CN117904509A - Fe-Co-based soft magnetic composite material with in-situ self-generated TiC and Ni added and controlled synergistically and preparation method thereof - Google Patents
Fe-Co-based soft magnetic composite material with in-situ self-generated TiC and Ni added and controlled synergistically and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an Fe-Co-based soft magnetic composite material with in-situ self-generated TiC and Ni added and regulated in a synergistic manner and a preparation method thereof. The Fe-Co-based soft magnetic composite material comprises Fe, co, ni, ti and C, wherein the content of Ni element is 9-30at% and the content of Ti element is 1.7-4.0at% according to the atomic percentage of metal elements; ti and C are present in the composite as in situ autogenous TiC. The invention is prepared by a mechanical alloying and spark plasma sintering process; the prealloyed powder sintered by the spark plasma retains a certain amount of cyclohexane as a residual process control agent, wherein the residual process control agent contained in the prealloyed powder is as follows: 0.4-1.0wt.%. Compared with the traditional Fe-Co-based soft magnetic alloy, the Fe-Co-based soft magnetic composite material prepared by the invention has the advantages that the strength and the plasticity are obviously improved, and meanwhile, the excellent soft magnetic performance can be maintained.
Description
Technical Field
The invention belongs to the technical field of soft magnetic metal materials, and particularly relates to an Fe-Co-based soft magnetic composite material with in-situ self-generated TiC and Ni added and controlled in a synergistic manner and a preparation method thereof.
Background
The soft magnetic material is a material which can rapidly respond to the change of an external magnetic field and can obtain high magnetic induction intensity with low loss, and is an important magnetic material in the industries of electronics, electric power, aerospace, automation, instruments and the like. In the 21 st century, with the rapid development of science and technology, the performance of electronic and mechanical equipment is continuously improved, and higher requirements are also put on the mechanical properties of soft magnetic devices. Therefore, development of a novel structure-function integrated soft magnetic material with excellent mechanical properties and soft magnetic properties has become an important research direction.
The Fe-Co-based soft magnetic alloy has the advantages of high saturation magnetization and low coercivity, is an ideal material indispensable in high-power equipment and instruments, but has low plasticity so as to limit the improvement space of mechanical properties (rare metal materials and engineering, 2013,42 (6): 1316-1320). Research shows that the Fe-Co based alloy mainly shows a B2 crystal structure at room temperature, and the ordered phase B2 is a main cause of alloy brittleness, so that the Fe-Co based alloy has poor processing performance and cannot be used in the fields of high-speed motors and the like. Table 1 below lists the compressive mechanical properties and soft magnetic properties of Fe 50Co50 alloys prepared by different SPS sintering processes (Journal of MATERIALS SCIENCE,2017, 52:13284-13295). As shown in Table 1, the yield strength of the Fe 50Co50 alloy under three different sintering process conditions is very low (330-340 MPa), and the compressive fracture strain is less than 4%, which indicates that the brittleness of the alloy is very high, and the application of the alloy in 'structure-function' integration is severely limited.
TABLE 1 compression mechanical Properties and Soft magnetic Properties of Fe 50Co50 alloys prepared by different SPS sintering Process
The industry generally adopts the method of adding a third element to improve the plasticity and toughness of the original binary alloy, and researches show that: after the ferromagnetic element Ni is added to the Fe-Co-based alloy, the original B2 crystal structure of the Fe-Co-based alloy is converted into a partial FCC (BCC+FCC) or full FCC structure, so that the addition of the Ni element can improve the plasticity and toughness of the alloy, and particularly the FeCoNi alloy with a single-phase FCC structure has outstanding soft magnetic performance and plasticity but lower yield strength. Meanwhile, a large number of studies indicate that: the in-situ self-generated nano second phase can improve the thermal stability of the matrix alloy, and simultaneously prevent element diffusion so as to inhibit the growth rate of grains in the sintering process, so that the nano second phase can be used for regulating and controlling microstructure so as to improve the mechanical property of the alloy. In SPS sintering, one of the reasons for forming these second phase particles is that a small amount of process control agent (toluene, cyclohexane, stearic acid, etc.) remains after the alloy powder after ball milling is not sufficiently dried, and the remaining process control agent can provide C, O atoms for the alloy during the subsequent sintering process, and perform in-situ autogenous reaction with metal elements (such as Ti) in the alloy to form nano second phase particles. However, the conventional method for preparing the metal matrix composite by adding the second phase is usually liquid stirring, powder metallurgy method and the like, and the method involves complex processes such as melt treatment, surface pretreatment of the second phase and the like, and the interfacial reaction and wettability between the reinforcement and the matrix are difficult to control, so that the complex processes and high cost always limit the application of the method.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide the Fe-Co-based soft magnetic composite material with the synergistic regulation and control of the addition of in-situ authigenic TiC and Ni and the preparation method thereof, so as to better meet the higher mechanical requirements of electronic and mechanical equipment on the soft magnetic material.
The invention aims to prepare the Fe-Co-based soft magnetic composite material by combining a short-flow process of mechanical alloying and Spark Plasma Sintering (SPS) and in-situ self-generated nano TiC, and the in-situ self-generated TiC and Ni addition are synergistically regulated and controlled, so that excellent combination of mechanical property and soft magnetic property is realized.
The invention discovers that after the ferromagnetic element Ni is added to the Fe-Co base alloy, the original B2 crystal structure of the Fe-Co base alloy is partially converted into FCC or completely converted into FCC structure after the short-flow process of mechanical alloying and Spark Plasma Sintering (SPS), and the plasticity of the Fe-Co base alloy containing the FCC structure is obviously improved. Therefore, the addition of Ni element can improve the plasticity of Fe-Co based alloy.
The invention discovers that when a 'mechanical alloying + Spark Plasma Sintering (SPS)' method is adopted to prepare the Fe-Co based soft magnetic composite material, ti element with better affinity with C element in the alloy can generate in-situ autogenous reaction with C source generated by the decomposition of a residual process control agent to form an endogenous carbide. However, the process control agent (toluene, stearic acid, etc.) decomposes oxygen element during pyrolysis, and the oxygen element is liable to cause oxidation reaction of the alloy element to form metal oxide, and the soft magnetic composite material will be degraded due to the introduction of metal oxide impurities. The invention utilizes the C source generated by the decomposition (C 6H12 =6C+12H) of the process control agent (cyclohexane) in the spark plasma sintering process to generate in-situ autogenous reaction (C+Ti=TiC) with Ti element, thereby avoiding the introduction of metal oxide impurities into the soft magnetic composite material. And in-situ authigenic TiC particles are uniformly distributed in the alloy matrix, so that a remarkable dispersion strengthening effect is generated, and the strength and plasticity of the material are improved.
Therefore, the invention provides an in-situ self-generated TiC and Ni added synergistic regulation Fe-Co-based soft magnetic composite material which has high strength and high plasticity, maintains excellent soft magnetic performance (high saturation magnetization and low coercivity), and finally realizes excellent combination of mechanical performance and soft magnetic performance.
The aim of the invention is realized by the following technical scheme:
an Fe-Co-based soft magnetic composite material with in-situ self-generated TiC and Ni added and controlled in a synergistic way comprises Fe, co, ni, ti and C, wherein the content of Ni element is 9-30at percent and the content of Ti element is 1.7-4.0at percent according to the atomic percentage of metal element; ti and C are present in the composite as in situ autogenous TiC.
Preferably, the content of Fe element is 30-50at.% and the content of Co element is 30-50at.% based on the atomic percentage of metal element.
Preferably, the content of Ni element is 14.5at.%, the content of Ti element is 2.9at.%, the content of Fe element is 38.9at.%, and the content of Co element is 43.7at.% in terms of atomic percent of metal element.
Preferably, the TiC content in volume percent is: 3-7vol.%.
The preparation method of the Fe-Co-based soft magnetic composite material with the synergistic regulation of the in-situ self-generated TiC and the Ni addition is prepared by a mechanical alloying and Spark Plasma Sintering (SPS) process, so that the Fe-Co-based soft magnetic composite material with the synergistic regulation of the in-situ self-generated TiC and the Ni addition is obtained; the prealloyed powder sintered by the spark plasma retains a certain amount of cyclohexane as a residual process control agent, wherein the residual process control agent contained in the prealloyed powder is as follows: 0.4-1.0wt.%.
Preferably, the mechanical alloying is a protective atmosphere ball milling technology, which comprises the following steps:
(1) And weighing and mixing Fe, co, ni, ti element powder or alloy powder according to a proportion to obtain a mixture.
(2) And (3) placing the mixture obtained in the step (1) into a powder mixer for uniform mixing to obtain mixed powder.
(3) And (3) adding the mixed powder obtained in the step (2) into cyclohexane which is a process control agent and a grinding ball for wet grinding under a protective atmosphere to obtain prealloyed powder.
(4) And (3) performing semi-drying treatment (the dried pre-alloyed powder retains cyclohexane with the mass fraction of 0.4-1.0 wt.%) on the pre-alloyed powder, and then heating to perform sintering treatment to obtain the Fe-Co-based soft magnetic composite material with in-situ self-generated TiC and Ni added and cooperatively regulated.
It is further preferred that the mixed powder of step (3) is totally immersed in a cyclohexane atmosphere, the amount of cyclohexane being 200-300mL per 100g of mixed powder.
It is further preferred that the elemental powder or alloy powder of step (1) of Fe, co, ni, ti has a purity of 99.7wt.% or more and a particle size of the powder of 45um or less.
It is further preferred that the mixing time in step (2) is 5-10 hours.
Further preferably, the wet milling time in the step (3) is 40-60 hours; the wet grinding rotating speed is more than or equal to 250rpm; the wet grinding ball material ratio is 10:1-20:1; the protective atmosphere is argon.
Further preferably, the temperature rise in the step (4) is a stepwise temperature rise, the temperature rise is performed at a rate of 80-90 ℃/min at room temperature to 200 ℃, and the temperature rise is performed at a rate of 100-150 ℃/min at 200-1000 ℃.
Further preferably, the sintering temperature in the step (4) is 900-1000 ℃; the sintering heat preservation time is 5-8min; the pressure of sintering treatment is 30-40MPa; the sintering vacuum degree is less than or equal to 8Pa.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The invention adopts the spark plasma sintering method, the activation energy is lower than that of the conventional heating mode, the reaction temperature is lower, the process operation is simple, the method is safe and reliable, the energy and time are saved, the environment is friendly, and the controllability is strong.
(2) After the ferromagnetic element Ni is added to the Fe-Co based alloy, the original B2 crystal structure of the Fe-Co based alloy is partially converted into FCC or completely converted into FCC structure after a short-flow process of mechanical alloying and Spark Plasma Sintering (SPS), and the plasticity of the Fe-Co based alloy containing the FCC structure is obviously improved. Therefore, the addition of Ni element can improve the plasticity of Fe-Co based alloy.
(3) The TiC is obtained by reacting titanium element (with better affinity with C element) with a carbon source generated by decomposing a process control agent (cyclohexane), so that in-situ self-generated nano TiC (average size is less than 100 nm) is formed, the in-situ self-generated TiC particles improve the thermal stability of the matrix alloy, and meanwhile, the diffusion of the elements is prevented so as to inhibit the growth rate of grains in the sintering process, so that the microstructure can be effectively regulated and controlled; and the nano TiC is uniformly distributed in the alloy matrix, so that a remarkable dispersion strengthening effect is generated, and the mechanical property of the alloy is further improved. Therefore, compared with the traditional Fe-Co-based alloy with the B2 ordered phase as the main phase, the strength and the plasticity of the Fe-Co-based soft magnetic composite material are obviously improved by the synergistic regulation and control of the in-situ self-generated TiC and the Ni addition.
(4) According to the invention, through the design of Ni element and TiC content, the composite material with high strength and high plasticity and excellent soft magnetic performance (high saturation magnetization and low coercivity) is obtained.
Drawings
FIG. 1 is a microstructure of an in-situ self-generated TiC and Ni-added synergistically regulated Fe-Co-based soft magnetic composite material prepared in example 1;
FIGS. 2 and 3 are respectively a room temperature compression stress-strain curve and a room temperature hysteresis loop of the in-situ self-generated TiC and Ni-added synergistically regulated Fe-Co-based soft magnetic composite material prepared in example 1;
FIG. 4 is a microstructure of the in-situ self-generated TiC and Ni-added synergistically regulated Fe-Co-based soft magnetic composite material prepared in example 2;
FIGS. 5 and 6 are, respectively, a room temperature compressive stress-strain curve and a room temperature hysteresis loop of the in-situ self-generated TiC and Ni-added synergistically regulated Fe-Co-based soft magnetic composite material prepared in example 2;
FIG. 7 is a microstructure of the in-situ self-generated TiC and Ni-added synergistically regulated Fe-Co-based soft magnetic composite material prepared in example 3;
FIGS. 8 and 9 are, respectively, a room temperature compressive stress-strain curve and a room temperature hysteresis loop of the in-situ self-generated TiC and Ni-added synergistically regulated Fe-Co-based soft magnetic composite material prepared in example 3;
FIG. 10 is a microstructure of the Ni-addition control Fe-Co-based alloy material prepared in comparative example 1;
FIGS. 11 and 12 are a room temperature compressive stress-strain curve and a room temperature hysteresis loop, respectively, of the Ni-addition regulation Fe-Co-based alloy material prepared in comparative example 1;
FIG. 13 is a microstructure of the in-situ self-generated TiC and Ni addition synergistic regulation Fe-Co-based soft magnetic composite material prepared in comparative example 2;
FIGS. 14 and 15 are, respectively, a room temperature compressive stress-strain curve and a room temperature hysteresis loop of an in-situ self-generated TiC and Ni-added synergistically regulated Fe-Co-based soft magnetic composite material prepared in comparative example 2;
FIG. 16 is a microstructure of an in-situ self-generated TiC and Ni addition synergistic regulation Fe-Co-based composite material prepared in comparative example 3;
Fig. 17 and 18 are a room temperature compressive stress-strain curve and a room temperature hysteresis loop, respectively, of the in-situ self-generated TiC and Ni added synergistic-controlled Fe-Co-based composite material prepared in comparative example 3.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but are not intended to limit the practice and protection of the invention. It should be noted that the following processes, if not specifically described in detail, can be realized or understood by those skilled in the art with reference to the prior art. The reagents or apparatus used were not manufacturer-specific and were considered conventional products commercially available.
The invention relates to a preparation method of an in-situ self-generated TiC and Ni added synergistic regulation Fe-Co-based soft magnetic composite material, which is prepared by a mechanical alloying and Spark Plasma Sintering (SPS) process, and the preparation method comprises the following steps:
(1) In the in-situ self-generated TiC and Ni added synergistic regulation Fe-Co-based soft magnetic composite material, the content of nickel elements is as follows according to the atomic percentage of metal elements: ni 9-30at% (in atomic percent); the TiC content is: 3-7vol.% (in volume percent) of the desired elemental or alloy powder is formulated and the powder is mixed. The grain diameter of each element powder is less than or equal to 45um, and the purity is more than or equal to 99.7 wt%.
(2) And (3) placing the mixture obtained in the step (1) into a powder mixer to mix for 5-10 hours to obtain mixed powder.
(3) Wet milling the mixed powder obtained in the step (2) in an argon atmosphere for 40-60 hours; the process control agent adopted by the wet grinding is cyclohexane, the mixed powder is fully immersed in the cyclohexane environment, the consumption of the cyclohexane is 200-300mL relative to the consumption of each 100g of the mixed powder, and the wet grinding rotating speed is more than or equal to 250rpm; the wet grinding ball material ratio is 10:1-20:1, and prealloyed powder is obtained.
(4) And (3) drying the alloy powder in the step (3) (the dried prealloy powder keeps cyclohexane with the residual mass fraction of 0.4-1.0 wt.%), and then heating to perform SPS sintering treatment to obtain the in-situ self-generated TiC and Ni added synergistic regulation Fe-Co-based soft magnetic composite material.
Example 1
The preparation method of the in-situ self-generated TiC and Ni added synergistic regulation Fe-Co-based soft magnetic composite material specifically comprises the following steps:
(1) The Fe-Co-based soft magnetic composite material is Fe 45Co45Ni10/TiC, wherein Fe, co, ni, ti element powder is weighed and prepared into mixed powder according to the atomic percentage of Fe44.2%, co 44.2%, ni 9.9% and Ti 1.7%, the particle size of each element powder is less than or equal to 45um, and the purity is more than or equal to 99.7wt.%;
(2) Placing the prepared mixed powder into a powder mixer to mix for 5 hours, and uniformly mixing;
(3) And (3) filling the uniformly mixed powder into a stainless steel vacuum ball milling tank, filling argon into the ball milling tank for protection, and then carrying out wet milling for 40 hours to obtain alloy powder. The process control agent is cyclohexane (C 6H12), the dosage of the cyclohexane is 260mL relative to the dosage of each 100g of mixed powder, the ball milling speed is 250rpm, and the ball-to-material ratio (mass ratio) is 10:1;
(4) Drying the wet-ground alloy powder in a vacuum drying oven (the dried prealloyed powder retains 0.4wt.% of cyclohexane), putting 80g of the dried alloy powder into a graphite sintering mold with the diameter of phi 20mm, and sintering into a block composite material by adopting discharge plasma; the sintering process parameters are as follows:
sintering temperature: 1000 ℃;
Rate of temperature rise: 85 ℃/min at room temperature to 200 ℃, 150 ℃/min at 200 ℃ to 100 ℃;
The heat preservation time is as follows: 8min; sintering pressure: 40MPa; sintering vacuum degree: 8Pa.
The in-situ self-generated TiC (volume fraction is 3 vol.%) prepared by the embodiment and Ni are added to synergistically regulate and control the Fe-Co-based soft magnetic composite material, and a microstructure picture is shown in figure 1, so that the microstructure is composed of an alloy matrix, in-situ self-generated TiC particles and a small number of holes. The room temperature compression stress strain curve of the material is shown in figure 2, and the yield strength, the breaking strength and the breaking strain are 890MPa, 1766MPa and 25% respectively, so that the material has excellent mechanical properties. The room-temperature hysteresis loop of the material is shown in figure 3, the saturation magnetization Ms=172.0 emu/g, the coercive force Hc=6.8 Oe, and the soft magnetic performance is excellent.
Example 2
The preparation method of the in-situ self-generated TiC and Ni added synergistic regulation Fe-Co-based soft magnetic composite material specifically comprises the following steps:
(1) The Fe-Co-based soft magnetic composite material is prepared from Fe 40Co45Ni15/TiC, wherein the Fe is 38.9% of Fe, the Co is 43.7% of Co, the Ni is 14.5% of Ti is 2.9% of Ti, fe, co, ni, ti element powder is weighed and prepared into mixed powder, the particle size of each element powder is less than or equal to 45um, and the purity is more than or equal to 99.7wt.%;
(2) Placing the prepared mixed powder into a powder mixer to mix for 6 hours, and uniformly mixing;
(3) And (3) filling the uniformly mixed powder into a stainless steel vacuum ball milling tank, filling argon into the ball milling tank for protection, and then carrying out wet milling for 50 hours to obtain alloy powder. The process control agent is cyclohexane (C 6H12), the dosage of the cyclohexane is 260mL relative to the dosage of each 100g of mixed powder, the ball milling speed is 300rpm, and the ball-to-material ratio (mass ratio) is 10:1;
(4) Placing the wet-ground alloy powder into a vacuum drying oven for drying (the dried prealloyed powder retains cyclohexane with the residual mass fraction of 0.7 percent), taking 80g of the dried alloy powder, placing the dried alloy powder into a graphite sintering mold with the diameter of phi 20mm, and sintering the powder into a block composite material by adopting discharge plasma; the sintering process parameters are as follows:
Sintering temperature: 950 ℃;
Rate of temperature rise: 90 ℃/min at room temperature to 200 ℃,120 ℃/min at 200 ℃ to 950 ℃;
The heat preservation time is as follows: 7min; sintering pressure: 30MPa; sintering vacuum degree: 8Pa.
The in-situ self-generated TiC (volume fraction is 5 vol.%) prepared by the embodiment and Ni are added to synergistically regulate and control the Fe-Co-based soft magnetic composite material, a microstructure picture is shown in figure 4, and the microstructure is composed of an alloy matrix, in-situ self-generated TiC particles and a small number of holes. The room temperature compression stress strain curve of the material is shown in figure 5, the yield strength, the breaking strength and the breaking strain are 1150MPa, 2748MPa and 42 percent respectively, and the mechanical property is excellent. The room temperature hysteresis loop of the material is shown in fig. 6, the saturation magnetization ms=174.6 emu/g, the coercive force hc=3.1 Oe, and the soft magnetic property is excellent.
Example 3
The preparation method of the in-situ self-generated TiC and Ni added synergistic regulation Fe-Co-based soft magnetic composite material specifically comprises the following steps:
(1) The Fe-Co-based soft magnetic composite material is Fe 35Co35Ni30/TiC, wherein Fe, co, ni, ti element powder is weighed and prepared into mixed powder according to the atomic percentage of Fe33.6%, co 33.6%, ni 28.8% and Ti4%, the particle size of each element powder is less than or equal to 45um, and the purity is more than or equal to 99.7wt.%;
(2) Placing the prepared mixed powder into a powder mixer to mix for 7 hours, and uniformly mixing;
(3) And (3) filling the uniformly mixed powder into a stainless steel vacuum ball milling tank, filling argon into the ball milling tank for protection, and then carrying out wet milling for 45h to obtain alloy powder. The process control agent is cyclohexane (C 6H12), the dosage of the cyclohexane is 260mL relative to the dosage of each 100g of mixed powder, the ball milling speed is 300rpm, and the ball-to-material ratio (mass ratio) is 15:1;
(4) Placing the wet-ground alloy powder into a vacuum drying oven for drying (the dried prealloyed powder retains cyclohexane with the residual mass fraction of 1.0 percent), taking 80g of the dried alloy powder, placing the dried alloy powder into a graphite sintering mold with the diameter of phi 20mm, and sintering the powder into a block composite material by adopting discharge plasma; the sintering process parameters are as follows:
Sintering temperature: 900 ℃;
Rate of temperature rise: 80 ℃/min at room temperature to 200 ℃, 125 ℃/min at 200 ℃ to 900 ℃;
the heat preservation time is as follows: 8min; sintering pressure: 30MPa; sintering vacuum degree: 8Pa.
The in-situ self-generated TiC (volume fraction is 7 vol.%) prepared by the embodiment and Ni are added to synergistically regulate and control the Fe-Co-based soft magnetic composite material, a microstructure picture is shown in figure 7, and the microstructure is composed of an alloy matrix, in-situ self-generated TiC particles and a small number of holes. The room temperature compression stress strain curve of the material is shown in figure 8, the yield strength, the breaking strength and the breaking strain are 1255MPa, 2509MPa and 31 percent respectively, and the mechanical property is excellent. The room temperature hysteresis loop of the material is shown in figure 9, the saturation magnetization ms= 149.0emu/g, the coercive force hc=6.9 Oe, and the soft magnetic property is excellent.
Comparative example 1
The preparation method of the Ni-added regulation Fe-Co-based alloy in the comparative example specifically comprises the following steps:
(1) The Fe-Co-based alloy material is Fe 45Co45Ni10, fe, co 45.0% and Ni 10.0% are weighed according to the atomic percentages of Fe 45.0%, fe, co and Ni element powder are prepared into mixed powder, the particle size of each element powder is less than or equal to 45um, and the purity is more than or equal to 99.7wt.%;
(2) Placing the prepared mixed powder into a powder mixer to mix for 5 hours, and uniformly mixing;
(3) And (3) filling the uniformly mixed powder into a stainless steel vacuum ball milling tank, filling argon into the ball milling tank for protection, and then carrying out wet milling for 40 hours to obtain alloy powder. The process control agent is cyclohexane (C 6H12), the dosage of the cyclohexane is 260mL relative to the dosage of each 100g of mixed powder, the ball milling speed is 250rpm, and the ball-to-material ratio (mass ratio) is 10:1;
(4) Drying the wet-ground alloy powder in a vacuum drying oven, putting 80g of dried alloy powder into a graphite sintering mold with the diameter of phi 20mm, and sintering into a block alloy material by adopting discharge plasma; the sintering process parameters are as follows:
sintering temperature: 1000 ℃;
Rate of temperature rise: 85 ℃/min at room temperature to 200 ℃, 150 ℃/min at 200 ℃ to 100 ℃;
The heat preservation time is as follows: 8min; sintering pressure: 40MPa; sintering vacuum degree: 8Pa.
The microstructure picture of Fe 45Co45Ni10 of the Fe-Co based alloy material prepared in the comparative example is shown in figure 10, and the microstructure is composed of an alloy matrix and a small number of holes. The room temperature compression stress strain curve of the material is shown in figure 11, the yield strength, the breaking strength and the breaking strain are 521MPa, 2144MPa and 32%, respectively, and the yield strength is reduced by 41% compared with that of the example 1. The room temperature hysteresis loop of the material is shown in fig. 12, the saturation magnetization ms=190.0 emu/g, the coercivity hc=13.1 Oe is improved by 10% compared with the embodiment 1, the coercivity hc=13.1 Oe is improved by 96% compared with the embodiment 1, the soft magnetic performance of the material is obviously reduced compared with the embodiment 1, and the material is beyond the coercivity (less than 12.5 Oe) range of the soft magnetic material.
Comparative example 2
The preparation method of the in-situ self-generated TiC and Ni added synergistic regulation Fe-Co-based soft magnetic composite material specifically comprises the following steps:
(1) The Fe-Co-based soft magnetic composite material is Fe 40Co45Ni15/TiC, wherein according to the atomic percentage, the Fe is 39.6%, the Co is 44.5%, the Ni is 14.9%, the Ti is 1.0%, fe, co, ni, ti element powder is weighed and prepared into mixed powder, the particle size of each element powder is less than or equal to 45um, and the purity is more than or equal to 99.7wt.%;
(2) Placing the prepared mixed powder into a powder mixer to mix for 5 hours, and uniformly mixing;
(3) And (3) filling the uniformly mixed powder into a stainless steel vacuum ball milling tank, filling argon into the ball milling tank for protection, and then carrying out wet milling for 40 hours to obtain alloy powder. The process control agent is cyclohexane (C 6H12), the dosage of the cyclohexane is 260mL relative to the dosage of each 100g of mixed powder, the ball milling speed is 250rpm, and the ball-to-material ratio (mass ratio) is 10:1;
(4) Drying the wet-ground alloy powder in a vacuum drying oven (the dried prealloyed powder retains 0.3wt.% of cyclohexane), putting 80g of the dried alloy powder into a graphite sintering mold with the diameter of phi 20mm, and sintering into a block composite material by adopting discharge plasma; the sintering process parameters are as follows:
Sintering temperature: 950 ℃;
Rate of temperature rise: 90 ℃/min at room temperature to 200 ℃,120 ℃/min at 200 ℃ to 950 ℃;
The heat preservation time is as follows: 7min; sintering pressure: 30MPa; sintering vacuum degree: 8Pa.
The in-situ self-generated TiC (volume fraction is 2 vol.%) prepared by the comparative example and Ni are added to synergistically regulate and control the Fe-Co-based soft magnetic composite material, and a microstructure picture is shown in figure 13, so that the microstructure is composed of an alloy matrix, in-situ self-generated TiC particles and a small number of holes. The room temperature compression stress strain curve of the material is shown in figure 14, the yield strength, the breaking strength and the breaking strain are 711MPa, 2079MPa and 26%, respectively, and the yield strength is reduced by 38% compared with that of the example 2. The room temperature hysteresis loop of the material is shown in figure 15, and the saturation magnetization Ms=179.0 emu/g is improved by 2% compared with that of the material in the example 2; the coercive force hc=4.5 Oe is improved by 45% compared with example 2, and the soft magnetic performance is obviously reduced compared with example 2.
Comparative example 3
The preparation method of the Fe-Co-based composite material with the synergistic regulation and control of the in-situ self-generated TiC and Ni addition specifically comprises the following steps:
(1) The Fe-Co-based composite material is Fe 35Co35Ni30/TiC, and Fe, co, ni, ti element powder is weighed and prepared into mixed powder according to the atomic percentage of Fe 33.4%, co 33.4%, ni 28.6% and Ti 4.6%, wherein the particle size of each element powder is less than or equal to 45um, and the purity is more than or equal to 99.7wt.%;
(2) Placing the prepared mixed powder into a powder mixer to mix for 7 hours, and uniformly mixing;
(3) And (3) filling the uniformly mixed powder into a stainless steel vacuum ball milling tank, filling argon into the ball milling tank for protection, and then carrying out wet milling for 45h to obtain alloy powder. The process control agent is cyclohexane (C 6H12), the dosage of the cyclohexane is 260mL relative to the dosage of each 100g of mixed powder, the ball milling speed is 300rpm, and the ball-to-material ratio (mass ratio) is 15:1;
(4) Drying the wet-ground alloy powder in a vacuum drying oven (the dried prealloyed powder retains 1.1wt.% of cyclohexane), putting 80g of the dried alloy powder into a graphite sintering mold with the diameter of phi 20mm, and sintering into a block composite material by adopting discharge plasma; the sintering process parameters are as follows:
Sintering temperature: 900 ℃;
Rate of temperature rise: 80 ℃/min at room temperature to 200 ℃, 125 ℃/min at 200 ℃ to 900 ℃;
the heat preservation time is as follows: 8min; sintering pressure: 30MPa; sintering vacuum degree: 8Pa.
The in-situ self-generated TiC (volume fraction is 8 vol.%) prepared by the comparative example and Ni are added to synergistically regulate and control the Fe-Co-based composite material, a microstructure picture is shown in figure 16, and the microstructure is composed of an alloy matrix, in-situ self-generated TiC particles and a small number of holes. The room temperature compression stress strain curve of the material is shown in figure 17, the yield strength, the breaking strength and the breaking strain are 1590MPa, 2022MPa and 18%, and the yield strength is improved by 27% compared with that of the example 3. The room temperature hysteresis loop of the material is shown in fig. 18, and the saturation magnetization ms=122 emu/g is reduced by 18% compared with that of the material in the embodiment 3; the coercivity hc=13.0 Oe is improved by 88% compared with example 3, the soft magnetic performance is obviously reduced compared with example 3, and the coercivity hc=13.0 Oe is beyond the coercivity (less than 12.5 Oe) range of the soft magnetic material.
The above description is only of the preferred embodiments of the present invention, and is not intended to limit the invention in any way, but other variations and modifications are possible without departing from the technical solution described in the claims.
Claims (10)
1. The Fe-Co-based soft magnetic composite material with the in-situ self-generated TiC and Ni added and regulated in a synergic manner is characterized by comprising Fe, co, ni, ti and C, wherein the content of Ni element is 9-30at percent and the content of Ti element is 1.7-4.0at percent according to the atomic percentage of metal elements; ti and C are present in the composite as in situ autogenous TiC.
2. The Fe-Co-based soft magnetic composite material with synergistic regulation of in-situ self-generated TiC and Ni addition according to claim 1, wherein the content of Fe element is 30-50at.% and the content of Co element is 30-50at.% in terms of atomic percentage of metal element.
3. The Fe-Co-based soft magnetic composite material with synergistic regulation of in-situ self-generated TiC and Ni addition according to claim 1, wherein the content of Ni element is 14.5 at%, the content of Ti element is 2.9 at%, the content of Fe element is 38.9 at%, and the content of Co element is 43.7 at%, based on the atomic percentage of metal elements.
4. The method for preparing the Fe-Co-based soft magnetic composite material with synergistic regulation and control of in-situ self-generated TiC and Ni addition as claimed in any one of claims 1 to 3, which is characterized in that: the Fe-Co-based soft magnetic composite material with the synergistic regulation and control of the in-situ self-generated TiC and Ni addition is obtained through the preparation of a mechanical alloying and spark plasma sintering process; the prealloyed powder sintered by the spark plasma retains a certain amount of cyclohexane as a residual process control agent, wherein the residual process control agent contained in the prealloyed powder is as follows: 0.4-1.0wt.%.
5. The method for preparing the Fe-Co-based soft magnetic composite material with the synergistic regulation and control of the addition of in-situ authigenic TiC and Ni according to claim 4, which is characterized by comprising the following steps:
(1) Element powder or alloy powder of Fe, co, ni, ti is weighed and mixed according to the proportion to obtain a mixture;
(2) Placing the mixture obtained in the step (1) into a powder mixer for uniform mixing to obtain mixed powder;
(3) Adding the mixed powder obtained in the step (2) into process control agent cyclohexane and grinding ball protective atmosphere for wet grinding to obtain prealloyed powder;
(4) And (3) performing semi-drying treatment on the prealloyed powder in the step (3), and then heating to perform sintering treatment to obtain the Fe-Co-based soft magnetic composite material with in-situ self-generated TiC and Ni added and cooperatively regulated.
6. The method for preparing an in-situ self-generated TiC and Ni-added Co-regulated Fe-Co-based soft magnetic composite according to claim 5, wherein the elemental powder or alloy powder of Fe, co, ni, ti in step (1) has a purity of 99.7wt.% or more and a powder particle size of 45 μm or less.
7. The method for preparing an in-situ self-generated TiC and Ni added synergistic controlled Fe-Co-based soft magnetic composite material according to claim 5, wherein the mixing time in the step (2) is 5-10 hours.
8. The method for preparing the Fe-Co-based soft magnetic composite material with the synergistic regulation and control of the addition of the in-situ self-generated TiC and the Ni according to claim 5, wherein the wet milling time in the step (3) is 40-60 hours; the wet grinding rotating speed is more than or equal to 250rpm; the wet grinding ball material ratio is 10:1-20:1; the protective atmosphere is argon.
9. The method for preparing an in-situ self-generated TiC and Ni added synergistic controlled Fe-Co based soft magnetic composite material according to claim 5, wherein the heating in the step (4) is sectional heating, the temperature is raised at a rate of 80-90 ℃/min when the temperature is between room temperature and 200 ℃, and the temperature is raised at a rate of 100-150 ℃/min when the temperature is between 200 and 1000 ℃.
10. The method for preparing the Fe-Co-based soft magnetic composite material with the synergistic regulation and control of the addition of in-situ self-generated TiC and Ni according to claim 5, wherein the sintering temperature in the step (4) is 900-1000 ℃; the sintering heat preservation time is 5-8min; the pressure of sintering treatment is 30-40MPa; the sintering vacuum degree is less than or equal to 8Pa.
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