CN112266272A - Surface-mounted fuse based on low-temperature co-fired ceramic technology and preparation method thereof - Google Patents
Surface-mounted fuse based on low-temperature co-fired ceramic technology and preparation method thereof Download PDFInfo
- Publication number
- CN112266272A CN112266272A CN202011178151.8A CN202011178151A CN112266272A CN 112266272 A CN112266272 A CN 112266272A CN 202011178151 A CN202011178151 A CN 202011178151A CN 112266272 A CN112266272 A CN 112266272A
- Authority
- CN
- China
- Prior art keywords
- temperature
- fuse
- low
- slurry
- parts
- 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
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
- C04B41/90—Coating or impregnation for obtaining at least two superposed coatings having different compositions at least one coating being a metal
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H69/00—Apparatus or processes for the manufacture of emergency protective devices
- H01H69/02—Manufacture of fuses
- H01H69/022—Manufacture of fuses of printed circuit fuses
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H85/00—Protective devices in which the current flows through a part of fusible material and this current is interrupted by displacement of the fusible material when this current becomes excessive
- H01H85/02—Details
- H01H85/38—Means for extinguishing or suppressing arc
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H85/00—Protective devices in which the current flows through a part of fusible material and this current is interrupted by displacement of the fusible material when this current becomes excessive
- H01H85/02—Details
- H01H85/47—Means for cooling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Fuses (AREA)
Abstract
The invention discloses a surface-mounted fuse based on a low-temperature co-fired ceramic technology and a preparation method thereof; the preparation method comprises the following steps: sequentially preparing low-temperature co-fired ceramic powder, an organic carrier, low-temperature co-fired ceramic slurry, fuse wire electrode slurry, terminal electrode slurry, a positive electrode layer and a back electrode layer, then sequentially printing the low-temperature co-fired ceramic slurry, the fuse wire electrode slurry and the terminal electrode slurry on a ceramic substrate, and then co-firing all printing slurry layers to obtain a semi-finished product of the surface-mounted fuse; then, manufacturing a glass protective layer and identification characters on the surface-mounted fuse semi-finished product, and finally obtaining a surface-mounted fuse finished product through a post-processing procedure; the preparation method solves the problems of diffusion and uneven surface when the fuse wire electrode slurry is printed by using a low-temperature co-fired ceramic technology, so that the pattern of the fuse wire is more complete and clear, and the controllability is higher; the prepared surface-mounted fuse has a rapid fusing process, and the phenomenon of arc discharge can not occur.
Description
Technical Field
The invention relates to the technical field of surface-mounted fuses, in particular to a surface-mounted fuse based on a low-temperature co-fired ceramic technology and a preparation method thereof.
Background
The principle of the surface-mounted fuse is that when a circuit breaks down or is abnormal, the fuse metal melt fuses and cuts off current to protect the circuit. The periphery of the metal melt is tightly adhered by the polymer material or the ceramic material of the matrix part, even the molten metal cannot shrink towards two ends and can only permeate or be absorbed by the surrounding material by means of diffusion towards the surrounding material, if overcurrent disappears (such as transient pulse phenomenon) or generated heat is rapidly dissipated by the base material in the process, and the diffusion or absorption process is still in progress, the phenomenon that the resistance is increased and the melt is not completely fused can be caused.
In addition, in the surface mount fuse, the milliampere-level fuse generates a small amount of heat due to a low current, and the ceramic substrate dissipates heat quickly, thereby affecting the fuse fusing effect. Furthermore, the existing surface-mount fuse uses glass glaze as a heat insulation layer, so that the phenomenon of silver eating caused by glass melting is caused, and the influence on the resistance value of the fuse is large, so that the milliampere-level fuse produced on a ceramic substrate has the problems of low yield and unstable performance.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a surface-mounted fuse based on a low-temperature co-fired ceramic technology and a preparation method thereof, wherein the preparation method utilizes the low-temperature co-fired ceramic technology to solve the problems of diffusion and uneven surface when the electrode slurry of the fuse is printed, so that the pattern of the fuse is more complete and clear, and the controllability is higher; the prepared surface-mounted fuse has a rapid fusing process, and the phenomenon of arc discharge can not occur.
In order to achieve the technical purpose and achieve the technical effect, the invention is realized by the following technical scheme:
a method for preparing a surface-mounted fuse based on a low-temperature co-fired ceramic technology comprises the following steps:
step one, preparing low-temperature co-fired ceramic powder
Weighing 30-40 parts of calcium oxide powder, 25-35 parts of boron oxide powder and 35-45 parts of silicon oxide powder, putting the mixture into a ball milling tank for ball milling, and separating the ball milled materials by using a screen to obtain mixed powder;
heating the mixed powder for 0.5-1h at the temperature of 1200-1300 ℃ to obtain a molten material, and putting the molten material into deionized water for water quenching to obtain glass slag;
putting the obtained glass slag into a ball milling tank, adding absolute ethyl alcohol, carrying out ball milling, separating the ball-milled materials by using a screen, and drying the obtained feed liquid to obtain Ca-B-Si series microcrystalline glass powder;
taking 80-90 parts of Ca-B-Si series microcrystalline glass powder and 10-20 parts of 1-2 mu m zirconia powder, placing the powder in a ball milling tank, carrying out ball milling, and separating the ball-milled materials by using a screen to obtain low-temperature co-fired ceramic powder; specifically, the low-temperature co-fired ceramic powder can be configured into two types with different proportions of microcrystalline glass powder and zirconia powder;
step two, preparing an organic carrier
The preparation raw materials of the organic carrier comprise acrylic resin, a solvent and a film-forming agent, wherein the content of the acrylic ester is 20-30%, and the content of the film-forming agent is 3-8%;
step three, preparing low-temperature co-fired ceramic slurry
Mixing an organic carrier and low-temperature co-fired ceramic powder, and rolling to obtain low-temperature co-fired ceramic slurry; the prepared low-temperature co-fired ceramic slurry comprises two types, wherein one type is the low-temperature co-fired ceramic slurry for the heat-insulating layer, and the other type is the low-temperature co-fired ceramic slurry for the arc-extinguishing layer; the solid content of the low-temperature co-fired ceramic slurry for the thermal insulation layer is 75-80%, the solid content of the low-temperature co-fired ceramic slurry for the arc extinguishing layer is 65-70%, and the relative dosage of zirconia in the low-temperature co-fired ceramic powder adopted by the low-temperature co-fired ceramic slurry for the arc extinguishing layer is higher than that in the low-temperature co-fired ceramic powder adopted by the low-temperature co-fired ceramic slurry for the thermal insulation layer;
step four, preparing fuse wire electrode slurry
Weighing the following components in parts by weight: 10-20 parts of Ca-B-Si series microcrystalline glass powder, 40-50 parts of 5-10 mu m chip type silver powder, 10-20 parts of spherical submicron silver powder, 5-10 parts of tin-bismuth alloy powder, 1-5 parts of solid powder dispersing agent, 1-5 parts of gas-phase silicon dioxide powder and 15-25 parts of organic carrier, uniformly mixing to obtain a fuse electrode mixture, and grinding the fuse electrode mixture to obtain fuse electrode slurry;
step five, preparing end electrode slurry and back electrode slurry
End electrode slurry: weighing 1-5 parts of high-temperature glass powder, 60-80 parts of 1-3 mu m spherical silver powder, 10-20 parts of spherical submicron silver powder and 10-15 parts of organic carrier according to parts by weight, uniformly mixing to obtain a terminal electrode mixture, and grinding the terminal electrode mixture to obtain terminal electrode slurry;
back electrode paste: respectively weighing 5-10 parts of high-temperature glass powder, 50-60 parts of 1-3 mu m spherical silver powder and 30-40 parts of organic carrier according to parts by weight, uniformly mixing to obtain a back electrode mixture, and grinding the back electrode mixture to obtain back electrode slurry;
step six, preparing a positive electrode layer and a back electrode layer
Printing the terminal electrode slurry prepared in the fifth step on the front end part of the ceramic substrate, printing the back electrode slurry prepared in the fifth step on the back end part of the ceramic substrate, and sintering to form a positive electrode layer and a back electrode layer;
step seven, printing the co-fired slurry
Printing low-temperature co-fired ceramic slurry with solid content of 75-80% for a thermal insulation layer on the surface of the ceramic substrate treated in the sixth step;
printing fuse wire electrode slurry on a low-temperature co-fired ceramic slurry layer for a thermal insulation layer according to a designed fuse wire pattern;
printing low-temperature co-fired ceramic slurry with solid content of 65-70% for an arc extinguishing layer on the fuse electrode slurry layer;
step eight, co-firing
Carrying out glue discharging treatment on the printed ceramic substrate, and sintering to obtain a semi-finished product of the surface-mounted fuse; after co-firing, a heat insulation layer, a fuse layer and an arc extinguishing layer are sequentially formed on the ceramic substrate.
Further, in the process of preparing the mixed powder in the step one, the ball-material ratio in the ball milling process is 4:1, the ball milling time is 4 hours, and the specification of a screen mesh adopted in the separation is 80 meshes;
in the process of preparing the Ca-B-Si series microcrystalline glass powder in the first step, the ball-to-material ratio in the ball milling process is 5:1, the rotating speed of a ball mill is 300rpm, the ball milling time is 12 hours, and the specification of a screen mesh adopted in the separation is 300 meshes;
in the first step, the Ca-B-Si series microcrystalline glass powder and the zirconia powder are placed in a ball milling tank for ball milling, the ball-to-material ratio is 4:1, the ball milling time is 4 hours, and the size of a screen mesh adopted during separation is 80 meshes.
Preferably, in the second step, the solvent used for preparing the organic carrier is one or a combination of two or more selected from terpineol, butyl carbitol acetate, DBE, tributyl citrate and DOP, and the film forming agent used is decaglycol ester.
Further, in the fourth step, the fuse electrode slurry is ground to the fineness of less than 10 μm; in the fifth step, the end electrode slurry is ground to the fineness of less than 5 μm.
Further, in the seventh step, the pattern of the fuse is designed according to the resistance requirement of the fuse.
Further, in the eighth step, the glue discharging temperature is set to 400-.
Further, after the co-firing is finished, low-temperature glass slurry is coated on the arc extinguishing layer of the surface-mounted semi-finished fuse to serve as protective layer slurry.
Furthermore, after the protective layer slurry is coated, marking slurry is printed on the surface of the surface-mounted fuse semi-finished product, and then the protective layer slurry and the marking slurry are sintered together to obtain the surface-mounted fuse semi-finished product with the glass protective layer and the marking characters.
Furthermore, the preparation method also comprises a post-treatment process, wherein the post-treatment process comprises stacking, sputtering, particle folding and electroplating which are sequentially carried out, and specifically comprises the following steps: and stacking the surface-mounted fuse semi-finished products into product strips, sputtering a layer of platable metal on the side surfaces of the product strips, folding the product strips into small-particle fuse device unit semi-finished products by using a granule folding machine, and electroplating the fuse device unit semi-finished products to obtain the surface-mounted fuse finished products.
The invention also provides a surface-mounted fuse prepared by the preparation method.
The invention has the beneficial effects that:
(1) the surface-mounted fuse prepared by the preparation method has the advantages of good fusing performance, concentrated fusing time, rapid fusing process and no arc discharge phenomenon; specifically, the thermal insulation layer of the surface-mounted fuse abandons the conventional glass material and adopts a low-temperature co-fired ceramic material, and the arc extinguishing layer also adopts the low-temperature co-fired ceramic material; the low-temperature co-fired ceramic material is prepared from Ca-B-Si series microcrystalline glass powder and zirconia powder, wherein the zirconia powder has low thermal conductivity and high melting point, so that the problem of heat dissipation in the process of electrifying the fuse wire can be well solved, the heat can be better concentrated in the fuse wire, the fusing process is rapid, and the arc discharge phenomenon can not occur; the Ca-B-Si series microcrystalline glass powder can improve the density of the low-temperature co-fired ceramic material; the ratio of the Ca-B-Si series microcrystalline glass powder to the zirconia powder is adjusted to control the density of the low-temperature co-fired ceramic material after firing and meet the performance requirements of a heat insulation layer and an arc extinguishing layer. The thermal insulation layer has higher density, and can prevent the diffusion of the fuse electrode slurry during screen printing and the penetration of the metal after melting in the sintering process; the arc extinguishing layer has low density, is a loose structure, cannot damage the fuse wire electrode slurry in the sintering process, and is beneficial to arc extinguishing of the fuse wire.
(2) The invention adopts the process of co-firing the heat insulation layer, the fuse wire layer and the arc extinguishing layer, so that in the process of printing the fuse wire electrode paste, the heat insulation layer is an unsintered layer and has better smoothness, the wetting property of the fuse wire electrode paste on the surface is better, the printed pattern of the paste is clearer and more concentrated, the phenomenon of flowing can not occur, the leveling property of the paste is better, and the resistance value is more concentrated and more stable after sintering. In addition, the invention adopts a co-firing process, and the arc extinguishing layer is a loose layer, thereby not influencing the fuse wire and avoiding the resistance rise caused by the damage of the arc extinguishing layer to the fuse wire in the sintering process.
(3) The invention adopts the process of co-firing the heat insulation layer, the fuse layer and the arc extinguishing layer, is different from the complex process of printing and sintering once in the traditional process, can reduce the sintering times, reduce the energy consumption and avoid the problem of fragment caused by excessive sintering procedures and the problem of yield reduction caused by over-sintering of fuses and the like.
(4) The invention adopts the sheet silver powder to replace gold powder as the main material of the fuse wire electrode slurry, thereby not only greatly reducing the cost, but also meeting the requirements of a mA-level fuse with thinner fuse wire and larger resistance value after high-temperature sintering.
(5) The milliampere-level patch fuse produced by the conventional printing thick film process has relatively large resistance value, the resistance value of 500 milliampere-level patch fuse is about 1 omega, the resistance value of 250 milliampere-level patch fuse is about 4 omega, the resistance value of 125 milliampere-level patch fuse is about 15 omega, and the current in the circuit can be greatly influenced. The invention adopts the unique low thermal conductivity of the fuse electrode slurry and the low-temperature co-fired ceramic material, so that the resistance of the 125 mA patch fuse can be reduced to about 4 omega, and the resistance of products with other specifications can be correspondingly reduced, thereby having little influence on circuits.
Drawings
Fig. 1 is a schematic structural view of a surface-mount fuse according to embodiment 1 of the present invention.
Fig. 2 is a schematic diagram of a fuse pattern in the surface mount fuse according to embodiment 1 of the present invention.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The method for preparing the surface-mount fuse based on the low-temperature co-fired ceramic technology in embodiment 1 includes the following steps:
step one, preparing low-temperature co-fired ceramic powder
Weighing 30 parts of calcium oxide powder, 25 parts of boron oxide powder and 35 parts of silicon oxide powder, putting the weighed materials into a ball-milling tank made of 500ml of zirconium oxide material, carrying out ball milling for 4 hours on the dry powder with the ball-material ratio of 4:1, cooling, ultrasonically screening the powder through a 80-mesh screen, and separating to obtain mixed powder;
preheating a 250ml platinum crucible in a high-temperature furnace at 1250 ℃ for 30min, then placing the mixed powder in the platinum crucible, heating the mixed powder in the high-temperature furnace at 1250 ℃ for 30min, taking out the platinum crucible when the oxide powder is not completely melted to obtain a molten material, and placing the molten material in deionized water for water quenching to obtain glass slag;
putting the obtained glass slag into a zirconia ball milling tank, adding 150ml of absolute ethyl alcohol at a ball-to-material ratio of 5:1, ball milling for 12 hours by a ball mill at the rotating speed of 300rpm, separating the ball-milled materials by a 300-mesh screen, and drying the obtained feed liquid for 4 hours at 150 ℃ to obtain Ca-B-Si series microcrystalline glass powder;
taking 80 parts of Ca-B-Si series microcrystalline glass powder and 10 parts of 1-2 mu m zirconia powder, putting the powder into a 500ml zirconia ball milling tank, wherein the ball-to-material ratio is 4:1, carrying out dry powder ball milling for 4 hours, cooling, then carrying out ultrasonic screening through a 80-mesh screen, and separating to obtain low-temperature co-fired ceramic powder I; and additionally, putting 80 parts of Ca-B-Si series microcrystalline glass powder and 13 parts of 1-2 mu m zirconia powder into a 500ml zirconia ball milling tank, wherein the ball-to-material ratio is 4:1, carrying out dry powder ball milling for 4 hours, cooling, then carrying out ultrasonic screening through a 80-mesh screen, and separating to obtain the low-temperature co-fired ceramic powder II. By adjusting the proportion of the microcrystalline glass powder and the zirconia powder, a compact heat insulation layer and a loose arc extinguishing layer can be obtained in the subsequent co-firing process;
step two, preparing an organic carrier
The preparation raw materials of the organic carrier comprise acrylic resin, terpineol and decaglycol ester, wherein the content of acrylic ester is 20%, the content of film-forming agent is 5%, and the balance is terpineol.
Step three, preparing low-temperature co-fired ceramic slurry
Taking an organic carrier and low-temperature co-fired ceramic powder, mixing, and rolling by a three-roller mill to obtain low-temperature co-fired ceramic slurry; the prepared low-temperature co-fired ceramic slurry comprises two types, wherein one type is the low-temperature co-fired ceramic slurry for the heat insulation layer, the other type is the low-temperature co-fired ceramic slurry for the arc extinguishing layer, and the other type is the low-temperature co-fired ceramic powder II; the solid content of the low-temperature co-fired ceramic slurry for the thermal insulation layer is 75 percent, and the solid content of the low-temperature co-fired ceramic slurry for the arc extinguishing layer is 65 percent;
the invention adopts acrylic resin as the adhesive of the sizing agent, and because the molecular weight of the acrylic resin is relatively small, the viscosity is relatively low, the binder is relatively clean in the sintering process under the air condition, and the carbon deposition phenomenon is not easy to occur, the surface of the sizing agent after sintering is relatively smooth and compact.
Step four, preparing fuse wire electrode slurry
Weighing the following components in parts by weight: 10 parts of Ca-B-Si series microcrystalline glass powder, 40 parts of 5-10 mu m piece type silver powder, 10 parts of spherical submicron silver powder, 5 parts of tin-bismuth alloy powder, 2 parts of solid powder dispersing agent, 2 parts of fumed silica powder and 15 parts of organic carrier, uniformly mixing to obtain a fuse electrode mixture, grinding the fuse electrode mixture by using a three-roll grinder to the fineness of below 10 mu m to obtain fuse electrode slurry;
the invention adopts 5-10 μm flake silver powder as the main conductive material, and the conductive layer formed after printing and sintering is thinner, thus being beneficial to fusing, and meanwhile, partial spherical submicron powder is added as auxiliary conductive powder, thus preventing the problem of wire breakage when the flake silver powder shrinks. Meanwhile, a certain amount of microcrystalline glass powder in a low-temperature co-fired ceramic system is added into the slurry, so that the matching degree of the microcrystalline glass powder and the chip silver powder is high in the co-firing process, and poor appearance caused by shrinkage mismatching cannot be generated. The added inorganic filler (solid powder dispersant and gas-phase silica powder) can increase the resistance of the fuse, and simultaneously has the function of arc extinction in the fusing process, thereby instantly pulling away the distance of a breakpoint and rapidly cutting off current. In order to better fuse the fuse wire, the electrode slurry of the fuse wire is added with the tin bismuth alloy with low melting point, and the melting point of the alloy is below 300 ℃, so that the fuse wire can be rapidly melted when being electrified to generate heat and fused with surrounding silver to form the tin bismuth silver alloy, and the tin bismuth silver alloy can be rapidly absorbed by surrounding arc extinguishing materials, so that the fusing process is safe and rapid.
The fumed silica added into the paste is also beneficial to fine line printing of the paste, the high thixotropy of the fumed silica can increase the viscosity of the paste and is beneficial to the contraction of a pattern, and the minimum line width printed by the fuse electrode paste after the fumed silica is added can reach 50 mu m.
Step five, preparing end electrode slurry and back electrode slurry
End electrode slurry: respectively weighing 5 parts of high-temperature glass powder, 60 parts of 1-3 mu m spherical silver powder, 20 parts of spherical submicron silver powder and 15 parts of organic carrier according to parts by weight, uniformly mixing to obtain a terminal electrode mixture, grinding the terminal electrode mixture by using a three-roll grinder until the fineness is below 5 mu m to obtain terminal electrode slurry;
back electrode paste: respectively weighing 10 parts of high-temperature glass powder, 50 parts of 1-3 mu m spherical silver powder and 40 parts of organic carrier according to parts by weight, uniformly mixing to obtain a back electrode mixture, grinding the back electrode mixture by using a three-roll grinder until the fineness is below 5 mu m, and obtaining back electrode slurry.
In order to ensure excellent conductivity of the terminal electrode and prevent poor fusing of a contact point caused by overlarge contact resistance between a fuse wire and the terminal electrode in a fusing process, the invention adopts terminal electrode slurry with silver content of more than 80%.
Step six, preparing a positive electrode layer and a back electrode layer
Printing the terminal electrode slurry prepared in the fifth step on the front end part of the ceramic substrate, printing the back electrode slurry prepared in the fifth step on the back end part of the ceramic substrate, and sintering to form a positive electrode layer and a back electrode layer; to ensure good subsequent contact with the fuse, the thickness and pattern size of the positive electrode screen is about 1.2-1.5 times that of the back electrode. The positive electrode layer and the back electrode layer are sintered at 850 ℃ and then are subjected to subsequent printing work.
Step seven, printing the co-fired slurry
Printing low-temperature co-fired ceramic slurry with solid content of 75% for a thermal insulation layer on the front surface of the ceramic substrate processed in the sixth step; printing by adopting a stainless steel wire mesh 2-time printing process, drying after the first printing is finished, rotating the ceramic substrate by 180 degrees, then finishing the second printing, and drying; the 2-time printing process of rotation ensures the flatness of the printed surface.
Designing a pattern of the fuse according to the resistance value requirement of the fuse, as shown in fig. 2, printing fuse electrode slurry on a low-temperature co-fired ceramic slurry layer for a thermal insulation layer according to the pattern; more specifically, in order to ensure the stability of the resistance value, the fuse adopts a mode of printing the fuse electrode paste for 2 times in the preparation process; the graphic design is according to the resistance formula: and R is rho L/S, and the longer the wire length is, the larger the resistance value is under the condition of the same thickness. The graphic design of this embodiment adopts the bending design, is equivalent to the line length and has increased one time, and under the equal resistance condition, thickness can increase one time, consequently can increase the printing number of times to guarantee the thickness homogeneity after the printing of fuse electrode thick liquids, be favorable to the homogeneity improvement of sintering back fuse resistance, also make fusing performance better. When the fuse electrode paste is printed, the low-temperature co-fired ceramic paste layer for the thermal insulation layer is not sintered, the surface of the printed fuse electrode paste has no tape casting phenomenon, the line width is better maintained, and the stability of the resistance value is also improved.
Then, printing low-temperature co-fired ceramic slurry with the solid content of 65% for an arc extinguishing layer on the fuse wire electrode slurry layer; the low-temperature co-fired ceramic slurry for the arc extinguishing layer has relatively low glass content, so that the density after firing is lower, the fuse slurry cannot be damaged in the sintering process, and arc extinguishing of a fuse can be facilitated; when the temperature rises sharply, the metal vapor generated by fusing the fuse wire can be quickly absorbed by the micropores on the surface, and the circuit is quickly cut off. In addition, as the density and the particle size of the Ca-B-Si series microcrystalline glass powder are lower than those of the added zirconia, the glass powder particles gradually move upwards along with the binder removal airflow during co-firing, so that the enrichment on the surface of the arc extinguishing layer is more, and holes are easily formed in the bottom area of the arc extinguishing layer; the arc extinguishing effect can be obviously improved by the formation of the hole, and the occurrence of arc discharge is prevented.
Step eight, co-firing
Placing the printed ceramic substrate in a chain furnace for binder removal, setting the binder removal temperature to 450 ℃, and preserving heat for 30min to fully binder remove all the printing slurry layers in the seventh step and prevent carbon deposition holes and microcracks caused by insufficient binder removal in subsequent sintering; then, sintering is carried out, the sintering temperature is set to be 840 ℃, and heat preservation is carried out for 15min, so that all printing paste layers can be fully melted and sintered; cooling after sintering, wherein the cooling time is set to be 30 min;
after co-firing, a heat insulation layer, a fuse layer and an arc extinguishing layer are sequentially formed on the ceramic substrate, so that a semi-finished product of the surface-mounted fuse is obtained.
Step ten, printing protective layer paste and marking paste
Since the sintered arc-extinguishing layer is relatively brittle and easily crushed in the subsequent grain-stacking and folding process, a glass protective layer needs to be added on the surface of the arc-extinguishing layer. The specific operation process is as follows: coating low-temperature glass slurry serving as protective layer slurry on the surface of the arc-extinguishing layer of the semi-finished product of the attached fuse after the step eight is co-fired, and enabling the protective layer slurry to uniformly and completely cover the heat-insulating layer, the fuse layer and the arc-extinguishing layer region;
because the resistance values of the fuse devices are different and the fusing characteristics are different, in order to distinguish different product models, identification characters need to be printed on the outermost surface of the fuse devices; in the embodiment, white glass slurry is used as the marking slurry;
in order to ensure the smoothness of the surface, the marking slurry and the protective layer slurry are sintered together, the smoothness of the surface is better after mutual fusion, and the problem of material throwing caused by uneven surface can be avoided.
Eleventh, post-treatment Process
The post-treatment process comprises stacking, sputtering, particle folding and electroplating, and specifically comprises the following steps: stacking the surface-mounted fuse semi-finished products obtained through the processing of the ten steps into product strips along stripping lines through a strip folding machine, then placing the product strips into a sputtering jig, sputtering a layer of platable metal on the side surfaces of the product strips through a sputtering furnace, and changing the thickness of the metal layer by adjusting sputtering time and current value; the sputtered product strip is folded into a semi-finished product of a fuse device unit with small particles according with the size specification by a particle folding machine; electroplating the semi-finished product of the fuse device unit which meets the size specification by using electroplating solution with neutral pH value to obtain a surface-mounted fuse finished product; the electroplating solution is neutral, so that the damage of the acid-base electroplating solution to products can be prevented; and before electroplating, the positive electrode layer, the back electrode layer and the sputtered metal layer are cleaned, the rolling speed is uniform during electroplating, and after the electrode layer of a product conforms to a specification range, electroplating is finished, so that the phenomenon that tin is prone during electroplating to influence the appearance yield of a device is avoided.
As shown in fig. 1, the surface-mount fuse obtained in embodiment 1 includes a ceramic substrate 1, a positive electrode layer 2 is disposed at an end of a front surface of the ceramic substrate 1, a back electrode layer 3 is disposed at an end of a back surface of the ceramic substrate, a thermal insulation layer 4, a fuse layer 5, an arc extinguishing layer 6, and a glass protection layer 7 are sequentially disposed on the front surface of the ceramic substrate 1 from bottom to top between the positive electrode layers at two ends, and an identification character is further disposed on an outermost surface of the surface-mount fuse; the side end of the surface-mounted fuse is also provided with a sputtered electroplated Sn metal layer 8.
Example 2
The method for manufacturing the surface mount fuse of the embodiment 2 is the same as the embodiment 1, and is different from the embodiment 1 in that:
the mixed powder of the first step in the embodiment 2 comprises 35 parts of calcium oxide powder, 30 parts of boron oxide powder and 40 parts of silicon oxide powder; in the first step, when preparing the low-temperature co-fired ceramic powder, the two low-temperature co-fired ceramic powders are respectively one of: the heat insulation material comprises 85 parts of Ca-B-Si series microcrystalline glass powder and 13 parts of zirconia powder and is used for a heat insulation layer; the other is as follows: the material comprises 85 parts of Ca-B-Si series microcrystalline glass powder and 16 parts of zirconia powder and is used for an arc extinguishing layer; the solid content in the low-temperature co-fired ceramic slurry for the thermal insulation layer is 76%, and the solid content in the low-temperature co-fired ceramic slurry for the arc extinguishing layer is 68%.
The fuse wire electrode paste in example 2 includes 15 parts of Ca-B-Si based microcrystalline glass powder, 45 parts of 5-10 μm chip-type silver powder, 15 parts of spherical submicron silver powder, 7 parts of tin-bismuth alloy powder, 3 parts of solid powder dispersant, 2 parts of fumed silica powder, and 20 parts of organic vehicle.
The terminal electrode paste of example 2 comprises 2 parts of high temperature glass powder, 70 parts of 1-3 μm spherical silver powder, 15 parts of spherical submicron silver powder and 13 parts of organic vehicle.
The back electrode paste of example 2 comprises 8 parts of high temperature glass frit, 55 parts of 1-3 μm spherical silver powder, and 37 parts of organic vehicle.
Example 3
The method for manufacturing the surface mount fuse of embodiment 3 is the same as that of embodiment 1, and is different from embodiment 1 in that:
the mixed powder of the first step in the embodiment 3 comprises 40 parts of calcium oxide powder, 35 parts of boron oxide powder and 45 parts of silicon oxide powder; in the first step, when preparing the low-temperature co-fired ceramic powder, the two low-temperature co-fired ceramic powders are respectively one of: the heat insulation material comprises 90 parts of Ca-B-Si series microcrystalline glass powder and 15 parts of zirconia powder and is used for a heat insulation layer; the other is as follows: it contains 90 parts of Ca-B-Si series microcrystalline glass powder and 20 parts of zirconia powder and is used for an arc extinguishing layer; the solid content in the low-temperature co-fired ceramic slurry for the thermal insulation layer is 80%, and the solid content in the low-temperature co-fired ceramic slurry for the arc extinguishing layer is 70%.
The fuse electrode paste in example 3 includes 20 parts of Ca-B-Si based microcrystalline glass powder, 50 parts of 5-10 μm chip-type silver powder, 20 parts of spherical submicron silver powder, 10 parts of tin-bismuth alloy powder, 5 parts of solid powder dispersing agent, 5 parts of fumed silica powder, and 25 parts of organic vehicle.
The terminal electrode paste in example 3 comprises 1 part of high temperature glass powder, 80 parts of 1-3 μm spherical silver powder, 10 parts of spherical submicron silver powder and 10 parts of organic vehicle.
The back electrode paste of example 3 comprises 5 parts of high temperature glass frit, 60 parts of 1-3 μm spherical silver powder, and 35 parts of organic vehicle.
The surface mount fuses obtained in examples 2 and 3 have the same structure as example 1.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A preparation method of a surface-mounted fuse based on a low-temperature co-fired ceramic technology is characterized by comprising the following steps:
step one, preparing low-temperature co-fired ceramic powder
Weighing 30-40 parts of calcium oxide powder, 25-35 parts of boron oxide powder and 35-45 parts of silicon oxide powder, putting the mixture into a ball milling tank for ball milling, and separating the ball milled materials by using a screen to obtain mixed powder;
heating the mixed powder for 0.5-1h at the temperature of 1200-1300 ℃ to obtain a molten material, and putting the molten material into deionized water for water quenching to obtain glass slag;
putting the obtained glass slag into a ball milling tank, adding absolute ethyl alcohol, carrying out ball milling, separating the ball-milled materials by using a screen, and drying the obtained feed liquid to obtain Ca-B-Si series microcrystalline glass powder;
taking 80-90 parts of Ca-B-Si series microcrystalline glass powder and 10-20 parts of 1-2 mu m zirconia powder, placing the powder in a ball milling tank, carrying out ball milling, and separating the ball-milled materials by using a screen to obtain low-temperature co-fired ceramic powder;
step two, preparing an organic carrier
The preparation raw materials of the organic carrier comprise acrylic resin, a solvent and a film-forming agent, wherein the content of the acrylic ester is 20-30%, and the content of the film-forming agent is 3-8%;
step three, preparing low-temperature co-fired ceramic slurry
Mixing an organic carrier and low-temperature co-fired ceramic powder, and rolling to obtain low-temperature co-fired ceramic slurry; the prepared low-temperature co-fired ceramic slurry comprises two types, wherein one type is the low-temperature co-fired ceramic slurry for the heat-insulating layer, and the other type is the low-temperature co-fired ceramic slurry for the arc-extinguishing layer; the solid content of the low-temperature co-fired ceramic slurry for the thermal insulation layer is 75-80%, and the solid content of the low-temperature co-fired ceramic slurry for the arc extinguishing layer is 65-70%;
step four, preparing fuse wire electrode slurry
Weighing the following components in parts by weight: 10-20 parts of Ca-B-Si series microcrystalline glass powder, 40-50 parts of 5-10 mu m chip type silver powder, 10-20 parts of spherical submicron silver powder, 5-10 parts of tin-bismuth alloy powder, 1-5 parts of solid powder dispersing agent, 1-5 parts of gas-phase silicon dioxide powder and 15-25 parts of organic carrier, uniformly mixing to obtain a fuse electrode mixture, and grinding the fuse electrode mixture to obtain fuse electrode slurry;
step five, preparing end electrode slurry and back electrode slurry
End electrode slurry: weighing 1-5 parts of high-temperature glass powder, 60-80 parts of 1-3 mu m spherical silver powder, 10-20 parts of spherical submicron silver powder and 10-15 parts of organic carrier according to parts by weight, uniformly mixing to obtain a terminal electrode mixture, and grinding the terminal electrode mixture to obtain terminal electrode slurry;
back electrode paste: weighing 5-10 parts of high-temperature glass powder, 50-60 parts of 1-3 mu m spherical silver powder and 30-40 parts of organic carrier according to parts by weight, uniformly mixing to obtain a back electrode mixture, and grinding the back electrode mixture to obtain back electrode slurry;
step six, preparing a positive electrode layer and a back electrode layer
Printing the terminal electrode slurry prepared in the fifth step on the front end part of the ceramic substrate, printing the back electrode slurry prepared in the fifth step on the back end part of the ceramic substrate, and sintering to form a positive electrode layer and a back electrode layer;
step seven, printing the co-fired slurry
Printing low-temperature co-fired ceramic slurry with solid content of 75-80% for a thermal insulation layer on the surface of the ceramic substrate treated in the sixth step;
printing fuse wire electrode slurry on a low-temperature co-fired ceramic slurry layer for a thermal insulation layer according to a designed fuse wire pattern;
printing low-temperature co-fired ceramic slurry with solid content of 65-70% for an arc extinguishing layer on the fuse electrode slurry layer;
step eight, co-firing
Carrying out glue discharging treatment on the printed ceramic substrate, and sintering to obtain a semi-finished product of the surface-mounted fuse; after co-firing, a heat insulation layer, a fuse layer and an arc extinguishing layer are sequentially formed on the ceramic substrate.
2. The method for preparing the surface-mounted fuse based on the low-temperature co-fired ceramic technology according to claim 1, wherein the method comprises the following steps:
in the process of preparing the mixed powder in the first step, the ball-material ratio in the ball milling process is 4:1, the ball milling time is 4 hours, and the specification of a screen mesh adopted in the separation process is 80 meshes;
in the process of preparing the Ca-B-Si series microcrystalline glass powder in the first step, the ball-to-material ratio in the ball milling process is 5:1, the rotating speed of a ball mill is 300rpm, the ball milling time is 12 hours, and the specification of a screen mesh adopted in the separation is 300 meshes;
in the first step, the Ca-B-Si series microcrystalline glass powder and the zirconia powder are placed in a ball milling tank for ball milling, the ball-to-material ratio is 4:1, the ball milling time is 4 hours, and the size of a screen mesh adopted during separation is 80 meshes.
3. The method for preparing the surface-mounted fuse based on the low-temperature co-fired ceramic technology according to claim 1, wherein the method comprises the following steps: in the second step, the solvent used for preparing the organic carrier is one or the combination of two or more of terpineol, butyl carbitol acetate, DBE, tributyl citrate and DOP, and the adopted film forming agent is decaglycol ester.
4. The method for preparing the surface-mounted fuse based on the low-temperature co-fired ceramic technology according to claim 1, wherein the method comprises the following steps: in the fourth step, the fuse electrode slurry is ground to the fineness of less than 10 μm; in the fifth step, the end electrode slurry is ground to the fineness of less than 5 μm.
5. The method for preparing the surface-mounted fuse based on the low-temperature co-fired ceramic technology according to claim 1, wherein the method comprises the following steps: and step seven, designing the graph of the fuse according to the resistance value requirement of the fuse.
6. The method for preparing the surface-mounted fuse based on the low-temperature co-fired ceramic technology according to claim 1, wherein the method comprises the following steps: in the eighth step, the glue discharging temperature is set to 400-plus-500 ℃, the glue discharging heat preservation time is 30min, the co-firing temperature is set to 800-plus-850 ℃, and the co-firing heat preservation time is 15 min.
7. The method for preparing the surface-mounted fuse based on the low-temperature co-fired ceramic technology according to claim 1, wherein the method comprises the following steps: and after the co-firing is finished, coating low-temperature glass slurry on the arc extinguishing layer of the surface-mounted semi-finished fuse as protective layer slurry.
8. The method for preparing the surface-mounted fuse based on the low-temperature co-fired ceramic technology according to claim 7, wherein the method comprises the following steps: after the protective layer slurry is coated, printing identification slurry on the surface of the surface-mounted fuse semi-finished product, and sintering the protective layer slurry and the identification slurry together to obtain the surface-mounted fuse semi-finished product with the glass protective layer and the identification characters.
9. The method for preparing the surface-mounted fuse based on the low-temperature co-fired ceramic technology according to claim 8, wherein the method comprises the following steps: still include the aftertreatment process, this aftertreatment process is including piling up, sputtering, folding grain and electroplating that carry out in proper order, specifically is: and stacking the surface-mounted fuse semi-finished products into product strips, sputtering a layer of platable metal on the side surfaces of the product strips, folding the product strips into small-particle fuse device unit semi-finished products by using a granule folding machine, and electroplating the fuse device unit semi-finished products to obtain the surface-mounted fuse finished products.
10. A surface-mount fuse produced by the production method according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011178151.8A CN112266272B (en) | 2020-10-29 | 2020-10-29 | Surface-mounted fuse based on low-temperature co-fired ceramic technology and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011178151.8A CN112266272B (en) | 2020-10-29 | 2020-10-29 | Surface-mounted fuse based on low-temperature co-fired ceramic technology and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112266272A true CN112266272A (en) | 2021-01-26 |
| CN112266272B CN112266272B (en) | 2022-04-12 |
Family
ID=74346159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011178151.8A Active CN112266272B (en) | 2020-10-29 | 2020-10-29 | Surface-mounted fuse based on low-temperature co-fired ceramic technology and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112266272B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113061024A (en) * | 2021-04-08 | 2021-07-02 | 山东国瓷功能材料股份有限公司 | Low-temperature co-fired material and prepared green ceramic chip and device for overcurrent protection |
| CN114133269A (en) * | 2021-12-06 | 2022-03-04 | 中国振华集团云科电子有限公司 | Preparation method of high-reliability multilayer co-fired ceramic heating element for electronic cigarette |
| CN114446718A (en) * | 2022-01-19 | 2022-05-06 | 苏州晶讯科技股份有限公司 | Low-current polymer patch fuse and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0242226A2 (en) * | 1986-04-18 | 1987-10-21 | Tektronix, Inc. | Glass-ceramic materials with low firing temperature |
| US4755490A (en) * | 1986-04-18 | 1988-07-05 | Tektronix, Inc. | Low firing temperature ceramic materials |
| CN101261914A (en) * | 2007-03-08 | 2008-09-10 | 诚佑科技股份有限公司 | Chip fuse and its making method |
| CN101944463A (en) * | 2010-08-31 | 2011-01-12 | 广东风华高新科技股份有限公司 | Film sheet fuse and preparation method thereof |
| CN102013368A (en) * | 2010-10-08 | 2011-04-13 | Aem科技(苏州)股份有限公司 | Fuse with built-in thermal-protective coating and manufacture process thereof |
| CN103265270A (en) * | 2013-05-22 | 2013-08-28 | 淮南舜陶应用材料科技有限公司 | Method for preparing low-temperature co-fired ceramic powder paste applied to LED (Light Emitting Diode) substrate |
| CN107602088A (en) * | 2017-10-31 | 2018-01-19 | 昆明云基新材料有限公司 | A kind of low-temperature co-burning ceramic material matched with high-temperature electric conduction silver paste height and preparation method thereof |
-
2020
- 2020-10-29 CN CN202011178151.8A patent/CN112266272B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0242226A2 (en) * | 1986-04-18 | 1987-10-21 | Tektronix, Inc. | Glass-ceramic materials with low firing temperature |
| US4755490A (en) * | 1986-04-18 | 1988-07-05 | Tektronix, Inc. | Low firing temperature ceramic materials |
| CN101261914A (en) * | 2007-03-08 | 2008-09-10 | 诚佑科技股份有限公司 | Chip fuse and its making method |
| CN101944463A (en) * | 2010-08-31 | 2011-01-12 | 广东风华高新科技股份有限公司 | Film sheet fuse and preparation method thereof |
| CN102013368A (en) * | 2010-10-08 | 2011-04-13 | Aem科技(苏州)股份有限公司 | Fuse with built-in thermal-protective coating and manufacture process thereof |
| CN103265270A (en) * | 2013-05-22 | 2013-08-28 | 淮南舜陶应用材料科技有限公司 | Method for preparing low-temperature co-fired ceramic powder paste applied to LED (Light Emitting Diode) substrate |
| CN107602088A (en) * | 2017-10-31 | 2018-01-19 | 昆明云基新材料有限公司 | A kind of low-temperature co-burning ceramic material matched with high-temperature electric conduction silver paste height and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113061024A (en) * | 2021-04-08 | 2021-07-02 | 山东国瓷功能材料股份有限公司 | Low-temperature co-fired material and prepared green ceramic chip and device for overcurrent protection |
| CN114133269A (en) * | 2021-12-06 | 2022-03-04 | 中国振华集团云科电子有限公司 | Preparation method of high-reliability multilayer co-fired ceramic heating element for electronic cigarette |
| CN114446718A (en) * | 2022-01-19 | 2022-05-06 | 苏州晶讯科技股份有限公司 | Low-current polymer patch fuse and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112266272B (en) | 2022-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112266272B (en) | Surface-mounted fuse based on low-temperature co-fired ceramic technology and preparation method thereof | |
| KR102048388B1 (en) | Thick-film pastes containing lead- and tellurium-oxides, and their use in the manufacture of semiconductor devices | |
| JP5536916B2 (en) | Conductive paste for fine line high aspect ratio screen printing in semiconductor device manufacturing | |
| EP2718938B1 (en) | Thick film paste containing bismuth-based oxide and its use in the manufacture of semiconductor devices | |
| US8845932B2 (en) | Thick film paste containing bismuth-tellurium-oxide and its use in the manufacture of semiconductor devices | |
| EP2677523A2 (en) | Method of manufacturing thick-film electrode | |
| EP2584566A1 (en) | Thick film silver paste and its use in the manufacture of semiconductor devices | |
| WO2012138930A2 (en) | Thick film paste containing bismuth-tellurium-oxide and its use in the manufacture of semiconductor devices | |
| US20210350948A1 (en) | Full-area aluminum back surface field back-side silver paste and preparation method and application thereof | |
| WO2013022620A1 (en) | Thick film paste containing lead-tellurium-lithium-titanium-oxide and its use in the manufacture of semiconductor devices | |
| CN102831949A (en) | Efficient lead-free silver paste on back of solar cell and preparation method of silver paste | |
| WO2012158905A1 (en) | Thick film paste containing bismuth-tellurium-oxide and its use in the manufacture of semiconductor devices | |
| JP2013239695A (en) | Thick-film composition containing antimony oxide and its use in manufacture of semiconductor devices | |
| JP2015170601A (en) | Conductive paste used for solar cell electrode | |
| EP2718937B1 (en) | Thick film paste containing bismuth-based oxide and its use in the manufacture of semiconductor devices | |
| KR102119623B1 (en) | Thick film resistor composition and thick film resistor paste comprising the same | |
| WO2021221173A1 (en) | Thick film resistor paste, thick film resistor, and electronic component | |
| CN102831952A (en) | Conductive silver paste for environmental-friendly lead-free silicon solar cell front electrode and preparation method of conductive silver paste | |
| CN112635096B (en) | Silver paste for sheet resistor | |
| CN105428166A (en) | Manufacturing method of chip fuse | |
| US20130014816A1 (en) | Conductive paste, method for manufacturing solar cell electrodes and solar cell electrodes | |
| WO2013031957A1 (en) | Lead-free glass composition for forming conductors | |
| CN107986631A (en) | A kind of pressure-sensitive aluminium paste lead-free glass powder and preparation method thereof | |
| JP7279551B2 (en) | Composition for thick film resistor, paste for thick film resistor, and thick film resistor | |
| JP7027719B2 (en) | Glass composition and glass powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |