WO2023061514A1 - 一种海洋工程用Cu-15Ni-8Sn基合金及其制备方法 - Google Patents

一种海洋工程用Cu-15Ni-8Sn基合金及其制备方法 Download PDF

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WO2023061514A1
WO2023061514A1 PCT/CN2022/135142 CN2022135142W WO2023061514A1 WO 2023061514 A1 WO2023061514 A1 WO 2023061514A1 CN 2022135142 W CN2022135142 W CN 2022135142W WO 2023061514 A1 WO2023061514 A1 WO 2023061514A1
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alloy
source
based alloy
melt
pure
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French (fr)
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周延军
杨少丹
宋克兴
杨冉
张彦敏
周菲
郁炎
陈纪东
柳亚辉
彭晓文
肖柱
郭慧稳
张学宾
岳鹏飞
张国赏
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河南科技大学
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
    • B22D27/02—Use of electric or magnetic effects
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D7/00—Casting ingots, e.g. from ferrous metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon

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  • the invention belongs to the technical field of metal materials, and in particular relates to a Cu-15Ni-8Sn-based alloy for marine engineering and a preparation method thereof.
  • Copper alloys are widely used in the fields of ships, offshore oil and gas exploitation, and comprehensive utilization of seawater resources due to their good mechanical properties, cold and hot processing properties, high heat transfer coefficient, excellent resistance to marine organisms, and seawater corrosion resistance.
  • the main application scenarios include: seawater pump valves and filters, condenser tubes for ship steam turbines, copper tubes for heat exchangers, propellers, oil drilling tools and equipment components, etc.
  • Commonly used corrosion-resistant copper alloy systems mainly include aluminum brass and tin brass such as HSn70-1 and HSn60-1, tin bronze such as QSn4-4-4, QSn-5-5 and QSn6-6-3, B10(Cu- 10Ni-1Fe-1Mn), B30 (Cu-30Ni-1Fe-1Mn) and other nickel nickel copper, and multi-component complex nickel-aluminum bronze, etc.
  • Cu-15Ni-8Sn alloy (corresponding to the US standard number C72900) was successfully developed by Bell Laboratories in the United States in the 1970s, and was named by the US production technology standard in the early 1980s.
  • the alloy has the characteristics of high strength, excellent wear resistance and self-lubrication and wear reduction, especially its strong resistance to high temperature stress relaxation, corrosion resistance in seawater or acidic, oil and gas environments, and wear resistance under high load conditions Both are superior to beryllium copper and aluminum bronze, and are widely used in key wear-resistant and corrosion-resistant parts in the fields of offshore oil and gas exploration, electronic information, and machinery manufacturing.
  • foreign companies that have achieved industrialized production mainly include American Materion Corporation, Swiss Metal and American AMETEK Corporation.
  • Cu-15Ni-8Sn alloy is a typical high-performance copper alloy based on amplitude-modulated decomposition strengthening.
  • the object of the present invention is to provide a kind of Cu-15Ni-8Sn base alloy and its preparation method for marine engineering, to solve or improve the Cu-Ni-Sn alloy in the prior art, which is easy to produce macroscopic component segregation or microscopic dendrite segregation, which is not conducive to At least one of subsequent processing deformation, strength and corrosion resistance needs to be improved.
  • the present invention provides the following technical solutions: a Cu-15Ni-8Sn-based alloy for marine engineering, comprising the following components in percentages: Ni 14%-16%, Sn 7%-9%, Zn 0.3%-2.0%, Si 0.2%-1.5%, Al 0.15%-2.0%, Mn 0.2%-1.6%, Ce 0.02%-0.8%, and Y 0.02%-1.0%, the balance is Cu.
  • the present invention also provides a method for preparing the above-mentioned Cu-15Ni-8Sn-based alloy for marine engineering, which adopts the following technical scheme: the method for preparing the above-mentioned Cu-15Ni-8Sn-based alloy for marine engineering includes the following The above steps: (1) Melting: first add electrolytic copper to the melting furnace to completely melt the electrolytic copper, then add Ni source, then add Mn source, Si source, Ce source and Y source, and finally add Zn source, Al source and Sn source Source, smelting at 1100-1200°C for 30-50min; (2) pouring: After the melt obtained in step (1) is in the shape of a mirror, let it stand for 1-3min, and pour the melt into the metal mold after standing , the melt is solidified to obtain an ingot; (3) performing homogenization annealing, hot extrusion deformation, solution heat treatment, cold drawing deformation and aging heat treatment on the ingot.
  • the present invention is on the basis of Cu-15Ni-8Sn alloy, by adding zinc (Zn), silicon (Si), aluminum (Al), manganese (Mn), cerium (Ce), yttrium (Y) and other microalloying elements, Improve the macroscopic composition and microscopic segregation in the solidification structure of the alloy, and synergistically improve the strength and corrosion resistance of the alloy.
  • Zn element can shorten the solid-liquidus temperature range of the alloy, which is beneficial to suppress segregation.
  • Si element can inhibit the formation of reverse segregation during solidification of the alloy, obtain fine grains, improve the processing deformation ability, and improve the strength of the alloy through the formation of a series of NiSi strengthening phases (Ni 2 Si, Ni 3 Si) between Si and Ni.
  • Al elements and Ni elements can form a series of NiAl strengthening phases (Ni 3 Al, Ni 2 Al), and work together with Si elements to make the alloy superimpose aging precipitation strengthening on the basis of solid solution strengthening, and significantly improve the strength of the alloy.
  • Al elements and Al 2 O 3 passivation film is easy to form during the corrosion process, which is beneficial to improve the corrosion resistance.
  • the Mn element can refine the as-cast grain structure, increase the peak age hardening strength of the alloy, inhibit the grain boundary reaction and grain coarsening, and significantly improve the alloy strength and corrosion resistance.
  • the added rare earth Ce element can purify the alloy melt, refine the as-cast structure, improve the deformability of the alloy, and increase the strength.
  • the addition of rare earth Y elements can accelerate the decomposition of alloy amplitude modulation, slow down the growth of grain boundary precipitates, improve the strength and plasticity of the alloy, reduce the segregation of the alloy, and can form NiSnY and Ni 2 Y compounds to improve the strength and corrosion resistance of the alloy. At the same time, due to the many added alloy components and different characteristics, the mechanisms for improving the strength and corrosion resistance of the alloy are different.
  • the Cu-15Ni-8Sn-based alloy for marine engineering of the present invention (1) the as-cast structure is uniform, and the dendrite segregation is significantly improved; (2) the mechanical properties are excellent: strength ⁇ 1100 MPa, elongation ⁇ 3%; (3) Excellent corrosion resistance: average corrosion rate ⁇ 0.01mm/a.
  • the multi-element, high-strength and high-corrosion-resistant copper alloy prepared by the method of the invention is suitable for key components of marine engineering.
  • Fig. 1 is the conventional Cu-15Ni-8Sn alloy microstructure diagram prepared
  • Fig. 2 is a microstructure diagram of a Cu-15Ni-8Sn-based alloy for marine engineering prepared in Example 2 of the present invention.
  • the present invention aims at at least one of the problems in the prior art that Cu-Ni-Sn alloys are prone to macroscopic component segregation or microscopic dendrite segregation, which is not conducive to subsequent processing deformation, and strength and wear resistance need to be improved, and proposes a marine engineering Use Cu-15Ni-8Sn-based alloy, including the following percentage components: Ni 14%-16%, Sn 7%-9%, Zn 0.3%-2.0% (, Si 0.2%-1.5%, Al 0.15 %-2.0%, Mn 0.2%-1.6%, Ce 0.02%-0.8%, and Y 0.02%-1.0%, the balance being Cu.
  • the contents of trace elements O, S and P are respectively: O ⁇ 5ppm, S ⁇ 3ppm, P ⁇ 3ppm.
  • the Cu-15Ni-8Sn-based alloy for marine engineering includes the following components in percentage: Ni 15%, Sn 8%, Zn 1.2%, Si 0.8%, Al 0.8%, Mn 1.2% , Ce 0.2% and Y 0.5%, the balance is Cu.
  • the tensile strength of the Cu-15Ni-8Sn-based alloy for marine engineering is ⁇ 1000 MPa, the elongation is ⁇ 3%, and the average corrosion rate is ⁇ 0.01 mm/a.
  • the present invention also proposes a method for preparing a Cu-15Ni-8Sn-based alloy for marine engineering.
  • the method for preparing the Cu-15Ni-8Sn-based alloy for marine engineering in the embodiment of the present invention includes the following steps: (1) Melting: first Add electrolytic copper to the melting furnace to melt the electrolytic copper completely, then add Ni source, then add Mn source, Si source, Ce source and Y source, and finally add Zn source, Al source and Sn source, and melt at 1100-1200°C for 30- 50min; (2) pouring: after the melt obtained in the step (1) is in a mirror shape, let it stand for 1-3min, and pour the melt into a metal mold after standing, and the melt solidifies to obtain an ingot; (3) Perform homogenization annealing, hot extrusion deformation, solution heat treatment, cold drawing deformation and aging heat treatment on the ingot.
  • step (1) in step (1), in step (1), Cu ⁇ 99.95wt% in electrolytic copper; Ni source is electrolytic nickel, electrolytic Ni ⁇ 99.96wt% in nickel; Sn source is pure tin, Sn ⁇ 99.99wt% in pure tin; Zn source is pure zinc, Zn ⁇ 98wt% in pure zinc; Si source is pure silicon, Si ⁇ 99.99wt% in pure silicon %; Al source is pure aluminum, Al ⁇ 99.7wt%; Mn source is Cu-Mn master alloy; Ce source is Cu-Ce master alloy; Y source is Cu-Y master alloy.
  • step (1) in the melting furnace, the molten liquid surface is completely covered by charcoal, and a pure phosphorus deoxidizer is used in the smelting process to carry out deoxidation and purification.
  • the dosage of phosphorus deoxidizer is 0.1%-0.3% of the total weight of the melt.
  • the smelting process also includes the steps of stirring with a graphite stirring rod and removing slag with a slag removing rod.
  • the pouring temperature is 1150-1250°C.
  • Pouring temperature is an important parameter in the melting and casting process of materials. If the pouring temperature is too low, the melt fluidity will be poor, and casting defects such as insufficient pouring or shrinkage cavities, holes, and cold shuts will easily occur; if the pouring temperature is too high, on the one hand, it will cause element burning On the other hand, it causes coarse grains in the solidified structure and a decrease in performance.
  • the preparation method of the Cu-15Ni-8Sn-based alloy for marine engineering of the present invention after the pouring is completed, it also includes the step of applying an electromagnetic field outside the metal mold; the current application range of the electromagnetic field is 20-100A.
  • the strength of the electromagnetic field is mainly controlled by adjusting the magnitude of the current, which mainly affects the magnitude of the stirring force exerted by the electromagnetic field on the melt, and the magnitude of the stirring force has a direct relationship with the extent to which the solidification process breaks the formation of dendrites. Therefore, the intensity of the electromagnetic field is controlled by different currents, thereby affecting the formation and distribution of the Sn-rich ⁇ phase, suppressing the effect of dendrite segregation, and improving the subsequent comprehensive performance of the alloy.
  • the present invention improves the segregation of the as-cast solidification structure through a series of operations such as adding different alloying elements and melting and casting links, especially microalloying elements + electromagnetic stirring, and the quality of the as-cast structure directly affects the difficulty of subsequent processing links. And it will affect the overall performance of the final material.
  • the temperature of homogenization annealing is 900-950°C
  • the temperature of hot extrusion deformation is 850-950°C
  • the temperature of solution heat treatment 750-900°C the cold drawing deformation is 50%-90%
  • the aging heat treatment temperature is 300-500°C.
  • the Cu-15Ni-8Sn-based alloy for marine engineering in this embodiment consists of the following components in weight percentage: Ni 15%, Sn 8%, Zn 0.3%, Si 0.2%, Al 0.15%, Mn 0.2%, Ce 0.02% and Y 0.02%, other trace elements O ⁇ 5ppm, S ⁇ 3ppm, P ⁇ 3ppm, the balance is Cu.
  • the preparation method of the Cu-15Ni-8Sn-based alloy for marine engineering of the present embodiment comprises the following steps:
  • Raw material preparation 1# electrolytic copper (Cu ⁇ 99.95%), 1# electrolytic nickel (Ni ⁇ 99.96%), pure tin (Sn ⁇ 99.99%), pure zinc produced by Henan Yixin Nonferrous Metal Materials Co., Ltd. (Zn ⁇ 98%), pure silicon (Si ⁇ 99.99%), pure aluminum (Al ⁇ 99.7%), Cu-Mn master alloy, Cu-Ce master alloy, Cu-Y master alloy, after cutting, drying and Surface degreasing treatment, ready to use.
  • the homogenization annealing temperature is 920°C
  • the hot extrusion temperature is 870°C
  • the solution temperature is 780°C
  • the cold drawing deformation is 60%
  • the aging temperature is 350°C.
  • the Cu-15Ni-8Sn-based alloy for ocean engineering prepared in this example the composition is uniform, and the as-cast microstructure is smaller and evenly distributed than the conventional Cu-15Ni-8Sn alloy; the tensile strength is 1107 MPa, and the elongation It is 5.1%; the average corrosion rate is 0.0093mm/a.
  • the Cu-15Ni-8Sn-based alloy for marine engineering in this embodiment is composed of the following components in weight percentage: Ni 15%, Sn 8%, Zn 1.2%, Si 0.8%, Al 0.8%, Mn 1.2%, Ce 0.2% and Y 0.5%, other trace elements O ⁇ 5ppm, S ⁇ 3ppm, P ⁇ 3ppm, the balance is Cu.
  • the preparation method of the Cu-15Ni-8Sn-based alloy for marine engineering of the present embodiment comprises the following steps:
  • Raw material preparation 1# electrolytic copper (Cu ⁇ 99.95%), 1# electrolytic nickel (Ni ⁇ 99.96%), pure tin (Sn ⁇ 99.99%), pure zinc produced by Henan Yixin Nonferrous Metal Materials Co., Ltd. (Zn ⁇ 98%), pure silicon (Si ⁇ 99.99%), pure aluminum (Al ⁇ 99.7%), Cu-Mn master alloy, Cu-Ce master alloy, Cu-Y master alloy, after cutting, drying and Surface degreasing treatment, ready to use.
  • the homogenization annealing temperature is 940°C
  • the hot extrusion temperature is 950°C
  • the solution heat treatment temperature is 820°C
  • the cold drawing deformation is 85%
  • the aging temperature is 450°C.
  • FIG. 2 The microstructure diagram of the Cu-15Ni-8Sn-based alloy for marine engineering in this embodiment is shown in FIG. 2 .
  • the Cu-15Ni-8Sn-based alloy for marine engineering prepared in this example the composition is uniform, the as-cast microstructure is smaller than the dendrite spacing of the conventional Cu-15Ni-8Sn alloy, the distribution is more uniform and the arrangement direction is consistent; the tensile strength It is 1162MPa, the elongation is 3.4%; the average corrosion rate is 0.0042mm/a.
  • the Cu-15Ni-8Sn-based alloy for marine engineering in this embodiment is composed of the following components in weight percentage: Ni 15%, Sn 8%, Zn 2%, Si 1.5%, Al 2.0%, Mn 1.6%, Ce 0.8% and Y 1.0%, other trace elements O ⁇ 5ppm, S ⁇ 3ppm, P ⁇ 3ppm, the balance is Cu.
  • the preparation method of the Cu-15Ni-8Sn-based alloy for marine engineering of the present embodiment comprises the following steps:
  • Raw material preparation 1# electrolytic copper (Cu ⁇ 99.95%), 1# electrolytic nickel (Ni ⁇ 99.96%), pure tin (Sn ⁇ 99.99%), pure zinc produced by Henan Yixin Nonferrous Metal Materials Co., Ltd. (Zn ⁇ 98%), pure silicon (Si ⁇ 99.99%), pure aluminum (Al ⁇ 99.7%), Cu-Mn master alloy, Cu-Ce master alloy, Cu-Y master alloy, after cutting, drying and Surface degreasing treatment, ready to use.
  • the homogenization annealing temperature is 950°C
  • the hot extrusion temperature is 950°C
  • the solution temperature is 900°C
  • the cold drawing deformation is 90%
  • the aging temperature is 500°C.
  • the Cu-15Ni-8Sn based alloy for marine engineering prepared in this example the composition is uniform, and the as-cast microstructure is smaller than the dendrite spacing of the conventional Cu-15Ni-8Sn alloy; the tensile strength is 1134MPa, and the elongation is 4.1%. ; The average corrosion rate is 0.0065mm/a.
  • the Cu-15Ni-8Sn-based alloy for marine engineering in this embodiment consists of the following components in weight percentage: Ni 14%, Sn 7%, Zn 1.5%, Si 1.2%, Al 1.5%, Mn 0.8%, Ce 0.5% and Y 0.8%, other trace elements O ⁇ 4ppm, S ⁇ 3ppm, P ⁇ 3ppm, the balance is Cu.
  • the preparation method of the Cu-15Ni-8Sn-based alloy for marine engineering of the present embodiment comprises the following steps:
  • Raw material preparation 1# electrolytic copper (Cu ⁇ 99.95%), 1# electrolytic nickel (Ni ⁇ 99.96%), pure tin (Sn ⁇ 99.99%), pure zinc produced by Henan Yixin Nonferrous Metal Materials Co., Ltd. (Zn ⁇ 98%), pure silicon (Si ⁇ 99.99%), pure aluminum (Al ⁇ 99.7%), Cu-Mn master alloy, Cu-Ce master alloy, Cu-Y master alloy, after cutting, drying and Surface degreasing treatment, ready to use.
  • the homogenization annealing temperature is 900°C
  • the hot extrusion temperature is 890°C
  • the solution temperature is 770°C
  • the cold drawing deformation is 65%
  • the aging temperature is 380°C.
  • the Cu-15Ni-8Sn-based alloy for ocean engineering prepared in this example the composition is uniform, and the as-cast microstructure is smaller than the dendrite spacing of the conventional Cu-15Ni-8Sn alloy and the distribution is uniform; the tensile strength is 1130 MPa, and the elongation It is 4.3%; the average corrosion rate is 0.0069mm/a.
  • the Cu-15Ni-8Sn-based alloy for marine engineering in this embodiment consists of the following components in weight percentage: Ni 16%, Sn 9%, Zn 0.7%, Si 0.4%, Al 0.5%, Mn 1.0%, Ce 0.08% and Y 0.12%, other trace elements O ⁇ 5ppm, S ⁇ 3ppm, P ⁇ 3ppm, the balance is Cu.
  • the preparation method of the Cu-15Ni-8Sn-based alloy for marine engineering of the present embodiment comprises the following steps:
  • Raw material preparation 1# electrolytic copper (Cu ⁇ 99.95%), 1# electrolytic nickel (Ni ⁇ 99.96%), pure tin (Sn ⁇ 99.99%), pure zinc produced by Henan Yixin Nonferrous Metal Materials Co., Ltd. (Zn ⁇ 98%), pure silicon (Si ⁇ 99.99%), pure aluminum (Al ⁇ 99.7%), Cu-Mn master alloy, Cu-Ce master alloy, Cu-Y master alloy, after cutting, drying and Surface degreasing treatment, ready to use.
  • the homogenization annealing temperature is 930°C
  • the hot extrusion temperature is 910°C
  • the solution temperature is 860°C
  • the cold drawing deformation is 55%
  • the aging temperature is 420°C.
  • the Cu-15Ni-8Sn-based alloy for ocean engineering prepared in this example the composition is uniform, and the as-cast microstructure is smaller and evenly distributed than the conventional Cu-15Ni-8Sn alloy; the tensile strength is 1159MPa, and the elongation It is 3.7%; the average corrosion rate is 0.0046mm/a.
  • the Cu-15Ni-8Sn-based alloy for marine engineering in this embodiment consists of the following components in weight percentage: Ni 14%, Sn 9%, Zn 2.0%, Si 0.2%, Al 1.2%, Mn 1.0%, Ce 0.02% and Y 1.0%, other trace elements O ⁇ 5ppm, S ⁇ 3ppm, P ⁇ 3ppm, the balance is Cu.
  • the preparation method of the Cu-15Ni-8Sn-based alloy for marine engineering of the present embodiment comprises the following steps:
  • Raw material preparation 1# electrolytic copper (Cu ⁇ 99.95%), 1# electrolytic nickel (Ni ⁇ 99.96%), pure tin (Sn ⁇ 99.99%), pure zinc produced by Henan Yixin Nonferrous Metal Materials Co., Ltd. (Zn ⁇ 98%), pure silicon (Si ⁇ 99.99%), pure aluminum (Al ⁇ 99.7%), Cu-Mn master alloy, Cu-Ce master alloy, Cu-Y master alloy, after cutting, drying and Surface degreasing treatment, ready to use.
  • the homogenizing annealing temperature is 910°C
  • the hot extrusion temperature is 930°C
  • the solution temperature is 820°C
  • the cold drawing deformation is 70%
  • the aging temperature is 410°C.
  • the Cu-15Ni-8Sn-based alloy for ocean engineering prepared in this example the composition is uniform, and the as-cast microstructure is smaller and evenly distributed than the conventional Cu-15Ni-8Sn alloy; the tensile strength is 1129MPa, and the elongation It is 4.2%; the average corrosion rate is 0.0039mm/a.
  • the conventional Cu-15Ni-8Sn alloy of this comparative example is composed of the following components in weight percentage: Ni 15% and Sn 8%, and the balance is Cu.
  • the conventional Cu-15Ni-8Sn alloy of this comparative example is prepared by a method comprising the following steps:
  • Electrolytic copper (Cu ⁇ 99.95%), electrolytic nickel (Ni ⁇ 99.96%), and pure tin (Sn ⁇ 99.99%) are melted in a non-vacuum melting furnace, and no Zn, Si, Al, Mn, Ce, Y are added during the melting process Alloying elements that are beneficial to improve the segregation and performance of the solidified structure; at the same time, the control range for other trace elements O, S, and P is relatively wide. Generally, the O content is greater than 10ppm, the S content is greater than 8ppm, and the P content is greater than 8ppm.
  • the melt After the melt is completely melted, pour it directly into the metal mold without applying electromagnetic field stirring, and then cool and solidify to obtain an ingot; then perform subsequent homogenization annealing ⁇ hot extrusion deformation ⁇ solution heat treatment ⁇ cold drawing Deformation ⁇ aging heat treatment. Due to the serious segregation problem in the solidification structure of the conventional process in the melting and casting stage, the subsequent deformation is more difficult and the yield of the material is reduced.
  • the homogenization annealing temperature is 940°C
  • the hot extrusion deformation temperature is 950°C
  • the solution heat treatment temperature is 820°C
  • the cold drawing deformation is 85%
  • the aging heat treatment temperature is 450°C.
  • Example 1 The difference between this comparative example and Example 1 is that the addition amount of Zn element is: 0.27% (less than 0.3%), and the rest are consistent with Example 1.
  • Example 2 The difference between this comparative example and Example 2 is only that the addition amount of Si element is: 0.19% (less than 0.2%), and the rest are consistent with Example 2.
  • Example 3 The difference between this comparative example and Example 3 is only that the addition amount of Al element is: 0.14% (less than 0.15%), and the rest are consistent with Example 3.
  • Example 4 The difference between this comparative example and Example 4 is only that the addition amount of Mn element is: 0.18% (less than 0.2%), and the rest are consistent with Example 4.
  • Example 5 The difference between this comparative example and Example 5 is only that the amount of Ce element added is: 0.017% (less than 0.02%), and the rest are consistent with Example 5.
  • Example 6 The difference between this comparative example and Example 6 is that the addition amount of Y element is: 0.018% (less than 0.02%), and the rest are consistent with Example 6.
  • Example 3 The difference between this comparative example and Example 3 is only that it consists of the following components in weight percentage: Ni 15%, Sn 8%, Zn 2.3%, Si 1.7%, Al 2.1%, Mn 1.8%, Ce 0.9% And Y 1.1%, the balance is Cu.
  • the test method of tensile strength is: use SHIMADZU (Shimadzu) AG-I250KN precision universal testing machine to carry out tensile test, the tensile rate is 1mm/min, and obtain the stress-strain curve and tensile strength value of the alloy.
  • the test method of elongation is: use SHIMADZU (Shimadzu) AG-I250KN precision universal testing machine to carry out the tensile test, the tensile rate is 1mm/min, obtain the stress-strain curve of the alloy, and measure the alloy before and after stretching by the extensometer Changes in the gauge length to obtain the elongation value.
  • the test method for the average corrosion rate is: soak the sample in an aqueous corrosion medium containing 3.5wt.% NaCl for a static full immersion test. After a certain period of corrosion, measure the mass damage of the sample before and after corrosion, and then calculate the average corrosion rate. rate.
  • Example 1 1107 5.1 0.0093
  • Example 2 1162 3.4 0.0042
  • Example 3 1134 4.1 0.0065
  • Example 4 1130 4.3 0.0069
  • Example 5 1159 3.7 0.0046
  • Example 6 1129 4.2 0.0039
  • Comparative example 1 1028 6.9 0.0207 Comparative example 2 1047 6.4 0.0395 Comparative example 3 1031 6.8 0.0253 Comparative example 4 1029 6.9 0.0331 Comparative example 5 1043 6.5 0.0218 Comparative example 6 1058 6.0 0.0226 Comparative example 7 1052 6.1 0.0309 Comparative example 8 1121 2.3 0.0225
  • the Cu-15Ni-8Sn-based alloy for marine engineering of the present invention has better tensile strength than conventional Cu-15Ni-8Sn alloy, and the average corrosion rate is significantly reduced, suitable for The key components of marine engineering are used.
  • the addition of Zn element can shorten the solid-liquidus temperature range of the alloy, which is beneficial to suppress segregation. If the content of Zn element is too low (less than 0.3%), the effect of inhibiting the formation of reverse segregation during solidification of the alloy will be weakened, and the corrosion resistance of the alloy will be reduced at the same time.
  • the addition of Si element can inhibit the formation of reverse segregation during solidification of the alloy, obtain fine grains, improve the processing deformation ability, and form a series of NiSi strengthening phases (Ni 2 Si, Ni 3 Si) enhances the strength of the alloy. If the content of Si element is too low (less than 0.2%), the effect of inhibiting the formation of reverse segregation during solidification of the alloy is weakened, and the grain size is not obvious, which is not conducive to the improvement of the hot/cold workability of the alloy. At the same time, due to the lack of formation of Si and Ni A series of NiSi strengthening phases reduces the strength of the alloy.
  • Al elements and Ni elements can form a series of NiAl strengthening phases (Ni 3 Al, Ni 2 Al), and work together with Si elements to make the alloy superimpose aging precipitation strengthening on the basis of solid solution strengthening, Significantly improve the strength of the alloy, and at the same time, the Al element and the Al 2 O 3 passivation film are easy to form during the corrosion process, which is beneficial to improve the corrosion resistance. If the Al element content is too low (less than 0.15%), the Al element and the Ni element cannot form a series of NiAl strengthening phases and passivation films, resulting in a significant reduction in alloy strength and corrosion resistance.
  • the Mn element can refine the as-cast grain structure, increase the peak age hardening strength of the alloy, inhibit the grain boundary reaction and grain coarsening, and significantly improve the strength and corrosion resistance of the alloy. If the Mn element content is too low (less than 0.2%), it will lead to coarse grains in the as-cast structure, and weaken the strength and wear resistance of the alloy.
  • the added rare earth Ce element can purify the alloy melt, refine the as-cast structure, improve the deformability of the alloy, and increase the strength. If the Ce element content is too low (less than 0.02%), it will affect the as-cast structure and subsequent deformation ability of the alloy, and reduce the strength of the alloy.
  • the addition of rare earth Y elements can accelerate the amplitude modulation decomposition of the alloy, slow down the growth of grain boundary precipitates, improve the strength and plasticity of the alloy, reduce the segregation of the alloy, and form NiSnY and Ni2Y compounds , improve alloy strength and corrosion resistance. If the Y element content is too low (less than 0.02%), the strength and wear resistance of the alloy will be reduced.
  • the present invention adopts multiple microalloying means, on the basis of the Cu-15Ni-8Sn alloy, by adding zinc (Zn), silicon (Si), aluminum (Al), manganese (Mn), cerium (Ce), yttrium (Y) and other microalloying elements can improve the macroscopic composition and microscopic segregation in the alloy solidification structure, and maintain good elongation
  • the strength and corrosion resistance of the alloy are synergistically improved: the tensile strength ⁇ 1100MPa, and the average corrosion rate ⁇ 0.01mm/a, which can meet the requirements of the comprehensive performance of the alloy in the field of marine engineering.

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Abstract

一种海洋工程用Cu-15Ni-8Sn基合金及其制备方法。海洋工程用Cu-15Ni-8Sn基合金包括下述百分含量的组分：Ni 14％-16％、Sn 7％-9％、Zn 0.3％-2.0％、Si 0.2％-1.5％、Al 0.15％-2.0％、Mn 0.2％-1.6％、Ce 0.02％-0.8％和Y 0.02％-1.0％，余量为Cu。海洋工程用Cu-15Ni-8Sn基合金铸态组织均匀，枝晶偏析得到明显改善；力学性能和耐腐蚀性能优良，适合海洋工程关键部件使用。

Description

一种海洋工程用Cu-15Ni-8Sn基合金及其制备方法 技术领域
本发明属于金属材料技术领域，具体涉及一种海洋工程用Cu-15Ni-8Sn基合金及其制备方法。
背景技术
铜合金因具有良好的力学性能、冷热加工性能、高的换热系数、优良的抗海洋生物附着能力以及耐海水腐蚀性能，在船舶、海洋油气开采、海水资源综合利用等领域得到广泛应用应用，主要应用场景包括：海水泵阀与滤器、舰船汽轮机用冷凝器管、热交换器用铜管、螺旋桨、石油钻探器具和设备部件等。常用的耐蚀铜合金体系主要有HSn70-1、HSn60-1等铝黄铜、锡黄铜，QSn4-4-4、QSn-5-5、QSn6-6-3等锡青铜，B10(Cu-10Ni-1Fe-1Mn)、B30(Cu-30Ni-1Fe-lMn)等镍白铜，以及多元复杂镍铝青铜等。
Cu-15Ni-8Sn合金(对应美标牌号C72900)于20世纪70年代由美国贝尔实验室研制成功，80年代初由美国生产技术标准定名。该合金具有高强度、优良的耐磨性和自润滑减磨等特性，特别是其抗高温应力松弛能力强，在海水或酸性、油气环境下的耐蚀性能以及高负载条件下的耐磨性能均优于铍铜、铝青铜，广泛应用于海洋油气开采、电子信息、机械制造等领域的关键耐磨耐蚀部件。目前国外已经实现工业化生产的公司主要包括美国Materion公司、瑞士金属及美国AMETEK公司，其中美国Materion公司是全球最大的C72900品生产商，主要产品形态为管、棒、环及带。我国海洋油气开采用C72900铜合金管棒材产品目前绝大部分仍购自美国Materion公司。因此，开发满足海洋工程领域用的高强高耐蚀Cu-15Ni-8Sn基合金对于实现国家重点领域关键材料自主可控具有重要意义。
Cu-15Ni-8Sn合金是一种典型的以调幅分解强化为基础的高性能铜合金，但由于合金中Sn含量高、熔点低、合金结晶温度范围宽，在传统凝固条件下容易造成Sn元素的宏观成分偏析和微观枝晶偏析，铸态凝固组织的不均匀性又会影响后续变形加工性能和应用过程中的耐磨耐蚀性能。因此， 如何通过微合金化手段和熔铸工艺调控，获得成分组织均匀的Cu-15Ni-8Sn基合金铸锭，可为提高其成品态的强度和耐蚀性能奠定基础。
因此，需要提供一种针对上述现有技术不足的改进技术方案。
发明内容
本发明的目的在于提供一种海洋工程用Cu-15Ni-8Sn基合金及其制备方法，以解决或改善现有技术中Cu-Ni-Sn合金易产生宏观成分偏析或微观枝晶偏析、不利于后续加工变形、强度和耐蚀性有待提高中的至少一项问题。
为了实现上述目的，本发明提供如下技术方案：一种海洋工程用Cu-15Ni-8Sn基合金，包括下述百分含量的组分：Ni 14％-16％、Sn 7％-9％、Zn 0.3％-2.0％、Si 0.2％-1.5％、Al 0.15％-2.0％、Mn 0.2％-1.6％、Ce 0.02％-0.8％和Y 0.02％-1.0％，余量为Cu。
本发明还提供了如上所述的海洋工程用Cu-15Ni-8Sn基合金的制备方法，其采用下述技术方案：如上所述的海洋工程用Cu-15Ni-8Sn基合金的制备方法，包括下述步骤：(1)熔炼：先向熔炉中加入电解铜，使电解铜熔化完全，之后加入Ni源，再加入Mn源、Si源、Ce源和Y源，最后加入Zn源、Al源和Sn源，1100-1200℃熔炼30-50min；(2)浇注：将经步骤(1)处理所得熔液呈镜面状后，静置1-3min，静置结束后将熔液浇注到金属铸型中，熔液凝固，得到铸锭；(3)对所述铸锭进行均匀化退火、热挤压变形、固溶热处理、冷拉拔变形和时效热处理。
有益效果：
本发明在Cu-15Ni-8Sn合金的基础上，通过添加锌(Zn)、硅(Si)、铝(Al)、锰(Mn)、铈(Ce)、钇(Y)等微合金化元素，改善合金凝固组织中的宏观成分和微观偏析，协同提升合金的强度和耐蚀性能。其中，Zn元素的添加可缩短了合金固-液相线温度范围，有利于抑制偏析。Si元素的添加可抑制合金凝固时反偏析的形成，获得细小晶粒，提升加工变形能力，并通过Si与Ni形成系列NiSi强化相(Ni 2Si、Ni 3Si)提升合金强度。Al元素与Ni元素可形成系列NiAl强化相(Ni 3Al、Ni 2Al)，并与Si元素共同作用，使合金在固溶强化基础上叠加时效析出强化，显著提高合金强度，同时Al元素和腐蚀过程中易形成Al 2O 3钝化膜，有利于提高耐腐蚀性能。Mn元素能 够细化铸态晶粒组织，提高合金时效硬化峰值强度，并抑制晶界反应及晶粒粗化，显著提高合金强度和耐蚀性能。添加的稀土Ce元素能够净化合金熔体，细化铸态组织，改善合金变形能力，提高强度。添加稀土Y元素能够加速合金调幅分解，减缓晶界析出物的长大，提高合金的强度及塑性，减小合金的偏析，并能形成NiSnY和Ni 2Y化合物，提高合金强度和耐蚀性能。同时，由于添加的合金组元多、且特性各不相同，对合金强度和耐蚀性能提升作用机制各异。
本发明的海洋工程用Cu-15Ni-8Sn基合金：(1)铸态组织均匀，枝晶偏析得到明显改善；(2)力学性能优异：强度≥1100MPa，伸长率≥3％；(3)耐腐蚀性能优良：平均腐蚀速率≤0.01mm/a。采用本发明方法制得的多元高强高耐蚀铜合金适合海洋工程关键部件使用。
附图说明
图1为制备的常规Cu-15Ni-8Sn合金微观组织图；
图2为本发明实施例2制备的海洋工程用Cu-15Ni-8Sn基合金的微观组织图。
具体实施方式
下面将结合实施例来详细说明本发明。需要说明的是，在不冲突的情况下，本发明中的实施例及实施例中的特征可以相互组合。
本发明针对目前现有技术中Cu-Ni-Sn合金易产生宏观成分偏析或微观枝晶偏析、不利于后续加工变形、强度和耐磨性有待提高中的至少一项问题，提出一种海洋工程用Cu-15Ni-8Sn基合金，包括下述百分含量的组分：Ni 14％-16％、Sn 7％-9％、Zn 0.3％-2.0％(、Si 0.2％-1.5％、Al 0.15％-2.0％、Mn 0.2％-1.6％、Ce 0.02％-0.8％和Y 0.02％-1.0％，余量为Cu。
本发明优选实施例中，海洋工程用Cu-15Ni-8Sn基合金中，微量元素O、S和P的含量分别为：O≤5ppm、S≤3ppm、P≤3ppm。
本发明优选实施例中，海洋工程用Cu-15Ni-8Sn基合金包括下述百分含量的组分：Ni 15％、Sn 8％、Zn 1.2％、Si 0.8％、Al 0.8％、Mn 1.2％、Ce 0.2％和Y 0.5％，余量为Cu。
本发明优选实施例中，海洋工程用Cu-15Ni-8Sn基合金的抗拉强度≥1000MPa、伸长率≥3％、平均腐蚀速率≤0.01mm/a。
本发明还提出了一种海洋工程用Cu-15Ni-8Sn基合金的制备方法，本发明实施例的海洋工程用Cu-15Ni-8Sn基合金的制备方法包括下述步骤：(1)熔炼：先向熔炉中加入电解铜，使电解铜熔化完全，之后加入Ni源，再加入Mn源、Si源、Ce源和Y源，最后加入Zn源、Al源和Sn源，1100-1200℃熔炼30-50min；(2)浇注：将经步骤(1)处理所得熔液呈镜面状后，静置1-3min，静置结束后将熔液浇注到金属铸型中，熔液凝固，得到铸锭；(3)对铸锭进行均匀化退火、热挤压变形、固溶热处理、冷拉拔变形和时效热处理。
本发明的海洋工程用Cu-15Ni-8Sn基合金的制备方法的优选实施例中，步骤(1)中，步骤(1)中，电解铜中Cu≥99.95wt％；Ni源为电解镍，电解镍中Ni≥99.96wt％；Sn源为纯锡，纯锡中Sn≥99.99wt％；Zn源为纯锌，纯锌中Zn≥98wt％；Si源为纯硅，纯硅中Si≥99.99wt％；Al源为纯铝，Al≥99.7wt％；Mn源为Cu-Mn中间合金；Ce源为Cu-Ce中间合金；Y源为Cu-Y中间合金。
本发明的海洋工程用Cu-15Ni-8Sn基合金的制备方法的优选实施例中，步骤(1)中，熔炉中，熔融液面被木炭完全覆盖，熔炼过程中采用纯磷脱氧剂进行脱氧纯磷脱氧剂的用量为熔液总重量的0.1％-0.3％。熔炼过程中，还包括采用石墨搅拌棒进行搅拌，扒渣棒进行扒渣的步骤。其中，由于纯磷脱氧剂中的磷元素会优先和熔体中氧反应，适量添加可起到净化熔体的作用，但如果添加量过高(超过熔体总重量的0.3％)，过多的磷会残留到合金中导致材料脆性增大，不利于后续塑性变形。
本发明的海洋工程用Cu-15Ni-8Sn基合金的制备方法的优选实施例中，步骤(2)中，浇注的温度为1150-1250℃。浇注温度在材料的熔铸环节是一个重要的参数，浇注温度过低，则熔体流动性差，容易出现浇注不满或者缩孔、孔洞、冷隔等铸造缺陷；浇注温度过高，一方面造成元素烧损，另一方面造成凝固组织晶粒粗大，性能下降。
本发明的海洋工程用Cu-15Ni-8Sn基合金的制备方法的优选实施例中，浇注结束后，还包括在金属铸型外施加电磁场的步骤；电磁场的电流施加范 围为20-100A。电磁场的强弱主要通过调整电流大小来控制，主要是影响电磁场对熔体施加的搅拌力的大小，而搅拌力的大小又会对凝固过程打破枝晶组织形成的程度有直接关系。因此，通过不同电流大小控制电磁场强度，进而影响富Sn的γ相的形成和分布，抑制枝晶偏析的效果，提升合金后续综合性能。本发明通过添加不同的合金化元素、熔铸环节等一系列操作，尤其是微合金元素+电磁搅拌改善铸态凝固组织的偏析，铸态组织的好坏直接影响了后续加工环节的难易程度，并且会影响到最终材料的综合性能。
本发明的海洋工程用Cu-15Ni-8Sn基合金的制备方法的优选实施例中，均匀化退火的温度为900-950℃，热挤压变形的温度为850-950℃，固溶热处理的温度为750-900℃，冷拉拔变形量为50％-90％，时效热处理的温度为300-500℃。
下面通过具体实施例对本发明的海洋工程用Cu-15Ni-8Sn基合金及其制备方法进行详细说明。
实施例1
本实施例的海洋工程用Cu-15Ni-8Sn基合金，由以下重量百分含量的组分组成：Ni 15％、Sn 8％、Zn 0.3％、Si 0.2％、Al 0.15％、Mn 0.2％、Ce 0.02％和Y 0.02％，其他微量元素O≤5ppm、S≤3ppm、P≤3ppm，余量为Cu。
本实施例的海洋工程用Cu-15Ni-8Sn基合金的制备方法，包括下述步骤：
(1)原材料准备：选用河南亿鑫有色金属材料有限公司生产的1#电解铜(Cu≥99.95％)、1#电解镍(Ni≥99.96％)、纯锡(Sn≥99.99％)、纯锌(Zn≥98％)、纯硅(Si≥99.99％)、纯铝(Al≥99.7％)、Cu-Mn中间合金、Cu-Ce中间合金、Cu-Y中间合金，之后经裁剪、烘干和表面除油处理，待用。
(2)配料：按本实施例的海洋工程用Cu-15Ni-8Sn基合金的组成称取经步骤(1)处理后的原材料；
(3)熔炼：先向熔炼炉中加入电解铜，加热使电解铜熔化，待电解铜完全熔化后加入纯镍，然后再加入Cu-Mn中间合金、纯硅、Cu-Ce中间合金、Cu-Y中间合金，最后加入纯锌、纯铝、纯锡。熔炼温度为1100℃，持续时间50分钟；
在加热熔化过程中保证熔融液面被木炭完全覆盖，通过木炭覆盖层隔绝大部分空气来实现熔化过程在微氧化气氛下进行，熔炼过程中采用纯磷脱氧 剂进行脱氧，脱氧剂的用量为熔液总重量的0.1％。熔炼过程中采用石墨搅拌棒搅拌，用扒渣棒扒渣。
(4)浇注：熔液表面无浮渣出现后，待熔液表面拨开熔液呈镜面状后并静置1分钟，将熔液直接浇注到金属铸型中，浇注温度为1150℃；同时为进一步改善凝固组织偏析，在金属铸型外面施加电磁场，当熔液浇注到金属铸型内后，通过调整电磁场的电流改变作用力大小，并对熔体凝固过程施加外力影响，电流施加范围30A。在电磁场和冷却装置的共同作用下，熔液凝固，得到铸锭。
(5)在熔铸制备的组织均匀的铸锭基础上，进行后续的均匀化退火→热挤压变形→固溶热处理→冷拉拔变形→时效热处理。其中，均匀化退火温度为920℃，热挤压温度为870℃，固溶温度为780℃，冷拉拔变形量为60％，时效温度为350℃。
本实施例制备的海洋工程用Cu-15Ni-8Sn基合金：成分均匀，铸态微观组织较常规Cu-15Ni-8Sn合金的枝晶间距变小且分布均匀；抗拉强度为1107MPa，伸长率为5.1％；平均腐蚀速率为0.0093mm/a。
实施例2
本实施例的海洋工程用Cu-15Ni-8Sn基合金，由以下重量百分含量的组分组成：Ni 15％、Sn 8％、Zn 1.2％、Si 0.8％、Al 0.8％、Mn 1.2％、Ce 0.2％和Y 0.5％，其他微量元素O≤5ppm、S≤3ppm、P≤3ppm，余量为Cu。
本实施例的海洋工程用Cu-15Ni-8Sn基合金的制备方法，包括下述步骤：
(1)原材料准备：选用河南亿鑫有色金属材料有限公司生产的1#电解铜(Cu≥99.95％)、1#电解镍(Ni≥99.96％)、纯锡(Sn≥99.99％)、纯锌(Zn≥98％)、纯硅(Si≥99.99％)、纯铝(Al≥99.7％)、Cu-Mn中间合金、Cu-Ce中间合金、Cu-Y中间合金，之后经裁剪、烘干和表面除油处理，待用。
(2)配料：按本实施例的海洋工程用Cu-15Ni-8Sn基合金的组成称取经步骤(1)处理后的原材料；
(3)熔炼：先向熔炼炉中加入电解铜，加热使电解铜熔化，待电解铜完全熔化后加入纯镍，然后再加入Cu-Mn中间合金、纯硅、Cu-Ce中间合金、Cu-Y中间合金，最后加入纯锌、纯铝、纯锡。熔炼温度为1150℃，持续时间45分钟；
在加热熔化过程中保证熔融液面被木炭完全覆盖，通过木炭覆盖层隔绝大部分空气来实现熔化过程在微氧化气氛下进行，熔炼过程中采用纯磷脱氧剂进行脱氧，脱氧剂的用量为熔液总重量的0.2％。熔炼过程中采用石墨搅拌棒搅拌，用扒渣棒扒渣。
(4)浇注：熔液表面无浮渣出现后，待熔液表面拨开熔液呈镜面状后并静置2.5分钟，将熔液直接浇注到金属铸型中，浇注温度为1200℃；同时为进一步改善凝固组织偏析，在金属铸型外面施加电磁场，当熔液浇注到金属铸型内后，通过调整电磁场的电流改变作用力大小，并对熔体凝固过程施加外力影响，电流施加范围60A。在电磁场和冷却装置的共同作用下，熔液凝固，得到铸锭。
(5)在熔铸制备的组织均匀的铸锭基础上，进行后续的均匀化退火→热挤压变形→固溶热处理→冷拉拔变形→时效热处理。其中，均匀化退火温度为940℃，热挤压温度为950℃，固溶热处理温度为820℃，冷拉拔变形量为85％，时效温度为450℃。
本实施例的海洋工程用Cu-15Ni-8Sn基合金的微观组织图如图2所示。
本实施例制备的海洋工程用Cu-15Ni-8Sn基合金：成分均匀，铸态微观组织较常规Cu-15Ni-8Sn合金的枝晶间距变小、分布更加均匀且排布方向一致；抗拉强度为1162MPa，伸长率为3.4％；平均腐蚀速率为0.0042mm/a。
实施例3
本实施例的海洋工程用Cu-15Ni-8Sn基合金，由以下重量百分含量的组分组成：Ni 15％、Sn 8％、Zn 2％、Si 1.5％、Al 2.0％、Mn 1.6％、Ce 0.8％和Y 1.0％，其他微量元素O≤5ppm、S≤3ppm、P≤3ppm，余量为Cu。
本实施例的海洋工程用Cu-15Ni-8Sn基合金的制备方法，包括下述步骤：
(1)原材料准备：选用河南亿鑫有色金属材料有限公司生产的1#电解铜(Cu≥99.95％)、1#电解镍(Ni≥99.96％)、纯锡(Sn≥99.99％)、纯锌(Zn≥98％)、纯硅(Si≥99.99％)、纯铝(Al≥99.7％)、Cu-Mn中间合金、Cu-Ce中间合金、Cu-Y中间合金，之后经裁剪、烘干和表面除油处理，待用。
(2)配料：按本实施例的海洋工程用Cu-15Ni-8Sn基合金的组成称取经步骤(1)处理后的原材料；
(3)熔炼：先向熔炼炉中加入电解铜，加热使电解铜熔化，待电解铜完 全熔化后加入纯镍，然后再加入Cu-Mn中间合金、纯硅、Cu-Ce中间合金、Cu-Y中间合金，最后加入纯锌、纯铝、纯锡。熔炼温度为1200℃，持续时间30分钟；
在加热熔化过程中保证熔融液面被木炭完全覆盖，通过木炭覆盖层隔绝大部分空气来实现熔化过程在微氧化气氛下进行，熔炼过程中采用纯磷脱氧剂进行脱氧，脱氧剂的用量为熔液总重量的0.3％。熔炼过程中采用石墨搅拌棒搅拌，用扒渣棒扒渣。
(4)浇注：熔液表面无浮渣出现后，待熔液表面拨开熔液呈镜面状后并静置3分钟，将熔液直接浇注到金属铸型中，浇注温度为1250℃；同时为进一步改善凝固组织偏析，在金属铸型外面施加电磁场，当熔液浇注到金属铸型内后，通过调整电磁场的电流改变作用力大小，并对熔体凝固过程施加外力影响，电流施加范围100A。在电磁场和冷却装置的共同作用下，熔液凝固，得到铸锭。
(5)在熔铸制备的组织均匀的铸锭基础上，进行后续的均匀化退火→热挤压变形→固溶热处理→冷拉拔变形→时效热处理。其中，均匀化退火温度为950℃，热挤压温度为950℃，固溶温度为900℃，冷拉拔变形量为90％，时效温度为500℃。
本实施例制备的海洋工程用Cu-15Ni-8Sn基合金：成分均匀，铸态微观组织较常规Cu-15Ni-8Sn合金的枝晶间距变小；抗拉强度为1134MPa，伸长率为4.1％；平均腐蚀速率为0.0065mm/a。
实施例4
本实施例的海洋工程用Cu-15Ni-8Sn基合金，由以下重量百分含量的组分组成：Ni 14％、Sn 7％、Zn 1.5％、Si 1.2％、Al 1.5％、Mn 0.8％、Ce 0.5％和Y 0.8％，其他微量元素O≤4ppm、S≤3ppm、P≤3ppm，余量为Cu。
本实施例的海洋工程用Cu-15Ni-8Sn基合金的制备方法，包括下述步骤：
(1)原材料准备：选用河南亿鑫有色金属材料有限公司生产的1#电解铜(Cu≥99.95％)、1#电解镍(Ni≥99.96％)、纯锡(Sn≥99.99％)、纯锌(Zn≥98％)、纯硅(Si≥99.99％)、纯铝(Al≥99.7％)、Cu-Mn中间合金、Cu-Ce中间合金、Cu-Y中间合金，之后经裁剪、烘干和表面除油处理，待用。
(2)配料：按本实施例的海洋工程用Cu-15Ni-8Sn基合金的组成称取经 步骤(1)处理后的原材料；
(3)熔炼：先向熔炼炉中加入电解铜，加热使电解铜熔化，待电解铜完全熔化后加入纯镍，然后再加入Cu-Mn中间合金、纯硅、Cu-Ce中间合金、Cu-Y中间合金，最后加入纯锌、纯铝、纯锡。熔炼温度为1120℃，持续时间50分钟；
在加热熔化过程中保证熔融液面被木炭完全覆盖，通过木炭覆盖层隔绝大部分空气来实现熔化过程在微氧化气氛下进行，熔炼过程中采用纯磷脱氧剂进行脱氧，脱氧剂的用量为熔液总重量的0.1％。熔炼过程中采用石墨搅拌棒搅拌，用扒渣棒扒渣。
(4)浇注：熔液表面无浮渣出现后，待熔液表面拨开熔液呈镜面状后并静置1分钟，将熔液直接浇注到金属铸型中，浇注温度为1170℃；同时为进一步改善凝固组织偏析，在金属铸型外面施加电磁场，当熔液浇注到金属铸型内后，通过调整电磁场的电流改变作用力大小，并对熔体凝固过程施加外力影响，电流施加范围45A。在电磁场和冷却装置的共同作用下，熔液凝固，得到铸锭。
(5)在熔铸制备的组织均匀的铸锭基础上，进行后续的均匀化退火→热挤压变形→固溶热处理→冷拉拔变形→时效热处理。其中，均匀化退火温度为900℃，热挤压温度为890℃，固溶温度为770℃，冷拉拔变形量为65％，时效温度为380℃。
本实施例制备的海洋工程用Cu-15Ni-8Sn基合金：成分均匀，铸态微观组织较常规Cu-15Ni-8Sn合金的枝晶间距变小且分布均匀；抗拉强度为1130MPa，伸长率为4.3％；平均腐蚀速率为0.0069mm/a。
实施例5
本实施例的海洋工程用Cu-15Ni-8Sn基合金，由以下重量百分含量的组分组成：Ni 16％、Sn 9％、Zn 0.7％、Si 0.4％、Al 0.5％、Mn 1.0％、Ce 0.08％和Y 0.12％，其他微量元素O≤5ppm、S≤3ppm、P≤3ppm，余量为Cu。
本实施例的海洋工程用Cu-15Ni-8Sn基合金的制备方法，包括下述步骤：
(1)原材料准备：选用河南亿鑫有色金属材料有限公司生产的1#电解铜(Cu≥99.95％)、1#电解镍(Ni≥99.96％)、纯锡(Sn≥99.99％)、纯锌(Zn≥98％)、纯硅(Si≥99.99％)、纯铝(Al≥99.7％)、Cu-Mn中间合金、Cu-Ce中间合 金、Cu-Y中间合金，之后经裁剪、烘干和表面除油处理，待用。
(2)配料：按本实施例的海洋工程用Cu-15Ni-8Sn基合金的组成称取经步骤(1)处理后的原材料；
(3)熔炼：先向熔炼炉中加入电解铜，加热使电解铜熔化，待电解铜完全熔化后加入纯镍，然后再加入Cu-Mn中间合金、纯硅、Cu-Ce中间合金、Cu-Y中间合金，最后加入纯锌、纯铝、纯锡。熔炼温度为1170℃，持续时间40分钟；
在加热熔化过程中保证熔融液面被木炭完全覆盖，通过木炭覆盖层隔绝大部分空气来实现熔化过程在微氧化气氛下进行，熔炼过程中采用纯磷脱氧剂进行脱氧，脱氧剂的用量为熔液总重量的0.1％。熔炼过程中采用石墨搅拌棒搅拌，用扒渣棒扒渣。
(4)浇注：熔液表面无浮渣出现后，待熔液表面拨开熔液呈镜面状后并静置1分钟，将熔液直接浇注到金属铸型中，浇注温度为1240℃；同时为进一步改善凝固组织偏析，在金属铸型外面施加电磁场，当熔液浇注到金属铸型内后，通过调整电磁场的电流改变作用力大小，并对熔体凝固过程施加外力影响，电流施加范围85A。在电磁场和冷却装置的共同作用下，熔液凝固，得到铸锭。
(5)在熔铸制备的组织均匀的铸锭基础上，进行后续的均匀化退火→热挤压变形→固溶热处理→冷拉拔变形→时效热处理。其中，均匀化退火温度为930℃，热挤压温度为910℃，固溶温度为860℃，冷拉拔变形量为55％，时效温度为420℃。
本实施例制备的海洋工程用Cu-15Ni-8Sn基合金：成分均匀，铸态微观组织较常规Cu-15Ni-8Sn合金的枝晶间距变小且分布均匀；抗拉强度为1159MPa，伸长率为3.7％；平均腐蚀速率为0.0046mm/a。
实施例6
本实施例的海洋工程用Cu-15Ni-8Sn基合金，由以下重量百分含量的组分组成：Ni 14％、Sn 9％、Zn 2.0％、Si 0.2％、Al 1.2％、Mn 1.0％、Ce 0.02％和Y 1.0％，其他微量元素O≤5ppm、S≤3ppm、P≤3ppm，余量为Cu。
本实施例的海洋工程用Cu-15Ni-8Sn基合金的制备方法，包括下述步骤：
(1)原材料准备：选用河南亿鑫有色金属材料有限公司生产的1#电解铜 (Cu≥99.95％)、1#电解镍(Ni≥99.96％)、纯锡(Sn≥99.99％)、纯锌(Zn≥98％)、纯硅(Si≥99.99％)、纯铝(Al≥99.7％)、Cu-Mn中间合金、Cu-Ce中间合金、Cu-Y中间合金，之后经裁剪、烘干和表面除油处理，待用。
(2)配料：按本实施例的海洋工程用Cu-15Ni-8Sn基合金的组成称取经步骤(1)处理后的原材料；
(3)熔炼：先向熔炼炉中加入电解铜，加热使电解铜熔化，待电解铜完全熔化后加入纯镍，然后再加入Cu-Mn中间合金、纯硅、Cu-Ce中间合金、Cu-Y中间合金，最后加入纯锌、纯铝、纯锡。熔炼温度为1180℃，持续时间40分钟；
在加热熔化过程中保证熔融液面被木炭完全覆盖，通过木炭覆盖层隔绝大部分空气来实现熔化过程在微氧化气氛下进行，熔炼过程中采用纯磷脱氧剂进行脱氧，脱氧剂的用量为熔液总重量的0.1％。熔炼过程中采用石墨搅拌棒搅拌，用扒渣棒扒渣。
(4)浇注：熔液表面无浮渣出现后，待熔液表面拨开熔液呈镜面状后并静置1分钟，将熔液直接浇注到金属铸型中，浇注温度为1260℃；同时为进一步改善凝固组织偏析，在金属铸型外面施加电磁场，当熔液浇注到金属铸型内后，通过调整电磁场的电流改变作用力大小，并对熔体凝固过程施加外力影响，电流施加范围75A。在电磁场和冷却装置的共同作用下，熔液凝固，得到铸锭。
(5)在熔铸制备的组织均匀的铸锭基础上，进行后续的均匀化退火→热挤压变形→固溶热处理→冷拉拔变形→时效热处理。其中，均匀化退火温度为910℃，热挤压温度为930℃，固溶温度为820℃，冷拉拔变形量为70％，时效温度为410℃。
本实施例制备的海洋工程用Cu-15Ni-8Sn基合金：成分均匀，铸态微观组织较常规Cu-15Ni-8Sn合金的枝晶间距变小且分布均匀；抗拉强度为1129MPa，伸长率为4.2％；平均腐蚀速率为0.0039mm/a。
对比例1
本对比例的常规Cu-15Ni-8Sn合金，由以下重量百分含量的组分组成：Ni 15％和Sn 8％，余量为Cu。
本对比例的常规Cu-15Ni-8Sn合金采用包括下述步骤的方法制备得到：
采用非真空熔炼炉将电解铜(Cu≥99.95％)、电解镍(Ni≥99.96％)、纯锡(Sn≥99.99％)进行熔化，熔化过程不添加Zn、Si、Al、Mn、Ce、Y等有利于改善凝固组织偏析和性能的合金化元素；同时，对于其它微量元素O、S、P的控制范围较为宽泛，一般O含量大于10ppm、S含量大于8ppm、P含量大于8ppm。待熔体全部熔化完后，直接浇注到金属铸型中，也不施加电磁场搅拌，通过冷却凝固，得到铸锭；然后进行后续的均匀化退火→热挤压变形→固溶热处理→冷拉拔变形→时效热处理。由于常规工艺在熔铸阶段的凝固组织存在严重的偏析问题，使得后续变形更加困难，材料成品率降低。其中，均匀化退火温度为940℃，热挤压变形温度为950℃，固溶热处理温度为820℃，冷拉拔变形量为85％，时效热处理温度为450℃。
对比例2
本对比例与实施例1的区别仅在于：Zn元素的添加量为：0.27％(小于0.3％)，其余均与实施例1保持一致。
对比例3
本对比例与实施例2的区别仅在于：Si元素的添加量为：0.19％(小于0.2％)，其余均与实施例2保持一致。
对比例4
本对比例与实施例3的区别仅在于：Al元素的添加量为：0.14％(小于0.15％)，其余均与实施例3保持一致。
对比例5
本对比例与实施例4的区别仅在于：Mn元素的添加量为：0.18％(小于0.2％)，其余均与实施例4保持一致。
对比例6
本对比例与实施例5的区别仅在于：Ce元素的添加量为：0.017％(小于0.02％)，其余均与实施例5保持一致。
对比例7
本对比例与实施例6的区别仅在于：Y元素的添加量为：0.018％(小于0.02％)，其余均与实施例6保持一致。
对比例8
本对比例与实施例3的区别仅在于：由以下重量百分含量的组分组成： Ni 15％、Sn 8％、Zn 2.3％、Si 1.7％、Al 2.1％、Mn 1.8％、Ce 0.9％和Y 1.1％，余量为Cu。
其余均与实施例3保持一致。
实验例
分别对实施例1-6的海洋工程用Cu-15Ni-8Sn基合金及对比例1的常规Cu-15Ni-8Sn合金及对比例2-8的Cu-15Ni-8Sn基合金的力学性能及耐蚀性能进行测试：
抗拉强度的测试方法为：采用SHIMADZU(岛津)AG-I250KN型精密万能试验机进行拉伸实验，拉伸速率为1mm/min，获得合金应力-应变曲线和抗拉强度数值。
伸长率的测试方法为：采用SHIMADZU(岛津)AG-I250KN型精密万能试验机进行拉伸实验，拉伸速率为1mm/min，获得合金应力-应变曲线，通过引伸计测量拉伸前后合金标距变化情况，获得伸长率数值。
平均腐蚀速率的测试方法为：将试样浸泡在含有3.5wt.％NaCl的水溶液腐蚀介质中进行静态全浸实验，腐蚀一定时间后，测量腐蚀前后试样的质量损伤量，进而计算出平均腐蚀速率。
对实施例1-3的海洋工程用Cu-15Ni-8Sn基合金及对比例1的常规Cu-15Ni-8Sn合金和对比例2-8的Cu-15Ni-8Sn基合金的力学性能、平均腐蚀速率进行对比，具体如下表1所示：
表1
合金体系 抗拉强度/MPa 伸长率/％ 平均腐蚀速率/(mm/a)
实施例1 1107 5.1 0.0093
实施例2 1162 3.4 0.0042
实施例3 1134 4.1 0.0065
实施例4 1130 4.3 0.0069
实施例5 1159 3.7 0.0046
实施例6 1129 4.2 0.0039
对比例1 1028 6.9 0.0207
对比例2 1047 6.4 0.0395
对比例3 1031 6.8 0.0253
对比例4 1029 6.9 0.0331
对比例5 1043 6.5 0.0218
对比例6 1058 6.0 0.0226
对比例7 1052 6.1 0.0309
对比例8 1121 2.3 0.0225
结合对比例1及实施例1-6，本发明的海洋工程用Cu-15Ni-8Sn基合金相对于常规Cu-15Ni-8Sn合金，具有更好的抗拉强度，且平均腐蚀速率显著降低，适合海洋工程关键部件使用。
结合对比例2和实施例1，Zn元素的添加可缩短合金固-液相线温度范围，有利于抑制偏析。如果Zn元素的含量过低(低于0.3％)，使得抑制合金凝固时反偏析形成的效果减弱，同时降低合金的耐蚀性能。
结合对比例3和实施例2，Si元素的添加可抑制合金凝固时反偏析的形成，获得细小晶粒，提升加工变形能力，并通过Si与Ni形成系列NiSi强化相(Ni 2Si、Ni 3Si)提升合金强度。如果Si元素的含量过低(低于0.2％)，使得抑制合金凝固时反偏析形成的效果减弱，晶粒细小不明显，不利于合金的热/冷加工性能提升，同时由于缺少了Si与Ni形成系列NiSi强化相，使得合金强度降低。
结合对比例4和实施例3，Al元素与Ni元素可形成系列NiAl强化相(Ni 3Al、Ni 2Al)，并与Si元素共同作用，使合金在固溶强化基础上叠加时效析出强化，显著提高合金强度，同时Al元素和腐蚀过程中易形成Al 2O 3钝化膜，有利于提高耐腐蚀性能。如果Al元素含量过低(低于0.15％)，使得Al元素与Ni元素无法形成系列NiAl强化相和钝化膜，导致合金强度和耐蚀性能大幅降低。
结合对比例5和实施例4，Mn元素能够细化铸态晶粒组织，提高合金时效硬化峰值强度，并抑制晶界反应及晶粒粗化，显著提高合金强度和耐蚀性能。如果Mn元素含量过低(低于0.2％)，将导致铸态组织晶粒粗大，弱化合金的强度和耐磨性能。
结合对比例6和实施例5，添加的稀土Ce元素能够净化合金熔体，细化铸态组织，改善合金变形能力，提高强度。如果Ce元素含量过低(低于0.02％)，将影响合金的铸态组织和后续变形能力，降低合金的强度。
结合对比例7和实施例6，添加稀土Y元素能够加速合金调幅分解，减缓晶界析出物的长大，提高合金的强度及塑性，减小合金的偏析，并能形成NiSnY和Ni 2Y化合物，提高合金强度和耐蚀性能。如果Y元素含量过低(低于0.02％)，将降低合金的强度和耐磨性能。
结合对比例8和实施例3，过量合金元素的添加，一方面将导致熔铸过程中多余的元素溶解不进去，形成粗大第二相残留在铸态组织中，导致晶粒尺寸粗大，不利于后续塑性变形；同时，热处理过程中会形成较多的金属间化合物，使得合金的脆性增大，以及过量的稀土元素Ce和Y会偏聚在晶界上，导致伸长率大幅降低、更容易发生腐蚀。
综上所述：通过实施例和对比例的抗拉强度、伸长率、平均腐蚀速率数据分析，发现本发明通过多元微合金化手段，在Cu-15Ni-8Sn合金的基础上，通过添加锌(Zn)、硅(Si)、铝(Al)、锰(Mn)、铈(Ce)、钇(Y)等微合金化元素，改善合金凝固组织中的宏观成分和微观偏析，在保持较好伸长率的同时(伸长率≥3％)，协同提升合金的强度和耐蚀性能：抗拉强度≥1100MPa，平均腐蚀速率≤0.01mm/a，能够满足海洋工程领域对合金综合性能的要求。

Claims (10)

  1. 一种海洋工程用Cu-15Ni-8Sn基合金，其特征在于，包括下述百分含量的组分：Ni 14％-16％、Sn 7％-9％、Zn 0.3％-2.0％、Si 0.2％-1.5％、Al 0.15％-2.0％、Mn 0.2％-1.6％、Ce 0.02％-0.8％和Y 0.02％-1.0％，余量为Cu。
  2. 根据权利要求1所述的海洋工程用Cu-15Ni-8Sn基合金，其特征在于，所述海洋工程用Cu-15Ni-8Sn基合金中，微量元素O、S和P的含量分别为：
    O≤5ppm、S≤3ppm、P≤3ppm。
  3. 根据权利要求2所述的海洋工程用Cu-15Ni-8Sn基合金，其特征在于，包括下述百分含量的组分：Ni 15％、Sn 8％、Zn 1.2％、Si 0.8％、Al 0.8％、Mn 1.2％、Ce 0.2％和Y 0.5％，余量为Cu。
  4. 根据权利要求1-3任一项所述的海洋工程用Cu-15Ni-8Sn基合金，其特征在于，所述海洋工程用Cu-15Ni-8Sn基合金的抗拉强度≥1100MPa、伸长率≥3％、平均腐蚀速率≤0.01mm/a。
  5. 根据权利要求1-4任一项所述的海洋工程用Cu-15Ni-8Sn基合金的制备方法，其特征在于，包括下述步骤：
    (1)熔炼：先向熔炉中加入电解铜，使电解铜熔化完全，之后加入Ni源，再加入Mn源、Si源、Ce源和Y源，最后加入Zn源、Al源和Sn源，1100-1200℃熔炼30-50min；
    (2)浇注：将经步骤(1)处理所得熔液呈镜面状后，静置1-3min，静置结束后将熔液浇注到金属铸型中，熔液凝固，得到铸锭；
    (3)对所述铸锭进行均匀化退火、热挤压变形、固溶热处理、冷拉拔变形和时效热处理。
  6. 根据权利要求5所述的海洋工程用Cu-15Ni-8Sn基合金的制备方法，其特征在于，步骤(1)中，所述电解铜中Cu≥99.95wt％；
    所述Ni源为电解镍，所述电解镍中Ni≥99.96wt％；
    所述Sn源为纯锡，所述纯锡中Sn≥99.99wt％；
    所述Zn源为纯锌，所述纯锌中Zn≥98wt％；
    所述Si源为纯硅，所述纯硅中Si≥99.99wt％；
    所述Al源为纯铝，Al≥99.7wt％；
    所述Mn源为Cu-Mn中间合金；
    所述Ce源为Cu-Ce中间合金；
    所述Y源为Cu-Y中间合金。
  7. 根据权利要求5所述的海洋工程用Cu-15Ni-8Sn基合金的制备方法，其特征在于，步骤(1)中，熔炉中，熔融液面被木炭完全覆盖，并采用纯磷脱氧剂进行脱氧；
    所述纯磷脱氧剂的用量为熔液总重量的0.1％-0.3％；
    熔炼过程中，还包括采用石墨搅拌棒进行搅拌，扒渣棒进行扒渣的步骤。
  8. 根据权利要求5所述的海洋工程用Cu-15Ni-8Sn基合金的制备方法，其特征在于，步骤(2)中，所述浇注的温度为1150-1250℃。
  9. 根据权利要求5所述的海洋工程用Cu-15Ni-8Sn基合金的制备方法，其特征在于，浇注结束后，还包括在金属铸型外施加电磁场的步骤；
    所述电磁场的电流施加范围为20-100A。
  10. 根据权利要求5-9任一项所述的海洋工程用Cu-15Ni-8Sn基合金的制备方法，其特征在于，所述均匀化退火的温度为900-950℃，热挤压变形的温度为850-950℃，固溶热处理的温度为750-900℃，冷拉拔变形量为50％-90％，时效热处理的温度为300-500℃。
PCT/CN2022/135142 2022-11-23 2022-11-29 一种海洋工程用Cu-15Ni-8Sn基合金及其制备方法 WO2023061514A1 (zh)

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