CN1881486B - Over-voltage protection element with surface insulation layer and its manufacturing method - Google Patents
Over-voltage protection element with surface insulation layer and its manufacturing method Download PDFInfo
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- CN1881486B CN1881486B CN200510077206A CN200510077206A CN1881486B CN 1881486 B CN1881486 B CN 1881486B CN 200510077206 A CN200510077206 A CN 200510077206A CN 200510077206 A CN200510077206 A CN 200510077206A CN 1881486 B CN1881486 B CN 1881486B
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Abstract
The invention relates to an over-voltage protective element, which comprises a main body and an iron insulated layer, wherein said iron insulated layer is at the surface of main body, for protecting the main body in the process that plating external electrode. The invention also provides a relative production.
Description
Technical field
The present invention relates to a kind of overvoltage protection element and its manufacture method, particularly a kind of in the method for formation iron content insulating barrier on the overvoltage protection element body surfaces with the described overvoltage protection element main body of protection in plating external electrode process.
Background technology
For in response to light, thin, short, little needs of electronic correlation product now; integrated circuit component is adopted in a large number; in order to protect these integrated circuit components not to be subjected to the damage of surging; the overvoltage protection element (over-voltage protecting device) that must employing can under three ten-day period of hot season spy's low-voltage, work; the lamination chip type rheostat of for example rheostat (varistor), so low voltage application comes into one's own gradually.Utilize laminating technique to make resistance change element except the volume of minimizing being arranged and make things convenient for the surface adhering technology uses, and it is special in tens of volts low pressure range accurately to maintain the three ten-day period of hot season.
Zinc oxide system rheostat is used the most widely in the existing rheostat.TaiWan, China is announced No. 231357 patent and is disclosed a kind of zinc oxide varistor, wherein except the zinc oxide that uses at least 90 moles of %, add the magnesium oxide of 0.001 to 2.0 mole of % and the rare earth oxide of 0.005 to 1.0 weight % simultaneously, thereby reduced rheostatic leakage current situation.TaiWan, China is announced No. 543043 patent and is disclosed and a kind ofly be the rheostat of principal component with zinc oxide and form on described rheostatic surface and have preferred alkali resistance or the acid proof film of separating out.In addition, United States Patent (USP) the 6th, 146 also discloses a kind of zinc oxide ceramics rheostat No. 552, and it is to add the synthetic powder be made up of bismuth oxide, titanium oxide and antimony oxide to promote rheostatic electrical characteristics and reliability in the zinc oxide material powder.
In the processing procedure of conventional zinc oxide varistor, make external electrode in order to utilize plating mode, at first must protect the zinc oxide varistor main body, electroplated simultaneously to prevent described zinc oxide varistor main body and the external electrode on it.
United States Patent (USP) the 5th; 614; 074 and 5,757, the technology of No. 263 announcement protection zinc oxide varistor main bodys; it at first soaks described zinc oxide varistor main body puts in a phosphate radical solution; protect described zinc oxide varistor main body to form a trbasic zinc phosphate overlay film, afterwards, described trbasic zinc phosphate overlay film is strengthened described trbasic zinc phosphate structure of film via heat treatment (being generally 600 ℃ to 800 ℃) again; be beneficial to protect described zinc oxide varistor main body in electroplating process, to avoid plating metal, as nickel or tin.
The shortcoming of above-mentioned conventional film mulching method is; in electroplating process; because described zinc oxide varistor main body must place acid electroplating liquid; and described trbasic zinc phosphate overlay film is very fast by the electroplate liquid corrosion in acid electroplating liquid; cause plating to spread phenomenon to such an extent as to can't effectively protect described zinc oxide varistor main body, described zinc oxide varistor function is worsened or forfeiture.
Therefore, this case inventor develops overvoltage protection element and its manufacture method of a kind of novelty, to address the above problem.
Summary of the invention
Main purpose of the present invention is to provide a kind of manufacture method of overvoltage protection element; it is before electroplating external electrode, forms an iron content insulating barrier earlier and do not corroded by electroplate liquid to protect described overvoltage protection element main body on the overvoltage protection element body surfaces.
Another object of the present invention is to provide a kind of manufacture method of overvoltage protection element; it is before electroplating external electrode; and on the overvoltage protection element body surfaces, form after the trbasic zinc phosphate insulating barrier; form a zinc iron phosphate insulating barrier by adding iron ion with the zinc ion that replaces in the part trbasic zinc phosphate; again about 600 ℃ to 900 ℃ via heat treatment to strengthen the crystallinity of zinc iron phosphate; do not corroded to protect described overvoltage protection element main body by electroplate liquid; thereby improve the shortcoming of the antiacid corrosivity deficiency of conventional trbasic zinc phosphate insulating barrier. in addition; make the method for overlay film with respect to other; zinc iron phosphate overlay film of the present invention just can reach and 100% cover the overvoltage protection element main body; and conventional film covering method can not take place is not that the covering deficiency is exactly to cover too much situation. therefore; when being applied to overvoltage protection element (as rheostat) group row, the present invention can reach the better protection effect.
Another object of the present invention is to provide a kind of manufacture method of overvoltage protection element; it is before electroplating external electrode; printing monoxide cream (oxidepaste) on the overvoltage protection element body surfaces; wherein said oxide paste comprises phosphorous oxides and ferriferous oxide at least; heat described oxide paste afterwards again, to form an insulating barrier.
Another object of the present invention is to provide a kind of manufacture method of overvoltage protection element; it is on the end face of the stacked body that the zinc oxide ceramics strip is stacked into and bottom surface an insulating barrier strip to be set respectively; or described insulating barrier strip inserted between the described zinc oxide ceramics strip, afterwards again with described insulating barrier strip and zinc oxide ceramics strip sintering together.Described insulating barrier strip can be protected described zinc oxide ceramics strip in the electroplating process that continues.
Embodiment
The present invention relates to the manufacture method of a kind of overvoltage protection element (a for example rheostat); it is before electroplating external electrode, is forming an iron content insulating barrier on the overvoltage protection element body surfaces to protect described overvoltage protection element main body electroplating not corroded by electroplate liquid in the external electrode process and to be electroplated earlier.
" iron ion " as herein described can be iron ion conventional in any technology, and it includes, but is not limited to Fe2+ and Fe3+.
For containing the overvoltage protection element of zinc, it is preferably formed with sintering by the zinc oxide ceramics strip pile up that has interior electrode on a plurality of surfaces " overvoltage protection element main body " as herein described.The usual manner manufacturing of overvoltage protection element main body of the present invention in can any technology, for example, the manufacturing step of described overvoltage protection element main body is as follows:
(1) provides a plurality of zinc oxide ceramics strips;
(2) electrode in the printing;
(3) pile up described zinc oxide ceramics strip to form a stacked body; With
(4) the described stacked body of sintering to be forming described overvoltage protection element main body,
Described manufacturing step preferably can be done following variation, step (1) also comprises provides at least one insulating barrier strip, the material of described insulating barrier strip is different from described zinc oxide ceramics strip, and step (3) is for piling up described zinc oxide ceramics strip and described insulating barrier strip to form a stacked body.
Electrode can be printed on the described zinc oxide ceramics strip and maybe can be printed on the described insulating barrier strip in wherein said.
In a preferred embodiment; described overvoltage protection element main body comprises the zinc oxide of at least 90 moles of % and the additive of 10 moles of % at the most; wherein said additive-package containing metal oxide and its mixture, the metal of described metal oxide is selected from the group that is made up of chromium, manganese, cobalt, antimony, aluminium and bismuth.
" surface of overvoltage protection element main body " as herein described comprises end face, bottom surface and two sides of described overvoltage protection element main body; but do not comprise two end face; the direction of wherein said end face and bottom surface is identical with described zinc oxide ceramics strip stacking direction; described two end faces are used for forming external electrode, and described two sides are with respect to described two end faces.
The manufacture method of described overvoltage protection element has following several.
First embodiment may further comprise the steps:
(a) provide an overvoltage protection element main body;
(b) form an external electrode at two end faces of described overvoltage protection element main body respectively;
(c) described overvoltage protection element main body is immersed in the monophosphate solution, on the surface of described overvoltage protection element main body, to form the insulating barrier of a trbasic zinc phosphate:
(d) iron ion is added in the described phosphate solution, make described insulating barrier comprise ferric phosphate; With
(e) electroplate described external electrode.
As mentioned before, the usual manner manufacturing of the overvoltage protection element main body of present embodiment in can any technology says that specifically wherein used phosphate solution and iron ion source are known in any technology.The characteristics of present embodiment are the producing method of insulating barrier, it is for forming a trbasic zinc phosphate insulating barrier with conventional method earlier, partly replace the zinc ion of described trbasic zinc phosphate insulating barrier with iron ion (for example Fe2+, from ferric sulfate (FeSO4)) more afterwards, and form a new zinc iron phosphate insulating barrier.
Yet be understandable that; above-mentioned steps (c) and order (d) can be exchanged mutually; promptly; iron ion can be added to earlier (step (d)) behind the monophosphate solution; again described overvoltage protection element main body is dipped in the phosphate solution of described iron content (step (c)), to generate the zinc iron phosphate insulating barrier.
Afterwards; again via at about 600 ℃ to about 900 ℃; be preferably about 700 ℃ to about 850 ℃; heat treatment is to strengthen the crystallinity of ferric phosphate and trbasic zinc phosphate; to protect described overvoltage protection element main body not corroded, has only the trbasic zinc phosphate composition and the shortcoming of antiacid corrosivity deficiency thereby improve conventional insulating barrier by electroplate liquid.The those skilled in the art is appreciated that at this embodiment on the other hand described iron ion also can all replace the zinc ion of described trbasic zinc phosphate insulating barrier, and forms a new ferric phosphate insulating barrier.
In a preferred embodiment, the reaction equation of step (c) is as follows:
3ZnO+2K3(PO4)→Zn3(PO4)2+3K2O
The trbasic zinc phosphate that is produced is Zn3 (PO4) 2.
The reaction equation of step (d) is as follows:
Zn3(PO4)2+3FeSO4→Fe3(PO4)2+3ZnSO4
The ferric phosphate that is produced is Fe3 (PO4) 2.
Be understandable that, can utilize other known in this technology modes to produce the ferric phosphate of FeHPO4.
Preferably, described dispatch from foreign news agency is silver electrode very, and described step (d) also comprises one afterwards at about 600 ℃ to about 900 ℃, be preferably the step of about 600 ℃ to 850 ℃ described insulating barriers of following heat treatment, and step (e) is electronickelling and tin.
The made overvoltage protection element of present embodiment comprises the insulating barrier of an overvoltage protection element main body, two external electrodes and a phosphoric acid iron.Described overvoltage protection element main body has an end face, a bottom surface, two sides and two end faces.Described external electrode lays respectively at two end faces of described overvoltage protection element main body.The insulating barrier of described phosphoric acid iron is positioned at the end face of described overvoltage protection element main body, a bottom surface and two sides.
Second embodiment may further comprise the steps:
(a) provide an overvoltage protection element main body;
(b) form an external electrode at two end faces of described overvoltage protection element main body respectively;
(c) described overvoltage protection element main body is immersed in the monophosphate solution, wherein said phosphate solution comprises phosphate anion and iron ion at least;
(d) on the surface of described overvoltage protection element main body, form the zinc iron phosphate precipitate;
(e) the described zinc iron phosphate precipitate of heating is to form an insulating barrier; With
(f) electroplate described external electrode.
The difference of the present embodiment and first embodiment is the producing method of described insulating barrier.In the present embodiment, the producing method of described insulating barrier is to form earlier the zinc iron phosphate precipitate, heats described zinc iron phosphate precipitate afterwards and forms a zinc iron phosphate compound (iron zinc phosphate) insulating barrier.The source of its iron ion is described in first embodiment.In a preferred embodiment, described zinc iron phosphate compound insulating barrier is [(Zn1-x, Fex) 3 (PO4) 2].In another preferred embodiment, described zinc iron phosphate compound insulating barrier then is [(Zn1-x, Fex) HPO4].
The made overvoltage protection element of present embodiment comprises the insulating barrier of an overvoltage protection element main body, two external electrodes and a zinc iron phosphate compound.Described overvoltage protection element main body has an end face, a bottom surface, two sides and two end faces.Described external electrode lays respectively at two end faces of described overvoltage protection element main body.The insulating barrier of described zinc iron phosphate compound is positioned at the end face of described overvoltage protection element main body, a bottom surface and two sides.
The 3rd embodiment may further comprise the steps:
(a) provide an overvoltage protection element main body;
(b) monoxide cream (oxide paste) is printed on the surface of described overvoltage protection element main body, wherein said oxide paste comprises phosphorous oxides and ferriferous oxide at least;
(c) the described oxide paste of heating is to form an insulating barrier;
(d) form an external electrode at two end faces of described overvoltage protection element main body respectively; With
(e) electroplate described external electrode.
The difference of the present embodiment and first embodiment is the producing method of described insulating barrier.In the present embodiment, the producing method of described insulating barrier contains the oxide paste of phosphorous oxides and ferriferous oxide for utilizing printing one.In a preferred embodiment, described oxide paste comprises the ferriferous oxide of 20 to 65 weight %, the phosphorous oxides of 20 to 65 weight %, the bismuth oxide of 0 to 10 weight % and the zinc oxide of 0 to 30 weight %, wherein said ferriferous oxide can be conventional ferriferous oxide, is preferably Fe2O3.Described phosphorous oxides can be conventional phosphorous oxides, is preferably P2O5.Described bismuth oxide can be conventional bismuth oxide, is preferably Bi2O3.Described zinc oxide can be conventional zinc oxide, is preferably ZnO.
The made overvoltage protection element of present embodiment comprises an overvoltage protection element main body, two external electrodes and an insulating barrier that contains phosphorous oxides and ferriferous oxide.Described overvoltage protection element main body has an end face, a bottom surface, two sides and two end faces.Described external electrode lays respectively at two end faces of described overvoltage protection element main body.The described insulating barrier that contains phosphorous oxides and ferriferous oxide is positioned at the end face of described overvoltage protection element main body, a bottom surface and two sides.
The 4th embodiment may further comprise the steps:
(a) provide a plurality of zinc oxide ceramics strips;
(b) provide at least one insulating barrier strip, the material of described insulating barrier strip is different from described zinc oxide ceramics strip;
(c) interior electrode is printed on described zinc oxide ceramics strip or the described insulating barrier strip;
(d) pile up described zinc oxide ceramics strip and described insulating barrier strip to form a stacked body;
(e) the described stacked body of sintering is to form an overvoltage protection element main body; With
(f) form external electrode at two end faces of described overvoltage protection element main body, to form an overvoltage protection element.
The different manufactures that are described overvoltage protection element main body in the characteristics of present embodiment that are in of present embodiment and above-mentioned three kinds of embodiment. in the present embodiment; described insulating barrier is a ceramic insulating layer strip; it piles up the back sintering and forms described overvoltage protection element main body with the zinc oxide ceramics strip. and described ceramic insulating layer strip can be positioned at the end face and the bottom surface of described overvoltage protection element main body, or inserts between the described zinc oxide ceramics strip. and the material of described ceramic insulating layer strip can be aluminium oxide, zirconia or glass ceramics etc.
The made overvoltage protection element of present embodiment comprises an overvoltage protection element main body and two external electrodes.Described overvoltage protection element main body has an end face, a bottom surface, two sides and two end faces.Described overvoltage protection element main body comprises a plurality of zinc oxide ceramics strips and two ceramic insulating layer strips, and described ceramic insulating layer strip lays respectively at the top of described a plurality of zinc oxide ceramics strips and below.Described external electrode lays respectively at two end faces of described overvoltage protection element main body.
Be understandable that; when the overvoltage protection element main body of utilizing present embodiment to manufacture has only up and down two insulating barrier strips; can utilize above-mentioned first to the 3rd embodiment again and form insulating barrier in described overvoltage protection element body surfaces; mainly be two sides, but also can form insulating barrier at end face and bottom surface.
Now with following example in detail the present invention, but do not mean the content that the present invention only is confined to these examples and is disclosed.
Example 1:
At first, chromium oxide (Cr2O3), bismuth oxide (Bi2O3) and the cobalt oxide (Co2O3) etc. with 94 moles of % zinc oxide (ZnO) powder, each 1.5 moles of % antimony oxide (Sb2O3) and manganese oxide (Mn2O3) and each 1 mole of % form a composition.Utilize conventional ceramic processing technology, described composition all added in the deionized water to mix disperseed 5 hours, afterwards, adhesive (the polyvinyl alcohol that adds 7.5 weight %, PVA), the plasticizer (polyethylene glycol of 3.0 weight %, PEG), release agent of the defoamer of 0.5 weight % (Triton is available from Air Products company) and 1.0 weight % etc. is to be prepared into a slurry.Then, described slurry is made a plurality of zinc oxide ceramics strips with the scraper forming technique.
Then, again with silver/palladium cream (Ag/Pd paste) (wherein silver is 80 weight %, and palladium is 20 weight %) silk screen printing on described ceramic strip as interior electrode, after drying, multilayer is piled up and with pressure compacting, is obtained a stacked body through the ceramic strip of printing.Afterwards, described stacked body is cut into be about 1.2mm, the monomer of wide about 0.65mm.Again described monomer is fired about 24 hours to remove organic bond under 300 ℃, make a zinc oxide varistor main body about 90 minutes of about 900 ℃ of following sintering afterwards.
Then, utilize routine techniques to remove acute angle (tumbling), form a silver medal external electrode at two end faces of described zinc oxide varistor main body respectively again, and the described silver-colored external electrode of sintering.
Then, described zinc oxide varistor main body is immersed in a potassium phosphate (K3 (the PO4)) solution, and temperature is controlled at about 70 ℃, stir simultaneously, the zinc oxide that is beneficial to described zinc oxide varistor main body can react with phosphate radical, and forms a trbasic zinc phosphate (Zn3 (PO4) 2) insulating barrier on the surface of described zinc oxide varistor main body.
Then, ferric sulfate (FeSO4) is added in the described potassium phosphate solution, and to produce iron ion (Fe2+), described iron ion partly replaces the zinc ion of described trbasic zinc phosphate insulating barrier and forms ferric phosphate (Fe3 (PO4) 2), thereby form a new insulating barrier, it comprises trbasic zinc phosphate and ferric phosphate.Afterwards, described insulating barrier is kept 10 minutes to 6 hours heat treatment to strengthen the crystallinity and the acid-resisting of ferric phosphate and trbasic zinc phosphate under about 700 ℃ to 850 ℃ temperature.
Afterwards, place a nickel solution to electroplate described zinc oxide varistor main body,, after the cleaning, place a solution of tin to carry out electrotinning 3 μ m again, promptly can be made into a zinc oxide varistor described external electrode electronickelling 2 μ m.
Example 2:
At first, with 94 moles of % zinc oxide (ZnO) powder, each 1.5 moles of % antimony oxides (Sb2O3) and manganese oxide (Mn2O3), chromium oxide (Cr2O3) with each 1 mole of %, bismuth oxide (Bi2O3) and cobalt oxide (Co2O3) etc. form a composition. utilize conventional ceramic processing technology, described composition all added in the deionized water to mix disperseed 5 hours, afterwards, adhesive (the polyvinyl alcohol that adds 7.5 weight %, PVA), 3.0 the plasticizer (polyethylene glycol of weight %, PEG), 0.5 the release agents of the defoamer of weight % (Triton is available from Air Products company) and 1.0 weight % etc. are to be prepared into a slurry.Then, described slurry is made a plurality of zinc oxide ceramics strips with the scraper forming technique.
Then, again with silver/palladium cream (Ag/Pd paste) (wherein silver is 80 weight %, and palladium is 20 weight %) silk screen printing on described ceramic strip as interior electrode, after drying, multilayer is piled up and with pressure compacting, is obtained a stacked body through the ceramic strip of printing.Afterwards, described stacked body is cut into be about 1.2mm, the monomer of wide about 0.65mm.Again described monomer is fired about 24 hours to remove organic bond under about 300 ℃, make a zinc oxide varistor main body about 90 minutes of about 900 ℃ of following sintering afterwards.
Then, utilize routine techniques to remove acute angle (tumbling), form a silver medal external electrode at two end faces of described zinc oxide varistor main body respectively again, and the described silver-colored external electrode of sintering.
Then, described zinc oxide varistor main body is immersed in a potassium phosphate (K3 (the PO4)) solution, has the iron ion of about 200ppm in this potassium phosphate solution.The surface for the treatment of described zinc oxide varistor main body forms the zinc iron phosphate precipitate, heated about 30 minutes down at about 700 ℃ subsequently, make it generate the insulating barrier of a zinc iron phosphate compound (iron zinc phosphate), the chemical formula of described zinc iron phosphate compound is [(Zn1-x, Fex) 3 (PO4) 2] or [(Zn1-x, Fex) HPO4].
Afterwards, place a nickel solution to electroplate described zinc oxide varistor main body,, after the cleaning, place a solution of tin to carry out electrotinning 3 μ m again, promptly can be made into a zinc oxide varistor described external electrode electronickelling 2 μ m.
Example 3:
At first, chromium oxide (Cr2O3), bismuth oxide (Bi2O3) and the cobalt oxide (Co2O3) etc. with 94 moles of % zinc oxide (ZnO) powder, each 1.5 moles of % antimony oxide (Sb2O3) and manganese oxide (Mn2O3) and each 1 mole of % form a composition.Utilize conventional ceramic processing technology, described composition all added in the deionized water to mix disperseed 5 hours, afterwards, adhesive (the polyvinyl alcohol that adds 7.5 weight %, PVA), the plasticizer (polyethylene glycol of 3.0 weight %, PEG), release agent of the defoamer of 0.5 weight % (Triton is available from Air Products company) and 1.0 weight % etc. is to be prepared into a slurry.Then, described slurry is made a plurality of zinc oxide ceramics strips with the scraper forming technique.
Then, again with silver/palladium cream (Ag/Pd paste) (wherein silver is 80 weight %, and palladium is 20 weight %) silk screen printing on described ceramic strip as interior electrode, after drying, multilayer is piled up and with pressure compacting, is obtained a stacked body through the ceramic strip of printing.Afterwards, described stacked body is cut into be about 1.2mm, the monomer of wide about 0.65mm.Again described monomer is fired about 24 hours to remove organic bond under about 300 ℃, make a zinc oxide varistor main body about 90 minutes of about 900 ℃ of following sintering afterwards.
Then, utilize routine techniques to remove acute angle (tumbling).
Then, to utilize screen printing technique printing monoxide cream on described zinc oxide varistor main body end face, bottom surface and two sides, wherein said oxide paste comprises the iron oxide (Fe2O3) of 40 weight %, the phosphorous oxide (P2O5) of 40 weight %, the bismuth oxide (Bi2O3) of 2 weight %, the zinc oxide (ZnO) of 18 weight %.Described in addition oxide paste also comprises other solvents (solvent) and adhesive (binder).
Heated described oxide paste about 30 minutes down at about 700 ℃ subsequently, make it generate an insulating barrier.Form a silver medal external electrode at two end faces of described zinc oxide varistor main body respectively again, and the described silver-colored external electrode of sintering.
Afterwards, place a nickel solution to electroplate described zinc oxide varistor main body,, after the cleaning, place a solution of tin to carry out electrotinning 3 μ m again, promptly can be made into a zinc oxide varistor described external electrode electronickelling 2 μ m.
Example 4:
At first, with 94 moles of % zinc oxide (ZnO) powder, each 1.5 moles of % antimony oxides (Sb2O3) and manganese oxide (Mn2O3), chromium oxide (Cr2O3) with each 1 mole of %, bismuth oxide (Bi2O3) and cobalt oxide formation one compositions such as (Co2O3). utilize conventional ceramic processing technology that described composition is all added to mix in the deionized water and disperseed 5 hours, afterwards, adhesive (the polyvinyl alcohol that adds 7.5 weight %, PVA), 3.0 the plasticizer (polyethylene glycol of weight %, PEG), 0.5 the defoamer (Triton of weight %, available from AirProducts company) and the release agent of 1.0 weight % etc. to be prepared into a slurry. then, described slurry is made a plurality of zinc oxide ceramics strips with the scraper forming technique.
Then, aluminium oxide (Al2O3) powder of 85 weight % and the borosilicate glass of 15 weight % are filled in the ball grinder, add water solids content is maintained to about 65 weight %.Afterwards, adhesive (the polyvinyl alcohol that adds 8.5 weight %, PVA), the plasticizer of 3.0 weight % (polyethylene glycol, PEG), the defoamer (Triton is available from Air Products company) of 0.5 weight % and release agent of 1.0 weight % etc. to be to be prepared into a slurry.Pressed casting slurry (cast slurry) to form ceramic insulating layer strip by blade again with 80 μ m thickness.
Then, again with silver/palladium cream (Ag/Pd paste) (wherein silver is 80 weight %, and palladium is 20 weight %) silk screen printing on described ceramic strip as interior electrode, after drying, with multilayer through the printing ceramic strip pile up, obtain a stacked body.Afterwards, described ceramic insulating layer strip is placed the end face and the bottom surface of described stacked body, suppress with pressure again.Described stacked body cut into be about 1.2mm, the monomer of wide about 0.65mm.Again described monomer is fired about 24 hours to remove organic bond under about 300 ℃,, and make a zinc oxide varistor main body afterwards about 90 minutes of about 900 ℃ of following sintering.
Example 5:
At first, make a zinc oxide varistor main body in the mode of example 4.Then, utilize routine techniques to remove acute angle (tumbling), form a silver medal external electrode at two end faces of described zinc oxide varistor main body respectively again.
Then, on the surface of described zinc oxide varistor main body, form an insulating barrier that comprises trbasic zinc phosphate and ferric phosphate with the producing method of insulating barrier in the example 1 again.
Afterwards, with electronickelling of described zinc oxide varistor main body and tin, promptly can be made into a zinc oxide varistor.
Example 6:
At first, make a zinc oxide varistor main body in the mode of example 4.Then, utilize routine techniques to remove acute angle (tumbling), form a silver medal external electrode at two end faces of described zinc oxide varistor main body respectively again.
Then, again according to example 2 described modes, on the surface of described zinc oxide varistor main body, form the insulating barrier of a zinc iron phosphate compound.
Afterwards, with electronickelling of described zinc oxide varistor main body and tin, promptly can be made into a zinc oxide varistor.
Example 7:
At first, make a zinc oxide varistor main body in the mode of example 4.Then, utilize routine techniques to remove acute angle (tumbling).
Then, again according to example 3 described modes, printing monoxide cream on described zinc oxide varistor main body.Yet be noted that therefore, two sides that described oxide paste only need be printed on described zinc oxide varistor main body get final product because the end face and the bottom surface of described zinc oxide varistor main body have a ceramic insulating layer strip respectively.Heated described oxide paste about 30 minutes down at about 700 ℃ subsequently, make it generate an insulating barrier.Form a silver medal external electrode at two end faces of described zinc oxide varistor main body respectively again.
Afterwards, with electronickelling of described zinc oxide varistor main body and tin, promptly can be made into a zinc oxide varistor.
Example 8:
This example is roughly the same with example 4, do not exist together and only be the material of described ceramic insulating layer strip. in this example, zirconia (ZrO2) powder of 85 weight % and the borosilicate glass of 15 weight % are filled in the ball grinder, add water solids content is maintained to after about 65 weight %., adhesive (the polyvinyl alcohol that adds 8.5 weight %, PVA), the plasticizer (polyethylene glycol of 3.0 weight %, PEG), release agent of the defoamer of 0.5 weight % (Triton is available from Air Products company) and 1.0 weight % etc. is to be prepared into a slurry.Pressed the casting slurry to form ceramic insulating layer strip by blade again with 80 μ m thickness.
Example 9:
This example is roughly the same with example 4, and not existing together only is the material of described ceramic insulating layer strip.In this example, glass ceramics (glass-ceramic) powder of 85 weight % and the borosilicate glass of 15 weight % are filled in the ball grinder, add water solids content is maintained to about 65 weight %.Afterwards, adhesive (the polyvinyl alcohol that adds 8.5 weight %, PVA), the plasticizer of 3.0 weight % (polyethylene glycol, PEG), the defoamer (Triton is available from Air Products company) of 0.5 weight % and release agent of 1.0 weight % etc. to be to be prepared into a slurry.Pressed the casting slurry to form ceramic insulating layer strip by blade again with 80 μ m thickness.
Example 10:
This example is roughly the same with example 4, and not existing together only is the material of described ceramic insulating layer strip.In this example, zirconia (ZrO2) powder of 42.5 weight %, glass ceramics (glass-ceramic) powder of 42.5 weight % and the borosilicate glass of 15 weight % are filled in the ball grinder, add water solids content is maintained to about 65 weight %.Afterwards, adhesive (the polyvinyl alcohol that adds 8.5 weight %, PVA), the plasticizer of 3.0 weight % (polyethylene glycol, PEG), the defoamer (Triton is available from Air Products company) of 0.5 weight % and release agent of 1.0 weight % etc. to be to be prepared into a slurry.Pressed the casting slurry to form ceramic insulating layer strip by blade again with 80 μ m thickness.
Material of the present invention, method and feature will be more obvious through above-mentioned example explanation, now will be appreciated that, modification of being carried out under the situation that does not break away from spirit of the present invention or change all are that the present invention is claimed.
Claims (43)
1. the manufacture method of an overvoltage protection element; it is characterized in that; before electroplating external electrode, on the surface of described overvoltage protection element main body, form an iron content insulating barrier earlier; the surface of wherein said overvoltage protection element main body comprises end face, bottom surface and two sides of described overvoltage protection element main body; the direction of wherein said end face and bottom surface is identical with zinc oxide ceramics strip stacking direction, and two end faces of described overvoltage protection element main body are used for forming external electrode.
2. the manufacture method of an overvoltage protection element, it may further comprise the steps:
(a) provide an overvoltage protection element main body;
(b) form an external electrode at two end faces of described overvoltage protection element main body respectively;
(c) described overvoltage protection element main body is immersed in the monophosphate solution, on the surface of described overvoltage protection element main body, to form the insulating barrier of a trbasic zinc phosphate;
(d) iron ion is added in the described phosphate solution, make described insulating barrier comprise ferric phosphate; With
(e) electroplate described external electrode.
3. method according to claim 2, wherein said overvoltage protection element main body comprise the zinc oxide of at least 90 moles of % and the additive of 10 moles of % at the most.
4. method according to claim 3, wherein said additive-package containing metal oxide and its mixture, the metal of described metal oxide is selected from the group that is made up of chromium, manganese, cobalt, antimony, aluminium and bismuth.
5. method according to claim 2, wherein said ferric phosphate be selected from by
The group that forms with its mixture.
6. method according to claim 2, the insulating barrier in the wherein said step (d) are a ferric phosphate layer.
7. method according to claim 2, the insulating barrier in the wherein said step (d) comprises ferric phosphate and trbasic zinc phosphate.
8. method according to claim 2, wherein said step (e) is electronickelling and tin.
9. method according to claim 2, wherein said step (d) also comprise one afterwards in about 600 ℃ of steps to about 900 ℃ of described insulating barriers of following heat treatment.
10. method according to claim 2, wherein said step (a) comprising:
(a1) provide a plurality of zinc oxide ceramics strips;
(a2) electrode in the printing;
(a3) pile up described zinc oxide ceramics strip to form a stacked body; With
(a4) the described stacked body of sintering is to form described overvoltage protection element main body.
11. method according to claim 10, wherein said step (a1) comprises that also one provides the step of at least one insulating barrier strip, the material of wherein said insulating barrier strip is different from described zinc oxide ceramics strip, and described step (a3) is piled up described zinc oxide ceramics strip and described insulating barrier strip.
12. method according to claim 11, wherein said step (a3), place described insulating barrier strip the end face and the bottom surface of the zinc oxide ceramics strip after described the piling up again for piling up described zinc oxide ceramics strip earlier.
13. method according to claim 11 wherein in described step (a3), is inserted described insulating barrier strip between the described zinc oxide ceramics strip.
14. the manufacture method of an overvoltage protection element, it may further comprise the steps:
(a) provide an overvoltage protection element main body;
(b) form an external electrode at two end faces of described overvoltage protection element main body respectively;
(c) described overvoltage protection element main body is immersed in the monophosphate solution, wherein said phosphate solution comprises phosphate anion and iron ion at least;
(d) on the surface of described overvoltage protection element main body, form the zinc iron phosphate precipitate;
(e) the described zinc iron phosphate precipitate of heating is to form an insulating barrier; With
(f) electroplate described external electrode.
15. method according to claim 14, wherein said overvoltage protection element main body comprise the zinc oxide of at least 90 moles of % and the additive of 10 moles of % at the most.
16. method according to claim 15, wherein said additive-package containing metal oxide and its mixture, the metal of described metal oxide is selected from the group that is made up of chromium, manganese, cobalt, antimony, aluminium and bismuth.
17. method according to claim 14, wherein said insulating barrier is selected from by [(Zn
1-x, Fe
x)
3(PO
4)
2], [(Zn
1-x, Fe
x) HPO
4] and the group that forms of its mixture.
18. method according to claim 14, wherein said step (f) is electronickelling and tin.
19. method according to claim 14, wherein said step (a) comprising:
(a1) provide a plurality of zinc oxide ceramics strips;
(a2) electrode in the printing;
(a3) pile up described zinc oxide ceramics strip to form a stacked body; With
(a4) the described stacked body of sintering is to form described overvoltage protection element main body.
20. method according to claim 19, wherein said step (a1) comprises that also one provides the step of at least one insulating barrier strip, the material of wherein said insulating barrier strip is different from described zinc oxide ceramics strip, and described step (a3) is for piling up described zinc oxide ceramics strip and described insulating barrier strip.
21. method according to claim 20, wherein said step (a3), place described insulating barrier strip the end face and the bottom surface of the zinc oxide ceramics strip after described the piling up again for piling up described zinc oxide ceramics strip earlier.
22. method according to claim 20 wherein in described step (a3), is inserted described insulating barrier strip between the described zinc oxide ceramics strip.
23. the manufacture method of an overvoltage protection element, it may further comprise the steps:
(a) provide an overvoltage protection element main body;
(b) printing monoxide cream on the surface of described overvoltage protection element main body, wherein said oxide paste comprises phosphorous oxides and ferriferous oxide at least;
(c) the described oxide paste of heating is to form an insulating barrier;
(d) form an external electrode at two end faces of described overvoltage protection element main body respectively; With
(e) electroplate described external electrode.
24. method according to claim 23, wherein said overvoltage protection element main body comprise the zinc oxide of at least 90 moles of % and the additive of 10 moles of % at the most.
25. method according to claim 24, wherein said additive-package containing metal oxide and its mixture, the metal of described metal oxide is selected from the group that is made up of chromium, manganese, cobalt, antimony, aluminium and bismuth.
26. method according to claim 23, wherein said step (e) is electronickelling and tin.
27. method according to claim 23, wherein said oxide paste comprise the ferriferous oxide of 20 to 65 weight % and the phosphorous oxides of 20 to 65 weight %.
28. method according to claim 27, wherein said ferriferous oxide are Fe2O3, described phosphorous oxides is P2O5.
29. method according to claim 23, wherein said oxide paste also comprise the bismuth oxide of 0 to 10 weight % and the zinc oxide of 0 to 30 weight %.
30. method according to claim 29, wherein said bismuth oxide is Bi2O3, and described zinc oxide is ZnO.
31. method according to claim 23, wherein said step (a) comprising:
(a1) provide a plurality of zinc oxide ceramics strips;
(a2) electrode in the printing;
(a3) pile up described zinc oxide ceramics strip to form a stacked body; With
(a4) the described stacked body of sintering is to form described overvoltage protection element main body.
32. method according to claim 31, wherein said step (a1) comprises that also one provides the step of at least one insulating barrier strip, the material of wherein said insulating barrier strip is different from described zinc oxide ceramics strip, and described step (a3) is for piling up described zinc oxide ceramics strip and described insulating barrier strip.
33. method according to claim 32, wherein said step (a3), place described insulating barrier strip the end face and the bottom surface of the zinc oxide ceramics strip after described the piling up again for piling up described zinc oxide ceramics strip earlier.
34. method according to claim 32 wherein in described step (a3), is inserted described insulating barrier strip between the described zinc oxide ceramics strip.
35. an overvoltage protection element, it comprises:
One overvoltage protection element main body has an end face, a bottom surface, two sides and two end faces;
Two external electrodes, it lays respectively at two end faces of described overvoltage protection element main body; With
The insulating barrier of one iron content, it is positioned at the end face of described overvoltage protection element main body, a bottom surface and two sides.
36. overvoltage protection element according to claim 35, wherein said overvoltage protection element are a zinc oxide varistor.
37. overvoltage protection element according to claim 35, the insulating barrier of wherein said iron content are ferric phosphate.
38. overvoltage protection element according to claim 35, the insulating barrier of wherein said iron content comprises trbasic zinc phosphate and ferric phosphate.
39. overvoltage protection element according to claim 35, the insulating barrier of wherein said iron content are the zinc iron phosphate compound.
40. overvoltage protection element according to claim 35, the insulating barrier of wherein said iron content comprises phosphorous oxides and ferriferous oxide.
41. overvoltage protection element according to claim 35; wherein said overvoltage protection element main body comprises a plurality of zinc oxide ceramics strips and two ceramic insulation strips, and described ceramic insulation strip lays respectively at the top of described zinc oxide ceramics strip and below.
42. overvoltage protection element according to claim 35, wherein said overvoltage protection element main body comprise a plurality of zinc oxide ceramics strips and at least one ceramic insulation strip, described ceramic insulation strip is inserted between the described zinc oxide ceramics strip.
43. according to the described overvoltage protection element of claim 41, wherein said insulating barrier strip comprises monoxide, described oxide is selected from the group that is made up of aluminium oxide, zirconia, glass ceramics and its mixture.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510077206A CN1881486B (en) | 2005-06-16 | 2005-06-16 | Over-voltage protection element with surface insulation layer and its manufacturing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200510077206A CN1881486B (en) | 2005-06-16 | 2005-06-16 | Over-voltage protection element with surface insulation layer and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1881486A CN1881486A (en) | 2006-12-20 |
| CN1881486B true CN1881486B (en) | 2010-05-05 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1086050C (en) * | 1995-05-08 | 2002-06-05 | 松下电器产业株式会社 | Lateral high-resistance additive for zinc oxide varistor, zinc oxide varistor produced using same, and process for producing said varistor |
| CN1571078A (en) * | 2004-05-13 | 2005-01-26 | 上海大学 | Method for preparing high throughflow nanometre composite lightning arrester valve plate |
-
2005
- 2005-06-16 CN CN200510077206A patent/CN1881486B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1086050C (en) * | 1995-05-08 | 2002-06-05 | 松下电器产业株式会社 | Lateral high-resistance additive for zinc oxide varistor, zinc oxide varistor produced using same, and process for producing said varistor |
| CN1571078A (en) * | 2004-05-13 | 2005-01-26 | 上海大学 | Method for preparing high throughflow nanometre composite lightning arrester valve plate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1881486A (en) | 2006-12-20 |
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