CN1789191A - Substrate for information recording medium and magnetic recording medium composed of crystallized glass - Google Patents
Substrate for information recording medium and magnetic recording medium composed of crystallized glass Download PDFInfo
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- CN1789191A CN1789191A CNA2005101135755A CN200510113575A CN1789191A CN 1789191 A CN1789191 A CN 1789191A CN A2005101135755 A CNA2005101135755 A CN A2005101135755A CN 200510113575 A CN200510113575 A CN 200510113575A CN 1789191 A CN1789191 A CN 1789191A
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Abstract
Provided is a substrate for information recording medium composed of such a crystallized glass as having high Young's modulus, strength and heat resistance, being excellent in surface smoothness, surface homogeneity and surface processability, as well as having a relatively low temperature of glass liquid phase and being capable of producing cheaply, and an information recording medium using this substrate. The crystallized glass substrate for information recording medium comprising 35-65 mol % of SiO2, 5-25 mol % of Al2O3, 10-40 mol % of MgO and 5-15 mol % of TiO2, in which the total amount of aforementioned composition is at least equal to or higher than 92 mol % and the main crystals are enstatite and/or its solid solution. The information recording medium having this substrate and a recording layer formed on said substrate.
Description
The application is dividing an application of application number is 00134401.3, the applying date is on July 7th, 2000 application for a patent for invention.
The present invention relates to be applicable to the devitrified glass that the substrate of information recording carriers such as disk, CD, photomagneto disk is used, the information recording carrier that is made of this devitrified glass is with substrate and use the information recording carrier of this information recording carrier with substrate.
The main composition element of computer equimagnetic memory storage is magnetic recording media and magnetic recording feedback magnetic head.As magnetic recording media is known floppy disk and hard disk arranged.Wherein hard disk mainly is to use aluminium alloy with substrate material.Recently, along with the microcomputer miniaturization of hard disk drive and the densification of magnetic recording, the float-amount of magnetic head significantly reduces.Simultaneously, the precision high to the surface smoothing requirement of magnetic disk substrate., in the occasion of aluminium alloy, because hardness is low, use high precision abrasive substance and machine to carry out attrition process, because this abrasive surface viscous deformation, it is difficult making the above high precision plane of certain degree.Even implement nickel plating-phosphorus in aluminum alloy surface, can not make surface roughness Ra is below 5 dusts.And along with the progress of hard disk drive miniaturization, slimming, the strong request disk is littler with substrate thickness.,, keep the intensity of regulation, and to make the hard disk attenuation be difficult according to the specification requirement of hard disk drive because intensity, the rigidity of aluminium alloy is low.
So, must high strength, the disk of high rigidity, high-impact, high surface smoothing occurs with glass substrate.Wherein, know useful ion exchange method and strengthen the chemically reinforced glass substrate of substrate surface and the crystallization substrate of execution crystallization treatment etc.
As ion-exchange chilled glass substrate, for example known spy of having opens disclosed glass in the flat 1-239036 communique.This ion-exchange chilled glass substrate is to contain (weight %) SiO
2: 50-65%, Al
2O
3: 0.5-14%, R
2O (but R is an alkalimetal ion): 10-32%, ZnO:1-15%, B
2O
3: the glass of 1.1-14% forms disk glass substrate that compressive stress layers strengthen by ion exchange method at glass substrate surface by basic ion.
In addition, as devitrified glass, for example there be No. 2516553 communique of patent to put down in writing.This devitrified glass is to contain (weight %) SiO
2: 65-83%, Li
2O:8-13%, K
2O:0-7%, MgO:0.5-5.5%, ZnO:0-5%, PbO:0-5% (but MgO+ZnO+PbO:0.5-5%), P
2O
5: 1-4%, Al
2O
3: 0-7%, As
2O
3+ Sb
2O
3: 0-2%, and contain tiny Li as primary crystallization
2O2SiO
2The disk devitrified glass of crystal grain.
Moreover the spy opens in the flat 7-291660 communique and also discloses devitrified glass.This devitrified glass is with by (weight %) SiO
238-50%, Al
2O
318-30%, MgO 10-20%, but by weight Al
2O
3/ MgO=1.2-2.3, B
2O
30-5%, CaO 0-5%, BaO 0-5%, SrO 0-5%, ZnO 0.5-7.5%, TiO
24-15%, ZrO
20-5%, As
2O
3And/or Sb
2O
3After glass melting that the composition of 0-2% constitutes and the shaping, thermal treatment obtains.This glass is characterized by that to contain trichroite as crystallization be crystalline trichroite microcrystalline glass in series.Moreover, the disk substrate that is made of this devitrified glass is also disclosed.
In addition, the spy opens in the flat 9-77531 communique (No. 5476821, United States Patent (USP)) and also discloses devitrified glass.This devitrified glass is a Young's modulus from about 14 * 10
6To about 24 * 10
6Psi (in 96～165GPa) the scope, fracture toughness property is greater than 1.0Mpam
1/2Glass and ceramic product.And, this devitrified glass by contain the remaining glass basis of many light-weight mutually in homodisperse spinel type crystallization of uniform size be that the main crystallization phases aggregate that constitutes constitutes, be that benchmark is represented with the weight percentage of oxide compound, in fact by the SiO of 35-60%
2, the Al of 20-35%
2O
3, the MgO of 0-25%, the ZnO of 0-25%, the TiO of 0-20%
2, the ZrO of 0-10%
2The Li of 0-2%
2The NiO of O and 0-8% constitutes, and the MgO+ZnO total is at least about 10%.Also can contain by BaO, CaO, PbO, SrO, P
2O
5, B
2O
3And Ga
2O
3Select any composition in the group that constitutes again, by Na up to 5%
2O, K
2O, Rb
2O and Cs
2The R of the 0-5% that selects in the group that O constitutes
2The transition metal oxide of O and 0-8% is at the Al that only contains not enough about 25% amount
2O
3Occasion, be to have TiO
2+ ZrO
2+ NiO total amount is the glass-ceramic of forming more than 5%.The disk substrate that is made of this glass-ceramic is also disclosed in above-mentioned communique.
In addition, in No. the 5491116th, the United States Patent (USP) devitrified glass is disclosed also.This devitrified glass be rupture factor at least about 15000psi, Knoop hardness surpasses about 760KHN, Young's modulus about 20 * 10
6Psi, fracture toughness property is greater than 1.0Mpam
1/2Glass and ceramic product.Primary crystallization is in fact by the SiO that contains (weight %) 35-60% by enstatite or its sosoloid and spinel (spinel type crystallization) formation
2, the Al of 10-30%
2O
3, the MgO of 12-30%, the ZnO of 0-10%, the TiO of 5-20%
2The devitrified glass of the composition at least 92% that constitutes with the NiO of 0-8%.Moreover, the disk substrate that this devitrified glass constitutes is also disclosed.Also have, the glass identical with the devitrified glass of putting down in writing in the above-mentioned patent also is disclosed in Journal of Non-Crystalline solids219 (1997) 219-227.
But along with the densification of the miniaturization of nearest hard disk, slimming, record, the low come-up of magnetic head and disk rotation high speed promptly make progress.For this reason, intensity and Young's modulus, the surface smoothing etc. to the magnetic disk substrate material have tighter requirement.Particularly because microcomputer and サ-バ-densification that writes down with 3.5 inches hard disk informations, surface smoothing and surface to substrate material have strict requirement, in addition, the high speed disk rotation number corresponding to data processing is to be necessary more than the 10000rpm.For this reason, the requirement of the rigidity of substrate material is become tighter, the limit of former aluminium substrate clearly.From now on, the high capacity of hard disk, the needs of the high speed rotatingization limit that is inevitable will be tangible as magnetic recording media with substrate material strong request high Young's modulus, high strength, superior surface, shock-resistance etc.
But, open disclosed chemically reinforced glass in the flat 1-239036 communique as above-mentioned spy, Young's modulus is about 80Gpa, can not adapt to the strict demand of hard disk from now on.So far ion-exchange is strengthened substrate glass and a large amount of alkali ions is imported in the glass Young's modulus of thus obtained most of chilled glass low (90Gpa) for ion-exchange.Moreover, because rigidity is low, can not adapt to 3.5 inches Ha イ エ Application De dish substrate and slimming magnetic disk substrate.In addition, implement chemical enhanced glass by ion-exchange and contain the many alkali compositions of quantity.Thus, as under high temperature, high humidity environment, using for a long time, the thin part of the pore part of magnetic film or the magnetic films such as peripheral part of magnetic film or separate out basic ion from the exposed portions serve of glass, this exists card machine, magnetic film corrosion or shortcoming such as rotten.Also have, in production process of magnetic recording media, after on the glass substrate magnetosphere being set, the heat treated situation of the regulation of execution is arranged for improving characteristics such as magnetospheric coercive force., because the glass transition temp of the ion-exchange chilled glass before above-mentioned is 500 ℃ at most,, there is the problem that can not get high coercive force owing to lack thermotolerance.
In addition, disclosed devitrified glass in the past is aspect Young's modulus and thermotolerance, more superior than above-mentioned chemically reinforced glass substrate in No. 2516553 communique of above-mentioned patent., surfaceness lacks surface smoothing more than 10 dusts, and the limit of the low come-up of magnetic head is arranged.Thus, existence can not adapt to the problem of magnetic recording densification.Moreover Young's modulus is 90-100Gpa at most, can not adapt to 3.5 inches Ha イ エ Application De dish substrates and slimming dish substrate.
In addition, above-mentioned spy opens disclosed devitrified glass in the flat 7-291660 communique, and its Young's modulus is 100-130GPa at most, is not enough.Moreover, the surface smoothing on own centre line mean roughness (Ra) the 8 Izod right sides only, smoothness is poor.There is the shortcoming of making difficulty in the liquidus temperature of glass up to about 1400 ℃ in addition.
Also have, above-mentioned spy opens disclosed devitrified glass in the flat 9-77531 communique, because its primary crystallization is a spinel, very difficult shortcoming of grinding is arranged.Moreover the liquidus temperature of glass has the shortcoming that is difficult to high melt and hot forming up to more than 1400 ℃.
Also have, the devitrified glass of United States Patent (USP) 5491116 and Journal of Non-Crystalline Solids219 (1997) 219-227 contains many spinels and enstatite.Thereby, consider that bit opens that disclosed devitrified glass is easy to grind in the flat 9-77531 communique., owing to still contain spinel, abrasive property is still not enough.That is, still grind for a long time, the problem of productivity difference is arranged for the surfaceness that obtains wishing.
Moreover the glass of putting down in writing in No. 2648673 communique of patent is thermotolerance glass-ceramic more than 1200 ℃ owing to be to use temperature, and it is difficult using with substrate as information recording carrier.That is, smelting temperature is high-leveled and difficult in manufacturing, moreover crystal size is big, can not obtain the surface smoothing of information recording carrier requirement.
At this, the objective of the invention is to consider the requirement of magnetic recording media in the near future with the slimming of substrate, high strength, high heat resistance, high-impact etc., provide by Young's modulus, intensity and thermotolerance height, surface smoothing and surperficial uniformity and surface working are superior, and the information recording carrier substrates such as disk of the relatively lower devitrified glass formation that also can cheaply make of the liquidus temperature of glass.
Another object of the present invention provides the information recording carrier of disk of the substrate that use is made of above-mentioned devitrified glass etc.
In addition, the present invention also provides the information recording carrier that is made of the above-mentioned devitrified glass manufacture method of substrate.
For achieving the above object, the inventor has carried out various researchs, found that to obtain having the above high Young's modulus of 140GPa and excellent surface smoothness and good surface processibility that the suitable information recording carrier that liquidus temperature the is lower devitrified glass of substrate has been finished the present invention.
The present invention relates to contain:
SiO
2: 35-65 mole %,
Al
2O
3: 5-25 mole %,
MgO:10-40 mole %,
TiO
2: 5-15 mole %,
Above-mentioned composition adds up to and is at least 92 moles more than the %, and primary crystallization is the information recording carrier that constitutes of the devitrified glass of enstatite and/or its sosoloid with substrate (to call substrate (1) in the following text).
In above-mentioned substrate (1), Al
2O
3Mol ratio (Al with MgO
2O
3/ MgO) be more than 0.2, be ideal less than 0.5.
In above-mentioned substrate (1), contain:
SiO
2: 40-60 mole %,
Al
2O
3: 7-22 mole %,
MgO:12-35 mole %,
TiO
2: 5.5-14 mole %,
It is ideal.In above-mentioned substrate (1), contain 10 moles of Y below the %
2O
3, contain the following ZrO of 10 moles of %
2It is ideal.
Only the invention still further relates to and have:
SiO
2: 35-65 mole %
Al
2O
3: 5-25 mole %
MgO:10-40 mole %
TiO
2: 5-15 mole %
Y
2O
3: 0-10 mole %
ZrO
2: 0-10 mole %
R
2O:0-5 mole % (but R represents to be selected from least a of Li, Na, K)
RO:0-5 mole % (but R represents to be selected from least a of Ca, Sr, Ba)
As
2O
3+ Sb
2O
3: 0-2 mole %
SiO
2+ Al
2O
3+ MgO+TiO
2: the above institute of 92 moles of % constitutes the devitrified glasses of composition, and primary crystallization is that the information recording carrier of devitrified glass formation of enstatite and/or its sosoloid is with substrate (to call substrate (2) in the following text).
Only the invention still further relates to and have:
SiO
2: 35-65 mole %
Al
2O
3: 5-25 mole %
MgO:10-40 mole %
TiO
2: 5-15 mole %
Y
2O
3: 0-10 mole %
ZrO
2: 0-10 mole %
R
2O:0-5 mole % (but R represents to be selected from least a of Li, Na, K)
RO:0-5 mole % (but R represents to be selected from least a of Ca, Sr, Ba)
As
2O
3+ Sb
2O
3: 0-2 mole %
SiO
2+ Al
2O
3+ MgO+TiO
2: the devitrified glass of the above compositions that constitute of 92 moles of %, degree of crystallinity are the information recording carrier that constitutes of the devitrified glass of 20-70 volume % with substrate (to call substrate (3) in the following text).
The Y that contains 0.3-8 mole % in above-mentioned substrate (1)～(3)
2O
3, contain the ZrO of 1～10 mole of %
2, further contain the ZrO of 1-5 mole %
2It is ideal.
In addition, in above-mentioned substrate (1), contain 5 moles of R below the %
2O (but R represents to be selected from least a of Li, Na, K), R
2O is K
2O is an ideal.
TiO in above-mentioned substrate (1)～(3)
2Content is that 8-14 mole % is an ideal.
In addition, the Young's modulus of above-mentioned substrate (1)～(3) is to be ideal more than the 140GPa.
Above-mentioned substrate (1) consists of:
SiO
2: 35-43 mole %
Al
2O
3: 9-20 mole %
MgO:30-39 mole %
Y
2O
3: 1-3 mole %
TiO
2: 8.5-15 mole %
ZrO
2: 1-5 mole % is an ideal, moreover, SiO in it is formed
2The mol ratio of/MgO is below 1.35 and be ideal more than the Young's modulus 160GPa.
In addition, the median size that forms the crystal grain of primary crystallization in above-mentioned substrate (1)～(3) is below the 100nm, and the median size that further forms the crystal grain of primary crystallization is to be ideal below the 70nm.
In addition, above-mentioned substrate (1)～(3) are that the substrate of the following abrasive surface of 1nm is an ideal for having surface roughness Ra.
Also have, the present invention relates to have surface roughness Ra is the following abrasive surface of 1nm, is the information recording carrier that constitutes of the devitrified glass of enstatite and/or its sosoloid with substrate (above title substrate (4)) by primary crystallization.
It is that the following abrasive surface of 0.5nm is an ideal that above-mentioned substrate (4) has surfaceness.
In addition, above-mentioned substrate (1)～(4) when 1mm is thick wavelength be that the transmitance of 600nm light is more than 10% and thermal expansivity is 65 * 10
-7～85 * 10
-7/ ℃ be ideal.
The invention still further relates to by containing primary crystallization enstatite and/or its sosoloid, and the information recording carrier that constitutes less than the devitrified glass of 100nm of the average crystal grain diameter of above-mentioned at least primary crystallization is with substrate (to call substrate (5) in the following text).
The average crystal grain diameter of above-mentioned at least primary crystallization is to be ideal below the 70nm in above-mentioned substrate (5).
The transmitance that the invention still further relates to 1mm wavelength 600nm light when thick is more than 10%, and primary crystallization is the information recording carrier that constitutes of the devitrified glass of enstatite with substrate (to call substrate (6) in the following text).
In addition, in above-mentioned substrate (1)～(6), degree of crystallinity is more than the 50 volume %, and enstatite and/or its sosoloid total amount are 70-90 volume %, titanate is 10-30 volume %, and enstatite and/or its sosoloid and titanate total amount are to be ideal more than the 90 volume %.
The invention still further relates to thermal expansivity is 65 * 10
-7～85 * 10
-7/ ℃, contain information recording carrier that the devitrified glass as the enstatite of primary crystallization and/or its sosoloid constitutes with substrate (to call substrate (7) in the following text).
The thermal expansivity of above-mentioned substrate (7) is 73 * 10
-7～83 * 10
-7/ ℃ be ideal.
Above-mentioned substrate (1)～(7) do not contain the quartz solid solution as primary crystallization in fact, and not containing as the spinel of crystallization phases in fact and not containing ZnO in fact is ideal.
For above-mentioned substrate (1)～(7), information recording carrier can be disk.
The invention still further relates to the recording layer that has above-mentioned substrate (1)～(7) and form on this substrate is the information recording carrier of feature.
For above-mentioned information recording carrier, recording layer can be magnetic recording layer.
The invention still further relates to and comprise frit in 1400-1650 ℃ of fusing, vitrified operation, the glass that will obtain in above-mentioned operation forms the operation of plate glass, the plate glass that obtains in the above-mentioned operation is warmed up to separates out the crystalline temperature and make the crystalline operation, contain SiO
2: 35-65 mole %, Al
2O
3: 5-25 mole %, MgO:10-40 mole % and TiO
2: 5-15 mole %, above-mentioned composition add up to 92 moles more than the %, and primary crystallization is the manufacture method (to call manufacture method (1)) of the information recording carrier that constitutes of the devitrified glass of enstatite and/or its sosoloid with substrate.
For above-mentioned manufacture method (1), frit contains K
2O, it is ideal that temperature of fusion is 1400-1650 ℃.1450～1550 ℃ even more ideal.
For above-mentioned manufacture method (1), frit contains Y
2O
3, it is ideal that molten glass is shaped as plate glass at 600-680 ℃.
The invention still further relates to and be included in 1400-1650 ℃, the glass that obtains in the above-mentioned operation is formed the operation of plate glass frit fusing, vitrified operation.The plate glass that will obtain in above-mentioned operation is warmed up to separates out the crystalline temperature and makes the crystalline operation, be only have by
SiO
2: 35-65 mole %
Al
2O
3: 5-25 mole %
MgO:10-40 mole %
TiO
2: 5-15 mole %
Y
2O
3: 0-10 mole %
ZrO
2: 0-10 mole %
R
2O:0-5 mole % (but R represents to be selected from least a of Li, Na, K)
RO:0-5 mole % (but R represents to be selected from least a of Ca, Sr, Ba)
As
2O
3+ Sb
2O
3: 0-2 mole %
SiO
2+ Al
2O
3+ MgO+TiO
2: the devitrified glass of the above compositions that constitute of 92 moles of %, primary crystallization are the manufacture method (to call manufacture method (2)) of the information recording carrier that constitutes of the devitrified glass of enstatite and/or its sosoloid with substrate.
The glass that is shaped being warmed up to 850-1150 ℃ in above-mentioned manufacture method (1) and (2), to make crystallization be ideal.
In addition, in above-mentioned manufacture method (1) or (2), about heating process, the glass that is shaped being warmed up to 500-850 ℃ with 5-50 ℃/minute, is ideal with 0.1-10 ℃ of/minute intensification after 500-850 ℃.
The invention still further relates to according to comprising and to contain SiO
2, Al
2O
3, MgO and TiO
2Glass the method for the operation of crystallization is made, by containing SiO
2: 35-65 mole %, Al
2O
3: 5-25 mole %, MgO:10-40 mole % and TiO
2: 5-15 mole %, above-mentioned composition add up to 92 moles more than the %, do not contain information recording carrier that the devitrified glass of ZnO constitutes with substrate (to call substrate (8) in the following text).
The invention still further relates to according to comprising and to contain SiO
2, Al
2O
3, MgO and TiO
2Glass 850-1150 ℃ of thermal treatment the operation of crystallization is made, only have by
SiO
2: 35-65 mole %
Al
2O
3: 5-25 mole %
MgO:10-40 mole %
TiO
2: 5-15 mole %
Y
2O
3: 0-10 mole %
ZrO
2: 0-10 mole %
R
2O:0-5 mole % (but R represents to be selected from least a of Li, Na, K)
RO:0-5 mole % (but R represents to be selected from least a of Ca, Sr, Ba)
As
2O
3+ Sb
2O
3: 0-2 mole %
SiO
2+ Al
2O
3+ MgO+TiO
2: the information recording carrier that the devitrified glass of the above compositions that constitute of 92 moles of % constitutes is with substrate (to call substrate (9) in the following text).
In above-mentioned substrate (8) and (9), above-mentioned thermal treatment was carried out 1-4 hour, and above-mentioned thermal treatment is ideal at 875-1000 ℃.
Information recording carrier of the present invention contains SiO with substrate
2: 35-65 mole %, Al
2O
3: 5-25 mole %, MgO:10-40 mole % and TiO
2: 5-15 mole %, above-mentioned composition add up to and are at least 92 moles more than the %, and are to be that the devitrified glass of enstatite and/or its sosoloid constitutes by primary crystallization.
Each composition that constitutes glass in the devitrified glass that constitutes substrate of the present invention the following describes.In addition, [%] below all expressions unless stated otherwise (mole %).
SiO
2Being the cancellated formation thing of glass, is mainly to separate out crystalline to have MgOSiO
2The enstatite of forming and have (MgAl) SiO
3The constituent of the enstatite sosoloid of forming.Because as SiO
2Content is very unstable less than the glass of 35% melting, have can not hot forming danger, and difficulty is separated out in above-mentioned crystallization.In addition, as SiO
2Content be less than 35%, the deteriorates chemical durability of remaining glass basis phase, thermotolerance also have the tendency of deterioration.On the other hand, as SiO
2Content surpass 65%, the primary crystallization enstatite separate out difficulty, the Young's modulus of glass has the tendency that sharply diminishes.For this reason, as considering to separate out crystallization kind and the amount of separating out, chemical durability, thermotolerance and shaping productivity, SiO
2Content in 35～65% scope.From the viewpoint for the devitrified glass that obtains having better rerum natura, SiO
2Better content is in 40～60% scope.
Also have, as described below, with the combination of other composition, surface smoothing is poor slightly, but can obtain having the devitrified glass of the above high Young's modulus of 160GPa, therefore has SiO
2Content be 35～43% ideal situation.
Al
2O
3Be the intermidate oxide in the glass, help the improvement of glass surface hardness.But, as Al
2O
3Content is less than 5%, and the chemical durability of glass basis phase descends, and has the tendency that is difficult to obtain substrate material institute desired strength.On the other hand, as Al
2O
3Content surpasses 25%, and as the difficulty of separating out of the enstatite of primary crystallization, melt temperature uprises simultaneously, the glass melting difficulty, and be easy to lose transparent and be easy to exist into the tendency of deformation difficulty.Therefore, consider glass melting, hot forming, separate out crystallization kind etc., Al
2O
3Content is in the scope of 5-25%, and better the scope at 7-22% is suitable.
Also have, as described below, with the combination of other composition, surface smoothing is poor slightly, but can obtain having the devitrified glass of the above high Young's modulus of 160GPa, therefore has Al
2O
3The ideal situation of content 9-20%.
MgO is the ornamental equivalent of glass, is to have MgOSiO
2The enstatite of forming and the main component of solid solution crystal thereof.Less than 10%, difficulty is separated out in above-mentioned crystallization as MgO content, and glass loses transparent tendency and temperature of fusion height, and the processing temperature amplitude of forming of glass has the tendency that narrows down.On the other hand, surpass 40%, the tendency that the rapid reduction of high temperature viscosity of glass and thermally labile, productivity worsen, have Young's modulus and weather resistance to reduce as MgO content.At this, as consider productivity, chemical durability, high temperature viscosity and the intensity etc. of glass, the content of MgO is in the 10-40% scope, and better the scope at 12-35% is suitable.
Also have, as described below, with the combination of other composition, surface smoothing is poor slightly, but can obtain having the devitrified glass of the above high Young's modulus of 160GPa, and therefore having MgO content is the ideal situation of 30-39%.
But, (Al
2O
3/ MgO) mol ratio should be adjusted MgO and Al less than 0.5
2O
3Content.As (Al
2O
3/ Mg) mol ratio is more than 0.5, the Young's modulus of devitrified glass has the tendency of rapid reduction.Al
2O
3/ MgO＜0.5 can obtain having the devitrified glass of the above high Young's modulus of 150GPa.Al more preferably
2O
3/ Mg＜0.45.But, as Al
2O
3The mol ratio of/MgO is too small, and the high temperature viscosity of glass has the tendency and the big danger of grain fineness number of reduction, so Al
2O
3/ MgO ratio is more than 0.2, more preferably is suitable more than 0.25.
TiO
2Be to have MgOSiO
2The enstatite of forming and have (MgAl) SiO
3The karyogenesis agent that the enstatite solid solution crystal of forming is separated out mutually.Also have, at SiO
2Poor occasion, TiO
2There is the glass of inhibition to lose transparent effect.But, at TiO
2Content is less than 5% occasion, can not obtain fully as the effect of primary crystallization karyogenesis agent, and the glass surface crystallization stops, and making the homogeneous devitrified glass has the tendency that becomes difficult.On the other hand, as TiO
2Content surpasses 15%, the high temperature viscosity of glass cross low and produce phase-splitting, again lose transparent, the tendency that has glass production to worsen very much.For this reason, as the productivity of considering glass, chemical durability, high temperature viscosity, nucleus generation etc., TiO
2Content is the 5-15% scope, and the scope that is preferably 5.5-14% is suitable.The scope of 8-14% more preferably.
Also have, as described below, with the combination of other composition,,, therefore there is TiO owing to can obtain having the devitrified glass of the above high Young's modulus of 160GPa comparing with surface smoothing when more paying attention to Young's modulus
2Content is the ideal situation of 8.5-15%.
In devitrified glass of the present invention, can contain Y
2O
3But, shown in the embodiment described as follows, for example, because the Y of importing 2%
2O
3, the Young's modulus of devitrified glass can increase about 10GPa, and liquidus temperature can reduce 50-100 ℃.That is, owing to import a spot of Y
2O
3Can significantly improve the characteristic and the productivity of glass.As Y
2O
3Content is more than 0.3%, can obtain above-mentioned Y
2O
3Effect.Y
2O
3Content is more preferably more than 0.5%.But, Y
2O
3Can keep restraint to the primary crystallization growth that contains in the above-mentioned glass.For this reason, as Y
2O
3Content is too much, is easily to cause surface crystallization in the thermal treatment carried out of glass crystallization in purpose, and have can not the manufacturing purpose devitrified glass tendency.From this point of view, Y
2O
3Content is suitable below 10%.Especially, Y
2O
3Content is preferably below 8%, more preferably below 3%.
Moreover devitrified glass of the present invention can contain the ZrO below 10%
2ZrO
2Improve the stability of glass, particularly can improve the stability of the glass that contains volume MgO and finish the work better.In addition, karyogenesis agent effect is also arranged, as TiO
2Auxiliary promotion preliminary treatment in the glass phase-splitting and help grain refining.But, as ZrO
2Content surpass 10% because the danger that exists glass high melt and uniformity to worsen, its add-on is that 1-10% is suitable.Moreover, as the high melt of consideration glass and the uniformity of crystal grain etc., ZrO
2Add-on be preferably 0-6%, 1-5% more preferably.
Devitrified glass of the present invention is from characteristic and homogeneous crystallinity viewpoints such as maintenance high Young's modulus, SiO
2, Al
2O
3, MgO and TiO
2Add up to more than 92%.SiO
2, Al
2O
3, MgO and TiO
2Total be preferably more than 93%, more preferably more than 95%.
As in above-mentioned scope, the composition as beyond above-mentioned in the scope of not damaging the desired characteristic of devitrified glass, also can contain alkalimetal oxide R
2O (Li for example
2O, Na
2O, K
2O etc.) and/or alkaline earth metal oxide RO compositions such as (for example CaO, SrO, BaO etc.).Alkalimetal oxide and/or alkaline earth metal oxide can use nitrate as frit.As when glass is made, using deaerating agent Sb
2O
3, platinum easily from glass melting with sneaking into the platinum crucible in the glass owing to use nitrate, can suppress platinum and sneak in the glass as frit.From obtaining the viewpoint of above-mentioned effect, the content of alkalimetal oxide and alkaline earth metal oxide respectively is to be ideal more than 0.1%.But, containing the occasion of alkalimetal oxide, owing to exist alkalimetal oxide to reduce the tendency of Young's modulus, its content is suitable below 5%.On the other hand, alkalimetal oxide has the effect that reduces the glass melting temperature and makes from the platinum tramp material ionization of platinum smelting furnace and the effect of melting.This situation is the effect of adding more than 0.1%.K particularly
2O, owing to have the effect of the smelting temperature that reduces glass and make from the platinum tramp material ionization of platinum smelting furnace and the effect of melting, and the effect that makes Young's modulus be difficult to reduce, be ideal therefore.Containing K
2The occasion of O, its content are to be suitable below 5%, are preferably 0.1～2%, more preferably 0.1～1%.
Moreover, containing the occasion of alkaline earth metal oxide, because alkalimetal oxide has the tendency that makes grain growth, so its content is suitable below 5%.Containing the occasion of alkalimetal oxide, particularly K
2O is 0.1～5%, is preferably 0.1～2%, more preferably 0.1～1%, and ideal.Containing the occasion of alkaline earth metal oxide, particularly SrO is 0.1～5%, is preferably 0.1～2%, ideal.Particularly from the stabilization viewpoint of glass, SrO is an ideal, and its content is 0.1～5%, more preferably 0.1～2%,
In addition, also can contain deaerating agent As for seeking homogenizing of glass
2O
3And/or Sb
2O
3Corresponding to forming the high temperature viscosity that changes, in glass, add an amount of As according to glass
2O
3, Sb
2O
3Or As
2O
3+ Sb
2O
3Can obtain the more glass of homogeneous.But, too much as the addition of deaerating agent, exist the proportion of glass to rise, also there is the situation that with the platinum crucible reaction crucible is damaged with melting in addition in the tendency that Young's modulus reduces.So the addition of deaerating agent is below 2%, better is suitable below 1.5%.
Except that above basal component, do not damage devitrified glass characteristic of the present invention and can contain impurities in raw materials, for example as Cl, F, the SO of glass fining agent
3Deng respectively below 1%.
Also have, it is ideal that devitrified glass of the present invention does not contain ZnO and NiO in fact.Be because ZnO makes and is easy to form hard crystalline spinel.In addition, from being easy to form the viewpoint of spinel and being the viewpoint that influences the composition of environment, do not contain NiO and wish.
Ideal information recording carrier of the present invention is SiO with a form of substrate
2: 35-65 mole %, Al
2O
3: 5-25 mole %, MgO:10-40 mole %, TiO
2: 5-15 mole %, Y
2O
3: 0-10 mole %, ZrO
2: 0-6 mole %, R
2O:0-5 mole % (but R represents to be selected from least a of Li, Na, K), RO:0-5 mole % (but R represents to be selected from least a of Ca, Sr, Ba), As
2O
3+ Sb
2O
3: 0-2 mole %, SiO
2+ Al
2O
3+ MgO+TiO
2: 92 moles more than the % is to be the substrate that the devitrified glass of enstatite and/or its sosoloid constitutes by primary crystallization.
So-called primary crystallization of the present invention is for obtaining the essential crystallization of effect of the present invention, is the maximum crystallization that contains in the crystallization of glass.Contain the above crystallization of 50 volume % in the crystallization that so-called ideal primary crystallization is a glass.Also have, devitrified glass of the present invention is that enstatite and/or its sosoloid are 70 volume % mostly, according to circumstances can contain more than the 80 volume %, also can contain more than the 90 volume %.The primary crystallization of devitrified glass of the present invention is for example to have MgOSiO
2(MgAl) SiO
3The enstatite of forming (comprising enstatite sosoloid).In addition, devitrified glass of the present invention, in the occasion that contains enstatite and sosoloid thereof, primary crystallization is the set of enstatite and sosoloid thereof.Also have, enstatite comprises clinoenstatite, former enstatite and enstatite.Moreover, except that above-mentioned crystallization, also can contain titanate.As the example of crystallization phases, the enstatite and/or its sosoloid total amount 50-100 volume % that separate out are arranged for example, titanate 50～0 volume %.In addition, the enstatite and/or its sosoloid 70-90 volume % that separate out are arranged for example, titanate 30-10 volume %.At this moment, be better more than the 90 volume % in the crystallization of total amount in glass of enstatite and/or its sosoloid and titanate, be 95 volume % are above better, be 99 volume % are above best.
Crystallization as beyond enstatite and/or its sosoloid and the titanate has mullite, forsterite, trichroite, quartz, quartz solid solution etc. for example.But do not contain spinel.Be highly susceptible to grinding because enstatite hardness low (Mohs' hardness 5.5), enstatite are the devitrified glass of primary crystallization, have the feature that in the relatively shorter time, can obtain wishing surfaceness.Moreover because the chain or the lamellated crystal form of enstatite enter glass ingredient between its slit, anticipation can obtain little particle size and high Young's modulus.To this, be scleroma brilliant (Mohs' hardness 8) because spinel is compared with enstatite, the effect of anticipation infringement easy grinding.It is ideal that devitrified glass of the present invention does not contain quartz solid solution.
In addition, the crystal area proportion (degree of crystallinity) in the glass of the present invention is about 20～70 volume %.At this, degree of crystallinity is more than 50 volume %, and this has in manufacturing aspect the substrate of high Young's modulus is ideal.But, as consider the difficulty of the back step operation after the crystallization, degree of crystallinity can be 20-50 volume %, further can be 20-30 volume %.In addition, in the occasion of comparing the height of paying attention to Young's modulus with the difficulty of back step operation after the crystallization, degree of crystallinity can be 50-70 volume %.
Moreover the mean value of the grain-size (particle diameter) that devitrified glass of the present invention is contained is to be preferably below the 100nm, is better below the 50nm, is best below the 30nm.Surpass 100nm as crystal size mean value, not only the physical strength of glass reduces, and causes that crystal grain loses the danger that worsens with the glass surface roughness when having attrition process.The control of such grain-size can mainly be carried out according to the kind and the aftermentioned heat-treat condition of contained crystallization phases.Can obtain in the present invention under the heat-treat condition of primary crystallization of the enstatite of essential composition and/or its sosoloid, it is possible obtaining above-mentioned fine grain size.
In addition, the thermal expansivity of the devitrified glass of formation substrate of the present invention is 65 * 10
-7～85 * 10
-7/ ℃, further can be 73 * 10
-7～83 * 10
-7/ ℃.The property settings that thermal expansivity can require with substrate according to information recording carrier is in above-mentioned scope.
The substrate that devitrified glass of the present invention constitutes can be made with the manufacture method of known glass substrate.For example, high-temperature melting method, the frit that is about to the ratio of stipulating is in air or melting in the non-active gas atmosphere, add whipping agent and deaerating agent and carry out homogenizing of glass with stirring to wait, according to known extrusion process with press down method formed glass sheets such as shaping,, carry out processing such as grinding, grinding, can obtain wishing the glasswork of size, shape thereafter.Devitrified glass of the present invention for example can be 1400-1650 ℃ of melting, and comprising can be at 1500-1650 ℃, and then 1550-1600 ℃ of melting.As mentioned above, for example add the K that conduct reduces the composition of smelting temperature
2O is an ideal.
The glasswork that obtains is carried out heat of crystallization to be handled.
Heat treating method is had no particular limits, can suitably select corresponding to the transition temperature of the content of crystallization promoter and glass, crystallization top temperature etc.But the stage is at lower temperature (for example, (transition temperature of glass (Tg)-30 ℃)～(Tg+60 ℃), Tg～(Tg+60 ℃) especially in the early stage) thermal treatment can produce many nucleus.These temperature are specifically 700-850 ℃ of scope., temperature be raised to 850-1150 ℃ make crystal growth, see it is ideal from the viewpoint of crystal refinement thereafter.At this moment, glass is separated out small grains after 500-850 ℃, and from preventing the viewpoint of sheet glass shape deformation, it is better that heat-up rate is 0.1-10 ℃/minute.But, glass to 500-850 ℃ especially without limits to heat-up rate, can be 5～50 ℃/minute.In addition, in the present invention, for manufacturing has identical or the devitrified glass that crystallization uniformity identical identical with grain size of Young's modulus, generation nucleus thermal treatment and the heat treated allowable temperature scope of grain growing can keep the temperature amplitude more than 30 ℃, so crystalline manufacturing process can easily control.
Moreover, have MgOSiO by thermal treatment of the present invention
2The enstatite of forming and have (MgAl) SiO
3The enstatite sosoloid of forming is separated out as primary crystallization and is heat-treat condition.Also have, except that these primary crystallizations, also can separate out other crystallizations such as forsterite, trichroite, titanate, mullite, the condition that enstatite and sosoloid thereof are separated out will be set.As such condition, handle as heat of crystallization, 850-1150 ℃ is ideal.Being heated to 875-1050 ℃ is ideal.Less than 850 ℃, enstatite and sosoloid thereof are separated out difficulty as Heating temperature.In addition, as surpassing 1150 ℃, the crystal beyond enstatite and the sosoloid thereof is separated out and is become different.In addition, because below 875-1000 ℃, the particle diameter of enstatite and sosoloid thereof can be smaller, for example is below the 100nm, more preferably below the 50nm.The crystalline heat treatment time, according to the relation of thermal treatment temp owing to the effect of degree of crystallinity, size of microcrystal, can suitably select by degree of crystallinity, the size of microcrystal of hope, 850-1150 ℃ thermal treatment occasion, 1-4 hour is ideal.
In addition, the karyogenesis treatment temp that to carry out before heat of crystallization is handled is set temperature than low 30 ℃ of the transition temperature (Tg) of glass to high 60 ℃ temperature, more preferably high 0～60 ℃ temperature than Tg, be preferably the temperature higher 10～50 ℃, see it is suitable from the viewpoint of the crystal grain of separating out the small grains diameter than Tg.
Finish heat treated devitrified glass molding and can grind on demand, Ginding process is not particularly limited.For example, use synthetic abrasive particle and natural abrasive particles such as natural diamond, cerium oxide such as diamond synthesis, silicon carbide, aluminum oxide, norbide, can grind by known method.Be shaped and finish, the molding before the crystallization can carry out above-mentioned crystallization treatment after grinding.
The information recording carrier that devitrified glass of the present invention constitutes can be made substrate shape with molding as stated above with substrate.
It is ideal that glass-ceramic substrate of the present invention has the following surface smoothing of measuring with AFM (atomic force microscope) of average roughness Ra 1nm.The occasion that particularly devitrified glass of the present invention is used for magnetic disk substrate, the average roughness Ra on surface is very big to the recording density influence of disk.Surpass 1nm as surfaceness, reach the high record density difficulty.As consider the high record densityization of disk with regard to the surfaceness of glass-ceramic substrate of the present invention, 0.7nm is following better, and 0.5nm is following best.
The substrate that contains the devitrified glass formation of the present invention of enstatite and sosoloid thereof as primary crystallization is high strength, high rigidity, high Young's modulus, and chemical durability and superior for heat resistance, therefore uses as magnetic disk substrate.Moreover, devitrified glass of the present invention, owing to be alkali-free or low alkali, in the occasion of making magnetic disk substrate, the corrosion of magnetic film and substrate can reduce widely, can preserve magnetic film best.
As mentioned above, glass-ceramic substrate of the present invention is the SiO of enstatite and/or its sosoloid by primary crystallization
2-Al
2O
3-MgO is that glass constitutes, and in addition, the present invention includes by SiO
2-Al
2O
3-MgO is the glass beyond the glass, and primary crystallization is that the glass of enstatite and/or its sosoloid constitutes, and has the information recording carrier glass-ceramic substrate of the following abrasive surface of surface roughness Ra 1nm.Also have, in the crystallization of this primary crystallization in glass, contain more than the 50 volume %.In many occasions, contain enstatite in this devitrified glass crystallization and/or more than its sosoloid 70 volume %, according to circumstances contain more than the 80 volume %, and then contain more than the 90 volume %.In addition, in this devitrified glass, the crystalline ratio is approximately 20～70% in the glass.
The mean value of the size of contained crystal grain (particle diameter) (median size of crystal grain) is to be ideal below the 0.5 μ m in the devitrified glass in such glass-ceramic substrate, is better below the 0.3 μ m, is optimal below the 0.1 μ m.The size mean value of contained crystal grain is preferably below the 50nm in the devitrified glass.Surpass 0.5 μ m as the mean value of crystal size, not only the physical strength of glass reduces, and causes that crystal grain loses and have the danger that the glass surface roughness is worsened during attrition process.The control of such grain-size can mainly be carried out according to the kind and the heat-treat condition described later of contained crystallization phases.In the present invention, in the heat-treat condition of acquisition for the primary crystallization of the enstatite of composition required in this invention and/or its sosoloid, it is possible obtaining above-mentioned fine grain size.
If size of microcrystal diminishes, then the transmitance of the crystallite glass substrate of the thick 1mm of wavelength 600nm polished rod then becomes big.For glass substrate of the present invention, higher more than 50% more than 10%, even 60%-90% also can obtain.
It is that the above high speed rotating substrate of 140GPa is an ideal that such glass-ceramic substrate is made Young's modulus.In addition, not contain the quartz solid solution as primary crystallization in fact be ideal to glass-ceramic substrate of the present invention.Also have, the spinel that glass-ceramic substrate of the present invention does not contain in fact as crystallization phases is an ideal.Because it is hard crystallization (Mohs' hardness 8) that spinel is compared with enstatite, grind difficulty, being difficult to obtain surface roughness Ra is the following abrasive surface of 1nm.
The necessity of high Young's modulus can illustrate by the following fact.Promptly, miniaturization, high capacity, high speed along with nearest HDD, the prediction thickness of magnetic recording media tegmen sheet in the future perhaps is thinned to 0.635mm from present 3.5 inches 0.8mm, 2.5 the 0.635mm of inch is thinned to 0.43mm, be thinned to 0.38mm again, the speed of rotation of substrate is from present top speed 10000rpm to 14000rpm and high speed rotatingization.Such magnetic recording media is thin more with substrate, is easy to produce deflection more with crooked.In addition, it is big more to envision the stress that high speed rotating substrate more is subjected to (based on the blast that is produced by rotation and act on the power of dish).Based on theory of mechanics, unit surface is born the following expression of amount of deflection W of the disk of load P.
In the formula, a is the outside diameter of disk, and h is the thickness of substrate, and E is the Young's modulus of disk material.Under static state, only for being added in gravity on the disk, be d as the proportion of disk material, amount of deflection can be expressed as:
Wherein G is the ratio spring rate (=Young's modulus/proportion) of disk material.
On the other hand, at the rotating state of disk, considering to ignore gravity and centrifugal force equilibrated occasion, the power that is added on the disk based on rotation can be blast, and blast is the function of disk speed of rotation, and ratio is its 2 power in general.Therefore, amount of deflection is represented by following formula during the disk high speed rotating:
From its result as can be known, be the substrate material of the essential high Young's modulus of amount of deflection of control high speed rotating substrate.By contriver's calculating, the thickness requirement of 2.5 inches substrates is thinned to 0.635～0.43mm, and the ratio spring rate that the thickness requirement of 3.5 inches substrates is thinned to 0.8～0.635mm and substrate material is at least more than the 37MNm/kg.In addition, come high speed from present 7200rpm to 10000rpm in the future as the speed of rotation of 3.5 inches Ha イ エ Application De substrates, the aluminium substrate with about 70GPa Young's modulus can not adapt to, and need have the new substrate material of the above Young's modulus of 110GPa at least.Ratio spring rate or Young's modulus as substrate material are high more, and it is big that not only rigidity height of substrate, and the shock-resistance of substrate and intensity also become simultaneously, thereby the strong request of HDD market has the glass material of height ratio spring rate and big Young's modulus.
Contain SiO among the present invention
2: 35-43 mole %, Al
2O
3: 9-20 mole %, MgO:30-39 mole %, Y
2O
3: 1-3 mole %, TiO
2: 8.5-15 mole %, ZrO
2: the substrate of 1-5 mole % has the above high Young's modulus of 160GPa.At this occasion, SiO
2/ MgO mol ratio is to be suitable below 1.35.
The magnetic disk substrate that devitrified glass of the present invention constitutes can satisfy surface smoothing as the magnetic disk substrate needs, flatness, intensity, hardness, chemical durability, thermotolerance etc. fully.In addition, with former devitrified glass (Li
2O-SiO
2Therefore microcrystalline glass in series) compare, have about 2 times Young's modulus, can suppress deflection by the disk high speed rotating, be fit to as the high TP1 hand disk wafer material of realization to littler.
Because thermotolerance, surface smoothing, chemical durability, optical property and the physical strength of devitrified glass of the present invention are superior, therefore electrooptics glass substrates such as glass substrate of using with substrate and photomagneto disk applicable to information recording carriers such as disks and CD.
Information recording carrier of the present invention is characterised in that the recording layer that has substrate of the present invention and form on this substrate.Below explanation forms magnetospheric disk (hard disk) at least on the major surfaces of the substrate that devitrified glass of the present invention constitutes
Layer except that magnetosphere has stratum basale, protective layer, lubricant film, control buckle layer etc. for example by the function face, can form as required.Form these layers and can utilize various film shaped technology.Magnetospheric material is had no particular limits.Magnetosphere has ferrite system, iron-rare earth system etc. for example except that Co system.Magnetosphere can be any magnetosphere of horizontal magnetic recording, perpendicular magnetic recording.
Specifically, Co is arranged for example is the magneticthin film of CoPt, CoCr, CoNi, CoNiCr, CoCrTa, CoPtCr and CoNiCrPt, CoNiCrTa, CoCrPtTa, the CoCrPtSiO etc. of principal constituent to magnetosphere.In addition, also magnetosphere can be separated with nonmagnetic layer, constitute so that reduce the multilayer of noise.
About magnetospheric stratum basale, can select according to magnetosphere.As stratum basale at least a above material of non-magnetic metal such as being selected from Cr, Mo, Ta, Ti, W, V, B, Al is arranged for example, or the stratum basale that constitutes such as its metal oxide, nitride, carbide.At Co is the magnetospheric occasion of principal constituent, and from improving the viewpoint of magnetic properties, Cr monomer and Cr alloy are ideal.Stratum basale is not limited to individual layer, for example also can be the laminated multilayered structure of identical or different layer.Multilayer such as Al/Cr/CrMo, Al/Cr/Cr stratum basale etc. for example.
In addition, between substrate and magnetosphere or magnetospheric top, the concavo-convex key-course that prevents magnetic head and disk absorption can be set.Owing to be provided with this concavo-convex key-course, can suitably adjust the surfaceness of disk, magnetic head and disk are not adsorbed, obtain the high disk of reliability.Concavo-convex key-course material and formation method be known to be had manyly, is not particularly limited.For example, at least a above metal that is selected from Al, Ag, Ti, Nb, Ta, Bi, Si, Zr, Cr, Cu, Au, Sn, Pd, Sb, Ge, Mg etc. is arranged for example as concavo-convex key-course material, or its alloy, or the stratum basale that constitutes such as its oxide compound, nitride, carbide.From the viewpoint of easy formation, Al simple substance and Al alloy, aluminum oxide, aluminium nitride be that the metal of principal constituent is wished with aluminium.
In addition, as consider the magnetic head friction, the stratified surfaceness Rmax=50 of machicolated form～300 dusts are preferably.Better scope is Rmax=100～200 dusts.Rmax is less than the occasion of 50 dusts, because that magnetic disk surface is bordering on is smooth, and magnetic head and disk absorption, magnetic head and disk are injured, cause the magnetic head fragmentation owing to adsorb, so are unfavorable.In addition, Rmax surpasses the occasion of 300 dusts, and the height that slides (it is high to slide) becomes big, causes that recording density reduces, and is unfavorable therefore.
Also have, concavo-convex key-course is not set, concavo-convex with the interpolation of means such as etch processes and laser radiation on glass substrate surface, also can carry out structure (テ Network ス チ ヤ リ Application グ) and handle.
As protective layer Cr film, Cr alloy film, carbon film, zirconium oxide film, silicon dioxide film etc. are arranged for example.These protective membranes can together be used formation continuously such as inline process type spray equipment with stratum basale, magnetosphere etc.In addition, these protective layers also can be individual layer or the multilayer that is made of identical or different film constitutes.
On above-mentioned protective layer or replace said protection film also can form other protective layer.For example, on the above-mentioned protective layer with the colloidal silicon dioxide microparticulate in the diluent of quaalkane oxosilane (テ ト ラ ア Le コ キ シ ラ Application) with the dilution of pure series solvent, and coating, calcining also can form silicon oxide (SiO again
2) film.Can finish protective membrane and concavo-convex key-course two aspect functions under this occasion.
Lubricant film has multiple motion, in general, will be the equal solvent dilution with tetrafluoro-methane for the PFPE of liquid lubricant, applies with pickling process, whirl coating, spraying method at dielectric surface, carries out heat treated as required and forms.
Embodiment
Below describe the present invention in detail with embodiment, these embodiment are to the present invention without limits.
The glass that embodiment 1-42 has been shown in table 1-5 is formed (mole % or weight %).Also have, the composition of putting down in writing among the table 1-5 is that raw material is formed, and the difference of in the devitrified glass of embodiment 1-15 raw material being formed result with the comparison of devitrified glass compositional analysis and be both is in ± 0.1 mole of %.Therefore, the raw material glass composition shown in the table 1-5 is identical with the devitrified glass composition in fact.
Raw material during in an embodiment, as these glass of melting can use SiO
2, Al
2O
3, Al (OH)
3, MgO, Y
2O
3, TiO
2, ZrO
2, KNO
3, Sr (NO
3)
2, Sb
2O
3Deng and in the regulation ratio weighing 250-300g of table shown in the 1-5.Also have, do not illustrate in the table, all glass contains Sb
2O
30.03 mole %.The raw material of weighing is mixed fully and make the blending batch of material, in the platinum crucible of packing into, in air, carried out while stirring glass melting 4-5 hour at 1550 ℃.After the melting, glass melt is flowed into be of a size of in the carbon mould of 180 * 15 * 25mm, be cooled to directly pack into after the transition point temperature of glass in the annealing furnace, in annealing furnace, cool off about 1 hour up to room temperature in the transformetion range of glass.The crystallization that the glass that obtains with microscopic examination is separated out.
After the glass of 180 * 15 * 25mm size ground by 100 * 10 * 10mm, 10 * 10 * 20mm, 10 * 1 * 20mm, pack in the heat treatment furnace, be warmed up to the thermal treatment temp first time shown in the table 1-5 with 1-5 ℃/minute heat-up rate, carried out the thermal treatment first time in 2-10 hour in this temperature insulation, thermal treatment for the first time finish the back directly from the first time thermal treatment temp be warmed up to 2-10 ℃/minute heat-up rate and show the thermal treatment temp second time shown in the 1-5, be incubated after 1-5 hour, make devitrified glass to room temperature at the stove internal cooling.Again the glass that obtains is ground by 95mm length, make the sample of measuring Young's modulus, proportion.The data that mensuration is obtained and the composition of glass together are shown in table 1-5.
For relatively, the glass substrate that the spy is opened record in No. the 2516553rd, the disclosed chemcor glass substrate and United States Patent (USP) in flat 1-239036 number respectively as a comparative example 1 and 2 will be formed and characteristic is recorded in the table 6.
[table 1]
| Form (mole %) | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| SiO 2 | 48.00 | 47.00 | 47.00 | 46.00 | 47.00 | 41.00 | 43.00 | 45.00 | 47.00 | 49.00 |
| Al 2O 3 | 11.00 | 10.50 | 10.50 | 10.50 | 12.50 | 12.50 | 12.50 | 12.50 | 12.50 | 10.50 |
| MgO | 30.00 | 30.00 | 28.50 | 31.00 | 28.50 | 34.50 | 32.50 | 30.50 | 28.50 | 29.50 |
| Y 2O 3 | 1.00 | 0.50 | 0.50 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 1.00 | |
| ZrO 2 | 2.00 | 2.00 | 2.00 | |||||||
| TiO 2 | 10.00 | 10.00 | 10.00 | 10.00 | 10.00 | 10.00 | 10.00 | 10.00 | 10.00 | 10.00 |
| Al 2O 3/MgO | 0.37 | 0.35 | 0.37 | 0.34 | 0.44 | 0.36 | 0.38 | 0.41 | 0.44 | 0.35 |
| SiO 2/MgO | 1.60 | 1.56 | 1.65 | 1.48 | 1.65 | 1.18 | 1.32 | 1.47 | 1.65 | 1.66 |
| S+A+M+T | 99 | 97.5 | 96 | 97.5 | 98 | 98 | 98 | 98 | 98 | 99 |
| Transition temperature Tg (℃) | 732 | 735 | 729 | 732 | 729 | 738 | 740 | 739 | 740 | 732 |
| Formation nucleus thermal treatment temp (℃) | Tg+28 | Tg+35 | Tg+31 | Tg+38 | Tg+31 | Tg+22 | Tg+30 | Tg+31 | Tg+20 | Tg+28 |
| Form nucleus heat treatment time (h) | 4 | 4 | 4 | 4 | 4 | 4 | 4 | 4 | 4 | 4 |
| Heat-up rate * (℃/h) | 300 | 300 | 300 | 300 | 300 | 300 | 300 | 300 | 300 | 300 |
| The heat of crystallization treatment temp (℃) | 1000 | 1000 | 1000 | 1000 | 1000 | 1000 | 1000 | 1000 | 1000 | 1000 |
| The heat of crystallization treatment time (h) | 4 | 4 | 4 | 4 | 4 | 4 | 4 | 4 | 4 | 4 |
| Heat-up rate ** (℃/h) | 240 | 240 | 240 | 240 | 240 | 240 | 240 | 240 | 240 | 240 |
| The surface of fracture kind | The glassiness | The glassiness | The glassiness | The glassiness | The glassiness | The glassiness | The glassiness | The glassiness | The glassiness | The glassiness |
| The transmitance of wavelength 600nm light | 75％ | 73％ | 78％ | 79％ | 76％ | 75％ | 73％ | 78％ | 79％ | 76％ |
| Proportion (g/cm 3) | 3.086 | 3.14 | 3.11 | 3.158 | 3.038 | 3.309 | 3.254 | 3.207 | 3.168 | 3.068 |
| Young's modulus (GPa) | 148.5 | 150.5 | 147 | 153.2 | 146.7 | 179.1 | 170 | 1634 | 157.3 | 149.1 |
| Poisson's ratio | 0.231 | 0.23 | 0.229 | 0.23 | 0.225 | 0.245 | 0.245 | 0.241 | 0.237 | 0.228 |
| The primary crystallization kind | Enstatite | Enstatite | Enstatite | Enstatite | Enstatite | Enstatite | Enstatite | Enstatite | Enstatite | Enstatite |
| Other crystallization kind | Titanate | Titanate | Titanate | Titanate | Titanate | Titanate | Titanate | Titanate | Titanate | Titanate |
| Than spring rate MNm/kg | 48.1 | 47.9 | 47.3 | 48.5 | 48.3 | 54.1 | 52.2 | 51.0 | 49.7 | 48.6 |
| The coefficient of expansion 10 -7/℃ | 72 | 72 | 75 | 74 | 70 | 83 | 81 | 76 | 72 | 77 |
| Median size (nm) | 30～40 | 30～40 | 40～50 | 20～30 | 50～70 | 100～ 150 | 80～ 120 | 50～70 | 50～70 | 40～50 |
| Ra(nm) | 0.3 | 0.3 | 0.3 | 0.25 | 0.4 | 0.5 | 0.5 | 0.4 | 0.4 | 0.3 |
Enstatite: enstatite and sosoloid thereof; Titanate: titanate
S+A+M+T＝SiO
2+Al
2O
3+MgO+TiO
2
*Heat-up rate to the temperature-rise period that forms the nucleus thermal treatment temp.
*From forming the heat-up rate of nucleus thermal treatment temp to the temperature-rise period of heat of crystallization treatment temp.
[table 2]
| Form (mole %) | 11 | 12 | 13 | 14 | 15 | 16 |
| SiO 2 | 46.00 | 46.00 | 46.00 | 46.00 | 46.00 | 46.00 |
| Al 2O 3 | 10.50 | 10.50 | 10.50 | 10.50 | 10.50 | 10.50 |
| MgO | 30.50 | 30.00 | 30.00 | 31.00 | 30.00 | 31.0 |
| K 2O | 0.50 | 0.50 | 0.50 | |||
| SrO | 1.00 | 1.50 | 1.00 | 0.50 | ||
| Y 2O 3 | 0.50 | 0.50 | 0.50 | 0.50 | 0.50 | |
| ZrO 2 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 | 2.00 |
| TiO 2 | 10.00 | 10.00 | 9.00 | 9.00 | 10.00 | 9.50 |
| Al 2O 3/MgO | 0.34 | 0.35 | 0.35 | 0.34 | 0.34 | 0.34 |
| SiO 2/MgO | 1.51 | 1.53 | 1.53 | 1.48 | 1.53 | 1.48 |
| S+A+M+T | 97 | 96.5 | 95.5 | 96.5 | 96.5 | 97 |
| Transition temperature Tg (℃) | 726 | 728 | 726 | 725 | 727 | 734 |
| Formation nucleus thermal treatment temp (℃) | Tg+30 | Tg+30 | Tg+30 | Tg+30 | Tg+30 | Tg+26 |
| Form nucleus heat treatment time (h) | 4 | 4 | 4 | 4 | 4 | 4 |
| Heat-up rate (℃/h) * | 300 | 300 | 300 | 300 | 300 | 300 |
| The heat of crystallization treatment temp (℃) | 1000 | 1000 | 1000 | 1000 | 1000 | 1000 |
| Heat of crystallization processing speed (h) | 4 | 4 | 4 | 4 | 4 | 4 |
| Heat-up rate (℃/h) ** | 240 | 240 | 240 | 240 | 240 | 240 |
| The surface of fracture kind | The glassiness | The glassiness | The glassiness | The glassiness | The glassiness | The glassiness |
| The transmitance of wavelength 600nm light | 82％ | 70％ | 67％ | 80％ | 80％ | 78％ |
| Proportion (g/cm 3) | 3.127 | 3.172 | 3.175 | 3.124 | 3.15 | 3.139 |
| Young's modulus (GPa) | 149.2 | 151.8 | 152.1 | 147.1 | 148.2 | 149.5 |
| Poisson's ratio | 0.232 | 0.234 | 0.234 | 0.231 | 0.232 | 0.229 |
| The primary crystallization kind | Enstatite | Enstatite | Enstatite | Enstatite | Enstatite | Enstatite |
| Other crystallization kind | Titanate | Titanate | Titanate | Titanate | Titanate | Titanate |
| Than spring rate (MNm/kg) | 47.7 | 47.9 | 47.9 | 47.1 | 47.0 | 47.6 |
| The coefficient of expansion 10 -7/℃ | 77.9 | 75.1 | 74.7 | 79.2 | 78.1 | 75 |
| Median size (nm) | 20～30 | 30～50 | 30～50 | 20～30 | 20～30 | 20～30 |
| Ra(nm) | 0.20 | 0.30 | 0.30 | 0.30 | 0.25 | 0.20 |
Enstatite: enstatite and sosoloid thereof; Titanate: titanate
S+A+M+T＝SiO
2+Al
2O
3+MgO+TiO
2
*Heat-up rate to the temperature-rise period that forms the nucleus thermal treatment temp.
*From forming the heat-up rate of nucleus thermal treatment temp to the temperature-rise period of heat of crystallization treatment temp.
[table 3]
| Form (mole %) | 17 | 18 | 19 | 20 | 21 | 22 | 23 | 24 | ||||||||
| Mole % | Weight % | Mole % | Weight % | Mole % | Weight % | Mole % | Weight % | Mole % | Weight % | Mole % | Weight % | Mole % | Weight % | Mole % | Weight % | |
| SiO 2 | 39.00 | 35.57 | 39.00 | 35.13 | 39.00 | 36.07 | 39.00 | 35.08 | 39.00 | 35.89 | 39.00 | 36.60 | 38.00 | 34.76 | 38.00 | 34.76 |
| Al 2O 3 | 12.50 | 19.35 | 12.50 | 19.11 | 11.00 | 17.27 | 14.00 | 21.37 | 12.50 | 19.52 | 12.50 | 19.91 | 12.50 | 19.41 | 12.50 | 19.41 |
| MgO | 33.50 | 20.49 | 32.50 | 19.63 | 35.00 | 21.72 | 32.00 | 19.31 | 35.00 | 21.61 | 34.50 | 21.72 | 34.50 | 21.17 | 34.50 | 21.17 |
| Y 2O 3 | 2.00 | 6.86 | 2.00 | 6.77 | 2.00 | 6.95 | 2.00 | 6.76 | 2.00 | 6.92 | 1.00 | 3.53 | 2.00 | 6.88 | 2.00 | 6.88 |
| TiO 2 | 10.00 | 12.13 | 10.00 | 11.98 | 10.00 | 12.30 | 10.00 | 11.96 | 8.50 | 10.40 | 10.00 | 12.48 | 10.00 | 12.16 | 10.00 | 12.16 |
| ZrO 2 | 3.00 | 5.61 | 4.00 | 7.39 | 3.00 | 5.69 | 3.00 | 5.53 | 3.00 | 5.66 | 3.00 | 5.77 | 3.00 | 5.63 | 3.00 | 5.63 |
| Tg | 743 | 744 | 741 | 746 | 750 | 741 | 742 | |||||||||
| Al 2O 3/MgO | 0.373 | 0.385 | 0.314 | 0.438 | 0.357 | 0.362 | 0.362 | 0.362 | ||||||||
| SiO 2/MgO | 1.16 | 1.2 | 1.114 | 1.22 | 1.114 | 1.13 | 1.13 | 1.101 | ||||||||
| S+A+M+T | 95 | 94 | 95 | 95 | 94.5 | 96 | 95 | 95 | ||||||||
| The transmitance (%) of wavelength 600nm light | 40 | 40 | 48 | 30 | 35 | 40 | 40 | 25 | ||||||||
| Median size (nm) | 120-200 | 120-200 | 100-150 | 200-250 | 150-220 | 120-200 | 120-200 | 150-200 | ||||||||
| Ra(nm) | 0.50 | 0.50 | 0.40 | 0.70 | 0.70 | 0.40 | 0.40 | 0.65 | ||||||||
| The coefficient of expansion (10 -7/℃) | 78 | 77 | 75 | 74 | 73 | 75 | 74 | 78 | ||||||||
| Young's modulus (GPa) | 175.00 | 168.90 | 177.00 | 172.90 | 175.70 | 182.50 | 175.40 | 188.50 | ||||||||
| Poisson's ratio υ | 0.250 | 0.251 | 0.250 | 0.251 | 0.256 | 0.246 | 0.255 | 0.245 | ||||||||
| Proportion (g/cm 3) | 3.401 | 3.389 | 3.425 | 3.349 | 3.404 | 3.381 | 3.416 | 3.435 | ||||||||
| Than spring rate (MNm/kg) | 51.5 | 49.8 | 51.7 | 51.6 | 51.6 | 54.0 | 51.3 | 54.9 | ||||||||
| Tn | 790℃/4h | 790℃/4h | 790℃/4h | 790℃/4h | 790℃/4h | 790℃/4h | 790℃/4h | 790℃/4h | ||||||||
| Heat-up rate * | 5℃/min | 5℃/min | 5℃/min | 5℃/min | 5℃/min | 5℃/min | 5℃/min | 5℃/min | ||||||||
| Tc | 1000℃/4h | 1000℃/4h | 1000℃/4h | 1000℃/4h | 1000℃/4h | 1000℃/4h | 1000℃/4h | 1000℃/4h | ||||||||
| Heat-up rate ** | 5℃/min | 5℃/min | 5℃/min | 5℃/min | 5℃/min | 5℃/min | 5℃/min | 5℃/min | ||||||||
| Crystalline state | Well | Well | Well | Well | Well | Well | Well | Well | ||||||||
| The primary crystallization kind | Enstatite | Enstatite | Enstatite | Enstatite | Enstatite | Enstatite | Enstatite | Enstatite | ||||||||
| Other crystallization kind | Titanate | Titanate | Titanate | Titanate | Titanate | Titanate | Titanate | Titanate | ||||||||
Enstatite: enstatite and sosoloid thereof; Titanate: titanate
S+A+M+T＝SiO
2+Al
2O
3+MgO+TiO
2
Tn: form nucleus thermal treatment temp and time T c: heat of crystallization treatment temp and time
*Heat-up rate to the temperature-rise period that forms the nucleus thermal treatment temp.
*From forming the heat-up rate of nucleus thermal treatment temp to the temperature-rise period of heat of crystallization treatment temp.
[table 4]
| Form (mole %) | 25 | 26 | 27 | 28 | 29 | 30 | 31 | 32 |
| SiO 2 | 58.00 | 55.00 | 47.00 | 48.00 | 38.00 | 46.00 | 46.00 | 39.00 |
| Al 2O 3 | 11.00 | 10.50 | 20.00 | 15.00 | 8.00 | 10.50 | 10.50 | 11.00 |
| MgO | 20.00 | 24.00 | 22.50 | 25.50 | 36.50 | 28.00 | 27.00 | 35.00 |
| K 2O | 4.00 | 1.00 | ||||||
| SrO | 3.50 | |||||||
| Y 2O 3 | 0.50 | 0.50 | O.50 | 5.00 | 0.50 | 0.50 | 1.00 | |
| ZrO 2 | 1.00 | 1.0 | 3.00 | 2.00 | 2.00 | 1.00 | ||
| TiO 2 | 10.00 | 10.00 | 10.00 | 10.00 | 9.50 | 9.00 | 9.50 | 13.00 |
| Al 2O 3/MgO | ||||||||
| SiO 2/MgO | 2.9 | 2.29 | 2.09 | 1.88 | 1.04 | 1.64 | 1.70 | 1.11 |
| S+A+M+T | 99 | 99.5 | 99.5 | 98.5 | 92 | 93 | 93 | 98 |
| Tg(℃) | 740 | 735 | 745 | 740 | 730 | 715 | 735 | 741 |
| Formation nucleus thermal treatment temp (℃) | Tg+30 | Tg+25 | Tg+25 | Tg+30 | Tg+50 | Tg+35 | Tg+25 | Tg+29 |
| Form nucleus heat treatment time (h) | 2 | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
| Heat-up rate (℃/h) * | 300 | 300 | 300 | 300 | 300 | 300 | 300 | 300 |
| The heat of crystallization treatment temp (℃) | 1000 | 1000 | 1000 | 1000 | 1000 | 1000 | 1000 | 1000 |
| The heat of crystallization treatment time (h) | 4 | 4 | 4 | 4 | 4 | 4 | 4 | 4 |
| Heat-up rate (℃/h) ** | 300 | 300 | 300 | 300 | 300 | 300 | 300 | 300 |
| The surface of fracture kind | The glassiness | The glassiness | The glassiness | The glassiness | The glassiness | The glassiness | The glassiness | The glassiness |
| The transmitance of wavelength 600nm light | 72％ | 76％ | 35％ | 55％ | 30％ | 75％ | 72％ | 62％ |
| Proportion (g/cc) | 3.12 | 3.14 | 3.05 | 3.08 | 3.41 | 3.012 | 3.124 | 3.39 |
| Young's modulus (GPa) | 145 | 149 | 139 | 142 | 191 | 138 | 146 | 182 |
| Poisson's ratio | 0.221 | 0.22 | 0.231 | 0.232 | 0.241 | 0.223 | 0.221 | 0.242 |
| Than spring rate (MNm/kg) | 46.5 | 47.5 | 45.6 | 46.1 | 56.0 | 45.8 | 46.7 | 53.7 |
| The primary crystallization kind | Enstatite | Enstatite | Enstatite | Enstatite | Enstatite | Enstatite | Enstatite | Enstatite |
| Other crystallization kind | Titante | Titante | Titante | Titante | Titante | Titante | Titante | Titante |
| The coefficient of expansion 10 -7/℃ | 68 | 72 | 62 | 65 | 82 | 72 | 74 | 81 |
| Median size (nm) | 20-30 | 20-30 | 50-70 | 30-50 | 50-80 | 15-30 | 15-30 | 30-60 |
| Ra(nm) | 0.3 | 0.3 | 0.5 | 0.4 | 0.4 | 0.2 | 0.2 | 0.4 |
Enstatite: enstatite and sosoloid thereof; Titanate: titanate
S+A+M+T＝SiO
2+Al
2O
3+MgO+TiO
2
*Heat-up rate to the temperature-rise period that forms the nucleus thermal treatment temp.
*From forming the heat-up rate of nucleus thermal treatment temp to the temperature-rise period of heat of crystallization treatment temp.
[table 5]
| Form (mole %) | 33 | 34 | 35 | 36 | 37 | 38 | 39 | 40 | 41 | 42 |
| SiO 2 Al 2O 3 MgO K 2O Y 2O 3 ZrO 2 TiO 2 Al 2O 3/MgO SiO 2/MgO S+A+M+T | 46.00 10.50 30.50 0.50 0.50 2.00 10.00 0.34 1.51 97 | 46.00 10.50 30.50 0.50 0.50 2.00 10.00 0.34 1.51 97 | 46.00 10.50 30.50 0.50 0.50 2.00 10.00 0.34 1.51 97 | 46.00 10.50 30.50 0.50 0.50 2.00 10.00 0.34 1.51 97 | 46.00 10.50 30.50 0.50 0.50 2.00 10.00 0.34 1.51 97 | 46.00 10.50 30.50 0.50 0.50 2.00 10.00 0.34 1.51 97 | 46.00 10.50 30.50 0.50 0.50 2.00 10.00 0.34 1.51 97 | 46.00 10.50 30.50 0.50 0.50 2.00 10.00 0.34 1.51 97 | 46.00 10.50 30.50 0.50 0.50 2.00 10.00 0.34 1.51 97 | 46.00 10.50 30.50 0.50 0.50 2.00 10.00 0.34 1.51 97 |
| Transition temperature Tg (℃) | 728 | 728 | 728 | 728 | 728 | 728 | 728 | 728 | 728 | 728 |
| Formation nucleus thermal treatment temp (℃) | 770 | 750 | 780 | 800 | 770 | 770 | 770 | 770 | 700 | 700 |
| Form nucleus heat treatment time (h) | 1 | 1 | 1 | 1 | 0.5 | 0.5 | 0.5 | 0.5 | 2 | 2 |
| Heat-up rate (℃/h) * | 1200 | 1200 | 1200 | 1200 | 1200 | 1200 | 1200 | 1200 | 1200 | 1200 |
| The heat of crystallization treatment temp (℃) | 980 | 980 | 980 | 980 | 980 | 980 | 875 | 970 | 970 | 1025 |
| The heat of crystallization treatment time (h) | 4 | 4 | 4 | 4 | 1 | 3 | 2 | 2 | 2 | 2 |
| Heat-up rate (℃/h) ** | 300 | 300 | 300 | 300 | 300 | 300 | 300 | 300 | 300 | 300 |
| The surface of fracture kind | The glassiness | The glassiness | The glassiness | The glassiness | The glassiness | The glassiness | The glassiness | The glassiness | The glassiness | The glassiness |
| The transmitance of wavelength 600nm light | 72％ | 72％ | 72％ | 72％ | 76％ | 72％ | 75％ | 75％ | 75％ | 75％ |
| Proportion (g/cm 3) | 3.115 | 3.113 | 3.113 | 3.111 | 3.104 | 3.110 | 3.057 | 3.101 | 3.111 | 3.111 |
| Young's modulus (GPa) | 146.2 | 146.0 | 146.1 | 146.0 | 145.5 | 145.4 | 137.8 | 144.1 | 144.70 | 144.70 |
| Poisson's ratio | 0.232 | 0.231 | 0.232 | 0.231 | 0.232 | 0.232 | 0.233 | 0.233 | 0.221 | 0.221 |
| The primary crystallization kind | Enstatite | Enstatite | Enstatite | Enstatite | Enstatite | Enstatite | Enstatite | Enstatite | Enstatite | Enstatite |
| Other crystallization kind | Titanate | Titanate | Titanate | Titanate | Titanate | Titanate | Titanate | Titanate | Titanate | Titanate |
| Than spring rate (MNm/kg) | 46.9 | 46.9 | 46.9 | 46.9 | 46.9 | 46.8 | 45.1 | 46.5 | 46.5 | 46.5 |
| The coefficient of expansion 10 -7/℃ | 73 | 73 | 73 | 73 | 73 | 73 | 71 | 73 | 73 | 73 |
| Median size (nm) | 20-30 | 20-30 | 20-30 | 20-30 | 20-30 | 20-30 | 15-20 | 20-30 | 20-30 | 20-30 |
| Ra(nm) | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.20 | 0.30 | 0.30 | 0.30 |
Enstatite: enstatite and sosoloid thereof; Titanate: titanate
S+A+M+T＝SiO
2+Al
2O
3+MgO+TiO
2
*Heat-up rate to the temperature-rise period that forms the nucleus thermal treatment temp.
*From forming the heat-up rate of nucleus thermal treatment temp to the temperature-rise period of heat of crystallization treatment temp.
Table 6
| Comparative example | 1 | 2 |
| Chemically reinforced glass | Commercially available TS-10 devitrified glass | |
| Oxide compound | Te Kaiping 1-239036 | United States Patent (USP) the 2516553rd |
| SiO 2 | 73.0 | |
| Al 2O 3 | 0.6 | |
| CaO | 7.0 | |
| Na 2O | 9.0 | |
| K 2O | 9.0 | |
| ZnO | 2.0 | |
| As 2O 3 | 0.2 | |
| Young's modulus (GPa) | 79 | 90-100 |
| Surface roughness Ra (nm) | 12 | 10-35 |
(1) determining of crystallization kind
The glass powder of the K α line that uses Cu after with regard to crystallization carries out X-ray diffraction and measures (device: マ Star Network サ イ エ Application ス system X-ray diffraction device MXP18A, tube voltage: 50KV, tube current: 300mA, scanning angle 10-90 °).Separating out crystalline from the X-ray diffraction peak value that obtains determines.
(2) physical property measurement method
Measure proportion (density)
With glass specimen itself as the specific gravity test sample.Device uses the electronics specific gravity hydrometer (ミ ラ-ジ エ trade (strain) system MD-200S) that utilizes Archimedes's method.Precision is ± 0.001g/cm
3
Measure Young's modulus
Use side area 10-20mm four directions, the parallel sample of length 50-100mm before the mensuration Young's modulus, is measured proportion (density) and is measured specimen length with slide calliper rule, and it is used as condition determination.Device uses (strain) ultrasound industry system UVM-2.When measuring compressional wave (TI1, TI2) and shear wave (TS1, TS2), as dark contact contact medium, longitudinal wave field share [water], and the shear wave occasion applies dark contact and sample end face with [ソ ニ コ-ト SHN20 or SHN-B25].Carry out compressional wave more than 2 times for same sample, the repeatedly mensuration of shear wave more than 5 times is calculated mean value.Also have, can obtain Poisson's ratio simultaneously according to this operation.The precision of Young's modulus is ± 1GPa that the precision of Poisson's ratio is ± 0.001.
Heat machinery is measured (Thermal Mechanical Analysis)
Cut out test piece by the devitrified glass sample after the crystallization, ground finish becomes the garden column of φ 5mm * 20mm, measures as TMA and uses sample.Determinator uses (strain) リ ガ Network system TAS100.Condition determination is that heat-up rate 4k/min, maximum temperature are 350 ℃.
Atomic force microscope (Atomic Force Microscopy)
Be processed into 30 * 25 * 1mm by the devitrified glass sample, precision optics grinds 2 planes of 30 * 15mm, it is measured as AFM use sample.Device uses the system Nano ScopeIII of Diqital Instrument society.Condition determination: press Tapping mode AFM measurement range 2 * 2 μ m or 5 * 5 μ m, sample is several 256 * 256, and sweep velocity is 1Hz, and the data processing condition is Planefit Auto order 3 (X.Y), Flatten Auto order 3.Integral gain, Proportion gain, Set point adjusts by each mensuration.Also have,, the sample that grinds is washed with pure water, IPA etc. in the large-scale scrubber in clean room as the processing before measuring.
Measure transmitance
Precision optics is ground thick the measuring as transmitance of 2 planar 1mm use sample.Device uses HITACHI optical splitter U-3410, and the mensuration wavelength is 600nm.
Measure degree of crystallinity
The devitrified glass sample is measured X-ray total scattering intensity, can obtain degree of crystallinity * (%) by following formula by its result.Use マ Star Network サ イ エ Application ス system X-ray diffraction device MXP18A as the X-ray diffraction device.
X＝(1-(∑1a/∑1a100))×100
X＝(∑1c/∑1c100)×100
1a: the scattering strength of the amorphous portion of unknown materials
1c: the scattering strength of the crystallising part of unknown materials
The scattering strength of 1a100:100% amorphous sample
The scattering strength of 1c100:100% crystallization sample
Measure thermal expansivity
Glass-cutting sample, ground finish become the garden column of φ 50nm * 20nm, measure used as TMA and use sample.Determinator uses (strain) リ ガ Network system TAS100.Condition determination: heat-up rate is that 4K/min, top temperature are 350 ℃, measures 100-300 ℃ thermal expansivity.
Result shown in the 1-5 shows by table, the devitrified glass Young's modulus of the present invention (more than the 140GPa) of embodiment 1-42 and bigger than the strength characteristics of spring rate (scope of 40-60MNm/kg) etc.Thus, use these glass as occasion such as the information recording carrier of magnetic recording media etc. with substrate, this glass substrate high speed rotating, the substrate difficulty bends and breaks, and hence one can see that can be adapted to the slimming more of substrate.In addition, when the glass before embodiment 1, embodiment 4 and embodiment 10 thermal treatments is measured liquidus temperature, be respectively 1300 ℃, 1290 ℃ and 1270 ℃, can satisfy the liquidus temperature (for example below 1350 ℃) that glass melting and shaping aspect require.In addition, for the devitrified glass of embodiment 1-42, when surveying the median size of crystal grain with transmission electron microscope (TEM), median size is from 20-30nm to 100-150nm.In addition, for the devitrified glass of whole embodiment, to using and carry out the buck face of opticglass grinding by measuring surfaceness, (AFM) carries out surface observation with atomic force microscope.Its result, the surfaceness (Ra) of devitrified glass is below the 0.5nm except that embodiment 20,21 and 24.The surfaceness of these devitrified glasses (Ra) for example can be used, and abrasives such as diamond synthesis, silicon carbide, calcium oxide, ferric oxide, cerium oxide are ground to below the 0.5nm according to common opticglass polishing.Thus, can obtain the superior substrate of flatness, can be used as and seek the low come-up of magnetic head and be the magnetic recording media glass substrate of purpose.Devitrified glass of the present invention is in the occasion of thickness 1mm.The transmitance of wavelength 600nm light is more than 50%, and the transparency is to a certain degree arranged.Such transparency is to obtain under the index of the crystallization kind that obtains wishing, crystallization particle diameter.In the occasion of devitrified glass of the present invention, can obtain for example 60-90% of above-mentioned transmitance.Size of microcrystal is more little, and above-mentioned transmitance is big more.
Corresponding, the chemically reinforced glass substrate surface smoothness and the flatness of the comparative example 1 shown in the table 6 are superior, and thermotolerance and Young's modulus equal strength characteristic are more very different than the present invention devitrified glass.Therefore, when making magnetic recording media, incomplete to the thermal treatment that magnetosphere carries out for obtaining high coercive force, can not get having the magnetic recording media of high coercive force, in addition, owing to contain excessive alkali in the glass of comparative example 1, magnetic film and substrate easily produce corrosion, and the danger that magnetic film is damaged is arranged.
In addition, the glass-ceramic substrate of comparative example 2 in Young's modulus with poorer than glass of the present invention aspect spring rate and smoothness.Particularly the existence owing to big crystal grain has damaged the smoothness of substrate, thereby is difficult to seek high density recording.
The manufacture method of disk
As shown in Figure 1, disk 1 of the present invention is to form concavo-convex key-course 3, stratum basale 4, magnetosphere 5, protective layer 6, lubricant film 7 successively to form on the glass-ceramic substrate 2 of the foregoing description 1.
Now each layer specified.Substrate 2 is garden radius 32.5mm, interior garden radius 10.0mm outside, processes on the garden sheet of thickness 0.43mm, and two major surfaces is finish grinded with surface roughness Ra=4 dusts, Rmax=40 dust.
Concavo-convex key-course is mean roughness 50 dusts, the AlN film of surperficial maximal roughness Rmax 150 dusts, nitrogen content 5-35%.
Stratum basale is the CrV film of about 600 dusts of thickness, ratio of components: Cr:83 atom %, V:17 atom %.
Magnetosphere is the CoPtCr film of about 300 dusts of thickness, ratio of components: Co:76 atom %, Pt:6.6 atom %, Cr:17.4 atom %.
Protective layer is the carbon film of about 100 dusts of thickness.
Lubricant film is to apply the layer that the lubricant film that is made of PFPE forms thickness 8 dusts by spin-coating method on carbon protective layer.
The following describes the manufacture method of disk
At first, garden radius 32.5mm outside, interior garden radius 10.0mm, the devitrified glass that ground finish embodiment 1 makes on the garden sheet of thickness 0.5mm, according to surface roughness Ra=4 dusts, the Rmax=40 dust finish grindes two major surfaces, obtains glass-ceramic substrate for magnetic disk.
Then, after settling above-mentioned glass substrate on the substrate holder, send in the chamber of online spray equipment, then, the seat of settling glass-ceramic substrate is sent into the Al target corrode in first Room, at pressure 4mtorr, 350 ℃ of substrate temperatures, Ar+N
2Gas (N
2=4%) sprays under the atmosphere.The result obtains surfaceness Rmax150 dust on glass-ceramic substrate, the AIN film of thickness 50 dusts (machicolated form stratification).
Then, the seat that arrangement has been formed the glass-ceramic substrate of AIN film is sent into continuously successively CrV (Cr:83 atom % is set, V:17 atom %) second Room of target, CoPtCr (Co:76 atom % is set, Pt:6.6 atom %, Cr:17.4 atom %) in the 3rd Room of target, film forming on substrate.At pressure 2mtorr, 350 ℃ of substrate temperatures spray these films in the Ar atmosphere, can obtain the CrV stratum basale of thickness 600 dusts, the CoPtCr magnetosphere of thickness 300 dusts.
Then, the concavo-convex key-course of formation, stratum basale, magnetospheric layered product are sent in the fourth ventricle of the well heater that heat treated is set.Make fourth ventricle this moment is Ar gas (pressure 2mtorr) atmosphere, changes thermal treatment temp and heat-treats.
Above-mentioned substrate is sent in the 5th Room that the carbon target is set, removed at Ar+H
2Gas (H
2=6%) in the atmosphere outside the film forming, under the filming condition identical with the CoPtCr magnetosphere, obtains the carbon protective layer of thickness 100 dusts with above-mentioned CrV stratum basale.
At last, the substrate that finally forms carbon protective layer is taken out from above-mentioned online spray equipment, on the surface of its carbon protective layer, form the lubricant film of thickness 8 dusts, obtain disk with inversion method coating PFPE.
Information recording carrier of the present invention can be shaped at an easy rate with glass-ceramic substrate, have above big Young's modulus of 140GPa and high thermotolerance, have superior surface working and surface smoothing (surface roughness Ra＜10 dusts), and can be used as hardness and the big substrate material use of intensity.
In addition, the substrate that devitrified glass of the present invention constitutes because the superior for heat resistance of this material, can substrate have distortion and improves the essential thermal treatment of magnetic film characteristic; Because flatness is superior, magnetic head can hang down come-up, can reach high density recordingization; Because Young's modulus with bigger than spring rate and intensity, can reach disk slimming and high speed rotatingization, has the advantage of avoiding the disk breakage simultaneously.
Moreover, devitrified glass of the present invention, acquisition that can be more stable is because easy industrial-scale production can very hopefully become cheap magnetic recording media substrate glass of future generation.
Fig. 1: the simple sectional view that on glass-ceramic substrate 2, forms the disk of the present invention 1 of concavo-convex key-course 3, stratum basale 4, magnetosphere 5, protective layer 6, lubricant film 7 successively.
Claims (47)
1, a kind of information recording carrier, it comprises the substrate that is made of devitrified glass, and this devitrified glass contains:
SiO
2: 35-65 mole %,
Al
2O
3: 5-25 mole %,
MgO:10-40 mole % and
TiO
2: 5-15 mole %,
Wherein the said components total is equal to or higher than 92 moles of %, and the contained oikocryst of this devitrified glass is enstatite and/or its sosoloid.
2, the information recording carrier of claim 1, wherein Al
2O
3Mol ratio (Al with MgO
2O
3/ MgO) be less than 0.5 more than or equal to 0.2.
3, claim 1 or 2 information recording carrier, wherein said devitrified glass contains:
SiO
2: 40-60 mole %,
Al
2O
3: 7-22 mole %,
MgO:12-35 mole % and
TiO
2: 5.5-14 mole %.
4, each information recording carrier of claim 1-3, wherein said devitrified glass contains the Y smaller or equal to 10 moles of %
2O
3
5, each information recording carrier of claim 1-4, wherein said devitrified glass contains the ZrO smaller or equal to 10 moles of %
2
6, a kind of information recording carrier substrate, it constitutes by forming following substantially devitrified glass:
SiO
2: 35-65 mole %,
Al
2O
3: 5-25 mole %,
MgO:10-40 mole %,
TiO
2: 5-15 mole %,
Y
2O
3: 0-10 mole %,
ZrO
2: 0-10 mole %,
R
2O:0-5 mole %, wherein R is selected from least a among Li, Na and the K,
RO:0-5 mole %, wherein R is selected from least a among Ca, Sr and the Ba,
As
2O
3+ Sb
2O
3: 0-2 mole %,
SiO
2+ Al
2O
3+ MgO+TiO
2: 92 moles of % or higher,
And contained oikocryst is enstatite and/or its sosoloid in this devitrified glass.
7, a kind of information recording carrier substrate, it constitutes by forming following substantially devitrified glass:
SiO
2: 35-65 mole %,
Al
2O
3: 5-25 mole %,
MgO:10-40 mole %,
TiO
2: 5-15 mole %,
Y
2O
3: 0-10 mole %,
ZrO
2: 0-10 mole %,
R
2O:0-5 mole %, wherein R is selected from least a among Li, Na and the K,
RO:0-5 mole %, wherein R is selected from least a among Ca, Sr and the Ba,
As
2O
3+ Sb
2O
3: 0-2 mole %,
SiO
2+ Al
2O
3+ MgO+TiO
2: 92 moles of % or higher,
And the degree of crystallinity of described devitrified glass is 20-70 volume %.
8, the substrate of each record of claim 1-7, wherein said devitrified glass contains the Y of 0.3-8 mole %
2O
3
9, the substrate of each record of claim 1-8, wherein said devitrified glass contains the ZrO of 1～10 mole of %
2
10, the substrate of claim 9 record, wherein said devitrified glass contains the ZrO of 1-5 mole %
2
11, the substrate of claim 1-5 and each record of 8-10, wherein said devitrified glass contain the following R of 5 moles of %
2O, wherein R is be selected from Li, Na and K at least a.
12, the substrate of claim 11 record is characterized in that R
2O is K
2O.
13, the substrate of each record of claim 1-12, TiO in the wherein said devitrified glass
2Content is 8-14 mole %.
14, the substrate of each record of claim 1-13 is characterized in that this substrate Young's modulus is more than or equal to 140GPa.
15, the substrate of claim 1 or 2 records, wherein said devitrified glass contains:
SiO
2: 35-43 mole %,
Al
2O
3: 9-20 mole %,
MgO:30-39 mole %,
Y
2O
3: 1-3 mole %,
TiO
2: 8.5-15 mole % and
ZrO
2: 1-5 mole %.
16, the substrate of claim 15 record, wherein SiO
2The mol ratio of/MgO is below 1.35.
17, the substrate of claim 15 or 16 records, wherein this substrate Young's modulus is more than the 160GPa.
18, the substrate of each record of claim 1-17, the median size of the crystal grain that wherein said devitrified glass is contained are below the 100nm.
19, the substrate of each record of claim 1-18, the median size of the crystal grain that wherein said devitrified glass is contained are below the 70nm.
20, the substrate of each record of claim 1-19, wherein to have surface roughness Ra be the following abrasive surface of 1nm to this substrate.
21, a kind of information recording carrier substrate constitutes by containing enstatite and/or its sosoloid devitrified glass as oikocryst, and described substrate to have surface roughness Ra be the following abrasive surface of 1nm.
22, the substrate of claim 21 record, wherein to have surface roughness Ra be the following abrasive surface of 0.5nm to this substrate.
23, the transmitance that the substrate of claim 1-22 record, its medium wavelength are 600nm light by the thick substrate of 1mm is more than 10%.
24, the substrate of claim 1-23 record, the thermal expansivity that it is characterized in that described devitrified glass is 65 * 10
-7～85 * 10
-7/ ℃.
25, a kind of information recording carrier substrate constitutes by containing enstatite and/or its sosoloid devitrified glass as oikocryst, and the mean diameter of the contained crystal grain of this devitrified glass is smaller or equal to 100nm.
26, the substrate of claim 25 record, wherein the mean diameter of the contained crystal grain of this devitrified glass is below the 70nm.
27, a kind of information recording carrier substrate constitutes by containing enstatite and/or its sosoloid devitrified glass as oikocryst, and when 1mm is thick, and the transmitance that wavelength is a 600nm light by the thick substrate of 1mm is more than 10%.
28, the substrate of each record of claim 1-27, the degree of crystallinity of wherein said devitrified glass are more than the 50 volume %.
29, the substrate of each record of claim 1-28 is characterized in that enstatite and/or its sosoloid total amount are 70-90 volume %, and titanate is 10-30 volume %, and enstatite and/or its sosoloid and titanate total amount are more than the 90 volume %.
30, a kind of information recording carrier substrate constitutes by containing enstatite and/or its sosoloid devitrified glass as oikocryst, and the thermal expansivity of this devitrified glass is 65 * 10
-7～85 * 10
-7/ ℃.
31, the substrate of claim 30 record, wherein the thermal expansivity of devitrified glass is 73 * 10
-7～83 * 10
-7/ ℃.
32, the substrate of each record of claim 1-31, wherein devitrified glass does not contain the quartz solid solution as oikocryst in fact.
33, the substrate of each record of claim 1-32 does not wherein contain the spinel as crystallization phases in fact.
34, the substrate of each record of claim 1-33 does not wherein contain ZnO in fact.
35, the substrate of each record of claim 1-33, wherein said information recording carrier is a disk.
36, a kind of information recording carrier wherein comprises recording layer on the substrate of each record of claim 1-34.
37, the information recording carrier of claim 36 record, wherein recording layer is a magnetic recording layer.
38, a kind of manufacturing information recording medium method of substrate, this substrate is by containing SiO
2: 35-65 mole %, Al
2O
3: 5-25 mole %, MgO:10-40 mole % and TiO
2: 5-15 mole %, above-mentioned composition adds up to 92 moles more than the %, oikocryst is that enstatite and/or its solid devitrified glass constitute, comprising the following step: with frit 1400-1650 ℃ of fusing with preparation glass, the forming of glass that obtains is become plate glass, the plate glass that obtains is warmed up to separates out the crystalline temperature and carry out crystallization.
39, the manufacture method of claim 38 record, wherein frit contains K
2O, smelting temperature are 1450-1600 ℃.
40, the manufacture method of claim 38 or 39 records, wherein frit contains Y
2O
3, melten glass is shaped as plate glass in 600-680 ℃ shaping die.
41, a kind of manufacturing information recording medium method of substrate, comprise the steps: with frit 1400-1550 ℃ of fusing with the system glass, the glass that obtains is formed plate glass, be warmed up to crystallization with the plate glass that will obtain and separate out temperature and make its crystallization, this substrate is made of the devitrified glass that contains following component:
SiO
2: 35-65 mole %,
Al
2O
3: 5-25 mole %,
MgO:10-40 mole %,
TiO
2: 5-15 mole %,
Y
2O
3: 0-10 mole %,
ZrO
2: 0-10 mole %,
R
2O:0-5 mole %, wherein R is be selected from Li, Na and K at least a,
RO:0-5 mole %, wherein R is be selected from Ca, Sr and Ba at least a,
As
2O
3+ Sb
2O
3: 0-2 mole %,
SiO
2+ Al
2O
3+ MgO+TiO
2: 92 moles more than the %,
Contained oikocryst is enstatite and/or its sosoloid in this devitrified glass.
42, the manufacture method of each record of claim 38-41 wherein is warmed up to 850-1150 ℃ with the glass that is shaped and makes crystallization.
43, the manufacture method of claim 42 record wherein is warmed up to 500-850 ℃ with molding glass with 5-10 ℃/minute in heating process, after 500-850 ℃ with 0.1-10 ℃ of/minute intensification.
44, a kind of information recording carrier substrate is characterized in that will containing SiO according to comprising
2, Al
2O
3, MgO and TiO
2Glass 850-1150 ℃ of thermal treatment the method for Crystallization Procedure is made, this substrate is made of the devitrified glass that contains following component:
SiO
2: 35-65 mole %,
Al
2O
3: 5-25 mole %,
MgO:10-40 mole % and
TiO
2: 5-15 mole %,
Above-mentioned composition adds up to 92 moles more than the %,
Contained oikocryst is enstatite and/or its sosoloid in this devitrified glass, and this devitrified glass does not contain ZnO.
45, a kind of information recording carrier substrate is characterized in that will containing SiO according to comprising
2, Al
2O
3, MgO and TiO
2Glass 850-1150 ℃ of thermal treatment the method for Crystallization Procedure is made, this substrate is by only having:
SiO
2: 35-65 mole %
Al
2O
3: 5-25 mole %
MgO:10-40 mole %
TiO
2: 5-15 mole %
Y
2O
3: 0-10 mole %
ZrO
2: 0-6 mole %
R
2O:0-5 mole % (but R represents to be selected from least a of Li, Na, K)
RO:0-5 mole % (but R represents to be selected from least a of Ca, Sr, Ba)
As
2O
3+ Sb
2O
3: 0-2 mole %
SiO
2+ Al
2O
3+ MgO+TiO
2: 92 moles more than the %
The devitrified glass of the composition that is constituted constitutes.
46, the substrates of claim 44 or 45 records is characterized in that above-mentioned thermal treatment carried out 1-4 hour.
47, the substrate of each record of claim 44～46 is characterized in that above-mentioned thermal treatment carries out at 875-1000 ℃.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP193574/99 | 1999-07-07 | ||
| JP19357499 | 1999-07-07 | ||
| JP293003/99 | 1999-10-14 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001344013A Division CN1230397C (en) | 1999-07-07 | 2000-07-07 | Substrate for information recording medium constructed of micro crystalline glass and information recording medium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1789191A true CN1789191A (en) | 2006-06-21 |
Family
ID=36787345
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005101135755A Pending CN1789191A (en) | 1999-07-07 | 2000-07-07 | Substrate for information recording medium and magnetic recording medium composed of crystallized glass |
| CNA2007101287827A Pending CN101092283A (en) | 1999-07-07 | 2000-07-07 | Substrate for information recording medium and magnetic recording medium composed of crystallized glass |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101287827A Pending CN101092283A (en) | 1999-07-07 | 2000-07-07 | Substrate for information recording medium and magnetic recording medium composed of crystallized glass |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN1789191A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112939471A (en) * | 2021-03-15 | 2021-06-11 | 武汉理工大学 | High-thermal-conductivity low-expansion low-dielectric microcrystalline glass and preparation method thereof |
| CN115304279A (en) * | 2022-07-27 | 2022-11-08 | 浙江大学 | Spinel crystal phase and indian stone crystal phase composite microcrystalline glass and preparation method thereof |
-
2000
- 2000-07-07 CN CNA2005101135755A patent/CN1789191A/en active Pending
- 2000-07-07 CN CNA2007101287827A patent/CN101092283A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112939471A (en) * | 2021-03-15 | 2021-06-11 | 武汉理工大学 | High-thermal-conductivity low-expansion low-dielectric microcrystalline glass and preparation method thereof |
| CN115304279A (en) * | 2022-07-27 | 2022-11-08 | 浙江大学 | Spinel crystal phase and indian stone crystal phase composite microcrystalline glass and preparation method thereof |
| CN115304279B (en) * | 2022-07-27 | 2024-03-29 | 浙江大学 | Spinel crystal phase and India Dan Jingxiang composite microcrystalline glass and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101092283A (en) | 2007-12-26 |
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Open date: 20060621 |