WO2007131988A1 - Structures frittées en verre ou vitrocéramique et procédés de production - Google Patents

Structures frittées en verre ou vitrocéramique et procédés de production Download PDF

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Publication number
WO2007131988A1
WO2007131988A1 PCT/EP2007/054641 EP2007054641W WO2007131988A1 WO 2007131988 A1 WO2007131988 A1 WO 2007131988A1 EP 2007054641 W EP2007054641 W EP 2007054641W WO 2007131988 A1 WO2007131988 A1 WO 2007131988A1
Authority
WO
WIPO (PCT)
Prior art keywords
frit
poly
recited
dispersed
minimum feature
Prior art date
Application number
PCT/EP2007/054641
Other languages
English (en)
Inventor
Yann Nedelec
Original Assignee
Corning Incorporated
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from EP20060300471 external-priority patent/EP1857423B1/fr
Application filed by Corning Incorporated filed Critical Corning Incorporated
Priority to JP2009510439A priority Critical patent/JP4875151B2/ja
Priority to CN2007800174891A priority patent/CN101443286B/zh
Publication of WO2007131988A1 publication Critical patent/WO2007131988A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06—Joining glass to glass by processes other than fusing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
    • B81C1/00023—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems without movable or flexible elements
    • B81C1/00055—Grooves
    • B81C1/00071—Channels
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/02—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass
    • C03C17/04—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass by fritting glass powder
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06—Joining glass to glass by processes other than fusing
    • C03C27/10—Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00819—Materials of construction
    • B01J2219/00824—Ceramic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00819—Materials of construction
    • B01J2219/00831—Glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C2201/00—Manufacture or treatment of microstructural devices or systems
    • B81C2201/01—Manufacture or treatment of microstructural devices or systems in or on a substrate
    • B81C2201/0174—Manufacture or treatment of microstructural devices or systems in or on a substrate for making multi-layered devices, film deposition or growing
    • B81C2201/019—Bonding or gluing multiple substrate layers

Definitions

  • the present invention relates generally to sintered glass and glass- ceramic structures and methods for their formation, and particularly sintered glass and glass-ceramic structures formed on a solid substrate and methods for formation of such.
  • One useful fabrication method for the formation of glass or glass- ceramic structures is to form a relatively fine 3-D structure, such as walls defining fluidic passages of a fluidic or microfluidic device, by shaping a glass frit and binder mixture, on or onto a substrate.
  • the substrate and frit together may then be stacked, with one or more other substrates each of which may have its own patterned frit 3-D structure, and sintered together to form a one-piece or unitary device.
  • U.S. Patent Number 6,769,444 assigned to the assignee of the present application.
  • the invention includes, according to one embodiment, a unitary structure comprised of two or more planar substrates fused together by a glass or glass-ceramic sintered patterned frit material disposed therebetween.
  • the pattern of the sintered patterned frit material defines passages therein, and the sintered patterned frit material has a characteristic first minimum feature size in a direction parallel to the substrates.
  • Particles of the frit material have a poly-dispersed size distribution up to a maximum frit particle size, in a maximum length dimension, and the first minimum feature size of the sintered patterned frit material is greater than 2 times the maximum frit particle size, desirably about 3 times or more, and less than 6.25 times the maximum frit particle size, desirably about 5 times or less, most desirably about 4 times or less. Setting the minimum feature size sufficiently low relative to the maximum frit particle size makes the structure more robust by preventing crack formation, while keeping it sufficiently high makes the structure more easily manufactured by assuring sufficient resolution in useful forming processes such as molding.
  • the invention also includes, according to another embodiment, a method for forming, on a substrate, a sintered structure having a desired pattern.
  • the method includes providing a poly-dispersed frit of a material subject to viscous sintering, mixed the frit with a sufficient amount of a binder to allow for forming of the frit-binder mixture.
  • the method further includes forming the frit-binder mixture onto a substrate in a desired pattern, the pattern having a first minimum feature size in a direction parallel to the substrate, then sintering the formed mixture to form a sintered structure.
  • the poly-dispersed frit has a maximum particle size greater than 0.16, desirably about 0.2 or more, most desirably about 0.25 or more times the first minimum feature size, and less than and less than 0.5, desirably about 0.3 or less times the minimum feature size. Choosing the particle size sufficiently high makes the resulting structure more robust, while keeping it sufficiently low makes the structure easier to produce.
  • the method may include providing a poly-dispersed frit by ball milling or similar suitable process, then sieving the frit in a sieve sized at one-half the maximum particle size for the frit, retaining all particles that pass for inclusion in the frit.
  • Figure 1 is a diagrammatic cross-section of one embodiment of a microfluidic device of the present invention.
  • Figures 2A-E are photomicrographs of portions of a frit structure 20.
  • Figure 3 is a graph showing the particle size distributions and the results of the frits used to make the structures of Figures 2A-E.
  • Figure 4 is a perspective photomicrograph of a layer 44 of 3-D frit structure after sintering, showing cracks at the base of a raised oval structure when
  • 63 ⁇ m sieved frit is used for structures of minimum width on the order of 1000 ⁇ m.
  • Figure 5 is a perspective photomicrograph of a layer 44 of 3-D frit structure after sintering, showing the absence of cracks at the base of a raised oval structure similar to that of Figure 4, but with 125 ⁇ m sieved frit used.
  • Figure 6 is a cross-sectional photomicrograph of portion of a device 10 like that of Figure 1, which has first been sectioned then etched to reveal the grain boundaries in the sintered structured material 20.
  • Microfluidic devices such as device 10 of Figure 1, may be comprised of a three-dimensional (3-D) sintered frit structure 20 that is sintered and thereby fused between two substrates 30 and 40 so as to define a monolithic device 10 with fluidic passages 70 therein.
  • 3-D three-dimensional
  • one layer 44 of 3-D frit structure is formed, desirably by molding, on a substrate, then sintered to another substrate having only a thin flat layer of frit 50, resulting in a fused joint within the 3-D frit structure 20, indicated by the dashed line 46.
  • two 3-D frit structures first formed on separate substrates may be sintered to each other.
  • the resulting patterned sintered frit structure 20 has a characteristic minimum feature size or dimension 60 in the direction parallel to the substrates 30, 40.
  • Dimension 60 corresponds to the characteristic minimum distance between free (unconstrained) surfaces of the frit structure 20, or to the characteristic wall thicknesses of passages 70.
  • the patterned sintered frit structure 20 also has a characteristic minimum feature size or dimension 62 or 64 in the direction perpendicular to the substrates 30, 40.
  • This dimension 62 or 64 corresponds to the characteristic minimum distance between constrained surfaces of the frit structure 20 (constrained by contract with substrate 30 or 40) and an unconstrained surface of the frit structure 20 (such as an interior surface of a passage 70).
  • Dimension 62 may also be referred to as the thickness of the residual layer, the residual layer being the substrate-covering layer of frit that is produced on the substrate 30 as part of forming the layer 44 of 3-D frit structure.
  • Dimension 64 may also be referred to as the thickness of the flat layer 50.
  • Dimensions 62 and 64 may be equal, but may also differ, in which case the smaller of the two dimensions represents the characteristic minimum feature size in the direction perpendicular to the substrates 30, 40.
  • Figures 2A-E are cross-sectional photomicrographs of a partially sintered or "presintered" frit structure 20. Such presintering may desirably be used to give physical strength and cohesion to a formed frit structure prior to assembly of the desired multiple substrates for final sintering. From left to right in the Figures 2A-E, the respective sieve sizes employed to produce the frit used to form the structure 20 were 20, 63, 80, 125, and 160 ⁇ m. Cracks 80 may be seen as white areas in the photomicrographs. As may be seen from the figures, cracks are present for sieve sizes 20, 63, and 80, but absent for sieve sizes 125 and 160.
  • Figure 3 shows the PSDs by cumulative volume percentage as a function of equivalent diameter of the particles in micrometers, as detected by a laser granulometer.
  • Traces 102, 104, 106, 108, and 110 show the distributions resulting from sieving below 20, 63, 80, 125, and 160 micrometers, respectively.
  • the quantity of binder used can also be reduced (from 20%wt binder to 17.6%wt with identical mixing, and all the way down to 15.3%wt with more thorough mixing), while maintaining the same viscosity of the frit and binder mixture.
  • the complete desired PSD can be very simply obtained, by dry grinding then sieving, compared to what is typically done in ceramics industry, where several mono-dispersed PSDs, prepared independently, must be mixed together in order to improve the initial compactness of the particles mixed with binder.
  • the global poly-dispersed PSD can be very simply obtained, by dry grinding then sieving, compared to what is typically done in ceramics industry, where several mono-dispersed PSDs, prepared independently, must be mixed together in order to improve the initial compactness of the particles mixed with binder.
  • PSD below one size value is kept after sieving, resulting in a continuous PSD with good resulting compactness, very small particles being generated intrinsically by the dry grinding itself.
  • the 3-D structures are preferably formed with a residual flat layer of frit having a thickness 62, such that the interface between the residual layer and substrate 30 is under constraint while top of the layer 44 is much freer during pre-sintering or early final sintering. In case of high shrinkage, the stress generated is high, resulting in cracks.
  • any materials that can undergo a viscous sintering process such as glass-ceramics and potentially some other ceramic materials can be used similarly.
  • the frit mixture may be prepared as follows.
  • the desired glass or glass ceramic may be ball milled, then sieved below the desired size (in the presently preferred case, a sieve of 125 ⁇ m is used), and all the fraction below the desired size is used for paste (frit and binder mixture) preparation.
  • a bigger sieve is added.
  • a 1 mm sieve may be used on top of the 125 ⁇ m sieve in order to protect it.
  • the grains typically obtained after grinding have an aspect ratio around 1:2, meaning that during sieving, the biggest particles able to go through the sieve have a length equal to about 2 times the size of the opening in the sieve.
  • the biggest dimension of biggest particles in a PSD sieved below 63 ⁇ m is around 126 ⁇ m, while it is around 250 ⁇ m for a PSD sieved below 125 ⁇ m.
  • These values also correspond to the highest values measured on PSD curves obtained by a laser granulometer where particles are characterized in all their dimensions. The lowest value on the PSD curve corresponds to the finest particle dimension detected, which is around 1.3 ⁇ m in all cases described here.
  • PSD is instead characterized by using equipment employing particle sedimentation in a solvent, only lengths of particles will be characterized because particles sediment in the direction of the lowest resistance to flowing, and the PSD curve will be different than the one obtained on a laser granulometer. Care must thus be taken in PSD curve interpretation, depending on the equipment used for PSD characterization, and particularly when particles are not very spherical.
  • Figures 2 and 3 show that the cracking problem is almost but not quite absent in the 80 ⁇ m sieved frit, where the minimum parallel feature size dimension 60 of Figure 1 is 1000 ⁇ m. Given the 2:1 aspect ratio of the particles, the 80 ⁇ m sieved frit has a maximum particle size, in the maximum size direction, of 160 ⁇ m.
  • the minimum parallel feature size be less than about 6.25 times the maximum particle size, desirably about 5 times the maximum particle size or less.
  • 125 ⁇ m sieved frit showed no cracks for a minimum parallel feature size of 1000 ⁇ m
  • 63 ⁇ m sieved frit showed no cracks for a minimum parallel feature size of 500 ⁇ m.
  • the minimum parallel feature size be about 4 times the maximum particle size or less.
  • the proportion of binder in the paste may be decreased from 20%wt to 17.6%wt while keeping a similar paste viscosity.
  • the quantity of binder may be decreased to only 15.3%wt to keep a similar paste viscosity.
  • the decreasing of binder quantity is going in the right direction to limit the global shrinkage from a molded or formed part to a sintered part, and can be explained by the fact that in switching to PSD sieved below 125 ⁇ m, there are fewer voids, due to the presence of additional bigger particles.
  • the maximum sized particles of the frits used are desirably large particles, as explained above, and while sintering large particles is feasible with viscous-sintering materials as shown above, still, if the biggest particles in the PSD are too big relative to the minimum feature size of the 3-D structure being formed, there is a risk of losing resolution, i.e., losing small or detailed features, in the course of the molding process desirably used to form the patterned structures.
  • the minimum parallel feature size be greater than 2 times the maximum frit particle size, more desirably at least about 3 times the maximum frit particle size or more, so that resolution issues do not arise.
  • Figure 4 is a perspective photomicrograph of a layer 44 of 3-D frit structure after sintering, showing cracks at the base of a raised oval structure when 63 ⁇ m sieved frit is used for structures of minimum width on the order of 1000 ⁇ m.
  • Figure 5 is a perspective photomicrograph of a layer 44 of 3-D frit structure after sintering, showing the absence of cracks at the base of a raised oval structure similar to that of Figure 4, but with 125 ⁇ m sieved frit used. No cracks are formed during pre-sintering.
  • Figure 6 is a cross-sectional photomicrograph of portion of a device 10 like that of Figure 1 , which has first been sectioned then etched to reveal the grain boundaries in the sintered patterned frit material 20. Without etching, grain boundaries cannot be seen and the sectioned structure appears uniform and smooth.
  • Passages 70 are defined within the 3-D sintered frit structure 20, and are separated by a characteristic minimum perpendicular distance 60 of about 1000 ⁇ m. As may be seen from the figure, after final sintering of the structure 20, no cracks are found anywhere in the corners of the passages 70.
  • the largest particles on the order of 125 ⁇ m, are sufficiently rare and their orientation is sufficiently random that no 125 ⁇ m particle is oriented along its long dimension in the cross section shown. Observing the largest particles along their largest dimension typically requires review of multiple sections.

Abstract

Selon la présente invention, une structure unitaire (10) est composée de deux ou plusieurs substrats plans (30, 40) fusionnés par un matériau fritté à motifs en verre ou vitrocéramique (20) disposé entre eux. Le motif dudit matériau forme des passages (70) dans celui-ci, et ledit matériau (20) présente une taille de caractéristique minimum représentative (60) dans un sens parallèle aux substrats. Les particules dudit matériau ont une granulométrie polydispersée allant jusqu'à une grosseur de particule frittée maximum, sur une longueur maximum, et la taille de caractéristique minimum (60) dudit matériau fritté est supérieure à 2 fois la grosseur de particule frittée maximum, de manière souhaitée environ 3 fois ou plus et moins de 6,25 fois celle-ci, de manière souhaitée environ 5 fois ou moins, idéalement environ 4 fois ou moins. La présente invention concerne également un procédé de fabrication de la structure (10).
PCT/EP2007/054641 2006-05-15 2007-05-14 Structures frittées en verre ou vitrocéramique et procédés de production WO2007131988A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2009510439A JP4875151B2 (ja) 2006-05-15 2007-05-14 焼結されたガラスおよびガラスセラミック構造および製造方法
CN2007800174891A CN101443286B (zh) 2006-05-15 2007-05-14 烧结的玻璃和玻璃-陶瓷结构及其制造方法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP20060300471 EP1857423B1 (fr) 2006-05-15 2006-05-15 Verre fritté et vitrocéramique et méthodes de fabrication
EP06300471.7 2006-05-15
US11/716,333 US8021739B2 (en) 2006-05-15 2007-03-09 Sintered glass and glass-ceramic structures and methods for producing
US11/716,333 2007-03-09

Publications (1)

Publication Number Publication Date
WO2007131988A1 true WO2007131988A1 (fr) 2007-11-22

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Country Link
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2077149A1 (fr) * 2007-12-21 2009-07-08 Corning Incorporated Ensemble de microréacteur incorporant un élément d'interconnexion et plusieurs microstructures fluidiques
US8105557B2 (en) 2007-12-21 2012-01-31 Corning Incorporated Microreactor assembly incorporating interconnect backbone and diverse fluidic microstructures

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5853446A (en) * 1996-04-16 1998-12-29 Corning Incorporated Method for forming glass rib structures
US20030192587A1 (en) * 2001-09-28 2003-10-16 Guillaume Guzman Microfluidic device and manufacture thereof
EP1415707A1 (fr) * 2002-10-29 2004-05-06 Corning Incorporated Réacteur et procédé pour des réactions photocatalytiques
WO2004050575A1 (fr) * 2002-12-03 2004-06-17 Corning Incorporated Compositions de verre borosilicate et utilisations de celles-ci

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5853446A (en) * 1996-04-16 1998-12-29 Corning Incorporated Method for forming glass rib structures
US20030192587A1 (en) * 2001-09-28 2003-10-16 Guillaume Guzman Microfluidic device and manufacture thereof
EP1415707A1 (fr) * 2002-10-29 2004-05-06 Corning Incorporated Réacteur et procédé pour des réactions photocatalytiques
WO2004050575A1 (fr) * 2002-12-03 2004-06-17 Corning Incorporated Compositions de verre borosilicate et utilisations de celles-ci

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2077149A1 (fr) * 2007-12-21 2009-07-08 Corning Incorporated Ensemble de microréacteur incorporant un élément d'interconnexion et plusieurs microstructures fluidiques
US8105557B2 (en) 2007-12-21 2012-01-31 Corning Incorporated Microreactor assembly incorporating interconnect backbone and diverse fluidic microstructures
WO2009099536A2 (fr) * 2008-01-30 2009-08-13 Corning Incorporated Ensemble microréacteur incorporant une structure principale d'interconnexion et diverses microstructures fluidiques
WO2009099536A3 (fr) * 2008-01-30 2010-02-25 Corning Incorporated Ensemble microréacteur incorporant une structure principale d'interconnexion et diverses microstructures fluidiques

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