CN108558216B

CN108558216B - Microcrystalline glass, chemically strengthened microcrystalline glass and application of chemically strengthened microcrystalline glass

Info

Publication number: CN108558216B
Application number: CN201810522251.4A
Authority: CN
Inventors: 袁坚; 郑伟宏; 田培静; 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: CN108558216A

Abstract

Micro-meterThe microcrystalline glass comprises the components of SiO in percentage by mass of oxides₂ 45～75％，Al₂O₃ 10～25％，Na₂O 8～20％，K₂O 1～4％，MgO 0～20％，ZrO₂ 0～20％，Li₂O 0～5％，TiO₂ 0～8％，ZnO 0～10％，Eu₂O₃ 0～3％，P₂O₅ 0～5％，Sb₂O₃ 0～3％，Fe₂O₃0 to 5 percent. The invention is suitable for protecting components such as portable electronic equipment, optical equipment and the like of a 5G mobile communication terminal, and the glass composition design is adopted to obtain the front cover glass ceramic material with higher visible light transmittance, higher strength and hardness and the rear cover glass ceramic material with high strength and low magnetic loss.

Description

Microcrystalline glass, chemically strengthened microcrystalline glass and application of chemically strengthened microcrystalline glass

Technical Field

The invention belongs to the technical field of microcrystalline glass, and relates to a glass application occasion which is applied to a 5G communication mobile terminal or other glass application occasions with requirements on the aspects of magnetic resistance, light transmittance, strength and the like.

Background

In portable electronic devices of communication mobile terminals, a glass material is generally adopted as a front cover to achieve a corresponding protection effect. However, as the size of the display screen of the mobile terminal is increased, the glass front cover becomes more and more susceptible to being broken. The mechanical property of the existing high-alumina glass can not meet the development requirement of the mobile terminal.

In addition, the rear cover of the mobile terminal generally adopts a metal material as the rear cover. With the development of communication technology, 5G communication is becoming the mainstream of the industry. The 5G communication technology raises the transmission signal to a higher frequency, and if a metal rear cover is adopted, the transmission of the signal is seriously influenced. Moreover, the development of wireless charging technology also puts higher demands on the rear cover of the mobile terminal. At present, high-alumina glass materials are also used as rear cover materials, but the mechanical properties of the high-alumina glass materials can not meet the application requirements. Since the thickness of the rear cover is thinner than that of the front cover, further improvement of mechanical properties is inevitably required.

The microcrystalline glass as a unique functional glass material can grow proper crystals in parent glass through a corresponding heat treatment process, and the coexistence structure of the glass phase and the crystal phase ensures that the microcrystalline glass has better performance than high-alumina glass.

Japanese patent laying-open No. 2014-114200 discloses a crystallized glass substrate for an information recording medium. The microcrystalline glass substrate has poor visible light transmittance and color balance. Further, when chemical strengthening is performed, a sufficient compressive stress value cannot be obtained, a deep stress layer cannot be formed, and the method cannot be applied to a mobile terminal.

CN106242299A discloses a glass ceramic and a substrate using the glass ceramic as a base material. Although the problem of poor color balance is solved, and a sufficient compression stress value can be obtained through an ion exchange process, a deeper stress layer still cannot be formed, so that the mobile phone is easy to damage in the falling process and cannot be used as a front cover or a rear cover of the mobile phone.

CN107963815A discloses a glass ceramic, which has relatively high thermal conductivity and strength, but for the related back cover for 5G mobile communication terminal, the requirement for wireless charging technology is high, the problem of low magnetic loss is not considered, and the mechanical property, transmittance and magnetic property of the glass ceramic cannot meet the requirement for the back cover material of 5G mobile communication and wireless charging technology.

Thus, in the prior comparable inventions, there are typically several problems: the mechanical property is low, the impact resistance is poor, and the development requirement of the mobile terminal cannot be met; low visible light transmittance, low hardness, and no scratch resistance, and is not suitable for the front cover protective member; the magnetic loss is large, the magnetic performance is poor, and the rear cover protective component and the 5G communication technology are not suitable for the rear cover protective component; the base glass has high viscosity, is difficult to form, has low productivity, has high cost, and is difficult to be used for a front cover or a rear cover of a mobile terminal.

Disclosure of Invention

The invention provides novel glass ceramics aiming at the application requirements of a protective component used by a 5G mobile communication terminal. The glass component design is adopted to obtain the front cover glass ceramic material with higher visible light transmittance, higher strength and hardness and the rear cover glass ceramic material with high strength and low magnetic loss. According to the technical scheme of the invention, the traditional and conventional glass preparation process is adopted, so that the ultrathin glass ceramics with the thickness of 0.05-2mm can be obtained.

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

the microcrystalline glass comprises the following components in percentage by mass of oxides (SiO)₂45～75％，Al₂O₃10～25％，Na₂O 8～20％，K₂O 1～4％，MgO 0～20％，ZrO₂0～20％，Li₂O 0～5％，TiO₂0～8％，ZnO 0～10％，Eu₂O₃0～3％，P₂O₅0～5％，Sb₂O₃0～3％，Fe₂O₃0～5％。

And also includes 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.

Control of (MgO + ZnO)/Al₂O₃The mass ratio of (A) is 0.3 to 0.88, and the mass ratio of ZnO/MgO is 0 to 1. By the control, a large amount of fine spinel (AB) is precipitated from the microcrystalline glass prepared by the invention₂O₄) A crystalline phase of structure, A being a divalent cation, e.g. Mg²⁺(ii) a B is a trivalent cation, e.g. Al³⁺，Fe³⁺，Eu³⁺And the like, and provides basic guarantee for the optical property, the magnetic property and the mechanical property of the final glass ceramics.

Controlling TiO₂/Na₂The mass ratio of O is 0.2 to 0.5. The mass ratio is controlled to ensure the coloring of the glass ceramics.

Control of ZrO₂/TiO₂The mass ratio of (A) to (B) is 0 to 3. The mass ratio is controlled so that TiO₂As a modifier for glass, [ TiO ] can be formed₄]Tetrahedral, is advantageous for ion exchange.

Control of Li₂O/Na₂The mass ratio of O is 0.2 to 1.

A chemically strengthened glass ceramics is prepared from the oxide (mass%) as componentOn a scale of composition, including SiO₂45～75％，Al₂O₃10～25％，Na₂O 4～17％，K₂O 1～6％，Li₂O0～5％，MgO 0～20％，ZnO 0～10％，TiO₂0～8％，ZrO₂0-20％，Eu₂O₃0～3％，P₂O₅0～5％，Sb₂O₃0～3％，Fe₂O₃0～5％，Cs₂0-2% of O. May also include Y₂O₃0 to 3%, and/or CeO₂0 to 3%, and/or Rb₂0 to 3% of O, and/or Ga₂O₃0 to 3 percent. The microcrystalline glass is chemically strengthened by adopting an ion exchange process, so that the strength and the shock resistance of the microcrystalline glass are further improved, and the performance requirements of 5G mobile communication on front and rear cover materials of a mobile terminal are met.

The use of a glass-ceramic or chemically strengthened glass-ceramic as described above in a communication device.

The microcrystalline glass or the chemically enhanced microcrystalline glass is applied to a 5G communication mobile terminal.

The invention has the beneficial effects that:

the microcrystalline glass has the advantages of high visible light transmittance, high strength, high hardness, low magnetic loss and the like, and is suitable for being used as a front cover and a rear cover of a 5G communication mobile terminal. The glass has the characteristics of low melting temperature, good forming performance and the like, and can be produced by the processes of float process, rolling, lattice process, downdraw process and the like.

The microcrystalline glass has low 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 micro-hardness of the microcrystalline glass is more than 5.5GPa, the four-point bending strength is more than 150MPa, and the fracture toughness is higher than 0.5 MPa.mm^0.5(ii) a After ion exchange enhancement, the microhardness is more than 7GPa, the four-point bending strength is more than 550MPa, and the surface compression stress value800MPa or more, stress depth value of 60 μm or more, and fracture toughness of 0.8 MPa-mm^0.5。

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 too high melting temperature and difficulty in melting, and further affects the forming processes such as later float process, rolling process, lattice process, drawing process and the like, so that the introduction amount thereof needs to be controlled 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, andthe formation of the intended main crystal phase is influenced during the crystallization process, so that the incorporation amount thereof needs to be controlled 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, can improve glass melting under the control of the content of the invention, and is added with ZnO and 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 components of the crystallized phase of the glass ceramics. 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 optional components. On the one hand, TiO₂The introduction of (A) effectively promotes the nucleation processPrecipitation of crystal nuclei, 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 content of the catalyst is controlled to be more than 0 wt% and less than 8 wt%.

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 incorporation causes difficulty in melting and the glass melt is liable to devitrify, affecting the forming process, so that the upper limit of incorporation is 15 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 functions of improving paramagnetism of the glass ceramic, reducing magnetic loss and improving mechanical property of the glass ceramic under the synergistic effect of the 3 components, is beneficial to being used as a front cover and a rear cover of a mobile terminal, and the introduction amount of the glass ceramic 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 constituent of the rear cover of microcrystalline glass, 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.

In order to further lower the glass melting temperature, improve the melting quality and improve the glass forming performance, thereby obtaining uniform and flawless mother glass and forming proper crystal phase in the crystallization process to obtain corresponding magnetic performance, Y can be preferably introduced into the composition₂O₃、CeO₂、Rb₂O、Ga₂O₃The preferable introduction amounts thereof are 0 wt% or more and 3 wt% or less, respectively.

If the color of the microcrystalline glass rear cover needs to be optimized, the following colorants can be used, but are not limited to: MnO 0-2 wt%; NiO 0-3 wt%.

Detailed Description

The microcrystalline glass of the present invention is formed by compounding a crystal phase and a glass phase, and the properties of the crystal phase and the glass phase are both considered, and the present invention will be further described with reference to specific 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 oxides₂50％，Al₂O₃15.5％，Na₂O 14％，K₂O 2％，MgO 13.2％，ZrO₂2％，P₂O₅4.3 percent. The microcrystalline glass can be used as high-transmittance and high-strength basic microcrystalline glass for a front cover of a 5G communication mobile terminal, the light transmittance of a 1 mm-thick sample with the wavelength of 550nm is 92% microhardness of 5.7GPa, the four-point bending strength is 180Mpa, and the fracture toughness is K_ICUp to 0.6 MPa.mm^0.5。

Example 2

The microcrystalline glass comprises the components of SiO in percentage by mass of oxides₂48.2％，Al₂O₃20.6％，Na₂O 13.5％，K₂O 1％，MgO 7.5％，ZrO₂2％，Li₂O3.7％，P₂O₅1.5％，Sb₂O₃1％，RbO₂1 percent. The microcrystalline glass can be used as high-transmittance and high-strength basic microcrystalline glass for a front cover of a 5G communication mobile terminal, the light transmittance of a 1 mm-thick sample with the wavelength of 550nm is 91.5%, the microhardness is 5.9GPa, the four-point bending strength is 160Mpa, and the fracture toughness is K_ICUp to 0.8 MPa.mm^0.5。

Example 3

The microcrystalline glass comprises the components of SiO in percentage by mass of oxides₂70％，Al₂O₃10％，Na₂O 8％，K₂O 2％，MgO 2％，TiO₂4％，ZnO 1％，Eu₂O₃1％，P₂O₅1％，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 4

The microcrystalline glass comprises the components of SiO in percentage by mass of oxides₂45％，Al₂O₃12％，Na₂O 10％，K₂O 1.5％，MgO 2.5％，ZrO₂10％，Li₂O 3％，TiO₂5％，ZnO 2％，Eu₂O₃3％，P₂O₅1％，Fe₂O₃4％，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, and has microhardness of 6.5GPa, four-point bending strength of 235Mpa and fracture toughness K_ICTo 0.9MPa·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 5

The microcrystalline glass comprises the components of SiO in percentage by mass of oxides₂45.1％，Al₂O₃10％，Na₂O 8％，K₂O 3％，MgO 4％，ZrO₂12％，TiO₂1％，Li₂O 2.4％，ZnO 1.5％，Eu₂O₃2％，P₂O₅5％，Fe₂O₃5％，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 6

The microcrystalline glass comprises the components of SiO in percentage by mass of oxides₂47.8％，Al₂O₃18％，Na₂O 12％，K₂O 1％，MgO 10％，ZrO₂1.5％，TiO₂2％，Li₂O 4.8％，Eu₂O₃0.4％，P₂O₅0.5％，Fe₂O₃1％，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 7

The microcrystalline glass comprises the components of SiO in percentage by mass of oxides₂45％，Al₂O₃10％，Na₂O 8％，K₂O 3.5％，MgO 3％，ZrO₂17％，TiO₂1％，Eu₂O₃2.5％，P₂O₅3％，Sb₂O₃1％，Fe₂O₃3％，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 8

The microcrystalline glass comprises the components of SiO in percentage by mass of oxides₂45％，Al₂O₃10％，Na₂O 8％，K₂O 2％，MgO 6％，ZrO₂3％，Li₂O 3.5％，TiO₂3.5％，ZnO 2.5％，Eu₂O₃2％，P₂O₅4％，Sb₂O₃0.5％，Fe₂O₃2％，Y₂O₃1％，CeO₂1.5％，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 9

The microcrystalline glass comprises the components of SiO in percentage by mass of oxides₂55％，Al₂O₃15％，Na₂O 13％，K₂O 3％，Li₂O 3％，MgO 7％，P₂O₅3％，Sb₂O₃1 percent. This implementationThe microcrystalline glass is a high-transmittance and high-strength basic microcrystalline glass for a front cover of a 5G communication mobile terminal, the transmittance of a 1mm sample at 550nm is 90 percent, the microhardness is 6.7GPa, the four-point bending strength is 219Mpa, and the fracture toughness K is_ICUp to 0.9 MPa.mm^0.5。

Example 10

The microcrystalline glass comprises the components of SiO in percentage by mass of oxides₂50％，Al₂O₃12％，Na₂O 13％，K₂O 2％，Li₂O 3％，MgO 7％，TiO₂6％，Eu₂O₃1％，P₂O₅3％，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 5.4X 10^-24J/T。

Example 11

A microcrystalline glass is prepared by soaking basic microcrystalline glass in KNO at 450 deg.C₃+NaNO₃+CsNO₃The mixed molten salt is subjected to long-time heat preservation to realize chemical enhancement, and the reinforced microcrystalline glass comprises the components of SiO in percentage by mass of oxides₂58.2％，Al₂O₃20％，Na₂O 7％，K₂O 3％，Li₂O1.4％，MgO 5.4％，Y₂O₃1％，P₂O₅3％，Cs₂And (3) O1%. The tempered glass ceramics of the embodiment can be used as high-transmittance high-strength glass ceramics of a front cover of a 5G communication mobile terminal, the light transmittance of a 1 mm-thick sample with the wavelength of 550nm is 91.7%, the microhardness is 8.3GPa, the four-point bending strength is 600MPa, the compression stress value of a compression stress layer can reach 850MPa, the compression stress layer can reach 70 mu m, and the fracture toughness K can reach K_ICUp to 1.3 MPa.mm^0.5。

Example 12

A microcrystalline glass having undergone cesium ionsIon exchange is carried out to realize chemical enhancement, and the microcrystalline glass comprises SiO in percentage by mass of oxides₂63％，Al₂O₃10％，Na₂O 7％，K₂O 4％，Li₂O 1.4％，MgO 5％，ZrO₂1.4％，ZnO 3.8％，TiO₂2.4％，Eu₂O₃1％，P₂O₅1％，Fe₂O₃0.5％，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 13

The microcrystalline glass comprises the components of SiO in percentage by mass of oxides₂65％，Al₂O₃10％，Na₂O 4％，K₂O 5.5％，MgO 3％，ZrO₂1.8％，Li₂O 1.6％，TiO₂2.6％，Eu₂O₃0.5％，P₂O₅1.0％，Fe₂O₃0.5％，Y₂O₃0.5％，CeO₂0.5％，Rb₂O 0.5％，Ga₂O₃1％，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 14

Microcrystalline glass, which is calculated by mass percent of oxidesThe component is SiO₂52％，Al₂O₃14.5％，Na₂O 6％，K₂O 6％，MgO 10％，ZrO₂2％，Li₂O 4％，Eu₂O₃0.5％，P₂O₅3％，Cs₂And (3) O2 percent. The strengthened glass ceramics of the embodiment can be used as the high-transmittance high-strength glass ceramics of the front cover of a 5G communication mobile terminal, the light transmittance of a 1mm thickness sample with the wavelength of 550nm is 91%, the microhardness is 8.5GPa, the four-point bending strength is 650MPa, the compression stress value of a compression stress layer can reach 900MPa, the compression stress layer can reach 85 mu m, and the fracture toughness K can reach K_ICUp to 1.3 MPa.mm^0.5。

Example 15

The microcrystalline glass comprises the components of SiO in percentage by mass of oxides₂49％，Al₂O₃15％，Na₂O 7％，K₂O 6％，MgO 5％，ZrO₂2％，Li₂O 2.7％，TiO₂3.3％，ZnO 2.0％，Eu₂O₃1.5％，P₂O₅0.5％，Fe₂O₃0.5％，Y₂O₃0.5％，CeO₂0.5％，Rb₂O 0.5％，Ga₂O₃1％，MnO₂0.5％，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 16

The microcrystalline glass comprises the components of SiO in percentage by mass of oxides₂55％，Al₂O₃10％，Na₂O 10％，K₂O1％，MgO 2％，ZrO₂1％，Li₂O 2％，TiO₂2％，ZnO 1％，Eu₂O₃1％，P₂O₅1％，Sb₂O₃1％，Fe₂O₃3％，Y₂O₃2％，Rb₂O 3％，Ga₂O₃2％，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。

Comparative example 1

Japanese patent laid-open No. 2014-114200 discloses a microcrystalline glass substrate for an information recording medium, which is carried out in the most preferable mode, and the obtained microcrystalline glass compressive stress layer has a compressive stress value of 513MPa and a compressive stress layer of 28.5 μm.

Comparative example 2

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 3

CN107963815A discloses a microcrystalline glass which can be used as a rear cover material, and the most preferable mode is that the compressive stress value of the obtained microcrystalline glass compressive stress layer can reach 514MPa, and the compressive stress layer can reach 5.2 mu m.

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: test groups: SiO 2₂49％，Al₂O₃15％，Na₂O 7％，K₂O 6％，MgO 5％，ZrO₂2％，Li₂O 2.7％，TiO₂3.3％，ZnO 2.0％，Eu₂O₃1.5％，P₂O₅0.5％，Fe₂O₃0.5％，Y₂O₃0.5％，CeO₂0.5％，Rb₂O 0.5％，Ga₂O₃1％，MnO₂0.5％，NiO 0.5％，Cs₂O 2％。

Control group 1: the microcrystalline glass comprises the components of SiO₂51.7％，Al₂O₃15％，Na₂O 7％，K₂O 6％，MgO 5％，ZrO₂2％，TiO₂3.3％，ZnO 2％，Eu₂O₃1.5％，P₂O₅0.5％，Fe₂O₃0.5％，Y₂O₃0.5％，CeO₂0.5％，Rb₂O 0.5％，Ga₂O₃1％，MnO₂0.5％，NiO 0.5％，Cs₂O 2％。

Control group 2: the microcrystalline glass comprises the components of SiO₂56％，Al₂O₃15％，K₂O 6％，MgO 5％，ZrO₂2％，Li₂O 2.7％，TiO₂3.3％，ZnO 2.0％，Eu₂O₃1.5％，P₂O₅0.5％，Fe₂O₃0.5％，Y₂O₃0.5％，CeO₂0.5％，Rb₂O 0.5％，Ga₂O₃1％，MnO₂0.5％，NiO 0.5％，Cs₂O 2％。

Control group 3: the microcrystalline glass comprises the components of SiO₂51％，Al₂O₃15％，Na₂O 7％，K₂O 6％，MgO 5％，ZrO₂2％，Li₂O 2.7％，TiO₂3.3％，Eu₂O₃1.5％，P₂O₅0.5％，Fe₂O₃0.5％，Y₂O₃0.5％，CeO₂0.5％，Rb₂O 0.5％，Ga₂O₃1％，MnO₂0.5％，NiO 0.5％，Cs₂O 2％。

Control group 4: the microcrystalline glass comprises the components of SiO₂54％，Al₂O₃15％，Na₂O 7％，K₂O 6％，ZrO₂2％，Li₂O 2.7％，TiO₂3.3％，ZnO 2.0％，Eu₂O₃1.5％，P₂O₅0.5％，Fe₂O₃0.5％，Y₂O₃0.5％，CeO₂0.5％，Rb₂O 0.5％，Ga₂O₃1％，MnO₂0.5％，NiO 0.5％，Cs₂O 2％

Control group 5: the microcrystalline glass comprises the components of SiO₂50.5％，Al₂O₃15％，Na₂O 7％，K₂O 6％，MgO 5％，ZrO₂2％，Li₂O 2.7％，TiO₂3.3％，ZnO 2.0％，P₂O₅0.5％，Fe₂O₃0.5％，Y₂O₃0.5％，CeO₂0.5％，Rb₂O 0.5％，Ga₂O₃1％，MnO₂0.5％，NiO 0.5％，Cs₂O 2％

The mechanical and magnetic properties were measured as 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 has the beneficial effects that the glass ceramic is cooperated with the above 5 components and mutually supports in function, so that the four-point bending strength, the hardness value, the surface layer compressive stress value and the ion diffusion depth of the strengthened glass ceramic can be improved, the paramagnetism can be improved, and the effect of improving the magnetic performance of the glass can be realized.

Claims

1. The microcrystalline glass is characterized in that the microcrystalline glass comprises SiO (silicon dioxide) in percentage by mass of oxides₂ 45～75％，Al₂O₃ 10～25％，Na₂O 8～20％，K₂O 1～4％，MgO 2～20％，ZrO₂ 0～20％，Li₂O 2.4～5％，TiO₂ 0～8％，ZnO 1.5～10％，Eu₂O₃ 0.4～3％，P₂O₅ 0～5％，Sb₂O₃ 0～3％，Fe₂O₃ 0～5％，

Wherein, (MgO + ZnO)/Al₂O₃The mass ratio is 0.3-0.88, and the mass ratio of ZnO/MgO is 0-1; li₂O/Na₂The mass ratio of O is 0.2-1;

the microcrystalline glass comprises a crystal phase of a spinel structure;

the micro-hardness of the microcrystalline glass is more than 5.5GPa, the four-point bending strength is more than 150MPa, the loss coefficient of electromagnetic waves above 6GHz is less than or equal to 11dB/cm, the microcrystalline glass has the paramagnetic characteristic, and the magnetic susceptibility is higher than 2 multiplied by 10^-8 m³A magnetic moment greater than 1 x 10^-24J/T。

2. The microcrystalline glass according to 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. A glass-ceramic according to claim 1, characterized in that the TiO is controlled₂/Na₂The mass ratio of O is 0.2 to 0.5.

4. A glass-ceramic according to claim 1, characterized in that ZrO control is carried out₂/TiO₂The mass ratio of (A) to (B) is 0 to 3.

5. The chemical reinforced microcrystal glass is characterized in that the chemical reinforced microcrystal glass comprises SiO (silicon dioxide) in percentage by mass of oxides₂ 45～75％，Al₂O₃ 10～25％，Na₂O 8～20％，K₂O 1～4％，MgO 2～20％，ZrO₂ 0～20％，Li₂O 2.4～5％，TiO₂ 0～8％，ZnO 1.5～10％，Eu₂O₃ 0.4～3％，P₂O₅ 0～5％，Sb₂O₃ 0～3％，Fe₂O₃ 0～5％，Cs₂O 0～2％；

the chemically strengthened glass ceramics comprises a crystal phase with a spinel structure;

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

6. Use of a glass-ceramic according to claim 1 or a chemically strengthened glass-ceramic according to claim 5 in a communication device.

7. The application of claim 6, wherein the microcrystalline glass or the chemically enhanced microcrystalline glass is applied to a 5G communication mobile terminal.