CN109574496A - 3D based on network structure regulation is molded hand-set lid glass - Google Patents
3D based on network structure regulation is molded hand-set lid glass Download PDFInfo
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- 239000011521 glass Substances 0.000 title claims abstract description 151
- 230000033228 biological regulation Effects 0.000 title claims abstract description 13
- 238000000465 moulding Methods 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 31
- 238000003426 chemical strengthening reaction Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims description 38
- 150000003839 salts Chemical class 0.000 claims description 29
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical group [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 238000012545 processing Methods 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 12
- 238000013459 approach Methods 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 8
- 235000010333 potassium nitrate Nutrition 0.000 claims description 6
- 239000004323 potassium nitrate Substances 0.000 claims description 6
- 230000003014 reinforcing effect Effects 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 239000000155 melt Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 37
- 229910052593 corundum Inorganic materials 0.000 abstract description 16
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 9
- 239000003513 alkali Substances 0.000 abstract description 8
- 239000005368 silicate glass Substances 0.000 abstract description 7
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052681 coesite Inorganic materials 0.000 abstract description 5
- 238000004891 communication Methods 0.000 abstract description 5
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 5
- 239000000377 silicon dioxide Substances 0.000 abstract description 5
- 229910052682 stishovite Inorganic materials 0.000 abstract description 5
- 229910052905 tridymite Inorganic materials 0.000 abstract description 5
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000748 compression moulding Methods 0.000 abstract description 3
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 abstract description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 230000004927 fusion Effects 0.000 description 9
- 230000006872 improvement Effects 0.000 description 8
- 238000005342 ion exchange Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000013461 design Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000005357 flat glass Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000005352 clarification Methods 0.000 description 3
- 230000002596 correlated effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 241000282575 Gorilla Species 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000008395 clarifying agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910017107 AlOx Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000167880 Hirundinidae Species 0.000 description 1
- 229910017976 MgO 4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910001491 alkali aluminosilicate Inorganic materials 0.000 description 1
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 1
- 229940024548 aluminum oxide Drugs 0.000 description 1
- 238000007507 annealing of glass Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 210000002583 cell-derived microparticle Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 238000013003 hot bending Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- -1 oxonium ion Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
-
- 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
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/004—Refining agents
-
- 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
- C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
- C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
- C03C21/002—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to perform ion-exchange between alkali ions
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Glass Compositions (AREA)
Abstract
3D molding hand-set lid glass based on network structure regulation belongs to glass art.Glass composition of the present invention illustrates are as follows: SiO based on mass percentage256.0±0.5；B2O33.0±0.3；Al2O320.0±0.2；Li2O 3.0±0.1；Na2O 9.5±0.2；MgO 5.0±0.2；ZnO 3.0±0.2；ZrO20.2±0.05；SO30.2±0.05；MoO30.1±0.05；And SiO2+Al2O3+ZrO2+MgO 81.2.Hand-set lid glass of the present invention had not only been able to satisfy 5G communication and 3D compression molding, but also had fine chemical strengthening performance, and the hand-set lid glass is alkali alumina silicate glass, and the hand-set lid glass composition includes Network former, intermediate, network outer body, auxiliary agent.3D molding hand-set lid glass highest chemical strengthening temperature of the invention meets T14.5-50 DEG C of temperature condition, and when being lower than the temperature, chemcor glass not recurring structure relaxation, surface stress can permanent retention.
Description
Technical field
The present invention relates to the 3D regulated and controled based on network structure to be molded hand-set lid glass, belongs to glass art.
Background technique
2007, the iPhone mobile phone that American Apple Inc sells opened the smart phone epoch, and smart phone is in addition to full
Sufficient wireless communication function, also support internet such as mobile office, entertain, take pictures at the functions.Smart phone has lightening, large-size screen monitors
Change, intelligent feature, abandoned cell phone keyboard, correlated inputs output operation and information browse are realized by touch screen.
Smart phone screen size accounts for 90% or more mobile phone plane, and when mobile phone screen size is generally greater than 5, intelligence
Screen easily causes surface scratching and impact damaged to mobile phone in use, therefore screen protection material must as smart phone
Indispensable critical component, it is desirable that screen protection material has transparent (front shroud has this requirement), lightening, impact resistance, resists
The characteristics such as scratch, in 5G communication era, it is a kind of can the ultra-thin alkali alumina silicate glass of chemical strengthening just become better than acrylic, poly-
The preferred material of ethylene, sapphire, ceramics, metal.
Corning Incorporated in 2007 is used successfully to iPhone using " gorilla (Gorilla) " glass of press over system production
The screen protection of first generation smart phone, be it is a kind of can chemical strengthening ultra-thin alkali alumina silicate glass.Mobile phone screen protection
Glass has the chemical strengthening technology invented the 1960s, ultra-thin forming technique, alkali alumina silicate glass three
Machine fusion has started alkali alumina silicate glass using the new era.
Hand-set lid glass plays important protective effect to screen, is also known as hand-set lid glass because it is located at mobile phone appearance
(Cover glass, CG), is known as front shroud positioned at screen side, is known as back shroud positioned at mobile phone back.
Short, molding difficulty of fusion temperature height, large viscosity, clarification difficulty, material property etc. one is presented in hand-set lid glass in production
Series of problems is primarily due in glass largely introduce " Al2O3" caused by, Al2O3Mass content reaches 5-24%, Al2O3It is more, glass
Hardness is big, scratch resistance, since the network structure elements of [AlOx] are big, glass structure gap is made to become larger, and easily promotes chemical strengthening
Ion exchange.Additionally, due to Al2O3Fusing point is up to 2045 DEG C, causes glass melting very difficult, secondly Al2O3Also result in glass
Glass surface tension increases, and will also result in very big difficulty to glass melt clarification.Hand-set lid glass chemistry forms mainly with bases
Metal oxide R2O(Li2O、Na2O、K2O)、Al2O3、SiO2Based on three type oxides, it is aided with other ingredients in glass, is used to
Improve and adjust glass physicochemical processes performance.
Tian Yingliang et al., which writes, is published in " University On The Mountain Of Swallows's journal " the 4th phase in 2017 " ultra-thin alkali manosil AS of chemical reinforcing type
Alkali alumina silicate glass component characteristic is clearly discussed in salt glass general situation of development and prospect " paper, wherein being formed about network
Body (SiO2、B2O3、P2O5), intermediate (Al2O3), network outer body (R2O、RO、RO2Deng) effect and recommend dosage give phase
It closes and discusses, and indicate alkali aluminosilicate cover board protection glass chemistry composition basic design criteria, but between composition used in glass
Synergistic effect and its influence of physicochemical processes performance is not provided and is clearly answered.
For the composition design of hand-set lid glass, need to cooperate with processing " physicochemical property-processing performance-application performance "
Relationship between three.For hand-set lid glass, physicochemical property needs to pay close attention to elasticity modulus；Processing performance needs
Pay close attention to fusion temperature T2 (T2 is that glass viscosity 102 moors corresponding temperature, thereafter), work temperature 4 and softening point temperature
T7.6；Application performance needs to pay close attention to the ion-exchange capacity and shock resistance of chemical strengthening, and the two, which exists, to be positively correlated.Springform
Amount is reflection material stiffness and hardness, can embody glass scratch resistance capability indirectly；Fusion temperature T2, work temperature 4 and soft
Change temperature T7.6 and reflect glass melting clarification, molding complexity respectively, glass melting will be made clear if T2 is greater than 1600 DEG C
It is difficult to clearly, T4 is excessively high greater than 1200 DEG C of molding feed temperatures, if less than 320 DEG C reflection frits of Δ T=T4-T7.6 are inclined
It is short, it is unfavorable for glass molding and extends and high surface accuracy, glass surface is easily made small wave and rough occur.
(below can abbreviation mobile phone) has become the important personal digital assistant device of the mankind, glass material currently, smart phone
Have become smart phone important component, such as front shroud, display screen, back shroud.Under 5G communication condition, cover board protects glass will
As machine back shroud optimal material because metal material can have to 5G high-frequency signal it is apparent absorb and shielding action, and glass
Material can make electromagnetic signal smoothly transmit and penetrate, and rear cover 9 piece-root graftings of needs of metal material are received and transmitting antenna, and glass back cover
2 antennas are only needed, illustrate that glass material does not generate signal shielding, there is good wave transparent ability.
In addition, metal back cover is almost without any application possibility, and glass material can as wireless charging technology develops
To be competent at very well.For the high-frequency signal of 5G, glass material has reduction dielectric constant, reduces dielectric loss characteristics,
Therefore high permeability (light transmission and wave transparent), high rigidity, the wearability of glass are to shield and shield comprehensively the preferred of curved surface hand-set lid comprehensively
Material, but the brittleness of glass and crash resistance deficiency are also its key, therefore the back shroud as smart phone, especially screen comprehensively
Or screen curved surface mobile phone, drop resistant performance are particularly important comprehensively.
In terms of improving cover board protection glass shock resistance, more energy and attention are placed on by many mechanisms and unit
Al2O3Content increases and the change of aluminum-oxide polyhedron ([ALOx], x=4,6), to coordinate scratch resistance and shock resistance effect.It is healthy and free from worry
Chemical composition range of the company earliest mentioned in the disclosed patent suitable for touch screen cover-plate glass is (mol%): SiO2
64~68, Al2O38~12, Na2O 12~16, K2O 2~5, MgO 4~6, CaO 0~5, wherein Na2O+K2O-Al2O34
In~10 ranges, therefore aluminium oxide is with [AlO4] tetrahedron is present in glass structure；And Na2O+K2O+MgO+CaO-Al2O3
>=10, but glass melting temperature is greater than 1600 DEG C, feed temperature is greater than 1200 DEG C, and Δ T is less than 320 DEG C, therefore glass melting
Become very difficult with molding.
Start within 2013 3D song screen mobile phone occur, 3D song screen mobile phone is by 3D moulding hand-set lid glass and flexible screen phase
Mutually cooperation is realized, screen display area can be made bigger, and frame is smaller, shields accounting up to 93% or more, visual display effect is more preferable.
What 3D hand-set lid glass was usually obtained with thickness 0.7-0.9mm plate glass original piece by hot bending shape, belong to
In glass secondary forming process, production efficiency is relatively low, and production cost is high, and product yield is low, perplexs and influence 3D always
Mobile Industry development, thus be badly in need of developing it is a kind of meet 3D cover-plate glass compression molding chemical composition and processing technology, need same
When to meet elasticity modulus big, fusion temperature is low, molding range is wide, strain point temperature is relatively high, the coefficient of expansion is moderate, chemical strengthening
The conditions such as effect is good.
But in hand-set lid glass composition is designed and developed, it often will appear two kinds extremely: 1) chemical strengthening performance and bullet
Property modulus is fine, but glass melting and processability are very poor；2) glass melting processability is good, but chemical strengthening performance and
Elasticity modulus is very poor.
Therefore be badly in need of finding a kind of hand-set lid that is suitable for and protect glass composition design method, have specific agreement criterion and
Mathematical relationship, for instructing hand-set lid glass formula to develop.
Summary of the invention
The present invention provides one kind and had not only been able to satisfy 5G communication and 3D compression molding, but also the hand-set lid with fine chemical strengthening
Glass composition design method, the hand-set lid glass are alkali alumina silicate glass, and the composition of the hand-set lid glass includes
Network former, intermediate, network outer body, auxiliary agent.
3D molding hand-set lid glass network former of the invention is SiO2、B2O3, it is the pass to form glass network structure
Key oxide, the structural unit ligancy of glass network are 3 or 4, and structure is triangle body or tetrahedron, are connected with apex angle, favorably
In glass physicochemical property.
3D molding hand-set lid glass network ectosome of the present invention is Li2O、Na2O、MgO、ZnO、ZrO2, cannot independently form
Glass is responsible for providing " free oxygen ", plays the role of suspension, reduce glass physicochemical property, be conducive to glazier except network
Skill performance.
3D molding hand-set lid glass intermediate of the present invention is Al2O3, glass cannot be independently formed, when acquisition is " free
After oxygen ", ligancy becomes 4 from 6, becomes glass network a part；When " free oxygen " deficiency when, in glass network it
Outside, it is acted on network outer body close.
3D molding hand-set lid glass agent of the present invention is clarifying agent and surfactant, and wherein clarifying agent is SO3, surface
Activating agent MoO3。
The present invention solves 3D molding hand-set lid glass melting clarifying temp, forming temperature scope and chemical strengthening method,
Main technical schemes are regulation glass network structure tightness degree, and glass structure tightness degree and K are closely related, K=O/ (Si+B
+ Al), O is glass oxonium ion moles total number, and Si+B+Al is silicon, boron, aluminium ion total amount in glass.
Present invention discover that glass structure is close, and glass melting is tired when the K value of 3D molding hand-set lid glass is less than 2.13
Difficulty, is unfavorable for ultra-thin molding, and ion exchange is difficult；When K is greater than 2.16, glass structure is more loose, although glass melting is easy,
But physicochemical property is deteriorated, and ion-exchange effect is deteriorated, and value of compressive stress is low；Therefore K value optimum range is 2.13-2.16.
Present invention discover that the glass network structure tightness degree of 3D molding hand-set lid glass is with the coefficient of expansion with very strong
Correlation, when K is in optimum range 2.13-2.16,20-300 DEG C of the coefficient of mean linear thermal expansion is (7.4-9.5) × 10-6/℃。
Present invention discover that 3D is molded hand-set lid glass modulus in addition to related to K value, and when K is 2.13-2.16, glass
Structure is moderately close, and elasticity modulus is relatively high, in addition to this also with key oxides Al2O3、ZrO2, MgO it is related.Al2O3、
ZrO2, MgO three's best in quality mass percent be 78.4-81.2, help to improve strain point temperature T14.5, preferably strain
Point temperature T14.5 is greater than 520 DEG C.
3D molding hand-set lid glass highest chemical strengthening temperature of the invention meets T14.5-50 DEG C of condition, is lower than the temperature
When spending, glass ion exchange will not recurring structure relaxation, surface stress can permanent retention, otherwise surface stress is difficult to maintain, very
To because glass relaxation causes surface that should decline.
3D is molded hand-set lid glass composition design method by the present invention, is illustrated with the chemical composition of optimization.
The further improvement of 3D molding hand-set lid glass of the present invention and limit value, based on mass percentage, wherein ± be
Tolerance range, the chemical composition (being defined as 1#) of the 3D molding hand-set lid glass are as follows:
The further improvement of 3D molding hand-set lid glass of the present invention and limit value, based on mass percentage, wherein ± be
Tolerance range, the chemical composition (being defined as 2#) of the 3D molding hand-set lid glass are as follows:
The further improvement of 3D molding hand-set lid glass of the present invention and limit value, based on mass percentage, wherein ± be
Tolerance range, the chemical composition (being defined as 3#) of the 3D molding hand-set lid glass are as follows:
The further improvement of 3D molding hand-set lid glass of the present invention and limit value, based on mass percentage, wherein ± be
Tolerance range, the chemical composition (being defined as 4#) of the 3D molding hand-set lid glass are as follows:
The further improvement of 3D molding hand-set lid glass of the present invention and limit value, based on mass percentage, wherein ± be
Tolerance range, the chemical composition (being defined as 5#) of the 3D molding hand-set lid glass are as follows:
The further improvement of 3D molding hand-set lid glass of the present invention and limit value, based on mass percentage, wherein ± be
Tolerance range, the chemical composition (being defined as 6#) of the 3D molding hand-set lid glass are as follows:
The further improvement of 3D molding hand-set lid glass of the present invention and limit value, based on mass percentage, wherein ± be
Tolerance range, the chemical composition (being defined as 7#) of the 3D molding hand-set lid glass are as follows:
The further improvement of 3D molding hand-set lid glass of the present invention and limit value, based on mass percentage, wherein ± be
Tolerance range, the chemical composition (being defined as 8#) of the 3D molding hand-set lid glass are as follows:
3D of the present invention molding hand-set lid glass chemistry forms preferred applicable raw materials, calculates glass formula, carry out fusing and
Molding, anneals, is subsequently processed into 0.7mm thin slice, by well known one-step method chemical strengthening technique and three-step approach chemical strengthening
Technique carries out Chemical enhancement.
Wherein one-step method chemical strengthening process conditions are as follows: reinforcing medium is potassium nitrate fused salt, strengthens 420 DEG C of temperature, is strengthened
Time 6h.
Wherein three-step approach chemical strengthening process conditions are as follows: the processing of first step fused salt, medium is composite fused salt, composite fused salt group
As 0-40wt%NaNO3And 60wt%-100wt%KNO3, 380-420 DEG C of heat treatment temperature, handle time 1-3h；Second step
Heat treatment, medium are air, and heat treatment temperature is 410-430 DEG C, handle time 0.3-1h；The processing of third step fused salt, medium
For 100% potassium nitrate fused salt, 420-450 DEG C of heat treatment temperature, time 1-2h is handled.
Specific embodiment
One-step method chemical strengthening process conditions are as follows: reinforcing medium is potassium nitrate fused salt, strengthens 420 DEG C of temperature, enhanced time
6h。
Wherein three-step approach chemical strengthening process conditions are as follows: the processing of first step fused salt, medium is composite fused salt, composite fused salt group
As 0-40wt%NaNO3And 60wt%-100wt%KNO3, 380-420 DEG C of heat treatment temperature, handle time 1-3h；Second step
Heat treatment, medium are air, and heat treatment temperature is 410-430 DEG C, handle time 0.3-1h；The processing of third step fused salt, medium
For 100% potassium nitrate fused salt, 420-450 DEG C of heat treatment temperature, time 1-2h is handled.
Three-step approach chemical strengthening process conditions in example are as follows: the processing of first step fused salt, medium is composite fused salt, composite fused salt
Group becomes 40wt%NaNO3And 60wt%KNO3, 400 DEG C of heat treatment temperature, handle time 2h；Second step heat treatment, medium are
Air, heat treatment temperature are 420 DEG C, handle time 1h；The processing of third step fused salt, medium are 100% potassium nitrate fused salt, heat treatment
440 DEG C of temperature, handle time 1h.
But the present invention is not limited to this, and one-step method chemical strengthening technique, three-step approach chemical strengthening technique is also existing
There is technology.
The physicochemical processes performance and chemical strengthening performance test method therefor and instrument of 3D molding hand-set lid glass of the present invention
Device is as follows:
Elastic modulus E measurement uses " the 6th part of colouless optical glass test method: Young mould GB/T 7962.6-2010
Amount, modulus of shearing and Poisson's ratio "；
The coefficient of mean linear thermal expansion a measurement uses GB/T 16920-2015 " measurement of glass the coefficient of mean linear thermal expansion ",
Take the average value within the scope of 20-300 DEG C；
Fusion temperature T2 and feed temperature T4 measurement uses " the electronic glass high temperature viscosity test side SJ/T 11040-1996
Method "；
Softening point temperature T7.6 measurement uses GB/T 28195-2011 " glass softening point test method "；
Strain point temperature T14.5 measurement uses " the test side of electronic glass annealing point and strain point SJ/T 11039-1996
Method "；
The surface stress that bearing stress (CS) and ion exchange layer depth (DOL) measurement are produced using Zhe Yuan company, Japan
Measuring instrument, one-step method and three-step approach Survey Software and photoelastic constant difference.
Table 1 is that eight groups of chemical compositions that the method for the present invention parses are prepared at glass, and have carried out every correlation
It is capable of measuring.From the point of view of elasticity modulus result, it is when aluminium oxide is 13wt% with being positively correlated property of alumina content
70.4GPa is 75.8GPa when aluminium oxide is 20wt%；Fusion temperature T2 is 1536-1575 DEG C, all less than 1600
DEG C, illustrate that glass of the present invention has fine pre-arcing characterisitics；Forming temperature scope Δ T is 357-361 DEG C, all greater than 320 DEG C, it was demonstrated that
Glass forming temperature wider range of the present invention.T14.5 is greater than 522 DEG C, illustrates that highest chemical strengthening temperature can use 472 DEG C, meets
Fused salt used in one-step method and three-step approach proposed by the present invention strengthens temperature requirement.
The present invention is based on after glass structure regulation, the elastic appropriateness of glass structure creates reasonable glass structure hole, favorably
In glass particle thermal vibration, the coefficient of expansion is (7.4-9.5) × 10-6/ DEG C, when it is in 380-450 DEG C of high-temperature molten salt, glass
The available appropriate expansion diastole of glass structure, the small Li of inside glass ionic radius+And Na+Promoted it de- by high temperature energy effect
It fetters from glass network structure covalent bond, is migrated to fused salt, and the K that the ionic radius in fused salt is big+And Na+It is spread and ion
Into inside glass surface ion exchange occurs between surface layer of glass and fused salt for migration, glass surface occur from
The big K of sub- radius+Replace Li+And Na+, extrusion stress is formed, impact and scuffing effect are resisted.As ion time extends, ion
It exchanges depth to increase, is finally reached balance.
3D of the present invention molding hand-set lid glass physicochemical property, processing performance and chemical strengthening aspect of performance compared to than
Compared with example U.S. CORNING the 5th generation cover-plate glass (GG5) product, show that its quality of alumina degree reaches in open source information
23% or more, its exclusive smelting technology and overflow molding are completely dependent on to realize production, fusion temperature is greater than 1650 DEG C,
It can also calculate and confirm that the glass melting temperature is really very high from 884 DEG C of its softening point temperature, but the present invention can be by glass
Fusion temperature reduces, and forming temperature scope is wider, is conducive to the fusing and molding of hand-set lid glass, and part of
The elasticity modulus and comparative example of glass are close.Chemically from the point of view of strengthening effect, the present invention is after reducing aluminium oxide dosage, in glass
Beneficial effect, the chemical strengthening effect beyond comparative example are obtained in terms of structure regulating.Sufficiently prove that glass composition of the invention is set
Meter method can be molded the exploitation of hand-set lid glass for 3D and point the direction, and reduce production difficulty, save human and material resources.
Table 1
Note: "-" is not express index value.
Claims (10)
1. the 3D based on network structure regulation is molded hand-set lid glass, which is characterized in that based on mass percentage, wherein ±
For tolerance range, glass chemistry composition are as follows:
2. the 3D based on network structure regulation is molded hand-set lid glass, which is characterized in that based on mass percentage, wherein ±
For tolerance range, glass chemistry composition are as follows:
3. the 3D based on network structure regulation is molded hand-set lid glass, which is characterized in that based on mass percentage, wherein ±
For tolerance range, glass chemistry composition are as follows:
4. the 3D based on network structure regulation is molded hand-set lid glass, which is characterized in that based on mass percentage, wherein ±
For tolerance range, glass chemistry composition are as follows:
5. the 3D based on network structure regulation is molded hand-set lid glass, which is characterized in that based on mass percentage, wherein ±
For tolerance range, glass chemistry composition are as follows:
6. the 3D based on network structure regulation is molded hand-set lid glass, which is characterized in that based on mass percentage, wherein ±
For tolerance range, glass chemistry composition are as follows:
7. the 3D based on network structure regulation is molded hand-set lid glass, which is characterized in that based on mass percentage, wherein ±
For tolerance range, glass chemistry composition are as follows:
8. the 3D based on network structure regulation is molded hand-set lid glass, which is characterized in that based on mass percentage, wherein ±
For tolerance range, glass chemistry composition are as follows:
9. the method for preparing the 3D molding hand-set lid glass as described in claim 1-8 any one, which is characterized in that will be former
Material melts and process is once molding formed, anneals, and then presses one-step method chemical strengthening technique and three-step approach chemical strengthening work
Skill carries out Chemical enhancement.
10. according to the method described in claim 9, wherein one-step method chemical strengthening process conditions are as follows: reinforcing medium is potassium nitrate
Fused salt strengthens 420 DEG C of temperature, enhanced time 6h；
Wherein three-step approach chemical strengthening process conditions are as follows: the processing of first step fused salt, medium is composite fused salt, and composite fused salt group becomes
0-40wt%NaNO3And 60wt%-100wt%KNO3, 380-420 DEG C of heat treatment temperature, handle time 1-3h；Second step heating
Processing, medium are air, and heat treatment temperature is 410-430 DEG C, handle time 0.3-1h；The processing of third step fused salt, medium is nitre
Sour potassium fused salt, handles time 1-2h by 420-450 DEG C of heat treatment temperature.
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