(19)
(11)EP 1 226 911 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
16.01.2008 Bulletin 2008/03

(21)Application number: 02250561.4

(22)Date of filing:  28.01.2002
(51)Int. Cl.: 
B28B 3/26  (2006.01)
C25D 7/00  (2006.01)
C23C 16/36  (2006.01)
B21C 25/02  (2006.01)
C23C 28/00  (2006.01)
C23C 16/34  (2006.01)
C23C 16/02  (2006.01)

(54)

Method of manufacturing honeycomb extrusion die and die manufactured according to this method

Verfahren zur Herstellung einer Strangpressdüse für Wabenstruktur sowie dadurch erhaltene Strangpressdüse

Procédé de fabrication d'une matrice d'extrusion pour structures en nid d'abeilles et matrice ainsi obtenue


(84)Designated Contracting States:
BE CH DE LI

(30)Priority: 29.01.2001 JP 2001019702

(43)Date of publication of application:
31.07.2002 Bulletin 2002/31

(73)Proprietor: NGK INSULATORS, LTD.
Nagoya-City, Aichi Pref. 467-8530 (JP)

(72)Inventors:
  • Asai, Yuji
    Nagoya City, Aichi Pref. (JP)
  • Furutani, Makoto
    Nagoya City, Aichi Pref. (JP)
  • Matsumoto, Keiji
    Nagoya City, Aichi Pref. (JP)

(74)Representative: Paget, Hugh Charles Edward et al
Mewburn Ellis LLP York House 23 Kingsway
London WC2B 6HP
London WC2B 6HP (GB)


(56)References cited: : 
DE-A- 19 810 076
US-A- 3 656 995
  
  • PATENT ABSTRACTS OF JAPAN vol. 018, no. 668 (C-1289), 16 December 1994 (1994-12-16) -& JP 06 264213 A (SEKISUI CHEM CO LTD), 20 September 1994 (1994-09-20)
  • PATENT ABSTRACTS OF JAPAN vol. 009, no. 057 (M-363), 13 March 1985 (1985-03-13) & JP 59 193713 A (HITACHI KINZOKU KK;OTHERS: 01), 2 November 1984 (1984-11-02)
  • PATENT ABSTRACTS OF JAPAN vol. 2000, no. 12, 3 January 2001 (2001-01-03) & JP 2000 246330 A (AISIN KEIKINZOKU CO LTD), 12 September 2000 (2000-09-12)
  
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description

Background of the invention


(1) Field of the Invention



[0001] The present invention relates to a method of manufacturing a honeycomb extrusion die used for extruding a ceramic honeycomb structural body and a honeycomb extrusion die.

(2) Prior Art Statement



[0002] Generally, as a die for extruding a ceramic honeycomb structural body, a honeycomb extrusion die is known in which a plurality of intersecting slits are arranged in a front surface of a die base metal and a plurality of raw material feeding holes communicated with the slits are arranged in a back surface of the die base metal. In such a honeycomb extrusion die, in order to improve a wear resistance of the slits, there is disclosed a technique in JP-A-60-145804 in which at least a part of the die base metals defining the slits is formed by coating iron boride, chromium carbide, aluminum oxide, titanium carbide, titanium nitride or titanium nitride carbide by means of CVD (chemical vapor deposition).

[0003] However, in the case that a TiN layer and a TiCN layer are to be formed successively on the die base metal made of for example martensite stainless steel by utilizing the CVD technique, it is known that, if a thickness of the TiN layer or the TiCN layer becomes thicker, a chipping (film peeling off after film formed) is easily generated. This chipping is easily generated particularly at round (R) portions formed by rounding corner portions of the die base metal defining the slits. If the chipping is generated, a coating defect occurs. Therefore, there is a problem such that a productivity of the ceramic honeycomb structural body becomes worse.

[0004] On the contrary, the applicant discloses a technique not for eliminating the chipping generation but for narrowing a slit width of the die base metal, in JP-A-10-309713, such that an electroless plating layer made of for example Ni is formed on the die base metal and the TiCN layer and a W2C layer is formed on the electroless plating layer by means of CVD. However, if this technique is utilized for eliminating the chipping generation, there occurs following problems. That is, P is included in the electroless plating layer made of for example Ni as an impurity. Therefore, if the TiN layer and the TiCN layer are formed on the electroless Ni-P plating layer by CVD, the plating layer and the CVD layer are reacted and it is not possible to obtain normal TiCN particles.
DE-A-19810076 describes a honeycomb extrusion die having a double coating layer on the slit surfaces. The first relatively thick coating layer is formed by electroless plating, preferably of Ni, and has a thickness of 10-70 µm. The second relatively thin coating layer of preferably TiCN or W2C formed by CVD has a thickness of 5 - 30 µm. The purpose is to form rounded portions at the corners of the cell blocks defining the slits.
JP-A-06-264213 describes formation of a thin Ti coating of thickness 0.1 to 1 µm and a TiN coating of thickness 1 to 3 µm on a metal surface of industrial tools or dies, to improve adhesion of a TiCN or TiC layer. The layers are all formed by ion plating.

Summary of the Invention



[0005] An object of the present invention is to eliminate the drawbacks mentioned above and to provide a method of manufacturing a honeycomb extrusion die and a die according to this method in which a coating layer with no chipping can be formed on a die base metal and a productivity of a ceramic honeycomb structural body during an extrusion operation can be improved.
According to a first aspect of the invention there is provided a method of manufacturing a honeycomb extrusion due as set out in claim 1.
Moreover, according to a second aspect of the invention there is provided a honeycomb extrusion as set out in claim 2.

[0006] In the present invention, since the electrolytic plating layer is arranged between the die base metal and the TiCN layer or between the die base metal and the TiN layer, a contact property therebetween can be improved, so that the chipping is not easily generated if a thickness of the film is thicker. Moreover, since the plating layer is made of the metal and the metal has an excellent stiffness, it is possible to reduce a heat stress between the die base metal and the TiCN layer or the TiN layer, and thus the chipping is not easily generated. Further, since the amount of impurity in the electrolytic plating layer is very small, it is possible to obtain normal TiCN particles.

Brief Description of the Drawing



[0007] For a better understanding of the present invention, explanations are made to the following drawings wherein:

Fig. I is a flowchart for explaining a method of manufacturing a honeycomb extrusion die according to the invention;

Figs. 2a and 2b are schematic views respectively showing one embodiment of a honeycomb extrusion die according to the invention;

Fig. 3 is a schematic view illustrating an enlarged part of the honeycomb extrusion die according to the invention;

Fig. 4 is a SEM photograph depicting a cross section of the die according to an example of the invention;

Fig. 5 is a SEM photograph showing a cross section of a die according to a comparative example; and

Fig. 6 is a SEM photograph illustrating a chipping state in the comparative example.


Description of the Preferred Embodiments



[0008] Fig. 1 is a flowchart for explaining a method of manufacturing a honeycomb extrusion die according to the invention. According to the flowchart shown in Fig. 1, two methods of manufacturing a honeycomb extrusion die according to the invention will be explained. At first, in the both embodiments, a die base metal, in which a plurality of intersecting slits are arranged in a front surface thereof and a plurality of raw material feeding holes communicated with the slits are arranged in a back surface thereof, is prepared (step 1). As a material of the die base metal, use may be made of all the materials that are conventionally used for the die base metal. For example, a martensite stainless steel can be preferably used. Moreover, workings of the slits and the raw material feeding holes may be performed by conventional methods. For example, the slits can be formed by EDM (Electro-discharged machining) process and/or wheel grinding process. Further, the raw material feeding holes can be formed by ECM (Electro-chemical machining) process.

[0009] Then, a plating layer is formed on the thus prepared die base metal by means of electrolytic plating (step 2). As a material of the plating layer, Ni is used.
In this case, since Ni used for electrolytic plating is a pure metal, it is possible to obtain normal TiCN particles. However, since Ni contains a little amount of Co as an impurity at a rate of 1/100 of Ni, Ni is not a pure metal but an alloy if strictly speaking. Moreover, as a method of forming the plating layer made of Ni by means of electrolytic plating, use may be made of the known methods such as method of using a wood-strike bath, method of using a sulfamic acid bath, method of using a watt bath and method of using an immersion nickel bath.
Further, in the case that a film is directly formed on the die base metal by means of CVD, a composition of the die base metal is limited (that is, in accordance with a composition of the die base metal, the film is formed normally in some cases but the film is not formed in the other cases). However, in the case that the film is formed by electrolytic plating, a composition of the die base metal is not limited (that is, all the compositions of the die base metal are used if only electrolytic plating can be performed on the die base metal). Furthermore, the thickness of the electrolytic plating layer is not less than 0.01 µm. If this thickness is less than 0.01 µm, nitriding and oxidizing of the die base metal occur, and a contacting performance after forming the film is decreased. However, an upper limit of this thickness is determined on the basis of the other conditions such as economical efficiency.

[0010] Then, in the first method of the invention, a TiCN layer is formed on the electrolytic plating layer by means of CVD (step 3). Moreover, in the second method of the invention, a TiN layer is formed on the electrolytic plating layer by means of CVD (step 4), and then a TiCN layer is formed on the TiN layer by means of CVD (step 5). In both embodiments, since the electrolytic plating layer is arranged, it is possible to achieve an excellent contacting performance with no chipping. In this case, since the TiCN layer limits a material of the electrolytic plating layer by means of CVD to achieve an excellent contacting performance, it is easy to use the second method of the invention using the TiN layer, which does not limit a material of the electrolytic plating layer by means of CVD as compared with the TiCN layer.

[0011] In the present invention mentioned above, it is possible to improve a contacting performance between the die base metal and the TiCN layer of between the die base metal and the TiN layer by arranging the electrolytic plating layer between the die base metal and the TiCN layer or between the die base metal and the TiN layer. This reason is estimated as follows. That is, in the case that the TiCN layer or the TiN layer is to be formed directly on the die base metal made of stainless steel by means of CVD, since stainless steel has a thin Cr oxide (a few nm) on its surface layer, a contacting performance is reduced due to this Cr oxide. In addition, in the case that the TiN layer and the TiCN layer are formed, N2 (nitrogen) gas is flowed during a TiN layer forming operation. In this case, a nitriding layer (CrN, FeN and so on) is formed due to this N2 gas, and thus this nitriding layer decreases its contacting strength. In the present invention, the electrolytic plating layer made of Ni is formed on a surface of the die base metal made of stainless steel, and the TiCN layer or the TiN layer and the TiCN layer is (are) formed on the electrolytic plating layer by means of CVD. Therefore, these phenomena such as a nitriding layer generation do not occur, and thus it is possible to improve the contacting performance between the die base metal and the TiCN layer or between the die base metal and the TiN layer. That is, since Ni is not easily oxidized or nitrided as compared with Cr or Fe, the above advantage can be obtained.

[0012] Moreover, in the present invention mentioned above, since the plating layer is made of a metal which shows an excellent stiffness, it is possible to reduce a heat stress between the die base metal and the TiCN layer or the TiN layer. For reference, thermal expansion coefficients of TiCN, TiN, martensite stainless steel, Ni and Co are shown in the following Table 1.
As is clearly understood from the thermal expansion coefficients shown in the following Table 1, since, in the present invention, Ni having an intermediate thermal expansion coefficient between those of the die base metal and the film is inserted between the die base metal and the film, it is possible to reduce a heat stress. Moreover, since Ni is a pure metal, it has excellent stiffness and thus it is possible to absorb a heat stress.

[0013] 
Table 1
MaterialThermal expansion coefficient (/°C)
TiCN 8.1 × 10-6
TiN 9.3×10-6
Ni 16.5× 10-6
Co 12.0× 10-6
Martensite stainless steel 19.5×10-6 (At descending temperature from film forming temperature of near 800°C to room temperature)


[0014] Fig. 2 is a schematic view showing one embodiment of a honeycomb extrusion die according to the invention, wherein Fig. 2a illustrates its plan view and Fig. 2b depicts its cross sectional view along A-A line. In the embodiment shown in Figs. 2a and 2b, a honeycomb extrusion die 1 is constructed in such a manner that intersecting slits 2 are arranged on its front surface by using a plurality of cell blocks 3 and raw material feeding holes 4 communicated with the slits 2 at its intersecting portion are arranged on its back surface. A batch to be formed is supplied through the raw material feeding holes 4 arranged on its back surface into the die 1, and a honeycomb formed body is extruded from the slits 2 arranged on its front surface. A feature of the honeycomb extrusion die 1 according to the invention is that, as shown in Fig. 3, respective cell blocks 3 comprises a die base metal 11, an electrolytic plating layer 14 arranged on the die base metal 11, a TiN layer 12 arranged on the electrolytic plating layer 14 by means of CVD, and a TiCN layer 13 arranged on the TiN layer 12 by means of CVD. In the case that the TiCN layer 13 is arranged directly on the electrolytic plating layer 14, the TiN layer 12 is not arranged in Fig. 3.

[0015] Hereinafter, an actual experiment will be explained.

Experiment



[0016] As the die base metal, use was made of martensite stainless steel. The slits and the raw material feeding holes were formed to the die base metal by performing ECM process and/or wheel grinding process. Moreover, R portion (formed by electrolytic process) having a round portion was arranged to corners of surfaces of respective die base metals to which the slit was formed. Then, with respect to the die base metal, electrolytic plating process using a material shown in the following Table 2 was performed, and a plating layer having a thickness shown in Table 2 was formed on a die surface. Conditions of electrolytic plating process were pH: not more than 1.5, bath temperature: room temperature and current density: 5-20 A/dm2 in the case of wood-strike bath and were pH: 3-5, bath temperature: 20-70°C and current density: 2-20 A/dm2 in the case of sulfamic acid bath, and the experiment was performed according to the plating methods shown in Table 2. After that, the single TiCN layer or the TiN layer and the TiCN layer in this order with a thickness shown in Table 2 was (were) formed as shown in Table 2 at a temperature of 700-850°C by means of CVD. In the case of forming the TiN layer and the TiCN layer, a thickness was calculated by their sum. In this manner, the die according to the example of the present invention was manufactured. Moreover, a die according to a comparative example, in which the electrolytic plating layer was not arranged, was also manufactured as shown in Table 2. With respect to the dies according to the example of the present invention and the comparative example, whether the chipping was generated or not and positions at which the chipping was generated were observed. The results were shown in Table 2.

[0017] 
Table 2
 Die base metalPlating materialPlating methodPlating thickness (µm)Film kindsFilm thickness (µm)Chipping state
Examples of present invention Martensite stainless steel Ni Wood-strike bath 0.1 TiN+TiCN 10 No Chipping
Martensite stainless steel Ni Wood-strike bath 0.1 TiN+TiCN 20 No Chipping
Martensite stainless steel Ni Wood-strike bath 0.1 TiN+TiCN 30 No Chipping
Martensite stainless steel Ni Wood-strike + sulfamic acid bath 1 TiN+TiCN 25 No Chipping
Martensite stainless steel Ni Wood-strike + sulfamic acid bath 3 TiN+TiCN 25 No Chipping
Martensite stainless steel Ni Wood-strike + sulfamic acid bath 8 TiN+TiCN 25 No Chipping
Martensite stainless steel Ni Wood-strike bath 0.1 TiCN 15 No Chipping
Martensite stainless steel Ni Wood-strike bath 0.1 TiCN 22 No Chipping
Comparative examples Martensite stainless steel No plating No plating - TiN+TiCN 15 Chipping (R portion)
Martensite stainless steel No plating No plating - TiN+TiCN 23 Chippings (R portion and edge portion)


[0018] As clearly understood from the results shown in Table 2, in the example of the present invention, the chipping was not generated, but, in the comparative example, the chipping was generated particularly at the R portions. For reference, a cross sectional photograph after forming the film according to the example of the present invention (die base metal + electrolytic Ni layer + TiN layer + TiCN layer) was shown in Fig. 4, and a cross sectional photograph after forming the film according to the comparative example (die base metal + TiN layer) was shown in Fig. 5. In both cases, a die cut-out cross section was polished and the etched, and then the cross section was observed by the scanning electron microscope (SEM). If the example of the present invention shown in Fig. 4 and the comparative example shown in Fig. 5 are compared, it is understood that, in the example of the present invention shown in Fig. 4, respective layers are contacted strongly, but, in the comparative example shown in Fig. 5, a corroded portion between the die base metal and the TiN layer is shown by black and a failure connection is generated between them. Moreover, Fig. 6 shows a chipping state after forming the film in the comparative example having a film thickness of 15 µm.

[0019] As clearly understood from the above explanations, according to the invention, since the electrolytic plating layer is arranged between the die base metal and the TiCN layer or between the die base metal and the TiN layer, a contact property therebetween can be improved, so that the chipping is not easily generated if a thickness of the film is thicker. Moreover, since the plating layer is made of the metal and the metal has an excellent stiffness, it is possible to reduce a heat stress between the die base metal and the TiCN layer or the TiN layer, and thus the chipping is not easily generated. Further, since an impurity in the electrolytic plating layer is very little, it is possible to obtain normal TiCN particles.


Claims

1. A method of manufacturing a honeycomb extrusion die (1) comprising the steps of:

preparing a die base metal in which a plurality of intersecting slits (2) are arranged in a front surface thereof and a plurality of raw material feeding holes (14) communicated with the slits (2) are arranged in a back surface thereof;

forming a plating layer on the-die base metal; and

either (i) forming a TiCN layer on the plating layer by means of chemical vapor deposition or (ii) forming a TiN layer on the plating layer by means of chemical vapor deposition and forming a TiCN layer on the TiN layer by means of chemical vapor deposition;

wherein the plating layer is made of Ni and is formed by electrolytic plating, and the plating layer has a thickness in the range 0.01 to 8 µm.


 
2. A honeycomb extrusion die (1) comprising a die base metal in which a plurality of intersecting slits (2) are arranged in a front surface thereof and a plurality of raw material feeding holes (14) communicated with the slits (2) are arranged in a back surface thereof, an electrolytically plated layer made of Ni having a thickness in the range 0.01 to 8 µm on the die base metal, and either (i) a TiCN layer formed by chemical vapor deposition on the electrolytically plated layer or (ii) a TiN layer formed by chemical vapor deposition on the electrolytically plated layer and a TiCN layer formed by chemical vapour deposition on the TiN layer.
 


Ansprüche

1. Verfahren zur Herstellung einer Wabenstruktur-Strangpressdüse (1), umfassend die folgenden Schritte:

Vorbereiten eines Düsenbasismetalls, in dem eine Vielzahl an sich kreuzenden Schlitzen (2) in einer vorderen Oberfläche desselben angeordnet ist und eine Vielzahl an Rohmaterial-Zufuhrlöchern (14), die mit den Schlitzen (2) in Kommunikation stehen, in einer hinteren Oberfläche desselben angeordnet ist,

Ausbilden einer Abscheidungsschicht auf dem Düsenbasismaterial und

entweder (i) Ausbilden einer TiCN-Schicht auf der Abscheidungsschicht mittels chemischer Gasphasenabscheidung oder (ii) Ausbilden einer TiN-Schicht auf der Abscheidungsschicht mittels chemischer Gasphasenabscheidung und Ausbilden einer TiCN-Schicht auf der TiN-Schicht mittels chemischer Gasphasenabscheidung,

wobei die Abscheidungsschicht aus Ni hergestellt ist und durch elektrolytisches Beschichten ausgebildet ist und die Abscheidungsschicht eine Dicke im Bereich von 0,01 bis 8 µm hat.


 
2. Wabenstruktur-Strangpressdüse (1), umfassend ein Düsenbasismetall, in welchem eine Vielzahl an sich kreuzenden Schlitzen (2) in einer vorderen Oberfläche desselben angeordnet ist und eine Vielzahl an Rohmaterial-Zufuhrlöchern (14), die in Kommunikation mit den Schlitzen (2) stehen, in einer hinteren Oberfläche desselben angeordnet ist, wobei eine elektrolytisch abgeschiedene Schicht aus Ni eine Dicke im Bereich von 0,01 bis 8 µm auf dem Düsenbasismaterial aufweist und entweder (i) eine TiCN-Schicht durch chemische Gasphasenabscheidung auf der elektrolytisch abgeschiedenen Schicht ausgebildet ist oder (ii) eine TiN-Schicht durch chemische Gasphasenabscheidung auf der elektrolytisch abgeschiedenen Schicht ausgebildet ist und eine TiCN-Schicht durch chemische Gasphasenabscheidung auf der TiN-Schicht ausgebildet ist.
 


Revendications

1. Procédé pour fabriquer une matrice d'extrusion en nid d'abeilles (1) comprenant les étapes consistant à :

préparer un métal de base de matrice dans lequel une pluralité de fentes d'intersection (2) est agencée sur sa surface avant et une pluralité de trous d'alimentation de matière première (14) en communication avec les fentes (2) est agencée sur sa surface arrière,

former une couche de placage sur le métal de base de matrice ; et

soit (i) former une couche de TiCN sur la couche de placage au moyen du dépôt chimique en phase de vapeur soit (ii) former une couche de TiN sur la couche de placage au moyen du dépôt chimique en phase de vapeur et former une couche de TiCN sur la couche de TiN au moyen du dépôt chimique en phase de vapeur;

dans lequel la couche de placage est réalisée à partir de Ni et est formée par placage électrolytique et la couche de placage a une épaisseur de l'ordre de 0,01 à 8 µm.


 
2. Matrice d'extrusion en nid d'abeilles (1) comprenant un métal de base de matrice dans lequel une pluralité de fentes d'intersection (2) est agencée sur sa surface avant et une pluralité de trous d'alimentation de matière première (14) en communication avec les fentes (2) est agencée sur sa surface arrière, une couche plaquée de manière électrolytique réalisée à partir de Ni ayant une épaisseur de l'ordre de 0,01 à 8 µm sur le métal de base de matrice et (i) une couche de TiCN formée par dépôt chimique en phase de vapeur sur la couche plaquée de manière électrolytique ou (ii) une couche de TiN formée par dépôt chimique en phase de vapeur sur la couche plaquée de manière électrolytique et une couche de TiCN formée par dépôt chimique en phase de vapeur sur la couche de TiN.
 




Drawing


















REFERENCES CITED IN THE DESCRIPTION



This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description