CN105369067B - The thermocouple material and preparation method of stable thermometric in oxide isolation - Google Patents
The thermocouple material and preparation method of stable thermometric in oxide isolation Download PDFInfo
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- CN105369067B CN105369067B CN201510740884.9A CN201510740884A CN105369067B CN 105369067 B CN105369067 B CN 105369067B CN 201510740884 A CN201510740884 A CN 201510740884A CN 105369067 B CN105369067 B CN 105369067B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/005—Alloys based on nickel or cobalt with Manganese as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/007—Alloys based on nickel or cobalt with a light metal (alkali metal Li, Na, K, Rb, Cs; earth alkali metal Be, Mg, Ca, Sr, Ba, Al Ga, Ge, Ti) or B, Si, Zr, Hf, Sc, Y, lanthanides, actinides, as the next major constituent
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
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- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
- G01K7/02—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements using thermoelectric elements, e.g. thermocouples
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Abstract
The present invention relates to a kind of thermocouple material of thermometric stable in oxide isolation, the percentage by weight of the material is：The percentage by weight of positive pole NiCoMn alloy material chemical compositions is：Co：14~23%；Mn：1.0~3.0%；Al：1.0~3.0%；Si：0.5~2.0%；Zr≤0.1%；Y≤0.03%；Ni is surplus；The percentage by weight of negative pole NiAlMn alloy material chemical compositions is：Al：1.7~5.0%；Mn：1.0~3.0%；Si：0.1~1.0%；Ce：0~0.7%；Nb≤0.2%；Ni is surplus.The material has the advantages that antioxygenic property is excellent, can be used for a long time in Strong oxdiative environment using the thermocouple of the material for a long time in room temperature to 1150 DEG C of steady operations.
Description
Technical field
The present invention relates to a kind of alloy, the thermocouple material of more particularly to a kind of thermometric stable in oxide isolation and preparation
Method.
Background technology
The stability of thermocouple, because of the environment used, residing surrounding medium is different, and its stability also has very big difference.
For example：In Powder Metallurgy Industry, molybdenum tube is commonly used as protecting tube, in 1600 DEG C of H2Under atmosphere, using effect compared with
It is good.However, above-mentioned molybdenum tube is in an oxidizing atmosphere, very short time just deteriorates because of oxidation.K-type, the N-type commonly used at present in industry
Thermocouple, suitable for being worked in the atmosphere such as air or inert gas, but in chlorine, oxygen, sodium dichromate, potassium permanganate, nitric acid
Deng in Strong oxdiative environment it is long-term in use, its material is oxidized easily and deteriorated, when high temperature is used for a long time, its deterioration will significantly add
It hurry up so that its temperature measurement accuracy is excessively poor.Therefore, the temperature thermocouple material used for a long time in Strong oxdiative environment is studied, is met
The thermocouple requirement used under particular surroundings, as currently more urgent task.
The content of the invention
The purpose of the present invention is situated between aiming at the not enough of existing high temperature Strong oxdiative environment thermocouple material there is provided one kind oxidation
The thermocouple material and preparation method of long-time stable thermometric in matter, the material have antioxygenic property is excellent, energy is long-term exist
The advantages of room temperature to 1150 DEG C of steady operations, can for a long time it be used in Strong oxdiative environment using the thermocouple of the material.
The technical scheme is that：
Stablize the thermocouple material of thermometric in oxide isolation, the percentage by weight of the material is：
The percentage by weight of positive pole NiCoMn alloy material chemical compositions is：
Co：14~23%；Mn：1.0~3.0%；Al：1.0~3.0%；Si：0.5~2.0%；Zr≤0.1%；Y≤
0.03%；Ni is surplus；
The percentage by weight of negative pole NiAlMn alloy material chemical compositions is：
Al：1.7~5.0%；Mn：1.0~3.0%；Si：0.1~1.0%；Ce：0~0.7%；Nb≤0.2%；Ni is
Surplus.
The oxide isolation thermocouple for measuring temperature material, preferable technical scheme is：
The percentage by weight of positive pole NiCoMn alloy material chemical compositions is：
Co：15~20%, Mn：1.5~2.5%, Al：1.5~3.0%, Si：1.0~1.6%, Zr：0.05~
0.08%th, Y：0.01~0.02%；Ni is surplus；
The percentage by weight of negative pole NiAlMn alloy material chemical compositions is：
Al：2.5~4.5%；Mn：1.2~2.0%；Si：0.30~0.80%；Ce：0.15~0.30%；Nb：0.06~
0.1%th, Ni is surplus.
The preparation method of the thermocouple material of stable thermometric, has to state step in oxide isolation：
A) vacuum induction melting：
On weigh each component by the percentage by weight for stating positive and negative electrode alloy material, melted respectively, vacuum >=
Under the conditions of 0.1Pa, vacuum refining 10~30 minutes；Stirring, temperature adjustment obtains ingot casting to middle 1530 DEG C of cast of low temperature；
B) swage：
Ingot casting is heated to 900~1200 DEG C, is incubated 1~3h, is machined to 2.0~φ of φ 18mm；
C) intermediate annealing：
Both positive and negative polarity alloy material after swaging, respectively hydrogen shield annealing heat-treats at 900~1200 DEG C；
D) drawing tube reducing：
By the alloy material drawing tube reducing after annealing, φ 0.02~φ 10mm wire rods are obtained；
E) it is heat-treated：
Wire rod described in step d) is placed in hydrogen shield stove or vacuum drying oven, positive pole：2 are incubated at 1100~1250 ± 5 DEG C
~10 hours, negative pole：2~10 hours are incubated at 1100~1250 ± 5 DEG C.
Fusing described in step a), melts 20~80Kw of power, power is gradually tuned up by small-power to fine melt.
Refining described in step a), its power is 15~35Kw.
C element requirement is less than 0.03% in alloy of the present invention, and high C content will be separated out with iron or aluminium formation compound,
So as to influence the performance of alloy；In addition, S or P also will be controlled strictly as the harmful element in alloy.Added in nickel cobalt (alloy)
Appropriate silicon, cobalt, can adjust the pyroelecthc properties value of alloy, increase inoxidizability and stability；Addition yttrium can improve high temperature
Stability, the service life ratio of the nickel cobalt manganese alloy containing yttrium 0.03% is significantly increased without yttrium person.Nickel aluminium manganese containing cerium is closed
The service life ratio of gold is significantly increased without yttrium person.
The main performance of this alloy is as follows：
1. thermocouple metal material can stablize thermometric in oxide isolation.
2. the thermocouple material of anti-oxidant thermometric steady in a long-term thermoelectrical potential change can be not more than 2 after 1000 DEG C, 720 hours
DEG C, possess long term high temperature stability good in the range of 300 to 1150 DEG C.
The thermocouple material of long-time stable thermometric has that antioxygenic property is excellent, energy in the oxide isolation of the invention
(in the Strong oxdiative medium thermocouple material of long-term stable thermometric, can be the advantages of room temperature to 1150 DEG C of steady operations for a long time
Thermoelectrical potential change is not more than 2 DEG C after 1000 DEG C, 720 hours in the media such as chlorine, oxygen, nitric acid), it can be widely applied to aoxidize ring
Border measuring and controlling instrument table.
Table 1 is the thermoelectrical potential of material of the present invention
The typical thermoelectrical potential of the material of the present invention of table 1
| Temperature/DEG C | Standard electrode potential/mv |
| 300 | 0.386 |
| 400 | 1.63 |
| 500 | 3.42 |
| 600 | 5.37 |
| 700 | 7.42 |
| 800 | 9.40 |
| 900 | 11.44 |
| 1000 | 13.37 |
| 1100 | 15.17 |
Illustrate book
Fig. 1 is the thermoelectrical potential figure of material of the present invention
Embodiment
Embodiment 1
The percentage by weight of positive pole NiCoMn alloy material chemical compositions is：
Co：16.5%th, Mn：2.3%th, Al：1.7%th, Si：1.3%th, Zr：0.08%th, Y：0.02%；Ni is surplus；
The percentage by weight of negative pole NiAlMn alloy material chemical compositions is：
Al：3.1%th, Mn：1.2%th, Si：0.60%th,；Ce：0.27%；Nb：0.1%th, Ni is surplus.
The preparation method of the thermocouple material of anti-oxidant thermometric steady in a long-term, it is characterised in that have following step：
Vacuum induction melting：Each component of alloy is weighed by above-mentioned percentage by weight, 20~80Kw of power is being melted, by
Small-power gradually tunes up power to fine melt, refining power 25Kw, vacuum and is better than under the conditions of 0.1Pa, vacuum refining 20 minutes；Machine
Tool adds electromagnetic agitation temperature adjustment to middle cast cold；
Swage：Ingot casting is heated to 1150 DEG C, is incubated 1h, and processing dimension is φ 10mm；
Intermediate annealing：Alloy material after swaging is carried out to 1150 DEG C of progress hydrogen shield annealing heat-treats respectively；
Drawing tube reducing：Alloy material after annealing is subjected to drawing tube reducing respectively, φ 2mm wire rods are processed into；
Heat treatment：Above-mentioned silk material is placed in hydrogen shield stove or vacuum drying oven, positive pole：5 hours are incubated at 1250 ± 5 DEG C,
Negative pole：5 hours are incubated at 1250 ± 5 DEG C, the thermocouple material of anti-oxidant thermometric steady in a long-term is obtained.
The main performance of this pairing thermocouple metal material is as follows：
1. thermocouple metal material can stablize thermometric in oxide isolation.
2. the thermocouple material of anti-oxidant stable thermometric long-term in oxygen atmosphere medium can be after 1000 DEG C, 720 hours
Thermoelectrical potential change is not more than 2 DEG C, possesses in the range of 300 to 1150 DEG C, good long term high temperature stability.1000 DEG C, 720 hours
Long term test performance is as shown in the table.
Contrasted before and after 2 1000 DEG C of table, 720 hours long term tests
Embodiment 2
The percentage by weight of positive pole NiCoMn alloy material chemical compositions is：
Co：19.5%th, Mn：1.7%th, Al：2.7%th, Si：1.0%th, Zr：0.05%th, Y：0.01%；Ni is surplus；
The percentage by weight of negative pole NiAlMn alloy material chemical compositions is：
Al：4.2%th, Mn：2.0%th, Si：0.30%th,；Ce：0.17%；Nb：0.07%th, Ni is surplus.
The main performance of this pairing thermocouple metal material is as follows：
1. thermocouple metal material can stablize thermometric in oxide isolation.
2. the thermocouple material of anti-oxidant stable thermometric long-term in oxygen atmosphere medium can be after 1000 DEG C, 720 hours
Thermoelectrical potential change is not more than 2 DEG C, possesses in the range of 300 to 1150 DEG C, good long term high temperature stability.
1000 DEG C, 720 hours long term test performances it is as shown in the table.
Contrasted before and after 3 1000 DEG C of table, 720 hours long term tests
Embodiment 3
The percentage by weight of positive pole NiCoMn alloy material chemical compositions is：
Co：15.6%th, Mn：1.6%th, Al：2.3%th, Si：1.6%th, Zr：0.06%th, Y：0.015%；Ni is surplus；
The percentage by weight of negative pole NiAlMn alloy material chemical compositions is：
Al：2.7%th, Mn：1.5%th, Si：0.80%th,；Ce：0.16%；Nb：0.06%th, Ni is surplus.
The main performance of this pairing thermocouple metal material is as follows：
1. thermocouple metal material can stablize thermometric in oxide isolation.
2. the thermocouple material of anti-oxidant stable thermometric long-term in oxygen atmosphere medium can be after 1000 DEG C, 720 hours
Thermoelectrical potential change is not more than 2 DEG C, possesses in the range of 300 to 1150 DEG C, good long term high temperature stability.1000 DEG C, 720 hours
Long term test performance is as shown in the table.
Contrasted before and after 4 1000 DEG C of table, 720 hours long term tests
Claims (5)
1. a kind of thermocouple material of thermometric stable in oxide isolation, it is characterised in that the percentage by weight of the material is：
The percentage by weight of positive pole NiCoMn alloy material chemical compositions is：Co:14~23%；Mn:1.0~3.0%；Al：1.0~
3.0%；Si:0.5~2.0%；Zr≤0.1%；Y≤0.03%；Ni is surplus；
The percentage by weight of negative pole NiAlMn alloy material chemical compositions is：Al：1.7~5.0%；Mn:1.0~3.0%；Si:0.1
~1.0%；Ce：0~0.7%；Nb≤0.2%；Ni is surplus, and the material is made using following methods：
a）Vacuum induction melting：
Each component is weighed by the percentage by weight of above-mentioned positive and negative electrode alloy material, is melted respectively, vacuum >=0.1Pa
Under the conditions of, vacuum refining 10 ~ 30 minutes；Stirring, temperature adjustment obtains ingot casting to middle 1530 DEG C of cast of low temperature；
b）Swage：
Ingot casting is heated to 900~1200 DEG C, is incubated 1~3h, is machined to 2.0~φ of φ 18mm；
c）Intermediate annealing：
Both positive and negative polarity alloy material after swaging, respectively hydrogen shield annealing heat-treats at 900~1200 DEG C；
d）Drawing tube reducing：
By the alloy material drawing tube reducing after annealing, φ 0.02~φ 10mm wire rods are obtained；
e）Heat treatment：
Step d）Described wire rod is placed in hydrogen shield stove or vacuum drying oven, positive pole：2~10 are incubated at 1100~1250 ± 5 DEG C
Hour, negative pole：2~10 hours are incubated at 1100~1250 ± 5 DEG C.
2. oxide isolation thermocouple for measuring temperature material according to claim 1, it is characterised in that the weight hundred of the material
Point ratio is：
The percentage by weight of positive pole NiCoMn alloy material chemical compositions is：
Co:15~20%, Mn:1.5~2.5%, Al：1.5~3.0%, Si:1.0~1.6%, Zr：0.05~0.08%, Y：0.01~
0.02%；Ni is surplus；
The percentage by weight of negative pole NiAlMn alloy material chemical compositions is：
Al：2.5~4.5%；Mn:1.2~2.0%；Si:0.30~0.80%；Ce：0.15~0.30%；Nb：0.06~0.1%,
Ni is surplus.
3. the preparation method of the thermocouple material of stable thermometric in oxide isolation, it is characterised in that have to state step：
a）Vacuum induction melting：
The percentage by weight of positive and negative electrode alloy material weighs each component as described in claim 1 or 2, is melted respectively, very
Under the conditions of reciprocal of duty cycle >=0.1Pa, vacuum refining 10 ~ 30 minutes；Stirring, temperature adjustment obtains ingot casting to middle 1530 DEG C of cast of low temperature；
b）Swage：
Ingot casting is heated to 900~1200 DEG C, is incubated 1~3h, is machined to 2.0~φ of φ 18mm；
c）Intermediate annealing：
Both positive and negative polarity alloy material after swaging, respectively hydrogen shield annealing heat-treats at 900~1200 DEG C；
d）Drawing tube reducing：
By the alloy material drawing tube reducing after annealing, φ 0.02~φ 10mm wire rods are obtained；
e）Heat treatment：
Step d）Described wire rod is placed in hydrogen shield stove or vacuum drying oven, positive pole：2~10 are incubated at 1100~1250 ± 5 DEG C
Hour, negative pole：2~10 hours are incubated at 1100~1250 ± 5 DEG C.
4. method according to claim 3, it is characterised in that：Step a）Described fusing, melts 20~80Kw of power, by
Small-power gradually tunes up power to fine melt.
5. method according to claim 3, it is characterised in that：Step a）Described refining, its power is 15~35Kw.
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| CN108411161B (en) * | 2018-04-25 | 2020-07-17 | 常州市潞城慧热电子厂 | Negative electrode alloy wire of K-type thermocouple and preparation process thereof |
| CN108486418B (en) * | 2018-04-25 | 2020-08-11 | 常州市潞城慧热电子厂 | Alloy wire for thermoelectric generator and preparation process thereof |
| CN114561570A (en) * | 2022-01-17 | 2022-05-31 | 上海中洲特种合金材料股份有限公司 | Nickel-based alloy Inconel601 and preparation method and application thereof |
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| JPH04329843A (en) * | 1991-05-01 | 1992-11-18 | Daido Steel Co Ltd | Manufacture of high strength nickel alloy resisting against seawater corrosion |
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