CN110760764B - Iron-nickel-based Al-containing high-strength constant-expansion alloy - Google Patents

Iron-nickel-based Al-containing high-strength constant-expansion alloy Download PDF

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CN110760764B
CN110760764B CN201911072151.7A CN201911072151A CN110760764B CN 110760764 B CN110760764 B CN 110760764B CN 201911072151 A CN201911072151 A CN 201911072151A CN 110760764 B CN110760764 B CN 110760764B
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王方军
刘应龙
王东哲
刘敏
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Chongqing Materials Research Institute 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
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/005—Modifying the physical properties by deformation combined with, or followed by, heat treatment of ferrous alloys
    • 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
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • 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
    • 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
    • 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
    • C22C38/52—Ferrous alloys, e.g. steel alloys containing chromium with nickel with cobalt

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Abstract

The invention relates to an iron-nickel-based Al-containing high-strength constant-expansion alloy which is characterized by comprising the following components in percentage by weight: ni: 35.0-35.9.0%; 0.4 to 0.6 percent of Nb; co: 0.8-1.2%; al: 0.10-0.30%; cr: 0.50-0.75%; ti is less than or equal to 0.1 percent; c is less than or equal to 0.03 percent; si is less than or equal to 0.40 percent; mn is less than or equal to 0.40 percent; s is less than or equal to 0.001 percent; p is less than or equal to 0.008 percent; the balance being Fe. The average linear expansion coefficient alpha of the alloy10‑30℃＝(1.3～1.8)×10‑6The alloy has high room temperature mechanical strength and dynamic elastic modulus, and can be applied to special requirements, such as aerospace engineering precision instruments and other precision instruments.

Description

Iron-nickel-based Al-containing high-strength constant-expansion alloy
Technical Field
The invention relates to a metal material, in particular to an iron-nickel-based Al-containing high-strength constant-expansion alloy.
Background
The expansion-determining alloy is mainly characterized in that the expansion coefficient of the alloy is close to that of sealed materials such as glass, ceramics and the like in a certain temperature range, so that the effect of matched (or unmatched) sealing can be achieved. Therefore, it may be called a sealing alloy. It is widely used as a lead and structural material in stationary camera lens supports, tubes, transistors and integrated circuits. The matched sealing means that the difference of the expansion coefficients of the alloy and the material to be sealed is less than 10% in the range from the sealing temperature to the room temperature, and if the difference of the expansion coefficients of the alloy and the material to be sealed is too large, large internal stress is easily generated, and the 'explosion' and gas leakage are caused.
The typical average linear expansion coefficient of the prior constant expansion alloy is more than or equal to 2.0 multiplied by 10 within the using temperature range-6/℃。
In order to meet the requirements of the new generation of high-precision and high-performance precision equipment for aerospace engineering on special constant expansion alloy, an average linear expansion coefficient alpha is required10-30℃＝(1.3～1.8)×10-6Very narrow range of constant expansion alloys per deg.C. Meanwhile, the alloy must meet the high mechanical property requirement: room temperature yield strength Rp0.2Not less than 300MPa, and the dynamic elastic modulus E not less than 140 GPa.
At present, no alloy meeting the performance is available on the market, and no document is recorded and reported.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an iron-nickel-based Al-containing high-strength constant-expansion alloy, which has an average linear expansion coefficient alpha10-30℃＝(1.3～1.8)×10-6The alloy has high room temperature mechanical strength and dynamic elastic modulus, and can be applied to special requirements, such as aerospace engineering precision instruments and other precision instruments.
In order to achieve the purpose, the invention adopts the following technical scheme:
an iron-nickel-based Al-containing high-strength constant-expansion alloy comprises the following components in percentage by weight: ni: 35.0-35.9%; 0.4 to 0.6 percent of Nb; co: 0.8-1.2%; al: 0.10-0.30%; cr: 0.50-0.75%; ti is less than or equal to 0.1 percent; c is less than or equal to 0.03 percent; si is less than or equal to 0.40 percent; mn is less than or equal to 0.40 percent; s is less than or equal to 0.001 percent; p is less than or equal to 0.008 percent; the balance being Fe.
The better technical scheme is that the alloy comprises the following components in percentage by weight: ni: 35.2-35.8%; 0.45 to 0.55 percent of Nb; co: 0.85-1.0%; al: 0.15-0.20%; cr: 0.65-0.72%; ti: 0.09-0.75%; c: 0.01-0.02%; si: 0 to 0.3 percent; mn: 0 to 0.3 percent; s: 0 to 0.001 percent; p: 0 to 0.008 percent; the balance being Fe.
The better technical scheme is that the alloy comprises the following components in percentage by weight: ni: 35.8 percent; nb: 0.55 percent; co: 1.0 percent; al: 0.15 percent; cr: 0.72 percent; ti: 0.09%; c: 0.02 percent; si: 0.3 percent; mn: 0.3 percent; the balance being Fe.
The better technical scheme is that the alloy comprises the following components in percentage by weight: ni: 35.20 percent; nb:0.45 percent; co: 0.85 percent; al: 0.20 percent; cr: 0.65 percent; ti: 0.75 percent; c: 0.01 percent; si: 0.10 percent; mn: 0.20 percent; the balance being Fe.
The high-strength fixed expansion alloy is prepared by the following method:
a) and smelting
Taking the components according to the proportion, melting the alloy by vacuum induction, and when carrying out the vacuum induction melting, adopting a secondary refining process, wherein the primary refining temperature is slightly higher and the time is slightly longer;
first refining
Charging a bottom material into the furnace: fe. And Co, Cr, Nb and Ni are smelted under the conditions that the temperature is higher than 1550 ℃ and the vacuum degree is controlled to be better than 10Pa, and the smelting is carried out according to the time of 0.6-0.8 min/kg.
Second refining
The second refining adopts low-temperature short-time refining, the rest alloy elements are put into a furnace, sufficient mechanical and electromagnetic stirring is carried out after feeding, the alloy is smelted at the temperature of more than 1520 ℃ according to the time of 0.4-0.6 min/kg, after the alloy is completely smelted, the vacuum degree is controlled to be better than 2Pa, argon is filled for protection, molten steel is kept stand, the temperature is adjusted to 1480 ℃, and then rapid pouring is carried out;
then electroslag remelting is carried out, CaF is adopted during remelting2-CaO2-Al2O3Ternary slag system (see patent No. CN 102127652A);
the remelting temperature is about 1700 ℃, the remelting speed is about 0.6-1.0 Kg/min, the depth, the current and the voltage of a slag pool are properly controlled to ensure the stability of the remelting process, and thermal feeding needs to be carried out for 4-6 times before the smelting is finished, so that the alloy steel ingot is finally obtained.
b) Forging the steel plate
The alloy hot forging temperature is 800-1120 ℃, and the heat preservation time is 120-180 minutes (the heat preservation time is determined according to the size of the steel ingot).
c) And solution treatment
The solution treatment system of the alloy comprises heat preservation temperature of 700-850 ℃, heat preservation time of 60-120 minutes and water cooling; the alloy delivery state is generally a solid solution state. The using state is a tempering treatment state, and the specific process parameters are related to specifications.
According to the alloy disclosed by the invention, a Fe-Ni alloy containing Fe, Ni, Co, Nb, Cr, Al and other elements is designed according to the influence relationship of alloy elements on the expansion performance, and meanwhile, the performance of the alloy elements such as C, Ti, Si, Mn and the like is optimized, so that an average linear expansion coefficient alpha is successfully and stably prepared10-30℃＝(1.3～1.8)×10-6Novel extremely narrow range constant expansion alloys at/° c. The alloy of the invention is suitable for the alloy with the required average linear expansion coefficient alpha10-30℃＝(1.3～1.8)×10-6Precise instrument and equipment for aerospace engineering at/DEG C and other sealing materials with the requirement on expansion performance. The alloy delivery is generally in a solution annealed state, and the service state is a part tempered state.
According to the influence relationship of Ni element on the average linear expansion coefficient of the alloy, the average linear expansion coefficient of the alloy can be ensured to be lower by controlling the Ni content.
Impurity elements of the alloy, such as S, P and the like, are controlled by selecting raw materials, vacuum induction melting and electroslag remelting, so that the purity of the alloy is improved, and the stability of the performance of the alloy is favorably ensured.
The small amount of Si added can slightly reduce the Curie point of the alloy, but has little influence on the expansion performance of the alloy, and can chemically react with oxygen in the alloy during smelting to generate silicon oxide scum which is discharged out of molten steel, thereby reducing non-metallic inclusions in the alloy, and the addition of Si with too high content can cause the processing plasticity of the alloy to be poor.
The trace amount of C and the small amount of Nb are added to ensure that the alloy has certain corrosion resistance and the strength of the alloy is improved, but the C content and the Nb content exceed those of the invention, so that the average linear expansion coefficient of the alloy is sharply improved, and brittle carbides are easily precipitated in the grain boundary of the alloy, thereby deteriorating the processing performance of the alloy.
The addition of Cr element content is favorable for improving the average linear expansion coefficient of the low-expansion alloy.
Adding a proper amount of Al and Mn elements,the alloy has the advantages of improving the hot working performance of the alloy, simultaneously improving the average linear expansion coefficient of the low-expansion alloy, being lower than the Al and Mn content of the alloy, being not beneficial to deoxidation during alloy smelting, increasing the non-metallic inclusion of the alloy and reducing the processing plasticity of the alloy when the Al and Mn content is higher than the Al and Mn content of the alloy. Most importantly, the addition of the Al element with larger atomic radius can cause lattice distortion of the alloy, increase the volume expansion of the alloy, partially offset the phenomenon of reverse expansion (negative expansion) of the low-expansion alloy caused by magnetic shrinkage due to heating, improve the average linear expansion coefficient of the alloy, and control the content of the Al element to be 0.10-0.30% in the invention is beneficial to ensuring that the average linear expansion coefficient of the alloy is (1.3-1.8) multiplied by 10-6The range/° c.
The addition of Ti element is favorable for improving the expansion coefficient of the alloy, and the Ti content higher than that of the invention can ensure that the expansion coefficient of the alloy is continuously improved to exceed 1.8 multiplied by 10-6/℃。
Compared with the existing highest-performance alloy of the same type, the alloy disclosed by the invention not only has good mechanical properties, especially has thermal expansion performance meeting specific requirements, fills the gap of the constant-expansion alloy in the area, but also can solve the problem that other alloys cannot solve or cannot solve the problem well, thereby promoting the technical progress and industrial development of related industries, and the economic benefit and the social benefit are obvious.
Drawings
FIG. 1 is a graph showing the average linear expansion coefficient values and the graphs of example 1;
FIG. 2 is a graph showing the average linear expansion coefficient values of example 2.
Detailed Description
The invention is further illustrated but is not intended to be limited thereby within the scope of the embodiments described.
Example 1:
the novel Fe-Ni-based Al-containing high-strength constant-expansion alloy comprises the following chemical components in percentage by weight: c: 0.02; si: 0.3; mn: 0.3; al: 0.15; ti: 0.09; ni: 35.8 of; nb: 0.55; co: 1.0; cr: 0.72; the balance being Fe;
the preparation method of the novel high-strength fixed expansion alloy is characterized by comprising the following steps of:
a) and smelting
Weighing the components according to the weight percentage of the chemical components, smelting the alloy by vacuum induction, and when carrying out the vacuum induction smelting, adopting a secondary refining process, wherein the primary refining temperature is slightly higher and the time is slightly longer;
first refining
Charging a bottom material into the furnace: fe. Smelting Co, Cr, Nb and Ni at the temperature higher than 1550 ℃ and under the condition of controlling the vacuum degree to be 5-10 Pa, and smelting according to the time of 0.7 min/kg;
second refining
The second refining adopts low-temperature short-time refining, C, Si, Mn, Al and Ti are added into a furnace, sufficient mechanical and electromagnetic stirring is carried out after the materials are added, smelting is carried out at the temperature of more than 1520 ℃ according to the time of 0.5min/kg, and the vacuum degree control at the final stage of refining is superior to 2 Pa;
after refining is finished, introducing argon into the furnace for protection, standing the molten steel for 10 minutes, and performing rapid pouring when the temperature of the molten steel is controlled to be 1480 ℃;
then electroslag remelting is carried out, CaF is adopted during remelting2-CaO-Al2O3A ternary slag system, wherein the remelting temperature is about 1700 ℃, the remelting speed is about 0.8Kg/min, the depth, the current and the voltage of a slag pool are properly controlled to ensure the stability of the remelting process, and hot feeding is carried out for 5 times before remelting is finished to finally obtain an alloy ingot;
b) forging the steel plate
The alloy hot forging temperature is 800-1120 ℃, and the heat preservation time is 80 minutes;
c) and solution treatment
After hot working, the alloy must be subjected to solution treatment at proper time to obtain a required tissue structure, and the solution treatment system comprises the heat preservation temperature of 750 ℃, the heat preservation time of 60 minutes and water cooling.
The produced alloy bar is turned and peeled to be made into an alloy bar which is applied to a precise instrument supporting piece.
Example 2:
a novel iron-nickel based Al-containing high-strength constant-expansion alloy comprises the following chemical components in percentage by weight: c: 0.01; si: 0.10; mn: 0.20; al: 0.20; ti: 0.75; ni: 35.20; nb:0.45 of; co: 0.85; cr: 0.65; and the balance of Fe, and the produced alloy ingot is subjected to hot processing and cold processing to form an alloy ring piece which is applied to a sealing piece.
The preparation method is the same as example 1.
Taking the alloys obtained in the examples 1 and 2, performing a mechanical property test, wherein the room-temperature mechanical property is as follows:
TABLE 1 mechanical properties of alloys in solid solution + stabilized state at room temperature
Figure BDA0002261292710000071
The density of the detected alloy is 8.12g/cm3(ii) a Detecting the room-temperature elastic modulus E of the alloy to be more than or equal to 140 GPa; mean linear expansion coefficient alpha10-30℃＝(1.3～1.8)×10-6/° c, see fig. 1 and 2.
And (4) conclusion: the alloy of the invention has good mechanical property and average linear expansion coefficient alpha10-30℃＝(1.3～1.8)×10-6The sealing material is suitable for precision instruments and equipment for aerospace engineering and other sealing materials with the requirement on expansion performance.
Although embodiments of the present invention have been described, various changes or modifications may be made by one of ordinary skill in the art within the scope of the appended claims. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.

Claims (4)

1. An iron-nickel-based Al-containing high-strength constant-expansion alloy is characterized by comprising the following components in percentage by weight: ni: 35.0-35.9%; 0.4 to 0.6 percent of Nb; co:0.8-1.2%; al: 0.10-0.30%; cr: 0.50-0.75%; ti is less than or equal to 0.75 percent; c is less than or equal to 0.03 percent; si is less than or equal to 0.40 percent; mn is less than or equal to 0.40 percent; s is less than or equal to 0.001 percent; p is less than or equal to 0.008 percent; the balance being Fe, the average linear expansion coefficient alpha of the constant expansion alloy10-30℃=（1.3～1.8）×10-6V. C, room temperature yield strength Rp0.2Not less than 300MPa, and the dynamic elastic modulus E not less than 140 GPa.
2. The alloy of claim 1, wherein the weight percentages of the components are: ni: 35.2-35.8%; 0.45 to 0.55 percent of Nb; co: 0.85-1.0%; al: 0.15-0.20%; cr: 0.65-0.72%; ti: 0.09-0.75%; c: 0.01-0.02%; si: 0 to 0.3 percent; mn: 0 to 0.3 percent; s: 0 to 0.001 percent; p: 0 to 0.008 percent; the balance being Fe.
3. The alloy of claim 1, wherein the weight percentages of the components are: ni: 35.8 percent; nb: 0.55 percent; co: 1.0 percent; al: 0.15 percent; cr: 0.72 percent; ti: 0.09%; c: 0.02 percent; si: 0.3 percent; mn: 0.3 percent; the balance being Fe.
4. The alloy of claim 1, wherein the weight percentages of the components are: ni: 35.20 percent; nb:0.45 percent; co: 0.85 percent; al: 0.20 percent; cr: 0.65 percent; ti: 0.75 percent; c: 0.01 percent; si: 0.10 percent; mn: 0.20 percent; the balance being Fe.
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