CN116023033A - Microcrystalline glass and preparation method and application thereof - Google Patents
Microcrystalline glass and preparation method and application thereof Download PDFInfo
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- CN116023033A CN116023033A CN202211505394.7A CN202211505394A CN116023033A CN 116023033 A CN116023033 A CN 116023033A CN 202211505394 A CN202211505394 A CN 202211505394A CN 116023033 A CN116023033 A CN 116023033A
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Abstract
The invention relates to the technical field of glass preparation, and discloses microcrystalline glass and a preparation method and application thereof. The microcrystalline glass comprises a microcrystalline glass body and nano SiO covered on the surface of the microcrystalline glass body 2 A coating; the glass ceramic body contains the following components in terms of oxide: 60-70wt% SiO 2 、13‑20wt％Al 2 O 3 、2‑5wt％Li 2 O、3‑7wt％ZnO、0‑6wt％MgO、0‑2wt％P 2 O 5 、0‑0.5wt％SnO 2 And 2 to 8wt% tetragonal ZrO 2 Whiskers; tetragonal ZrO 2 The whisker size satisfies: a diameter of 6nm or more and an aspect ratio of 40 or less; the main crystal phase in the microcrystalline glass is (Mg x Zn 1‑x )Al 2 O 4 (0.ltoreq.x < 1). The glass ceramics has good mechanical property, wear resistance and ultraviolet light resistanceThe glass can be widely applied to the front cover protection glass and the rear cover protection glass of mobile electronic terminal equipment.
Description
Technical Field
The invention relates to the technical field of glass preparation, in particular to microcrystalline glass and a preparation method and application thereof.
Background
With the rapid development of 5G communication technology, such as: mobile electronic devices such as smart phones and tablets have become an indispensable part of human life as important communication tools for people. However, the conventional mobile electronic device generally adopts a metal rear cover, which can generate electromagnetic shielding problem for the 5G communication signal, so that the ceramic rear cover or the high-strength glass or glass ceramic rear cover becomes a main alternative of the current 5G communication tool. The zirconia ceramic can be used as a backboard material of a mobile phone or a flat board, but has high hardness and difficult processing, which is extremely unfavorable for the production yield and the production efficiency of the backboard product applied to the mobile phone. In contrast, glass or glass-ceramic materials perform better than ceramics in subsequent processing. But the glass material has the biggest characteristics of larger brittleness and general fracture toughness of 0.7 MPa.m 1/2 And microcracks are easy to generate in the mobile phone, so that the mechanical strength actually achieved by the mobile phone is 2-3 orders of magnitude lower than the theoretical value, and therefore, the mobile phone can not meet the use requirements of people when being used as a back plate material of a mobile phone or a flat plate and the like.
At present, a layer of compressive stress layer can be formed on the surface layer of glass by a chemical strengthening technology so as to be used for blocking the penetration of cracks, and considering that the depth of the stress layer generated by the current chemical strength technology is generally in the range of 50-100 mu m, the penetration resistance of the cracks is limited, and when the cracks gradually propagate through the region of the compressive stress layer and enter the glass or microcrystalline glass body, the penetration resistance fails. Although the chemical strength provides a certain resistance to crack penetration, the fracture toughness of glass or glass-ceramics is a property ofThe inherent properties of the material are not affected by chemical strengthening. There is also a prior art proposal to introduce ZrO into glass ceramics 2 Component (b) ZrO induced by stress 2 Phase transition toughening is carried out to improve the fracture toughness of the microcrystalline glass, but the microcrystalline glass is prepared by adopting a melting method, because of ZrO 2 Is high in melting point, and ZrO with high melting point is directly added 2 Can raise the melting temperature of glass, increase the melting difficulty, and simultaneously, zrO 2 With SiO 2 The reaction is easy to occur to form zirconite, thereby losing the toughening effect. Therefore, how to improve the mechanical properties of glass or glass ceramics in terms of drop resistance, fracture toughness and the like is an important point of current attention.
When glass or glass ceramic materials are applied to mobile phones or flat plates, the glass or glass ceramic materials are often contacted with other objects, friction is inevitably generated, and the surface of electronic equipment such as the mobile phones or flat plates is worn along with the extension of the service time, so that the attractiveness of the electronic equipment is affected. Therefore, there is also a current focus on how to improve the wear resistance of the backplate material of mobile electronic products.
In addition, the back plate material applied to electronic equipment such as mobile phones or flat plates is generally subjected to ultraviolet radiation pretreatment for removing organic matters existing on the surface of the back plate material so as to eliminate the influence of the surface organic matters on the subsequent process treatment of the back plate material. However, in the case of glass or glass-ceramic materials, when some multivalent transition metal ions or rare earth metal ions are present in the interior, this can adversely affect the transparency of the glass and the color exhibited by the glass itself when exposed to ultraviolet light.
Disclosure of Invention
The invention aims to solve the problem that the existing microcrystalline glass backboard material cannot be good in mechanical property, wear resistance and ultraviolet light resistance.
In order to achieve the above object, a first aspect of the present invention provides a glass-ceramic comprising a glass-ceramic body and nano SiO coated on the surface of the glass-ceramic body 2 A coating;
wherein the microcrystalline glassThe body contains the following components in terms of oxide: 60-70wt% SiO 2 、13-20wt％Al 2 O 3 、2-5wt％Li 2 O、3-7wt％ZnO、0-6wt％MgO、0-2wt％P 2 O 5 、0-0.5wt％SnO 2 And 2 to 8wt% tetragonal ZrO 2 Whiskers; the tetragonal ZrO 2 The whisker size satisfies: a diameter of 6nm or more and an aspect ratio of 40 or less;
the main crystal phase in the microcrystalline glass is zinc spinel-spinel (Mg x Zn 1-x )Al 2 O 4 (0≤x＜1)。
In a second aspect, the present invention provides a method for preparing the glass-ceramic according to the first aspect, which comprises:
(1) Sequentially carrying out melting treatment, clarification and homogenization, water quenching, ball milling and sieving on the raw materials of each component in the precursor glass composition of the microcrystalline glass body to obtain a material I;
wherein the precursor glass composition comprises SiO 2 、Al 2 O 3 、Li 2 O, znO, optionally MgO, optionally P 2 O 5 And optionally SnO 2 ；
(2) Mixing the material I with tetragonal ZrO 2 Mixing the whisker and PVA binder for granulation to obtain a material II; wherein, based on the raw materials of each component in the precursor glass composition, tetragonal ZrO 2 The total mass of the whisker and the PVA binder, wherein the dosage of the PVA binder is not less than 4wt%;
(3) Molding the material II to obtain a material III; wherein the molding pressure of the molding treatment is not lower than 4MPa;
(4) Sequentially carrying out high-temperature sintering and crystallization treatment on the material III to obtain a microcrystalline glass body;
(5) Nano SiO is deposited on the surface of the microcrystalline glass body through chemical vapor deposition 2 Particles to form nano SiO 2 Coating to obtain the microcrystalline glass.
The third aspect of the invention provides an application of the glass ceramics in the front cover protection glass and the rear cover protection glass of mobile electronic terminal equipment.
Through the technical scheme, the method for preparing the microcrystalline glass is provided by the invention, and the method is realized by introducing the zinc spinel-spinel ((Mg) into the microcrystalline glass x Zn 1-x )Al 2 O 4 X is more than or equal to 0 and less than 1) as a main crystal phase, and the microcrystalline glass with the zinc spinel-spinel main crystal phase has high hardness and can perform ion exchange; at the same time, tetragonal ZrO is also introduced into the glass ceramics 2 Whisker which can generate stress-induced phase change toughening, phase change induced microcrack toughening and microcrack deflection toughening by itself, and at the same time, tetragonal ZrO 2 The fiber structure of the whisker can also improve the toughness of the microcrystalline glass, and the tetragonal ZrO can be reasonably controlled under the preferable condition 2 Whisker size to maximize toughening effect.
In addition, the method provided by the invention adopts the sintering method process to prepare the ZrO containing tetragonal 2 Microcrystalline glass of whisker and tetragonal ZrO 2 The proportion of the whisker and the glass can be arbitrarily adjusted, and the tetragonal ZrO can be realized 2 The whisker is uniformly arranged in the microcrystalline glass, so that the overall fracture toughness of the microcrystalline glass is improved; on the basis, the method provided by the invention deposits nano SiO on the surface of the glass ceramic body in a chemical vapor deposition mode 2 Particles to form nano SiO 2 The coating can increase the reflection of the microcrystalline glass on ultraviolet light so as to eliminate the influence of the ultraviolet light on the transparency and the color of the microcrystalline glass, and meanwhile, the nano SiO 2 The coating can permeate into micropores on the surface of the glass ceramics, and the porosity of the glass ceramics prepared by a sintering method is reduced, so that the adverse effect of weakening the micropores on the surface on the glass ceramics body is achieved. In addition, nano SiO 2 The coating can also properly increase the wear resistance of the glass ceramics.
In a word, the microcrystalline glass prepared by the method provided by the invention has good mechanical property, wear resistance and ultraviolet light resistance, and can be widely applied to front and rear cover protection glasses of mobile electronic terminal equipment.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, the room temperature represents 25.+ -. 2 ℃ unless otherwise stated.
The term "optional" as used in the present invention means that the operation is performed or not performed, or that the material is added or not added, unless explicitly stated otherwise.
The first aspect of the invention provides a glass-ceramic, which comprises a glass-ceramic body and nano SiO covered on the surface of the glass-ceramic body 2 A coating;
wherein, the glass ceramic body contains the following components in terms of oxide: 60-70wt% SiO 2 、13-20wt％Al 2 O 3 、2-5wt％Li 2 O、3-7wt％ZnO、0-6wt％MgO、0-2wt％P 2 O 5 、0-0.5wt％SnO 2 And 2 to 8wt% tetragonal ZrO 2 Whiskers; the tetragonal ZrO 2 The whisker size satisfies: a diameter of 6nm or more and an aspect ratio of 40 or less;
the main crystal phase in the microcrystalline glass is zinc spinel-spinel (Mg x Zn 1-x )Al 2 O 4 (0≤x＜1)。
According to some embodiments of the invention, siO 2 As the main component of the microcrystalline glass network structure, siO is added 2 The content of (2) can improve the chemical stability of the glass ceramics and the mechanical property of the glass surface, but takes SiO into account 2 Higher melting point of (C) if SiO in glass ceramics 2 Is excessively high, which increases the difficulty of glass melting, so that the formability of the precursor glass for forming glass-ceramics is lowered, and thus, siO is reduced 2 The content of (C) is controlled to be 60-70wt%.
According to some embodiments of the inventionMode, al 2 O 3 As a component for improving strength and scratch resistance of the glass-ceramics, at the same time, it also provides aluminum necessary for glass-ceramization for forming a zinc spinel-spinel crystal phase, but Al 2 O 3 Too high a content tends to cause an increase in the viscosity of the glass melt, and also reduces the formability of the glass, and therefore Al 2 O 3 The content of (2) is controlled to be 13-20wt%.
According to some embodiments of the invention, li 2 O, which is one of the components for achieving ion-exchange properties of glass ceramics, can also improve the meltability of the precursor glass.
According to some embodiments of the present invention, both ZnO and MgO act as glass network exosomes, and the introduction of an amount of zinc and/or magnesium, both of which promote melting of the glass, reduce the melting temperature of the glass precursor composition, and at the same time, are also necessary for ceramization of the glass precursor to form a microcrystalline glass to form zinc spinel and/or spinel solid solution crystalline phases.
According to some embodiments of the invention, P 2 O 5 As a nucleating agent, it can promote phase separation, form nuclei, reduce the activation energy of nucleation, and at the same time, P 2 O 5 The introduction of the glass ceramic can be beneficial to the densification of the glass ceramic prepared by adopting a sintering method.
According to some embodiments of the invention, snO 2 As a fining agent in the melting process of a glass precursor composition for glass-ceramic.
According to some embodiments of the invention, tetragonal ZrO 2 Whisker is used as toughening phase in microcrystalline glass and is prepared by ZrO 2 The existing phase change toughening, phase change induced microcrack toughening and microcrack deflection toughening mechanisms can improve the fracture toughness of the microcrystalline glass; at the same time, tetragonal ZrO 2 The whisker also provides a whisker toughening mechanism, and the microcrystalline glass is beneficial to improving the fracture toughness of the microcrystalline glass while ensuring good wear resistance and ultraviolet light resistance through the plurality of toughening mechanisms.
According to some embodiments of the invention, preferably, the nano SiO 2 Particle size of the coatingNot more than 60nm, preferably 10-60nm.
According to some embodiments of the invention, preferably, the nano SiO 2 The thickness of the coating is 0.2-0.6 mu m.
According to some embodiments of the invention, preferably, the glass-ceramic body has a crystallinity of 15-60wt%.
According to some embodiments of the invention, preferably, the size of the primary crystalline phase is no greater than 50nm. The size of the main crystal phase refers to the average size of crystal grains, which can be obtained by XRD (X-ray diffractometer) or SEM (scanning electron microscope) test, and is not particularly limited. In the present invention, the size of the main crystal phase is measured by XRD.
According to some embodiments of the invention, preferably, the tetragonal ZrO 2 The diameter of the whisker is 10-50nm. The adoption of the preferred embodiment is beneficial to further improving the fracture toughness of the microcrystalline glass and the transmittance of the microcrystalline glass in a visible light region (380-760 nm) while ensuring the favorable wear resistance and ultraviolet light resistance of the microcrystalline glass.
According to some embodiments of the invention, preferably, the tetragonal ZrO 2 The length-diameter ratio of the whisker is 10-30. The adoption of the preferred embodiment is beneficial to further improving the fracture toughness of the microcrystalline glass while ensuring that the microcrystalline glass has good wear resistance and ultraviolet light resistance.
According to some embodiments of the invention, the glass-ceramic body preferably has a hardness of 8.2-12.4GPa.
According to some embodiments of the invention, preferably, the glass-ceramic body has a fracture toughness of 3-4.5 MPa-m 1/2 。
According to some embodiments of the invention, the glass ceramic preferably has an ultraviolet reflectance of 99.9% or more in the wavelength range of 250-380 nm.
According to some embodiments of the present invention, preferably, the glass ceramic has a visible light transmittance of 38% or more in a wavelength range of 380-760 nm.
According to some embodiments of the invention, the glass-ceramic has good mechanical properties, wear resistance and ultraviolet light resistance.
In a second aspect, the present invention provides a method for preparing the glass-ceramic according to the first aspect, which comprises:
(1) Sequentially carrying out melting treatment, clarification and homogenization, water quenching, ball milling and sieving on the raw materials of each component in the precursor glass composition of the microcrystalline glass body to obtain a material I;
wherein the precursor glass composition comprises SiO 2 、Al 2 O 3 、Li 2 O, znO, optionally MgO, optionally P 2 O 5 And optionally SnO 2 ；
(2) Mixing the material I with tetragonal ZrO 2 Mixing the whisker and PVA binder for granulation to obtain a material II; wherein, based on the raw materials of each component in the precursor glass composition, tetragonal ZrO 2 The total mass of the whisker and the PVA binder, wherein the dosage of the PVA binder is not less than 4wt%;
(3) Molding the material II to obtain a material III; wherein the molding pressure of the molding treatment is not lower than 4MPa;
(4) Sequentially carrying out high-temperature sintering and crystallization treatment on the material III to obtain a microcrystalline glass body;
(5) Nano SiO is deposited on the surface of the microcrystalline glass body through chemical vapor deposition 2 Particles to form nano SiO 2 Coating to obtain the microcrystalline glass.
According to some embodiments of the invention, preferably, in step (1), the method further comprises mixing the component raw materials in the precursor glass composition prior to performing the melting treatment, so as to further improve the uniformity of distribution of the component raw materials.
According to some embodiments of the present invention, in the step (1), the melting treatment, clarification and homogenization, water quenching, ball milling and sieving may be performed with reference to the prior art, which is not particularly limited in this regard, and can achieve the object of the present invention to some extent.
According to some embodiments of the invention, preferably, in step (1), the conditions of the melting treatment include: the temperature is 1600-1700 ℃ and the time is 5-10 hours.
According to some embodiments of the invention, preferably, in step (1), the mesh number of the sieving is 100-300 mesh.
According to some embodiments of the invention, preferably, in step (2), the average particle size of the material II is 0.5-3mm.
According to some embodiments of the invention, in step (2), the tetragonal ZrO 2 Whiskers are commercially available or can be prepared according to the methods disclosed in the prior art, and are not particularly limited as long as the tetragonal ZrO 2 The whisker can meet the requirements. For example, it is available from Shandong Industrial ceramic design institute.
According to some embodiments of the invention, preferably, in step (2), the tetragonal ZrO based on the starting materials of the components in the precursor glass composition 2 The total mass of the whisker and the PVA binder is 4-8wt%. The adoption of the preferred embodiment is beneficial to further improving the fracture toughness of the microcrystalline glass while ensuring that the microcrystalline glass has good wear resistance and ultraviolet light resistance.
According to some embodiments of the invention, preferably, in step (3), the molding pressure of the molding treatment is not lower than 5MPa, preferably 5 to 30MPa. The adoption of the preferred embodiment is beneficial to further improving the hardness and fracture toughness of the microcrystalline glass while ensuring that the microcrystalline glass has good ultraviolet light resistance.
According to some embodiments of the invention, preferably, in step (3), the conditions of the molding process further include: the dwell time is not less than 20min, preferably 20-60min.
According to some embodiments of the invention, preferably, in step (3), the molding treatment is performed in a molding die including a female die and a male die, and the molding die is rapidly pressurized to be compression molded. The molding treatment comprises the following steps: spreading the material II in a female die of a forming die, covering a male die, and integrally placing the forming die with the material II in a die press to perform the forming treatment under the above conditions. The shaping treatment may be performed at room temperature.
According to some embodiments of the present invention, in step (4), the material III is subjected to a high temperature sintering and crystallization in sequence, during which the PVA (polyvinyl alcohol) binder is subjected to a high temperature treatment, which converts to CO 2 And water vapor to be completely decomposed.
According to some embodiments of the invention, preferably, in step (4), the high temperature sintering comprises a stage I and a stage II performed sequentially, and the temperature of the stage I is lower than the temperature of the stage II, which is lower than the temperature of the crystallization treatment. The high-temperature sintering is mainly used for decomposing the PVA adhesive, and considering that the PVA is decomposed at different temperature stages, the PVA is decomposed faster at a low temperature stage, and in order to prevent microcracks from being generated in the decomposition process, the temperature rising rate of the stage I is more preferably lower than that of the stage II.
According to some embodiments of the invention, preferably, the conditions of stage I comprise: the temperature is 400-500 ℃, the heat preservation time is 2-5h, the heating rate is not more than 40 ℃/h, and the preferable heating rate is 20-40 ℃/h.
According to some embodiments of the invention, preferably, the phase II conditions include: the temperature is 630-660 ℃, the heat preservation time is 1-2h, the heating rate is not more than 60 ℃/h, and the preferable heating rate is 30-60 ℃/h.
According to some embodiments of the invention, preferably, the crystallization treatment conditions include: the temperature is 730-770 ℃, the heat preservation time is 0.5-4h, the heating rate is not lower than 120 ℃/h, and the preferable heating rate is 120-300 ℃/h.
According to some embodiments of the present invention, in the step (5), the chemical vapor deposition may be performed with reference to the prior art, which is not particularly limited as long as nano SiO can be deposited on the surface of the glass-ceramic body 2 Particles and form nano SiO meeting the above requirements 2 Coating.
According to some embodiments of the present invention,preferably, in the step (5), the deposition temperature of the chemical vapor deposition is 200-400 ℃. The adoption of the preferred embodiment is favorable for further forming nano SiO meeting the requirements on the surface of the microcrystalline glass body 2 And (3) coating.
According to some embodiments of the invention, preferably, in step (5), the chemical vapor deposition is performed in a chemical vapor deposition furnace.
According to some embodiments of the present invention, preferably, before performing the chemical vapor deposition in step (5), the method further includes grinding and polishing the glass ceramic body to further improve nano SiO 2 Deposition effect of particles.
The third aspect of the invention provides an application of the glass ceramics in the front cover protection glass and the rear cover protection glass of mobile electronic terminal equipment.
The present invention will be described in detail by examples. In the following examples and comparative examples, all the raw materials used are commercially available products unless otherwise specified. Wherein:
tetragonal ZrO 2 Whiskers were purchased from Shandong institute of Industrial ceramic design and the dimensions are shown in Table 1;
nano SiO 2 The granularity and thickness of the coating were measured by SEM;
crystallinity was measured by XRD;
the hardness is measured by a nano indentation meter;
fracture toughness is measured by indentation test of the material;
the size of the main crystalline phase was measured by XRD;
the ultraviolet reflectance and the visible light transmittance can be measured by an ultraviolet-visible spectrophotometer.
Example 1
(1) Mixing the raw materials of all the components in the precursor glass composition of the microcrystalline glass body to obtain a mixture, and then sequentially carrying out melting treatment, clarification homogenization, water quenching, ball milling and sieving on the mixture to obtain a material I;
wherein, the types and the contents of the raw materials of each component in the precursor glass composition are shown in Table 1; the conditions of the melting treatment are as follows: the temperature is 1650 ℃ and the time is 7.5 hours; the number of the sieved meshes is shown in table 1;
(2) Mixing material I with tetragonal ZrO 2 Mixing the whisker and PVA binder for granulation to obtain a material II; wherein the average grain diameter of the material II is 1.5mm; tetragonal ZrO 2 The whisker content and the PVA binder amount are shown in Table 1;
(3) Molding the material II to obtain a material III;
the molding treatment is carried out in a molding die, the molding die comprises a female die and a male die, and the molding treatment comprises the following steps: spreading the material II in a female die of a forming die, covering a male die, integrally placing the forming die with the material II in a die press, and maintaining the pressure for a period of time under a certain pressure; the conditions of the molding treatment are shown in Table 1;
(4) Sequentially carrying out high-temperature sintering and crystallization treatment on the material III to obtain a microcrystalline glass body;
wherein, the high-temperature sintering comprises a stage I and a stage II which are sequentially carried out, the temperature of the stage I is lower than that of the stage II, the temperature of the stage II is lower than that of crystallization treatment, and the specific conditions are shown in the table 1;
(5) Grinding and polishing the microcrystalline glass body, and then depositing nano SiO on the surface of the microcrystalline glass body by chemical vapor deposition 2 Particles to form nano SiO 2 Coating to obtain microcrystalline glass, wherein specific characteristic parameters of the microcrystalline glass are shown in table 1;
wherein, chemical vapor deposition is carried out in a chemical vapor deposition furnace; the deposition temperatures of the chemical vapor deposition are shown in table 1.
The preparation of glass ceramics was carried out in the same manner as in example 1 except that the glass ceramics were used in the same manner as in comparative example 1.
The glass ceramics prepared in the examples and comparative examples were subjected to the related performance test, respectively, and the test results are shown in Table 1.
TABLE 1
Note that: raw materials of the respective components in the precursor glass composition and tetragonal ZrO 2 Whisker content in terms of oxide and in terms of the constituent raw materials and tetragonal ZrO in the precursor glass composition 2 The total mass of the whisker is taken as a reference.
As can be seen from the above results, comparative example 1 and comparative example 1, when tetragonal ZrO 2 When the diameter of the whisker is smaller than 6nm, the whisker has larger influence on the fracture toughness of microcrystalline glass, mainly tetragonal ZrO 2 When the diameter of the whisker is too small, the ability of the whisker to prevent the crack from continuing to propagate is relatively insufficient, so that the fracture toughness value of the glass-ceramic of comparative example 1 is 50% lower than that of the glass-ceramic of example 1, and therefore, in order to improve the fracture toughness of the glass-ceramic, it is necessary to use tetragonal ZrO 2 The diameter of the whisker is controlled within the range of more than or equal to 6 nm;
in comparative examples 1 and 2, when the pressure of the molding treatment is reduced to 3MPa, the hardness and fracture toughness properties of the resulting glass ceramics are insufficient, because the pressure of the molding treatment is insufficient, so that the structure between particles in the pressed biscuit is relatively loose, and the bonding strength in the obtained glass ceramics after sintering and crystallization is insufficient, and therefore, the hardness and fracture toughness properties are adversely affected, and therefore, in order to improve the hardness and fracture toughness properties of the glass ceramics, the pressure of the molding treatment needs to be controlled within a range of 4MPa or more;
in comparative example 1 and comparative example 3, when the amount of the PVA based binder is 3wt%, since the amount of the PVA based binder is too small, a biscuit having a certain strength cannot be obtained at the time of molding treatment, and the subsequent process treatment cannot be performed, it is necessary to control the amount of the PVA based binder to be not less than 4%.
Table 1 (subsequent)
Note that: raw materials of the respective components in the precursor glass composition and tetragonal ZrO 2 Whisker content in terms of oxide and in terms of the constituent raw materials and tetragonal ZrO in the precursor glass composition 2 The total mass of the whisker is taken as a reference.
As can be seen from the above results, comparative example 2 and example 3, tetragonal ZrO 2 The length-diameter ratio of the whisker has larger influence on the fracture toughness of the microcrystalline glass, and when tetragonal ZrO 2 When the aspect ratio of the whiskers reaches 40 (i.e., outside the preferred range defined in the present invention), the glass-ceramic obtained in example 3 exhibits a fracture toughness value reduced to 2.8 MPa-m 1/2 The fracture toughness value of the glass ceramics obtained in example 2 was reduced by 1.7 MPa.m compared with that of the glass ceramics obtained in example 2 in the preferable range 1/2 The reason may be that tetragonal ZrO 2 The aspect ratio of the whisker is too high, so that tetragonal ZrO 2 Whiskers exhibit a longer ZrO character when mixed with glass frit (material I) 2 Is easy to agglomerate together, and influences the uniformity of the mixed materials, thereby influencing the overall fracture toughness of the glass ceramics. The above results show that when tetragonal ZrO 2 When the length-diameter ratio of the whisker is in the preferred range defined by the invention, the fracture toughness of the microcrystalline glass is further improved;
for example 4, which is different from example 2 in the amount of PVA binder added during mixing, the amount of PVA binder introduced in example 4 is 10wt%, considering that PVA is mainly introduced into the glass-ceramic system as a binder to improve the bonding strength of the green body after molding, it is gradually carbonized to become gas and volatilized during sintering, and if the amount of PVA added is too large, it causes a large amount of gas to be generated during sintering, so that the porosity inside the sintered glass-ceramic is high, and the fracture toughness is reduced. The above results demonstrate that when the amount of PVA binder is within the preferred range defined in the present invention, it is advantageous to further improve the fracture toughness of glass ceramics;
for comparative example 4, which is different from example 2 in that the glass-ceramic of comparative example 4 was not subjected to chemical vapor deposition during the preparation process, the glass-ceramic obtained did not contain nano SiO 2 As is clear from the above results, the ultraviolet reflectance of the glass ceramics obtained in comparative example 4 is significantly reduced, which indicates that the nano SiO in the glass ceramics provided by the invention 2 The reflectivity of the microcrystalline glass in the ultraviolet light region (250-380 nm) can be improved by introducing the coating. In addition, the glass ceramics obtained in comparative example 4 also have a reduced fracture toughness value compared to example 2, probably due to the formation of nano SiO by chemical vapor deposition 2 In the coating process, part of nano SiO 2 The particles are filled in the pores on the surface of the glass ceramics, so that the overall fracture toughness of the glass ceramics can be properly improved.
Table 1 (subsequent)
Note that: raw materials of the respective components in the precursor glass composition and tetragonal ZrO 2 Whisker content in terms of oxide and in terms of the constituent raw materials and tetragonal ZrO in the precursor glass composition 2 The total mass of the whisker is taken as a reference.
As can be seen from the above results, when example 5 and example 6 are compared, tetragonal ZrO 2 When the diameter of the whisker is within the preferred range defined by the invention, the transmittance of the prepared microcrystalline glass in the visible light region (380-760 nm) is further improved;
for example 5 and example 7, the difference between them is the tetragonal ZrO introduced in example 7 2 The length-diameter ratio of the whisker is 5, and the fracture toughness value of the prepared microcrystalline glass is 3.6 MPa-m 1/2 Reduced to 2.2 MPa.m 1/2 Description of tetragonal ZrO 2 When the length-diameter ratio of the whisker is in the preferred range defined by the invention, the fracture toughness of the prepared microcrystalline glass is further improved;
finally, for comparative example 5, the difference between it and example 5 is that tetragonal ZrO was not added 2 Whisker, and the fracture toughness value of the obtained microcrystalline glass is only 1.2 MPa-m 1/2 Description of tetragonal ZrO 2 The whisker introduction has obvious effect on improving the fracture toughness of the microcrystalline glass.
In a word, the microcrystalline glass prepared by the method provided by the invention has good mechanical property, wear resistance and ultraviolet light resistance, and can be widely applied to front and rear cover protection glasses of mobile electronic terminal equipment.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. The glass ceramic is characterized by comprising a glass ceramic body and nano SiO (silicon dioxide) covered on the surface of the glass ceramic body 2 A coating;
wherein, the glass ceramic body contains the following components in terms of oxide: 60-70wt% SiO 2 、13-20wt％Al 2 O 3 、2-5wt％Li 2 O、3-7wt％ZnO、0-6wt％MgO、0-2wt％P 2 O 5 、0-0.5wt％SnO 2 And 2 to 8wt% tetragonal ZrO 2 Whiskers; the tetragonal ZrO 2 The whisker size satisfies: a diameter of 6nm or more and an aspect ratio of 40 or less;
the main crystal phase in the microcrystalline glass is zinc spinel-spinel (Mg x Zn 1-x )Al 2 O 4 (0≤x＜1)。
2. The glass ceramic according to claim 1, wherein the nano SiO 2 The granularity of the coating is not more than 60nm, preferably 10-60nm;
and/or, the nano SiO 2 The thickness of the coating is 0.2-0.6 mu m.
3. The glass-ceramic according to claim 1, wherein the glass-ceramic body has a crystallinity of 15-60wt%; and/or the size of the main crystalline phase is not greater than 50nm;
and/or, the tetragonal ZrO 2 The whisker size satisfies: the diameter is 10-50nm, and the length-diameter ratio is 10-30.
4. A glass-ceramic according to any one of claims 1 to 3, wherein the glass-ceramic body has a hardness of 8.2-12.4GPa; fracture toughness of 3-4.5 MPa.m 1/2 ；
And/or the ultraviolet reflectivity of the microcrystalline glass corresponding to the wavelength range of 250-380nm is more than 99.9%;
and/or the visible light transmittance of the microcrystalline glass corresponding to the wavelength range of 380-760nm is more than 38%.
5. A method of making the glass-ceramic of any of claims 1-4, comprising:
(1) Sequentially carrying out melting treatment, clarification and homogenization, water quenching, ball milling and sieving on the raw materials of each component in the precursor glass composition of the microcrystalline glass body to obtain a material I;
wherein the precursor glass composition comprises SiO 2 、Al 2 O 3 、Li 2 O, znO, optionally MgO, optionally P 2 O 5 And optionally SnO 2 ；
(2) Mixing the material I with tetragonal ZrO 2 Mixing the whisker and PVA binder for granulation to obtain a material II; wherein, based on the raw materials of each component in the precursor glass composition, tetragonal ZrO 2 The total mass of the whisker and the PVA binder, wherein the dosage of the PVA binder is not less than 4wt%;
(3) Molding the material II to obtain a material III; wherein the molding pressure of the molding treatment is not lower than 4MPa;
(4) Sequentially carrying out high-temperature sintering and crystallization treatment on the material III to obtain a microcrystalline glass body;
(5) Nano SiO is deposited on the surface of the microcrystalline glass body through chemical vapor deposition 2 Particles to form nano SiO 2 Coating to obtain the microcrystalline glass.
6. The method according to claim 5, wherein in step (1), the conditions of the melt processing include: the temperature is 1600-1700 ℃ and the time is 5-10 hours;
and/or, in the step (1), the mesh number of the sieving is 100-300 mesh;
and/or in the step (2), the average particle size of the material II is 0.5-3mm;
and/or, in step (2), based on the starting materials of the components in the precursor glass composition, tetragonal ZrO 2 The total mass of the whisker and the PVA binder is 4-8wt%.
7. The method of claim 5, wherein in step (3), the conditions of the molding process include: the molding pressure is not lower than 5MPa, preferably 5-30MPa; the dwell time is not less than 20min, preferably 20-60min.
8. The method according to any one of claims 5 to 7, wherein in step (4), the high temperature sintering comprises a stage I and a stage II performed in this order, and the temperature of the stage I is lower than the temperature of the stage II, and the temperature of the stage II is lower than the temperature of the crystallization treatment;
and/or, the conditions of stage I include: the temperature is 400-500 ℃, the heat preservation time is 2-5h, the heating rate is not more than 40 ℃/h, and the preferable heating rate is 20-40 ℃/h;
and/or, the phase II conditions include: the temperature is 630-660 ℃, the heat preservation time is 1-2h, the heating rate is not more than 60 ℃/h, and the preferable heating rate is 30-60 ℃/h;
and/or, the crystallization treatment conditions include: the temperature is 730-770 ℃, the heat preservation time is 0.5-4h, the heating rate is not lower than 120 ℃/h, and the preferable heating rate is 120-300 ℃/h.
9. The method according to any one of claims 5 to 7, wherein in step (5), the deposition temperature of the chemical vapor deposition is 200 to 400 ℃.
10. Use of the glass-ceramic according to any one of claims 1 to 4 in front and rear cover glasses for mobile electronic terminal devices.
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| CN202211505394.7A CN116023033A (en) | 2022-11-28 | 2022-11-28 | Microcrystalline glass and preparation method and application thereof |
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| CN202211505394.7A CN116023033A (en) | 2022-11-28 | 2022-11-28 | Microcrystalline glass and preparation method and application thereof |
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