WO2025080191A1

WO2025080191A1 - An object which is a steel or a bar

Info

Publication number: WO2025080191A1
Application number: PCT/SE2024/050870
Authority: WO
Inventors: Ulf KIVISÄKK; Mats HÄTTESTAND; Charlotte Ulfvin
Original assignee: Alleima Tube AB
Current assignee: Alleima Tube AB
Priority date: 2023-10-11
Filing date: 2024-10-10
Publication date: 2025-04-17
Anticipated expiration: 2026-04-11

Abstract

The present invention relates to an object which is a sheet or a bar of a duplex stainless steel comprising the following elements in weight%: C max 0.030; Si max 0.30; 5 Mn 0.20 to 2.50; P max 0.030; S max 0.030; Cr 28.5 to 30.5; Ni 6.0 to 8.0; 0 Mo 0.70 to 3.00; W 2.00 to 4.40; Cu ≤ 0.50; N 0.30 to 0.55; Balance is Fe and unavoidable impurities; 5 and wherein the ferrite content is of 40-60 vol%; and wherein the duplex stainless steel fulfills the requirements of: a. [Cr] + 4.0*[Mo] + 2.0*[W] < 42.5 wherein the values of [Cr], [Mo] and [W] are in weight%; and b. having less than 10% coverage of quenched-in nitrides in the ferrite grain 0 boundaries when in solution annealed condition.

Description

An object which is a sheet or bar

TECHNICAL FIELD

The present invention relates to an object which is a bar or a sheet of a duplex stainless steel having a high Cr-, W- and N-content.

The present invention also relates to a device for connecting an umbilical to well head, wherein said device is made from said bar. The present invention also relates to a vessel made from at least one said sheet.

BACKGROUND

Duplex stainless steels have been used for many years, they are designed to provide corrosion resistance, particularly chloride stress corrosion and chloride pitting corrosion,

There is a risk that in future applications that the duplex stainless steels of today may not possess enough corrosion resistance and may also create problems during welding due to formation of sigma phase, especially in the heat affected zone. Thus, there is always a need for duplex stainless steels which can withstand higher pressure and additionally withstand corrosion as well as being weldable.

The aim of the present invention is therefore to provide an object which will solve or at least reduce the problems mentioned above. The present invention therefore relates to an object comprising anew duplex stainless steel which will have high strength and high corrosion resistance both in the stainless steel itself and when used in combination with welding.

FIGURES

The present disclosure is further illustrated by the following non-limiting Figures:

FIGURE 1A shows a LOM picture of Heat 7 in a representative site of 0.05 mm²;

FIGURE IB shows the same LOM picture as Figure 1A but also showing the 10 randomly orientated test lines in a representative site of 0.05 mm²; FIGURE 2A shows a LOM picture of Heat 8 in a representative site of 0.05 mm²;

FIGURE 2B shows the same LOM picture as Figure 2A but also showing the 10 randomly orientated test lines in a representative site of 0.05 mm²;

FIGURE 3 A shows a LOM picture of Heat 13 in a representative site of 0.05 mm²;

FIGURE 3B shows the same LOM picture as Figure 3 A but also showing the 10 randomly orientated test lines in a representative site of 0.05 mm²;

FIGURE 4A shows a LOM picture of Heat 14 in a representative site of 0.05 mm²;

FIGURE 4B shows the same LOM picture as Figure 4A but also showing the 10 randomly orientated test lines in a representative site of 0.05 mm² ;

FIGURE 5 A shows a LOM picture of Heat 9 in a representative site of 0.05 mm²;

FIGURE 5B shows the same LOM picture as Figure 5 A but also showing the 10 randomly orientated test lines in a representative site of 0.05 mm²;

FIGURE 6 shows a LOM picture of Heat 26 in a representative site of 0.05 mm².

DETAILED DESCRIPTION

The present disclosure provides an object, which is a sheet or a bar of a duplex stainless steel, which steel will provide the object, i.e. the sheet or the bar, with a combination of high strength and excellent corrosion resistance as the duplex stainless steel will contain a low coverage of quenched-in nitrides in the ferrite grain boundaries in its final form. Further, the present duplex stainless steel and thereby the object will essentially not contain any sigma phase in itself and in a heat affected zone when exposed to welding. The low coverage of quenched-in nitrides in the ferrite grain boundaries will increase the corrosion resistance and the impact resistance. Additionally, the low content of sigma phase will increase the corrosion resistance. Both these properties are important for the endurance of products in operation. By the term “final form” is meant that the duplex stainless steel as defined hereinabove or hereinafter has been exposed to the metallurgy processes necessary for being used in different applications. Hence, the sheet or the bar of said duplex stainless steel as defined hereinafter will contain low amounts of sigma phase or essentially no sigma phase both in the steel as such and in the Heat Affected Zone (HAZ) after welding. Additionally, said duplex stainless steel and thereby the object will have low coverage of quenched-in nitrides in the ferrite grain boundaries after being subjected to solution annealing and quenching.

The present disclosure therefore relates to an object which is a sheet or a bar of a duplex stainless steel having the ranges of elements as disclosed hereinbelow. For said duplex stainless steel, the inventors have carefully adapted both which elements and which ranges of these elements to be used in order to obtain a sheet or a bar having the properties as mentioned hereinabove or hereinafter.

Thus, present disclosure provides a sheet or a bar of a duplex stainless steel comprising the following elements in weight%:

C max 0.030;

Si max 0.30;

Mn 0.20 to 2.50;

P max 0.030;

S max 0.030;

Cr 28.5 to 30.5;

Ni 6.0 to 8.0;

Mo 0.70 to 3.00;

W 2.00 to 4.40;

Cu max 0.50;

N 0.30 to 0.55;

Balance is Fe and unavoidable impurities; and wherein the ferrite content is of 40-60 vol%; and wherein the duplex stainless steel fulfills the requirements of: a. [Cr] + 4.0*[Mo] + 2.0*[W] < 42.5 wherein the values of [Cr], [Mo] and [W] are in weight%; and b) having less than 10% coverage of quenched-in nitrides in the ferrite grain boundaries when in solution annealed condition. Hence, in other words, the duplex stainless steel will have a low coverage of quenched-in nitrides in the ferrite grain boundaries after solution annealing followed by quenching.

The coverage of quenched-in nitrides in the ferrite grain boundaries is measured as described in the method of the Examples, Example 4. Further, said duplex stainless steel will provide the sheet or the bar, due to its composition, with resistance against formation of sigma phase in the Heat Affected Zone (HAZ) and therefore will essentially no sigma phase be present.

In the present disclosure, the term "solution annealed condition" is intended to mean the condition obtained after subjecting the present duplex stainless steel to a heat treatment, for the purpose of solution annealing, followed by cooling from the solution annealing temperature to a temperature of about 900 to about 1000 °C, and thereafter quenching. Further, in the present disclosure, the term “solution annealing” is intended to include both heat treatment and cooling from the solution annealing temperature to a temperature between about 900 to about 1000 °C.

In the present disclosure the term “quenched-in nitrides” refers to the nitrides which are formed at the ferrite grain boundaries when a steel is cooled fast as the elements will have no time to migrate between the phases and therefore will be precipitated in the ferrite grain boundaries.

The coverage of quenched-in nitrides in the ferrite grain boundaries is measured as according to the method as described in the Example.

According to the present invention, another term for “sheet” is “plate”. Thus, when the term “sheet” is mentioned herein it is interchangeable with the term “plate”.

The inventors have found that it is important, in order to obtain the properties of the present sheet or bar, to balance the elements of the duplex stainless steel which have an impact on the sigma phase formation during welding, as the sigma phase has a negative impact on the strength. The inventors have thus found that if the following condition is fulfilled: [Cr] + 4.0*[Mo] + 2.0*[W] < 42.5 (equation 1) wherein the numerical values should be in weight%, the content of sigma phase of the present duplex stainless steel of present object will be low, i.e., it will be less than 0.2 vol% when the present object and thereby the duplex stainless steel is cooled with a cooling rate of 40 °C/min from the solution annealing temperature to room temperature as shown in the Examples, Table 2. This is turn implies that content of sigma phase will be low or essentially zero in the HAZ after welding. Thus, this low content of sigma phase means that the strength and the impact toughness will be high. Furthermore, as the content of sigma phase will be low in the the heat affected zone, the problem with brittleness will be reduced and instead the impact toughness and the strength will be increased. According to the present disclosure, equation 1, may also fulfill the following: 40 < [Cr] +4.0* [Mo] + 2.0*[W] < 42.

The ferrite content of the present duplex stainless steel of the sheet or the bar is between 40-60 vol%, the reminder is essentially composed of austenite. If the ferrite content is too low, the mechanical strength will be too low and if the ferrite content is too high, the corrosion properties will deteriorate. For example, the resistance to hydrogen induced cracking will deteriorate if the ferrite content is too high. According to embodiments, the ferrite content is at least 44 vol%, the reminder being essentially austenite. The phase balance is important as it helps to obtain the optimum mechanical properties and corrosion resistance. Additionally, the ferrite content has been adapted so that phase balance is still within acceptable ranges in the heat affected zone. This is important as the ferrite content in the heat affected zone is often increased, which will have a negative impact on the mechanical properties and the corrosion resistance.

In solution annealing with subsequent quenching, the quenched-in nitrides formed in the ferrite grain boundaries, will as, mentioned above, have a negative impact on both corrosion resistance and mechanical properties. It is therefore important to avoid formation of these quenched-in nitrides. The present inventors have found that a sheet or a bar of the duplex stainless steel as defined hereinabove or hereinafter having the specified element ranges as defined hereinabove or hereinafter will have a low coverage of quenched-in nitrides in the ferrite grain boundaries in a solution annealed condition. Hence, in other words, by a low coverage of quenched-in nitrides in the ferrite grain boundaries is meant that the percentage of ferrite grain boundaries covered with quenched-in nitrides is less than 10%. With typical expected grain sizes, a 10% coverage of ferrite grain boundaries with quenched-in nitrides will correspond to a very low fraction of quenched-in nitrides in the material as a whole. Therefore, less than 10% of ferrite grain boundaries covered with quenched-in nitrides is considered to be a low coverage of quenched-in nitrides. The terms “weight%” and “wt%” are used interchangeably herein.

The terms “HAZ” or “heat affected zone” are used interchangeably and is the non-melted area of metal that has undergone changes in material properties or microstructure as a result of being exposed to the heat generated by welding. The HAZ is thus the area between the weld and the unaffected base metal. In the present duplex steel, the selected ranges of elements together with the condition that balance certain element will significantly reduce sigma phase formation in HAZ.

The advantages of having an object, which is a sheet or a bar, of the present duplex stainless steel and the selection of the ranges of the elements of the duplex stainless steel which render the unexpected superiority of the present object are described in a more detail below. It should be noted that the inventors have adapted the composition both in regard to the selected elements and to the ranges of these in order to obtain an object which is a sheet or a bar having the desired properties as discussed herein. Upper and lower limits of the individual elements of the composition can be freely combined within the broadest limits set out in the claims, unless explicitly disclosed otherwise. Additionally, when ranges are disclosed in the present disclosure, such ranges include the respective end values of the range, unless explicitly disclosed otherwise. Similarly, when an open range is disclosed, the open range also include the single end value of the open range, unless explicitly disclosed otherwise.

Chromium (Cf)

Chromium is an essential element, and the range has been selected in order for the present duplex stainless steel and thereby the sheet or the bar made thereof to have good strength and corrosion resistance. In order to have good strength properties and resistance to corrosion, the content of chromium should be at least 28.5 weight%.

However, even though chromium is a beneficial element, the content should not exceed 30.5 weight% as high contents of Cr will increase the risk of formation of sigma phase both during cooling in manufacturing processes and in HAZ. Additionally, the formation of quenched-in nitrides during solution annealing will be increased.

Further, it has been found that it is important that the contents of chromium, molybdenum, and tungsten, respectively, are balanced in order to avoid formation of sigma phase and to obtain the maximum strength. More specifically, the contents of chromium, molybdenum and tungsten are balanced such that the condition according to Equation 1, discussed above, is fulfilled.

Hence, the chromium content is therefore 28.5 to 30.5 weight%. In order to even further ensure that the above-mentioned properties are obtained, according to the present disclosure, the chromium content may be 29.0 to 30.5 wt%, such as 29.5 to 30.5 wt%. According to the present disclosure, the chromium content may be from 29.1, 29.2, 29.3, 29.4 or 29.5 to 29.6, 29.7, 29.8, 29.9, 30.0, 30.1, 30.2, 30.3, 30.4 or 30.5 wt%.

Nickel (Ni)

Ni is used as an austenite-stabilizing element. In order to obtain a ferrite content of between 40- 60 vol%, the content of nickel should be at least 6.0 weight%. Additionally, if there is a too high Ni content, the austenite content will be increase which will lead to lower strength. However, as nickel is an expensive element, it is desirable to limit its content. According to the present disclosure, the highest content of nickel is 8.0 weight%.

According to the present disclosure, the content of Ni may be less than 7.9, 7.8, 7.7 or 7.6 weight%. According to the present disclosure, the lowest amount of Ni may be 6.0 weight%. According to the present disclosure, the range may be between 6.0 to 7.6 wt%.

Molybdenum (Mo)

Mo is an active element which improves the strength and resistance to corrosion in chloride environments as well as in reducing acids.

However, an excessive Mo content in combination with a high Cr-content will increase the risk of the formation of sigma phase. Molybdenum may sometimes be replaced with tungsten. It is generally accepted in the art that replacement of molybdenum with tungsten may be performed in such a ratio that 1 weight% of Mo would be replaced by 2 weight% of W. However, too low amounts of Mo, will lead to the formation of too high amount of quenched-in nitrides in the ferrite grain boundaries during solution annealing with subsequent quenching. Thus, it is important that the content of chromium, molybdenum and tungsten in the duplex stainless steel is optimized in order to avoid formation of sigma phase and to obtain the maximum strength. Hence, the content of Mo should be in the range of at least 0.70 weight% and the content of Mo should be no more than 3.00 wt%. According to the present disclosure, the content of Mo may be from at least 0.70 to 2.00 wt%., such as from at least 0.70 to 1.70 wt%, such as from at least 0.90 to 1.70 wt%.

Tungsten tW)

W will improve the resistance to corrosion in chloride environments as well the resistance to pitting and crevice corrosion. However, a too high W content in combination with a high Cr content increase the risk of precipitation of sigma phase. Hence, it is very important that the combined amount of chromium, molybdenum and tungsten is balanced to avoid formation of sigma phase. More specifically, the contents of chromium, molybdenum and tungsten are balanced such that the condition according to Equation 1, discussed above, is fulfilled.

The W-content is therefore 2.00 to 4.40 wt%. According to the present disclosure, the content of W may be 2.50 to 4.40 wt%, such as 3.00 to 4.00 wt%.

Nitrogen (N)

N is a very active element which increases the resistance to corrosion as well as the strength of the duplex stainless steel. In order to obtain a good effect at least 0.30 weight % N should be added.

However, as added N must be solved in the duplex stainless steel in order to provide the increase in strength and corrosion resistance, the range of N must be carefully selected as too high content of N will increase the risk of precipitation of chromium nitrides, especially when the content of chromium is also high. The N-content should therefore be limited to maximum 0.55 weight%. Hence, the content of nitrogen is 0.30 to 0.55 weight%.

According to the present disclosure, the content of N may be from 0.35 to 0.55 wt%; such as 0.38 to 0.55 wt%, such as 0.38 to 0.50 wt%.

Manganese (Mn)

Mn is added in order to increase the solubility of N in the steel. However, Mn may also form manganese sulphides, which act as initiation points for pitting corrosion. The content of Mn is therefore greater than or equal to 0.20 weight% but equal to or less than 2.50 weight %. According to the present disclosure, the content of Mn may be 0.30 to 2.00 weight%.

Silicon (Si)

Si is frequently utilized as a deoxidizer during steel production. However, it is known that high silicon content stabilizes the sigma phase. The content of silicon should therefore be limited to max 0.30 weight%. According to the present disclosure, the content of silicon may be 0.10 to 0.30 weight%.

Carbon (C)

Carbon is an element which is very difficult to completely avoid in a duplex stainless steel. Striving towards very low carbon contents would unduly increase the manufacturing costs. Therefore, carbon may be present in an amount of at least 0.005 weight% at least for cost reasons.

C strengthens duplex stainless steel but also promotes the formation of chromium carbides which are harmful to corrosion. Carbon has also a limited solubility in both ferrite and austenite. The carbon content should therefore be limited to max 0.030 weight%, such as max 0.025 weight%.

Copper (Cu)

Cu may be added in order to improve resistance to certain corrosive environments such as acid environments and it also decreases susceptibility to stress corrosion cracking. Furthermore, Cu will increase the strength and also reduce the formation of sigma phase.

However, Cu will have a negative effect on nitrogen solubility as less nitrogen is solved in the stainless steel and formation of chromium nitrides will therefore be increased. Hence, if copper is added, it is very important to carefully adjust its content. The content of Cu is therefore limited max 0.50 wt%, such as less than 0.50 wt%. According to an embodiment, Cu is added, and the content of Cu is between 0.15 to < 0.50 wt%, According embodiments, the Cu content may be 0.25 to 0.45 wt%. Sulfur (S)

Sulfur is an impurity element normally contained in duplex stainless steel. The sulfur content should not be more than 0.030 wt% as it will have an impact on the hot workability above said range.

Phosphorus (P)

Phosphorus is also an impurity element normally contained in duplex stainless steel.

The phosphorus content should not be more than 0.030 wt% as it will have an impact on the hot workability above said range.

The balance of the duplex stainless steel is iron (Fe) and unavoidable impurities. The unavoidable impurities are elements which are not added on purpose but may be in the present steel due to the scrap and/or manufacturing process used for providing the duplex stainless steel. Examples but not limited to such elements are Co, V, Ti, Nb, Pb, Sn and Ce. The combined content of these elements is less than 1.0 wt%

Further, the duplex stainless steel of the present disclosure may optionally comprise one or more, elements which may have been added in order to improve the manufacturing process. Examples but not limiting to such manufacturing process improving elements are Aluminium (Al), Magnesium (Mg), Calcium (Ca) and Boron (B). The combined content of these improving elements is less than 0.50 weight%, such as less than 0.30 weight% with the condition that content of Al cannot be more the 0.050 weight% and with the condition that the content of B cannot be more than 0.050 weight%.

According to embodiments, the duplex stainless steel of present object which is a sheet or a bar may comprise or consist of the elements mentioned herein in any of the ranges of the specific elements mentioned herein and fulfilling the requirements mentioned herein. According to embodiment, the sheet or the bar is in solution annealed condition.

Further, according to embodiments, the present disclosure also relates to a device, which is connected to the top of the well, namely a penetrator comprising or consisting of the bar as defined hereinabove or hereinafter. According to embodiments, the penetrator is made of the bar as defined hereinabove or hereinafter. A penetrator may be used for connecting an umbilical to the subsea equipment. This connection is performed by welding. According to embodiment, the bar is in solution annealed condition. However, other devices manufactured from the present bar are also possible, such as but not limited to flanges.

According to embodiments, the present disclosure also relates to a vessel which is made of at least one sheet as defined hereinabove or hereinafter.

Thus, the present disclosure relates to an object, which is a sheet or a bar of a duplex stainless steel, wherein said duplex stainless steel comprises the following elements in weight%:

C max 0.030;

Si max 0.30;

Mn 0.20 to 2.50;

P max 0.030;

S max 0.030;

Cr 28.5 to 30.5;

Ni 6.0 to 8.0;

Mo 0.70 to 3.00;

W 2.00 to 4.40;

Cu max 0.50;

N 0.30 to 0.55;

Balance is Fe and unavoidable impurities; and wherein the ferrite content is of 40-60 vol%; and wherein the duplex stainless steel fulfills the requirements of: a) [Cr] + 4.0*[Mo] + 2.0*[W] < 42.5 wherein the values of [Cr], [Mo] and [W] are in weight%; and b) having less than 10% coverage of quenched-in nitrides in the ferrite grain boundaries when in solution annealed condition.

Hence, the present disclosure also relates to a bar or a sheet comprising or consisting of a duplex stainless steel comprising the following elements in wt%: max 0.030

Si max 0.30

Mn 0.30 to 2.50 P max 0.030

S max 0.030

Cr 28.5 to 30.5

Ni 6.0 to 8.0

Mo 0.70 to 3.00

W 2.00 to 4.40

Cu max 0.50

N 0.30 to 0.55

Fe and unavoidable impurities Balance and fulfilling the condition of a) [Cr] + 4.0* [Mo] + 2.0*[W] < 42 wherein the values of [Cr], [Mo] and [W] are in weight%; and wherein the ferrite content is of 40-60 vol%; and b) wherein the ferrite grain boundaries in solution annealed condition have less than 10% coverage of quenched-in nitrides.

According to embodiments, the present object may have Rp0.2 higher than 650 MPa, ISO 6892-1, 2019, measured in room temperature. A Rp0.2 higher than 650 MPa, ISO 6892-1,2019, in room temperature, means that for example a sheet may be used in applications where the sheet is in the form of for example a vessel which is exposed to the high internal pressures.

According to embodiments, the present object may have a diameter of 016 to 0200 mm, such as for example 030 to 090 mm. According to embodiments, the bar may have a diameter of 016 to 0200 mm, such as for example 030 to 090 mm.

According to embodiments, the present disclosure also relates to an object, which is a sheet or bar, comprising or consisting of duplex stainless steel comprising the following elements in wt%:

C max 0.030

Si max 0.30

Mn 0.30 to 2.50

P max 0.030

S max 0.030 Cr 28.5 to 30.5

Ni 6.0 to 8.0

Mo 0.70 to 3.00

W 2.00 to 4.40

Cu max 0.50

N 0.30 to 0.55

Fe and unavoidable impurities Balance and fulfilling the condition of a) [Cr] + 4.0* [Mo] + 2.0*[W] < 42 wherein the values of [Cr], [Mo] and [W] are in weight%; and wherein the ferrite content is of 40-60 vol%; and b) wherein the ferrite grain boundaries in solution annealed condition have less than 10% coverage of quenched-in nitrides; and c) wherein Rp0.2 higher than 650 MPa, ISO 6892-1, 2019, in room temperature.

The present disclosure also relates to a process for manufacturing an object, which is a sheet or a bar, of the duplex stainless steel defined hereinabove or hereinafter, wherein said process comprises the steps of:

Melting the raw material;

The melting may be performed by a high frequency induction furnace or an arc furnace.

Casting;

Hot working;

The hot working may be performed by forging and/or rolling.

Optionally cold working;

The cold working may be performed by rolling.

Solution annealing;

The solution annealing is performed at a temperature range of to about 1000 to about 1200°C, such as about 1050 to about 1150°C;

Cooling;

Cooling may be performed in room temperature and the cooling may be performed in air. The cooling is performed from the solution annealing temperature to a temperature of about 900 to about 1000 °C. Quenching;

The quenching may be performed in water. The quenching should be performed so that the formation of sigma phase is avoided.

Optionally other steps may be performed such as straightening, machining and the like.

The term “about” is intended to mean 10% deviation from the numerical value.

The present disclosure is further described by the following non-limiting examples.

Examples

Example 1 - Manufacturing of samples

Heats having a chemical composition according to Table 1 were melted in a high frequency induction furnace as 50 kg heats or 270 kg heats and then cast to ingots using a mold.

After casting, the molds were removed, and the ingots were heat treated by solution annealing and following quenching. A sample for chemical analysis was taken from each ingot. The chemical analyses were performed by using X-Ray Fluorescence Spectrometry and Spark Atomic Emission Spectrometry and combustion technique as different elements require different methods for measuring the content.

The obtained ingots were forged or hot rolled to billets. The obtained billets were if needed machined to smaller billets.

After hot working (rolling or forging), the billets were cold rolled to 7 to 10 mm samples and then solution annealed in a temperature of 1050 to 1150°C and then cooled in room temperature to a temperature between 950 to 1000 °C and subsequent water quenched.

Example 2 - Sigma phase measurements

The result of sigma phase measurements is shown in Table 2

Samples were taken after solution annealing and quenching. After that and in order to simulate the environment of a heat affected zone, the samples were heated to about 1100°C. The cooling of the samples was controlled, and the cooling rate was 40 °C/min from about 1100 °C to room temperature. The fraction of sigma phase formed during cooling was measured using SEM and image analysis evaluation of ten image fields covering a total area of 0.4 mm|2 of the sample. As this test simulates the reality for welding operations, a product can be welded with low formation of sigma phase in the HAZ if containing no or low sigma phase. As stated before, if no or low sigma phase can be found, there will be the corrosion resistance as well as the impact toughness will be excellent.

Example 3 - RpO.2 measurements

Rp0.2 was measured according to ISO 6892-1,2019, in room temperature. The results are as can be seen from Table 2., All the inventive stainless steels heats have a RpO.2 higher than 650 MPa, such as higher than 660 MPa.

Table 2 - The table shows the sigma phase content of each alloy and the Rp0.2. The heats marked with are inventive heats.

Example 4 - Measurement of the coverage of quenched-in nitride in the ferrite grain boundaries

The coverage of quenched-in nitrides in the ferrite grain boundaries was measured in solution annealed condition. Samples were taken from Example 1. Standard Light Optical Microscopy (LOM) micrographs taken at 500x magnification and an intercept method using 10 randomly orientated test lines in a representative site of 0.05 mm² were used to measure the percentage of ferrite grain boundaries covered with quenched-in nitrides. Specimens for LOM were prepared by surface polishing followed by electrolytical etching in HNO3 and NaOH. The percentage of ferrite grain boundaries covered with quenched-in nitrides was calculated by dividing the number of intercepts between test lines and ferrite grain boundaries covered with quenched-in nitrides with the total number of intercepts between test lines and ferrite grain boundaries. Examples of this is shown in FIGURES 1A to 5B and the result from these calculations is shown in Table 3. Table 3: Heats having less than 10% coverage of quenched-in nitrides in ferrite grain boundaries as measured as described in Example 4. The heats marked with are inventive heats.

Example 5 - Ferrite measurements

The ferrite amount was measured using LOM and manual point counting according to ASTM E562. The reminder is essentially austenite. The ferrite was measured on cold rolled and solution annealed and quenched samples.

Table 4: The result of the samples ferrite amount - the reminder is essentially austenite, The heats marked with are inventive heats.

Table 1 Composition of the heats. The numbers are given in weight% The heats marked with ” *” are inventive heats. The other heats are comparative heats. Balance for each heat is Fe and unavoidable impurities. Note that some of impurities are also mentioned in the table.

Claims

1. An object, which is a sheet or a bar, of a duplex stainless steel, wherein said duplex stainless steel comprises the following elements in weight%:

C max 0.030;

Si max 0.30;

Mn 0.20 to 2.50;

P max 0.030;

S max 0.030;

Cr 28.5 to 30.5;

Ni 6.0 to 8.0;

Mo 0.70 to 3.00;

W 2.00 to 4.40;

Cu < 0.50;

N 0.30 to 0.55;

2. The object according to claim 1, wherein the content of Cr is from 29.0 to 30.5 wt%.

3. The object according to any one of claims 1 to 2, wherein the content of Ni is from 6.0 to 7.6 wt%.

4. The object according to any one of claims 1 to 3, wherein the content of Mo is from at least 0.70 to 2.00 wt%.

5. An object according to any one of claims 1 to 4, wherein the content of W is from 2.50 to 4.40 wt% or 3.00 to 4.00 wt%.

6. The object according to any one of claims 1 to 5, wherein the content of Mn is from 0.30 to 2.00 weight%.

7. The object according to any one of claims 1 to 6, wherein the content of Si is 0.10 to 0.30 weight%.

8. The object according to any one of claims 1 to 7, wherein the content of Cu is 0.15 to 0.50 weight%.

9. The object according to any one of claims 1 to 8, wherein the content of N is from 0.35 to 0.55 weight% or 0.38 to 0.55 weight% or 0.38 to 0.50 weight%.

10. The object according to any one of claims 1 to 9, wherein said object has a Rp0.2 higher than 650 MPa, ISO 6892-1, 2019.

11. The object according to any of claims 1 to 10, wherein said object is in solution annealed condition.

12. The object according to any one of claims 1 to 11, wherein said object will contain less than 0.2 vol% sigma phase after cooling 40 °C/min from 1 100°C to room temperature when in solution annealed condition.

13. The object according to any one of claims 1 to 12, wherein said object is a device, such as a penetrator, or a vessel.

14. A process for manufacturing an object, which is a sheet or a bar, according to any one of claims 1 to 13 comprising the steps of where

Melting;

Casting;

Hot working;

Optionally cold working;

Solution annealing which is performed at a temperature range of to about 1000 to about 1200°C, such as about 1050 to about 1150°C;

Cooling from the solution annealing temperature to a temperature of about 900 to about 1000 °C Quenching.