CN115415488A - Horizontal continuous casting preparation process for ultra-high quality single crystal copper - Google Patents
Horizontal continuous casting preparation process for ultra-high quality single crystal copper Download PDFInfo
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- CN115415488A CN115415488A CN202210895503.4A CN202210895503A CN115415488A CN 115415488 A CN115415488 A CN 115415488A CN 202210895503 A CN202210895503 A CN 202210895503A CN 115415488 A CN115415488 A CN 115415488A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/04—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds
- B22D11/045—Continuous casting of metals, i.e. casting in indefinite lengths into open-ended moulds for horizontal casting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/14—Plants for continuous casting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
- B22D11/16—Controlling or regulating processes or operations
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Abstract
The invention relates to a preparation process of single crystal copper, in particular to a horizontal continuous casting preparation process of ultra-high quality single crystal copper, which comprises the following steps: s1: preparing a single-crystal copper rod having a (001) orientation; s2: preparing the prepared single crystal copper rod with the (001) orientation into a single crystal copper horizontal continuous casting draw bar; s3: the prepared single crystal copper horizontal continuous casting draw bar is matched with a hot type horizontal continuous casting machine to prepare the single crystal copper. Compared with the prior art, the invention provides a high-quality single crystal copper rod/wire preparation method based on epitaxial growth, and particularly relates to a single crystal copper rod/wire orientation control method, which can not only eliminate the columnar crystal phenomenon in the horizontal continuous casting preparation process of the single crystal copper rod/wire and improve the horizontal continuous casting preparation qualification rate of the single crystal copper, but also strictly control the crystal orientation of the horizontal continuous casting single crystal copper rod/wire, obtain the single crystal copper rod/wire with the (001) orientation completely coincident with the axial direction, and greatly improve the comprehensive performance of the single crystal copper.
Description
Technical Field
The invention relates to a preparation process of single crystal copper, in particular to a horizontal continuous casting preparation process of ultrahigh-quality single crystal copper.
Background
Because the crystal boundary of a resistance generation source and a signal attenuation source is eliminated, the single crystal copper has excellent electrical and signal transmission performance, excellent corrosion resistance and good plastic processing performance, and is widely applied to the fields of communication (mainly focusing on acoustic horns, power lines, audio connecting lines, microphone lines, HDMI cables, various connectors and the like), electronic packaging (connection of chips and external leads in large-scale integrated circuits) and the like. In recent years, with the rapid development of the semiconductor industry in China, the demand for high-quality single crystal copper in China is explosively increased.
Currently, single-crystal copper wire is mainly prepared by a hot continuous casting method (OCC), which was originally invented by professor dahlia koenii in japan, and is an improvement of the conventional horizontal continuous casting process (a heated mold is used to replace a water-cooled mold for horizontal continuous casting, and the temperature gradient in the axial direction of the mold is relatively increased by reducing the temperature gradient in the radial direction of the mold, so that the formation of lateral grains is avoided, and the growth of axial grains is promoted). Therefore, in essence, the preparation of single crystal copper by the hot continuous casting method is a continuous directional solidification process, when a draw bar introduces a copper melt into a casting mold, the copper melt rapidly nucleates on the end face of the draw bar to form a crystal with free orientation, then other crystal grains are gradually eliminated under the action of competitive growth along with the continuous drawing of the draw bar, and finally a certain crystal grain with a preferred direction is retained and gradually grows to form a single crystal. From the results of the crystal competition growth we can obtain: 1) If 2 or more than 2 (001) crystals are formed in the free nucleation process, due to the consistency of kinetics and thermodynamics, the crystal grains with consistent orientation can keep a 'flush and go' growth state, and finally a columnar crystal structure is obtained; 2) If no crystal grain coinciding with the axial direction of the single crystal rod/line is obtained in the process of free nucleation (namely, a certain included angle exists between the (001) direction of the copper crystal and the axial direction of the single crystal rod/line), after the competitive growth, the copper crystal grain with the minimum included angle grows into a single crystal, and finally, a single crystal structure with deviated orientation is obtained. It is obvious that the two situations can have great influence on the structure and the final performance of the copper single crystal bar/wire, and the quality consistency and the reliability of the high-quality single crystal copper wire are damaged.
Disclosure of Invention
The concept of epitaxial growth (epitaxy) comes from greek, and the core idea is that when a melt nucleates on a substrate with a specific orientation (generally the habit), a solidification structure obtains the specific orientation, and for nearly two centuries, epitaxy has been widely used in the field of semiconductor coating, including CVD, PVD, MED, and chemical epitaxy, among others. The invention aims to provide a high-quality single crystal copper rod/wire preparation method based on epitaxial growth, and particularly relates to a single crystal copper rod/wire orientation control method.
The purpose of the invention is realized by the following technical scheme:
a horizontal continuous casting preparation process of ultra-high quality monocrystalline copper comprises the following steps:
s1: preparing a single crystal copper rod having a (001) orientation;
s2: preparing the single crystal copper rod with the (001) orientation prepared in the step S1 into a single crystal copper horizontal continuous casting draw bar;
s3: and (4) preparing the single crystal copper by utilizing the single crystal copper horizontal continuous casting draw bar prepared in the step (S2) and matching with a hot type horizontal continuous casting machine.
Preferably, step S1 includes the following steps:
s11: directional solidification of the single crystal copper rod;
s12: cutting a single crystal copper rod with (001) orientation;
in step S11, HRS method is adopted for directional solidification;
in step S12, the cutting is: the single crystal copper rod was calibrated for (001) orientation by a laey diffractometer and subsequently cut by wire cutting.
Preferably, in step S11, a graphite mold or an alumina mold with a spiral crystal selector is selected in the directional solidification process.
Preferably, in step S11, the holding temperature in the directional solidification process is 1200 ℃, and the drawing speed is 3mm/min.
Preferably, in step S2, the single crystal copper rod with (001) orientation is screwed with a tool steel or stainless steel rod to form a single crystal copper horizontal continuous casting drawbar.
Preferably, in step S2, the length of the single crystal copper rod having the (001) orientation is not less than 80mm.
Preferably, when the diameter ratio of the single crystal copper horizontal continuous casting draw bar to the single crystal copper product is less than 0.5, a stepped gradual shouldering structure is adopted. The stepped gradual shouldering structure can avoid the formation of mixed crystals, thereby ensuring the accuracy and reliability of orientation. The single crystal copper product as referred to herein means a single crystal copper product obtained by final crystallization.
Preferably, step S3 includes the following steps:
s31: 3N-6N high-purity copper is filled into a crucible of a hot type horizontal continuous casting machine, and a single-crystal copper horizontal continuous casting draw bar is placed into a hot type crystallizer of the hot type horizontal continuous casting machine;
s32: heating the crucible to heat the high purity copper;
s33: after the high-purity copper in the crucible is converted into a copper melt and reaches a set temperature, setting the temperature of a hot crystallizer and rapidly heating;
s34: and after the hot type crystallizer reaches the set temperature, setting the drawing speed of the single crystal copper horizontal continuous casting draw bar and drawing uniformly, so that the copper melt is drawn out of the hot type crystallizer along with the single crystal copper horizontal continuous casting draw bar and grows into the single crystal copper.
Preferably, in step S32, the set temperature of the heating crucible is 1180-1280 ℃; in the step S33, the set temperature of the hot crystallizer is 700-950 ℃; in step S34, the drawing speed of the single crystal copper horizontal continuous casting draw bar is 3-9mm/min.
Preferably, in step S3, the single crystal copper is a single crystal copper rod or a single crystal copper wire.
The core of the preparation process is that the single crystal copper part at the front end of the single crystal copper draw bar (namely the single crystal copper horizontal continuous casting draw bar) is completely fused with the copper melt after being melted by controlling the temperature of the hot crystallizer. In the subsequent drawing process, under the condition of axial heat dissipation, the melt at the front edge of the standard (001) single crystal copper interface at the front end of the drawing rod is subjected to epitaxial growth, so that a high-performance single crystal copper rod/wire rod with the orientation completely consistent with that of the standard (001) single crystal copper draw rod is obtained.
Compared with the prior art, the invention has the following beneficial effects:
by adopting the method, the columnar crystal phenomenon in the horizontal continuous casting preparation process of the single crystal copper rod/wire can be avoided, the horizontal continuous casting preparation qualification rate of the single crystal copper is improved, the crystal orientation of the horizontal continuous casting single crystal copper rod/wire can be strictly controlled, the single crystal copper rod/wire with the (001) orientation completely coincident with the axial direction is obtained, and the comprehensive performance of the single crystal copper is greatly improved. Meanwhile, the invention improves the production stability and reliability of the single crystal copper from the process, is beneficial to reducing the detection requirement and the detection steps of the single crystal copper product, can greatly improve the production efficiency of the single crystal copper product and reduce the production cost of the single crystal copper product.
Drawings
FIG. 1 is a Laue diffraction pattern of a cross-section of a single crystal copper rod obtained by HRS directional solidification in example 1;
FIG. 2 is a Laue diffraction pattern of a cross section of a front end of a single crystal copper horizontal continuous casting drawbar in example 1;
fig. 3 is a schematic structural view of a single-crystal copper horizontal continuous casting drawbar in embodiment 1;
fig. 4 is a schematic view showing the assembly of a horizontal continuous casting drawbar of single crystal copper and a hot mold of a hot type horizontal continuous casting machine in example 1;
FIG. 5 is a Laue diffraction pattern of a cross section of a horizontal continuous cast product in example 1;
in the figure: 11-standard (001) copper single crystal; 12-tool steel; 21-a crucible; 22-a heater; 23-a thermal type crystallizer; 24-a single crystal copper horizontal continuous casting draw bar; 25-copper melt.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
1) Preparing a single crystal copper rod having a (001) orientation;
in the embodiment, a HRS directional solidification furnace produced by Coui metallurgical equipment science and technology Limited is used for carrying out (001) oriented single crystal copper bar, a graphite mold with a spiral crystal selector is used, and the main structure of the mold is a cylinder with the diameter of 20mm. The main technological parameters in the directional solidification process comprise: the heat preservation temperature of the copper melt is as follows: 1200 ℃; directional solidification drawing speed: 3mm/min;
in this example, a crystal orientation of a single crystal copper rod was calibrated by a laey diffractometer, a test bar was fixed on a three-dimensional rotating chuck and loaded into the laey diffractometer, and the initial calibration of the crystal orientation was performed, and fig. 1 shows the laey diffraction result of the cross section of the single crystal test bar, which was measured, and the angle between the crystal orientation of the copper single crystal (001) and the normal of the end face of the test bar was 5.179 °. And rotating the three-dimensional rotating clamp according to the diffraction result to adjust the position of the test bar, and calibrating the Laue diffractometer again. By continuously adjusting the three-dimensional rotating fixture, the (001) direction of the crystal is almost completely consistent with the normal line.
2) Manufacturing a single crystal horizontal continuous casting draw bar by using a single crystal copper rod with standard (001) orientation;
taking the special fixture off the Laue diffractometer, installing the special fixture on a linear cutting device, cutting a standard (001) copper single crystal with the diameter of 8mm on a single crystal copper rod by adopting linear cutting, and preparing a single crystal horizontal continuous casting draw bar by utilizing the copper single crystal. FIG. 2 shows the Laue diffraction results of a cross section of the front end of a single-crystal horizontal continuous casting drawbar, in which the angle between the crystal orientation of the front copper single crystal (001) and the normal of the end face of the drawbar was measured to be 0.891 deg.. Fig. 3 is a schematic view of a single crystal horizontal drawbar having a standard (001) copper single crystal 11 at the front end and a tool steel 12 at the rear end, which are screwed together.
In this embodiment, the front end length of the single crystal horizontal continuous casting drawbar is 80mm, and the rear end length is 520mm.
3) Preparing single crystal copper by using a single crystal copper draw bar and matching with a hot type horizontal continuous casting machine;
in this embodiment, the horizontal continuous casting machine used is a self-made horizontal continuous casting machine of 15 kg level, and the assembly of the crystallizer and the single crystal horizontal continuous casting pulling rod is shown in fig. 4.
In the horizontal continuous casting process, first, 3N to 6N of high purity copper is charged into a crucible 21 of a hot type horizontal continuous casting machine, and a single crystal copper horizontal continuous casting drawbar 24 is placed into a horizontal continuous casting hot type mold 23. Then, the heating temperature of the crucible 21 is set to 1200 ℃, then the high purity copper is started to be heated, and after the temperature of the copper melt 25 reaches 1200 ℃, the hot type crystallizer 23 is rapidly heated by the heater 22, and the heating temperature is 900 ℃. When the temperature of the hot type crystallizer 23 reaches the set temperature, the drawing speed is set to be 3mm/min, and the single crystal copper horizontal continuous casting draw bar 24 and the copper melt 25 are drawn out of the crystallizer together.
FIG. 5 shows the experimental results of Laue diffraction of the cross section of the sample at 5mm from the front end of the horizontal drawbar of the single crystal, and it can be seen from the figure that the diffraction spot of the sample is a standard (001) plane diffraction spot, and the angle between the (001) crystal direction and the normal of the horizontal section of the copper single crystal is only 0.576 degrees. By adopting the method, the single crystal copper rod/wire with the (001) orientation completely coincident with the axial direction is obtained, the orientation of the single crystal copper is strictly controlled, and the comprehensive performance of the single crystal copper is greatly improved.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A horizontal continuous casting preparation process of ultra-high quality monocrystalline copper is characterized by comprising the following steps:
s1: preparing a single crystal copper rod having a (001) orientation;
s2: preparing the single crystal copper rod with the (001) orientation prepared in the step S1 into a single crystal copper horizontal continuous casting draw bar;
s3: and (4) preparing the single crystal copper by utilizing the single crystal copper horizontal continuous casting draw bar prepared in the step (S2) and matching with a hot type horizontal continuous casting machine.
2. The horizontal continuous casting preparation process of ultra-high quality monocrystalline copper according to claim 1, characterized in that step S1 comprises the following steps:
s11: directional solidification of the single crystal copper rod;
s12: cutting a single crystal copper rod with (001) orientation;
in step S11, HRS method is adopted for directional solidification;
in step S12, the cutting is: the single crystal copper rod was calibrated for (001) orientation by a laey diffractometer and subsequently cut by wire cutting.
3. The horizontal continuous casting preparation process of ultra-high quality single crystal copper according to claim 2, wherein in step S11, a graphite mold or an alumina mold with a spiral crystal selector is selected in the directional solidification process.
4. The horizontal continuous casting preparation process of ultra-high quality single crystal copper according to claim 2, wherein in step S11, the holding temperature during the directional solidification is 1200 ℃ and the drawing speed is 3mm/min.
5. The ultra-high quality single crystal copper horizontal continuous casting preparation process according to claim 1, wherein in step S2, the single crystal copper rod with (001) orientation is screwed with a tool steel or stainless steel rod to form a single crystal copper horizontal continuous casting drawbar.
6. The horizontal continuous casting preparation process of ultra-high quality single crystal copper according to claim 1 or 5, wherein in step S2, the length of the single crystal copper rod with (001) orientation is not less than 80mm.
7. The horizontal continuous casting preparation process of ultra-high quality monocrystalline copper according to claim 1, wherein in step S2, when the ratio of the diameter of the single crystal copper horizontal continuous casting draw bar to the single crystal copper product is less than 0.5, a stepped gradual shouldering structure is adopted.
8. The horizontal continuous casting preparation process of ultra-high quality monocrystalline copper according to claim 1, characterized in that step S3 comprises the following steps:
s31: 3N-6N high-purity copper is filled into a crucible of a hot type horizontal continuous casting machine, and a single-crystal copper horizontal continuous casting draw bar is placed into a hot type crystallizer of the hot type horizontal continuous casting machine;
s32: heating the crucible to heat the high purity copper;
s33: after the high-purity copper in the crucible is converted into a copper melt and reaches a set temperature, setting the temperature of the hot crystallizer and rapidly heating;
s34: and after the hot crystallizer reaches the set temperature, setting the drawing speed of the single crystal copper horizontal continuous casting draw bar and drawing uniformly, so that the copper melt is drawn out of the hot crystallizer along with the single crystal copper horizontal continuous casting draw bar and grows into the single crystal copper.
9. The horizontal continuous casting preparation process of ultra-high quality monocrystalline copper according to claim 8, characterized in that, in step S32, the set temperature of the heating crucible is 1180-1280 ℃; in the step S33, the set temperature of the hot crystallizer is 700-950 ℃; in step S34, the drawing speed of the single crystal copper horizontal continuous casting draw bar is 3-9mm/min.
10. The horizontal continuous casting process for preparing ultra-high quality single crystal copper according to claim 1, wherein in step S3, the single crystal copper is a single crystal copper rod or a single crystal copper wire.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0181567A1 (en) * | 1984-11-03 | 1986-05-21 | MANNESMANN Aktiengesellschaft | Equipment for casting metal strip, especially steel strip |
| JPH1110312A (en) * | 1997-06-26 | 1999-01-19 | Sumitomo Chem Co Ltd | Method for continuously producing single crystal |
| US5906717A (en) * | 1994-04-28 | 1999-05-25 | Sumitomo Chemical Company, Limited | Sputtering target of single crystal aluminum alloy |
| CN101817072A (en) * | 2010-04-14 | 2010-09-01 | 北京科技大学 | Casting equipment and method using solid-liquid two-phase region temperature as casting mold temperature |
| CN106270427A (en) * | 2016-11-01 | 2017-01-04 | 东莞市逸昊金属材料科技有限公司 | A kind of amorphous master alloy ingot continuous casting system and using method thereof |
| CN111364096A (en) * | 2020-03-30 | 2020-07-03 | 上海交通大学 | Substrate-triggered single crystal high-temperature alloy directional solidification process |
| CN216938343U (en) * | 2022-03-15 | 2022-07-12 | 东北大学 | Combined type guide rod device capable of regulating and controlling orientation of high-purity copper single crystal |
-
2022
- 2022-07-27 CN CN202210895503.4A patent/CN115415488A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0181567A1 (en) * | 1984-11-03 | 1986-05-21 | MANNESMANN Aktiengesellschaft | Equipment for casting metal strip, especially steel strip |
| US5906717A (en) * | 1994-04-28 | 1999-05-25 | Sumitomo Chemical Company, Limited | Sputtering target of single crystal aluminum alloy |
| JPH1110312A (en) * | 1997-06-26 | 1999-01-19 | Sumitomo Chem Co Ltd | Method for continuously producing single crystal |
| CN101817072A (en) * | 2010-04-14 | 2010-09-01 | 北京科技大学 | Casting equipment and method using solid-liquid two-phase region temperature as casting mold temperature |
| CN106270427A (en) * | 2016-11-01 | 2017-01-04 | 东莞市逸昊金属材料科技有限公司 | A kind of amorphous master alloy ingot continuous casting system and using method thereof |
| CN111364096A (en) * | 2020-03-30 | 2020-07-03 | 上海交通大学 | Substrate-triggered single crystal high-temperature alloy directional solidification process |
| CN216938343U (en) * | 2022-03-15 | 2022-07-12 | 东北大学 | Combined type guide rod device capable of regulating and controlling orientation of high-purity copper single crystal |
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