EP3438303B1 - Degradable mg alloy - Google Patents
Degradable mg alloy Download PDFInfo
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- EP3438303B1 EP3438303B1 EP16896913.7A EP16896913A EP3438303B1 EP 3438303 B1 EP3438303 B1 EP 3438303B1 EP 16896913 A EP16896913 A EP 16896913A EP 3438303 B1 EP3438303 B1 EP 3438303B1
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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
- C22C23/00—Alloys based on magnesium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
Definitions
- the present invention relates to a degradable Mg alloy whose corrosion rate can be arbitrarily adjusted.
- AM type Mg alloys in which Al and Mn are added and AZ type Mg alloys in which Al, Mn, and Zn are added are known as general purpose magnesium alloys (Mg alloys).
- Mg alloys general purpose magnesium alloys
- Patent Document 1 describes an Mg alloy in which Mg is from 67 to 85% (atomic ratio), Si is from 5 to 20% (atomic ratio), and the balance is Ni. Patent Document 1 describes that an amorphous powder or a nanocrystal powder is produced by a mechanical alloying method (mechanical alloying) using a raw material powder having such a composition. Such an Mg alloy shows excellent corrosion resistance, and is an alloy which is resistant to degradation and corrosion.
- Patent Document 2 describes an Mg alloy containing Al: from 0.1% to 15.0%; Li: from 0.01% to 10.0%; Ca: from 0.1% to 10.0%; Zn: from 0.1% to 6.5%; In: from 0.01% to 3.0%; Ga: from 0.0% to 2.0%; Si: from 0.1% to 1.5%; Mn: from 0.0% to 0.8%; Zr: from 0.0% to 1.0%; Fe: from 0.016% to 1.0%; Ni: from 0.016% to 5.0%; and Cu: from 0.15% to 5.0%, by mass ratio.
- This is a degradable Mg alloy used as a member which is introduced into oil wells and natural gas wells to temporarily support the structure and is degraded when it becomes unnecessary.
- Patent Document 3 also describes as a degradable Mg alloy an alloy containing Al: from 3.0% to 7.0%; Li: from 0.01% to 1.0%; Ca: from 0.5% to 1.0%; Y: from 0.3% to 2.3%; Si: from 0.3% to 2.0%; Ni: from 0.016% to 0.8%; Cu: from 0.05% to 1.0%; and Fe: from 0.016% to 1.0%, by mass ratio.
- Patent Document 4 describes an Mg alloy for casting containing Cu: from 0.5% to 10%, Ca: from 0.01 to 3%, and Al: from 0 to 3%, by mass ratio.
- Patent Document 4 describes an Mg alloy that has excellent creep resistance by containing Cu and Ca and is suitable for use under high temperature environment.
- degradable Mg alloys used for structural materials to be introduced in oil fields or natural gas fields need to have sufficient mechanical properties for withstanding underground high pressure environment. Meanwhile, since such degradable Mg alloys are introduced into unrecoverable environments, such alloys are desirably degraded without being left in the ground for a long time after the introduction.
- the degradable Mg alloy described in Patent Document 2 contains Si which has an adverse effect on elongation or toughness as an essential element. An extremely expensive In is contained as an essential element for use in a disposable member.
- the degradable Mg alloy described in Patent Document 3 uses Si which has an adverse effect on elongation or toughness as an essential element, and the minimum content of Si is higher than that of the degradable Mg alloy of Patent Document 2.
- the alloy of Patent Document 1 is an Mg alloy which has enhanced corrosion resistance by generating an amorphous phase or nanocrystals by using a mechanical alloying method, not by improving the degradability by the composition, and the use of the alloy is different.
- an object of the present invention is to provide a degradable Mg alloy having a composition having a little kinds of essential elements and having strength required for a structural member that can withstand high pressure and capable of arbitrarily controlling the corrosion rate.
- the content of Ni is 0.01% by mass or more and 0.3% by mass or less.
- the content of Ni is in the range of 0.01 % by mass or more and 0.3% by mass or less, a correlation is established to such an extent that the relationship between the content of Ni and the corrosion rate can be approximated to a linear function.
- the content of Cu is 1.5% by mass or more and 7% mass or less.
- the content of Ni is in the range of 1.5% by mass or more and 7.0% by mass or less, a correlation is established to such an extent that the relationship between the content of Cu and the corrosion rate can be approximated to a linear function.
- the degradable Mg alloy has sufficient mechanical strength while requiring a few kinds of essential elements, the corrosion rate can be adjusted according to the content of Ni and Cu, and the life of a degradable structural material using the degradable Mg alloy can be arbitrarily adjusted.
- the present invention relates to a degradable Mg alloy capable of accelerating corrosion at high speed mainly in an aqueous environment in which water is interposed, a degradable structural member using the same, and a method of adjusting the corrosion rate of the degradable structural member.
- the content of Al in the degradable Mg alloy according to the present invention is needed to be 3.9% by mass or more, and is preferably 7.0% by mass or more.
- the degradable Mg alloy has an effect of improving the strength by addition of Al, but when the content of Al is less than 3.9% by mass, such an effect is insufficient.
- the strength is insufficient, the durability in a high-pressure environment is insufficient, and there is a high possibility that a member is destroyed before being degraded according to the adjusted degradation rate described below.
- the Al content is required to be 14.0% by mass or less, and is preferably 13.0% by mass or less.
- the content of Mn in the degradable Mg alloy according to the present invention needs to be 0.1% by mass or more. Mn has an effect of removing some elements contained as impurities, and when the Mn is too small, the corrosion rate of the degradable Mg alloy greatly deviates from the value adjusted by Ni and Cu, which will be described later, and the controllability may be insufficient.
- the content of Mn needs to be 0.6% by mass or less, and is preferably 0.5% by mass or less. This is because when the content of Mn is too large, precipitation of a large amount of an intermetallic compound of Mn and Al and an Mn simple substance will make a member brittle and the strength will be lowered.
- the degradable Mg alloy according to the present invention may contain Zn in an amount of 1.0% by mass or less.
- Zn has an effect of improving a strength (particularly proof stress).
- ductility is insufficient, not only a process of forming a structural member such as extrusion processing and forging processing becomes difficult but also an effect of suppressing the corrosion rate appears, which is not preferable for a degradable structural member.
- Zn may not be contained, or Zn may be contained within the range of inevitable impurities contained in the alloy, which will be described below.
- the degradable Mg alloy according to the present invention needs to contain both Ni and Cu. By including predetermined amounts of Ni and Cu, it is possible to arbitrarily adjust the corrosion rate in the aqueous environment of an alloy. In other words, it is possible to degrade a degradable structural member made of the degradable Mg alloy at a timing when the member becomes unnecessary. Although both Ni and Cu contribute to degradability, their influences are different from each other, and therefore the range of desirable content that can be adjusted to the optimum corrosion rate varies.
- the degradable Mg alloy according to the present invention contains Ni, wherein the content is required to be 0.01% by mass or more. Ni has a greater effect on corrosion rate than Cu, but when the content is less than 0.01% by mass, it is still difficult to obtain sufficient effect as a degradable Mg alloy. On the other hand, the content of Ni is 0.3% by mass or less. Even when Ni is excessively contained, the corrosion rate is not extremely improved, and the physical properties are difficult to control. When too much Ni is used, the cost burden becomes too large.
- the corrosion rate (mg/cm 2 /day) can be linearly approximated to the logarithm of the content of Ni.
- the corrosion rate of a degradable structural member produced using the degradable Mg alloy can be set with high accuracy.
- the "corroded state" which is a criterion of the above-described corrosion rate means a state of being decomposed from a mass of the original alloy, being dissolved or dispersed in an aqueous solvent, and being not integral with the mass.
- the content is required to be 1.5% by mass or more.
- Cu has less influence on the corrosion rate than Ni, and when the content is less than 1.5% by mass, it is difficult to obtain a sufficient effect as a degradable Mg alloy.
- the Cu content is 7% by mass or less. Even when Cu is excessively contained, the corrosion rate is not extremely improved, and the physical properties are difficult to control.
- the corrosion rate (mg/cm 2 /day) can be linearly approximated to the logarithm of the content of Cu.
- the corrosion rate of a degradable structural member produced using the degradable Mg alloy according to the content of Cu can be set with high accuracy.
- Cu has less influence than Ni, adjustment with high precision becomes easy.
- the degradable Mg alloy according to the present invention contains both Ni and Cu, and each content may be appropriately adjusted to set an optimum corrosion rate. Since the degree of influence depends on the content, it is preferable to use this difference in adjustment. For example, fine adjustment can be made finely with Cu having a relatively small influence by the content while securing a sufficient corrosion rate with Ni having a relatively strong influence.
- the degradable Mg alloy according to the present invention may contain other elements than the above elements as inevitable impurities. These inevitable impurities are inevitably contained contrary to intention due to manufacturing problems or problems on raw materials. Examples thereof include an element such as Ag, Fe, Pb, Cd, Se, Y, Si, Li, In, Ca, Ti, Zr, Ga, or Mm (misch metal).
- the contents of inevitable impurities need to be in a range not inhibiting characteristics of the degradable Mg alloy according to the present invention, and the content per element is preferably less than 0.2% by mass, and more preferably less than 0.1% by mass.
- the contents of Si, Li, In, and Ca are preferably less than 0.1% by mass, and more preferably less than 0.05% by mass.
- the smaller the content of any element which is an inevitable impurity the more preferable, because this reduces uncertain factors to be considered in adjusting the corrosion rate by Ni and Cu. It is particularly preferable that the content is less than the detection limit.
- the degradable Mg alloy can be prepared by a general method using raw materials containing the above elements in such a manner that the respective contents fall within the above range in terms of % by mass and the alloy has a desired corrosion rate.
- the above value of the mass% unit is not based on the raw material, but is based on a prepared alloy or a degradable structural member produced by casting, sintering or the like. It is noted that when a degradable structural member which is particularly required to have strength is produced, it is preferable to perform processing such as extruding or forging to reduce the crystal size of the alloy texture to increase the strength.
- the crystal size is about from 100 to 200 ⁇ m, and when the crystal size is reduced to about 10 ⁇ m or more and 20 ⁇ m or less by the above extrusion, forging, wroughting, or the like, the strength is improved, which is preferable. Even when the crystal size is miniaturized in this manner, the corrosion rate does not change significantly and the corrosion rate can be arbitrarily adjusted depending on the contents of Ni and Cu.
- Ni is limited to a range of 0.01% by mass or more and 0.3% by mass or less and Cu is limited to a range of 1.5% by mass or more and 7.0% by mass or less
- an increase in the corrosion rate can be suitably approximated to a linear function with respect to an increase in the logarithms of the contents of Ni and Cu.
- the fluctuation of the content of Al, Mn, and inevitable impurities is made as small as possible, the corrosion rate of the decomposable Mg alloy corresponding to the limited range of the content of Ni or Cu is measured for a plurality of points, the inclination and intercept of the corrosion rate with respect to the logarithm of the content of Ni or Cu is calculated, the content of Ni or Cu corresponding to the required corrosion rate is determined, and the composition of the degradable Mg alloy suitable for a degradable structural member to be produced may be determined.
- a general method such as a least-squares method may be used.
- the degradable structural member according to the present invention has a smaller coefficient of grain size (the above-mentioned slope) than one produced by casting when the grain size is reduced by applying pressure by a technique such as extrusion, and adjustment of the corrosion rate is easier to be performed.
- Examples of a product to which a degradable structural member made of the degradable Mg alloy according to the present invention is applied include tools for drilling oil wells, natural gas wells, and the like. Since such a product is introduced deep under the ground, a strength that can withstand a high pressure environment is required. On the other hand, when such a product becomes unnecessary, the product can be removed by being corroded and degraded at an appropriate timing by being exposed to an aqueous solution introduced for excavation work without taking time to take out from deep underground.
- Example 1 (None of the example alloys fall within the scope of the present invention) Composition Corrosion rate [mg/cm 2 /day] Ni content [mass%] Al content [mass%] Mn content [mass%] as-cast as-extruded
- Example 1 0.011 8.09 0.20 374.8 513.7
- Example 2 0.024 8.32 0.18 915.2 581.4
- Example 3 0.031 8.00 0.18 892.9 741
- Example 4 0.064 8.09 0.15 2115.9 1112.9
- Example 5 0.025 8.37 0.17 1098.1 762
- Example 6 0.201 11.14 0.18 2196.6 1470.8
- Example 8 0.030 7.99 0.18 1030.5 -
- Example 9 0.047 8.03 0.17 1403.9
- Example 10 0.068 8.39 0.15 1773.9 -
- Example 11 0.110 3.92 0.18 1989.1 735.2
- Example 12 0.153 6.63 0.17
- Fig. 1 shows a graph in which Ni contents are plotted on a common logarithm scale on the horizontal axis and the corrosion rate on the vertical axis for Examples 1 to 10. However, with respect to Examples 8 to 10, only data of casting is shown.
- Example 11 and 12 the corrosion rates of Examples 11 and 12 in which the amount of Al was reduced were measured, and the corrosion rate was measured in the same manner as in Example 1.
- values of the corrosion rate as a degradable Mg alloy were practical.
- the calculated value of the corrosion rate of as-cast should be 2.0 ⁇ 10 3 mcd and 2.2 ⁇ 10 3 mcd, respectively, and the calculated corrosion rate of as-extruded should be 1.2 x 10 3 mcd and 1.3 x 10 3 mcd, respectively.
- Examples 11 and 12 were values which were particularly largely deviated from those of the extruded materials as compared with these calculated values. Thus, it is shown that, since the corrosion rate is not approximated linearly depending on the variation of the value of Al, it is desirable to unify the Al content to some extent in order to adjust the corrosion rate value with high accuracy.
- the tensile strength, 0.2% proof stress, elongation after extrusion were measured. The measurement method is shown below and the results are shown in Table 2. In all cases, the tensile strength exceeded 275 MPa, and sufficient tensile properties and corrosion rate were exhibited as degradable structural materials to be introduced into oil fields, and the like.
- a sample extruded as a round bar of ⁇ 16 was processed to be a 14A test piece prescribed in JIS Z2241 (ISO6892-1). The specific shape is as shown in Fig. 2 .
- the diameter d 0 of a rod-shaped portion was 10 mm
- the original gauge length L 0 was 50 mm
- the length L c of a cylindrical parallel portion was 70 mm
- a tensile test was carried out in accordance with JIS Z2241 (ISO6892-1), and the tensile strength: R m (MPa), 0.2% proof stress: R p0.2 (MPa), and elongation: A (%) were evaluated as follows.
- the tensile strength was defined as the maximum test force Fm that was tolerated during the test until the test piece showed discontinuous yield in the test.
- the 0.2% proof stress is a stress when the plastic elongation is equal to 0.2% of the gauge distance L e of an extensometer.
- the elongation is a value obtained by expressing the permanent elongation of a test piece after being tested until the test piece breaks as a percentage with respect to the original gauge length L 0 .
- Example 1 0.011 8.09 0.20 306.8 209.0 17.8
- Example 2 0.024 8.32 0.18 311.7 218.5 16.0
- Example 3 0.031 8.00 0.18 310.8 216.9 17.3
- Example 6 0.201 11.14 0.18 325.7 243.6 13.3
- Example 7 0.261 13.27 0.17 333.2 256.9 9.6
- Example 11 0.110 3.92 0.18 280.3 204.0 22.9
- Example 12 0.153 6.63 0.17 300.3 206.3 19.5
- a test specimen was prepared by casting so as to have the composition shown in Table 3 by the same procedure as the Ni-containing alloy test described above, and the corrosion rate was measured by the same procedure. The results are shown in Table 3. For Examples 13 to 16, the corrosion rate after forging (as-forged) at a sample temperature of 430°C was measured. Further, in Examples 17 to 23, test specimens were prepared by extrusion processing in the same manner as in the above Examples 1 to 7, and the corrosion rate was measured by the same procedure. The results are also shown in Table 3. In this Cu-containing alloy test, the value of Cu is not a measured value after the alloy was prepared but a target value at the time of addition of a material.
- Fig. 3 shows a graph in which Cu contents are plotted on a logarithm scale on the horizontal axis and the corrosion rate on the vertical axis for Examples 17 to 23.
- Linear approximation by the least-squares method was performed on the logarithm of Cu content and the corrosion rate value.
- the section was -4.0 ⁇ 10 2
- the slope was 3.1 ⁇ 10 3 . This showed that, when casting a degradable structural material containing about 8.0 by mass of Al and about 0.18% by mass of Mn, the corrosion rate can be adjusted by the content of Cu according to the following Formula (3).
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Description
- The present invention relates to a degradable Mg alloy whose corrosion rate can be arbitrarily adjusted.
- AM type Mg alloys in which Al and Mn are added and AZ type Mg alloys in which Al, Mn, and Zn are added are known as general purpose magnesium alloys (Mg alloys). A variety of Mg alloys having improved corrosion resistance by adding elements other than these elements or by adjusting the manufacturing method have been proposed.
- Patent Document 1 below describes an Mg alloy in which Mg is from 67 to 85% (atomic ratio), Si is from 5 to 20% (atomic ratio), and the balance is Ni. Patent Document 1 describes that an amorphous powder or a nanocrystal powder is produced by a mechanical alloying method (mechanical alloying) using a raw material powder having such a composition. Such an Mg alloy shows excellent corrosion resistance, and is an alloy which is resistant to degradation and corrosion.
- Meanwhile, Patent Document 2 below describes an Mg alloy containing Al: from 0.1% to 15.0%; Li: from 0.01% to 10.0%; Ca: from 0.1% to 10.0%; Zn: from 0.1% to 6.5%; In: from 0.01% to 3.0%; Ga: from 0.0% to 2.0%; Si: from 0.1% to 1.5%; Mn: from 0.0% to 0.8%; Zr: from 0.0% to 1.0%; Fe: from 0.016% to 1.0%; Ni: from 0.016% to 5.0%; and Cu: from 0.15% to 5.0%, by mass ratio. This is a degradable Mg alloy used as a member which is introduced into oil wells and natural gas wells to temporarily support the structure and is degraded when it becomes unnecessary. This contains a variety of elements as essential elements in order to have degradability as well as strength characteristics needed for supporting the structure under high pressure environment.
- Patent Document 3 below also describes as a degradable Mg alloy an alloy containing Al: from 3.0% to 7.0%; Li: from 0.01% to 1.0%; Ca: from 0.5% to 1.0%; Y: from 0.3% to 2.3%; Si: from 0.3% to 2.0%; Ni: from 0.016% to 0.8%; Cu: from 0.05% to 1.0%; and Fe: from 0.016% to 1.0%, by mass ratio.
- Meanwhile, Patent Document 4 below describes an Mg alloy for casting containing Cu: from 0.5% to 10%, Ca: from 0.01 to 3%, and Al: from 0 to 3%, by mass ratio. Patent Document 4 describes an Mg alloy that has excellent creep resistance by containing Cu and Ca and is suitable for use under high temperature environment.
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- Patent Document 1:
JP2002-249801A - Patent Document 2:
CN104004950A - Patent Document 3:
CN104651691A - Patent Document 4:
WO2008/072435 - However, degradable Mg alloys used for structural materials to be introduced in oil fields or natural gas fields need to have sufficient mechanical properties for withstanding underground high pressure environment. Meanwhile, since such degradable Mg alloys are introduced into unrecoverable environments, such alloys are desirably degraded without being left in the ground for a long time after the introduction. On the other hand, the degradable Mg alloy described in Patent Document 2 contains Si which has an adverse effect on elongation or toughness as an essential element. An extremely expensive In is contained as an essential element for use in a disposable member.
- Likewise, the degradable Mg alloy described in Patent Document 3 uses Si which has an adverse effect on elongation or toughness as an essential element, and the minimum content of Si is higher than that of the degradable Mg alloy of Patent Document 2.
- Furthermore, since these degradable Mg alloys described in Patent Documents 2 and 3 contain many kinds of essential elements, mechanical properties other than degradability are not easily secured, and the material itself tends to be expensive, which is problematic. It is inevitably difficult to arbitrarily control the corrosion rate because there are too many influencing elements.
- On the other hand, the alloy of Patent Document 1 is an Mg alloy which has enhanced corrosion resistance by generating an amorphous phase or nanocrystals by using a mechanical alloying method, not by improving the degradability by the composition, and the use of the alloy is different.
- With respect to the alloy of Patent Document 4, degradation and corrosion characteristics are not taken into consideration at all and Ca, which is strongly influential to corrosion characteristics, is also added, and therefore, it is also difficult to control the corrosion rate.
- Accordingly, an object of the present invention is to provide a degradable Mg alloy having a composition having a little kinds of essential elements and having strength required for a structural member that can withstand high pressure and capable of arbitrarily controlling the corrosion rate.
- In the present invention, the above problem is solved by a degradable Mg alloy containing:
- 3.9% by mass or more and 14.0% by mass or less of Al and 0.1% by mass or more and 0.6% by mass or less of Mn;
- 0.01% by mass or more and 10.0% by mass or less of Ni, Cu, or both of Ni and Cu; and
- the balance composed of Mg and inevitable impurities. The Mg alloy satisfying these range conditions has sufficient tensile strength properties. Furthermore, the Mg alloy has the property that the corrosion rate can be adjusted by the blending amount of Ni and Cu. The alloy may contain 0.0% by mass or more and 1.0% by mass or less of Zn.
- The content of Ni is 0.01% by mass or more and 0.3% by mass or less. When the content of Ni is in the range of 0.01 % by mass or more and 0.3% by mass or less, a correlation is established to such an extent that the relationship between the content of Ni and the corrosion rate can be approximated to a linear function.
- The content of Cu is 1.5% by mass or more and 7% mass or less. When the content of Ni is in the range of 1.5% by mass or more and 7.0% by mass or less, a correlation is established to such an extent that the relationship between the content of Cu and the corrosion rate can be approximated to a linear function.
- The degradable Mg alloy has sufficient mechanical strength while requiring a few kinds of essential elements, the corrosion rate can be adjusted according to the content of Ni and Cu, and the life of a degradable structural material using the degradable Mg alloy can be arbitrarily adjusted.
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Fig. 1 is a graph of the corrosion rate with respect to the content of Ni in Examples. -
Fig. 2 is a schematic diagram of the shape of a test material used in Examples. -
Fig. 3 is a graph of the corrosion rate with respect to the content of Cu in Examples. - Hereinafter, the present invention will be described in detail.
- The present invention relates to a degradable Mg alloy capable of accelerating corrosion at high speed mainly in an aqueous environment in which water is interposed, a degradable structural member using the same, and a method of adjusting the corrosion rate of the degradable structural member.
- The content of Al in the degradable Mg alloy according to the present invention is needed to be 3.9% by mass or more, and is preferably 7.0% by mass or more. The degradable Mg alloy has an effect of improving the strength by addition of Al, but when the content of Al is less than 3.9% by mass, such an effect is insufficient. When the strength is insufficient, the durability in a high-pressure environment is insufficient, and there is a high possibility that a member is destroyed before being degraded according to the adjusted degradation rate described below. On the other hand, the Al content is required to be 14.0% by mass or less, and is preferably 13.0% by mass or less. This is because when too much Al is used, not only the toughness (elongation) decreases but also there is a fear that the strength tends to decrease due to easy creep deformation in a medium to high temperature environment, and when the content of Al exceeds 14.0% by mass, there is a possibility that the shape of a member is difficult to be maintained.
- The content of Mn in the degradable Mg alloy according to the present invention needs to be 0.1% by mass or more. Mn has an effect of removing some elements contained as impurities, and when the Mn is too small, the corrosion rate of the degradable Mg alloy greatly deviates from the value adjusted by Ni and Cu, which will be described later, and the controllability may be insufficient. On the other hand, the content of Mn needs to be 0.6% by mass or less, and is preferably 0.5% by mass or less. This is because when the content of Mn is too large, precipitation of a large amount of an intermetallic compound of Mn and Al and an Mn simple substance will make a member brittle and the strength will be lowered.
- The degradable Mg alloy according to the present invention may contain Zn in an amount of 1.0% by mass or less. Zn has an effect of improving a strength (particularly proof stress). When the content of Zn exceeds 1.0% by mass, ductility is insufficient, not only a process of forming a structural member such as extrusion processing and forging processing becomes difficult but also an effect of suppressing the corrosion rate appears, which is not preferable for a degradable structural member. On the other hand, Zn may not be contained, or Zn may be contained within the range of inevitable impurities contained in the alloy, which will be described below.
- The degradable Mg alloy according to the present invention needs to contain both Ni and Cu. By including predetermined amounts of Ni and Cu, it is possible to arbitrarily adjust the corrosion rate in the aqueous environment of an alloy. In other words, it is possible to degrade a degradable structural member made of the degradable Mg alloy at a timing when the member becomes unnecessary. Although both Ni and Cu contribute to degradability, their influences are different from each other, and therefore the range of desirable content that can be adjusted to the optimum corrosion rate varies.
- The degradable Mg alloy according to the present invention contains Ni, wherein the content is required to be 0.01% by mass or more. Ni has a greater effect on corrosion rate than Cu, but when the content is less than 0.01% by mass, it is still difficult to obtain sufficient effect as a degradable Mg alloy. On the other hand, the content of Ni is 0.3% by mass or less. Even when Ni is excessively contained, the corrosion rate is not extremely improved, and the physical properties are difficult to control. When too much Ni is used, the cost burden becomes too large.
- When the amount of Ni contained in the degradable Mg alloy is in the range of 0.01% by mass or more and 0.3% by mass or less, the corrosion rate (mg/cm2/day) can be linearly approximated to the logarithm of the content of Ni. In other words, it is possible to adjust the corrosion rate of a degradable structural member produced using the degradable Mg alloy according to the content of Ni. By utilizing this property, the time until a degradable structural member produced using the degradable Mg alloy to collapse can be set with high accuracy. Herein, the "corroded state" which is a criterion of the above-described corrosion rate means a state of being decomposed from a mass of the original alloy, being dissolved or dispersed in an aqueous solvent, and being not integral with the mass.
- When the degradable Mg alloy according to the present invention contains Cu, the content is required to be 1.5% by mass or more. Cu has less influence on the corrosion rate than Ni, and when the content is less than 1.5% by mass, it is difficult to obtain a sufficient effect as a degradable Mg alloy. On the other hand, the Cu content is 7% by mass or less. Even when Cu is excessively contained, the corrosion rate is not extremely improved, and the physical properties are difficult to control.
- When the amount of Cu contained in the degradable Mg alloy is in the range of 1.5% by mass or more to 7.0% by mass or less, the corrosion rate (mg/cm2/day) can be linearly approximated to the logarithm of the content of Cu. In other words, it is possible to adjust the corrosion rate of a degradable structural member produced using the degradable Mg alloy according to the content of Cu. By utilizing this property, the time until a degradable structural member produced using the degradable Mg alloy to collapse can be set with high accuracy. Particularly, since Cu has less influence than Ni, adjustment with high precision becomes easy.
- The degradable Mg alloy according to the present invention contains both Ni and Cu, and each content may be appropriately adjusted to set an optimum corrosion rate. Since the degree of influence depends on the content, it is preferable to use this difference in adjustment. For example, fine adjustment can be made finely with Cu having a relatively small influence by the content while securing a sufficient corrosion rate with Ni having a relatively strong influence.
- The degradable Mg alloy according to the present invention may contain other elements than the above elements as inevitable impurities. These inevitable impurities are inevitably contained contrary to intention due to manufacturing problems or problems on raw materials. Examples thereof include an element such as Ag, Fe, Pb, Cd, Se, Y, Si, Li, In, Ca, Ti, Zr, Ga, or Mm (misch metal). The contents of inevitable impurities need to be in a range not inhibiting characteristics of the degradable Mg alloy according to the present invention, and the content per element is preferably less than 0.2% by mass, and more preferably less than 0.1% by mass. Among them, the contents of Si, Li, In, and Ca are preferably less than 0.1% by mass, and more preferably less than 0.05% by mass. The smaller the content of any element which is an inevitable impurity, the more preferable, because this reduces uncertain factors to be considered in adjusting the corrosion rate by Ni and Cu. It is particularly preferable that the content is less than the detection limit.
- The degradable Mg alloy can be prepared by a general method using raw materials containing the above elements in such a manner that the respective contents fall within the above range in terms of % by mass and the alloy has a desired corrosion rate. The above value of the mass% unit is not based on the raw material, but is based on a prepared alloy or a degradable structural member produced by casting, sintering or the like. It is noted that when a degradable structural member which is particularly required to have strength is produced, it is preferable to perform processing such as extruding or forging to reduce the crystal size of the alloy texture to increase the strength. When the degradable Mg alloy is cast, the crystal size is about from 100 to 200 µm, and when the crystal size is reduced to about 10 µm or more and 20 µm or less by the above extrusion, forging, wroughting, or the like, the strength is improved, which is preferable. Even when the crystal size is miniaturized in this manner, the corrosion rate does not change significantly and the corrosion rate can be arbitrarily adjusted depending on the contents of Ni and Cu.
- In particular, when Ni is limited to a range of 0.01% by mass or more and 0.3% by mass or less and Cu is limited to a range of 1.5% by mass or more and 7.0% by mass or less, an increase in the corrosion rate can be suitably approximated to a linear function with respect to an increase in the logarithms of the contents of Ni and Cu. By utilizing this property, the fluctuation of the content of Al, Mn, and inevitable impurities is made as small as possible, the corrosion rate of the decomposable Mg alloy corresponding to the limited range of the content of Ni or Cu is measured for a plurality of points, the inclination and intercept of the corrosion rate with respect to the logarithm of the content of Ni or Cu is calculated, the content of Ni or Cu corresponding to the required corrosion rate is determined, and the composition of the degradable Mg alloy suitable for a degradable structural member to be produced may be determined. For calculation of slope and intercept, a general method such as a least-squares method may be used. Although it is possible to make a linear approximation to some extent even when the contents are less than the above-mentioned limited range, and when the amount of Ni or Cu is too small, it becomes difficult to adjust the actual content with high precision. On the other hand, when the amount of Ni or Cu is too large, the deviation from the linear function is unignorable.
- The degradable structural member according to the present invention has a smaller coefficient of grain size (the above-mentioned slope) than one produced by casting when the grain size is reduced by applying pressure by a technique such as extrusion, and adjustment of the corrosion rate is easier to be performed.
- Examples of a product to which a degradable structural member made of the degradable Mg alloy according to the present invention is applied include tools for drilling oil wells, natural gas wells, and the like. Since such a product is introduced deep under the ground, a strength that can withstand a high pressure environment is required. On the other hand, when such a product becomes unnecessary, the product can be removed by being corroded and degraded at an appropriate timing by being exposed to an aqueous solution introduced for excavation work without taking time to take out from deep underground.
- An example in which the degradable Mg alloy was actually prepared and the corrosion rate was measured is shown. First, for an Ni-containing alloy, raw materials were prepared so as to have the composition shown in Table 1, heated to 700°C, and a test specimen was produced by casting. For some examples (Examples 1 to 3, 6, 7, 11, and 12), test specimens subjected to extrusion processing under the conditions of a die temperature of 400°C and a billet temperature of 350°C were prepared. Elements other than those described are Mg and inevitable impurities each less than 0.1% by mass. Each test specimen was immersed in a 2% KCl aqueous solution (93°C), and the corrosion weight loss (mg) of the specimen and the area before and after the test were measured to calculate the corrosion rate per day (mg/cm2/day: mcd). The values are shown in Table 1. In the table, "as-cast" is the measurement result of the test specimen by casting and "as-extruded" is the measurement result of the test specimen by extrusion processing.
[Table 1] (None of the example alloys fall within the scope of the present invention) Composition Corrosion rate [mg/cm2/day] Ni content [mass%] Al content [mass%] Mn content [mass%] as-cast as-extruded Example 1 0.011 8.09 0.20 374.8 513.7 Example 2 0.024 8.32 0.18 915.2 581.4 Example 3 0.031 8.00 0.18 892.9 741 Example 4 0.064 8.09 0.15 2115.9 1112.9 Example 5 0.025 8.37 0.17 1098.1 762 Example 6 0.201 11.14 0.18 2196.6 1470.8 Example 7 0.261 13.27 0.17 2465.9 1546.2 Example 8 0.030 7.99 0.18 1030.5 - Example 9 0.047 8.03 0.17 1403.9 - Example 10 0.068 8.39 0.15 1773.9 - Example 11 0.110 3.92 0.18 1989.1 735.2 Example 12 0.153 6.63 0.17 1402.9 838.6 Comparative Example 1 0.002 8.16 0.20 4.7 - Comparative Example 2 0.009 8.14 0.18 63.5 - Comparative Example 3 < 0.0001 5.99 0.24 7.0 - -
Fig. 1 shows a graph in which Ni contents are plotted on a common logarithm scale on the horizontal axis and the corrosion rate on the vertical axis for Examples 1 to 10. However, with respect to Examples 8 to 10, only data of casting is shown. - Linear approximation by the least-squares method was performed on the logarithm of Ni content and the corrosion rate value. In the casting "as-cast", the section was 3.4 × 103, and the slope was 1.5 × 103. This showed that, when casting a degradable structural material containing about from 8 to 13% by mass of Al and about 0.18% by mass of Mn, the corrosion rate can be adjusted by the content of Ni according to the following Formula (1). In the extrusion processing "as-extruded", the section was 2.0 × 103, and the slope was 8.1 × 102. This showed that, when a degradable structural material containing about from 8 to 13% by mass of Al and about 0.18% by mass of Mn was produced by extrusion processing, the corrosion rate can be adjusted by the content of Ni according to the following Formula (2). These approximate straight lines are also shown in
Fig. 1 . It was shown that, since, particularly by performing extrusion processing, the coefficient related to an increase in the corrosion rate was suppressed as compared with the case of casting, control of the corrosion rate became easier. - Further, the corrosion rates of Examples 11 and 12 in which the amount of Al was reduced were measured, and the corrosion rate was measured in the same manner as in Example 1. As a result, values of the corrosion rate as a degradable Mg alloy were practical. However, according to the above-described Formula (1) obtained from Examples 1 to 10 in which the above-mentioned Al was measured in the range of about from 8 to 13% by mass, when Ni = 0.110% by mass and 0.153% by mass, the calculated value of the corrosion rate of as-cast should be 2.0 × 103 mcd and 2.2 × 103 mcd, respectively, and the calculated corrosion rate of as-extruded should be 1.2 x 103 mcd and 1.3 x 103 mcd, respectively. The actual values of Examples 11 and 12 were values which were particularly largely deviated from those of the extruded materials as compared with these calculated values. Thus, it is shown that, since the corrosion rate is not approximated linearly depending on the variation of the value of Al, it is desirable to unify the Al content to some extent in order to adjust the corrosion rate value with high accuracy.
- On the other hand, in Comparative Examples 1 to 3 in which the content of Ni was less than 0.01% by mass, the corrosion rate was remarkably low, and a corrosion rate improving effect by addition of Ni was not sufficiently obtained.
- In addition, for some Examples, the tensile strength, 0.2% proof stress, elongation after extrusion were measured. The measurement method is shown below and the results are shown in Table 2. In all cases, the tensile strength exceeded 275 MPa, and sufficient tensile properties and corrosion rate were exhibited as degradable structural materials to be introduced into oil fields, and the like.
- A sample extruded as a round bar of ϕ16 was processed to be a 14A test piece prescribed in JIS Z2241 (ISO6892-1). The specific shape is as shown in
Fig. 2 . This test piece is a proportional test piece in which the original cross section S0 and the original gauge length L0 of a parallel portion have a relation of L0 = 5.65 × S0 0.5. The diameter d0 of a rod-shaped portion was 10 mm, the original gauge length L0 was 50 mm, the length Lc of a cylindrical parallel portion was 70 mm, and the radius R of a shoulder portion was 15 mm (L0 = 5.65 × (5 × 5 × π)0.5 = 50.07). - For this test piece, a tensile test was carried out in accordance with JIS Z2241 (ISO6892-1), and the tensile strength: Rm (MPa), 0.2% proof stress: Rp0.2 (MPa), and elongation: A (%) were evaluated as follows. The tensile strength was defined as the maximum test force Fm that was tolerated during the test until the test piece showed discontinuous yield in the test. The 0.2% proof stress is a stress when the plastic elongation is equal to 0.2% of the gauge distance Le of an extensometer. The elongation is a value obtained by expressing the permanent elongation of a test piece after being tested until the test piece breaks as a percentage with respect to the original gauge length L0. All of Examples showed favorable values.
[Table 2] (None of the example alloys fall within the scope of the invention) Composition Tensile properties (as-extruded) Ni content [mass%] Al content [mass%] Mn content [mass%] Tensile strength [MPa] 0.2%proof stress [MPa] Elongation [%] Example 1 0.011 8.09 0.20 306.8 209.0 17.8 Example 2 0.024 8.32 0.18 311.7 218.5 16.0 Example 3 0.031 8.00 0.18 310.8 216.9 17.3 Example 6 0.201 11.14 0.18 325.7 243.6 13.3 Example 7 0.261 13.27 0.17 333.2 256.9 9.6 Example 11 0.110 3.92 0.18 280.3 204.0 22.9 Example 12 0.153 6.63 0.17 300.3 206.3 19.5 - A test specimen was prepared by casting so as to have the composition shown in Table 3 by the same procedure as the Ni-containing alloy test described above, and the corrosion rate was measured by the same procedure. The results are shown in Table 3. For Examples 13 to 16, the corrosion rate after forging (as-forged) at a sample temperature of 430°C was measured. Further, in Examples 17 to 23, test specimens were prepared by extrusion processing in the same manner as in the above Examples 1 to 7, and the corrosion rate was measured by the same procedure. The results are also shown in Table 3. In this Cu-containing alloy test, the value of Cu is not a measured value after the alloy was prepared but a target value at the time of addition of a material.
[Table 3] (All of the alloys fall outside of the scope of the invention) Composition Corrosion rate [mg/cm2/day] as-cast Corrosion rate [mg/cm2/day] Cu content [mass%] Al content [mass%] Mn content [mass%] as-extruded as-forged Example 13 1.0 5.9 0.19 359.8 - 470.4 Example 14 3.0 6.1 0.17 1896.2 - 1538.7 Example 15 5.0 6.4 0.18 3551.5 - 2557.4 Example 16 7.0 6.5 0.18 3176.5 - 3078.1 Example 17 1.5 8.1 0.20 269.6 213.4 - Example 18 2.0 8.1 0.16 506.7 374.1 - Example 19 2.5 8.1 0.18 791.5 496.7 - Example 20 3.0 8.3 0.21 954.6 555.8 - Example 21 4.0 8.5 0.17 1561.9 749.4 - Example 22 5.0 8.1 0.15 1941.1 1032.3 - Example 23 7.0 8.3 0.26 2214.9 1274.5 - Comparative Example 4 < 0.001 6.0 0.24 7.0 - - - Furthermore,
Fig. 3 shows a graph in which Cu contents are plotted on a logarithm scale on the horizontal axis and the corrosion rate on the vertical axis for Examples 17 to 23. Linear approximation by the least-squares method was performed on the logarithm of Cu content and the corrosion rate value. In the casting "as-cast", the section was -4.0 × 102, and the slope was 3.1 × 103. This showed that, when casting a degradable structural material containing about 8.0 by mass of Al and about 0.18% by mass of Mn, the corrosion rate can be adjusted by the content of Cu according to the following Formula (3). In the extrusion processing "as-extruded", the section was -1.2 × 102, and the slope was 1.6 × 103. This showed that, when a degradable structural material containing about 8.0% by mass of Al and about 0.18% by mass of Mn was produced by extrusion processing, the corrosion rate can be adjusted by the content of Cu according to the following Formula (4). These approximate straight lines are also shown inFig. 3 . As in the case of Ni, also in the Cu-containing alloy, it was shown that, since, by performing extrusion processing, the coefficient related to an increase in the corrosion rate was suppressed as compared with the case of casting, control of the corrosion rate became easier. - For Examples 17 to 23, the same tensile test as above was carried out. As a result, all Examples showed favorable values.
[Table 4] (Noe of the example alloys fall within the scope of the present invention) Composition Tensile properties (as-extruded) Cu content [mass%] Al content [mass%] Mn content [mass%] Tensile strength [MPa] 0.2%proof stress [MPa] Elongation [%] Example 17 1.5 8.1 0.20 309.5 216.7 16.9 Example 18 2.0 8.1 0.16 302.6 204.6 16.8 Example 19 2.5 8.1 0.18 301.8 206.0 15.9 Example 20 3.0 8.3 0.21 298.9 201.2 16.6 Example 21 4.0 8.5 0.17 289.6 193.7 16.4 Example 22 5.0 8.1 0.15 283.3 190.0 15.9 Example 23 7.0 8.3 0.26 279.2 185.9 14.7
Claims (4)
- A degradable Mg alloy consisting of:3.9% by mass or more and 14.0% by mass or less of Al and 0.1% by mass or more and 0.6% by mass or less of Mn;0.01% by mass or more and 10.0% by mass or less of both of Ni and Cu, wherein the content of Ni is 0.01% by mass or more and 0.3% by mass or less, wherein the content of Cu is 1.5% by mass or more and 7.0% by mass or less;wherein the balance is composed of Mg and inevitable impurities, and
wherein the degradable Mg alloy optionally further comprises 1.0% by mass or less of Zn. - A degradable structural member consisting of the degradable Mg alloy according to claim 1.
- A method of adjusting the corrosion rate of a degradable structural member, wherein the corrosion rate is adjusted by the content of Ni and Cu in the degradable structural member using the degradable Mg alloy according to claim 1.
- Use of a degradable Mg alloy according to claim 1 for adjusting the corrosion rate of the degradable structural member, wherein the corrosion rate is adjusted by the content of Ni and Cu.
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| CN110129643A (en) * | 2019-06-13 | 2019-08-16 | 苏州市美新迪斯医疗科技有限公司 | A kind of Ultra-fine Grained biodegradable magnesium alloy material and preparation method thereof |
| WO2021075552A1 (en) | 2019-10-18 | 2021-04-22 | 株式会社栗本鐵工所 | Degradable magnesium alloy |
| CN110952013B (en) * | 2019-12-24 | 2020-12-29 | 岳阳宇航新材料有限公司 | Degradable magnesium alloy downhole tool bridge plug material and preparation method thereof |
| CN111996428A (en) * | 2020-08-28 | 2020-11-27 | 深圳市苏德技术有限公司 | Soluble magnesium alloy and preparation method and application thereof |
| CN116529413A (en) * | 2020-11-30 | 2023-08-01 | 三协立山株式会社 | Mg alloy, method for producing Mg alloy, and civil engineering material and biological material using Mg alloy |
| CN113667871A (en) * | 2021-08-10 | 2021-11-19 | 郑州轻研合金科技有限公司 | High-ductility soluble magnesium-lithium alloy and preparation method and application thereof |
| US20230392235A1 (en) * | 2022-06-03 | 2023-12-07 | Cnpc Usa Corp | Dissolvable magnesium alloy |
| CN115466890B (en) * | 2022-09-19 | 2023-12-01 | 重庆科技学院 | High-strength and high-toughness Cu-containing magnesium alloy material capable of being rapidly degraded and preparation method thereof |
| CN117327951A (en) * | 2023-08-28 | 2024-01-02 | 鹤壁恒镁新材料科技有限公司 | Aluminum-containing high-strength and toughness soluble magnesium alloy and preparation method thereof |
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| JP2007284743A (en) * | 2006-04-17 | 2007-11-01 | Tetsuichi Mogi | Mg ALLOY |
| EP2088217A1 (en) | 2006-12-11 | 2009-08-12 | Kabushiki Kaisha Toyota Jidoshokki | Casting magnesium alloy and process for production of cast magnesium alloy |
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