KR101201388B1 - Ceramic heater and heating iron using it - Google Patents

Abstract

In order to provide a highly durable ceramic heater having excellent durability even under severe conditions such as high temperature, vibration, and exhaust gas atmosphere, and high reliability against rapid heating and cooling, the ceramic heater is connected to a built-in conductor and the conductor. A ceramic body having a metallization layer and a lead member joined to the metallization layer with a brazing filler material, wherein a covering area covering the lead member of the brazing filler material is closest to the metallization layer in the lead member. It is set in the range of 40 to 99% of the distance from the stage and the uppermost side away from the metallization layer.

Description

CERAMIC HEATER AND HEATING IRON USING IT}

The present invention relates to a ceramic heater and a heating iron configured using the same.

Background Art Conventionally, ceramic heaters have been widely used as heat sources for petroleum vaporizers such as semiconductor heating heaters, soldering irons, hair irons, petroleum fan heaters, and the like, or as heat sources in glow systems and the like. Moreover, in recent years, the use of the ceramic heater for vehicle mounting, especially for air-fuel ratio detection sensor (oxygen sensor) heating, is increasing.

This ceramic heater has various shapes such as a flat plate, a cylinder, and a cylindrical shape, but any of them is a conductor made of a high melting point metal such as W, Re, Mo, or the like in a ceramic base containing alumina as a main component. It is comprised by embedding. 11 shows a cylindrical ceramic heater as an example. The ceramic heater is composed of a ceramic body in which a conductor is embedded, a terminal mounting electrode portion 106 formed on the surface thereof, and a lead member 110 joined to the surface by a brazing filler material 111. This terminal electrode part 106 consists of a metallization layer and a Ni plating layer, and the embedded conductor and the metallization layer are connected in order to supply electric power to the embedded conductor (patent document 1).

Moreover, in recent years, the ceramic heater which prescribed | regulated the range of the angle which the tangent in the brazing material end of a brazing material outer edge and the tangent in contact with the brazing material end point of an electrode outer edge in order to improve reliability is also proposed (patented) Document 2).

Patent Document 1: Japanese Patent Application Laid-Open No. 8-109063

(Patent Document 2) Japanese Unexamined Patent Publication No. 2000-286047

However, in recent years, in-vehicle ceramic heaters, which are in increasing demand, have been subjected to harsh use environments such as high temperature, vibration, and waste gas atmospheres, so that high reliability is required, particularly in the joint portion fixing the lead member. It has come to be.

Moreover, in recent years, in the apparatus comprised using the ceramic heater, the fast heat-generating characteristic was calculated | required, and in the ceramic heater which requires such a rapid heat generation, the temperature change in a junction part is also severe and high reliability is calculated | required at the junction part. That is, a stress concentrates on this soldering part by the thermal expansion difference of the brazing material and ceramic base for fixing a lead member to a terminal installation electrode part, and the problem that the durability of a ceramic heater falls.

Particularly, for example, in a ceramic heater in which a heat generating area is wide and the whole ceramic heater is held in the holding member, such as a hair curler, the electrode extraction portion is rapidly heated at the same time as heating, thereby improving durability.

Therefore, an object of the present invention is to provide a highly durable ceramic heater that is excellent in durability even under severe conditions such as high temperature, vibration, and exhaust gas atmosphere, and has high reliability against rapid heating and cooling.

The present invention also aims to provide a heating iron having high durability.

In order to achieve the above object, the 1st ceramic heater which concerns on this invention is equipped with the ceramic body which has a built-in conductor and the metallization layer electrically connected with the conductor, and the lead member joined to the said metallization layer by the brazing material, The covering area covering the lead member of the brazing filler material is set in the range of 40 to 99% of the distance from the closest end closest to the metallization layer in the lead member and the uppermost side away from the metallization layer. It is characterized by.

In addition, the second ceramic heater according to the present invention includes a ceramic body having a built-in conductor and a metallization layer conductive with the conductor, and a lead member bonded to the metallization layer with a brazing filler material, wherein the brazing filler material is two or more kinds. It is made by containing a metal, It is characterized by the above-mentioned two or more types of metals which exist distinguishably in the said brazing filler metal, respectively.

In the present invention, the identifiable means that two or more kinds of metals are not mixed with a solid solution and are mixed. For example, a cross section of a soldering portion is used to scan a reflection electron image (BEI) using a scanning electron microscope (SEM). It means that each metal phase can be identified by looking at it. The magnification at the time of observation is 50 times or more, for example.

In addition, the heating iron according to the present invention is characterized in that the first or second ceramic heater according to the present invention is used as a heat generating means.

(Effects of the Invention)

In the first ceramic heater according to the present invention configured as described above, the junction area between the lead wire and the brazing material can be secured by setting the range of the covering region of the brazing material to the lead member in the junction, and the stress generated by the thermal cycle can be reduced. have.

Therefore, according to the first ceramic heater according to the present invention, it is possible to form a highly reliable junction having excellent durability and to provide a ceramic heater having high durability.

Moreover, the 2nd ceramic heater which concerns on this invention contains the 2 or more types of metal as a brazing material, and exists in the state which can identify this 2 or more types of metals, and is the composition part of the lower resistance side of the 2 or more types of metal which comprise a brazing material. Since it is related to this electricity supply, it becomes possible to reduce an electrical resistance value. As a result, the amount of heat generated in the brazing filler metal can be reduced, and the reliability of joining the brazing filler metal, the metallization layer, and the lead member can be improved, and a highly durable ceramic heater can be provided.

1A is a perspective view of a ceramic heater of Embodiment 1 according to the present invention.

1B is a cross-sectional view of the ceramic heater of the first embodiment.

FIG. 2 is a cross-sectional view for illustrating a junction of the lead member 10 in the ceramic heater of the first embodiment.

3A is a perspective view showing a first step in the step of manufacturing the ceramic heater of the first embodiment.

3B is a perspective view illustrating a second step in the manufacturing step of the ceramic heater of the first embodiment.

3C is a perspective view illustrating a third step in the manufacturing step of the ceramic heater of the first embodiment.

3D is a perspective view illustrating a fourth step in the manufacturing step of the ceramic heater of the first embodiment.

4 is a perspective view of the ceramic heater 100 of Embodiment 2 according to the present invention.

5 is a schematic cross-sectional view of the soldering portion of the ceramic heater 100 shown in FIG. 4.

6 is a cross-sectional photograph showing an example of a cross section of a soldering portion of the ceramic heater 100 of the second embodiment.

FIG. 7 is an enlarged photograph of the region E shown in FIG. 6.

FIG. 8 is an enlarged photograph of the region D shown in FIG. 6.

FIG. 9 is an enlarged photograph of the region C shown in FIG. 6.

10 is a perspective view showing a heating iron according to an embodiment of the present invention.

11 is a perspective view of a conventional ceramic heater.

12 is a cross-sectional photograph of a soldering part of a conventional ceramic heater.

Description of the Related Art

1, 100: ceramic heater 2: ceramic core material,

3: ceramic sheet 4: conductor

5: lead lead portion 6: terminal take out electrode

6a: metallization layer 6b: plating layer

7: via hole 8: adhesive layer

9: ceramic body 10: lead member

11: Lead material 12: Electrode extraction part

13: void

14: Diffusion layer of lead member component to brazing filler metal

16: proximal 17 distal

18: coating height of coating area 22: ceramic core material

23: ceramic green sheet 24: conductor

25: lead lead portion 26: metallization layer

27 through hole for via hole 28 electrode extraction unit

EMBODIMENT OF THE INVENTION Hereinafter, embodiment which concerns on this invention is described, referring drawings.

Embodiment 1

1: A is a perspective view which shows typically the ceramic heater of Embodiment 1 which concerns on this invention, FIG. 1B is sectional drawing with respect to the A-A line | wire in FIG. 1A, and FIG. 2 is sectional drawing which shows the detailed structure of a junction part.

In the ceramic heater 1 of the first embodiment, as shown in FIGS. 1A and 1B, a ceramic sheet wound around a cylindrical columnar ceramic core material 2 and the ceramic core material 2 via an adhesive layer 8 is provided. (3), and the conductor 4, the lead lead-out part 5, and the electrode lead-out part 12 are embedded between the ceramic core material 2 and the ceramic sheet 3. The electrode extraction portion 12 is connected to the metallization layer 6a formed on the outside of the ceramic sheet 3. In addition, a plating layer 6b made of Ni is formed on the surface of the metallization layer 6a, and the terminal extraction electrode 6 is formed by the metallization layer 6a and the plating layer 6b. 6) and the lead member 10 are joined and fixed by the brazing filler material 11. In addition, the electrode extraction part 12 and the metallization layer 6a are connected through the via hole 7 formed under the metallization layer 6a of the ceramic sheet 3, as shown in FIG. In the ceramic heater 1 configured as described above, the conductive material 4 generates heat by energizing the metallization layer 6a via the lead member 10 to function as a heater.

And in the ceramic heater of this Embodiment 1, the coating height 18 of the coating | coating area | region which is the area | region where the brazing material 11 covers the lid member 10 is the terminal mounting electrode 6 in the lid member 10. As shown in FIG. It is characterized in that it is set in the range of 40 to 99% of the distance between the closest end closest to and the upper end farthest from the terminal mounting electrode 6 of the lead member 10.

That is, in the junction part of the terminal mounting electrode 6 and the lead member 10, the coating height 18 in the cross section of the lead member 10 is the closest end 16 which is closest to the terminal mounting electrode 6; To less than 40% of the distance from the terminal mounting electrode 6 to the far end 17 (hereinafter referred to as lead height in the present specification), the interface between the lead member 10 and the brazing filler material 11 is less than 40%. Because of the small area, the initial lead bonding strength is low and the nonuniformity increases. However, as in the first embodiment, when the coating height of the brazing filler material 11 is 40% to 99% of the lead height, since the joint area can be sufficiently secured, the initial lead bonding strength can be increased. Moreover, nonuniformity can be made small.

As shown in FIG. 2, when the lead member 10 is a wire rod having a circular cross section, the lead height is the diameter of the circular cross section of the lead member 10.

In addition, when the coating height 18 in which the brazing material 11 covers the lid member 10 is covered with the brazing material in excess of 99% of the lid height, the lead member 10 and Cracks tend to occur at the interface of the brazing filler material 11, and the lead bonding strength decreases.

In other words, if the lead member 10 is covered with the brazing filler metal in a range in which the lead height exceeds 99% of the covering height 18, the lead member 10 is caused by the linear thermal expansion difference between the lid member 10 and the brazing filler metal 11. Stress occurs at the interface between and the brazing material, and cracks occur at the interface because there is no stress evacuation site. Further, when the values of the linear thermal expansion of the lead member 10 and the brazing filler material 11 are compared, the lead member 10 < Specifically, when the lead member is subjected to the heat cycle test with the entire circumferential direction covered with the brazing filler material, cracks occur at the interface between the lead member and the brazing filler metal.

On the other hand, when the covering height 18 with respect to the lead height is set in the range of 40%-99%, a part of the lead member 10 was not covered by the brazing filler material 11, and the thermal cycle test was done. In this case, the stress caused by the thermal expansion difference between the lead member 10 and the brazing filler material 11 can be alleviated, and cracks do not occur at the interface between the lead member and the brazing filler metal by the thermal cycle test.

In the present ceramic heater, the coating height 18 is preferably in the range of 60% to 99% with respect to the lead height in order to more effectively prevent the occurrence of cracks at the interface between the lead member and the brazing material in the heat cycle test. Set to.

The range of the coating height 18 with respect to the lead height can be controlled by the wettability of the lead member 10 and the brazing material. More specifically, the material and the surface roughness of the lead member 10, the material of the brazing material, and the bonding. It is controlled by the temperature and atmosphere of the city. In the first embodiment, it is particularly preferable to control the surface roughness of the lead member 10, and by this control, the cover height can be set within a predetermined range relatively simply and surely.

Moreover, in this Embodiment 1, it is preferable that the void 13 exists in the interface of the lead member 10 and a brazing filler material. In the absence of voids at the interface between the lead member 10 and the brazing filler material, the thermal conductivity from the ceramic body 9 to the lead member 10 is good at the time of heating of the ceramic heater 1, so that the surface temperature of the lead member becomes high. However, when the void 13 is present at the interface, the thermal conductivity from the ceramic body 9 to the lead member 10 is inhibited, and the lead member surface temperature is lower than that without the void. Therefore, when the void 13 is present at the interface between the lead member 10 and the brazing filler material, the thermal stress of the joint is reduced, and the deterioration of the lead joint strength after the heat cycle test can be reduced.

As a result of confirming the size of the void 13 and the initial lead bonding strength, when the void 13 is 0.1 to 200 µm, the lead bonding strength after the initial and thermal cycle tests is high and there is almost no difference. In the case of), the lead bonding strength after the initial and thermal cycle tests is low, and in the case of the voids 13 of less than 0.1 µm, the initial lead bonding strength is high because the surface temperature of the lead member 11 is high. The lead lead strength after this fell.

Moreover, when the void 13 generate | occur | produced in the range larger than 40% of an interface, the initial lead bonding strength became low. From these things, in order to lower the surface temperature of the lead member and to increase the lead bonding strength after the initial stage and the heat cycle test, the void 13 having a diameter of 0.1 to 200 µm exists in the range of 20 to 40% of the interface. More preferred.

In addition, in this Embodiment 1, when there is no diffusion layer 14 to the brazing filler material 11 of the component of the lead member 10, the lead bonding strength after an initial stage and a heat cycle is low, and there exists a diffusion layer 14 in an interface. In this case, the initial lead bonding strength is increased. This is considered to be due to the diffusion of the components of the lead member 10 into the brazing filler material 11 so that a part of the interface is changed from physical bonding to chemical bonding, whereby the lead bonding strength is increased.

Therefore, in the present invention, it is preferable that the components of the lead member 10 are diffused into the brazing filler material 11.

In order to raise lead bonding strength effectively, 0.1-30 micrometers is preferable and, as for the distance (thickness) of the diffusion layer 14 in an interface, 3-30 micrometers is more preferable. When the diffusion layer 14 is less than 0.1 μm, the effect of improving the lead bonding strength is less. When the diffusion layer is larger than 30 μm, the components of the lead member 10 are diffused into the brazing material 11 in a large amount. 11) increases the hardness, cracks tend to occur in the brazing filler material 11 after the heat cycle test, there is a risk of lowering the lead bonding strength.

In addition, the arithmetic mean surface roughness (Ra) on the surface of the lead member 10 is in the range of 0.05 to 5 μm in order to stably produce the diffusion layer 14 and to obtain an effective anchoring effect to increase the lead bonding strength. It is preferable. If the arithmetic mean surface roughness Ra on the surface of the lead member 10 is less than 0.05 µm, the diffusion layer 14 may only be produced at 0.05 µm, resulting in little effect of improving the lead bonding strength after the heat cycle. If the arithmetic mean surface roughness Ra is greater than 5 µm, when the lead bonding strength after the heat cycle is measured, cracks may develop from the lead surface due to the heat cycle and lead wire breakage may occur.

Next, the manufacturing method of the ceramic heater 1 of Embodiment 1 is demonstrated.

When manufacturing the ceramic heater 1, the method including the process shown to FIG. 3A-FIG. 3D is used.

First, after the ceramic green sheet 23 is produced, the through hole 27 for the via hole is formed in the ceramic green sheet 23 (see FIG. 3A).

Subsequently, after filling the through paste 27 with a conductor paste, a conductor paste layer consisting of the conductor 24 and the lead lead-out portion 25 is formed and dried (see FIG. 3B).

Subsequently, the ceramic green sheet 23 is inverted to form a conductor paste layer serving as the metallization layer 26 on the rear surface thereof (see FIG. 3C).

The ceramic green sheet 23 is wound around the ceramic core 22 to be inverted once again, thereby producing a product formed of a raw material before sintering (see FIG. 3D).

The ceramic body 9 is obtained by baking the molded product thus formed in a reducing atmosphere at 1500 to 1650 ° C., and then a plating layer 6b made of Ni on the surface of the metallization layer 6a as shown in FIG. 1. After the formation, the ceramic heater 1 is obtained by fixing the lead member 10 with the brazing filler material 11.

As the material of the ceramic heater 1, it is possible to use alumina, silicon nitride, aluminum nitride, silicon carbide, mullite and the like.

For example, as alumina, those composed of 88 to 95% by weight of Al ₂ O ₃ , 2 to 7% by weight of SiO ₂ , 0.5 to 3% by weight of CaO, 0.5 to 3% by weight of MgO, and 0 to 3% by weight of ZrO ₂ can be used. have. If the content of Al ₂ O ₃ is less than this, the glass quality increases, which is not preferable because the migration during energization becomes large. On the contrary, when the Al ₂ O ₃ content is increased from this, the amount of glass diffused in the metal layer of the heat generating resistor 4 to be incorporated decreases, which is not preferable because the durability of the ceramic heater 1 is degraded.

Examples of silicon nitride, Si ₃ N ₄ 85 ~ 95 wt%, rare earth element oxides 2-12% by weight, such as Y ₂ O ₃ or _{Yb 2 O 3, Er 2 O} 3, Al 2 O 3 0.3 ~ 2.0% by weight, in which in addition it is possible to use that as the oxygen-containing SiO ₂ in terms of 0.5 to 3% by weight. As the aluminum nitride, AlN 85 ~ 97% by weight, Y ₂ O ₃ or Yb ₂ O _3, Er ₂ rare earth element oxide 2-8% by weight, such as O _3, CaO 0 ~ 5 wt%, the oxygen Al as an impurity thereto with ₂ O ₃ conversion, it is possible to use in that it contains 0 to 1% by weight. Examples of mullite, it is possible to use that with Al ₂ O ₃ 58 ~ 75% by weight, SiO ₂ 25 ~ 42% by weight, consisting of unavoidable impurities less than 1% by weight.

In addition, the shape of the ceramic heater 1 may be a plate-shaped thing in addition to a cylinder and cylinder shape.

The ceramic heater of this invention is not limited to these, A various change is possible as long as it is a range which does not deviate from the summary of this invention.

Embodiment 2 Fig.

Next, the ceramic heater 100 of Embodiment 2 which concerns on this invention is demonstrated, referring drawings.

The ceramic heater 100 of this Embodiment 2 shown in FIG. 4 and FIG. 5 is comprised by carrying out the conductor 4 in the inside of the ceramic base 9 like Embodiment 1, and to the surface of the ceramic base 9 The metallization layer 6a connected to the electrode extraction unit 12 is formed on the extending electrode extraction unit 12, and the lead member (6) is provided on the terminal mounting electrode 6 constituted by the metalization layer 6a. 10) has a structure in which the brazing material 11 is soldered. In addition, the metallization layer 6a is provided with a plating layer as needed (not shown), and the terminal mounting electrode 6 is formed by the metallization layer 6a and the plating layer.

In addition, the ceramic base 9 produces a green sheet (part after which baking becomes the sheet | seat 3) by the doctor blade method, for example, and produces the molded object which becomes the cylindrical ceramic core material 2 by the extrusion molding method. And by integrating them. As the material of the ceramic substrate 9, oxide ceramics such as alumina, mullite, posterite, and non-oxide ceramics such as silicon nitride and aluminum nitride can be used. Among them, oxide ceramics are preferable. For example, in the case of using alumina ceramics as the material of the ceramic substrate 9, 88 to 95% by weight of Al ₂ O ₃ , 2 to 7% by weight of SiO ₂ , 0.5 to 3% by weight of CaO, and 0.5 to 3% by weight of MgO %, the composition consisting of ZrO ₂ 1 ~ 3% by weight is employed. Moreover, it is not limited to alumina ceramics, Silicon nitride ceramics, aluminum nitride ceramics, silicon carbide ceramics, etc. can also be employ | adopted.

At this time, the conductor 4 is printed on the green sheet by the screen printing method, and the electrode extraction portion 12 is formed in the through hole previously formed by punching or the like at a predetermined position on the green sheet. The materials of the conductor 4 and the electrode extraction portion 12 are mainly composed of W, Mo, and Re, and alloys thereof, or metal silicides such as TiN and WC, and metal carbide are added. It is preferable that the conductor 4 and the electrode extraction portion 12 adjust these materials so that the resistance of the conductor 4 becomes high and the resistance of the electrode extraction portion 12 is low, and screen-prints them respectively.

Here, bridge the step height between the green sheet and the conductor (4), in order to close contact with the green sheet to an article having a cylindrical shape, composed mainly of Al ₂ O ₃ on conductor 4, and that the addition of SiO _2, MgO, etc. It is preferable to apply | coat a binder and adding what was made into paste form with the organic solvent by screen printing etc.

And the integrated molded object can obtain a desired sintered compact by baking in 1500 degreeC-1650 degreeC reducing atmosphere.

The paste which has W as a main component is apply | coated to the electrode extraction part 12 of the obtained sintered compact, it bakes in vacuum, and the metallization layer 6a is formed. As a material of the metallization layer 6a, it is preferable to contain what consists of W, Mo, Re, and these alloy which are high melting-point metals as electroconductive powder. About the thickness of the metallization layer 6a, it is preferable to set it as 10 micrometers or more. If the thickness is less than 10 mu m, the adhesion strength with the ceramic base 9 of the electrode extraction section 4 is low, and thus the durability of the tensile strength of the lead member 10 with respect to the thermal cycle in use decreases, which is not preferable. More preferably, the thickness is preferably 15 µm or more, ideally 20 µm or more. The reason why the thickness of the metallization layer 6a affects the tensile strength of the lead member 10 is that the metallization layer 6a is a porous sintered body of a high melting point metal made of W, Mo, Re, and the like. This is because the grain boundary glass component diffuses from the ceramic base 9, and the strength increases due to this anchor effect. Therefore, as the thickness of the metallization layer 6a increases, the tensile strength of the bonded lead member 10 increases.

After the metallization layer 6a is formed, the metallization layer 6a may be plated, and the plating is preferably made of Ni as a main component.

The lead member 10 is attached to the metallization layer 6a by vacuum soldering.

As a material of the lead member 10, it is preferable to use Ni-type, Fe-Ni-type alloy etc. with favorable heat resistance. This is because the heat transfer from the conductor 4 may cause the temperature of the lead member 10 to rise during use, resulting in deterioration. Especially, when Ni or Fe-Ni alloy is used as a material of the lead member 10, it is preferable to make the average grain size into 400 micrometers or less. When the average particle diameter exceeds 400 µm, it is not preferable because the lead member near the soldering portion is fatigued and cracks due to vibration and thermal cycle during use. For other materials, for example, when the particle diameter of the lead member 10 is larger than the thickness of the lead member 10, cracks are generated due to stress concentration on particles near the boundary between the lead material 11 and the lead member 10. Not desirable In order to reduce the average grain size of the lead member 10 to 400 µm or less, the temperature at the time of soldering may be lowered as much as possible and the processing time may be shortened.

The feature of the present invention lies in the structure of the brazing filler material 11. That is, as shown in FIGS. 6-9, a brazing filler metal contains two or more types of metals, Preferably two types of metals are provided, and it has a structure where the metal exists as a stain | difference or a scattering structure. Here, in this specification, "it exists as a stain" and "disperse" means that these two or more types of metal exist in the state which can respectively identify using a microscope etc., for example. 6 has shown by the example which used the lead member 10a which has a rectangular cross section. In addition, it is preferable that two or more metal which becomes a spot form is selected from the elements of at least group 10 (Ni, Pd, Pt etc.) or group 11 (Cu, Ag, Au etc.) as a main component. This is because the elements of Groups 10 and 11 are difficult to form a uniform phase since the diffusion coefficient is relatively small and the diffusion of the metal is suppressed, and also because the intrinsic electrical resistance is small and the conductivity is excellent.

As such a brazing material 11, although Ag-Cu solder, Au-Cu solder, etc. are mentioned, Ag-Cu solder is more preferable.

In this way, after soldering the lead member 10 to the metallization layer 6a, in order to present or scatter two or more kinds of metals (eg, Ag and Cu) as stains in the brazing filler metal 11, It is necessary to adjust the holding time during soldering. For example, when using BAg-8 (JIS Z3261) in Ag-Cu solder, the melting time (melting point) of BAg-8 is about 780 ° C, so the holding time is 5 to 40 minutes from 780 ° C to 800 ° C. It is preferable to set it as this, and by setting in this range, Ag and Cu can be existed or scattered in the inside of the brazing filler material 11 as a stain.

When the brazing filler metal 11 made of Ag and Cu is kept at the soldering temperature for 60 minutes or more, the diffusion occurs, and Ag and Cu tend to be uniformly melted alloys. When melted uniformly, the resistance value inside the brazing filler material becomes high compared with the staining structure capable of selectively energizing Ag having a lower resistance value, and hence the heat generation inside the brazing filler metal causes problems in bonding strength after durability. Remains. For this reason, in order to form a staining structure of Ag and Cu in the brazing filler material, it is preferable that the holding time at the soldering temperature is less than 60 minutes. In addition, the holding time at the said brazing temperature requires at least 5 minutes for sufficient melting of a brazing filler metal.

Conventionally, since the holding time was not adjusted and moved out of the above range, it was melted uniformly. FIG. 12 is a sectional photograph showing a soldering portion made of a brazing filler material 111 in the ceramic heater shown in FIG. 11. As the brazing filler metal 111, an brazing filler metal of Ag-Cu or Au-Cu system composed of two or more metals is used. As shown in FIG. 12, the cross section of the brazing filler material after soldering exists as a uniform metal without segregation of the metal composition to be constituted. On the other hand, in the present invention, the staining structure can be obtained by adjusting the holding time within the above range and lowering it below the soldering temperature before uniformly melting.

In order to form Ag and Cu staining structures in the brazing filler metal, it is preferable that the holding time at the soldering temperature is less than 60 minutes, and then the Ag content is set to 60 to 90% by weight, more preferably the Ag content is 70%. It is good to set it as -75 weight%. As a result, the melting temperature of the Ag-Cu solder is close to the process point (the temperature at which Ag and Cu melt together and does not exist as a solid), and the temperature at which Ag and Cu become liquid to each other is lowered. Can be lowered, and the residual stress after soldering is also reduced.

In this way, since the stain structure is formed inside the brazing filler metal 11, when the ceramic heater 100 is powered from the lead member 10, it is selectively energized to the Ag side having a lower resistance value, so that the resistance of the brazing filler material 11 is reduced. Is reduced, the temperature rise of the brazing filler material 11 is suppressed, and the reliability of joining improves.

6 is an enlarged photograph of the region E (near the interface between the brazing material and the metallization layer) in FIG. As shown in FIG. 9, which is an enlarged photograph of the region C (near the interface between the brazing filler material and the lead member) in FIG. 6, the interface between the brazing filler material 11 and the metallization layer 6a, and the brazing filler material 11 and the lead member 10, respectively. At a portion adjacent to at least one of the interfaces, it is preferable that the Cu layer 6c is formed in the brazing filler material 11 made of a metal layer having a Young's modulus of 180 kPa or less, for example, Ag and Cu, not in the shape of a stain. Since the Cu layer 6c adjacent to the interface between the brazing filler metal 11 and the metallization layer 6a functions as a stress relaxation layer with respect to the residual stress after soldering, the residual stress of this portion is reduced, and The bonding strength of the lead member 7 is improved, and the bonding strength after the durability is improved.

In order to form this Cu layer 6c, it is effective to apply Cu plating to the part where the metallization layer 6a and the lead member 10 contact the brazing filler material 11 by soldering beforehand. In Ag and Cu, since Cu has a small surface tension, Cu is likely to be selectively wetted at a portion where the brazing filler material 11 melts and contacts at the time of soldering. Using this, the Cu layer 6c can be formed in the site | part adjacent to the interface with the metallizing layer 6a which contacts a brazing filler metal, and a lead member.

And this Cu layer 6c has an unevenness | corrugation on the opposite side to the interface with the metallization layer 6a, It is preferable that the thickness of this convex part is 10 micrometers or less, and the thickness of the whole Cu layer 6c containing the convex part is included. It is preferable that it is 20 micrometers or less. The Cu layer 6c forms irregularities at the interface with the dissimilar material in contact with this, and because the irregularities function as a stress relaxation layer, the bonding strength after durability is improved.

In addition, although the uneven surface of Cu layer 6c was demonstrated here as a preferable example, this invention is not limited to Cu, It has a convex part whose height is 10 micrometers or less, and the thickness of the whole layer containing the said convex part. Even when a metal layer other than Cu having a thickness of 20 µm or less is present at the interface, the adhesion strength at the interface can be improved, and the reliability and durability can be improved.

However, when the thickness of the convex portion of the Cu layer is 10 µm or more and the thickness including the convex portion is 20 µm or more, the adhesion strength of the brazing filler material is not preferable. In this case, it is preferable that the holding time at the melting temperature of the brazing filler is 5 to 20 minutes.

Although the metallizing layer 6a is baked in the vacuum in the ceramic base 9, in order to reduce the residual stress by the thermal expansion difference with the ceramic base 9, it is preferable to use the electrically-conductive material with small thermal expansion rate. As for the main component of the metallization layer 6a, it is more preferable that it is ^{5.5x10 <-6>} / degreeC or less in terms of thermal expansion coefficient. Specifically, it is preferable to have W or Mo having the above physical properties as a main component. Thereby, the residual stress at the time of baking of the metallization layer 6a which arises at the interface of the ceramic base 9 and the metallization layer 6a is alleviated. In other words, the diffusion of such metal into the brazing material reduces the thermal expansion coefficient of the brazing material, reduces the residual stress after solder generated at the interface with the metallization layer, and improves the reliability of joining the electrode extraction portion, the brazing material and the lead member. It can improve and the reliability and durability of a ceramic heater can be improved more.

However, in the metallization layer 6a and the brazing filler metal 11, a large residual stress occurs after soldering because the difference in thermal expansion rate is very large. Therefore, it is necessary to reduce the thermal expansion rate of the brazing filler material. In order to reduce the thermal expansion rate of the brazing material, the main component of the metallization layer 6a having a low thermal expansion rate may be diffused in the brazing material. This is possible by performing heat treatment after soldering. It is preferable to perform this heat processing below the melting temperature of a lead material in a reducing atmosphere containing hydrogen gas etc., and it is more preferable to carry out at 700 degreeC-750 degreeC. By this heat treatment, a metal or an alloy having a thermal expansion rate of 5.5 × 10 ⁻⁶ / ° C. or less is diffused in the brazing material, the thermal expansion rate of the brazing material is reduced, and the strength after the durability of the soldered portion is improved.

Moreover, it is preferable to form the plating layer which consists of Ni on the surface of the brazing filler material 11 in order to protect the brazing filler material 11 from high temperature durability improvement and corrosion. In order to make this Ni plating layer function as a protective layer, the particle diameter of the crystal | crystallization which comprises a plating layer should just be 10 micrometers or less, and it can exist as a dense and dense plating layer on the surface of a soldering part. If the particle diameter is 5 占 퐉 or less, the surface plating layer is further densified and Ni can be diffused into the brazing filler material 11. Since Ni has a Young's modulus of 250 MPa, Ni diffused into the brazing material 11 increases the hardness of the brazing material 11, so that the strength inside the brazing material 11 is improved. It is possible to improve the initial bonding strength with the lead material and the lead member and the bonding strength after durability. As a result, the reliability and durability of the ceramic heater can be improved.

As the plating layer, it is preferable to use a boron-based electroless Ni plating. The electroless plating can be coated with a phosphorus-based electroless plating layer in addition to the boron-based electroless plating. However, when there is a possibility that it can be used in a high temperature environment, boron-based electroless Ni plating is generally performed.

10 is a perspective view showing an example of a heating iron using the ceramic heater 1 or the ceramic heater 100 of the present invention. This heating iron inserts hair between the arms 32 of the tip, presses the handle 31 and pressurizes the hair while heating the hair. The ceramic heater 1 or the ceramic heater 100 is inserted into the arm 32, and the metal plate 33 such as aluminum, the metal plate coated with the surface, the ceramic plate, etc. are placed at the portion in direct contact with the hair. It is installed. The outer side of the arm 32 has a structure in which a heat-resistant plastic cover is attached to prevent burns.

(Example 1)

By the method shown next, the ceramic heater of this invention was produced.

First, alumina was used as a main component, and a raw material containing 6 wt% SiO ₂ , 2 wt% MgO, 2 wt% CaO, and 1.5 wt% ZrO ₂ was prepared as a sintering aid. Using this prepared raw material, the ceramic core 2 and the ceramic green sheet 23 of 800 micrometers in thickness were prepared by the extrusion molding and the tape casting method.

Next, a conductor 24 made of tungsten (W), a lead lead-out portion 25 and an electrode lead-out portion 28 were printed on one main surface of the ceramic green sheet 23. Then, the metallization layer 26 was printed on the rear surface of the end of the electrode extraction portion 28, and through-holes for via holes were formed in the metallization layer 26. In addition, the via hole 7 was formed by filling a paste made of tungsten (W) into the through hole to connect the electrode extraction portion 28 and the metallization layer 26.

The raw ceramic body 9 thus prepared was calcined and sintered at 1600 ° C. in a reducing atmosphere, and 5 µm of the plating layer 6b was formed on the surface of the metallization layer 6a by electroless plating.

Although the lead member 10 is soldered on the terminal mounting electrode 6 of the sample obtained as mentioned above, in this Example 1, the amount of the brazing material 11 which consists of Ag solder is changed, and joining of the lead member 10 is carried out. And the evaluation height was produced in the range where the coating height 18 of the brazing filler metal on the surface of the lead member 10 was 20 to 100% of the lead height. And about these samples for evaluation, the lead bonding strength of the initial stage, the thermal bond test (25 degreeC-3 minutes-400 degreeC-3 minutes), the lead bonding strength after 3,000 cycle tests, and the crack generation rate of an interface were confirmed, respectively. .

The lead bonding strength was measured by pulling the lead member 10 in a direction perpendicular to the terminal electrode 6.

Table 1 shows the result of determining the coverage area 18 on the surface of the lead member 10, the initial lead bonding strength, and the lead bonding strength after the heat cycle test (3000 cycles).

No. Sheath Height to Lead Height Bond strength (N) Generation of cracks at the interface Judgment Early After heat cycle test One 20 60 31 none × 2 40 109 57 none ○ 3 60 118 61 none ◎ 4 80 120 63 none ◎ 5 99 123 62 none ◎ 6 100 124 29 has exist ×

No. 1 and 6 are outside the scope of the present invention. In addition, the data after the heat cycle test in a table | surface is data after repeating a heat cycle test 3000 cycles. In addition, the value of "the coating height with respect to the lead height" in Table 1 is the value which measured the part with the highest coating height with respect to the lead height in the longitudinal direction of a lead member.

The initial lead bonding strength was 85 N or more, and the lead bonding strength after the heat cycle test was determined to be 35 to 50 △, 50 to 60 N for ,, and 60 N or more for ◎.

As is apparent from Table 1, the coverage area 18 on the surface of the lead member 10 of Nos. 2 to 5 within the range of the first embodiment of the present invention is 40 to 99%. The average value of the lead joint strength after the heat cycle test was high and good results were obtained. Especially, very good result was obtained that the coverage area | region 18 on the surface of the lead member 10 of Nos. 3-5 was 60 to 99%.

However, when the coverage area 18 on the surface of the lead member 10 of No. 1 as a comparative example is 20%, the lead bonding strength after initial and thermal cycle tests is low, and the lead member 10 of No. 6 is reduced. 100% of the coating region 18 on the surface was high in initial lead bonding strength, but was lower in lead bonding strength after the thermal cycle test.

40% to 99% of the coverage area 18 on the surface of the lead members 10 of Nos. 2 to 5, which is the first embodiment of the present invention, is less deteriorated in lead bonding strength because there is no crack at the interface. I think I lost.

However, when the coverage area 18 of No. 6 as a comparative example is 100%, it is considered that the lead bonding strength is also low because cracks are generated at the interface.

The crack which generate | occur | produces in an interface is considered to generate | occur | produce by the difference of the thermal expansion rate of the lead member 10 and the brazing filler material 11. Therefore, it is considered that 100% of the covering region 18 is difficult to relieve the stress caused by the thermal expansion difference, and cracks easily occur at the interface.

In addition, the relationship between the void occupancy of the void 13 and the interface generated at the interface, the lead bonding strength after the initial stage and the heat cycle test, and the surface temperature of the lead member when the ceramic heater was heated at 800 ° C was confirmed. Table 2 shows the results of the initial lead bonding strength of 85 N or more, the lead bonding strength after heat cycle test of 35 to 50 N, △, 50 to 60 N of ○, and 60 N or more.

No. Share of voids at interface (%) Size of void (μm) Bond strength (N) Surface temperature of lead member at 800 ℃ heating (℃) Judgment Early After thermal cycle test (after 3000 cycles) 7 0 0 121 48 157 △ 8 One 250 110 47 151 △ 9 One 200 119 56 146 ○ 10 One 50 125 57 143 ○ 11 One 0.1 121 59 141 ○ 12 20 250 98 45 144 △ 13 20 200 112 62 136 ◎ 14 20 50 119 65 135 ◎ 15 20 0.1 117 63 135 ◎ 16 40 250 94 47 133 △ 17 40 200 104 62 132 ◎ 18 40 50 110 64 125 ◎ 19 40 0.1 108 66 126 ◎ 20 50 250 87 41 130 △ 21 50 200 90 43 127 △ 22 50 50 92 43 120 △ 23 50 0.1 93 47 119 △

Either sample is 60% coating height.

The size of the void 13 which arises in the interface of Nos. 13-15 and 17-19 which is Example 1 of this invention is 0.1-200 micrometers, and the occupancy rate of the void 13 of an interface is 20 to 40%. A very good result was obtained with a lead bonding strength of 60 N or more after the thermal cycle test.

In addition, the range of the void 13 which generate | occur | produces in the interface of Nos. 9-11 is 0.1-200 micrometers, and the occupancy rate of the void 13 of an interface is 0.1-20%, and the lead bond strength after a thermal cycling test is 50-. Good results were obtained with 60N. This is considered to be because the void 13 at the interface inhibits the heat conduction from the ceramic body 9 and the lead member surface temperature is lowered.

However, since No. 7 has a high lead member surface temperature, the lead bonding strength after the thermal cycle test decreases, and Nos. 20 to 23 have a large occupancy rate of 50% of the void 13 in the interface. Is lower than -20 DEG C, but the bonding strength is low, and No. 12 and 16 are considered to have low lead bonding strength because the size of the void 13 is 250 mu m.

In addition, a sample in which the distance of the diffusion layer 14 was changed from the interface by changing the junction temperature and time was prepared, and the lead bonding strength after the initial stage and the heat cycle test was measured, and the initial lead bonding strength was 85 N or more and after the thermal cycle test. Table 3 shows the results of determining that the lead bonding strength was 35 to 50 N for △, 50 to 60 N for ○ and 60 N or more.

No. Height of Diffusion Layer (㎛) Bond strength (N) Judgment Early After heat cycle 24 0 94 41 △ 25 0.1 112 52 ○ 26 3 114 63 ◎ 27 5 118 66 ◎ 28 15 120 62 ◎ 29 30 119 65 ◎ 30 45 118 38 △

The range where the distance of the diffusion layer 14 from the interface of Nos. 26 to 29, which is Example 1 of the present invention, was 3 to 30 µm, the lead bonding strength after the heat cycle test was higher than 60 N, and very good results were obtained. . Moreover, when the distance of the diffusion layer 14 from the interface of No. 25 was 0.1 micrometer, the lead bonding strength after a thermal cycling test became 50-60N, and the favorable result was obtained. This is considered to be because the lead bonding strength is increased because the interface of the lead member is diffused into the brazing material and the interface is changed from physical bonding to chemical bonding.

However, No. 24 having no diffusion layer has a low lead bonding strength after initial and thermal cycle tests, and No. 30 having a diffusion layer 14 of 45 μm diffuses a large amount of components of the lead member into the brazing filler material 11. As a result, the hardness of the brazing filler metal 11 became high, and cracks occurred in the brazing filler material 11 after the heat cycle test, and the lead bonding strength was lowered.

In addition, the arithmetic mean surface roughness (Ra) of the lead member 10 used for the bonding and the lead bonding strength after the initial and thermal cycle tests were measured. The initial lead bonding strength was 85 N or more, and the lead bonding strength after the thermal cycle test was 35. Table 4 shows the results of the determination of? To 50N of?, 50 to 60N of?, And of 60N or more.

No. Arithmetic Average Surface Roughness Ra (㎛) Thickness of Diffusion Layer (㎛) Bond strength (N) Judgment Early After heat cycle 31 0.01 0.05 104 43 △ 32 0.05 3 116 63 ◎ 33 0.5 9 123 62 ◎ 34 One 10 119 65 ◎ 35 2 9 123 63 ◎ 36 3 9 115 62 ◎ 37 5 12 117 61 ◎ 38 7 9 119 36 (lead broken) △

The heat cycle is data after 3000 cycles of the thermal cycle test.

The arithmetic mean surface roughness (Ra) of the lead member 10 of No. 32-37 which is Example 1 of this invention is 0.05-5 micrometers, and the lead bonding strength after a heat cycle test is 60N or more, and it is very favorable. The result was obtained. As the arithmetic mean surface roughness Ra of the lead member 10 increases from the evaluation result, the diffusion layer 14 tends to be easily formed from the interface, and the arithmetic mean surface roughness Ra of the lead member 10 is increased. As becomes larger, the lead bonding strength after the heat cycle test tends to be increased by the anchor effect.

However, in No. 31, the lead bond strength after the thermal cycle test was not obtained because a sufficient anchoring effect was not obtained because the distance of the diffusion layer 14 from the interface was small and the arithmetic mean surface roughness Ra of the lead member 10 was small. It is considered to be low, and No. 38 shows that the distance of the diffusion layer from the interface is 9 µm and the lead bonding strength is sufficient, but since the arithmetic mean surface roughness Ra of the lid member 10 is 7 µm, Since cracks advanced from the surface of the lead member 10 by this, it was broken in the mode of lead disconnection at 36N.

(Example 2)

Al ₂ O ₃ is the main component, SiO ₂ , CaO, MgO, ZrO ₂ is adjusted to within 10% by weight in total, a ceramic sheet is produced by the doctor blade method, and a paste made of W is formed on the surface of the ceramic sheet. It printed and the conductor 4 and the electrode extraction part 12 were formed.

Furthermore, by the extrusion molding method, a cylindrical shaped body was produced, the ceramic sheet printed with the conductors 4 was wound around the cylindrical shaped body, and brought into close contact with each other, fired in a reducing atmosphere at 1600 ° C, and the ceramic heaters 100 were each 20. Ready.

Then, electroless Ni plating having a thickness of 5 µm was applied to the surface of the electrode extraction unit 12, and a paste containing W as a main component was applied to the electrode extraction unit 12 and baked in a vacuum furnace.

Thereafter, a Ni wire having a diameter of 1.0 mm was soldered using Ag-Cu solder (BAg-8) as the lead member.

At this time, soldering was performed by dividing the soldering conditions into soldering temperatures of 780 ° C, 800 ° C, 820 ° C, and holding time for 5 minutes, 10 minutes, 40 minutes, and 60 minutes, respectively.

In order to confirm durability in continuous use, the initial tensile strength and the tensile strength after continuous energizing at 400 ° C. for 800 hours were measured. In the tensile test, the end of the lead member 4 was pulled in a direction perpendicular to the main surface of the ceramic heater 100 to measure its peel strength. In addition, the section of each lot was observed with the electron microscope, and the structure inside the brazing filler material was confirmed. The results are shown in Table 5.

No. Soldering Temperature (℃) Retention time (minutes) Initial tensile strength (N) Tensile strength after durability (N) Stain inside Layer of Lead Material Interface * 39 780 5 340 178 none Ag / Cu alloy 40 780 10 345 303 has exist Cu 41 780 40 342 311 has exist Cu * 42 780 60 339 188 none Ag / Cu alloy * 43 800 5 338 191 none Ag / Cu alloy 44 800 10 341 307 has exist Cu 45 800 40 345 305 has exist Cu * 46 800 60 337 183 none Ag / Cu alloy * 47 820 5 344 188 none Ag / Cu alloy 48 820 10 348 302 has exist Cu 49 820 40 339 307 has exist Cu * 50 820 60 343 173 none Ag / Cu alloy

Here, the layer of a brazing filler metal interface means the layer in the interface between a metallizing layer and a brazing filler material, and the interface between a lead member and a brazing filler metal.

In addition, the sample of * mark is outside the scope of the present invention.

As can be seen from Table 5, No. 39, 42, 43, 46, 47, and 50, in which the staining structure as shown in Figs. 7 to 9, were not found inside the brazing filler material, the tensile strength after the endurance test was 200 N. It fell below. On the other hand, No. 40, 41, 44, 45, 48, and 49 in which the staining structure as shown in Figs.

Claims (12)

A ceramic body having a built-in conductor and a metallization layer conductive with the conductor, and a lead member bonded to the metallization layer with a lead material, The covering area covering the lead member of the brazing filler material is set in the range of 40 to 99% of the distance from the closest end closest to the metallization layer in the lead member and the uppermost distance from the metallization layer. Arithmetic mean surface roughness Ra of said lead member is 0.05-5 micrometers, The ceramic heater characterized by the above-mentioned. The ceramic heater according to claim 1, wherein a void having a diameter of 0.1 to 200 µm exists at an interface between the lead member and the brazing filler metal. The ceramic heater according to claim 2, wherein a contact area between the lead member and the brazing filler material is 60 to 99% of the entire interface by the voids. The ceramic heater according to claim 2, wherein a component of the lead member is diffused into the brazing filler material, and its diffusion depth is in the range of 0.1 µm to 30 µm from the interface. delete A ceramic body having a built-in conductor and a metallization layer conductive with the conductor, and a lead member bonded to the metallization layer with a lead material, The brazing filler metal contains two or more kinds of metals, and the two or more kinds of metals are present in an identifiable state in the brazing filler material, respectively. One of the two or more kinds of metals is a first metal having a Young's modulus of 180 GPa or less, and the first metal is at the boundary of at least one of the boundary between the solder and the lead member and the boundary between the solder and the metallization layer. Ceramic heater. The ceramic heater according to claim 6, wherein the two or more kinds of metals are selected from the group consisting of Group 10 metals and Group 11 metals of the periodic table. delete The said 1st metal has an unevenness | corrugation on the opposite side to the interface with the said lead member or the said metallizing layer, The height of the convex part among the unevenness | corrugations is 10 micrometers or less, and includes the said convex part. A ceramic heater, wherein the thickness of the whole layer is 20 µm or less. The ceramic heater according to claim 6, wherein the metallization layer contains a metal having a thermal expansion coefficient of 5.5x10 ^-6 / 占 폚 or less as a main component, and the metal is diffused in the brazing filler metal. The ceramic heater according to claim 6, wherein Ni is diffused in the brazing material. A heating iron using the ceramic heater according to any one of claims 1 to 4, 6 to 7, and 9 to 11 as a heat generating means.

Images