CN114908280B - High-strength-toughness rapidly-degraded Mg-Er-Ni alloy for underground fracturing and preparation method thereof - Google Patents
High-strength-toughness rapidly-degraded Mg-Er-Ni alloy for underground fracturing and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-strength and high-toughness fast degradation Mg-Er-Ni alloy for underground fracturing, which comprises the following components in percentage by mass: er:6-15%, ni:1-5%, the molar ratio of Er/Ni is 1.3-1.8, and the balance is Mg and inevitable impurity elements; wherein Mg, ni and Er mainly form Ni-LPSO phase which is layered and blocky and coexists, and the volume fraction of the Ni-LPSO phase is 15-36%. The invention also discloses a preparation method and application of the Mg-Er-Ni alloy. The Mg-Er-Ni alloy provided by the invention takes magnesium as a base material, and Ni and Er are added; and through regulating the molar ratio of Er/Ni, the solution treatment temperature, time and cooling speed and finally homogenizing heat treatment in short time before extrusion, layered LPSO phase which is not precipitated in the Mg matrix in the rapid cooling process is precipitated to prepare alloy containing blocky and layered Ni-LPSO phases, so that brittle Mg is avoided 2 Ni phase and low potential MgEr rare earth phase are generated, and simultaneously, the synergistic promotion of the obdurability and the degradation characteristic is realized.
Description
Technical Field
The invention belongs to the technical field of oil and gas exploitation materials, and particularly relates to a high-strength and high-toughness rapidly-degradable Mg-Er-Ni alloy for underground fracturing and a preparation method thereof.
Background
The reserves of oil and gas resources in China are rich, but over 70 percent of the oil and gas resources are unconventional oil and gas resources, the current production rate of the oil and gas resources is less than 10 percent, and the reason is the development technical limit of fracturing tools for unconventional oil and gas exploitation. The existing drillable fracturing tool has obvious limitations due to the defects of high construction difficulty, time and labor consumption, high increase and the like, and the soluble fracturing tool has the advantages of simple construction, low cost, reliability, complete solubility and the like, quickly occupies the market and is put into the exploitation of unconventional oil gas. However, in the face of the requirements of higher efficiency, deeper exploitation depth and more complex exploitation environment of oil and gas exploitation, a fracturing tool with high strength and rapid degradation is urgently needed to be developed.
At present, the development of soluble fracturing tools is based on magnesium with high specific strength, low density and low corrosion resistance as a raw material, and a series of alloying and deformation processing means are adopted to develop the soluble magnesium alloy fracturing tools. The currently developed Mg-Al series and Mg-Zn series fracturing tools have the problems of low strength or poor degradation performance more or less, and cannot better meet the use requirements of the fracturing tools in high-pressure complex environments. And the highest strength of the Mg-RE-Ni alloy containing multiple second phases can reach 510MPa, but the highest degradation rate is 2400mm/a, so that the magnesium alloy material for rapid degradation and fracturing with high strength is urgently needed to be developed.
Disclosure of Invention
The present invention is directed to solving, at least in part, one of the technical problems in the related art. Therefore, the invention mainly aims to provide a high-strength and high-toughness rapidly-degradable Mg-Er-Ni alloy for underground fracturing, and aims to solve the problem that the existing magnesium alloy cannot give consideration to both strength and degradation rate.
The purpose of the invention is realized by the following technical scheme:
a high-strength and high-toughness rapidly-degradable Mg-Er-Ni alloy for underground fracturing comprises the following components in percentage by mass: er:6-15%, ni:1-5%, the molar ratio of Er/Ni is 1.3-1.8, and the balance is Mg and inevitable impurity elements; wherein Mg, ni and Er mainly form Ni-LPSO phase which is layered and blocky and coexists, and the volume fraction of the Ni-LPSO phase is 15-36%.
In certain embodiments, the Er/Ni molar ratio is 1.4 to 1.6 and the volume fraction of the Ni-LPSO phase is 24 to 36%.
The invention also provides a preparation method of the Mg-Er-Ni alloy, which comprises the following steps: uniformly mixing a nickel source, a magnesium source and an erbium source, and carrying out alloying treatment to obtain the high-strength-toughness rapidly-degraded Mg-Er-Ni alloy.
In certain embodiments, the nickel source is selected from elemental nickel and/or nickel alloys;
further, the nickel alloy is selected from magnesium-nickel alloy;
in certain embodiments, the magnesium source is selected from elemental magnesium and/or magnesium alloys;
further, the magnesium alloy is selected from magnesium-nickel alloys;
in certain embodiments, the erbium source comprises at least one of a magnesium erbium alloy, a nickel erbium alloy;
in certain embodiments, the alloying process is a melt casting process and a powder alloying process;
further, alloying treatment is carried out by adopting a smelting and casting method;
in certain embodiments, the melt casting method comprises the steps of:
(a) Casting: uniformly mixing a nickel source, a magnesium source and an erbium source, and carrying out smelting casting to obtain an as-cast alloy;
(b) And (3) heat treatment: and carrying out homogenization treatment and extrusion deformation treatment on the as-cast alloy in sequence to obtain the high-strength high-toughness rapidly-degraded Mg-Er-Ni alloy.
Further, in the step (a), when smelting and casting are carried out, firstly heating to 760-800 ℃, preserving heat and stirring to completely melt the raw materials, then preserving heat for 10-20min at 760-780 ℃, and finally carrying out rapid cooling through a brine bath at 5-10 ℃ to obtain an as-cast alloy;
furthermore, inert gas is adopted for protection during smelting and casting; the inert gas is at least one of helium, argon, carbon dioxide and sulfur hexafluoride;
further: in step (b), the homogenization treatment is carried out at 380-420 deg.C for 25-35min.
Further, in the step (b), the extrusion ratio when carrying out extrusion deformation treatment is 9-15, and the extrusion deformation speed is 0.3-0.4m/min; preferably, the temperature at which the extrusion deformation treatment is carried out is 380 to 420 ℃.
The invention also aims to provide application of the Mg-Er-Ni alloy in the field of oil and gas development.
Compared with the prior art, the invention has at least the following advantages:
1) The high-strength and high-toughness rapidly-degradable Mg-Er-Ni alloy for underground fracturing provided by the invention takes magnesium as a base material, is melted at 760-800 ℃ by adding Ni and Er, is subjected to heat preservation treatment at 760-780 ℃ for 10-20min, and is rapidly cooled by a brine bath at 5-10 ℃ to regulate and control the structure form of a second phase; controlling the molar ratio of Er/Ni to generate Ni-LPSO phase only; finally, the lamellar LPSO phase which is not precipitated in the Mg matrix in the rapid cooling process is precipitated through the homogenization heat treatment in a short time before the extrusion, and the alloy containing the blocky and lamellar Ni-LPSO phases is prepared, so that the brittle Mg is avoided 2 A Ni phase and a low-potential MgEr rare earth phase are generated, and the synergistic promotion of the toughness and the degradation characteristic is realized at the same time.
2) The high-strength and high-toughness rapidly-degraded Mg-Er-Ni alloy for underground fracturing has the advantages of simple process flow, no need of solid solution and aging heat treatment, simplified working procedures and reduced cost, and the adopted equipment such as a resistance furnace, an extruder and the like are conventional equipment, so that the Mg-Er-Ni alloy is convenient for industrial application.
Drawings
In order to more clearly illustrate the embodiments of the present invention, reference will now be made briefly to the embodiments or to the accompanying drawings that are needed in the description of the prior art.
FIG. 1 is an SEM image of a Mg-Er-Ni alloy provided in example 2 of the present invention;
FIG. 2 is an ImagePro test chart of Mg-Er-Ni alloy provided in example 2 of the present invention;
FIG. 3 is a TEM image of Mg-Er-Ni alloy provided in example 2 of the present invention;
FIG. 4 is an engineering force diagram of Mg-Er-Ni alloys provided in examples 1-6 of the present invention.
Detailed Description
The present invention will be further described with reference to the following drawings and examples, which are illustrative only and not intended to be limiting, and the scope of the present invention is not limited thereby. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the examples below, pure magnesium, mg-30wt.% Er and Mg-30wt.% Ni master alloys are purchased from Shandong Ruifeng metalworking, inc., carbon dioxide (CO) 2 ) And sulfur hexafluoride (SF) 6 ) Purchased from Chongqing Ruiko gas Co., ltd, and the corrosion rate measuring bottle KCl purchased from Chongqing Huanghui chemical hazardous articles marketing Co., ltd.
In the following examples, the mechanical properties were measured by an electronic universal tensile testing machine (GB/T1177-2018) (test method), the type of the equipment used was CMT-5105, the degradation rate was measured by the alloy immersion test (GB/T16886.15) (test method), the equipment used was a digital display constant temperature water bath, the type of which was HH-2; testing the volume fraction of a phase body in the alloy by adopting Image Pro phase volume fraction analysis software; phase identification was performed using SEM and Transmission Electron Microscope (TEM).
Example 1
The invention provides a high-strength and high-toughness rapidly-degraded Mg-Er-Ni alloy for underground fracturing, which comprises the following components in percentage by mass: er:6.2%, ni:1.5 percent of Mg and inevitable impurity elements (the mass percentage of the inevitable impurity elements in the alloy is not higher than 0.2 percent), wherein the molar ratio of Er/Ni is 1.45.
The invention provides a preparation method of a high-strength, high-toughness and fast-degradation Mg-Er-Ni alloy for underground fracturing, which comprises the following steps of:
1) Weighing commercial pure magnesium blocks and intermediate alloys of Mg, er and Ni in the weight percentages of 30-30 and Mg, ni in the weight percentages of 30, polishing the surfaces of the raw materials, removing surface oxidation layers, sequentially placing the raw materials in industrial alcohol, and cleaning the raw materials in an ultrasonic cleaner;
2) Setting the temperature of the resistance furnace at 760 ℃ in carbon dioxide(CO 2 ) And sulfur hexafluoride (SF) 6 ) Under the protection of the mixed gas, firstly, filling a pure Mg block and Mg-30wt.% Er intermediate alloy into a crucible, putting the crucible into a resistance furnace, after the materials are melted, then adding Mg-30wt.% Ni intermediate alloy, and after the materials are completely melted, keeping the temperature for 20min at 760 ℃; after the heat preservation is finished, taking the crucible out of the resistance furnace, and quickly cooling the crucible by using a brine bath at 5 ℃ to prepare as-cast alloy;
3) Turning the cast alloy to prepare an extrusion ingot with the diameter of 80mm and the height of 60mm, peeling the extrusion ingot, preheating the extrusion ingot to 380 ℃, maintaining for 35min for homogenization treatment, and then placing the extrusion ingot into an extrusion cylinder for extrusion, wherein the extrusion temperature is 380 ℃, the extrusion ratio is 15, and the extrusion speed is 0.3m/min, so as to obtain the extrusion rod.
For the alloy in the short-time homogenized state prepared in the embodiment, the Scanning Electron Microscope (SEM) is used for shape scanning, the Transmission Electron Microscope (TEM) is used for shape scanning analysis, and the Image Pro analysis software is used for performance detection of the volume fraction of the second phase, so that Mg, er and Ni in the alloy in the short-time homogenized state form a Ni-LPSO-containing phase coexisting in a layered and blocky manner, and the volume fraction of the phase is 15.2%.
Example 2
The invention provides a high-strength high-toughness fast-degradation Mg-Er-Ni alloy for underground fracturing, which comprises the following components in percentage by mass: er7.6%, ni:1.9 percent of Mg and inevitable impurity elements (the mass percentage of the inevitable impurity elements in the alloy is not higher than 0.2 percent), wherein the molar ratio of Er/Ni is 1.41.
The invention provides a preparation method of a high-strength high-toughness fast-degradation Mg-Er-Ni alloy for underground fracturing, which comprises the following steps of:
1) Weighing commercial pure magnesium blocks, mg-30wt.% Er and Mg-30wt.% Ni intermediate alloy according to the components of the alloy, polishing the surface of the raw material, removing a surface oxide layer, sequentially placing the raw material in industrial alcohol, and placing the industrial alcohol in an ultrasonic cleaner for cleaning;
2) The temperature of the resistance furnace was set to 770 ℃ in carbon dioxide (CO) 2 ) And sulfur hexafluoride (SF) 6 ) Under the protection of the mixed gas, firstly, filling a pure Mg block and Mg-30wt.% Er intermediate alloy into a crucible, putting the crucible into a resistance furnace, after the materials are melted, then adding Mg-30wt.% Ni intermediate alloy, and after the materials are completely melted, keeping the temperature for 18min at 760 ℃; after the heat preservation is finished, taking the crucible out of the resistance furnace, and quickly cooling the crucible by using a brine bath at 5 ℃ to prepare as-cast alloy;
3) Turning the cast alloy to prepare an extrusion ingot with the diameter of 80mm and the height of 60mm, peeling the extrusion ingot, preheating the extrusion ingot to 400 ℃, maintaining for 30min for homogenization treatment, and then putting the extrusion ingot into an extrusion cylinder for extrusion, wherein the extrusion temperature is 400 ℃, the extrusion ratio is 11, and the extrusion speed is 0.3m/min, so as to obtain the extrusion rod.
As shown in fig. 1, 2 and 3, it is known that Mg, er and Ni in the alloy in the short-time homogenized state formed a Ni — LPSO-containing phase in which layers and blocks coexisted, the volume fraction of the phase was 19.1%, and the Er/Ni molar ratio was 1.41, as a result of performing morphology scanning with a Scanning Electron Microscope (SEM), morphology scanning analysis with a Transmission Electron Microscope (TEM), and performance detection of the volume fraction of the second phase with Image Pro analysis software.
Example 3
The invention provides a high-strength high-toughness fast-degradation Mg-Er-Ni alloy for underground fracturing, which comprises the following components in percentage by mass: er:8.8%, ni:2.3 percent of Mg and the balance of inevitable impurity elements (the mass percentage of the inevitable impurity elements in the alloy is not higher than 0.2 percent), wherein the molar ratio of Er/Ni is 1.33.
The invention provides a preparation method of a high-strength high-toughness fast-degradation Mg-Er-Ni alloy for underground fracturing, which comprises the following steps of:
1) Weighing commercial pure magnesium blocks, mg-30wt.% Er and Mg-30wt.% Ni intermediate alloy according to the components of the alloy, polishing the surface of the raw material, removing a surface oxide layer, sequentially placing the raw material in industrial alcohol, and placing the industrial alcohol in an ultrasonic cleaner for cleaning;
2) Setting the temperature of the resistance furnace at 780 ℃ in carbon dioxide (CO) 2 ) And sulfur hexafluoride (SF) 6 ) Under the protection of the mixed gas, firstly, filling pure Mg blocks and Mg-30wt.% Er intermediate alloy into a crucible, putting the crucible into a resistance furnace, after the materials are molten, then adding Mg-30wt.% Ni intermediate alloy, and after the materials are completely molten, preserving heat for 15min at 770 ℃; after the heat preservation is finished, taking the crucible out of the resistance furnace, and quickly cooling the crucible by using a saline bath at 6 ℃ to prepare as-cast alloy;
3) Turning the cast alloy to prepare an extrusion ingot with the diameter of 80mm and the height of 60mm, peeling the extrusion ingot, preheating the extrusion ingot to 400 ℃, maintaining for 25min for homogenization treatment, and then placing the extrusion ingot into an extrusion cylinder for extrusion, wherein the extrusion temperature is 400 ℃, the extrusion ratio is 9, and the extrusion speed is 0.3m/min, so as to obtain the extrusion rod.
For the alloy in the short-time homogenized state prepared in this example, the alloy was subjected to shape scanning by using a Scanning Electron Microscope (SEM), shape scanning analysis by using a Transmission Electron Microscope (TEM), and performance detection of the volume fraction of the second phase by using Image Pro analysis software, it was found that Mg, er, and Ni in the alloy in the short-time homogenized state formed a Ni — LPSO-containing phase coexisting in a layered and massive state, and the volume fraction of the phase was 24.2%. (ii) a
Example 4
The invention provides a high-strength and high-toughness rapidly-degraded Mg-Er-Ni alloy for underground fracturing, which comprises the following components in percentage by mass: er:10.6%, ni:2.8 percent of Mg and inevitable impurity elements (the mass percentage of the inevitable impurity elements in the alloy is not higher than 0.2 percent), wherein the molar ratio of Er/Ni is 1.32.
The invention provides a preparation method of a high-strength high-toughness fast-degradation Mg-Er-Ni alloy for underground fracturing, which comprises the following steps of:
1) Weighing commercial pure magnesium blocks, mg-30wt.% Er and Mg-30wt.% Ni intermediate alloy according to the components of the alloy, polishing the surface of the raw material, removing a surface oxide layer, sequentially placing the raw material in industrial alcohol, and placing the industrial alcohol in an ultrasonic cleaner for cleaning;
2) The temperature of the resistance furnace was set to 790 ℃ in carbon dioxide (CO) 2 ) And sulfur hexafluoride (f)SF 6 ) Under the protection of the mixed gas, firstly, filling pure Mg blocks and Mg-30wt.% Er intermediate alloy into a crucible, putting the crucible into a resistance furnace, after the materials are melted, then adding Mg-30wt.% Ni intermediate alloy, and after the materials are completely melted, keeping the temperature at 770 ℃ for 13min; after the heat preservation is finished, taking the crucible out of the resistance furnace, and quickly cooling the crucible by using a saline bath at the temperature of 8 ℃ to prepare an as-cast alloy;
3) Turning the cast alloy to prepare an extrusion ingot with the diameter of 80mm and the height of 60mm, peeling the extrusion ingot, preheating the extrusion ingot to 420 ℃, maintaining for 25min for homogenization treatment, and then putting the extrusion ingot into an extrusion cylinder for extrusion, wherein the extrusion temperature is 420 ℃, the extrusion ratio is 12, and the extrusion speed is 0.4m/min, so as to obtain the extrusion rod.
For the alloy in the short-time homogenized state prepared in the embodiment, the Scanning Electron Microscope (SEM) is used for shape scanning, the Transmission Electron Microscope (TEM) is used for shape scanning analysis, and the Image Pro analysis software is used for performance detection of the volume fraction of the second phase, so that Mg, er and Ni in the alloy in the short-time homogenized state form a Ni-LPSO-containing phase with layered and blocky coexisting layers, and the volume fraction of the phase is 28.3%.
Example 5
The invention provides a high-strength and high-toughness rapidly-degraded Mg-Er-Ni alloy for underground fracturing, which comprises the following components in percentage by mass: er:13.2%, ni:3.4 percent of Mg and inevitable impurity elements (the mass percentage of the inevitable impurity elements in the alloy is not higher than 0.2 percent), wherein the molar ratio of Er to Ni is 1.36.
The invention provides a preparation method of a high-strength high-toughness fast-degradation Mg-Er-Ni alloy for underground fracturing, which comprises the following steps of:
1) Weighing commercial pure magnesium blocks, mg-30wt.% Er and Mg-30wt.% Ni intermediate alloy according to the components of the alloy, polishing the surface of the raw material, removing a surface oxide layer, sequentially placing the raw material in industrial alcohol, and placing the industrial alcohol in an ultrasonic cleaner for cleaning;
2) The temperature of the resistance furnace was set to 790 ℃ in carbon dioxide (CO) 2 ) And sulfur hexafluoride (SF) 6 ) Mixed gas of (2)Under protection, firstly putting a pure Mg block and Mg-30wt.% Er master alloy into a crucible, putting the crucible into a resistance furnace, after the materials are molten, putting Mg-30wt.% Ni master alloy into the crucible, and after the materials are completely molten, keeping the temperature for 13min at 775 ℃; after the heat preservation is finished, taking the crucible out of the resistance furnace, and quickly cooling the crucible by using a saline water bath at the temperature of 8 ℃ to prepare an as-cast alloy;
3) Turning the cast alloy to prepare an extrusion ingot with the diameter of 80mm and the height of 60mm, peeling the extrusion ingot, preheating the extrusion ingot to 410 ℃, maintaining for 30min for homogenization treatment, and then placing the extrusion ingot into an extrusion cylinder for extrusion, wherein the extrusion temperature is 410 ℃, the extrusion ratio is 13, and the extrusion speed is 0.4m/min, so as to obtain the extrusion rod.
For the alloy in the short-time homogenized state prepared in the embodiment, the Scanning Electron Microscope (SEM) is used for shape scanning, the Transmission Electron Microscope (TEM) is used for shape scanning analysis, and the Image Pro analysis software is used for performance detection of the volume fraction of the second phase, so that Mg, er and Ni in the alloy in the short-time homogenized state form a Ni-LPSO-containing phase with layered and blocky coexisting layers, and the volume fraction of the phase is 32.2%.
Example 6
The invention provides a high-strength and high-toughness rapidly-degraded Mg-Er-Ni alloy for underground fracturing, which comprises the following components in percentage by mass: er:14.8%, ni:3.9 percent of Mg and the balance of inevitable impurity elements (the mass percentage of the inevitable impurity elements in the alloy is not higher than 0.2 percent), wherein the molar ratio of Er/Ni is 1.33.
The invention provides a preparation method of a high-strength high-toughness fast-degradation Mg-Er-Ni alloy for underground fracturing, which comprises the following steps of:
1) Weighing commercial pure magnesium blocks, mg-30wt.% Er and Mg-30wt.% Ni intermediate alloy according to the components of the alloy, polishing the surface of the raw material, removing a surface oxide layer, sequentially placing the raw material in industrial alcohol, and placing the industrial alcohol in an ultrasonic cleaner for cleaning;
2) Setting the temperature of the resistance furnace at 800 deg.C in carbon dioxide (CO) 2 ) And sulfur hexafluoride (SF) 6 ) Under the protection of mixed gas of (2), firstly mixing pure Mg blocks withPutting Mg-30wt.% Er intermediate alloy into a crucible, putting the crucible into a resistance furnace, after the material is melted, putting Mg-30wt.% Ni intermediate alloy into the crucible, and after the material is completely melted, keeping the temperature at 780 ℃ for 10min; after the heat preservation is finished, taking the crucible out of the resistance furnace, and quickly cooling the crucible by using a 9 ℃ brine bath to prepare as-cast alloy;
3) Turning the cast alloy to prepare an extrusion ingot with the diameter of 80mm and the height of 60mm, peeling the extrusion ingot, preheating the extrusion ingot to 400 ℃, maintaining for 30min for homogenization treatment, and then putting the extrusion ingot into an extrusion cylinder for extrusion, wherein the extrusion temperature is 400 ℃, the extrusion ratio is 11, and the extrusion speed is 0.3m/min, so as to obtain the extrusion rod.
For the alloy in the short-time homogenized state prepared in the embodiment, the Scanning Electron Microscope (SEM) is used for shape scanning, the Transmission Electron Microscope (TEM) is used for shape scanning analysis, and the Image Pro analysis software is used for performance detection of the volume fraction of the second phase, so that Mg, er and Ni in the alloy in the short-time homogenized state form a Ni-LPSO-containing phase with layered and blocky coexisting layers, and the volume fraction of the phase is 36.0%.
Comparative example 1
The Mg-Er-Ni alloy of this comparative example has substantially the same composition as that of example 2 except that the Ni content is the same, but the molar Er/Ni ratio is 1.0, and is prepared in the same manner as in example 2.
And performing morphology scanning on the short-time homogenized alloy prepared in the comparative example by using a Scanning Electron Microscope (SEM), performing morphology scanning analysis by using a Transmission Electron Microscope (TEM), and performing performance detection on the volume fraction of the second phase by using Image Pro analysis software to obtain that the alloy sample not only contains a blocky Ni-LPSO phase, but also contains Mg 2 Ni phase, and bulk Ni-LPSO phase and Mg 2 The volume fractions of the Ni phase were 9.8 and 4.8, respectively.
Comparative example 2
The Mg-Er-Ni alloy of this comparative example has substantially the same composition as that of example 2, except that the Er content is the same, but the molar Er/Ni ratio is 2.8, and is prepared in the same manner as in example 2.
And performing shape scanning on the short-time homogenized alloy prepared in the comparative example by using a Scanning Electron Microscope (SEM), performing shape scanning analysis by using a Transmission Electron Microscope (TEM), and performing performance detection on the volume fraction of the second phase by using Image Pro analysis software to obtain that the alloy sample not only contains a blocky Ni-LPSO phase, but also contains a MgEr phase, and the volume fractions of the Ni-LPSO phase and the MgEr phase are 14.1% and 9.4% respectively.
Comparative example 3
The Mg-Er-Ni alloy provided by the comparative example has the same composition as that of example 2, and the preparation method is basically the same as that of example 2, except that the homogenization treatment of the extruded ingot is performed at 380-420 ℃ for 10min.
And performing morphology scanning on the alloy prepared in the short-time homogenized state by adopting a Scanning Electron Microscope (SEM), performing morphology scanning analysis by adopting a Transmission Electron Microscope (TEM), and performing performance detection on the volume fraction of the second phase by adopting Image Pro analysis software to obtain that the alloy sample contains a layered and blocky Ni-LPSO phase, and the volume fraction of the Ni-LPSO phase is 14.2%.
Comparative example 4
The Mg-Er-Ni alloy provided by the comparative example has the same composition as that of the Mg-Er-Ni alloy provided by the example 2, and the preparation method of the Mg-Er-Ni alloy is basically the same as that of the Mg-Er-Ni alloy provided by the example 2, except that the homogenization treatment of an extrusion ingot is carried out at the temperature of 380-420 ℃ for 60min.
The alloy sample in the short-time homogenized state prepared by the comparative example is subjected to shape scanning by a Scanning Electron Microscope (SEM), shape scanning analysis by a Transmission Electron Microscope (TEM) and performance detection by Image Pro analysis software on the volume fraction of the second phase, so that the alloy sample is mainly in a layered Ni-LPSO phase, and the volume fraction of the Ni-LPSO phase is 22.5%.
Comparative example 5
The Mg-Er-Ni alloy provided by the comparative example has the same components as those of the example 2, and the preparation method is the same as that of the example 2, except that the cast alloy is smelted at 770 ℃, kept at 680 ℃ for 18min and cooled by brine at room temperature (25-35 ℃).
In the alloy prepared in the embodiment, the alloy in a short-time homogenized state is subjected to shape scanning analysis by a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM), and the performance of the alloy is detected by Image Pro analysis software, so that Mg, er and Ni in the alloy sample only form a blocky Ni-LPSO phase, and the volume fraction of the Ni-LPSO phase is 19.8%.
Comparative example 6
The Mg-Er-Ni alloy provided by the comparative example has the same components as those of the example 2, and the preparation method is the same as that of the example 2, except that the cast alloy is smelted at 770 ℃, kept at 650 ℃ for 18min and cooled by salt water at room temperature (25-35 ℃).
In the short-time homogenized alloy prepared in the embodiment, the appearance scanning analysis is performed by using a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM), and the performance detection is performed on the volume fraction of the second phase by using Image Pro analysis software, so that Mg, er and Ni in an alloy sample only form a bulk Ni-LPSO phase, and the volume fraction of the Ni-LPSO phase is 19.5%.
And (4) performance testing:
the Mg-Er-Ni alloy prepared in the embodiments 1-6 and the comparative examples 1-4 is subjected to performance test, wherein the mechanical property is detected by GB/T1177-2018, the degradation rate is GB/T16886.15, the Mg-Er-Ni alloy is tested in KCl solution at 93 ℃ and 3wt.%, and the specific results are shown in FIG. 4 and Table 1:
TABLE 1 mechanical Properties and composition phases of Mg-Er-Ni alloys
According to the table, in the Er/Ni molar ratio of 1.3-1.8, melting at 760-800 ℃, rapidly cooling after maintaining the temperature at 760-780 ℃ for 10-20min, homogenizing at 400 ℃ for 25-35min before extrusion, only having single Ni-LPSO phase containing layers and blocks, wherein the volume fraction of the Ni-LPSO phase is 15-36%, with the increase of the content of the Ni-LPSO phase, the tensile strength of the Mg-Er-Ni alloy is 330-530MPa, and the degradation rate is 85.1Mg/cm 2 The/h is increased to 142.1mg/cm 2 However, when the molar ratio of Er/Ni is outside this range, the specific ratio of 1.0 as in comparative example 1, the strength was reduced from 360MPa to 345MPa, and the plasticity was reduced from 12.6% to 8.1%, due to the generation of Mg 2 The Ni phase not only reduces the strength of the alloy, but also degrades the plasticity of the alloy, and in addition, the generation of the phase only produces blocky LPSO phase under the same Ni content, and simultaneously reduces the content of Ni-LPSO, so that the degradation rate of the alloy is from 94.3mg/cm 2 The flow rate is reduced to 62.7mg/cm 2 H is used as the reference value. In addition, the specific ratio of 2.80 in comparative example 2, the reason for the decrease in mechanical properties is that the alloy has bulk Ni-LPSO phase and MgEr phase, and the decrease in Ni-LPSO content, and the coarsening and growth of crystal grains during deformation cannot inhibit the dynamic recrystallization process, so that the strength of the alloy can be decreased from 360MPa to 335MPa, and in addition, the low potential and low content of the MgRE phase provide decreased galvanic corrosion characteristics, so that the degradation rate of the alloy is 94.3mg/cm 2 The/h is reduced to 33.9mg/cm 2 /h。
When the homogenization time before extrusion is changed, as in the homogenization treatment of comparative example 3 before extrusion for 10min, the Er/Ni molar ratio is 1.41, the strength is reduced from 360MPa to 320MPa, the reason is that the heat treatment time is shorter, the preheating treatment of the alloy can not be realized, in addition, after the short-time treatment, the content of the layered LPSO phase is less, the content of the Ni-LPSO phase is reduced from 19.1 percent to 14.2 percent, the content of the Ni-LPSO phase is reduced under the same Ni content, the quantity of galvanic corrosion which can be provided is less, and the degradation rate of the alloy is enabled to be reduced from 94.3mg/cm 2 The/h is reduced to 82.5mg/cm 2 H is used as the reference value. In addition, when homogenization treatment is carried out 60min before extrusion, the Er/Ni molar ratio is 1.41, the strength is increased from 360MPa to 375MPa, the reason is that a large amount of layered Ni-LPSO is precipitated in a magnesium matrix after long-time heat treatment, so that the alloy is mainly based on a layered LPSO phase, wherein the layered Ni-LPSO phase increases more nucleation sites, promotes dynamic recrystallization, refines crystal grains and plays a role in short fiber reinforcement, and a uniform corrosion product film is easily formed in the corrosion process due to the precipitation of the large amount of the layered Ni-LPSO phase to form a corrosion barrier, so that the degradation rate of the alloy is 94.3mg/cm 2 The/h is reduced to 58.2mg/cm 2 /h。
In addition, after the holding time and the cooling condition of the melting thermometer are changed, as comparative examples 5 and 6, 770 ℃ is melted, 680 ℃ is held for 18min, 650 ℃ is held for 18min, and room temperature saline water is cooled, the strength of the alloy is reduced from 360MPa to 320MPa and 300MPa, because the melt holding temperature is lower, the cooling rate is slower, the alloy almost has no layered structure, and all the Ni-LPSO phases are precipitated to form blocky Ni-LPSO phases, no layered Ni-LPSO phases are precipitated in the short-time homogenization treatment process, more nucleation sites cannot be increased, dynamic recrystallization is promoted, crystal grains are refined, the short fiber strengthening effect is achieved, the strength of the alloy is obviously reduced, in addition, because the non-layered Ni-LPSO phases exist in the alloy, the corrosion couple quantity of the alloy is reduced, and the degradation rate of the alloy is 94.3mg/cm 2 The/h is reduced to 89.3mg/cm 2 H and 83.2mg/cm 2 /h。
The strength and degradation characteristics of the alloy are comprehensively considered, the alloy is melted at 760-800 ℃ when the Er/Ni molar ratio is within 1.3-1.8, is kept at 760-780 ℃ for 10-20min, is rapidly cooled by a low-temperature saline bath, is subjected to short-time homogenization treatment at 400 ℃ for 25-35min before extrusion, only has a single Ni-LPSO phase containing layers and blocks, and has the optimal mechanical and degradation characteristics when the volume fraction of the Ni-LPSO phase is 15-36%.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the embodiments of the present invention, and they should be construed as being covered by the appended claims and their equivalents.
Claims (12)
1. The high-strength and high-toughness rapidly-degradable Mg-Er-Ni alloy for underground fracturing is characterized by comprising the following components in percentage by mass: er:6-15%, ni:1-5%, the molar ratio of Er/Ni is 1.3-1.8, and the balance is Mg and inevitable impurity elements; wherein Mg, ni and Er mainly form a Ni-LPSO phase which is layered and blocky and coexists, and the volume fraction of the Ni-LPSO phase is 15-36%; the Mg-Er-Ni alloy is prepared by the following method: (a) casting: uniformly mixing a nickel source, a magnesium source and an erbium source, and smelting and casting to obtain an as-cast alloy; (b) heat treatment: carrying out homogenization treatment and extrusion deformation treatment on the as-cast alloy in sequence to obtain the high-strength high-toughness rapidly-degradable Mg-Er-Ni alloy; wherein in the step (a), when smelting and casting are carried out, the temperature is firstly raised to 760-800 ℃, the temperature is preserved, the raw materials are stirred to be completely melted, then the temperature is preserved for 10-20min at 760-780 ℃, and finally the raw materials are rapidly cooled by adopting a brine bath at 5-10 ℃ to obtain an as-cast alloy; in step (b), the homogenization treatment is carried out at 380-420 ℃ for 25-35min.
2. The Mg-Er-Ni alloy of claim 1, wherein said Er/Ni molar ratio is 1.4-1.6 and the volume fraction of said Ni-LPSO phase is 24-36%.
3. The Mg-Er-Ni alloy of claim 1, wherein said nickel source is selected from elemental nickel and/or a nickel alloy.
4. The Mg-Er-Ni alloy of claim 3, wherein said nickel alloy is selected from the group consisting of magnesium-nickel alloys.
5. The Mg-Er-Ni alloy of claim 1, wherein said magnesium source is selected from the group consisting of elemental magnesium and/or magnesium alloys.
6. The Mg-Er-Ni alloy of claim 5, wherein said magnesium alloy is selected from magnesium alloys.
7. The Mg-Er-Ni alloy of claim 1, wherein said erbium source comprises at least one of a magnesium erbium alloy and a nickel erbium alloy.
8. The Mg-Er-Ni alloy of claim 1, wherein said melting and casting is carried out with an inert gas blanket.
9. The Mg-Er-Ni alloy of claim 8, wherein said inert gas is selected from at least one of helium, argon, carbon dioxide and sulfur hexafluoride.
10. The Mg-Er-Ni alloy according to claim 9, wherein in step (b), the extrusion deformation treatment is carried out at an extrusion ratio of 9 to 15 and an extrusion deformation speed of 0.3 to 0.4m/min.
11. The Mg-Er-Ni alloy of claim 10, wherein said extrusion temperature is 380 to 420 ℃.
12. Use of a Mg-Er-Ni alloy according to any of claims 1 to 11 in the field of oil and gas development.
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