CN101023040B - Coated component consisting of quartz glass, and method for producing said component - Google Patents
Coated component consisting of quartz glass, and method for producing said component Download PDFInfo
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- CN101023040B CN101023040B CN2005800282100A CN200580028210A CN101023040B CN 101023040 B CN101023040 B CN 101023040B CN 2005800282100 A CN2005800282100 A CN 2005800282100A CN 200580028210 A CN200580028210 A CN 200580028210A CN 101023040 B CN101023040 B CN 101023040B
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Abstract
The present invention relates to methods for producing a coated component consisting of quartz glass, according to which the component surface is at least partially provided with a SiO2 glass composition that differs from the quartz glass of the base body. The aim of the invention is to provide a novel way of coating a quartz glass component with a SiO2 glass composition that can be produced in a cost-effective, reproducible manner, with any thickness, and can fulfil various functions according to the concrete embodiment thereof. To this end, an amorphous slip containing SiO2 particles is produced and applied to the surface of the base body, forming a slip layer which is dried and then vitrified, forming a SiO2 glass composition. The quartz glass components coated in this way can be advantageously used especially in the production of semiconductors.
Description
The present invention relates to comprise the silica glass component of quartz glass substrate, described quartz glass substrate has the surface that is covered by optics, physics or the chemical property glass substance different with the silica glass of this matrix to small part.
In addition, the present invention relates to a kind of by using SiO
2The method of the silica glass component that applies, wherein SiO are made in glass substance to the surface of small part covering quartz glass substrate
2The optics of glass substance, physics or chemical property are different with the matrix silica glass.
Further, the present invention relates to a kind of method of making silica glass component by following step: by SiO
2Particulate and liquid are made slurry (slip), are formed the porous green compact and are passed through the described base substrate of sintering densification completely or partially by described slurry by die casting and drying.
The characteristics of silica glass are optical transparence and the high resistance to chemicals product and the thermotolerance of low thermal coefficient of expansion, wide wavelength region.Silica glass component is used in a lot of the application, for example, in the manufacturing of lamp as the radiator (radiators) of coated pipe, bulb, cover plate or the reverberator carrier of lamp and ultraviolet, infrared and visible spectrum range, or in semi-conductive manufacturing, be used to handle semiconductor subassembly with the form of quartz glass reactor and instrument, anchor clamps, Bell jar, crucible, protective shield or simple silica glass component, for example pipe, rod, plate, flange, ring or piece.For producing special property, silica glass will mix with other material.
Particularly when being used for the semi-conductor manufacturing, silica glass component is exposed in high thermal stress and the chemical corrosion environment.For such application, good heat insulating ability, high-temperature stability or resistance to sudden heating and high resistance to chemicals moral character and pollution-freely have a vital role.Life-span to these silica glass components has proposed ever-increasing requirements at the higher level.
For the life-span of silica glass component, must note elching resistant and not have bubble at nearly surf zone.For example, begin to be closed in the quartz glass reactor of conductor etching facility and in use owing to removing the bubble that material is opened, usually cause in the reactor processed semi-conductive pollution, thereby stop work-ing life of described quartz glass reactor.With the fluorine-containing process gas of quartz glass reaction CHF for example
3Or CF
4, because the work-ing life that effect also can be shortened silica glass component is removed in etching.
In addition, at semiconductor fabrication process for example in sputter or the gas-phase deposition, often exist material layer depositions on all surface of inside reactor, particularly also be deposited on the lip-deep problem of silica glass.Described material layer may break away from also thereby cause particle issues.For avoiding such situation, constantly clean corresponding silica glass surface, this normally by with fluoro-containing medium particularly hydrofluoric acid etch carry out.Cleaning procedure is not only time-consuming and expensive, but also causes silica glass to be removed reduction gradually with the silica glass component wall thickness.Also be so limited the work-ing life of silica glass component.Known these material layers can adhere to uneven surface better, thereby can reduce required cleaning round-robin frequency and thereby prolong and work-ing life of expensive silica glass component.Required surfaceness is for example to grind or sandblast by the machinery method of removing, perhaps by using special etching solution to obtain.All there is shortcoming in described these two class methods.In the mechanical treatment on surface, for example can crack, and next these crackles can cause the problem relevant with particulate.
For preventing to pollute, beyond all doubt, use the silica glass component of synthetic quartz glass, particularly in semi-conductive manufacturing.And this is expensive.Compare more cheap substituting selection with it and be recorded among the DE69806628T2, the document discloses equally and has been used for the silica glass component that semi-conductor makes and the method for the above-mentioned type.Suggestion should be made the synthetic quartz glass layer on the silica glass component of natural matter in the document, and the silica glass component of wherein said natural matter is made in independent method steps in advance.For this purpose, make SiO by the flame hydrolysis of siliceous initial compounds in deposition burner
2Particulate and described particulate are deposited on the surface of assembly and are formed transparent, still, the fine and close and slick upper layer of synthetic quartz glass immediately by vitrifying (vitrified).
Described upper layer forms by the relative movement between deposition burner and the assembly surface to be coated, and the number of stream sedimentation rate and layer is depended in the growth of layer.
By the circulation ratio manufacturing that this deposition method is made upper layer, particularly uniform layer thickness, it is equipment and the plenty of time tediously long and need be a large amount of.
The another kind of method of making smooth transparent surface layer from porous green compact (making by the slurry casting) is described in the DE4440104 C2.Manufacturing has 99.9%SiO
2The SiO of chemical purity
2The aq suspension of particulate also is cast in the gypsum mold.The surface of the porous green compact that obtain then is by the high temperature of oxyhydrogen flame local heating to 1650 ℃-2200 ℃, thereby described opaque porous matrix material is converted into transparency silica glass (=vitrifying) at the thickness of the nearly about 0.5mm of surf zone.
But, have been found that the layer thickness that uses currently known methods can not obtain surpassing 2mm.Obviously, played the effect of heat insulator by vitrified transparent surface layer, this makes and fully heats difficult more to the layer that is positioned at it under.This problem can not solve by higher flame temperature, because this causes the viscous deformation of assembly and the evaporation of gaseous state silicon monoxide (SiO).
Therefore, target of the present invention provides a kind of cheap silica glass component especially for the semi-conductor manufacturing, the characteristics of described silica glass component are high purity and high etching resistence (thereby having the long lifetime), and if possible it does not produce any particle issues.
In addition, target of the present invention provides a kind of SiO that particularly makes on silica glass component in semi-conductive manufacturing
2The method of glass substance, thickness and the shape that any desired obtains be made and be had to described glass substance can with low relatively cost with in reproducible mode, and depend on that its specific design can realize different functions.
For described method, the target that originates from aforesaid method is implemented according to the present invention, wherein makes and contains amorphous Si O
2The slurry of particulate and the surface that is applied to matrix form layer of slurry, and dry then this layer of slurry and vitrifying subsequently form described SiO
2Glass substance.
In the method for the invention, make the coating of quartz glass substrate by the slurry route.SiO
2The volume of glass substance fully or at least on the certain degree by SiO
2Form SiO
2Glass substance is by the manufacturing of slurry method and provide.Although a special technological challenge is to prevent that layer of slurry the volume of any tearing-described layer occurs in the condition that shrink-also the matrix silica glass can not placed the generation surrender during drying or vitrifying.
For this purpose, at first prepare aqueous, uniform, stable and slurry that can cast, described slurry contains amorphous Si O
2Particulate.Slurry is applied on the matrix as " layer of slurry " and is dried subsequently and vitrifying.Because interaction amorphous Si O
2Particulate is the described layer of slurry and the acceleration of sintering effect of stabilized slurry and drying regime already, and this allows to form fine and close and flawless SiO in the layer of slurry of low relatively temperature sintering drying
2Glass substance.
SiO
2Particulate is by the synthetic SiO that makes
2Or form by purified naturally occurring starting material, as mentioning among above-mentioned DE 4440104 C2.SiO
2The particle diameter of particulate and distribution are to the rheological property of slurry, the dry shrinkage and the resulting SiO of layer of slurry
2The surfaceness of glass substance has influence.For example, use quite coarse grained SiO
2Particulate helps to strengthen limiting viscosity or pseudo-plasticity, reduces dry shrinkage and increases SiO
2The surfaceness of glass substance.
Described layer of slurry by room temperature, by the heating or remove moisture by lyophilize and carry out drying.Layer of slurry is by being heated to high temperature by vitrifying after dry, and this has realized SiO
2The sintering of particulate and fine and close and flawless opaque, part is opaque and partially transparent or transparent SiO fully
2The formation of glass substance, described glass substance cover the whole surface of matrix or the part surface of matrix.SiO
2Glass substance is constructed to the form of smooth layer, and perhaps it takes to form the shape of assembly function parts, for example as thickening layer (thickening) or projection (bead).
Matrix is a quartz glass body, and it is made by synthetic that make or naturally occurring starting material.The silica glass of matrix can be transparent or opaque (translucent).
Preferably, use SiO
2Particulate forms glass substance, and the size of particulate is no more than 500 μ m, preferably is no more than 100 μ m, and particle diameter is the SiO of 1 μ m-50 μ m
2Particulate constitutes the maximum volume mark.
The SiO of this grade
2Particulate demonstrates favourable sintering characteristic and relative low dry shrinkage.Have been found that under the situation of such slurry, layer of slurry can be especially easily dry and vitrifying and do not form crackle.This may be because suitably little dry shrinkage and because SiO
2The interaction that particulate is mutual, this may even cause forming molecule SiO
2Key and promotion drying and sintering.
This is by the polarity person's character of the water of slurry and by wherein by wet-milling SiO
2Initial granule manufacture SiO
2The step of particulate promotes.
Here Qi Wang size distribution is adjusted SiO by the homogeneity process of aqueous slurry
2Particulate (for example is that the particle of 200 μ m-5000 μ m begins by thick relatively diameter) is pulverized in the homogeneity process according to their fixed (consolidation) degree.During wet-milling, at the inner SiO that forms arbitrary dimension of slurry
2Particulate, or even because the particulate of the above-mentioned key of formation in slurry already that interacts, this has improved the stability of layer of slurry.
Dry SiO
2The amount of cristobalite should be no more than 1wt% in the layer of slurry, because otherwise during the vitrifying of layer of slurry, crystallisation process can take place, this can cause the waste of assembly.
The roughening of matrix surface brings to layer of slurry with by the fine and close SiO of layer of slurry by the vitrifying manufacturing
2The improved adhesion of glass substance.Roughening (for example by grind or sandblast) or chemical mode (by etching) mechanically carries out, and the surface should have the average surface roughness R of at least 0.5 μ m herein
a
Known Technology itself, is flooded, suppresses, is extracted and peel off (cutter is coated with method) or sprawl at for example injection, static secondary injection, overflow (flooding), throwing (flinging), all is applicable to apply slurry.
In addition, forming risk of crack during vitrifying can be lowered by suitable temperature control.Dry layer of slurry is preferably 1000 ℃-1600 ℃ maximum temperature vitrifying, and preferred 1100 ℃-1400 ℃, it is lower that described maximum temperature is compared with aforesaid method.
Lower maximum temperature prevents the too fast densification of the outer surface region of layer of slurry during vitrifying.Because its heat insulating function, this quick densifying will prevent further developing of vitrifying sharp side, thereby cause complete vitrifying or form heavy sheet glass layer difficulty more.
In the particularly preferred variant of the inventive method, the vitrifying in nitrogen atmosphere of exsiccant layer of slurry.
Because its high rate of diffusion in quartzy ratio, hydrogen are specially adapted to conduct heat.Good heat transfer has following effect: between high temperature and low temperature, form smooth as far as possible thermograde, wherein high temperature mainly on the surface and low temperature mainly at SiO
2Glass substance is inner or in not vitrified porous dry layer of slurry part also.Even at low Tg this has also guaranteed the development of fusing sharp side from external-to-internal, thereby the inside that guarantees layer of slurry is by vitrifying.For this purpose, at least 70% hydrogen richness is just enough.Therefore, this variant of the inventive method is particularly conducive to and forms the complete transparent SiO that bed thickness is up to several millimeters scopes
2Glass substance.Except hydrogen, the atmosphere during the vitrifying also can contain for example nitrogen, preferred helium.
But, because need security measures, so the method for vitrification in hydrogen is relatively costly.For wherein opaque or not too thick transparent SiO
2Glass substance is with regard to enough application, and the exsiccant layer of slurry also can vitrifying in air.Vitrifying obtains opaque SiO usually in air
2Glass substance.But, have been found that if matrix itself is made up of transparency silica glass, so layer of slurry even can in air, be glassed to the transparent layer that layer thickness reaches as high as about 4mm.Vitrifying is without any need for special security measures in air, thereby is cheap.
As to vitrified substituting selection in smelting furnace, found that also by burner flame vitrifying exsiccant layer of slurry also be feasible.
This variant of the inventive method obtains the surface that does not have crackle equally of flame polish, and described heat effect continues the short time and can easily be limited to be treated vitrified SiO
2The zone that layer of slurry covers, thus viscous deformation can be avoided basically.
By using laser (CO for example
2Laser) carry out vitrifying and can obtain same advantageous effects.
Unexpectedly, and compare by the vitrified surface of burner flame, the surface by laser glassization demonstrates less relatively bubble.This can be by following facts explain: cause forming and introducing in silica glass the standard burner gas of water or hydroxyl, for example oxygen and hydrogen do not exist or only exist with small number in " laser glassization " process.This causes the remarkable improvement of assembly etching resistence and small particle generation simultaneously.
The SiO of big especially thickness if desired
2Glass substance, described layer can strengthen continuously by repeatedly implementing method of the present invention.For example work as SiO
2When glass substance forms the partial thickening layer of matrix, advantageously can use this variant of the inventive method.
This partial thickening layer of matrix can be realized a lot of functions.For example, it can be used for the cylindrical matrix conduct around projection, be used for fixing when contacting with mating parts or sealing, perhaps it can be configured to bar-shaped or the terminal thickening layer of tubular matrix (mechanically forming predetermined net shape by it, for example spherical base parts or flange).
In addition, when in slurry, adding the doping agent of yttrium, aluminium, nitrogen, carbon or their compound form, also be feasible.
In this variant of the inventive method, at SiO
2Introduce one or more in the glass substance and in silica glass, bring the doping agent of special role (for example pigmentation or glass structure enhancement).For example, in the silica glass of glass substance, add aluminium and form Al
2O
3Thereby its etching resistence that strengthens silica glass prolongs the work-ing life of quartz glass parts.Add nitrogen or carbon and demonstrate similar effects in quartz glass structure, they add with the form of nitride or carbide and glass structure are produced sclerization and thereby also produces improved etching resistence.Suitable initial substance, for example silazane or siloxanes are distributed in the slurry in uniform especially mode, in the end obtain the even doping to the silica glass of glass substance.The particularly advantageous effect relevant with the dried etching resistence of assembly obtains by adding yttrium, yttrium in silica glass as Y
2O
3Exist.
The SiO of Zhi Zaoing in this way
2The characteristics of glass substance are the high-adhesiveness of silica glass and can be by changing for example second-order transition temperature or add doping agent and easily change its character of technology, and are applicable to a large amount of application-specific.The suitable configurations that is used for the semi-conductor manufacturing will be described in further detail below.
Under extreme case, thick SiO
2Layer is transparent fully and spreads on the whole silica glass component.But, in this case, need special measure for the parent material that will use with for processing condition.This will be described in more detail below.
Therefore, the method according to this invention has realized above-mentioned target, and it begins second method of mentioning from the outset, wherein SiO
2Particulate is unbodied (by wet-milling SiO in liquid
2Initial granules preparation) particle diameter is no more than 500 μ m and during die casting, and particle diameter is at the SiO of 1 μ m-50 μ m
2Particulate constitutes the maximum volume part, and makes the green compact densification by heating in hydrogenous atmosphere.
As long as need the transparent " SiO of big especially thickness
2Glass substance ", just can use this embodiment of the inventive method, it comprises the whole wall thickness of silica glass component under extreme case.Under in the end a kind of situation, itself thereby the green compact manufacturing of forming and in the slurry casting process, obtaining by vitrifying by the body that does not have pore or have a considerably less pore.Use currently known methods, if avoid the fusing fully of green compact, also can only obtain opaque and contain the sintered products of pore from this green compact usually so even under high glass transition temperature.Even use very high temperature, the also transparent surface layer that can only on opaque green compact, obtain approaching, just as described above.
Have been found that and form of parent material and the vitrifying condition all very high requirement of much thick vitrifying transparent layer slurry.To describe these requirements below.
1. on the one hand, according to the present invention, the formation of green compact need be used such slurry, wherein amorphous Si O
2Particulate exists as follows: described SiO
2Particulate is by wet-milling SiO in the liquid of slurry
2Initial granule manufacture also has the size distribution that particle diameter is no more than 500 μ m, wherein SiO
2Particulate comprises that particle diameter is the particulate that 1 μ m-50 μ m constitutes the maximum volume part.
As top already as described in, the SiO of this grade
2Particulate demonstrates favourable sintering characteristic.Have been found that under the situation of such slurry, can be especially easily dry and vitrifying and do not form crackle, this is because low dry shrinkage and because of SiO
2Interaction between the particulate, this is in liquid phase even may cause forming molecule SiO
2Key and in green compact, " freeze " and promote drying and sintering.
SiO
2Particulate is by the synthetic SiO that makes
2Form or by the forming of purifying, as described in DE 4440104 C1 with naturally occurring starting material.
2. in the method for the invention, vitrifying is undertaken by heating green compact in hydrogenous atmosphere under reductive condition.Green compact are by hot consolidation in this process, and at least the surface by fully with SiO
2The form vitrifying of glass substance.Because the high rate of diffusion of hydrogen in silica glass, hydrogen is guaranteed to be implemented in during the sintering mainly in the high temperature and the main fast temperature compensation between the low temperature of green compact inside on surface.Resulting especially little thermograde has promoted the development of fusing sharp side from external-to-internal, although at the maximum temperature of surf zone relatively low (it does not also cause dense sintering completely).
Have been found that to make and to realize that in this way layer thickness is up to the complete nonporous glassization of the layer of 10mm.If avoid crystallization during sintering, the content of cristobalite should be no more than 1wt% (based on the dry-matter of green compact) in the parent material.
Preferably, amorphous Si O during die casting
2The particle diameter of particulate is no more than 50 μ m.The characteristics of littler particulate are higher sintering activity and promote the complete vitrifying of described layer.
Ideally, sintering carries out in pure hydrogen atmosphere.Particularly because security reason (danger of blast) hydrogen content during sintering is 70 volume % at least.
Except hydrogen, described atmosphere can also contain for example nitrogen and preferred helium during vitrifying.At least 70% hydrogen richness is just enough.
Second-order transition temperature is no more than 1700 ℃, preferably is no more than 1400 ℃, and can not cause nearly surf zone " dense sintering " and therefore can not cause formation too early as the vitrifying layer of " thermal insulation layer ".Sintering temperature and low is to realize by the low temperature gradient that above-mentioned parent material and hydrogeneous sintering atmosphere are brought.
For silica glass component, realized the above-mentioned target that begins by above-mentioned silica glass component by the present invention, wherein glass substance contains amorphous Si O by exsiccant
2The vitrifying slurry material of particulate is made.
Such SiO
2Glass substance contains SiO by applying at matrix surface
2The slurry material of particulate, and the then dry and described material of vitrifying obtains, as the top detailed description of doing at method of the present invention.Described SiO
2Glass substance is fully or substantially by SiO
2Form SiO
2By the manufacturing of slurry method and apply, and the whole surface of covering assemblies or surface, cover part only.It forms flat bed and the geometrical shape of assembly is had contribution at assembly surface, thereby forms the funtion part of assembly, for example thickening layer or projection, and it can be as for example flange or base member.Smooth and fine and close if desired surface, so such surface are preferably chiseled (fire polishing) by fire and are obtained.
The SiO of Zhi Zaoing by this way
2The surface of glass substance is used burner flame or is not used any instrument to obtain in melt-flow by vitrifying in smelting furnace, its feature is not contain crackle at least, and it can be processed with chemistry or mechanical system, for example by grinding, polish or sandblasting.
But, preferably, described SiO
2Glass substance forms the surface with following character: without any crackle and not tool using be shaped, and have the average surface roughness Ra of at least 0.5 μ m.
SiO after the vitrifying
2The surface of glass substance is not very smooth.On the contrary, it has certain surfaceness.Described surfaceness is owing to its manufacture method of utilizing the inventive method realizes, and method of the present invention is because use contains SiO
2The slurry of particulate is used to form glass substance.Depend on the amorphous Si O that contains in the slurry
2The particle diameter of particulate and size distribution obtain surfaceness automatically after vitrifying, and without any need for other measure, for example roughening engraving method or mechanically roughened surface are handled.
" natural " surfaceness of assembly of the present invention has been predetermined it and has been used for semi-conductor manufacturing, causes littler particle loaded (particle load) because it has brought improved material layer to adhere to also thereby at described assembly between the usage period of semi-conductor manufacturing.In addition, described assembly makes cleaning cycle longer, and this brings longer work-ing life.
Surfaceness R
aDefinition abide by ENISO4287, and measuring condition is deferred to EN ISO4288 (this is applicable to the situation of aperiodicity surface profile).SiO
2The average surface roughness R of glass substance
aAt least being 0.5 μ m, preferably is 1.0 μ m at least.
Work as SiO
2Glass substance by the material with the kind relevant (spacies) characteristic with matrix form the time be favourable.
" material with kind of class feature " is interpreted as the SiO of glass substance and matrix in the present invention
2Difference between the content be no more than at most 3wt% and the doping agent in being present in glass substance or matrix silica glass in the presence of, these doping agents influence both coefficients of expansion in a similar fashion.This has realized the extra high adhesivity of glass substance to matrix, and the extra high resistance to sudden heating of this species complex.
Described SiO
2That that glass substance can be made is opaque, part is opaque and transparent or fully transparent.
If the high-density of focusing on, pore-free and high etching resistence, so preferred SiO
2Glass substance is fully transparent.
On the contrary, if SiO
2Glass substance is as thermofin, has opaque so or to the opaque SiO of small part
2The embodiment of the silica glass component of the present invention of glass substance is preferred.Opaque SiO
2Therefore glass substance is white normally, and reflected infra-red radiation also demonstrates great heat insulating function.
In the further preferred embodiment of assembly of the present invention, SiO
2Glass substance forms the thickening of matrix.
The described part that thickens for example forms the projection or the terminal portions of cylindrical matrix.Be in and make the crude form in back or after ornamenting was handled, it was endowed given function, for example fixation kit.
Depend on the intended use of silica glass component, work as SiO
2Glass substance is favourable when containing the doping agent of yttrium, aluminium, nitrogen, carbon or their compound form.Please refer to above-mentioned at the given corresponding description of the inventive method.
Explain the present invention in further detail below with reference to embodiment and accompanying drawing.Accompanying drawing at length provides
Fig. 1 is used to explain the SiO of having made according to the method for the present invention
2The schema of the process of the silica glass component of glass substance, described parts are used for semi-conductor manufacturing;
Fig. 2 is the heating curve figure of the layer of slurry on the vitrifying quartz glass substrate and sintering green compact according to the present invention;
Fig. 3 is the schematic sectional view that is used for the silica glass flange of single-chip support, and its surface is fully by transparent SiO
2Glass substance forms; With
Fig. 4 is the half-finished synoptic diagram that is used for spherical grinding.
1. on quartz glass substrate, prepare layer of slurry
Embodiment 1
Prepare uniform basic slurry.Basic slurry (SiO for 10kg
2-water slurry body), be in about 20 liter Barrate type shredder to mix less than the deionized water of 3 μ S at the interior silica glass volume that is lined with the amorphous quartz glass particle (particle diameter is 250 μ m-650 μ m) of 8.2kg natural material and 1.8kg specific conductivity.Described silica glass particle is purifying in the thermal chlorination method before.Be noted that cristobalite content will be lower than 1wt%.
This mixture ground 3 days by the silica glass mill ball at 23rpm on roller block, was 79% even basic slurry until obtaining solids content.During process of lapping, because SiO
2Dissolving pH is reduced to about 4.
Other amorphous Si O that in the even basic slurry that obtains, adds the about 5 μ m of particle diameter
2Particle reaches 84wt% up to solids content.Mixture in the Barrate type shredder with 25rpm speed homogenize 12 hours.The solids content of the slurry that obtains is 84%, and density is 2.0g/cm
3The SiO that after grinding silica glass particle, obtains in the slurry 14
2The feature of the size distribution that particulate shows is D
50Value is about 8 μ m and D
90Value is about 40 μ m.
To be used for several seconds of annular silica glass flange immersion slurry of the external diameter 300 of single-chip support, average surface roughness R is adjusted to by chemical milling (deep refrigeration) in advance in its surface
aBe 2 μ m.
Thereby on the silica glass flange, form the uniform sealing layer of slurry of thickness for about 0.35mm.This layer of slurry at first about 5 hours in drying at room temperature, and then in the air by IR radiator drying.Dried layer of slurry does not have crackle and mean thickness less than about 0.3mm.
For this smooth of silica glass flange applied, employed slurry is dilatancy (dilatant) preferably.The rheological property of this slurry, it is called " dilatancy ", shows that its viscosity increases with shearing rate.This has such effect, after the cancellation shearing force, and promptly after slurry is applied to silica glass component as layer of slurry, viscosity degradation, this helps forming the layer of slurry of uniform thickness.
As top embodiment 1 is described, make basic slurry.Other amorphous Si O that does not add the about 5 μ m of particle diameter
2Particle adds other amorphous Si O of the about 40 μ m of particle diameter on the contrary
2Particle reaches 84wt% up to solids content in uniform stability fundamental slurry.Mixture in the Barrate type shredder with 25rpm speed homogenize 12 hours.The solids content of the slurry that obtains is 84%, and density is 2.Og/cm
3The SiO that after grinding silica glass particle, obtains in the slurry 14
2The feature of the size distribution that particulate shows is D
50Value is about 14 μ m and D
90Value is about 40 μ m.
Except amorphous Si O
2Beyond the particulate, described slurry also can contain and is used to form SiO
2The precursor component of particulate.These are to be used in to be used to make SiO
2Sol-gel process in the hydrolyzable silicon compound.Because theirs water-disintegrable, these precursor component form molecular linkage in layer of slurry, and they bring fixed and thereby help sintering.But on the other hand, they cause that also sizable dry shrinkage also may cause the formation of crackle in high density, and this has limited the ratio of these precursor component in slurry.
The end of quartz glass tube, its surface are adjusted into average surface roughness R in advance by chemical milling (deep refrigeration)
aBe 2 μ m, be dipped into several seconds in the slurry, the about 3cm of the degree of depth.Owing to this disposable short steeping process, form the sealing layer of slurry of the about 0.4mm of thickness at the end of quartz glass tube.This layer of slurry about 10 minutes in drying at room temperature.Described dipping and drying process repeat many times, so that form the slurry material of the convex shape thickening layer form of the about 15mm of mean thickness at the end of quartz glass tube.Subsequently at this thickening layer of air drying.
In the applying of this domain mode to quartz glass tube, the slurry of use is preferably pseudoplastic.The rheological property of this slurry, it is called " pseudo-plasticity ", shows that its viscosity descends with shearing rate.This has such effect, and after the cancellation shearing force, promptly after applying slurry, viscosity increases, and this helps forming the layer of slurry of convex shape.
2. the vitrifying of layer of slurry
Based on heating curve shown in Figure 2, make and dry and be provided in layer of slurry vitrifying in the sintering smelting furnace in pure hydrogen atmosphere subsequently on the silica glass flange according to embodiment 1.
Described heating curve comprises initial rapid heating oblique line, and layer of slurry is by from the low Heating temperature of room temperature at hour internal heating to 1000 ℃ in this part.Keep 1 hour then by the higher Heating temperature of the second smooth heating oblique line in this low Heating temperature layer of slurry at 4 hours internal heating to 1400 ℃.In this embodiment, it is 2 hours in the residence time of this higher Heating temperature.After this process, this layer of slurry is by vitrifying fully, and is transparent and do not contain bubble.
Ensuing cooling is cooled to 500 ℃ temperature with 15 ℃/minute controlled chilling speed in smelting furnace in hydrogen, then naturally cooling in the smelting furnace of still sealing.
Fig. 3 schematically shows coating ground silica glass flange by this way with the form of sectional view.This flange is made of the ring-type matrix 30 of transparency silica glass, matrix 30 at all faces all by flawless and transparent SiO
2Layer 31 surrounds, for purposes of illustration, and SiO
2Layer 31 is represented with exaggerative thickness in Fig. 3.Central shaft is represented with reference number 32.
SiO on the silica glass flange matrix 30
2Layer 31 has the average layer thickness of about 0.2mm.Its characteristics are that the density of density and silica glass is corresponding and are high thermal-shock resistance.Because its final processing in the sintering smelting furnace, it has on average " natural " surfaceness (R
a) be the flawless surface of about 1.2 μ m, this roughness is to contain SiO because use purely
2The manufacturing of particulate slurry obtains, and does not promptly use any further processing.Material layer adheres to the surface in firm especially mode, causes comparing with known silica glass flange cleaning cycle and prolongs, and thereby obtain longer work-ing life.
As described in Example 1, on the silica glass flange, form uniform sealing layer of slurry and the drying of the about 0.35mm of thickness.Pass through CO then
2This layer of slurry of laser glassization, wherein lasing beam diameter expands to about 5mm by Optical devices, and is treating vitrifying surface guided laser bundle with raster mode with the switching rate of 500mm/min.Constant distance between laser exit and the surface remains on 300mm.
This has obtained flawless and transparent SiO
2Layer, its characteristics are low especially air bubble content, its feature and quality are corresponding to the layer of describing among above-mentioned Fig. 3 31 in addition.
Convex at the quartz glass tube end thickens layer of slurry, and it serves as that make and drying on the basis with embodiment 1, subsequently by the vitrifying of oxygen hydrogen burner.For this purpose, thickening layer is carried out long-time heating up to obtaining transparent, flame polish and fine and close surface fully.
Fig. 4 shows the silica glass work in-process 40 that obtain by the form of sectional view.These work in-process 40 are used to make the spherical base parts of silica glass.For this reason, at the end of quartz glass tube 41, its external diameter is 25mm, wall thickness 2mm, and it is the SiO of 15mm that maximum ga(u)ge is provided
2 Vitrifying thickening layer 42, thickening layer 42 are as described previously by using SiO
2Slurry is made.Subsequently, thickening layer 42 is carried out mechanical treatment and flame polish.Its characteristics are not have crackle and the high-density suitable with the density of silica glass.
In another embodiment, as described at embodiment 1,, be to make layer of slurry on the 250wt ppm quartz glass bar at hydroxy radical content transparent, synthetic manufacturing by dipping and subsequent drying.The thickness of layer of slurry is 0.3mm after drying.Carry out vitrifying in smelting furnace in air, heating curve has more detailed description corresponding to curve shown in Figure 2 and in embodiment 3, but difference is to be omitted in 2 hours retention time of 1400 ℃ of maximum temperatures.Begin to cool down immediately later on reaching described temperature.
Unexpectedly, the vitrifying SiO that obtains
2Glass substance is fully transparent, and its mean thickness is 0.2mm, mean roughness R
aBe 1.2 μ m.
With embodiment 6 serve as the dry layer of slurry on quartz glass bar, made of basis be introduced into carry out in the sintering smelting furnace vitrifying and therein in air by vitrifying.
Heating curve has more detailed description corresponding to curve shown in Figure 2 and in embodiment 3, be not 1400 ℃ but 1050 ℃ but difference is maximum temperature.In this temperature, the quartz glass bar of coating keeps cooling then in 2 hours.
Though also fixed by the described layer of slurry of this Temperature Treatment by tight burning, the SiO that obtains
2Glass substance demonstrates about 2.15g/cm
3Density, but still be opaque basically.Opacity shows at 190nm that to the wavelength between the 2650nm directly spectral-transmission favtor is lower than 10%.
Preparation is by 95wt%SiO
2And 5wt%Y
2O
3The initial particle of forming.For this purpose, median size is that the pure quartz glass powder of about 200 μ m mixes with the yttrium oxide powder of the about 5 μ m of median size, and powdered mixture melts in electric smelter in graphite jig in a vacuum.The silica glass that is doped with yttrium oxide of Zhi Zaoing by this way, as described in embodiment 1, pulverizing and be processed as solids content by wet-milling is 79% even basic slurry.By the particle diameter that adds other is the Y that is doped with of about 5 μ m
2O
3Silica glass particle obtain the solids content of 84wt%.
Mixture as described in the further processing as described in the embodiment 1, thus in the slurry through adulterated SiO
2The feature of the size distribution that particulate shows is D
50Value is about 8 μ m and D
90Value is about 40 μ m.
As described in the embodiment 1, on flange, make even sealing layer of slurry and dry this layer that thickness is about 35mm by using described slurry.Then the layer of slurry that obtains is glassed to and is doped with 5wt%Y
2O
3The transparency silica glass layer.Its characteristics are extra high anti-etching gaseousness.
3. make and green compact that sintering obtains by the slurry casting
The complete vitrifying of green compact manufacturing and the transparent quartz glass body that obtain according to the slurry casting process by sintering are explained in more detail referring now to the schema of Fig. 1.
As described in the embodiment 1, make the slurry body of silica glass particle 11 and water 12.In addition, with the amount of 500wt ppm (based on SiO
2Part) with finely divided Al
2O
3Powder 16 joins in the slurry.Mixture 13 is that solids content is 82% even slurry 14 in the Barrate type grinding machine for grinding.The SiO that obtains after in slurry 14, grinding
2The size distribution of particulate is that particle diameter is between the 0.45 μ m-50 μ m, and particle diameter is at the SiO of 1 μ m-10 μ m
2Particulate constitutes maximum volume part (D
50Value).The glycerine (based on remaining liquid phase) that in this mixture, adds 16wt% extraly, glycerine is used as needle growth inhibitor 15, and with mixture homogenize 12 hours.Homogenize is carried out in the Barrate type shredder with the speed of 25rpm.
Then by these uniform slurry 14 preparation green compact 20.For this purpose, slurry 14 is cast in the tubular film mould of silicon of vacuum moulded, this mould is embedded in the dry ice (dry ice).This causes slurry 14 quick freezing is that external diameter is that the urgency of the bar form of 10mm is frozen precast body (blue body) 22.The adding of glycerine helps to form the uniform texture that does not contain ice needle structure (ice needlestructures).Quick-frozen precast body 22 is taken out from film die and directly puts into the forced air convection loft drier that is preheated to 80 ℃ with freezing state, and in this temperature drying a few hours therein.Because from surperficial consecutive evaporation with remove moisture, therefore prevented the condensation again of moisture and repeated surface freezing (superficial freezing) (its must cause form needle crystal and disturb green compact structure).
Exsiccant green compact 20 are that sintering is carried out on the basis with the heating curve shown in Fig. 2 in smelting furnace in pure hydrogen atmosphere then, are 4 hours (rather than 2 hours) in the residence time of higher Heating temperature.
Therefore, finish the complete vitrifying of green compact, obtain the bar-shaped cast member 21 of external diameter for about 10mm, this cast member is made of transparency silica glass.
Claims (12)
1. one kind by using SiO
2The method of the silica glass component that applies, wherein SiO are made in glass substance (31,42) to the surface of small part covering quartz glass substrate (30,41)
2Optics, physics or the chemical property of glass substance (31,42) and matrix (30,41) silica glass difference, this method feature are to make and contain amorphous Si O
2The slurry of particulate and the surface that is applied to matrix (30,41) form layer of slurry, and dry this layer of slurry is also carried out vitrifying and formed SiO by being heated to 1000 ℃ to the 1600 ℃ temperature in the scope subsequently
2Glass substance (31,42), thereby SiO
2The particle diameter of particulate is no more than 100 μ m, thereby particle diameter is the SiO of 1 μ m-50 μ m
2Particulate constitutes the maximum volume part, thereby and by wet-milling SiO
2Initial granule manufacture SiO
2Particulate.
2. the method for claim 1 is characterized in that the temperature by being heated to 1100 ℃-1400 ℃, and the layer of slurry of drying is carried out vitrifying.
3. claim 1 or 2 method is characterized in that layer of slurry vitrifying in nitrogen atmosphere of drying.
4. claim 1 or 2 method, the layer of slurry that it is characterized in that drying is by the burner flame vitrifying.
5. claim 1 or 2 method, the layer of slurry that it is characterized in that drying is by laser glassization.
6. claim 1 or 2 method is characterized in that SiO
2Glass substance (31,42) forms as the part that thickens at matrix (30,41).
7. claim 1 or 2 method is characterized in that the doping agent of the form of yttrium, aluminium, nitrogen, carbon or their compound is added in the slurry.
8. silica glass component that comprises quartz glass substrate (30,41), wherein said matrix (30,41) have to small part by SiO
2The surface that glass substance covers, wherein SiO
2The optics of glass substance, physics or chemical property and matrix (30,41) silica glass difference is characterized in that glass substance (31,42) is by containing amorphous Si O
2Vitrified slurry material of the drying of particulate is made, thus SiO
2Glass substance (31,42) be opaque or to small part opaque and its constitute by material with kind class feature relevant with matrix (30,41), its mode is the SiO of glass substance and matrix
2Difference between the content be no more than at most 3wt% and the doping agent in being present in glass substance or matrix silica glass in the presence of, these doping agents influence both coefficients of expansion in a similar fashion.
9. the silica glass component of claim 8 is characterized in that SiO
2Glass substance (31,42) is formed the surface with following character: this surface does not have crackle and not tool using shaping, has the average surface roughness R of at least 0.5 μ m
a
10. the silica glass component of claim 9 is characterized in that SiO
2The surface of glass substance (31,42) has the average surface roughness R of at least 1.0 μ m
a
11. each silica glass component of claim 8-10 is characterized in that SiO
2Glass substance (42) has the part that thickens of matrix (41).
12. each silica glass component of claim 8-10 is characterized in that SiO
2Glass substance contains the doping agent of the form of yttrium, aluminium, nitrogen, carbon or their compound.
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| DE102004040833.5 | 2004-08-23 | ||
| DE102004040833 | 2004-08-23 | ||
| DE102004052312A DE102004052312A1 (en) | 2004-08-23 | 2004-10-28 | Coated quartz glass component and method of manufacturing the component |
| DE102004052312.6 | 2004-10-28 | ||
| PCT/EP2005/009073 WO2006021415A2 (en) | 2004-08-23 | 2005-08-23 | Coated component consisting of quartz glass, and method for producing said component |
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| CN101023040A CN101023040A (en) | 2007-08-22 |
| CN101023040B true CN101023040B (en) | 2011-08-03 |
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| CN2005800282168A Active CN101023041B (en) | 2004-08-23 | 2005-08-23 | Component with a reflector layer and method for producing the same |
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| DE102008028233A1 (en) * | 2008-06-16 | 2009-12-17 | Heraeus Noblelight Gmbh | Compact UV irradiation module |
| US9957431B2 (en) * | 2013-11-11 | 2018-05-01 | Heraeus Quarzglas Gmbh & Co. Kg | Composite material, heat-absorbing component, and method for producing the composite material |
| JP6702213B2 (en) * | 2017-01-31 | 2020-05-27 | 信越化学工業株式会社 | Base material for synthetic quartz glass lid, synthetic quartz glass lid, and manufacturing method thereof |
| EP3428132B1 (en) | 2017-07-10 | 2023-08-30 | Heraeus Quarzglas GmbH & Co. KG | Quartz glass component having high thermal stability, semi-finished product for same and method of manufacturing the same |
| NL2021322B1 (en) * | 2018-06-28 | 2020-01-06 | Corning Inc | Continuous methods of making glass ribbon and as-drawn glass articles from the same |
| CN110361909A (en) * | 2019-08-19 | 2019-10-22 | 深圳海森堡科技有限公司 | Integrated eyeglass and manufacturing method |
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| EP0366090A2 (en) * | 1988-10-25 | 1990-05-02 | Asahi Glass Company Ltd. | Cathode ray tube |
| EP0367269A2 (en) * | 1988-11-04 | 1990-05-09 | Asahi Glass Company Ltd. | Method for reinforcing glass, film-forming composition for the reinforcement of glass and reinforced glass articles |
| CN1105650A (en) * | 1993-11-12 | 1995-07-26 | 赫罗伊斯石英玻璃有限公司 | Formed body with high silicon dioxide content and preparation of same |
| US5766680A (en) * | 1994-05-18 | 1998-06-16 | Institut Fur Neue Materialien Gemeinnutzige Gmbh | Method of producing structured inorganic layers |
| DE10243954B3 (en) * | 2002-09-20 | 2004-07-08 | Heraeus Quarzglas Gmbh & Co. Kg | Manufacture of opaque quartz glass composite material, used as starting material of permanent shaping-die manufacture of solar silicon melting, involves forming composite slip by mixing quartz glass granules and homogenous base slip |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2159296C (en) * | 1994-10-14 | 2007-01-30 | Michel J. Soubeyrand | Glass coating method and glass coated thereby |
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| EP0366090A2 (en) * | 1988-10-25 | 1990-05-02 | Asahi Glass Company Ltd. | Cathode ray tube |
| EP0367269A2 (en) * | 1988-11-04 | 1990-05-09 | Asahi Glass Company Ltd. | Method for reinforcing glass, film-forming composition for the reinforcement of glass and reinforced glass articles |
| CN1105650A (en) * | 1993-11-12 | 1995-07-26 | 赫罗伊斯石英玻璃有限公司 | Formed body with high silicon dioxide content and preparation of same |
| US5766680A (en) * | 1994-05-18 | 1998-06-16 | Institut Fur Neue Materialien Gemeinnutzige Gmbh | Method of producing structured inorganic layers |
| DE10243954B3 (en) * | 2002-09-20 | 2004-07-08 | Heraeus Quarzglas Gmbh & Co. Kg | Manufacture of opaque quartz glass composite material, used as starting material of permanent shaping-die manufacture of solar silicon melting, involves forming composite slip by mixing quartz glass granules and homogenous base slip |
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| CN101023040A (en) | 2007-08-22 |
| CN101023041B (en) | 2012-08-01 |
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