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 heatThe 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 downThe 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 changeThe 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 pointTemperature 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 heatThe 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 -40～80DEG C when thermal coefficient of expansion be 0 ± 0.3 × 10-7/ DEG C within, in sintered glass ceramics, adjust separate out crystallization species, crystallizationDegree (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 hundredRatio 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 solutionPrimary 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 phaseCancel 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, canThe 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 treatmentChange, 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, crystallizingThe 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 phaseThe 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 phaseMutually offset, the oriented negative direction of thermal coefficient of expansion of sintered glass ceramics becomes big tendency, by change in size caused by temperature changeEasily 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 senseTo, 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 phaseThe 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 ceramicsBecome 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 orSiO in beta-eucryptite solid solution2Solid solubility n with molar ratio computing as more than 6.9.By solid solubility n is set to mol ratioMore 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 directionExcessive, 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 solutionN 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 inclinesTo, 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 nWith 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 treatmentThe 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 treatmentThe 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 phaseThe 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 intoFor 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 crystallizationThe 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 phaseCancel 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, temperatureThe little sintered glass ceramics of change in size caused by change.If however, content tails off, with Li2O·Al2O3·nSiO2RepresentSiO in β-quartz solid solution or beta-eucryptite solid solution2Solid solubility n easily diminish, having makes the thermal expansion system of crystalline phaseNumber 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 heatThe 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 toThe 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 changeMany, then in crystallizing SiO2Solid solubility n easily diminish, having makes the thermal coefficient of expansion of crystalline phase become too much to negative directionTendency, 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 treatmentThe 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 changeThe 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 glassThe 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, difficultTo 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, thenSiO 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 treatmentThe 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 changeLittle sintered glass ceramics.However, if content tails off, the thermal coefficient of expansion of crystalline phase easily becomes big, crystalline phase and glass phaseThermal 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 toThe 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%.IfThese 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 useThe 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 theseComposition 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 makeThe 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 instituteThe 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 crystallizationβ-quartz solid solution or beta-eucryptite solid solution are easily solid into the β-spodumene with positive thermal coefficient of expansion in low-temperature transformationSolution, 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 changeThe 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 leadThe 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 glassGlass is mutually the phase with such composition, then be difficult to occur by glass phase caused by heat treatment structure change, be readily obtained byThe 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 SiO2ContentBecome 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 makeThe 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 changeThe 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 treatmentCause 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 justDirection 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'sMore 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 phaseNumber 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 heatThe 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 holdsIt is variable big, cause thermal coefficient of expansion to change due to the structure change of glass phase in heat treatment, or make crystallization glassThe 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 changeSintered 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 glassThe 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 phaseChange, 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 changeThe little sintered glass ceramics of caused change in size.However, if content tails off, the thermal coefficient of expansion of glass phase easily diminishes, knotThe 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 directionTendency, 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 OFor 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 theseComposition 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 andCause 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 toObtain 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 obtainThe 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 theseComposition 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 changeIt 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, temperatureThe 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 excellentScope 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 madeThe 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 changeThe 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 theseComposition 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 phaseChange 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 eachFrom 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%, 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%, Na2O 0～4.0%, K2The composition of O 0～4.0%.If crystallization glassGlass is the glass with such composition, then easily become above-mentioned crystalline phase and glass phase, be readily obtained by heat treatment, temperatureThe 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 asUnder.
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, makeThe 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 treatmentNumber 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 is15.0～30.0%.If Al2O3Content tail off, then the precipitation of the crystallization of defined becomes difficult, and in glass phaseAl2O3Content 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 phaseChange 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 inclineTo, 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 changeThe 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 OTail 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 treatmentCoefficient 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 heatThe 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 compositionsIt 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 gahniteBody 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 ZnORespectively 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 eachFor 0～4.0%.If these compositions is more containing quantitative change, easy devitrification when by glass melting, molding, it is difficult to obtain homogenizingGlass.TiO2And ZrO2More preferably scope be respectively 0～3.5%.If in addition, TiO2And ZrO2Total amount it is very few, then be difficult toInsufficient to required degree of crystallinity, or nucleation, the crystallization of particle diameter that cannot be required makes crystallization be separated out when separating outβ-quartz solid solution or beta-eucryptite solid solution easily in low-temperature transformation into β-spodumene solid solution, as a result, crystallizationThe 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 changeCrystallized glass.In addition, on the other hand, if TiO2And ZrO2Total amount become excessive, then easily lose when by glass melting, moldingThoroughly, 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 becomeObtain 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 preferablyScope 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 containAmount 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 heatCause 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 ceramicsNumber 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 improvedSrO, CaO, B of the composition of glass meltbility and mouldability2O3Deng or as the SnO of clarifier2、Cl、Sb2O3、As2O3Deng with total amountMeter 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 ChuCause 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 ceramicsBecome 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.SeparatelyOutward, 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 needWill, 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 glassGlass.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 instituteThe 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 temperatureIt 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 toObtain 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 intoThe 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 turnsBecome 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 toThe little sintered glass ceramics of change in size to caused by by temperature change.However, if crystallized temperature is too low, crystallization time mistakeShort, 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 changeChange in size easily become big.In addition, in the case where crystallization time is long, as the effect of crystallization is constant, can causeThe 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 crystallinityCrystallization 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 treatmentDifference (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 treatment0 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 crucibleIt 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 rollerAfter 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 knotThe 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 intoThe 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, crystallizationThe 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 treatmentCaused 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 outCrystalline 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 is0.09×10-7/ 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, is0mm.Further, thermal coefficient of expansion during -40～80 DEG C after heat treatment is -0.09 × 10-7/ DEG C, very little, after heat treatmentCaused 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 crystallinityFor 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 heatThermal 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 treatmentChange 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 systemsThe 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 methodPenetrate pattern to be parsed using Rietveld methods, try to achieve the crystallization content (matter of β-quartz solid solution or beta-eucryptite solid solutionAmount %), ZrTiO4The content (quality %) of the brilliant crystallization content (quality %) of tying and glass phase, by the crystallization content of each crystalline phaseAmount 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 orThe interplanar distance of beta-eucryptite solid solution.Then, using the interplanar distance determined by X-ray diffraction method, calculated by formula (1) and tiedSiO 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 orSiO in beta-eucryptite solid solution2Between specific interplanar distance in content and lattice, proportional relation is set up, therefore passes throughInterplanar 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 solidThe 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 couplingPlasma (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 method4TyingBrilliant 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 crystallizationWhole 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 ceramicsThe 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 solutionLong, 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-axisThe 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 withAnd before heat treatment after change in size evaluated；It is for by change in size caused by the temperature change after heat treatment, logicalCross 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 becomesChange, made the columned sample for being processed into diameter 4.0mm, length 20mm, by average thermal expansion system when -40～80 DEG CNumber is measured using dilatometer.Then, after sample being carried out heat treatment under conditions of 400 DEG C, 24 hours, again p- 40Mean 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 treatmentThe 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 CChange 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 sensorThe 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.