(19)
(11)EP 3 322 830 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
18.03.2020 Bulletin 2020/12

(21)Application number: 16738798.4

(22)Date of filing:  14.07.2016
(51)Int. Cl.: 
C21D 7/06  (2006.01)
C21D 9/52  (2006.01)
C22C 38/02  (2006.01)
C22C 38/06  (2006.01)
C22C 38/50  (2006.01)
C22C 38/42  (2006.01)
C22C 38/44  (2006.01)
C22C 38/54  (2006.01)
C21D 9/22  (2006.01)
C21D 1/25  (2006.01)
C22C 38/04  (2006.01)
C22C 38/46  (2006.01)
C22C 38/52  (2006.01)
C22C 38/48  (2006.01)
C21D 6/00  (2006.01)
C22C 38/58  (2006.01)
(86)International application number:
PCT/EP2016/066808
(87)International publication number:
WO 2017/009435 (19.01.2017 Gazette  2017/03)

(54)

MARTENSITIC STAINLESS STEEL

MARTENSITISCHER ROSTFREIER STAHL

ACIER INOXYDABLE MARTENSITIQUE


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 16.07.2015 EP 15176999

(43)Date of publication of application:
23.05.2018 Bulletin 2018/21

(73)Proprietor: Sandvik Intellectual Property AB
811 81 Sandviken (SE)

(72)Inventors:
  • WENNBERG, Anna
    81290 Storvik (SE)
  • ANTONSSON, Tomas
    SE-811 35 Sandviken (SE)
  • NYLÖF, Lars
    SE-806 28 Gävle (SE)

(74)Representative: Sandvik 
Sandvik Intellectual Property AB
811 81 Sandviken
811 81 Sandviken (SE)


(56)References cited: : 
WO-A1-2009/008798
CN-A- 103 614 649
CN-A- 102 586 695
US-A- 5 714 114
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    TECHNICAL FIELD



    [0001] The present disclosure relates to a martensitic stainless steel suitable for drill rods. Furthermore, the present disclosure also relates to the use of the martensitic stainless steel and to a product manufactured thereof, especially a drill rod.

    BACKGROUND



    [0002] During rock drilling, shock waves and rotation are transferred from a drill rig via one or more rods or tubes to a cemented carbide equipped drill bit. The drill rod is subjected to severe mechanical loads as well as corrosive environment. This applies in particular to underground drilling, where water is used as flushing medium and where the environment, in general, is humid. The corrosion is particularly serious in the most stressed parts, i.e. thread bottoms and thread clearances.

    [0003] Normally, low-alloyed case hardened steels are used for the drilling application. Such steels have the limitation of a relatively short service life due to corrosion fatigue, which results in an accelerated breakage of the drill rod, caused by dynamic loads and insufficient corrosion resistance of the rod material. Another problem related to drill rods is the rate by which the drill rods wear out and have to be replaced due to abrasion, i.e. insufficient hardness of the rod material, which has a direct impact on the total cost for the drilling operation. A further problem related to drill rods is the strength and toughness of the rod material, especially impact toughness, i.e. the ability of the drill rod to withstand the static and dynamic loads, as well as shock loads, caused by rock drilling. If a rod breaks, it may take considerable time to retrieve it from the drill hole. The breaking of a rod may also disturb the calculated drill pattern for the optimized blasting. Additional problems relating to the breaking of drill rods and drill bits is the damage to the mining and tunnelling equipment, e.g. crushers and sieves.

    [0004] Both WO0161064 and WO2009008798 disclose martensitic steels for rock drilling. Even though these steels will solve or reduce the above problem with corrosion fatigue, these martensitic steels will not possess impact toughness high enough to be fully operative during rock drilling. This will mean that the drill components made thereof will have an obvious risk of easy breakage when subjected to shock loads during rock drilling, which may lead to the same consequences as mentioned above.

    [0005] Both CN 102586695 and US 5714114 relate to a martensitic steel. However, the martensitic stainless steels disclosed therein are used for other applications than drill rods. Thus, the requirements and important mechanical properties of the martensitic stainless steels disclosed therein are different compared to a martensitic stainless steel used for drill rods.

    [0006] Consequently, it is an object of the present disclosure to solve and/or to reduce at least one of the above-mentioned problems. In particular, it is an aspect of the present disclosure to achieve an improved martensitic steel composition with a microstructure allowing for the manufacturing of a drill rod with good corrosion resistance and well-balanced and optimized mechanical properties, thus resulting in an increased service life. A further aspect of the present disclosure is to achieve a cost efficient drill component which can be used for a long period of time.

    SUMMARY



    [0007] The present disclosure therefore relates to a martensitic stainless steel comprising the following in weight% (wt%):
    C 0.21 to 0.27;
    Si less than or equal to 0.7;
    Mn 0.2 to 2.5;
    P less than or equal to 0.03;
    S less than or equal to 0.05;
    Cr 11.9 to 14.0;
    Ni more than 0.5 to 3.0;
    Mo 0.4 to 1.5;
    N less than or equal to 0.060;
    Cu less than or equal to 1.2;
    V less than or equal to 0.06;
    Nb less than or equal to 0.03;
    Al less than or equal to 0.050;
    Ti less than or equal to 0.05;
    balance Fe and unavoidable impurities;
    wherein the martensitic stainless steel comprises more than or equal to 75 % martensite phase and less than or equal to 25 % retained austenite phase and
    wherein said martensitic stainless steel has a PRE-value (pitting resistance equivalent value) more than or equal to 14, the PRE value is calculated by the following equation PRE = Cr + 3.3 Mo, wherein Cr and Mo correspond to the contents of the elements in weight percent (wt%); and
    wherein the chemical composition of the said martensitic stainless steel is within an area formed in a Schaeffler diagram, which diagram is based on the following equations:




    wherein the values of Cr, Mo, Si, Nb, Ni, Mn, N and C are in weight%; and which area of the martensitic stainless steel is defined by the following coordinates:
     CreqNieq
    A1 12.300 9.602
    B1 12.300 11.990
    B4 15.702 9.199
    A3 14.482 7.864


    [0008] The martensitic stainless steel as defined hereinabove or hereinafter has thus a hardened and tempered martensitic microstructure containing retained austenite, meaning that the martensitic microstructure comprises both martensite phase and retained austenite phase. The martensite phase will provide the desired hardness and tensile strength and also the desired resistance to wear. The retained austenite phase, which is softer and more ductile compared to the martensite phase, will reduce the brittleness of the martensitic microstructure and thereby provide a necessary improvement in the mechanical properties of the steel, such as impact toughness. The martensitic stainless steel as defined herein above or hereinafter will due to both its chemical composition and its microstructure have a unique combination of hardness, impact toughness, strength, and corrosion resistance. Furthermore, the present disclosure also relates to the use of the martensitic stainless steel as defined hereinabove or hereinafter for manufacturing of a drill rod, such as a top hammer drill rod and water flushed top hammer drill rods, and the manufacture thereof.

    DESCRIPTION OF THE FIGURES



    [0009] 
    Figure 1
    shows the Schaeffler diagram wherein the area and the corresponding coordinates have been drawn
    Figure 2
    shows the same Schaeffler diagram as Figure 1 but the manufactured alloys of the Examples have been marked in the diagram
    Figure 3
    shows the hardness and impact toughness curves for some of the alloys of the Examples.

    DETAILED DESCRIPTION



    [0010] The present disclosure relates to a martensitic stainless steel having the following composition in wt%:
    C 0.21 to 0.27;
    Si less than or equal to 0.7;
    Mn 0.2 to 2.5;
    P less than or equal to 0.03;
    S less than or equal to 0.05;
    Cr 11.9 to 14.0;
    Ni more than 0.5 to 3.0;
    Mo 0.4 to 1.5;
    N less than or equal to 0.060;
    Cu less than or equal to 1.2;
    V less than or equal to 0.06;
    Nb less than or equal to 0.03;
    Al less than or equal to 0.050;
    Ti less than or equal to 0.05;
    balance Fe and unavoidable impurities;
    wherein the martensitic stainless steel comprises more than or equal to 75 % martensite phase and less than or equal to 25 % retained austenite phase and
    wherein said martensitic stainless steel has a PRE-value more than or equal to 14; and
    wherein the chemical composition of the said martensitic stainless steel is within an area formed in a Schaeffler diagram, which diagram is based on the following equations:




    wherein the values of Cr, Mo, Si, Nb, Ni, Mn, N and C are in weight%; and which area of the martensitic stainless steel is defined by the following coordinates:
     CreqNieq
    A1 12.300 9.602
    B1 12.300 11.990
    B4 15.702 9.199
    A3 14.482 7.864


    [0011] The present martensitic stainless steel will have high tensile strength and high wear resistance due to a high hardness of the martensite phase. The martensite phase is however brittle. In the present disclosure, it has been found that by combining the martensite phase with a certain amount of retained austenite phase(such that the microstructure comprises more than or equal to 75 % martensite phase and less than or equal to 25 % retained austenite phase),and further by combining this with a balanced addition of alloying elements, especially Ni, Mn and Mo, the impact toughness of the martensitic stainless steel will be greatly improved. The martensite phase will, as mentioned above, provide the desired hardness and tensile strength and also the desired resistance to wear while the retained austenite phase, which is softer and more ductile compared to the martensite phase, will reduce the brittleness of the martensitic microstructure and thereby provide a necessary improvement in the mechanical properties. It is however necessary that there is not a too high amount of retained austenite phase as this will reduce the hardness of the martensitic microstructure too much. Thus, the amount of martensite phase and the amount of retained austenite phase is as defined hereinabove or hereinafter. According to one embodiment, the martensitic stainless steel as defined hereinabove or hereinafter does not contain any ferrite phase after hardening, which in this context is considered to be a soft and brittle phase.

    [0012] The martensitic stainless steel as defined herein above or hereinafter has a PRE-value which is more than or equal to 14. By having a PRE-value more than or equal to 14, the desired pitting corrosion resistance is obtained.

    [0013] Furthermore, the chemical composition of the martensitic stainless steel as defined hereinabove or hereinafter is as already stated above represented by an area defined by specific coordinates in a Schaeffler diagram according to its Cr- and Ni-equivalents (see Figure 1). This Schaeffler diagram is used to predict the presence and amount of austenite (A), ferrite (F) and martensite (M) phases in the microstructure of a steel after fast cooling from a high temperature and is based on the chemical composition of the steel. The specific coordinates of the area of the present disclosure in the Schaeffler diagram have been determined by calculating the Cr- and Ni-equivalents (Creq and Nieq) according to the following equations (see Figure 1):



    wherein the values of Cr, Mo, Si, Nb, Ni, Mn, N and C are in weight%; and where the area of the martensitic stainless steel is defined by the coordinates presented in Figure 1 and Figure 2. Hence, the present disclosure provides a martensitic stainless steel having a unique combination of high hardness and high impact toughness as well as good corrosion resistance. Further, the present disclosure provides a martensitic stainless steel having a chemical composition and microstructure giving an object made thereof an optimal combination of corrosion resistance and hardness and impact toughness throughout the whole object, whereby the cost efficiency will be much improved as well as the operation time in service.

    [0014] According to another embodiment of the present disclosure, the martensitic stainless steel as defined hereinabove or hereinafter comprises of from 80 to 95 % martensite phase and of from 5 to 20 % retained austenite phase.

    [0015] The alloying elements of the martensitic stainless steel according to the present disclosure will now be described. The terms "weight%" and "wt%" are used interchangeably:

    Carbon (C): 0.21 to 0.27 wt%



    [0016] C is a strong austenite phase stabilizing alloying element. C is necessary for the martensitic stainless steel so that said steel has the ability to be hardened and strengthened by heat treatment. The C-content is therefore set to be at least 0.21 wt% so as to sufficiently achieve the before mentioned effects. However, an excess of C will increase the risk of forming chromium carbide, which would thus reduce various mechanical properties and other properties, such as ductility, impact toughness and corrosion resistance. The mechanical properties are also affected by the amount of retained austenite phase after hardening and this amount will depend on the C-content. Accordingly, the C-content is set to be at most 0.27 wt%, thus the carbon content of the present martensitic stainless steel is of from about 0.21 to 0.27 wt%, such as of from 0.21 to 0.26 wt%.

    Silicon (Si): max 0.7 wt%



    [0017] Si is a strong ferrite phase stabilizing alloying element and therefore its content will also depend on the amounts of the other ferrite forming elements, such as Cr and Mo. Si is mainly used as a deoxidizer agent during melt refining. If the Si-content is excessive, ferrite phase as well as intermetallic precipitates may be formed in the microstructure, which will reduce various mechanical properties. Accordingly, the Si-content is set to be max 0.7 wt%, such as max 0.4 wt%.

    Manganese (Mn): 0.2 to 2.5 wt%



    [0018] Mn is an austenite phase stabilizing alloying element. Mn will promote the solubility of C and N in the austenite phase and will increase the deformation hardening. Furthermore, Mn will also increase hardenability when the martensitic stainless steel is heat treated. Mn will further reduce the detrimental effect of sulphur by forming MnS precipitates, which in turn will enhance the hot ductility and the impact toughness, but MnS precipitates may also impair the pitting corrosion resistance somewhat. Therefore, the lowest Mn-content is set to be 0.2 wt%. However, if the Mn-content is excessive, the amount of retained austenite phase may become too large and various mechanical properties, as well as hardness and corrosion resistance, may be reduced. Also, a too high content of Mn will reduce the hot working properties and also impair the surface quality. The Mn-content is therefore set to be at most 2.5 wt%. Hence, the content of Mn is of from 0.2 to 2.5 wt%, such as 0.3 to 2.4 wt%. Additionally, in the present disclosure, the content of Mn, Ni and Mo comprised in the martensitic stainless steel is balanced together in order to obtain the desired properties of said martensitic stainless steel.

    Chromium (Cr): 11.9 to 14.0 wt%



    [0019] Cr is one of the basic alloying elements of a stainless steel and an element which will provide corrosion resistance to the steel. The martensitic stainless steel as defined hereinabove or hereinafter comprises at least 11.9 wt% in order to achieve a Cr-oxide layer and/or a passivation of the surface of the steel in air or water, thereby obtaining the basic corrosion resistance. Cr is also a ferrite phase stabilizing alloying element. However, if Cr is present in an excessive amount, the impact toughness may be decreased and additionally ferrite phase and chromium carbides may be formed upon hardening. The formation of chromium carbides will reduce the mechanical properties of the martensitic stainless steel. An increase of the Cr-content above the level for passivation of the steel surface will have only weak effects on the corrosion resistance of the martensitic stainless steel. The Cr-content is therefore set to be at most 14.0 wt%. Hence, the content of Cr is of from 11.9 to 14.0 wt%, such as 12.0 to 13.8 wt%.

    Molybdenum (Mo): 0.4 to 1.5 wt%



    [0020] Mo is a strong ferrite phase stabilizing alloying element and thus promotes the formation of the ferrite phase during annealing or hot-working. One major advantage of Mo is that it contributes strongly to the pitting corrosion resistance. Mo is also known to reduce the temper embrittlement in martensitic steels and thereby improves the mechanical properties. However, Mo is an expensive element and the effect on corrosion resistance is obtained even in low amounts. The lowest content of Mo is therefore 0.4 wt%. Furthermore, an excessive amount of Mo affects the austenite to martensite transformation during hardening and eventually the retained austenite phase content. Therefore, the upper limit of Mo is set at 1.5 wt%. Hence, the content of Mo is of from 0.4 to 1.5 wt%, such as 0.5 to 1.4 wt%.

    Nickel (Ni): more than 0.5 to 3.0 wt%



    [0021] Ni is an austenite phase stabilizing alloying element and thereby stabilize the retained austenite phase after a hardening heat treatment. It has also been discovered that Ni will provide a much improved impact toughness in addition to the general toughness contribution which is provided by the retained austenite phase. In the present disclosure, it has been found that by balancing the amount of Ni, Mn and Mo in the martensitic stainless steel, the best combination of hardness, impact toughness and corrosion resistance will be provided. More than 0.5 wt% Ni is required to provide a substantial effect. However, if the Ni-content is excessive, the amount of retained austenite phase will be too high and the hardness will then be insufficient. The maximum content of Ni is therefore limited to 3.0 wt%. Hence, the content of Ni is from more than 0.5 to 3.0 wt%, such as from more than 0.5 to 2.4 wt%.

    Tungsten (W): less than or equal to 0.5 wt%



    [0022] W is a ferrite phase stabilizing alloying element and if present it may to some extent replace Mo as an alloying element, due to similar chemical properties. W has a positive effect on the resistance against pitting corrosion, but the effect is much weaker than the effect of Mo, if the dissolved matrix contents are compared, which normally is the reason why W is excluded from the PRE-formula. In order to replace Mo, a much higher W-content therefore becomes necessary. W is also a carbide forming element and at high contents of W, the wear resistance will be improved, as well as hardness and strength. However, at W-contents where the above properties are improved, the amount of W-carbides will considerably decrease the impact toughness of the steel. The required W-contents will also result in an increased temperature stability of the carbides, and in order to increase the content of dissolved W in the matrix, much higher hardening temperatures are needed. The content of W is therefore set to be less than or equal to 0.5 wt%, such as less than or equal to 0.05 wt%.

    Cobalt (Co): less than or equal to 1.0 wt%,



    [0023] Cobalt has a strong solid solution effect and gives rise to a strengthening effect, which also remains at higher temperatures. Therefore, Co is often used as an alloying element to improve the high temperature strength, as well as the hardness and resistance to abrasive wear at elevated temperatures. However, at Co-contents where the effects on these properties are significantly improved, the Co-content also has an opposite effect on the hot working properties, causing higher deformation forces. Co is the only alloying element that destabilizes the austenite phase and thus facilitates the transformation of austenite, as well as retained austenite, into martensite phase or ferrite containing phases, on cooling. Due to the complex effects of Co, but also due to the fact that it is toxic, and regarded as an impurity in scrap material used for production of stainless steels intended for atomic energy applications, the content of Co, if present, is therefore set to be less than or equal to 1.0 wt%, such as less than or equal to 0.10 wt%.

    Aluminum (Al) less than or equal to 0.050 wt%



    [0024] Al is an optional element and is commonly used as a deoxidizing agent as it is effective in reducing the oxygen content during steel production. However, a too high content of Al may reduce the mechanical properties. The content of Al is therefore less than or equal to 0.050 wt%.

    Nitrogen (N): less than or equal to 0.060 wt%



    [0025] N is an optional element and is an austenite phase stabilizing alloying element and has a very strong interstitial solid solution strengthening effect. However, a too high content of N may reduce the hot working properties at high temperatures and may also reduce the impact toughness at room temperature for the present martensitic stainless steel. The N-content is therefore set to be less than or equal to 0.060 wt%, such as less than or equal to 0.035 wt%.

    Vanadium (V): less than or equal to 0.06 wt%



    [0026] V is an optional element and is a ferrite phase stabilizing alloying element which has a high affinity to C and N. V is a precipitation hardening element and is regarded as a micro-alloying element in the martensitic stainless steel and may be used for grain refinement. Grain refinement refers to a method to control grain size at high temperatures by introducing small precipitates in the microstructure, which will restrict the mobility of the grain boundaries and thereby will reduce the austenite grain growth during hot working or heat treatment. A small austenite grain size is known to improve the mechanical properties of the martensitic microstructure formed upon hardening. However, an excessive amount of V will generate a too high fraction of precipitates in the microstructure and especially increase the risk of the formation of coarser V precipitations in the prior austenite grain boundaries of the martensitic microstructure, thus reducing the ductility, especially the impact toughness. The content of V is therefore less than or equal to 0.06 wt%.

    Niobium (Nb): less than or equal to 0.03 wt%



    [0027] Nb is an optional element which is a ferrite phase stabilizing alloying element and has a high affinity to C and N. Thus, Nb is a precipitation hardening element and may be used for grain refinement, however, Nb also forms coarse precipitations. An excessive amount of Nb may therefore reduce the ductility and impact toughness of the martensitic stainless steel and the content of Nb therefore is less than or equal to 0.03 wt%.

    Zirconium (Zr): less than or equal to 0.03 wt%



    [0028] Zr is an optional element which has a very high affinity to C and N. Zirconium nitrides and carbides are stable at high temperatures and may be used for grain refinement. If the Zr-content is too high, coarse precipitations may be formed, which will decrease the impact toughness. The content of Zr is therefore less than or equal to 0.03 wt%.

    Tantalum (Ta): less than or equal to 0.03 wt%



    [0029] Ta is an optional element which has a very high affinity to C and N. Tantalum nitrides and carbides are stable at high temperatures and may be used for grain refinement. If the Ta-content is too high, coarse precipitations may be formed, which will decrease the impact toughness. The content of Ta is therefore less than or equal to 0.03 wt%.

    Hafnium (Hf): less than or equal to 0.03 wt%



    [0030] Hf is an optional element which has a very high affinity to C and N. Hafnium nitrides and carbides are stable at high temperatures and may be used for grain refinement. If the Hf-content is too high, coarse precipitations may be formed, which will decrease the impact toughness. The content of Hf is therefore less than or equal to 0.03 wt%.

    Phosphorous (P): less than or equal to 0.03 wt%



    [0031] P is an optional element and may be included as an impurity and is regarded as a harmful element. Therefore, it is desirable to have less than 0.03 wt% P.

    Sulphur (S): less than or equal to 0.05 wt%



    [0032] S is an optional element and may be included in order to improve the machinability. However, S may form grain boundary segregations and inclusions and will therefore restrict the hot working properties and also reduce the mechanical properties and corrosion resistance. Hence, the content of S should not exceed 0.05 wt%.

    Titanium (Ti): less than or equal to 0.05 wt%



    [0033] Ti is an optional element which is a ferrite phase stabilizing alloying element and has a very high affinity to C and N. Titanium nitrides and carbides are stable at high temperatures and may be used for grain refinement. If the Ti-content is too high, coarse precipitations may be formed, which will decrease the impact toughness. The content of Ti is therefore less than or equal to 0.05 wt%.

    Copper (Cu) less than or equal to 1.2 wt%



    [0034] Cu is an austenite phase stabilizing alloying element and has rather limited effects on the martensitic stainless steel in small amounts. Cu may to some extent replace Ni or Mn as austenite phase stabilizers in the martensitic stainless steel but the ductility will then be reduced compared to e.g. an addition of Ni. Cu may have a positive effect on the general corrosion resistance of the steel but higher amounts of Cu will affect the hot working properties negatively. The content of Cu is therefore less than or equal to 1.2 wt%, such as less than or equal to 0.8 wt%.

    [0035] Optionally small amounts of other alloying elements may be added to the martensitic stainless steel as defined hereinabove or hereinafter in order to improve e.g. the machinability or the hot working properties, such as the hot ductility. Example, but not limiting, of such elements are Ca, Mg, B, Pb and Ce. The amounts of one or more of these elements are of max. 0.05 wt%.

    [0036] When the terms "max" or "less than or equal to" are used, the skilled person knows that the lower limit of the range is 0 wt% unless another number is specifically stated.

    [0037] The remainder of elements of the martensitic stainless steel as defined hereinabove or hereinafter is Iron (Fe) and normally occurring impurities.

    [0038] Examples of impurities are elements and compounds which have not been added on purpose, but cannot be fully avoided as they normally occur as impurities in e.g. the raw material or the additional alloying elements used for manufacturing of the martensitic stainless steel.

    [0039] According to one embodiment of the present disclosure, the chemical composition of the martensitic stainless steel as defined hereinabove or hereinafter may be represented by an area in a Schaeffler diagram defined by the following coordinates (see Figure 1 and Figure 2):
     CreqNieq
    A2 12.923 9.105
    B2 12.923 11.479
    B4 15.702 9.199
    A3 14.482 7.864


    [0040] According to one embodiment of the present disclosure, the chemical composition of the martensitic stainless steel as defined hereinabove or hereinafter may be represented by an area in a Schaeffler diagram defined by the following coordinates (see Figure 1 and Figure 2):
     CreqNieq
    A1 12.300 9.602
    B1 12.300 11.990
    B3 14.482 10.200
    A3 14.482 7.864


    [0041] According to a further embodiment of the present disclosure, the chemical composition of the martensitic stainless steel as defined hereinabove or hereinafter may be represented by an area in a Schaeffler diagram defined by the following coordinates (see Figure 1 and Figure 2):
     CreqNieq
    A2 12.923 9.105
    B2 12.923 11.479
    B3 14.482 10.200
    A3 14.482 7.864


    [0042] The martensitic stainless steel as defined hereinabove or hereinafter and the drill rod manufactured thereof are made by conventional steel production and steel machining processes and conventional drill rod production and drill rod machining processes. In order to obtain the desired martensitic structure, the martensitic stainless steel has to be hardened and tempered. The mechanical properties of the surface may be further improved by induction heating of the surface or by applying surface treatment methods, such as but not limited to shot peening. The obtained martensitic steel and/or objects made thereof will have good corrosion resistance in combination with optimized and well-balanced mechanical properties, such as high hardness, resistance against wear and abrasion, high tensile strength and high impact toughness.

    [0043] The martensitic stainless steel according to the present disclosure is intended, as mentioned herein, for manufacturing of drill rods, such as top hammer drill rods. The martensitic stainless steel according to the present disclosure will provide the drill rods with high hardness, resistance against wear and abrasion, high tensile strength, high impact toughness and good corrosion resistance, it should be noted that there are today no drill rods commercially available, which are made of stainless steel.

    [0044] Hence, the present disclosure also relates to a drill rod comprising the martensitic stainless steel as defined hereinabove or hereinafter, which will have all the properties mentioned above, i.e. having a combination of good corrosion resistance and optimized and well-balanced mechanical properties.

    [0045] The present disclosure is further illustrated by the following non-limiting examples.

    EXAMPLES


    Example 1



    [0046] The alloys of Example 1 have been produced by melting in a high frequency furnace and thereafter ingot cast using 9" steel moulds. The weights of the ingots were approximately 270 kg. The ingots were heat-treated by soft annealing at 650 °C for 4 hours and then air cooled to room temperature followed by grinding of the ingot surface.

    [0047] After the heat treatment, the ingots were forged in a hammer to bars having a round dimension of approximately 145 mm. The obtained round bars were then hot rolled at 1200°C in a rolling mill to solid hexagonal 35 mm dimension.

    [0048] Samples from these bars were used for corrosion and mechanical testing.

    [0049] The chemical composition of the different alloys and their corresponding alloy No. is found in Table 1. Alloys outside the scope of the disclosure are marked with an "x" in all tables.

    [0050] The Cr- and Ni-equivalents, i.e. the Creq and the Nieq values, for all alloys of the examples are shown in Table 2 and in Figure 2. The Creq and the Nieq values have been calculated according to the formulas given above in the present disclosure. The PRE-values for each alloy were calculated according to the following equation: PRE = Cr (wt%) + 3.3 Mo (wt%).

    [0051] The corrosion testing was performed by dynamic polarization measurements, either by (Corr 1) immersing a sample in a NaCl-solution (600 mg/l) at room temperature using a voltage scan rate of 10 mV/min, or by (Corr 2) immersing a sample in a NaCl-solution (600 mg/l) at room temperature using a voltage scan rate of 75 mV/min. The breakthrough potential, Ep (V), of the passive oxide film on the steel surface was then measured. The results are based on the average of two samples for each alloy. Before corrosion testing, all samples had been hardened at 1030-1050°C/ 0.5 h, quenched in oil, and tempered at 200-225°C/ 1 h. The result of the corrosion testing is shown in Table 2.

    [0052] Mechanical testing in the form of hardness testing (HRC) and impact toughness testing on notched Charpy-V samples with the dimensions of 10x10x55 mm, was performed at room temperature on all alloys. The samples were hardened at 1030°C/ 0.5h1) or 1050°C/ 1h2), quenched in oil and thereafter tempered at different temperatures, 175-275°C for 1 h. The results of the as-hardened conditions are based on the average of two Charpy-V samples, while the results of the tempered conditions are based on the average of three Charpy-V samples.

    [0053] The result of the mechanical testing is shown in Tables 3A and 3B.

    [0054] Table 4 summarizes a relative ranking of the hot working properties, mechanical properties and the corrosion resistance, based on the experiences during the manufacturing and testing of the alloys of the Example.














    Claims

    1. A martensitic stainless steel consisting of in weight% (wt%):
    C 0.21 to 0.27;
    Si less than or equal to 0.7;
    Mn 0.2 to 2.5;
    P less than or equal to 0.03;
    S less than or equal to 0.05;
    Cr 11.9 to 14.0;
    Ni more than 0.5 to 3.0;
    Mo 0.4 to 1.5;
    W less than or equal to 0.5;
    N less than or equal to 0.060;
    Cu less than or equal to 1.2;
    Co less than or equal to 1.0;
    V less than or equal to 0.06;
    Nb less than or equal to 0.03;
    Zr less than or equal to 0.03;
    Ta less than or equal to 0.03;
    Hf less than or equal to 0.03;
    Al less than or equal to 0.050;
    Ti less than or equal to 0.05;

    and one or more-alloying elements, such as Ca, Mg, B, Pb and Ce, to improve the machinability or the hot working properties max. 0.05 wt%;

    balance Fe and unavoidable impurities;

    wherein the martensitic stainless steel comprises more than or equal to 75 % martensite phase and less than or equal to 25 % retained austenite phase and
    wherein said martensitic stainless steel has a PRE-value more than or equal to 14;
    and wherein the chemical composition of the said martensitic stainless steel is within an area formed in a Schaeffler diagram, which diagram is based on the following equations:



    wherein the values of Cr, Mo, Si, Nb, Ni, Mn, N and C are in weight%; and which area of the martensitic stainless steel is defined by the following coordinates:
     CreqNieq
    A1 12.300 9.602
    B1 12.300 11.990
    B4 15.702 9.199
    A3 14.482 7.864

     
    2. The martensitic stainless steel according to claim 1, wherein said martensitic stainless steel comprises of from 80 to 95 % martensite phase and of from 5 to 20% retained austenite phase.
     
    3. The martensitic stainless steel according to claim 1 or claim 2, wherein the content of Si is less than or equal to 0.4 wt%.
     
    4. The martensitic stainless steel according to any one of claims 1 to 3 wherein the content of N is less than or equal to 0.035 wt%.
     
    5. The martensitic stainless steel according to any one of claims 1 to 4, wherein the content of Cu is less than or equal to 0.8 wt%.
     
    6. The martensitic stainless steel according to any one of claims 1 to 5, wherein the content of C is of from 0.21 to 0.26 wt%.
     
    7. The martensitic stainless steel according to any one of claims 1 to 6, wherein the content of Cr is of from 12 to 13.8 wt%.
     
    8. The martensitic stainless steel according to any one of claims 1 to 7, wherein the content of Mn is of from 0.3 to 2.4 wt%.
     
    9. The martensitic stainless steel according to any one of claims 1 to 8, wherein the content of Ni is more than 0.5 to 2.4 wt%.
     
    10. The martensitic stainless steel according to any one of claims 1 to 9, wherein the content of Mo is of from 0.5 to 1.4 wt%.
     
    11. The martensitic stainless steel according to any one of claims 1 to 10, wherein said chemical composition is within an area formed in a Schaeffler diagram, and wherein said area is defined by the following coordinates:
     CreqNieq
    A2 12.923 9.105
    B2 12.923 11.479
    B4 15.702 9.199
    A3 14.482 7.864

     
    12. The martensitic stainless steel according to any one of claims 1 to 10, wherein said chemical composition is within an area formed in a Schaeffler diagram, and wherein said area is defined by the following coordinates:
     CreqNieq
    A1 12.300 9.602
    B1 12.300 11.990
    B3 14.482 10.200
    A3 14.482 7.864

     
    13. The martensitic stainless steel according to any one of claims 1 to 10, wherein said chemical composition is within an area formed in a Schaeffler diagram, and wherein said area is defined by the following coordinates:
     CreqNieq
    A2 12.923 9.105
    B2 12.923 11.479
    B3 14.482 10.200
    A3 14.482 7.864

     
    14. Use of the martensitic stainless steel according to any one of claims 1 to 13 for manufacturing a drill rod.
     
    15. A drill rod comprising the martensitic stainless steel according to any one of claims 1 to 13.
     


    Ansprüche

    1. Martensitischer rostfreier Stahl, bestehend in Gewichtsprozent (Gew.-%) aus:
    C 0,21 bis 0,27;
    Si weniger als oder gleich 0,7;
    Mn 0,2 bis 2,5;
    P weniger als oder gleich 0,03;
    S weniger als der gleich 0,05;
    Cr 11,9 bis 14,0;
    Ni mehr als 0,5 bis 3,0;
    Mo 0,4 bis 1,5;
    W weniger als der gleich 0,5;
    N weniger als oder gleich 0,06;
    Cu weniger als oder gleich 1,2;
    Co weniger als oder gleich 1,0;
    V weniger als oder gleich 0,06;
    Nb weniger als der gleich 0,03;
    Zr weniger als der gleich 0,03;
    Ta weniger als der gleich 0,03;
    Hf weniger als der gleich 0,03;
    A1 weniger als oder gleich 0,05;
    Ti weniger als oder gleich 0,05;

    und einem oder mehreren Legierungselementen, wie Ca, Mg, B, Pb und Ce, zur Verbesserung der Bearbeitbarkeit oder der Warmumformbarkeitseigenschaften mit max. 0,05 Gew.-%;

    Rest Fe und unvermeidbare Verunreinigungen;

    wobei der martensitische rostfreie Stahl mehr als oder gleich 75 % Martensitphase und weniger als oder gleich 25 % Restaustenitphase umfasst und wobei der martensitische rostfreie Stahl einen PRE-Wert von mehr als oder gleich 14 aufweist; und wobei die chemische Zusammensetzung des martensitischen rostfreien Stahls innerhalb eines in einem Schaeffler-Diagramm gebildeten Bereichs liegt, wobei das Diagramm auf folgenden Gleichungen basiert:



    wobei die Werte von Cr, Mo, Si, Nb, Ni, Mn, N und C in Gew.-% sind; und wobei der Bereich des martensitischen rostfreien Stahls durch folgende Koordinaten definiert wird:

     CreqNieq
    A1 12,300 9,602
    B1 12,300 11,990
    B4 15,702 9,199
    A3 14,482 7,864


     
    2. Martensitischer rostfreier Stahl nach Anspruch 1, wobei der martensitische rostfreie Stahl 80 bis 95 % Martensitphase und 5 bis 20 % Restaustenitphase umfasst.
     
    3. Martensitischer rostfreier Stahl nach Anspruch 1 oder Anspruch 2, wobei der Si-Gehalt weniger als 0,4 Gew.-% beträgt.
     
    4. Martensitischer rostfreier Stahl nach einem der Ansprüche 1 bis 3, wobei der N-Gehalt weniger als 0,035 Gew.-% beträgt.
     
    5. Martensitischer rostfreier Stahl nach einem der Ansprüche 1 bis 4, wobei der Cu-Gehalt weniger als 0,8 Gew.-% beträgt.
     
    6. Martensitischer rostfreier Stahl nach einem der Ansprüche 1 bis 5, wobei der C-Gehalt 0,21 bis 0,26 Gew.-% beträgt.
     
    7. Martensitischer rostfreier Stahl nach einem der Ansprüche 1 bis 6, wobei der Cr-Gehalt 12 bis 13,8 Gew.-% beträgt.
     
    8. Martensitischer rostfreier Stahl nach einem der Ansprüche 1 bis 7, wobei der Mn-Gehalt 0,3 bis 2,4 Gew.-% beträgt.
     
    9. Martensitischer rostfreier Stahl nach einem der Ansprüche 1 bis 8, wobei der Ni-Gehalt mehr als 0,5 bis 2,4 Gew.-% beträgt.
     
    10. Martensitischer rostfreier Stahl nach einem der Ansprüche 1 bis 9, wobei der Mo-Gehalt 0,5 bis 1,4 Gew.-% beträgt.
     
    11. Martensitischer rostfreier Stahl nach einem der Ansprüche 1 bis 10, wobei sich die chemische Zusammensetzung innerhalb eines in einem Schaeffler-Diagramm gebildeten Bereichs befindet und wobei der Bereich durch folgende Koordinaten definiert wird:
     CreqNieq
    A1 12,923 9,105
    B1 12,923 11,479
    B4 15,702 9,199
    A3 14,482 7,864

     
    12. Martensitischer rostfreier Stahl nach einem der Ansprüche 1 bis 10, wobei sich die chemische Zusammensetzung innerhalb eines in einem Schaeffler-Diagramm gebildeten Bereichs befindet und wobei der Bereich durch folgende Koordinaten definiert wird:
     CreqNieq
    A1 12,300 9,602
    B1 12,300 11,990
    B4 14,482 10,200
    A3 14,482 7,864

     
    13. Martensitischer rostfreier Stahl nach einem der Ansprüche 1 bis 10, wobei sich die chemische Zusammensetzung innerhalb eines in einem Schaeffler-Diagramm gebildeten Bereichs befindet und wobei der Bereich durch folgende Koordinaten definiert wird:
     CreqNieq
    A1 12,923 9,105
    B1 12,923 11,479
    B4 14,482 10,200
    A3 14,482 7,864

     
    14. Verwendung des martensitischen rostfreien Stahls nach einem der Ansprüche 1 bis 13 zur Herstellung eines Bohrgestänges.
     
    15. Bohrgestänge, umfassend den martensitischen rostfreien Stahl nach einem der Ansprüche 1 bis 13.
     


    Revendications

    1. Un acier inoxydable martensitique composé de % en poids (% en poids) :
    C 0,21 à 0,27 ;
    Si inférieur ou égal à 0,7 ;
    Mn 0,2 à 2,5 ;
    P inférieur ou égal à 0,03 ;
    S inférieur ou égal à 0,05 ;
    Cr 11,9 à 14,0 ;
    Ni supérieur à 0,5 à 3,0 ;
    Mo 0,4 à 1,5 ;
    W inférieur ou égal à 0,5 ;
    N inférieur ou égal à 0,060 ;
    Cu inférieur ou égal à 1,2 ;
    Co inférieur ou égal à 1,0 ;
    V inférieur ou égal à 0,06 ;
    Nb inférieur ou égal à 0,03 ;
    Zr inférieur ou égal à 0,03 ;
    Ta inférieur ou égal à 0,03 ;
    Hf inférieur ou égal à 0,03 ;
    A1 inférieur ou égal à 0,050 ;
    Ti inférieur ou égal à 0,05 ;

    et un ou plusieurs éléments d'alliage, tels que Ca, Mg, B, Pb et Ce, pour améliorer l'usinabilité ou les propriétés de travail à chaud max. 0,05 % en poids ;

    équilibre en Fe et impuretés inévitables ;

    dans lequel l'acier inoxydable martensitique comprend plus de ou l'équivalent à 75 % de phase de martensite et moins de ou l'équivalent à 25 % de phase d'austénite conservée et dans lequel ledit acier inoxydable martensitique a une valeur PRÉLIMINAIRE supérieure ou égale à 14 ; et dans lequel la composition chimique dudit acier inoxydable martensitique se trouve dans une zone formée dans un diagramme de Schaeffler, lequel diagramme est sur base des équations suivantes :



    dans lequel les valeurs de Cr, Mo, Si, Nb, Ni, Mn, N et C sont en % en poids ; et laquelle zone de l'acier inoxydable martensitique est définie par les coordonnées suivantes :

     CreqNieq
    A1 12,300 9,602
    B1 12,300 11,990
    B4 15,702 9,199
    A3 14,482 7,864


     
    2. Acier inoxydable martensitique selon la revendication 1, dans lequel ledit acier inoxydable martensitique comprend de 80 à 95 % de phase de martensite et de 5 à 20 % de phase d'austénite conservée.
     
    3. Acier inoxydable martensitique selon la revendication 1 ou la revendication 2, dans lequel la teneur en Si est inférieure ou égale à 0,4 % en poids.
     
    4. Acier inoxydable martensitique selon l'une quelconque des revendications 1 à 3, dans lequel la teneur en N est inférieure ou égale à 0,035 % en poids.
     
    5. Acier inoxydable martensitique selon l'une quelconque des revendications 1 à 4, dans lequel la teneur en Cu est inférieure ou égale à 0,8 % en poids.
     
    6. Acier inoxydable martensitique selon l'une quelconque des revendications 1 à 5, dans lequel la teneur en C est de 0,21 à 0,26 % en poids.
     
    7. Acier inoxydable martensitique selon l'une quelconque des revendications 1 à 6, dans lequel la teneur en Cr est de 12 à 13,8 % en poids.
     
    8. Alliage inoxydable martensitique selon l'une quelconque des revendications 1 à 7, dans lequel la teneur en Mn est de 0,3 à 2,4 % en poids.
     
    9. Acier inoxydable martensitique selon l'une quelconque des revendications 1 à 8, dans lequel la teneur en Ni est supérieure à 0,5 à 2,4 % en poids.
     
    10. Acier inoxydable martensitique selon l'une quelconque des revendications 1 à 9, dans lequel la teneur en Mo est de 0,5 à 1,4 % en poids.
     
    11. Acier inoxydable martensitique selon l'une quelconque des revendications 1 à 10, dans lequel ladite composition chimique se trouve dans une zone formée dans un diagramme de Schaeffler, et dans lequel ladite zone est définie par les coordonnées suivantes :
     CreqNieq
    A1 12,923 9,105
    B1 12,923 11,479
    B4 15,702 9,199
    A3 14,482 7,864

     
    12. Acier inoxydable martensitique selon l'une quelconque des revendications 1 à 10, dans lequel ladite composition chimique se trouve dans une zone formée dans un diagramme de Schaeffler, et dans lequel ladite zone est définie par les coordonnées suivantes :
     CreqNieq
    A1 12,300 9,602
    B1 12,300 11,990
    B4 14,482 10,200
    A3 14,482 7,864

     
    13. Acier inoxydable martensitique selon l'une quelconque des revendications 1 à 10, dans lequel ladite composition chimique se trouve dans une zone formée dans un diagramme de Schaeffler, et dans lequel ladite zone est définie par les coordonnées suivantes :
     CreqNieq
    A1 12,923 9,105
    B1 12,923 11,479
    B4 14,482 10,200
    A3 14,482 7,864

     
    14. Utilisation de l'acier inoxydable martensitique selon l'une quelconque des revendications 1 à 13 pour la fabrication d'une tige de forage.
     
    15. Tige de forage comprenant l'acier inoxydable martensitique selon l'une quelconque des revendications 1 à 13.
     




    Drawing












    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description