A sulfur-resistant thick film resistor

Abstract

The present invention relates to the field of resistor technology, and in particular to a sulfur-resistant thick-film resistor, comprising: a tin plating layer, a nickel plating layer arranged inside the tin plating layer, a conductor layer located on both sides of the nickel plating layer, a substrate arranged in the middle of the conductor layer, and a resistor layer arranged on the substrate, wherein electrode assemblies are arranged above and below the substrate, and a resistor protection layer is arranged on the upper side of the electrode assembly arranged above; the resistor protection layer comprises a sacrificial layer and a stabilizing layer, the stabilizing layer is arranged on the upper side of the electrode assembly, the sacrificial layer is fixed on the upper side of the stabilizing layer, the stabilizing layer is made of a highly sulfur-resistant material, and the sacrificial layer is made of a low-activity conductive phase material; a self-repairing layer is arranged on the upper side of the resistor layer, the self-repairing layer comprises micro-repair capsules, and a corrosion inhibitor is arranged inside the micro-repair capsules. The present invention breaks through the bottlenecks of existing technologies from the perspectives of structural protection and dynamic repair, respectively. The combination of the two can significantly improve the reliability of sulfur-resistant thick-film resistors.

Description

Technical Field

[0001] The present invention relates to the technical field of resistors, and in particular to a sulfurization-resistant thick-film resistor. Background Art

[0002] Thick film resistors are made by printing thick film resistor paste on a substrate and then sintering it at high temperature. Sulfur resistance may refer to the ability of this resistor to resist corrosion from sulfides, because in certain sulfur-containing environments, sulfides can cause resistor performance degradation or even failure.

[0003] Chinese patent publication number CN219370711U discloses a sulfur-resistant, high-voltage-resistant thick-film chip resistor comprising a first tin layer, a ceramic substrate, a second tin layer, and a silver electrode. The first tin layer has a first notch in the center, into which one end of the ceramic substrate is inserted. The second tin layer has a second notch in the center, into which the other end of the ceramic substrate is inserted. This patent application incorporates a specially designed extended circuit printed in the center of the silver electrode to enable higher voltage resistance. It also includes first and second protective layers.

[0004] However, the existing resistor layer cannot repair itself after being damaged, which reduces its resistance to sulfide and affects the normal use of the resistor layer. Summary of the Invention

[0005] The purpose of the present invention is to solve the shortcomings of the prior art that after being damaged, the resistor cannot self-repair, thereby reducing the resistance to sulfurization and affecting the normal use of the resistor layer, and to propose a sulfurization-resistant thick film resistor.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] A sulfurization-resistant thick film resistor, comprising: a tin plating layer, a nickel plating layer disposed within the tin plating layer, conductor layers disposed on both sides of the nickel plating layer, a substrate disposed in the middle of the conductor layer, and a resistor layer disposed on the substrate, wherein an electrode assembly is disposed above and below the substrate, and a resistor protection layer is disposed on the upper side of the electrode assembly disposed above the substrate;

[0008] The resistance protection layer includes a sacrificial layer and a stabilizing layer, wherein the stabilizing layer is arranged on the upper side of the electrode assembly, and the sacrificial layer is fixed on the upper side of the stabilizing layer. The stabilizing layer is made of a highly sulfidation-resistant material, and the sacrificial layer is made of a low-activity conductive phase material;

[0009] A self-repairing layer is provided on the upper side of the resistance layer. The self-repairing layer includes micro-repairing capsules. The interior of the micro-repairing capsules is provided with a corrosion inhibitor, and the outer shell is provided with two layers, namely, a heat-resistant layer located on the outside and a wrapping layer located on the inside.

[0010] Preferably, the electrode assembly includes two upper electrode blocks and two lower electrode blocks, the two upper electrode blocks are arranged on both sides above the substrate, and the two lower electrode blocks are arranged on both sides below the substrate.

[0011] Preferably, a plurality of arc-shaped raised strips are provided on the upper surface of the sacrificial layer, and diversion ramps are provided between the plurality of arc-shaped raised strips. The diversion ramps are inclined toward both sides for diverting fluid from the middle to both sides.

[0012] Preferably, a glass glaze protective layer is provided above the resistance layer, and the interior of the glass glaze protective layer is filled with silicon dioxide or oxide nanoparticles.

[0013] Preferably, the stabilizing layer is made of ruthenium dioxide for maintaining resistance stability, and the sacrificial layer is made of tungsten carbide for sacrificially blocking sulfur corrosion.

[0014] Preferably, the self-repairing layer further comprises slurry, the micro-repairing capsules are mixed inside the slurry, and the self-repairing layer is arranged between the resistance protection layer and the resistance layer to protect the resistance layer.

[0015] Preferably, the micro-repair capsules are spherical, and the size of the micro-repair capsules needs to be smaller than the conductive phase particles in the slurry.

[0016] Preferably, the corrosion inhibitor is zincate, the heat-resistant layer is a rigid layer made of silicon dioxide, and the wrapping layer is a flexible layer made of polyimide.

[0017] Preferably, silicon carbide nanowires are provided inside the heat-resistant layer, and chitosan response strips are provided inside the wrapping layer.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] 1. The resistor protection layer design builds a multi-layer resistor structure, utilizing the physical and chemical properties of different materials for synergistic protection. The self-healing layer embeds micro-repair capsules to achieve dynamic protection, breaking through existing technical bottlenecks from the perspectives of structural protection and dynamic repair. The combination of the two can significantly improve the reliability of sulfur-resistant thick-film resistors.

[0020] 2. By providing multiple arc-shaped raised strips on the sacrificial layer, the infiltrated sulfur is diverted and dispersed on the sacrificial layer. At the same time, an inclined diversion slope is provided under the multiple arc-shaped raised strips to guide the infiltrated sulfur to both sides. The moved sulfur will evenly contact and react with the low-activity conductive material on the sacrificial layer, thereby increasing the service life of the entire sacrificial layer and ensuring the sulfur barrier effect.

[0021] 3. The inner layer uses high-stability materials, such as ruthenium dioxide, to maintain the long-term stability of the resistance value and avoid performance failure due to corrosion of the outer layer. The outer layer can use low-cost materials to reduce the amount of precious metals and reduce the overall cost. In addition, multi-layer printing technology has been maturely applied in the manufacture of thick film resistors.

[0022] 4. Fill the glass glaze protective layer with 5-10% silica or oxide nanoparticles by mass. Nanoparticles fill micropores, improve density, reduce sulfur penetration paths, and thus improve the protection effect;

[0023] 5. Since the micro-repair capsule has the risk of sintering and cracking during use, silicon carbide nanowires are used to reinforce the wall material inside the heat-resistant layer to improve the thermal shock resistance of the micro-repair capsule;

[0024] 6. In order to avoid the premature release of corrosion inhibitors, pH-responsive wall materials are designed so that the micro-repair capsules dissolve only in the acidic environment caused by sulfides, reducing the waste of corrosion inhibitors. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 This is a schematic diagram of the cross-sectional structure of a sulfur-resistant thick film resistor proposed by the present invention;

[0026] Figure 2 This is a schematic diagram of the front structure of a sulfur-resistant thick film resistor proposed by the present invention;

[0027] Figure 3 A schematic diagram of the internal structure of a sulfur-resistant thick-film resistor proposed by the present invention;

[0028] Figure 4 This is a schematic diagram of the structure of the glass glaze protective layer of a sulfurization-resistant thick film resistor proposed by the present invention;

[0029] Figure 5 This is a schematic diagram of the self-repairing layer structure of a sulfur-resistant thick film resistor proposed by the present invention;

[0030] Figure 6 A schematic diagram of the stabilizing layer structure of a sulfur-resistant thick film resistor proposed by the present invention;

[0031] Figure 7 This is a schematic diagram of the micro-repair capsule structure of a sulfur-resistant thick-film resistor proposed by the present invention.

[0032] In the figure: 1. Tin plating; 2. Nickel plating; 3. Conductor layer; 4. Substrate; 5. Resistor layer; 6. Electrode assembly; 61. Upper electrode block; 62. Lower electrode block; 7. Resistor protection layer; 71. Sacrificial layer; 72. Stabilization layer; 8. Self-repairing layer; 81. Micro-repair capsule; 811. Corrosion inhibitor; 812. Heat-resistant layer; 813. Wrapping layer; 82. Slurry; 9. Arc-shaped raised strip; 10. Glass glaze protective layer; 11. Silicon carbide nanowire; 12. Chitosan response strip. DETAILED DESCRIPTION

[0033] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments.

[0034] The terms "upper", "lower", "left", "right", "middle" and "one" used in the present invention are only for the convenience of description and are not intended to limit the scope of the present invention. Changes or adjustments to their relative relationships should be regarded as within the scope of the present invention without substantially changing the technical content.

[0035] Reference Figure 1-Figure 7 A sulfurization-resistant thick film resistor, comprising: a tin plating layer 1, a nickel plating layer 2 disposed within the tin plating layer 1, conductor layers 3 located on both sides of the nickel plating layer 2, a substrate 4 disposed in the middle of the conductor layer 3, and a resistor layer 5 disposed on the substrate 4, wherein an electrode assembly 6 is disposed on the upper and lower sides of the substrate 4, and a resistor protection layer 7 is disposed on the upper side of the electrode assembly 6 disposed on the upper side;

[0036] The resistance protection layer 7 includes a sacrificial layer 71 and a stabilizing layer 72. The stabilizing layer 72 is arranged on the upper side of the electrode assembly 6. The sacrificial layer 71 is fixed on the upper side of the stabilizing layer 72. The stabilizing layer 72 is made of a highly sulfidation-resistant material, and the sacrificial layer 71 is made of a low-activity conductive phase material.

[0037] A self-repairing layer 8 is provided on the upper side of the resistance layer 5. The self-repairing layer 8 includes micro-repairing capsules 81. The interior of the micro-repairing capsules 81 is provided with a corrosion inhibitor 811, and the outer shell is provided with two layers, namely, a heat-resistant layer 812 located on the outside and a wrapping layer 813 located on the inside.

[0038] In the embodiment applying the above technical solution, the sulfidation problem of the resistor may be caused by the reaction of sulfides in the environment with the metal in the resistor material to generate metal sulfide, which causes the resistance value to change or even open circuit.

[0039] The resistor protection layer 7 is designed by constructing a multi-layer resistor structure and utilizing the physical and chemical properties of different materials for synergistic protection. The self-repairing layer 8 achieves dynamic protection by embedding micro-repair capsules 81.

[0040] The resistor protection layer 7 breaks through the existing technical bottlenecks from the perspectives of structural protection and dynamic repair through gradient design and the addition of the self-repairing layer 8. The combination of the two can significantly improve the reliability of the sulfurization-resistant thick film resistor.

[0041] The preferred technical solution in this embodiment is:

[0042] Reference Figure 3-4 The electrode assembly includes two upper electrode blocks 61 and two lower electrode blocks 62. The two upper electrode blocks 61 are arranged on both sides above the substrate 4, and the two lower electrode blocks 62 are arranged on both sides below the substrate 4.

[0043] During normal use, electricity is supplied through the upper and lower electrode blocks. When current flows through, electrons flow in the paths between the conductive particles in the resistance layer 5, thereby generating resistance.

[0044] Reference Figure 5-6 , a plurality of arc-shaped raised strips 9 are provided on the upper surface of the sacrificial layer 71, and a diversion ramp is provided between the plurality of arc-shaped raised strips 9, and the diversion ramp is inclined to both sides for diverting the flow from the middle to both sides;

[0045] The stabilizing layer 72 is made of ruthenium dioxide for maintaining resistance stability, and the sacrificial layer 71 is made of tungsten carbide for sacrificially preventing sulfur corrosion.

[0046] The existing sacrificial layer 71 is usually protected by a single passivation film. The traditional single material layer is prone to failure due to local corrosion. In this application, a gradient resistance layer 5 is designed to construct a multi-layer resistance structure and utilize the physical and chemical properties of different materials for synergistic protection. The outer sacrificial layer 71 is mostly a low-activity conductive material, such as tungsten carbide or doped metal oxide, which preferentially reacts with sulfides to form a dense passivation film, thereby delaying the penetration of sulfur.

[0047] However, during the sulfur penetration process, it is easy for the sulfur to penetrate a fixed position, causing the sacrificial layer 71 to be broken through at a single point, thereby reducing the service life of the entire sacrificial layer 71. By providing a plurality of arc-shaped raised strips 9 on the sacrificial layer 71, the infiltrated sulfur is diverted and dispersed on the sacrificial layer 71. At the same time, an inclined guide slope is provided under the plurality of arc-shaped raised strips 9 to guide the infiltrated sulfur to both sides. The moved sulfur will evenly contact and react with the low-activity conductive material on the sacrificial layer 71, thereby improving the service life of the entire sacrificial layer 71 and ensuring the sulfur barrier effect.

[0048] The inner layer is made of highly stable materials, such as ruthenium dioxide, to maintain the long-term stability of the resistance value and avoid performance failure due to corrosion of the outer layer.

[0049] The outer layer can be made of low-cost materials, reducing the use of precious metals and lowering the overall cost. In addition, multi-layer printing technology has been maturely applied in the manufacture of thick film resistors.

[0050] Reference Figure 4 A glass glaze protective layer 10 is provided above the resistor layer 5, and the interior of the glass glaze protective layer 10 is filled with silicon dioxide or oxide nanoparticles;

[0051] A glass glaze protective layer 10 is provided on the resistor layer 5, and the interior of the glass glaze protective layer 10 is filled with silicon dioxide or oxide nanoparticles with a mass ratio of 5-10%. The nanoparticles fill micropores, improve density, reduce sulfur penetration paths, and thus improve the protection effect.

[0052] Reference Figure 4-7 The self-repairing layer 8 further includes a slurry 82, the micro-repairing capsules 81 are mixed inside the slurry 82, and the self-repairing layer 8 is arranged between the resistance protection layer 7 and the resistance layer 5 to protect the resistance layer 5;

[0053] The micro-repair capsule 81 is spherical and needs to be smaller than the conductive phase particles in the slurry 82;

[0054] The corrosion inhibitor 811 is zincate, the heat-resistant layer 812 is a rigid layer made of silicon dioxide, and the wrapping layer 813 is a flexible layer made of polyimide.

[0055] The self-healing corrosion inhibitor 811 achieves dynamic protection by embedding micro-repair capsules 81 in the resistor slurry 82, where the corrosion inhibitor 811 is such as zincate or organic amine. Traditional corrosion inhibitors 811 are easily ineffective when released once, and the self-healing design can respond to corrosion signals multiple times, thereby improving protection efficiency.

[0056] The micro-repair capsules 81 are generally made into spherical shapes. When prepared through processes such as spray drying and emulsion polymerization, the surface tension of the liquid causes the droplets to naturally shrink into spherical shapes. The spherical shapes have good fluidity and are easy to be evenly dispersed in the thick film slurry 82. They also have high mechanical strength, consistent wall thickness, and strong resistance to sintering thermal shock.

[0057] Reference Figure 7 Silicon carbide nanowires 11 are arranged inside the heat-resistant layer 812, and chitosan response strips 12 are arranged inside the wrapping layer 813.

[0058] Since the micro-repair capsule 81 has the risk of sintering and cracking during use, silicon carbide nanowires 11 are used to reinforce the wall material inside the heat-resistant layer 812 to improve the thermal shock resistance of the micro-repair capsule 81;

[0059] At the same time, in order to avoid the premature release of the corrosion inhibitor 811, a pH-responsive wall material is designed through the chitosan response strip 12, so that the micro-repair capsule 81 dissolves only in the acidic environment caused by sulfide, reducing the waste of the corrosion inhibitor 811.

[0060] When sulfide intrusion causes local pH changes or mechanical stress, the micro-repair capsule 81 ruptures to release the corrosion inhibitor 811, which neutralizes the sulfide through adsorption or film-forming reaction. The precise release reduces the amount of corrosion inhibitor 811 used and reduces its toxic impact on the environment.

[0061] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solution and inventive concept of the present invention, should be covered by the scope of protection of the present invention.

Claims

1. A sulfur-resistant thick film resistor comprising: A tin plating layer, a nickel plating layer disposed inside the tin plating layer, a conductor layer located on both sides of the nickel plating layer, a substrate disposed in the middle of the conductor layer, and a resistor layer disposed on the substrate, wherein an electrode assembly is disposed on the upper and lower sides of the substrate, and a resistor protection layer is disposed on the upper side of the electrode assembly disposed on the upper side; The resistance protection layer includes a sacrificial layer and a stabilizing layer, wherein the stabilizing layer is arranged on the upper side of the electrode assembly, and the sacrificial layer is fixed on the upper side of the stabilizing layer. The stabilizing layer is made of a highly sulfidation-resistant material, and the sacrificial layer is made of a low-activity conductive phase material; A self-repairing layer is provided on the upper side of the resistance layer. The self-repairing layer includes micro-repairing capsules. The interior of the micro-repairing capsules is provided with a corrosion inhibitor, and the outer shell is provided with two layers, namely, a heat-resistant layer located on the outside and a wrapping layer located on the inside; The upper surface of the sacrificial layer is provided with a plurality of arc-shaped raised strips, and a diversion ramp is provided between the plurality of arc-shaped raised strips. The diversion ramp is inclined toward both sides and is used to divert the flow from the middle to both sides. The corrosion inhibitor is zincate, the heat-resistant layer is a rigid layer made of silicon dioxide, and the wrapping layer is a flexible layer made of polyimide; Silicon carbide nanowires are arranged inside the heat-resistant layer, and chitosan response strips are arranged inside the wrapping layer.

2. The sulfur-resistant thick film resistor according to claim 1, characterized in that: The electrode assembly includes two upper electrode blocks and two lower electrode blocks. The two upper electrode blocks are arranged on both sides above the substrate, and the two lower electrode blocks are arranged on both sides below the substrate.

3. The sulfurization-resistant thick film resistor according to claim 1, characterized in that: A glass glaze protective layer is arranged above the resistance layer, and the interior of the glass glaze protective layer is filled with silicon dioxide or oxide nanoparticles.

4. The sulfur-resistant thick film resistor according to claim 1, characterized in that: The stabilizing layer is made of ruthenium dioxide for maintaining resistance stability, and the sacrificial layer is made of tungsten carbide for sacrificially blocking sulfur corrosion.

5. The sulfurization-resistant thick film resistor according to claim 1, characterized in that: The self-repairing layer further comprises slurry, the micro-repairing capsules are mixed inside the slurry, and the self-repairing layer is arranged between the resistance protection layer and the resistance layer to protect the resistance layer.

6. The sulfurization-resistant thick film resistor according to claim 5, characterized in that: The micro-repair capsule is spherical, and the size of the micro-repair capsule needs to be smaller than the conductive phase particles in the slurry.

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