CN1114715C - Martensitic stainless steel with high mechanical strength and anti-corrosion - Google Patents
Martensitic stainless steel with high mechanical strength and anti-corrosion Download PDFInfo
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Abstract
The present invention relates to a martensitic stainless steel for manufacturing products with high mechanical strength and high corrosion resistance, such as shafts, or impellers, etc. The martensitic stainless steel contains less than 0.06 wt. % of C, less than 2.5 wt. % of Si, less than 2.5 wt. % of Mn, 1.0 to 6.0 wt. % of Ni, 10.0 to 19.0 wt. % of Cr, 0.5 to 6.0 wt. % of W, less than 3.5 wt. % of Mo, less than 0.5 wt. % of Nb, less than 0.5 wt. % of V, less than 3.0 wt. % of Cu, 0.05 to 0.25 wt. % of N, Fe and small quantity of impurities.
Description
The invention relates to Martensite Stainless Steel, especially about requiring spendable Martensite Stainless Steel in high mechanical strength and the anticorrosive goods as bearing, impeller or cutter etc. in manufacturing.
General stainless steel is classified according to its main component, as Martensite Stainless Steel, austenitic stainless steel, ferrite stainless steel, duplex stainless steel, PH Stainless Steel and super stainless steel.
These stainless steels guarantee to have desired physical strength and resistance to corrosion.Therefore, they are widely applied in the manufacturing of the industrial equipments that requires this specific character and parts.
Especially well-known 410 or 420 Martensite Stainless Steels have very high physical strength, have been used as manufacturing and can have born the boiler pump impeller of high centrifugal force or the material that conveying contains abrasive particle fluidic pipeline.
The power-equipment of up-to-date development and Design is to improve fuel efficiency by the temperature in that increases the boiler turbine, and, also increased the speed of rotation of turbo-pump.Therefore, require a kind of material that can bear the power-equipment rigor condition.
Especially boiler charging pump is because it must carry the oxycompound incrustation scale or can produce abrasive tiny solid particulate fluid to parts as coal, sand, so the parts of boiler charging pump must have very high anticorrosive, wear-resistant and very high physical strength.
Yet 410 and 420 Martensite Stainless Steels have been used to make the parts of common boiler charging pump, have very high physical strength, but also have quite low not corrosion-resistant shortcoming.
That is, because Martensite Stainless Steel contains quite high carbon of weight and 12-18% chromium, so by heat treatment process, its physical strength rises to very high level.But because the carbon content height, chromium carbide is deposited on around the particle, is easy to form the layer that chromium exhausts, thereby has reduced resistance to corrosion.
As everyone knows, by a kind of super martensitic alloy 248SV that Avesta Sheffield company develops, be used as the material of making the boiler charging pump, this alloy has improved resistance to corrosion by reducing the carbon amount, increase the chromium amount and adding nickel.Yet, because the nickel that adds is the stable element of a kind of austenite, thus be difficult to make alloy to have the martensitic structure of higher percent, thus the physical strength of this alloy is very low.
Order this patent JP-1030665 discloses a kind of stainless steel, improved seawater and other fluidic resistance to corrosions, yet, because this stainless steel contains the cobalt of 3.5-7.0%, thus manufacturing expense increased, and, the carbon amount surpasses 0.08%, has reduced resistance to corrosion again.
Therefore, require a kind of very high mechanical strength that both had, have the stainless steel of very high resistance to corrosion again, this stainless steel optimum is used for making the impeller and the axle of boiler charging pump.
The present invention who studies through great efforts and finish can satisfy above requirement.
For satisfying above-mentioned requirements, the invention provides a kind of Martensite Stainless Steel, contain less than 0.06 weight %C, less than the Si of 2.5 weight %, less than the W of Cr, the 0.5-6.0 weight % of Ni, the 10.0-19.0 weight % of Mn, the 1.0-6.0 weight % of 2.5 weight %, less than the Mo of 3.5 weight %, less than the V of 0.8 weight %, less than the Cu of 3.0 weight %, the N of 0.04-0.25 weight %, all the other are Fe and a spot of impurity.
This Martensite Stainless Steel preferably further contains at least a less than among the Ta of the Ti of 0.8Wt% or 1.0Wt%.
According to another aspect of the present invention, this Martensite Stainless Steel contains less than the Si of the C of 0.035 weight %, little 2.0 weight %, less than the W of Cr, the 0.5-4.5 weight % of Ni, the 12.0-16.0 weight % of Mn, the 1.5-4.5 weight % of 2.0 weight %, less than the Mo of 2.5 weight %, less than the V of 0.3 weight %, less than the Cu of 2.0 weight %, the N of 0.08-0.20 weight %, and all the other are Fe and small amount of impurities.
According to a further aspect in the invention, make the method for this Martensite Stainless Steel, comprise the steps: that melting contains the stainless steel of following composition, that is, less than the C of 0.06 weight %, less than the Si of 2.5 weight %, less than the W of Cr, the 0.5-0.6 weight % of Ni, the 10.0-19.0 weight % of Mn, the 1.0-6.0 weight % of 2.5 weight %, less than the Mo of 3.5 weight %, less than the V of 0.8 weight %, less than the N of Cu, the 0.04-0.25 weight % of 3.0 weight %, all the other are Fe and small amount of impurities; Make the stainless steel of melting bear austenite thermal treatment under 800-1150 ℃ and/or under 350-575 ℃, make this stainless steel bear temper.
According to a further aspect of the invention, make the method for this Martensite Stainless Steel, comprise the steps: that melting contains the stainless steel of following composition, that is, less than the C of 0.06 weight %, less than the Si of 2.5 weight %, less than the W of Cr, the 0.5-6.0 weight % of Ni, the 10.0-19.0 weight % of Mn, the 1.0-6.0 weight % of 2.5 weight %, less than the Mo of 3.5 weight t%, less than the Nb of 0.8 weight %, less than the N of Cu, the 0.04-0.25 weight % of 3.0 weight %, all the other are Fe and small amount of impurities; This stainless steel is carried out mechanical treatment, make this stainless steel produce workhardness; Make the stainless steel of mechanical treatment bear austenite thermal treatment under 800-1150 ℃ and/or under 350-575 ℃, make this stainless steel bear temper.
Follow in the specification sheets, and constitute the accompanying drawing of a specification sheets part, embodiments of the invention are described, and the joint specification sheets is explained principle of the present invention.
Fig. 1 is the graphic representation that the yielding stress of test sample in the most preferred embodiment of the present invention changes with tempering temperature.
Fig. 2 is the graphic representation that the unit elongation of test sample in the most preferred embodiment of the present invention changes with tempering temperature.
With reference to description of drawings most preferred embodiment of the present invention.
Martensite Stainless Steel of the present invention comprises less than the C of 0.06 weight %, less than the Si of 2.5 weight %, less than the W of Cr, the 0.5-6.0 weight % of Ni, the 10.0-19.0 weight % of Mn, the 1.0-6.0 weight % of 2.5 weight %, less than the Mo of 3.5 weight %, less than the Nb of 0.8 weight %, less than the V of 0.8 weight t%, less than the N of Cu, the 0.04-0.25 weight % of 3.0 weight %, all the other are Fe and small amount of impurities.The composition of Martensite Stainless Steel also will be described in detail.
Carbon is and metallic element in conjunction with the element that forms carbide, can increase stainless intensity as Cr, Mo, W, Nb and V.When the carbon amount in the 410 common martensitic steels is increased to 0.15 weight %, the settled layer of chromium carbide will increase, and among the present invention, add the carbon less than 0.06 weight %, best carbon less than 0.035 weight %.
Silicon is a kind of tramp element in the smelting metal, can be used as smelting agent and adds, and increases the degree of mobilization of liquid metal, and restriction reduces to prevent mechanical characteristics less than 2.5 weight %, preferably adds the silicon of little 2.0 weight %.
As Mn during greater than 2.0 weight %, can reduce as the mechanical characteristicies such as extensibility of metal, preferably add Mn less than 2.0 weight %.
Ni is the austenitic element of a kind of formation, among the present invention, because the C amount is less than 0.06 weight %, so the Ni amount at least should be more than 1.0 weight %.Yet when the Ni amount was higher than 6.0 weight %, martensitic transformation point and eutectic temperature (AC1) can reduce greatly, and produce the overaging phenomenon, reduce anti-quenching capacity.Therefore, preferably add the Ni of 1.0-6.0 weight %.Yet, preferably further add Ni to 1.50-4.5wt%, forming uniform martensitic structure, and improve physical strength.
Adding Cr is for the improvement resistance to corrosion, therefore can effectively prevent high temperature oxidation and corrosion, yet when Cr measured less than 10 weight %, resistance to corrosion reduced, and when being higher than 19 weight %, influenced by stable δ-ferrite, and reduced physical strength.Therefore, preferably add the Cr of 12.0-16.0 weight %.
Interpolation W can improve physical strength and the tempering resistance under the high-temperature, combines with C and forms carbide, as M
2C (M is a metallic element).Especially, W can improve pitting corrosion resistant performance under predetermined PH.Yet, when the W that adds less than 0.5 weight %, but can not obtain this effect, when being higher than 6.0 weight %, can form a large amount of ferrites, intensity reduces, and reduces the martensitic transformation point, be difficult to obtain martensitic structure, therefore, preferably add the W of 0.5-4.5 weight %.
Add Mo and can improve pitting corrosion resistant performance and physical strength, preferably add Mo less than 3.5 weight %, particularly good less than 2.5 weight %.
Add Nb and V and can form NbC and V respectively
4C
3, therefore can increase the physical strength under the high temperature.If each adds Nb and V greater than 0.8 weight %, toughness and extensibility reduce.Therefore, Nb and V add best less than 0.8 weight % separately, and be particularly good less than 0.3 weight %.
Adding Cu can improve the hardenability of resistance to corrosion and high temperature resistance steam by improving the particulate size, can cause the ingot fractional condensation by depositing a kind of Cu, makes material degradation.Therefore, preferably add Cu less than 2.0 weight %.
Among the present invention, when relatively the time, having reduced the C amount with common Martensite Stainless Steel, add N extraly, to reduce δ-ferrite and stable austenite, in addition, N deferrable steel converts big carbide to, as M
23C
6To such an extent as to, can prevent that Cr from exhausting and cause the reduction of resistance to corrosion, for obtaining this effect, should add the N greater than 0.04 weight %.Yet, when N measures greater than 0.25 weight %, can reduce the temperature that martensite begins to change, therefore, reduced stainless toughness.Therefore preferably add the N of 0.08-0.2 weight %.
Martensite Stainless Steel with foregoing description composition can be used as the melting goods, perhaps forms sheet material or bar by forging, roll-in and extrusion processing later on.
In addition, Martensite Stainless Steel can be used as the welding wire of drawing, forms high performance element on common steel surface.
When utilizing Martensite Stainless Steel to make the melting goods by simple mechanical workout, as grinding, and can not produce work hardening, be preferably in and carry out austenite thermal treatment under 800-1150 ℃, to such an extent as to remove the casting liquate, and make the microtexture homogenizing.After finishing austenite thermal treatment, preferably be chosen in and carry out temper under 350-575 ℃, to improve the mechanical characteristics of goods.
When mechanical workout by generation work hardening, picture forges, roll-in, and extrusion processing, during with the Martensite Stainless Steel fabricated product, be preferably in and bear austenite thermal treatment under 800-1150 ℃ and/or under 350-575 ℃, carry out temper, to improve the mechanical features of goods.
According to concrete instance preferred plan of the present invention is described now.
Example
Listed the composition of each sample example of the Martensite Stainless Steel relevant with the foregoing description invention and comparative example in the following table 1, the steel that will have composition shown in the following table 1 melts in vacuum melting furnace, and is cast into the ingot casting of 150 * 150 * 300mm.
Table 1
| Composition (weight %) | ||||||||||||||
| C | Si | Mn | Ni | Cr | Mo | W | Nb | V | Cu | Ti | Ta | N | Fe | |
| Sample example 1 | 0.03 | 0.32 | 0.4 | 2.0 | 12.5 | 1.5 | 1.0 | 0.1 | 0.1 | - | - | - | 0.12 | All the other |
| Sample example 2 | 0.03 | 0.31 | 0.5 | 2.0 | 13.0 | 1.5 | 1.0 | - | - | - | 0.05 | 0.1 | 0.21 | All the other |
| Sample example 3 | 0.02 | 0.40 | 0.4 | 5.0 | 16.0 | 1.0 | 0.5 | 0.1 | 0.1 | 0.5 | - | - | 0.08 | All the other |
| Sample example 4 | 0.03 | 0.25 | 0.4 | 2.0 | 16.0 | 0.5 | 3.0 | 0.1 | 0.2 | 0.4 | - | - | 0.21 | All the other |
| Sample example 5 | 0.02 | 0.32 | 0.3 | 3.0 | 18.0 | 1.0 | 0.5 | 0.15 | 0.12 | 0.7 | - | - | 0.20 | All the other |
| Sample example 6 | 0.02 | 0.35 | 0.7 | 2.1 | 13.2 | 1.7 | 1.1 | 0.1 | 0.1 | - | - | - | 0.11 | All the other |
| Sample example 7 | 0.03 | 0.40 | 0.5 | 2.0 | 15.8 | 0.6 | 3.2 | 0.1 | 0.2 | 0.4 | - | - | 0.15 | All the other |
| Sample example 8 | 0.05 | 0.43 | 0.6 | 2.1 | 13.6 | 2.0 | 1.0 | 0.1 | 0.1 | - | - | - | 0.13 | All the other |
| Comparative example 1 | 0.15 | 0.40 | 0.7 | - | 12.1 | - | - | - | - | - | - | - | 0.01 | All the other |
| Comparative example 2 | 0.21 | 0.41 | 0.7 | - | 12.8 | - | - | - | - | - | - | - | 0.01 | All the other |
| Comparative example 3 | 0.32 | 0.5 | 0.6 | - | 13.1 | - | - | - | - | - | - | - | 0.01 | All the other |
| Comparative example 4 | 0.02 | 0.42 | 0.7 | 5.0 | 16.0 | 1.0 | - | - | - | - | - | - | 0.01 | All the other |
| Comparative example 5 | 0.10 | 0.40 | 0.6 | 2.0 | 13.8 | 2.2 | 1.0 | 0.1 | 0.1 | - | - | - | 0.13 | All the other |
| Comparative example 6 | 0.19 | 0.42 | 0.6 | 2.1 | 13.7 | 2.0 | 1.0 | 0.1 | 0.1 | - | - | - | 0.12 | All the other |
Ingot casting is cut into 75 * 75 * 150mm size, then, make it under 1100 ℃, bear austenite thermal treatment in 2 hours, make test sample.
Utilize Vickers hardness tester to measure hardness, utilize universal testing machine to measure yield strength and unit elongation.In addition, utilize the critical pitting temperature of measuring to estimate corrosion characteristics.
In addition, according to the ASTMG48A standard, use 10% FeCl3.6H
2O solution, transformation temperature is 0-10 ℃ simultaneously, carries out the resistance to corrosion test.According to the ASTMG46A standard, use 10% Fecl3.6H
2O measures erosion rate.
The hardness of sample, unit elongation, resistance to corrosion are shown in following table 2.
Table 2
| Hardness (Hv) | Yield strength (Pa) | Unit elongation (%) | Critical pitting temperature (℃) | |
| Sample example 1 | 418 | 103.7×10 7 | 10.2 | ＜10.0 |
| Sample example 2 | 475 | 118.3×10 7 | 8.6 | ＜20.0 |
| Sample example 3 | 392 | 96.8×10 7 | 12.0 | ＜10.0 |
| Sample example 4 | 425 | 103.8×10 7 | 11.0 | ＜30.0 |
| Sample example 5 | 430 | 107.3×10 7 | 12.0 | ＜30.0 |
| Sample example 6 | 429 | 108.0×10 7 | 11.0 | ＜10.0 |
| Sample example 7 | 312 | 78.9×10 7 | 11.2 | ＜20.0 |
| Comparative example 1 | 307 | 76.9×10 7 | 17.0 | ＜0.0 |
| Comparative example 2 | 381 | 97.0×10 7 | 11.2 | ＜0.0 |
| Comparative example 3 | 412 | 103.1×10 7 | 9.8 | ＜0.0 |
| Comparative example 4 | 302 | 76.4×10 7 | 14.5 | ＜0.0 |
As shown in table 2, when comparing with comparative example 1-4, sample example 1-7 is being improved aspect hardness and the yield strength made in accordance with the present invention, and when comparing with comparative example, the hardness and the yield strength of some sample have improved 30%.And the unit elongation of sample example is almost consistent with the unit elongation of comparative example.
In addition, the critical pitting temperature of sample example 1-7 forms down being lower than 10-30 ℃, and the critical pitting temperature of comparative example is to form down being lower than 0 ℃, and this just shows with comparative example compares, and is improved by the anticorrosive feature of the sample example of manufacturing of the present invention.
The erosion rate of sample example and comparative example has been shown in the following table 3.
Table 3
| Erosion rate (mm/) | |
| Sample example 6 | 1.7 |
| Sample example 7 | 2.5 |
| Sample example 8 | 2.9 |
| Comparative example 5 | 3.7 |
| Comparative example 6 | 6.4 |
As shown in table 3, when the C amount increased, erosion rate also increased.This just shows that stainless C amount is low more, and erosion rate is also low more.
Erosion rate when following table 4 shows the thermal treatment Martensite Stainless Steel.
Table 4
| Erosion rate (mm/) | ||
| Sample example 6 | Sample example 7 | |
| During melting | 13.0 | 17.3 |
| After the austenite thermal treatment | 1.7 | 2.5 |
As shown in table 4, only carry out melting and do not carry out any heat treated sample erosion rate far away faster than carrying out the heat treated sample erosion rate of austenite.This just shows by heat-treating, can improve stainless resistance to corrosion greatly.
The mechanical characteristics of this test sample, and change tempering temperature, prepare sample by austenite thermal treatment, can under 350-750 ℃, carry out tempering heat treatment 2 hours.
Fig. 1 shows stainless steel and have the highest intensity under 350-575 ℃ tempering temperature.The yield strength change curve is almost consistent with the curve of other samples.
The unit elongation that Fig. 2 shows sample example 6 changes the curve that changes with tempering temperature.
This curve shows that when austenite processing of stainless steel process and temper, unit elongation has very big increase, and the unit elongation change curve is almost consistent with the curve of other samples.
Though below described most preferred embodiment of the present invention in detail, but should know any variation and/or the improvement made based on those skilled in the art person that notion of the present invention enlightens clearly, all will belong to spirit of the present invention and category, as defined in the claim.
Claims (8)
1. Martensite Stainless Steel, it is characterized in that comprising following composition: less than the C of 0.06 weight %, less than the Si of 2.5 weight %, less than the W of Cr, the 0.5-6.0 weight % of Ni, the 10.0-19.0 weight % of 2.5 weight %Mn, 1.0-6.0 weight %, less than the Mo of 3.5 weight %, less than the Nb of 0.5 weight %, less than the V of 0.5 weight %, less than the Cu of 3.0 weight %, the N of 0.05-0.25 weight %, all the other are Fe and a spot of impurity.
2. according to the Martensite Stainless Steel of claim 1, feature is further to contain: at least a among 0.8 weight %Ti and/or the 1.0 weight %Ta.
3. according to the Martensite Stainless Steel of claim 1, feature is further to contain: less than the Si of the C of 0.035 weight %, little 2.0 weight %, less than the W of Cr, the 0.5-4.5 weight % of Ni, the 12.0-16.0 weight % of Mn, the 1.5-4.5 weight % of 2.0 weight %, less than the Mo of 2.5 weight %, less than the Nb of 0.3 weight %, less than the V of 0.3 weight %, less than the Cu of 2.0 weight %, the N of 0.08-0.20 weight %.
4. according to the Martensite Stainless Steel of claim 3, feature is further to contain at least a among 0.8 weight %Ti and/or the 1.0 weight %Ta.
5. method of making Martensite Stainless Steel, feature is may further comprise the steps: melting contains the stainless steel of following composition, promptly, C less than 0.06 weight %, Si less than 2.5 weight %, less than 2.5 weight %Mn, 1.0-6.0 the Ni of weight %, 10.0-19.0 the Cr of weight t%, 0.5-6.0 the W of weight %, Mo less than 3.5 weight %, Nb less than 0.5 weight %, V less than 0.5 weight %, with Cu less than 3.0 weight %, 0.05-0.25 the N of weight %, all the other are Fe and a spot of impurity
Make the stainless steel of melting bear austenite thermal treatment under 800-1150 ℃ and/or under 350-575 ℃, make this stainless steel bear temper.
6. according to the method for claim 5, it is characterized in that: stainless steel further contains at least a among 0.8 weight %Ti and/or the 1.0 weight %Ta.
7. according to the method for claim 5, it is characterized in that may further comprise the steps: the mechanical treatment stainless steel, and after the step of smelting stainless steel and stainless steel is born before the austenite thermal treatment, make it produce workhardness at stainless steel.
8 methods according to claim 7, feature are that stainless steel further contains: at least a among 0.8 weight %Ti and/or the 1.0 weight %Ta.
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