CN115110008B - Pitting corrosion resistant martensitic hardened stainless steel - Google Patents
Pitting corrosion resistant martensitic hardened stainless steel Download PDFInfo
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Abstract
The application provides pitting corrosion resistant martensitic hardening stainless steel and a preparation method thereof, and relates to the field of metallurgy. The pitting corrosion resistant martensitic hardening stainless steel comprises the following components in percentage by mass: less than or equal to 0.07 percent of C, 0.35 to 0.68 percent of Mn, 0.32 to 0.70 percent of Si, less than or equal to 0.035 percent of P, less than or equal to 0.030 percent of S, 3.8 to 5.2 percent of Nis, 14.0 to 16.8 percent of Crs, 2.8 to 4.3 percent of Cu2, 0.3 to 1.5 percent of Mo0.050 to 0.10 percent of V, less than 0.005 percent of Al, 0.15 to 0.25 percent of Nb, less than or equal to 0.030 percent of Te and the balance of Fe and inevitable impurities; wherein 0.35 < [ Te ]/[ S ] < 1.0. The pitting corrosion resistant martensitic hardened stainless steel provided by the application realizes effective regulation and control of inclusions in the steel and promotes the pitting corrosion resistance of the material.
Description
Technical Field
The application relates to the field of metallurgy, in particular to pitting corrosion resistant martensitic hardening stainless steel and a preparation method thereof.
Background
The 15-5PH stainless steel is a martensite precipitation hardening stainless steel, has good processing technology performance and good mechanical property, and is often applied in the fields of aviation parts, airplane parts and the like. However, the existing research shows that the corrosion resistance of the 15-5PH stainless steel is general and is often faced with more serious pitting corrosion, which is mainly related to the microstructure such as inclusions in the steel. In order to improve the pitting corrosion resistance of the material, at present, additive manufacturing technologies such as 3D printing and the like are studied to improve microstructure defects such as inclusions in steel, but such methods are too high in cost and are not easy to produce in large quantities.
Disclosure of Invention
The present application aims to provide a pitting corrosion resistant martensitic hardened stainless steel and a method for manufacturing the same to solve the above problems.
In order to achieve the purpose, the following technical scheme is adopted in the application:
a pitting corrosion resistant martensitic hardened stainless steel, the composition of which is calculated by mass percentage and comprises:
less than or equal to 0.07 percent of C, 0.35 to 0.68 percent of Mn, 0.32 to 0.70 percent of Si, less than or equal to 0.035 percent of P, less than or equal to 0.030 percent of S, 3.8 to 5.2 percent of Nis, 14.0 to 16.8 percent of Cr0, 2.8 to 4.3 percent of Cu2, 0.3 to 1.5 percent of Mo0, 0.050 to 0.10 percent of V, less than 0.005 percent of Al, 0.15 to 0.25 percent of Nb, less than or equal to 0.030 percent of Te and the balance of Fe and inevitable impurities;
wherein 0.35 < [ Te ]/[ S ] < 1.0.
Preferably, the pitting corrosion resistant martensitic hardened stainless steel has a lath martensite structure.
The application also provides a preparation method of the pitting corrosion resistant martensitic hardened stainless steel, which comprises the following steps:
smelting the raw materials by using a vacuum induction furnace to obtain molten steel, and cooling to obtain a steel ingot;
and forging the steel ingot, then carrying out first heat treatment, then rolling and second heat treatment, and cooling to obtain the pitting corrosion resistant martensitic hardening stainless steel.
Preferably, the smelting is carried out under the protection of argon, and the pressure is 0.04 MPa-0.06 MPa.
Preferably, before the vacuum induction furnace is filled with the argon, the vacuum induction furnace is vacuumized to 2 x 10 -3 Pa-3×10 -3 Pa。
Preferably, the smelting temperature is 1575-1650 ℃, and the heat preservation time is 25-30 min.
Preferably, the first heat treatment comprises:
heating to 1100-1200 deg.c and maintaining for 70-90 min.
Preferably, the rolling reduction is 50-70%.
Preferably, the second heat treatment includes a normalizing treatment, a first solution treatment, and a second solution treatment, which are sequentially performed.
Preferably, the temperature of the normalizing treatment is 1120-1200 ℃, and the time is 100-150 min;
the temperature of the first solution treatment is 1000-1080 ℃, and the time is 40-70 min;
the temperature of the first solution treatment is 480-550 ℃, and the time is 120-180 min.
Compared with the prior art, the beneficial effect of this application includes:
according to the pitting corrosion resistant martensitic hardening stainless steel, te alloying is realized by introducing Te element, the size, the components and the structure of inclusions in the steel are improved, effective regulation and control of the inclusions in the steel are realized by regulating and controlling the Te/S ratio, and the pitting corrosion resistance of the material is improved. The addition of a proper amount of Te element can also promote the formation of Te (OH) with strong oxidizing property on the surface of the metal 6 Etc. can promote Cr on the surface of stainless steel 2 O 3 And Cr (OH) 3 And the formation of substances promotes the densification of the passive film on the surface of the stainless steel, reduces the number of defects in the passive film and improves the corrosion resistance of the stainless steel. When excessive Te element is added, teO having reducibility is formed on the metal surface 2 And TeCl 4 Etc. which would block Cr on the surface of stainless steel 2 O 3 And Cr (OH) 3 And the like, and the corrosion resistance of the material is reduced.
The preparation method of the pitting corrosion resistant martensitic hardened stainless steel provided by the application is simple in process, and the obtained steel is good in pitting corrosion resistance.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments are briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is an SEM photograph of a steel product obtained in example 2;
FIG. 2 is an SEM photograph of a steel material obtained in comparative example 1;
FIG. 3 is an SEM photograph of a steel material obtained in comparative example 5;
FIG. 4 is a photograph showing the morphology and elemental analysis of inclusions in the steel material obtained in comparative example 1;
FIG. 5 is a photograph showing the morphology and elemental analysis of inclusions in the steel material obtained in example 2;
FIG. 6 is a photograph showing the morphology and elemental analysis of inclusions in the steel material obtained in comparative example 5;
FIG. 7 is a graph showing the size distribution of inclusions in the steels obtained in comparative examples 1, 2 and 5;
FIG. 8 is a graph showing electrochemical polarization curves of the steels obtained in comparative example 1, example 2 and comparative example 5.
Detailed Description
The terms as used herein:
"by 8230; \ 8230; preparation" is synonymous with "comprising". As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains" or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of 8230% \8230comprises" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of 8230' \8230"; composition "appears in a clause of the subject matter of the claims and not immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4," "1 to 3," "1 to 2 and 4 to 5," "1 to 3 and 5," and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent an arbitrary unit mass, for example, 1g or 2.689 g. If the parts by mass of the component A are a parts and the parts by mass of the component B are B parts, the mass ratio of the component A to the component B is expressed as a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
A pitting corrosion resistant martensitic hardened stainless steel comprises the following components in percentage by mass:
less than or equal to 0.07 percent of C, 0.35 to 0.68 percent of Mn, 0.32 to 0.70 percent of Si, less than or equal to 0.035 percent of P, less than or equal to 0.030 percent of S, 3.8 to 5.2 percent of Nis, 14.0 to 16.8 percent of Crs, 2.8 to 4.3 percent of Cu2, 0.3 to 1.5 percent of Mo0.050 to 0.10 percent of V, less than 0.005 percent of Al, 0.15 to 0.25 percent of Nb, less than or equal to 0.030 percent of Te and the balance of Fe and inevitable impurities;
wherein 0.35 < [ Te ]/[ S ] < 1.0.
The content of Mn is preferably 0.35% to 0.65%.
C is an element which has the greatest influence on corrosion resistance in steel, and in order to improve the strength of the martensitic stainless steel, a proper amount of C element needs to be added in the steel, but the existence of the C element can precipitate a large amount of carbide in the steel, so that potential difference among different microstructures in the steel is caused, the corrosion driving force is increased, the corrosion resistance of the material is reduced, the content of C in the steel is properly reduced, the corrosion rate of the material can be remarkably reduced, and the plasticity and the toughness of the material can be improved.
P is an effective alloy element for improving the corrosion resistance of the steel, is an effective anode depolarizer, accelerates the uniform dissolution of the steel, promotes the formation of alpha-FeOOH on the surface of the material, inhibits the formation of gamma-FeOOH, increases the resistance of a rust layer, hinders the transfer of a medium, and improves the protection of the rust layer, however, in the stainless steel, the corrosion resistance of the steel is mainly realized by a passive film on the surface of a sample, so that P is not needed to improve the corrosion resistance of the material, and in order to ensure the toughness of the material and prevent the occurrence of cold brittleness, the lower the P content in the steel is, the better;
cr is an important element for improving the corrosion resistance of the material, can effectively improve the corrosion potential of the material and promote the surface of the material to form a layer of compact oxide film, cr in stainless steel can promote the formation of a compact passive film on the surface of the material, the defects of the passive film on the surface of the material are gradually reduced along with the increase of the content of Cr, the protection of the passive film can be effectively improved, and the addition of Cr can also improve the strength of the material.
Cu is an effective alloy element for improving the corrosion resistance of the material, and can be enriched between the matrix and the rust layer, so that the compactness and the protection of the passive film on the surface of the stainless steel are improved; excessive Cu element can increase the hot brittleness of steel, and the defects of cracks and the like appear in the rolling process, so that the corrosion resistance of the material is reduced; therefore, the corrosion resistance of the stainless steel can be effectively improved by adding a proper amount of Cu element;
the Mo and Ni elements have an important effect on the protection of the stainless steel surface passivation film, a response oxide can be formed on the stainless steel surface by adding a proper amount of the Mo and Ni elements, the compactness and the protection of the passivation film are improved, and simultaneously, the formation of carbides in the steel can be promoted by adding the Mo and Ni elements, so that the strength and the toughness of the material are improved;
the S element has obvious negative influence on the corrosion resistance of the stainless steel, can be combined with Mn element in the steel to generate MnS inclusion, and the MnS inclusion and a steel matrix have larger potential difference, so that pitting corrosion initiation is easily induced, and the pitting corrosion resistance of the stainless steel is reduced;
the Te element is generally considered as a harmful element in steel, excessive Te element can cause the mechanical property of the material, but a proper amount of Te element can increase the wear resistance and the cutting property of steel, and the proper amount of Te element is added into stainless steel, so that MnS inclusion can be effectively modified, the potential difference between the inclusion and a steel matrix can be reduced, the pitting corrosion resistance of the stainless steel can be improved, but excessive Te element can cause the formation of large-size TeMn inclusion, the number of the inclusion can be obviously improved, the number of pitting corrosion initiation points in the stainless steel can be increased, and the pitting corrosion resistance of the material can be reduced.
In order to ensure the hardness, plasticity and production cost of the steel bar, on one hand, the added microalloy elements are ensured to play a role in solid solution strength and precipitation strengthening, and the hardness and plasticity of the material are improved after the content of C is reduced; on the other hand, a compact, electronegative and high-protective passive film is formed on the surface of the material to ensure the corrosion resistance of the material.
Optionally, the pitting corrosion resistant martensitic hardening stainless steel has the composition, and the content of C may be 0, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07% or any value between 0 and 0.07% by mass; the content of Mn can be 0.35%, 0.40%, 0.45%, 0.50%, 0.55%, 0.60%, 0.65%, 0.68%, or any value between 0.35% and 0.68%; the content of Si can be any value between 0.32%, 0.35%, 0.40%, 0.45%, 0.50%, 0.55%, 0.60%, 0.65%, 0.70% or 0.32% -0.70%; the content of P can be 0, 0.005%, 0.010%, 0.015%, 0.020%, 0.025%, 0.030%, 0.035% or any value between 0 and 0.035%; the content of S may be 0.005%, 0.010%, 0.015%, 0.020%, 0.025%, 0.030%, or any value between 0 and 0.030%; the content of Ni may be any value between 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5.0%, 5.1%, 5.2%, or 3.8% -5.2%; the content of Cr can be 14.0%, 14.5%, 15.0%, 15.5%, 16.0%, 16.5%, 16.8% or any value between 14.0% and 16.8%; the content of Cu may be 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, or any value between 2.8% and 4.3%; the content of Mo may be 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, or any value between 0.3% and 1.5%; the content of V can be any value between 0.050%, 0.060%, 0.070%, 0.080%, 0.090%, 0.10% or 0.050% and 0.10%; the content of Al can be any value between 0.001%, 0.002%, 0.003%, 0.004% or more than 0 and less than 0.005%; the content of Nb can be any value between 0.15%, 0.20%, 0.25% or 0.15% -0.25%; the content of Te may be 0.005%, 0.010%, 0.020%, 0.030%, or 0 or more and 0.030% or less.
The pitting corrosion resistant martensitic hardening stainless steel has a structure of lath martensite.
The application also provides a preparation method of the pitting corrosion resistant martensitic hardened stainless steel, which comprises the following steps:
smelting the raw materials by using a vacuum induction furnace to obtain molten steel, and cooling to obtain a steel ingot;
and forging the steel ingot, then carrying out first heat treatment, then rolling and second heat treatment, and cooling to obtain the pitting corrosion resistant martensitic hardening stainless steel.
In an alternative embodiment, the smelting is carried out under the protection of argon at a pressure of 0.04MPa to 0.06MPa to control the oxygen content in the steel and reduce the amount of oxide inclusions in the steel.
Optionally, the smelting is performed under the protection of argon, and the pressure may be 0.04MPa, 0.05MPa, 0.06MPa or any value between 0.04MPa and 0.06MPa.
In an alternative embodiment, the vacuum induction furnace is evacuated to 2 × 10 before being filled with the argon gas - 3 Pa-3×10 -3 Pa to reduce the residual amount of oxygen in the induction furnace and prevent the residual amount of oxygen from being applied to [ O ] in the molten steel]Influence of the content.
Optionally, the vacuum induction furnaceBefore filling the argon, the mixture was evacuated to 2X 10 -3 Pa、2.5×10 -3 Pa、3×10 -3 Pa or 2X 10 -3 Pa-3×10 -3 Pa, or any other value between Pa.
In an optional embodiment, the smelting temperature is 1575-1650 ℃, the heat preservation time is 25-30 min, the molten steel is promoted to be fully melted and mixed, and the uniformity of the material is ensured.
Optionally, the smelting temperature may be 1575 ℃, 1580 ℃, 1585 ℃, 1590 ℃, 1595 ℃, 1600 ℃, 1605 ℃, 1610 ℃, 1615 ℃, 1620 ℃, 1625 ℃, 1630 ℃, 1635 ℃, 1640 ℃, 1645 ℃, 1650 ℃ or any value between 1575 ℃ and 1650 ℃, and the heat preservation time may be any value between 25min, 26min, 27min, 28min, 29min, 30min or any value between 25min and 30min.
In an alternative embodiment, the first heat treatment comprises:
heating to 1100-1200 deg.c, maintaining for 70-90 min to promote the complete austenitizing of steel.
Optionally, in the first heat treatment, the temperature rise end point may be any value between 1100 ℃ and 1150 ℃, 1200 ℃ or 1100 ℃ to 1200 ℃, and the heat preservation time may be any value between 70min, 80min, 90min or 70min to 90min.
In an alternative embodiment, the rolling is performed with a reduction of 50% to 70%.
Alternatively, the rolling reduction may be 50%, 60%, 70%, or any value between 50% and 70%.
In an alternative embodiment, the second heat treatment includes a normalizing treatment, a first solution treatment, and a second solution treatment performed in this order to promote sufficient precipitation of a solid solution phase and formation of martensite.
In an optional embodiment, the temperature of the normalizing treatment is 1120-1200 ℃ and the time is 100-150 min;
the temperature of the first solution treatment is 1000-1080 ℃, and the time is 40-70 min;
the temperature of the first solution treatment is 480-550 ℃, and the time is 120-180 min.
Optionally, the normalizing temperature may be 1120 ℃, 1130 ℃, 1140 ℃, 1150 ℃, 1160 ℃, 1170 ℃, 1180 ℃, 1190 ℃, 1200 ℃, or 1120 ℃ to 1200 ℃, and the normalizing time may be 100min, 110min, 120min, 130min, 140min, 150min, or 100min to 150min; the temperature of the first solution treatment can be any value between 1000 ℃, 1010 ℃, 1020 ℃, 1030 ℃, 1040 ℃, 1050 ℃, 1060 ℃, 1070 ℃, 1080 ℃ or 1000-1080 ℃, and the time can be any value between 40min, 50min, 60min, 70min or 40min-70min; the temperature of the first solution treatment can be any value between 480 ℃, 490 ℃, 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃ or 480 ℃ to 550 ℃, and the time can be any value between 120min, 130min, 140min, 150min, 160min, 170min, 180min or 120min to 180min.
Embodiments of the present application will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
Example 1
The embodiment provides pitting corrosion resistant martensitic hardening stainless steel, which comprises the following components in percentage by mass of 100 percent: 0.057% of C, 0.68% of Mn, 0.43% of Si, 0.032% of P, 0.024% of S, 3.98% of Nis, 16.04% of Cr16, 3.08% of Cu0.59% of Mo0.085% of V, 0.0012% of Al0.2%, 0.2% of Nb0.0125% of Te0.0125% of Fe and the balance of inevitable impurities; where [ Te ]/[ S ] =0.52.
The preparation method of the pitting corrosion resistant martensitic hardened stainless steel comprises the following steps:
adding various alloy raw materials into a vacuum induction furnace according to the mixture ratio for smelting, and vacuumizing to 2.5 multiplied by 10 -3 Pa, then filling argon to 0.05MPa, heating the electromagnetic induction furnace to 1595 ℃, keeping the temperature for 25min, then turning off the power supply, and finally turning on the power supplyAnd pouring the molten steel into a mold, and cooling to room temperature by water cooling.
And forging the steel ingot, heating to 1150 ℃, preserving the heat for 80min, and then rolling, wherein the pressing amount of the steel plate is 65%.
Carrying out heat treatment on the rolled stainless steel, wherein the heat treatment process comprises the following steps: normalizing at 1180 deg.C for 120min, solid-solution treating at 1050 deg.C for 50min, solid-solution treating at 520 deg.C for 130min, and air cooling.
Example 2
The embodiment provides pitting corrosion resistant martensitic hardening stainless steel, which comprises the following components in percentage by mass of 100 percent: 0.062% of C, 0.64% of Mn, 0.42% of Si, 0.034% of P, 0.024% of S, 4.01% of Ni0.01% of Cr16.01% of Cu, 3.08% of Mo0.68% of V, 0.085% of Al, 0.0017% of Nb0.2% of Ti, and 0.0151% of Ti, and the balance of Fe and inevitable impurities; where [ Te ]/[ S ] =0.63.
The preparation method of the pitting corrosion resistant martensitic hardened stainless steel comprises the following steps:
adding various alloy raw materials into a vacuum induction furnace according to the proportion for smelting, and vacuumizing to 2.8 multiplied by 10 -3 Pa, then flushing argon to 0.05MPa, heating the electromagnetic induction furnace to 1610 ℃, keeping the temperature for 27min, then turning off a power supply, pouring molten steel into a mold, and carrying out water cooling to room temperature.
And (3) forging the steel ingot, heating to 1160 ℃, preserving heat for 82min, and then rolling, wherein the pressing amount of the steel plate is 60%.
Carrying out heat treatment on the rolled stainless steel, wherein the heat treatment process comprises the following steps: normalizing at 1160 deg.C for 120min, dissolving at 1060 deg.C for 52min, dissolving at 525 deg.C for 125min, and air cooling.
The SEM photograph of the steel material is shown in FIG. 1.
Example 3
The embodiment provides pitting corrosion resistant martensitic hardening stainless steel, which comprises the following components in percentage by mass of 100 percent: 0.062% of C, 0.63% of Mn, 0.44% of Si, 0.032% of P, 0.023% of S, 4.03% of Nis, 16.12% of Cr16.08% of Cu3.08% of Mo0.62% of V, 0.084% of Al0.0016% of Nb0.2% of Te0.0186% of Fe and inevitable impurities in balance; where [ Te ]/[ S ] =0.81.
The preparation method of the pitting corrosion resistant martensitic hardened stainless steel comprises the following steps:
adding various alloy raw materials into a vacuum induction furnace according to the proportion for smelting, and vacuumizing to 2.510 -3 Pa, then flushing argon to 0.06MPa, heating the electromagnetic induction furnace to 1630 ℃, keeping the temperature for 26min, then turning off the power supply, pouring the molten steel into the mold, and carrying out water cooling to room temperature.
And forging the steel ingot, heating to 1130 ℃, preserving the heat for 72min, and then rolling, wherein the pressing amount of the steel plate is 55%.
Carrying out heat treatment on the rolled stainless steel, wherein the heat treatment process comprises the following steps: normalizing at 1120-1200 deg.C for 100-150 min, dissolving at 1000-1080 deg.C for 40-70 min, dissolving at 480-550 deg.C for 120-180 min, and air cooling.
Comparative example 1
The comparative example provides a stainless steel, which comprises the following components in percentage by mass of 100%: 0.058% of C, 0.65% of Mn, 0.47% of Si, 0.032% of P, 0.025% of S, 4.03% of Nis, 16.13% of CrC, 3.08% of Cu0.52% of Mo0.086% of V, 0.0012% of Al, 0.2% of Nb0.2% of Te and the balance of Fe and inevitable impurities; where [ Te ]/[ S ] =0.
The preparation method of the stainless steel comprises the following steps:
adding various alloy raw materials into a vacuum induction furnace according to the proportion for smelting, and vacuumizing to 2.610 -3 And Pa, then flushing argon to 0.04MPa, heating the electromagnetic induction furnace to 1585 ℃, keeping the temperature for 27min, then turning off a power supply, pouring molten steel into a mold, and carrying out water cooling to room temperature.
And (3) forging the steel ingot, heating to 1135 ℃, preserving heat for 84min, and then rolling, wherein the pressing amount of the steel plate is 59%.
Carrying out heat treatment on the rolled stainless steel, wherein the heat treatment process comprises the following steps: normalizing at 1190 deg.C for 115min, solid-dissolving at 1050 deg.C for 60min, solid-dissolving at 540 deg.C for 128min, and air cooling.
The SEM photograph of the steel material is shown in FIG. 2.
Comparative example 2
The comparative example provides stainless steel, which comprises the following components in percentage by mass of 100 percent: 0.058% of C, 0.65% of Mn, 0.44% of Si, 0.033% of P, 0.025% of S, 4.01% of Ni4, 16.15% of CrC, 3.08% of Cu0.53% of Mo0.084% of V, 0.0013% of Al, 0.2% of Nb0.0038% of Te0.0038% of Fe and the balance of inevitable impurities; wherein [ Te ]/[ S ] =0.15.
The preparation method of the stainless steel comprises the following steps:
adding various alloy raw materials into a vacuum induction furnace according to the proportion for smelting, vacuumizing to 2.9Pa, then flushing argon to 0.06MPa, heating the electromagnetic induction furnace to 1620 ℃, keeping the temperature for 25min, then turning off a power supply, pouring molten steel into a mold, and carrying out water cooling to room temperature.
And forging the steel ingot, heating to 1190 ℃, preserving heat for 72min, and then rolling, wherein the pressing amount of the steel plate is 63%.
Carrying out heat treatment on the rolled stainless steel, wherein the heat treatment process comprises the following steps: 1190 deg.C for 105min, 1075 deg.C for 42min, 482 deg.C for 160min, and air-cooling.
Comparative example 3
The comparative example provides stainless steel, which comprises the following components in percentage by mass of 100 percent: 0.06% of C, 0.64% of Mn, 0.45% of Si, 0.033% of P, 0.024% of S, 4.01% of Ni4, 16.08% of Cr16, 3.07% of Cu3, 0.62% of Mo0, 0.084% of V, 0.0015% of Al0, and 0.0091% of Te0.0091%, and the balance of Fe and inevitable impurities; where [ Te ]/[ S ] =0.38.
The preparation method of the stainless steel comprises the following steps:
adding various alloy raw materials into a vacuum induction furnace according to the proportion for smelting, and vacuumizing to 2.2 multiplied by 10 -3 Pa, then flushing argon to 0.04MPa, heating the electromagnetic induction furnace to 1620 ℃, keeping the temperature for 25min, then turning off a power supply, pouring molten steel into a mold, and carrying out water cooling to room temperature.
And (3) forging the steel ingot, heating to 1120 ℃, preserving heat for 82min, and then rolling, wherein the pressing amount of the steel plate is 55%.
Carrying out heat treatment on the rolled stainless steel, wherein the heat treatment process comprises the following steps: normalizing at 1180 deg.C for 115min, performing solid solution treatment at 1075 deg.C for 45min, performing solid solution treatment at 520 deg.C for 150min, and air cooling.
Comparative example 4
The comparative example provides stainless steel, which comprises the following components in percentage by mass of 100 percent: 0.059% of C, 0.64% of Mn, 0.46% of Si, 0.034% of P, 0.025% of S, 3.99% of Nis, 15.98% of Cr15, 3.07% of Cu3, 0.61% of Mo0, 0.084% of V, 0.0015% of Al0, 0.2% of Nb0 and 0.0288% of the balance of Fe and inevitable impurities; wherein [ Te ]/[ S ] =1.15.
The preparation method of the stainless steel comprises the following steps:
adding various alloy raw materials into a vacuum induction furnace according to the proportion for smelting, and vacuumizing to 3 multiplied by 10 -3 Pa, then flushing argon to 0.04MPa, heating the electromagnetic induction furnace to 1625 ℃, keeping the temperature for 26min, then turning off the power supply, pouring the molten steel into the mold, and carrying out water cooling to room temperature.
And forging the steel ingot, heating to 1150 ℃, preserving heat for 82min, and then rolling, wherein the pressing amount of the steel plate is 66%.
Carrying out heat treatment on the rolled stainless steel, wherein the heat treatment process comprises the following steps: normalizing at 1160 deg.C for 125min, dissolving at 1050 deg.C for 60min, dissolving at 535 deg.C for 140min, and cooling in air.
Comparative example 5
The comparative example provides a stainless steel, which comprises the following components in percentage by mass of 100%: 0.058% of C, 0.66% of Mn, 0.42% of Si, 0.033% of P, 0.024% of S, 4.02% of Ni4, 16.07% of Cr16, 3.08% of Cu0.64% of Mo0.084% of V, 0.0014% of Al0.0014%, 0.2% of Nb0.0331% of Te0.0331% and the balance of Fe and inevitable impurities; where [ Te ]/[ S ] =1.38.
The preparation method of the stainless steel comprises the following steps:
adding various alloy raw materials into a vacuum induction furnace according to the proportion for smelting, and vacuumizingTo 2.6X 10 -3 Pa, then flushing argon to 0.05MPa, heating the electromagnetic induction furnace to 1630 ℃, keeping the temperature for 27min, then turning off the power supply, pouring the molten steel into a mold, and carrying out water cooling to room temperature.
And forging the steel ingot, heating to 1180 ℃, preserving heat for 72min, and then rolling, wherein the pressing amount of the steel plate is 68%.
Carrying out heat treatment on the rolled stainless steel, wherein the heat treatment process comprises the following steps: normalizing at 1165 deg.C for 132min, solution treating at 1060 deg.C for 58min, solution treating at 490 deg.C for 136min, and air cooling.
The SEM photograph of the steel material is shown in FIG. 3.
Comparative example 6
The comparative example provides pitting corrosion resistant martensitic hardening stainless steel, which comprises the following components in percentage by mass of 100 percent: 0.061% of C, 0.63% of Mn, 0.43% of Si, 0.034% of P, 0.024% of S, 4.0% of Ni0%, 16.04% of Cr16, 3.08% of Cu0.67%, 0.084% of V, 0.0017% of Al, 0.2% of Nb0.0154% of Te0.0154%, and the balance of Fe and inevitable impurities; where [ Te ]/[ S ] =0.64.
The preparation method of the stainless steel comprises the following steps:
adding various alloy raw materials into a vacuum induction furnace according to the mixture ratio for smelting, and vacuumizing to 2.7 multiplied by 10 -3 Pa, then flushing argon to 0.05MPa, heating the electromagnetic induction furnace to 1608 ℃, keeping the temperature for 26min, then turning off the power supply, pouring the molten steel into the mold, and carrying out water cooling to the room temperature.
And (3) forging the steel ingot, heating to 1158 ℃, preserving heat for 85min, and then rolling, wherein the pressing amount of the steel plate is 58%.
Carrying out heat treatment on the rolled stainless steel, wherein the heat treatment process comprises the following steps: normalizing at 1080 deg.C for 60min, solid-solution treating at 960 deg.C for 20min, solid-solution treating at 625 deg.C for 80min, and air cooling.
Comparative example 7
The comparative example provides pitting corrosion resistant martensitic hardening stainless steel, which comprises the following components in percentage by mass of 100 percent: 0.063% of C, 0.65% of Mn, 0.41% of Si, 0.034% of P, 0.025% of S, 4.05% of NiNi, 16.08% of CrC, 3.1% of Cu0.65% of Mo0.65% of V, 0.081% of Al0.0018%, 0.2% of Nb0.2% of Te0.0158% of Fe and inevitable impurities in balance; where [ Te ]/[ S ] =0.632.
The preparation method of the stainless steel comprises the following steps:
adding various alloy raw materials into a vacuum induction furnace according to the mixture ratio for smelting, and vacuumizing to 2.7 multiplied by 10 -3 And Pa, then flushing argon to 0.05MPa, heating the electromagnetic induction furnace to 1612 ℃, keeping the temperature for 28min, then closing a power supply, pouring molten steel into a mold, and carrying out water cooling to room temperature.
And forging the steel ingot, heating to 1161 ℃, preserving heat for 85min, and then rolling, wherein the pressing amount of the steel plate is 66%.
Carrying out heat treatment on the rolled stainless steel, wherein the heat treatment process comprises the following steps: normalizing at 1085 deg.C for 80min, solution-treating at 952 deg.C for 80min, then solution-treating at 450 deg.C for 110min, and air-cooling.
The properties of the steels obtained in the examples and comparative examples were measured, and the results are shown in the following Table 1:
TABLE 1 Performance data of the steels obtained in the examples and comparative examples
As can be seen from Table 1, when Te is properly added to steel, the corrosion resistance of the material is obviously changed, wherein when w ([ Te ])/w ([ S ]) <0.3, the material is in a passivated state, but no obvious difference is seen between the pitting potential and the Vicat current density, and the corrosion resistance of the material is not obviously changed. When w ([ Te ])/w ([ S ]) is between 0.3 to 1.0, the pitting potential of the material is obviously improved, the Vicat current density is obviously reduced, and when w ([ Te ])/w ([ S ]) is near 0.63, the maximum pitting potential and the minimum Vicat current density are shown, and the best corrosion resistance is shown. And when w ([ Te ])/w ([ S ]) is more than 1, the material is directly converted from a passivated state to an activated state, which shows that the corrosion resistance of the material is sharply deteriorated.
The morphology and composition of inclusions in the steels obtained in comparative example 1, example 2 and comparative example 5 were analyzed, and the results are shown in fig. 4, fig. 5 and fig. 6. FIG. 7 is a graph showing the size distribution of inclusions in three steel materials, wherein each set of histograms corresponds to comparative example 1, example 2, and comparative example 5, from left to right.
As can be seen, the steel of comparative example 1, to which no Te was added, exhibited passivation properties in solution, with a pitting potential of-0.0626V vsSCE and a Vicat current density of 2.450. Mu.A/cm -2 (ii) a Example 2 the steel was a 15-5PH stainless steel with a trace of Te added thereto [ Te]/[S]=0.63, and an electrochemical result shows that the passivation performance is obviously improved, the pitting potential of the material is 0.099V vsSCE, and the Vicat current density is 0.890 mu A/cm -2 (ii) a Comparative example 5 Steel after addition of Te, [ Te ]]/[S]And =1.42, the electrochemical result shows that the anodic process of the material shows activated dissolution performance and no longer has a passivated state, which indicates that the corrosion resistance of the material is the worst.
The electrochemical polarization curves of the steels obtained in comparative example 1, example 2 and comparative example 5 are shown in FIG. 8. Wherein 1, 2, 3 correspond to comparative example 1, example 2 and comparative example 5, respectively.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present application, and not to limit the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the scope of the technical solutions of the embodiments of the present application.
Moreover, those of skill in the art will understand that although some embodiments herein include some features included in other embodiments, not others, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art that is already known to a person skilled in the art.
Claims (7)
1. A pitting corrosion resistant martensitic hardened stainless steel is characterized in that the components thereof by mass percentage comprise:
less than or equal to 0.07 percent of C, 0.35 to 0.68 percent of Mn, 0.32 to 0.70 percent of Si, less than or equal to 0.035 percent of P, less than or equal to 0.030 percent of S, 3.8 to 5.2 percent of Nis, 14.0 to 16.8 percent of Cr0, 2.8 to 4.3 percent of Cu2, 0.3 to 1.5 percent of Mo0, 0.050 to 0.10 percent of V, less than 0.005 percent of Al, 0.15 to 0.25 percent of Nb, less than or equal to 0.030 percent of Te and the balance of Fe and inevitable impurities;
wherein 0.35 < [ Te ]/[ S ] < 1.0;
the preparation method of the pitting corrosion resistant martensitic hardened stainless steel comprises the following steps:
smelting the raw materials by using a vacuum induction furnace to obtain molten steel, and cooling to obtain a steel ingot;
forging the steel ingot, then carrying out first heat treatment, then rolling and second heat treatment, and cooling to obtain the pitting corrosion resistant martensitic hardening stainless steel;
the second heat treatment comprises normalizing treatment, first solution treatment and second solution treatment which are sequentially carried out;
the normalizing treatment temperature is 1120-1200 ℃, and the normalizing treatment time is 100-150 min;
the temperature of the first solution treatment is 1000-1080 ℃, and the time is 40-70 min;
the temperature of the second solution treatment is 480-550 ℃, and the time is 120-180 min.
2. The pitting corrosion resistant martensitic hardened stainless steel of claim 1, wherein its microstructure is lath martensite.
3. The pitting corrosion resistant martensitic stainless steel of claim 1 wherein the smelting is performed under argon protection at a pressure of 0.04MPa to 0.06MPa.
4. The pitting corrosion resistant martensitic hardened stainless steel of claim 3, wherein the vacuum induction furnace is evacuated to 2 x 10 prior to the argon gas being charged therein -3 Pa-3×10 -3 Pa。
5. The pitting corrosion resistant martensitic hardened stainless steel of claim 1, wherein the temperature of the smelting is 1575-1650 ℃ and the holding time is 25-30 min.
6. The pitting corrosion resistant martensitic hardened stainless steel of claim 1, wherein the first heat treatment comprises:
heating to 1100-1200 deg.c and maintaining for 70-90 min.
7. The pitting corrosion resistant martensitic hardened stainless steel of claim 1, wherein the amount of reduction in rolling is 50% -70%.
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Inventor after: Liu Chao Inventor after: Zhang Shasha Inventor after: Li Xiaogang Inventor after: Che Zhichao Inventor after: Liu Wei Inventor after: Yang Shufeng Inventor after: Cheng Xuequn Inventor before: Liu Chao Inventor before: Zhang Shasha Inventor before: Li Xiaogang Inventor before: Che Zhichao Inventor before: Liu Wei Inventor before: Yang Shufeng Inventor before: Cheng Xuequn |