CN113802024A - Modification method of aluminum-copper alloy and aluminum-copper-calcium alloy - Google Patents
Modification method of aluminum-copper alloy and aluminum-copper-calcium alloy Download PDFInfo
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Abstract
The invention provides a primary or eutectic theta-Al in an aluminum-copper alloy2A method for modifying Cu phase by adding 0.01-2% of calcium element to Al-Cu alloy to obtain primary or eutectic theta-Al2The Cu phase has reduced size and changed appearance. The modification method is simple and easy to operate, and has low production cost. The invention also provides an Al-Cu-Ca alloy containing 0.01-2% of calcium element obtained after modification treatment by the method.
Description
Technical Field
The invention belongs to the technical field of alloy materials, and particularly relates to eutectic and primary Al in aluminum-copper alloy2A method for modifying Cu phase, and an aluminum-copper-calcium alloy obtained after modification.
Background
Aluminum-based aluminum-copper alloys having copper contents below 51wt.% are a class of high strength and high hardness aluminum-based alloys commonly used in production. The copper element in the alloy is combined with aluminum to generate theta-Al2When the Cu phase contains less than 33.2% of copper, eutectic structures (alpha-Al + theta-Al) are formed at the grain boundaries among primary alpha-Al grains under the production conditions of common casting or fusion welding and the like2Cu), eutectic theta-Al therein2The Cu phase is easy to grow to form a thicker and longer flaky structure, even surrounds the aluminum crystal grains, so that the aluminum crystal grains are disconnected with each other; when the copper content exceeds about 33.2%, except for (alpha-Al + theta-Al)2Cu) eutectic structure, aluminum-copperCoarse primary theta-Al in the form of bar or tree is also present in the alloy matrix2A Cu phase. Flake eutectic theta-Al with larger size2Cu or coarse primary theta-Al2The Cu phase causes the alloy to become brittle, the mechanical property is greatly reduced, and simultaneously the casting process property and the welding process property such as fluidity are also rapidly reduced. To improve the performance of aluminum-copper alloys, eutectic or primary theta-Al in the aluminum-copper alloy structure is required2The Cu phase is modified to achieve the purposes of reducing the size and changing the shape. Document "pandeming, special casting and non-ferrous alloys, 2009, 29 (8): 713-716' mechanically stirring semi-solid (between solid and liquidus temperatures) Al-40Cu alloy to make primary theta-Al in the matrix2Under the action of mechanical force, the Cu phase is converted from thick long strip shape and dendritic shape into small-size near-equiaxial crystals, so that the alloy performance is greatly improved. However, this method can only be applied to nascent theta-Al2Cu phase acts on eutectic theta-Al2The Cu phase has no function, and the special method is difficult to be universally applied to the production process conditions of conventional casting or various welding and the like.
Disclosure of Invention
In view of the above problems, the present invention provides a primary or eutectic θ -Al in an aluminum-copper alloy with a copper content below 51wt.%2A method for modifying Cu phase. By adding a certain proportion of calcium element into the aluminum-copper alloy, the calcium element is opposite to primary or eutectic theta-Al in the process of solidifying the alloy2Grain nucleation or growth of Cu is affected to make theta-Al2The Cu phase is increased, the modification treatment effect of size reduction or shape change is achieved, and meanwhile, the aluminum-copper-calcium alloy which takes aluminum-copper as a matrix and contains calcium is obtained.
The technical scheme of the invention is as follows:
primary or eutectic theta-Al in aluminum-copper alloy2The modification treatment method of the Cu phase comprises the following steps: adding a substance containing calcium element to the aluminum-copper alloy;
in the modification method, the addition amount of the substance containing the calcium element meets the condition that the content of the calcium element in the aluminum-copper alloy is 0.01-2% of the mass of the aluminum-copper alloy;
in the above method, preferably, the content of the calcium element in the aluminum-copper alloy is 0.1 to 1% by mass of the aluminum-copper alloy;
primary or eutectic theta-Al in the above aluminum-copper alloy2The method for modifying the Cu phase specifically comprises the following steps:
(1) melting the aluminum-copper alloy to be treated to a temperature range above the liquidus line of the aluminum-copper alloy to obtain an alloy melt;
(2) adding a certain amount of substances containing calcium element into the alloy melt in the step (1), and then uniformly distributing the calcium element in the aluminum-copper alloy melt;
(3) and (3) cooling the alloy melt obtained in the step (2), and solidifying to obtain the alloy subjected to modification treatment.
Preferably, the primary or eutectic θ -Al in the aluminum-copper alloy is2In the step (2) of the modification treatment method of the Cu phase, the substance containing the calcium element is one or more of aluminum-calcium master alloy, copper-calcium master alloy and magnesium-calcium master alloy.
The primary or eutectic theta-Al in the aluminum-copper alloy is adopted2The aluminum-copper-calcium alloy obtained by modification treatment of the Cu phase has a copper content of more than 0wt.% and less than 51wt.%, a calcium content of more than or equal to 0.01 wt.% and less than or equal to 2wt.%, and the balance of aluminum and other elements brought by calcium-containing substances during modification treatment or contained in the aluminum-copper alloy before modification treatment.
Preferably, the primary or eutectic theta-Al in the aluminum-copper alloy is adopted2The aluminum-copper-calcium alloy obtained by modification treatment of the Cu phase has the copper content of more than 0wt.% and less than 51wt.%, the calcium content of more than or equal to 0.01 wt.% and less than or equal to 2wt.%, and the balance of aluminum and inevitable impurity elements.
Preferably, the primary or eutectic theta-Al in the aluminum-copper alloy is adopted2An aluminum-copper-calcium alloy obtained by modification treatment of Cu phase contains copper more than 0wt.% and less than 51wt.%, calcium more than 0.1 wt.% and less than 1wt.%, and aluminum and calcium-containing substance introduced during modification treatmentOr other elements contained in the aluminum-copper alloy before the modification treatment.
Preferably, the primary or eutectic theta-Al in the aluminum-copper alloy is adopted2The aluminum-copper-calcium alloy obtained by modification treatment of the Cu phase has a copper content of more than 0wt.% and less than 51wt.%, a calcium content of more than or equal to 0.1 wt.% and less than or equal to 1wt.%, and the balance of aluminum and inevitable impurity elements.
The invention has the advantages of：The calcium element added into the aluminum-copper alloy melt can be used for eutectic or primary Al in the subsequent alloy solidification process2The grain nucleation of the Cu phase is promoted or the growth process is inhibited, thereby producing Al2The modification treatment effect of Cu phase size reduction and morphology change improves the organization structure and performance of the alloy. The aluminum-copper-calcium alloy containing calcium element obtained by the modification treatment method has a tissue structure and performance superior to those of aluminum-copper alloy without calcium. A small amount of calcium element is added into the aluminum-copper alloy and is uniformly distributed, the operation is simple and easy to implement, and the method is suitable for various production processes of casting or welding and the like for carrying out melt treatment on the aluminum-copper alloy; meanwhile, the price of calcium element is lower, so the production cost of modification treatment is also lower.
Drawings
FIG. 1 is a structural view of an optical microscope of an Al-40Cu alloy which has not been subjected to a modification treatment. Wherein the shiny strip or dendritic phase is nascent theta-Al2Cu phase with eutectic structure (alpha-Al + theta-Al) in dark area2Cu）。
Fig. 2 is a structural diagram of an optical microscope of an Al-40Cu alloy modified by adding 0.2wt.% of calcium according to an embodiment of the present invention. Wherein the shiny phase is nascent theta-Al2A Cu phase.
FIG. 3 is a structural diagram of an optical microscope of an Al-40Cu alloy after modification treatment with 0.4wt.% of Ca according to example II of the present invention; wherein the shiny phase is nascent theta-Al2A Cu phase.
FIG. 4 is a structural diagram of an optical microscope of an Al-40Cu alloy after modification treatment by adding 0.6wt.% of Ca element in the third embodiment of the present invention; whereinThe shiny phase is nascent theta-Al2A Cu phase.
FIG. 5 is a scanning electron microscope backscattered electron image of the Al-10Cu alloy without modification treatment of the fourth example; the bright part is coarse flake eutectic theta-Al surrounding alpha-Al crystal grains (dark matrix)2A Cu phase.
FIG. 6 is a scanning electron microscope backscattered electron image of an Al-10Cu alloy modified by adding 0.4wt.% of Ca element to the Al-10Cu alloy according to example IV; the bright flaky phase among alpha-Al crystal grains (dark matrix) is eutectic theta-Al2The Cu phase forms a eutectic structure with the dark flaky aluminum phase therebetween.
FIG. 7 is a scanning electron microscope backscattered electron image of the Al-10Cu alloy obtained in example V after adding 1.0wt.% of Ca element; the lamellar structure of alpha-Al crystal grains (dark matrix) in the grain boundary region with alternate light and dark is eutectic structure, wherein the bright lamellar phase is eutectic theta-Al2A Cu phase.
Detailed Description
The invention is further illustrated by the following specific examples. The following examples are only for explaining the present invention and do not limit the content of the present invention.
Example one
Calcium element is used for carrying out primary theta-Al in Al-40Cu alloy (wherein the mass percentage of Cu is 40 percent)2The Cu phase is modified, the adding proportion of calcium element is 0.2wt%, and Al-40Cu-0.2Ca alloy with improved tissue structure is obtained (wherein the mass percentage of Ca is 0.2%, the mass percentage of Cu is 40.47%, and the balance is aluminum and inevitable impurity elements).
The concrete modification treatment steps are as follows.
(1) The Al-40Cu alloy was melted to 770 ℃ (about 200 ℃ above the liquidus) to give an alloy melt.
(2) Adding a certain amount of Cu-30wt.% Ca intermediate alloy into the melt to enable the content proportion of the calcium element in the alloy melt to be 0.2wt.%, preserving heat for 20 minutes, and stirring the melt to enable the Ca element to be uniformly distributed in the melt.
(3) And then pouring the obtained melt into a mold, and cooling to obtain the Al-40Cu-0.2Ca alloy subjected to modification treatment.
Primary generation of theta-Al before Al-40Cu alloy deterioration2The Cu phase is a dendritic crystal with developed branches, the size of the primary branches is more than 500 μm, the size of the secondary branches is more than 150 μm (figure 1), and the primary theta-Al contained in the Al-40Cu-0.2Ca alloy obtained after modification by the embodiment2The Cu phase branches are obviously reduced, the length and width sizes are reduced, the size of a primary branch is mostly below 150 mu m, the size of a secondary branch existing in a small amount is about 25 mu m (figure 2), and obvious modification effect is generated.
Example two
Calcium element is used for carrying out primary theta-Al in Al-40Cu alloy (wherein the mass percentage of Cu is 40 percent)2The Cu phase is modified, the adding proportion of calcium element is 0.4wt%, and Al-40Cu-0.4Ca alloy with improved tissue structure is obtained (wherein the mass percentage of Ca is 0.4%, the mass percentage of Cu is 40%, magnesium with the mass percentage of 0.93% is also contained, and the balance is aluminum and inevitable impurity elements).
The concrete modification treatment steps are as follows.
(1) The Al-40Cu alloy was melted to 700 ℃ (about 130 ℃ above the liquidus) to give an alloy melt.
(2) Adding a certain amount of Mg-30wt.% Ca intermediate alloy into the melt to enable the content proportion of the calcium element in the alloy melt to be 0.4wt.%, preserving heat for 20 minutes, and stirring the melt to enable the Ca element to be uniformly distributed in the melt.
(3) And then pouring the obtained melt into a mold, and cooling to obtain the Al-40Cu-0.4Ca alloy subjected to modification treatment.
FIG. 3 is a structural view of an Al-40Cu-0.4Ca alloy obtained after modification of the present example, comparing with FIG. 1, as-formed θ -Al2The Cu phase branches are obviously reduced, the size is reduced, the size of a primary branch is mostly below 110 mu m, the size of a secondary branch existing in a smaller amount is about 15 mu m, and isometric crystals with the size of about 20 mu m appear.
EXAMPLE III
Calcium element to Al-40CuPrimary theta-Al in alloy (Cu content 40 wt.%)2The Cu phase is modified, the adding proportion of calcium element is 0.6wt%, and Al-40Cu-0.6Ca alloy with improved tissue structure is obtained (wherein the mass percentage of Ca is 0.6%, the mass percentage of Cu is 40%, and the balance is aluminum and inevitable impurity elements).
The concrete modification treatment steps are as follows.
(1) The Al-40% Cu alloy was melted to 750 ℃ (about 180 ℃ above the liquidus) to give an alloy melt.
(2) And (2) mixing Cu-30wt.% Ca and Al-30wt.% Ca master alloy in a mass ratio of 4:6, adding the mixture into the melt to enable the content ratio of the calcium element in the alloy melt to be 0.6wt.%, keeping the temperature for 20 minutes, and stirring the melt to enable the Ca element to be uniformly distributed in the melt.
(3) And then pouring the obtained melt into a mold, and cooling to obtain the Al-40Cu-0.6Ca alloy subjected to modification treatment.
As compared with before-modification (FIG. 1), the example shows nascent theta-Al in Al-40Cu-0.6Ca alloy obtained after modification2The Cu phase has almost no secondary branching, and the primary dendrite particle size is greatly reduced to 30 μm or less (FIG. 4), and the modification effect is very remarkable.
Example four
Calcium element is used for eutectic structure (alpha-Al + theta-Al) of Al-10Cu alloy (wherein the mass percentage of Cu is 10 percent)2theta-Al in Cu)2The Cu phase is modified, the adding proportion of calcium element is 0.4wt%, and Al-10Cu-0.4Ca alloy with improved tissue structure is obtained (wherein the mass percentage of Ca is 0.4%, the mass percentage of Cu is 10%, and the balance is aluminum and inevitable impurity elements).
The concrete modification treatment steps are as follows.
(1) The Al-10Cu alloy was melted to 710 ℃ (about 100 ℃ above the liquidus) to give an alloy melt.
(2) And (2) mixing Cu-20wt.% Ca and Al-20wt.% Ca master alloy in a mass ratio of 1:9, adding the mixture into the melt to enable the content ratio of the calcium element in the alloy melt to be 0.4wt.%, keeping the temperature for 20 minutes, and stirring the melt to enable the Ca element to be uniformly distributed in the melt.
(3) And then pouring the obtained melt into a mold, and cooling to obtain the Al-10Cu-0.4Ca alloy subjected to modification treatment.
FIG. 5 is a structural diagram of an Al-10Cu alloy before modification: the eutectic theta-Al which is in a shape of a coarse-long sheet and surrounds the primary alpha-Al crystal grains is generated on the crystal boundary between the primary alpha-Al crystal grains2Cu phase, failing to form typical alpha-Al and-Al2Cu is distributed at intervals. Using the Al-10Cu-0.4Ca alloy obtained after modification of this example, a coarse-long flaky form of theta-Al2The Cu phase is broken and more numerous, finer (shorter, narrower) and dispersed theta-Al particles appear on the grain boundaries between primary alpha-Al grains2Cu phase, thereby forming a larger amount of (alpha-Al + theta-Al) with the aluminum phase2Cu) eutectic structure (fig. 6).
EXAMPLE five
Calcium element is used for eutectic structure (alpha-Al + theta-Al) of Al-10Cu alloy (wherein the mass percentage of Cu is 10 percent)2Al in Cu)2The Cu phase is subjected to modification treatment, the adding proportion of calcium element is 1wt.%, and Al-10Cu-1Ca alloy with improved tissue structure is obtained (wherein the mass percent of Ca is 1%, the mass percent of Cu is 10%, and the balance is aluminum and inevitable impurity elements).
The concrete modification treatment steps are as follows.
(1) The Al-10Cu alloy was melted to 730 ℃ (about 120 ℃ above the liquidus) to give an alloy melt.
(2) And (2) mixing Cu-30wt.% Ca and Al-30wt.% Ca master alloy in a mass ratio of 1:9, adding the mixture into the melt to enable the content ratio of the calcium element in the alloy melt to be 1wt.%, keeping the temperature for 15 minutes, and stirring the melt to enable the Ca element to be uniformly distributed in the melt.
(3) And then pouring the obtained melt into a mold, and cooling to obtain the Al-10Cu-1Ca alloy subjected to modification treatment.
The microstructure of the Al-10Cu-1Ca alloy obtained after modification by the present example is shown in FIG. 7, and it can be seen that a large number of eutectic crystals having a fine size and being distributed at intervals appear at the grain boundaries between primary alpha-Al grainsθ-Al2A Cu phase in which a large amount of (alpha-Al + theta-Al) is formed at grain boundaries2Cu) eutectic structure, completely eliminates coarse and long flaky theta-Al surrounding primary alpha-Al crystal grains before deterioration2Cu phase (fig. 5).
Claims (9)
1. Primary or eutectic theta-Al in aluminum-copper alloy2A method for modifying a Cu phase, characterized by adding a substance containing a calcium element to an aluminum-copper alloy.
2. The method of modification treatment according to claim 1, wherein the calcium-containing substance is added in an amount such that the content of calcium in the aluminum-copper alloy is 0.01 wt.% or more and 2wt.% or less.
3. The method of modification treatment according to claim 1 or 2, wherein the calcium-containing substance is added in an amount such that the content of calcium in the aluminum-copper alloy is 0.1 wt.% or more and 1wt.% or less.
4. A method of spoiling treatment according to claim 1 or 2 or 3, comprising the steps of:
(1) melting the aluminum-copper alloy to be modified to a temperature range above the liquidus line of the aluminum-copper alloy to obtain an alloy melt;
(2) adding a substance containing calcium element into the alloy melt in the step (1) to ensure that the calcium element is uniformly distributed in the aluminum-copper alloy melt;
(3) and (3) cooling the alloy melt obtained in the step (2), and solidifying to obtain the alloy subjected to modification treatment.
5. The deterioration processing method according to claim 4, wherein: the substance containing the calcium element in the step (2) is one or more of aluminum-calcium intermediate alloy, copper-calcium intermediate alloy and magnesium-calcium intermediate alloy.
6. An aluminum-copper-calcium alloy modified by the modification method according to claim 1 or 2, or 3 or 4, wherein: the copper content is more than 0wt.% and less than 51wt.%, the calcium content is more than or equal to 0.01 wt.% and less than or equal to 2wt.%, and the balance is aluminum and other elements added by adding a calcium-containing substance during modification treatment or contained in the aluminum-copper alloy before modification treatment.
7. An aluminum-copper-calcium alloy according to claim 6, wherein: the copper content is more than 0wt.% and less than 51wt.%, the calcium content is more than or equal to 0.01 wt.% and less than or equal to 2wt.%, and the balance is aluminum and inevitable impurity elements.
8. The aluminum-copper-calcium alloy of claim 6, wherein: the copper content is more than 0wt.% and less than 51wt.%, the calcium content is more than or equal to 0.1 wt.% and less than or equal to 1wt.%, and the balance is aluminum and other elements added by adding a calcium-containing substance during modification treatment or contained in the aluminum-copper alloy before modification treatment.
9. An aluminum-copper-calcium alloy according to claim 6 or 8, wherein: the copper content is more than 0wt.% and less than 51wt.%, the calcium content is more than or equal to 0.1 wt.% and less than or equal to 1wt.%, and the balance is aluminum and inevitable impurity elements.
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Cited By (1)
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| CN115725878A (en) * | 2022-11-16 | 2023-03-03 | 南京航空航天大学 | Al-Ca series heat-treatment-free aluminum alloy and preparation method thereof |
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| CN115725878A (en) * | 2022-11-16 | 2023-03-03 | 南京航空航天大学 | Al-Ca series heat-treatment-free aluminum alloy and preparation method thereof |
| CN115725878B (en) * | 2022-11-16 | 2024-02-23 | 南京航空航天大学 | Al-Ca series heat treatment-free aluminum alloy and preparation method thereof |
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Application publication date: 20211217 |