EP3309800A1 - Method for producing a layer structure using a paste based on a resistance alloy - Google Patents

Method for producing a layer structure using a paste based on a resistance alloy Download PDF

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Publication number
EP3309800A1
EP3309800A1 EP16193341.1A EP16193341A EP3309800A1 EP 3309800 A1 EP3309800 A1 EP 3309800A1 EP 16193341 A EP16193341 A EP 16193341A EP 3309800 A1 EP3309800 A1 EP 3309800A1
Authority
EP
European Patent Office
Prior art keywords
paste
weight
layer
weight percent
glass
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.)
Granted
Application number
EP16193341.1A
Other languages
German (de)
French (fr)
Other versions
EP3309800B1 (en
Inventor
Jochen Langer
Melanie BAWOHL
Christina Modes
Steffen Burk
Jan Marien
Paul Kalemba
Anja Desch
Roland Reul
Jessica Reitz
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.)
IsabellenHuette Heusler GmbH and Co KG
Heraeus Deutschland GmbH and Co KG
Original Assignee
IsabellenHuette Heusler GmbH and Co KG
Heraeus Deutschland GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to ES16193341T priority Critical patent/ES2730825T3/en
Application filed by IsabellenHuette Heusler GmbH and Co KG, Heraeus Deutschland GmbH and Co KG filed Critical IsabellenHuette Heusler GmbH and Co KG
Priority to EP16193341.1A priority patent/EP3309800B1/en
Priority to KR1020197011773A priority patent/KR102298321B1/en
Priority to CN201780062982.9A priority patent/CN109906491A/en
Priority to JP2019519641A priority patent/JP2019537838A/en
Priority to PCT/EP2017/073421 priority patent/WO2018068989A1/en
Priority to US16/340,611 priority patent/US20200051719A1/en
Priority to TW106134416A priority patent/TWI765919B/en
Publication of EP3309800A1 publication Critical patent/EP3309800A1/en
Application granted granted Critical
Publication of EP3309800B1 publication Critical patent/EP3309800B1/en
Priority to US17/388,676 priority patent/US20220051834A1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/06—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material including means to minimise changes in resistance with changes in temperature
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
    • H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
    • H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
    • H01C17/06553—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of a combination of metals and oxides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/05—Alloys based on copper with manganese as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
    • H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
    • H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
    • H01C17/06526—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
    • H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
    • H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
    • H01C17/06533—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
    • H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
    • H01C17/06593—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the temporary binder
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/003—Thick film resistors

Definitions

  • the invention relates to a method for producing a layer structure on a substrate using a resistor alloy based paste, as well as the resulting layer structure and its use.
  • alloys with a low temperature coefficient of electrical resistance are used.
  • Such alloys with a low TCR value are referred to as resistance alloys in the context of the invention.
  • a typical resistance alloy with a low TCR value is, for example, ISOTAN® (also known as CuNi44, material No. 2.0842).
  • ISOTAN® also known as CuNi44, material No. 2.0842.
  • the alloy layers are applied to a substrate having a surface of a glass or ceramic material.
  • resistance alloys in the form of films or sheets, by roll-bonding or lamination are combined with substrate materials customary in electrical engineering.
  • resistance alloys as a paste to substrate materials by means of simple printing techniques, in particular screen printing or stencil printing, since this makes possible more flexible layer geometries.
  • Such pastes consist at least of a powder of the relevant resistance alloy and an organic medium. By firing, the constituents of the organic medium volatilize and the fused alloy of the resistance alloy remains.
  • organic media available, in which powder of these resistance alloys can be formulated and which basically guarantee a printability.
  • pastes, which consist only of resistance alloy powder and organic medium show only a slight adhesion to the ceramic substrates used after firing.
  • Improved adhesion of printed resistor alloys to glass or ceramic surfaces can basically be achieved by adding a glass frit to a resistance alloy paste.
  • Layer structures of a ceramic substrate and a glass-containing resistance alloy paste, or the resulting layer structures after baking, are known in the art.
  • the EP0829886A2 teaches, for example, a glass frit containing resistance alloy paste deposited on an Al 2 O 3 substrate is applied.
  • a glass frit is added to resistance alloy paste, it has the disadvantage that the TCR value of the post-baked layer may differ from the TCR value of the bulk resistive alloy, so that the advantageous electrical properties of the resistance alloy in the composite thus formed can not come to fruition.
  • the object underlying the present invention is to provide a method for producing layers of resistance alloys on glass or ceramic surfaces, in which resistance alloys can be applied by printing a paste and allow strong adhesion of the resistance alloys on the ceramic substrate, without impairing the electrical properties of the resistance alloys in the layer structure produced. It is also an object to provide a layer structure in which the resistance alloy is mechanically stably connected to the glass or ceramic surface of a substrate after firing.
  • a substrate with a glass or ceramic surface is provided.
  • the substrate thus has a surface comprising a ceramic or a glass, wherein the ceramic material of the surface may preferably be selected from the group consisting of oxide ceramics, nitride ceramics and carbide ceramics.
  • suitable ceramics are forsterite, mullite, steatite, alumina, aluminum nitride, silicon carbide and hard porcelain.
  • the ceramic surface contains alumina or consists of alumina.
  • the glass of the glass surface is preferably a silicate glass.
  • a paste A is applied to at least a part of the glass or ceramic surface of the substrate.
  • the application can be effected for example by screen printing, stencil printing, knife coating or spraying.
  • a layer of paste A is obtained.
  • Paste A contains at least a glass frit and an organic medium or consists of at least one glass frit and an organic medium.
  • paste A contains 50-90% by weight of glass frit and 10-50% by weight of organic medium, based on the total weight of paste A.
  • the glass frit of the paste A contains at least two mutually different elements as oxides. These elements may be selected from the group consisting of Li, Na, K, Ca, Mg, Sr, Ba, B, Al, Si, Sn, Pb, P, Sb, Bi, Te, La, Ti, Zr, V, Nb, Mn, Fe, Co, Ni, Cu, Ag, Zn, and Cd.
  • the glass frit may be made of oxides, fluorides or other salts (eg, carbonates, nitrates, phosphates) of these elements.
  • Examples of starting compounds for preparing the glass frit may be selected from the group consisting of B 2 O 3 , H 3 BO 3 , Al 2 O 3 , SiO 2 , PbO, P 2 O 5 , Pb 3 O 4 , PbF 2 , MgO, MgCO 3 , CaO, CaCO 3 , SrO, SrCO 3 , BaO, BaCOs, Ba (NO 3 ) 2 , Na 2 B 4 O 7 , ZnO, ZnF 2 , Bi 2 O 3 , Li 2 O, Li 2 CO 3 , Na 2 O, NaCO 3 , NaF, K 2 O, K 2 CO 3 , KF, TiO 2 , Nb 2 O 5 , Fe 2 O 3 , ZrO 2 CuO, Cu 2 O, MnO, MnO 2 , Mn 3 O 4 , CdO, SnO 2 , TeO 2 , Sb 2 O 3 , Co 3 O 4 , Co 2 O 3 , CoO, La 2
  • the transformation temperature T g of the glass frit of the paste A is in the range of 600-750 ° C., in particular in the range of 690-740 ° C.
  • the transformation temperature T g can be determined for the purposes of the invention according to DIN ISO 7884-8: 1998-02.
  • the glass frit contained in paste A preferably comprises silicon, aluminum, boron and at least one alkaline earth metal in each case as an oxide.
  • the alkaline earth metal is particularly preferably calcium.
  • the organic medium may contain at least one organic solvent and at least one binder.
  • the organic solvent may be selected from the group consisting of texanol, terpineol and other high boiling point organic solvents having a boiling point of at least 140 ° C.
  • the binder may be selected from acrylate resins, ethylcelluloses and other polymers such as e.g. Butyralen.
  • the organic medium of paste A may contain other ingredients which may be selected from the group consisting of thixotropic agents, stabilizers and emulsifiers. By adding these ingredients, e.g. the printability or storage stability of pastes can be improved.
  • step c) a drying step and optionally firing of the layer of paste A is carried out.
  • the drying can be carried out at temperatures in the range of 20-180 ° C, in particular in the range of 120-180 ° C, e.g. in a dry bar.
  • the layer of paste A can be fixed on the substrate.
  • the dried layer of paste A can already be so mechanically robust that a layer of paste B can be applied directly.
  • the layer of paste A may optionally be fired after drying.
  • the firing can take place at temperatures in the range of 750-950 ° C.
  • the layer of paste A is fired so that the organic medium is substantially removed and the glass frit sinters together as homogeneously as possible.
  • the fired layer of paste A has at least one glass or consists of a glass.
  • the fired layer of paste A may also be called layer A.
  • the firing can be carried out either under atmospheric conditions or under inert gas conditions (eg N 2 atmosphere).
  • the layer of paste A is first dried in step c) and then fired. If the layer of paste A is already fired in step c), in the subsequent step d. Paste B may possibly be better applied.
  • paste B is added to at least a portion of the layer of step c to obtain a layer of paste B.
  • the paste B of the present invention contains at least a powder of a resistance alloy and an organic medium.
  • paste B may additionally contain a glass frit.
  • a glass-free paste B may have the advantage that the electrical properties of the resistance alloy, in particular the TCR value, are not adversely affected by the presence of glass.
  • paste B may also be preferred for paste B to contain a glass frit.
  • paste B does not contain more than 15% by weight, preferably not more than 12% by weight of glass frit, based on the total weight of paste B.
  • T. -Shock storage the bond strength of the layer structure can be varied with frequent temperature changes (T. -Shock storage) can be improved.
  • paste B contains at least 3% by weight Glass frit, in particular at least 5 weight percent based on the total weight of paste B.
  • the content of resistance alloy in paste B may preferably be in the range of 60-98% by weight and the content of organic medium may be in the range of 2-40% by weight, in particular in the range of 2-37% by weight, based in each case on the total weight of paste B.
  • the resistance alloys usable for the powder have a temperature coefficient of electrical resistance of less than 150 ppm / K, preferably less than 100 ppm / K and more preferably less than 50 ppm / K.
  • the temperature coefficient of the electrical resistance specified in the context of the invention relates to the measurement of the bulk alloy and can in the context of the invention on a wire or a film of the corresponding alloy according to the standard DIN EN 60115-1: 2016-03 (with drying method I ).
  • the resistance alloy may include, for example, elements selected from the group consisting of chromium, aluminum, silicon, manganese, iron, nickel and copper.
  • the resistance alloy may preferably be selected from the group consisting of CuNi, CuNiMn, CuSnMn and NiCuAlSiMnFe.
  • the resistance alloy may be selected from the group consisting of the alloys: I. copper 53.0-57.0 weight percent nickel 42.0 - 46.0 weight percent manganese 0.5-1.2 weight percent other elements ⁇ 10,000 ppm by weight II. copper 83.0 - 89.0 weight percent nickel 1-3% by weight manganese 10.0 - 14.0 weight percent other elements ⁇ 10,000 ppm by weight III.
  • the powder of the resistance alloy can be prepared by methods known to those skilled in the art, such as gas atomization under inert gas, water atomization or grinding.
  • the average particle diameter d 50 of the powder of the resistance alloy is preferably 0.2 ⁇ m-15 ⁇ m.
  • paste B contains an organic medium.
  • paste B contains the organic medium in an amount of 2-40% by weight.
  • the organic medium of paste B may contain at least one organic solvent and at least one binder.
  • the organic solvent can be selected from the group consisting of texanol, terpineol, iso-tridecyl alcohol or other high-boiling organic solvents having a boiling point of at least 140 ° C.
  • the binder may be selected from acrylate resins, ethylcelluloses or other polymers.
  • the organic medium of paste B may contain other ingredients which may be selected from the group consisting of thixotropic agents, stabilizers and emulsifiers. By adding these ingredients, e.g. the printability or storage stability of the paste can be improved.
  • the optionally contained glass frit of paste B contains at least two mutually different elements as oxides.
  • the elements can be selected from the group consisting of Li, Na, K, Ca, Mg, Sr, Ba, B, Al, Si, Sn, Pb, P, Sb, Bi, Te, La, Ti, Zr, V, Nb, Mn, Fe, Co, Ni, Cu, Ag, Zn, and Cd.
  • the glass frit can be prepared from oxides, fluorides or other salts (eg carbonates, nitrates, phosphates) of these elements.
  • Examples of starting compounds for the glass frit may be selected from the group consisting of B 2 O 3 , H 3 BO 3 , Al 2 O 3 , SiO 2 , PbO, P 2 O 5 , Pb 3 O 4 , PbF 2 , MgO, MnCO 3 , CaO, CaCO 3 , SrO, SrCO 3 , BaO, BaCO 3 , Ba (NO 3 ) 2 , Na 2 B 4 O 7 , ZnO, ZnF 2 , Bi 2 O 3 , Li 2 O, Li 2 CO 3 , Na 2 O, NaCO 3 , NaF, K 2 O, K 2 CO 3 , KF,, TiO 2 , Nb 2 O 5 , Fe 2 O 3 , ZrO 2 CuO, MnO, Mn 3 O 4 , MnO 2 , CdO, SnO 2 , TeO 2 , Sb 2 O 3 , Co 3 O 4 , Co 2 O 3 , CoO, La 2 O 3 ,
  • the glass frit of paste B may contain silicon, aluminum, boron and at least one alkaline earth metal, each as oxide.
  • the glass frit of the paste B may be the same as the glass frit of the paste A or different.
  • the glass frit of paste B may contain at least two elements as oxides contained in the glass frit of paste A.
  • the glass frits of the pastes A and B are the same, as this can improve the compatibility of the layers A and B with each other.
  • the layer of paste B is accordingly applied to layer A.
  • a so-called precursor (dt. Precursor structure) is prepared.
  • the precursor thus contains a substrate on which a layer of paste A is applied, which may optionally already be fired (then also called layer A).
  • the precursor contains a layer of paste B on the layer of paste A, wherein the layer of paste B is not fired.
  • the paste B is applied to an already in step c. fired layer A applied.
  • the precursor may be configured so that the layer of paste B completely covers the layer of paste A.
  • step e) the precursor is fired, thereby obtaining the layer structure according to the invention.
  • the firing may be preceded by a drying step.
  • the drying can be carried out at a temperature in the range of 20-180 ° C., in particular in the range of 120-180 ° C., for example in a dry bar or an infrared belt dryer.
  • the burning of the precursor is preferably carried out at a temperature in the range of 700-1000 ° C, in particular in the range of 850-900 ° C.
  • the precursor is preferably fired in such a way that the constituents of the organic medium in the precursor volatilize and the powder of the resistance alloy and the glass frit sinter together.
  • the firing may take place either under atmospheric conditions in the presence of O 2 or under inert gas conditions (eg N 2 atmosphere).
  • the layer of paste A as explained above, the layer A is obtained, and by firing the layer of paste B, layer B is obtained.
  • the layers of paste A and paste B are burned simultaneously by the firing of the precursor .
  • the layer A is forcibly refired when the layer of paste B is fired.
  • Layer A which at least partially covers the glass or ceramic surface of the substrate, comprises the glass obtained by firing the glass frit from paste A.
  • the glass in layer A contains the sintered glass frit of paste A.
  • this glass frit is homogeneously sintered to the glass over the entire extent of layer A and has no non-sintered regions.
  • layer B has the resistance alloy of paste B and is mechanically firmly connected to layer A.
  • the mechanical strength of adhesion can be determined by various tests.
  • Layer B of the layer structure may have a TCR value substantially equal to the bulk value of the resistance alloy.
  • the adhesion can be checked by the following tests: A strip of adhesive tape of the brand Scotch®-Magic (3M Germany GmbH) is glued to the fired layer structure and, for example, firmly brushed with a fingernail. Subsequently, the adhesive film is removed again. Resistant alloy layers with low adhesion to the glass or ceramic surface of the substrate adhere to the adhesive film. Layered structures with a medium adhesive strength remain partly on the adhesive film and layer structures with a high adhesive strength are not detached from the adhesive film.
  • layer A can act as a bonding agent between the glass or ceramic surface of the substrate and the layer B containing the resistance alloy.
  • the present invention can provide a layer of resistance alloy mechanically stably bonded to the substrate surface.
  • the layer B contains the resistance alloy in the amount originally used in paste B.
  • layer B additionally has a glass made from the glass frit of paste B
  • the adhesion of layer B to layer A can be further improved.
  • the glass content of layer B is determined by the amount of glass frit used in paste B.
  • layer B comprises not more than 20% by weight of glass, in particular not more than 15% by weight of glass, based on the total weight of layer B.
  • the layer structure following step e) can be provided with a seal (also called protective glaze , or overglaze ).
  • a seal also called protective glaze , or overglaze .
  • this seal is made of a glass. This seal is used in particular to protect the layer structure from environmental influences, such as moisture.
  • the layer structure according to the invention can be used inter alia to produce precision resistors.
  • Paste A was prepared by mixing 22% by weight of organic medium (85% by weight of Texanol, 15% by weight of ethylcellulose (75% N7, 25% N50)) and 78% by weight of a glass frit according to Table 1. The pastes were homogenized by means of a three-roll chair.
  • a powder of the resistance alloy isotan (average particle diameter d 50 : 8 microns, prepared by gas atomizing a melt under N 2 atmosphere), an organic medium (65 wt.% Texanol and 35 wt.% Acrylate binder) and, if necessary, a glass frit combined in the specified amounts and homogenized using a three-roll chair.
  • the pastes produced have a viscosity of about 30-90 Pas at 20-25 ° C. ⁇ b> Table 2 ⁇ / b> % By weight Glass frit 7 Isotanpulver Organic medium Paste B1 6 84 10
  • the glass pastes A containing the glass frits from Table 1 were applied by screen printing on Al 2 O 3 substrates having a size of 101.6 ⁇ 101.6 mm and a thickness of 0.63 mm (Rubalit 708 S, CeramTec). For this purpose, a sieve from Koenen GmbH, Germany was used with an EKRA Microtronic II printer (type M2H). The emulsion thickness was about 50 ⁇ m (sieving parameter: 80 mesh and 65 ⁇ m wire diameter (stainless steel)). Printing parameters: 63 N squeegee pressure, squeegee speed 100 mm / s and a jump of 1.0 mm. The layer thickness after printing (wet) was about 90 ⁇ m.
  • the samples were placed in an infrared belt dryer (BTU international, type HHG-2) for 20 min dried at 150 ° C.
  • the layer thickness after drying was about 60 microns.
  • the printed glass layers were fired in a nitrogen atmosphere (N 2 5.0) in an oven (ATV Technologie GmbH, type PEO 603). The temperature was increased from 25 ° C to 850 ° C, held at 850 ° C for 10 and then cooled to 25 ° C within 20 min. (Total throughput time 82 min)
  • the layer thickness after firing was about 50 ⁇ m.
  • the resistance alloy paste B was applied to the previously prepared layer by screen printing. For this purpose, a sieve made by Koenen GmbH, Germany was used with an EKRA Microtronic II printer (type M2H).
  • the emulsion thickness was about 50 ⁇ m, screen parameters: 80 mesh and 65 ⁇ m wire diameter (stainless steel).
  • the printed resistance alloy pastes (including the precursor ) were fired in a nitrogen atmosphere (N 2 5.0) in an oven (ATV Technology GmbH, type PEO 603). The temperature was increased from 25 ° C to 900 ° C, held for 10 min at 900 ° C and cooled within 20 min to 25 ° C (total flow time 82 min). The layer thickness after firing was about 50 ⁇ m.
  • Glass frit 7 Isotanpulver Organic medium Paste B2 0 90 10 Paste B3 3 87 10 Paste B4 6 84 10 Paste B5 9 81 10 layer structure substratum Glass layer (layer A) Alloy layer (layer B) Liability before T-shock storage Replacement after T-Shock storage 9 Al 2 O 3 Paste A made of glass 7 Paste B2 Good 20 cycles 10 Paste B3 Good 100 cycles 11 Paste B4 Good > 500 cycles 12 Paste B5 Good > 500 cycles
  • the prepared layer structures were each stored for 15 minutes in a chamber with a temperature of -40 ° C and + 150 ° C, respectively.
  • the transition from one chamber to another was automated and lasted about 4s.
  • One cycle contains storage at -40 ° C and one at + 150 ° C.
  • the adhesion was checked after various numbers of cycles with an adhesive strip as described above.
  • the TCR values were measured in the temperature range 20-60 ° C. according to the standard DIN EN 60115-1: 2016-03 (drying method I): ⁇ b> Table 6 ⁇ / b> layer structure Quantity of glass frit in paste B TCR 9 0% by weight -25 to -14 ppm / K 12 9% by weight -37 to -21 ppm / K
  • TCR bulk value for isotan (as a wire) ranges from -80 to +40 ppm / K.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)
  • Non-Adjustable Resistors (AREA)
  • Conductive Materials (AREA)
  • Apparatuses And Processes For Manufacturing Resistors (AREA)

Abstract

Die vorliegende Erfindung betrifft einen Schichtaufbau aufweisend: ein Substrat mit einer Glas-oder Keramikoberfläche, eine Schicht A, die die Glas- oder Keramikoberfläche des Substrats wenigstens teilweise bedeckt, wobei Schicht A ein Glas aufweist, in dem wenigstens zwei voneinander verschiedene Elemente als Oxide enthalten sind und eine Schicht B, die Schicht A wenigstens teilweise bedeckt. Schicht B weist folgende Bestandteile auf: eine Widerstandslegierung mit einem Temperaturkoeffizienten der elektrischen Widerstandes weniger als 150 ppm/K, und optional ein Glas, das wenigstens zwei voneinander verschiedene Elemente als Oxide enthält. Schicht B enthält nicht mehr als 20 Gewichtsprozent Glas, bezogen auf das Gesamtgewicht der Schicht B.The present invention relates to a layer structure comprising: a substrate having a glass or ceramic surface, a layer A at least partially covering the glass or ceramic surface of the substrate, wherein layer A comprises a glass in which at least two different elements are included as oxides and a layer B, the layer A at least partially covered. Layer B comprises the following components: a resistance alloy having a temperature coefficient of electrical resistance of less than 150 ppm / K, and optionally a glass containing at least two mutually different elements as oxides. Layer B contains no more than 20% by weight of glass, based on the total weight of layer B.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung eines Schichtaufbaus auf einem Substrat unter Verwendung einer Paste auf Basis einer Widerstandslegierung, sowie den erhaltenen Schichtaufbau und dessen Verwendung.The invention relates to a method for producing a layer structure on a substrate using a resistor alloy based paste, as well as the resulting layer structure and its use.

Insbesondere für die Herstellung von Präzisionswiderständen werden Legierungen mit einem niedrigen Temperaturkoeffizient des elektrischen Widerstandes (TCR) eingesetzt. Solche Legierungen mit einem niedrigen TCR-Wert werden im Rahmen der Erfindung als Widerstandslegierungen bezeichnet. Eine typische Widerstandslegierung mit einem niedrigen TCR-Wert ist z.B. ISOTAN® (auch bekannt als CuNi44, Werkstoffnr. 2.0842). Zur Herstellung von Präzisionswiderständen werden die Legierungsschichten auf ein Substrat mit einer Oberfläche aus einem gläsernen oder keramischen Material aufgetragen. Meistens werden Widerstandslegierungen in Form von Folien oder Blechen, durch Walzplattieren oder Laminieren mit in der Elektrotechnik üblichen Substratmaterialien verbunden. Es besteht der Bedarf, Widerstandslegierungen als Paste mittels einfacher Drucktechniken, insbesondere Siebdruck oder Schablonendruck, auf Substratmaterialien aufzubringen, da dadurch flexiblere Schichtgeometrien ermöglicht werden. Dazu ist es erforderlich, Widerstandslegierungen in Form von druckbaren Pasten bereitzustellen, die nach dem Aufbringen auf das Substrat eingebrannt werden können. Solche Pasten bestehen zumindest aus einem Pulver der betreffenden Widerstandslegierung und einem organischen Medium. Durch das Brennen verflüchtigen sich die Bestandteile des organischen Mediums und das zusammengeschmolzene oder zusammengesinterte Pulver der Widerstandslegierung bleibt zurück. Es steht eine große Auswahl an organischen Medien zur Verfügung, in die Pulver dieser Widerstandslegierungen formuliert werden können und die grundsätzlich eine Verdruckbarkeit gewährleisten. Allerdings hat sich herausgestellt, dass Pasten, die nur aus Widerstandslegierungspulver und organischem Medium bestehen, auf den verwendeten Keramiksubstraten nach dem Einbrennen nur eine geringe Haftung zeigen. Eine verbesserte Haftung von gedruckten Widerstandslegierungen auf Glas- oder Keramikoberflächen kann grundsätzlich dadurch erreicht werden, dass einer Widerstandslegierungspaste eine Glasfritte zugesetzt wird. Schichtaufbauten aus einem Keramiksubstrat und einer glashaltigen Widerstandslegierungspaste, beziehungsweise die daraus resultierenden Schichtaufbauten nach dem Einbrennen, sind im Stand der Technik bekannt. Die EP0829886A2 lehrt beispielsweise eine Glasfritte enthaltende Widerstandslegierungspaste, die auf ein Al2O3-Substrat aufgebracht wird. Wenn Widerstandslegierungspaste jedoch eine Glasfritte zugesetzt wird, so hat dies den Nachteil, dass der TCR-Wert der nach dem Einbrennen gebildeten Schicht von dem TCR-Wert der Bulk-Widerstandslegierung abweichen kann, so dass die vorteilhaften elektrischen Eigenschaften der Widerstandslegierung in dem so gebildeten Verbund nicht zum Tragen kommen können.Especially for the production of precision resistors, alloys with a low temperature coefficient of electrical resistance (TCR) are used. Such alloys with a low TCR value are referred to as resistance alloys in the context of the invention. A typical resistance alloy with a low TCR value is, for example, ISOTAN® (also known as CuNi44, material No. 2.0842). To produce precision resistors, the alloy layers are applied to a substrate having a surface of a glass or ceramic material. In most cases, resistance alloys in the form of films or sheets, by roll-bonding or lamination are combined with substrate materials customary in electrical engineering. There is a need to apply resistance alloys as a paste to substrate materials by means of simple printing techniques, in particular screen printing or stencil printing, since this makes possible more flexible layer geometries. For this it is necessary to provide resistance alloys in the form of printable pastes which can be baked on the substrate after application. Such pastes consist at least of a powder of the relevant resistance alloy and an organic medium. By firing, the constituents of the organic medium volatilize and the fused alloy of the resistance alloy remains. There is a wide range of organic media available, in which powder of these resistance alloys can be formulated and which basically guarantee a printability. However, it has been found that pastes, which consist only of resistance alloy powder and organic medium, show only a slight adhesion to the ceramic substrates used after firing. Improved adhesion of printed resistor alloys to glass or ceramic surfaces can basically be achieved by adding a glass frit to a resistance alloy paste. Layer structures of a ceramic substrate and a glass-containing resistance alloy paste, or the resulting layer structures after baking, are known in the art. The EP0829886A2 teaches, for example, a glass frit containing resistance alloy paste deposited on an Al 2 O 3 substrate is applied. However, when a glass frit is added to resistance alloy paste, it has the disadvantage that the TCR value of the post-baked layer may differ from the TCR value of the bulk resistive alloy, so that the advantageous electrical properties of the resistance alloy in the composite thus formed can not come to fruition.

Die Aufgabe, die der vorliegenden Erfindung zu Grunde liegt, besteht darin, ein Verfahren zum Herstellen von Schichten von Widerstandslegierungen auf Glas- oder Keramikoberflächen bereitzustellen, bei dem Widerstandslegierungen durch Drucken einer Paste aufgetragen werden können und eine starke Haftung der Widerstandslegierungen auf dem Keramiksubstrat ermöglichen, ohne dass die elektrischen Eigenschaften der Widerstandslegierungen im erzeugten Schichtaufbau beeinträchtigt werden. Ferner besteht die Aufgabe, einen Schichtaufbau bereitzustellen, in dem die Widerstandslegierung nach dem Einbrennen mechanisch stabil mit der Glas- oder Keramikoberfläche eines Substrats verbunden ist.The object underlying the present invention is to provide a method for producing layers of resistance alloys on glass or ceramic surfaces, in which resistance alloys can be applied by printing a paste and allow strong adhesion of the resistance alloys on the ceramic substrate, without impairing the electrical properties of the resistance alloys in the layer structure produced. It is also an object to provide a layer structure in which the resistance alloy is mechanically stably connected to the glass or ceramic surface of a substrate after firing.

Diese Aufgaben werden gelöst durch ein Verfahren zur Herstellung eines Schichtaufbaus umfassend die aufeinanderfolgenden Schritte:

  1. a. Bereitstellung eines Substrats mit einer Glas - oder Keramikoberfläche,
  2. b. Aufbringen einer Paste A auf wenigstens einen Teil der Glas-oder Keramikoberfläche des Substrats unter Erhalt einer Schicht aus Paste A, wobei Paste A folgende Bestandteile enthält:
    1. I. eine Glasfritte, die wenigstens zwei voneinander verschiedene Elemente als Oxide enthält und eine Transformationstemperatur Tg im Bereich von 600 bis 750°C aufweist und
    2. II. ein organisches Medium,
  3. c. Trocknen und gegebenenfalls Brennen der Schicht aus Paste A
  4. d. Aufbringen einer Paste B auf wenigstens einen Teil der Schicht aus Schritt c. unter Erhalt eines Schicht aus Paste B, wobei Paste B folgende Bestandteile enthält:
    1. I. Ein Pulver einer Widerstandslegierung mit einem Temperaturkoeffizienten des elektrischen Widerstandes von weniger als 150 ppm/K
    2. II. ein organisches Medium,
    3. III. 0 - 15 Gewichtsprozent Glasfritte, bezogen auf das Gesamtgewicht von Paste B, und
  5. e. Brennen und optional vor dem Brennen Trocknen der Schichten aus Paste B.
These objects are achieved by a method for producing a layer structure comprising the successive steps:
  1. a. Providing a substrate having a glass or ceramic surface,
  2. b. Applying a paste A to at least part of the glass or ceramic surface of the substrate to obtain a layer of paste A, wherein paste A contains the following components:
    1. I. a glass frit which contains at least two mutually different elements as oxides and has a transformation temperature T g in the range of 600 to 750 ° C and
    2. II. An organic medium,
  3. c. Drying and optionally firing the layer of paste A
  4. d. Applying a paste B to at least a portion of the layer of step c. to obtain a layer of paste B, wherein paste B contains the following components:
    1. I. A powder of a resistance alloy having a temperature coefficient of electrical resistance of less than 150 ppm / K
    2. II. An organic medium,
    3. III. 0 to 15 weight percent glass frit, based on the total weight of paste B, and
  5. e. Burning and optionally before firing drying the layers of paste B.

Dem Fachmann ist anhand der vorangegangenen Formulierung klar, dass die Abfolge der Schritte eingehalten werden muss, wobei nicht ausgeschlossen ist, dass optional zwischen den genannten Schritten jeweils auch weitere Schritte durchgeführt werden können, solange die Reihenfolge nicht geändert wird.It is clear to the person skilled in the art from the preceding formulation that the sequence of steps must be adhered to, wherein it is not excluded that further steps can optionally also be carried out between the named steps as long as the sequence is not changed.

Es wurde gefunden, dass mit dem erfindungsgemäßen Verfahren ein Schichtaufbau hergestellt werden kann, der eine verbesserte mechanische Stabilität, insbesondere eine bessereIt has been found that the method according to the invention can be used to produce a layer structure which has improved mechanical stability, in particular a better one

Langzeitstabilität aufweist, ohne dass dadurch der TCR der Widerstandslegierung im Wesentlichen verändert würde.Having long term stability, without thereby the TCR of the resistance alloy would be substantially changed.

Überraschender Weise wurde gefunden, dass besonders gute Schichtaufbauten hergestellt werden können, wenn vor dem Aufbringen der Paste B auf der Glas- oder Keramikoberfläche eines Substrats eine Paste A aufgebracht wird und gleichzeitig der Gewichtsanteil an Glasfritte in Paste B so eingestellt wird, dass die Paste B nicht mehr als 15 Gewichtsprozent enthält.Surprisingly, it has been found that particularly good layer constructions can be produced if, prior to the application of the paste B, a paste A is applied to the glass or ceramic surface of a substrate and at the same time the proportion by weight of glass frit in paste B is adjusted so that the paste B not more than 15% by weight.

In Schritt a) wird ein Substrat mit einer Glas- oder Keramikoberfläche bereitgestellt. Das Substrat hat also eine Oberfläche, die eine Keramik oder ein Glas aufweist, wobei das keramische Material der Oberfläche bevorzugt ausgewählt sein kann aus der Gruppe bestehend aus Oxidkeramiken, Nitridkeramiken und Carbidkeramiken. Bespiele für geeignete Keramiken sind Forsterit, Mullit, Steatit, Aluminiumoxid, Aluminiumnitrid, Siliziumcarbid und Hartporzellan. Insbesondere enthält die Keramikoberfläche Aluminiumoxid oder besteht aus Aluminiumoxid. Das Glas der Glasoberfläche ist bevorzugt ein Silikatglas.In step a) a substrate with a glass or ceramic surface is provided. The substrate thus has a surface comprising a ceramic or a glass, wherein the ceramic material of the surface may preferably be selected from the group consisting of oxide ceramics, nitride ceramics and carbide ceramics. Examples of suitable ceramics are forsterite, mullite, steatite, alumina, aluminum nitride, silicon carbide and hard porcelain. In particular, the ceramic surface contains alumina or consists of alumina. The glass of the glass surface is preferably a silicate glass.

In Schritt b) wird eine Paste A auf wenigstens einen Teil der Glas- oder Keramikoberfläche des Substrats aufgebracht. Das Aufbringen kann beispielsweise durch Siebdruck, Schablonendruck, Rakeln oder Aufspritzen erfolgen. Durch das Aufbringen wird eine Schicht aus Paste A erhalten. Paste A enthält mindestens eine Glasfritte und ein organisches Medium oder besteht aus mindestens einer Glasfritte und einem organischen Medium. Bevorzugt enthält Paste A 50 - 90 Gewichtsprozent Glasfritte und 10 - 50 Gewichtsprozent organisches Medium, bezogen auf das Gesamtgewicht von Paste A.In step b), a paste A is applied to at least a part of the glass or ceramic surface of the substrate. The application can be effected for example by screen printing, stencil printing, knife coating or spraying. By applying a layer of paste A is obtained. Paste A contains at least a glass frit and an organic medium or consists of at least one glass frit and an organic medium. Preferably, paste A contains 50-90% by weight of glass frit and 10-50% by weight of organic medium, based on the total weight of paste A.

Die Glasfritte der Paste A enthält wenigstens zwei voneinander verschiedene Elemente als Oxide. Diese Elemente können ausgewählt sein aus der Gruppe bestehend aus Li, Na, K, Ca, Mg, Sr, Ba, B, Al, Si, Sn, Pb, P, Sb, Bi, Te, La, Ti, Zr, V, Nb, Mn, Fe, Co, Ni, Cu, Ag, Zn, und Cd. Die Glasfritte kann hergestellt sein aus Oxiden, Fluoriden oder sonstigen Salzen (z.B. Carbonaten, Nitraten, Phosphaten) dieser Elemente. Beispiele für Ausgangsverbindungen zur Herstellung der Glasfritte können ausgewählt sein aus der Gruppe bestehend aus B2O3, H3BO3, Al2O3, SiO2, PbO, P2O5, Pb3O4, PbF2, MgO, MgCO3, CaO, CaCO3, SrO, SrCO3, BaO, BaCOs, Ba(NO3)2, Na2B4O7, ZnO, ZnF2, Bi2O3, Li2O, Li2CO3, Na2O, NaCO3, NaF, K2O, K2CO3, KF, TiO2, Nb2O5, Fe2O3, ZrO2 CuO,Cu2O, MnO, MnO2, Mn3O4, CdO, SnO2, TeO2, Sb2O3, Co3O4, Co2O3, CoO, La2O3, Ag2O, NiO, V2O5, Li3PO4, Na3PO4, K3PO4, Ca3(PO4)2, Mg3(PO4)2, Sr3(PO4)2, Ba3(PO4)2 und komplexen Mineralien, wie z.B. Colemanit und Dolomit.The glass frit of the paste A contains at least two mutually different elements as oxides. These elements may be selected from the group consisting of Li, Na, K, Ca, Mg, Sr, Ba, B, Al, Si, Sn, Pb, P, Sb, Bi, Te, La, Ti, Zr, V, Nb, Mn, Fe, Co, Ni, Cu, Ag, Zn, and Cd. The glass frit may be made of oxides, fluorides or other salts (eg, carbonates, nitrates, phosphates) of these elements. Examples of starting compounds for preparing the glass frit may be selected from the group consisting of B 2 O 3 , H 3 BO 3 , Al 2 O 3 , SiO 2 , PbO, P 2 O 5 , Pb 3 O 4 , PbF 2 , MgO, MgCO 3 , CaO, CaCO 3 , SrO, SrCO 3 , BaO, BaCOs, Ba (NO 3 ) 2 , Na 2 B 4 O 7 , ZnO, ZnF 2 , Bi 2 O 3 , Li 2 O, Li 2 CO 3 , Na 2 O, NaCO 3 , NaF, K 2 O, K 2 CO 3 , KF, TiO 2 , Nb 2 O 5 , Fe 2 O 3 , ZrO 2 CuO, Cu 2 O, MnO, MnO 2 , Mn 3 O 4 , CdO, SnO 2 , TeO 2 , Sb 2 O 3 , Co 3 O 4 , Co 2 O 3 , CoO, La 2 O 3 , Ag 2 O, NiO, V 2 O 5 , Li 3 PO 4 , Na 3 PO 4 , K 3 PO 4 , Ca 3 (PO 4 ) 2 , Mg 3 (PO 4 ) 2 , Sr 3 (PO 4 ) 2 , Ba 3 (PO 4 ) 2 and complex minerals such as colemanite and dolomite.

Die Transformationstemperatur Tg der Glasfritte der Paste A liegt im Bereich von 600 - 750°C, insbesondere im Bereich von 690 - 740°C. Die Transformationstemperatur Tg kann für die Zwecke der Erfindung gemäß DIN ISO 7884-8:1998-02 bestimmt werden.The transformation temperature T g of the glass frit of the paste A is in the range of 600-750 ° C., in particular in the range of 690-740 ° C. The transformation temperature T g can be determined for the purposes of the invention according to DIN ISO 7884-8: 1998-02.

Bevorzugt umfasst die in Paste A enthaltene Glasfritte Silizium, Aluminium, Bor und mindestens ein Erdalkalimetall jeweils als Oxid auf. Besonders bevorzugt ist das Erdalkalimetall Calcium.The glass frit contained in paste A preferably comprises silicon, aluminum, boron and at least one alkaline earth metal in each case as an oxide. The alkaline earth metal is particularly preferably calcium.

Um eine besonders gute Haftung zu erzielen, kann die Glasfritte in einer bevorzugten Ausführungsform hergestellt sein aus:

  1. a. 25 - 55 Gewichtsprozent Siliziumoxid,
  2. b. 20 - 45 Gewichtsprozent Calciumcarbonat,
  3. c. 10 - 30 Gewichtsprozent Aluminiumoxid und
  4. d. 1 - 10 Gewichtsprozent Boroxid.
In order to achieve a particularly good adhesion, the glass frit can be produced in a preferred embodiment from:
  1. a. 25-55% by weight silica,
  2. b. 20-45% by weight calcium carbonate,
  3. c. 10 to 30 weight percent alumina and
  4. d. 1 - 10 weight percent boron oxide.

Das organische Medium kann mindestens ein organisches Lösungsmittel und mindestens einen Binder enthalten. Das organische Lösungsmittel kann ausgewählt sein aus der Gruppe bestehend aus Texanol, Terpineol und anderen hochsiedenden organischen Lösungsmitteln mit einem Siedepunkt von mindesten 140°C. Der Binder kann ausgewählt sein aus Acrylatharzen, Ethylcellulosen und anderen Polymeren wie z.B. Butyralen. Optional kann das organische Medium der Paste A weitere Bestandteile enthalten, die ausgewählt sein können aus der Gruppe bestehend aus Thixotropiemitteln, Stabilisatoren und Emulgatoren. Durch Zugabe dieser Bestandteile können z.B. die Verdruckbarkeit oder Lagerstabilität von Pasten verbessert werden.The organic medium may contain at least one organic solvent and at least one binder. The organic solvent may be selected from the group consisting of texanol, terpineol and other high boiling point organic solvents having a boiling point of at least 140 ° C. The binder may be selected from acrylate resins, ethylcelluloses and other polymers such as e.g. Butyralen. Optionally, the organic medium of paste A may contain other ingredients which may be selected from the group consisting of thixotropic agents, stabilizers and emulsifiers. By adding these ingredients, e.g. the printability or storage stability of pastes can be improved.

In Schritt c) erfolgen ein Trocknungsschritt und gegebenenfalls ein Brennen der Schicht aus Paste A. Das Trocknen kann bei Temperaturen im Bereich von 20 - 180°C, insbesondere im Bereich von 120-180 °C erfolgen, z.B. in einem Trockenschank. Durch das Trocknen kann die Schicht aus Paste A auf dem Substrat fixiert werden. Die getrocknete Schicht aus Paste A kann bereits so mechanisch robust sein, dass direkt eine Schicht aus Paste B aufgetragen werden kann.In step c), a drying step and optionally firing of the layer of paste A is carried out. The drying can be carried out at temperatures in the range of 20-180 ° C, in particular in the range of 120-180 ° C, e.g. in a dry bar. By drying, the layer of paste A can be fixed on the substrate. The dried layer of paste A can already be so mechanically robust that a layer of paste B can be applied directly.

Die Schicht aus Paste A kann nach dem Trocknen optional gebrannt werden. Das Brennen kann bei Temperaturen im Bereich von 750 - 950°C erfolgen. Bevorzugt wird die Schicht aus Paste A so gebrannt, dass das organische Medium im Wesentlichen entfernt wird und die Glasfritte möglichst homogen zusammensintert. Die gebrannte Schicht aus Paste A weist mindestens ein Glas auf oder besteht aus einem Glas. Die gebrannte Schicht aus Paste A kann auch Schicht A genannt werden. Das Brennen kann entweder unter Atmosphärenbedingungen oder unter Inertgasbedingungen (z.B. N2-Atmosphäre) erfolgen. In einer bevorzugten Ausführungsform der Erfindung wird die Schicht aus Paste A in Schritt c) zuerst getrocknet und anschließend gebrannt. Wenn die Schicht aus Paste A in Schritt c) schon gebrannt wird, kann im darauf folgenden Schritt d. Paste B möglicher Weise besser aufgetragen werden.The layer of paste A may optionally be fired after drying. The firing can take place at temperatures in the range of 750-950 ° C. Preferably, the layer of paste A is fired so that the organic medium is substantially removed and the glass frit sinters together as homogeneously as possible. The fired layer of paste A has at least one glass or consists of a glass. The fired layer of paste A may also be called layer A. The firing can be carried out either under atmospheric conditions or under inert gas conditions (eg N 2 atmosphere). In a preferred embodiment of the invention, the layer of paste A is first dried in step c) and then fired. If the layer of paste A is already fired in step c), in the subsequent step d. Paste B may possibly be better applied.

In Schritt d) wird Paste B unter Erhalt einer Schicht aus Paste B auf wenigstens einen Teil der Schicht aus Schritt c. aufgebracht. Die Paste B der vorliegenden Erfindung enthält mindestens ein Pulver einer Widerstandslegierung und ein organisches Medium. Optional kann Paste B zusätzlich eine Glasfritte enthalten. Es kann jedoch auch bevorzugt sein, dass Paste B keine Glasfritte enthält. Eine glasfreie Paste B kann den Vorteil haben, dass die elektrischen Eigenschaften der Widerstandslegierung, insbesondere der TCR-Wert, nicht negativ durch die Anwesenheit von Glas beeinflusst werden.In step d), paste B is added to at least a portion of the layer of step c to obtain a layer of paste B. applied. The paste B of the present invention contains at least a powder of a resistance alloy and an organic medium. Optionally, paste B may additionally contain a glass frit. However, it may also be preferred that paste B contains no glass frit. A glass-free paste B may have the advantage that the electrical properties of the resistance alloy, in particular the TCR value, are not adversely affected by the presence of glass.

Um die Haftung von Schicht B auf Schicht A im fertigen Schichtaufbau weiter zu verbessern, kann es auch bevorzugt sein, dass Paste B eine Glasfritte enthält. Paste B enthält jedoch nicht mehr als 15 Gewichtsprozent, bevorzugt nicht mehr als 12 Gewichtsprozent Glasfritte, bezogen auf das Gesamtgewicht von Paste B. Wie in Tabelle 5 zu erkennen ist, kann durch eine Glasfritte in Paste B die Haftfestigkeit des Schichtaufbaus bei häufigen Temperaturwechseln (T-Shock-Lagerung) verbessert werden. Bevorzugt enthält Paste B mindestens 3 Gewichtsprozent Glasfritte, insbesondere mindestens 5 Gewichtsprozent bezogen auf das Gesamtgewicht von Paste B. Besonders bevorzugt kann Paste B Glasfritte in einer Menge von 3 - 15 Gewichtsprozent, ganze besonders bevorzugt in einer Menge von 5 - 12 Gewichtsprozent, bezogen auf das Gesamtgewicht von Paste B enthalten. Der Gehalt an Widerstandslegierung in Paste B kann bevorzugt im Bereich von 60 - 98 Gewichtsprozent liegen und der Gehalt an organischem Medium kann im Bereich von 2 - 40 Gewichtsprozent, insbesondere im Bereich von 2 - 37 Gewichtsprozent liegen, jeweils bezogen auf das Gesamtgewicht von Paste B.In order to further improve the adhesion of layer B to layer A in the finished layer structure, it may also be preferred for paste B to contain a glass frit. However, paste B does not contain more than 15% by weight, preferably not more than 12% by weight of glass frit, based on the total weight of paste B. As can be seen in Table 5, by a glass frit in paste B the bond strength of the layer structure can be varied with frequent temperature changes (T. -Shock storage) can be improved. Preferably, paste B contains at least 3% by weight Glass frit, in particular at least 5 weight percent based on the total weight of paste B. More preferably, paste B glass frit in an amount of 3 to 15 weight percent, more preferably in an amount of 5 to 12 weight percent, based on the total weight of paste B. The content of resistance alloy in paste B may preferably be in the range of 60-98% by weight and the content of organic medium may be in the range of 2-40% by weight, in particular in the range of 2-37% by weight, based in each case on the total weight of paste B. ,

Die für das Pulver verwendbaren Widerstandslegierungen weisen einen Temperaturkoeffizienten des elektrischen Widerstandes von weniger als 150 ppm/K, bevorzugt von weniger als 100 ppm/K und besonders bevorzugt von weniger als 50 ppm/K, auf. Der im Rahmen der Erfindung angegebene Temperaturkoeffizienten des elektrischen Widerstandes bezieht sich auf die Messung der Bulk-Legierung und kann im Rahmen der Erfindung an einem Draht oder einer Folie der entsprechenden Legierung gemäß der Norm DIN EN 60115-1:2016-03 (mit Trocknungsverfahren I) bestimmt werden.The resistance alloys usable for the powder have a temperature coefficient of electrical resistance of less than 150 ppm / K, preferably less than 100 ppm / K and more preferably less than 50 ppm / K. The temperature coefficient of the electrical resistance specified in the context of the invention relates to the measurement of the bulk alloy and can in the context of the invention on a wire or a film of the corresponding alloy according to the standard DIN EN 60115-1: 2016-03 (with drying method I ).

Die Widerstandslegierung kann beispielsweise Elemente enthalten, die ausgewählt sind aus der Gruppe bestehend aus Chrom, Aluminium, Silizium, Mangan, Eisen, Nickel und Kupfer. Die Widerstandslegierung kann vorzugsweise ausgewählt sein aus der Gruppe bestehend aus CuNi, CuNiMn, CuSnMn und NiCuAlSiMnFe. In einer besonders bevorzugten Ausführungsform kann die Widerstandslegierung ausgewählt sein aus der Gruppe bestehend aus den Legierungen:
I. Kupfer 53,0 - 57,0 Gewichtsprozent Nickel 42,0 - 46,0 Gewichtsprozent Mangan 0,5 - 1,2 Gewichtsprozent sonstiger Elemente ≤10000 Gew. ppm II. Kupfer 83,0 - 89,0 Gewichtsprozent Nickel 1 - 3 Gewichtsprozent Mangan 10,0 - 14,0 Gewichtsprozent sonstiger Elemente ≤10000 Gew. ppm III. Kupfer 88,0 - 93,0 Gewichtsprozent Zinn 2 - 3 Gewichtsprozent Mangan 5,0 - 9,0 Gewichtsprozent sonstiger Elemente ≤10000 Gew. ppm IV. Kupfer 61,0 - 69,0 Gewichtsprozent Nickel 8 - 12 Gewichtsprozent Mangan 23,0 - 27,0 Gewichtsprozent sonstiger Elemente ≤10000 Gew. ppm oder
V. Nickel 70,0 - 78,0 Gewichtsprozent Chrom 18,0 - 22,0 Gewichtsprozent Aluminium 3 - 4 Gewichtsprozent Silizium ,5 - 1,5 Gewichtsprozent Mangan 0,2 - 0,8 Gewichtsprozent Eisen 0,2 - 0,8 Gewichtsprozent sonstiger Elemente ≤10000 Gew. ppm The resistance alloy may include, for example, elements selected from the group consisting of chromium, aluminum, silicon, manganese, iron, nickel and copper. The resistance alloy may preferably be selected from the group consisting of CuNi, CuNiMn, CuSnMn and NiCuAlSiMnFe. In a particularly preferred embodiment, the resistance alloy may be selected from the group consisting of the alloys:
I. copper 53.0-57.0 weight percent nickel 42.0 - 46.0 weight percent manganese 0.5-1.2 weight percent other elements ≤ 10,000 ppm by weight II. copper 83.0 - 89.0 weight percent nickel 1-3% by weight manganese 10.0 - 14.0 weight percent other elements ≤ 10,000 ppm by weight III. copper 88.0 - 93.0 weight percent tin 2 - 3 weight percent manganese 5.0-9.0 weight percent other elements ≤ 10,000 ppm by weight IV. copper 61.0-69.0 weight percent nickel 8-12% by weight manganese 23.0 - 27.0 weight percent other elements ≤ 10,000 ppm by weight or
V. nickel 70.0-78.0 weight percent chrome 18.0 - 22.0 weight percent aluminum 3 - 4 percent by weight silicon , 5-1.5% by weight manganese 0.2-0.8 weight percent iron 0.2-0.8 weight percent other elements ≤ 10,000 ppm by weight

Das Pulver der Widerstandslegierung kann durch dem Fachmann bekannte Verfahren, wie z.B. Gasverdüsen unter Inertgas, Wasserverdüsen oder Mahlen, hergestellt werden. Die mittlere Teilchendurchmesser d50 des Pulvers der Widerstandslegierung beträgt vorzugsweise 0,2 µm-15 µm.The powder of the resistance alloy can be prepared by methods known to those skilled in the art, such as gas atomization under inert gas, water atomization or grinding. The average particle diameter d 50 of the powder of the resistance alloy is preferably 0.2 μm-15 μm.

Neben dem Pulver der Widerstandslegierung enthält Paste B ein organisches Medium. In einer bevorzugten Ausführungsform enthält Paste B das organische Medium in einer Menge von 2 - 40 Gewichtsprozent. Das organische Medium der Paste B kann mindestens ein organisches Lösungsmittel und mindestens einen Binder enthalten. Das organische Lösungsmittel kann ausgewählt sein aus der Gruppe bestehend aus Texanol, Terpineol, iso-Tridecylalkohol oder anderen hochsiedenden organischen Lösungsmitteln mit einem Siedepunkt von mindestens 140°C. Der Binder kann ausgewählt sein aus Acrylatharzen, Ethylcellulosen oder anderen Polymeren. Optional kann das organische Medium der Paste B weitere Bestandteile enthalten, die ausgewählt sein können aus der Gruppe bestehend aus Thixotropiemitteln, Stabilisatoren und Emulgatoren. Durch Zugabe dieser Bestandteile können z.B. die Verdruckbarkeit oder Lagerstabilität der Paste verbessert werden.In addition to the powder of the resistance alloy, paste B contains an organic medium. In a preferred embodiment, paste B contains the organic medium in an amount of 2-40% by weight. The organic medium of paste B may contain at least one organic solvent and at least one binder. The organic solvent can be selected from the group consisting of texanol, terpineol, iso-tridecyl alcohol or other high-boiling organic solvents having a boiling point of at least 140 ° C. The binder may be selected from acrylate resins, ethylcelluloses or other polymers. Optionally, the organic medium of paste B may contain other ingredients which may be selected from the group consisting of thixotropic agents, stabilizers and emulsifiers. By adding these ingredients, e.g. the printability or storage stability of the paste can be improved.

Die optional enthaltene Glasfritte der Paste B enthält wenigstens zwei voneinander verschiedene Elemente als Oxide. Die Elemente können ausgewählt sein aus der Gruppe bestehend aus Li, Na, K, Ca, Mg, Sr, Ba, B, Al, Si, Sn, Pb, P, Sb, Bi, Te, La, Ti, Zr, V, Nb, Mn, Fe, Co, Ni, Cu, Ag, Zn, und Cd. Die Glasfritte kann hergestellt werden aus Oxiden, Fluoriden oder sonstigen Salzen (z.B. Carbonaten, Nitraten, Phosphaten) dieser Elemente. Beispiele für Ausgangsverbindungen für die Glasfritte können ausgewählt sein aus der Gruppe bestehend aus B2O3, H3BO3, Al2O3, SiO2, PbO, P2O5, Pb3O4, PbF2, MgO, MnCO3, CaO, CaCO3, SrO, SrCO3, BaO, BaCO3, Ba(NO3)2, Na2B4O7, ZnO, ZnF2, Bi2O3, Li2O, Li2CO3, Na2O, NaCO3, NaF, K2O, K2CO3, KF, , TiO2, Nb2O5, Fe2O3, ZrO2 CuO, MnO, Mn3O4, MnO2, CdO, SnO2, TeO2, Sb2O3, Co3O4, Co2O3, CoO, La2O3, Ag2O, NiO, V2O5, Li3PO4, Na3PO4, K3PO4, Ca3(PO4)2, Mg3(PO4)2, Sr3(PO4)2, Ba3(PO4)2. und komplexen Mineralien, wie z.B. Colemanit und Dolomit.The optionally contained glass frit of paste B contains at least two mutually different elements as oxides. The elements can be selected from the group consisting of Li, Na, K, Ca, Mg, Sr, Ba, B, Al, Si, Sn, Pb, P, Sb, Bi, Te, La, Ti, Zr, V, Nb, Mn, Fe, Co, Ni, Cu, Ag, Zn, and Cd. The glass frit can be prepared from oxides, fluorides or other salts (eg carbonates, nitrates, phosphates) of these elements. Examples of starting compounds for the glass frit may be selected from the group consisting of B 2 O 3 , H 3 BO 3 , Al 2 O 3 , SiO 2 , PbO, P 2 O 5 , Pb 3 O 4 , PbF 2 , MgO, MnCO 3 , CaO, CaCO 3 , SrO, SrCO 3 , BaO, BaCO 3 , Ba (NO 3 ) 2 , Na 2 B 4 O 7 , ZnO, ZnF 2 , Bi 2 O 3 , Li 2 O, Li 2 CO 3 , Na 2 O, NaCO 3 , NaF, K 2 O, K 2 CO 3 , KF,, TiO 2 , Nb 2 O 5 , Fe 2 O 3 , ZrO 2 CuO, MnO, Mn 3 O 4 , MnO 2 , CdO, SnO 2 , TeO 2 , Sb 2 O 3 , Co 3 O 4 , Co 2 O 3 , CoO, La 2 O 3 , Ag 2 O, NiO, V 2 O 5 , Li 3 PO 4 , Na 3 PO 4 , K 3 PO 4 , Ca 3 (PO 4 ) 2 , Mg 3 (PO 4 ) 2 , Sr 3 (PO 4 ) 2 , Ba 3 (PO 4 ) 2 . and complex minerals, such as colemanite and dolomite.

In einer bevorzugten Ausführungsform kann die Glasfritte der Paste B Silizium, Aluminium, Bor und mindestens einem Erdalkalimetall jeweils als Oxid enthalten. Die Glasfritte der Paste B kann gleich sein mit der Glasfritte der Paste A oder verschieden. Die Glasfritte von Paste B kann wenigstens zwei Elemente als Oxide enthalten, die in der Glasfritte von Paste A enthalten sind. In einer bevorzugten Ausführungsform sind die Glasfritten der Pasten A und B gleich, da dies die Kompatibilität der Schichten A und B miteinander verbessern kann.In a preferred embodiment, the glass frit of paste B may contain silicon, aluminum, boron and at least one alkaline earth metal, each as oxide. The glass frit of the paste B may be the same as the glass frit of the paste A or different. The glass frit of paste B may contain at least two elements as oxides contained in the glass frit of paste A. In a preferred embodiment, the glass frits of the pastes A and B are the same, as this can improve the compatibility of the layers A and B with each other.

Für den Fall, das die Schicht aus Paste A in Schritt c) schon zur Schicht A gebrannt wurde, wird die Schicht aus Paste B demgemäß auf Schicht A aufgebracht. Durch das Aufbringen der Paste B auf die Schicht aus Schritt c) wird ein sogenannter Precursor (dt. Vorläuferstruktur) hergestellt. Der Precursor enthält somit ein Substrat, auf dem eine Schicht aus Paste A aufgebracht ist, die optional bereits gebrannt sein kann (dann auch Schicht A genannt). Weiterhin enthält der Precursor eine Schicht aus Paste B auf der Schicht aus Paste A, wobei die Schicht aus Paste B nicht gebrannt ist. In einer bevorzugten Ausführungsform wird die Paste B auf eine bereits in Schritt c. gebrannte Schicht A aufgebracht. In einer Ausführungsform kann der Precursor so ausgeführt sein, dass die Schicht aus Paste B die Schicht aus Paste A vollständig bedeckt.In the event that the layer of paste A has already been fired to layer A in step c), the layer of paste B is accordingly applied to layer A. By applying the paste B to the layer from step c), a so-called precursor (dt. Precursor structure) is prepared. The precursor thus contains a substrate on which a layer of paste A is applied, which may optionally already be fired (then also called layer A). Furthermore, the precursor contains a layer of paste B on the layer of paste A, wherein the layer of paste B is not fired. In a preferred embodiment, the paste B is applied to an already in step c. fired layer A applied. In one embodiment, the precursor may be configured so that the layer of paste B completely covers the layer of paste A.

In Schritt e) wird der Precursor gebrannt und dadurch der erfindungsgemäße Schichtaufbau erhalten. Optional kann dem Brennen ein Trockenschritt vorgelagert sein. Das Trocknen kann bei einer Temperatur im Bereich von 20 - 180°C, insbesondere im Bereich von 120-180°C erfolgen, z.B. in einem Trockenschank oder einem Infrarot-Bandtrockner.In step e), the precursor is fired, thereby obtaining the layer structure according to the invention. Optionally, the firing may be preceded by a drying step. The drying can be carried out at a temperature in the range of 20-180 ° C., in particular in the range of 120-180 ° C., for example in a dry bar or an infrared belt dryer.

Das Brennen des Precursors geschieht bevorzugt bei einer Temperatur im Bereich von 700-1000°C, insbesondere im Bereich von 850 - 900°C. Der Precursor wird vorzugsweise so gebrannt, dass sich die im Precursor befindlichen Bestandteile des organischen Mediums verflüchtigen und das Pulver der Widerstandslegierung sowie die Glasfritte zusammensintern. Das Brennen kann entweder unter Atmosphärenbedingungen in Anwesenheit von O2 oder unter Inertgasbedingungen (z.B. N2-Atmosphäre) erfolgen. Durch das Brennen der Schicht aus Paste A wird, wie weiter oben erläutert, die Schicht A erhalten und durch das Brennen der Schicht aus Paste B wird Schicht B erhalten. Für den Fall, dass die Schicht aus Paste A nicht bereits in Schritt c) gebrannt wurde, werden durch das Brennen des Precursors gleichzeitig die Schichten aus Paste A und Paste B gebrannt. Für den Fall, dass in Schritt c) die Schicht aus Paste A schon gebrannt wurde, wird die Schicht A beim Brennen der Schicht aus Paste B zwangsläufig erneut gebrannt.The burning of the precursor is preferably carried out at a temperature in the range of 700-1000 ° C, in particular in the range of 850-900 ° C. The precursor is preferably fired in such a way that the constituents of the organic medium in the precursor volatilize and the powder of the resistance alloy and the glass frit sinter together. The firing may take place either under atmospheric conditions in the presence of O 2 or under inert gas conditions (eg N 2 atmosphere). By firing the layer of paste A, as explained above, the layer A is obtained, and by firing the layer of paste B, layer B is obtained. In the case that the layer of paste A has not already been fired in step c), the layers of paste A and paste B are burned simultaneously by the firing of the precursor . In the case where the layer of paste A has already been fired in step c), the layer A is forcibly refired when the layer of paste B is fired.

Der erfindungsgemäße Schichtaufbau, der nach Schritt e) vorliegt, enthält:

  1. a. ein Substrat mit einer Glas- oder Keramikoberfläche,
  2. b. eine Schicht A, die die Glas- oder Keramikoberfläche des Substrats wenigstens teilweise bedeckt, wobei Schicht A ein Glas aufweist, in dem wenigstens zwei voneinander verschiedene Elemente als Oxide enthalten sind und eine Transformationstemperatur Tg im Bereich von 600 bis 750°C aufweist,
  3. c. eine Schicht B, die Schicht A wenigstens teilweise bedeckt, wobei Schicht B folgende Bestandteile aufweist:
    1. I. eine Widerstandslegierung mit einem Temperaturkoeffizienten der elektrischen Widerstandes weniger als 150 ppm/K, und
    2. II. optional ein Glas, das wenigstens zwei voneinander verschiedene Elemente als Oxide enthält,
    wobei Schicht B nicht mehr als 20 Gewichtsprozent Glas bezogen auf das Gesamtgewicht der Schicht B enthält.
The layer structure according to the invention which is present after step e) contains:
  1. a. a substrate with a glass or ceramic surface,
  2. b. a layer A which at least partially covers the glass or ceramic surface of the substrate, wherein layer A comprises a glass in which at least two different elements are contained as oxides and has a transformation temperature T g in the range of 600 to 750 ° C,
  3. c. a layer B which at least partially covers layer A, layer B having the following constituents:
    1. I. a resistance alloy having a temperature coefficient of electrical resistance less than 150 ppm / K, and
    2. II. Optionally a glass containing at least two different elements as oxides,
    wherein layer B contains not more than 20% by weight of glass based on the total weight of layer B.

Schicht A, die die Glas- oder Keramikoberfläche des Substrats wenigstens teilweise bedeckt, weist das Glas auf, dass durch Brennen der Glasfritte aus Paste A erhalten wird. Typischer Weise enthält das Glas in Schicht A die zusammengesinterte Glasfritte aus Paste A. Bevorzugt ist diese Glasfritte über die gesamte Ausdehnung der Schicht A homogen zum Glas zusammengesintert und weist keine nicht-gesinterten Bereiche auf.Layer A, which at least partially covers the glass or ceramic surface of the substrate, comprises the glass obtained by firing the glass frit from paste A. Typically, the glass in layer A contains the sintered glass frit of paste A. Preferably, this glass frit is homogeneously sintered to the glass over the entire extent of layer A and has no non-sintered regions.

Im Schichtaufbau weist Schicht B die Widerstandslegierung aus Paste B auf und ist mechanisch fest mit Schicht A verbunden. Die mechanische Festigkeit der Haftung kann mittels verschiedener Tests bestimmt werden. Schicht B kann des Schichtaufbaus kann einen TCR-Wert aufweisen, der dem Bulk-Wert der Widerstandslegierung im Wesentlichen entspricht.In the layer structure, layer B has the resistance alloy of paste B and is mechanically firmly connected to layer A. The mechanical strength of adhesion can be determined by various tests. Layer B of the layer structure may have a TCR value substantially equal to the bulk value of the resistance alloy.

Die Haftfestigkeit kann durch folgende Tests überprüft werden: Auf den gebrannten Schichtaufbau wird ein Streifen Klebefilm der Marke Scotch®- Magic (3M Deutschland GmbH) aufgeklebt und zum Beispiel mit dem Fingernagel fest aufgestrichen. Anschließend wird der Klebefilm wieder abgezogen. Widerstandslegierungsschichten mit geringer Haftfestigkeit zur Glas- oder Keramikoberfläche des Substrats haften am Klebefilm. Schichtaufbauten mit einer mittleren Haftfestigkeit verbleiben teilweise am Klebefilm und Schichtaufbauten mit einer hohen Haftfestigkeit werden nicht vom Klebefilm abgelöst.The adhesion can be checked by the following tests: A strip of adhesive tape of the brand Scotch®-Magic (3M Germany GmbH) is glued to the fired layer structure and, for example, firmly brushed with a fingernail. Subsequently, the adhesive film is removed again. Resistant alloy layers with low adhesion to the glass or ceramic surface of the substrate adhere to the adhesive film. Layered structures with a medium adhesive strength remain partly on the adhesive film and layer structures with a high adhesive strength are not detached from the adhesive film.

In dem Schichtaufbau kann Schicht A als Haftvermittler zwischen der Glas- oder Keramikoberfläche des Substrats und der, die Widerstandslegierung enthaltenden, Schicht B wirken. Durch die vorliegende Erfindung kann somit eine Schicht einer Widerstandslegierung erhalten werden, die mechanisch stabil mit der Substratoberfläche verbunden ist. Die Schicht B enthält, die Widerstandslegierung in der ursprünglich in Paste B eingesetzten Menge.In the layer structure, layer A can act as a bonding agent between the glass or ceramic surface of the substrate and the layer B containing the resistance alloy. Thus, the present invention can provide a layer of resistance alloy mechanically stably bonded to the substrate surface. The layer B contains the resistance alloy in the amount originally used in paste B.

Für den optionalen Fall, dass Schicht B zusätzlich ein Glas aufweist, dass aus der Glasfritte der Paste B hergestellt wurde, kann die Haftung der Schicht B auf der Schicht A weiter verbessert werden. Der Glasgehalt der Schicht B bestimmt sich nach der eingesetzten Menge an Glasfritte in Paste B. In einer bevorzugten Ausführungsform weist die Schicht B nicht mehr als 20 Gewichtsprozent Glas, insbesondere nicht mehr als 15 Gewichtsprozent Glas auf, bezogen auf das Gesamtgewicht der Schicht B.For the optional case that layer B additionally has a glass made from the glass frit of paste B, the adhesion of layer B to layer A can be further improved. The glass content of layer B is determined by the amount of glass frit used in paste B. In a preferred embodiment, layer B comprises not more than 20% by weight of glass, in particular not more than 15% by weight of glass, based on the total weight of layer B.

Optional kann der Schichtaufbau im Anschluss an Schritt e) mit einer Versiegelung (auch Schutzglasur, oder Overglaze genannt) versehen werden. Typischer Weise besteht diese Versiegelung aus einem Glas. Diese Versiegelung dient insbesondere dazu, den Schichtaufbau vor Umwelteinflüssen, wie z.B. Feuchtigkeit, zu schützen.Optionally, the layer structure following step e) can be provided with a seal (also called protective glaze , or overglaze ). Typically, this seal is made of a glass. This seal is used in particular to protect the layer structure from environmental influences, such as moisture.

Der erfindungsgemäße Schichtaufbau kann unter anderem dazu verwendet werden, Präzisionswiderstände herzustellen.The layer structure according to the invention can be used inter alia to produce precision resistors.

BeispieleExamples Allgemeine Herstellung der Paste AGeneral preparation of paste A

Pasten A wurde durch Mischen von 22 Gew.% organischem Medium (85 Gew.% Texanol, 15 Gew.% Ethylcellulose (75% N7, 25% N50)) und 78 Gew.% einer Glasfritte gemäß Tabelle 1 hergestellt. Die Pasten wurden mittels einem Drei-Walzen-Stuhl homogenisiert. Tabelle 1: Verwendete Gläser Glasfritte 1 Glasfritte 2 Glasfritte 3 Glasfritte 4 Glasfritte 5 Glasfritte 6 Glasfritte 7 Gew% Gew% Gew% Gew% Gew% Gew% Gew% SiO2 43,0 50,0 48,0 16,8 43,0 57,0 42,0 Al2O3 9,0 10,0 10,0 9,0 12,0 18,0 MgO 3,0 2,0 3,0 CaO 6,0 10,0 8,0 6,0 9,0 35,0 SrO 5,0 22,0 5,0 BaO 30,0 9,0 5,0 47,8 30,0 Na2O 1,0 K2O 2,0 4,0 2,0 2,0 5,0 B2O3 2,0 15,0 4,0 35,5 2,0 17,0 5,0 Summe 100,0 100 100,0 100,0 100 100 100,0 Paste A was prepared by mixing 22% by weight of organic medium (85% by weight of Texanol, 15% by weight of ethylcellulose (75% N7, 25% N50)) and 78% by weight of a glass frit according to Table 1. The pastes were homogenized by means of a three-roll chair. <b> Table 1: Used glasses </ b> Glass frit 1 Glass frit 2 Glass frit 3 Glass frit 4 Glass frit 5 Glass frit 6 Glass frit 7 wt% wt% wt% wt% wt% wt% wt% SiO2 43.0 50.0 48.0 16.8 43.0 57.0 42.0 Al 2 O 3 9.0 10.0 10.0 9.0 12.0 18.0 MgO 3.0 2.0 3.0 CaO 6.0 10.0 8.0 6.0 9.0 35.0 SrO 5.0 22.0 5.0 BaO 30.0 9.0 5.0 47.8 30.0 Na 2 O 1.0 K 2 O 2.0 4.0 2.0 2.0 5.0 B 2 O 3 2.0 15.0 4.0 35.5 2.0 17.0 5.0 total 100.0 100 100.0 100.0 100 100 100.0

Allgemeine Herstellung Pasten BGeneral production pastes B

Ein Pulver der Widerstandslegierung Isotan (mittlerer Teilchendurchmesser d50: 8 µm, hergestellt durch Gasverdüsen einer Schmelze unter N2-Atmosphäre), ein organisches Medium (65 Gew.% Texanol und 35 Gew.% Acrylat-Binder) und ggfs. eine Glasfritte wurden in den spezifizierten Mengen zusammengegeben und mittels einem Drei-Walzen-Stuhl homogenisiert. Die hergestellten Pasten weisen eine Viskosität von etwa 30-90 Pas bei 20-25°C auf. Tabelle 2 Gew. % Glasfritte 7 Isotanpulver Organisches Medium Paste B1 6 84 10 A powder of the resistance alloy isotan (average particle diameter d 50 : 8 microns, prepared by gas atomizing a melt under N 2 atmosphere), an organic medium (65 wt.% Texanol and 35 wt.% Acrylate binder) and, if necessary, a glass frit combined in the specified amounts and homogenized using a three-roll chair. The pastes produced have a viscosity of about 30-90 Pas at 20-25 ° C. <b> Table 2 </ b> % By weight Glass frit 7 Isotanpulver Organic medium Paste B1 6 84 10

Herstellung des SchichtaufbausProduction of the layer structure

Die Glaspasten A, enthaltend die Glasfritten aus Tabelle 1, wurden durch Siebdruck auf Al2O3 Substraten mit einer Größe von 101,6 x 101,6 mm und einer Dicke von 0,63 mm (Rubalit 708 S, CeramTec) aufgebracht. Dafür wurde ein Sieb der Firma Koenen GmbH, Deutschland mit einem EKRA Microtronic II Drucker (type M2H) verwendet. Die Emulsionsdicke betrug etwa 50 µm (Siebparameter: 80 mesh und 65 µm Drahtdurchmesser (Edelstahl)). Druckparameter: 63 N Rakeldruck, Rakelgeschwindigkeit 100 mm/s und einem Absprung von 1.0 mm. Die Schichtdicke nach dem Drucken (nass) betrug etwa 90 µm. 10 Minuten nach dem Drucken wurden die Proben in einem Infrarot-Bandtrockner (BTU international, Type HHG-2) für 20 min bei 150°C getrocknet. Die Schichtdicke nach dem Trocknen betrug etwa 60 µm. Die gedruckten Glasschichten wurden unter Stickstoffatmosphäre (N2 5.0) in einem Ofen gebrannt (ATV Technologie GmbH, Typ PEO 603). Die Temperatur wurde von 25°C auf 850°C erhöht, für 10 bei 850°C gehalten und anschließend innerhalb von 20 min auf 25°C abgekühlt. (Gesamtdurchlaufzeit 82 min) Die Schichtdicke nach dem Brennen betrug etwa 50 µm. Die Widerstandslegierungspaste B wurden mittels Siebdruck auf die zuvor hergestellte Schicht aufgebracht. Dafür wurde ein Sieb der Firma Koenen GmbH, Deutschland mit einem EKRA Microtronic II Drucker (Typ M2H) verwendet. Die Emulsionsdicke betrug etwa 50 µm, Siebparameter: 80 mesh und 65 µm Drahtdurchmesser (Edelstahl).The glass pastes A containing the glass frits from Table 1 were applied by screen printing on Al 2 O 3 substrates having a size of 101.6 × 101.6 mm and a thickness of 0.63 mm (Rubalit 708 S, CeramTec). For this purpose, a sieve from Koenen GmbH, Germany was used with an EKRA Microtronic II printer (type M2H). The emulsion thickness was about 50 μm (sieving parameter: 80 mesh and 65 μm wire diameter (stainless steel)). Printing parameters: 63 N squeegee pressure, squeegee speed 100 mm / s and a jump of 1.0 mm. The layer thickness after printing (wet) was about 90 μm. 10 minutes after printing, the samples were placed in an infrared belt dryer (BTU international, type HHG-2) for 20 min dried at 150 ° C. The layer thickness after drying was about 60 microns. The printed glass layers were fired in a nitrogen atmosphere (N 2 5.0) in an oven (ATV Technologie GmbH, type PEO 603). The temperature was increased from 25 ° C to 850 ° C, held at 850 ° C for 10 and then cooled to 25 ° C within 20 min. (Total throughput time 82 min) The layer thickness after firing was about 50 μm. The resistance alloy paste B was applied to the previously prepared layer by screen printing. For this purpose, a sieve made by Koenen GmbH, Germany was used with an EKRA Microtronic II printer (type M2H). The emulsion thickness was about 50 μm, screen parameters: 80 mesh and 65 μm wire diameter (stainless steel).

Die gedruckten Widerstandslegierungspasten (also auch der Precursor) wurden unter Stickstoffatmosphäre (N2 5.0) in einem Ofen gebrannt (ATV Technologie GmbH, Typ PEO 603). Die Temperatur wurde von 25°C auf 900°C erhöht, für 10 min bei 900°C gehalten und innerhalb von 20 min auf 25°C abgekühlt (Gesamtdurchlaufzeit 82 min). Die Schichtdicke nach dem Brennen betrug etwa 50 µm.The printed resistance alloy pastes (including the precursor ) were fired in a nitrogen atmosphere (N 2 5.0) in an oven (ATV Technology GmbH, type PEO 603). The temperature was increased from 25 ° C to 900 ° C, held for 10 min at 900 ° C and cooled within 20 min to 25 ° C (total flow time 82 min). The layer thickness after firing was about 50 μm.

Beispiel 1example 1

Tabelle 3: Haftungsversuche mit Glaspasten (Paste A) mit unterschiedlichen GlasfrittenTable 3: Adhesion tests with glass pastes (paste A) with different glass frits Schichtaufbaulayer structure Substratsubstratum Glasfritte (Paste A)Glass frit (paste A) Isotan-PasteIsotan paste Haftung Isotan auf SubstratAdhesion Isotan on substrate + = gut; o = mäßig; - = schlecht+ = good; o = moderate; - = bad 11 11 ++ 22 22 ++ 33 33 ++ 44 Al2O3 Al 2 O 3 44 Paste B1 (6% Glas 7)Paste B1 (6% glass 7) ++ 55 55 ++ 66 66 ++ 77 77 ++ 88th kein Glasno glass --

Beispiel 2Example 2

Haftung Schichtaufbau in Abhängigkeit der Glasmenge in Paste B Tabelle 4 Widerstandslegierungspasten (Paste B) mit unterschiedlichem Gehalt an Glasfritte [Gew.%] Glassfritte 7 Isotanpulver Organisches Medium Paste B2 0 90 10 Paste B3 3 87 10 Paste B4 6 84 10 Paste B5 9 81 10 Tabelle 5 Haftung Schichtaufbau in Abhängigkeit der Glasmenge in Paste B vor und nach T-Shock Lagerung Schichtaufbau Substrat Glasschicht (Schicht A) Legierungsschicht (Schicht B) Haftung vor T-Shock Lagerung Ablösung nach T-Shock Lagerung 9 Al2O3 Paste A aus Glas 7 Paste B2 gut 20 Zyklen 10 Paste B3 gut 100 Zyklen 11 Paste B4 gut >500 Zyklen 12 Paste B5 gut >500 Zyklen Adhesion Layer structure depending on the amount of glass in paste B <b> Table 4 Resistance alloy pastes (Paste B) with different content of glass frit </ b> [Wt.%] Glass frit 7 Isotanpulver Organic medium Paste B2 0 90 10 Paste B3 3 87 10 Paste B4 6 84 10 Paste B5 9 81 10 layer structure substratum Glass layer (layer A) Alloy layer (layer B) Liability before T-shock storage Replacement after T-Shock storage 9 Al 2 O 3 Paste A made of glass 7 Paste B2 Good 20 cycles 10 Paste B3 Good 100 cycles 11 Paste B4 Good > 500 cycles 12 Paste B5 Good > 500 cycles

T-Shock-Lagerung:T-Shock Storage:

Die Hergestellten Schichtaufbauten wurden jeweils 15 min in einer Kammer mit einer Temperatur von -40°C bzw. +150°C gelagert. Der Übergang von einer Kammer zur anderen erfolgte automatisiert und dauerte ca. 4s. Ein Zyklus beinhaltet jeweils eine Lagerung bei -40°C und eine bei +150°C. Die Haftung wurde nach verschiedenen Anzahlen von Zyklen mit einem Klebestreifen, wie oben beschrieben, überprüft.The prepared layer structures were each stored for 15 minutes in a chamber with a temperature of -40 ° C and + 150 ° C, respectively. The transition from one chamber to another was automated and lasted about 4s. One cycle contains storage at -40 ° C and one at + 150 ° C. The adhesion was checked after various numbers of cycles with an adhesive strip as described above.

Für Schichtaufbau 9 und Schichtaufbau 12 wurden die TCR-Werte im Temperaturbereich 20-60°C gemäß der Norm DIN EN 60115-1:2016-03 (Trocknungsverfahren I) gemessen: Tabelle 6 Schichtaufbau Menge Glasfritte in Paste B TCR 9 0 Gew.% -25 bis -14 ppm/K 12 9 Gew.% -37 bis -21 ppm/K For layer structure 9 and layer structure 12, the TCR values were measured in the temperature range 20-60 ° C. according to the standard DIN EN 60115-1: 2016-03 (drying method I): <b> Table 6 </ b> layer structure Quantity of glass frit in paste B TCR 9 0% by weight -25 to -14 ppm / K 12 9% by weight -37 to -21 ppm / K

Zum Vergleich Der TCR Bulk-Wert für Isotan (als Draht) liegt im Bereich von -80 bis +40 ppm/K.For comparison The TCR bulk value for isotan (as a wire) ranges from -80 to +40 ppm / K.

Claims (14)

Verfahren zur Herstellung eines Schichtaufbaus umfassend die aufeinander folgenden Schritte: a. Bereitstellung eines Substrats mit einer Glas - oder Keramikoberfläche, b. Aufbringen einer Paste A auf wenigstens einen Teil der Glas-oder Keramikoberfläche des Substrats unter Erhalt einer Schicht aus Paste A, wobei Paste A folgende Bestandteile enthält: I. eine Glasfritte, die wenigstens zwei voneinander verschiedene Elemente als Oxide enthält und eine Transformationstemperatur Tg im Bereich von 600 bis 750°C aufweist und II. ein organisches Medium, c. Trocknen und gegebenenfalls Brennen der Schicht aus Paste A d. Aufbringen einer Paste B auf wenigstens einen Teil der Schicht aus Schritt c. unter Erhalt eines Schicht aus Paste B, wobei Paste B folgende Bestandteile enthält: I. Ein Pulver einer Widerstandslegierung mit einem Temperaturkoeffizienten des elektrischen Widerstandes von weniger als 150 ppm/K II. ein organisches Medium, III. 0 - 15 Gewichtsprozent Glasfritte, bezogen auf das Gesamtgewicht von Paste B, und e. Brennen und optional vor dem Brennen Trocknen der Schichten aus Paste B. Process for producing a layer structure comprising the successive steps: a. Providing a substrate having a glass or ceramic surface, b. Applying a paste A to at least part of the glass or ceramic surface of the substrate to obtain a layer of paste A, wherein paste A contains the following components: I. a glass frit which contains at least two mutually different elements as oxides and has a transformation temperature T g in the range of 600 to 750 ° C and II. An organic medium, c. Drying and optionally firing the layer of paste A d. Applying a paste B to at least a portion of the layer of step c. to obtain a layer of paste B, wherein paste B contains the following components: I. A powder of a resistance alloy having a temperature coefficient of electrical resistance of less than 150 ppm / K II. An organic medium, III. 0 to 15 weight percent glass frit, based on the total weight of paste B, and e. Burning and optionally before firing drying the layers of paste B. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass Paste B eine Glasfritte enthält, die wenigstens zwei voneinander verschiedene Elemente als Oxide enthält.A method according to claim 1, characterized in that paste B contains a glass frit containing at least two mutually different elements as oxides. Verfahren nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, dass Paste B nicht mehr als 12 Gewichtsprozent und vorzugsweise 5 - 12 Gewichtsprozent, Glasfritte, bezogen auf das Gesamtgewicht von Paste B enthält.Method according to one of claims 1 or 2, characterized in that paste B contains not more than 12% by weight, and preferably from 5 to 12% by weight, of glass frit, based on the total weight of paste B. Verfahren nach einem der Ansprüche 1 - 3, wobei die Widerstandslegierung der Paste B einen Temperaturkoeffizienten der elektrischen Widerstandes von weniger als 50 ppm/K aufweist.A method according to any one of claims 1-3, wherein the resistance alloy of the paste B has a temperature coefficient of electrical resistance of less than 50 ppm / K. Verfahren nach einem der Ansprüche 1 - 4, wobei die Widerstandslegierung der Paste B ausgewählt ist aus der Gruppe bestehend aus : Legierung I. a. 53,0 - 57,0 Gewichtsprozent Kupfer, b. 42,0 - 46,0 Gewichtsprozent Nickel, c. 0,5 - 1,2 Gewichtsprozent Mangan und d. Nicht mehr als 10000 Gew. ppm sonstiger Elemente. Legierung II. a. 83,0 - 89,0 Gewichtsprozent Kupfer, b. 10,0 - 14,0 Gewichtsprozent Mangan, c. 1 - 3 Gewichtsprozent Nickel und d. Nicht mehr als 10000 Gew. ppm sonstiger Elemente. Legierung III. a. 88,0 - 93,0 Gewichtsprozent Kupfer, b. 5,0 - 9,0 Gewichtsprozent Mangan, c. 2 - 3 Gewichtsprozent Zinn und d. Nicht mehr als 10000 Gew. ppm sonstiger Elemente. Legierung IV. a. 61,0 - 69,0 Gewichtsprozent Kupfer, b. 23,0 - 27,0 Gewichtsprozent Mangan, c. 8 - 12 Gewichtsprozent Nickel und d. Nicht mehr als 10000 Gew. ppm sonstiger Elemente.
und Legierung V. a. 70,0 - 78,0 Gewichtsprozent Nickel, b. 18,0 - 22,0 Gewichtsprozent Chrom, c. 3 - 4 Gewichtsprozent Aluminium, d. 0,5 - 1,5 Gewichtsprozent Silicium, e. 0,2 - 0,8 Gewichtsprozent Mangan, f. 0,2 - 0,8 Gewichtsprozent Eisen, g. Nicht mehr als 10000 Gew. ppm sonstiger Elemente. The method of any one of claims 1-4, wherein the resistive alloy of paste B is selected from the group consisting of: Alloy I. a. 53.0-57.0 weight percent copper, b. 42.0-46.0 weight percent nickel, c. 0.5 - 1.2 weight percent manganese and d. Not more than 10000 ppm by weight of other elements. Alloy II. a. 83.0-89.0 weight percent copper, b. 10.0 - 14.0 weight percent manganese, c. 1 - 3 weight percent nickel and d. Not more than 10000 ppm by weight of other elements. Alloy III. a. 88.0 - 93.0 weight percent copper, b. 5.0-9.0 weight percent manganese, c. 2 - 3 weight percent tin and d. Not more than 10000 ppm by weight of other elements. Alloy IV. a. 61.0-69.0 weight percent copper, b. 23.0 - 27.0 weight percent manganese, c. 8 - 12 weight percent nickel and d. Not more than 10000 ppm by weight of other elements.
and Alloy V. a. 70.0-78.0 weight percent nickel, b. 18.0-22.0 weight percent chromium, c. 3 to 4 weight percent aluminum, d. 0.5 to 1.5 weight percent silicon, e. 0.2 - 0.8 weight percent manganese, f. 0.2-0.8 weight percent iron, G. Not more than 10000 ppm by weight of other elements. Verfahren nach einem der Ansprüche 1 - 5, dadurch gekennzeichnet, dass Paste A 50 - 90 Gewichtsprozent Glasfritte und 10 - 50 Gewichtsprozent organisches Medium, bezogen auf das Gesamtgewicht von Glasfritte und organischem Medium, enthält.A method according to any one of claims 1-5, characterized in that paste A contains 50-90% by weight of glass frit and 10-50% by weight of organic medium, based on the total weight of glass frit and organic medium. Verfahren nach einem der Ansprüche 1 - 6, dadurch gekennzeichnet, dass die Glasfritten von Paste A und/oder Paste B Silizium, Bor, Aluminium und ein Erdalkalimetall jeweils als Oxid enthalten.Method according to one of claims 1-6, characterized in that the glass frits of paste A and / or paste B silicon, boron, aluminum and an alkaline earth metal each contain as oxide. Verfahren nach einem der Ansprüche 1 - 7, dadurch gekennzeichnet, dass die Glasfritte von Paste B wenigstens zwei Elemente als Oxide enthält, die in der Glasfritte von Paste A enthalten sind.Method according to one of claims 1-7, characterized in that the glass frit of paste B contains at least two elements as oxides, which are contained in the glass frit of paste A. Verfahren nach einem der Ansprüche 1 - 8, dadurch gekennzeichnet, dass Paste B 60 - 95 Gewichtsprozent der Widerstandslegierung, 3 - 15 Gewichtsprozent Glasfritte und 2 - 37 Gewichtsprozent organisches Medium, bezogen auf das Gesamtgewicht von Paste B, enthält.Process according to any one of claims 1-8, characterized in that paste B contains 60-95% by weight of the resistance alloy, 3-15% by weight of glass frit and 2-37% by weight of organic medium, based on the total weight of paste B. Schichtaufbau aufweisend: a. ein Substrat mit einer Glas-oder Keramikoberfläche, b. eine Schicht A, die die Glas- oder Keramikoberfläche des Substrats wenigstens teilweise bedeckt, wobei Schicht A ein Glas aufweist, in dem wenigstens zwei voneinander verschiedene Elemente als Oxide enthalten sind und das eine Transformationstemperatur Tg im Bereich von 600 bis 750°C aufweist, c. eine Schicht B, die Schicht A wenigstens teilweise bedeckt, wobei Schicht B folgende Bestandteile aufweist: I. eine Widerstandslegierung mit einem Temperaturkoeffizienten der elektrischen Widerstandes weniger als 150 ppm/K, und II. optional ein Glas, das wenigstens zwei voneinander verschiedene Elemente als Oxide enthält,
wobei Schicht B nicht mehr als 20 Gewichtsprozent Glas, bezogen auf das Gesamtgewicht der Schicht B enthält. Having a layer structure: a. a substrate with a glass or ceramic surface, b. a layer A which at least partially covers the glass or ceramic surface of the substrate, wherein layer A comprises a glass in which at least two different elements are contained as oxides and which has a transformation temperature T g in the range of 600 to 750 ° C, c. a layer B which at least partially covers layer A, layer B having the following constituents: I. a resistance alloy having a temperature coefficient of electrical resistance less than 150 ppm / K, and II. Optionally a glass containing at least two different elements as oxides,
wherein layer B contains not more than 20% by weight of glass, based on the total weight of layer B. Paste aufweisend a. Ein Pulver einer Widerstandslegierung mit einem Temperaturkoeffizienten der elektrischen Widerstandes weniger als 150 ppm/K b. eine Glasfritte aufweisend Silizium, Bor, Aluminium und ein Erdalkalimetall jeweils als Oxid, c. ein organisches Medium. Having paste a. A powder of a resistance alloy having a temperature coefficient of electrical resistance less than 150 ppm / K b. a glass frit comprising silicon, boron, aluminum and an alkaline earth metal each as oxide, c. an organic medium. Paste nach Anspruch 11, dadurch gekennzeichnet, dass das Erdalkalimetall Calcium ist.Paste according to claim 11, characterized in that the alkaline earth metal is calcium. Paste nach einem der Ansprüche 11 oder 12, dadurch gekennzeichnet, dass die Glasfritte hergestellt ist aus a. 25 - 55 Gewichtsprozent Siliziumoxid, b. 20 - 45 Gewichtsprozent Calciumcarbonat, c. 10 - 30 Gewichtsprozent Aluminiumoxid und d. 1 - 10 Gewichtsprozent Boroxid. Paste according to one of claims 11 or 12, characterized in that the glass frit is made from a. 25-55% by weight silica, b. 20-45% by weight calcium carbonate, c. 10 to 30 weight percent alumina and d. 1 - 10 weight percent boron oxide. Verwendung des Schichtaufbaus gemäß Anspruch 10, zur Herstellung von Präzisionswiderständen.Use of the layer structure according to claim 10, for the production of precision resistors.
EP16193341.1A 2016-10-11 2016-10-11 Method for producing a layer structure using a paste based on a resistance alloy Active EP3309800B1 (en)

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EP16193341.1A EP3309800B1 (en) 2016-10-11 2016-10-11 Method for producing a layer structure using a paste based on a resistance alloy
ES16193341T ES2730825T3 (en) 2016-10-11 2016-10-11 Procedure for producing a layered structure using a paste based on a strength alloy
CN201780062982.9A CN109906491A (en) 2016-10-11 2017-09-18 Method for producing a layered structure using a paste based on a resistive alloy
JP2019519641A JP2019537838A (en) 2016-10-11 2017-09-18 Method for producing layered structure using paste based on resistance alloy
KR1020197011773A KR102298321B1 (en) 2016-10-11 2017-09-18 A method for manufacturing a layer structure using a paste containing a resistance alloy
PCT/EP2017/073421 WO2018068989A1 (en) 2016-10-11 2017-09-18 Method for producing a layer structure using a paste on the basis of a resistive alloy
US16/340,611 US20200051719A1 (en) 2016-10-11 2017-09-18 Method for producing a layer structure using a paste on the basis ofa resistive alloy
TW106134416A TWI765919B (en) 2016-10-11 2017-10-05 Method and layered structure for producing layered structures using resistive alloy-based pastes
US17/388,676 US20220051834A1 (en) 2016-10-11 2021-07-29 Method for producing a layer structure using a paste on the basis ofa resistive alloy

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CN109906491A (en) 2019-06-18
WO2018068989A1 (en) 2018-04-19
TW201841174A (en) 2018-11-16
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