CN111593260B - B2 nanoparticle coherent precipitation strengthened ultrahigh-strength maraging stainless steel and preparation method thereof - Google Patents

B2 nanoparticle coherent precipitation strengthened ultrahigh-strength maraging stainless steel and preparation method thereof Download PDF

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CN111593260B
CN111593260B CN202010555730.3A CN202010555730A CN111593260B CN 111593260 B CN111593260 B CN 111593260B CN 202010555730 A CN202010555730 A CN 202010555730A CN 111593260 B CN111593260 B CN 111593260B
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王清
王镇华
董闯
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Dalian University of Technology
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Abstract

The B2 nano particle coherent precipitation strengthened ultrahigh-strength maraging stainless steel belongs to the field of high-strength stainless steel, and comprises Fe, Cr, Ni, Al, Mo, W, Nb, C and B elements, wherein Si, Mn, S, P, O and N are impurity elements, and the mass percentage (wt.%) of alloy components is Cr: 4.0-6.0, Ni: 13.0 to 15.0, Al: 3.0 to 4.0, Mo: 1.0 to 2.0, W: 0.3 to 0.7, Nb: 0.2-0.4, C: 0.03 to 0.05, B: 0.004-0.008, less than or equal to 0.20 of Si, less than or equal to 0.20 of Mn, less than or equal to 0.01 of S, less than or equal to 0.02 of P, less than or equal to 0.005 of O, less than or equal to 0.02 of N, Fe: the balance, the atomic percent ratio of Nb to C is 1:1, and the atomic percent ratio of Cr/(Mo + W) is 8: 1. According to the invention, the uniform coherent precipitation of high-density B2 phase nanoparticles on a martensite matrix is realized through alloy component design, so that the alloy has ultrahigh strength with the strength higher than 2.0GPa, good uniform plastic deformation capability and excellent corrosion resistance; the preparation process is simple, the material cost is greatly reduced, and the novel ultrahigh-strength maraging stainless steel is provided.

Description

B2 nanoparticle coherent precipitation strengthened ultrahigh-strength maraging stainless steel and preparation method thereof
Technical Field
The invention belongs to the field of high-strength stainless steel, and particularly relates to BCC-based ultrahigh-strength maraging stainless steel with enhanced coherent precipitation of B2 nanoparticles and a preparation method thereof, wherein the strength of the steel exceeds 2.0GPa, and the elongation of the steel exceeds 8.0%.
Background
The maraging steel as the ultrahigh-strength steel is widely applied to the advanced fields of aviation, aerospace, military and the like, and has higher engineering application value and scientific research significance. The traditional maraging steel takes ultra-low carbon (or no carbon) lath martensite (BCC base) with high density dislocation as a matrix, and forms a plurality of intermetallic compounds (Ni) which are not coherent or semi-coherent with the matrix after aging treatment3Ti、Ni3Mo and Fe2(Mo, Ti)) is strengthened. These precipitated phases often have a large interfacial energy with the matrix, have a high nucleation barrier, and are prone to nucleation at defects such as grain boundaries, resulting in low density and non-uniform precipitation of the strengthening phase. Meanwhile, in the aging process, a precipitated phase is easy to grow along the direction of low mismatching degree and easy to coarsen, so that the alloy is sensitive to process abnormity; and large lattice distortion exists between the precipitated phase and the matrix, and stress concentration is easily generated in the dislocation motion process, so that crack initiation is induced, and the uniform plastic deformation capability of the alloy is extremely poor. In order to increase the density of the precipitated phase, the steel is generally added with high content of Ni and Co elements, which further increases the use cost of the steel. Conventional maraging steels therefore have certain limitations.
Unlike conventional maraging steels, maraging steels that are precipitation strengthened with the B2-NiAl nanoparticle coherent precipitation avoid these limitations. The lattice constant (0.2887nm) of the ordered superstructure B2-NiAl phase of BCC is similar to that (0.2866nm) of alpha-Fe, the coherent precipitated phase interface energy is lower, the required nucleation power is smaller, and the uniform coherent precipitation of high-density B2 nano particles on a martensite matrix is ensured, so that the maraging steel has ultrahigh strength and good ductility and toughness.
The requirement of the maraging steel on corrosion resistance is continuously increased while ultrahigh strength and plasticity are pursued. The addition of the Cr element imparts excellent corrosion resistance to maraging steel, but inevitably leads to an increase in brittleness of such steel, resulting in a decrease in strength. Like typical maraging stainless steel 13-8Mo (Fe-13Cr-8Ni-2Mo-1Al-0.05C, wt.%), Cr is added to improve the corrosion resistance of the steel, and although B2 nanoparticles are also used for coherent precipitation strengthening, the room temperature yield strength of the steel is only 1400MPa, which does not meet the ultra-high strength requirements of the maraging steel, indicating that the alloy composition of the steel still needs to be further adjusted and optimized to obtain the ultra-high strength maraging stainless steel.
Therefore, two core problems that restrict the development and application of current high strength maraging stainless steels: on one hand, the plasticity and toughness are ensured while the ultrahigh strength is obtained; on the other hand, the corrosion resistance is improved, and the plasticity and toughness of the alloy are not reduced. In view of the above, the invention provides a novel ultra-high strength maraging stainless steel with good corrosion resistance and strong plastic matching, which is strengthened by coherent precipitation of B2 nano-particles, the strength of the novel ultra-high strength maraging stainless steel exceeds 2.0GPa, and the elongation of the novel ultra-high strength maraging stainless steel is more than 8.0%.
Disclosure of Invention
The invention designs and develops B2 nano-particle coherent precipitation strengthened ultrahigh-strength maraging stainless steel. The invention aims to realize uniform coherent precipitation on a martensite matrix through high-density B2 nano-particles, so that the maraging stainless steel with ultrahigh strength, good plasticity and corrosion resistance is designed.
The technical scheme adopted by the invention is as follows:
the B2 nano particle coherent precipitation strengthened ultrahigh-strength maraging stainless steel comprises Fe, Cr, Ni, Al, Mo, W, Nb, C and B elements, wherein Si, Mn, S, P, O and N are impurity elements, and the alloy components of the ultrahigh-strength maraging stainless steel in percentage by mass (wt.%) are as follows, Cr: 4.0-6.0, Ni: 13.0 to 15.0, Al: 3.0 to 4.0, Mo: 1.0 to 2.0, W: 0.3 to 0.7, Nb: 0.2-0.4, C: 0.03 to 0.05, B: 0.004-0.008, less than or equal to 0.20 of Si, less than or equal to 0.20 of Mn, less than or equal to 0.01 of S, less than or equal to 0.02 of P, less than or equal to 0.005 of O, less than or equal to 0.02 of N, Fe: the balance; and the atomic percent ratio of Nb to C is 1:1, and the atomic percent ratio of Cr/(Mo + W) is 8: 1.
The maraging stainless steel has a specific structure and appearance: high density of>1024m-3) The B2 phase nano particles (3-5 nm) are uniformly precipitated on the lath martensite matrix in a coherent manner, so that the strength of the steel is higher than 2.0 GPa.
A preparation method of the B2 nano particle coherent precipitation strengthened ultrahigh-strength maraging stainless steel comprises the following steps: firstly, putting the alloy components into vacuum arc melting according to the mass percentage for at least four times to obtain an alloy ingot; secondly, homogenizing the alloy ingot by adopting a muffle furnace, wherein the treatment temperature is 1250 ℃, the treatment time is 2 hours, and then, carrying out multi-pass cold rolling, wherein the total deformation is about 70%; and finally, annealing for 15min at 950 ℃, and aging for 4-48 h at 500 ℃.
The conception for realizing the technical scheme is as follows: the composition design of the maraging stainless steel was carried out by the applicant's cluster composition design method. The component design method is based on a structure model of 'cluster + connecting atom', and divides a stable solid solution structure into two parts of cluster and connecting atom, wherein the cluster is a nearest neighbor coordination polyhedron formed by taking a certain atom as a center, for example, the cluster in an FCC (fluid catalytic cracking) structure is a cuboctahedron with a coordination number of CN12, and the connecting atom is arranged at a gap position of a cluster stack and is usually positioned at the next nearest neighbor shell layer of the cluster. Thus, a simple cluster composition [ cluster ] can be determined](connecting atom)xI.e. one cluster is matched to x connecting atoms. The cluster component design method is successfully applied to the design of various engineering alloys such as high-temperature austenitic stainless steel, low-elasticity beta-Ti alloy and the like, and provides a new idea and method for the component design of high-performance engineering alloys.
According to previous work by the applicant, in a ternary Fe-Ni-Cr alloy system, we obtained the lowest limit cluster composition of the austenite (FCC) [ Ni-Fe ]12]Cr3Wherein Ni and Fe have strong interaction, Ni occupies central atomic position, and Cr occupies connecting atomic position. After the high temperature solid solution + water quenching treatment, the alloy of the composition is transformed into a complete martensite structure. When Al element is added on the basis, Al occupies the central position of the cluster due to stronger interaction between Al and Fe, and correspondingly, Ni and Cr are both positioned at connecting atom positions, so that the cluster type [ Al-Fe ] is finally obtained12](Ni,Cr)3. In addition, the structural stability of Austenite (FCC)There is a direct relationship with the Ni equivalent and Cr equivalent of the alloy. For the cluster composition formula [ Al-Fe12](Ni2Cr) (═ Fe-6.00Cr-13.57Ni-3.11Al wt.%) constituent alloy with Ni equivalent of Nieq=1.0×cNi13.57 wt.%, Cr equivalent is Creq=1.0×cCr+2.5×cAl13.8 wt.%, satisfies the condition of austenite stabilization, and ensures that the alloy with the composition can form a complete martensite structure after solution quenching.
The addition of Mo and W elements can improve the pitting corrosion resistance of the steel while playing a role in solid solution strengthening. In addition, Mo is added in a quaternary system of Fe-Cr-Ni-Al, so that the lattice constant of a BCC matrix can be increased, the lattice mismatch between the BCC matrix and a precipitated phase B2 is reduced, and the coherent precipitation of a B2 phase is facilitated. Therefore, Mo and W are added in an atomic ratio of Cr/(Mo + W) of 8:1 in place of the Cr element in the cluster formula. In addition, the MC type carbide not only can refine the prior austenite grains and strengthen the second phase, but the addition of C in an excessively high amount causes a reduction in the weldability of the alloy and a reduction in the plasticity of the steel. Therefore, the addition of C element is controlled between 0.03-0.05 wt.%. At the same time, to suppress coarse Cr23C6The precipitation of carbide needs to add the same atomic percent of Nb element. The addition of trace element B (0.004-0.008 wt.%) can improve the bonding force of grain boundaries, thereby improving the plasticity of steel. Finally, the components of the B2 nano particle coherent precipitation strengthened ultrahigh-strength maraging stainless steel are determined to be Fe- (4.0-6.0) Cr- (13.0-15.0) Ni- (3.0-4.0) Al- (1.0-2.0) Mo- (0.3-0.7) W- (0.2-0.4) Nb- (0.03-0.05) C- (0.004-0.008) B, and Si, Mn, S, P, O and N are impurity elements: si is less than or equal to 0.20, Mn is less than or equal to 0.20, S is less than or equal to 0.01, P is less than or equal to 0.02, O is less than or equal to 0.005, and N is less than or equal to 0.02 (wt.%).
The preparation method of the invention comprises the following steps: high-purity metal materials are adopted and mixed according to the mass percentage. The ingredients are melted repeatedly for at least four times by adopting a vacuum non-consumable arc melting furnace under the protection of argon atmosphere to obtain an alloy ingot with uniform components and the mass of about 100g, and the mass loss is not more than 0.1 percent in the melting process. Homogenizing the alloy ingot in a muffle furnaceThe treatment temperature is 1250 ℃ and the treatment time is 2 h. And then, carrying out multi-pass cold rolling, wherein the reduction amount of each pass is not more than 0.2mm, and the total deformation amount is about 70%, so as to obtain a plate sample with the thickness of about 3 mm. And then annealing the alloy plate at 950 ℃ for 15min, and finally performing aging treatment at 500 ℃ for 4-48 h. Using metallographic microscope (OM), Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM) and X-ray diffractometer (XRD, Cu K)αRadiation, λ 0.15406nm) to detect alloy structure and structure; using an HVS-1000 Vickers hardness tester to perform hardness tests on the series alloy in different heat treatment states; testing the tensile mechanical property at room temperature by using a UTM5504 electronic universal tensile testing machine; corrosion resistance testing of the alloys was performed using the CS350 electrochemical workstation in a 3.5 wt.% NaCl aqueous solution. Thus, the invention is determined to be the B2 nano particle coherent precipitation strengthened ultrahigh-strength maraging stainless steel. The alloy comprises the following components in percentage by mass (wt.%): 4.0-6.0, Ni: 13.0 to 15.0, Al: 3.0 to 4.0, Mo: 1.0 to 2.0, W: 0.3 to 0.7, Nb: 0.2-0.4, C: 0.03 to 0.05, B: 0.004-0.008, less than or equal to 0.20 of Si, less than or equal to 0.20 of Mn, less than or equal to 0.01 of S, less than or equal to 0.02 of P, less than or equal to 0.005 of O, less than or equal to 0.02 of N, Fe: the balance; and the atomic percent ratio of Nb to C is 1:1, and the atomic percent ratio of Cr/(Mo + W) is 8: 1. The indexes of the structure and the room temperature performance of the material are as follows: the alloy has a room temperature hardness of HV 570-620 kgf mm-2Room temperature yield strength σsGreater than or equal to 1820MPa and tensile strength sigmabNot less than 2000MPa, and elongation delta after fracture not less than 8%; the self-corrosion potential of the alloy in a 3.5 wt.% aqueous NaCl solution is Ecorr0.45-0.32V, and the self-corrosion current is Icorr=2.1~4.3μA·cm-2(ii) a After the alloy is aged for 4-48 h at 500 ℃, (C)>1024m-3) The B2 phase nano particles (3-5 nm) are uniformly precipitated on the lath martensite matrix in a coherent manner.
Compared with the prior art, the invention has the beneficial effects that:
the invention designs and develops the B2 nano particle coherent precipitation strengthened ultrahigh strength maraging stainless steel according to a cluster composition method developed by self. Different from the traditional maraging stainless steel which adopts non-coherent or semi-coherent precipitation strengthening, the invention adopts a brand new idea of coherent precipitation strengthening, and realizes the purpose of ultrahigh strength of the maraging stainless steel by coherent precipitation of high-density B2 phase nano particles on a martensite matrix; meanwhile, uniform precipitation and a coherent phase interface caused by coherent precipitation, and high-density movable dislocation in lath martensite hinder the initiation of cracks, and the uniform plastic deformation capacity of the novel horse aged stainless steel is improved. The co-addition of Cr and Al leads the alloy to have excellent corrosion resistance which is equivalent to that of the conventional maraging stainless steel Custom465(Fe-12Cr-11Ni-1Mo-1.65Ti-0.03C wt.%), and has good ductility and toughness while ultrahigh strength is obtained. In addition, the novel maraging stainless steel adopts cheap elements such as Al and Cr to replace the expensive elements such as Co and Ti in the traditional maraging steel, and adds the C element avoided by the traditional maraging steel, so that the preparation process is simple, and the material cost is greatly reduced.
The invention has the advantages that: firstly, an ultra-high strength maraging stainless steel strengthened by coherent precipitation of B2 nano particles is developed, and the mass percentage (wt.%) of alloy components is Cr: 4.0-6.0, Ni: 13.0 to 15.0, Al: 3.0 to 4.0, Mo: 1.0 to 2.0, W: 0.3 to 0.7, Nb: 0.2-0.4, C: 0.03 to 0.05, B: 0.004-0.008, less than or equal to 0.20 of Si, less than or equal to 0.20 of Mn, less than or equal to 0.01 of S, less than or equal to 0.02 of P, less than or equal to 0.005 of O, less than or equal to 0.02 of N, Fe: the balance; secondly, the novel maraging stainless steel adopts cheap elements such as Al and Cr to replace the expensive elements such as Co and Ti in the traditional maraging steel, and adds C elements avoided by the traditional maraging steel, so that the preparation process is simple, and the material cost is greatly reduced; and thirdly, the novel maraging stainless steel has ultrahigh strength with the strength higher than 2.0GPa, good uniform plastic deformation capacity and excellent corrosion resistance through coherent precipitation strengthening of the high-density B2 phase particles.
Drawings
FIG. 1 is a TEM microstructure of the alloy prepared in example 1, with high density of B2 phase nanoparticles coherently precipitated on a martensitic matrix.
Detailed Description
The following describes the embodiments of the present invention in detail with reference to the technical solutions.
Example 1: fe-5.30Cr-13.47Ni-3.10Al-1.22Mo-0.50W-0.23Nb-0.03C-0.005B (wt.%) alloy
The method comprises the following steps: alloy preparation
High-purity metal materials are adopted and mixed according to the mass percentage. The ingredients are melted repeatedly for at least four times by adopting a vacuum non-consumable arc melting furnace under the protection of argon atmosphere to obtain an alloy ingot with uniform components and the mass of about 100g, and the mass loss is not more than 0.1 percent in the melting process. The alloy ingot was homogenized at 1250 ℃ for 2 hours in a muffle furnace. And then, carrying out multi-pass cold rolling, wherein the reduction amount of each pass is not more than 0.2mm, and the total deformation amount is about 70%, so as to obtain a plate sample with the thickness of about 3 mm. Then, the alloy plate is annealed at 950 ℃/15min, and finally, the aging is carried out at 500 ℃/8 h.
Step two: testing the organization structure, mechanical property and corrosion resistance of the alloy
The OM, SEM and XRD are used for detecting the structure and structure of the alloy after the stabilizing treatment, and the result shows that the alloy is a lath martensite structure, and high-density B2 phase nano particles are coherently precipitated on a martensite matrix, as shown in figure 1; hardness test was carried out by using a Vickers hardness tester (HV) 605 kgf. mm-2And the mechanical property data at room temperature is measured by using a UTM5504 electronic universal tensile testing machine: yield strength sigmas1935MPa tensile Strength σb2128MPa, elongation after fracture delta of 8.3 percent and uniform elongation of 5.4 percent; corrosion resistance data for the alloy measured using the CS350 electrochemical workstation in a 3.5 wt.% NaCl aqueous solution: self-etching potential of Ecorr-0.423V, self-corrosion current Icorr=4.233μA·cm-2
Example 2: fe-4.0Cr-15.0Ni-3Al-1Mo-0.70W-0.2Nb-0.03C-0.004B (wt.%) alloy
The method comprises the following steps: alloy preparation
High-purity metal materials are adopted and mixed according to the mass percentage. The ingredients are melted repeatedly for at least four times by adopting a vacuum non-consumable arc melting furnace under the protection of argon atmosphere to obtain an alloy ingot with uniform components and the mass of about 100g, and the mass loss is not more than 0.1 percent in the melting process. The alloy ingot was homogenized at 1250 ℃ for 2 hours in a muffle furnace. And then, carrying out multi-pass cold rolling, wherein the reduction amount of each pass is not more than 0.2mm, and the total deformation amount is about 70%, so as to obtain a plate sample with the thickness of about 3 mm. Then, the alloy plate is annealed at 950 ℃/15min, and finally, the aging is carried out at 500 ℃/12 h.
Step two: alloy texture Structure and mechanical Property testing
The alloy structure and structure after the stabilization treatment are detected by OM, SEM and XRD, and the result shows that the alloy of the invention is a lath martensite structure, and high-density B2 phase nano-particles are coherently precipitated on a martensite matrix, similar to the embodiment 1; hardness test was carried out by using a Vickers hardness tester HV 590kgf mm-2And measuring mechanical property parameters at room temperature by using a UTM5504 electronic universal tensile testing machine: yield strength sigmas1890MPa tensile Strength σb2050MPa, elongation after break δ of 8.9%, uniform elongation of 5.8%; corrosion resistance data for the alloy using the CS350 electrochemical workstation measured in a 3.5 wt.% NaCl aqueous solution was a self-corrosion potential Ecorr-0.406V, self-corrosion current Icorr=3.654μA·cm-2
Example 3: fe-6.0Cr-13.0Ni-4.0Al-2.0Mo-0.50W-0.40Nb-0.05C-0.008B (wt.%) alloy
The method comprises the following steps: alloy preparation
High-purity metal materials are mixed according to mass percentage. The ingredients are melted repeatedly for at least four times by adopting a vacuum non-consumable arc melting furnace under the protection of argon atmosphere to obtain an alloy ingot with uniform components and the mass of about 100g, and the mass loss is not more than 0.1 percent in the melting process. The alloy ingot was homogenized at 1250 ℃ for 2 hours in a muffle furnace. And then, carrying out multi-pass cold rolling, wherein the reduction amount of each pass is not more than 0.2mm, and the total deformation amount is about 70%, so as to obtain a plate sample with the thickness of about 3 mm. Then, the alloy plate is annealed at 950 ℃/15min, and finally, the aging is carried out at 500 ℃/48 h.
Step two: testing the organization structure, mechanical property and corrosion resistance of the alloy
The OM, SEM and XRD are used for detecting the structure and structure of the alloy after the stabilizing treatment, and the result shows that the alloy is a lath martensite structure, and high-density B2 phase nano particles are coherently precipitated on a martensite matrix, and the method is similar to the method in example 1; hardness test was carried out by using a Vickers hardness tester (HV: 587 kgf. mm)-2And the mechanical property data at room temperature is measured by using a UTM5504 electronic universal tensile testing machine: yield strength sigmas1875MPa tensile Strength σb2017MPa, the elongation delta after breakage is 9.1 percent, and the uniform elongation is 6.0 percent; corrosion resistance data for the alloy measured using the CS350 electrochemical workstation in a 3.5 wt.% NaCl aqueous solution: self-etching potential of Ecorr-0.378V, self-corrosion current Icorr=4.156μA·cm-2
The above-mentioned embodiments only express the embodiments of the present invention, but not should be understood as the limitation of the scope of the invention patent, it should be noted that, for those skilled in the art, many variations and modifications can be made without departing from the concept of the present invention, and these all fall into the protection scope of the present invention.

Claims (2)

1. The ultra-high strength maraging stainless steel strengthened by coherent precipitation of B2 nano-particles is characterized by comprising Fe, Cr, Ni, Al, Mo, W, Nb, C and B elements, wherein Si, Mn, S, P, O and N are impurity elements, and the alloy components of the ultra-high strength maraging stainless steel are as follows in percentage by mass (wt.%), and Cr: 4.0-6.0, Ni: 13.0 to 15.0, Al: 3.0 to 4.0, Mo: 1.0 to 2.0, W: 0.3 to 0.7, Nb: 0.2-0.4, C: 0.03 to 0.05, B: 0.004-0.008, less than or equal to 0.20 of Si, less than or equal to 0.20 of Mn, less than or equal to 0.01 of S, less than or equal to 0.02 of P, less than or equal to 0.005 of O, less than or equal to 0.02 of N, Fe: the balance; the atomic percent ratio of Nb to C is 1:1, and the atomic percent ratio of Cr/(Mo + W) is 8: 1;
the maraging stainless steel has a specific structure and appearance: the uniform coherent precipitation of high density B2 phase nanoparticles on lath martensite matrix allows for ultra-high strength maragingThe strength of the stainless steel is higher than 2.0GPa, the particle diameter of the nano particles is 3-5 nm, and the high density is>1024m-3
2. A method of making the B2 nanoparticle coherent precipitation-strengthened ultra-high strength maraging stainless steel of claim 1, comprising: firstly, putting the alloy components into vacuum arc melting according to the mass percentage for at least four times to obtain an alloy ingot; secondly, homogenizing the alloy ingot by adopting a muffle furnace, wherein the treatment temperature is 1250 ℃, the treatment time is 2 hours, and then, carrying out multi-pass cold rolling, wherein the total deformation is about 70%; and finally, annealing for 15min at 950 ℃, and aging for 4-48 h at 500 ℃.
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