CN106573826A - Crystallized glass - Google Patents
Crystallized glass Download PDFInfo
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- CN106573826A CN106573826A CN201580041093.5A CN201580041093A CN106573826A CN 106573826 A CN106573826 A CN 106573826A CN 201580041093 A CN201580041093 A CN 201580041093A CN 106573826 A CN106573826 A CN 106573826A
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- expansion
- change
- thermal coefficient
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- glass ceramics
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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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
-
- 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
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
-
- 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
- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
- C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
-
- 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
- C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
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- 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)
- Ceramic Engineering (AREA)
- Glass Compositions (AREA)
- Re-Forming, After-Treatment, Cutting And Transporting Of Glass Products (AREA)
Abstract
Provided is a crystallized glass that makes it possible to minimize changes in size even when heat treatment is performed at a temperature that is equal to or less than the glass transition point temperature thereof and the crystallized glass is subsequently left in an environment in which the temperature is liable to change. This crystallized glass is characterized in that: the difference (Delta Alfa) in the thermal expansion coefficient before and after heat treatment is within 0+/-0.20*10-7/DEGC when heat treatment is performed for 24 hours at a temperature from 300 DEG C to the glass transition point temperature; and the thermal expansion coefficient at -40 to 80 DEGC after the heat treatment is within 0+/-0.3*10-7/DEGC.
Description
Technical field
The present invention relates to a kind of sintered glass ceramics.
Background technology
The resonator of interference of light be make use of as the wavelength filter function of narrow-band, therefore it is multiple to be used for wavelength
With the plurality of devices in optical communication system.Wherein, etalon is the wavelength locking for making the wavelength stabilization of semiconductor laser
The important resonator of the equalizer of device or optical signal etc..Etalon is by a pair of parallel flat with high flatness and the depth of parallelism
Face semi-transparent semi-reflecting lens are constituted, with multi interference is carried out between semi-transparent semi-reflecting lens by making to be injected into light therein, so that right
The property that should be transmitted in the photoperiodism of the wavelength for interfering number of times.
In addition, cavity will be referred to as between semi-transparent semi-reflecting lens and semi-transparent semi-reflecting lens.For cavity, it is desirable to which transmission peak wavelength is not with making
Temperature change with and change.Specifically, it is desirable to even if temperature changes, refractive index or semi-transparent semi-reflecting lens are each other
Interval also do not change so that optical path length is not varied with temperature and is changed.
Therefore, it is filled with cavity relative to the minimum air of the variations in refractive index of temperature.In addition, sky will be used in cavity
In the case that gas is full of, spacer is set between semi-transparent semi-reflecting lens and semi-transparent semi-reflecting lens and the air gap is formed.
Even if in addition, in order to temperature changes, not making the mutual interval occurred change of semi-transparent semi-reflecting lens, as isolation yet
Thing is using the little sintered glass ceramics of thermal coefficient of expansion as Patent Document 1.
In addition, when spacer and semi-transparent semi-reflecting lens are engaged, becoming with the temperature in use as bonding agent can become
The reason for changing and be widely varied semi-transparent semi-reflecting lens mutual interval occurred, so the optical contact by not using bonding agent
Method is engaged.In addition, in optical contact method, in order to the engagement for improving spacer and semi-transparent semi-reflecting lens at short notice it is strong
Degree, after docking spacer and semi-transparent semi-reflecting lens sometimes, is heated to the temperature below glass transition point and is engaged.
Prior art literature
Patent documentation
Patent documentation 1：Japanese Unexamined Patent Publication 2004-29723 publications
The content of the invention
Invent problem to be solved
However, in the case where spacer is heated while being engaged with semi-transparent semi-reflecting lens, although will not be because connecing
Heat treatment during conjunction makes the change in size of spacer, but causes isolation due to the temperature change carried out in the use after heat treatment
The change in size of thing, exists and can not be certain by semi-transparent semi-reflecting lens mutual distance maintaining and cannot obtain required optics
The problem of characteristic.
It is an object of the present invention to provide even if a kind of temperature with below glass transition point is heat-treated, and it
After be exposed in the environment of temperature changes, it is also possible to suppress the sintered glass ceramics of change in size.
Method for solving problem
That is, sintered glass ceramics of the invention is characterised by, carries out 24 hours with the temperature of 300 DEG C～glass transition point
Heat treatment, the difference (Δ α) of the thermal coefficient of expansion before and after heat treatment is ± 0.20 × 10-7/ DEG C within, also, after above-mentioned heat treatment
- 40～80 DEG C when thermal coefficient of expansion be 0 ± 0.3 × 10-7/ DEG C within.
The effect of invention
Even if the sintered glass ceramics of the present invention is heat-treated with the temperature below glass transition point, and is exposed to afterwards
In the environment of temperature changes, it is also possible to suppress by change in size caused by temperature change.Therefore, it is particular enable to be suitable as
Spacer of the requirement according to the etalon of the dimensional stability of temperature change.
Specific embodiment
The sintered glass ceramics of the present invention carries out 24 hours heat treatments with the temperature of 300 DEG C～glass transition point, at heat
The difference (Δ α) of the thermal coefficient of expansion before and after reason is set to ± 0.20 × 10-7/ DEG C within, i.e., -0.20 × 10- 7/ DEG C～+0.20 ×
10-7/ DEG C as in little scope, thus suppress, by the change of the thermal coefficient of expansion of sintered glass ceramics caused by heat treatment, to press down
The change in size of sintered glass ceramics processed, also, the thermal coefficient of expansion of -40 after by heat treatment～80 DEG C is set to 0 ± 0.3
×10-7/ DEG C within, i.e., -0.3 × 10-7/ DEG C～+0.3 × 10-7/ DEG C, suppress by sintered glass ceramics caused by temperature change
The change of thermal coefficient of expansion, suppresses the change in size of sintered glass ceramics.Even if accordingly, it is capable to accessing with below glass transition point
Temperature carry out heat treatment, and in the environment of being exposed to temperature change afterwards, the also little sintered glass ceramics of change in size.At heat
The preferred scope of the difference (Δ α) of the thermal coefficient of expansion before and after reason is ± 0.15 × 10-7/ DEG C within, i.e., -0.15 × 10-7/℃
～+0.15 × 10-7/ DEG C, the preferred scope of thermal coefficient of expansion during -40 after heat treatment～80 DEG C is 0 ± 0.25 × 10-7/ DEG C within, i.e., -0.25 × 10-7/ DEG C～+0.25 × 10-7/℃。
In addition, in order that the difference (Δ α) of thermal coefficient of expansion before and after heat treatment is little, and make after heat treatment -40～80
DEG C when thermal coefficient of expansion be 0 ± 0.3 × 10-7/ DEG C within, in sintered glass ceramics, adjust separate out crystallization species, crystallization
Degree (ratio of the crystallization of precipitation), the composition of crystallization, the ratio of glass phase, composition of glass phase etc..
Specifically, β-quartz solid solution or beta-eucryptite solid solution is preferably made to separate out as the species of primary crystallization,
And, degree of crystallinity sintered glass ceramics by percentage to the quality for 72～80%.The preferred scope of degree of crystallinity is with quality hundred
Ratio is divided to be calculated as 73～79%.It is used as by making the β-quartz solid solution with negative thermal coefficient of expansion or beta-eucryptite solid solution
Primary crystallization is separated out, and degree of crystallinity is set to mass percent is calculated as 73～79%, so as to the negative thermal coefficient of expansion of crystalline phase
Cancel out each other with the positive thermal coefficient of expansion of glass phase, the thermal coefficient of expansion of sintered glass ceramics can be made to be close to 0 × 10-7/℃
(zero), it is readily obtained by the little sintered glass ceramics of change in size caused by temperature change.In addition, in sintered glass ceramics, can
The ratio for being caused the glass phase of structure change by heat treatment is reduced, therefore, it is possible to suppress by thermal coefficient of expansion caused by heat treatment
Change, be readily obtained by the little sintered glass ceramics of change in size caused by heat treatment.If in addition, degree of crystallinity is too low, crystallizing
The oriented negative direction of thermal coefficient of expansion of phase becomes big tendency, and, the SiO of glass phase2Content increase, have the heat of glass phase
The tendency that the coefficient of expansion is reduced.Therefore, the positive thermal coefficient of expansion of the negative thermal coefficient of expansion and glass phase of crystalline phase can not phase
Mutually offset, the oriented negative direction of thermal coefficient of expansion of sintered glass ceramics becomes big tendency, by change in size caused by temperature change
Easily become big.However, if degree of crystallinity is too high, the thermal coefficient of expansion of sintered glass ceramics has inclining from the positive direction change of negative sense
To, and, the SiO of glass phase2Content reduce, have the tendency of to make the thermal coefficient of expansion of glass phase to become big.Therefore, crystalline phase
The thermal coefficient of expansion of thermal coefficient of expansion and glass phase can not be cancelled out each other, the oriented positive direction of thermal coefficient of expansion of sintered glass ceramics
Become big tendency, easily become big by change in size caused by temperature change.
In addition, the sintered glass ceramics of the present invention, preferably with Li2O·Al2O3·nSiO2β-the quartz solid solution of expression or
SiO in beta-eucryptite solid solution2Solid solubility n with molar ratio computing as more than 6.9.By solid solubility n is set to mol ratio
More than 6.9 are calculated as, β-quartz solid solution or the thermal coefficient of expansion of beta-eucryptite solid solution can be suppressed to become in negative direction
Excessive, the thermal coefficient of expansion of sintered glass ceramics when making after heat treatment -40～80 DEG C is close to 0 × 10-7/ DEG C (zero).If solid solution
N is too small for degree, then the oriented negative direction of the thermal coefficient of expansion of β-quartz solid solution or beta-eucryptite solid solution becomes too much and inclines
To, it is difficult to the difference (Δ α) of the thermal coefficient of expansion before and after heat treatment is diminished and is made the thermal coefficient of expansion of sintered glass ceramics be close to 0
×10-7/ DEG C, it is difficult to obtain by the little sintered glass ceramics of change in size caused by temperature change.The preferred scope of solid solubility n
With molar ratio computing as more than 7.0.
In addition, the sintered glass ceramics of the present invention, the thermal coefficient of expansion of crystalline phase when preferably 20～300 DEG C is -11 ×
10-7～0 × 10-7/℃.If the thermal coefficient of expansion of crystalline phase becomes too much in negative direction, the heat for being difficult to make before and after heat treatment
The heat of the sintered glass ceramics of the sintered glass ceramics when difference (Δ α) of the coefficient of expansion diminishes and makes -40～80 DEG C after heat treatment
The coefficient of expansion is close to 0 × 10-7/ DEG C, it is difficult to obtain by the little sintered glass ceramics of change in size caused by temperature change.Crystalline phase
The preferred scope of thermal coefficient of expansion is -10.5 × 10-7～0 × 10-7/℃。
In addition, the sintered glass ceramics of the present invention, preferred crystalline phase contains SiO by percentage to the quality265.0～80.0%,
Al2O310.0～18.0%, Li2O 3.0～6.0%, MgO 0～2.0%, ZnO 0～2.0%, TiO20.5～4.0%,
ZrO20.5～4.0%, P2O50～0.5%.If crystalline phase has such composition, make β-quartz solid solution or β-
Eucryptite solid solution as primary crystallization species separate out, and easily make degree of crystallinity, solid solubility n, crystallization thermal coefficient of expansion into
For in above range, therefore it is readily obtained by the little sintered glass ceramics of change in size caused by heat treatment, temperature change.Will crystallization
The reasons why compositing range of phase is set to above-mentioned is as follows.
SiO2It is the composition that crystallization is constituted in crystalline phase, its content is 65.0～80.0%.If SiO2It is many containing quantitative change,
Then have the tendency of can not from the thermal coefficient of expansion of the positive direction change of negative sense, crystalline phase and glass phase for the thermal coefficient of expansion of crystalline phase
Cancel out each other, have the tendency of to make the thermal coefficient of expansion of sintered glass ceramics to become big to positive direction, it is difficult to obtain by heat treatment, temperature
The little sintered glass ceramics of change in size caused by change.If however, content tails off, with Li2O·Al2O3·nSiO2Represent
SiO in β-quartz solid solution or beta-eucryptite solid solution2Solid solubility n easily diminish, having makes the thermal expansion system of crystalline phase
Number becomes tendencies too much to negative direction, it is difficult to the difference (Δ α) of the thermal coefficient of expansion before and after heat treatment is diminished and is made heat
The thermal coefficient of expansion of the sintered glass ceramics of sintered glass ceramics during -40 after process～80 DEG C is close to 0 × 10-7/ DEG C, it is difficult to
The little sintered glass ceramics of change in size to caused by by temperature change.SiO2More preferably scope be 70.0～78.0%.
Al2O3It is the composition that crystallization is constituted in crystalline phase, its content is 10.0～18.0%.If Al2O3Containing quantitative change
Many, then in crystallizing SiO2Solid solubility n easily diminish, having makes the thermal coefficient of expansion of crystalline phase become too much to negative direction
Tendency, it is difficult to when the difference (Δ α) of the thermal coefficient of expansion before and after heat treatment is diminished and is made -40～80 DEG C after heat treatment
The thermal coefficient of expansion of the sintered glass ceramics of sintered glass ceramics is close to 0 × 10-7/ DEG C, it is difficult to obtain by size caused by temperature change
The little sintered glass ceramics of change.However, if content tails off, the thermal coefficient of expansion of crystalline phase easily becomes big, crystalline phase and glass
The thermal coefficient of expansion of phase can not be cancelled out each other, and have the tendency of to make the thermal coefficient of expansion of sintered glass ceramics to become big to positive direction, difficult
To obtain by the little sintered glass ceramics of change in size caused by heat treatment, temperature change.Al2O3More preferably scope be 13.0～
18.0%.
Li2O is the composition that crystallization is constituted in crystalline phase, and its content is 3.0～6.0%.If Li2O's is more containing quantitative change, then
SiO in crystallization2Solid solubility n easily diminish, have the tendency of to make the thermal coefficient of expansion of crystalline phase to become too much to negative direction,
The difference (Δ α) of the thermal coefficient of expansion for being difficult to make before and after heat treatment diminishes and makes the crystallization at -40～80 DEG C after heat treatment
The thermal coefficient of expansion for changing the sintered glass ceramics of glass is close to 0 × 10-7/ DEG C, it is difficult to obtain by change in size caused by temperature change
Little sintered glass ceramics.However, if content tails off, the thermal coefficient of expansion of crystalline phase easily becomes big, crystalline phase and glass phase
Thermal coefficient of expansion can not be cancelled out each other, and have the tendency of to make the thermal coefficient of expansion of sintered glass ceramics to become big to positive direction, it is difficult to
The little sintered glass ceramics of change in size to caused by by heat treatment, temperature change.Li2The more preferably scope of O is 3.0～5.5%.
MgO and ZnO are the compositions that crystallization is solid-solution in crystalline phase, and the content of these compositions is respectively 0～2.0%.If
These compositions it is many containing quantitative change, then in addition to β-quartz solid solution or beta-eucryptite solid solution, spinelle, gahnite etc.
Heterocrystal also easily separate out, having makes the thermal coefficient of expansion of crystalline phase become big or due to temperature change when heat treatment or use
The worry for causing sintered glass ceramics impaired.The more preferably scope of MgO and ZnO is respectively 0～1.5%.
TiO2And ZrO2It is the crystal nucleon component in crystalline phase, the content of these compositions is respectively 0.5～4.0%.If these
Composition it is many containing quantitative change, then heterocrystal is easily separated out, and having makes the thermal coefficient of expansion of crystalline phase become big or due to heat treatment or make
The temperature change of used time causes the impaired worry of sintered glass ceramics.If however, the content of these compositions tails off, being difficult to obtain institute
The degree of crystallinity of requirement, or the formation of core is insufficient, the crystallization of particle diameter that cannot be required, is separated out when separating out crystallization
β-quartz solid solution or beta-eucryptite solid solution are easily solid into the β-spodumene with positive thermal coefficient of expansion in low-temperature transformation
Solution, as a result, the thermal coefficient of expansion of sintered glass ceramics is difficult to be close to 0 × 10-7/ DEG C (zero), it is difficult to obtain being led by temperature change
The little sintered glass ceramics of the change in size of cause.TiO2And ZrO2More preferably scope be respectively 0.5～3.5%.
P2O5It is the composition that can become nucleus in crystalline phase, its content is 0～0.5%.If P2O5It is many containing quantitative change,
Then heterocrystal is easily separated out, have make the thermal coefficient of expansion of crystalline phase become it is big or due to heat treatment or using when temperature change lead
The worry for causing sintered glass ceramics impaired.P2O5More preferably scope be 0～0.4%.
In addition, the sintered glass ceramics of the present invention preferably has in glass phase, it is SiO by percentage to the quality230.0～
50.0%th, Al2O331.0～45.0%, Li2O 1.0～3.0%, MgO 0～1.0%, ZnO 0～1.0%, TiO20～
5.0%th, ZrO20～5.0%, P2O50～9.0%, BaO 0～8.0%, Na2O 0～4.0%, K2O 0～4.0%.If glass
Glass is mutually the phase with such composition, then be difficult to occur by glass phase caused by heat treatment structure change, be readily obtained by
The little sintered glass ceramics of change in size caused by heat treatment.The reasons why compositing range of glass phase is set to above range is as follows.
SiO2It is the composition of the skeleton that glass is formed in glass phase, its content is 30.0～50.0%.If SiO2Content
Become many, then the thermal coefficient of expansion of glass phase easily diminishes, and the thermal coefficient of expansion of crystalline phase and glass phase can not be cancelled out each other, and make
The thermal coefficient of expansion of sintered glass ceramics becomes big tendency to negative direction, it is difficult to obtain by chi caused by heat treatment, temperature change
The little sintered glass ceramics of very little change.However, if content tails off, the thermal coefficient of expansion of glass phase easily becomes big, in heat treatment
Cause thermal coefficient of expansion to change due to the structure change of glass phase, or have the thermal coefficient of expansion for making sintered glass ceramics to just
Direction become big tendency, it is difficult to obtain by the little sintered glass ceramics of change in size caused by heat treatment, temperature change.SiO2's
More preferably scope is 32.0～48.0%.
Al2O3With SiO2Similarly, be in glass phase formed glass skeleton composition, its content be 31.0～
45.0%.If Al2O3It is many containing quantitative change, then the thermal coefficient of expansion of glass phase easily diminishes, the thermal expansion system of crystalline phase and glass phase
Number can not be cancelled out each other, and have the tendency of to make the thermal coefficient of expansion of sintered glass ceramics to become big to negative direction, it is difficult to obtain by heat
The little sintered glass ceramics of change in size caused by reason, temperature change.However, if content tails off, the thermal coefficient of expansion of glass phase holds
It is variable big, cause thermal coefficient of expansion to change due to the structure change of glass phase in heat treatment, or make crystallization glass
The thermal coefficient of expansion of glass becomes big tendency to positive direction, it is difficult to obtain little by change in size caused by heat treatment, temperature change
Sintered glass ceramics.Al2O3More preferably scope be 32.0～42.0%.
Li2O is glass-modified composition in glass phase, and its content is 1.0～3.0.If Li2O's is more containing quantitative change, then glass
The thermal coefficient of expansion of phase easily becomes big, causes thermal coefficient of expansion to occur to become in heat treatment due to the structure change of glass phase
Change, or have the tendency of to make the thermal coefficient of expansion of sintered glass ceramics to become big to positive direction, it is difficult to obtain by heat treatment, temperature change
The little sintered glass ceramics of caused change in size.However, if content tails off, the thermal coefficient of expansion of glass phase easily diminishes, knot
The thermal coefficient of expansion of crystalline phase and glass phase can not be cancelled out each other, and have the thermal coefficient of expansion for making sintered glass ceramics to become big to negative direction
Tendency, it is difficult to obtain by the little sintered glass ceramics of change in size caused by heat treatment, temperature change.Li2The more preferably scope of O
For 1.5～3.0%.
MgO and ZnO is glass-modified composition in glass phase, and the content of these compositions is respectively 0～1.0%.If these
Composition it is many containing quantitative change, then the thermal coefficient of expansion of glass phase easily becomes big, in heat treatment due to glass phase structure change and
Cause thermal coefficient of expansion to change, or have the tendency of to make the thermal coefficient of expansion of sintered glass ceramics to become big to positive direction, it is difficult to
Obtain by the little sintered glass ceramics of change in size caused by heat treatment, temperature change.In addition, the easy devitrification of meeting, it is difficult to obtain
The glass of matter.The more preferably scope of MgO and ZnO is respectively 0～0.8%.
TiO2And ZrO2It is glass-modified composition in glass phase, the content of these compositions is respectively 0～5.0%.If these
Composition it is many containing quantitative change, then can easy devitrification, it is difficult to obtain the glass of homogenizing.TiO2And ZrO2More preferably scope be respectively 0～
4.0%.
P2O5It is the composition of the skeleton that glass is formed in glass phase, its content is 0～9.0%.If P2O5Containing quantitative change
It is many, then there is to make the thermal coefficient of expansion of sintered glass ceramics significantly to become big to positive direction, it is difficult to obtain by heat treatment, temperature
The little sintered glass ceramics of change in size caused by change.In addition, the easy devitrification of meeting, it is difficult to obtain the glass of homogenizing.P2O5It is more excellent
Scope is selected to be 0～7.0%.
BaO is glass-modified composition in glass phase, and its content is 0～8.0%.If BaO's is more containing quantitative change, knot is made
The thermal coefficient of expansion of crystallized glass significantly becomes big tendency to positive direction, it is difficult to obtain by caused by heat treatment, temperature change
The little sintered glass ceramics of change in size.In addition, the easy devitrification of meeting, it is difficult to obtain the glass of homogenizing.The more preferably scope of BaO is 0
～7.0%.
Na2O and K2O is glass-modified composition in glass phase, and the content of these compositions is respectively 0～4.0%.If these
Composition it is many containing quantitative change, then the thermal coefficient of expansion of glass phase becomes big to positive direction, in heat treatment due to the structure of glass phase
Change and cause thermal coefficient of expansion to change, have the tendency of to make the thermal coefficient of expansion of sintered glass ceramics to become big to positive direction,
It is difficult to obtain by the little sintered glass ceramics of change in size caused by heat treatment, temperature change.Na2O and K2The more preferably scope of O is each
From for 0～3.0%.
In addition, it is SiO by percentage to the quality that the sintered glass ceramics of the present invention preferably has255.0～70.0%, Al2O3
15.0～30.0%, Li2O 2.0～6.0%, MgO 0～2.0%, ZnO 0～2.0%, TiO20～4.0%, ZrO20～
4.0%, P2O50～4.0%, BaO 0～2.0%, Na2O 0～4.0%, K2The composition of O 0～4.0%.If crystallization glass
Glass is the glass with such composition, then easily become above-mentioned crystalline phase and glass phase, be readily obtained by heat treatment, temperature
The little sintered glass ceramics of change in size caused by change.The reasons why compositing range of sintered glass ceramics is set to above range is such as
Under.
SiO2Be the skeleton to form glass composition and be constitute crystallization composition, its content be 55.0～70.0%.
If SiO2Content tail off, then the precipitation of the crystallization of defined becomes difficult, and the SiO in glass phase2Content tail off, make
The thermal coefficient of expansion of glass phase becomes big to positive direction, causes thermal expansion system due to the structure change of glass phase in heat treatment
Number changes, or has the tendency of to make the thermal coefficient of expansion of sintered glass ceramics to become big to positive direction, it is difficult to obtain by heat treatment,
The little sintered glass ceramics of change in size caused by temperature change.If however, many containing quantitative change, the meltbility of glass easily deteriorates,
It is difficult to obtain the glass of homogenizing.SiO2More preferably scope be 60.0～70.0%.
Al2O3With SiO2Similarly, it is the composition of the skeleton to form glass and is the composition for constituting crystallization, its content is
15.0～30.0%.If Al2O3Content tail off, then the precipitation of the crystallization of defined becomes difficult, and in glass phase
Al2O3Content tail off, make the thermal coefficient of expansion of glass phase become big to positive direction, in heat treatment due to the structure of glass phase
Change and cause thermal coefficient of expansion to change, or have and make the thermal coefficient of expansion of sintered glass ceramics become big to positive direction to incline
To, it is difficult to obtain by the little sintered glass ceramics of change in size caused by heat treatment, temperature change.If however, glass many containing quantitative change
The meltbility of glass easily deteriorates, it is difficult to obtain the glass of homogenizing.Al2O3More preferably scope be 17.0～28.0%.
Li2O is to constitute the composition of crystallization and is glass-modified composition, and its content is 2.0～6.0%.If Li2The content of O
Tail off, then the precipitation of required crystallization becomes difficult.If however, Li in glass phase many containing quantitative change2O's is more containing quantitative change,
Make the thermal coefficient of expansion of glass phase become big to positive direction, thermal expansion is caused due to the structure change of glass phase in heat treatment
Coefficient changes, or has the tendency of to make the thermal coefficient of expansion of sintered glass ceramics to become big to positive direction, it is difficult to obtain by heat
The little sintered glass ceramics of change in size caused by reason, temperature change.Li2The more preferably scope of O is 2.0～5.5%.
MgO and ZnO are the compositions being solid-solubilized in crystallization, and the content of these compositions is respectively 0～2.0%.If these compositions
It is many containing quantitative change, then in addition to β-quartz solid solution or beta-eucryptite solid solution, the heterogeneous crystalline substance such as spinelle or gahnite
Body is also easily separated out, and is had due to temperature change when heat treatment or use and impaired worry.The more preferably scope of MgO and ZnO
Respectively 0～1.5%.
TiO2And ZrO2It is the Nucleated elements for being used for separating out crystallization in crystallization step, the content of these compositions is each
For 0～4.0%.If these compositions is more containing quantitative change, easy devitrification when by glass melting, molding, it is difficult to obtain homogenizing
Glass.TiO2And ZrO2More preferably scope be respectively 0～3.5%.If in addition, TiO2And ZrO2Total amount it is very few, then be difficult to
Insufficient to required degree of crystallinity, or nucleation, the crystallization of particle diameter that cannot be required makes crystallization be separated out when separating out
β-quartz solid solution or beta-eucryptite solid solution easily in low-temperature transformation into β-spodumene solid solution, as a result, crystallization
The thermal coefficient of expansion of glass is difficult to be close to 0 × 10-7/ DEG C (zero), it is difficult to obtain by the little knot of change in size caused by temperature change
Crystallized glass.In addition, on the other hand, if TiO2And ZrO2Total amount become excessive, then easily lose when by glass melting, molding
Thoroughly, it is difficult to obtain the glass of homogenizing.TiO2And ZrO2Total amount more preferably 1.5～6.0%.
P2O5It is the composition for making the easy nucleation of glass, its content is 0～4.0%.If P2O5It is many containing quantitative change, then glass become
Obtain and be easily separated, it is difficult to obtain the glass of homogenizing.P2O5Preferred scope be 0～3.0%.
BaO is the viscosity for reducing glass and the composition for improving glass melting and mouldability, and its content is 0～2.0%.
If BaO's is more containing quantitative change, easy devitrification when by glass melting, molding, it is difficult to obtain the glass of homogenizing.BaO is more preferably
Scope is 0～1.8%.
Na2O and K2O is to reduce the viscosity of glass and improve the composition of glass melting and mouldability, and these compositions contain
Amount is respectively 0～4.0%.If these compositions is more containing quantitative change, the thermal coefficient of expansion of glass phase becomes big to positive direction, in heat
Cause thermal coefficient of expansion to change due to the structure change of glass phase during process, or have the thermal expansion system for making sintered glass ceramics
Number becomes big tendency to positive direction, it is difficult to obtain by the little sintered glass ceramics of change in size caused by heat treatment, temperature change.
Na2O and K2The more preferably scope of O is respectively 0～2.0%.
In addition, in the range of the characteristic for not damaging defined, using the viscosity as reduction glass and glass can be improved
SrO, CaO, B of the composition of glass meltbility and mouldability2O3Deng or as the SnO of clarifier2、Cl、Sb2O3、As2O3Deng with total amount
Meter contains up to 10%.If these compositions is more containing quantitative change, the thermal coefficient of expansion of glass phase becomes big to positive direction, in Re Chu
Cause thermal coefficient of expansion to change due to the structure change of glass phase during reason, or have the thermal coefficient of expansion for making sintered glass ceramics
Become big tendency to positive direction, it is difficult to obtain by the little sintered glass ceramics of change in size caused by heat treatment, temperature change.Separately
Outward, it becomes difficult to separate out required crystallization.
The sintered glass ceramics of the present invention can be manufactured in the following way.
First, prepare frit so as to by percentage to the quality be SiO255.0～70.0%, Al2O3 15.0
～30.0%, Li2O 2.0～6.0%, MgO 0～2.0%, ZnO 0～2.0%, TiO20～4.0%, ZrO20～
4.0%, P2O50～4.0%, BaO 0～2.0%, Na2O 0～4.0%, K2The composition of O 0～4.0%.In addition, according to need
Will, can add for improve glass meltbility and mouldability composition and clarifier etc..
Then, the frit of preparation is carried out into molding after 1550～1750 DEG C of temperature melting, obtains crystallinity glass
Glass.In addition, molding can be carried out by the various forming methods such as float method, pressing, roll-in method as forming method.
Then, by the crystallinity glass of molding at 600～800 DEG C, after heat treatment forms nucleus in 1～10 hour, further,
Heat treatment is carried out 0.5～5 hour at 800～1000 DEG C, make Li2O·Al2O3·nSiO2The crystallization of system is separated out as primary crystallization,
So as to obtain the sintered glass ceramics of the present invention.
If in addition, nucleation temperature is too high or too low, or nucleation time is too short, then nucleation is insufficient, cannot get institute
The crystallization of the particle diameter of requirement, makes β-quartz solid solution that crystallization separated out when separating out or beta-eucryptite solid solution easily in low temperature
It is transformed into β-spodumene solid solution, as a result, the thermal coefficient of expansion of sintered glass ceramics is difficult to be close to 0 × 10-7/ DEG C (zero), it is difficult to
Obtain by the little sintered glass ceramics of change in size caused by temperature change.In addition, in the case where nucleation time is long, due to into
The effect of core is constant, can cause the rising of manufacturing cost.
In addition, if crystallized temperature is too high, the β-quartz solid solution or beta-eucryptite solid solution for being separated out easily turns
Become β-spodumene solid solution, as a result, the thermal coefficient of expansion of sintered glass ceramics is difficult to be close to 0 × 10-7/ DEG C (zero), it is difficult to
The little sintered glass ceramics of change in size to caused by by temperature change.However, if crystallized temperature is too low, crystallization time mistake
Short, then degree of crystallinity is too low, has the tendency of to make the thermal coefficient of expansion of sintered glass ceramics to become big to negative direction, is caused by temperature change
Change in size easily become big.In addition, in the case where crystallization time is long, as the effect of crystallization is constant, can cause
The rising of manufacturing cost.
In addition, the sintered glass ceramics of the present invention is as described above, (separated out by adjusting the species of the crystallization for separating out, degree of crystallinity
Crystallization ratio), the composition of crystallization, the ratio of glass phase, the composition of glass phase etc., make the thermal coefficient of expansion before and after heat treatment
Difference (Δ α) diminish, and, the thermal coefficient of expansion after the heat treatment of sintered glass ceramics when making -40～80 DEG C after heat treatment
0 is close to, therefore, it is possible to suppress by change in size caused by heat treatment, temperature change.
In addition, the sintered glass ceramics to obtaining can implement to cut, grind, the rear processing such as film forming.
Embodiment
Hereinafter, the sintered glass ceramics of the present invention is described in detail according to embodiment.
Table 1 illustrates examples and comparative examples of the present invention.
[table 1]
Each sample in table is made by the following method.
First, preparation raw material becomes quality % glass composition as shown in Table, after mix homogeneously, is put into platinum crucible
It is interior, the melting of 20 hours is carried out at 1600 DEG C.Then, melten glass is poured on carbon flat board, the thick plates of 5mm are shaped to using roller
After shape body, room temperature is cooled to 100 DEG C/h of cooling rate from 700 DEG C using annealing furnace, makes crystallinity glass plate.
Then, for the crystallinity glass plate for obtaining, after 780 DEG C of nucleation implemented 1 hour are processed, in 925 DEG C of knot
The crystallization that crystallization temperature is carried out 1 hour is processed, and is cooled to room temperature, has been made sintered glass ceramics, as each sample.
In addition, the programming rate from room temperature to nucleation temperature is set to 250 DEG C/h, will from nucleation temperature to crystal into
The programming rate of long temperature is set to 54 DEG C/h, and the cooling rate from crystal growth temperature to room temperature is set to 54 DEG C/h.
Crystalline phase, the composition of glass phase and sintered glass ceramics, the species of crystallization for so obtained each sample, crystallization
The difference and change in size of the thermal coefficient of expansion before and after degree, the thermal coefficient of expansion of solid solubility n, crystalline phase, heat treatment, by heat treatment
Caused by temperature change afterwards, thermal coefficient of expansion and change in size are determined.
As table 1 is expressed, the β-quartz solid solution with negative thermal coefficient of expansion is separated out in embodiment and is tied as separating out
Crystalline substance, degree of crystallinity are 75%.In addition, solid solubility n is also high, it is 7.6.In addition, the difference (Δ α) of the thermal coefficient of expansion before and after heat treatment is
0.09×10-7/ DEG C, the change by thermal coefficient of expansion caused by heat treatment is little, also little by change in size caused by heat treatment, is
0mm.Further, thermal coefficient of expansion during -40～80 DEG C after heat treatment is -0.09 × 10-7/ DEG C, very little, after heat treatment
Caused by temperature change, change in size is also little, is -2.2 × 10-5mm。
Although in contrast, the β-quartz solid solution with negative thermal coefficient of expansion is separated out in comparative example having, degree of crystallinity
For 80%, very high, solid solubility n is 6.8, very low.In addition, the difference (Δ α) of the thermal coefficient of expansion before and after heat treatment is 0.35 × 10-7/ DEG C, the change by thermal coefficient of expansion caused by heat treatment is big, is also 0mm by change in size caused by heat treatment.Further, at heat
Thermal coefficient of expansion during -40 after reason～80 DEG C is 0.48 × 10-7/ DEG C, very greatly, caused by the temperature change after heat treatment
Change in size is also big, is 11.5 × 10-5mm。
In addition, for the species and degree of crystallinity, solid solubility n of crystallization, using X-ray diffraction method (Co., Ltd.'s RIGAKU systems
The SmartLab for making) it is measured.
Specifically, degree of crystallinity is calculated by the following method：To spreading out for the sintered glass ceramics that obtained by X-ray diffraction method
Penetrate pattern to be parsed using Rietveld methods, try to achieve the crystallization content (matter of β-quartz solid solution or beta-eucryptite solid solution
Amount %), ZrTiO4The content (quality %) of the brilliant crystallization content (quality %) of tying and glass phase, by the crystallization content of each crystalline phase
Amount to and calculate as degree of crystallinity (quality %).
In addition, solid solubility n determines by the following method.First, by X-ray diffraction method determine β-quartz solid solution or
The interplanar distance of beta-eucryptite solid solution.Then, using the interplanar distance determined by X-ray diffraction method, calculated by formula (1) and tied
SiO in crystalline phase2Content x (mole %), then, calculates solid solubility n (mol ratio) by formula (2).
Formula (1)：SiO2Content x=(0.1004-d (406))/6.752 × 10-5
Formula (2)：Solid solubility n=2x/ (100-x)
In addition, as described in 505-510 page of Japanization association will (1974), due in β-quartz solid solution or
SiO in beta-eucryptite solid solution2Between specific interplanar distance in content and lattice, proportional relation is set up, therefore passes through
Interplanar distance is determined, the SiO in crystalline phase can be tried to achieve2Content x (mole %).In formula (1), d (406) represents that β-quartz is solid
The interplanar distance (nm) in (406) face in the lattice of solution or beta-eucryptite solid solution (hexagonal crystal).
For the composition of sintered glass ceramics, Li2The content of O is by atomic absorption analysis method, B2O3Content pass through inductance coupling
Plasma (ICP) emission spectrometry is closed, the content of the composition beyond these is determined by fluorescent X-ray spectrometry method.
For the composition of crystalline phase, by by solid solubility n and ZrTiO calculated using above-mentioned X-ray diffraction method4Tying
Brilliant crystallization content calculates the content of each composition in crystalline phase to try to achieve.In addition, for MgO and ZnO, being each contained in crystallization
Whole amount in glass, tries to achieve as the amount in being solid-solubilized in β-quartz solid solution or beta-eucryptite solid solution.
For the composition of glass phase, by deducting above-mentioned crystalline phase in the content from each composition of above-mentioned sintered glass ceramics
The content of each composition, determines contained each component content in residual glass phase.In addition, SiO2、Al2O3、Li2O、MgO、ZnO、
TiO2、ZrO2Composition in addition, all tries to achieve as the composition being included in glass phase.
For the thermal coefficient of expansion of crystalline phase, by X-ray diffraction method (SmartLab of Co., Ltd. RIGAKU manufactures),
In the temperature province from 20 DEG C to 300 DEG C, for lattice paprmeter (a axles of β-quartz solid solution or beta-eucryptite solid solution
Long, c-axis length) temperature dependency be determined, body is tried to achieve by the volume from a axial lengths and the long unit of account lattice of c-axis
The product coefficient of expansion, by the coefficient of cubical expansion divided by 3, so as to calculate thermal coefficient of expansion.
For by change in size caused by heat treatment, by determine the difference (Δ α) of the thermal coefficient of expansion before and after heat treatment with
And before heat treatment after change in size evaluated；It is for by change in size caused by the temperature change after heat treatment, logical
Cross determine heat treatment after -40～80 DEG C when change in size evaluated.
In addition, size during -40～80 DEG C after the difference (Δ α) and heat treatment of thermal coefficient of expansion before and after heat treatment becomes
Change, made the columned sample for being processed into diameter 4.0mm, length 20mm, by average thermal expansion system when -40～80 DEG C
Number is measured using dilatometer.Then, after sample being carried out heat treatment under conditions of 400 DEG C, 24 hours, again p- 40
Mean thermal expansion coefficients and swell increment when～80 DEG C is measured, using the difference of mean thermal expansion coefficients as before and after heat treatment
The difference (Δ α) of thermal coefficient of expansion illustrate, using swell increment when -40～80 DEG C as during -40 after heat treatment～80 DEG C
Change in size is illustrated.
In addition, for the change in size after before heat treatment, being determined before heat treatment using differential transformation type displacement sensor
The length of sample afterwards, the difference of the length before and after heat treatment is illustrated as change in size.
Industrial utilizability
The sintered glass ceramics of the present invention is not limited to the purposes as the spacer for etalon, it is also possible to used as example,
For the substrate of light wavelength division multiplexing, linear encoder position's measuring device (linear encoder position scale) etc.
The part of accurate measurement device, the structure member of precision instrument, the base material of accurate mirror use.
Claims (7)
1. a kind of sintered glass ceramics, it is characterised in that：
24 hours heat treatments, the difference (Δ of the thermal coefficient of expansion before and after heat treatment are carried out with the temperature of 300 DEG C～glass transition point
It is α) ± 0.20 × 10-7/ DEG C within, also, thermal coefficient of expansion during -40～80 DEG C after the heat treatment be 0 ± 0.3 ×
10-7/ DEG C within.
2. sintered glass ceramics as claimed in claim 1, it is characterised in that：
Make β-quartz solid solution or beta-eucryptite solid solution separate out as primary crystallization to form, also, degree of crystallinity is with quality percentage
Than being calculated as 72～80%.
3. sintered glass ceramics as claimed in claim 1 or 2, it is characterised in that：
With Li2O·Al2O3·nSiO2SiO in the β-quartz solid solution or beta-eucryptite solid solution of expression2Solid solubility n with
Molar ratio computing is more than 6.9.
4. the sintered glass ceramics as any one of claims 1 to 3, it is characterised in that：
The thermal coefficient of expansion of crystalline phase when 20～300 DEG C is -11 × 10-7～0 × 10-7/℃。
5. the sintered glass ceramics as any one of Claims 1 to 4, it is characterised in that：
Crystalline phase is SiO by percentage to the quality265.0～80.0%, Al2O310.0～18.0%, Li2O 3.0～6.0%,
MgO 0～2.0%, ZnO 0～2.0%, TiO20.5～4.0%, ZrO20.5～4.0%, P2O50～0.5%.
6. the sintered glass ceramics as any one of Claims 1 to 5, it is characterised in that：
Glass is mutually SiO by percentage to the quality230.0～50.0%, Al2O331.0～45.0%, Li2O 1.0～3.0%,
MgO 0～1.0%, ZnO 0～1.0%, TiO20～5.0%, ZrO20～5.0%, P2O50～9.0%, BaO 0～
8.0%th, Na2O 0～4.0%, K2O 0～4.0%.
7. the sintered glass ceramics as any one of claim 1～6, it is characterised in that：
With by percentage to the quality be SiO255.0～70.0%, Al2O315.0～30.0%, Li2O 2.0～6.0%,
MgO 0～2.0%, ZnO 0～2.0%, TiO20～4.0%, ZrO20～4.0%, P2O50～4.0%, BaO 0～
2.0%th, Na2O 0～4.0%, K2The composition of O 0～4.0%.
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| JP2014-154646 | 2014-07-30 | ||
| JP2014154646 | 2014-07-30 | ||
| PCT/JP2015/070369 WO2016017435A1 (en) | 2014-07-30 | 2015-07-16 | Crystallized glass |
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| CN106573826A true CN106573826A (en) | 2017-04-19 |
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|---|---|
| JP (1) | JP6627760B2 (en) |
| CN (1) | CN106573826A (en) |
| TW (1) | TW201609581A (en) |
| WO (1) | WO2016017435A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109867447A (en) * | 2017-12-01 | 2019-06-11 | 成都光明光电股份有限公司 | Devitrified glass and its substrate |
| CN111646704A (en) * | 2020-06-08 | 2020-09-11 | 重庆两江新区夏美西科技合伙企业(有限合伙) | Glass ceramic doped with beta-eucryptite whisker, preparation method thereof and chemically strengthened glass ceramic |
| CN113710625A (en) * | 2019-04-23 | 2021-11-26 | 日本电气硝子株式会社 | Li2O－Al2O3－SiO2Crystallized glass of system |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11104607B2 (en) * | 2017-02-24 | 2021-08-31 | Ohara Inc. | Crystallized glass |
| JPWO2020189115A1 (en) * | 2019-03-15 | 2020-09-24 |
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| CN104995146B (en) * | 2013-02-21 | 2018-06-15 | 日本电气硝子株式会社 | Sintered glass ceramics and its manufacturing method |
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- 2015-07-16 JP JP2016538265A patent/JP6627760B2/en active Active
- 2015-07-16 WO PCT/JP2015/070369 patent/WO2016017435A1/en active Application Filing
- 2015-07-16 CN CN201580041093.5A patent/CN106573826A/en active Pending
- 2015-07-21 TW TW104123575A patent/TW201609581A/en unknown
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| US4285728A (en) * | 1975-02-06 | 1981-08-25 | Owens-Illinois, Inc. | Method of making low expansion crystallized glass-ceramics and telescope mirror blanks made thereby |
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| CN109867447A (en) * | 2017-12-01 | 2019-06-11 | 成都光明光电股份有限公司 | Devitrified glass and its substrate |
| CN113710625A (en) * | 2019-04-23 | 2021-11-26 | 日本电气硝子株式会社 | Li2O－Al2O3－SiO2Crystallized glass of system |
| CN111646704A (en) * | 2020-06-08 | 2020-09-11 | 重庆两江新区夏美西科技合伙企业(有限合伙) | Glass ceramic doped with beta-eucryptite whisker, preparation method thereof and chemically strengthened glass ceramic |
| CN111646704B (en) * | 2020-06-08 | 2022-02-22 | 重庆鑫景特种玻璃有限公司 | Glass ceramic doped with beta-eucryptite whisker, preparation method thereof and chemically strengthened glass ceramic |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201609581A (en) | 2016-03-16 |
| WO2016017435A1 (en) | 2016-02-04 |
| JP6627760B2 (en) | 2020-01-08 |
| JPWO2016017435A1 (en) | 2017-04-27 |
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