CN101633989A - Electrode material - Google Patents
Electrode material Download PDFInfo
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- CN101633989A CN101633989A CN200910160230A CN200910160230A CN101633989A CN 101633989 A CN101633989 A CN 101633989A CN 200910160230 A CN200910160230 A CN 200910160230A CN 200910160230 A CN200910160230 A CN 200910160230A CN 101633989 A CN101633989 A CN 101633989A
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Abstract
The invention relates to an electrode material having a glass pipe the inner wall surface of which is provided with a fluorophor layer and the inside of which is enclosed with rare gas and mercury, and a pair of electrodes arranged on two ends of the glass pipe; wherein the electrode is constituted by following Ni alloy which contains at least an element which is selected from a standard group composed of Ti, Hf, Zr, V, Fe, Nb, Mo, Mn, W, Sr, Ba, B, Th, Be, Si, Al, Y, Mg, In and rare earth elements and is more than or equal to 0.001% or less than or equal to 5.0% by mass, and the balance of Ni and impurities. The electrode is not constituted by Ni simple substance but the Ni alloy with the components as above, thus improving the electric discharge performance, oxidation resistance, sputtering resistance and reaction resistance to mercury, and realizing high brightness and long service life.
Description
The application is for Sumitomo Electrics Industry Ltd and to live be entitled as " electrode materials ", the application number that electric accurate conductor company limited submits to Patent Office of the People's Republic of China on May 25th, 2006 be dividing an application of 200610084559.2 Chinese patent application.
Technical field
The present invention relates to the electrode materials that in the electrode of cold-cathode fluorescence lamp, is suitable for, manufacture method and the cold-cathode fluorescence lamp that passes through this electrode materials manufacturing electrode for cold-cathode fluorescent lamp.Particularly relate to the cold-cathode fluorescence lamp that brightness is higher, the life-span is longer.
Background technology
At present, as the irradiation of the original copy of image reading apparatus with liquid crystal indicators (liquid-crystal display) such as the monitoring lcd device of light source, PC, LCD TV be called the various light sources of back of the body irradiation with light source, cold-cathode fluorescence lamp by utilization fully (for example: with reference to the spy open the 2004-71276 communique, the spy opens flat 10-144255 communique).Cold-cathode fluorescence lamp has for example structure shown in Fig. 1.Fig. 1 is one of cold-cathode fluorescence lamp example, is the sectional view of its schematic configuration of expression.This cold-cathode fluorescence lamp 100 has at inner-wall surface and is provided with luminescent coating 101 and encloses rare gas and the Glass tubing 102 of mercury, be disposed at the pair of electrodes 103 in the Glass tubing 102.Luminescent coating 101 was located on the almost full week and total length of Glass tubing 102 inner-wall surfaces, in pipe 102, was mainly luminescent part between two electrodes 103, was non-luminescent part near the electrode 103.Electrode 103 is an end opening, and the other end has the cup-shaped at the end, with the mode relative with peristome be configured in the Glass tubing 102 (with reference to the spy open the 2004-71276 communique, the spy opens flat 10-144255 communique).Another distolateral (bottom side) at the electrode 103 of opening not connects lead (outer conductor 104), applies voltage via these lead 104 counter electrode 103.Connect inside conductor 105 between electrode 103 and the outer conductor 104, this inside conductor 105 is by the formation such as Kovar alloy (Kovar) material of etc.ing that is adjusted into the thermal expansivity of the thermal expansivity equal extent of Glass tubing 102.At the deposited granulated glass sphere of the periphery of inside conductor 105 (bead glass) 106.Utilize this granulated glass sphere 106 that electrode 103 is fixed in the Glass tubing 102, should manage 102 sealings simultaneously, thus the air seal state in the holding tube 102 stably.In addition, the no mercury luminescent lamp of only having enclosed rare gas in Glass tubing 102 is also arranged.
Such luminescent lamp 100 is luminous according to following principle.When applying high-voltage via lead 104 between two electrodes 103, the electronics that exists only in the Glass tubing 102 is attracted at a high speed to collide to electrode 103, at this moment, emits secondary electron from electrode 103 and discharges.By this discharge, the mercury molecules that exist in electronics that is attracted by anode and the Glass tubing 102 etc. collide and the radiation ultraviolet ray, this ultraviolet ray excited fluor, and fluor sends visible light.
As the formation material of above-mentioned electrode, (Ni) is representative for nickel.As the formation material of other electrode, open to record in the 2004-71276 communique the spy and use Ti, Zr, Hf, Nb or Ta, open to record in the 2004-207056 communique the spy and use Mo, Nb, Ta.
In recent years, at the back light unit that is used for liquid-crystal display etc., it was slim, light weight, high brightness, long lifetime are much accounted of.Therefore, for the cold-cathode fluorescence lamp that utilizes with light source as back of the body irradiation, also expect further with its miniaturization, high brightnessization and long lifetime consumingly.In addition, in image reading apparatus, high speed, long lifetime etc. also is much accounted of, even for the cold-cathode fluorescence lamp as light source, also expects high brightnessization, long lifetime strongly.
In existing cold-cathode fluorescence lamp, when lighting, collide, thereby cause electrode substance in Glass tubing, to splash and be piled up in the sputtering phenomenon of inside pipe wall by the mercury ion of discharge generation and electrode with the electrode that constitutes by nickel.When causing sputter, electrode is consumed.Particularly, only some is concentrated consumption and forms the hole in this part owing to electrode, thus electrode can not be used for discharging, thus luminescent lamp has arrived life span.In addition, sputtering layer (by vaporized electrode substance constitute the layer) with mercury form mercury alloys.Therefore, if light for a long time, then mercury is almost all obtained by sputtering layer, and ultraviolet thus radiation can not fully be carried out, and the brightness of lamp is very low, and luminescent lamp has arrived life span.That is, in luminescent lamp in the past,, above-mentioned sputter is easier to shorten owing to making the life-span with the electrode that constitutes by nickel.
When the shape with electrode has formed bottom tube-like, utilize the hollow cathode effect, can suppress sputter in a way, but for the enough structures of can not saying so of the requirement of high brightnessization, long lifetime further.For the requirement of high brightnessization, consider to increase the electric current of lamp, but because the increase of electric current increases the electrode load, so cause sputter easily.That is, sputtering rate is accelerated.Consequently, the consumption of accelerating electrode and the formation of mercury alloys cause the life-span of luminescent lamp to be reduced.If electrode is maximized, then can reduce the unfavorable condition that causes because of sputter, but there are the following problems in this case: 1, the requirement with slimming, miniaturization deviates from mutually; 2, non-luminescent part becomes big.
On the other hand, such as the spy open in 2004-71276 communique and the Te Kai 2004-207056 communique record, consider by with the material beyond the nickel as electrode materials, or the layer that is made of the material beyond the nickel is set in the main body that constitutes by nickel, suppress sputter thus.But there are the following problems for materials such as Mo, Nb, Ta, be difficult to counter electrode process, even or can counter electrode processing, the electrode that is made of this material also is difficult to engage with inside conductor etc.In addition, the spy opens the price comparison height that 2004-71276 communique, spy are opened materials such as the Mo, the Nb that put down in writing in the 2004-207056 communique, Ta, and when using the electrode that is made of this material, cost is quite high.
On the other hand, motion has the material of counter electrode coating promotion release electronics, for example lanthanum compound, Cesium compound, yttrium compound, barium compound etc.But these materials that discharge electronics disperse owing to the ionic that is subjected to discharge generation during lighting at lamp collides, and therefore are difficult to further long lifetime.
Summary of the invention
Main purpose of the present invention is to provide a kind of can help the long lifetime of cold-cathode fluorescence lamp, the electrode materials of high brightnessization.In addition, other purpose of the present invention is to provide a kind of manufacture method of electrode for cold-cathode fluorescent lamp that is suitable for being formed with by this electrode materials the electrode of bottom tube-like.And then other purpose of the present invention is to provide the cold-cathode fluorescence lamp that a kind of life-span is longer, brightness is higher.
In order to obtain more high brightness, long-service-life cold cathode fluorescent lamp more, the present inventor is conceived to electrode especially and has carried out research with keen determination in the building block of lamp.And, following opinion is arranged, promptly in order to realize high brightness, long-service-life cold cathode fluorescent lamp, as the necessary characteristic of electrode be: 1, discharge easily; 2, the difficult oxidation of electrode surface; 3, be difficult to form mercury alloys with mercury; 4, sputtering rate is slow.
When electrode was difficult to discharge, the electronics that discharges tailed off, and consequently: ultraviolet ray can not fully discharge, and is difficult to improve brightness.Relative therewith, easily the electrode of discharge improves brightness easily, therefore, with the same brightness of the electrode that is difficult to discharge under when using, the life-span is longer.In addition, the electrode that is easy to discharge discharges owing to carrying out electronics with lower electric power, so also can reduce specific power consumption.Therefore, expectation constitutes electrode by the material of easy discharge.
In addition, if at electrode surface the oxidation overlay film is arranged, then discharge property is hindered.That is, electrode is difficult to discharge.At this, when making electrode or the electrode that obtains of use when making luminescent lamp (when electrode and inside conductor engage etc.) electrode materials and electrode can be heated.When the easy adsorption of oxygen of electrode materials,, be easy to form the oxidation overlay film at electrode surface by carrying out such heating.To this, by the electrode that the electrode materials that is difficult to adsorption of oxygen constitutes, its surface is difficult to form the oxidation overlay film, can reduce the decline of discharge property.Therefore, expectation constitutes electrode by the material of difficult adsorption of oxygen.
And when electrode materials during easily with mercury formation mercury alloys, the electrode that is made of this electrode materials has been accelerated mercury consumption when sputter, and the result has shortened the life-span of luminescent lamp.To this, by the electrode that the electrode materials that is difficult to form mercury alloys constitutes, mercury consumption is slowed down, further prolongs life.Therefore, electrode preferably is made of the material that is difficult to form mercury alloys.
And when electrode causes sputter easily, when promptly sputtering rate was fast, the consumption of electrode was accelerated, and its result has shortened the life-span of luminescent lamp.To this, be difficult to cause that the electrode of sputter can weaken the reduction of brightness owing to difficult formation sputtering layer in Glass tubing, so compare with the electrode that is easy to generate sputter, high brightness is for a long time.Therefore, expectation is that the slow material of sputtering rate constitutes electrode by being difficult to that sputter takes place.
On the basis of above-mentioned characteristic, present inventors are in order further to reduce cost, and use the electrode materials (composition) of high price materials such as Mo and Nb to study to simple substance not.Its result learns: as the composition of electrode materials, preferably used the Ni alloy of the relatively cheap Ni of price.Therefore, electrode materials of the present invention is made of the Ni alloy.
The electrode materials of first aspect present invention, it can use in the electrode of cold-cathode fluorescence lamp, it is characterized in that, contain total more than or equal to 0.001 quality %, be less than or equal at least a element 5.0 quality %, that from the benchmark group that constitutes by Ti, Hf, Zr, V, Fe, Nb, Mo, Mn, W, Sr, Ba, B, Th, Be, Si, Al, Y, Mg, In, rare earth element, select, remainder is made of Ni and impurity.That is, this electrode materials is characterised in that, is made of the Ni alloy of the specific interpolation element that contains specified range.The electrode made from this electrode materials that is made of the Ni alloy of specific composition discharges easily, and sputtering rate is slow.In addition, the electrode that is made of this electrode materials is difficult to form the oxidation overlay film, is difficult to form mercury alloys.Therefore, the electrode by the electrode materials that uses by the invention described above constitutes obtains high brightness, long-service-life cold cathode fluorescent lamp.
The electrode materials of second aspect present invention, it is an operable electrode materials in the electrode of cold-cathode fluorescence lamp, it is characterized in that, is made of the Ni alloy, its work function is less than 4.7eV.So-called work function is meant, need an electronics be fetched into least energy required the vacuum from solid surface.It is more little to can be described as work function, the material that easy more taking-up electronics promptly discharges easily.Present inventors have estimated the discharge characteristic of the electrode expectation of cold-cathode fluorescence lamp with work function, and its result learns: be preferably less than 4.7eV.Based on this opinion, electrode materials of the present invention is made of the Ni alloy, will satisfy specific work function simultaneously.By using the electrode that constitutes by such electrode materials of the present invention, can obtain high brightness, long-service-life cold cathode fluorescent lamp.
The electrode materials of third aspect present invention, it is the electrode materials that uses in the electrode of cold-cathode fluorescence lamp, it is characterized in that, is made of the Ni alloy, its etch-rate is less than 22nm/min.If electrode causes sputter, then in electrode, collide the part generation corrosion pitting that discharges atom and make surface irregularity by the mercury ionic.The easy more electrode that causes sputter, the degree of depth of the corrosion pitting of time per unit is big more.As etch-rate, present inventors estimate the sputter state of expecting in the electrode of cold-cathode fluorescence lamp with etch-rate with the mean depth of the corrosion pitting of this time per unit, and its result learns: be preferably less than 22nm/min.Based on this opinion, this electrode materials of the present invention is made of the Ni alloy, will satisfy specific etch-rate simultaneously.By using the electrode that constitutes by such electrode materials of the present invention, can obtain high brightness, long-service-life cold cathode fluorescent lamp.In addition, implication is identical in fact with sputtering rate for etch-rate, uses etch-rate among the present invention.
Below, the present invention will be described in more detail.
Electrode materials of the present invention is made of the Ni alloy.Particularly, as adding element, the preferably at least a element of from the benchmark group that constitutes by Ti, Hf, Zr, V, Fe, Nb, Mo, Mn, W, Sr, Ba, B, Th, Be, Si, Al, Y, Mg, In, rare earth element, selecting.Adding element can be a kind of element of selecting from the said reference group, also can be a plurality of elements more than or equal to two kinds.The content that adds element is preferably greater than or equals 0.001 quality %, is less than or equal to 5.0 quality %.When containing the Ni alloy of multiple interpolation element, add up to content to adjust to and satisfy above-mentioned scope.At the content that adds element during, can not improve effectively by containing and add element and the high brightnessization that produces, the characteristic of long lifetime less than 0.001 quality %.On the one hand, the effect tendency improved of this characteristic improves with the increase of the content that adds element, but can think that the content that adds element is that 5.0 quality % are saturated.In addition, surpass 5.0 quality %, then rise because of the increase of adding element causes cost if add the content of element.And the increase of adding element can reduce the plastic working when reaching by this electrode materials manufacturing electrode when making electrode materials.Electrode materials of the present invention as described later, after melt-casting, to cast material be rolled processing and the such plastic working of Wire Drawing make.In addition, when using electrode materials of the present invention to make electrode, the counter electrode material carries out punch process and the such plastic working of forging described later processing is made.Therefore, in order not reduce the plastic working of the starting material and the electrode materials that are used to make electrode materials, the upper content limit of adding element is set at 5.0 quality %.
The said reference group is divided into, be made of Ti, Hf, Zr, V, Fe, Nb, Mo, Mn, W, Sr, Ba, B, Th, Mg, In first group and second group of being made of Be, Si, Al, Y, rare earth element also can be with the element that contained in any one group as adding element.Particularly, serving as when adding element to be selected from above-mentioned first group at least a element (hereinafter referred to as element I), its content for example more than or equal to 0.001 quality %, be less than or equal to 2.0 quality %.That is, electrode materials of the present invention can be for adding up to more than or equal to 0.001 quality %, being less than or equal at least a element from above-mentioned first group selection of 2.0 quality %, and remainder is made of Ni and impurity.Constitute electrode materials by Ni alloy, can obtain having the electrode of above-mentioned 1～4 characteristic with lower cost by the element I that contains this scope.In addition, the cast material that is made of this Ni alloy has the processibility of the degree of the such plastic working of the processing of being rolled and Wire Drawing, can carry out above-mentioned plastic working and makes electrode.And this electrode materials is made electrode owing to have enough carried out punch process and the processibility of the plastic working degree that casting processing is such so can carry out above-mentioned plastic working.Element I can be a kind of element, also can be a plurality of elements more than or equal to two kinds.When being multiple element with element I, total content is adjusted into 0.001～2.0 quality % and adds among the Ni.If the content of element I is less than 0.001 quality %, the characteristic that just can not obtain obtaining based on containing element I is improved effect.On the other hand, this characteristic is improved effect and is tended to saturated when the content of element I is 2.0 quality %.In addition, add element I, manufacturing cost is risen, or reduce plastic working if surpass 2.0 quality %.Therefore, if consider manufacturing cost and plastic working, the content of element I is preferably and is less than or equal to 2.0 quality %.As element I, the ideal element is the element of selecting from Mg, Ti, Hf, Ti and Zr, Hf and Zr more.Particularly the interpolation of Mg has the effect of the plastic working that improves above-mentioned cast material.Element I ideal content more adds up to more than or equal to 0.01 quality %, is less than or equal to 1.0 quality %.Add element by further minimizing, can reduce the cost of electrode materials.
Can be only with at least a element (hereinafter referred to as element II) from above-mentioned second group, selected as adding element, but also the element I and the element II of above-mentioned specified range can be added together as the interpolation element.In the latter case, the content of element II for example more than or equal to 0.001 quality %, be less than or equal to 3.0 quality %.Promptly, electrode materials of the present invention also can contain add up to 0.001～2.0 quality % from above-mentioned first group, select more than or equal to a kind of element and also contain add up to 0.001～3.0 quality % from above-mentioned second group, select more than or equal to a kind of element, remainder is made of Ni and impurity.On the basis of element I, the electrode materials that utilizes the Ni alloy contain 0.001～3.0 quality % element II to constitute can further improve discharge property, scale resistance, anti-sputter by the electrode of this electrode materials manufacturing.In addition, even contain the element II of 0.001～3.0 quality %, also the plastic working of counter electrode material brings influence hardly.This element II can be a kind of element, also can be a plurality of elements more than or equal to two kinds.When element II was multiple element, total content was adjusted into 0.001～3.0 quality % and adds among the Ni.If the content of element II just can not obtain the effect that obtains based on containing element II less than 0.001 quality %.On the other hand, this effect has saturated tendency when the content of element II is 3.0 quality %, adds if surpass 3.0 quality %, then may cause the reduction of the plastic working of the rising of cost and electrode materials.Therefore, if consider manufacturing cost and plastic working, the content of element II preferably is less than or equal to 3.0 quality %.As element II, the ideal element is Si, Al, Y more.Particularly with Y when adding element because precipitate is present in the grain boundary, thus the growth and the oxidation of the crystal grain can prevent to heat the time.Element II ideal content more adds up to more than or equal to 0.01 quality %, is less than or equal to 2.0 quality %.Add element by further minimizing, can reduce the cost of electrode material.
Ni alloy as having added element II for example has the Ni-Y alloy.When adding to the Y of easily oxidation among the Ni, it is difficult that an amount of Y is contained among the Ni equably, or the tendency of the plastic working deterioration that makes the Ni alloy is arranged.Therefore, be when adding element with Y, be purpose with deoxidation, the deterioration that suppresses plastic working, preferably add Si, Mg with above-mentioned scope.In addition, be preferably on the basis of adding Si, Mg, the content with C is adjusted into specific scope as described later.Electrode materials of the present invention can utilize such Ni-Y alloy and Ni-Y class alloy.
The metal that constitutes electrode materials of the present invention is the Ni alloy, Ni as main component, for example as long as use pure Ni (more than or equal to Ni and the impurity of 99.0 quality %), and in this pure Ni, add the element of from said reference group or first group, second group, selecting and obtain getting final product.Also can utilize the pure Ni of market sale.In the pure Ni of market sale (more than or equal to the Ni of 99 quality %), contain C, S material as impurity.Learn after present inventors investigate: the electrode that the total amount of C and S surpasses 0.10 quality % causes the reduction in brightness and life-span.In addition, learn: though the many electrode materialss of the content of C improve brightness, its plastic working decline on the contrary, the electrode materials generation embrittlement that the content of S is many, plastic working still reduces.Therefore, the content of preferred C of electrode materials of the present invention and S adds up to and is less than or equal to 0.10 quality %.On the other hand, if the content of C or S is less than 0.001 quality %, the insufficient strength of electrode materials then, or constitute electrode materials the Ni alloy thickization of crystal grain and can and forge processibility and bring detrimentally affect the punching press processibility.Therefore, the content of preferred C, S adds up to more than or equal to 0.001 quality % in the Ni alloy.Make the content of C, S add up to more than or equal to 0.001 quality %, be less than or equal to 0.10 quality %, then for example utilize the poor Ni of C, S, or reduce by refining.
The work function of the electrode materials of the present invention that is made of the Ni alloy is less than 4.7eV, and discharge property is good.Therefore, the electrode that is made of electrode materials of the present invention discharges easily, and realizes high brightnessization.In addition, when utilizing the electrode that constitutes by electrode materials of the present invention with the same brightness of electrode in the past ground, further prolongs life, and can obtain high brightness with littler electric current, therefore, also can seek the reduction of consumed power.Work function can change by kind and the content that suitable adjustment is added on the interpolation element in the Ni alloy.If the content of above-mentioned interpolation element increases, then work function diminishes easily.In addition, work function is more little, and the brightness of electrode is tended to raise more.Preferred work function is for being less than or equal to 4.3eV, and best work function is for being less than or equal to 4.0eV.Work function for example can be measured by ultraviolet electronics spectrum analysis method.
In addition, by the electrode materials of the present invention that the Ni alloy constitutes, sputter rate is less than 22nm/min, and anti-sputter is good.Therefore, the electrode that is made of electrode materials of the present invention is owing to be difficult to by sputter, so even use for a long time, brightness can not reduce yet, and the realization long lifetime.In addition, when to utilize the electrode that is made of electrode materials of the present invention to make its and existing electrode be same life-span, the electrode that is made of electrode materials of the present invention was owing to be difficult to by sputter, thus can the high state of long term maintenance brightness, the realization high brightnessization.In addition, owing to be difficult to,, can reduce the reduction in lowering of luminance and life-span so the electrode that is made of electrode materials of the present invention is difficult to form sputtering layer when improving brightness by big electric current by sputter.Sputter rate can change by kind and the content that suitable adjustment is added on the interpolation element in the Ni alloy.If the content of above-mentioned interpolation element increases, then sputter rate diminishes easily.In addition, sputter rate is more little, and the life-span is tended to elongated more.It is desirable to, sputter rate is less than or equal to 20nm/min, it is desirable to more, and sputter rate is less than or equal to 18nm/min, preferably is less than or equal to 16nm/min.The following mensuration of sputter rate.Configured electrodes material in vacuum unit, carry out the ion exposure of the inert element of specified time, measure the surfaceness of postradiation electrode materials, will by irradiation time remove surfaceness and the value (surfaceness/irradiation time) that obtains as sputter rate.
Electrode materials of the present invention can be a sheet material, also can be wire rod (electric wire).Sheet material for example obtains by fusing → casting → hot rolling → cold rolling and thermal treatment.Wire rod for example obtains by fusing → casting → hot rolling → cold drawn silk and thermal treatment.More particularly, prepare main component Ni and add element, particularly the element of selecting from benchmark group, first group, second group arbitrary group obtains the Ni alloy solution with their fusings in vacuum melting stove and air melting stove etc.Suitably adjust this solution (for example when utilizing the fusing of vacuum melting stove, carry out the temperature adjustment, utilizing air melting stove when fusing, remove or reduce impurity and inclusion by concise grade, or carry out the temperature adjustment), obtain ingot casting by the casting of so-called vacuum casting.When electrode materials of the present invention is sheet material, this ingot casting is implemented hot rolling, obtain rolled plate.This rolled plate is carried out cold rolling and thermal treatment repeatedly, obtain tabular electrode materials of the present invention.On the other hand, when electrode materials of the present invention is wire rod, ingot casting is implemented hot rolling, obtain rolled wire.This rolled wire is carried out cold drawn silk and thermal treatment repeatedly, obtain the electrode materials of the present invention of wire.Even electrode materials of the present invention is in sheet material, the wire rod any, final thermal treatment (the softening processing) also preferably under hydrogen environment or under the nitrogen environment, with 700～1000 ℃, particularly carry out about 800～900 ℃.
The content of the hydrogen that contains in the electrode materials of the present invention that obtains as described above, preferred mass ratio more than or equal to 0.1ppm, be less than or equal to 20ppm.If the hydrogen richness of electrode materials surpasses 20ppm, then the electrode that is obtained by this electrode materials and the easy embrittlement in bonding part of inside conductor cause the decline of bond strength, or this electrode becomes the generation source that produces foreign gas, because foreign gas takes place in lamp, reduce relevant with the life-span of lamp.On the other hand, at the mass ratio of hydrogen richness during less than 0.1ppm, on the electrode that constitutes by this electrode materials during the deposited inside conductor that constitutes by Kovar alloy etc., the easy oxidation stain of electrode.The mass ratio of preferred hydrogen richness more than or equal to 1ppm, be less than or equal to 10ppm.The mass ratio of hydrogen richness that makes electrode materials more than or equal to 0.1ppm, be less than or equal to 20ppm, for example when carrying out the manufacturing of above-mentioned electrode materials, adjust above-mentioned final heat treated atmosphere surrounding.For example when making final heat treated atmosphere surrounding be hydrogen environment, adjust hydrogen richness, or be hydrogen atmosphere surrounding in addition such as nitrogen environment.The electrode that carries out final heat treated electrode materials and be made of this electrode materials under nitrogen environment, the mass ratio of its hydrogen richness is less than or equal to 10ppm.
In addition, present inventors learn after studying, and under the fine situation of the crystal grain of the alloy that constitutes electrode materials, are effective to long lifetime, the high brightnessization of the electrode that is made of this electrode materials.Specifically, average crystal grain diameter preferably is less than or equal to 70 μ m.It is desirable to more, average crystal grain diameter is less than or equal to 50 μ m, preferably is less than or equal to 20 μ m.The average crystal grain diameter that constitutes the alloy of electrode materials can the final heat-treat condition when adjusting the kind of adding element and content or electrode materials and make be adjusted.For example: in final thermal treatment,, then can not promote crystal grain-growth if make Heating temperature (thermal treatment temp) for than higher temperature and shorten heat-up time.Specifically, for example making thermal treatment temp is 700～1000 ℃, particularly about 800 ℃, when adopting sheet material, makes translational speed more than or equal to 50 ℃/sec, when adopting wire rod, makes linear speed more than or equal to 50 ℃/sec.If increase translational speed and linear speed, then average crystal grain diameter just has the tendency that diminishes.When the electrode materials that uses average crystal grain diameter to be less than or equal to 70 μ m was made electrode, by punch process or forging and pressing processing, with engaging of inside conductor etc., some variations took place in the crystal grain diameter of the Ni alloy of formation electrode.But the crystal grain diameter of electrode depends on the crystal grain diameter of above-mentioned electrode materials basically, and average crystal grain diameter is below about or equals 70 μ m.
When making electrode materials of the present invention be sheet material,, can make the electrode of cup-shaped simply by this plate stamping is processed into the regulation shape.If by the electrode of punch process manufacturing cup-shaped, then,, easily cause cost correspondingly to raise so effective rate of utilization is reduced owing on sheet material, produce discarded part.But,,, can seek the reduction of cost by reducing equipment cost owing to can use existing electrode manufacturing apparatus (decompressor).
On the other hand, when making electrode materials of the present invention be wire rod (electric wire), can obtain rhoptry electrode or goblet electrode simply.Under the former situation,, can make stick electrode by electric wire is cut into specified length, in the latter case, the cut-out wire-shaped becomes the short code shape material of specified length, shapes to bottom tube-like is arranged by this short code shape material is implemented to forge, and can make cup-shape electrode.Electrode materials of the present invention is owing to be made of the Ni alloy, thereby not only can seek high brightnessization, long lifetime, can also suppress as described above, can fully implement to forge this plastic working of forcing the worker of processing by the reduction of adding the plastic working that element brings.Like this, the electrode materials of the present invention of wire is because can be by cutting off or forge the processing and manufacturing electrode, therefore, even making under any situation of stick electrode, cup-shape electrode, owing to produce discarded part hardly,, can seek the reduction of the manufacturing cost of electrode so yield rate is good.In addition, when the electrode materials of the present invention of above-mentioned wire is implemented to forge the electrode of processing and fabricating cup-shaped, can make the thickness of bottom thicker simply than the thickness of lateral parts.If use the thick electrode of bottom thickness, then can further improve the bond strength of electrode bottom surface and the inside conductor that constitutes by Kovar alloy etc., high-quality luminescent lamp can be provided.When electrode bottom surface and inside conductor being engaged by deposited grade, for prevent bond strength less than, it is effective making the thickness of electrode bottom thicker than electrode lateral parts.In general, if the thickness of electrode bottom is about 4 times of thickness of lateral parts, be effective then to obtaining sufficient joint strength.When sheet material being implemented punch process and makes cup-shape electrode, be limited to thickening bottom only, be that 2 times of lateral parts exceed with maximum.To this, when the electrode of processing and manufacturing cup-shaped is forged in enforcement to thread like body (short code shape material), only the electrode bottom is thickeied more than or equal to twice easily.Therefore, under the situation that is the wire electrode material, when making electrode, not only can improve yield rate and cost degradation, but also can further improve the quality of lamp.
Owing to possess the electrode that constitutes by the Ni alloy that contains above-mentioned specific composition, therefore can obtain more high brightness, long-service-life cold cathode fluorescent lamp.That is, this cold-cathode fluorescence lamp has: luminescent coating is arranged and enclose the Glass tubing of rare gas and mercury in inside at inner-wall surface, or luminescent coating is arranged and enclose the Glass tubing of rare gas in inside at internal surface; Be disposed at the electrode of the end of this pipe, wherein, electrode contain total more than or equal to 0.001 quality %, be less than or equal at least a element 5.0 quality %, that from the benchmark group that constitutes by Ti, Hf, Zr, V, Fe, Nb, Mo, Mn, W, Sr, Ba, B, Th, Be, Si, Al, Y, Mg, In, rare earth element, select, remainder is made of Ni and impurity, more than the luminescent lamp of the present invention that constitutes like this realized brightnessization, long lifetime.Particularly, electrode is an end opening, when the other end has the cup-shaped at the end, then can seek the raising based on the anti-sputter of hollow cathode effect.This cup-shape electrode can obtain simply by electrode materials of the present invention being implemented punch process or being forged processing as mentioned above.Also can prepare a pair of this cup-shape electrode, the peristome of two electrodes relatively is configured in two electrodes in the Glass tubing and constitutes luminescent lamp, can also prepare this cup-shape electrode, only it is configured in the end in the Glass tubing and constitute luminescent lamp.
Above-mentioned electrode can for: 1, contain total more than or equal to 0.001 quality %, be less than or equal at least a element 2.0 quality %, that from constitute by Ti, Hf, Zr, V, Fe, Nb, Mo, Mn, W, Sr, Ba, B, Th, Mg, In first group, select, remainder is made of Ni and impurity; 2, contain add up to 0.001～2.0 quality % from above-mentioned first group, select more than or equal to a kind of element, and also can contain add up to 0.001～3.0 quality % from constitute by Be, Si, Al, Y, rare earth element second group, select more than or equal to a kind of element, remainder is made of Ni and impurity.
By electrode and electrode materials of the present invention that the Ni alloy that contains above-mentioned specific composition constitutes, its scale resistance is good, is difficult to form the oxidation overlay film when engaging when electrode is made and with inside conductor etc.Specifically, can make the thickness of the oxidation overlay film that forms at electrode surface be less than or equal to 1 μ m.Therefore, the deterioration of the discharge of this electrode may be reduced, the high brightnessization and the long lifetime of lamp can be sought.The more preferably thickness of oxidation overlay film is for being less than or equal to 0.3 μ m.As adding element, under the situation of the electrode that constitutes by the Ni alloy that contains Ti, Zr, Hf, particularly be difficult to form the oxidation overlay film, can make its thickness be less than or equal to 0.3 μ m.The formation easness of oxidation overlay film is influential to the composition of the alloy of formation electrode, and under the situation of the electrode that the Ni alloy by above-mentioned specific composition forms, the thickness of oxidation overlay film is less than or equal to 1 μ m.In addition, when making electrode materials, under the atmosphere surrounding beyond the oxygen, carry out, can prevent from electrode materials, to form the oxidation overlay film by making thermal treatment.
The electrode materials of the present invention that is made of the Ni alloy satisfies the desired discharge of electrode of cold-cathode fluorescence lamp, anti-sputter.Particularly the electrode materials of the present invention that is made of the Ni alloy of specific composition fully has the desired discharge of electrode, scale resistance, the anti-reactivity to mercury, anti-sputter of cold-cathode fluorescence lamp.Therefore, the cold-cathode fluorescence lamp with the electrode that constitutes by the electrode of electrode materials manufacturing of the present invention or by the Ni alloy of above-mentioned specific composition can not make electrode maximize, and can realize further high brightnessization, long lifetime.
In addition, electrode materials of the present invention not only has the desired characteristic of above-mentioned electrode, and punch process or to forge the such plasticity of processing also good.Particularly by wire electrode material of the present invention being implemented to forge processing, can be simply and make the good cup-shape electrode of anti-sputter at low cost.
Electrode materials of the present invention can be suitable for utilizing in the electrode of cold-cathode fluorescence lamp.In addition, the manufacture method of electrode of the present invention is suitable for utilizing in the manufacturing of the electrode for cold-cathode fluorescent lamp of the cup-shaped of being made by wire electrode material of the present invention.And, luminescent lamp of the present invention for example: the back of the body irradiation that can be used as liquid-crystal display suitably utilizes with the light source of original copys such as light source, duplicating machine and scanner irradiation with the so various power equipments of cancellation usefulness (イ レ イ サ one usefulness) light source of light source, duplicating machine with the preceding irradiation of light source, miniscope.
Description of drawings
Fig. 1 is the sectional view that the summary of expression cold-cathode fluorescence lamp constitutes.
Embodiment
The following describes embodiments of the present invention.Use the Ni alloy of the moiety (metal No 1～36) shown in the table 1,2 to make electrode for cold-cathode fluorescent lamp.Electrode is made by two kinds of variform electrode materialss.Specifically, prepare wire electrode materials and plate electrode material.By the wire electrode material being implemented to forge the electrode that cup-shaped is made in processing, by the plate electrode material is implemented the electrode that punch process is made cup-shaped.
Table 1
Table 2
＜wire electrode material 〉
The following making of wire electrode material.Use general vacuum melting stove to make the metallic solution that contains the moiety shown in the table 1,2, suitably adjust solution temperature, obtain ingot casting by vacuum casting.By hot rolling the ingot casting that obtains is processed as 5.5mm
Line footpath, obtain rolled wire.Cold drawn silk and thermal treatment are implemented in this rolled wire combination, and the wire rod that obtains is implemented final thermal treatment (the softening processing), obtain line footpath 1.6mm
Softwood.The softening processing in temperature is that 800 ℃, linear velocity are suitably selected in the scope of 10～150 ℃/sec, carries out (in the test portion of expression, the test portion that hydrogen richness is less than or equal to 10ppm is a nitrogen environment in table 3～6) under nitrogen environment or hydrogen environment.In addition, the pure Ni (more than or equal to the Ni of 99 quality %) as the Ni of main component uses market sale makes the total content of C and S change (in this, plate electrode material described later too) by changing concise situation.
＜plate electrode material 〉
The following making of plate electrode material.With with the same method of above-mentioned wire electrode material, make ingot casting by the metallic solution of the moiety shown in the table 1,2.The ingot casting that obtains is implemented hot rolling, obtain the rolled plate that thickness is 4.2mm.After this rolled plate is implemented thermal treatment, cutting surface, obtaining thickness is the processing sheet material of 4.0mm.This processing sheet material is carried out cold rolling and thermal treatment repeatedly, the sheet material that obtains is implemented final thermal treatment (the softening processing), obtaining thickness is the tabular softwood of 0.2mm.Softening processing is 800 ℃, translational speed suitably selection in the scope of 10～150 ℃/sec in temperature, carries out under nitrogen environment or hydrogen environment.
To wire softwood and the tabular softwood that obtains, measure average crystal grain diameter (μ m), work function (eV), the etch-rate (nm/min) of the metal of hydrogen richness (mass ratio ppm), formation softwood.Its result of expression in table 3～6.In addition, table 3 and 4 is for using the test portion of wire electrode material, and table 5 and 6 is for using the test portion of plate electrode material.Hydrogen richness utilize in the rare gas melt-thermal conduction degree method measures (determinator: the hole field makes made EMGA-620).The average crystal grain diameter of metal is that benchmark is measured with the method shown in the JIS G0551.Work function utilizes ultraviolet electronics spectrum analysis method to measure.Specifically, as pre-treatment, after several minutes Ar ion etching of enforcement, use composite electron spectroscopy apparatus (the attached UV-150HI of PHI system ESCA-5800) to measure, wherein, ultraviolet source: He I (21.22eV)/8W, survey periodic vacuum tightness: 3 * 10
-9～6 * 10
-9Torr (0.4 * 10
-9～0.8 * 10
-9KPa), measure preceding base vacuum degree: 4 * 10
-10Torr (5.3 * 10
-11Kpa), apply bias voltage: pact-10V, energy resolution: 0.13eV, analyzed area:
800 μ m ellipses, analysis depth: about 1nm.Etch-rate is to measure surfaceness after the interior softwood irradiation argon ion to mirror ultrafinish of vacuum unit, is tried to achieve by irradiation time and surfaceness.As pre-treatment, software is carried out part carry out ion exposure after covering.Ion exposure uses X linear light electronics spectroscopy apparatus (PHI makes Quantum-2000) to carry out, wherein, and acceleration voltage: 4kV, ionic species: Ar
+, irradiation time: 120min, vacuum tightness: 2 * 10
-8～4 * 10
-8Torr (2.7 * 10
-9～5.3 * 10
-9KPa), argon is pressed: about 15mPa, incident angle: test portion face about 45 is spent relatively.The mensuration of surfaceness uses contact pin type surface shape measuring device (Vecco corporate system Dektak-3030) to carry out, and wherein, contact pilotage: diamond radius=5 μ m, pin are pressed: 20mg, scanning distance: 2mm, sweep velocity: Medium.Forming the position (position of not crested) of corrosion pitting in softwood on the surface by ion exposure, is surfaceness with the mean depth of corrosion pitting, with surfaceness/irradiation time (120min) as etch-rate.
Secondly, the wire softwood that obtains is cut into specified length (1.0mm), the short code shape material that obtains is implemented cold forging make processing, make cup-shape electrode.Consequently: the softwood that contains any composition also can access cup-shape electrode (external diameter 1.6mm
, length 3.0mm, peristome diameter 1.4mm
, the degree of depth 2.6mm of peristome, the thickness 0.4mm of bottom).
In addition, the tabular softwood that obtains is cut into the size (the every limit of 10mm) of regulation, the plate-like tile that obtains is implemented cold stamping processing, make the electrode of cup-shaped.Its result, the softwood that contains any composition also can access cup-shape electrode (external diameter 1.6mm
, length 3.0mm, peristome diameter 1.4mm
The thickness 0.2mm of the degree of depth 2.8mm of peristome, bottom).
To the electrode that obtains, measure the thickness (μ m) of the oxidation overlay film of the metal that constitutes electrode.Its result is illustrated in (table 3,4: use the test portion of wire electrode material, table 5,6: the test portion that uses the plate electrode material) in 3～6.The thickness of oxidation overlay film is by cutting off electrode and utilizing the Auger electron optical spectroscopy to measure electrode surface and obtain.In addition, for the electrode that obtains, with above-mentioned same, when measuring hydrogen richness, average crystal grain diameter and the situation of softwood roughly the same.
Secondly, use the electrode that obtains to make cold-cathode fluorescence lamp shown in Figure 1.Make in the following order particularly.Will be deposited with the outer conductor that constitutes by resin coated copper Ni alloy by the inside conductor that Kovar alloy constitutes, the deposited and connection inside conductor in the bottom surface of above-mentioned electrode is at the deposited granulated glass sphere of the periphery of inside conductor.Prepare two such electrod assemblies.In addition, preparation has the Glass tubing of luminescent coating (in this experiment for halogen-phosphate luminescent coating) and both ends open at inner-wall surface, inserts an electrod assembly at an end of the Glass tubing of opening, and granulated glass sphere is deposited with pipe, one end of sealed tube, and electrod assembly is fixed in the pipe.Secondly, import rare gas (being Ar gas this experiment) and mercury, similarly, fix another electrod assembly, the while sealed glass tube from the other end vacuum attraction of the Glass tubing of opening.According to this order, obtain making the relative cold-cathode fluorescence lamp that disposes of peristome of pair of electrodes.The electrode of each composition is made above-mentioned pair of electrodes parts respectively, use these electrod assemblies to make cold-cathode fluorescence lamp.These luminescent lamps are investigated its brightness and life-span.In this experiment, establish the central brightness (43000cd/m of the cold-cathode fluorescence lamp of test portion No.50A, 50B with the electrode that constitutes by nickel
2) and the life-span be 100, relatively represent brightness and the life-span of other test portion No.1A～38A, 1B～38B.Its result is illustrated in table 3～6.In addition, the life-span is meant that central brightness is 50% o'clock life-span.
Table 3 uses the test portion of wire electrode material
| Test portion No | Metal No | Hydrogen richness (ppm) | Average crystal grain diameter (μ m) | Oxidation overlay film thickness (nm) | Work function (eV) | Etch-rate (nm/min) | Brightness | Life-span |
| ??1A | ??1 | ??7.2 | ??43 | ??0.04 | ??4.3 | ??20.4 | ??200 | ??200 |
| ??2A | ??2 | ??0.8 | ??62 | ??0.4 | ??4.4 | ??17.1 | ??190 | ??360 |
| ??3A | ??3 | ??7.3 | ??38 | ??0.03 | ??4.5 | ??13.5 | ??190 | ??390 |
| ??4A | ??4 | ??6.1 | ??42 | ??0.04 | ??4.3 | ??20.2 | ??200 | ??210 |
| ??5A | ??5 | ??5.8 | ??35 | ??0.02 | ??4.2 | ??19.1 | ??200 | ??280 |
| ??6A | ??6 | ??2.4 | ??31 | ??0.03 | ??4.1 | ??18.5 | ??220 | ??300 |
| ??7A | ??6 | ??23.7 | ??48 | ??0.02 | ??4.2 | ??19.4 | ??180 | ??180 |
| ??8A | ??7 | ??6.5 | ??27 | ??0.05 | ??3.9 | ??20.5 | ??230 | ??200 |
| ??9A | ??7 | ??9.6 | ??93 | ??0.04 | ??4.5 | ??21.3 | ??190 | ??180 |
| ??10A | ??8 | ??0.6 | ??37 | ??0.5 | ??4.4 | ??19.8 | ??190 | ??250 |
| ??11A | ??9 | ??8.1 | ??39 | ??0.02 | ??4.2 | ??17.8 | ??200 | ??340 |
| ??12A | ??10 | ??6.4 | ??16 | ??0.02 | ??4.3 | ??18.0 | ??200 | ??330 |
| ??13A | ??11 | ??2.6 | ??18 | ??0.03 | ??3.4 | ??19.2 | ??310 | ??280 |
| ??14A | ??12 | ??12.1 | ??14 | ??0.05 | ??3.8 | ??19.3 | ??250 | ??240 |
| ??15A | ??13 | ??9.1 | ??44 | ??0.02 | ??4.2 | ??18.3 | ??210 | ??320 |
| ??16A | ??14 | ??6.7 | ??28 | ??0.04 | ??4.1 | ??18.0 | ??210 | ??310 |
| ??17A | ??15 | ??7.1 | ??45 | ??0.05 | ??3.8 | ??19.2 | ??240 | ??270 |
| ??18A | ??16 | ??8.5 | ??36 | ??0.03 | ??3.9 | ??19.2 | ??230 | ??260 |
| ??19A | ??17 | ??7.7 | ??30 | ??0.05 | ??4.6 | ??19.3 | ??180 | ??270 |
| ??20A | ??18 | ??8.3 | ??28 | ??0.03 | ??3.6 | ??15.6 | ??290 | ??370 |
Table 4 uses the test portion of wire electrode material
| Test portion No | Metal No | Hydrogen richness (ppm) | Average crystal grain diameter (μ m) | Oxidation overlay film thickness (nm) | Work function (eV) | Etch-rate (nm/min) | Brightness | Life-span |
| ??21A | ??19 | ??6.9 | ??45 | ??0.05 | ??3.7 | ??19.5 | ??280 | ??260 |
| ??22A | ??20 | ??7 | ??31 | ??0.05 | ??3.1 | ??19.3 | ??320 | ??260 |
| ??23A | ??21 | ??0.9 | ??33 | ??0.06 | ??3.5 | ??17.2 | ??290 | ??350 |
| ??24A | ??22 | ??5.9 | ??27 | ??0.07 | ??3.4 | ??16.9 | ??300 | ??360 |
| ??25A | ??23 | ??6.6 | ??36 | ??0.06 | ??3.7 | ??17.7 | ??280 | ??340 |
| ??26A | ??24 | ??9.3 | ??22 | ??0.05 | ??3.2 | ??16.5 | ??320 | ??360 |
| ??27A | ??25 | ??2.4 | ??51 | ??0.07 | ??3.5 | ??20.1 | ??290 | ??210 |
| ??28A | ??26 | ??3.5 | ??40 | ??0.08 | ??2.9 | ??19.8 | ??330 | ??240 |
| ??29A | ??27 | ??1.4 | ??47 | ??0.09 | ??3.8 | ??20.0 | ??240 | ??220 |
| ??30A | ??28 | ??6.1 | ??38 | ??0.02 | ??3.8 | ??18.7 | ??240 | ??300 |
| ??31A | ??29 | ??2.8 | ??28 | ??0.03 | ??2.9 | ??18.1 | ??330 | ??310 |
| ??32A | ??30 | ??4.1 | ??38 | ??0.03 | ??3.7 | ??17.5 | ??290 | ??340 |
| ??33A | ??31 | ??3.9 | ??33 | ??0.02 | ??4.4 | ??14.7 | ??190 | ??350 |
| ??34A | ??32 | ??3.5 | ??18 | ??0.01 | ??4.1 | ??12.7 | ??220 | ??430 |
| ??35A | ??33 | ??6.6 | ??22 | ??0.02 | ??3.4 | ??13.4 | ??300 | ??390 |
| ??36A | ??34 | ??2.3 | ??29 | ??0.02 | ??4.1 | ??14.1 | ??230 | ??360 |
| ??37A | ??35 | ??4.9 | ??41 | ??0.04 | ??4.2 | ??18.9 | ??210 | ??290 |
| ??38A | ??36 | ??7.1 | ??19 | ??0.02 | ??3.3 | ??13.9 | ??310 | ??370 |
| ??50A | ??50 | ??8.8 | ??91 | ??1.3 | ??4.7 | ??22.0 | ??100 | ??100 |
Table 5 uses the test portion of plate electrode material
| Test portion No | Metal No | Hydrogen richness (ppm) | Average crystal grain diameter (μ m) | Oxidation overlay film thickness (nm) | Work function (eV) | Etch-rate (nm/min) | Brightness | Life-span |
| ??1B | ??1 | ??7.1 | ??41 | ??0.03 | ??4.3 | ??20.2 | ??200 | ??210 |
| ??2B | ??2 | ??0.9 | ??64 | ??0.42 | ??4.4 | ??17.5 | ??180 | ??350 |
| ??3B | ??3 | ??7.5 | ??37 | ??0.05 | ??4.5 | ??14.0 | ??190 | ??380 |
| ??4B | ??4 | ??6.1 | ??42 | ??0.04 | ??4.3 | ??20.1 | ??200 | ??210 |
| ??5B | ??5 | ??5.8 | ??38 | ??0.03 | ??4.2 | ??19.1 | ??210 | ??280 |
| ??6B | ??6 | ??2.5 | ??29 | ??0.02 | ??4.1 | ??18.1 | ??220 | ??300 |
| ??7B | ??6 | ??23.4 | ??49 | ??0.02 | ??4.2 | ??19.4 | ??180 | ??180 |
| ??8B | ??7 | ??6.4 | ??28 | ??0.04 | ??3.9 | ??20.6 | ??230 | ??200 |
| ??9B | ??7 | ??9.8 | ??96 | ??0.06 | ??4.5 | ??21.1 | ??190 | ??190 |
| ??10B | ??8 | ??0.5 | ??36 | ??0.55 | ??4.4 | ??19.5 | ??190 | ??270 |
| ??11B | ??9 | ??8.1 | ??42 | ??0.03 | ??4.2 | ??17.9 | ??200 | ??340 |
| ??12B | ??10 | ??6.7 | ??19 | ??0.02 | ??4.3 | ??18.4 | ??200 | ??310 |
| ??13B | ??11 | ??2.3 | ??20 | ??0.05 | ??3.4 | ??19.0 | ??310 | ??280 |
| ??14B | ??12 | ??12.6 | ??17 | ??0.04 | ??3.8 | ??19.5 | ??260 | ??250 |
| ??15B | ??13 | ??8.8 | ??42 | ??0.04 | ??4.2 | ??18.7 | ??210 | ??300 |
| ??16B | ??14 | ??6.9 | ??33 | ??0.02 | ??4.1 | ??17.8 | ??210 | ??340 |
| ??17B | ??15 | ??6.9 | ??45 | ??0.05 | ??3.8 | ??19.1 | ??250 | ??280 |
| ??18B | ??16 | ??8.6 | ??37 | ??0.04 | ??3.9 | ??19.4 | ??230 | ??270 |
| ??19B | ??17 | ??7.8 | ??34 | ??0.03 | ??4.6 | ??18.5 | ??180 | ??300 |
| ??20B | ??18 | ??8.2 | ??31 | ??0.04 | ??3.6 | ??15.4 | ??290 | ??370 |
Table 6 uses the test portion of plate electrode material
| Test portion No | Metal No | Hydrogen richness (ppm) | Average crystal grain diameter (μ m) | Oxidation overlay film thickness (nm) | Work function (eV) | Etch-rate (nm/min) | Brightness | Life-span |
| ??21B | ??19 | ??6.9 | ??46 | ??0.02 | ??3.7 | ??19.1 | ??280 | ??280 |
| ??22B | ??20 | ??7.3 | ??32 | ??0.04 | ??3.1 | ??19.6 | ??320 | ??260 |
| ??23B | ??21 | ??1.1 | ??36 | ??0.05 | ??3.5 | ??17.4 | ??290 | ??350 |
| ??24B | ??22 | ??5.7 | ??29 | ??0.06 | ??3.4 | ??16.6 | ??300 | ??360 |
| ??25B | ??23 | ??6.7 | ??39 | ??0.07 | ??3.7 | ??17.9 | ??290 | ??330 |
| ??26B | ??24 | ??9.1 | ??27 | ??0.07 | ??3.2 | ??16.1 | ??320 | ??370 |
| ??27B | ??25 | ??2.1 | ??51 | ??0.09 | ??3.5 | ??19.9 | ??290 | ??240 |
| ??28B | ??26 | ??3.5 | ??43 | ??0.07 | ??2.9 | ??19.9 | ??330 | ??250 |
| ??29B | ??27 | ??1.2 | ??48 | ??0.09 | ??3.8 | ??20.3 | ??240 | ??200 |
| ??30B | ??28 | ??6 | ??36 | ??0.03 | ??3.8 | ??18.8 | ??240 | ??300 |
| ??31B | ??29 | ??2.7 | ??31 | ??0.03 | ??2.9 | ??18.3 | ??330 | ??310 |
| ??32B | ??30 | ??4.0 | ??36 | ??0.04 | ??3.7 | ??17.7 | ??280 | ??340 |
| ??33B | ??31 | ??4.5 | ??31 | ??0.03 | ??4.4 | ??14.8 | ??190 | ??350 |
| ??34B | ??32 | ??3.1 | ??20 | ??0.01 | ??4.1 | ??12.9 | ??220 | ??420 |
| ??35B | ??33 | ??5.9 | ??21 | ??0.02 | ??3.4 | ??13.5 | ??310 | ??390 |
| ??36B | ??34 | ??2.8 | ??31 | ??0.03 | ??4.1 | ??14.3 | ??220 | ??360 |
| ??37B | ??35 | ??6.7 | ??46 | ??0.04 | ??4.2 | ??18.7 | ??210 | ??300 |
| ??38B | ??36 | ??8.2 | ??19 | ??0.02 | ??3.3 | ??14.0 | ??310 | ??370 |
| ??50B | ??50 | ??8.5 | ??96 | ??1.2 | ??4.7 | ??22.1 | ??100 | ??100 |
Shown in table 3,4, the luminescent lamp with test portion No.1A～38A of the electrode that is made of the Ni alloy is compared with the luminescent lamp of the test portion No.50A with the electrode that is made of nickel, and brightness height and life-span are long.In addition, shown in table 5,6, the luminescent lamp with test portion No.1B～38B of the electrode that is made of the Ni alloy is compared with the luminescent lamp of the test portion No.50B with the electrode that is made of nickel, and brightness height and life-span are long.This think because, metal No.1～36 are compared with the metal No.50 of nickel simple substance, are the little materials of work function and etch-rate, promptly discharge easily and the slow material of sputtering rate.In addition, being compared with the metal No.50 of nickel simple substance by metal No.1～36 that the Ni alloy constitutes, owing to be difficult to form the oxidation overlay film, so be difficult to make the deterioration of discharge property, is the material that is difficult to form with mercury mercury alloys.
In the luminescent lamp of test portion No.1A～38A, 1B～38B, handle the Ni alloy that reduces hydrogen richness by under nitrogen environment, softening, specifically, have mass ratio by hydrogen richness be less than or equal to its life-span of luminescent lamp of the electrode that the Ni alloy of 10ppm constitutes longer, brightness is higher.And linear velocity or translational speed are more than or equal to the test portion of 50 ℃/sec, and the average crystal grain diameter of its Ni alloy is less than or equal to 70 μ m.And, in the luminescent lamp of test portion No.1A～38A, 1B～38B, have by average crystal grain diameter be less than or equal to its life-span of luminescent lamp of the electrode that the Ni alloy of 70 μ m constitutes longer, brightness is higher.And in the luminescent lamp of test portion No.1A～38A, 1B～38B, its life-span of luminescent lamp that has total content by C and S and be an electrode that the Ni alloy of 0.001～0.1 quality % constitutes is longer, brightness is higher.
Claims (6)
1, a kind of electrode materials, it is characterized in that, contain total more than or equal to 0.001 quality %, be less than or equal to 5.0 quality %, from by Be, Si, Al, Y and remove at least a element of selecting the element set that the rare earth element of Y constitutes, remainder is made of Ni and impurity, this electrode materials is used for the electrode of cold-cathode fluorescence lamp.
2, electrode materials as claimed in claim 1 is characterized in that, contains to add up to be less than or equal at least a element 3.0 quality %, that select from described element set.
3, electrode materials as claimed in claim 1 is characterized in that, contains the Y of 0.1 quality %～0.9 quality %.
4, electrode materials as claimed in claim 1 is characterized in that, contains the Y of 0.1 quality %～0.9 quality %, and, add up to contain 0.001 quality %～3.0 quality % from Si, at least a element of selecting among the Al.
5, electrode materials as claimed in claim 4 is characterized in that, add up to contain be less than or equal to 2.0 quality % from Si, at least a element of selecting among the Al.
6, electrode materials as claimed in claim 1 is characterized in that, contains the Y of 0.1 quality %～0.9 quality %, and, contain the Mg of 0.001 quality %～0.1 quality %.
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| CN2006100845592A Expired - Fee Related CN1873876B (en) | 2005-05-25 | 2006-05-25 | Electrode material |
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| Country | Link |
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| CN (2) | CN101633989A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102597284A (en) * | 2009-12-24 | 2012-07-18 | 日本特殊陶业株式会社 | Spark plug |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102306608A (en) * | 2008-04-17 | 2012-01-04 | 住友电气工业株式会社 | Cold cathode fluorescent lamp, power supply for electrical equipment, liquid crystal display device and electrode component for cold cathode fluorescent lamp |
| JP5267979B2 (en) * | 2008-06-25 | 2013-08-21 | Ｎｅｃライティング株式会社 | Fluorescent lamp electrode, manufacturing method thereof, and fluorescent lamp |
| KR20100032336A (en) * | 2008-09-16 | 2010-03-25 | 스탠리 일렉트릭 컴퍼니, 리미티드 | Electrode for cold cathod fluorescent tube and cold cathod fluorescent tube using the same |
| CN104091740A (en) * | 2014-01-24 | 2014-10-08 | 朱惠冲 | High-strength rare earth molybdenum tube cold cathode and manufacturing process thereof |
| CN104532064A (en) * | 2014-12-25 | 2015-04-22 | 春焱电子科技（苏州）有限公司 | Alloy for electronic material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003515885A (en) * | 1999-11-24 | 2003-05-07 | コーニンクレッカ フィリップス エレクトロニクス エヌ ヴィ | Low pressure mercury discharge lamp |
-
2006
- 2006-05-25 CN CN200910160230A patent/CN101633989A/en active Pending
- 2006-05-25 CN CN2006100845592A patent/CN1873876B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102597284A (en) * | 2009-12-24 | 2012-07-18 | 日本特殊陶业株式会社 | Spark plug |
| CN102597284B (en) * | 2009-12-24 | 2013-12-04 | 日本特殊陶业株式会社 | Spark plug |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1873876A (en) | 2006-12-06 |
| CN1873876B (en) | 2010-05-12 |
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