CN107567507A - Martensitic stain less steel, by the steel making process of semi-finished and the cutting element made of semi-finished product - Google Patents

Martensitic stain less steel, by the steel making process of semi-finished and the cutting element made of semi-finished product Download PDF

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CN107567507A
CN107567507A CN201680025863.1A CN201680025863A CN107567507A CN 107567507 A CN107567507 A CN 107567507A CN 201680025863 A CN201680025863 A CN 201680025863A CN 107567507 A CN107567507 A CN 107567507A
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steel
semi
temperature
finished product
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弗朗西斯·夏瑟尼
弗朗索瓦斯·黑格里
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AI PULUN
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AI PULUN
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/005—Manufacture of stainless steel
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
    • C21C7/04—Removing impurities by adding a treating agent
    • C21C7/068—Decarburising
    • C21C7/0685—Decarburising of stainless steel
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00—Heat treatment of ferrous alloys
    • C21D6/002—Heat treatment of ferrous alloys containing Cr
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D7/00—Modifying the physical properties of iron or steel by deformation
    • C21D7/02—Modifying the physical properties of iron or steel by deformation by cold working
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
    • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
    • C21D8/1216—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties the working step(s) being of interest
    • C21D8/1222—Hot rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00—Microstructure comprising significant phases
    • C21D2211/008—Martensite
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/18—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for knives, scythes, scissors, or like hand cutting tools

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  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Manufacturing & Machinery (AREA)
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  • Heat Treatment Of Steel (AREA)
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Abstract

The present invention relates to a kind of martensitic stain less steel, it is characterised in that the composition of the martensitic stain less steel consists of by weight percentage：0.10%≤C≤0.45%；Trace≤Mn≤1.0%；Trace≤Si≤1.0%；Trace≤S≤0.01%；Trace≤P≤0.04%；15.0%≤Cr≤18.0%, trace≤Ni≤0.50%；Trace≤Mo≤0.50%；Trace≤Cu≤0.50%；Trace≤V≤0.50%；Trace≤Nb≤0.03%；Trace≤Ti≤0.03%；Trace≤Zr≤0.03%；Trace≤Al≤0.010%；Trace≤O≤0.0080%；Trace≤Pb≤0.02%；Trace≤Bi≤0.02%；Trace≤Sn≤0.02%；0.10%≤N≤0.20%；C+N >=0.25%；Cr+16N 5C >=16.0%；It is preferred that 17Cr+500C+500N≤570%；Remaining is iron and the impurity as caused by production.It is used to manufacture the process of semi-finished made of foregoing martensitic stain less steel, and one kind cutting element made of the semi-finished product the invention further relates to one kind.

Description

Martensitic stain less steel, by the steel making process of semi-finished and made of semi-finished product Cutting element
Technical field
The present invention relates to a kind of martensitic stain less steel.This steel mainly for the manufacture of cutting element, particularly cutter, such as Scalpel, scissor blade or table knife blade or household food processor.
Background technology
Steel for cutter must have very high corrosion resistance, wear intensity and hardness.
Currently used for producing the martensitic stain less steel of coated cutting tool, such as EN 1.4021, EN 1.4028 and EN 1.4034 grades of steel, there is Cr contents levels and variable C content level less than or equal to 14wt% or 14.5wt%, i.e. EN 1.4021 be 0.16%~0.25%, EN 1.4028 be 0.26%~0.35%, EN 1.4034 be 0.43%~ 0.50%.The firmness level of steel depends primarily on C content level.
When pursuing more preferable corrosion resistance, EN 1.4419 can be used, it has 0.36~0.42%C, 13.0~ 14.5%Cr and 0.60~1.00%Mo.
In the fabrication process, these steel generally melt in AOD or VOD converters, and then direct casting is into slab (slabs), the form of block base (blooms) or small billet (billets), then hot rolling is to obtain coil of strip, rolling rod or wire rod. Next they are annealed to obtain the ferrite structure of carbide-containing, its is sufficiently soft, and it is flat to obtain can to carry out cold rolling Flat products, or forging hot rolled semi-finished product to be easy to sawing before obtaining long products.
Next recrystallization annealing is carried out to product.In the ferritic soft state of the carbide-containing of this recrystallization Under, before being heat-treated, its net shape, such as the shape of table knife blade are cut the product into, wherein, the heat treatment bag Include and generally carry out influence of high austenizing temp between 950 DEG C to 1150 DEG C, be then quenched to environment temperature, this mainly to produce horse Family name's body structure.
Under this martensitic state, product has high rigidity, and when carbon content is high, hardness is higher, but also highly brittle.So The annealing generally between 100 DEG C to 300 DEG C is carried out afterwards, to reduce fragility but not reduce hardness too much.Next it is right Blade carries out various operations, including sharpening and polishing, makes it have cutting power and beautiful outward appearance.
The steel of aforementioned four grade can not all have good corrosion resistance, good simultaneously on the premise of reasonable cost Surface state and high rigidity.
EN 1.4419 has good corrosion resistance and high rigidity, but due to the addition of substantial amounts of Mo, it is with high costs.
EN 1.4034 has high rigidity, but outward appearance is general after a polish, because the steel C content of the grade is horizontal high, deposits In the carbide not dissolved during austenitizing largely.Corrosion resistance is also insufficient, because Cr contents levels are insufficient in matrix Height, particularly part Cr are trapped in the carbide not dissolved.Further, since go out during continuously casting at the end of solidification Crevice corrosion would generally occur for the crackle of existing most of carbide, the cutting edge of blade.
The hardness of EN 1.4021 and 1.4028 containing less C is relatively low, and because Cr contents levels are too low without foot Enough corrosion resistances.
The content of the invention
Present invention seek to address that above mentioned problem.Particularly seek to provide a kind of martensitic stain less steel for cutting element, It has cost benefit as high as possible, while has good corrosion resistance, good wear intensity and high rigidity.
Therefore, the present invention relates to a kind of martensitic stain less steel, it is characterised in that the composition of the martensitic stain less steel is with weight Amount percentages consist of：
0.10%≤C≤0.45%, preferably 0.20%≤C≤0.38%, preferably, 0.20%≤C≤0.35% are best 0.30%≤C≤0.35%；
Trace≤Mn≤1.0%；It is preferred that trace≤Mn≤0.6%；
Trace≤Si≤1.0%；
Trace≤S≤0.01%；It is preferred that trace≤S≤0.005%；
Trace≤P≤0.04%；
15.0%≤Cr≤18.0%, preferably 15.0%≤Cr≤17.0%, preferably, 15.2%≤Cr≤17.0%, Best 15.5%≤Cr≤16.0%；
Trace≤Ni≤0.50%；
Trace≤Mo≤0.50%；It is preferred that trace≤Mo≤0.1%；Preferably, trace≤Mo≤0.05%；
Trace≤Cu≤0.50%；It is preferred that trace≤Cu≤0.3%；
Trace≤V≤0.50%；It is preferred that trace≤V≤0.2%；
Trace≤Nb≤0.03%；
Trace≤Ti≤0.03%；
Trace≤Zr≤0.03%；
Trace≤Al≤0.010%；
Trace≤O≤0.0080%；
Trace≤Pb≤0.02%；
Trace≤Bi≤0.02%；
Trace≤Sn≤0.02%；
0.10%≤N≤0.20%, preferably 0.15%≤N≤0.20%；
C+N >=0.25%；It is preferred that C+N >=0.30%；Preferably, C+N >=0.45%；
Cr+16N-5C >=16.0%；
It is preferred that 17Cr+500C+500N≤570%；
Remaining is iron and the impurity as caused by melting.
The micro-structural of the martensitic stain less steel preferably includes at least 75% martensite.The invention further relates to one kind to be used for Manufacture process of semi-finished made of martensitic stain less steel, it is characterised in that：
By the steel with aforementioned component come the semi-finished product that melt and cast；
The semi-finished product are heated to the temperature more than or equal to 1000 DEG C；
Hot rolling is carried out to the semi-finished product to obtain sheet material, bar or wire rod；
The sheet material, bar or wire rod are annealed at a temperature of between 700 DEG C to 900 DEG C；With
Operation is formed to the sheet material, bar or wire rod.
The semi-finished product can be sheet material, and the shaping operation can be cold rolling.
The semi-finished product can be bar or wire rod, and the shaping operation can be forging.
The formed semi-finished product, if its Cr contents level between 15% to 17%, next can be at 950 DEG C Austenitizing is carried out between to 1150 DEG C, the temperature less than or equal to 20 DEG C is then cooled to at least 15 DEG C/s speed, so Annealed afterwards at a temperature of between 100 DEG C to 300 DEG C.
Next the formed semi-finished product can carry out austenitizing between 950 DEG C to 1150 DEG C, then so that Few 15 DEG C/s speed is cooled to the temperature less than or equal to 20 DEG C, then carries out low temperature at a temperature of -220 DEG C to -50 DEG C Processing, is then annealed at a temperature of between 100 DEG C to 300 DEG C.
The invention further relates to a kind of cutting element, it is characterised in that the cutting element according to preceding method by manufacturing Semi-finished product are made.
The cutting element can be the cutters such as table knife blade, food processing machine knife blade, scalpel or scissor blade.
It will be appreciated that the invention reside in produce skiver with a kind of martensitic stain less steel with specific composition Tool, the stainless steel is without the very high expensive element of contents level, and the content range well to limit contains relatively great amount of nitrogen. The particular balance of Cr, C and N content level is also necessary.
Brief description of the drawings
After reading is described below, other features and advantages of the present invention, which would indicate that, to be come, and is described below as example There is provided and 1 carry out referring to the drawings, the figure shows based on after to carrying out austenitizing, quenching and annealing according to the steel of the present invention Martensite is horizontal, under 1kg load, the change of the Vickers hardness of the steel.
Embodiment
Chemical composition on the steel according to the present invention, there is provided following supports.It must be clear that, it is considered to be it is preferable The contents level scope of each element is independent of each other, and any combination of the scope limited in the following description is considered to In the context of the present invention, as long as at the same time meet must between them according to the present invention for the respective contents level of C, N and Cr Relation existing for palpus.
The hardness of martensitic state of the C increases after austenitizing, quenching and annealing.However, it also contributes to solidifying Period major carbonization thing M7C3Precipitation, it can be stripped during polishing or sharpening blade, and this can reduce the table of product Face outward appearance.Position existing for these carbide may also turn into the position of crevice corrosion before polishing.According to austenitizing temperature Degree, too high C content level also result in C content level too high in austenitic matrix, and this to be no longer able to annealing Enough martensite fractions are obtained afterwards, or can cause the carbide M not dissolved23C6Lasting presence, it can consume austenite Cr in matrix.Therefore they reduce corrosion resistance, and are unfavorable for polishability.
Therefore, C content level must be at least 0.10% to obtain enough hardness, and no more than 0.45% with acquisition Satisfactory appearance after good corrosion resistance and polishing.However, according to used casting and clotting method, for This method is in process of setting it cannot be guaranteed that steel has enough uniformities to avoid major carbonization thing M7C3The situation of precipitation, It is favourable that maximum C content level is limited higher by proof.In this case it is advisable to C content is limited to 0.38%, It is preferred that 0.20%≤C≤0.38%.Preferably, 0.20%≤C≤0.35%；Best 0.30%≤C≤0.35%.
Particularly, optimum range can avoid high rigidity, while the formation of carbide is limited in into acceptable ratio model In enclosing, due to maximum C content horizontally relative to the reduction of more typically scope and may caused by Hardness loss can be by being deposited for this Enough nitrogen compensate, this will be described later.
In addition, C content level must be fulfilled for it is horizontal with N content and it is associated with N and Cr contents levels Formula, this will be explained later.
Mn is so-called gamma property element (gammagenous element), because its stable austenite structure.Excessive Mn contents levels cause the horizontal deficiency of martensite after austenitizing and Quenching Treatment, and this causes hardness to reduce.Therefore, Mn contents Level must as caused by melting trace between 1.0%.Preferably, its contents level is limited to 0.6% to contribute to Obtain optimal low Ms temperature.
In steelmaking process, Si is a kind of useful element.Its height reduce, therefore can in AOD or VOD converters Steel reduction phase after decarburizing phase reduces Cr oxides.However, the Si contents levels in final steel must be in trace To between 1.0%, because the element has thermmohardening effect, which has limited the possibility of the thermal deformation during hot rolling or forging. Preferably, its contents level is limited to 0.6% to help to obtain optimal low Ms temperature.
S and P is the impurity for reducing high-temperature ductility.P easily in boundary segregation and facilitates its cleavage fracture.Further, since with Mn forms the compound as the starting point corroded as caused by spot corrosion, and S reduces the resistance to this kind of corrosion.Therefore, S and P contents level must be respectively in trace to 0.01wt% and trace between 0.04wt%.Preferably, S contents levels do not surpass 0.005% is crossed to better assure that enough corrosion resistances.
Cr is the essential elements of corrosion resistance.However, it is necessary to limit its contents level, have because high content is horizontal by temperature Degree Mf (temperature at the end of martensite transfor mation) decreases below the risk of environment temperature.This can cause in austenitizing and quenching Martensite transfor mation is excessively incomplete after to environment temperature, hardness deficiency.Due to these a variety of causes, Cr contents levels must be 15.0wt% is between 18.0wt%.It is suggested, however, that Cr contents levels are limited in into 15.0~17.0%, be preferably 15.2~ 17.0%, preferably it is 15.5~16.0%, particularly when without the low-temperature treatment of steel, above range causes do not had Temperature Ms when high martensite transfor mation starts, and excessive retained austenite is therefore will not leave behind, excessive retained austenite Hardness can be limited, and therefore limits tensile strength Rm, this is undesirable in martensite steel.If desired, contained by maximum Cr Corrosion resistance caused by the horizontal reduction of amount reduces can be horizontal by the high N content in the range of elsewhere herein defined To compensate.
However, when Cr contents levels reduce, dissolubilities of the N in liquid metal reduces, so as to Cr less than 15% no longer The N of enough dissolvings can be kept in liquid metals under the setting temperature of steel, this causes to form N during solidification2Bubble, And N is no longer able to compensate the reduction of Cr contents in terms of corrosion resistance.It is molten on N when when solidification, ferrostatic pressure reduces The Cr content lower limits of solution property also increase.According to the type of casting method used and casting condition, preferably by minimum Cr contents Level increases to 15.2% or 15.5% to form N to prevent from 15.0%2Any risk of bubble.
Cr contents levels must also meet that this will hereinafter be solved by itself and N and the horizontal associated formula of C content Release.
Element Ni, Cu, Mo and V are expensive, and also reduce temperature Mf.Therefore, it is necessary to by each in these elements Contents level be limited in trace between 0.50wt%, be preferably no greater than 0.10% for Mo.Therefore, after fused raw material These any elements need not be added.It should further be appreciated that Mo contents levels are no more than 0.05%, to help to obtain optimal low temperature Ms.Similarly, preferably Cu contents levels are no more than 0.3%, and V content is horizontal to be no more than 0.2%.
Nb, Ti and Zr are so-called " stability " elements, and this refers to them in the presence of N and C and formed at high temperature Carbide and nitride than Cr more stable carbide and nitride.However, these elements are undesirable, because they are each From carbide and nitride once formed in the fabrication process, the no longer easily dissolving during austenitizing, which has limited Austria C and N contents level in family name's body, and therefore limit the corresponding hardness of martensite after quenching.Therefore, each in these elements Contents level must be between trace to 0.03%.
Equally, Al content level must avoid the formation of Al nitride between trace to 0.010%, its solution temperature mistake Height, and the N content that can reduce austenite is horizontal, therefore reduce the hardness of martensite after quenching.
O content level is by the manufacture method of steel and produced by forming.It must be in trace to maximum 0.0080% Between (80ppm), to avoid the formation of too many and/or excessive oxide inclusion, these oxide inclusions may form rush Into the starting point of spot corrosion, and it can also be peeled off during polishing so that the appearance of product is undesirable.O content is horizontal Also the mechanical performance of steel is influenceed, optionally it can be traditionally set as being no more than according to the requirement of final products user 80ppm limiting value.
Pb, Bi and Sn contents level can be limited to the trace as caused by melting, and each must be no more than 0.02%, in case thermal deformation becomes difficult.
On the contents level well limited, control N content level is an important aspect of the invention.As C, when When in solid solution, it can improve the hardness of martensite, without forming the shortcomings that precipitating during solidification.It is undesirable that C Contents level is too high to avoid the formation of too many precipitation, then Hardness loss can be compensated by adding N.Nitride is in the temperature less than carbide Degree is lower to be formed, and this causes them to be easier to enter in solution during austenitizing.N presence also improves corrosion resistant in solid solution Corrosion.
However, too high N content level no longer allows it to be completely dissolved during solidification, and result in N2Bubble, The bubble forms stomata (hole) during steel solidifies, and the internal state of metal is harmful to.
Due to these a variety of causes, N content level must be in 0.10wt% between 0.20wt%, preferably in 0.15wt% To between 0.20wt%.
N content level must also meet itself and Cr and the horizontal associated formula of C content.
In fact, the hardness of martensite depends on its C and N content is horizontal.Present inventors have demonstrated that both elements Hardening effect is similar, therefore total content level of the hardness of martensite depending on its C+N.Present inventor have demonstrated that if abide by Below equation is followed, then the hardness after quenching and annealing is enough：
C+N >=0.25%, preferably C+N >=0.30%
In a preferred embodiment of the invention, if following below equation, it can be obtained after quenching and annealing The hardness of even more high：
C+N >=0.45%.
Three kinds of element influences corrosion resistances.Cr and N is beneficial, and C has negative effect, because during austenitizing It is generally impossible to dissolve all Cr carbide, because in industrial practice, is limited for the reason for productivity ratio and cost aspect Processing time and temperature.The Cr carbide not dissolved reduces the Cr contents levels of austenitic matrix, so as to reduce corrosion resistant Corrosion.
According to the corrosion resistance research of the martensite steel to Cr, N and C with different weight content, the inventors discovered that Make the associated formula of these various elements, the formula may insure extraordinary corrosion resistance.
Cr+16N-5C >=16.0%
One preferred but non-imposed condition is：
17Cr+500C+500N≤570%
The condition may insure that temperature Ms will not be too high, because relative to the upper limit for meeting selected C, N and Cr simultaneously The Ms that contents level is allowed, it then follows the formula causes Ms to reduce about 60 DEG C.
Quenched with the cooling velocity more than 100 DEG C/s in 20 DEG C of water, then carry out annealing it at 200 DEG C Before, at different temperatures to having carried out austenitizing test according to the steel of the present invention, to change the carbide proportion of dissolving, thus The carbon content changed in austenite is horizontal, and the carbon content then changed after quenching in martensite is horizontal.Measure martensite level And Vickers hardness, to follow the trail of hardness with the horizontal change of martensite, and by with the steel of embodiment I4 composition in table 1 As a result it is shown in Figure 1.
Fig. 1 shows to reduce as martensite is horizontal, and hardness starts to increase, because martensite is hardened due to carbon enrichment.Firmly Degree reaches maximum, and then when martensite level becomes too low, hardness reduces.Martensite less than 75%, the hardening of martensite It is no longer cancel out the related softening of the presence of the retained austenite relatively low to hardness.Therefore, in a preferred embodiment of the invention In, it is suitable for manufacturing cutting element by cast steel, is quenched in austenitizing, with least 15 DEG C/s speed less than or equal to 20 DEG C then at 100 DEG C~300 DEG C, the martensite level of the steel after usually annealing at a temperature of 200 DEG C is more than or equal to 75%.
If carried out after being quenched under 20 DEG C or lower temperature and before 100 DEG C~300 DEG C of annealing is carried out Low-temperature treatment, i.e. in the medium of -220 DEG C to -50 DEG C of very low temperature, generally in -196 DEG C of liquid nitrogen or -80 DEG C two Quenched in carbonoxide snow, the high martensite level that acquisition can reach 100% can be better assured that.
When martensite content level is not reaching to 100%, remaining micro-structural is generally mainly made up of retained austenite. There may also be ferrite.
As non-limiting example, following result will show the favorable characteristics of the present invention.
The composition of each test steel sample as expressed in weight percent is shown in Table 1.The value of mark underscore is not meet this The value of invention.We also reported the C+N values, Cr+16N-5C values and 17Cr+500C+500N values of each sample.
Table 1：The composition of test sample
After casting, these steel are heated above to 1100 DEG C of temperature, are hot-rolled down to 3mm thickness, at a temperature of 800 DEG C Annealing, then pickling and it is cold-rolled to 1.5mm thickness.
Next steel plate is annealed at a temperature of 800 DEG C.
Next annealed steel plate carries out austenitizing processing 15 minutes at 1050 DEG C, then in quenching-in water to 20 ℃。
, into after two parts, next a wherein part is immersed in by plate cutting in -80 DEG C of constant temperature bath 10 minutes, Can assess relative to only also having carried out the effect of low-temperature treatment in quenching-in water.
Next at 200 DEG C each sheet material portions are carried out with annealing 1 hour.
Table 2 shows the test and observation result to these steel.The value of mark underscore corresponds to the performance for being considered as deficiency It is horizontal.
After pouring, the internal state of original curdled appearance is assessed, learns that subsequent transition operation will not be damaged Internal state.
After 20 DEG C of quenching-in water and after by quenching progress low-temperature treatment at -80 DEG C, martensite level is measured, Wherein, the annealing at 200 DEG C has been carried out after quenching or second of quenching in these quenchings.Quenched when in 20 DEG C of water Martensite is horizontal after fire when being more than or equal to 75%, and other results provided in table 2 are related at 20 DEG C quenching and then at 200 DEG C The state of lower annealing.When martensite is horizontal after 20 DEG C of quenching-in water is less than or equal to 75%, other provided in table 2 are tied Fruit, which is related at -80 DEG C, carries out low-temperature treatment (be quenched to low-down temperature, such as carried out in dry ice), Ran Hou State after being annealed at 200 DEG C.
By in pH 6.6 times and the spot corrosion occurred at 23 DEG C in the environment being made up of NaCl 0.02M, passing through electricity Chemical attack is tested, and corrosion resistance is assessed.The electro-chemical test carried out to 24 samples can determine potential E0.1, Electrical piting probability is equal to 0.1cm under the potential-2.If the potential E that the calomel electrode for having KCl relative to saturation measures0.1It is less than 350mV (350mV/ECS), it is believed that corrosion resistance is undesirable.If potential E0.1In 350mV/ECS to 450mV/ECS Between, it is believed that corrosion resistance is satisfactory.If potential E0.1More than 450mV/ECS, it is believed that corrosion resistance is to meet very much It is required that.
According to standard EN ISO 6507, in the case where 1kg has the load of tapered ledge the pressure of the drill head of square basal plane, in mirror Vickers hardness is measured in the thickness of mirror polish cutting.The average value of the hardness of acquisition is calculated with 10 impressions.It is if average Hardness is less than 500HV, it is believed that hardness is insufficient.If average hardness is in 500HV between 550HV, it is believed that hardness is to meet It is required that.If average hardness is in 551HV between 600HV, it is believed that hardness is very satisfactory.If average hardness is big In 600HV, it is believed that hardness is excellent.
By being entered successively using SiC 180,320,500,800 and 1200 sand paper with 30N power to the sample of intermediate gauge Row flat polish, it is then 3 μm with particle diameter, then sheet material is thrown under 20N power with the diamond slurry that particle diameter is 1 μm Light, measure polishability.Followed by the observation by light microscope surface that multiplication factor is 100.If conventionally referred to as " broom The flaw concentration of tail " is more than or equal to 100/cm2, it is believed that polishability is insufficient.If the density is in 10/cm2To 99/cm2It Between, it is believed that polishability is satisfactory.If the density is in 1/cm2To 9/cm2Between, it is believed that polishability is to conform to very much Ask.If the density is less than 1/cm2, it is believed that polishability is excellent.
The otch that original solidified steel is observed by using the optical metallographic microscope that multiplication factor is 25 have evaluated internal state. If it is observed that spherical empty (stomata) of nitrogen bubble being formed during reflection solidification, then internal state is undesirable, and Represented in table 2 by being worth " 0 ".Otherwise it is assumed that internal state is satisfactory, and represented in table 2 by being worth " 1 ".
Pass through intensity of the X-ray diffraction measurement compared to the martensite characteristic ray of austenite characteristic ray intensity, measurement Martensite is horizontal, learns in all test samples, they only exist two-phase.Generally, however not excluded that in the sample according to the present invention Other phases can be slightly observed in product.In the context of the present invention, overriding concern is martensite level.
In 20 DEG C of quenchings and after 200 DEG C of annealing, martensite is horizontal more than or equal to 75%, or is quenched at 20 DEG C ,- Low-temperature treatment is carried out at 80 DEG C and martensite is horizontal more than or equal to 75% after 200 DEG C of annealing, then is met the requirements.If pass through The martensite that one of these processing can not obtain more than 75% is horizontal, it is believed that the sample is undesirable.
Table 2：The result tested the sample of table 1
Good corrosion resistance, hardness and polishing performance are combined with according to the steel I1 to I6 of the present invention and steel I8 to I0, It is and horizontal with the martensite more than or equal to 75% after being quenched with good internal state and at 20 DEG C.
Good corrosion resistance, hardness and polishing performance are combined with according to the steel I7 of the present invention, and with well interior Portion's health and the martensite level more than or equal to 75%, but be based at -80 DEG C under conditions of progress low-temperature treatment.It is real On border, only after 20 DEG C of quenching-in water, martensite level is still insufficient, and this is with Cr with higher than other samples according to the present invention Contents level exist it is relevant.
In the case where N content is on close level, it can be seen that be on the one hand samples of the C between 0.10% to 0.20% I1、I2；On the other hand it is sample I3 of the C between 0.20% to 0.30%, and most important C is 0.30% to 0.35% I8, I9, I10 between hardness increase.
C content is still very high and the I14 of N content as before has the hardness lower than them, because after quenching Martensite fraction start to reduce because temperature Mf is reduced, wherein, temperature Mf reduction and 17Cr+500C+500N summation Very big (being shown in Table 1) is relevant.Equally, in the case where N is suitable with other indispensable element contents, it can be seen that Cr content increases can To improve corrosion resistance (see sample I8 and I9).However, the increase of Cr contents levels is tended to reduce hardness；See sample I8, I10 And I11, the significant difference that they are formed are only that Cr.Cr contents can improve corrosion resistance more than 18%, but cause C and N Contents level is reduced to keep satisfactory Ms, and can no longer ensure that suitable hardness.
Reference steel R1 to R3 Cr and N content, and C+N and/or Cr+16N-5C summations do not comply with requirement, and it can not Enough corrosion resistances are provided.
Reference steel R4 and R5 Cr contents deficiency.Compensated not over addition N, steel R4 also has the Cr+ of deficiency 16N-5C is combined, and causes its corrosion resistance undesirable.It is again resistance to by the shortage for adding N compensation Cr for steel R5 Corrosivity meets the requirements, but is no longer able to ensure good internal state, because Cr contents levels are no longer enough to allow N in liquid It is completely dissolved in metal.
Reference steel R6 C content is too high, the horizontal deficiency of N content.Due to forming excessive carbide, too high C content water It is flat not have enough polishabilities.
Reference steel R7 N content level is too high, damages internal state.Reference steel R14 is also such.Reference steel R8 C contains Amount is horizontal too high, and this causes poor polishability and too low martensite horizontal, after carrying out low temperature quenching at -80 DEG C So.Reference steel R9 contains too many Cr, and this causes the horizontal deficiency of martensite, after carrying out low temperature quenching at -80 DEG C So.
Reference steel R10 and R11 C content are too low, and C+N summations deficiency, cause hardness too low.Reference steel R12 and R13 Meet the composition according to the present invention for the respective contents level of every kind of element, but their Cr+16N-5C contents levels are low In 16.0%, be not sufficient to ensure that and meet all aspects of the invention requirement steel (including Cr+16N-5C summation only slightly more than Those of 16.0%) there is same high corrosion resistance.
There is the reasons why fine to be used to produce cutting element according to the steel of the present invention, for example, scalpel, scissors, table knife blade or Food processing machine circular shear blade.

Claims (9)

1. a kind of martensitic stain less steel, it is characterised in that the composition of the martensitic stain less steel is by weight percentage by following Composition：
0.10%≤C≤0.45%, preferably 0.20%≤C≤0.38%, preferably, 0.20%≤C≤0.35% are best 0.30%≤C≤0.35%；
Trace≤Mn≤1.0%；It is preferred that trace≤Mn≤0.6%；
Trace≤Si≤1.0%；
Trace≤S≤0.01%；It is preferred that trace≤S≤0.005%；
Trace≤P≤0.04%；
15.0%≤Cr≤18.0%, preferably 15.0%≤Cr≤17.0%, preferably, 15.2%≤Cr≤17.0% are best 15.5%≤Cr≤16.0%；
Trace≤Ni≤0.50%；
Trace≤Mo≤0.50%；It is preferred that trace≤Mo≤0.1%；Preferably, trace≤Mo≤0.05%；
Trace≤Cu≤0.50%；It is preferred that trace≤Cu≤0.3%；
Trace≤V≤0.50%；It is preferred that trace≤V≤0.2%；
Trace≤Nb≤0.03%；
Trace≤Ti≤0.03%；
Trace≤Zr≤0.03%；
Trace≤Al≤0.010%；
Trace≤O≤0.0080%；
Trace≤Pb≤0.02%；
Trace≤Bi≤0.02%；
Trace≤Sn≤0.02%；
0.10%≤N≤0.20%, preferably 0.15%≤N≤0.20%；
C+N >=0.25%；It is preferred that C+N >=0.30%；Preferably, C+N >=0.45%；
Cr+16N-5C >=16.0%；
It is preferred that 17Cr+500C+500N≤570%；
Remaining is iron and the impurity as caused by production.
2. steel according to claim 1, it is characterised in that its micro-structural includes at least 75% martensite.
3. one kind is used to manufacture the process of semi-finished made of martensitic stain less steel, it is characterised in that：
By with the steel formed described in claim 1 come the semi-finished product that produce and cast；
The semi-finished product are heated to the temperature more than or equal to 1000 DEG C；
Hot rolling is carried out to the semi-finished product to obtain sheet material, bar or wire rod；
The sheet material, bar or wire rod are annealed at a temperature of between 700 DEG C to 900 DEG C；With
Operation is formed to the sheet material, bar or wire rod.
4. according to the method for claim 3, it is characterised in that the semi-finished product are sheet material, and the shaping operation is Cold rolling.
5. according to the method for claim 3, it is characterised in that the semi-finished product are bar or wire rod, and the shaping Operation is forging.
6. the method according to any one of claim 3 to 5, it is characterised in that the steel has according to claim 2 institute The composition stated, next the formed semi-finished product carry out austenitizing between 950 DEG C to 1150 DEG C, then with least 15 DEG C/s speed is cooled to temperature less than or equal to 20 DEG C, then annealed at a temperature of between 100 DEG C to 300 DEG C.
7. the method according to any one of claim 3 to 5, it is characterised in that the steel have according to claim 1 or Next composition described in 2, the formed semi-finished product carry out austenitizing between 950 DEG C to 1150 DEG C, then so that Few 15 DEG C/s speed is cooled to the temperature less than or equal to 20 DEG C, then carries out low temperature at a temperature of -220 DEG C to -50 DEG C Processing, is then annealed at a temperature of between 100 DEG C to 300 DEG C.
8. a kind of cutting element, it is characterised in that the cutting element is as the side any one of according to claim 3 to 7 The semi-finished product of method manufacture are made.
9. cutting element according to claim 8, it is characterised in that the cutting element is such as table knife blade, food Process the cutter of machine knife blade, scalpel or scissor blade etc..
CN201680025863.1A 2015-04-30 2016-04-29 Martensitic stain less steel, by the steel making process of semi-finished and the cutting element made of semi-finished product Pending CN107567507A (en)

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