CN113816611B - Microcrystalline glass for 5G intelligent communication equipment backboard and preparation method thereof - Google Patents
Microcrystalline glass for 5G intelligent communication equipment backboard and preparation method thereof Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 92
- 238000004891 communication Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 16
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 13
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 11
- 239000002241 glass-ceramic Substances 0.000 claims description 27
- 238000002425 crystallisation Methods 0.000 claims description 19
- 230000008025 crystallization Effects 0.000 claims description 19
- 238000000137 annealing Methods 0.000 claims description 17
- 238000002844 melting Methods 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 12
- 238000010899 nucleation Methods 0.000 claims description 10
- 230000006911 nucleation Effects 0.000 claims description 10
- 239000006121 base glass Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000006060 molten glass Substances 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- NWXHSRDXUJENGJ-UHFFFAOYSA-N calcium;magnesium;dioxido(oxo)silane Chemical compound [Mg+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O NWXHSRDXUJENGJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052637 diopside Inorganic materials 0.000 claims description 4
- 229910052634 enstatite Inorganic materials 0.000 claims description 4
- BBCCCLINBSELLX-UHFFFAOYSA-N magnesium;dihydroxy(oxo)silane Chemical compound [Mg+2].O[Si](O)=O BBCCCLINBSELLX-UHFFFAOYSA-N 0.000 claims description 4
- 229910001676 gahnite Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000156 glass melt Substances 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract description 9
- 230000017525 heat dissipation Effects 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 description 22
- 229910052596 spinel Inorganic materials 0.000 description 19
- 239000011029 spinel Substances 0.000 description 19
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052611 pyroxene Inorganic materials 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 238000007496 glass forming Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- -1 magnesium aluminate Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052612 amphibole Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008395 clarifying agent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
- C03C10/0036—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition containing SiO2, Al2O3 and a divalent metal oxide as main constituents
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B32/00—Thermal after-treatment of glass products not provided for in groups C03B19/00, C03B25/00 - C03B31/00 or C03B37/00, e.g. crystallisation, eliminating gas inclusions or other impurities; Hot-pressing vitrified, non-porous, shaped glass products
- C03B32/02—Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Glass Compositions (AREA)
Abstract
The invention relates to microcrystalline glass for a 5G intelligent communication equipment backboard and a preparation method thereof. The microcrystalline glass comprises the following raw materials in percentage by weight: SiO 2 2 35‑40％；ZnO 20‑25％；Al 2 O 3 15‑20％；MgO 5‑10％；CaO 5‑10％；SrO 0.5‑3％；BaO 0.5‑3％；B 2 O 3 0.5‑3％；ZrO 2 0‑5％；TiO 2 5‑10％；Sb 2 O 3 0 to 1 percent. The microcrystalline glass has the characteristics of high hardness (Vickers hardness is more than 8GPa), high strength (bending strength is more than 300MPa), good heat dissipation performance (thermal conductivity is more than 3W/(m.K)), excellent dielectric property (dielectric constant is less than 8, 3GHz) and the like, is suitable for being applied to 5G intelligent communication equipment backplanes, and is low in preparation cost, simple in process and suitable for actual mass production.
Description
Technical Field
The invention relates to microcrystalline glass for a 5G intelligent communication equipment back plate and a preparation method thereof, belonging to the technical field of glass ceramics.
Background
At present, the communication equipment back plate (such as a mobile phone back plate) made of inorganic nonmetal materials on the market mainly comprises high alumina glass and zirconia ceramics.
High alumina glass is excellent in mechanical strength, electrical insulation and chemical stability, but has problems in that the surface hardness is low (mohs hardness of 6), and the surface is easily scratched; secondly, the heat dissipation performance is poor (the heat conductivity coefficient is about 1W/(m.K)), which is not beneficial to the heat dissipation of the communication equipment; in addition, the SiO in the high-alumina glass component 2 And Al 2 O 3 The content is high, the glass melting temperature is high, bubbles and stripes in the glass are not easy to remove, and the preparation difficulty is high.
The zirconia ceramic has high surface hardness, bending strength and fracture toughness, can meet the mechanical property requirement of a communication equipment rear cover, but has a plurality of problems. For example, the dielectric constant of the material is high (about 30), which has a certain effect on electromagnetic wave signals; secondly, the zirconia ceramics have poor heat dissipation performance (the thermal conductivity is about 2W/(m.K)), which is not beneficial to the heat dissipation of communication equipment; besides, the zirconia ceramics need to be processed by nano-scale powder preparation, slurry preparation, granulation, molding, sintering, post-processing and other processes, the preparation process is complex, the yield of products is low (20% -30%), the price is high, and the popularization and the application are not facilitated.
CN104478219A discloses a nano spinel glass ceramics, which comprises the following components by weight percent: SiO 2 2 56-62％；Al 2 O 3 19-23％；MgO 2-6.5％；ZnO 6-15％，ZrO 2 2-7％；TiO 2 2 to 6 percent. The nano spinel microcrystalline glass has the bending strength of 110MPa, the Vickers hardness of 5GPa, the dielectric constant of 5 and the corresponding grain size of 30 nm.
CN108516688A discloses a spinel glass-ceramic prepared by using aluminum ash as main raw material. The microcrystalline glass has a main crystal phase of spinel and a secondary crystal phase of amphibole; the bending strength is 70-90 MPa, the compressive strength is 400-500 MPa, and the Mohs hardness is 7-8.
CN109809696A discloses a magnesium aluminate spinel microcrystalline glass, which comprises the following components in percentage by weight: SiO 2 2 25-60％；Al 2 O 3 20-45％；MgO 8-18％；ZrO 2 0-5％；TiO 2 3-10％；P 2 O 5 0-3％；Li 2 O 0-2％；Na 2 O 0-2％；K 2 O 0-2％；Sb 2 O 3 0.5 to 3 percent. The microcrystalline glass has a main crystal phase of magnesium aluminate spinel and a secondary crystal phase of zirconium titanate; the bending strength is 140-200 MPa, and the Vickers hardness is 910-1000 Hv.
CN111615500A discloses a high hardness and modulus transparent zinc spinel-spinel glass ceramic. The weight percentage composition of the material comprises: SiO 2 2 55.0-70.0％；Al 2 O 3 15.0 to 20.0 percent; 0-10.0% of MgO; 0-12.5% of ZnO, the microcrystalline glass contains various alkali metal oxides, and can be subjected to ion exchangeAnd it must contain one of MgO or ZnO. The microcrystalline glass contains spinel crystals, and the Mohs hardness of the spinel crystals is more than 7.
In summary, the spinel microcrystalline glass disclosed at present is mainly concerned with improving the mechanical properties, especially the hardness. However, when the material is applied to 5G intelligent communication equipment back plates, the material needs to have excellent scratch resistance, and the bending strength, the heat dissipation performance, the dielectric performance and the like of the material need to be considered.
Disclosure of Invention
The invention provides microcrystalline glass for a 5G intelligent communication equipment backboard and a preparation method thereof, aiming at the problems of small hardness, low strength, poor heat dissipation, high dielectric constant and the like of the traditional glass backboard. The preparation method not only can obviously improve the problems, but also has low preparation cost and simple process and is suitable for actual mass production.
The invention adopts the following technical scheme for achieving the purpose:
the microcrystalline glass for the 5G intelligent communication equipment back plate comprises the following raw materials: the weight percentage composition is as follows: SiO 2 2 35-40％；ZnO 20-25％；Al 2 O 3 15-20％；MgO 5-10％；CaO 5-10％；SrO 0.5-3％；BaO 0.5-3％；B 2 O 3 0.5-3％；ZrO 2 0-5％；TiO 2 5-10％；Sb 2 O 3 0-1％。
Further, the preparation method of the microcrystalline glass for the 5G intelligent communication equipment backboard comprises the following steps:
(a) ingredients
Weighing the raw materials according to the weight percentage, and uniformly mixing to obtain the batch.
(b) Melting
And heating the batch to 1500-.
(c) Shaping and annealing
And pouring the molten glass into a pre-preheated copper mold, forming, transferring to an annealing furnace, annealing at the temperature of 500-600 ℃ for 1-2 hours, and cooling to room temperature along with the furnace to obtain the base glass.
(d) Thermal treatment
And (2) putting the basic glass into a crystallization furnace for heat treatment, nucleating at the temperature of 700-750 ℃ for 1-2 hours, crystallizing at the temperature of 950-1000 ℃ for 1-2 hours, and annealing to obtain the glass ceramics, wherein the crystalline phase of the glass ceramics has a complex phase structure of gahnite, enstatite and diopside. Preferably, the nucleation temperature is 720 ℃, and the nucleation time is 2 hours; the crystallization temperature is 950-.
Furthermore, the optimal content of each glass component of the microcrystalline glass is as follows:
SiO 2 is a glass network former oxide. When SiO is present 2 When the content is too high, the melting temperature of the glass is too high, a quartz crystal phase is easy to separate out, and the mechanical property of the microcrystalline glass is poor; when SiO is present 2 When the content is too low, the glass forming ability is poor and crystallization is easy. SiO in the glass component 2 The optimum content is 35-40 wt%.
Al 2 O 3 Is a glass network intermediate oxide. When Al is present 2 O 3 The content is too high, the number of columnar pyroxene crystals is small, the length-diameter ratio of the columnar pyroxene crystals is small, and the mechanical property of the microcrystalline glass is poor; when Al is present 2 O 3 The content is too low, the microcrystalline glass is not easy to be crystallized integrally, and the mechanical property and the heat-conducting property of the microcrystalline glass are influenced. Al in glass component 2 O 3 The optimal content is 15-20 wt%.
ZnO is an important constituent of the zinc spinel crystal phase in the glass-ceramic. The proper increase of the ZnO content is beneficial to the overall crystallization and the improvement of the heat conductivity coefficient of the microcrystalline glass; when the content of ZnO is too high, the crystallization tendency of the microcrystalline glass is increased, the crystallization is easily caused in the glass forming process, and the optimal content of ZnO in the glass component is 20-25 wt%.
MgO and CaO are important components of enstatite and diopside crystal phases in the glass ceramics. When the content of the pyroxene phase and the pyroxene phase is too low, the microcrystalline glass has low fracture toughness; on the contrary, when the content of the two is too high, zinc spinel phase is not favorably separated out, and the microcrystalline glass has low thermal conductivity coefficient. The optimal content of MgO and CaO in the glass component is 5-10 wt%.
BaO and SrO are exonic oxides. The proper amount of the glass ceramics can increase the density of the glass ceramics, improve the heat conductivity coefficient of the glass ceramics and accelerate the melting and the clarification of the glass. The optimum content of BaO and SrO in the glass component is 0.5-3 wt%.
B 2 O 3 The microcrystalline glass mainly has the functions of adjusting the expansion coefficient of a glass phase and preventing the microcrystalline glass from cracking due to the mismatch of the expansion coefficients of the crystal phase and the glass phase; meanwhile, the glass melting agent also plays a role in fluxing and accelerates the melting and the clarification of the glass. Notably, B is 2 O 3 The content should not be too high, otherwise the mechanical properties of the glass-ceramic will be affected. In the glass component B 2 O 3 The optimum content is 0.5-3 wt%.
TiO 2 And ZrO 2 Is a crystal nucleus agent. The crystallization performance of the microcrystalline glass can be obviously improved by properly increasing the content of the nucleating agent, and the microcrystalline glass has excellent mechanical property and heat-conducting property; when the content of the crystal nucleating agent is too high, other unnecessary crystal phases are easy to precipitate in the microcrystalline glass, and the mechanical property and the heat conducting property of the microcrystalline glass are influenced; in addition TiO 2 The content is too high, and the dielectric constant of the microcrystalline glass is large. TiO 2 2 And ZrO 2 The optimum content of the crystal nucleus agent is 5-10 wt% and 0-5 wt%, respectively.
Sb 2 O 3 Is a clarifying agent, and the optimal content is 0-1 wt%.
Furthermore, in each glass component of the microcrystalline glass, SiO is controlled 2 /Al 2 O 3 The mass ratio of (1): 1.8-2.2.
Further, SiO control 2 (CaO + MgO) mass ratio of 1: 2.5-3.4.
Furthermore, the mass sum of ZnO and MgO is controlled to be 22-27 percent of the total mass of all the components of the glass.
More preferably, SiO is controlled in each glass component of the microcrystalline glass 2 /Al 2 O 3 The mass ratio of (1): 1.9-2.1; control of SiO 2 (CaO + MgO) mass ratio of 1: 2.5 to 3.2, and the mass sum of ZnO and MgO is controlled to be 23 to 27 percent of the total mass of all components of the glass.
More preferably, a 5G smartThe microcrystalline glass for the communication equipment back plate is composed of the following raw materials in percentage by weight: SiO 2 2 37％；ZnO 17％；Al 2 O 3 20％；MgO 6％；CaO 8％；SrO 1.2％；BaO 1％；B 2 O 3 1％；ZrO 2 0.8％；TiO 2 7.5％；Sb 2 O 3 0.5％。
Compared with the prior art, the invention has the following beneficial effects:
(1) the spinel microcrystalline glass disclosed at present mainly focuses on improving the hardness of the glass, and the spinel microcrystalline glass provided by the invention has the advantages of high hardness, high strength, high thermal conductivity, low dielectric constant and excellent comprehensive performance.
(2) The mechanical properties of the spinel glass ceramics disclosed are provided mainly by the spinel crystal phase having a high elastic modulus. The microcrystalline glass provided by the invention not only contains a spinel crystal phase with high elastic modulus, but also forms an interlocking microstructure with columnar pyroxene crystals in staggered distribution, and the structure can effectively change the expansion path of the microcrack when the microcrack expands, thereby improving the mechanical strength of the microcrystalline glass.
(3) The gaps among the columnar pyroxene crystals of the microcrystalline glass are filled by spinel crystals with fine grain sizes, the crystals are densely stacked, and the density and the heat conductivity of the microcrystalline glass can be further improved.
(4) The spinel glass ceramics disclosed in the prior art usually incorporate alkali metal oxides to lower the melting temperature of the glass, and the glass ceramics of the present invention use mixed alkaline earth metal oxides instead of alkali metal oxides. The melting temperature of the glass can be reduced, and the reduction of the density of a glass network structure (reduction of mechanical properties) caused by the introduction of alkali metal ions and the influence of the precipitation of the alkali metal ions in the glass material on electronic equipment are avoided.
Through composition design and process optimization, controllable crystallization of various crystals is realized, and the microcrystalline glass is cut and polished to prepare high-hardness, high-strength, high-heat-conductivity and low-dielectric microcrystalline glass with the thickness of less than 0.7mm, so that the microcrystalline glass can be applied to backboards of communication equipment such as 5G smart phones and the like, and meets the performance requirements of wireless charging, chip heat dissipation, scratch resistance, drop resistance and the like.
Detailed Description
In order to better understand the technical content of the invention, specific examples are provided below to further illustrate the invention.
The experimental methods used in the examples of the present invention are all conventional methods unless otherwise specified.
The materials, reagents and the like used in the examples of the present invention are commercially available unless otherwise specified.
A preparation method of microcrystalline glass for a 5G intelligent communication equipment backboard,
the method comprises the following steps:
(a) ingredients
Weighing the following raw materials in percentage by weight: SiO 2 2 35-40％；ZnO 20-25％；Al 2 O 3 15-20％；MgO 5-10％；CaO 5-10％；SrO 0.5-3％；BaO 0.5-3％；B 2 O 3 0.5-3％；ZrO 2 0-5％；TiO 2 5-10％；Sb 2 O 3 0 to 1 percent. The raw materials are uniformly mixed to be used as a batch.
(b) Melting
And heating the batch to 1500-.
(c) Shaping and annealing
And pouring the molten glass into a pre-preheated copper mold, forming, transferring to an annealing furnace, annealing at the temperature of 500-600 ℃ for 1-2 hours, and cooling to room temperature along with the furnace to obtain the base glass.
(d) Thermal treatment
And (2) putting the basic glass into a crystallization furnace for heat treatment, nucleating at the temperature of 700-750 ℃ for 1-2 hours, crystallizing at the temperature of 950-1000 ℃ for 1-2 hours, and annealing to obtain the glass ceramics, wherein the crystalline phase of the glass ceramics has a complex phase structure of gahnite, enstatite and diopside.
Examples 1 to 5
In each example, the raw materials were weighed according to the compositions corresponding to those in table 1 and mixed uniformly; heating to a melting system corresponding to the melting system in the table 2, and melting, clarifying and homogenizing to obtain molten glass; pouring the molten glass into a pre-preheated copper mold, transferring the molded glass to an annealing furnace, annealing at the temperature of 500 ℃ for 1-2 hours, and cooling to room temperature along with the furnace to obtain base glass; the obtained basic glass is put into a crystallization furnace for heat treatment according to the nucleation and crystallization system corresponding to the table 2, and the microcrystalline glass of the invention is obtained after annealing.
Comparative examples 1 to 2
Weighing the raw materials according to the corresponding compositions in the table 1 in each proportion, and uniformly mixing; heating to a melting system corresponding to the melting system in the table 2, and melting, clarifying and homogenizing to obtain molten glass; pouring the molten glass into a pre-preheated copper mold, transferring the molded glass to an annealing furnace, annealing at the temperature of 500 ℃ for 1-2 hours, and cooling to room temperature along with the furnace to obtain base glass; the obtained base glass is put into a crystallization furnace to be subjected to heat treatment according to the nucleation and crystallization system corresponding to the table 2, and the microcrystalline glass of the comparative example is obtained after annealing.
TABLE 1 compositions and control requirements (unit: wt%) of examples and comparative examples
TABLE 2 preparation Process and Performance parameters of the examples and comparative examples
TABLE 3 Properties of crystallized glasses obtained in examples and comparative examples
As is clear from the data of the examples in Table 2, the glass-ceramics of the present invention 1 to 5 are characterized by high hardness (Vickers hardness > 8GPa), high strength (bending strength > 300MPa), good heat dissipation properties (thermal conductivity > 3W/(m.K)), and excellent dielectric properties (dielectric constant < 8, 3 GHz).
Comparative example 1 SiO in comparison with example 2 2 Addition of excess amounts, with simultaneous induction of "SiO 2 /Al 2 O 3 And SiO 2 The mass ratio of CaO + MgO exceeds the control range, so that the prepared microcrystalline glass has low bending strength and thermal conductivity and high dielectric constant.
Compared with example 2, the nucleation and crystallization temperatures of comparative example 2 are out of the control range, resulting in poor bending strength, low thermal conductivity and low vickers hardness of the obtained glass-ceramic.
The above specific examples of the crystallized glass of the present invention are given by way of illustration only for illustrating the performance of the crystallized glass of the present invention, and are not intended to limit the embodiments of the present invention. Variations or modifications in other variations will be apparent to persons skilled in the art based on the foregoing description. All embodiments are not necessarily or exclusively enumerated herein. And such obvious variations or modifications are intended to be included within the scope of the present invention as expressed in the following claims.
Claims (8)
1. The microcrystalline glass for the 5G intelligent communication equipment backboard is characterized by comprising the following raw materials in percentage by weight: SiO 2 2 35-40％；ZnO 17-22％；Al 2 O 3 15-20％；MgO 5-10％；CaO 5-10％；SrO 0.5-3％；BaO 0.5-3％；B 2 O 3 0.5-3％；ZrO 2 0-5％；TiO 2 5-10％；Sb 2 O 3 0 to 1 percent; SiO in the raw material composition 2 And Al 2 O 3 The mass ratio of (1): 1.8-2.2; SiO in the raw material composition 2 The mass of the CaO-MgO is 2.5 to 3.2 times of the total mass of the CaO and the MgO;
the preparation method of the microcrystalline glass for the 5G intelligent communication equipment backboard comprises the following steps: firstly, mixing and melting raw materials to prepare molten glass; preparing base glass from the molten glass; finally, putting the base glass into a crystallization furnace for nucleation and crystallization heat treatment, wherein the nucleation temperature is 700-750 ℃, and the nucleation time is 1-2 hours; the crystallization temperature is 950 ℃ and 1000 ℃, and the crystallization time is 1-2 hours; and annealing to obtain the target glass ceramics.
2. The glass-ceramic according to claim 1, wherein the sum of the mass of ZnO and MgO in the raw material composition is 22 to 27% of the total mass of the glass-ceramic raw materials.
3. The glass-ceramic according to claim 2,
SiO in the raw material composition 2 And Al 2 O 3 The mass ratio of (1): 1.9-2.1;
SiO in the raw material composition 2 The mass of the CaO-MgO is 2.5 to 3.2 times of the total mass of the CaO and the MgO;
the sum of the mass of ZnO and MgO in the raw material composition is 23-27% of the total mass of the microcrystalline glass raw material.
4. The microcrystalline glass according to claim 3, wherein the microcrystalline glass consists of the following raw materials in percentage by weight: SiO 2 2 37％；ZnO 17％；Al 2 O 3 20％；MgO 6％；CaO 8％；SrO 1.2％；BaO 1％；B 2 O 3 1％；ZrO 2 0.8％；TiO 2 7.5％；Sb 2 O 3 0.5％。
5. The glass-ceramic according to claim 1, wherein the crystalline phase of the glass-ceramic has a complex phase structure of gahnite, enstatite and diopside.
6. The glass-ceramic according to claim 1, wherein the nucleation temperature is 720 ℃ and the nucleation time is 2 hours; the crystallization temperature is 950-.
7. The glass-ceramic according to claim 6, wherein the melting temperature is 1500-.
8. The microcrystalline glass according to claim 7, wherein the glass melt is used for preparing a base glass by the following specific operation steps: and pouring the molten glass into a pre-preheated copper mold, forming, transferring to an annealing furnace, annealing at the temperature of 500-600 ℃ for 1-2 hours, and cooling to room temperature along with the furnace to obtain the base glass.
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| JPH05116986A (en) * | 1991-02-27 | 1993-05-14 | Sumitomo Metal Mining Co Ltd | Opaque glass and sintered and laminated ceramic wiring board obtained therefrom |
| US5476821A (en) * | 1994-11-01 | 1995-12-19 | Corning Incorporated | High modulus glass-ceramics containing fine grained spinel-type crystals |
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