US20070123410A1 - Crystallization-free glass frit compositions and frits made therefrom for microreactor devices - Google Patents

Crystallization-free glass frit compositions and frits made therefrom for microreactor devices Download PDF

Info

Publication number
US20070123410A1
US20070123410A1 US11/594,657 US59465706A US2007123410A1 US 20070123410 A1 US20070123410 A1 US 20070123410A1 US 59465706 A US59465706 A US 59465706A US 2007123410 A1 US2007123410 A1 US 2007123410A1
Authority
US
United States
Prior art keywords
mol
glass
frit
composition
less
Prior art date
Legal status (The legal status 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 status listed.)
Abandoned
Application number
US11/594,657
Other languages
English (en)
Inventor
Robert Morena
Paulo Marques
Henry Hagy
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Corning Inc
Original Assignee
Corning Inc
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
Application filed by Corning Inc filed Critical Corning Inc
Assigned to CORNING INCORPORATED reassignment CORNING INCORPORATED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MARQUES, PAULO JORGE, HAGY, HENRY EDWIN, MORENA, ROBERT MICHAEL
Publication of US20070123410A1 publication Critical patent/US20070123410A1/en
Priority to US12/692,662 priority Critical patent/US20100120603A1/en
Priority to US13/415,286 priority patent/US8252708B2/en
Abandoned legal-status Critical Current

Links

Images

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
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • 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
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • 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
    • 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
    • B01J2219/00889—Mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
    • B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
    • B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
    • B01L3/5027—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip

Definitions

  • the invention is directed to crystallization-free glass frits that are suitable for the manufacturing of glass microreactor using micro-molding technology and to the glass compositions used to make such frits; and in particular to glass frits that exhibit resistance to thermal shock and have excellent chemical durability.
  • microreactors are finding application in pharmaceutical and biological research, development and analysis.
  • a microreactor is a device that enables chemical reactions, either gaseous or liquid, to be done on the low milliliter scale (5-10 ml) as opposed to earlier laboratory “bench top” or pilot plant scales that varied in size from many tens of milliliters to liters in the former and up to a hundred liters, or more, in the latter.
  • the microreactor is generally a continuous flow reactor that brings the reaction components together in a small reactor channel.
  • FIG. 1 is a top view illustrating one of the simplest designs, a “T-shaped” microreactor 10 .
  • a T-shape is etched into a plate 20 to a selected depth (for example, 50 ⁇ m deep by 100 ⁇ m wide) and the etched plate is then covered with another plate ( 14 in FIG. 2 ) so that the etched portion form an enclosed channel.
  • the cover plate has openings (three illustrated in FIG. 1 ) so that fluids (gaseous or liquid) can be added and removed from the reactor.
  • a reaction is be carried out by pumping a first fluid containing a first reactant through opening 22 and a second fluid containing a second reactant through opening 24 .
  • FIG. 2 is a side view illustrating etched plate 20 , top plate 14 , openings 22 , 24 and 30 , and fluid illustrated as light grey in the reactor.
  • the dashed line 16 illustrates the junction of placed 14 and 20 .
  • FIG. 1 While the simple design illustrated in FIG. 1 is satisfactory for some reactions, for others a more complex design is required. For example, it may be desirous to add mixing baffles; openings for the further addition of reactants as the fluids travel from the beginning to the end of the reactor; space for heating and/or cooling elements with their associated connections; thermocouples and their connections; and other elements as may be need to carry out, control or monitor the reactions that occur within the microreactor. As a result the design of the reactor can become quite complicated; which in turn means that the construction of the reactor itself becomes complicated and expensive if etching techniques are used to construct parts of the microreactor.
  • microreactors While materials such as metals, silicon and certain polymers can be used to fabricate microreactors, these materials are not well suited for chemical reactions at high temperature and/or that use corrosive reactants. As a result of the foregoing problems, a simplified method for making microreactors is desirous; and it is further desired that such reactors be made of glass or ceramic materials due to their high thermal stability and their chemical durability and/or inertness to the vast majority of chemicals and solvents.
  • a frit is a powdered glass that sinters to form a structure that incorporates, for example, microreactor features and/or elements.
  • the frit is typically sandwiched between two substrate layers that may themselves incorporate some microreactor elements such as the openings for reactant(s) entry and exit, control leads for heaters and other elements, some of which have been described above.
  • the resulting “sandwiched” microreactor must be “fluid tight” so that reactants and/or solvents do not escape.
  • 2004/0152580 A1 (assigned to Corning Incorporated) describes borosilicate glass compositions and their use to make microfluidic devices such as the microreactors described above.
  • the problem with PYREX® glass frits is that they undergo devitrification (that is, crystals of different materials are formed) during sintering at temperatures in the range of 700-800° C.
  • devitrification that is, crystals of different materials are formed
  • U.S. 2004/0152580 A1 proposed that alumina be added to the borosilicate glass composition.
  • the addition of alumina causes the sintering ability of the frit to decrease and reduces the fluidity of the frit.
  • the materials describes in U.S. 2004/0152580 A1 resulted in an improved frit material, further improvements are needed to both frit compositions and to the method of making frits that can be used in microreactors.
  • the present invention is directed to improved compositions that can be used to make glass frits that can be used in microreactor and the methods of making such frits.
  • the invention is directed to glass compositions having a low softening point low CTE, high acid and alkali chemical resistance, and high crystallization resistance that are suitable for manufacturing glass frits for microreactors.
  • the glasses of the invention are borosilicate glasses containing either (a) lithium oxide plus aluminum oxide or (b) sodium oxide or potassium oxide.
  • the glasses of the invention have a crystallized depth layer, as measured by the HTS method described herein using bulk glass, of less than 30 ⁇ m, preferably less than 20 ⁇ m, and most preferable 10 ⁇ m or less.
  • the substrates used in practicing the invention can have a CTE in the range of 25-40 ⁇ 10 ⁇ 7 /° C., preferably in the range of 30 to 40 ⁇ 10 ⁇ 7 /° C.
  • the invention is further directed to borosilicate glasses and glass frits having a base composition in mole percent (mol %) of:
  • the invention is directed to glasses, and frits made therefrom, having the following compositions:
  • SiO 2 72.6 ⁇ 0.5 mol %
  • B 2 O 3 13.4 ⁇ 0.5 mol %
  • Al 2 O 3 6.5 ⁇ 0.4 mol %
  • Li 2 O 6.9 ⁇ 0.4 mol %
  • ZrO 2 0.5 ⁇ 0.1 mol %.
  • the glass compositions according to the invention that are suitable for frit use have and have a crystallized depth layer, as measured by the HTS method described herein using bulk glass, of less than 30 ⁇ m as measured after sintering on frit bars, preferably less than 20 ⁇ m, and most preferable 10 ⁇ m or less. Further, the glass compositions according have a softening point less than 825° C., preferably less than 800° C., and CTE ⁇ 35 ⁇ 10 ⁇ /° C.
  • FIG. 1 is a top view of a microreactor having a T-shaped reaction structure microreactor that has been etched into a substrate.
  • FIG. 2 is a side view of the microreactor of FIG. 1 that further illustrates the placement of a top plate over the substrate having the reactor structure etched therein.
  • FIG. 3 illustrates a process for making a microreactor, in this illustration the microreactor being a multi-level complex design.
  • FIG. 4 is a side view of a microreactor illustrating a bottom substrate, a frit with the microreactor design therein as represented by the horizontal lines and a top substrate having at least openings for the entry and exit of fluids.
  • FIG. 5 is a microphotograph of a B 2 O 3 /Al 2 O 3 /Li 2 O/SiO 2 glass frit according to the illustrating that the frits according to the invention do not crystallize even when alumina particles (as illustrated by the arrows) are present as a result of steps such as cutting and grinding using alumina saws and grinding devices.
  • FIG. 6 is a microphotograph illustrating the crystals (as illustrated by the arrows) found in a composition containing fluorine and the oxides of sodium, lithium, aluminum, calcium, boron and silicon
  • FIG. 7 is a microphotograph illustrating a composition not of the invention containing alumina and lithium that contains an amount of stuffed P-quartz crystals after sintering.
  • FIG. 8 is a microphotograph of a glass composition according to the invention that shows no crystallization after sintering.
  • FIG. 9 is an illustration of the thermal expansion dynamic mismatch curves for composition 723 CWF frit layers in slight tension or compression.
  • FIG. 10 illustrates of the mismatch in the butt seal using a BM 5 composition frit and Eagle 2000 substrate following 680° C. presintering and 800° C.
  • FIG. 11 illustrates butt seal mismatch for composition BM 5-721UP on Eagle 2000 substrate.
  • FIG. 12 illustrates butt seal mismatch for composition BM 5-721UP on Eagle 2000 substrate, presintered and sintered cooling data with 1 hour 38 minute hold at 526° C. and a cooling rate of 4° C./minute.
  • FIG. 13 illustrates thermal expansion mismatch versus time for a BM 5-721UP frit on Eagle 2000 substrate (presintered and sintered) during a hold at 526° C.
  • FIG. 14 illustrates butt seal mismatch for BM 5-721UP, Blend 6500 and Blend 6513 frits on Eagle 2000 substrate after presintering and sintering.
  • a process for the manufacturing of microreactors can be based on micro-molding of glass frit structures onto a substrate and then covering the frit with an appropriate cover layer of material. This process is based on the micro-molding techniques disclosed in U.S. Pat. No. 5,853,446 (the '446 patent) that are used to make formed glass structures that are particularly useful for forming barrier rib structures for use in plasma display units.
  • FIG. 2 of the '446 patent illustrates a frit bonded (adhered) to the substrate.
  • two substrates first or bottom and second or top substrates
  • the frit would be sandwiched between them as illustrated in FIG. 4 of this application.
  • the first firing step or heat treatment is made at a temperature at which the viscosity of the frit is approximately 1 ⁇ 10 10 poise and for a time in the range of 25-40 minutes to ensure initial densification of the frits glass composition.
  • This first heat treatment is needed to achieve sufficient frit structure strength and to provide adequate adhesion of the frit layer to a substrate prior to any further processing or machining (for example: dicing, drilling, polishing, etching or other processing steps).
  • a second firing or heat treatment step (also called the sintering or curing cycle) is needed to seal the stacked layers and the frit and the substrate together, complete full densification and achieve gas tightness of the frit structures.
  • This final curing is made at a frit viscosity of approximately 1 ⁇ 10 7 poise for a time in the range 20-45 minutes.
  • FIG. 3 illustrates, in a very general way, a molding process for making a microreactor, in this case a microreactor having a complex, multi-layer design.
  • Box 100 represents the mask design and production of the master mold which is used to make a production mold 120 out of a material such as a silicone.
  • a suitable substrate 110 is selected and the frit composition 112 is placed on substrate 110 .
  • the mold 120 is then applied to the composition 114 on substrate 110 to form the frit design as indicated at 126 ; and after removal of the mold the composition is pre-sintered as described above.
  • a top substrate 128 is placed over the frit/substrate combination represented by 126 and appropriate openings are drilled as indicated by numeral 140 .
  • FIG. 4 represents a very simple microreactor such as the T-shaped microreactor illustrated in FIG. 1 .
  • the microreactor 200 is comprised of a bottom substrate 210 , a molded frit 220 with the reactor design therein as represented by 230 and top substrate 240 that has openings 250 therethrough for the entry and exit of fluids.
  • the substrate glasses are commercially available borosilicate and boroaluminosilicate glasses such as Corning 7740, 1737, 7761 and Eagle 2000 glasses, all of which are commercially available.
  • Frits of the present invention are made from glass compositions that have a crystallized depth layer, as measured by the HTS method described herein using bulk glass, of less than 30 ⁇ m as measured after sintering on frit bars, preferably less than 20 ⁇ m, and most preferable 10 ⁇ m or less.
  • the glass substrate be made of a low thermal expansion glass, preferably one having a thermal expansion in the range of 25 to 40 ⁇ 10 ⁇ 7 /° C., preferably in the range of 30 to 40 ⁇ 10 ⁇ 7 /° C.
  • the material used to make the frit should be made of a low thermal expansion material; should also have a softening point temperature that does not exceed 850° C., and preferably less than 800° C., in order to prevent deformation (creping) of the substrate 1737 or Eagle 2000 during firing; should have high crystallization resistance in order to insure full densification and good strength; and should have a high chemical resistance to acids and alkalies the better (the higher the better).
  • the frit compositions according to the invention satisfy these criteria.
  • the borosilicate glass frits of the present invention have a base composition in mole percent (mol %) of:
  • the glass compositions suitable for frit use have a crystallized layer depth, as measured on bulk glass using the HTS method described herein, of 30 ⁇ m or less, preferably 20 ⁇ m or less, and most preferably 10 ⁇ m or less.
  • a preferred composition is:
  • compositions are:
  • the foregoing glass compositions suitable for frit use have, afterheat treatment, a crystallized layer depth of 30 ⁇ m or less, preferably 20 ⁇ m or less, and most preferably 10 ⁇ m or less.
  • Borosilicate glass powders described in the present invention were prepared from quartz, anhydrous boric oxide, boric acid, calcined alumina, alkali carbonates and, optionally, alkaline-earth carbonates. After mixing, the vitrifiable mixture was melted in an induction furnace at 1650° C. for 6 hours in a platinum-rhodium crucible. The melted glasses were then quenched in water and milled under dry conditions using an alumina ball mill. The ball-milled powder was then sieved (to ⁇ 63 ⁇ m) and paste samples were prepared from the sieved powder mixed with wax material (for example, MX4462) by molding a flat layer onto a selected substrate; for example, a Corning 1737 or Eagle 2000 glass substrate. The samples were then heated (pre-sintered and sintered) according to the two-step process described above.
  • wax material for example, MX4462
  • XRD x-ray diffraction
  • SEM scanning electron microscope
  • HTS specific test designated “HTS” herein was used to evaluate the crystallization resistance of “bulk” glasses by heat treating a polished piece of glass (for example, a bulk glass obtained from the crucible melt described in the previous paragraph, or cored/sawed from a large boule) for forty-eight (48) hours at the glass softening point temperature (typically corresponding to a viscosity in the range of 10 7 to 10 8 poise for the glasses described herein).
  • the extent of crystallization was compared from one composition to another by measuring the thickness of the crystallized layer and the dimensions of the crystals.
  • HTS values of 30 ⁇ m or less are preferred, with values less than 20 ⁇ m being especially preferred.
  • a glass having a HTS value of approximately 10 ⁇ m or less is deemed to be totally amorphous when used in powder form after the two-step firing process.
  • the polishing of the glass piece used for the HTS test was carried out using cerium oxide and standard glass polishing methods known in the art, for example, methods described or referenced in the Handbook of Ceramic Grinding and Polishing , eds. I. M. Marinescu et al (Park Ridge, N.J. USA, Noyes Publications 2000), pp. 374-389.
  • the thermal expansion of the frits was measured by thermal mechanical analysis (“TMA”) or by dilatometry.
  • Glasses according to the invention have a coefficient of thermal expansion (CTE), measured as bulk glass, in the range of 25-40 ⁇ 10 ⁇ 7 /° C.
  • CTE coefficient of thermal expansion
  • the CTE value should be smaller than that of the substrate glass in order to avoid tensile stresses building up during use and fracturing the reactor.
  • the glasses of the invention also have a softening point less than 800° C. As a general rule, the softening point of the frit glass should be less than that of the substrate. Consequently, some adjustment of the glass composition may be necessary if the substrate glass is changed. Seal stresses were examined via polarimetric techniques and mismatch as a function of temperature also recorded.
  • Alumina in a borosilicate glass composition inhibits, and may even prevent, the formation of polymorph silica crystals in alkali borosilicate frits.
  • the softening point temperature of the glass, or a glass frit made with the composition increases drastically. Consequently, in order to maintain a low softening point and to satisfy maximum processing temperature requirements, it is necessary to add flux components, or to increase the amount of the flux components if they are already present, to balance the alumina effect. Since a strong coupling occurs in glass networks between Li+ and Al13+, Li 2 O was selected as the flux material to soften the glass.
  • a borosilicate glass composition designated in Table 1 as REAC 66 was found to have good crystallization resistance and very good chemical resistance. This glass composition contains Al 2 O 3 and Li 2 O. However, even if crystallization of polymorph silica crystals is actually inhibited by alumina, there is always a concern that when alumina and lithium are present together in a frit composition, a minor amount of stuffed P-quartz crystals will frequently still occur during sintering (see FIG. 6 , Sample REAC 70).
  • the invention has resulted in new alkali borosilicate frits which are more resistant to crystallization than prior compositions.
  • the sintered structures made with these frits remained totally amorphous after the two-firing step process.
  • the new frits do not crystallize during sintering even if particles such as alumina particles (see FIG. 5 ) coming from grinding or others impurities are present into the paste before sintering.
  • This great level of crystallization resistance is achieved by increasing the boron content of the glass frit composition.
  • the glasses designate BM 5 and 723 CWF bulk glass exhibit only a small amount of crystallization after the long duration heat treatment of the HTS test.
  • the glass compositions according to the invention have very good level of acid resistance, their acid resistance as determined by DIN 12116 (see Tables 1 and 2) being similar to 7740 glass which is a Pyrex® glass used to make laboratory glassware (see values for BM 5 and BM 7). However, by increasing boron content above 13% (mol), there is some lowering of the alkali resistance (ISO 695 values in Tables 1 and 2)) of the glasses. Values for alkali tests increase from 102 mg/dm2 (7740 glass) to values of 374 and 1220 for the BM 5 and 723 CWF compositions, respectively.
  • the magnitude and sign of seal stress can be managed over a large temperature range by adjusting the thermal cycle on cooling step that occurs after the final assembly.
  • all frit layers of 723 CWF are typically in slight tension after cooling as shown in thermal expansion dynamic mismatch curves (see FIG. 9 ).
  • the glass compositions according to the invention impart an advantage over previously known borosilicate glass frits by providing new families of borosilicate frits that have similar properties of thermal expansion, chemical stability and viscosity as Pyrex® 7740 or 7761 frit glasses, and additionally have a very strong crystallization resistance not found in glass frits made from 7740 glass.
  • the new frits according to the invention did not crystallize during the two-firing steps as used in conducting the experiments reported herein in spite of the presence of impurities that may be present in the paste.
  • the glass frit compositions according to the invention can form hermetic sintered channels on glass substrates in accordance with the process described in U.S. Pat. No. 5,853,446 (3).
  • microreactor channels formed in the frits are vitreous, translucent, chemically durable and resistant to thermal shock.
  • the frits can also be matched to different substrate materials, for example a 1737 or Eagle2000 substrate, over a large temperature range (300° C.), and the sign and magnitude of mismatch can be tailored by the thermal cycle.
  • Tables 1 and 2 describe a number of glass compositions that were prepared and evaluated for use as frits.
  • Compositions REAC 66, 720 CWF and BM 5 were found to most closely match frit requirement for substrates made of 1737 glass which is commercially available from Coming Incorporated.
  • Other glass compositions that can be used are the REAC 70 and REAC 82 which have a crystalline layer less than 20 ⁇ m. All glass composition according to the invention have a CTE close matched to substrate CTE values and also have softening points that are below that of the substrate and are below 825° C. to ensure that the glass can be properly sealed to the substrate without requiring high temperatures that may induce the composition to form crystals or deform the substrate.
  • a preferred substrate for microreactor devices is Corning's commercially available Eagle 2000 glass. Because the glass frits defining the microreactor structure seal directly to the substrate, CTE compatibility between the substrate and the frit is a major concern.
  • the CTE of the Eagle 2000 glass is in the range of 30-32 ⁇ 10 ⁇ 7 /° C. While, as indicated above in Experiment 1, the 7761 and 7740 glasses could be used as frit materials, they are not ideal for the Eagle 2000 substrate because either the softening point is too high or because they fail the crystallization test.
  • the softening point should be less than 800° C., preferable less than approximately 780° C., and the crystallized layer should be less than 30 ⁇ m and preferably 10 ⁇ m or less.
  • BM 5 glass shown above in Table 2 meets both these criteria.
  • a series of experiments was performed to optimize the BM 5 composition for use with the Eagle 2000 substrate. This was carried out by replacing K 2 O with Na 2 O in the composition.
  • Table 3 gives the results of these experiments.
  • BM 5-721UP is the same composition as BM 5 in Table 2.
  • FIG. 10 shows expansion mismatch data obtained on a butt seal sample of BM-5 frit (melted as 721UJ), and Eagle 2000 glass.
  • the butt seal sample was first fired to 680° C. for presintering, re-heated in a different furnace (one equipped with a polarimeter) to approximately 580° C. to relieve all mismatch strains, and then cooled slowly to monitor the re-appearance of the mismatch strains. Following this, the sample was then heated to 800° C. for sintering, and then re-heated in the polarimeter furnace as per the above procedure, so that mismatch strains corresponding to the sintering schedule could be measured during cooling.
  • mismatch values shown in FIG. 10 correspond to those in the substrate glass at the frit-substrate interface.
  • mismatch values >0 i.e., positive
  • transient values for the frit measured during the sintering schedule approach 180 ppm, a high strain state, and one not desired for a seal involving brittle materials.
  • Preferred glass composition have mismatch values less than ⁇ 20 (that is, are more negative than ⁇ 20), and preferably less than ⁇ 50
  • BM-5 despite its good expansion compatibility with 1737 seen in Table 2, does not have the best expansion-match to the lower CTE substrate, Eagle 2000 .
  • BM-5 is a potassium borosilicate glass.
  • replacement of modifying cations such as potassium in a silicate glass by species of smaller size (but with the same charge) results in a lower CTE, since the higher field strength of the substituting ions produce an overall tightening of the silica tetrahedral framework.
  • FIG. 12 The effect after annealing after 800° C. sintering hold is illustrated in FIG. 12 by the mismatch readings for a 721UT-Eagle 2000 butt seal that was held at 526° C. during the cool-down from the 800° C. sintering hold.
  • the maximum value of transient strain during cooling was reduced by approximately half (from +200 ppm to +100 ppm), and that the residual (or room temperature) mismatch now shows the frit in desirable compression.
  • the actual relief of the mismatch strains during the annealing hold at 526° C. is shown in FIG. 13 for the 721UT-Eagle 2000 butt seal. Note that mismatch strain follows a classic Maxwell-type decay relationship.
  • fillers The effect of fillers is to adjust the CTE of the frit to achieve a more acceptable mismatch.
  • a blend most of the fillers that have been used to lower CTE of the resulting frit mixture (termed “a blend”) have been low CTE compounds obtained through the glass ceramic process.
  • materials that can be used as fillers include:
  • FIG. 14 illustrates the mismatch data for butt seals to Eagle 2000 following the 800° C. sintering schedule. Shown are 721UT (from FIG. 10 ), and two blends made with BM 5-721UT (simply numbered as 721UT below and in FIG. 14 ) and stuffed Zn-containing ⁇ -quartz designated 88MOC. These blends are identified as Blend 6500 (90% 721UT +10% 88MOC, wt. basis), and Blend 6513 (15% 88MOC or 85% 721UT+15% 88MOC). Note the progressive improvement of mismatch (i.e., frit becomes progressively in lower tension) with increasing filler addition. Also, it is to be understood that the presence of any of the foregoing fillers in the composition is not to be considered as impacting HTS crystallization depth layer and must be excluded from any determination of the HTS crystallization depth layer.
  • the invention can be further considered as being directed to a microreactor having at least the elements of a first substrate, a second substrate and a microreactor frit between the two substrates; where at least one of the top and bottom substrates has an entry opening and/or an exit opening for the entry and exit of the reaction fluids that are passed through the microreactor, and the frit has at least one channel, passageway or path from the entry opening to the exit opening, the frit being made of any glass composition recited herein.
  • the microreactor can also have baffles for mixing, heating elements with leads passing through the frit of a substrate, addition openings for the entry of additional substance to the reaction fluids while they travel from the entry opening to the exit opening, sensors with leads, sample ports and other elements such as are known in the art for monitoring, sampling, heating, and cooling.
  • the microreactor can contain a single frit or a plurality of microreactor frits as has been described herein and is illustrated in exemplary manner in FIG. 3 .
  • Preferred glass compositions include:
  • SiO 2 72.6 ⁇ 0.5 mol %
  • B 2 O 3 13.4 ⁇ 0.5 mol %
  • Al 2 O 3 6.5 ⁇ 0.4 mol %
  • Li 2 O 6.9 ⁇ 0.4 mol %
  • ZrO 2 0.5 ⁇ 0.1 mol %.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Clinical Laboratory Science (AREA)
  • Glass Compositions (AREA)
US11/594,657 2005-11-30 2006-11-08 Crystallization-free glass frit compositions and frits made therefrom for microreactor devices Abandoned US20070123410A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US12/692,662 US20100120603A1 (en) 2005-11-30 2010-01-25 Crystallization-free glass frit compositions and frits made therefrom for microreactor devices
US13/415,286 US8252708B2 (en) 2005-11-30 2012-03-08 Crystallization-free glass frit compositions and frits made therefrom for microreactor devices

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP05292534.4 2005-11-30
EP05292534 2005-11-30

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US12/692,662 Division US20100120603A1 (en) 2005-11-30 2010-01-25 Crystallization-free glass frit compositions and frits made therefrom for microreactor devices

Publications (1)

Publication Number Publication Date
US20070123410A1 true US20070123410A1 (en) 2007-05-31

Family

ID=35788300

Family Applications (3)

Application Number Title Priority Date Filing Date
US11/594,657 Abandoned US20070123410A1 (en) 2005-11-30 2006-11-08 Crystallization-free glass frit compositions and frits made therefrom for microreactor devices
US12/692,662 Abandoned US20100120603A1 (en) 2005-11-30 2010-01-25 Crystallization-free glass frit compositions and frits made therefrom for microreactor devices
US13/415,286 Expired - Fee Related US8252708B2 (en) 2005-11-30 2012-03-08 Crystallization-free glass frit compositions and frits made therefrom for microreactor devices

Family Applications After (2)

Application Number Title Priority Date Filing Date
US12/692,662 Abandoned US20100120603A1 (en) 2005-11-30 2010-01-25 Crystallization-free glass frit compositions and frits made therefrom for microreactor devices
US13/415,286 Expired - Fee Related US8252708B2 (en) 2005-11-30 2012-03-08 Crystallization-free glass frit compositions and frits made therefrom for microreactor devices

Country Status (8)

Country Link
US (3) US20070123410A1 (enExample)
EP (2) EP1963235B1 (enExample)
JP (1) JP5355090B2 (enExample)
KR (1) KR20080072082A (enExample)
CN (1) CN101316799B (enExample)
AT (1) ATE506330T1 (enExample)
DE (1) DE602006021471D1 (enExample)
WO (1) WO2007063092A1 (enExample)

Cited By (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009051814A1 (en) * 2007-10-19 2009-04-23 Corning Incorporated Method of forming structured sintered articles
US20090139590A1 (en) * 2007-11-30 2009-06-04 Paulo Gaspar Jorge Marques Durable Frit Composition and Composites and Devices Comprised Thereof
US20100178214A1 (en) * 2007-05-18 2010-07-15 Paulo Gaspar Jorge Marques Glass Microfluidic Devices and Methods of Manufacture Thereof
WO2010126992A1 (en) * 2009-04-28 2010-11-04 Corning Incorporated Microreactors with connectors sealed thereon; their manufacturing
US20120138215A1 (en) * 2010-12-03 2012-06-07 Samsung Electro-Mechanics Co., Ltd. Nano glass powder for sintering additive and method for fabricating the same
WO2013082257A1 (en) * 2011-11-30 2013-06-06 Corning Incorporated Complex structures in refractory bodies and methods of forming
US8551898B2 (en) 2011-10-25 2013-10-08 Corning Incorporated Glass compositions with improved chemical and mechanical durability
US20140117559A1 (en) * 2012-03-30 2014-05-01 Paul A. Zimmerman Process and material for preventing deleterious expansion of high aspect ratio copper filled through silicon vias (tsvs)
US9145329B2 (en) 2011-10-25 2015-09-29 Corning Incorporated Alkaline earth alumino-silicate glass compositions with improved chemical and mechanical durability
US9186295B2 (en) 2011-10-25 2015-11-17 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9517966B2 (en) 2011-10-25 2016-12-13 Corning Incorporated Glass compositions with improved chemical and mechanical durability
US9603775B2 (en) 2013-04-24 2017-03-28 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9700485B2 (en) 2013-04-24 2017-07-11 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9700486B2 (en) 2013-04-24 2017-07-11 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9707153B2 (en) 2013-04-24 2017-07-18 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9707154B2 (en) 2013-04-24 2017-07-18 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9707155B2 (en) 2013-04-24 2017-07-18 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9713572B2 (en) 2013-04-24 2017-07-25 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9717648B2 (en) 2013-04-24 2017-08-01 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9717649B2 (en) 2013-04-24 2017-08-01 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9839579B2 (en) 2013-04-24 2017-12-12 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9849066B2 (en) 2013-04-24 2017-12-26 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US10273049B2 (en) 2012-06-28 2019-04-30 Corning Incorporated Delamination resistant glass containers with heat-tolerant coatings
US10350139B2 (en) 2011-10-25 2019-07-16 Corning Incorporated Pharmaceutical glass packaging assuring pharmaceutical sterility
US10364182B2 (en) * 2014-10-08 2019-07-30 Corning Incorporated Glasses and glass ceramics including a metal oxide concentration gradient
US11021393B2 (en) 2014-11-04 2021-06-01 Corning Incorporated Deep non-frangible stress profiles and methods of making
US11079309B2 (en) 2013-07-26 2021-08-03 Corning Incorporated Strengthened glass articles having improved survivability
US11084756B2 (en) 2014-10-31 2021-08-10 Corning Incorporated Strengthened glass with ultra deep depth of compression
US11174197B2 (en) 2016-04-08 2021-11-16 Corning Incorporated Glass-based articles including a metal oxide concentration gradient
US11267228B2 (en) 2015-07-21 2022-03-08 Corning Incorporated Glass articles exhibiting improved fracture performance
US11472734B2 (en) 2015-12-11 2022-10-18 Corning Incorporated Fusion-formable glass-based articles including a metal oxide concentration gradient
US11492291B2 (en) 2012-02-29 2022-11-08 Corning Incorporated Ion exchanged glasses via non-error function compressive stress profiles
US11613103B2 (en) 2015-07-21 2023-03-28 Corning Incorporated Glass articles exhibiting improved fracture performance
US11634359B2 (en) 2014-02-24 2023-04-25 Corning Incorporated Strengthened glass with deep depth of compression
US11878941B2 (en) 2014-06-19 2024-01-23 Corning Incorporated Glasses having non-frangible stress profiles
US11963320B2 (en) 2016-04-08 2024-04-16 Corning Incorporated Glass-based articles including a stress profile comprising two regions

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070123410A1 (en) * 2005-11-30 2007-05-31 Morena Robert M Crystallization-free glass frit compositions and frits made therefrom for microreactor devices
EP2216093A1 (en) 2009-01-30 2010-08-11 Corning Incorporated In situ formation and deposition of palladium Pd(0) in reactors
WO2014055840A2 (en) 2012-10-04 2014-04-10 Corning Incorporated Compressively stressed laminated glass article via photosensitive glass and method of making the article
CN104936912A (zh) * 2012-10-04 2015-09-23 康宁股份有限公司 具有玻璃层和玻璃陶瓷层的制品以及该制品的制造方法
JP6701541B2 (ja) * 2014-11-25 2020-05-27 日本電気硝子株式会社 ガラス粉末、複合粉末及び絵付層付き低膨張基板
WO2016084627A1 (ja) * 2014-11-25 2016-06-02 日本電気硝子株式会社 ガラス粉末、複合粉末及び絵付層付き低膨張基板
JP6881312B2 (ja) * 2015-10-30 2021-06-02 日本電気硝子株式会社 結晶性ガラス封止材
JP2018019033A (ja) * 2016-07-29 2018-02-01 太陽誘電株式会社 コイル部品及びその製造方法

Citations (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2319816A (en) * 1938-10-29 1943-05-25 Polaroid Corp Light polarizer and process of manufacture
US3499976A (en) * 1964-10-02 1970-03-10 Jerome H Lemelson Magnetic recording apparatus and method for moving a transducer into engagement with a selected portion of a record
US3540793A (en) * 1968-07-03 1970-11-17 Corning Glass Works Photochromic polarizing glasses
US3653863A (en) * 1968-07-03 1972-04-04 Corning Glass Works Method of forming photochromic polarizing glasses
US3873329A (en) * 1973-07-02 1975-03-25 Corning Glass Works Glass-ceramic article
US3954485A (en) * 1974-09-16 1976-05-04 Corning Glass Works Silver-free polarizing photochromic glasses
US4017318A (en) * 1976-01-02 1977-04-12 Corning Glass Works Photosensitive colored glasses
US4118214A (en) * 1977-06-22 1978-10-03 Corning Glass Works Treating polychromatic glass in reducing atmospheres
US4125405A (en) * 1976-11-05 1978-11-14 Corning Glass Works Colored, dichroic, birefringent glass articles produced by optical alteration of additively-colored glasses containing silver and silver halides
US4125404A (en) * 1976-11-05 1978-11-14 Corning Glass Works Photochromic glasses exhibiting dichroism, birefringence and color adaptation
US4134747A (en) * 1977-03-16 1979-01-16 Corning Glass Works Method of forming transparent and opaque portions in a reducing atmosphere glass
US4226628A (en) * 1979-07-30 1980-10-07 Corning Glass Works Cuprous copper and/or silver halophosphate glasses
US4282022A (en) * 1980-04-28 1981-08-04 Corning Glass Works Method for making polarizing glasses through extrusion
US4304584A (en) * 1980-04-28 1981-12-08 Corning Glass Works Method for making polarizing glasses by extrusion
US4315991A (en) * 1980-12-19 1982-02-16 Corning Glass Works Very low expansion sealing frits
US4726981A (en) * 1985-06-10 1988-02-23 Corning Glass Works Strengthened glass articles and method for making
US4814297A (en) * 1987-04-01 1989-03-21 Corning Glass Works Strengthened glass article and method
US4980318A (en) * 1989-05-10 1990-12-25 Corning Incorporated High refractive index photochromic glasses
US4979975A (en) * 1989-08-07 1990-12-25 Corning Incorporated Fast response photosensitive opal glasses
US5057018A (en) * 1986-05-13 1991-10-15 American Dental Association - Health Foundation Microcrystalline inserts for megafilled composite dental restorations
US5071793A (en) * 1990-08-23 1991-12-10 Aluminum Company Of America Low dielectric inorganic composition for multilayer ceramic package
US5374595A (en) * 1993-01-22 1994-12-20 Corning Incorporated High liquidus viscosity glasses for flat panel displays
US5413971A (en) * 1993-09-14 1995-05-09 Mcpherson; Donald M. Laser absorbing filter glass
US5430573A (en) * 1993-12-15 1995-07-04 Corning Incorporated UV-absorbing, polarizing glass article
US5517356A (en) * 1993-12-15 1996-05-14 Corning Incorporated Glass polarizer for visible light
US5625427A (en) * 1993-12-15 1997-04-29 Corning Incorporated Ophthalmic lens
US5627114A (en) * 1994-11-07 1997-05-06 Corning Incorporated Laser eyewear protection
US5729381A (en) * 1994-11-07 1998-03-17 Corning Incorporated Glasses for laser protection
US5747395A (en) * 1993-09-28 1998-05-05 Cookson Matthey Ceramics & Materials Limited Cobalt glass compositions for coatings
US5747399A (en) * 1995-09-14 1998-05-05 Nippon Electric Glass Co., Ltd. Glass for a fluorescent lamp
US5853446A (en) * 1996-04-16 1998-12-29 Corning Incorporated Method for forming glass rib structures
US6221480B1 (en) * 1996-12-04 2001-04-24 Corning Incorporated Broadband contrast polarizing glass
US6298691B1 (en) * 1997-04-24 2001-10-09 Corning Incorporated Method of making glass having polarizing and non-polarizing regions
US6444076B1 (en) * 1997-06-26 2002-09-03 Corning Incorporated Optical devices and their method of assembly
US6461734B1 (en) * 1998-02-04 2002-10-08 Corning Incorporated Substrate for array printing
US6466297B1 (en) * 1999-07-02 2002-10-15 Merck Patent Geselleschaft Mit Beschrankter Haftung Method of preparing a broadband reflective polarizer
US6536236B2 (en) * 1999-03-23 2003-03-25 Corning, Incorporated Method of making a polarizing glass
US6563639B1 (en) * 2002-01-24 2003-05-13 Corning Incorporated Polarizing glasses
US6599736B2 (en) * 2000-08-25 2003-07-29 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. Configurable microreactor network
US6635592B1 (en) * 1999-11-29 2003-10-21 Nippon Electric Glass Co., Ltd. Tungsten seal glass for fluorescent lamp
US20040152580A1 (en) * 2002-12-03 2004-08-05 Paulo Marques Borsilicate glass compositions and uses thereof
US20050128588A1 (en) * 1998-05-14 2005-06-16 Borrelli Nicholas F. Ultra-thin glass polarizers and method of making same

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3499776A (en) * 1966-07-13 1970-03-10 Owens Illinois Inc Alkali metal borosilicate glass compositions containing zirconia
FR2558152B1 (fr) * 1984-01-13 1992-03-27 Corning Glass Works Verres a usage ophtalmique de faible densite, absorbant les radiations ultraviolettes et ayant une haute transmission dans le visible et lentilles correctrices constituees de ces verres
DE3722130A1 (de) * 1987-07-02 1989-01-12 Schott Glaswerke Borosilikatglas
EP0518610B1 (en) * 1991-06-14 1995-10-18 COOKSON GROUP plc Glass compositions
GB9401818D0 (en) * 1994-01-31 1994-03-23 Cookson Group Plc Glass compositions
JP3680367B2 (ja) * 1994-08-19 2005-08-10 株式会社日立製作所 配線基板
JPH0986955A (ja) * 1995-09-29 1997-03-31 Murata Mfg Co Ltd 絶縁体用ガラス組成物、絶縁体ペースト、および厚膜印刷回路
JPH11116272A (ja) * 1997-10-20 1999-04-27 Murata Mfg Co Ltd 高周波用ガラス粉末およびそれを用いた電気絶縁層
JP3287303B2 (ja) * 1998-02-27 2002-06-04 株式会社村田製作所 誘電体磁器組成物およびそれを用いたセラミック電子部品
EP0999459A3 (en) 1998-11-03 2001-12-05 Corning Incorporated UV-visible light polarizer and methods
JP3995902B2 (ja) * 2001-05-31 2007-10-24 Ｈｏｙａ株式会社 情報記録媒体用ガラス基板及びそれを用いた磁気情報記録媒体
FR2830206B1 (fr) * 2001-09-28 2004-07-23 Corning Inc Dispositif microfluidique et sa fabrication
JP3772123B2 (ja) * 2002-03-19 2006-05-10 オリンパス株式会社 微小流路素子
DE20220582U1 (de) * 2002-08-24 2003-11-13 Schott Glas, 55122 Mainz Borosilicatglas
US20070123410A1 (en) * 2005-11-30 2007-05-31 Morena Robert M Crystallization-free glass frit compositions and frits made therefrom for microreactor devices

Patent Citations (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2319816A (en) * 1938-10-29 1943-05-25 Polaroid Corp Light polarizer and process of manufacture
US3499976A (en) * 1964-10-02 1970-03-10 Jerome H Lemelson Magnetic recording apparatus and method for moving a transducer into engagement with a selected portion of a record
US3540793A (en) * 1968-07-03 1970-11-17 Corning Glass Works Photochromic polarizing glasses
US3653863A (en) * 1968-07-03 1972-04-04 Corning Glass Works Method of forming photochromic polarizing glasses
US3873329A (en) * 1973-07-02 1975-03-25 Corning Glass Works Glass-ceramic article
US3954485A (en) * 1974-09-16 1976-05-04 Corning Glass Works Silver-free polarizing photochromic glasses
US4017318A (en) * 1976-01-02 1977-04-12 Corning Glass Works Photosensitive colored glasses
US4057408A (en) * 1976-01-02 1977-11-08 Corning Glass Works Method for making photosensitive colored glasses
US4125404A (en) * 1976-11-05 1978-11-14 Corning Glass Works Photochromic glasses exhibiting dichroism, birefringence and color adaptation
US4125405A (en) * 1976-11-05 1978-11-14 Corning Glass Works Colored, dichroic, birefringent glass articles produced by optical alteration of additively-colored glasses containing silver and silver halides
US4134747A (en) * 1977-03-16 1979-01-16 Corning Glass Works Method of forming transparent and opaque portions in a reducing atmosphere glass
US4118214A (en) * 1977-06-22 1978-10-03 Corning Glass Works Treating polychromatic glass in reducing atmospheres
US4226628A (en) * 1979-07-30 1980-10-07 Corning Glass Works Cuprous copper and/or silver halophosphate glasses
US4282022A (en) * 1980-04-28 1981-08-04 Corning Glass Works Method for making polarizing glasses through extrusion
US4304584A (en) * 1980-04-28 1981-12-08 Corning Glass Works Method for making polarizing glasses by extrusion
US4315991A (en) * 1980-12-19 1982-02-16 Corning Glass Works Very low expansion sealing frits
US4726981A (en) * 1985-06-10 1988-02-23 Corning Glass Works Strengthened glass articles and method for making
US5057018A (en) * 1986-05-13 1991-10-15 American Dental Association - Health Foundation Microcrystalline inserts for megafilled composite dental restorations
US4814297A (en) * 1987-04-01 1989-03-21 Corning Glass Works Strengthened glass article and method
US4980318A (en) * 1989-05-10 1990-12-25 Corning Incorporated High refractive index photochromic glasses
US4979975A (en) * 1989-08-07 1990-12-25 Corning Incorporated Fast response photosensitive opal glasses
US5071793A (en) * 1990-08-23 1991-12-10 Aluminum Company Of America Low dielectric inorganic composition for multilayer ceramic package
US5374595A (en) * 1993-01-22 1994-12-20 Corning Incorporated High liquidus viscosity glasses for flat panel displays
US5413971A (en) * 1993-09-14 1995-05-09 Mcpherson; Donald M. Laser absorbing filter glass
US5747395A (en) * 1993-09-28 1998-05-05 Cookson Matthey Ceramics & Materials Limited Cobalt glass compositions for coatings
US5430573A (en) * 1993-12-15 1995-07-04 Corning Incorporated UV-absorbing, polarizing glass article
US5517356A (en) * 1993-12-15 1996-05-14 Corning Incorporated Glass polarizer for visible light
US5625427A (en) * 1993-12-15 1997-04-29 Corning Incorporated Ophthalmic lens
US5627114A (en) * 1994-11-07 1997-05-06 Corning Incorporated Laser eyewear protection
US5729381A (en) * 1994-11-07 1998-03-17 Corning Incorporated Glasses for laser protection
US5747399A (en) * 1995-09-14 1998-05-05 Nippon Electric Glass Co., Ltd. Glass for a fluorescent lamp
US5853446A (en) * 1996-04-16 1998-12-29 Corning Incorporated Method for forming glass rib structures
US6221480B1 (en) * 1996-12-04 2001-04-24 Corning Incorporated Broadband contrast polarizing glass
US6298691B1 (en) * 1997-04-24 2001-10-09 Corning Incorporated Method of making glass having polarizing and non-polarizing regions
US6444076B1 (en) * 1997-06-26 2002-09-03 Corning Incorporated Optical devices and their method of assembly
US6461734B1 (en) * 1998-02-04 2002-10-08 Corning Incorporated Substrate for array printing
US20050128588A1 (en) * 1998-05-14 2005-06-16 Borrelli Nicholas F. Ultra-thin glass polarizers and method of making same
US6536236B2 (en) * 1999-03-23 2003-03-25 Corning, Incorporated Method of making a polarizing glass
US6466297B1 (en) * 1999-07-02 2002-10-15 Merck Patent Geselleschaft Mit Beschrankter Haftung Method of preparing a broadband reflective polarizer
US6635592B1 (en) * 1999-11-29 2003-10-21 Nippon Electric Glass Co., Ltd. Tungsten seal glass for fluorescent lamp
US6599736B2 (en) * 2000-08-25 2003-07-29 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. Configurable microreactor network
US6563639B1 (en) * 2002-01-24 2003-05-13 Corning Incorporated Polarizing glasses
US6775062B2 (en) * 2002-01-24 2004-08-10 Corning Incorporated Polarizing glasses
US20040152580A1 (en) * 2002-12-03 2004-08-05 Paulo Marques Borsilicate glass compositions and uses thereof

Cited By (79)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100178214A1 (en) * 2007-05-18 2010-07-15 Paulo Gaspar Jorge Marques Glass Microfluidic Devices and Methods of Manufacture Thereof
WO2009051814A1 (en) * 2007-10-19 2009-04-23 Corning Incorporated Method of forming structured sintered articles
US7767135B2 (en) 2007-10-19 2010-08-03 Corning Incorporated Method of forming a sintered microfluidic device
US20090139590A1 (en) * 2007-11-30 2009-06-04 Paulo Gaspar Jorge Marques Durable Frit Composition and Composites and Devices Comprised Thereof
US8162005B2 (en) * 2007-11-30 2012-04-24 Corning Incorporated Durable frit composition and composites and devices comprised thereof
WO2010126992A1 (en) * 2009-04-28 2010-11-04 Corning Incorporated Microreactors with connectors sealed thereon; their manufacturing
US20120138215A1 (en) * 2010-12-03 2012-06-07 Samsung Electro-Mechanics Co., Ltd. Nano glass powder for sintering additive and method for fabricating the same
US9517966B2 (en) 2011-10-25 2016-12-13 Corning Incorporated Glass compositions with improved chemical and mechanical durability
US11707410B2 (en) 2011-10-25 2023-07-25 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US10413483B2 (en) 2011-10-25 2019-09-17 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US8753994B2 (en) 2011-10-25 2014-06-17 Corning Incorporated Glass compositions with improved chemical and mechanical durability
US10350139B2 (en) 2011-10-25 2019-07-16 Corning Incorporated Pharmaceutical glass packaging assuring pharmaceutical sterility
US8980777B2 (en) 2011-10-25 2015-03-17 Corning Incorporated Glass compositions with improved chemical and mechanical durability
US9145329B2 (en) 2011-10-25 2015-09-29 Corning Incorporated Alkaline earth alumino-silicate glass compositions with improved chemical and mechanical durability
US9186295B2 (en) 2011-10-25 2015-11-17 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9198829B2 (en) 2011-10-25 2015-12-01 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9241869B2 (en) 2011-10-25 2016-01-26 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9340447B2 (en) 2011-10-25 2016-05-17 Corning Incorporated Glass compositions with improved chemical and mechanical durability
US9474689B2 (en) 2011-10-25 2016-10-25 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9474688B2 (en) 2011-10-25 2016-10-25 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US10413481B2 (en) 2011-10-25 2019-09-17 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US12275671B2 (en) 2011-10-25 2025-04-15 Corning Incorporated Glass compositions with improved chemical and mechanical durability
US9617183B2 (en) 2011-10-25 2017-04-11 Corning Incorporated Glass compositions with improved chemical and mechanical durability
US9624125B2 (en) 2011-10-25 2017-04-18 Corning Incorporated Glass compositions with improved chemical and mechanical durability
US8551898B2 (en) 2011-10-25 2013-10-08 Corning Incorporated Glass compositions with improved chemical and mechanical durability
US11707409B2 (en) 2011-10-25 2023-07-25 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US11707408B2 (en) 2011-10-25 2023-07-25 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US10413482B2 (en) 2011-10-25 2019-09-17 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US11325855B2 (en) 2011-10-25 2022-05-10 Corning Incorporated Glass compositions with improved chemical and mechanical durability
US10196298B2 (en) 2011-10-25 2019-02-05 Corning Incorporated Glass compositions with improved chemical and mechanical durability
US11168017B2 (en) 2011-10-25 2021-11-09 Corning Incorporated Alkaline earth alumino-silicate glass compositions with improved chemical and mechanical durability
US9718721B2 (en) 2011-10-25 2017-08-01 Corning Incorporated Alkaline earth alumino-silicate glass compositions with improved chemical and mechanical durability
US10597322B2 (en) 2011-10-25 2020-03-24 Corning Incorporated Glass compositions with improved chemical and mechanical durability
US10441505B2 (en) 2011-10-25 2019-10-15 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US10577274B2 (en) 2011-10-25 2020-03-03 Corning Incorporated Alkaline earth alumino-silicate glass compositions with improved chemical and mechanical durability
US10577287B2 (en) 2011-11-30 2020-03-03 Corning Incorporated Complex structures in refractory bodies and methods of forming
US9714729B2 (en) 2011-11-30 2017-07-25 Corning Incorporated Complex structures in refractory bodies and methods of forming
WO2013082257A1 (en) * 2011-11-30 2013-06-06 Corning Incorporated Complex structures in refractory bodies and methods of forming
CN104185504A (zh) * 2011-11-30 2014-12-03 康宁股份有限公司 耐火体中的复杂结构及其形成方法
US11492291B2 (en) 2012-02-29 2022-11-08 Corning Incorporated Ion exchanged glasses via non-error function compressive stress profiles
US9786559B2 (en) 2012-03-30 2017-10-10 Intel Corporation Process and material for preventing deleterious expansion of high aspect ratio copper filled through silicon vias (TSVs)
US20140117559A1 (en) * 2012-03-30 2014-05-01 Paul A. Zimmerman Process and material for preventing deleterious expansion of high aspect ratio copper filled through silicon vias (tsvs)
US10273048B2 (en) 2012-06-07 2019-04-30 Corning Incorporated Delamination resistant glass containers with heat-tolerant coatings
US12391600B2 (en) 2012-06-28 2025-08-19 Corning Incorporated Delamination resistant glass containers with heat-tolerant coatings
US10273049B2 (en) 2012-06-28 2019-04-30 Corning Incorporated Delamination resistant glass containers with heat-tolerant coatings
US9839579B2 (en) 2013-04-24 2017-12-12 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9707154B2 (en) 2013-04-24 2017-07-18 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9717649B2 (en) 2013-04-24 2017-08-01 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9717648B2 (en) 2013-04-24 2017-08-01 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9849066B2 (en) 2013-04-24 2017-12-26 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9603775B2 (en) 2013-04-24 2017-03-28 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9713572B2 (en) 2013-04-24 2017-07-25 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9700485B2 (en) 2013-04-24 2017-07-11 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9700486B2 (en) 2013-04-24 2017-07-11 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9707153B2 (en) 2013-04-24 2017-07-18 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US9707155B2 (en) 2013-04-24 2017-07-18 Corning Incorporated Delamination resistant pharmaceutical glass containers containing active pharmaceutical ingredients
US11079309B2 (en) 2013-07-26 2021-08-03 Corning Incorporated Strengthened glass articles having improved survivability
US11634359B2 (en) 2014-02-24 2023-04-25 Corning Incorporated Strengthened glass with deep depth of compression
US11878941B2 (en) 2014-06-19 2024-01-23 Corning Incorporated Glasses having non-frangible stress profiles
US12297145B2 (en) 2014-06-19 2025-05-13 Corning Incorporated Glasses having non-frangible stress profiles
US11220456B2 (en) 2014-10-08 2022-01-11 Corning Incorporated Glasses and glass ceramics including a metal oxide concentration gradient
US11465937B2 (en) 2014-10-08 2022-10-11 Corning Incorporated Glasses and glass ceramics including a metal oxide concentration gradient
US12187639B2 (en) 2014-10-08 2025-01-07 Corning Incorporated Glasses and glass ceramics including a metal oxide concentration gradient
US10364182B2 (en) * 2014-10-08 2019-07-30 Corning Incorporated Glasses and glass ceramics including a metal oxide concentration gradient
US11459270B2 (en) 2014-10-08 2022-10-04 Corning Incorporated Glasses and glass ceramics including a metal oxide concentration gradient
US11746046B2 (en) 2014-10-31 2023-09-05 Corning Incorporated Strengthened glass with ultra deep depth of compression
US11084756B2 (en) 2014-10-31 2021-08-10 Corning Incorporated Strengthened glass with ultra deep depth of compression
US11377388B2 (en) 2014-11-04 2022-07-05 Corning Incorporated Deep non-frangible stress profiles and methods of making
US11021393B2 (en) 2014-11-04 2021-06-01 Corning Incorporated Deep non-frangible stress profiles and methods of making
US11267228B2 (en) 2015-07-21 2022-03-08 Corning Incorporated Glass articles exhibiting improved fracture performance
US11613103B2 (en) 2015-07-21 2023-03-28 Corning Incorporated Glass articles exhibiting improved fracture performance
US12297141B2 (en) 2015-12-11 2025-05-13 Corning Incorporated Fusion-formable glass-based articles including a metal oxide concentration gradient
US11878936B2 (en) 2015-12-11 2024-01-23 Corning Incorporated Fusion-formable glass-based articles including a metal oxide concentration gradient
US11472734B2 (en) 2015-12-11 2022-10-18 Corning Incorporated Fusion-formable glass-based articles including a metal oxide concentration gradient
US11279652B2 (en) 2016-04-08 2022-03-22 Corning Incorporated Glass-based articles including a metal oxide concentration gradient
US12116311B2 (en) 2016-04-08 2024-10-15 Corning Incorporated Glass-based articles including a metal oxide concentration gradient
US11963320B2 (en) 2016-04-08 2024-04-16 Corning Incorporated Glass-based articles including a stress profile comprising two regions
US11174197B2 (en) 2016-04-08 2021-11-16 Corning Incorporated Glass-based articles including a metal oxide concentration gradient
US11691913B2 (en) 2016-04-08 2023-07-04 Corning Incorporated Glass-based articles including a metal oxide concentration gradient

Also Published As

Publication number Publication date
JP2009517319A (ja) 2009-04-30
US20100120603A1 (en) 2010-05-13
CN101316799A (zh) 2008-12-03
WO2007063092A1 (en) 2007-06-07
ATE506330T1 (de) 2011-05-15
DE602006021471D1 (de) 2011-06-01
US20120172191A1 (en) 2012-07-05
US8252708B2 (en) 2012-08-28
EP1963235A1 (en) 2008-09-03
JP5355090B2 (ja) 2013-11-27
EP2269959A1 (en) 2011-01-05
CN101316799B (zh) 2013-03-27
EP1963235B1 (en) 2011-04-20
KR20080072082A (ko) 2008-08-05

Similar Documents

Publication Publication Date Title
US8252708B2 (en) Crystallization-free glass frit compositions and frits made therefrom for microreactor devices
EP3717423B1 (en) Black lithium silicate glass ceramics
CN105683106A (zh) 含硼和磷的可离子交换玻璃
KR102804605B1 (ko) 블랙 베타-스포듀민 리튬 실리케이트 유리 세라믹
EP2065347A1 (en) Durable frit composition and composites and devices comprised thereof
Zaid Effect of sintering on crystallization and structural properties of soda lime silica glass
Sharma et al. A new formulation of barium–strontium silicate glasses and glass-ceramics for high-temperature sealant
Bai et al. Non-isothermal crystallization kinetics of stoichiometric lithium disilicate-based glasses with Al2O3 additives
Sharma et al. Synergic effect of V2O5 and P2O5 on the sealing properties of barium–strontium–alumino-silicate glass/glass–ceramics
Shelby Properties and morphology of barium germanate glasses
Oliver Crystal nucleation and growth in soda-lime-silica glasses.
Agersted et al. Commercial alkaline earth boroaluminosilicate glasses for sealing solid oxide cell stacks. Part I: Development of glass‐ceramic microstructure and thermomechanical properties
Yu The application of waste float glass, recycled in structural beams made with the glass casting method
Bengisu et al. Glasses and glass-ceramics in the SrO–TiO2–Al2O3–SiO2–B2O3 system and the effect of P2O5 additions
Pagnotta Packaging Glasses from Containers to Encapsulation: Composition, Performance, and Sustainability Pathways
WO2019121992A1 (en) Sealing compositions
CN105246848B (zh) 含有硬硼酸钙石的新钠钙硅酸盐玻璃组合物及其制备方法
Criscenti et al. Tailored Property and Processing Particle-Filled-Glass Composite Design and Development.
da Rocha Fernandes Development of lithium disilicate based glass-ceramics
Kölker A systematic approach to fibre glass development
Bouche et al. Nucleation and crystal growth kinetics of glass-ceramics in the BaO-CaO-Al2O3-SiO2-B2O3 system
Goel Clinopyroxene based glasses and glass-ceramics for functional applications

Legal Events

Date Code Title Description
AS Assignment

Owner name: CORNING INCORPORATED, NEW YORK

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MORENA, ROBERT MICHAEL;MARQUES, PAULO JORGE;HAGY, HENRY EDWIN;REEL/FRAME:018593/0410;SIGNING DATES FROM 20060925 TO 20061018

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION