WO2018127527A1 - Low melting glass for protecting oxygen sensitive organics - Google Patents

Low melting glass for protecting oxygen sensitive organics Download PDF

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Publication number
WO2018127527A1
WO2018127527A1 PCT/EP2018/050161 EP2018050161W WO2018127527A1 WO 2018127527 A1 WO2018127527 A1 WO 2018127527A1 EP 2018050161 W EP2018050161 W EP 2018050161W WO 2018127527 A1 WO2018127527 A1 WO 2018127527A1
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WIPO (PCT)
Prior art keywords
optically transparent
mixture
low melting
transparent mixture
organic luminescent
Prior art date
Application number
PCT/EP2018/050161
Other languages
French (fr)
Inventor
Paulus Hubertus Gerardus Offermans
Michael Maria Johannes VAN LIEROP
Ronaldus Mathias Hubertus Steijvers
Nicolaas Petrus Willard
Original Assignee
Koninklijke Philips N.V.
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Publication of WO2018127527A1 publication Critical patent/WO2018127527A1/en

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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
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/16—Silica-free oxide glass compositions containing phosphorus
    • 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
    • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • C03C14/004—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of particles or flakes
    • 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
    • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • C03C14/008—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in molecular form
    • 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
    • C03C4/00—Compositions for glass with special properties
    • C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
    • 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
    • C03C2214/00—Nature of the non-vitreous component
    • C03C2214/04—Particles; Flakes
    • 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
    • C03C2214/00—Nature of the non-vitreous component
    • C03C2214/30—Methods of making the composites
    • 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
    • C03C2214/00—Nature of the non-vitreous component
    • C03C2214/34—Nature of the non-vitreous component comprising an impregnation by molten glass step
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6434—Optrodes
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N2021/7769—Measurement method of reaction-produced change in sensor
    • G01N2021/7786—Fluorescence

Definitions

  • the invention relates generally to sensors for analysis of gas. Specifically, the invention relates to a low melting glass for protection of oxygen sensitive organics, such as for protection of organic luminescent reference material for use in C0 2 sensors.
  • CO2 Carbon Dioxide
  • an organic luminescent reference material is often used.
  • Such sensors can be used to sense concentration of CO2 in a gas og from contact with a person's skin for transcutaneous blood CO2 concentration.
  • CO2 sensor An example of a CO2 sensor may be seen in WO 2004/077035.
  • optical sensor material which has a long life time also in environments where it is exposed to oxygen.
  • the invention provides an optically transparent mixture comprising
  • Such mixture is advantageous, since a dye of such mixture can be used in sensors for optical sensing of e.g. CO2, where the dye may come into contact with a fluid.
  • low melting glass will protect the organic reference material which is preferably spatially distributed as particles and embedded in the low melting glass to form a dye, because oxygen diffusion through the low melting glass material does not occur.
  • the organic reference material can be provided in such mixture at a temperature low enough to ensure that the organic material is not damaged.
  • ow transparent low melting glass is a solution because oxygen diffusion through the material does not occur.
  • the low melting glass composition comprises TinPhosphate glass.
  • the TinPhosphate glass may comprise SnP0 4 ranging from 58 to 65 molar percentage of Sn and from 35 to 42 molar percentage of P0 4 .
  • the low melting glass composition is preferably selected such that it has a glass transition temperature in the temperature range 160 °C to 250 °C.
  • organic luminescent reference material forms a fraction of 0.01 to 1 % mass of the mixture, especially the organic luminescent reference material may form a fraction of 0.05 to 0.5 % mass of the mixture.
  • the organic luminescent reference material is preferably stable at a
  • luminescent material it is preferred that it has an emission decay time within the interval 10 ns to 100 ⁇ , and most preferably within the interval 0.1 to 10 ⁇ .
  • luminescent materials with such optical properties are organo metal complexes, e.g. Pt, Ru, Ir, Re and Os as metal ion.
  • the preferred organic luminescent reference material comprises [Ru(bpy)3]Cb, such as 90-100% of [Ru(bpy)3]Cb. However it is to be understood that other materials may be used as an alternative or additionally to [Ru(bpy)3]Cb.
  • the organic luminescent reference material is preferably distributed as a plurality of particles embedded in the low melting glass composition, and most preferably shaped as a dye for use in an optical sensor for sensing of e.g. C0 2 , where the dye is arranged for fluid contact.
  • the mixture is preferably optically transparent at least in the wavelength interval of 400 nm to 800 nm.
  • Optically transparent' is understood at least 60%
  • the invention provides a sensor device comprising
  • such sensor device may comprise a dye of the mixture arranged in or on a supporting structure, so as to allow an optical sensor, as known in the art, to sense an optical signal from the optically transparent mixture.
  • the optical sensor may be arranged to provide an output in accordance with an amount of CO2 being in contact with a surface of the optically transparent mixture.
  • the optical sensor is arranged to sense a property of a gas.
  • the optical sensor is a transcutaneous sensor arranged to sense a property of e.g. a blood in a subject transcutaneously.
  • the invention provides a method of manufacturing an optically transparent mixture, the method comprises
  • the method of manufacturing may comprise heating the low melting glass blend to a maximum temperature in the range 350 °C to 450 °C.
  • FIG. 3 illustrates a method embodiment. DESCRIPTION OF EMBODIMENTS
  • FIGs. la and lb show photos the same dye of a glass mixture embodiment MX.
  • the particles of luminescent organic reference material is barely visible in the low melting glass GL, whereas in FIG. lb, these particles LM are clearly visible as light spotsin the glass GL, due to the use of confocal fluorescence microscopy.
  • 3D resolution is accomplished by actively suppressing any signal coming from out-of- focus planes. Light originating from an in-focus plane is imaged by the microscope objective whereas light coming from out-of- focus planes is largely blocked.
  • FIG. 2 shows an example of a dye of glass mixture MX arranged as a disposable part of a sensor device for transcutaneous optical sensing of C0 2 level in a person's blood.
  • the sensor layer with the reference material is preferably only used once.
  • the glass mixture MX is positioned below an optical window W, and in a liquid filled cavity above a grid or mesh MSH which contacts the skin SKN of the person.
  • the grid of mesh MSH may be made of metal and may be formed as part of an adhesive tape TP which is arranged to stick onto the skin SKN.
  • a connecting structure CN is arranged for positioning of an optical sensor which can then sense optical signals from the glass mixture MX through the optical window W.
  • the glass mixture MX Due to the low melting glass properties of the glass mixture MX, it can serve many purposes in optical parts or devices, serve as organic host material, and in particularly as non-penetrable gas/water barrier sealing material. All conventional polymers are water absorbing and water penetrablepermeable, rendering non hygroscopic (attraction of water) low melting glasses highly desirable for many sealing applications.
  • FIG. 3 shows steps of a method of manufacturing embodiment.
  • the method comprises first providing P GB a low melting glass blend of at least two different materials, preferably in powder form. Next, heating H GB this low melting glass blend to a temperature of at least 350 °C to obtain a melted homogeneous glass blend. Next, decreasing temperature D TPl of the melted homogeneous glass blend at a moderate rate, e.g. at a rate of less than 20 °C per minute. Then adding A LM a portion of an organic luminescent reference material, e.g. in powder form, to the melted homogeneous glass blend after temperature has been decreased to less than 300 °C, e.g.
  • the temperature of the glass mixture is slowly, preferably at a rate of less than 20 °C per minute decreased to 250 °C and 2 mgram of Tris(bipyridine)ruthenium(II) chloride (Ru DPP C12 i.e [Ru(bpy)3]Cl 2 ) is added to obtain a 0,1 % mixture.
  • the mixture is again stirred until a homogeneous mixture is obtained.
  • the mixture is then cooled to room temperature (such as 15-30°C) and the luminescent properties of the organic dye may be measured.
  • the mixture is stable in water and in high humidity conditions and can be used in chemo-optical C0 2 sensors.
  • the invention provides an optically transparent mixture comprising an organic luminescent reference material, and a low melting glass composition.
  • This can be used as an attractive component in optical C0 2 sensors, since the protection of the organic material against oxygen when embedded in the low melting class serves to provide a long life time for such organic luminescent reference material.
  • the low melting glass composition may comprise TinPhosphate glass
  • the organic luminescent reference material may comprise [Ru(bpy)3]Cl 2 .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

An optically transparent mixture comprising an organic luminescent reference material, and a low melting glass composition. This can be used as an attractive component in optical CO2 sensors, since the protection of the organic material against oxygen when embedded in the low melting class serves to provide a long life time for such organic luminescent reference material. Especially, the low melting glass composition may comprise TinPhosphate glass, and the organic luminescent reference material may comprise [Ru(bpy)3]Cl2.

Description

LOW MELTING GLASS FOR PROTECTING OXYGEN SENSITIVE ORGANICS
FIELD OF THE INVENTION
The invention relates generally to sensors for analysis of gas. Specifically, the invention relates to a low melting glass for protection of oxygen sensitive organics, such as for protection of organic luminescent reference material for use in C02 sensors.
BACKGROUND OF THE INVENTION
In a Carbon Dioxide (CO2) sensors, an organic luminescent reference material is often used. Such sensors can be used to sense concentration of CO2 in a gas og from contact with a person's skin for transcutaneous blood CO2 concentration.
It is a problem with such sensors, that the reference material is oxygen sensitive and thus has to be protected from any fluid contact. Packing in transparent organic material is insufficient, since oxygen diffuses through the organic network over time, thereby limiting the lifetime.
An example of a CO2 sensor may be seen in WO 2004/077035.
SUMMARY OF THE INVENTION
Following the above, the inventors of the present invention have appreciated that an improved material for optical sensors, e.g. for sensing CO2, is advantageous.
In particular, it may be seen as an object of the present invention to provide an optical sensor material which has a long life time also in environments where it is exposed to oxygen.
In a first aspect, the invention provides an optically transparent mixture comprising
- an organic luminescent reference material, and
- a low melting glass composition.
Such mixture is advantageous, since a dye of such mixture can be used in sensors for optical sensing of e.g. CO2, where the dye may come into contact with a fluid. It is based on the insigtht of the inventors that low melting glass will protect the organic reference material which is preferably spatially distributed as particles and embedded in the low melting glass to form a dye, because oxygen diffusion through the low melting glass material does not occur. Further, the it is based on the insight of the inventors, that the organic reference material can be provided in such mixture at a temperature low enough to ensure that the organic material is not damaged. Further, it is based on the insight that ow transparent low melting glass is a solution because oxygen diffusion through the material does not occur.
Thus, by mixing the luminescent reference particles in a melt of the low melting glass, an excellent and optically transparent protection of the organics is gained obtained and the mixing temperature is that low that degradation of the luminescent organic material does not occur.
Transparent mixture of polymers and low melting glass is possible with commercial techniques. Melting temperatures of both the glass as the organic
materials/polymers is in the temperature range.
In the following, preferred embodiments or features of the first aspect will be described.
In preferred embodiments, the low melting glass composition comprises TinPhosphate glass. Especially, the TinPhosphate glass may comprise SnP04 ranging from 58 to 65 molar percentage of Sn and from 35 to 42 molar percentage of P04. The
TinPhosphate glass may comprise P2O5 at a fraction of 30-60 molar percentage.
The low melting glass composition is preferably selected such that it has a glass transition temperature in the temperature range 160 °C to 250 °C.
It is preferred, that organic luminescent reference material forms a fraction of 0.01 to 1 % mass of the mixture, especially the organic luminescent reference material may form a fraction of 0.05 to 0.5 % mass of the mixture.
The organic luminescent reference material is preferably stable at a
temperature of up to at least 250 °C, preferably it is stable up to a temperature of such as 275 °C or up to 300 °C or even more than 300 °C. Regarding optical properties of the
luminescent material, it is preferred that it has an emission decay time within the interval 10 ns to 100 μβ, and most preferably within the interval 0.1 to 10 μβ. Examples of luminescent materials with such optical properties are organo metal complexes, e.g. Pt, Ru, Ir, Re and Os as metal ion.
Specific examples of luminescent materials to be selected as the organic luminescent reference material are: 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin platinum(II), (l,10-phenanthroline)ruthenium(II) dichloride, [Ru(bpy)3]Cl2, Europium(III) tris( 1 ,3-diphenyl- 1 ,3-propanedionato) mono( 1 , 10-phenanthroline), [Re( N-N)(CO) py- - mal)](CF3S03) [N-N = 1,10-phenanthroline, phen (1), 2,9-dimethyl- 1,10-phenanthroline, 2,9- Me?-phen (2), 3,4,7,8-tetramethyl-l,10 -phcnanthro!ine, 3,4.7,8-Met-phen (3), 4,7-diphenyl- 1.10-phenanthroline, 4,7-Ph.2-phen (4), 2,9-dimeth.yl-4,7-diphenyl-l,10-phenanth.roline, 2,9- Mc?-4,7-Ph:'-phen (5), 2.2'-biqumonine, biq (6); py-3-mal = - ( - p y r i d y I ) m a I e i m i d e | , iridium(III) bipyridinc-aldehyde complexes [Ir(N-C) 2(bpy-CHO)] (PF 6) (HN-C 2- phenylpyridine, Hppy (1); 2-(4-methylphenyl)pyridine, Hmppy (2); 1 -phenylpyrazole, Hppz (3); 3-mothyl- 1 -phenylpyrazolc, Hmppz (4); 7,8-bcnzoquino!ine, Hbzq (5); 2- phenylqiiinoline, Hpq (6); bpy-CHO=4-formyl- 4 -methy!-2,2 -bi pyridine).
The preferred organic luminescent reference material comprises [Ru(bpy)3]Cb, such as 90-100% of [Ru(bpy)3]Cb. However it is to be understood that other materials may be used as an alternative or additionally to [Ru(bpy)3]Cb.
The organic luminescent reference material is preferably distributed as a plurality of particles embedded in the low melting glass composition, and most preferably shaped as a dye for use in an optical sensor for sensing of e.g. C02, where the dye is arranged for fluid contact.
The mixture is preferably optically transparent at least in the wavelength interval of 400 nm to 800 nm. By Optically transparent' is understood at least 60%
transparent, preferably at least 80% transparent, most preferably at least 90% transparent.
In a second aspect, the invention provides a sensor device comprising
- an optically transparent mixture according to the first aspect.
Especially, such sensor device may comprise a dye of the mixture arranged in or on a supporting structure, so as to allow an optical sensor, as known in the art, to sense an optical signal from the optically transparent mixture.
Especially, the sensor device may comprise an optical sensor arranged adjacent to the optically transparent mixture, so as to sense an optical signal from the organic luminescent material, and to provide an output accordingly. Such optical sensor may form a fixed part of the sensor device, or it can form a separate part arranged to be mounted onto a separate part comprising the optically transparent mixture, when in use. The separate part comprising the optically transparent mixture may be in the form of a disposable part, whereas the optical sensor part may be reused.
Especially, the optical sensor may be arranged to provide an output in accordance with an amount of CO2 being in contact with a surface of the optically transparent mixture. In one sensor embodiment, the optical sensor is arranged to sense a property of a gas. In another sensor embodiment, the optical sensor is a transcutaneous sensor arranged to sense a property of e.g. a blood in a subject transcutaneously.
In a third aspect, the invention provides a method of manufacturing an optically transparent mixture, the method comprises
- providing a low melting glass blend of at least two different materials,
- heating the low melting glass blend to at least 350 °C to obtain a melted homogeneous glass blend,
- decreasing temperature of the melted homogeneous glass blend at a moderate rate,
- adding a portion of an organic luminescent reference material to the melted homogeneous glass blend after temperature has been decreased to less than 300 °C to form a homogeneous mixture, and
- decreasing temperature to below glass transition temperature of the homogeneous mixture, thereby forming the optically transparent mixture.
Especially, the method of manufacturing may comprise heating the low melting glass blend to a maximum temperature in the range 350 °C to 450 °C.
It is to be understood that said at least two different materials are in the form of a powder or the like before being blended and heated. The portion of organic luminescent reference material is also added as a powder or at least fractioned so as to form particles in the final mixture. By 'decreasing temperature at a moderate rate' is understood a rate of decrease of 30 °C per minute or less, preferably a rate of 20 °C per minute or less.
In general, it is appreciated that the various aspects of the invention may be combined and coupled in any way possible within the scope of the invention. These and other aspects, features and/or advantages of the invention will be apparent from and elucidated with reference to the embodiments described hereinafter.
BRIEF DESCRIPTION OF THE DRAWINGS
Embodiments of the invention will be described, by way of example only, with reference to the drawings, in which
FIGs. la and lb show photos of a dye of a glass mixture embodiment,
FIG. 2 illustrates a sketch of a transcutaneous optical sensor embodiment,
FIG. 3 illustrates a method embodiment. DESCRIPTION OF EMBODIMENTS
FIGs. la and lb show photos the same dye of a glass mixture embodiment MX. In FIG. la, the particles of luminescent organic reference material is barely visible in the low melting glass GL, whereas in FIG. lb, these particles LM are clearly visible as light spotsin the glass GL, due to the use of confocal fluorescence microscopy. Hereby true 3D resolution is accomplished by actively suppressing any signal coming from out-of- focus planes. Light originating from an in-focus plane is imaged by the microscope objective whereas light coming from out-of- focus planes is largely blocked.
FIG. 2 shows an example of a dye of glass mixture MX arranged as a disposable part of a sensor device for transcutaneous optical sensing of C02 level in a person's blood. The sensor layer with the reference material is preferably only used once. The glass mixture MX is positioned below an optical window W, and in a liquid filled cavity above a grid or mesh MSH which contacts the skin SKN of the person. The grid of mesh MSH may be made of metal and may be formed as part of an adhesive tape TP which is arranged to stick onto the skin SKN. A connecting structure CN is arranged for positioning of an optical sensor which can then sense optical signals from the glass mixture MX through the optical window W.
Due to the low melting glass properties of the glass mixture MX, it can serve many purposes in optical parts or devices, serve as organic host material, and in particularly as non-penetrable gas/water barrier sealing material. All conventional polymers are water absorbing and water penetrablepermeable, rendering non hygroscopic (attraction of water) low melting glasses highly desirable for many sealing applications.
FIG. 3 shows steps of a method of manufacturing embodiment. The method comprises first providing P GB a low melting glass blend of at least two different materials, preferably in powder form. Next, heating H GB this low melting glass blend to a temperature of at least 350 °C to obtain a melted homogeneous glass blend. Next, decreasing temperature D TPl of the melted homogeneous glass blend at a moderate rate, e.g. at a rate of less than 20 °C per minute. Then adding A LM a portion of an organic luminescent reference material, e.g. in powder form, to the melted homogeneous glass blend after temperature has been decreased to less than 300 °C, e.g. decreased to 250 °C, and stirring it, so as to form a homogeneous mixture. Finally, decreasing temperature D TP2 to below glass transition temperature of the homogeneous mixture, thereby forming a dye of the optically transparent mixture. In the following a specific example of manufacturing a glass mixture is described. A mixture of 1 gram Sn P04 and 1 gram P205 is mixed and heated to 450 °C until a homogeneous mixture is obtained. The temperature of the glass mixture is slowly, preferably at a rate of less than 20 °C per minute decreased to 250 °C and 2 mgram of Tris(bipyridine)ruthenium(II) chloride (Ru DPP C12 i.e [Ru(bpy)3]Cl2) is added to obtain a 0,1 % mixture. The mixture is again stirred until a homogeneous mixture is obtained. The mixture is then cooled to room temperature (such as 15-30°C) and the luminescent properties of the organic dye may be measured. The mixture is stable in water and in high humidity conditions and can be used in chemo-optical C02 sensors.
To sum up, the invention provides an optically transparent mixture comprising an organic luminescent reference material, and a low melting glass composition. This can be used as an attractive component in optical C02 sensors, since the protection of the organic material against oxygen when embedded in the low melting class serves to provide a long life time for such organic luminescent reference material. Especially, the low melting glass composition may comprise TinPhosphate glass, and the organic luminescent reference material may comprise [Ru(bpy)3]Cl2.
While the invention has been illustrated and described in detail in the drawings and foregoing description, such illustration and description are to be considered illustrative or exemplary and not restrictive; the invention is not limited to the disclosed embodiments. Other variations to the disclosed embodiments can be understood and effected by those skilled in the art in practicing the claimed invention, from a study of the drawings, the disclosure, and the appended claims. In the claims, the word "comprising" does not exclude other elements or steps, and the indefinite article "a" or "an" does not exclude a plurality. A single processor or other unit may fulfill the functions of several items recited in the claims. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage. A computer program may be stored/distributed on a suitable medium, such as an optical storage medium or a solid-state medium supplied together with or as part of other hardware, but may also be distributed in other forms, such as via the Internet or other wired or wireless
telecommunication systems. Any reference signs in the claims should not be construed as limiting the scope.

Claims

1. An optically transparent mixture (MX) comprising - an organic luminescent reference material (LM), and - a low melting glass composition (GL).
2. The optically transparent mixture (MX) according to claim 1, wherein the low melting glass composition (GL) comprises TinPhosphate glass.
3. The optically transparent mixture (MX) according to claim 1, wherein said TinPhosphate glass (GL) comprises SnP04 ranging from 58 to 65 molar percentage of Sn and from 35 to 42 molar percentage of P04.
4. The optically transparent mixture (MX) according to claim 3, wherein said TinPhosphate glass (GL) comprises P2O5 at a fraction of 30-60 molar percentage.
5. The optically transparent mixture (MX) according to claim 1, wherein the low melting glass composition (GL) is selected to have a glass transition temperature in the temperature range 160 °C to 250 °C.
6. The optically transparent mixture (MX) according to claim 1, wherein the organic luminescent reference material (LM) is distributed as a plurality of particles embedded in the low melting glass composition (GL), and wherein the organic luminescent reference material (LM) forms a fraction of 0.01 to 1 % mass of the mixture (MX).
7. The optically transparent mixture (MX) according to claim 1, wherein the organic luminescent reference material (LM) is selected such that it is stable at temperatures of up to at least 250 °C.
8. The optically transparent mixture (MX) according to claim 1, wherein the organic luminescent reference material (LM) is selected to have optical properties with an emission decay time being within the interval 10 ns to 100 μβ.
9. The optically transparent mixture (MX) according to claim 1, wherein the organic luminescent reference material (LM) comprises [Ru(bpy)3]Ck.
10. The optically transparent mixture (MX) according to claim 1, wherein the mixture (MX) is optically transparent at least in the wavelength interval of 400 nm to 800 nm.
11. A sensor device comprising an optically transparent mixture (MX) according to claim 1.
12. The sensor device according to claim 11, comprising an optical sensor arranged adjacent to the optically transparent mixture (MX), so as to sense an optical signal from the organic luminescent material (LM), and to provide an output accordingly.
13. The sensor device according to claim 11, wherein the optical sensor is arranged to provide an output in accordance with an amount of C02 being in contact with a surface of the optically transparent mixture (MX).
14. A method of manufacturing an optically transparent mixture (MX), the method comprises
- providing (P GB) a low melting glass blend of at least two different materials, - heating (H GB) the low melting glass blend to at least 350 °C to obtain a melted homogeneous glass blend,
- decreasing temperature (D TPl) of the melted homogeneous glass blend at a moderate rate, - adding (A LM) a portion of an organic luminescent reference material to the melted homogeneous glass blend after temperature has been decreased to less than 300 °C to form a homogeneous mixture, and - decreasing temperature (D TP2) to below glass transition temperature of the homogeneous mixture, thereby forming the optically transparent mixture (MX).
15. The method of manufacturing according to claim 14, comprising heating the low melting glass blend to a maximum temperature in the range 350 °C to 450 °C.
PCT/EP2018/050161 2017-01-05 2018-01-04 Low melting glass for protecting oxygen sensitive organics WO2018127527A1 (en)

Applications Claiming Priority (2)

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US201762442570P 2017-01-05 2017-01-05
US62/442,570 2017-01-05

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4379070A (en) * 1982-04-26 1983-04-05 Corning Glass Works Tin-phosphorus oxyfluoride glass containing aromatic organic compound
WO2004077035A1 (en) 2003-02-28 2004-09-10 Gas Sensors Solutions Limited Optical co2 and combined 02/co2 sensors

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4379070A (en) * 1982-04-26 1983-04-05 Corning Glass Works Tin-phosphorus oxyfluoride glass containing aromatic organic compound
WO2004077035A1 (en) 2003-02-28 2004-09-10 Gas Sensors Solutions Limited Optical co2 and combined 02/co2 sensors

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