Temperature sensor with heat-sensitive paste
11333560 · 2022-05-17
Assignee
Inventors
Cpc classification
H01C17/00
ELECTRICITY
International classification
G01K7/00
PHYSICS
Abstract
A heat-sensitive resistor with a negative or positive temperature coefficient comprises respectively an antimony-doped tin oxide-based resistive element or a carbon black-based resistive element, containing a polymer having a dielectric constant between 2 and 3, a molar mass between 50000 and 150000 g/mol, and a glass transition temperature Tg between 40 and 100° C.
Claims
1. A circuit comprising a support and, on the support, a heat-sensitive resistor of negative or positive temperature coefficient, respectively comprising a resistive element based on antimony tin oxide, said resistive element also containing a polymer having a dielectric constant between 2 and 3, a molar mass between 50,000 and 150,000 g/mol, and a glass transition temperature Tg between 40 and 100° C., and wherein the polymer belongs to the family of styrenic polymers or to the family of fluorinated polymers.
2. The circuit of claim 1, wherein the resistive element comprises from 5% to 40% by mass of dry extract of the polymer with respect to the total mass of the resistive element.
3. The circuit of claim 1, wherein the heat-sensitive resistor further comprises a resistive element based on carbon black, said resistive element also containing a polymer having a dielectric constant between 2 and 3, a molar mass between 50,000 and 150,000 g/mol, and a glass transition temperature Tg between 40 and 100° C.
4. The circuit of claim 3, wherein the heat sensitive resistor is of positive temperature coefficient having an adjustable threshold temperature with a resistance which is constant below said threshold and which increases along with temperature above said threshold comprising a first resistive track made of a heat-sensitive paste of positive temperature coefficient, PTC, arranged in electrical series with a second resistive track made of a heat-sensitive paste of negative temperature coefficient, NTC.
5. A method of manufacturing a heat-sensitive resistor of negative or positive temperature coefficient, comprising the steps of: forming a first solution comprising antimony tin oxide, said first solution also containing a polymer having a dielectric constant between 2 and 3, a molar mass between 50,000 and 150,000 g/mol, and a glass transition temperature Tg between 40 and 100° C., and wherein the polymer belongs to the family of styrenic polymers or to the family of fluorinated polymers; forming portions of the first solution on a support; and heating the portions.
6. The method of claim 5, wherein the step of manufacturing the first solution comprises the step of: providing a second solution comprising antimony tin oxide or carbon black and a first solvent; providing a third solution comprising the polymer and a second solvent; and mixing the second and third solutions to provide the first solution.
7. The method of claim 6, wherein the third solution is by a mass proportion smaller than 30%, preferably from 10 to 30% with respect to the total mass of the first solution.
8. The method of claim 6, the third solution comprises from 15 to 30% by mass, for example, 25%, of the polymer in from 85 to 70% by mass, for example, 75%, of the second solvent.
9. The method of claim 6, wherein the first solvent is selected from the group comprising cyclopentanone, ethyl acetate, tetrahydrofuran, acetone, 3-hexanone, and 2-pentanone for antimony tin oxide or the group comprising cyclopentanone, dibutyl carbitol, and ethylene glycol diacetate for carbon black.
10. The method of claim 6, wherein the second solvent has an evaporation temperature in the range from 100 to 170° C.
11. The method of claim 6, wherein the second solvent is selected from the group comprising toluene or butyl acetate for styrenic polymers or perfluorotributylamine (FC43) for fluorinated polymers.
12. The method of claim 6, wherein the evaporation temperature of the first solvent is greater than the evaporation temperature of the second solvent.
13. The method of claim 5, further comprising the steps of: forming a fourth solution comprising carbon black containing a polymer having a dielectric constant between 2 and 3, a molar mass between 50,000 and 150,000 g/mol, and a glass transition temperature Tg between 40 and 100° C., and wherein the polymer belongs to the family of styrenic polymers or to the family of fluorinated polymers; forming portions of the fourth solution on a support; and heating the portions.
14. The method of claim 13 of manufacturing a heat-sensitive resistor of positive temperature coefficient having an adjustable temperature threshold with a resistance which is constant below said threshold and which increases along with temperature above said threshold, comprising the steps of: forming in series on the support a first portion made of a heat-sensitive paste of positive temperature coefficient, PTC, and a second portion made of a heat-sensitive paste of negative temperature coefficient, NTC, the first and/or the second portion being formed with the first solution; and heating the first and second portions to form first and second resistive tracks.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The foregoing and other features and advantages of the present invention will be discussed in detail in the following non-limiting description of specific embodiments in connection with the accompanying drawings, among which:
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DETAILED DESCRIPTION
(15) For clarity, the same elements have been designated with the same reference numerals in the various drawings and, further, the various drawings are not to scale. In the following description, unless otherwise indicated, terms “substantially”, “approximately”, and “in the order of” mean “to within 10%”. Further, only those elements which are useful to the understanding of the present description have been shown and will be described. In particular, the processing of the signals provided by the temperature sensors are well known by those skilled in the art and are not described any further.
(16) It should be noted that, in the following, the examples are given for sensors formed of heat-sensitive ink deposited on flexible substrates of PEN (polyethylene naphthalate) or PET (polyethylene terephthalate) type. However, the present invention also applies to the case where the substrate is a rigid substrate, for example, a glass substrate.
(17) Also, the examples are given in the case where detection temperatures from 50 to 120° C. are targeted.
(18) Generally, it is provided herein to add a polymer to a conventional NTC or PTC resistor ink, for example, an ink based on Sb.sub.2O.sub.5SnO.sub.2 for the NTC ink and an ink based on carbon black for the PTC ink. The polymer has a dielectric constant in the range from 2 to 3, a molar mass (characterizing the chain length) in the range from 50,000 g/mol to 150,000 g/mol, and a glass transition temperature Tg in the range from 40° C. to 100° C. This polymer may belong to the family of styrenic polymers or to the family of fluorinated polymers. The dielectric constant of a material, also called relative permittivity, is equal to the ratio of the permittivity of the material to the permittivity of vacuum.
(19) NTC Ink:
(20) The NTC resistive paste or ink comprises a solution of ATO ink (Sb.sub.2O.sub.5SnO.sub.2) and of a polymer (P) such as defined hereabove.
(21) The method of preparing the NTC ink is the following. A solution of the polymer is prepared. The insulating polymer may be dissolved in a solvent having an evaporation temperature in the range from 100 to 170° C., for example, toluene (110° C. evaporation temperature), butyl acetate (118° C. evaporation temperature) for styrenic polymers or perfluorotributylamine (FC43, 165° C. evaporation temperature) for fluorinated polymers, with the following proportions relative to the total mass of the polymer solution: from 15 to 30% by mass, for example 25%, of the polymer and from 85 to 70% by mass, for example 75%, of the solvent.
(22) A solution of ATO ink which may correspond to the product commercialized by DuPont under trade name D7164 is further used.
(23) The solution of ATO ink may comprise one of the following solvents: cyclopentanone, ethyl acetate, tetrahydrofuran, 3-hexanone, 2-pentanone, or acetone. The ATO ink solution may comprise from 20% to 80% by mass of ATO and from 20% to 80% by mass of solvent.
(24) The obtained polymer solution is mixed with the solution of ATO ink (Sb.sub.2O.sub.5SnO.sub.2) with proportions by mass smaller than 30%, preferably from 10 to 30% with respect to the total mass of the obtained solution containing the polymer and the ATO. The obtained solution comprising the polymer and the ATO is then stirred for from 10 to 30 minutes at ambient temperature. The proportions used to manufacture the mixture enable to adapt the viscosity to a silk screening deposition.
(25) PTC Ink
(26) The PTC resistive paste or ink comprises a solution of carbon black and of a polymer (P) such as defined hereabove.
(27) The method of preparing the PTC ink is the following. A solution of the polymer is prepared. The insulating polymer may be dissolved in a solvent having an evaporation temperature in the range from 100 to 170° C., for example, toluene (110° C. evaporation temperature), butyl acetate (118° C. evaporation temperature) for styrenic polymers, or perfluorotributylamine (FC43, 165° C. evaporation temperature) for fluorinated polymers, with the following percentages with respect to the total mass of the polymer solution: from 15 to 30% by mass, for example 25%, of the polymer and from 85 to 70% by mass, for example 75%, of the solvent.
(28) A solution of carbon black which may correspond to the product commercialized by DuPont under trade name D7282 is further used. The carbon black solution may comprise cyclopentanone, dibutyl carbitol, or diacetate ethylene glycol as a solvent. The carbon black solution may comprise from 40% to 90% by mass of carbon black and from 10% to 60% by mass of solvent.
(29) The obtained polymer solution is mixed with the solution of carbon black with mass proportions smaller than 30%, preferably from 10 to 30% with respect to the total mass of the obtained solution containing the polymer and the carbon black. The obtained solution comprising the polymer and the carbon black is then stirred for from 10 to 30 minutes at ambient temperature. The proportions used to manufacture the mixture enable to adapt the viscosity to a silk screening deposition.
(30) The inventors have shown that, if a proportion of 30% by mass of the polymer solution in the solution containing the polymer and the ATO or the solution containing the polymer and the carbon black is exceeded, the printed layers may exhibit pores (holes), which may very strongly degrade the operation of the printed temperature sensor.
(31) Heat-sensitive resistors using the resistive pastes modified by addition of a polymer such as described hereabove may be manufactured on a flexible plastic substrate of polyethylene naphthalate (PEN) type or of polyethylene terephthalate (PET) type, or even on glass, for example, according to a method mainly comprising the steps described hereafter.
(32) The manufacturing method comprises a step of depositing portions of the polymer solution and of ATO ink and/or of depositing portions of the polymer solution and of carbon black. This deposition step is followed by a drying step to evaporate all the solvents of the polymer and ATO ink solution and/or of the polymer and carbon black solution.
(33) After drying, the obtained dry NTC ink comprises from 5% to 40%, preferably from 10% to 30%, by mass of dry polymer extract and from 60% to 95%, preferably from 70% to 90%, by mass of dry ATO extract with respect to the total mass of the dry NTC ink.
(34) After drying, the obtained dry PTC ink comprises from 5% to 40%, preferably from 10% to 30%, by mass of dry polymer extract and from 60% to 95%, preferably from 70% to 90%, by mass of dry carbon black extract with respect to the total mass of the dry PTC ink.
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(38) It can be observed that the introduction of the polymer into the ATO increases the resistivity and the temperature sensitivity thereof. With 30% by mass of polymer solution with respect to the total mass of the solution containing the polymer and the ATO, at 20° C., a resistance per square of 100/instead of 30/without polymer is reached. The temperature coefficient of resistance (TCR), equal to (1/R)×(dR/dT), increases in absolute value (it is negative in the case of the NTC ink); this increase is particularly significant in the range from 20 to 55° C.
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(41) The inks described herein may advantageously be used in temperature sensors with a Wheatstone bridge assembly.
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(43) Wheatstone bridge 20 may be formed by implementing the embodiment of manufacturing method previously described in relation with
(44) Wheatstone bridge 20 comprises two input terminals A and B between which is applied a power supply voltage V.sub.in and two output terminals C and D having a voltage V.sub.G measured therebetween. Wheatstone bridge 20 comprises two PTC resistors 22, 24 and two NTC resistors 26, 28 and four conductive tracks 30, 32, 34, and 36. One end of PTC resistor 22 is connected to terminal A by conductive track 30 and the other end of PTC resistor 22 is connected to terminal D by conductive track 36. One end of PTC resistor 24 is connected to terminal B by conductive track 32 and the other end of PTC resistor 24 is connected to terminal C by conductive track 34. One end of NTC resistor 26 is connected to terminal A by conductive track 30 and the other end of NTC resistor 26 is connected to terminal C by conductive track 34. One end of NTC resistor 28 is connected to terminal B by conductive track 32 and the other end of NTC resistor 28 is connected to terminal D by conductive track 36.
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(46) The polymer has a very strong effect on the sensitivity increase. Sensitivities of 100 mV/° C. at 60° C. may be reached for a temperature sensor supplied at 4.8 V and with 30% by mass of the polymer solution in the two NTC and PTC resistive inks, while with 0% of polymer, the sensitivity is only 30 mV/° C. at 60° C.
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(50) It should be noted that the shapes of the curves of
(51) An object of an embodiment is to make the resistance-vs.-temperature characteristic of resistive paste heat-sensitive resistors adjustable.
(52) According to an embodiment, the detection threshold of a temperature sensor is adjusted to target a defined detection range. According to an embodiment, a PTC paste which has a defined threshold, for example, a 35° C. threshold (that is, substantially no variation of the resistance value according to temperature below 35° C. and an exponential variation above this threshold) is used. To set this threshold, that is, to increase or to decrease it, one uses, in series with the PTC resistor, a NTC resistor which has no threshold but a substantially linear variation of the resistance according to temperature. Further, an adapted polymer may be added in each resistive paste to increase their temperature coefficient of resistance (TCR), that is, to increase their temperature sensitivity. The fact of serializing the PTC and NTC resistors enables to adjust the detection threshold of the PTC sensitive paste. The series assembly of the PTC and NTC resistors may then be integrated in an electric circuit of Wheatstone bridge type.
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(56) To obtain more varied variations of the characteristics of mixed resistors, it is here provided to use PTC and NTC resistors modified by addition of a selected proportion of a polymer as previously described. More specifically, it is provided herein to add a polymer to a conventional NTC or PTC resistor ink, for example, an ink based on Sb.sub.2O.sub.5SnO.sub.2 for the NTC ink and an ink based on carbon black for the PTC ink. As previously described, the polymer has a dielectric constant in the range from 2 to 3, a molar mass (characterizing the chain length) in the range from 50,000 g/mol to 150,000 g/mol, and a glass transition temperature Tg in the range from 40 to 100° C. This polymer may for example belong to the family of styrenic polymers or to the family of fluorinated polymers.
(57) Thus, by forming mixed resistors where one and/or the other of the NTC and PTC resistors is modified by addition of a variable quantity of a polymer of the above-described type, and by selecting the number of squares of each of these resistors, mixed resistors of desired characteristics may be formed, which have, in particular, a change of slope of their resistance at selected temperatures.
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According to an embodiment, resistors based on heat-sensitive pastes are deposited on flexible substrates of PEN (polyethylene naphthalate) or PET (polyethylene terephthalate) type. However, the foregoing also applies to the case where the substrate is a rigid substrate, for example, a glass substrate.