CN112851122A - High-fracture-toughness microcrystalline glass for mobile phone back plate and preparation method thereof - Google Patents
High-fracture-toughness microcrystalline glass for mobile phone back plate and preparation method thereof Download PDFInfo
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- CN112851122A CN112851122A CN202110205191.5A CN202110205191A CN112851122A CN 112851122 A CN112851122 A CN 112851122A CN 202110205191 A CN202110205191 A CN 202110205191A CN 112851122 A CN112851122 A CN 112851122A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0009—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing silica as main constituent
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
Abstract
The invention relates to the technical field of microcrystalline glass, and provides high fracture toughness microcrystalline glass for a mobile phone back plate, which comprises the following components in part by weight: 30-60% of a primary crystalline phase, 5-10% of a secondary crystalline phase, and the balance of a glass phase, wherein the primary crystalline phase is xonotlite and the secondary crystalline phase is one or two of xonotlite and calcium fluoride; the composite material comprises the following components in percentage by mass: 50-63% SiO2、1～5％Al2O3、15～20％CaO、6～12％Na2O、2～6％K2O、3～5％Li2O、3～6％CaF2、0～2％TiO2、1～3％ZrO2、0～3％Y2O3、3～7％B2O3、0～3％P2O5、0.1～0.5％Sb2O3. By the technical schemeThe problem that the microcrystalline glass in the prior art cannot have fracture toughness and chemical strengthening property at the same time is solved.
Description
Technical Field
The invention relates to the technical field of microcrystalline glass, in particular to high-fracture toughness microcrystalline glass for a mobile phone back plate and a preparation method thereof.
Background
With the advent of the 5G era, smart phones have become an indispensable part as an important communication tool, and glass/glass ceramic materials are one of indispensable parts in these electronic devices. As is known to all, currently, general aluminosilicate high-strength glass plays a very important role in smart phone cover plate materials, and a mobile phone back plate is also used as an important component to protect a mobile phone. In recent years, the demand of 5G communication and wireless charging technology has led to strong competition that high-strength glass/glass ceramics material is regarded as a material of a mobile phone rear cover in order to reduce the electromagnetic shielding effect generated by the conventional metal material back plate. Since the backplane has no requirement for optical properties, the important concern is mechanical and electrical properties. The zirconia ceramics can be used as the mobile phone backboard, but the hardness is high, the processing is extremely difficult, and the production efficiency and the yield when the zirconia ceramics is used as the mobile phone backboard are greatly reduced. In contrast, the glass/glass ceramics is easy to realize in preparation method and process, and the glass ceramics with high fracture toughness has lower hardness and is easy to process and form, so that the glass/glass ceramics is more suitable for being used as a mobile phone back plate. But the structural characteristics of the glass material make itHas high brittleness and breaking toughness of 0.7 MPa-m1/2On the other hand, the strength of the non-reinforced 4PB is generally about 80-110 MPa, and can reach about 700MPa after being reinforced, but the reinforced 4PB is still brittle and has insufficient drop resistance, and the possibility of fracture of the mobile phone is high when the mobile phone is dropped. Therefore, how to improve the fracture toughness of glass becomes important.
At present, the main approach for improving the strength of the glass material is to form a relatively large compressive stress layer and a large stress layer depth on the surface of the glass by adopting a chemical strengthening method, so that the bending strength and the impact strength of the glass are increased. Several glass companies now often design glass compositions that incorporate chemical strengthening, i.e., compositions that are amenable to one-step or two-step or multi-step chemical strengthening. For example, glass compositions incorporating both Na and Li, KNO for strengthening3And NaNO3The mixed molten salt has the advantages that Na ions and Li ions are rapidly exchanged, the exchange depth is large, K ions and Na ions are exchanged, the surface compression stress can be greatly increased, deep DOL and large CS can be obtained by combining the Na ions and the K ions, the expansion of cracks on the surface of the glass can be effectively controlled, and therefore the glass strengthening, impacting and falling performance is obviously improved. However, since the depth of the compressive stress layer after chemical strengthening is usually only about 75 to 150 μm, when the micro-cracks on the surface of the glass break through the depth of the compressive stress layer, the cracks rapidly propagate in the glass, and the glass is broken. Both research and practice show that the root cause of rapid crack propagation is that the fracture toughness of the glass is too low, and the fracture toughness of the existing mobile phone panel glass is only 0.69 MPa.m1/2On the other hand, this is also a value for the fracture toughness of conventional glasses, which is not effective in preventing crack propagation within the glass. Thus, if there is a material which can be effectively chemically strengthened while having a sufficiently large fracture toughness value, the development of cracks inside the glass can be very effectively hindered, and the risk of breakage is greatly reduced.
The zirconia ceramics can be used as the mobile phone backboard, but the hardness is high, the processing is extremely difficult, and the production efficiency and the yield when the zirconia ceramics is used as the mobile phone backboard are greatly reduced.
The majority of the patents and academic papers disclosed at presentThe research focuses on the influence of the chemical strengthening method on the magnitude of the surface compressive stress of the glass and the depth of a surface compressive stress layer, the fracture toughness of the glass is neglected, and only a few published patents mention the problem that the fracture toughness of the glass or the fracture toughness of a glass material as a mobile phone back plate is high and is not suitable for chemical strengthening. If the glass material is suitable for chemical strengthening and has low fracture toughness or the glass material has high fracture toughness and is not suitable for chemical strengthening, the requirement of drop resistance is difficult to meet. CN110357438A mentions a polycrystalline phase microcrystalline glass, the main crystal phase of which is wollastonite, but the microcrystalline glass has higher fracture toughness but is not suitable for chemical strengthening and is mainly used for building decoration materials. CN104176938A relates to a microcrystalline glass material with high fracture toughness, and the main crystal phase is a calcium fluosilicate (NaCa) as the main crystal phase2<Si2O5>2F) It is mainly used for building decoration, and the composition is not suitable for chemical strengthening.
Disclosure of Invention
The invention provides high-fracture-toughness microcrystalline glass for a mobile phone back plate and a preparation method thereof, and solves the problem that the microcrystalline glass in the prior art cannot have fracture toughness and chemical reinforcement at the same time.
The technical scheme of the invention is as follows:
a high fracture toughness microcrystalline glass for a mobile phone backboard comprises:
a main crystal phase which is 30-60% of canasite by mass;
a secondary crystal phase, the mass content of which is 5-10%, and the secondary crystal phase is one or two of xonotlite and calcium fluoride;
the balance being a glassy phase.
As a further technical scheme, the high fracture toughness microcrystalline glass for the mobile phone back plate comprises the following components in percentage by mass: 50-63% SiO2、1～5％Al2O3、15～20％CaO、6～12％Na2O、2～6％K2O、3～5％Li2O、3～6％CaF2、0～2％TiO2、1～3％ZrO2、0～3％Y2O3、3～7％B2O3、0～3％P2O5、0.1～0.5％Sb2O3。
As a further technical scheme, the high-fracture toughness microcrystalline glass for the mobile phone back plate comprises 3-5% of Li in the basic glass composition2O, and Li2O/(Na2O+K2O) is 1/4-1/2.
As a further technical scheme, the high-fracture-toughness microcrystalline glass for the mobile phone back plate is CaF2Is introduced as a primary nucleating agent, TiO2+ZrO2As a secondary nucleating agent, and TiO2+ZrO2The sum of the contents is less than CaF2And (4) content.
As a further technical scheme, the high fracture toughness microcrystalline glass for the mobile phone back plate comprises the following components in percentage by mass: 52-63% SiO2、1.5～4.5％Al2O3、15～19％CaO、11～18％Na2O+K2O+Li2O、3～6％CaF2、1～5％TiO2+ZrO2、0～5％B2O3+P2O5、0.5～3％Y2O3、0.1～0.5％Sb2O3。
As a further technical scheme, the high fracture toughness microcrystalline glass for the mobile phone back plate comprises the following components in percentage by mass: SiO 2258.9％、Al2O3 2.8％、CaO16.5％、Na2O+K2O+Li2O 11.5％、CaF24％、TiO2+ZrO2 1.2％、B2O3+P2O5 3.8％、Y2O3 0.8％、0.5％Sb2O3。
The invention also provides a preparation method of the high-fracture toughness microcrystalline glass for the mobile phone back plate, which comprises the following steps:
s1, preparing base glass: weighing the materials, and melting the materials at 1350-1450 ℃ for 6-12 hours;
s2, forming, annealing and cold working;
s3, low-temperature nucleation and high-temperature crystallization;
s4, chemical strengthening.
In the step S3, the low-temperature nucleation temperature is 500-650 ℃, the heat preservation time is 0.5-12 h, the high-temperature crystallization temperature is 730-950 ℃, and the heat preservation time is 0.5-12 h.
As a further technical scheme, in the step S4, the chemical strengthening is performed by one-step or two-step ion exchange, and the salt containing potassium, sodium or cesium is used, wherein the salt comprises one or more of potassium nitrate, sodium nitrate and cesium nitrate, and the microcrystalline glass is soaked in the composite molten salt at 350-480 ℃ for 0.5-24 hours.
As a further technical scheme, through the heat treatment process of low-temperature nucleation and high-temperature crystallization, the total crystal content of the microcrystalline glass is 40-70%, and the fracture toughness of the microcrystalline glass is 1.8-3.0 M.Pam1/2。
The function analysis of each component of the invention is as follows:
SiO2: the weight percent is controlled between 50wt percent and 63wt percent. SiO 22As a primary network former for glass, the glass has improved strength, modulus of elasticity, hardness and chemical stability, while increasing brittleness, viscosity and softening point. If the content is less than 50 wt%, the prepared glass is easy to phase separate and has poor chemical stability; if SiO2An excessively high content, exceeding 70 wt%, results in an excessively high melting temperature, which makes melting difficult and affects the post-forming process.
Al2O3：Al2O3Is an important network intermediate, is beneficial to improving the glass structure and improving the strength, the elastic modulus, the hardness and the durability of the microcrystalline glass. By [ AlO ]4]Instead of SiO2Later, the molecular volume increases, the structural network voids increase, and ion exchange is facilitated. However, in the present glass system, too much alumina is disadvantageous in precipitation of crystals, and inhibition or presence of crystal phase transition during the precipitation of crystals makes it impossible to obtain desired crystals for the purpose of design and affects the fracture toughness of the glass ceramics, so that it is necessary to control Al2O3The content is 1 to 5 weight percent, and preferably 1 to 3 weight percent.
Li2O: the weight percent is controlled between 3 percent and 5 percent. Li2The introduction of O as the external body of the glass network can greatly reduce the melting temperature of the glass, improve the melting quality and improve the glass forming. During chemical strengthening, the glass can be rapidly exchanged with Na in molten salt to form a deeper ion exchange depth, which is beneficial to the breakage resistance of the glass. In addition, with alkali metal Na2O and K2O can act synergistically to form a mixed alkali effect, which is beneficial to the structural stability and performance improvement of the glass, but the content of the O is too high, so that the phase separation of the basic glass is caused, the chemical stability of the glass is poor, and the cost is increased.
Na2O: the weight percent is controlled between 6 percent and 12 percent. The main oxide of the wollastonite microcrystal is formed, and the wollastonite microcrystal exchanges potassium ions in molten salt in the chemical strengthening of the microcrystalline glass, so that a proper surface compressive stress value and diffusion depth can be obtained. The content of Na incorporated in the crystal structure is at least 6%, and if it is too small, the crystal cannot be efficiently incorporated and the formation of a wollastonite crystal is difficult, but if it exceeds 12%, the glass structure changes, the liquid phase temperature is low, and the crystal precipitation is suppressed, and the preferable content is 6 to 9%.
K2O: controlled between 4 wt% and 9 wt%, and forming wollastonite (Na)4～3K2～3Ca5<Si12O30>F4) The content of the microcrystalline main oxide, namely K which is taken into the crystal structure, is at least 4 percent, if the content is too small, the crystal cannot be effectively added due to insufficient content, and the xonotlite crystal is difficult to form, but if the content is more than 9 percent, the glass structure is changed, the expected main crystal phase can be influenced, and the preferable content is 5-7 percent. The invention defines the alkali metal Li2O/Na2O/K2Relation of O, Li2O/(Na2O+K2O) 1/4 to 1/2, and if the ratio is more than 1/2, microcrystals such as a xonotlite crystal which are difficult to obtain with high fracture toughness exist, and lithium-containing crystals such as lithium silicates are easy to produce; if the ratio is less than 1/4, lithium is less contained, and chemical strengthening such as Na+-Li+Disadvantageously, it is difficult to obtain a large stress value and a large depth of stress layer, which is disadvantageous to the enhancement of the glass strength, and therefore, the control is requiredSystem ratio of Li2O/(Na2O+K2O) 1/4 to 1/2, preferably controlled Li2O/(Na2O+K2O)＝1/4～1/3。
CaO: controlled between 15 wt% and 20 wt%, and forming wollastonite (Na)4～3K2～3Ca5<Si12O30>F4) The microcrystalline main oxide is an important component of a precipitated crystal phase of the microcrystalline glass, has high content, can reduce the melting temperature of the glass, is easier to melt and clarify, can promote the crystallization of the glass, is easy to obtain the microcrystalline glass, and can obtain the wollastonite and the calcium-containing crystal by controlling a heat treatment system. If the content is too small below 15%, the crystallization of the glass is not favorable, and even desired crystals cannot be obtained, but if the content is too large, the formation of the desired main crystal phase is affected, and the preferred content is in the range of 15 to 18%.
TiO2: the content is controlled between 0 wt% and 4 wt%. The crystal nucleus agent is introduced as a microcrystalline glass crystal nucleus agent, can effectively promote the formation of crystal nucleus, can improve the glass structure and is beneficial to the proceeding of ion exchange, but TiO2Coloring is easily caused, the optical properties of the glass are affected, and the addition amount is strictly controlled during the introduction.
ZrO2: the content is controlled between 0 wt% and 4 wt%. The crystal nucleus agent is introduced as a microcrystalline glass crystal nucleus agent, can effectively promote the formation of crystal nucleus, can improve the glass structure and is beneficial to the proceeding of ion exchange, but TiO2Coloring is easily caused, the optical properties of the glass are affected, and the addition amount is strictly controlled during the introduction.
P2O5: the content is controlled between 0 wt% and 3 wt%. The introduction of the glass-ceramic as a network former with an open glass network structure is an important composition of the glass ceramics, and the introduction of the glass-ceramic is beneficial to improving the melting of the glass and increasing the ZrO2Solubility in glass melts, elevated ZrO2The amount introduced. Furthermore, P2O5The introduction of (2) has a promoting effect on the later-stage ion exchange process.
B2O3: the weight percent is controlled between 3 percent and 7 percent. Introduced as a network former to open the glass network structure and promote phase separation of the glassIn devitrification, the introduction of which is advantageous for improving the melting of the glass, B2O3The introduction of (2) has a promoting effect on the later-stage ion exchange process.
Y2O3: 0 wt% -3 wt%. Can improve the mechanical properties of the microcrystalline glass, such as elastic modulus, hardness and the like.
CaF2: 3 to 6 weight percent. The main oxide of the wollastonite microcrystal is formed, and is an important component of a crystal phase precipitated from the microcrystalline glass. Too much or too little can affect the formation of the desired primary crystalline phase. TiO 22/ZrO2/CaF2The crystal nucleating agent is important for the crystallization of glass and can influence the crystallization type and the crystal size of the glass, and the precipitated main crystal is the xonotlite, so the small CaF is initially precipitated through experiments2Crystals, inducing precipitation of crystalline sillimanite, thus CaF2The effect of (A) is evident, while this sub-example of the patent incorporates ZrO2Or TiO2The control of crystallization is enhanced, and auxiliary effects are achieved, such as grain refinement, so that a secondary crystal nucleating agent TiO is required to be controlled2+ZrO2Sum less than CaF2And (4) content.
The principle and the beneficial effects of the invention are as follows:
1. the glass/glass ceramics is easy to realize in preparation method and process, and the glass ceramics with high fracture toughness has lower hardness and is easy to process and form, so the glass/glass ceramics is more suitable for being used as a mobile phone backboard. The high-fracture-toughness microcrystalline glass provided by the invention contains 30-60% of main crystalline phase by mass, and is wollastonite; a secondary crystal phase, the mass content of which is 5-10%, and the secondary crystal phase is one or two of xonotlite and calcium fluoride; the balance being a glassy phase. The material has excellent fracture toughness value, can well meet the chemical strengthening requirement and take the advantages of both the material and the material into consideration, has excellent breaking strength, excellent fracture toughness and other properties, can further strengthen and improve the hardness, bending strength and fracture toughness of the microcrystalline glass, and has better scratch resistance, ideal drop resistance and other properties.
2. The microcrystalline glass of the invention is the crystalline glass containing high fracture toughness canasite, and can be made into different color systems by ion coloring. The wollastonite crystal has a hinge structure in the microcrystalline glass, so that a microcrack expansion path can be effectively blocked and deflected, and the falling resistance of the glass is better improved.
3. The invention is characterized in that the microcrystalline glass containing the crystalline of the canasite has better average breaking strength, quite prominent fracture toughness and other properties compared with the conventional microcrystalline glass. Secondly, compared with the characteristic that the common microcrystalline glass is difficult to carry out ion exchange, the invention ensures that chemical strengthening is easier to carry out and effective ion exchange can be carried out by controlling the proportion of alkali metal, alkaline earth metal and network ions, and the crystal content of the microcrystalline glass can be controlled by a heat treatment system, and Li+Does not participate in the formation of a crystal structure, and is beneficial to the subsequent ion exchange. In addition, the microcrystalline glass has very outstanding fracture toughness, and is combined with a large depth of a compression stress layer (namely an ion exchange layer) formed in the subsequent chemical strengthening, so that the performances of surface hardness, breaking strength, fracture toughness, scratch resistance of glass, capability of resisting generation and expansion of surface cracks and the like can be further improved, and the microcrystalline glass has excellent drop performance.
4. The inventors summarize through a large number of experimental studies and test analyses: the precipitation of the crystalline of the wollastonite is closely related to the composition of the glass and also closely related to a heat treatment system, and the type and the content of the crystalline are required to be obtained only by strictly controlling the precipitation of the crystalline of the wollastonite and the glass; k in glass+And Na+There are mainly two distribution states: a network modifier in the glass phase, which can participate in the enhanced ion exchange; the other is not accessible for exchange when incorporated into the crystal structure to form the desired crystals. When Na is in the glass phase+The content of Na in the crystal structure is greater than or equal to+When the glass ceramics are used, the glass ceramics are easy to strengthen; when Na is in the glass phase+The content of Na in the crystal structure is less than that of Na+Is not good for strengthening ion exchange, but another ion Li+Is not incorporated into crystal structure and can be mixed with K in molten salt+And Na+Fully exchanged, resulting in large stress depths and stress values.
5. Compared with the existing high-alumina glass, the microcrystalline glass is easy to melt and form, has low requirement on equipment, is more economical and is easier to produce; compared with zirconia ceramics, the zirconia ceramics has high fracture toughness, but has high cost, low yield and difficult processing, and the glass of the invention is suitable for satisfying the mainstream method of the current glass production, namely an overflow method, a float method, a rolling method and a pouring method, can be produced in large batch, has high efficiency and low cost, and has great competitive advantage.
Drawings
FIG. 1 is an XRD pattern of examples 7 and 12 and comparative example 5, wherein ■ represents canasite; tangle-solidup represents xonotlite Δ represents calcium fluoride;
FIG. 2 is a graph showing the stress distribution of the base glass of example 12.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any inventive step, are intended to be within the scope of the present invention.
Example 1
S1, weighing raw materials serving as various components, selecting corresponding raw materials such as oxides, hydroxides, carbonates, nitrates, fluorides, chlorides, hydroxides, metaphosphoric acid compounds and the like according to the following weight percentage: 50% SiO2、5％Al2O3、19.2％CaO、12％Na2O、2％K2O、4.7％Li2O、3％CaF2、1％ZrO2、3％B2O3、0.1％Sb2O3Preparing base glass, and melting at 1350 ℃ for 12 hours; wherein (Li)2O)/(Na2O+K2O)＝0.34，CaF2/(TiO2+ZrO2)＝3；
S2, forming, annealing and cold working;
s3, low-temperature nucleation and high-temperature crystallization, wherein the low-temperature nucleation temperature is 650 ℃, the heat preservation time is 0.5h, the high-temperature crystallization temperature is 950 ℃, and the heat preservation time is 0.5 h;
s4, two-step chemical strengthening: firstly 85% NaNO3+15％KNO3Soaking in composite molten salt at 350 deg.C for 12 hr, and adding 10% NaNO3+90％KNO3Soaking in composite molten salt at 480 deg.C for 0.5 h.
Example 2
S1, weighing raw materials serving as various components, selecting corresponding raw materials such as oxides, hydroxides, carbonates, nitrates, fluorides, chlorides, hydroxides, metaphosphoric acid compounds and the like according to the following weight percentage: 63% SiO2、1％Al2O3、15％CaO、6％Na2O、2％K2O、3％Li2O、3％CaF2、1％ZrO2、3％B2O3、1％TiO2、0.5％Sb2O3、1.5％P2O5Preparing base glass, and melting at 1450 ℃ for 6 hours; wherein (Li)2O)/(Na2O+K2O)＝0.38，CaF2/(TiO2+ZrO2)＝1.5；
S2, forming, annealing and cold working;
s3, low-temperature nucleation and high-temperature crystallization, wherein the low-temperature nucleation temperature is 500 ℃, the heat preservation time is 12 hours, the high-temperature crystallization temperature is 730 ℃, and the heat preservation time is 12 hours;
s4, two-step chemical strengthening: firstly 85% NaNO3+15％KNO3Soaking in composite molten salt at 350 deg.C for 12 hr, and adding 10% NaNO3+90％KNO3Soaking in composite molten salt at 480 deg.C for 0.5 h.
Example 3
S1, weighing raw materials serving as various components, selecting corresponding raw materials such as oxides, hydroxides, carbonates, nitrates, fluorides, chlorides, hydroxides, metaphosphoric acid compounds and the like according to the following weight percentage: 50% SiO2、1％Al2O3、20％CaO、6％Na2O、6％K2O、5％Li2O、3％CaF2、2％ZrO2、3％B2O3、0.1％Sb2O3、0.9％Y2O3、3％P2O5Preparing base glass, and melting at 1350 ℃ for 12 hours; wherein (Li)2O)/(Na2O+K2O)＝0.42，CaF2/(TiO2+ZrO2)＝1.5；
S2, forming, annealing and cold working;
s3, low-temperature nucleation and high-temperature crystallization, wherein the low-temperature nucleation temperature is 600 ℃, the heat preservation time is 3 hours, the high-temperature crystallization temperature is 800 ℃, and the heat preservation time is 4 hours;
s4, two-step chemical strengthening: firstly 85% NaNO3+15％KNO3Soaking in composite molten salt at 400 deg.C for 15 hr, and adding 10% NaNO3+90％KNO3Soaking in composite molten salt at 480 deg.C for 4 hr.
Example 4
S1, weighing raw materials serving as various components, selecting corresponding raw materials such as oxides, hydroxides, carbonates, nitrates, fluorides, chlorides, hydroxides, metaphosphoric acid compounds and the like according to the following weight percentage: 53.5% SiO2、2％Al2O3、18％CaO、6％Na2O、3％K2O、3％Li2O、5％CaF2、2％TiO2、1％ZrO2、3％B2O3、0.5％Sb2O3、3％Y2O3Preparing base glass, and melting at 1350 ℃ for 12 hours; wherein (Li)2O)/(Na2O+K2O)＝0.33，CaF2/(TiO2+ZrO2)＝1.67；
S2, forming, annealing and cold working;
s3, low-temperature nucleation and high-temperature crystallization, wherein the low-temperature nucleation temperature is 550 ℃, the heat preservation time is 4 hours, the high-temperature crystallization temperature is 750 ℃, and the heat preservation time is 2 hours;
s4, two-step chemical strengthening: firstly 85% NaNO3+15％KNO3Soaking in composite molten salt at 500 deg.C for 8 hr, and adding 10% NaNO3+90％KNO3Soaking in composite molten salt at 400 deg.C for 4 hr.
Example 5
S1, weighing raw materials serving as various components, selecting corresponding raw materials such as oxides, hydroxides, carbonates, nitrates, fluorides, chlorides, hydroxides, metaphosphoric acid compounds and the like according to the following weight percentage: 58.9% SiO2、2.8％Al2O3、16.5％CaO、5％Na2O、3％K2O、3.5％Li2O、4％CaF2、0.2％TiO2、1％ZrO2、3％B2O3、0.8％P2O5、0.8％Y2O3、0.5％Sb2O3Preparing base glass, and melting at 1350 ℃ for 12 hours; wherein (Li)2O)/(Na2O+K2O)＝0.44，CaF2/(TiO2+ZrO2)＝1.67；
S2, forming, annealing and cold working;
s3, low-temperature nucleation and high-temperature crystallization, wherein the low-temperature nucleation temperature is 550 ℃, the heat preservation time is 6 hours, the high-temperature crystallization temperature is 730 ℃, and the heat preservation time is 2 hours;
s4, two-step chemical strengthening: firstly 85% NaNO3+15％KNO3Soaking in composite molten salt at 500 deg.C for 8 hr, and adding 10% NaNO3+90％KNO3Soaking in composite molten salt at 400 deg.C for 4 hr.
Example 6
S1, weighing raw materials serving as various components, selecting corresponding raw materials such as oxides, hydroxides, carbonates, nitrates, fluorides, chlorides, hydroxides, metaphosphoric acid compounds and the like according to the following weight percentage: 56% SiO2、1.5％Al2O3、16％CaO、8％Na2O、4％K2O、4％Li2O、4％CaF2、1％TiO2、2％ZrO2、3％B2O3、0.5％Sb2O3Preparing base glass, and melting at 1350-1450 ℃ for 6-12 hours; wherein (Li)2O)/(Na2O+K2O)＝1/3，CaF2/(TiO2+ZrO2)＝1.33；
S2, forming, annealing and cold working;
s3, low-temperature nucleation and high-temperature crystallization, wherein the low-temperature nucleation temperature is 550 ℃, the heat preservation time is 4 hours, the high-temperature crystallization temperature is 750 ℃, and the heat preservation time is 2 hours;
s4, two-step chemical strengthening: firstly 85% NaNO3+15％KNO3Soaking in composite molten salt at 390 deg.C for 6 hr, and then 10% NaNO3+90％KNO3Soaking in composite molten salt at 425 deg.C for 4 hr.
Example 7
S1, weighing raw materials serving as various components, selecting corresponding raw materials such as oxides, hydroxides, carbonates, nitrates, fluorides, chlorides, hydroxides, metaphosphoric acid compounds and the like according to the following weight percentage: 56% SiO2、1.5％Al2O3、6％Na2O、6％K2O、4％Li2O、4％CaF2、16％CaO、1％TiO2、2％ZrO2、3％B2O3、0.5％Sb2O3Preparing base glass, and melting at 1350-1450 ℃ for 6-12 hours; wherein (Li)2O)/(Na2O+K2O)＝1/3，CaF2/(TiO2+ZrO2)＝2.5；
S2, forming, annealing and cold working;
s3, low-temperature nucleation and high-temperature crystallization, wherein the low-temperature nucleation temperature is 550 ℃, the heat preservation time is 4 hours, the high-temperature crystallization temperature is 750 ℃, and the heat preservation time is 2 hours;
s4, two-step chemical strengthening: firstly 85% NaNO3+15％KNO3Soaking in composite molten salt at 390 deg.C for 6 hr, and then 10% NaNO3+90％KNO3Soaking in composite molten salt at 425 deg.C for 4 hr.
Example 8
Different from example 7 in that S4 is one-step chemical strengthening, 10% NaNO3+90％KNO3Soaking in composite molten salt at 400 deg.C for 4 hr.
The remaining examples and comparative examples were conducted in accordance with the experimental methods of the above examples, according to the raw material composition and the data of the preparation process of table 1, and are omitted herein.
The invention discloses a method for detecting various data as follows:
1. microhardness of glass ceramics: the load and the length of the depression when the diamond pyramid pressure head with the included angle of 136 degrees on the opposite surface is pressed into the pyramid-shaped depression on the test surface are calculated by adopting an equipment microhardness meter, the force application is 0.2kgN, the time is 15 s.
2. Fracture toughness of glass ceramics: a microcomputer controlled electronic universal tester is adopted to test by taking GB/T23806-.
3. Four-point bending strength of microcrystalline glass: the test is carried out by adopting a microcomputer control electronic universal tester and taking ASTMC 158-.
4. Impact resistance test of glass ceramics: a falling ball testing machine is adopted, a steel ball with the mass of 110g impacts 9 different parts of the sample, and the testing result is expressed by the maximum impact energy which can be borne.
5. And 3D complete machine drop resistance test of the microcrystalline glass: and testing by adopting a numerical control drop machine.
6. Since the microcrystalline glass after microcrystallization has poor transparency, only the ion-exchanged stress value and the stress depth of the mother glass are tested so that both CS and DOL of the present microcrystalline glass in the table are the test values of the mother glass.
TABLE 1 oxide compositions and test data for inventive and comparative examples
Comparative example 1 due to Li2Low content of O, (Li)2O)/(Na2O+K2O) less than 1/4, less lithium, chemical strengthening such as Na+-Li+Disadvantageously, large stress values and stress layer depths are difficult to obtain, the improvement of the glass strength is not favorable, and the impact and drop test data are poorer than those of the embodiment of the invention
Comparative example 2 due to CaF2Low content of (C), CaF2/(TiO2+ZrO2) Less than 1, the method is unfavorable for inducing precipitation of the high fracture toughness crystalline phase of the wollastonite, the breakage resistance of the microcrystalline glass is influenced, and the impact and drop test data are poorer than those of the embodiment of the invention.
Comparative example 3 due to Li2High content of O, (Li)2O)/(Na2O+K2O) is large and 1/2, contains lithium higher than the original standard, affects the crystal phase type of the microcrystalline glass, the main crystal phase is lithium silicate, Li enters the crystal structure, the depth of the stress layer becomes shallow, the fracture toughness is lower than 1.8 MPa.mm0.5The damage resistance of the microcrystalline glass is influenced, and the data of the impact test and the drop test are poorer than those of the embodiment of the invention.
Compared with the example 8 and the comparative example 4, the other parts are the same, the example 8 is subjected to primary strengthening, the comparative example 4 is not subjected to chemical strengthening, and the test data of the three parts shows that the performances of the three parts are obviously reduced in comparison with the impact and drop test data, which shows that the performance of the microcrystalline glass is obviously improved by the chemical strengthening, and the mechanical performance is obviously improved by the multi-step chemical strengthening compared with the one-step chemical strengthening.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The utility model provides a high fracture toughness microcrystalline glass for cell-phone backplate which characterized in that includes:
a main crystal phase which is 30-60% of canasite by mass;
a secondary crystal phase, the mass content of which is 5-10%, and the secondary crystal phase is one or two of xonotlite and calcium fluoride;
the balance being a glassy phase.
2. The microcrystalline glass with high fracture toughness for the mobile phone back plate according to claim 1, which is characterized by comprising the following components in percentage by mass: 50-63% SiO2、1～5％Al2O3、15～20％CaO、6～12％Na2O、2～6％K2O、3～5％Li2O、3～6％CaF2、0～2％TiO2、1～3％ZrO2、0～3％Y2O3、3～7％B2O3、0～3％P2O5、0.1～0.5％Sb2O3。
3. The microcrystalline glass with high fracture toughness for mobile phone back plates as claimed in claim 2, wherein the base glass composition contains 3-5% of Li2O, and Li2O/(Na2O+K2O) is 1/4-1/2, and the microcrystalline glass is prepared from the base glass.
4. The microcrystalline glass with high fracture toughness for mobile phone back plates as claimed in claim 2, wherein F is CaF2Is introduced as a primary nucleating agent, TiO2+ZrO2As a secondary nucleating agent, and TiO2+ZrO2The sum of the mass contents of the components is less than CaF2And (4) content.
5. The microcrystalline glass with high fracture toughness for the mobile phone back plate according to any one of claims 1 to 4, which is characterized by comprising the following components in percentage by mass: 52-63% SiO2、1.5～4.5％Al2O3、15～19％CaO、11～18％Na2O+K2O+Li2O、3～6％CaF2、1～5％TiO2+ZrO2、0～5％B2O3+P2O5、0.5～3％Y2O3、0.1～0.5％Sb2O3。
6. The microcrystalline glass with high fracture toughness for the mobile phone back plate according to claim 2, which is characterized by comprising the following components in percentage by mass: SiO 2258.9％、Al2O3 2.8％、CaO16.5％、Na2O+K2O+Li2O 11.5％、CaF24％、TiO2+ZrO2 1.2％、B2O3+P2O5 3.8％、Y2O3 0.8％、0.5％Sb2O3。
7. A preparation method of high fracture toughness microcrystalline glass for a mobile phone backboard is characterized by comprising the following steps:
s1, preparing base glass: weighing the materials, and melting the materials at 1350-1450 ℃ for 6-12 hours;
s2, forming, annealing and cold working;
s3, low-temperature nucleation and high-temperature crystallization;
s4, chemical strengthening.
8. The method for preparing microcrystalline glass with high fracture toughness for a mobile phone backplate, according to claim 7, wherein in step S3, the low-temperature nucleation temperature is 500-650 ℃, the heat preservation time is 0.5-12 h, the high-temperature crystallization temperature is 730-950 ℃, and the heat preservation time is 0.5-12 h.
9. The method for preparing the microcrystalline glass with high fracture toughness for the back plane of the mobile phone as claimed in claim 7, wherein said step S4 is performed by one-step or two-step ion exchange, wherein said salt comprises one or more of potassium, sodium or cesium, and said salt comprises potassium nitrate, sodium nitrate and cesium nitrate, and said microcrystalline glass is soaked in a composite melting salt at 350-480 ℃ for 0.5-24 hours.
10. The preparation method of the microcrystalline glass with high fracture toughness for the mobile phone back plate as claimed in claim 7, wherein the total crystal content of the microcrystalline glass is 40-70% through the heat treatment process of low-temperature nucleation and high-temperature crystallization, and the fracture toughness of the microcrystalline glass is 1.8-3.0M-Pam1/2。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114477771A (en) * | 2022-04-01 | 2022-05-13 | 河北省沙河玻璃技术研究院 | High-elasticity-modulus high-hardness transparent microcrystalline glass and preparation method thereof |
| CN116477843A (en) * | 2022-01-17 | 2023-07-25 | 荣耀终端有限公司 | Glass ceramic, reinforced glass, preparation method of glass ceramic, shell of electronic equipment, display screen of electronic equipment and electronic equipment |
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2021
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| 宋树欣等: "Al2O3对 R2O－CaO－SiO2－F统微晶玻璃结构及析晶的影响", 《玻璃与搪瓷》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116477843A (en) * | 2022-01-17 | 2023-07-25 | 荣耀终端有限公司 | Glass ceramic, reinforced glass, preparation method of glass ceramic, shell of electronic equipment, display screen of electronic equipment and electronic equipment |
| CN114477771A (en) * | 2022-04-01 | 2022-05-13 | 河北省沙河玻璃技术研究院 | High-elasticity-modulus high-hardness transparent microcrystalline glass and preparation method thereof |
| CN114477771B (en) * | 2022-04-01 | 2023-09-05 | 河北省沙河玻璃技术研究院 | Transparent glass ceramic with high elastic modulus and high hardness and preparation method thereof |
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