CN1873876B - Electrode material - Google Patents
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- CN1873876B CN1873876B CN2006100845592A CN200610084559A CN1873876B CN 1873876 B CN1873876 B CN 1873876B CN 2006100845592 A CN2006100845592 A CN 2006100845592A CN 200610084559 A CN200610084559 A CN 200610084559A CN 1873876 B CN1873876 B CN 1873876B
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Abstract
The invention relates to electrode material which is characterized in that it has a fluorophor layer on its inner wall, a glass tube with rare gas and mercury sealed in it and a pair of electrodes which are equipped on the two ends of the glass tube. Wherein the electrodes are comprised with Ni alloys, the Ni alloys comprise at least one element out of the basic group comprised with rare-earth element Ti, Hf, Zr, V, Fe, Nb, Mo, Mn, W, Sr, Ba, B, Th, Be, Si, Al, Y, Mg, In, which total mass is greater or equal to 0.001 mass percentages and less or equal to 5.0 mass percentages, and the rest of the alloys is Ni and other foreign materials. As the electrode is comprised with Ni alloys, it has the advantages of having good discharge character, oxidation resistance, sputter resistance and reaction resistance of mercury.
Description
Technical field
The present invention relates to the electrode material 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 material 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 (LCD) 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 profile of its schematic configuration of expression.This cold-cathode fluorescence lamp 100 has at internal face and is provided with luminescent coating 101 and encloses rare gas and the glass tube 102 of mercury, be disposed at the pair of electrodes 103 in the glass tube 102.Luminescent coating 101 was located on the almost full week and total length of glass tube 102 internal faces, in pipe 102, was mainly illuminating part between two electrodes 103, was non-illuminating 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 tube 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 104 pairs of electrodes 103 of this lead.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 coefficient of expansion of the thermal coefficient of expansion equal extent of glass tube 102.At the deposited bead of the periphery of inside conductor 105 (bead glass) 106.Utilize this bead 106 that electrode 103 is fixed in the glass tube 102, should manage 102 sealings simultaneously, thus the air seal state in the holding tube 102 stably.In addition, the no mercury fluorescent lamp of only having enclosed rare gas in glass tube 102 is also arranged.
Such fluorescent 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 tube 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 tube 102 etc. collide and the radiation ultraviolet ray, this ultraviolet ray excited fluorophor, and fluorophor 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 LCD etc., it was slim, light weight, high brightness, long-life 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 with the electrode that constitutes by nickel, mercury ion and electrode by discharge generation when lighting collide, thereby cause electrode substance in glass tube, to splash and be piled up in the sputtering phenomenon of inside pipe wall. when causing sputter, electrode is consumed. particularly, because only some concentrates consumption and forms the hole in this part electrode, so electrode can not be used for discharge, thereby fluorescent lamp has arrived life span. in addition, sputtering layer (by vaporized electrode substance constitute the layer) with mercury form mercury alloy. therefore, if light for a long time, then mercury is almost all obtained by sputtering layer, ultraviolet thus radiation can not fully be carried out, and the brightness of lamp is very low, and fluorescent lamp has arrived life span. promptly, in fluorescent 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 alloy cause the life-span of fluorescent 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-illuminating 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 material, 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 electrode is processed, even or can electrode be processed, 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 pair material of electrode coating promotion release electronics, for example lanthanum compound, cesium compound, yttrium compound, barium compound etc.But therefore these materials that discharge electronics are difficult to further long lifetime owing to the collision that is subjected to the ion of discharge generation during lighting at lamp is dispersed.
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 material 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 material 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 alloy 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 consumption rate.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 fluorescent lamp (when electrode and inside conductor engage etc.) electrode material and electrode can be heated.When the easy adsorption of oxygen of electrode material,, be easy to form the oxidation overlay film at electrode surface by carrying out such heating.To this, by the electrode that the electrode material 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 material during easily with mercury formation mercury alloy, the electrode that is made of this electrode material is when sputter, accelerated mercury consumption, the result has shortened the life-span of fluorescent lamp. and to this, by the electrode that the electrode material that is difficult to form mercury alloy constitutes, mercury consumption is slowed down, further life-saving. therefore, electrode preferably is made of the material that is difficult to form mercury alloy.
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 fluorescent 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 tube, 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 material (composition) of high price materials such as Mo and Nb to study to simple substance not.Its result learns: as the composition of electrode material, preferably used the Ni alloy of the relatively cheap Ni of price.Therefore, electrode material of the present invention is made of the Ni alloy.
The electrode material 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 material is characterised in that, is made of the Ni alloy of the specific interpolation element that contains particular range.The electrode made from this electrode material 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 material is difficult to form the oxidation overlay film, is difficult to form mercury alloy.Therefore, the electrode by the electrode material that uses by the invention described above constitutes obtains high brightness, long-service-life cold cathode fluorescent lamp.
The electrode material of second aspect present invention, it is an operable electrode material 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 the surface of solids.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 flash-over 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 material 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 material of the present invention, can obtain high brightness, long-service-life cold cathode fluorescent lamp.
The electrode material of third aspect present invention, it is the electrode material 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 the part that the collision by the mercury ion discharges atom in electrode produces corrosion pitting and makes rough surface.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 material 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 material 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 material of the present invention is made of the Ni alloy. particularly, as adding element, preferably from by Ti, Hf, Zr, V, Fe, Nb, Mo, Mn, W, Sr, Ba, B, Th, Be, Si, Al, Y, Mg, In, at least a element of selecting in the benchmark group that rare earth element constitutes. 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 %, being less than or equal to 5.0 quality %. is 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 less than 0.001 quality %, can not improve the high brightnessization of adding element and producing effectively by containing, the characteristic of long lifetime. 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 % if add the content of element, then, the increase of adding element rises because of causing cost. and, the increase of adding element can reduce the plastic working when reaching by this electrode material manufacturing electrode when making electrode material. and electrode material of the present invention is as described later, after melt-casting, to founding materials be rolled processing and the such plastic working of Wire Drawing make. in addition, when using electrode material of the present invention to make electrode, electrode material is carried out the such plastic working of punch process and forging described later processing to be made. therefore, in order not reduce the plastic working of the raw material and the electrode material that are used to make electrode material, 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 material 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 material 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 founding materials that is made of this Ni alloy has the processability 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 material is made electrode owing to have enough carried out punch process and the processability 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, more desirable element is the element of selecting from Mg, Ti, Hf, Ti and Zr, Hf and Zr.Particularly the interpolation of Mg has the effect of the plastic working that improves above-mentioned founding materials.The content that element I is more desirable 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 material.
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 particular range can be added together as adding element. in the latter case, the content of element II is for example more than or equal to 0.001 quality %, be less than or equal to 3.0 quality %. promptly, electrode material 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 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, utilization contains the electrode material of the Ni alloy formation of 0.001～3.0 quality % element II, electrode by this electrode material manufacturing can further improve discharge, oxidative resistance, anti-sputter. in addition, even contain the element II of 0.001～3.0 quality %, also hardly the plastic working of electrode material being brought influence. 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 is multiple element, total content is adjusted into 0.001～3.0 quality % and adds among the Ni. if the content of element II is less than 0.001 quality %, just can not obtain the effect that obtains based on containing element II. on the other hand, this effect has saturated tendency when the content of element II is 3.0 quality %, if surpassing 3.0 quality % adds, then may cause the reduction of the plastic working of the rising of cost and electrode material. 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, more desirable element is Si, Al, Y. particularly with Y when adding element, because precipitate is present in the grain boundary, thereby the growth of the crystal grain in the time of can preventing to heat and oxidation. the content that element II is more desirable adds up to more than or equal to 0.01 quality %, be less than or equal to 2.0 quality %. and add element, can reduce the cost of electrode material by further reducing.
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 material of the present invention can utilize such Ni-Y alloy and Ni-Y class alloy.
The metal that constitutes electrode material 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 materials of the content of C improve brightness, its plastic working decline on the contrary, the electrode material generation embrittlement that the content of S is many, plastic working still reduces.Therefore, the content of preferred C of electrode material 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 material then, or constitute electrode material the Ni alloy thickization of crystal grain and can and forge processability and bring harmful effect the punching press processability.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 material 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 material of the present invention discharges easily, and realizes high brightnessization.In addition, when utilizing the electrode that constitutes by electrode material of the present invention with the same brightness of electrode in the past ground, further life-saving, 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 material 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 material 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 material of the present invention to make its and existing electrode be same life-span, the electrode that is made of electrode material 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 material 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 plant, carry out the ion exposure of the inert element of stipulated time, measure the surface roughness of postradiation electrode material, will by irradiation time remove surface roughness and the value (surface roughness/irradiation time) that obtains as sputter rate.
Electrode material 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 heat treatment. and wire rod for example obtains by fusing → casting → hot rolling → cold drawn silk and heat treatment. more particularly, prepare main component Ni and add element, particularly from the benchmark group, first group, the element of selecting in second group arbitrary group, in vacuum fusion stove and air melting stove etc., their fusings are obtained the Ni alloy solution. suitably adjust this solution (for example when utilizing the fusing of vacuum fusion stove, carry out the temperature adjustment, when utilizing the fusing of air melting stove, remove or reduce impurity and field trash by concise grade, or carry out the temperature adjustment), casting by so-called vacuum pressing and casting obtains ingot casting. when electrode material 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 heat treatment repeatedly, obtain tabular electrode material of the present invention. on the other hand, when electrode material 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 heat treatment repeatedly, even obtain the electrode material of the present invention of wire. electrode material of the present invention is a sheet material, in the wire rod any, final heat treatment (the softening processing) is 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 material 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 content of electrode material surpasses 20ppm, then the electrode that is obtained by this electrode material 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 content during less than 0.1ppm, on the electrode that constitutes by this electrode material during the deposited inside conductor that constitutes by Kovar alloy etc., the easy oxidation stain of electrode.The mass ratio of preferred hydrogen content more than or equal to 1ppm, be less than or equal to 10ppm.The mass ratio of hydrogen content that makes electrode material 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 material, adjust above-mentioned final heat treated gaseous environment.For example when making final heat treated gaseous environment be hydrogen environment, adjust hydrogen content, or be hydrogen gaseous environment in addition such as nitrogen environment.The electrode that carries out final heat treated electrode material and be made of this electrode material under nitrogen environment, the mass ratio of its hydrogen content 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 material, are effective to long lifetime, the high brightnessization of the electrode that is made of this electrode material.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 material can the final heat-treat condition when adjusting the kind of adding element and content or electrode material and make be adjusted.For example: in final heat treatment,, then can not promote crystal grain-growth if make heating-up temperature (heat treatment temperature) for than higher temperature and shorten heating time.Specifically, for example making heat treatment temperature 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 material 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 material basically, and average crystal grain diameter is below about or equals 70 μ m.
When making electrode material 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 material of the present invention be wire rod (electric wire), can obtain clava electrode or goblet electrode simply. under the former situation, by electric wire is cut into specific length, can make stick electrode, in the latter case, the cut-out wire-shaped becomes the short code shape material of specific length, by being implemented to forge, this short code shape material shapes to bottom tube-like is arranged, can make cup-shape electrode. electrode material 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 by the reduction of adding the plastic working that element brings, can fully implement to forge this plastic working of forcing the worker of processing. like this, the electrode material of the present invention of wire is because can be by cutting off or forge the processing and manufacturing electrode, therefore, even making stick electrode, under the situation of any of cup-shape electrode, owing to produce discarded part hardly, so rate of finished products is good, can seek the reduction of the manufacturing cost of electrode. in addition, when the electrode material of the present invention of above-mentioned wire is implemented to forge the electrode of processing and fabricating cup-shaped, if can make the thickness of bottom thicker simply than the thickness of lateral parts. 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 fluorescent 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 making cup-shape electrode, to only thickening the bottom is limited, with maximum is that 2 times of lateral parts exceed. to this, when thread like body (short code shape material) is implemented to forge the electrode of processing and manufacturing cup-shaped, 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, rate of finished products and cost degradation not only can be improved, but also the quality of lamp can be further improved.
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 tube of rare gas and mercury in inside at internal face, or luminescent coating is arranged and enclose the glass tube of rare gas in inside at inner 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 fluorescent 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 material 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 tube and constitutes fluorescent lamp, can also prepare this cup-shape electrode, only it is configured in the end in the glass tube and constitute fluorescent 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 material of the present invention that the Ni alloy that contains above-mentioned specific composition constitutes, its oxidative 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 material, under the gaseous environment beyond the oxygen, carry out, can prevent from electrode material, to form the oxidation overlay film by making heat treatment.
The electrode material of the present invention that is made of the Ni alloy satisfies the desired discharge of electrode of cold-cathode fluorescence lamp, anti-sputter. and particularly the electrode material of the present invention that is made of the Ni alloy of specific composition fully has the desired discharge of electrode, oxidative resistance, the anti-reactivity to mercury, anti-sputter of cold-cathode fluorescence lamp. therefore, cold-cathode fluorescence lamp with the electrode that constitutes by the electrode of electrode material 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 material 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 material 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, fluorescent lamp of the present invention for example: the back of the body irradiation that can be used as LCD suitably utilizes with the light source of original copys such as light source, photocopier and scanner irradiation with the so various power equipments of cancellation usefulness (イ レ イ サ one usefulness) light source of light source, photocopier with the preceding irradiation of light source, miniscope.
Description of drawings
Fig. 1 is the profile 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 constituent (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 materials.Specifically, prepare wire electrode material 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 fusion stove to make the metallic solution that contains the constituent shown in the table 1,2, suitably adjust solution temperature, obtain ingot casting by vacuum pressing and casting.By hot rolling the ingot casting that obtains is processed as
Line footpath, obtain rolled wire.Cold drawn silk and heat treatment are implemented in this rolled wire combination, and the wire rod that obtains is implemented final heat treatment (the softening processing), obtain the line footpath
Softwood. the softening processing in temperature is that 800 ℃, linear velocity are suitably selected in the scope of 10～150 ℃/sec, under nitrogen environment or hydrogen environment, carry out (in the test portion of representing in table 3～6, the test portion that hydrogen content is less than or equal to 10ppm is a nitrogen environment). in addition, use the pure Ni (more than or equal to the Ni of 99 quality %) of market sale as the Ni of main component, make the total content of C and S change (in this, plate electrode material described later is 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 constituent 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 heat treatment, cutting surface, obtaining thickness is the processing sheet material of 4.0mm.This processing sheet material is carried out cold rolling and heat treatment repeatedly, the sheet material that obtains is implemented final heat 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 content (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 content utilize in the rare gas melt-heat 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(ic) 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, the vacuum degree when measuring: 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:
Ellipse, analysis depth: about 1nm.Etch-rate is to measure surface roughness after the interior softwood irradiation argon ion to mirror ultrafinish of vacuum plant, is tried to achieve by irradiation time and surface roughness.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 accelerating voltage: 4kV, ionic species: Ar
+, irradiation time: 120min, vacuum degree: 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 surface roughness 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 speed: Medium.Forming the position (position of not crested) of corrosion pitting in softwood on the surface by ion exposure, is surface roughness with the mean depth of corrosion pitting, with surface roughness/irradiation time (120min) as etch-rate.
Secondly, the wire softwood that obtains is cut into specific 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
The diameter of length 3.0mm, peristome
The thickness 0.4mm of the degree of depth 2.6mm of peristome, 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
The diameter of length 3.0mm, peristome
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 electrons optical spectroscopy to measure electrode surface and obtain.In addition, for the electrode that obtains, with above-mentioned same, when measuring hydrogen content, average crystal grain diameter and the situation of softwood roughly the same.
Secondly, the electrode that use obtains is made cold-cathode fluorescence lamp shown in Figure 1. makes in the following order particularly. and will be deposited with the outer conductor that constitutes by resin coated copper Ni alloy by the inside conductor that Kovar alloy constitutes, deposited and the connection inside conductor in the bottom surface of above-mentioned electrode, at the deposited bead of the periphery of inside conductor. prepare two such electrod assemblies. in addition, preparation has the glass tube of luminescent coating (in this experiment for halogen-phosphate luminescent coating) and both ends open at internal face, end at the glass tube of opening inserts an electrod assembly, bead 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 from the other end vacuum attraction of the glass tube of opening, similarly, fix another electrod assembly, the while sealed glass tube. 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 fluorescent lamps are investigated its brightness and life-span. in this experiment, establish test portion No.50A with the electrode that constitutes by nickel, central brightness (the 43000cd/m of the cold-cathode fluorescence lamp of 50B
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 content (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 |
| Test portion No | Metal No | Hydrogen content (ppm) | Average crystal grain diameter (μ m) | Oxidation overlay film thickness (nm) | Work function (eV) | Etch-rate (nm/min) | Brightness | Life-span |
| 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 content (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 |
| Test portion No | Metal No | Hydrogen content (ppm) | Average crystal grain diameter (μ m) | Oxidation overlay film thickness (nm) | Work function (eV) | Etch-rate (nm/min) | Brightness | Life-span |
| 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 content (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 |
| Test portion No | Metal No | Hydrogen content (ppm) | Average crystal grain diameter (μ m) | Oxidation overlay film thickness (nm) | Work function (eV) | Etch-rate (nm/min) | Brightness | Life-span |
| 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 content (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 |
| Test portion No | Metal No | Hydrogen content (ppm) | Average crystal grain diameter (μ m) | Oxidation overlay film thickness (nm) | Work function (eV) | Etch-rate (nm/min) | Brightness | Life-span |
| 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 fluorescent lamp with test portion No.1A～38A of the electrode that is made of the Ni alloy is compared with the fluorescent 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 fluorescent lamp with test portion No.1B～38B of the electrode that is made of the Ni alloy is compared with the fluorescent 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 alloy.
In the fluorescent lamp of test portion No.1A～38A, 1B～38B, handle the Ni alloy that reduces hydrogen content by under nitrogen environment, softening, specifically, have mass ratio by hydrogen content be less than or equal to its life-span of fluorescent 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 fluorescent 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 fluorescent lamp of the electrode that the Ni alloy of 70 μ m constitutes longer, brightness is higher.And in the fluorescent lamp of test portion No.1A～38A, 1B～38B, its life-span of fluorescent 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 (14)
1. electrode material, 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 Ti, Hf, Zr, V, Fe, Nb, Mo, Mn, W, Sr, Ba, B, Th, Be, Si, Al, Y, Mg, In and remove at least a element of selecting the benchmark group that the rare earth element of Y constitutes, remainder is made of Ni and impurity
In the element of described benchmark group, 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, and contain total more than or equal to 0.001 quality %, be less than or equal to 3.0 quality %, from Be, Si, Al, Y and remove at least a element of selecting second group that the rare earth element of Y constitutes, this electrode material is used for the electrode of cold-cathode fluorescence lamp.
2. electrode material as claimed in claim 1 is characterized in that work function is less than 4.7eV.
3. electrode material as claimed in claim 1 is characterized in that its etch-rate is less than 22nm/min.
4. electrode material as claimed in claim 1 is characterized in that, the content of C, S adds up to more than or equal to 0.001 quality %, is less than or equal to 0.10 quality %.
5. electrode material as claimed in claim 1 is characterized in that, hydrogen content more than or equal to 0.1ppm, be less than or equal to 20ppm.
6. electrode material as claimed in claim 1 is characterized in that, the average crystal grain diameter that constitutes the metal of electrode material is less than or equal to 70 μ m.
7. electrode material as claimed in claim 1 is characterized in that, electrode material is a board-like material.
8. electrode material as claimed in claim 1 is characterized in that, electrode material is a filamentary material.
9. the manufacture method of an electrode for cold-cathode fluorescent lamp is characterized in that, has following operation: cut off the described filamentary material of claim 8, obtain the short code shape material of specific length; Described short code shape material is implemented to forge processing, be formed with bottom tube-like and obtain electrode.
10. cold-cathode fluorescence lamp is characterized in that having: internal face has luminescent coating and the inner glass tube of enclosing rare gas and mercury or rare gas; Be disposed at the electrode of the end in the described glass tube, described electrode contains total more than or equal to 0.001 quality %, be less than or equal to 5.0 quality %'s, from by Ti, Hf, Zr, V, Fe, Nb, Mo, Mn, W, Sr, Ba, B, Th, Be, Si, Al, Y, Mg, In and remove at least a element of selecting in the benchmark group that the rare earth element of Y constitutes, remainder is made of Ni and impurity, in the element of described benchmark group, contain total more than or equal to 0.001 quality %, be less than or equal to 2.0 quality %'s, from by Ti, Hf, Zr, V, Fe, Nb, Mo, Mn, W, Sr, Ba, B, Th, Mg, at least a element of selecting in first group that In constitutes, and contain total more than or equal to 0.001 quality %, be less than or equal to 3.0 quality %'s, from Be, Si, Al, Y and remove at least a element of selecting in second group that the rare earth element of Y constitutes; And be an end opening, the other end has the cup-shaped at the end.
11. cold-cathode fluorescence lamp as claimed in claim 10 is characterized in that, the content of C and S adds up to more than or equal to 0.001 quality %, is less than or equal to 0.10 quality % in the electrode.
12. cold-cathode fluorescence lamp as claimed in claim 10 is characterized in that, in the electrode content of hydrogen more than or equal to 0.1ppm, be less than or equal to 20ppm.
13. cold-cathode fluorescence lamp as claimed in claim 10 is characterized in that, the average crystal grain diameter that constitutes the metal of electrode is less than or equal to 70 μ m.
14. cold-cathode fluorescence lamp as claimed in claim 10 is characterized in that, the thickness that is formed at the oxidation overlay film of electrode surface is less than or equal to 1 μ m.
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| JP2006055558A JP4367954B2 (en) | 2005-05-25 | 2006-03-01 | Electrode material |
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| 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 |
| CN101677054B (en) * | 2008-09-16 | 2011-07-13 | 斯坦雷电气株式会社 | Electrode of cold cathode fluorescent tube and cold cathode fluorescent tube employing the same |
| US8283846B2 (en) * | 2009-12-24 | 2012-10-09 | Ngk Spark Plug Co., Ltd. | Spark plug containing specific ratio content |
| 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 |
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|---|---|---|---|---|
| CN1344423A (en) * | 1999-11-24 | 2002-04-10 | 皇家菲利浦电子有限公司 | Low-pressure mercury-vapor discharge lamp |
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2006
- 2006-05-25 CN CN2006100845592A patent/CN1873876B/en not_active Expired - Fee Related
- 2006-05-25 CN CN200910160230A patent/CN101633989A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1344423A (en) * | 1999-11-24 | 2002-04-10 | 皇家菲利浦电子有限公司 | Low-pressure mercury-vapor discharge lamp |
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| Title |
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| JP特开2004-207056A 2004.07.22 |
| JP特开2004-235072A 2004.08.19 |
| JP特开2004-71276A 2004.03.04 |
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| CN1873876A (en) | 2006-12-06 |
| CN101633989A (en) | 2010-01-27 |
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