CN115233041B - Low-expansion alloy with tensile plasticity and preparation method thereof - Google Patents
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Abstract
The invention belongs to the field of functional materials, and relates to a low expansion alloy with tensile plasticity and a preparation method thereof, wherein the atomic percentage of alloy components is Fe-xCo-yCr-zNi-aM, wherein x is 45-55%, y is 8-15%, z is 0-10%, a is 0-1.0%, and M is one or more of N, C, B, mo; the low expansion alloy matrix structure with tensile plasticity is single-phase fcc, and the surface of the low expansion alloy matrix structure is provided with stress-induced bcc phase. The beneficial effects of the invention are as follows: the austenitic stable elements Ni, C, N and Fe-Co-Cr are alloyed by designing alloy components, so that the low-expansion alloy which can keep good stability after 100 times of cold and hot cycles and 30 days of storage under liquid nitrogen is successfully prepared, has tensile plasticity, has a more stable austenitic structure compared with the traditional stainless invar, has smaller thermal expansion coefficient compared with the invar alloy, and has important application prospect and commercial value.
Description
Technical Field
The invention belongs to the field of functional materials, and relates to a preparation method of a low-expansion alloy with tensile plasticity.
Background
Low expansion alloys play an extremely important role in production and life, such as in lng ships, aerospace, mechanical watches, gratings, etc., as key components, because their dimensions do not change with temperature. For example, space telescopes can have a diurnal temperature differential of over 200 ℃ (-100 to 100 ℃) and the resulting dimensional changes in the material can significantly affect their accuracy of observation, thus necessitating the use of low expansion alloys as their core support materials. However, existing low expansion alloys are mostly intermetallic compounds, and their inherent brittleness results in limited practical applications. In addition, the negative expansion intermetallic compound and the positive expansion material are compounded, and the low expansion composite material with certain strength can be obtained, but the thermal crack is easy to be generated in the thermal cycle process due to the fact that the thermal expansion between different phases in the material is not matched and the phase interface appears, and the composite material is difficult to have tensile plasticity. Refractory high-entropy alloys generally have a coefficient of thermal expansion higher than 6 and have a relatively large coefficient of thermal expansion as low-expansion alloys and limited applications (ZL 201410319113.8). The low expansion alloy which is currently applied industrially on a large scale is invar alloy (Fe-36 Ni) developed at the end of the 19 th century, but invar alloy has a large thermal expansion coefficient and poor corrosion resistance, which has hindered its application in many fields to some extent. The 20 th century reports that stainless invar (Fe-54.5 Co-9 Cr) and super invar (Fe-31 Ni-5 Co) alloys have lower coefficients of thermal expansion than invar alloys, but are prone to martensitic transformation in the tens of temperature regions nearby, rendering thermal expansion non-recyclable. Therefore, the development of the novel low-expansion alloy with tensile plasticity and thermal expansion circulation has important application prospect and scientific value.
Disclosure of Invention
The invention discloses a low expansion alloy with stretching plasticity and a preparation method thereof, which are used for solving any one of the above and other potential problems in the prior art.
In order to solve the problems, the technical scheme of the invention is as follows: a low expansion alloy with tensile plasticity is characterized in that the atomic percentage of the low expansion alloy component is Fe-xCo-yCr-zNi, wherein x is more than or equal to 45 and less than or equal to 55%, y is more than or equal to 8 and less than or equal to 15%, and z is more than or equal to 0 and less than or equal to 10%.
Further, the low expansion alloy also includes M, which is one or more of N, C, B, mo;
the atomic percentage of M is more than or equal to 0 and less than or equal to 1.0 percent.
Furthermore, the austenite stabilizing elements of the alloy are Ni, C and N, and the austenite stabilizing elements and Fe-Co-Cr are alloyed, so that the generation of matrix martensite phase can be inhibited, and fcc low-expansion alloy with better stability can be successfully prepared.
Further, the alloy structural matrix of the low expansion alloy with tensile plasticity is single-phase fcc, and the surface of the alloy structural matrix is provided with a martensite phase of a part of stress-induced bcc structure.
Further, the low expansion alloy with stretch plasticity comprises the following atomic percent: 48.055 at% Co, 10.5 at% Cr, 3.5 at% Ni, and the balance of Fe and unavoidable impurities,
the ductility of the alloy is 35%, and the thermal expansion coefficient is within the temperature range of 100K-400K: 0.8×10 -6 。
further, the low expansion alloy with stretch plasticity comprises the following atomic percent: 46.5 at% Co, 15 at% Cr, 5 at% Ni, 0.3 at% B, the balance Fe and unavoidable impurities,
the ductility of the alloy is 25%, and the thermal expansion coefficient is within the temperature range of 100K-300K: 1.5X10 -6 。
Further, the low expansion alloy with stretch plasticity comprises the following atomic percent: 50 at% Co, 12 at% Cr, 4 at% Ni, 0.1 at% C, 0.1 at% N, the balance being Fe and unavoidable impurities,
the ductility of the alloy is 30%, and the thermal expansion coefficient is within the temperature range of 100K-350K: 1.7X10 -6 。
Another object of the present invention is to provide a method for preparing a low expansion alloy having stretch plasticity, which specifically comprises the steps of:
step 1: according to the designed alloy chemical components, respectively weighing Fe, co, cr, ni and M, and removing a surface oxide layer;
step 2: after the treated raw materials are mixed, the mixture is placed in a vacuum arc furnace for smelting for a plurality of times until the mixture is uniform, and an alloy cast ingot is obtained;
step 3: and adding the alloy cast ingot which is uniformly smelted and M into a vacuum arc furnace for smelting and then carrying out suction casting to obtain the low-expansion alloy with tensile plasticity.
Further, fe in the raw material is cast iron containing C, N, the purity is required to be more than 99%, and the Mn and Si contents are less than 0.5%; the purity of other raw materials is more than or equal to 99.95 percent.
Further, the elongation of the low expansion alloy with tensile plasticity is 20-50%, and the thermal expansion coefficient is within the temperature range of 100K-400K: 0.05-3×10 -6 。
A low expansion alloy having stretch-plasticity, which is produced by the above-described method.
The low expansion alloy is kept for 30 days under liquid nitrogen, does not generate martensitic transformation, still keeps good thermal expansion stability after 100 times of cold and hot circulation, and has the linear expansion coefficient of near room temperature: 0.05-3×10 -6 。
The austenite stabilizing elements of the alloy are Ni, C and N, and the austenite stabilizing elements and Fe-Co-Cr are alloyed, so that the generation of matrix martensite phase can be successfully restrained, and fcc low-expansion alloy with better stability can be successfully prepared.
Compared with the prior art, the alloy has the following technical effects:
1. the low-expansion alloy disclosed by the invention has the advantages that the size does not change obviously along with temperature change, the thermal expansion coefficient is lower, and the shape/size thermal stability and the precision are excellent;
2. the low-expansion alloy can be stored for one month under liquid nitrogen, has high low-temperature stability compared with the traditional stainless invar alloy, and can be used at the temperature of liquid nitrogen;
3. the low expansion alloy surface of the invention has stress induced bcc phase, and the surface hardness is higher than the invar alloy of pure fcc phase.
Because thermal expansion is extremely composition sensitive, it is not necessary for any product embodying the invention to achieve all of the technical effects described above at the same time.
Drawings
FIG. 1 is a xrd map of a low expansion alloy (examples 1-6) designed according to this invention.
FIG. 2 is a graph showing the thermal expansion characteristics of the low expansion alloys of the present invention (examples 1-6).
FIG. 3 is a schematic representation of the thermal cycle of the zero expansion component example 1 of the present invention and the linear expansion of the storage for various periods of time under liquid nitrogen.
FIG. 4 is a graphical representation of the room temperature pull-up curve of the zero expansion component of example 1 of the present invention as cast.
Detailed Description
The invention provides a preparation method of a low expansion alloy with stretching plasticity, and the technical scheme of the invention is better understood, and the preparation method is described in detail below with reference to the accompanying drawings and specific examples.
The invention relates to a low expansion alloy with stretching plasticity, the atomic percentage of the components of the low expansion alloy is Fe-xCo-yCr-zNi, wherein, x is more than or equal to 45 and less than or equal to 55%, y is more than or equal to 8 and less than or equal to 15%, z is more than or equal to 0 and less than or equal to 10%,
the low expansion alloy further comprises M, wherein M is one or more of N, C, B, mo;
the atomic percentage of M is more than or equal to 0 and less than or equal to 1.0 percent.
The alloy structure matrix of the low expansion alloy with the tensile plasticity is single-phase FCC, and the surface of the alloy structure matrix is provided with a part of stress-induced bcc structure martensitic phase.
Atomic percent of the low expansion alloy with stretch plasticity: 48.055 at% Co, 10.5 at% Cr, 3.5 at% Ni, and the balance of Fe and unavoidable impurities,
the ductility of the alloy is 35%, and the thermal expansion coefficient is within the temperature range of 100K-400K: 0.8X10 -6 。
Atomic percent of the low expansion alloy with stretch plasticity: 46.5 at% Co, 15 at% Cr, 5 at% Ni, 0.3 at% B, the balance Fe and unavoidable impurities,
the ductility of the alloy is 25%, and the thermal expansion coefficient is within the temperature range of 100K-300K: 1.5X10 -6 。
Atomic percent of the low expansion alloy with stretch plasticity: 50 at% Co, 12 at% Cr, 4 at% Ni, 0.1 at% C, 0.1 at% N, the balance being Fe and unavoidable impurities,
the ductility of the alloy is 30%, and the thermal expansion coefficient is within the temperature range of 100K-350K: 1.7X10 -6 。
The invention also provides a preparation method of the low-expansion alloy with tensile plasticity, which specifically comprises the following steps:
step 1: according to the designed alloy chemical components, respectively weighing Fe, co, cr, ni and M, and removing a surface oxide layer;
step 2: after the treated raw materials are mixed, the mixture is placed in a vacuum arc furnace for smelting for a plurality of times until the mixture is uniform, and an alloy cast ingot is obtained;
step 3: and adding the alloy cast ingot which is uniformly smelted and M into a vacuum arc furnace for smelting and then carrying out suction casting to obtain the low-expansion alloy with tensile plasticity.
Fe in the raw material is cast iron containing C, N, the purity is more than 99%, and the Mn and Si contents are less than 0.5%; the purity of other raw materials is more than or equal to 99.95 percent.
The extensibility of the low expansion alloy with the tensile plasticity is 20-50%, and the thermal expansion coefficient is as follows within the temperature range of 100K-400K: 0.05-3×10 -6 。
A low expansion alloy having stretch-plasticity, which is produced by the above-described method.
Example 1:
the low expansion alloy with the components of Fe-48.055 Co-10.5Cr-3.5Ni-0.1B-0.3Mo is prepared by adopting a vacuum arc furnace smelting method, and the reaction equation is as follows:
37.545×Fe + 48.055×Co + 10.5×Cr + 3.5Ni+0.1B+0.3Mo= Fe-48.055 Co-11.5Cr-3.5Ni-0.1B-0.3Mo
the specific operation is carried out according to the following steps:
step 1: weighing Fe, co, cr, ni, B, mo raw materials with the atomic percentages of 37.545: 48.055:10.5:3.5:0.1:0.3 respectively;
step 2: weighing the raw materials Fe, co, cr, ni, B, mo in the step 1 according to specific chemical components, mixing, and smelting in a vacuum arc furnace for multiple times until the raw materials are uniform;
step 3: mixing the alloy cast ingot which is uniformly smelted with a stable austenite element, smelting in a vacuum arc furnace, and then carrying out suction casting;
the characteristics are as follows: as shown in FIG. 1, the prepared alloy matrix structure is face-centered cubic, and the surface of the alloy matrix structure contains stress-induced bcc martensite; as shown in fig. 4, the elongation of the prepared alloy reaches 35%; as shown in fig. 3, the thermal expansion coefficient of the prepared alloy is within the temperature range of 100K-400K: 0.7X10 -6 And remain stable for 30 days under 100 cold and hot cycles and liquid nitrogen.
Example 2
The low expansion alloy with the components of Fe-46.5Co-15Cr-5Ni-0.3B is prepared and synthesized by adopting a vacuum arc furnace smelting method, and the reaction equation is as follows:
33.5×Fe + 46.5×Co + 15×Cr + 5Ni + 0.3B= Fe-46.5Co-15Cr-5Ni-0.3B
the specific operation is carried out according to the following steps:
step 1: weighing Fe, co, cr, ni, B raw materials with the molar ratio of 33.5:46.5:15:5:0.3 respectively;
step 2: weighing the raw materials Fe, co, cr, ni, B in the step 1 according to specific chemical components, mixing, and smelting in a vacuum arc furnace for multiple times until the raw materials are uniform;
step 3: mixing the alloy cast ingot which is uniformly smelted with a stable austenite element, smelting in a vacuum arc furnace, and then carrying out suction casting;
the characteristics are as follows: the sample structure is face-centered cubic, the yield strength is 300MPa, and the thermal expansion coefficient is in a temperature range of 100-300K: 1.5X10 -6 。
Example 3
The low-expansion alloy with the components of Fe-50Co-12Cr-4Ni-0.1C-0.1N is prepared and synthesized by adopting a vacuum arc furnace smelting method, and the reaction equation is as follows:
33.8×Fe + 50×Co + 12×Cr + 4Ni +0.1C +0.1N = Fe-50Co-12Cr-4Ni-0.1C-0.1N
the specific operation is carried out according to the following steps:
step 1: weighing Fe, co, cr, ni, C, N raw materials with the molar ratio of 33.8:50:12:4:0.1:0.1 respectively;
step 2: weighing the raw materials Fe, co, cr, ni, C, N in the step 1 according to specific chemical components, mixing, and smelting in a vacuum arc furnace for multiple times until the raw materials are uniform;
step 3: mixing the alloy cast ingot which is uniformly smelted with a stable austenite element, smelting in a vacuum arc furnace, and then carrying out suction casting; the alloy structure is single-phase FCC, the yield strength is 400MPa, and the elongation is 25%.
Example 4
The low-expansion alloy with the components of Fe-45Co-11Cr-3.7Ni-0.2Mo-0.3N is prepared by adopting a vacuum arc furnace smelting method, and the reaction equation is as follows:
39.8×Fe + 45×Co + 11×Cr + 3.7Ni + 0.2Mo + 0.3N = Fe-45Co-11Cr-3.7Ni-0.2Mo-0.3N
the specific operation is carried out according to the following steps:
step 1: weighing Fe, co, cr, ni, mo, N raw materials with the molar ratio of 39.8:45:11:3.7:0.2:0.3 respectively;
step 2: weighing the raw materials Fe, co, cr, ni, mo, N in the step 1 according to specific chemical components, mixing, and smelting in a vacuum arc furnace for multiple times until the raw materials are uniform;
step 3: mixing the alloy cast ingot which is uniformly smelted with a stable austenite element, smelting in a vacuum arc furnace, and then carrying out suction casting;
the characteristics are as follows: the alloy structural matrix is single-phase FCC, and a small amount of bcc martensite exists on the surface. The yield strength is 500MPa, the elongation is 20%, and the thermal expansion coefficient is within the range of 100-350K: 1.8X10 -6 。
Example 5
The low-expansion alloy with the components of Fe-47Co-15Cr-5Ni-0.3Mo-0.1C-0.2N is prepared and synthesized by adopting a vacuum arc furnace smelting method, and the reaction equation is as follows:
32.4×Fe + 47×Co + 15×Cr + 5Ni + 0.3Mo + 0.1C + 0.2N = Fe-52Co-15Cr-5Ni-0.3Mo-0.1C-0.2N
the specific operation is carried out according to the following steps:
step 1: weighing Fe, co, cr, ni, mo, C, N raw materials with the molar ratio of 32.4:47:15:5:0.5:0.1:0.2 respectively;
step 2: weighing the raw materials Fe, co, cr, ni, mo, C, N in the step 1 according to specific chemical components, mixing, and smelting in a vacuum arc furnace for multiple times until the raw materials are uniform;
step 3: mixing the alloy cast ingot which is uniformly smelted with a stable austenite element, smelting in a vacuum arc furnace, and then carrying out suction casting; the alloy structural matrix is single-phase FCC, and a small amount of bcc martensite exists on the surface. The yield strength is 350MPa, the elongation is 31%, and the thermal expansion coefficient is within the range of 100-350K: 2.3X10 -6 。
Example 6
The low expansion alloy with the components of Fe-50Co-9Cr-7Ni-0.3Mo-0.2B is prepared and synthesized by adopting a vacuum arc furnace smelting method, and the reaction equation is as follows:
33.5×Fe + 50×Co + 9×Cr + 7Ni + 0.3Mo+ 0.2B = Fe-50Co-9Cr-7Ni-0.3Mo-0.2B
the specific operation is carried out according to the following steps:
step 1: weighing Fe, co, cr, ni, mo, B raw materials with the molar ratio of 33.5:50:9:7:0.3 respectively;
step 2: weighing the raw materials Fe, co, cr, ni, mo, B in the step 1 according to specific chemical components, mixing, and smelting in a vacuum arc furnace for multiple times until the raw materials are uniform;
step 3: mixing the alloy cast ingot which is uniformly smelted with a stable austenite element, smelting in a vacuum arc furnace, and then carrying out suction casting, wherein the alloy structural matrix is single-phase FCC, the yield strength is 500MPa, the elongation is 17%, and the thermal expansion coefficient is within a range of 100-300K; 1.3X10 -6 。
The low expansion alloy with tensile plasticity and the preparation method thereof provided by the embodiment of the application are described in detail. The above description of embodiments is only for aiding in understanding the method of the present application and its core ideas; meanwhile, as those skilled in the art will have modifications in the specific embodiments and application scope in accordance with the ideas of the present application, the present description should not be construed as limiting the present application in view of the above.
Certain terms are used throughout the description and claims to refer to particular components. Those of skill in the art will appreciate that a hardware manufacturer may refer to the same component by different names. The description and claims do not take the form of an element differentiated by name, but rather by functionality. As referred to throughout the specification and claims, the terms "comprising," including, "and" includes "are intended to be interpreted as" including/comprising, but not limited to. By "substantially" is meant that within an acceptable error range, a person skilled in the art is able to solve the technical problem within a certain error range, substantially achieving the technical effect. The description hereinafter sets forth the preferred embodiment for carrying out the present application, but is not intended to limit the scope of the present application in general, for the purpose of illustrating the general principles of the present application. The scope of the present application is defined by the appended claims.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a product or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such product or system. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a commodity or system comprising such elements.
It should be understood that the term "and/or" as used herein is merely one relationship describing the association of the associated objects, meaning that there may be three relationships, e.g., a and/or B, may represent: a exists alone, A and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.
While the foregoing description illustrates and describes the preferred embodiments of the present application, it is to be understood that this application is not limited to the forms disclosed herein, but is not to be construed as an exclusive use of other embodiments, and is capable of many other combinations, modifications and environments, and adaptations within the scope of the teachings described herein, through the foregoing teachings or through the knowledge or skills of the relevant art. And that modifications and variations which do not depart from the spirit and scope of the present invention are intended to be within the scope of the appended claims.
Claims (7)
1. The low expansion alloy with tensile plasticity is characterized in that the atomic percentage of the low expansion alloy component is Fe-xCo-yCr-zNi, wherein x is more than or equal to 45% and less than or equal to 55%, y is more than or equal to 8% and less than or equal to 15%, and z is more than or equal to 0 and less than or equal to 10%; the low expansion alloy also comprises M, wherein M is one or more of N, C, B, mo, and the atomic percentage of M is more than 0 and less than 1.0%;
the alloy structure matrix of the low expansion alloy with the tensile plasticity is single-phase fcc, and the surface of the alloy structure matrix is provided with a stress-induced bcc structure martensitic phase;
the elongation of the low expansion alloy with tensile plasticity is 20-50%, and the thermal expansion coefficient is within a temperature range of 100K-400K: 0.05-3×10 -6 。
2. The low expansion alloy with stretch-plasticity according to claim 1, characterized in that it comprises, in atomic percent: 48.055 at% Co, 10.5 at% Cr, 3.5 at% Ni, and the balance of Fe and unavoidable impurities,
the ductility of the alloy is 35%, and the thermal expansion coefficient is within the temperature range of 100K-400K: 0.7X10 -6 。
3. The low expansion alloy with stretch-plasticity according to claim 1, characterized in that it comprises, in atomic percent: 46.5 at% Co, 15 at% Cr, 5 at% Ni, 0.3 at% B, the balance Fe and unavoidable impurities,
the ductility of the alloy is 25%, and the thermal expansion coefficient is within the temperature range of 100K-300K: 1.5X10 -6 。
4. The low expansion alloy with stretch-plasticity according to claim 1, characterized in that it comprises, in atomic percent: 50 at% Co, 12 at% Cr, 4 at% Ni, 0.1 at% C, 0.1 at% N, the balance being Fe and unavoidable impurities,
the ductility of the alloy is 30%, and the thermal expansion coefficient is within the temperature range of 100K-350K: 1.7X10 -6 。
5. A method for preparing a low expansion alloy having stretch-plasticity according to claim 1, characterized in that it comprises in particular the following steps:
step 1: according to the designed alloy chemical components, respectively weighing Fe, co, cr, ni and M, and polishing to remove a surface oxide layer;
step 2: mixing the Fe, co, cr and Ni treated in the step S1), and then smelting for many times in a vacuum arc furnace until the mixture is uniform to obtain an alloy cast ingot;
step 3: and adding the alloy cast ingot which is uniformly smelted and M into a vacuum arc furnace for smelting and then carrying out suction casting to obtain the low-expansion alloy with tensile plasticity.
6. The method according to claim 5, wherein the Fe in the raw material is cast iron containing C, N, the purity is required to be more than 99%, and the Mn and Si contents are less than 0.5%; the purity of other raw materials is more than or equal to 99.95 percent.
7. A low expansion alloy having stretch-plasticity, characterized in that the low expansion alloy having stretch-plasticity is produced by the method according to any one of claims 5 or 6.
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