WO2019001587A1 - Low-nickel copper-containing type t/p92 steel weld material for combating high temperature creep - Google Patents

Low-nickel copper-containing type t/p92 steel weld material for combating high temperature creep Download PDF

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WO2019001587A1
WO2019001587A1 PCT/CN2018/097698 CN2018097698W WO2019001587A1 WO 2019001587 A1 WO2019001587 A1 WO 2019001587A1 CN 2018097698 W CN2018097698 W CN 2018097698W WO 2019001587 A1 WO2019001587 A1 WO 2019001587A1
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content
weld
steel
welding
copper
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王学
杜成超
刘洪�
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武汉大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
    • B23K35/3053—Fe as the principal constituent
    • B23K35/308—Fe as the principal constituent with Cr as next major constituent
    • B23K35/3086—Fe as the principal constituent with Cr as next major constituent containing Ni or Mn
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0255—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in welding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/02—Iron or ferrous alloys
    • B23K2103/04—Steel or steel alloys

Definitions

  • the invention belongs to the technical field of heat-resistant steel, and particularly relates to a high-temperature creep resistant T/P92 steel welding material for an ultra-supercritical thermal power unit.
  • T/P92 steel is a new type of martensitic heat-resistant steel which is obtained by adding a certain amount of tungsten element to the T/P91 steel, appropriately reducing the content of molybdenum and adding a trace amount of boron. It is widely used in ultra-super Thick-walled pipes such as main steam pipes and headers of critical units, and heated surface pipes such as superheaters and reheaters, and casting materials (C92) are also used to manufacture cylinders and valves.
  • the main methods for welding T/P92 steel are manual arc welding (SMAW), submerged arc welding (SAW) and tungsten argon arc welding (GATW). Welding materials such as welding rods and welding wires are required for welding.
  • SMAW manual arc welding
  • SAW submerged arc welding
  • GATW tungsten argon arc welding
  • T/P92 steel is filled with more high-temperature strengthening elemental tungsten. Its welding consumable metal or weld seam is easy to form ⁇ -ferrite during solidification, which reduces the impact toughness of the material. And high temperature creep strength. Therefore, preventing the formation of ⁇ -ferrite in the deposited metal or weld is the primary problem to be solved in the design of T/P92 steel welding materials. At present, there are two methods for suppressing the formation of ⁇ -ferrite in the deposited metal of T/P92 steel consumables.
  • One method is to increase the content of manganese and nickel in the deposited metal, such as Bole Welding Group (formerly Mison 616 series of electrodes and wires from Thyssen Welding, Chromet 92 electrodes and 9CrWV welding wire from Manchester United Welding Materials, Inc.; another method to add cobalt in the deposited metal to the base metal, such as Olympus, Switzerland ALCROMOCORD 92 welding rod and ALCROMO WF 92 welding wire, Japan's Kobelco CR-12S welding rod and US-12CRSD welding wire.
  • Bole Welding Group formerly Mison 616 series of electrodes and wires from Thyssen Welding, Chromet 92 electrodes and 9CrWV welding wire from Manchester United Welding Materials, Inc.
  • another method to add cobalt in the deposited metal to the base metal such as Olympus, Switzerland ALCROMOCORD 92 welding rod and ALCROMO WF 92 welding wire, Japan's Kobelco CR-12S
  • the disadvantage of the former composition design method is that both manganese and nickel expand the austenite phase region elements, and increasing their content significantly reduces the A C1 point of the deposited metal, and there is a risk of re-forming austenite during post-weld heat treatment. For this reason, it is necessary to limit the upper limit content of Mn+Ni, resulting in the remaining ⁇ -ferrite remains in the deposited metal. In addition, increasing the nickel content adversely affects the high temperature long-term creep properties of the material. The latter component design method has little effect on the deposited metal A C1 point, but the cobalt is expensive and increases the cost of the welding consumable. Therefore, it is necessary to provide a special welding material for T/P92 steel which can suppress the formation of ⁇ -ferrite of the deposited metal, and has a high A C1 point of the deposited metal, excellent high temperature creep resistance and low cost.
  • Low-nickel copper-containing T/P92 steel welding material resistant to high temperature creep characterized in that the welding consumable comprises the following components C, Mn, Si, Cr, Ni, W, Mo, Nb, V, N, B, Al, Ti, S, P, Fe and Cu.
  • the copper content (wt.%) in the consumable is: 0.8-1.5.
  • the content (wt.%) of each component in the welding consumable is: C 0.07-0.12, Mn 0.30-0.60, Si ⁇ 0.40, Cr 8.50-9.50, Ni ⁇ 0.40, W 1.50-2.00, Mo 0.30-0.60, Cu 0.8-1.5, Nb 0.04-0.07, V 0.15-0.25, N 0.03-0.07, B 0.001-0.005, Al ⁇ 0.03, Ti ⁇ 0.01, S ⁇ 0.01, P ⁇ 0.02, and the balance is Fe.
  • the technical scheme of the invention is to obtain the minimum copper content required for inhibiting the formation of ⁇ -ferrite by calculating the chromium equivalent of the deposited metal and the observation of the optical metal phase; quantitatively studying the copper content on the deposited metal by thermodynamic calculation and thermal expansion method of the material The influence of A C1 point; the effect of copper content on the creep properties of deposited metal was studied by high temperature creep rupture test, and the distribution and size of copper particles in the deposited metal creep sample were studied by microscopic analysis experiments such as electron microscopy.
  • the high temperature strengthening mechanism of the element in T/P92 steel determines the range of copper content that has the best strengthening effect. Based on the results of the above three aspects, the copper content of the copper-containing T/P92 steel welding consumable metal was determined, and the austenitizing elements such as manganese and nickel were adjusted accordingly.
  • composition characteristics of the deposited metal of the T/P92 steel welding material for high temperature creep resistance of the present invention take into account the following factors:
  • C is an austenite stabilizing element that stabilizes the tempered martensite microstructure and forms carbides to increase creep strength.
  • the C content is less than 0.07%, the weld is liable to form ⁇ -ferrite, and the amount of carbide is small, which is unfavorable for creep strength.
  • the C content is too high to increase the weld crack sensitivity, so the C content range of the present invention is controlled to be 0.07 to 0.12%.
  • Mn is an austenite stabilizing element, which is beneficial to inhibit ⁇ -ferrite.
  • Mn has deoxidation and desulfurization, which can increase the strength and toughness of the weld.
  • the Mn content is too high, which significantly reduces the A C1 point of the weld, resulting in the austenite being re-formed at the highest post-weld heat treatment temperature.
  • the Mn content exceeding 1.5% significantly reduces the creep strength.
  • Ni is also an austenite forming element and has a positive effect on suppressing the formation of ⁇ -ferrite and stabilizing the martensite structure, so that the impact toughness of the weld can be improved.
  • the European BS EN standard stipulates that the highest Ni content is 0.8% or even 1.0%, which is significantly higher than T/P91.
  • the upper limit of the Ni content of T/P92 steel (0.4%).
  • increasing the Ni content significantly reduces the A C1 point, causing the weld to re-form austenite at the highest post-weld heat treatment temperature.
  • studies have shown that when the Ni content in the high chromium heat-strength steel exceeds 0.4%, the acceleration is accelerated.
  • the roughening of the M 23 C 6 type carbide during the creep process and the formation of the Z phase reduce the creep properties.
  • the present invention controls the Mn content to be 0.30-1.0%, the Ni content to be controlled within 0.40%, and the total content of Mn+Ni is controlled to be less than 1.0%, which is higher than the current foreign brands such as MTS616, Chromet 92 and 9CrWV.
  • the Ni content of the deposited metal of the steel consumables and the total content of Mn+Ni are reduced by about 50%.
  • Si is an important deoxidizer and can improve the oxidation resistance of the weld.
  • a suitably low Si content is beneficial to improve the toughness of the weld metal.
  • the Si content of the weld is required to be less than 0.30%, and the Si content of the present invention is controlled to be 0.1%-0.40%, which is higher than the Si content of the P92 steel.
  • the upper limit (0.5%) is lower.
  • Chromium Cr is the most important element to ensure resistance to steam oxidation and hot corrosion. As the Cr content increases, the weld's resistance to steam corrosion is better. However, Cr is a ferrite forming element, and when the content is too high, ⁇ -ferrite is generated in the weld, and the impact toughness and creep strength of the weld are lowered. Therefore, the Cr content of the present invention is controlled to be 8.5 to 9.5%.
  • Tungsten and Molybdenum Both W and Mo are ferrite forming elements, which are not conducive to the formation of ⁇ -ferrite in welds, but they are the most important solid solution strengthening elements in T/P92 steel and can improve the stability of carbides. Sexuality plays an indirect strengthening role.
  • the W and Mo content ranges of the present invention are comparable to those of the T/P92 steel, which are 1.5-2.0% and 0.3-0.6%, respectively.
  • Copper Adding Cu is the main innovation of the present invention because both T/P92 steel and existing T/P92 steel welding materials do not contain Cu.
  • the main functions of Cu are: Cu is an austenite forming element, which can inhibit the formation of ⁇ -ferrite in the weld.
  • the inventors' experimental research shows that the copper-containing T/P92 steel weld is subjected to post-weld heat treatment.
  • the solid solution of Cu in the as-welded state is precipitated by ⁇ -Cu particles, which are dispersed in the slats and the slats, and have a high number density at the slab boundary, as shown in FIG.
  • the determination of the range of Cu content should consider the three factors of inhibiting the formation of ferrite, fully exerting its high-temperature strengthening effect, and avoiding a significant decrease in the A C1 point.
  • the present invention determines the content range thereof: the ferrite content calculation method determined according to the chromium equivalent concept (refer to Chinese patent ZL201210192206.X), Cu is equivalent to Co in suppressing ferrite formation ability, and is about 1.5 of Mn. The ratio is about 60% of Ni, that is, the same effect of suppressing ferrite is maintained.
  • ZL201210131877.5 shows that Cu reduces the A C1 point by less than Mn and Ni.
  • Thermodynamic calculations and measured results show that when the Cu content exceeds 0.7%, the Cu content is continuously increased, and there is almost no influence on the A C1 point, as shown in Fig. 5-7.
  • the copper content of the present invention ranges from 0.8 to 1.5%.
  • Nb is a strong carbide forming element, which forms a finely dispersed MX type second phase precipitate with C and N, which is very stable at high temperatures, thereby improving the high temperature creep strength of the weld.
  • the content is less than 0.04%, the amount of precipitates is small, and sufficient strengthening effect cannot be obtained, but it has been found that the Nb content is high and the impact toughness of the weld is lowered.
  • the present invention controls the Nb content to be 0.04% to 0.07%, and the upper limit is slightly lower than 0.09% of the T/P92 steel.
  • Vanadium is a strong carbide forming element, which forms a finely dispersed and stable MX type second phase precipitate with C and N, which improves the high temperature creep strength of the weld.
  • the influence on the weld toughness is small.
  • the V content of the present invention is equivalent to that of the T/P92 steel, and is controlled at 0.15% to 0.25%.
  • N forms a finely dispersed MX type second phase precipitate with Nb and V, which significantly improves the high temperature creep strength of the weld.
  • the influence on the weld toughness is small.
  • the N content of the present invention is equivalent to that of the T/P92 steel, and is controlled at 0.04%-0.07%.
  • B is a grain boundary strengthening element, which can improve the high temperature creep strength of the weld, but boron is easily burned during the welding process.
  • the B content of the present invention is controlled to be 0.001% to 0.005%, which is slightly lower than the upper limit value (0.006%) of the T/P92 steel.
  • Al is added as a deoxidizer in the consumables.
  • the residual Al content in the weld is too high, which reduces the permanent plasticity of the weld.
  • Al is easily combined with N preferentially, so that the N dissolved in the weld is approximately zero, and precipitation strengthening is not formed, and the high temperature creep strength of the weld is lowered.
  • the Al content of the present invention is controlled to be 0.03% or less.
  • Titanium is a very strong carbide forming element, which affects the combination of Nb and V with C and N, and forms TiN once, which is not conducive to the precipitation strengthening effect. Therefore, the Ti content of the present invention is controlled to be 0.01% or less.
  • S and P are inevitable impurity elements in the weld, which increase the tendency of the weld to crack and reduce the creep fracture plasticity of the weld. Therefore, the present invention controls the S and P contents to be within 0.01% and 0.02%, respectively.
  • the welding material of the invention is added with copper, the nickel element content is reduced, the precious element cobalt is not added, the material cost is reduced, and the deposited metal suppresses the formation of ferrite while avoiding a significant decrease of the A C1 point, and Its normal temperature mechanical properties meet or exceed the existing high nickel or cobalt added T/P92 steel welding consumables;
  • the welding consumable of the invention has excellent high temperature creep resistance, and the long-term and long-lasting fracture life of the deposited metal is closest to the average value of the P92 steel.
  • Figure 1 shows the precipitated phase of the deposited metal of the welding consumable of the present invention after tempering at 760 ° C for 4 h;
  • Figure 2 is a precipitation phase of the embodiment of the welding consumable of the present invention after a long-term test at 650 ° C / 100 Ma / 4897.1 h;
  • Figure 3 shows the precipitated phase of 1.6% Cu T/P92 consumable deposited metal after tempering at 760 ° C ⁇ 4 h;
  • Figure 4 shows the precipitated phase of the T/P92 consumable deposited metal containing 1.69% Cu after 650 ° C / 100 Ma / 3896.5 h long-term test;
  • Figure 5 is a thermodynamic calculation of the effect of copper content on the A C1 point of the P92 weld
  • Figure 6 shows the results of the thermal expansion method of the deposited metal A C1 point of the welding material embodiment of the present invention
  • Figure 7 is a graph showing the results of thermal expansion of the comparatively deposited metal A C1 point of the welding consumable of the present invention.
  • Figure 8 is a microstructure (electrode arc welding) of the welding consumable metal of the present invention after tempering at 760 ° C for 4 h;
  • Figure 9 is a comparison of the welding material examples and comparative examples of the present invention at a permanent breaking time of 650 ° C / 100 Ma;
  • FIG. 1-9 The technical solution of the present invention will be further specifically described below by way of embodiments and with reference to the accompanying drawings, as shown in FIG. 1-9:
  • the weld metal is ⁇ -Cu precipitated on the martensite lath after tempering at 760 ° C ⁇ 4 h. Although the particles were fine, they showed significant aggregation growth after a long-term test at 650 ° C / 100 Ma / 3896.5 h.
  • the A C1 point of the weld metal of the welding material of the present invention is 809 ° C, which is 49 ° C higher than the post-weld heat treatment temperature (760 ° C), and the post-weld heat treatment temperature is 20-30 ° C lower than the A C1 point.
  • the above requirements have a large margin.
  • the weld metal of the welding material of the present invention is a tempered lath martensite structure without ferrite.
  • the weld metal (1#) of the T/P92 steel welding material of the present invention has the longest life at 650 ° C / 100 Ma, and exceeds the average life of the T / P 92 steel, which is significantly higher than the existing high.
  • the durability of the T/P92 consumable deposited metal (5#) containing 1.69% Cu is lower than that of 1#, indicating that when the Cu content exceeds the upper limit of the invention (1.5%), the adverse effect on the long-term performance is large.
  • the distribution characteristics of the material group after the tempering of the deposited metal of the welding consumable at 760 ° C ⁇ 4 h :
  • the weld is a fully tempered martensite structure without ferrite
  • composition range of the present invention a plurality of sets of examples are described for the low nickel copper-containing T/P92 steel welding material of the present invention, and the copper element is added through the coating or the welding core.
  • the copper content of Comparative Example 1 exceeded the upper limit (1.5%) of the present invention in order to explain the effect of excessive copper content on weld bead performance.
  • the performance test results of the embodiments of the present invention are shown in Table 2 - Table 3. It can be seen from Table 2 that the room temperature mechanical properties of the deposited metal of the electrode of the present invention are comparable to those of the MTS616 electrode deposited metal, and the room temperature impact toughness is lower than that of the CR-12S electrode deposited metal, but the tensile strength and impact toughness at room temperature are better than ALCROMOCORD 92 overall.
  • the electrode is deposited with metal. It can be seen from Table 3 that the impact work of the electrode deposited metal of the present invention after long-term aging is equivalent to that of MTS616, CR-12S and ALCROMOCORD 92 electrodes.
  • the long-term durability of the electrode deposited metal of the present invention is significantly better than that of the CR-12S electrode deposited metal in terms of the most important performance index of the welding material for high temperature creep resistance, and is superior to MTS616 and ALCROMOCORD 92.
  • the electrode deposited metal has a creep rupture life at 650 ° C / 100 MPa exceeding the average creep creep life of P92 steel published by the ECCC in 2005 (4735 h).
  • the copper content of Comparative Example 1 exceeded the upper limit of the present invention, and its endurance life was decreased as compared with the examples.
  • the high temperature creep resistant P92 welding material of the present invention adopts a low cost copper element instead of a nickel element or an expensive alloying alloy component design to ensure the room temperature mechanical properties and long-term aging of the deposited metal. Under the premise of impact energy, the most important performance index of the long-term performance of the deposited metal is improved, and the cost performance is high.

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Abstract

A low-nickel copper-containing type T/P92 steel weld material for combating high temperature creep, comprising C, Mn, Si, Cr, Ni, W, Mo, Nb, V, N, B, Al, Ti, S, P, Fe and Cu, the amount of copper content (wt. %) in said material being 0.8-1.5. Copper is added to the weld material to reduce the amount of nickel, and the noble element cobalt is not added so as to reduce the cost of the material. The deposited metal in the invention both inhibits the formation of ferrites and prevents a marked reduction of the AC1 temperature, and the mechanical properties at room temperature reach or surpass current T/P92 steel weld material that has high nickel content or that has cobalt added thereto. The weld material has an outstanding ability to combat high-temperature creep, and the endurance and fracture life of the deposited metal is closest to the average value for P92 steel.

Description

一种抗高温蠕变的低镍含铜型T/P92钢焊材Low nickel copper-containing T/P92 steel welding material resistant to high temperature creep 技术领域Technical field
本发明属于耐热钢技术领域，具体涉及一种超超临界火电机组用抗高温蠕变T/P92钢焊接材料。The invention belongs to the technical field of heat-resistant steel, and particularly relates to a high-temperature creep resistant T/P92 steel welding material for an ultra-supercritical thermal power unit.
背景技术Background technique
T/P92钢是在T/P91钢的基础上添加一定量的钨元素、适当降低钼元素含量，并添加微量硼元素而得到的一种新型马氏体耐热钢，被广泛用于超超临界机组主蒸汽管、集箱等厚壁管道，以及过热器、再热器等受热面管，其铸件材料(C92)还被用于制造气缸和阀门。目前焊接T/P92钢的主要方法为手工电弧焊(SMAW)、埋弧焊(SAW)和钨极氩弧焊(GATW)等，焊接时需添加填充材料，即焊条和焊丝等焊接材料。T/P92 steel is a new type of martensitic heat-resistant steel which is obtained by adding a certain amount of tungsten element to the T/P91 steel, appropriately reducing the content of molybdenum and adding a trace amount of boron. It is widely used in ultra-super Thick-walled pipes such as main steam pipes and headers of critical units, and heated surface pipes such as superheaters and reheaters, and casting materials (C92) are also used to manufacture cylinders and valves. At present, the main methods for welding T/P92 steel are manual arc welding (SMAW), submerged arc welding (SAW) and tungsten argon arc welding (GATW). Welding materials such as welding rods and welding wires are required for welding.
与T/P91钢相比，T/P92钢中加入了较多的高温强化元素钨，其焊材熔敷金属或焊缝在凝固过程中易形成δ-铁素体，它降低材料的冲击韧性和高温蠕变强度。因此，防止熔敷金属或焊缝中形成δ-铁素体是T/P92钢焊接材料设计中需解决的首要问题。目前，抑制T/P92钢焊材熔敷金属形成δ-铁素体的成分设计方法有2种，一种方法是提高熔敷金属中的锰元素和镍元素的含量，如伯乐焊接集团(原蒂森焊接)的MTS616系列焊条和焊丝、英国曼彻特焊接材料公司的Chromet 92焊条和9CrWV焊丝等；另一种方法在熔敷金属中添加母材所没有的钴元素，如瑞士奥林康的ALCROMOCORD 92焊条和ALCROMO WF 92焊丝、日本神钢的CR-12S焊条和US-12CRSD焊丝等。前一种成分设计方法的弊端在于锰、镍均为扩大奥氏体相区元素，提高它们的含量会显著降低熔敷金属的A C1点，在焊后热处理时有重新形成奥氏体风险,为此不得不限制Mn+Ni的上限含量，导致熔敷金属仍有δ-铁素体残留。此外，提高镍含量对材料的高温 长时蠕变性能有不利影响。后一种成分设计方法虽对熔敷金属A C1点的影响很小，但钴的价格昂贵，增加了焊材成本。因此有必要提供一种既可抑制熔敷金属形成δ-铁素体，同时又具有熔敷金属A C1点高、抗高温蠕变性能优良且成本低的T/P92钢专用焊材。 Compared with T/P91 steel, T/P92 steel is filled with more high-temperature strengthening elemental tungsten. Its welding consumable metal or weld seam is easy to form δ-ferrite during solidification, which reduces the impact toughness of the material. And high temperature creep strength. Therefore, preventing the formation of δ-ferrite in the deposited metal or weld is the primary problem to be solved in the design of T/P92 steel welding materials. At present, there are two methods for suppressing the formation of δ-ferrite in the deposited metal of T/P92 steel consumables. One method is to increase the content of manganese and nickel in the deposited metal, such as Bole Welding Group (formerly Mison 616 series of electrodes and wires from Thyssen Welding, Chromet 92 electrodes and 9CrWV welding wire from Manchester United Welding Materials, Inc.; another method to add cobalt in the deposited metal to the base metal, such as Olympus, Switzerland ALCROMOCORD 92 welding rod and ALCROMO WF 92 welding wire, Japan's Kobelco CR-12S welding rod and US-12CRSD welding wire. The disadvantage of the former composition design method is that both manganese and nickel expand the austenite phase region elements, and increasing their content significantly reduces the A C1 point of the deposited metal, and there is a risk of re-forming austenite during post-weld heat treatment. For this reason, it is necessary to limit the upper limit content of Mn+Ni, resulting in the remaining δ-ferrite remains in the deposited metal. In addition, increasing the nickel content adversely affects the high temperature long-term creep properties of the material. The latter component design method has little effect on the deposited metal A C1 point, but the cobalt is expensive and increases the cost of the welding consumable. Therefore, it is necessary to provide a special welding material for T/P92 steel which can suppress the formation of δ-ferrite of the deposited metal, and has a high A C1 point of the deposited metal, excellent high temperature creep resistance and low cost.
发明内容Summary of the invention
针对现有技术存在的问题，本发明为解决现有技术中存在的问题采用的技术方案如下：In view of the problems existing in the prior art, the technical solution adopted by the present invention to solve the problems existing in the prior art is as follows:
一种抗高温蠕变的低镍含铜型T/P92钢焊材，其特征在于：该焊材包括如下组分C、Mn、Si、Cr、Ni、W、Mo、Nb、V、N、B、Al、Ti、S、P、Fe和Cu。Low-nickel copper-containing T/P92 steel welding material resistant to high temperature creep, characterized in that the welding consumable comprises the following components C, Mn, Si, Cr, Ni, W, Mo, Nb, V, N, B, Al, Ti, S, P, Fe and Cu.
所述焊材中铜含量(wt.％)为：0.8-1.5。The copper content (wt.%) in the consumable is: 0.8-1.5.
所述焊材中各组分的含量(wt.％)为：C 0.07-0.12、Mn 0.30-0.60、Si≤0.40、Cr 8.50-9.50、Ni≤0.40、W 1.50-2.00、Mo 0.30-0.60、Cu 0.8-1.5、Nb 0.04-0.07、V 0.15-0.25、N 0.03-0.07、B 0.001-0.005、Al≤0.03、Ti≤0.01、S≤0.01、P≤0.02、余量为Fe。The content (wt.%) of each component in the welding consumable is: C 0.07-0.12, Mn 0.30-0.60, Si≤0.40, Cr 8.50-9.50, Ni≤0.40, W 1.50-2.00, Mo 0.30-0.60, Cu 0.8-1.5, Nb 0.04-0.07, V 0.15-0.25, N 0.03-0.07, B 0.001-0.005, Al ≤ 0.03, Ti ≤ 0.01, S ≤ 0.01, P ≤ 0.02, and the balance is Fe.
本发明的技术方案是通过计算熔敷金属铬当量和光学金相观察分析，得到抑制δ-铁素体形成所需的最低铜含量；通过材料热力学计算和热膨胀法定量研究铜含量对熔敷金属A C1点的影响；通过高温蠕变断裂试验研究铜含量对熔敷金属蠕变性能的影响，并通过电镜等微观分析实验手段研究熔敷金属蠕变试样中铜粒子分布及尺寸，掌握铜元素在T/P92钢中的高温强化机制，确定强化效果最佳的铜含量范围。综合上述3个方面的研究结果，确定含铜型T/P92钢焊材熔敷金属的铜含量范围，并对锰和镍等奥氏体化元素含量进行相应调整。 The technical scheme of the invention is to obtain the minimum copper content required for inhibiting the formation of δ-ferrite by calculating the chromium equivalent of the deposited metal and the observation of the optical metal phase; quantitatively studying the copper content on the deposited metal by thermodynamic calculation and thermal expansion method of the material The influence of A C1 point; the effect of copper content on the creep properties of deposited metal was studied by high temperature creep rupture test, and the distribution and size of copper particles in the deposited metal creep sample were studied by microscopic analysis experiments such as electron microscopy. The high temperature strengthening mechanism of the element in T/P92 steel determines the range of copper content that has the best strengthening effect. Based on the results of the above three aspects, the copper content of the copper-containing T/P92 steel welding consumable metal was determined, and the austenitizing elements such as manganese and nickel were adjusted accordingly.
本发明的抗高温蠕变用T/P92钢焊接材料熔敷金属的成分特点考虑了如下因素：The composition characteristics of the deposited metal of the T/P92 steel welding material for high temperature creep resistance of the present invention take into account the following factors:
碳：C是奥氏体稳定化元素，可以稳定回火马氏体显微组织，并且形成碳化物提高蠕变强度。当C含量低于0.07％时，焊缝易形成δ-铁素体，且碳化物数量少，对蠕变强度不利。但C含量过高，增大焊接裂纹敏感性，因此本发明的C含量范围控制在0.07-0.12％。Carbon: C is an austenite stabilizing element that stabilizes the tempered martensite microstructure and forms carbides to increase creep strength. When the C content is less than 0.07%, the weld is liable to form δ-ferrite, and the amount of carbide is small, which is unfavorable for creep strength. However, the C content is too high to increase the weld crack sensitivity, so the C content range of the present invention is controlled to be 0.07 to 0.12%.
锰和镍：Mn是奥氏体稳定化元素，有利于抑制δ-铁素体，同时Mn有脱氧去硫作用，能增加焊缝的强度和韧性。但是Mn含量过高，明显降低焊缝的A C1点，导致焊缝在最高焊后热处理温度下重新形成奥氏体，此外Mn含量超过1.5％显著降低蠕变强度。Ni也是奥氏体形成元素，对抑制δ-铁素体形成和稳定马氏体组织有积极作用，故可以提高焊缝的冲击韧性。为了抑制T/P91、T/P92等新型9％Cr热强钢焊缝形成δ-铁素体，欧洲BS EN标准规定了最高Ni含量为0.8％，甚至1.0％，明显高于T/P91、T/P92钢的Ni含量上限值(0.4％)。但是，提高Ni含量显著降低A C1点，导致焊缝在最高焊后热处理温度下重新形成奥氏体，此外，有研究表明，当高铬热强钢中的Ni含量超过0.4％时，加速长期蠕变过程中M 23C 6型碳化物的粗化和Z相的形成，降低蠕变性能。综合考虑，本发明将Mn含量控制在0.30-1.0％，Ni含量控制在0.40％以内，且Mn+Ni的总含量控制在1.0％以下，比目前MTS616、Chromet 92和9CrWV等国外牌号T/P92钢焊材熔敷金属的Ni含量和Mn+Ni的总含量降低50％左右。 Manganese and Nickel: Mn is an austenite stabilizing element, which is beneficial to inhibit δ-ferrite. At the same time, Mn has deoxidation and desulfurization, which can increase the strength and toughness of the weld. However, the Mn content is too high, which significantly reduces the A C1 point of the weld, resulting in the austenite being re-formed at the highest post-weld heat treatment temperature. In addition, the Mn content exceeding 1.5% significantly reduces the creep strength. Ni is also an austenite forming element and has a positive effect on suppressing the formation of δ-ferrite and stabilizing the martensite structure, so that the impact toughness of the weld can be improved. In order to suppress the formation of δ-ferrite in the new 9%Cr heat-strength steel welds such as T/P91 and T/P92, the European BS EN standard stipulates that the highest Ni content is 0.8% or even 1.0%, which is significantly higher than T/P91. The upper limit of the Ni content of T/P92 steel (0.4%). However, increasing the Ni content significantly reduces the A C1 point, causing the weld to re-form austenite at the highest post-weld heat treatment temperature. In addition, studies have shown that when the Ni content in the high chromium heat-strength steel exceeds 0.4%, the acceleration is accelerated. The roughening of the M 23 C 6 type carbide during the creep process and the formation of the Z phase reduce the creep properties. Considering comprehensively, the present invention controls the Mn content to be 0.30-1.0%, the Ni content to be controlled within 0.40%, and the total content of Mn+Ni is controlled to be less than 1.0%, which is higher than the current foreign brands such as MTS616, Chromet 92 and 9CrWV. The Ni content of the deposited metal of the steel consumables and the total content of Mn+Ni are reduced by about 50%.
硅：Si是一种重要的脱氧剂，且可以提高焊缝的抗氧化性能。适当低的Si含量有利于提高焊缝金属的韧性，根据美国一些技术标准规定焊缝的Si含量需低于0.30％，本发明的Si含量控制在0.1％-0.40％，比P92钢的Si含量上限(0.5％) 更低。Silicon: Si is an important deoxidizer and can improve the oxidation resistance of the weld. A suitably low Si content is beneficial to improve the toughness of the weld metal. According to some technical standards in the United States, the Si content of the weld is required to be less than 0.30%, and the Si content of the present invention is controlled to be 0.1%-0.40%, which is higher than the Si content of the P92 steel. The upper limit (0.5%) is lower.
铬：Cr是保证抗蒸汽氧化和热腐蚀最重要的元素。随着Cr含量的增加，焊缝的抗蒸汽腐蚀性能越好。但是，Cr为铁素体形成元素，其含量过高时，焊缝中将产生δ-铁素体，降低焊缝的冲击韧性和蠕变强度。因此，本发明的Cr含量控制在8.5-9.5％。Chromium: Cr is the most important element to ensure resistance to steam oxidation and hot corrosion. As the Cr content increases, the weld's resistance to steam corrosion is better. However, Cr is a ferrite forming element, and when the content is too high, δ-ferrite is generated in the weld, and the impact toughness and creep strength of the weld are lowered. Therefore, the Cr content of the present invention is controlled to be 8.5 to 9.5%.
钨和钼：W和Mo都为铁素体形成元素，不利于防止焊缝形成δ-铁素体，但它们是T/P92钢中最重要的固溶强化元素，并且能提高碳化物的稳定性而起到间接强化作用。为保证焊缝的高温蠕变强度，本发明的W和Mo含量范围与T/P92钢相当，分别为1.5-2.0％和0.3-0.6％。Tungsten and Molybdenum: Both W and Mo are ferrite forming elements, which are not conducive to the formation of δ-ferrite in welds, but they are the most important solid solution strengthening elements in T/P92 steel and can improve the stability of carbides. Sexuality plays an indirect strengthening role. In order to ensure the high temperature creep strength of the weld, the W and Mo content ranges of the present invention are comparable to those of the T/P92 steel, which are 1.5-2.0% and 0.3-0.6%, respectively.
铜：加Cu是本发明的主要创新点，因为T/P92钢及现有的T/P92钢焊接材料熔敷金属中均不含Cu。Cu的主要作用有：Cu为奥氏体形成元素，可抑制焊缝中形成δ-铁素体，此外，发明人的试验研究表明，含铜的T/P92钢焊缝在经历焊后热处理后，焊态下固溶的Cu以ε-Cu粒子析出，它在板条内和板条界分散分布，且在板条界的数量密度较高，如图1所示。因此，与M 23C 6型碳化物一样，它可以在长期蠕变过程中阻止亚晶界的迁移而提高蠕变强度，如图2所示。Cu含量范围的确定需考虑抑制铁素体形成、充分发挥其高温强化作用以及避免A C1点明显降低这3个因素。本发明是这样确定其含量范围的：根据铬当量思想确定的铁素体含量计算方法(参考中国专利ZL201210192206.X)，在抑制铁素体形成能力上，Cu与Co相当，约为Mn的1.5倍，约为Ni的60％，即保持相同的抑制铁素体效果，焊缝中每加入1％的Cu，可减少1.5％的Mn，或减少0.6％的Ni。对于高温强化的影响，当Cu含量低于0.5％时，Cu元素基本上固溶在基体中，析出的ε-Cu数量很少，沉淀强化效果不大；试验研究表明，当 Cu含量超过1.5％时，ε-Cu在长期蠕变过程中聚集粗化(图3和图4)，不仅减弱强化效果，而且降低持久塑性。关于Cu含量对A C1点的影响，Cu虽为扩大奥氏体相区元素，降低A C1点，但专利号为ZL201210131877.5的专利表明，Cu降低A C1点的幅度小于Mn和Ni，此外，热力学计算和实测结果表明，当Cu含量超过0.7％时，继续增加Cu含量，对A C1点几乎没有影响，如图5-图7所示。综合考虑上述3个因素的铜加入量，最终确定本发明的铜含量范围为：0.8-1.5％。 Copper: Adding Cu is the main innovation of the present invention because both T/P92 steel and existing T/P92 steel welding materials do not contain Cu. The main functions of Cu are: Cu is an austenite forming element, which can inhibit the formation of δ-ferrite in the weld. In addition, the inventors' experimental research shows that the copper-containing T/P92 steel weld is subjected to post-weld heat treatment. The solid solution of Cu in the as-welded state is precipitated by ε-Cu particles, which are dispersed in the slats and the slats, and have a high number density at the slab boundary, as shown in FIG. Therefore, like the M 23 C 6 type carbide, it can prevent the migration of the subgrain boundary and increase the creep strength during long-term creep, as shown in Fig. 2. The determination of the range of Cu content should consider the three factors of inhibiting the formation of ferrite, fully exerting its high-temperature strengthening effect, and avoiding a significant decrease in the A C1 point. The present invention determines the content range thereof: the ferrite content calculation method determined according to the chromium equivalent concept (refer to Chinese patent ZL201210192206.X), Cu is equivalent to Co in suppressing ferrite formation ability, and is about 1.5 of Mn. The ratio is about 60% of Ni, that is, the same effect of suppressing ferrite is maintained. For every 1% of Cu added in the weld, 1.5% of Mn can be reduced, or 0.6% of Ni can be reduced. For the effect of high temperature strengthening, when the Cu content is less than 0.5%, Cu element is basically dissolved in the matrix, the amount of ε-Cu precipitated is small, and the precipitation strengthening effect is not large; experimental research shows that when the Cu content exceeds 1.5% At the same time, ε-Cu aggregates and coarsens during long-term creep (Fig. 3 and Fig. 4), which not only weakens the strengthening effect but also reduces the long-lasting plasticity. Regarding the effect of Cu content on the A C1 point, although Cu expands the austenite phase region element and lowers the A C1 point, the patent No. ZL201210131877.5 shows that Cu reduces the A C1 point by less than Mn and Ni. Thermodynamic calculations and measured results show that when the Cu content exceeds 0.7%, the Cu content is continuously increased, and there is almost no influence on the A C1 point, as shown in Fig. 5-7. Considering the copper addition amount of the above three factors, it is finally determined that the copper content of the present invention ranges from 0.8 to 1.5%.
铌：Nb是强碳化物形成元素，它与C、N形成细小弥散的MX型第二相析出物，其在高温下非常稳定，从而提高焊缝的高温蠕变强度。当其含量低于0.04％时，析出物量少，不能得到充足的强化效果，但是研究发现Nb含量高，降低焊缝的冲击韧性。为此，本发明将Nb含量控制在0.04％-0.07％，上限比T/P92钢的0.09％稍低。铌: Nb is a strong carbide forming element, which forms a finely dispersed MX type second phase precipitate with C and N, which is very stable at high temperatures, thereby improving the high temperature creep strength of the weld. When the content is less than 0.04%, the amount of precipitates is small, and sufficient strengthening effect cannot be obtained, but it has been found that the Nb content is high and the impact toughness of the weld is lowered. To this end, the present invention controls the Nb content to be 0.04% to 0.07%, and the upper limit is slightly lower than 0.09% of the T/P92 steel.
钒：V是强碳化物形成元素，它与C、N形成细小弥散、稳定的MX型第二相析出物，提高焊缝的高温蠕变强度。其对焊缝韧性的影响较小，为了保证焊缝的抗高温蠕变性能，本发明的V含量与T/P92钢相当，控制在0.15％-0.25％。Vanadium: V is a strong carbide forming element, which forms a finely dispersed and stable MX type second phase precipitate with C and N, which improves the high temperature creep strength of the weld. The influence on the weld toughness is small. In order to ensure the high temperature creep resistance of the weld, the V content of the present invention is equivalent to that of the T/P92 steel, and is controlled at 0.15% to 0.25%.
氮：N与Nb、V形成细小弥散的MX型第二相析出物，显著提高焊缝的高温蠕变强度。其对焊缝韧性的影响较小，为了保证焊缝的抗高温蠕变性能，本发明的N含量与T/P92钢相当，控制在0.04％-0.07％。Nitrogen: N forms a finely dispersed MX type second phase precipitate with Nb and V, which significantly improves the high temperature creep strength of the weld. The influence on the weld toughness is small. In order to ensure the high temperature creep resistance of the weld, the N content of the present invention is equivalent to that of the T/P92 steel, and is controlled at 0.04%-0.07%.
硼：B是晶界强化元素，可以提高焊缝的高温蠕变强度，但是硼在焊接过程中易烧损。为了保证焊缝的抗高温蠕变性能，本发明的B含量控制在0.001％-0.005％，略低于T/P92钢的上限值(0.006％)。Boron: B is a grain boundary strengthening element, which can improve the high temperature creep strength of the weld, but boron is easily burned during the welding process. In order to ensure the high temperature creep resistance of the weld, the B content of the present invention is controlled to be 0.001% to 0.005%, which is slightly lower than the upper limit value (0.006%) of the T/P92 steel.
铝：Al在焊材中是作为脱氧剂加入的，焊缝中残留的Al含量过高，降低焊缝的持久塑性。此外，Al容易与N优先结合，使得焊缝中固溶的N近似为零， 无法形成析出强化作用，降低焊缝的高温蠕变强度。为此，本发明的Al含量控制在0.03％以下。Aluminium: Al is added as a deoxidizer in the consumables. The residual Al content in the weld is too high, which reduces the permanent plasticity of the weld. In addition, Al is easily combined with N preferentially, so that the N dissolved in the weld is approximately zero, and precipitation strengthening is not formed, and the high temperature creep strength of the weld is lowered. For this reason, the Al content of the present invention is controlled to be 0.03% or less.
钛：Ti是一种极强的碳化物形成元素，影响Nb、V与C、N的结合，同时会形成一次TiN，不利于发挥沉淀强化作用。因此，本发明的Ti含量控制在0.01％以下。Titanium: Ti is a very strong carbide forming element, which affects the combination of Nb and V with C and N, and forms TiN once, which is not conducive to the precipitation strengthening effect. Therefore, the Ti content of the present invention is controlled to be 0.01% or less.
硫和磷：S和P是焊缝中不可避免的杂质元素，它们增大焊缝的裂纹倾向，并且降低焊缝的蠕变断裂塑性。因此，本发明将S和P含量分别控制在0.01％和0.02％以内。Sulfur and Phosphorus: S and P are inevitable impurity elements in the weld, which increase the tendency of the weld to crack and reduce the creep fracture plasticity of the weld. Therefore, the present invention controls the S and P contents to be within 0.01% and 0.02%, respectively.
本发明具有如下优点：The invention has the following advantages:
(1)本发明焊材加入铜，减少了镍元素含量，不加贵重元素钴，降低了材料成本，其熔敷金属在抑制铁素体形成的同时，避免了A C1点的显著降低，且其常温力学性能达到或超过现有高镍或加钴的T/P92钢焊材； (1) The welding material of the invention is added with copper, the nickel element content is reduced, the precious element cobalt is not added, the material cost is reduced, and the deposited metal suppresses the formation of ferrite while avoiding a significant decrease of the A C1 point, and Its normal temperature mechanical properties meet or exceed the existing high nickel or cobalt added T/P92 steel welding consumables;
(2)本发明焊材具有优异的抗高温蠕变性能，其熔敷金属的长时持久断裂寿命最接近于P92钢的平均值。(2) The welding consumable of the invention has excellent high temperature creep resistance, and the long-term and long-lasting fracture life of the deposited metal is closest to the average value of the P92 steel.
附图说明DRAWINGS
图1本发明焊材熔敷金属在760℃×4h回火后的析出相；Figure 1 shows the precipitated phase of the deposited metal of the welding consumable of the present invention after tempering at 760 ° C for 4 h;
图2本发明焊材实施例在650℃/100Ma/4897.1h持久试验后的析出相；Figure 2 is a precipitation phase of the embodiment of the welding consumable of the present invention after a long-term test at 650 ° C / 100 Ma / 4897.1 h;
图3含1.69％Cu的T/P92焊材熔敷金属在760℃×4h回火后的析出相；Figure 3 shows the precipitated phase of 1.6% Cu T/P92 consumable deposited metal after tempering at 760 ° C × 4 h;
图4含1.69％Cu的T/P92焊材熔敷金属在650℃/100Ma/3896.5h持久试验后的析出相；Figure 4 shows the precipitated phase of the T/P92 consumable deposited metal containing 1.69% Cu after 650 ° C / 100 Ma / 3896.5 h long-term test;
图5为铜含量对P92焊缝A C1点影响的热力学计算结果； Figure 5 is a thermodynamic calculation of the effect of copper content on the A C1 point of the P92 weld;
图6本发明焊材实施例熔敷金属A C1点的热膨胀法实测结果； Figure 6 shows the results of the thermal expansion method of the deposited metal A C1 point of the welding material embodiment of the present invention;
图7本发明焊材对比例熔敷金属A C1点的热膨胀法实测结果； Figure 7 is a graph showing the results of thermal expansion of the comparatively deposited metal A C1 point of the welding consumable of the present invention;
图8为本发明焊材熔敷金属在760℃×4h回火后的显微组织(焊条电弧焊)；Figure 8 is a microstructure (electrode arc welding) of the welding consumable metal of the present invention after tempering at 760 ° C for 4 h;
图9本发明焊材实施例和对比例在650℃/100Ma持久断裂时间的比较；Figure 9 is a comparison of the welding material examples and comparative examples of the present invention at a permanent breaking time of 650 ° C / 100 Ma;
具体实施方式Detailed ways
下面通过实施例，并结合附图，对本发明的技术方案作进一步具体的说明，如图1-9所示：The technical solution of the present invention will be further specifically described below by way of embodiments and with reference to the accompanying drawings, as shown in FIG. 1-9:
由附图1看出，本发明焊材熔敷金属在760℃×4h回火后，马氏体板条界上除析出M 23C 6型碳化物外，还析出较细小的ε-Cu粒子。 It can be seen from Fig. 1 that after the tempered metal of the welding consumable of the present invention is tempered at 760 ° C for 4 h, in addition to the M 23 C 6 type carbide precipitated on the martensite lath boundary, fine ε-Cu particles are precipitated. .
由附图2看出，本发明焊材熔敷金属在650℃/100Ma/4897.1h蠕变后，马氏体板条界上的ε-Cu粒子非常稳定，没有明显聚集长大。It can be seen from Fig. 2 that after the creeping of the consumable deposited metal of the present invention at 650 ° C / 100 Ma / 4897.1 h, the ε-Cu particles on the martensite lath boundary are very stable and do not significantly aggregate and grow.
由附图3和附图4看出，当T/P92焊缝中的Cu含量超过1.5％时，焊缝金属在760℃×4h回火后的马氏体板条界上析出的ε-Cu粒子虽较细小，但在650℃/100Ma/3896.5h持久试验后出现明显的聚集长大。3 and 4, when the Cu content in the T/P92 weld is more than 1.5%, the weld metal is ε-Cu precipitated on the martensite lath after tempering at 760 ° C × 4 h. Although the particles were fine, they showed significant aggregation growth after a long-term test at 650 ° C / 100 Ma / 3896.5 h.
由附图5看出，当Cu含量超过0.7％时，继续增加Cu含量，对A C1点几乎没有影响。 As seen from Fig. 5, when the Cu content exceeds 0.7%, the Cu content is continuously increased, and there is almost no influence on the A C1 point.
由附图6看出，本发明焊材焊缝金属的A C1点为809℃，较焊后热处理温度(760℃)高出49℃，满足焊后热处理温度比A C1点低20-30℃以上的要求，余量较大。 It can be seen from Fig. 6 that the A C1 point of the weld metal of the welding material of the present invention is 809 ° C, which is 49 ° C higher than the post-weld heat treatment temperature (760 ° C), and the post-weld heat treatment temperature is 20-30 ° C lower than the A C1 point. The above requirements have a large margin.
由附图7看出，含1.69％Cu的焊材焊缝金属的A C1点为805℃，与含0.86Cu％的焊缝金属A C1点差别不大，实验证实了当Cu含量超过0.7％时，继续增加Cu含量，对T/P92焊缝金属A C1点几乎没有影响。 It can be seen from Fig. 7 that the A C1 point of the weld metal containing 1.69% Cu is 805 ° C, which is not much different from the weld metal A C1 point containing 0.86 Cu%. The experiment confirmed that when the Cu content exceeds 0.7% At the same time, increasing the Cu content has almost no effect on the A/ C1 point of the T/P92 weld metal.
由附图8看出，本发明焊材焊缝金属为回火板条马氏体组织，没有铁素体。As seen from Fig. 8, the weld metal of the welding material of the present invention is a tempered lath martensite structure without ferrite.
由附图9看出，本发明T/P92钢焊材焊缝金属(1#)在650℃/100Ma的持久寿命最长，超过T/P92钢持久寿命的平均值，明显高于现有高镍或加钴的T/P92钢焊材焊缝金属(6#-8#)。It can be seen from Fig. 9 that the weld metal (1#) of the T/P92 steel welding material of the present invention has the longest life at 650 ° C / 100 Ma, and exceeds the average life of the T / P 92 steel, which is significantly higher than the existing high. Nickel or cobalt-added T/P92 steel welding consumable metal (6#-8#).
而含1.69％Cu的T/P92焊材熔敷金属(5#)的持久寿命较1#降低，说明当Cu含量超过本发明的上限时(1.5％)，对持久性能的不利影响较大。The durability of the T/P92 consumable deposited metal (5#) containing 1.69% Cu is lower than that of 1#, indicating that when the Cu content exceeds the upper limit of the invention (1.5%), the adverse effect on the long-term performance is large.
按照本发明技术方案中的材料组分配比设计焊材的熔敷金属在760℃×4h回火后的组织特征和性能：According to the technical solution of the present invention, the distribution characteristics of the material group after the tempering of the deposited metal of the welding consumable at 760 ° C × 4 h:
(1)焊缝为全回火马氏体组织，没有铁素体；(1) The weld is a fully tempered martensite structure without ferrite;
(2)焊缝A C1点≥805℃； (2) Weld A C1 point ≥ 805 ° C;
(3)焊缝的室温力学性能：R p0.2(σ 0.2)≥550MPa，R m(σ b)≥680MPa,A(δ 0.5)≥18，KV 2≥47J，满足GB/T5118-2012标准和ASME SFA-5.5-2015标准对T/P92钢焊材熔敷金属室温力学性能的要求：R p0.2(σ 0.2)≥530MPa，R m(σ b)≥620MPa,A(δ 0.5)≥15或17％(GB/T5118标准规定为15％，ASME标准规定为17％)； (3) The room temperature mechanical properties of the weld: R p0.2 (σ 0.2 ) ≥ 550 MPa, R m (σ b ) ≥ 680 MPa, A (δ 0.5 ) ≥ 18, KV 2 ≥ 47 J, meeting the GB/T 5118-2012 standard And ASME SFA-5.5-2015 standard for the mechanical properties of T/P92 steel welding consumables at room temperature: R p0.2 (σ 0.2 ) ≥ 530MPa, R m (σ b ) ≥ 620MPa, A (δ 0.5 ) ≥ 15 or 17% (15% for GB/T5118 and 17% for ASME);
(4)持久性能：650℃/100MPa下的持久寿命≥4500h。(4) Durable performance: long-lasting life at 650 ° C / 100 MPa ≥ 4500 h.
根据本发明的成分范围，以焊条为例，对本发明低镍含铜型T/P92钢焊材做了多组实施例，铜元素通过药皮或焊芯添加。对比例1的铜含量范围超过本发明的上限(1.5％)，是为了说明铜含量过高对焊缝性能的影响。为了对比，在相同焊接工艺(预热200-250℃、电流130-180A，电压24-30V、层间温度≤350℃)和焊后热处理工艺(760℃×4h)条件下，与目前3种典型T/P92钢焊条——德国蒂森MTS616焊条(提高锰元素和镍元素含量)、日本神钢CR-12S焊条(加钴元素)、奥林康的ALCROMOCORD 92焊条(加钴元素)，进行了熔敷金属性 能的比较。表1列出了7种T/P92钢焊条熔敷金属的化学成分。According to the composition range of the present invention, a plurality of sets of examples are described for the low nickel copper-containing T/P92 steel welding material of the present invention, and the copper element is added through the coating or the welding core. The copper content of Comparative Example 1 exceeded the upper limit (1.5%) of the present invention in order to explain the effect of excessive copper content on weld bead performance. For comparison, under the same welding process (preheating 200-250 ° C, current 130-180 A, voltage 24-30 V, interlayer temperature ≤ 350 ° C) and post-weld heat treatment process (760 ° C × 4 h), and currently 3 kinds Typical T/P92 steel welding rod - Germany Thyssen MTS616 electrode (increased manganese and nickel content), Japan Kobelco CR-12S electrode (cobalt added), Olympus' ALCROMOCORD 92 electrode (plus cobalt), A comparison of the properties of deposited metal. Table 1 lists the chemical composition of the seven T/P92 steel electrode deposited metals.
表1 实施例及对比例熔敷金属的化学成分(wt％)Table 1 Chemical composition (wt%) of the deposited metal of the examples and comparative examples
Figure PCTCN2018097698-appb-000001
Figure PCTCN2018097698-appb-000001
本发明实施例的各项性能测试结果如表2-表3所示。由表2看出，本发明焊条熔敷金属的室温力学性能与MTS616焊条熔敷金属相当，室温冲击韧性低于CR-12S焊条熔敷金属，但室温拉伸强度和冲击韧性整体优于ALCROMOCORD 92焊条熔敷金属。从表3看出，本发明焊条熔敷金属在长期时效后的冲击功与MTS616、CR-12S和ALCROMOCORD 92焊条熔敷金属相当。从表4看出，在抗高温蠕变用焊材最重要的性能指标方面，本发明焊条熔敷金属的长时持久性能明显好于CR-12S焊条熔敷金属，也优于MTS616、ALCROMOCORD 92焊条熔敷金属，其在650℃/100MPa下的蠕变断裂寿命超过了2005年ECCC公布的P92钢蠕变断裂寿命平均值(4735h)。对比例1的铜 含量范围超过本发明的上限，其持久寿命较实施例有所下降。The performance test results of the embodiments of the present invention are shown in Table 2 - Table 3. It can be seen from Table 2 that the room temperature mechanical properties of the deposited metal of the electrode of the present invention are comparable to those of the MTS616 electrode deposited metal, and the room temperature impact toughness is lower than that of the CR-12S electrode deposited metal, but the tensile strength and impact toughness at room temperature are better than ALCROMOCORD 92 overall. The electrode is deposited with metal. It can be seen from Table 3 that the impact work of the electrode deposited metal of the present invention after long-term aging is equivalent to that of MTS616, CR-12S and ALCROMOCORD 92 electrodes. It can be seen from Table 4 that the long-term durability of the electrode deposited metal of the present invention is significantly better than that of the CR-12S electrode deposited metal in terms of the most important performance index of the welding material for high temperature creep resistance, and is superior to MTS616 and ALCROMOCORD 92. The electrode deposited metal has a creep rupture life at 650 ° C / 100 MPa exceeding the average creep creep life of P92 steel published by the ECCC in 2005 (4735 h). The copper content of Comparative Example 1 exceeded the upper limit of the present invention, and its endurance life was decreased as compared with the examples.
表2 实施例及对比例的室温力学性能Table 2 Room temperature mechanical properties of the examples and comparative examples
Figure PCTCN2018097698-appb-000002
Figure PCTCN2018097698-appb-000002
表3 实施例及对比例在650℃时效后的室温冲击功(J)Table 3 Room temperature impact work after aging at 650 ° C in the examples and comparative examples (J)
Figure PCTCN2018097698-appb-000003
Figure PCTCN2018097698-appb-000003
表4 实施例及对比例在650℃不同应力下的持久断裂时间(h)Table 4 Long-term rupture time (h) of the examples and comparative examples at different stresses at 650 ° C
Figure PCTCN2018097698-appb-000004
Figure PCTCN2018097698-appb-000004
综上所述，本发明抗高温蠕变P92焊材所采取的以低成本的铜元素替代镍 元素或昂贵的钴元素的合金组分设计，在保证熔敷金属的室温力学性能和长时时效冲击功的前提下，提高了熔敷金属长时持久性能这一最重要的性能指标，具有性价比高的优点。In summary, the high temperature creep resistant P92 welding material of the present invention adopts a low cost copper element instead of a nickel element or an expensive alloying alloy component design to ensure the room temperature mechanical properties and long-term aging of the deposited metal. Under the premise of impact energy, the most important performance index of the long-term performance of the deposited metal is improved, and the cost performance is high.
本发明的保护范围并不限于上述的实施例，显然，本领域的技术人员可以对本发明进行各种改动和变形而不脱离本发明的范围和精神。倘若这些改动和变形属于本发明权利要求及其等同技术的范围内，则本发明的意图也包含这些改动和变形在内。The scope of the present invention is not limited to the embodiments described above, and it is obvious that those skilled in the art can make various modifications and changes to the invention without departing from the scope and spirit of the invention. Such changes and modifications are intended to be included within the scope of the appended claims.

Claims (3)

  1. 一种抗高温蠕变的低镍含铜型T/P92钢焊材，其特征在于：该焊材包括如下组分C、Mn、Si、Cr、Ni、W、Mo、Nb、V、N、B、Al、Ti、S、P、Fe和Cu。Low-nickel copper-containing T/P92 steel welding material resistant to high temperature creep, characterized in that the welding consumable comprises the following components C, Mn, Si, Cr, Ni, W, Mo, Nb, V, N, B, Al, Ti, S, P, Fe and Cu.
  2. 如权利要求1所述的一种抗高温蠕变的低镍含铜型T/P92钢焊材，其特征在于：所述焊材中铜含量(wt.％)为：0.8-1.5。A low-nickel copper-containing T/P92 steel welding material resistant to high temperature creep according to claim 1, wherein the welding material has a copper content (wt.%) of 0.8-1.5.
  3. 如权利要求1所述的一种抗高温蠕变的低镍含铜型T/P92钢焊材，其特征在于：所述焊材中各组分的含量(wt.％)为：C 0.07-0.12、Mn 0.30-0.60、Si≤0.40、Cr 8.50-9.50、Ni≤0.40、W 1.50-2.00、Mo 0.30-0.60、Cu 0.8-1.5、Nb 0.04-0.07、V 0.15-0.25、N 0.03-0.07、B 0.001-0.005、Al≤0.03、Ti≤0.01、S≤0.01、P≤0.02、余量为Fe。A low-nickel copper-containing T/P92 steel welding material resistant to high temperature creep according to claim 1, wherein the content (wt.%) of each component in the welding consumable is: C 0.07- 0.12, Mn 0.30-0.60, Si≤0.40, Cr 8.50-9.50, Ni≤0.40, W 1.50-2.00, Mo 0.30-0.60, Cu 0.8-1.5, Nb 0.04-0.07, V 0.15-0.25, N 0.03-0.07, B 0.001-0.005, Al ≤ 0.03, Ti ≤ 0.01, S ≤ 0.01, P ≤ 0.02, and the balance is Fe.
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CN107138876B (en) * 2017-06-30 2022-05-24 武汉大学 High-temperature creep resistant low-nickel copper-containing T/P92 steel welding material
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CN110142530B (en) * 2019-06-18 2021-02-09 清河县联盛焊接材料有限公司 Welding electrode suitable for welding of various steel grades, application and preparation method thereof
US11772207B2 (en) * 2019-09-20 2023-10-03 Lincoln Global, Inc. High chromium creep resistant weld metal for arc welding of thick walled steel members
US11772206B2 (en) * 2019-09-20 2023-10-03 Lincoln Global, Inc. High chromium creep resistant weld metal for arc welding of thin walled steel members
CN112935620B (en) * 2021-01-14 2023-06-06 僖昴晰(上海)新材料有限公司 Metal composition for welding

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000301377A (en) * 1999-04-16 2000-10-31 Sumitomo Metal Ind Ltd Welded joint of ferritic heat resistant steel and welding material
JP2004042116A (en) * 2002-07-12 2004-02-12 Kobe Steel Ltd WELDING WIRE FOR HIGH Cr FERRITIC HEAT RESISTANT STEEL
CN1727108A (en) * 2004-05-18 2006-02-01 株式会社神户制钢所 Welding wire for modified 9Cr-1Mo steel, and submerged-arc welding material
CN101407002A (en) * 2008-11-28 2009-04-15 中国电力科学研究院 Back slag self-protecting flux-cored wire for T92/P92 steel tungsten electrode argon arc backing weld
CN102189352A (en) * 2010-10-15 2011-09-21 东方电气集团东方锅炉股份有限公司 P92 steel submerged arc welding wire
CN107138876A (en) * 2017-06-30 2017-09-08 武汉大学 A kind of low nickel cupric type T/P92 steel wldings of high temperature creep-resisting

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103336102B (en) * 2012-06-12 2015-01-14 武汉大学 Method for determination of delta-ferrite content in martensite refractory steel welding seam with 9-12% of Cr
CN102747287A (en) * 2012-07-31 2012-10-24 宝山钢铁股份有限公司 High-temperature resistant pipe suitable for delayed coking process and producing method of high-temperature resistant pipe
CN103045962B (en) * 2012-12-26 2014-11-05 钢铁研究总院 Steel for steam-temperature ultra-supercritical thermal power unit and preparation method thereof
CN105970099B (en) * 2016-06-28 2017-12-19 哈尔滨工程大学 A kind of steel of crack arrest containing Cu and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000301377A (en) * 1999-04-16 2000-10-31 Sumitomo Metal Ind Ltd Welded joint of ferritic heat resistant steel and welding material
JP2004042116A (en) * 2002-07-12 2004-02-12 Kobe Steel Ltd WELDING WIRE FOR HIGH Cr FERRITIC HEAT RESISTANT STEEL
CN1727108A (en) * 2004-05-18 2006-02-01 株式会社神户制钢所 Welding wire for modified 9Cr-1Mo steel, and submerged-arc welding material
CN101407002A (en) * 2008-11-28 2009-04-15 中国电力科学研究院 Back slag self-protecting flux-cored wire for T92/P92 steel tungsten electrode argon arc backing weld
CN102189352A (en) * 2010-10-15 2011-09-21 东方电气集团东方锅炉股份有限公司 P92 steel submerged arc welding wire
CN107138876A (en) * 2017-06-30 2017-09-08 武汉大学 A kind of low nickel cupric type T/P92 steel wldings of high temperature creep-resisting

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