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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• Non-Adjustable Resistors (AREA)
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• 2016
  • 2016-10-11 ES ES16193341T patent/ES2730825T3/es active Active
  • 2016-10-11 EP EP16193341.1A patent/EP3309800B1/fr active Active
• 2017
  • 2017-09-18 CN CN201780062982.9A patent/CN109906491A/zh active Pending
  • 2017-09-18 WO PCT/EP2017/073421 patent/WO2018068989A1/fr active Application Filing
  • 2017-09-18 JP JP2019519641A patent/JP2019537838A/ja active Pending
  • 2017-09-18 US US16/340,611 patent/US20200051719A1/en not_active Abandoned
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