JP6749052B2 - Welding end tab - Google Patents

Description

The present disclosure relates to welding end tabs.

Conventionally, when welding members to be welded together, the relative positions of the members to be welded are fixed, and in order to realize a good weld state without interruption by suppressing the dripping of molten metal caused by welding, End tabs are used.

As such a welding end tab, Patent Document 1 proposes a welding auxiliary agent (tab) made of ceramics having low adhesion to molten metal.

JP-A-4-351297

In welding of members to be welded, if air bubbles are mixed into the molten metal in the welded joint, the strength of the welded joint may be reduced. In addition, when such bubbles are removed during the welding work in order to maintain the strength of the welded joint, there is a problem that the welding work becomes complicated. Therefore, there is a demand for a welding end tab capable of joining members to be welded together without complicated work. The welding end tabs of the present disclosure have been devised in view of the above requirements.

The welding end tab of the present disclosure has at least a facing surface that faces the member to be welded. Welding end-tab is made of porous ceramics mainly the silicofluoride-containing nitride, the opposing surface comprises a plurality of first open pores, wherein the facing surface, Ru der 40 atomic% or more carbon content.

The welding end tab of the present disclosure can join the members to be welded to each other without complicated work.

It is a perspective view which shows an example of the welding operation using the welding end tab of this indication. It is a perspective view which shows the other example of the welding operation using the welding end tab of this indication. It is a schematic diagram which shows the 1st open hole in the opposing surface of the welding end tab of this indication. It is a schematic diagram which expands and shows a 1st open hole.

Hereinafter, a plurality of embodiments of a welding end tab of the present disclosure will be described in detail with reference to the drawings. However, in all the drawings of the present specification, the same reference numerals are given to the same portions unless the confusion occurs, and the description thereof will be omitted as appropriate.

FIG. 1 is a perspective view showing an example of a welding operation using the welding end tab of the present disclosure. Figure 1
The welding end tab 10 of the example shown in is used for welding the respective end surfaces of the first metal member 1 and the second metal member 2, which are the members to be welded. In the example shown in FIG. 1, all the members to be welded are plate-shaped, but the shape of the members to be welded is not limited to this.

The welding end tab 10 of the present disclosure is used for fixing the relative positions of the members to be welded during welding and for preventing the molten metal from leaking to the outside. In the example shown in FIG. 1, two welding end tabs 10 are arranged. The two welding end tabs 10 are arranged in a portion where the end surface of the first metal member 1 and the end surface of the second metal member 2 are welded. The two welding end tabs 10 are fixed to the respective side surfaces of the first metal member 1 and the second metal member 2 while being pressed by the clamp wire 5. As described above, the welding end tab 10 has the facing surface 10 a that faces and contacts the side surfaces of the first metal member 11 and the second metal member 2, which are the members to be welded.

In addition, FIG. 2 is a perspective view showing another example of a state of welding work using the welding end tab 10 of the present disclosure. In the example shown in FIG. 2, the welding end tab 10 is used to weld the end surface of the fourth metal member 4 which is the member to be welded to one main surface of the third metal member 3 which is the member to be welded. The fourth metal member 4 is supported by a backing plate 6 that is temporarily fixed to the third metal member 3.

The welding end tab 10 has a facing surface 10a arranged to face the member to be welded, and a portion including the facing surface 10a is made of silicon nitride, silicon carbonitride, silicon carbide, or aluminum titanate as a main component. And porous ceramics. As described above, since the welding end tab 10 is made of porous ceramics, the facing surface 10a has the plurality of first open pores 9.

Since the main component of the porous ceramics that constitutes the welding end tab 10 of the present disclosure is hard to wet the molten metal, the molten metal is unlikely to adhere to the welding end tab 10, and the welding end tab 10 and the welded member It is difficult to join. Therefore, the welding end tab 10 can be peeled off with a comparatively small force without performing an extra costly extra step such as a step of cutting the cohesive portion in order to remove the welding end tab 10.

Further, since the facing surface 10a of the welding end tab 10 is provided with the plurality of first open pores 9, bubbles mixed in the molten metal easily escape to the first open pores 9. By performing welding using the welding end tab 10 of the present disclosure, it is possible to suppress the inclusion of air bubbles into the inside of the weld metal, and therefore the welding is performed without complicated and extra work for removing the air bubbles. be able to. That is, by using the welding end tab 10, relatively strong welding can be realized in a short working time. Further, since the welding end tab 10 has a small amount of metal components fixed as described above, the welding end tab 10 can be repeatedly used without requiring extra regeneration work or the like.

Further, the welding end tab 10 may include a second open hole communicating with the first open hole 9 inside the welding end tab 10 on a surface portion different from the facing surface 10a. In this case, the bubbles that have escaped into the first open holes 9 pass through the inside of the welding end tab 10 and are discharged from the second open holes, so that the inclusion of bubbles into the inside of the weld metal can be further suppressed. You can Whether or not the first open hole 9 communicates with the second open hole depends on whether the air flows out from the other surface portion of the welding end tab 10 when the compressed air is sent from the first open hole 9. You can confirm by checking.

The porous ceramics that constitutes the welding end tab 10 of the present disclosure refers to ceramics having a porosity of 10% by volume or more and 50% by volume or less. The porosity of the porous ceramics can be determined by the mercury porosimetry method.

FIG. 3 is a schematic diagram showing the first open pores 9 in the facing surface 10a of the welding end tab 10 of the present embodiment. FIG. 4 is a schematic view showing the first open pores 9 of FIG. 3 in an enlarged manner. The welding end tab 10 may have first open pores 9 in the facing surface 10a, and a plurality of columnar crystals 7 of silicon nitride may be located inside the first open pores 9 so as to intersect with each other.

In the porous ceramic containing silicon nitride as a main component, the grain boundary phase 8 is more easily wetted by the molten metal than the columnar crystal 7 of silicon nitride. However, since the plurality of first open pores 9 are located so that the columnar crystals 7 of silicon nitride intersect each other, it is difficult to wet the molten metal, and the molten metal is unlikely to adhere to the welding end tab 10.

The main component in the porous ceramics means a component that occupies 70% by mass or more of the total 100% by mass of all the components constituting the porous ceramics, and particularly preferably 80% by mass or more. The component (crystal structure) that constitutes the porous ceramics may be identified by using an X-ray diffractometer (XRD). In addition, the content is calculated based on the identified crystal structure by determining the content of the metal element using an ICP (Inductively Coupled Plasma) emission spectroscopy analyzer (ICP) or a fluorescent X-ray analyzer (XRF). You can ask for it. For example, the presence of silicon nitride can be confirmed by measurement using XRD, the silicon content obtained by ICP is converted to silicon nitride, and the silicon nitride content obtained by the conversion is 70% by mass or more. If so, it can be said that silicon nitride is the main component.

Next, an example of the composition of the porous ceramics that constitutes the portion including the facing surface of the welding end tab 10 of the present disclosure will be described. This porous ceramics contains silicon nitride as a main component, and components other than silicon nitride include, for example, rare earth elements, aluminum, silicon, calcium and the like.

The porous ceramics may contain chromium, manganese, iron, copper, tungsten, molybdenum, etc. in addition to the above components, and contains a first silicide which is a silicide containing any one of these. It may be one.

When the above-mentioned first silicide is contained, the porous ceramics can be made to have a color tone with a lower brightness, so that the stain due to welding can be made inconspicuous. The first silicide is, for example, a component whose composition formula is represented by CrSi ₂ , MnSi ₂ , FeSi ₂ , CuSi ₂ , W ₅ Si ₃ (JCPDS#81-1916), MoSi _{2, and the} like. The content of chromium, manganese, iron, copper, tungsten, molybdenum constituting the first silicide is 0.02 in terms of silicide out of 100% by mass of all components constituting the porous ceramics. It is preferable that the content is at least 2% by mass.

The first silicide can be identified by measurement using XRD. Further, with regard to the respective contents of these silicides, the above respective elements obtained by XRF or ICP may be converted into silicides.

The facing surface 10a may contain carbon, and the content thereof may be 40 atomic% or more. In this case, the electrical conductivity in the facing surface 10a becomes high, and the arc can be stably generated, so that the occurrence of welding defects can be suppressed. The carbon content in the facing surface 10a can be measured using an X-ray photoelectron spectroscopy analyzer. The carbon content in the facing surface 10a is preferably 70 atomic% or less.

The facing surface 10a of the porous ceramics may have an arithmetic average roughness (Ra) of the portion excluding the first open pores 9 of, for example, 1 to 50 μm. In this case, the wettability with respect to the molten metal can be further lowered.

As a method of increasing the arithmetic mean roughness (Ra) of the welding end tab 10, a pressing/pressurizing surface side, which is a transfer surface of a mold, is formed when the powder containing silicon nitride as a main component is molded into a desired shape. The so-called electric discharge embossing method may be used, or a relatively coarse spreading powder may be spread on the shelf plate when the ceramic molded body is sintered. Further, a method of performing blasting using relatively coarse abrasive grains may be used, and the method of adjusting the arithmetic average roughness (Ra) is not particularly limited.

[Embodiment 1 of Porous Ceramics]
The porous ceramics forming the portion including the facing surface of the welding end tab 10 contains silicon nitride in an amount of 80% by mass or more, the grain boundary phase 8 contains Y ₂ SiAlO ₅ N, and 2θ= in the X-ray diffraction chart. When the peak intensity of Y ₂ SiAlO ₅ N at 32 to 33° is X and the peak intensity of silicon nitride at 2θ=33.2 to 34.2° is Y, the ratio X/Y is 0.1 or more and 0.5 or more. The following silicon nitride ceramics may be used.

When the above-mentioned configuration is satisfied, the grain boundary phase 8 contains Y ₂ SiAlO ₅ N but also an amorphous phase that bonds the silicon nitride crystal. Few. Therefore, the mechanical strength of the porous ceramics satisfying the above-mentioned configuration is relatively high.

Note that silicon nitride and Y ₂ SiAlO ₅ N can be identified using XRD or a transmission electron microscope (TEM). Further, the ratio X/Y can be obtained from the X-ray diffraction chart obtained by XRD.

Next, an example of the composition of the porous ceramics will be described. The porous ceramics contains 80 mass% or more of silicon nitride. Examples of components other than silicon nitride include yttrium (Y), aluminum (Al), and silicon (Si). Then, the content of these components, Y is _Y 2 _{O 3} 14 wt% 7 wt% or more in terms of less, Al is _Al 2 _{O 3} 5 wt% or more 2% by mass in terms of less, Si is in terms of SiO ₂ And is 0.5% by mass or more and 2% by mass or less.

Next, an example of a method for measuring the content of each component in the porous ceramics will be described. First, the oxygen content in the porous ceramics is determined by an infrared absorption method using an oxygen analyzer (EMGA-650FA manufactured by Horiba Ltd.).

Next, quantitative analysis of Y and Al is performed using ICP. Then, the quantitative values of Y and Al obtained by the quantitative analysis are converted into Y ₂ O ₃ and Al ₂ O ₃ , respectively. This makes it possible to obtain the contents when Y is converted into Y ₂ O ₃ and Al is converted into Al ₂ O ₃ . Next, the amount of oxygen required in terms of oxide is subtracted from the content of oxygen in the porous ceramics, the amount of oxygen thus subtracted is converted to SiO ₂ , and this value is calculated when Si is converted to SiO _2. Content.

[Manufacturing Method of First Embodiment of Porous Ceramics]
The welding end tab of the first embodiment can be manufactured by adding a pore-forming agent during the preparation of the slurry.

First, silicon powder (average particle size D ₅₀ =0.5 to ₁₀₀ μm) and silicon nitride powder (alpha conversion rate of 50% or more, average particle size D ₅₀ =0.5 to 10 μm), and a sintering aid. , Yttrium oxide powder (average particle size D ₅₀ =0.5 to 10 μm) and aluminum oxide powder (average particle size D ₅₀ =0.5 to 10 μm) are prepared. Then, the powder of silicon nitride and the powder of the sintering aid are mixed to obtain a first starting material. The mass ratio between the silicon powder and the silicon nitride powder is 80:20 to 90:10.

In addition, each of the yttrium oxide, aluminum oxide, and silicon dioxide powders contains yttrium oxide powder of 10.2% by mass or more and 20% by mass or less and aluminum oxide powder of 2%, based on the total 100% by mass of the first starting material. It is weighed so as to be 9.9% by mass or more and 7.3% by mass or less.

In order to obtain a porous ceramic containing a first silicide which is a silicide containing at least one of chromium, manganese, iron and copper, chromium oxide, manganese oxide, ferric oxide and copper oxide Any one kind of powder may be appropriately weighed and added to the first starting material. The added chromium oxide, manganese oxide, ferric oxide, and copper oxide powders react with silicon during firing to desorb oxygen and become a thermodynamically stable silicide, which makes porous ceramics have low brightness. Can be in color.

In order to obtain a porous ceramic containing a first silicide which is a silicide of tungsten or molybdenum, a powder of tungsten oxide or molybdenum oxide may be appropriately weighed and added to the first starting material. The added powder of tungsten oxide or molybdenum oxide reacts with silicon at the time of firing to desorb oxygen, exists as a silicide in the grain boundary phase, and allows the porous ceramics to have a color tone with low brightness.

Then, the first starting material and the like are mixed with various binders such as polyvinyl alcohol (PVA) and polyethylene glycol (PEG). At this time, a pore forming agent is added together. As the pore-forming agent, for example, a pore-forming agent such as suspension-polymerized non-crosslinking styrene polymer or styrene-acrylic copolymer can be used. The first starting material, binder, and pore-forming agent are put into, for example, a barrel mill, a rotary mill, a vibration mill, a bead mill, a sand mill, or an agitator mill, and mixed and pulverized by a wet process to obtain a slurry. Here, the addition amount of the pore-forming agent is, for example, 7 parts by mass or more and 11 parts by mass or less with respect to 100 parts by mass in total of the first starting material and the binder. Further, a thickening stabilizer, a dispersant, a pH adjuster and the like may be added.

The slurry is then spray dried using a spray dryer to granulate. Then, the granules are filled in a molding die and pressed using a uniaxial pressing method to obtain a molded product having a predetermined shape.

Next, the molded body is degreased in a nitrogen atmosphere or a vacuum atmosphere for a holding time of 15 hours or more and 48 hours or less to obtain a degreased body. The degreasing temperature at this time varies depending on the type of binder added, but is preferably 900° C. or lower, and particularly preferably 400° C. or higher and 800° C. or lower.

Next, a nitride is obtained by nitriding this degreased body at a partial pressure of nitrogen of 50 kPa to 1.1 MPa at a temperature of 1000° C. or higher and 1400° C. or lower.

Then, the nitride is baked at a nitrogen partial pressure of 50 kPa to 300 kPa at a temperature of 1640° C. or higher and lower than 1800° C. for 1 to 10 hours, and then left to cool to room temperature to weld for welding of the present embodiment. You can get the end tabs.

Further, in order to obtain a welding end tab made of porous ceramics containing Y ₂ SiAlO ₅ N in the grain boundary phase and having X/Y of 0.1 or more and 0.5 or less, a closed firing container made of silicon nitride is used. The welding end tab obtained by the method described above is placed therein, heat-treated at a temperature of 1750° C. to 1900° C. in a nitrogen atmosphere, and the temperature decreasing rate from the maximum temperature to 800° C. is 10° C./min to 11.2. It can be obtained by cooling to 0° C./min and then allowing to cool to room temperature.

[Embodiment 2 of porous ceramics]
The porous ceramics that constitutes the portion including the facing surface of the welding end tab 10 contains silicon nitride as a main component, contains oxides of calcium, aluminum, and a rare earth element, and contains a total of oxides of calcium, aluminum, and a rare earth element. Of 100 mass%, the content of calcium converted to oxide is 0.3 mass% to 1.5 mass%, and the content of aluminum converted to oxide is 14.2 mass% to 48.8 mass%. or less, with the remainder being oxides of rare earth elements, silicon nitride has an average grain size expressed by a composition formula _{Si 6-Z Al Z O Z} N 8-Z (z = 0.1~1) May be 20 μm or less (excluding 0 μm), but β-sialon may be used.

When the above-mentioned configuration is satisfied, the number of crystal grains that have grown abnormally is small, the variation in crystal grain size is small, and the bulk density of the porous ceramics is high and the rigidity is high. Can be suppressed. Further, even if the temperature of the member to be welded is high, since the number of abnormally grown crystal grains is small, the mechanical strength is hardly reduced, and the crystal symmetry of β-Si ₃ N ₄ is hardly impaired. The thermal conductivity does not easily decrease, and the thermal shock resistance can be maintained.

Here, the solid solution amount z can be calculated as follows. First, the sample was pulverized until it passed through a mesh with a particle size number of 200, and the obtained powder was a high-purity α-silicon nitride powder (Ube Industries, Ltd. E- 10 grades, aluminum content is 20 mass ppm or less) and 60 mass% are added and mixed so as to be uniform in a mortar, and an analysis range 2θ is set to 33 to 37° by a powder X-ray diffraction method, and a scanning step width is The profile intensity is measured with Cu-Kα ray (λ=1.54056Å) at 0.002°. The angle is corrected using the maximum value of the peak obtained from the angle correction sample. Then, a difference (Δ2θ ₁ ) between the average 2θ and 34.565° of the top 10 points of the peak intensity obtained every 0.002° of α(102) appearing near 2θ=34.565°, and 2θ=35. The difference (Δ2θ ₂ ) between the average 2θ of the top 10 points of the peak intensity obtained every 0.002° of α(210) appearing near .333° and 35.333° (Δ2θ ₂ ) is obtained, and the average of the differences (Δ2θ ₂ Let ₁ + Δ2θ ₂ )/2 be the correction Δ2θ.

Next, the average 2θ of the top 10 points of the peak intensity obtained every 0.002° of β(210) appearing near 2θ=36.055° is corrected by Δ2θ and the angle of β(210) of the sample is corrected. The position is (2θ _β ). Then, the peak position _{(2θ β), λ = 1.54056Å} , calculates the (hkl) = (210), are substituted into the following equation to the lattice constant of the c = c-axis lattice constant a (Å). sin ² θ _β =λ ² (h ² +hk+k ² )/(3a ² )+λ ² l ² /(4c ² ), and the lattice constant a(Å) calculated by this formula and K. H. Jack, J.; Mater. Sci. , 11 (1976) 1135-1158, Fig. The solid solution amount z can be obtained from the graph of the lattice constant a(Å)-solid solution amount z described in 13. In particular, the solid solution amount z is more preferably 0.35 or more and 0.70 or less.

Further, the average crystal grain size of β-sialon is based on JIS R 1670-2006, and a scanning electron microscope is used to set the magnification to, for example, 2000 times to 4000 times, and the surface of the porous ceramics that is broken and polished is photographed. It can be obtained from the image.

[Manufacturing Method of Embodiment 2 of Porous Ceramics]
In order to obtain the second embodiment of the porous ceramics, the second starting material may be used instead of the first starting material. As the second starting material, a powder of silicon nitride having a composition amount represented by Si _6-Z Al _Z O _Z N _8-Z and a solid solution amount z of 0.5 or less (α conversion rate of 50% or more, Powders of average particle diameter D ₅₀ =0.5 to 4 μm) and calcium oxide, aluminum oxide and oxides of rare earth elements are prepared as sintering aids. In addition, in order to obtain silicon nitride which is a β-sialon represented by the composition formula of Si _6-Z Al _Z O _Z N _8-Z (z=0.1-1), the solid solution amount z is 0.
． It is sufficient to use silicon nitride powder having a content of 05 or more and 0.5 or less.

Here, the total of each powder of calcium oxide, aluminum oxide, and oxide of a rare earth element, which are sintering aids, was 100% by mass with respect to the total of the silicon nitride powder and the total of these sintering aid powders. At times, the content may be 3% by mass or more and 19.2% by mass or less, and the content of each sintering aid may be 100% by mass with respect to the total of 100% by mass of calcium oxide, aluminum oxide and oxides of rare earth elements. Then, the content of calcium oxide and aluminum oxide may be 0.3 mass% or more and 1.5 mass% or less, 14.2 mass% or more and 48.8 mass% or less, and the balance may be an oxide of a rare earth element.

Various binders such as polyvinyl alcohol (PVA) and polyethylene glycol (PEG) are used as the second starting material, and a pore-forming agent such as suspension-polymerized non-crosslinkable styrene polymer or styrene-acrylic copolymer. At the same time, for example, a barrel mill, a rotary mill, a vibration mill, a bead mill, a sand mill, an agitator mill, or the like is put therein, and the mixture is wet mixed and pulverized to obtain a slurry, which is manufactured through the same steps as the manufacturing method of the first embodiment. You can Here, the addition amount of the pore-forming agent is, for example, 7 parts by mass or more and 11 parts by mass or less based on 100 parts by mass of the total of the second starting material and the binder.

Embodiment 3 of Porous Ceramics
Further, the porous ceramics that constitutes the portion including the facing surface of the welding end tab 10 contains silicon nitride as a main component, contains grainenite in the grain boundary phase 8, and has a grainenite at 2θ=31° to 32° in the X-ray diffraction chart. The silicon nitride ceramics may have a half-value width of the peak intensity of 0.5° or less. When the grain boundary phase 8 contains gehlenite, the amount of the amorphous phase that is easily corroded by the acid or alkali component in the grain boundary phase 8 is relatively small, so that the mechanical strength can be further increased. Further, since the amorphous phase in the grain boundary phase 8 becomes relatively smaller, it becomes more difficult to deform even when exposed to high temperature.

When the half-value width of the peak intensity of gehrenite at 2θ=31° to 32° in the X-ray diffraction chart is 0.5° or less, distortion of crystals of gehrenite becomes small, and thermal conductivity and rigidity of the porous ceramics are reduced. Both can be raised. The compositional formula of gehrenite is shown as Ca ₂ Al ₂ SiO ₇ , for example, but is not limited to the stoichiometric composition. Further, in the porous ceramic, it is preferable that magnesium and sodium are in solid solution in gehlenite. When magnesium and sodium are solid-dissolved in gehlenite, the proportion of crystals (gerhenite) in the grain boundary phase 8 is high and the proportion of amorphous phase is low, so that the deformation of the grain boundary phase 8 is suppressed. Therefore, the rigidity of the porous ceramics can be increased.

The composition formula of gehlenite magnesium and sodium are dissolved in, for _{example, ((Ca 1- (a +} b), Na a, Mg b) 2 (Al 1- (c + d), Si c, Mg d) 2 _{(Si 1- (e + f)} , Al e, Mg f) O 7) ( where it can be expressed as 0 <a + b <1,0 < c + d <1,0 <e + f <1). Further, the presence of gehlenite in the grain boundary phase 8 of the porous ceramic can be confirmed by using XRD. In addition, regarding the solid solution of magnesium and sodium in gehlenite, use a transmission electron microscope (TEM) equipped with an energy dispersive X-ray spectrometer (EDS) or a wavelength dispersive X-ray spectrometer (WDS). You can

[Manufacturing Method of Embodiment 3 of Porous Ceramics]
In order to obtain the third embodiment of the porous ceramics, the third starting material may be used instead of the first starting material and the second starting material. First, a metal silicon powder and a silicon nitride powder having a β-conversion rate of 20% or less are prepared, and (metal silicon powder)/(silicon nitride powder)
The first powder is obtained by mixing so that the mass ratio is 1 or more and 10 or less. Here, depending on the particle size of the metal silicon powder, it may cause insufficient nitriding and insufficient sintering. Therefore, the metal silicon powder is accumulated when the total volume of the particle size distribution curve is 100%. The particle diameter (D ₉₀ ) of which volume is 90% is 10 μm or less, preferably 6 μm or less.

Further, as a sintering aid, a second powder obtained by weighing the powder of magnesium aluminate and the powder of the first metal compound is obtained.

Here, when the total of the first powder and the second powder is 100% by mass, the powder weighed so that the second powder is 10% by mass or more and 23% by mass or less is the third starting material. The first metal compound is aluminum oxide, silicon dioxide, calcium carbonate, or the like. Further, instead of the powder of magnesium aluminate, powder of magnesium hydroxide, magnesium oxide, magnesium carbonate or the like may be used. These mixed powders and powders such as sintering aids are suspension-polymerized with various binders such as polyvinyl alcohol (PVA) and polyethylene glycol (PEG), and non-crosslinkable styrene polymers and styrene-acrylic copolymers. With the pore-forming agent of, for example, a barrel mill, a rotary mill, a vibration mill, a bead mill, a sand mill, an agitator mill, etc., are mixed and pulverized by a wet process to obtain a slurry, and the same steps as in the manufacturing method of the first embodiment are performed. Can be manufactured. Here, the addition amount of the pore forming agent is, for example, 7 parts by mass or more and 11 parts by mass or less with respect to 100 parts by mass in total of the third starting material and the binder.

[Fourth Embodiment of Porous Ceramics]
Further, the porous ceramics that constitutes the portion including the facing surface of the welding end tab 10 contains silicon nitride as a main component, contains an oxide of a rare earth element, magnesium and aluminum, and the content of aluminum is converted into an oxide. The silicon nitride ceramics may be 0.6% by mass or less (excluding 0% by mass).

When the porous ceramic contains oxides of rare earth elements, magnesium and aluminum, the oxide acts as a sintering aid to enhance the mechanical properties of the porous ceramic. In addition, since the content of aluminum oxide is 0.6% by mass or less (excluding 0% by mass), the corrosion resistance of the porous ceramics to acid can be increased, so that the acid slag is generated during welding. When many occur, it can be preferably used for a long period of time.

Furthermore, when the porous ceramic contains rare earth elements, oxides of magnesium and aluminum, the oxide of magnesium and aluminum may be magnesium aluminate. With such a configuration, the mechanical properties of the porous ceramics can be enhanced, and the corrosion resistance of the porous ceramics to alkali can be enhanced. Therefore, during welding, if a large amount of basic slag is generated, It can be preferably used for a long period of time.

The contents of the rare earth elements, the oxides of magnesium and aluminum may be converted into oxides based on the contents of the respective elements obtained by XRF or ICP.

The grain boundary phase 8 may include at least one of RESiO ₂ N, RE ₂ Si ₃ O ₃ N ₄ , RE ₄ Si ₂ O ₇ N ₂ and RE ₅ Si ₃ O ₁₂ N (RE: rare earth element). Good.

When these silicate oxynitrides are contained in the grain boundary phase 8, the abundance ratio of the amorphous phase composed of the easily deformable oxide of the metal element is relatively small in the grain boundary phase 8. Since the deformation of the field phase 8 can be suppressed, the rigidity of the molten metal end tab can be increased.

Further, since the heat resistance is improved as compared with the case where the grain boundary phase 8 contains only the amorphous phase and the oxide, the deformation at high temperature can be suppressed.

The form of magnesium aluminate and siliconitride can be confirmed by measuring with an X-ray diffractometer (XRD) or an X-ray microanalyzer (EPMA).

[Manufacturing Method of Embodiment 4 of Porous Ceramics]
In order to obtain the fourth embodiment of the porous ceramics, first, a third powder obtained by weighing the powder of the second metal compound as a sintering aid is obtained. Here, when the total amount of the third powder and the first powder used in the manufacturing method of the third embodiment is 100% by mass, the content of the third powder is 8.6% by mass or more and 18.6% by mass or less. The powder weighed in the above is used as the fourth starting material. The second metal compound is a rare earth oxide, a magnesium compound such as magnesium hydroxide, magnesium oxide or magnesium carbonate, aluminum oxide or the like. More specifically, when the total amount of the first powder and the third powder is 100% by mass, the powder of rare earth oxide is 7% by mass or more and 14% by mass or less, and the powder of magnesium hydroxide, magnesium oxide or magnesium carbonate is 1 mass% or more and 4 mass% or less, and the powder of aluminum oxide may be 0.6 mass% or less (however, 0 mass% is not included).

The fourth starting material together with various binders such as polyvinyl alcohol (PVA) and polyethylene glycol (PEG), and a pore-forming agent such as suspension-polymerized non-crosslinkable styrene polymer or styrene-acrylic copolymer, For example, a barrel mill, a rotary mill, a vibration mill, a bead mill, a sand mill, an agitator mill, or the like may be charged and wet-mixed and pulverized to form a slurry, which can be manufactured through the same steps as the manufacturing method of the first embodiment. .. Here, the addition amount of the pore-forming agent is, for example, 7 parts by mass or more and 11 parts by mass or less with respect to 100 parts by mass of the total of the fourth starting material and the binder.

Hereinafter, a method for manufacturing the porous ceramics having a main component different from silicon nitride will be described.

[Method for producing porous ceramics whose main component is silicon carbonitride]
First, a powder of silicon carbide and a powder of silicon nitride, and a powder of yttrium oxide and a powder of magnesium oxide are prepared as a sintering aid. Then, the powder of silicon carbide, the powder of silicon nitride, and the powder of the sintering aid are mixed to obtain a fifth starting material. The mass ratio of the silicon carbide powder to the silicon nitride powder is 10:90 to 20:80.

Moreover, each powder of yttrium oxide and magnesium oxide is 3 mass% or more and 8 mass% or less of yttrium oxide powder, and 5 mass% or more and 15 mass% of magnesium oxide powder among 100 mass% of the total of the fifth starting material. Weigh it so that it does not exceed %.

Then, the fifth starting material is mixed with various binders such as polyvinyl alcohol (PVA) and polyethylene glycol (PEG), and a pore-forming agent such as suspension-polymerized non-crosslinkable styrene polymer or styrene-acrylic copolymer. At the same time, for example, a barrel mill, a rotary mill, a vibration mill, a bead mill, a sand mill, an agitator mill, or the like is charged and wet mixed and pulverized to obtain a slurry. Here, the addition amount of the pore forming agent is, for example, 7 parts by mass or more and 11 parts by mass or less based on 100 parts by mass of the total amount of the fifth starting material and the binder. Further, a thickening stabilizer, a dispersant, a pH adjuster and the like may be added. For granulation, molding and degreasing, the same method as the method of manufacturing the porous ceramic according to the first embodiment may be used.

Then, the degreased body is fired by keeping the temperature at 1640° C. or higher and lower than 1800° C. for 1 to 10 hours in an inert gas atmosphere, and then allowed to cool to room temperature, whereby the welding end tab of the present embodiment is obtained. Obtainable.

[Method for producing porous ceramics whose main component is silicon carbide]
First, a powder of silicon carbide, a powder of boron carbide as a sintering aid, and a carbon source of lignin sulfonate and lignin carboxylate or phenol are prepared. Then, the powder of silicon carbide, the powder of boron carbide and the carbon source are mixed to obtain a sixth starting material. Then, the sixth starting material is mixed with various binders such as polyvinyl alcohol (PVA) and polyethylene glycol (PEG), and a pore-forming agent such as suspension-polymerized non-crosslinkable styrene polymer or styrene-acrylic copolymer. At the same time, for example, a barrel mill, a rotary mill, a vibration mill, a bead mill, a sand mill, an agitator mill, or the like is charged and wet mixed and pulverized to obtain a slurry. Here, the addition amount of the pore-forming agent is, for example, 7 parts by mass or more and 11 parts by mass or less based on 100 parts by mass of the sixth starting material and the binder. Further, a thickening stabilizer, a dispersant, a pH adjuster and the like may be added. For granulation, molding and degreasing, the same method as the method shown in the manufacturing method of the first embodiment of the porous ceramics may be used.

Then, the degreased body is fired by holding the temperature at 1800° C. or higher and 2200° C. or lower for 1 to 10 hours in an inert gas atmosphere, and then allowed to cool to room temperature, whereby the welding end tab of the present embodiment is obtained. Obtainable.

[Method for producing porous ceramics whose main component is aluminum titanate]
First, the powder of aluminum oxide was 27 to 33 mass %, the powder of ferric oxide was 13 to 17 mass %, the powder of magnesium oxide was 7 to 13 mass %, and the balance was titanium oxide powder, and these powders were prepared. The compounding ingredients are mixed to obtain a seventh starting material. Then, the slurry obtained by mixing the seventh starting material with water, acetone or 2-propanol is dried by a spray drying method or the like to obtain, for example, granules having an average particle size of 50 μm or more and 300 μm or less. It is preferable that each of the above-mentioned powders to be used has a high purity, and the purity thereof is 99.0% by mass or more, and particularly preferably 99.5% by mass or more. If magnesium titanate (MgTi ₂ O ₅ ) and iron titanate (Fe ₂ TiO ₅ ) can be dissolved in aluminum titanate (Al ₂ TiO ₅ ) as a solid solution, in addition to these metal oxide powders, Powders such as carbonates, hydroxides and nitrates may be used, or powders of these compounds may be used.

Next, the obtained granules are calcinated in the atmosphere at a temperature of 1400° C. or higher and 1500° C. or lower for 1 hour or more and 5 hours or less, so that the pseudo-brookite in which the elements Ti, Al, Mg and Fe form a solid solution with each other. A calcined powder consisting of mold crystals can be obtained.

This calcined powder is passed through a mesh sieve having a particle size number of 230 described in ASTM E 11-61 to obtain, for example, a calcined powder having a particle size of 25 μm or more and 61 μm or less. Then, for example, the average particle size is 1 μm or more and 3 μm or less, and the addition amount is 0.4 parts by mass or more and 1.2 parts by mass or less with respect to 100 parts by mass of the calcining powder. A powder of silicon oxide, a pore-forming agent such as graphite, starch or polyethylene resin whose addition amount is 1 part by mass or more and 13 parts by mass or less with respect to 100 parts by mass of the calcined powder, polyvinyl alcohol (PVA), Along with various binders such as polyethylene glycol (PEG), for example, a barrel mill, a rotary mill, a vibration mill, a bead mill, a sand mill or an agitator mill is put and mixed and pulverized by a wet method to obtain a slurry. Further, a thickening stabilizer, a dispersant, a pH adjuster and the like may be added. For granulation, molding and degreasing, the same method as the method shown in the manufacturing method of the first embodiment of the porous ceramics may be used.

Then, the degreased body is fired by holding the temperature at 1300° C. or more and 1500° C. or less for 1 to 10 hours in the air atmosphere, and then allowed to cool to room temperature to obtain the welding end tab of the present embodiment. You can

Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and it goes without saying that various improvements and modifications may be made without departing from the scope of the present invention. is there.

1: First Metal Member 2: Second Metal Member 3: Third Metal Member 4: Fourth Metal Member 5: Clamping Wire 6: Backing Metal 7: Silicon Nitride Crystal 8: Grain Boundary Phase 9: First Opening Pore 10: End tab for welding

Claims (9)

A welding end tab having a facing surface arranged to face a member to be welded,
Portion including the facing surface, a porous ceramic mainly containing silicofluoride-containing nitride,
The facing surface includes a plurality of first open pores, wherein the facing surface, end tabs for welding the carbon content, characterized in der Rukoto 40 atomic% or more. A second open pore is provided on a surface portion different from the facing surface,
The welding end tab according to claim 1, wherein the second open hole communicates with the first open hole. The main component of the porous ceramics is silicon nitride, and a plurality of columnar crystals of silicon nitride are located inside the first open pores so as to intersect with each other. End tab for welding. 4. The porous ceramics, whose main component is silicon nitride, contains a silicide containing at least one of chromium, manganese, iron, copper, tungsten and molybdenum. The welding end tab described in. The main component of the porous ceramics is silicon nitride, Y2SiAlO5N is contained in the grain boundary phase, and the peak intensity of Y2SiAlO5N at 2θ=32 to 33° in the X-ray diffraction chart is X, 2θ=33.2 to 34. The welding end tab according to any one of claims 1 to 4 , wherein the ratio X/Y is 0.1 or more and 0.5 or less, where Y is the peak intensity of 2° of silicon nitride. .. The porous ceramics is mainly composed of β-sialon represented by a composition formula of Si6-ZAlZOZN8-Z (z=0.1-1), contains calcium, aluminum and an oxide of a rare earth element, Of the total 100 mass% of aluminum and oxides of rare earth elements, the calcium content is 0.3 mass% to 1.5 mass% in terms of oxide, and the aluminum content is in oxide. The content is 14.2% by mass or more and 48.8% by mass or less, and the balance is an oxide of a rare earth element, and the average particle size of the crystal particles of β-sialon is 20 μm or less (excluding 0 μm). The welding end tab according to any one of claims 1 to 5 . The main component of the porous ceramics is silicon nitride, which contains gehlenite, and the half value width of the peak intensity of the gehrenite at 2θ=31° to 32° in the X-ray diffraction chart is 0.5° or less. The welding end tab according to any one of claims 1 to 6 . The main component of the porous ceramics is silicon nitride and contains oxides of rare earth elements, magnesium and aluminum, and the content of aluminum is 0.6% by mass or less (however, 0% by mass is calculated as oxides). Is not included.) The welding end tab according to any one of claims 1 to 7 . The main component of the porous ceramics is silicon nitride, contains an oxide of a rare earth element, and contains at least one of RESiO2N, RE2Si3O3N4, RE4Si2O7N2 and RE5Si3O12N (RE: rare earth element) in the grain boundary phase. The welding end tab according to any one of claims 1 to 8 .

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