CN114959435B - Nb-Cr-Fe ternary intermediate alloy and preparation method and application thereof - Google Patents
Nb-Cr-Fe ternary intermediate alloy and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a Nb-Cr-Fe ternary intermediate alloy and a preparation method and application thereof, belongs to the technical field of metal materials, and aims to solve the problem that the existing NbFe melting point exceeds the melting points of medium-high carbon steel and cast iron molten steel, so that NbFe cannot be fully melted and diffused in the medium-high carbon steel and cast iron. The Nb-Cr-Fe ternary intermediate alloy comprises the following elements in percentage by mass: nb:5% -25%, cr:20 to 45 percent of the total weight of the alloy, and the balance of Fe. The melting point range of the Nb-Cr-Fe ternary intermediate alloy is 1350-1440 ℃. The Nb-Cr-Fe ternary intermediate alloy has low melting point, and can be fully melted and diffused when being used as a raw material for preparing medium-high carbon steel or cast iron, so that the yield of Nb and Cr elements can be remarkably improved.
Description
Technical Field
The invention belongs to the technical field of metal materials, and particularly relates to a Nb-Cr-Fe ternary intermediate alloy as well as a preparation method and application thereof.
Background
Nb is a high-melting-point metal, is an important high-temperature refractory metal element, is an important alloy element in high-temperature alloy and heat-resistant steel, has a melting point of 2468 +/-10 ℃, can remarkably improve the hardenability of the steel by trace solid-solution Nb, has a solid-solution Nb strengthening grain boundary effect larger than Mo, W and V, and can improve the high-temperature durability. The addition of trace Nb can effectively inhibit the growth of austenite grains, obviously prevent the recrystallization of deformed austenite, improve the carbon content of a eutectoid point, reduce the decarburization tendency, improve the high-temperature strength, the elastic modulus, the corrosion resistance and the like of steel.
NbFe is mainly used for high-temperature alloy, stainless steel and high-strength low-alloy steel. Nb is added into the permanent magnetic alloy, so that the coercive force performance of the alloy can be improved. Nb is added into the cast iron, which is beneficial to spheroidization and formation of pearlite structure, and plays a role in inoculation and casting structure refinement. Nb can improve the strength, toughness, hardness and service life of the casting at high temperature. The welding rod uses NbFe as a welding flux component to improve the welding quality.
However, the use amount and the function of NbFe in steel are not fully embodied because NbFe50 has a melting point of 1540-1620 ℃, nbFe60 has a melting point of 1560-1620 ℃, nbFe70 has a melting point of 1410-1600 ℃, and low-carbon microalloyed steel has a melting point of 1620 ℃ or higher, medium-high carbon steel has a melting point of about 1500 ℃, and cast iron has a melting point of 1400 ℃ or lower, so that NbFe can only be used in low-carbon microalloyed steel, and cannot be fully melted and diffused in medium-high carbon steel and cast iron.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a Nb-Cr-Fe ternary intermediate alloy, and a preparation method and application thereof, for solving the following technical problems: the problem that the melting point of the prior NbFe exceeds the melting points of medium-high carbon steel and cast iron molten steel, so that the NbFe can not be fully melted and diffused in the medium-high carbon steel and the cast iron is solved.
The purpose of the invention is mainly realized by the following technical scheme:
on one hand, the invention provides a Nb-Cr-Fe ternary intermediate alloy, which comprises the following elements in percentage by mass: nb:5% -25%, cr:20 to 45 percent of the total weight of the alloy, and the balance of Fe.
Furthermore, the melting point range of the Nb-Cr-Fe ternary intermediate alloy is 1350-1440 ℃.
Further, the Nb-Cr-Fe ternary intermediate alloy comprises the following elements in percentage by mass: nb:10% -20%, cr:25 to 40 percent of Fe, and the balance of Fe.
Furthermore, the melting point range of the Nb-Cr-Fe ternary intermediate alloy is 1370-1420 ℃.
The invention also provides a preparation method of the Nb-Cr-Fe ternary intermediate alloy, which is used for preparing the Nb-Cr-Fe ternary intermediate alloy and comprises the following steps:
s1, filling pure iron, ferrochrome, ferrocolumbium and crucible carbon into a vacuum induction furnace;
s2, vacuumizing a melting chamber of the vacuum induction furnace, and then transmitting electricity to heat furnace burden;
s3, after furnace burden is melted and cleared out of a molten pool, gradually improving the vacuum degree;
s4, adjusting the power to be low, and refining to remove O, N and H;
s5, controlling the temperature of the molten steel to be 1430-1470 ℃, electrically pouring the molten steel into an ingot mold in order to avoid temperature drop and mixing an oxide film into an injection flow, and naturally cooling;
s6, discharging gas, breaking the cavity, opening a furnace cover and taking out the ingot mold;
and S7, crushing the alloy blocks in the ingot mold according to the finished product shaping.
Further, in step S2, when the vacuum degree is less than 15Pa, the furnace burden is started to be heated by power transmission.
Further, in the step S2, when the furnace burden is heated, the initial power is 8-10kW, the power is gradually increased to 25-30kW at the rate of increasing 5-6kW every 10min.
Further, in the step S3, the control power is 25-30kW.
Further, in step S3, refining is controlled for 8-15min, and the vacuum degree is less than or equal to 5Pa.
Further, in step S5, naturally cooling for 5-10min.
The invention also provides an application of the Nb-Cr-Fe ternary intermediate alloy, and the ternary intermediate alloy is used as a raw material for preparing medium-high carbon steel or cast iron.
Compared with the prior art, the invention can realize at least one of the following beneficial effects:
a) The Nb-Cr-Fe ternary intermediate alloy ensures the low melting point of the Nb-Cr-Fe ternary intermediate alloy by accurately controlling the contents of Nb, cr and Fe, and ensures the melting point of the Nb-Cr-Fe ternary intermediate alloy to be 1350-1440 ℃.
b) The preparation method of the invention firstly adopts the vacuum induction furnace for smelting, reduces the oxygen content in the Nb-Cr-Fe ternary alloy, has uniform components and lower melting point, prevents splashing by accurately controlling the process parameters, and ensures the production safety.
c) When the Nb-Cr-Fe ternary intermediate alloy is used as a raw material for preparing medium-high carbon steel or cast iron, the melting point of the Nb-Cr-Fe ternary intermediate alloy is low, so that when the Nb-Cr-Fe ternary intermediate alloy is used as a raw material for preparing medium-high carbon steel or cast iron, the Nb-Cr-Fe ternary intermediate alloy can be fully melted and diffused, and the yield of Nb and Cr elements can be obviously improved. For example, the yield of Cr element is increased by 6% or more, and the yield of Nb element is increased by 11% or more. The Nb-Cr-Fe ternary intermediate alloy has wide application range.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description.
Detailed Description
The following detailed description of the preferred embodiments of the invention, which are given for the purpose of illustrating the principles of the invention and are not to be taken in a limiting sense.
Nb is a high-melting-point metal, is an important high-temperature refractory metal element, is an important alloy element in high-temperature alloy and heat-resistant steel, can obviously improve the hardenability of the steel by trace amount of solid-solution Nb, has a stronger grain boundary effect than Mo, W and V, and can improve the high-temperature durability. The addition of trace Nb can effectively inhibit the growth of austenite grains, obviously prevent the recrystallization of deformed austenite, improve the carbon content of a eutectoid point, reduce the decarburization tendency, improve the high-temperature strength, the elastic modulus, the corrosion resistance and the like of steel. Nb is added into the permanent magnetic alloy, so that the coercive force performance of the alloy can be improved. Nb is added into the cast iron, which is beneficial to spheroidization and formation of pearlite structures, and plays a role in inoculation and casting structure refinement. Nb can improve the strength, toughness, hardness and service life of the casting at high temperature. The welding rod uses NbFe as a welding flux component to improve the welding quality.
In the prior art, nb is mostly provided by adopting NbFe, but because the melting point of NbFe50 is 1540-1620 ℃, the melting point of NbFe60 is 1560-1620 ℃, the melting point of NbFe70 is 1410-1600 ℃, and the melting point of low-carbon microalloyed steel is above 1620 ℃, the melting point of medium-high carbon steel is about 1500 ℃, and the melting point of cast iron is below 1400 ℃, nbFe can only be used in the low-carbon microalloyed steel, and cannot be fully melted and diffused in the medium-high carbon steel and the cast iron, the usage amount and the function of NbFe in steel are not fully embodied.
In view of this, the invention provides a Nb-Cr-Fe ternary intermediate alloy, which comprises the following elements in percentage by mass: nb:5% -25%, cr:20 to 45 percent of the total weight of the alloy, and the balance of Fe.
Specifically, the melting point range of the Nb-Cr-Fe ternary intermediate alloy is 1350-1440 ℃.
Specifically, the Nb-Cr-Fe ternary intermediate alloy comprises the following elements in percentage by mass: nb:10% -20%, cr:25 to 40 percent of Fe, and the balance of Fe.
Specifically, the melting point range of the Nb-Cr-Fe ternary master alloy is 1370-1420 ℃.
It should be noted that the Nb-Cr-Fe ternary intermediate alloy ensures the low melting point of the Nb-Cr-Fe ternary intermediate alloy and the melting point of the Nb-Cr-Fe ternary intermediate alloy to be 1350 ℃ -1440 ℃ by accurately controlling the contents of Nb, cr and Fe.
Specifically, the preparation method of the Nb-Cr-Fe ternary intermediate alloy comprises the following steps:
s1, filling pure iron, ferrochrome, ferrocolumbium and crucible carbon into a vacuum induction furnace;
s2, vacuumizing a smelting chamber of the vacuum induction furnace, and then transmitting power to heat furnace burden;
s3, after furnace burden is melted and cleared out of a molten pool, gradually improving the vacuum degree;
s4, adjusting the power to be low, and refining to remove O, N, H and the like;
s5, controlling the temperature of the molten steel to be 1430-1470 ℃, electrically pouring the molten steel into an ingot mold in order to avoid temperature drop and mixing an oxide film into an injection flow, and naturally cooling;
s6, deflating, breaking the cavity, opening a furnace cover and taking out the ingot mold;
and S7, crushing the alloy blocks in the ingot mold according to the finished product shaping.
Specifically, in step S2, when the degree of vacuum is less than 15Pa, the charging is started to be electrically heated.
Specifically, in the step S2, when the furnace burden is heated, the initial power is 8-10kW, and the power is gradually increased to 25-30kW at the rate of increasing 5-6kW every 10min.
Specifically, in the step S3, the control power is 25-30kW to avoid splashing.
Specifically, in step S4, in order to ensure that the gas content is reduced, refining is controlled for 8-15min, and the vacuum degree is less than or equal to 5Pa.
Specifically, in the step S5, the temperature is naturally reduced for 5-10min.
Specifically, the Nb-Cr-Fe ternary master alloy prepared by the preparation method has low gas content such as O:20ppm or less, N: below 70ppm, homogeneous components, 1350-1440 deg.c melting point and low melting point.
The invention also provides application of the Nb-Cr-Fe ternary intermediate alloy. The high-carbon steel can be used as a raw material for preparing medium-high carbon steel or cast iron. Because the melting point of the Nb-Cr-Fe ternary intermediate alloy is low, when the Nb-Cr-Fe ternary intermediate alloy is used as a raw material for preparing medium-high carbon steel or cast iron, the Nb-Cr-Fe ternary intermediate alloy can be fully melted and diffused, and the yield of Nb and Cr elements can be obviously improved. For example, the yield of Cr element is increased by 6% or more, and the yield of Nb element is increased by 11% or more.
The advantages of the Nb-Cr-Fe ternary intermediate alloy of the invention will be demonstrated below in specific examples and comparative examples.
Example 1
The embodiment provides an Nb-Cr-Fe ternary intermediate alloy, and in the embodiment, the Nb-Cr-Fe ternary intermediate alloy comprises the following components in percentage by mass: nb:10%, cr:25% and the balance Fe.
The equipment adopts a 10kg vacuum induction melting furnace with the ultimate vacuum degree of 6.67 multiplied by 10 -2 Pa, power supply power of 50kW, frequency of 4000Hz, and charging amount of 5.5kg. Casting into alloy blocks, and crushing the alloy blocks into 5-50mm by a crusher.
In this embodiment, the preparation method of the Nb-Cr-Fe ternary intermediate alloy specifically includes the following steps:
(1) Charging pure iron, ferrochromium, ferrocolumbium and crucible carbon into a furnace;
(2) Evacuating a melting chamber of the vacuum induction furnace, starting to transmit power to heat furnace materials when the vacuum degree is less than 15Pa, wherein the power is 9kW, and gradually increasing the power to 30kW at a rate of increasing 5kW every 10 min;
(3) After furnace burden is melted and cleared out of a molten pool, the power is controlled to be 26kW, splashing is avoided, and the vacuum degree is gradually improved;
(4) Adjusting the power to be low, refining for 10min, removing O, N, H and the like, wherein the vacuum degree is less than or equal to 5 Pa;
(5) Controlling the temperature of the molten steel to 1440-1450 ℃, in order to avoid temperature drop and oxide film mixing into the injection flow, electrically pouring into an ingot mold, and naturally cooling for 5min;
(6) Deflating, breaking the cavity, opening the furnace cover and taking out the ingot mold;
(7) And (4) according to the finished product sizing, crushing the alloy blocks in the ingot mould into 5-50mm by using a crusher.
In the present example, the gas content of the Nb-Cr-Fe ternary master alloy is low, for example, O:20ppm, N:70ppm, uniform components, stable quality and high yield.
Through the test of STA-449C type synchronous thermal analyzer (DSC), the melting point of the Nb-Cr-Fe ternary intermediate alloy is as follows: 1380.8 ℃.
Example 2
The embodiment provides a Nb-Cr-Fe ternary intermediate alloy, and in the embodiment, the Nb-Cr-Fe ternary intermediate alloy comprises the following components in percentage by mass: nb:15%, cr:30 percent and the balance of Fe.
The equipment adopts a 10kg vacuum induction melting furnace with the ultimate vacuum degree of 6.67 multiplied by 10 -2 Pa, power supply power of 50kW, frequency of 4000Hz, and charging amount of 5.5kg. Casting into alloy blocks, and then crushing the alloy blocks into 5-50mm by a crusher.
In this embodiment, the preparation method of the Nb-Cr-Fe ternary intermediate alloy specifically includes the following steps:
(1) Charging pure iron, ferrochromium, ferrocolumbium and crucible carbon into a furnace;
(2) Evacuating a melting chamber of the vacuum induction furnace, starting to transmit power to heat furnace materials when the vacuum degree is less than 15Pa, wherein the power is 10kW, and gradually increasing the power to 30kW at a rate of increasing 5kW every 10 min;
(3) After furnace burden is melted and cleared out of a molten pool, the power is controlled to be 28kW, splashing is avoided, and the vacuum degree is gradually improved;
(4) Adjusting the power to be low, refining the mixture to 10Min with the vacuum degree less than or equal to 5Pa, removing O, N, H and the like;
(5) Controlling the temperature of the molten steel to 1450-1460 ℃, electrically pouring the molten steel into an ingot mold in order to avoid temperature drop and oxide film mixing into the injection flow, and naturally cooling for 7min;
(6) Deflating, breaking the cavity, opening the furnace cover and taking out the ingot mold;
(7) And (4) crushing the alloy blocks in the ingot mould into 5-50mm by a crusher according to the finished product sizing.
In the present example, the gas content of the Nb — Cr — Fe ternary master alloy is low, for example, O:18ppm, N:65ppm, uniform components, stable quality and high yield.
Through the test of STA-449C type synchronous thermal analyzer (DSC), the melting point of the Nb-Cr-Fe ternary intermediate alloy is as follows: 1383.9 ℃.
Example 3
The embodiment provides a Nb-Cr-Fe ternary intermediate alloy, and in the embodiment, the Nb-Cr-Fe ternary intermediate alloy comprises the following components in percentage by mass: nb:20%, cr:40 percent, and the balance being Fe.
The equipment adopts a 10kg vacuum induction melting furnace with the ultimate vacuum degree of 6.67 multiplied by 10 -2 Pa, power supply power of 50kW, frequency of 4000Hz, and charging amount of 5.5kg. Casting into alloy blocks, and crushing the alloy blocks into 5-50mm by a crusher.
In this embodiment, the preparation method of the Nb-Cr-Fe ternary intermediate alloy specifically includes the following steps:
(1) Charging pure iron, ferrochromium, ferrocolumbium and crucible carbon into a furnace;
(2) Evacuating a melting chamber of the vacuum induction furnace, starting to transmit power to heat furnace materials when the vacuum degree is less than 15Pa, wherein the power is 10kW, and gradually increasing the power to 30kW at a rate of increasing 5kW every 10 min;
(3) After furnace burden is melted and cleared out of a molten pool, the power is controlled to be 28kW, splashing is avoided, and the vacuum degree is gradually improved; .
(4) Adjusting the power to be low, refining for 10min, removing O, N, H and the like, wherein the vacuum degree is less than or equal to 5 Pa;
(5) Controlling the temperature of the molten steel to be 1450-1470 ℃, electrically pouring the molten steel into an ingot mold in order to avoid temperature drop and oxide film mixing into the injection flow, and naturally cooling for 5min;
(6) Deflating, breaking the cavity, opening the furnace cover and taking out the ingot mold;
(7) And (4) crushing the alloy blocks in the ingot mould into 5-50mm by a crusher according to the finished product sizing.
In the present example, the gas content of the Nb — Cr — Fe ternary master alloy is low, for example, O:20ppm, N:70ppm, uniform components, stable quality and high yield.
Through the test of an STA-449C type synchronous thermal analyzer (DSC), the melting point of the Nb-Cr-Fe ternary intermediate alloy is as follows: 1415.4 ℃.
Example 4
The embodiment provides application of the Nb-Cr-Fe ternary intermediate alloy, wherein the Nb-Cr-Fe ternary intermediate alloy in the embodiment 1 and common metals NbFe, crFe and Fe are adopted to prepare medium-high carbon steel 6Cr15MoNb, the two preparation processes are controlled according to the same feeding sequence and smelting process, the influence of other factors is reduced as much as possible, the yield of Nb and Cr elements is compared, and the practical effect of the Nb-Cr-Fe ternary intermediate alloy in production is verified.
The results of the yields of Nb and Cr are shown in Table 1 below.
TABLE 1Nb and Cr element yield results
By adopting the processes of the ternary master alloys of the embodiments 2 and 3, the yield improvement of the Cr element is respectively 7.3 percent and 7.5 percent, and the yield improvement of the Nb element is respectively 12.4 percent and 12.5 percent, so that the yield of the Nb element and the Cr element is obviously improved when the ternary master alloy is used for preparing medium-high carbon steel, and the Nb-Cr-Fe ternary master alloy has obvious effect on the element yield improvement.
According to the results, the Nb-Cr-Fe ternary intermediate alloy ensures the low melting point of the Nb-Cr-Fe ternary intermediate alloy by accurately controlling the contents of Nb, cr and Fe, and ensures the melting point of the Nb-Cr-Fe ternary intermediate alloy to be 1350-1440 ℃. Therefore, when the Nb-Cr-Fe ternary intermediate alloy is used as a raw material for preparing medium-high carbon steel or cast iron, the Nb-Cr-Fe ternary intermediate alloy can be fully melted and diffused, and the yield of Nb and Cr elements can be obviously improved. When the Nb-Cr-Fe ternary intermediate alloy is used for preparing cast iron, the yield of the Cr element is improved by more than 6 percent, and the yield of the Nb element is improved by more than 11 percent.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (8)
1. The application of the Nb-Cr-Fe ternary intermediate alloy is characterized in that the Nb-Cr-Fe ternary intermediate alloy comprises the following elements in percentage by mass: nb:15% -25%, cr: 30-45% of Fe and the balance of Fe;
the melting point range of the Nb-Cr-Fe ternary intermediate alloy is 1350-1440 ℃;
the Nb-Cr-Fe ternary intermediate alloy is used as a raw material for preparing medium-high carbon steel or cast iron.
2. The use of the Nb-Cr-Fe ternary intermediate alloy according to claim 1, wherein the Nb-Cr-Fe ternary intermediate alloy comprises the following elements in percentage by mass: nb:15% -20%, cr:30 to 40 percent of Fe, and the balance of Fe.
3. The use of the Nb-Cr-Fe ternary master alloy as set forth in claim 2, wherein the Nb-Cr-Fe ternary master alloy has a melting point in the range of 1370 ℃ to 1420 ℃.
4. Use of a Nb-Cr-Fe ternary intermediate alloy according to any of the claims 1 to 3, characterized in that the method for the preparation of the Nb-Cr-Fe ternary intermediate alloy comprises the following steps:
s1, filling pure iron, ferrochromium, ferrocolumbium and crucible carbon into a vacuum induction furnace;
s2, vacuumizing a smelting chamber of the vacuum induction furnace, and then transmitting power to heat furnace burden;
s3, after furnace burden is melted and cleared out of a molten pool, gradually improving the vacuum degree;
s4, adjusting the power to be low, and refining to remove O, N and H;
s5, controlling the temperature of the molten steel to be 1430-1470 ℃, pouring the molten steel into an ingot mold in an electrified manner in order to avoid temperature drop and oxide film mixing into an injection flow, and naturally cooling;
s6, discharging gas, breaking the cavity, opening a furnace cover and taking out the ingot mold;
and S7, crushing the alloy blocks in the ingot mold according to the finished product shaping.
5. The use of the Nb-Cr-Fe ternary intermediate alloy according to claim 4, wherein in the step S2, the charge is electrically heated when the vacuum degree is less than 15 Pa.
6. The use of the Nb-Cr-Fe ternary intermediate alloy according to claim 4, wherein in the step S2, the charge is heated with an initial power of 8-10kW, with a gradual increase of the power to 25-30kW at a rate of 5-6kW per 10min.
7. The use of the Nb-Cr-Fe ternary intermediate alloy according to claim 4, wherein in the step S3, refining is controlled for 8-15min, and the vacuum degree is less than or equal to 5Pa.
8. The use of the Nb-Cr-Fe ternary intermediate alloy in accordance with claim 4, wherein the temperature in step S5 is naturally decreased for 5-10min.
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