CN108640520B

CN108640520B - Microcrystalline glass and reinforced microcrystalline glass applied to rear cover of 5G communication mobile terminal

Info

Publication number: CN108640520B
Application number: CN201810522901.5A
Authority: CN
Inventors: 田培静; 郑伟宏; 袁坚; 彭志钢
Original assignee: Glass Technology Research Institute Of Shahe City Of Hebei Province
Current assignee: Glass Technology Research Institute Of Shahe City Of Hebei Province
Priority date: 2018-05-28
Filing date: 2018-05-28
Publication date: 2021-08-10
Anticipated expiration: 2038-05-28
Also published as: CN108640520A

Abstract

Microcrystalline glass and reinforced microcrystalline glass applied to rear cover of 5G communication mobile terminal, belonging to the field of microcrystalline glassThe technical field is that the components of the microcrystalline glass comprise SiO in percentage by mass of oxides₂ 45～75％，Al₂O₃ 10～25％，Na₂O 8～20％，K₂O 1～4％，Li₂O 0～5％，MgO0～20％，ZnO 0～10％，TiO₂ 1～8％，ZrO₂ 0～20％，Eu₂O₃ 0～3％，P₂O₅ 0～5％，Sb₂O₃ 0～3％，Fe₂O₃0 to 5 percent. The microcrystalline glass has the properties of high strength and low magnetic loss, and the property of the reinforced microcrystalline glass is further improved.

Description

Microcrystalline glass and reinforced microcrystalline glass applied to rear cover of 5G communication mobile terminal

Technical Field

The invention belongs to the technical field of microcrystalline glass, and relates to microcrystalline glass applied to a rear cover of a 5G communication mobile terminal.

Background

With the development of 5G technology and wireless charging technology, higher requirements are put on the rear cover material used by the mobile terminal, because the metal rear cover can affect the millimeter wave transmission of 5G communication and hinder wireless charging, and cannot meet the development requirements of future mobile terminals. The mainstream of the current market is a glass rear cover and a ceramic rear cover. Although the performance of the ceramic rear cover is excellent, the ceramic rear cover has the problems of difficult processing, single color, low yield and the like.

At present, the rear cover of the mobile terminal glass in the market is mostly made of high-alumina glass, and although the mechanical property of the glass is improved through a surface treatment process, the development requirement of the mobile terminal cannot be met. In order to further improve the strength of the glass and to color the glass, a crystalline phase may be precipitated in the glass to produce a glass-ceramic.

In patent CN106242299A, a glass-ceramic is mentioned, which precipitates MgAl₂O₄、MgTi₂O₄The mechanical properties of the crystal phases are improved to a certain extent, but the surface hardness value is still lower, the ion diffusion depth is still shallow, and the application requirements of the mobile terminal cannot be met.

In patent CN105601115A, a glass-ceramic is mentioned, which is a spinel precipitated glass-ceramic with mohs hardness of 7.5-8 and can have different colors, overcoming the scratching problem of the building glass-ceramic with wollastonite as main crystal phase. But the patent is primarily concerned with applications in the field of architectural decoration. The performance of the microcrystalline glass can not meet the application requirements of the mobile terminal.

In patent CN104478219A, a spinel glass-ceramic is mentioned, which has a flexural strength of only 110MPa and a vickers hardness of only 5 GPa. The microcrystalline glass material disclosed in the above patent cannot meet the requirements of the rear cover of the 5G mobile terminal in terms of flexural strength, surface hardness value and ion diffusion depth.

Therefore, it is necessary to develop a high-strength and low-magnetic-loss glass ceramic to meet the performance requirements of 5G communication on the rear cover material of the mobile terminal.

Disclosure of Invention

The invention provides a high-strength and low-magnetic-loss microcrystalline glass which is suitable for being used as a rear cover of a 5G communication mobile terminal to solve the problems. The microcrystalline glass composition has the characteristics of low melting temperature, good forming performance and the like, and can be used for producing original glass by adopting the processes of float process, rolling, lattice process, downdraw process and the like. The microcrystalline glass can be chemically enhanced by adopting a one-step method or a multi-step method, the mechanical property of the microcrystalline glass is further highlighted, the magnetic loss coefficient is low, and the performance requirement of 5G communication on a rear cover material for a mobile terminal can be met. According to the technical scheme of the invention, the ultrathin glass with the thickness of 0.05-2mm can be obtained by adopting the traditional glass preparation process.

The technical scheme adopted by the invention for realizing the purpose is as follows:

the microcrystalline glass comprises the components of SiO in percentage by mass of oxides, and is applied to a rear cover of a 5G communication mobile terminal₂ 45～75％，Al₂O₃ 10～25％，Na₂O 8～20％，K₂O 1～4％，Li₂O 0～5％，MgO 0～20％，ZnO 0～10％，TiO₂ 1～8％，ZrO₂ 0～20％，Eu₂O₃ 0～3％，P₂O₅ 0～5％，Sb₂O₃ 0～3％，Fe₂O₃ 0～5％。

Bag for returningDraw Y₂O₃0 to 3%, and/or CeO₂0 to 3%, and/or Rb₂0 to 3% of O, and/or Ga₂O₃0-3%, and/or 0-2% of MnO, and/or 0-3% of NiO.

The microcrystalline glass comprises the components of SiO in percentage by mass of oxides, and is applied to a rear cover of a 5G communication mobile terminal₂ 50％，Al₂O₃ 12％，Na₂O 13％，K₂O 2％，Li₂O 3％，MgO 7％，TiO₂6％，Eu₂O₃ 1％，P₂O₅ 3％，Sb₂O₃ 1％，Fe₂O₃ 2％。

The reinforced microcrystalline glass is subjected to chemical enhancement treatment, and the chemically enhanced microcrystalline glass comprises SiO (silicon dioxide) in percentage by mass of oxides₂ 45～75％，Al₂O₃10～25％，Na₂O 4～17％，K₂O 1～6％，Li₂O 0～5％，MgO 0～20％，ZnO 0～10％，TiO₂ 1～8％，ZrO₂ 0～20％，Eu₂O₃ 0～3％，P₂O₅ 0～5％，Sb₂O₃ 0～3％，Fe₂O₃ 0～5％，Cs₂0-2% of O. Preferred components also include Y₂O₃0 to 3%, and/or CeO₂0 to 3%, and/or Rb₂0 to 3% of O, and/or Ga₂O₃0 to 3 percent. Preferably, if the cover glass rear cover color is considered, the colorant composition can adopt the following but is not limited to: 0-2% of MnO and 0-3% of NiO.

The invention has the beneficial effects that:

1) according to the invention, a novel microcrystalline glass rear cover can be obtained, is suitable for protecting components such as portable electronic equipment and optical equipment of a 5G mobile communication terminal, and can be adjusted and designed to obtain a microcrystalline glass material with high strength, high hardness, impact resistance and low magnetic loss.

2) The microcrystalline glass rear cover disclosed by the invention can be prepared by forming methods such as a float method, a rolling method, a lattice method, a pull-down method and the like due to the fact that the proper content is selected in the given composition range, and can obtain higher mechanical property and lower magnetic loss.

3) The micro-hardness of the microcrystalline glass is more than 5.5GPa, and the four-point bending strength is more than 150 MPa; after ion exchange enhancement, the microhardness is more than 7GPa, the four-point bending strength is more than 550MPa, the surface compression stress value is more than 800MPa, the stress depth value can reach more than 60 mu m, and the fracture toughness is higher than 0.8 MPa.mm^0.5。

4) The microcrystalline glass has lower loss for high-frequency communication electromagnetic waves above 6GHz, and the loss coefficient is less than 20 dB/cm. The microcrystalline glass has paramagnetic characteristic and magnetic susceptibility higher than 1 x 10^-9m³Magnetic moment of generally greater than 1X 10 per mol^-24J/T is more than or equal to J/T.

The function analysis of each component of the invention is as follows:

SiO₂as the most important network former of silicate glass, it is an essential component for forming a network structure of microcrystalline glass, and if the content thereof is less than 45 wt%, the prepared glass is easy to phase separate and has poor chemical stability. On the other hand, if SiO₂If the content is too high, more than 75 wt%, the melting temperature is too high, and the melting is difficult, thereby affecting the forming processes such as later float process, rolling process, lattice process, drawing process and the like.

Al₂O₃Is also a very important network former, but the coordination structure is closely related to the concentration of free oxygen in the glass network. When mixed with MgO, ZnO and Eu₂O₃In the case of co-introduction, Al₂O₃Can promote the precipitation of expected crystalline phase and improve the mechanical property and the magnetic property of the microcrystalline glass. Al (Al)₂O₃The content is more than 10 wt%, and Al is controlled at the same time₂O₃/R₂O is less than or equal to 1, and the strength and the chemical stability of the microcrystalline glass can be improved. However, Al₂O₃The content is too high, which causes the over-high melting temperature and difficult melting, and further influences the forming processes such as later float process, rolling process, lattice process, drawing process and the like, so the introduction amount needs to be controlledThe content is below 25 wt%.

Na₂O is taken as a very important network exosome, and the introduction of the O can reduce the polymerization degree of a glass network structure, lower the melting temperature of the glass and improve the melting performance of the glass. In the presence of TiO₂When the Ti ions are introduced together, the coordination condition of the Ti ions can be effectively regulated and controlled. Simultaneous introduction of Li into the glass composition₂And O, exchanging with potassium ions in the molten salt in the chemical strengthening process of the glass ceramics to obtain a proper surface compressive stress value and diffusion depth. Therefore, the amount of incorporation thereof needs to be controlled to 8 wt% or more, and TiO₂/Na₂The mass ratio of O is 0.2-0.5, Li₂O/Na₂The mass ratio of O is 0.2-1. But excessive Na₂O causes deterioration of chemical stability of the glass and affects formation of a desired main crystal phase during crystallization, so that it is necessary to control the amount of incorporation to 20 wt% or less.

K₂The O is used as a glass network outer body, and the introduction of the O can reduce the melting temperature of the glass, improve the melting quality and improve the optical performance of the glass. In addition, in Li₂O and Na₂In the case of co-introduction of O, by K₂The introduction of O is beneficial to improving the ion exchange depth and the mechanical property and the optical property of the chemically reinforced microcrystalline glass. Thus K₂The amount of O to be introduced must be controlled to 1 wt% or more and 4 wt% or less.

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. In Na₂O and K₂And under the condition of co-introduction of O, the deeper ion exchange depth is favorably formed. However, too high a content thereof may affect the chemical stability of the glass and exert a series of influences on the forming process. Therefore, the amount of the catalyst to be incorporated is controlled to be 0 wt% or more and 5 wt% or less. When Li is present₂The O is introduced in an amount of more than 2 wt% to increase the ion exchange depth to more than 60 μm, whereas if not introduced, the ion exchange depth will be less than 60 μm.

MgO is a glass network intermediate and can improve glass melting under the control of the content of the invention. In ZnO, Al₂O₃、Eu₂O₃When the components are introduced together, the MgO content can control the crystallization process of the microcrystalline glass and adjust the microstructure of the microcrystalline glass. However, too high a content can have a negative effect, leading to uncontrolled devitrification of the glass melt. Therefore, the content of the catalyst is controlled to be more than 0 wt% and less than 20 wt%.

ZnO is one of the constituents of the intended crystalline phase of the glass-ceramic. The introduction of ZnO can improve the melting of glass and improve the optical performance of the glass. However, too high a content adversely affects the melting and forming of the glass, and tends to cause phase separation between the melt and the glass. Therefore, the amount of the catalyst is controlled to be more than 0 wt% and less than 10 wt%.

TiO₂As a crystal nucleus agent, it is one of the essential components. On the one hand, TiO₂The introduction of (A) effectively promotes the precipitation of crystal nuclei in the nucleation process, and on the other hand, TiO₂The introduction of the (B) can easily cause the phase change of the melt, cause the uncontrollable crystallization of the melt and influence the forming of the glass. Thus TiO₂The amount of (2) to be incorporated is controlled to 1 wt% or more and 8 wt% or less.

ZrO₂As a crystal nucleus agent, it is one of the optional components. ZrO (ZrO)₂The introduction of the crystal can not only effectively promote crystal nucleus, but also play a role in refining crystal grains and promote the precipitation of nano-scale crystals in the microcrystalline glass. Furthermore, ZrO₂Is beneficial to improving the chemical stability of the glass and the visible light transmittance. Thus ZrO₂The content is preferably 2 wt% or more. At P₂O₅When co-introduced, ZrO can be improved₂Solubility in glass melt, improved glass forming performance and raised crystallized microcrystal glass strength. But ZrO₂Too high an amount of introduction causes difficulty in melting, and the glass melt is liable to devitrify, affecting the forming process. Therefore, the upper limit of its incorporation is 20 wt%.

Eu₂O₃As a network outer body, the introduction of the glass can obviously improve the glass melting effect and is beneficial to forming. More importantly, in Li₂O、Na₂By introducing Eu in the presence of O, MgO and ZnO₂O₃The glass ceramic has the synergistic effect with the 3 components, supports each other functionally, and also has the functions of improving the paramagnetism of the glass ceramic, reducing the magnetic loss,The microcrystalline glass has the function of improving the mechanical property, is beneficial to being used as a front cover and a rear cover of a mobile terminal, and the introduction amount of the microcrystalline glass needs to be controlled to be more than 0 wt% and less than 3 wt%. When Li is present₂O、Na₂O、MgO、ZnO、Eu₂O₃When the magnetic material exists at the same time, the magnetic material has lower loss for high-frequency communication electromagnetic waves above 6GHZ, the loss coefficient is less than or equal to 11dB/cm, and the magnetic susceptibility is higher than 2 multiplied by 10^-8m³Per mol; when one or more of the components are absent, the loss of the high-frequency communication electromagnetic wave above 6GHZ is low, the loss coefficient is higher than 11dB/cm and less than 20dB/cm, and the magnetic susceptibility cannot reach 2 multiplied by 10^-8m³Per mol, but with a magnetic susceptibility higher than 1X 10^-9m³/mol。

P₂O₅As the network former, it is an important composition of the glass ceramics, and its introduction is advantageous for improving glass melting. And in ZrO₂When co-introduced, ZrO can be improved₂Solubility in glass melts, elevated ZrO₂The amount introduced. But P is₂O₅When the amount of the glass is too large, phase separation tends to occur and devitrification of the glass tends to occur, so that the amount of the glass to be introduced needs to be controlled to be 0 wt% or more and 5 wt% or less.

Sb₂O₃As an important clarifying agent of glass, the introduction of the glass refining agent is beneficial to reducing the formation of gas defects in a glass melt, reducing the number of bubbles in the melt and improving the clarifying effect, and is important for preparing the glass ceramics meeting the use requirement of a mobile terminal, and the introduction amount of the glass refining agent needs to be controlled to be more than 0 wt% and less than 3 wt%.

Fe₂O₃Is an important composition of the microcrystalline glass rear cover. In Eu₂O₃、Al₂O₃The MgO and the ZnO are introduced together, so that the glass rear cover can obtain the expected color, the magnetic performance of the glass can be further improved, and the magnetic loss of the glass ceramics can be reduced. But Fe₂O₃The amount of the incorporation is too high, which tends to make the melting difficult, and therefore the amount of the incorporation needs to be controlled to 0 wt% or more and 5 wt% or less.

To further reduce the glass melting temperature, improve the melting quality and improve the glass forming performanceTo obtain a homogeneous, defect-free matrix glass and to form a suitable crystalline phase during crystallization to obtain the corresponding magnetic properties, it is preferable to introduce Y into the composition₂O₃、CeO₂、Rb₂O、Ga₂O₃The introduction amount is controlled to be 0 wt% or more and 3 wt% or less, respectively.

Detailed Description

The present invention will be further described with reference to the following examples.

The invention discloses equipment for detecting various data, which comprises the following steps:

1. for the transmittance test of 1mm thickness, the spectral transmittance of 240-800 nm is measured by a U-4000 spectrophotometer.

2. The chemical strengthening molten salt is KNO₃、NaNO₃、CsNO₃The compressive stress value of the surface of the tempered glass ceramics and the depth of the compressive stress layer are measured by a glass surface stress meter FSM-6000 LE. The refractive index of the sample was 1.536 and the optical elastic constant was 28.7[ (nm/cm)/MPa]And (6) performing calculation.

3. The microhardness and fracture toughness of the microcrystalline glass are calculated by dividing the load of a diamond quadrangular pyramid pressure head with an included angle of 136 degrees on a test surface when the diamond quadrangular pyramid pressure head is pressed into a pyramid-shaped recess on the test surface by the length of the recess by adopting equipment HXD-3000.

4. The four-point bending strength is tested by adopting a microcomputer controlled electronic universal tester TY8000-5000N and taking ASTM C158-.

5. The loss coefficient is measured by using an Agilent E8267D vector signal generator with a power amplifier as a transmitting source to emit continuous wave signals and receiving the signals by an Agilent N9030A spectrum analyzer.

6. Magnetic susceptibility and magnetic moment, and magnetic property test of the sample by using a LakeShore7407 type vibration sample magnetometer.

Detailed description of the preferred embodiments

Example 1

The microcrystalline glass comprises the components of SiO in percentage by mass of oxides₂ 50％，Al₂O₃ 12％，Na₂O 13％，K₂O 2％，Li₂O 3％，MgO 7％，TiO₂ 6％，Eu₂O₃ 1％，P₂O₅ 3％，Fe₂O₃2％，Sb₂O₃1 percent. The microcrystalline glass is a high-strength low-magnetic-loss basic microcrystalline glass of a rear cover of a 5G communication mobile terminal, and has microhardness of 7.6GPa, four-point bending strength of 216MPa and fracture toughness K_ICUp to 0.9 MPa.mm^0.5(ii) a The loss coefficient of the electromagnetic wave for the high-frequency communication of 7GHz is 14dB/cm, and the magnetic susceptibility is 3.8 multiplied by 10^-9m³Permol, magnetic moment of 4.8X 10^-24J/T。

Example 2

The microcrystalline glass comprises the components of SiO in percentage by mass of oxides₂ 70％，Al₂O₃ 10％，Na₂O 8％，K₂O 2％，MgO 2％，TiO₂ 4％，ZnO 1％，Eu₂O₃ 1％，P₂O₅ 1％，Fe₂O₃1 percent. The microcrystalline glass can be used as a high-strength low-magnetic-loss base microcrystalline glass of a rear cover of a 5G communication mobile terminal, and has microhardness of 5.6GPa, four-point bending strength of 163MPa and fracture toughness K_ICUp to 0.6 MPa.mm^0.5(ii) a For the high-frequency communication of 7GHz, the loss coefficient of the electromagnetic wave is 18dB/cm, and the magnetic susceptibility is 3.5 multiplied by 10^-9m³Permol, magnetic moment of 5.6X 10^-24J/T。

Example 3

The microcrystalline glass comprises the components of SiO in percentage by mass of oxides₂ 45％，Al₂O₃ 12％，Na₂O 10％，K₂O 1.5％，MgO 2.5％，ZrO₂ 10％，Li₂O 3％，TiO₂ 5％，ZnO 2％，Eu₂O₃ 3％，P₂O₅ 1％，Fe₂O₃ 4％，Y₂O₃1 percent. The microcrystalline glass can be used as a high-strength low-magnetic-loss base microcrystalline glass of a rear cover of a 5G communication mobile terminal, the microhardness is 6.5GPa, and the microcrystalline glass is bent at four pointsBending strength 235MPa, fracture toughness K_ICUp to 0.9 MPa.mm^0.5(ii) a For the high-frequency communication of 7GHz, the loss coefficient of the electromagnetic wave is 10dB/cm, and the magnetic susceptibility is 2.1 multiplied by 10^-8m³Permol, magnetic moment of 2.1X 10^-23J/T。

Example 4

The microcrystalline glass comprises the components of SiO in percentage by mass of oxides₂ 45.1％，Al₂O₃ 10％，Na₂O 8％，K₂O 3％，MgO 4％，ZrO₂ 12％，TiO₂ 1％，Li₂O 2.4％，ZnO 1.5％，Eu₂O₃ 2％，P₂O₅ 5％，Fe₂O₃ 5％，CeO₂1 percent. The microcrystalline glass can be used as a high-strength low-magnetic-loss base microcrystalline glass of a rear cover of a 5G communication mobile terminal, and has microhardness of 7.3GPa, four-point bending strength of 253Mpa and fracture toughness K_ICUp to 1.1 MPa.mm^0.5(ii) a For the high-frequency communication of 7GHz, the loss coefficient of the electromagnetic wave is 10dB/cm, and the magnetic susceptibility is 2.1 multiplied by 10^-8m³Permol, magnetic moment of 2.9X 10^-23J/T。

Example 5

The microcrystalline glass comprises the components of SiO in percentage by mass of oxides₂ 47.8％，Al₂O₃ 18％，Na₂O 12％，K₂O 1％，MgO 10％，ZrO₂ 1.5％，TiO₂ 2％，Li₂O 4.8％，Eu₂O₃0.4％，P₂O₅ 0.5％，Fe₂O₃ 1％，Ga₂O₃1 percent. The microcrystalline glass can be used as a high-strength low-magnetic-loss base microcrystalline glass of a rear cover of a 5G communication mobile terminal, and has microhardness of 6.5GPa, four-point bending strength of 170Mpa and fracture toughness K_ICUp to 0.8 MPa.mm^0.5(ii) a The loss coefficient of the electromagnetic wave for high-frequency communication of 7GHz is 15dB/cm, and the magnetic susceptibility is 4.3 multiplied by 10^-9m³Permol, magnetic moment of 5.7X 10^-24J/T。

Example 6

A microcrystalline glass, which is prepared from oxideThe microcrystalline glass comprises the components of SiO in percentage by weight₂ 45％，Al₂O₃ 10％，Na₂O 8％，K₂O 3.5％，MgO 3％，ZrO₂ 17％，TiO₂ 1％，Eu₂O₃ 2.5％，P₂O₅ 3％，Sb₂O₃ 1％，Fe₂O₃ 3％，CeO₂1%, MnO 1%, NiO 1%. The microcrystalline glass can be used as a high-strength low-magnetic-loss base microcrystalline glass of a rear cover of a 5G communication mobile terminal, and has microhardness of 9.3GPa, four-point bending strength of 330MPa and fracture toughness K_ICUp to 1.5 MPa.mm^0.5(ii) a For the high-frequency communication of 7GHz, the loss coefficient of the electromagnetic wave is 12dB/cm, and the magnetic susceptibility is 2.4 multiplied by 10^-9m³Permol, magnetic moment of 3.9X 10^-24J/T。

Example 7

The microcrystalline glass comprises the components of SiO in percentage by mass of oxides₂ 45％，Al₂O₃ 10％，Na₂O 8％，K₂O 2％，MgO 6％，ZrO₂ 3％，Li₂O 3.5％，TiO₂ 3.5％，ZnO 2.5％，Eu₂O₃ 2％，P₂O₅ 4％，Sb₂O₃ 0.5％，Fe₂O₃ 2％，Y₂O₃ 1％，CeO₂ 1.5％，Rb₂O 1.5％，Ga₂O₃1%, MnO 2%, NiO 1%. The microcrystalline glass can be used as a high-strength low-magnetic-loss base microcrystalline glass of a rear cover of a 5G communication mobile terminal, and has microhardness of 6.8GPa, four-point bending strength of 224Mpa and fracture toughness K_ICUp to 1.0 MPa.mm^0.5(ii) a For the high-frequency communication of 7GHz, the loss coefficient of the electromagnetic wave is 10dB/cm, and the magnetic susceptibility is 5.6 multiplied by 10^-8m³Permol, 6.3X 10 magnetic moment^-23J/T is more than or equal to J/T.

Example 8

The microcrystalline glass realizes chemical enhancement through ion exchange of cesium ions, and comprises the components of SiO in percentage by mass of oxides₂ 63％，Al₂O₃ 10％，Na₂O 7％，K₂O 4％，Li₂O 1.4％，MgO 5％，ZrO₂ 1.4％，ZnO 3.8％，TiO₂ 2.4％，Eu₂O₃ 1％，P₂O₅ 1％，Fe₂O₃ 0.5％，Cs₂And 1.5 percent of O. The tempered glass ceramics of the embodiment can be used as high-strength low-magnetic-loss glass ceramics of a rear cover of a 5G communication mobile terminal, the microhardness is 7.4GPa, the four-point bending strength is 560MPa, the compression stress value of a compression stress layer can reach 820MPa, the compression stress layer can reach 65 mu m, and the fracture toughness K is_ICUp to 1.1 MPa.mm^0.5(ii) a The loss coefficient of the electromagnetic wave for high-frequency communication of 7GHz is 11dB/cm, and the magnetic susceptibility is 2.4 multiplied by 10^-8m³Permol, magnetic moment of 3.4X 10^-23J/T。

Example 9

The microcrystalline glass comprises the components of SiO in percentage by mass of oxides₂ 65％，Al₂O₃ 10％，Na₂O 4％，K₂O 5.5％，MgO 3％，ZrO₂ 1.8％，Li₂O 1.6％，TiO₂ 2.6％，Eu₂O₃0.5％，P₂O₅ 1.0％，Fe₂O₃ 0.5％，Y₂O₃ 0.5％，CeO₂ 0.5％，Rb₂O 0.5％，Ga₂O₃ 1％，Cs₂And (3) O2 percent. The embodiment is the ion-strengthened microcrystalline glass which can be used as a high-strength low-magnetic-loss microcrystalline glass of a rear cover of a 5G communication mobile terminal, the microhardness is 8.5GPa, the four-point bending strength is 647MPa, the compression stress value of a compression stress layer can reach 872MPa, the compression stress layer can reach 75 mu m, and the fracture toughness K is_ICUp to 1.2 MPa.mm^0.5(ii) a The loss coefficient of the electromagnetic wave for high-frequency communication of 7GHz is 15dB/cm, and the magnetic susceptibility is 4.5 multiplied by 10^-9m³Permol, 6.9X 10 magnetic moment^-24J/T。

Example 10

The microcrystalline glass comprises the components of SiO in percentage by mass of oxides₂ 49％，Al₂O₃ 15％，Na₂O 7％，K₂O 6％，MgO 5％，ZrO₂ 2％，Li₂O 2.7％，TiO₂ 3.3％，ZnO 2.0％，Eu₂O₃ 1.5％，P₂O₅ 0.5％，Fe₂O₃ 0.5％，Y₂O₃ 0.5％，CeO₂ 0.5％，Rb₂O 0.5％，Ga₂O₃ 1％，MnO₂ 0.5％，NiO 0.5％，Cs₂And (3) O2 percent. The strengthened glass ceramics of the embodiment can be used as high-strength low-magnetic glass ceramics of a rear cover of a 5G communication mobile terminal, the microhardness is 8.5GPa, the four-point bending strength is 680MPa, the compression stress value of a compression stress layer can reach 950MPa, the compression stress layer can reach 100 mu m, and the fracture toughness K is K_ICUp to 1.4 MPa.mm^0.5(ii) a For the high-frequency communication of 7GHz, the loss coefficient of the electromagnetic wave is 8dB/cm, and the magnetic susceptibility is 3.8 multiplied by 10^-8m³Permol, magnetic moment of 4.8X 10^-23J/T。

Example 11

The microcrystalline glass comprises the components of SiO in percentage by mass of oxides₂ 55％，Al₂O₃ 10％，Na₂O 10％，K₂O1％，MgO 2％，ZrO₂ 1％，Li₂O 2％，TiO₂ 2％，ZnO 1％，Eu₂O₃1％，P₂O₅ 1％，Sb₂O₃ 1％，Fe₂O₃ 3％，Y₂O₃ 2％，Rb₂O 3％，Ga₂O₃ 2％，MnO 1％，NiO 1％，Cs₂And (3) O1%. The strengthened glass ceramics of the embodiment can be used as high-strength low-magnetic glass ceramics of a rear cover of a 5G communication mobile terminal, the microhardness is 8.2GPa, the four-point bending strength is 665MPa, the compression stress value of a compression stress layer can reach 900MPa, the compression stress layer can reach 95 mu m, and the fracture toughness K is_ICUp to 1.4 MPa.mm^0.5(ii) a For the high-frequency communication of 7GHz, the loss coefficient of the electromagnetic wave is 7dB/cm, and the magnetic susceptibility is 4.6 multiplied by 10^-8m³Permol, magnetic moment of 5.9X 10^-23J/T。

Example 12

The microcrystalline glass is applied to a rear cover of a 5G communication mobile terminal and comprises the following componentsOxide mass percent of SiO₂ 45％，Al₂O₃ 24％，Na₂O 8％，K₂O 4％，MgO 3％，ZrO₂ 2％，TiO₂ 1％，Eu₂O₃ 3％，P₂O₅ 3％，Fe₂O₃ 5％，Y₂O₃ 1％，CeO₂1 percent. The microhardness of the basic microcrystalline glass of the embodiment is 6.1GPa, the four-point bending strength is 182MPa, and the fracture toughness K is_ICUp to 0.6 MPa.mm^0.5The loss coefficient of electromagnetic wave for high frequency communication at 7GHZ is 15dB/cm, and the magnetic susceptibility is 3.4 multiplied by 10^-9m³Permol, magnetic moment of 4.4X 10^-24J/T。

Example 13

The microcrystalline glass comprises the components of SiO in percentage by mass of oxides, and is applied to a rear cover of a 5G communication mobile terminal₂ 55％，Al₂O₃ 10％，Na₂O 20％，K₂O 1％，MgO 1％，TiO₂ 2％，ZrO₂5％，Eu₂O₃ 1％，P₂O₅ 1％，Sb₂O₃ 1％，Fe₂O₃1%, MnO 1%, NiO 1%. The microhardness of the basic microcrystalline glass of the embodiment is 6.2GPa, the four-point bending strength is 218MPa, and the fracture toughness K is_ICUp to 0.8 MPa.mm^0.5The loss coefficient of electromagnetic wave for high frequency communication at 7GHZ is 17dB/cm, and the magnetic susceptibility is 2.8 multiplied by 10^-9m³Permol, magnetic moment of 3.1X 10^-24J/T。

Example 14

The microcrystalline glass comprises the components of SiO in percentage by mass of oxides, and is applied to a rear cover of a 5G communication mobile terminal₂ 55％，Al₂O₃ 11％，Na₂O 10％，K₂O 3％，Li₂O 1％，MgO 2％，ZnO 1％，ZrO₂ 6％，TiO₂ 5％，Eu₂O₃ 2％，P₂O₅ 2％，Fe₂O₃ 1％，CeO₂1 percent. Microhardness of the basic glass-ceramics of the exampleDegree of 5.8GPa, four-point bending strength of 192MPa, and fracture toughness K_ICUp to 0.7 MPa.mm^0.5For high frequency communication at 7GHZ, the loss coefficient of electromagnetic wave is 7dB/cm, and the magnetic susceptibility is 2.9 × 10^-8m³Permol, magnetic moment of 3.4X 10^-23J/T。

Example 15

The microcrystalline glass comprises the components of SiO in percentage by mass of oxides, and is applied to a rear cover of a 5G communication mobile terminal₂ 45％，Al₂O₃ 13％，Na₂O 10％，K₂O 1％，Li₂O 5％，MgO 6％，ZnO 1％，ZrO₂ 9％，TiO₂ 3％，Eu₂O₃ 1％，P₂O₅ 1％，Sb₂O₃ 2％，Fe₂O₃ 1％，Rb₂O 1％，Cs₂And (3) O1%. The microhardness of the toughened microcrystalline glass of the embodiment is 8.1GPa, and the fracture toughness K_ICUp to 1.5 MPa.mm^0.5Four-point bending strength 629MPa, surface compression stress value 803MPa, stress layer depth value 66 μm, loss coefficient of electromagnetic wave for high-frequency communication at 7GHz of 10dB/cm and magnetic susceptibility of 2.1 × 10^-8m³Permol, magnetic moment of 3.3X 10^-23J/T。

Comparative example 1

The microcrystalline glass and the substrate using the microcrystalline glass as the base material disclosed in CN106242299A are carried out in the most preferable mode, the compressive stress value of the obtained microcrystalline glass compressive stress layer can reach 806MPa, and the compressive stress layer can reach 8.3 mu m.

Comparative example 2

CN10560115A, which is the most preferred way to do this, the resulting glass-ceramic has a mohs hardness of 8.

Comparative example 3

CN104478219A discloses a spinel glass-ceramic, which is obtained in the most preferable mode, and has a bending strength of only 110MPa and a vickers hardness of only about 5 GPa.

Second, analytical experiment

Example 15 was used as a test group, control 1 containing no lithium oxide, control 2 containing no sodium oxide, control 3 containing no zinc oxide, control 4 containing no magnesium oxide, and control 5 containing no europium oxide.

The components are as follows:

test groups: the microcrystalline glass comprises the components of SiO in percentage by mass of oxides₂ 45％，Al₂O₃13％，Na₂O 10％，K₂O 1％，Li₂O 5％，MgO 6％，ZnO 1％，ZrO₂ 9％，TiO₂ 3％，Eu₂O₃ 1％，P₂O₅1％，Sb₂O₃ 2％，Fe₂O₃ 1％，Rb₂O 1％，Cs₂O 1％。

Control group 1: SiO 2₂ 50％，Al₂O₃ 13％，Na₂O 10％，K₂O 1％，MgO 6％，ZnO 1％，ZrO₂9％，TiO₂ 3％，Eu₂O₃ 1％，P₂O₅ 1％，Sb₂O₃ 2％，Fe₂O₃ 1％，Rb₂O 1％，Cs₂O 1％。

Control group 2: SiO 2₂ 55％，Al₂O₃ 13％，K₂O 1％，Li₂O 5％，MgO 6％，ZnO 1％，ZrO₂ 9％，TiO₂ 3％，Eu₂O₃ 1％，P₂O₅ 1％，Sb₂O₃ 2％，Fe₂O₃ 1％，Rb₂O 1％，Cs₂O 1％。

Control group 3: SiO 2₂ 46％，Al₂O₃ 13％，Na₂O 10％，K₂O 1％，Li₂O 5％，MgO 6％，ZrO₂9％，TiO₂ 3％，Eu₂O₃ 1％，P₂O₅ 1％，Sb₂O₃ 2％，Fe₂O₃ 1％，Rb₂O 1％，Cs₂O 1％。

Control group 4: SiO 2₂ 51％，Al₂O₃ 13％，Na₂O 10％，K₂O 1％，Li₂O 5％，ZnO 1％，ZrO₂9％，TiO₂ 3％，Eu₂O₃ 1％，P₂O₅ 1％，Sb₂O₃ 2％，Fe₂O₃ 1％，Rb₂O 1％，Cs₂O 1％。

Control group 5: SiO 2₂ 46％，Al₂O₃ 13％，Na₂O 10％，K₂O 1％，Li₂O 5％，MgO 6％，ZnO 1％，ZrO₂ 9％，TiO₂ 3％，P₂O₅ 1％，Sb₂O₃ 2％，Fe₂O₃ 1％，Rb₂O 1％，Cs₂O 1％。

The test properties are shown in Table 1 below.

TABLE 1

As can be seen from Table 1, in Li₂O、Na₂In the coexistence of O, ZnO and MgO, Eu is introduced₂O₃The glass ceramic and the 5 components are cooperated to support each other in function, so that the paramagnetism of the glass ceramic can be improved, and the effect of improving the magnetic performance of the glass can be realized.

Claims

1. The microcrystalline glass applied to the rear cover of the 5G communication mobile terminal is characterized in that the microcrystalline glass comprises SiO (silicon oxide) in percentage by mass₂ 45~75％，Al₂O₃ 10~25％，Na₂O 4~20％，K₂O 1~4%，Li₂O 1~5%，MgO 2~20％，ZnO 1~10%，TiO₂ 1~8%，ZrO₂ 1~20%，Eu₂O₃ 1~3%，P₂O₅ 0.5~5%，Sb₂O₃ 0~3%，Fe₂O₃ 0.5~5％；

Wherein the microcrystalline glass has a thickness of 0.05-2mm and a microhardness of 5.5GPa or moreFour-point bending strength of more than 150 MPa; the loss coefficient of the high-frequency communication electromagnetic wave above 6GHz is less than or equal to 11dB/cm, the magnetic material has paramagnetic characteristic, and the magnetic susceptibility is higher than 2 multiplied by 10^-8m³A magnetic moment greater than 1 x 10^-24J/T。

2. The microcrystalline glass applied to a rear cover of a 5G communication mobile terminal as claimed in claim 1, further comprising Y₂O₃0 to 3%, and/or CeO₂0 to 3%, and/or Rb₂0 to 3% of O, and/or Ga₂O₃0-3%, and/or 0-2% of MnO, and/or 0-3% of NiO.

3. The reinforced microcrystalline glass applied to the rear cover of a 5G communication mobile terminal is characterized in that the microcrystalline glass of claim 1 is subjected to chemical enhancement treatment, and the chemically enhanced microcrystalline glass comprises the components of SiO in percentage by mass of oxides₂ 45~75％，Al₂O₃ 10~25％，Na₂O 4~17％，K₂O 1~4%，Li₂O 1~5%，MgO 2~20％，ZnO 1~10%， TiO₂ 1~8%，ZrO₂ 1~20%，Eu₂O₃ 1~3%，P₂O₅ 0.5~5%，Sb₂O₃ 0~3%，Fe₂O₃ 0.5~5％，Cs₂O 0~2％；

Wherein the microhardness of the reinforced glass ceramics is more than 7GPa, the four-point bending strength is more than 550MPa, the surface compression stress value is more than 800MPa, and the stress depth value is more than 60 mu m; the loss coefficient of the high-frequency communication electromagnetic wave above 6GHz is less than or equal to 11dB/cm, the magnetic material has paramagnetic characteristic, and the magnetic susceptibility is higher than 2 multiplied by 10^-8m³A magnetic moment greater than 1 x 10^-24J/T。