HIGH-STRENGTH STAINLESS STEEL MATERIAL
By alloying 13Cr martensitic stainless steel with Ni, Mo, W, Ti, and V, and applying heat treatments, the material's toughness and resistance to hydrogen sulfide cracking are enhanced, addressing the limitations of existing alloys in wellbore operations.
Patent Information
- Application Number
- FR2022007531
- Authority / Receiving Office
- FR · FR
- Patent Type
- Patents
- Current Assignee / Owner
- Priority Date
- 2022-04-22
- Filing Date
- 2022-07-22
- Publication Date
- 2025-12-26
- Estimated Expiration
- 2042-07-22
AI Technical Summary
Martensitic stainless steel alloys used in wellbore operations are susceptible to sulfide stress cracking in the presence of hydrogen sulfide and lack adequate toughness and corrosion resistance, particularly at higher yield strengths required for downhole operations.
Alloying 13Cr martensitic stainless steel with small amounts of Ni, Mo, W, Ti, and V, and austenitizing the material to maintain its martensitic microstructure, combined with heat treatments like quenching and tempering, to enhance toughness and resistance to hydrogen sulfide.
The modified 13Cr material achieves higher yield strengths of 95/105/110/125 ksi with improved toughness and stress crack resistance, offering a more economical alternative to nickel alloys for downhole use.
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Abstract
Description
Title of the invention: HIGH-STRENGTH STAINLESS STEEL MATERIAL technical field
[0001] This disclosure generally relates to wellbore completion operations and, more specifically (though not necessarily exclusively), the use of high-strength stainless steel material in wellbore completion operations. Context
[0002] Hydrocarbons, such as oil and gas, can be extracted from subsurface formations that may be located onshore or offshore. Hydrocarbons can be extracted through a well drilled into the subsurface formation. Well drilling operations to extract hydrocarbons may include drilling operations, completion operations, and production operations. Some or all of these well drilling operations may involve well drilling tools that may be exposed to corrosive or otherwise harmful fluids in the wellbore, such as hydrogen sulfide. In many cases, these well drilling tools are made of stainless steel alloys, such as austenitic stainless steel alloys and martensitic stainless steel alloys.Martensitic stainless steel alloys generally do not contain nickel and exhibit relatively high strength but low ductility and corrosion resistance. Austenitic stainless steel alloys generally contain relatively high amounts of nickel and exhibit relatively low strength but high ductility and corrosion resistance. Stainless steel alloys, particularly martensitic stainless steel alloys, can be susceptible to sulfide stress cracking in the presence of hydrogen sulfide. Brief description of the drawings
[0003] Fig. 1 is a diagram of a well system comprising a well tool according to an example in this disclosure.
[0004] Figure 2 is a flowchart of a method for improving the toughness of a 13Cr material as per an example in this disclosure.
[0005] Figure 3 is a diagram of the microstructure of a 13Cr material according to a example of disclosure. Detailed description
[0006] Certain aspects and examples in this disclosure relate to improving the toughness of a 13Cr-type martensitic stainless steel material, referred to herein as 13Cr material, to higher yield strengths for use in a wellbore operation without altering the core microstructure of the 13Cr material. The 13Cr material can be used in materials and tools in a downhole environment, for example, in tools used during the wellbore completion stage. The toughness of the 13Cr material can be improved by alloying the stainless steel material with relatively small amounts of Ni, Mo, W, Ti, Nb, and V, and by austenitizing the 13Cr material while substantially preserving its martensitic microstructure.
[0007] Stainless steels with minimum yield strength (MY) levels of 95 / 105 / 110 / 125 ksi that have both adequate toughness and significant resistance to hydrogen sulfide (H2S) for use in a downhole oil and gas production environment are desirable. Such a material can provide a more economical solution than alternative grades, such as nickel alloys, in the presence of H2S to ensure safe operation and prevent environmental cracking. For example, H2S can cause wellbore tools made of such materials to undergo stress sulfide cracking (SSC). Currently, 13Cr materials are known to have favorable resistance to MY forces of 80 ksi.Heat treatment of this grade at higher strengths such as MY of 95 / 105 / 110 / 125 ksi can lead to a reduction in toughness, which is not currently considered acceptable for service requiring resistance to environmental cracking in the presence of H2S. By modifying the material chemistry of 13Cr, without changing the core microstructure, a stainless steel material with adequate toughness and stress crack resistance for downhole use can be created.
[0008] As a general rule, 13Cr materials may have very little retained austenite due to their very low Ni content. This contrasts with other grades of stainless steel, where the intentional addition of Ni, such as more than 1 wt%, can lead to a metastable austenite-martensite stainless steel material or a Super 13Cr martensitic stainless steel material. These stainless steel grades may have microstructures exhibiting both retained or inverted martensite and austenite, about 5 wt% Ni, and, in some cases, N. Notably, Super 13Cr martensitic stainless steel materials may not have superior toughness compared to 13Cr materials.
[0009] To improve the toughness of the 13Cr material, Mo, W, Ti, Nb, and V can be added. Furthermore, treatments including single or double austenitizing, single or double quenching, and single or double heat tempering can further refine the microstructure of the 13Cr material to make it predominantly martensitic. The improved 13Cr materials can then exhibit increased toughness at higher MY strength levels of 95 / 105 / 110 / 125 ksi. The refined microstructure would also provide better SSC strength compared to Super 13Cr martensitic stainless steel materials for use in down-the-hole operations.
[0010] Illustrative examples are given to introduce the reader to the general subject matter discussed here and are not intended to limit the scope of the disclosed concepts. The following sections describe various additional features and examples with reference to the drawings in which similar numbers indicate similar elements, and directional descriptions are used to describe the illustrative aspects, but, like the illustrative aspects, are not to be used to limit this disclosure.
[0011] Figure 1 is a schematic of a well system 100 comprising a well tool according to an example in this disclosure. As shown in Figure 1, the well tool may be a completion column 102. During the completion stage of a wellbore, a completion column 102 may be positioned inside a wellbore 104. The wellbore 104 may be formed beneath a surface 106 in an underground formation. The completion column 102 may include a 13Cr material formed according to aspects of this disclosure to improve toughness and resistance to environmental cracking at higher strengths. Additional tools may be used during the completion stage, and one or more of these additional tools may include the 13Cr material formed according to aspects of this disclosure.
[0012] Fig. 2 is a flowchart of a process for improving the toughness of a 13Cr material according to an example in this disclosure. In block 302, a 13Cr material containing at least 11% by weight of Cr and between 0.01% by weight and 0.5% by weight (for example, from about 0.05% by weight to about 0.5% by weight, from about 0.10% by weight to about 0.5% by weight, from about 0.15% by weight to about 0.5% by weight, from about 0.20% by weight to about 0.5% by weight, from about 0.25% by weight to about 0.5% by weight, from about 0.30% by weight to about 0.5% by weight, from about 0.35% by weight to about 0.5% by weight, from about 0.40% by weight to about 0.5% by weight, from about 0.45% by weight to about 0.5% by weight, from about 0.01 ... weight at approximately 0.4% by weight, from approximately 0.05% by weight to approximately 0.4% by weight, from approximately 0.10% by weight to approximately 0.4% by weight, from approximately 0.15% by weight weight to approximately 0.4% by weight, from approximately 0.20% by weight to approximately 0.4% by weight, from approximately 0.25% by weight to approximately 0.4% by weight, from approximately 0.30% by weight to approximately 0.4% by weight, from approximately 0.35% by weight to approximately 0.4% by weight, from approximately 0.01% by weight to approximately 0.3% by weight, from approximately 0.05% by weight to approximately 0.3% by weight, from approximately 0.10% by weight to approximately 0.3% by weight, from approximately 0.15% by weight to approximately 0.3% by weight, from approximately 0.20% by weight to approximately 0.3% by weight, from approximately 0.25% by weight to approximately 0.3% by weight, from approximately 0.01% by weight to approximately 0.2% by weight, from approximately 0.05% by weight to approximately 0.2% by weight weight, from about 0.10% by weight to about 0.2% by weight, from about 0.15% by weight to about 0.2% by weight, from about 0.01% by weight to about 0.1% by weight or from about 0.05% by weight to about 0.1% by weight) of Ni is melted.For example, the material may contain 0.01% by weight, 0.02% by weight, 0.03% by weight, 0.04% by weight, 0.05% by weight, 0.06% by weight, 0.07% by weight, 0.08% by weight, 0.09% by weight, 0.1% by weight, 0.11% by weight, 0.12% by weight, 0.13% by weight, 0.14% by weight, 0.15% by weight, 0.16% by weight, 0.17% by weight, 0.18% by weight, 0.19% by weight, 0.20% by weight, 0.21% by weight, 0.22% by weight, 0.23% by weight, 0.24% by weight, 0.25% by weight, 0.26% by weight, 0.27% in weight, . 0.28% by weight, 0.29% by weight, 0.30% by weight, 0.31% by weight, 0.32% by weight, 0.33% by weight, 0.34% by weight, 0.35% by weight, 0.36% by weight, 0.37% by weight, 0.38% by weight, 0.39% by weight, 0.40% by weight, 0.41% by weight, 0.42% by weight, 0.43% by weight, 0.44% by weight, 0.45% by weight, 0.46% by weight, 0.47% by weight, 0.48% by weight, 0.49% by weight or 0.50% by weight of Ni. The relatively low presence of Ni can increase the toughness of the 13Cr material without a significant impact on the martensitic microstructure of the 13Cr material.
[0013] At block 204, Mo, W, Ti, Nb and V are added to the 13Cr material. Each of Mo, W, Ti, Nb and V can be added in an amount greater than 0% by weight. In some examples, no more than 0.25% by weight (for example, from about 0.01% by weight to about 0.25% by weight, from about 0.05% by weight to about 0.25% by weight, from about 0.10% by weight to about 0.25% by weight, from about 0.15% by weight to about 0.25% by weight, from about 0.20% by weight to about 0.25% by weight, from about 0.01% by weight to about 0.20% by weight, from about 0.05% by weight to about 0.20% by weight, from about 0.10% by weight to about 0.20% by weight, from about 0.15% by weight to about 0.20% by weight, from about 0.05% by weight to about 0.10% by weight to about 0.20% by weight, from about 0.05 ...20% by weight to about 0.20% by weight, from about 0.20% by weight to about 0.20% by weight, from about 0.20% by weight to about 0.20% by weight, from about 0.20% by weight to about 0.20% by weight, from about 0.20% by weight to about 0.20% by weight % by weight to 0.15% by weight, from about 0.10% by weight to 0.15% by weight, from about 0.01% by weight to about 0.10% by weight or from about 0.05% by weight to about 0.10% by weight) of Mo can be added.For example, the 13Cr material may contain 0.01% by weight, 0.02% by weight, 0.03% by weight, 0.04% by weight, 0.05% by weight, 0.06% by weight, 0.07% by weight, 0.08% by weight, 0.09% by weight, 0.1% by weight, 0.11% by weight, 0.12% by weight, 0.13% by weight, 0.14% by weight. % by weight, 0.15% by weight, 0.16% by weight, 0.17% by weight, 0.18% by weight, 0.19% by weight, 0.20% by weight, 0.21% by weight, 0.22% by weight, 0.23% by weight, 0.24% by weight or 0.25% by weight of Mo.
[0014] In some examples, not more than 0.1% by weight of W (for example, from about 0.01% by weight to about 0.1% by weight, from about 0.02% by weight to about 0.1% by weight, from about 0.03% by weight to about 0.1% by weight, from about 0.04% by weight to about 0.1% by weight, from about 0.05% by weight to about 0.1% by weight, from about 0.06% by weight to about 0.1% by weight, from about 0.07% by weight to about 0.1% by weight, from about 0.08% by weight to about 0.1% by weight, from about 0.09% by weight to about 0.1% by weight, from about 0.01% by weight to about 0.09% by weight, from about 0.02% by weight to approximately 0.09% by weight, from approximately 0.03% by weight to approximately 0.09% by weight, from approximately 0.04% by weight to approximately 0.09% by weight, from approximately 0.05% by weight to approximately 0.09% by weight, from approximately 0.06% by weight to approximately 0.09% by weight, from approximately 0.07% by weight to approximately 0.09% by weight, from approximately 0.08% by weight to approximately 0.09% by weight, from approximately 0,0.1% by weight to approximately 0.08% by weight, from approximately 0.02% by weight to approximately 0.08% by weight, from approximately 0.03% by weight to approximately 0.08% by weight, from approximately 0.04% by weight to approximately 0.08% by weight, from approximately 0.05% by weight to approximately 0.08% by weight, from approximately 0.06% by weight to approximately 0.08% by weight, from approximately 0.07% by weight to approximately 0.08% by weight, from approximately 0.01% by weight to approximately 0.07% by weight, from approximately 0.02% by weight to approximately 0.07% by weight, from approximately 0.03% by weight to approximately 0.07% by weight, from approximately 0.04% by weight to approximately 0.07% by weight, from approximately 0.05% (approximately 0.07% by weight or approximately 0.06% by weight to approximately 0.07% by weight) can be added. For example, the 13Cr material may contain 0.01% by weight, 0.02% by weight, 0.03% by weight, 0.04% by weight, 0.05% by weight, 0.06% by weight, 0.07% by weight, 0.08% by weight, 0.09% by weight, or 0.1% by weight of W.
[0015] In some examples, not more than 0.1% by weight of Ti (for example, from about 0.01% by weight to about 0.1% by weight, from about 0.02% by weight to about 0.1% by weight, from about 0.03% by weight to about 0.1% by weight, from about 0.04% by weight to about 0.1% by weight, from about 0.05% by weight to about 0.1% by weight, from about 0.06% by weight to about 0.1% by weight, from about 0.07% by weight to about 0.1% by weight, from about 0.08% by weight to about 0.1% by weight, from about 0.09% by weight to about 0.1% by weight, from about 0.01% by weight to about 0.09% by weight, from about 0.02% by weight to approximately 0.09% by weight, from approximately 0.03% by weight to approximately 0.09% by weight, from approximately 0.04% by weight to approximately 0.09% by weight, from approximately 0.05% by weight to approximately 0.09% by weight, from approximately 0.06% by weight to approximately 0.09% by weight, from approximately 0.07% by weight to approximately 0.09 % by weight, from approximately 0.08% by weight to approximately 0.09% by weight, from approximately 0.01% by weight to approximately 0.08% by weight, from approximately 0.02% by weight to approximately 0.08% by weight, from approximately 0.03% by weight to approximately 0.08% by weight, from approximately 0.04% by weight to approximately 0.08% by weight, from approximately 0.05% by weight to approximately 0.08% by weight, from approximately 0.06% by weight to approximately 0.08% by weight, from approximately 0.07% by weight to approximately 0.08% by weight, from approximately 0.01% by weight to approximately 0.07% by weight, from approximately 0.02% by weight to approximately 0.07% by weight, from approximately 0.03% by weight to approximately 0.07% by weight, (approximately 0.04% by weight to approximately 0.07% by weight, approximately 0.05% by weight to approximately 0.07% by weight, or approximately 0.06% by weight to approximately 0.07% by weight) may be added. For example, the 13Cr material may contain 0.01% by weight, 0.02% by weight, 0.03% by weight, 0.04% by weight, 0.05% by weight, 0.06% by weight, 0.07% by weight, 0.08% by weight, 0.09% by weight, or 0.1% by weight of Ti.
[0016] In some examples, not more than 0.1% by weight of Nb (for example, from about 0.01% by weight to about 0.1% by weight, from about 0.02% by weight to about 0.1% by weight, from about 0.03% by weight to about 0.1% by weight, from about 0.04% by weight to about 0.1% by weight, from about 0.05% by weight to about 0.1% by weight, from about 0.06% by weight to about 0.1% by weight, from about 0.07% by weight to about 0.1% by weight, from about 0.08% by weight to about 0.1% by weight, from about 0.09% by weight to about 0.1% by weight, from about 0.01% by weight to about 0.09% by weight, from about 0.02 % by weight to approximately 0.09% by weight, from approximately 0.03% by weight to approximately 0.09% by weight, from approximately 0.04% by weight to approximately 0.09% by weight, from approximately 0.05% by weight to approximately 0.09% by weight, from approximately 0.06% by weight to approximately 0.09% by weight, from approximately 0.07% by weight to approximately 0.09% by weight, from approximately 0.08% by weight to approximately 0.09% by weight, from approximately 0.0.1% by weight to approximately 0.08% by weight, from approximately 0.02% by weight to approximately 0.08% by weight, from approximately 0.03% by weight to approximately 0.08% by weight, from approximately 0.04% by weight to approximately 0.08% by weight, from approximately 0.05% by weight to approximately 0.08% by weight, from approximately 0.06% by weight to approximately 0.08% by weight, from approximately 0.07% by weight to approximately 0.08% by weight, from approximately 0.01% by weight to approximately 0.07% by weight, from approximately 0.02% by weight to approximately 0.07% by weight, from approximately 0.03% by weight to approximately 0.07% by weight, from approximately 0.04% by weight to approximately 0.07% by weight, from approximately 0.05% (approximately 0.07% by weight or approximately 0.06% by weight to approximately 0.07% by weight) can be added. For example, the 13Cr material may contain 0.01% by weight, 0.02% by weight, 0.03% by weight, 0.04% by weight, 0.05% by weight, 0.06% by weight, 0.07% by weight, 0.08% by weight, 0.09% by weight or 0.1% by weight of Nb.
[0017] In some examples, not more than 0.1% by weight of V (for example, from about 0.01% by weight to about 0.1% by weight, from about 0.02% by weight to about 0.1% by weight, from about 0.03% by weight to about 0.1% by weight, from about 0.04% by weight to about 0.1% by weight, from about 0.05% by weight to about 0.1% by weight, from about 0.06% by weight to about 0.1% by weight, from about 0.07% by weight to about 0.1% by weight, from about 0.08% by weight to about 0.1% by weight, from about 0.09% by weight to about 0.1% by weight, from about 0.01% by weight to about 0.09% by weight, from about 0.02% by weight to approximately 0.09% by weight, from approximately 0.03% by weight to approximately 0.09% by weight, from approximately 0.04% by weight to approximately 0.09% by weight, from approximately 0.05% by weight to approximately 0.09% by weight, from approximately 0.06% by weight to approximately 0.09% by weight, from approximately 0.07% by weight to approximately 0.09% by weight, from approximately 0.08% by weight to approximately 0.09% by weight, from approximately 0,0.1% by weight to approximately 0.08% by weight, from approximately 0.02% by weight to approximately 0.08% by weight, from approximately 0.03% by weight to approximately 0.08% by weight, from approximately 0.04% by weight to approximately 0.08% by weight, from approximately 0.05% by weight to approximately 0.08% by weight, from approximately 0.06% by weight to approximately 0.08% by weight, from approximately 0.07% by weight to approximately 0.08% by weight, from approximately 0.01% by weight to approximately 0.07% by weight, from approximately 0.02% by weight to approximately 0.07% by weight, from approximately 0.03% by weight to approximately 0.07% by weight, from approximately 0.04% by weight to approximately 0.07% by weight, from approximately 0.05% (approximately 0.07% by weight or approximately 0.06% by weight to approximately 0.07% by weight) can be added. For example, the 13Cr material may contain 0.01% by weight, 0.02% by weight, 0.03% by weight, 0.04% by weight, 0.05% by weight, 0.06% by weight, 0.07% by weight, 0.08% by weight, 0.09% by weight or 0.1% by weight of V.
[0018] Optionally, additional elements may be added to the 13Cr material. In one particular embodiment, no more than 0.020 wt% of S, no more than 0.020 wt% of P, no more than 0.25 wt% of Cu, between 0.01 wt% and 1.0 wt% of Mn, between 0.01 wt% and 1.0 wt% of Si, and no more than 0.25 wt% of C may be added to a 13Cr material that comprises Mo, W, Ti, Nb, V, at least 11 wt% of Cr, and between 0.01 wt% and 0.5 wt% of Ni. In some examples, such an embodiment may not involve an intentional addition of N.
[0019] Exemplary areas of S present in such an embodiment may comprise from about 0.001% by weight to about 0.020% by weight, from about 0.005% by weight to about 0.020% by weight, from about 0.010% by weight to about 0.020% by weight, from about 0.015% by weight to about 0.020% by weight, from about 0.001% by weight to about 0.015% by weight, from about 0.005% by weight to about 0.015% by weight, from about 0.01 % by weight to about 0.010% by weight, from about 0.005% by weight to about 0.010% by weight, or from about 0.001% by weight to about 0.005% by weight. Examples of percentages of S present in such an embodiment may include 0.001% by weight, 0.002% by weight, 0.003% by weight, 0.004% by weight, 0.005% by weight, 0.006% by weight, 0.007% by weight, 0.008% by weight, 0.009% by weight, 0.01% by weight, 0.011% by weight, 0.012% by weight, 0.013% by weight, 0.014% by weight, 0.015% by weight, 0.016% by weight, 0.017% by weight, 0.018% by weight, 0.019% by weight or 0.020% by weight.
[0020] Exemplary ranges of P present in such an embodiment may comprise from about 0.001% by weight to about 0.020% by weight, from about 0.005% by weight to about 0.020% by weight, from about 0.010% by weight to about 0.020% by weight, from about 0.015% by weight to about 0.020% by weight, from about 0.001% by weight to about 0.015% by weight, from about 0.005% by weight to about 0.015% by weight, from about 0.010% by weight to about 0.015% by weight, from about 0.001% by weight to about 0.010% by weight, from about 0.005% by weight to about 0.010% by weight, or about 0.001% by weight at approximately 0.005% by weight.Examples of percentages of P present in such an embodiment may include 0.001% by weight, 0.002% by weight, 0.003% by weight, 0.004% by weight, 0.005% by weight, 0.006% by weight, 0.007% by weight, 0.008% by weight, 0.009% by weight, 0.01% by weight, 0.011% by weight, 0.012% by weight, 0.013% by weight, 0.014% by weight, 0.015% by weight, 0.016% by weight, 0.017% by weight, 0.018% by weight, 0.019% by weight or 0.020% by weight.
[0021] Exemplary Cu ranges present in such an embodiment may comprise from approximately 0.01% by weight to approximately 0.25% by weight, from approximately 0.05% by weight to approximately 0.25% by weight, from approximately 0.10% by weight to approximately 0.25% by weight, from approximately 0.15% by weight to approximately 0.25% by weight, from approximately 0.20% by weight to approximately 0.25% by weight, from approximately 0.01% by weight to approximately 0.20% by weight, from approximately 0.05% by weight to approximately 0.20% by weight, from approximately 0.10% by weight to approximately 0.20% by weight, from approximately 0.15% by weight to approximately 0.20% by weight, from approximately 0.01% by weight to 0.15% by weight, from approximately 0.05% by weight to 0.15% by weight, from approximately 0.10% by weight to 0.15% by weight, from approximately 0.01% by weight to approximately 0.10% by weight, or from approximately 0.05% to approximately 0.10% by weight. Examples of Cu percentages present in such an embodiment may include 0.01% by weight, 0.02% by weight, 0.03% by weight, 0.04% by weight, 0.05% by weight, 0.06% by weight. % by weight, 0.07% by weight, 0.08% by weight, 0.09% by weight, 0.1% by weight, 0.11 % by weight, 0.12% by weight, 0.13% by weight, 0.14% by weight, 0.15% by weight, 0.16 % by weight, 0.17% by weight, 0.18% by weight, 0.19% by weight, 0.20% by weight, 0.21 % by weight, 0.22% by weight, 0.23% by weight, 0.24% by weight or 0.25% by weight.
[0022] Specimen Mn ranges present in such an embodiment may comprise from about 0.01% by weight to about 1.0% by weight, from about 0.10% by weight to about 1.0% by weight, from about 0.20% by weight to about 1.0% by weight, from about 0.30% by weight to about 1.0% by weight, from about 0.40% by weight to about 1.0% by weight, from about 0.50% by weight to about 1.0% by weight, from about 0.60% by weight to about 1.0% by weight, from about 0.70% by weight to about 1.0% by weight, from about 0.80% by weight to about 1.0% by weight, from about 0.90% by weight to about 1.0% by weight, from about 0.01% by weight to about 0.9% by weight, from approximately 0.10% by weight to approximately 0.9% by weight, from approximately 0.20% by weight to approximately 0.9% by weight, from approximately 0.30% by weight to approximately 0.9% by weight, from approximately 0.40% by weight to approximately 0.9% by weight, from approximately 0.50% by weight to approximately 0.9% by weight, from approximately 0.60% by weight to approximately 0.9% by weight, from approximately 0,70% by weight to approximately 0.9% by weight, from approximately 0.80% by weight to approximately 0.9% by weight, from approximately 0.01% by weight to approximately 0.8% by weight, from approximately 0.10% by weight to approximately 0.8% by weight, from approximately 0.20% by weight to approximately 0.8% by weight, from approximately 0.30% by weight to approximately 0.8% by weight, from approximately 0.40% by weight to approximately 0.8% by weight, from approximately 0.50% by weight to approximately 0.8% by weight, from approximately 0.60% by weight to approximately 0.8% by weight, from approximately 0.70% by weight to approximately 0.8% by weight, from approximately 0.01% by weight to approximately 0.7% by weight, from approximately 0.10% by weight to approximately 0.7% by weight weight, from approximately 0.20% by weight to approximately 0.7% by weight, from approximately 0.30% by weight to approximately 0.7% by weight, from approximately 0.40% by weight to approximately 0.7% by weight, from approximately 0.50% by weight to approximately 0.7% by weight, or from approximately 0.60% by weight to approximately 0.7% by weight. Examples of Mn percentages present in such an embodiment may include 0.01% by weight, 0.02% by weight,0.03% by weight, 0.04% by weight, 0.05% by weight, 0.06% by weight, 0.07% by weight, 0.08% by weight, 0.09% by weight, 0.1% by weight, 0.11% by weight, 0.12% by weight, 0.13% by weight, 0.14% by weight, 0.15% by weight, 0.16% by weight, 0.17% by weight, 0.18%, by weight, 0.19% by weight, 0.20% by weight, 0.21% by weight, 0.22% by weight, 0.23% by weight, 0.24% by weight, 0.25% by weight, 0.26% by weight, 0.27% by weight, 0.28% by weight, 0.29% by weight, 0.30% by weight, 0.31% by weight, 0.32% by weight, 0.33% by weight, 0.34% by weight, 0.35% by weight, 0.36% by weight, 0.37% by weight, 0.38% by weight, 0.39% by weight, 0.40% by weight, 0.41% by weight, 0.42% by weight, 0.43% by weight, 0.44% by weight, 0.45% by weight, 0.46% by weight, 0.47% by weight, 0.48% by weight, 0.49% by weight, 0.50% by weight, 0.51% by weight, 0.52% by weight, 0.53% by weight, 0.54% by weight, 0.55% by weight, 0.56% by weight, 0.57% by weight, 0.58% by weight, 0.59% by weight, 0.60% by weight, 0.61% by weight, 0.62% by weight, 0.63% by weight, 0.64% by weight, 0.65% by weight, 0.66% by weight, 0.67% by weight, 0.68% by weight, 0.69% by weight, 0.70% by weight, 0.71% by weight, 0.72% by weight, 0.73% by weight, 0.74% by weight, 0.75% by weight, 0.76% by weight, 0.77% by weight, 0.78% by weight, 0.79% by weight, 0.80% by weight, 0.81% by weight, 0.82% by weight, 0.83% by weight, 0.84% by weight, 0.85% by weight, 0.86% by weight, 0.87% by weight, 0.88% by weight, 0.89% by weight, 0.90% by weight, 0.91% by weight, 0.92% by weight, 0.93% by weight, 0.94% by weight, 0.95% by weight, 0.96% by weight, 0.97% by weight, 0.98% by weight, 0.99% by weight or 1.0% by weight.
[0023] The exemplary ranges of Si present in such an embodiment may include from approximately 0.01% by weight to approximately 1.0% by weight, from approximately 0.10% by weight to approximately 1.0% by weight, from approximately 0.20% by weight to approximately 1.0% by weight, from approximately 0.30% by weight to 1.0% by weight, from approximately 0.40% by weight to approximately 1.0% by weight, from approximately 0.50% by weight to approximately 1.0% by weight, from approximately 0.60% by weight to approximately 1.0% by weight, from approximately 0.70% by weight to approximately 1.0% by weight, from approximately 0.80% by weight to approximately 1.0% by weight, from approximately 0.90% by weight to approximately 1.0% by weight, from approximately 0.01% by weight to approximately 0.9 % by weight, from approximately 0.10% by weight to approximately 0.9% by weight, from approximately 0.20% by weight to approximately 0.9% by weight, from approximately 0.30% by weight to approximately 0.9% by weight, from approximately 0.40% by weight to approximately 0.9% by weight, from approximately 0.50% by weight to approximately 0.9% by weight, from approximately 0.60% by weight to approximately 0.9% by weight, from approximately 0,70% by weight to approximately 0.9% by weight, from approximately 0.80% by weight to approximately 0.9% by weight, from approximately 0.01% by weight to approximately 0.8% by weight, from approximately 0.10% by weight to approximately 0.8% by weight, from approximately 0.20% by weight to approximately 0.8% by weight, from approximately 0.30% by weight to approximately 0.8% by weight, from approximately 0.40% by weight to approximately 0.8% by weight, from approximately 0.50% by weight to approximately 0.8% by weight, from approximately 0.60% by weight to approximately 0.8% by weight, from approximately 0.70% by weight to approximately 0.8% by weight, from approximately 0.01% by weight to approximately 0.7% by weight, from approximately 0.10% by weight to approximately 0.7% by weight weight, from about 0.20% by weight to about 0.7% by weight, from about 0.30% by weight to about 0.7% by weight, from about 0.40% by weight to about 0.7% by weight, from about 0.50% by weight to about 0.7% by weight, or from about 0.60% by weight to about 0.7% by weight. Examples of percentages of Si present in such an embodiment may include 0.01% by weight, 0.02% by weight,0.03% by weight, 0.04% by weight, 0.05% by weight, 0.06% by weight, 0.07% by weight, 0.08% by weight, 0.09% by weight, 0.1% by weight, 0.11% by weight, 0.12% by weight, 0.13% by weight, 0.14% by weight, 0.15% by weight, 0.16% by weight, 0.17% by weight, 0.18% by weight, 0.19% by weight, 0.20% by weight, 0.21% by weight, 0.22% by weight, 0.23% by weight, 0.24% by weight, 0.25% by weight, 0.26% by weight, 0.27% by weight, 0.28% by weight, 0.29% by weight, 0.30% by weight, 0.31% by weight, 0.32% by weight, 0.33% by weight, 0.34% by weight, 0.35% by weight, 0.36% by weight, 0.37% by weight, 0.38% by weight, 0.39% by weight, 0.40% by weight, 0.41% by weight, 0.42% by weight, 0.43% by weight, 0.44% by weight, 0.45% by weight, 0.46% by weight, 0.47% by weight, 0.48% by weight, 0.49% by weight, 0.50% by weight, 0.51% by weight, 0.52% by weight, 0.53% by weight, 0.54% by weight, 0.55% by weight, 0.56% by weight, 0.57% by weight, 0.58% by weight, 0.59% by weight, 0.60% by weight, 0.61% by weight, 0.62% by weight, 0.63% by weight, 0.64% by weight, 0.65% by weight, 0.66% by weight, 0.67% by weight, 0.68% by weight, 0.69% by weight, 0.70% by weight, 0.71% by weight, 0.72% by weight, 0.73% by weight, 0.74% by weight, 0.75% by weight, 0.76% by weight, 0.77% by weight, 0.78% by weight, 0.79% by weight, 0.80% by weight, 0.81% by weight, 0.82% by weight, 0.83% by weight, 0.84% by weight, 0.85% by weight, 0.86% by weight, 0.87% by weight, 0.88% by weight, 0.89% by weight, 0.90% by weight, 0.91% by weight, 0.92% by weight, 0.93% by weight, 0.94% by weight, 0.95% by weight, 0.96% by weight, 0.97% by weight, 0.98% by weight, 0.99% by weight or 1.0% by weight.
[0024] Exemplary areas of C present in such an embodiment may comprise from about 0.01% by weight to about 0.25% by weight, from about 0.05% by weight to about 0.25% by weight, from about 0.10% by weight to about 0.25% by weight, from about 0.15% by weight to about 0.25% by weight, from about 0.20% by weight to about 0.25% by weight, from about 0.01% by weight to about 0.20% by weight, from about 0.05% by weight to about 0.20% by weight, from about 0.10% by weight to about 0.20% by weight, from about 0.15% by weight to about 0.20% by weight, from about 0.01% by weight to 0.15% by weight, from about 0.05% by weight to 0.15% by weight, from approximately 0.10% by weight to 0.15% by weight, from approximately 0.01% by weight to approximately 0.10% by weight, or from approximately 0.05% to approximately 0.10% by weight. Examples of percentages of C present in such an embodiment might include 0.01% by weight, 0.02% by weight, 0.03% by weight, 0.04% by weight, 0.05% by weight, 0.06% by weight. % by weight, 0.07% by weight, 0.08% by weight, 0.09% by weight, 0.1% by weight, 0.11 % by weight, 0.12% by weight, 0.13% by weight, 0.14% by weight, 0.15% by weight, 0.16 % by weight, 0.17% by weight, 0.18% by weight, 0.19% by weight, 0.20% by weight, 0.21 % by weight, 0.22% by weight, 0.23% by weight, 0.24% by weight or 0.25% by weight.
[0025] In another particular embodiment, no more than 0.5% by weight of C, no more than 0.040% by weight of S and no more than 0.040% by weight of P may be added to a 13Cr material comprising Mo, W, Ti, Nb, V, at least 11% by weight of Cr and between 0.01% by weight and 1% of Ni. Exemplary areas of C present in such an embodiment may comprise from about 0.05% by weight to about 0.5% by weight, from about 0.10% by weight to about 0.5% by weight, from about 0.15% by weight to about 0.5% by weight, from about 0.20% by weight to about 0.5% by weight, from about 0.25% by weight to about 0.5% by weight, from about 0.30% by weight to about 0.5% by weight, from about 0.35% by weight to about 0.5% by weight, from about 0.40% by weight to about 0.5% by weight, from about 0.45% by weight to about 0.5% by weight by weight, from approximately 0.01% by weight to approximately 0.4% by weight, from approximately 0.05% by weight to approximately 0.4% by weight, from approximately 0.10% by weight to approximately 0.4% by weight, from approximately 0.15% by weight to approximately 0.4% by weight, from approximately 0.20% by weight to approximately 0.4% by weight, from approximately 0.25% by weight to approximately 0.4% by weight, from approximately 0.30% by weight to approximately 0.4% by weight, from approximately 0.35% by weight to approximately 0.4% by weight, from approximately 0.01% by weight to approximately 0.3% by weight, from approximately 0.05% by weight to approximately 0.3% by weight, from approximately 0.10% by weight to approximately 0.3% by weight, from approximately 0.15% by weight to approximately 0.3% by weight, from about 0.20 to about 0.3% by weight, from about 0.25 to about 0.3% by weight, from about 0.01% by weight to about 0.2% by weight, from about 0.05% by weight to about 0.2% by weight, from about 0.10% by weight to about 0.2% by weight, from about 0.15% by weight to about 0.2% by weight, from about 0.01% by weight to about 0.1% by weight or from about 0.05% by weight to about 0.1% by weight.Examples of percentages of C present in such an embodiment may include 0.01% by weight, 0.02% by weight, 0.03% by weight, 0.04% by weight, 0.05% by weight, 0.06% by weight, 0.07% by weight, 0.08% by weight, 0.09% by weight, 0.1% by weight, 0.11% by weight, 0.12% by weight, 0.13% by weight, 0.14% by weight, 0.15%. by weight, 0.16% by weight, 0.17% by weight, 0.18% by weight, 0.19% by weight, 0.20% by weight, 0.21% by weight, 0.22% by weight, 0.23% by weight, 0.24% by weight, 0.25% by weight, 0.26% by weight, 0.27% by weight, 0.28% by weight, 0.29% by weight, 0.30% by weight, 0.31% by weight, 0.32% by weight, 0.33% by weight, 0.34% by weight, 0.35% by weight, 0.36% by weight, 0.37% by weight, 0.38% by weight, 0.39% by weight, 0.40% by weight, 0.41% by weight, 0.42% by weight, 0.43% by weight, 0.44% by weight, 0.45% by weight, 0.46% by weight, 0.47% by weight, 0.48% by weight, 0.49% by weight or 0.50% by weight.
[0026] Exemplary areas of S present in such an embodiment may comprise from approximately 0.0001% by weight to approximately 0.040% by weight, from approximately 0.001% by weight to approximately 0.040% by weight, from approximately 0.010% by weight to approximately 0.040% by weight, from approximately 0.015% by weight to approximately 0.020% by weight, from approximately 0.025% by weight to approximately 0.040% by weight, from approximately 0.030% by weight to approximately 0.040% by weight, from approximately 0.035% by weight to approximately 0.040% by weight, from approximately 0.0001% by weight to approximately 0.035% by weight, from approximately 0.001% by weight to approximately 0.035% by weight, from approximately from 0.010% by weight to approximately 0.035% by weight, from approximately 0.015% by weight to approximately 0.035% by weight, from approximately 0.020% by weight to approximately 0.035% by weight, from approximately 0.025% by weight to approximately 0.035% by weight, from approximately 0.030% by weight to approximately 0.035% by weight, from approximately 0.0001% by weight to approximately 0.030% by weight, from approximately 0.001% by weight to approximately 0.030% by weight, from approximately 0.0.010% by weight to approximately 0.030% by weight, from approximately 0.015% by weight to approximately 0.020% by weight, from approximately 0.025% by weight to approximately 0.030% by weight, from approximately 0.0001% by weight, weight to approximately 0.0025% by weight, from approximately 0.001% by weight to approximately 0.0025% by weight, from approximately 0.01% by weight to approximately 0.0025% by weight, from approximately 0.015% by weight to approximately 0.0025% by weight, from approximately 0.020% by weight to approximately 0.0025% by weight, from approximately 0.0001% by weight to approximately 0.0020% by weight, from approximately 0.001% by weight to approximately 0.0020% by weight, from approximately 0.01% by weight to approximately 0.0020% by weight, from approximately 0.015% by weight to approximately 0.0020% by weight, from approximately 0.0001% by weight to approximately 0.015% by weight, from approximately 0.001% by weight to about 0.015% by weight, from about 0.01% by weight to about 0.015% by weight, from about 0.0001% by weight to about 0.010% by weight or from about 0.001% by weight to about 0.010% by weight.Examples of percentages of S present in such an embodiment may include 0.0001% by weight, 0.0002% by weight, 0.0003% by weight, 0.0004% by weight, 0.0005% by weight, 0.0006% by weight, 0.0007% by weight, 0.0008% by weight, 0.0009% by weight, 0.01% by weight, 0.011% by weight, 0.012% by weight, 0.013% by weight, 0.14% by weight, 0.015% by weight, 0.016% by weight, 0.017% by weight, 0.018% by weight, 0.019% by weight, 0.020% by weight, 0.021% by weight, 0.022% by weight, 0.023% by weight, 0.024% by weight, 0.025% by weight, 0.026% by weight, 0.027% by weight, 0.028% by weight, 0.029% by weight, 0.030% by weight, 0.031% by weight, 0.032% by weight, 0.033% by weight, 0.034% by weight, 0.035% by weight, 0.036% by weight, 0.037% by weight, 0.038% by weight, 0.039% by weight or 0.040% by weight.
[0027] Exemplary ranges of P present in such an embodiment may comprise from about 0.0001% by weight to about 0.040% by weight, from about 0.001% by weight to about 0.040% by weight, from about 0.010% by weight to about 0.040% by weight, from about 0.015% by weight to about 0.020% by weight, from about 0.025% by weight to about 0.040% by weight, from about 0.030% by weight to about 0.040% by weight, from about 0.035% by weight to about 0.040% by weight, from about 0.0001% by weight to about 0.035% by weight, from about 0.001% by weight to about 0.035% by weight, from about from 0.010% by weight to approximately 0.035% by weight, from approximately 0.015% by weight to approximately 0.035% by weight, from approximately 0.020% by weight to approximately 0.035% by weight, from approximately 0.025% by weight to approximately 0.035% by weight, from approximately 0.030% by weight to approximately 0.035% by weight, from approximately 0.0001% by weight to approximately 0.030% by weight, from approximately 0.001% by weight to approximately 0.030% by weight, from approximately 0.0.10% by weight to approximately 0.030% by weight, from approximately 0.015% by weight to approximately 0.020% by weight, from approximately 0.025% by weight to approximately 0.030% by weight, from approximately 0.0001% by weight to approximately 0.0025% by weight, from approximately 0.001% by weight to approximately 0.0025% by weight, from approximately 0.01% by weight to approximately 0.0025% by weight, from approximately 0.015% by weight to approximately 0.0025% by weight, from approximately 0.020% by weight to approximately 0.0025% by weight, from approximately 0.0001% by weight to approximately 0.0020% by weight, from approximately 0.001% by weight to approximately 0.0020% by weight, from approximately 0.01% by weight to approximately 0.0020%, in weight, from about 0.015% in weight to about 0.0020% in weight, from about 0.0001% in weight to about 0.015% in weight, from about 0.001% in weight to about 0.015% in weight, from about 0.01% in weight to about 0.015% in weight, from about 0.0001% in weight to about 0.010% in weight, or from about 0.001% in weight to about 0.010% in weight.Examples of percentages of P present in such an embodiment may include 0.0001% by weight, 0.0002% by weight, 0.0003% by weight, 0.0004% by weight, 0.0005% by weight, 0.0006% by weight, 0.0007% by weight, 0.0008% by weight, 0.0009% by weight, 0.01% by weight, 0.011% by weight, 0.012% by weight, 0.013% by weight, 0.14% by weight, 0.015% by weight, 0.016% by weight, 0.017% by weight, 0.018% by weight, 0.019% by weight, 0.020% by weight, 0.021% by weight, 0.022% by weight, 0.023% by weight, 0.024% by weight, 0.025% by weight, 0.026% by weight, 0.027% by weight, 0.028% by weight, 0.029% by weight, 0.030% by weight, 0.031% by weight, 0.032% by weight, 0.033% by weight, 0.034% by weight, 0.035% by weight, 0.036% by weight, 0.037% by weight, 0.038% by weight, 0.039% by weight or 0.040% by weight.
[0028] In block 206, a treatment can be carried out on the 13Cr material. The treatment. The process may involve one or more cycles of austenitizing, quenching, thermal tempering, or annealing treatments. In some examples, the quenching treatment may be a freezing treatment. The treatment can increase the hardness of the 13Cr material, for example, to MY strengths of 95 / 100 / 105 / 110 / 115 / 120 / 125 ksi. Furthermore, the treatment can increase the toughness of the 13Cr material, resulting in increased resistance to hydrogen stress cracking and sulfide stress cracking. Despite the austenitizing treatment, due to the relatively low nickel content and the presence of additional elements such as Mo, W, Ti, Nb, and V, the microstructure of the 13Cr material may remain predominantly martensitic. This can be seen in the example diagram in [Fig.3] which shows the martensitic microstructure of an improved 13Cr 300 material according to a disclosure example.
[0029] In the particular embodiment where the 13Cr material comprises at least 11% by weight of Cr, between 0.01% by weight and 0.5% by weight of Ni, between 0.001% by weight and 0.020% by weight of S, between 0.001% by weight and 0.020% by weight of P, between 0.01% by weight and 0.25% by weight of Cu, between 0.01% by weight and 1.0% by weight of Mn, between 0.01% by weight and 1.0% by weight of Si, between 0.01% by weight and 0.25% by weight of C, Mo, W, Ti, Nb and V, the treatment may involve an austenitizing treatment, a quenching treatment and a thermal tempering treatment. Alternatively, the treatment may involve an austenitizing treatment, a quenching treatment, another austenitizing treatment, another quenching treatment, and a thermal tempering treatment. Such a treatment can produce a 13Cr material with a MY strength between 95 and 125 ksi, and a predominantly martensitic exhibiting very few austenitic or ferrite phases after a final thermal tempering treatment.
[0030] In the particular embodiment where the 13Cr material comprises at least 11% by weight of Cr, between 0.1% and 1.0% by weight of Ni, between 0.01% and 0.5% by weight of C, between 0.001% and 0.040% by weight of S, and between 0.001% and 0.040% by weight of P, Mo, W, Ti, Nb, and V, the treatment may involve annealing and heat tempering treatments, in some cases with or without quenching treatments as well. One or more of the quenching treatments may be a freezing treatment. Alternatively or in addition, the treatment may involve at least two quenching treatments and at least two heat tempering treatments. Such a treatment may produce a 13Cr material having a MY strength of 80 ksi or less. Additional processes, such as additive manufacturing, can be used to obtain the desired microstructure exhibiting primarily martensitic characteristics.
[0031] In some examples, the 13Cr material may exhibit a tensile strength of 110 ksi to 140 ksi (for example, from about 115 ksi to about 140 ksi, from about 120 ksi to about 140 ksi, from about 125 ksi to about 140 ksi, from about 130 ksi to about 140 ksi, from about 135 ksi to about 140 ksi, from about 110 ksi to about 135 ksi, from about 115 ksi to about 135 ksi, from about 120 ksi to about 135 ksi, from about 125 ksi to about 135 ksi, from about 130 ksi to about 135 ksi, from about 110 ksi to about 130 ksi, from about 115 ksi to about 130 ksi, from about 120 ksi to about 130 ksi, from about 125 ksi to about 130 ksi, from about 110 ksi to about 125 ksi, from about 115 ksi to about 125 ksi, from about 120 ksi to about 125 ksi, from about 110 ksi to about 120 ksi, from about 115 ksi to about 120 ksi or from about 110 ksi to about 115 ksi).Examples of tensile strengths may include 110 ksi, 111 ksi, 112 ksi, 113 ksi, 114 ksi, 115 ksi, 116 ksi, 117 ksi, 118 ksi, 119 ksi, 120 ksi, . 121 ksi, 122 ksi, 123 ksi, 124 ksi, 125 ksi, 126 ksi, 127 ksi, 128 ksi, 129 ksi, 130 ksi, 131 ksi, 132 ksi, 133 ksi, 134 ksi, 135 ksi, 136 ksi, 137 ksi, 138 ksi, 139 ksi or 140 ksi.
[0032] In some examples, after undergoing a notched Charpy impact test in V, the 13Cr material can exhibit a Charpy impact value of 20 J to 40 J (for example, from approximately 25 J to approximately 40 J, from approximately 30 J to approximately 40 J, from approximately 35 J to approximately 40 J, from approximately 20 J to approximately 35 J, from approximately 25 J to approximately 35 J, from approximately 30 J to approximately 35 J, from approximately 20 J to approximately 30 J, from approximately 25 J to approximately 30 J, or from approximately 20 J to approximately 25 J) at 0°C. Examples of Charpy impact values might include 20 J, 21 J, 22 J, 23 J, 24 J, 25 J, 26 J, 27 J, 28 J, 29 J, 30 J, 31 J, 32 J, 33 J J, 34 J, 35 J, 36 J, 38 J, 39 J or 40 J.
[0033] In some examples, the percentage elongation between the original length of the 13Cr material and the breaking point can be from 10% to 20% (for example, from approximately 12% to approximately 20%, from approximately 14% to approximately 20%, from approximately 16% to approximately 20%, from approximately 18% to approximately 20%, from approximately 10% to approximately 19%, from approximately 12% to approximately 19%, from approximately 14% to approximately 19%, from approximately 16% to approximately 19%, from approximately 18% to approximately 19%, from approximately 10% to approximately 18%, from approximately 12% to approximately 18%, from approximately 14% to approximately 18%, from approximately 16% to approximately 18%, from approximately 10% to approximately 17%, from approximately 12% to approximately 17%, from approximately 14% to approximately 17%, from approximately 16% to approximately 17%, from approximately 10% to approximately 16%, from approximately 12% to approximately 16% from approximately 14% to approximately 16%, from approximately 10% to approximately 15%, from approximately 12% to approximately 15%, from approximately 14% to approximately 15%, from approximately 10% to approximately 14%, from approximately 12% to approximately 14%, from approximately 10% to approximately 13%, from approximately 12% to approximately 13%, or from approximately 10% to approximately 12%. Examples of percentage increases may include 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, or 20%.
[0034] Aspects of the invention can be better understood by reference to the following non-limiting examples.
[0035] EXAMPLE - HIGH STRENGTH LOW NICKEL STAINLESS STEEL MATERIAL ACCORDING TO ASPECTS OF THIS DISCLOSURE COMPARED TO A HIGH NICKEL SUPER 13Cr STAINLESS STEEL MATERIAL
[0036] The following experiment demonstrates the characteristics of three low-nickel 13Cr materials (LN-1, LN-2, LN-3) improved with a composition and treatment, according to aspects of this disclosure, to enable increased toughness and SSC strength. The composition of each of LN-1, LN-2, and LN-3 is described in Table 1. [Tables 1] LN-1 LN-2 LN-3 % C 0.2 0.188 0.19 % Mn 0.86 0.84 0.73 % Si 0.44 0.40 0.26 % P 0.019 0.014 0.011 % S 0.002 0.007 0.0022 % Cr 13.25 13.20 13.18% Ni 0.13 0.13 0.14% Mo 0.04 ND 0.03% Cu 0.05 0.06 0.06% Nb (Cb) 0.04 ND ND % Ti 0.004 ND <0.01% V ND ND ND Table 1 - Details of the chemistry.
[0037] LN-1, LN-2 and LN-3 were then treated with a first treatment austenitizing, a quenching treatment, a second austenitizing treatment, a second quenching treatment and a thermal tempering treatment as indicated in Table 2 to achieve yield strengths of at least 95 ksi. [Tables 2] Details of the first austenitizing Details of the second austenitizing Details of the quenching process LN-1 998 °C (1828 °F) for 3 hours, oil quench 930 °C (1706 °F) for 3 hours, polymer quench 610 °C (1130 °F) for 4 hours and 45 minutes, air cooling LN-2 1000 °C (1832 °F) for 4 hours, oil quench 900 °C (1652 °F) for 4 hours, oil quench 610 °C (1130 °F) for 6 hours, air cooling LN-3 996 °C (1825 °F) for 3 hours, air quench 913 °C (1675 °F) for 3 hours, quench in oil at 591 °C (1095 °F) for 5 hours, air cooling Table 2 - Treatment details.
[0038] The resulting improved LN-1, LN-2 and LN-3 materials were then tested on their tensile properties, V-notch Charpy impact properties and SSC resistivity, as illustrated in Table 3, Table 4 and Table 5, respectively. [Tables 3] Yield strength, ksi Tensile strength, ksi % elongation % surface area reduction LN-1 119.1 136.4 15.8 58 LN-2 101.1 117.9 18.8 67 LN-3 114.1 132.3 17.0 55 Table 3 - Details of tensile properties.
[0039] [Tables4] Average Charpy Impact Test Temperature LN-1 0 °C (32 °F) 25 ft-lb (34 joules) LN-2 0 °C (32 °F) 17 ft-lb (23 joules) LN-3 0 °C (32 °F) 19 ft-lb (26 joules) Table 4 - V-notch Charpy impact properties. [Tables 5] H2S Test Temperature (psi) Chloride, mg / L pH % of stress Results LN-1 Room Temperature 14.5 140,000 4.5 90% AYS Pass LN-2 Room Temperature 14.5 140,000 4.5 90% AYS Pass LN-3 Room Temperature 14.5 140,000 4.5 90% AYS Pass Table 5 - Sulfide stress cracking (SSC) test data.
[0040] In addition, another control experiment was conducted to demonstrate the characteristics of three high-nickel Super 13Cr materials (HN-1, HN-2, HN-3). The composition of each of HN-1, HN-2 and HN-3 is described in Table 6. [Tables] HN-1 HN-2 HN-3 % C 0.22 0.19 0.019 % Mn 0.77 0.23 0.55 % Si 0.30 0.35 0.21 % P 0.018 0.012 0.016 % S 0.0007 0.0022 0.0004 % Cr 13.37 12.22 12.53% Ni 4.79 5.37 5.54% Mo 1.63 1.93 1.72% Cu 0.08 0.08 0.059% Nb (Cb) ND ND 0.043% Ti <0.15 <0.01 0.004% V <0.10 0.18 0.031% of N 0.08 0.018 0.061 Table 6 - Details of the chemistry.
[0041] HN-1, HN-2 and HN-3 were then treated with austenitizing treatment, a quenching treatment, a first thermal tempering treatment and, in some cases, a second thermal tempering treatment as indicated in Table 7 to achieve yield strengths of at least 95 ksi. [Paintings?] Austenitizing Details Quenching Details Second Quenching Details HN-1 932 °C (1710 °F) for 4 hours and 40 minutes, air quench 620 °C (1148 °F) for 14 hours, air cooling NA HN-2 950 °C (1742 °F) for 2 hours and 3 minutes, oil quench 620 °C (1148 °F) for 5 hours and 4 minutes, air cooling 550 °C (1022 °F) for 2 hours, air cooling HN-3 980 °C (1796 °F) for 5 hours, air quench 600 °C (1112 °F) for 10 hours, air cooling NA Table 7 - Treatment details.
[0042] The resulting HN-1, HN-2 and HN-3 materials were then tested for their tensile properties, V-notch Charpy impact properties and SSC resistivity, as illustrated in Table 8, Table 9 and Table 10, respectively. [Tables 8] Yield strength, ksi Tensile strength, ksi % elongation % surface area reduction HN-1 100.0 130.0 20.0 53 HN-2 108.0 129.0 22.5 66 HN-3 125.0 140.0 21.0 60 Table 8 - Details of tensile properties.
[0043] [Tables9] Test Temperature Medium Charpy Impact HN-1 -10°C(14°F) 109 ft-lb (148 joules) HN-2 -10°C(14°F) 139 ft-lb (189 joules) HN-3 -10°C(14°F) 137 ft-lb (186 joules) Table 9 - V-notch Charpy impact properties. [Tables 10] H2S Test Temperature (psi) Chloride, mg / L pH % Stress Results HN-1 Room Temperature 0.3 140,000 4.5 90% AYS Pass HN-2 Room Temperature 0.3 140,000 4.5 90% AYS Pass HN-1 Room Temperature 0.45 140,000 4.5 90% AYS Fail HN-2 Room Temperature 0.45 140,000 4.5 90% AYS Fail HN-1 Room Temperature 0.45 66,000 4.5 90% AYS Fail HN-2 Room Temperature 0.45 66,000 4.5 90% AYS Fail HN-3 Room Temperature 0.15 140,000 4.5 90% AYS Success HN-3 Ambient Temperature 0.73 140,000 5.5 90% AYS Failure Table 10 - Sulfide stress cracking (SSC) test data.
[0044] Table 3 shows the actual tensile properties at room temperature for two low-nickel 13Cr materials with a yield strength greater than 110 ksi and one low-nickel 13Cr material with a yield strength greater than 95 ksi. This is compared to Table 8, which shows all high-nickel Super 13Cr materials with a yield strength greater than 95 ksi and one high-nickel Super 13Cr material with a yield strength greater than 110 ksi. Thus, overall, the low-nickel 13Cr materials have slightly lower ductility (via the percentage elongation) compared to the high-nickel Super 13Cr materials.
[0045] Table 4 presents Charpy impact toughness data for low-nickel 13Cr materials according to aspects of this disclosure, which can be compared to Table 9 for high-nickel Super 13Cr materials. It should be noted that lower test temperatures may increase the severity of the test, but overall tests at 0 °C (32 °F) and -10 °C (14 °F) can range between 2 and 3 ft-lb, with tests at -10 °C (14 °F) leading to lower values compared to 0 °C (32 °F). Comparing the two datasets (Table 4 compared to Table 9), low nickel 13Cr materials according to aspects of this disclosure have lower toughness compared to high nickel Super 13Cr materials.
[0046] Table 5 provides sulfide stress cracking (SSC) test data results for low-nickel 13Cr materials according to aspects of this disclosure, compared to Table 10 for high-nickel Super 13Cr materials. All tests were performed at room temperature (RT), and these systems may be more susceptible to SSC at lower temperatures (close to room temperature) than at higher temperatures. All tests were performed at 90% of AYS (where AYS stands for actual yield strength under heat), in accordance with the industry protocol for testing the stress to be used for general qualification limits. Higher percentages of AYS, lower pH, and higher chloride content may increase the severity of SSC.Based on this, comparing the SSC performance of low-nickel 13Cr materials to high-nickel Super 13Cr materials of similar strength, the low-nickel 13Cr materials exhibit significantly higher SSC resistance than the high-nickel Super 13Cr materials. Therefore, it is likely that, according to aspects of this disclosure, low-nickel 13Cr materials may more effectively resist SSC in wellbore systems containing higher amounts of H2S, lower pH, and higher chloride concentrations than high-nickel Super 13Cr materials.
[0047] In certain aspects, an apparatus and a method for high-strength stainless steel materials are provided according to one or more of the following examples:
[0048] As used below, any reference to a series of examples should be understood as a reference to each of those examples in a disjunctive manner (for example, "Examples 1 to 4" should be understood as "Examples 1, 2, 3 or 4").
[0049] Example 1 is a stainless steel material comprising: at least about 11% by weight of Cr; between about 0.01% by weight and about 1.0% by weight of Ni; more than 0% by weight of Mo; more than 0% by weight of W; more than 0% by weight of Ti; more than 0% by weight of Nb; and more than 0% by weight of V.
[0050] Example 2 is the stainless steel material of Example 1(s), further comprising: not more than about 0.020% by weight of S; not more than about 0.020% by weight of P; not more than about 0.25% by weight of Cu; between about 0.01% by weight and about 1.0% by weight of Mn; between about 0.01% by weight and about 1.0% by weight of Si; and not more than about 0.25% by weight of C.
[0051] Example 3 is the stainless steel material of example(s) 1 to 2, further comprising: not more than about 0.5% by weight of C; not more than about 0.040% by weight of S; and not more than about 0.040% by weight of P.
[0052] Example 4 is the stainless steel material of example(s) 1 to 3, in which the stainless steel material comprises a minimum yield strength of less than 80 ksi.
[0053] Example 5 is the stainless steel material of example(s) 1 to 4, in which the stainless steel material has a tensile strength of about 110 ksi to about 140 ksi.
[0054] Example 6 is the stainless steel material of Examples 1 to 5, in which the stainless steel material has a Charpy impact value of about 20 J to about 40 J at about 0 °C.
[0055] Example 7 is the stainless steel material of example(s) 1 to 6, in which the stainless steel material has an elongation of about 10% to about 20%.
[0056] Example 8 is the stainless steel material of example(s) 1 to 7, further comprising: not more than 0.25% by weight of Mo; not more than 0.1% by weight of W; not more than 0.1% by weight of Ti; not more than 0.1% by weight of Nb; and not more than 0.1% by weight of V.
[0057] Example 9 is the stainless steel material of example(s) 1 to 8, wherein the stainless steel material comprises between 0.01% by weight and 0.5% by weight of Ni.
[0058] Example 10 is the stainless steel material of example(s) 1 to 9, in which the stainless steel material comprises a minimum yield strength of 95 to 125 ksi.
[0059] Example 11 is a process for forming a stainless steel material comprising: melting a material comprising: at least 11% by weight of Cr; and between 0.01% by weight and 1.0% by weight of Ni; and adding Mo, W, Ti, Nb and V to the material.
[0060] Example 12 is the process of example or examples 11, further comprising: carrying out at least one quenching treatment on the material.
[0061] Example 13 is the process of Examples 11 and 12, in which at least one quenching treatment includes a freezing treatment.
[0062] Example 14 is the process of Examples 11 to 13, further comprising: carrying out at least one austenitizing treatment on the material.
[0063] Example 15 is the process of Examples 11 to 14, further comprising: carrying out at least one thermal tempering treatment on the material.
[0064] Example 16 is the process of Examples 11 to 15, in which the melting of the material further comprises the material further comprising: not more than 0.020% by weight of S; not more than 0.020% by weight of P; not more than 0.25% by weight of Cu; between 0.01% by weight and 1.0% by weight of Mn; between 0.01% by weight and 1.0% by weight of Si; and not more than 0.25% by weight of C.
[0065] Example 17 is the process of Examples 11 to 16, in which the melting of the material further comprises the material further comprising: not more than 0.5% by weight of C; not more than 0.040% by weight of S; and not more than 0.040% by weight of P.
[0066] Example 18 is the process of Examples 11 to 17, in which the addition of Mo, W, Ti, Nb and V to the material further includes the addition of: not more than 0.25% by weight of Mo; not more than 0.1% by weight of W; not more than 0.1% by weight of Ti; not more than 0.1% by weight of Nb; and not more than 0.1% by weight of V.
[0067] Example 19 is the process of Examples 11 to 18, in which the melting of the material further comprises the material further comprising between 0.01 wt% and 0.5 wt% of Ni.
[0068] Example 20 is the process of Examples 11 to 19, in which the material has a minimum yield strength of 95 to 125 ksi.
[0069] The preceding description of certain examples, including illustrated examples, is provided for illustrative and descriptive purposes only and is not intended to be exhaustive or to limit disclosure to the specific forms disclosed. Many modifications, adaptations, and uses thereof will be obvious to a person skilled in the art without departing from the scope of disclosure.
Claims
Demands
1. Stainless steel material comprising: at least 11% by weight of Cr; 0.01% by weight - 0.5% by weight of Ni; 0.001% by weight - 0.020% by weight of S, 0.001% by weight - 0.020% by weight of P, 0.01% by weight - 0.25% by weight of Cu, 0.01% by weight - 1.0% by weight of Mn, 0.01% by weight - 1.0% by weight of Si, 0.01% by weight - 0.25% by weight of C, Mo, W, Ti, Nb, and V, wherein Ti is between 0.09% by weight and 0.1% by weight.
2. Stainless steel material according to claim 1, wherein the stainless steel material comprises a tensile strength of 110 ksi to 140 ksi.
3. Stainless steel material according to claim 1, wherein the stainless steel material has a Charpy impact value of 20 J to 40 J at 0 °C.
4. Stainless steel material according to claim 1, wherein the stainless steel material comprises a minimum yield strength of 95 to 125 ksi.
5. A process for forming a stainless steel material comprising: melting a material comprising: at least 11% by weight of Cr; and 0.01% - 0.5% by weight of Ni; and adding: 0.001% by weight - 0.020% by weight of S, 0.001% by weight - 0.020% by weight of P, 0.01% by weight - 0.25% by weight of Cu, 0.01% by weight - 1.0% by weight of Mn, 0.01% by weight - 1.0% by weight of Si, 0.01% by weight - 0.25% by weight of C, Mo, W, Ti, Nb, and V, wherein Ti is added at a rate of 0.09% by weight to 0.1% by weight.
6. A method according to claim 5, further comprising: carrying out at least one quenching treatment on the stainless steel material comprising a freezing treatment.
7. A method according to claim 5, further comprising: carrying out at least one austenitizing treatment on the stainless steel material and carrying out at least one thermal tempering treatment on the material.