Preparation method of transition metal ion doped eutectic crystal

Abstract

The invention discloses a preparation method of a transition metal ion doped eutectic crystal, and relates to the technical field of eutectic crystals. Doping the transition metal ions into the eutectic crystal for growth; wherein the transition metal ions are chromium ions or cobalt ions, and the eutectic crystal body is a binary eutectic crystal body Al2O3-Y3Al5O12 or a ternary eutectic crystal body Al2O3-Y3Al5O12-ZrO2; transition metal ion chromium or cobalt is doped in Al2O3-Y3Al5O12 or Al2O3-Y3Al5O12-ZrO2 to respectively form red and blue colored eutectic crystals, and the color gradient from light red and blue color to dark red and blue color is formed by regulating and controlling the ion concentration of chromium or cobalt.

Description

Technical Field

[0001] The present invention relates to the field of eutectic crystals, and in particular to a method for preparing a transition metal ion-doped eutectic crystal. Background Art

[0002] Eutectic crystals have high strength, high hardness, high melting point, excellent stability and processing performance, and are widely used in the fields of aerospace, large turbine blades, internal combustion engine manufacturing, etc., and have been widely studied by scientific researchers all over the world so far; Al 2 O 3 -Y 3 Al 5 O 12 and Al 2 O 3 -Y 3 Al 5 O 12 -ZrO 2 are the two most important eutectic crystals, which can be directionally and rapidly solidified in a high-temperature melt, have a melting point greater than 1500 °C and can work stably in a high-temperature oxygen environment, and exhibit excellent physical, chemical and mechanical processing properties.

[0003] In the new era of the 21st century, with the continuous development and in-depth research, the huge industrial value of rare earth ion- and transition metal ion-doped eutectic crystals in the fields of light-emitting diodes (LEDs), high-end jewelry, etc. has put forward higher and newer requirements for eutectic crystals. Summary of the Invention

[0004] The purpose of the present invention is to provide a method for preparing a transition metal ion-doped eutectic crystal.

[0005] To achieve the above purpose, the present invention provides the following technical solution: A method for preparing a transition metal ion-doped eutectic crystal, growing the transition metal ion-doped eutectic crystal;

[0006] wherein the transition metal ion is a chromium ion or a cobalt ion, and the eutectic crystal is a binary eutectic crystal Al 2 O 3 -Y 3 Al 5 O 12 or a ternary eutectic crystal Al 2 O 3 -Y 3 Al 5 O 12 -ZrO 2 .

[0007] Furthermore, grow the transition metal-doped eutectic crystal by the micro-pulling-down method.

[0008] Further, it includes the following steps:

[0009] Weigh the raw materials and mix them evenly in an agate mortar, then shape them into rods, seal them, perform cold isostatic pressing, and sinter them in air. After sintering, load them into a micro-pulling furnace and conduct eutectic growth through the micro-pulling method.

[0010] Further, the doping concentration of the transition metal ions is 0.4 at% - 1.9 at%.

[0011] Further, the mass percentage of the raw materials in the binary eutectic crystal is: 80% of Al 2 O 3 and 20% of Y 3 O 2 .

[0012] Further, the mass percentage of the raw materials in the ternary eutectic crystal is: 65% of Al 2 O 3 、16% of Y 2 O 3 and 19% of ZrO 2 .

[0013] Further, perform cold isostatic pressing at 50 MPa for 2 minutes, then sinter in air at 1200 °C for 24 hours, load into a micro-pulling furnace, and then heat up to melt and prepare for growth.

[0014] Further, the micro-pulling speed in the micro-pulling furnace is 0.3 mm / min. After the eutectic crystal growth is completed, slowly cool it to room temperature and take out the eutectic crystal.

[0015] Further, the raw materials used are Cr 2 O 3 、Co 3 O 4 、Al 2 O 3 、Y 2 O 3 and ZrO 2 .

[0016] Further, the purity of the raw materials used is Cr 2 O 3 ≥99.99%, Co 3 O 4 ≥99.99%, Al 2 O 3 ≥99.99%, Y 2 O 3 ≥99.99%, ZrO 2 ≥99.99%.

[0017] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0018] 1. In the present invention, by doping transition metal ions chromium or cobalt into Al 2 O 3 -Y 3 Al 5 O 12 or Al 2 O 3 -Y 3 Al 5 O 12 -ZrO 2 red and blue colored eutectic crystals are respectively formed. By regulating the ion concentration of chromium or cobalt, a color gradient from light red and blue to dark red and blue is formed;

[0019] 2. The present invention uses the micro-pulling-down method for eutectic growth, which can achieve rapid crystal growth, save a large amount of time cost, grow crystals with uniform diameter and use less raw materials, thus reducing the cost required for experiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 are the photos of the eutectic crystals of Examples 1-8 of the present invention;

[0021] Figure 2 are the photos of the eutectic crystals of Examples 9-16 of the present invention

[0022] Figure 3 are the CIE spectra of the eutectic crystals of Examples 1-8 of the present invention;

[0023] Figure 4 are the CIE spectra of the eutectic crystals of Examples 9-16 of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0024] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments.

[0025] The present invention provides a technical solution: a preparation method of a transition metal ion-doped eutectic crystal, growing a transition metal ion-doped eutectic crystal;

[0026] wherein the transition metal ion is a chromium ion or a cobalt ion, and the eutectic crystal is a binary eutectic crystal Al 2 O 3 -Y 3 Al 5 O 12 or a ternary eutectic crystal Al 2 O 3 -Y3 A l 5 O 12 -ZrO 2 。

[0027] In a further embodiment of this example, transitional metal-doped eutectic crystals are grown by the micro-pulling method.

[0028] In a further embodiment of this example, the following steps are included:

[0029] Weigh the raw materials and mix them evenly in an agate mortar, then shape them into rods, seal them, perform cold isostatic pressing, sinter them in air, and load them into a micro-pulling furnace for eutectic growth by the micro-pulling method.

[0030] In a further embodiment of this example, the doping concentration of the transitional metal ions is 0.4 at% - 1.9 at%.

[0031] In a further embodiment of this example, the mass percentage of the raw materials in the binary eutectic crystal is: 80% A l 2 O 3 and 20% Y 3 O 2 。

[0032] In a further embodiment of this example, the mass percentage of the raw materials in the ternary eutectic crystal is: 65% A l 2 O 3 、16% Y 2 O 3 and 19% ZrO 2 。

[0033] In a further embodiment of this example, perform cold isostatic pressing at 50 MP for 2 min, then sinter in air at 1200 °C for 24 h, load into a micro-pulling furnace, and then heat up to melt for growth preparation.

[0034] In a further embodiment of this example, the micro-pulling speed in the micro-pulling furnace is 0.3 mm / min. After the eutectic crystal growth is completed, slowly cool it to room temperature and take out the eutectic crystal.

[0035] In a further embodiment of this example, the raw materials used are Cr 2 O 3 、Co 3 O 4 、Al 2 O 3 、Y 2 O 3 and ZrO 2 。

[0036] In a further embodiment of this example, the purity of the raw materials used is Cr 2 O 3 ≥99.99%, Co 3 O 4 ≥99.99%, Al 2 O 3 ≥99.99%, Y 2 O 3 ≥99.99%, ZrO 2 ≥99.99%.

[0037] Example 1

[0038] Weigh the high-purity raw materials of Cr 2 O 3 , Al 2 O 3 , Y 2 O 3 at 0.4 at% Cr, with a total weight of 7.5 g. Then mix them evenly in an agate mortar, shape them into a rod, seal it, perform cold isostatic pressing at 50 MP for 2 min, sinter in air at 1200 °C for 24 h, load it into a micro-pulling furnace, and then heat it up to melt for crystal growth preparation. The micro-pulling speed is 0.3 mm / min. After crystal growth is completed, slowly cool it to room temperature and take out the crystal.

[0039] Example 2

[0040] Weigh the high-purity raw materials of Cr 2 O 3 , Al 2 O 3 , Y 2 O 3 at 0.7% Cr, with a total weight of 7.5 g. Then mix them evenly in an agate mortar, shape them into a rod, seal it, perform cold isostatic pressing at 50 MP for 2 min, sinter in air at 1200 °C for 24 h, load it into a micro-pulling furnace, and then heat it up to melt for crystal growth preparation. The micro-pulling speed is 0.3 mm / min. After crystal growth is completed, slowly cool it to room temperature and take out the crystal.

[0041] Example 3

[0042] Weigh the high-purity raw materials of Cr 2 O 3 , Al 2 O 3 , Y 2 O 3The high-purity raw materials are weighed according to 1.5% Cr, with a total weight of 7.5 g. Then they are mixed evenly in an agate mortar, shaped into a rod, sealed, cold isostatically pressed at 50 MP for 2 min, sintered in air at 1200 °C for 24 h, loaded into a micro-pulling furnace, and then heated to melt for crystal growth preparation. The micro-pulling speed is 0.3 mm / min. After crystal growth is completed, it is slowly cooled to room temperature and the crystal is taken out.

[0043] Example 4

[0044] The Cr 2 O 3 , Al 2 O 3 , Y 2 O 3 The high-purity raw materials are weighed according to 1.9% Cr, with a total weight of 7.5 g. Then they are mixed evenly in an agate mortar, shaped into a rod, sealed, cold isostatically pressed at 50 MP for 2 min, sintered in air at 1200 °C for 24 h, loaded into a micro-pulling furnace, and then heated to melt for crystal growth preparation. The micro-pulling speed is 0.3 mm / min. After crystal growth is completed, it is slowly cooled to room temperature and the crystal is taken out.

[0045] Example 5

[0046] The Cr 2 O 3 , Al 2 O 3 , Y 2 O 3 and ZrO 2 The high-purity raw materials are weighed according to 0.4% Cr, with a total weight of 7.5 g. Then they are mixed evenly in an agate mortar, shaped into a rod, sealed, cold isostatically pressed at 50 MP for 2 min, sintered in air at 1200 °C for 24 h, loaded into a micro-pulling furnace, and then heated to melt for crystal growth preparation. The micro-pulling speed is 0.3 mm / min. After crystal growth is completed, it is slowly cooled to room temperature and the crystal is taken out.

[0047] Example 6

[0048] The Cr 2 O 3 , Al 2 O 3 , Y 2 O 3 and ZrO 2 The high-purity raw materials are weighed according to 0.7% Cr, with a total weight of 7.5 g. Then they are mixed evenly in an agate mortar, shaped into a rod, sealed, cold isostatically pressed at 50 MP for 2 min, sintered in air at 1200 °C for 24 h, loaded into a micro-pulling furnace, and then heated to melt for crystal growth preparation. The micro-pulling speed is 0.3 mm / min. After crystal growth is completed, it is slowly cooled to room temperature and the crystal is taken out.

[0049] Example 7

[0050] Weigh the high-purity raw materials of Cr 2 O 3 , Al 2 O 3 , Y 2 O 3 and ZrO 2 at a weight ratio of 1.5% Cr, with a total weight of 7.5 g. Then mix them evenly in an agate mortar, shape them into a rod, seal it, perform cold isostatic pressing at 50 MPa for 2 min, sinter in air at 1200 °C for 24 h, load it into a micro-pulling furnace, and then heat it up to melt for crystal growth preparation. The micro-pulling speed is 0.3 mm / min. After crystal growth is completed, slowly cool it to room temperature and take out the crystal.

[0051] Example 8

[0052] Weigh the high-purity raw materials of Cr 2 O 3 , Al 2 O 3 , Y 2 O 3 and ZrO 2 at a weight ratio of 1.9% Cr, with a total weight of 7.5 g. Then mix them evenly in an agate mortar, shape them into a rod, seal it, perform cold isostatic pressing at 50 MPa for 2 min, sinter in air at 1200 °C for 24 h, load it into a micro-pulling furnace, and then heat it up to melt for crystal growth preparation. The micro-pulling speed is 0.3 mm / min. After crystal growth is completed, slowly cool it to room temperature and take out the crystal.

[0053] Example 9

[0054] Weigh the high-purity raw materials of Co 3 O 4 , Al 2 O 3 , Y 2 O 3 at a weight ratio of 0.4% Cr, with a total weight of 7.5 g. Then mix them evenly in an agate mortar, shape them into a rod, seal it, perform cold isostatic pressing at 50 MPa for 2 min, sinter in air at 1200 °C for 24 h, load it into a micro-pulling furnace, and then heat it up to melt for crystal growth preparation. The micro-pulling speed is 0.3 mm / min. After crystal growth is completed, slowly cool it to room temperature and take out the crystal.

[0055] Example 10

[0056] Weigh the high-purity raw materials of Co 3 O 4 , Al 2 O 3 , Y 2 O3 The high-purity raw materials are weighed according to 0.7% Cr, with a total weight of 7.5 g. Then they are mixed evenly in an agate mortar, shaped into a rod, sealed, cold isostatically pressed at 50 MP for 2 min, sintered in air at 1200 °C for 24 h, loaded into a micro-pulling furnace, and then heated to melt for crystal growth preparation. The micro-pulling speed is 0.3 mm / min. After crystal growth is completed, it is slowly cooled to room temperature and the crystal is taken out.

[0057] Example 11

[0058] Take Co 3 O 4 , Al 2 O 3 , Y 2 O 3 The high-purity raw materials are weighed according to 1.5% Cr, with a total weight of 7.5 g. Then they are mixed evenly in an agate mortar, shaped into a rod, sealed, cold isostatically pressed at 50 MP for 2 min, sintered in air at 1200 °C for 24 h, loaded into a micro-pulling furnace, and then heated to melt for crystal growth preparation. The micro-pulling speed is 0.3 mm / min. After crystal growth is completed, it is slowly cooled to room temperature and the crystal is taken out.

[0059] Example 12

[0060] Take Co 3 O 4 , Al 2 O 3 , Y 2 O 3 The high-purity raw materials are weighed according to 1.9% Cr, with a total weight of 7.5 g. Then they are mixed evenly in an agate mortar, shaped into a rod, sealed, cold isostatically pressed at 50 MP for 2 min, sintered in air at 1200 °C for 24 h, loaded into a micro-pulling furnace, and then heated to melt for crystal growth preparation. The micro-pulling speed is 0.3 mm / min. After crystal growth is completed, it is slowly cooled to room temperature and the crystal is taken out.

[0061] Example 13

[0062] Take Co 3 O 4 , Al 2 O 3 , Y 2 O 3 and ZrO 2 The high-purity raw materials are weighed according to 0.4% Cr, with a total weight of 7.5 g. Then they are mixed evenly in an agate mortar, shaped into a rod, sealed, cold isostatically pressed at 50 MP for 2 min, sintered in air at 1200 °C for 24 h, loaded into a micro-pulling furnace, and then heated to melt for crystal growth preparation. The micro-pulling speed is 0.3 mm / min. After crystal growth is completed, it is slowly cooled to room temperature and the crystal is taken out.

[0063] Example 14

[0064] Weigh Co 3 O 4 , Al 2 O 3 , Y 2 O 3 and ZrO 2 High-purity raw materials are weighed according to 0.7% Cr, with a total weight of 7.5 g. Then they are mixed evenly in an agate mortar, shaped into a rod and sealed, cold isostatically pressed at 50 MP for 2 min, sintered in air at 1200 °C for 24 h, loaded into a micro-pulling furnace, and then heated to melt for growth preparation. The micro-pulling speed is 0.3 mm / min. After crystal growth is completed, it is slowly cooled to room temperature and the crystal is taken out.

[0065] Example 15

[0066] Weigh Co 3 O 4 , Al 2 O 3 , Y 2 O 3 and ZrO 2 High-purity raw materials are weighed according to 0.7% Cr, with a total weight of 7.5 g. Then they are mixed evenly in an agate mortar, shaped into a rod and sealed, cold isostatically pressed at 50 MP for 2 min, sintered in air at 1200 °C for 24 h, loaded into a micro-pulling furnace, and then heated to melt for growth preparation. The micro-pulling speed is 0.3 mm / min. After crystal growth is completed, it is slowly cooled to room temperature and the crystal is taken out.

[0067] Example 16

[0068] Weigh Co 3 O 4 , Al 2 O 3 , Y 2 O 3 and ZrO 2 High-purity raw materials are weighed according to 1.9% Cr, with a total weight of 7.5 g. Then they are mixed evenly in an agate mortar, shaped into a rod and sealed, cold isostatically pressed at 50 MP for 2 min, sintered in air at 1200 °C for 24 h, loaded into a micro-pulling furnace, and then heated to melt for growth preparation. The micro-pulling speed is 0.3 mm / min. After crystal growth is completed, it is slowly cooled to room temperature and the crystal is taken out.

[0069] For the details of the eutectic crystals in Examples 1-8, please refer to Figure 1 , and for the CIE spectra, please refer to Figure 3 For the details of the eutectic crystals in Examples 9-16, please refer to Figure 2, and its CIE spectrum is referred to Figure 4 , where Figure 1 and Figure 3 the corresponding relationships between the eutectic crystals in Figure 2 and Figure 4 and the examples are shown in Table 1,

[0070] Table 1

[0071]

[0072] Table 2

[0073]

[0074] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and without departing from the spirit or basic characteristics of the present invention, the present invention can be implemented in other specific forms. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention. Any reference signs in the claims should not be regarded as limiting the claims involved.

Claims

1. A method for preparing transition metal ion-doped eutectic crystals; characterized in that: doping eutectic crystal growth with transition metal ions; The transition metal ion is a chromium ion or a cobalt ion, and the eutectic crystal is a binary eutectic crystal Al2O3-Y3Al5O 12 Or ternary eutectic crystal Al2O3-Y3Al5O 12 -ZrO2.

2. The method for preparing transition metal ion-doped eutectic crystals according to claim 1, characterized in that: Transition metal doped eutectic crystals were grown by micro pull-down method.

3. The method for preparing transition metal ion-doped eutectic crystals according to claim 1, characterized in that: The following steps are involved: The raw materials are weighed and mixed evenly in an agate mortar, then molded into a rod shape and sealed, and sintered in air after cold isostatic pressing. After sintering, they are loaded into a micro-pull-down furnace and subjected to eutectic growth through a micro-pull-down method.

4. The method for preparing a transition metal ion-doped eutectic crystal according to claim 1, characterized in that: The transition metal ion doping concentration is 0.4 at%-1.9 at%.

5. The method for preparing a transition metal ion-doped eutectic crystal according to claim 1, characterized in that: The mass percentages of the raw materials in the binary eutectic are: 80% Al2O3 and 20% Y3O2.

6. The method for preparing a transition metal ion-doped eutectic crystal according to claim 1, characterized in that: The mass percentages of the raw materials in the ternary eutectic crystal are: 65% Al2O3, 16% Y2O3 and 19% ZrO2.

7. The method for preparing a transition metal ion-doped eutectic crystal according to claim 3, characterized in that: It was cold isostatically pressed at 50 MP for 2 min, then sintered at 1200 °C in air for 24 h, loaded into a micro-pull-down furnace, and then heated and melted to prepare for growth.

8. The method for preparing a transition metal ion-doped eutectic crystal according to claim 7, characterized in that: The micro-pulling speed in the micro-pulling furnace is 0.3 mm / min. After the eutectic crystal growth is completed, it is slowly cooled to room temperature and the eutectic crystal is taken out.

9. The method for preparing a transition metal ion-doped eutectic crystal according to claim 1, characterized in that: The raw materials used are Cr2O3, Co3O4, Al2O3, Y2O3 and ZrO2.

10. The method for preparing a transition metal ion-doped eutectic crystal according to claim 9, characterized in that: The purity of the raw materials used is Cr2O3≥99.99%, Co3O4≥99.99%, Al2O3≥99.99%, Y2O3≥99.99%, and ZrO2≥99.99%.

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