CN109694976B - Low-cost soluble magnesium alloy and preparation method and application thereof - Google Patents
Low-cost soluble magnesium alloy and preparation method and application thereof Download PDFInfo
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 79
- 239000000956 alloy Substances 0.000 claims abstract description 79
- 239000011777 magnesium Substances 0.000 claims abstract description 35
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 26
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- 239000012535 impurity Substances 0.000 claims abstract description 16
- 229910002482 Cu–Ni Inorganic materials 0.000 claims abstract description 11
- 238000005516 engineering process Methods 0.000 claims abstract description 11
- 239000003079 shale oil Substances 0.000 claims abstract description 11
- 238000011161 development Methods 0.000 claims abstract description 8
- 238000001125 extrusion Methods 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 23
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- 229910052749 magnesium Inorganic materials 0.000 claims description 17
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 238000007670 refining Methods 0.000 claims description 11
- 238000003723 Smelting Methods 0.000 claims description 9
- 238000001192 hot extrusion Methods 0.000 claims description 9
- 238000000265 homogenisation Methods 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 241001062472 Stokellia anisodon Species 0.000 claims description 6
- 229910019083 Mg-Ni Inorganic materials 0.000 claims description 5
- 229910019403 Mg—Ni Inorganic materials 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 5
- 229910019086 Mg-Cu Inorganic materials 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 abstract description 12
- 238000012545 processing Methods 0.000 abstract description 6
- 239000007769 metal material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 17
- 239000002994 raw material Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 6
- 229910000838 Al alloy Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229910019758 Mg2Ni Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
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- Continuous Casting (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
本发明属于金属材料及加工技术领域,涉及一种低成本可溶性镁合金及其制备方法和应用,其可以用于制备页岩油气开采用多级滑套分段压裂技术的相关零部件。所述合金为Mg‑Al‑Ca‑Mn‑Cu‑Ni镁合金,由以下质量百分比的元素组成:Al 0.20~0.50wt%、Ca 0.20~1.00wt%、Mn 0.30~1.10wt%、Cu 0.10~1.20wt%、Ni 0.10~0.50wt%,其余为Mg及不可避免的杂质元素。本发明制备的低成本可溶性镁合金的抗拉强度≥280MPa,屈服强度≥240MPa,延伸率≥14%;在93℃、3%KCl溶液中的溶解速率为50‑60mg cm‑ 2h‑1。
The invention belongs to the technical field of metal materials and processing, and relates to a low-cost soluble magnesium alloy and a preparation method and application thereof, which can be used to prepare relevant parts of shale oil and gas development using multi-stage sliding sleeve staged fracturing technology. The alloy is a Mg-Al-Ca-Mn-Cu-Ni magnesium alloy, which is composed of the following elements by mass percentage: Al 0.20-0.50wt%, Ca 0.20-1.00wt%, Mn 0.30-1.10wt%, Cu 0.10- 1.20wt%, Ni 0.10-0.50wt%, and the rest are Mg and unavoidable impurity elements. The low-cost soluble magnesium alloy prepared by the invention has a tensile strength of ≥280 MPa, a yield strength of ≥240 MPa and an elongation of ≥14%; the dissolution rate in a 93° C., 3% KCl solution is 50-60 mg cm - 2 h -1 .
Description
技术领域technical field
本发明属于金属材料及加工技术领域,特别涉及一种低成本可溶性镁合金及其制备方法和应用,其可以用于制备页岩油气开采用多级滑套分段压裂技术的相关零部件。The invention belongs to the technical field of metal materials and processing, and in particular relates to a low-cost soluble magnesium alloy and a preparation method and application thereof, which can be used to prepare relevant parts of shale oil and gas development using multi-stage sliding sleeve staged fracturing technology.
背景技术Background technique
科学技术的发展促使全球工业自动化水平不断提高,这导致能源的需求进一步增加。页岩油气作为当前和未来一段时间内能源领域发展的重要方向之一,具有较高的经济价值,相关开采技术在美国已经取得成功并逐步推广到全球。据统计,我国的页岩气储量居世界第一位,页岩油储量居世界第三位,未来发展前景广阔。然而相关开采技术仍然处于起步价段,目前主流技术为水平井开采常用的多级滑套分段压裂技术。该技术的一个关键部件是压裂工具,包括暂堵球、球座、桥塞和滑套等。上述工具在压裂过程中要具有可溶解以及较好的强度和延伸率等特点。The development of science and technology promotes the continuous improvement of the global industrial automation level, which leads to a further increase in the demand for energy. Shale oil and gas, as one of the important directions of the development of the energy field at present and in the future, has high economic value. The related extraction technology has been successful in the United States and gradually spread to the world. According to statistics, my country's shale gas reserves rank first in the world, and shale oil reserves rank third in the world, with broad prospects for future development. However, the relevant mining technology is still in the starting price range, and the current mainstream technology is the multi-stage sliding sleeve staged fracturing technology commonly used in horizontal well mining. A key component of the technology is the fracturing tool, including temporary plugging balls, ball seats, bridge plugs, and sliding sleeves. The above tools should have the characteristics of dissolvability and good strength and elongation during the fracturing process.
目前国内外针对上述工具开发的可溶解材料多为高分子材料、复合材料、铝合金和镁合金。高分子材料的力学性能较低,并且在高温腐蚀介质中不易分解。复合材料多采用纳米级金属粉,极大的增加了材料成本,也阻碍了其应用推广。At present, the dissolvable materials developed for the above tools at home and abroad are mostly polymer materials, composite materials, aluminum alloys and magnesium alloys. The mechanical properties of polymer materials are low, and they are not easily decomposed in high-temperature corrosive media. Most of the composite materials use nano-scale metal powder, which greatly increases the material cost and hinders its application and promotion.
专利“一种耐压快速降解的铸造铝合金及其制备方法”(申请号201710327729.3)和专利“一种轻质耐压快速分解的铸造镁合金”(申请号CN201310284659.X)分别公布了一种可快速溶解的铸造铝合金和铸造镁合金。然而本发明人发现:通过铸造工艺得到铝合金和镁合金产品具有明显铸造组织特征:树枝晶结构、晶粒较为粗大和不同程度的成分偏析;这会导致产品的力学性能偏低和溶解过程的不均匀稳定。The patent "A pressure-resistant and fast-degrading cast aluminum alloy and its preparation method" (application number 201710327729.3) and the patent "a light-weight pressure-resistant and rapidly decomposing cast magnesium alloy" (application number CN201310284659.X) respectively announced a Fast dissolving cast aluminium alloys and cast magnesium alloys. However, the inventors found that the aluminum alloy and magnesium alloy products obtained by the casting process have obvious casting structure characteristics: dendritic structure, relatively coarse grains and different degrees of component segregation; this will lead to low mechanical properties of the products and poor dissolution process. Uneven and stable.
发明内容SUMMARY OF THE INVENTION
针对以上所述问题,本发明提供一种低成本可溶性镁合金及其制备方法和应用。本发明可溶性镁合金中不含价格昂贵的稀土元素,在实现低成本的基础上,既具有良好的力学性能,又具备均一、稳定的溶解速率;该合金是一种综合性能良好的可溶解镁合金。本发明可溶性镁合金制备过程中采用挤压速度可高达20m/min。In view of the above problems, the present invention provides a low-cost soluble magnesium alloy and a preparation method and application thereof. The soluble magnesium alloy of the invention does not contain expensive rare earth elements, and on the basis of realizing low cost, it has both good mechanical properties and a uniform and stable dissolution rate; the alloy is a kind of soluble magnesium with good comprehensive performance. alloy. In the preparation process of the soluble magnesium alloy of the present invention, the extrusion speed can be as high as 20 m/min.
本发明采用以下技术方案:The present invention adopts following technical scheme:
本发明第一个方面,提供一种低成本可溶性镁合金,所述低成本可溶性镁合金为Mg-Al-Ca-Mn-Cu-Ni镁合金,由以下质量百分比的元素组成:Al 0.20~0.50wt%、Ca 0.20~1.00wt%、Mn 0.30~1.10wt%、Cu 0.10~1.20wt%、Ni 0.10~0.50wt%,其余为Mg及不可避免的杂质元素。A first aspect of the present invention provides a low-cost soluble magnesium alloy, the low-cost soluble magnesium alloy is a Mg-Al-Ca-Mn-Cu-Ni magnesium alloy, and is composed of the following elements by mass percentage: Al 0.20-0.50 wt%, Ca 0.20-1.00wt%, Mn 0.30-1.10wt%, Cu 0.10-1.20wt%, Ni 0.10-0.50wt%, and the rest are Mg and inevitable impurity elements.
本发明中不可避免杂质≤0.050%。In the present invention, unavoidable impurities≤0.050%.
本发明第二个方面,提供以上所述低成本可溶性镁合金的制备方法,包括以下步骤:称取纯镁锭、纯铝锭、Mg-Ca中间合金、Mg-Mn中间合金、Mg-Cu中间合金、Mg-Ni中间合金;通入保护气体并进行熔炼,浇注成铸锭;将铸锭进行均匀化处理,切成相应尺寸的坯料并去皮;热挤压成棒材;所述热挤压条件为:挤压温度350~400℃、挤压比为4~10、挤压速度10~20m/min;优选挤压温度350℃。In a second aspect of the present invention, a method for preparing the above-mentioned low-cost soluble magnesium alloy is provided, comprising the following steps: weighing pure magnesium ingot, pure aluminum ingot, Mg-Ca master alloy, Mg-Mn master alloy, and Mg-Cu intermediate Alloy, Mg-Ni intermediate alloy; pass in protective gas and smelt, cast into ingot; homogenize the ingot, cut into billets of corresponding size and peel; hot extrusion into rod; the hot extrusion The pressing conditions are as follows: the extrusion temperature is 350-400°C, the extrusion ratio is 4-10, and the extrusion speed is 10-20 m/min; the extrusion temperature is preferably 350°C.
本发明第三个方面,提供以上所述的低成本可溶性镁合金在制备页岩油气开采过程中的可溶解零部件中应用。The third aspect of the present invention provides the application of the above-mentioned low-cost soluble magnesium alloy in the preparation of soluble parts in the process of shale oil and gas exploitation.
本发明取得有益成果:The present invention achieves beneficial results:
(1)本发明Mg-Al-Ca-Mn-Cu-Ni合金通过Mn和Ca细化铸锭晶粒尺寸,进而降低铸锭偏析,使得材料中的Cu和Ni均匀分布,形成细小弥散的Mg2Cu和Mg2Ni,达到均匀溶解的目的。本发明制备的低成本可溶性镁合金的抗拉强度≥280MPa,屈服强度≥240MPa,延伸率≥14%;在93℃、3%KCl溶液中的溶解速率为50~60mg cm-2h-1。(1) The Mg-Al-Ca-Mn-Cu-Ni alloy of the present invention refines the grain size of the ingot through Mn and Ca, thereby reducing the segregation of the ingot, making the Cu and Ni in the material evenly distributed, and forming fine and dispersed Mg 2 Cu and Mg 2 Ni to achieve the purpose of uniform dissolution. The low-cost soluble magnesium alloy prepared by the invention has a tensile strength of ≥280 MPa, a yield strength of ≥240 MPa and an elongation of ≥14%; the dissolution rate in a 93° C., 3% KCl solution is 50-60 mg cm -2 h -1 .
(2)本发明的合金通过Ca元素的加入,弱化了镁合金的基面织构,进而提高材料的延伸率。另外,Ca本身具有阻燃和抗氧化效果,提高了合金的燃点。因而,在熔炼过程中降低了保护气体的用量;在均匀化处理过程中不需要气体保护,并且挤压过程采用挤压速率可高达20m/min。(2) The alloy of the present invention weakens the basal texture of the magnesium alloy by adding Ca element, thereby increasing the elongation of the material. In addition, Ca itself has flame retardant and anti-oxidation effects, which improves the ignition point of the alloy. Therefore, the amount of shielding gas is reduced during the smelting process; gas shielding is not required during the homogenization process, and the extrusion rate can be as high as 20m/min during the extrusion process.
(3)本发明在合金中加入少量Al元素,一方面通过固溶强化方式提高材料的强度,另一方面可以形成少量高熔点的(Mg,Al)2Ca和Al8Mn5的第二相,通过弥散强化的方式提高材料的强度。(3) In the present invention, a small amount of Al element is added to the alloy. On the one hand, the strength of the material is improved by solid solution strengthening, and on the other hand, a small amount of high melting point (Mg, Al) 2 Ca and Al 8 Mn 5 can be formed in the second phase. , to improve the strength of the material by means of dispersion strengthening.
(4)本发明可溶性镁合金可以在350-400℃高温、小于10的挤压比条件下快速挤压得到良好力学性能的可溶性镁合金。“通入保护气体变形”和“小挤压比”,一方面可以降低加工过程中变形抗力,提高成形速率,降低设备损耗;另一方面可以采用小吨位设备加工大尺寸产品,减少设备等固定资产投入。(4) The soluble magnesium alloy of the present invention can be rapidly extruded at a high temperature of 350-400° C. and an extrusion ratio of less than 10 to obtain a soluble magnesium alloy with good mechanical properties. "Deformation through shielding gas" and "small extrusion ratio" can reduce deformation resistance during processing, increase forming rate, and reduce equipment loss; asset investment.
(5)本发明可溶性镁合金中仅添加了少量较贵的Ni元素,对合金成本增加较少;同时,材料加工速率高、成本低,因此应用前景较好。(5) Only a small amount of relatively expensive Ni element is added to the soluble magnesium alloy of the present invention, which increases the cost of the alloy less; at the same time, the material processing rate is high and the cost is low, so the application prospect is good.
附图说明Description of drawings
构成本发明的一部分的说明书附图用来提供对本发明的进一步理解,本发明的示意性实施例及其说明用于解释本发明,并不构成对本发明的不当限定。The accompanying drawings forming a part of the present invention are used to provide further understanding of the present invention, and the exemplary embodiments of the present invention and their descriptions are used to explain the present invention, and do not constitute an improper limitation of the present invention.
图1为试验例组1制备得到的镁合金的显微组织。FIG. 1 shows the microstructure of the magnesium alloy prepared in Test Example Group 1.
图2为试验例组6制备得到的镁合金的显微组织。FIG. 2 is the microstructure of the magnesium alloy prepared in Test Example Group 6. FIG.
具体实施方式Detailed ways
应该指出,以下详细说明都是示例性的,旨在对本发明提供进一步的说明。除非另有指明,本文使用的所有技术和科学术语具有与本发明所属技术领域的普通技术人员通常理解的相同含义。It should be noted that the following detailed description is exemplary and intended to provide further explanation of the invention. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
需要注意的是,这里所使用的术语仅是为了描述具体实施方式,而非意图限制根据本发明的示例性实施方式。如在这里所使用的,除非上下文另外明确指出,否则单数形式也意图包括复数形式,此外,还应当理解的是,当在本说明书中使用术语“包含”和/或“包括”时,其指明存在特征、步骤、操作和/或它们的组合。It should be noted that the terminology used herein is for the purpose of describing specific embodiments only, and is not intended to limit the exemplary embodiments according to the present invention. As used herein, unless the context clearly dictates otherwise, the singular is intended to include the plural as well, furthermore, it is to be understood that when the terms "comprising" and/or "including" are used in this specification, it indicates that There are features, steps, operations, and/or combinations thereof.
针对背景技术中所述问题,本发明第一个方面,提供一种低成本可溶性镁合金,所述低成本可溶性镁合金为Mg-Al-Ca-Mn-Cu-Ni镁合金,由以下质量百分比的元素组成:Al0.20~0.50wt%、Ca 0.20~1.00wt%、Mn 0.30~1.10wt%、Cu 0.10~1.20wt%、Ni 0.10~0.50wt%,其余为Mg及不可避免的杂质元素。In view of the problems described in the background art, the first aspect of the present invention provides a low-cost soluble magnesium alloy, the low-cost soluble magnesium alloy is a Mg-Al-Ca-Mn-Cu-Ni magnesium alloy, which is composed of the following mass percentages Elemental composition: Al 0.20-0.50wt%, Ca 0.20-1.00wt%, Mn 0.30-1.10wt%, Cu 0.10-1.20wt%, Ni 0.10-0.50wt%, and the rest are Mg and inevitable impurity elements.
进一步地,所述低成本可溶性镁合金由以下质量百分比的元素组成:Al 0.30~0.50wt%、Ca 0.80~1.00wt%、Mn 0.30~0.70wt%、Cu 0.30~0.90wt%、Ni 0.20~0.40wt%,其余为Mg及不可避免的杂质元素。Further, the low-cost soluble magnesium alloy is composed of the following elements by mass percentage: Al 0.30-0.50wt%, Ca 0.80-1.00wt%, Mn 0.30-0.70wt%, Cu 0.30-0.90wt%, Ni 0.20-0.40 wt%, and the rest are Mg and inevitable impurity elements.
进一步地,所述低成本可溶性镁合金由以下质量百分比的元素组成:Al0.50wt%、Ca 0.90wt%、Mn 0.55wt%、Cu 0.40wt%、Ni 0.30wt%,其余为Mg及不可避免的杂质元素。Further, the low-cost soluble magnesium alloy is composed of the following elements by mass percentage: Al 0.50wt%, Ca 0.90wt%, Mn 0.55wt%, Cu 0.40wt%, Ni 0.30wt%, and the rest are Mg and unavoidable impurity elements.
镁合金由于化学性质活泼,在没有保护的情况下,熔炼和铸造过程极易发生氧化燃烧,适度的合金化可以提高合金的燃点温度,降低熔炼、铸造过程中的成本和事故风险;另外镁合金属于密排六方金属结构,室温滑移系较少,需要热成形加工,而高合金化会增加材料成本,同时降低其成形性能—挤压过程中容易出现氧化、裂纹等缺陷。因此,合金化元素的选择和含量的控制对材料的加工成本和产品质量、力学性能、溶解速率都具有显著的影响。本发明镁合金通过优化合金元素及其含量,达到了低成本、易成形、中等强度和延伸率、可溶解的目的。Due to its active chemical properties, magnesium alloys are prone to oxidative combustion during smelting and casting without protection. Moderate alloying can increase the ignition temperature of the alloy and reduce costs and accident risks during smelting and casting. In addition, magnesium alloys It belongs to the close-packed hexagonal metal structure, with less slip system at room temperature, and requires hot forming processing, while high alloying will increase the material cost and reduce its forming performance at the same time. Defects such as oxidation and cracks are prone to occur during extrusion. Therefore, the selection and content control of alloying elements have a significant impact on the processing cost and product quality, mechanical properties, and dissolution rate of the material. The magnesium alloy of the present invention achieves the goals of low cost, easy forming, medium strength and elongation, and solubility by optimizing alloy elements and their contents.
Al是最经济的提高变形镁合金强度的元素。Ca元素可以显著提高镁合金的燃点温度,并且细化铸锭组织。Mn元素也可以细化镁合金铸锭晶粒组织。另外,Al和Ca可以与Mg形成熔点较高的(Mg,Al)2Ca相;Al和Mn元素也可以形成高熔点的Al8Mn5相。通过Al、Ca、Mn的微合金化既提高了镁合金强度,又保持了较好的延伸率。Al is the most economical element for enhancing the strength of wrought magnesium alloys. Ca element can significantly increase the ignition temperature of magnesium alloys and refine the ingot structure. Mn element can also refine the grain structure of magnesium alloy ingots. In addition, Al and Ca can form a higher melting point (Mg,Al) 2 Ca phase with Mg; Al and Mn elements can also form a high melting point Al 8 Mn 5 phase. The microalloying of Al, Ca and Mn not only improves the strength of magnesium alloy, but also maintains a good elongation.
传统上认为Cu和Ni属于杂质元素,会提高镁合金腐蚀速度。本发明通过控制Cu和Ni元素的含量,在镁合金组织得到细小的Mg2Cu和Mg2Ni相,从而可以制备可溶解镁合金。Traditionally, it is believed that Cu and Ni are impurity elements that increase the corrosion rate of magnesium alloys. By controlling the contents of Cu and Ni elements, the invention obtains fine Mg2Cu and Mg2Ni phases in the magnesium alloy structure, so that the soluble magnesium alloy can be prepared.
本发明第二个方面,提供以上所述低成本可溶性镁合金的制备方法,包括以下步骤:称取纯镁锭、纯铝锭、Mg-Ca中间合金、Mg-Mn中间合金、Mg-Cu中间合金、Mg-Ni中间合金;通入保护气体并进行熔炼,浇注成铸锭;将铸锭进行均匀化处理,切成相应尺寸的坯料并去皮;热挤压成棒材;所述热挤压条件为:挤压温度350~400℃、挤压比为4~10、挤压速度10~20m/min;优选挤压温度350℃。本发明方法挤压比小,挤压速度大,降低设备损耗。In a second aspect of the present invention, a method for preparing the above-mentioned low-cost soluble magnesium alloy is provided, comprising the following steps: weighing pure magnesium ingot, pure aluminum ingot, Mg-Ca master alloy, Mg-Mn master alloy, and Mg-Cu intermediate Alloy, Mg-Ni intermediate alloy; pass in protective gas and smelt, cast into ingot; homogenize the ingot, cut into billets of corresponding size and peel; hot extrusion into rod; the hot extrusion The pressing conditions are as follows: the extrusion temperature is 350-400°C, the extrusion ratio is 4-10, and the extrusion speed is 10-20 m/min; the extrusion temperature is preferably 350°C. In the method of the invention, the extrusion ratio is small, the extrusion speed is large, and the equipment loss is reduced.
进一步地,所述热挤压条件为:挤压温度350℃、挤压比为8、挤压速度20m/min。在该热挤压条件下制备得到的可溶性镁合金溶解性、抗拉强度、延伸率等性能最佳。本发明采用上述较低的挤压比可以制备较大尺寸的棒材,同时可以降低所需挤压机设备的吨位。Further, the hot extrusion conditions are: extrusion temperature of 350° C., extrusion ratio of 8, and extrusion speed of 20 m/min. The soluble magnesium alloy prepared under the hot extrusion conditions has the best properties such as solubility, tensile strength and elongation. By adopting the above-mentioned lower extrusion ratio, the present invention can prepare rods of larger size, and at the same time, the tonnage of the required extruder equipment can be reduced.
进一步地,所述熔炼,浇注成铸锭的步骤包括:将纯镁锭、纯铝锭、Mg-Ca中间合金、Mg-Mn中间合金、Mg-Cu中间合金、Mg-Ni中间合金按照配比称重,通入保护气体,在720~740℃熔炼,保温40~60min,搅拌5~10min,并精炼20~30min,精炼后升温至740~760℃静置30~40min,在720~740℃浇注成铸锭;优选的,在730℃熔炼,保温60min,搅拌10min,并精炼20min,精炼后升温至760℃静置40min,在720℃浇注成铸锭。Further, the steps of smelting and pouring into ingots include: mixing pure magnesium ingots, pure aluminum ingots, Mg-Ca master alloys, Mg-Mn master alloys, Mg-Cu master alloys, and Mg-Ni master alloys according to the proportions. Weigh, introduce protective gas, smelt at 720~740℃, keep warm for 40~60min, stir for 5~10min, and refine for 20~30min. Pouring into an ingot; preferably, smelting at 730°C, holding for 60 minutes, stirring for 10 minutes, and refining for 20 minutes. After refining, the temperature is raised to 760°C and left to stand for 40 minutes.
进一步地,所用保护气体为CO2和SF6的混合气体,CO2和SF6体积比为200~400:1;优选的,CO2和SF6体积比为300:1。该混合气体防止合金制备过程中发生氧化作用效果最显著。Further, the protective gas used is a mixed gas of CO 2 and SF 6 , and the volume ratio of CO 2 and SF 6 is 200-400:1; preferably, the volume ratio of CO 2 and SF 6 is 300:1. The mixed gas has the most significant effect of preventing oxidation during the alloy preparation process.
进一步地,所述均匀化处理的条件是在480~520℃下进行均匀化处理保温时间1~4h,冷却方式为风冷,然后切成相应的坯料并去皮;优选的,在500℃下进行均匀化处理保温时间2h。本发明采用较高的均匀化温度,一方面可以促进微量合金尽快固溶到镁合金基体中,降低热处理成本;另一方面可缩短均匀化保温时间,防止铸态组织粗化。Further, the conditions of the homogenization treatment are to carry out the homogenization treatment at 480-520°C for a holding time of 1-4h, the cooling method is air cooling, and then cut into corresponding blanks and peeled; preferably, at 500°C The homogenization treatment was carried out for a holding time of 2h. The invention adopts a higher homogenization temperature, on the one hand, it can promote the microalloy to dissolve into the magnesium alloy matrix as soon as possible, and reduce the heat treatment cost;
本发明第三个方面,提供以上所述的低成本可溶性镁合金在制备页岩油气开采过程中的可溶解零部件中应用。The third aspect of the present invention provides the application of the above-mentioned low-cost soluble magnesium alloy in the preparation of soluble parts in the process of shale oil and gas exploitation.
进一步地,以上所述的低成本可溶性镁合金在制备页岩油气开采用多级滑套分段压裂技术的相关零部件中的应用。本发明可溶性镁合金具有溶解速率快、抗拉强度大等优势,在制备页岩油气开采用多级滑套分段压裂技术的相关零部件中应用前景广阔。Further, the application of the above-mentioned low-cost soluble magnesium alloy in the preparation of relevant parts for shale oil and gas development using multi-stage sliding sleeve staged fracturing technology. The soluble magnesium alloy of the invention has the advantages of fast dissolution rate, high tensile strength and the like, and has broad application prospects in the preparation of related parts and components of the multi-stage sliding sleeve staged fracturing technology for shale oil and gas development.
为了使得本领域技术人员能够更加清楚地了解本发明的技术方案,以下将结合具体的实施例与对比例详细说明本发明的技术方案。In order to enable those skilled in the art to understand the technical solutions of the present invention more clearly, the technical solutions of the present invention will be described in detail below with reference to specific embodiments and comparative examples.
实施例1一种低成本可溶性镁合金Embodiment 1 A kind of low-cost soluble magnesium alloy
所述低成本可溶性镁合金为Mg-Al-Ca-Mn-Cu-Ni镁合金,由以下质量百分比的元素组成:Al 0.50wt%、Ca 0.90wt%、Mn 0.55wt%、Cu 0.40wt%、Ni 0.30wt%,其余为Mg及不可避免的杂质元素。The low-cost soluble magnesium alloy is a Mg-Al-Ca-Mn-Cu-Ni magnesium alloy, which is composed of the following elements by mass percentage: Al 0.50wt%, Ca 0.90wt%, Mn 0.55wt%, Cu 0.40wt%, Ni is 0.30wt%, and the rest is Mg and inevitable impurity elements.
实施例2一种低成本可溶性镁合金Embodiment 2 A kind of low-cost soluble magnesium alloy
所述低成本可溶性镁合金为Mg-Al-Ca-Mn-Cu-Ni镁合金,由以下质量百分比的元素组成:Al 0.40wt%、Ca 0.50wt%、Mn 0.45wt%、Cu 0.90wt%、Ni 0.10wt%,其余为Mg及不可避免的杂质元素。The low-cost soluble magnesium alloy is a Mg-Al-Ca-Mn-Cu-Ni magnesium alloy, which is composed of the following elements by mass percentage: Al 0.40wt%, Ca 0.50wt%, Mn 0.45wt%, Cu 0.90wt%, Ni is 0.10wt%, and the rest is Mg and unavoidable impurity elements.
实施例3一种低成本可溶性镁合金Embodiment 3 A kind of low-cost soluble magnesium alloy
所述低成本可溶性镁合金为Mg-Al-Ca-Mn-Cu-Ni镁合金,由以下质量百分比的元素组成:Al 0.30wt%、Ca 1.00wt%、Mn 0.90wt%、Cu 1.0wt%、Ni 0.50wt%,其余为Mg及不可避免的杂质元素。The low-cost soluble magnesium alloy is a Mg-Al-Ca-Mn-Cu-Ni magnesium alloy, which is composed of the following elements by mass percentage: Al 0.30wt%, Ca 1.00wt%, Mn 0.90wt%, Cu 1.0wt%, Ni is 0.50wt%, and the rest is Mg and unavoidable impurity elements.
实施例4一种低成本可溶性镁合金Embodiment 4 A kind of low-cost soluble magnesium alloy
所述低成本可溶性镁合金为Mg-Al-Ca-Mn-Cu-Ni镁合金,由以下质量百分比的元素组成:Al 0.40wt%、Ca 1.00wt%、Mn 1.00wt%、Cu 1.2wt%、Ni 0.50wt%,其余为Mg及不可避免的杂质元素。The low-cost soluble magnesium alloy is a Mg-Al-Ca-Mn-Cu-Ni magnesium alloy, which is composed of the following elements by mass percentage: Al 0.40wt%, Ca 1.00wt%, Mn 1.00wt%, Cu 1.2wt%, Ni is 0.50wt%, and the rest is Mg and unavoidable impurity elements.
实施例5一种低成本可溶性镁合金制备方法Embodiment 5 A kind of preparation method of low-cost soluble magnesium alloy
原料为:纯镁锭、纯铝锭、Mg-25%Ca中间合金、Mg-10%Mn中间合金、Mg-30%Cu中间合金、Mg-25%Ni中间合金。The raw materials are: pure magnesium ingot, pure aluminum ingot, Mg-25%Ca master alloy, Mg-10%Mn master alloy, Mg-30%Cu master alloy, Mg-25%Ni master alloy.
按配比称重原料,上述原料采用纯镁锭、纯铝锭、Mg-25%Ca中间合金、Mg-10%Mn中间合金;在CO2+SF6混合气体(体积比为300:1)保护条件下,在720℃熔炼,保温60min,搅拌10min,并精炼20min,精炼后升温至740℃静置30min,在720℃浇注成铸锭。The raw materials are weighed according to the proportion. The above raw materials are pure magnesium ingot, pure aluminum ingot, Mg-25%Ca master alloy, Mg-10%Mn master alloy; protected by CO 2 +SF 6 mixed gas (volume ratio of 300:1) Under the condition of smelting at 720 ℃, heat preservation for 60 minutes, stirring for 10 minutes, and refining for 20 minutes, after refining, the temperature was raised to 740 ℃ and left to stand for 30 minutes, and cast into ingots at 720 ℃.
将上述铸锭在520℃下进行均匀化处理保温时间2h,冷却方式为风冷,然后切成相应的坯料并去皮。The above-mentioned ingots were homogenized at 520° C. for a holding time of 2 hours, and the cooling method was air cooling, and then cut into corresponding billets and peeled.
将上一步得到的坯料,经过挤压机在挤压温度350℃、挤压比为5、挤压速度20m/min条件下,挤压成棒材,即得。The blank obtained in the previous step is extruded into a rod through an extruder at an extrusion temperature of 350° C., an extrusion ratio of 5, and an extrusion speed of 20 m/min.
实施例6一种低成本可溶性镁合金制备方法Embodiment 6 A kind of preparation method of low-cost soluble magnesium alloy
原料为:纯镁锭、纯铝锭、Mg-25%Ca中间合金、Mg-10%Mn中间合金、Mg-30%Cu中间合金、Mg-25%Ni中间合金。The raw materials are: pure magnesium ingot, pure aluminum ingot, Mg-25%Ca master alloy, Mg-10%Mn master alloy, Mg-30%Cu master alloy, Mg-25%Ni master alloy.
按配比称重原料,上述原料采用纯镁锭、纯铝锭、纯锡锭、Mg-25%Ca中间合金、Mg-10%Mn中间合金;在CO2+SF6混合气体(体积比为400:1)保护条件下,在740℃熔炼,保温40min,搅拌5min,并精炼30min,精炼后升温至760℃静置40min,在740℃浇注成铸锭。The raw materials are weighed according to the proportion, and the above raw materials are pure magnesium ingot, pure aluminum ingot, pure tin ingot, Mg-25%Ca master alloy, Mg-10%Mn master alloy; in CO 2 +SF 6 mixed gas (volume ratio is 400 : 1) Under the protection conditions, smelting at 740 ℃, heat preservation for 40 minutes, stirring for 5 minutes, and refining for 30 minutes, after refining, the temperature is raised to 760 ℃ and left to stand for 40 minutes, and cast into an ingot at 740 ℃.
将上述铸锭在500℃下进行均匀化处理保温时间2h,冷却方式为风冷,然后切成相应的坯料并去皮。The above-mentioned ingots were homogenized at 500° C. for a holding time of 2 hours, and the cooling method was air cooling, and then cut into corresponding billets and peeled.
将上一步得到的坯料,经过挤压机在挤压温度400℃、挤压比为8、挤压速度20m/min条件下,挤压成棒材。The billet obtained in the previous step is extruded into a bar through an extruder at an extrusion temperature of 400° C., an extrusion ratio of 8, and an extrusion speed of 20 m/min.
实施例7一种低成本可溶性镁合金制备方法Embodiment 7 A kind of preparation method of low-cost soluble magnesium alloy
原料为:纯镁锭、纯铝锭、Mg-25%Ca中间合金、Mg-10%Mn中间合金、Mg-30%Cu中间合金、Mg-25%Ni中间合金。The raw materials are: pure magnesium ingot, pure aluminum ingot, Mg-25%Ca master alloy, Mg-10%Mn master alloy, Mg-30%Cu master alloy, Mg-25%Ni master alloy.
按配比称重原料,上述原料采用纯镁锭、纯铝锭、纯锡锭、Mg-25%Ca中间合金、Mg-10%Mn中间合金;在CO2+SF6混合气体(体积比为400:1)保护条件下,在720℃熔炼,保温40min,搅拌5min,并精炼30min,精炼后升温至750℃静置30min,在730℃浇注成铸锭。The raw materials are weighed according to the proportion, and the above raw materials are pure magnesium ingot, pure aluminum ingot, pure tin ingot, Mg-25%Ca master alloy, Mg-10%Mn master alloy; in CO 2 +SF 6 mixed gas (volume ratio is 400 : 1) Under the protection conditions, smelt at 720°C, keep warm for 40min, stir for 5min, and refine for 30min. After refining, heat up to 750°C and let stand for 30min, and cast into an ingot at 730°C.
将上述铸锭在510℃下进行均匀化处理保温时间1h,冷却方式为风冷,然后切成相应的坯料并去皮。The above-mentioned ingots were homogenized at 510° C. for a holding time of 1 hour, and the cooling method was air cooling, and then cut into corresponding billets and peeled.
将上一步得到的坯料,经过挤压机在挤压温度390℃、挤压比为10、挤压速度10m/min条件下,挤压成棒材。The billet obtained in the previous step was extruded into a rod through an extruder at an extrusion temperature of 390° C., an extrusion ratio of 10, and an extrusion speed of 10 m/min.
实施例8一种低成本可溶性镁合金制备方法Embodiment 8 A kind of preparation method of low-cost soluble magnesium alloy
原料为:纯镁锭、纯铝锭、Mg-25%Ca中间合金、Mg-10%Mn中间合金、Mg-30%Cu中间合金、Mg-25%Ni中间合金。The raw materials are: pure magnesium ingot, pure aluminum ingot, Mg-25%Ca master alloy, Mg-10%Mn master alloy, Mg-30%Cu master alloy, Mg-25%Ni master alloy.
按配比称重原料,上述原料采用纯镁锭、纯铝锭、纯锡锭、Mg-25%Ca中间合金、Mg-10%Mn中间合金;在CO2+SF6混合气体(体积比为300:1)保护条件下,在720℃熔炼,保温40min,搅拌10min,并精炼30min,精炼后升温至740℃静置30min,在720℃浇注成铸锭。The raw materials are weighed according to the proportion, and the above-mentioned raw materials are pure magnesium ingot, pure aluminum ingot, pure tin ingot, Mg-25%Ca master alloy, Mg-10%Mn master alloy; in CO 2 +SF 6 mixed gas (volume ratio of 300 : 1) Under the protection conditions, smelt at 720°C, keep warm for 40min, stir for 10min, and refine for 30min. After refining, heat up to 740°C and let stand for 30min, and cast it into an ingot at 720°C.
将上述铸锭在500℃下进行均匀化处理保温时间2h,冷却方式为风冷,然后切成相应的坯料并去皮。The above-mentioned ingots were homogenized at 500° C. for a holding time of 2 hours, and the cooling method was air cooling, and then cut into corresponding billets and peeled.
将上一步得到的坯料,经过挤压机在挤压温度380℃、挤压比为10、挤压速度5m/min条件下,挤压成棒材。The billet obtained in the previous step is extruded into a rod through an extruder at an extrusion temperature of 380° C., an extrusion ratio of 10, and an extrusion speed of 5 m/min.
对比例1Comparative Example 1
对比合金为铸态AZ91D镁合金,该合金的化学成分为:Mg-9.0wt%Al-0.80wt%Zn-0.3wt%Mn-0.025wt%Cu,合金配料(原料为:纯镁锭、纯铝锭、纯锌锭、Mg-10%Mn中间合金、Mg-30%Cu中间合金)。The comparison alloy is as-cast AZ91D magnesium alloy, the chemical composition of the alloy is: Mg-9.0wt%Al-0.80wt%Zn-0.3wt%Mn-0.025wt%Cu, alloy ingredients (raw materials: pure magnesium ingot, pure aluminum ingot, pure zinc ingot, Mg-10%Mn master alloy, Mg-30%Cu master alloy).
对比例2:Comparative Example 2:
与实施例1的区别在于,Mg-Al-Ca-Mn-Cu-Ni合金元素的质量百分比为:Al0.70wt%、Ca 1.20wt%、Mn 1.00wt%、Cu 1.5wt%、Ni 1.50wt%其余为Mg及不可避免的杂质元素。The difference from Example 1 is that the mass percentages of Mg-Al-Ca-Mn-Cu-Ni alloy elements are: Al 0.70wt%, Ca 1.20wt%, Mn 1.00wt%, Cu 1.5wt%, Ni 1.50wt% The rest are Mg and inevitable impurity elements.
对比例3:Comparative Example 3:
与实施例1的区别在于,Mg-Al-Ca-Mn-Cu-Ni合金元素的质量百分比为:Al0.30wt%、Ca 0.20wt%、Mn 0.10wt%、Cu 0.05wt%、Ni 0.05wt%其余为Mg及不可避免的杂质元素。The difference from Example 1 is that the mass percentages of Mg-Al-Ca-Mn-Cu-Ni alloy elements are: Al 0.30wt%, Ca 0.20wt%, Mn 0.10wt%, Cu 0.05wt%, Ni 0.05wt% The rest are Mg and inevitable impurity elements.
对比例4Comparative Example 4
与实施例7的区别在于,挤压温度450℃,挤压比为10,挤压速度10m/min条件下,挤压成棒材。The difference from Example 7 is that the extrusion temperature is 450° C., the extrusion ratio is 10, and the extrusion speed is 10 m/min.
对比例5Comparative Example 5
与实施例5的区别在于,挤压比为40,挤压速度10m/min条件下,挤压成棒材。The difference from Example 5 is that the extrusion ratio is 40 and the extrusion speed is 10 m/min, and the rod is extruded.
对比例6Comparative Example 6
与实施例5的区别在于,挤压比为80,挤压速度10m/min条件下,挤压成棒材。The difference from Example 5 is that the extrusion ratio is 80 and the extrusion speed is 10 m/min, and the rod is extruded.
试验例Test example
组1:实施例1合金按实施例5方法制备;Group 1: The alloy of Example 1 was prepared according to the method of Example 5;
组2:实施例2合金按实施例6方法制备;Group 2: The alloy of Example 2 was prepared by the method of Example 6;
组3:实施例3合金按实施例7方法制备;Group 3: The alloy of Example 3 was prepared by the method of Example 7;
组4:实施例4合金按实施例8方法制备;Group 4: The alloy of Example 4 was prepared according to the method of Example 8;
组5:对比例1合金按实施例5方法制备;Group 5: Comparative Example 1 alloy was prepared by the method of Example 5;
组6:对比例2合金按实施例5方法制备;Group 6: Comparative Example 2 alloy was prepared by the method of Example 5;
组7:对比例3合金按实施例5方法制备;Group 7: Comparative Example 3 alloy was prepared by the method of Example 5;
组8:实施例1合金按对比例4方法制备;Group 8: The alloy of Example 1 was prepared by the method of Comparative Example 4;
组9:实施例1合金按对比例5方法制备;Group 9: The alloy of Example 1 was prepared by the method of Comparative Example 5;
组10:实施例1合金按对比例6方法制备;Group 10: The alloy of Example 1 was prepared by the method of Comparative Example 6;
对各组合金的力学性能及溶解性进行测定;The mechanical properties and solubility of each combination of gold were measured;
力学性能测试方法依据GB T 228.1-2010执行。The mechanical properties test method is performed according to GB T 228.1-2010.
溶解性能测试条件为:将的试样置于93℃的质量分数为3%KCl水溶液中,测试每小时溶解的重量。溶解速率为:溶解的重量/(试样表面积×时间)。The dissolution performance test conditions are: The sample was placed in a 3% KCl aqueous solution at 93°C, and the dissolved weight per hour was measured. The dissolution rate is: weight dissolved/(sample surface area x time).
表1镁合金室温力学性能与高温溶解速率Table 1 Room temperature mechanical properties and high temperature dissolution rate of magnesium alloys
比较实施例与对比例的镁合金室温力学性能与高温溶解速率,可以看出:本发明的制备的低成本可溶解镁合金的室温力学性能明显优于对比例合金,而且本发明的合金在93℃、3%KCl溶液中的溶解速率明显优于对比例合金。Comparing the room temperature mechanical properties and high temperature dissolution rate of the magnesium alloys of the examples and the comparative examples, it can be seen that the room temperature mechanical properties of the low-cost soluble magnesium alloy prepared by the present invention are obviously better than those of the comparative example alloy, and the alloy of the present invention is 93 The dissolution rate in ℃, 3% KCl solution is obviously better than that of the comparative alloy.
从试验例组1和试验例组6合金的显微组织形貌可以看出:本发明制备材料的晶粒尺寸均匀细小;并且第二相更加弥散(如图1、图2所示)。因而,其室温力学性能明显优于对比例合金。It can be seen from the microstructures of the alloys of Test Example Group 1 and Test Example Group 6: the grain size of the material prepared by the present invention is uniform and fine; and the second phase is more dispersed (as shown in Figure 1 and Figure 2). Therefore, its room temperature mechanical properties are significantly better than those of the comparative alloys.
对比试验例组1、9和10,可以看出:材料的力学性能随着挤压比增大而进一步增强。本发明采用较小的挤压比即可达到较好的性能,有利于该合金及制备方法的推广应用。Comparing the test example groups 1, 9 and 10, it can be seen that the mechanical properties of the material are further enhanced as the extrusion ratio increases. The invention can achieve better performance by adopting a smaller extrusion ratio, which is beneficial to the popularization and application of the alloy and the preparation method.
综上所述,本发明的低成本可溶解镁合金能满足页岩油气开采过程中多级滑套分段压裂技术相关的不同零部件性能需求。To sum up, the low-cost dissolvable magnesium alloy of the present invention can meet the performance requirements of different components related to the multi-stage sliding sleeve staged fracturing technology in the shale oil and gas exploitation process.
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。The above-mentioned embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above-mentioned embodiments, and any other changes, modifications, substitutions, combinations, The simplification should be equivalent replacement manners, which are all included in the protection scope of the present invention.
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