CN1957642A - Ceramic heater, and oxygen sensor and hair iron using the ceramic heater - Google Patents
Ceramic heater, and oxygen sensor and hair iron using the ceramic heater Download PDFInfo
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- CN1957642A CN1957642A CN 200580016753 CN200580016753A CN1957642A CN 1957642 A CN1957642 A CN 1957642A CN 200580016753 CN200580016753 CN 200580016753 CN 200580016753 A CN200580016753 A CN 200580016753A CN 1957642 A CN1957642 A CN 1957642A
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Abstract
A highly durable ceramic heater is provided. The ceramic heater is provided with a ceramic base, a heat element buried in the ceramic base, an external electrode, which is electrically connected with the heat element, is provided on the surface of the ceramic base and has a thickness of 5-200mum, and a lead member soldered to the external electrode.
Description
Technical field
The present invention relates to the heater of the air-fuel ratio detecting sensor heating usefulness that automobile uses or gasifier with heater, soldering iron with employed ceramic heater in the heater etc. with adopt the lambda sensor of this ceramic heater and hair-waving to cut.
Background technology
In the past, for example, the heater as the employed air-fuel ratio sensor of automobile adopted ceramic heater more.This ceramic heater, for example by being in the ceramic matrix of principal component with the aluminium oxide, the built-in heating resistor that is made of refractory metals such as W, Re, Mo is via outer electrode jointing metal system terminal (lead member) and constitute (with reference to patent documentation 1, patent documentation 2) on this heating resistor.
This ceramic heater, for example, by preparing ceramic core and potsherd, on the one side of potsherd, print the cream of refractory metals such as W, Re, Mo, after forming heating resistor and electrode lead-out part, become inboard mode with the face that forms them and on ceramic core, twine potsherd, integrated through burning till formation, so make (patent documentation 1).
More specifically, formation heating resistor and connected contact conductor on potsherd form outer electrode at its back side.In addition, the electrode lead-out part of potsherd is connected with outer electrode by through hole.In through hole, inject conductor paste as required.
In addition, the ceramic heater shown in Fig. 8 A, Fig. 8 B is the ceramic heater 51 shown in the patent documentation 3.In the ceramic heater of this Fig. 8, connect taking-up electrode 57 at the two ends of heating resistor 53, this taking-up electrode 57 exposes by the peristome 58 that is located on the ceramic matrix 52, by solder brazing lead member 54 such as slicken solders.
Make and take out the peristome 58 that electrode 57 exposes, be used for the zone that electrode 57 and lead member 54 are taken out in the regulation soldering,, be formed on the end of ceramic matrix 52 by utilizing the perforate on the ceramic green sheet that becomes ceramic matrix 52 in advance of stamping-out processing method.
In the ceramic heater of patent documentation 3, peristome 58 forms the diameter corresponding concave part 56 of size and lead member 54 on its sidewall, in the time of soldering heating resistor 53 in peristome 58 and lead member 54, by in recess 56, inserting lead member 54, can be with the central portion of lead member 54 contraposition correctly at heating resistor 53, simultaneously thus with lead member 54 very securely soldering be installed on the heating resistor 53.
Patent documentation 1: the spy opens flat 5-34313 communique
Patent documentation 2: the spy opens flat 5-161955 communique
Patent documentation 3: the spy opens flat 06-196253 communique
But ceramic heater is in the past applying under the situation of thermal change repeatedly to electrode part, has the junction surface deterioration, the problem that durability significantly descends.
In recent years, it is strict that the regulation of the exhaust of relevant automobile becomes, and in air-fuel ratio is controlled with employed lambda sensor, requires to accelerate accelerating velocity, also requires to accelerate the accelerating performance of its employed ceramic heater.Under situation so, above-mentioned problem becomes prior problem.
That is, require to quicken the used ceramic heater of device of driven nature, service condition is harsh, has to take out the tendency that near the temperature of electrode raises.Owing to the thermal expansion difference because of solder and ceramic matrix, stress concentrates on this soldering portion thus, so require higher durability.Especially, for the employed ceramic heater of automobile,, therefore require high durability owing to require high reliability.
In addition, for example, cut as hair-waving, in the whole ceramic heater that is clamped in the holding member of, ceramic heater broad at heating region, owing to heat the taking-up electrode simultaneously rapidly with heating, so in the demanding durability of soldering part.
Summary of the invention
For this reason, the ceramic heater that provides a kind of durability high is provided the 1st purpose of the present invention.
In addition, the lambda sensor that provides a kind of durability high is provided the 2nd purpose of the present invention.
In addition, the 3rd purpose of the present invention is to provide the high hair-waving of a kind of durability to cut.
For achieving the above object,, it is characterized in that having: ceramic matrix according to the 1st ceramic heater of the present invention; Be embedded in the heating resistor in the described ceramic matrix; Outer electrode is electrically connected with described heating resistor, is located on the surface of described ceramic matrix, thick 5～200 μ m; The lead member of soldering on described outer electrode.
In addition, according to the 2nd ceramic heater of the present invention, it is characterized in that having: ceramic matrix; Be embedded in the heating resistor in the described ceramic matrix; Outer electrode is electrically connected with described heating resistor, is located on the surface of described ceramic matrix, and thick 5～50 μ m contain the additive that is made of the composition identical with the principal component of described ceramic matrix by the cooperation ratio of 1～10 weight %; The lead member of soldering on described outer electrode.
According to lambda sensor of the present invention, it is characterized in that: possess according to the of the present invention the 1st or the 2nd ceramic heater.
According to the 3rd ceramic heater of the present invention, it is characterized in that: the taking-up electrode that has ceramic matrix, is built in heating resistor in the described ceramic matrix, exposes and be electrically connected from the peristome that is located on the described ceramic matrix with described heating resistor, at least one portion of the periphery upper end at least one of the bight of the wall on the described peristome and/or the described peristome is from being select the group that constitutes of C face more than the 0.05mm or the R face more than the radius 0.05mm at least a by chamfer dimesion.
In addition, in the present invention, so-called " C face ", what say is the state that is the part at the angle that ground, inclined-plane fillet surface and hand-deliver fork-shaped become, what is called " R face ", what say is the state of the part at the angle that becomes with the fork-shaped of delivering personally of curved surface shape fillet surface.
In addition, according to the 4th ceramic heater of the present invention, it is characterized in that: have ceramic matrix, be built in heating resistor in the described ceramic matrix, from being located at taking-up electrode that peristome on the described ceramic matrix exposes and be electrically connected with described heating resistor, utilizing the lip-deep lead member of solder brazing at described taking-up electrode; Described solder has the layer structure that is made of the metal level more than 3 layers.
In addition, hair-waving according to the present invention is cut, and it is characterized in that: as electro-heat equipment, adopt according to any ceramic heater in the of the present invention the 1st～the 4th.
So constitute according to the 1st ceramic heater of the present invention, since soldering the described outer electrode of described lead member have the thickness of 5～200 μ m, so can improve the durability of outer electrode portion and periphery thereof, and can improve the bond strength of lead member.
In addition, according to the 2nd ceramic heater of the present invention, since soldering the thickness of described outer electrode of described lead member be 5～50 μ m, cooperation ratio by 1～10 weight % contains the additive that is made of the composition identical with the principal component of described ceramic matrix, so can improve the durability of outer electrode portion and periphery thereof more, and can improve the bond strength of lead member.
In addition, according to the 3rd ceramic heater of the present invention, because at least one portion of the periphery upper end at least one of the bight of the wall on the peristome and/or the peristome, be from being select the group that constitutes of C face more than the 0.05mm or the R face more than the radius 0.05mm at least a by chamfer dimesion, so can relax stress that the thermal expansion difference because of solder and ceramic matrix forms the concentrating of described periphery upper end, can prevent from this periphery upper end, crackle to take place.
In addition, according to the 4th ceramic heater of the present invention, because solder has the layer structure that is made of the metal level more than 3 layers, so can utilize solder to engage described taking-up electrode and lead member more firmly.
So,, can provide durability high ceramic heater according to the 1st～the 4th ceramic heater of the present invention.
In addition, according to lambda sensor of the present invention, owing to possess according to the of the present invention the 1st or the 2nd ceramic heater, so can provide durability high lambda sensor.
In addition, hair-waving according to the present invention is cut, because as electro-heat equipment, adopts according to any ceramic heater in the of the present invention the 1st～the 4th, so can provide the high hair-waving of durability to cut.
Description of drawings
Figure 1A is the stereogram of partly cut-away that is used to illustrate according to the embodiment of the present invention the formation of 1 ceramic heater.
Figure 1B is the expanded view of the ceramic matrix 2 on the ceramic heater of execution mode 1.
Fig. 2 is the section part sectioned view that amplifies the junction surface on the ceramic heater of representing execution mode 1.
Fig. 3 A is a stereogram of representing according to the embodiment of the present invention the formation of 2 ceramic heater.
Fig. 3 B is the vertical view that is used to make the potsherd 22a on the ceramic heater of execution mode 2.
Fig. 3 C is the vertical view that is used to make the potsherd 22b on the ceramic heater of execution mode 2.
Fig. 4 is the vertical view that amplifies the taking-up electrode on the ceramic heater of representing execution mode 2.
Fig. 5 A is the profile (1) of taking-up electrode of the ceramic heater of execution mode 2.
Fig. 5 B is the profile (2) of taking-up electrode of the ceramic heater of execution mode 2.
Fig. 5 C is the profile (3) of taking-up electrode of the ceramic heater of execution mode 2.
Fig. 6 amplifies the expression profile of the soldering part of 3 ceramic heater according to the embodiment of the present invention.
Fig. 7 is the stereogram that expression adopts an example hair-waving of ceramic heater of the present invention to cut.
Fig. 8 A is the vertical view of ceramic heater in the past.
Fig. 8 B is the stereogram that amplifies the taking-up electrode of expression ceramic heater in the past.
Among the figure: 1,22-ceramic heater, 2, the 22-ceramic matrix, 3, the 23-heating resistor, 3a-electrode lead-out part, the 4-outer electrode, 5-coating, 6, the 25-solder, 7, the 24-lead member, 8,22a, 22b-potsherd, 9-through hole, 10-pottery core, 20-cream, the 21c-C face, 22s-wall, 26-recess, the bight of the wall on the 26e-recess, 27-takes out electrode, 28-peristome, the bight of the wall on the 28e-peristome, 29-coating, 30e-periphery upper end.
Embodiment
Below, with reference to description of drawings according to the embodiment of the present invention.
Execution mode 1
Figure 1A is the stereogram of partly cut-away that is used to illustrate according to the embodiment of the present invention the formation of 1 ceramic heater, and Figure 1B is the expanded view of its ceramic matrix 2 parts.
Shown in Figure 1A, the ceramic heater 1 of present embodiment 1, built-in heating resistive element 3 in ceramic matrix 2.In addition, the ceramic heater 1 of execution mode 1 has the outer electrode 4 of switching on heating resistor 3 on the surface of ceramic matrix 2, form coating 5 on this outer electrode 4, is lead member 7 via solder 6 jointing metal system terminals.Herein, especially the ceramic heater 1 of present embodiment 1 is characterized in that, the thickness of outer electrode 4 is 5～200 μ m.
The ceramic heater 1 of present embodiment 1 is by following making.
At first, prepare ceramic core 10 and potsherd 8, on the one side of potsherd 8, print the cream of refractory metals such as W, Re, Mo, form heating resistor 3 and electrode lead-out part 3a.
Then, be the inboard with the face that forms heating resistor 3 and electrode lead-out part 3a, on ceramic core 10, twine potsherd 8, make integral body integrated through burning till.
So, potsherd 8 is bonded on the ceramic core 10, makes the ceramic matrix 2 of built-in heating resistive element 3 by become inboard mode with heating resistor 3.
As the ceramic material that constitutes ceramic matrix 2, can adopt various potteries such as aluminium oxide ceramics, silicon nitride ceramics, aluminium nitride ceramics, silicon carbide ceramics, but, preferred employing principal component is the ceramic material of aluminium oxide or silicon nitride, can access the ceramic heater of intensification rapidly and excellent in te pins of durability thus.For example, when adopting aluminium oxide ceramics, preferably by the Al of 88～95 weight %
2O
3, 2～7 weight % SiO
2, 0.5～3 weight % MgO, the ZrO of 1～3 weight % of CaO, 0.5～3 weight %
2The composition that constitutes.In addition, except that mentioned component, also can contain the impurity of trace.If Al
2O
3Content is lower than 88 weight %, because the nature of glass increases the misgivings that the migration when therefore energising being arranged increases.In addition, if Al
2O
3Content surpasses 95 weight %, and the oriented amount of glass that spreads in the metal level of the heating resistor 3 in the ceramic matrix 2 that is built in reduces the misgivings of the durability deterioration of ceramic heater 1.In addition, preferred when adopting silicon nitride ceramics, with respect to the silicon nitride of principal component,, in sintered body, mix the rare earth oxide of 3～12 weight % and the Al of 0.5～3 weight % as sintering aid
2O
3, in addition as the SiO that is contained in the sintered body
2Amount is mixed SiO in the mode that reaches 1.5～5 weight %
2About SiO shown here
2Amount is the SiO that is generated by impurity oxygen contained in the silicon nitride raw material
2, as the SiO of impurity contained in other additive
2, and the SiO that have a mind to add
2Summation.In addition, by in the mother metal silicon nitride, disperseing MoSi
2Or WSi
2, the coefficient of thermal expansion by making mother metal can improve the durability of heating resistor 3 near the coefficient of thermal expansion of heating resistor 3.
In addition, when adopting aluminium nitride, the preferred use: be added with Y as sintering aid by 2～8 weight % with respect to aluminium nitride
2O
3Deng rare earth oxide or CaO.
In addition, in execution mode 1, the ceramic matrix 2 that constitutes by ceramic core 10 and potsherd 8, for example, cylinder or cylindrical shape for external diameter 2～20mm, long 40～200mm scope, especially under the situation that the air-fuel ratio sensor that is used for automobile is used, cylinder or the cylindrical shape of preferred external diameter 2～4mm, long 40～65mm.In addition, in present embodiment 1, be defined as drum, but the present invention is not limited thereto, also can be writing board shape.
Especially, by this thickness D is set in 5～50 μ m, can improve durability more effectively.This outer electrode 4, can with the formation of heating resistor 3 and electrode lead-out part 3a in the same manner, adopt methods such as printing or duplicating, be formed on the opposing party's the interarea of potsherd 8 at the back side of meeting electrode lead-out part 3a.
In addition, as the method for this outer electrode 4 of thickening formation, by improving the mesh aperture opening ratio of the plate-making of in press using, can be than thickening ground formation in the past.But if excessively thickening, because the flatness of each face of the outer electrode 4 that forms goes wrong, therefore, this has carried out comprising the research of other parameter.Its result shows, along with the research of the mesh aperture opening ratio of above-mentioned plate-making, the translational speed of same squeegee (squeegee) by accelerating the employed coating usefulness of printing can more form with thickening.In addition, when printing,, can more form by improving the pressure that pushes described squeegee by the top with thickening.In addition, the shape of the contact portion of described squeegee and plate-making is also very important, by forming the shape of this contact portion more circularly, also can more form with thickening.In addition, by the mode of the described squeegee that fell with the moving direction at squeegee, angle block gauge is fixed on below 90 degree, thickening forms easily.In addition, the viscosity about the outer electrode of the paste before printing by tackifying, also can form with thickening, but must take into full account from the release property of making a plate.In addition, the thickness of thickening plate-making itself is also very effective.
So, this, when thickening forms outer electrode 4, viscosity and the release property of plate-making and the thickness and the whole balance of plate-making body of the outer electrode by considering aperture opening ratio or squeegee speed and pressure and squeegee shape or gradient, paste have found to thicken the optimum condition of formation.
In addition, width H1 by making the lip-deep outer electrode 4 that is formed on ceramic matrix 2 is greater than the width H of lead member 7 described later, can make solder 6 successfully flow into the end of outer electrode,, can seek the stabilisation of intensity by forming the meniscus of solder., be not less than the width H of lead member 7 herein by the width H1 that makes outer electrode 4, but proof strength, but, can improve bond strength more more preferably by H1 being set in more than 1.1 times of H.
In addition, the additive (not shown) that constitutes by the principal component that contains in the electrode 4 externally by ceramic matrix 2, this additive is to ceramic matrix 2 diffusion, in addition by ceramic matrix 2 itself also to outer electrode 4 phase counterdiffusion, can strengthen the adhesion strength of outer electrode 4 and ceramic matrix 2.Herein, the cooperation ratio in the outer electrode 4 of the additive that constitutes by the principal component of ceramic matrix 2, preferred 1～30 weight %, more preferably 1～10 weight %, the adhesion strength that can seek further to improve outer electrode thus by the phase counterdiffusion.
Especially because the thickness D of outer electrode 4 is 5～50 μ m, and the additive that constitutes by the principal component of ceramic matrix 2 externally the cooperation ratio in the electrode be 1～10 weight %, so can access intensity and the most excellent ceramic heater of durability.
In addition, externally on the surface of electrode 4, as shown in Figure 2, also can form coating 5.By externally forming coating 5 on the electrode 4, can play the flowability of improving solder 6, improve the effect of soldering strength.As the material of coating 5, be that the composite material etc. of principal component constitutes by Ni, Cr or with them, form by the thickness of 1～5 μ m.
Then, externally adopting solder 6 solderings on the electrode 4 is the lead member 7 that alloy etc. constitutes as the metallic terminal by thermal endurance good Ni system, Fe-Ni.Solder 6, employing is principal component as its material with Ag-Cu, Au-Cu, Ag, Cu, Au etc., the solder that contains the resin that becomes adhesive or reactive metal such as metals such as Ti, Mo, V as required forms, and forms by make its sclerosis in containing the reducing atmosphere of steam.
Below, the manufacture method of the ceramic heater of execution mode 1 is described.
At first, prepare by moulding with aluminium oxide to contain the SiO of 4～12 weight % by total amount as sintering aid as principal component
2, CaO, MgO, ZrO
2Ceramic ointment and the potsherd 8 that forms.
On an interarea of potsherd 8, method forms heating resistor 3 and electrode lead-out part 3a to adopt printing or duplicate etc., is bumping on another interarea of the potsherd 8 that connects with the back side of electrode lead-out part 3a, adopts printing or method such as duplicate forms outer electrode 4 equally.
Then, between electrode lead-out part 3a and outer electrode 4, form through hole 9, by filling in this through hole 9 or in the coating of the medial surface of through hole 9 with at least a kind among W, Mo, the Re electric conducting material as principal component, can carry out the electrical connection of electrode lead-out part 3a and outer electrode 4.
Then, when on heating resistor 3 and electrode lead-out part 3a, form by with potsherd 8 roughly equal form the coating that constitutes after, around ceramic core 10 around bonded ceramics sheet 8, the formed body of moulding tubular.In 1500～1650 ℃ reducing atmosphere, burn till the formed body that so obtains, as ceramic matrix 2.
Then, by utilizing electroplating method or electroless plating method, externally form the coating that constitutes by metals such as Ni, Cr on the surface of electrode 4.
Then, adopting with Au-Cu is the solder of principal component, engages outer electrode 4 and lead member 7 in containing the reducing atmosphere of steam.
Below, with reference to Fig. 3 A～Fig. 3 C, 2 ceramic heater according to the embodiment of the present invention is described.
The ceramic heater 21 of present embodiment 2 is the flat ceramic heaters that possess at the ceramic matrix 22 of inner built-in heating resistive element 23, is the structure of soldering anchor leg parts 24 on the taking-up electrode 27 that the peristome 28 by ceramic matrix 22 exposes.
The ceramic heater 21 of present embodiment 2, shown in Fig. 3 B, can be by on the surface of potsherd 22a, forming heating resistor 23 and connected taking-up electrode 27, in the above, shown in Fig. 3 C, another potsherd 22b that overlapping bonding is formed with peristome 28 and recess 26 burns till in 1500～1650 ℃ reducing atmosphere, makes.
The ceramic heater of execution mode 2, it is characterized in that: at least one portion of the periphery upper end at least one of the bight of the wall on the peristome and/or the peristome is from comprising that chamfer dimesion is select the group that constitutes of C face more than the 0.05mm or the R face more than the radius 0.05mm at least a.
When being ceramic heater shown in Figure 4, form R face more than the radius 0.05mm at the bight of the wall on the peristome 28 28e.Thus, can improve the durability of electrode part.In addition, also can be at the R face more than the bight of the wall on the recess 26 26e formation radius 0.05mm.
If this C face or the processing of R face are lower than 0.05mm, the stress that the thermal expansion difference of solder and pottery forms concentrates on bight 28e, the difficult durability that improves electrode part effectively.In addition,, more preferably C face or the processing of R face are defined in more than the 0.1mm, most preferably are defined in more than the 0.2mm in order to improve the durability of electrode part more.
In addition, preferred, also wall 22s and the border above the ceramic matrix 2 at peristome 28 (or recess 26) is on the periphery upper end 30e (with reference to Fig. 5 B), forms the above C face 21c (with reference to Fig. 5 C) of chamfer dimesion 0.05mm.In addition, on the 30e of periphery upper end, also can form the above R face of radius 0.05mm.In addition, preferably, implement in full C face or the processing of R face of periphery upper end 30e on the whole in the periphery of peristome 28 and recess 26, but also can on the 30e of periphery upper end, on the part of concentrating the stress that forms by solder and ceramic thermal expansion difference easily, implement C face or the processing of R face.
In addition, shown in Fig. 5 C,, can prevent damage lead member 24 when lead member 24 is set if on the periphery upper end 30e of the wall 22s of peristome 28, form C face 21c (or R face).Because this damage becomes the reason for corrosion that takes place in the use of ceramic heater 1, therefore so C face 21c (or R face) also helps to improve durability.
This C face or the processing of R face, because when processing on potsherd 22b during peristome, the generation that can suppress to process bits, therefore can prevent from advance to process consider to be worth doing the potsherd 22a, the 22b that are clipped in bonding between, imperfect bonding takes place, and reduces the problem of the durability of heating resistor 23.
In addition, preferred as shown in Figure 4, being embedded in more than 50% in the ceramic matrix 22 of the periphery (outside) of the taking-up electrode 27 that exposes by peristome 28.Under the situation of soldering lead member 24 on the taking-up electrode 27, since different with the coefficient of thermal expansion of ceramic matrix 22, therefore when solder flow into the periphery of taking out electrode 27, concentrate the stress of thermal expansion difference formation in its periphery.Therefore, expose if take out not being embedded in more than 50% in the pottery of periphery of electrode 27, easily at the outer peripheral portion generation crackle that exposes because of the thermal cycle in using.
According to reason so,, can prevent to prevent the reduction of durability at outer peripheral portion generation crackle by in ceramic matrix 22, burying more than 50% of periphery that takes out electrode 27 underground.More preferably, by in ceramic matrix 22, burying more than 75% of periphery that takes out electrode 27 underground, more effectively prevent crackle.In addition, preferably wall 22s on the peristome 28 and the angle θ that takes out electrode 27 formation are set in 60～110 °.Herein, the angle θ that wall 22s and taking-up electrode 27 form shown in Fig. 5 A, is the angle that is embedded in the top and wall 22s formation of the part in the ceramic matrix 22 that takes out electrode 27.
If this angle θ surpasses 110 °, the stress the when expansion that is formed near the solder 25 the wall 22s is shunk is in the end of solder 25, on the ceramic matrix 22 of the end of solder 25 crackle takes place easily.
In addition, if angle θ is lower than 60 °, when overlapping bonding potsherd 22b on potsherd 22a, because difficulty is exerted pressure to the interface of taking-up electrode 27 on the peristome 28 and potsherd 22a, the bonding variation produces the gap, it is little to prevent to take out the effect that electrode 27 peels off, and is not preferable range therefore.
In addition, more preferably angle θ is set in 60～90 °.
In addition, if the angle θ that this wall 22s and taking-up electrode 27 form, at the near interface that takes out electrode 27 and wall 22s (for example, from the border in the scope of 0.2mm), be set in below 110 °, more preferably be set in below 90 °, the concentrating of the stress the when expansion that can prevent the solder 5 on the end of solder 25 is shunk, thus can prevent the crackle of ceramic matrix 22.
In addition, shown in Fig. 5 B, when boning on the bonding interface of described peristome 28 and taking-up electrode 27, the cream 20 of configuration and ceramic matrix 22 homogeneities also burns till, and can not make solder 25 flow to the wall 22s of peristome 28.
So, flow to the wall 22s of peristome 28,, also can prevent because of pushing away the stress of wall 22s in the thermal expansion that utilizes solder 25, and crackle takes place in the end of the taking-up electrode 27 in peristome 28 even angle θ reaches more than 110 ° by not making solder 25.
In addition, when under the situation of overlapping use metallic plate on the ceramic heater 21, can prevent near C face 21c (or R face), to take place fragment.
In addition, about taking out the thickness of electrode 27, preferably be located at more than the 10 μ m, if this thickness is lower than 10 μ m, because it is low with the adhesion strength of ceramic matrix 22 to take out electrode 27, reduce with respect to the durability of the tensile strength of the lead member 24 of the thermal cycle in using, so preferred this thickness.
More preferably be defined in more than the 15 μ m, most preferably be defined in more than the 20 μ m.
The reason of the tensile strength of the thickness effect lead member 24 of taking-up electrode 27 is as follows.That is, take out electrode 27, in the gap of the refractory metal that porous sintering is made of W, Mo, Re etc., the glass ingredient of crystal boundary spreads in described gap from ceramic matrix 22, gains in strength with this connection effect.So the thickness that takes out electrode 27 is thick more, increase the tensile strength of lead member 24 more.
In addition, as the material that is used for heating resistor 23, also can adopt monomer or metal silicides such as their alloy or TiN, WC, the metal carbides etc. of W, Mo, Re.
As the material of heating resistor 23,,, improve durability owing to can not in use carry out the sintering of metal if adopt these dystectic materials.
Shown in Fig. 5 A,, can improve the bond strength that takes out electrode 27 if between ceramic matrix 22, sandwich the periphery that takes out electrode 27.
Shown in Fig. 5 B,, once form coating 29 as required, the flowability of the solder 25 in the time of can improving soldering lead member 24 by on the surface of taking out electrode 27.At this moment, if the brazing temperature of the solder 25 of anchor leg parts 24 is set in below 1000 ℃, owing to can reduce residual stress after the soldering, so preferably undertaken by this.
In addition, when in the high atmosphere of humidity, using ceramic heater 21, owing to adopt the solder 25 of Au system, Cu system to be difficult for moving, so preferably undertaken by this.As solder 25, can use the solder of Au, Cu, Au-Cu, Au-Ni, Ag, Ag-Cu system.As the Au-Cu solder, regulation Au content as the Au-Ni solder, uses the solder of Au content as 50-95 weight % at 25-95 weight %.As the Ag-Cu solder, if Ag content is defined in 60～90 weight %, more preferably be defined in 70～75 weight %, owing to become the composition of eutectic point, the generation of the alloy that the xenogenesis the when intensification in the time of can preventing soldering, cooling is formed, thereby can reduce after the soldering residual stress, so preferably select this scope.
In addition, when in the high atmosphere of humidity, using, preferably adopt the solder 25 of Au system, Cu system, move with difficult.
In addition, preferably form 2 coating that are made of Ni usually on the surface of solder 25, with the raising high temperature durability, and protection solder 25 is not corroded.
In addition, in order to improve durability, it is effectively that the particle diameter that constitutes the crystallization of 2 coating is defined in below the 5 μ m, if this particle diameter is greater than 5 μ m, because the intensity fragility of 2 coating has at high temperature and places the misgivings that crackle takes place under the environment.
In addition, though reason is also indeterminate, because it is more little to form the particle diameter of crystallization of 2 coating, the packing of coating good more (the density height of coating) so think and can prevent microdefect, as these 2 coating, is preferably adopted the electroless plating Ni of boron system.
In addition, the kind of electroless plating, except that the electroless plating of boron system, the electroless plating of the phosphorus that also can be covered system, but when the possibility of using under hot environment is arranged, the general electroless plating Ni that implements common boron system by changing the heat treatment temperature behind the coating 2 times, can control the particle diameter of 2 coating.
As the material of lead member 24, preferably using thermal endurance good Ni system, Fe-Ni is alloy etc., and this is because by transmitting the heat of heating resistor 23, the temperature rising of lead member 24 in the use, the possibility of deterioration are arranged.
Wherein, material as lead member 24, when using Ni or Fe-Ni to be alloy, preferably its average crystallite particle diameter is defined in below the 400 μ m, if average grain diameter surpasses 400 μ m, since vibration and thermal cycle when using, near lead member 24 fatigues the soldering portion, crackle takes place, so not preferred this scope.
For other material, if for example the particle diameter of lead member 24 is greater than the thickness of lead member 24, because stress concentrates on the crystal boundary of the boundary vicinity of solder 25 and lead member 24, crackle takes place, so not preferred this scope.
In addition, heat treatment during soldering, in order to reduce the deviation between sample, need have at fusing point under the high temperature of sufficient surplus and heat-treat than solder 25, but for the average crystallite particle diameter that makes lead member 24 less than below the 400 μ m, as long as the temperature when reducing soldering as far as possible, the shortening processing time just can.
In addition, as the material of ceramic heater 21, when adopting aluminium oxide, the preferred Al that uses by 88～95 weight %
2O
3, 2～7 weight % SiO
2, 0.5～3 weight % MgO, the ZrO of 1～3 weight % of CaO, 0.5～3 weight %
2The aluminium oxide that constitutes.Herein, as pottery, illustration aluminium oxide, but be not limited to aluminium oxide ceramics shown in the present invention, also can adopt silicon nitride ceramics, aluminium nitride ceramics, silicon carbide ceramics etc., in addition, just to ceramic heater 1, be that whole ceramic heaters of soldering all are fit to implementing Au.
Below, with reference to accompanying drawing, 3 ceramic heater according to the embodiment of the present invention is described.
The ceramic heater of present embodiment 3, except that soldering take out the solder 35 of electrode 27 and lead member 24 different, constitute in the same manner with execution mode 2.
In the soldering portion 35 that takes out between electrode 27 and the lead member 24, as shown in Figure 6, become from taking out electrode 27 side formation successively by the 1st layer of 35a, 3 layers of layer that constitutes such as the 2nd layer of 35b, the 3rd layer of 35c, form the structure of eutectic part 35d then in the above.
For forming so structure, on the surface of taking out electrode 27, implement coating, with Ag-Cu solder solders such as (BAg-8), soldering lead member 24.At this moment,, the fusion temperature (brazing temperature) and the fusing time (retention time) of solder are adjusted to defined terms, the electric conducting material that takes out in the electrode 27 and the composition in the solder are spread in coating by according to the material that constitutes solder and coating.Thus, between the part 35d that takes out electrode 27 and eutectic, form 3 layers of the 1st layer of 35a, the 2nd layer of 35b, the 3rd layer of 35c etc.
Be fit to use the alloy of Ni or Fe-Ni system as the material of lead member 24, for example Fe-Ni-Co alloy etc.
In addition, as the electric conducting material (being expressed as Me) that takes out electrode 27, be fit to use the monomer or the alloy of refractory metals such as W, Mo, Re.
The 1st layer of 35a of the electric conducting material 27 of the most approaching taking-up electrode 27, be by to being formed on the coating that constitutes by Ni that takes out on the electrode 27, from taking out electrode 27 diffusion electric conducting material Me, the layer that forms from solder diffusion Cu is to be Ni (Me) the Cu layer of principal component with Ni.In execution mode 3, improve the bond strength that takes out electrode 27 and solder by this Ni (Me) Cu layer.In addition, the 1st layer of 35a preferably is the NiWCu layer of principal component with Ni, can utilize this NiWCu layer to make the bond strength that takes out electrode 27 and solder more strong.The 1st layer of 35a by this NiWCu constitutes can take out electrode 27 by utilizing W to form, and from taking out electrode 27 to the Ni layer diffusion W that takes out on the electrode 27, forms from solder diffusion Cu.
In addition, being formed on the 2nd layer of 35b on the 1st layer of 35a, is to be the NiCu layer of principal component with Ni.In the 2nd layer of 35b, it is maximum to contain Ni.The 2nd layer of 35b of so rich Ni, Ni by being formed on the lip-deep coating that takes out electrode 27 before soldering and the Cu in the solder 35 constitute.The 2nd layer of 35b has the effect as the protective layer of the 1st layer of 35a of solid solution W.
In addition, being formed on the 3rd layer of 35c on described the 2nd layer of 35b, is to be the CuNi layer of principal component with Cu.In the 3rd layer of 35c, it is maximum to contain Cu.In addition, in the 3rd layer of 35c, also contain Ag sometimes.The 3rd layer of 35c has the effect with the stress relaxation layer of the stress of the thermal expansion difference formation of taking out electrode 27 as the original eutectic part 35d that relaxes the Ag-Cu solder.
The 2nd layer of 35b and the 3rd layer of 35c owing to form difference as mentioned above, for example can utilize SEM (scanning electron microscope) photo, discern according to the difference of tone.
In the ceramic heater of the execution mode 3 that so constitutes, between eutectic part 35d and taking-up electrode 27, by forming the 1st layer of above-mentioned 35a, the 2nd layer of 35b, the 3rd layer of 35c, can improve the tensile strength of lead member 24, can improve durability simultaneously.
Above-mentioned the 1st layer of 35a, the 2nd layer of 35b, the 3rd layer of 35c, preferred average thickness separate provision is 2～30 μ m, more preferably is defined as 2～20 μ m, most preferably is defined as 2～12 μ m.
If above-mentioned thickness is lower than 2 μ m, can not improve the tensile strength of lead member 24 effectively, in addition, if described thickness surpasses 30 μ m, especially, the tendency that becomes fragile is arranged because of the effect of the characteristic difference of each interlayer, along with the prolongation tensile strength reduction of service time, not preferable range therefore.
The thickness of the 2nd layer of 35b is formed on the influence of the thickness that takes out the Ni coating on the electrode 27, and the thickness of this Ni coating preferably is defined in 2～30 μ m.
The 3rd layer of 35c is as both react the intermediate layer of generation and generate between the eutectic layer of Ag-Cu solder and Ni coating.
The thickness of the 1st layer of 35a, the 2nd layer of 35b, the 3rd layer of 35c is subjected to the fusion temperature (brazing temperature) and fusing time (retention time) influence of solder.The brazing temperature of solder and retention time, the suitable decision of material according to the material that constitutes solder, formation coating does not limit especially.For example adopting BAg-8 (JIS standard), brazing temperature to be set in 800～900 ℃ scope as the Ag-Cu solder when, its retention time can be adjusted at 0.5～5 hour scope, preferably 1～5 hour scope, more preferably 1～2 hour scope.
In addition, in the ceramic heater of above execution mode 2 and execution mode 3, as the material of ceramic matrix 22, can use oxide ceramics such as aluminium oxide, mullite, forsterite or non-oxide ceramicses such as silicon nitride, aluminium nitride etc., but preferably use oxide ceramics.
In addition, Fig. 7 is that expression adopts according to the embodiment of the present invention 2 and the stereogram cut of an example hair-waving of execution mode 3 described ceramic heaters.
This hair-waving is cut, by hair is inserted in its front end cut arm 42 between, the handle 41 of holding with a firm grip pressurizes while heat hair, so processes hair.In the inside of cutting arm 42, insert ceramic heater 46, with part that hair directly contacts metallic plates 43 such as stainless steel are being set.
In addition, be formed on the structure that the cover be used to prevent the heat resistant plastice system of scalding is installed in the outside of cutting arm 42.
More than, the ceramic heater according to present embodiment has been described, but the present invention is not limited to above-mentioned execution mode, in the scope that does not break away from aim of the present invention, can carry out numerous variations.
Embodiment
Embodiment 1
In embodiment 1, for confirming validity, make trial target according to the invention of execution mode 1, implemented following test.
At first, for obtaining ceramic heater sample shown in Figure 1, as ceramic matrix 2, with Al
2O
3Be principal component, with SiO
2, CaO, MgO, ZrO
2Adjust to reach and add up in the 10 weight %, make potsherd 8, print heating resistor 3 that constitutes by W-Re and the electrode lead-out part 3a that constitutes by W in the above.In addition, printing outer electrode 4 on the back side of potsherd 8.
Then, form through hole, by injecting cream herein, between conducting outer electrode 4 and the electrode lead-out part 3a at the end of the electrode lead-out part 3a that constitutes by W.The position of through hole under the situation of implementing soldering, forms in the inboard mode that enters soldering portion.
Then, on the surface of heating resistor 3, form by the coating that constitutes with the roughly the same composition of potsherd 8, after intensive drying, coating makes the binding liquid of disperseing with the pottery of potsherd 8 roughly the same compositions again, with the potsherd of so preparing 8 be bonded in ceramic core 10 around, burn till with 1500～1600 ℃.
In addition, on the surface of said external electrode 4, form the coating 5 that constitutes by Ni, in reducing atmosphere with after 700～800 ℃ of heat treatments, the solder 6 that employing is made of Au-Cu, the lead member 7 of the diameter 0.8mm that in reducing atmosphere, constitutes by Ni with 830 ℃ of solderings, in addition in its surface, form the coating that constitutes by Ni in the end, with 700 ℃ of heat treatments.
About by the above-mentioned ceramic heater that obtains,, make sample by the thickness and the additive mix proportion of multiple change outer electrode 4.
Adopt digital multimeter, measure the resistance value of distinguishing the ceramic heater sample that obtains, see to have or not floating of data value, confirm stability.
Then, the horizontal positioned ceramic heater is fixed with the maintenance anchor clamps, to the direction vertical with the faying face of lead member, and the stretching lead member, the dynamometer of usefulness numeric type is measured the initial stage bond strength of lead member 7.
In addition, the durability of the high temperature of the sample electrodes portion of the ceramic heater that obtains is estimated.With the ceramic heater durable stove of high temperature of packing into, 400 ℃ place 3 minutes after, continue to be implemented in 3 minutes and reach the circulation evaluation that is lower than 100 ℃, the tensile strength of 3000 lead member after the circulation is implemented in investigation.Its investigation result sees Table 1.
Table 1
| Sample No. | Outer electrode thickness (μ m) | Additive mix proportion (%) | Initial stage bond strength (N) | Bond strength (N) after implementing to circulate | Resistance stability |
| *1 | 3 | 0 | 46 | 5 | ○ |
| *2 | 5 | 77 | 14 | ○ | |
| 3 | 5 | 0 | 72 | 51 | ○ |
| 4 | 1 | 115 | 115 | ○ | |
| 5 | 5 | 119 | 113 | ○ | |
| 6 | 10 | 121 | 114 | ○ | |
| 7 | 30 | 108 | 89 | ○ | |
| 8 | 40 | 109 | 79 | △ | |
| 9 | 7 | 0 | 76 | 55 | ○ |
| 10 | 5 | 117 | 114 | ○ | |
| 11 | 10 | 0 | 81 | 58 | ○ |
| 12 | 5 | 107 | 109 | ○ | |
| 13 | 30 | 0 | 85 | 61 | ○ |
| 14 | 5 | 115 | 114 | ○ | |
| 15 | 50 | 0 | 78 | 54 | ○ |
| 16 | 1 | 114 | 112 | ○ | |
| 17 | 5 | 122 | 114 | ○ | |
| 18 | 10 | 117 | 107 | ○ | |
| 19 | 30 | 106 | 89 | ○ | |
| 20 | 40 | 105 | 94 | △ | |
| 21 | 100 | 0 | 76 | 53 | ○ |
| 22 | 5 | 103 | 89 | ○ | |
| 23 | 200 | 0 | 80 | 53 | ○ |
| 24 | 1 | 106 | 87 | ○ | |
| 25 | 5 | 107 | 92 | ○ | |
| 26 | 10 | 109 | 83 | ○ | |
| 27 | 30 | 105 | 90 | ○ | |
| 28 | 40 | 104 | 79 | △ | |
| *29 | 250 | 0 | 77 | 23 | ○ |
| *30 | 5 | 119 | 27 | ○ |
As shown in table 1, the sample that ceramic heater according to the present invention is thick 5～200 μ m of outer electrode (No.3～28) has the above initial stage bond strength of 70N, can guarantee enough intensity.In addition, the bond strength of the lead member 7 after implementing about circulation also can be guaranteed the intensity of no problem in practicality that 50N is above.
Wherein, externally electrode cooperates the sample (No.4～8,10,12,14,16～20,22,24～28) of additive, has the above initial stage bond strength of 100N, and the bond strength after implementing to circulate also can be guaranteed enough intensity also up to more than the 70N.
In addition, wherein, cooperate the sample (No.4～7,10,12,14,16～19,22,24～27) of ratio for additive at 1 weight %～30 weight %, the bond strength after fully guaranteeing the initial stage bond strength and implementing circulation, resistance is also stable, do not have and float, the stability of the characteristic of goods is also good.
In addition, thickness for outer electrode is that 5 μ m～50 μ m, additive cooperate the sample (No.4～6,10,12,14,16～18) of ratio at 1 weight %～10 weight %, even implement the bond strength of the lead member after the circulation, also have and intensity more than the almost unconverted 100N of initial stage bond strength, we can say excellent.
Below, by the thickness of each outer electrode, change the width H1 of the outer electrode 4 of ceramic heater, make sample.
Then, with above-mentioned same, the bond strength of the lead member 7 after the initial stage bond strength of investigation ceramic heater sample and 3000 circulations of enforcement long duration test.It the results are shown in Table 2.
Table 2
| Sample No. | Outer electrode thickness (μ m) | The width of outer electrode H1 (with respect to the ratio of the width H of lead member) | Initial stage bond strength (N) | Bond strength (N) after implementing to circulate |
| 31 | 5 | 0.9H | 70 | 53 |
| 32 | 1.0H | 109 | 82 | |
| 33 | 1.1H | 115 | 109 | |
| 34 | 1.5H | 117 | 101 | |
| 35 | 2.0H | 114 | 104 | |
| 36 | 30 | 0.9H | 79 | 60 |
| 37 | 1.0H | 110 | 79 | |
| 38 | 1.1H | 115 | 108 | |
| 39 | 1.5H | 115 | 109 | |
| 40 | 2.0H | 116 | 105 | |
| 41 | 100 | 0.9H | 79 | 59 |
| 42 | 1.0H | 112 | 91 | |
| 43 | 1.1H | 114 | 110 | |
| 44 | 1.5H | 117 | 106 | |
| 45 | 2.0H | 116 | 106 |
As shown in table 2, for the width H1 of outer electrode sample (No.32～35,37～40,42～45) greater than the width H of lead member, has the above initial stage bond strength of 100N, even and for the bond strength of implementing the lead member 7 after the circulation, also have the above intensity of 70N, can guarantee enough intensity.
Wherein, for the width H1 of outer electrode the big sample (No.33～35,38～40,43～45) more than 1.1 times of width H than lead member, even bond strength for the lead member 7 after the enforcement circulation, also have the intensity more than the 100N that does not almost have to change with the initial stage bond strength, we can say excellent.
The embodiment 2～5 that the following describes is relevant embodiment of 2 according to the embodiment of the present invention.
With Al
2O
3Be principal component, with SiO
2, CaO, MgO, ZrO
2Adjust to reach and add up in the 10 weight %, make potsherd 22a, on the surface of this potsherd 22a, shown in Fig. 3 B, the cream that printing is made of W forms heating resistor 23 and takes out electrode 27.
Thereafter, on another potsherd 22b, form numerous variations shaped aperture portion 28 and recess 26, overlapping bonding potsherd 22b burns till in 1600 ℃ reducing atmosphere on described potsherd 22a, makes the potsherd 1 of each 20 long 100mm, wide 10mm, thick 1.2mm respectively.
At this moment, the shape of peristome 28 and recess 26, for 28 the bight 28e on 4 limits of peristome at rectangular shape, the mold shape that change peristome 28 stamping-outs are used changes to 0.01mm, 0.03mm, 0.05mm, 0.10mm, 0.20mm, 0.30mm, 0.50mm with the size of C face or R face.
Then, electroless plating Ni is implemented on the surface of the taking-up electrode 27 that exposes at peristome 28, thereafter, with the Ni line of Ag-Cu solder (BAg-8) braze wire footpath 0.6mm.
Two sides at the ceramic heater of so preparing 21, the aluminium sheet of long 110mm, wide 12mm, thick 5mm is set in the mode that covers ceramic heater 21 integral body, be bonded and fixed at the central portion of ceramic heater 21 respectively, as accelerated test, 5 minutes applied voltages, make the maximum temperature portion of ceramic heater 21 reach 300 ℃, blew air then in 5 minutes, make below the whole forced air-cooling to 40 ℃, 3000 circulation repeated thermal cycles test like this confirms that the tensile strength of the lead member 24 of ceramic heater 1 changes.
The average result that tensile strength is got N=10 respectively sees Table 3.
Table 3
| No. | Chamfer dimesion (mm) | Initial stage bond strength (N) | After the long duration test (N) | Remarks |
| 46 * | Do not have | 120 | 22 | The C face |
| 47 * | 0.01 | 120 | 27 | ↑ |
| 48 * | 0.03 | 120 | 29 | ↑ |
| 49 | 0.05 | 120 | 46 | ↑ |
| 50 | 0.10 | 120 | 48 | ↑ |
| 51 | 0.20 | 120 | 62 | ↑ |
| 52 | 0.30 | 120 | 58 | ↑ |
| 53 | 0.50 | 120 | 60 | ↑ |
| 54 * | 0.03 | 120 | 30 | The R face |
| 55 | 0.10 | 120 | 61 | ↑ |
| 56 | 0.50 | 120 | 64 | ↑ |
*: beyond the claimed range of the present invention.
Can be differentiated by table 3, not implement the No.46 of C surface chamfer, the No.47,48 that C surface chamfer size is lower than 0.05mm, the tensile strength after the long duration test drops to below the 30N.
To this, No.49～53 that C surface chamfer size 0.05mm is above demonstrate the above intensity of 40N.
In addition, No.51～53 that C surface chamfer size 0.2mm is above demonstrate the intensity about 60N, even for the No.55,56 that the C surface chamfer is changed to the R surface chamfer, also demonstrate same result, but the tensile strength after the long duration test of No.54 drops to below the 30N.
In this example, on the peristome 28 of ceramic heater 21, the ratio that is embedded in the periphery of the taking-up electrode 27 in the ceramic matrix 22 is changed to 30%, 50%, 70%, 90%, press ceramic heater 21 monomers, ceramic heater 21 put in 400 ℃ the thermostat, kept 10 minutes, and made temperature stabilization, take out then, blew air 5 minutes, be cooled to below 40 ℃, thermal cycling test is implemented in 2000 circulations like this, measures the tensile strength of lead member 24.
Described tensile strength is to the end of the direction stretching lead member 24 vertical with the side face of ceramic heater 21, measures its peel strength.
In addition, as lead member 24, adopt the Ni line of line footpath 0.6mm, solder 25 adopts Ag-Cu solder (BAg-8).
Tensile strength is got the average of N=10 respectively, makes sample by the method identical with embodiment 2, and the measurement result of sample sees Table 4.
Table 4
| Sample No. | Bury ratio (%) underground | Early strength (N) | Durable back intensity (N) |
| 57 | 30 | 120 | 20 |
| 58 | 50 | 120 | 50 |
| 59 | 70 | 120 | 65 |
| 60 | 90 | 120 | 75 |
Can differentiate by table 4, the ratio that is embedded in the periphery of the taking-up electrode 2 in the ceramic matrix 22 is 30% No.57, the peel strength of the lead member 24 after the long duration test is 20N, but ratio demonstrates the above good tensile strength of 50N in the No.58 more than 50%～60.
In this example, measure wall 22s and the angle θ of taking-up electrode 27 formation and the tensile strength of the lead member 24 after the thermal cycle long duration test of the peristome 28 of ceramic heater 21.
Preparation changes to angle θ on 50 °, 60 °, 80 °, 90 °, 100 °, 110 °, 120 ° sample.
Estimate long duration test in the same manner with embodiment 3, estimate n=10 respectively, on average the results are shown in Table 5 as what data were put down in writing with this.
Table 5
| Sample No. | Angle (θ) | Early strength (N) | Durable back intensity (N) |
| 61 | 50 | 120 | 45 |
| 62 | 60 | 120 | 60 |
| 63 | 80 | 120 | 64 |
| 64 | 90 | 120 | 66 |
| 65 | 100 | 120 | 65 |
| 66 | 110 | 120 | 65 |
| 67 | 120 | 120 | 46 |
Can be differentiated by table 5, angle θ is 50 ° No.61, and the tensile strength after the long duration test reaches below the 50N, in addition, angle θ is that the tensile strength of 120 ° No.67 also reaches below the 50N, and angle θ is 60～110 ° No.62～66, and tensile strength demonstrates the above high value of 60N.
In this example, the thickness of electrode 27 and the relation of the tensile strength after the long duration test are taken out in research.
Preparing 20 varied in thickness that will take out electrode 27 respectively is the sample of 5 μ m, 10 μ m, 20 μ m, 40 μ m, 60 μ m, 80 μ m, 100 μ m, estimates intensity after the long duration test in the same manner with embodiment 3, and evaluation result sees Table 6.
Table 6
| Sample No. | Take out thickness of electrode (μ m) | Early strength (N) | Durable back intensity (N) |
| 68 | 5 | 100 | 30 |
| 69 | 10 | 120 | 55 |
| 70 | 20 | 120 | 60 |
| 71 | 40 | 120 | 62 |
| 72 | 60 | 120 | 65 |
| 73 | 80 | 120 | 65 |
| 74 | 100 | 120 | 66 |
Can be differentiated by table 6, the finger gauge of taking out electrode 27 is decided to be the No.68 of 5 μ m, the tensile strength after the long duration test is low to 30N, but described finger gauge is decided to be No.69～74 of 10～100 μ m, demonstrates favorable durability.
In addition, wherein, described finger gauge is decided to be No.70～74 more than the 20 μ m, demonstrates the above intensity of 60N.
Embodiment 6
According to embodiments of the invention 6, be embodiment about execution mode 3.
With Al
2O
3Be principal component, with SiO
2, CaO, MgO, ZrO
2Adjust to reach and add up in the 10 weight %, make potsherd 22a, on the surface of this potsherd 22a, shown in Fig. 3 B, the cream 10 that printing is made of W forms heating resistor 23 and takes out electrode 27.
Then, form peristome 28 and recess 26 on another potsherd 22b, overlapping bonding potsherd 22b burns till in 1600 ℃ reducing atmosphere on described potsherd 22a, makes the potsherd 21 of each 20 long 100mm, wide 10mm, thick 1.2mm respectively.
Then, the electroless plating Ni of thick 5 μ m is implemented on the surface of the taking-up electrode 27 that exposes at peristome 28, with the Ni line of Ag-Cu solder (BAg-8) braze wire footpath 0.6mm Φ.
In addition, replace electroless plating Ni to implement the sample of electroless plating Cr, also together estimate.
At this moment, the condition of soldering is changed to 800 ℃, 850 ℃, 900 ℃ respectively, will be changed to 0.5 hour the retention time, 1 hour, 2 hours, 5 hours, implement soldering.
Then, the durability in order to confirm to use is continuously measured the tensile strength at initial stage and 400 ℃ * 800 hours tensile strength after the energising continuously.Described tensile strength is to the end of the direction stretching lead member 24 vertical with the interarea of ceramic heater 21, measures its peel strength.
In addition, with every group of 2 sections of electron microscope observation, confirm the tissue of the near interface of taking-up electrode 27 and solder.
In addition, as lead member 24, adopt the Ni line of line footpath 1.0mm.
Observed result sees Table 7 (table 7-1, table 7-2).
Table 7-1
| Sample No. | The 1st layer | The 2nd layer | The 3rd layer | The upper strata |
| 75 * | Ni-W | - | - | Eutectic |
| 76 | Ni-W | Ni-Cu | Cu-Ni | Eutectic |
| 77 | Ni-W | Ni-Cu | Cu-Ni | Eutectic |
| 78 | Ni-W | Ni-Cu | Cu-Ni | Eutectic |
| 79 * | Ni-W | Ni-Cu | - | Eutectic |
| 80 | Ni-W | Ni-Cu | Cu-Ni | Eutectic |
| 81 | Ni-W | Ni-Cu | Cu-Ni | Eutectic |
| 82 | Ni-W | Ni-Cu | Cu-Ni | Eutectic |
| 83 | Ni-W | Ni-Cu | Cu-Ni | Eutectic |
| 84 | Ni-W | Ni-Cu | Cu-Ni | Eutectic |
| 85 | Ni-W | Ni-Cu | Cu-Ni | Eutectic |
| 86 | Ni-W | Ni-Cu | Cu-Ni | Eutectic |
| 87 | Cr-W | Cr-Cu | Cu-Cr | Eutectic |
*: beyond the claimed range of the present invention.
Table 7-2
| No. | Brazing temperature (℃) | Retention time (hour) | Initial stage tensile strength (N) | Durable back tensile strength (N) |
| 75 * | 800 | 0.5 | 340 | 178 |
| 76 | ↑ | 1 | 340 | 245 |
| 77 | ↑ | 2 | 340 | 258 |
| 78 | ↑ | 5 | 340 | 280 |
| 79 * | 850 | 0.5 | 340 | 195 |
| 80 | ↑ | 1 | 340 | 264 |
| 81 | ↑ | 2 | 340 | 266 |
| 82 | ↑ | 5 | 340 | 285 |
| 83 | 900 | 0.5 | 340 | 232 |
| 84 | ↑ | 1 | 340 | 264 |
| 85 | ↑ | 2 | 340 | 267 |
| 86 | ↑ | 5 | 340 | 273 |
| 87 | ↑ | 5 | 340 | 273 |
*: beyond the claimed range of the present invention.
Can differentiate by table 7, at the near interface that takes out electrode 27 and solder, do not find the No.75,79 of 3-tier architecture shown in Figure 6, tensile strength after the long duration test is reduced to below the 200N, but the No.76,77,78,80～87 at described near interface discovery 3-tier architecture obtains the above high tensile strength of 200N.
According to embodiments of the invention 7, also be embodiment about execution mode 3.In this example, the thickness of coating is adjusted into 1,2,4,8,12 μ m, confirm its influence by long duration test.
As solder, adopt the BAg-8 of Ag-Cu solder, under 900 ℃ * 1 hour condition, carry out soldering and handle.For others, with embodiment 6 in the same manner, make the sample shown in the table 8.
On the two sides of the ceramic heater of so preparing 21, the aluminium sheet of long 110mm, wide 12mm, thick 5mm is set in the mode that covers ceramic heater 21 integral body, be bonded and fixed at the central portion of ceramic heater 21 respectively, as accelerated test, 5 minutes applied voltages make the maximum temperature portion of ceramic heater 21 reach 300 ℃, blew air then in 5 minutes, make below the whole forced air-cooling to 40 ℃, the resistance variations of ceramic heater 21 is confirmed in 3000 circulation repeated thermal cycles test like this.
In addition, about the manufacture method of sample, make sample by the method identical with embodiment 6.
The results are shown in Table 8.
Table 8
| No. | Ni thickness of coating (μ m) | The 1st layer thickness (μ m) | The 2nd layer thickness (μ m) | The 3rd layer thickness (μ m) | Initial stage tensile strength (N) | Durable back tensile strength (N) |
| 88 | 1 | 0.4 | 0.8 | 2.6 | 340 | 72 |
| 89 | 2 | 1.2 | 1.4 | 2.8 | 340 | 152 |
| 90 | 4 | 1.8 | 3.1 | 2.6 | 340 | 158 |
| 91 | 8 | 2.6 | 6.3 | 2.9 | 340 | 165 |
| 92 | 12 | 2.8 | 11.5 | 2.8 | 340 | 181 |
| 93 | 20 | 3.1 | 18.8 | 2.9 | 340 | 171 |
| 94 | 30 | 3.3 | 28.9 | 3.2 | 340 | 143 |
| 95 | 40 | 3.2 | 39.8 | 3.0 | 340 | 98 |
| 96 | 12 | 3.8 | 13.8 | 28.8 | 340 | 138 |
Can be differentiated by table 8, the No.88 of thickness of coating 1 μ m after the long duration test, has to the tensile strength below the 100N, but No.89～92 of thickness of coating 2～12 μ m after the long duration test, demonstrate the above good tensile strength of 100N.
Claims (18)
1. ceramic heater,
Have:
Ceramic matrix,
Be embedded in the heating resistor in the described ceramic matrix, and
Outer electrode is electrically connected with described heating resistor, is located at the surface of described ceramic matrix, and thickness is 5～200 μ m;
Lead member, soldering is at described outer electrode.
2. ceramic heater as claimed in claim 1, wherein: the width of described outer electrode is bigger than described lead member.
3. ceramic heater as claimed in claim 1 or 2, wherein: described outer electrode contains the additive that is made of the composition identical with the principal component of described ceramic matrix.
4. ceramic heater as claimed in claim 3, wherein: the cooperation ratio of the described additive in the described outer electrode is 1～30 weight %.
5. ceramic heater,
Have:
Ceramic matrix,
Be embedded in the heating resistor in the described ceramic matrix, and
Outer electrode is electrically connected with described heating resistor, is located at the surface of described ceramic matrix, and thickness is 5～50 μ m, contains the additive that is made of the composition identical with the principal component of described ceramic matrix with the cooperation ratio of 1～10 weight %;
Lead member, soldering is at described outer electrode.
6. as each described ceramic heater in the claim 1 to 5, wherein: described ceramic matrix is cylindric or cylindric.
7. as each described ceramic heater in the claim 1 to 6, wherein: the principal component of described ceramic matrix is aluminium oxide or silicon nitride.
8. as each described ceramic heater in the claim 1 to 7, wherein: described outer electrode contains tungsten or tungsten compound as principal component.
9. a lambda sensor is characterized in that: possess each described ceramic heater in the claim 1 to 8.
10. ceramic heater,
Possess:
Ceramic matrix,
Be embedded in the heating resistor in the described ceramic matrix, and
Take out electrode, expose, be electrically connected with described heating resistor from the peristome that is located on the described ceramic matrix,
At least a portion of periphery upper end at least a portion in the bight of the wall on the described peristome and/or the described peristome is that being selected from by chamfer dimesion is at least a in the group that constitutes of C face more than the 0.05mm or the R face more than the radius 0.05mm.
11. ceramic heater as claimed in claim 10, wherein: being embedded in the ceramic matrix more than 50% of the periphery of the described taking-up electrode on the described peristome.
12. ceramic heater as claimed in claim 11, wherein: the wall of described peristome is defined as 60～110 ° with the angle θ that the surface that is embedded in the taking-up electrode in the described ceramic matrix forms.
13. as each described ceramic heater in the claim 10 to 12, wherein: the finger gauge of described taking-up electrode is decided to be more than the 10 μ m.
14. as each described ceramic heater in the claim 10 to 13, wherein: on described taking-up electrode, be provided with coating.
15. a ceramic heater,
Possess:
Ceramic matrix,
Be built in the heating resistor in the described ceramic matrix, and
Take out electrode, expose, be electrically connected with described heating resistor from the peristome that is located on the described ceramic matrix,
Lead member, by the surface of solder brazing at described taking-up electrode,
Described solder has the layer structure that is made of the metal level more than three layers.
16. ceramic heater as claimed in claim 15, wherein:
Described metal level contains the 1st metal level, the 2nd metal level and the 3rd metal level successively from described taking-up electrode side;
Described the 1st metal level is to be the NiWCu layer of principal component with Ni, and described the 2nd metal level is to be the NiCu layer of principal component with Ni, and described the 3rd metal level is to be the CuNi layer of principal component with Cu.
17. as claim 15 or 16 described ceramic heaters, wherein: the average thickness of described the 1st metal level, described the 2nd metal level and described the 3rd metal level is set in the scope of 2～30 μ m respectively.
18. a hair-waving is cut, and it is characterized in that: adopt any one described ceramic heater in claim 1～8 and the claim 10～17 as electro-heat equipment.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP158443/2004 | 2004-05-27 | ||
| JP158444/2004 | 2004-05-27 | ||
| JP2004158443 | 2004-05-27 | ||
| JP185146/2004 | 2004-06-23 |
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| Publication Number | Publication Date |
|---|---|
| CN1957642A true CN1957642A (en) | 2007-05-02 |
| CN100536621C CN100536621C (en) | 2009-09-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005800167530A Active CN100536621C (en) | 2004-05-27 | 2005-05-26 | Ceramic heater, and oxygen sensor and hair iron using the ceramic heater |
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| Country | Link |
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| CN (1) | CN100536621C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103477704A (en) * | 2011-03-31 | 2013-12-25 | 京瓷株式会社 | Ceramic heater |
| CN110521279A (en) * | 2017-04-26 | 2019-11-29 | 京瓷株式会社 | Heater |
-
2005
- 2005-05-26 CN CNB2005800167530A patent/CN100536621C/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103477704A (en) * | 2011-03-31 | 2013-12-25 | 京瓷株式会社 | Ceramic heater |
| CN103477704B (en) * | 2011-03-31 | 2015-12-02 | 京瓷株式会社 | Ceramic heater |
| CN110521279A (en) * | 2017-04-26 | 2019-11-29 | 京瓷株式会社 | Heater |
| CN110521279B (en) * | 2017-04-26 | 2021-11-23 | 京瓷株式会社 | Heating device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100536621C (en) | 2009-09-02 |
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