CN110482866A - Crystallized glass article, devitrified glass and its manufacturing method - Google Patents

Crystallized glass article, devitrified glass and its manufacturing method Download PDF

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CN110482866A
CN110482866A CN201910774198.1A CN201910774198A CN110482866A CN 110482866 A CN110482866 A CN 110482866A CN 201910774198 A CN201910774198 A CN 201910774198A CN 110482866 A CN110482866 A CN 110482866A
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glass
sio
component
devitrified
host
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CN110482866B (en
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原保平
于天来
陈雪梅
聂小兵
刘振禹
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Chengdu Guangming Optoelectronics Co Ltd
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Chengdu Guangming Optoelectronics Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C10/00—Devitrified glass ceramics, i.e. glass ceramics having a crystalline phase dispersed in a glassy phase and constituting at least 50% by weight of the total composition
    • C03C10/0018—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 monovalent metal oxide as main constituents
    • C03C10/0027—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 monovalent metal oxide as main constituents containing SiO2, Al2O3, Li2O as main constituents

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

The present invention provides a kind of crystallized glass article, and the component of the crystallized glass article in terms of weight percentage, contains: SiO2: 50~59.5%；Al2O3: 15~25%；Li2O:4~10%；Na2O:5~15%；P2O5: 0.1~10%；ZrO2: 0~10%.It is designed by reasonable component, so that crystallized glass article of the invention has high transmitance and low mist degree, is suitable for electronic equipment or display equipment.

Description

Crystallized glass article, devitrified glass and its manufacturing method
Technical field
The present invention relates to a kind of crystallized glass article and devitrified glass, more particularly to a kind of high transmittance, low haze Crystallized glass article, devitrified glass and its manufacturing method.
Background technique
Devitrified glass is a kind of material that crystallization is precipitated in inside glass and being heat-treated to host glass, is had Mechanical performance more higher than host glass, and due to forming crystallite in glass, toughness, wear-resisting property etc. are relative to general Glass have apparent advantage, and higher intensity is further obtained by chemical strengthening.
Based on the above advantage, has at present and devitrified glass or crystallized glass article are applied to drop resistant, resistance to compression, scratch-resistant requirement height Display equipment or electronic equipment in.Due to containing the crystal of certain content in devitrified glass, the mist degree of glass can be improved, is reduced The transmitance of glass is unfavorable for the use to the demanding equipment of transmitance.Therefore a intensity with higher, ground fog are developed The crystallized glass article of degree and high transmitance, the target pursued at numerous scientific research personnel.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of intensity with higher, low haze and high transmitances Crystallized glass article.
The present invention solve technical problem the technical solution adopted is that:
(1) crystallized glass article, component in terms of weight percentage, contain: SiO2: 50~59.5%；Al2O3: 15~ 25%；Li2O:4~10%；Na2O:5~15%；P2O5: 0.1~10%；ZrO2: 0~10%.
(2) crystallized glass article according to (1), component in terms of weight percentage, also contain: ZnO:0~ 10%；And/or MgO:0~10%；And/or K2O:0~10%；And/or SrO:0~5%；And/or BaO:0~5%；And/or TiO2: 0~5%；And/or Y2O3: 0~5%；And/or B2O3: 0~6%；And/or clarifying agent: 0~2%.
(3) crystallized glass article, component contain SiO2、Al2O3、Li2O and Na2O, component in terms of weight percentage, Wherein (Li2O+Na2O)/(SiO2+Al2O3) be 0.15~0.35,0.55mm thickness crystallized glass article mist degree be 0.3% with Under.
(4) crystallized glass article contains SiO2、Al2O3、Li2O and Na2O is as necessary component, the crystallized glass article Falling ball impact test height be 1000mm or more.
(5) according to any crystallized glass article in (3)~(4), component in terms of weight percentage, contains: SiO2: 50~59.5%；Al2O3: 15~25%；Li2O:4~10%；Na2O:5~15%；P2O5: 0.1~10%；ZrO2: 0~ 10%；ZnO:0~10%；MgO:0~10%；K2O:0~10%；SrO:0~5%；BaO:0~5%；TiO2: 0~5%； Y2O3: 0~5%；B2O3: 0~6%；Clarifying agent: 0~2%.
(6) according to any crystallized glass article in (1)~(5), component in terms of weight percentage, contains: SiO2: 52~58%；And/or Al2O3: 16~23%；And/or Li2O:4~8%；And/or Na2O:8~12%；And/or P2O5: 0.5~5%；And/or ZrO2: 0.1~10%；And/or ZnO:1~8%；And/or MgO:0.5~5%；And/or K2O:0~ 5%；And/or SrO:0~1%；And/or BaO:0~1%；And/or TiO2: 0~1%；And/or Y2O3: 0~1%；And/or B2O3: 0.1~4%；And/or clarifying agent: 0~1%.
(7) according to any crystallized glass article in (1)~(6), component in terms of weight percentage, contains: ZrO2: 0.5~6%, preferably ZrO2: 1~4%；And/or Li2O:5~7%；And/or P2O5: 1~4%.
(8) according to any crystallized glass article in (1)~(7), component in terms of weight percentage, (Li2O+ Na2O)/(SiO2+Al2O3) it is 0.15~0.35, preferably (Li2O+Na2O)/(SiO2+Al2O3) it is 0.16~0.32, more preferably (Li2O+Na2O)/(SiO2+Al2O3) it is 0.17~0.30.
(9) according to any crystallized glass article in (1)~(8), component in terms of weight percentage, (Li2O+ Na2O)/Al2O3It is 0.5~1.4, preferably (Li2O+Na2O)/Al2O3It is 0.53~1.3, more preferable (Li2O+Na2O)/Al2O3 It is 0.55~1.2.
(10) according to any crystallized glass article in (1)~(9), component in terms of weight percentage, Li2O/ Na2O is 0.28~1.2, preferably Li2O/Na2O is 0.29~1.1, more preferable Li2O/Na2O is 0.30~1.0.
(11) according to any crystallized glass article in (1)~(10), the mist degree of the crystallized glass article of 0.55mm thickness For 0.3% hereinafter, preferably 0.25% hereinafter, more preferably 0.2% or less；And/or the crystallized glass article of 0.55mm thickness, The mean transmissivity of 400~800nm wavelength is 85% or more, preferably 88% or more, more preferably 90% or more；And/or The crystallized glass article of 0.55mm thickness, the transmitance of 550nm wavelength are 85% or more, preferably 89% or more, more preferably 91% or more.
(12) according to any crystallized glass article in (1)~(11), the surface stress of the crystallized glass article is 300MPa or more, preferably 500MPa or more, more preferably 700MPa or more；And/or ion exchange layer depth is 10 μm or more, Preferably 15 μm or more, more preferable 20 μm or more, further preferably 25 μm or more.
(13) according to any crystallized glass article in (1)~(12), the falling ball impact test of the crystallized glass article is high Degree is 1000mm or more, preferably 1100mm or more, more preferably 1200nm or more；And/or fracture toughness is 1MPam1/2With On, preferably 1.3MPam1/2More than, more preferably 1.5MPam1/2More than；And/or Vickers hardness (Hv) it is 600kgf/mm2 More than, preferably 650kgf/mm2More than, more preferably 700kgf/mm2More than.
(14) according to any crystallized glass article in (1)~(13), the crystallinity of the crystallized glass article is 20% or more, preferably 30% or more, more preferably 40% or more, further preferably 50% or more；And/or crystallite dimension is 70nm hereinafter, preferably 50nm hereinafter, more preferably 40nm hereinafter, further preferably 30nm hereinafter, still more preferably 20nm or less.
(15) according to any crystallized glass article in (1)~(14), the crystal phase of the crystallized glass article contains one Lithium metasilicate；And/or aluminum phosphate；And/or aluminium metaphosphate；And/or lithium phosphate；And/or quartz crystal；And/or zirconium silicate crystal.
(16) according to any crystallized glass article in (1)~(15), the crystallized glass article also contains colorant, It can make crystallized glass article that different colours be presented.
(17) crystallized glass article according to (16), colorant in terms of weight percentage, contain: NiO:0~ 4%；And/or Ni2O3: 0~4%；And/or CoO:0~2%；And/or Co2O3: 0~2%；And/or Fe2O3: 0~7%；And/or MnO2: 0~4%；And/or Er2O3: 0~8%；And/or Nd2O3: 0~8%；And/or Cu2O:0~4%；And/or Pr2O5: 0~ 8%；And/or CeO2: 0~4%.
(18) according to any crystallized glass article in (16)~(17), colorant in terms of weight percentage, contains Have: NiO:0.1~3%；And/or Ni2O3: 0.1~3%；And/or CoO:0.05~1.8%；And/or Co2O3: 0.05~ 1.8%；And/or Fe2O3: 0.2~5%；And/or MnO2: 0.1~3%；And/or Er2O3: 0.4~6%；And/or Nd2O3: 0.4 ~6%；And/or Cu2O:0.5~3%；And/or Pr2O5: 0.4~6%；And/or CeO2: 0.5~3%.
The present invention also provides a kind of devitrified glasses.
The present invention solve technical problem the technical solution adopted is that:
(19) devitrified glass, component in terms of weight percentage, contain: SiO2: 50~59.5%；Al2O3: 15~ 25%；Li2O:4~10%；Na2O:5~15%；P2O5: 0.1~10%；ZrO2: 0~10%.
(20) devitrified glass according to power (19), component in terms of weight percentage, also contain: ZnO:0~ 10%；And/or MgO:0~10%；And/or K2O:0~10%；And/or SrO:0~5%；And/or BaO:0~5%；And/or TiO2: 0~5%；And/or Y2O3: 0~5%；And/or B2O3: 0~6%；And/or clarifying agent: 0~2%.
(21) devitrified glass, component contain SiO2、Al2O3、Li2O and Na2O, component in terms of weight percentage, In (Li2O+Na2O)/(SiO2+Al2O3) it be the mist degree of devitrified glass of 0.15~0.35,0.55mm thickness is 0.3% or less.
(22) devitrified glass according to (21), component in terms of weight percentage, contain: SiO2: 50~ 59.5%；Al2O3: 15~25%；Li2O:4~10%；Na2O:5~15%；P2O5: 0.1~10%；ZrO2: 0~10%； ZnO:0~10%；MgO:0~10%；K2O:0~10%；SrO:0~5%；BaO:0~5%；TiO2: 0~5%；Y2O3: 0~ 5%；B2O3: 0~6%；Clarifying agent: 0~2%.
(23) according to any devitrified glass in (19)~(22), component in terms of weight percentage, contains: SiO2: 52~58%；And/or Al2O3: 16~23%；And/or Li2O:4~8%；And/or Na2O:8~12%；And/or P2O5: 0.5~5%；And/or ZrO2: 0.1~10%；And/or ZnO:1~8%；And/or MgO:0.5~5%；And/or K2O:0~ 5%；And/or SrO:0~1%；And/or BaO:0~1%；And/or TiO2: 0~1%；And/or Y2O3: 0~1%；And/or B2O3: 0.1~4%；And/or clarifying agent: 0~1%.
(24) according to any devitrified glass in (19)~(23), component in terms of weight percentage, contains: ZrO2: 0.5~6%, preferably ZrO2: 1~4%；And/or Li2O:5~7%；And/or P2O5: 1~4%.
(25) according to any devitrified glass in (19)~(24), component in terms of weight percentage, (Li2O+ Na2O)/(SiO2+Al2O3) it is 0.15~0.35, preferably (Li2O+Na2O)/(SiO2+Al2O3) it is 0.16~0.32, more preferably (Li2O+Na2O)/(SiO2+Al2O3) it is 0.17~0.30.
(26) according to any devitrified glass in (19)~(24), component in terms of weight percentage, (Li2O+ Na2O)/Al2O3It is 0.5~1.4, preferably (Li2O+Na2O)/Al2O3It is 0.53~1.3, more preferable (Li2O+Na2O)/Al2O3 It is 0.55~1.2.
(27) according to any devitrified glass in (19)~(26), component in terms of weight percentage, Li2O/Na2O It is 0.28~1.2, preferably Li2O/Na2O is 0.29~1.1, more preferable Li2O/Na2O is 0.30~1.0.
(28) according to any devitrified glass in (19)~(27), the mist degree of the devitrified glass of 0.55mm thickness is 0.3% Hereinafter, preferably 0.25% hereinafter, more preferably 0.2% or less；And/or the devitrified glass of 0.55mm thickness, 400~800nm wave Long mean transmissivity is 85% or more, preferably 88% or more, more preferably 90% or more；And/or the crystallite of 0.55mm thickness Glass, the transmitance of 550nm wavelength are 85% or more, preferably 89% or more, more preferably 91% or more.
(29) according to any devitrified glass in (19)~(28), the crystallinity of the devitrified glass is 20% or more, Preferably 30% or more, more preferably 40% or more, further preferably 50% or more；And/or crystallite dimension be 70nm hereinafter, Preferably 50nm hereinafter, more preferably 40nm hereinafter, further preferably 30nm hereinafter, still more preferably 20nm or less.
(30) according to any devitrified glass in (19)~(29), the refractive index (nd) of the devitrified glass is 1.500 ~1.540, preferably 1.510~1.530；And/or thermal expansion coefficient (α20℃-120℃) it is 70~120 × 10-7/ K, preferably 86 ~100 × 10-7/K。
(31) according to any devitrified glass in (19)~(30), the crystal phase of the devitrified glass contains a lithium metasilicate； And/or aluminum phosphate；And/or aluminium metaphosphate；And/or lithium phosphate；And/or quartz crystal；And/or zirconium silicate crystal.
(32) according to any devitrified glass in (19)~(31), the devitrified glass also contains colorant, can make micro- Different colours are presented in crystal glass.
(33) devitrified glass according to (32), colorant in terms of weight percentage, contain: NiO:0~4%； And/or Ni2O3: 0~4%；And/or CoO:0~2%；And/or Co2O3: 0~2%；And/or Fe2O3: 0~7%；And/or MnO2: 0~4%；And/or Er2O3: 0~8%；And/or Nd2O3: 0~8%；And/or Cu2O:0~4%；And/or Pr2O5: 0~ 8%；And/or CeO2: 0~4%.
(34) according to any devitrified glass in (32)~(33), colorant in terms of weight percentage, contains: NiO:0.1~3%；And/or Ni2O3: 0.1~3%；And/or CoO:0.05~1.8%；And/or Co2O3: 0.05~1.8%； And/or Fe2O3: 0.2~5%；And/or MnO2: 0.1~3%；And/or Er2O3: 0.4~6%；And/or Nd2O3: 0.4~6%； And/or Cu2O:0.5~3%；And/or Pr2O5: 0.4~6%；And/or CeO2: 0.5~3%.
The present invention also provides a kind of host glasses.
The present invention solve technical problem the technical solution adopted is that:
(35) host glass, component in terms of weight percentage, contain: SiO2: 50~59.5%；Al2O3: 15~ 25%；Li2O:4~10%；Na2O:5~15%；P2O5: 0.1~10%；ZrO2: 0~10%.
(36) host glass according to (34), component in terms of weight percentage, also contain: ZnO:0~10%； And/or MgO:0~10%；And/or K2O:0~10%；And/or SrO:0~5%；And/or BaO:0~5%；And/or TiO2: 0 ~5%；And/or Y2O3: 0~5%；And/or B2O3: 0~6%；And/or clarifying agent: 0~2%.
(37) according to (35) or (36) any host glass, component in terms of weight percentage, contains: SiO2: 52~58%；And/or Al2O3: 16~23%；And/or Li2O:4~8%；And/or Na2O:8~12%；And/or P2O5: 0.5~5%；And/or ZrO2: 0.1~10%；And/or ZnO:1~8%；And/or MgO:0.5~5%；And/or K2O:0~ 5%；And/or SrO:0~1%；And/or BaO:0~1%；And/or TiO2: 0~1%；And/or Y2O3: 0~1%；And/or B2O3: 0.1~4%；And/or clarifying agent: 0~1%.
(38) according to any host glass in (35)~(37), component in terms of weight percentage, contains: ZrO2: 0.5~6%, preferably ZrO2: 1~4%；And/or Li2O:5~7%；And/or P2O5: 1~4%.
(39) according to any host glass in (35)~(38), component in terms of weight percentage, (Li2O+ Na2O)/(SiO2+Al2O3) it is 0.15~0.35, preferably (Li2O+Na2O)/(SiO2+Al2O3) it is 0.16~0.32, more preferably (Li2O+Na2O)/(SiO2+Al2O3) it is 0.17~0.30.
(40) according to any host glass in (35)~(39), component in terms of weight percentage, (Li2O+ Na2O)/Al2O3It is 0.5~1.4, preferably (Li2O+Na2O)/Al2O3It is 0.53~1.3, more preferable (Li2O+Na2O)/Al2O3 It is 0.55~1.2.
(41) according to any host glass in (35)~(40), component in terms of weight percentage, Li2O/Na2O It is 0.28~1.2, preferably Li2O/Na2O is 0.29~1.1, more preferable Li2O/Na2O is 0.30~1.0.
(42) according to any host glass in (35)~(41), the refractive index (nd) of the host glass is 1.500 ~1.530, preferably 1.505~1.525；And/or thermal expansion coefficient (α20℃-120℃) it is 60~85 × 10-7/ K, preferably 70~ 85×10-7/K。
(43) according to any host glass in (35)~(42), the host glass also contains colorant, can make micro- Different colours are presented in crystal glass product.
(44) host glass according to (43), colorant in terms of weight percentage, contain: NiO:0~4%； And/or Ni2O3: 0~4%；And/or CoO:0~2%；And/or Co2O3: 0~2%；And/or Fe2O3: 0~7%；And/or MnO2: 0~4%；And/or Er2O3: 0~8%；And/or Nd2O3: 0~8%；And/or Cu2O:0~4%；And/or Pr2O5: 0~ 8%；And/or CeO2: 0~4%.
(45) according to any host glass in (43)~(44), colorant in terms of weight percentage, contains: NiO:0.1~3%；And/or Ni2O3: 0.1~3%；And/or CoO:0.05~1.8%；And/or Co2O3: 0.05~1.8%； And/or Fe2O3: 0.2~5%；And/or MnO2: 0.1~3%；And/or Er2O3: 0.4~6%；And/or Nd2O3: 0.4~6%； And/or Cu2O:0.5~3%；And/or Pr2O5: 0.4~6%；And/or CeO2: 0.5~3%.
The present invention also provides a kind of glass cover-plates.
(46) glass cover-plate is made of any crystallized glass article in (1)~(18), and/or use (19)~ (34) any devitrified glass is made, and/or is made of any host glass in (35)~(45).
The present invention also provides a kind of glass components.
(47) glass component is made of any crystallized glass article in (1)~(18), and/or uses (19) Any devitrified glass in~(34) is made, and/or is made of any host glass in (35)~(45).
The present invention also provides a kind of glass display devices.
(48) equipment is shown, including any crystallized glass article in (1)~(18), and/or including (19)~(34) Any devitrified glass, and/or including any host glass in (35)~(45), and/or including described in (46) Glass cover-plate.
The present invention also provides a kind of electronic equipment.
(49) electronic equipment, including any crystallized glass article in (1)~(18), and/or including (19)~(34) Any devitrified glass, and/or including any host glass in (35)~(45), and/or including described in (46) Glass cover-plate, and/or including glass component described in (47).
The present invention also provides a kind of manufacturing method of crystallized glass article.
(50) manufacturing method of crystallized glass article, the described method comprises the following steps:
Host glass is formed, component in terms of weight percentage, contains: SiO2: 50~59.5%；Al2O3: 15~ 25%；Li2O:4~10%；Na2O:5~15%；P2O5: 0.1~10%；ZrO2: 0~10%；ZnO:0~10%；MgO:0~ 10%；K2O:0~10%；SrO:0~5%；BaO:0~5%；TiO2: 0~5%；Y2O3: 0~5%；B2O3: 0~6%；Clarification Agent: 0~2%.
Devitrified glass is formed by crystallization process to the host glass, then chemical strengthening work is passed through to the devitrified glass Skill forms crystallized glass article.
(51) manufacturing method of the crystallized glass article according to (50), the host glass, component is with weight hundred Divide than indicating, contains: SiO2: 52~58%；And/or Al2O3: 16~23%；And/or Li2O:4~8%, preferably Li2O:5~ 7%；And/or Na2O:8~12%；And/or P2O5: 0.5~5%；And/or ZrO2: 0.1~10%, preferably ZrO2: 0.5~6%, More preferable ZrO2: 1~4%；And/or ZnO:1~8%；And/or MgO:0.5~5%；And/or K2O:0~5%；And/or SrO:0 ~1%；And/or BaO:0~1%；And/or TiO2: 0~1%；And/or Y2O3: 0~1%；And/or B2O3: 0.1~4%；With/ Or clarifying agent: 0~1%；And/or (Li2O+Na2O)/(SiO2+Al2O3) it is 0.15~0.35, preferably (Li2O+Na2O)/(SiO2+ Al2O3) it is 0.16~0.32, more preferable (Li2O+Na2O)/(SiO2+Al2O3) it is 0.17~0.30；And/or (Li2O+Na2O)/ Al2O3It is 0.5~1.4, preferably (Li2O+Na2O)/Al2O3It is 0.53~1.3, more preferable (Li2O+Na2O)/Al2O3It is 0.55 ~1.2；And/or Li2O/Na2O is 0.28~1.2, preferably Li2O/Na2O is 0.29~1.1, more preferable Li2O/Na2O is 0.30 ~1.0.
(52) according to the manufacturing method of (50) or (51) any crystallized glass article, the host glass, group Divide in terms of weight percentage, contains: NiO:0~4%；And/or Ni2O3: 0~4%；And/or CoO:0~2%；And/or Co2O3: 0~2%；And/or Fe2O3: 0~7%；And/or MnO2: 0~4%；And/or Er2O3: 0~8%；And/or Nd2O3: 0~ 8%；And/or Cu2O:0~4%；And/or Pr2O5: 0~8%；And/or CeO2: 0~4%.
(53) according to the manufacturing method of any crystallized glass article in (50)~(52), the host glass, group Divide in terms of weight percentage, contains: NiO:0.1~3%；And/or Ni2O3: 0.1~3%；And/or CoO:0.05~1.8%； And/or Co2O3: 0.05~1.8%；And/or Fe2O3: 0.2~5%；And/or MnO2: 0.1~3%；And/or Er2O3: 0.4~ 6%；And/or Nd2O3: 0.4~6%；And/or Cu2O:0.5~3%；And/or Pr2O5: 0.4~6%；And/or CeO2: 0.5~ 3%.
(54) according to the manufacturing method of any crystallized glass article in (50)~(53), the crystallization process include with Lower step: its temperature is kept for the regular hour after reaching heat treatment temperature by Crystallizing treatment temperature as defined in being warming up to, Then cool down again.The temperature of the Crystallizing treatment be 480~700 DEG C, preferably 520~600 DEG C, at a temperature of Crystallizing treatment Retention time be 0~8 hour, preferably 1~6 hour.
(55) according to the manufacturing method of any crystallized glass article in (50)~(53), the crystallization process include with Lower step: carrying out the processing of nucleation technique at a temperature of the 1st, then carries out at a temperature of the higher than nucleation technological temperature the 2nd brilliant The processing of body growth technique.
(56) manufacturing method of the crystallized glass article according to (55), the crystallization process is the following steps are included: the 1st Temperature is 480~550 DEG C, and the 2nd temperature is 550~700 DEG C；Retention time at a temperature of the 1st is 0~24 hour, preferably 2 ~15 hours；Retention time at a temperature of the 2nd is 0~10 hour, preferably 0.5~6 hour.
(57) according to the manufacturing method of any crystallized glass article in (50)~(56), the chemical strengthening technique packet Include: devitrified glass is immersed in the salt bath of the melting Na salt of 430 DEG C~470 DEG C of temperature 6~20 hours, and preferred range is 435 DEG C~460 DEG C, preferably time range is 8~13 hours；And/or devitrified glass is immersed at a temperature of 400 DEG C~450 DEG C It melts in the salt bath of K salt 1~8 hour, preferably time range is 2~4 hours.
(58) manufacturing method of any crystallized glass article in basis (50)~(57), the crystallized glass article Crystal phase contains a lithium metasilicate；And/or aluminum phosphate；And/or aluminium metaphosphate；And/or lithium phosphate；And/or quartz crystal；And/or silicon Sour zirconium crystal.
(59), according to the manufacturing method of any crystallized glass article in (50)~(58), the crystallite glass of 0.55mm thickness The mist degree of glass product is for 0.3% hereinafter, preferably 0.25% hereinafter, more preferably 0.2% or less；And/or 0.55mm thickness is micro- Crystal glass product, the mean transmissivity of 400~800nm wavelength are 85% or more, preferably 88% or more, more preferably 90% with On；And/or the crystallized glass article of 0.55mm thickness, the transmitance of 550nm wavelength are 85% or more, preferably 89% or more, more Preferably 91% or more；And/or the surface stress of crystallized glass article be 300MPa or more, preferably 500MPa or more, it is more excellent It is selected as 700MPa or more；And/or the ion exchange layer depth of crystallized glass article be 10 μm or more, preferably 15 μm or more, more It is preferred that 20 μm or more, further preferably 25 μm or more；And/or the falling ball impact test height of crystallized glass article be 1000mm with On, preferably 1100mm or more, more preferably 1200nm or more；And/or the fracture toughness of crystallized glass article is 1MPam1/2 More than, preferably 1.3MPam1/2More than, more preferably 1.5MPam1/2More than；And/or the Vickers of crystallized glass article is hard Spend (Hv) it is 600kgf/mm2More than, preferably 650kgf/mm2More than, more preferably 700kgf/mm2More than；And/or crystallite glass The crystallite dimension of glass product be 70nm hereinafter, preferably 50nm hereinafter, more preferably 40nm hereinafter, further preferably 30nm with Under, still more preferably 20nm or less.
(60) manufacturing method of any crystallized glass article in basis (50)~(59), the crystallized glass article Crystallinity is 20% or more, preferably 30% or more, more preferably 40% or more, further preferably 50% or more.
The present invention also provides a kind of manufacturing method of devitrified glass.
(61) manufacturing method of devitrified glass, the described method comprises the following steps:
Host glass is formed, component in terms of weight percentage, contains: SiO2: 50~59.5%；Al2O3: 15~ 25%；Li2O:4~10%；Na2O:5~15%；P2O5: 0.1~10%；ZrO2: 0~10%；ZnO:0~10%；MgO:0~ 10%；K2O:0~10%；SrO:0~5%；BaO:0~5%；TiO2: 0~5%；Y2O3: 0~5%；B2O3: 0~6%；Clarification Agent: 0~2%.
Devitrified glass is formed by crystallization process to the host glass.
(62) manufacturing method of the devitrified glass according to (61), the host glass, component is with weight percent It indicates, contains: SiO2: 52~58%；And/or Al2O3: 16~23%；And/or Li2O:4~8%, preferably Li2O:5~7%； And/or Na2O:8~12%；And/or P2O5: 0.5~5%；And/or ZrO2: 0.1~10%, preferably ZrO2: 0.5~6%, it is more excellent Select ZrO2: 1~4%；And/or ZnO:1~8%；And/or MgO:0.5~5%；And/or K2O:0~5%；And/or SrO:0~ 1%；And/or BaO:0~1%；And/or TiO2: 0~1%；And/or Y2O3: 0~1%；And/or B2O3: 0.1~4%；And/or Clarifying agent: 0~1%；And/or (Li2O+Na2O)/(SiO2+Al2O3) it is 0.15~0.35, preferably (Li2O+Na2O)/(SiO2+ Al2O3) it is 0.16~0.32, more preferable (Li2O+Na2O)/(SiO2+Al2O3) it is 0.17~0.30；And/or (Li2O+Na2O)/ Al2O3It is 0.5~1.4, preferably (Li2O+Na2O)/Al2O3It is 0.53~1.3, more preferable (Li2O+Na2O)/Al2O3It is 0.55 ~1.2；And/or Li2O/Na2O is 0.28~1.2, preferably Li2O/Na2O is 0.29~1.1, more preferable Li2O/Na2O is 0.30 ~1.0.
(63) according to the manufacturing method of (60) or (61) any devitrified glass, the host glass, component with Weight percent indicates, contains: NiO:0~4%；And/or Ni2O3: 0~4%；And/or CoO:0~2%；And/or Co2O3: 0 ~2%；And/or Fe2O3: 0~7%；And/or MnO2: 0~4%；And/or Er2O3: 0~8%；And/or Nd2O3: 0~8%； And/or Cu2O:0~4%；And/or Pr2O5: 0~8%；And/or CeO2: 0~4%.
(64) according to the manufacturing method of (60) or (61) any devitrified glass, the host glass, component with Weight percent indicates, contains: NiO:0.1~3%；And/or Ni2O3: 0.1~3%；And/or CoO:0.05~1.8%；With/ Or Co2O3: 0.05~1.8%；And/or Fe2O3: 0.2~5%；And/or MnO2: 0.1~3%；And/or Er2O3: 0.4~6%； And/or Nd2O3: 0.4~6%；And/or Cu2O:0.5~3%；And/or Pr2O5: 0.4~6%；And/or CeO2: 0.5~3%.
(65) according to the manufacturing method of any devitrified glass in (60)~(64), the crystallization process includes following step Rapid: its temperature is kept for the regular hour, then after reaching heat treatment temperature by Crystallizing treatment temperature as defined in being warming up to Cool down again.The temperature of the Crystallizing treatment be 480~700 DEG C, preferably 520~600 DEG C, guarantor at a temperature of Crystallizing treatment Holding the time is 0~8 hour, preferably 1~6 hour.
(66) according to the manufacturing method of any devitrified glass in (60)~(64), the crystallization process includes following step It is rapid: the processing of nucleation technique to be carried out at a temperature of the 1st, it is raw then to carry out crystal at a temperature of the higher than nucleation technological temperature the 2nd The processing of long technique.
(67) manufacturing method of the devitrified glass according to (66), the crystallization process is the following steps are included: the 1st temperature It is 480~550 DEG C, the 2nd temperature is 550~700 DEG C；Retention time at a temperature of the 1st is 0~24 hour, preferably 2~15 Hour；Retention time at a temperature of the 2nd is 0~10 hour, preferably 0.5~6 hour.
(68) according to the manufacturing method of any devitrified glass in (60)~(67), the crystal phase of the devitrified glass contains One lithium metasilicate；And/or aluminum phosphate；And/or aluminium metaphosphate；And/or lithium phosphate；And/or quartz crystal；And/or zirconium silicate crystal.
(69) according to the manufacturing method of any devitrified glass in (60)~(68), the mist of the devitrified glass of 0.55mm thickness Degree is for 0.3% hereinafter, preferably 0.25% hereinafter, more preferably 0.2% or less；And/or the crystallized glass article of 0.55mm thickness, The mean transmissivity of 400~800nm wavelength is 85% or more, preferably 88% or more, more preferably 90% or more；And/or The crystallized glass article of 0.55mm thickness, the transmitance of 550nm wavelength are 85% or more, preferably 89% or more, more preferably 91% or more；And/or the crystallite dimension of devitrified glass be 70nm hereinafter, preferably 50nm hereinafter, more preferably 40nm hereinafter, into One step is preferably 30nm hereinafter, still more preferably 20nm or less；And/or thermal expansion coefficient (the α of devitrified glass20℃-120℃) be 70~120 × 10-7/ K, preferably 86~100 × 10-7/K。
(70) according to the manufacturing method of any devitrified glass in (60)~(69), the crystallinity of the devitrified glass is 20% or more, preferably 30% or more, more preferably 40% or more, further preferably 50% or more.
The beneficial effects of the present invention are: being designed by reasonable component, so that devitrified glass and devitrified glass of the invention Product has high transmitance and low mist degree, is suitable for electronic equipment or display equipment.
Specific embodiment
Devitrified glass and crystallized glass article of the invention is the material with crystal phase and glass phase, is different from noncrystalline Solid.What the crystal phase of devitrified glass and crystallized glass article can occur in the X-ray diffraction pattern by X-ray diffraction analysis Peak angle distinguish and/or measured by TEMEDX.
The present inventor passes through repetition test and research, for constituting the specific of devitrified glass and crystallized glass article Ingredient is obtained by the way that its content and content ratio are defined as particular value and make it that specific crystal phase be precipitated with lower cost Devitrified glass or crystallized glass article of the invention are arrived.
In the following, being carried out to the range of each component (ingredient) of host glass of the present invention, devitrified glass and crystallized glass article Explanation.In the present specification, if without specified otherwise, the content of each component is all using relative to the group for being converted into oxide At host glass or devitrified glass or the weight percent of crystallized glass article substance total amount indicate.Herein, described " to change It is counted as the composition of oxide " refer to, the original as host glass of the invention, devitrified glass or crystallized glass article constituent In the case that oxide, complex salt and the hydroxide etc. expected and used decompose when melting and are changed into oxide, by the oxidation The substance total amount of object is as 100%.In addition, being the host glass before crystallization, matrix when being only called glass in the present specification It is known as devitrified glass after glass crystallization, crystallized glass article refers to the devitrified glass after chemical strengthening.
Unless in particular situations it is further noted that numberical range listed herein includes upper and lower bound value, " more than " " following " includes endpoint value, all integers and score in the range, and is not limited to listed specific when limited range Value.Term as used herein " about " assignment side, parameter and other quantity and feature be not and need not to be accurate, if any It needs, can be approximate and/or bigger or lower, this reflection tolerance, conversion factor and measurement error etc..Herein referred "and/or" It is inclusive, such as " A；And/or B ", refer to only A, perhaps only B or has A and B simultaneously.
Crystal phase in devitrified glass or crystallized glass article of the present invention contains a lithium metasilicate；And/or aluminum phosphate；And/or partially Aluminum phosphate；And/or lithium phosphate；And/or quartz crystal；And/or zirconium silicate crystal etc..
Crystal phase accounts for devitrified glass in the present invention or the weight percentage ranges of crystallized glass article reach 20~80%；One In a little embodiments, weight percentage ranges reach 25~70%；In some embodiments, weight percentage ranges reach 30 ~70%.
SiO2It is the neccessary composition of glass of the invention, is one of the component of formation crystal after heat treatment, if SiO2's Content is 50% hereinafter, glass glass forming ability variation, is not easy to form glass.Therefore, SiO2The lower limit of content be 50%, preferably under It is limited to 52%.If SiO2Content is unfavorable for the chemical strengthening of glass, and can reduce crystallized glass article 59.5% or more With the falling ball impact test height of devitrified glass.Therefore, SiO2The upper limit of content is 59.5%, preferred upper limit 58%.In some realities It applies in mode, can include about 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 59.5% SiO2。
Al2O3It is to form glass network structure neccessary composition, reduces host glass and the devitrified glass coefficient of expansion, can refine Crystal grain reduces the mist degree of devitrified glass and crystallized glass article, is conducive to the energy that devitrified glass chemical strengthening improves ion exchange Power, but if its content is less than 15%, then said effect is bad.Therefore, Al2O3The lower limit of content is 15%, and preferred lower limit is 16%.On the other hand, if Al2O3Content be more than 25%, then glass fusing degree of difficulty increase, hinder the formation of crystal, Reduce the fracture toughness and falling ball impact test height of devitrified glass and crystallized glass article.Therefore Al2O3The upper limit of content is 25%, Preferred upper limit is 23%.In some embodiments, can include about 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25% Al2O3。
Li2O can reduce the viscosity of glass and promote Crystallization, be the required component of crystal phase composition, while be also ion The component mainly replaced with sodium, potassium ion in exchange process, it is possible to increase chemical strengthening rear surface stress, but if its content It is less than 4%, then ineffective, therefore, Li2The lower limit of O content is 4%, preferred lower limit 5%.On the other hand, if too much Contain Li2O influences the ion exchange layer depth and surface stress of crystallized glass article instead, leads to the strong of crystallized glass article Degree decline.Therefore, Li2The upper limit of O content is 10%, preferred upper limit 8%, and the further preferred upper limit is 7%.In some implementations In mode, can include about 4%, 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7%, 6.8%, 6.9%, 7%, 8%, 9%, 10% Li2O。
Na2O can reduce the fusion temperature of glass raw material, reduce glass solid-state low temperature viscosity, effectively facilitate glass heat treatment When precipitate crystal, be conducive to the chemical strengthening of devitrified glass, but glass excessively contains Na2O reduces host glass and crystallite glass Stability that glass is moisture resistance, and easily keep devitrified glass crystallization rate too fast, reduce the intensity of devitrified glass.Therefore, Na2O content it is upper It is limited to 15%, preferred upper limit 12%.On the other hand, what glass was very few contains Na2O, host glass and devitrified glass cannot obtain Expected thermal expansion coefficient is obtained, it is unfavorable to process to postorder, reduces Na ion and K ion exchange content in devitrified glass, and reduction is micro- The surface stress of crystal glass product, to reduce the intensity of crystallized glass article, therefore Na2The lower limit of O content is 5%, preferably Lower limit is 8%.In some embodiments, can include about 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5%, 15% Na2O。
The present inventor's lot of experiments discovery, by controlling SiO2、Al2O3、Na2O and Li2O is introduced in certain proportion, Can influence the thermal expansion coefficient of host glass and devitrified glass, the hardness of devitrified glass and crystallized glass article, bending strength and Fracture toughness, especially (Li2O+Na2O)/(SiO2+Al2O3) be 0.15~0.35 in the range of when, host glass or micro- can be made Crystal glass has suitable thermal expansion coefficient, and more crystal grain is obtained after crystallization, improves devitrified glass and devitrified glass system The hardness and fracture toughness of product, in some embodiments, it is preferred (Li2O+Na2O)/(SiO2+Al2O3) it is 0.16~0.32, more Preferably 0.17~0.30, also can get high bending strength, in some embodiments, four-point bending intensity be 600MPa with On, preferably 650MPa or more, more preferably 700MPa or more.In some embodiments, (Li2O+Na2O)/(SiO2+ Al2O3) value can for 0.15,0.16,0.17,0.18,0.19,0.20,0.21,0.22,0.23,0.24,0.25,0.26, 0.27、0.28、0.29、0.30、0.31、0.32、0.33、0.34、0.35。
Pass through control (Li in the present invention2O+Na2O)/Al2O3Value in 0.5~1.4 range, devitrified glass can be optimized Chemical strengthening performance improves the ion exchange layer depth and surface stress, especially (Li of crystallized glass article2O+Na2O)/ Al2O3Value preferably in 0.53~1.3 range, the falling ball impact test height of crystallized glass article also can be improved, more preferable (Li2O+ Na2O)/Al2O3Value be 0.55~1.2.In some embodiments, (Li2O+Na2O)/Al2O3Value can for 0.5,0.53, 0.55、0.57、0.60、0.65、0.7、0.75、0.8、0.85、0.9、0.95、1.0、1.05、1.10、1.15、1.20、1.25、 1.30、1.35、1.4。
In the present invention, as control Li2O and Na2O introduction volume ratio Li2O/Na2When O is in 0.28~1.2 range, it can optimize The Properties of Crystallization of host glass makes devitrified glass and crystallized glass article have suitable grain size, to make devitrified glass And crystallized glass article has excellent performance, preferably Li2O/Na2O is 0.29~1.1, more preferably 0.30~1.0, crystallite glass Glass and crystallized glass article falling ball impact test height become larger, in some embodiments, the falling ball impact test height of crystallized glass article Preferably 1000mm or more, more preferably 1100mm or more, further preferably 1200mm or more, still more preferably for 1500mm or more.In some embodiments, Li2O/Na2The value of O can for 0.28,0.30,0.32,0.34,0.36,0.38, 0.40、0.42、0.44、0.46、0.48、0.50、0.52、0.54、0.56、0.58、0.60、0.62、0.64、0.66、0.68、 0.70、0.72、0.74、0.76、0.78、0.80、0.82、0.84、0.86、0.88、0.90、0.92、0.94、0.96、0.98、 1.0、1.02、1.04、1.06、1.08、1.10、1.12、1.14、1.16、1.18、1.20。
K2O contributes to improve the optional component of host glass meltdown property and processability, but if containing too much K2O is then easy to generate the reduction of the chemical stability of host glass or devitrified glass and the raising of thermal expansion coefficient.Cause This, K2The content of O is 0~10%, preferably 0~5%.In some embodiments, can include about 0%, be greater than 0%, 0.1%, 0.3%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% K2O。
ZrO2It is optional components in the present invention, has the function of that crystallization is precipitated and form nucleus, while helping to improve base The chemical stability of matter glass and devitrified glass.The study found that ZrO2It can also be by significantly being dropped during forming host glass Low glass devitrification risk.ZrO in the present invention2The lower limit of content is preferably 0.1%, and more preferably 0.5%, further preferably 1%；But if containing ZrO too much2, then the devitrification resistance of host glass is easily reduced instead, while host glass crystallization mistake Process control difficulty increases.Therefore, ZrO2The upper limit of content is 10%, preferred upper limit 6%, and the more preferable upper limit is 4%.Some In embodiment, can include about 0%, 0.1%, 0.3%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% ZrO2。
P2O5The component for contributing to improve the melting of host glass, can form nucleus in host glass, improve base Thermal expansion stability of the matter glass in crystallization process, P2O5The lower limit of content is preferably 0.1%, and more preferably 0.5%, into one Step preferably 1%；But if containing P too much2O5, then being easy to, which makes host glass generate devitrification resistance, reduces, and crystallite glass Glass, crystallized glass article mechanical performance have the tendency that deterioration.Therefore, P2O5The upper limit of content is 10%, preferred upper limit 5%, more Preferred upper limit is 4%.In some embodiments, can include about 0.1%, 0.3%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% P2O5。
MgO helps to reduce the viscosity of glass, inhibits when molding to refine crystal grain when devitrification of glass and crystallization, also having improves The effect of meltdown property, MgO are optional component, preferred lower limit 0.5% in the present invention；But if content of MgO is excessively high, can draw Devitrification resistance decline is played, undesirable crystal can be obtained after crystallization, under the performance for leading to devitrified glass and crystallized glass article Drop.Therefore, the upper limit of content of MgO is 10%, preferred upper limit 5%.In some embodiments, it can include about 0%, be greater than 0%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% MgO.
ZnO can improve the meltdown property of host glass, improve the chemical stability of host glass, and when crystallization refines crystal grain, ZnO is optional component in the present invention, and preferred content is 1% or more；The upper limit of ZnO content is controlled 10% hereinafter, can be with Prevent host glass crystal grain in crystallization process excessive, therefore, the upper limit of ZnO content is 10%, preferred upper limit 8%.One In a little embodiments, can include about 0%, be greater than 0%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% ZnO.
SrO be improve host glass melting and inhibit host glass molding crystallization optional component, the present invention in it is excellent Selected control SrO is 5% hereinafter, devitrified glass and crystallized glass article can be made to be easier to obtain excellent grain size, more preferably Its content is below 1%.In some embodiments, it is preferred not introducing SrO.In some embodiments, can include about 0%, SrO greater than 0%, 0.3%, 0.5%, 1%, 2%, 3%, 4%, 5%.
BaO contributes to improve the optional component of the glass forming ability of host glass, when its content is more than 5%, matrix glass The devitrification resistance of glass reduces, therefore BaO content is preferably controlled in 5% hereinafter, more preferably 1% or less in the present invention.Some In embodiment, BaO is not preferably introduced.In some embodiments, can include about 0%, be greater than 0%, 0.3%, 0.5%, 1%, 2%, 3%, 4%, 5% BaO.
TiO2It is a kind of optional component for helping to reduce the fusion temperature of host glass, improve chemical stability, this hair 5% TiO below of bright middle introducing2, host glass crystallization process can be made to become easy control, preferably 1% or less.Some In embodiment, TiO is not preferably introduced2.In some embodiments, can include about 0%, be greater than 0%, 0.3%, 0.5%, 1%, 2%, 3%, 4%, 5% TiO2。
Y2O3It is the hardness for improving host glass, the optional component of chemical stability, but its content excessively then easily causes base Matter glass forms crystallization, and content is 5% hereinafter, preferably 1% or less.In some embodiments, it is preferred not introducing Y2O3。 In some embodiments, it can include about the 0%, Y greater than 0%, 0.3%, 0.5%, 1%, 2%, 3%, 4%, 5%2O3。
B2O3The melting behaviour for facilitating optimization host glass, when its too high levels, host glass chemical stability drop It is low, therefore B2O3Content is 6% hereinafter, it is preferred that B2O3Content be 0.1~4%, in some embodiments, can include about 0%, be greater than 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 5.0%, 5.5%, 6% B2O3。
Sb2O3、SnO2、SnO、CeO2One or more of component as clarifying agent be added, Sb2O3Upper content limit is 2%, Preferably 1%, more preferably 0.5%.SnO2、SnO、CeO2Respective upper content limit is respectively 2%, and preferably 1%, more preferably It is 0.5%.In some embodiments, one of above 4 kinds of clarifying agents or more than one content are about 0%, are greater than 0%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%.
In some embodiments, As can also be used2O3, the compound of Cl, the compound of Br etc. be used as clarifying agent, contain Amount is respectively 2% hereinafter, preferably 1% hereinafter, more preferably 0.5% or less.
To obtain suitable crystallite dimension and crystal phase type in the present invention, La can be introduced in some embodiments2O3、 Cs2O、Tb2O3、GeO2With the ingredients such as CaO, but its independent or total content is preferably below 2%.PbO and As2O3It is Toxic Matter, even if a small amount of requirement for not meeting environmental protection addition, therefore the present invention in some embodiments preferably without containing PbO and As2O3。
In some embodiments of the present invention, the coloured matrix glass of tool is prepared by the way that colorant is added in the feed Glass, devitrified glass or crystallized glass article can make host glass, devitrified glass or crystallized glass article that different colors be presented, Colorant contains: NiO:0~4%；And/or Ni2O3: 0~4%；And/or CoO:0~2%；And/or Co2O3: 0~2%；With/ Or Fe2O3: 0~7%；And/or MnO2: 0~4%；And/or Er2O3: 0~8%；And/or Nd2O3: 0~8%；And/or Cu2O:0 ~4%；And/or Pr2O5: 0~8%；And/or CeO2: 0~4%.Its colourant weights degree and its effect are described in detail such as Under:
Brown prepared by the present invention or green host glass, devitrified glass or crystallized glass article, use NiO, Ni2O3Or Pr2O5For colorant.NiO and Ni2O3For colorant, it is used to prepare brown or green host glass, devitrified glass or devitrified glass Product, two kinds of components can be used alone or are used in mixed way, distinguish content be generally 4% hereinafter, preferably 3% hereinafter, If content is more than 4%, colorant cannot be dissolved in very well in host glass, devitrified glass or crystallized glass article, respectively Content lower limit is such as lower than 0.1%, host glass, devitrified glass or crystallized glass article color are unobvious 0.1% or more.In In some embodiments, can include about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0% NiO or Ni2O3.When being such as used in mixed way, NiO and Ni2O3 Total amount be generally 4% hereinafter, total amount lower limit 0.1% or more.In some embodiments, can include about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0% NiO and Ni2O3.Use Pr2O5As green host glass, devitrified glass or crystallized glass article Colorant is used alone, and general content is 8% hereinafter, preferred content is 6% hereinafter, its content lower limit is 0.4% or more, such as Lower than 0.4%, host glass, devitrified glass or crystallized glass article color are unobvious.In some embodiments, it can include about 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3.0%, 3.2%, 3.4%, 3.6%, 3.8%, 4.0%, 4.2%, 4.4%, 4.6%, 4.8%, 5.0%, 5.2%, 5.4%, 5.6%, 5.8%, 6.0%, 6.2%, 6.4%, 6.6%, 6.8%, 7.0%, 7.2%, 7.4%, 7.6%, 7.8%, 8.0% Pr2O5。
Blue substrate glass, devitrified glass or crystallized glass article prepared by the present invention, use CoO or Co2O3For coloring Agent, two kinds of colorant components can be used alone or are used in mixed way, and content respectively is all generally 2% hereinafter, preferably 1.8% hereinafter, colorant cannot be dissolved in host glass, devitrified glass or crystallized glass article very well if content has been more than 2% In, content lower limit respectively is such as lower than 0.05%, host glass, devitrified glass or crystallized glass article 0.05% or more Color is unobvious.In some embodiments, can include about 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0% CoO or Co2O3.When being such as used in mixed way, CoO and Co2O3Total amount is no more than 2%, under total amount Limit is 0.05% or more.In some embodiments, can include about 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0% CoO and Co2O3。
Yellow host glass, devitrified glass or crystallized glass article prepared by the present invention, use Cu2O or CeO2For coloring Agent, two kinds of colorant components are used alone or are used in mixed way, and content lower limit respectively is such as lower than 0.5% or more 0.5%, host glass, devitrified glass or crystallized glass article color are unobvious, and Cu is used alone2O is 4% hereinafter, preferably 3% if content is more than 4% hereinafter, be easy to make host glass crystallization.In some embodiments, can include about 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0% Cu2O.Individually Use CeO2Content is generally 4% hereinafter, preferably 3% hereinafter, if content is more than 4%, host glass, devitrified glass or crystallite Glassware gloss is bad.In some embodiments, can include about 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0% CeO2.Meanwhile a small amount of CeO2Being added in glass has The effect of de-bubble, CeO2It is also used as clarifying agent use in glass.If two kinds of colorants are used in mixed way, total amount Generally 4% hereinafter, total amount lower limit 0.5% or more.In some embodiments, can include about 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0% CeO2And Cu2O。
Fe is used alone in black prepared by the present invention or smoky gray host glass, devitrified glass or crystallized glass article2O3 For colorant；Or use Fe2O3With two kinds of colorants being used in mixed way of CoO；Or use Fe2O3And Co2O3Two kinds of mixing make Colorant；Or use Fe2O3, tri- kinds of colorants being used in mixed way of CoO and NiO；Or use Fe2O3、Co2O3And NiO Three kinds of colorants being used in mixed way.Prepare the colorant of black and smoky gray host glass, devitrified glass or crystallized glass article Mainly use Fe2O3Coloring, content be 7% hereinafter, preferably 5% hereinafter, its content lower limit 0.2% or more, in some implementations In mode, can include about 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5%, 7.0% Fe2O3.CoO and Co2O3Have absorption in visible light, the coloring degree of host glass, devitrified glass or crystallized glass article can be deepened, generally with Fe2O3Respective content is 0.6% hereinafter, lower limit is 0.2% or more when being used in mixed way.In some embodiments, it can include about 0.2%, 0.3%, 0.4%, 0.5%, 0.6% CoO and/or Co2O3.NiO has absorption in visible light, can deepen matrix glass The coloring degree of glass, devitrified glass or crystallized glass article, its content is 1% hereinafter, total amount lower limit when generally mixing with use 0.2% or more.In some embodiments, can include about 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0% NiO.
Purple host glass, devitrified glass or crystallized glass article prepared by the present invention, use MnO2For colorant, use Content is generally 4% hereinafter, it is preferred that 3% hereinafter, its content lower limit is 0.1% or more, is such as lower than 0.1%, host glass, micro- Crystal glass or crystallized glass article color are unobvious.In some embodiments, can include about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3.0%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0% MnO2。
Pink colour host glass, devitrified glass or crystallized glass article prepared by the present invention, use Er2O3For colorant, use Content is generally 8% hereinafter, it is preferred that below 6%.Due to rare earth element er2O3Coloration efficiency is low, is more than 8% when using content, The color of host glass, devitrified glass or crystallized glass article can not be made further to deepen, increase cost, content instead Lower limit is such as lower than 0.4%, host glass, devitrified glass or crystallized glass article color are unobvious 0.4% or more.Some In embodiment, can include about 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3.0%, 3.2%, 3.4%, 3.6%, 3.8%, 4.0%, 4.2%, 4.4%, 4.6%, 4.8%, 5.0%, 5.2%, 5.4%, 5.6%, 5.8%, 6.0%, 6.2%, 6.4%, 6.6%, 6.8%, 7.0%, 7.2%, 7.4%, 7.6%, 7.8%, 8.0% Er2O3。
Aubergine host glass, devitrified glass or crystallized glass article prepared by the present invention, use Nd2O3For colorant, make 8% is generally hereinafter, it is preferred that below 6% with content.Due to rare earth element nd2O3Coloration efficiency is low, is more than using content 8%, the color of host glass, devitrified glass or crystallized glass article can not be made further to deepen, increase cost instead, Content lower limit is such as lower than 0.4%, host glass, devitrified glass or crystallized glass article color are unobvious 0.4% or more.In In some embodiments, can include about 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3.0%, 3.2%, 3.4%, 3.6%, 3.8%, 4.0%, 4.2%, 4.4%, 4.6%, 4.8%, 5.0%, 5.2%, 5.4%, 5.6%, 5.8%, 6.0%, 6.2%, 6.4%, 6.6%, 6.8%, 7.0%, 7.2%, 7.4%, 7.6%, 7.8%, 8.0% Nd2O3。
Red host glass, devitrified glass or crystallized glass article prepared by the present invention, use Er2O3、Nd2O3And MnO2It is mixed Colorant is closed, Er ion has absorption in 400-500nm in glass, and Mn ion mainly has absorption at 500nm, and Nd ion mainly exists There is strong absorption at 580nm, the mixing of three kinds of substances can prepare red host glass, devitrified glass or crystallized glass article, Due to Er2O3And Nd2O3For rare earth coloring, colorability is weaker, Er2O3Usage amount is within 6%, Nd2O3Usage amount is 4% Within, MnO2Color strength, usage amount in 2% range, using mixed colorant total amount lower limit 0.9% or more.
" not introducing " " not containing " " 0% " described herein refers to not deliberately by the compound, molecule or element etc. It is added in host glass of the present invention, devitrified glass or crystallized glass article as raw material；But as production host glass, crystallite The raw material and/or equipment of glass or crystallized glass article, can exist certain is not the impurity deliberately added or component, and meeting is most A small amount of or trace contains in whole host glass, devitrified glass or crystallized glass article, and such situation is also in the invention patent In protection scope.
In some embodiments of the present invention, crystal phase contains a lithium metasilicate in devitrified glass and crystallized glass article；And/or Aluminum phosphate；And/or aluminium metaphosphate；And/or lithium phosphate；And/or quartz crystal；And/or zirconium silicate crystal etc., it is crystallite of the present invention Glass and crystallized glass article provide high intensity, and devitrified glass and crystallized glass article fracture toughness are got higher；Devitrified glass and The falling ball impact test height and four-point bending intensity of crystallized glass article become larger.Devitrified glass of the present invention it is also ion-exchangeable with Obtain additional mechanical strength.The present invention is designed by reasonable component, can make devitrified glass and crystallized glass article of the present invention Suitable grain size is obtained, makes devitrified glass and crystallized glass article of the present invention that there is high intensity.
The crystallite dimension and mist degree of devitrified glass or crystallized glass article of the present invention will affect devitrified glass or devitrified glass The transmitance of product, i.e. influence light percent of pass, the smaller transmitance of crystal grain are higher；Mist degree is smaller, and transmitance is higher.In some implementations In mode, the mist degree of the crystallized glass article of 0.55mm thickness or devitrified glass be 0.3% hereinafter, preferably 0.25% hereinafter, More preferably 0.2% or less.In some embodiments, the crystallite dimension of crystallized glass article or devitrified glass be 70nm with Under, preferably 50nm hereinafter, more preferably 40nm hereinafter, further preferably 30nm hereinafter, still more preferably for 20nm with Under.On the other hand, by the study found that the refringence of crystal phase and glass phase is away from smaller, devitrified glass or micro- in devitrified glass The transmitance of crystal glass product is higher.
High transmitance is presented in devitrified glass or crystallized glass article of the present invention in visible-range.In some embodiment party The average light transmission rate of 400~800nm of the crystallized glass article of 0.55mm thickness or devitrified glass is 85% or more in formula, preferably It is 88% or more, more preferably 90% or more.In some preferred embodiments, the crystallized glass article of 0.55mm thickness or The light transmission rate of devitrified glass 550nm is 80% or more, preferably 85% or more, more preferably 89% or more, further preferably It is 91% or more.
In some embodiments, antimicrobial composition can be added to host glass, devitrified glass or devitrified glass system In product.
Host glass, devitrified glass and crystallized glass article of the invention can be produced and be made by the following method It makes:
It generates host glass: raw material being uniformly mixed according to component ratio, uniform mixture is put into platinum system or quartz In the crucible of system, according to the fusing difficulty that glass forms, in 1250~1650 DEG C of temperature range in electric furnace or gas furnace It is interior melt within 5~24 hours, after stirring keeps its uniform, it is down to temperature appropriate and is cast in mold, Slow cooling forms.
Host glass of the invention can be formed by well-known method.In some embodiments, this hair The refractive index (nd) of bright host glass is 1.500~1.530, preferably 1.505~1.525.
Host glass of the invention carries out Crystallizing treatment by crystallization process after shaping or after processing and forming, in glass It is internal that crystallization is equably precipitated.The Crystallizing treatment can be carried out by 1 stage, can also be carried out by 2 stages, preferably be adopted Crystallizing treatment is carried out with 2 stages.The processing of nucleation technique is carried out at a temperature of the 1st, then higher than nucleation technological temperature The processing of crystal growth technique is carried out at a temperature of 2nd.The Crystallizing treatment carried out at a temperature of the 1st is known as the 1st Crystallizing treatment, it will The Crystallizing treatment carried out at a temperature of the 2nd is known as the 2nd Crystallizing treatment.
In order to make devitrified glass obtain desired physical property, preferred crystallization process are as follows:
Crystallizing treatment is carried out above by 1 stage, can continuously carry out core formation process and crystalline growth technique. That is, its temperature is kept for the regular hour, then after reaching heat treatment temperature by Crystallizing treatment temperature as defined in being warming up to Cool down again.The temperature of the Crystallizing treatment is preferably at 480~700 DEG C, in order to which desired crystal phase is precipitated, more preferably It is 520~600 DEG C, retention time at a temperature of Crystallizing treatment, preferably 0~8 hour, more preferably 1~6 hour.
When carrying out Crystallizing treatment above by 2 stages, the 1st temperature is preferably 480~550 DEG C, and the 2nd temperature is preferably 550~700 DEG C.Retention time at a temperature of the 1st, preferably 0~24 hour, more preferably 2~15 hours.In the 2nd temperature Under retention time, preferably 0~10 hour, more preferably 0.5~6 hour.
0 hour above-mentioned retention time referred to and started to cool down or heat up again less than 1 minute after reaching its temperature.
In some embodiments, the present invention is by the refractive index (nd) of the obtained devitrified glass of crystallization process 1.500~1.540, preferably 1.510~1.530.
In some embodiments, can by various techniques by host glass as described herein or devitrified glass manufacture at Body, the formed body include but is not limited to sheet material, and the technique includes but is not limited to slot draw, float glass process, roll-in and ability The well known technique that other form sheet material in domain.Alternatively, matrix glass can be formed by float glass process known in the field or roll-in method Glass or devitrified glass.
Host glass or devitrified glass of the invention, can be using the glass of the methods of grinding or polishing manufacture sheet material Formed body, but the method for manufacturing glass shaping body, are not limited to these methods.
Host glass or devitrified glass formed body of the invention can use the methods of hot bending or die mould at a certain temperature Preparation forms various shape, is not limited to these methods.
Host glass, devitrified glass and crystallized glass article of the present invention can have rationally useful any thickness.
Devitrified glass of the invention improves except mechanical property except through being precipitated to crystallize, and can also be answered by forming compression Power layer obtains higher intensity, so that crystallized glass article be made.
In some embodiments, host glass or devitrified glass can be processed into sheet material and/or moulding (such as punching, heat It is curved etc.), it polishes and/or clears off after setting, then chemical strengthening is carried out by chemical strengthening technique.
Chemical strengthening of the present invention is ion-exchange.Host glass of the invention, devitrified glass are all that can lead to It crosses method well known to the art and carries out ion exchange.In ion exchange process, in host glass or devitrified glass Lesser metal ion is by the displacement of larger metal ion or " friendship with identical valence state close to host glass or devitrified glass It changes ".With the lesser ion of biggish ion exchange, compression stress is constructed in host glass or devitrified glass, is formed compression and is answered Power layer.
In some embodiments, metal ion is monovalent alkali metal ions (such as Na+、K+、Rb+、Cs+Deng), ion is handed over Change by salt bath that host glass or devitrified glass are immersed in at least one fuse salt comprising biggish metal ion come It carries out, which is used to replace the lesser metal ion in host glass.Alternatively, other valent metal ions Such as Ag+、Tl+、Cu+Etc. can also be used for exchange monovalention.For one kind or more of chemical strengthening host glass or devitrified glass Different kinds of ions exchange process may include but be not limited to: be immersed into single salt bath, or be immersed into identical or In multiple salt baths of difference composition, there are washing and/or annealing steps between submergence.
In some embodiments, host glass or devitrified glass can be by being immersed in about 430 DEG C~470 DEG C of temperature Melting Na salt (such as NaNO3) salt bath in carry out ion exchange within about 6~20 hours, preferred range is 435 DEG C~460 DEG C, preferably time range is 8~13 hours.In this embodiment, in Na ion exchange host glass or devitrified glass Part Li ion, to form surface compressive layer and high-mechanical property is presented.In some embodiments, host glass or crystallite Glass can by be immersed in about 400 DEG C~450 DEG C at a temperature of melt K salt (such as KNO3) salt bath in carry out within 1~8 hour Ion exchange, preferably time range are 2~4 hours.
In some preferred embodiments, by 450 DEG C of melting Na salt (such as NaNO3) salt bath in about 8 hours, from Son exchange layer depth is up to 20 μm or more, and preferably 25 μm or more.
In some embodiments, the ion implantation of the surface layer of also oriented host glass or devitrified glass injection ion, And host glass or devitrified glass are heated, the hot tempering method being then quickly cooled down.
Host glass, devitrified glass and/or crystallized glass article performance indexes of the present invention are tested using following methods:
[refractive index]
Refractive index (nd) is tested according to method as defined in GB/T7962.1-2010.
[mist degree]
It is surveyed with 0.55mm heavy sheet glass sample preparation by standard of GB2410-80 using mist degree tester EEL57D Examination.
[crystallite dimension]
It is measured using SEM scanning electron microscope, devitrified glass in HF acid by being surface-treated, then to devitrified glass Surface carries out metal spraying, and surface scan is carried out under SEM scanning electron microscope, determines the size of its crystal grain.
[light transmission rate]
Light transmission rate as described herein is external transmitance, sometimes abbreviation transmitance.
Sample is processed into 0.55mm thickness and carries out opposite face parallel polished, utilizes Hitachi U-41000 shape spectrophotometric The average light transmission rate of 400~800nm of meter measurement.
Sample is processed into 0.55mm thickness and carries out opposite face parallel polished, utilizes Hitachi U-41000 shape spectrophotometric The light transmission rate of meter measurement 550nm.
[crystallinity]
XRD diffraction maximum and database map are compared, crystallinity is by calculating crystalline phase diffracted intensity in entirety In map intensity obtained by proportion, and internal calibration is carried out by using pure quartz crystal.
[surface stress] and [ion exchange layer depth]
Surface stress measurement is carried out using glass surface stress gauge FSM-6000LEUV.
The measurement of ion exchange layer depth is carried out using glass surface stress gauge SLP-2000.
It with the refractive index of sample is 1.54 as determination condition, Photoelasticity constant is that 25.3 [(nm/cm)/Mpa] are carried out It calculates.
[falling ball impact test height]
The sample of 150 × 57 × 0.55mm is placed on glass carrying fixture, falls the steel ball of 132g from specified altitude Under, sample does not occur to be broken and the maximum falling ball impact test height of impact that is able to bear.Specifically, testing from falling ball impact test height Degree 800mm comes into effect, and in cases where no fracturing is occurring, successively changes height by 850mm, 900mm, 950,1000 or more Degree.For the embodiment with " falling ball impact test height ", using crystallized glass article as subjects.It is recorded as in embodiment The test data of 1000mm, expression do not occur to be broken and hold making steel ball fall crystallized glass article from the height of 1000mm yet By impact.
[fracture toughness]
Using directly measure impression running crack size method, size of sample be 2mm × 4mm × 20mm, by chamfering, It polishes and polishes, after the completion of sample preparation, add the power of 49N on sample with Vickers hardness penetrator and maintain the time of 30s, to get After impression, its breaking strength is measured with the method for three-point bending.
[four-point bending intensity]
Using microcomputer controlled electronic universal tester CMT6502,150 × 57 × 0.55mm of glass size, with ASTM C 158-2002 is that standard is tested.
[Vickers hardness]
The diamond quadrangular pyramid pressure head for being 136 ° with opposite face angle is when being pressed into the recess of Pyramid on test face Load (N) divided by by recess length gauge calculate surface area (mm2) value indicate.Make test load 100 (N), protect The time is held as 15 (seconds) progress.
[coefficient of expansion]
Thermal expansion coefficient (α20℃-120℃) tested according to method as defined in GB/T7962.16-2010.
Host glass of the present invention has the following performance:
1) in some embodiments, refractive index (nd) is 1.500~1.530, preferably 1.505~1.525.
2) in some embodiments, thermal expansion coefficient (α20℃-120℃) it is 60~85 × 10-7/ K, preferably 70~85 × 10-7/K。
Devitrified glass of the present invention has the following performance:
1) in some embodiments, the crystallinity of devitrified glass is 20% or more, preferably 30% or more, more preferably 40% or more, further preferably 50% or more.
2) in some embodiments, the crystallite dimension of devitrified glass is 70nm hereinafter, preferably 50nm is hereinafter, preferably 40nm hereinafter, more preferably 30nm hereinafter, further preferably 20nm or less.
3) in some embodiments, the mist degree of the devitrified glass of 0.55mm thickness be 0.3% hereinafter, preferably 0.25% with Under, more preferably 0.2% or less.
4) in some embodiments, the devitrified glass of 0.55mm thickness, the mean transmissivity of 400~800nm wavelength are 85% or more, preferably 88% or more, more preferably 90% or more.
5) in some embodiments, the devitrified glass of 0.55mm thickness, the transmitance of 550nm wavelength is 85% or more, excellent It is selected as 89% or more, more preferably 91% or more.
6) in some embodiments, the refractive index (nd) of devitrified glass be 1.500~1.540, preferably 1.510~ 1.530。
7) in some embodiments, the thermal expansion coefficient (α of devitrified glass20℃-120℃) it is 70~120 × 10-7/ K, preferably It is 86~100 × 10-7/K。
Crystallized glass article of the present invention has the following performance:
1) in some embodiments, the surface stress of crystallized glass article be 300MPa or more, preferably 500MPa with On, more preferably 700MPa or more.
2) in some embodiments, the four-point bending intensity of crystallized glass article is 600MPa or more, preferably 650MPa or more, more preferably 700MPa or more.
3) in some embodiments, the ion exchange layer depth of crystallized glass article is 10 μm or more, preferably 15 μm More than, more preferable 20 μm or more, further preferably 25 μm or more.
4) in some embodiments, the falling ball impact test height of crystallized glass article is 1000mm or more, preferably 1100mm or more, more preferably 1200nm or more.
5) in some embodiments, the fracture toughness of crystallized glass article is 1MPam1/2More than, preferably 1.3MPa·m1/2More than, more preferably 1.5MPam1/2More than.
6) in some embodiments, the Vickers hardness (H of crystallized glass articlev) it is 600kgf/mm2More than, preferably 650kgf/mm2More than, more preferably 700kgf/mm2More than.
7) in some embodiments, the crystallinity of crystallized glass article is 20% or more, preferably 30% or more, more excellent It is selected as 40% or more, further preferably 50% or more.
8) in some embodiments, the crystallite dimension of crystallized glass article is 70nm hereinafter, preferably 50nm is hereinafter, more Preferably 40nm hereinafter, further preferably 30nm hereinafter, still more preferably 20nm or less.
9) in some embodiments, the mist degree of the crystallized glass article of 0.55mm thickness is 0.3% hereinafter, preferably 0.25% hereinafter, more preferably 0.2% or less.
10) in some embodiments, the crystallized glass article of 0.55mm thickness, the mean transmissivity of 400~800nm wavelength It is 85% or more, preferably 88% or more, more preferably 90% or more.
11) in some embodiments, the crystallized glass article of 0.55mm thickness, the transmitance of 550nm wavelength be 85% with On, preferably 89% or more, more preferably 91% or more.
12) in some embodiments, the refractive index (nd) of crystallized glass article is 1.500~1.540, preferably 1.510~1.530.
13) in some embodiments, the thermal expansion coefficient (α of crystallized glass article20℃-120℃) it is 70~120 × 10-7/ K, preferably 86~100 × 10-7/K。
Devitrified glass, crystallized glass article and host glass of the invention, can be extensive due to above-mentioned excellent performance It is fabricated to glass cover-plate or glass component；Meanwhile devitrified glass of the present invention, crystallized glass article and host glass are applied to electricity In sub- equipment or display equipment, such as mobile phone, wrist-watch, computer, touch display screen.
Embodiment
In order to further clearly illustrate and illustrate technical solution of the present invention, non-limiting embodiment below is provided. The embodiment of the present invention passes through many effort to ensure the accuracy of numerical value (such as quantity, temperature etc.), but must take into account and deposit In some errors and deviation.It forms itself to provide based on oxide with weight %, and has been standardized into 100%.
It is host glass embodiment shown in following table 1~2
Table 1.
Table 2.
It is devitrified glass embodiment shown in following table 3~4
Table 3.
Table 4.
It is crystallized glass article embodiment shown in following table 5~6
Table 5.
Table 6.
It is colour devitrified glass Articles Example shown in following table 7~9
Table 7.
Table 8.
Table 9.

Claims (49)

1. crystallized glass article, which is characterized in that its component in terms of weight percentage, contains: SiO2: 50~59.5%； Al2O3: 15~25%；Li2O:4~10%；Na2O:5~15%；P2O5: 0.1~10%；ZrO2: 0~10%.
2. crystallized glass article according to claim 1, which is characterized in that its component in terms of weight percentage, also contains Have: ZnO:0~10%；And/or MgO:0~10%；And/or K2O:0~10%；And/or SrO:0~5%；And/or BaO:0~ 5%；And/or TiO2: 0~5%；And/or Y2O3: 0~5%；And/or B2O3: 0~6%；And/or clarifying agent: 0~2%.
3. crystallized glass article, which is characterized in that its component contains SiO2、Al2O3、Li2O and Na2O, component is with weight percent Than indicating, wherein (Li2O+Na2O)/(SiO2+Al2O3) it is that the mist degree of crystallized glass article of 0.15~0.35,0.55mm thickness is 0.3% or less.
4. crystallized glass article according to claim 3, which is characterized in that its component in terms of weight percentage, contains: SiO2: 50~59.5%；Al2O3: 15~25%；Li2O:4~10%；Na2O:5~15%；P2O5: 0.1~10%；ZrO2: 0~ 10%；ZnO:0~10%；MgO:0~10%；K2O:0~10%；SrO:0~5%；BaO:0~5%；TiO2: 0~5%； Y2O3: 0~5%；B2O3: 0~6%；Clarifying agent: 0~2%.
5. crystallized glass article described in any claim according to claim 1~4, which is characterized in that its component is with weight Percentage indicates, contains: SiO2: 52~58%；And/or Al2O3: 16~23%；And/or Li2O:4~8%, preferably Li2O:5~ 7%；And/or Na2O:8~12%；And/or P2O5: 0.5~5%, preferably P2O5: 1~4%；And/or ZrO2: 0.1~10%, it is excellent Select ZrO2: 0.5~6%, more preferable ZrO2: 1~4%；And/or ZnO:1~8%；And/or MgO:0.5~5%；And/or K2O:0 ~5%；And/or SrO:0~1%；And/or BaO:0~1%；And/or TiO2: 0~1%；And/or Y2O3: 0~1%；And/or B2O3: 0.1~4%；And/or clarifying agent: 0~1%.
6. crystallized glass article described in any claim according to claim 1~4, which is characterized in that its component is with weight Percentage expression, (Li2O+Na2O)/(SiO2+Al2O3) it is 0.15~0.35, preferably (Li2O+Na2O)/(SiO2+Al2O3) be 0.16~0.32, more preferable (Li2O+Na2O)/(SiO2+Al2O3) it is 0.17~0.30.
7. crystallized glass article described in any claim according to claim 1~4, which is characterized in that its component is with weight Percentage expression, (Li2O+Na2O)/Al2O3It is 0.5~1.4, preferably (Li2O+Na2O)/Al2O3It is 0.53~1.3, more preferably (Li2O+Na2O)/Al2O3It is 0.55~1.2.
8. crystallized glass article described in any claim according to claim 1~4, which is characterized in that its component is with weight Percentage expression, Li2O/Na2O is 0.28~1.2, preferably Li2O/Na2O is 0.29~1.1, more preferable Li2O/Na2O is 0.30 ~1.0.
9. crystallized glass article described in any claim according to claim 1~4, which is characterized in that the devitrified glass The crystal phase of product contains a lithium metasilicate；And/or aluminum phosphate；And/or aluminium metaphosphate；And/or lithium phosphate；And/or quartz crystal； And/or zirconium silicate crystal.
10. crystallized glass article described in any claim according to claim 1~4, which is characterized in that the devitrified glass Product also contains colorant, can make crystallized glass article that different colours be presented.
11. crystallized glass article according to claim 15, which is characterized in that its colorant in terms of weight percentage, Contain: NiO:0~4%, preferably NiO:0.1~3%；And/or Ni2O3: 0~4%, preferably Ni2O3: 0.1~3%；And/or CoO:0~2%, preferably CoO:0.05~1.8%；And/or Co2O3: 0~2%, preferably Co2O3: 0.05~1.8%；And/or Fe2O3: 0~7%, preferably Fe2O3: 0.2~5%；And/or MnO2: 0~4%, preferably MnO2: 0.1~3%；And/or Er2O3: 0 ~8%, preferably Er2O3: 0.4~6%；And/or Nd2O3: 0~8%, preferably Nd2O3: 0.4~6%；And/or Cu2O:0~4%, It is preferred that Cu2O:0.5~3%；And/or Pr2O5: 0~8%, preferably Pr2O5: 0.4~6%；And/or CeO2: 0~4%, preferably CeO2: 0.5~3%.
12. devitrified glass, which is characterized in that its component in terms of weight percentage, contains: SiO2: 50~59.5%；Al2O3: 15~25%；Li2O:4~10%；Na2O:5~15%；P2O5: 0.1~10%；ZrO2: 0~10%.
13. devitrified glass according to claim 12, which is characterized in that its component in terms of weight percentage, also contains: ZnO:0~10%；And/or MgO:0~10%；And/or K2O:0~10%；And/or SrO:0~5%；And/or BaO:0~ 5%；And/or TiO2: 0~5%；And/or Y2O3: 0~5%；And/or B2O3: 0~6%；And/or clarifying agent: 0~2%.
14. devitrified glass, which is characterized in that its component contains SiO2、Al2O3、Li2O and Na2O, component is with weight percent table Show, wherein (Li2O+Na2O)/(SiO2+Al2O3) be 0.15~0.35,0.55mm thickness devitrified glass mist degree be 0.3% with Under.
15. devitrified glass according to claim 14, which is characterized in that its component in terms of weight percentage, contains: SiO2: 50~59.5%；Al2O3: 15~25%；Li2O:4~10%；Na2O:5~15%；P2O5: 0.1~10%；ZrO2: 0~ 10%；ZnO:0~10%；MgO:0~10%；K2O:0~10%；SrO:0~5%；BaO:0~5%；TiO2: 0~5%； Y2O3: 0~5%；B2O3: 0~6%；Clarifying agent: 0~2%.
16. devitrified glass described in 2~15 any claims according to claim 1, which is characterized in that its component is with weight hundred Divide than indicating, contains: SiO2: 52~58%；And/or Al2O3: 16~23%；And/or Li2O:4~8%, preferably Li2O:5~ 7%；And/or Na2O:8~12%；And/or P2O5: 0.5~5%, preferably P2O5: 1~4%；And/or ZrO2: 0.1~10%, it is excellent Select ZrO2: 0.5~6%, more preferable ZrO2: 1~4%；And/or ZnO:1~8%；And/or MgO:0.5~5%；And/or K2O:0 ~5%；And/or SrO:0~1%；And/or BaO:0~1%；And/or TiO2: 0~1%；And/or Y2O3: 0~1%；And/or B2O3: 0.1~4%；And/or clarifying agent: 0~1%.
17. devitrified glass described in 2~15 any claims according to claim 1, which is characterized in that its component is with weight hundred Divide than indicating, (Li2O+Na2O)/(SiO2+Al2O3) it is 0.15~0.35, preferably (Li2O+Na2O)/(SiO2+Al2O3) it is 0.16 ~0.32, more preferable (Li2O+Na2O)/(SiO2+Al2O3) it is 0.17~0.30.
18. devitrified glass described in 2~15 any claims according to claim 1, which is characterized in that its component is with weight hundred Divide than indicating, (Li2O+Na2O)/Al2O3It is 0.5~1.4, preferably (Li2O+Na2O)/Al2O3It is 0.53~1.3, more preferably (Li2O+Na2O)/Al2O3It is 0.55~1.2.
19. devitrified glass described in 2~15 any claims according to claim 1, which is characterized in that its component is with weight hundred Divide than indicating, Li2O/Na2O is 0.28~1.2, preferably Li2O/Na2O is 0.29~1.1, more preferable Li2O/Na2O be 0.30~ 1.0。
20. devitrified glass described in 2~15 any claims according to claim 1, which is characterized in that the devitrified glass Crystal phase contains a lithium metasilicate；And/or aluminum phosphate；And/or aluminium metaphosphate；And/or lithium phosphate；And/or quartz crystal；And/or silicon Sour zirconium crystal.
21. devitrified glass described in 2~15 any claims according to claim 1, which is characterized in that the devitrified glass is also Containing colorant, it can make devitrified glass that different colours be presented.
22. devitrified glass according to claim 21, which is characterized in that its colorant in terms of weight percentage, contains: NiO:0~4%, preferably NiO:0.1~3%；And/or Ni2O3: 0~4%, preferably Ni2O3: 0.1~3%；And/or CoO:0~ 2%, preferably CoO:0.05~1.8%；And/or Co2O3: 0~2%, preferably Co2O3: 0.05~1.8%；And/or Fe2O3: 0~ 7%, preferably Fe2O3: 0.2~5%；And/or MnO2: 0~4%, preferably MnO2: 0.1~3%；And/or Er2O3: 0~8%, it is excellent Select Er2O3: 0.4~6%；And/or Nd2O3: 0~8%, preferably Nd2O3: 0.4~6%；And/or Cu2O:0~4%, preferably Cu2O: 0.5~3%；And/or Pr2O5: 0~8%, preferably Pr2O5: 0.4~6%；And/or CeO2: 0~4%, preferably CeO2: 0.5~ 3%.
23. host glass, which is characterized in that its component in terms of weight percentage, contains: SiO2: 50~59.5%；Al2O3: 15~25%；Li2O:4~10%；Na2O:5~15%；P2O5: 0.1~10%；ZrO2: 0~10%.
24. host glass according to claim 23, which is characterized in that its component in terms of weight percentage, also contains: ZnO:0~10%；And/or MgO:0~10%；And/or K2O:0~10%；And/or SrO:0~5%；And/or BaO:0~ 5%；And/or TiO2: 0~5%；And/or Y2O3: 0~5%；And/or B2O3: 0~6%；And/or clarifying agent: 0~2%.
25. according to host glass described in claim 23 or 24 any claims, which is characterized in that its component is with weight hundred Divide than indicating, contains: SiO2: 52~58%；And/or Al2O3: 16~23%；And/or Li2O:4~8%, preferably Li2O:5~ 7%；And/or Na2O:8~12%；And/or P2O5: 0.5~5%, preferably P2O5: 1~4%；And/or ZrO2: 0.1~10%, it is excellent Select ZrO2: 0.5~6%, more preferable ZrO2: 1~4%；And/or ZnO:1~8%；And/or MgO:0.5~5%；And/or K2O:0 ~5%；And/or SrO:0~1%；And/or BaO:0~1%；And/or TiO2: 0~1%；And/or Y2O3: 0~1%；And/or B2O3: 0.1~4%；And/or clarifying agent: 0~1%.
26. according to host glass described in claim 23 or 24 any claims, which is characterized in that its component is with weight hundred Divide than indicating, (Li2O+Na2O)/(SiO2+Al2O3) it is 0.15~0.35, preferably (Li2O+Na2O)/(SiO2+Al2O3) it is 0.16 ~0.32, more preferable (Li2O+Na2O)/(SiO2+Al2O3) it is 0.17~0.30.
27. according to host glass described in claim 23 or 24 any claims, which is characterized in that its component is with weight hundred Divide than indicating, (Li2O+Na2O)/Al2O3It is 0.5~1.4, preferably (Li2O+Na2O)/Al2O3It is 0.53~1.3, more preferably (Li2O+Na2O)/Al2O3It is 0.55~1.2.
28. according to host glass described in claim 23 or 24 any claims, which is characterized in that its component is with weight hundred Divide than indicating, Li2O/Na2O is 0.28~1.2, preferably Li2O/Na2O is 0.29~1.1, more preferable Li2O/Na2O be 0.30~ 1.0。
29. according to host glass described in claim 23 or 24 any claims, which is characterized in that the host glass is also Containing colorant, it can make crystallized glass article that different colours be presented.
30. host glass according to claim 29, which is characterized in that its colorant in terms of weight percentage, contains: NiO:0~4%, preferably NiO:0.1~3%；And/or Ni2O3: 0~4%, preferably Ni2O3: 0.1~3%；And/or CoO:0~ 2%, preferably CoO:0.05~1.8%；And/or Co2O3: 0~2%, preferably Co2O3: 0.05~1.8%；And/or Fe2O3: 0~ 7%, preferably Fe2O3: 0.2~5%；And/or MnO2: 0~4%, preferably MnO2: 0.1~3%；And/or Er2O3: 0~8%, it is excellent Select Er2O3: 0.4~6%；And/or Nd2O3: 0~8%, preferably Nd2O3: 0.4~6%；And/or Cu2O:0~4%, preferably Cu2O: 0.5~3%；And/or Pr2O5: 0~8%, preferably Pr2O5: 0.4~6%；And/or CeO2: 0~4%, preferably CeO2: 0.5~ 3%.
31. glass cover-plate, which is characterized in that using crystallized glass article system described in claim 1~11 any claim At, and/or use devitrified glass described in claim 12~22 any claim to be made, and/or use claim 23 Host glass described in~30 any claims is made.
32. glass component, which is characterized in that using crystallized glass article described in claim 1~11 any claim It is made, and/or is made of devitrified glass described in claim 12~22 any claim, and/or use claim Host glass described in 23~30 any claims is made.
33. showing equipment, which is characterized in that including crystallized glass article described in claim 1~11 any claim, And/or it is any including devitrified glass described in claim 12~22 any claim, and/or including claim 23~30 Host glass described in claim, and/or including the glass cover-plate described in claim 31.
34. electronic equipment, which is characterized in that including crystallized glass article described in claim 1~11 any claim, And/or it is any including devitrified glass described in claim 12~22 any claim, and/or including claim 23~30 Host glass described in claim, and/or including the glass cover-plate described in claim 31, and/or including claim 32 The glass component.
35. the manufacturing method of crystallized glass article, which is characterized in that the described method comprises the following steps:
Host glass is formed, component in terms of weight percentage, contains: SiO2: 50~59.5%；Al2O3: 15~25%； Li2O:4~10%；Na2O:5~15%；P2O5: 0.1~10%；ZrO2: 0~10%；ZnO:0~10%；MgO:0~10%； K2O:0~10%；SrO:0~5%；BaO:0~5%；TiO2: 0~5%；Y2O3: 0~5%；B2O3: 0~6%；Clarifying agent: 0 ~2%.
Devitrified glass is formed by crystallization process to the host glass, then chemical strengthening technique shape is passed through to the devitrified glass At crystallized glass article.
36. the manufacturing method of crystallized glass article according to claim 35, which is characterized in that the host glass, Component in terms of weight percentage, contains: SiO2: 52~58%；And/or Al2O3: 16~23%；And/or Li2O:4~8%, It is preferred that Li2O:5~7%；And/or Na2O:8~12%；And/or P2O5: 0.5~5%；And/or ZrO2: 0.1~10%, preferably ZrO2: 0.5~6%, more preferable ZrO2: 1~4%；And/or ZnO:1~8%；And/or MgO:0.5~5%；And/or K2O:0~ 5%；And/or SrO:0~1%；And/or BaO:0~1%；And/or TiO2: 0~1%；And/or Y2O3: 0~1%；And/or B2O3: 0.1~4%；And/or clarifying agent: 0~1%；And/or (Li2O+Na2O)/(SiO2+Al2O3) it is 0.15~0.35, preferably (Li2O+Na2O)/(SiO2+Al2O3) it is 0.16~0.32, more preferable (Li2O+Na2O)/(SiO2+Al2O3) it is 0.17~0.30； And/or (Li2O+Na2O)/Al2O3It is 0.5~1.4, preferably (Li2O+Na2O)/Al2O3It is 0.53~1.3, more preferable (Li2O+ Na2O)/Al2O3It is 0.55~1.2；And/or Li2O/Na2O is 0.28~1.2, preferably Li2O/Na2O is 0.29~1.1, more excellent Select Li2O/Na2O is 0.30~1.0.
37. according to the manufacturing method of crystallized glass article described in claim 35 or 36 any claims, which is characterized in that The host glass, component in terms of weight percentage, contain: NiO:0~4%, preferably NiO:0.1~3%；And/or Ni2O3: 0~4%, preferably Ni2O3: 0.1~3%；And/or CoO:0~2%, preferred CoO:0.05~1.8%；And/or Co2O3: 0~2%, preferably Co2O3: 0.05~1.8%；And/or Fe2O3: 0~7%, preferably Fe2O3: 0.2~5%；And/or MnO2: 0~ 4%, preferably MnO2: 0.1~3%；And/or Er2O3: 0~8%, preferably Er2O3: 0.4~6%；And/or Nd2O3: 0~8%, it is excellent Select Nd2O3: 0.4~6%；And/or Cu2O:0~4%, preferably Cu2O:0.5~3%；And/or Pr2O5: 0~8%, preferably Pr2O5: 0.4~6%；And/or CeO2: 0~4%, preferably CeO2: 0.5~3%.
38. according to the manufacturing method of crystallized glass article described in claim 35~37 any claim, which is characterized in that The crystallization process is warm by it after reaching heat treatment temperature the following steps are included: Crystallizing treatment temperature as defined in being warming up to Degree is kept for the regular hour, is then cooled down again.The temperature of the Crystallizing treatment be 480~700 DEG C, preferably 520~600 DEG C, retention time at a temperature of Crystallizing treatment is 0~8 hour, preferably 1~6 hour.
39. according to the manufacturing method of crystallized glass article described in claim 35~37 any claim, which is characterized in that The crystallization process at a temperature of the 1st the following steps are included: carry out the processing of nucleation technique, then higher than nucleation technological temperature The 2nd at a temperature of carry out crystal growth technique processing.
40. the manufacturing method of crystallized glass article according to claim 39, which is characterized in that the crystallization process includes Following steps: the 1st temperature is 480~550 DEG C, and the 2nd temperature is 550~700 DEG C；Retention time at a temperature of the 1st is 0~24 Hour, preferably 2~15 hours；Retention time at a temperature of the 2nd is 0~10 hour, preferably 0.5~6 hour.
41. according to the manufacturing method of crystallized glass article described in claim 35~37 any claim, which is characterized in that The chemical strengthening technique includes: 6~20 in the salt bath of the melting Na salt for the temperature that devitrified glass is immersed in 430 DEG C~470 DEG C Hour, preferred range is 435 DEG C~460 DEG C, and preferably time range is 8~13 hours；And/or devitrified glass is immersed in It is melted at a temperature of 400 DEG C~450 DEG C in the salt bath of K salt 1~8 hour, preferably time range is 2~4 hours.
42. according to the manufacturing method of crystallized glass article described in claim 35~37 any claim, which is characterized in that The crystal phase of the crystallized glass article contains a lithium metasilicate；And/or aluminum phosphate；And/or aluminium metaphosphate；And/or lithium phosphate；With/ Or quartz crystal；And/or zirconium silicate crystal.
43. the manufacturing method of devitrified glass, which is characterized in that the described method comprises the following steps:
Host glass is formed, component in terms of weight percentage, contains: SiO2: 50~59.5%；Al2O3: 15~25%； Li2O:4~10%；Na2O:5~15%；P2O5: 0.1~10%；ZrO2: 0~10%；ZnO:0~10%；MgO:0~10%； K2O:0~10%；SrO:0~5%；BaO:0~5%；TiO2: 0~5%；Y2O3: 0~5%；B2O3: 0~6%；Clarifying agent: 0 ~2%.
Devitrified glass is formed by crystallization process to the host glass.
44. the manufacturing method of devitrified glass according to claim 58, which is characterized in that the host glass, component In terms of weight percentage, contain: SiO2: 52~58%；And/or Al2O3: 16~23%；And/or Li2O:4~8%, preferably Li2O:5~7%；And/or Na2O:8~12%；And/or P2O5: 0.5~5%；And/or ZrO2: 0.1~10%, preferably ZrO2: 0.5~6%, more preferable ZrO2: 1~4%；And/or ZnO:1~8%；And/or MgO:0.5~5%；And/or K2O:0~5%； And/or SrO:0~1%；And/or BaO:0~1%；And/or TiO2: 0~1%；And/or Y2O3: 0~1%；And/or B2O3: 0.1 ~4%；And/or clarifying agent: 0~1%；And/or (Li2O+Na2O)/(SiO2+Al2O3) it is 0.15~0.35, preferably (Li2O+ Na2O)/(SiO2+Al2O3) it is 0.16~0.32, more preferable (Li2O+Na2O)/(SiO2+Al2O3) it is 0.17~0.30；And/or (Li2O+Na2O)/Al2O3It is 0.5~1.4, preferably (Li2O+Na2O)/Al2O3It is 0.53~1.3, more preferable (Li2O+ Na2O)/Al2O3It is 0.55~1.2；And/or Li2O/Na2O is 0.28~1.2, preferably Li2O/Na2O is 0.29~1.1, more excellent Select Li2O/Na2O is 0.30~1.0.
45. according to the manufacturing method of devitrified glass described in claim 43 or 44 any claims, which is characterized in that described Host glass, component in terms of weight percentage, contain: NiO:0~4%, preferably NiO:0.1~3%；And/or Ni2O3: 0 ~4%, preferably Ni2O3: 0.1~3%；And/or CoO:0~2%, preferred CoO:0.05~1.8%；And/or Co2O3: 0~ 2%, preferably Co2O3: 0.05~1.8%；And/or Fe2O3: 0~7%, preferably Fe2O3: 0.2~5%；And/or MnO2: 0~ 4%, preferably MnO2: 0.1~3%；And/or Er2O3: 0~8%, preferably Er2O3: 0.4~6%；And/or Nd2O3: 0~8%, it is excellent Select Nd2O3: 0.4~6%；And/or Cu2O:0~4%, preferably Cu2O:0.5~3%；And/or Pr2O5: 0~8%, preferably Pr2O5: 0.4~6%；And/or CeO2: 0~4%, preferably CeO2: 0.5~3%.
46. according to the manufacturing method of devitrified glass described in claim 43~45 any claim, which is characterized in that described Crystallization process is the following steps are included: Crystallizing treatment temperature as defined in being warming up to protects its temperature after reaching heat treatment temperature It holds the regular hour, then cools down again.The temperature of the Crystallizing treatment be 480~700 DEG C, preferably 520~600 DEG C, In Retention time at a temperature of Crystallizing treatment is 0~8 hour, preferably 1~6 hour.
47. according to the manufacturing method of devitrified glass described in claim 43~45 any claim, which is characterized in that described Crystallization process at a temperature of the 1st the following steps are included: carry out the processing of nucleation technique, then higher than nucleation technological temperature the The processing of crystal growth technique is carried out at a temperature of 2.
48. the manufacturing method of devitrified glass according to claim 47, which is characterized in that the crystallization process includes following Step: the 1st temperature is 480~550 DEG C, and the 2nd temperature is 550~700 DEG C；Retention time at a temperature of the 1st is 0~24 small When, preferably 2~15 hours；Retention time at a temperature of the 2nd is 0~10 hour, preferably 0.5~6 hour.
49. according to the manufacturing method of devitrified glass described in claim 43~45 any claim, which is characterized in that described The crystal phase of devitrified glass contains a lithium metasilicate；And/or aluminum phosphate；And/or aluminium metaphosphate；And/or lithium phosphate；And/or quartz-crystal Body；And/or zirconium silicate crystal.
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CN113831021A (en) * 2021-11-15 2021-12-24 清远南玻节能新材料有限公司 Microcrystalline glass, preparation method thereof, glass protective layer, glass cover plate and electronic device
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CN113831021A (en) * 2021-11-15 2021-12-24 清远南玻节能新材料有限公司 Microcrystalline glass, preparation method thereof, glass protective layer, glass cover plate and electronic device

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