Patent Application
20220220590
The present disclosure relates to the technical field of magnesium alloy materials, and particularly relates to a fast-dissolved high-plasticity soluble magnesium alloy material and a preparation method thereof.
In recent years, a large number of unconventional oil and gas resources that are difficult to exploit have been found in China, and these unconventional oil and gas resources are exploited depending on reservoir reconstruction process technologies such as hydraulic fracturing. In a hydraulic fracturing technology, between different layer sections, packing tools (such as fracturing balls and bridge plugs) need to be used to perform separation and then perform fracturing reconstruction layer by layer, so as to realize oil and gas exploitation. At present, commonly used packing tools are mostly prepared from insoluble materials (steel, lithium alloys, polymer materials, etc.). The tools prepared from the insoluble materials have the defects in use that they have difficulty in drilling and milling, consume a lot of time, make powder/fragments after drilling difficult to flow back, and the like, and these defects seriously affect the construction progress, efficiency and safety. Therefore, a plugging tool prepared from composite materials has been developed internationally. Although the material reduces the problems that are likely to occur during construction, it still has the problem of easy jamming because it cannot be completely dissolved, and raw materials are produced and processed depending on imports, so that it is very high in cost, and severely restricted by foreign countries.
A magnesium alloy has low density, high specific strength, high specific rigidity, and low electrode potential, is relatively active in chemical property, and is prone to corrosion in most solutions. According to its characteristics, magnesium alloy materials can be used to prepare fracturing and packing tools applied in the field of oil and gas exploitation. However, the existing magnesium alloy materials have a plurality of problems such as low corrosion rate or low strength or poor plasticity, cannot meet the actual needs of oil and gas exploitation tools, and are relatively high in production cost. It is necessary to provide a novel magnesium alloy material with relatively high plasticity and a good corrosion rate to meet the needs of industrial production.
The present disclosure provides a fast-dissolved high-plasticity soluble magnesium alloy material and a preparation method thereof.
According to the scheme of the present disclosure:
a fast-dissolved high-plasticity soluble magnesium alloy material includes the following elements by mass percentage:
9.2-11.5% of Al;
0.8-6% of Zn;
0.06-0.4% of Ni;
0.01-0.08% of Au;
0.14-0.35% of Sb;
0.2-1.5% of Cr;
0.05-0.3% of Cu;
2.1-3.5% of Sn;
0.1-0.28% of Fe;
0.05-0.18% of Mn; and
the balance Mg.
As a preferred technical solution, the fast-dissolved high-plasticity soluble magnesium alloy material includes the following elements by mass percentage:
9.3-9.5% of Al;
0.8-2.6% of Zn;
0.15-0.22% of Ni;
0.025-0.04% of Au;
0.25-0.28% of Sb;
0.8-1.2% of Cr;
0.15-0.25% of Cu;
2.4-2.8% of Sn;
0.15-0.23% of Fe;
0.1-0.15% of Mn; and
the balance Mg.
As a preferred technical solution, the fast-dissolved high-plasticity soluble magnesium alloy material includes the following elements by mass percentage:
9.4% of Al;
1.6% of Zn;
0.18% of Ni;
0.03% of Au;
0.26% of Sb;
1% of Cr;
0.2% of Cu;
2.6% of Sn;
0.18% of Fe;
0.11% of Mn; and
the balance Mg.
The present disclosure further provides a preparation method for the fast-dissolved high-plasticity soluble magnesium alloy material, including the following steps:
1) making preparations: removing oxidized surfaces of various metals required, and then respectively weighing the raw material metals according to ratios of raw materials;
2) smelting: putting the prepared raw materials into a graphite crucible, heating and smelting, stirring after melting, and controlling a temperature to be stable;
3) refining: spraying a refining agent into a melted solution to perform first-time refining, performing slagging-off operation after the first-time refining, stirring by controlling a pressure in a refining furnace, then standing to perform second-time slagging-off operation, then spraying the refining agent into the solution for the second time to perform second-time refining, performing slagging-off after the second-time refining, and stirring uniformly;
4) casting: introducing the magnesium alloy solution into a crystallizer to carry out semi-continuous casting of an alloy;
5) homogenizing treatment: keeping temperature of obtained ingots at a certain temperature for a period of time;
6) hot extrusion: performing hot extrusion on the obtained ingot at a certain temperature to obtain the soluble magnesium alloy material; and
7) aging treatment: performing aging treatment on the extruded alloy material at a certain temperature.
As the preferred technical solution, in a smelting process of step 2), a melting temperature is 700-900° C., and SF6+CO2 mixed gas needs to be used for protection in a melting process, and in step 3), a refining temperature is 700-730° C., and SF6+CO2 mixed gas needs to be used for protection in a refining process.
As the preferred technical solution, in a casting process of step 4), cooling water needs to be continuously supplied to the crystallizer, and a drawing casting speed of the alloy is 10-30 cm/min.
As the preferred technical solution, in homogenizing treatment of step 5), a heat-preserving temperature is in a range of 380-420° C. for 5-50 h.
As the preferred technical solution, in a hot extrusion process of step 6), an extrusion temperature is 350-370° C., and an extrusion ratio is in a range of 3-30.
As the preferred technical solution, in aging treatment of step 7), a temperature is in a range of 260-300° C. for 10-100 h.
As the preferred technical solution, a weight of the refining agent charged in the first time accounts for 20-30% of a weight of the raw material metal, a weight of the refining agent charged in the second time accounts for 10-15% that of the raw material metal, the refining agent includes magnesium chloride, sodium chloride, potassium chloride, magnesium fluoride, magnesium oxide and calcium-based bentonite, and a feed ratio among them is 30-40:4-8:25-36:7-10:8-10:5-6.
By adopting the above-mentioned technical solution, according to the fast-dissolved high-plasticity soluble magnesium alloy material and the preparation method thereof, 1) making preparations: removing the oxidized surfaces of the various metals required, and then respectively weighing the raw material metals according to the ratios of the raw materials; 2) smelting: putting the prepared raw materials into the graphite crucible, heating and smelting, stirring after melting, and controlling the temperature to be stable; 3) refining: spraying the refining agent into the melted solution to perform first-time refining, performing slagging-off operation after the first-time refining, stirring by controlling the pressure in the refining furnace, then standing to perform second-time slagging-off operation, then spraying the refining agent into the solution for the second time to perform second-time refining, performing slagging-off after the second-time refining, and stirring uniformly; 4) casting: introducing the magnesium alloy solution into the crystallizer to carry out semi-continuous casting of the alloy; 5) homogenizing treatment: keeping temperature of the obtained ingots at a certain temperature for a period of time; 6) hot extrusion: performing hot extrusion on the obtained ingot at a certain temperature to obtain the soluble magnesium alloy material; and 7) aging treatment: performing aging treatment on the extruded alloy material at a certain temperature.
The present disclosure has the advantages that the soluble magnesium material produced by the present disclosure is high in mechanical strength, good in plasticity and capable of being fast dissolved in a salt solution, and exhibits very excellent tensile strength and plastic extension strength and obvious percentage elongation after fracture during performance testing, proving that the soluble magnesium of the present disclosure has good plasticity;
it is suitable for processing fracturing tools used in the fracturing process of oil and gas fields, and the fracturing tools processed from this material have sufficient strength to ensure smooth downhole construction, and can be autonomously dissolved in an electrolyte solution after service is completed, eliminating a subsequent flowback, and milling process and improving construction efficiency.
In order to overcome the above defects, the present disclosure provides a fast-dissolved high-plasticity soluble magnesium alloy material and a preparation method thereof to solve the problems in the above background.
A fast-dissolved high-plasticity soluble magnesium alloy material includes the following elements by mass percentage:
9.2-11.5% of Al;
0.8-6% of Zn;
0.06-0.4% of Ni;
0.01-0.08% of Au;
0.14-0.35% of Sb;
0.2-1.5% of Cr;
0.05-0.3% of Cu;
2.1-3.5% of Sn;
0.1-0.28% of Fe;
0.05-0.18% of Mn; and
the balance Mg.
The fast-dissolved high-plasticity soluble magnesium alloy material includes the following elements by mass percentage:
9.3-9.5% of Al;
0.8-2.6% of Zn;
0.15-0.22% of Ni;
0.025-0.04% of Au;
0.25-0.28% of Sb;
0.8-1.2% of Cr;
0.15-0.25% of Cu;
2.4-2.8% of Sn;
0.15-0.23% of Fe;
0.1-0.15% of Mn; and
the balance Mg.
The fast-dissolved high-plasticity soluble magnesium alloy material includes the following elements by mass percentage:
9.4% of Al;
1.6% of Zn;
0.18% of Ni;
0.03% of Au;
0.26% of Sb;
1% of Cr;
0.2% of Cu;
2.6% of Sn;
0.18% of Fe;
0.11% of Mn; and
the balance Mg.
The present disclosure further provides a preparation method for the fast-dissolved high-plasticity soluble magnesium alloy material, including the following steps:
1) making preparations: removing oxidized surfaces of various metals required, and then respectively weighing the raw material metals according to ratios of raw materials;
2) smelting: putting the prepared raw materials into a graphite crucible, heating and smelting, stirring after melting, and controlling a temperature to be stable;
3) refining: spraying a refining agent into a melted solution to perform first-time refining, performing slagging-off operation after the first-time refining, stirring by controlling a pressure in a refining furnace, then standing to perform second-time slagging-off operation, then spraying the refining agent into the solution for the second time to perform second-time refining, performing slagging-off after the second-time refining, and stirring uniformly;
4) casting: introducing the magnesium alloy solution into a crystallizer to carry out semi-continuous casting of an alloy;
5) homogenizing treatment: keeping temperature of obtained ingots at a certain temperature for a period of time;
6) hot extrusion: performing hot extrusion on the obtained ingot at a certain temperature to obtain the soluble magnesium alloy material; and
7) aging treatment: performing aging treatment on the extruded alloy material at a certain temperature.
In a smelting process of step 2), a melting temperature is 700-900° C., and SF6+CO2 mixed gas needs to be used for protection in a melting process, and in step 3), a refining temperature is 700-730° C., and SF6+CO2 mixed gas needs to be used for protection in a refining process.
In a casting process of step 4), cooling water needs to be continuously supplied to the crystallizer, and a drawing casting speed of the alloy is 10-30 cm/min.
In homogenizing treatment of step 5), a heat-preserving temperature is in a range of 380-420° C. for 5-50 h.
In a hot extrusion process of step 6), an extrusion temperature is 350-370° C., and an extrusion ratio is in a range of 3-30.
In aging treatment of step 7), a temperature is in a range of 260-300° C. for 10-100 h.
A weight of the refining agent charged in the first time accounts for 20-30% of a weight of the raw material metal, a weight of the refining agent charged in the second time accounts for 10-15% that of the raw material metal, the refining agent includes magnesium chloride, sodium chloride, potassium chloride, magnesium fluoride, magnesium oxide and calcium-based bentonite, and a feed ratio among them is 30-40:4-8:25-36:7-10:8-10:5-6.
In order to make the technical means, creative features, purposes, and effects achieved by the present disclosure be readily understood, the present disclosure will be further described with reference to specific examples.
The soluble magnesium alloy material is prepared and includes the following elements by mass percentage:
9.2% of Al;
0.8% of Zn;
0.06% of Ni;
0.01% of Au;
0.14% of Sb;
0.2% of Cr;
0.05% of Cu;
2.1% of Sn;
0.1% of Fe;
0.05% of Mn; and
the balance Mg and inevitable impurities, and the mass percentage sum of the elements is 100%.
1) Making preparations: removing oxidized surfaces of the above-mentioned metals required, and then respectively weighing the raw material metals according to ratios of raw materials;
2) smelting: putting the prepared raw materials into a graphite crucible, heating and smelting, stirring after melting, and controlling a temperature to be stable;
3) refining: spraying a refining agent into a melted solution to perform first-time refining, performing slagging-off operation after the first-time refining, stirring by controlling a pressure in a refining furnace, then standing to perform second-time slagging-off operation, then spraying the refining agent into the solution for the second time to perform second-time refining, performing slagging-off after the second-time refining, and stirring uniformly;
4) casting: introducing the magnesium alloy solution into a crystallizer to carry out semi-continuous casting of an alloy;
5) homogenizing treatment: keeping temperature of obtained ingots at a certain temperature for a period of time;
6) hot extrusion: performing hot extrusion on the obtained ingot at a certain temperature to obtain the soluble magnesium alloy material; and
7) aging treatment: performing aging treatment on the extruded alloy material at a certain temperature.
In a smelting process of step 2), a melting temperature is 700° C., and SF6+CO2 mixed gas needs to be used for protection in a melting process, and in step 3), a refining temperature is 700° C., and SF6+CO2 mixed gas needs to be used for protection in a refining process.
In a casting process of step 4), cooling water needs to be continuously supplied to the crystallizer, and a drawing casting speed of the alloy is 10 cm/min.
In homogenizing treatment of step 5), a heat-preserving temperature is 380° C. for 5 h.
In a hot extrusion process of step 6), an extrusion temperature is 350° C., and an extrusion ratio is 3.
In aging treatment of step 7), a temperature is 260° C. for 10 h.
A weight of the refining agent charged in the first time accounts for 20% of a weight of the raw material metal, a weight of the refining agent charged in the second time accounts for 10% that of the raw material metal, the refining agent includes magnesium chloride, sodium chloride, potassium chloride, magnesium fluoride, magnesium oxide and calcium-based bentonite, and a feed ratio among them is 30:4:25:7:8:5.
The soluble magnesium alloy material is prepared and includes the following elements by mass percentage:
11.5% of Al;
6% of Zn;
0.4% of Ni;
0.08% of Au;
0.35% of Sb;
1.5% of Cr;
0.3% of Cu;
3.5% of Sn;
0.28% of Fe;
0.18% of Mn; and
the balance Mg and inevitable impurities, and the mass percentage sum of the elements is 100%.
1) Making preparations: removing oxidized surfaces of various metals required, and then respectively weighing the raw material metals according to ratios of raw materials;
2) smelting: putting the prepared raw materials into a graphite crucible, heating and smelting, stirring after melting, and controlling a temperature to be stable;
3) refining: spraying a refining agent into a melted solution to perform first-time refining, performing slagging-off operation after the first-time refining, stirring by controlling a pressure in a refining furnace, then standing to perform second-time slagging-off operation, then spraying the refining agent into the solution for the second time to perform second-time refining, performing slagging-off after the second-time refining, and stirring uniformly;
4) casting: introducing the magnesium alloy solution into a crystallizer to carry out semi-continuous casting of an alloy;
5) homogenizing treatment: keeping temperature of obtained ingots at a certain temperature for a period of time;
6) hot extrusion: performing hot extrusion on the obtained ingot at a certain temperature to obtain the soluble magnesium alloy material; and
7) aging treatment: performing aging treatment on the extruded alloy material at a certain temperature.
In a smelting process of step 2), a melting temperature is 900° C., and SF6+CO2 mixed gas needs to be used for protection in a melting process, and in step 3), a refining temperature is 730° C., and SF6+CO2 mixed gas needs to be used for protection in a refining process.
In a casting process of step 4), cooling water needs to be continuously supplied to the crystallizer, and a drawing casting speed of the alloy is 30 cm/min.
In homogenizing treatment of step 5), a heat-preserving temperature is 420° C. for 50 h.
In a hot extrusion process of step 6), an extrusion temperature is 370° C., and an extrusion ratio is 30.
In aging treatment of step 7), a temperature is 300° C. for 100 h.
A weight of the refining agent charged in the first time accounts for 30% of a weight of the raw material metal, a weight of the refining agent charged in the second time accounts for 15% that of the raw material metal, the refining agent includes magnesium chloride, sodium chloride, potassium chloride, magnesium fluoride, magnesium oxide and calcium-based bentonite, and a feed ratio among them is 40:8:36:10:10:6.
The soluble magnesium alloy material is prepared and includes the following elements by mass percentage:
9.3% of Al;
0.8% of Zn;
0.15% of Ni;
0.025% of Au;
0.25% of Sb;
0.8% of Cr;
0.15% of Cu;
2.4% of Sn;
0.15% of Fe;
0.1% of Mn; and
the balance Mg and inevitable impurities, and the mass percentage sum of the elements is 100%.
The present disclosure further provides a preparation method for the fast-dissolved high-plasticity soluble magnesium alloy material, including the following steps:
1) making preparations: removing oxidized surfaces of various metals required, and then respectively weighing the raw material metals according to ratios of raw materials;
2) smelting: putting the prepared raw materials into a graphite crucible, heating and smelting, stirring after melting, and controlling a temperature to be stable;
3) refining: spraying a refining agent into a melted solution to perform first-time refining, performing slagging-off operation after the first-time refining, stirring by controlling a pressure in a refining furnace, then standing to perform second-time slagging-off operation, then spraying the refining agent into the solution for the second time to perform second-time refining, performing slagging-off after the second-time refining, and stirring uniformly;
4) casting: introducing the magnesium alloy solution into a crystallizer to carry out semi-continuous casting of an alloy;
5) homogenizing treatment: keeping temperature of obtained ingots at a certain temperature for a period of time;
6) hot extrusion: performing hot extrusion on the obtained ingot at a certain temperature to obtain the soluble magnesium alloy material; and
7) aging treatment: performing aging treatment on the extruded alloy material at a certain temperature.
In a smelting process of step 2), a melting temperature is 720° C., and SF6+CO2 mixed gas needs to be used for protection in a melting process, and in step 3), a refining temperature is 710° C., and SF6+CO2 mixed gas needs to be used for protection in a refining process.
In a casting process of step 4), cooling water needs to be continuously supplied to the crystallizer, and a drawing casting speed of the alloy is 15 cm/min.
In homogenizing treatment of step 5), a heat-preserving temperature is 390° C. for 10 h.
In a hot extrusion process of step 6), an extrusion temperature is 360° C., and an extrusion ratio is 7.
In aging treatment of step 7), a temperature is 280° C. for 20 h.
A weight of the refining agent charged in the first time accounts for 22% of a weight of the raw material metal, a weight of the refining agent charged in the second time accounts for 12% that of the raw material metal, the refining agent includes magnesium chloride, sodium chloride, potassium chloride, magnesium fluoride, magnesium oxide and calcium-based bentonite, and a feed ratio among them is 32:5:27:8:8:5.
The soluble magnesium alloy material is prepared and includes the following elements by mass percentage:
9.5% of Al;
2.6% of Zn;
0.22% of Ni;
0.04% of Au;
0.28% of Sb;
1.2% of Cr;
0.25% of Cu;
2.8% of Sn;
0.23% of Fe;
0.15% of Mn; and
the balance Mg and inevitable impurities, and the mass percentage sum of the elements is 100%.
1) Making preparations: removing oxidized surfaces of various metals required, and then respectively weighing the raw material metals according to ratios of raw materials;
2) smelting: putting the prepared raw materials into a graphite crucible, heating and smelting, stirring after melting, and controlling a temperature to be stable;
3) refining: spraying a refining agent into a melted solution to perform first-time refining, performing slagging-off operation after the first-time refining, stirring by controlling a pressure in a refining furnace, then standing to perform second-time slagging-off operation, then spraying the refining agent into the solution for the second time to perform second-time refining, performing slagging-off after the second-time refining, and stirring uniformly;
4) casting: introducing the magnesium alloy solution into a crystallizer to carry out semi-continuous casting of an alloy;
5) homogenizing treatment: keeping temperature of obtained ingots at a certain temperature for a period of time;
6) hot extrusion: performing hot extrusion on the obtained ingot at a certain temperature to obtain the soluble magnesium alloy material; and
7) aging treatment: performing aging treatment on the extruded alloy material at a certain temperature.
In a smelting process of step 2), a melting temperature is 800° C., and SF6+CO2 mixed gas needs to be used for protection in a melting process, and in step 3), a refining temperature is 725° C., and SF6+CO2 mixed gas needs to be used for protection in a refining process.
In a casting process of step 4), cooling water needs to be continuously supplied to the crystallizer, and a drawing casting speed of the alloy is 25 cm/min.
In homogenizing treatment of step 5), a heat-preserving temperature is 410° C. for 45 h.
In a hot extrusion process of step 6), an extrusion temperature is 365° C., and an extrusion ratio is 25.
In aging treatment of step 7), a temperature is 290° C. for 85 h.
A weight of the refining agent charged in the first time accounts for 28% of a weight of the raw material metal, a weight of the refining agent charged in the second time accounts for 14% that of the raw material metal, the refining agent includes magnesium chloride, sodium chloride, potassium chloride, magnesium fluoride, magnesium oxide and calcium-based bentonite, and a feed ratio among them is 37:7:32:9:9:6.
The soluble magnesium alloy material is prepared and includes the following elements by mass percentage:
9.4% of Al;
1.6% of Zn;
0.18% of Ni;
0.03% of Au;
0.26% of Sb;
1% of Cr;
0.2% of Cu;
2.6% of Sn;
0.18% of Fe;
0.11% of Mn; and
the balance Mg and inevitable impurities, and the mass percentage sum of the elements is 100%.
1) Making preparations: removing oxidized surfaces of various metals required, and then respectively weighing the raw material metals according to ratios of raw materials;
2) smelting: putting the prepared raw materials into a graphite crucible, heating and smelting, stirring after melting, and controlling a temperature to be stable;
3) refining: spraying a refining agent into a melted solution to perform first-time refining, performing slagging-off operation after the first-time refining, stirring by controlling a pressure in a refining furnace, then standing to perform second-time slagging-off operation, then spraying the refining agent into the solution for the second time to perform second-time refining, performing slagging-off after the second-time refining, and stirring uniformly;
4) casting: introducing the magnesium alloy solution into a crystallizer to carry out semi-continuous casting of an alloy;
5) homogenizing treatment: keeping temperature of obtained ingots at a certain temperature for a period of time;
6) hot extrusion: performing hot extrusion on the obtained ingot at a certain temperature to obtain the soluble magnesium alloy material; and
7) aging treatment: performing aging treatment on the extruded alloy material at a certain temperature.
In a smelting process of step 2), a melting temperature is 730° C., and SF6+CO2 mixed gas needs to be used for protection in a melting process, and in step 3), a refining temperature is 720° C., and SF6+CO2 mixed gas needs to be used for protection in a refining process.
In a casting process of step 4), cooling water needs to be continuously supplied to the crystallizer, and a drawing casting speed of the alloy is 20 cm/min.
In homogenizing treatment of step 5), a heat-preserving temperature is 390° C. for 30 h.
In a hot extrusion process of step 6), an extrusion temperature is 360° C., and an extrusion ratio is 20.
In aging treatment of step 7), a temperature is 280° C. for 50 h.
A weight of the refining agent charged in the first time accounts for 26% of a weight of the raw material metal, a weight of the refining agent charged in the second time accounts for 12% that of the raw material metal, the refining agent includes magnesium chloride, sodium chloride, potassium chloride, magnesium fluoride, magnesium oxide and calcium-based bentonite, and a feed ratio among them is 35:6:30:8:9:6.
The soluble magnesium alloy material in Example 5 is prepared into soluble magnesium test blocks with a length of 25.4 mm, a width of 20.30 mm, a height of 15.2 mm and a weight of 11.555 g, and a soluble magnesium alloy material in the prior art is prepared into soluble magnesium comparison blocks with a length of 25.4 mm, a width of 20.30 mm, a height of 15.2 mm and a weight of 11.555 g; and the soluble magnesium test block and the soluble magnesium comparison block are tested, and
data of the soluble magnesium test block are shown in Table 1 as follows:
However, a dissolution rate of the soluble magnesium comparison block in the prior art is 50 mg/cm2/hr, and this shows that the dissolution rate of the soluble magnesium alloy material of the present application is high, and the dissolution rate of the present disclosure is significantly increased.
A mechanical test is carried out on Sample 7 of a soluble magnesium bar prepared from the soluble magnesium alloy material in Example 4 and Sample 2 of a soluble magnesium bar prepared from the soluble magnesium alloy material in Example 5, test time: 337.866669 s; a test speed: 5 mm/min; Table 2 below and
From the mechanical property testing of
The basic principles, principal features, and advantages of the present disclosure are displayed and described above. It should be understood by those skilled in the art that the present disclosure is not limited by the examples described above, merely the principles of the present disclosure are described in the above-mentioned examples and the description, and various changes and improvements may be made for the present disclosure without departing from the spirit and scope of the present disclosure, and these changes and improvements fall into a protection range claimed by the present disclosure. The protection range claimed by the present disclosure is defined by the appended claims and equivalents thereof.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/CN2021/070840 | Jan 2021 | US |
| Child | 17565504 | US |
