GLASS MATERIAL, AND PREPARATION METHOD AND PRODUCT THEREOF

Abstract

The present invention discloses a glass material, and a preparation method and a product thereof. The glass material contains a lithium salt crystalline phase and a phosphate crystalline phase. For the entire material, the crystallinity is 40-95%, the lithium salt crystalline phase accounts for 40-90 wt % of the entire material, and the phosphate crystalline phase accounts for 2-15 wt % of the entire material, wherein the lithium salt crystalline phase is one or more of lithium silicate, lithium disilicate and petalite, and the phosphate crystalline phase is aluminum phosphate or/and aluminum metaphosphate. After the glass material of the present invention is toughened, the Vickers hardness (Hv) is 900 kgf/mm.sup.2 or above. The glass material or a substrate of the present invention is suitable for protective members such as mobile terminal equipment and optical equipment and has high hardness and strength. Furthermore, the present invention may also be used for other decorations such as outer frame members of portable electronic equipment.

Claims

1. A glass material, comprising a lithium salt crystalline phase and a phosphate crystalline phase, wherein for the entire material, crystallinity is 40-95%, the lithium salt crystalline phase accounts for 40-90 wt % of the entire material, and the phosphate crystalline phase accounts for 2-15 wt % of the entire material, wherein the lithium salt crystalline phase is one or more of lithium silicate, lithium disilicate and petalite, and wherein the phosphate crystalline phase is aluminum phosphate or/and aluminum metaphosphate.

2. The glass material according to claim 1, wherein the lithium salt crystalline phase accounts for 50-75 wt % and the phosphate crystalline phase accounts for 3-10 wt %.

3. The glass material according to claim 1, comprising 1-5 wt % of zirconia.

4. The glass material according to claim 3, further comprising a coloring agent.

5. The glass material according to claim 4, wherein the coloring agent is a mixture of CoO, CuO, MnO.sub.2, Cr.sub.2O.sub.3, NiO, CeO.sub.2 and TiO.sub.2 and a mixture of CdS and ZnO.

6. A method of preparing the glass material of claim 1, comprising the steps of: step 1, uniformly mixing the following raw materials in percentage by mass: 68-74% of SiO.sub.2, 4-10% of Al.sub.2O.sub.3, 8-12% of Li.sub.2O, 0.1-3% of Na.sub.2O, 0.1-1% of K.sub.2O and 3-9% of P.sub.2O.sub.5, and putting a mixture in a platinum or alumina crucible; step 2, heating the mixture for 10-30 h in an electric furnace at a temperature ranging from 1250° C. to 1450° C. for uniformly melting the mixture, and forming a basic glass plate with a thickness of 0.2-2 mm with a cast ingot cutting method and a rolling process; and step 3, implementing thermal treatment on the obtained basic glass plate in order to conduct nucleation and crystal growth, and preparing the glass material.

7. The method of preparing the glass material according to claim 6, further comprising step 4 of: conducting ion strengthening on the prepared glass material; wherein the specific operation comprises step 1, soaking the glass material in a NaNO.sub.3 molten salt bath for 5-16 h at a temperature of about 420-460° C. for ion exchange; and step 2, soaking the glass material in a KNO.sub.3 molten salt bath for about 2-16 h at a temperature of about 400-460° C. for ion exchange.

8. The method of preparing the glass material according to claim 6, wherein in the step 1, the following components are further added in the raw materials in percentage by mass: 1-6% of ZrO.sub.2, 0-2% of CaO, 0-1% of BaO, 0-2% of Sb.sub.2O.sub.3, 0-3% of MgO, 0-6% of ZnO, 0-5% of Y.sub.2O.sub.3, 0-5% of La.sub.2O.sub.3, 0-2% of Eu.sub.2O.sub.3, 0-2% of Gd.sub.2O.sub.3 and 0-4% of TiO.sub.2.

9. The method of preparing the glass material according to claim 6, wherein in the step 3, the thermal treatment process comprises the steps of: keeping the basic glass plate for 2-6 h at a temperature of 600-650° C. and then for 2-10h at a temperature of 690-770° C.

10. A glass cover plate product, prepared by conducting cutting and polishing processes on the glass material prepared by the method of claim 6 and preparing a cover plate with a target thickness and size.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0056] FIG. 1 is a curve of differential scanning calorimetry (DSC) for measuring Embodiment 1.

[0057] FIG. 2 is a curve of the transmittance for measuring Embodiment 2.

[0058] FIG. 3 is an XRD pattern for measuring Embodiment 1.

[0059] FIG. 4 is an XRD pattern for measuring Embodiment 2.

[0060] FIG. 5 is an XRD pattern for measuring Embodiment 3.

[0061] FIG. 6 is an XRD pattern for measuring Embodiment 4.

[0062] FIG. 7 measures an SEM morphology of crystals after Embodiment 3 is corroded by HF.

[0063] FIG. 8 measures line scanning of energy spectrum of potassium and sodium elements on a section of Embodiment 3.

[0064] FIG. 9 is a display picture of FSM-6000 for measuring Embodiment 3.

[0065] FIG. 10 is impressions for measuring a hardness test for measuring Embodiment 3.

[0066] FIG. 11 is a glass size schematic view for a ball falling test.

DETAILED DESCRIPTION OF THE INVENTION

[0067] A composition range of various components of the glass ceramics of the present invention is described below. In this description, the contents of various components are expressed by employing a weight percentage relative to a glass material total weight of the composition converted into oxides, unless otherwise noted. Here, the “composition converted into oxides” refers to that under the condition that oxides, mixed salts and the like which are used as the raw materials of the composition of the glass ceramics of the present invention are totally decomposed and converted into oxides when molten, the material total weight of the oxides is taken as 100%.

EMBODIMENT

Embodiment 1

Step 1, Weighing and Mixing of Components

[0068] According to various components and mass percentages thereof listed in example 1 in Table 1, corresponding raw materials were selected and uniformly mixed, and a uniformly mixed mixture was put in a platinum or alumina crucible.

Step 2, Preparation of a Basic Glass Plate

[0069] According to the degree of difficulty of melting of the glass composition, heat preservation was conducted on the mixture for 20 h in an electric furnace at a temperature of 1450° C., the mixture was uniformly molten, and a basic glass plate with a thickness of 0.1 mm was formed with a cast ingot cutting method.

Step 3, Thermal Treatment for Crystallization

[0070] Thermal treatment for crystallization was conducted on the obtained basic glass plate, the specific method of which comprises the steps that thermal insulation was performed on the basic glass plate for 2 h at 650° C. for nucleation and then for 8 h at 760° C. for crystal growth, and then furnace cooling was conducted to prepare glass ceramics. Process systems of thermal treatment for crystallization of the glasses of other examples are as shown in the table.

Step 4, Machining of the Glass Ceramics

[0071] A prepared glass ceramic sheet was subjected to treatment with processes of cutting, edging, polishing and the like by using a machine, and a glass sheet in a specified size and with a thickness of 160×70×0.6 mm was prepared.

Step 5, Chemical Strengthening of the Glass Ceramics

[0072] A compressive stress layer was formed on the surface of the glasses with a high-temperature ion exchange method to achieve strengthening of a glass cover plate. A two-step high-temperature ion exchange method was uniformly selected for strengthening and comprises the following specific steps that step 1, the glass material was soaked in a NaNO.sub.3 molten salt bath for about 8 h at a temperature of 450° C.; and step 2, the glass material was soaked in a KNO.sub.3 molten salt bath for 2 h at a temperature of 400° C.

[0073] Performance tests were conducted on the obtained glass material cover plate product, and each performance data is shown as corresponding data in Table 1.

Embodiment 2

Step 1, Weighing and Mixing of Components

[0074] According to various components and mass percentages thereof listed in example 2 in Table 1, corresponding raw materials were selected and uniformly mixed, and a uniformly mixed mixture was put in a platinum crucible.

Step 2, Preparation of a Basic Glass Plate

[0075] According to the degree of difficulty of melting of the glass composition, heat preservation was conducted on the mixture for 20 h in an electric furnace at a temperature of 1420° C., the mixture was uniformly molten, and a basic glass plate with a thickness of 2.0 mm was formed with a cast ingot cutting method.

Step 3, Thermal Treatment for Crystallization

[0076] Thermal treatment for crystallization was conducted on the obtained basic glass plate, the specific method of which comprises the steps that thermal insulation was performed on the basic glass plate for 4 h at 630° C. for nucleation and then for 3 h at 730° C. for crystal growth, and then furnace cooling was conducted to prepare glass ceramics.

Step 4, Machining of the Glass Ceramics

[0077] A prepared glass ceramic sheet was subjected to treatment with processes of cutting, edging, polishing and the like by using a machine, and a glass sheet in a specified size and with a thickness of 160×70×0.6 mm was prepared.

[0078] Performance tests were conducted on the obtained glass material cover plate product, and each performance data is shown as corresponding data in Table 1.

[0079] For crystalline phases of the glass ceramics before high-temperature ion strengthening in Embodiments 1-14, by using an X-ray diffractometer and comparing with a standard PDF card, corresponding crystalline phases in the glass ceramics were analyzed, and corresponding crystallinity was calculated.

[0080] Average grain size: determination was conducted by using a scanning electron microscope, surface treatment was conducted on the glass ceramics in HF acid, coating with gold spraying was conducted on the surfaces of the glass ceramics, surface scanning was conducted under the scanning electron microscope to observe diameters of grains, average diameter sizes of all the grains are added together, and a sum was divided by an amount of crystalline grains in an image.

[0081] Transmittance: test was conducted by using an ultraviolet and visible spectrophotometer. Vickers hardness: measurement was conducted by using Vickers, wherein a loading force was 200 g, and a loading time was 15 s.

[0082] CS: that is the surface compressive stress layer formed by potassium ions, and determination was conducted by using a glass surface stress gauge FSM-6000.

[0083] DOC: that is a depth of a sodium ion strengthened layer, and determination was conducted by using a glass surface stress gauge SLP-1000 from Japan ORIHARA.

[0084] DOL: that is a depth of a potassium ion strengthened layer, and determination was conducted by using a glass surface stress gauge FSM-6000 from Japan ORIHARA.

[0085] Ball falling height: that is a maximal ball falling height obtained in such a way that a strengthened glass ceramic plate in a size of 160×70×0.8 mm was put on a rubber frame for fixing after two surfaces of the strengthened glass ceramic plate were polished, 102 g steel ball fallen down from a specified height, and the glass sheet was not broken and could bear the impact. Particularly, test data recorded as 380-420 mm in the embodiments expresses the impact borne by the glass plate without being broken although the steel ball falls onto the glass sheet from a height of 400 mm.

[0086] Colors in the embodiments are those of corresponding glass plates, obtained through visual inspection.

TABLE-US-00001 TABLE 1 Component Embodiment (wt %) 1 2 3 4 5 6 7 SiO.sub.2 68 69 70 71 72 73 74 Al.sub.2O.sub.3 10 7 9 5 6.5 7.2 5.5 TiO.sub.2 0 1.2 1.6 1.2 2 0.1 0.5 CaO 0.5 0.8 1 0.5 0.2 0.1 0.2 Li.sub.2O 10 9 8 8 9 10 12 Na.sub.2O 1 3 1.5 1.8 1 0.2 0.5 K.sub.2O 0.1 0.3 0.4 0.5 0.7 0.1 0.4 P.sub.2O.sub.5 3 4.5 5 9 6 3 4 ZrO.sub.2 5 2 1 1 1 5 1.8 BaO 0 1 0.5 0 0 0 Sb.sub.2O.sub.3 2 1.8 2 2 1.5 1.3 1.1 MgO 0.2 0.2 ZnO 0.2 Y.sub.2O.sub.3 0.2 La.sub.2O.sub.3 0.2 Eu.sub.2O.sub.3 0.2 Gd.sub.2O.sub.3 0.1 SiO.sub.2/Li.sub.2O 6.8 7.7 8.8 8.9 8.0 7.3 6.2 ZrO.sub.2 + P2O.sub.5 + TiO.sub.2 8 7.7 7.6 7.8 9 8.1 6.3 Melting process 1450° C. 1420° C. 1400° C. 1430° C. 1360° C. 1340° C. 1400° C. 20 h 20 h 20 h 30 h 20 h 30 h 25 h Nucleation  650° C.  630° C.  620° C.  620° C.  620° C.  630° C.  620° C. process  2 h  4 h  4 h  4 h  4 h  4 h  4 h Crystallization  760° C.  730° C.  720° C.  700° C.  700° C.  720° C.  720° C. process  8 h  3 h  3 h  6 h  6 h  3 h  3 h Crystalline phase Zirconia Aluminum Petalite Petalite Petalite Petalite Petalite Aluminum silicate Lithium Aluminum Aluminum Lithium Lithium phosphate Aluminum disilicate metaphos- metaphos- disilicate disilicate Lithium phosphate Aluminum phate phate Aluminum Aluminum disilicate Lithium metaphos- metaphos- metaphor- disilicate phate phate sphate CS (MPa) 400 300 380 400 360 395 432 DOC (μm) 100 95 110 105 90 110 93 DOL (μm) 7 8 8 7 6 8 7 Vickers hardness 1055 950 970 925 930 950 1000 (Kgf/mm.sup.2) Ball falling 400 400 400 400 400 450 450 height (mm) Color Opacified Transparent Transparent Transparent Transparent Transparent Transparent

TABLE-US-00002 TABLE 2 Embodiment Component 1 2 3 4 5 6 7 SiO.sub.2 68 69 70 71 70 71 73 Al.sub.2O.sub.3 9 6 8 5 6 5 5 TiO.sub.2 0.3 0.1 0.5 0.8 1 0 0.6 CaO 0.4 0.8 1 0.5 0.8 0.2 0.6 Li.sub.2O 9 11.5 12 12 9 12 11 Na.sub.2O 0.3 0.5 0.7 1.5 1 1.5 0.5 K.sub.2O 0.1 0.3 0.4 0.7 0.5 0.4 0.2 P.sub.2O.sub.5 9 3.5 4 6 6 5 3 ZrO.sub.2 1.5 5 1 1 3 3.5 4.6 BaO 0 1 0.4 0 0.2 0 Sb.sub.2O.sub.3 2 1.8 2 1.5 1.5 1.4 1.5 MgO 0.2 0.5 1 ZnO 0.2 0 SiO.sub.2/Li.sub.2O 7.6 6.0 5.8 5.9 7.8 5.9 6.6 ZrO.sub.2 + P2O.sub.5 + TiO.sub.2 10.8 8.6 5.5 7.8 10 8.5 8.2 Melting process 1450° C. 1420° C. 1380° C. 1400° C. 1360° C. 1400° C. 1400° C. 20 h 20 h 20 h 30 h 20 h 30 h 25 h Melting 1450° C. 1450° C. 1340° C. 1360° C. 1380° C. 1400° C. 1450° C. temperature/° C. Nucleation  640° C.  630° C.  620° C.  630° C.  630° C.  620° C.  630° C. process/° C.  2 h  4 h  5 h  4 h  4 h  4 h  6 h Crystallization  730° C.  740° C.  720° C.  700° C.  720° C.  720° C.  760° C. process/° C.  4 h  3 h  3 h  6 h  3 h  3.5 h    4 h Crystalline phase Petalite Lithium Petalite Petalite Petalite Lithium Lithium Lithium silicate Lithium Lithium Lithium silicate silicate disilicate Lithium disilicate disilicate disilicate Lithium Lithium Aluminum disilicate Aluminum Aluminum Aluminum disilicate disilicate metaphosphate Aluminum metaphosphate metaphosphate metaphosphate Aluminum Aluminum phosphate phosphate phosphate CS (MPa) 380 390 410 420 400 420 430 DOC (μm) 100 105 105 100 98 93 95 DOL (μm) 9 10 9 9 8 7 8 Vickers hardness 1000 950 970 930 950 1000 1010 (Kgf/mm.sup.2) Ball falling 400 380 400 390 400 420 405 height (mm) Color Transparent Transparent Transparent Transparent Transparent Transparent Transparent

TABLE-US-00003 TABLE 3 Embodiment Component 8 9 10 11 12 13 14 SiO.sub.2 70.5 69 70 71 70 68 70 Al.sub.2O.sub.3 8 7 6 9 6.5 6 4.5 TiO.sub.2 0 1.2 1.6 1.5 4 2 0 CaO 0.5 0.8 1 1.4 0.5 1.8 0.5 Li.sub.2O 12 9 9 8 9 8 12 Na.sub.2O 1 2.5 1.5 1.8 1 1.5 0.5 K.sub.2O 0.1 0.3 0.4 0.5 0.6 1 0.4 P.sub.2O.sub.5 3.5 4.5 3 3 4 3 5 ZrO.sub.2 1 2 1 1.3 1 1 2 BaO 0 1 0.5 0 0 0.2 0 Sb.sub.2O.sub.3 2 1.8 2 2 1.5 1.3 1.1 MgO 0.2 0.2 ZnO 0.2 5 CoO 1 0.2 CuO 0.7 MnO.sub.2 4 Cr.sub.2O.sub.3 0.5 1 NiO 0.7 CeO.sub.2 CdS 1.2 Nd.sub.2O.sub.3 4 SiO.sub.2/Li.sub.2O 79.5 78 77 80.3 77.5 75 76.5 ZrO.sub.2 + P.sub.2O.sub.5 + TiO.sub.2 5.9 7.7 7.8 8.9 7.8 8.5 5.4 Melting 1430° C. 1420° C. 1350° C. 1420° C. 1350° C. 1340° C. 1340° C. temperature 20 h 20 h 25 h 25 h 20 h 15 h 20 h Nucleation  620° C.  620° C.  620° C.  620° C.  620° C.  620° C.  620° C. process  4 h  4 h  4 h  4 h  4 h  4 h  4 h Crystallization  720° C.  720° C.  720° C.  720° C.  720° C.  720° C.  720° C. process  3 h  3 h  3 h  3 h  3 h  3 h  3 h Crystalline Petalite Petalite Petalite Petalite Petalite Petalite Petalite phase Lithium Lithium Lithium Lithium Lithium Cadmium Lithium disilicate disilicate disilicate disilicate disilicate sulfide disilicate Aluminum Aluminum Aluminum Aluminum Aluminum Aluminum Aluminum metaphos- metaphos- metaphos- metaphos- metaphos- metaphos- metaphos- phate phate phate phate phate phate phate CS (MPa) 400 300 380 410 380 385 420 DOC (μm) 100 95 110 105 88 91 120 DOL (μm) 7 8 8 7 9 7 8 Vickers hardness 950 950 950 950 950 1000 950 (Kgf/mm.sup.2) Ball falling height (mm) 400 400 350 400 400 400 400 Color Color Blue Green Brownish Green Opacifying White Lavender yellow green

[0087] The above are only embodiments of the present invention and do not limit the patent scope of the present invention. Any equivalent structure or equivalent process modification used according to the contents of the description and accompanying drawings in the present invention, no matter whether it is directly or indirectly used in any other related technical field, should be included within the patent protection scope of the present invention.