A glass-ceramics and its preparation method and application

Abstract

The present invention belongs to the field of materials, and particularly relates to a glass-ceramics and its preparation method and application. In terms of mass percentage, the raw material composition of the glass-ceramics provided by the present invention is as follows: silicon oxide 54-63 wt%, aluminum oxide 15-28 wt%, lithium oxide 3-5.5 wt%, magnesium oxide 2.5-5 wt%, zinc oxide 8-18 wt%, sodium oxide 2-5 wt%, potassium oxide 0.6-1.2 wt%, boron oxide 0.6-1.5 wt%, zirconium oxide 1-10 wt%, calcium fluoride 0-3 wt%, and phosphorus pentoxide 0-5 wt%. By adjusting the glass-ceramics formula, the present invention obtains a low-lithium and high-aluminum glass-ceramics with zinc aluminate and cubic zirconia as the main crystal phases. On the one hand, this solution reduces the lithium consumption of the glass-ceramics, thereby reducing the production cost of the glass-ceramics; on the other hand, it improves the intrinsic strength, hardness, impact resistance and corrosion resistance of the glass-ceramics, ensuring its safe and long-term use in deep-sea exploration.

Description

Technical Field

[0001] The present invention belongs to the field of materials, and particularly relates to a glass-ceramics and its preparation method and application. Background Art

[0002] With the continuous development of science and technology in the era, deep-sea exploration technology has become increasingly important strategically. As one of the key components of deep-sea exploration, the glass window has very strict requirements for its performance, and it needs to withstand a static pressure of more than 100 MPa at a depth of 10,000 m and have a high impact resistance.

[0003] Glass-ceramics have excellent mechanical properties, and at the same time have advantages such as corrosion resistance and easy processing, and are widely used in various life scenarios. However, there is little research on glass-ceramics as window glass in deep-sea exploration. The main reason is that the existing glass-ceramics are still difficult to meet the strict usage requirements of window glass. For example, in Chinese Patent CN113582549A, the maximum Vickers hardness of the glass-ceramics is 715.9 kgf / mm 2 , and the mass loss of acid and alkali resistance is 0.1869%, which cannot meet the requirements of deep-sea exploration in terms of hardness and acid and alkali resistance; another example is Chinese Patent CN110372204A, where the maximum anti-bending property of the prepared matrix glass is 70 MPa, which cannot meet the requirement that the window glass must withstand a static pressure of more than 100 MPa and have good impact resistance. Moreover, this formula contains a large amount of rare earth elements (21-30 wt%), resulting in an increase in the cost of the glass. Summary of the Invention

[0004] In view of this, the purpose of the present invention is to provide a glass-ceramics and its preparation method and application. The glass-ceramics provided by the present invention have high intrinsic strength, hardness, impact resistance and erosion resistance, and can be used for a long time in deep-sea exploration.

[0005] The present invention provides a glass-ceramics, and its raw material composition in terms of mass percentage is as follows:

[0006]

[0007]

[0008] Preferably, in terms of mass percentage, the raw material composition is as follows:

[0009]

[0010] The present invention provides a preparation method of the glass-ceramics according to the above technical solution, including the following steps:

[0011] a) Mix each raw material according to the mass percentage to obtain a batch;

[0012] b) The batch material is successively melted, formed, annealed and heat-treated to obtain the glass-ceramics.

[0013] Preferably, the melting temperature is 1610 - 1650 °C; the holding time for melting is 2 - 6 h.

[0014] Preferably, the specific forming method is: pouring the molten glass liquid into a mold for forming.

[0015] Preferably, the annealing temperature is 500 - 700 °C; the holding time for annealing is 2 - 6 h.

[0016] Preferably, the specific process of the heat treatment includes: the glass after the annealing treatment is first heated to the nucleation temperature for holding, and then continuously heated to the crystallization temperature for holding.

[0017] Preferably, the nucleation temperature is 620 - 700 °C; the heating rate to the nucleation temperature is 5 - 15 °C / min; the holding time after heating to the nucleation temperature is 4 - 8 h.

[0018] Preferably, the crystallization temperature is 730 - 830 °C; the heating rate to the crystallization temperature is 5 - 15 °C / min; the holding time after heating to the crystallization temperature is 4 - 8 h.

[0019] The present invention provides an application of the glass-ceramics described in the above technical solution or the glass-ceramics prepared by the preparation method described in the above technical solution in deep-sea exploration.

[0020] Compared with the prior art, the present invention provides a glass-ceramics and its preparation method and application. In terms of mass percentage, the raw material composition of the glass-ceramics provided by the present invention is: silicon oxide 54 - 63 wt%, aluminum oxide 15 - 28 wt%, lithium oxide 3 - 5.5 wt%, magnesium oxide 2.5 - 5 wt%, zinc oxide 8 - 18 wt%, sodium oxide 2 - 5 wt%, potassium oxide 0.6 - 1.2 wt%, boron oxide 0.6 - 1.5 wt%, zirconium oxide 1 - 10 wt%, calcium fluoride 0 - 3 wt%, phosphorus pentoxide 0 - 5 wt%. By adjusting the glass-ceramics formula, the present invention obtains a low-lithium and high-aluminum glass-ceramics with zinc aluminate spinel and cubic zirconia as the main crystal phases. On the one hand, this solution reduces the lithium consumption of the glass-ceramics, thereby reducing the production cost of the glass-ceramics; on the other hand, it improves the intrinsic strength, hardness, impact resistance and erosion resistance of the glass-ceramics, ensuring its safe and long-term use in deep-sea exploration. Specific Embodiments

[0021] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0022] The present invention provides a glass-ceramics, and its raw material composition in terms of mass percentage is as follows:

[0023]

[0024]

[0025] In the glass-ceramics provided by the present invention, the content of silicon oxide in the raw materials can specifically be 54wt%, 54.5wt%, 55wt%, 55.5wt%, 56wt%, 56.5wt%, 57wt%, 57.5wt%, 58wt%, 58.5wt%, 59wt%, 59.5wt%, 60wt%, 60.5wt%, 61wt%, 61.5wt%, 62wt%, 62.5wt% or 63wt%.

[0026] In the glass-ceramics provided by the present invention, the content of aluminum oxide in the raw materials can specifically be 15wt%, 15.5wt%, 16wt%, 16.5wt%, 17wt%, 17.5wt%, 18wt%, 18.5wt%, 19wt%, 19.5wt%, 20wt%, 20.5wt%, 21wt%, 21.5wt%, 22wt%, 22.5wt%, 23wt%, 23.5wt%, 24wt%, 24.5wt%, 25wt%, 25.5wt%, 26wt%, 26.5wt%, 27wt%, 27.5wt% or 28wt%.

[0027] In the glass-ceramics provided by the present invention, the content of lithium oxide in the raw materials can specifically be 3wt%, 3.1wt%, 3.2wt%, 3.3wt%, 3.4wt%, 3.5wt%, 3.6wt%, 3.7wt%, 3.8wt%, 3.9wt%, 4wt%, 4.1wt%, 4.2wt%, 4.3wt%, 4.4wt%, 4.5wt%, 4.6wt%, 4.7wt%, 4.8wt%, 4.9wt%, 5wt%, 5.1wt%, 5.2wt%, 5.3wt%, 5.4wt% or 5.5wt%.

[0028] In the glass-ceramics provided by the present invention, the content of magnesium oxide in the raw materials can specifically be 2.5 wt%, 2.6 wt%, 2.7 wt%, 2.8 wt%, 2.9 wt%, 3 wt%, 3.1 wt%, 3.2 wt%, 3.3 wt%, 3.4 wt%, 3.5 wt%, 3.6 wt%, 3.7 wt%, 3.8 wt%, 3.9 wt%, 4 wt%, 4.1 wt%, 4.2 wt%, 4.3 wt%, 4.4 wt%, 4.5 wt%, 4.6 wt%, 4.7 wt%, 4.8 wt%, 4.9 wt% or 5 wt%.

[0029] In the glass-ceramics provided by the present invention, the content of zinc oxide in the raw materials can specifically be 8 wt%, 8.4 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, 10 wt%, 10.5 wt%, 11 wt%, 11.5 wt%, 12 wt%, 12.5 wt%, 13 wt%, 13.5 wt%, 14 wt%, 14.5 wt%, 15 wt%, 15.5 wt%, 16 wt%, 16.5 wt%, 17 wt%, 17.5 wt% or 18 wt%.

[0030] In the glass-ceramics provided by the present invention, the content of sodium oxide in the raw materials can specifically be 2 wt%, 2.1 wt%, 2.2 wt%, 2.3 wt%, 2.4 wt%, 2.5 wt%, 2.6 wt%, 2.7 wt%, 2.8 wt%, 2.9 wt%, 3 wt%, 3.1 wt%, 3.2 wt%, 3.3 wt%, 3.4 wt%, 3.5 wt%, 3.6 wt%, 3.7 wt%, 3.8 wt%, 3.9 wt%, 4 wt%, 4.1 wt%, 4.2 wt%, 4.3 wt%, 4.4 wt%, 4.5 wt%, 4.6 wt%, 4.7 wt%, 4.8 wt%, 4.9 wt% or 5 wt%.

[0031] In the glass-ceramics provided by the present invention, the content of potassium oxide in the raw materials can specifically be 0.6 wt%, 0.65 wt%, 0.7 wt%, 0.75 wt%, 0.8 wt%, 0.85 wt%, 0.9 wt%, 0.95 wt%, 1 wt%, 1.05 wt%, 1.1 wt%, 1.15 wt% or 1.2 wt%.

[0032] In the glass-ceramics provided by the present invention, the content of boron oxide in the raw materials can specifically be 0.6 wt%, 0.65 wt%, 0.7 wt%, 0.75 wt%, 0.8 wt%, 0.85 wt%, 0.9 wt%, 0.95 wt%, 1 wt%, 1.05 wt%, 1.1 wt%, 1.15 wt%, 1.2 wt%, 1.25 wt%, 1.3 wt%, 1.35 wt%, 1.4 wt%, 1.45 wt%, 1.5 wt%, 1.55 wt% or 1.6 wt%.

[0033] In the glass-ceramics provided by the present invention, the content of zirconium oxide in the raw materials can specifically be 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 3.5 wt%, 4 wt%, 4.5 wt%, 5 wt%, 5.5 wt%, 6 wt%, 6.5 wt%, 7 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt% or 10 wt%.

[0034] In the glass-ceramics provided by the present invention, the content of calcium fluoride in the raw materials can specifically be 0 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt% or 3 wt%.

[0035] In the glass-ceramics provided by the present invention, the content of phosphorus pentoxide in the raw materials can specifically be 0 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt% or 5 wt%.

[0036] The present invention also provides a method for preparing the glass-ceramics according to the above technical solution, comprising the following steps:

[0037] a) Mixing each raw material according to the mass percentage to obtain a batch;

[0038] b) Melting, forming, annealing and heat-treating the batch in sequence to obtain the glass-ceramics.

[0039] In the preparation method provided by the present invention, the melting is preferably carried out in a high-temperature melting furnace; the melting temperature is preferably 1610-1650 °C, specifically 1610 °C, 1615 °C, 1620 °C, 1625 °C, 1630 °C, 1635 °C, 1640 °C, 1645 °C or 1650 °C; the holding time of the melting is preferably 2-6 h, specifically 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h or 6 h.

[0040] In the preparation method provided by the present invention, the specific manner of the forming is preferably: pouring the glass liquid obtained after melting into a mold for forming. Among them, the mold is preferably a graphite mold.

[0041] In the preparation method provided by the present invention, the annealing is preferably carried out in an annealing furnace; the annealing temperature is preferably 500-700 °C, specifically 500 °C, 510 °C, 520 °C, 530 °C, 540 °C, 550 °C, 560 °C, 570 °C, 580 °C, 590 °C, 600 °C, 610 °C, 620 °C, 630 °C, 640 °C, 650 °C, 660 °C, 670 °C, 680 °C, 690 °C or 700 °C; the holding time of the annealing is preferably 2-6 h, specifically 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h or 6 h.

[0042] In the preparation method provided by the present invention, the heat treatment is preferably carried out in a muffle furnace; the specific process of the heat treatment preferably includes: the glass that has completed the annealing treatment is first heated to the nucleation temperature for holding, and then continued to be heated to the crystallization temperature for holding.

[0043] In the preparation method provided by the present invention, the nucleation temperature is preferably 620-700 °C, specifically 620 °C, 625 °C, 630 °C, 635 °C, 640 °C, 645 °C, 650 °C, 655 °C, 660 °C, 665 °C, 670 °C, 675 °C, 680 °C, 685 °C, 690 °C, 695 °C or 700 °C; the heating rate to the nucleation temperature is preferably 5-15 °C / min, specifically 5 °C / min, 6 °C / min, 7 °C / min, 8 °C / min, 9 °C / min, 10 °C / min, 11 °C / min, 12 °C / min, 13 °C / min, 14 °C / min or 15 °C / min; the holding time after heating to the nucleation temperature is preferably 4-8 h, specifically 4 h, 4.5 h, 5 h, 5.5 h, 6 h, 6.5 h, 7 h, 7.5 h or 8 h.

[0044] In the preparation method provided by the present invention, the crystallization temperature is preferably 730 - 830 °C, specifically it can be 730 °C, 735 °C, 740 °C, 745 °C, 750 °C, 755 °C, 760 °C, 765 °C, 770 °C, 775 °C, 780 °C, 785 °C, 790 °C, 795 °C, 800 °C, 805 °C, 810 °C, 815 °C, 820 °C, 825 °C or 830 °C; the heating rate to the crystallization temperature is 5 - 15 °C / min, specifically it can be 5 °C / min, 6 °C / min, 7 °C / min, 8 °C / min, 9 °C / min, 10 °C / min, 11 °C / min, 12 °C / min, 13 °C / min, 14 °C / min or 15 °C / min; the holding time after heating to the crystallization temperature is 4 - 8 h, specifically it can be 4 h, 4.5 h, 5 h, 5.5 h, 6 h, 6.5 h, 7 h, 7.5 h or 8 h.

[0045] The present invention also provides an application, applying the glass-ceramics described in the above technical solution or the glass-ceramics prepared by the preparation method described in the above technical solution to deep-sea exploration. More specifically, using the glass-ceramics as a window glass in a deep-sea detector.

[0046] The technical solution provided by the present invention obtains a low-lithium high-aluminum glass-ceramics with zinc aluminate spinel and tetragonal zirconia as the main crystal phases by adjusting the glass-ceramics formula. On the one hand, this solution reduces the lithium consumption of the glass-ceramics, thereby reducing the production cost of the glass-ceramics; on the other hand, it improves the intrinsic strength, hardness, impact resistance and erosion resistance of the glass-ceramics, ensuring its safe and long-term use in deep-sea exploration.

[0047] For clarity, the following is a detailed description through the following examples.

[0048] Example 1

[0049] According to the formula in Table 1, mix the raw materials to obtain a batch; use the melting method to melt the batch at 1650 °C, after holding for 2 hours, pour the glass melt into a graphite mold to obtain a block of glass; then move the mold and the glass together to an annealing furnace at 580 °C and hold for 4 hours; then put the glass into a muffle furnace, heat it to the nucleation temperature (680 °C) at a heating rate of 10 °C / min and hold for 4 hours, and then heat it to the crystallization temperature (830 °C) at 10 °C / min and hold for 4 hours to obtain a block of glass-ceramics.

[0050] Example 2

[0051] According to the formula in Table 1, mix the raw materials to obtain a batch mixture; use the melting method to melt the batch mixture at 1610 °C, keep it warm for 2 hours, then pour the glass melt into a graphite mold to obtain block-shaped glass; then move the mold and the glass together to an annealing furnace at 550 °C and keep it warm for 4 hours; afterwards, put the glass into a muffle furnace, heat it up to the nucleation temperature (680 °C) at a heating rate of 10 °C / min and keep it warm for 4 hours, and then heat it up to the crystallization temperature (740 °C) at 10 °C / min and keep it warm for 4 hours to obtain block-shaped glass-ceramics.

[0052] Example 3

[0053] According to the formula in Table 1, mix the raw materials to obtain a batch mixture; use the melting method to melt the batch mixture at 1620 °C, keep it warm for 2 hours, then pour the glass melt into a graphite mold to obtain block-shaped glass; then move the mold and the glass together to an annealing furnace at 550 °C and keep it warm for 4 hours; afterwards, put the glass into a muffle furnace, heat it up to the nucleation temperature (650 °C) at a heating rate of 10 °C / min and keep it warm for 4 hours, and then heat it up to the crystallization temperature (750 °C) at 10 °C / min and keep it warm for 4 hours to obtain block-shaped glass-ceramics.

[0054] Example 4

[0055] According to the formula in Table 1, mix the raw materials to obtain a batch mixture; use the melting method to melt the batch mixture at 1620 °C, keep it warm for 2 hours, then pour the glass melt into a graphite mold to obtain block-shaped glass; then move the mold and the glass together to an annealing furnace at 550 °C and keep it warm for 4 hours; afterwards, put the glass into a muffle furnace, heat it up to the nucleation temperature (660 °C) at a heating rate of 10 °C / min and keep it warm for 4 hours, and then heat it up to the crystallization temperature (760 °C) at 10 °C / min and keep it warm for 4 hours to obtain block-shaped glass-ceramics.

[0056] Example 5

[0057] According to the formula in Table 1, mix the raw materials to obtain a batch mixture; use the melting method to melt the batch mixture at 1630 °C, keep it warm for 2 hours, then pour the glass melt into a graphite mold to obtain block-shaped glass; then move the mold and the glass together to an annealing furnace at 570 °C and keep it warm for 4 hours; afterwards, put the glass into a muffle furnace, heat it up to the nucleation temperature (680 °C) at a heating rate of 10 °C / min and keep it warm for 4 hours, and then heat it up to the crystallization temperature (780 °C) at 10 °C / min and keep it warm for 4 hours to obtain block-shaped glass-ceramics.

[0058] Example 6

[0059] According to the formula in Table 1, mix the raw materials to obtain a batch mixture; use the melting method to melt the batch mixture at 1620 °C, keep it warm for 2 hours, then pour the glass liquid into a graphite mold to obtain a block of glass; then move the mold and the glass together to an annealing furnace at 560 °C and keep it warm for 4 hours; afterwards, put the glass into a muffle furnace, heat it at a heating rate of 10 °C / min to the nucleation temperature (660 °C), keep it warm for 4 hours, and then heat it at 10 °C / min to the crystallization temperature (780 °C) and keep it warm for 4 hours to obtain a block of glass-ceramics.

[0060] Example 7

[0061] According to the formula in Table 1, mix the raw materials to obtain a batch mixture; use the melting method to melt the batch mixture at 1640 °C, keep it warm for 2 hours, then pour the glass liquid into a graphite mold to obtain a block of glass; then move the mold and the glass together to an annealing furnace at 580 °C and keep it warm for 4 hours; afterwards, put the glass into a muffle furnace, heat it at a heating rate of 10 °C / min to the nucleation temperature (680 °C), keep it warm for 4 hours, and then heat it at 10 °C / min to the crystallization temperature (780 °C) and keep it warm for 4 hours to obtain a block of glass-ceramics.

[0062] Example 8

[0063] According to the formula in Table 1, mix the raw materials to obtain a batch mixture; use the melting method to melt the batch mixture at 1630 °C, keep it warm for 2 hours, then pour the glass liquid into a graphite mold to obtain a block of glass; then move the mold and the glass together to an annealing furnace at 570 °C and keep it warm for 4 hours; afterwards, put the glass into a muffle furnace, heat it at a heating rate of 10 °C / min to the nucleation temperature (650 °C), keep it warm for 4 hours, and then heat it at 10 °C / min to the crystallization temperature (790 °C) and keep it warm for 4 hours to obtain a block of glass-ceramics.

[0064] Table 1 Raw material ratios of Examples 1 - 8 of the present invention

[0065]

[0066] Performance test

[0067] Perform performance tests on the block of glass-ceramics obtained in the examples of the present invention according to the following method. The specific test items and test methods (or test standards) are as follows:

[0068] Vickers hardness: Test under the conditions of an experimental load of 200 gf and a holding time of 10 s.

[0069] Acid resistance stability: Test according to GB / T 7962.14 - 2010;

[0070] Moisture resistance stability: Test according to GB / T 7962.15 - 2010;

[0071] Anti-drop height: Drop the glass from a certain height and record the height at which the glass breaks;

[0072] Flexural strength: Flexural strength (mechanical property): Fix the sintered strip-shaped glass-ceramic sample on a CTM-6104 type electronic universal testing machine, apply pressure to the sample until it breaks, that is, the three-point bending strength test method;

[0073] The results are shown in Table 2:

[0074] Table 2 Performance test results of the glass-ceramics in Examples 1-8 of the present invention

[0075]

[0076] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be regarded as the protection scope of the present invention.

Claims

1. A method for preparing glass-ceramics, comprising the following steps: a) Mixing the raw materials according to mass percentages to obtain a batch; Calculated by mass percentage, the raw material composition is: b) Subjecting the batch to melting, forming, annealing and heat treatment in sequence to obtain glass-ceramics; The melting temperature is 1610 - 1650 °C; the holding time for melting is 2 - 6 h; The specific forming method is: pouring the molten glass obtained after melting into a mold for forming; The annealing temperature is 500 - 700 °C; the holding time for annealing is 2 - 6 h; The specific process of the heat treatment includes: the glass after annealing treatment is first heated to the nucleation temperature for holding, and then continuously heated to the crystallization temperature for holding; wherein, the nucleation temperature is 620 - 700 °C; the heating rate to the nucleation temperature is 5 - 15 °C / min; the holding time after heating to the nucleation temperature is 4 - 8 h; the crystallization temperature is 730 - 830 °C; the heating rate to the crystallization temperature is 5 - 15 °C / min; the holding time after heating to the crystallization temperature is 4 - 8 h.

2. Application of the glass-ceramics prepared by the preparation method according to Claim 1 in deep-sea exploration.

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