alloys, its chemical formula is Cr20Ni80Al, and its composition of raw materials, count by weight percentage, contained amount composition is as follows:
C：≤0.03%； Si：1.40~1.60 Mn：≤0.30~0.50%
P：≤0.020% S：≤0.015% Cr：20.5~21.50%
Ti ≤0.10% AL ≤3.5~3.7% Fe：≤1.00%
Zr :≤0.2%; Surplus is Ni and inevitable impurity.
2. the preparation technology of above-mentioned high-resistance electrothermic alloy, its concrete steps are as follows:
A, to prepare burden by above-mentioned design mix content;
B, vacuum induction furnace smelting;
C, forging;
D, hot rolling;
E, wire rod are annealed and are carried out pickling;
F, multi-pass: drawing-annealing-drawing;
G, drawing adopt bicycle to carry out.
3. preparation technology according to claim 2, is characterized in that: the refining temperature of described step B is 1460-1500 DEG C; Refining time: be greater than 30 minutes, tapping temperature 1500-1520 DEG C.
4. the preparation technology according to Claims 2 or 3, is characterized in that: after described step B completes, before step C starts, and carries out reconditioning process.
5. preparation technology according to claim 2, is characterized in that: after the forging of described step C completes, before the hot rolling of step D starts, carry out ultrasonic test.
6. the preparation technology according to claim 2 or 5, is characterized in that: it is 1110 DEG C-1130 DEG C that forging temperature is opened in the forging of described step C, final forging temperature >=960 DEG C.
7. preparation technology according to claim 2, is characterized in that: the hot-rolled temperature of described step D is 1130 DEG C-1150 DEG C, finishing temperature >=950 DEG C.
8. preparation technology according to claim 2, is characterized in that: the temperature that described step e carries out wire rod annealing is 950 DEG C-970 DEG C.
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| CN108866434A (en) * | 2018-07-02 | 2018-11-23 | 江苏新华合金电器有限公司 | Novel acidproof heat-proof electrothermal alloy 0Cr21Al4ZrTi and preparation method |
| CN111621674A (en) * | 2020-06-08 | 2020-09-04 | 重庆材料研究院有限公司 | Preparation method of microalloyed high-strength precise nickel-chromium resistance alloy material |
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| CN113106298A (en) * | 2021-04-16 | 2021-07-13 | 江苏兄弟合金有限公司 | High-precision heating wire round wire with diameter of 0.03mm and preparation method thereof |
| CN113106298B (en) * | 2021-04-16 | 2022-02-25 | 江苏兄弟合金有限公司 | High-precision heating wire round wire with diameter of 0.03mm and preparation method thereof |
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| CN116179894A (en) * | 2021-11-26 | 2023-05-30 | 江苏新华合金有限公司 | Preparation method of novel high-resistance electrothermal alloy Cr20Ni80Al |
| CN114635062A (en) * | 2022-03-18 | 2022-06-17 | 西安聚能高温合金材料科技有限公司 | Nickel-chromium intermediate alloy |
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Application publication date: 20150722 |